Development of high active catalyst for fuel cell by controlling interface and electronic state of interface

• Project/Area Number: 17H03410
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Structural/Functional materials
• Research Institution: University of Yamanashi
• Principal Investigator: KAKINUMA Katsuyoshi 山梨大学, 大学院総合研究部, 特任教授 (60312089)
• Co-Investigator(Kenkyū-buntansha): 内田 誠 山梨大学, 大学院総合研究部, 教授 (10526734)
• Project Period (FY): 2017-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥17,810,000 (Direct Cost: ¥13,700,000、Indirect Cost: ¥4,110,000); Fiscal Year 2019: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000); Fiscal Year 2018: ¥8,710,000 (Direct Cost: ¥6,700,000、Indirect Cost: ¥2,010,000); Fiscal Year 2017: ¥6,370,000 (Direct Cost: ¥4,900,000、Indirect Cost: ¥1,470,000)
• Keywords: 電極触媒 / 固体高分子形燃料電池 / 触媒活性 / 耐久性 / 相互作用 / 電気伝導性 / 電子構造 / 微細構造 / 貴金属担持触媒 / 多孔性材料 / 電子輸送特性 / 燃料電池 / ナノ粒子 / 電子状態 / 固固界面 / カソード触媒 / 酸化物 / 白金 / 酸素還元活性 / 電極材料 / ナノ材料 / 界面

Outline of Final Research Achievements

The highly active and durable electrocatalysts for polymer electrolyte fuel cells were inventied. The innovative electrocatalysts showed the higher electronic conductivity and oxygen reduction reaction activity rather than those of commercial electrocatalysts. These improvements relies on the metal- support interactions induced by the electronic donation from noble metal to oxide supports. The three phase boundary of Pt/support/gas was constructed by applying the hydrophilic surface of the supports, which improved the catalyst layer performances. The atmospheric resistive switching mechanism of the Pt catalyst supported on oxides were also invented to mitigate the degradation of the cathode catalysts under the high potential at the startup/shutdown process.

Academic Significance and Societal Importance of the Research Achievements

触媒活性及び耐久性を格段に向上させた電極触媒の開発すると共に、Pt/担体/気相による新たな三相界面の設計方法や“大気抵抗スイッチングメカニズム”を提唱し、家庭用・自動車用固体高分子形燃料電池の耐久性、性能向上に大きく貢献した。また、触媒の電子輸送特性と酸素還元活性の向上要因となる触媒-担体相互作用のメカニズム及びその学理の解明に成功した。

Research Products

• [Int'l Joint Research] Boston University(米国)
• [Journal Article] Electronic States and Transport Phenomena of Pt Nanoparticle Catalysts Supported on Nb-Doped SnO2 for Polymer Electrolyte Fuel Cells (2019)
  • Author(s): Kakinuma Katsuyoshi、Suda Kohei、Kobayashi Ryo、Tano Tetsuro、Arata Chisato、Amemiya Isao、Watanabe Sumitaka、Matsumoto Masashi、Imai Hideto、Iiyama Akihiro、Uchida Makoto
  • Journal Title: ACS Applied Materials & Interfaces Volume: 11 Issue: 38 Pages: 34957-34963
  • DOI: 10.1021/acsami.9b11119
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis and Evaluation of High Durable Electrocatalysts Using Oxide Supports for Polymer Electrolyte Fuel Cells (Second Report) (2019)
  • Author(s): 柿沼 克良、小椋 文昭、松谷 耕一、飯山 明裕、内田 誠、雨宮 功、荒田 知里、渡辺 純貴、石田 稔、李 牧、秋山 朋弘
  • Journal Title: Transactions of Society of Automotive Engineers of Japan Volume: 50 Issue: 6 Pages: 1549-1553
  • DOI: 10.11351/jsaeronbun.50.1549
  • NAID: 130007751117
  • ISSN: 0287-8321, 1883-0811
  • Peer Reviewed / Open Access
• [Journal Article] Influence of Ionomer Content on Both Cell Performance and Load Cycle Durability for Polymer Electrolyte Fuel Cells Using Pt/Nb-SnO2 Cathode Catalyst Layers (2018)
  • Author(s): Katsuyoshi Kakinuma,Ryo Kobayashi, Akihiro Iiyama, Makoto Uchida
  • Journal Title: Journal of Electrochemical Society Volume: 165 Issue: 15 Pages: J3083-J3089
  • DOI: 10.1149/2.0141815jes
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis and evaluation of double-layer electrodes using a Ni–BaCe_0.50Zr_0.27Y_0.20Ni_0.03O_{3−δ} cermet with a fused-aggregate network structure as the hydrogen electrode of solid oxide cells (2018)
  • Author(s): Ryosuke NISHIKAWA, Hanako NISHINO, Manuel E. BRITO and Katsuyoshi KAKINUMA
  • Journal Title: Journal of the Ceramic Society of Japan Volume: 126 Issue: 3 Pages: 208-213
  • DOI: 10.2109/jcersj2.17258
  • NAID: 130006407830
  • ISSN: 1348-6535, 1882-0743
  • Peer Reviewed / Open Access
• [Journal Article] Electrochemical Oxidation of Hydrolyzed Poly-Oxymethylene-Dimethylether by Pt and PtRu Catalysts on Ta-Doped SnO2 Supports for Direct Oxidation Fuel Cells (2017)
  • Author(s): Katsuyoshi Kakinuma, Naoki Hirayama, Akihiro Iiyama, Masahiro Watanabe,and Makoto Uchida
  • Journal Title: Journal of The Electrochemical Society Volume: 164 Issue: 12 Pages: F1226-F1233
  • DOI: 10.1149/2.1461712jes
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis and Evaluation of Ni Catalysts Supported on BaCe0.5Zr0.3-xY0.2NixO3 with Fused-Aggregate Network Structure for the Hydrogen Electrode of Solid Oxide Electrolysis Cell (2017)
  • Author(s): Ryosuke Nishikawa, Katsuyoshi Kakinuma, Hanako Nishino, Manuel E. Brito,Srikanth Gopalan, and Hiroyuki Uchida
  • Journal Title: Catalysts Volume: 7 Issue: 7 Pages: 1-11
  • DOI: 10.3390/catal7070223
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Presentation] セラミックス担体を用いたPEFC用高耐久・高活性触媒の開発 (2020)
  • Author(s): 柿沼克良
  • Organizer: FC-EXPO
  • Invited
• [Presentation] Highly Durable and Active Electrocatalysts using Ceramic Supports for Polymer Electrolyte Fuel Cells (2019)
  • Author(s): K.Kakinuma, M. Uchida, A. Iiyama
  • Organizer: ACEPS-10
  • Int'l Joint Research / Invited
• [Presentation] Pt・Pt合金担持セラミックス触媒を用いた固体高分子形燃料電池の性能 (2019)
  • Author(s): 柿沼克良
  • Organizer: 第17回 燃料電池基盤技術研究懇話会
  • Invited
• [Presentation] Pt担持セラミックス触媒を用いた固体高分子形 燃料電池用カソード触媒の性能 (2019)
  • Author(s): 柿沼克良，飯山明裕，内田誠，雨宮功，荒田知里，渡辺純貴
  • Organizer: 第60回電池討論会
• [Presentation] 燃料電池の基礎及び開発動向 (2019)
  • Author(s): 柿沼克良
  • Organizer: 電気化学会・普及委員会・電気化学セミナー4
  • Invited
• [Presentation] 燃料電池材料及びその評価方法について (2019)
  • Author(s): 柿沼克良
  • Organizer: COMS-NANO
  • Invited
• [Presentation] PEFCの高温作動に伴う課題とPt担持セラミックス触媒の挑戦 (2019)
  • Author(s): 柿沼克良
  • Organizer: 公益社団法人 高分子学会 2019年度水素・燃料電池材料研究会
  • Invited
• [Presentation] Improvement of the performance of Pt catalysts supported on Nb-doped SnO2 via well-controlled interfaces (2019)
  • Author(s): Katsuyoshi Kakinuma, Ryo Kobayashi, Tetsuro Tano, Takayuki Asakwawa, Isao Amemiya, Chisato Arata, Sumitaka Watanabe, Akihiro Iiyama, and Makoto Uchida
  • Organizer: 236th, ECS Meeting
  • Int'l Joint Research
• [Presentation] 次世代燃料電池に向けた材料開発の方向性 (2019)
  • Author(s): 柿沼克良
  • Organizer: 水素機器用エラストマー材料研究分科会 ゴム技術シンポジウム
  • Invited
• [Presentation] PEFC用高活性・高耐久性触媒の実用化への挑戦 (2019)
  • Author(s): 柿沼克良
  • Organizer: 電気化学セミナー１ 「最先端電池技術-2019」
  • Invited
• [Presentation] Pt担持酸化チタンをアノードに用いたPEFCの性能評価 (2019)
  • Author(s): 筒井慎一郎, 柿沼克良, 内田誠, 飯山明裕
  • Organizer: 電気化学会第８６回大会
• [Presentation] Influence of Ionomer Content on Cell Performance and Load Cycle Durability of Membrane-Electrode Assemblies Using Pt/Nb-SnO2 Cathode Catalyst Layers (2018)
  • Author(s): R. Kobayashi, K. Kakinuma, A. Iiyama, M. Uchida
  • Organizer: 22nd Topical Meeting of the International Society of Electrochemistry
  • Int'l Joint Research
• [Presentation] Relationship between Ionomer Content and Load Cycle Durability of Membrane-Electrode Assemblies Using Pt/Nb-SnO2 Cathode Catalyst Layers (2018)
  • Author(s): R. Kobayashi, K. Kakinuma, A. Iiyama, M. Uchida
  • Organizer: The 7th International Seminar “Green Energy Conversion Science and Technology”
  • Int'l Joint Research
• [Presentation] Enhancement of the Catalytic Activity and Durability of Pt and Pt Alloy Catalysts on SnO2 (2018)
  • Author(s): K. Kakinuma, M. Hayashi, A. Iiyama, M. Uchida
  • Organizer: 69th Annual Meeting of the International Society of Electrochemistry
  • Int'l Joint Research
• [Presentation] Effects of Ionomer Content on Both Performance and Load Cycle Durability for PEFCs Using Pt/Nb-SnO2 Cathode Catalyst Layers (2018)
  • Author(s): K. Kakinuma, R. Kobayashi, A. Iiyama, M. Uchida
  • Organizer: 234th Meeting of the Electrochemical Society
  • Int'l Joint Research
• [Presentation] Highly active and durable PEFC cathode catalyst of Pt supported on SnO2 nanoparticles with fine-controlled microstructure and interfaces (2018)
  • Author(s): K. Kakinuma
  • Organizer: 2nd International Workshop on Phase Interfaces for Highly Efficient Energy Utilization
  • Int'l Joint Research
• [Presentation] Synthesis and Evaluation of High Durable Electrocatalysts using Oxide Supports for Polymer Electrolyte Fuel Cells (2018)
  • Author(s): 柿沼克良, 内田誠, 飯山明裕
  • Organizer: 公益社団法人 自動車技術会 2018年春季大会
• [Presentation] Pt系触媒用酸化物担体の検討 (2018)
  • Author(s): 柿沼克良
  • Organizer: 一般社団法人触媒学会第11回新電極触媒シンポジウム
  • Invited
• [Presentation] New Developments in Structured Oxide Supports for Exceptionally Durable Anode and Cathode Pt and Pt Alloy Catalysts (2017)
  • Author(s): K. Kakinuma, A. Iiyama, M. Watanabe, M. Uchida
  • Organizer: CARISMA 2017
  • Int'l Joint Research
• [Presentation] Improvement of Cell Performance in Low-Pt-Loading PEFC Cathode Catalyst Layers with Pt/Ta-SnO2 Prepared by the Electrospray Method (2017)
  • Author(s): M. Uchida, K. Takahashi, K. Kakinuma
  • Organizer: 21th International Conference on Solid State Ionics
  • Int'l Joint Research / Invited
• [Presentation] Improvement of Cell Performance in Low-Pt-Loading PEFC Cathode Catalyst Layers with Pt/Ta-SnO2 Prepared by the Electrospray Method (2017)
  • Author(s): M. Uchida, K. Takahashi, K. Kakinuma
  • Organizer: 68th Annual Meeting of the International Society of Electrochemistry
  • Int'l Joint Research
• [Presentation] Pt and PtCo Alloy Catalysts Supported on SnO2 with Fused-Aggregate Network Structure for PEFC Cathodes (2017)
  • Author(s): K. Kakinuma, M. Hayashi, A. Iiyama, M. Uchida
  • Organizer: 68th Annual Meeting of the International Society of Electrochemistry
  • Int'l Joint Research
• [Presentation] Effect of Heat Treatment of IrOx/Sb-SnO2 Catalysts on Oxygen Evolution Activity in Polymer Electrolyte Membrane Water Electrolysis (2017)
  • Author(s): H. Ohno, S. Nohara, K. Kakinuma, M. Uchida, H. Uchida
  • Organizer: The 6th International Seminar for Special Doctoral Program‘Green Energy Conversion Science and Technology
  • Int'l Joint Research
• [Presentation] Evaluation of the Cell Performance and Load Cycle Durability for Polymer Electrolyte Fuel Cells Using Pt/Nb-SnO2 Cathode Catalyst layers with Various Ionomer Contents (2017)
  • Author(s): R. Kobayashi, K. Kakinuma, A. Iiyama, M. Uchida
  • Organizer: The 6th International Seminar for Special Doctoral Program‘Green Energy Conversion Science and Technology
  • Int'l Joint Research
• [Presentation] Evaluation of the Cell Performance and Load Cycle Durability for Membrane Electrode Assemblies Using Pt/Nb-SnO2 Cathode Catalyst Layers with Various Ionomer Contents (2017)
  • Author(s): R. Kobayashi, K. Kakinuma, A. Iiyama, M. Uchida
  • Organizer: 232nd ECS Meeting
  • Int'l Joint Research
• [Presentation] Recent R & D of Electrocatalysts and Polymer Electrolytes to Realize Superlative, Stable, and Scalable Performance Fuel Cells (2017)
  • Author(s): A.Iiyama, K. Kakinuma, M. Uchida, H. Yano, J.Inukai, J. Miyake, K. Miyatake, H. Uchida
  • Organizer: International Symposium on Novel Energy Nanomaterials, Catalysts and Surfaces for Future Earth
  • Int'l Joint Research
• [Presentation] High Durable and Active Pt and PtCo Alloy Catalysts Supported on SnO2 with Fused-Aggregated Network Structure for Polymer Electrolyte Fuel Cells (2017)
  • Author(s): K. Kakinuma, A. Iiyama, M. Uchida
  • Organizer: ICAE 2017
  • Int'l Joint Research / Invited
• [Presentation] 高耐久性・高活性を有するPt・PtCo担持SnO2触媒の評価 (2017)
  • Author(s): 柿沼克良、飯山明裕、内田誠
  • Organizer: 第24回燃料電池シンポジウム
• [Presentation] Recent R&D of Electrocatalysts and Polymer Electrolytes for Superlative, Stable, and Scalable Performance Fuel Cell (2017)
  • Author(s): A. Iiyama, M. Watanabe, K. Kakinuma, M. Uchida, H. Yano, K. Miyatake, H. Uchida
  • Organizer: 第24回燃料電池シンポジウム
• [Presentation] 自動車用燃料電池材料の最先端 (2017)
  • Author(s): 飯山明裕、内田誠、柿沼克良、矢野啓、宮武健治、三宅純平、内田裕之
  • Organizer: 日本化学会秋季事業 第7回CSJ化学フェスタ2017
• [Presentation] PEFC用MEAの高性能化・高耐久化の取り組み (2017)
  • Author(s): 内田誠
  • Organizer: 公益社団法人高分子学会水素・燃料電池材料研究会 2017年度水素・燃料電池材料研究会講座
  • Invited
• [Presentation] 静電スプレー(ES)法によるPEFC 用低白金担持Pt/GCB (2017)
  • Author(s): 内田誠
  • Organizer: 第16回燃料電池基盤技術研究懇話会
  • Invited
• [Presentation] Pt/Nb-SnO2カソード触媒層を用いたMEAの発電性能及び微細構造との関係 (2017)
  • Author(s): 小林諒、柿沼克良、飯山明裕、内田誠
  • Organizer: 電気化学会第85回大会
• [Patent(Industrial Property Rights)] 担持金属触媒、電気化学セル (2019)
  • Inventor(s): 柿沼克良、内田誠
  • Industrial Property Rights Holder: 国立大学法人山梨大学 日本化学産業株式会社
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2019-225491
  • Filing Date: 2019
• [Patent(Industrial Property Rights)] 担持金属触媒及びその製造方法、燃料電池セル (2019)
  • Inventor(s): 柿沼克良、内田誠、飯山明裕
  • Industrial Property Rights Holder: 国立大学法人 山梨大学
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2019-013778
  • Filing Date: 2019
• [Patent(Industrial Property Rights)] 担持金属触媒及びその製造方法 (2018)
  • Inventor(s): 柿沼克良、内田誠、飯山明裕、鹿島肇、荒田知里
  • Industrial Property Rights Holder: 国立大学法人 山梨大学 日本化学産業（株）
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2018-197385
  • Filing Date: 2018