研究者詳細 - 長尾　征洋

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

Lv, P; Ito, T; Oogushi, A; Nakashima, K; Nagao, M; Hibino, T

SCIENTIFIC REPORTS 6 巻頁： 37463 2016年11月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Scientific Reports

In recent years, exhaust sensors have become increasingly attractive for use in energy and environmental technologies. Important issues regarding practical applications of these sensors, especially for soot measurements, include the further development of ion-conductive electrolytes and active electrode catalysts for meeting performance and durability requirements. Herein, we design a proton conductor with a high breakdown voltage and a sensing electrode with high sensitivity to electrochemical carbon oxidation, enabling continuous soot monitoring with self-regeneration of the sensor. A Si0.97 Al0.03 Hx P2 O7 layer with an excellent balance between proton conductivity and voltage endurance was grown on the surface of a Si0.97 Al0.03 O2 substrate by reacting it with liquid H3 PO4 at 600 °C. Specific reactivity of the electrochemically formed active oxygen toward soot was accomplished by adding a Pt-impregnated Sn0.9 In0.1Hx P2 O7 catalyst into a Pt sensing electrode. To make the best use of these optimized materials, a unipolar electrochemical device was fabricated by configuring the sensing and counter electrodes on the same surface of the electrolyte layer. The resulting amperometric mode sensor successfully produced a current signal that corresponded to the quantity of soot.

DOI： 10.1038/srep37463

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

PubMed

Hibino, T; Kobayashi, K; Nagao, M

SCIENTIFIC REPORTS 6 巻頁： 31691 2016年8月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Scientific Reports

Numerous studies have examined the switching properties of semi-or ion-conductors and isolators; however, most of these have focused on the ohmic resistance characteristics. Here, we report a new type of polarity-dependent switching phenomenon obtained for electrical devices with the configuration: metal working electrode |Si0.97Al0.03H0.03P2O7-polytetrafluoroethylene composite electrolyte |Pt/C counter electrode. The counter electrode is reversibly active for the water vapor oxidation and evolution reactions. The composite electrolyte exhibits high withstanding voltage capability in the bias voltage range of ± 7 V. When titanium was employed as the working electrode, the anodic polarization resistance was approximately two orders of magnitude greater than the cathodic polarization resistance. The ohmic resistance of the device was almost unchanged, regardless of the bias voltage polarity. Moreover, kinetically induced high-resistance/low-resistance states could be cyclically switched through positive/negative bias voltage pulses, and these states were also confirmed to be memorized at open circuit.

DOI： 10.1038/srep31691

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

PubMed

Kobayashi, K; Nagao, M; Hibino, T

CHEMISTRY LETTERS 45 巻 ( 2 ) 頁： 161 - 163 2016年2月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：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

Rechargeable Metal-Air Proton-Exchange Membrane Batteries for Renewable Energy Storage

Nagao, M; Kobayashi, K; Yamamoto, Y; Yamaguchi, T; Oogushi, A; Hibino, T

CHEMELECTROCHEM 3 巻 ( 2 ) 頁： 247 - 255 2016年2月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ChemElectroChem

Rechargeable proton-exchange membrane batteries that employ organic chemical hydrides as hydrogen-storage media have the potential to serve as next-generation power sources; however, significant challenges remain regarding the improvement of the reversible hydrogen-storage capacity. Here, we address this challenge through the use of metal-ion redox couples as energy carriers for battery operation. Carbon, with a suitable degree of crystallinity and surface oxygenation, was used as an effective anode material for the metal redox reactions. A Sn0.9In0.1P2O7-based electrolyte membrane allowed no crossover of vanadium ions through the membrane. The V4+/V3+, V3+/V2+, and Sn4+/Sn2+ redox reactions took place at a more positive potential than that for hydrogen reduction, so that undesired hydrogen production could be avoided. The resulting electrical capacity reached 306 and 258mAhg-1 for VOSO4 and SnSO4, respectively, and remained at 76 and 91% of their respective initial values after 50 cycles.

DOI： 10.1002/celc.201500473

Rechargeable metal-air proton -exchange membrane batteries for renewable energy storage 査読有り

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

ChemElectroChem 3 巻頁： 247-255 2016年

Kinetically driven switching and memory phenomena at the interface between a proton-conductive electrolyte and a titanium electrode 査読有り

Takashi Hibino, Kazuyo Kobayashi, Masahiro Nagao

Scientific Reports 6 巻頁： 31691 2016年

A self-regenerable soot sensor with a proton-conductive thin electrolyte and a nanostructured platinum sensing electrode 査読有り

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

Scientific Reports 6 巻頁： 37463 2016年

A Sensitive and Self-Regenerable Particulate Matter Sensor with a H3PO4-Modified BaZr0.8Y0.2O3-δ Electrolyte and an IrO2-Catalyzed Sensing Electrode

Lv, PL; Oogushi, A; Nakashima, K; Kobayashi, K; Nagao, M; Hibino, T

JOURNAL OF THE ELECTROCHEMICAL SOCIETY 163 巻 ( 14 ) 頁： B761 - B767 2016年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：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

Design of a Rechargeable Fuel-Cell Battery with Enhanced Performance and Cyclability

Hibino, T; Kobayashi, K; Nagao, M; Yamamoto, Y

JOURNAL OF THE ELECTROCHEMICAL SOCIETY 163 巻 ( 7 ) 頁： A1420 - A1428 2016年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of the Electrochemical Society

Electrochemical devices integrating a fuel cell with a hydrogen storage medium are able to function as secondary batteries. Batteries incorporating a partially oxygenated carbon anode with a RuO2/C cathode exhibit excellent reversibility, but their performance is not yet sufficient for secondary battery applications. This is due to excessive oxygenation of the anode, degradation of the cathode and the excess weight of the electrolyte membrane. In the present work, we addressed these challenges through various improvements in the design of a rechargeable proton-exchange membrane battery. These included coating the surface of a significantly oxygenated carbon anode (O/C atomic ratio 0.131) with carbon black nanoparticles, nanocrystallization of a carbon-free RuO2 cathode (avg. crystallite size 1.1 nm) and the synthesis of an inorganic-organic composite electrolyte membrane. As a result of these optimizations, coulombic efficiencies of over 95% were achieved during charge/discharge over the voltage range of 0.0–1.5 V at 75°C. The resulting device exhibited an initial capacity of 330 mAh g−1 and was stable over 300 cycles, with maximum energy and power densities of 47 Wh kg−1 and 1114 W kg−1, respectively.

DOI： 10.1149/2.1341607jes

A Direct Urine Fuel Cell Operated at Intermediate Temperatures

A Sensitive and Self-Regenerable Particulate Matter Sensor with a H3PO4-Modified BaZr0.8Y0.2O3-δ Electrolyte and an IrO2-Catalyzed Sensing Electrode 査読有り

長尾征洋

Journal of The Electrochemical Society 163 巻 2016年

Diversity oriented multi-objective island based genetic algorithm for flexible job shop scheduling considering setup operator regulation 査読有り

Masahiro Nagao, Takuya Sugimoto, Yasuhiko Morinaga, and Mitsuru Sano

Journal of Human Environmental Studies 12 巻 ( 1 ) 頁： 1-12 2015年6月

Nagao, M; Kobayashi, K; Hibino, T

CHEMISTRY LETTERS 44 巻 ( 3 ) 頁： 363 - 365 2015年3月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemistry Letters

Direct utilization of urine in fuel cells is a promising technology for conversion into electricity. Here, we report the design of anode materials for high-temperature direct urine fuel cells and the performance of a fuel cell with an optimized anode at 300 °C. The resultant peak power densities reached 16.7mW cm-2 for urine and 26.5mW cm-2 for urea.

DOI： 10.1246/cl.141067

High-temperature supercapacitor with a proton-conducting metal pyrophosphate electrolyte

Hibino, T; Kobayashi, K; Nagao, M; Kawasaki, S

SCIENTIFIC REPORTS 5 巻頁： 7903 2015年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Scientific Reports

Expanding the range of supercapacitor operation to temperatures above 100°C is important because this would enable capacitors to operate under the severe conditions required for next-generation energy storage devices. In this study, we address this challenge by the fabrication of a solid-state supercapacitor with a proton-conducting Sn 0.95 Al0.05H0.05P2O7 (SAPO)-polytetrafluoroethylene (PTFE) composite electrolyte and a highly condensed H3 PO4 electrode ionomer. At a temperature of 200°C, the SAPO-PTFE electrolyte exhibits a high proton conductivity of 0.02 S cm-1 and a wide withstanding voltage range of ±2 V. The H3PO4 ionomer also has good wettability with micropore-rich activated carbon, which realizes a capacitance of 210 F g-1 at 200°C. The resulting supercapacitor exhibits an energy density of 32 Wh kg-1 at 3 A g-1 and stable cyclability after 7000 cycles from room temperature to 150°C.

DOI： 10.1038/srep07903

段取り作業者を考慮した生産スケジューリングへの多様性指向型多目的GAの適用

PubMed

長尾征洋, 杉本拓弥, 森永泰彦, 佐野充

人間環境学研究 13 巻 ( 1 ) 頁： 1 - 12 2015年

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：人間環境学研究会

製品生産現場における生産スケジュールの定式化として、フレキシブルジョブスケジューリング問題が研究の対象とされている。各ジョブショップにリソースとして製品（群）・機械・オペレータが割り当てられる研究例は多いが、段取り作業および段取り従事者に注目した研究は見られない。多品種少量生産の現場では、段取り作業者資源の効率的な配分が生産性の向上につながる。一方、人的な資源であるために、従事者の満足度は軽視できない。本研究では、段取り作業者を取り入れたフレキシブルジョブショップ問題を取り上げ、多様性指向型多目的遺伝的アルゴリズムによる解法を提案する。納期遅れ指数と段取り作業者の負荷指数を評価関数とすることで、顧客と作業従事者の視点に立った最適化が可能になった。提案手法により短時間で生産スケジュールを作成することができ、実生産データを用いた場合においても、適用可能なスケジュールを導出することができた。

DOI： 10.4189/shes.13.1

Rechargeable PEM Fuel-Cell Batteries Using Porous Carbon Modified with Carbonyl Groups as Anode Materials 国際共著

Kobayashi, K; Nagao, M; Yamamoto, Y; Heo, P; Hibino, T

JOURNAL OF THE ELECTROCHEMICAL SOCIETY 162 巻 ( 8 ) 頁： F868 - F877 2015年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of the Electrochemical Society

Rechargeable fuel-cell batteries (RFCBs) operate by hydrogen storage and release at the anode, while oxygen evolution and reduction reactions occur at the cathode. High-surface-area porous carbon was treated with HNO3 to produce an anode material with carbonyl and phenol groups on the surface, thereby providing redox sites for hydrogen storage and release. The HNO3-activated carbon anodes were characterized with respect to use in a RFCB operated from room temperature to 75°C with a voltage range of 0-2.0 V. The quantity of carbonyl groups and the corresponding reduced phenol groups increased with the O/C atomic ratio of the oxygenated carbon, by which the electrical capacity was increased to reach a maximum of 125 mAh g-1 at an O/C atomic ratio of 0.114. The optimal temperature and charge voltage for performance and cyclability were determined to be 50°C and 1.25 V, respectively. The charge and discharge times remained at ca. 93% of the respective initial values after 300 cycles. The RFCB with the modified porous carbon anode provided energy densities of 2.5-13.8 Wh kg-1 and power densities of 46.4-296.3 W kg-1 (normalized according to the mass of the entire cell).

DOI： 10.1149/2.0581508jes

Rechargeable PEM Fuel-Cell Batteries Using Quinones as Hydrogen Carriers

Nagao, M; Kobayashi, K; Yamamoto, Y; Hibino, T

JOURNAL OF THE ELECTROCHEMICAL SOCIETY 162 巻 ( 4 ) 頁： F410 - F418 2015年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of the Electrochemical Society

Rechargeable fuel-cell batteries (RFCBs) that employ organic chemical hydrides as hydrogen storage media have potential as nextgeneration power sources; however, the reversible storage and release of hydrogen remains a significant challenge. In particular, the hydrogenation of organic compounds during cell charge is difficult to achieve with 100% conversion. However, this report demonstrates that quinones, especially anthraquinone (AQ), can function as a hydrogen carrier for RFCBs, where AQ is hydrogenated to anthrahydroquinone (AH2Q) during charge and AH2Q is dehydrogenated to AQ during discharge. This redox reaction occurred at a more positive potential than that for hydrogen reduction, so that undesired hydrogen production can be avoided by adjusting the charge voltage to 1 V. The resulting RFCB maintained 100% electrical capacity at room temperature, 91% at 50°C, and 63% at 75°C of the respective initial performance with coulombic efficiencies greater than 90% after 300 cycles. Moreover, the RFCB functioned as a secondary battery with energy densities of 0.8.3.4 Wh kg-1, power densities of 9.5-258.9 W kg-1, and as a fuel cell with power densities of 0.001-0.26 W cm-3. Based on the performance and degradation data, the limitations of this RFCB and directions for future research are discussed.

DOI： 10.1149/2.0611504jes

Low-temperature Sintering of Yttria-stabilized Zirconia Using Bismuth-Vanadium Oxide as a Sintering Aid at 800 °C

Nagao, M; Kobayashi, K; Hibino, T

CHEMISTRY LETTERS 43 巻 ( 12 ) 頁： 1887 - 1889 2014年12月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：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