Updated on 2022/04/08

写真a

 
HIBINO, Takashi
 
Organization
Graduate School of Environmental Studies Department of Environmental Engineering and Architecture Functional Materials and Environment Professor
Graduate School
Graduate School of Environmental Studies
Undergraduate School
School of Engineering Architecture
Title
Professor
Contact information
メールアドレス

Degree 1

  1. 工学博士 ( 1991.3   名古屋大学 ) 

Research Interests 5

  1. エネルギー材料

  2. 燃料電池

  3. 水素生成

  4. 廃バイオマス・プラスチック

  5. 炭素資源活用

Research Areas 2

  1. Environmental Science/Agriculture Science / Environmental materials and recycle technology  / 資源・水素製造

  2. Energy Engineering / Earth resource engineering, Energy sciences  / エネルギー・燃料電池発電

Current Research Project and SDGs 4

  1. 廃バイオマス・プラスチック利用

  2. 燃料電池開発

  3. 水素製造

  4. CO2電解

Research History 4

  1. 名古屋大学工学部助手

    1991.4 - 1994.12

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    Country:Japan

  2. 通商産業省工業技術院名古屋工業技術研究所(現、独立行政法人産業技術総合研究所)主任研究員

    1995.1 - 2004.3

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    Country:Japan

  3. 名古屋大学大学院環境学研究科教授

    2004.4

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    Country:Japan

  4. Nagoya University   Director in General

    2006.4 - 2009.3

Education 1

  1. Nagoya University   Graduate School, Division of Engineering

    - 1991

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    Country: Japan

Professional Memberships 5

  1. 電気化学会   東海支部幹事

    2000.4 - 2013.12

  2. 電気化学会   編集委員

    2007.4 - 2010.3

  3. 化学センサ研究会   編集委員

    2009.4

  4. 化学センサ研究会   理事

  5. 日本セラミックス協会

Awards 6

  1. Certificate of Collaboration & Appreciation

    2019.12   Chinese Academy of Sciences  

    Takashi Hibino

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    Country:China

  2. 日本セラミックス協会学術賞

    2011.6   日本セラミックス協会  

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    Country:Japan

  3. 永井科学技術財団学術賞

    2011.3   永井科学技術財団  

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    Country:Japan

  4. 化学センサ研究会清山賞

    2009.1   化学センサ研究会  

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    Country:Japan

  5. 触媒学会奨励賞

    2002.3   触媒学会  

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    Country:Japan

  6. 東海化学工業会学術賞

    1998.5   東海化学工業会  

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    Country:Japan

▼display all

 

Papers 408

  1. Solid oxide fuel cell using plastic waste directly as fuel Reviewed

    Takashi Hibino, Kazuyo Kobayashi, Takuma Hitomi

    Chemistry Letters   Vol. 50 ( 10 ) page: 1729 - 1732   2021.10

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1246/cl.210321

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  2. Biomass solid oxide fuel cell using solid weed waste as fuel Reviewed

    Takashi Hibino, Kazuyo Kobayashi, Takuma Hitomi

    Electrochimica Acta   Vol. 388   page: 138681   2021.8

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1016/j.electacta.2021.138681

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  3. Solid oxide fuel cell using municipal solid waste directly as fuel: biomass, resin, plastic, and food waste Reviewed

    Takashi Hibino, Kazuyo Kobayashi, Shinya Teranishi, Takuma Hitomi

    ACS Sustainable Chemistry & Engineering   Vol. 9 ( 8 ) page: 3124 - 3136   2021.3

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/acssuschemeng.0c07657

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  4. A NiRhS fuel cell catalyst-lessons from hydrogenase Reviewed

    Seiji Ogo, Tatsuya Ando, Le Tu Thi Minh, Yuki Mori, Takahiro Matsumoto, Takeshi Yatabe, Ki-Seok Yoon, Yukio Sato, Takashi Hibino, Kenji Kaneko

    Chemical Communications   Vol. 56 ( 79 ) page: 11787 - 11790   2020.10

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/d0cc04789a

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  5. Ionic conductive and photocatalytic properties of cementitious materials: calcium silicate hydrate and calcium aluminoferrite Reviewed

    Masahiro Nagao, Kazuyo Kobayashi, Yongcheng Jin, Ippei Maruyama, Takashi Hibino

    Journal of Materials Chemistry A   Vol. 8 ( 30 ) page: 15157 - 15166   2020.8

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/d0ta04866f

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  6. Fuel cell and electrolyzer using plastic waste directly as fuel Reviewed

    Tetsuya Hori, Kazuyo Kobayashi, Shinya Teranishi, Masahiro Nagao, Takashi Hibino

    Waste Management   Vol. 102   page: 30 - 39   2020.2

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1016/j.wasman.2019.10.019

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  7. A cellulose electrolysis cell with metal-free carbon electrodes Reviewed

    Yaorong Li, Masahiro Nagao, Kazuyo Kobayashi, Yongcheng Jin, Takashi Hibino

    Catalysts   Vol. 10 ( 1 ) page: 106   2020.1

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.3390/catal10010106

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  8. Humidity driven transition from insulator to ionic conductor in portland cement Reviewed

    Masahiro Nagao, Kazuyo Kobayashi, Tetsuya Hori, Yaorong Li, Takashi Hibino

    Materials   Vol. 12 ( 22 ) page: 3701   2019.11

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.3390/ma12223701

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  9. Electrolysis of humidified methane to hydrogen and carbon dioxide at low temperatures and voltages Reviewed

    Tetsuya Hori, Qiang Ma, Kazuyo Kobayashi, Masahiro Nagao, Shinya Teranishi, Takashi Hibino

    International Journal of Hydrogen Energy   Vol. 44 ( 5 ) page: 2454 - 2460   2019.1

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1016/j.ijhydene.2018.12.044

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  10. Intermediate-temperature electrolysis of energy grass Miscanthus sinensis for sustainable hydrogen production Reviewed

    Masaya Ito, Tetsuya Hori, Shinya Teranishi, Masahiro Nagao, Takashi Hibino

    Scientific Reports   Vol. 8 ( 1 ) page: 16186   2018.11

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1038/s41598-018-34544-y

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  11. Direct electrolysis of waste newspaper for sustainable hydrogen production: an oxygen-functionalized porous carbon anode Reviewed

    Hibino Takashi, Kobayashi Kazuyo, Ito Masaya, Nagao Masahiro, Fukui Mai, Teranishi Shinya

    APPLIED CATALYSIS B-ENVIRONMENTAL   Vol. 231   page: 191 - 199   2018.9

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:Applied Catalysis B: Environmental  

    Biomass electrolysis enables hydrogen (H2) production at onset voltages of less than 1 V, depending on the fuel species. However, biofuel derived from biomass not categorized as food and produced from environmentally friendly processes is needed for the development of sustainable strategies. In addition, the biofuel should not require special and expensive procedures for processing. The present report describes the direct electrolysis of waste newspaper for H2 production. Cellulose and lignin included in the newspaper were subject to dissolution and hydrolysis in a phosphoric acid solvent at the anode in a temperature range of 100–175 °C. The resulting decomposition products were electrolyzed to H2 and carbon dioxide (CO2), at low onset voltages (ca. 0.2 V) and high current efficiencies (H2: 1.0, CO2: 0.9). Carbon black functionalized with carbonyl groups showed greater catalytic activity than a Pt/C catalyst for the anode reaction. H2 yield reached ca. 0.2 g per 1 g of newspaper in a batch cell. H2 was produced continuously in a current-density range of 0.15–0.25 A cm−2 while maintaining plateau-like voltage behavior in a flow cell. The energy consumed for electrolysis at a current density of 0.15 A cm−2 was as low as 1.27 kWh (Nm3)−1.

    DOI: 10.1016/j.apcatb.2018.03.021

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  12. Efficient hydrogen production by direct electrolysis of waste biomass at intermediate temperatures Reviewed

    Takashi Hibino, Kazuyo Kobayashi, Masaya Ito, Qiang Ma, Masahiro Nagao, Mai Fukui, Shinya Teranishi

    ACS Sustainable Chemistry & Engineering   Vol. 6 ( 7 ) page: 9360 - 9368   2018.7

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/acssuschemeng.8b01701

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  13. Hydrogen production by direct Lignin electrolysis at intermediate temperatures Reviewed

    Takashi Hibino, Kazuyo Kobayashi, Masahiro Nagao, Shinya Teranishi,

    ChemElectroChem   Vol. 4 ( 12 ) page: 3032 - 3036   2017.12

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1002/celc.201700917

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  14. High performance anode for direct cellulosic biomass fuel cells operating at intermediate temperatures Reviewed

    Takashi Hibino, Kazuyo Kobayashi, Peiling Lv, Masahiro Nagao, Shinya Teranishi

    Bulletin of the Chemical Society of Japan   Vol. 90 ( 9 ) page: 1017 - 1026   2017.9

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1246/bcsj.20170163

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  15. NOx sensing characteristics of semiconductor gas sensors under controlled oxygen activity conditions using a proton-conducting electrolyte Reviewed

    Masahiro Nagao, Kazuyo Kobayashi, Peiling Lv, Shinya Teranishi, Takashi Hibino

    Journal of The Electrochemical Society   Vol. 164 ( 9 ) page: B397 - B402   2017

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1149/2.0361709jes

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  16. An intermediate-temperature biomass fuel cell using wood sawdust and pulp directly as fuel Reviewed

    Takashi Hibino, Kazuyo Kobayashi, Peiling Lv, Masahiro Nagao, Shinya Teranishi, Toshiyuki Mori,

    Journal of The Electrochemical Society   Vol. 164 ( 6 ) page: F557 - F563   2017

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1149/2.0511706jes

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  17. A self-regenerable soot sensor with a proton-conductive thin electrolyte and a nanostructured platinum sensing electrode Reviewed

    Peiling Lv, Takenori Ito, Akihide Oogushi, Kensaku Nakashima, Masahiro Nagao, Takashi Hibino,

    Scientific Reports   Vol. 6   page: 37463   2016.11

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1038/srep37463

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  18. Kinetically driven switching and memory phenomena at the interface between a proton-conductive electrolyte and a titanium electrode Reviewed

    Takashi Hibino, Kazuyo Kobayashi, Masahiro Nagao,

    Scientific Reports   Vol. 6   page: 31691   2016.8

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1038/srep31691

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  19. A Rechargeable Tin-Air PEM Battery Using SnSO4 as an Anode-active Material Reviewed

    Kobayashi Kazuyo, Nagao Masahiro, Hibino Takashi

    CHEMISTRY LETTERS   Vol. 45 ( 2 ) page: 161 - 163   2016.2

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:Chemistry Letters  

    SnSO4 was employed as an anode-active material for rechargeable batteries, where Sn4+ and Sn2+ ions are reduced to Sn2+ and Sn, respectively during charge while the inverse reactions occur during discharge. Undesired hydrogen production was substantially avoided by adjusting the charge voltage to 1.5V. The resulting cell functioned as a battery with an electrical capacity of 258mA hg-1 at 10mA cm-2 and as a fuel cell with power densities of 55-125 mW cm-2 at 0.8V.

    DOI: 10.1246/cl.151015

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  20. Rechargeable metal-air proton -exchange membrane batteries for renewable energy storage Reviewed

    Masahiro Nagao, Kazuyo Kobayashi, Yuta Yamamoto, Togo Yamaguchi, Akihide Oogushi, Takashi Hibino,

    ChemElectroChem   Vol. 3 ( 2 ) page: 247 - 255   2016.2

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    DOI: 10.1002/celc.201500473

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  21. Design of a rechargeable fuel-cell battery with enhanced performance and cyclability Reviewed

    Takashi Hibino, Kazuyo Kobayashi, Masahiro Nagao, Yuta Yamamoto,

    Journal of The Electrochemical Society   Vol. 163 ( 7 ) page: A1420 - A1428   2016

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    DOI: 10.1149/2.1341607jes

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  22. A sensitive and self-regenerable particulate matter sensor with a H<inf>3</inf>PO<inf>4</inf>-modified BaZr<inf>0.8</inf>Y<inf>0.2</inf>O<inf>3-δ</inf> electrolyte and an IrO<inf>2</inf>-catalyzed sensing electrode Reviewed

    Peiling L., Oogushi A., Nakashima K., Kobayashi K., Nagao M., Hibino T.

    Journal of the Electrochemical Society   Vol. 163 ( 14 ) page: B761 - B767   2016

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:Journal of the Electrochemical Society  

    There have been many attempts to develop solid-state sensor devices for detecting particulate matter (PM) in diesel exhaust; however, in most of these, the accumulated PM must be burned intermittently to allow subsequent sensing cycles. Here, we report a self-regenerable PM sensor using a proton conductive solid electrolyte and an active working electrode for PM oxidation. The withstanding voltage capability of BaZr0.8Y0.2O3-δ was greatly improved by the growth of a dense Zr1-xYxP2O7 film on the electrolyte surface. The reaction of PM with active oxygen under anodic polarization was further enhanced by the addition of IrO2 to the working electrode. As a result of these combined modifications, when the working electrode was anodically polarized, PM was oxidized to CO2 according to a four-electron reaction (C + 2H2O → CO2 + 4H+ + 4e-) while remaining below the self-ignition temperature. This amperometric sensor successfully produced a current signal corresponding to the quantity of PM in a gas stream at an operating temperature of 300°C. These results demonstrate that the sensor can carry out continuous monitoring of PM concentrations while self-regenerating.

    DOI: 10.1149/2.1281614jes

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  23. 総説:中温プロトン伝導体のエネルギーデバイスへの応用

    小林和代、長尾征洋、日比野高士

      Vol. 33 ( 4 ) page: 128-133   2015.10

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    Authorship:Lead author   Language:Japanese  

  24. 総説:高温対応「イオン伝導性セラミックス」自動車へのキャパシター性能向上、効率化へ貢献

    長尾征洋、小林和代、日比野高士

      Vol. 15 ( 4 ) page: 61-63   2015.7

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    Authorship:Lead author   Language:Japanese  

  25. A direct urine fuel cell operated at intermediate temperatures Reviewed

    Masahiro Nagao, Kazuyo Kobayashi, Takashi Hibino,

    Chemistry Letters   Vol. 44 ( 3 ) page: 363 - 365   2015.3

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    DOI: 10.1246/cl.141067

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  26. High-temperature supercapacitor with a proton-conducting metal pyrophosphate electrolyte Reviewed

    Takashi Hibino, Kazuyo Kobayashi, Masahiro Nagao, Shinji Kawasaki,

    Scientific Reports   Vol. 5   page: 7903   2015.1

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1038/srep07903

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  27. Rechargeable PEM fuel-cell batteries using quinones as hydrogen carriers Reviewed

    Masahiro Nagao, Kazuyo Kobayashi, Yuta Yamamoto, Takashi Hibino,

    Journal of The Electrochemical Society   Vol. 162 ( 4 ) page: F410 - F418   2015

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1149/2.0611504jes

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  28. Rechargeable PEM fuel-cell batteries using porous carbon modified with carbonyl groups as anode materials Reviewed

    Kazuyo Kobayashi, Masahiro Nagao, Yuta Yamamoto, Pilwon Heo, Takashi Hibino,

    Journal of The Electrochemical Society   Vol. 162 ( 8 ) page: F868 - F877   2015

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1149/2.0581508jes

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  29. An IrSi oxide film as a highly active water-oxidation catalyst in acidic media Reviewed

    Viet-Ha Tran, Takeshi Yatabe, Takahiro Matsumoto, Hidetaka Nakai, Kazuharu Suzuki, Takao Enomoto, Takashi Hibino, Kenji Kaneko, Seiji Ogo,

    Chemical Communication   Vol. 51 ( 63 ) page: 12589 - 12592   2015

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/c5cc04286k

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  30. Low-temperature Sintering of Yttria-stabilized Zirconia Using Bismuth-Vanadium Oxide as a Sintering Aid at 800 degrees C Reviewed

    Nagao Masahiro, Kobayashi Kazuyo, Hibino Takashi

    CHEMISTRY LETTERS   Vol. 43 ( 12 ) page: 1887 - 1889   2014.12

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:Chemistry Letters  

    The effect of the addition of copper-doped bismuth-vanadium oxide to yttria-stabilized zirconia (YSZ) on the sinterability and electrical conductivity, especially in reducing atmospheres, has been investigated. When Bi2Cu0.1V0.9O5.35 was used as a sintering aid, the sintering temperature could be reduced to 800°C, whereas the conventional sintering process requires temperatures above 1300°C. Although the conductivity of YSZ with 1.5 mol% Bi2Cu0.1V0.9O5.35 was slightly lower than that of pure YSZ si ntered at 1300°C, no PO2 dependence was observed under reducing conditions (e.g., PO2 = 10-5-10-24 atm), which indicates that the electrolyte is applicable to solid-oxide fuel cells.

    DOI: 10.1246/cl.140712

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  31. [NiFe]Hydrogenase from Citrobacter sp S-77 Surpasses Platinum as an Electrode for H-2 Oxidation Reaction Reviewed

    Matsumoto Takahiro, Eguchi Shigenobu, Nakai Hidetaka, Hibino Takashi, Yoon Ki-Seok, Ogo Seiji

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 53 ( 34 ) page: 8895 - 8898   2014.8

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:Angewandte Chemie - International Edition  

    Reported herein is an electrode for dihydrogen (H2) oxidation, and it is based on [NiFe]Hydrogenase from Citrobacter sp. S-77 ([NiFe] S77). It has a 637 times higher mass activity than Pt (calculated based on 1 mg of [NiFe]S77 or Pt) at 50 mV in a hydrogen half-cell. The [NiFe]S77 electrode is also stable in air and, unlike Pt, can be recovered 100% after poisoning by carbon monoxide. Following characterization of the [NiFe]S77 electrode, a fuel cell comprising a [NiFe] S77 anode and Pt cathode was constructed and shown to have a a higher power density than that achievable by Pt. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

    DOI: 10.1002/anie.201404701

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  32. Feo.4Ta0.5P2O7-based composite membrane for high-temperature, low-humidity proton exchange membrane fuel cells Reviewed

    Pilwon Heo, Yanbai Shen, Keijiro Kojima, Chanho Pak, Kyoung Hwan Choi, Takashi Hibino

    Electrochimica Acta   Vol. 128   page: 287 - 291   2014.5

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    DOI: 10.1016/j.electacta.2013.08.107

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  33. Mixed Potential Response for Hydrocarbons in a Proton-Conductive Electrochemical Cell Operated at Room Temperature Reviewed

    Hibino Takashi, Kobayashi Kazuyo

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 161 ( 5 ) page: H326 - H331   2014

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:Journal of the Electrochemical Society  

    Themixed potential response for various hydrocarbons at room temperaturewas investigated using proton-conductive Sn0.9In0.1P 2O7 as an electrolyte. Among the tested electrodes, Pt/C exhibited the most negative potential in a feed mixture of 1000 ppm propene, 10% oxygen, and ca. 3% water vapor. The potential of this electrode was further shifted to a more negative value by the addition of Sn0.9In 0.1P2O7 to the electrode. The resultant potential vs. an air electrode reached ?78 mV at 1000 ppm propene, which is a significant deviation from that calculated from the Nernst equation. This non-Nernstian potential also became enhanced as the concentration and carbon number of the hydrocarbon increased, with the C-C linkage unsaturated, and with a branched chain structure. These enhancement effects could be explained by the polarization curves for hydrocarbon and oxygen, where CO2 formation through hydrocarbon oxidation and water vapor formation through oxygen reduction were in competition with each other. It should be emphasized that the heterogeneous catalytic reaction of the hydrocarbon with oxygen did not occur over the electrode, which allowed not only for a simple mixed potential theory, but also for the potential properties to be independent of the supply gas flow rate. © 2014 The Electrochemical Society. All rights reserved.

    DOI: 10.1149/2.054405jes

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  34. Erratum: Room-temperature proton transport and its effect on thermopower in a solid ionic semiconductor, TTFCOONH<inf>4</inf> (Journal of Materials Chemistry A (2013) 1 (5089-5096) (DOI:10.1039/C3TA00011G)) Reviewed

    Kobayashi Y., Fujii T., Terasaki I., Kino H., Jin Y., Hibino T., Kobayashi T., Nishibori E., Sawa H., Yoshikawa H., Terauchi T., Sumi S.

    Journal of Materials Chemistry A   Vol. 1 ( 48 )   2013.12

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:Journal of Materials Chemistry A  

    DOI: 10.1039/c3ta90280c

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  35. Oxygen reduction reaction over nitrogen-doped graphene oxide cathodes in acid and alkaline fuel cells at intermediate temperatures Reviewed

    Takashi Hibino, Kazuyo Kobayashi, Pilwon Heo

    Electrochimica Acta   Vol. 112   page: 82 - 89   2013.12

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    DOI: 10.1016/j.electacta.2013.08.101

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  36. Organometallic Catalysts for Use in a Fuel Cell Reviewed

    Matsumoto Takahiro, Kim Kyoungmok, Nakai Hidetaka, Hibino Takashi, Ogo Seiji

    CHEMCATCHEM   Vol. 5 ( 6 ) page: 1368 - 1373   2013.6

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:ChemCatChem  

    We report the successful increase in performance of a fuel cell based on organometallic catalysis. An organometallic [NiIIRuIV] peroxo complex functions as cathode catalyst and was designed following mechanistic consideration of the cell. It was confirmed that the organometallic [NiIIRuIV] peroxo catalyst could function in the fuel cell with a 240% increase in power output over our previous systems. This organometallic catalyst can act in both solid and solution phases and allows observation of the mechanism, hence providing us further opportunity for future improvement. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

    DOI: 10.1002/cctc.201200595

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  37. Proton-conductor-supported ultra-low loading Pt-Rh three-way catalysts Reviewed

    Xue Dong, Masakazu Nishida, Takashi Hibino

    The Journal of Physical Chemistry C   Vol. 117 ( 4 ) page: 1827 - 1832   2013.1

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/jp312213x

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  38. An intermediate-temperature alkaline fuel cell using an Sn0.92Sb0.08P2O7-based hydroxide-ion-conducting electrolyte and electrodes Reviewed

    Takashi Hibino, Kazuyo Kobayashi

    Journal of Materials Chemistry A   Vol. 1 ( 4 ) page: 1134 - 1140   2013

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/c2ta00368f

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  39. Hydroxide ion conduction in molybdenum(VI)-doped tin pyrophosphate at intermediate temperatures Reviewed

    Takashi Hibino, Kazuyo Kobayashi

    Journal of Materials Chemistry A   Vol. 1 ( 23 ) page: 6934 - 6941   2013

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/c3ta10769h

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  40. Intermediate-temperature alkaline fuel cells with non-platinum electrodes Reviewed

    Takashi Hibino, Kazuyo Kobayashi

    Journal of Materials Chemistry A   Vol. 1 ( 24 ) page: 7019 - 7022   2013

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/c3ta11118k

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  41. Design of proton-conducting Sn0.95Al0.05P2O7 with mesoporous structure Reviewed

    Takashi Hibino, Kazuyo Kobayashi, Satoru Fujita

    Journal of Materials Chemistry A   Vol. 1 ( 42 ) page: 13082 - 13088   2013

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/c3ta12525d

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  42. An all-solid-state rechargeable aluminum-air battery with a hydroxide ion-conducting Sb(v)-doped SnP2O7 electrolyte Reviewed

    Takashi Hibino, Kazuyo Kobayashi, Masahiro Nagao,

    Journal of Materials Chemistry A   Vol. 1 ( 47 ) page: 14844 - 14848   2013

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/c3ta12707a

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  43. Room-temperature proton transport and its effect on thermopower in a solid ionic semiconductor, TTFCOONH4 Reviewed

    Kobayashi Yuka, Fujii Takenori, Terasaki Ichiro, Kino Hiori, Jin Yongcheng, Hibino Takashi, Kobayashi Tetsuya, Nishibori Eiji, Sawa Hiroshi, Yoshikawa Hideki, Terauchi Takeshi, Sumi Satoshi

    JOURNAL OF MATERIALS CHEMISTRY A   Vol. 1 ( 16 ) page: 5089 - 5096   2013

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    Ammonium proton in a solid ionic semiconductor, TTFCOONH4, is shown to be mobile under anhydrous conditions at room temperature by the hydrogen concentration cell method. Isotope substituted TTFCOOND4 exhibits a 2.2 H/D isotope effect in ion carrier mobility with TTFCOONH 4. First-principles calculations reveal that an efficient proton-transfer pathway via low-barrier N⋯H+⋯N hydrogen bonds reduces the activation energy to 0.12 eV, which is quite small and comparable to that reported in a bulk water system. The ac conductivity of TTFCOONH4 and TTFCOOND4 is similar at room temperature, reflecting similar hole carrier concentrations. In sharp contrast, the thermopower exhibits a large isotope effect: TTFCOONH4 shows 260 μV K-1, which is twice as large as that predicted by the hole carrier concentration and the value of TTFCOOND4, with 138 μV K-1. The 1.9 H/D isotope effect in thermopower closely relates to the 2.2 H/D isotope effect in ion carrier mobility. Proton carriers in the temperature gradient enhance thermopower without cancelling out the effect of holes in the solid state owing to possession of the same positive charge. © The Royal Society of Chemistry 2013.

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  44. Intermediate-temperature, non-humidified proton exchange membrane fuel cell with a highly proton-conducting Fe0.4Ta0.5P2O7 electrolyte Reviewed

    Yanbai Shen, Pilwon Heo, Chanho Pak, Hyuk Chang, Takashi Hibino

    Electrochemistry Communications   Vol. 24 ( 1 ) page: 82 - 84   2012.10

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    DOI: 10.1016/j.elecom.2012.08.020

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  45. 総説:中温プロトン伝導体のエネルギー・環境技術への応用

    日比野高士

    化学工業   Vol. 63 ( 10 ) page: 8-16   2012.10

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  46. A solid-state particulate matter sensor based on electrochemical oxidation of carbon by active oxygen Reviewed

    Shen Y. B., Harada T., Teranishi S., Hibino T.

    SENSORS AND ACTUATORS B-CHEMICAL   Vol. 162 ( 1 ) page: 159 - 165   2012.2

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    The carbon oxidation activity and sensing performance of an electrochemical sensor incorporating a robust SnP 2O 7-SnO 2 composite ceramic as a solid electrolyte were investigated at an operating temperature of 200°C. Specific reactivity of the electrochemically formed active oxygen toward carbon was accomplished with a high current efficiency estimated from the four-electron reaction (C + 2H 2O → CO 2 + 4H + + 4e -). However, this reaction did not occur over the entire electrode layer, which resulted in low sensitivity and a slow response speed. This problem could be overcome by distributing a SnP 2O 7 ionomer over the working electrode at a level of several micrometers. Moreover, an additional benefit of the present sensor for practical applications is that little interference was encountered when sensing carbon at levels of 1000 ppm CO and 1000 ppm C 3H 8 in the sample gas. The resulting amperometric mode sensor could successfully produce a current signal that corresponded to the quantity of particulate matter (PM) in the bench test apparatus. These results demonstrate that the present sensor is able to continuously monitor the PM concentration while self-regenerating. © 2011 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.snb.2011.12.057

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  47. Alternating current electrolysis for production of phenol from benzene Reviewed

    Byungik Lee, Hiroto Naito, Masahiro Nagao, Takashi Hibino

    Angewandte Chemie-International Edition   Vol. 51 ( 28 ) page: 6961 - 6965   2012

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    DOI: 10.1002/anie.201202159

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  48. Proton conduction in A0.5B0.5P2O7 compounds at intermediate temperatures Reviewed

    Yanbai Shen, Keijiro Kojima, Masakazu Nishida, Pilwon Heo, Kyoung Hwan Choi, Hyuk Chang, Takashi Hibino

    Journal of Materials Chemistry   Vol. 22 ( 30 ) page: 14907 - 14915   2012

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    DOI: 10.1039/c2jm31887c

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  49. Hydroxide ion conducting antimony(Ⅴ)-doped tin pyrophosphate electrolyte for intermediate-temperature alkaline fuel cells Reviewed

    Takashi Hibino, Yanbai Shen, Masakazu Nishida, Masahiro Nagao

    Angewandte Chemie-International Edition   Vol. 51 ( 43 ) page: 10786 - 10790   2012

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    DOI: 10.1002/anie.201205022

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  50. Electrochemical Oxidation of Benzene to Phenol Reviewed

    Lee Byungik, Naito Hiroto, Hibino Takashi

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 51 ( 2 ) page: 440 - 444   2012

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    Gas-phase electrochemistry: The direct hydroxylation of benzene to phenol was investigated using an electrochemical cell. The production of phenol over a VO x anode was found to be significant at 50 °C. The resultant current efficiency for phenol production and selectivity toward phenol reached 76.5 and 94.7 %, respectively. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

    DOI: 10.1002/anie.201105229

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  51. Proton conduction in non-doped and acceptor-doped metal pyrophosphate (MP2O7) composite ceramics at intermediate temperatures Reviewed

    Sato Yousuke, Shen Yanbai, Nishida Masakazu, Kanematsu Wataru, Hibino Takashi

    JOURNAL OF MATERIALS CHEMISTRY   Vol. 22 ( 9 ) page: 3973 - 3981   2012

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    Proton conductors capable of operating in the temperature range of 100-600°C have received great interest for many application areas such as fuel cells, sensors, and electrolyzers; however, very few materials that can satisfy these demands have been reported to date. Here, we report a promising candidate for a solid electrolyte in intermediate-temperature electrochemical devices. First, MP 2O 7-MO 2 composite ceramics (M = Sn, Si, Ti, and Zr) were prepared by reacting a porous MO 2 substrate with an 85% H 3PO 4 solution at 600°C. Although all the tested MO 2 could react with H 3PO 4 to form the corresponding metal pyrophosphate layers on the surfaces of the exterior and interior substrate, the extent of MP 2O 7 growth in the obtained samples and their relative density were strongly dependent on the M species. These factors were the best for the SnP 2O 7-SnO 2 composite ceramic, yielding the highest electrical conductivity in the temperature range of interest. Next, different low valence cations (cation = Mg 2+, Sc 3+, Ga 3+, Y 3+, In 3+, La 3+, Sm 3+, Eu 3+, and Gd 3+) were doped into the SnP 2O 7-SnO 2 composite ceramic. The most positive effect on the electrical conductivity was observed when Sm 3+ was used as the dopant; the electrical conductivity of this sample was approximately one order of magnitude higher than that of the non-doped sample, especially at low temperatures below 250°C. Fourier transform infrared (FTIR) and proton magic angle spinning (MAS) nuclear magnetic resonance (NMR) analyses revealed that the quantity of protons incorporated in the SnP 2O 7 layer and their mobility were increased by the doping of Sm into the composite ceramic. As a consequence, the electrical conductivity of the Sm-doped SnP 2O 7-SnO 2 composite ceramic reached ∼10 -2 S cm -1 in the temperature range of 100-600°C. Proton conduction in this sample was also investigated by various electrochemical techniques. The protons function as the predominant charge carrier in the sample, and the proton transport number was almost unity in both static and dynamic conditions. © 2012 The Royal Society of Chemistry.

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  52. 総説:ナノ局所電池デバイスのエネルギー・環境技術への応用

    日比野高士

    ケミカルエンジニヤリング   Vol. 56 ( 10 ) page: 48-54   2011.10

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  53. Intermediate-temperature proton conductors and their applications to energy and environmental devices Reviewed

    Hibino Takashi

    JOURNAL OF THE CERAMIC SOCIETY OF JAPAN   Vol. 119 ( 1393 ) page: 677 - 686   2011.9

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    The development of proton conductors has proceeded rapidly in recent years. A number of organic or inorganic materials show proton conductivities of ∼10-2Scm-1 at temperatures below 100°C. However, although there is great current demand for proton conductors capable of operating in the temperature range of 100400° C in practical applications, very few materials that can satisfy this demand have been reported to date. Acceptor-doped SnP2O7 are promising candidate materials because their proton conductivities reach >10-1Scm-1 in the temperature range of interest. This paper presents an overview of the current status of acceptor-doped SnP2O7, highlighting the mechanism and kinetics of proton conduction and the development of electrochemical devices using these materials. New insights for proton insertion and conduction are proposed that use electrochemical techniques. Two approaches to designing SnP2O7-based composite electrolytes with good mechanical properties have also been developed for different operating temperatures. In addition, the benefits of intermediate-temperature operation using these materials are discussed in terms of practical applications, especially in fuel cells, exhaust sensors, and solid catalysts. © 2011 The Ceramic Society of Japan. All rights reserved.

    DOI: 10.2109/jcersj2.119.677

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  54. Ultra-low loading Pt Rh/Sn0.9In0.1P2O7 three-way catalyst for propane + NO + O-2 reaction Reviewed

    Dong Xue, Tsuneyama Kota, Hibino Takashi

    APPLIED CATALYSIS B-ENVIRONMENTAL   Vol. 106 ( 3-4 ) page: 503 - 509   2011.8

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    Propane oxidation and NO reduction at the proton conductor-electrocatalyst interface were investigated using electrochemical cells and impregnated catalysts. Sn0.9In0.1P2O7 and Pt or Pt-Rh were used as the proton conductor and electrocatalyst, respectively. In a gaseous mixture of propane, H2O, and NO, H2O is dissociated into protons and electrons at anodic sites at the interface and the resultant active oxygen oxidizes propane to CO2. Separately, NO reacts with protons and electrons to form N2O at cathodic sites at the interface. Under stoichiometric conditions, including 1000ppm propane, 1000ppm NO, 3% H2O, and 4500ppm O2, the temperatures at which the above series of reactions could successfully achieve 50% conversion (T50%) was reduced to 310 and 385°C for propane and NO, respectively, over a 0.01wt.% Pt/Sn0.9In0.1P2O7 catalyst. These were much lower than T50% of 430 and 535°C for propane and NO, respectively, over a 0.01wt.% Pt/γ-Al2O3 catalyst. Moreover, the addition of 0.005wt.% Rh to the Pt/Sn0.9In0.1P2O7 catalyst enhanced NO reduction by promoting the dissociative adsorption of NO, thus providing a further reduction of T50% for the NO reaction to 355°C. © 2011 Elsevier B.V.

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  55. An H3PO4-doped polybenzimidazole/Sn0.95Al0.05P2O7 composite membrane for high-temperature proton exchange membrane fuel cells Reviewed

    Jin Y. C., Nishida M., Kanematsu W., Hibino T.

    JOURNAL OF POWER SOURCES   Vol. 196 ( 15 ) page: 6042 - 6047   2011.8

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    A polybenzimidazole (PBI)/Sn0.95Al0.05P 2O7 (SAPO) composite membrane was synthesized by an in situ reaction of SnO2 and Al(OH)3-mixed powders with an H3PO4 solution in a PBI membrane. The formation of a single phase of SAPO in the PBI membrane was completed at a temperature of 250 °C. Thermogravimetric analysis showed that the PBI membrane was not subject to a serious damage by the presence of SAPO until 500 °C. Scanning electron microscopy revealed that SAPO particles with a diameter of approximately 300 nm were homogeneously dispersed and separated from each other in the PBI matrix. Proton magic angle spinning nuclear magnetic resonance spectra confirmed the presence of new protons originating from the SAPO particles in the composite membrane. As a consequence of the interaction of protons in the SAPO with those in the free H3PO4, the H3PO4-doped PBI/SAPO composite membrane exhibited conductivities several times higher than those of an H3PO4-doped PBI membrane at room temperature to 300 °C, which could contribute to the improved performance of H 2/O2 fuel cells. © 2011 Elsevier B.V. All rights reserved.

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  56. A comparative study of Pt/C cathodes in Sn0.9In0.1P2O7 and H3PO4 ionomers for high-temperature proton exchange membrane fuel cells Reviewed

    Jin Y. C., Okada M., Hibino T.

    JOURNAL OF POWER SOURCES   Vol. 196 ( 11 ) page: 4905 - 4910   2011.6

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    New Pt/C cathodes with many reaction sites for the oxygen reduction reaction as well as high tolerance to Pt corrosion have been designed for high-temperature proton exchange membrane fuel cells (PEMFCs), wherein a composite mixture of Sn0.9In0.1P2O7 (SIPO) and sulfonated polystyrene-b-poly(ethylene/butylene)-b-polystyrene (sSEBS) functioned as an ionomer. The microstructure of the Pt-SIPO-sSEBS/C cathode was characterized by homogeneous distribution of the ionomer over the catalyst layer and close contact between the ionomer and the Pt/C powder. As a result, the activation and concentration overpotentials of the Pt-SIPO-sSEBS/C cathode between 100 and 200 °C were lower than those of an H 3PO4-impregnated Pt/C cathode, which suggests that the present ionomer can avoid poisoning of Pt by phosphate anions and the limitation of gas diffusion through the catalyst layer. Moreover, agglomeration of Pt in the Pt-SIPO-sSEBS/C cathode was not observed during a durability test at 150 °C for 6 days, although it was significant in the Pt-H3PO 4/C cathode. Therefore, it is concluded that the Pt-SIPO-sSEBS/C electrode is a very promising cathode candidate for high-temperature PEMFCs. © 2011 Elsevier B.V.

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  57. Efficient and selective formation of methanol from methane in a fuel cell-type reactor Reviewed

    Lee Byungik, Hibino Takashi

    JOURNAL OF CATALYSIS   Vol. 279 ( 2 ) page: 233 - 240   2011.4

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    Direct oxidation of methane to methanol at low temperatures was investigated using a fuel cell-type reactor, where a mixture of methane and H2O vapor was supplied to the anode and air to the cathode. Methanol was scarcely produced over a Pt/C anode from 50 to 250 °C. However, through trial and error, the production of methanol over a V2O 5/SnO2 anode was significant at 100 °C; the current efficiency for methanol production and the selectivity toward methanol were as high as 61.4% and 88.4%, respectively. Methanol was produced by the reaction of methane with an active oxygen species over the V2O5 catalyst. Cyclic voltammetry of the anode indicated that the generation of such active oxygen species was strongly dependent on the anode potential. Moreover, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy measurements confirmed that highly dispersed and partially reduced vanadium species were present on the SnO2 surface. These vanadium species are considered to be active sites for the formation of the active oxygen species, probably anion radicals (O2·- and O·-). © 2010 Elsevier Inc. All rights reserved.

    DOI: 10.1016/j.jcat.2010.12.020

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  58. Efficient and selective formation of methanol from methane in a fuel cell type reactor Reviewed

    Byungik Lee, Takashi Hibino

    Journal of Catalysis   Vol. 279   page: 233-240   2011.4

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  59. 総説:ナノ分極型高選択反応性電極の創製

    日比野高士

    Electrochemistry   Vol. 79 ( 4 ) page: 274-279   2011.4

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  60. Design of a highly sensitive and responsive electrode for particulate matter monitoring Reviewed

    Shen Y. B., Takeuchi T., Hibino T.

    SENSORS AND ACTUATORS B-CHEMICAL   Vol. 153 ( 1 ) page: 226 - 231   2011.3

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    In a previous sensor device based on a PtSn0.9In 0.1P2O7Pt electrode system, electrochemical carbon oxidation was realized over the surface of a working electrode, enabling continuous carbon monitoring with self-regeneration of the sensor. Specific reactivity of the active oxygen species for carbon was demonstrated along with a high current efficiency. However, this reaction did not occur over the entire electrode layer, limiting the sensing properties and giving a low sensitivity and response speed. The main reason for carbon oxidation being limited to the surface region was the lack of proton conduction in the working electrode. To overcome this problem, we added proton-conducting Sn0.9In 0.1P2O7 particles as an ionomer to the working electrode. The Sn0.9In0.1P2O7 ionomer was successfully distributed over the working electrode at the level of a few micrometers, providing reaction sites for carbon oxidation over the entire electrode layer. The resulting amperometric sensor provided a sensitivity to carbon that was 1.4 times greater than that of the ionomer-free working electrode, as determined by the current at which carbon oxidation had ceased. Moreover, carbon floating in a glass container could be transported to reaction sites present on the external surface of the working electrode, allowing for a large current and a rapid response. © 2010 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.snb.2010.10.042

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  61. Design of a highly sensitive and responsive electrode for monitoring diesel particulate matter Reviewed

    Yanbai Shen, Takashi Takeuchi, Takashi Hibino

    Sensors and Actuators B: Chemical   Vol. 153   page: 226-231   2011.3

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  62. Synthesis and characterization of dense SnP2O7-SnO2 composite ceramics as intermediate-temperature proton conductors Reviewed

    Yanbai Shen, Masakazu Nishida, Wataru Kanematsu, Takashi Hibino

    Journal of Materials Chemistry   Vol. 21   page: 663-670   2011.1

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  63. Compact bipolar plate-free direct methanol fuel cell stacks Reviewed

    Dong Xue, Takahashi Motohiro, Nagao Masahiro, Hibino Takashi

    CHEMICAL COMMUNICATIONS   Vol. 47 ( 18 ) page: 5292 - 5294   2011

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    Fuel cells with a PtAu/C anode and a Pr-doped Mn2O3/C cathode were stacked without using a bipolar plate, and their discharge properties were investigated in a methanol aqueous solution bubbled with air. A three-cell stack exhibited a stack voltage of 2330 mV and a power output of 21 mW. © The Royal Society of Chemistry 2011.

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  64. Synthesis and characterization of dense SnP2O7-SnO2 composite ceramics as intermediate-temperature proton conductors Reviewed

    Shen Yanbai, Nishida Masakazu, Kanematsu Wataru, Hibino Takashi

    JOURNAL OF MATERIALS CHEMISTRY   Vol. 21 ( 3 ) page: 663 - 670   2011

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    Dense SnP2O7-SnO2 composite ceramics were prepared by reacting a porous SnO2 substrate with an 85% H3PO4 solution at elevated temperatures. At 300 °C and higher, SnO2 reacted with H3PO4 to form an SnP2O7 layer on exterior and interior surfaces in the substrate, the growth rate of which increased with increasing reaction temperature. Finally, at 600 °C, the pores of this composite ceramic were perfectly closed and its electrical conductivity became several orders of magnitude higher than that of the SnO2 substrate alone. Proton conduction was demonstrated in this composite ceramic using electrochemical measurements and various analytical techniques. Comparison of the observed electromotive force with the theoretical value in two gas concentration cells demonstrated that this composite ceramic is a pure ion conductor, wherein the predominant ion species are protons. Fourier transform infrared (FT-IR) and proton magic angle spinning (MAS) nuclear magnetic resonance (NMR) analyses revealed that the protons interacted with lattice oxide ions in the SnP2O7 layer to form hydrogen bonds. An H/D isotope effect suggested that proton conduction in this composite ceramic was based on a proton-hopping mechanism. The proton conductivity in this material reached ∼10-2 S cm-1 in the temperature range of 250-600 °C. © The Royal Society of Chemistry.

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  65. A proton-conducting composite membrane Sn0 95Al0 05P2O7 and polystyrene-b-poly(ethylene/propylene)-b-polystyrene Reviewed

    Jin Yongcheng, Hibino Takashi

    ELECTROCHIMICA ACTA   Vol. 55 ( 28 ) page: 8371 - 8375   2010.12

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    An anhydrous proton conductor, Sn0.95Al0.05P 2O7 (SAPO), composed of polystyrene-b-poly(ethylene/ propylene)-b-polystyrene (SEPS), was developed and characterized using morphological, structural, and electrochemical analyses. In the composite membrane with 20 wt% SEPS, a homogeneous distribution of SAPO particles in the matrix was obtained in the thickness range of 65-90 μm, yielding a proton conductivity of 3.4 × 10-3 S cm-1 at 200 °C, tensile strength of 4.6 MPa and an elongation at break of 711.0% at room temperature. Fuel cell tests verified that the open-circuit voltage was maintained at a constant value of approximately 1 V between 100 and 250 °C. The peak power densities achieved with unhumidified H2 and air were 77.0 mW cm-2 at 100 °C, 121.0 mW cm-2 at 150 °C, and 163.1 mW cm-2 at 225 °C. © 2010 Elsevier Ltd All rights reserved.

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  66. A proton-conducting composite membrane: Sn0.95Al0.05P2O7 and polystyrene-b-poly(ethylene/propylene)-b-polystyrene Reviewed

    Yongcheng Jin, Takashi Hibino

    Electrochimica Acta   Vol. 55   page: 8371-8375   2010.12

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  67. Separator-free fuel cell stacks operating in a mixture of hydrogen and air Reviewed

    Masahiro Nagao, Motohiro Takahashi, Takashi Hibino

    Energy & Environmental Science   Vol. 3   page: 1934-1940   2010.12

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  68. Separator-free fuel cell stacks operating in a mixture of hydrogen and air Reviewed

    Nagao Masahiro, Takahashi Motohiro, Hibino Takashi

    ENERGY & ENVIRONMENTAL SCIENCE   Vol. 3 ( 12 ) page: 1934 - 1940   2010.12

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    Fuel cells for vehicular and residential applications have encountered a key technical challenge in cost reduction. This challenge can be avoided by operating a fuel cell stack without the use of gas separators, which are expensive and voluminous and therefore comprise a significant portion of the cost of a fuel cell stack. Single-chamber fuel cells (SCFCs) have the potential of realizing such operation, because there is no need for separation between fuel and air. In this paper, we present a selective anode (PtAu/C) and cathode (Pr-doped Mn2O3/C) for respective electrochemical hydrogen oxidation and oxygen reduction reactions in a SCFC. A single cell with these electrodes operated at 50 °C generated an open-circuit voltage of 1204 mV and a peak power density of 50 mW cm-2 in a feed mixture of 80% hydrogen and 20% air at a flow rate of 30 mL min-1. The high selectivity of these electrodes also enabled the design of two different separator-free fuel cell stacks, parallel and perpendicular to the gas stream. Both cell stacks exhibited increasing stack voltage and power output almost proportionally to the increase in the number of single cells. These results demonstrate that the separator-free fuel cell stack shows high potential for a significant reduction of the cost of fuel cell systems. © The Royal Society of Chemistry.

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  69. Partially proton-exchanged WP2O7 with high conductivity at intermediate temperatures Reviewed

    Yongcheng Jin, Lu Yang, Masakazu Nishida, Wataru Kanematsu, Takashi Hibino

    Electrochemical and Solid-State Letters   Vol. 13 ( 11 ) page: B123-B126   2010.11

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  70. Development and application of SnP<inf>2</inf>O<inf>7</inf>-based proton conductors to intermediate-temperature fuel cells Reviewed

    Jin Y., Lee B., Hibino T.

    Journal of the Japan Petroleum Institute   Vol. 53 ( 1 ) page: 12 - 23   2010.10

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    Much attention has been devoted to efforts to operate polymer electrolyte fuel cells (PEFCs) at temperatures above 100°C in order to avoid the problem of serious CO poisoning of the anode catalyst. It is also of great con cern to operate PEFCs under low-humidity conditions, because the space and energy required for external humidi fication are eliminated or minimized in the fuel cell system. Thus, proton-conducting materials that can satisfy the above criteria have been proposed, developed, and evaluated worldwide. In particular, recent research efforts have been increasingly focusing on the design of anhydrous proton conductors, since these materials, at least in principle, do not need the presence of water as a charge carrier. We have recently found that In, Al, or Mg-doped SnP2O7 show high proton conductivities>10-1 S. cm-1 between 150 and 350 °C under water-free conditions. Attempts to apply these materials as electrolytes in some electrochemical devices were also made. This paper presents an overview of the current status of doped SnP22O 7 with principal emphasis on the materials aspect. In addition, the benefits of intermediate-temperature fuel cells using these materials are briefy summarized in terms of cell design, electrolyte and electrode materials.

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  71. Low-temperature carbon combustion over proton conductor plus electrocatalyst-mixed powders Reviewed

    Tsuneyama Kota, Sakamoto Yosuke, Suzuki Kenzi, Hibino Takashi

    APPLIED CATALYSIS B-ENVIRONMENTAL   Vol. 100 ( 1-2 ) page: 205 - 211   2010.10

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    Catalytic carbon combustion is a potential approach for eliminating particulate matter emissions from diesel engine vehicles. In this study, we report low-temperature carbon combustion by active oxygen formed at the interface of the mixed powders of a proton conductor (Sn0.9In0.1P2O7) and electrocatalyst (Pt or Mo2C). In a gaseous mixture of H2O and O2, H2O dissociated into protons and electrons at an anodic site of the interface and the resultant active oxygen oxidized carbon to CO2. Separately, O2 reacted with protons and electrons to form H2O at a cathodic site of the interface, resulting in formation of a local electrochemical cell at the proton conductor-electrocatalyst interface, which then self-discharged. This series of reactions could successfully reduce the ignition temperature for carbon to 200°C for Pt and 300°C for Mo2C. © 2010 Elsevier B.V.

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  72. Cathodes for high-temperature PEM fuel cells based on a Si0.97Al0.03C promoter and a Sn0.95In0.05P2O7 ionomer Reviewed

    Toshihiko Harada, Yongcheng Jin, Pilwon Heo, Takashi Hibino

    Fuel Cells   Vol. 10   page: 798-803   2010.10

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  73. Low-temperature carbon combustion over proton conductor+electrocatalyst-mixed powders Reviewed

    Kota Tsuneyama, Yosuke Sakamoto, Kenzi Suzuki, Takashi Hibino

    Applied Catalysis B: Environmental   Vol. 100   page: 205-211   2010.10

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  74. Cathodes for High-Temperature PEM Fuel Cells Based on a Si0.97Al0.03C Promoter and a Sn0.95In0.05P2O7 Ionomer Reviewed

    Harada T., Jin Y. C., Heo P., Hibino T.

    FUEL CELLS   Vol. 10 ( 5 ) page: 798 - 803   2010.10

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    This paper presents a promising approach to reduce the quantity of Pt required in cathodes for high-temperature proton exchange membrane (PEM) fuel cells. Based on preliminary experiments, thermally stable Si 0.97Al0.03C and Sn0.95In0.05P 2O7 were selected as promoter and ionomer, respectively. Si0.97Al0.03C particles (∼40 nm) and Sn 0.95In0.05P2O7 particles (∼45 nm) were successfully produced on a carbon support. Pt particles (∼9 nm) were selectively impregnated in the vicinity of the ionomer. Polarisation measurements revealed that the Pt-Sn0.95In0.05P 2O7-Si0.97Al0.03C/C cathode exhibited much higher oxygen reduction reaction (ORR) activity than that observed for a pure Pt/C cathode, due to the enhanced dissociative oxygen adsorption on the Si0.97Al0.03C particles and the increased number of reaction sites for the ORR provided by the Sn 0.95In0.05P2O7 particles. Fuel cell operation tests demonstrated that a Pt-Sn0.95In0.05P 2O7-Si0.97Al0.03C/C cathode with a low Pt loading of 0.1 mg cm-2 provides better cell performance than a Pt/C cathode with a Pt loading of 1.0 mg cm-2. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

    DOI: 10.1002/fuce.200900162

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  75. Proton conduction in metal pyrophosphates (MP2O7) at intermediate temperatures Reviewed

    Yongcheng Jin, Yanbai Shen, Takashi Hibino

    Journal of Materials Chemistry   Vol. 20   page: 6214-6217   2010.8

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  76. Low-temperature hydrocarbon combustion over proton conductor/metal-mixed catalysts Reviewed

    Tsuneyama Kota, Tetanishi Shinya, Hibino Takashi, Nagao Satoshi, Hirata Hirohito, Matsumoto Shin-ichi

    JOURNAL OF CATALYSIS   Vol. 273 ( 1 ) page: 59 - 65   2010.7

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    Catalytic combustion of hydrocarbons is a highly active field of research, particularly in relation to the reduction of pollutant emissions from automobiles. In this study, we report on hydrocarbon oxidation at the internal interfaces of a mixed catalyst consisting of Sn0.9In 0.1P2O7 and Pt powders. In a gaseous mixture of propane, H2O, and O2, the H2O dissociates into protons, electrons and active oxygen species at anodic interface sites, leading to oxidation of the hydrocarbon to CO2. On the other hand, O 2 reacts with protons and electrons to form H2O at cathodic interface sites. As a consequence, local electrochemical cells are formed at the interfaces, and undergo self-discharge. It was shown that the mixed catalyst had a high turnover frequency for Pt, yielding high catalytic activity for Pt contents of as low as 0.1 wt% and an initiation temperature for hydrocarbon oxidation of 150 °C. © 2010 Elsevier Inc.

    DOI: 10.1016/j.jcat.2010.04.022

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  77. Low-temperature hydrocarbon combustion over proton conductor/metal-mixed catalysts Reviewed

    Kota Tsuneyama, Shinya Teranishi, Takashi Hibino, Satoshi Nagao, Hirohito Hirata, Shin-ichi Matsumoto

    Journal of Catalysis   Vol. 273   page: 59-65   2010.7

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  78. Direct oxidation of methane to methanol over proton conductor/metal mixed catalysts Reviewed

    Lee Byungik, Sakamoto Yosuke, Hirabayashi Daisuke, Suzuki Kenzi, Hibino Takashi

    JOURNAL OF CATALYSIS   Vol. 271 ( 2 ) page: 195 - 200   2010.5

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    The intermediate-temperature and low-pressure production of methanol from methane in a one-pass process was investigated using a micro- or nanosized electrocatalyst system. The powdered catalyst was prepared by mixing proton-conducting Sn0.9In0.1P2O7 particles with high-activity Pd-Au-Cu/C particles to provide numerous electrolyte-electrode interfaces as reaction sites for methane oxidation. For a feed mixture of H2O, O2, and methane, a local electrochemical cell can be formed at the electrode-electrolyte interface: H2O → 1/2O2 + 2H+ + 2e- at the anode site; O2 + CH4 + 2H+ + 2e- → CH3OH + H2O at the cathode site. In addition, the electrode also functions as a lead wire that short-circuits the cell. Therefore, the overall reaction can be expected to be CH4 + 1/2O2 → CH3OH. The series of reactions successfully resulted in reduction in the temperature for initiation of methane oxidation to 250 °C and increased the methanol yield while maintaining a very high selectivity toward methanol for temperatures up to 400 °C. © 2010 Elsevier Inc. All rights reserved.

    DOI: 10.1016/j.jcat.2010.01.011

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  79. Direct oxidation of methane to methanol over proton conductor/metal mixed catalysts Reviewed

    Byung Ik Lee, Yosuke Sakamoto, Daisuke Hirabayashi, Kenzi Suzuki, Takashi Hibino

    Journal of Catalysis   Vol. 271   page: 195-200   2010.5

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  80. Alumina substrate-supported electrochemical device for potential application as a diesel particulate matter sensor Reviewed

    Shen Yanbai, Takeuchi Takashi, Teranishi Shinya, Hibino Takashi

    SENSORS AND ACTUATORS B-CHEMICAL   Vol. 145 ( 2 ) page: 708 - 712   2010.3

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    The carbon oxidation activity and sensing performance of an alumina substrate-supported sensor comprised of Sn0.9In0.1P2O7 as a proton conductor and Pt as an electrocatalyst were investigated. Electrochemically formed active oxygen species exhibited high activity for carbon oxidation, where the current efficiency was estimated from the four-electron reaction (C + 2H2O → CO2 + 4H+ + 4e-) and reached approximately 90%. An operating temperature of 225 °C was found to be the most effective to achieve the highest possible electrochemical carbon oxidation and the lowest possible non-electrochemical carbon oxidation. When carbon introduced to the Sn0.9In0.1P2O7-Pt interface was oxidized by active oxygen, a large potential jump was observed due to a significant increase in the polarization resistance, which was strongly dependent on the carbon content in the working electrode. Two types of carbon sensors, amperometric and potentiometric, were tested in a feed mixture of 3 vol% water vapor and 10 vol% O2. In the case of the amperometric sensor, the current increased linearly with increasing carbon content, which enabled the determination of a wide range of carbon content from the current signal. In the case of the potentiometric sensor, a threshold quantity of carbon could be recognized by selection of the current and subsequent monitoring of the sudden potential increase. © 2010 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.snb.2010.01.030

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  81. Alumina substrate-supported electrochemical device for potential application as a diesel particulate matter sensor Reviewed

    Yanbai Shen, Takashi Takeuchi, Shinya Teranishi, Takashi Hibino

    Sensors and Actuators B: Chemical   Vol. 145   page: 708-712   2010.3

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  82. High-temperature low-humidity proton exchange membrane based on an inorganic-organic hybrid structure Reviewed

    Yongcheng Jin, keisuke Fujiwara, Takashi Hibino

    Electrochemical and Solid-State Letters   Vol. 13 ( 2 ) page: B8-B10   2010.2

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  83. Development and application of SnP2O7-based proton conductors to intermediate-temperature fuel cells Invited Reviewed

    Yongcheng Jin, Byung Ik Lee, Takashi Hibino

    Journal of the Japan Petroleum Institute   Vol. 53 ( 1 ) page: 12-23   2010.1

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  84. Development and Application of SnP2O7-based Proton Conductors to Intermediate-temperature Fuel Cells Reviewed

    Jin Yongcheng, Lee Byungik, Hibino Takashi

    JOURNAL OF THE JAPAN PETROLEUM INSTITUTE   Vol. 53 ( 1 ) page: 12 - 23   2010.1

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  85. 総説:燃料電池による排ガスからのエネルギー回収

    日比野高士,内山靖之,内山直樹

    セラミックス   Vol. 45   page: 548-552   2010

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  86. High Temperature, Low Humidity Proton Exchange Membrane Based on an Inorganic-Organic Hybrid Structure Reviewed

    Jin Yongcheng, Fujiwara Keisuke, Hibino Takashi

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 13 ( 2 ) page: B8 - B10   2010

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    A high temperature and low humidity composite membrane consisting of Sn0.95 Al0.05 P2 O7 and sulfonated polystyrene- b -poly(ethylene/butylene)- b -polystyrene (sSEBS) as inorganic and organic materials, respectively, was prepared and characterized. A homogeneous distribution of the Sn0.95 Al0.05 P2 O 7 particles in the matrix was accomplished in the thickness range of 25-80 μm, providing an elongation at break above 400%, which is approximately two times higher than that for Nafion. Moreover, moderate proton conductivities of sSEBS improved proton transfer between the Sn0.95 Al 0.05 P2 O7 particles in the matrix, resulting in a proton conductivity of approximately 0.01 S cm-1 at 130°C without any humidification, which is 3 or more orders of magnitude higher than that for Nafion under the same conditions. © 2009 The Electrochemical Society.

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  87. Partially Proton-Exchanged WP2O7 with High Conductivity at Intermediate Temperatures Reviewed

    Jin Y. C., Yang L., Nishida M., Kanematsu W., Hibino T.

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 13 ( 11 ) page: B123 - B126   2010

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    Proton conduction is reported in partially proton-exchanged WP2 O7 at intermediate temperatures. Electrochemical measurements demonstrated that proton conduction occurs in this material. Proton magic angle spinning nuclear magnetic resonance and Fourier transform IR analyses revealed that the ion-exchanged protons interact with the lattice oxide ions in WP 2 O7 to form hydrogen bonds. The H/D isotope effect suggests that proton conduction in this material is based on the hopping mechanism. Consequently, the electrical conductivity of this material reached 1.1× 10-3 S cm-1 at 250°C and 1.7× 10 -2 S cm-1 at 500°C. © 2010 The Electrochemical Society.

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  88. Proton conduction in metal pyrophosphates (MP2O7) at intermediate temperatures Reviewed

    Jin Yongcheng, Shen Yanbai, Hibino Takashi

    JOURNAL OF MATERIALS CHEMISTRY   Vol. 20 ( 30 ) page: 6214 - 6217   2010

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    Intermediate-temperature fuel cells have received much recent attention as next generation energy sources. In particular, current efforts are devoted to developing proton conductors that operate at 120°C or more and at low relative humidity. Proton conduction in several metal pyrophosphates (MP 2O7, M = Sn, Ti, Si, Ge, Ce, and Zr) that have the potential to meet the demands for intermediate-temperature fuel cell applications are reviewed with an emphasis on the material aspects. © 2010 The Royal Society of Chemistry.

    DOI: 10.1039/b924188d

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  89. Proton-conducting thin film grown on Yttria-stabilized Zirconia surface for Ammonia gas sensing technologies Reviewed

    Shinya Teranishi, Kyohei Kondo, Masakazu Nishida, Wataru Kanematsu, Takashi Hibino

    Electrochemical and Solid-State Letters   Vol. 12 ( 9 ) page: J73-J76   2009.9

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  90. Proton conductivity and solid acidity of Mg-, In-, and Al-doped SnP2O7 Reviewed

    Kouji Genzaki, Pilwon Heo, Mitsuru Sano, Takashi Hibino

    Journal of the Electrochemical Society   Vol. 156 ( 7 ) page: B806-B810   2009.7

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  91. Selective electrochemical oxidation of carbon by active oxygen for potential application as a sensor for diesel particulates Reviewed

    Teranishi Shinya, Kondo Kyohei, Tsuge Akihito, Hibino Takashi

    SENSORS AND ACTUATORS B-CHEMICAL   Vol. 140 ( 1 ) page: 170 - 175   2009.6

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    The formation of active oxygen by electrochemical oxidation of H2O vapor, coupled with carbon detection using those oxygen species, has been investigated by utilizing Sn0.9In0.1P2O7 as a proton conductor and Pt as an electrocatalyst. The H2O vapor was dissociated into protons and electrons at a Pt-carbon working electrode, which produced active oxygen on the carbon surface. This oxygen species showed high activity for carbon oxidation at temperatures of 50 °C or higher, where CO2 formation increased with temperature and reached the theoretical value calculated from the four-electron reaction (C + H2O → CO2 + 4H+ + 4e-) at 200 °C. When the formation rate of active oxygen was greater than the oxidation rate of carbon at the working electrode, the electrode potential increased rapidly due to a significant increase in polarization resistance. The timing of the potential jump was strongly dependent on both the carbon content in the working electrode and the current to the working electrode, which provides information on the quantity of carbon. In addition, little interference was encountered in sensing for carbon at 1000 ppm CO and 1000 ppm C3H8 in the sample gas. The high selectivity toward carbon was based on different mechanisms for CO and C3H8; almost all of the CO was catalytically oxidized to CO2 before reacting with active oxygen, while C3H8 experienced little reaction with active oxygen. These results demonstrate that the present sensor sensitively and selectively detects carbon while self-regenerating. © 2009 Elsevier B.V. All rights reserved.

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  92. *Selective electrochemical oxidation of carbon by active oxygen for potential application as a sensor for diesel particulates Reviewed

    Shinya Teranishi, Kyohei Kondo, Akihito Tsuge, Takashi Hibino

    Sensors and Actuators B: Chemical   Vol. 140   page: 170-175   2009.6

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  93. Nanostructured Pt-Sn1-xInxP2O7 cathodes for high-temrerature proton exchange membrane fuel cells Reviewed

    Pilwon Heo, Toshihiko Harada, Takashi Hibino

    Electrochemical and Solid State Letters   Vol. 12 ( 1 ) page: B1-B4   2009.1

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  94. 総説:電極触媒活性の精密制御に基づいたガスセンシング技術の開発と各種デバイスへの応用展開

    日比野高士

      Vol. 25   page: 38-40   2009

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  95. Nanostructured Pt-Sn(1-x)In(x)P(2)O(7) Cathodes for High-Temperature Proton Exchange Membrane Fuel Cells Reviewed

    Heo Pilwon, Harada Toshihiko, Hibino Takashi

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 12 ( 1 ) page: B1 - B4   2009

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    Nanosized proton-conducting Sn0.95 In0.05 P2 O7 ionomers were grown on carbon supports by the coprecipitation of tin and indium chlorides with excess ammonia water and subsequent solid-state reaction with phosphoric acid. The resulting homogeneous networks of Sn0.95 In0.05 P2 O7 ionomers enhanced the activity of a Pt catalyst for the oxygen reduction reaction in the temperature range of 150-250°C. In addition, the Pt catalyst showed high corrosion resistance in the cathode environment while maintaining high performance levels. A comparison of the cathode performance between Sn0.95 In0.05 P2 O7 and H3 P O4 ionomers further demonstrated that the Sn0.95 In0.05 P2 O7 nanoparticles are promising candidates for cathode ionomer materials at high temperatures. © 2008 The Electrochemical Society.

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  96. Proton-Conducting Thin Film Grown on Yttria-Stabilized Zirconia Surface for Ammonia Gas Sensing Technologies Reviewed

    Teranishi Shinya, Kondo Kyohei, Nishida Masakazu, Kanematsu Wataru, Hibino Takashi

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 12 ( 9 ) page: J73 - J76   2009

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    We demonstrate an approach to impart both proton conduction and solid acidity to the surface of yttria-stabilized zirconia (YSZ). By reacting a YSZ substrate with liquid H3PO4 at 500°C, a thin Zr 1-xYx P2O7 film is grown on the substrate, which shows proton conductivity dependence on humidity and strong acid sites interacting with basic ammonia gas. This technique can be applied to gas sensor devices, yielding a remarkably sensitive and selective response to low concentrations (parts per million) of ammonia. Another important achievement of this technique is the realization of sensing properties in spite of using a conventional Pt electrode. © 2009 The Electrochemical Society.

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  97. Proton Conductivity and Solid Acidity of Mg-, In-, and Al-Doped SnP2O7 Reviewed

    Genzaki Kouji, Heo Pilwon, Sano Mitsuru, Hibino Takashi

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 156 ( 7 ) page: B806 - B810   2009

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    Mg-, In-, and Al-doped SnP2 O7 were synthesized, and their potential as electrolytes for fuel cells was evaluated in terms of their performance and durability. The overall conductivity of Mg-doped SnP2 O7 increased with increasing Mg2+ content and reached a maximum at 10 mol %. However, this was smaller than that obtained for doping with 10 mol % In3+ and 5 mol % Al3+, especially at temperatures below 300°C. This result was interpreted to be a consequence of lower proton mobility rather than of smaller proton concentration in Mg-doped SnP2 O7, probably due to the electrostatic restriction by Mg2+ against proton transport. Moreover, to investigate the influence of the Mg2+ doping on the fuel-cell properties, fuel-cell tests were conducted using Sn0.9 Mg0.1 P2 O7, Sn0.9 In0.1 P2 O7, and Sn0.95 Al0.05 P2 O7 as electrolytes at a temperature of 150°C. Compared with Sn0.9 In0.1 P2 O7 and Sn0.95 Al0.05 P2 O7 cells, the Sn0.9 Mg0.1 P2 O7 cell showed a somewhat higher Ohmic resistance but exhibited a comparable polarization resistance, which is the main component of the total electrical resistance. More importantly, the Mg2+ doping led to an improved stability of the Pt catalyst and carbon support at high potentials. This beneficial effect was attributed to a large reduction in the acidity of SnP2 O7 resulting from the basicity of MgO. © 2009 The Electrochemical Society.

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  98. Nano-sized electrochemical reactors for selective NOx reduction Reviewed

    Shinya Teranishi, Akihito Tuge, Atsuko Tomita, Mitsuru Sano, Takashi Hibino

    Electrochemical and Solid-State Letters   Vol. 11 ( 10 ) page: P9-P12   2008.10

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  99. A single-chamber SOFC stack:energy recovery from engin exhaust Reviewed

    Masahiro Nagao, Masaya Yano, Kohsuke Okamoto, Atsuko Tamita, Yasuyuki Uchiyama, Naoki Uchiyama, Takashi Hibino

    Fuel Cells   Vol. 08 ( 5 ) page: 322-329   2008.10

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  100. A Single-Chamber SOFC Stack: Energy Recovery from Engine Exhaust Reviewed

    Nagao M., Yano M., Okamoto K., Tomita A., Uchiyama Y., Uchiyama N., Hibino T.

    FUEL CELLS   Vol. 8 ( 5 ) page: 322 - 329   2008.10

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    The feasibility of applying single-chamber solid oxide fuel cells (SC-SOFCs) to power generators for exhaust energy recovery was investigated using both model and actual exhaust gases. In the experiments with model exhaust gases, a single cell, Ni-Ce0.8Sm0.2O1.9/YSZ/ La0.8Sr0.2MnO3, was operated in a mixture of gases containing ppm levels of CH4, C2H6, C3H3, C4H10and O2. The cell performance was considerably affected by the molar ratio of total hydrocarbons to O2, the operating temperature and the gas flow rate. The optimal operating conditions of the SC-SOFC were found to be similar to those found in actual exhaust from gasoline engines. Thermal and mechanical loading performance tests demonstrated high tolerance towards thermal cycling and breakage of the electrolyte. Performance tests with and without a gas separator suggested that there is no requirement for a gas separator in an actual exhaust. In the experiments with actual exhaust gases, a 12-cell stack was installed to a 250-cm3 engine. The open circuit voltages (OCVs) were between 5 and 8 V and independent of the number of revolutions, but were lower than the values expected from the model exhaust results. This was considered to be due to the deviation of the actual exhaust gases from the model gases. Nevertheless, the stack performance was reproducible and stable in the range from 1,500 to 5,500 rpm. The resultant peak power reached above 1 W at 4,500 rpm. © 2008 WILEY-VCH Verlag GmbH & Co. KGaA.

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  101. De-NOx reactor and NOx sensor using In3+-doped SnP2O7 with PtRhBa/C electrode Reviewed

    Nagao Masahiro, Yoshii Takeshi, Namekata Yousuke, Teranishi Shinya, Sano Mitsuru, Tomita Atsuko, Hibino Takashi

    SOLID STATE IONICS   Vol. 179 ( 27-32 ) page: 1655 - 1661   2008.9

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    An electrochemical cell using an In3+-doped SnP2O7 proton conductor as the electrolyte exhibited comparable NO reduction and sensing properties at around 250 °C. NO was reduced to N2 most effectively when using a PtRhBa/C cathode by applying current to the cell. High electrocatalytic activity was maintained even in the presence of CO2 and H2O. PtRhBa/C was also found to be the most effective electrode material for NOx sensing. The sensor exhibited electromotive force (EMF) response towards the positive direction with increasing NO and NO2 concentrations. The polarization curves of NO/NO2 and water vapor indicated that the sensing mechanism is based on the mixed potential. The effects of added Rh and Ba to the Pt/C electrode were explained in terms of selective reduction and adsorption of NO/NO2 over the electrode surface, respectively. © 2008 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.ssi.2008.03.033

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  102. Pt-free intermediate-temperature fuel cells Reviewed

    Heo Pilwon, Shibata Hidetaka, Nagao Masahiro, Hibino Takashi

    SOLID STATE IONICS   Vol. 179 ( 27-32 ) page: 1446 - 1449   2008.9

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    Pt-free fuel cells were investigated using a proton-conducting Sn0.9In0.1P2O7 electrolyte at intermediate temperatures between 150 and 300 °C. Transition metal oxides were applied as non Pt cathode catalysts. A ZrO2/C catalyst showed the highest catalytic activity for the oxygen reduction reaction among the metal oxides tested. The catalytic activity of ZrO2/C was further improved by optimizing the heat-treatment temperature for ZrO2/C. XRD measurements revealed that the high catalytic activity was attributed to the crystal structure of tetragonal ZrO2. Finally, we evaluated performance of a Pt-free fuel cell using the ZrO2/C cathode with a Mo2C-ZrO2/C anode that shows Pt-like behavior in reducing atmospheres. Reasonable performance was achieved by operating the Pt-free fuel cell at intermediate temperatures above 200 °C. © 2008 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.ssi.2007.12.090

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  103. Pt-free intermediate-temperature fuel cells Reviewed

    Pilwon Heo, Hidetaka Sibata, Masahiro Nagao, Takashi Hibino

    Solid State Ionics   Vol. 179   page: 1446-1449   2008.9

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  104. A proton-conducting fuel cell operating with hydrocarbon fuels Reviewed

    Pilwon Heo, Kenichi Ito, Atsuko Tomita, Takashi Hibino

    Angewandte Chemie-international edition   Vol. 120   page: 7959-7962   2008.9

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  105. De-NOx reactor and Nox sensor using In3+-doped SnP2O7 with PtRhBa/c electrode Reviewed

    Masahiro Nagao, Takeshi Yoshii, Yousuke Namekata, Shinya Teranishi, Mitsuru Sano, Atsuko Tomita, Takashi Hibino

    Solid State Ionics   Vol. 179   page: 1655-1661   2008.9

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  106. Proton conduction in Sn0.95Al0.05P2O7-PBI-PTFE composite membrane Reviewed

    Pilwon Heo, Norikazu Kajiyama, Kazuyo Kobayashi, Masahiro Nagao, Mitsuru Sano, Takashi Hibino

    Electrochemical and Solid State Letters   Vol. 11 ( 6 ) page: B91-B95   2008.6

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  107. Blocking of electronic current through a Ce0.9Gd0.1O1.95 electrolyte film by growth of a thin BaCe1-xGdxO3-alpha layer Reviewed

    Atsuko Tomita, Yuki Tachi, Takashi Hibino

    Electrochemical and Solid State Letters   Vol. 11 ( 5 ) page: B68-B70   2008.5

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  108. *A singie-chamber SOFC stack operating in engine exhaust Reviewed

    Masaya Yano, Masahiro Nagao, Kohsuke Okamoto, Atsuko Tomita, Yasuyuki Uchiyama, Naoki Uchiyama, Takashi Hibino

    Electrochemical and Solid-State Letters   Vol. 11 ( 3 ) page: B29-B33   2008.3

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  109. Direct dimethyl ether fuel cella at intermediate temperatures Reviewed

    Pilwon Heo, Masahiro Nagao, Mitsuru Sano, Takashi Hibino

    Journal of The Electrochemical Society   Vol. 155 ( 1 ) page: B92-B95   2008.1

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  110. Direct oxidation of methane to methanol at low temperature and pressure in an electrochemical fuel cell Reviewed

    Atsuko Tomita, Junya Nakajima, Takashi Hibino

    Angewandte Chemie-international edition   Vol. 47   page: 1462-1464   2008.1

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  111. A proton-conducting fuel cell operating with hydrocarbon fuels Reviewed

    Heo Pilwon, Ito Kenichi, Tomita Atsuko, Hibino Takashi

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 47 ( 41 ) page: 7841 - 7844   2008

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    Low temperature, high voltage! Direct oxidation of hydrocarbon fuels, including methane, ethane, propane, and butane, occurs over Pt-free anodes in a proton-conducting fuel cell in the temperature range 100-300°C. A Mo 2C-ZrO2/C anode (30 mg Mo2C-ZrO2 per cm2) yields power densities equal to those obtained from Pt/C anodes (1-7 mg Pt per cm2) and generates higher open-circuit voltages than the Pt/C anodes. (Figure Presented) © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

    DOI: 10.1002/anie.200801667

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  112. Blocking of electronic current through a Ce0.9Gd0.1O1.95 electrolyte film by growth of a thin BaCe1-xGdxO3-alpha layer Reviewed

    Tomita Atsuko, Tachi Yuki, Hibino Takashi

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 11 ( 5 ) page: B68 - B70   2008

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    A BaCe1-x Gdx O3-α (BCG) layer was grown between Ce0.9 Gd0.1 O1.95 (GDC) layers. This was accomplished by a solid-state reaction of a BaO layer with the GDC layer. In the multilayered GDC/BCG/GDC electrolyte film, all layers showed dense and homogeneous junction structure. When a hydrogen-air fuel cell with the multilayered electrolyte cell was tested at 550-800°C, the BCG layer could partially block the electronic current through the cell. The resulting open-circuit voltage and power density were increased by a maximum of 127 mV and 202 mW cm-2, respectively, compared with those for a single-layered GDC electrolyte cell under the same conditions. © 2008 The Electrochemical Society.

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  113. A single-chamber SOFC stack operating in engine exhaust Reviewed

    Yano Masaya, Nagaoa Masahiro, Okamoto Kohsuke, Inoa Atsuko Tomitab, Uchiyarna Yasuyuki, Uchiyama Naoki, Hibino Takashi

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 11 ( 3 ) page: B29 - B33   2008

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    Heat engines emit huge amounts of exhaust which contain considerable quantities of heat and chemical energies. An increasing public awareness of global warming and oil depletion has required the development of innovative methods of recovering energy from such exhaust. A promising approach is to produce electricity from unburned fuel by using a fuel cell system. The exhaust includes cracked-light hydrocarbons, offering the possibility of applying this system to a power generator. Solid oxide fuel cells (SOFCs) can work at elevated temperatures but have poor thermal and mechanical shock resistance. In this study, we address this problem by operating the fuel cell system in a single-chamber mode, wherein no separation between fuel and oxidant gases is required. This operation provides high tolerance toward thermal cycling and breakage of the electrolyte. As a result, a twelve-cell stack exhibits stable and high performance in the exhaust from a motorcycle. © 2007 The Electrochemical Society.

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  114. Direct dimethyl ether fuel cells at intermediate temperatures Reviewed

    Heo Pilwon, Nagao Masahiro, Sano Mitsuru, Hibino Takashi

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 155 ( 1 ) page: B92 - B95   2008

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    Direct dimethyl ether fuel cells (DDMEFCs) were investigated using proton-conducting Sn0.9 In0.1 P2 O7 as an electrolyte at intermediate temperatures between 150 and 300°C. Fuel cell operation at intermediate temperatures allowed a PtC anode to achieve excellent CO tolerance and high catalytic activity for the anode reaction of DME. The catalytic activity of the PtC anode was further improved by the addition of Ru to Pt, especially at elevated temperatures. The anodic overpotential and anode product measurements revealed that the H2 produced by the reforming reaction of DME was electrochemically oxidized at the PtRuC anode, which proceeded in parallel with the direct oxidation reaction of DME. As a result, DDMEFCs with the PtRuC anode achieved a peak power density of 31, 52, and 78 mW cm-2 at 200, 250, and 300°C, respectively. © 2007 The Electrochemical Society.

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  115. Direct oxidation of methane to methanol at low temperature and pressure in an electrochemical fuel cell Reviewed

    Tomita Atsitko, Nakajima Junya, Hibino Takashi

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 47 ( 8 ) page: 1462 - 1464   2008

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    (Chemical Equation Presented) Fuel for thought? The direct oxidation of methane to methanol occurs at atmospheric pressure between 50 and 250°C in a fuel-cell-type reactor (see picture). The efficiency of the electrochemical activation of oxygen is higher than that for the catalytic activation of oxygen. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

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  116. Nano-sized electrochemical reactors for selective NOx reduction Reviewed

    Teranishi Shinya, Tsuge Akihito, Tomita Atsuko, Sano Mitsuru, Hibino Takashi

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 11 ( 10 ) page: P9 - P12   2008

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    The present study proposed a scheme for the reaction between NOx and C3 H6 in the presence of excess O2 over a proton-conducting Sn0.9 In0.1 P2 O7 -supported PtRh catalyst. C3 H6 dissociated to protons and electrons at an anodic site of the PtRh catalyst, causing a negative potential. NOx reacted with protons and electrons to form N2 and H2 O at a cathodic site of the PtRh catalyst, resulting in a positive potential. As a result, an electrochemical local cell was formed at the PtRh Sn0.9 In0.1 P2 O7, followed by self-discharge. This series of reactions could be clearly distinguished from conventional catalytic reduction of NOx by C3 H6. © 2008 The Electrochemical Society. All rights reserved.

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  117. Proton conduction in Sn(0.95)Al(0.05)P(2)O(7)-PBI-PTFE composite membrane Reviewed

    Heo Pilwon, Kajiyama Norikazu, Kobayashi Kazuyo, Nagao Masahiro, Sano Mitsuru, Hibino Takashi

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 11 ( 6 ) page: B91 - B95   2008

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    Proton-conducting composite membranes were fabricated by blending Sn0.95 Al0.05 P2 O7 having an excess of phosphates with polybenzimidazole (PBI) and polytetrafluoroethylene (PTFE). The addition of PBI to Sn0.95 Al0.05 P2 O7 - Px Oy powder stabilized the conductivity of the composite, providing higher conductivities than those of stoichiometric Sn0.95 Al0.05 P2 O7. The addition of PTFE to Sn0.95 Al0.05 P2 O7 - Px Oy -PBI powder reduced the conductivity but increased the tensile strength. The resulting composite membrane exhibited a conductivity of 0.04 S cm-1 at 200°C and a tensile strength of 2.30 MPa. Moreover, a fuel cell made with this composite membrane yielded high power densities exceeding 200 mW cm-2 above 100°C and good durability under unhumidified conditions. © 2008 The Electrochemical Society.

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  118. Intermediate-temperature proton conduction in Al3+-doped SnP2O7 Reviewed

    Atsuko Tomita, Norikazu Kajiyama, Toshio Kamiya, Masahiro Nagao, Takashi Hibino

    Journal of The Electrochemical Society   Vol. 154 ( 12 ) page: B1265-B1269   2007.12

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  119. Single-chamber SOFCs using dimethyl ether and ethanol Reviewed

    Masaya Yano, Takanori Kawai, Kosuke Okamoto, Masahiro Nagao, Mitsuru Sano, Atsuko Tomita, Takashi Hibino

    Journal of The Electrochemical Society   Vol. 154 ( 8 ) page: B865-B870   2007.8

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  120. Room-temperature hydrogen sensors based on an In3+-doped SnP2O7 proton conductor Reviewed

    Atsuko Tomita, Yosuke Namekata, Masahiro Nagao, Takashi Hibino

    Journal of The Electrochemical Society   Vol. 154 ( 5 ) page: J172-J176   2007.5

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  121. Selective catalytic reduction of NOx by H-2 using proton conductors as catalyst supports Reviewed

    Tomita Atsuko, Yoshii Takeshi, Teranishi Shinya, Nagao Masahiro, Hibino Takashi

    JOURNAL OF CATALYSIS   Vol. 247 ( 2 ) page: 137 - 144   2007.4

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    The selective catalytic reduction (SCR) of NOx by H2 was studied using proton-conducting Sn0.9In0.1P2O7 as a catalyst support at 50-350 °C. When a mixture of 800 ppm NO, 1400-8400 ppm H2, and 5% O2 in Ar was introduced to the Pt/C working electrode, NOx was reduced to N2 with N2 selectivity values > 80 %. The reaction mechanism was shown to be based on a mixed potential at the Pt/C working electrode. This mechanism was also applicable to a Sn0.9In0.1P2O7-supported Pt catalyst. H2 SCR over the Pt/Sn0.9In0.1P2O7 catalyst was characterized by a wide operating temperature window (50-350 °C) and remarkable N2 selectivity values (> 80 %). Catalyst performance could be further improved by the addition of Rh to Pt, in which NOx conversion was a maximum 1.4 times higher than that over the Pt/Sn0.9In0.1P2O7 catalyst and N2 selectivity was increased to > 89 % at all temperatures tested. © 2007 Elsevier Inc. All rights reserved.

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  122. Selective catalytic reduction of NOx by H-2 using proton conductors as catalyst supports Reviewed

    Atsuko Tomita, Takeshi Yosii, Shinya Teranishi, Masahiro Nagao, Takashi Hibino

    Jounal of Catalysis   Vol. 247 ( 2 ) page: 137-144   2007.4

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  123. Recent advances in single-chamber solid oxide fuel cells: A review Reviewed

    Yano Masaya, Tomita Atsuko, Sano Mitsuru, Hibino Takashi

    SOLID STATE IONICS   Vol. 177 ( 39-40 ) page: 3351 - 3359   2007.1

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    Solid oxide fuel cells (SOFCs) have received much recent attention as next generation alternative energy sources. In particular, current efforts are devoted to reducing SOFC costs by downsizing fuel cell systems and lowering the operating temperature. Single-chamber SOFCs (SC-SOFCs) have the potential of meeting the demands. This type of fuel cell consists of only one gas chamber, wherein the anode and cathode are exposed to the same mixture of fuel and oxidant gas. This simplified design offers the possibility of reducing stack components and eliminating the need for sealing. Furthermore, since the principle of operation in the mixture is based on exothermic partial oxidation of the fuel that evolves a large amount of reaction heat, the cell temperature can be efficiently increased, enhancing the ion conductivity of the electrolyte and the catalytic activity of the electrodes. This paper reviews the current status of SC-SOFCs with principal emphasis on the materials aspect. In addition, the benefits and limitations of SC-SOFCs are discussed based on the cell design, performance, and energy efficiency. © 2006 Elsevier B.V. All rights reserved.

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  124. A high-performance Mo2C-ZrO2 anode catalyst for intermediate-temperature fuel cells Reviewed

    Pilwon Heo, Masahiro Nagao, Mitsuru Sano, Takashi Hibino

    Journal of The Electrochemical Society   Vol. 154 ( 1 ) page: B53-B56   2007.1

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  125. *Recent advances in single-chamber solid oxide fuel cells: A review Reviewed

    Masaya Yano, Atsuko Tomita, Mitsuru Sano, Takashi Hibino

    Solid State Ionics   Vol. 177 ( 39-40 ) page: 3351-3359   2007.1

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  126. Sn0.9In0.1P2O7-based organic/inorganic composite membranes Reviewed

    Pilwon Heo, Masahiro Nagao, Toshio Kamiya, Mitsuru Sano, Atsuko Tomita, Takashi Hibino

    Journal of The Electrochemical Society   Vol. 154 ( 1 ) page: B63-B67   2007.1

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  127. 総説:機能性デバイス材料への応用展開

    矢野正也,冨田衷子,日比野高士

    セラミックス   Vol. 42   page: 867-871   2007

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  128. A high-performance Mo2C-ZrO2 anode catalyst for intermediate-temperature fuel cells Reviewed

    Heo Pilwon, Nagao Masahiro, Sano Mitsuru, Hibino Takashi

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 154 ( 1 ) page: B53 - B56   2007

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    Anode performance of non-Pt catalysts for hydrogen oxidation was investigated in intermediate-temperature proton exchange membrane fuel cells. Molybdenum carbide (Mo2 C) showed the highest catalytic activity among the transition metal carbides tested. Furthermore, the catalytic activity of Mo2 C was significantly improved by the addition of ZrO2 to the anode. Transmission electron microscopy and X-ray diffraction measurements revealed that Mo2 C was more highly dispersed in the Mo2 C- ZrO2 C than in the Mo2 CC, suggesting that the particle growth of Mo2 C was suppressed by the addition of ZrO2. We also tested the performance of a fuel cell using Mo2 C- ZrO2 C and Sn0.9 In0.1 P2 O7 as the anode and electrolyte materials, respectively, between 150 and 300°C. At 250°C or higher, the Mo2 C- ZrO2 C anode showed a cell performance comparable to that of the PtC anode. However, cell performance was strongly dependent on the operating temperature, reflecting that the catalytic activity of Mo2 C- ZrO2 was greatly lowered by the decrease in operating temperature. Thus it was concluded that the Mo2 C- ZrO2 catalyst is a promising alternative anode material to Pt, especially at intermediate temperatures. © 2006 The Electrochemical Society.

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  129. Improved LiMn2O4/graphite Li-ion cells at 55 degrees C Reviewed

    Sano Mitsuru, Hattori Takayuki, Hibino Takashi, Fujita Miho

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 10 ( 12 ) page: A270 - A273   2007

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    Sodium phosphate additives and mixed electrolytes of Li (C2 F5 SO2) 2 N (LiBETI) and LiPF6 were examined to improve cycle performances of Li1.04 Mn1.96 O4 /graphite cells at high temperatures. The cycle performance of those cells exceeded 80% at 100 cycles at 55°C in an optimum combination of a 0.975 M LiBETI and 0.025 M LiPF6 /ethylene carbonate (EC):dimethylcarbonate (DMC) (1:2) electrolyte solution containing 5% of Na4 P2 O7 or 5% of Na5 P3 O10 additive. Such a cycle performance is considered to fulfill the requirement for practical use. © 2007 The Electrochemical Society.

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  130. Intermediate-temperature proton conduction in Al3+-doped SnP2O7 Reviewed

    Tomita Atsuko, Kajiyama Norikazu, Kamiya Toshio, Nagao Masahiro, Hibino Takashi

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 154 ( 12 ) page: B1265 - B1269   2007

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    Al3+ -doped Sn P2 O7 proton conductors were prepared by controlling the initial composition of the reactants [Sn O2, Al (OH)3, and H3 P O4]. Sn1-x Alx Py Oz with y<2 displayed conductivities approximately two orders of magnitude lower than Sn1-x Alx P2 O7, while those of Sn1-x Alx Py Oz with y>2 exhibited conductivities at a maximum of 1.99 times higher. However, because the conductivity values of Sn1-x Alx Py Oz with y>2 were not stable, the optimal value of y in Sn1-x Alx Py Oz was determined to be 2. Partial substitution of Al3+ for Sn4+ in Sn1-x Alx P2 O7 led to an increase in the conductivity up until x=0.05. As a result, the conductivity reached 0.045 S cm-1 at 100°C, 0.15 S cm-1 at 200°C, and 0.19 S cm-1 at 300°C when the x and y values were 0.05 and 2, respectively. A hydrogen concentration cell with this material demonstrated that the ionic transport number was ∼1, and a fuel cell using this material demonstrated that the dc conductivity was comparable to the ac conductivity. © 2007 The Electrochemical Society.

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  131. Room-temperature hydrogen sensors based on an In3+-doped SnP2O7 proton conductor Reviewed

    Tomita Atsuko, Namekata Yousuke, Nagao Masahiro, Hibino Takashi

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 154 ( 5 ) page: J172 - J176   2007

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    A potentiometric solid-state gas sensor was fabricated using a proton-conducting Sn0.9 In0.1 P2 O7 electrolyte with an active PtC working electrode in order to study its sensing properties for small quantities (100 ppm 3%) of H2 in air at room temperature. The sensor showed electromotive force (emf) response in the negative direction to changes in the H2 concentration. Furthermore, the emf value varied linearly with the logarithm of the H2 concentration, while it was minimally affected by the water-vapor concentration. The sensing mechanism was shown to be based on the mixed potential at the working electrode through measurements of the polarization curves of H2 and air. The Sn0.9 In0.1 P2 O7 electrolyte was also applied in two single-chamber H2 sensors, wherein PtC and carbon were used as active and inactive electrodes, respectively; these electrodes were attached on the opposite surfaces or on the same surface of the electrolyte. Both single-chamber sensors could exhibit comparable H2 sensitivities, compared to the dual-chamber sensor. © 2007 The Electrochemical Society.

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  132. Single-chamber SOFCs using dimethyl ether and ethanol Reviewed

    Yano Masaya, Kawai Takanori, Okamoto Kohsuke, Nagao Masahiro, Sano Mitsuru, Tomita Atsuko, Hibino Takashi

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 154 ( 8 ) page: B865 - B870   2007

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    An anode-supported single-chamber solid oxide fuel cell (SC-SOFC), consisting of a Ce0.9 Gd0.1 O1.9 electrolyte, a Ni- Ce0.8 Sm0.2 O1.8 (SDC) cermet anode, and a Sm0.5 Sr0.5 Co O3 cathode, was operated in a mixture feed of dimethyl ether (DME), ethanol or butane, and air at a furnace temperature of 300°C. This SC-SOFC showed comparatively poor performance for DME and ethanol fuels when compared to the performance for butane fuel, resulting from the relatively small difference in catalytic activity for DME and ethanol oxidation between the anode and the cathode. An effective improvement was achieved by attaching Ru/SDC/Ni and CuZnAl catalyst layers for DME and ethanol, respectively, on the anode surface. As a result, peak power densities of 64 and 117 mW cm-2 were obtained for DME and ethanol, respectively. © 2007 The Electrochemical Society.

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  133. Sn0.9In0.1P2O7-based organic/inorganic composite membranes application to intermediate-temperature fuel cells Reviewed

    Heo Pilwon, Nagao Masahiro, Kamiya Toshio, Sano Mitsuru, Tomita Atsuko, Hibino Takashi

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 154 ( 1 ) page: B63 - B67   2007

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    An anhydrous proton conductor, 10 mol % In3+ -doped SnP2 O7 (Sn0.9 In0.1 P2 O7), was composed by 1,8-bis(triethoxysilyl)octane (TES-Oct) and 3-(trihydroxysilyl)-1-propanesulfonic acid ((THS)Pro- SO3 H) and was characterized by structural and electrochemical analysis. The composite membrane with 90 wt % Sn0.9 In0.1 P2 O7 showed high proton conductivities of 0.04 S cm-1 or more between 150 and 200°C in unhumidified air. The packing of the Sn0.9 In0.1 P2 O7 particles in the matrix was relatively uniform, with no formation of pinholes observed. Fuel cell tests verified that the open-circuit voltage was maintained at a constant value of ∼970 mV regardless of the electrolyte thickness (60-200 μm), while the Ohmic resistance was decreased to 0.24 cm2 by reducing the electrolyte thickness to 60 μm. The peak power densities achieved with unhumidified H2 and air were 109 mW cm-2 at 100°C, 149 mW cm-2 at 150°C, and 187 mW cm-2 at 200°C. Furthermore, fuel cell performance was improved by hot-pressing an intermediate layer consisting of Sn0.9 In0.1 P2 O7, PtC, TES-Oct, and (THS)Pro- SO3 H between the electrolyte and cathode. © 2006 The Electrochemical Society.

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  134. Chemical and redox stabilities of a solid oxide fuel cell with BaCe0.8Y0.2O3-alpha functioning as an electrolyte and as an anode Reviewed

    Tomita Atsuko, Tsunekawa Kiyoka, Hibino Takashi, Teranishi Shinya, Tachi Yuki, Sano Mtsuru

    SOLID STATE IONICS   Vol. 177 ( 33-34 ) page: 2951 - 2956   2006.11

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    The operation of a solid oxide fuel cell (SOFC) based on BaCe0.8Y0.2O3-α (BCY20) at 800 °C was studied without using an anode material. A porous, Ce-rich phase with a fluorite structure was formed at a depth of approximately 10 μm from the BCY20 surface by heat treatment at 1700 °C. This was due to the vaporization of BaO from the BCY20 surface. This treatment improved the cell performance and chemical stability to CO2 because the Ce-rich phase functioned as an electrically conducting and protective layer. The heat-treated BCY20 also had better chemical and redox stabilities over a Ni-Ce0.8Sm0.2O1.9 (SDC) cermet anode attached to the SDC electrolyte. The cell with the heat-treated BCY20 operated well on unhumidified methane, ethane, propane, and butane without carbon deposition, while the cell with the Ni-SDC cermet anode degraded within a few hours. Moreover, the BCY20 showed higher tolerance to 10 ppm H2S and stability over 20 times redox cycling in comparison to the Ni-SDC cermet anode. © 2006 Elsevier B.V. All rights reserved.

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  135. Chemical and redox stabilities of a solid oxide fuel cell with BaCe0.8Y0.2O3-alpha functioning as an electrolyte and as an anode Reviewed

    Atsuko Tomita, Kiyoka Tsunekawa, Takashi Hibino, Shinya Teranishi, Yuki Tachi, Mitsuru Sano

    Solid State Ionics   Vol. 177 ( 33-34 ) page: 2951-2956   2006.11

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  136. Proton conduction in In3+-doped SnP2O7 at intermediate temperatures Reviewed

    Masahiro Nagao, Toshio Kamiya, Pilwon Heo, Atsuko Tomita, Takashi Hibino, Mitsuru Sano

    Journal of The Electrochemical Society   Vol. 153 ( 8 ) page: A1604-A1609   2006.8

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  137. Comparative performance of anode-supported SOFCs using a thin Ce0.9Gd0.1O1.95 electrolyte with an incorporated BaCe0.8Y0.2O3– layer in hydrogen and methane Reviewed

    Atsuko Tomita, Shinya Teranishi, Masahiro Nagao, Takashi Hibino, Mitsuru Sano

    Journal of The Electrochemical Society   Vol. 153 ( 6 ) page: A956-A960   2006.6

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  138. Intermediate-temperature NOx sensor based on an in3+-doped SnP2O7 proton conductor Reviewed

    Masahiro Nagao, Yosuke Namekata, Takashi Hibino, Mitsuru Sano, Atsuko Tomita

    Electrochemical and Solid-State Letters   Vol. 9 ( 6 ) page: H48-H51   2006.6

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  139. Performance of an intermediate-temperature fuel cell using a proton-conducting Sn0.9In0.1P2O7 electrolyte Reviewed

    Pilwon Heo, Hidetaka Shibata, Masahiro Nagao, Takashi Hibino, Mitsuru Sano

    Journal of The Electrochemical Society   Vol. 153 ( 5 ) page: A897-A901   2006.5

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  140. *A proton-conducting In3+-doped SnP2O7 electrolyte for intermediate-temperature fuel cells Reviewed

    Masahiro Nagao, Akihiko Takeuchi, Pilwon Heo, Takashi Hibino, Mitsuru Sano, Atsuko Tomita

    Electrochemical and Solid-State Letters   Vol. 9 ( 3 ) page: A105-A109   2006.3

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  141. Electrochemical reduction of NOx at intermediate temperatures using a proton-conducting In3+-doped SnP2O7 electrolyte Reviewed

    Masahiro Nagao, Takeshi Yoshii, Takashi Hibino, Mitsuru Sano, Atsuko Tomita

    Electrochemical and Solid-State Letters   Vol. 9   page: J1-J4   2006.2

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  142. A high performance Pt-free anode for intermediate-temperature fuel cells Reviewed

    Heo P., Nagao M., Sano M., Hibino T.

    ECS Transactions   Vol. 3 ( 1 ) page: 453 - 458   2006

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    Proton exchange membrane fuel cells (PEMFCs) are among the most promising power sources for vehicular and residential applications because of their clean and efficient energy conversion. However, these fuel cells require expensive Pt-based electrodes, which raise the cost of fuel-cell systems considerably. Here, we propose an approach to solving this problem by combining a molybdenum carbide (Mo2C) catalyst with an In3+-doped SnP 2O7 electrolyte. The resulting fuel cell can operate in the temperature range of 150 to 300°C, providing the high catalytic activity of Mo2C for electrochemical hydrogen oxidation, which is comparable to that of a Pt anode catalyst. Another important advantage of this fuel cell is that the Mo2C anode catalyst showed perfect tolerance to 10%CO. copyright The Electrochemical Society.

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  143. Comparative performance of anode-supported SOFCs using a thin Ce0.9Gd0.1O1.95 electrolyte with an incorporated BaCe0.8Y0.2O3-alpha layer in hydrogen and methane Reviewed

    Tomita A, Teranishi S, Nagao M, Hibino T, Sano M

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 153 ( 6 ) page: A956 - A960   2006

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    Multilayered Ce0.9 Gd0.1 O1.95 Ba Ce0.8 Y0.2 O3-α Ce0.9 Gd0.1 O1.95 (GDCBCYGDC) electrolytes were prepared by tape casting on a Ni- Ce0.8 Sm0.2 O1.9 anode support. The overall electrolyte thickness ranged from 30 to 35 μm, including a 3 μm thick BCY layer. When the multilayered electrolyte cell was tested with hydrogen at the anode and air at the cathode in the temperature range of 500-700°C, it yielded open-circuit voltages (OCVs) of 846-1024 mV, which were higher than the OCVs of 753-933 mV obtained for a single-layered GDC electrolyte cell under the same conditions. The corresponding peak power densities reached 273, 731, and 1025 mW cm-2 at 500, 600, and 700°C, respectively. The multilayered electrolyte cell could also be applied to direct methane solid oxide fuel cell (SOFC) and single-chamber SOFC operating in a mixture of methane and air. These SOFCs yielded OCVs of 880-950 mV and reasonable power densities without coking. © 2006 The Electrochemical Society.

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  144. A proton-conducting In3+-doped SnP2O7 electrolyte for intermediate-temperature fuel cells Reviewed

    Nagao M, Takeuchi A, Heo P, Hibino T, Sano M, Tomitab A

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 9 ( 3 ) page: A105 - A109   2006

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    We report proton conduction in In3+ -doped Sn P2 O7 in the temperature range from 100 to 300°C, and the performance of a H2 -air fuel cell using this material as the electrolyte. The proton conductivity of In3+ -doped Sn P2 O7 was more than 10-1 S cm-1 between 125 and 300°C, and a conductivity value of 1.95× 10-1 S cm-1 was achieved at 250°C. The resulting fuel cell exhibited a reasonable power density of 264 mW cm-2 at 250°C (electrolyte thickness=0.35 mm), together with perfect tolerance toward 10% CO and good thermal stability in unhumidified conditions. © 2006 The Electrochemical Society. All rights reserved.

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  145. Electrochemical reduction of NOx at intermediate temperatures using a proton-conducting In3+-doped SnP2O7 electrolyte Reviewed

    Nagao M, Yoshii T, Hibino T, Sano M, Tomita A

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 9 ( 2 ) page: J1 - J4   2006

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    In 3+-doped SnP 2O 7 was used as the electrolyte in an electrochemical cell for the reduction of NO between 150 and 300°C in the presence of excess O 2. NO was reduced to N 2 at a Pt/C cathode when current was applied to the cell. The electrocatalytic activity of the cathode for the reduction of NO was shown to be highest at 250°C. The addition of Ba species (an oxide/carbonate mixture) to the cathode further promoted the reduction of NO by adsorbing NO more selectively than O 2 on the surface. A resulting current efficiency of 5.81% was achieved in a 2% O 2 atmosphere. © 2005 The Electrochemical Society. All rights reserved.

    DOI: 10.1149/1.2149213

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  146. Intermediate-temperature NOx sensor based on an In3+-doped SnP2O7 proton conductor Reviewed

    Nagao M, Namekata Y, Hibino T, Sano M, Tomita A

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 9 ( 6 ) page: H48 - H51   2006

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    A potentiometric NOx sensor using a proton-conducting Sn0.9 In0.1 P2 O7 electrolyte with a PtRhC working electrode was fabricated to study sensing properties for NO and N O2 at intermediate temperatures. The sensor showed electromotive force (emf) responses to changes in NO and N O2 concentrations. Interestingly, the emf values for both NO and N O2 increased in the positive direction with increasing gas concentration. The sensing mechanism was shown to be based on a mixed potential at the working electrode through measurements of the polarization curves of NO or N O2 and water vapor. © 2006 The Electrochemical Society.

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  147. Proton conduction in In<sup>3+</sup>-doped SnP<inf>2</inf>O<inf>7</inf> with various P/(Sn+In) ratios Reviewed

    Nagao M., Heo P., Kamiya T., Hibino T., Sano M., Tomita A.

    ECS Transactions   Vol. 2 ( 10 ) page: 43 - 49   2006

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    A proton conducting, 10 mol% In3+-doped SnP2O 7 (Sn0.9In0.1 P2O7) was characterized by thermogravimetric analysis (TGA), transmission electron microscope (TEM) measurement, and electrochemical techniques. We prepared Sn0.9In0.1P2=x07±x samples with various P/(Sn+In) molar ratios from 1.7 to 2.6 through the control of the amount of phosphoric acid at the preparation process in order to examine electrochemical properties and thermal stabilities. Sn0.9In 0.1P2O7 with a stoichiometric P/(Sn+In) molar ratio of 2.0 showed a proton conductivity of about 0.19 S cm-1 at 250°C under unhumidified conditions. When the P/(Sn+In) molar ratios were over 2.0, the formation of amorphous layer composed of phosphorus compounds were observed over the surface of Sn0.9In0.1P 2O7 particles. The proton conductivity slightly increased with increasing the P/(Sn+In) molar ratios from 2.0 to 2.6. It is considered that the amorphous layer enhanced the proton conductivity by surface conduction. On the other hand, the thermal stability of this amorphous layer during heating-cooling cycle was not enough high to apply to electrochemical devises. As a result, it is important to prepare Sn0.9In0.1P 2O7 with the P/(Sn+In) molar ratio of 2.0 to achieve both sufficient proton conductivity and high thermal stability. Copyright The Electrochemical Society.

    DOI: 10.1149/1.2408942

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  148. Proton conduction in In3+-doped SnP2O7 at intermediate temperatures Reviewed

    Nagao Masahiro, Kamiya Toshio, Heo Pilwon, Tomita Atsuko, Hibino Takashi, Sano Mitsuru

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 153 ( 8 ) page: A1604 - A1609   2006

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    SnP2 O7 -based proton conductors were characterized by Fourier transform infrared spectroscopy (FTIR), temperature-programmed desorption (TPD), X-ray diffraction (XRD), and electrochemical techniques. Undoped SnP2 O7 showed overall conductivities greater than 10-2 S cm-1 in the temperature range of 75-300°C. The proton transport numbers of this material at 250°C under various conditions were estimated, based on the ratio of the electromotive force of the galvanic cells to the theoretical values, to be 0.97-0.99 in humidified H2 and 0.89-0.92 under fuel cell conditions. Partial substitution of In3+ for Sn4+ led to an increase in the proton conductivity (from 5.56× 10-2 to 1.95× 10-1 S cm-1 at 250°C, for example). FTIR and TPD measurements revealed that the effects of doping on the proton conductivity could be attributed to an increase in the proton concentration in the bulk Sn1-x Inx P2 O7. The deficiency of P2 O7 ions in the Sn1-x Inx P2 O7 bulk decreased the proton conductivity by several orders of magnitude, which was explained as due to a decrease in the proton mobility rather than the proton concentration. The mechanism of proton incorporation and conduction is examined and discussed in detail. © 2006 The Electrochemical Society. All rights reserved.

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  149. Performance of an intermediate-temperature fuel cell using a proton-conducting Sn0.9In0.1P2O7 electrolyte Reviewed

    Heo P, Shibata H, Nagao M, Hibino T, Sano M

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 153 ( 5 ) page: A897 - A901   2006

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    Performance of a fuel cell using Sn0.9 In0.1 P2 O7 as the electrolyte was evaluated in the temperature range of 150-300°C under unhumidified conditions. The IR drop and electrode overpotential of the cell were measured separately by the current interruption method. The dc conductivity values of the electrolyte between 150 and 300°C, estimated from the IR drop, were comparable to the ac conductivity values (1.48× 10-1 -1.95× 10-1 S cm-1) of the electrolyte. The cell performance was improved by forming an intermediate layer consisting of Sn0.9 In0.1 P2 O7 and PtC catalyst powders at the interface between the electrolyte and cathode, which significantly reduced the cathode polarization. As a result, the peak power density reached 264 mW cm-2 at 250°C using the 0.35-mm -thick electrolyte. The present fuel cell also showed high stability at low relative humidities (p H2 O ≈0.0075 atm) and 10% CO concentration. © 2006 The Electrochemical Society. All rights reserved.

    DOI: 10.1149/1.2183927

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  150. Surface modification of a doped BaCeO3 to function as an erectrolyte and as an anode for SOFCs Reviewed

    Atsuko Tomita, Takashi Hibino, Mitsuru Sano

    Electrochemical and Solid-State Letters   Vol. 8   page: A333-A336   2005.7

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  151. Improvement of a reduction-resistant Ce0.8Sm0.2O1.9 electrolyte by optimizing a thin BaCe1-xSmxO3-alpha layer for intermediate-temperature SOFCs Reviewed

    Hirabayashi D, Tomita A, Teranishi S, Hibino T, Sano M

    SOLID STATE IONICS   Vol. 176 ( 9-10 ) page: 881 - 887   2005.3

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    Sm3+-doped ceria (SDC) electrolytes growing various BaCe 1-xSmxO3-α (BCS) layers over the electrolyte surface were investigated in order to develop high-performance solid oxide fuel cells in the temperature range of 600-900°C. The BCS layers were grown by a solid-state reaction of the electrolyte substrate and a BaO film spin-coated previously over the substrate surface under different preparation conditions. The thickness of the layer was controlled with a precision of micrometer by the number of coats. The composition of the layer was optimized by the sintering temperature. As a result, a dense and microcrack-free BCS layer was formed over the electrolyte surface, and the junction between the electrolyte and layer was almost homogeneous. A hydrogen-air fuel cell with the improved electrolyte showed open-circuit voltages (OCVs) ranging from 857 (900°C) to 1002 mV (600°C). Furthermore, the peak power densities of this fuel cell were higher than those of a fuel cell with an uncoated SDC electrolyte. © 2004 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.ssi.2004.12.007

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  152. Improvement of a reduction-resistant Ce0.8Sm0.2o1.9 electrolyte by optimizing a thin BaCe1-xSmxO3-α layer for intermediate-temperature SOFCs Reviewed

    Daisuke Hirabayashi, Atsuko Tomita, Shinya Teranishi, Takashi Hibino, Mitsuru Sano

    Solid State Ionics   Vol. 176   page: 881-887   2005.3

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  153. Single-chamber SOFCs with a Ce0.9Gd0.1O1.95 electrolyte film for low-temperature operation Reviewed

    Atsuko Tomita, Daisuke Hirabayashi, Takashi Hibino, Masahiro Nagao, Mitsuru Sano

    Electrochemical and Solid-State Letters   Vol. 8 ( 1 ) page: A63-A65   2005.1

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  154. 総説:マイクロリアクターによる水素製造

    冨田衷子,日比野高士,佐野 充

    ケミカルエンジニアリング   Vol. 50   page: 18-23   2005

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  155. 総説:MP2O7系固体電解質のプロトン導電性とその応用

    長尾征洋,冨田衷子,日比野高士,佐野 充

      Vol. 73   page: 846-850   2005

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  156. Single-chamber SOFCs with a Ce0.9Gd0.1O1.95 electrolyte film for low-temperature operation Reviewed

    Tomita A, Hirabayashi D, Hibino T, Nagao M, Sano M

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 8 ( 1 ) page: A63 - A65   2005

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    Single-chamber solid oxide fuel cells (SOFCs) with an anode-supported Ce0.9Gd0.1O1.95 electrolyte were operated in a mixture of butane and air at furnace temperatures of 200-300°C. The electromotive force (emf) of the cell and the voltage drop were strongly influenced by the catalytic activity of the anode for the partial oxidation of butane. The promotion of hydrogen formation by the addition of Ru to the anode caused an increase in the emf and a reduction in the voltage drop. As a result, stable power densities of 44 and 176 mW cm-2 were obtained at 200 and 300°C, respectively. © 2004 The Electrochemical Society. All rights reserved.

    DOI: 10.1149/1.1836120

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  157. Surface modification of a doped BaCeO3 to function as an electrolyte and as an anode for SOFCs Reviewed

    Tomita A, Hibino T, Sano M

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 8 ( 7 ) page: A333 - A336   2005

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    Dual functions of BaCe0.8Y0.2O3-α, (BCY) as an electrolyte and as an anode were improved for solid oxide fuel cell (SOFC) applications. A porous Ce-rich phase with fluorite structure was formed with a depth of ∼10 μm from the BCY surface by vaporization of BaO from the BCY surface at 1700°C. The resulting BCY surface showed enough electronic conductivity to provide electrical collection and a high electrocatalytic activity for hydrogen oxidation. A hydrogen-air fuel cell with the BCY electrolyte exhibited reasonable performances without using an anode material between 750 and 950°C. © 2005 The Electrochemical Society. All rights reserved.

    DOI: 10.1149/1.1928230

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  158. SOFC-type microreactors that generate hydrogen for PEFC applications Reviewed

    Tomita A., Hirabayashi D., Nagao M., Sano M., Hibino T.

    Solid State Ionics   Vol. 174 ( 1-4 ) page: 9 - 13   2004.10

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    A fuel cell-type microreader that generates both hydrogen and electrical power from dry butane around 700°C is presented for polymer-electrolyte fuel cell (PEFC) applications. To demonstrate this concept, solid-oxide fuel cells (SOFCs) with different Fe2O3-based anodes were fabricated, and their performances were evaluated. A Fe2O3/Cr 2O3 composite anode met this criterion the most; hydrogen was produced with increasing current density; CO2/CO concentration ratios in the outlet gases were more than 2; polarization resistances were about 1 Ω cm2; carbon deposition was much more suppressed with these anodes than with a Ni/SDC cermet anode. The resulting peak power density was 110 mW cm-2 by using a 0.25-mm-thick Ce0.9Gd 0.1O1.95 (GDC) electrolyte. The effect of Cr 2O3 added into the Fe2O3 anode was also discussed in detail. © 2004 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.ssi.2004.07.023

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  159. Design of a reduction-resistant Ce0.8Sm0.2O1.9 electrolyte through growth of a thin BaCe1-xSmxO3-α layer over electrolyte surface Reviewed

    Daisuke Hirabayashi, Atsuko Tomita, Takashi Hibino, Masahiro Nagao, Mitsuru Sano

    Electorochemical and Solid-State Letters   Vol. 7   page: A318-A320   2004.10

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  160. Electrochemical properties of lithium manganese oxides with different surface areas for lithium ion batteries Reviewed

    Takahashi K, Saitoh M, Asakura N, Hibino T, Sano M, Fujita M, Kifune K

    JOURNAL OF POWER SOURCES   Vol. 136 ( 1 ) page: 115 - 121   2004.9

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    Two lithium manganese oxides, Li1.03Mn1.96O 4, with different surface areas of 3.55 and 0.68m2/g were prepared and their electrochemical properties were studied as positive electrodes for lithium ion batteries. Cycle performance tests gave capacity losses of 9 and 18% at 25°C, and 28 and 33% at 55°C for the samples with larger and smaller surface areas, respectively. The recovery of capacity losses have been found on the addition of the conductor after cycles. The defect of the conductivity between the active materials and the conductors was found mostly responsible for the capacity loss in the smaller surface sample at 25°C. Cycle performance tests in each region of the charge states divided into five regions show that larger capacity losses are observed in rather lower potential states. Storage performances show the largest capacity loss at 10 and 20% of SOC and the less capacity losses at both 0 and 50-100% of SOC in both of the samples. However, in every region, the capacity loss is much smaller in the larger surface sample than in the smaller surface sample. The maximum Mn dissolution is observed to occur at 100% of SOC (4.5V) and the next is found around 10-20% of SOC in either sample. © 2004 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.jpowsour.2004.05.014

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  161. Bi-based oxide anodes for direct hydrocarbon SOFCs at intermediate temperatures Reviewed

    Daisuke Hirabayashi, Atsuko Hashimoto, Takashi Hibino, Ushio Harada,Mitsuru Sano

    Electrochemical and Solid-State Letters   Vol. 7   page: A108-A110   2004.5

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  162. Proton conduction at the surface of Y-doped BaCeO3 and its application to an air/fuel sensor Reviewed

    Tomita A, Hibino T, Suzuki M, Sano M

    JOURNAL OF MATERIALS SCIENCE   Vol. 39 ( 7 ) page: 2493 - 2497   2004.4

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  163. Proton conduction at the surface of Y-doped BaCeO<inf>3</inf> and its application to an air/fuel sensor Reviewed

    Tomita A., Hibino T., Suzuki M., Sano M.

    Journal of Materials Science   Vol. 39 ( 7 ) page: 2493 - 2497   2004.4

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    25 mol% Y3+-doped BaCeO3 (BCY25) showed an extremely low activation energy of 0.3 eV for proton conduction at the surface. The resulting overall conductivity at the surface reached 8.24 × 10 -3 S cm-1 at 400°C, which was 3, 8, and 28 times higher than those in the bulk of BCY25, 20 mol% Sm3+-doped ceria, and 8 mol% yttria-stabilized zirconia, respectively. Such fast proton conduction enabled an air/fuel (A/F) sensor using BCY25 as the solid electrolyte to work above 150°C for H2 and above 250°C for C2H 4. © 2004 Kluwer Academic Publishers.

    DOI: 10.1023/B:JMSC.0000020015.80430.d8

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  164. Proton conduction at the surface of Y-doped BaCeO3 and its application to an air/fuel sensor Reviewed

    Atsuko Hashimoto, Takashi Hibino, Masanori Suzuki, Mitsuru Sano

    Journal Of Materials Science   Vol. 39   page: 2493-2497   2004.4

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  165. Solid oxide fuel cells operating without using an anode material Reviewed

    Hirabayashi D, Tomita A, Brito ME, Hibino T, Harada U, Nagao M, Sano M

    SOLID STATE IONICS   Vol. 168 ( 1-2 ) page: 23 - 29   2004.3

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  166. Solid oxide fuel cells operating without using an anode material Reviewed

    Hirabayashi D., Tomita A., Brito M.E., Hibino T., Harada U., Nagao M., Sano M.

    Solid State Ionics   Vol. 168 ( 1-2 ) page: 23 - 29   2004.3

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    We proposed a new type of solid oxide fuel cell (SOFC) operating without using an anode material, where the anode was spontaneously formed by reduction of the electrolyte surface under reducing gas conditions. A BaCe 0.76Y0.20Pr0.04O3-α electrolyte most successfully met this criterion. This material showed high mixed protonic-electronic conduction, whereas the open circuit voltage (OCV) of the cell was slightly lower than the theoretical value. The resulting SOFC exhibited reasonable fuel cell performances together with a good stability to thermal and redox cyclings and high resistance to carbon deposition up to 800 °C for dry methane, ethane, and propane. © 2004 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.ssi.2004.01.024

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  167. SOFC-type microreactors that generate Hydrogen for PEFC applications Reviewed

    Atsuko Tomita, Daisuke Hirabayashi, Masahiro Nagao, Mitsuru Sano, Takashi Hibino

    Solid State Ionics   Vol. 174   page: 9-13   2004

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  168. Solid oxide fuel cells operating without using an anode material Reviewed

    Daisuke Hirabayashi, Atsuko Tomita, M.E.Brito, Takashi Hibino, Ushio Harada, Masahiro Nagao, Mitsuru Sano

    Solid State Ionics   Vol. 168   page: 23-29   2004

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  169. Bi-based oxide anodes for direct hydrocarbon SOFCs at intermediate temperatures Reviewed

    Hirabayashi D, Hashimoto A, Hibino T, Harada U, Sano M

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 7 ( 5 ) page: A108 - A110   2004

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    Doped Bi-based oxides were investigated as potential anode materials for direct hydrocarbon solid oxide fuel cells (SOFCs) at intermediate temperatures. (Bi2O3)0.85(Ta2O5) 0.15 met this criterion most successfully. A fraction of Bi 2O3 in this material was reduced to BiO and Bi metal under fuel conditions, which yielded high conductivities (>1 S cm-1) based on oxide ions and electrons above 500°C. Carbon deposition was successfully prevented when butane was used as the fuel below 800°C. The catalytic activities for hydrocarbon oxidation were high enough to promote the complete oxidation of butane during cell operation. These abilities provided an enhanced anode performance with increasing temperature from 600 to 750°C, and the resulting polarization resistance reached 1.4 Ω cm2 at 750°C. © 2004 The Electrochemical Society. All rights reserved.

    DOI: 10.1149/1.1667791

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  170. Design of a reduction-resistant Ce0.8Sm0.2O1.9 electrolyte through growth of a thin BaCe1-xSmxO3-alpha a layer over electrolyte surface Reviewed

    Hirabayashi D, Tomita A, Hibino T, Nagao M, Sano M

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 7 ( 10 ) page: A318 - A320   2004

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    A method that can block off electronic current through a samaria-doped ceria (SDC, Ce0.8Sm0.2O1.9) electrolyte is proposed. A thin BaCeO3-based layer 12 μm thick was grown by a solid-state reaction of the electrolyte substrate and a BaO film deposited previously over the substrate surface at 1500°C. A homogeneous junction between the layer and the electrolyte was formed, thus allowing no delamination and cracking of the layer. Tolerance of this layer to CO2 was high enough to suppress decomposition into BaCO3 and CeO2. Open-circuit voltages of a hydrogen-air fuel cell with the coated SDC electrolyte were near 1 V or more in the range of 600-950°C. The resulting peak power density was higher than that of a fuel cell with an uncoated SDC electrolyte. © 2004 The Electrochemical Society.

    DOI: 10.1149/1.1786231

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  171. Intermediate-temperature SOFCs with Ru-catalyzed Ni-cermet anodes Reviewed

    Hashimoto A., Hirabayashi D., Hibino T., Sano M.

    Key Engineering Materials   Vol. 269   page: 151 - 154   2004

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    The promotion of the direct electrochemical oxidation of hydrocarbons in a solid oxide fuel cell was investigated using a ceria-based electrolyte with different noble metals-containing anode at 600°C. The attempted approach toward this objective was to avoid interference from a large amount of steam and CO2 products, because they degrade the anode performance. Ru was an effective catalyst for removing these gases from the anode surface due to its high catalytic activity for the steam and CO2 reforming of hydrocarbons. This permitted a smooth access of the unreacted hydrocarbons to the three-phase boundary, thus resulting in a noticeably high anode performance. The resulting peak power density reached 750 mW cm-2 with dry methane, which was comparable to the peak power density of 769 mW cm -2 with wet hydrogen.

    DOI: 10.4028/www.scientific.net/kem.269.151

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  172. Ru-catalyzed anode materials for direct hydrocarbon SOFCs Reviewed

    Hibino T, Hashimoto A, Yano M, Suzuki M, Sano M

    ELECTROCHIMICA ACTA   Vol. 48 ( 17 ) page: 2531 - 2537   2003.7

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    A solid oxide fuel cell using a thin ceria-based electrolyte film with a Ru-catalyzed anode was directly operated on hydrocarbons, including methane, ethane, and propane, at 600 °C. The role of the Ru catalyst in the anode reaction was to promote the reforming reaction of the unreacted hydrocarbons by the produced steam and CO2, which avoided interference from steam and CO2 in the gas-phase diffusion of the fuels. The resulting peak power density reached 750 mW cm-2 with dry methane, which was comparable to the peak power density of 769 mW cm-2 with wet (2.9 vol.% H2O) hydrogen. More important was the fact that the cell performance was maintained at a high level regardless of the change in the methane utilization from 12 to 46% but was significantly reduced by increasing the hydrogen utilization from 13 to 42%. While the anodic reaction of hydrogen was controlled by the slow gas diffusion, the anodic reaction of methane was not subject to the onset of such a gas-diffusion process. © 2003 Elsevier Science Ltd. All rights reserved.

    DOI: 10.1016/S0013-4686(03)00296-2

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  173. A resistor-type sensor for the detection of CO in reformed gases Reviewed

    Atsuko Hashimoto, Takashi Hibino, Kazuyo Kobayashi, Mitsuru Sano

    Electrochemistry   Vol. 71   page: 398-401   2003.6

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  174. A resistor-type sensor for the detection of CO in reformed gases Reviewed

    Hashimoto A, Hibino T, Kobayashi K, Sano M

    ELECTROCHEMISTRY   Vol. 71 ( 6 ) page: 398 - 401   2003.6

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  175. A resistor-type sensor for the detection of CO in reformed gases Reviewed

    Hashimoto A., Hibino T., Kobayashi K., Sano M.

    Electrochemistry   Vol. 71 ( 6 ) page: 398 - 401   2003.6

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    Resistor-type sensor devices using a samaria-doped ceria electrolyte with different working electrodes were fabricated for detecting carbon monoxide (CO) in reformed gases between 250 and 425°C. The electrochemical oxidation of H2 over a Pd working electrode was the most sensitive to a reversible poisoning by 50-4000 ppm CO in the presence of 50% hydrogen, 10% carbon dioxide, and 6% water vapor, which provided an increase in the electrode-reaction resistance at the electrode-electrolyte interface. The resulting sensor signal was strongly dependent on the CO concentration, where linear relationships between the signal and the logarithm of the CO concentration were obtained, especially below 1000 ppm with 90% response and 90% recovery times of about 20 seconds. An improvement in the CO-sensing properties of the present sensor device above 300°C was also carried out by the addition of Au to the Pd working electrode.

    DOI: 10.5796/electrochemistry.71.398

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  176. Ru-catalyzed anode materials for direct hydrocarbon SOFCs Reviewed

    Takashi Hibino, Atsuko Hashimoto, Masaya Yano, Masanori Suzuki, Mitsuru Sano

    Electrochimica Acta   Vol. 48   page: 2531-2537   2003

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  177. 総説:高性能デバイスの開発を目指して

    鈴木憲司,日比野高士

      Vol. 16   page: 42-42   2003

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  178. 総説:SOFCの低温作動と混合ガス発電を可能にする電極触媒の開発

    日比野高士

    燃料電池   Vol. 2   page: 36-41   2003

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  179. An intermediate-temperature solid oxide fuel cell providing higher performance with hydrocarbons than with hydrogen Reviewed

    Takashi Hibino, Atsuko Hashimoto, Kazuyo Asano, Masaya Yano, Mosanori Suzuki, Shin-ichiro Yoshida, Mitsuru Sano

    Electrochemical and Solid-State Letters   Vol. 5   page: A242-A244   2002.11

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  180. A solid oxide fuel cell using Y-doped BaCeO3 with Pd-loaded FeO anode and Ba0.5Pr0.5CoO3 cathode at low temperatures Reviewed

    Takashi Hibino, Atsuko Hashimoto, Masanori Suzuki, Mitsuru Sano

    Journal of the Electrochemical Society   Vol. 149   page: A1503-A1508   2002.11

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  181. A solid oxide fuel cell using Y-doped BaCeO3 with Pd-loaded FeO anode and Ba0.5Pr0.5CoO3 cathode at low temperatures Reviewed

    Hibino T, Hashimoto A, Suzuki M, Sano M

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 149 ( 11 ) page: A1503 - A1508   2002.11

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    The performance of a solid oxide fuel cell (SOFC) with the configuration, H2, 3 wt % Pd-loaded FeO|25 mol % Y3+-doped BaCeO3 (BCY25)|Ba0.5Pr0.5CoO3, air, was studied between 350 and 600°C. The BCY25 electrolyte showed higher ion conductivities than 8 mol % yttria-stabilized zirconia (YSZ) below 800°C and 20 mol % Sm3+-doped ceria (SDC) below 600°C, thus having the smallest ohmic resistance loss during cell discharge below 600°C among the three electrolytes. The overpotentials of the Pd-loaded FeO anode and the Ba0.5Pr0.5CoO3 cathode at 600°C were 25 and 53 mV, respectively, at 200 mA cm-2, which were less than one-fourth those of a Pt electrode. The resulting peak power density was higher than those obtained for two SOFCs using the YSZ and SDC electrolytes with a Ni-SDC anode and a Sm0.5Sr0.5CoO3 cathode below 600°C.

    DOI: 10.1149/1.1513983

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  182. An intermediate-temperature solid oxide fuel cell providing higher performance with hydrocarbons than with hydrogen Reviewed

    Hibino T, Hashimoto A, Asano K, Yano M, Suzuki M, Sano M

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 5 ( 11 ) page: A242 - A244   2002.11

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    The promotion of direct electrochemical oxidation of hydrocarbons in a solid oxide fuel cell was investigated using a ceria-based electrolyte with different noble metals-containing anode at 600°C. The objective was to avoid interference from a large amount of steam and CO2 being produced by discharging the cell, because these gases degrade the anode performance, especially at a high fuel utilization. Ru was an effective catalyst for removing these gases from the anode surface due to its high catalytic activity for the steam and CO2 reforming of hydrocarbons. The resulting peak power densities reached 750 mW cm-2 with dry methane, which was comparable to the peak power density of 769 mW cm-2 with wet (2.9 vol % H2O) hydrogen. The cell performance was maintained at a high level regardless of the change in methane utilization from 12 to 46% but was significantly reduced by increasing hydrogen utilization from 13 to 42%. The anodic reaction of hydrogen was controlled by the slow surface diffusion of hydrogen, while the anodic reaction of methane was not subject to the onset of such a gas-diffusion process.

    DOI: 10.1149/1.1508551

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  183. Solid oxide fuel cells that enable the detection of CO in reformed gases Reviewed

    Atsuko Hashimoto, Takashi Hibino, Mitsuru Sano

    Sensors and Actuators B   Vol. 86   page: 12-19   2002.9

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  184. Solid oxide fuel cells that enable the detection of CO in reformed gases Reviewed

    Hashimoto A, Hibino T, Sano M

    SENSORS AND ACTUATORS B-CHEMICAL   Vol. 86 ( 1 ) page: 12 - 19   2002.8

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  185. Solid oxide fuel cells that enable the detection of CO in reformed gases Reviewed

    Hashimoto A., Hibino T., Sano M.

    Sensors and Actuators, B: Chemical   Vol. 86 ( 1 ) page: 12 - 19   2002.8

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    Solid oxide fuel cells (SOFCs) using Pd metal as the anode were fabricated for detection of CO in a flowing mixture of 0-4000 ppm CO, 50% H2, 10% CO2 and 6% H2O vapor between 300 and 400 °C. When 20 mol% Sm3+-doped CeO2 (SDC) was used as the electrolyte, the Pd anode was subjected to a large and reversible change in the anodic-reaction resistance with the CO concentration. This behavior brought about an almost linear relationship between the electromotive force (EMF) generated from the cell or the short-circuit current through the cell and the logarithm of the CO concentration. In both signals, the minimum detectable CO concentration was 50 ppm, and the 90% response and 90% recovery times were about 60 s. However, the EMF of the cell at a CO concentration of 0ppm significantly deviated from the theoretical value, which made it difficult to obtain reproducible data. In addition, the current signal of a few μA at a CO concentration of 4000 ppm was not large enough to monitor the CO concentration exactly. The improvement of these problems could be achieved by using 25 mol% Y3+-doped BaCeO3 (BCY25) with higher ionic conduction as the electrolyte: the EMF of the cell at a CO concentration of 0 ppm was near the theoretical value; the current signal reached 66 μA at a CO concentration of 4000 ppm. © 2002 Elsevier Science B.V. All rights reserved.

    DOI: 10.1016/S0925-4005(02)00068-0

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  186. A fuel-cell-type sensor for detection of carbon monoxide in reformed gases Reviewed

    Atsuko Hashimoto, Takashi Hibino, Mitsuru Sano

    Electrochemical and Solid-State Letters   Vol. 5   page: H1-H3   2002.2

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  187. A solid oxide fuel cell with a novel geometry that eliminates the need for preparing a thin electrolyte film Reviewed

    Takashi Hibino, Atsuko Hashimoto, Masanori Suzuki, Masaya Yano, Shin-ichiro Yoshida, Mitsuru Sano

    Journal of the Electrochemical Society   Vol. 149   page: A195-A200   2002.2

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  188. High performance anodes for SOFCs operating in methane-air mixture at reduced temperatures Reviewed

    Takashi Hibino, Atsuko Hashimoto, Masaya Yano, Masanori Suzuki, Shin-ichiro Yoshida, Mitsuru Sano

    Journal of The Electrochemical Society   Vol. 149   page: A133-A136   2002.2

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  189. A fuel-cell-type sensor for detection of carbon monoxide in reformed gases Reviewed

    Hashimoto A, Hibino T, Sano M

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 5 ( 2 ) page: H1 - H3   2002.2

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    A solid oxide fuel cell using a sumaria-doped ceria electrolyte with a Pd anode was fabricated for detecting carbon monoxide (CO) in reformed gases at 300°C. The CO concentration in a flowing mixture of 0-4000 ppm CO, 50% hydrogen, 10% carbon dioxide, and 6% water vapor was related to a decrease in both the electromotive force generated from the cell and the short-circuits current through the cell due to a reversible change in the anodic resistance with the CO concentration. In both signals, the minimum detectable concentration was 50 ppm, and the 90% response and 90% recovery times were as short as 20 s.

    DOI: 10.1149/1.1432243

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  190. A solid oxide fuel cell with a novel geometry that eliminates the need for preparing a thin electrolyte film Reviewed

    Hibino T, Hashimoto A, Suzuki M, Yano M, Yoshida S, Sano M

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 149 ( 2 ) page: A195 - A200   2002.2

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    We propose a solid oxide fuel cell design based on a configuration of two electrodes on the same surface of the electrolyte in a flowing mixture of different hydrocarbons and air between 500 and 600°C. The ohmic resistance can be reduced without using a thin electrolyte film due to a significantly enhanced performance by the approach of the two electrodes to each other on the smooth electrolyte surface. The fuel cell performance, especially at reduced temperatures, is further improved by using a more reactive hydrocarbon fuel and a more catalytically active anode. The resulting power density reaches 122 mW cm-2 using 2 mm thicer electrolyte at 500°C. © 2002 The Electrochemical Society. All rights reserved.

    DOI: 10.1149/1.1431573

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  191. High performance anodes for SOFCs operating in methane-air mixture at reduced temperatures Reviewed

    Hibino T, Hashimoto A, Yano M, Suzuki M, Yoshida S, Sano M

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 149 ( 2 ) page: A133 - A136   2002.2

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    Electrocatalytic oxidation of methane over anodes in single-chamber solid oxide fuel cells, 0-10 wt % Pd-30 wt % Ce0.8Sm0.2O1.9 (samaria-doped ceria, SDC)-Ni|SDC|Sm0.5Sr0.5CoO3, was studied in a mixture of methane and air between 450 and 550°C. The addition of a small amount of Pd (0.145 mg cm-2) to the anode significantly promoted the partial oxidation of methane by oxygen to form hydrogen and carbon monoxide, which resulted in electromotive forces of ca. 900 mV from the cell and extremely small electrode-reaction resistances of the anode. The peak power densities, when using a 0.15 mm thick SDC electrolyte, reached 644, 467, and 269 mW cm-2 at 550, 500, and 450°C, respectively. © 2002 The Electrochemical Society. All rights reserved.

    DOI: 10.1149/1.1430226

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  192. 総説:燃料・空気混合ガス発電を可能にする単室式SOFC

    日比野高士

    電池技術   Vol. 14   page: 101-106   2002

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  193. High-temperature hydrocarbon sensors based on a stabilized zirconia electrolyte and proton conductor-containing platinum electrode Reviewed

    Hashimoto A, Hibino T, Mori KT, Sano M

    SENSORS AND ACTUATORS B-CHEMICAL   Vol. 81 ( 1 ) page: 55 - 63   2001.12

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  194. High-temperature hydrocarbon sensors based on a stabilized zirconia electrolyte and proton conductor-containing platinum electrode Reviewed

    Hashimoto A., Hibino T., Mori K.t., Sano M.

    Sensors and Actuators, B: Chemical   Vol. 81 ( 1 ) page: 55 - 63   2001.12

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    The non-Nernstian behavior of zirconia-based oxygen sensors for 0-1000ppm C1-C5 hydrocarbons, carbon monoxide, and hydrogen was studied using various ion conductor-containing Pt electrodes in the presence of 10vol.% of oxygen at 600°C. The addition of a proton conductor, especially SrCe0.95Yb0.05O3-α (SCY), to the Pt electrode improved the sensitivity for the hydrocarbons over other reducing gases: -122mV for 1000ppm propene; -24mV for 1000ppm carbon monoxide; and -23mV for 1000ppm hydrogen. The EMF value of the cell was enhanced by the increasing carbon number of the hydrocarbons, the unsaturation of the C-C linkage, and the branching of the chain structure. A similar conclusion also applied to aromatic hydrocarbons: -81mV for 500ppm benzene; -96mV for 500ppm toluene; and -102mV for 500ppm p-xylene. This enhanced effect, as well as the addition effect of SCY, was discussed on the basis of the measurements of polarization curves for hydrocarbons and oxygen and the non-electrochemical oxidation of the hydrocarbons by oxygen. It was found that the added SCY did not inhibit the catalytic activities for the hydrocarbons, but decreased the cathodic reaction rate of oxygen, thus, shifting the mixed potential for the hydrocarbons to more negative values. © 2001 Elsevier Science B.V. All rights reserved.

    DOI: 10.1016/S0925-4005(01)00931-5

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  195. Proton conduction at the surface of Y-doped BaCeO3 Reviewed

    Hibino T, Hashimoto A, Suzuki M, Sano M

    JOURNAL OF PHYSICAL CHEMISTRY B   Vol. 105 ( 46 ) page: 11399 - 11401   2001.11

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    In our work, 25 mol % of Y3+-doped BaCeO3 (BCY25) showed an extremely low activation energy of 0.3 eV for proton conduction at the surface. The resulting overall conductivity at the surface reached 8.24 × 10-3 S cm-1 at 400 °C, which was 3, 8, and 28 times higher than conductivities in the bulk of BCY25, 20 mol % Sm3+-doped ceria, and 8 mol % yttriia-stabilized zirconia, respectively. A large H/D isotope effect strongly suggested that the enhanced proton conductivities were due to an advantageous jump of protons between adjacent oxide ions at the surface. Such fast proton conduction enabled an air/fuel sensor using BCY25 as the solid electrolyte to work at 200 °C or less.

    DOI: 10.1021/jp0124342

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  196. Mixed potentials at metal-electrode and proton-conducting electrolyte interfaces in hydrocarbon-oxygen mixtures Reviewed

    Hibino T, Hashimoto A, Mori K, Sano M

    JOURNAL OF PHYSICAL CHEMISTRY B   Vol. 105 ( 43 ) page: 10648 - 10652   2001.11

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  197. Mixed potentials at metal-electrode and proton-conducting electrolyte interfaces in hydrocarbon-oxygen mixtures Reviewed

    Hibino T., Hashimoto A., Mori K.T., Sano M.

    Journal of Physical Chemistry B   Vol. 105 ( 43 ) page: 10648 - 10652   2001.11

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    Potentiometric sensors using different solid electrolytes, including proton, oxide-ion, and mixed proton and oxide-ion conductors, were fabricated to investigate a relationship between the mixed potential for C1-C4 hydrocarbons and ion conduction in the electrolyte in a mixture of hydrocarbons and oxygen at 600 °C. There was an increase in the mixed potential for the hydrocarbons with increasing proton conductivity or decreasing oxide-ion conductivity. The sensor using a SrCe0.95Yb0.05O3-α (SCY) electrolyte with a Pt electrode showed an enhancement of the mixed potential for the hydrocarbons by increasing the carbon number, branching the chain structure, and unsaturating the C-C linkage. The polarization curves for hydrocarbon oxidation and for oxygen reduction at the Pt/SCY interface were also measured. These results revealed that the mixed potential at the Pt/SCY interface was strongly dependent on the rate of abstraction of hydrogen atom from the hydrocarbon molecules.

    DOI: 10.1021/jp012094k

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  198. Proton conduction at the surface of Y-doped BaCeO3 Reviewed

    Takashi Hibino, Atsuko hashimoto, Masanori Suzuki, Mitsuru Sano

    The Journal of Physical Chemistry B   Vol. 105   page: 11399-11401   2001.11

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  199. A solid oxide fuel cell using an exothermic reaction as the heat source Reviewed

    Takashi Hibino, Atsuko Hashimoto, Takao Inoue, Jun-ichi Tokuno, Shin-ichiro Yoshida, Mitsuru Sano

    Journal of the Electrochemical Society   Vol. 148   page: A544-A549   2001.6

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  200. A solid oxide fuel cell using an exothermic reaction as the heat source Reviewed

    Hibino T, Hashimoto A, Inoue T, Tokuno J, Yoshida S, Sano M

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 148 ( 6 ) page: A544 - A549   2001.6

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    Performance of a single-chamber solid oxide fuel cell was evaluated using a 0.15 mm thick Sm-doped ceria (SDC) electrolyte together with a 30 wl % SDC-Ni anode and a Sm0.5Sr0.5CoO3 cathode at heating temperatures below 500°C in a flowing mixture of butane and air. A large quantity of reaction heat, which was evolved by the partial oxidation of butane by oxygen at the anode, caused a temperature rise of more than 100°C at the anode, followed by thermal conduction to the cathode through the electrolyte. Simultaneously, the cell generated a large electromotive force of ca. 900 mV between the two electrodes. The resulting peak power density reached 245, 180, 105, and 38 mW cm 2 at heating temperatures of 450, 400, 350, and 300°C, respectively. The comparison of the butane fuel with the other hydrocarbon fuels showed that the fuel cell performance became enhanced, especially at reducing temperatures, as the carbon number of the hydrocarbon increased, and the chain structure was branched. © 2001 The Electrochemical Society. [DOI: 10.1149/1.1368098] All rights reserved.

    DOI: 10.1149/1.1368098

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  201. A mixed-potential gas sensor using a SrCe0.95Yb0.05O3-α electrolyte with a platinum electrode for detection of hydrocarbons Reviewed

    Takashi Hibino, Atsuko Hashimoto, Ken-taro Mori, Mitsuru Sano

    Electrochemical and Solid-State Letters   Vol. 4   page: H9-H11   2001.5

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  202. A mixed-potential gas sensor using a SrCe0.95Yb0.05O3-alpha electrolyte with a platinum electrode for detection of hydrocarbons Reviewed

    Hibino T, Hashimoto A, Mori K, Sano M

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 4 ( 5 ) page: H9 - H11   2001.5

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  203. A mixed-potential gas sensor using a SrCe<inf>0.95</inf>Yb<inf>0.05</inf>O<inf>3-α</inf> electrolyte with a platinum electrode for detection of hydrocarbons Reviewed

    Hibino T., Hashimoto A., Mori K.T., Sano M.

    Electrochemical and Solid-State Letters   Vol. 4 ( 5 )   2001.5

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    Mixed-potential type sensors using different ion conducting electrolytes with a Pt working electrode have been fabricated to investigate a relationship between the sensing properties for hydrocarbons and ion conduction in the electrolyte under oxidizing conditions at 600°C. There was an increase in the mixed potential for propene with increasing proton conduction or decreasing oxide ion conduction. The sensor using a SrCe0.95Yb0.05O3-α electrolyte showed an enhanced mixed potential for C1-C4 hydrocarbons by increasing the carbon number, unsaturating the C-C linkage, and branching the chain structure. In addition, this sensor barely showed the mixed potential for hydrogen, carbon monoxide, and nitrogen monoxide.

    DOI: 10.1149/1.1363128

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  204. Zirconia-based potentiometric sensors using metal oxide electrodes for detection of hydrocarbons Reviewed

    Takashi Hibino, Atsuko Hashimoto, Shiro Kakimoto, Mitsuru Sano

    Journal of The Electrochemical Society   Vol. 148   page: H1-H5   2001.1

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  205. Zirconia-based potentiometric sensors using metal oxide electrodes for detection of hydrocarbons Reviewed

    Hibino T, Hashimoto A, Kakimoto S, Sano M

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 148 ( 1 ) page: H1 - H5   2001.1

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  206. Zirconia-based potentiometric sensors using metal oxide electrodes for detection of hydrocarbons Reviewed

    Hibino T., Hashimoto A., Kakimoto S., Sano M.

    Journal of the Electrochemical Society   Vol. 148 ( 1 )   2001.1

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    The non-Nernstian behavior of zirconia-based electrochemical cells with various metal oxide electrodes for 0-500 ppm C1-C4 hydrocarbons, hydrogen, and carbon monoxide was studied in the presence of 10% oxygen at 600 °C. The cell using an In2O3 electrode exhibited a largely negative electromotive force (emf) for propene but gave moderately negative emfs for hydrogen and carbon monoxide. The addition of 0.1 wt % MnO2 to the In2O3 electrode significantly improved the selectivity of the parent electrode for propene over hydrogen and carbon monoxide. The negative emf of the cell using the MnO2-containing In2O3 electrode for the hydrocarbons became enhanced as the carbon number of the hydrocarbon increased, the C-C linkage was unsaturated, and the chain structure was branched. This enhanced effect, as well as the addition effect of MnO2, was discussed on the basis of the measurements of the polarization curves of the MnO2-containing In2O3 electrode for the hydrocarbons and oxygen and the nonelectrochemical oxidation of the hydrocarbons by oxygen. In addition, the MnO2-containing In2O3 electrode for the hydrocarbons was compared with an Au electrode with respect to sensitivity to the hydrocarbons and reproducibility of the sensing properties.

    DOI: 10.1149/1.1344558

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  207. High-temperature hydrocarbon sensors based on a stabilized zirconia electrolyte and proton conductor-containing platinum electrode Reviewed

    Atsuko Hashimoto, Takashi Hibino, Ken-taro Mori, Mitsuru Sano

    Sensors and Actuators B   Vol. 81   page: 55-63   2001

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  208. Mixed potentials at metal-electrode and proton-conducting electrolyte interfaces in hydrocarbon-oxygen mixtures Reviewed

    Takashi Hibino, Atsuko hashimoto, Ken-taro Mori, Mitsuru sano

    The Journal of Physical Chemistry B   Vol. 105   page: 10648-10652   2001

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  209. 総説:単室作動形燃料電池の研究

    日比野高士

    セラミックス   Vol. 36   page: 486-488   2001

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  210. Selective catalytic reduction of nitric oxide by ethane using sOxide membranes Reviewed

    Takashi Hibino, Takao Inoue, Mitsuru Sano

    Journal of the Electrochemical Society   Vol. 147   page: 3745-3750   2000.10

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  211. Selective catalytic reduction of nitric oxide by ethane using solid oxide membranes Reviewed

    Hibino T, Inoue T, Sano M

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 147 ( 10 ) page: 3745 - 3750   2000.10

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  212. Selective catalytic reduction of nitric oxide by ethane using solid oxide membranes Reviewed

    Hibino T., Inoue T., Sano M.

    Journal of the Electrochemical Society   Vol. 147 ( 10 ) page: 3745 - 3750   2000.10

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    The Pt-catalyzed reduction of nitric oxide (NOx) using ethane as a reductant can be promoted by the application of positive potentials to the cell NO, C2H6, O2, Pt or (Pt + MxOy)|YSZ|Pt, air between 600 and 700°C. At an O2 concentration of 0% in the reactant gas stream, almost all of the oxygen species transported to the Pt catalyst through the yttria-stabilized zirconia is consumed in the reaction with NO and ethane, which cannot proceed by the supply of gaseous O2 in an amount equimolar to the transported oxygen species under open-circuit conditions. At O2 concentrations of 2-12% in the reactant gas stream, the oxygen species transported to the Pt catalyst shows a certain promotional effect on the reduction of NO by ethane. The promotional effect is further enhanced by the addition of 15 wt% Mn2O3 or 15 wt% MoO3 to the Pt catalyst: Both reaction rates at potentials of 2 V are ca. four times those under open-circuit conditions, although the reaction over the MoO3-containing Pt catalyst is accelerated by the application of not positive but negative potentials to the cell. The mechanism of the promotional effect is discussed on the overall kinetic studies.

    DOI: 10.1149/1.1393968

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  213. Single-chamber solid oxide fuel cells at intermediate temperatures with various hydrocarbon-air mixtures Reviewed

    Takashi Hibino, Atsuko Hashimoto, Takao Inoue, Jun-ichi Tokuno, Shin-ichiro Yoshida, Mitsuru Sano

    Journal of the Electrochemical Society   Vol. 147   page: 2888-2892   2000.8

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  214. Single-chamber solid oxide fuel cells at intermediate temperatures with various hydrocarbon-air mixtures Reviewed

    Hibino T, Hashimoto A, Inoue T, Tokuno J, Yoshida S, Sano M

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 147 ( 8 ) page: 2888 - 2892   2000.8

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  215. Single-chamber solid oxide fuel cells at intermediate temperatures with various hydrocarbon-air mixtures Reviewed

    Hibino T., Hashimoto A., Inoue T., Tokuno J.I., Yoshida S.I., Sano M.

    Journal of the Electrochemical Society   Vol. 147 ( 8 ) page: 2888 - 2892   2000.8

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    The performance of a single-chamber solid oxide fuel cell (SOFC) was studied between 350 and 900 °C in flowing mixtures of methane, ethane, propane, or liquefied petroleum gas and air with a fuel/air volume ratio of one, where their oxidation proceeded safely without explosion. Among all tested electrode materials, Ni-Ce0.8Sm0.2O1.9 cermet and Sm0.5Sr0.5CoO3 oxide functioned best as the anode and cathode, respectively, in various gas mixtures. A cell constructed from a La0.9Sr0.1Ga0.8Mg0.2O3 electrolyte with the two electrodes generated>900 mV in a methane-air mixture between 600 and 800 °C and in an ethane-air mixture between 450 and 650 °C. A small electrode reaction resistance resulted in increasing power density with decreasing electrolyte thickness. The peak power density at 450 °C increased from 34 to 101 mW cm-2 with decreasing electrolyte thickness from 0.50 to 0.18 mm. The working mechanism of the single-chamber SOFC at different temperatures was also studied by measuring the catalytic activities of the two electrodes, for partial oxidation of the hydrocarbons.

    DOI: 10.1149/1.1393621

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  216. A low-operating-temperature solid oxide fuel cell in hydrocarbon-air mixtures Reviewed

    Hibino T, Hashimoto A, Inoue T, Tokuno J, Yoshida S, Sano M

    SCIENCE   Vol. 288 ( 5473 ) page: 2031 - 2033   2000.6

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  217. A low-operating-temperature solid oxide fuel cell in hydrocarbon-air mixtures Reviewed

    Hibino T., Hashimoto A., Inoue T., Tokuno J.I., Yoshida S.I., Sano M.

    Science   Vol. 288 ( 5473 ) page: 2031 - 2033   2000.6

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    The performance of a single-chamber solid oxide fuel cell was studied using a ceria-based solid electrolyte at temperatures below 773 kelvin. Electromotive forces of ~900 millivolts were generated from the cell in a flowing mixture of ethane or propane and air, where the solid electrolyte functioned as a purely ionic conductor. The electrode-reaction resistance was negligibly small in the total internal resistances of the cell. The resulting peak power density reached 403 and 101 milliwatts per square centimeter at 773 and 623 kelvin, respectively.

    DOI: 10.1126/science.288.5473.2031

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  218. A low-operating-temperature solid oxide fuel-cell in hydrocarbon-air mixtures Reviewed

    Takashi Hibino, Atsuko Hashimoto, Takao Inoue, Jun-ichi Tokuno, Shin-ichiro Yoshida, Mitsuru Sano

    Science   Vol. 288   page: 2031-2033   2000.6

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  219. Electrochemical reduction of NO by alternating current electrolysis using yttria-stabilized zirconia as the solid electrolyte: Part I. Characterizations of alternating current electrolysis of NO Reviewed

    Hibino T., Inoue T., Sano M.

    Solid State Ionics   Vol. 130 ( 1 ) page: 19 - 29   2000.5

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    The electrochemical promotion of the decomposition of NO in the presence of excess O2 was carried out by applying AC voltages lower than 6 V at frequencies from 0.01 to 103 Hz to a YSZ cell having two same-metal electrodes, Au, Pd, Pt or Rh. The Pd and Pt electrodes were relatively effective for this reaction. This could be explained by their electrochemical oxygen-pumping properties and catalytic activities for the reduction of NO. The promotional effect was the most enhanced at a frequency of 0.1 Hz and became larger as the concentration of NO increased or the concentration of O2 decreased. Most of the product was N2, although a small amount of N2O was observed at low conversion of NO. The comparison of AC electrolysis with DC electrolysis showed that the former had a somewhat lower current efficiency for the decomposition of NO than the latter at lower than 3 V, above which the opposite result was observed. In addition, DC electrolysis brought about a significant deterioration of the cell, but AC electrolysis did not result in such a deterioration even at a high voltage of 4 V.

    DOI: 10.1016/S0167-2738(00)00581-6

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  220. Electrochemical reduction of NO by alternating current electrolysis using yttria-stabilized zirconia as the solid electrolyte: Part II. Modification of Pd electrode by coating with Rh Reviewed

    Hibino T., Inoue T., Sano M.

    Solid State Ionics   Vol. 130 ( 1 ) page: 31 - 39   2000.5

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    The electrochemical promotion of the decomposition of NO by applying an AC voltage to a YSZ cell having two Pd electrodes has been modified by calcining the Pd electrode at 1450 °C and then coating the obtained Pd electrode with Rh metal. The calcination of the Pd electrode at 1450 °C depressed the oxidation of Pd to PdO at temperatures lower than 800 °C. The coating of the Pd electrode with Rh increased the catalytic activity for the decomposition of NO at temperatures lower than 800 °C. As a result, these modifications enhanced the current efficiency for the decomposition of NO at low temperatures from 650 to 450 °C and at high concentrations of O2 from 2 to 13%. No negative effect on the decomposition of NO was observed in the presence of 5% water vapor and 5% CO2, while a positive effect on this reaction was found for the presence of 500 ppm CH4, C3H8 and C5H12. Based on the measurements of the selectivity for N2 over N2O and the decomposition of N2O, it was concluded that NO is reduced to N2 via intermediate N2O, especially at low temperatures.

    DOI: 10.1016/S0167-2738(00)00508-7

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  221. Electrochemical reduction of NO by alternating current electrolysis using yttria-stabilized zirconia as the solid electrolyte Part Ⅰ. characterizations of alternating current electrolysis of NO Reviewed

    Takashi Hibino, Takao Inoue, Mitsuru Sano

    Solid State Ionics   Vol. 130   page: 19-29   2000.5

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  222. Electrochemical reduction of NO by alternating current electrolysis using yttria-stabilized zirconia as the solid electrolyte Part Ⅱ. modification of Pd electrode by coating with Rh Reviewed

    Takashi Hibino, Takao Inoue, Mitsuru Sano

    Solid State Ionics   Vol. 130   page: 31-39   2000.5

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  223. Electrochemical reduction of NO by alternating current electrolysis using yttria-stabilized zirconia as the solid electrolyte Part I. Characterizations of alternating current electrolysis of NO Reviewed

    Hibino T, Inoue T, Sano M

    SOLID STATE IONICS   Vol. 130 ( 1-2 ) page: 19 - 29   2000.5

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  224. Electrochemical reduction of NO by alternating current electrolysis using yttria-stabilized zirconia as the solid electrolyte Part II. Modification of Pd electrode by coating with Rh Reviewed

    Hibino T, Inoue T, Sano M

    SOLID STATE IONICS   Vol. 130 ( 1-2 ) page: 31 - 39   2000.5

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    Web of Science

  225. Improvement of a single-chamber solid-oxide fuel cell and evaluation of new cell designs Reviewed

    Takashi Hibino, Hajime Tsunekawa, Satoshi Tanimoto, Mitsuru Sano

    Journal of the Electrochemical Society   Vol. 2000   page: 1338-1343   2000.4

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  226. Improvement of a single-chamber solid-oxide fuel cell and evaluation of new cell designs Reviewed

    Hibino T, Tsunekawa H, Tanimoto S, Sano M

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 147 ( 4 ) page: 1338 - 1343   2000.4

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  227. Improvement of a single-chamber solid-oxide fuel cell and evaluation of new cell designs Reviewed

    Hibino T., Tsunekawa H., Tanimoto S., Sano M.

    Journal of the Electrochemical Society   Vol. 147 ( 4 ) page: 1338 - 1343   2000.4

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    The performance of a single-chamber solid-oxide fuel cell (SOFC) made from an yttria-stabilized zirconia solid electrolyte with a 25 wt% Ce0.8Gd0.2O1.9 (GDC)-containing Ni anode and a 15 wt% MnO2-containing La0.8Sr0.2MnO3 cathode was found to be significantly enhanced by the deposition of Mn, Ga, Cr, Ce, and Lu oxide layers on the YSZ surface. In particular, the deposition of the Mn oxide layer increased the maximum power density from 161 to 213 mW cm-2 in a mixture of methane and air having a volume ratio of methane to oxygen of 1/1 at a flow rate of 300 mL min-1 (methane 52 mL min-1, oxygen 52 mL min-1, nitrogen 196 mL min-1), and at an operating temperature of 950°C. This effect was the result of the promoted anodic and cathodic reactions. Two types of cell designs were examined for the single-chamber SOFC; the two electrodes were deposited on opposite surfaces (A-type cell) and on the same face (B-type cell) of the solid electrolyte. The A-type cell showed an increasing power density with decreasing thickness of the solid electrolyte. The maximum power density was 256 mW cm-2 at a solid electrolyte thickness of 0.3 mm. The B-type cell showed an increased power density for a decreased gap between the two electrodes. The maximum power density was 143 mW cm-2 for a gap of 0.5 mm between the two electrodes. In addition, the long-term stability of the single-chamber SOFC was also studied and found to have a direct relationship with the carbon deposition on the GDC-containing Ni electrode.

    DOI: 10.1149/1.1393359

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  228. One-chamber solid oxide fuel cell constructed from a YSZ electrolyte with a Ni anode and LSM cathode Reviewed

    Hibino T., Wang S., Kakimoto S., Sano M.

    Solid State Ionics   Vol. 127 ( 1-2 ) page: 89 - 98   2000.1

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    An excellent SOFC performance in a mixture of methane and air is achieved by constructing a one-chamber cell from a YSZ solid electrolyte with a 25 wt.% Ce0.8Gd0.2O1.9 (GDC)-added Ni anode and 15 wt.% MnO2-added La0.8Sr0.2MnO3 (LSM) cathode, which are deposited on opposite surfaces (A-type cell) or the same face (B-type cell) of the solid electrolyte. Experiments are carried out in a mixture of methane and air having a volume ratio of methane to oxygen of 1/1 at a flow rate of 300 ml min-1 (methane 52 ml min-1; oxygen 52 ml min-1; nitrogen 196 ml min-1) and at an operating temperature of 950 °C. The A-type cell shows an increasing power density with decreasing thickness of the solid electrolyte. The maximum power density is 204 mW cm-2 at a solid electrolyte thickness of 0.3 mm. The B-type cell shows an increasing power density with decreasing gap between the two electrodes. The maximum power density is 102 mW cm-2 for a gap between the two electrodes of 1 mm. The working mechanism of the one-chamber SOFC and the addition effects of GDC and MnO2 are studied using a two-chamber cell which permits independent evaluations of the Ni- and LSM-based electrodes.

    DOI: 10.1016/S0167-2738(99)00253-2

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  229. One-chamber solid oxide fuel cell constructed from a YSZ electrolyte with a Ni anode and LSM cathode Reviewed

    Takashi Hibino, Shuqiang Wang, Siro Kakimoto, Mitsuru Sano

    Solid State Ionics   Vol. 127   page: 89-98   2000.1

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  230. One-chamber solid oxide fuel cell constructed from a YSZ electrolyte with a Ni anode and LSM cathode Reviewed

    Hibino T, Wang SQ, Kakimoto S, Sano M

    SOLID STATE IONICS   Vol. 127 ( 1-2 ) page: 89 - 98   2000.1

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  231. 総説:新しい固体電解質型燃料電池の開発

    日比野高士

    エコインダストリー   Vol. 5   page: 5-10   2000

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  232. A novel sensor for C1-C8 hydrocarbons using two zirconia-based electrochemical cells Reviewed

    Hibino T, Wang SQ

    SENSORS AND ACTUATORS B-CHEMICAL   Vol. 61 ( 1-3 ) page: 12 - 18   1999.12

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  233. Novel sensor for C1-C8 hydrocarbons using two zirconia-based electrochemical cells Reviewed

    Hibino T., Wang S.

    Sensors and Actuators, B: Chemical   Vol. 61 ( 1 ) page: 12 - 18   1999.12

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    An electrochemical device for detecting various hydrocarbons at high temperatures has been fabricated by attaching two Pd|YSZ|Au cells together in which the Pd electrodes are located on the inside of the assembly. The sensing properties for C1-C6 alkanes, C2-C4 alkenes and C6-C8 aromatic hydrocarbons were investigated at 700 °C. When the sample gases containing 0-1000 ppm hydrocarbon and 250-1000 ppm oxygen were supplied to the device at a flow rate of 100 cm3 min-1, large electromotive force (EMF) values were generated from one cell and then compensated by electrochemically pumping oxygen from the other cell. The current applied to the latter cell increased with increasing hydrocarbon concentration and was not significantly affected by changing the oxygen concentration. In addition, the sensitivity to the hydrocarbons became higher as the carbon number of the hydrocarbons increased, although this did not hold for the aromatic hydrocarbons.

    DOI: 10.1016/S0925-4005(99)00247-6

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  234. A novel sensor for C1 - C8 hydrocarbons using two zirconia-based electrochemical cells Reviewed

    Takashi Hibino, Shuqiang Wang

    Sensors and Actuators B   Vol. 61   page: 12-18   1999.12

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  235. High-temperature hydrocarbon sensors based on a stabilized zirconia electrolyte and metal oxide electrodes Reviewed

    Takashi Hibino, Satoshi Tanimoto, Shiro Kakimoto, Mitsuru Sano

    Electrochemical and Solid-State Letters   Vol. 2   page: 651-653   1999.12

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  236. High-temperature hydrocarbon sensors based on a stabilized zirconia electrolyte and metal oxide electrodes Reviewed

    Hibino T, Tanimoto S, Kakimoto S, Sano M

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 2 ( 12 ) page: 651 - 653   1999.12

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  237. High-temperature hydrocarbon sensors based on a stabilized zirconia electrolyte and metal oxide electrodes Reviewed

    Hibino T., Tanimoto S., Kakimoto S., Sano M.

    Electrochemical and Solid-State Letters   Vol. 2 ( 12 ) page: 651 - 653   1999.12

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    The sensing properties of zirconia-based electrochemical cells with various metal oxide electrodes for 0-500 ppm hydrocarbons (primarily propene), hydrogen, and carbon monoxide were studied in the presence of 10% oxygen at 600 °C. The addition of 0.1 wt % manganese oxide (MnO2) to an indium oxide (In2O3) electrode significantly improved the selectivity of the parent electrode to propene over hydrogen and carbon monoxide. This addition effect was based on the promotion of nonelectrochemical oxidations of hydrogen and carbon monoxide in preference to that of propene. The sensor using the 0.1 wt % MnO2-added In2O3 electrode was more reproducible and sensitive to the hydrocarbons than that using a gold electrode.

    DOI: 10.1149/1.1390937

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  238. Non-nernstian behaviors at modified Au electrodes for hydrocarbon gas sensing Reviewed

    Takashi Hibino, Siro Kakimoto, Mitsuru Sano

    Journal of the Electrochemical Society   Vol. 146   page: 3361-3366   1999.9

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  239. Non-Nernstian behavior at modified Au electrodes for hydrocarbon gas sensing Reviewed

    Hibino T, Kakimoto S, Sano M

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 146 ( 9 ) page: 3361 - 3366   1999.9

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  240. Non-Nernstian behavior at modified Au electrodes for hydrocarbon gas sensing Reviewed

    Hibino T., Kakimoto S., Sano M.

    Journal of the Electrochemical Society   Vol. 146 ( 9 ) page: 3361 - 3366   1999.9

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    It was found that the non-Nernstian behavior of a stabilized zirconia cell using a gold (Au) working electrode for saturated and unsaturated hydrocarbon gases can be markedly enhanced by adding tantalum oxide (Ta2O5) to the Au electrode. The non-ideal emf value of the cell using the 10 wt% Ta2O5-added Au electrode for propene is typically three times the value of the cell using the parent Au electrode. The enhancing effect is explained by a promotion of the anodic reaction of propene in preference to the cathodic reaction of oxygen, which simultaneously occurs at the working electrode. The non-ideal emf value for hydrocarbons becomes more negative as the carbon number increases, the C-C linkage is unsaturated, and the chain structure is branched. The enhancing effect due to the calcination of the Au electrode at high temperatures was also studied and was found to be based on a depression of the cathodic reaction of oxygen rather than the anodic reaction of propene.

    DOI: 10.1149/1.1392478

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  241. Effect of electrode and electrolyte modification on the performance of one-chamber solid oxide fuel cell Reviewed

    Takashi Hibino, Yoshitaka Kuwahara, Shuqiang Wang

    Journal of the Electrochemical Society   Vol. 146   page: 2821-2826   1999.8

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  242. Effect of electrode and electrolyte modification on the performance of one-chamber solid oxide fuel cell Reviewed

    Hibino T, Kuwahara Y, Wang S

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 146 ( 8 ) page: 2821 - 2826   1999.8

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  243. Effect of electrode and electrolyte modification on the performance of one-chamber solid oxide fuel cell Reviewed

    Hibino T., Kuwahara Y., Wang S.

    Journal of the Electrochemical Society   Vol. 146 ( 8 ) page: 2821 - 2826   1999.8

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    A one-chamber solid oxide fuel cell (working in a methane-air mixture) with yttria-stabilized zirconia (YSZ) electrolyte was modified by adding oxide to the anode (Pt) and cathode (Au). It was determined that the addition of MnO2 to both electrodes significantly improved the cell discharge characteristics. The short-circuit current density of a cell using 15 wt % MnO2 added to the Pt and 20 wt % MnO2 added to the Au was about 50 times larger than that of a cell using Pt and Au electrodes. Moreover, the cell performance was enhanced further when 1 wt % MnO2 was doped into the YSZ electrolyte. Microstructural observations of the YSZ electrolyte/electrodes interfaces that both the electrode porosity and the contact areas between electrodes and YSZ electrolyte increased markedly for the MnO2-containing Pt and Au electrodes. In addition, the electrocatalytical property of MnO2 added in the electrodes may also contribute to the improved cell performance.

    DOI: 10.1149/1.1392014

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  244. Single chamber solid fuel cell constructed from an yttria-stabilized zirconia electrolyte Reviewed

    Takashi Hibino, Shuqiang Wang, Shiro Kakimoto, Mitsuru Sano

    Electrochemical and Solid-State Letters   Vol. 2   page: 317-319   1999.7

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  245. Single chamber solid oxide fuel cell constructed from an yttria-stabilized zirconia electrolyte Reviewed

    Hibino T, Wang SQ, Kakimoto S, Sano M

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 2 ( 7 ) page: 317 - 319   1999.7

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  246. Single chamber solid oxide fuel cell constructed from an yttria-stabilized zirconia electrolyte Reviewed

    Hibino T., Wang S., Kakimoto S., Sano M.

    Electrochemical and Solid-State Letters   Vol. 2 ( 7 ) page: 317 - 319   1999.7

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    A single chamber cell constructed from an yttria-stabilized zirconia solid electrolyte with a nickel anode and a strontium-doped lanthanum manganese oxide (La0.8Sr0.2MnO3) cathode can generate an electromotive force (emf) of 795 mV and a power density of 121 mW cm-2 in a mixture of methane and air at a flow rate of 300 mL min-1 and 950 °C. The simultaneous additions of 25 wt % gadolinium-doped cerium oxide (Ce0.8G0.2dO1.9) and 15 wt % manganese oxide (MnO2) to the anode and cathode, respectively, further increased the emf to 833 mV and the power density to 162 mW cm-2.

    DOI: 10.1149/1.1390822

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  247. Detection of propylene using two zirconia-based electrochemical cells Reviewed

    Takashi Hibino, Yoshitaka Kuwahara, Shuqiang Wang

    Journal of the Electrochemical Society   Vol. 146   page: 382-386   1999.1

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  248. Detection of propylene using two zirconia-based electrochemical cells Reviewed

    Hibino T, Kuwahara Y, Wang SG

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 146 ( 1 ) page: 382 - 386   1999.1

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  249. 総説:単室型燃料電池の開発と特性

    日比野高士

    化学工業   Vol. 50   page: 743-747   1999

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  250. 総説:固体電解質の資源環境エネルギーへの応用

    日比野高士

      Vol. 12   page: 13-17   1999

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  251. Detection of propylene using two zirconia-based electrochemical cells Reviewed

    Hibino T., Kuwahara Y.

    Journal of the Electrochemical Society   Vol. 146 ( 1 ) page: 382 - 386   1999

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    A sensor element detecting propylene at high temperatures has been fabricated by attaching two Pd or Pt|YSZ|Au cells together where the Pd or Pt electrodes were located on the inside of the assembly. The sensing properties of the sensor at 750°C were investigated using a flowing mixture of propylene, methane, carbon monoxide, and oxygen, the concentrations of which were in the range of 100 to 700 ppm. The sensor element using the Pd electrode had a high sensitivity to propylene, but a low selectivity to propylene over methane. The use of the Pt electrode made it possible to significantly improve the selectivity to propylene over methane, because the catalytic activities of the Pt electrode for the oxidation of methane were far lower than that of the Pd electrode and as low as that of the Au electrode. The current signal at a fixed oxygen concentration of 300 ppm was almost proportional to the propylene concentration. In addition, the current signal at a fixed propylene concentration of 350 ppm was not significantly affected by changing the oxygen concentration. © 1999 The Electrochemical Society. S0013-4651(98)04-049-X. All rights reserved.

    DOI: 10.1149/1.1391618

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  252. Nonideal electromotive force of zirconia sensors for unsaturated hydrocarbon gases Reviewed

    Hibino T, Kuwahara Y, Wang SQ, Kakimoto S, Sano M

    ELECTROCHEMICAL AND SOLID STATE LETTERS   Vol. 1 ( 4 ) page: 197 - 199   1998.10

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  253. Nonideal electromotive force of zirconia sensors for unsaturated hydrocarbon gases Reviewed

    Hibino T., Kuwahara Y., Wang S., Kakimoto S., Sano M.

    Electrochemical and Solid-State Letters   Vol. 1 ( 4 ) page: 197 - 199   1998.10

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    Non-Nernstian behaviors of a zirconia-based oxygen sensor for 0-500 ppm saturated and unsaturated hydrocarbon gases were studied in the presence of 10% oxygen at 600°C. The sensor, using an Au sensing electrode, produced large electromotive forces (emfs) for the unsaturated hydrocarbons which were aliphatic as well as aromatic. The emf values of the sensor for the hydrocarbons were strongly affected by their unsaturation fraction, carbon number, and chain structure. © 1998 The Electrochemical Society. All rights reserved.

    DOI: 10.1149/1.1390683

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  254. Detection of propylene under oxidizing conditions using zirconia-based potentiometric sensor Reviewed

    Hibino T, Wang SQ, Kakimoto S, Sano M

    SENSORS AND ACTUATORS B-CHEMICAL   Vol. 50 ( 2 ) page: 149 - 155   1998.7

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  255. NOx detection using the electrolysis of water vapor in a YSZ cell Part II. Electrochemical oxygen pump Reviewed

    Hibino T., Kuwahara Y., Otsuka T., Ishida N., Oshima T.

    Solid State Ionics   Vol. 107 ( 3-4 ) page: 217 - 220   1998.4

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    The detection of NO in the presence of excess oxygen has been carried out using four electrochemical cells, Pt|YSZ|Pt, which serve as an electrochemical pumping cell, an electrolysis cell and two oxygen sensors, respectively. Their operation temperature was 800°C. A mixture of 0-2500 ppm NO, 1-7% oxygen, 3-10% water vapor and 0-10% carbon dioxide in argon was used as a sample gas. At the electrochemical pumping cell, oxygen in the sample gas was removed down to a constant concentration of 1800 ppm, which was monitored by the oxygen sensor. At the electrolysis cell, water vapor in the sample gas was electrolyzed, and the resulting hydrogen reacted with NO in the sample gas. Finally, the sample gas was fed into another oxygen sensor. Two potentiometric and amperometric methods were adopted to detect NO. In the potentiometric method, the EMF value of the oxygen sensor decreased with increasing NO concentration. In the amperometric method, the current applied to the electrolysis cell was proportional to the concentration of NO. Additionally, the influences of the coexisting oxygen, water vapor and carbon dioxide in the sample gas on the detection of NO were investigated in detail. © 1998 Elsevier Science B.V. All rights reserved.

    DOI: 10.1016/s0167-2738(97)00539-0

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  256. NOx detection using the electrolysis of water vapour in a YSZ cell Part I. NOx detection Reviewed

    Hibino T., Kuwahara Y., Otsuka T., Ishida N., Oshima T.

    Solid State Ionics   Vol. 107 ( 3-4 ) page: 213 - 216   1998.4

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    The reaction of NO with the hydrogen formed by electrolyzing water vapour in a YSZ cell has been applied to detect NO with output signal of magnitude in millivolt or milliampere. The experimental apparatus consisted of two YSZ cells, Pt|YSZ|Pt, which served as an electrolysis cell and an oxygen sensor, respectively. A mixture of 0-3000 ppm NO and 3% H2O in argon was successively fed to the two cells at 800°C. In the upstream cell, the hydrogen formed by electrolyzing water vapour in the sample gas reacted with NO in the sample gas. In the downstream cell, the electromotive force (EMF) value was measured using air as a reference gas. The EMF value of the oxygen sensor was used as a sensor signal, when a current of 6.7 mA was applied to the electrolysis cell. The EMF signal decreased with increasing NO concentration in the sample gas. Furthermore, the current applied to the electrolysis cell was used as another sensor signal, when the EMF value of the oxygen sensor was held at 700 mV. The current signal increased with increasing NO concentration in the sample gas. © 1998 Elsevier Science B.V. All rights reserved.

    DOI: 10.1016/s0167-2738(97)00538-9

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  257. Nonideal electromotive force of zirconia sensors for unsaturated hydrocarbon gases Reviewed

    Takashi Hibino, Yoshitaka Kuwahara, Shuqiang Wang, Shiro Kakimoto, Mitsuru Sano

    Electrochemical and Solid-State Letters   Vol. 1   page: 197-199   1998.4

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  258. NOx detection using the electrolysis of water vapor in a YSZ cell - Part II. Electrochemical oxygen pump Reviewed

    Hibino T, Kuwahara Y, Otsuka T, Ishida N, Oshima T

    SOLID STATE IONICS   Vol. 107 ( 3-4 ) page: 217 - 220   1998.4

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  259. NOx detection using the electrolysis of water vapour in a YSZ cell - Part I. NOx detection Reviewed

    Hibino T, Kuwahara Y, Otsuka T, Ishida N, Oshima T

    SOLID STATE IONICS   Vol. 107 ( 3-4 ) page: 213 - 216   1998.4

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  260. NOx detection using the electrolysis of water vapor in a YSZ cell Part Ⅰ. NOx detection Reviewed

    Takashi Hibino, Yoshitaka Kuwahara, T. Otsuka, N. Ishida, T. Oshima

    Solid State Ionics   Vol. 107   page: 213-216   1998

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  261. Detection of propylene under oxidizing conditions using zirconia-based potentiometric sensor Reviewed

    Takashi Hibino, Shuqiang Wang, Shiro Kakimoto, Mitsuru Sano

    Sensors and Actuators B   Vol. 50   page: 149-155   1998

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  262. NOx detection using the electrolysis of water vapor in a YSZ cell. Part Ⅱ. electrochemical oxygen pump Reviewed

    Takashi Hibino, Yoshitaka Kuwahara, T. Otsuka, N. Ishida, T. Oshima

    Solid State Ionics   Vol. 107   page: 217-220   1998

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  263. Detection of propylene under oxidizing conditions using zirconia-based potentiometric sensor Reviewed

    Hibino T., Wang S., Kakimoto S., Sano M.

    Sensors and Actuators, B: Chemical   Vol. 50 ( 2 ) page: 149 - 155   1998

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    A sensor device detecting propylene under oxidizing conditions at high temperatures has been fabricated using a yttria-stabilized zirconia (YSZ) as the solid electrolyte. When the sample gas containing 0-500 ppm propylene and 10 vol.% O2 was fed to various metal electrodes at 600°C, the Pt, Pd and Ni electrodes had a small or negligible EMF response, but the Au electrode had a large EMF response, which was based on a mixed potential. The mixed potentials of the Au electrode for H2, CO and CH4 were very small and that for propylene was independent of the presence of water vapor and CO2. However, since this sensor was an oxygen concentration cell, the mixed potential for propylene was affected by changing the O2 concentration. This problem was appreciably solved using a one-compartment cell attached with the Au and Pt electrodes, where their sensitivities to O2 were compensated by each other. In addition, the mechanism of the mixed potential for propylene was discussed by measuring the polarization curve of the Au electrode and its catalytic activity. © 1998 Elsevier Science S.A. All rights reserved.

    DOI: 10.1016/S0925-4005(98)00217-2

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  264. Solid electrolyte HC sensor on gasoline engines Reviewed

    Hibino T., Kuwahara Y., Kuroki Y., Oshima T., Inoue R., Kitanoya S., Fuma T.

    Solid State Ionics   Vol. 104 ( 1-2 ) page: 163 - 166   1997.12

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    A sensor for detecting CH4 in exhaust gases from gasoline engines has been constructed from two Pd|YSZ| Au cells, which are attached to each other with their Pd electrodes in the interior side of the assembly. When the sample gases consisting of CH4, O2 and H2O were fed to the sensor element at 750°C, EMF values were generated from the one cell and then compensated by pumping O2 electrochemically from the other cell. Currents applied to the latter cell linearly increased with CH4 concentration, but were not influenced by changing O2 concentration.

    DOI: 10.1016/s0167-2738(97)00405-0

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  265. Solid electrolyte HC sensor on gasoline engines Reviewed

    Hibino T, Kuwahara Y, Kuroki Y, Oshima T, Inoue R, Kitanoya S, Fuma T

    SOLID STATE IONICS   Vol. 104 ( 1-2 ) page: 163 - 166   1997.12

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  266. Mechanism of NO decomposition in a solid electrolyte reactor by SEP method Reviewed

    Hibino T., Ushiki K., Kuwahara Y.

    Solid State Ionics   Vol. 98 ( 3-4 ) page: 185 - 190   1997.6

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    The mechanism of the NO decomposition in the presence of excess O2, H2O and CO2 using a ceria-based oxide ionic conductor with a Pd electrode has been studied by solid electrolyte potentiometry (SEP) method. A single compartment cell for measuring PO2 , Pt|YSZ|Pt, are attached to another single compartment cell for decomposing NO, Pd|Ce0.8Sm0.2O1.9|Pd, where their working electrodes come into contact with each other. Experiments were carried out with a mixture of 2611 ppm NO, 0.1-4% O2, 0-5% H2O and 0-5% CO2 in argon at 800°C. A PO2 measurement in the neighborhood of the Pd electrode during NO decomposition confirms that the NO decomposition is initiated after the electrochemical oxygen pump is completed. A comparison of the Pd electrodes heated at 850°C with that heated at 1300°C shows that the poorer the oxygen pumping property, the better the NO decomposition. On the basis of these results, the mechanism of the NO decomposition is discussed in detail. In addition, the SEP method also gives information about the influences of the coexistent O2, H2O and CO2 on the NO decomposition.

    DOI: 10.1016/s0167-2738(97)00116-1

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  267. Mechanism of NO decomposition in a solid electrolyte reactor by SEP method Reviewed

    Hibino T, Ushiki K, Kuwahara Y

    SOLID STATE IONICS   Vol. 98 ( 3-4 ) page: 185 - 190   1997.6

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  268. Electrochemical oxygen pump using CeO2-based solid electrolyte for NOx detection independent of O-2 concentration Reviewed

    Hibino T, Ushiki K, Kuwahara Y

    SOLID STATE IONICS   Vol. 93 ( 3-4 ) page: 309 - 314   1997.1

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  269. Electrochemical oxygen pump using CeO<inf>2</inf>-based solid electrolyte for NOx detection independent of O<inf>2</inf> concentration Reviewed

    Hibino T., Ushiki K., Kuwahara Y.

    Solid State Ionics   Vol. 93 ( 3-4 ) page: 309 - 314   1997.1

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    The electrochemical oxygen pump has been studied using Ceo0.8Sm0.2O1.9 as a solid electrolyte and gold metal as an electrode. The O2 concentration in the flow of a mixture of 1000 ppm NO, 1-10% O2, 5% H2O and 5% CO2 at a flow-rate of 20 ml min-1 was electrochemically controlled to a constant value of 5% by applying anodic or cathodic currents to the cell at 900°C. During oxygen pumping, NO was not electrolyzed at all and the pumping amount of oxygen obeyed Faraday's law. A potentiometic-or amperometric-type sensor for NOx when introduced into the resulting gas stream, exhibited an output signal without influence of the O2 concentration.

    DOI: 10.1016/s0167-2738(96)00541-3

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  270. Electrochemical oxygen pump using CeO2-based solid electrolyte for NOx detection independent of O2 concentration Reviewed

    Takashi Hibino, Ken-ichi Ushiki, Yoshitaka Kuwahara

    Solid State Ionics   Vol. 93   page: 309-314   1997

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  271. Solid electrolyte HC sensor on gasoline engines Reviewed

    Takashi Hibino, Yoshitaka Kuwahara, Y. Kuroki, T. Oshima, R. Inoue, S. Kitanoya, T. Fuma

    Solid state Ionics   Vol. 104   page: 163-166   1997

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  272. Mechanism of NO decomposition in a solid electrolyte reactor by SEP method Reviewed

    Takashi Hibino, Ken-ichi Ushiki, Yositaka Kuwahara

    Solid State Ionics   Vol. 98   page: 185-190   1997

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  273. 総説:固体電解質を使用した排ガスセンサ

    日比野高士

    触媒   Vol. 39   page: 660-663   1997

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  274. 総説:化石燃料発電システムとクリーンテクノロジー:炭酸ガスが発生しない発電システム

    日比野高士

    化学装置   Vol. 39   page: 78-80   1997

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  275. Fluidizing behaviour of magnesia and silica ultra-fine powders at elevated temperature Reviewed

    Ushiki K., Hibino T., Sato T., Mizuno M.

    Kagaku Kogaku Ronbunshu   Vol. 22 ( 2 ) page: 332 - 333   1996.12

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    The influence of initial agglomerate-size, gas velocity, and temperature on fluidizing behaviour and bed expansion of ultra-fine powders was examined by the use of a transparent set-up. The fluidizing behaviour was observed through transparent walls. Its behaviour was related to the change in primary agglom erate-size and the assumed secondary-one. The results showed that initial agglomerates were preservable to a certain degree during fluidization and that the size of the initial agglomerate considerably affected the fluidizing behaviour. Adsorbed water even binded strongly to the particle surface influencing secondary-agglomerate-size, and thus the amount of the adsorbed water significantly affected the fluidizing behaviour in the case of magnesia powder. Due to the formation of secondary agglomerates, incipient gas velocity increased at elevated temperature with decreasing initial agglomerate-size. It was found that a rise in gas velocity and bed expansion of up to 2 or 3 times cause almost no change in size of an assumed secondary agglomerate, at least in an uniform bed.

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  276. Electrochemical removal of NO and CH4 in the presence of excess O-2, H2O and CO2 using Sm2O3-doped CeO2 as a solid electrolyte Reviewed

    Hibino T, Ushiki K, Kuwahara Y, Mizuno M

    JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS   Vol. 92 ( 21 ) page: 4297 - 4300   1996.11

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  277. Electrochemical removal of NO and CH<inf>4</inf> in the presence of excess O<inf>2</inf>, H<inf>2</inf>O and CO<inf>2</inf> using Sm<inf>2</inf>O<inf>3</inf>-doped CeO<inf>2</inf> as a solid electrolyte Reviewed

    Hibino T., Ushiki K.I., Kuwahara Y., Mizuno M.

    Journal of the Chemical Society - Faraday Transactions   Vol. 92 ( 21 ) page: 4297 - 4300   1996.11

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    Electrochemical removal of NO and CH4 from a gas stream containing excess O2, H2O and CO2 has been carried out between 400 and 800°C using a single-compartment reactor, which is constructed from CeO2-based solid electrolyte with two palladium electrodes. At all temperatures studied, both NO and CH4 were decomposed by applying a direct current to the reactor. NO was decomposed to N2 in two different ways depending on the applied current. At low currents, NO was electrolysed together with O2 at the palladium cathode; and, at high currents, NO was catalytically reduced over the palladium surface free from adsorbed oxygen. By investigating the influences of the concentration of NO, H2O, CO2, CH4 or C3H8 contained in the reactant gas to these two decompositions, their mechanisms are discussed in detail.

    DOI: 10.1039/ft9969204297

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  278. Ultra-fine grinding of La0.8Sr0.2MnO3 oxide by vibration mill Reviewed

    Hibino T, Suzuki K, Ushiki K, Kuwahara Y, Mizuno M

    APPLIED CATALYSIS A-GENERAL   Vol. 145 ( 1-2 ) page: 297 - 306   1996.10

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  279. Ultra-fine grinding of La<inf>0.8</inf>Sr<inf>0.2</inf>MnO<inf>3</inf> oxide by vibration mill Reviewed

    Hibino T., Suzuki K., Ushiki K.I., Kuwahara Y., Mizuno M.

    Applied Catalysis A: General   Vol. 145 ( 1-2 ) page: 297 - 306   1996.10

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    The grinding operation of La0.8Sn0.2MnO3 (LSM) powder by a vibration mill has been carried out with the intention of giving a higher surface area and a good thermal stability. The specific surface area of the LSM powder increased with operation time and reached up to 34 m2 g-1 for 350 h. XRD measurement and chemical analysis showed that during the grinding operation, the crystal structure of the LSM powder was kept and that the extent of the contamination was negligibly small. In CH4 oxidation at 400°C and N2O reduction at 450°C over the ground LSM powder, both conversions were raised proportional to the increasing specific surface area. Furthermore, the thermal stability of the ground LSM powder was improved by grinding it together with CeO2 powder. The fine dispersion of CeO2 particles around the LSM particles effectively depressed the sintering of the LSM powder at elevated temperatures.

    DOI: 10.1016/0926-860X(96)00166-4

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  280. New concept for simplifying SOFC system Reviewed

    Hibino T., Ushiki K., Kuwahara Y.

    Solid State Ionics   Vol. 91 ( 1-2 ) page: 69 - 74   1996.10

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    A novel design for the solid oxide fuel cell (SOFC) has been proposed. By attaching palladium and gold electrodes on the same face of BaCe0.8Gd0.2O3-α electrolyte and feeding a mixture of CH4 and O2 (CH4:O2 mole ratio = 2:1) to the cell at 950°C, electric power could be generated from the cell. The main advantages are that the ohmic resistance of the cell decreased with reducing distance between the two electrodes and that some unit cells were connected in series and parallel with one another on the same electrolyte. In addition, the surface ionic conduction of oxide ion was studied from the standpoint of the surface morphology of the electrolyte.

    DOI: 10.1016/s0167-2738(96)00437-7

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  281. New concept for simplifying SOFC system Reviewed

    Hibino T, Ushiki K, Kuwahara Y

    SOLID STATE IONICS   Vol. 91 ( 1-2 ) page: 69 - 74   1996.10

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  282. Electrochemical removal of NO in the presence of excess O<inf>2</inf>, H<inf>2</inf>O and CO<inf>2</inf> using Sm<inf>2</inf>O<inf>3</inf>-doped CeO<inf>2</inf> as a solid electrolyte Reviewed

    Hibino T., Ushiki K., Kuwahara Y., Mizuno M.

    Solid State Ionics   Vol. 89 ( 1-2 ) page: 13 - 16   1996.8

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    Electrochemical removal of NO from a gas stream containing 2% O2, 5% H2O and 5% CO2 has been carried out between 400 and 800°C using a single-compartment reactor, constructed from CeO2-based solid electrolyte with two palladium electrodes. At all temperatures studied, NO was decomposed to N2 at the palladium cathode by applying a direct current to the reactor. The dependence of the conversion of NO to N2 on the concentration of NO, O2, H2O or CO2 was investigated at 450°C in detail.

    DOI: 10.1016/0167-2738(96)00257-3

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  283. An electrochemical steam pump using a proton conducting ceramic Reviewed

    Iwahara H, Hibino T, Sunano T

    JOURNAL OF APPLIED ELECTROCHEMISTRY   Vol. 26 ( 8 ) page: 829 - 832   1996.8

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  284. Electrochemical removal of NO in the presence of excess O-2, H2O and CO2 using Sm2O3-doped CeO2 as a solid electrolyte Reviewed

    Hibino T, Ushiki K, Kuwahara Y, Mizuno M

    SOLID STATE IONICS   Vol. 89 ( 1-2 ) page: 13 - 16   1996.8

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  285. Oxidative coupling of CH4 using alkali-metal ion conductors as a solid electrolyte Reviewed

    Hibino T, Ushiki K, Kuwahara Y, Masegi A, Iwahara H

    JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS   Vol. 92 ( 13 ) page: 2393 - 2396   1996.7

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  286. Oxidative coupling of CH<inf>4</inf> using alkali-metal ion conductors as a solid electrolyte Reviewed

    Hibino T., Ushiki K.I., Kuwahara Y., Masegi A., Iwahara H.

    Journal of the Chemical Society - Faraday Transactions   Vol. 92 ( 13 ) page: 2393 - 2396   1996.7

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    The oxidative coupling of CH4 to C2H4 and C2H6 (C2-hydrocarbons) has been carried out using an Li+ ion conductor as a solid electrolyte. A single-compartment cell is constructed from (Li2O)0.17(BaO)0.07(TiO2) 0.76 (LBT) ceramic with two gold electrodes. Alternative current voltages are applied between the two electrodes with a mixture of 8.3% CH4 and 1.6% O2 in argon. The experiments are carried out under various conditions. The formation of C2-hydrocarbons is the most effectively enhanced at a temperature of 850°C or a frequency of 10 Hz. For example, the conversion of CH4 and the selectivity of C2-hydrocarbons at 3 V are 2 and 1.5 times more than those at the open circuit, respectively. The applications of a dc voltage to a two-compartment cell suggested that the active sites are generated via the cathodic reaction. The mechanism for the formation of C2-hydrocarbons is discussed in detail.

    DOI: 10.1039/ft9969202393

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  287. Studies on solid electrolytes for a new-type SOFC using methane-air mixture Reviewed

    Asano K, Hibino T, Iwahara H

    DENKI KAGAKU   Vol. 64 ( 6 ) page: 649 - 653   1996.6

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  288. New concept for simplifying SOFC system Reviewed

    Takashi Hibino, Ken-ichi Ushiki, Yoshitaka Kuwahara

    Solid State Ionics   Vol. 91   page: 69-74   1996

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  289. Studies on solid electrolytes for a new-type SOFC using methane-air mixture Reviewed

    Koichi Asano, Takashi Hibino, Hiroyasu Iwahara

    Denkikagaku   Vol. 64   page: 649-653   1996

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  290. Electrochemical removal of NO and CH4 in the presence of excess O2, H2O and CO2 using Sm2O3-doped CeO2 as a solid electrolyte Reviewed

    Takashi Hibino, Ken-ichi Usiki, Yoshitaka Kuwahara, Mitsukuni Mizuno

    Journal of the Chemical Society, Faraday Transactions   Vol. 92   page: 4297-4300   1996

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  291. Ultra-fine grinding of La0.8Sr0.2MnO3 oxide by vibration mill Reviewed

    Takashi Hibino, Kazuo Suzuki, Ken-ichi Ushiki, Yoshitaka Kuwahara, Mitsukuni Mizuno

    Applied Catalysis A   Vol. 145   page: 297-306   1996

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  292. Electrochemical removal of NO in the presence of excess O2, H2O and CO2 using Sm2O3-doped CeO2 as a solid electrolyte Reviewed

    Takashi Hibino, Ken-ichi Ushiki, Yositaka Kuwahara, Mitsukuni Mizuno

    Solid State Ionics   Vol. 89   page: 13-16   1996

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  293. Oxidative coupling of CH4 using alkali-metal ion conductors as a solid electrolyte Reviewed

    Takashi Hibino, Ken-ichi Usiki, Yoshitaka Kuwahara, Akihiko Masegi, HIroyasu Iwahara

    Journal of the Chemical Society, Faraday Transactions   Vol. 92   page: 2393-2396   1996

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  294. An electrochemical steam pump using a proton conducting ceramic Reviewed

    Hiroyasu Iwahara, Takashi Hibino, T. Sunano

    Journal of Applied Electrochemistry   Vol. 26   page: 829-832   1996

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  295. 総説:触媒技術を利用した固体電解質の新しい応用

    日比野高士

    触媒   Vol. 38   page: 332-333   1996

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  296. 総説:酸素分離セラミックス膜

    日比野高士

    工業材料   Vol. 44   page: 102-104   1996

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  297. An electrochemical steam pump using a proton conducting ceramic Reviewed

    Iwahara H., Hibino T., Sunano T.

    Journal of Applied Electrochemistry   Vol. 26 ( 8 ) page: 829 - 832   1996

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    An electrochemical steam pump was operated at temperatures of 700-900deg;C using a high-temperature type protonic conductor, SrCe0.95Yb0.05O3-α, as a solid electrolyte. When wet air and dry air were introduced into the anode and cathode, respectively, and direct current was applied to the solid electrolyte, the partial pressure of water vapour decreased at the anode, while it increased at the cathode. At low current densities, the pumping rate of water vapour was increased by decreasing the operating temperature and increasing the partial pressure of water vapour at the anode. This is due to the change in proton transport number in SrCe0.95Yb0.05O3-α which depends on the operating condition. At high current densities, the pumping rate was limited by the diffusion rate of water vapour through the porous anode. © 1996 Chapman & Hall.

    DOI: 10.1007/BF00683745

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  298. Studies on solid electrolytes for a new-type SOFC using methane-air mixture Reviewed

    Asano K., Hibino T., Iwahara H.

    Denki Kagaku   Vol. 64 ( 6 ) page: 649 - 653   1996

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    In order to find out a suitable electrolyte for a new-type SOFC (one chamber with methane - air mixture), YSZ (8 mol% Y2O3) doped with TiO2 was tested as a solid electrolyte. In the case of non-doped YSZ, the open - circuit voltage of the cell decreased with time, and the electric power density was extremely smaller than the value obtained in a conventional SOFC using YSZ as a solid electrolyte. However, in the case of YSZ doped with TiO2 (5 mol%), the electric power density was about 6 times higher than that in the case of YSZ only, although the terminal voltage of the cell-slightly decreased with time. This was based on the difference in cathodic polarization and transitional change in the potential between these electrolytes.

    DOI: 10.5796/kogyobutsurikagaku.64.649

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  299. Membrane reactor for oxidative coupling of CH4 with an oxide ion-electron hole mixed conductor Reviewed

    Hibino T, Sato T, Ushiki K, Kuwahara Y

    JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS   Vol. 91 ( 24 ) page: 4419 - 4422   1995.12

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  300. Medium-temperature electrolysis of NO and CH<inf>4</inf> under lean-burn conditions using ytrria-stabilized zirconia as a solid electrolyte Reviewed

    Hibino T., Ushiki K.I., Kuwahara Y., Mizuno M., Masegi A., Iwahara H.

    Journal of the Chemical Society, Faraday Transactions   Vol. 91 ( 13 ) page: 1955 - 1959   1995.12

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    Electrolysis of NO and CH4 in the presence of excess O2 has been studied using a single-compartment reactor, constructed from yttria-stabilized zirconia (YSZ), with two palladium electrodes. The palladium electrodes were attached by an electroless plating method. Experiments were conducted between 550 and 900 °C with a mixture of 1000 ppm NO, 1000 ppm CH4, 2% O2, 5% H2O and 5% CO2 in argon at a flow rate of 50 ml min-1. The reduction of NO to N2 and the oxidation of CH4 to CO2 were promoted by applying a direct current between the two palladium electrodes. The current efficiency for the reduction of NO was about 1.5% at all measured temperatures, while that for the oxidation of CH4 decreased from 2.7 to 0.3% with increasing temperature from 550 to 900 °C. The dc resistance of the reactor was mainly due to the ohmic resistance of the electrolyte. The transport properties of O2- through the electrolyte followed Faraday's law under operating conditions. These results were strongly dependent on the morphology and thickness of the palladium electrode.

    DOI: 10.1039/FT9959101955

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  301. Oxidative coupling reaction of CH<inf>4</inf> using oxide ion and electron hole mixed conductive BaCe<inf>0.8</inf>Gd<inf>0.2</inf>O<inf>3-α</inf> ceramic as a membrane reactor Reviewed

    Hibino T., Ushiki K.I., Kuwahara Y.

    Journal of the Chemical Society, Chemical Communications   ( 10 ) page: 1001 - 1002   1995.12

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    When CH4 and O2 are fed into opposite sides of an electrochemical reactor using BaCe0.8Gd0.2O 3-α ceramic as a solid oxide membrane, the formation of C 2 hydrocarbons is enhanced by self-short circuiting the reactor owing to oxide ion and electron hole mixed conduction in the ceramic.

    DOI: 10.1039/C39950001001

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  302. Membrane reactor for oxidative coupling of CH<inf>4</inf> with an oxide ion-electron hole mixed conductor Reviewed

    Hibino T., Sato T., Ushiki K.I., Kuwahara Y.

    Journal of the Chemical Society, Faraday Transactions   Vol. 91 ( 24 ) page: 4419 - 4422   1995.12

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    A membrane reactor for the oxidative coupling of CH4 has been constructed with an oxide ion-electron hole mixed conductor, BaCe0.8Gd0.2O3-α. 10% CH4 diluted with Ar and an O2-Ar mixture at a given ratio were fed into opposite sides of the membrane at 1173 K. The formation rate of C2-hydrocarbons (ethane and especially ethene) in the CH4 compartment increased with Po2 in the O2-Ar compartment. This enhancement was due to electrochemical oxygen permeation, causing the conductor to short-circuit itself, resulting form the mixed conduction. For comparison, 10% CH4 and a small amount of O2 were co-fed into one side of the membrane. The membrane operation gave a C2 selectivity two times that of the co-feed operation for all CH4 conversions. From a catalytic study using BaCe1-xGdxO3-α powders as catalyst, it was found that increasing both the oxide-ion and electron-hole conductivities enhanced the formation of C2 hydrocarbons, but reduced that of CO2. On the basis of these results, a mechanism for the oxidative coupling of CH4 of the mixed-conductor membrane was proposed.

    DOI: 10.1039/FT9959104419

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  303. A NOVEL CELL DESIGN FOR SIMPLIFYING SOFC SYSTEM Reviewed

    HIBINO T, USHIKI K, SATO T, KUWAHARA Y

    SOLID STATE IONICS   Vol. 81 ( 1-2 ) page: 1 - 3   1995.10

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  304. A NOVEL SOLID OXIDE FUEL-CELL SYSTEM USING THE PARTIAL OXIDATION OF METHANE Reviewed

    ASANO K, HIBINO T, IWAHARA H

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 142 ( 10 ) page: 3241 - 3245   1995.10

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  305. A Novel Solid Oxide Fuel Cell System Using the Partial Oxidation of Methane Reviewed

    Asano K., Hibino T., Iwahara H.

    Journal of the Electrochemical Society   Vol. 142 ( 10 ) page: 3241 - 3245   1995.10

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    A novel solid oxide fuel cell (SOFC) system, which does not need to separate the supply of fuel and oxidant gases and generates electric power as well as chemicals, was studied. The fuel cell consisted of PtiBaCe08gY0.2O3_alAu, in which two electrodes were exposed to the same mixture of CH4 and air. Electromotive forces (EMFs) were about 700 ~ 800 mV at operating temperatures between 750 and 950°C, and terminal voltages were about 420 mV with discharge a current density of about 400 mA cm-2 (0.17 W cm-2) at 950°C and 350 mV with 75 mA cm-2 (0.03 W cm-2) at 750°C. The working mechanism of the fuel cell was clarified to be based on the difference in catalytic activity for the partial oxidation of methane between two electrode materials: the Pt catalyzes the partial oxidation of methane to form hydrogen and carbon monoxide, while the Au is inactive to this reaction. Therefore, the Pt acts as a fuel electrode, while the Au acts as an oxygen electrode at which electrochemical reduction of oxygen takes place on discharging the cell. © 1995, The Electrochemical Society, Inc. All rights reserved.

    DOI: 10.1149/1.2049968

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  306. A novel cell design for simplifying SOFC system Reviewed

    Hibino T., Ushiki K., Sato T., Kuwahara Y.

    Solid State Ionics   Vol. 81 ( 1-2 ) page: 1 - 3   1995.10

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    A novel design for the solid oxide fuel cell (SOFC) has been proposed. By attaching palladium and gold electrodes on the same face of BaCe0.8Gd0.2O3-α electrolyte and feeding a mixture of CH4 and O2 (CH4:O2 mole ratio = 2:1) to the cell at 950 °C, an electric power could be generated from the cell. The main advantages are that the ohmic resistance of the cell decreased with reducing distance between the two electrodes and that some unit cells were connected in series and parallel with one another on the same electrolyte. © 1995.

    DOI: 10.1016/0167-2738(95)00197-E

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  307. Electrocatalytic Oxidation of Methane by Alternating Current Electrolysis Using Yttria-Stabilized Zirconia Reviewed

    Hibino T., Iwahara H.

    Journal of the Electrochemical Society   Vol. 142 ( 10 ) page: 3262 - 3267   1995.10

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    The activity and selectivity of a palladium catalyst for the partial oxidation of methane have been improved by attaching two palladium catalysts to the faces of a zirconia-based ceramic and by applying an ac voltage between the two catalysts. Experiments were conducted between 873 and 1273 K with a mixture of 6.6% methane and 3.3% oxygen in argon. AC voltages at a frequency of 60 Hz were applied to the reactor. Above 1073 K, the amounts of unreacted methane and oxygen decreased, and the yields of hydrogen and carbon monoxide (synthesis gas) increased. At an ac voltage of 3 V at 1273 K, the yield of synthesis gas was up to two times more than that under the open-circuit condition. This enhancement was better than that found by applying a dc voltage of 3 V, in which case the yield of synthesis gas was 1.3 times more than that under the open-circuit condition. © 1995, The Electrochemical Society, Inc. All rights reserved.

    DOI: 10.1149/1.2049972

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  308. ELECTROCATALYTIC OXIDATION OF METHANE BY ALTERNATING-CURRENT ELECTROLYSIS USING YTTRIA-STABILIZED ZIRCONIA Reviewed

    HIBINO T, MASEGI A, IWAHARA H

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 142 ( 10 ) page: 3262 - 3267   1995.10

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  309. MEDIUM-TEMPERATURE ELECTROLYSIS OF NO AND CH4 UNDER LEAN-BURN CONDITIONS USING YTRRIA-STABILIZED ZIRCONIA AS A SOLID-ELECTROLYTE Reviewed

    HIBINO T, USHIKI K, KUWAHARA Y, MIZUNO M, MASEGI A, IWAHARA H

    JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS   Vol. 91 ( 13 ) page: 1955 - 1959   1995.7

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  310. Electrochemical studies on ionic conduction in Ca-doped BaCeO<inf>3</inf> Reviewed

    Iwahara H., Mori T., Hibino T.

    Solid State Ionics   Vol. 79 ( C ) page: 177 - 182   1995.7

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    BaCeO3-based ceramics exhibit both protonic and oxide ionic conduction at high temperatures. In order to investigate the relation between ionic conduction in these oxides and the valence of the dopant cation, divalent Ca-doped BaCeO3 oxides were synthesized and their conduction properties were studied comparing them with those of trivalent Y-doped ones. When the dopant cation was changed from Y to Ca, both protonic and oxide ionic conductivities decreased. TPD analysis and electrochemical tracer experiment showed that the decrease in protonic conductivity could be ascribed to the decrease both in proton concentration and its mobility in the oxides. © 1995.

    DOI: 10.1016/0167-2738(95)00058-E

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  311. ELECTROCHEMICAL STUDIES ON IONIC-CONDUCTION IN CA-DOPED BACEO3 Reviewed

    IWAHARA H, MORI T, HIBINO T

    SOLID STATE IONICS   Vol. 79   page: 177 - 182   1995.7

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  312. OXIDATIVE COUPLING REACTION OF CH4 USING OXIDE-ION AND ELECTRON-HOLE MIXED CONDUCTIVE BACE0.8GD0.2O3-ALPHA CERAMIC AS A MEMBRANE REACTOR Reviewed

    HIBINO T, USHIKI K, KUWAHARA Y

    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS   ( 10 ) page: 1001 - 1002   1995.5

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  313. ELECTROCATALYTIC OXIDATION OF METHANE TO C-2 HYDROCARBONS USING AN LI+ ION CONDUCTOR Reviewed

    HIBINO T, MASEGI A, IWAHARA H

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 142 ( 5 ) page: L72 - L73   1995.5

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  314. Electrocatalytic Oxidation of Methane to C<inf>2</inf> Hydrocarbons Using an Li<sup>+</sup> Ion Conductor Reviewed

    Hibino T., Masegi A., Iwahara H.

    Journal of the Electrochemical Society   Vol. 142 ( 5 ) page: L72 - L73   1995.4

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    The electrocatalytic oxidation of methane to ethane and ethylene has been carried out using an Li+ ion conductor as a solid electrolyte. The electrochemical cell used was Au I (Li2O)0.17(BaO)0.07(TiO2)o.761 Au, and the experiments were conducted at 850°C with a mixture of 8.3% methane and 1.6% oxygen in argon. By applying an ac voltage of 3 V at a frequency of 10 Hz to the cell, the conversion of methane and the selectivity to C2 hydrocarbons were enhanced 2 and 1.5 times more than at the open circuit, respectively. © 1995, The Electrochemical Society, Inc. All rights reserved.

    DOI: 10.1149/1.2048653

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  315. ELECTROCHEMICAL REMOVAL OF BOTH NO AND CH4 UNDER LEAN-BURN CONDITIONS Reviewed

    HIBINO T

    JOURNAL OF APPLIED ELECTROCHEMISTRY   Vol. 25 ( 3 ) page: 203 - 207   1995.3

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  316. Electrochemical removal of both NO and CH<inf>4</inf> under lean-burn conditions Reviewed

    Hibino T.

    Journal of Applied Electrochemistry   Vol. 25 ( 3 ) page: 203 - 207   1995.3

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    An electrochemical cell, Pd|YSZ|Pd, was constructed in order to remove both NO and CH4 in the presence of excess oxygen. When direct current was supplied to the cell with a flow of a mixture of NO, CH4, O2, H2O and CO2 at 700° C, NO was reduced to nitrogen at the cathode, and CH4 was oxidized to COx at both the anode and cathode. At the cathode, the reduction of NO and the oxidation of CH4 proceeded with the removal of chemisorbed oxygen species from the Pd surface, and at the anode, the oxidation of CH4 was enhanced by forming an active oxygen atom. © 1995 Chapman & Hall.

    DOI: 10.1007/BF00262956

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  317. Detection of hydrocarbons in air and purification of exhaust gas under lean-burn conditions using solid electrolytes Reviewed

    Hibino T., Masegi A., Iwahara H.

    Research on Chemical Intermediates   Vol. 21 ( 2 ) page: 181 - 191   1995.1

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    A chemical sensor and an electrochemical reactor without the need for the geometry of two electrode compartments have been fabricated using high temperature-type proton and oxide ion conductors, respectively. Pd|CaZr0.9In0.1O3-α Au, responds quickly to dilute hydrocarbons (CH4, C2H6 and C3Hg) in air at 700 °C and changes an electromotive force (EMF) in proportion to the hydrocarbon content. Pd | yttria-stabilized zirconia (YSZ) | Pd, can remove both NO and CH4 in the presence of excess O2 at 700 °C. By passing the direct current through the cell, NO is reduced to N2 at the cathode, and CH4 is oxidized to COx at the anode. The efficiency of removal is independent of the presence of H2O and CO2. © 1995 Springer.

    DOI: 10.1163/156856795X00161

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  318. A novel solid oxide fuel cell system using the partial oxidation of methane Reviewed

    Koichi Asano, Takashi Hibino, Hiroyasu Iwahara

    Journal of The Electrochemical Society   Vol. 142   page: 3241-3245   1995

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  319. Detection of hydrocarbons in air and purification of exhaust gas under lean-bburn conditions using solid electrolyte Reviewed

    Takashi Hibino, Akihiko Masegi, Hiroyasu Iwahara

    Res. Chem. Intermed.   Vol. 21 ( 2 ) page: 181-189   1995

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  320. Electrochemical removal of both NO and CH4 under lean-burn conditions Reviewed

    Takashi Hibino

    Journal of Applied Electrochemistry   Vol. 25   page: 203-207   1995

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  321. Membrane reactor for oxidation of CH4 with an oxide ion-electron hole mixed conductor Reviewed

    Takashi Hibino, Teruyuki Sato, Ken-ichi Ushiki, Yoshitaka Kuwahara

    Journal of the Chemical Society, Faraday Transactions   Vol. 91   page: 4419-4422   1995

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  322. Electrocatalytic oxidation of methane by AC electrolysis using yttria-stabilized zirconia Reviewed

    Takashi Hibino, Akihiko Masegi, Hiroyasu Iwahara

    Journal of the Electrochemical Society   Vol. 142   page: 3262-3267   1995

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  323. A novel cell design for simplifying SOFC system Reviewed

    Takashi Hibino, Ken-ichi Ushiki, Teruyuki Sato, Yositaka Kueahara

    Solid State Ionics   Vol. 81   page: 1-3   1995

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  324. Electrochemical studies on ionic conduction in Ca-doped BaCeO3 Reviewed

    Hiroyasu Iwahara, T. Mori, Takashi Hibino

    Solid State Ionics   Vol. 79   page: 177-182   1995

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  325. Medium-temperature electrolysis of NO and CH4 under lean-burn conditions using YSZ as a solid electrolyte Reviewed

    Takashi Hibino, Ken-ichi Ushiki, Yoshitaka Kuwahara, Mitsukuni Mizuno, Akihiko Masegi, Hiroyasu Iwahara

    Journal of the Chemical Society, Faraday Transactions   Vol. 91   page: 1955-1959   1995

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  326. Oxidative coupling reaction of CH4 using oxide ion and electron hole mixed conductive BaCe0.3Gd0.2O3-α ceramic as a membrane reactor Reviewed

    Takashi Hibino, Ken-ichi Ushiki, Yoshitaka Kuwahara

    Journal of the Chemical Society Chemical Communication     page: 1001-1002   1995

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  327. Electrocatalytic oxidation of methane to C2 -hydrocarbons using an Li+ ion conductor Reviewed

    Takashi Hibino, Akihiko Masegi, Hiroyasu Iwahara

    Journal of the Electrochemical Society   Vol. 142   page: L72-L73   1995

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  328. 総説:新しいSOFC:セパレターを必要としない均一ガス作動型システム

    日比野高士

    セラミックス   Vol. 30   page: 337-340   1995

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  329. DETECTION OF HYDROCARBONS IN AIR AND PURIFICATION OF EXHAUST-GAS UNDER LEAN-BURN CONDITIONS USING SOLID ELECTROLYTES Reviewed

    HIBINO T, MASEGI A, IWAHARA H

    RESEARCH ON CHEMICAL INTERMEDIATES   Vol. 21 ( 2 ) page: 181 - 191   1995

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  330. AMPEROMETRIC SENSOR FOR MEASUREMENT OF D2O CONCENTRATION IN MIXTURE OF H2O AND D2O USING HIGH-TEMPERATURE PROTONIC CONDUCTOR Reviewed

    HIBINO T, IWAHARA H

    SOLID STATE IONICS   Vol. 74 ( 3-4 ) page: 285 - 290   1994.12

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  331. Amperometric sensor for measurement of D<inf>2</inf>O concentration in mixture of H<inf>2</inf>O and D<inf>2</inf>O using high temperature protonic conductor Reviewed

    Hibino T., Iwahara H.

    Solid State Ionics   Vol. 74 ( 3-4 ) page: 285 - 290   1994.12

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    An amperometric sensor to detect D2O in a mixture of H2O and D2O has been studied using CaZr0.9In0.1O3-α as a high temperature protonic conductor. When the sensor heated at 900°C was exposed to air passed through the H2O+D2O mixture at 20°C, it could respond to D2O in the concentration range of 5% to 100% with a 90% response time of about 15 min. The sensing mechanism was based on a H/D isotope effect on resistance of both bulk oxide and electrode reaction. From temperature programmed desorption (TPD) and complex impedance methods, it was found that an increase in bulk resistance was ascribed to a decrease in mobility of the charge carrier. Current interruption method indicated that overpotentials of both anodic and cathodic reactions were increased by replacing protons with deuterons. © 1994.

    DOI: 10.1016/0167-2738(94)90223-2

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  332. DETECTION OF D2O IN WATER ISOTOPES USING A HIGH-TEMPERATURE PROTONIC CONDUCTOR Reviewed

    HIBINO T, IWAHARA H

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 141 ( 9 ) page: L125 - L126   1994.9

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  333. Detection of D<inf>2</inf>O in Water Isotopes Using a High-Temperature Protonic Conductor Reviewed

    Hibino T., Iwahara H.

    Journal of the Electrochemical Society   Vol. 141 ( 9 ) page: L125 - L126   1994.9

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    An amperometric sensor for the measurement of D2O concentration in a mixture of H2O and D2O has been studied using CaZr0.9 ln0.13-a as a high temperature protonic conductor. When the sensor heated at 1173 K was exposed to air passed through the H20 + D20 mixture at 293 K, it could respond to D20 in the concentration range of 5 to 100% with a 90% response time of about 15 min. © 1994, The Electrochemical Society, Inc. All rights reserved.

    DOI: 10.1149/1.2055176

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  334. ELECTROCHEMICAL HYDROGEN PERMEATION IN A PROTON-HOLE MIXED CONDUCTOR AND ITS APPLICATION TO A MEMBRANE REACTOR Reviewed

    HAMAKAWA S, HIBINO T, IWAHARA H

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 141 ( 7 ) page: 1720 - 1725   1994.7

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  335. Electrochemical Hydrogen Permeation in a Proton-Hole Mixed Conductor and Its Application to a Membrane Reactor Reviewed

    Hamakawo S., Hibino T., Iwahara H.

    Journal of the Electrochemical Society   Vol. 141 ( 7 ) page: 1720 - 1725   1994.7

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    A proton-hole mixed conduction in SrCe0.95Yb005O3_α ceramic has been studied under an asymmetrical atmosphere with respect to hydrogen species. The following electrochemical cell was constructed; (I) 1% hydrogen, Pt I specimen ceramic Pt, O2-Ar mixture (II) and electrochemical hydrogen permeation through this sample was examined under open and closed-circuit conditions. When the circuit was closed, the hydrogen or water vapor evolution rates at the cathode decreased with increasing partial pressure of oxygen in the cathode. From the conductivity measurement under various po2, it was confirmed that the main charge carrier except protons was a positive hole, and that this ceramic behaved as a proton-hole mixed conductor under the asymmetrical condition. When the circuit was open, water vapor evolved spontaneously, and its formation rates were enhanced with increasing po2, in compartment (II). These phenomena indicate that this cell is a self-short-circuited via hole conduction in the bulk, and that hydrogen permeates electrochemically from compartment (I) to (II). Further, based on the principle of hydrogen permeation due to the proton-hole mixed conduction, CH4 dimerization was carried out at 1173 K using SrCe0.95Yb0.05O3_a ceramic as a membrane reactor. Formation rates of C2-hy-drocarbons were enhanced markedly by self-short-circuiting the electrochemical reactor due to the mixed conduction. To clarify the mechanism for the acceleration of CH4 dimerization, the electrolytic synthesis of ethane from CH4 was carried out at 948 K using SrCe0.95Yb0.05O3-α, ceramic as a membrane reactor. © 1994, The Electrochemical Society, Inc. All rights reserved.

    DOI: 10.1149/1.2054993

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  336. SOLID OXIDE FUEL-CELL WHICH CAN WORK IN UNIFORM-GAS PHASE USING PARTIAL OXIDATION OF METHANE Reviewed

    HIBINO T, ASANO K, IWAHARA H

    NIPPON KAGAKU KAISHI   ( 7 ) page: 600 - 604   1994.7

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  337. ELECTROCHEMICAL REMOVAL OF NO AND CH4 FROM OXIDIZING ATMOSPHERE Reviewed

    HIBINO T

    CHEMISTRY LETTERS   ( 5 ) page: 927 - 930   1994.5

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  338. ELECTROLYTIC SYNTHESIS OF ETHANE USING A PROTON CONDUCTING CERAMIC BASED ON SRCEO3 Reviewed

    HAMAKAWA S, HIBINO T, IWAHARA H

    DENKI KAGAKU   Vol. 62 ( 4 ) page: 346 - 347   1994.4

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  339. A HYDROCARBON SENSOR USING A HIGH TEMPERATURE-TYPE PROTON CONDUCTOR Reviewed

    HIBINO T, IWAHARA H

    JOURNAL OF APPLIED ELECTROCHEMISTRY   Vol. 24 ( 3 ) page: 268 - 270   1994.3

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  340. A hydrocarbon sensor using a high temperature-type proton conductor Reviewed

    Hibino T., Iwahara H.

    Journal of Applied Electrochemistry   Vol. 24 ( 3 ) page: 268 - 270   1994.3

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    Using a CaZrO3-based proton conductor as a solid electrolyte, a hydrocarbon sensor has been constructed. The test cell with gold metal and La0.6Ba0.4CoO3 oxide as electrode material gives rise to stable e.m.f.'s on introducing air containing hydrocarbons (CH4, C2H6 or C3H8). This sensing mechanism is based on a steam concentration cell, which results from the difference in combustion activity for hydrocarbons between two electrode materials. © 1994 Chapman & Hall.

    DOI: 10.1007/BF00242895

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  341. IMPROVEMENT OF CAPCIUS CELL USING SRCE0.95YB0.05O3-ALPHA AS A SOLID-ELECTROLYTE Reviewed

    HIBINO T, ASANO K, IWAHARA H

    CHEMISTRY LETTERS   ( 3 ) page: 485 - 488   1994.3

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  342. Recycling of carbon dioxide using a proton conductor as a solid electrolyte Reviewed

    Hibino T., Hamakawa S., Suzuki T., Iwahara H.

    Journal of Applied Electrochemistry   Vol. 24 ( 2 ) page: 126 - 130   1994.2

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    Using a proton conductor based on SrZrO3 or CaZrO3 as a solid electrolyte, three attempts have been made to react CH4 with CO2 efficiently. When the mixture of CH4 and CO2 was used as a fuel gas for a SOFC, the cell provided stable electric power. Furthermore, the electrochemical hydrogen pump accelerated both the reforming of CH4 with CO2 and the oxidative coupling of CH4 with CO2. © 1994 Chapman & Hall.

    DOI: 10.1007/BF00247783

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  343. RECYCLING OF CARBON-DIOXIDE USING A PROTON CONDUCTOR AS A SOLID-ELECTROLYTE Reviewed

    HIBINO T, HAMAKAWA S, SUZUKI T, IWAHARA H

    JOURNAL OF APPLIED ELECTROCHEMISTRY   Vol. 24 ( 2 ) page: 126 - 130   1994.2

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  344. Reactant Shape-selectivity for Cracking of Linear Paraffin on HZSM-5 Modified by CVD of Silicon Alkoxide: A Strong Dependence upon the Reaction Temperature Reviewed

    Niwa M., Senoh N., Hibino T., Nakatsuka Y., Murakami Y.

    Studies in Surface Science and Catalysis   Vol. 83 ( C ) page: 155 - 162   1994.1

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    Chemical vapor deposition (CVD) method of silicon alkoxide was applied to HZSM-5 zeolite in order to enhance the shape-selectivity in cracking of octane isomers. Adsorption experiments using octane and 3-methylheptane showed that silica deposited on the external surface controlled the pore-opening size finely to retard the diffusion of 3-methylheptane only. Shape-selectivity for cracking of linear paraffin was observed at 773 K, but not at lower temperatures; a strong temperature dependence was observed. Mechanism of cracking on HZSM-5 was so complex, and strongly held residues such as large olefinic compounds seemed to retard the reaction at lower temperatures. This was, however, substantial, because cracking of paraffin is usually performed at higher temperatures. © 1994 Kodansha Ltd.

    DOI: 10.1016/S0167-2991(08)63253-X

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  345. Recycling of carbon dioxide using a proton conductor as a solid electrolyte Reviewed

    Takashi Hibino, Satoshi Hamakawa, T. Suzuki, Hiroyasu Iwahara

    Journal of Applied Electrochemistry   Vol. 24   page: 126-130   1994

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  346. Amperometric sensor for measurement of D2O concentration in mixture of H2O and D2O using high temperature protonic conductor Reviewed

    Takashi Hibino, Hiroyasu Iwahara

    Solid State Ionics   Vol. 74   page: 285-290   1994

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  347. Detection of D2O in water isotopes using a high-temperature protonic conductor Reviewed

    Takashi Hibino, Hiroyasu Iwahara

    Journal of the Electrochemical Society   Vol. 141   page: L125-L126   1994

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  348. Electrochemical hydrogen permeation in a proton-hole mixed conductor and its application to a membrane reactor Reviewed

    Satoshi Hamakawa, Takashi Hibino, Hiroyasu Iwahara

    Journal of the Electrochemical Society   Vol. 141   page: 1720-1725   1994

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  349. メタンの部分酸化反応を利用した均一ガス作動型燃料電池 Reviewed

    日比野高士、浅野浩一、岩原弘育

    日本化学会誌     page: 600-604   1994

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  350. Electrochemical removal of NO and CH4 from oxidizing atmosphere Reviewed

    Takashi Hibino

    Chemistry Letters     page: 927-930   1994

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  351. Improvement of CAPCIUS cell using SrCe0.95Yb0.05O3-α as a solid electrolyte Reviewed

    Takashi Hibino, Koichi Asano, Hiroyasu Iwahara

    Chemistry Letters     page: 485-488   1994

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  352. A hydrocarbon sensor using a high temperature-type proton conductor Reviewed

    Takashi Hibino, Hiroyasu Iwahara

    Journal of Applied Electrochemistry   Vol. 24   page: 268-270   1994

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  353. The Hydrogen Isotope Separation by the Steam Electrolysis Using the High Temperature-Type Protonic Conductor Reviewed

    Hibino T., Iwahara H.

    Nippon Kagaku Kaishi   Vol. 1994 ( 6 ) page: 518 - 523   1994

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    The hydrogen isotope separation was carried out by the steam electrolysis using the high temperature-type protonic conductor as a solid electrolyte at 900 °C. The total current and the electrolytic amount were reduced by replacing gaseous H2O with D2O. This was based on the increase in resistances of the bulk, anodic and cathodic reactions. The TPD (Temperature Programmed Desorption) and complex impedance methods suggested that the increase in bulk resistance was attributed to the decrease in mobility of the charge carrier. H2 was preferentially produced at the cathode by electrolyzing the mixture of gaseous H2O and D2O. In this case, the H/D atomic ratio for the gas evolved at the cathode was 1.61, and the separation factor was 1.44. © 1994, The Chemical Society of Japan. All rights reserved.

    DOI: 10.1246/nikkashi.1994.518

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  354. PROTONIC CONDUCTION OF MORDENITE-TYPE ZEOLITE Reviewed

    HIBINO T, AKIMOTO T, IWAHARA H

    SOLID STATE IONICS   Vol. 67 ( 1-2 ) page: 71 - 76   1993.12

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  355. Protonic conduction of mordenite-type zeolite Reviewed

    Hibino T., Akimoto T., Iwahara H.

    Solid State Ionics   Vol. 67 ( 1-2 ) page: 71 - 76   1993.12

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    The protonic conduction of H-mordenite has been investigated by various measurements. A hydrogen concentration cell using mordenite as a solid electrolyte gave rise to a stable EMF, in which the potential of the electrode with high partial pressure of hydrogen was negative. In addition, a stable and steady current could be drawn from a hydrogen-air fuel cell. The proton conductivity of mordenite at RT was 1.07 × 10-5 S cm-1. As the temperature increased, the conductivity once decreased, but then increased according to Arrhenius behavior. TGA measurement suggested that the decrease in conductivity with temperature was due to a decrease in amount of the adsorbed water. From the compositional dependence of the conductivity and the H/D isotope effect on the conductivity, two conduction mechanisms were proposed. © 1993.

    DOI: 10.1016/0167-2738(93)90311-P

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  356. H/D Isotope Effect on Electrochemical Pumps of Hydrogen and Water Vapor Using a Proton-Conductive Solid Electrolyte Reviewed

    Hibino T., Mizutani K., Iwahara H.

    Journal of the Electrochemical Society   Vol. 140 ( 9 ) page: 2588 - 2592   1993.9

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    From the standpoint of an H/D isotope effect, the electrochemical pumping of hydrogen or water vapor has been studied using a high temperature proton conductor as a solid electrolyte. When a potential was applied to the cell at 1173 K, the pumping rate of deuterium was remarkably smaller than that of hydrogen. During hydrogen pumping, the total current was depressed by replacing H+ and D+. In addition, an increase in cathodic overpotential was observed by the current-interruption method. Similar behavior was recognized in the pumping of water vapor, except that the transport number of the conducting ion decreased with replacement of D+ by H+. © 1993, by The Electrochemical Society, Inc. All rights reserved.

    DOI: 10.1149/1.2220867

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  357. Inactivation of external surface of mordenite and ZSM-5 by chemical vapor deposition of silicon alkoxide Reviewed

    Hibino T., Niwa M., Murakami Y.

    Zeolites   Vol. 13 ( 7 ) page: 518 - 523   1993.9

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    The present paper describes the inactivation of the external surfaces of mordenite and ZSM-5 zeolites using chemical vapor deposition (CVD) of Si(OCH3)4. The external surfaces of H mordenites with different Si/Al atomic ratios, Na mordenite, and HZSM-5 were deactivated by a silica layer. The silicon concentration required for the inactivation did not depend upon the included cation and the atomic ratio of Si/Al. Si(OCH3)4 reacted equivalently with terminal hydroxides and acidic hydroxides. © 1993.

    DOI: 10.1016/0144-2449(93)90228-U

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  358. H/D ISOTOPE EFFECT ON ELECTROCHEMICAL PUMPS OF HYDROGEN AND WATER-VAPOR USING A PROTON-CONDUCTIVE SOLID-ELECTROLYTE Reviewed

    HIBINO T, MIZUTANI K, IWAHARA H

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 140 ( 9 ) page: 2588 - 2592   1993.9

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  359. STUDIES ON PROTON CONDUCTING CERAMICS BASED ON PEROVSKITE-TYPE OXIDES Reviewed

    IWAHARA H, HIBINO T, YAJIMA T

    NIPPON KAGAKU KAISHI   ( 9 ) page: 1003 - 1011   1993.9

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  360. SIMPLIFICATION OF SOLID OXIDE FUEL-CELL SYSTEM USING PARTIAL OXIDATION OF METHANE Reviewed

    HIBINO T, IWAHARA H

    CHEMISTRY LETTERS   ( 7 ) page: 1131 - 1134   1993.7

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  361. Performance of Solid Oxide Fuel Cell Using Proton and Oxide Ion Mixed Conductors Based on BaCe<inf>1-x</inf>Sm<inf>x</inf>O<inf>3-α</inf> Reviewed

    Iwahara H., Yajima T., Hibino T., Ushida H.

    Journal of the Electrochemical Society   Vol. 140 ( 6 ) page: 1687 - 1691   1993.6

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    BaCe1-xSmxO3α (x = 0.05, 0.10, 0.15) ceramics were synthesized and their ionic conduction was investigated. These ceramics showed protonic and oxide ionic mixed conduction under fuel cell condition. While protonic conduction was predominant below 1027 K, oxide ionic conduction became significant as the temperature increased. Using these oxides as solid electrolyte, hydrogen-air fuel cell could be constructed. BaCe0.9Sm0.1O3α exhibited the best cell performance among the electrolytes examined. The maximum short-circuit current density was about 900 mA/cm2 at 1273 K. The polarization at each electrode was low. Porous nickel could be used as anode material instead of expensive platinum and La0.6Ba0.4CoO3 as cathode material. © 1993, The Electrochemical Society, Inc. All rights reserved.

    DOI: 10.1149/1.2221624

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  362. PERFORMANCE OF SOLID OXIDE FUEL-CELL USING PROTON AND OXIDE-ION MIXED CONDUCTORS BASED ON BACE1-XSMXO3-ALPHA Reviewed

    IWAHARA H, YAJIMA T, HIBINO T, USHIDA H

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 140 ( 6 ) page: 1687 - 1691   1993.6

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  363. CO2 SENSORS USING BACEO3-BASED CERAMICS Reviewed

    HIBINO T, IWAHARA H

    SENSORS AND ACTUATORS B-CHEMICAL   Vol. 13 ( 1-3 ) page: 483 - 485   1993.5

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  364. CO<inf>2</inf> sensors using BaCeO<inf>3</inf>-based ceramics Reviewed

    Hibino T., Iwahara H.

    Sensors and Actuators: B. Chemical   Vol. 13 ( 1-3 ) page: 483 - 485   1993.5

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    The resistivity of a BaCe0.95Y0.05O3-α ceramic element is very sensitive to CO2 in a moist atmosphere. A reproducible linear relationship between the resistivity and the CO2 concentration is observed in the range 200-300 ppm. In situ FT-IR spectra indicate that hydroxides are formed on the BaCe0.95Y0.05O3-α surface in the moist atmosphere and react with CO2 to form carbonates. From various electrochemical measurements, it is found that the carbonates formed do not increase the bulk resistivity of BaCe0.95Y0.05O3-α but the resistivity of the interface between the electrolyte and the electrode. © 1993.

    DOI: 10.1016/0925-4005(93)85433-B

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  365. PROTONIC CONDUCTION IN CALCIUM, STRONTIUM AND BARIUM ZIRCONATES Reviewed

    IWAHARA H, YAJIMA T, HIBINO T, OZAKI K, SUZUKI H

    SOLID STATE IONICS   Vol. 61 ( 1-3 ) page: 65 - 69   1993.5

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  366. Protonic conduction in calcium, strontium and barium zirconates Reviewed

    Iwahara H., Yajima T., Hibino T., Ozaki K., Suzuki H.

    Solid State Ionics   Vol. 61 ( 1-3 ) page: 65 - 69   1993.5

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    Electrical conduction in sintered oxides based on calcium, strontium or barium zirconate at high temperature was investigated electrochemically. When Zr in MZrO3 (M=Ca, Sr or Ba) was partially replaced by trivalent element such as In, Sc, Y, etc., the resultant solid solutions exhibited protonic conduction under hydrogen-containing atmosphere at elevated temperatures. In general, the protonic conductivities of BaZrO3- and SrZrO3-based ceramics were higher than those of CaZrO3-based one although the values were low compared to those of SrCeO3 or BaCeO3-based ceramics. Clear isotope effects in IR spectrum and conductivity were observed between protonated and deuteronated SrZr0.95Y0.05O3-α. © 1993.

    DOI: 10.1016/0167-2738(93)90335-Z

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  367. DEHYDROGENATION OF ETHANE USING SOLID ELECTROLYTES AS MEMBRANE REACTOR Reviewed

    HIBINO T, HAMAKAWA S, IWAHARA H

    NIPPON KAGAKU KAISHI   ( 3 ) page: 238 - 242   1993.3

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  368. ELECTROCHEMICAL METHANE COUPLING USING PROTONIC CONDUCTORS Reviewed

    HAMAKAWA S, HIBINO T, IWAHARA H

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   Vol. 140 ( 2 ) page: 459 - 462   1993.2

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  369. Protonic conduction in calcium, strontium and barium zirconates Reviewed

    Hiroyasu Iwahara, Tamotsu Yajima, Takashi Hibino, K. Ozaki, H. Suzuki

    Solid State Ionics   Vol. 61   page: 65-69   1993

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  370. Performance of solid oxide fuel cell using proton and oxide-ion mixed conductors based on BaCe1-xSmxO3-a Reviewed

    Hiroyasu Iwahara, Tamotsu Yajima, Takashi Hibino, Haruhisa Ushida

    Journal of The Electrochemical Society   Vol. 140   page: 1687-1691   1993

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  371. 固体電解質をメンブレンリアクターに用いたエタンの脱水素 Reviewed

    日比野高士、浜川 聡、岩原弘育

    日本化学会誌   Vol. 3   page: 238-242   1993

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  372. Protonic conduction of mordenite-type zeolite Reviewed

    Takashi Hibino, T. Akimoto, Hiroyasu Iwahara

    Solid State Ionics,   Vol. 67   page: 71-76   1993

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  373. H/D isotope effect on electrochemical pumps of hydrogen and water vapor using a proton-conductive solid electrolyte Reviewed

    Takashi Hibino, Keigo Mizutani, Hiroyasu Iwahara

    Journal of the Electrochemical Society   Vol. 140   page: 2588-2592   1993

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  374. Inactivation of external surface of mordenite and ZSM-5 by chemical vapor deposition of silicon alkoxide Reviewed

    Takashi Hibino, Miki Niwa, Yuichi Murakami

    Zeolites   Vol. 13   page: 518-523   1993

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  375. Simplification of solid oxide fuel cell system using partial oxidation of methane Reviewed

    Takashi Hibino, Hiroyasu Iwahara

    Chemistry Letters     page: 1131-1134   1993

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  376. Electrochemical methane coupling using protonic conductors Reviewed

    Satoshi Hamakawa, Takashi Hibino, Hiroyasu Iwahara

    Journal of the Electrochemical Society   Vol. 140   page: 459-462   1993

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  377. CO2 sensors using BaCeO3-based ceramics Reviewed

    Takashi Hibino, Hiroyasu Iwahara

    Sensors and Actuators B   Vol. 13-14   page: 483-485   1993

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  378. Dehydrogenation of Ethane Using Solid Electrolytes as Membrane Reactor Reviewed

    Hibino T., Hamakawa S., Iwahara H.

    Nippon Kagaku Kaishi   Vol. 1993 ( 3 ) page: 238 - 242   1993

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    The membrane reactors using three kinds of ionic conductors have been constructed in order to control the oxidative dehydrogenation of ethane electrochemically (Fig. 1). SrCe0.95. Yb0.05O3_a, Yttria-stabilized zirconia (YSZ) and BaCe0.9Y0.1O3-a were employed as protonic, oxide ionic and their mixed ionic conductors, respectively. When ethane and air were introduced at 700 °C into the anode and the cathode, respectively, and the direct current was passed through the reactor, the formation rate of ethylene became larger as the current density increased in all the reactors (Fig. 4). From the measurement of the anodic potential, one can speculate that the activation of ethane is based on the decrease in partial pressure of hydrogen in the pore of the anode (Fig. 5). The current efficiency for the formation of ethylene decreased in the order of SrCe0.95Yb0.05O3_a, BaCe0.9Y0.1 O3-aand YSZ (Table 1). This order can be explained by the thermal energy generated by changing the entropy of proton in the anodic reaction (Fig. 6). On the other hand, the formation rate of carbon dioxide increased with increasing the basicity of ionic conductors (Table 1). © 1993, The Chemical Society of Japan. All rights reserved.

    DOI: 10.1246/nikkashi.1993.238

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  379. Electrochemical Methane Coupling Using Protonic Conductors Reviewed

    Hamakawa S., Hibino T., Iwahara H.

    Journal of the Electrochemical Society   Vol. 140 ( 2 ) page: 459 - 462   1993

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    Coupling of methane was performed using SrCe0.95Ybo.o503-a ceramic as a membrane reactor at 1173 K. The electrochemical cell used was Ag/SrCe0.95Yb005O3_a/Ag. On introducing methane and Ar into the anode and the cathode, respectively, and on passing the direct current through the cell, formation rates of C2-compounds increased from 0.23 to 0.52 mmol min-1 cm-2. From themeasurement of the polarization characteristic, the partial pressure of hydrogen in theporous silver at the anode was found to be reduced by the electrochemical hydrogen pump. In addition, using a mixed conduction (protonic and p-type electronic conduction) of this ceramic, formation rates of C2-products were accelerated further. © 1993, The Electrochemical Society, Inc. All rights reserved.

    DOI: 10.1149/1.2221068

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  380. INACTIVATION OF EXTERNAL SURFACE OF MORDENITE AND ZSM-5 BY CHEMICAL-VAPOR-DEPOSITION OF SILICON ALKOXIDE Reviewed

    HIBINO T, NIWA M, MURAKAMI Y

    ZEOLITES   Vol. 13 ( 7 ) page: 518 - 523   1993

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  381. Studies on Proton Conducting Ceramics Based on Perovskite-type Oxides Reviewed

    Imaizumi H., Hibino T., Yajima T.

    Nippon Kagaku Kaishi   Vol. 1993 ( 9 ) page: 1003 - 1011   1993

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    Good proton conducting solids usuable at high temperature are applicable to a solid electrolyte for high electrolytic current devices like a fuel cell, an electrolyser for hydrogen production, a hydrogen separator etc. as well as for a high temperature-type chemical sensor. Such materials had been scarcely known until we found a series of oxide ceramics which have appreciable protonic conduction under hydrogen-containing stmosphere at high temprature. They are perovskite-type oxides based on SrCeO3 or BaCeO3 in which some trivalent cations are partially substituted for cerium. SrCe0.95 Yb0.05O3-α, B aCe0.9Nd0.1 O3-α etc. belong to this class of conductors. Later, some zirconate-base sintered oxides were also confirmed to be proton conductors under hydrogen containg atmosphere at high temperature. These oxide ceramics exhibit p-type electronic conduction in an atmosphere free from hydrogen or water vapor. However, when water vapor or hydrogen is introduced to the atmosphere at high temperature, electronic conductivity decreases and protonic conduction appears. When the ceramics are exposed to the hydrogen gas, they become almost pure protonic conductors, the conductivities of which are multi 10-2 S cm-1 at 1000 °C and multi 10-3 S cm-1 at 600 °C. Protonic conduction in these solids could be verified by means of electrochemical permeation of hydrogen across the ceramics. These oxides are unique ionic conductors in respect that they have no host constituents which liberate conducting ion (proton). Using these ceramics as a solid electrolyte, several types of electrochemical devices have been demonstrated by way of experiment. Based on the principle of hydrogen concentration cell, hydrogen sensors have put to practical use for molten aluminum in casting process. © 1993, The Chemical Society of Japan. All rights reserved.

    DOI: 10.1246/nikkashi.1993.1003

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  382. CHARACTERIZATION OF PROTON IN Y-DOPED SRZRO3 POLYCRYSTAL BY IR SPECTROSCOPY Reviewed

    HIBINO T, MIZUTANI K, YAJIMA T, IWAHARA H

    SOLID STATE IONICS   Vol. 58 ( 1-2 ) page: 85 - 88   1992.11

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  383. Characterization of proton in Y-doped SrZrO<inf>3</inf> polycrystal by IR spectroscopy Reviewed

    Hibino T., Mizutani K., Yajima T., Iwahara H.

    Solid State Ionics   Vol. 58 ( 1-2 ) page: 85 - 88   1992.11

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    To characterize proton in Y-doped SrZrO3 polycrystal, protonic conductivities and infrared spectra were measured. IR spectra exhibited two OH bands in 3500-2800 and 2650-2300 cm-1 regions, indicating that proton was bound to lattice oxide ion and that its strength of bonding was rather weak. The decrease in conductivity by replacing H+ with D+ suggested that the conducting ion was not hydroxide ion but proton and that it migrated via the dissociation of O-H bond. © 1992.

    DOI: 10.1016/0167-2738(92)90014-G

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  384. EVALUATION OF PROTON CONDUCTIVITY IN SRCEO3, BACEO3, CAZRO3 AND SRZRO3 BY TEMPERATURE PROGRAMMED DESORPTION METHOD Reviewed

    HIBINO T, MIZUTANI K, YAJIMA T, IWAHARA H

    SOLID STATE IONICS   Vol. 57 ( 3-4 ) page: 303 - 306   1992.10

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  385. Evaluation of proton conductivity in SrCeO<inf>3</inf>, BaCeO<inf>3</inf>, CaZrO<inf>3</inf> and SrZrO<inf>3</inf> by temperature programmed desorption method Reviewed

    Hibino T., Mizutani K., Yajima T., Iwahara H.

    Solid State Ionics   Vol. 57 ( 3-4 ) page: 303 - 306   1992.10

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    To better understand protonic conduction of perovskite-type oxides based on SrCeO3, CaZrO3 and SrZrO3, their TPD spectra were measured. By estimating the amount of water vapor evolved from these oxides, proton concentrations were found to be smaller in the order SrCe0.95Yb0.05O3-α, BaCe0.95Y0.05O3-α, SrZr0.95Y0.05O3-α and CaZr0.9In 0.1O3-α. Peak maximum temperatures gave the order of proton mobilities as: BaCe0.95Y0.05O3-α>SrZr0.95Y0.05O3-α>CaZr0.9In0.1O3-α>SrCe 0.95Yb0.05O3-α. Protonic conductivity could be explained by these two orders. © 1992.

    DOI: 10.1016/0167-2738(92)90162-I

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  386. ELECTROCHEMICAL METHANE ACTIVATION TO C-2-HYDROCARBONS USING PROTONIC CONDUCTOR Reviewed

    HIBINO T, HAMAKAWA S, IWAHARA H

    CHEMISTRY LETTERS   ( 9 ) page: 1715 - 1716   1992.9

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  387. AMPEROMETRIC-TYPE SENSOR FOR CO2 USING BACEO3-BASED CERAMIC Reviewed

    HIBINO T, IWAHARA H

    CHEMISTRY LETTERS   ( 7 ) page: 1221 - 1224   1992.7

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  388. BACE03-BASED PROTONIC CONDUCTOR SENSITIVE TO ETHANOL Reviewed

    HIBINO T, IWAHARA H

    CHEMISTRY LETTERS   ( 7 ) page: 1225 - 1228   1992.7

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  389. Evaluation of proton conductivity in SrCeO3, BaCeO3, CaZrO3 and SrZrO3 by temperature programmed deposition method Reviewed

    Takashi Hibino, Keigo Mizutani, Tamotsu Yajima, Hiroyasu Iwahara

    Solid State Ionics   Vol. 57   page: 303-306   1992

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  390. Amperometric-type sensor for CO2 using BaCeO3-based ceramic Reviewed

    Takashi Hibino, Hiroyasu Iwahara

    Chemistry Letters     page: 1221-1224   1992

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  391. Characterization of proton in Y-doped SrZrO3 polycrystal by IR spectroscopy Reviewed

    Takashi Hibino, Keigo Mizutani, Hiroyasu Iwahara

    Solid State Ionics   Vol. 58   page: 85-88   1992

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  392. Electrochemical methane activation to C2-hydrocarbons using protonic conductor Reviewed

    Takashi Hibino, Satoshi Hamakawa, Hiroyasu Iwahara

    Chemistry Letters     page: 1715-1716   1992

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  393. BaCeO3-based protonic conductor sensitive to ethanol Reviewed

    Takashi Hibino, Hiroyasu Iwahara

    Chemistry Letters     page: 1225-1228   1992

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  394. Shape-selectivity over hzsm-5 modified by chemical vapor deposition of silicon alkoxide Reviewed

    Hibino T., Niwa M., Murakami Y.

    Journal of Catalysis   Vol. 128 ( 2 ) page: 551 - 558   1991.4

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    Alkylation of toluene with methanol and toluene disproportionation have been carried out over HZSM-5 zeolites modified by chemical vapor deposition of silicon alkoxide. As the silica amount increased, the selectivity to m- and o-xylenes decreased, whereas that to p-xylene increased. The fraction of the para isomer in xylenes increased to more than 98%. From adsorption measurements and test reactions, it was found that this modification resulted in the narrowing of the pore-opening size and the inactivation of the external surface. The high para-selectivity was caused primarily by the narrowing of the pore-opening size. © 1991.

    DOI: 10.1016/0021-9517(91)90312-R

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  395. SHAPE-SELECTIVITY OVER HZSM-5 MODIFIED BY CHEMICAL VAPOR-DEPOSITION OF SILICON ALKOXIDE Reviewed

    HIBINO T, NIWA M, MURAKAMI Y

    JOURNAL OF CATALYSIS   Vol. 128 ( 2 ) page: 551 - 558   1991.4

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  396. Growth of Silica and its Controlling of Pore-opening Size on CVD Zeolites Reviewed

    Hibino T., Niwa M., Kawashima Y., Murakami Y.

    Studies in Surface Science and Catalysis   Vol. 60 ( C ) page: 151 - 158   1991.1

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    This paper describes how silica grows on the external surface of zeolite, and how it controls the pore-opening size. Silica growth and control of pore-opening size is not affected by the kind of cation but only by the composition of zeolite. The larger the silica content, the more similar the silica layer to the basal plane grows. Due to the subtle difference between overlayer and zeolite, the pore-opening size can be narrowed. Because of the similarity, thicker layers are required for control in the highly siliceous zeolites. © 1991 Kodansha Ltd.

    DOI: 10.1016/S0167-2991(08)61894-7

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  397. Shape-selectivity over ZSM-5 modified by chemical vapor deposition of silicon alkoxide Reviewed

    Takashi Hibino, Miki Niwa, Yuichi Murakami

    Journal of Catalysis   Vol. 128   page: 551-558   1991

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  398. Structure of germanium oxide on CVD zeolites by extended X-ray absorption fine structure and X-ray photoelectron spectroscopy Reviewed

    Hibino T., Niwa M., Murakami Y., Sano M.

    Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases   Vol. 85 ( 8 ) page: 2327 - 2334   1989.12

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    Chemical vapour deposition of GeO2 from Ge(OCH3) 4 on two kinds of H-mordenite with different silica to alumina ratios has been accomplished, and the deposited GeO2 has been characterized by EXAFS and XPS measurements. Shape-selectivity in cracking of octane isomers was strongly dependent on the composition of mordenite and similar in behaviour to the deposited silica from Si(OCH3)4. The amount of deposited GeO2 required to achieve the shape-selectivity on HM10 (Si/Al = 4.9) was less than that on HM20 (Si/Al = 10.0). On the other hand, the XPS measurement on these CVD mordenites yielded similar results as for the depth distribution of deposited GeO2. Furthermore, from the EXAFS measurement, the coordination numbers of the second-nearest Ge neighbours around the deposited Ge atoms on these CVD mordenites was less than that in α-quartz type GeO2. Based upon these findings, we can make some speculations about the structure of deposited GeO2 on these CVD mordenites: GeO2 is deposited on the external surface, apparently as a thin layer. Therefore, the difference in the shape-selectivity is caused by a difference not in the location but in the structure of the deposited GeO 2 between these CVD mordenites.

    DOI: 10.1039/F19898502327

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  399. STRUCTURE OF DEPOSITED GERMANIUM DIOXIDE WHICH CONTROLS THE PORE-OPENING SIZE OF MORDENITE Reviewed

    HIBINO T, NIWA M, MURAKAMI Y, SANO M, KOMAI S, HANAICHI T

    JOURNAL OF PHYSICAL CHEMISTRY   Vol. 93 ( 23 ) page: 7847 - 7850   1989.11

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  400. Structure of deposited germanium dioxide which controls the pore-opening size of mordenite Reviewed

    Hibino T., Niwa M., Murakami Y., Sano M., Komai S., Hanaichi T.

    Journal of physical chemistry   Vol. 93 ( 23 ) page: 7847 - 7850   1989.11

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    To better understand the fine control of pore-opening size of zeolites by the deposition of silicon alkoxide, germanium alkoxide has been employed as a model reagent for silicon alkoxide, and the structure of deposited GeO2 has been analyzed. When the CVD mordenite was stored under a condition of 100% humidity, followed by heating at 773 K, the deposited GeO2 was found to be transformed from an ultrathin layer into bulky particles on the external surface. Additionally, the shape selectivity gradually deteriorated with the growth of particle. In conclusion, the local protrusion of deposited GeO2 into the pore results into the heterogeneous narrowing of the pore-opening size, and the GeO2 must deposit as an ultrathin layer to improve the shape selectivity effectively. These conclusions may also be applicable to the deposition of silicon alkoxide.

    DOI: 10.1021/j100360a024

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  401. STRUCTURE OF GERMANIUM OXIDE ON CVD ZEOLITES BY EXTENDED X-RAY ABSORPTION FINE-STRUCTURE AND X-RAY PHOTOELECTRON-SPECTROSCOPY Reviewed

    HIBINO T, NIWA M, MURAKAMI Y, SANO M

    JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS I   Vol. 85   page: 2327 - 2334   1989.8

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  402. A SILICA MONOLAYER ON ALUMINA AND EVIDENCE OF LACK OF ACIDITY OF SILANOL ATTACHED TO ALUMINA Reviewed

    NIWA M, HIBINO T, MURATA H, KATADA N, MURAKAMI Y

    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS   ( 5 ) page: 289 - 290   1989.3

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  403. Structure of deposited germanium oxide which controls the pore-opening size of mordenite Reviewed

    Takashi Hibino, Miki Niwa, Yuichi Murakami, Mitsuru Sano, Shin-ichi Komai

    Journal of Physical Chemistry   Vol. 93   page: 7847-7850   1989

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  404. Structure of germanium oxide on CVD zeolites by extended X-ray adsorption fine structure and X-ray photoelectron spectroscopy Reviewed

    Takashi Hibino, Miki Niwa, Yuichi Murakami, Mitsuru Sano

    Journal of the Chemical Society, Faraday Transactions   Vol. 85   page: 2327-2334   1989

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  405. A silica monolayer on alumina and evidence of lack of acidity of silanol attached to alumina Reviewed

    Miki Niwa, Takashi Hibino, Haruhiko Murata, Naonobu Katada, Yuichi Murakami

    Journal of the Chemical Society, Chemical Communications     page: 289-290   1989

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  406. A silica monolayer on alumina and evidence of lack of acidity of silanol attached to alumina Reviewed

    Niwa M., Hibino T., Murata H., Katada N., Murakami Y.

    Journal of the Chemical Society, Chemical Communications   ( 5 ) page: 289 - 290   1989

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    A silica monolayer on alumina was formed by chemical vapour deposition of silicon methoxide; almost all the silanol attached to the alumina did not form Brønsted acid site.

    DOI: 10.1039/C39890000289

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  407. Chemical vapor deposition method for fine-control of the pore-opening size of Na-mordenite Reviewed

    Takashi Hibino, Miki Niwa, Akitaka Hattori, Yuichi Murakami

    Applied Catalysis   Vol. 44   page: 95-103   1988

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  408. Mechanism of chemical vapor deposition of silicon alkoxide on mordenites Reviewed

    Miki Niwa, Yoshimi Kawashima, Takashi Hibino, Yuichi Murakami

    Journal of the Chemical Society, Faraday Transctions   Vol. 84   page: 4327-4336   1988

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    Language:English   Publishing type:Research paper (scientific journal)  

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Books 11

  1. Encyclopedia of Applied Electrochemistry

    Takashi Hibino( Role: Sole author)

    Springer  2014 

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    Language:English

  2. 燃料電池要素技術

    日比野高士( Role: Joint author)

    情報機構  2011.12 

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    Language:Japanese

  3. 触媒調整ハンドブック

    日比野高士( Role: Sole author)

    エヌ・ティー・エス  2011.4 

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    Language:Japanese

  4. セラミック機能化ハンドブック

    日比野高士( Role: Sole author)

    エヌ・ティー・エス  2011.1 

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    Language:Japanese

  5. Nanomaterials for Energy Strage Applications

    Takashi Hibino( Role: Sole author)

    American Scientific Publishers  2009 

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    Language:English

  6. Ceramic Data Book

    冨田衷子,許 弼源,日比野高士( Role: Joint author)

    工業製品技術協会  2008 

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    Language:Japanese

  7. ナノイオニクス~最新技術とその展望~

    長尾征洋,日比野高士,佐野充( Role: Joint author)

    シー・エム・シー  2008 

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    Language:Japanese

  8. 燃料電池コージェネレーションシステム

    日比野高士( Role: Sole author)

    シー・エム・シー  2006 

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    Language:Japanese

  9. イオン伝導性材料の設計・合成とその応用

    日比野高士( Role: Sole author)

    ティー・アイ・シィー  2005 

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    Language:Japanese

  10. 環境学研究ソースブック

    名古屋大学環境学研究科編( Role: Joint author)

    藤原書店  2005 

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    Language:Japanese

  11. 分散型エネルギーシステムと燃料電池

    日比野高士( Role: Sole author)

    シーエムシー  2001 

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    Language:Japanese

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Presentations 38

  1. リグノセルロース系バイオマス資源を直接使用した燃料電池開発と水素製造

    日比野高士

    分子系の複合電子機能第181委員会 第30回研究会 

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    Event date: 2018.7

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Venue:東京大学本郷キャンパス   Country:Japan  

  2. 固体電解質膜を用いた各種プロトン型キャパシタの設計

    日比野高士

    2015年電気化学秋季大会 

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    Event date: 2015.9

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Venue:埼玉工業大学   Country:Japan  

  3. 固体酸及びアルカリ形燃料電池の研究開発と展望

    日比野高士

    燃料電池セミナー 

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    Event date: 2013.12

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Venue:名古屋商工会議所   Country:Japan  

  4. 無機系水酸化物イオン導電体とそのアルカリ形燃料電池への応用

    日比野高士

    第1回日本MRS講演会 

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    Event date: 2013.12

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Venue:横浜市   Country:Japan  

  5. 中温プロトン導電体のエネルギー・環境技術への応用

    日比野高士

    日本セラミックス協会2012年年会 

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    Event date: 2012.3

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Venue:京都大学   Country:Japan  

  6. 燃料電池に関連する有望な開発技術

    日比野高士

    経営者のための次世代自動車最新技術・動向講座 

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    Event date: 2012.1

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Venue:愛知県産業技術研究所(刈谷市)   Country:Japan  

  7. 中温プロトン導電体のコンポジット化技術

    日比野高士

    第59回固体イオニクス研究会 

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    Event date: 2012.1

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Venue:北海道大学   Country:Japan  

  8. Intermediate temperature proton conductors and their applications to PEMFCs

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    Event date: 2011.12

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  9. 中温プロトン導電体のコンポジット化技術

    日比野高士

    平成23年度日本セラミックス協会東海支部学術研究発表会 

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    Event date: 2011.12

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Venue:愛知県名古屋市   Country:Japan  

  10. セラミックス材料とエネルギー・環境技術

    日比野高士

    第2回長野県ファインセラミックス技術研究会 

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    Event date: 2011.10

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Venue:長野県長野市   Country:Japan  

  11. 固体高分子形燃料電池の高温・低湿度作動化に向けての材料開発

    日比野高士

    第30回石油化学会中国・四国支部講演会 

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    Event date: 2010.11

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Venue:鳥取県鳥取市   Country:Japan  

  12. 燃料電池電解質の設計と機能評価

    日比野高士

    電気化学を指向した「ものつくり」講習会 

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    Event date: 2010.9

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  13. In3+-Doped SnP2O7プロトン伝導体の酸化反応への応用

    日比野高士

    第106回触媒討論会 

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    Event date: 2010.9

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  14. 新規イオン導電体の設計とそれをを利用したエネルギー・環境技術への応用

    日比野高士

    第161回応用セラミックス研究所講演会「第6回先端無機材料講演会」 

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    Event date: 2010.3

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  15. 固体高分子形燃料電池の進展・今後の展望

    日比野高士

    「東海発!燃料電池研究開発の最前線」研究会 

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    Event date: 2009.11

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  16. 固体酸化物形燃料電池の進展・今後の展望

    日比野高士

    「東海発!燃料電池研究開発の最前線」研究会 

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    Event date: 2009.10

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  17. 電極触媒活性の精密制御に基づいたガスセンシング技術の開発と各種デバイスへの応用展開

    日比野高士

    第48回化学センサ研究発表会 

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    Event date: 2009.9

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  18. PEMFCの高温作動によるPt低減化技術

    日比野高士

    「次世代を展望するPEFC燃料電池のカソード触媒と担体」学術講演会 

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    Event date: 2009.7

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  19. 固体高分子形燃料電池用セパレータにおける現状と課題

    日比野高士

    燃料電池に関する最新の技術研究会 

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    Event date: 2008.12

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  20. 固体高分子形燃料電池用電解質膜における現状と課題

    日比野高士

    燃料電池に関する最新の技術研究会 

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    Event date: 2008.12

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  21. 固体高分子形燃料電池用触媒における現状と課題

    日比野高士

    燃料電池に関する最新の技術研究会 

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    Event date: 2008.11

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  22. 自動車・家庭用燃料電池の高温作動化に向けた材料開発

    日比野高士

    広域産学交流会2008 in 長野 

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    Event date: 2008.10

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  23. リン酸二量体ハイブリッド電解質における中温燃料電池の開発とその評価、応用

    日比野高士

    燃料電池で期待される有機無機ハイブリッド電解質膜の材料設計と耐久性評価、クラック対策 

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    Event date: 2007.4

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  24. リン酸二量体化合物から成る中温・無加湿燃料電池

    日比野高士

    第2回先端的燃料電池技術研究会 

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    Event date: 2006.6

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  25. 燃料電池技術

    日本弁理士会/先端技術研修会 

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    Event date: 2005.11

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  26. SnP2O7のプロトン導電性と固体電解質としての応用

    日比野高士

    第40回固体イオニクス研究会 

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    Event date: 2005.10

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  27. リン酸二量体MP2O7系プロトン導電体とその応用

    日比野高士

    第96回触媒討論会 

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    Event date: 2005.9

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  28. セリア系電解質を中心とした固体酸化物型燃料電池の開発

    日比野高士

    平成16年度触媒学会関西地区名古屋講演会 

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    Event date: 2004.11

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  29. セラミックスから成る燃料電池

    日比野高士

    第5回岐阜シンポジウム 

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    Event date: 2003.12

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  30. 炭化水素を燃料ガスに使用した次世代固体酸化物形燃料電池

    日比野高士

    人工粘土研究会第57回講演会 

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    Event date: 2003.1

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  31. 固体電解質担持触媒の電気化学的な活性制御:燃料電池への適用

    日比野高士

    第90回触媒討論会 

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    Event date: 2002.9

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  32. 燃料電池・ガスセンサ・メンブレンリアクタにおける電極触媒の開発

    日比野高士

    第29回環境触媒フォーラム 

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    Event date: 2002.8

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  33. 新概念に基づくSOFCとその可能性

    日比野高士

    近畿化学協会、近化セミナー・ここまできた燃料電池開発 

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    Event date: 2002.3

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  34. 燃料・空気混合ガス発電を可能にする単室SOFC

    日比野高士

    第307回電池技術委員会講演会 

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    Event date: 2001.9

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  35. 燃料電池の開発状況と課題 Invited

    日比野高士

    日本金属学会・日本鉄鋼協会東海支部、第34回若手材料研究会 

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    Event date: 2001.6

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  36. 自動車用としての固体酸化物形燃料電池の開発動向

    日比野高士

    第32回新技術動向セミナー 

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    Event date: 2001.6

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  37. 燃料電池の開発状況:システムと材料

    日比野高士

    愛知県工業技術センター、第26回工業技術研究大会 

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    Event date: 2001.6

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  38. 燃料電池開発の現状

    日比野高士

    日本金属学会・鉄鋼協会東海支部、平成12年度学術討論会 

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    Event date: 2001.1

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

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Research Project for Joint Research, Competitive Funding, etc. 26

  1. プロトン伝導材料およびプロトン伝導膜に関する技術指導

    2020.4

    学術コンサルティング 

  2. 電子貯蔵触媒技術による新プロセスの構築

    2018.10

    戦略的創造研究推進事業 

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    Grant type:Competitive

  3. 低温炭素成分燃焼触媒に関する研究

    2018.6 - 2019.9

    企業との共同研究 

  4. 炭化水素化合物の電気変換技術に関する基礎研究

    2017.4

    企業との共同研究 

  5. 電極状態の電気化学制御によるガスセンシング技術に関する基礎研究

    2016.8 - 2017.3

    企業との共同研究 

  6. SOFCのセル劣化現象に関する研究

    2013.11 - 2018.3

    企業との共同研究 

  7. 炭素成分検出センサ開発

    2013.6 - 2018.3

    企業との共同研究 

  8. 中温燃料電池用有機‐無機プロトン伝導性電解質膜に関する研究

    2011.12 - 2012.12

    企業との共同研究 

  9. 活性酸素を利用したディーゼルパティキュレートセンサの開発

    2010.4 - 2012.3

    企業との共同研究 

  10. NOx選択性が高く、低温での活性が高い電極の開発、NOxリアクタ開発

    2010.2 - 2011.1

    企業からの受託研究 

  11. プロトン導電体による酸素の活性化と触媒技術への応用

    2009.4 - 2012.5

    企業との共同研究 

  12. 活性酸素を利用したディーゼルパティキュレートセンサの開発

    2009.4 - 2012.3

    地域イノベーション創出総合支援事業 

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    Grant type:Competitive

  13. 電解質材料の特性改善、及びNOxセンサ高性能化の検証

    2009.4 - 2011.3

    企業との共同研究 

  14. リン酸二量体ベース燃料電池に関する研究

    2009.4 - 2010.3

    企業との共同研究 

  15. プロトン導電体を使用した電気化学デバイスに関する共同研究

    2008.6 - 2009.3

    企業との共同研究 

  16. 高性能高分子電解質膜・膜‐電極接合体に関する研究

    2008.4 - 2012.3

    企業との共同研究 

  17. 中温作動燃料電池用有機・無機ハイブリッド膜の研究

    2008.4 - 2011.3

    企業との共同研究 

  18. 中温域燃料電池用電解質に関する共同研究

    2007.8 - 2009.3

    企業との共同研究 

  19. 中温型電解質膜の家庭用燃料電池への適用

    2007.6 - 2010.3

    企業との共同研究 

  20. ピロリン酸スズ系プロトン導電体を使用した中温型燃料電池技術の定置用燃料電池への応用研究

    2007.5 - 2009.3

    企業との共同研究 

  21. 還元的酸素分子の活性化に基づく新しい環境調和型物質転換

    2007.4 - 2011.3

    特色ある大学教育支援プログラム 

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    Grant type:Competitive

  22. リン酸二量体ハイブリット電解質膜を使用した中温燃料電池の研究開発

    2006.10 - 2010.3

    固体高分子形燃料電池実用化戦略的技術開発/次世代技術開発 

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    Grant type:Competitive

  23. ペロブスカイト型酸化物薄膜のイオン電導,抵抗層解析

    2006.5 - 2007.3

    企業との共同研究 

  24. エタノール・シングルチャンバーSOFCに関する研究

    2005.12 - 2006.3

    企業との共同研究 

  25. 高プロトン導電体を使用した中温作動型燃料電池の試験研究

    2005.9 - 2006.3

    可能性試験(FS委託研究) 

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    Grant type:Competitive

  26. 中温領域作動酸化物燃料電池用セリア系電解質の高性能化研究

    2005.8 - 2007.3

    企業との共同研究 

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KAKENHI (Grants-in-Aid for Scientific Research) 9

  1. 都市廃棄物発電の高効率化を図るダイレクト廃棄物燃料電池の開発

    Grant number:21H03661  2021.4

    科学研究費補助金   基盤研究(B)

    日比野高士

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    Authorship:Principal investigator  Grant type:Competitive

  2. 活性酸素駆動による自己再生型ディーゼル・パティキュレート・マターセンサ

    Grant number:17H01895  2017.4 - 2021.3

    科学研究費補助金  基盤研究(B)

    日比野高士

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    Authorship:Principal investigator 

  3. 廃棄木質資源をダイレクトに燃料として利用する革新的バイオマス燃料電池

    Grant number:17K19087  2017.4 - 2019.3

    科学研究費補助金  挑戦的研究(萌芽)

    日比野高士

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    Authorship:Principal investigator 

  4. ヒドロゲナーゼと光合成の融合によるエネルギー変換サイクルの創成

    Grant number:26000008  2014.4 - 2019.3

    科学研究費補助金  特別推進研究

    小江誠司

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    Authorship:Coinvestigator(s) 

  5. 中温アルカリ形燃料電池用超水酸化物イオン導電体の開発

    2013.4 - 2018.3

    科学研究費補助金  基盤研究(B)

    日比野高士

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    Authorship:Principal investigator 

  6. セパレーターフリー単室燃料電池スタックの開発

    2011.4 - 2013.3

    科学研究費補助金  挑戦的萌芽研究

    日比野高士

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    Authorship:Principal investigator 

  7. 電気化学リアクターのナノサイズ化に基づく新しい触媒設計技術

    2009.4 - 2013.3

    科学研究費補助金  基盤研究(B)

    日比野高士

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    Authorship:Principal investigator 

  8. プロトン導電性リン酸二量体電解質を用いた中温領域型燃料電池の創製

    2005.4 - 2009.3

    科学研究費補助金  基盤研究(B)

    日比野高士

      More details

    Authorship:Principal investigator 

  9. ナノ分極型高選択反応性電極の創製

    2004.4 - 2009.3

    科学研究費補助金  特定領域研究

    日比野高士

      More details

    Authorship:Principal investigator 

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Industrial property rights 42

  1. 水素生成装置

    寺西真哉、山本亮平、福井舞、堀哲也、西川郁奈、今村弘男、日比野高士、長尾征洋

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    Applicant:株式会社SOKEN、株式会社デンソー、国立大学法人名古屋大学

    Application no:2019-201672  Date applied:2019.11

    Country of applicant:Domestic  

  2. 水素生成装置

    寺西真哉、福井舞、堀哲也、山本亮平、西川郁奈、今村弘男、日比野高士、長尾征洋

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    Applicant:株式会社SOKEN、株式会社デンソー、国立大学法人名古屋大学

    Application no:2019-201673  Date applied:2019.11

    Country of applicant:Domestic  

  3. 電気化学装置

    寺西真哉、福井舞、山本亮平、堀哲也、佐藤郁奈、今村弘男、日比野高士、長尾征洋

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    Applicant:株式会社SOKEN、株式会社デンソー、国立大学法人東海国立大学機構

    Application no:特願2019-056474  Date applied:2019.3

    Announcement no:特開2020-161225  Date announced:2020.10

  4. 炭化水素及び炭素の燃焼触媒並びに該燃焼触媒の製造方法

    平田裕人,長尾 諭,松本伸一,稲冨雄作,日比野高士

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    Application no:特願2011-029793  Date applied:2011

    Country of applicant:Domestic  

  5. 触媒層形成用組成物、ガス拡散電極、膜-電極接合体及び燃料電池

    仲野武史,山下竹友,小野友裕,須郷 望,日比野高士

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    Application no:特願2010-249168  Date applied:2010

    Country of applicant:Domestic  

  6. プロトン導電体、及びその製造方法、並びに炭素量検出センサ

    原田敏彦,水谷圭吾,寺西真哉,中村 聡,福田雄史,日比野高士,沈 岩柏

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    Application no:特願2010-195339  Date applied:2010

    Country of applicant:Domestic  

  7. 炭化水素及び炭素の燃焼触媒

    平田裕人,長尾 諭,松本伸一,日比野高士

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    Application no:特願2010-043106  Date applied:2010

    Country of applicant:Domestic  

  8. 電解質,電解質膜,膜-電極接合体及び燃料電池

    仲野武史,清水和哉,久保敬次,須郷 望,日比野高士,金 永成

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    Application no:特願2010-023525  Date applied:2010

    Country of applicant:Domestic  

  9. 有機-無機複合電解質,電解質膜,膜-電極接合体及び燃料電池

    仲野武史,小野友裕,久保啓次,須郷 望,日比野高士,許 弼源

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    Application no:特願2008-310279  Date applied:2008

    Country of applicant:Domestic  

  10. 有機-無機複合電解質,電解質膜,膜-電極接合体及び燃料電池

    仲野武史,小野友裕,久保啓次,須郷 望,日比野高士,許 弼源

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    Application no:特願2008-301810  Date applied:2008

    Country of applicant:Domestic  

  11. 有機-無機複合電解質,電解質膜,膜-電極接合体及び燃料電池

    仲野武史,小野友裕,須郷 望,久保啓次,日比野高士,許 弼源

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    Application no:特願2008-274874  Date applied:2008

    Country of applicant:Domestic  

  12. アンモニアセンサ素子及びプロトン導電性固体電解質体の製造方法

    加藤哲也,寺西真哉,度会武宏,澤田高志,日比野高士,冨田衷子,

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    Announcement no:特許公開2011-069705 

    Country of applicant:Domestic  

  13. 電解質

    日比野高士,許 弼源,永坂圭介,

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    Announcement no:特許公開2010-153109 

    Country of applicant:Domestic  

  14. 固体高分子形燃料電池用電解質膜,固体高分子形燃料電池用電解質膜の製造方法,固体高分子形燃料電池および燃料電池システム

    佐藤康司,水野環樹,関 友里,日比野高士,

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    Announcement no:特許公開2010-103000 

    Country of applicant:Domestic  

  15. 電極触媒

    日比野高士,許 弼源,永坂圭介,

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    Announcement no:特許公開2101-149008 

    Country of applicant:Domestic  

  16. 炭素量検出センサ

    寺西真哉,水谷圭吾,日比野高士,冨田衷子,

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    Announcement no:特許公開2010-054432 

    Country of applicant:Domestic  

  17. 電極触媒及び電極触媒の製造方法

    日比野高士,長尾征洋,許 弼源,永坂圭介,

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    Announcement no:特許公開2009-158131 

    Country of applicant:Domestic  

  18. ハイブリッド電解質膜及びハイブリッド電解質膜の製造方法

    日比野高士,長尾征洋,許 弼源,永坂圭介,

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    Announcement no:特許公開2009-158130 

    Country of applicant:Domestic  

  19. 単室型燃料電池及び修飾酸化マンガンの製造方法

    日比野高士,長尾征洋,永坂圭介,

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    Announcement no:特許公開2009-070733 

    Country of applicant:Domestic  

  20. 電極、電極触媒組成物および燃料電池

    日比野高士,長尾征洋,行方陽介,岩崎克彦,田中利彦,

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    Announcement no:特許公開2008-270181 

    Country of applicant:Domestic  

  21. 電極触媒組成物、電極および燃料電池

    日比野高士,長尾征洋,行方陽介,岩崎克彦,田中利彦,

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    Announcement no:特許公開2008-270180 

    Country of applicant:Domestic  

  22. 複合イオン伝導材料

    町田洋一郎,岩崎克彦,田中利彦,日比野高士,吉村 研,

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    Announcement no:特許公開2008-218408 

    Country of applicant:Domestic  

  23. 金属リン酸塩とその製造方法

    日比野高士,田中利彦,服部武司,

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    Announcement no:特許公開2008-053225 

    Country of applicant:Domestic  

  24. 金属リン酸塩

    日比野高士,田中利彦,服部武司,

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    Announcement no:特許公開2008-053224 

    Country of applicant:Domestic  

  25. セリア系固体電解質及びその製造方法

    日比野高士,星野和友,高橋和明,国崎敏哉,

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    Announcement no:特許公開2005-243473 

    Country of applicant:Domestic  

  26. 固体電解質型燃料電池

    日比野高士,石川浩也,飯尾 聡,

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    Announcement no:特許公開2004-103338 

    Country of applicant:Domestic  

  27. 固体電解質型燃料電池及びその製造方法

    日比野高士,石川浩也,飯尾 聡,

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    Announcement no:特許公開2003-282123 

    Country of applicant:Domestic  

  28. 一酸化炭素ガスセンサ

    日比野高士,柿元志郎,井上隆治,石田 昇,

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    Announcement no:特許公開2003-207482 

    Country of applicant:Domestic  

  29. 可燃性ガスセンサ及び可燃性ガス濃度測定方法

    日比野高士,柿元志郎,井上隆治,石田 昇,

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    Announcement no:特許公開2003-083929 

    Country of applicant:Domestic  

  30. 単室型固体電解質型燃料電池及びその製造方法

    日比野高士,柿元志郎,

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    Announcement no:特許公開2002-280017 

    Country of applicant:Domestic  

  31. 単室型固体電解質型燃料電池及びその製造方法

    日比野高士,柿元志郎,

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    Announcement no:特許公開2002-280015 

    Country of applicant:Domestic  

  32. ガスセンサ及びガス濃度測定方法並びに炭化水素ガスセンサ及び炭化水素ガス濃度測定方法

    日比野高士,井上隆治,柿元志郎,石田 昇,

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    Announcement no:特許公開2002-277430 

    Country of applicant:Domestic  

  33. ガスセンサ及び炭化水素ガスセンサ

    日比野高士,井上隆治,柿元志郎,石田 昇,

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    Announcement no:特許公開2002-202281 

    Country of applicant:Domestic  

  34. 活性酸素の電気化学的生成とそれによるNOx選択還元反応の促進方法

    日比野高士,

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    Announcement no:特許公開2001-096138 

    Country of applicant:Domestic  

  35. 単室型固体電解質型燃料電池

    日比野高士,

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    Announcement no:特許公開2000-243412 

    Country of applicant:Domestic  

  36. ガスセンサ並びに炭化水素ガスセンサ及び水素ガスセンサ

    日比野高士,桑原好孝,井上隆治,大島崇文,加藤倫朗,

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    Announcement no:特許公開2000-146902 

    Country of applicant:Domestic  

  37. 固体電解質を利用した高NOx還元作用を有する電極材及びNOx削減方法

    日比野高士,

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    Announcement no:特許公開2000-140564 

    Country of applicant:Domestic  

  38. 排気ガスセンサ及び排気ガスセンサシステム

    井上隆治,夫馬智弘,黒木由美,北野谷昇治,大島崇文,日比野高士,

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    Announcement no:特許公開平10-197479 

    Country of applicant:Domestic  

  39. コージェネレーション用非隔膜式固体電解質型燃料電池

    日比野高士,宇敷建一,桑原好孝,

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    Announcement no:特許公開平08-264195 

    Country of applicant:Domestic  

  40. 炭化水素センサ

    岩原 弘育,日比野高士,矢嶋 保,

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    Announcement no:特許公開平06-242060 

    Country of applicant:Domestic  

  41. 炭酸ガスセンサ素子および炭酸ガス濃度測定方法

    岩原 弘育,日比野高士,山内則義,磯部隆昌,

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    Announcement no:特許公開平06-186193 

    Country of applicant:Domestic  

  42. 不飽和炭化水素系化合物の製造方法

    岩原 弘育,日比野高士,濱川 聡,出口 隆,

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    Announcement no:特許公開平06-088080 

    Country of applicant:Domestic  

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Teaching Experience (On-campus) 3

  1. Fundamentals of Chemistry I

    2020

  2. Functional Molecules for Environment

    2020

  3. Seminar on Materials and Environment 1A

    2020

Teaching Experience (Off-campus) 2

  1. 大学院特別講義

    2006.4 - 2007.3 Nagoya Institute of Technology)

  2. 学部講義

    2003.4 - 2004.3 Gifu University)

 

Social Contribution 1

  1. クラウドファンディング

    Role(s):Planner

    2020.8

Media Coverage 1

  1. 古新聞から効率良く水素抽出 Newspaper, magazine

    中日新聞社  中日新聞  朝刊一面  2017.9

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    Author:Other 

Academic Activities 1

  1. Scientific Reports Editorial Member International contribution

    Role(s):Peer review

    2015

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    Type:Peer review