JP5286887B2 - Membrane / electrode assembly with reinforcing sheet for polymer electrolyte fuel cell and method for producing the same - Google Patents

Membrane / electrode assembly with reinforcing sheet for polymer electrolyte fuel cell and method for producing the same Download PDF

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JP5286887B2
JP5286887B2 JP2008091989A JP2008091989A JP5286887B2 JP 5286887 B2 JP5286887 B2 JP 5286887B2 JP 2008091989 A JP2008091989 A JP 2008091989A JP 2008091989 A JP2008091989 A JP 2008091989A JP 5286887 B2 JP5286887 B2 JP 5286887B2
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reinforcing sheet
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美和 長田
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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

本発明は固体高分子型燃料電池用の補強シート付き膜・電極接合体およびその製造方法に関する。   The present invention relates to a membrane / electrode assembly with a reinforcing sheet for a polymer electrolyte fuel cell and a method for producing the same.

固体高分子型燃料電池は、プロトン伝導性を有する固体高分子膜を電解質膜とし、この膜の両面に燃料極および空気極を接合して構成され、燃料極に水素等、空気極に酸素あるいは空気を供給して電気化学反応により発電するシステムである。各電極では例えば下記の反応が起こっている。   A polymer electrolyte fuel cell has a solid polymer membrane having proton conductivity as an electrolyte membrane, and a fuel electrode and an air electrode are joined to both surfaces of the membrane. This is a system that generates air by electrochemical reaction by supplying air. For example, the following reactions occur at each electrode.

燃料極：Ｈ2 → ２Ｈ+ ＋ ２ｅ-
空気極：（１／２）Ｏ2 ＋ ２Ｈ+ ＋ ２ｅ- → Ｈ2Ｏ
全反応：Ｈ2 ＋ （１／２）Ｏ2 → Ｈ2Ｏ Fuel electrode: H 2 → 2H + + 2e −
Air electrode: (1/2) O 2 + 2H + + 2e − → H 2 O
Total reaction: H 2 + (1/2) O 2 → H 2 O

これらの反応式からわかるように、発電時に生成するのは水のみである。燃料電池は、従来の内燃機関とは異なり二酸化炭素等の環境負荷ガスを発生しないために、次世代のクリーンエネルギーシステムとして注目されている。   As can be seen from these reaction equations, only water is generated during power generation. Unlike conventional internal combustion engines, fuel cells are attracting attention as next-generation clean energy systems because they do not generate environmentally harmful gases such as carbon dioxide.

固体高分子型燃料電池は、電解質膜として水素イオン（プロトン）伝導性高分子電解質膜を用いている。固体高分子型燃料電池を構成する固体高分子型燃料電池用膜・電極接合体（以下、単に「膜・電極接合体」と称する場合もある。）のうち、電解質膜の両主面側に触媒層を配置したもの（即ち、触媒層／電解質膜／触媒層の層構成のもの）は、３層ＭＥＡと称されており、さらに、その３層ＭＥＡに電極基材を配置したもの（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、５層ＭＥＡと称されている。固体高分子型燃料電池は、燃料および酸化剤の漏出を防ぐため、かつ、電解質膜とセパレータとを絶縁するためのガスケットを備えている。   The polymer electrolyte fuel cell uses a hydrogen ion (proton) conductive polymer electrolyte membrane as an electrolyte membrane. Of the membrane / electrode assembly for a polymer electrolyte fuel cell constituting the polymer electrolyte fuel cell (hereinafter, also simply referred to as “membrane / electrode assembly”), it is disposed on both main surfaces of the electrolyte membrane. The one in which the catalyst layer is disposed (that is, the layer structure of catalyst layer / electrolyte membrane / catalyst layer) is called a three-layer MEA, and further, the electrode substrate is disposed in the three-layer MEA (that is, Electrode base material / catalyst layer / electrolyte membrane / catalyst layer / electrode base material layer structure) is referred to as a five-layer MEA. The polymer electrolyte fuel cell includes a gasket for preventing leakage of fuel and oxidant and for insulating the electrolyte membrane from the separator.

従来の固体高分子形燃料電池は、例えば下記構造を有している。   A conventional polymer electrolyte fuel cell has, for example, the following structure.

従来の固体高分子型燃料電池の一例では、２層の触媒層の間に電解質膜が配置され、触媒層と電解質膜の平面形状がほぼ等しい。この３層構造体の周縁部が２枚の補強膜で挟まれており、各触媒層上にはガス拡散層が配置されている。上記２枚の補強膜は、１対のガスシール材で挟まれており、補強膜は、粘着、熱圧着等の方法により、触媒層に接合されている（特許文献１）。
特開２００４−４７２３０号広報 In an example of a conventional polymer electrolyte fuel cell, an electrolyte membrane is disposed between two catalyst layers, and the planar shapes of the catalyst layer and the electrolyte membrane are substantially equal. The peripheral portion of the three-layer structure is sandwiched between two reinforcing films, and a gas diffusion layer is disposed on each catalyst layer. The two reinforcing membranes are sandwiched between a pair of gas seal materials, and the reinforcing membranes are joined to the catalyst layer by a method such as adhesion or thermocompression bonding (Patent Document 1).
Japanese Laid-Open Patent Publication No. 2004-47230

しかし、特許文献１に記載の固体高分子型燃料電池では、触媒層と電解質膜の平面形状がほぼ等しく、そのためガスシール材が触媒層上に乗り上げているので、電解質膜に触媒層が食い込むおそれがある。電解質膜に触媒層が食い込むと、セルの長期耐久性が損なわれる。また、ガスシール材と電解質膜の間に配置された補強膜が粘着剤により電極に接合される場合、粘着剤から溶出する溶出物によって、セルの長期耐久性が損なわれるおそれがある。   However, in the polymer electrolyte fuel cell described in Patent Document 1, since the planar shape of the catalyst layer and the electrolyte membrane is substantially equal, and the gas seal material runs on the catalyst layer, the catalyst layer may bite into the electrolyte membrane. There is. If the catalyst layer bites into the electrolyte membrane, the long-term durability of the cell is impaired. Moreover, when the reinforcement film | membrane arrange | positioned between a gas sealing material and an electrolyte membrane is joined to an electrode with an adhesive, the long-term durability of a cell may be impaired by the eluate eluted from an adhesive.

本発明は、電解質膜が受ける機械的負荷等によるダメージが抑制された、固体高分子型燃料電池用補強シート付き膜・電極接合体を提供する。   The present invention provides a membrane / electrode assembly with a reinforcing sheet for a polymer electrolyte fuel cell, in which damage due to a mechanical load applied to the electrolyte membrane is suppressed.

本発明の固体高分子型燃料電池用補強シート付き膜・電極接合体は、
電解質膜と、
前記電解質膜の両主面の中央部に前記電解質膜を挟むように接合された、１対の触媒層と、
連続した細孔を有する多孔質体からなり、各触媒層の周囲に配置され、前記触媒層の端面に接した、１対の補強シートと、を含む。 The membrane / electrode assembly with a reinforcing sheet for a polymer electrolyte fuel cell of the present invention is:
An electrolyte membrane;
A pair of catalyst layers joined so as to sandwich the electrolyte membrane at the center of both main surfaces of the electrolyte membrane;
A pair of reinforcing sheets made of a porous body having continuous pores, disposed around each catalyst layer, and in contact with the end face of the catalyst layer.

本発明の固体高分子型燃料電池用補強シート付き膜・電極接合体の製造方法は、電解質膜と、前記電解質膜の両主面の中央部に前記電解質膜を挟むように接合された、１対の触媒層と、各触媒層の周囲に配置され前記触媒層の端面に接した１対の補強シートとを含む、固体高分子型燃料電池用補強シート付き膜・電極接合体の製造方法であって、
前記電解質膜の両主面上に、各々、前記触媒層の平面形状に対応した形状の開口を有し、連続した細孔を有する多孔質体からなる前記補強シートを配置する工程と、
支持基材と前記支持基材上に配置された触媒含有層とを含む積層体の前記触媒含有層の一部を、前記補強シートの前記開口から露出した前記電解質膜に熱転写して、前記電解質膜の両主面に各々触媒層を形成するとともに前記補強シートを各々前記電解質膜の両主面に固定する工程と、を含む。 In the method for producing a membrane / electrode assembly with a reinforcing sheet for a polymer electrolyte fuel cell according to the present invention, the electrolyte membrane and the electrolyte membrane are joined so as to sandwich the electrolyte membrane between the center portions of both main surfaces. A method for producing a membrane / electrode assembly with a reinforcing sheet for a polymer electrolyte fuel cell, comprising: a pair of catalyst layers; and a pair of reinforcing sheets disposed around each catalyst layer and in contact with an end face of the catalyst layer There,
Disposing the reinforcing sheet made of a porous body having openings corresponding to the planar shape of the catalyst layer on both main surfaces of the electrolyte membrane and having continuous pores; and
A portion of the catalyst-containing layer of the laminate including a support substrate and a catalyst-containing layer disposed on the support substrate is thermally transferred to the electrolyte membrane exposed from the opening of the reinforcing sheet, and the electrolyte Forming a catalyst layer on each main surface of the membrane and fixing the reinforcing sheet to each main surface of the electrolyte membrane.

本発明によれば、電解質膜が受ける機械的負荷等によるダメージが抑制された、固体高分子型燃料電池用補強シート付き膜・電極接合体を提供できる。   ADVANTAGE OF THE INVENTION According to this invention, the membrane-electrode assembly with the reinforcement sheet | seat for polymer electrolyte fuel cells in which the damage by the mechanical load etc. which an electrolyte membrane receives was suppressed can be provided.

図１は、本発明の固体高分子型燃料電池用補強シート付き膜・電極接合体（以下、「補強シート付き膜・電極接合体」と称する場合もある。）の一例の平面図であり、図２は、図１のＩ−Ｉ'模式断面図である。図３は、図１に示した補強シート付き膜・電極接合体を含むガスケット付き膜・電極接合体の一例の平面図であり、図４は、図３のII−II'模式断面図である。なお、図１〜４を用いて説明する本発明の膜・電極接合体の一例は、補強シート付き５層ＭＥＡであるが、本発明の膜・電極接合体は、補強シート付き３層ＭＥＡをも含む。   FIG. 1 is a plan view of an example of a membrane / electrode assembly with a reinforcing sheet for a polymer electrolyte fuel cell according to the present invention (hereinafter also referred to as “membrane / electrode assembly with a reinforcing sheet”). FIG. 2 is a schematic cross-sectional view taken along the line II ′ of FIG. 3 is a plan view of an example of a membrane / electrode assembly with a gasket including the membrane / electrode assembly with a reinforcing sheet shown in FIG. 1, and FIG. 4 is a schematic cross-sectional view taken along the line II-II ′ of FIG. . An example of the membrane / electrode assembly of the present invention described with reference to FIGS. 1 to 4 is a five-layer MEA with a reinforcing sheet, but the membrane / electrode assembly of the present invention is a three-layer MEA with a reinforcing sheet. Including.

図１および図２に示すように、電解質膜１の一方の主面の中央部には、第１触媒層４と第１ガス拡散層５とからなる燃料極６が配置され、電解質膜１の他方の主面の中央部には、第２触媒層４’と第２ガス拡散層５'とからなる空気極７が配置されている。以下、第１触媒層４と第２触媒層４'を総称して単に触媒層と、第１ガス拡散層５と第２ガス拡散層５'を総称して単にガス拡散層と称する場合もある。   As shown in FIGS. 1 and 2, a fuel electrode 6 composed of a first catalyst layer 4 and a first gas diffusion layer 5 is disposed at the center of one main surface of the electrolyte membrane 1. An air electrode 7 composed of a second catalyst layer 4 ′ and a second gas diffusion layer 5 ′ is disposed at the center of the other main surface. Hereinafter, the first catalyst layer 4 and the second catalyst layer 4 ′ may be collectively referred to simply as a catalyst layer, and the first gas diffusion layer 5 and the second gas diffusion layer 5 ′ may be simply referred to as a gas diffusion layer. .

図２に示すように、補強シート付き膜・電極接合体１００は、第１触媒層４、第２触媒層４’の平面形状に対応した形状の開口を有する、１対の補強シート９、９'を備えている（図５Ｂ参照）。補強シート９、９'は、電解質膜１の両面のうちの、第１触媒層４、第２触媒層４’によって被覆されていない部分（外縁部）に各々固定されている。第１触媒層４、第２触媒層４’は、各々補強シート９、９'の開口内に収容されており、第１触媒層４、第２触媒層４’の端面は、補強シートの端面９１、９１'に接している（図５Ｂ参照）。これにより、触媒層と補強シートが重なり合うことがない為、触媒層が電解質膜に食い込まず、また電解質膜が露出することなく補強シートで覆われている為、燃料電池の耐久性が向上する。   As shown in FIG. 2, the membrane / electrode assembly 100 with a reinforcing sheet has a pair of reinforcing sheets 9, 9 having openings corresponding to the planar shapes of the first catalyst layer 4 and the second catalyst layer 4 ′. '(See FIG. 5B). The reinforcing sheets 9 and 9 ′ are respectively fixed to portions (outer edge portions) of both surfaces of the electrolyte membrane 1 that are not covered with the first catalyst layer 4 and the second catalyst layer 4 ′. The first catalyst layer 4 and the second catalyst layer 4 ′ are respectively accommodated in the openings of the reinforcing sheets 9 and 9 ′, and the end surfaces of the first catalyst layer 4 and the second catalyst layer 4 ′ are the end surfaces of the reinforcing sheet. 91 and 91 '(refer FIG. 5B). Thereby, since the catalyst layer and the reinforcing sheet do not overlap with each other, the catalyst layer does not bite into the electrolyte membrane and is covered with the reinforcing sheet without exposing the electrolyte membrane, so that the durability of the fuel cell is improved.

図２に示すように、第１触媒層４、第２触媒層４’上には、各々、第１ガス拡散層５、第２ガス拡散層５’が接して配置されている。第１ガス拡散層５、第２ガス拡散層５’の平面形状は、補強シート９、９'が有する開口の平面形状よりも大きい（図５Ｃ参照）。また、補強シート９、９'は、その厚みが、第１触媒層４、第２触媒層４’のそれよりも厚い（図５Ｂ参照）。そのため、補強シート９、９'の一部は、各々、第１ガス拡散層５、第２ガス拡散層５’により押し潰されている（図５Ｂおよび図５Ｃ参照）。また、図２に示すように、補強シート９、９'は、その厚みが、燃料極６、空気極７のそれよりも薄い。そのため、第１触媒層４および第２触媒層４’は補強シート９、９'の開口内にその全体が収容されているが、第１ガス拡散層５、第２ガス拡散層５’は、その一部が補強シート９、９'内に収容され、残部は、補強シート９、９'の開口から突出している。   As shown in FIG. 2, the first gas diffusion layer 5 and the second gas diffusion layer 5 ′ are disposed on and in contact with the first catalyst layer 4 and the second catalyst layer 4 ′, respectively. The planar shapes of the first gas diffusion layer 5 and the second gas diffusion layer 5 'are larger than the planar shape of the openings of the reinforcing sheets 9 and 9' (see FIG. 5C). Further, the reinforcing sheets 9 and 9 'are thicker than the first catalyst layer 4 and the second catalyst layer 4' (see FIG. 5B). Therefore, some of the reinforcing sheets 9 and 9 ′ are crushed by the first gas diffusion layer 5 and the second gas diffusion layer 5 ′, respectively (see FIGS. 5B and 5C). Further, as shown in FIG. 2, the reinforcing sheets 9 and 9 ′ are thinner than those of the fuel electrode 6 and the air electrode 7. Therefore, the first catalyst layer 4 and the second catalyst layer 4 ′ are entirely accommodated in the openings of the reinforcing sheets 9, 9 ′, but the first gas diffusion layer 5 and the second gas diffusion layer 5 ′ are A part thereof is accommodated in the reinforcing sheets 9 and 9 ′, and the remaining portion protrudes from the opening of the reinforcing sheets 9 and 9 ′.

第１ガス拡散層５と重なった補強シート９の一部とその直上の第１ガス拡散層５、すなわち、第１ガス拡散層５のうちの第１触媒層４に接していない部分とその真下の補強シート９には、樹脂が含浸されて封止部８が形成されている（図５Ｃおよび図５Ｄ参照）。これにより、第１ガス拡散層５が補強シート９に固定されるとともに、ガスのリークが防止される。また、第２ガス拡散層５'と重なった補強シート９'の一部とその直上の第２ガス拡散層５'、すなわち、第２ガス拡散層５'のうちの第２触媒層４'に接していない部分とその真下の補強シート９'には、樹脂が含浸されて封止部８'が形成される（図５Ｃおよび図５Ｄ参照）。これにより、第２ガス拡散層５'が補強シート９'に固定されるとともに、ガスのリークが防止される。   A part of the reinforcing sheet 9 that overlaps the first gas diffusion layer 5 and the first gas diffusion layer 5 immediately above it, that is, a portion of the first gas diffusion layer 5 that is not in contact with the first catalyst layer 4 and directly below it. The reinforcing sheet 9 is impregnated with resin to form a sealing portion 8 (see FIGS. 5C and 5D). Thus, the first gas diffusion layer 5 is fixed to the reinforcing sheet 9 and gas leakage is prevented. Further, a part of the reinforcing sheet 9 ′ overlapping with the second gas diffusion layer 5 ′ and the second gas diffusion layer 5 ′ immediately above it, that is, the second catalyst layer 4 ′ of the second gas diffusion layer 5 ′ are formed. The portion that is not in contact with the reinforcing sheet 9 ′ immediately below is impregnated with resin to form a sealing portion 8 ′ (see FIGS. 5C and 5D). Thereby, the second gas diffusion layer 5 ′ is fixed to the reinforcing sheet 9 ′ and gas leakage is prevented.

図３および図４に示されるように、ガスケット１０、１０'は、結合されることにより膜・電極接合体を収容する空間を形成しており、その空間内に補強シート付き膜・電極接合体１００が配置されている。ガスケット１０、１０'の、外表面１０ａ，１０ａ’と、第１ガス拡散層５、第２ガス拡散層５'の外表面５ａ、５ａ'とは、同一平面内にある。ガスケット１０、１０'の外表面１０ａ，１０ａ’側には、各々セパレータ（図示せず）が配置される。これにより、単セルが構成される。   As shown in FIGS. 3 and 4, the gaskets 10 and 10 ′ are joined to form a space for accommodating the membrane / electrode assembly, and the membrane / electrode assembly with a reinforcing sheet is formed in the space. 100 is arranged. The outer surfaces 10a and 10a 'of the gaskets 10 and 10' and the outer surfaces 5a and 5a 'of the first gas diffusion layer 5 and the second gas diffusion layer 5' are in the same plane. Separators (not shown) are respectively disposed on the outer surfaces 10a and 10a 'of the gaskets 10 and 10'. Thereby, a single cell is constituted.

本発明の補強シート付き膜・電極接合体の一例は、後述する、本発明の補強シート付き膜・電極接合体の製造方法の一例によって作製され、補強シート９、９'としてクッション性を有する多孔質体を用いているので、その製造過程における、電解質膜への触媒層の食い込み、ガス拡散層の割れ等の、機械的負荷によるダメージ、が抑制されている。   An example of a membrane / electrode assembly with a reinforcing sheet of the present invention is produced by an example of a method for producing a membrane / electrode assembly with a reinforcing sheet of the present invention, which will be described later, and a porous sheet having cushioning properties as the reinforcing sheets 9 and 9 ′. Since the material is used, damage due to mechanical load such as biting of the catalyst layer into the electrolyte membrane and cracking of the gas diffusion layer in the production process is suppressed.

また、上記本発明の補強シート付き膜・電極接合体の一例では、第１ガス拡散層５と第１触媒層４、第２ガス拡散層５’と第２触媒層４’とが、各々、隙間を有することなく接しているので、第１ガス拡散層５と第１触媒層４との接触、第２ガス拡散層５’と第２触媒層４’との接触が良好である。   In the example of the membrane / electrode assembly with a reinforcing sheet of the present invention, the first gas diffusion layer 5 and the first catalyst layer 4, the second gas diffusion layer 5 ′ and the second catalyst layer 4 ′ are respectively Since the contact is made without a gap, the contact between the first gas diffusion layer 5 and the first catalyst layer 4 and the contact between the second gas diffusion layer 5 ′ and the second catalyst layer 4 ′ are good.

さらに、上記本発明の補強シート付き膜・電極接合体の一例では、第１ガス拡散層５、第２ガス拡散層５'の外表面５ａ、５ａ'には、何ら配置されておらず、セパレータが向かい合うこととなるガス拡散層の表面は平坦である。そのため、補強シート付き膜・電極接合体の電極とセパレータとの間において良好な電気的接触が確保される。   Furthermore, in the example of the membrane / electrode assembly with a reinforcing sheet of the present invention, the outer surfaces 5a and 5a ′ of the first gas diffusion layer 5 and the second gas diffusion layer 5 ′ are not arranged at all. The surfaces of the gas diffusion layers facing each other are flat. Therefore, good electrical contact is ensured between the electrode of the membrane / electrode assembly with a reinforcing sheet and the separator.

次に、図１および図２に示した補強シート付き膜・電極接合体の製造方法の一例について、図５を用いて説明する。   Next, an example of a manufacturing method of the membrane / electrode assembly with a reinforcing sheet shown in FIGS. 1 and 2 will be described with reference to FIG.

図５Ａに示されるように、まず、電解質膜１を、第１触媒層４の平面形状に対応した形状の開口部を有する補強シート９と、第２触媒層４'の平面形状に対応した形状の開口部を有する補強シート９'とにより、挟む。   As shown in FIG. 5A, first, the electrolyte membrane 1 has a shape corresponding to the planar shape of the reinforcing sheet 9 having an opening corresponding to the planar shape of the first catalyst layer 4 and the second catalyst layer 4 ′. It is sandwiched between the reinforcing sheets 9 ′ having the openings.

一方で、支持基材１１上に第１触媒含有層１２を形成し、支持基材１１'上に第２触媒含有層１２'を形成して、積層体１３、１３'を用意する。   On the other hand, the first catalyst-containing layer 12 is formed on the support base material 11 and the second catalyst-containing layer 12 ′ is formed on the support base material 11 ′ to prepare the laminates 13 and 13 ′.

次に、積層体１３、１３'を、各々、第１触媒含有層１２、第２触媒含有層１２'が、補強シート９、９'付きの電解質膜１の両主面に向かい合うように対向させる。次いで、補強シート９、９'をマスクとし、補強シート９、９'から露出した電解質膜１に、第１触媒含有層１２の一部、第２触媒含有層１２'の一部を熱転写して、第１触媒層４、第２触媒層４'を形成する（図５Ｂ参照）。第１触媒含有層１２の一部、第２触媒含有層１２'の一部の熱転写は、同時に行ってもよいし、いずれか一方の熱転写を先に行ってから、他方の熱転写を行ってもよいが、同時に行う方が好ましい。また、第１触媒含有層１２、第２触媒含有層１２'を熱転写するとともに、補強シート９、９'を熱圧着等により電解質膜１に固定すると好ましい。   Next, the laminated bodies 13 and 13 ′ are opposed to each other so that the first catalyst-containing layer 12 and the second catalyst-containing layer 12 ′ face the main surfaces of the electrolyte membrane 1 with the reinforcing sheets 9 and 9 ′, respectively. . Next, a part of the first catalyst-containing layer 12 and a part of the second catalyst-containing layer 12 ′ are thermally transferred to the electrolyte membrane 1 exposed from the reinforcing sheets 9, 9 ′ using the reinforcing sheets 9, 9 ′ as a mask. First catalyst layer 4 and second catalyst layer 4 ′ are formed (see FIG. 5B). The thermal transfer of a part of the first catalyst-containing layer 12 and a part of the second catalyst-containing layer 12 ′ may be performed at the same time, or after either one of the thermal transfer is performed first and the other thermal transfer is performed. Although it is good, it is preferable to carry out simultaneously. In addition, it is preferable that the first catalyst-containing layer 12 and the second catalyst-containing layer 12 ′ are thermally transferred and the reinforcing sheets 9 and 9 ′ are fixed to the electrolyte membrane 1 by thermocompression bonding or the like.

次に、図５Ｃに示されるように、第１触媒層４、第２触媒層４'に接するように、第１ガス拡散層５、第２ガス拡散層５'を配置する。より具体的には、まず、平面形状（面積）が第１触媒層４、第２触媒層４'よりもが大きい第１ガス拡散層５、第２ガス拡散層５'を用意する。次いで、第１ガス拡散層５、第２ガス拡散層５'を、補強シート９、９'上に各々配置し、第１ガス拡散層５、第２ガス拡散層５'を、それぞれ、第１触媒層４、第２触媒層４'に接するまで押し下げ、補強シート９、９'の一部を、第１ガス拡散層５、第２ガス拡散層５'で押し潰す。   Next, as shown in FIG. 5C, the first gas diffusion layer 5 and the second gas diffusion layer 5 ′ are disposed so as to be in contact with the first catalyst layer 4 and the second catalyst layer 4 ′. More specifically, first, a first gas diffusion layer 5 and a second gas diffusion layer 5 ′ having a planar shape (area) larger than the first catalyst layer 4 and the second catalyst layer 4 ′ are prepared. Next, the first gas diffusion layer 5 and the second gas diffusion layer 5 ′ are respectively disposed on the reinforcing sheets 9 and 9 ′, and the first gas diffusion layer 5 and the second gas diffusion layer 5 ′ are respectively set to the first gas diffusion layer 5 and the second gas diffusion layer 5 ′. It pushes down until it contacts the catalyst layer 4 and the second catalyst layer 4 ′, and part of the reinforcing sheets 9 and 9 ′ is crushed by the first gas diffusion layer 5 and the second gas diffusion layer 5 ′.

次に、この状態で、第１ガス拡散層５と重なった補強シート９の一部とその直上の第１ガス拡散層５に樹脂を含浸させて、封止部８を形成し、第１ガス拡散層５を補強シート９に固定させる。同様に、第２ガス拡散層５'と重なった補強シート９'の一部とその直上の第２ガス拡散層５'に樹脂を含浸させて、封止部８'を形成し、第２ガス拡散層５'を補強シート９'に固定させる。   Next, in this state, a part of the reinforcing sheet 9 overlapped with the first gas diffusion layer 5 and the first gas diffusion layer 5 immediately above the resin sheet are impregnated with the resin to form the sealing portion 8. The diffusion layer 5 is fixed to the reinforcing sheet 9. Similarly, a part of the reinforcing sheet 9 ′ overlapping the second gas diffusion layer 5 ′ and the second gas diffusion layer 5 ′ immediately above the resin sheet are impregnated with resin to form a sealing portion 8 ′, and the second gas The diffusion layer 5 ′ is fixed to the reinforcing sheet 9 ′.

このように、本発明の補強シート付き膜・電極接合体の製造方法の一例では、補強シートとしてクッション性を有する多孔質膜を用いる。そのため、第１触媒層４、第２触媒層４'よりも厚みが厚い補強シート９，９'を用いても、第１触媒含有層１２の一部、および第２触媒含有層１２'の一部を電解質膜１に容易に熱転写でき、触媒層が電解質膜１に食い込む恐れが低減されている。   Thus, in an example of the method for producing a membrane / electrode assembly with a reinforcing sheet of the present invention, a porous membrane having cushioning properties is used as the reinforcing sheet. Therefore, even if the reinforcing sheets 9 and 9 ′ having a thickness larger than that of the first catalyst layer 4 and the second catalyst layer 4 ′ are used, a part of the first catalyst-containing layer 12 and one part of the second catalyst-containing layer 12 ′ are used. The portion can be easily thermally transferred to the electrolyte membrane 1, and the possibility that the catalyst layer bites into the electrolyte membrane 1 is reduced.

また、補強シート９，９'としてクッション性を有する多孔質膜を用いているので、第１ガス拡散層５、第２ガス拡散層５'を、第１触媒層４、第２触媒層４'上に配置する際に、第１ガス拡散層５および第２ガス拡散層５'が割れる恐れが低減されている。そのため、ガス拡散層に機械的不可によるダメージをもたらすことなく、触媒層とガス拡散層とを、各々その間に隙間を有するとこなく相互に接した状態にすることができる。これにより、触媒層とガス拡散層との間に良好な接触を確保できる。   Further, since the porous sheet having cushioning properties is used as the reinforcing sheets 9 and 9 ′, the first gas diffusion layer 5 and the second gas diffusion layer 5 ′ are replaced with the first catalyst layer 4 and the second catalyst layer 4 ′. When arranged on top, the risk of the first gas diffusion layer 5 and the second gas diffusion layer 5 'breaking is reduced. Therefore, the catalyst layer and the gas diffusion layer can be brought into contact with each other without having a gap between them without causing mechanical damage to the gas diffusion layer. Thereby, a favorable contact can be ensured between the catalyst layer and the gas diffusion layer.

補強シート９，９'は、連続した細孔を有する多孔質体であるので、ガス拡散層と重なった補強シートの一部とその直上のガス拡散層に樹脂を容易に含浸させることができ、ガス拡散層を補強シートに容易に固定でき、ガスのリークを防止する封止部８、８'を容易に形成できる。   Since the reinforcing sheets 9 and 9 ′ are porous bodies having continuous pores, a part of the reinforcing sheet overlapping with the gas diffusion layer and the gas diffusion layer immediately above the resin sheet can be easily impregnated, The gas diffusion layer can be easily fixed to the reinforcing sheet, and the sealing portions 8 and 8 ′ for preventing gas leakage can be easily formed.

また、本発明の補強シート付き膜・電極接合体の製造方法の一例では、第１ガス拡散層５、第２ガス拡散層５'の外表面５ａ、５ａ'には、何ら配置されていないので、セパレータが向かい合うこととなるガス拡散層の表面は平坦である。そのため、補強シート付き膜・電極接合体の電極とセパレータとの間において良好な電気的接触が確保できる。   In the example of the method for producing a membrane / electrode assembly with a reinforcing sheet according to the present invention, there is no arrangement on the outer surfaces 5a and 5a ′ of the first gas diffusion layer 5 and the second gas diffusion layer 5 ′. The surface of the gas diffusion layer where the separator faces is flat. Therefore, good electrical contact can be secured between the electrode of the membrane / electrode assembly with a reinforcing sheet and the separator.

このように、本発明の補強シート付き膜・電極接合体の製造方法の一例によれば、機械的負荷によるダメージが抑制される。さらに、図５に示されるような方法で、ガス拡散層を触媒層上に配置し、ガス拡散層を補強シートに固定すれば、触媒層とガス拡散層との接触が良好で、かつ、電極とセパレータとの電気的接触が良好な、補強シート付き膜・電極接合体を提供できる。   Thus, according to an example of the method for producing a membrane / electrode assembly with a reinforcing sheet of the present invention, damage due to a mechanical load is suppressed. Further, if the gas diffusion layer is disposed on the catalyst layer and fixed to the reinforcing sheet by the method shown in FIG. 5, the contact between the catalyst layer and the gas diffusion layer is good, and the electrode It is possible to provide a membrane-electrode assembly with a reinforcing sheet that has good electrical contact with the separator.

第１触媒層４および第２触媒層４’は、ともに触媒粒子を担持させた炭素粒子（触媒担持炭素粒子）と、水素イオン伝導性高分子電解質とを含有している。触媒粒子としては、例えば、白金、白金化合物等が挙げられる。白金化合物としては、例えば、ルテニウム、パラジウム、ニッケル、モリブデン、イリジウム、鉄、コバルト等からなる群から選ばれる少なくとも１種の金属と白金との合金等が挙げられる。   Both the first catalyst layer 4 and the second catalyst layer 4 ′ contain carbon particles carrying catalyst particles (catalyst-carrying carbon particles) and a hydrogen ion conductive polymer electrolyte. Examples of the catalyst particles include platinum and platinum compounds. Examples of the platinum compound include an alloy of platinum and at least one metal selected from the group consisting of ruthenium, palladium, nickel, molybdenum, iridium, iron, cobalt, and the like.

水素イオン伝導性高分子電解質としては、例えば、パーフルオロスルホン酸系のフッ素イオン交換樹脂等が挙げられる。上記触媒担持炭素粒子と水素イオン伝導性高分子電解質の配合比は、固形分量の重量比率で１：０．１〜１：１であると好ましく、１：０．２〜１：０．５であるとより好ましい。   Examples of the hydrogen ion conductive polymer electrolyte include perfluorosulfonic acid-based fluorine ion exchange resins. The mixing ratio of the catalyst-supporting carbon particles and the hydrogen ion conductive polymer electrolyte is preferably 1: 0.1 to 1: 1 by weight ratio of the solid content, and is preferably 1: 0.2 to 1: 0.5. More preferably.

第１触媒層４および第２触媒層４’の厚さは、通常、１０〜５０μｍであると好ましく、１５〜３０μｍであるとより好ましい。   The thicknesses of the first catalyst layer 4 and the second catalyst layer 4 ′ are usually preferably 10 to 50 μm and more preferably 15 to 30 μm.

電解質膜１には、公知のものを用いることができるが、例えば、パーフルオロスルホン酸系のフッ素イオン交換樹脂膜、より具体的には、炭化水素系イオン交換膜のＣ−Ｈ結合をフッ素で置換したパーフルオロカーボンスルホン酸系ポリマー（ＰＦＳ系ポリマー）等の、プロトン伝導性高分子電解質からなる膜が挙げられる。電気陰性度の高いフッ素原子を導入することで、化学的に非常に安定し、スルホン酸基の解離度が高く、高いイオン伝導性が実現できる。このようなプロトン伝導性高分子電解質膜の具体例としては、例えば、デュポン社製の「Ｎａｆｉｏｎ」（登録商標）、旭硝子（株）製の「Ｆｌｅｍｉｏｎ」（登録商標）、旭化成（株）製の「Ａｃｉｐｌｅｘ」（登録商標）、ゴア（Ｇｏｒｅ）社製の「Ｇｏｒｅ Ｓｅｌｅｃｔ」（登録商標）等が挙げられる。   As the electrolyte membrane 1, known ones can be used. For example, perfluorosulfonic acid-based fluorine ion exchange resin membranes, more specifically, C—H bonds of hydrocarbon-based ion exchange membranes with fluorine are used. Examples include membranes made of proton conductive polymer electrolytes such as substituted perfluorocarbon sulfonic acid polymers (PFS polymers). By introducing a fluorine atom having high electronegativity, it is chemically very stable, the dissociation degree of the sulfonic acid group is high, and high ion conductivity can be realized. Specific examples of such a proton conductive polymer electrolyte membrane include, for example, “Nafion” (registered trademark) manufactured by DuPont, “Flemion” (registered trademark) manufactured by Asahi Glass Co., Ltd., and manufactured by Asahi Kasei Corporation. “Aciplex” (registered trademark), “Gore Select” (registered trademark) manufactured by Gore, and the like.

補強シート付き膜・電極接合体の製造に用いられる電解質膜の膜厚は、通常２０〜２５０μｍであると好ましく、２０〜８０μｍであるとより好ましい。   The thickness of the electrolyte membrane used for the production of the membrane / electrode assembly with a reinforcing sheet is usually preferably 20 to 250 μm, and more preferably 20 to 80 μm.

第１ガス拡散層５および第２ガス拡散層５'としては、公知のものを用いることができる。例えば、燃料である燃料ガス等を効率よく第１触媒層４および第２触媒層４'に供給可能な、多孔質の導電性基材、より具体的には、カーボンペーパーまたはカーボンクロス等を用いることができる。   A well-known thing can be used as 1st gas diffusion layer 5 and 2nd gas diffusion layer 5 '. For example, a porous conductive substrate that can efficiently supply fuel gas or the like as fuel to the first catalyst layer 4 and the second catalyst layer 4 ′, more specifically, carbon paper or carbon cloth is used. be able to.

補強シート９、９‘の電解質膜１への固定は、例えば、ロールプレス、平面プレス等を用いた熱圧着等により行える。これらの固定の際のプレス機に設定される圧力は、１〜１００ｋｇｆ／ｃｍ2であると好ましく、１０〜５０ｋｇｆ／ｃｍ2であるとより好ましい。プレス機表面の温度は、８０〜２００℃であると好ましく、１００〜１７０℃であるとより好ましい。 The reinforcing sheets 9 and 9 ′ can be fixed to the electrolyte membrane 1 by, for example, thermocompression using a roll press, a flat press or the like. The pressure to be set in the press machine during these fixed, preferable to be 1~100kgf / cm 2, more preferably a 10~50kgf / cm 2. The temperature of the press machine surface is preferably 80 to 200 ° C, more preferably 100 to 170 ° C.

支持基材１１、１１'としては、触媒と電解質バインダーの分散状態が良好で、細孔構造が均質な第１触媒含有層１２、第２触媒含有層１２’を形成可能であれば特に制限はないが、例えば、平坦な表面を有する、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、ポリイミド、ポリアミド、アセタール樹脂、ポリフェニレンオキシドポリエチレン、ポリプロピレン、ポリテトラフルオロエチレン等の熱可塑性樹脂等からなる樹脂シート等が挙げられる。なかでも、第１触媒含有層１２または第２触媒含有層１２’の離型性が良好な、ポリプロピレン、ポリエチレンテレフタレート、ポリテトラフルオロエチレン等が好ましい。   The support bases 11 and 11 ′ are not particularly limited as long as the first catalyst-containing layer 12 and the second catalyst-containing layer 12 ′ can be formed with a good dispersion state of the catalyst and the electrolyte binder and a uniform pore structure. For example, a resin sheet having a flat surface, such as polyethylene terephthalate, polybutylene terephthalate, polyimide, polyamide, acetal resin, polyphenylene oxide polyethylene, polypropylene, polytetrafluoroethylene, etc. It is done. Among these, polypropylene, polyethylene terephthalate, polytetrafluoroethylene and the like, which have good releasability of the first catalyst-containing layer 12 or the second catalyst-containing layer 12 ′, are preferable.

支持基材１１、１１'の厚さについて特に制限はないが、取り扱い性が良好かつＲｏｌｌ ｔｏ Ｒｏｌｌ対応巻取装置への適応が良好であるので、通常、１０μｍ〜１００μｍが好ましく、２０μｍ〜６０μｍがより好ましい。   Although there is no restriction | limiting in particular about the thickness of the support base materials 11 and 11 ', Since handling property is favorable and the adaptation to Roll to Roll corresponding | compatible winding apparatus is favorable, 10 micrometers-100 micrometers are preferable normally, and 20 micrometers-60 micrometers are preferable. More preferred.

第１触媒含有層１２および第２触媒含有層１２’の形成には、触媒担持炭素粒子と水素イオン伝導性高分子電解質とを適当な溶剤中で混合し分散することにより得られる、触媒含有ペーストを用いる。   For the formation of the first catalyst-containing layer 12 and the second catalyst-containing layer 12 ′, a catalyst-containing paste obtained by mixing and dispersing the catalyst-supporting carbon particles and the hydrogen ion conductive polymer electrolyte in an appropriate solvent. Is used.

上記溶剤としては、例えば、各種アルコール類、各種エーテル類、各種ジアルキルスルホキシド類、水又はこれらの混合物等が挙げられる。   Examples of the solvent include various alcohols, various ethers, various dialkyl sulfoxides, water, or a mixture thereof.

触媒含有ペーストの塗布方法は、特に限定されるものではなく、例えば、ナイフコーター、バーコーター、スプレー、ディップコーター、スピンコーター、ロールコーター、ダイコーター、カーテンコーター、スクリーン印刷等の一般的な方法を適用できる。   The method for applying the catalyst-containing paste is not particularly limited. For example, a general method such as knife coater, bar coater, spray, dip coater, spin coater, roll coater, die coater, curtain coater, screen printing, etc. Applicable.

第１触媒含有層１２および第２触媒含有層１２’の厚さは、通常、１０〜５０μｍであると好ましく、１５〜３０μｍであるとより好ましい。   The thicknesses of the first catalyst-containing layer 12 and the second catalyst-containing layer 12 ′ are usually preferably 10 to 50 μm and more preferably 15 to 30 μm.

第１触媒含有層１２および第２触媒含有層１２’の熱転写は、例えば、ロールプレス、平面プレスにより行える。熱転写の際のプレス機に設定される圧力は、１〜１００ｋｇｆｋｇｆ／ｃｍ2であると好ましく、１０〜５０ｋｇｆ／ｃｍ2であるとより好ましい。プレス機表面の温度は、８０〜２００℃であると好ましく、１００〜１７０℃であるとより好ましい。 The thermal transfer of the first catalyst-containing layer 12 and the second catalyst-containing layer 12 ′ can be performed by, for example, a roll press or a plane press. The pressure to be set in the press machine during the thermal transfer, preferable to be 1~100kgfkgf / cm 2, more preferably a 10~50kgf / cm 2. The temperature of the press machine surface is preferably 80 to 200 ° C, more preferably 100 to 170 ° C.

補強シート９、９'は、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリビニリデンジフルオライド（ＰＶＤＦ）、ニトロセルロース、再生セルロース、ポリカーボネート、または、親水化処理されたポリテトラフルオロエチレンを含む多孔質体であると、機械特性に優れるので、好ましい。より具体的には、ＰＴＦＥ多孔質膜、ＰＶＤＦ多孔質膜、セルロース混合エステル多孔質膜、セルロースアセテート多孔質膜、ＰＴＦＥ多孔質膜にポリプロピレンネットが積層された積層膜、親水化処理されたＰＴＦＥ多孔質膜等が好ましい。なかでも、耐久性が良好な、ＰＴＦＥ、ＰＶＤＦ等のフッ素樹脂からなる多孔質膜が好ましい。   The reinforcing sheets 9 and 9 ′ are porous bodies containing polytetrafluoroethylene (PTFE), polyvinylidene difluoride (PVDF), nitrocellulose, regenerated cellulose, polycarbonate, or hydrophilized polytetrafluoroethylene. It is preferable because it has excellent mechanical properties. More specifically, a PTFE porous film, a PVDF porous film, a cellulose mixed ester porous film, a cellulose acetate porous film, a laminated film in which a polypropylene net is laminated on a PTFE porous film, and a hydrophilic PTFE porous film A membrane is preferred. Among these, a porous membrane made of a fluororesin such as PTFE or PVDF having good durability is preferable.

補強シート９、９'の形態は、電解質膜にダメージを及ぼすことなく、触媒層を形成可能であり、ガス拡散層を触媒層上に配置可能であり、かつ、樹脂の含浸が良好に行われる限り特に制限はないが、上記多孔質膜の孔径は、樹脂の含浸がより良好におこなわれるという理由から、０．１〜１０μｍであると好ましく、０．５〜５μｍであるとより好ましい。多孔質膜の空隙率は、樹脂の含浸がより良好におこなわれ、かつ、高い機械特性が確保できるという理由から、５０〜９５％であると好ましく、７０〜９５％であるとより好ましい。   The form of the reinforcing sheets 9 and 9 ′ can form a catalyst layer without damaging the electrolyte membrane, the gas diffusion layer can be disposed on the catalyst layer, and the resin is satisfactorily impregnated. Although there is no particular limitation, the pore diameter of the porous membrane is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm, because the resin is more effectively impregnated. The porosity of the porous membrane is preferably 50 to 95%, more preferably 70 to 95%, because the resin can be more satisfactorily impregnated and high mechanical properties can be secured.

補強シートの厚さＷ（図５Ａ参照）は、触媒層のそれよりも厚いと好ましいが、触媒層とガス拡散層とからなる積層体の厚みよりも薄いと好ましい。この場合、ガス拡散層と重なった補強シートの一部とその直上のガス拡散層に樹脂を含浸させやすく、封止部８、８'を容易に形成できる。補強シートの厚さＷは、具体的には、２０〜２５０μｍが好ましく、５０〜１００μｍがより好ましい。   The thickness W (see FIG. 5A) of the reinforcing sheet is preferably thicker than that of the catalyst layer, but is preferably thinner than the thickness of the laminate composed of the catalyst layer and the gas diffusion layer. In this case, a part of the reinforcing sheet overlapping the gas diffusion layer and the gas diffusion layer immediately above the part can be easily impregnated with the resin, and the sealing portions 8 and 8 ′ can be easily formed. Specifically, the thickness W of the reinforcing sheet is preferably 20 to 250 μm, and more preferably 50 to 100 μm.

ガス拡散層および補強シートに含浸させる樹脂としては、例えば、ポリテトラフルオロエチレン等のフッ素樹脂、２液硬化型接着剤、紫外線硬化樹脂、または電子線硬化型樹脂が挙げられるが、化学的安定性が良好であるという理由から、ポリテトラフルオロエチレン、紫外線硬化樹脂等が好ましい。   Examples of the resin impregnated in the gas diffusion layer and the reinforcing sheet include a fluorine resin such as polytetrafluoroethylene, a two-component curable adhesive, an ultraviolet curable resin, and an electron beam curable resin. Polytetrafluoroethylene, ultraviolet curable resin, and the like are preferable for the reason that is good.

以下に実施例によって本発明をより詳細に説明するが、本発明はこれらに限定されない。［実施例１］
下記成分を分散機で分散することにより触媒含有ペーストを調整した。
［触媒含有ペーストの組成］
触媒（TEC10E70TPM、田中貴金属（株）製） １重量部
電解質（nafionDE2020 CS デュポン社製） ０．２５重量部
水 ２重量部
ｎ−ブタノール ６重量部 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. [Example 1]
A catalyst-containing paste was prepared by dispersing the following components with a disperser.
[Composition of catalyst-containing paste]
Catalyst (TEC10E70TPM, Tanaka Kikinzoku Co., Ltd.) 1 part by weight electrolyte (by nafionDE2020 CS DuPont) 0.25 part by weight Water 2 parts by weight n-butanol 6 parts by weight

得られた触媒含有ペーストを、ＰＥＴ基材（東洋紡製、Ｅ３１２０，厚さ１２μｍ、５．５ｃｍ×５．５ｃｍ）に塗工した後、塗布された触媒含有ペーストを風乾して、触媒含有層（厚さ２０μｍ）を形成した。触媒含有ペーストは、Ｐｔ担持量が０．５ｍｇ／ｃｍ2となるよう塗工した。ＰＥＴ基材と触媒含有層（厚さ２４μｍ、Ｐｔ担持量が０．５ｍｇ／ｃｍ2）とからなる積層体をもう一つ用意した。 The obtained catalyst-containing paste was applied to a PET substrate (Toyobo, E3120, thickness 12 μm, 5.5 cm × 5.5 cm), and then the applied catalyst-containing paste was air-dried to obtain a catalyst-containing layer ( A thickness of 20 μm) was formed. The catalyst-containing paste was applied so that the amount of Pt supported was 0.5 mg / cm 2 . Another laminate comprising a PET substrate and a catalyst-containing layer (thickness 24 μm, Pt loading 0.5 mg / cm 2 ) was prepared.

次に、電解質膜（デュポン社製、nafion212 CS、７．５ｃｍ×７．５ｃｍ）と、２枚の補強シート（親水性ＰＴＦＥメンブレンフィルター アドバンテック東洋社製、Ｔ０８０Ａ３３０、厚み７５μｍ、孔径３．００μｍ、空隙率８３％）を用意した。補強シートは、その中央部に５．０ｃｍ×５．０ｃｍの開口を有する。電解質膜の両主面上に各々補強シートを配置した。なお、補強シートの孔径はバブルポイント法により測定された値であり、具体的には下記のようにして測定された値である。   Next, an electrolyte membrane (manufactured by DuPont, nafion212 CS, 7.5 cm × 7.5 cm) and two reinforcing sheets (hydrophilic PTFE membrane filter, manufactured by Advantech Toyo Co., Ltd., T080A330, thickness 75 μm, pore diameter 3.00 μm, voids 83%). The reinforcing sheet has an opening of 5.0 cm × 5.0 cm at the center thereof. Reinforcing sheets were respectively disposed on both main surfaces of the electrolyte membrane. In addition, the hole diameter of a reinforcement sheet is the value measured by the bubble point method, and is specifically the value measured as follows.

（バブルポイント法）
イソプロピルアルコールで補強シートを完全に濡らしてあらかじめ膜の細孔内にイソプロピルアルコールを吸収させておき、補強シートの裏側から空気圧をかけて、補強シートの表面に気泡の発生が観察できる最小圧力（ＭＰａ，バブルポイント）を測定する。液体の表面張力とこの圧力との関係式から細孔径が推算できる。 (Bubble point method)
Wet the reinforcing sheet completely with isopropyl alcohol to absorb isopropyl alcohol in the pores of the membrane beforehand, apply air pressure from the back side of the reinforcing sheet, and observe the minimum pressure (MPa) , Bubble point). The pore diameter can be estimated from the relational expression between the surface tension of the liquid and this pressure.

次に、ＰＥＴ基材と触媒含有層とからなる積層体２つを、各々、触媒含有層が電解質膜と向かい合うように、電解質膜に対向させ、熱プレス（１１０℃、５０ｋｇｆ）により、補強シートをマスクとして、電解質膜に触媒含有層の一部を熱転写するとともに、補強シートを熱プレスにより電解質膜に固定した。その後、転写された触媒含有層からＰＥＴ基材を剥離した。このようにして、電解質膜の一方の主面に第１触媒層（厚さ２０μｍ）を、他方の主面に第２触媒層（厚さ２４μｍ）を形成した。   Next, the two laminates composed of the PET base material and the catalyst-containing layer are respectively opposed to the electrolyte membrane so that the catalyst-containing layer faces the electrolyte membrane, and the reinforcing sheet is formed by hot pressing (110 ° C., 50 kgf). As a mask, a part of the catalyst-containing layer was thermally transferred to the electrolyte membrane, and the reinforcing sheet was fixed to the electrolyte membrane by hot pressing. Thereafter, the PET substrate was peeled from the transferred catalyst-containing layer. In this way, a first catalyst layer (thickness 20 μm) was formed on one main surface of the electrolyte membrane, and a second catalyst layer (thickness 24 μm) was formed on the other main surface.

次に、第１触媒層および第２触媒層の上に、各々、ガス拡散層（ＳＧＬカーボン社製、カーボンペーパー２４ＢＡ、厚さ２００μｍ、５．３ｃｍ×５．３ｃｍ）を配置した。次いで、ガス拡散層により押し潰された補強シートとその直上のガス拡散層に紫外線硬化脂を含浸させた。具体的には、ガス拡散層により押し潰された補強シートとその直上のガス拡散層に樹脂が含浸されるように、ガス拡散層上にマスクを配置し、マスクにより被覆されていない部分に塗布により紫外線硬化樹脂を供給した。次いで、紫外線を照射して、含浸された紫外線硬化樹脂を硬化させ、封止部を形成した。   Next, gas diffusion layers (manufactured by SGL Carbon, carbon paper 24BA, thickness 200 μm, 5.3 cm × 5.3 cm) were disposed on the first catalyst layer and the second catalyst layer, respectively. Next, the reinforcing sheet crushed by the gas diffusion layer and the gas diffusion layer immediately above the impregnated sheet were impregnated with ultraviolet curable fat. Specifically, a mask is placed on the gas diffusion layer so that the resin is impregnated into the reinforcing sheet crushed by the gas diffusion layer and the gas diffusion layer directly above it, and applied to the part not covered by the mask. UV curable resin was supplied. Next, ultraviolet rays were irradiated to cure the impregnated ultraviolet curable resin, thereby forming a sealing portion.

本発明の補強シート付き膜・電極接合体の一例は、その製造過程において、電解質膜やガス拡散層等が受ける機械的負荷によるダメージが抑制されており、触媒層とガス拡散層との接触が良好で、かつ、電極とセパレータとの電気的接触が良好であるので、有用である。   An example of the membrane / electrode assembly with a reinforcing sheet of the present invention is such that damage due to a mechanical load applied to the electrolyte membrane, the gas diffusion layer, and the like is suppressed in the manufacturing process, and the contact between the catalyst layer and the gas diffusion layer is prevented. It is useful because it is good and the electrical contact between the electrode and the separator is good.

図１は、本発明の補強シート付き膜・電極接合体の一例の平面図FIG. 1 is a plan view of an example of a membrane / electrode assembly with a reinforcing sheet of the present invention. 図２は、図１のＩ−Ｉ'模式断面図2 is a schematic cross-sectional view taken along the line II ′ of FIG. 図３は、ガスケット付き膜・電極接合体の一例の平面図3 is a plan view of an example of a membrane / electrode assembly with gasket. 図４は、図３のII−II'模式断面図4 is a schematic cross-sectional view taken along the line II-II ′ of FIG. 図５のＡ〜Ｄは、本発明の補強シート付き膜・電極接合体の製造方法の一例を説明する工程模式断面図5A to 5D are process schematic cross-sectional views illustrating an example of a method for producing a membrane-electrode assembly with a reinforcing sheet of the present invention.

符号の説明Explanation of symbols

１ 電解質膜
４ 第１触媒層
４’ 第２触媒層
５ 第１ガス拡散層
５’ 第２ガス拡散層
６ 燃料極
７ 空気極
８，８' 封止部
９，９' 補強シート
１０、１０' ガスケット
１１、１１' 支持基材
１２ 第１触媒含有層
１２' 第２触媒含有層
１００ 補強シート付き膜・電極接合体 DESCRIPTION OF SYMBOLS 1 Electrolyte membrane 4 1st catalyst layer 4 '2nd catalyst layer 5 1st gas diffusion layer 5' 2nd gas diffusion layer 6 Fuel electrode 7 Air electrode 8, 8 'Sealing part 9, 9' Reinforcement sheet 10, 10 ' Gasket 11, 11 ′ Support base material 12 First catalyst-containing layer 12 ′ Second catalyst-containing layer 100 Membrane / electrode assembly with reinforcing sheet

Claims (10)

電解質膜と、
前記電解質膜の両主面の中央部に前記電解質膜を挟むように接合された、１対の触媒層と、
前記触媒層の平面形状に対応した形状の開口を有し、連続した細孔を有する多孔質体からなり、各触媒層の周囲に配置され、前記触媒層の端面に接した、１対の補強シートと、を含む固体高分子型燃料電池用補強シート付き膜・電極接合体。 An electrolyte membrane;
A pair of catalyst layers joined so as to sandwich the electrolyte membrane at the center of both main surfaces of the electrolyte membrane;
A pair of reinforcements having a shape corresponding to the planar shape of the catalyst layer, made of a porous body having continuous pores, arranged around each catalyst layer and in contact with the end face of the catalyst layer And a membrane / electrode assembly with a reinforcing sheet for a polymer electrolyte fuel cell. 各触媒層上に配置され、平面形状が前記触媒層のそれより大きいガス拡散層をさらに含む、請求項１に記載の固体高分子型燃料電池用補強シート付き膜・電極接合体。   The membrane-electrode assembly with a reinforcing sheet for a polymer electrolyte fuel cell according to claim 1, further comprising a gas diffusion layer disposed on each catalyst layer and having a planar shape larger than that of the catalyst layer. 前記補強シートの厚みが、前記触媒層よりも厚く、前記触媒層と前記ガス拡散層とからなる積層体よりも薄い、請求項２に記載の固体高分子型燃料電池用補強シート付き膜・電極接合体。   The membrane / electrode with a reinforcing sheet for a polymer electrolyte fuel cell according to claim 2, wherein the thickness of the reinforcing sheet is thicker than the catalyst layer and thinner than a laminate comprising the catalyst layer and the gas diffusion layer. Joined body. 前記補強シートの一部が前記ガス拡散層により押し潰されており、前記ガス拡散層と重なった前記補強シートの一部とその直上の前記ガス拡散層に樹脂が含浸されて、前記ガス拡散層が前記補強シートに固定されている、請求項３に記載の固体高分子型燃料電池用補強シート付き膜・電極接合体。   A part of the reinforcing sheet is crushed by the gas diffusion layer, a part of the reinforcing sheet overlapping the gas diffusion layer and the gas diffusion layer immediately above the resin sheet are impregnated with the resin, and the gas diffusion layer The membrane / electrode assembly with a reinforcing sheet for a polymer electrolyte fuel cell according to claim 3, wherein is fixed to the reinforcing sheet. 前記樹脂が、フッ素樹脂、２液硬化型接着剤、紫外線硬化樹脂、または電子線硬化型樹脂を含む請求項４に記載の固体高分子型燃料電池用補強シート付き膜・電極接合体。   The membrane / electrode assembly with a reinforcing sheet for a polymer electrolyte fuel cell according to claim 4, wherein the resin comprises a fluororesin, a two-component curable adhesive, an ultraviolet curable resin, or an electron beam curable resin. 前記補強シートは、ポリテトラフルオロエチレン、ポリビニリデンジフルオライド、ニトロセルロース、再生セルロース、ポリカーボネート、または、親水化処理されたポリテトラフルオロエチレンを含む多孔質体からなる請求項１〜５のいずれかの項に記載の、固体高分子型燃料電池用補強シート付き膜・電極接合体。   The reinforcing sheet is made of polytetrafluoroethylene, polyvinylidene difluoride, nitrocellulose, regenerated cellulose, polycarbonate, or a porous body containing hydrophilized polytetrafluoroethylene. The membrane / electrode assembly with a reinforcing sheet for a polymer electrolyte fuel cell according to the section. 前記補強シートの孔径が、０．１〜１０μｍである請求項１〜６のいずれかの項に記載の固体高分子型燃料電池用補強シート付き膜・電極接合体。   The membrane / electrode assembly with a reinforcing sheet for a polymer electrolyte fuel cell according to any one of claims 1 to 6, wherein the pore diameter of the reinforcing sheet is 0.1 to 10 µm. 請求項１〜７のいずれかの項に記載の固体高分子型燃料電池用補強シート付き膜・電極接合体を含む固体高分子型燃料電池。   A polymer electrolyte fuel cell comprising the membrane / electrode assembly with a reinforcing sheet for polymer electrolyte fuel cell according to any one of claims 1 to 7. 電解質膜と、前記電解質膜の両主面の中央部に前記電解質膜を挟むように接合された、１対の触媒層と、各触媒層の周囲に配置され前記触媒層の端面に接した１対の補強シートとを含む、固体高分子型燃料電池用補強シート付き膜・電極接合体の製造方法であって、
前記電解質膜の両主面上に、各々、前記触媒層の平面形状に対応した形状の開口を有し、連続した細孔を有する多孔質体からなる前記補強シートを配置する工程と、
支持基材と前記支持基材上に配置された触媒含有層とを含む積層体の前記触媒含有層の一部を、前記補強シートの前記開口から露出した前記電解質膜に熱転写して、前記電解質膜の両主面に各々触媒層を形成するとともに前記補強シートを各々前記電解質膜の両主面に固定する工程と、を含む固体高分子型燃料電池用補強シート付き膜・電極接合体の製造方法。 An electrolyte membrane, a pair of catalyst layers joined so as to sandwich the electrolyte membrane between the main portions of both main surfaces of the electrolyte membrane, and 1 in contact with an end face of the catalyst layer disposed around each catalyst layer A method for producing a membrane / electrode assembly with a reinforcing sheet for a polymer electrolyte fuel cell, comprising a pair of reinforcing sheets,
Disposing the reinforcing sheet made of a porous body having openings corresponding to the planar shape of the catalyst layer on both main surfaces of the electrolyte membrane and having continuous pores; and
A portion of the catalyst-containing layer of the laminate including a support substrate and a catalyst-containing layer disposed on the support substrate is thermally transferred to the electrolyte membrane exposed from the opening of the reinforcing sheet, and the electrolyte Forming a catalyst layer on each main surface of the membrane and fixing the reinforcing sheet to each main surface of the electrolyte membrane, and manufacturing a membrane-electrode assembly with a reinforcing sheet for a polymer electrolyte fuel cell Method. 各触媒層上にガス拡散層を配置するガス拡散層形成工程を含み、
前記ガス拡散層形成工程において、平面形状が前記触媒層のそれより大きいガス拡散層が前記触媒層に接するまで、前記触媒層よりも厚い前記補強シートの一部を前記ガス拡散層で押し潰し、この状態で、前記ガス拡散層と重なった前記補強シートの一部とその直上
のガス拡散層に樹脂を含浸させて、前記ガス拡散層を前記補強シートに固定させる、請求項９に記載の固体高分子型燃料電池用補強シート付き膜・電極接合体の製造方法。 Including a gas diffusion layer forming step of disposing a gas diffusion layer on each catalyst layer;
In the gas diffusion layer forming step, until a gas diffusion layer whose planar shape is larger than that of the catalyst layer contacts the catalyst layer, a part of the reinforcing sheet thicker than the catalyst layer is crushed by the gas diffusion layer, 10. The solid according to claim 9, wherein in this state, a part of the reinforcing sheet overlapping the gas diffusion layer and the gas diffusion layer immediately above the resin diffusion sheet are impregnated with resin to fix the gas diffusion layer to the reinforcing sheet. A method for producing a membrane / electrode assembly with a reinforcing sheet for a polymer fuel cell.
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