JP2006040575A - Anode electrode for fuel cell - Google Patents

Anode electrode for fuel cell Download PDF

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JP2006040575A
JP2006040575A JP2004214514A JP2004214514A JP2006040575A JP 2006040575 A JP2006040575 A JP 2006040575A JP 2004214514 A JP2004214514 A JP 2004214514A JP 2004214514 A JP2004214514 A JP 2004214514A JP 2006040575 A JP2006040575 A JP 2006040575A
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conductive
fuel cell
conductive porous
catalyst
anode electrode
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Toku Nagasawa
徳 長沢
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Nitto Denko 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
    • 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

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anode electrode for a fuel cell and a membrane electrode junction as well as a solid polymer fuel cell using the same through restraint of poisoning of electrode catalyst by carbon monoxide contained in reformed hydrogen. <P>SOLUTION: The anode electrode for the fuel cell is provided with: a conductive porous base material; a conductive porous water-repellent layer fitted on the surface of the conductive porous base material or so as to be partly impregnated inside it with a thickness of 30 to 500 μm with a mixture containing fluorine group polymer fine particles and conductive carbon fine particles bonded; and a catalyst layer fitted beside the conductive porous water-repellent layer and containing catalyst particles containing an alloy including platinum-ruthenium and a proton-conductive polymer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、白金を触媒として含有する燃料電池用アノード電極および膜電極接合体、並びにそれを用いた固体高分子型燃料電池に関し、詳しくは、白金触媒をより有効に機能させて高い出力を発現することができる燃料電池用アノード電極、固体高分子型燃料電池等に関する。   TECHNICAL FIELD The present invention relates to a fuel cell anode electrode and membrane electrode assembly containing platinum as a catalyst, and a solid polymer fuel cell using the same, and more specifically, a platinum catalyst is made to function more effectively to produce a high output. The present invention relates to a fuel cell anode electrode, a polymer electrolyte fuel cell, and the like.

近年、固体高分子電解質膜を挟んで、白金を担持させたアノードとカソードとを配設して、電極／固体電解質膜／電極の構造とし、内側に流路を形成した一対の集電体にて上記構造体の両側を挟み、上記集電体の二つの流路にそれぞれ燃料及び酸素を供給して発電するようにした燃料電池が開発されている。更に、このような燃料電池の単位セルを積層したり、又は平面的に接続して、電圧、出力を向上させ、これをシステムに組み込むことについても研究されている。   In recent years, an anode / cathode carrying platinum is disposed across a solid polymer electrolyte membrane to form an electrode / solid electrolyte membrane / electrode structure. Thus, a fuel cell has been developed in which both sides of the structure are sandwiched to generate power by supplying fuel and oxygen to the two flow paths of the current collector, respectively. Furthermore, research is also being conducted on stacking unit cells of such fuel cells or connecting them in a planar manner to improve the voltage and output and to incorporate them into the system.

このような燃料電池は、クリーンで且つ高効率であり、更に、従来の二次電池のように長時間の充電が不要であって、燃料を供給し続ければ、実質的に連続して用いることができる。かかる特徴から、種々の用途、特に、電気自動車用電源、家庭用分散型電源、携帯機器用電源等として注目されている。   Such a fuel cell is clean and highly efficient. Further, unlike a conventional secondary battery, it does not require charging for a long time and can be used substantially continuously if fuel is continuously supplied. Can do. Because of such characteristics, it has been attracting attention for various uses, particularly as a power source for electric vehicles, a distributed power source for home use, a power source for portable devices, and the like.

一方、アノードに供給する燃料としては、代表的なものとして、純水素や、改質触媒を用いてアルコール類や炭化水素類等の燃料から生成させた水素（以後、改質水素ということがある）等の気体燃料、メタノール、ジメチルエーテル、エチレングリコール、多価アルコール等と水との混合液体燃料等が検討されている。しかし、課題も残されており、一般に、液体燃料を用いる燃料電池は出力が低く、一方、気体燃料を用いる燃料電池は、貯蔵、運搬の点で体積エネルギー密度が低い。   On the other hand, as a typical fuel to be supplied to the anode, pure hydrogen or hydrogen generated from a fuel such as alcohols or hydrocarbons using a reforming catalyst (hereinafter referred to as reformed hydrogen may be used). Gas fuels such as methanol, dimethyl ether, ethylene glycol, polyhydric alcohols, etc., and mixed liquid fuels are being studied. However, problems still remain, and in general, a fuel cell using liquid fuel has a low output, while a fuel cell using gaseous fuel has a low volumetric energy density in terms of storage and transportation.

そこで、燃料電池本体だけでなく、改質器もシステムに搭載して、液体燃料から改質水素を発生させながら、同時に発電する方法が提案されている。しかし、改質水素には、改質反応によって発生する一酸化炭素が残留しており、これが白金触媒を被毒して、燃料電池の出力を低下させるという問題がある。このため、一酸化炭素を除去する装置を改質器に付加する方策もあるが、このような方策によれば、システム全体が大型化するので、スペースの限られた携帯機器用途や車載用途では問題となる。かくして、被毒の影響がなくなるレベルまで、一酸化炭素の含量を減らすことができないのが現状である。   In view of this, a method has been proposed in which not only the fuel cell body but also a reformer is mounted in the system to generate reformed hydrogen from liquid fuel and simultaneously generate power. However, carbon monoxide generated by the reforming reaction remains in the reformed hydrogen, which has a problem that the platinum catalyst is poisoned to reduce the output of the fuel cell. For this reason, there is a measure to add a device for removing carbon monoxide to the reformer. However, according to such a measure, the entire system is enlarged, so that it is not suitable for portable equipment or in-vehicle use where space is limited. It becomes a problem. Thus, the current situation is that the carbon monoxide content cannot be reduced to a level at which the influence of poisoning is eliminated.

一方、別の方法として、白金よりも被毒を受け難い電極触媒として、白金とルテニウムの合金に代表される種々の白金合金触媒が提案されている（例えば、特許文献１〜２参照）。これらの触媒を使用する場合、カーボンペーパー等の導電性多孔質基材に、触媒を担持させたカーボン粒子とバインダー樹脂を含む液体を塗布して乾燥させ、導電性多孔質基材の構成繊維表面に触媒層が形成された電極としている。   On the other hand, as another method, various platinum alloy catalysts represented by alloys of platinum and ruthenium have been proposed as electrode catalysts that are less susceptible to poisoning than platinum (see, for example, Patent Documents 1 and 2). When these catalysts are used, a liquid containing carbon particles carrying a catalyst and a binder resin is applied to a conductive porous substrate such as carbon paper and dried to form the surface of the fiber constituting the conductive porous substrate. The electrode is provided with a catalyst layer.

しかしながら、導電性多孔質基材に上記の如き触媒層を形成してアノード電極を作製すると、触媒層の水分濃度が低下するため、一酸化炭素による被毒の抑制効果が十分得られないことが判明した。
特開平７−８５８７４号公報 特開２００２−３５８９７１号公報 However, when an anode electrode is produced by forming a catalyst layer as described above on a conductive porous substrate, the moisture concentration of the catalyst layer is lowered, so that the effect of suppressing poisoning by carbon monoxide may not be sufficiently obtained. found.
JP-A-7-85874 JP 2002-358971 A

そこで、本発明の目的は、上述した問題を解決するべく、改質水素に含まれる一酸化炭素による電極触媒の被毒を抑制して、高い出力を発現することができる燃料電池用アノード電極および膜電極接合体、並びにそれを用いた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-described problems, and to suppress poisoning of the electrode catalyst by carbon monoxide contained in the reformed hydrogen and to produce a high output, and an anode for a fuel cell. It is an object of the present invention to provide a membrane electrode assembly and a polymer electrolyte fuel cell using the same.

本発明者らは、上記目的を達成すべく、アノード電極の触媒層の水分濃度を制御することについて鋭意研究したところ、フッ素系ポリマー微粒子及び導電性炭素微粒子を含む混合物が結着した一定範囲の厚みの導電性多孔質撥水層を、導電性多孔質基材と触媒層との間に介在させることで、一酸化炭素による電極触媒の被毒を効果的に抑制できることを見出し、本発明を完成するに至った。   In order to achieve the above-mentioned object, the present inventors diligently studied to control the moisture concentration of the catalyst layer of the anode electrode. As a result, a certain range of the mixture containing the fluorine-based polymer fine particles and the conductive carbon fine particles was bound. It has been found that by interposing a conductive porous water repellent layer having a thickness between the conductive porous substrate and the catalyst layer, poisoning of the electrode catalyst by carbon monoxide can be effectively suppressed. It came to be completed.

即ち、本発明の燃料電池用アノード電極は、導電性多孔質基材と、その導電性多孔質基材の表面に又は一部が内部に含浸するように設けられ、フッ素系ポリマー微粒子及び導電性炭素微粒子を含む混合物が結着した厚み３０〜５００μｍの導電性多孔質撥水層と、その導電性多孔質撥水層の側に設けられ、白金−ルテニウムを含む合金を含有する触媒粒子及びプロトン伝導性ポリマーを含有する触媒層とを備えたことを特徴とする。   That is, the anode electrode for a fuel cell according to the present invention is provided with a conductive porous substrate, and the surface of the conductive porous substrate or a part thereof so as to be impregnated therein. A conductive porous water-repellent layer having a thickness of 30 to 500 μm to which a mixture containing carbon fine particles is bound, and catalyst particles and protons provided on the side of the conductive porous water-repellent layer and containing an alloy containing platinum-ruthenium And a catalyst layer containing a conductive polymer.

本発明の燃料電池用アノード電極によると、フッ素系ポリマー微粒子及び導電性炭素微粒子を含む混合物が結着した厚み３０〜５００μｍの導電性多孔質撥水層を、導電性多孔質基材と触媒層との間に介在させるため、導電性多孔質基材から触媒層への燃料ガスの拡散性を維持しながら、触媒層における水分濃度を従来より高く維持することができる。このため、実施例の結果が示すように、改質水素に含まれる一酸化炭素による電極触媒の被毒を抑制して、高い出力を発現することができる。   According to the anode electrode for a fuel cell of the present invention, a conductive porous water-repellent layer having a thickness of 30 to 500 μm, in which a mixture containing fluoropolymer fine particles and conductive carbon fine particles is bound, a conductive porous substrate and a catalyst layer Therefore, the moisture concentration in the catalyst layer can be maintained higher than before while maintaining the diffusibility of the fuel gas from the conductive porous substrate to the catalyst layer. For this reason, as shown in the results of the examples, it is possible to suppress the poisoning of the electrode catalyst by carbon monoxide contained in the reformed hydrogen and to express a high output.

上記において、前記フッ素系ポリマー微粒子の光散乱法で測定される平均粒子径が、１０〜５００ｎｍであることが好ましい。このような粒子径のフッ素系ポリマー微粒子を用いることによって、導電性多孔質撥水層のガス拡散性を良好に維持しながら、撥水機能によって触媒層の水分濃度を好適に制御することができる。   In the above, it is preferable that the average particle diameter measured by the light-scattering method of the said fluoropolymer fine particle is 10-500 nm. By using the fluorine-based polymer fine particles having such a particle size, the water concentration of the catalyst layer can be suitably controlled by the water repellent function while maintaining good gas diffusibility of the conductive porous water repellent layer. .

一方、本発明の膜電極接合体は、上記の燃料電池用アノード電極と、プロトン伝導性を有する固体高分子電解質膜と、白金を含有する触媒粒子及びプロトン伝導性ポリマーを含有する触媒層を導電性多孔質基材に担持させてなるカソード電極とを積層一体化したものである。   On the other hand, the membrane electrode assembly of the present invention conducts the fuel cell anode electrode, the proton conductive solid polymer electrolyte membrane, the catalyst particles containing platinum and the catalyst layer containing the proton conductive polymer. And a cathode electrode formed on a porous porous substrate.

また、本発明の固体高分子型燃料電池は、上記の膜電極接合体を用いて、前記アノード電極に水素を含むガスを接触させ、前記カソード電極に酸素を含むガスを接触させるように構成したものである。   Further, the polymer electrolyte fuel cell of the present invention is configured such that a gas containing hydrogen is brought into contact with the anode electrode and a gas containing oxygen is brought into contact with the cathode electrode, using the membrane electrode assembly. Is.

従って、何れも本発明の燃料電池用アノード電極を用いるため、改質水素に含まれる一酸化炭素による電極触媒の被毒を抑制して、高い出力を発現することができる燃料電池が実現できる。   Therefore, since both use the anode electrode for fuel cells of the present invention, it is possible to realize a fuel cell capable of suppressing the poisoning of the electrode catalyst by carbon monoxide contained in the reformed hydrogen and exhibiting high output.

本発明の燃料電池用アノード電極は、導電性多孔質基材と、その導電性多孔質基材の表面に又は一部が内部に含浸するように設けられ、フッ素系ポリマー微粒子及び導電性炭素微粒子を含む混合物が結着した厚み３０〜５００μｍの導電性多孔質撥水層と、その導電性多孔質撥水層の側に設けられ、白金−ルテニウムを含む合金を含有する触媒粒子及びプロトン伝導性ポリマーを含有する触媒層とを備えたものである。また、本発明の膜電極接合体は、このようなアノード電極と、プロトン伝導性を有する固体高分子電解質膜と、白金を含有する触媒粒子及びプロトン伝導性ポリマーを含有する触媒層を導電性多孔質基材に担持させてなるカソード電極とを積層一体化したものである。   The anode electrode for a fuel cell according to the present invention is provided with a conductive porous substrate, and the surface of the conductive porous substrate or a part thereof so as to be impregnated therein. A conductive porous water-repellent layer having a thickness of 30 to 500 μm, to which a mixture containing a catalyst is bound, catalyst particles containing an alloy containing platinum-ruthenium provided on the side of the conductive porous water-repellent layer, and proton conductivity And a catalyst layer containing a polymer. Further, the membrane electrode assembly of the present invention comprises such an anode electrode, a solid polymer electrolyte membrane having proton conductivity, a catalyst particle containing platinum and a catalyst layer containing a proton conductive polymer. A cathode electrode supported on a porous substrate is laminated and integrated.

導電性多孔質基材としては、カーボンペーパー、カーボン繊維不織布などの繊維質カーボン、導電性高分子繊維の集合体などの電導性多孔質材が使用できる。   As the conductive porous base material, conductive carbon such as carbon paper, fibrous carbon such as carbon fiber nonwoven fabric, and conductive polymer fiber aggregates can be used.

導電性多孔質撥水層は、導電性多孔質基材の表面に又は一部が内部に含浸するように設けられる。その厚み（一部が含浸する場合は総厚み）は、３０〜５００μｍであり、好ましくは、１００〜３００μｍである。導電性多孔質撥水層の厚みが３０μｍ未満であれば、撥水機能による水分濃度の向上による被毒抑制効果が得られない。また５００μｍを超えると、燃料ガスの拡散に支障をきたすため出力が低下し、高出力が得られない。   The conductive porous water-repellent layer is provided so that the surface of the conductive porous substrate is partially impregnated therein. Its thickness (when partly impregnated, the total thickness) is 30 to 500 μm, preferably 100 to 300 μm. If the thickness of the conductive porous water repellent layer is less than 30 μm, the poisoning suppression effect due to the improvement of the water concentration by the water repellent function cannot be obtained. On the other hand, if it exceeds 500 μm, the fuel gas diffusion will be hindered, so the output will be reduced and a high output cannot be obtained.

用いられるフッ素系ポリマー微粒子としてはポリテトラフルオロエチレン、パーフルオロアルコキシアルカン、ポリフッ化ビニル、ポリフッ化ビニリデン、パーフルオロエチレンプロペンコポリマー、ポリクロロトリフルオロエチレン、エチレン−クロロトリフルオロエチレンコポリマー、エチレン−テトラフルオロエチレンコポリマー、およびテトラフルオロエチレン−パーフルオロジイソキソールコポリマー等から選ばれる少なくとも一種類以上の粒子が好適に使用できる。   Fluoropolymer fine particles used include polytetrafluoroethylene, perfluoroalkoxyalkane, polyvinyl fluoride, polyvinylidene fluoride, perfluoroethylene propene copolymer, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer, ethylene-tetrafluoro. At least one kind of particles selected from an ethylene copolymer, a tetrafluoroethylene-perfluorodiisoxol copolymer, and the like can be suitably used.

フッ素系ポリマー微粒子の光散乱法で測定される平均粒子径は、１０〜５００ｎｍが好ましく、２０〜３００ｎｍがより好ましい。フッ素系ポリマー微粒子の平均粒子径が１０ｎｍ未満であると、分散液の分散性が悪くなり、塗布物の表面平滑性が悪化する傾向があり、５００ｎｍを超えても分散液の分散性が悪くなり、塗布物の表面平滑性が悪化する傾向がある。   10-500 nm is preferable and, as for the average particle diameter measured by the light-scattering method of a fluorine-type polymer microparticle, 20-300 nm is more preferable. If the average particle size of the fluorine-based polymer fine particles is less than 10 nm, the dispersibility of the dispersion tends to deteriorate, and the surface smoothness of the coated product tends to deteriorate, and even if it exceeds 500 nm, the dispersibility of the dispersion deteriorates. The surface smoothness of the coated product tends to deteriorate.

導電性多孔質撥水層に含有される導電性炭素微粒子としては、各種製法で得られるカーボンブラック粉末が何れも使用でき、なかでも一次平均粒子径が１０〜５００ｎｍであることが好ましい。   As the conductive carbon fine particles contained in the conductive porous water-repellent layer, any carbon black powder obtained by various production methods can be used, and the primary average particle diameter is preferably 10 to 500 nm.

フッ素系ポリマー微粒子／導電性炭素微粒子の重量比は、導電性多孔質撥水層の導電性と撥水性のバランスを良好にする観点から、９／１〜１／９が好ましい。   The weight ratio of fluoropolymer fine particles / conductive carbon fine particles is preferably 9/1 to 1/9 from the viewpoint of improving the balance between the conductivity and water repellency of the conductive porous water-repellent layer.

導電性多孔質撥水層はカーボンペーパー等の導電性多孔質基材上に塗布されるが、係る基材は多孔質であるため導電性多孔質撥水層のディスパージョンが内部まで含浸する場合がある。この場合は含浸した基材部分の厚みも含め３０μｍ乃至５００μｍである事が必要である。   The conductive porous water-repellent layer is coated on a conductive porous substrate such as carbon paper, but the substrate is porous so that the dispersion of the conductive porous water-repellent layer is impregnated to the inside. There is. In this case, it is necessary that the thickness is 30 μm to 500 μm including the thickness of the impregnated base material portion.

また、触媒層は、導電性多孔質撥水層の存在する側に設けられ、白金−ルテニウムを含む合金を含有する触媒粒子及びプロトン伝導性ポリマーを含有するものである。白金／ルテニウム重量比は、電極触媒の被毒を効果的に抑制する観点から、１／４〜４／１が好ましい。   The catalyst layer is provided on the side where the conductive porous water repellent layer is present, and contains catalyst particles containing an alloy containing platinum-ruthenium and a proton conductive polymer. The platinum / ruthenium weight ratio is preferably 1/4 to 4/1 from the viewpoint of effectively suppressing the poisoning of the electrode catalyst.

触媒粒子としては、例えば、貴金属微粒子を担持させたカーボンブラック粉末あるいは金属微粒子単独からなるメタルブラック等の触媒粒子が使用される。プロトン伝導性ポリマーは、電気化学反応によって発生するプロトンの伝導体となる。   As the catalyst particles, for example, catalyst particles such as carbon black powder supporting noble metal fine particles or metal black made of metal fine particles alone are used. The proton conductive polymer becomes a conductor of protons generated by an electrochemical reaction.

また、触媒層には必要に応じて、導電助剤としてのカーボンブラック粉末、これらを結着させる結着剤を含有してもよい。触媒層の表面には、電気化学反応によって発生するプロトンを、効率良く固体高分子電解質膜へ伝導するために、必要に応じて、プロトン伝導性ポリマーからなる層を形成することができる。   In addition, the catalyst layer may contain carbon black powder as a conductive auxiliary agent and a binder for binding them as necessary. On the surface of the catalyst layer, in order to efficiently conduct protons generated by the electrochemical reaction to the solid polymer electrolyte membrane, a layer made of a proton conductive polymer can be formed as necessary.

一方、カソード電極は、白金を含有する触媒粒子及びプロトン伝導性ポリマーを含有する触媒層を導電性多孔質基材に担持させてなるため、触媒金属の種類と導電性多孔質撥水層の有無の点のみで、アノード電極と異なる。   On the other hand, since the cathode electrode has catalyst particles containing platinum and a catalyst layer containing a proton conductive polymer supported on a conductive porous substrate, the type of catalyst metal and the presence or absence of a conductive porous water repellent layer This is different from the anode electrode only in this point.

カソード電極の触媒層に含有される白金を含む触媒粒子としては、例えば、貴金属微粒子を担持させたカーボンブラック粉末、あるいは貴金属微粒子そのものからなるメタルブラックを使う事ができる。又、触媒金属としては、白金元素を必須成分とし、これ以外に必要に応じルテニウムとの合金、さらにはこれらに加えモリブデン、タングステン、コバルト、鉄、ニッケル、銅、錫、および金から選ばれる少なくとも一種類以上の元素を加えた多元系合金などが適宜使用できる。   As catalyst particles containing platinum contained in the catalyst layer of the cathode electrode, for example, carbon black powder carrying noble metal fine particles or metal black made of noble metal fine particles themselves can be used. Further, as the catalytic metal, platinum element is an essential component, and in addition to this, an alloy with ruthenium as necessary, and in addition to these, at least selected from molybdenum, tungsten, cobalt, iron, nickel, copper, tin, and gold A multi-element alloy to which one or more elements are added can be used as appropriate.

従って、カソードは、例えば、次のようにして製造される。即ち、白金微粒子を担持させた導電性カーボンブラック粉末と導電助剤としてのカーボンブラックを適宜の結着剤（例えば、ポリフッ化ビニリデン樹脂のＮ−メチル−２−ピロリドン溶液やデュポン社製のナフィオン（登録商標）のようなパーフルオロスルホン酸樹脂溶液）を用いてペーストとし、これを導電性多孔質基材（例えば、東レ（株）製カーボンペーパー）上に塗布し、加熱、乾燥させた後、更に、その上にプロトン伝導性イオン交換電解質ポリマー（例えば、デュポン社製のナフィオン）の溶液を塗布し、加熱、乾燥させることによって、カソードを得ることができる。しかし、本発明において、カソードの製造方法は、特に限定されるものではない。   Therefore, a cathode is manufactured as follows, for example. That is, conductive carbon black powder supporting platinum fine particles and carbon black as a conductive auxiliary agent are combined with an appropriate binder (for example, N-methyl-2-pyrrolidone solution of polyvinylidene fluoride resin or Nafion (manufactured by DuPont) (Registered trademark) using a perfluorosulfonic acid resin solution) as a paste, applying this onto a conductive porous substrate (for example, carbon paper manufactured by Toray Industries, Inc.), heating and drying, Furthermore, a cathode can be obtained by applying a solution of a proton conductive ion exchange electrolyte polymer (for example, Nafion manufactured by DuPont) thereon and heating and drying. However, in the present invention, the method for producing the cathode is not particularly limited.

アノードも同様に次のようにして製造される。即ち、導電性カーボンブラック粉末とフッ素系ポリマーとのディスパージョンを導電性多孔質基材（例えば、東レ（株）製カーボンペーパー）上に塗布し、加熱乾燥後、さらに高温焼成して導電性多孔質撥水層とし、次いで白金とルテニウム合金の微粒子を担持させた導電性カーボンブラック粉末と導電助剤としてのカーボンブラックを上述したような適宜の結着剤を用いてペーストとし、これをさらに塗布し、加熱、乾燥させたものに、さらにその上にプロトン伝導性イオン交換電解質ポリマー（例えば、デュポン社製のナフィオン）の溶液を塗布し、加熱、乾燥させることによって、アノードを得ることができる。導電性多孔質撥水層は所定の厚みとなるまで塗布乾燥を繰り返して後、高温焼成する事もできる。以上は本発明におけるアノードの製造方法の一例であり、特に限定されるものではない。   Similarly, the anode is manufactured as follows. That is, a dispersion of conductive carbon black powder and a fluorine-based polymer is applied on a conductive porous substrate (for example, carbon paper manufactured by Toray Industries, Inc.), dried by heating, and further baked at a high temperature to be conductive porous. Then, the conductive carbon black powder carrying fine particles of platinum and ruthenium alloy and the carbon black as the conductive auxiliary agent are made into a paste using the appropriate binder as described above, and further coated. The anode can be obtained by applying a solution of a proton conductive ion exchange electrolyte polymer (for example, Nafion manufactured by DuPont) to the heated and dried product, followed by heating and drying. The conductive porous water repellent layer can be fired at a high temperature after repeated coating and drying until a predetermined thickness is reached. The above is an example of the anode manufacturing method in the present invention, and is not particularly limited.

本発明においては、プロトン伝導性を有する固体高分子電解質膜としては、従来の固体高分子膜型電池に用いられているようなパーフルオロスルホン酸樹脂からなる陽イオン交換膜、例えば、ナフィオン（登録商標）が好適に用いられるが、しかし、これに限定されるものではない。   In the present invention, as the polymer electrolyte membrane having proton conductivity, a cation exchange membrane made of perfluorosulfonic acid resin as used in a conventional polymer electrolyte membrane battery, for example, Nafion (registered) (Trademark) is preferably used, but is not limited thereto.

従って、例えば、ポリテトラフルオロエチレン等のフッ素樹脂からなる多孔質膜に上記ナフィオンや他のイオン伝導性物質を含浸させたものや、ポリエチレンやポリプロピレン等のポリオレフィン樹脂からなる多孔質膜や不織布に上記ナフィオンや他のイオン伝導性物質を担持させたものでもよい。   Therefore, for example, a porous membrane made of a fluororesin such as polytetrafluoroethylene impregnated with the above Nafion or other ion conductive material, or a porous membrane or nonwoven fabric made of a polyolefin resin such as polyethylene or polypropylene A material carrying Nafion or another ion conductive material may be used.

本発明の固体高分子型燃料電池は、以上のような膜電極接合体を用いて、前記アノード電極に水素を含むガスを接触させ、前記カソード電極に酸素を含むガスを接触させるように構成したものである。   The polymer electrolyte fuel cell according to the present invention is configured such that a gas containing hydrogen is brought into contact with the anode electrode and a gas containing oxygen is brought into contact with the cathode electrode, using the membrane electrode assembly as described above. Is.

本発明による燃料電池においては、カソードに酸素が気体で供給され、アノードに一酸化炭素を含む水素が気体で供給される。上記酸素は、空気であってもよい。また、一酸化炭素を含む水素としては、例えば、改質触媒を用いてアルコール類や炭化水素類等の燃料から生成させた改質水素が好ましく用いられる。特に、本発明による燃料電池においては、一酸化炭素を１０〜５０００ｐｐｍの範囲で含む改質水素を燃料としても、アノードの電極触媒の被毒をよく抑制して、長期間にわたって、高い出力を得ることができる。   In the fuel cell according to the present invention, oxygen is supplied as a gas to the cathode, and hydrogen containing carbon monoxide is supplied as a gas to the anode. The oxygen may be air. Moreover, as hydrogen containing carbon monoxide, for example, reformed hydrogen generated from fuel such as alcohols and hydrocarbons using a reforming catalyst is preferably used. In particular, in the fuel cell according to the present invention, even when the reformed hydrogen containing carbon monoxide in the range of 10 to 5000 ppm is used as the fuel, poisoning of the anode electrode catalyst is well suppressed and high output is obtained over a long period of time. be able to.

改質水素を製造する方法は、既によく知られており、例えば、メタノールの改質であれば、改質触媒を用いてメタノールを水蒸気改質すると共に、一酸化炭素改質を行って、水素と二酸化炭素を得ることができる。このようなメタノールの改質による改質水素は、尚、多くの一酸化炭素を含むので、一酸化炭素を選択的に二酸化炭素に接触酸化すれば、一酸化炭素を数百ｐｐｍまで低減することができる。しかし、本発明において、燃料として用いる一酸化炭素を含む水素の由来は、特に限定されるものではない。   A method for producing reformed hydrogen is already well known. For example, in the case of reforming of methanol, methanol is steam reformed using a reforming catalyst and carbon monoxide reforming is performed. And get carbon dioxide. Such reformed hydrogen produced by reforming methanol still contains a large amount of carbon monoxide, so that carbon monoxide can be reduced to several hundred ppm by selectively oxidizing carbon monoxide to carbon dioxide. Can do. However, in the present invention, the origin of hydrogen containing carbon monoxide used as fuel is not particularly limited.

電極にガスを接触させるための構造としては、集電機能を有するセパレータの両側にガスの流路を形成したものを、膜電極接合体に積層する構造や、膜電極接合体の電極の両側に、集電機能を有しガスの流路を形成した集電板（例えばエッチングやプレス加工で流路を形成した金属板）を設けた構造などが例示できる。   As a structure for bringing the gas into contact with the electrode, a structure in which a gas flow path is formed on both sides of a separator having a current collecting function is laminated on the membrane electrode assembly, or on both sides of the electrode of the membrane electrode assembly. A structure provided with a current collecting plate having a current collecting function and having a gas flow path (for example, a metal plate having a flow path formed by etching or pressing) can be exemplified.

また、本発明による燃料電池の作動温度は、通常、０℃以上であり、１５〜１２０℃の範囲が好ましく、特に、３０〜１００℃の範囲が好ましい。作動温度が高すぎるときは用いる材料の劣化や剥離等が起こるおそれがある。   Moreover, the operating temperature of the fuel cell according to the present invention is usually 0 ° C. or higher, preferably in the range of 15 to 120 ° C., particularly preferably in the range of 30 to 100 ° C. When the operating temperature is too high, the material used may be deteriorated or peeled off.

以下、本発明の構成と効果を具体的に示す実施例等について説明する。   Examples and the like specifically showing the configuration and effects of the present invention will be described below.

実施例１
白金を２０重量％担持させた導電性カーボンブラック粉末１８０ｍｇ、導電性カーボンブラック３６ｍｇ、ポリフッ化ビニリデン２４ｍｇ及びＮ−メチル−２−ピロリドン９４０ｍｇを乳鉢にて混合して、ペーストとした。このペーストの一部を２．３ｃｍ角のカーボンペーパーの片面上に塗布し、８０℃で６０分間加熱して、乾燥させた。この白金担持カーボンペーパーにおいて、固形分担持量は２０ｍｇであり、そのうち、白金の担持量は３ｍｇであった。次いで、この白金担持カーボンペーパーの白金担持表面の上にプロトン伝導性イオン交換電解質ポリマーであるナフィオン（登録商標）の５重量％アルコール系溶液（アルドリッチ社製）を塗布し、８０℃で３０分間、加熱し、乾燥させて、カソードとした。 Example 1
180 mg of conductive carbon black powder carrying 20% by weight of platinum, 36 mg of conductive carbon black, 24 mg of polyvinylidene fluoride and 940 mg of N-methyl-2-pyrrolidone were mixed in a mortar to obtain a paste. A part of this paste was applied on one side of a 2.3 cm square carbon paper, heated at 80 ° C. for 60 minutes, and dried. In this platinum-supported carbon paper, the solid content was 20 mg, of which the platinum content was 3 mg. Next, a 5% by weight alcohol-based solution (manufactured by Aldrich) of Nafion (registered trademark), which is a proton-conductive ion exchange electrolyte polymer, is applied onto the platinum-supporting surface of the platinum-supporting carbon paper, and 30 minutes at 80 ° C. Heated and dried to form the cathode.

アノードは次に示す方法により作成した。PTFE（ポリテトラフルオロエチレン）粒子（光散乱法測定による平均粒子径 ０．２５μｍ）４ｇ、導電性カーボンブラック（平均一次粒子径４０ｎｍ）４ｇ、界面活性剤０．２ｇ、水３０ｇ、およびプロピルアルコール４０ｇをボールミルにて攪拌混合しディスパージョンとした。このディスパージョンをカーボンペーパー上に塗布し８０℃で３０分乾燥した。更に塗布、乾燥工程を６回繰り返した後、４００℃で１０分間、空気中で焼成した。SEMにて断面観察の結果、基材上の撥水層厚みは５０μｍで基材中には３５０μｍ含浸していた。   The anode was prepared by the following method. 4 g of PTFE (polytetrafluoroethylene) particles (average particle size 0.25 μm by light scattering measurement), 4 g of conductive carbon black (average primary particle size 40 nm), 0.2 g of surfactant, 30 g of water, and 40 g of propyl alcohol Was stirred and mixed in a ball mill to form a dispersion. This dispersion was applied onto carbon paper and dried at 80 ° C. for 30 minutes. Further, the coating and drying steps were repeated 6 times, followed by baking in air at 400 ° C. for 10 minutes. As a result of cross-sectional observation by SEM, the thickness of the water-repellent layer on the substrate was 50 μm, and the substrate was impregnated with 350 μm.

塗工面上に更にアノード触媒層を次の方法で設けた。白金−ルテニウム合金（白金／ルテニウム重量比２／１）を３０重量％担持させた導電性カーボンブラック粉末１２０ｍｇ、導電性カーボンブラック９６ｍｇ、ポリフッ化ビニリデン２４ｍｇ及びＮ−メチル−２−ピロリドン９４０ｍｇを乳鉢にて混合して、ペーストとした。このペーストの一部を先の撥水層塗布基材の２．３ｃｍ角上に塗布し、８０℃で６０分間加熱乾燥した。固形分の担持量は１０ｍｇであり、そのうち、白金−ルテニウム合金の担持量は１．５ｍｇであった。次いで、この白金−ルテニウム合金担持カーボンペーパーの触媒担持表面の上にプロトン伝導性イオン交換電解質ポリマーであるナフィオン（登録商標）の５重量％アルコール系溶液（アルドリッチ社製）を塗布し、８０℃で３０分間、加熱乾燥させて、アノードとした。   An anode catalyst layer was further provided on the coated surface by the following method. In a mortar, 120 mg of conductive carbon black powder, 96 mg of conductive carbon black, 24 mg of polyvinylidene fluoride and 940 mg of N-methyl-2-pyrrolidone supporting 30 wt% of a platinum-ruthenium alloy (platinum / ruthenium weight ratio 2/1) To make a paste. A part of this paste was applied onto a 2.3 cm square of the water repellent layer-coated substrate and dried by heating at 80 ° C. for 60 minutes. The supported amount of solid content was 10 mg, of which the supported amount of platinum-ruthenium alloy was 1.5 mg. Next, a 5 wt% alcohol-based solution (manufactured by Aldrich) of Nafion (registered trademark), which is a proton conductive ion exchange electrolyte polymer, is applied onto the catalyst supporting surface of the platinum-ruthenium alloy supporting carbon paper at 80 ° C. It was heat-dried for 30 minutes to obtain an anode.

このようにして得られたカソードとアノードとの間にプロトン伝導性イオン交換電解質膜として酸型ナフィオン膜（デュポン社製ナフィオン１１２）を置き、金型を用いて、窒素雰囲気中、温度１３５℃の条件下、ホットプレスにて加熱加圧して、電極−プロトン交換膜接合体を得、これを用いて試験用の単層の燃料電池セルを組み立てた。   An acid type Nafion membrane (Nafion 112 manufactured by DuPont) was placed between the cathode and the anode thus obtained as a proton-conductive ion exchange electrolyte membrane, and the temperature was 135 ° C. in a nitrogen atmosphere using a mold. Under the conditions, heating and pressurization were performed with a hot press to obtain an electrode-proton exchange membrane assembly, and a single-layer fuel cell for testing was assembled using this.

この燃料電池セルを燃料電池評価装置（東陽テクニカ（株）製）に組み込み、セル温度３０℃とし、加湿器温度３０℃で酸素ガスを５００ｍＬ／分の割合でカソードに供給すると共に、加湿器温度３０℃で水素／二酸化炭素混合ガス（水素／二酸化炭素モル比７５／２５、一酸化炭素を２００ｐｐｍ含む。）を５００ｍＬ／分の割合でアノードに供給した。供給ガス圧力は常圧とした。この条件下で測定した電流電圧特性（Ｉ−Ｖ特性）から算出した出力密度は、電圧０．６Ｖで４０ｍＷ／ｃｍ２であった。 This fuel cell is incorporated into a fuel cell evaluation apparatus (manufactured by Toyo Technica Co., Ltd.), and the cell temperature is set to 30 ° C. The oxygen gas is supplied to the cathode at a humidifier temperature of 30 ° C. at a rate of 500 mL / min. A hydrogen / carbon dioxide mixed gas (hydrogen / carbon dioxide molar ratio 75/25, containing 200 ppm of carbon monoxide) was supplied to the anode at a rate of 500 mL / min at 30 ° C. The supply gas pressure was normal pressure. The output density calculated from the current-voltage characteristics (IV characteristics) measured under these conditions was 40 mW / cm 2 at a voltage of 0.6V.

実施例２
実施例１において、撥水層を塗布した基材を次に示す方法により作成する以外は実施例１と同様にして燃料電池セルの組み立て及び性能評価を行った。その結果、出力密度４２ｍＷ／ｃｍ２を得た。ＰＴＦＥ（ポリテトラフルオロエチレン）粒子（光散乱法測定による平均粒子径０．２５μｍ）４ｇ、導電性カーボンブラックであるバルカンＸＣ７２Ｒ（キャボットスペシャルティーケミカルズ社製）４ｇ、界面活性剤０．２ｇ、水２０ｇ、およびプロピルアルコール３０ｇをボールミルにて攪拌混合しディスパージョンとした。このディスパージョンをカーボンペーパー上に塗布し８０℃で３０分乾燥後、４００℃で１０分間、空気中で焼成した。ＳＥＭにて断面観察の結果、基材上の撥水層厚みは２０μｍで基材中には１０μｍ含浸していた。 Example 2
In Example 1, the assembly and performance evaluation of the fuel cell were performed in the same manner as in Example 1 except that the substrate coated with the water repellent layer was prepared by the following method. As a result, an output density of 42 mW / cm 2 was obtained. 4 g of PTFE (polytetrafluoroethylene) particles (average particle diameter of 0.25 μm as measured by light scattering method), 4 g of Vulcan XC72R (manufactured by Cabot Specialty Chemicals) as conductive carbon black, 0.2 g of surfactant, 20 g of water And 30 g of propyl alcohol were stirred and mixed in a ball mill to form a dispersion. This dispersion was applied onto carbon paper, dried at 80 ° C. for 30 minutes, and then fired at 400 ° C. for 10 minutes in air. As a result of cross-sectional observation by SEM, the thickness of the water-repellent layer on the substrate was 20 μm, and the substrate was impregnated with 10 μm.

実施例３
実施例１において、撥水層を塗布した基材を次に示す方法により作成する以外は実施例１と同様にして燃料電池セルの組み立て及び性能評価を行った。その結果、出力密度、５０ｍＷ／ｃｍ２を得た。ＦＥＰ（パーフルオロエチレンプロペンコポリマー）粒子（光散乱法測定による平均粒子径０．２０μｍ）４ｇ、導電性カーボンブラックであるバルカンＸＣ７２Ｒ（キャボットスペシャルティーケミカルズ社製）４ｇ、界面活性剤０．２ｇ、水２５ｇ、およびプロピルアルコール３５ｇをボールミルにて攪拌混合しディスパージョンとした。このディスパージョンをカーボンベーハー上に塗布し８０℃で３０分乾燥した。更に塗布、乾燥工程を２回繰り返した後、３３０℃で１０分間、空気中で焼成した。ＳＥＭにて断面観察の結果、基材上の撥水層厚みは１５０μｍで基材中には１５０μｍ含浸していた。 Example 3
In Example 1, the assembly and performance evaluation of the fuel cell were performed in the same manner as in Example 1 except that the substrate coated with the water repellent layer was prepared by the following method. As a result, a power density of 50 mW / cm 2 was obtained. 4 g of FEP (perfluoroethylene propene copolymer) particles (average particle diameter 0.20 μm as measured by light scattering method), 4 g of Vulcan XC72R (manufactured by Cabot Specialty Chemicals) which is conductive carbon black, 0.2 g of surfactant, water 25 g and propyl alcohol 35 g were stirred and mixed in a ball mill to form a dispersion. This dispersion was applied on a carbon wafer and dried at 80 ° C. for 30 minutes. Further, the coating and drying steps were repeated twice, followed by baking in air at 330 ° C. for 10 minutes. As a result of cross-sectional observation by SEM, the thickness of the water-repellent layer on the substrate was 150 μm, and the substrate was impregnated with 150 μm.

比較例１
導電性多孔質撥水層を設けない事以外は実施例１と同様にして燃料電池セルの組み立て及び性能評価を行った。その結果、出力密度は０．６Ｖで１０ｍＷ／ｃｍ２であった。 Comparative Example 1
The fuel cell assembly and performance evaluation were performed in the same manner as in Example 1 except that the conductive porous water-repellent layer was not provided. As a result, the output density was 10 mW / cm 2 at 0.6V.

比較例２
撥水層厚みを基材上に１０μｍ、基材中には１０μｍとする以外は実施例１と同様にして燃料電池セルの組み立て及び性能評価を行った。その結果、出力密度は０．６Ｖで１５ｍＷ／ｃｍ２であった。 Comparative Example 2
The fuel cell assembly and performance evaluation were performed in the same manner as in Example 1 except that the water-repellent layer thickness was 10 μm on the substrate and 10 μm in the substrate. As a result, the output density was 15 mW / cm 2 at 0.6V.

比較例３
撥水層厚みを基材上に２５０μｍ、基材中には３５０μｍとする以外は実施例１と同様にして燃料電池セルの組み立て及び性能評価を行った。その結果、出力密度は０．６Ｖで１７ｍＷ／ｃｍ２であった。 Comparative Example 3
The fuel cell assembly and performance evaluation were performed in the same manner as in Example 1 except that the water-repellent layer thickness was 250 μm on the substrate and 350 μm in the substrate. As a result, the output density was 17 mW / cm 2 at 0.6V.

Claims (4)

導電性多孔質基材と、その導電性多孔質基材の表面に又は一部が内部に含浸するように設けられ、フッ素系ポリマー微粒子及び導電性炭素微粒子を含む混合物が結着した厚み３０〜５００μｍの導電性多孔質撥水層と、その導電性多孔質撥水層の側に設けられ、白金−ルテニウムを含む合金を含有する触媒粒子及びプロトン伝導性ポリマーを含有する触媒層とを備えた燃料電池用アノード電極。   Conductive porous substrate and a thickness of 30 to 30 which is provided so that the surface of the conductive porous substrate or a part of the porous substrate is impregnated therein, and a mixture containing fluorine-based polymer fine particles and conductive carbon fine particles is bound. 500 μm conductive porous water repellent layer, provided on the side of the conductive porous water repellent layer, catalyst particles containing an alloy containing platinum-ruthenium and a catalyst layer containing a proton conductive polymer Anode electrode for fuel cell. 前記フッ素系ポリマー微粒子の光散乱法で測定される平均粒子径が、１０〜５００ｎｍである請求項１記載の燃料電池用アノード電極。   The anode electrode for a fuel cell according to claim 1, wherein an average particle diameter of the fluoropolymer fine particles measured by a light scattering method is 10 to 500 nm. 請求項１又は２に記載の燃料電池用アノード電極と、プロトン伝導性を有する固体高分子電解質膜と、白金を含有する触媒粒子及びプロトン伝導性ポリマーを含有する触媒層を導電性多孔質基材に担持させてなるカソード電極とを積層一体化した膜電極接合体。   A conductive porous substrate comprising the anode electrode for a fuel cell according to claim 1 or 2, a solid polymer electrolyte membrane having proton conductivity, catalyst particles containing platinum and a catalyst layer containing a proton conductive polymer A membrane electrode assembly obtained by laminating and integrating a cathode electrode carried on a substrate. 請求項３に記載の膜電極接合体を用いて、前記アノード電極に水素を含むガスを接触させ、前記カソード電極に酸素を含むガスを接触させるように構成した固体高分子型燃料電池。   4. A polymer electrolyte fuel cell comprising the membrane electrode assembly according to claim 3, wherein a gas containing hydrogen is brought into contact with the anode electrode, and a gas containing oxygen is brought into contact with the cathode electrode.
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Cited By (2)

* Cited by examiner, † Cited by third party
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WO2011065349A1 (en) * 2009-11-24 2011-06-03 三菱レイヨン株式会社 Porous electrode base material and process for production thereof
JP2013534707A (en) * 2010-07-12 2013-09-05 スリーエム イノベイティブ プロパティズ カンパニー Fuel cell electrode with conductive network

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011065349A1 (en) * 2009-11-24 2011-06-03 三菱レイヨン株式会社 Porous electrode base material and process for production thereof
JP5433588B2 (en) * 2009-11-24 2014-03-05 三菱レイヨン株式会社 Porous electrode substrate and method for producing the same
JP2013534707A (en) * 2010-07-12 2013-09-05 スリーエム イノベイティブ プロパティズ カンパニー Fuel cell electrode with conductive network
JP2016119308A (en) * 2010-07-12 2016-06-30 スリーエム イノベイティブ プロパティズ カンパニー Fuel cell electrodes with conduction networks
JP2017041454A (en) * 2010-07-12 2017-02-23 スリーエム イノベイティブ プロパティズ カンパニー Fuel cell electrode with conduction network
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