JP3643552B2 - Catalyst for air electrode of solid polymer electrolyte fuel cell and method for producing the catalyst - Google Patents
Catalyst for air electrode of solid polymer electrolyte fuel cell and method for producing the catalyst Download PDFInfo
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- JP3643552B2 JP3643552B2 JP2001333877A JP2001333877A JP3643552B2 JP 3643552 B2 JP3643552 B2 JP 3643552B2 JP 2001333877 A JP2001333877 A JP 2001333877A JP 2001333877 A JP2001333877 A JP 2001333877A JP 3643552 B2 JP3643552 B2 JP 3643552B2
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- 239000003054 catalyst Substances 0.000 title claims description 114
- 239000000446 fuel Substances 0.000 title claims description 28
- 239000005518 polymer electrolyte Substances 0.000 title claims description 16
- 239000007787 solid Substances 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 136
- 229910052697 platinum Inorganic materials 0.000 claims description 62
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 54
- 229910052751 metal Inorganic materials 0.000 claims description 48
- 239000002184 metal Substances 0.000 claims description 48
- 229910052742 iron Inorganic materials 0.000 claims description 27
- 239000010941 cobalt Substances 0.000 claims description 23
- 229910017052 cobalt Inorganic materials 0.000 claims description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 21
- 238000005275 alloying Methods 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 description 19
- 239000001301 oxygen Substances 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 18
- 230000000694 effects Effects 0.000 description 18
- 229910045601 alloy Inorganic materials 0.000 description 11
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- 238000011068 loading method Methods 0.000 description 10
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- 229920000642 polymer Polymers 0.000 description 9
- 239000007784 solid electrolyte Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 7
- 229910001260 Pt alloy Inorganic materials 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 229910000531 Co alloy Inorganic materials 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
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Images
Classifications
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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
Description
【０００１】
【発明の属する技術分野】
本発明は高分子固体電解質形燃料電池用の触媒に関する。特に、高分子固体電解質形燃料電池の空気極に使用される触媒に関する。
【０００２】
【従来の技術】
燃料電池は次世代の発電システムとして大いに期待されるものであり、その中で高分子固体電解質を電解質として用いる高分子固体電解質形燃料電池は、リン酸形燃料電池等の他形式の燃料電池と比較して動作温度が低く、かつコンパクトであることから、電気自動車用電源として有望視されている。
【０００３】
高分子固体電解質形燃料電池は、水素極及び空気極の２つの電極と、これら電極に挟持される高分子固体電解質膜とからなる積層構造を有し、水素極には水素を含む燃料を供給し、空気極には酸素又は空気を供給することで、それぞれの電極で生じる酸化、還元反応により電力を取り出すようにしている。これらの両電極は、電気化学的反応を促進させるための触媒と固体電解質との混合体が一般に適用されている。そして、この電極を構成する触媒としては、触媒活性が良好な白金を担持させた白金触媒が広く用いられている。
【０００４】
ところで、この高分子固体電解質形燃料電池電極用の触媒に要求される特性は水素極と空気極とでは異なるものがあると考えられる。即ち、水素極においては単に触媒活性が高いというだけではなく、耐久性特に耐一酸化炭素触媒被毒性が要求される。これは水素極へ燃料として供給される水素としては、その取り扱い性や、経済性等の観点から、メタノール等から得られる改質水素の適用が有力視されているが、この改質水素中には不純物として一酸化炭素が含まれており、これが触媒粒子に吸着し触媒を失活させるという問題があるからである。そのため、燃料極用の触媒については、触媒活性を維持しつつ耐一酸化炭素触媒被毒性を改善するために多くの研究がなされている。
【０００５】
【発明が解決しようとする課題】
一方、空気極に関しては水素極とは燃料が異なり、燃料中に一酸化炭素が含まれていないこともあり、上記一酸化炭素による触媒被毒を考慮した触媒の設計は不要であり、触媒活性の向上が要求される。ここで従来の空気極用の触媒の活性改善の手法としては、担体の特性の改善や触媒粒子となる白金の微細化、分散性の向上等が行なわれている。
【０００６】
しかしながら、担体の特性の改善や白金粒子の微細化等の物理的な特性の変更には限界があり、これらにより達成される触媒活性の向上も無制限に可能であるはずはない。本発明は、以上のような背景のもとになされたものであり、高分子固体電解質形燃料電池の空気極用の触媒について、従来の方法とは異なる観点から製造され高い触媒活性を有する触媒を明らかとし、これを提供することを目的とし、更に、かかる触媒の製造方法を提供することを目的としたものである。
【０００７】
【課題を解決するための手段】
本発明者らは、上記目的を達成すべく、触媒活性向上の手段として、補助金属の適用を検討した、補助金属とは、白金のような触媒金属以外の金属であり触媒金属の触媒活性や耐久性を向上させる機能を有するものをいう。かかる補助触媒金属の適用は、触媒の分野においては必ずしも新規のものではなく、燃料電池用触媒でもリン酸形燃料電池用の触媒については適用例もある。これに対し、本発明の対象である高分子固体電解質形燃料電池の空気極用触媒においては、このような補助金属を担持した触媒についての成功例は少ないことから純粋な白金触媒が一般に使用されている。これは、補助金属が触媒から脱離し、高分子膜に混入し高分子膜の特性を悪化させるおそれがあるからであり、その悪化の程度も無視できないものがあるからである。
【０００８】
そこで、本発明者等は、高分子固体電解質形燃料電池の空気極用触媒に対して最適の補助触媒金属を見出すと共に、上記高分子膜への補助金属の混入を抑制する手段を検討した結果、触媒活性を向上させることのできる補助触媒金属としては鉄、コバルトを用いるのが適当であることを見出し、更に、白金とこれら補助金属とを合金化することで補助金属を拘束し、高分子膜への補助金属の混入を抑制することができることに想到し本発明を完成させるに至った。
【０００９】
即ち、本発明は、炭素粉末担体上に白金と１の補助金属とを合金化してなる触媒粒子が担持された高分子固体電解質形燃料電池の空気極用の触媒であって、前記補助金属は、鉄又はコバルトであり、白金と補助金属との配合比は６：１〜３：２（モル比）であることを特徴とする高分子固体電解質形燃料電池の空気極用の触媒である。
【００１０】
本発明において、鉄、コバルトを補助触媒金属とすることにより触媒活性が向上する理由については必ずしも明らかではないが、鉄又はコバルトを白金に合金化することで白金の原子間距離が変化し、酸素分子との結合力が増大するために酸素の還元力が増加する仮説や、合金化により白金の電子状態が酸素を還元しやすい状態に変化したとする仮説、更には合金化により触媒粒子表面の表面状態（ラフネス）が変化したためという仮説が挙げられ、本発明においてもこれらのいずれかが作用して触媒活性を向上させているものと考えられる。そして、本発明においては白金と補助金属とを合金化することにより補助金属が担体から脱離し高分子膜へ混入することを防止するものである。
【００１１】
この触媒粒子を構成する白金と補助金属との配合比は、モル比で６：１〜３：２とする。６：１より補助金属の割合が低い場合、補助金属としての効果（活性の向上）が発揮されないからである。また、本発明においても主に触媒活性を発揮するのは白金であるから、補助金属の比率が高くなっても触媒活性が低下し、また、製造工程において合金化されずに単独で担持される補助金属の発生割合が増えるおそれがある。但し、補助金属の比率を上げることで白金の使用量を減少させ触媒コストを低下させることもできるというメリットもあることから、これらを勘案し補助金属の比率は最大で３：２とする。
【００１２】
ここで、本発明に係る触媒は、電極（空気極）としたときの特性を考慮すれば、白金と補助金属とが合金化された触媒粒子の担持密度を４０〜６５％とするのが好ましい。担持密度とは、担体に担持させる触媒粒子質量（本発明においては、白金質量と補助金属質量との合計重量）の触媒全体の担体質量に対する比をいう。担持密度をこのような範囲とするのは、電極としたときの特性及び本発明のような合金触媒において合金化を有効に生じさせるためである。即ち、燃料電池電極の設計にあたっては、使用する触媒の量は触媒自体の量ではなく担持されている触媒粒子の量を基準とする。従って、担持密度の低い触媒を適用とすると、触媒の量を増大させる必要があるが、触媒の量を増大させると当然に電極の厚みも増大する。かかる厚みの大きい電極では物質移動に制約が生じ、酸素の拡散効率の低下、水の排出効率の低下の要因となり、その結果、電極特性が低下する。また、本発明のような合金触媒では、担持密度が低くなると（担持させる白金粒子、鉄粒子又はコバルト粒子の数が低下すると）金属粒子同士の距離が大きくなりそれらの合金化が困難となる。このような事情を勘案し、電極特性を確保し、合金化を生じさせるために担持密度の最小値を４０％とするものである。一方、担持密度が高いと、担体に担持される触媒粒子の量が過大となり、合金化したときに合金触媒粒子が粗大化する。そこで、担持密度の最大値は６５％とするものである。
【００１３】
以上のように、本発明においては、従来の白金に補助触媒金属として鉄又はコバルトを所定比率で合金化しこれを担持させることで、優れた触媒活性を示すものである。ここで、本発明者らは、この触媒をより有効に機能させるため、この触媒粒子を担持させる担体について更に検討を行った。その結果、比表面積が６００〜１２００ｍ２/g の炭素粉末が担体として特に好ましいとの結論に至った。比表面積を６００ｍ２／ｇ以上とすることで、触媒が付着する面積を増加させることができるので触媒粒子を高い状態で分散させ有効表面積を高くすることができる一方、比表面積が１２００ｍ２／ｇを超えると、電極を形成する際にイオン交換樹脂の浸入できない超微細細孔（約２０Å未満）の存在割合が高くなり触媒粒子の利用効率が低くなるからである。そこで、比表面積を上記の範囲とすることで、貴金属粒子を高い状態で分散させ触媒単位質量あたりの活性を向上させる一方、触媒の利用効率を確保するものである。
【００１４】
次に、本発明に係る高分子固体電解質形燃料電池空気極用の触媒の製造方法について述べる。本発明に係る触媒の製造方法は、担体に触媒粒子を構成する白金と補助金属である鉄又はコバルトを担持する工程と、担持された白金と鉄又はコバルトとを合金化させる工程とからなる。
【００１５】
これらの工程について、まず担体に白金及び補助金属を担持する工程については特に限定はない。従って、従来のように白金塩溶液、補助金属となる金属塩溶液を担体に含浸させることで白金及び補助金属を担持させることができる。尚、白金の担持と補助金属の担時の順序については、いずれが先であっても又は同時であっても特に影響はない。
【００１６】
そして、担持された白金と補助金属との合金化についてであるが、上記のように本発明において白金と補助金属とを合金化する目的は、触媒活性の向上もあるが同時に補助金属が触媒から脱離し高分子固体電解質膜を汚染しないようにするためである。従って、本発明においては十分な合金状態を実現することが必要である。本発明者等はこの合金化の条件として、担体を水素還元雰囲気下で８００℃〜１２００℃加熱するのが適正であるとする。ここで、反応雰囲気の水素濃度は略１００％とするのが好ましい。
【００１７】
上記製造方法により得られる本発明に係る触媒によれば、優れた触媒活性を有し、且つ、高分子固体電解質膜を汚染することのない空気極用の触媒とすることができる。ここで、空気極は、イオン交換樹脂と触媒とを混合することにより製造されるが、このイオン交換樹脂と触媒との混合比は、０．７〜１．６（重量比）とするのが好ましい。混合比が０．７未満ではイオン交換樹脂による触媒の被覆が十分に達成できず、触媒の利用効率が低下すること及びプロトン導電性を十分確保できなことにより触媒の反応効率が低下するからである。また、混合比が１．６を超えると、ガス拡散及び水の排出に貢献する細孔が減少してしまい、触媒の反応効率が低下するからである。
【００１８】
【発明の実施の形態】
以下に本発明の好適な実施の形態を図面と共に説明する。
【００１９】
第１実施形態：本実施形態では、白金／鉄合金触媒を製造した。この合金系触媒は、予め上記炭素粉末に白金を担持させた白金触媒を作製し、これを鉄化合物溶液に含浸させることで鉄を担持させ、そして担体を熱処理することにより製造した。以下に詳しく説明する。
【００２０】
〔担体の選択〕 本実施形態で使用した担体は、炭素微粉末（商品名：ケッチェンブラックＥＣ）である。このこの担体の比表面積は、ＢＥＴ１点法にて測定したところ、８００ｍ２／ｇであった。
【００２１】
[白金触媒の調整] 白金溶液として、白金濃度０．８ｗｔ％のジニトロジアンミン白金硝酸溶液を１０００ｇ（白金含有量：８ｇ）に前記炭素粉末を１２ｇ浸漬させ攪拌後、還元剤として１００％エタノールを１００ｍｌ添加した。この溶液を沸点（約９５℃）で７時間、攪拌、混合し、白金を炭素粉末に担持させた。そして、濾過、乾燥後白金触媒とした。
【００２２】
[鉄の担持] 鉄溶液として、鉄濃度０．６３ｗｔ％の塩化鉄水溶液を６０ｇ（鉄含有量：０．３８ｇ）に、上記白金触媒１０ｇを浸漬させた。そして、この溶液を１時間攪拌し、６０℃で乾燥させた。
【００２３】
[熱処理] 以上の工程により白金及び鉄を担持させた担体につき、白金と鉄との合金化熱処理を行なった。この合金化熱処理は、１００％水素ガス中で、２時間、１０００℃に保持することにより行った。
【００２４】
以上の操作により製造される、白金／鉄合金触媒の各担持金属の比率は３：１である。また、白金及び鉄の担持密度は４２％である。これらの値は、担体に含浸させる白金溶液中の白金含有量、白金触媒に含浸させる鉄塩溶液中の鉄含有量を変化させることにより容易に制御することができる。
【００２５】
以上の製造方法により製造した白金／鉄合金触媒について、白金と鉄との担持比率を変化させたものを製造し、これらから空気極を製造した。空気極は、イオン交換樹脂（商品名：ナフィオン、Ｄｕｐｏｎ社製）の５％溶液をスプレードライにより製造した樹脂粉末１．２ｇと触媒１ｇとを、１−プロパノールの水溶液２４ｍＬに入れ、これをボールミルにて１００分間混合させて触媒ペーストを製造した。そして、カーボンペーパーにカーボンとＰＴＦＥとを表層へコーティングして製造したガス拡散層に前記触媒ペーストを白金量が０．２５ｍｇ／ｃｍ２となるように塗布印刷した。更に、これを１００℃で乾燥させた後、１３０℃、２０ｋｇ／ｃｍ２で１分間ホットプレスして電極とした。
【００２６】
実験例１：そして、これらの空気極を用いて、酸素質量活量を測定すべく、高分子電解質膜としてナフィオン１１２（商品名：Ｄｕｐｏｎ社製）を用いてシングルセルテストを行った。この酸素質量活量は、所定電位（０．９Ｖ）において酸素の還元により得られる電流値である。測定条件は、以下のようにした。
【００２７】
電極面積：２５ｃｍ２
温度：８０℃
圧力：大気圧
酸素：１００％
【００２８】
そして、本実施形態で製造した白金／鉄触媒により製造された空気極の酸素質量活量及び合金化していない従来の白金触媒の酸素活量の測定結果を表１に示す。
【００２９】
【表１】
表１から、本実施形態で製造した触媒は、鉄の合金化をしない場合よりもいずれも酸素質量活量が高いが、白金：鉄＝３：１の合金比率をピークとし、白金：鉄＝３：２と鉄の合金比率が高くなると酸素質量活量が低下することが確認された。
【００３１】
実験例２：次に、白金と鉄の担持比率を３：１に固定し、担持密度を変化させて空気極を製造し、実験例と同様の条件にて酸素活量を測定した。その結果を表２に示す。
【００３２】
【表２】
この結果から、担持密度４０〜６５％の間においては、担持密度５０％前後においてピークを示すが、補助触媒金属の添加のないものに比して高い酸素活性を有することが確認された。
【００３４】
第２実施形態：本実施形態では、白金／コバルト合金触媒を製造した。但し、本実施形態における合金触媒で使用した担体、及び、白金の担持工程、及び、熱処理については、第１実施形態と同様である。従って、重複する記載は避け、特徴のあるコバルトの担持工程のみについて説明する。
【００３５】
〔コバルトの担持〕 コバルト溶液として、コバルト濃度０．６６ｗｔ％の塩化コバルト水溶液を６０ｇ（コバルト含有量：０．４ｇ）に、上記白金触媒１０ｇを浸漬させた。そして、この溶液を１時間攪拌し、６０℃で乾燥させた。
【００３６】
以上の操作により製造される、白金／コバルト合金触媒の各担持金属の比率は３：１である。この比率は、第１実施形態と同様、白金触媒に含浸させるコバルト塩溶液中のコバルト含有量を変化させることにより容易に制御することができる。
【００３７】
実験例３：以上の製造方法により製造した白金／コバルト合金触媒について、第１実施形態と同様に白金とコバルトの合金比率を変化させた触媒を製造し、これらから空気極を製造した。そして、これらの空気極について、シングルセルテストにより酸素質量活量を測定した。測定条件は第１実施形態と同様である。この測定結果を表３に示す。
【００３８】
【表３】
表３から、本実施形態で製造した触媒は、第１実施形態同様、コバルトの合金化をしない場合よりもいずれも酸素質量活量が高く、白金：コバルト＝３：１の合金比率をピークとし、白金：コバルト＝３：２において酸素質量活量が低下することが確認された。
【００４０】
実験例４：上記酸素活量の測定に加え、実際の空気極の電池特性の検討を行った。このときの触媒の白金と補助触媒金属（鉄、コバルト）との担持比率は３：１とし、担持密度は４２％のものを用いた。電池特性は、所定の電流密度におけるセル電圧を基に評価し、測定条件は以下の通りとした。
【００４１】
電極面積：２５ｃｍ２
設定利用効率：４０％
温度：８０℃
圧力：大気圧
アノードガス：純水素
加湿条件：アノード 湿度１００％
カソード 湿度８０％
【００４２】
この結果を図１に示すが、図１からわかるように、補助触媒として鉄、コバルトを適用した本実施形態に係る触媒は、白金単独担持触媒よりも実用領域において高い電極特性を有することが確認された。
【００４３】
【発明の効果】
以上説明したように本発明は、従来、白金のみを担持した触媒が用いられていた高分子固体電解質形燃料電池の空気極用触媒に対し、補助触媒金属として鉄又はコバルトを用いるものである。これにより従来の空気極用触媒よりも高い触媒活性を発揮することができる。そして、本発明はこれら補助触媒金属を白金に合金化させることで補助触媒金属が触媒から脱離し高分子固体電解質膜に混入することを防止することができる。
【図面の簡単な説明】
【図１】 実験例４における空気極の電極特性の測定結果を示す図。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a catalyst for a solid polymer electrolyte fuel cell. In particular, the present invention relates to a catalyst used for an air electrode of a polymer solid electrolyte fuel cell.
[0002]
[Prior art]
A fuel cell is highly expected as a next-generation power generation system. Among them, a polymer solid electrolyte fuel cell using a polymer solid electrolyte as an electrolyte is different from other types of fuel cells such as a phosphoric acid fuel cell. Compared to its low operating temperature and compact size, it is considered promising as a power source for electric vehicles.
[0003]
A polymer electrolyte fuel cell has a laminated structure composed of two electrodes, a hydrogen electrode and an air electrode, and a polymer solid electrolyte membrane sandwiched between these electrodes, and a fuel containing hydrogen is supplied to the hydrogen electrode. In addition, by supplying oxygen or air to the air electrode, electric power is taken out by oxidation and reduction reaction generated at each electrode. A mixture of a catalyst and a solid electrolyte for promoting an electrochemical reaction is generally applied to both of these electrodes. And as a catalyst which comprises this electrode, the platinum catalyst which carry | supported platinum with favorable catalytic activity is widely used.
[0004]
By the way, it is considered that characteristics required for the catalyst for the polymer electrolyte fuel cell electrode are different between the hydrogen electrode and the air electrode. That is, the hydrogen electrode not only has high catalytic activity, but also requires durability, particularly carbon monoxide catalyst poisoning. As hydrogen supplied to the hydrogen electrode as a fuel, it is considered that reformed hydrogen obtained from methanol or the like is promising from the viewpoint of its handleability and economical efficiency. This is because carbon monoxide is contained as an impurity, which is adsorbed on the catalyst particles and deactivates the catalyst. For this reason, many studies have been conducted on fuel electrode catalysts in order to improve the poisoning of carbon monoxide catalyst while maintaining the catalytic activity.
[0005]
[Problems to be solved by the invention]
On the other hand, the air electrode is different from the hydrogen electrode in that the fuel does not contain carbon monoxide, so there is no need to design a catalyst that takes into account the above-mentioned catalyst poisoning by carbon monoxide. Improvement is required. Here, as a conventional method for improving the activity of the catalyst for the air electrode, improvement of the characteristics of the carrier, refinement of platinum serving as catalyst particles, improvement of dispersibility, and the like are performed.
[0006]
However, there is a limit to the change in physical properties such as improvement of the properties of the support and refinement of the platinum particles, and the improvement of the catalytic activity achieved by these cannot be unlimited. The present invention has been made based on the background as described above, and is a catalyst for air electrode of a polymer solid electrolyte fuel cell, which is produced from a viewpoint different from the conventional method and has high catalytic activity. It is an object of the present invention to provide such a catalyst and to provide a method for producing such a catalyst.
[0007]
[Means for Solving the Problems]
In order to achieve the above object, the present inventors examined the application of an auxiliary metal as a means for improving the catalytic activity. The auxiliary metal is a metal other than the catalytic metal such as platinum, and the catalytic activity of the catalytic metal It has a function to improve durability. The application of such an auxiliary catalyst metal is not necessarily new in the field of catalysts, and there are application examples for catalysts for fuel cells and phosphoric acid fuel cells. On the other hand, in the catalyst for the air electrode of a polymer electrolyte fuel cell that is the object of the present invention, pure platinum catalyst is generally used because there are few successful examples of such a catalyst supporting an auxiliary metal. ing. This is because the auxiliary metal may be detached from the catalyst and mixed into the polymer film to deteriorate the characteristics of the polymer film, and the degree of the deterioration cannot be ignored.
[0008]
Therefore, the present inventors have found an optimum auxiliary catalyst metal for the air electrode catalyst of the polymer solid electrolyte fuel cell, and have studied a means for suppressing the inclusion of the auxiliary metal into the polymer membrane. In addition, it has been found that it is appropriate to use iron or cobalt as an auxiliary catalyst metal capable of improving the catalytic activity, and further, the auxiliary metal is constrained by alloying platinum and these auxiliary metals, and a polymer is obtained. The inventors have conceived that the auxiliary metal can be prevented from being mixed into the film and have completed the present invention.
[0009]
That is, the present invention is a catalyst for an air electrode of a solid polymer electrolyte fuel cell in which catalyst particles formed by alloying platinum and one auxiliary metal are supported on a carbon powder support, wherein the auxiliary metal is The catalyst for the air electrode of a solid polymer electrolyte fuel cell, characterized in that the compounding ratio of platinum and auxiliary metal is 6: 1 to 3: 2 (molar ratio).
[0010]
In the present invention, the reason why the catalytic activity is improved by using iron or cobalt as the auxiliary catalyst metal is not necessarily clear, but the interatomic distance of platinum changes by alloying iron or cobalt with platinum, and oxygen The hypothesis that the reducing power of oxygen increases due to the increased binding force with the molecule, the hypothesis that the electronic state of platinum has changed to a state where oxygen can be easily reduced by alloying, and further the alloying of the catalyst particle surface There is a hypothesis that the surface state (roughness) has changed, and it is considered that any of these acts in the present invention to improve the catalytic activity. In the present invention, platinum and an auxiliary metal are alloyed to prevent the auxiliary metal from being detached from the carrier and mixed into the polymer film.
[0011]
The compounding ratio of platinum and auxiliary metal constituting the catalyst particles is 6: 1 to 3: 2 in molar ratio. This is because when the ratio of the auxiliary metal is lower than 6: 1, the effect as the auxiliary metal (improvement of activity) is not exhibited. Also, in the present invention, it is platinum that mainly exerts the catalytic activity, so that the catalytic activity decreases even when the ratio of the auxiliary metal is increased, and it is supported alone without being alloyed in the manufacturing process. There is a risk that the generation rate of auxiliary metals will increase. However, since there is a merit that the amount of platinum used can be reduced and the catalyst cost can be reduced by increasing the ratio of the auxiliary metal, the ratio of the auxiliary metal is set to 3: 2 in consideration of these.
[0012]
Here, considering the characteristics when the catalyst according to the present invention is an electrode (air electrode), it is preferable that the loading density of the catalyst particles in which platinum and the auxiliary metal are alloyed is 40 to 65%. . The supported density refers to the ratio of the mass of catalyst particles supported on the support (in the present invention, the total weight of the platinum mass and the auxiliary metal mass) to the overall support mass of the catalyst. The reason why the loading density is in such a range is to effectively cause alloying in the characteristics of the electrode and the alloy catalyst as in the present invention. That is, in designing the fuel cell electrode, the amount of catalyst used is based on the amount of supported catalyst particles, not the amount of the catalyst itself. Therefore, when a catalyst having a low loading density is applied, the amount of the catalyst needs to be increased. However, when the amount of the catalyst is increased, the thickness of the electrode naturally increases. With such a thick electrode, mass transfer is restricted, which causes a reduction in oxygen diffusion efficiency and a reduction in water discharge efficiency. As a result, electrode characteristics are deteriorated. In addition, in the alloy catalyst as in the present invention, when the loading density is low (when the number of platinum particles, iron particles, or cobalt particles to be carried is reduced), the distance between the metal particles becomes large and it becomes difficult to alloy them. In consideration of such circumstances, the minimum value of the support density is set to 40% in order to ensure electrode characteristics and cause alloying. On the other hand, if the loading density is high, the amount of catalyst particles carried on the carrier becomes excessive, and the alloy catalyst particles become coarse when alloyed. Therefore, the maximum value of the carrying density is 65%.
[0013]
As described above, in the present invention, iron or cobalt as an auxiliary catalyst metal is alloyed at a predetermined ratio and supported on conventional platinum, thereby exhibiting excellent catalytic activity. Here, in order to make this catalyst function more effectively, the present inventors have further investigated a carrier for supporting the catalyst particles. As a result, it was concluded that carbon powder having a specific surface area of 600 to 1200 m 2 / g is particularly preferable as a support. By setting the specific surface area to 600 m 2 / g or more, the area to which the catalyst adheres can be increased, so that the catalyst particles can be dispersed in a high state to increase the effective surface area, while the specific surface area is 1200 m 2 / g. This is because when the electrode is formed, the existence ratio of ultrafine pores (less than about 20 mm) into which the ion exchange resin cannot enter when forming the electrode is increased, and the utilization efficiency of the catalyst particles is decreased. Therefore, by setting the specific surface area within the above range, the precious metal particles are dispersed in a high state to improve the activity per unit mass of the catalyst, while ensuring the utilization efficiency of the catalyst.
[0014]
Next, a method for producing a catalyst for a polymer electrolyte membrane fuel cell air electrode according to the present invention will be described. The method for producing a catalyst according to the present invention comprises a step of supporting platinum constituting catalyst particles and iron or cobalt as an auxiliary metal on a support, and a step of alloying the supported platinum and iron or cobalt.
[0015]
Regarding these steps, there is no particular limitation on the step of supporting platinum and auxiliary metals on the carrier. Therefore, platinum and the auxiliary metal can be supported by impregnating the carrier with a platinum salt solution and a metal salt solution serving as an auxiliary metal as in the prior art. Note that there is no particular effect on the order of loading platinum and supporting metal, whichever comes first or at the same time.
[0016]
And as for the alloying of the supported platinum and the auxiliary metal, as described above, the purpose of alloying the platinum and the auxiliary metal in the present invention is to improve the catalytic activity, but at the same time, the auxiliary metal is removed from the catalyst. This is to prevent the polymer solid electrolyte membrane from being detached and contaminated. Therefore, in the present invention, it is necessary to realize a sufficient alloy state. The inventors of the present invention assume that it is appropriate to heat the support at 800 ° C. to 1200 ° C. in a hydrogen reducing atmosphere as the alloying conditions. Here, the hydrogen concentration in the reaction atmosphere is preferably about 100%.
[0017]
According to the catalyst of the present invention obtained by the above production method, it is possible to obtain an air electrode catalyst that has excellent catalytic activity and does not contaminate the solid polymer electrolyte membrane. Here, the air electrode is manufactured by mixing the ion exchange resin and the catalyst, and the mixing ratio of the ion exchange resin and the catalyst is 0.7 to 1.6 (weight ratio). preferable. If the mixing ratio is less than 0.7, coating of the catalyst with the ion exchange resin cannot be sufficiently achieved, and the catalyst utilization efficiency is lowered and the proton conductivity cannot be sufficiently secured, thereby reducing the reaction efficiency of the catalyst. is there. On the other hand, if the mixing ratio exceeds 1.6, pores contributing to gas diffusion and water discharge decrease, and the reaction efficiency of the catalyst decreases.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Preferred embodiments of the present invention will be described below with reference to the drawings.
[0019]
First Embodiment : In this embodiment, a platinum / iron alloy catalyst was manufactured. This alloy catalyst was produced by preparing a platinum catalyst in which platinum was supported on the carbon powder in advance, impregnating the platinum catalyst in an iron compound solution to support iron, and heat-treating the support. This will be described in detail below.
[0020]
[Selection of Carrier] The carrier used in this embodiment is carbon fine powder (trade name: Ketjen Black EC). The specific surface area of this carrier was 800 m 2 / g as measured by the BET 1-point method.
[0021]
[Preparation of platinum catalyst] As a platinum solution, 12 g of the carbon powder was immersed in 1000 g (platinum content: 8 g) of a dinitrodiammine platinum nitric acid solution having a platinum concentration of 0.8 wt%, and then 100 ml of 100% ethanol as a reducing agent was stirred. Added. This solution was stirred and mixed at the boiling point (about 95 ° C.) for 7 hours, and platinum was supported on the carbon powder. And after filtering and drying, it was set as the platinum catalyst.
[0022]
[Iron loading] As an iron solution, 10 g of the platinum catalyst was immersed in 60 g of iron chloride aqueous solution having an iron concentration of 0.63 wt% (iron content: 0.38 g). The solution was stirred for 1 hour and dried at 60 ° C.
[0023]
[Heat Treatment] An alloying heat treatment of platinum and iron was performed on the carrier carrying platinum and iron by the above steps. This alloying heat treatment was performed by holding at 1000 ° C. for 2 hours in 100% hydrogen gas.
[0024]
The ratio of each supported metal of the platinum / iron alloy catalyst produced by the above operation is 3: 1. The supported density of platinum and iron is 42%. These values can be easily controlled by changing the platinum content in the platinum solution impregnated in the support and the iron content in the iron salt solution impregnated in the platinum catalyst.
[0025]
About the platinum / iron alloy catalyst manufactured by the above manufacturing method, what changed the supporting ratio of platinum and iron was manufactured, and the air electrode was manufactured from these. For the air electrode, 1.2 g of a resin powder produced by spray drying a 5% solution of an ion exchange resin (trade name: Nafion, manufactured by Dupon) and 1 g of a catalyst are put in 24 mL of an aqueous solution of 1-propanol, and this is ball milled. Was mixed for 100 minutes to prepare a catalyst paste. And the said catalyst paste was apply | coated and printed so that the amount of platinum might be set to 0.25 mg / cm < 2 > on the gas diffusion layer manufactured by coating carbon and PTFE on the surface layer to carbon paper. Furthermore, after drying this at 100 degreeC, it hot-pressed for 1 minute at 130 degreeC and 20 kg / cm < 2 >, and was set as the electrode.
[0026]
Experimental Example 1 : Using these air electrodes, a single cell test was performed using Nafion 112 (trade name: manufactured by Dupon Co.) as a polymer electrolyte membrane in order to measure the oxygen mass activity. This oxygen mass activity is a current value obtained by reduction of oxygen at a predetermined potential (0.9 V). Measurement conditions were as follows.
[0027]
Electrode area: 25 cm 2
Temperature: 80 ° C
Pressure: Atmospheric pressure Oxygen: 100%
[0028]
Table 1 shows the measurement results of the oxygen mass activity of the air electrode produced by the platinum / iron catalyst produced in the present embodiment and the oxygen activity of the conventional platinum catalyst not alloyed.
[0029]
[Table 1]
From Table 1, the catalyst produced in this embodiment has a higher oxygen mass activity than when no alloying of iron is performed, but the peak is an alloy ratio of platinum: iron = 3: 1, and platinum: iron = It was confirmed that the oxygen mass activity decreased as the alloy ratio of 3: 2 and iron increased.
[0031]
Experimental Example 2 : Next, the support ratio of platinum and iron was fixed at 3: 1, the support density was changed to produce an air electrode, and the oxygen activity was measured under the same conditions as in the experimental example. The results are shown in Table 2.
[0032]
[Table 2]
From this result, it was confirmed that when the loading density was 40 to 65%, a peak was observed at around 50% loading density, but the oxygen activity was higher than that without the addition of the auxiliary catalyst metal.
[0034]
Second Embodiment : In this embodiment, a platinum / cobalt alloy catalyst was manufactured. However, the carrier used in the alloy catalyst in the present embodiment, the platinum supporting step, and the heat treatment are the same as in the first embodiment. Therefore, only the characteristic cobalt loading process will be described while avoiding repeated description.
[0035]
[Supporting cobalt] As a cobalt solution, 10 g of the platinum catalyst was immersed in 60 g of cobalt chloride aqueous solution having a cobalt concentration of 0.66 wt% (cobalt content: 0.4 g). The solution was stirred for 1 hour and dried at 60 ° C.
[0036]
The ratio of each supported metal of the platinum / cobalt alloy catalyst produced by the above operation is 3: 1. Similar to the first embodiment, this ratio can be easily controlled by changing the cobalt content in the cobalt salt solution impregnated in the platinum catalyst.
[0037]
Experimental example 3 : About the platinum / cobalt alloy catalyst manufactured by the above manufacturing method, the catalyst which changed the alloy ratio of platinum and cobalt was manufactured similarly to 1st Embodiment, and the air electrode was manufactured from these. And about these air electrodes, the oxygen mass activity was measured by the single cell test. The measurement conditions are the same as in the first embodiment. The measurement results are shown in Table 3.
[0038]
[Table 3]
From Table 3, the catalyst manufactured in this embodiment has a higher oxygen mass activity than the case where no alloying of cobalt is performed, and the alloy ratio of platinum: cobalt = 3: 1 is a peak as in the first embodiment. It was confirmed that the oxygen mass activity was decreased at platinum: cobalt = 3: 2.
[0040]
Experimental Example 4 : In addition to the measurement of the oxygen activity, the battery characteristics of the actual air electrode were examined. At this time, the supporting ratio of platinum and auxiliary catalyst metals (iron, cobalt) of the catalyst was 3: 1, and the supporting density was 42%. The battery characteristics were evaluated based on the cell voltage at a predetermined current density, and the measurement conditions were as follows.
[0041]
Electrode area: 25 cm 2
Setting utilization efficiency: 40%
Temperature: 80 ° C
Pressure: Atmospheric pressure Anode gas: Pure hydrogen humidification condition: Anode Humidity 100%
Cathode humidity 80%
[0042]
The results are shown in FIG. 1. As can be seen from FIG. 1, it is confirmed that the catalyst according to the present embodiment, in which iron and cobalt are applied as auxiliary catalysts, has higher electrode characteristics in the practical range than the platinum-supported catalyst. It was done.
[0043]
【The invention's effect】
As described above, the present invention uses iron or cobalt as an auxiliary catalyst metal for a catalyst for an air electrode of a solid polymer electrolyte fuel cell that conventionally uses a catalyst supporting only platinum. Thereby, higher catalytic activity than the conventional catalyst for air electrodes can be exhibited. The present invention can prevent the auxiliary catalyst metal from being detached from the catalyst and mixed into the polymer solid electrolyte membrane by alloying these auxiliary catalyst metals with platinum.
[Brief description of the drawings]
1 is a graph showing measurement results of electrode characteristics of an air electrode in Experimental Example 4. FIG.
Claims (3)
前記補助金属は、コバルトであり、白金とコバルトとの配合比は６：１〜３：１（モル比）とし、
比表面積６００〜１２００ｍ２／ｇの炭素粉末からなる担体に、触媒粒子を担持密度４０〜６５％で担持してなる高分子固体電解質形燃料電池の空気極用の触媒。A catalyst for an air electrode of a solid polymer electrolyte fuel cell in which catalyst particles formed by alloying platinum and one auxiliary metal are supported on a carbon powder support,
The auxiliary metal is cobalt, and the blending ratio of platinum and cobalt is 6: 1 to 3: 1 (molar ratio).
A catalyst for an air electrode of a solid polymer electrolyte fuel cell in which catalyst particles are supported at a support density of 40 to 65% on a support made of carbon powder having a specific surface area of 600 to 1200 m 2 / g.
担体に白金と鉄又はコバルトと６：１〜３：１（モル比）の配合比で担持させた後、担体を水素還元雰囲気下で８００℃〜１２００℃で加熱する方法。A method for producing a catalyst for an air electrode of a solid polymer electrolyte fuel cell according to claim 1,
A method of heating a support at 800 ° C. to 1200 ° C. in a hydrogen reduction atmosphere after supporting the support at a blending ratio of 6: 1 to 3: 1 (molar ratio) with platinum and iron or cobalt.
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| US5068161A (en) * | 1990-03-30 | 1991-11-26 | Johnson Matthey Public Limited Company | Catalyst material |
| JPH07256107A (en) * | 1994-03-18 | 1995-10-09 | Tanaka Kikinzoku Kogyo Kk | Production of noble metal alloy catalyst |
| JP3389393B2 (en) * | 1995-12-04 | 2003-03-24 | 田中貴金属工業株式会社 | Anode catalyst for polymer electrolyte fuel cell and method for producing the same |
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| DE50013678D1 (en) * | 1999-08-27 | 2006-12-14 | Umicore Ag & Co Kg | Electrocatalyst for fuel cells |
| JP2001357857A (en) * | 2000-06-12 | 2001-12-26 | Asahi Glass Co Ltd | Solid high polymer type fuel cell and its manufacturing method |
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| US9105936B2 (en) | 2006-11-20 | 2015-08-11 | Samsung Sdi Co., Ltd. | Fuel cell catalyst, method of preparing same, and membrane-electrode assembly for fuel cell and fuel cell system including same |
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