JP5130690B2 - Electrode-electrolyte membrane assembly - Google Patents

Electrode-electrolyte membrane assembly Download PDF

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JP5130690B2
JP5130690B2 JP2006269801A JP2006269801A JP5130690B2 JP 5130690 B2 JP5130690 B2 JP 5130690B2 JP 2006269801 A JP2006269801 A JP 2006269801A JP 2006269801 A JP2006269801 A JP 2006269801A JP 5130690 B2 JP5130690 B2 JP 5130690B2
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resin film
electrolyte membrane
catalyst layer
barrier resin
gas barrier
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礼 弘光
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Dai Nippon Printing Co Ltd
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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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Description

本発明は、新規な電極−電解質膜接合体及びその製造方法に関する。   The present invention relates to a novel electrode-electrolyte membrane assembly and a method for producing the same.

燃料電池の一種である固体高分子形燃料電池は、電解質膜として水素イオン伝導性高分子電解質膜を用い、その両面に触媒層、電極基材及びセパレータが順次積層された構造となっている。このうち、電解質膜の両面に触媒層及び電極基材を順次積層させたもの（即ち、電極基材／触媒層／電解質膜／触媒層／電極基材の層構成のもの）は、電極−電解質膜接合体（MEA）と称されている。   A polymer electrolyte fuel cell, which is a type of fuel cell, has a structure in which a hydrogen ion conductive polymer electrolyte membrane is used as an electrolyte membrane, and a catalyst layer, an electrode base material, and a separator are sequentially laminated on both sides. Among these, a catalyst layer and an electrode base material sequentially laminated on both surfaces of the electrolyte membrane (that is, electrode base material / catalyst layer / electrolyte film / catalyst layer / electrode base material layer structure) is an electrode-electrolyte. It is called a membrane assembly (MEA).

電極−電解質膜接合体には、クロスリークによる電池性能劣化という問題がある。すなわち、固体高分子電解質形燃料電池では、燃料極側から流入する水素がガス拡散電極を通じて燃料極側の触媒層で反応（水素イオン化）、及び酸化剤極側から流入する酸素が酸化剤極側の触媒層で反応（水素イオンと結合）することにより、発電を行う。しかし、ガス拡散層を通過した水素又は酸素が、燃料極側又は酸化剤極側の触媒層を経ず、触媒層の外周部を伝って、直接電解質を経て、反対側の触媒層で反応してしまい、目的とする発電反応が生じない場合がある。これをクロスリークという。クロスリークを起こすと、電池性能が劣化したり、運転不能となる場合もある。   The electrode-electrolyte membrane assembly has a problem of battery performance deterioration due to cross leak. That is, in the solid polymer electrolyte fuel cell, hydrogen flowing from the fuel electrode side reacts with the catalyst layer on the fuel electrode side through the gas diffusion electrode (hydrogen ionization), and oxygen flowing from the oxidant electrode side moves to the oxidant electrode side. Power is generated by reacting (bonding with hydrogen ions) in the catalyst layer. However, hydrogen or oxygen that has passed through the gas diffusion layer does not pass through the catalyst layer on the fuel electrode side or oxidant electrode side, but travels along the outer periphery of the catalyst layer, directly through the electrolyte, and reacts with the catalyst layer on the opposite side. The target power generation reaction may not occur. This is called cross leak. If a cross leak occurs, the battery performance may be deteriorated or operation may become impossible.

このようなクロスリークを防止する方法として、例えば、特許文献１には、外周面及び／又は周辺部にガス不透過処理を施したガス拡散電極が提案されている。このガス拡散電極は、その側面全体（外周面）を、フッ素樹脂膜等で添貼したり、シリコン、フッ素樹脂若しくは塩化ビニル系の充填剤、接着剤又はグリースを塗布させたりすることにより、側面全部及び上下面の一部を覆った形状としている。   As a method for preventing such cross leak, for example, Patent Literature 1 proposes a gas diffusion electrode in which a gas impermeability treatment is performed on an outer peripheral surface and / or a peripheral portion. This gas diffusion electrode has its entire side surface (outer peripheral surface) attached with a fluororesin film or the like, or by applying silicon, fluororesin or vinyl chloride filler, adhesive or grease. The shape covers all and part of the upper and lower surfaces.

しかしながら、このようなフッ素樹脂の添貼、充填剤での塗布は、ガス拡散層の細孔を閉塞し、ガス拡散性能を低下させ、電池性能が悪化する可能性がある。また、クロスリークにおいても十分解決されたとは言い難く、改良の余地がある。
特許第３３１３２３８号 However, such application of fluororesin and application with a filler may clog the pores of the gas diffusion layer, reduce the gas diffusion performance, and may deteriorate the battery performance. In addition, it is difficult to say that the cross leak has been sufficiently solved, and there is room for improvement.
Japanese Patent No. 3313238

本発明の課題は、ガス拡散性能等を低下させず、クロスリークを防止し、電池性能に優れた電極−電解質膜接合体を提供することとする。   An object of the present invention is to provide an electrode-electrolyte membrane assembly that does not deteriorate gas diffusion performance, prevents cross leak, and has excellent battery performance.

本発明者は、上記課題を解決すべく、鋭意研究を重ねて来た。その結果、特定の構造を有する電極−電解質膜接合体を採用することにより、ガスのクロスリークを防止でき、電池反応を阻害することなく、優れた電池性能を発揮できる燃料電池を製造できることを見出した。本発明は、このような知見に基づき完成されたものである。   The present inventor has intensively studied to solve the above problems. As a result, it has been found that by adopting an electrode-electrolyte membrane assembly having a specific structure, it is possible to produce a fuel cell capable of preventing gas cross-leakage and exhibiting excellent cell performance without inhibiting cell reaction. It was. The present invention has been completed based on such findings.

すなわち、本発明は、下記に示す電極−電解質膜接合体及びその製造方法に係る。   That is, this invention relates to the electrode-electrolyte membrane assembly shown below and its manufacturing method.

項１．高分子電解質膜の一方面又は両面上に触媒層及びガスバリア性樹脂フィルムが同一の膜厚で形成され、更に触媒層及びガスバリア性樹脂フィルム上にガス拡散基材が形成された電極−電解質膜接合体であって、
前記ガスバリア性樹脂フィルムは、触媒層の外周部に形成されており、
前記ガスバリア性樹脂フィルムは熱接着性樹脂フィルムを含む、
電極−電解質膜接合体。 Item 1. Electrode-electrolyte membrane bonding in which a catalyst layer and a gas barrier resin film are formed with the same film thickness on one or both surfaces of a polymer electrolyte membrane, and a gas diffusion substrate is further formed on the catalyst layer and the gas barrier resin film Body,
The gas barrier resin film is formed on the outer periphery of the catalyst layer,
The gas barrier resin film includes a thermal adhesive resin film,
Electrode-electrolyte membrane assembly.

項２．前記触媒層及びガスバリア性樹脂フィルムの合計面積とガス拡散基材の面積とが同一である、項１に記載の電極−電解質膜接合体。   Item 2. Item 2. The electrode-electrolyte membrane assembly according to Item 1, wherein the total area of the catalyst layer and the gas barrier resin film is the same as the area of the gas diffusion base material.

項３．前記ガスバリア性樹脂フィルムが、酸素バリア性樹脂フィルムである、項１又は２に記載の電極−電解質膜接合体。   Item 3. Item 3. The electrode-electrolyte membrane assembly according to Item 1 or 2, wherein the gas barrier resin film is an oxygen barrier resin film.

項４．前記ガスバリア性樹脂フィルムが、水素バリア性樹脂フィルムである、項１又は２に記載の電極−電解質膜接合体。   Item 4. Item 3. The electrode-electrolyte membrane assembly according to Item 1 or 2, wherein the gas barrier resin film is a hydrogen barrier resin film.

項５．ガスバリア性樹脂フィルムが少なくとも２層の樹脂フィルムで構成されている、項１〜４のいずれかに記載の電極−電解質膜接合体。   Item 5. Item 5. The electrode-electrolyte membrane assembly according to any one of Items 1 to 4, wherein the gas barrier resin film is composed of at least two resin films.

項６．ガスバリア性樹脂フィルムは、熱接着性樹脂フィルム／酸素バリア性樹脂フィルム又は水素バリア性樹脂フィルム／熱接着性樹脂フィルムの少なくとも３層で構成されている、項５に記載の電極−電解質膜接合体。   Item 6. Item 6. The electrode-electrolyte membrane assembly according to Item 5, wherein the gas barrier resin film is composed of at least three layers of thermal adhesive resin film / oxygen barrier resin film or hydrogen barrier resin film / thermal adhesive resin film. .

項７．（１）電解質膜上に触媒層が積層された触媒層−電解質膜積層体上にある当該触媒層の外周部にガスバリア性樹脂フィルムを配置し、
（２）当該触媒層及びガスバリア性樹脂フィルム上にガス拡散基材を配置し、熱プレスする、
ことにより得られる、電極−電解質膜接合体。 Item 7. (1) Catalyst layer in which a catalyst layer is laminated on an electrolyte membrane-Disposing a gas barrier resin film on the outer periphery of the catalyst layer on the electrolyte membrane laminate,
(2) A gas diffusion base material is disposed on the catalyst layer and the gas barrier resin film and hot pressed.
The electrode-electrolyte membrane assembly obtained by this.

項８．（１）電解質膜上に触媒層が積層された触媒層−電解質膜積層体上にある当該触媒層の外周部にガスバリア性樹脂フィルムを配置する工程、及び
（２）当該触媒層及びガスバリア性樹脂フィルム上にガス拡散基材を配置し、熱プレスする工程、
を備えた電極−電解質接合体の製造方法。 Item 8. (1) a catalyst layer having a catalyst layer laminated on an electrolyte membrane—a step of disposing a gas barrier resin film on the outer periphery of the catalyst layer on the electrolyte membrane laminate; and (2) the catalyst layer and the gas barrier resin. Placing a gas diffusion substrate on the film and hot pressing,
A method for producing an electrode-electrolyte assembly comprising:

本発明の電極−電解質膜接合体は、高分子電解質膜の一方面又は両面上に触媒層及びガスバリア性樹脂フィルム層が同一の膜厚で形成され、更に触媒層及びガスバリア性樹脂フィルム上にガス拡散基材が形成された電極−電解質膜接合体であって、前記ガスバリア性樹脂フィルムは、触媒層の外周部に形成されていることを特徴とする。なお、電極−電解質膜接合体のうち電極は、触媒層及びガス拡散基材が積層された部材を示す。   In the electrode-electrolyte membrane assembly of the present invention, the catalyst layer and the gas barrier resin film layer are formed with the same film thickness on one or both surfaces of the polymer electrolyte membrane, and further the gas is formed on the catalyst layer and the gas barrier resin film. An electrode-electrolyte membrane assembly in which a diffusion substrate is formed, wherein the gas barrier resin film is formed on an outer peripheral portion of a catalyst layer. In the electrode-electrolyte membrane assembly, an electrode indicates a member in which a catalyst layer and a gas diffusion base material are laminated.

本発明の電極−電解質膜接合体の平面図を図１に示し、平面図のＢ−Ｂ断面の断面図を図２に示す。本発明の触媒層は、図１に示したように、前記触媒層及びガスバリア性樹脂フィルムの合計面積とガス拡散基材の面積とが平面図において同一であることが好ましい。   A plan view of the electrode-electrolyte membrane assembly of the present invention is shown in FIG. As for the catalyst layer of this invention, as shown in FIG. 1, it is preferable that the total area of the said catalyst layer and a gas barrier resin film and the area of a gas diffusion base material are the same in a top view.

ガスバリア性樹脂フィルム
ガスバリア性樹脂フィルムは、触媒層の外周部に形成されている。すなわち、ガスバリア性樹脂フィルムが額縁状（すなわち、中抜き）になっており、その中に触媒層がはめ込まれている。 Gas barrier resin film The gas barrier resin film is formed on the outer periphery of the catalyst layer. That is, the gas barrier resin film has a frame shape (that is, a hollow), and the catalyst layer is fitted therein.

額縁状の外形及び中抜きの形は限定的でないが、通常長方形、正方形等である。額縁状の幅は限定的でないが、通常０．０５mm〜２０ｍｍ程度の範囲内である。   The shape of the frame and the shape of the hollow are not limited, but are usually rectangular, square and the like. The width of the frame shape is not limited, but is usually in the range of about 0.05 mm to 20 mm.

触媒層とガスバリア性樹脂フィルムとの膜厚は同一であり、ガスバリア性樹脂フィルムの平均厚みは６〜８０μｍ程度が好ましく、より好ましくは８〜６０μｍ程度である。   The film thickness of the catalyst layer and the gas barrier resin film is the same, and the average thickness of the gas barrier resin film is preferably about 6 to 80 μm, more preferably about 8 to 60 μm.

図１に示すように、触媒層及びガスバリア性樹脂フィルムは全面が電解質膜上に積層されており、電解質膜の面積が触媒層及びガスバリア性樹脂フィルムの合計面積よりも大きい。より具体的には、図１に示すように、電解質膜がガス拡散基材からはみ出すように構成されていることが望ましい。また、触媒層及びガスバリア性樹脂フィルム上にガス拡散基材が積層されており、触媒層及びガスバリア性樹脂フィルムの合計面積と、ガス拡散基材面積とは実質的に同一であることが好ましい。   As shown in FIG. 1, the entire surface of the catalyst layer and the gas barrier resin film is laminated on the electrolyte membrane, and the area of the electrolyte membrane is larger than the total area of the catalyst layer and the gas barrier resin film. More specifically, as shown in FIG. 1, it is desirable that the electrolyte membrane is configured to protrude from the gas diffusion base material. Moreover, the gas diffusion base material is laminated | stacked on the catalyst layer and the gas barrier resin film, and it is preferable that the total area of a catalyst layer and a gas barrier resin film and a gas diffusion base material area are substantially the same.

触媒層とガス拡散基材とは積層されているが、触媒層よりもガス拡散基材の方が大きくなっており、ガス拡散基材には、触媒層が積層されていない箇所（触媒層非積層基材部）が生じる。このときの当該触媒層非積層基材部は額縁状（すなわち、中抜き状）となることが好ましい。この額縁の幅（図１に示したＡの幅）は限定的でないが、通常、０．０５mm〜２０ｍｍ程度の範囲内とすればよい。なお、触媒層及びガスバリア性樹脂フィルムの合計面積と、ガス拡散基材との面積は同一である場合、触媒層非積層部とガスバリア性樹脂フィルムとは同一平面形状及び同一面積であることが好ましい。   The catalyst layer and the gas diffusion base material are laminated, but the gas diffusion base material is larger than the catalyst layer, and the gas diffusion base material has a portion where the catalyst layer is not laminated (catalyst layer non-layer). (Laminated substrate part) is generated. At this time, the catalyst layer non-laminated base material portion is preferably in a frame shape (that is, a hollow shape). The width of the frame (the width of A shown in FIG. 1) is not limited, but is usually in the range of about 0.05 mm to 20 mm. When the total area of the catalyst layer and the gas barrier resin film is the same as the area of the gas diffusion substrate, the catalyst layer non-laminated portion and the gas barrier resin film are preferably the same planar shape and the same area. .

ガスバリア性樹脂フィルムは、水素及び／又は酸素を透過しない樹脂フィルムであればよい。燃料極に当該樹脂フィルムを設置する場合は、水素を透過しないフィルム（水素バリア性樹脂フィルム）であり、酸化剤極側に当該樹脂フィルムを設置する場合は、酸素を透過しないフィルム（酸素バリア性樹脂フィルム）である。水素及び酸素の両方を透過しないフィルムの場合は、酸化剤極側及び燃料極側のどちらに使用してもよい。   The gas barrier resin film may be a resin film that does not transmit hydrogen and / or oxygen. When installing the resin film on the fuel electrode, it is a film that does not transmit hydrogen (hydrogen barrier resin film). When installing the resin film on the oxidizer electrode side, it does not transmit oxygen (oxygen barrier property). Resin film). In the case of a film that does not transmit both hydrogen and oxygen, it may be used on either the oxidant electrode side or the fuel electrode side.

また、これらのフィルムは、フィルム自体にガスバリア性を有していてもよく、樹脂基材にガスバリア性膜を積層させたガスバリア性膜積層フィルムであってもよい。本発明では、これらをまとめて、ガスバリア性樹脂フィルムという。   In addition, these films may have a gas barrier property on the film itself, or may be a gas barrier film laminated film in which a gas barrier film is laminated on a resin base material. In the present invention, these are collectively referred to as a gas barrier resin film.

酸素バリア性樹脂フィルムを構成する酸素バリア性樹脂としては、酸素を透過しないものであれば限定的でないが、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル樹脂、ナイロン等のポリアミド樹脂、ポリイミド樹脂、エチレン−ビニルアルコール共重合樹脂などが好ましく挙げられる。これらの中でも、高融点（融点１００℃以上、好ましくは１２０〜１８０℃）であることが好ましい。酸素バリア性を有する高融点樹脂を採用することにより、酸素バリア性を発揮することはもちろん、固体高分子燃料電池の運転温度（通常８０℃程度）で運転しても熱による溶融を防止するため、寸法安定性に優れ、形状が変化しない。   The oxygen barrier resin constituting the oxygen barrier resin film is not limited as long as it does not transmit oxygen. For example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyamide resins such as nylon Preferred examples include polyimide resin and ethylene-vinyl alcohol copolymer resin. Among these, it is preferable that it is high melting | fusing point (melting | fusing point 100 degreeC or more, Preferably it is 120-180 degreeC). By adopting a high-melting point resin having oxygen barrier properties, in addition to exhibiting oxygen barrier properties, in order to prevent melting due to heat even when operating at the operating temperature of the polymer electrolyte fuel cell (usually about 80 ° C.) , Excellent in dimensional stability and shape does not change.

また、他の酸素バリア性樹脂フィルムとして、物理蒸着法又は化学蒸着法（ＣＶＤ法）により酸化膜、窒化膜、酸窒化膜等の無機物膜が樹脂基材上に形成された樹脂フィルムも挙げられる。これら無機物膜及び樹脂基材は水素バリア性樹脂フィルムで後述するものが挙げられる。無機物質の平均膜厚は、５〜１００ｎｍ程度が好ましい。   In addition, as other oxygen barrier resin film, a resin film in which an inorganic film such as an oxide film, a nitride film, or an oxynitride film is formed on a resin substrate by a physical vapor deposition method or a chemical vapor deposition method (CVD method) can also be cited. . Examples of the inorganic film and the resin base material include a hydrogen barrier resin film which will be described later. The average film thickness of the inorganic substance is preferably about 5 to 100 nm.

次に、水素バリア性樹脂フィルムとしては、上記酸素バリア性樹脂のうち水素バリア性を有する樹脂を使用できる。このような樹脂としては、日本合成化学（株）から「ソアノール」として市販されているエチレン−ビニルアルコール共重合樹脂を好ましく例示できる。他の水素バリア性樹脂フィルムとしては、物理蒸着法又は化学蒸着法（ＣＶＤ法）により酸化膜、窒化膜、酸窒化膜等の水素バリア性無機物膜が樹脂基材上に形成された樹脂フィルムが好ましく挙げられる。無機物膜の種類としては、具体的には、酸化アルミニウム、酸化珪素、酸化マグネシウム、酸化チタンなどが挙げられる。無機物質の平均膜厚は、５〜１００ｎｍ程度が好ましい。   Next, as the hydrogen barrier resin film, a resin having a hydrogen barrier property among the oxygen barrier resins can be used. As such a resin, an ethylene-vinyl alcohol copolymer resin commercially available as “Soanol” from Nippon Synthetic Chemical Co., Ltd. can be preferably exemplified. As another hydrogen barrier resin film, a resin film in which a hydrogen barrier inorganic film such as an oxide film, a nitride film, and an oxynitride film is formed on a resin substrate by a physical vapor deposition method or a chemical vapor deposition method (CVD method). Preferably mentioned. Specific examples of the inorganic film include aluminum oxide, silicon oxide, magnesium oxide, and titanium oxide. The average film thickness of the inorganic substance is preferably about 5 to 100 nm.

特に、物理蒸着法のうちスパッタ法により形成された無機物膜が、水素原子を実質的に含有せず、水素バリア性に優れる点で好ましい。スパッタ法としては公知の方法により行うことができるが、水素バリア性の観点から、特に電子サイクロトロン共鳴（ＥＣＲ）プラズマを用いたスパッタ法（ＥＣＲスパッタ法）等が好ましい。本発明では、特にＥＣＲスパッタ法により得られた酸化アルミニウム膜が好ましい。   In particular, an inorganic film formed by sputtering among physical vapor deposition methods is preferable in that it does not substantially contain hydrogen atoms and is excellent in hydrogen barrier properties. As a sputtering method, a known method can be used, but from the viewpoint of hydrogen barrier properties, a sputtering method using electron cyclotron resonance (ECR) plasma (ECR sputtering method) is particularly preferable. In the present invention, an aluminum oxide film obtained by ECR sputtering is particularly preferable.

一方、ＣＶＤ法も経済性の観点から好ましく、ＣＶＤの中でも、特にプラズマＣＶＤが好ましい。具体的には、ＳｉＨ４及びＮ２Ｏを原料とするプラズマＣＶＤにより形成された酸化珪素膜（特にＳｉＯ２膜）は、優れた水素バリア性を発揮することができる。 On the other hand, the CVD method is also preferable from the viewpoint of economy, and plasma CVD is particularly preferable among the CVD methods. Specifically, a silicon oxide film (particularly a SiO 2 film) formed by plasma CVD using SiH 4 and N 2 O as raw materials can exhibit excellent hydrogen barrier properties.

樹脂基材としては、例えば、ポリエステルフィルム、ポリエチレンナフタレートフィルム、ポリアミドフィルム、ポリオレフィンフィルム、ポリイミドフィルム、ポリプロピレンフィルム等から群から選択される少なくとも１種であって、且つ一軸ないし二軸延伸された延伸フィルム等を挙げることができる。   The resin base material is, for example, at least one selected from the group consisting of a polyester film, a polyethylene naphthalate film, a polyamide film, a polyolefin film, a polyimide film, a polypropylene film, etc., and stretched uniaxially or biaxially. A film etc. can be mentioned.

特に、本発明では、上記水素バリア性無機物膜を形成させる樹脂基材に、酸素バリア性を有する高融点樹脂を採用することが好ましい。すなわち、酸素バリア性樹脂フィルムに上記水素バリア性無機物膜を形成させた樹脂フィルム（水素バリア性無機物膜形成酸素バリア性樹脂フィルム）が好ましい。これにより、高い酸素バリア性及び水素バリア性を発揮でき、クロスリークをより低減することできる。   In particular, in the present invention, it is preferable to employ a high melting point resin having oxygen barrier properties for the resin base material on which the hydrogen barrier inorganic film is formed. That is, a resin film obtained by forming the hydrogen barrier inorganic film on an oxygen barrier resin film (hydrogen barrier inorganic film-forming oxygen barrier resin film) is preferable. Thereby, high oxygen barrier property and hydrogen barrier property can be exhibited, and cross leak can be further reduced.

また、本発明では、上記ガスバリア性樹脂フィルムは、少なくとも２層の樹脂フィルムから構成されていることが好ましい。特に、上記水素バリア性樹脂フィルム又は酸素バリア性樹脂フィルムの片面若しくは両面（特に両面）に熱接着性樹脂フィルム（熱接着性樹脂層）が積層されたものであることが好ましい。すなわち、熱接着性樹脂フィルム／酸素バリア性樹脂フィルム又は水素バリア性樹脂フィルム／熱接着性樹脂フィルムであることが好ましく、もっとも好ましくは、熱接着性樹脂フィルム／水素バリア性無機物膜形成酸素バリア性樹脂フィルム／熱接着性樹脂フィルムであることが好ましい。なお、水素バリア性無機物膜と酸素バリア性樹脂フィルムとはいずれが電解質側に近い方に積層されていてもよい。このような熱接着性樹脂フィルムが積層させた構造を採用することにより、電解質膜とガス拡散基材とを熱接着性樹脂フィルムを介して、より簡便に接着することができる。   In the present invention, the gas barrier resin film is preferably composed of at least two resin films. In particular, it is preferable that a thermal adhesive resin film (thermal adhesive resin layer) is laminated on one side or both sides (particularly both sides) of the hydrogen barrier resin film or oxygen barrier resin film. That is, it is preferably a thermal adhesive resin film / oxygen barrier resin film or a hydrogen barrier resin film / thermal adhesive resin film, most preferably a thermal adhesive resin film / hydrogen barrier inorganic film-forming oxygen barrier property. A resin film / thermoadhesive resin film is preferred. Note that either the hydrogen barrier inorganic film or the oxygen barrier resin film may be laminated closer to the electrolyte side. By adopting such a structure in which the heat-adhesive resin films are laminated, the electrolyte membrane and the gas diffusion base material can be more easily bonded via the heat-adhesive resin film.

熱接着性樹脂フィルムは熱接着性を有する限り限定的でないが、融点が１８０℃以下（特に１５０℃以下）であることが好ましい。下限は限定的でなく、１００℃程度とすればよい。具体的には、ポリエチレン、ポリプロピレン、エチレン−ビニルアルコール共重合樹脂等からなる群から選択される少なくとも１種が挙げられる。   The thermal adhesive resin film is not limited as long as it has thermal adhesiveness, but the melting point is preferably 180 ° C. or lower (in particular 150 ° C. or lower). The lower limit is not limited and may be about 100 ° C. Specific examples include at least one selected from the group consisting of polyethylene, polypropylene, ethylene-vinyl alcohol copolymer resin, and the like.

熱接着性樹脂フィルム、ガスバリア性樹脂フィルム等の膜厚は限定的でなく、その合計厚みが、隣接する触媒層の厚みと同一であればよいが、例えば上記熱接着性樹脂フィルム／酸素バリア性樹脂フィルム又は水素バリア性樹脂フィルム／熱接着性樹脂フィルムの場合、６〜２５μｍ／６〜３０μｍ／６〜２５μｍ程度、好ましくは、８〜２０μｍ／８〜２０μｍ／８〜２０μｍ程度とすればよい。   The film thickness of the heat-adhesive resin film, gas barrier resin film, etc. is not limited, and the total thickness may be the same as the thickness of the adjacent catalyst layer. For example, the above-mentioned heat-adhesive resin film / oxygen barrier property In the case of a resin film or a hydrogen barrier resin film / thermal adhesive resin film, it may be about 6 to 25 μm / 6 to 30 μm / 6 to 25 μm, and preferably about 8 to 20 μm / 8 to 20 μm / 8 to 20 μm.

なお、熱接着性樹脂フィルムを設ける場合は、当該熱接着性樹脂フィルムと酸素バリア性樹脂フィルム又は水素バリア性樹脂フィルムとの間に、必要に応じて、アンカーコート剤及び接着剤を塗布することにより、アンカーコート層及び接着層を設けてもよい。これらアンカーコート剤及び接着剤は限定的でなく公知又は市販のものを用いればよい。   In addition, when providing a heat-adhesive resin film, an anchor coat agent and an adhesive agent are applied between the heat-adhesive resin film and the oxygen barrier resin film or the hydrogen barrier resin film as necessary. Thus, an anchor coat layer and an adhesive layer may be provided. These anchor coating agents and adhesives are not limited, and known or commercially available ones may be used.

ガス拡散基材
ガス拡散基材は、導電性を有し、多孔質のものであれば、特に制限されず、公知又は市販のものを使用できる。例えば、カーボンペーパ、カーボンクロス、カーボンフェルト等が挙げられる。膜厚は特に制限されないが、通常は２０μｍ〜４００μm程度、好ましくは1００μｍ〜３００μm程度である。 Gas diffusion base material The gas diffusion base material is not particularly limited as long as it has conductivity and is porous, and a known or commercially available one can be used. For example, carbon paper, carbon cloth, carbon felt and the like can be mentioned. The film thickness is not particularly limited, but is usually about 20 μm to 400 μm, preferably about 100 μm to 300 μm.

触媒層
触媒層は、水素イオン伝導性高分子電解質及び触媒粒子を含有している限り、限定的でなく、公知又は市販のものを使用できる。触媒層は、例えば、公知又は市販の水素イオン伝導性高分子電解質含有溶液及び触媒担持炭素粒子を混合し、乾燥させることにより、製造することもできる。 The catalyst layer is not limited as long as it contains a hydrogen ion conductive polymer electrolyte and catalyst particles, and a known or commercially available one can be used. The catalyst layer can also be produced, for example, by mixing a known or commercially available hydrogen ion conductive polymer electrolyte-containing solution and catalyst-supported carbon particles and drying.

電解質膜
電解質膜は、水素イオン伝導性のものであれば限定的でなく、公知又は市販のものを使用できる。電解質膜の具体例としては、デュポン社製の「Nafion」膜、旭硝子（株）製の「Flemion」膜、旭化成（株）製の「Aciplex」膜、ゴア（Gore）社製の「Gore Select」膜等が挙げられる。電解質膜の膜厚は、通常２０〜２５０μｍ程度、好ましくは２０〜８０μｍ程度である。 The electrolyte membrane is not limited as long as it is hydrogen ion conductive, and a known or commercially available membrane can be used. Specific examples of electrolyte membranes include “Nafion” membrane manufactured by DuPont, “Flemion” membrane manufactured by Asahi Glass Co., Ltd., “Aciplex” membrane manufactured by Asahi Kasei Co., Ltd., and “Gore Select” manufactured by Gore. Examples include membranes. The thickness of the electrolyte membrane is usually about 20 to 250 μm, preferably about 20 to 80 μm.

本発明の電解質膜の合計面積は、触媒層及びガスバリア性樹脂フィルムの合計面積と同一又は大きく、触媒層及びガスバリア層が電解質膜上にはみ出さずに積層している。   The total area of the electrolyte membrane of the present invention is the same as or larger than the total area of the catalyst layer and the gas barrier resin film, and the catalyst layer and the gas barrier layer are laminated without protruding on the electrolyte membrane.

製造方法
本発明の電極−電解質膜接合体の製造方法は、
（１）電解質膜上に触媒層が積層された触媒層−電解質膜積層体上にある当該触媒層の外周部にガスバリア性樹脂フィルムを配置する工程、及び
（２）当該触媒層及びガスバリア性樹脂フィルム上にガス拡散基材を配置し、熱プレスする工程、を備えることを特徴とする。 Manufacturing method The manufacturing method of the electrode-electrolyte membrane assembly of the present invention is:
(1) a catalyst layer having a catalyst layer laminated on an electrolyte membrane—a step of disposing a gas barrier resin film on the outer periphery of the catalyst layer on the electrolyte membrane laminate; and (2) the catalyst layer and the gas barrier resin. A step of disposing a gas diffusion base material on the film and performing hot pressing.

本発明で使用する触媒層−電解質膜積層体の製造方法は限定的でなく、例えば、公知又は市販の触媒転写フィルムを熱プレス法等により電解質膜上に形成することにより得られる。   The method for producing the catalyst layer-electrolyte membrane laminate used in the present invention is not limited, and can be obtained, for example, by forming a known or commercially available catalyst transfer film on the electrolyte membrane by a hot press method or the like.

ガスバリア性樹脂フィルムは、上記積層体に積層された触媒層の形状に合わせて、中抜きに削除し、額縁状とした後、当該額縁状のガスバリア性樹脂フィルムを触媒層にはめ込み、当該フィルムを電解膜に積層させることにより、触媒層の外周部に配置させる。   In accordance with the shape of the catalyst layer laminated on the laminate, the gas barrier resin film is removed in a hollow shape to form a frame, and then the frame-shaped gas barrier resin film is fitted into the catalyst layer, and the film is By laminating on the electrolytic membrane, it is arranged on the outer periphery of the catalyst layer.

その後、当該触媒層及びガスバリア性樹脂フィルム上にガス拡散基材を配置し、熱プレスすればよい。この熱プレスにより、ガスバリア性樹脂フィルムが融着及び固化して接着効果を発揮するため、当該樹脂フィルムを介してガス拡散基材、触媒層及び電解質膜が強固に固定される。このため、触媒層の反応有効面積及びガス拡散基材のガス拡散性能を損なうことなく、電極−電解質膜接合体を簡便に作製することができる。   Thereafter, a gas diffusion base material may be disposed on the catalyst layer and the gas barrier resin film and hot pressed. Since the gas barrier resin film is fused and solidified by this hot pressing and exhibits an adhesive effect, the gas diffusion base material, the catalyst layer, and the electrolyte membrane are firmly fixed through the resin film. For this reason, an electrode-electrolyte membrane assembly can be easily produced without impairing the reaction effective area of the catalyst layer and the gas diffusion performance of the gas diffusion substrate.

特にガスバリア性樹脂フィルムが少なくとも２層構造である場合、より好ましくは、熱接着性樹脂フィルム／酸素バリア性樹脂フィルム又は水素バリア性樹脂フィルム／熱接着性樹脂フィルム等である場合、熱接着性樹脂フィルムがより接着効果を発揮するため、より簡便に電極−電解質膜接合体を製造することができる。   In particular, when the gas barrier resin film has at least a two-layer structure, more preferably, when the gas barrier resin film is a thermal adhesive resin film / oxygen barrier resin film or a hydrogen barrier resin film / thermal adhesive resin film, the thermal adhesive resin Since the film exhibits a more adhesive effect, the electrode-electrolyte membrane assembly can be more easily produced.

熱プレスの方法は、限定的でなく、常法に従って行えばよい。加圧レベルは、通常０．５〜２０ＭＰａ程度、好ましくは１〜１０ＭＰａ程度、より好ましくは１〜５ＭＰa程度がよい。また、この加圧の際に、転写不良を避けるために、加圧面を加熱するのが好ましい。加熱温度は、ガスバリア性樹脂フィルムが溶融する温度（好ましくは熱接着性樹脂フィルムが溶融する温度であればよく、通常１００〜２００℃程度（好ましくは１２０〜１５０℃）がよい。   The method of hot pressing is not limited and may be performed according to a conventional method. The pressure level is usually about 0.5 to 20 MPa, preferably about 1 to 10 MPa, and more preferably about 1 to 5 MPa. In addition, it is preferable to heat the pressure surface during the pressurization in order to avoid transfer defects. The heating temperature may be a temperature at which the gas barrier resin film melts (preferably a temperature at which the heat-adhesive resin film melts), and is usually about 100 to 200 ° C. (preferably 120 to 150 ° C.).

本発明によれば、特定のガスバリア性樹脂フィルムを触媒層の外周部に配置しているため、クロスリークを低減でき、優れた電池性能を有する燃料電池を製造することができる。   According to the present invention, since the specific gas barrier resin film is disposed on the outer peripheral portion of the catalyst layer, the cross leak can be reduced and a fuel cell having excellent battery performance can be manufactured.

本発明によれば、固体高分子燃料電池の運転温度（通常８０℃程度）で運転しても熱による溶融を防止でき、寸法安定性に優れ、形状が変化しない。   According to the present invention, even when the polymer electrolyte fuel cell is operated at an operating temperature (usually about 80 ° C.), melting due to heat can be prevented, dimensional stability is excellent, and the shape does not change.

本発明の製造方法によれば、ガスバリア性樹脂フィルムを触媒層周辺部に配置するだけであるので、クロスリークが低減された電極−電解質膜積層体を簡易に製造することができる。   According to the production method of the present invention, since the gas barrier resin film is only disposed on the periphery of the catalyst layer, an electrode-electrolyte membrane laminate with reduced cross leak can be easily produced.

実施例及び比較例を用いて、本発明をさらに詳述する。なお、本発明は下記の実施例に限定されない。   The present invention will be described in further detail using examples and comparative examples. In addition, this invention is not limited to the following Example.

実施例１
白金触媒担持炭素粒子（Ｐｔ：４６ｗｔ％、田中貴金属工業社製、「ＴＥＣ１０Ｅ５０Ｅ」）１０ｇ及び５重量％水素イオン伝導性高分子電解質含有溶液（デュポン社製、溶剤：水、1-プロパノール及びメタノール、エタノール）１００ｇに、蒸留水３０ｇ、及び２−プロパノール（キシダ化学製）１００ｇを配合し、分散機にて攪拌混合することでペースト組成物を調製した。次に調製したペースト組成物を、ドクターブレードにより乾燥後の白金量が０．５ｍｇ/ｃｍ２になるように、ポリエチレンテレフタラート（Ｅ３１２０、東洋紡社製）フィルム上に塗工後、大気雰囲気中で９５℃の条件で１５分間より乾燥させ、酸化剤極用の触媒転写フィルムを作製した。 Example 1
Platinum catalyst-supported carbon particles (Pt: 46 wt%, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., “TEC10E50E”) and 5 wt% hydrogen ion conductive polymer electrolyte-containing solution (manufactured by DuPont, solvent: water, 1-propanol and methanol, A paste composition was prepared by blending 30 g of distilled water and 100 g of 2-propanol (manufactured by Kishida Chemical Co.) with 100 g of ethanol and stirring and mixing with a disperser. Next, the prepared paste composition was coated on a polyethylene terephthalate (E3120, manufactured by Toyobo Co., Ltd.) film so that the amount of platinum after drying with a doctor blade was 0.5 mg / cm 2 , and then in the atmosphere. A catalyst transfer film for an oxidant electrode was produced by drying at 95 ° C. for 15 minutes.

白金ルテニウム触媒担持炭素粒子（ＰｔＲｕ：５４ｗｔ％、田中貴金属工業社製、「ＴＥＣ６１Ｅ５４」）１０ｇ及び５重量水素イオン伝導性高分子電解質含有溶液（デュポン社製、溶剤：水、1−プロパノール、メタノール及びエタノール）１００ｇに、蒸留水３０ｇ、プロピレングリコール（キシダ化学製）２ｇ 及び２-プロパノール（キシダ化学製）１００ｇを配合し、分散機にて攪拌混合することでペースト組成物を調製した。次に調製したペースト組成物を、ドクターブレードにより乾燥後の白金量が０．５ｍｇ/ｃｍ２になるように、ポリエチレンテレフタラートフィルム（東洋紡社製、「Ｅ３１２０」）上に塗工後、大気雰囲気中で９５℃の条件で１５分間より乾燥させ、燃料極用触媒転写フィルムを作製した。 Platinum ruthenium catalyst-supported carbon particles (PtRu: 54 wt%, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., “TEC61E54”) and a 5 weight hydrogen ion conductive polymer electrolyte-containing solution (manufactured by DuPont, solvent: water, 1-propanol, methanol, and A paste composition was prepared by blending 30 g of distilled water, 2 g of propylene glycol (manufactured by Kishida Chemical Co., Ltd.) and 100 g of 2-propanol (manufactured by Kishida Chemical Co., Ltd.) with 100 g of ethanol and stirring and mixing with a disperser. Next, the prepared paste composition was coated on a polyethylene terephthalate film (“E3120” manufactured by Toyobo Co., Ltd.) so that the platinum amount after drying with a doctor blade was 0.5 mg / cm 2 , and then the atmosphere Then, it was dried at 95 ° C. for 15 minutes to produce a fuel electrode catalyst transfer film.

上記で作製した酸化剤極用転写フィルム及び燃料極用触媒転写フィルムを５０ｍｍ×５０ｍｍに切り出し、水素イオン伝導性電解質膜（Ｎａｆｉｏｎ１１２、Ｄｕｐｏｎｔ社製）１０ｃｍ×１０ｃｍを介して対面するように配置し、１５０℃、５ＭＰａの条件にて３分間熱プレスする事により触媒層−電解質膜積層体を作製した。   The oxidant electrode transfer film and the fuel electrode catalyst transfer film prepared above were cut out to 50 mm × 50 mm and arranged so as to face each other through a hydrogen ion conductive electrolyte membrane (Nafion 112, manufactured by Dupont) 10 cm × 10 cm. A catalyst layer-electrolyte membrane laminate was produced by hot pressing at 150 ° C. and 5 MPa for 3 minutes.

酸化剤極側及び燃料極側の樹脂フィルムとして、酸素バリア性及び水素バリア性を有するエチレン−ビニルアルコール共重合樹脂フィルム（ソアノール、日本合成化学（株）製、厚み２５μｍ）を６０×６０ｍｍサイズの中央の５０×５０ｍｍを切り出し枠状に加工した。   As a resin film on the oxidizer electrode side and fuel electrode side, an ethylene-vinyl alcohol copolymer resin film (Soarnol, manufactured by Nippon Synthetic Chemical Co., Ltd., thickness 25 μm) having oxygen barrier properties and hydrogen barrier properties is 60 × 60 mm in size. The center 50 × 50 mm was cut into a frame shape.

ガス拡散基材は、カーボンペーパ（ＴＧＰ−Ｈ−０９０、東レ（株）製）を６０×６０ｍｍに切り出し、ガス拡散基材と触媒層−電解質膜接合体をエチレン−ビニルアルコール共重合樹脂フィルムを介して、触媒層上にガス拡散基材を配置し、熱プレスにより１５０℃、５ＭＰａにて３０秒間プレスすることにより電極−電解質膜接合体を作製した。   For the gas diffusion base material, carbon paper (TGP-H-090, manufactured by Toray Industries, Inc.) is cut out to 60 × 60 mm, and the gas diffusion base material and the catalyst layer-electrolyte membrane assembly are combined with an ethylene-vinyl alcohol copolymer resin film. Then, a gas diffusion base material was disposed on the catalyst layer, and the electrode-electrolyte membrane assembly was produced by pressing at 150 ° C. and 5 MPa for 30 seconds by hot pressing.

実施例２
酸化剤極側の酸素バリア性樹脂フィルムとして、エチレン−ビニルアルコール共重合樹脂フィルム（「ソアノール」、日本合成化学（株）製、厚み２５μｍ）を６０×６０ｍｍサイズの中央の５０×５０ｍｍを切り出し枠状に加工した。 Example 2
As an oxygen barrier resin film on the oxidizer electrode side, an ethylene-vinyl alcohol copolymer resin film ("Soarnol", manufactured by Nippon Synthetic Chemical Co., Ltd., thickness 25 μm) is cut into a 60 × 60 mm center 50 × 50 mm frame. Processed into a shape.

燃料極側の水素バリア性樹脂フィルムとして、スパッタ法（アルバック社製、ＳＨ４００、原料；ＳｉＨ４及びＮ２Ｏ）によりエチレン−ビニルアルコール共重合樹脂（ソアノール、日本合成化学（株）製、厚み２５μｍ）上に酸化珪素膜（平均厚み約１０ｎｍ）を形成することにより得られたフィルムを用いた以外は、実施例１と同様にして、電極−電解質膜接合体を作製した。 As a hydrogen barrier resin film on the fuel electrode side, an ethylene-vinyl alcohol copolymer resin (Soarnol, Nippon Synthetic Chemical Co., Ltd., thickness: 25 μm) is formed by a sputtering method (manufactured by ULVAC, SH400, raw materials; SiH 4 and N 2 O). ) An electrode-electrolyte membrane assembly was prepared in the same manner as in Example 1 except that a film obtained by forming a silicon oxide film (average thickness of about 10 nm) on the top was used.

実施例３
ポリエチレンナフタレート（ＰＥＮ）フィルム（テイジン製、テオネックス、１２μｍ）の片面にＣＶＤ法により酸化アルミニウム（Ａｌ２Ｏ３）皮膜（平均厚み約１０ｎｍ）を蒸着させた後、得られたアルミニウム皮膜フィルムの両面にアンカーコートを施した。次いで、得られたフィルムの両面に、ポリプロピレン（ＣＰＰ）樹脂（三井化学製、「アドマー」）を平均膜厚が９μｍとなるように溶融押し出し法により形成することにより、ガスバリア性樹脂フィルム（ＣＰＰ／アルミニウム皮膜形成ＰＥＮ／ＣＰＰの層構成）を得た。上記ガスバリア性樹脂フィルムを酸化極側のガスバリア性樹脂フィルム及び燃料極側のガスバリア性樹脂フィルムとして使用した。 Example 3
After vapor-depositing an aluminum oxide (Al 2 O 3 ) film (average thickness of about 10 nm) on one side of a polyethylene naphthalate (PEN) film (made by Teijin, Teonex, 12 μm) by the CVD method, both sides of the obtained aluminum film An anchor coat was applied. Next, a polypropylene (CPP) resin (manufactured by Mitsui Chemicals, “Admer”) is formed on both surfaces of the obtained film by a melt extrusion method so as to have an average film thickness of 9 μm, whereby a gas barrier resin film (CPP / A layer structure of aluminum film-forming PEN / CPP) was obtained. The gas barrier resin film was used as a gas barrier resin film on the oxidation electrode side and a gas barrier resin film on the fuel electrode side.

このガスバリア性樹脂フィルムを使用した以外は、実施例１と同様にして、電極−電解質膜接合体を作製した。   An electrode-electrolyte membrane assembly was produced in the same manner as in Example 1 except that this gas barrier resin film was used.

実施例４
アルミニウム皮膜ポリエチレンテレフタレート（ＰＥＴ）フィルム（東洋紡製、「エコシアール ＶＥ５００」、１５μｍ）の両面に、ポリプロピレン（ＣＰＰ）樹脂（三井化学製、「アドマー」）を膜厚が８μｍとなるように溶融押し出し法により形成することにより、ガスバリア性樹脂フィルム（ＣＰＰ／ＰＥＮ／ＣＰＰの層構成）を得た。上記ガスバリア性樹脂フィルムを酸化極側のガスバリア性樹脂フィルム及び燃料極側のガスバリア性樹脂フィルムとして使用した。 Example 4
An aluminum-coated polyethylene terephthalate (PET) film (Toyobo, “Ecosiale VE500”, 15 μm) is fused and extruded with a polypropylene (CPP) resin (Mitsui Chemicals, “Admer”) to a thickness of 8 μm. By forming it, a gas barrier resin film (CPP / PEN / CPP layer structure) was obtained. The gas barrier resin film was used as a gas barrier resin film on the oxidation electrode side and a gas barrier resin film on the fuel electrode side.

このガスバリア性樹脂フィルムを使用した以外は、実施例１と同様にして、電極−電解質膜接合体を作製した。   An electrode-electrolyte membrane assembly was produced in the same manner as in Example 1 except that this gas barrier resin film was used.

比較例１
酸化剤極側及び燃料極側の樹脂フィルムとして、ガスバリア性を持たない二軸延伸ポリプロピレンフィルム（ＦＯＨ、二村化学工業（株）製）を使用した以外は実施例１と同様にして電極−電解質膜接合体を作製した。 Comparative Example 1
The electrode-electrolyte membrane was the same as in Example 1 except that a biaxially stretched polypropylene film (FOH, manufactured by Nimura Chemical Industry Co., Ltd.) having no gas barrier property was used as the resin film on the oxidant electrode side and the fuel electrode side. A joined body was produced.

比較例２
酸化剤極側及び燃料極側の樹脂フィルムとして、ガスバリア性を持たない二軸延伸ナイロンフィルム（ユニロン、出光ユニテック（株）製）を使用した以外は、実施例１と同様にして電極−電解質膜接合体を作製した。 Comparative Example 2
The electrode-electrolyte membrane was the same as in Example 1 except that a biaxially stretched nylon film (Unilon, manufactured by Idemitsu Unitech Co., Ltd.) having no gas barrier property was used as the resin film on the oxidant electrode side and the fuel electrode side. A joined body was produced.

比較例３
ガスバリア性樹脂フィルム等の樹脂フィルムを使用しなかった以外は、実施例１と同様にして触媒層−電解質膜接合体を作製した。 Comparative Example 3
A catalyst layer-electrolyte membrane assembly was produced in the same manner as in Example 1 except that a resin film such as a gas barrier resin film was not used.

試験例
作製した電極−電解質膜接合体を単セルとし１０００時間の連続発電試験を行った。表１に発電開始時及び２０００時間後の開回路電圧の測定結果を示す。 Test Example A 1000-hour continuous power generation test was conducted using the prepared electrode-electrolyte membrane assembly as a single cell. Table 1 shows the measurement results of the open circuit voltage at the start of power generation and after 2000 hours.

Figure 0005130690
Figure 0005130690

図１は、本発明の電極−触媒層接合体の平面図を示す。FIG. 1 shows a plan view of the electrode-catalyst layer assembly of the present invention. 図２は、本発明の電極−触媒層接合体の断面図を示す。FIG. 2 shows a cross-sectional view of the electrode-catalyst layer assembly of the present invention.

Claims (8)

高分子電解質膜の一方面又は両面上に触媒層及びガスバリア性樹脂フィルムが同一の膜厚で形成され、更に触媒層及びガスバリア性樹脂フィルム上にガス拡散基材が形成された電極−電解質膜接合体であって、
前記ガスバリア性樹脂フィルムは、触媒層の外周部に形成されており、
前記ガスバリア性樹脂フィルムは熱接着性樹脂フィルムを含む、
電極−電解質膜接合体。 Electrode-electrolyte membrane bonding in which a catalyst layer and a gas barrier resin film are formed with the same film thickness on one or both surfaces of a polymer electrolyte membrane, and a gas diffusion substrate is further formed on the catalyst layer and the gas barrier resin film Body,
The gas barrier resin film is formed on the outer periphery of the catalyst layer,
The gas barrier resin film includes a thermal adhesive resin film,
Electrode-electrolyte membrane assembly. 前記触媒層及びガスバリア性樹脂フィルムの合計面積とガス拡散基材の面積とが同一である、請求項１に記載の電極−電解質膜接合体。   The electrode-electrolyte membrane assembly according to claim 1, wherein the total area of the catalyst layer and the gas barrier resin film is the same as the area of the gas diffusion base material. 前記ガスバリア性樹脂フィルムが、酸素バリア性樹脂フィルムである、請求項１又は２に記載の電極−電解質膜接合体。   The electrode-electrolyte membrane assembly according to claim 1 or 2, wherein the gas barrier resin film is an oxygen barrier resin film. 前記ガスバリア性樹脂フィルムが、水素バリア性樹脂フィルムである、請求項１又は２に記載の電極−電解質膜接合体。   The electrode-electrolyte membrane assembly according to claim 1 or 2, wherein the gas barrier resin film is a hydrogen barrier resin film. ガスバリア性樹脂フィルムが少なくとも２層の樹脂フィルムで構成されている、請求項１〜４のいずれかに記載の電極−電解質膜接合体。   The electrode-electrolyte membrane assembly according to any one of claims 1 to 4, wherein the gas barrier resin film is composed of at least two resin films. ガスバリア性樹脂フィルムは、熱接着性樹脂フィルム／酸素バリア性樹脂フィルム又は水素バリア性樹脂フィルム／熱接着性樹脂フィルムの少なくとも３層で構成されている、請求項５に記載の電極−電解質膜接合体。   The electrode-electrolyte membrane bonding according to claim 5, wherein the gas barrier resin film is composed of at least three layers of a thermal adhesive resin film / oxygen barrier resin film or a hydrogen barrier resin film / thermal adhesive resin film. body. （１）電解質膜上に触媒層が積層された触媒層−電解質膜積層体上にある当該触媒層の外周部にガスバリア性樹脂フィルムを配置し、
（２）当該触媒層及びガスバリア性樹脂フィルム上にガス拡散基材を配置し、熱プレスする、
ことにより得られる、電極−電解質膜接合体。 (1) Catalyst layer in which a catalyst layer is laminated on an electrolyte membrane-Disposing a gas barrier resin film on the outer periphery of the catalyst layer on the electrolyte membrane laminate,
(2) A gas diffusion base material is disposed on the catalyst layer and the gas barrier resin film and hot pressed.
The electrode-electrolyte membrane assembly obtained by this. （１）電解質膜上に触媒層が積層された触媒層−電解質膜積層体上にある当該触媒層の外周部にガスバリア性樹脂フィルムを配置する工程、及び
（２）当該触媒層及びガスバリア性樹脂フィルム上にガス拡散基材を配置し、熱プレスする工程、
を備えた電極−電解質接合体の製造方法。 (1) a catalyst layer having a catalyst layer laminated on an electrolyte membrane—a step of disposing a gas barrier resin film on the outer periphery of the catalyst layer on the electrolyte membrane laminate; and (2) the catalyst layer and the gas barrier resin. Placing a gas diffusion substrate on the film and hot pressing,
A method for producing an electrode-electrolyte assembly comprising:
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