JP2012099296A - Catalyst for fuel batteries, method of manufacturing the same, film-electrode assembly, and fuel battery - Google Patents
Catalyst for fuel batteries, method of manufacturing the same, film-electrode assembly, and fuel battery Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 250
- 239000000446 fuel Substances 0.000 title claims abstract description 172
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 72
- 229920005989 resin Polymers 0.000 claims abstract description 54
- 239000011347 resin Substances 0.000 claims abstract description 54
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000012528 membrane Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 239000004640 Melamine resin Substances 0.000 claims description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 4
- 229920000180 alkyd Polymers 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 239000009719 polyimide resin Substances 0.000 claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 230000000694 effects Effects 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000006229 carbon black Substances 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000012018 catalyst precursor Substances 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910001339 C alloy Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000010757 Reduction Activity Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003929 acidic solution Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- OEZXFVMHAJJKKK-UHFFFAOYSA-N cobalt;1,10-phenanthroline Chemical compound [Co].C1=CN=C2C3=NC=CC=C3C=CC2=C1 OEZXFVMHAJJKKK-UHFFFAOYSA-N 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000005539 carbonized material Substances 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- OJTMBXWTXBFVQN-UHFFFAOYSA-N iron;1,10-phenanthroline Chemical compound [Fe].C1=CN=C2C3=NC=CC=C3C=CC2=C1 OJTMBXWTXBFVQN-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002078 nanoshell Substances 0.000 description 1
- MFNHWMTWXSYINF-UHFFFAOYSA-N nickel;1,10-phenanthroline Chemical compound [Ni].C1=CN=C2C3=NC=CC=C3C=CC2=C1 MFNHWMTWXSYINF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
本発明は、埋蔵量が少なく高価なＰｔ（白金）の代替となる、資源的制約の少ない炭素材料を有効成分とする高活性な燃料電池用触媒、およびその製造方法、並びに前記燃料電池用触媒を用いた膜電極接合体および燃料電池に関するものである。 The present invention relates to a highly active fuel cell catalyst comprising, as an active ingredient, a carbon material with less resource constraints, which is an alternative to expensive Pt (platinum) with a small reserve, a method for producing the same, and the fuel cell catalyst And a fuel cell.
昨今の原油高に加え、中国、インドなどの急速な経済発展により、化石燃料の枯渇と二酸化炭素の排出が世界的な問題となっている。このため、現在、脱石油化に向け、燃料電池を始め、リチウムイオン電池、バイオ燃料、太陽電池などの研究開発が活発に行われている。ナフィオン（登録商標）を代表とするプロトン導電膜を使用する燃料電池には、メタノールをアノード極燃料とする直接メタノール型燃料電池（Ｄｉｒｅｃｔ Ｍｅｔｈａｎｏｌ Ｆｕｅｌ Ｃｅｌｌ：ＤＭＦＣ）と、水素ガスをアノード極燃料とする固体高分子型燃料電池（Ｐｏｌｙｍｅｒ Ｅｌｅｃｔｒｏｌｙｔｅ Ｆｕｅｌ Ｃｅｌｌ：ＰＥＦＣ）とがある。 In addition to the recent rise in crude oil prices, rapid economic development in China, India and other countries has led to global problems of fossil fuel depletion and carbon dioxide emissions. For this reason, research and development of fuel cells, lithium-ion batteries, biofuels, solar cells, etc. are being actively carried out for the de-oiling. A fuel cell using a proton conductive film typified by Nafion (registered trademark) includes a direct methanol fuel cell (DMFC) using methanol as an anode fuel, and hydrogen gas as an anode fuel. There is a polymer polymer fuel cell (PEFC).
前記ＤＭＦＣおよびＰＥＦＣは、比較的低温作動が可能で、発電システムも簡便で小型化が可能なことから、施設の非常用電源や、軍事、業務用の携帯機器の非常電源、ノートパソコンや携帯音楽プレーヤー、携帯電話などの充電器として期待が持たれている。 The DMFC and PEFC can operate at relatively low temperatures, and the power generation system is simple and can be downsized. Therefore, emergency power supplies for facilities, emergency power supplies for military and commercial mobile devices, laptop computers, and portable music. Expectation is expected as a charger for players and mobile phones.
ＤＭＦＣは燃料にメタノールを、また、ＰＥＦＣは燃料に水素を使用し、それぞれアノード触媒層／プロトン導電膜／カソード触媒層から構成される膜電極接合体を導電性のガス拡散層で挟み、アノード極およびカソード極に設けた集電板により外部回路と繋いだ電池システムである。ＤＭＦＣのアノード触媒層側に液体燃料であるメタノールを供給すると、下記式（１）に示す化学反応により、メタノールが酸化されて二酸化炭素（ＣＯ２）に変化し、プロトン（Ｈ＋）と電子（ｅ−）とが発生する。
ＣＨ３ＯＨ ＋ Ｈ２Ｏ → ＣＯ２ ＋ ６Ｈ＋ ＋ ６ｅ− （１）
DMFC uses methanol as the fuel and PEFC uses hydrogen as the fuel. The membrane electrode assembly composed of the anode catalyst layer / proton conductive film / cathode catalyst layer is sandwiched between the conductive gas diffusion layers. And a battery system connected to an external circuit by a current collecting plate provided on the cathode electrode. When methanol, which is a liquid fuel, is supplied to the anode catalyst layer side of the DMFC, the methanol is oxidized and converted into carbon dioxide (CO 2 ) by a chemical reaction represented by the following formula (1), and protons (H + ) and electrons ( e -) and is generated.
CH 3 OH + H 2 O → CO 2 + 6H + + 6e − (1)
この反応によって発生したプロトンと電子とは、カソード触媒層に供給される酸素ガスと下記式（２）の反応により、水（Ｈ２Ｏ）を生成する。
Ｏ２ ＋ ４Ｈ＋ ＋ ４ｅ− → ２Ｈ２Ｏ （２）
The protons and electrons generated by this reaction generate water (H 2 O) by the reaction of oxygen gas supplied to the cathode catalyst layer and the following formula (2).
O 2 + 4H + + 4e − → 2H 2 O (2)
従って、電池全体として下記式（３）の反応が進行し、この際に発生する電子を外部回路で取り出して、電気エネルギーを得ることができる。
ＣＨ３ＯＨ ＋ ３／２Ｏ２ → ＣＯ２ ＋ ２Ｈ２Ｏ （３）
Therefore, the reaction of the following formula (3) proceeds as a whole battery, and electrons generated at this time can be taken out by an external circuit to obtain electric energy.
CH 3 OH + 3 / 2O 2 → CO 2 + 2H 2 O (3)
ところで、現在、ＤＭＦＣおよびＰＥＦＣの電極には、実用触媒としてＰｔ系触媒が使用されているが、Ｐｔはレアメタルであり、かつ非常に高価であることから、その使用量の削減が必須の課題となっている。 By the way, Pt-based catalysts are currently used as practical catalysts for DMFC and PEFC electrodes. However, since Pt is a rare metal and very expensive, reduction of the amount of use is an essential issue. It has become.
こうした問題を解決する手段として、例えば、触媒粒子の径を小さくし、触媒の比表面積を大きくすることで、触媒の単位質量あたりの活性を高め、これによって触媒使用量の削減を図る試みがなされている（特許文献１、２）。 As means for solving these problems, for example, attempts are made to increase the activity per unit mass of the catalyst by reducing the diameter of the catalyst particles and increasing the specific surface area of the catalyst, thereby reducing the amount of catalyst used. (Patent Documents 1 and 2).
また、更なるＰｔ使用量の削減を図るべく、Ｐｔを使用しない触媒の開発も試みられている。例えば、特許文献３、４には、窒素原子やホウ素原子がドープされた炭素系触媒であるカーボンアロイ微粒子を基材とする燃料電池用触媒が報告されている。 In addition, in order to further reduce the amount of Pt used, an attempt has been made to develop a catalyst that does not use Pt. For example, Patent Documents 3 and 4 report fuel cell catalysts based on carbon alloy fine particles, which are carbon-based catalysts doped with nitrogen atoms or boron atoms.
前記のカーボンアロイ微粒子は窒素原子やホウ素原子のドープによって、その活性の向上を図ったものであるが、実際には、例えば、活性サイトが不足していたり、活性サイトがカーボンアロイ微粒子中の細孔内に形成されてしまうことで、活性サイトの形成箇所での反応物質の拡散が良好に進まないなどの理由によって、想定しているだけの活性が十分に確保できない問題がある。 The carbon alloy fine particles described above have been improved in activity by doping with nitrogen atoms or boron atoms. However, in practice, for example, the active sites are insufficient or the active sites are fine particles in the carbon alloy fine particles. Due to the formation in the holes, there is a problem that sufficient activity cannot be secured due to the reason that the diffusion of the reactants at the active site formation site does not proceed well.
本発明は、前記事情に鑑みてなされたものであり、その目的は、Ｐｔを使用することなく高い触媒活性を示す燃料電池用触媒、およびその製造方法、並びに前記触媒を用いた膜電極接合体および燃料電池を提供することにある。 The present invention has been made in view of the above circumstances, and its object is to provide a fuel cell catalyst exhibiting high catalytic activity without using Pt, a method for producing the same, and a membrane electrode assembly using the catalyst. And providing a fuel cell.
前記目的を達成し得た本発明の燃料電池用触媒は、樹脂由来の炭素系触媒と、担体とを有する燃料電池用触媒であって、前記炭素系触媒は、前記担体の表面の少なくとも一部を被覆しており、比表面積が１００〜８００ｍ２／ｇであることを特徴とするものである。 The fuel cell catalyst of the present invention that has achieved the above object is a fuel cell catalyst comprising a resin-derived carbon-based catalyst and a carrier, wherein the carbon-based catalyst is at least part of the surface of the carrier. It has a specific surface area of 100 to 800 m 2 / g.
また、本発明の製造方法は、本発明の燃料電池用触媒を製造する方法であって、
（１）炭素系触媒の原料となる樹脂が溶剤に溶解または分散した液に、少なくとも１種の金属錯体を添加するステップと、
（２）前記（１）のステップで得られた液から溶剤を除去して、樹脂と金属錯体との混合物を調製するステップと、
（３）前記樹脂と金属錯体との混合物に、少なくとも１種の担体を添加して、樹脂と金属錯体と担体との混合物を調製するステップと、
（４）前記樹脂と金属錯体と担体との混合物を、非酸化性雰囲気中で、６００〜１２００℃で焼成するステップと、
（５）前記（４）のステップで得られた焼成物から金属を除去するステップとを有することを特徴とする。
The production method of the present invention is a method of producing the fuel cell catalyst of the present invention,
(1) adding at least one metal complex to a liquid in which a resin as a raw material for a carbon-based catalyst is dissolved or dispersed in a solvent;
(2) removing the solvent from the liquid obtained in the step (1) to prepare a mixture of a resin and a metal complex;
(3) adding at least one carrier to the mixture of the resin and the metal complex to prepare a mixture of the resin, the metal complex, and the carrier;
(4) firing the mixture of the resin, the metal complex, and the carrier in a non-oxidizing atmosphere at 600 to 1200 ° C .;
(5) A step of removing metal from the fired product obtained in the step (4).
更に、本発明の膜電極接合体は、カソード触媒層と、アノード触媒層と、前記カソード触媒層と前記アノード触媒層との間に間挿されたプロトン導電膜とからなり、前記カソード触媒層が、本発明の燃料電池用触媒を含むことを特徴とするものである。 Furthermore, the membrane electrode assembly of the present invention comprises a cathode catalyst layer, an anode catalyst layer, and a proton conductive film interposed between the cathode catalyst layer and the anode catalyst layer. The fuel cell catalyst of the present invention is included.
また、本発明の燃料電池は、カソード触媒層と、アノード触媒層と、前記カソード触媒層と前記アノード触媒層との間に間挿されたプロトン導電膜とからなる膜電極接合体を有しており、前記カソード触媒層が、本発明の燃料電池用媒を含むことを特徴とするものである。 The fuel cell of the present invention has a membrane electrode assembly comprising a cathode catalyst layer, an anode catalyst layer, and a proton conductive film interposed between the cathode catalyst layer and the anode catalyst layer. The cathode catalyst layer contains the fuel cell medium of the present invention.
本発明によれば、Ｐｔを使用することなく高い触媒活性を示し、かつ安価で資源に左右されることの少ない燃料電池用触媒と、その製造方法とを提供することができる。また、本発明の膜電極接合体は、優れた電池特性を有する燃料電池を構成できる。更に、本発明の燃料電池は、優れた電池特性を有している。 ADVANTAGE OF THE INVENTION According to this invention, the catalyst for fuel cells which shows a high catalyst activity without using Pt, is cheap and hardly depends on resources, and its manufacturing method can be provided. Moreover, the membrane electrode assembly of the present invention can constitute a fuel cell having excellent battery characteristics. Furthermore, the fuel cell of the present invention has excellent battery characteristics.
前記の通り、従来のカーボンアロイ微粒子では、活性サイトが不足していたり、また、十分な数の活性サイトを確保し得ても、反応に関与し得ない箇所に形成される活性サイト数が多くなったりして、活性サイトの形成箇所での反応物質の拡散が良好に進まず、想定しているだけの活性が十分に確保できない問題がある。従来のカーボンアロイ微粒子において、活性サイトが反応に関与し得ない箇所に形成される場合としては、微粒子の細孔内に活性サイトが形成されるケースが挙げられ、また、例えば、特許文献４に記載の燃料電池用電極触媒では、触媒である炭素化物がシェルを構成し、内部が空洞のナノシェル構造を取ることを主眼としているものの、内部も炭素化物で充填された構造のものも生じやすく、この場合、触媒の内部側に形成された活性サイトが反応に関与できなくなる。 As described above, in the conventional carbon alloy fine particles, the number of active sites is insufficient, or even if a sufficient number of active sites can be secured, the number of active sites formed in a place where the reaction cannot be involved is large. As a result, there is a problem in that the diffusion of the reactants at the site where the active site is formed does not proceed well and sufficient activity cannot be ensured. In the case of the conventional carbon alloy fine particles, the case where the active sites are formed at a place where the active sites cannot participate in the reaction includes a case where the active sites are formed in the pores of the fine particles. In the fuel cell electrode catalyst described, although the carbonized material as a catalyst constitutes a shell and the inside is mainly intended to take a hollow nanoshell structure, the inside is also likely to have a structure filled with a carbonized material, In this case, active sites formed on the inner side of the catalyst cannot participate in the reaction.
これに対し、本発明では、樹脂由来の炭素系触媒と担体とで燃料電池用触媒を構成し、前記炭素系触媒で担体表面を被覆することに加えて、燃料電池用触媒全体が特定の比表面積を有するようにし、これにより、炭素系触媒における活性サイトが良好に反応に関与でき、活性サイトの形成箇所での反応物質の拡散が良好に進むようにして、Ｐｔを使用することなく高い触媒活性の確保を可能としている。 On the other hand, in the present invention, a fuel cell catalyst is composed of a resin-derived carbon-based catalyst and a carrier, and in addition to coating the surface of the carrier with the carbon-based catalyst, the entire fuel cell catalyst has a specific ratio. The active site in the carbon-based catalyst can participate in the reaction satisfactorily, and the diffusion of the reactant at the site where the active site is formed proceeds favorably, so that high catalytic activity can be achieved without using Pt. It is possible to secure.
本発明の燃料電池用触媒は、樹脂由来の炭素系触媒と、担体とを有しており、炭素系触媒が、担体の表面の少なくとも一部を被覆している。このような構造の燃料電池用触媒であれば、炭素系触媒の有するより多くの活性サイトが反応物質と良好に接触できるようになるため、活性の高い燃料電池用触媒となる。 The fuel cell catalyst of the present invention has a carbon catalyst derived from a resin and a carrier, and the carbon catalyst covers at least a part of the surface of the carrier. In the fuel cell catalyst having such a structure, more active sites of the carbon-based catalyst can be satisfactorily brought into contact with the reactant, so that the fuel cell catalyst has high activity.
本発明の燃料電池用触媒では、活性サイト数を多く確保して、高い活性を確保する観点から、全体の比表面積（炭素系触媒および担体を含む燃料電池用触媒全体の比表面積。以下同じ。）を、１００ｍ２／ｇ以上とする。ただし、燃料電池用触媒の全体の比表面積が大きすぎると、炭素系触媒が担体の細孔内に担持されるようになり、活性サイトが担体の細孔内部に形成されることによって反応物質の拡散が低下し、所望の活性を確保できない虞がある。よって、燃料電池用触媒全体の比表面積は、８００ｍ２／ｇ以下とし、６００ｍ２／ｇ以下とすることが好ましい。 In the fuel cell catalyst of the present invention, from the viewpoint of securing a large number of active sites and ensuring high activity, the entire specific surface area (the specific surface area of the entire fuel cell catalyst including the carbon-based catalyst and the support; hereinafter the same). ) Is 100 m 2 / g or more. However, if the total specific surface area of the fuel cell catalyst is too large, the carbon-based catalyst comes to be supported in the pores of the support, and the active sites are formed in the pores of the support, so There is a possibility that the diffusion is lowered and the desired activity cannot be ensured. Therefore, the specific surface area of the whole fuel cell catalyst is preferably 800 m 2 / g or less, and preferably 600 m 2 / g or less.
本明細書でいう比表面積（燃料電池用触媒全体の比表面積、および後述する担体の比表面積）は、Ｎ２ガス吸着を利用した多点式のＢＥＴ測定装置（Ｓｙｓｍｅｘ社製「Ａｕｔｏｓｏｒｂ １」）を用いて、前処理として、Ｎ２ガスフロー中、１５０℃の環境下で１時間保持した後に測定することにより得られる値である。 The specific surface area in this specification (the specific surface area of the entire fuel cell catalyst and the specific surface area of the carrier described later) is a multipoint BET measuring device (“Autosorb 1” manufactured by Sysmex) using N 2 gas adsorption. Is a value obtained by measuring after maintaining for 1 hour in an environment of 150 ° C. in an N 2 gas flow as a pretreatment.
燃料電池用触媒に係る炭素系触媒の結晶子径は、例えば、３．０ｎｍ以上であることが好ましく、３．５ｎｍ以上であることがより好ましく、また、１０．０ｎｍ以下であることが好ましく、６．０ｎｍ以下であることがより好ましい。 The crystallite diameter of the carbon-based catalyst related to the fuel cell catalyst is, for example, preferably 3.0 nm or more, more preferably 3.5 nm or more, and preferably 10.0 nm or less. More preferably, it is 6.0 nm or less.
本明細書でいう燃料電池用触媒に係る炭素系触媒の結晶子径は、Ｘ線回折法により、２θ＝２６〜２７°付近の炭素（００２）ピークの半値幅から、シェラーの式を用いて求められる結晶子径Ｌｃ（００２）である。 The crystallite diameter of the carbon-based catalyst related to the fuel cell catalyst referred to in the present specification is calculated using the Scherrer equation from the half-value width of the carbon (002) peak around 2θ = 26 to 27 ° by the X-ray diffraction method. The required crystallite diameter Lc (002).
本発明の燃料電池用触媒に係る炭素系触媒は、樹脂由来のものであり、具体的には樹脂を炭素化して得られるものである。炭素系触媒の原料、すなわち炭素系触媒の前駆体となる樹脂としては、例えば、後述する本発明法により燃料電池用触媒を製造する場合に、担体や金属錯体などと均一に混合しやすいことから、フェノール樹脂、エポキシ樹脂、メラミン樹脂、ポリイミド樹脂、尿素樹脂、アルキド樹脂、アクリル樹脂などが好ましく、これらのうちの１種のみを用いてもよく、２種以上を併用してもよい。ただし、担体や金属錯体と均一に混合できるものであれば、前記例示の樹脂以外の樹脂を用いてもよい。 The carbon-based catalyst according to the fuel cell catalyst of the present invention is derived from a resin, and specifically is obtained by carbonizing a resin. As a raw material of the carbon-based catalyst, that is, a resin that is a precursor of the carbon-based catalyst, for example, when a fuel cell catalyst is produced by the method of the present invention described later, it is easy to uniformly mix with a carrier or a metal complex. Phenol resin, epoxy resin, melamine resin, polyimide resin, urea resin, alkyd resin, acrylic resin and the like are preferable, and only one of them may be used or two or more may be used in combination. However, as long as it can be uniformly mixed with the carrier and the metal complex, a resin other than the resin exemplified above may be used.
本発明の燃料電池用触媒に係る担体としては、例えば、カーボンブラック、アセチレンブラック、カーボンナノチューブなどが好適であり、これらのうちの１種のみを用いてもよく、２種以上を併用してもよい。 As the carrier related to the fuel cell catalyst of the present invention, for example, carbon black, acetylene black, carbon nanotubes and the like are suitable, and only one of these may be used, or two or more may be used in combination. Good.
担体の比表面積は、燃料電池用触媒全体の比表面積を大きくして、その活性を良好に高める観点から、２００ｍ２／ｇ以上であることが好ましく、２５０ｍ２／ｇ以上であることがより好ましい。また、燃料電池用触媒全体の比表面積を制限して、その活性を良好に高める観点から、担体の比表面積は、１２００ｍ２／ｇ以下であることが好ましく、８０００ｍ２／ｇ以下であることがより好ましい。 The specific surface area of the support is preferably 200 m 2 / g or more, and more preferably 250 m 2 / g or more, from the viewpoint of increasing the specific surface area of the entire fuel cell catalyst and improving its activity satisfactorily. . Further, from the viewpoint of favorably enhancing the activity by limiting the specific surface area of the entire fuel cell catalyst, the specific surface area of the support is preferably 1200 m 2 / g or less, and preferably 8000 m 2 / g or less. More preferred.
また、担体の平均粒子径は、１０〜１００ｎｍであることが好ましい。このような平均粒子径の担体を用い、後述する本発明法によって製造することで、燃料電池用触媒の平均粒子径を前記好適値に制御することができる。 Moreover, it is preferable that the average particle diameter of a support | carrier is 10-100 nm. By using the carrier having such an average particle size and producing the carrier by the method of the present invention described later, the average particle size of the fuel cell catalyst can be controlled to the above preferred value.
本明細書でいう担体の平均粒子径は、透過型電子顕微鏡を使用し、２０万倍の倍率で観察した担体１００個について求めた粒子径の数平均値を意味している。 The average particle diameter of the carrier referred to in this specification means the number average value of the particle diameters obtained for 100 carriers observed using a transmission electron microscope at a magnification of 200,000 times.
本発明の燃料電池用触媒は、担体表面の一部のみを炭素系触媒で被覆してもよく、担体表面の全面を炭素系触媒で被覆してもよいが、担体表面のうち、炭素系触媒で被覆される領域を大きくして、より良好な活性を確保する観点から、炭素系触媒と担体との合計１００質量％中の炭素系触媒の量で表される担持率（以下、単に「担持率」という）が、３５質量％以上であることが好ましく、４０質量％以上であることがより好ましい。ただし、担持率が高すぎると、例えば、担体表面を被覆する炭素系触媒の厚みが大きくなりすぎて、活性の向上効果が小さくなる虞があることから、燃料電池用触媒における担持率は、８０質量％以下であることが好ましく、６０質量％以下であることがより好ましい。 In the fuel cell catalyst of the present invention, only a part of the surface of the support may be coated with the carbon-based catalyst, or the entire surface of the support may be coated with the carbon-based catalyst. From the viewpoint of ensuring a better activity by enlarging the region covered with the catalyst, the loading ratio represented by the amount of the carbon-based catalyst in the total 100% by mass of the carbon-based catalyst and the support (hereinafter simply referred to as “supporting”). The ratio is preferably 35% by mass or more, and more preferably 40% by mass or more. However, if the loading rate is too high, for example, the thickness of the carbon-based catalyst that coats the surface of the carrier becomes too large and the effect of improving the activity may be reduced. The content is preferably at most mass%, more preferably at most 60 mass%.
本発明の燃料電池用触媒において、担体表面の面積のうち、炭素系触媒で被覆されている領域の面積割合（以下、「被覆率」という）は、１０％以上であることが好ましい。また、燃料電池用触媒における被覆率の好適上限値は、前記の通り、担体表面の全面が炭素系触媒で被覆されていてもよいことから、１００％である。 In the fuel cell catalyst of the present invention, the area ratio (hereinafter referred to as “coverage”) of the area covered with the carbon-based catalyst in the area of the support surface is preferably 10% or more. Further, the preferable upper limit value of the coverage in the fuel cell catalyst is 100% because the entire surface of the support may be coated with the carbon-based catalyst as described above.
本明細書でいう燃料電池用触媒の被覆率は、前記のＢＥＴ測定装置を用いて測定した炭素系触媒の比表面積を担体の比表面積で除し、１から引いた値を百分率に直したものである。 The coverage of the fuel cell catalyst referred to in the present specification is obtained by dividing the specific surface area of the carbon-based catalyst measured using the BET measuring apparatus by the specific surface area of the carrier, and subtracting the value from 1 to the percentage. It is.
本発明の燃料電池用触媒は、以下の（１）〜（５）のステップを有する本発明法により製造することができる。すなわち、本発明法によれば、担体の表面を樹脂由来の炭素系触媒で良好に被覆することが可能であり、活性の高い燃料電池用触媒を安定して製造することができる。 The fuel cell catalyst of the present invention can be produced by the method of the present invention having the following steps (1) to (5). That is, according to the method of the present invention, the surface of the support can be satisfactorily coated with the resin-derived carbon-based catalyst, and a highly active fuel cell catalyst can be stably produced.
本発明法の（１）のステップでは、炭素系触媒の原料となる樹脂が溶剤に溶解または分散した液に、少なくとも１種の金属錯体を添加する。 In step (1) of the method of the present invention, at least one metal complex is added to a liquid in which a resin that is a raw material for the carbon-based catalyst is dissolved or dispersed in a solvent.
炭素系触媒の原料となる樹脂を溶解または分散させるための溶剤には、例えば、メタノール、エタノール、イソプロパノールなどのアルコール類；アセトンなどのケトン類；キシレン、トルエンなどの芳香族炭化水素類；ジメチルエーテル、ジエチルエーテルなどのエーテル類；ジメチルホルムアミドなどのアミド類；などを使用することができる。 Solvents for dissolving or dispersing the resin used as the raw material for the carbon-based catalyst include, for example, alcohols such as methanol, ethanol and isopropanol; ketones such as acetone; aromatic hydrocarbons such as xylene and toluene; dimethyl ether, Ethers such as diethyl ether; Amides such as dimethylformamide; and the like can be used.
炭素系触媒の原料となる樹脂が溶剤に溶解または分散した液において、前記樹脂の量は、例えば、１〜１０質量％とすることが好ましい。 In the liquid in which the resin used as the raw material for the carbon-based catalyst is dissolved or dispersed in the solvent, the amount of the resin is preferably 1 to 10% by mass, for example.
炭素系触媒の原料となる樹脂が溶剤に溶解または分散した液に添加する金属錯体としては、例えば、コバルトフェナントロリン錯体、コバルトフタロシアニン錯体、鉄フェナントロリン錯体、鉄フタロシアニン錯体、ニッケルフェナントロリン錯体、ニッケルフタロシアニン錯体などが挙げられ、これらのうちの１種のみを用いてもよく、２種以上を併用してもよい。 Examples of the metal complex added to the liquid in which the resin used as the raw material for the carbon-based catalyst is dissolved or dispersed in the solvent include a cobalt phenanthroline complex, a cobalt phthalocyanine complex, an iron phenanthroline complex, an iron phthalocyanine complex, a nickel phenanthroline complex, and a nickel phthalocyanine complex. 1 type of these may be used, and 2 or more types may be used in combination.
炭素系触媒の原料となる樹脂が溶剤に溶解または分散した液に添加する金属錯体の量は、例えば、最終的に形成される炭素系触媒１００質量部に対して、５〜２０質量部となる量とすることが好ましい。 The amount of the metal complex added to the liquid in which the resin that is the raw material for the carbon-based catalyst is dissolved or dispersed in the solvent is, for example, 5 to 20 parts by mass with respect to 100 parts by mass of the carbon-based catalyst that is finally formed. It is preferable to use an amount.
本発明法の（２）のステップでは、前記（１）のステップで得られた液から溶剤を除去して、樹脂と金属錯体との混合物を調製する。溶剤を除去する方法については特に制限はなく、例えば、公知の減圧乾燥法などにより行えばよい。また、乾燥条件についても特に制限はなく、例えば使用した溶剤の沸点などを考慮して適宜設定すればよい。 In the step (2) of the method of the present invention, the solvent is removed from the liquid obtained in the step (1) to prepare a mixture of resin and metal complex. The method for removing the solvent is not particularly limited, and may be performed by, for example, a known vacuum drying method. Also, the drying conditions are not particularly limited, and may be set as appropriate in consideration of, for example, the boiling point of the solvent used.
本発明法の（３）のステップでは、（２）のステップで得られた樹脂と金属錯体との混合物に、少なくとも１種の担体を添加して、樹脂と金属錯体と担体との混合物を調製する。なお、担体の使用量は、樹脂１００質量部に対して２０〜１５０質量部とすることが好ましく、このような比率で樹脂と担体とを使用することで、燃料電池用触媒の担持率や被覆率を前記の好適値に制御することができる。 In step (3) of the method of the present invention, at least one carrier is added to the mixture of resin and metal complex obtained in step (2) to prepare a mixture of resin, metal complex and carrier. To do. The amount of the carrier used is preferably 20 to 150 parts by mass with respect to 100 parts by mass of the resin. By using the resin and the carrier at such a ratio, the supporting rate of the fuel cell catalyst and the coating amount can be increased. The rate can be controlled to the preferred value.
本発明法の（４）のステップでは、（３）のステップで得られた樹脂と金属錯体と担体との混合物を、非酸化性雰囲気中で焼成する。この（４）のステップによって、担体表面を樹脂で被覆しつつ、この樹脂を炭素化する。 In the step (4) of the method of the present invention, the mixture of the resin, the metal complex and the carrier obtained in the step (3) is baked in a non-oxidizing atmosphere. By the step (4), the resin is carbonized while the support surface is coated with the resin.
焼成を行う系内を非酸化雰囲気とするための非酸化性ガスとしては、例えば、窒素ガス、アルゴンガス、アンモニアガス、水素ガスなどが挙げられる。焼成を行う系内は、これらの非酸化性ガスのうちの１種のみ（純窒素ガス、純アルゴンガス、純アンモニアガス、純水素ガス）を含んでいてもよく、２種以上（アンモニアを含有する窒素ガス、水素を含有する窒素ガス、アンモニアを含有するアルゴンガスなど）を含んでいてもよいが、純窒素ガスを含んでいることが特に好ましい。 Examples of the non-oxidizing gas for making the inside of the firing system a non-oxidizing atmosphere include nitrogen gas, argon gas, ammonia gas, and hydrogen gas. The system for firing may contain only one of these non-oxidizing gases (pure nitrogen gas, pure argon gas, pure ammonia gas, pure hydrogen gas) or two or more (containing ammonia). A nitrogen gas containing hydrogen, a nitrogen gas containing hydrogen, an argon gas containing ammonia, etc.), but it is particularly preferred that pure nitrogen gas is contained.
樹脂と金属錯体と担体との混合物を焼成する際の温度は、樹脂を良好に炭素化する観点から、６００℃以上であり、８００℃以上であることが好ましい。ただし、焼成温度が高すぎると、樹脂から形成される炭素化物の結晶化度が高くなりすぎて活性サイトが減少し、所望の性能が得られなくなる虞がある。よって、樹脂と金属錯体と担体との混合物を焼成する際の温度は、１２００℃以下であり、１０００℃以下であることが好ましい。 The temperature at which the mixture of the resin, the metal complex and the carrier is baked is 600 ° C. or higher and preferably 800 ° C. or higher from the viewpoint of satisfactorily carbonizing the resin. However, if the firing temperature is too high, the degree of crystallinity of the carbonized product formed from the resin becomes too high, reducing the active sites, and the desired performance may not be obtained. Therefore, the temperature at which the mixture of the resin, the metal complex, and the carrier is baked is 1200 ° C. or less, and preferably 1000 ° C. or less.
また、樹脂と金属錯体と担体との混合物を焼成する際の時間は、例えば、１〜６時間であることが好ましい。 Moreover, it is preferable that the time at the time of baking the mixture of resin, a metal complex, and a support | carrier is 1 to 6 hours, for example.
本発明法の（５）のステップでは、（４）のステップで得られた焼成物から金属を除去する。このステップで除去する金属は金属錯体由来のものであり、この金属を除去することで、樹脂由来の炭素化物に活性サイトが形成されて、炭素系触媒となる。 In step (5) of the method of the present invention, the metal is removed from the fired product obtained in step (4). The metal to be removed in this step is derived from a metal complex. By removing this metal, an active site is formed in the carbonized product derived from the resin, and becomes a carbon-based catalyst.
焼成物から金属を除去する方法については特に制限はなく、例えば、塩酸、硫酸、硝酸などの酸性溶液で洗浄する方法などが挙げられる。また、酸性溶液で洗浄する場合、金属の除去作用をより高めるために、煮沸してもよい。 There is no restriction | limiting in particular about the method of removing a metal from baking products, For example, the method etc. which wash | clean with acidic solutions, such as hydrochloric acid, a sulfuric acid, and nitric acid, are mentioned. Moreover, when wash | cleaning with an acidic solution, in order to improve the metal removal effect | action, you may boil.
（５）のステップを経て得られた生成物（燃料電池用触媒）については、例えば、前記の酸性溶液で洗浄することで金属を除去した場合には、酸性溶液から濾別し、水洗、乾燥すればよい。 For the product (catalyst for fuel cell) obtained through the step (5), for example, when the metal is removed by washing with the acidic solution, it is filtered from the acidic solution, washed with water and dried. do it.
本発明の燃料電池用触媒は、燃料電池用の膜電極接合体のカソード触媒層用の触媒として使用される。 The catalyst for a fuel cell of the present invention is used as a catalyst for a cathode catalyst layer of a membrane electrode assembly for a fuel cell.
すなわち、本発明の膜電極接合体は、カソード触媒層と、アノード触媒層と、前記カソード触媒層と前記アノード触媒層との間に間挿されたプロトン導電膜とからなり、前記カソード触媒層が、本発明の燃料電池用触媒を含んでいればよく、その他の構成および構造については特に制限はなく、従来から知られている燃料電池（メタノールを燃料とする直接メタノール型電池、水素を燃料とする固体高分子型燃料電池など）用の膜電極接合体で採用されている構成および構造を適用することができる。 That is, the membrane electrode assembly of the present invention comprises a cathode catalyst layer, an anode catalyst layer, and a proton conductive film interposed between the cathode catalyst layer and the anode catalyst layer. As long as the fuel cell catalyst of the present invention is included, there is no particular limitation on the other configurations and structures. Conventionally known fuel cells (direct methanol type fuel cell using methanol as fuel, hydrogen as fuel) The structure and structure employed in the membrane / electrode assembly for a polymer electrolyte fuel cell, etc.) can be applied.
また、本発明の燃料電池は、カソード触媒層と、アノード触媒層と、前記カソード触媒層と前記アノード触媒層との間に間挿されたプロトン導電膜とからなる膜電極接合体を有しており、前記カソード触媒層が、本発明の燃料電池用触媒を含んでいればよく、その他の構成および構造については特に制限はなく、従来から知られている燃料電池（メタノールを燃料とする直接メタノール型電池、水素を燃料とする固体高分子型燃料電池など）で採用されている構成および構造を適用することができる。 The fuel cell of the present invention has a membrane electrode assembly comprising a cathode catalyst layer, an anode catalyst layer, and a proton conductive film interposed between the cathode catalyst layer and the anode catalyst layer. The cathode catalyst layer only needs to contain the fuel cell catalyst of the present invention, and there is no particular limitation on the other configurations and structures. Conventionally known fuel cells (direct methanol using methanol as fuel) The configuration and the structure employed in a type cell, a solid polymer type fuel cell using hydrogen as a fuel, and the like can be applied.
以下、実施例に基づいて本発明を詳細に述べる。ただし、下記実施例は、本発明を制限するものではない。 Hereinafter, the present invention will be described in detail based on examples. However, the following examples do not limit the present invention.
実施例１
５０ｍｌのエタノール中に炭素系触媒前駆体であるフェノール樹脂：１．０ｇを分散させた液に、コバルトフェナントロリン錯体０．００２ｍｏｌを添加し、攪拌した。この混合液を減圧乾燥してフェノール樹脂とコバルトフェナントロリン錯体との混合物とし、更にこの混合物に、担体であるカーボンブラック（ライオン社製「ケッチェンブラックＥＣ３００Ｊ」、比表面積：８００ｍ２／ｇ）：０．４ｇを加え、乳鉢中で均一に混合した。この混合物を石英ボートに均一に入れ、管状電気炉へ投入した。この管状電気炉内に窒素ガスを１００ｍｌ／ｍｉｎ．の速度で流入させて非酸化性雰囲気にした状態で、９００℃の温度で焼成を行った。次に、得られた焼成物を３ｍｏｌ／ｌ濃度の塩酸水溶液中で煮沸することで余分な金属成分を除去した後、ろ過、洗浄、乾燥して、燃料電池用触媒を得た。この燃料電池用触媒の比表面積は１５０ｍ２／ｇであった。
Example 1
0.002 mol of cobalt phenanthroline complex was added to a liquid in which 1.0 g of a phenolic resin as a carbon-based catalyst precursor was dispersed in 50 ml of ethanol, followed by stirring. This mixed solution was dried under reduced pressure to obtain a mixture of a phenol resin and a cobalt phenanthroline complex. Further, carbon black as a carrier (“Ketjen Black EC300J” manufactured by Lion, specific surface area: 800 m 2 / g): 0 .4 g was added and mixed uniformly in the mortar. This mixture was uniformly placed in a quartz boat and put into a tubular electric furnace. In this tubular electric furnace, nitrogen gas was supplied at 100 ml / min. Firing was carried out at a temperature of 900 ° C. in a non-oxidizing atmosphere by flowing at a rate of 5 ° C. Next, the obtained fired product was boiled in a 3 mol / l hydrochloric acid aqueous solution to remove excess metal components, and then filtered, washed, and dried to obtain a fuel cell catalyst. The specific surface area of this fuel cell catalyst was 150 m 2 / g.
なお、この燃料電池用触媒について、透過型電子顕微鏡（ＴＥＭ）により表面観察を行った。これにより得られたＴＥＭ写真を図１に、また、燃料電池用触媒に使用した担体であるカーボンブラックのＴＥＭ写真を図２に示す。図１では、担体であるカーボンブラックの表面に炭素系触媒（図中で示している線状の部分）が存在していることが確認でき、担体の表面が樹脂由来の炭素系触媒で被覆された構造を有していることが分かる。 The surface of the fuel cell catalyst was observed with a transmission electron microscope (TEM). FIG. 1 shows a TEM photograph obtained in this manner, and FIG. 2 shows a TEM photograph of carbon black, which is a carrier used for a fuel cell catalyst. In FIG. 1, it can be confirmed that the carbon-based catalyst (the linear portion shown in the figure) exists on the surface of the carbon black as the support, and the surface of the support is coated with the carbon-based catalyst derived from the resin. It can be seen that it has a structure.
実施例２
担体であるカーボンブラックの添加量を０．８ｇに変更した以外は、実施例１と同様にして燃料電池用触媒を製造した。この燃料電池用触媒について、ＴＥＭにより表面観察を行い、担体の表面が樹脂由来の炭素系触媒で被覆された構造を有していることを確認した。また、この燃料電池用触媒の比表面積は７００ｍ２／ｇであった。
Example 2
A fuel cell catalyst was produced in the same manner as in Example 1 except that the amount of carbon black as the carrier was changed to 0.8 g. The surface of this fuel cell catalyst was observed by TEM, and it was confirmed that the surface of the carrier had a structure coated with a resin-derived carbon-based catalyst. The specific surface area of this fuel cell catalyst was 700 m 2 / g.
実施例３
炭素系触媒前駆体をエポキシ樹脂：１．０ｇに変更した以外は、実施例１と同様にして燃料電池用触媒を製造した。この燃料電池用触媒について、ＴＥＭにより表面観察を行い、担体の表面が樹脂由来の炭素系触媒で被覆された構造を有していることを確認した。また、この燃料電池用触媒の比表面積は１５５ｍ２／ｇであった。
Example 3
A fuel cell catalyst was produced in the same manner as in Example 1 except that the carbon-based catalyst precursor was changed to 1.0 g of epoxy resin. The surface of this fuel cell catalyst was observed by TEM, and it was confirmed that the surface of the carrier had a structure coated with a resin-derived carbon-based catalyst. The specific surface area of this fuel cell catalyst was 155 m 2 / g.
実施例４
炭素系触媒前駆体をメラミン樹脂：１．０ｇに変更した以外は、実施例１と同様にして燃料電池用触媒を製造した。この燃料電池用触媒について、ＴＥＭにより表面観察を行い、担体の表面が樹脂由来の炭素系触媒で被覆された構造を有していることを確認した。また、この燃料電池用触媒の比表面積は１６７ｍ２／ｇであった。
Example 4
A fuel cell catalyst was produced in the same manner as in Example 1 except that the carbon-based catalyst precursor was changed to 1.0 g of melamine resin. The surface of this fuel cell catalyst was observed by TEM, and it was confirmed that the surface of the carrier had a structure coated with a resin-derived carbon-based catalyst. The specific surface area of this fuel cell catalyst was 167 m 2 / g.
実施例５
炭素系触媒前駆体をポリイミド樹脂：１．０ｇに変更した以外は、実施例１と同様にして燃料電池用触媒を製造した。この燃料電池用触媒について、ＴＥＭにより表面観察を行い、担体の表面が樹脂由来の炭素系触媒で被覆された構造を有していることを確認した。また、この燃料電池用触媒の比表面積は１３０ｍ２／ｇであった。
Example 5
A fuel cell catalyst was produced in the same manner as in Example 1 except that the carbon-based catalyst precursor was changed to 1.0 g of polyimide resin. The surface of this fuel cell catalyst was observed by TEM, and it was confirmed that the surface of the carrier had a structure coated with a resin-derived carbon-based catalyst. The specific surface area of this fuel cell catalyst was 130 m 2 / g.
実施例６
炭素系触媒前駆体を尿素樹脂：１．０ｇに変更した以外は、実施例１と同様にして燃料電池用触媒を製造した。この燃料電池用触媒について、ＴＥＭにより表面観察を行い、担体の表面が樹脂由来の炭素系触媒で被覆された構造を有していることを確認した。また、この燃料電池用触媒の比表面積は１５０ｍ２／ｇであった。
Example 6
A fuel cell catalyst was produced in the same manner as in Example 1 except that the carbon-based catalyst precursor was changed to 1.0 g of urea resin. The surface of this fuel cell catalyst was observed by TEM, and it was confirmed that the surface of the carrier had a structure coated with a resin-derived carbon-based catalyst. The specific surface area of this fuel cell catalyst was 150 m 2 / g.
実施例７
炭素系触媒前駆体をアルキド樹脂：１．０ｇに変更した以外は、実施例１と同様にして燃料電池用触媒を製造した。この燃料電池用触媒について、ＴＥＭにより表面観察を行い、担体の表面が樹脂由来の炭素系触媒で被覆された構造を有していることを確認した。また、この燃料電池用触媒の比表面積は１９１ｍ２／ｇであった。
Example 7
A fuel cell catalyst was produced in the same manner as in Example 1 except that the carbon-based catalyst precursor was changed to 1.0 g of alkyd resin. The surface of this fuel cell catalyst was observed by TEM, and it was confirmed that the surface of the carrier had a structure coated with a resin-derived carbon-based catalyst. The specific surface area of this fuel cell catalyst was 191 m 2 / g.
実施例８
炭素系触媒前駆体をアクリル樹脂：１．０ｇに変更した以外は、実施例１と同様にして燃料電池用触媒を製造した。この燃料電池用触媒について、ＴＥＭにより表面観察を行い、担体の表面が樹脂由来の炭素系触媒で被覆された構造を有していることを確認した。また、この燃料電池用触媒の比表面積は１２０ｍ２／ｇであった。
Example 8
A fuel cell catalyst was produced in the same manner as in Example 1 except that the carbon-based catalyst precursor was changed to 1.0 g of acrylic resin. The surface of this fuel cell catalyst was observed by TEM, and it was confirmed that the surface of the carrier had a structure coated with a resin-derived carbon-based catalyst. The specific surface area of this fuel cell catalyst was 120 m 2 / g.
実施例９
担体であるカーボンブラックを、キャボット社製「バルカンＸＣ７２Ｒ」（比表面積：２７０ｍ２／ｇ）に変更した以外は、実施例１と同様にして燃料電池用触媒を製造した。この燃料電池用触媒について、ＴＥＭにより表面観察を行い、担体の表面が樹脂由来の炭素系触媒で被覆された構造を有していることを確認した。また、この燃料電池用触媒の比表面積は１１０ｍ２／ｇであった。
Example 9
A fuel cell catalyst was produced in the same manner as in Example 1 except that the carbon black as the support was changed to “Vulcan XC72R” (specific surface area: 270 m 2 / g) manufactured by Cabot. The surface of this fuel cell catalyst was observed by TEM, and it was confirmed that the surface of the carrier had a structure coated with a resin-derived carbon-based catalyst. The specific surface area of this fuel cell catalyst was 110 m 2 / g.
実施例１０
担体であるカーボンブラックの添加量を０．６ｇに変更した以外は、実施例１と同様にして燃料電池用触媒を製造した。この燃料電池用触媒の比表面積は１８０ｍ２／ｇであった。
Example 10
A fuel cell catalyst was produced in the same manner as in Example 1 except that the amount of carbon black as a support was changed to 0.6 g. The specific surface area of this fuel cell catalyst was 180 m 2 / g.
実施例１１
担体であるカーボンブラックの添加量を１．０ｇに変更した以外は、実施例１と同様にして燃料電池用触媒を製造した。この燃料電池用触媒の比表面積は３００ｍ２／ｇであった。
Example 11
A fuel cell catalyst was produced in the same manner as in Example 1 except that the amount of carbon black as a support was changed to 1.0 g. The specific surface area of this fuel cell catalyst was 300 m 2 / g.
実施例１２
担体であるカーボンブラックの添加量を１．２ｇに変更した以外は、実施例１と同様にして燃料電池用触媒を製造した。この燃料電池用触媒の比表面積は３５０ｍ２／ｇであった。
Example 12
A fuel cell catalyst was produced in the same manner as in Example 1 except that the amount of carbon black as a support was changed to 1.2 g. The specific surface area of this fuel cell catalyst was 350 m 2 / g.
実施例１３
担体であるカーボンブラックの添加量を１．５ｇに変更した以外は、実施例１と同様にして燃料電池用触媒を製造した。この燃料電池用触媒の比表面積は３８０ｍ２／ｇであった。
Example 13
A fuel cell catalyst was produced in the same manner as in Example 1 except that the amount of carbon black as a support was changed to 1.5 g. The specific surface area of this fuel cell catalyst was 380 m 2 / g.
比較例１
担体を添加しなかった以外は、実施例１と同様にして燃料電池用触媒を製造した。この燃料電池用触媒の比表面積は８０ｍ２／ｇであった。
Comparative Example 1
A fuel cell catalyst was produced in the same manner as in Example 1 except that no carrier was added. The specific surface area of this fuel cell catalyst was 80 m 2 / g.
比較例２
担体であるカーボンブラックの添加量を２．０ｇに変更した以外は、実施例１と同様にして燃料電池用触媒を製造した。この燃料電池用触媒の比表面積は９２０ｍ２／ｇであった。
Comparative Example 2
A fuel cell catalyst was produced in the same manner as in Example 1 except that the amount of carbon black as a support was changed to 2.0 g. The specific surface area of this fuel cell catalyst was 920 m 2 / g.
比較例３
担体であるカーボンブラックを、比表面積が８０ｍ２／ｇのものに変更した以外は、実施例１と同様にして燃料電池用触媒を製造した。この燃料電池用触媒の比表面積は７０ｍ２／ｇであった。
Comparative Example 3
A fuel cell catalyst was produced in the same manner as in Example 1 except that the carbon black as the support was changed to one having a specific surface area of 80 m 2 / g. The specific surface area of this fuel cell catalyst was 70 m 2 / g.
比較例４
担体であるカーボンブラックを、比表面積が１３００ｍ２／ｇのものに変更した以外は、実施例１と同様にして燃料電池用触媒を製造した。この燃料電池用触媒の比表面積は９００ｍ２／ｇであった。
Comparative Example 4
A fuel cell catalyst was produced in the same manner as in Example 1 except that the carbon black as the support was changed to one having a specific surface area of 1300 m 2 / g. The specific surface area of this fuel cell catalyst was 900 m 2 / g.
実施例および比較例の燃料電池用触媒を用いて標準的な３電極セルを組み、これらの酸素還元触媒活性を回転ディスク電極法により評価した。 Standard three-electrode cells were assembled using the fuel cell catalysts of Examples and Comparative Examples, and their oxygen reduction catalytic activity was evaluated by the rotating disk electrode method.
まず、純水中に２．０ｍｇ／ｍｌで分散させた燃料電池用触媒をマイクロピペットで２０μｌ取り、これを回転ディスク用グラッシーカーボン電極上に塗布し、乾燥した後、この上にイオン伝導性ポリマー分散液［Ａｌｄｒｉｃｈ社製「Ｎａｆｉｏｎ（登録商標）」］を５μｌ塗布し乾燥したものを作用極とした。また、対極にはＰｔ線を、参照極にはＡｇ／ＡｇＣｌ電極を用意した。そして、これらの作用極、対極および参照極を、０．５ｍｏｌ／ｌ濃度の硫酸水溶液中に浸漬して３電極セルとし、前記硫酸水溶液中に窒素を吹き込んで飽和させた状態で、０Ｖから１．２Ｖの間で速度２００ｍＶ／秒で電位を走査するサイクルを１０サイクル行い、燃料電池用触媒の表面を洗浄した。次に、作用極を４００ｒｐｍの速度で回転させつつ、０Ｖから１．１Ｖの間で速度１０ｍＶ／秒で電位を走査するサイクルを１サイクル行い、バックグランド電流を測定した。その後、硫酸水溶液中への窒素の吹き込みを停止し、代わりに酸素を吹き込んで飽和させた状態で、作用極を４００ｒｐｍの速度で回転させつつ、０Ｖから１．１Ｖの間で速度１０ｍＶ／秒で電位を走査するサイクルを１サイクル行い、燃料電池用触媒の酸素還元電位を測定した。得られた酸素還元電流からバックグラウンド電流を除き、１μＡの電流が流れたときの電位を求めることで、燃料電池用触媒の酸素還元活性を評価した。すなわち、１μＡの電流が流れたときの電位が高く、酸素の酸化還元電位である１．２３Ｖに近いほど、燃料電池用触媒の酸素還元活性が高いと評価できる。 First, 20 μl of a fuel cell catalyst dispersed at 2.0 mg / ml in pure water is taken with a micropipette, applied onto a glassy carbon electrode for a rotating disk, dried, and then an ion conductive polymer is deposited thereon. A working electrode was prepared by applying 5 μl of a dispersion (“Nafion (registered trademark)” manufactured by Aldrich) and drying it. A Pt line was prepared for the counter electrode, and an Ag / AgCl electrode was prepared for the reference electrode. Then, these working electrode, counter electrode, and reference electrode are immersed in a 0.5 mol / l sulfuric acid aqueous solution to form a three-electrode cell, and nitrogen is blown into the sulfuric acid aqueous solution to saturate it. 10 cycles of scanning the electric potential at a speed of 200 mV / sec between 2 V were performed to clean the surface of the fuel cell catalyst. Next, while rotating the working electrode at a speed of 400 rpm, one cycle of scanning the potential at a speed of 10 mV / sec between 0 V and 1.1 V was performed, and the background current was measured. Thereafter, the nitrogen blowing into the sulfuric acid aqueous solution was stopped, and instead the oxygen was blown and saturated, and while rotating the working electrode at a speed of 400 rpm, the speed was changed from 0 V to 1.1 V at a speed of 10 mV / sec. One cycle of scanning the potential was performed, and the oxygen reduction potential of the fuel cell catalyst was measured. The oxygen reduction activity of the fuel cell catalyst was evaluated by removing the background current from the obtained oxygen reduction current and determining the potential when a current of 1 μA flows. That is, it can be evaluated that the oxygen reduction activity of the fuel cell catalyst is higher as the potential when a current of 1 μA flows is higher and closer to the oxygen redox potential of 1.23 V.
実施例１、２、１０〜１３および比較例１、２の燃料電池用触媒の酸素還元活性評価結果を、燃料電池用触媒全体の比表面積、炭素系触媒の結晶子径、並びに燃料電池用触媒における担持率および被覆率と併せて表１に示す。 The results of evaluating the oxygen reduction activity of the fuel cell catalysts of Examples 1, 2, 10 to 13 and Comparative Examples 1 and 2 are shown as follows. The specific surface area of the entire fuel cell catalyst, the crystallite diameter of the carbon-based catalyst, and the fuel cell catalyst The results are shown in Table 1 together with the loading and covering ratio.
表１に示す通り、担体を有しておらず、全体の比表面積が８０ｍ２／ｇの比較例１の燃料電池用触媒は、１μＡの酸素還元電流が流れる電位が０．６Ｖであるのに対し、担体として比表面積が８００ｍ２／ｇのカーボンブラックを用いた実施例１の燃料電池用触媒は、全体の比表面積が１５０ｍ２／ｇと比較例１の燃料電池用触媒よりも大きく、１μＡの酸素還元電流が流れる電位が０．８５Ｖと、比較例１の燃料電池用触媒よりも０．２５Ｖも高い電位で１μＡの酸素還元電流が得られており、高い活性を有している。 As shown in Table 1, the fuel cell catalyst of Comparative Example 1 having no carrier and having an overall specific surface area of 80 m 2 / g has a potential at which an oxygen reduction current of 1 μA flows is 0.6V. On the other hand, the fuel cell catalyst of Example 1 using carbon black having a specific surface area of 800 m 2 / g as a carrier has an overall specific surface area of 150 m 2 / g, which is larger than that of the fuel cell catalyst of Comparative Example 1 and 1 μA. An oxygen reduction current of 1 μA is obtained at a potential of 0.85 V, which is higher by 0.25 V than the fuel cell catalyst of Comparative Example 1, and has high activity.
また、全体の比表面積が７００ｍ２／ｇである実施例２の燃料電池用触媒は、１μＡの酸素還元電流が流れる電位が０．８３Ｖであり、全体の比表面積が９２０ｍ２／ｇである比較例２の燃料電池用触媒における１μＡの酸素還元電流が流れる電位（０．７５Ｖ）よりも０．０８Ｖも高い。これらの結果から、担体を使用し、その表面を樹脂由来の炭素系触媒で被覆すると共に、全体の比表面積を適正な値に制御することで、燃料電池用触媒の活性を飛躍的に高め得ることが分かる。 Further, the fuel cell catalyst of Example 2 having an overall specific surface area of 700 m 2 / g has a potential at which an oxygen reduction current of 1 μA flows is 0.83 V, and the overall specific surface area is 920 m 2 / g. It is 0.08 V higher than the potential (0.75 V) at which the 1 μA oxygen reduction current flows in the fuel cell catalyst of Example 2. From these results, it is possible to dramatically increase the activity of the fuel cell catalyst by using a support and coating the surface with a resin-derived carbon catalyst and controlling the entire specific surface area to an appropriate value. I understand that.
更に、全体の比表面積が適正であり、かつ担持率および被覆率を好適な範囲内で実施例１、２の燃料電池用触媒から変えた実施例１０〜１３の燃料電池用触媒も、担体を使用していない比較例１の燃料電池用触媒や、全体の比表面積が不適であり、かつ担持率および被覆率も好適値でない比較例２の燃料電池用触媒よりも、１μＡの酸素還元電流が流れる電位が高く、高い活性を有している。 Furthermore, the fuel cell catalysts of Examples 10 to 13 in which the entire specific surface area is appropriate and the loading rate and the covering rate are changed from the fuel cell catalysts of Examples 1 and 2 within a suitable range also include the carrier. Oxygen reduction current of 1 μA is higher than that of the fuel cell catalyst of Comparative Example 1 that is not used, or the fuel cell catalyst of Comparative Example 2 in which the overall specific surface area is unsuitable and the loading and coverage are not suitable values. The flowing electric potential is high and it has high activity.
次に、実施例３〜８の燃料電池用触媒の酸素還元活性評価結果を、燃料電池用触媒全体の比表面積、炭素系触媒の結晶子径、並びに燃料電池用触媒における担持率および被覆率と併せて表２に示す。 Next, the oxygen reduction activity evaluation results of the fuel cell catalysts of Examples 3 to 8 are shown as follows: the specific surface area of the entire fuel cell catalyst, the crystallite diameter of the carbon-based catalyst, and the loading rate and coverage in the fuel cell catalyst. The results are also shown in Table 2.
エポキシ樹脂由来の炭素系触媒を有する実施例３の燃料電池用触媒、メラミン樹脂由来の炭素系触媒を有する実施例４の燃料電池用触媒、ポリイミド樹脂由来の炭素系触媒を有する実施例５の燃料電池用触媒、尿素樹脂由来の炭素系触媒を有する実施例６の燃料電池用触媒、アルキド樹脂由来の炭素系触媒を有する実施例７の燃料電池用触媒、およびアクリル樹脂由来の炭素系触媒を有する実施例８の燃料電池用触媒は、１μＡの酸素還元電流が流れる電位が０．８２〜０．８４Ｖであり、フェノール樹脂由来の炭素系触媒を有する実施例１の燃料電池用触媒における前記電位０．８５Ｖとほぼ同等の値を示している。これらの結果から、各実施例で使用した各樹脂が、燃料電池用触媒における炭素系触媒の前駆体として良好に機能していることが分かる。 Fuel cell catalyst of Example 3 having a carbon-based catalyst derived from an epoxy resin, catalyst for fuel cell of Example 4 having a carbon-based catalyst derived from melamine resin, fuel of Example 5 having a carbon-based catalyst derived from a polyimide resin A catalyst for a battery, a catalyst for a fuel cell of Example 6 having a carbon-based catalyst derived from a urea resin, a catalyst for a fuel cell of Example 7 having a carbon-based catalyst derived from an alkyd resin, and a carbon-based catalyst derived from an acrylic resin The fuel cell catalyst of Example 8 has a potential at which an oxygen reduction current of 1 μA flows from 0.82 to 0.84 V, and the potential 0 in the fuel cell catalyst of Example 1 having a phenolic resin-derived carbon-based catalyst. The value is almost equivalent to .85V. From these results, it can be seen that each resin used in each example functions well as a precursor of the carbon-based catalyst in the fuel cell catalyst.
次に、実施例１、９および比較例３、４の燃料電池用触媒の酸素還元活性評価結果を、燃料電池用触媒全体および使用した担体の比表面積、炭素系触媒の結晶子径、並びに燃料電池用触媒における担持率および被覆率と併せて表３に示す。 Next, the results of evaluating the oxygen reduction activity of the fuel cell catalysts of Examples 1 and 9 and Comparative Examples 3 and 4 are shown. The specific surface area of the entire fuel cell catalyst and the carrier used, the crystallite diameter of the carbon-based catalyst, and the fuel The results are shown in Table 3 together with the supporting rate and the covering rate in the battery catalyst.
比表面積が好適値にある担体を使用した実施例１、９の燃料電池用触媒は、全体の比表面積が適正な値となっており、それに起因して、１μＡの酸素還元電流が流れる電位が０．８５Ｖ（実施例１）、０．８２Ｖ（実施例９）と高く、高い活性を示している。これに対し、比表面積が好適値にない担体を使用した比較例３、４の燃料電池用触媒は、全体の比表面積が不適な値となっており、それに起因して、１μＡの酸素還元電流が流れる電位が０．７４Ｖ（比較例３）、０．７５Ｖ（比較例４）と、実施例の燃料電池用触媒よりも低く、活性が劣っている。これらの結果から、使用する担体の比表面積の選択によって、燃料電池用触媒全体の比表面積を制御可能であることが分かる。 The fuel cell catalysts of Examples 1 and 9 using the carrier having a suitable specific surface area have appropriate values for the entire specific surface area, and as a result, the potential at which an oxygen reduction current of 1 μA flows is obtained. 0.85V (Example 1) and 0.82V (Example 9) are high, indicating high activity. On the other hand, the fuel cell catalysts of Comparative Examples 3 and 4 using a carrier whose specific surface area is not at a suitable value have an inappropriate value for the entire specific surface area, and as a result, an oxygen reduction current of 1 μA. Is lower than the fuel cell catalyst of the example, and is inferior in activity, 0.74 V (Comparative Example 3) and 0.75 V (Comparative Example 4). From these results, it can be seen that the specific surface area of the entire fuel cell catalyst can be controlled by selecting the specific surface area of the carrier used.
以上の通り、本発明の燃料電池用触媒は、Ｐｔに比べて安価であり資源的制約の少ない炭素材料を有効成分としつつ高い活性を備えていることから、優れた電池特性を有する燃料電池および該燃料電池に使用される膜電極接合体を構成することができる。 As described above, the fuel cell catalyst of the present invention has a high activity while being made of a carbon material that is less expensive and less resource-constrained than Pt, and has an excellent component. A membrane electrode assembly used in the fuel cell can be constituted.
本発明の燃料電池用触媒は、直接メタノール型燃料電池や固体高分子型燃料電池のカソード用触媒として有用である。また、本発明の燃料電池は、例えば、各種機器の電源として有用である。 The catalyst for a fuel cell of the present invention is useful as a catalyst for a cathode of a direct methanol fuel cell or a polymer electrolyte fuel cell. The fuel cell of the present invention is useful as a power source for various devices, for example.
Claims (7)
前記炭素系触媒は、前記担体の表面の少なくとも一部を被覆しており、
比表面積が１００〜８００ｍ２／ｇであることを特徴とする燃料電池用触媒。 A fuel cell catalyst comprising a resin-derived carbon-based catalyst and a carrier,
The carbon-based catalyst covers at least a part of the surface of the support,
A fuel cell catalyst having a specific surface area of 100 to 800 m 2 / g.
（１）炭素系触媒の原料となる樹脂が溶剤に溶解または分散した液に、少なくとも１種の金属錯体を添加するステップと、
（２）前記（１）のステップで得られた液から溶剤を除去して、樹脂と金属錯体との混合物を調製するステップと、
（３）前記樹脂と金属錯体との混合物に、少なくとも１種の担体を添加して、樹脂と金属錯体と担体との混合物を調製するステップと、
（４）前記樹脂と金属錯体と担体との混合物を、非酸化性雰囲気中で、６００〜１２００℃で焼成するステップと、
（５）前記（４）のステップで得られた焼成物から金属を除去するステップとを有することを特徴とする燃料電池用触媒の製造方法。 A method for producing a fuel cell catalyst according to any one of claims 1 to 4,
(1) adding at least one metal complex to a liquid in which a resin as a raw material for a carbon-based catalyst is dissolved or dispersed in a solvent;
(2) removing the solvent from the liquid obtained in the step (1) to prepare a mixture of a resin and a metal complex;
(3) adding at least one carrier to the mixture of the resin and the metal complex to prepare a mixture of the resin, the metal complex, and the carrier;
(4) firing the mixture of the resin, the metal complex, and the carrier in a non-oxidizing atmosphere at 600 to 1200 ° C .;
(5) A method for producing a fuel cell catalyst, comprising: removing a metal from the fired product obtained in the step (4).
前記カソード触媒層が、請求項１〜４のいずれかに記載の燃料電池用触媒を含むことを特徴とする膜電極接合体。 A membrane electrode assembly comprising a cathode catalyst layer, an anode catalyst layer, and a proton conductive film interposed between the cathode catalyst layer and the anode catalyst layer,
The said cathode catalyst layer contains the catalyst for fuel cells in any one of Claims 1-4, The membrane electrode assembly characterized by the above-mentioned.
前記カソード触媒層が、請求項１〜４のいずれかに記載の燃料電池用媒を含むことを特徴とする燃料電池。 A fuel cell having a membrane electrode assembly comprising a cathode catalyst layer, an anode catalyst layer, and a proton conductive film interposed between the cathode catalyst layer and the anode catalyst layer,
A fuel cell, wherein the cathode catalyst layer contains the fuel cell medium according to claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014156966A2 (en) * | 2013-03-26 | 2014-10-02 | ダイハツ工業株式会社 | Oxygen reduction catalyst, and fuel cell |
| JP2016203133A (en) * | 2015-04-28 | 2016-12-08 | ダイハツ工業株式会社 | Oxygen reduction catalyst |
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| WO2014156966A2 (en) * | 2013-03-26 | 2014-10-02 | ダイハツ工業株式会社 | Oxygen reduction catalyst, and fuel cell |
| WO2014156966A3 (en) * | 2013-03-26 | 2014-11-20 | ダイハツ工業株式会社 | Oxygen reduction catalyst, and fuel cell |
| JP2016203133A (en) * | 2015-04-28 | 2016-12-08 | ダイハツ工業株式会社 | Oxygen reduction catalyst |
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