JP4939051B2 - Method for producing catalyst electrode of polymer electrolyte fuel cell - Google Patents

Method for producing catalyst electrode of polymer electrolyte fuel cell Download PDF

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JP4939051B2
JP4939051B2 JP2005378700A JP2005378700A JP4939051B2 JP 4939051 B2 JP4939051 B2 JP 4939051B2 JP 2005378700 A JP2005378700 A JP 2005378700A JP 2005378700 A JP2005378700 A JP 2005378700A JP 4939051 B2 JP4939051 B2 JP 4939051B2
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catalyst
platinum
fuel cell
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catalyst electrode
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JP2007179932A (en
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和也 宮崎
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Canon Inc
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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

本発明は、固体高分子型燃料電池の触媒電極の製造方法に関する。 The present invention relates to a method for producing a catalyst electrode of a polymer electrolyte fuel cell.

固体高分子形燃料電池は、エネルギー変換効率が高いこと、クリーンであること、静かであることなどから、将来のエネルギー生成装置として期待されている。とりわけ、近年では、自動車や家庭用発電機などの用途だけではなく、そのエネルギー密度の高さから携帯電話やノート型パソコン、デジタルカメラなど小型の電気機器に搭載することによって、従来の２次電池に比べ長時間駆動できる可能性があり、注目を集めている。しかしながら、車載用、家庭用に関しては、まだまだコストの削減が必要であり、その一手段として触媒使用量を減らすことが望まれている。また、小型の電気機器用としての実用化には、システム全体のコンパクト化、発電効率の向上が必須である。   The polymer electrolyte fuel cell is expected as a future energy generation device because of its high energy conversion efficiency, cleanliness, and quietness. In particular, in recent years, not only applications such as automobiles and household power generators, but also because of their high energy density, they can be installed in small electrical devices such as mobile phones, laptop computers, and digital cameras, thereby making conventional secondary batteries. It has the potential to be driven for a long time compared to, and is attracting attention. However, for in-vehicle use and home use, it is still necessary to reduce the cost, and it is desired to reduce the amount of catalyst used as one means. Also, for practical use as a small electric device, it is essential to make the entire system compact and improve the power generation efficiency.

これまで、触媒を微粒子化し、カーボン粒子などに担持させて３次元的に分散させることで、表面積を増大させ、触媒の利用効率を高めるという試みがなされてきた。また、一方では、触媒層を厚さ数μｍ程度と非常に薄く形成することで、物質輸送を良くし、触媒層が電解質膜近傍に集中することで、触媒有効面積を増大させる試みもなされてきた。特に、燃料電池を小型電気機器に搭載する場合においては、電池自体も小型化する必要があり、空気はポンプやブロワーなどを用いずに通気孔から自然拡散によって空気極へ供給される方式（ａｉｒ ｂｒｅａｔｈｉｎｇ）が多く採られている。このような場合、空気極での物質輸送が反応の律速となる場合が多く、触媒層を薄くすることは、有効な手段となると考えられる。   Up to now, attempts have been made to increase the surface area and increase the utilization efficiency of the catalyst by making the catalyst fine particles, supporting them on carbon particles, etc., and dispersing them three-dimensionally. On the other hand, attempts have been made to increase the effective catalyst area by improving the material transport by forming the catalyst layer as thin as several μm, and by concentrating the catalyst layer in the vicinity of the electrolyte membrane. It was. In particular, when the fuel cell is mounted on a small electric device, the cell itself needs to be miniaturized, and air is supplied to the air electrode by natural diffusion from the vent hole without using a pump or a blower (air). Breathing) is often used. In such a case, mass transport at the air electrode is often the rate-limiting reaction, and it is considered that thinning the catalyst layer is an effective means.

触媒利用率の向上と触媒層の膜厚方向の導電性向上を解決する手段として、特許文献１には、カーボンフナノァイバー表面上に触媒微粒子を担持して形成した燃料電池用電極が開示されている。
特開２００２−２９８８６１号公報 Patent Document 1 discloses a fuel cell electrode formed by supporting catalyst fine particles on the surface of a carbon fiber as a means for solving an improvement in catalyst utilization and an improvement in conductivity in the thickness direction of the catalyst layer. Yes.
JP 2002-298661 A

しかしながら、より汎用性があり簡易な方法により触媒電極を製造し、その触媒電極の触媒利用率をさらに向上するという課題は、これまで十分に検討が為されてきたとは言えない。   However, it cannot be said that the problem of producing a catalyst electrode by a more versatile and simple method and further improving the catalyst utilization rate of the catalyst electrode has been sufficiently studied.

そこで、本発明は、以上の課題に対して鋭意検討を行って為されたものであり、触媒利用率を向上した触媒電極を汎用性がある簡易な方法によって製造できる固体高分子型燃料電池の触媒電極の製造方法を提供するものである。 Accordingly, the present invention has been made by intensively studying the above problems, and is a solid polymer fuel cell that can produce a catalyst electrode with improved catalyst utilization by a versatile and simple method. A method for producing a catalyst electrode is provided.

上記の課題を解決するための固体高分子型燃料電池の触媒電極の製造方法は、固体高分子型燃料電池の触媒電極であって、前記触媒電極は触媒と、触媒を担持する炭素繊維を有し、前記触媒は薄片状のナノ構造を有する固体高分子型燃料電池の触媒電極の製造方法において、前記触媒を反応性真空蒸着法によって形成する工程を有することを特徴とする。A method for producing a catalyst electrode of a polymer electrolyte fuel cell for solving the above problems is a catalyst electrode of a polymer electrolyte fuel cell, wherein the catalyst electrode has a catalyst and carbon fibers supporting the catalyst. In the method for producing a catalyst electrode of a polymer electrolyte fuel cell having a flaky nanostructure, the catalyst has a step of forming the catalyst by a reactive vacuum deposition method.

前記触媒が、薄片状のナノ構造単位を有した樹枝状構造であることが好ましい。
前記触媒は、白金酸化物、白金酸化物と白金以外の金属元素の酸化物との複合酸化物、前記白金酸化物または複合酸化物を還元処理してなる白金または白金を含んだ多元金属、白金と白金以外の金属元素の酸化物との混合物あるいは白金を含んだ多元金属と白金以外の金属元素の酸化物との混合物であることが好ましい。 It is preferable that the catalyst has a dendritic structure having flaky nanostructure units.
The catalyst includes platinum oxide, a composite oxide of platinum oxide and an oxide of a metal element other than platinum, platinum formed by reducing the platinum oxide or composite oxide, or a multi-metal containing platinum, platinum And a mixture of an oxide of a metal element other than platinum or a mixture of a multi-element metal containing platinum and an oxide of a metal element other than platinum.

前記白金以外の金属元素は、Ａｌ，Ｓｉ，Ｔｉ，Ｖ，Ｃｒ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎ，Ｇｅ，Ｚｒ，Ｎｂ，Ｍｏ，Ｒｕ，Ｒｈ，Ｐｄ，Ａｇ，Ｉｎ，Ｓｎ，Ｈｆ，Ｔａ，Ｗ，Ｏｓ，Ｉｒ，Ａｕ，Ｌａ，Ｃｅ，Ｎｄから選ばれる少なくとも一種類以上の金属からなることが好ましい。   The metal elements other than platinum are Al, Si, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ge, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Hf, It is preferably made of at least one metal selected from Ta, W, Os, Ir, Au, La, Ce, and Nd.

前記触媒の薄片の最大厚さが５ｎｍ以上５０ｎｍ以下であることが好ましい。
前記炭素繊維はナノチューブまたはナノファイバーであることが好ましい。
前記炭素繊維の平均直径は５ｎｍ以上５００ｎｍ以下で、平均長さは１μｍ以上１００μｍ以下であることが好ましい。 The maximum thickness of the catalyst flakes is preferably 5 nm or more and 50 nm or less.
The carbon fibers are preferably nanotubes or nanofibers.
The carbon fiber preferably has an average diameter of 5 nm to 500 nm and an average length of 1 μm to 100 μm.

前記炭素繊維は熱ＣＶＤ法によって形成することが好ましい。ＣＶＤとは、Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ（化学気相成長）の略である。 The carbon fiber is preferably formed by a thermal CVD method. CVD is an abbreviation for Chemical Vapor Deposition .

本発明によれば、触媒利用率を向上した触媒電極を汎用性がある簡易な方法によって製造できる固体高分子型燃料電池の触媒電極の製造方法を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the catalyst electrode of the polymer electrolyte fuel cell which can manufacture the catalyst electrode which improved the catalyst utilization factor by a versatile simple method can be provided.

以下、図面を参照して、本発明の固体高分子型燃料電池の触媒電極およびその製造方法について、好適な実施の形態を例示的に詳しく説明する。ただし、この実施の形態に記載されている構成部材の材質、寸法、形状、その相対配置等は、特に特定的な記載がない限りは、本発明の範囲を限定するものではない。同様に以下に記述する製造方法も唯一のものではない。   Hereinafter, with reference to the drawings, preferred embodiments of the catalyst electrode of the polymer electrolyte fuel cell of the present invention and the manufacturing method thereof will be described in detail by way of example. However, the materials, dimensions, shapes, relative arrangements, and the like of the constituent members described in this embodiment do not limit the scope of the present invention unless otherwise specified. Similarly, the manufacturing method described below is not the only one.

図１は、本発明の触媒電極を用いた固体高分子型燃料電池の単セルの断面構成の一例を表す模式図である。図１において、１は固体高分子電解質膜、これを挟んで一対のカソード触媒電極４、アノード触媒電極５が配置され、さらにその外側にはカソードガス拡散層６、アノードガス拡散層７及びカソード電極８、アノード電極９が配置される。   FIG. 1 is a schematic diagram showing an example of a cross-sectional configuration of a single cell of a polymer electrolyte fuel cell using the catalyst electrode of the present invention. In FIG. 1, reference numeral 1 denotes a solid polymer electrolyte membrane, and a pair of cathode catalyst electrode 4 and anode catalyst electrode 5 are disposed across the membrane, and a cathode gas diffusion layer 6, an anode gas diffusion layer 7 and a cathode electrode are disposed on the outside thereof. 8. An anode electrode 9 is disposed.

本実施例においては、両極ともに薄片状のナノ構造、あるいは薄片状のナノ構造単位を有した樹枝状構造を有する触媒を炭素繊維上に形成した触媒電極を配置した例を示す。しかし、触媒電極の配置構成としてはこれに限定するものではなく、例えばカソード側のみ本発明の触媒電極を配置する場合、あるいはアノード側のみ本発明の触媒電極を配置する場合をも含んでおり、種々の構成を好ましく選択することができる。   In this embodiment, an example is shown in which a catalyst electrode in which a catalyst having a flaky nanostructure or a dendritic structure having a flaky nanostructure unit is formed on a carbon fiber is disposed on both electrodes. However, the arrangement configuration of the catalyst electrode is not limited to this, and includes, for example, the case where the catalyst electrode of the present invention is arranged only on the cathode side, or the case where the catalyst electrode of the present invention is arranged only on the anode side, Various configurations can be preferably selected.

さらに、図１において、２は触媒、３は触媒を担持する炭素繊維であり、これらから触媒電極４が構成される。
触媒２は薄片状のナノ構造を有することを特徴とする。特に、触媒は薄片状のナノ構造単位を有した樹枝状構造であることが好ましい。 Furthermore, in FIG. 1, 2 is a catalyst, 3 is carbon fiber which supports a catalyst, and the catalyst electrode 4 is comprised from these.
The catalyst 2 is characterized by having a flaky nanostructure. In particular, the catalyst preferably has a dendritic structure having flaky nanostructure units.

前記触媒は、白金酸化物、白金酸化物と白金以外の金属元素の酸化物との複合酸化物、前記白金酸化物または複合酸化物を還元処理してなる白金または白金を含んだ多元金属、白金と白金以外の金属元素の酸化物との混合物あるいは白金を含んだ多元金属と白金以外の金属元素の酸化物との混合物を好適に使用することができる。   The catalyst includes platinum oxide, a composite oxide of platinum oxide and an oxide of a metal element other than platinum, platinum formed by reducing the platinum oxide or composite oxide, or a multi-metal containing platinum, platinum It is possible to suitably use a mixture of a metal element oxide other than platinum or a mixture of a multielement metal containing platinum and an oxide of a metal element other than platinum.

前記白金以外の金属元素は、Ａｌ，Ｓｉ，Ｔｉ，Ｖ，Ｃｒ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎ，Ｇｅ，Ｚｒ，Ｎｂ，Ｍｏ，Ｒｕ，Ｒｈ，Ｐｄ，Ａｇ，Ｉｎ，Ｓｎ，Ｈｆ，Ｔａ，Ｗ，Ｏｓ，Ｉｒ，Ａｕ，Ｌａ，Ｃｅ，Ｎｄから選ばれる少なくとも一種類以上の金属を好ましく用いることができる。   The metal elements other than platinum are Al, Si, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ge, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Hf, At least one metal selected from Ta, W, Os, Ir, Au, La, Ce, and Nd can be preferably used.

以上述べた形態、組成、構成、寸法の触媒は、反応性真空蒸着法によって好適に形成することができる。例えば、薄片状のナノ構造を有する白金酸化物は、白金ターゲットを使用した反応性スパッタによって、炭素繊維上に容易に被覆形成することができる。   The catalyst having the form, composition, configuration and dimensions described above can be suitably formed by a reactive vacuum deposition method. For example, a platinum oxide having a flaky nanostructure can be easily formed on a carbon fiber by reactive sputtering using a platinum target.

炭素繊維３はグラファイト構造を有する繊維を示し、グラフェンのＣ軸が繊維長方向と平行なプレートレット型グラファイトナノファイバー（以下、ＧＮＦと称す）を使用することができる。また、グラフェンのＣ軸が繊維長方向と傾きを持ったへリングボーン型ＧＮＦ、グラフェンのＣ軸が繊維長方向と垂直な、所謂カーボンナノチューブ（以下、ＣＮＴと称す）等を使用することができる。   The carbon fiber 3 is a fiber having a graphite structure, and a platelet-type graphite nanofiber (hereinafter referred to as GNF) in which the C axis of graphene is parallel to the fiber length direction can be used. Further, a herringbone GNF in which the C axis of graphene has an inclination with respect to the fiber length direction, a so-called carbon nanotube (hereinafter referred to as CNT) in which the C axis of graphene is perpendicular to the fiber length direction, and the like can be used. .

ＧＮＦあるいはＣＮＴは、Ｐｄ、Ｆｅ、Ｃｏ、Ｎｉ、あるいはこれらの合金を炭素繊維の生成触媒として配置した基体を、炭素含有ガスあるいは水素ガスと混合した炭素含有ガスを含む減圧雰囲気反応炉内にて、３００℃〜８００℃に加熱する。所謂熱ＣＶＤ法によって形成することができる。   GNF or CNT is formed in a reduced-pressure atmosphere reactor containing a carbon-containing gas or a carbon-containing gas mixed with hydrogen gas on a substrate on which Pd, Fe, Co, Ni, or an alloy thereof is arranged as a carbon fiber production catalyst. Heat to 300 ° C to 800 ° C. It can be formed by a so-called thermal CVD method.

前記炭素繊維の直径は、生成触媒の膜厚、若しくは還元凝集処理後の生成触媒粒径によって制御することができ、平均直径５ｎｍ以上５００ｎｍ以下、さらに好適には５０ｎｍ以上３００ｎｍ以下の範囲である。また、前記炭素繊維の長さは、その成長時間によって制御することができ、平均長さ１μｍ以上１００μｍ以下、さらに好適には１０μｍ以上５０μｍ以下の範囲である。   The diameter of the carbon fiber can be controlled by the film thickness of the produced catalyst or the produced catalyst particle diameter after the reductive aggregation treatment, and has an average diameter of 5 nm to 500 nm, more preferably 50 nm to 300 nm. The length of the carbon fiber can be controlled by the growth time, and the average length is in the range of 1 μm to 100 μm, more preferably 10 μm to 50 μm.

こうして炭素繊維上に形成した、薄片状のナノ構造、あるいは薄片状のナノ構造単位を有した樹枝状構造を有する触媒は、これを直接高分子電解質膜に転写する方法を採ってもよい。また、基体から剥離した触媒電極を電解質溶液、有機溶媒、水と混合して触媒スラリーを作製した後にこれを電解質膜に直接塗布する方法を採ってもよい。あるいはこの触媒スラリーをブレード法にて転写層としてのテフロン（登録商標）シート上に形成した後、これを電解質膜に転写する方法（ＤｅＣａｌ法）を採用することもできる。   The catalyst having a flaky nanostructure or a dendritic structure having a flaky nanostructure unit thus formed on the carbon fiber may be directly transferred to a polymer electrolyte membrane. Alternatively, a method may be employed in which the catalyst electrode peeled from the substrate is mixed with an electrolyte solution, an organic solvent, and water to prepare a catalyst slurry and then directly applied to the electrolyte membrane. Alternatively, a method (DeCal method) in which the catalyst slurry is formed on a Teflon (registered trademark) sheet as a transfer layer by a blade method and then transferred to an electrolyte membrane can be employed.

固体高分子電解質膜としては、弗化炭素骨格にスルホン酸基を末端につけた側鎖が結合した構造のパーフルオロスルホン酸ポリマーを好適に使用することができる。
パーフルオロスルホン酸ポリマーは弗化炭素骨格が架橋しておらず、骨格部分がファンデルワールス力で結合した結晶を形成しており、さらにスルホン酸基はいくつかが凝集して逆ミセル構造をとっており、ここがプロトンＨ+の伝導チャネルとなっている。なお、プロトンＨ+が電解質膜中をカソード側に向かって移動する場合には水分子を媒体として移動するので、電解質膜は水分子を保有する機能も有する。 As the solid polymer electrolyte membrane, a perfluorosulfonic acid polymer having a structure in which a side chain having a sulfonic acid group at the end is bonded to a fluorocarbon skeleton can be preferably used.
Perfluorosulfonic acid polymers do not have a cross-linked fluorocarbon skeleton, form crystals in which the skeleton is bonded by van der Waals forces, and some sulfonic acid groups aggregate to form a reverse micelle structure. This is the proton H + conduction channel. When proton H + moves in the electrolyte membrane toward the cathode side, it moves using water molecules as a medium, so that the electrolyte membrane also has a function of retaining water molecules.

したがって、固体高分子電解質膜の機能としては、アノード側で生成したプロトンＨ+をカソード側に伝達するとともに未反応の反応ガス（水素および酸素）を通さないこと、所定の保水機能を要する。この条件を満たすものであれば、任意のものを選択して使用することができる。 Therefore, as a function of the solid polymer electrolyte membrane, proton H + generated on the anode side is transmitted to the cathode side, unreacted reaction gases (hydrogen and oxygen) are not passed, and a predetermined water retention function is required. Any one satisfying this condition can be selected and used.

ガス拡散層５は、電極反応を効率良く行わせるために、燃料ガスまたは空気を燃料極または空気極の触媒電極中の電極反応領域へ、面内で均一に充分に供給する。それとともに、アノード電極反応によって生じる電荷を単セル外部に放出させること、さらに反応生成水や未反応ガスを単セル外部に効率よく排出する役割を担うものである。ガス拡散層としては、電子伝導性を有する多孔質体、例えばカーボンクロスやカーボンペーパーを好ましく用いることができる。   The gas diffusion layer 5 supplies the fuel gas or air uniformly and sufficiently in a plane to the electrode reaction region in the catalyst electrode of the fuel electrode or the air electrode in order to perform the electrode reaction efficiently. At the same time, the charge generated by the anode electrode reaction is released to the outside of the single cell, and the reaction product water and unreacted gas are efficiently discharged to the outside of the single cell. As the gas diffusion layer, a porous body having electron conductivity such as carbon cloth or carbon paper can be preferably used.

本発明の触媒電極および固体高分子型燃料電池の製造方法としては様々な方法があるが、図２に示す走査電子顕微鏡で示した触媒電極を例として、以下にその製造方法の一例を説明する。図２は、実施例１の触媒電極の触媒の粒子構造を示す走査電子顕微鏡（ＳＥＭ）写真（倍率：５万倍）である。具体的には、図２に示す触媒電極は、ＧＮＦ担体上に樹枝状の構造を有する酸化白金触媒を形成した例である。   There are various methods for producing the catalyst electrode and the polymer electrolyte fuel cell of the present invention. An example of the production method will be described below by taking the catalyst electrode shown in the scanning electron microscope shown in FIG. 2 as an example. . FIG. 2 is a scanning electron microscope (SEM) photograph (magnification: 50,000 times) showing the particle structure of the catalyst of the catalyst electrode of Example 1. Specifically, the catalyst electrode shown in FIG. 2 is an example in which a platinum oxide catalyst having a dendritic structure is formed on a GNF support.

（工程１）触媒担体としてのＧＮＦを準備する。
Ｓｉ基体上にＧＮＦ形成触媒となるＰｄ−Ｃｏ微粒子をＣｏ５０原子％の組成比で約２０ｎｍの膜厚で成膜する。これを熱ＣＶＤ装置の反応容器内に配置し、真空排気後６００℃、１０分の加熱によりＰｄ−Ｃｏ微粒子を還元凝集せしめ、さらに１％アセチレン（９９％ヘリウム）ガスおよび１００％水素ガスをそれぞれ２０ｓｃｃｍづつ導入して、反応容器内の全圧を２ｋＰａに保持する。次いで反応容器内の基板温度を８００℃まで上昇させて２０分間保持し、Ｓｉ基体上に直径約５０ｎｍのＧＮＦを厚さ約２０μｍ成長させる。 (Step 1) Prepare GNF as a catalyst carrier.
Pd—Co fine particles serving as a GNF forming catalyst are formed on a Si substrate with a composition ratio of Co 50 atomic% and a film thickness of about 20 nm. This was placed in a reaction vessel of a thermal CVD apparatus, Pd—Co fine particles were reduced and aggregated by heating at 600 ° C. for 10 minutes after evacuation, and further 1% acetylene (99% helium) gas and 100% hydrogen gas were respectively added. 20 sccm is introduced at a time, and the total pressure in the reaction vessel is maintained at 2 kPa. Next, the substrate temperature in the reaction vessel is raised to 800 ° C. and held for 20 minutes, and GNF having a diameter of about 50 nm is grown on the Si substrate to a thickness of about 20 μm.

（工程２）次に、上記工程によって作製した基体をスパッタ装置に移動し、樹枝状構造を有する酸化白金触媒を膜厚約１００ｎｍ成膜する。
スパッタ室内圧力を１．０×１０-4Ｐａまで排気した後、Ａｒ、Ｏ2を其々２．５、２０．０ｓｃｃｍ導入し、オリフィスにて全圧を６．０Ｐａに調整する。 (Step 2) Next, the substrate prepared in the above step is moved to a sputtering apparatus, and a platinum oxide catalyst having a dendritic structure is formed to a thickness of about 100 nm.
After the sputtering chamber pressure is evacuated to 1.0 × 10 −4 Pa, Ar and O 2 are introduced to 2.5 and 20.0 sccm, respectively, and the total pressure is adjusted to 6.0 Pa at the orifice.

ＲＦ投入パワー４．０Ｗ／ｃｍ2にて反応性スパッタを行い、樹枝状構造を有する酸化 白金を膜厚約１００ｎｍ成膜する。
このとき、スパッタされた原子は基体に対して指向性を持たずに入射、堆積するので、酸化白金はＧＮＦ表面にほぼ１００％の被覆率で有効に形成される。 Reactive sputtering is performed at an RF input power of 4.0 W / cm 2 to form a platinum oxide having a dendritic structure with a film thickness of about 100 nm.
At this time, since the sputtered atoms are incident and deposited without directivity to the substrate, platinum oxide is effectively formed on the GNF surface with a coverage of almost 100%.

成膜が終了した基体は、１０ｋＰａの２％Ｈ2／Ｈｅに暴露することによって容易に還元される。
（工程３）還元処理まで行った触媒電極に対して、アイオノマー処理を行う。すなわち濃度、溶媒等を調整したＮａｆｉｏｎ分散溶液を触媒電極表面に滴下する。 The substrate after film formation is easily reduced by exposure to 10 kPa of 2% H 2 / He.
(Step 3) An ionomer treatment is performed on the catalyst electrode that has been subjected to the reduction treatment. That is, a Nafion dispersion solution adjusted in concentration, solvent, etc. is dropped on the surface of the catalyst electrode.

（工程４）こうして作製した触媒電極によって固体高分子電解質膜（Ｄｕｐｏｎｔ製、Ｎａｆｉｏｎ１１２）を挟みこんでホットプレスを行う。さらにＳｉ基板を剥離することにより、一対の触媒電極を固体高分子電解質膜に転写して、電解質膜と一対の触媒電極を接合する。   (Step 4) Hot pressing is performed by sandwiching a solid polymer electrolyte membrane (manufactured by Dupont, Nafion 112) between the catalyst electrodes thus produced. Further, by peeling the Si substrate, the pair of catalyst electrodes is transferred to the solid polymer electrolyte membrane, and the electrolyte membrane and the pair of catalyst electrodes are joined.

（工程５）この接合体をガス拡散層としてのカーボンクロス（Ｅ−ＴＥＫ製 ＬＴ１４００−Ｗ）、さらに燃料極電極および空気極電極によって挟んで単セルを作製する。
以上、図２に示した触媒電極の場合を例として、固体高分子型燃料電池の単セルの作製方法を説明した。 (Step 5) A single cell is produced by sandwiching the joined body between a carbon cloth (LT1400-W manufactured by E-TEK) as a gas diffusion layer, and a fuel electrode and an air electrode.
As described above, the method for producing a single cell of the polymer electrolyte fuel cell has been described taking the case of the catalyst electrode shown in FIG. 2 as an example.

本発明はこの単セル構成の固体高分子型燃料電池に限定されるものではなく、単セルを複数スタックした構成の固体高分子型燃料電池をも含むものである。   The present invention is not limited to the polymer electrolyte fuel cell having a single cell configuration, but includes a polymer electrolyte fuel cell having a configuration in which a plurality of single cells are stacked.

次に、上記実施の形態に基づく、より具体的な実施例を詳細に説明する。
実施例１
本実施例は、実施形態中で述べた、ＧＮＦ担体上に樹枝状の構造を有する白金触媒を形成した場合の例である。 Next, more specific examples based on the above embodiment will be described in detail.
Example 1
This example is an example in which a platinum catalyst having a dendritic structure is formed on a GNF support described in the embodiment.

以下、本実施例に係わる固体高分子型燃料電池の製造工程を詳細に説明する。
（工程１）
先ず、触媒担体としてのＧＮＦを準備する。 Hereinafter, the manufacturing process of the polymer electrolyte fuel cell according to the present embodiment will be described in detail.
(Process 1)
First, GNF as a catalyst carrier is prepared.

Ｓｉ基体上にＧＮＦ形成触媒となるＰｄ−Ｃｏ微粒子をＣｏ５０原子％の組成比で約２０ｎｍの膜厚で成膜した。これを熱ＣＶＤ装置の反応容器内に配置した。真空排気後、６００℃、１０分の加熱によりＰｄ−Ｃｏ微粒子を還元凝集せしめ、さらに１％アセチレン（９９％ヘリウム）ガスおよび１００％水素ガスをそれぞれ２０ｓｃｃｍづつ導入して、反応容器内の全圧を２ｋＰａに保持した。次いで反応容器内の基体温度を８００℃まで上昇させて２０分間保持し、Ｓｉ基体上に直径約５０ｎｍのＧＮＦを厚さ約２０μｍ成長させた。   Pd—Co fine particles serving as a GNF forming catalyst were formed on a Si substrate with a composition ratio of Co 50 atomic% and a film thickness of about 20 nm. This was placed in a reaction vessel of a thermal CVD apparatus. After evacuation, Pd—Co fine particles were reduced and aggregated by heating at 600 ° C. for 10 minutes, and further, 1% acetylene (99% helium) gas and 100% hydrogen gas were introduced in 20 sccm increments, and the total pressure in the reaction vessel was increased. Was maintained at 2 kPa. Next, the substrate temperature in the reaction vessel was raised to 800 ° C. and held for 20 minutes, and GNF having a diameter of about 50 nm was grown on the Si substrate to a thickness of about 20 μm.

（工程２）
次に、上記工程によって作製した基体をスパッタ装置に移動し、樹枝状構造を有する酸化白金触媒を成膜する。 (Process 2)
Next, the substrate manufactured by the above process is moved to a sputtering apparatus, and a platinum oxide catalyst having a dendritic structure is formed.

スパッタ室内圧力を１．０×１０-4Ｐａまで排気した後、Ａｒ、Ｏ2を其々２．５、２０．０ｓｃｃｍ導入し、オリフィスにて全圧を６．０Ｐａに調整した。
ＲＦ投入パワー４．０Ｗ／ｃｍ2にて反応性スパッタを行い、ＧＮＦ表面上に樹枝状構造を有する酸化白金をアノード用５０μｇ／ｃｍ2、カソード用０．５ｍｇ／ｃｍ2でそれぞれ成膜した。 After evacuating the sputtering chamber pressure to 1.0 × 10 −4 Pa, Ar and O 2 were introduced to 2.5 and 20.0 sccm, respectively, and the total pressure was adjusted to 6.0 Pa with the orifice.
Reactive sputtering was performed at an RF input power of 4.0 W / cm 2 , and platinum oxide having a dendritic structure on the GNF surface was formed at 50 μg / cm 2 for the anode and 0.5 mg / cm 2 for the cathode, respectively.

このとき、スパッタされた原子は基体に対して指向性を持たずに入射、堆積するので、酸化白金はＧＮＦ表面にほぼ１００％の被覆率で有効に形成されていた。図２は、実施例１の触媒電極、すなわちグラファイトナノファイバー上に、酸化白金の薄片が集合して形成された樹枝状の構造を有する触媒電極の触媒の粒子構造を示す走査電子顕微鏡（ＳＥＭ）写真（倍率：５万倍）である。   At this time, since the sputtered atoms are incident and deposited without directivity to the substrate, platinum oxide was effectively formed on the GNF surface with a coverage of almost 100%. FIG. 2 is a scanning electron microscope (SEM) showing the particle structure of the catalyst of the catalyst electrode of Example 1, that is, a catalyst electrode having a dendritic structure formed by assembling platinum oxide flakes on graphite nanofibers. It is a photograph (magnification: 50,000 times).

酸化白金の成膜が終了した基体は、１０ｋＰａの２％Ｈ2／Ｈｅに１０分間暴露することによって容易に還元された。
（工程３）
還元処理まで行った触媒電極に対して、アイオノマー処理を行う。すなわち濃度、溶媒等を調整したＮａｆｉｏｎ分散溶液を触媒電極表面に滴下した。アノード側の触媒電極、カソード側の触媒電極をそれぞれ作製した。 The substrate on which the platinum oxide film was formed was easily reduced by exposure to 10 kPa of 2% H 2 / He for 10 minutes.
(Process 3)
The ionomer treatment is performed on the catalyst electrode that has been subjected to the reduction treatment. That is, a Nafion dispersion solution adjusted in concentration, solvent and the like was dropped on the surface of the catalyst electrode. A catalyst electrode on the anode side and a catalyst electrode on the cathode side were prepared.

（工程４）
こうして作製した触媒電極によって固体高分子電解質膜（Ｄｕｐｏｎｔ製、Ｎａｆｉｏｎ１１２）を挟みこんでホットプレスを行った。さらにＰＴＦＥシートを剥離することにより、一対の触媒電極を高分子電解質膜に転写して、電解質膜と一対の触媒電極を接合した。 (Process 4)
Hot pressing was performed by sandwiching a solid polymer electrolyte membrane (manufactured by Dupont, Nafion 112) with the catalyst electrode thus prepared. Further, by peeling the PTFE sheet, the pair of catalyst electrodes was transferred to the polymer electrolyte membrane, and the electrolyte membrane and the pair of catalyst electrodes were joined.

この接合体をガス拡散層としてのカーボンクロス（Ｅ−ＴＥＫ製 ＬＴ１４００−Ｗ）、さらに燃料極電極および空気極電極によって挟んで単セルを作製した。
以上の工程によって作製した単セルに関して、図３に示した構成の評価装置を用いて特性評価を行った。アノード電極側に水素ガスを、カソード電極側に空気を流し、電池温度８０℃にて放電試験を行った。 This joined body was sandwiched between carbon cloth (LT1400-W, manufactured by E-TEK) as a gas diffusion layer, and a fuel electrode and an air electrode to produce a single cell.
With respect to the single cell manufactured through the above steps, the characteristics were evaluated using the evaluation apparatus having the configuration shown in FIG. A discharge test was conducted at a battery temperature of 80 ° C. by flowing hydrogen gas to the anode electrode side and air to the cathode electrode side.

このとき、比較例１として白金担持カーボンのＤｅｃａｌ法により作製した単セルに関して同様の試験を行った。
まず反応律速領域である９００ｍＶでの電流密度を比較すると、本実施例１が７．４ｍＡ／ｃｍ2であったのに対し、比較例１では２．０ｍＡ／ｃｍ2であった。さらに、これを触媒担持量（カソード触媒換算）で除した触媒比活性を比較すると、本実施例１が１４．８Ａ／ｇであったのに対し、比較例１では５．７Ａ／ｇであった。 At this time, as Comparative Example 1, a similar test was performed on a single cell produced by the Decal method of platinum-supported carbon.
First, comparing the current density at 900mV within a reaction rate-limiting region, the first embodiment whereas was 7.4 mA / cm 2, was 2.0 mA / cm 2 in Comparative Example 1. Furthermore, when the specific activity of the catalyst obtained by dividing this by the amount of catalyst supported (cathode catalyst conversion) was compared, it was 14.8 A / g in Example 1, whereas it was 5.7 A / g in Comparative Example 1. It was.

また限界電流領域で比較すると、本実施例１の単セルが６００ｍＡ／ｃｍ2以上の電流密度であるのに対し、比較例１では５２０ｍＡ／ｃｍ2であった。すなわち、本実施例１の触媒電極は比較例１の触媒電極に対し、活性分極、抵抗分極および拡散分極のいずれにおいても、特性を大幅に向上にすることができた。 Further, when compared in the limit current region, the single cell of Example 1 has a current density of 600 mA / cm 2 or more, whereas in Comparative Example 1, it was 520 mA / cm 2 . That is, the catalyst electrode of Example 1 was able to greatly improve the characteristics in all of active polarization, resistance polarization, and diffusion polarization compared to the catalyst electrode of Comparative Example 1.

さらに単セルの初期状態を揃えて、起動特性の試験を行ったところ、比較例１のセルでは起動初期に十分な特性が得られなかったのに対し、本実施例１のセルでは起動初期からほぼ定格出力を得ることができた。   Furthermore, when the initial characteristics of the single cells were aligned and the start-up characteristics were tested, the cell of Comparative Example 1 did not provide sufficient characteristics at the start of the start, whereas the cell of Example 1 had the initial start-up characteristics. Almost rated output was obtained.

以上のように、固体高分子型燃料電池の触媒電極として本実施例１に係わる触媒電極を用いることにより、触媒活性が大幅に向上でき、優れた電池特性を有する燃料電池が得られた。さらに本実施例１にかかわる触媒電極の製造方法は、簡易かつ安価で再現性のよいプロセスであるため、安定な特性を持った固体高分子型燃料電池を低コストで実現できた。   As described above, by using the catalyst electrode according to Example 1 as the catalyst electrode of the polymer electrolyte fuel cell, the catalytic activity can be greatly improved, and a fuel cell having excellent cell characteristics was obtained. Furthermore, since the method for producing the catalyst electrode according to Example 1 is a simple, inexpensive, and reproducible process, a solid polymer fuel cell having stable characteristics could be realized at low cost.

実施例２
本実施例２は、実施例１と同様の方法で、ＧＮＦ担体上に樹枝状の構造を有する白金−パラジウム複合酸化物触媒を形成した場合の触媒電極の例である。以下では本実施例２に係わる固体高分子型燃料電池の製造工程を、実施例１と構成および製法上異なる（工程１）〜（工程３）のみ説明する。 Example 2
Example 2 is an example of a catalyst electrode when a platinum-palladium composite oxide catalyst having a dendritic structure is formed on a GNF support in the same manner as Example 1. In the following, only the steps (step 1) to (step 3), which are different from the first embodiment in terms of configuration and manufacturing method, will be described for the manufacturing process of the polymer electrolyte fuel cell according to the second embodiment.

（工程１）
先ず、触媒担体としてのＧＮＦを準備する。
Ｓｉ基体上にＧＮＦ形成触媒となるＮｉ微粒子を約２０ｎｍの膜厚で成膜して、これを熱ＣＶＤ装置の反応容器内に配置した。真空排気後、６００℃、１０分の加熱により還元凝集せしめ、さらに１％アセチレン（９９％ヘリウム）ガスおよび１００％水素ガスをそれぞれ２０ｓｃｃｍづつ導入して、反応容器内の全圧を２ｋＰａに保持した。次いで反応容器内の基体温度を８００℃まで上昇させて２０分間保持し、Ｓｉ基体上に直径約１００ｎｍのＧＮＦを厚さ約３０成長させた。 (Process 1)
First, GNF as a catalyst carrier is prepared.
Ni fine particles serving as a GNF forming catalyst were formed on a Si substrate with a film thickness of about 20 nm, and this was placed in a reaction vessel of a thermal CVD apparatus. After evacuation, the mixture was reduced and aggregated by heating at 600 ° C. for 10 minutes, and further, 1% acetylene (99% helium) gas and 100% hydrogen gas were introduced in 20 sccm each, and the total pressure in the reaction vessel was maintained at 2 kPa. . Next, the temperature of the substrate in the reaction vessel was raised to 800 ° C. and held for 20 minutes, and GNF having a diameter of about 100 nm was grown on the Si substrate to a thickness of about 30.

（工程２）
次に、上記工程によって作製した基体をスパッタ装置に移動し、樹枝状構造を有する白金−パラジウム複合酸化物触媒を成膜する。 (Process 2)
Next, the substrate manufactured by the above process is moved to a sputtering apparatus, and a platinum-palladium composite oxide catalyst having a dendritic structure is formed.

スパッタ室内圧力を１．０×１０-4Ｐａまで排気した後、Ａｒ、Ｏ2を其々２．５、２０．０ｓｃｃｍ導入し、オリフィスにて全圧を６．０Ｐａに調整した。
白金、パラジウムターゲットに対して、ＲＦ投入パワーをそれぞれ４．０Ｗ／ｃｍ2、２．５Ｗ／ｃｍ2にて反応性スパッタを行い、ＧＮＦ表面上に樹枝状構造を有する酸化白金をアノード用５０μｇ／ｃｍ2、カソード用０．４ｍｇ／ｃｍ2でそれぞれ成膜した。 After evacuating the sputtering chamber pressure to 1.0 × 10 −4 Pa, Ar and O 2 were introduced to 2.5 and 20.0 sccm, respectively, and the total pressure was adjusted to 6.0 Pa with the orifice.
Platinum for palladium target, respectively 4.0 W / cm 2 of RF input power, 2.5 W / cm 2 performs reactive sputtering at, for the anode of platinum oxide having a dendritic structure on GNF surface 50 [mu] g / cm 2, at the cathode for the 0.4mg / cm 2 was formed, respectively.

このとき、スパッタされた原子は基体に対して指向性を持たずに入射、堆積するので、白金−パラジウム複合酸化物はＧＮＦ表面にほぼ１００％の被覆率で有効に形成されていた。   At this time, since the sputtered atoms were incident and deposited without directivity to the substrate, the platinum-palladium composite oxide was effectively formed on the GNF surface with a coverage of almost 100%.

成膜が終了した基体は、１０ｋＰａの２％Ｈ2／Ｈｅに１０分間暴露することによって容易に還元された。
（工程３）
還元処理まで行った触媒電極に対して、アイオノマー処理を行う。すなわち濃度、溶媒等を調整したＮａｆｉｏｎ分散溶液を触媒電極表面に滴下した。 The substrate after film formation was easily reduced by exposure to 10 kPa of 2% H 2 / He for 10 minutes.
(Process 3)
The ionomer treatment is performed on the catalyst electrode that has been subjected to the reduction treatment. That is, a Nafion dispersion solution adjusted in concentration, solvent and the like was dropped on the surface of the catalyst electrode.

以上の工程によって作製した単セルに関して、図３に示した構成の評価装置を用いて特性評価を行った。アノード電極側に水素ガスを、カソード電極側に空気を流し、電池温度８０℃にて放電試験を行った。このとき、比較例１として白金担持カーボン触媒を用いて作製した単セルに関して同様の試験を行った。   With respect to the single cell manufactured through the above steps, the characteristics were evaluated using the evaluation apparatus having the configuration shown in FIG. A discharge test was conducted at a battery temperature of 80 ° C. by flowing hydrogen gas to the anode electrode side and air to the cathode electrode side. At this time, the same test was conducted on a single cell produced using a platinum-supported carbon catalyst as Comparative Example 1.

まず反応律速領域である９００ｍＶでの電流密度を比較すると、本実施例２が７．２ｍＡ／ｃｍ2であったのに対し、比較例１では２．０ｍＡ／ｃｍ2であった。さらに、これを触媒担持量（カソード触媒換算）で除した触媒比活性を比較すると、本実施例２が９．０Ａ／ｇであったのに対し、比較例１では５．７Ａ／ｇであった。 First, comparing the current density at 900mV within a reaction rate-limiting region, the second embodiment whereas was 7.2 mA / cm 2, was 2.0 mA / cm 2 in Comparative Example 1. Furthermore, when the specific activity of the catalyst obtained by dividing this by the amount of catalyst supported (cathode catalyst equivalent) was compared, it was 9.0 A / g in Example 2, whereas it was 5.7 A / g in Comparative Example 1. It was.

また限界電流領域で比較すると、本実施例２の単セルが６００ｍＡ／ｃｍ2以上の電流密度であるのに対し、比較例１では５２０ｍＡ／ｃｍ2であった。すなわち、本実施例の触媒電極は比較例１の触媒電極に対し、活性分極、抵抗分極および拡散分極のいずれにおいても、特性を大幅に向上にすることができた。 Further, when compared in the limit current region, the single cell of Example 2 has a current density of 600 mA / cm 2 or more, whereas in Comparative Example 1, it was 520 mA / cm 2 . That is, the catalyst electrode of this example was able to greatly improve the characteristics of any of active polarization, resistance polarization and diffusion polarization compared to the catalyst electrode of Comparative Example 1.

さらに単セルの初期状態を揃えて、起動特性の試験を行ったところ、比較例１のセルでは起動初期に十分な特性が得られなかったのに対し、本実施例２のセルでは起動初期からほぼ定格出力を得ることができた。   Furthermore, when the start-up characteristics were tested with the initial state of the single cells aligned, the cell of Comparative Example 1 did not provide sufficient characteristics at the start-up stage, whereas the cell of Example 2 from the start-up stage. Almost rated output was obtained.

以上のように、固体高分子型燃料電池の触媒電極として本実施例２に係わる触媒電極を用いることにより、触媒活性が大幅に向上でき、優れた電池特性を有する燃料電池が得られた。さらに本実施例にかかわる触媒電極の製造方法は、簡易かつ安価で再現性のよいプロセスであるため、安定な特性を持った固体高分子型燃料電池を低コストで実現できた。   As described above, by using the catalyst electrode according to Example 2 as the catalyst electrode of the polymer electrolyte fuel cell, the catalytic activity can be greatly improved, and a fuel cell having excellent cell characteristics was obtained. Furthermore, since the catalyst electrode manufacturing method according to this example is a simple, inexpensive, and reproducible process, a solid polymer fuel cell having stable characteristics can be realized at low cost.

本発明によれば、触媒利用率を向上した構成の触媒電極を汎用性がある簡易な方法で製造できるので、前記触媒電極を長期間渡って均一で安定な発電特性を有する固体高分子型燃料電池に利用することができる。   According to the present invention, a catalyst electrode having an improved catalyst utilization rate can be produced by a simple method having versatility, so that the polymer electrode has a uniform and stable power generation characteristic over a long period of time. It can be used for batteries.

触媒電極を用いた固体高分子型燃料電池の単セルの断面構成の一例を表す模式図である。It is a schematic diagram showing an example of the section composition of the single cell of the polymer electrolyte fuel cell using a catalyst electrode. 実施例１の触媒電極の触媒の粒子構造を示す走査電子顕微鏡（ＳＥＭ）写真（倍率：５万倍）である。2 is a scanning electron microscope (SEM) photograph (magnification: 50,000 times) showing the particle structure of the catalyst of the catalyst electrode of Example 1. FIG. 固体高分子型燃料電池の評価装置の模式図である。It is a schematic diagram of the evaluation apparatus of a polymer electrolyte fuel cell.

符号の説明Explanation of symbols

１ 固体高分子電解質膜
２ 触媒
３ 炭素繊維
４ カソード触媒電極
５ アノード触媒電極
６ カソードガス拡散層
７ アノードガス拡散層
８ カソード電極
９ アノード電極
１０ 膜−電極接合体 DESCRIPTION OF SYMBOLS 1 Solid polymer electrolyte membrane 2 Catalyst 3 Carbon fiber 4 Cathode catalyst electrode 5 Anode catalyst electrode 6 Cathode gas diffusion layer 7 Anode gas diffusion layer 8 Cathode electrode 9 Anode electrode 10 Membrane-electrode assembly

Claims (8)

固体高分子型燃料電池の触媒電極であって、前記触媒電極は触媒と、触媒を担持する炭素繊維を有し、前記触媒は薄片状のナノ構造を有する固体高分子型燃料電池の触媒電極の製造方法において、前記触媒を反応性真空蒸着法によって形成する工程を有することを特徴とする固体高分子型燃料電池の触媒電極の製造方法。   A catalyst electrode of a polymer electrolyte fuel cell, wherein the catalyst electrode includes a catalyst and a carbon fiber supporting the catalyst, and the catalyst is a catalyst electrode of a polymer electrolyte fuel cell having a flaky nanostructure A method for producing a catalyst electrode of a polymer electrolyte fuel cell, comprising the step of forming the catalyst by a reactive vacuum deposition method. 前記触媒が、薄片状のナノ構造単位を有した樹枝状構造であることを特徴とする請求項１に記載の固体高分子型燃料電池の触媒電極の製造方法。 2. The method for producing a catalyst electrode of a polymer electrolyte fuel cell according to claim 1, wherein the catalyst has a dendritic structure having flaky nanostructure units. 前記触媒は、白金酸化物、白金酸化物と白金以外の金属元素の酸化物との複合酸化物、前記白金酸化物または複合酸化物を還元処理してなる白金または白金を含んだ多元金属、白金と白金以外の金属元素の酸化物との混合物あるいは白金を含んだ多元金属と白金以外の金属元素の酸化物との混合物であることを特徴とする請求項１または２に記載の固体高分子型燃料電池の触媒電極の製造方法。 The catalyst includes platinum oxide, a composite oxide of platinum oxide and an oxide of a metal element other than platinum, platinum formed by reducing the platinum oxide or composite oxide, or a multi-metal containing platinum, platinum 3. The solid polymer type according to claim 1, which is a mixture of a metal element oxide other than platinum or a mixture of a multielement metal containing platinum and an oxide of a metal element other than platinum. A method for producing a catalyst electrode of a fuel cell. 前記白金以外の金属元素は、Ａｌ，Ｓｉ，Ｔｉ，Ｖ，Ｃｒ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎ，Ｇｅ，Ｚｒ，Ｎｂ，Ｍｏ，Ｒｕ，Ｒｈ，Ｐｄ，Ａｇ，Ｉｎ，Ｓｎ，Ｈｆ，Ｔａ，Ｗ，Ｏｓ，Ｉｒ，Ａｕ，Ｌａ，Ｃｅ，Ｎｄから選ばれる少なくとも一種類以上の金属からなることを特徴とする請求項３に記載の固体高分子型燃料電池の触媒電極の製造方法。 The metal elements other than platinum are Al, Si, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ge, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Hf, 4. The method for producing a catalyst electrode for a polymer electrolyte fuel cell according to claim 3 , comprising at least one metal selected from Ta, W, Os, Ir, Au, La, Ce, and Nd. 前記触媒の薄片の最大厚さが５ｎｍ以上５０ｎｍ以下であることを特徴とする請求項１乃至４のいずれかの項に記載の固体高分子型燃料電池の触媒電極の製造方法。 5. The method for producing a catalyst electrode of a polymer electrolyte fuel cell according to claim 1, wherein the maximum thickness of the catalyst flakes is 5 nm or more and 50 nm or less. 前記炭素繊維は熱ＣＶＤ法によって形成することを特徴とする請求項１に記載の固体高分子型燃料電池の触媒電極の製造方法。 2. The method for producing a catalyst electrode of a polymer electrolyte fuel cell according to claim 1 , wherein the carbon fiber is formed by a thermal CVD method. 前記炭素繊維はナノチューブまたはナノファイバーであることを特徴とする請求項１または６に記載の固体高分子型燃料電池の触媒電極の製造方法。 The carbon fiber production method of the catalyst electrode of a polymer electrolyte fuel cell according to claim 1 or 6 characterized in that it is a nanotube or nanofiber. 前記炭素繊維の平均直径は５ｎｍ以上５００ｎｍ以下で、平均長さは１μｍ以上１００μｍ以下であることを特徴とする１、６または７のいずれかの項に記載の固体高分子型燃料電池の触媒電極の製造方法。 The catalyst electrode of a polymer electrolyte fuel cell according to any one of 1 , 6 and 7 , wherein the carbon fiber has an average diameter of 5 nm to 500 nm and an average length of 1 μm to 100 μm. Manufacturing method .
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