JP5912942B2 - Electrolyte membrane / electrode structure with resin frame and fuel cell - Google Patents

Electrolyte membrane / electrode structure with resin frame and fuel cell Download PDF

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JP5912942B2
JP5912942B2 JP2012154615A JP2012154615A JP5912942B2 JP 5912942 B2 JP5912942 B2 JP 5912942B2 JP 2012154615 A JP2012154615 A JP 2012154615A JP 2012154615 A JP2012154615 A JP 2012154615A JP 5912942 B2 JP5912942 B2 JP 5912942B2
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electrolyte membrane
gas diffusion
electrode
diffusion layer
recess
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JP2014017150A (en
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満田　直樹
直樹 満田
相馬　浩
浩 相馬
之人 田中
之人 田中
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Honda Motor 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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本発明は、段差電解質膜・電極構造体と樹脂製枠部材とを備える樹脂枠付き電解質膜・電極構造体及び燃料電池に関する。   The present invention relates to an electrolyte membrane / electrode structure with a resin frame comprising a stepped electrolyte membrane / electrode structure and a resin frame member, and a fuel cell.

一般的に、固体高分子型燃料電池は、高分子イオン交換膜からなる固体高分子電解質膜を採用している。この燃料電池は、固体高分子電解質膜の両側に、それぞれ触媒層（電極触媒層）とガス拡散層（多孔質カーボン）とからなるアノード電極及びカソード電極を配設した電解質膜・電極構造体（ＭＥＡ）を、セパレータ（バイポーラ板）によって挟持している。この燃料電池は、所定の数だけ積層して燃料電池スタックを構成するとともに、例えば、車載用燃料電池スタックとして使用されている。   In general, a polymer electrolyte fuel cell employs a polymer electrolyte membrane made of a polymer ion exchange membrane. This fuel cell comprises an electrolyte membrane / electrode structure in which an anode electrode and a cathode electrode each comprising a catalyst layer (electrode catalyst layer) and a gas diffusion layer (porous carbon) are disposed on both sides of a solid polymer electrolyte membrane ( MEA) is sandwiched between separators (bipolar plates). A predetermined number of fuel cells are stacked to form a fuel cell stack, and the fuel cell is used as, for example, an in-vehicle fuel cell stack.

この種の電解質膜・電極構造体では、一方のガス拡散層が固体高分子電解質膜よりも小さな表面積に設定されるとともに、他方のガス拡散層が前記固体高分子電解質膜と同一の表面積に設定される、所謂、段差ＭＥＡを構成する場合がある。その際、比較的高価な固体高分子電解質膜の使用量を削減させるとともに、薄膜状で強度が低い前記固体高分子電解質膜を保護するために、樹脂製枠部材を組み込んだ枠付きＭＥＡが採用されている。   In this type of electrolyte membrane / electrode structure, one gas diffusion layer is set to have a smaller surface area than the solid polymer electrolyte membrane, and the other gas diffusion layer is set to the same surface area as the solid polymer electrolyte membrane. The so-called step MEA may be configured. At that time, in order to reduce the amount of the relatively expensive solid polymer electrolyte membrane used, and to protect the solid polymer electrolyte membrane having a thin film shape and low strength, an MEA with a frame incorporating a resin frame member is adopted. Has been.

例えば、特許文献１に開示されている電解質膜−電極接合体が知られている。この電解質膜−電極接合体では、図１６に示すように、膜１の一方の側には、アノード触媒層２ａとアノード拡散層２ｂとが配置されるとともに、前記膜１の他方の側には、カソード触媒層３ａとカソード拡散層３ｂとが配置されて段差ＭＥＡ４が構成されている。   For example, an electrolyte membrane-electrode assembly disclosed in Patent Document 1 is known. In this electrolyte membrane-electrode assembly, as shown in FIG. 16, an anode catalyst layer 2a and an anode diffusion layer 2b are arranged on one side of the membrane 1, and on the other side of the membrane 1. The step catalyst MEA 4 is configured by arranging the cathode catalyst layer 3a and the cathode diffusion layer 3b.

アノード拡散層２ｂは、カソード拡散層３ｂよりも大きな面積に設定されており、前記カソード拡散層３ｂ側の膜１の外周部とガスケット構造体５の内周突部５ａとは、接着層６を介して接合されている。   The anode diffusion layer 2b is set to have a larger area than the cathode diffusion layer 3b, and the outer peripheral portion of the film 1 on the cathode diffusion layer 3b side and the inner peripheral protrusion 5a of the gasket structure 5 form the adhesive layer 6. Are joined through.

特開２００７−６６７６６号公報JP 2007-66766 A

ところで、上記の特許文献１では、段差ＭＥＡ４とガスケット構造体５とが、接着層６を介して接合される際、前記ＭＥＡ４と前記ガスケット構造体５との隙間から前記接着層６がはみ出すおそれがある。このため、電解質膜−電極接合体の表面には、例えば、はみ出し接着剤６ａ、６ｂが設けられてしまう。従って、はみ出し接着剤６ａ、６ｂを除去する作業が必要になり、段差ＭＥＡ４とガスケット構造体５との接合作業が煩雑化するとともに、作業性が低下するという問題がある。   By the way, in the above Patent Document 1, when the step MEA 4 and the gasket structure 5 are joined via the adhesive layer 6, the adhesive layer 6 may protrude from the gap between the MEA 4 and the gasket structure 5. is there. For this reason, for example, the protruding adhesives 6a and 6b are provided on the surface of the electrolyte membrane-electrode assembly. Therefore, it is necessary to remove the protruding adhesives 6a and 6b, which complicates the joining operation of the step MEA 4 and the gasket structure 5 and reduces the workability.

本発明は、この種の問題を解決するものであり、簡単且つ経済的な構成で、接着剤が外部にはみ出すことを良好に抑制することができ、作業性を向上させることが可能な樹脂枠付き電解質膜・電極構造体及び燃料電池を提供することを目的とする。   The present invention solves this type of problem, and with a simple and economical configuration, can effectively suppress the adhesive from protruding to the outside, and can improve the workability. It is an object of the present invention to provide an attached electrolyte membrane / electrode structure and a fuel cell.

本発明は、固体高分子電解質膜の一方の面に、第１触媒層及び第１ガス拡散層を有する第１電極が配設され、且つ前記固体高分子電解質膜の他方の面に、第２触媒層及び第２ガス拡散層を有する第２電極が配設されるとともに、前記第１ガス拡散層の平面寸法は、前記第２ガス拡散層の平面寸法よりも大きな寸法に設定される段差電解質膜・電極構造体と、前記固体高分子電解質膜の外周を周回する枠形状を有しており、段部を介し最外周部よりも薄肉状に形成されて前記第２ガス拡散層側に突出する内周突部が設けられる樹脂製枠部材とを備える樹脂枠付き電解質膜・電極構造体及び前記樹脂枠付き電解質膜・電極構造体が組み込まれる燃料電池に関するものである。   In the present invention, a first electrode having a first catalyst layer and a first gas diffusion layer is disposed on one surface of a solid polymer electrolyte membrane, and a second electrode is disposed on the other surface of the solid polymer electrolyte membrane. A step electrolyte in which a second electrode having a catalyst layer and a second gas diffusion layer is disposed, and a planar dimension of the first gas diffusion layer is set to be larger than a planar dimension of the second gas diffusion layer It has a frame shape that circulates around the outer periphery of the membrane / electrode structure and the solid polymer electrolyte membrane, and is formed thinner than the outermost peripheral part via the step part and protrudes toward the second gas diffusion layer side The present invention relates to an electrolyte membrane / electrode structure with a resin frame provided with a resin-made frame member provided with an inner peripheral projection, and a fuel cell in which the electrolyte membrane / electrode structure with a resin frame is incorporated.

樹脂枠付き電解質膜・電極構造体では、段差電解質膜・電極構造体の段差部側と樹脂製枠部材の段部側とは、接着剤により互いに固定されるとともに、前記段差部と前記段部との境界部位には、前記接着剤を溜めるための凹部が設けられている。   In the electrolyte membrane / electrode structure with a resin frame, the step portion side of the step electrolyte membrane / electrode structure and the step portion side of the resin frame member are fixed to each other by an adhesive, and the step portion and the step portion A recess for storing the adhesive is provided at the boundary portion.

また、この樹脂枠付き電解質膜・電極構造体では、凹部は、樹脂製枠部材の内周突部の端面に、第２ガス拡散層に対向して設けられるとともに、前記内周突部の内周に沿って周回する第１凹部と、前記内周突部の平面部に、前記第２ガス拡散層の端部から外方に露出する固体高分子電解質膜に対向して設けられるとともに、前記第１凹部よりも外側で前記段部に沿って周回する第２凹部とを有する。 Further, in this electrolyte membrane / electrode structure with a resin frame, the recess is provided on the end surface of the inner peripheral protrusion of the resin frame member so as to face the second gas diffusion layer, and the inner periphery of the inner peripheral protrusion A first concave portion that circulates along a circumference, and a flat portion of the inner circumferential protrusion, provided opposite to the solid polymer electrolyte membrane exposed outward from the end of the second gas diffusion layer , and that having a second recess circulating along said stepped portion on the outside than the first recess.

本発明によれば、段差電解質膜・電極構造体の段差部側と樹脂製枠部材の段部側とが、接着剤により互いに固定される際、前記接着剤は、前記段差部と前記段部との境界部位に沿って移動し、凹部に溜められる。このため、接着剤は、樹脂枠付き電解質膜・電極構造体の外部に漏れ出すことがない。   According to the present invention, when the stepped portion side of the stepped electrolyte membrane / electrode structure and the stepped portion side of the resin frame member are fixed to each other by the adhesive, the adhesive is separated from the stepped portion and the stepped portion. It moves along the boundary part and is stored in the recess. For this reason, the adhesive does not leak out of the electrolyte membrane / electrode structure with a resin frame.

従って、段差部と段部との境界部位に凹部を設けるだけでよい。これにより、簡単且つ経済的な構成で、接着剤が外部にはみ出すことを良好に抑制することができ、作業性を向上させることが可能になる。   Therefore, it is only necessary to provide a recess at the boundary between the stepped portion and the stepped portion. Thereby, it is possible to satisfactorily suppress the adhesive from protruding to the outside with a simple and economical configuration, and to improve workability.

本発明の実施形態に係る樹脂枠付き電解質膜・電極構造体が組み込まれる固体高分子型燃料電池の要部分解斜視説明図である。 Implementation according to the resin frame equipped membrane electrode assembly of the present invention is an exploded perspective view showing main components of a solid polymer electrolyte fuel cell to be incorporated. 前記燃料電池の、図１中、ＩＩ−ＩＩ線断面説明図である。FIG. 2 is a sectional view of the fuel cell taken along line II-II in FIG. 1. 前記樹脂枠付き電解質膜・電極構造体のカソード電極側の正面説明図である。It is front explanatory drawing by the side of the cathode electrode of the said electrolyte membrane-electrode structure with a resin frame. 前記樹脂枠付き電解質膜・電極構造体を製造する方法の説明図である。It is explanatory drawing of the method to manufacture the said electrolyte membrane-electrode structure with a resin frame. 前記樹脂枠付き電解質膜・電極構造体を製造する方法の説明図である。It is explanatory drawing of the method to manufacture the said electrolyte membrane-electrode structure with a resin frame. 第１参考例に係る樹脂枠付き電解質膜・電極構造体が組み込まれる固体高分子型燃料電池の要部断面説明図である。It is principal part cross-sectional explanatory drawing of the polymer electrolyte fuel cell in which the electrolyte membrane and electrode structure with a resin frame concerning a 1st reference example is integrated. 第２参考例に係る樹脂枠付き電解質膜・電極構造体が組み込まれる固体高分子型燃料電池の要部断面説明図である。It is principal part cross-sectional explanatory drawing of the polymer electrolyte fuel cell in which the electrolyte membrane and electrode structure with a resin frame concerning a 2nd reference example is integrated. 別の凹部の形状を示す説明図である。It is explanatory drawing which shows the shape of another recessed part. また別の凹部の形状を示す説明図である。It is explanatory drawing which shows the shape of another recessed part. さらに別の凹部の形状を示す説明図である。It is explanatory drawing which shows the shape of another recessed part. さらにまた別の凹部の形状を示す説明図である。It is explanatory drawing which shows the shape of another recessed part. 他の凹部の形状を示す説明図である。It is explanatory drawing which shows the shape of another recessed part. また他の凹部の形状を示す説明図である。It is explanatory drawing which shows the shape of another recessed part. さらに他の凹部の形状を示す説明図である。It is explanatory drawing which shows the shape of another recessed part. さらにまた他の凹部の形状を示す説明図である。Furthermore, it is explanatory drawing which shows the shape of another recessed part. 特許文献１に開示された電解質膜−電極接合体の説明図である。6 is an explanatory diagram of an electrolyte membrane-electrode assembly disclosed in Patent Document 1. FIG.

図１及び図２に示すように、本発明の実施形態に係る樹脂枠付き電解質膜・電極構造体１０は、固体高分子型燃料電池１２に組み込まれる。燃料電池１２は、矢印Ａ方向（例えば、水平方向）に複数積層されることにより、例えば、車載用燃料電池スタックが構成される。 As shown in FIGS. 1 and 2, the resin frame equipped membrane electrode assembly 10 according to the implementation embodiments of the present invention is incorporated in a polymer electrolyte fuel cell 12. For example, an in-vehicle fuel cell stack is configured by stacking a plurality of fuel cells 12 in the direction of arrow A (for example, the horizontal direction).

燃料電池１２は、樹脂枠付き電解質膜・電極構造体１０を第１セパレータ１４及び第２セパレータ１６で挟持する。第１セパレータ１４及び第２セパレータ１６は、例えば、鋼板、ステンレス鋼板、アルミニウム板、めっき処理鋼板、あるいはその金属表面に防食用の表面処理を施した金属板や、カーボン部材等で構成されている。   In the fuel cell 12, the electrolyte membrane / electrode structure 10 with a resin frame is sandwiched between the first separator 14 and the second separator 16. The first separator 14 and the second separator 16 are made of, for example, a steel plate, a stainless steel plate, an aluminum plate, a plated steel plate, a metal plate whose surface is subjected to anticorrosion treatment, a carbon member, or the like. .

図２に示すように、樹脂枠付き電解質膜・電極構造体１０は、段差電解質膜・電極構造体１０ａを備える。段差電解質膜・電極構造体１０ａは、例えば、パーフルオロスルホン酸の薄膜に水が含浸された固体高分子電解質膜１８と、前記固体高分子電解質膜１８を挟持するカソード電極（第１電極）２０及びアノード電極（第２電極）２２とを有する。固体高分子電解質膜１８は、フッ素系電解質の他、ＨＣ（炭化水素）系電解質が使用される。   As shown in FIG. 2, the electrolyte membrane / electrode structure 10 with a resin frame includes a stepped electrolyte membrane / electrode structure 10a. The step electrolyte membrane / electrode structure 10a includes, for example, a solid polymer electrolyte membrane 18 in which a perfluorosulfonic acid thin film is impregnated with water, and a cathode electrode (first electrode) 20 sandwiching the solid polymer electrolyte membrane 18. And an anode electrode (second electrode) 22. The solid polymer electrolyte membrane 18 uses an HC (hydrocarbon) electrolyte in addition to a fluorine electrolyte.

アノード電極２２は、固体高分子電解質膜１８及びカソード電極２０よりも小さな平面寸法（表面積）を有する。なお、アノード電極２２とカソード電極２０の平面寸法の大小関係が反対になって、前記カソード電極２０は、前記アノード電極２２よりも小さな平面寸法（表面積）を有していてもよい。   The anode electrode 22 has a smaller planar dimension (surface area) than the solid polymer electrolyte membrane 18 and the cathode electrode 20. In addition, the magnitude relationship of the planar dimensions of the anode electrode 22 and the cathode electrode 20 may be reversed, and the cathode electrode 20 may have a smaller planar dimension (surface area) than the anode electrode 22.

カソード電極２０は、固体高分子電解質膜１８の一方の面１８ａに配置されるとともに、アノード電極２２は、前記固体高分子電解質膜１８の他方の面１８ｂに配置される。   The cathode electrode 20 is disposed on one surface 18 a of the solid polymer electrolyte membrane 18, and the anode electrode 22 is disposed on the other surface 18 b of the solid polymer electrolyte membrane 18.

カソード電極２０は、固体高分子電解質膜１８の面１８ａに接合される第１電極触媒層（第１触媒層）２０ａと、前記第１電極触媒層２０ａに積層される第１ガス拡散層２０ｂとを有する。第１電極触媒層２０ａと第１ガス拡散層２０ｂとは、同一の平面寸法に設定される。   The cathode electrode 20 includes a first electrode catalyst layer (first catalyst layer) 20a joined to the surface 18a of the solid polymer electrolyte membrane 18, and a first gas diffusion layer 20b laminated on the first electrode catalyst layer 20a. Have The first electrode catalyst layer 20a and the first gas diffusion layer 20b are set to have the same planar dimensions.

アノード電極２２は、固体高分子電解質膜１８の面１８ｂに接合される第２電極触媒層（第２触媒層）２２ａと、前記第２電極触媒層２２ａに積層される第２ガス拡散層２２ｂとを有する。第２電極触媒層２２ａと第２ガス拡散層２２ｂとは、同一の平面寸法に設定される。第１電極触媒層２０ａは、第２電極触媒層２２ａよりも大きな平面寸法を有しているが、前記第１電極触媒層２０ａは、前記第２電極触媒層２２ａと、同一の平面寸法に設定されてもよい。   The anode electrode 22 includes a second electrode catalyst layer (second catalyst layer) 22a joined to the surface 18b of the solid polymer electrolyte membrane 18, and a second gas diffusion layer 22b laminated on the second electrode catalyst layer 22a. Have The second electrode catalyst layer 22a and the second gas diffusion layer 22b are set to have the same planar dimensions. The first electrode catalyst layer 20a has a larger planar dimension than the second electrode catalyst layer 22a, but the first electrode catalyst layer 20a is set to have the same planar dimension as the second electrode catalyst layer 22a. May be.

第１電極触媒層２０ａ及び第２電極触媒層２２ａは、カーボンブラックに白金粒子を担持した触媒粒子と、イオン導伝性バインダーとして高分子電解質を使用し、この高分子電解質の溶液中に前記触媒粒子を均一に混合して作製された触媒ペーストを、固体高分子電解質膜１８の両方の面１８ａ、１８ｂに印刷、塗布又は転写することによって構成される。   The first electrode catalyst layer 20a and the second electrode catalyst layer 22a use catalyst particles in which platinum particles are supported on carbon black and a polymer electrolyte as an ion conductive binder, and the catalyst is contained in a solution of the polymer electrolyte. The catalyst paste prepared by uniformly mixing the particles is configured by printing, applying or transferring the catalyst paste on both surfaces 18a and 18b of the solid polymer electrolyte membrane 18.

第１ガス拡散層２０ｂ及び第２ガス拡散層２２ｂは、カーボンブラック及びＰＴＦＥ（ポリテトラフルオロエチレン）粒子を含む下地層をカーボンペーパの膜側に塗布して形成される。下地層は、カーボンペーパと同じ表面寸法に設定されている。なお、下地層は、必要に応じて設ければよい。また、カソード電極２０及びアノード電極２２は、上記の各層以外の層を有していてもよい。第１ガス拡散層２０ｂの平面寸法は、第２ガス拡散層２２ｂの平面寸法よりも大きな寸法に設定される。段差電解質膜・電極構造体１０ａは、第２ガス拡散層２２ｂの端部外方に、固体高分子電解質膜１８が露呈する段差部２３を有する。   The first gas diffusion layer 20b and the second gas diffusion layer 22b are formed by applying a base layer containing carbon black and PTFE (polytetrafluoroethylene) particles to the film side of the carbon paper. The underlayer has the same surface dimensions as the carbon paper. In addition, what is necessary is just to provide a base layer as needed. Moreover, the cathode electrode 20 and the anode electrode 22 may have layers other than said each layer. The planar dimension of the first gas diffusion layer 20b is set to be larger than the planar dimension of the second gas diffusion layer 22b. The step electrolyte membrane / electrode structure 10a has a step portion 23 where the solid polymer electrolyte membrane 18 is exposed outside the end of the second gas diffusion layer 22b.

図１及び図２に示すように、樹脂枠付き電解質膜・電極構造体１０は、固体高分子電解質膜１８の外周を周回するとともに、アノード電極２２及びカソード電極２０に接合される樹脂製枠部材２４を備える。樹脂製枠部材２４の両側面とカソード電極２０の側面及びアノード電極２２の側面とは、矢印Ｃ方向に沿って段差のない平坦な形状に設定される。   As shown in FIGS. 1 and 2, the electrolyte membrane / electrode structure 10 with a resin frame circulates around the outer periphery of the solid polymer electrolyte membrane 18 and is joined to the anode electrode 22 and the cathode electrode 20. 24. Both side surfaces of the resin frame member 24, the side surfaces of the cathode electrode 20, and the side surfaces of the anode electrode 22 are set to have a flat shape with no step along the arrow C direction.

樹脂製枠部材２４は、例えば、ＰＰＳ（ポリフェニレンサルファイド）、ＰＰＡ（ポリフタルアミド）、ＰＥＮ（ポリエチレンナフタレート）、ＰＥＳ（ポリエーテルサルフォン）、ＬＣＰ（リキッドクリスタルポリマー）、ＰＶＤＦ（ポリフッ化ビニリデン）、シリコーンゴム、ＰＰ（ポリプロピレン）、ＰＥ（ポリエチレン）、フッ素ゴム又はＥＰＤＭ（エチレンプロピレンゴム）等で構成される。   The resin frame member 24 is, for example, PPS (polyphenylene sulfide), PPA (polyphthalamide), PEN (polyethylene naphthalate), PES (polyethersulfone), LCP (liquid crystal polymer), PVDF (polyvinylidene fluoride). , Silicone rubber, PP (polypropylene), PE (polyethylene), fluorine rubber or EPDM (ethylene propylene rubber).

樹脂製枠部材２４は、枠形状を有するとともに、段部２５を介して最外周部よりも薄肉状に形成され、アノード電極２２の外周側に突出して固体高分子電解質膜１８の外周縁部１８ｂｅに当接する内周突部２４ａを有する。固体高分子電解質膜１８の外周縁部１８ｂｅは、アノード電極２２を構成する第２ガス拡散層２２ｂの外周端から外方に延在する。   The resin frame member 24 has a frame shape and is formed thinner than the outermost peripheral portion via the step portion 25, protrudes to the outer peripheral side of the anode electrode 22, and the outer peripheral edge portion 18 be of the solid polymer electrolyte membrane 18. Has an inner circumferential protrusion 24a. The outer peripheral edge portion 18be of the solid polymer electrolyte membrane 18 extends outward from the outer peripheral end of the second gas diffusion layer 22b constituting the anode electrode 22.

内周突部２４ａは、アノード電極２２と同一の肉厚を有する。固体高分子電解質膜１８及びカソード電極２０の合計の厚さは、樹脂製枠部材２４の段部２５の厚さ（樹脂製枠部材２４の厚さから内周突部２４ａの厚さを引いた寸法）と同一の厚さに設定される。   The inner peripheral protrusion 24 a has the same thickness as the anode electrode 22. The total thickness of the solid polymer electrolyte membrane 18 and the cathode electrode 20 is the thickness of the step portion 25 of the resin frame member 24 (the thickness of the inner peripheral projection 24a is subtracted from the thickness of the resin frame member 24). Dimension) is set to the same thickness.

段差電解質膜・電極構造体１０ａの段差部２３側、例えば、固体高分子電解質膜１８の外周縁部１８ｂｅと、樹脂製枠部材２４の段部２５側、例えば、内周突部２４ａとは、接着層２６により互いに固定される。接着層２６は、反応性の液状接着剤や常温で固形状のホットメルト接着剤等が使用される。   The stepped portion 23 side of the stepped electrolyte membrane / electrode structure 10a, for example, the outer peripheral edge 18be of the solid polymer electrolyte membrane 18, and the stepped portion 25 side of the resin frame member 24, for example, the inner peripheral protrusion 24a, They are fixed to each other by the adhesive layer 26. For the adhesive layer 26, a reactive liquid adhesive, a hot melt adhesive that is solid at room temperature, or the like is used.

反応性液状接着剤としては、例えば、シリコーン系接着剤、ウレタン系、フッ素系又はエポキシ系の接着剤が使用される。ホットメルト接着剤としては、例えば、ウレタン系、エステル系、エポキシ系、アミド系又はオレフィン系の接着剤が使用される。接着剤の塗工方法としては、スプレー、ディスペンサー、スクリーン印刷、インクジェット又は浸漬等の種々の方法が採用される。   As the reactive liquid adhesive, for example, a silicone-based adhesive, urethane-based, fluorine-based, or epoxy-based adhesive is used. As the hot melt adhesive, for example, urethane, ester, epoxy, amide, or olefin adhesives are used. As a method for applying the adhesive, various methods such as spraying, dispenser, screen printing, ink jetting or dipping are employed.

段差部２３と段部２５との境界部位には、上記の接着剤を溜めるための凹部２８が設けられる。凹部２８は、樹脂製枠部材２４の内周突部２４ａの端面に、第２ガス拡散層２２ｂに対向して設けられる第１凹部２８ａと、前記内周突部２４ａの内側平面（平面部）２４ａｓに、前記第２ガス拡散層２２ｂの端部から外方に露出する固体高分子電解質膜１８の外周縁部１８ｂｅの先端縁部に対向して設けられる第２凹部２８ｂとを有する。   A concave portion 28 for storing the adhesive is provided at a boundary portion between the step portion 23 and the step portion 25. The recess 28 includes a first recess 28a provided on the end surface of the inner peripheral projection 24a of the resin frame member 24 so as to face the second gas diffusion layer 22b, and an inner plane (planar portion) of the inner peripheral projection 24a. 24 a has a second recess 28 b provided facing the tip edge of the outer peripheral edge 18 be of the solid polymer electrolyte membrane 18 exposed outward from the end of the second gas diffusion layer 22 b.

第１凹部２８ａ及び第２凹部２８ｂは、開口断面矩形状を有するとともに、接着層２６の両端に設けられる。第１凹部２８ａは、樹脂製枠部材２４の内周突部２４ａの端面を周回する額縁形状を有する。第２凹部２８ｂは、図２及び図３に示すように、内周突部２４ａの基端縁部（段部２５を形成する壁面の近傍）を周回する額縁形状を有する。   The first recess 28 a and the second recess 28 b have a rectangular opening cross section and are provided at both ends of the adhesive layer 26. The first recess 28 a has a frame shape that goes around the end face of the inner peripheral protrusion 24 a of the resin frame member 24. As shown in FIGS. 2 and 3, the second recess 28 b has a frame shape that circulates around the base end edge portion (in the vicinity of the wall surface forming the step portion 25) of the inner circumferential protrusion 24 a.

図１に示すように、燃料電池１２の矢印Ｂ方向（図１中、水平方向）の一端縁部には、積層方向である矢印Ａ方向に互いに連通して、酸化剤ガス、例えば、酸素含有ガスを供給するための酸化剤ガス入口連通孔３０ａ、冷却媒体を供給するための冷却媒体入口連通孔３２ａ、及び燃料ガス、例えば、水素含有ガスを排出するための燃料ガス出口連通孔３４ｂが、矢印Ｃ方向（鉛直方向）に配列して設けられる。   As shown in FIG. 1, one end edge of the fuel cell 12 in the arrow B direction (horizontal direction in FIG. 1) communicates with each other in the arrow A direction, which is the stacking direction, and contains an oxidant gas, for example, oxygen An oxidant gas inlet communication hole 30a for supplying gas, a cooling medium inlet communication hole 32a for supplying a cooling medium, and a fuel gas outlet communication hole 34b for discharging a fuel gas, for example, a hydrogen-containing gas, Arranged in the direction of arrow C (vertical direction).

燃料電池１２の矢印Ｂ方向の他端縁部には、矢印Ａ方向に互いに連通して、燃料ガスを供給するための燃料ガス入口連通孔３４ａ、冷却媒体を排出するための冷却媒体出口連通孔３２ｂ、及び酸化剤ガスを排出するための酸化剤ガス出口連通孔３０ｂが、矢印Ｃ方向に配列して設けられる。   The other end edge of the fuel cell 12 in the direction of arrow B communicates with each other in the direction of arrow A, a fuel gas inlet communication hole 34a for supplying fuel gas, and a cooling medium outlet communication hole for discharging the cooling medium. 32b and an oxidant gas outlet communication hole 30b for discharging the oxidant gas are arranged in the direction of arrow C.

第２セパレータ１６の樹脂枠付き電解質膜・電極構造体１０に向かう面１６ａには、酸化剤ガス入口連通孔３０ａと酸化剤ガス出口連通孔３０ｂとに連通する酸化剤ガス流路３６が設けられる。   An oxidant gas flow path 36 communicating with the oxidant gas inlet communication hole 30a and the oxidant gas outlet communication hole 30b is provided on the surface 16a of the second separator 16 facing the electrolyte membrane / electrode structure 10 with a resin frame. .

第１セパレータ１４の樹脂枠付き電解質膜・電極構造体１０に向かう面１４ａには、燃料ガス入口連通孔３４ａと燃料ガス出口連通孔３４ｂとに連通する燃料ガス流路３８が形成される。第１セパレータ１４の面１４ｂと第２セパレータ１６の面１６ｂとの間には、冷却媒体入口連通孔３２ａと冷却媒体出口連通孔３２ｂとに連通する冷却媒体流路４０が形成される。   A fuel gas flow path 38 communicating with the fuel gas inlet communication hole 34a and the fuel gas outlet communication hole 34b is formed on the surface 14a of the first separator 14 facing the electrolyte membrane / electrode structure 10 with a resin frame. Between the surface 14 b of the first separator 14 and the surface 16 b of the second separator 16, a cooling medium flow path 40 communicating with the cooling medium inlet communication hole 32 a and the cooling medium outlet communication hole 32 b is formed.

図１及び図２に示すように、第１セパレータ１４の面１４ａ、１４ｂには、この第１セパレータ１４の外周端部を周回して、第１シール部材４２が一体化される。第２セパレータ１６の面１６ａ、１６ｂには、この第２セパレータ１６の外周端部を周回して、第２シール部材４４が一体化される。   As shown in FIGS. 1 and 2, the first seal member 42 is integrated with the surfaces 14 a and 14 b of the first separator 14 around the outer peripheral end of the first separator 14. The second seal member 44 is integrated with the surfaces 16 a and 16 b of the second separator 16 around the outer peripheral end portion of the second separator 16.

図２に示すように、第１シール部材４２は、樹脂枠付き電解質膜・電極構造体１０を構成する樹脂製枠部材２４の内周突部２４ａに当接する第１凸状シール４２ａと、第２セパレータ１６の第２シール部材４４に当接する第２凸状シール４２ｂとを有する。第２シール部材４４は、第２凸状シール４２ｂに当接する面が平面を有する平面シールを構成する。なお、第２凸状シール４２ｂに代えて、第２シール部材４４に凸状シール（図示せず）を設けてもよい。   As shown in FIG. 2, the first seal member 42 includes a first convex seal 42 a that contacts the inner peripheral protrusion 24 a of the resin frame member 24 constituting the electrolyte membrane / electrode structure 10 with resin frame, And a second convex seal 42b in contact with the second seal member 44 of the two separator 16. The second seal member 44 constitutes a flat seal having a flat surface that contacts the second convex seal 42b. Instead of the second convex seal 42b, the second seal member 44 may be provided with a convex seal (not shown).

第１及び第２シール部材４２、４４には、例えば、ＥＰＤＭ、ＮＢＲ、フッ素ゴム、シリコーンゴム、フロロシリコーンゴム、ブチルゴム、天然ゴム、スチレンゴム、クロロプレーン又はアクリルゴム等のシール材、クッション材、あるいはパッキン材等の弾性を有するシール部材が用いられる。   The first and second sealing members 42 and 44 include, for example, EPDM, NBR, fluorine rubber, silicone rubber, fluorosilicone rubber, butyl rubber, natural rubber, styrene rubber, chloroprene or acrylic rubber, a cushioning material, Alternatively, an elastic seal member such as a packing material is used.

図１に示すように、第１セパレータ１４には、燃料ガス入口連通孔３４ａを燃料ガス流路３８に連通する供給孔部４６と、前記燃料ガス流路３８を燃料ガス出口連通孔３４ｂに連通する排出孔部４８とが形成される。   As shown in FIG. 1, the first separator 14 has a supply hole portion 46 that communicates the fuel gas inlet communication hole 34a with the fuel gas passage 38, and the fuel gas passage 38 communicates with the fuel gas outlet communication hole 34b. A discharge hole 48 is formed.

次いで、樹脂枠付き電解質膜・電極構造体１０を製造する方法について、以下に説明する。   Next, a method for producing the resin frame-attached electrolyte membrane / electrode structure 10 will be described below.

先ず、図４に示すように、段差ＭＥＡである段差電解質膜・電極構造体１０ａが作製される。具体的には、触媒と溶媒との混合物にイオン導電性バインダー溶液を投入し、所定のインク粘度まで混合した電極インクを、ＰＥＴフィルムからなるＰＥＴシートにスクリーン印刷により塗工した電極シートを形成し、前記電極シート間に固体高分子電解質膜１８を挟持してホットプレスを行う。その後、ＰＥＴシートを剥がすことにより、固体高分子電解質膜１８の面１８ａ及び面１８ｂには、第１電極触媒層２０ａ及び第２電極触媒層２２ａが形成される。   First, as shown in FIG. 4, a step electrolyte membrane / electrode structure 10a which is a step MEA is manufactured. Specifically, an ion conductive binder solution is put into a mixture of a catalyst and a solvent, and an electrode sheet is formed by applying electrode ink mixed to a predetermined ink viscosity to a PET sheet made of a PET film by screen printing. The solid polymer electrolyte membrane 18 is sandwiched between the electrode sheets and hot pressing is performed. Then, the first electrode catalyst layer 20a and the second electrode catalyst layer 22a are formed on the surface 18a and the surface 18b of the solid polymer electrolyte membrane 18 by peeling the PET sheet.

さらに、第１ガス拡散層２０ｂ及び第２ガス拡散層２２ｂの製造工程では、カーボンブラック及びＰＴＦＥ（ポリテトラフルオロエチレン）粒子を含む混合物をエチレングリコールに均一に分散させたスラリーが形成される。このスラリーは、カーボンペーパに塗布して乾燥されることにより、前記カーボンペーパに下地層が設けられた第１ガス拡散層２０ｂ及び第２ガス拡散層２２ｂが作製される。   Furthermore, in the manufacturing process of the first gas diffusion layer 20b and the second gas diffusion layer 22b, a slurry in which a mixture containing carbon black and PTFE (polytetrafluoroethylene) particles is uniformly dispersed in ethylene glycol is formed. The slurry is applied to carbon paper and dried to produce a first gas diffusion layer 20b and a second gas diffusion layer 22b in which a base layer is provided on the carbon paper.

そこで、固体高分子電解質膜１８の面１８ａ側に、すなわち、第１電極触媒層２０ａに第１ガス拡散層２０ｂが配置されるとともに、前記固体高分子電解質膜１８の面１８ｂに、すなわち、第２電極触媒層２２ａに第２ガス拡散層２２ｂが配置される。これらが一体に積層されてホットプレス処理されることにより、段差電解質膜・電極構造体１０ａが作製される。   Therefore, the first gas diffusion layer 20b is disposed on the surface 18a side of the solid polymer electrolyte membrane 18, that is, the first electrode catalyst layer 20a, and the first polymer gas diffusion layer 20b is disposed on the surface 18b of the solid polymer electrolyte membrane 18. The second gas diffusion layer 22b is disposed on the two-electrode catalyst layer 22a. The step electrolyte membrane / electrode structure 10a is manufactured by stacking these together and performing hot pressing.

一方、樹脂製枠部材２４は、金型（図示せず）を用いて射出成形することにより、予め成形される。樹脂製枠部材２４は、最外周部よりも肉薄形状の内周突部２４ａを有するとともに、前記内周突部２４ａには、第１凹部２８ａ及び第２凹部２８ｂが一体成形される。   On the other hand, the resin frame member 24 is preliminarily molded by injection molding using a mold (not shown). The resin frame member 24 has an inner peripheral protrusion 24a that is thinner than the outermost peripheral part, and a first recess 28a and a second recess 28b are integrally formed in the inner peripheral protrusion 24a.

次に、樹脂製枠部材２４の内周突部２４ａの内側平面２４ａｓには、接着層２６を構成する接着剤２６ａが全周に亘って塗布された後、前記樹脂製枠部材２４の段部２５に段差電解質膜・電極構造体１０ａの段差部２３が重ね合わされる。具体的には、樹脂製枠部材２４の内側平面２４ａｓと、段差電解質膜・電極構造体１０ａを構成する固体高分子電解質膜１８の外周縁部１８ｂｅとが、接着剤２６ａを介して重ね合わされる（図５参照）。   Next, an adhesive 26a constituting the adhesive layer 26 is applied to the inner flat surface 24as of the inner peripheral projection 24a of the resin frame member 24 over the entire circumference, and then the step portion of the resin frame member 24 is formed. 25, the stepped portion 23 of the stepped electrolyte membrane / electrode structure 10 a is overlaid. Specifically, the inner flat surface 24as of the resin frame member 24 and the outer peripheral edge portion 18be of the solid polymer electrolyte membrane 18 constituting the stepped electrolyte membrane / electrode structure 10a are overlapped with each other via an adhesive 26a. (See FIG. 5).

そして、接着剤２６ａは、化学反応や加熱処理、冷却処理等により接着層２６として、内側平面２４ａｓと固体高分子電解質膜１８の外周縁部１８ｂｅとを接着する。その際、液状の接着剤２６ａは、加圧されるため、段差部２３と段部２５との境界部位に沿って移動する。   The adhesive 26a adheres the inner flat surface 24as and the outer peripheral edge 18be of the solid polymer electrolyte membrane 18 as the adhesive layer 26 by chemical reaction, heat treatment, cooling treatment, or the like. At that time, since the liquid adhesive 26 a is pressurized, it moves along the boundary portion between the stepped portion 23 and the stepped portion 25.

この場合、本実施形態では、樹脂製枠部材２４の内周突部２４ａの端面に、第２ガス拡散層２２ｂに対向して第１凹部２８ａが設けられている。一方、内周突部２４ａの内側平面（平面部）２４ａｓに、第２ガス拡散層２２ｂの端部から外方に露出する固体高分子電解質膜１８の外周縁部１８ｂｅの先端縁部に対向して第２凹部２８ｂが設けられている。 In this case, in the present embodiment, a first recess 28a is provided on the end surface of the inner peripheral projection 24a of the resin frame member 24 so as to face the second gas diffusion layer 22b. On the other hand, the inner flat surface (planar portion) 24as of the inner peripheral protrusion 24a faces the front edge of the outer peripheral edge 18be of the solid polymer electrolyte membrane 18 exposed outward from the end of the second gas diffusion layer 22b. A second recess 28b is provided.

このため、接着剤２６ａの一部は、固体高分子電解質膜１８の先端側に移動し、この固体高分子電解質膜１８の先端部からアノード電極２２の先端に沿って移動する（図５中、矢印ｈ１方向）。従って、接着剤２６ａの一部は、第２ガス拡散層２２ｂに対向する第１凹部２８ａに収容され、外部に漏れ出すことがない。一方、接着剤２６ａの他の一部は、内周突部２４ａの基端部側（段部２５の壁面側）に移動する（図５中、矢印ｈ２方向）。これにより、接着剤２６ａの他の一部は、第２凹部２８ｂに収容されて、外部に漏れ出すことがない。   Therefore, a part of the adhesive 26a moves to the tip side of the solid polymer electrolyte membrane 18, and moves from the tip of the solid polymer electrolyte membrane 18 along the tip of the anode electrode 22 (in FIG. 5, Arrow h1 direction). Accordingly, a part of the adhesive 26a is accommodated in the first recess 28a facing the second gas diffusion layer 22b and does not leak to the outside. On the other hand, the other part of the adhesive 26a moves to the base end side of the inner peripheral projection 24a (the wall surface side of the step 25) (in the direction of arrow h2 in FIG. 5). Thereby, the other part of the adhesive 26a is accommodated in the second recess 28b and does not leak outside.

このように、本実施形態では、段差電解質膜・電極構造体１０ａの段差部２３側と樹脂製枠部材２４の段部２５側とが、接着剤２６ａにより互いに固定される際、前記接着剤２６ａは、前記段差部２３と前記段部２５との境界部位に沿って移動し、凹部２８（第１凹部２８ａ及び第２凹部２８ｂ）に良好に溜められる。 Thus, in the present embodiment, when the stepped portion 23 side of the stepped electrolyte membrane / electrode structure 10a and the stepped portion 25 side of the resin frame member 24 are fixed to each other by the adhesive 26a, the adhesive 26a Moves along the boundary portion between the stepped portion 23 and the stepped portion 25, and is well stored in the recess 28 (the first recess 28a and the second recess 28b).

このため、段差部２３と段部２５との境界部位に、凹部２８を設けるだけでよく、簡単且つ経済的な構成で、接着剤２６ａが樹脂枠付き電解質膜・電極構造体１０の外部にはみ出すことを良好に抑制することができる。従って、作業性を良好に向上させることが可能になるという効果が得られる。   Therefore, it is only necessary to provide the recess 28 at the boundary between the stepped portion 23 and the stepped portion 25, and the adhesive 26a protrudes outside the electrolyte membrane / electrode structure 10 with a resin frame with a simple and economical configuration. This can be suppressed satisfactorily. Therefore, the effect that it becomes possible to improve workability | operativity favorable is acquired.

次に、樹脂枠付き電解質膜・電極構造体１０は、図２に示すように、第１セパレータ１４及び第２セパレータ１６により挟持される。第１セパレータ１４は、第１凸状シール４２ａを介して樹脂製枠部材２４の内周突部２４ａに当接し、第２セパレータ１６と共に樹脂枠付き電解質膜・電極構造体１０に荷重を付与する。さらに、燃料電池１２は、所定数だけ積層されて燃料電池スタックが構成されるとともに、図示しないエンドプレート間に締め付け荷重が付与される。   Next, the resin membrane-attached electrolyte membrane / electrode structure 10 is sandwiched between the first separator 14 and the second separator 16 as shown in FIG. The first separator 14 contacts the inner peripheral protrusion 24a of the resin frame member 24 via the first convex seal 42a, and applies a load to the electrolyte membrane / electrode structure 10 with a resin frame together with the second separator 16. . Furthermore, a predetermined number of fuel cells 12 are stacked to form a fuel cell stack, and a clamping load is applied between end plates (not shown).

このように構成される燃料電池１２の動作について、以下に説明する。   The operation of the fuel cell 12 configured as described above will be described below.

先ず、図１に示すように、酸化剤ガス入口連通孔３０ａに酸素含有ガス等の酸化剤ガスが供給されるとともに、燃料ガス入口連通孔３４ａに水素含有ガス等の燃料ガスが供給される。さらに、冷却媒体入口連通孔３２ａに純水やエチレングリコール、オイル等の冷却媒体が供給される。   First, as shown in FIG. 1, an oxidant gas such as an oxygen-containing gas is supplied to the oxidant gas inlet communication hole 30a, and a fuel gas such as a hydrogen-containing gas is supplied to the fuel gas inlet communication hole 34a. Further, a cooling medium such as pure water, ethylene glycol, or oil is supplied to the cooling medium inlet communication hole 32a.

このため、酸化剤ガスは、酸化剤ガス入口連通孔３０ａから第２セパレータ１６の酸化剤ガス流路３６に導入され、矢印Ｂ方向に移動して段差電解質膜・電極構造体１０ａのカソード電極２０に供給される。一方、燃料ガスは、燃料ガス入口連通孔３４ａから供給孔部４６を通って第１セパレータ１４の燃料ガス流路３８に導入される。燃料ガスは、燃料ガス流路３８に沿って矢印Ｂ方向に移動し、段差電解質膜・電極構造体１０ａのアノード電極２２に供給される。   Therefore, the oxidant gas is introduced from the oxidant gas inlet communication hole 30a into the oxidant gas flow path 36 of the second separator 16, moves in the direction of arrow B, and the cathode electrode 20 of the step electrolyte membrane / electrode structure 10a. To be supplied. On the other hand, the fuel gas is introduced from the fuel gas inlet communication hole 34 a through the supply hole 46 into the fuel gas flow path 38 of the first separator 14. The fuel gas moves in the direction of arrow B along the fuel gas flow path 38 and is supplied to the anode electrode 22 of the step electrolyte membrane / electrode structure 10a.

従って、各段差電解質膜・電極構造体１０ａでは、カソード電極２０に供給される酸化剤ガスと、アノード電極２２に供給される燃料ガスとが、電極触媒層内で電気化学反応により消費されて発電が行われる。   Therefore, in each step electrolyte membrane / electrode structure 10a, the oxidant gas supplied to the cathode electrode 20 and the fuel gas supplied to the anode electrode 22 are consumed by an electrochemical reaction in the electrode catalyst layer to generate power. Is done.

次いで、カソード電極２０に供給されて消費された酸化剤ガスは、酸化剤ガス出口連通孔３０ｂに沿って矢印Ａ方向に排出される。同様に、アノード電極２２に供給されて消費された燃料ガスは、排出孔部４８を通り燃料ガス出口連通孔３４ｂに沿って矢印Ａ方向に排出される。   Next, the oxidant gas consumed by being supplied to the cathode electrode 20 is discharged in the direction of arrow A along the oxidant gas outlet communication hole 30b. Similarly, the fuel gas consumed by being supplied to the anode electrode 22 passes through the discharge hole 48 and is discharged in the direction of arrow A along the fuel gas outlet communication hole 34b.

また、冷却媒体入口連通孔３２ａに供給された冷却媒体は、第１セパレータ１４と第２セパレータ１６との間の冷却媒体流路４０に導入された後、矢印Ｂ方向に流通する。この冷却媒体は、段差電解質膜・電極構造体１０ａを冷却した後、冷却媒体出口連通孔３２ｂから排出される。   The cooling medium supplied to the cooling medium inlet communication hole 32a is introduced into the cooling medium flow path 40 between the first separator 14 and the second separator 16, and then flows in the direction of arrow B. The cooling medium is discharged from the cooling medium outlet communication hole 32b after the stepped electrolyte membrane / electrode structure 10a is cooled.

図６に示すように、第１参考例に係る樹脂枠付き電解質膜・電極構造体６０は、固体高分子型燃料電池６１に組み込まれる。なお、本実施形態に係る樹脂枠付き電解質膜・電極構造体１０及び燃料電池１２と同一の構成要素には、同一の参照符号を付して、その詳細な説明は省略する。また、以下に説明する第２参考例においても同様に、その詳細な説明は省略する。 As shown in FIG. 6, an electrolyte membrane / electrode structure 60 with a resin frame according to a first reference example is incorporated in a solid polymer fuel cell 61. The same components as those in the electrolyte membrane / electrode structure 10 with a resin frame and the fuel cell 12 according to this embodiment are denoted by the same reference numerals, and detailed description thereof is omitted. Similarly, in the second reference example described below, detailed description thereof is omitted.

樹脂枠付き電解質膜・電極構造体６０は、段差電解質膜・電極構造体６０ａと樹脂製枠部材６２とを備える。樹脂製枠部材６２は、段差部２３と段部２５との境界部位に、接着剤２６ａを溜めるための凹部６４が設けられる。凹部６４は、樹脂製枠部材２４の内周突部２４ａの端面に、第２ガス拡散層２２ｂに対向して設けられる第１凹部６４ａと、段部２５の端面に、第１ガス拡散層２０ｂに対向して設けられる第２凹部６４ｂとを有する。   The resin membrane-attached electrolyte membrane / electrode structure 60 includes a stepped electrolyte membrane / electrode structure 60 a and a resin frame member 62. The resin frame member 62 is provided with a concave portion 64 for storing the adhesive 26 a at a boundary portion between the step portion 23 and the step portion 25. The recess 64 includes a first recess 64a provided on the end surface of the inner peripheral projection 24a of the resin frame member 24 so as to face the second gas diffusion layer 22b, and a first gas diffusion layer 20b on the end surface of the step portion 25. And a second recess 64b provided opposite to the first recess 64b.

このように構成される第１参考例では、凹部６４を構成する第１凹部６４ａと第２凹部６４ｂとの間隔が大きくなる。すなわち、第２ガス拡散層２２ｂに対向する位置から第１ガス拡散層２０ｂに対向する位置まで及んでいる。従って、段差電解質膜・電極構造体６０ａと樹脂製枠部材６２との接合強度が一層向上するという効果が得られる。 In the first reference example configured as described above, the distance between the first recess 64a and the second recess 64b constituting the recess 64 is increased. That is, it extends from a position facing the second gas diffusion layer 22b to a position facing the first gas diffusion layer 20b. Therefore, the effect of further improving the bonding strength between the step electrolyte membrane / electrode structure 60a and the resin frame member 62 can be obtained.

図７に示すように、第２参考例に係る樹脂枠付き電解質膜・電極構造体７０は、固体高分子型燃料電池７１に組み込まれる。 As shown in FIG. 7, the electrolyte membrane / electrode structure 70 with a resin frame according to the second reference example is incorporated in a solid polymer fuel cell 71.

樹脂枠付き電解質膜・電極構造体７０は、段差電解質膜・電極構造体７０ａと樹脂製枠部材７２とを備える。段差電解質膜・電極構造体７０ａは、段差部２３と段部２５との境界部位に、接着剤２６ａを溜めるための凹部７４が設けられる。凹部７４は、第２ガス拡散層２２ｂの端面に、樹脂製枠部材２４の内周突部２４ａの端面に対向して設けられる第１凹部７４ａと、第１ガス拡散層２０ｂの端面に、段部２５の端面に対向して設けられる第２凹部７４ｂとを有する。   The resin membrane-attached electrolyte membrane / electrode structure 70 includes a stepped electrolyte membrane / electrode structure 70 a and a resin frame member 72. The stepped electrolyte membrane / electrode structure 70 a is provided with a recess 74 for storing the adhesive 26 a at the boundary between the stepped portion 23 and the stepped portion 25. The recess 74 is provided on the end surface of the second gas diffusion layer 22b on the end surface of the first gas diffusion layer 20b and the first recess 74a provided opposite to the end surface of the inner peripheral projection 24a of the resin frame member 24. And a second recess 74 b provided to face the end surface of the portion 25.

このように構成される第２参考例では、樹脂製枠部材７２側に代えて、段差電解質膜・電極構造体７０ａ側に凹部７４が設けられている。このため、上記の実施形態及び第１参考例と同様の効果が得られる。 In the second reference example configured as described above, a recess 74 is provided on the step electrolyte membrane / electrode structure 70a side instead of the resin frame member 72 side. Therefore, implementation embodiment and the first same effect as the reference example described above can be obtained.

なお、凹部２８、６４及び７４は、開口断面矩形状を有しているが、これに限定されるものではない。例えば、図８に示すように、開口断面半円形状の凹部８０、図９に示すように、角部にＲを有する開口断面矩形状の凹部８２、図１０に示すように、開口断面楕円形状の凹部８４を用いることができる。角部にＲを有することにより、応力集中が発生し難くなるとともに、液状接着剤が円滑に流れることが可能になる。   In addition, although the recessed parts 28, 64, and 74 have an opening cross-sectional rectangular shape, it is not limited to this. For example, as shown in FIG. 8, a concave portion 80 having a semicircular shape in the opening cross section, a concave portion 82 having a rectangular shape in the opening cross section having R at the corners as shown in FIG. 9, and an elliptical shape in the opening cross section as shown in FIG. The recess 84 can be used. By having R at the corners, stress concentration is less likely to occur, and the liquid adhesive can flow smoothly.

さらに、図１１に示すように、開口断面楕円形状の凹部８６、図１２に示すように、底部にＲを有する開口断面三角形状の凹部８８、図１３に示すように、開口断面台形状の凹部９０ａ、９０ｂの複数の凹部及び図１４に示すように、開口断面円弧形状の凹部９２ａと開口断面台形状の凹部９２ｂとの複数の凹部が使用可能である。また、図１５に示すように、複数の独立した円形、四角形、多角形、線状の凹みからなる凹部９４を全周に亘って設けて用いてもよい。   Further, as shown in FIG. 11, a concave portion 86 having an elliptical opening cross section, as shown in FIG. 12, a concave portion 88 having a triangular opening cross section having R at the bottom, and a concave portion having a trapezoidal shape as shown in FIG. As shown in FIG. 14, a plurality of recesses 90 a and 90 b and a plurality of recesses 92 a having a circular arc shape of the opening cross section and a recess 92 b having a trapezoidal shape of the opening cross section can be used. Further, as shown in FIG. 15, a plurality of independent circular, quadrangular, polygonal, or linear recesses 94 may be provided over the entire circumference.

１０、６０、７０…樹脂枠付き電解質膜・電極構造体
１０ａ、６０ａ、７０ａ…段差電解質膜・電極構造体
１２、６１、７１…燃料電池
１４、１６…セパレータ １８…固体高分子電解質膜
２０…カソード電極 ２０ａ、２２ａ…電極触媒層
２０ｂ、２２ｂ…ガス拡散層 ２２…アノード電極
２３…段差部 ２４、６２、７２…樹脂製枠部材
２４ａ…内周突部 ２５…段部
２６…接着層 ２６ａ…接着剤
２８、２８ａ、２８ｂ、６４、６４ａ、６４ｂ、７４、７４ａ、７４ｂ、８０、８２、８４、８６、８８、９０ａ、９０ｂ、９２ａ、９２ｂ、９４…凹部
３０ａ…酸化剤ガス入口連通孔 ３０ｂ…酸化剤ガス出口連通孔
３２ａ…冷却媒体入口連通孔 ３２ｂ…冷却媒体出口連通孔
３４ａ…燃料ガス入口連通孔 ３４ｂ…燃料ガス出口連通孔
３６…酸化剤ガス流路 ３８…燃料ガス流路
４０…冷却媒体流路 ４２、４４…シール部材 DESCRIPTION OF SYMBOLS 10, 60, 70 ... Electrolyte membrane / electrode structure 10a, 60a, 70a with resin frame ... Step electrolyte membrane / electrode structure 12, 61, 71 ... Fuel cell 14, 16 ... Separator 18 ... Solid polymer electrolyte membrane 20 ... Cathode electrode 20a, 22a ... Electrode catalyst layer 20b, 22b ... Gas diffusion layer 22 ... Anode electrode 23 ... Stepped portion 24, 62, 72 ... Resin frame member 24a ... Inner peripheral projection 25 ... Stepped portion 26 ... Adhesive layer 26a ... Adhesive 28, 28a, 28b, 64, 64a, 64b, 74, 74a, 74b, 80, 82, 84, 86, 88, 90a, 90b, 92a, 92b, 94 ... recess 30a ... oxidant gas inlet communication hole 30b ... Oxidant gas outlet communication hole 32a ... Cooling medium inlet communication hole 32b ... Cooling medium outlet communication hole 34a ... Fuel gas inlet communication hole 34b ... Fuel gas outlet communication hole 36 ... Oxidant Scan channel 38 ... fuel gas flow path 40 ... coolant flow 42, 44 ... sealing member

Claims (2)

固体高分子電解質膜の一方の面に、第１触媒層及び第１ガス拡散層を有する第１電極が配設され、且つ前記固体高分子電解質膜の他方の面に、第２触媒層及び第２ガス拡散層を有する第２電極が配設されるとともに、前記第１ガス拡散層の平面寸法は、前記第２ガス拡散層の平面寸法よりも大きな寸法に設定される段差電解質膜・電極構造体と、
前記固体高分子電解質膜の外周を周回する枠形状を有しており、段部を介し最外周部よりも薄肉状に形成されて前記第２ガス拡散層側に突出する内周突部が設けられる樹脂製枠部材と、
を備え、燃料電池に組み込まれる樹脂枠付き電解質膜・電極構造体であって、
前記段差電解質膜・電極構造体の段差部側と前記樹脂製枠部材の前記段部側とは、接着剤により互いに固定されるとともに、
前記段差部と前記段部との境界部位には、前記接着剤を溜めるための凹部が設けられ、
前記凹部は、
前記樹脂製枠部材の前記内周突部の端面に、前記第２ガス拡散層に対向して設けられるとともに、前記内周突部の内周に沿って周回する第１凹部と、
前記内周突部の平面部に、前記第２ガス拡散層の端部から外方に露出する前記固体高分子電解質膜に対向して設けられるとともに、前記第１凹部よりも外側で前記段部に沿って周回する第２凹部と、を有することを特徴とする樹脂枠付き電解質膜・電極構造体。 A first electrode having a first catalyst layer and a first gas diffusion layer is disposed on one surface of the solid polymer electrolyte membrane, and a second catalyst layer and a second electrode are disposed on the other surface of the solid polymer electrolyte membrane. A step electrolyte membrane / electrode structure in which a second electrode having two gas diffusion layers is disposed, and a planar dimension of the first gas diffusion layer is set larger than a planar dimension of the second gas diffusion layer Body,
It has a frame shape that circulates around the outer periphery of the solid polymer electrolyte membrane, and is provided with an inner peripheral protrusion that is formed thinner than the outermost peripheral portion via a step portion and protrudes toward the second gas diffusion layer. A resin frame member,
An electrolyte membrane / electrode structure with a resin frame incorporated in a fuel cell,
The stepped portion side of the stepped electrolyte membrane / electrode structure and the stepped portion side of the resin frame member are fixed to each other by an adhesive,
In the boundary portion between the stepped portion and the stepped portion, a recess for storing the adhesive is provided ,
The recess is
A first recess provided on the end surface of the inner peripheral protrusion of the resin frame member so as to face the second gas diffusion layer, and circulates along the inner periphery of the inner peripheral protrusion;
The flat portion of the inner peripheral projection is provided to face the solid polymer electrolyte membrane exposed outward from the end of the second gas diffusion layer, and the stepped portion outside the first recess. resin framed membrane electrode assembly of the second recess, the Rukoto that having a characterized orbiting along. 固体高分子電解質膜の一方の面に、第１触媒層及び第１ガス拡散層を有する第１電極が配設され、且つ前記固体高分子電解質膜の他方の面に、第２触媒層及び第２ガス拡散層を有する第２電極が配設されるとともに、前記第１ガス拡散層の平面寸法は、前記第２ガス拡散層の平面寸法よりも大きな寸法に設定される段差電解質膜・電極構造体と、
前記固体高分子電解質膜の外周を周回する枠形状を有しており、段部を介し最外周部よりも薄肉状に形成されて前記第２ガス拡散層側に突出する内周突部が設けられる樹脂製枠部材と、
を備える樹脂枠付き電解質膜・電極構造体を組み込む燃料電池であって、
前記段差電解質膜・電極構造体の段差部側と前記樹脂製枠部材の前記段部側とは、接着剤により互いに固定されるとともに、
前記段差部と前記段部との境界部位には、前記接着剤を溜めるための凹部が設けられ、
前記凹部は、
前記樹脂製枠部材の前記内周突部の端面に、前記第２ガス拡散層に対向して設けられるとともに、前記内周突部の内周に沿って周回する第１凹部と、
前記内周突部の平面部に、前記第２ガス拡散層の端部から外方に露出する前記固体高分子電解質膜に対向して設けられるとともに、前記第１凹部よりも外側で前記段部に沿って周回する第２凹部と、を有することを特徴とする燃料電池。 A first electrode having a first catalyst layer and a first gas diffusion layer is disposed on one surface of the solid polymer electrolyte membrane, and a second catalyst layer and a second electrode are disposed on the other surface of the solid polymer electrolyte membrane. A step electrolyte membrane / electrode structure in which a second electrode having two gas diffusion layers is disposed, and a planar dimension of the first gas diffusion layer is set larger than a planar dimension of the second gas diffusion layer Body,
It has a frame shape that circulates around the outer periphery of the solid polymer electrolyte membrane, and is provided with an inner peripheral protrusion that is formed thinner than the outermost peripheral portion via a step portion and protrudes toward the second gas diffusion layer. A resin frame member,
A fuel cell incorporating an electrolyte membrane / electrode structure with a resin frame comprising:
The stepped portion side of the stepped electrolyte membrane / electrode structure and the stepped portion side of the resin frame member are fixed to each other by an adhesive,
In the boundary portion between the stepped portion and the stepped portion, a recess for storing the adhesive is provided ,
The recess is
A first recess provided on the end surface of the inner peripheral protrusion of the resin frame member so as to face the second gas diffusion layer, and circulates along the inner periphery of the inner peripheral protrusion;
The flat portion of the inner peripheral projection is provided to face the solid polymer electrolyte membrane exposed outward from the end of the second gas diffusion layer, and the stepped portion outside the first recess. fuel cell according to claim Rukoto that having a, a second recess circulating along.
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