JP5531313B2 - Composite electrode catalyst and method for producing the same - Google Patents
Composite electrode catalyst and method for producing the same Download PDFInfo
- Publication number
- JP5531313B2 JP5531313B2 JP2010134688A JP2010134688A JP5531313B2 JP 5531313 B2 JP5531313 B2 JP 5531313B2 JP 2010134688 A JP2010134688 A JP 2010134688A JP 2010134688 A JP2010134688 A JP 2010134688A JP 5531313 B2 JP5531313 B2 JP 5531313B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- tin oxide
- platinum
- carbon
- supported
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims description 118
- 239000002131 composite material Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 229910001887 tin oxide Inorganic materials 0.000 claims description 60
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 54
- 239000003575 carbonaceous material Substances 0.000 claims description 37
- 239000007864 aqueous solution Substances 0.000 claims description 28
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 claims description 23
- -1 tin oxide modified carbon Chemical class 0.000 claims description 21
- 239000010419 fine particle Substances 0.000 claims description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 10
- 229940071182 stannate Drugs 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 74
- 239000002245 particle Substances 0.000 description 42
- 229910052697 platinum Inorganic materials 0.000 description 37
- 239000006229 carbon black Substances 0.000 description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 21
- 229910052799 carbon Inorganic materials 0.000 description 16
- 230000004048 modification Effects 0.000 description 16
- 238000012986 modification Methods 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 14
- 239000000446 fuel Substances 0.000 description 14
- 229910044991 metal oxide Inorganic materials 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 150000004706 metal oxides Chemical class 0.000 description 11
- 230000005540 biological transmission Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000005518 polymer electrolyte Substances 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QEDCEMKTASAIQH-UHFFFAOYSA-O azanium;platinum;nitrate Chemical compound [NH4+].[Pt].[O-][N+]([O-])=O QEDCEMKTASAIQH-UHFFFAOYSA-O 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Images
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
Landscapes
- Fuel Cell (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Description
本発明は、高い耐久性を有する固体高分子形燃料電池等に用いる複合電極触媒およびその製造方法に関するものである。 The present invention relates to a composite electrode catalyst used for a polymer electrolyte fuel cell having high durability and a method for producing the same.
燃料電池用の電極触媒の製造に関する従来技術としてカーボンブラックのような炭素材料や金属酸化物を担体として用いる触媒。カーボンブラックに白金粒子を担持後、酸化タングステンを担持した触媒。カーボンナノチューブに金属酸化物を担持して白金粒子を担持した触媒がある。
燃料電池用電極触媒の製造方法としては前出の例があるが、現在、固体高分子形燃料電には触媒担体に炭素材料であるカーボンブラックを用い、それに白金を担持した白金担持カーボン電極触媒が用いられている。
一方で、同燃料電池のさらなる普及に向け、白金使用量を低減する必要がある。白金使用量を低減するにはできるだけ小粒径の白金粒子を効率的に用いることが必要であり、現在のところ約2 nmの白金粒子がカーボンブラックに分散担持された電極触媒が用いられている。しかしながら、そのような粒径の白金粒子の耐久性は実用上十分でなく、実際に同燃料電池発電中の空気極では、白金の溶解最析出による大径化が進行し、触媒の有効表面積が低下して、電池の性能が低下することがわかっている。また、触媒担体であるカーボンブラックも発電中、特に起動停止時に酸化されて白金粒子が脱離して、触媒の有効表面積が低下して、電池の性能が低下することも明らかになっている。以上のように、固体高分子形燃料電池の普及には、電極触媒を構成する白金粒子と触媒担体の高耐久性が必須となっている。
A catalyst using a carbon material such as carbon black or a metal oxide as a carrier as a conventional technique for producing an electrode catalyst for a fuel cell. A catalyst in which platinum particles are supported on carbon black and then tungsten oxide is supported. There is a catalyst in which platinum particles are supported by supporting metal oxides on carbon nanotubes.
There is the above-mentioned example as a method for producing an electrode catalyst for a fuel cell, but at present, a platinum-supported carbon electrode catalyst in which carbon black, which is a carbon material, is used as a catalyst carrier and platinum is supported on a solid polymer fuel cell. Is used.
On the other hand, it is necessary to reduce the amount of platinum used for further diffusion of the fuel cell. In order to reduce the amount of platinum used, it is necessary to use platinum particles with the smallest possible particle size as efficiently as possible. Currently, electrocatalysts in which platinum particles of about 2 nm are dispersed and supported on carbon black are used. . However, the durability of platinum particles having such a particle size is not sufficient in practical use, and in the air electrode during actual power generation of the fuel cell, the increase in diameter due to dissolution and precipitation of platinum proceeds, and the effective surface area of the catalyst is reduced. It has been found that the battery performance is degraded. It has also been clarified that carbon black, which is a catalyst carrier, is oxidized during power generation, particularly at the time of starting and stopping, and platinum particles are desorbed, reducing the effective surface area of the catalyst and reducing the battery performance. As described above, the high durability of the platinum particles and the catalyst carrier constituting the electrode catalyst is indispensable for the spread of the polymer electrolyte fuel cell.
非特許文献1で白金粒子の高耐久性化には、同燃料電池の電極触媒層内の電解質材料を改善することが効果的であると報告されている。一方、電極触媒自身の耐久性を向上させる手法として、カーボンブラックよりも耐久性の高い金属酸化物粒子を担体として用いる手法や金属酸化物を電極触媒に被覆する手法が報告されている。非特許文献2では、粒径50 nm程度の酸化スズ粒子を電極触媒担体として用いる電極触媒の製造方法とその空気極触媒としての性能が報告されていて、カーボンブラックを用いるよりも耐久性が優れていることが示されている。しかしながら、酸化スズは導電率が高くなく電極触媒として満足できるものでない。そこで、金属酸化物粒子とカーボン材料の複合材料を担体として用いる電極触媒の開発もなされてきた。 Non-Patent Document 1 reports that it is effective to improve the electrolyte material in the electrode catalyst layer of the fuel cell to increase the durability of platinum particles. On the other hand, as a method for improving the durability of the electrode catalyst itself, a method using metal oxide particles having higher durability than carbon black as a carrier and a method for coating a metal oxide on an electrode catalyst have been reported. Non-Patent Document 2 reports a method for producing an electrode catalyst using tin oxide particles having a particle diameter of about 50 nm as an electrode catalyst carrier and its performance as an air electrode catalyst, and is superior in durability to using carbon black. It is shown that. However, tin oxide does not have high conductivity and is not satisfactory as an electrode catalyst. Accordingly, an electrode catalyst using a composite material of metal oxide particles and a carbon material as a support has been developed.
その一例として、特許文献1では焼成により金属酸化物となる金属化合物をカーボン材料上に付着させ、それを300℃以下で焼成して金属酸化物担持カーボン材料を得て、それに白金を担持して触媒を得る方法が提供されている。このようにして作製された金属酸化物粒子担持電極触媒は固体高分子形燃料電池の触媒として、金属酸化物粒子がないものよりも高活性であるとされており、金属化合物としては硝酸塩や金属アルコキシドを用いることが望ましいとされている。しかしながら、それら化合物は空気中で分解する等の理由から扱い難く、生産性が低いあるいは生産コストがかかることが考えられる。また、非特許文献3にてそれら金属酸化物とカーボン材料の複合材料を用いる電極触媒の耐久性は優れていると報告されているが、製造方法は明確にされていない。また、特許文献2では、導電性担体上に貴金属粒子とタングステン酸化物粒子が互いに独立して担持されている耐久性の高い電極触媒の製造方法が提供されている。しかし、耐久性は明確にされておらず不明である。また、非特許文献4では、カーボンナノチューブに化学的処理により欠陥構造を導入してそこに塩化スズを前駆体として酸化スズ微粒子を担持した担体材料にさらに白金微粒子を担持した電極触媒が作製され、そのメタノール酸化活性が高いことが報告されているが、空気極触媒としての性能は報告されておらず不明である。
以上の従来技術の問題に対し、本発明は、従来の複合電極触媒の2倍以上程度の耐久性を有する複合電極触媒とその製造方法を提供するものである。 In response to the above problems of the prior art, the present invention provides a composite electrode catalyst having a durability about twice or more that of a conventional composite electrode catalyst and a method for producing the same.
本発明は上記の課題を満足するものでその特徴とすると技術条件は次の(1)〜(2)の通りである。
(1)、フッ化スズ又はフッ化スズ酸アンモニウム錯体との水溶液中にカーボン材料を分散させて、このカーボン材料の表面にスズフッ化物を吸着させた後、このスズフッ化物吸着カーボン材料を濾別、洗浄後、ホウ酸水溶液に分散させてスズフッ化物を酸化スズにした後、この酸化スズ吸着カーボン材料を洗浄、乾燥した後熱処理して酸化スズ修飾カーボン担体を得、この酸化スズ修飾カーボン材料に、白金微粒子を担持させることを特徴とする複合電極触媒の製造方法。
(2)、カーボン材料の表面に粒径が20 nm以下の酸化スズが修飾され、この酸化スズ修飾カーボン材料に、粒径が5 nm以下の白金微粒子を担持させてなることを特徴とする複合電極触媒。
The present invention satisfies the above-described problems and is characterized by the following technical conditions (1) to (2).
(1) After dispersing the carbon material in an aqueous solution with tin fluoride or ammonium fluoride stannate complex and adsorbing tin fluoride on the surface of the carbon material, the tin fluoride adsorbing carbon material is filtered off, After washing, dispersed in boric acid aqueous solution to convert tin fluoride into tin oxide, this tin oxide adsorbed carbon material was washed, dried and then heat treated to obtain a tin oxide modified carbon carrier, to this tin oxide modified carbon material, A method for producing a composite electrode catalyst, comprising supporting platinum fine particles.
(2) A composite characterized in that tin oxide having a particle size of 20 nm or less is modified on the surface of the carbon material, and platinum fine particles having a particle size of 5 nm or less are supported on the tin oxide-modified carbon material. Electrocatalyst.
本発明の固体高分子形燃料電池等に用いる複合電極触媒とその製造方法は、従来方法とそれによる複合電極触媒に比べ性能は向上し、且つ耐久性(:寿命)は2倍以上と優れた効果が得られる。
本発明において、適用する炭素材料としては、原理的にカーボンブラック、活性炭、炭素繊維および熱処理カーボン材料及びカーボンナノチューブ等その他の炭素材料を適用することができ、幅広い応用が可能である。
The composite electrode catalyst used in the polymer electrolyte fuel cell and the like of the present invention and the production method thereof have improved performance compared to the conventional method and composite electrode catalyst produced thereby, and the durability (: life) is more than doubled. An effect is obtained.
In the present invention, as a carbon material to be applied, other carbon materials such as carbon black, activated carbon, carbon fiber, heat treated carbon material, and carbon nanotube can be applied in principle, and a wide range of applications are possible.
本発明において製造方法は、まずスズフッ化物を出発材料とし、吸着過程を経る液相析出法により約5〜15 nm程度の粒径のカーボンからなる複合材料を製造し、その後、2 〜3 nmの粒径の白金微粒子を担持して複合電極触媒を得る。
即ち、フッ化スズ水溶液あるいはフッ化スズ酸アンモニウム錯体水溶液にカーボン基材(カーボン材料)を12時間〜48時間分散して、カーボン基材の表面にスズフッ化物を吸着させ、これを濾別した後に、ホウ酸水溶液に分散して得た生成物(酸化スズ修飾カーボン基材)をアルゴン雰囲気下で熱処理し整粒する。
BET比表面積で数m2g-1程度のカーボン基材には0.00001〜0.001 mol dm-3の濃度の水溶液が、また数百m2g-1程度のカーボン基材には0.001〜0.1 mol dm-3の濃度の水溶液を用いるのが最適であり、50 mLに対して0.01〜0.1 gの割合で撹拌混合させ、吸着させるのが最適である。また、濃度が上記範囲から逸脱し、高い濃度の場合、金属の仕込み量が過剰となってカーボン基材に担持されない酸化スズ量が多くなり、生産性が低下する。低い濃度の場合、金属の仕込み量が小さくなり、酸化スズが均一に担持された炭素材料を得ることは難しい。
吸着時間は数ナノメートル程度の酸化スズを得るために12〜48時間でなかでも24時間、特に、数ナノメートル程度の酸化スズ金属酸化物を得るにはアンモニウムイオンを有するフルオロ錯体(例(NH4)2SnF6)を用いるのがよい。
カーボン材料表面に吸着したスズフッ化物を分解するにはホウ酸水溶液が望ましく、上記炭素材料0.1 gに対して、濃度0.00001〜0.1 mol dm-3で50 mLを用いるのが適当である。より望ましくは0.1 mol dm-3である。反応時間は24時間〜96時間で24時間が最適である。なお、スズフッ化物の吸着やホウ酸水溶液への分散時間を上記範囲以上としても酸化スズ修飾カーボン材料を得ることは可能であるが、酸化スズの修飾量に顕著な変化はない。
また、その後の熱処理は炭素基材の消耗を抑えるためにアルゴンやヘリウムなど不活性雰囲気で行うのが適当であるが、時間と温度の条件は所望する金属酸化物の結晶性により可変である。 例えば、昇温速度毎分4〜7℃好ましくは5℃として500℃まで昇温後1時間保持し、その後自然放冷するより高い温度で熱処理すると金属酸化物が大径化する傾向にある。
以上のようにして作製した酸化スズ修飾カーボン材料に白金微粒子を担持するには、一般的な担持方法であるイオン交換法や含浸法、化学的析出法などが適用できる。なかでも含浸法が簡便である。すなわち、塩化白金酸や塩化白金酸カリウムあるいはアンモニウム白金硝酸塩などを白金の前駆体として用い、それを酸化スズ修飾カーボン材料に含浸した後、水素気流中あるいは水素化ホウ素ナトリウムなどの化学的還元剤にて還元する。例えば、炭酸ナトリウム水溶液と塩化白金酸水溶液とを混合して毎分2〜10℃好ましくは5℃として80℃まで昇温後、ホルムアルデヒド液を徐々に添加しながら4時間攪拌し、その後濾別、窒素雰囲気下で乾燥させることで白金担持酸化スズ修飾カーボン触媒を得ることができる。この際、用いる酸化スズ修飾カーボン材料と塩化白金酸の比率で白金担持量を調整することができるが、望ましくは2%〜80%の範囲である。特に2 nm程度の粒径の白金微粒子を得るには、5%〜50%が望ましい。
本発明の実施例を以下に示す。
In the present invention, the production method first produces a composite material composed of carbon having a particle size of about 5 to 15 nm by a liquid phase precipitation method using tin fluoride as a starting material and then undergoes an adsorption process. A composite electrode catalyst is obtained by supporting platinum fine particles having a particle size.
That is, after dispersing the carbon base material (carbon material) in the tin fluoride aqueous solution or the ammonium fluoride stannate complex aqueous solution for 12 hours to 48 hours to adsorb the tin fluoride on the surface of the carbon base material and filtering it off. Then, the product (tin oxide-modified carbon substrate) obtained by dispersing in an aqueous boric acid solution is heat-treated in an argon atmosphere and sized.
An aqueous solution with a concentration of 0.00001 to 0.001 mol dm -3 is used for a carbon substrate having a BET specific surface area of about several m 2 g -1, and 0.001 to 0.1 mol dm for a carbon substrate having a few hundred m 2 g -1. It is optimal to use an aqueous solution having a concentration of −3 , and it is optimal to stir and mix at a ratio of 0.01 to 0.1 g with respect to 50 mL and adsorb. Further, when the concentration deviates from the above range and the concentration is high, the amount of metal charged becomes excessive and the amount of tin oxide not supported on the carbon base material increases, resulting in a decrease in productivity. When the concentration is low, the amount of metal charged becomes small, and it is difficult to obtain a carbon material in which tin oxide is uniformly supported.
The adsorption time is 12 to 48 hours to obtain tin oxide of about several nanometers, especially 24 hours.In particular, to obtain tin oxide metal oxide of several nanometers, a fluoro complex having an ammonium ion (example (NH 4 ) 2 SnF 6 ) should be used.
An aqueous boric acid solution is desirable for decomposing tin fluoride adsorbed on the surface of the carbon material. It is appropriate to use 50 mL at a concentration of 0.00001 to 0.1 mol dm −3 with respect to 0.1 g of the carbon material. More desirably, it is 0.1 mol dm −3 . The reaction time is 24 hours to 96 hours, and 24 hours is optimal. Although the tin oxide-modified carbon material can be obtained even when the adsorption time of tin fluoride or the dispersion time in the boric acid aqueous solution is longer than the above range, there is no significant change in the modification amount of tin oxide.
Further, the subsequent heat treatment is suitably performed in an inert atmosphere such as argon or helium in order to suppress the consumption of the carbon base material, but the time and temperature conditions are variable depending on the desired crystallinity of the metal oxide. For example, if the temperature rise rate is 4 to 7 ° C. per minute, preferably 5 ° C., the temperature is raised to 500 ° C. and held for 1 hour, and then heat-treated at a higher temperature than naturally cooled, the metal oxide tends to increase in diameter.
In order to support the platinum fine particles on the tin oxide-modified carbon material produced as described above, a general supporting method such as an ion exchange method, an impregnation method, and a chemical precipitation method can be applied. Of these, the impregnation method is simple. In other words, chloroplatinic acid, potassium chloroplatinate, or ammonium platinum nitrate is used as a platinum precursor, impregnated in a tin oxide-modified carbon material, and then used as a chemical reducing agent in a hydrogen stream or sodium borohydride. To reduce. For example, a sodium carbonate aqueous solution and a chloroplatinic acid aqueous solution are mixed and heated up to 2 to 10 ° C./min, preferably 5 ° C. to 80 ° C., and stirred for 4 hours while gradually adding formaldehyde solution, and then filtered. A platinum-supported tin oxide-modified carbon catalyst can be obtained by drying in a nitrogen atmosphere. At this time, the amount of platinum supported can be adjusted by the ratio of the tin oxide-modified carbon material to be used and chloroplatinic acid, but it is preferably in the range of 2% to 80%. In particular, in order to obtain platinum fine particles having a particle diameter of about 2 nm, 5% to 50% is desirable.
Examples of the present invention are shown below.
0.1 mol dm-3含むスズフッ化物水溶液中に炭素材料としてカーボンブラック(BET比表面積 約800 m2 g-1)を24時間分散させると共にそのカーボンブラック表面にフッ化スズを吸着させた後、濾別、洗浄後、ホウ酸水溶液に分散させ、24時間反応後、洗浄、乾燥させた後、アルゴン雰囲気下500℃で1時間の熱処理を施して酸化スズ担持量大の酸化スズ修飾カーボンブラックを得た。
さらに、塩化白金酸水溶液とホルムアルデヒド水溶液を用いることにより、白金担持量15wt%の白金担持酸化スズ修飾カーボンブラック触媒を得た。これを触媒Aとする。この触媒Aの透過型電子顕微鏡像を図1に示す。粒径で5〜15 nm程度の酸化スズ粒子と粒径で2 nm程度の白金微粒子がそれぞれカーボンブラック上に担持されている様子が確認された。また、白金粒子は酸化スズ粒子とカーボンブラック上のどちらにも担持されている様子が確認された。
Disperse carbon black (BET specific surface area about 800 m 2 g -1 ) as a carbon material in tin fluoride aqueous solution containing 0.1 mol dm -3 for 24 hours and adsorb tin fluoride on the carbon black surface, then filter After washing, dispersed in an aqueous boric acid solution, reacted for 24 hours, washed and dried, and then heat treated at 500 ° C. for 1 hour in an argon atmosphere to obtain a tin oxide-modified carbon black having a large amount of tin oxide supported. .
Further, by using a chloroplatinic acid aqueous solution and a formaldehyde aqueous solution, a platinum-supported tin oxide-modified carbon black catalyst having a platinum support amount of 15 wt% was obtained. This is referred to as catalyst A. A transmission electron microscope image of the catalyst A is shown in FIG. It was confirmed that tin oxide particles having a particle size of about 5 to 15 nm and platinum fine particles having a particle size of about 2 nm were supported on carbon black. Further, it was confirmed that the platinum particles were supported on both the tin oxide particles and the carbon black.
0.01 mol dm-3含むスズフッ化物水溶液中に炭素材料としてカーボンブラック(BET比表面積 約800 m2 g-1)を24時間分散させると共にそのカーボンブラック表面にフッ化スズを吸着させた後、濾別、洗浄後、ホウ酸水溶液に分散させ、24時間反応後、洗浄、乾燥させた後、アルゴン雰囲気下500℃で1時間の熱処理を施して酸化スズ担持量中の酸化スズ修飾カーボンブラックを得た。
さらに、塩化白金酸水溶液とホルムアルデヒド水溶液を用いることにより、白金担持量15wt%の白金担持酸化スズ修飾カーボンブラック触媒を得た。これを触媒Bとする。この触媒Bの透過型電子顕微鏡像を図2に示す。粒径で5〜15 nm程度の酸化スズ粒子と粒径で2 nm程度の白金微粒子がそれぞれカーボンブラック上に担持されている様子が確認された。また、白金粒子は酸化スズ粒子とカーボンブラック上のどちらにも担持されている様子が確認された。
Carbon black (BET specific surface area of about 800 m 2 g -1 ) as a carbon material is dispersed in tin fluoride aqueous solution containing 0.01 mol dm -3 for 24 hours, and tin fluoride is adsorbed on the surface of the carbon black, followed by filtration. After washing, dispersed in an aqueous boric acid solution, reacted for 24 hours, washed and dried, and then subjected to heat treatment at 500 ° C. for 1 hour in an argon atmosphere to obtain tin oxide modified carbon black in the amount of tin oxide supported .
Further, by using a chloroplatinic acid aqueous solution and a formaldehyde aqueous solution, a platinum-supported tin oxide-modified carbon black catalyst having a platinum support amount of 15 wt% was obtained. This is catalyst B. A transmission electron microscope image of the catalyst B is shown in FIG. It was confirmed that tin oxide particles having a particle size of about 5 to 15 nm and platinum fine particles having a particle size of about 2 nm were supported on carbon black. Further, it was confirmed that the platinum particles were supported on both the tin oxide particles and the carbon black.
0.001 mol dm-3含むスズフッ化物水溶液中に炭素材料としてカーボンブラック(BET比表面積 約800 m2 g-1)を24時間分散させると共にそのカーボンブラック表面にフッ化スズを吸着させた後、濾別、洗浄後、ホウ酸水溶液に分散させ、24時間反応後、洗浄、乾燥させた後、アルゴン雰囲気下500℃で1時間の熱処理を施して酸化スズ修飾カーボンブラックを得た。これを熱重量分析測定によって1000℃での重量残存率を測定した結果、酸化スズが3wt%含まれているとわかった。
さらに、塩化白金酸水溶液とホルムアルデヒド水溶液を用いることにより、白金担持量15wt%の白金担持酸化スズ修飾カーボンブラック触媒を得た。これを触媒Cとする。この触媒Cを透過型電子顕微鏡像で観察した結果、粒子がカーボンブラック上に担持されている様子は観察できたが、酸化スズと白金微粒子の区別をつけることはできなかった。
Disperse carbon black (BET specific surface area about 800 m 2 g -1 ) as a carbon material in 0.001 mol dm -3 tin fluoride aqueous solution for 24 hours and adsorb tin fluoride on the carbon black surface, then filter After washing, it was dispersed in an aqueous boric acid solution, reacted for 24 hours, washed and dried, and then heat treated at 500 ° C. for 1 hour in an argon atmosphere to obtain tin oxide-modified carbon black. As a result of measuring the weight residual ratio at 1000 ° C. by thermogravimetric analysis, it was found that 3 wt% of tin oxide was contained.
Further, by using a chloroplatinic acid aqueous solution and a formaldehyde aqueous solution, a platinum-supported tin oxide-modified carbon black catalyst having a platinum support amount of 15 wt% was obtained. This is referred to as catalyst C. As a result of observing the catalyst C with a transmission electron microscope image, it was possible to observe that the particles were supported on carbon black, but it was not possible to distinguish between tin oxide and platinum fine particles.
実施例1〜3で得た触媒AとBおよび同様の方法で得た酸化スズ修飾量小の触媒C、酸化スズ非修飾触媒をそれぞれグラッシーカーボン円板上に載せ、それを回転電極装置に取り付けて、室温条件下、酸素を飽和させた0.1 mol dm-3過塩素酸水溶液中で各触媒の酸素還元反応に対する電流を測定した。いずれの触媒でも酸素還元反応に対して有効な触媒活性を持つことがわかった。測定された電流から触媒活性を求めた結果を表1に示す。なお、表では白金の担持重量で除した質量活性として示している。触媒A〜Cの触媒活性は酸化スズ修飾量により増加する傾向が見られたが、誤差範囲とも考えられ、概ね、どの触媒も酸化スズ非修飾触媒とほぼ同程度の触媒活性であった。よって、白金担持酸化スズ修飾カーボン触媒は酸化スズ非修飾と同程度の触媒活性を有する空気極触媒であるとわかった。 Catalysts A and B obtained in Examples 1 to 3 and a catalyst C with a small amount of tin oxide modification obtained by the same method and a catalyst not modified with tin oxide were placed on a glassy carbon disk, and attached to a rotating electrode device. The current for the oxygen reduction reaction of each catalyst was measured in a 0.1 mol dm -3 perchloric acid aqueous solution saturated with oxygen at room temperature. It was found that any catalyst has an effective catalytic activity for the oxygen reduction reaction. Table 1 shows the results of the catalytic activity obtained from the measured current. In the table, it is shown as mass activity divided by the supported weight of platinum. Although the catalyst activities of the catalysts A to C tended to increase depending on the tin oxide modification amount, it was considered as an error range, and in general, all the catalysts had almost the same catalyst activity as that of the tin oxide non-modified catalyst. Therefore, it was found that the platinum-supported tin oxide modified carbon catalyst was an air electrode catalyst having a catalytic activity comparable to that of the tin oxide non-modified.
上記のようにして得た触媒A〜Cおよび酸化スズ非修飾触媒をそれぞれグラッシーカーボン円板上に載せ、60℃の窒素飽和の0.1 mol dm-3過塩素酸水溶液中で可逆水素電極に対して1.0 V〜1.5 Vの範囲で電位サイクル加速劣化試験を行った。各試験回数後での各触媒の可逆水素電極に対して0.4 V〜0.7 Vの電気二重層容量の変化を図4に示す。このとき、電気二重層容量の増大がないことが、触媒の耐久性が高いことを意味する。全体的に試験回数が増加するにつれて電気二重層容量は増大した。酸化スズ修飾量が大である触媒Aは試験終了時での容量増加率は150%程度、触媒Bでは175%程度、触媒Cでは160%程度で、酸化スズ非修飾触媒では190%程度であって、酸化スズ非修飾触媒と比べて触媒A〜Cの増大率は低かった。また、触媒A〜Cの結果から酸化スズ修飾量が増大するにつれてその増大率が抑制されることがわかった。よって、酸化スズを含む複合触媒A〜Cの本試験条件における耐久性は酸化スズ非修飾触媒よりも高い。よって、白金担持酸化スズ修飾カーボン触媒は固体高分子形燃料電池用の高耐久性化に有用な電極触媒であるとわかった。
Catalysts A to C and tin oxide non-modified catalyst obtained as described above were each placed on a glassy carbon disk, and against a reversible hydrogen electrode in a 0.1 mol dm -3 perchloric acid aqueous solution saturated with nitrogen at 60 ° C. A potential cycle accelerated deterioration test was conducted in the range of 1.0 V to 1.5 V. FIG. 4 shows the change in electric double layer capacity of 0.4 V to 0.7 V with respect to the reversible hydrogen electrode of each catalyst after each test. At this time, the absence of an increase in the electric double layer capacity means that the durability of the catalyst is high. As a whole, the electric double layer capacity increased as the number of tests increased. Catalyst A with a large amount of tin oxide modification has a capacity increase rate of about 150% at the end of the test, catalyst B is about 175%, catalyst C is about 160%, and tin oxide unmodified catalyst is about 190%. Thus, the increase rate of the catalysts A to C was low as compared with the tin oxide non-modified catalyst. Moreover, it turned out that the increase rate is suppressed as the tin oxide modification amount increases from the results of the catalysts A to C. Therefore, the durability of the composite catalysts A to C containing tin oxide under the test conditions is higher than that of the unmodified tin oxide catalyst. Therefore, it was found that the platinum-supported tin oxide-modified carbon catalyst is an electrode catalyst useful for improving the durability of the polymer electrolyte fuel cell.
上記のようにして得た触媒A〜Cおよび酸化スズ非修飾触媒をそれぞれグラッシーカーボン円板上に載せ、60℃の窒素飽和の0.1 mol dm-3過塩素酸水溶液中で可逆水素電極に対してパルス状に1.0 Vと0.6 Vの電圧を印加し、加速劣化試験を行った。各試験回数後での各触媒の可逆水素電極に対して0.05 V〜0.4 Vの電気二重層容量から白金微粒子の残有効表面積を求め、その変化を図4に示す。試験初期では残有効表面積が100%を超えたが、その後、試験回数が増加するにつれて残有効表面積は減少した。酸化スズ修飾量が大である触媒Aは試験終了時での残有効表面積は95%程度、触媒Bでは87%程度、触媒Cでは76%程度で、酸化スズ非修飾触媒では75%程度で、酸化スズ非修飾触媒と比べて触媒A〜Cの残有効表面積は高かった。この結果より、酸化スズを含む複合触媒A〜Cの本試験条件における耐久性は酸化スズ非修飾触媒よりも高く、触媒A〜Cの結果から酸化スズ修飾量が増大するにつれて耐久性が増大することがわかった。よって、白金担持酸化スズ修飾カーボン触媒は固体高分子形燃料電池用の高耐久性化に有用な電極触媒であるとわかった。
Catalysts A to C and tin oxide non-modified catalyst obtained as described above were each placed on a glassy carbon disk, and against a reversible hydrogen electrode in a 0.1 mol dm -3 perchloric acid aqueous solution saturated with nitrogen at 60 ° C. Voltages of 1.0 V and 0.6 V were applied in the form of pulses, and an accelerated deterioration test was conducted. The residual effective surface area of the platinum fine particles was determined from the electric double layer capacity of 0.05 V to 0.4 V with respect to the reversible hydrogen electrode of each catalyst after each test, and the change is shown in FIG. The remaining effective surface area exceeded 100% at the beginning of the test, but thereafter, the remaining effective surface area decreased as the number of tests increased. Catalyst A with a large amount of tin oxide modification has a remaining effective surface area of about 95% at the end of the test, catalyst B is about 87%, catalyst C is about 76%, and tin oxide unmodified catalyst is about 75%. Compared with the unmodified tin oxide catalyst, the remaining effective surface area of catalysts AC was higher. From these results, the durability of the composite catalysts A to C containing tin oxide in this test condition is higher than that of the unmodified tin oxide catalyst, and the durability increases as the tin oxide modification amount increases from the results of the catalysts A to C. I understood it. Therefore, it was found that the platinum-supported tin oxide-modified carbon catalyst is an electrode catalyst useful for improving the durability of the polymer electrolyte fuel cell.
実施例5で示した加速劣化試験後、触媒A〜Cおよび酸化スズ非修飾触媒をそれぞれグラッシーカーボン円板上に載せ、それを回転電極装置に取り付けて、室温条件下、酸素を飽和させた0.1 mol dm-3過塩素酸水溶液中で各触媒の酸素還元反応に対する電流を測定し、活性支配電流を計算し、白金の触媒中の担持重量で除して触媒(質量)活性を求めた。加速劣化試験前との比較から、各触媒の活性保持率と低下率を算出した。その結果を表2に示す。酸化スズ非修飾触媒では、活性低下率は57%と試験前に比べ約半分まで低下したが、酸化スズ修飾量大の触媒Aでは、82%と非常に高いことがわかった。また、酸化スズ修飾量中の触媒Bでも酸化スズ非修飾触媒よりも高く、酸化スズ修飾量が小の触媒Cでは、酸化スズ非修飾触媒とほぼ同程度の活性保持率と低下率であった。酸化スズ非修飾触媒と触媒Aの活性低下率との比較から、触媒Aは酸化スズ非修飾触媒に比べ二倍以上程度の耐久性を有するとわかった。よって、白金担持酸化スズ修飾カーボン触媒は固体高分子形燃料電池用の高耐久性化に有用な電極触媒であるとわかった。 After the accelerated deterioration test shown in Example 5, the catalysts A to C and the tin oxide non-modified catalyst were each placed on a glassy carbon disk and attached to a rotating electrode device. The current for the oxygen reduction reaction of each catalyst was measured in an aqueous solution of mol dm -3 perchloric acid, the activity-dominated current was calculated, and the catalyst (mass) activity was determined by dividing by the supported weight of platinum in the catalyst. From the comparison with before the accelerated deterioration test, the activity retention rate and the decrease rate of each catalyst were calculated. The results are shown in Table 2. With the unmodified tin oxide catalyst, the rate of decrease in activity was 57%, which was about half that before the test, but with the catalyst A with a large amount of tin oxide modification, it was found to be very high at 82%. In addition, the catalyst B in the tin oxide modification amount was higher than the non-tin oxide modification catalyst, and the catalyst C with a small tin oxide modification amount had approximately the same activity retention and reduction rate as the non-tin oxide modification catalyst. . From a comparison of the activity reduction rate of the tin oxide non-modified catalyst and the catalyst A, it was found that the catalyst A had durability twice or more that of the tin oxide non-modified catalyst. Therefore, it was found that the platinum-supported tin oxide-modified carbon catalyst is an electrode catalyst useful for improving the durability of the polymer electrolyte fuel cell.
0.1 mol dm-3含むフッ化スズ水溶液中に炭素材料として熱処理炭素(BET比表面積 数m2 g-1)を24時間分散させると共にその表面にフッ化スズを吸着させた後、濾別、洗浄後、ホウ酸水溶液に分散させ、24時間反応後、洗浄、乾燥させた後、アルゴン雰囲気下500℃で1時間の熱処理を施して酸化スズ修飾熱処理炭素を得た。
さらに、塩化白金酸水溶液とホルムアルデヒド水溶液を用いることにより、白金担持量4wt%の白金担持酸化スズ修飾熱処理炭素複合電極触媒を得た。この触媒Bの透過型電子顕微鏡像を図5に示す。粒径で5〜15 nm程度の酸化スズ粒子が凝集して存在しており、ところどころ粒径で2 nm程度の白金微粒子がそれぞれ熱処理炭素材料上に担持されている様子が確認された。また、白金粒子は酸化スズ粒子と熱処理炭素材料上のどちらにも担持されている様子が確認された。
Heat treated carbon (BET specific surface area of several m 2 g -1 ) as a carbon material is dispersed in a tin fluoride aqueous solution containing 0.1 mol dm -3 for 24 hours, and tin fluoride is adsorbed on the surface, followed by filtration and washing. Thereafter, the resultant was dispersed in an aqueous boric acid solution, reacted for 24 hours, washed and dried, and then heat-treated at 500 ° C. for 1 hour in an argon atmosphere to obtain tin oxide-modified heat-treated carbon.
Furthermore, by using an aqueous chloroplatinic acid solution and an aqueous formaldehyde solution, a platinum-supported tin oxide-modified heat-treated carbon composite electrode catalyst having a platinum support amount of 4 wt% was obtained. A transmission electron microscope image of the catalyst B is shown in FIG. It was confirmed that tin oxide particles having a particle size of about 5 to 15 nm were aggregated and that platinum fine particles having a particle size of about 2 nm were supported on the heat-treated carbon material. Further, it was confirmed that the platinum particles were supported on both the tin oxide particles and the heat-treated carbon material.
0.0001 mol dm-3含むフッ化スズ水溶液中に炭素材料として熱処理炭素(BET比表面積 数m2 g-1)を24時間分散させると共にその表面にフッ化スズを吸着させた後、濾別、洗浄後、ホウ酸水溶液に分散させ、24時間反応後、洗浄、乾燥させた後、アルゴン雰囲気下500℃で1時間の熱処理を施して酸化スズ修飾熱処理炭素を得た。
さらに、塩化白金酸水溶液とホルムアルデヒド水溶液を用いることにより、白金担持量4wt%の白金担持酸化スズ修飾熱処理炭素複合電極触媒Bを得た。この触媒Bの透過型電子顕微鏡像を図6に示す。粒径で5〜15 nm程度の酸化スズ粒子が粗に分散して存在しており、ところどころ粒径で2 nm程度の白金微粒子がそれぞれ熱処理炭素材料上に担持されている様子が確認された。また、白金粒子は酸化スズ粒子と熱処理炭素材料上のどちらにも担持されている様子が確認された。
Heat treated carbon (BET specific surface area number m 2 g -1 ) as a carbon material is dispersed for 24 hours in a tin fluoride aqueous solution containing 0.0001 mol dm -3, and tin fluoride is adsorbed on the surface, followed by filtration and washing. Thereafter, the resultant was dispersed in an aqueous boric acid solution, reacted for 24 hours, washed and dried, and then heat-treated at 500 ° C. for 1 hour in an argon atmosphere to obtain tin oxide-modified heat-treated carbon.
Furthermore, a platinum-supported tin oxide-modified heat-treated carbon composite electrode catalyst B having a platinum-supported amount of 4 wt% was obtained by using a chloroplatinic acid aqueous solution and a formaldehyde aqueous solution. A transmission electron microscope image of the catalyst B is shown in FIG. It was confirmed that tin oxide particles having a particle size of about 5 to 15 nm were roughly dispersed and platinum fine particles having a particle size of about 2 nm were supported on the heat-treated carbon material. Further, it was confirmed that the platinum particles were supported on both the tin oxide particles and the heat-treated carbon material.
本発明は、固体高分子形燃料電池等に用いる複合電極触媒とその製造方法であり、同電池の性能向上、及び耐久性の向上に資するものである。今後はコアーシェル触媒用電極触媒担体としても有用である。 The present invention relates to a composite electrode catalyst used for a polymer electrolyte fuel cell and the like and a method for producing the same, and contributes to improving the performance and durability of the battery. In the future, it will be useful as an electrode catalyst carrier for core-shell catalysts.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010134688A JP5531313B2 (en) | 2010-06-14 | 2010-06-14 | Composite electrode catalyst and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010134688A JP5531313B2 (en) | 2010-06-14 | 2010-06-14 | Composite electrode catalyst and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2012000525A JP2012000525A (en) | 2012-01-05 |
JP5531313B2 true JP5531313B2 (en) | 2014-06-25 |
Family
ID=45533158
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2010134688A Active JP5531313B2 (en) | 2010-06-14 | 2010-06-14 | Composite electrode catalyst and method for producing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5531313B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9343750B2 (en) * | 2012-06-26 | 2016-05-17 | Samsung Sdi Co., Ltd. | Supporter for fuel cell, and electrode for fuel cell, membrane-electrode assembly for a fuel cell, and fuel cell system including same |
JP2019096624A (en) * | 2019-03-08 | 2019-06-20 | 国立大学法人九州大学 | Electrode material |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007105699A (en) * | 2005-10-17 | 2007-04-26 | Nippon Sheet Glass Co Ltd | Noble metal fine particle-supporting material and its manufacturing method |
JP5150141B2 (en) * | 2007-06-11 | 2013-02-20 | 株式会社東芝 | Fuel cell catalyst material, membrane electrode assembly using fuel cell catalyst material, and fuel cell using membrane electrode assembly |
JP5407062B2 (en) * | 2008-11-17 | 2014-02-05 | Tdk株式会社 | Active material and electrode manufacturing method, active material, electrode and lithium ion secondary battery |
-
2010
- 2010-06-14 JP JP2010134688A patent/JP5531313B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
JP2012000525A (en) | 2012-01-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9385377B2 (en) | Method for producing a catalyst for fuel cells | |
CN105377428B (en) | Electrode catalyst for fuel cell and method for activating catalyst | |
JP5456797B2 (en) | Fuel cell electrode catalyst | |
WO2011055739A1 (en) | Carbon catalyst, process for production of same, and electrode and battery each utilizing same | |
WO2017199653A1 (en) | Cell electrode, composition for cell electrode catalyst layer, and cell | |
US9666877B2 (en) | Metal-oxide catalysts for fuel cells | |
CN111725524B (en) | Fuel cell cathode catalyst, preparation method thereof, membrane electrode and fuel cell | |
JP2008290062A (en) | Catalytic carrier, catalyst, method for manufacturing the catalytic carrier and method for manufacturing the catalyst | |
JP5531313B2 (en) | Composite electrode catalyst and method for producing the same | |
CN110600752B (en) | H2Method for preparing carbon-supported Pt alloy catalyst by gas-phase thermal reduction | |
JPWO2011136186A1 (en) | Electrode material | |
JP2019169289A (en) | Air electrode catalyst for fuel cell, manufacturing method of the same, and fuel cell using fuel cell air electrode catalyst | |
JP6331580B2 (en) | Electrode catalyst, catalyst layer precursor, catalyst layer, and fuel cell | |
WO2012127540A1 (en) | Metal oxide-platinum compound catalyst and method for producing same | |
JP6668018B2 (en) | Electrode catalyst for fuel cell, fuel cell, and method for producing the electrode catalyst | |
WO2011061941A1 (en) | (metal oxide)-platinum composite catalyst, and process for production thereof | |
JP2006092957A (en) | Cathode catalyst for solid polymer fuel cell, cathode electrode equipped with catalyst, solid polymer fuel cell equipped with electrode, and manufacturing method of catalyst | |
JP6668019B2 (en) | Electrode catalyst for fuel cell, fuel cell, and method for producing the electrode catalyst | |
WO2023063265A1 (en) | Electrode catalyst for hydrogen fuel cell anode | |
WO2023068086A1 (en) | Electrode catalyst for hydrogen fuel cell anodes | |
JP4915758B1 (en) | Metal oxide / platinum composite catalyst for oxygen reduction and process for producing the same | |
JP5581884B2 (en) | Method for producing catalyst-supported powder for fuel cell, method for producing electrode for fuel cell | |
JP2021034128A (en) | Graphitization carbon porous body for fuel cell catalyst support, fuel cell catalyst, and manufacturing method of fuel cell catalyst layer | |
JP5626968B2 (en) | ELECTRODE CATALYST FOR FUEL CELL, PROCESS FOR PRODUCING THE SAME, AND MEMBRANE ELECTRODE ASSEMBLY FOR POLYUMER | |
JP2019053901A (en) | Method for manufacturing electrode catalyst |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20121122 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121127 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130913 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131015 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140318 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140331 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5531313 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |