JP6202629B2 - 燃料電池用の金属−窒素−炭素電極触媒の製造方法 - Google Patents
燃料電池用の金属−窒素−炭素電極触媒の製造方法 Download PDFInfo
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- JP6202629B2 JP6202629B2 JP2014516017A JP2014516017A JP6202629B2 JP 6202629 B2 JP6202629 B2 JP 6202629B2 JP 2014516017 A JP2014516017 A JP 2014516017A JP 2014516017 A JP2014516017 A JP 2014516017A JP 6202629 B2 JP6202629 B2 JP 6202629B2
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- silica
- catalyst
- aapyr
- nitrogen
- precursor
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- 239000003054 catalyst Substances 0.000 title claims description 213
- 229910052799 carbon Inorganic materials 0.000 title claims description 18
- 239000000446 fuel Substances 0.000 title claims description 18
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 301
- 239000000377 silicon dioxide Substances 0.000 claims description 133
- 238000000034 method Methods 0.000 claims description 63
- 239000002243 precursor Substances 0.000 claims description 54
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N 4-aminoantipyrine Chemical group CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 claims description 46
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- 239000002245 particle Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 239000010411 electrocatalyst Substances 0.000 claims description 16
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- 239000000463 material Substances 0.000 description 9
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
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- OOOQNKMJLOLMHC-UHFFFAOYSA-N 5-[[3,4-diethyl-5-[[5-formyl-3-(3-hydroxypropyl)-4-methyl-1h-pyrrol-2-yl]methyl]-1h-pyrrol-2-yl]methyl]-4-(3-hydroxypropyl)-3-methyl-1h-pyrrole-2-carbaldehyde Chemical compound N1C(CC2=C(C(C)=C(C=O)N2)CCCO)=C(CC)C(CC)=C1CC=1NC(C=O)=C(C)C=1CCCO OOOQNKMJLOLMHC-UHFFFAOYSA-N 0.000 description 2
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- 229910002546 FeCo Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
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- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
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- 238000005118 spray pyrolysis Methods 0.000 description 2
- 238000000547 structure data Methods 0.000 description 2
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- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- 230000002378 acidificating effect Effects 0.000 description 1
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
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- 238000010668 complexation reaction Methods 0.000 description 1
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
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- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 1
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- 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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- 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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- H01M4/90—Selection of catalytic material
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
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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
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- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
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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
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- Electrochemistry (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Ceramic Engineering (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Description
UHPN2雰囲気流量:100ccmin−1
HT温度:800℃
HT昇温率:10℃min−1
HT時間:1時間
UHPN2雰囲気流量:100ccmin−1
HT温度:800℃
HT昇温率:10℃min−1
HT時間:1時間
UHPN2雰囲気流量:100ccmin−1
HT温度:800℃
HT昇温率:10℃min−1
HT時間:1時間
UHPN2雰囲気流量:100ccmin−1
HT温度:850℃
HT昇温率:10℃min−1
HT時間:4時間
UHPN2雰囲気流量:100ccmin−1
HT温度:800℃
HT昇温率:10℃min−1
HT時間:1時間
UHPN2雰囲気流量:100ccmin−1
HT温度:800℃
HT昇温率:10℃min−1
HT時間:1時間
UHPN2雰囲気流量:100ccmin−1
HT温度:800℃
HT昇温率:10℃min−1
HT時間:1時間
Claims (14)
- 燃料電池に使用するのに好適な金属‐窒素‐炭素電極触媒の製造方法であって、
多モード孔分布をもつ電極触媒を製造するため、分散された複数の犠牲的なテンプレート粒子であって、該テンプレート粒子が少なくとも2つの集団の粒子からなり、各集団の平均粒子径が他の集団とは異なるものを準備し、
一つかそれ以上の遷移金属前駆体および含窒素炭素質前駆体を前記犠牲的なテンプレート粒子表面に凝結させて、分散前駆体を製造し、
この分散前駆体を熱分解し、そして、
前記犠牲的なテンプレート粒子を除去して、分散度の高い自己担持形で高表面積の多モード孔分布をもつ電極触媒を製造することからなることを特徴とする金属‐窒素‐炭素電極触媒の製造方法。
- 前記含窒素炭素質前駆体が、鉄錯体を形成する請求項1に記載の方法。
- 前記含窒素炭素質前駆体が、4−アミノアンチピリンである請求項1に記載の方法。
- 前記遷移金属前駆体が、鉄前駆体である請求項1に記載の方法。
- 一つかそれ以上の前記遷移金属前駆体を、Ce、Cr、Cu、Mo、Ni、Ru、Ta、Ti、V、WおよびZrの前駆体からなる群から選択する請求項1に記載の方法。
- 少なくとも2種類の異なる金属前駆体を使用して、複数の金属からなる触媒を製造する請求項1に記載の方法。
- 前記電極触媒の反応機構が4e−経路にシフトするように、前記犠牲的なテンプレート粒子および含窒素炭素質前駆体を選択する請求項1に記載の方法。
- 前記電極触媒の第1集団の孔が20〜60nmの平均径をもち、そして第2集団の孔が100〜200nmの平均径をもつ請求項1に記載の方法。
- 前記犠牲的なテンプレート粒子をシリカから形成する請求項1に記載の方法。
- 各集団のシリカ粒子を異なる種類のシリカから形成する請求項9に記載の方法。
- 各集団における前記粒子を形成するシリカを、HS5シリカ、M4シリカ、LM130シリカ、A90シリカ、L90シリカ、A200シリカおよびA380シリカからなる群から選択する請求項10に記載の方法。
- 燃料電池に使用するのに好適な金属‐窒素‐炭素電極触媒の製造方法であって、
一つかそれ以上の遷移金属前駆体および含窒素炭素質前駆体を、分散された複数の犠牲的なテンプレート粒子であって、該テンプレート粒子が少なくとも2つの集団の粒子からなり、各集団の平均粒子径が他の集団とは異なるものと混合し、
混合物を噴霧して粉末を形成し、
この粉末を回収して、そして
前記粉末を熱処理し、前記犠牲的なテンプレート粒子を除去して、分散度の高い自己担持形で高表面積の多モード孔分布をもつ電極触媒を製造することからなることを特徴とする金属‐窒素‐炭素電極触媒の製造方法。
- 前記含窒素炭素質前駆体が、ピラゾロン、アミン官能化フェニル、アミン官能化アルコールおよびピロリジンジオンからなる群から選択されるものである請求項1に記載の方法。
- 前記含窒素炭素質前駆体が、4−アミノアンチピリン、フェニレンジアミン、ヒドロキシスクシンイミドおよびエタノールアミンからなる群から選択されるものである請求項1に記載の方法。
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PCT/US2012/042609 WO2012174344A2 (en) | 2011-06-15 | 2012-06-15 | Non-pgm cathode catalysts for fuel cell application derived from heat treated heteroatomic amines precursors |
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US9673456B2 (en) | 2013-01-16 | 2017-06-06 | Alexey Serov | Non-PGM catalysts for ORR based on charge transfer organic complexes |
CN103326041B (zh) * | 2013-06-19 | 2015-03-25 | 厦门大学 | 一种氧还原电催化剂及其制备方法 |
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