JP5209474B2 - 電極触媒、電極触媒の製造方法及び触媒粒子の粗大化を抑制する方法 - Google Patents
電極触媒、電極触媒の製造方法及び触媒粒子の粗大化を抑制する方法 Download PDFInfo
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
- Catalysts (AREA)
Description
(実施例1)
(1−1.アルミニウムリン酸系化合物がコーティングされた白金担持カーボン触媒の調製)
所定量の蒸留水にリン酸アンモニウムを添加して十分に撹拌して溶かした後、アルミニウム窒酸塩を添加して同じく十分に撹拌した。このとき、リン酸アンモニウムとアルミニウム窒酸塩の重量比は、0.38:1になるようにした。反応が進められるにつれてアルミニウムリン酸系化合物が形成されつつ、白い色を呈するコーティング液が得られ、このコーティング液に平均粒径2.6nm程度の白金粒子を担持した所定量の白金担持カーボンを入れた。このとき、白金とアルミニウムリン酸系化合物とのモル比を3:1に合わせた。コーティングされた白金担持カーボンを90℃以下のオーブンで完全に乾燥した後、200℃で2時間にかけて熱処理を施してアルミニウムリン酸系化合物が白金担持カーボン表面上にコーティングされるようにした。
実施例1−1で得られたアルミニウムリン酸系化合物でコーティングされた白金担持カーボンを高い水素イオン伝導性を有するナフィオン・インクと混合し、それをカーボン電極に塗布して酸素極の電極を用意し、燃料極の方には、Johnson−Matthey社の商用触媒(Hispec 9100)を利用して、同方法にて燃料極の電極を用意した。このとき、酸素極の電極側の白金担持量は、0.25mgPt/cm2にし、また、燃料極の電極側の白金担持量は、0.5mgPt/cm2にした。
上記実施例1−2で得られた両電極の間にナフィオン電解質膜を熱的、機械的に挟み込んで膜電極接合体を製造し、これを利用して水素イオン交換膜燃料電池を製造した(図2参照)。
熱処理温度を200℃から300℃に変更したことを除いては、上記実施例1と同方法にて電極触媒、膜電極接合体及び水素イオン交換膜燃料電池を製造した。
アルミニウムリン酸系化合物でコーティングしていない白金担持カーボン触媒を使用したことを除いては、上記実施例1と同方法にて膜電極接合体及びこれを含む燃料電池を製造した。
本発明に係る電極触媒に対する分析を下記のように遂行した。
本発明に係る電極触媒の粗大化傾向を評価するために、下記のような実験を遂行した。
本発明に係る電極触媒を利用した単位電池の性能テストを、下記のとおり実施した。
Claims (14)
- (a)担体と、
(b)前記担体に担持され、触媒活性を有する金属または前記金属含有合金からなる触媒粒子、及び
(c)前記触媒粒子同士の隙間及び前記担体と前記触媒粒子との接触部位とからなる群より選択された少なくとも一つの領域上に分散され、前記触媒より高い粗大化温度を有する粗大化抑制化合物と、
を含み、
前記粗大化抑制化合物(c)が、アルミニウムリン酸系化合物であり、前記触媒活性を有する金属または前記金属含有合金(b)より前記担体(a)に対する親和度が高い、電極触媒。 - 前記粗大化温度は、結晶粒の成長が発生する温度であることを特徴とする請求項1に記載の電極触媒。
- 前記触媒粒子(b)は、300℃以下の粗大化温度を有し、粗大化抑制化合物(c)は、300℃以上の粗大化温度を有することを特徴とする請求項1に記載の電極触媒。
- 前記触媒活性を有する金属または金属含有合金粒子は、白金(Pt)、ルテニウム(Ru)、ロジウム(Rh)、パラジウム(Pd)、金(Au)、銀(Ag)、イリジウム(Ir)、及びオスミウム(Os)からなる群より選択された少なくとも1種であることを特徴とする請求項1に記載の電極触媒。
- 前記触媒活性を有する金属または金属含有合金粒子の粒径は、1ないし10nmの範囲であることを特徴とする請求項1に記載の電極触媒。
- 前記粗大化抑制化合物がコーティングまたは分散された厚さは、1ないし5nmの範囲であることを特徴とする請求項1に記載の電極触媒。
- 前記担体(a)は、多孔性炭素、伝導性高分子、及び金属酸化物からなる群より選択されたことを特徴とする請求項1に記載の電極触媒。
- (a)第1の触媒層を有する第1の電極と、
(b)第2の触媒層を有する第2の電極、及び
(c)前記第1の電極と前記第2の電極との間に介在した電解質膜と、
を含んでなる燃料電池用膜電極接合体であって、
第1の触媒層、第2の触媒層、または第1の触媒層及び第2の触媒層は、請求項1ないし7のいずれかに記載の電極触媒を含むことを特徴とする膜電極接合体(MEA)。 - 請求項8に記載の膜電極接合体(MEA)を含む燃料電池。
- 前記燃料電池は、水素イオン交換膜燃料電池(PEMFC)であることを特徴とする請求項9に記載の燃料電池。
- (a)触媒活性を有する金属または前記金属含有合金より粗大化温度の高い粗大化抑制化合物を溶媒に分散または溶解させて分散液または溶液を用意する段階と、
(b)触媒活性を有する金属または前記金属含有合金からなる触媒粒子が担持された担体を段階(a)で得られた分散液または溶液に添加及びコーティングした後、乾燥する段階、及び
(c)前記段階(b)で得られた乾燥物を熱処理する段階と、
を含む、請求項1に記載の電極触媒の製造方法。 - 前記段階(b)で得られた分散液または溶液に触媒粒子が担持された担体を添加するに際し、触媒粒子に対する粗大化抑制化合物のモル比が1〜5:1であることを特徴とする請求項11に記載の製造方法。
- 前記熱処理温度は、触媒粒子の粗大化発生温度より低い範囲であることを特徴とする請求項11に記載の製造方法。
- 担体に担持され、触媒活性を有する金属または前記金属含有合金からなる触媒粒子同士の隙間及び担体と触媒粒子との接触部位からなる群より選択された少なくとも一つの領域上に、前記触媒より粗大化温度の高い粗大化抑制化合物を分散させて前記触媒粒子の粗大化を抑制する方法であって、前記粗大化抑制化合物が、アルミニウムリン酸系化合物であり、前記触媒活性を有する金属または前記金属含有合金より前記担体に対する親和度が高い、方法。
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