JP4875266B2 - Cathode electrode catalyst for fuel cell and production method thereof - Google Patents
Cathode electrode catalyst for fuel cell and production method thereof Download PDFInfo
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- JP4875266B2 JP4875266B2 JP2001288050A JP2001288050A JP4875266B2 JP 4875266 B2 JP4875266 B2 JP 4875266B2 JP 2001288050 A JP2001288050 A JP 2001288050A JP 2001288050 A JP2001288050 A JP 2001288050A JP 4875266 B2 JP4875266 B2 JP 4875266B2
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- 239000003054 catalyst Substances 0.000 title claims description 34
- 239000000446 fuel Substances 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229910002839 Pt-Mo Inorganic materials 0.000 claims description 38
- 229910045601 alloy Inorganic materials 0.000 claims description 23
- 239000000956 alloy Substances 0.000 claims description 23
- 239000005518 polymer electrolyte Substances 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 47
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 43
- 229910052799 carbon Inorganic materials 0.000 description 39
- 239000000243 solution Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229920000557 Nafion® Polymers 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003411 electrode reaction Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000005574 cross-species transmission Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000009790 rate-determining step (RDS) Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002849 PtRu Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- 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
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- Catalysts (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、固体高分子型燃料電池用カソード電極触媒およびその製造方法に関するものである。
【０００２】
【従来の技術】
燃料電池は、水素と酸素から水を得る電池反応によって起電力を得ている。原料の水素は、メタノールなどの原燃料と水を改質触媒の存在下に反応させて得られる。このような燃料電池のうち、特に、固体高分子型燃料電池（ＰＥＦＣ：Ｐｏｌｙｍｅｒ Ｅｌｅｃｔｒｏｌｙｔｅ Ｆｕｅｌ Ｃｅｌｌ）が優れた性能を発揮できるものとして注目されている。すなわち、固体高分子型燃料電池では、水素を燃料とし、アノード（燃料極）、カソード（空気極）における電極反応によって起電力を得ている。ここでカソードでは、酸素の還元反応が起こっている。しかし、この還元反応が遅く、電極反応の律速段階を構成していると推測される。このカソードにおける電極反応には、白金触媒が用いられていることが多い。かかる白金触媒の触媒性能を上げることが望まれていた。
【０００３】
【発明が解決しようとする課題】
本発明は上記事情に対してなされたもので、カソードにおける酸素の還元反応の速度を上昇させるようにした固体高分子型燃料電池用カソード電極触媒およびその製造方法を提供することを目的とする。
【０００４】
【課題を解決するための手段】
上記目的を達成するため、本発明に係る固体高分子型燃料電池用カソード電極触媒は、Ｐｔ−Ｍｏ合金を担持した担体に、Ｓｂ２Ｏ４とＣｅＯ２から成るグループから選択した少なくとも一を担持させて成ることを特徴とする。
【０００５】
本発明は、別の側面として固体高分子型燃料電池用カソード電極触媒の製造方法であり、Ｐｔ−Ｍｏ合金担持担体をセリウム溶液に含浸し、空気中で１５０〜２００℃で焼成し、Ｐｔ−Ｍｏ合金−ＣｅＯ２担持担体から成る固体高分子型燃料電池用カソード電極触媒を得ることを特徴とする。
【０００６】
Ｐｔ−Ｍｏ合金−ＣｅＯ２担持担体は、Ｐｔ−Ｍｏ合金担持担体を微粒子状ＣｅＯ２と機械的に混合することによっても得られる。
【０００７】
さらに、本発明に係る固体高分子型燃料電池用カソード電極触媒の製造方法は、別の形態で、Ｓｂ２Ｏ３粉末を５００℃以上で空気中で焼成し、Ｐｔ−Ｍｏ合金担持担体と機械的に混合し、Ｐｔ−Ｍｏ合金−Ｓｂ２Ｏ４担持担体を得るようにしている。
【０００８】
【発明の実施の形態】
以下、本発明に係る固体高分子型燃料電池用カソード電極触媒およびその製造方法をその実施の形態等についてさらに詳細に説明する。
【０００９】
燃料電池では、その一実施の形態として、固体高分子膜を挟んで燃料極側の白金触媒層と、空気極側の白金触媒層とを備えている。ここで、アノード（燃料極）、カソード（空気極）では、下記のような反応が行われる。
【００１０】
アノードにおいて白金触媒層により、以下の反応を起こさせる。
Ｈ２ → ２Ｈ＋＋２ｅ−
この反応によって生じるＨ＋が拡散する。
一方、カソードにおいて白金触媒層により、以下の反応を起こさせる。
２Ｈ＋＋２ｅ―＋１／２Ｏ２ → Ｈ２Ｏ
これらの反応を合わせて電池反応が構成され、起電力を得ることができる。
【００１１】
ここで、前記したように、カソード側の空気の還元反応の抵抗が大きく律速段階を構成しているものと思われる。本発明らは、白金触媒層に用いるＰｔ−Ｍｏ合金を用いた電極触媒について、鋭意検討した結果、さらにＳｂ２Ｏ４とＣｅＯ２から成るグループから選択した少なくとも一の助触媒を用いることによって、このような抵抗が大幅に減少することを見出した。
その原理については、完全には裏付けられていないものの、ほぼ図１について以下に説明するところによると思われる。
図１に示すように、まず、担体粒子１上の助触媒粒子２に酸素分子３が捕獲される。該酸素分子３は、Ｐｔ−Ｍｏ合金の粒子４中のＭｏ成分に引かれてＰｔ−Ｍｏ合金粒子４にスピルオーバーする。これによって、Ｐｔ成分の触媒特性が発揮され、酸素の還元反応が速やかに進行する。なお、本発明者らは、Ｓｂ２Ｏ４を助触媒とする場合には、Ｐｔ−Ｍｏ合金でなければ効果が確認できないのに対し、ＣｅＯ２で単にＰｔだけを担持した担体上に担持するだけで抵抗低減の効果を確認している。したがって、図１のメカニズムのように酸素のスピルオーバーは、ＣｅＯ２を用いた場合、Ｍｏがなくても進行するものと推測される。
【００１２】
前記担体の粉末は、炭素粉末が好ましく、例えば、黒鉛、カーボンブラック、電気導電性を有する活性炭等を挙げることができる。特に、固体高分子型燃料電池用電極触媒には、ケッチェンカーボン、バルカンカーボンが好ましい。
【００１３】
Ｐｔ−Ｍｏ合金を用いる場合、固体高分子型燃料電池用カソード電極触媒に含まれるＰｔ−Ｍｏ合金成分中のＭｏの比率は１〜９９モル％、Ｐｔ−Ｍｏ合金をカーボンに担持した場合のＰｔ−Ｍｏ合金担持カーボン中のＰｔ−Ｍｏ合金の比率は、１〜９９ｗｔ％であることが好ましい。また、Ｐｔ−Ｍｏ合金を用いる場合、助触媒としてのＣｅＯ２、Ｓｂ２Ｏ４の担持量は、Ｐｔ−Ｍｏ合金担持カーボンの重量に対し、０．０１〜１０倍が好ましい。
【００１４】
次いで、本発明に係る固体高分子型燃料電池用カソード電極触媒の製造方法について、カーボン担体に触媒活性成分を担持する場合を挙げてその実施の形態を説明する。
【００１５】
Ｐｔのモル量が所定の量になるようにＰｔ溶液を調製する。
【００１６】
Ｐｔ溶液としては、Ｈ２ＰｔＣｌ６溶液、Ｐｔ（ＮＯ２）２（ＮＨ３）２等のＰｔ錯イオン溶液を挙げることができる。このＰｔ溶液を沸騰した水／エタノール混合溶液中に混合し、Ｐｔイオンを還元する。冷却後カーボン担体となるケッチェンカーボン等のカーボン粉末を添加し、カーボン粉末にＰｔを吸着担持させる。その後、ろ過、乾燥し、水素雰囲気中で熱処理し、Ｐｔ担持カーボンを得る。
【００１７】
次に、Ｐｔのモル数の０．１〜２倍のＭｏ量の５塩化モリブデン水溶液等のモリブデン水溶液にＰｔ担持カーボンを含浸し、水素で２５０℃〜８００℃で還元し、Ｐｔ−Ｍｏ合金担持カーボンを得る。次に、Ｐｔの重量に対して０．０１〜１０倍のＣｅＯ２を含むように硝酸セリウム水溶液等のセリウム水溶液をＰｔＭｏ担持カーボンに含浸し、空気中１５０〜２００℃で焼成し、Ｐｔ−Ｍｏ合金−ＣｅＯ２担持カーボンを得る。
【００１８】
また、Ｐｔ−Ｍｏ合金担持カーボンを得た後、ＣｅＯ２の代わりに、Ｓｂ２Ｏ４を担持させて、Ｐｔ−Ｍｏ合金−Ｓｂ２Ｏ４ 担持カーボンを得ることができる。
【００１９】
この場合、Ｐｔ−Ｍｏ合金担持カーボンの重量の０．０１〜１０倍のＳｂ２Ｏ４となるようにＳｂ２Ｏ３粉末（粒径０．１μｍ以下）を５００℃以上で空気中で焼成し、Ｐｔ−Ｍｏ合金担持カーボンと機械的に混合し、Ｐｔ−Ｍｏ合金−Ｓｂ２Ｏ４担持カーボンを得ることができる。機械的に混合するのは、５００℃以上におけるＳｂ２Ｏ４の焼成と同時に行うと、カーボン成分が燃えてしまうためである。
【００２０】
なお、Ｐｔ−Ｍｏ合金担持カーボン（ＰｔＭｏ／Ｃ）は、市販品をそのまま用いることもできる。
Ｐｔ−Ｍｏ合金−ＣｅＯ２担持カーボンはＰｔ−Ｍｏ合金担持カーボンに微粒子状ＣｅＯ２を機械的に混合して得ることもできる。
【００２１】
【実施例】
実施例１
Ｐｔのモル量が０．６ｍｍｏｌになるようにＨ２ＰｔＣｌ６溶液（Ｐｔ含有量１００ｇ／ｌ）を１ｇ金属／ｌに希釈した。
イオン交換水１４４０ｇ、エタノール１１４０ｇ、ポリビニルアルコール０．４ｇの溶液を沸騰させた。この沸騰した溶液に、先に調製したＰｔイオン溶液を添加し、１５分（通常、１０分〜２４時間）反応させ、Ｐｔイオンを還元した。冷却後、カーボン粉末（比表面積が８００ｍ２／ｇのケッチェンカーボン）１２０ｍｇを添加、攪拌し、カーボンにＰｔを吸着担持させた。その後、ろ過、乾燥し、水素雰囲気中で２５０℃、１時間（通常、０．５〜６時間）熱処理し、ポリビニルアルコールを熱分解除去し、Ｐｔ担持カーボン触媒を得た。
【００２２】
次に、Ｐｔのモル数の１倍（通常、０．１〜２倍）のＭｏ量の５塩化モリブデン水溶液にＰｔ担持カーボンを含浸し、水素で５００℃（通常、２５０℃〜８００℃）で還元し、Ｐｔ−Ｍｏ合金担持カーボンを得た。
次に、硝酸セリウム水溶液をＰｔ−Ｍｏ合金担持カーボンに含浸し、空気中２００℃で焼成し、Ｐｔ−Ｍｏ合金−ＣｅＯ２担持カーボンを得た。
【００２３】
実施例２
Ｐｔのモル量が０．６ｍｍｏｌになるようにＨ２ＰｔＣｌ６溶液（Ｐｔ含有量１００ｇ／ｌ）を１ｇ金属／ｌに希釈した。
イオン交換水１４４０ｇ、エタノール１１４０ｇ、ポリビニルアルコール０．４ｇの溶液を沸騰させた。この沸騰した溶液に、先に調製したＰｔイオン溶液を添加し、１５分（通常、１０分〜２４時間）反応させ、Ｐｔイオンを還元した。冷却後、カーボン粉末（比表面積が８００ｍ２／ｇのケッチェンカーボン）１２０ｍｇを添加、攪拌し、カーボンにＰｔを吸着担持させた。その後、ろ過、乾燥し、水素雰囲気中で２５０℃、１時間（通常、０．５〜６時間）熱処理し、ポリビニルアルコールを熱分解除去し、Ｐｔ担持カーボン触媒を得た。
次に、Ｐｔのモル数の１倍（通常、０．１〜２倍）のＭｏ量の５塩化モリブデン水溶液にＰｔ担持カーボンを含浸し、水素で２５０℃〜８００℃で還元し、Ｐｔ−Ｍｏ合金担持カーボンを得た。
次に、Ｐｔ−Ｍｏ合金担持カーボンの重量の２倍（通常、０．０１〜１０倍）のＳｂ２Ｏ４となるようにＳｂ２Ｏ３粉末（粒径０．１μｍ以下）を５００℃以上で空気中で焼成し、Ｐｔ−Ｍｏ合金担持カーボンと機械的に混合し、Ｐｔ−Ｍｏ合金−Ｓｂ２Ｏ４担持カーボンを得た。
【００２４】
実施例３
実施例１、２のカソード電極触媒を用いて固体高分子型燃料電池を製造し、その試験を行い、発電性能を評価した。
【００２５】
（電池セルの調製）
アノード電極触媒（ＰｔＲｕ合金担持カーボン）に水／エタノール混合液並びに高分子電解質溶液としてナフィオン溶液を添加して超音波攪拌にてスラリーを調製した。得られたスラリーをテフロン（登録商標）シートに塗布して膜厚５０μｍの固体高分子膜（デュポン社製で、商品名がナフィオン膜）の片面に転写し、アノード極を形成した。アノード極中のＰｔ量は０．５ｍｇ／ｃｍ２で、Ｒｕ量は０．５ｍｇ／ｃｍ２で、ナフィオン量は１ｍｇ／ｃｍ２であった。
【００２６】
一方、実施例１、２のカソード電極触媒に水／エタノール混合液並びに高分子電解質溶液としてナフィオン溶液を添加して超音波攪拌にてスラリーを調製した。得られたスラリーをテフロンシートに塗布して膜厚５０μｍの固体高分子膜（デュポン社製で、商品名がナフィオン膜）のアノードを転写した面と反対側の面に転写し、カソード極を形成した。カソード極中のＰｔ量は０．５ｍｇ／ｃｍ２で、ナフィオン量は０．５ｍｇ／ｃｍ２であった。アノード極及びカソード極それぞれにカーボンペーパを貼り付けた後、これらを１対のセパレータで挟み、５ｃｍ四方の電極セルを作製した。
【００２７】
＜発電性能評価＞
得られた電極セル１、２について、下記に説明する試験条件で発電試験を行い、その結果を下記表１に示す。
【００２８】
アノード側：Ｈ２ ６０％、ＣＯ２ ２０％、Ｎ２ ２０％、ＣＯ１０ｐｐｍ、２ａｔａ、温度８０℃、水素利用率８０％カソード側：空気（Ａｉｒ）、２ａｔａ、温度８０℃、空気利用率４０％
【表１】
表１から明らかなように、試作触媒１、２を用いた電極セル１、２は、従来セルに比べ高性能であることがわかる。
【００３０】
【発明の効果】
上記したところから明らかなように、本発明によれば、カソードにおける酸素の還元反応の速度を上昇させるようにした固体高分子型燃料電池用カソード電極触媒およびその製造方法が提供される。
【図面の簡単な説明】
【図１】 本発明における酸素の還元のメカニズムを説明する概念図である。
【符号の説明】
１ 担体粒子
２ 助触媒粒子
３ 酸素分子
４ 合金粒子[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a cathode electrode catalyst for a polymer electrolyte fuel cell and a method for producing the same.
[0002]
[Prior art]
A fuel cell obtains an electromotive force by a cell reaction that obtains water from hydrogen and oxygen. The raw material hydrogen is obtained by reacting raw fuel such as methanol and water in the presence of a reforming catalyst. Among such fuel cells, in particular, a polymer electrolyte fuel cell (PEFC) has been attracting attention as being able to exhibit excellent performance. That is, in a polymer electrolyte fuel cell, hydrogen is used as a fuel, and an electromotive force is obtained by an electrode reaction at an anode (fuel electrode) and a cathode (air electrode). Here, a reduction reaction of oxygen occurs at the cathode. However, this reduction reaction is slow, and is presumed to constitute a rate-determining step for the electrode reaction. A platinum catalyst is often used for the electrode reaction at the cathode. It has been desired to improve the catalytic performance of such platinum catalysts.
[0003]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a cathode electrode catalyst for a polymer electrolyte fuel cell and a method for producing the same that increase the rate of oxygen reduction reaction at the cathode.
[0004]
[Means for Solving the Problems]
In order to achieve the above object, a cathode electrode catalyst for a polymer electrolyte fuel cell according to the present invention carries at least one selected from the group consisting of Sb 2 O 4 and CeO 2 on a carrier carrying a Pt—Mo alloy. It is characterized by being made to do.
[0005]
Another aspect of the present invention is a method for producing a cathode electrode catalyst for a polymer electrolyte fuel cell, wherein a Pt—Mo alloy-supported carrier is impregnated with a cerium solution, calcined in air at 150 to 200 ° C., Pt— A cathode electrode catalyst for a polymer electrolyte fuel cell comprising a Mo alloy-CeO 2 carrier is obtained.
[0006]
Pt-Mo alloy -CeO 2 loaded carrier can also be obtained by mixing the Pt-Mo alloy-supporting carrier in particulate CeO 2 and mechanical.
[0007]
Furthermore, the method for producing a cathode electrode catalyst for a polymer electrolyte fuel cell according to the present invention is another embodiment, in which Sb 2 O 3 powder is fired in air at 500 ° C. or higher, and a Pt—Mo alloy-supported carrier and machine To obtain a Pt—Mo alloy—Sb 2 O 4 carrier.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the cathode electrode catalyst for a polymer electrolyte fuel cell and the method for producing the same according to the present invention will be described in more detail with respect to embodiments thereof.
[0009]
In one embodiment, the fuel cell includes a platinum catalyst layer on the fuel electrode side and a platinum catalyst layer on the air electrode side with a solid polymer film interposed therebetween. Here, the following reaction is performed at the anode (fuel electrode) and the cathode (air electrode).
[0010]
The following reaction is caused by the platinum catalyst layer at the anode.
H 2 → 2H + + 2e −
H + produced by this reaction diffuses.
On the other hand, the following reaction is caused by the platinum catalyst layer at the cathode.
2H + + 2e − + 1 / 2O 2 → H 2 O
A battery reaction is constituted by combining these reactions, and an electromotive force can be obtained.
[0011]
Here, as described above, it is considered that the resistance of the cathode side reduction reaction is large and constitutes a rate-determining step. As a result of intensive studies on an electrode catalyst using a Pt—Mo alloy used for the platinum catalyst layer, the present inventors have further used at least one promoter selected from the group consisting of Sb 2 O 4 and CeO 2 . It has been found that such resistance is greatly reduced.
Although the principle is not fully supported, it is believed that it is almost as described below with respect to FIG.
As shown in FIG. 1, first, oxygen molecules 3 are captured by the
[0012]
The carrier powder is preferably carbon powder, and examples thereof include graphite, carbon black, and activated carbon having electrical conductivity. In particular, ketjen carbon and vulcan carbon are preferred for the electrode catalyst for a polymer electrolyte fuel cell.
[0013]
When a Pt—Mo alloy is used, the proportion of Mo in the Pt—Mo alloy component contained in the cathode electrode catalyst for a polymer electrolyte fuel cell is 1 to 99 mol%, and Pt when the Pt—Mo alloy is supported on carbon. The ratio of the Pt—Mo alloy in the —Mo alloy-supporting carbon is preferably 1 to 99 wt%. When a Pt—Mo alloy is used, the supported amount of CeO 2 and Sb 2 O 4 as promoters is preferably 0.01 to 10 times the weight of the Pt—Mo alloy supporting carbon.
[0014]
Next, an embodiment of the method for producing a cathode electrode catalyst for a polymer electrolyte fuel cell according to the present invention will be described with reference to a case where a catalytically active component is supported on a carbon support.
[0015]
A Pt solution is prepared so that the molar amount of Pt becomes a predetermined amount.
[0016]
Examples of the Pt solution include Pt complex ion solutions such as H 2 PtCl 6 solution and Pt (NO 2 ) 2 (NH 3 ) 2 . This Pt solution is mixed in a boiling water / ethanol mixed solution to reduce Pt ions. After cooling, carbon powder such as ketjen carbon which becomes a carbon carrier is added, and Pt is adsorbed and supported on the carbon powder. Then, it is filtered and dried, and heat-treated in a hydrogen atmosphere to obtain Pt-supported carbon.
[0017]
Next, a Pt-supported carbon is impregnated in a molybdenum aqueous solution such as a molybdenum pentachloride aqueous solution having an Mo amount of 0.1 to 2 times the number of moles of Pt, reduced at 250 ° C. to 800 ° C. with hydrogen, and Pt—Mo alloy supported Get carbon. Next, a PtMo-supported carbon is impregnated with a cerium aqueous solution such as a cerium nitrate aqueous solution so as to contain 0.01 to 10 times as much CeO 2 as the weight of Pt, and fired at 150 to 200 ° C. in air. obtain an alloy -CeO 2 on carbon.
[0018]
Further, after obtaining Pt—Mo alloy-supported carbon, Sb 2 O 4 can be supported instead of CeO 2 to obtain Pt—Mo alloy—Sb 2 O 4 -supported carbon.
[0019]
In this case, calcined in air at Pt-
[0020]
In addition, a commercial item can also be used for Pt-Mo alloy carrying | support carbon (PtMo / C) as it is.
The Pt—Mo alloy-CeO 2 supported carbon can also be obtained by mechanically mixing fine particles of CeO 2 with the Pt—Mo alloy supported carbon.
[0021]
【Example】
Example 1
The H 2 PtCl 6 solution (Pt content 100 g / l) was diluted to 1 g metal / l so that the molar amount of Pt was 0.6 mmol.
A solution of 1440 g of ion-exchanged water, 1140 g of ethanol and 0.4 g of polyvinyl alcohol was boiled. The previously prepared Pt ion solution was added to the boiled solution and reacted for 15 minutes (usually 10 minutes to 24 hours) to reduce Pt ions. After cooling, 120 mg of carbon powder (Ketjen carbon having a specific surface area of 800 m 2 / g) was added and stirred to adsorb and carry Pt on the carbon. Then, it filtered and dried and heat-processed in hydrogen atmosphere at 250 degreeC for 1 hour (usually 0.5-6 hours), the polyvinyl alcohol was thermally decomposed and the Pt carrying | support carbon catalyst was obtained.
[0022]
Next, Pt-supported carbon is impregnated in a molybdenum pentachloride aqueous solution having an amount of Mo that is 1 time (usually 0.1 to 2 times) the number of moles of Pt, and is hydrogenated at 500 ° C. (usually 250 ° C. to 800 ° C.). Reduction was performed to obtain carbon supported on a Pt—Mo alloy.
Next, Pt—Mo alloy-supported carbon was impregnated with an aqueous cerium nitrate solution and fired in air at 200 ° C. to obtain Pt—Mo alloy-CeO 2 -supported carbon.
[0023]
Example 2
The H 2 PtCl 6 solution (Pt content 100 g / l) was diluted to 1 g metal / l so that the molar amount of Pt was 0.6 mmol.
A solution of 1440 g of ion-exchanged water, 1140 g of ethanol and 0.4 g of polyvinyl alcohol was boiled. The previously prepared Pt ion solution was added to the boiled solution and reacted for 15 minutes (usually 10 minutes to 24 hours) to reduce Pt ions. After cooling, 120 mg of carbon powder (Ketjen carbon having a specific surface area of 800 m 2 / g) was added and stirred to adsorb and carry Pt on the carbon. Then, it filtered and dried and heat-processed in hydrogen atmosphere at 250 degreeC for 1 hour (usually 0.5-6 hours), the polyvinyl alcohol was thermally decomposed and the Pt carrying | support carbon catalyst was obtained.
Next, Pt-supported carbon is impregnated in a molybdenum pentachloride aqueous solution having a Mo amount that is 1 time (usually 0.1 to 2 times) the number of moles of Pt, and reduced at 250 to 800 ° C. with hydrogen. Alloy-supporting carbon was obtained.
Next, the Sb 2 O 3 powder (particle size of 0.1 μm or less) is 500 ° C. or higher so that the Sb 2 O 4 is twice (usually 0.01 to 10 times) the weight of the Pt—Mo alloy-supported carbon. And then mechanically mixed with Pt—Mo alloy-carrying carbon to obtain Pt—Mo alloy-Sb 2 O 4 -carrying carbon.
[0024]
Example 3
A polymer electrolyte fuel cell was manufactured using the cathode electrode catalyst of Examples 1 and 2, the test was performed, and the power generation performance was evaluated.
[0025]
(Preparation of battery cells)
A water / ethanol mixed solution and a Nafion solution as a polymer electrolyte solution were added to an anode electrode catalyst (PtRu alloy-supported carbon), and a slurry was prepared by ultrasonic stirring. The obtained slurry was applied to a Teflon (registered trademark) sheet and transferred to one side of a 50 μm thick solid polymer film (manufactured by DuPont, product name is Nafion film) to form an anode electrode. The amount of Pt in the anode electrode was 0.5 mg / cm 2 , the amount of Ru was 0.5 mg / cm 2 , and the amount of Nafion was 1 mg / cm 2 .
[0026]
Meanwhile, a water / ethanol mixed solution and a Nafion solution as a polymer electrolyte solution were added to the cathode electrode catalysts of Examples 1 and 2, and a slurry was prepared by ultrasonic stirring. The obtained slurry was applied to a Teflon sheet and transferred to the surface opposite to the surface to which the anode of a solid polymer film (made by DuPont, product name is Nafion film) with a thickness of 50 μm was transferred to form a cathode electrode. did. The amount of Pt in the cathode electrode was 0.5 mg / cm 2 and the amount of Nafion was 0.5 mg / cm 2 . Carbon paper was affixed to each of the anode electrode and the cathode electrode, and these were sandwiched between a pair of separators to produce a 5 cm square electrode cell.
[0027]
<Evaluation of power generation performance>
The obtained
[0028]
Anode side: H 2 60%, CO 2 20%, N 2 20%, CO 10 ppm, 2 ata, temperature 80 ° C., hydrogen utilization rate 80% Cathode side: air, air, temperature 80 ° C., air utilization rate 40%
[Table 1]
As can be seen from Table 1, the
[0030]
【Effect of the invention】
As is apparent from the above description, according to the present invention, there are provided a cathode electrode catalyst for a polymer electrolyte fuel cell and a method for producing the same which increase the rate of oxygen reduction reaction at the cathode.
[Brief description of the drawings]
FIG. 1 is a conceptual diagram illustrating the mechanism of oxygen reduction in the present invention.
[Explanation of symbols]
DESCRIPTION OF
Claims (4)
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| US7566388B2 (en) | 2002-12-17 | 2009-07-28 | Asahi Kasei Chemicals Corporation | Electrode catalyst for oxygen reduction and gas diffusion electrode |
| CN1906783A (en) * | 2004-01-22 | 2007-01-31 | 丰田自动车株式会社 | Fuel cell cathode and polymer electrolyte fuel cell having same |
| JP4872206B2 (en) * | 2004-11-05 | 2012-02-08 | トヨタ自動車株式会社 | Fuel cell system |
| JP4901143B2 (en) * | 2005-06-28 | 2012-03-21 | 株式会社東芝 | Electrode catalyst, electrode for fuel electrode, fuel cell device, and method for producing electrode catalyst |
| KR101397020B1 (en) * | 2007-11-20 | 2014-05-21 | 삼성에스디아이 주식회사 | Electrocatalyst for fuel cell, method for preparing the same and fuel cell including the electrode comprising the electrocatalyst |
| KR20100069492A (en) * | 2008-12-16 | 2010-06-24 | 삼성전자주식회사 | Electrode catalyst for fuel cell and fuel cell including electrode comprising the electrode catalyst |
| JP5493085B2 (en) * | 2009-03-27 | 2014-05-14 | 独立行政法人物質・材料研究機構 | Cathode material |
| KR20130087292A (en) * | 2012-01-27 | 2013-08-06 | 삼성전자주식회사 | Composite, catalyst including the composite, fuel cell including the same, and lithium air battery including the same |
| JP2017174562A (en) * | 2016-03-22 | 2017-09-28 | 三菱自動車工業株式会社 | Electrode catalyst for fuel cell |
| JP6465083B2 (en) * | 2016-08-01 | 2019-02-06 | トヨタ自動車株式会社 | Fuel cell system |
| KR20220084361A (en) * | 2019-10-18 | 2022-06-21 | 젠셀 리미티드 | Nickel-based catalyst for fuel cell anode |
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| CA1088149A (en) * | 1976-06-15 | 1980-10-21 | Gerda M. Kohlmayr | Method of fabricating a fuel cell electrode |
| JPH04284361A (en) * | 1991-03-14 | 1992-10-08 | Sanyo Electric Co Ltd | Fuel cell |
| JPH05144444A (en) * | 1991-11-25 | 1993-06-11 | Toshiba Corp | Fuel cell and electrode manufacturing method |
| JPH05217586A (en) * | 1992-02-07 | 1993-08-27 | Fuji Electric Co Ltd | Fuel cell and manufacture thereof |
| JP3588930B2 (en) * | 1996-08-08 | 2004-11-17 | アイシン精機株式会社 | Air electrode for fuel cell and method of manufacturing the same |
| JPH1085586A (en) * | 1996-09-13 | 1998-04-07 | Toshiba Corp | Functional materials, oxidation catalysts, combustion catalysts, methanol reforming catalysts, and electrode catalysts |
| JP3351285B2 (en) * | 1997-03-27 | 2002-11-25 | 三菱電機株式会社 | Anode electrode catalyst for polymer electrolyte fuel cells |
| JPH11214013A (en) * | 1997-11-18 | 1999-08-06 | Fuji Electric Co Ltd | Phosphoric acid fuel cell |
| US6165636A (en) * | 1998-04-14 | 2000-12-26 | De Nora S.P.A. | Composition of a selective oxidation catalyst for use in fuel cells |
| JP3243502B2 (en) * | 1999-09-28 | 2002-01-07 | 独立行政法人産業技術総合研究所 | Electrochemical generation of active oxygen and method for promoting NOx selective reduction reaction |
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