JP2005224800A - Pt-BASED CATALYST AND METHANOL FUEL CELL USING THE SAME - Google Patents
Pt-BASED CATALYST AND METHANOL FUEL CELL USING THE SAME Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000011865 Pt-based catalyst Substances 0.000 title claims abstract description 25
- 239000000446 fuel Substances 0.000 title claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 7
- 239000010419 fine particle Substances 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 230000010718 Oxidation Activity Effects 0.000 abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 10
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- RTZYCRSRNSTRGC-LNTINUHCSA-K (z)-4-oxopent-2-en-2-olate;ruthenium(3+) Chemical compound [Ru+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O RTZYCRSRNSTRGC-LNTINUHCSA-K 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 229910002849 PtRu Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- FTDZDYKQOAOCRU-UHFFFAOYSA-N platinum(3+) Chemical compound [Pt+3] FTDZDYKQOAOCRU-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid 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
Abstract
Description
本発明は、Pt系合金触媒に関するものであり、更に詳細には、直接メタノール型燃料電池用触媒として好適なPt系触媒およびそれを用いた直接メタノール型燃料電池に関する。 The present invention relates to a Pt-based alloy catalyst, and more particularly to a Pt-based catalyst suitable as a direct methanol fuel cell catalyst and a direct methanol fuel cell using the same.
メタノールを燃料として用いた燃料電池は、一般的には白金系の触媒をカーボンに担持させ触媒層をカーボンシートやカーボンクロス上に形成し、これらをメタノール極および酸素極とし、その間にプロトン導電性のある有機膜を挟持したものが知られている。 A fuel cell using methanol as a fuel generally has a platinum-based catalyst supported on carbon and a catalyst layer formed on a carbon sheet or carbon cloth, which is used as a methanol electrode and an oxygen electrode, with proton conductivity therebetween. An organic film with a gap is known.
メタノール極ではPt系触媒上で式(1)で示したようにメタノールがCO2に酸化される。
CH3OH＋H２O → CO２＋６H＋＋６e− 式(1)
この反応過程で発生するCOはPtと化学結合しやすく、Pt触媒の活性点は次第にCOで覆われ、最終的にはPtの触媒活性が失われる。この現象をCOによる触媒被毒と呼ぶ。現在ではこの被毒を抑えるため、PtRu合金触媒が使用されている（例えば、特許文献１参照）。RuはPt上に化学吸着したCOをCO2に酸化し、COによる被毒を抑える助触媒である。
At the methanol electrode, methanol is oxidized to CO 2 on the Pt catalyst as shown by the formula (1).
CH 3 OH + H 2 O → CO 2 + 6H + + 6e - formula (1)
CO generated in this reaction process is likely to chemically bond with Pt, and the active site of the Pt catalyst is gradually covered with CO, and eventually the catalytic activity of Pt is lost. This phenomenon is called catalyst poisoning by CO. Currently, a PtRu alloy catalyst is used to suppress this poisoning (see, for example, Patent Document 1). Ru is a co-catalyst that oxidizes CO chemisorbed on Pt to CO 2 and suppresses poisoning by CO.
一般にPt系触媒の性能はその粒径に大きく依存している。粒径の減少と共に触媒の表面積が増加して触媒活性が向上する。通常、Pt系触媒の粒径は〜5nmであるが、より好ましくは1〜2nmである。Pt系触媒の粒径はその合成方法により大きく影響されるが、合成方法はノウハウ的な要素が多く広く開示されていないのが現状である。 In general, the performance of a Pt-based catalyst greatly depends on its particle size. As the particle size decreases, the surface area of the catalyst increases and the catalytic activity improves. Usually, the particle size of the Pt-based catalyst is ˜5 nm, more preferably 1-2 nm. The particle size of the Pt-based catalyst is greatly influenced by its synthesis method, but the synthesis method has many know-how elements and is not widely disclosed at present.
上述したように、Pt系触媒の粒径を1〜2nmに保つ手段については不明な点が多かった。
本発明は、Pt系触媒の粒径を1〜2nmに保ち、メタノール酸化活性の高い燃料電池用Pt系触媒を提供することを目的とする。
As described above, there are many unclear points regarding the means for maintaining the particle size of the Pt-based catalyst at 1 to 2 nm.
An object of the present invention is to provide a Pt-based catalyst for a fuel cell having a high methanol oxidation activity while keeping the particle size of the Pt-based catalyst at 1 to 2 nm.
本発明は、Pt系触媒において、Pt系触媒に硫黄元素を含ませる事により解決される。 The present invention is solved by adding a sulfur element to a Pt catalyst in the Pt catalyst.
本発明者は、Pt系触媒合成時にその系内に硫黄の供給源を添加する事で硫黄を含有したPt系触媒が合成され、Pt系触媒の粒径を1〜2nmに保つ事が可能となることを見出した。硫黄添加元素が、Pt又はPt系合金の結晶化を妨げる働きをし、粒子の粗大化を抑止したと考えられる。 The present inventor can synthesize a Pt-based catalyst containing sulfur by adding a sulfur supply source into the Pt-based catalyst during synthesis, and can maintain the particle size of the Pt-based catalyst at 1 to 2 nm. I found out that It is considered that the sulfur-added element functions to prevent crystallization of Pt or a Pt-based alloy and suppresses the coarsening of the particles.
前記添加元素の供給源として以下の試薬を用いる事ができる。硫黄に対しては亜硫酸ナトリウム、亜硫酸アンモニウム、チオ硫酸ナトリウム、チオ硫酸アンモニウムである。これらの試薬を触媒合成用の試薬に含まれるPt系金属イオン総量に対して1〜50％添加して硫黄を含むPt系触媒を合成する。1%未満ではPt系触媒の微粒子化の効果が十分でなく、50%を越えるとその効果が飽和する。 The following reagents can be used as a source of the additive element. For sulfur, sodium sulfite, ammonium sulfite, sodium thiosulfate, and ammonium thiosulfate. These reagents are added in an amount of 1 to 50% with respect to the total amount of Pt metal ions contained in the reagent for catalyst synthesis to synthesize a Pt catalyst containing sulfur. If it is less than 1%, the effect of making the Pt catalyst fine is not sufficient, and if it exceeds 50%, the effect is saturated.
触媒担持用の炭素粉末としては導電性カーボンブラック、アセチレンブラック、グラファイト、カーボンナノチューブなどが好適である。 As the carbon powder for supporting the catalyst, conductive carbon black, acetylene black, graphite, carbon nanotube and the like are suitable.
Ptの供給源としてはビス（アセチルアセトナト）白金(II)或いは六塩化白金酸、Ruの供給源としてはトリス（アセチルアセトナト）白金（III）或いは塩化ルテニウム水和物が使用できる。 Bis (acetylacetonato) platinum (II) or hexachloroplatinic acid can be used as the Pt supply source, and tris (acetylacetonato) platinum (III) or ruthenium chloride hydrate can be used as the Ru supply source.
本発明によれば、Pt系触媒に硫黄元素を含ませる事により、その非晶質化効果によってPt系触媒の粒径を1〜2nmに保つ事が可能となり、Pt系触媒のメタノール酸化活性を高める事ができる。 According to the present invention, by including sulfur element in the Pt-based catalyst, it becomes possible to keep the particle size of the Pt-based catalyst at 1 to 2 nm due to the amorphization effect, and the methanol oxidation activity of the Pt-based catalyst is increased. Can be increased.
本実施形態では、炭素粉末存在下、アルコール中に、Ptの供給源、Ruの供給源及び添加元素の供給源を溶解させ、不活性雰囲気中で加熱還流するアルコール還元法により触媒の製造を行った。その詳細は以下の通りである。 In the present embodiment, a catalyst is produced by an alcohol reduction method in which a Pt supply source, a Ru supply source, and an additive element supply source are dissolved in alcohol in the presence of carbon powder and heated to reflux in an inert atmosphere. It was. The details are as follows.
ビス（アセチルアセトナト）白金（II）１．６９mmolとトリス（アセチルアセトナト）ルテニウム（III）１．６９mmol及び亜硫酸ナトリウム０．６７６ｍｍｏｌをそれぞれ１００ｍｌのエチレングリコールに溶解させ、炭素粉末０．５ｇを分散させた１００ｍｌのエチレングリコール溶液を加えた。窒素雰囲気下、２００℃でこの溶液を攪拌しながら還流し、PtRuS微粒子を炭素粉末に担持させた。反応終了後、濾過、洗浄して乾燥させ触媒を得た。 Dissolve 1.69 mmol of bis (acetylacetonato) platinum (II), 1.69 mmol of tris (acetylacetonato) ruthenium (III) and 0.676 mmol of sodium sulfite in 100 ml of ethylene glycol, and disperse 0.5 g of carbon powder. 100 ml of the ethylene glycol solution was added. This solution was refluxed with stirring at 200 ° C. in a nitrogen atmosphere, and PtRuS fine particles were supported on carbon powder. After completion of the reaction, the mixture was filtered, washed and dried to obtain a catalyst.
ビス（アセチルアセトナト）白金（II）１．６９mmolとトリス（アセチルアセトナト）ルテニウム（III）１．６９mmol及びジメチルアミンボラン０．６７６mmolをそれぞれ１００ｍｌのエチレングリコールに溶解させ、炭素粉末０．５ｇを分散させた１００ｍｌのエチレングリコール溶液を加えた。窒素雰囲気下、２００℃でこの溶液を攪拌しながら還流し、PtRuB微粒子を炭素粉末に担持させた。反応終了後、濾過、洗浄して乾燥させ触媒を得た。 1.69 mmol of bis (acetylacetonato) platinum (II), 1.69 mmol of tris (acetylacetonato) ruthenium (III) and 0.676 mmol of dimethylamine borane are dissolved in 100 ml of ethylene glycol, and 0.5 g of carbon powder is dissolved. Dispersed 100 ml ethylene glycol solution was added. This solution was refluxed with stirring at 200 ° C. in a nitrogen atmosphere, and PtRuB fine particles were supported on carbon powder. After completion of the reaction, the mixture was filtered, washed and dried to obtain a catalyst.
ビス（アセチルアセトナト）白金（II）１．６９mmolとトリス（アセチルアセトナト）ルテニウム（III）１．６９mmol及び次亜燐酸ナトリウム０．６７６mmolをそれぞれ１００ｍｌのエチレングリコールに溶解させ、炭素粉末０．５ｇを分散させた１００ｍｌのエチレングリコール溶液を加えた。窒素雰囲気下、２００℃でこの溶液を攪拌しながら還流し、PtRuP合金微粒子を炭素粉末に担持させた。反応終了後、濾過、洗浄して乾燥させ触媒を得た。 1.69 mmol of bis (acetylacetonato) platinum (II), 1.69 mmol of tris (acetylacetonato) ruthenium (III) and 0.676 mmol of sodium hypophosphite are dissolved in 100 ml of ethylene glycol, respectively, and 0.5 g of carbon powder is obtained. 100 ml of ethylene glycol solution in which was dispersed was added. This solution was refluxed with stirring at 200 ° C. in a nitrogen atmosphere, and PtRuP alloy fine particles were supported on carbon powder. After completion of the reaction, the mixture was filtered, washed and dried to obtain a catalyst.
ビス（アセチルアセトナト）白金（II）１．６９mmolとトリス（アセチルアセトナト）ルテニウム（III）１．６９mmol及びグリシン０．６７６mmolをそれぞれ１００ｍｌのエチレングリコールに溶解させ、炭素粉末０．５ｇを分散させた１００ｍｌのエチレングリコール溶液を加えた。窒素雰囲気下、２００℃でこの溶液を攪拌しながら還流し、PtRuC微粒子を炭素粉末に担持させた。反応終了後、濾過、洗浄して乾燥させ触媒を得た。
（比較例１）
Dissolve 1.69 mmol of bis (acetylacetonato) platinum (II), 1.69 mmol of tris (acetylacetonato) ruthenium (III) and 0.676 mmol of glycine in 100 ml of ethylene glycol, and disperse 0.5 g of carbon powder. 100 ml of ethylene glycol solution was added. This solution was refluxed with stirring at 200 ° C. in a nitrogen atmosphere, and PtRuC fine particles were supported on carbon powder. After completion of the reaction, the mixture was filtered, washed and dried to obtain a catalyst.
(Comparative Example 1)
ビス（アセチルアセトナト）白金（II）１．６９mmolとトリス（アセチルアセトナト）ルテニウム（III）１．６９mmolをそれぞれ１００ｍｌのエチレングリコールに溶解させ、炭素粉末０．５ｇを分散させた１００ｍｌのエチレングリコール溶液を加えた。窒素雰囲気下、２００℃でこの溶液を攪拌しながら還流し、PtRu微粒子を炭素粉末に担持させた。反応終了後、濾過、洗浄して乾燥させ触媒を得た。 100 ml of ethylene glycol in which 1.69 mmol of bis (acetylacetonato) platinum (II) and 1.69 mmol of tris (acetylacetonato) ruthenium (III) are dissolved in 100 ml of ethylene glycol and 0.5 g of carbon powder is dispersed. The solution was added. This solution was refluxed with stirring at 200 ° C. in a nitrogen atmosphere, and PtRu fine particles were supported on carbon powder. After completion of the reaction, the mixture was filtered, washed and dried to obtain a catalyst.
実施例１〜４及び比較例１で得られた触媒の粒径を電子顕微鏡で調べた。その結果を表１に示す。実施例では触媒の粒径が1.5nm以下となっているのに対し、比較例では触媒の粒径は5nmとなっている。 The particle diameters of the catalysts obtained in Examples 1 to 4 and Comparative Example 1 were examined with an electron microscope. The results are shown in Table 1. In the examples, the particle size of the catalyst is 1.5 nm or less, whereas in the comparative example, the particle size of the catalyst is 5 nm.
実施例1〜4及び比較例1で得られたカーボン担持触媒をカーボン担持触媒：Nafion = 7：6 になるようにスラリー作製し、これを厚さ200μm、直径20mmのカーボンペーパ（東レ製）上に1.5mgPtRuX(X:S,B,P,C,-)/cm2となるように塗布した。乾燥後、100kg/cm2でプレスを行い、電極とした。電極特性評価を温度25℃、メタノール濃度20wt%、電解質1.5M H2SO4の条件で行った。電位0.6V(vs.NHE)における電流を表2に示す。 The carbon-supported catalysts obtained in Examples 1 to 4 and Comparative Example 1 were slurried so as to have a carbon-supported catalyst: Nafion = 7: 6, and this was formed on a carbon paper (made by Toray) having a thickness of 200 μm and a diameter of 20 mm. And 1.5 mg PtRuX (X: S, B, P, C,-) / cm 2 . After drying, pressing was performed at 100 kg / cm 2 to obtain an electrode. The electrode characteristics were evaluated under the conditions of a temperature of 25 ° C., a methanol concentration of 20 wt%, and an electrolyte of 1.5 MH 2 SO 4 . Table 2 shows current at a potential of 0.6 V (vs. NHE).
表2から明らかなように、実施例では比較例に比べて大きな電流がえられ、メタノール酸化活性が向上した事が分かる。 As is clear from Table 2, it can be seen that a larger current was obtained in the example than in the comparative example, and the methanol oxidation activity was improved.
本発明の方法により製造されたＰｔ系触媒は、メタノール燃料電池のメタノール極用触媒として特に有用である。また、固体高分子燃料電池等のその他の種類の燃料電池においても使用することも可能である。
The Pt-based catalyst produced by the method of the present invention is particularly useful as a methanol electrode catalyst for methanol fuel cells. It can also be used in other types of fuel cells such as solid polymer fuel cells.
Claims (6)
6. The fuel cell catalyst according to claim 5, wherein the carbon powder is conductive carbon black, acetylene black, graphite, or carbon nanotube.
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| JP2005070212A Withdrawn JP2005224800A (en) | 2005-03-14 | 2005-03-14 | Pt-BASED CATALYST AND METHANOL FUEL CELL USING THE SAME |
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| JP (1) | JP2005224800A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005205394A (en) * | 2003-12-26 | 2005-08-04 | Hitachi Maxell Ltd | Catalyst for fuel cell and manufacturing method thereof |
| JP2007066908A (en) * | 2005-08-31 | 2007-03-15 | Samsung Sdi Co Ltd | Catalyst for cathode electrode of fuel cell and its manufacturing method, as well as, membrane electrode assembly for fuel cell |
| JP2007090157A (en) * | 2005-09-27 | 2007-04-12 | Furukawa Electric Co Ltd:The | Cathode catalyst for fuel cell and fuel cell using the same |
| JP2007519514A (en) * | 2004-01-28 | 2007-07-19 | デ・ノラ・エレートローディ・ソチエタ・ペル・アツィオーニ | Synthesis of noble metal sulfide catalysts in aqueous environment free of sulfide ions |
-
2005
- 2005-03-14 JP JP2005070212A patent/JP2005224800A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005205394A (en) * | 2003-12-26 | 2005-08-04 | Hitachi Maxell Ltd | Catalyst for fuel cell and manufacturing method thereof |
| JP4498843B2 (en) * | 2003-12-26 | 2010-07-07 | 日立マクセル株式会社 | Catalyst for fuel cell and method for producing the same |
| JP2007519514A (en) * | 2004-01-28 | 2007-07-19 | デ・ノラ・エレートローディ・ソチエタ・ペル・アツィオーニ | Synthesis of noble metal sulfide catalysts in aqueous environment free of sulfide ions |
| JP4805168B2 (en) * | 2004-01-28 | 2011-11-02 | インドゥストリエ・デ・ノラ・ソチエタ・ペル・アツィオーニ | Synthesis of noble metal sulfide catalysts in aqueous environment free of sulfide ions |
| JP2007066908A (en) * | 2005-08-31 | 2007-03-15 | Samsung Sdi Co Ltd | Catalyst for cathode electrode of fuel cell and its manufacturing method, as well as, membrane electrode assembly for fuel cell |
| US8685594B2 (en) | 2005-08-31 | 2014-04-01 | Samsung Sdi Co., Ltd. | Catalyst for cathode of fuel cell, and membrane-electrode assembly for fuel cell |
| JP2007090157A (en) * | 2005-09-27 | 2007-04-12 | Furukawa Electric Co Ltd:The | Cathode catalyst for fuel cell and fuel cell using the same |
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