JP2007227088A - Electrode for polymer electrolyte fuel cell, its manufacturing method and treating method, and polymer electrolyte fuel cell - Google Patents

Electrode for polymer electrolyte fuel cell, its manufacturing method and treating method, and polymer electrolyte fuel cell Download PDF

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JP2007227088A
JP2007227088A JP2006045367A JP2006045367A JP2007227088A JP 2007227088 A JP2007227088 A JP 2007227088A JP 2006045367 A JP2006045367 A JP 2006045367A JP 2006045367 A JP2006045367 A JP 2006045367A JP 2007227088 A JP2007227088 A JP 2007227088A
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fuel cell
electrode
polymer electrolyte
electrolyte fuel
catalyst
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Hideo Sugiyama
秀夫 杉山
Shinichi Toyosawa
真一 豊澤
Shinichiro Sugi
信一郎 杉
Kinya Suzuki
欽也 鈴木
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Bridgestone Corp
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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
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    • 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
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrode for a polymer electrolyte fuel cell capable of shortening a preliminary operation period; and to provide the manufacturing method of the electrode for the polymer electrolyte fuel cell. <P>SOLUTION: The manufacturing method of the electrode for the polymer electrolyte fuel cell having a catalyst carrier and a metal catalyst carried on the catalyst carrier contains a process carrying the metal catalyst on the catalyst carrier, and a process chemically reducing the catalyst carrier carried with the metal catalyst with a reduction agent. The electrode for the polymer electrolyte fuel cell manufactured by this method is used. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、固体高分子型燃料電池用電極、該固体高分子型燃料電池用電極の製造方法及び処理方法、並びに該固体高分子型燃料電池用電極を備えた固体高分子型燃料電池に関し、特に固体高分子型燃料電池の予備運転時間を短縮することが可能な固体高分子型燃料電池用電極に関するものである。   The present invention relates to a polymer electrolyte fuel cell electrode, a method for producing and processing the polymer electrolyte fuel cell electrode, and a polymer electrolyte fuel cell including the polymer electrolyte fuel cell electrode. In particular, the present invention relates to an electrode for a polymer electrolyte fuel cell capable of shortening the preliminary operation time of the polymer electrolyte fuel cell.

昨今、発電効率が高く、環境への負荷が小さい電池として、燃料電池が注目を集めており、広く研究開発が行われている。燃料電池の中でも、出力密度が高く作動温度が低い固体高分子型燃料電池は、小型化や低コスト化が他のタイプの燃料電池よりも容易なことから、電気自動車用電源、分散発電システム、家庭用のコージェネレーションシステムとして広く普及することが期待されている。   In recent years, fuel cells have attracted attention as a battery having high power generation efficiency and a low environmental load, and extensive research and development has been conducted. Among fuel cells, solid polymer fuel cells with high power density and low operating temperature are easier to reduce in size and cost than other types of fuel cells. It is expected to spread widely as a household cogeneration system.

一般に固体高分子型燃料電池は、固体高分子電解質膜及び該固体高分子電解質膜の両側に配置された電極（燃料極及び酸化極）からなる膜電極接合体（ＭＥＡ）と、該膜電極接合体の外側に配置された導電性のセパレータとを備える。ここで、電極は、固体高分子電解質膜に隣接する触媒層と、該触媒層の外側に配置されたガス拡散層とからなる。該触媒層は、一般に炭素質の担持体上にＰｔ等の貴金属を担持し、更に任意に高分子電解質を塗布して形成されており、燃料極において、２Ｈ2→４Ｈ+＋４ｅ-で示される反応に触媒作用を示すと共に、酸化極では、Ｏ2＋４Ｈ+＋４ｅ-→２Ｈ2Ｏで表される反応に触媒作用を示す。また、上記ガス拡散層は、触媒層への燃料ガス及び酸化剤ガスの供給や、生成した水のセパレータへの排出をスムーズにする役割を担い、該ガス拡散層としては、一般にカーボンペーパーやカーボンクロス等が使用されている。また、上記セパレータは、その表面にガス流路が形成されており、燃料ガスや酸化剤ガスを通過させると同時に、上記ガス拡散層から電流を外部に伝え、電気エネルギーを取り出す役割を担う（非特許文献１及び２参照）。 In general, a polymer electrolyte fuel cell includes a membrane electrode assembly (MEA) comprising a solid polymer electrolyte membrane and electrodes (fuel electrode and oxidation electrode) disposed on both sides of the solid polymer electrolyte membrane, and the membrane electrode junction. And a conductive separator disposed outside the body. Here, the electrode includes a catalyst layer adjacent to the solid polymer electrolyte membrane and a gas diffusion layer disposed outside the catalyst layer. The catalyst layer is generally formed by supporting a noble metal such as Pt on a carbonaceous support and further optionally applying a polymer electrolyte, and is represented by 2H 2 → 4H + + 4e − at the fuel electrode. In addition to showing a catalytic action in the reaction, the oxidation electrode shows a catalytic action in a reaction represented by O 2 + 4H + + 4e − → 2H 2 O. The gas diffusion layer plays a role of smoothly supplying fuel gas and oxidant gas to the catalyst layer and discharging the generated water to the separator. As the gas diffusion layer, carbon paper or carbon is generally used. A cloth or the like is used. The separator has a gas flow path formed on the surface thereof, and allows fuel gas and oxidant gas to pass therethrough, and at the same time, transmits current from the gas diffusion layer to the outside to take out electric energy (non-container). (See Patent Documents 1 and 2).

日本化学会編，「化学総説Ｎｏ.４９，新型電池の材料化学」，学会出版センター，２００１年，ｐ．１８０−１８２The Chemical Society of Japan, “Chemical Review No. 49, Material Chemistry of New Batteries”, Academic Publishing Center, 2001, p. 180-182 「固体高分子型燃料電池＜２００１年版＞」，技術情報協会，２００１年，ｐ．１４−１５“Polymer fuel cell <2001 edition>”, Technical Information Association, 2001, p. 14-15

ところで、本発明者らが、従来の電極、特に、炭素質の担持体上に電気メッキや無電解メッキ法で主に貴金属を析出させてなる触媒層を備える電極を用いた固体高分子型燃料電池について電池性能を検討したところ、運転初期は電池性能が低く、運転を継続するに従って電池性能の向上が見られ、やがて、一定の電池性能を発揮することが分った。このため、従来の電極を用いた場合、燃料電池の電池性能が一定になるまでに、予備運転を相当期間行う必要であり、また、どの程度の期間に渡って予備運転を行う必要があるかを判断する必要がある。   By the way, the present inventors have used a conventional polymer, particularly a polymer electrolyte fuel using an electrode provided with a catalyst layer formed by precipitating a noble metal mainly by electroplating or electroless plating on a carbonaceous support. As a result of examining the battery performance of the battery, it was found that the battery performance was low in the initial stage of operation, and that the battery performance was improved as the operation was continued. For this reason, when conventional electrodes are used, it is necessary to perform preliminary operation for a considerable period until the cell performance of the fuel cell becomes constant, and for how long it is necessary to perform preliminary operation It is necessary to judge.

そこで、本発明の目的は、上記従来技術の問題を解決し、運転初期から一定の電池性能を発揮するまでの期間、即ち、予備運転期間を短縮することが可能な固体高分子型燃料電池用電極並びにその製造方法及び処理方法を提供することにある。また、本発明の他の目的は、かかる電極を備え、予備運転期間が短い固体高分子型燃料電池を提供することにある。   Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and for a polymer electrolyte fuel cell capable of shortening a period from the initial operation to a certain cell performance, that is, a preliminary operation period. The object is to provide an electrode and a method of manufacturing and processing the same. Another object of the present invention is to provide a polymer electrolyte fuel cell comprising such an electrode and having a short preliminary operation period.

本発明者らは、上記目的を達成するために鋭意検討した結果、触媒担持体と該触媒担持体上に担持された金属触媒とを備える固体高分子型燃料電池用電極を還元剤を用いて化学的に還元処理し、還元処理後の固体高分子型燃料電池用電極を用いることで、固体高分子型燃料電池の予備運転期間を短縮できることを見出し、本発明を完成させるに至った。   As a result of intensive studies to achieve the above object, the present inventors have used a reducing agent for a polymer electrolyte fuel cell electrode comprising a catalyst carrier and a metal catalyst supported on the catalyst carrier. It has been found that the preliminary operation period of the polymer electrolyte fuel cell can be shortened by chemically reducing and using the electrode for the polymer electrolyte fuel cell after the reduction treatment, and the present invention has been completed.

即ち、本発明の固体高分子型燃料電池用電極の製造方法は、触媒担持体と、該触媒担持体上に担持された金属触媒とを備える固体高分子型燃料電池用電極の製造方法であって、
触媒担持体に金属触媒を担持する工程と、金属触媒が担持された触媒担持体を還元剤を用いて化学的に還元処理する工程とを含むことを特徴とする。 That is, the method for producing a polymer electrolyte fuel cell electrode of the present invention is a method for producing a polymer electrolyte fuel cell electrode comprising a catalyst carrier and a metal catalyst supported on the catalyst carrier. And
The method includes a step of supporting a metal catalyst on a catalyst support, and a step of chemically reducing the catalyst support on which the metal catalyst is supported using a reducing agent.

本発明の固体高分子型燃料電池用電極の製造方法の好適例においては、前記触媒担持体が、芳香環を有する化合物を酸化重合してフィブリル状ポリマーを生成させ、該フィブリル状ポリマーを焼成炭化して生成させた３次元連続状炭素繊維である。   In a preferred example of the method for producing an electrode for a polymer electrolyte fuel cell of the present invention, the catalyst carrier generates a fibril polymer by oxidative polymerization of a compound having an aromatic ring, and the fibril polymer is calcined and carbonized. It is the three-dimensional continuous carbon fiber produced | generated in this way.

本発明において、前記金属触媒は、貴金属を含むことが好ましく、Ｐｔを含むことが更に好ましい。   In the present invention, the metal catalyst preferably contains a noble metal, and more preferably contains Pt.

本発明の固体高分子型燃料電池用電極の製造方法の他の好適例においては、電気メッキ又は無電解メッキにより、前記触媒担持体に金属触媒を担持する。   In another preferred embodiment of the method for producing an electrode for a polymer electrolyte fuel cell of the present invention, a metal catalyst is supported on the catalyst support by electroplating or electroless plating.

本発明において、前記固体高分子型燃料電池用電極は、更に多孔質支持体を備え、該多孔質支持体上に前記触媒担持体が配置されていることが好ましい。   In the present invention, the polymer electrolyte fuel cell electrode preferably further comprises a porous support, and the catalyst support is disposed on the porous support.

また、本発明の固体高分子型燃料電池用電極は、上記の方法で製造されたことを特徴とし、本発明の固体高分子型燃料電池は、該電極を備えることを特徴とする。   In addition, the polymer electrolyte fuel cell electrode of the present invention is manufactured by the above-described method, and the polymer electrolyte fuel cell of the present invention includes the electrode.

更に、本発明の固体高分子型燃料電池用電極の処理方法は、触媒担持体と該触媒担持体上に担持された金属触媒とを備える固体高分子型燃料電池用電極を、還元剤を用いて化学的に還元処理することを特徴とする。   Furthermore, in the method for treating a polymer electrolyte fuel cell electrode according to the present invention, a solid polymer fuel cell electrode comprising a catalyst carrier and a metal catalyst supported on the catalyst carrier is obtained by using a reducing agent. It is characterized by being chemically reduced.

本発明によれば、触媒担持体と該触媒担持体上に担持された金属触媒とを備える固体高分子型燃料電池用電極を還元剤を用いて化学的に還元処理することで、固体高分子型燃料電池の予備運転期間を短縮することが可能な固体高分子型燃料電池用電極を提供することができる。また、かかる電極を備え、予備運転期間が短い固体高分子型燃料電池を提供することができる。   According to the present invention, a solid polymer type fuel cell electrode comprising a catalyst carrier and a metal catalyst supported on the catalyst carrier is chemically reduced using a reducing agent to obtain a solid polymer. It is possible to provide a polymer electrolyte fuel cell electrode capable of shortening the preliminary operation period of the fuel cell. In addition, a polymer electrolyte fuel cell including such an electrode and having a short preliminary operation period can be provided.

＜固体高分子型燃料電池用電極＞
以下に、本発明を詳細に説明する。本発明の固体高分子型燃料電池用電極の製造方法は、触媒担持体と、該触媒担持体上に担持された金属触媒とを備える固体高分子型燃料電池用電極の製造方法であって、触媒担持体に金属触媒を担持する工程と、金属触媒が担持された触媒担持体を還元剤を用いて化学的に還元処理する工程とを含むことを特徴とし、また、本発明の固体高分子型燃料電池用電極は、かかる方法で製造されたことを特徴とする。還元剤を用いて上記固体高分子型燃料電池用電極を化学的に還元処理することで、触媒表面の酸化物層が除去されることにより活性が向上する等の理由で、還元処理後の固体高分子型燃料電池用電極を用いることで、固体高分子型燃料電池の予備運転期間を短縮することができる。 <Electrode for polymer electrolyte fuel cell>
The present invention is described in detail below. The method for producing a polymer electrolyte fuel cell electrode of the present invention is a method for producing a polymer electrolyte fuel cell electrode comprising a catalyst carrier and a metal catalyst supported on the catalyst carrier, And a step of carrying a metal catalyst on the catalyst carrier and a step of chemically reducing the catalyst carrier carrying the metal catalyst using a reducing agent. The fuel cell electrode is manufactured by such a method. The solid polymer fuel cell electrode is reduced for the reason that the oxide layer on the catalyst surface is removed by chemically reducing the polymer electrolyte fuel cell electrode using a reducing agent. By using the polymer fuel cell electrode, the preliminary operation period of the solid polymer fuel cell can be shortened.

本発明において、上記触媒担持体としては、炭素質の担持体が好ましく、芳香環を有する化合物を酸化重合してフィブリル状ポリマーを生成させ、該フィブリル状ポリマーを焼成炭化して生成させた３次元連続状炭素繊維が特に好ましい。該３次元連続状炭素繊維は、表面積が広く、導電性に優れるため、電極用の触媒担持体として特に好適である。ここで、フィブリル状ポリマーの原料となる芳香環を有する化合物としては、ベンゼン環を有する化合物、芳香族複素環を有する化合物を挙げることができる。また、ベンゼン環を有する化合物としては、アニリン及びアニリン誘導体が好まく、芳香族複素環を有する化合物としては、ピロール、チオフェン及びこれらの誘導体が好ましい。これら芳香環を有する化合物は、一種単独で用いてもよいし、二種以上の混合物として用いてもよい。   In the present invention, the catalyst carrier is preferably a carbonaceous carrier, and a three-dimensional product formed by oxidative polymerization of a compound having an aromatic ring to produce a fibril polymer, and then firing and carbonizing the fibril polymer. Continuous carbon fibers are particularly preferred. Since the three-dimensional continuous carbon fiber has a large surface area and excellent conductivity, it is particularly suitable as a catalyst support for electrodes. Here, examples of the compound having an aromatic ring as a raw material for the fibril-like polymer include a compound having a benzene ring and a compound having an aromatic heterocyclic ring. As the compound having a benzene ring, aniline and aniline derivatives are preferred, and as the compound having an aromatic heterocycle, pyrrole, thiophene and derivatives thereof are preferred. These compounds having an aromatic ring may be used singly or as a mixture of two or more.

上記芳香環を有する化合物を酸化重合して得られるフィブリル状ポリマーは、一般に三次元連続構造を有し、直径が30nm〜数百nmであることが好ましく、40nm〜500nmであることが更に好ましく、長さが0.5μm〜100mmであることが好ましく、1μm〜10mmであることが更に好ましい。   The fibrillar polymer obtained by oxidative polymerization of the compound having an aromatic ring generally has a three-dimensional continuous structure, and preferably has a diameter of 30 nm to several hundred nm, more preferably 40 nm to 500 nm, The length is preferably 0.5 μm to 100 mm, and more preferably 1 μm to 10 mm.

上記酸化重合法としては、電解酸化重合法及び化学的酸化重合法等の種々の方法が利用できるが、中でも電解酸化重合法が好ましい。また、酸化重合においては、原料の芳香環を有する化合物と共に、酸を混在させることが好ましい。この点について更に詳述すると、例えば、重合原料としてアニリンを用いた場合、アニリンをＨＢＦ4を混在させた状態で酸化重合して得られるポリアニリンは、通常下記式（Ａ）〜（Ｄ）：

Figure 2007227088
に示した４種のポリアニリンが混在した状態、即ち、ベンゾノイド＝アミン状態（式Ａ）、ベンゾノイド＝アンモニウム状態（式Ｂ）、ドープ＝セミキノンラジカル状態（式Ｃ）及びキノイド＝ジイミン状態（式Ｄ）の混合状態になる。ここで、上記各状態の混合比率は特に制限されるものではないが、ドープ＝セミキノンラジカル状態（式Ｃ）を多く含んでいる方がキノイド＝ジイミン状態（式Ｄ）が大部分であるよりも最終的に得られる炭素繊維の残炭率が高くなる。従って、ドープ＝セミキノンラジカル状態（式Ｃ）を多く含むポリアニリンを得るためには、重合時に酸を混在させることが好ましい。なお、重合の際に混在させる酸としては、上記ＨＢＦ4に限定されるものではなく、種々のものを使用することができ、ＨＢＦ4の他、Ｈ2ＳＯ4、ＨＣｌ、ＨＣｌＯ4等を例示することができる。ここで、該酸の濃度は、0.1〜3mol/Lの範囲が好ましく、0.5〜2.5mol/Lの範囲が更に好ましい。 As the oxidative polymerization method, various methods such as an electrolytic oxidative polymerization method and a chemical oxidative polymerization method can be used. Among them, the electrolytic oxidative polymerization method is preferable. Moreover, in oxidative polymerization, it is preferable to mix an acid with the compound which has a raw material aromatic ring. More specifically, for example, when aniline is used as a polymerization raw material, polyaniline obtained by oxidative polymerization of aniline in a state where HBF 4 is mixed is usually represented by the following formulas (A) to (D):
Figure 2007227088
 In the state where the four polyanilines shown in FIG. 4 are mixed, that is, benzonoid = amine state (formula A), benzonoid = ammonium state (formula B), dope = semiquinone radical state (formula C) and quinoid = diimine state (formula D) ). Here, the mixing ratio of each of the above states is not particularly limited, but the quinoid = diimine state (formula D) is mostly contained when the dope = semiquinone radical state (formula C) is contained in a large amount. However, the remaining carbon ratio of the finally obtained carbon fiber is increased. Therefore, in order to obtain polyaniline containing a large amount of dope = semiquinone radical state (formula C), it is preferable to mix an acid during polymerization. As the acid to be mixed in the polymerization, is not limited to the above HBF 4, can be used various ones, other HBF 4, H 2 SO 4, HCl, illustrate HClO 4, etc. can do. Here, the concentration of the acid is preferably in the range of 0.1 to 3 mol / L, and more preferably in the range of 0.5 to 2.5 mol / L.

上記ドープ＝セミキノンラジカル状態（式Ｃ）の含有割合（ドーピングレベル）は適宜調節することができ、この含有割合（ドーピングレベル）を調節することにより、得られる炭素繊維の残炭率を制御することができ、ドーピングレベルを高くすることにより得られる炭素繊維の残炭率が高くなる。なお、特に限定されるものではないが、このドープ＝セミキノンラジカル状態（式Ｃ）の含有割合（ドーピングレベル）は、通常0.01〜50％の範囲とすることが好ましい。   The content ratio (doping level) of the dope = semiquinone radical state (formula C) can be appropriately adjusted, and the residual carbon ratio of the resulting carbon fiber is controlled by adjusting the content ratio (doping level). The residual carbon ratio of the carbon fiber obtained by increasing the doping level can be increased. Although not particularly limited, the content ratio (doping level) of the dope = semiquinone radical state (formula C) is usually preferably in the range of 0.01 to 50%.

電解酸化重合によりフィブリル状ポリマーを得る場合には、芳香環を有する化合物を含む溶液中に作用極及び対極となる一対の電極板を浸漬し、両極間に前記芳香環を有する化合物の酸化電位以上の電圧を印加するか、または該芳香環を有する化合物が重合するのに充分な電圧が確保できるような条件の電流を通電すればよく、これにより作用極上にフィブリル状ポリマーが生成する。この電解酸化重合法によるフィブリル状ポリマーの合成方法の一例を挙げると、作用極及び対極としてステンレススチール、白金、カーボン等の良導電性物質からなる板や多孔質材等を用い、これらをＨ2ＳＯ4、ＨＢＦ4等の酸及び芳香環を有する化合物を含む電解溶液中に浸漬し、両極間に0.1〜1000mA/cm2、好ましくは0.2〜100mA/cm2の電流を通電して、作用極側にフィブリル状ポリマーを重合析出させる方法などが例示される。ここで、芳香環を有する化合物の電解溶液中の濃度は、0.05〜3mol/Lの範囲が好ましく、0.25〜1.5mol/Lの範囲が更に好ましい。また、電解溶液には、上記成分に加え、ｐＨを調製するために可溶性塩等を適宜添加してもよい。 In the case of obtaining a fibrillated polymer by electrolytic oxidation polymerization, a pair of electrode plates serving as a working electrode and a counter electrode are immersed in a solution containing a compound having an aromatic ring, and the oxidation potential of the compound having an aromatic ring between both electrodes is exceeded. Or a current having such a condition that a voltage sufficient to polymerize the compound having an aromatic ring may be applied, whereby a fibril polymer is formed on the working electrode. Used As an example of methods for the synthesis of fibrillar polymer by electrolytic oxidative polymerization method, stainless steel as a working electrode and a counter electrode, platinum, a plate or a porous material or the like made of a good conductive material such as carbon, these and H 2 SO 4, was immersed in an electrolyte solution containing a compound having an acid and an aromatic ring of HBF 4, etc., 0.1~1000mA / cm 2 between the electrodes, preferably by passing current of 0.2~100mA / cm 2, a working electrode Examples thereof include a method of polymerizing and depositing a fibrillated polymer on the side. Here, the concentration of the compound having an aromatic ring in the electrolytic solution is preferably in the range of 0.05 to 3 mol / L, and more preferably in the range of 0.25 to 1.5 mol / L. Moreover, in addition to the said component, you may add a soluble salt etc. to an electrolyte solution suitably in order to adjust pH.

上述のように、炭素繊維のドーピングレベルを調節することにより、得られる炭素繊維の残炭率を制御することができるが、ドーピングレベルの調節は、得られたフィブリル状ポリマーを何らかの方法で還元すればよく、その手法に特に制限はない。具体例としては、アンモニア水溶液又はヒドラジン水溶液などに浸漬する方法、電気化学的に還元電流を付加する方法などが挙げられる。この還元レベルによりフィブリル状ポリマーに含まれるドーパント量の制御を行うことができ、この場合、還元処理によってフィブリル状ポリマー中のドーパント量は減少する。また、重合時において酸濃度を制御することにより重合過程でドーピングレベルをある程度調節することもできるが、ドーピングレベルが大きく異なる種々のサンプルを得ることは難しく、このため上記還元法が好適に採用される。なお、このように含有割合を調節したドーパントは、後述する焼成炭化処理後も、その条件を制御することによって得られる炭素繊維中に保持され、これにより炭素繊維の残炭率が制御される。   As described above, by adjusting the doping level of the carbon fiber, it is possible to control the residual carbon ratio of the obtained carbon fiber. However, the adjustment of the doping level can be achieved by reducing the obtained fibrillated polymer in some way. There is no particular limitation on the method. Specific examples include a method of immersing in an aqueous ammonia solution or an aqueous hydrazine solution, a method of electrochemically applying a reduction current, and the like. The amount of dopant contained in the fibril-like polymer can be controlled by this reduction level. In this case, the amount of dopant in the fibril-like polymer is reduced by the reduction treatment. Although the doping level can be adjusted to some extent during the polymerization process by controlling the acid concentration during the polymerization, it is difficult to obtain various samples with greatly different doping levels. Therefore, the above reduction method is preferably employed. The In addition, the dopant which adjusted the content rate in this way is hold | maintained in the carbon fiber obtained by controlling the conditions after the baking carbonization process mentioned later, and, thereby, the residual carbon rate of carbon fiber is controlled.

上記のようにして作用極上に得られたフィブリル状ポリマーを、水や有機溶剤等の溶媒で洗浄し、乾燥させた後、焼成、好ましくは非酸化性雰囲気中で焼成して炭化することで、３次元連続状の炭素繊維が得られる。ここで、乾燥方法としては、特に制限されるものではないが、風乾、真空乾燥の他、流動床乾燥装置、気流乾燥機、スプレードライヤー等を使用した方法を例示することができる。また、焼成条件としては、特に限定されるものではないが、温度500〜3000℃、好ましくは600〜2800℃で、0.5〜6時間とすることが好ましい。なお、非酸化性雰囲気としては、窒素雰囲気、アルゴン雰囲気、ヘリウム雰囲気等を挙げることができ、場合によっては水素雰囲気とすることもできる。   The fibrillated polymer obtained on the working electrode as described above is washed with a solvent such as water or an organic solvent, dried, then fired, preferably fired in a non-oxidizing atmosphere and carbonized. A three-dimensional continuous carbon fiber is obtained. Here, the drying method is not particularly limited, and examples thereof include a method using a fluidized bed drying device, an air dryer, a spray dryer, etc., in addition to air drying and vacuum drying. In addition, the firing conditions are not particularly limited, but it is preferable that the temperature is 500 to 3000 ° C, preferably 600 to 2800 ° C, and 0.5 to 6 hours. Note that examples of the non-oxidizing atmosphere include a nitrogen atmosphere, an argon atmosphere, and a helium atmosphere, and in some cases, a hydrogen atmosphere can also be used.

上記フィブリル状ポリマーを焼成炭化して得られる炭素繊維は、直径が30nm〜数百nmであることが好ましく、40nm〜500nmであることが更に好ましく、長さが0.5μm〜100mmであることが好ましく、1μm〜10mmであることが更に好ましい。また、該炭素繊維は、残炭率が95〜30％であることが好ましく、90〜40％であることが更に好ましい。   The carbon fiber obtained by calcining the fibrillated polymer preferably has a diameter of 30 nm to several hundreds of nm, more preferably 40 nm to 500 nm, and a length of preferably 0.5 μm to 100 mm. 1 μm to 10 mm is more preferable. Further, the carbon fiber preferably has a residual carbon ratio of 95 to 30%, and more preferably 90 to 40%.

本発明では、上記炭素繊維等の触媒担持体に金属触媒を担持する。ここで、触媒担持体に担持される金属触媒は、貴金属を含むことが好ましく、Ｐｔを含むことが更に好ましい。なお、本発明においては、Ｐｔを単独で用いてもよいし、Ｒｕ等の他の金属との合金として用いてもよい。金属触媒としてＰｔを選択し、本発明の電極を固体高分子型燃料電池に用いることで、100℃以下の低温でも水素を高効率で酸化することができる。また、ＰｔとＲｕ等の合金を用いることで、ＣＯによるＰｔの被毒を防止して、触媒の活性低下を防止することができる。なお、担持される金属触媒は、微粒子状、繊維状、ワイヤー状、薄膜状等のいずれでもよいが、微粒子状であることが好ましく、粒径が0.5〜100nmであることが好ましく、1〜50nmであることが更に好ましい。該金属触媒の担持率は、触媒担持体1gに対して0.05〜5gの範囲が好ましい。ここで、上記金属触媒の触媒担持体上への担持法としては、特に限定されるものではなく、例えば、電気メッキ法（電解還元法）、無電解メッキ法、含浸法、スパッタ法等が挙げられるが、本発明の効果が顕著な点で、電気メッキ法及び無電解メッキ法が好ましい。   In the present invention, a metal catalyst is supported on a catalyst support such as the carbon fiber. Here, the metal catalyst supported on the catalyst support preferably contains a noble metal, and more preferably contains Pt. In the present invention, Pt may be used alone or as an alloy with another metal such as Ru. By selecting Pt as the metal catalyst and using the electrode of the present invention for a polymer electrolyte fuel cell, hydrogen can be oxidized with high efficiency even at a low temperature of 100 ° C. or lower. Further, by using an alloy such as Pt and Ru, it is possible to prevent poisoning of Pt by CO and prevent a decrease in the activity of the catalyst. The supported metal catalyst may be in the form of fine particles, fibers, wires, thin films, etc., but is preferably in the form of fine particles, preferably having a particle size of 0.5 to 100 nm, and 1 to 50 nm. More preferably. The loading ratio of the metal catalyst is preferably in the range of 0.05 to 5 g with respect to 1 g of the catalyst carrier. Here, the method for supporting the metal catalyst on the catalyst support is not particularly limited, and examples thereof include an electroplating method (electrolytic reduction method), an electroless plating method, an impregnation method, and a sputtering method. However, the electroplating method and the electroless plating method are preferable in that the effect of the present invention is remarkable.

本発明では、上記金属触媒が担持された触媒担持体を還元剤を用いて化学的に還元処理する。ここで、還元剤としては、特に限定されるものではないが、ヒドラジン、水素化ホウ素ナトリウム等を挙げることができる。また、還元処理は、例えば、水等の溶媒に還元剤を溶解させ、得られた溶液に金属触媒が担持された触媒担持体を浸漬することで実施できる。なお、還元処理の温度は、使用する還元剤及び担持された金属触媒の種類等に応じて適宜調整することが好ましい。また、還元処理時間も、上記還元処理の温度等に応じて適宜調整することが好ましい。   In the present invention, the catalyst support on which the metal catalyst is supported is chemically reduced using a reducing agent. Here, although it does not specifically limit as a reducing agent, A hydrazine, sodium borohydride, etc. can be mentioned. The reduction treatment can be performed, for example, by dissolving a reducing agent in a solvent such as water and immersing a catalyst carrier on which a metal catalyst is supported in the obtained solution. In addition, it is preferable to adjust the temperature of a reduction process suitably according to the kind of the reducing agent to be used, the supported metal catalyst, etc. Further, the reduction treatment time is preferably adjusted as appropriate according to the temperature of the reduction treatment.

上記金属触媒が担持された触媒担持体には、更に高分子電解質を含浸させてもよく、該高分子電解質としては、イオン伝導性のポリマーを使用することができ、該イオン伝導性のポリマーとしては、スルホン酸、カルボン酸、ホスホン酸、亜ホスホン酸等のイオン交換基を有するポリマーを挙げることができ、該ポリマーはフッ素を含んでも、含まなくてもよい。該イオン伝導性のポリマーとしては、ナフィオン（登録商標）等のパーフルオロカーボンスルホン酸系ポリマー等が挙げられる。該高分子電解質の含浸量は、触媒担持体100質量部に対して高分子電解質10〜500質量部の範囲が好ましい。なお、触媒担持体層の厚さは、特に限定されるものではないが、0.1〜100μmの範囲が好ましい。また、金属触媒担持量は、前記担持率と触媒担持体層の厚さにより定まり、好ましくは0.001〜0.8mg/cm2の範囲である。 The catalyst carrier on which the metal catalyst is supported may be further impregnated with a polymer electrolyte. As the polymer electrolyte, an ion conductive polymer can be used, and as the ion conductive polymer, Can include polymers having ion exchange groups such as sulfonic acid, carboxylic acid, phosphonic acid, phosphonous acid, etc., and the polymer may or may not contain fluorine. Examples of the ion conductive polymer include perfluorocarbon sulfonic acid polymers such as Nafion (registered trademark). The amount of impregnation of the polymer electrolyte is preferably in the range of 10 to 500 parts by mass of the polymer electrolyte with respect to 100 parts by mass of the catalyst support. The thickness of the catalyst carrier layer is not particularly limited, but is preferably in the range of 0.1 to 100 μm. The amount of metal catalyst supported is determined by the loading rate and the thickness of the catalyst support layer, and is preferably in the range of 0.001 to 0.8 mg / cm 2 .

本発明の固体高分子型燃料電池用電極は、更に多孔質支持体を備え、該多孔質支持体上に前記触媒担持体が配置されていることが好ましい。ここで、該多孔質支持体は、金属触媒が担持された触媒担持体（即ち、触媒層）へ水素ガス等の燃料、或いは、酸素や空気等の酸素含有ガスを供給するガス拡散層としての機能と、発生した電子の授受を行う集電体としての機能を担う。該多孔質支持体としては、多孔質で且つ電子伝導性を有するものが好ましく、具体的には、カーボンペーパー、多孔質のカーボン布等が挙げられ、カーボンペーパーが好ましい。なお、電解酸化重合における作用極として多孔質支持体を用い、該多孔質支持体上にフィブリル状ポリマーを生成させ、更に該フィブリル状ポリマーを多孔質支持体上で焼成炭化して、多孔質支持体上に炭素繊維を作製することで、金属触媒の担持工程及び還元剤による還元処理の作業性が向上する。   The electrode for a polymer electrolyte fuel cell of the present invention preferably further comprises a porous support, and the catalyst support is disposed on the porous support. Here, the porous support serves as a gas diffusion layer for supplying a fuel such as hydrogen gas or an oxygen-containing gas such as oxygen or air to a catalyst support (that is, a catalyst layer) on which a metal catalyst is supported. Functions and functions as a current collector that exchanges generated electrons. The porous support is preferably porous and has electron conductivity, and specific examples thereof include carbon paper and porous carbon cloth, and carbon paper is preferred. In addition, a porous support is used as a working electrode in electrolytic oxidation polymerization, a fibril-like polymer is formed on the porous support, and the fibril-like polymer is calcined and carbonized on the porous support to obtain a porous support. By producing the carbon fiber on the body, the workability of the metal catalyst loading process and the reduction treatment with the reducing agent is improved.

＜固体高分子型燃料電池＞
次に、本発明の固体高分子型燃料電池を図１を参照しながら説明する。図示例の固体高分子型燃料電池は、膜電極接合体（ＭＥＡ）１とその両側に位置するセパレータ２とを備える。膜電極接合体（ＭＥＡ）１は、固体高分子電解質膜３とその両側に位置する燃料極４Ａ及び空気極４Ｂとからなる。燃料極４Ａでは、２Ｈ2→４Ｈ+＋４ｅ-で表される反応が起こり、発生したＨ+は固体高分子電解質膜３を経て空気極４Ｂに至り、また、発生したｅ-は外部に取り出されて電流となる。一方、空気極４Ｂでは、Ｏ2＋４Ｈ+＋４ｅ-→２Ｈ2Ｏで表される反応が起こり、水が発生する。ここで、本発明の固体高分子型燃料電池には、上述の電極が使用されているため、早期に一定の電池性能を発揮することができ、必要とする予備運転時間が短いという格別の効果を奏する。 <Solid polymer fuel cell>
Next, the polymer electrolyte fuel cell of the present invention will be described with reference to FIG. The illustrated polymer electrolyte fuel cell includes a membrane electrode assembly (MEA) 1 and separators 2 located on both sides thereof. The membrane electrode assembly (MEA) 1 includes a solid polymer electrolyte membrane 3 and fuel electrodes 4A and air electrodes 4B located on both sides thereof. In the fuel electrode 4A, a reaction represented by 2H 2 → 4H + + 4e − occurs, the generated H + passes through the solid polymer electrolyte membrane 3 to the air electrode 4B, and the generated e − is taken out to the outside. Current. On the other hand, in the air electrode 4B, a reaction represented by O 2 + 4H + + 4e − → 2H 2 O occurs, and water is generated. Here, since the above-mentioned electrode is used in the polymer electrolyte fuel cell of the present invention, it is possible to exert a certain battery performance at an early stage, and a special effect that a required pre-operation time is short. Play.

上記燃料極４Ａ及び空気極４Ｂは、触媒層５及びガス拡散層６からなり、触媒層５が固体高分子電解質膜３に接触するように配置されている。ここで、触媒層５は、触媒担持体に金属触媒を担持してなる。また、ガス拡散層６としては、上述の多孔質支持体を使用することができる。更に、固体高分子電解質膜３としては、イオン伝導性のポリマーを使用することができ、該イオン伝導性のポリマーとしては、上記金属触媒が担持された触媒担持体に含浸させることが可能な高分子電解質として例示したものを用いることができる。また、セパレータ２としては、表面に燃料、空気及び生成した水等の流路（図示せず）が形成された通常のセパレータを用いることができる。   The fuel electrode 4A and the air electrode 4B are composed of a catalyst layer 5 and a gas diffusion layer 6, and are arranged so that the catalyst layer 5 is in contact with the solid polymer electrolyte membrane 3. Here, the catalyst layer 5 is formed by supporting a metal catalyst on a catalyst support. Moreover, as the gas diffusion layer 6, the above-mentioned porous support can be used. Furthermore, an ion conductive polymer can be used as the solid polymer electrolyte membrane 3, and the ion conductive polymer can be impregnated in a catalyst support on which the metal catalyst is supported. What was illustrated as a molecular electrolyte can be used. Moreover, as the separator 2, the normal separator with which flow paths (not shown), such as fuel, air, and produced | generated water, were formed in the surface can be used.

以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。   Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

（実施例１）
6×6cmのサイズにカットしたカーボンペーパー［東レ製］を作用極とし、ステンレスメッシュを対極とし、アニリン 0.5モル/L及び硫酸 1.5モル/Lを含む水溶液から、アニリンを電解酸化重合させ作用極上にポリアニリンを得た。なお、電解酸化重合における電流密度は25mA/cm2で、通電電荷量は3Ｃ/cm2とした。次に、カーボンペーパー上に得られたポリアニリンを十分洗浄後、乾燥し、減圧アルゴン雰囲気下1200℃で2時間焼成し、炭化させた。 Example 1
Carbon paper (made by Toray) cut to a size of 6 x 6 cm is used as the working electrode, stainless steel mesh is used as the counter electrode, and aniline is electrolytically polymerized from an aqueous solution containing 0.5 mol / L of aniline and 1.5 mol / L of sulfuric acid. Polyaniline was obtained. In addition, the current density in electrolytic oxidation polymerization was 25 mA / cm 2 , and the current carrying amount was 3 C / cm 2 . Next, the polyaniline obtained on the carbon paper was sufficiently washed, dried, and calcined at 1200 ° C. for 2 hours in a reduced pressure argon atmosphere to be carbonized.

次に、得られた炭化物（炭素繊維）／カーボンペーパー複合体を作用極とし、白金メッシュを対極として、0.02モル/Lの塩化白金酸水溶液から、白金を炭化物上に析出させた。なお、白金の析出は、パルス法で行い、電流密度が50mA/cm2で、オンタイム 0.02秒、オフタイム 0.2秒で、600サイクル行った。重量変化から白金の担持量を求めたところ、白金量は0.2mg/cm2であった。 Next, platinum was deposited on the carbide from a 0.02 mol / L chloroplatinic acid aqueous solution using the obtained carbide (carbon fiber) / carbon paper composite as a working electrode and a platinum mesh as a counter electrode. Platinum was deposited by the pulse method, and the current density was 50 mA / cm 2 , the on-time was 0.02 seconds, the off-time was 0.2 seconds, and 600 cycles were performed. When the amount of platinum supported was determined from the change in weight, the amount of platinum was 0.2 mg / cm 2 .

次に、得られた白金が担持された炭化物／カーボンペーパー複合体を5wt％のヒドラジン水溶液に浸漬し、室温で30分間放置して還元処理を施し、その後、純水で洗浄し、乾燥した。   Next, the obtained carbide / carbon paper composite carrying platinum was immersed in a 5 wt% hydrazine aqueous solution, left to stand at room temperature for 30 minutes, subjected to reduction treatment, then washed with pure water and dried.

上記のようにして作製した複合体２枚を5×5cmのサイズにカットし、5wt％のナフィオン溶液を刷毛で塗布し、100℃で30分乾燥した。重量変化からナフィオン量を求めたところ、0.8mg/cm2であった。次に、ナフィオンが塗布された複合体（即ち、電極）２枚で、厚さ50μmのナフィオン膜を挟み込み、150℃のプレスで5分間加圧、接着して、膜電極接合体（ＭＥＡ）を作製した。 Two composites produced as described above were cut into a size of 5 × 5 cm, 5 wt% Nafion solution was applied with a brush, and dried at 100 ° C. for 30 minutes. The amount of Nafion was determined from the change in weight and found to be 0.8 mg / cm 2 . Next, two composites (ie, electrodes) coated with Nafion are sandwiched with a Nafion film having a thickness of 50 μm, and pressed and bonded with a press at 150 ° C. for 5 minutes to form a membrane electrode assembly (MEA). Produced.

得られた膜電極接合体をエレクトロケミカル社製の試験セル（ＥＦＣ２５−０１ＳＰ）に組み込んで燃料電池を組み立て、電池性能を評価した。なお、セル温度は80℃とし、燃料ガスとしては水素を用い、水素流量0.3L/分、水素の加湿温度80℃とし、一方、酸化剤ガスとしては酸素を用い、酸素流量0.3L/分、酸素の加湿温度75℃とした。作製した燃料電池は、初回測定時の開放端電圧が0.92Ｖであった。また、該燃料電池を用い、0.1A/秒の走査速度で放電し、0.5Ｖまで低下したところで同じ速度で0Aまで戻す操作を繰り返した。放電を繰り返すに従い電池性能の向上が見られ、放電時の電圧が上昇した。なお、放電5サイクル目の0.2A/cm2放電時の電圧は0.81Ｖであり、放電30サイクル目の0.2A/cm2放電時の電圧は0.82Ｖであった。結果を表１に示す。 The obtained membrane electrode assembly was assembled in a test cell (EFC25-01SP) manufactured by Electrochemical Co., and a fuel cell was assembled to evaluate the battery performance. The cell temperature is 80 ° C., hydrogen is used as the fuel gas, the hydrogen flow rate is 0.3 L / min, the humidification temperature of hydrogen is 80 ° C., while the oxygen gas is used as the oxidant gas, and the oxygen flow rate is 0.3 L / min. The humidification temperature of oxygen was 75 ° C. The produced fuel cell had an open-circuit voltage of 0.92 V at the first measurement. Further, using the fuel cell, discharging was performed at a scanning speed of 0.1 A / second, and when the voltage decreased to 0.5 V, an operation of returning to 0 A at the same speed was repeated. As the discharge was repeated, the battery performance was improved and the voltage during discharge increased. The discharge 5 th cycle 0.2 A / cm 2 the voltage during discharge is 0.81 V, discharge 30 th cycle 0.2 A / cm 2 the voltage in discharging was 0.82 V. The results are shown in Table 1.

（実施例２）
5wt％のヒドラジン水溶液に代えて2wt％の水素化ホウ素ナトリウム水溶液を用いて還元処理を施す以外は、実施例１と同様にして燃料電池を作製し、電池性能を評価した。結果を表１に示す。 (Example 2)
A fuel cell was produced in the same manner as in Example 1 except that the reduction treatment was performed using a 2 wt% aqueous sodium borohydride solution instead of the 5 wt% hydrazine aqueous solution, and the cell performance was evaluated. The results are shown in Table 1.

（比較例）
ヒドラジン水溶液による還元処理を行わない以外は、実施例１と同様にして燃料電池を作製し、電池性能を評価した。得られた燃料電池は、初回測定時の開放端電圧が0.84Ｖであり、放電30サイクル目の0.2A/cm2放電時の電圧が0.79Ｖであった。結果を表１に示す。 (Comparative example)
A fuel cell was produced in the same manner as in Example 1 except that the reduction treatment with an aqueous hydrazine solution was not performed, and the cell performance was evaluated. The obtained fuel cell had an open-circuit voltage of 0.84V at the first measurement, and a voltage of 0.29 / cm 2 discharge at the discharge 30th cycle was 0.79V. The results are shown in Table 1.

Figure 2007227088
Figure 2007227088

表１から、実施例の燃料電池は、比較例の燃料電池に比べ、初回測定時の開放端電圧が高く、また、30サイクル後の各電流密度における電圧値も高く、更に、内部抵抗が低く、即ち、早期に電池性能が向上しているため、必要とする予備運転期間を短縮できることが分る。   From Table 1, the fuel cell of the example has a higher open-ended voltage at the first measurement, a higher voltage value at each current density after 30 cycles, and a lower internal resistance than the fuel cell of the comparative example. That is, it can be seen that the required preliminary operation period can be shortened because the battery performance is improved early.

本発明の固体高分子型燃料電池の一例の断面図である。It is sectional drawing of an example of the polymer electrolyte fuel cell of this invention.

符号の説明Explanation of symbols

１ 膜電極接合体（ＭＥＡ）
２ セパレータ
３ 固体高分子電解質膜
４Ａ 燃料極
４Ｂ 空気極
５ 触媒層
６ ガス拡散層

1 Membrane electrode assembly (MEA)
2 Separator 3 Solid polymer electrolyte membrane 4A Fuel electrode 4B Air electrode 5 Catalyst layer 6 Gas diffusion layer

Claims (9)

触媒担持体と、該触媒担持体上に担持された金属触媒とを備える固体高分子型燃料電池用電極の製造方法であって、
触媒担持体に金属触媒を担持する工程と、金属触媒が担持された触媒担持体を還元剤を用いて化学的に還元処理する工程とを含むことを特徴とする固体高分子型燃料電池用電極の製造方法。 A method for producing an electrode for a polymer electrolyte fuel cell comprising a catalyst carrier and a metal catalyst supported on the catalyst carrier,
An electrode for a solid polymer fuel cell, comprising: a step of supporting a metal catalyst on a catalyst support; and a step of chemically reducing the catalyst support on which the metal catalyst is supported using a reducing agent. Manufacturing method. 前記触媒担持体が、芳香環を有する化合物を酸化重合してフィブリル状ポリマーを生成させ、該フィブリル状ポリマーを焼成炭化して生成させた３次元連続状炭素繊維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用電極の製造方法。   The catalyst carrier is a three-dimensional continuous carbon fiber produced by oxidative polymerization of a compound having an aromatic ring to produce a fibril polymer, and calcining and carbonizing the fibril polymer. 2. A method for producing an electrode for a polymer electrolyte fuel cell according to 1. 前記金属触媒が、貴金属を含む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用電極の製造方法。   The method for producing an electrode for a polymer electrolyte fuel cell according to claim 1, wherein the metal catalyst contains a noble metal. 前記金属触媒が、Ｐｔを含む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用電極の製造方法。   4. The method for producing an electrode for a polymer electrolyte fuel cell according to claim 3, wherein the metal catalyst contains Pt. 電気メッキ又は無電解メッキにより、前記触媒担持体に金属触媒を担持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用電極の製造方法。   2. The method for producing an electrode for a polymer electrolyte fuel cell according to claim 1, wherein a metal catalyst is supported on the catalyst support by electroplating or electroless plating. 前記固体高分子型燃料電池用電極が更に多孔質支持体を備え、該多孔質支持体上に前記触媒担持体が配置されてい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用電極の製造方法。   2. The polymer electrolyte fuel according to claim 1, wherein the electrode for the polymer electrolyte fuel cell further includes a porous support, and the catalyst support is disposed on the porous support. Manufacturing method of battery electrode. 請求項１〜６のいずれかに記載の方法で製造された固体高分子型燃料電池用電極。   An electrode for a polymer electrolyte fuel cell produced by the method according to claim 1. 請求項７に記載の電極を備えた固体高分子型燃料電池。   A polymer electrolyte fuel cell comprising the electrode according to claim 7. 触媒担持体と該触媒担持体上に担持された金属触媒とを備える固体高分子型燃料電池用電極を、還元剤を用いて化学的に還元処理することを特徴とする固体高分子型燃料電池用電極の処理方法。

A polymer electrolyte fuel cell characterized by chemically reducing a polymer electrolyte fuel cell electrode comprising a catalyst carrier and a metal catalyst supported on the catalyst carrier using a reducing agent. Electrode processing method.

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013035741A1 (en) * 2011-09-06 2013-03-14 住友化学株式会社 Method for producing dispersion liquid of electrode catalyst, dispersion liquid of electrode catalyst, method for producing electrode catalyst, electrode catalyst, electrode structure, membrane electrode assembly, fuel cell, and air cell
US9260053B2 (en) 2011-05-23 2016-02-16 Sl Corporation Automotive headlamp system and method of controlling the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9260053B2 (en) 2011-05-23 2016-02-16 Sl Corporation Automotive headlamp system and method of controlling the same
WO2013035741A1 (en) * 2011-09-06 2013-03-14 住友化学株式会社 Method for producing dispersion liquid of electrode catalyst, dispersion liquid of electrode catalyst, method for producing electrode catalyst, electrode catalyst, electrode structure, membrane electrode assembly, fuel cell, and air cell
JPWO2013035741A1 (en) * 2011-09-06 2015-03-23 住友化学株式会社 Electrocatalyst dispersion manufacturing method, electrode catalyst dispersion, electrode catalyst manufacturing method, electrode catalyst, electrode structure, membrane electrode assembly, fuel cell and air cell

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