JP6400688B2 - 燃料電池のための貴金属不含の触媒系 - Google Patents
燃料電池のための貴金属不含の触媒系 Download PDFInfo
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- JP6400688B2 JP6400688B2 JP2016519382A JP2016519382A JP6400688B2 JP 6400688 B2 JP6400688 B2 JP 6400688B2 JP 2016519382 A JP2016519382 A JP 2016519382A JP 2016519382 A JP2016519382 A JP 2016519382A JP 6400688 B2 JP6400688 B2 JP 6400688B2
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/70—Constitutive chemical elements of heterogeneous catalysts of Group VII (VIIB) of the Periodic Table
- B01J2523/72—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/842—Iron
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
- H01M4/8832—Ink jet printing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Organic Chemistry (AREA)
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- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Description
最初に、アニリンの0.5MのHCl溶液を金属前駆体であるFeCl3及び/又はMnCl2と混合し、そして、30分間撹拌した。引き続いて、撹拌を続けながら、酸化剤であるアンモニウムペルオキシ二硫酸(NH4)2S2O8の0.5MのHCl溶液を滴下して添加することによって、5℃でアニリンの重合を開始させた。その重合が終了した後、ポリアニリン(PANI)及び遷移金属のFe/Mnからなるポリマー錯体が生じ、これに、超音波分散物として炭素含有の支持材料の0.5MのHCl分散液を添加した。Vulcan XC−72、Ketjen EC 300J及びKetjen EC600Jを含む、市場から得られる様々な炭素含有の支持材料を使用した。90℃で還流しながら24時間撹拌し、減圧下で溶媒を除去し、そして真空下で残留物を乾燥させ、均一な生成物として、炭素含有の支持材料に結合したポリアニリン−金属−触媒を得た。この粗生成物を、それから1時間、N2−又はNH3雰囲気下において900℃で熱処理した。冷却後、80℃において2時間にわたりこの生成物を2MのH2SO4と混合し、未結合の金属を洗浄し、そして引き続き、脱イオン水で洗浄した。その後、新たに、N2−又はNH3雰囲気下において900℃で3時間該生成物を加熱した。前述したように、2MのH2SO4を用いてこの生成物を部分的に再度洗浄し、そして熱処理した。この生成物中の金属含有量は、使用したアニリン及び金属前駆体のモル比に依存して、それぞれ17、21及び25重量%であった。
17重量%のMnを有するポリアニリン−Mn−触媒(Mn17 PANIとも言う)
21重量%のMnを有するポリアニリン−Mn−触媒(Mn21 PANI)
25重量%のMnを有するポリアニリン−Mn−触媒(Mn25 PANI)
25重量%のMn+Feを有するポリアニリン−Mn3Fe−触媒(Mn3Fe PANI)
25重量%のMn+Feを有するポリアニリン−MnFe−触媒(MnFe PANI)
25重量%のMn+Feを有するポリアニリン−MnFe3−触媒(MnFe3 PANI)
25重量%のFeを有するポリアニリン−Fe−触媒(Fe PANI)。
カソードの触媒を含有する膜を、インキ印刷法による公知の方法で製造した。そのインキ混合物は、1gの金属−PANI−触媒、4.4gの2−プロパノール及び1gのナフィオン(Nafion)溶液(スルホン化テトラフルオロエチレンポリマー、20%濃度)を含有し、そして、ボールミルで新たに製造した(24時間の撹拌、ジルコニウムボール)。Rackelを用いて、ETFE膜(ETFE=エチレンテトラフルオロエチレン)上に均質に得られた分散液を塗工し、それから乾燥させた。
12 Fe PANI−触媒を有する膜電極アレイの分極曲線
14 Mn PANI−触媒を有する膜電極アレイの分極曲線
Claims (8)
- 燃料電池のカソード反応に用いられる、炭素をベースとする支持材料及び該支持材料に結合した、N 2 −又はNH 3 雰囲気下において900℃で熱処理したポリアニリン金属触媒を有する触媒系であって、該ポリアニリン金属触媒が鉄(Fe)及びマンガン(Mn)を含有することを特徴とする、上記の触媒系。
- 前記ポリアニリン金属触媒が、ポリアニリン−Mn/Fe−触媒であることを特徴とする、請求項1に記載の触媒系。
- MnのFeに対するモル比が、1:100〜100:1の範囲内にあることを特徴とする、請求項1又は2に記載の触媒系。
- MnのFeに対するモル比が、1:5〜5:1の範囲内にあることを特徴とする、請求項3に記載の触媒系。
- MnのFeに対するモル比が、1:1.5〜1.5:1の範囲内にあることを特徴とする、請求項4に記載の触媒系。
- MnのFeに対するモル比が、1:1であることを特徴とする、請求項5に記載の触媒系。
- 前記金属が、前記触媒系の全重量の10〜40重量%の割合を有することを特徴とする、請求項1〜6のいずれか一つに記載の触媒系。
- 請求項1〜7のいずれか一つに記載の触媒系を含有することを特徴とする、燃料電池。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE102013219937.6 | 2013-10-01 | ||
DE201310219937 DE102013219937A1 (de) | 2013-10-01 | 2013-10-01 | Edemetallfreies Katalysatorsystem für eine Brennstoffzelle |
PCT/EP2014/070275 WO2015049128A1 (de) | 2013-10-01 | 2014-09-23 | Edelmetallfreies katalysatorsystem für eine brennstoffzelle |
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JP2016533868A JP2016533868A (ja) | 2016-11-04 |
JP6400688B2 true JP6400688B2 (ja) | 2018-10-03 |
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JP2016519382A Active JP6400688B2 (ja) | 2013-10-01 | 2014-09-23 | 燃料電池のための貴金属不含の触媒系 |
Country Status (6)
Country | Link |
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US (1) | US20160240860A1 (ja) |
JP (1) | JP6400688B2 (ja) |
KR (1) | KR102131140B1 (ja) |
CN (1) | CN105579133A (ja) |
DE (1) | DE102013219937A1 (ja) |
WO (1) | WO2015049128A1 (ja) |
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KR102077195B1 (ko) * | 2018-01-19 | 2020-02-13 | 대구대학교 산학협력단 | 망간-철의 나노복합체를 포함하는 산소 환원용 및 산소 발생용의 이중 기능성 전극 촉매 및 그의 제조 방법 |
KR102123148B1 (ko) * | 2018-04-18 | 2020-06-15 | 인천대학교 산학협력단 | 금속착물을 활용한 탄소껍질을 가진 금속 촉매의 합성방법 |
DE102018214403A1 (de) * | 2018-08-27 | 2020-02-27 | Audi Ag | Verfahren zur Herstellung eines edelmetall-freien Katalysators, edelmetall-freier Katalysator, Brennstoffzelle sowie Kraftfahrzeug |
CN112086652B (zh) * | 2020-09-15 | 2022-02-25 | 香港科技大学深圳研究院 | 一种空心碳球/石墨烯双功能催化剂及其制备方法和应用 |
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KR100536257B1 (ko) * | 2004-06-29 | 2005-12-12 | 삼성에스디아이 주식회사 | 연료 전지용 막/전극 접합체 및 그를 포함하는 연료 전지 |
DE102005044433A1 (de) * | 2005-09-16 | 2007-03-22 | Universität Bremen | Katalytisch aktive Zusammensetzung, Membran-Elektroden-Einheit mit der Zusammensetzung und Katalysator mit/aus der Zusammensetzung |
US20070082253A1 (en) * | 2005-10-06 | 2007-04-12 | The Regents Of The University Of California | Metal-polymer composite catalysts |
KR101077704B1 (ko) * | 2007-02-13 | 2011-10-27 | 가부시키가이샤 히타치세이사쿠쇼 | 금속 클러스터 촉매를 이용한 연료 전지 |
TW200838607A (en) * | 2007-03-30 | 2008-10-01 | Tatung Co | Preparation of mangania-iron-supported nano-gold catalysts and using the same |
US7785498B2 (en) * | 2007-07-19 | 2010-08-31 | Nanotek Instruments, Inc. | Method of producing conducting polymer-transition metal electro-catalyst composition and electrodes for fuel cells |
US20110287174A1 (en) * | 2008-08-21 | 2011-11-24 | Board Of Trustees Of Michigan State University | Novel catalyst for oxygen reduction reaction in fuel cells |
CN101702437B (zh) * | 2009-10-21 | 2011-11-09 | 华东理工大学 | 铁锰联合修饰材料的制备方法及其在微生物燃料电池中的应用 |
US8709295B2 (en) | 2010-04-26 | 2014-04-29 | Los Alamos National Security, Llc | Nitrogen-doped carbon-supported cobalt-iron oxygen reduction catalyst |
US20120088187A1 (en) | 2010-10-06 | 2012-04-12 | Los Alamos National Security, Llc | Non-precious fuel cell catalysts comprising polyaniline |
WO2012174344A2 (en) * | 2011-06-15 | 2012-12-20 | Stc.Unm | Non-pgm cathode catalysts for fuel cell application derived from heat treated heteroatomic amines precursors |
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2013
- 2013-10-01 DE DE201310219937 patent/DE102013219937A1/de active Pending
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2014
- 2014-09-23 KR KR1020167010691A patent/KR102131140B1/ko active IP Right Grant
- 2014-09-23 CN CN201480054583.4A patent/CN105579133A/zh active Pending
- 2014-09-23 JP JP2016519382A patent/JP6400688B2/ja active Active
- 2014-09-23 WO PCT/EP2014/070275 patent/WO2015049128A1/de active Application Filing
- 2014-09-23 US US15/026,549 patent/US20160240860A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
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DE102013219937A1 (de) | 2015-04-02 |
KR102131140B1 (ko) | 2020-07-07 |
US20160240860A1 (en) | 2016-08-18 |
CN105579133A (zh) | 2016-05-11 |
WO2015049128A1 (de) | 2015-04-09 |
JP2016533868A (ja) | 2016-11-04 |
KR20160064150A (ko) | 2016-06-07 |
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