JP5928554B2 - Method for producing catalyst ink - Google Patents
Method for producing catalyst ink Download PDFInfo
- Publication number
- JP5928554B2 JP5928554B2 JP2014214408A JP2014214408A JP5928554B2 JP 5928554 B2 JP5928554 B2 JP 5928554B2 JP 2014214408 A JP2014214408 A JP 2014214408A JP 2014214408 A JP2014214408 A JP 2014214408A JP 5928554 B2 JP5928554 B2 JP 5928554B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer electrolyte
- catalyst
- carbon particles
- electrode
- ink
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims description 216
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000005518 polymer electrolyte Substances 0.000 claims description 151
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 83
- 229910052799 carbon Inorganic materials 0.000 claims description 78
- 239000002245 particle Substances 0.000 claims description 73
- 239000000463 material Substances 0.000 claims description 66
- 239000000446 fuel Substances 0.000 claims description 45
- 239000000126 substance Substances 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 33
- 229910052723 transition metal Inorganic materials 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
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- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 5
- 230000036961 partial effect Effects 0.000 claims description 4
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZUBJEHHGZYTRPH-KTKRTIGZSA-N [(z)-octadec-9-enyl] hydrogen sulfate Chemical compound CCCCCCCC\C=C/CCCCCCCCOS(O)(=O)=O ZUBJEHHGZYTRPH-KTKRTIGZSA-N 0.000 description 1
- YYCVEQAJBXLGEQ-UHFFFAOYSA-N acetic acid;n,n-diethylethanamine;octadecanamide Chemical group CC(O)=O.CCN(CC)CC.CCCCCCCCCCCCCCCCCC(N)=O YYCVEQAJBXLGEQ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- YSJGOMATDFSEED-UHFFFAOYSA-M behentrimonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCCCCCC[N+](C)(C)C YSJGOMATDFSEED-UHFFFAOYSA-M 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
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- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
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- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001337 iron nitride Inorganic materials 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- MGYNCLRTNAGJHZ-UHFFFAOYSA-N n,n-diethylethanamine;octadecanamide;hydrochloride Chemical group Cl.CCN(CC)CC.CCCCCCCCCCCCCCCCCC(N)=O MGYNCLRTNAGJHZ-UHFFFAOYSA-N 0.000 description 1
- OZYPPHLDZUUCCI-UHFFFAOYSA-N n-(6-bromopyridin-2-yl)-2,2-dimethylpropanamide Chemical compound CC(C)(C)C(=O)NC1=CC=CC(Br)=N1 OZYPPHLDZUUCCI-UHFFFAOYSA-N 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 229940070891 pyridium Drugs 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229940043230 sarcosine Drugs 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HWCHICTXVOMIIF-UHFFFAOYSA-M sodium;3-(dodecylamino)propanoate Chemical compound [Na+].CCCCCCCCCCCCNCCC([O-])=O HWCHICTXVOMIIF-UHFFFAOYSA-M 0.000 description 1
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- VDWRUZRMNKZIAJ-UHFFFAOYSA-N tetradecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCN VDWRUZRMNKZIAJ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Description
本発明は、固体高分子形燃料電池用の触媒インクに関するものであり、特に、非白金触媒を用いて高い発電特性を示す電極触媒層を形成する触媒インクに関するものである。 The present invention relates to a catalyst ink for a polymer electrolyte fuel cell, and more particularly to a catalyst ink for forming an electrode catalyst layer exhibiting high power generation characteristics using a non-platinum catalyst.
燃料電池は、水素を含有する燃料ガスと酸素を含む酸化剤ガスとを、触媒を含む電極で水の電気分解の逆反応を起こさせ、熱と同時に電気を生み出す発電システムである。この発電システムは、従来の発電方式と比較して高効率で低環境負荷、低騒音などの特徴を有し、将来のクリーンなエネルギー源として注目されている。用いるイオン伝導体の種類によってタイプがいくつかあり、プロトン伝導性高分子膜を用いたものは、固体高分子形燃料電池と呼ばれる。 A fuel cell is a power generation system that generates electricity simultaneously with heat by causing a hydrogen gas-containing fuel gas and an oxygen-containing oxidant gas to undergo reverse reaction of water electrolysis at an electrode including a catalyst. This power generation system has features such as high efficiency, low environmental load, and low noise as compared with conventional power generation systems, and is attracting attention as a clean energy source in the future. There are several types depending on the type of ion conductor used, and those using proton conductive polymer membranes are called solid polymer fuel cells.
燃料電池の中でも固体高分子形燃料電池は、室温付近で使用可能なことから、車載用電源や家庭据置用電源などへの使用が有望視されており、近年、様々な研究開発が行われている。固体高分子形燃料電池は、膜電極接合体（Ｍｅｍｂｒａｎｅ ａｎｄ Ｅｌｅｃｔｒｏｄｅ Ａｓｓｅｍｂｌｙ；以下「ＭＥＡ」と称すことがある。）と呼ばれる高分子電解質膜の両面に一対の電極を配置させた接合体を、前記電極の一方に水素を含有する燃料ガスを供給し、前記電極の他方に酸素を含む酸化剤ガスを供給するためのガス流路を形成した一対のセパレーター板で挟持した電池である。ここで、燃料ガスを供給する電極を燃料極、酸化剤を供給する電極を空気極と呼んでいる。これらの電極は、一般に、白金系の貴金属などの触媒物質を担持したカーボン粒子と高分子電解質を積層してなる電極触媒層と、ガス通気性と電子伝導性を兼ね備えたガス拡散層からなる。 Among fuel cells, polymer electrolyte fuel cells can be used near room temperature, so they are considered promising for use in in-vehicle power sources and household stationary power sources. In recent years, various research and development have been conducted. Yes. The polymer electrolyte fuel cell comprises a membrane electrode assembly (Membrane and Electrode Assembly; hereinafter referred to as “MEA”) in which a pair of electrodes are disposed on both sides of a polymer electrolyte membrane. In this battery, a fuel gas containing hydrogen is supplied to one of the electrodes, and a gas passage for supplying an oxidant gas containing oxygen to the other electrode is sandwiched between a pair of separator plates. Here, the electrode for supplying the fuel gas is called a fuel electrode, and the electrode for supplying the oxidant is called an air electrode. These electrodes generally comprise an electrode catalyst layer formed by laminating carbon particles carrying a catalyst substance such as a platinum-based noble metal and a polymer electrolyte, and a gas diffusion layer having both gas permeability and electronic conductivity.
固体高分子形燃料電池の実用化に向けての課題は、出力密度や耐久性の向上などが挙げられるが、最大の課題は低コスト化である。 Issues for the practical application of polymer electrolyte fuel cells include improvements in power density and durability, but the biggest issue is cost reduction.
現在の固体高分子形燃料電池には、高価な白金が電極触媒として用いられており、本格普及には、代替材料の開発が強く求められている。特に、空気極では、燃料極よりも多くの白金を使用しているため、空気極において高い酸素還元触媒能を示す白金代替材料（非白金触媒）の開発が盛んである。 In current polymer electrolyte fuel cells, expensive platinum is used as an electrode catalyst, and development of alternative materials is strongly required for full-scale spread. In particular, since the air electrode uses more platinum than the fuel electrode, the development of platinum substitute materials (non-platinum catalysts) that exhibit high oxygen reduction catalytic ability in the air electrode is actively performed.
空気極における非白金触媒の例として、例えば特許文献１には、遷移金属である鉄の窒化物と貴金属の混合物が記載されている。また、特許文献２には、遷移金属であるモリブデンの窒化物が記載されている。しかし、特許文献１および特許文献２で記載されているような触媒物質は、酸性電解質中での酸素還元能が不充分であり、且つ、触媒物質が溶解する場合がある。 As an example of the non-platinum catalyst in the air electrode, for example, Patent Document 1 describes a mixture of iron nitride and noble metal, which is a transition metal. Patent Document 2 describes a nitride of molybdenum, which is a transition metal. However, the catalyst materials described in Patent Document 1 and Patent Document 2 have insufficient oxygen reducing ability in the acidic electrolyte, and the catalyst material may be dissolved.
一方、非特許文献１には、部分酸化されたタンタルの炭窒化物が記載されており、優れた安定性と触媒能を持つことを示している。しかし、この酸化物系非白金触媒は、触媒単体として高い酸素還元触媒能を示しているが、白金触媒のように炭素粒子に担持されておらず、電極触媒層の作製手法を最適化する必要がある。 On the other hand, Non-Patent Document 1 describes a partially oxidized tantalum carbonitride, which indicates that it has excellent stability and catalytic ability. However, although this oxide-based non-platinum catalyst shows high oxygen reduction catalytic ability as a single catalyst, it is not supported on carbon particles like platinum catalyst, and it is necessary to optimize the preparation method of the electrode catalyst layer There is.
また、特許文献３には、非白金触媒を用いたＭＥＡが記載されているが、その電極触媒層の作製手法は、例えば、特許文献４および特許文献５などに記載されている白金触媒で用いられる従来の作製手法であるため、非白金触媒に適していないという問題点がある。 In addition, Patent Document 3 describes MEA using a non-platinum catalyst. The electrode catalyst layer is prepared by using, for example, the platinum catalyst described in Patent Document 4 and Patent Document 5, for example. Therefore, there is a problem that it is not suitable for a non-platinum catalyst.
本発明は、触媒物質として、特に、酸化物系非白金触媒を用いて、高い発電特性を示す燃料電池用の触媒インクを提供することを目的とする。 An object of the present invention is to provide a catalyst ink for a fuel cell exhibiting high power generation characteristics, particularly using an oxide-based non-platinum catalyst as a catalyst substance.
本発明者は鋭意検討を重ねた結果、上記課題を解決することができ、本発明を完成するに至った。 As a result of intensive studies, the present inventor has been able to solve the above-mentioned problems and has completed the present invention.
本発明の請求項１に係る発明は、高分子電解質、触媒物質および炭素粒子を有する燃料電池用電極触媒層の触媒インクの製造方法において、炭素粒子より比表面積が小さい触媒物質と第一の高分子電解質とを、重量比１：０．０１〜１：３０の範囲内で溶媒に分散し温度範囲が３０℃以上１４０℃以下の範囲内で乾燥してなる第一の高分子電解質で包埋した触媒物質と、前記触媒物質より比表面積が大きい前記炭素粒子と第二の高分子電解質とを、重量比１：０．１〜１：２０の範囲内で溶媒に分散し温度範囲が３０℃以上１４０℃以下の範囲内で乾燥してなる第二の高分子電解質で包埋した炭素粒子とを有し、無溶媒で混合し温度範囲が５０℃以上１８０℃以下の範囲内で熱処理した前記第一の高分子電解質で包埋した触媒物質と前記第二の高分子電解質で包埋した炭素粒子とを、第三の高分子電解質とともに溶媒に分散してなり、前記第一の高分子電解質及び前記第二の高分子電解質及び前記第三の高分子電解質はそれぞれフッ素系高分子電解質又は炭化水素系高分子電解質であることを特徴とする触媒インクの製造方法である。
According to the first aspect of the present invention, there is provided a method for producing a catalyst ink for an electrode catalyst layer for a fuel cell having a polymer electrolyte, a catalyst substance, and carbon particles. A molecular electrolyte is embedded in a first polymer electrolyte that is dispersed in a solvent in a weight ratio of 1: 0.01 to 1:30 and dried in a temperature range of 30 ° C. or higher and 140 ° C. or lower. The catalyst material, the carbon particles having a larger specific surface area than the catalyst material, and the second polymer electrolyte are dispersed in a solvent within a weight ratio of 1: 0.1 to 1:20, and the temperature range is 30 ° C. The carbon particles embedded with the second polymer electrolyte dried in the range of 140 ° C. or lower, mixed without solvent, and heat-treated in the temperature range of 50 ° C. or higher and 180 ° C. or lower. The catalyst material embedded with the first polymer electrolyte and the second Carbon particles embedded with a polymer electrolyte are dispersed in a solvent together with a third polymer electrolyte, and the first polymer electrolyte, the second polymer electrolyte, and the third polymer electrolyte are: The catalyst ink production method is characterized in that each is a fluorine-based polymer electrolyte or a hydrocarbon-based polymer electrolyte.
本発明の請求項２に係る発明は、前記触媒物質が、固体高分子形燃料電池の空気極として用いられる酸素還元電極用の電極活物質であって、Ｔａ、Ｎｂ、Ｔｉ、Ｚｒから選択される、少なくとも一つの遷移金属元素を含むことを特徴とする。
The invention according to claim 2 of the present invention, the catalytic material, an electrode active material for the oxygen reduction electrode for use as an air electrode of a solid polymer electrolyte fuel cell, the selected Ta, Nb, Ti, from Zr that, characterized in that it comprises at least one transition metal element.
本発明の請求項３に係る発明は、前記触媒物質が、前記遷移金属元素の炭窒化物の部分酸化物、または、前記遷移金属元素の酸化物であることを特徴とする。 The invention according to claim 3 of the present invention, the catalytic material, partial oxidation of carbonitride of the transition metal element, or wherein the an oxide of a transition metal element.
本発明によれば、高分子電解質、触媒物質と炭素粒子を有する触媒インクにおいて、炭素粒子よりも小さい比表面積の触媒物質に対して高分子電解質を包埋した触媒物質と、触媒物質よりも大きい比表面積の炭素粒子に対して高分子電解質を包埋し炭素粒子の比表面積を小さくする処理を行った炭素粒子とすることにより、電極触媒層の形成時に触媒表面のプロトン伝導性を高めることで、反応活性点を増加させ、出力性能の向上した電極触媒層、膜電極接合体および固体高分子形燃料電池を提供することができる。 According to the present invention, in a catalyst ink having a polymer electrolyte, a catalyst material, and carbon particles, a catalyst material in which the polymer electrolyte is embedded in a catalyst material having a specific surface area smaller than that of the carbon particles, and larger than the catalyst material By increasing the proton conductivity of the catalyst surface during the formation of the electrode catalyst layer by embedding a polymer electrolyte in the carbon particles with a specific surface area to make the carbon particles treated to reduce the specific surface area of the carbon particles. Thus, it is possible to provide an electrode catalyst layer, a membrane electrode assembly, and a polymer electrolyte fuel cell with increased reaction active points and improved output performance.
また、触媒物質と炭素粒子に対してそれぞれ高分子電解質を包埋することで、それぞれの包埋量制御を可能にさせる。その結果、包埋量の最適化検討を容易に行うことができる。 Further, by embedding the polymer electrolyte in each of the catalyst substance and the carbon particles, the embedding amount can be controlled. As a result, it is possible to easily perform the optimization examination of the embedding amount.
以下に、本発明の実施の形態に係る膜電極接合体について説明する。なお、本発明の実施の形態は、以下に記載する実施の形態に限定されうるものではなく、当業者の知識に基づいて設計の変更などの変形を加えることも可能であり、そのような変形が加えられた実施の形態も本発明の実施の形態の範囲に含まれうるものである。 Below, the membrane electrode assembly which concerns on embodiment of this invention is demonstrated. The embodiments of the present invention are not limited to the embodiments described below, and modifications such as design changes can be added based on the knowledge of those skilled in the art. Embodiments to which is added can also be included in the scope of the embodiments of the present invention.
図１は、本発明の実施の形態に係る触媒インクを電極触媒層に適用した膜電極接合体１１を示す概略断面図である。図１に示すように、本発明の実施の形態に係るの触媒インクを電極触媒層に適用した膜電極接合体１１は、高分子電解質膜１と、高分子電解質膜１の一方の面に設けた空気極側の電極触媒層２と、高分子電解質膜１のもう一方の面に設けた燃料極側の電極触媒層３を備え、さらに、空気極側の電極触媒層２の高分子電解質膜１と接する面の反対の面に設けた空気極側のガス拡散層４と、燃料極側の電極触媒層３の高分子電解質膜１と接する面の反対の面に設けた燃料極側のガス拡散層５を備えている。 FIG. 1 is a schematic cross-sectional view showing a membrane electrode assembly 11 in which a catalyst ink according to an embodiment of the present invention is applied to an electrode catalyst layer. As shown in FIG. 1, a membrane electrode assembly 11 in which a catalyst ink according to an embodiment of the present invention is applied to an electrode catalyst layer is provided on one surface of a polymer electrolyte membrane 1 and a polymer electrolyte membrane 1. The electrode catalyst layer 2 on the air electrode side and the electrode catalyst layer 3 on the fuel electrode side provided on the other surface of the polymer electrolyte membrane 1, and further the polymer electrolyte membrane of the electrode catalyst layer 2 on the air electrode side The gas diffusion layer 4 on the air electrode side provided on the surface opposite to the surface in contact with 1, and the gas on the fuel electrode side provided on the surface opposite to the surface in contact with the polymer electrolyte membrane 1 of the electrode catalyst layer 3 on the fuel electrode side A diffusion layer 5 is provided.
図２は、本発明の実施の形態に係る固体高分子形燃料電池１２の分解模式図である。本発明の触媒インクを電極触媒層に適用した膜電極接合体を採用した固体高分子形燃料電池１２は、高分子電解質膜１の両面に設けられた空気極側の電極触媒層２および燃料極側の電極触媒層３と対向して、空気極側のガス拡散層４および燃料極側のガス拡散層５が配置される。これにより、それぞれ空気極（カソード）６および燃料極（アノード）７が構成される。そして、ガス流通用のガス流路８を備え、相対する主面に冷却水流通用の冷却水流路９を備えた導電性でかつ不透過性の材料よりなる一組のセパレーター１０が配置される。燃料極７側のセパレーター１０のガス流路８からは燃料ガスとして、例えば水素ガスが供給される。一方、空気極６側のセパレーター１０のガス流路８からは、酸化剤ガスとして、例えば酸素を含むガスが供給される。そして、燃料ガスの水素と酸素ガスとを触媒の存在下で電極反応させることにより、燃料極と空気極の間に起電力を生じることができる。 FIG. 2 is an exploded schematic view of the polymer electrolyte fuel cell 12 according to the embodiment of the present invention. A polymer electrolyte fuel cell 12 employing a membrane electrode assembly in which the catalyst ink of the present invention is applied to an electrode catalyst layer includes an electrode catalyst layer 2 on the air electrode side provided on both surfaces of the polymer electrolyte membrane 1 and a fuel electrode. A gas diffusion layer 4 on the air electrode side and a gas diffusion layer 5 on the fuel electrode side are arranged to face the electrode catalyst layer 3 on the side. Thereby, an air electrode (cathode) 6 and a fuel electrode (anode) 7 are formed. Then, a set of separators 10 made of a conductive and impermeable material having a gas flow path 8 for gas flow and a cooling water flow path 9 for cooling water flow on the opposing main surface is disposed. For example, hydrogen gas is supplied as a fuel gas from the gas flow path 8 of the separator 10 on the fuel electrode 7 side. On the other hand, a gas containing oxygen, for example, is supplied as an oxidant gas from the gas flow path 8 of the separator 10 on the air electrode 6 side. An electromotive force can be generated between the fuel electrode and the air electrode by causing an electrode reaction between hydrogen and oxygen gas of the fuel gas in the presence of the catalyst.
図２に示した固体高分子形燃料電池１２は、一組のセパレーターに高分子電解質膜１、電極触媒層２、３、ガス拡散層４、５が狭持された。いわゆる単セル構造の固体高分子形燃料電池であるが、本発明にあっては、セパレーター１０を介して複数のセルを積層して燃料電池とすることもできる。 In the polymer electrolyte fuel cell 12 shown in FIG. 2, the polymer electrolyte membrane 1, the electrode catalyst layers 2, 3 and the gas diffusion layers 4, 5 are sandwiched between a pair of separators. Although it is a solid polymer fuel cell having a so-called single cell structure, in the present invention, a plurality of cells can be stacked via a separator 10 to form a fuel cell.
本発明の触媒インクは、炭素粒子よりも小さい比表面積の触媒物質に対して高分子電解質を包埋し、さらに触媒物質よりも大きい比表面積の炭素粒子に対して高分子電解質を包埋することで触媒表面のプロトン伝導性を高めることで、反応活性点を増加させることができる。触媒物質と炭素粒子に対して、高分子電解質の包埋を行わない従来の触媒インクを用いた電極触媒層では、電極触媒層の形成時に、比表面積の大きい炭素粒子が高分子電解質で優先的に包埋されるため、触媒表面のプロトン伝導性が低く、反応活性点を増加させることはできない。また、従来の製造方法でも、高分子電解質を高濃度にすることで触媒表面のプロトン伝導性を高めることもできるが、炭素粒子に対しては過剰な量の添加となり、出力性能を向上させることは困難である。 The catalyst ink of the present invention embeds a polymer electrolyte in a catalyst material having a specific surface area smaller than that of carbon particles, and further embeds the polymer electrolyte in carbon particles having a specific surface area larger than that of the catalyst material. The reaction active point can be increased by increasing the proton conductivity of the catalyst surface. In the electrode catalyst layer using the conventional catalyst ink that does not embed the polymer electrolyte in the catalyst material and carbon particles, carbon particles with a large specific surface area are preferred in the polymer electrolyte when the electrode catalyst layer is formed. Embedded in the catalyst, the proton conductivity on the catalyst surface is low, and the reaction active sites cannot be increased. In addition, the conventional manufacturing method can also increase the proton conductivity of the catalyst surface by increasing the concentration of the polymer electrolyte, but an excessive amount is added to the carbon particles to improve the output performance. It is difficult.
上記の炭素粒子よりも小さい比表面積の触媒物質に対して高分子電解質を包埋する場合、触媒物質と高分子電解質との重量比は、１：０．０１〜１：３０の範囲内であることが好ましい。触媒物質に対して、高分子電解質の重量比が０．０１に満たない場合にあっては、触媒表面のプロトン伝導性が変化せず、反応活性点を増加せることが困難であることから、出力性能が向上しない場合がある。また、触媒物質に対して、高分子電解質の重量比が３０を超える場合にあっては、反応活性点へのガス拡散性が阻害され、出力性能が向上しない場合がある。 When embedding the polymer electrolyte in a catalyst material having a specific surface area smaller than that of the carbon particles, the weight ratio of the catalyst material to the polymer electrolyte is in the range of 1: 0.01 to 1:30. It is preferable. When the weight ratio of the polymer electrolyte to the catalyst substance is less than 0.01, the proton conductivity on the catalyst surface does not change, and it is difficult to increase the reactive site, Output performance may not improve. Further, when the weight ratio of the polymer electrolyte to the catalyst substance exceeds 30, gas diffusivity to the reaction active site may be hindered and output performance may not be improved.
さらに上記の触媒物質よりも大きい比表面積の炭素粒子に対して高分子電解質を包埋する場合、炭素粒子と高分子電解質との重量比は、１：０．１〜１：２０の範囲内であることが好ましい。炭素粒子に対して、高分子電解質の重量比が０．１に満たない場合にあっては、炭素粒子の比表面積を小さくすることが困難であることから、出力性能が向上しない場合がある。また、炭素粒子に対して、高分子電解質の重量比が２０を超える場合にあっては、炭素粒子に対しては過剰な量の添加となり、反応活性点へのガス拡散性が阻害され、出力性能が向上しない場合がある。 Further, when the polymer electrolyte is embedded in carbon particles having a specific surface area larger than that of the catalyst material, the weight ratio of the carbon particles to the polymer electrolyte is within the range of 1: 0.1 to 1:20. Preferably there is. When the weight ratio of the polymer electrolyte to the carbon particles is less than 0.1, it is difficult to reduce the specific surface area of the carbon particles, and thus the output performance may not be improved. Further, when the weight ratio of the polymer electrolyte to the carbon particles exceeds 20, an excessive amount is added to the carbon particles, the gas diffusibility to the reaction active point is inhibited, and the output Performance may not improve.
また、高分子電解質で包埋した触媒物質と、高分子電解質で包埋した炭素粒子と、高分子電解質とを、溶媒に分散させた触媒インクを作製する工程にあっては、触媒インクを作製する前に、高分子電解質で包埋した触媒物質と、高分子電解質で包埋した炭素粒子とを、無溶媒で混合させる工程を備えることが好ましい。この工程を実施しない場合にあっては、触媒物質と炭素粒子の接触性が低く、反応活性点を増加せることが困難であることから、出力性能が向上しない場合がある。 In addition, in the process of preparing a catalyst ink in which a catalyst material embedded with a polymer electrolyte, carbon particles embedded with a polymer electrolyte, and a polymer electrolyte are dispersed in a solvent, a catalyst ink is prepared. Before the step, it is preferable to include a step of mixing the catalyst material embedded with the polymer electrolyte and the carbon particles embedded with the polymer electrolyte in the absence of a solvent. When this step is not performed, the output performance may not be improved because the contact between the catalyst substance and the carbon particles is low and it is difficult to increase the reaction active point.
上記の場合、無溶媒で混合させる工程の後に、熱処理の工程を備えることが好ましい。この工程を実施しない場合にあっては、触媒インクを作製する工程で、反応活性点が減少する場合がある。この熱処理の工程にあっては、温度が５０℃以上１８０℃以下であることが好ましい。乾燥させる温度が５０℃に満たない場合にあっては、触媒インクを作製する工程で、触媒物質および炭素粒子を包埋する多くの高分子電解質が溶媒に溶解し、形成した反応活性点の減少によって出力性能が向上しない場合がある。また、乾燥させる温度が１８０℃を超える場合にあっても、触媒物質および炭素粒子を包埋する高分子電解質のプロトン伝導性が阻害され、出力性能が向上しない場合がある。 In the above case, it is preferable to provide a heat treatment step after the step of mixing without solvent. If this step is not performed, the reaction active point may decrease in the step of producing the catalyst ink. In this heat treatment step, the temperature is preferably 50 ° C. or higher and 180 ° C. or lower. When the drying temperature is less than 50 ° C., many polymer electrolytes embedding the catalyst substance and carbon particles are dissolved in the solvent in the process of preparing the catalyst ink, and the reaction active sites formed are reduced. Depending on the case, the output performance may not improve. Even when the drying temperature exceeds 180 ° C., the proton conductivity of the polymer electrolyte embedding the catalyst substance and the carbon particles is hindered, and the output performance may not be improved.
本発明の実施の形態に係る触媒物質は、白金などの一般的に用いられているものを使用してもよい。本発明において、好ましくは、白金代替材料として固体高分子形燃料電池の空気極として用いられる、Ｔａ、Ｎｂ、Ｔｉ、Ｚｒから選択される、少なくとも一つの遷移金属元素を含む物質を使用してもよい。また、より好ましくは、これらの遷移金属元素の炭窒化物の部分酸化物、または、これらの遷移金属元素の酸化物であることが好ましい。触媒物質として白金を用いる場合、電極触媒層は、空気極側の電極触媒層でも、燃料極側の電極触媒層でも用いることができる。一方、触媒物質として上記遷移金属元素を含む物質を用いる場合、電極触媒層は、空気極側の電極触媒層として用いる。 As the catalyst material according to the embodiment of the present invention, a commonly used material such as platinum may be used. In the present invention, preferably, a substance containing at least one transition metal element selected from Ta, Nb, Ti, and Zr, which is used as an air electrode of a polymer electrolyte fuel cell, is used as a platinum substitute material. Good. More preferably, it is a partial oxide of a carbonitride of these transition metal elements or an oxide of these transition metal elements. When platinum is used as the catalyst material, the electrode catalyst layer can be used as an electrode catalyst layer on the air electrode side or an electrode catalyst layer on the fuel electrode side. On the other hand, when a material containing the transition metal element is used as the catalyst material, the electrode catalyst layer is used as an electrode catalyst layer on the air electrode side.
遷移金属元素の炭窒化物の部分酸化物としては、具体的には、Ｔａの炭窒化物（ＴａＣＮ）を、酸素を含む雰囲気中で部分酸化した物質（ＴａＣＮＯ）であり、その比表面積は、凡そ１ｍ２／ｇ以上２０ｍ２／ｇ以下である。 Specifically, the transition metal element carbonitride partial oxide is a substance (TaCNO) obtained by partially oxidizing Ta carbonitride (TaCN) in an oxygen-containing atmosphere, and its specific surface area is: It is about 1 m 2 / g or more and 20 m 2 / g or less.
本発明の実施の形態に係る炭素粒子は、微粒子状で導電性を有し、触媒におかされないものであればどのようなものでも構わないが、カーボンブラックやグラファイト、黒鉛、活性炭、カーボンファイバー、カーボンナノチューブ、フラーレンが使用できる。カーボン粒子の粒径は、小さすぎると電子伝導パスが形成されにくくなり、また大きすぎると電極触媒層のガス拡散性が低下したり、触媒の利用率が低下したりするので、１０ｎｍ以上１０００ｎｍ以下が好ましい。より好ましくは、１０ｎｍ以上１００ｎｍ以下が良い。また、これらの炭素粒子の比表面積は、凡そ１００ｍ２／ｇ以上１５００ｍ２／ｇ以下である。 The carbon particles according to the embodiment of the present invention may be any particles as long as they are in the form of fine particles and have electrical conductivity and are not affected by the catalyst. Carbon black, graphite, graphite, activated carbon, carbon fiber, Carbon nanotubes and fullerenes can be used. If the particle size of the carbon particles is too small, it becomes difficult to form an electron conduction path. If the particle size is too large, the gas diffusibility of the electrode catalyst layer decreases or the utilization factor of the catalyst decreases. Is preferred. More preferably, it is 10 nm or more and 100 nm or less. The specific surface area of these carbon particles is about 100 m 2 / g or more and 1500 m 2 / g or less.
さらに詳細に本発明の実施の形態に係る触媒インクを電極触媒層に適用した膜電極接合体および電極触媒層を採用した固体高分子形燃料電池について説明する。 In more detail, a membrane electrode assembly in which the catalyst ink according to the embodiment of the present invention is applied to an electrode catalyst layer and a polymer electrolyte fuel cell employing the electrode catalyst layer will be described.
本発明の実施の形態に係る高分子電解質膜としては、プロトン伝導性を有するものであればよく、フッ素系高分子電解質、炭化水素系高分子電解質を用いることができる。フッ素系高分子電解質としては、例えば、デュポン社製Ｎａｆｉｏｎ（登録商標）、旭硝子（株）製Ｆｌｅｍｉｏｎ（登録商標）、旭化成（株）製Ａｃｉｐｌｅｘ（登録商標）、ゴア社製Ｇｏｒｅ Ｓｅｌｅｃｔ（登録商標）などを用いることができる。炭化水素系高分子電解質膜としては、スルホン化ポリエーテルケトン、スルホン化ポリエーテルスルホン、スルホン化ポリエーテルエーテルスルホン、スルホン化ポリスルフィド、スルホン化ポリフェニレンなどの電解質膜を用いることができる。中でも、高分子電解質膜としてデュポン社製Ｎａｆｉｏｎ（登録商標）系材料を好適に用いることができる。炭化水素系高分子電解質膜としては、スルホン化ポリエーテルケトン、スルホン化ポリエーテルスルホン、スルホン化ポリエーテルエーテルスルホン、スルホン化ポリスルフィド、スルホン化ポリフェニレンなどの電解質膜を用いることができる。 The polymer electrolyte membrane according to the embodiment of the present invention only needs to have proton conductivity, and a fluorine-based polymer electrolyte and a hydrocarbon-based polymer electrolyte can be used. Examples of the fluoropolymer electrolyte include Nafion (registered trademark) manufactured by DuPont, Flemion (registered trademark) manufactured by Asahi Glass Co., Ltd., Aciplex (registered trademark) manufactured by Asahi Kasei Co., Ltd., and Gore Select (registered trademark) manufactured by Gore. Etc. can be used. As the hydrocarbon polymer electrolyte membrane, electrolyte membranes such as sulfonated polyether ketone, sulfonated polyethersulfone, sulfonated polyetherethersulfone, sulfonated polysulfide, and sulfonated polyphenylene can be used. Among these, a Nafion (registered trademark) material manufactured by DuPont can be suitably used as the polymer electrolyte membrane. As the hydrocarbon polymer electrolyte membrane, electrolyte membranes such as sulfonated polyether ketone, sulfonated polyethersulfone, sulfonated polyetherethersulfone, sulfonated polysulfide, and sulfonated polyphenylene can be used.
本発明の実施の形態に係る高分子電解質としては、プロトン伝導性を有するものであれば良く、高分子電解質膜と同様のフッ素系高分子電解質、炭化水素系高分子電解質を用いることができる。フッ素系高分子電解質としては、例えば、デュポン社製Ｎａｆｉｏｎ（登録商標）系材料などを用いることができる。また、炭化水素系高分子電解質膜としては、スルホン化ポリエーテルケトン、スルホン化ポリエーテルスルホン、スルホン化ポリエーテルエーテルスルホン、スルホン化ポリスルフィド、スルホン化ポリフェニレンなどの電解質膜を用いることができる。中でも、高分子電解質膜としてデュポン社製Ｎａｆｉｏｎ（登録商標）系材料を好適に用いることができる。なお、電極触媒層と高分子電解質膜の密着性を考慮すると、高分子電解質膜と同一の材料を用いることが好ましい。 The polymer electrolyte according to the embodiment of the present invention may be any one having proton conductivity, and the same fluorine-based polymer electrolyte and hydrocarbon-based polymer electrolyte as the polymer electrolyte membrane can be used. As the fluorine-based polymer electrolyte, for example, a Nafion (registered trademark) material manufactured by DuPont can be used. As the hydrocarbon polymer electrolyte membrane, electrolyte membranes such as sulfonated polyether ketone, sulfonated polyethersulfone, sulfonated polyetherethersulfone, sulfonated polysulfide, and sulfonated polyphenylene can be used. Among these, a Nafion (registered trademark) material manufactured by DuPont can be suitably used as the polymer electrolyte membrane. In consideration of the adhesion between the electrode catalyst layer and the polymer electrolyte membrane, it is preferable to use the same material as the polymer electrolyte membrane.
また、本発明の高分子電解質には、触媒物質を包埋する高分子電解質と、炭素粒子を包埋する高分子電解質と、高分子電解質で包埋した触媒物質と高分子電解質で包埋した炭素粒子と混合される高分子電解質があるが、それぞれ同一の高分子電解質でもよく、また、異なる高分子電解質でもよい。 The polymer electrolyte of the present invention is embedded in a polymer electrolyte that embeds a catalyst material, a polymer electrolyte that embeds carbon particles, a catalyst material that is embedded in a polymer electrolyte, and a polymer electrolyte. There are polymer electrolytes mixed with carbon particles, but the same polymer electrolytes or different polymer electrolytes may be used.
触媒物質もしくは炭素粒子を高分子電解質で包埋するときの分散媒、または、触媒インクの分散媒として使用される溶媒は、触媒物質や高分子電解質を浸食することがなく、高分子電解質を流動性の高い状態で溶解または微細ゲルとして分散できるものあれば特に制限はない。しかし、揮発性の有機溶媒が少なくとも含まれることが望ましく、特に限定されるものではないが、メタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、２−ブタノール、イソブチルアルコール、ｔｅｒｔ−ブチルアルコール、ペンタノールなどのアルコール類、アセトン、メチルエチルケトン、ペンタノン、メチルイソブチルケトン、へプタノン、シクロヘキサノン、メチルシクロヘキサノン、アセトニルアセトン、ジイソブチルケトンなどのケトン系溶剤、テトラヒドロフラン、ジオキサン、ジエチレングリコールジメチルエーテル、アニソール、メトキシトルエン、ジブチルエーテルなどのエーテル系溶剤、その他ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン、エチレングリコール、ジエチレングリコール、ジアセトンアルコール、１−メトキシ−２−プロパノールなどの極性溶剤などが使用される。また、これらの溶剤のうち二種以上を混合させたものも使用できる。 The solvent used when embedding the catalyst substance or carbon particles with the polymer electrolyte or the solvent used as the dispersion medium for the catalyst ink flows through the polymer electrolyte without eroding the catalyst substance or the polymer electrolyte. There is no particular limitation as long as it can be dissolved or dispersed as a fine gel in a highly soluble state. However, it is desirable that at least a volatile organic solvent is contained, and although not particularly limited, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl Alcohols such as alcohol and pentanol, acetone, methyl ethyl ketone, pentanone, methyl isobutyl ketone, heptanone, cyclohexanone, methyl cyclohexanone, acetonyl acetone, diisobutyl ketone and other ketone solvents, tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, anisole, methoxytoluene , Ether solvents such as dibutyl ether, other dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol Le, diethylene glycol, diacetone alcohol, such as a polar solvent such as 1-methoxy-2-propanol is used. Moreover, what mixed 2 or more types of these solvents can also be used.
また、溶媒として低級アルコールを用いたものは発火の危険性が高く、このような溶媒を用いる際は水との混合溶媒にするのが好ましい。高分子電解質となじみがよい水が含まれていてもよい。水の添加量は、高分子電解質が分離して白濁を生じたり、ゲル化したりしない程度であれば特に制限はない。 In addition, those using lower alcohol as the solvent have a high risk of ignition, and when using such a solvent, it is preferable to use a mixed solvent with water. Water that is compatible with the polymer electrolyte may be contained. The amount of water added is not particularly limited as long as the polymer electrolyte is not separated to cause white turbidity or gelation.
高分子電解質で包埋した触媒物質と、高分子電解質で包埋した炭素粒子を分散させるために、触媒インクに分散剤が含まれていても良い。分散剤としては、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤、非イオン界面活性剤などを挙げることができる。 In order to disperse the catalyst material embedded with the polymer electrolyte and the carbon particles embedded with the polymer electrolyte, the catalyst ink may contain a dispersant. Examples of the dispersant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.
上記アニオン界面活性剤としては、具体的には、例えば、アルキルエーテルカルボン酸塩、エーテルカルボン酸塩、アルカノイルザルコシン、アルカノイルグルタミン酸塩、アシルグルタメート、オレイン酸・Ｎ−メチルタウリン、オレイン酸カリウム・ジエタノールアミン塩、アルキルエーテルサルフェート・トリエタノールアミン塩、ポリオキシエチレンアルキルエーテルサルフェート・トリエタノールアミン塩、特殊変成ポリエーテルエステル酸のアミン塩、高級脂肪酸誘導体のアミン塩、特殊変成ポリエステル酸のアミン塩、高分子量ポリエーテルエステル酸のアミン塩、特殊変成燐酸エステルのアミン塩、高分子量ポリエステル酸アミドアミン塩、特殊脂肪酸誘導体のアミドアミン塩、高級脂肪酸のアルキルアミン塩、高分子量ポリカルボン酸のアミドアミン塩、ラウリン酸ナトリウム、ステアリン酸ナトリウム、オレイン酸ナトリウムなどのカルボン酸型界面活性剤、ジアルキルスルホサクシネート、スルホこはく酸ジアルキル塩、１，２−ビス（アルコキシカルボニル）−１−エタンスルホン酸塩、アルキルスルホネート、アルキルスルホン酸塩、パラフィンスルホン酸塩、アルファオレフィンスルホネート、直鎖アルキルベンゼンスルホネート、アルキルベンゼンスルホネート、ポリナフチルメタンスルホネート、ポリナフチルメタンスルホン酸塩、ナフタレンスルホネート−ホルマリン縮合物、アルキルナフタレンスルホネート、アルカノイルメチルタウリド、ラウリル硫酸エステルナトリウム塩、セチル硫酸エステルナトリウム塩、ステアリル硫酸エステルナトリウム塩、オレイル硫酸エステルナトリウム塩、ラウリルエーテル硫酸エステル塩、アルキルベンゼンスルホン酸ナトリウム、油溶性アルキルベンゼンスルホン酸塩、α−オレフィンスルホン酸塩などのスルホン酸型界面活性剤、アルキル硫酸エステル塩、硫酸アルキル塩、アルキルサルフェート、アルキルエーテルサルフェート、ポリオキシエチレンアルキルエーテルサルフェート、アルキルポリエトキシ硫酸塩、ポリグリコールエーテルサルフェート、アルキルポリオキシエチレン硫酸塩、硫酸化油、高度硫酸化油などの硫酸エステル型界面活性剤、リン酸（モノまたはジ）アルキル塩、（モノまたはジ）アルキルホスフェート、（モノまたはジ）アルキルりん酸エステル塩、りん酸アルキルポリオキシエチレン塩、アルキルエーテルホスフェート、アルキルポリエトキシ・りん酸塩、ポリオキシエチレンアルキルエーテル、りん酸アルキルフェニル・ポリオキシエチレン塩、アルキルフェニルエーテル・ホスフェート、アルキルフェニル・ポリエトキシ・りん酸塩、ポリオキシエチレン・アルキルフェニル・エーテルホスフェート、高級アルコールリン酸モノエステルジナトリウム塩、高級アルコールリン酸ジエステルジナトリウム塩、ジアルキルジチオリン酸亜鉛などのりん酸エステル型界面活性剤などが挙げられる。 Specific examples of the anionic surfactant include alkyl ether carboxylate, ether carboxylate, alkanoyl sarcosine, alkanoyl glutamate, acyl glutamate, oleic acid / N-methyltaurine, potassium oleate / diethanolamine Salt, alkyl ether sulfate / triethanolamine salt, polyoxyethylene alkyl ether sulfate / triethanolamine salt, amine salt of special modified polyether ester acid, amine salt of higher fatty acid derivative, amine salt of special modified polyester acid, high molecular weight Polyamine ester acid amine salt, special modified phosphate amine salt, high molecular weight polyester acid amide amine salt, special fatty acid derivative amide amine salt, higher fatty acid alkyl amine salt, high molecular weight polyester Amidoamine salt of carboxylic acid, carboxylic acid type surfactant such as sodium laurate, sodium stearate, sodium oleate, dialkyl sulfosuccinate, dialkyl salt of sulfosuccinic acid, 1,2-bis (alkoxycarbonyl) -1-ethane Sulfonate, alkyl sulfonate, alkyl sulfonate, paraffin sulfonate, alpha olefin sulfonate, linear alkyl benzene sulfonate, alkyl benzene sulfonate, polynaphthyl methane sulfonate, polynaphthyl methane sulfonate, naphthalene sulfonate-formalin condensate, alkyl naphthalene Sulfonate, alkanoylmethyl tauride, lauryl sulfate sodium salt, cetyl sulfate sodium salt, stearyl sulfate ester Sodium salt, oleyl sulfate sodium salt, lauryl ether sulfate ester salt, sodium alkylbenzene sulfonate, oil-soluble alkylbenzene sulfonate, α-olefin sulfonate, etc., alkyl sulfate ester salt, alkyl sulfate salt , Sulfate surfactants such as alkyl sulfate, alkyl ether sulfate, polyoxyethylene alkyl ether sulfate, alkyl polyethoxy sulfate, polyglycol ether sulfate, alkyl polyoxyethylene sulfate, sulfated oil, highly sulfated oil, Phosphoric acid (mono or di) alkyl salt, (mono or di) alkyl phosphate, (mono or di) alkyl phosphate ester salt, alkyl polyoxyethylene salt of phosphate, alkyl ether phosphate Fate, alkylpolyethoxy phosphate, polyoxyethylene alkyl ether, alkylphenyl phosphate polyoxyethylene salt, alkylphenyl ether phosphate, alkylphenyl polyethoxy phosphate, polyoxyethylene alkylphenyl ether phosphate And phosphoric acid ester type surfactants such as higher alcohol phosphoric acid monoester disodium salt, higher alcohol phosphoric acid diester disodium salt and zinc dialkyldithiophosphate.
上記カチオン界面活性剤としては、具体的には、例えば、ベンジルジメチル｛２−［２−（Ｐ−１，１，３，３−テトラメチルブチルフェノオキシ）エトオキシ］エチル｝アンモニウムクロライド、オクタデシルアミン酢酸塩、テトラデシルアミン酢酸塩、オクタデシルトリメチルアンモニウムクロライド、牛脂トリメチルアンモニウムクロライド、ドデシルトリメチルアンモニウムクロライド、ヤシトリメチルアンモニウムクロライド、ヘキサデシルトリメチルアンモニウムクロライド、ベヘニルトリメチルアンモニウムクロライド、ヤシジメチルベンジルアンモニウムクロライド、テトラデシルジメチルベンジルアンモニウムクロライド、オクタデシルジメチルベンジルアンモニウムクロライド、ジオレイルジメチルアンモニウムクロライド、１−ヒドロキシエチル−２−牛脂イミダゾリン４級塩、２−ヘプタデセニルーヒドロキシエチルイミダゾリン、ステアラミドエチルジエチルアミン酢酸塩、ステアラミドエチルジエチルアミン塩酸塩、トリエタノールアミンモノステアレートギ酸塩、アルキルピリジウム塩、高級アルキルアミンエチレンオキサイド付加物、ポリアクリルアミドアミン塩、変成ポリアクリルアミドアミン塩、パーフルオロアルキル第４級アンモニウムヨウ化物などが挙げられる。 Specific examples of the cationic surfactant include benzyldimethyl {2- [2- (2- (P-1,1,3,3-tetramethylbutylphenoxy) ethoxy] ethyl} ammonium chloride, octadecylamine acetic acid. Salt, tetradecylamine acetate, octadecyltrimethylammonium chloride, tallow trimethylammonium chloride, dodecyltrimethylammonium chloride, palm trimethylammonium chloride, hexadecyltrimethylammonium chloride, behenyltrimethylammonium chloride, palm dimethylbenzylammonium chloride, tetradecyldimethylbenzylammonium Chloride, octadecyldimethylbenzylammonium chloride, dioleyldimethylammonium chlora 1-hydroxyethyl-2-tallow imidazoline quaternary salt, 2-heptadecenyl-hydroxyethyl imidazoline, stearamide ethyl diethylamine acetate, stearamide ethyl diethylamine hydrochloride, triethanolamine monostearate formate, alkyl pyridium Examples thereof include a palladium salt, a higher alkylamine ethylene oxide adduct, a polyacrylamideamine salt, a modified polyacrylamideamine salt, and a perfluoroalkyl quaternary ammonium iodide.
上記両性界面活性剤としては、具体的には、例えば、ジメチルヤシベタイン、ジメチルラウリルベタイン、ラウリルアミノエチルグリシンナトリウム、ラウリルアミノプロピオン酸ナトリウム、ステアリルジメチルベタイン、ラウリルジヒドロキシエチルベタイン、アミドベタイン、イミダゾリニウムベタイン、レシチン、３−［ω−フルオロアルカノイル−Ｎ−エチルアミノ］−１−プロパンスルホン酸ナトリウム、Ｎ−［３−（パーフルオロオクタンスルホンアミド）プロピル］−Ｎ，Ｎ−ジメチル−Ｎ−カルボキシメチレンアンモニウムベタインなどが挙げられる。 Specific examples of the amphoteric surfactant include dimethyl coconut betaine, dimethyl lauryl betaine, sodium laurylaminoethylglycine, sodium laurylaminopropionate, stearyl dimethyl betaine, lauryl dihydroxyethyl betaine, amide betaine, imidazolinium. Betaine, lecithin, sodium 3- [ω-fluoroalkanoyl-N-ethylamino] -1-propanesulfonate, N- [3- (perfluorooctanesulfonamido) propyl] -N, N-dimethyl-N-carboxymethylene Examples include ammonium betaine.
上記非イオン界面活性剤としては、具体的には、例えば、ヤシ脂肪酸ジエタノールアミド（１：２型）、ヤシ脂肪酸ジエタノールアミド（１：１型）、牛脂肪酸ジエタノールアミド（１：２型）、牛脂肪酸ジエタノールアミド（１：１型）、オレイン酸ジエタノールアミド（１：１型）、ヒドロキシエチルラウリルアミン、ポリエチレングリコールラウリルアミン、ポリエチレングリコールヤシアミン、ポリエチレングリコールステアリルアミン、ポリエチレングリコール牛脂アミン、ポリエチレングリコール牛脂プロピレンジアミン、ポリエチレングリコールジオレイルアミン、ジメチルラウリルアミンオキサイド、ジメチルステアリルアミンオキサイド、ジヒドロキシエチルラウリルアミンオキサイド、パーフルオロアルキルアミンオキサイド、ポリビニルピロリドン、高級アルコールエチレンオキサイド付加物、アルキルフェノールエチレンオキサイド付加物、脂肪酸エチレンオキサイド付加物、ポリプロピレングリコールエチレンオキサイド付加物、グリセリンの脂肪酸エステル、ペンタエリスリットの脂肪酸エステル、ソルビットの脂肪酸エステル、ソルビタンの脂肪酸エステル、砂糖の脂肪酸エステルなどが挙げられる。 Specific examples of the nonionic surfactant include coconut fatty acid diethanolamide (1: 2 type), coconut fatty acid diethanolamide (1: 1 type), bovine fatty acid diethanolamide (1: 2 type), and cattle. Fatty acid diethanolamide (1: 1 type), oleic acid diethanolamide (1: 1 type), hydroxyethyl lauryl amine, polyethylene glycol lauryl amine, polyethylene glycol palm amine, polyethylene glycol stearyl amine, polyethylene glycol beef tallow amine, polyethylene glycol beef tallow propylene Diamine, polyethylene glycol diolylamine, dimethyl lauryl amine oxide, dimethyl stearyl amine oxide, dihydroxyethyl lauryl amine oxide, perfluoroalkylamine ox Id, polyvinyl pyrrolidone, higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, fatty acid ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, fatty acid ester of glycerin, fatty acid ester of pentaerythritol, fatty acid ester of sorbit, sorbitan Examples include fatty acid esters and sugar fatty acid esters.
上記界面活性剤の中でもアルキルベンゼンスルホン酸、油溶性アルキルベンゼンスルホン酸、α−オレフィンスルホン酸、アルキルベンゼンスルホン酸ナトリウム、油溶性アルキルベンゼンスルホン酸塩、α−オレフィンスルホン酸塩などのスルホン酸型の界面活性剤は、カーボンの分散効果、分散剤の残存による触媒性能の変化などを考慮すると、好適である。 Among the above surfactants, sulfonic acid type surfactants such as alkylbenzene sulfonic acid, oil-soluble alkyl benzene sulfonic acid, α-olefin sulfonic acid, sodium alkyl benzene sulfonate, oil-soluble alkyl benzene sulfonate and α-olefin sulfonate are Considering the carbon dispersion effect and the change in catalyst performance due to the remaining dispersant, it is preferable.
触媒インクは、必要に応じて分散処理がおこなわれる。触媒インクの粘度、粒子のサイズは、触媒インクの分散処理の条件によって制御することができる。分散処理は、様々な装置を用いておこなうことができる。例えば、分散処理としては、ボールミルやロールミルによる処理、せん断ミルによる処理、湿式ミルによる処理、超音波分散処理などが挙げられる。また、遠心力で攪拌を行うホモジナイザーなどを用いても良い。 The catalyst ink is subjected to a dispersion treatment as necessary. The viscosity and particle size of the catalyst ink can be controlled by the conditions for the dispersion treatment of the catalyst ink. Distributed processing can be performed using various devices. For example, as the dispersion treatment, treatment with a ball mill or roll mill, treatment with a shear mill, treatment with a wet mill, ultrasonic dispersion treatment, and the like can be given. Moreover, you may use the homogenizer etc. which stir with centrifugal force.
触媒インク中の固形分含有量は、多すぎると触媒インクの粘度が高くなるため電極触媒層表面にクラックが入りやすくなり、また、逆に少なすぎると成膜レートが非常に遅く、生産性が低下してしまうため、１質量％以上５０質量％以下であることが好ましい。固形分は触媒物質および炭素粒子と高分子電解質からなるが、炭素粒子を多くすると同じ固形分含有量でも粘度は高くなり、少なくすると粘度は低くなる。そのため、固形分に占める炭素粒子の割合は１０質量％以上８０質量％以下が好ましい。また、このときの触媒インクの粘度は、０．１ｃＰ以上５００ｃＰ以下程度が好ましく、さらに好ましくは５ｃＰ以上１００ｃＰ以下が良い。また、触媒インクの分散時に分散剤を添加することで、粘度の制御をすることもできる。 If the content of the solid content in the catalyst ink is too large, the viscosity of the catalyst ink will increase, so that the surface of the electrode catalyst layer will easily crack, and conversely if it is too small, the film formation rate will be very slow and productivity will be low. Since it will fall, it is preferable that they are 1 mass% or more and 50 mass% or less. The solid content is composed of a catalyst substance, carbon particles, and a polymer electrolyte. When the carbon particles are increased, the viscosity is increased even when the solid content is the same, and when the carbon content is decreased, the viscosity is decreased. Therefore, the proportion of carbon particles in the solid content is preferably 10% by mass or more and 80% by mass or less. Further, the viscosity of the catalyst ink at this time is preferably about 0.1 cP or more and 500 cP or less, and more preferably 5 cP or more and 100 cP or less. Further, the viscosity can be controlled by adding a dispersing agent when dispersing the catalyst ink.
また、触媒インクに造孔剤が含まれても良い。造孔剤は、電極触媒層の形成後に除去することで、細孔を形成することができる。酸やアルカリ、水に溶ける物質や、ショウノウなどの昇華する物質、熱分解する物質などを挙げることができる。温水で溶ける物質であれば、発電時に発生する水で取り除いても良い。 The catalyst ink may contain a pore forming agent. By removing the pore-forming agent after the formation of the electrode catalyst layer, pores can be formed. Examples include substances that are soluble in acids, alkalis, and water, substances that sublime such as camphor, and substances that thermally decompose. If the substance is soluble in hot water, it may be removed with water generated during power generation.
酸やアルカリ、水に溶ける造孔剤としては、炭酸カルシウム、炭酸バリウム、炭酸マグネシウム、硫酸マグネシウム、酸化マグネシウムなどの酸可溶性無機塩類、アルミナ、シリカゲル、シリカゾルなどのアルカリ水溶液に可溶性の無機塩類、アルミニウム、亜鉛、スズ、ニッケル、鉄などの酸またはアルカリに可溶性の金属類、塩化ナトリウム、塩化カリウム、塩化アンモニウム、炭酸ナトリウム、硫酸ナトリウム、リン酸一ナトリウムなどの水溶性無機塩類、ポリビニルアルコール、ポリエチレングリコールなどの水溶性有機化合物類などが挙げられ、二種以上併用することも有効である。 Examples of pore-forming agents that are soluble in acids, alkalis, and water include acid-soluble inorganic salts such as calcium carbonate, barium carbonate, magnesium carbonate, magnesium sulfate, and magnesium oxide, inorganic salts soluble in alkaline aqueous solutions such as alumina, silica gel, and silica sol, aluminum Metals soluble in acids or alkalis such as zinc, tin, nickel and iron, water-soluble inorganic salts such as sodium chloride, potassium chloride, ammonium chloride, sodium carbonate, sodium sulfate and monosodium phosphate, polyvinyl alcohol, polyethylene glycol It is also effective to use two or more types in combination.
本発明の触媒インクは、それぞれ高分子電解質で包埋した触媒物質と炭素粒子は、高分子電解質とともに溶媒に分散させたインクを作製し、そのインクを乾燥させることで得られる。例えば、それぞれ高分子電解質で包埋した触媒物質と炭素粒子、高分子電解質を溶媒に分散させたインクを転写シートなどに塗布し、乾燥させることで得られる。または、乾燥雰囲気中にスプレーすることでもそれぞれ高分子電解質で包埋した触媒物質と炭素粒子が直接得られる。 The catalyst ink of the present invention is obtained by preparing an ink in which a catalyst substance and carbon particles embedded in a polymer electrolyte are dispersed in a solvent together with the polymer electrolyte, and drying the ink. For example, it can be obtained by applying a catalyst material and carbon particles embedded in a polymer electrolyte, and an ink in which the polymer electrolyte is dispersed in a solvent, to a transfer sheet and drying it. Alternatively, the catalyst material and carbon particles embedded in the polymer electrolyte can be directly obtained by spraying in a dry atmosphere.
インクを乾燥させるときの温度範囲は、３０℃以上１４０℃以下であることが好ましい。インクを乾燥させるときの温度が３０℃に満たない場合にあっては、インクを作製する工程で、触媒物質を包埋する多くの高分子電解質が溶媒に溶解し、出力性能が向上しない場合がある。また、インクを乾燥させるときの温度が１４０℃を超える場合にあっても、触媒物質を包埋する高分子電解質のプロトン伝導性が阻害され、出力性能が向上しない場合がある。 The temperature range for drying the ink is preferably 30 ° C. or more and 140 ° C. or less. If the temperature at which the ink is dried is less than 30 ° C., the output performance may not be improved because many polymer electrolytes embedding the catalyst substance are dissolved in the solvent in the step of preparing the ink. is there. Even when the temperature at which the ink is dried exceeds 140 ° C., the proton conductivity of the polymer electrolyte that embeds the catalyst substance is hindered, and the output performance may not be improved.
本発明の触媒インクにおいて、高分子電解質で包埋した触媒物質と、高分子電解質で包埋した炭素粒子と、高分子電解質を溶媒に分散させた触媒インクから電極触媒層を作製する工程では、触媒インクを基材上に塗布し、乾燥工程を経て電極触媒層を形成する。基材として、ガス拡散層または転写シートを用いた場合には、接合工程によって高分子電解質膜の両面に電極触媒層は接合される。また、本発明の膜電極接合体にあっては、基材として高分子電解質膜を用い、高分子電解質膜の両面に直接触媒インクを塗布し、高分子電解質膜両面に直接電極触媒層を形成することもできる。 In the catalyst ink of the present invention, in the step of producing an electrode catalyst layer from a catalyst material embedded in a polymer electrolyte, carbon particles embedded in the polymer electrolyte, and a catalyst ink in which the polymer electrolyte is dispersed in a solvent, A catalyst ink is applied on a substrate, and an electrode catalyst layer is formed through a drying process. When a gas diffusion layer or a transfer sheet is used as the substrate, the electrode catalyst layers are bonded to both surfaces of the polymer electrolyte membrane by a bonding process. In the membrane / electrode assembly of the present invention, a polymer electrolyte membrane is used as a base material, a catalyst ink is directly applied to both sides of the polymer electrolyte membrane, and an electrode catalyst layer is directly formed on both sides of the polymer electrolyte membrane. You can also
このとき、塗布方法としては、ドクターブレード法、ディッピング法、スクリーン印刷法、ロールコーティング法、スプレー法などを用いることができる。例えば、加圧スプレー法、超音波スプレー法、静電噴霧法などのスプレー法は、塗工された触媒インクを乾燥させる際に凝集が起こりにくく、均質で空孔率の高い触媒層が得ることができる。 At this time, as a coating method, a doctor blade method, a dipping method, a screen printing method, a roll coating method, a spray method, or the like can be used. For example, spraying methods such as pressure spraying, ultrasonic spraying, and electrostatic spraying are not likely to agglomerate when the coated catalyst ink is dried, resulting in a homogeneous and highly porous catalyst layer. Can do.
上記の通り、本発明の電極触媒層の製造方法における基材としては、ガス拡散層、転写シート、高分子電解質膜から選択されるいずれかのものを用いることが好ましい。 As described above, it is preferable to use any one selected from a gas diffusion layer, a transfer sheet, and a polymer electrolyte membrane as the substrate in the method for producing an electrode catalyst layer of the present invention.
基材として用いられる転写シートとしては、転写性がよい材質であればよく、例えばエチレンテトラフルオロエチレン共重合体（ＥＴＦＥ）、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（ＦＥＰ）、テトラフルオロパーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、ポリテトラフルオロエチレン（ＰＴＦＥ）などのフッ素系樹脂を用いることができる。また、ポリイミド、ポリエチレンテレフタラート、ポリアミド（ナイロン）、ポリサルホン、ポリエーテルサルホン、ポリフェニレンサルファイド、ポリエーテル・エーテルケトン、ポリエーテルイミド、ポリアリレート、ポリエチレンナフタレートなどの高分子シート、高分子フィルムを転写シートとして用いることができる。基材として転写シートを用いた場合には、高分子電解質膜に電極触媒層を接合後に転写シートを剥離し、高分子電解質膜の両面に触媒層を備える膜電極接合体とすることができる。 The transfer sheet used as the substrate may be any material that has good transferability, such as ethylene tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and tetrafluoroperfluoro. A fluorine resin such as an alkyl vinyl ether copolymer (PFA) or polytetrafluoroethylene (PTFE) can be used. Also, polymer sheets such as polyimide, polyethylene terephthalate, polyamide (nylon), polysulfone, polyethersulfone, polyphenylene sulfide, polyether ether ketone, polyetherimide, polyarylate, polyethylene naphthalate, etc. are transferred. It can be used as a sheet. When a transfer sheet is used as the base material, the electrode catalyst layer is bonded to the polymer electrolyte membrane, and then the transfer sheet is peeled off to obtain a membrane / electrode assembly having catalyst layers on both sides of the polymer electrolyte membrane.
ガス拡散層としては、ガス拡散性と導電性とを有する材質のものを用いることができる。具体的にはガス拡散層としてはカーボンクロス、カーボンペーパー、不織布などのポーラスカーボン材を用いることができる。ガス拡散層は基材として用いることもできる。このとき、接合工程後にガス拡散層である基材を剥離する必要は無い。 As the gas diffusion layer, a material having gas diffusibility and conductivity can be used. Specifically, porous carbon materials such as carbon cloth, carbon paper, and non-woven fabric can be used as the gas diffusion layer. The gas diffusion layer can also be used as a substrate. At this time, it is not necessary to peel off the base material that is the gas diffusion layer after the joining step.
ガス拡散層を基材として用いる場合には、触媒インクを塗布する前に、予め、ガス拡散層上に目処め層を形成させてもよい。目処め層は、触媒インクがガス拡散層の中に染み込むことを防止する層であり、触媒インクの塗布量が少ない場合でも目処め層上に堆積して三相界面を形成する。このような目処め層は、例えばフッ素系樹脂溶液にカーボン粒子を分散させ、フッ素系樹脂の融点以上の温度で焼結させることにより形成することができる。フッ素系樹脂としては、ポリテトラフルオロエチレン（ＰＴＦＥ）などが利用できる。 When the gas diffusion layer is used as a base material, a coating layer may be formed on the gas diffusion layer in advance before applying the catalyst ink. The mesh layer is a layer that prevents the catalyst ink from permeating into the gas diffusion layer, and deposits on the mesh layer to form a three-phase interface even when the coating amount of the catalyst ink is small. Such a sealing layer can be formed, for example, by dispersing carbon particles in a fluorine resin solution and sintering at a temperature equal to or higher than the melting point of the fluorine resin. As the fluororesin, polytetrafluoroethylene (PTFE) or the like can be used.
セパレーターとしては、カーボンタイプあるいは金属タイプのものなどを用いることができる。なお、ガス拡散層とセパレーターは一体構造となっていても構わない。また、セパレーターもしくは電極触媒層が、ガス拡散層の機能を果たす場合にはガス拡散層は省略されていても構わない。燃料電池としては、ガス供給装置、冷却装置などその他付随する装置を組み立てることにより製造される。 As the separator, a carbon type or a metal type can be used. The gas diffusion layer and the separator may be integrated. In addition, when the separator or the electrode catalyst layer functions as a gas diffusion layer, the gas diffusion layer may be omitted. The fuel cell is manufactured by assembling other accompanying devices such as a gas supply device and a cooling device.
本発明における触媒インクおよび本発明の触媒インクを用いた燃料電池用電極触媒層の製造方法について、以下に具体的な実施例および比較例を挙げて説明するが、本発明は下記実施例によって制限されるものではない。 The catalyst ink in the present invention and the method for producing a fuel cell electrode catalyst layer using the catalyst ink of the present invention will be described below with reference to specific examples and comparative examples. However, the present invention is limited by the following examples. Is not to be done.
（実施例）および（比較例）について示す。 (Example) and (Comparative Example) will be described.
（実施例）
〔高分子電解質で包埋した触媒物質の形成方法〕
触媒物質（ＴａＣＮＯ、比表面積９ｍ２／ｇ）と、２０質量％高分子電解質溶液（ナフィオン：登録商標、デュポン社製）を溶媒中で混合し、遊星型ボールミル（商品名：Ｐ−７、フリッチュ・ジャパン社製）で分散処理を行った。ボールミルのポット、ボールにはジルコニア製のものを用いた。インクの組成比は、触媒物質と高分子電解質の質量比で１：０．２５とした。溶媒は超純水、１−プロパノールを体積比で１：１とし、固形分含有量は１４質量％とした。ＰＴＦＥシートをインクの乾燥用の基材として使用した。ドクターブレードにより、インクを基材上に塗布し、そして大気雰囲気中８０℃で５分間乾燥させた。その後、高分子電解質で包埋した触媒物質を基材上から回収した。
(Example)
[Method of forming catalyst material embedded in polymer electrolyte]
A catalyst material (TaCNO, specific surface area 9 m 2 / g) and a 20% by mass polymer electrolyte solution (Nafion: registered trademark, manufactured by DuPont) are mixed in a solvent, and a planetary ball mill (trade name: P-7, Fritsch) is mixed. (Distributed by Japan). Ball mill pots and balls made of zirconia were used. The composition ratio of the ink was 1: 0.25 in terms of the mass ratio of the catalyst substance and the polymer electrolyte. The solvent was ultrapure water and 1-propanol in a volume ratio of 1: 1, and the solid content was 14% by mass. A PTFE sheet was used as a substrate for drying the ink. The ink was applied onto the substrate with a doctor blade and dried in air at 80 ° C. for 5 minutes. Thereafter, the catalyst material embedded with the polymer electrolyte was recovered from the substrate.
〔高分子電解質で包埋した炭素粒子の形成方法〕
炭素粒子（Ｋｅｔｊｅｎ Ｂｌａｃｋ、商品名：ＥＣ−３００Ｊ、ライオン社製、比表面積８００ｍ２／ｇ）と、２０質量％高分子電解質溶液（ナフィオン：登録商標、デュポン社製）を溶媒中で混合し、遊星型ボールミル（商品名：Ｐ−７、フリッチュ・ジャパン社製）で分散処理を行った。ボールミルのポット、ボールにはジルコニア製のものを用いた。インクの組成比は、炭素粒子と高分子電解質の質量比で１：０．５とした。溶媒は超純水、１−プロパノールを体積比で１：１とし、固形分含有量は１４質量％とした。ＰＴＦＥシートをインクの乾燥用の基材として使用した。ドクターブレードにより、インクを基材上に塗布し、そして大気雰囲気中８０℃で５分間乾燥させた。その後、高分子電解質で包埋した炭素粒子を基材上から回収した。
[Method of forming carbon particles embedded in polymer electrolyte]
Carbon particles (Ketjen Black, trade name: EC-300J, manufactured by Lion, specific surface area 800 m 2 / g) and a 20% by mass polymer electrolyte solution (Nafion: registered trademark, manufactured by DuPont) were mixed in a solvent, Dispersion treatment was performed with a planetary ball mill (trade name: P-7, manufactured by Fritsch Japan). Ball mill pots and balls made of zirconia were used. The composition ratio of the ink was 1: 0.5 in terms of the mass ratio between the carbon particles and the polymer electrolyte. The solvent was ultrapure water and 1-propanol in a volume ratio of 1: 1, and the solid content was 14% by mass. A PTFE sheet was used as a substrate for drying the ink. The ink was applied onto the substrate with a doctor blade and dried in air at 80 ° C. for 5 minutes. Thereafter, the carbon particles embedded with the polymer electrolyte were recovered from the substrate.
〔高分子電解質で包埋した触媒物質と、高分子電解質で包埋した炭素粒子との混合および熱処理〕
高分子電解質で包埋した触媒物質と、高分子電解質で包埋した炭素粒子を遊星型ボールミルにて無溶媒で混合した。ボールミルのポット、ボールにはジルコニア製のものを用いた。高分子電解質で包埋した触媒物質と、高分子電解質で包埋した炭素粒子の組成比は、触媒物質および炭素粒子の質量比で１：１とした。
[Mixing and heat treatment of catalyst material embedded with polymer electrolyte and carbon particles embedded with polymer electrolyte]
The catalyst material embedded with the polymer electrolyte and the carbon particles embedded with the polymer electrolyte were mixed without solvent in a planetary ball mill. Ball mill pots and balls made of zirconia were used. The composition ratio of the catalyst material embedded with the polymer electrolyte and the carbon particles embedded with the polymer electrolyte was 1: 1 as the mass ratio of the catalyst material and the carbon particles.
〔触媒インクの調製〕
高分子電解質で包埋した触媒物質と、高分子電解質で包埋した炭素粒子の混合物に熱処理を加えたものと、２０質量％高分子電解質溶液を溶媒中で混合し、遊星型ボールミルで分散処理を行った。ボールミルのポット、ボールにはジルコニア製のものを用いた。触媒インクの組成比は、触媒物質および炭素粒子、高分子電解質の質量比で１：１：０．８とした。溶媒は超純水、１−プロパノールを体積比で１：１とした。また、固形分含有量は１４質量％とした。ＰＴＦＥシートを転写シートとして使用した。
[Preparation of catalyst ink]
A mixture of a catalyst material embedded with a polymer electrolyte and carbon particles embedded with a polymer electrolyte and a 20% by mass polymer electrolyte solution are mixed in a solvent and dispersed with a planetary ball mill. Went. Ball mill pots and balls made of zirconia were used. The composition ratio of the catalyst ink was 1: 1: 0.8 in terms of the mass ratio of the catalyst substance, carbon particles, and polymer electrolyte. The solvent was 1: 1 by volume ratio of ultrapure water and 1-propanol. The solid content was 14% by mass. A PTFE sheet was used as a transfer sheet.
〔電極触媒層の形成方法〕
ドクターブレードにより、触媒インクを転写シートに塗布し、そして大気雰囲気中８０℃で５分間乾燥させた。電極触媒層の厚さは、触媒物質担持量が０．４ｍｇ／ｃｍ２になるように調整し、空気極側の電極触媒層２を形成した。
[Method for forming electrode catalyst layer]
The catalyst ink was applied to the transfer sheet with a doctor blade and dried at 80 ° C. for 5 minutes in an air atmosphere. The thickness of the electrode catalyst layer was adjusted so that the amount of the catalyst substance supported was 0.4 mg / cm 2, and the electrode catalyst layer 2 on the air electrode side was formed.
（比較例）
〔触媒インクの調製〕
触媒物質と炭素粒子および２０質量％高分子電解質溶液を溶媒中で混合し、遊星型ボールミルで分散処理を行った。ボールミルのポット、ボールにはジルコニア製のものを用いた。触媒インクの組成比は、触媒物質と炭素粒子および高分子電解質の質量比が１：１：０．８としたものを触媒インクとした。溶媒は超純水、１−プロパノ−ルを体積比で１：１とした。また、固形分含有量は１４質量％とした。基材には、実施例と同じ転写シートを使用した。
(Comparative example)
[Preparation of catalyst ink]
The catalyst substance, carbon particles, and 20% by mass polymer electrolyte solution were mixed in a solvent, and dispersed with a planetary ball mill. Ball mill pots and balls made of zirconia were used. The composition ratio of the catalyst ink was such that the mass ratio of the catalyst substance, the carbon particles, and the polymer electrolyte was 1: 1: 0.8. The solvent used was ultrapure water and 1-propanol in a volume ratio of 1: 1. The solid content was 14% by mass. The same transfer sheet as in the example was used as the substrate.
〔電極触媒層の作製方法〕
実施例と同様の手法で、転写シートに触媒インクを塗布し、乾燥させた。電極触媒層の厚さは触媒物質担持量が０．４ｍｇ／ｃｍ２になるように調節し、空気極側の電極触媒層２を形成した。
[Method for producing electrode catalyst layer]
The catalyst ink was applied to the transfer sheet and dried in the same manner as in the example. The thickness of the electrode catalyst layer was adjusted so that the amount of the catalyst substance supported was 0.4 mg / cm 2, and the electrode catalyst layer 2 on the air electrode side was formed.
〔燃料極用電極触媒層の作製〕
白金担持量が５０質量％である白金担持カーボン触媒（商品名：ＴＥＣ１０Ｅ５０Ｅ、田中貴金属工業製）と、２０質量％高分子電解質溶液を溶媒中で混合し、遊星型ボールミルで分散処理をおこなった。分散時間を６０分間としたものを触媒インクとした。触媒インクの組成比は、白金担持カーボン中のカーボンと、高分子電解質は質量比で１：１とし、溶媒は超純水、１−プロパノールを体積比で１：１とした。また、固形分含有量は１０質量％とした。電極触媒層２と同様の手法で、基材に触媒インクを塗布し、乾燥させた。電極触媒層の厚さは触媒物質担持量が０．３ｍｇ／ｃｍ２になるように調整し、燃料極側の電極触媒層３を形成した。
[Preparation of electrode catalyst layer for fuel electrode]
A platinum-supported carbon catalyst (trade name: TEC10E50E, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) having a platinum-supporting amount of 50% by mass and a 20% by mass polymer electrolyte solution were mixed in a solvent and subjected to dispersion treatment with a planetary ball mill. A catalyst ink having a dispersion time of 60 minutes was used. The composition ratio of the catalyst ink was 1: 1 in the mass ratio of carbon in the platinum-supported carbon and the polymer electrolyte, and the solvent was 1: 1 in the volume ratio of ultrapure water and 1-propanol. The solid content was 10% by mass. In the same manner as in the electrode catalyst layer 2, the catalyst ink was applied to the substrate and dried. The thickness of the electrode catalyst layer was adjusted so that the amount of the catalyst material supported was 0.3 mg / cm 2, and the electrode catalyst layer 3 on the fuel electrode side was formed.
（膜電極接合体の作製）
（実施例）および（比較例）において作製した空気極側電極触媒層２が形成された基材と、燃料極側電極触媒層３を形成された基材を５ｃｍ２の正方形に打ち抜き、高分子電解質膜（ナフィオン（登録商標名）２１２、デュポン社製）の両面に対面するように転写シートを配置し、１３０℃、１０分間の条件でホットプレスを行い、膜電極接合体１２を得た。得られた膜電極接合体１２の両面に、ガス拡散層として目処め層が形成されたカーボンペーパー４、５を配置し、更に、一対のセパレーター１０で挟持し、単セルの固体高分子形燃料電池を作製した。
(Production of membrane electrode assembly)
The base material on which the air electrode side electrode catalyst layer 2 produced in (Example) and (Comparative Example) was formed and the base material on which the fuel electrode side electrode catalyst layer 3 was formed were punched into a square of 5 cm 2 to form a polymer. A transfer sheet was placed so as to face both surfaces of the electrolyte membrane (Nafion (registered trademark) 212, manufactured by DuPont), and hot pressing was performed at 130 ° C. for 10 minutes to obtain a membrane electrode assembly 12. Carbon papers 4 and 5 each having a sealing layer formed as a gas diffusion layer are disposed on both surfaces of the membrane electrode assembly 12 thus obtained, and are further sandwiched between a pair of separators 10 to provide a single cell solid polymer fuel. A battery was produced.
〔発電特性〕
（評価条件）
エヌエフ回路設計ブロック社製の燃料電池測定装置を用いて、セル温度８０℃で、アノードおよびカソードともに１００％ＲＨの条件で発電特性評価を行った。燃料ガスとして純水素、酸化剤ガスとして純酸素を用い、流量一定による流量制御を行った。
[Power generation characteristics]
(Evaluation conditions)
Using a fuel cell measuring device manufactured by NF Circuit Design Block Co., Ltd., power generation characteristics were evaluated at a cell temperature of 80 ° C. and at 100% RH for both the anode and cathode. Using pure hydrogen as the fuel gas and pure oxygen as the oxidant gas, the flow rate was controlled at a constant flow rate.
（測定結果）
（実施例）で作製した膜電極接合体は、（比較例）で作製した膜電極接合体よりも優れた発電性能を示した。特に０．６Ｖ付近の発電性能が向上し、（実施例）は（比較例）と比べて約２．２倍の発電性能を示した。これは、（実施例）では、触媒物質を高分子電解質で包埋することで、また、炭素粒子の比表面積が調整されることで触媒表面のプロトン伝導性が高められ、反応活性点が増加したためと推察した。これに対して、（比較例）では、触媒物質と炭素粒子および高分子電解質を一段階で溶媒中に分散させるため、触媒物質よりも比表面積の大きい炭素粒子に対して高分子電解質が優先的に吸着したことで、触媒物質の表面では十分なプロトン伝導性が確保されなかったためと推察した。
(Measurement result)
The membrane / electrode assembly produced in (Example) showed power generation performance superior to the membrane / electrode assembly produced in (Comparative Example). In particular, the power generation performance in the vicinity of 0.6 V was improved, and (Example) showed power generation performance about 2.2 times that of (Comparative Example). In (Example), the proton conductivity of the catalyst surface is increased by embedding the catalyst substance with a polymer electrolyte, and the specific surface area of the carbon particles is adjusted, thereby increasing the reaction active point. I guessed that. On the other hand, in (Comparative Example), the catalyst material, the carbon particles, and the polymer electrolyte are dispersed in a solvent in one step, so the polymer electrolyte is preferential to the carbon particles having a larger specific surface area than the catalyst material. It was presumed that sufficient proton conductivity was not ensured on the surface of the catalyst material by adsorbing on the surface of the catalyst material.
本発明は、高分子電解質および触媒物質と炭素粒子を有する電極触媒層を形成する触媒インクであり、炭素粒子よりも小さい比表面積の触媒物質に対して高分子電解質を包埋する触媒物質と、触媒物質よりも大きい比表面積の炭素粒子に対しても高分子電解質を包埋する炭素粒子とすることで、予め触媒表面のプロトン伝導性を高めることができ、反応活性点が増加し、また、炭素粒子の比表面積を小さくする処理を行うことで、電極触媒層の形成時に触媒表面のプロトン伝導性も高められる。その結果、出力性能の向上した電極触媒層、膜電極接合体および固体高分子形燃料電池を提供することができる。特に、触媒物質に酸化物系非白金触媒を使用した触媒インクにおいては、従来の触媒インクよりも触媒物質の潜在能力を引き出すことができるという顕著な効果を奏するので、産業上の利用価値が高い。 The present invention is a catalyst ink for forming an electrocatalyst layer having a polymer electrolyte and a catalyst substance and carbon particles, a catalyst substance for embedding the polymer electrolyte in a catalyst substance having a specific surface area smaller than that of the carbon particles, By making the carbon particles embedding the polymer electrolyte with respect to carbon particles having a specific surface area larger than that of the catalyst substance, the proton conductivity on the catalyst surface can be increased in advance, the reaction active point is increased, By performing the treatment for reducing the specific surface area of the carbon particles, the proton conductivity on the catalyst surface can be increased when the electrode catalyst layer is formed. As a result, an electrode catalyst layer, a membrane electrode assembly and a polymer electrolyte fuel cell with improved output performance can be provided. In particular, the catalyst ink using an oxide-based non-platinum catalyst as the catalyst material has a remarkable effect that the potential of the catalyst material can be brought out more than the conventional catalyst ink, and thus has high industrial utility value. .
１ 高分子電解質膜
２ 空気極側の電極触媒層
３ 燃料極側の電極触媒層
４ 空気極側のガス拡散層
５ 燃料極側のガス拡散層
６ 空気極（カソード）
７ 燃料極（アノード）
８ ガス流路
９ 冷却水流路
１０ セパレーター
１１ 膜電極接合体
１２ 固体高分子形燃料電池
DESCRIPTION OF SYMBOLS 1 Polymer electrolyte membrane 2 Electrode catalyst layer on the air electrode side 3 Electrode catalyst layer on the fuel electrode side 4 Gas diffusion layer on the air electrode side 5 Gas diffusion layer on the fuel electrode side 6 Air electrode (cathode)
7 Fuel electrode (anode)
8 Gas channel 9 Cooling water channel 10 Separator 11 Membrane electrode assembly 12 Polymer electrolyte fuel cell
Claims (3)
炭素粒子より比表面積が小さい触媒物質と第一の高分子電解質とを、重量比１：０．０１〜１：３０の範囲内で溶媒に分散し温度範囲が３０℃以上１４０℃以下の範囲内で乾燥してなる第一の高分子電解質で包埋した触媒物質と、
前記触媒物質より比表面積が大きい前記炭素粒子と第二の高分子電解質とを、重量比１：０．１〜１：２０の範囲内で溶媒に分散し温度範囲が３０℃以上１４０℃以下の範囲内で乾燥してなる第二の高分子電解質で包埋した炭素粒子とを有し、
無溶媒で混合し温度範囲が５０℃以上１８０℃以下の範囲内で熱処理した前記第一の高分子電解質で包埋した触媒物質と前記第二の高分子電解質で包埋した炭素粒子とを、第三の高分子電解質とともに溶媒に分散してなり、
前記第一の高分子電解質及び前記第二の高分子電解質及び前記第三の高分子電解質はそれぞれフッ素系高分子電解質又は炭化水素系高分子電解質であることを特徴とする触媒インクの製造方法。 In a method for producing a catalyst ink for an electrode catalyst layer for a fuel cell having a polymer electrolyte, a catalyst substance, and carbon particles,
A catalyst material having a specific surface area smaller than that of carbon particles and the first polymer electrolyte are dispersed in a solvent within a weight ratio of 1: 0.01 to 1:30, and a temperature range of 30 ° C. to 140 ° C. A catalyst material embedded in a first polymer electrolyte dried with
The carbon particles having a larger specific surface area than the catalyst material and the second polymer electrolyte are dispersed in a solvent within a weight ratio of 1: 0.1 to 1:20, and the temperature range is 30 ° C. or higher and 140 ° C. or lower. Carbon particles embedded with a second polymer electrolyte that is dried within the range,
A catalyst material embedded in the first polymer electrolyte and carbon particles embedded in the second polymer electrolyte, which are mixed without solvent and heat-treated in a temperature range of 50 ° C. or higher and 180 ° C. or lower; It is dispersed in a solvent together with the third polymer electrolyte,
The method for producing a catalyst ink , wherein the first polymer electrolyte, the second polymer electrolyte, and the third polymer electrolyte are respectively a fluorine-based polymer electrolyte or a hydrocarbon-based polymer electrolyte.
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