JP2012009196A - Film electrode diffusion layer junction and method for manufacturing the same - Google Patents

Film electrode diffusion layer junction and method for manufacturing the same Download PDF

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JP2012009196A
JP2012009196A JP2010142482A JP2010142482A JP2012009196A JP 2012009196 A JP2012009196 A JP 2012009196A JP 2010142482 A JP2010142482 A JP 2010142482A JP 2010142482 A JP2010142482 A JP 2010142482A JP 2012009196 A JP2012009196 A JP 2012009196A
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Hiroshi Suzuki
弘 鈴木
Takuo Yanagi
拓男 柳
Shinpei Nono
晋平 野納
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Toyota Motor Corp
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Abstract

PROBLEM TO BE SOLVED: To provide a film electrode diffusion layer junction having an integrated structure in which interface formation between each layer is prevented.SOLUTION: A first catalyst precursor layer is formed by coating one surface of a electrolyte precursor film with a catalyst layer material, and the surface of the electrolyte precursor film is fused by fluorine solvent included in the catalyst layer material, so that the electrolyte precursor film and the first catalyst precursor layer are integrated. A diffusion layer material is bonded to the upper face of the first catalyst precursor layer before the fluorine solvent is dried, and a part of the catalyst layer material is impregnated into the diffusion layer material, so that the first catalyst precursor layer and the diffusion layer material are integrated. A second catalyst precursor layer is formed by coating the other surface of the electrolyte precursor film with the catalyst layer material, and the surface of the electrolyte precursor film is fused by the fluorine solvent included in the catalyst layer material, so that the electrolyte precursor film and the second catalyst precursor layer are integrated. Ionomer impregnated into the first catalyst precursor layer, the second catalyst precursor layer, electrolyte precursor film, and the diffusion layer material is sulfonated by performing a water-added decomposition treatment from the second catalyst precursor layer side.

Description

本発明は、固体高分子電解質型燃料電池に用いられる膜電極拡散層接合体、特に、電解質膜から触媒層および拡散層までの各部材の境界における界面形成を防止するように形成された一体的な構造を有する膜電極拡散層接合体に関する。   The present invention relates to a membrane electrode diffusion layer assembly for use in a solid polymer electrolyte fuel cell, and more particularly, to integrally form an interface at the boundary of each member from the electrolyte membrane to the catalyst layer and the diffusion layer. The present invention relates to a membrane electrode diffusion layer assembly having a unique structure.

燃料電池は、燃料ガスとしての水素と酸化ガスとしての酸素との電気化学反応によって発電する装置である。なお、以下では、燃料ガスや酸化ガスを、特に区別することなく単に「反応ガス」あるいは「ガス」と呼ぶ場合もある。燃料電池は、通常、燃料電池セルを、セパレータを介して複数個積層して構成される。１つの燃料電池セルは、プロトン（Ｈ+）伝導性を有する固体高分子電解質膜（以下、単に「電解質膜」とも呼ぶ）の両面に触媒電極層（以下、単に「触媒層」とも呼ぶ）を接合した膜電極接合体（ＭＥＡ：Membrane-Electrode Assembly）を用い、ＭＥＡの両面にガス拡散層を配置した膜電極ガス拡散層接合体（ＭＥＧＡ：Membrane Electrode & Gas Diffusion Layer Assembly）により構成される場合が多い。 A fuel cell is a device that generates electricity by an electrochemical reaction between hydrogen as a fuel gas and oxygen as an oxidizing gas. Hereinafter, the fuel gas and the oxidizing gas may be simply referred to as “reaction gas” or “gas” without particular distinction. A fuel cell is usually configured by stacking a plurality of fuel cells via a separator. One fuel cell has a catalyst electrode layer (hereinafter also simply referred to as “catalyst layer”) on both sides of a solid polymer electrolyte membrane (hereinafter also simply referred to as “electrolyte membrane”) having proton (H + ) conductivity. When a membrane electrode assembly (MEA) is used and a MEA (Membrane Electrode & Gas Diffusion Layer Assembly) with gas diffusion layers on both sides of the MEA There are many.

従来、電解質膜は水・アルコール類を溶媒とした電解質の分散溶液を用いて形成されており、触媒層も水・アルコール類を溶媒とした触媒担時カーボンの分散溶液を用いて形成されている。このため、ＭＥＡの形成時においては、電解質膜および触媒層のどちらも親水状態で成形しなければならず、前後の工程において例えば疎水物性部材が用いられるような場合に親水性部材と疎水物性部材との融合が難しい。また、電解質膜および触媒層のどちらも、溶媒としての水・アルコール類の乾燥のために長時間を要す必要があった。   Conventionally, the electrolyte membrane is formed using an electrolyte dispersion solution using water / alcohol as a solvent, and the catalyst layer is also formed using a catalyst-supported carbon dispersion solution using water / alcohol as a solvent. . Therefore, at the time of forming the MEA, both the electrolyte membrane and the catalyst layer must be formed in a hydrophilic state. For example, when a hydrophobic physical member is used in the previous and subsequent steps, the hydrophilic member and the hydrophobic physical member are used. Fusion with is difficult. Further, both the electrolyte membrane and the catalyst layer required a long time for drying water and alcohols as a solvent.

また、ＭＥＧＡに含まれる拡散層には、通常、電気化学反応による生成水の排水性向上のために、疎水物性部材が用いられる。一方、ＭＥＡの触媒層は上記のように親水性の高い部材である。従って、この拡散層と触媒層とは互いに相反する特性を有するものであるため、例えば、拡散層を触媒層に熱圧着して接合させたとしても接合力が弱く、発電時や低温時における電解質膜の膨潤／収縮により接合部に働く応力によって拡散層の剥離が発生し易く、大幅な性能低下を招く可能性がある、という問題がある。また、拡散層は、表面の凹凸が大きい（荒い）ため、触媒層との密着性が悪く剥離し易いという問題もある。   Moreover, a hydrophobic physical member is usually used for the diffusion layer contained in MEGA in order to improve the drainage of generated water by an electrochemical reaction. On the other hand, the catalyst layer of MEA is a highly hydrophilic member as described above. Therefore, since the diffusion layer and the catalyst layer have mutually opposite characteristics, for example, even when the diffusion layer is bonded to the catalyst layer by thermocompression bonding, the bonding force is weak, and the electrolyte during power generation or low temperature There is a problem that the diffusion layer is likely to be peeled off by the stress acting on the joint due to the swelling / shrinkage of the film, which may lead to a significant decrease in performance. In addition, since the diffusion layer has large (rough) surface irregularities, there is also a problem that the adhesion with the catalyst layer is poor and it is easy to peel.

また、拡散層と触媒層との結合力を高める一つの手段として、電解質（以下、「Ｈ」と記す場合もある）アイオノマと導電性部材を用いた接着層を、拡散層と触媒層との間に介挿することも行なわれる。しかしながら、この場合、拡散層、接着層、および、触媒層として、それぞれ予め成形された部材を用いることになるため、それぞれの部材間における界面ができやすく、ＭＥＧＡにおける電極間の抵抗成分が増加してしまう、という問題が発生する。また、接着層を用いることにより高コスト化という問題も発生する。   In addition, as one means for increasing the bonding force between the diffusion layer and the catalyst layer, an adhesive layer using an electrolyte (hereinafter sometimes referred to as “H”) ionomer and a conductive member is formed between the diffusion layer and the catalyst layer. Intervening is also performed in between. However, in this case, since preformed members are used as the diffusion layer, the adhesive layer, and the catalyst layer, an interface between the members is easily formed, and the resistance component between the electrodes in MEGA increases. Problem occurs. Moreover, the problem of high cost also arises by using an adhesive layer.

また、ＭＥＧＡ全体の強度を高めるために、拡散層によりＭＥＧＡの強度を確保する場合があるが、この場合には、発電時の膨潤／収縮により拡散層の接合部に働く応力により、剥離や破断が起こり易いという問題もある。   In addition, in order to increase the strength of the entire MEGA, the strength of the MEGA may be ensured by the diffusion layer. In this case, peeling or rupture is caused by the stress acting on the junction of the diffusion layer due to swelling / shrinkage during power generation. There is also a problem that is likely to occur.

特開２００２−５４３５７８号公報JP 2002-543578 A 特開２００８−３１１１９７号公報JP 2008-3111197 A 特開２００８−２７００５３号公報JP 2008-270053 A

本発明は、上述した従来の課題を解決するためになされたものであり、電解質膜から触媒層および拡散層までの各部材の境界における界面形成を防止するように形成された一体的な構造を有する膜電極拡散層接合体を実現する技術を提供することを目的とする。   The present invention has been made in order to solve the above-described conventional problems, and has an integrated structure formed so as to prevent the formation of an interface at the boundary between each member from the electrolyte membrane to the catalyst layer and the diffusion layer. It aims at providing the technique which implement | achieves the membrane electrode diffusion layer assembly which has.

本発明は、上述の課題の少なくとも一部を解決するためになされたものであり、以下の形態又は適用例として実現することが可能である。   SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following forms or application examples.

［適用例１］
膜電極拡散層接合体の作製方法であって
ＳＯ２Ｆ基を有する電解質前駆体により構成されたイオン交換基能を備えない電解質前駆体膜を準備する工程と、
ＳＯ２Ｆ基を有するアイオノマをフッ素溶媒に溶融分散させたアイオノマ溶液と、疎水物性を有する触媒反応物質と、を混合した触媒層部材を準備する工程と、
疎水物性を有する拡散層部材を準備する工程と、
前記電解質前駆体膜の一方の面に前記触媒層部材を塗工して第１の触媒前駆体層を形成し、前記触媒層部材に含まれる前記フッ素溶媒により前記電解質前駆体膜の表面を溶融させることにより、前記電解質前駆体膜と前記第１の触媒前駆体層とを一体化する工程と、
前記触媒層部材の塗工後前記フッ素溶媒が乾燥する前に、前記第１の触媒前駆体層上面に前記拡散層部材を貼り合わせて、前記触媒層部材の一部を前記拡散層部材内に浸透させることにより、前記第１の触媒前駆体層と前記拡散層部材とを一体化する工程と、
前記電解質前駆体膜の他方の面に前記触媒層部材を塗工して第２の触媒前駆体層を形成し、前記触媒層部材に含まれる前記フッ素溶媒により前記電解質前駆体膜の表面を溶融させることにより、前記電解質前駆体膜と前記第２の触媒前駆体層とを一体化する工程と、
前記拡散層部材と前記第１の触媒前駆体層と前記電解質前駆体膜と前記第２の触媒前駆体層とが一体化された積層体を、前記第２の触媒前駆体層側から加水分解処理して、前記第１の触媒前駆体層、前記第２の触媒前駆体層、前記電解質前駆体膜、および、前記拡散層部材内に浸透した前記アイオノマをスルホン化させることにより、前記第１の触媒前駆体層、前記第２の触媒前駆体層、および、前記電解質前駆体膜を、イオン交換基能を備える電解質を有する第１の触媒層、第２の触媒層、および、電解質膜に変成させる工程と、
を備えることを特徴とする膜電極拡散層接合体の作製方法。
適用例１の作製方法によれば、膜電極拡散層接合体を全体として一体化した構造とすることができるとともに、親水物性を有する電解質膜および触媒層と疎水物性を有する拡散層を、それぞれの境界において界面を持たず連続的に形成された構造とすることができる。
［適用例２］
膜電極拡散層接合体の作製方法であって
多孔部材で構成される補強層部材を準備する工程と、
ＳＯ２Ｆ基を有する電解質前駆体により構成されたイオン交換基能を備えない電解質前駆体膜を準備する工程と、
ＳＯ２Ｆ基を有するアイオノマをフッ素溶媒に溶融分散させたアイオノマ溶液と、疎水物性を有する触媒反応物質と、を混合した触媒層部材を準備する工程と、
疎水物性を有する拡散層部材を準備する工程と、
前記補強層部材の一方の面に前記触媒層部材を塗工して第１の触媒前駆体層を形成し、前記補強層部材内に前記触媒層部材の一部を浸透させることにより、前記補強層部材と前記第１の触媒前駆体層とを一体化する工程と、
前記触媒層部材の塗工後前記フッ素溶媒が乾燥する前に、前記第１の触媒前駆体層上面に前記拡散層部材を貼り合わせて、前記触媒層部材の一部を前記拡散層部材内に浸透させることにより、前記第１の触媒前駆体層と前記拡散層部材とを一体化する工程と、
前記補強層部材の他方の面に前記電解質前駆体膜の一方の面を貼り合わせて加熱することにより、前記電解質前駆体膜中の前記電解質前駆体を溶融させて、前記補強層部材内に浸透させるとともに、前記第１の触媒前駆体層中の前記アイオノマを軟化させることにより、前記電解質前駆体膜と前記第１の触媒前駆体層とを一体化させる工程と、
前記電解質前駆体膜の他方の面上に前記触媒層部材を塗工して第２の触媒前駆体層を形成し、前記触媒層部材に含まれる前記フッ素溶媒により前記電解質前駆体膜の表面を溶融させることにより、前記電解質前駆体膜と前記第２の触媒前駆体層とを一体化する工程と、
前記拡散層部材と前記第１の触媒前駆体層と前記電解質前駆体膜と前記第２の触媒前駆体層とが一体化された積層体を、前記第２の触媒前駆体層側から加水分解処理して、前記第１の触媒前駆体層、前記第２の触媒前駆体層、前記電解質前駆体膜、および、前記拡散層部材内に浸透した前記アイオノマをスルホン化させることにより、前記第１の触媒前駆体層、前記第２の触媒前駆体層、および、前記電解質前駆体膜を、イオン交換基能を備える電解質を有する第１の触媒層、第２の触媒層、および、電解質膜に変成させる工程と、
を備えることを特徴とする膜電極拡散層接合体の作製方法。
適用例２の作製方法によっても、膜電極拡散層接合体を全体として一体化した構造とすることができるとともに、親水物性を有する電解質膜および触媒層と疎水物性を有する拡散層を、それぞれの境界において界面を持たず連続的に形成された構造とすることができる。また、適用例２の作製方法によれば、補強層を備えているので、適用例１の作製方法よりも強度を高めることが可能である。 [Application Example 1]
A method for preparing a membrane electrode diffusion layer assembly, the step of preparing an electrolyte precursor membrane that does not have an ion-exchange base ability and is constituted by an electrolyte precursor having an SO2F group;
Preparing a catalyst layer member in which an ionomer solution in which an ionomer having an SO2F group is melt-dispersed in a fluorine solvent and a catalytic reactant having hydrophobic properties are mixed;
Preparing a diffusion layer member having hydrophobic properties;
The catalyst layer member is applied to one surface of the electrolyte precursor film to form a first catalyst precursor layer, and the surface of the electrolyte precursor film is melted by the fluorine solvent contained in the catalyst layer member By integrating the electrolyte precursor film and the first catalyst precursor layer,
After the application of the catalyst layer member and before the fluorine solvent is dried, the diffusion layer member is bonded to the upper surface of the first catalyst precursor layer, and a part of the catalyst layer member is placed in the diffusion layer member. Integrating the first catalyst precursor layer and the diffusion layer member by infiltrating;
The catalyst layer member is applied to the other surface of the electrolyte precursor film to form a second catalyst precursor layer, and the surface of the electrolyte precursor film is melted by the fluorine solvent contained in the catalyst layer member. By integrating the electrolyte precursor film and the second catalyst precursor layer,
The laminated body in which the diffusion layer member, the first catalyst precursor layer, the electrolyte precursor film, and the second catalyst precursor layer are integrated is hydrolyzed from the second catalyst precursor layer side. The first catalyst precursor layer, the second catalyst precursor layer, the electrolyte precursor film, and the ionomer that has penetrated into the diffusion layer member are sulfonated by the treatment. The catalyst precursor layer, the second catalyst precursor layer, and the electrolyte precursor film are used as the first catalyst layer, the second catalyst layer, and the electrolyte film having an electrolyte having an ion exchange group ability. A transformation process;
A method for producing a membrane electrode diffusion layer assembly, comprising:
According to the production method of Application Example 1, a membrane electrode diffusion layer assembly can be integrated as a whole, and an electrolyte membrane having a hydrophilic property, a catalyst layer, and a diffusion layer having a hydrophobic property can be provided respectively. It can be set as the structure formed continuously without having an interface in a boundary.
[Application Example 2]
A method for producing a membrane electrode diffusion layer assembly, the step of preparing a reinforcing layer member composed of a porous member,
Preparing an electrolyte precursor film that does not have an ion-exchange group ability and is constituted by an electrolyte precursor having a SO2F group;
Preparing a catalyst layer member in which an ionomer solution in which an ionomer having an SO2F group is melt-dispersed in a fluorine solvent and a catalytic reactant having hydrophobic properties are mixed;
Preparing a diffusion layer member having hydrophobic properties;
The catalyst layer member is coated on one surface of the reinforcement layer member to form a first catalyst precursor layer, and a part of the catalyst layer member is infiltrated into the reinforcement layer member, whereby the reinforcement Integrating a layer member and the first catalyst precursor layer;
After the application of the catalyst layer member and before the fluorine solvent is dried, the diffusion layer member is bonded to the upper surface of the first catalyst precursor layer, and a part of the catalyst layer member is placed in the diffusion layer member. Integrating the first catalyst precursor layer and the diffusion layer member by infiltrating;
By bonding one surface of the electrolyte precursor film to the other surface of the reinforcing layer member and heating, the electrolyte precursor in the electrolyte precursor film is melted and penetrated into the reinforcing layer member And integrating the electrolyte precursor film and the first catalyst precursor layer by softening the ionomer in the first catalyst precursor layer;
The catalyst layer member is coated on the other surface of the electrolyte precursor film to form a second catalyst precursor layer, and the surface of the electrolyte precursor film is covered with the fluorine solvent contained in the catalyst layer member. Integrating the electrolyte precursor film and the second catalyst precursor layer by melting,
The laminated body in which the diffusion layer member, the first catalyst precursor layer, the electrolyte precursor film, and the second catalyst precursor layer are integrated is hydrolyzed from the second catalyst precursor layer side. The first catalyst precursor layer, the second catalyst precursor layer, the electrolyte precursor film, and the ionomer that has penetrated into the diffusion layer member are sulfonated by the treatment. The catalyst precursor layer, the second catalyst precursor layer, and the electrolyte precursor film are used as the first catalyst layer, the second catalyst layer, and the electrolyte film having an electrolyte having an ion exchange group ability. A transformation process;
A method for producing a membrane electrode diffusion layer assembly, comprising:
Also by the production method of Application Example 2, the membrane / electrode diffusion layer assembly can be integrated as a whole, and the electrolyte membrane having a hydrophilic property and the catalyst layer and the diffusion layer having a hydrophobic property can be separated from each other. The structure can be formed continuously without an interface. Further, according to the manufacturing method of Application Example 2, since the reinforcing layer is provided, the strength can be increased as compared with the manufacturing method of Application Example 1.

［適用例３］
膜電極拡散層接合体の作製方法であって
多孔部材で構成される２つの補強層部材を準備する工程と、
ＳＯ２Ｆ基を有する電解質前駆体により構成されたイオン交換基能を備えない電解質前駆体膜を準備する工程と、
ＳＯ２Ｆ基を有するアイオノマをフッ素溶媒に溶融分散させたアイオノマ溶液と、疎水物性を有する触媒反応物質と、を混合した触媒層部材を準備する工程と、
疎水物性を有する拡散層部材を準備する工程と、
それぞれの前記補強層部材の一方の面に前記触媒層部材を塗工して第１と第２の触媒前駆体層を形成し、前記補強層部材内に前記触媒層部材の一部を浸透させることにより、前記補強層部材と前記第１と第２の触媒前駆体層とを一体化する工程と、
前記第１の触媒前駆体層の形成後前記触媒層部材中の前記フッ素溶媒が乾燥する前に、前記第１の触媒前駆体層上面に前記拡散層部材を貼り合わせて、前記触媒層部材の一部を前記拡散層部材内に浸透させることにより、前記第１の触媒前駆体層と前記拡散層部材とを一体化する工程と、
前記第１の触媒前駆体層が形成された前記補強層部材の他方の面に前記電解質前駆体膜の一方の面を貼り合わせるとともに、前記電解質前駆体膜の他方の面上に前記第２の触媒前駆体層が形成された前記補強層部材の他方の面を貼り合わせて加熱することにより、前記電解質前駆体膜中の前記電解質前駆体を溶融させて、前記第１と第２の触媒前駆体層が形成されたそれぞれの前記補強層部材内に浸透させるとともに、前記第１と第２の触媒前駆体層中の前記アイオノマを軟化させることにより、前記電解質前駆体膜と前記第１と第２の触媒前駆体層とを一体化させる工程と、
前記拡散層部材と前記第１の触媒前駆体層と前記電解質前駆体膜と前記第２の触媒前駆体層とが一体化された積層体を、前記第２の触媒前駆体層側から加水分解処理して、前記第１の触媒前駆体層、前記第２の触媒前駆体層、前記電解質前駆体膜、および、前記拡散層内に浸透した前記アイオノマをスルホン化させることにより、前記第１の触媒前駆体層、前記第２の触媒前駆体層、および、前記電解質前駆体膜を、イオン交換基能を備える電解質を有する第１の触媒層、第２の触媒層、および、電解質膜に変成させる工程と、
を備えることを特徴とする膜電極拡散層接合体の作製方法。
適用例３の作製方法によっても、膜電極拡散層接合体を全体として一体化した構造とすることができるとともに、親水物性を有する電解質膜および拡散層と疎水物性を有する拡散層を、それぞれの境界において界面を持たず連続的に形成された構造とすることができる。また、適用例３の作製方法によれば、電解質膜の両側に補強層を備えているので、適用例２の作製方法よりもさらに強度を高めることが可能である。 [Application Example 3]
A method for producing a membrane electrode diffusion layer assembly, comprising preparing two reinforcing layer members composed of porous members;
Preparing an electrolyte precursor film that does not have an ion-exchange group ability and is constituted by an electrolyte precursor having a SO2F group;
Preparing a catalyst layer member in which an ionomer solution in which an ionomer having an SO2F group is melt-dispersed in a fluorine solvent and a catalytic reactant having hydrophobic properties are mixed;
Preparing a diffusion layer member having hydrophobic properties;
The catalyst layer member is applied to one surface of each of the reinforcing layer members to form first and second catalyst precursor layers, and a part of the catalyst layer member is infiltrated into the reinforcing layer member. A step of integrating the reinforcing layer member and the first and second catalyst precursor layers;
Before the fluorine solvent in the catalyst layer member is dried after the formation of the first catalyst precursor layer, the diffusion layer member is bonded to the upper surface of the first catalyst precursor layer, and the catalyst layer member Integrating the first catalyst precursor layer and the diffusion layer member by infiltrating a portion thereof into the diffusion layer member;
The one surface of the electrolyte precursor film is bonded to the other surface of the reinforcing layer member on which the first catalyst precursor layer is formed, and the second surface is formed on the other surface of the electrolyte precursor film. The first and second catalyst precursors are melted by laminating and heating the other surface of the reinforcing layer member on which the catalyst precursor layer is formed, thereby melting the electrolyte precursor in the electrolyte precursor film. The electrolyte precursor film and the first and second electrolyte layers are infiltrated into each of the reinforcing layer members on which the body layer is formed, and the ionomer in the first and second catalyst precursor layers is softened. Integrating the two catalyst precursor layers;
The laminated body in which the diffusion layer member, the first catalyst precursor layer, the electrolyte precursor film, and the second catalyst precursor layer are integrated is hydrolyzed from the second catalyst precursor layer side. Treating the first catalyst precursor layer, the second catalyst precursor layer, the electrolyte precursor membrane, and the ionomer that has penetrated into the diffusion layer, thereby sulfonating the first catalyst precursor layer; The catalyst precursor layer, the second catalyst precursor layer, and the electrolyte precursor film are converted into a first catalyst layer, a second catalyst layer, and an electrolyte film having an electrolyte having an ion exchange group ability. A process of
A method for producing a membrane electrode diffusion layer assembly, comprising:
Also by the production method of Application Example 3, the membrane / electrode diffusion layer assembly can be integrated as a whole, and the electrolyte membrane having the hydrophilic property and the diffusion layer having the hydrophobic property and the diffusion layer having the hydrophobic property can be separated from each other. The structure can be formed continuously without an interface. Further, according to the manufacturing method of Application Example 3, since the reinforcing layers are provided on both sides of the electrolyte membrane, the strength can be further increased as compared with the manufacturing method of Application Example 2.

［適用例４］
膜電極接合体の作製方法であって
ＳＯ２Ｆ基を有する電解質前駆体により構成されたイオン交換基能を備えない電解質前駆体膜を準備する工程と、
ＳＯ２Ｆ基を有するアイオノマをフッ素溶媒に溶融分散させたアイオノマ溶液と、疎水物性を有する触媒反応物質と、を混合した触媒層部材を準備する工程と、
カーボンと撥水部材とフッ素溶媒とを混合した導電機能層用ペーストを準備する工程と、
疎水物性を有する拡散層部材を準備する工程と、
前記電解質前駆体膜の一方の面に前記触媒層部材を塗工して第１の触媒前駆体層を形成し、前記触媒層部材に含まれる前記フッ素溶媒により前記電解質前駆体膜の表面を溶融させることにより、前記電解質前駆体膜と前記第１の触媒前駆体層とを一体化する工程と、
前記触媒層部材の塗工後前記フッ素溶媒が乾燥する前に、前記第１の触媒前駆体層上面に前記導電機能層用ペーストを塗工して導電機能層を形成することにより、前記第１の触媒電駆体層と前記導電機能層とを一体化する工程と、
前記導電機能層用ペーストの塗工後前記フッ素溶媒が乾燥する前に、前記導電機能層上面に前記拡散層部材を貼り合わせて、前記拡散層部材の表面の凹凸面を前記導電機能層中に食い込ませ、前記フッ素溶媒の乾燥により前記導電機能層と前記拡散層部材とを一体化する工程と、
前記電解質前駆体膜の他方の面に前記触媒層部材を塗工して第２の触媒前駆体層を形成し、前記触媒層部材に含まれる前記フッ素溶媒により前記電解質前駆体膜の表面を溶融させることにより、前記電解質前駆体膜と前記第２の触媒前駆体層とを一体化する工程と、
前記拡散層部材と前記第１の触媒前駆体層と前記電解質前駆体膜と前記第２の触媒前駆体層とが一体化された積層体を、前記第２の触媒前駆体層側から加水分解処理して、前記第１の触媒前駆体層、前記第２の触媒前駆体層、前記電解質前駆体膜、および、前記拡散層部材内に浸透した前記アイオノマをスルホン化させることにより、前記第１の触媒前駆体層、前記第２の触媒前駆体層、および、前記電解質前駆体膜を、イオン交換基能を備える電解質を有する第１の触媒層、第２の触媒層、および、電解質膜に変成させる工程と、
を備えることを特徴とする膜電極拡散層接合体の作製方法。
適用例４の作製方法によっても、膜電極拡散層接合体を全体として一体化した構造とすることができるとともに、親水物性を有する電解質膜および拡散層と疎水物性を有する拡散層を、それぞれの境界において界面を持たず連続的に形成された構造とすることができる。また、適用例４の作製方法によれば、導電機能層用ペーストによる導電機能層を介して第１の触媒前駆体層上に拡散層を形成している。これにより、拡散層の表面の凹凸面を容易に吸収して第１の触媒前駆体層と導電機能層と拡散層とを一体化することができる。また、加熱圧着や焼成工程を省略することが可能である。
［適用例５］
膜電極拡散層接合体の作製方法であって
多孔部材で構成される補強層部材を準備する工程と、
ＳＯ２Ｆ基を有する電解質前駆体により構成されたイオン交換基能を備えない電解質前駆体膜を準備する工程と、
ＳＯ２Ｆ基を有するアイオノマをフッ素溶媒に溶融分散させた前駆体アイオノマ溶液と、疎水物性を有する触媒反応物質と、を混合した触媒層部材を準備する工程と、
カーボンと撥水部材とフッ素溶媒とを混合した導電機能層用ペーストを準備する工程と、
疎水物性を有する拡散層部材を準備する工程と、
前記補強層部材の一方の面に前記触媒層部材を塗工して第１の触媒前駆体層を形成し、前記補強層部材内に前記触媒層部材の一部を浸透させることにより、前記補強層部材と前記第１の触媒前駆体層を一体化する工程と、
前記触媒層部材の塗工後前記フッ素溶媒が乾燥する前に、前記第１の触媒前駆体層上面に前記導電機能層用ペーストを塗工して導電機能層を形成することにより、前記第１の触媒前駆体層と前記導電機能層とを一体化する工程と、
前記導電機能層用ペーストの塗工後前記フッ素溶媒が乾燥する前に、前記導電機能層上面に前記拡散層部材を貼り合わせて、前記拡散層部材の表面の凹凸面を前記導電機能層中に食い込ませ、前記フッ素溶媒の乾燥により前記導電機能層と前記拡散層部材とを一体化する工程と、
前記補強層部材の他方の面に前記電解質前駆体膜の一方の面を貼り合わせて加熱することにより、前記電解質前駆体膜中の前記電解質前駆体を溶融させて、前記補強層部材内に浸透させるとともに、前記第１の触媒前駆体層中の前記アイオノマを軟化させることにより、前記電解質前駆体膜と前記第１の触媒前駆体層とを一体化させる工程と、
前記電解質前駆体膜の他方の面上に前記触媒層部材を塗工して第２の触媒前駆体層を形成し、前記触媒層部材に含まれる前記フッ素溶媒により前記電解質前駆体膜の表面を溶融させることにより、前記電解質前駆体膜と前記第２の触媒前駆体層とを一体化する工程と、
前記拡散層部材と前記第１の触媒前駆体層と前記電解質前駆体膜と前記第２の触媒前駆体層とが一体化された積層体を、前記第２の触媒前駆体層側から加水分解処理して、前記第１の触媒前駆体層、前記第２の触媒前駆体層、前記電解質前駆体膜、および、前記拡散層部材内に浸透した前記アイオノマをスルホン化させることにより、前記第１の触媒前駆体層、前記第２の触媒前駆体層、および、前記電解質前駆体膜を、イオン交換基能を備える電解質を有する第１の触媒層、第２の触媒層、および、電解質膜に変成させる工程と、
を備えることを特徴とする膜電極拡散層接合体の作製方法。
適用例５の作製方法によっても、膜電極拡散層接合体を全体として一体化した構造とすることができるとともに、親水物性を有する電解質膜および拡散層と疎水物性を有する拡散層を、それぞれの境界において界面を持たず連続的に形成された構造とすることができる。また、適用例５の作製方法によれば、導電機能層用ペーストによる導電機能層を介して第１の触媒前駆体層上に拡散層を形成している。これにより、拡散層表面の凹凸面を容易に吸収して第１の触媒前駆体層と導電機能層と拡散層とを一体化することができる。また、加熱圧着や焼成工程を省略することが可能である。さらに、また、適用例５の作製方法によれば、補強層を備えているので、適用例４の作製方法よりも強度を高めることが可能である。 [Application Example 4]
A method for preparing a membrane electrode assembly, the step of preparing an electrolyte precursor membrane that does not have an ion exchange group ability and is constituted by an electrolyte precursor having an SO2F group;
Preparing a catalyst layer member in which an ionomer solution in which an ionomer having an SO2F group is melt-dispersed in a fluorine solvent and a catalytic reactant having hydrophobic properties are mixed;
Preparing a conductive functional layer paste in which carbon, a water repellent member, and a fluorine solvent are mixed;
Preparing a diffusion layer member having hydrophobic properties;
The catalyst layer member is applied to one surface of the electrolyte precursor film to form a first catalyst precursor layer, and the surface of the electrolyte precursor film is melted by the fluorine solvent contained in the catalyst layer member By integrating the electrolyte precursor film and the first catalyst precursor layer,
By applying the conductive functional layer paste on the upper surface of the first catalyst precursor layer to form the conductive functional layer after the application of the catalyst layer member and before the fluorine solvent is dried, A step of integrating the catalytic conductor layer and the conductive functional layer,
After the application of the conductive functional layer paste and before the fluorine solvent is dried, the diffusion layer member is bonded to the upper surface of the conductive functional layer so that the uneven surface on the surface of the diffusion layer member is in the conductive functional layer. Biting and integrating the conductive functional layer and the diffusion layer member by drying the fluorine solvent;
The catalyst layer member is applied to the other surface of the electrolyte precursor film to form a second catalyst precursor layer, and the surface of the electrolyte precursor film is melted by the fluorine solvent contained in the catalyst layer member. By integrating the electrolyte precursor film and the second catalyst precursor layer,
The laminated body in which the diffusion layer member, the first catalyst precursor layer, the electrolyte precursor film, and the second catalyst precursor layer are integrated is hydrolyzed from the second catalyst precursor layer side. The first catalyst precursor layer, the second catalyst precursor layer, the electrolyte precursor film, and the ionomer that has penetrated into the diffusion layer member are sulfonated by the treatment. The catalyst precursor layer, the second catalyst precursor layer, and the electrolyte precursor film are used as the first catalyst layer, the second catalyst layer, and the electrolyte film having an electrolyte having an ion exchange group ability. A transformation process;
A method for producing a membrane electrode diffusion layer assembly, comprising:
Also by the production method of Application Example 4, the membrane / electrode diffusion layer assembly can be integrated as a whole, and the electrolyte membrane having the hydrophilic property and the diffusion layer having the hydrophobic property can be separated from each boundary. The structure can be formed continuously without an interface. Moreover, according to the manufacturing method of the application example 4, the diffusion layer is formed on the first catalyst precursor layer via the conductive functional layer made of the conductive functional layer paste. Thereby, the uneven | corrugated surface of the surface of a diffusion layer can be absorbed easily, and a 1st catalyst precursor layer, a conductive functional layer, and a diffusion layer can be integrated. Further, it is possible to omit the thermocompression bonding and the firing step.
[Application Example 5]
A method for producing a membrane electrode diffusion layer assembly, the step of preparing a reinforcing layer member composed of a porous member,
Preparing an electrolyte precursor film that does not have an ion-exchange group ability and is constituted by an electrolyte precursor having a SO2F group;
Preparing a catalyst layer member in which a precursor ionomer solution in which an ionomer having an SO2F group is melt-dispersed in a fluorine solvent and a catalytic reactant having hydrophobic properties are mixed;
Preparing a conductive functional layer paste in which carbon, a water repellent member, and a fluorine solvent are mixed;
Preparing a diffusion layer member having hydrophobic properties;
The catalyst layer member is coated on one surface of the reinforcement layer member to form a first catalyst precursor layer, and a part of the catalyst layer member is infiltrated into the reinforcement layer member, whereby the reinforcement Integrating a layer member and the first catalyst precursor layer;
By applying the conductive functional layer paste on the upper surface of the first catalyst precursor layer to form the conductive functional layer after the application of the catalyst layer member and before the fluorine solvent is dried, The step of integrating the catalyst precursor layer and the conductive functional layer,
After the application of the conductive functional layer paste and before the fluorine solvent is dried, the diffusion layer member is bonded to the upper surface of the conductive functional layer so that the uneven surface on the surface of the diffusion layer member is in the conductive functional layer. Biting and integrating the conductive functional layer and the diffusion layer member by drying the fluorine solvent;
By bonding one surface of the electrolyte precursor film to the other surface of the reinforcing layer member and heating, the electrolyte precursor in the electrolyte precursor film is melted and penetrated into the reinforcing layer member And integrating the electrolyte precursor film and the first catalyst precursor layer by softening the ionomer in the first catalyst precursor layer;
The catalyst layer member is coated on the other surface of the electrolyte precursor film to form a second catalyst precursor layer, and the surface of the electrolyte precursor film is covered with the fluorine solvent contained in the catalyst layer member. Integrating the electrolyte precursor film and the second catalyst precursor layer by melting,
The laminated body in which the diffusion layer member, the first catalyst precursor layer, the electrolyte precursor film, and the second catalyst precursor layer are integrated is hydrolyzed from the second catalyst precursor layer side. The first catalyst precursor layer, the second catalyst precursor layer, the electrolyte precursor film, and the ionomer that has penetrated into the diffusion layer member are sulfonated by the treatment. The catalyst precursor layer, the second catalyst precursor layer, and the electrolyte precursor film are used as the first catalyst layer, the second catalyst layer, and the electrolyte film having an electrolyte having an ion exchange group ability. A transformation process;
A method for producing a membrane electrode diffusion layer assembly, comprising:
Also by the manufacturing method of Application Example 5, the membrane / electrode diffusion layer assembly can be integrated as a whole, and the electrolyte membrane having the hydrophilic property and the diffusion layer having the hydrophobic property can be separated from each boundary. The structure can be formed continuously without an interface. Further, according to the manufacturing method of Application Example 5, the diffusion layer is formed on the first catalyst precursor layer through the conductive functional layer made of the conductive functional layer paste. Thereby, the uneven surface on the surface of the diffusion layer can be easily absorbed, and the first catalyst precursor layer, the conductive functional layer, and the diffusion layer can be integrated. Further, it is possible to omit the thermocompression bonding and the firing step. Furthermore, according to the manufacturing method of Application Example 5, since the reinforcing layer is provided, the strength can be increased as compared with the manufacturing method of Application Example 4.

なお、本発明は、種々の形態で実現することが可能であり、例えば、膜電極拡散層接合体の作製方法だけでなく、この作製方法により作製された膜電極拡散層接合体、この膜電極拡散層接合体を用いた燃料電池、この燃料電池を用いた燃料電池システム等の種々の形態で実現することが可能である。   The present invention can be realized in various forms, for example, not only a method for producing a membrane electrode diffusion layer assembly, but also a membrane electrode diffusion layer assembly produced by this production method, and this membrane electrode. It can be realized in various forms such as a fuel cell using a diffusion layer assembly and a fuel cell system using the fuel cell.

第１実施例の膜電極拡散層接合体の作製方法について示す説明図である。It is explanatory drawing shown about the preparation methods of the membrane electrode diffusion layer assembly of 1st Example. 図１により示した作製方法により作製されたＭＥＧＡを用いたセル性能と比較例として従来の作製方法により作製されたＭＥＧＡを用いたセル性能について示す説明図である。It is explanatory drawing which shows the cell performance using MEGA produced by the conventional preparation method as a comparative example and the cell performance using MEGA produced by the preparation method shown by FIG. 第２実施例の膜電極拡散層接合体の作製方法について示す説明図である。It is explanatory drawing shown about the preparation methods of the membrane electrode diffusion layer assembly of 2nd Example. 第３実施例の膜電極拡散層接合体の作製方法について示す説明図である。It is explanatory drawing shown about the preparation methods of the membrane electrode diffusion layer assembly of 3rd Example. 第４実施例の膜電極拡散層接合体の作製方法について示す説明図である。It is explanatory drawing shown about the preparation methods of the membrane electrode diffusion layer assembly of 4th Example. 導電機能層用ペーストを作製する方法について示す説明図である。It is explanatory drawing shown about the method of producing the paste for conductive functional layers. 図５により示した作製方法により作製されたＭＥＧＡを用いたセル性能と比較例として従来の作製方法により作製されたＭＥＧＡを用いたセル性能について示す説明図である。It is explanatory drawing which shows the cell performance using MEGA produced by the conventional preparation method as a comparative example and the cell performance using MEGA produced by the preparation method shown by FIG. 従来の膜電極接合体に導電機能層を介して拡散層を一体化形成することによる膜電極拡散層接合体の作製方法について示す説明図である。It is explanatory drawing shown about the preparation method of the membrane electrode diffusion layer assembly by integrally forming a diffusion layer through the conductive functional layer in the conventional membrane electrode assembly. 第５実施例の膜電極拡散層接合体の作製方法について示す説明図である。It is explanatory drawing shown about the preparation methods of the membrane electrode diffusion layer assembly of 5th Example.

Ａ．第１実施例：
図１は、第１実施例の膜電極拡散層接合体の作製方法について示す説明図である。以下で説明する作製方法の実行に先立って、まず、Ｆ型電解質層用部材、Ｆ型触媒層用インク、拡散層用部材を準備する。Ｆ型電解質層用部材は、図示しない膜形成シート、例えば、ＰＥＴシート上に、ＳＯ２Ｆ基を有するアイオノマ（「Ｆ型アイオノマ」とも呼ばれる）をフッ素溶媒(ＨＦＥ等））に溶融分散させたアイオノマ溶液を塗布し乾燥させた後、膜形成シートを剥離することにより形成することができる。このＦ型電解質層用部材を用いて構成されるＦ型電解質層（膜）が本発明の「電解質前駆体膜」に相当する。また、Ｆ型触媒層用インクは、例えば、Ｆ型アイオノマをフッ素溶媒(例えば、非水系の高沸点（７０℃以上のＨＦＥ等））に溶融分散させたアイオノマ溶液と、疎水物性を有する触媒反応物質（例えば、ＰｔＣｏ担持カーボン等）と、を混合することにより作成することができる。このＦ型触媒層用インクが本発明の「触媒層用部材」に相当し、後述するように、Ｆ型触媒層用インクを用いて形成されるＦ型触媒層が本発明の「触媒前駆体層」に相当する。また、拡散層部材としては、疎水物性を有する多孔部材、例えば、空孔率の大きな導電性部材、例えば、撥水処理が施されたカーボンペーパやカーボンクロス等を用いることができる。 A. First embodiment:
FIG. 1 is an explanatory view showing a method for producing a membrane electrode diffusion layer assembly of the first embodiment. Prior to the execution of the production method described below, first, an F-type electrolyte layer member, an F-type catalyst layer ink, and a diffusion layer member are prepared. The F-type electrolyte layer member is an ionomer solution in which an ionomer having an SO2F group (also referred to as “F-type ionomer”) is melt-dispersed in a fluorine solvent (HFE or the like) on a film forming sheet (not shown) such as a PET sheet. After coating and drying, the film-forming sheet can be peeled off. The F-type electrolyte layer (film) configured using this F-type electrolyte layer member corresponds to the “electrolyte precursor film” of the present invention. The ink for the F-type catalyst layer includes, for example, an ionomer solution in which F-type ionomer is melt-dispersed in a fluorine solvent (for example, non-aqueous high boiling point (such as HFE of 70 ° C. or higher)) and a catalytic reaction having hydrophobic properties. It can be prepared by mixing a substance (for example, PtCo-supported carbon or the like). This F-type catalyst layer ink corresponds to the “catalyst layer member” of the present invention. As will be described later, the F-type catalyst layer formed using the F-type catalyst layer ink of the present invention is the “catalyst precursor” of the present invention. Corresponds to “layer”. In addition, as the diffusion layer member, a porous member having a hydrophobic property, for example, a conductive member having a large porosity, for example, carbon paper or carbon cloth subjected to water repellent treatment can be used.

［１］まず、Ｆ型電解質層用部材をＦ型電解質層１０として用い、Ｆ型電解質層１０の一方の面上に、Ｆ型触媒層用インク２０ｐを塗工して、第１のＦ型触媒層２０ａを形成する。なお、このとき、Ｆ型触媒層用インク２０ｐに含まれるフッ素溶液により、Ｆ型電解質層１０の表面が溶けてＦ型電解質層１０と第１のＦ型触媒層２０ａとが一体化形成されるともに、それぞれの境界において界面を持たず連続的に形成された構造となる。 [1] First, the F-type electrolyte layer member is used as the F-type electrolyte layer 10, and the F-type catalyst layer ink 20 p is applied on one surface of the F-type electrolyte layer 10. A catalyst layer 20a is formed. At this time, the surface of the F-type electrolyte layer 10 is melted by the fluorine solution contained in the F-type catalyst layer ink 20p, and the F-type electrolyte layer 10 and the first F-type catalyst layer 20a are integrally formed. Both have a structure formed continuously without having an interface at each boundary.

［２］そして、Ｆ型触媒層用インク２０ｐの塗工後、これに含まれるフッ素溶媒が乾燥する前に、形成された第１のＦ型触媒層２０ａの上面に、拡散層部材により構成される拡散層３０を貼り合わせる。このとき、Ｆ型触媒層インク２０ｐの一部が拡散層３０内に浸透し、これに含まれるＦ型アイオノマにより拡散層３０が第１のＦ型触媒層２０ａに定着され、第１のＦ型触媒層２０ａと拡散層３０とが一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された構造となる。この結果、Ｆ型電解質層１０と第１のＦ型触媒層２０ａと拡散層３０とが一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された構造となる。 [2] After the application of the F-type catalyst layer ink 20p, before the fluorine solvent contained therein is dried, the diffusion layer member is formed on the upper surface of the formed first F-type catalyst layer 20a. A diffusion layer 30 is attached. At this time, a part of the F-type catalyst layer ink 20p penetrates into the diffusion layer 30, and the diffusion layer 30 is fixed to the first F-type catalyst layer 20a by the F-type ionomer contained therein, and the first F-type catalyst layer 20a is fixed. The catalyst layer 20a and the diffusion layer 30 are integrally formed, and have a structure formed continuously without having an interface at each boundary. As a result, the F-type electrolyte layer 10, the first F-type catalyst layer 20 a, and the diffusion layer 30 are integrally formed, and the structure is formed continuously without having an interface at each boundary.

［３］また、Ｆ型電解質層１０の他方の面上に、Ｆ型触媒層用インク２０ｐを塗工して、第２のＦ型触媒層２０ｂを形成する。［１］と同様に、Ｆ型触媒層用インク２０ｐに含まれるフッ素溶液により、Ｆ型電解質層１０の表面が溶けてＦ型電解質層１０と第２のＦ型触媒層２０ｂとが一体化形成されるともに、それぞれの境界において界面を持たず連続的に形成された構造となる。この結果、拡散層３０と第１のＦ型触媒層２０ａとＦ型電解質層１０と第２のＦ型触媒層２０ｂとが一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された構造となる。 [3] Further, the F-type catalyst layer ink 20p is applied on the other surface of the F-type electrolyte layer 10 to form the second F-type catalyst layer 20b. Similarly to [1], the surface of the F-type electrolyte layer 10 is melted by the fluorine solution contained in the F-type catalyst layer ink 20p, and the F-type electrolyte layer 10 and the second F-type catalyst layer 20b are integrally formed. At the same time, the structure is formed continuously without having an interface at each boundary. As a result, the diffusion layer 30, the first F-type catalyst layer 20a, the F-type electrolyte layer 10 and the second F-type catalyst layer 20b are integrally formed, and continuously without any interface at each boundary. The formed structure.

［４］次に、拡散層３０と第１のＦ型触媒層２０ａとＦ型電解質層１０と第２のＦ型触媒層２０ｂとが一体化形成された積層体を、第２のＦ型触媒２０ｂ側から加水分解処理をすることにより、第１のＦ型触媒層２０ａ、Ｆ型電解質層１０、第２のＦ型触媒層２０ｂ、および、拡散層３０に含まれるＦ型アイオノマのＳＯ２Ｆ基を、イオン交換機能を示すスルホン酸基（ＳＯ３Ｈ基）化させることにより、第１のＦ型触媒層２０ａ、Ｆ型電解質層１０、および、第２のＦ型触媒層２０ｂを、イオン交換基能を備える電解質を有するＨ型の第１の触媒層２０ａＨ、電解質層１０Ｈ、および、第２の触媒層２０ｂＨに変性させる。この結果、片側に拡散層を備え、各層が一体化形成されるとともに、各層の境界において界面を持たず連続的に形成された構造を有する膜電極拡散層接合体（ＭＥＧＡ）を形成することができる。 [4] Next, a laminate in which the diffusion layer 30, the first F-type catalyst layer 20a, the F-type electrolyte layer 10, and the second F-type catalyst layer 20b are integrally formed is used as a second F-type catalyst. By performing the hydrolysis treatment from the 20b side, the SO2F group of the F-type ionomer contained in the first F-type catalyst layer 20a, the F-type electrolyte layer 10, the second F-type catalyst layer 20b, and the diffusion layer 30 is obtained. By converting the first F-type catalyst layer 20a, the F-type electrolyte layer 10 and the second F-type catalyst layer 20b to ion exchange base ability by converting them to a sulfonic acid group (SO3H group) having an ion exchange function. The H-type first catalyst layer 20aH, the electrolyte layer 10H, and the second catalyst layer 20bH having the electrolyte to be provided are modified. As a result, a diffusion layer is provided on one side, each layer is integrally formed, and a membrane electrode diffusion layer assembly (MEGA) having a structure formed continuously without an interface at the boundary of each layer can be formed. it can.

なお、本実施例の片側にのみ拡散層を備えるＭＥＧＡは、拡散層を有しない触媒層側に拡散層が密接するように、例えば、ＭＥＧＡの拡散層を有しない触媒層側に拡散層を配置し、それを両側に設けたターミナルにより圧力をかけて挟持することにより、使用される。   In addition, the MEGA having the diffusion layer only on one side of the present embodiment is arranged, for example, on the catalyst layer side without the MEGA diffusion layer so that the diffusion layer is in close contact with the catalyst layer side without the diffusion layer. And it is used by pinching it by applying pressure to the terminals provided on both sides.

図２は、図１により示した作製方法により作製されたＭＥＧＡを用いたセル性能と、比較例として従来の作製方法により作製されたＭＥＧＡを用いたセル性能について示す説明図である。セル性能としては、カソード（Ｃａ）側に無加湿でガスを供給する場合において、負荷電流１．２Ａ／ｃｍ2とした場合のセル電圧とセル抵抗の温度特性を示している。また、比較例としての従来の作製方法は、イオン交換基能を備える電解質を有する電解質膜の両面に、電解質を含む触媒インクを塗工することにより、触媒層を形成してＭＥＡを作製し、そのＭＥＡの両面に拡散層を熱圧着あるいは接着層を介して貼り合わせてＭＥＧＡを形成するものである。ここでは、ＭＥＡに拡散層を１３０℃で熱圧着してＭＥＧＡを形成したものを用いる。また、膜厚は２０μｍとする。 FIG. 2 is an explanatory diagram showing cell performance using MEGA manufactured by the manufacturing method shown in FIG. 1 and cell performance using MEGA manufactured by a conventional manufacturing method as a comparative example. As the cell performance, the temperature characteristics of the cell voltage and the cell resistance when the load current is 1.2 A / cm 2 in the case of supplying gas to the cathode (Ca) without humidification are shown. In addition, a conventional production method as a comparative example is to form an MEA by forming a catalyst layer by applying a catalyst ink containing an electrolyte on both surfaces of an electrolyte membrane having an electrolyte having an ion exchange base ability, A diffusion layer is bonded to both surfaces of the MEA through thermocompression bonding or an adhesive layer to form a MEGA. Here, a MEGA formed by thermocompression bonding of the diffusion layer to the MEA at 130 ° C. is used. The film thickness is 20 μm.

図２からわかるように、本実施例により作製されたＭＥＧＡは、比較例としての従来のＭＥＧＡに比べて、セル電圧特性およびセル抵抗特性の両方とも向上していることがわかる。特に、７０℃以下の中温域以下の出力（セル電圧）が向上し、発電により発生する生成水のマネジメント能力が向上していることがわかる。   As can be seen from FIG. 2, the MEGA fabricated according to this example is improved in both cell voltage characteristics and cell resistance characteristics as compared with the conventional MEGA as a comparative example. In particular, it can be seen that the output (cell voltage) below the middle temperature range of 70 ° C. or less is improved, and the management ability of the generated water generated by power generation is improved.

以上のように、上記第１実施例の膜電極拡散層接合体の作製方法によれば、作製された膜電極拡散層接合体において、拡散層、第１の触媒層、電解質層、および、第２の触媒層の各層間を一体化して形成することができるとともに、各層の境界に界面を持たず連続するように形成することができる。これにより、従来例で説明した問題点、拡散層の剥離強度や、抵抗成分の増加等の問題を改善することができる。   As described above, according to the manufacturing method of the membrane electrode diffusion layer assembly of the first embodiment, in the manufactured membrane electrode diffusion layer assembly, the diffusion layer, the first catalyst layer, the electrolyte layer, and the first Each layer of the two catalyst layers can be formed integrally, and can be formed continuously without having an interface at the boundary between the layers. Thereby, problems such as the problems described in the conventional example, the peel strength of the diffusion layer, and the increase of the resistance component can be improved.

Ｂ．第２実施例：
図３は、第２実施例の膜電極拡散層接合体の作製方法について示す説明図である。この第２実施例は、膜電極拡散層接合体の剛性を高めるために、補強層が加えられており、以下で説明するように、これに応じた作製方法となっている点が第１実施例と異なっている。 B. Second embodiment:
FIG. 3 is an explanatory view showing a method for producing the membrane electrode diffusion layer assembly of the second embodiment. In the second embodiment, a reinforcing layer is added in order to increase the rigidity of the membrane electrode diffusion layer assembly, and as described below, the manufacturing method according to this is the first embodiment. It is different from the example.

まず、第２実施例の膜電極拡散層接合体の作製方法の実行に先立って、第１実施例と同様に、Ｆ型電解質層用部材、Ｆ型触媒層用インク、拡散層用部材を準備するのに加えて、補強層部材を準備する。なお、この補強層部材としては、疎水物性を有する多孔部材、例えば、ＰＴＦＥ等を用いることができる。   First, prior to the execution of the method for producing the membrane electrode diffusion layer assembly of the second example, as in the first example, the F-type electrolyte layer member, the F-type catalyst layer ink, and the diffusion layer member were prepared. In addition, the reinforcing layer member is prepared. As the reinforcing layer member, a porous member having hydrophobic properties, such as PTFE, can be used.

［１］まず、補強層部材を補強層（補強膜）１５として用い、補強層１５の一方の面上に、Ｆ型触媒層用インク２０ｐを塗工して、第１のＦ型触媒層２０ａを形成する。なお、このとき、Ｆ型触媒層用インク２０ｐは補強層１５の多孔部分に浸透して、第１のＦ型触媒層２０ａは補強層１５内にも形成され、第１のＦ型触媒層２０ａと補強層１５とが一体化される。例えば、膜厚が１μｍ以上で気孔率６０％以上の多孔部材への浸透を、触媒層の１０〜７０％とし、後述する電解質層と触媒層との融合安定性を確保するように設定する。 [1] First, the reinforcing layer member is used as the reinforcing layer (reinforcing film) 15, and the F-type catalyst layer ink 20 p is applied on one surface of the reinforcing layer 15, so that the first F-type catalyst layer 20 a is applied. Form. At this time, the F-type catalyst layer ink 20p penetrates into the porous portion of the reinforcing layer 15, and the first F-type catalyst layer 20a is also formed in the reinforcing layer 15, and the first F-type catalyst layer 20a. And the reinforcing layer 15 are integrated. For example, the penetration into the porous member having a film thickness of 1 μm or more and a porosity of 60% or more is set to 10 to 70% of the catalyst layer so as to ensure fusion stability between the electrolyte layer and the catalyst layer described later.

［２］そして、第１実施例の工程［２］と同様に、Ｆ型触媒層用インク２０ｐの塗工後、これに含まれるフッ素溶媒が乾燥する前に、形成された第１のＦ型触媒層２０ａの上面に、拡散層部材により構成される拡散層３０を貼り合わせる。これにより、第１のＦ型触媒層２０ａと拡散層３０とが一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された構造となる。 [2] In the same manner as in the step [2] of the first embodiment, the first F-type formed after the application of the F-type catalyst layer ink 20p and before the fluorine solvent contained therein is dried. A diffusion layer 30 composed of a diffusion layer member is bonded to the upper surface of the catalyst layer 20a. As a result, the first F-type catalyst layer 20a and the diffusion layer 30 are integrally formed and have a structure in which the first F-type catalyst layer 20a and the diffusion layer 30 are continuously formed without an interface at each boundary.

［３］また、補強層１５の他方の面上に、Ｆ型電解質層用部材をＦ型電解質層１０として貼り合わせる。 [3] Further, an F-type electrolyte layer member is bonded as the F-type electrolyte layer 10 on the other surface of the reinforcing layer 15.

［４］そして、全体を加熱することにより、Ｆ型電解質層１０を溶融させて補強層１５内に含浸させるとともに、第１のＦ型触媒層２０ａに含まれるＦ型アイオノマも軟化することで、毛細管現象により補強層１５内への含浸が促進され、Ｆ型電解質層１０と第１のＦ型触媒層２０ａとが一体化形成されるとともに、その境界において界面を持たず連続的に形成された構造となる。この結果、Ｆ型電解質層１０と第１のＦ型触媒層２０ａと拡散層３０とが一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された構造となる。 [4] By heating the whole, the F-type electrolyte layer 10 is melted and impregnated in the reinforcing layer 15, and the F-type ionomer contained in the first F-type catalyst layer 20a is also softened. The impregnation into the reinforcing layer 15 is promoted by the capillary phenomenon, and the F-type electrolyte layer 10 and the first F-type catalyst layer 20a are integrally formed, and are continuously formed without an interface at the boundary. It becomes a structure. As a result, the F-type electrolyte layer 10, the first F-type catalyst layer 20 a, and the diffusion layer 30 are integrally formed, and the structure is formed continuously without having an interface at each boundary.

［５］また、Ｆ型電解質層１０の第１のＦ型触媒層２０ａに接する側とは反対側の面上に、Ｆ型触媒層用インク２０ｐを塗工して、第２のＦ型触媒層２０ｂを形成する。［１］と同様に、Ｆ型触媒層用インク２０ｐに含まれるフッ素溶液により、Ｆ型電解質層１０の表面が溶けてＦ型電解質層１０と第２のＦ型触媒層２０ｂとが一体化形成されるともに、その境界において界面を持たず連続的に形成された構造となる。この結果、拡散層３０と第１のＦ型触媒層２０ａとＦ型電解質層１０と第２のＦ型触媒層２０ｂとが一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された構造となる。 [5] Further, the F-type catalyst layer ink 20p is applied to the surface of the F-type electrolyte layer 10 opposite to the side in contact with the first F-type catalyst layer 20a, so that the second F-type catalyst is obtained. Layer 20b is formed. Similarly to [1], the surface of the F-type electrolyte layer 10 is melted by the fluorine solution contained in the F-type catalyst layer ink 20p, and the F-type electrolyte layer 10 and the second F-type catalyst layer 20b are integrally formed. At the same time, the structure is formed continuously without an interface at the boundary. As a result, the diffusion layer 30, the first F-type catalyst layer 20a, the F-type electrolyte layer 10 and the second F-type catalyst layer 20b are integrally formed, and continuously without any interface at each boundary. The formed structure.

［６］次に、拡散層３０と第１のＦ型触媒層２０ａと補強層１５を含むＦ型電解質層１０と第２のＦ型触媒層２０ｂとが一体化形成された積層体を、第２のＦ型触媒２０ｂ側から加水分解処理をすることにより、第１のＦ型触媒層２０ａ、Ｆ型電解質層１０、第２のＦ型触媒層２０ｂ、および、拡散層３０に含まれるＦ型アイオノマのＳＯ２Ｆ基を、イオン交換機能を示すスルホン酸基（ＳＯ３Ｈ基）化させることにより、第１のＦ型触媒層２０ａ、Ｆ型電解質層１０、および、第２のＦ型触媒層２０ｂを、イオン交換基能を備える電解質を有するＨ型の第１の触媒層２０ａＨ、電解質層１０Ｈ、および、第２の触媒層２０ｂＨに変性させる。この結果、片側に拡散層を備え、各層が一体化形成されるとともに、各層の境界において界面を持たず連続的に形成された構造を有する膜電極拡散層接合体（ＭＥＧＡ）を形成することができる。 [6] Next, a laminate in which the diffusion layer 30, the first F-type catalyst layer 20a, the F-type electrolyte layer 10 including the reinforcing layer 15 and the second F-type catalyst layer 20b are integrally formed is The F-type contained in the first F-type catalyst layer 20a, the F-type electrolyte layer 10, the second F-type catalyst layer 20b, and the diffusion layer 30 by performing a hydrolysis treatment from the F-type catalyst 20b side of 2 By converting the ionomer SO2F group into a sulfonic acid group (SO3H group) having an ion exchange function, the first F-type catalyst layer 20a, the F-type electrolyte layer 10, and the second F-type catalyst layer 20b are obtained. The H-type first catalyst layer 20aH, the electrolyte layer 10H, and the second catalyst layer 20bH having an electrolyte having ion exchange base ability are modified. As a result, a diffusion layer is provided on one side, each layer is integrally formed, and a membrane electrode diffusion layer assembly (MEGA) having a structure formed continuously without an interface at the boundary of each layer can be formed. it can.

以上のように、上記第２実施例の膜電極拡散層接合体の作製方法によっても、第１実施例と同様に、作製された膜電極拡散層接合体において、拡散層、第１の触媒層、電解質層、および、第２の触媒層の各層間を一体化して形成することができるとともに、各層の境界に界面を持たず連続するように形成することができる。これにより、従来例で説明した問題点、拡散層の剥離強度や、抵抗成分の増加等の問題を改善することができる。さらに、第２実施例においては、補強層１５により電解質層の剛性を第１実施例に比べて高めることができる。   As described above, in the method for manufacturing the membrane electrode diffusion layer assembly of the second embodiment, as in the first embodiment, in the manufactured membrane electrode diffusion layer assembly, the diffusion layer and the first catalyst layer In addition, the electrolyte layer and the second catalyst layer can be integrally formed, and can be formed continuously without having an interface at the boundary between the layers. Thereby, problems such as the problems described in the conventional example, the peel strength of the diffusion layer, and the increase in resistance component can be improved. Further, in the second embodiment, the rigidity of the electrolyte layer can be increased by the reinforcing layer 15 as compared with the first embodiment.

Ｃ．第３実施例：
図４は、第３実施例の膜電極拡散層接合体の作製方法について示す説明図である。この第３実施例は、膜電極拡散層接合体の剛性を高めるために、電解質層の両側に補強層が加えられており、以下で説明するように、これに応じた作製方法となっている点が第２実施例と異なっている。 C. Third embodiment:
FIG. 4 is an explanatory view showing a method for producing the membrane electrode diffusion layer assembly of the third embodiment. In this third embodiment, a reinforcing layer is added to both sides of the electrolyte layer in order to increase the rigidity of the membrane electrode diffusion layer assembly, and as described below, the manufacturing method is in accordance with this. This is different from the second embodiment.

まず、第３実施例の膜電極拡散層接合体の作製方法の実行に先立って、第２実施例と同様に、Ｆ型電解質層用部材、Ｆ型触媒層用インク、拡散層用部材を準備するのに加えて、補強層部材を準備する。   First, prior to execution of the manufacturing method of the membrane electrode diffusion layer assembly of the third example, as in the second example, the F-type electrolyte layer member, the F-type catalyst layer ink, and the diffusion layer member were prepared. In addition, the reinforcing layer member is prepared.

［１］まず、第２実施例の工程［１］と同様に、補強層部材を補強層（補強膜）１５として用い、二つの補強層１５のそれぞれの一方の面上に、Ｆ型触媒層用インク２０ｐを塗工して、第１のＦ型触媒層２０ａおよび第２のＦ型触媒層２０ｂを形成する。 [1] First, similarly to the step [1] of the second embodiment, the reinforcing layer member is used as the reinforcing layer (reinforcing membrane) 15 and the F-type catalyst layer is formed on one surface of each of the two reinforcing layers 15. The ink 20p is applied to form the first F-type catalyst layer 20a and the second F-type catalyst layer 20b.

［２］そして、第１実施例の工程［２］と同様に、Ｆ型触媒層用インク２０ｐの塗工後、これに含まれるフッ素溶媒が蒸散乾燥する前に、形成された第１のＦ型触媒層２０ａの上面に、拡散層部材により構成される拡散層３０を貼り合わせる。これにより、第１のＦ型触媒層２０ａと拡散層３０とが一体化形成されるとともに、その境界において界面を持たず連続的に形成された構造となる。 [2] In the same manner as in the step [2] of the first embodiment, the first F formed after the application of the F-type catalyst layer ink 20p and before the fluorine solvent contained therein is evaporated and dried. A diffusion layer 30 composed of a diffusion layer member is bonded to the upper surface of the mold catalyst layer 20a. As a result, the first F-type catalyst layer 20a and the diffusion layer 30 are integrally formed, and the boundary is formed continuously without having an interface.

［３］また、第１のＦ型触媒層２０ａが形成された補強層１５の他方の面上に、Ｆ型電解質層用部材をＦ型電解質層１０として貼り合わせるとともに、Ｆ型電解質層１０の上面に、第２のＦ型触媒層２０ｂが形成された補強層１５の他方の面側を貼り合わせる。 [3] Further, the F-type electrolyte layer member is bonded as the F-type electrolyte layer 10 on the other surface of the reinforcing layer 15 on which the first F-type catalyst layer 20a is formed. The other surface side of the reinforcing layer 15 on which the second F-type catalyst layer 20b is formed is bonded to the upper surface.

［４］そして、全体を加熱することにより、Ｆ型電解質層１０を溶融させて両側の補強層１５内に含浸させるとともに、第１のＦ型触媒層２０ａおよび第２のＦ型触媒層２０ｂに含まれるＦ型アイオノマも軟化することで、毛細管現象により補強層１５内への含浸が促進され、Ｆ型電解質層１０と第１のＦ型触媒層２０ａとが一体化形成され、かつ、Ｆ型電解質層１０と第２のＦ型触媒層とが一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された構造となる。この結果、第２のＦ型触媒層２０ｂと両側に補強層１５を含むＦ型電解質層１０と第１のＦ型触媒層２０ａと拡散層３０とが一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された構造となる。 [4] Then, by heating the whole, the F-type electrolyte layer 10 is melted and impregnated in the reinforcing layers 15 on both sides, and the first F-type catalyst layer 20a and the second F-type catalyst layer 20b are formed. By softening the contained F-type ionomer, the impregnation into the reinforcing layer 15 is promoted by capillary action, the F-type electrolyte layer 10 and the first F-type catalyst layer 20a are integrally formed, and the F-type The electrolyte layer 10 and the second F-type catalyst layer are integrally formed and have a structure in which they are continuously formed without an interface at each boundary. As a result, the second F-type catalyst layer 20b, the F-type electrolyte layer 10 including the reinforcing layers 15 on both sides, the first F-type catalyst layer 20a, and the diffusion layer 30 are integrally formed, and at each boundary. The structure is formed continuously without an interface.

［５］次に、拡散層３０と第１のＦ型触媒層２０ａと両側に補強層１５を含むＦ型電解質層１０と第２のＦ型触媒層２０ｂとが一体化形成された積層体を、第２のＦ型触媒２０ｂ側から加水分解処理をすることにより、第１のＦ型触媒層２０ａ、Ｆ型電解質層１０、第２のＦ型触媒層２０ｂ、および、拡散層３０に含まれるＦ型アイオノマのＳＯ２Ｆ基を、イオン交換機能を示すスルホン酸基（ＳＯ３Ｈ基）化させることにより、第１のＦ型触媒層２０ａ、Ｆ型電解質層１０、および、第２のＦ型触媒層２０ｂを、イオン交換基能を備える電解質を有するＨ型の第１の触媒層２０ａＨ、電解質層１０Ｈ、第２の触媒層２０ｂＨに変性させる。この結果、片側に拡散層を備え、各層が一体化形成されるとともに、各層の境界において界面を持たず連続的に形成された構造を有する膜電極拡散層接合体（ＭＥＧＡ）を形成することができる。 [5] Next, a laminated body in which the diffusion layer 30, the first F-type catalyst layer 20a, the F-type electrolyte layer 10 including the reinforcing layers 15 on both sides, and the second F-type catalyst layer 20b are integrally formed. By being subjected to a hydrolysis treatment from the second F-type catalyst 20b side, it is included in the first F-type catalyst layer 20a, the F-type electrolyte layer 10, the second F-type catalyst layer 20b, and the diffusion layer 30. By converting the SO2F group of the F-type ionomer into a sulfonic acid group (SO3H group) having an ion exchange function, the first F-type catalyst layer 20a, the F-type electrolyte layer 10, and the second F-type catalyst layer 20b Is modified into an H-type first catalyst layer 20aH, an electrolyte layer 10H, and a second catalyst layer 20bH having an electrolyte having an ion exchange base ability. As a result, a diffusion layer is provided on one side, each layer is integrally formed, and a membrane electrode diffusion layer assembly (MEGA) having a structure formed continuously without an interface at the boundary of each layer can be formed. it can.

以上のように、上記第３実施例の膜電極拡散層接合体の作製方法によっても、第１，第２実施例と同様に、作製された膜電極拡散層接合体において、拡散層、第１の触媒層、電解質層、および、第２の触媒層の各層間を一体化して形成することができるとともに、各層の境界に界面を持たず連続するように形成することができる。これにより、従来例で説明した問題点、拡散層の剥離強度や、抵抗成分の増加等の問題を改善することができる。さらに、第３実施例においては、両側に補強層を含む電解質層が形成されるので、電解質層の剛性を第１，第２実施例に比べて高めることができる。   As described above, even in the method for manufacturing the membrane electrode diffusion layer assembly of the third embodiment, in the manufactured membrane electrode diffusion layer assembly, the diffusion layer, the first The catalyst layer, the electrolyte layer, and the second catalyst layer can be integrally formed, and can be formed continuously without having an interface at the boundary between the layers. Thereby, problems such as the problems described in the conventional example, the peel strength of the diffusion layer, and the increase of the resistance component can be improved. Further, in the third embodiment, since the electrolyte layer including the reinforcing layer is formed on both sides, the rigidity of the electrolyte layer can be increased as compared with the first and second embodiments.

Ｄ．第４実施例：
図５は、第４実施例の膜電極拡散層接合体の作製方法について示す説明図である。この第４実施例は、導電機能層を介して触媒層と拡散層とが一体化された構造を有しており、以下で説明するように、これに応じた作製方法となっている点が第１実施例と異なっている。 D. Fourth embodiment:
FIG. 5 is an explanatory view showing a method for producing the membrane electrode diffusion layer assembly of the fourth embodiment. The fourth embodiment has a structure in which the catalyst layer and the diffusion layer are integrated with each other through the conductive functional layer. As described below, the fourth embodiment has a manufacturing method according to this structure. This is different from the first embodiment.

まず、第４実施例の膜電極拡散層接合体の作製方法の実行に先立って、第１実施例と同様に、Ｆ型電解質層用部材、Ｆ型触媒層用インク、拡散層用部材を準備するのに加えて、導電機能層用ペーストを準備する。補強層部材を準備する。   First, prior to execution of the manufacturing method of the membrane electrode diffusion layer assembly of the fourth example, as in the first example, the F-type electrolyte layer member, the F-type catalyst layer ink, and the diffusion layer member were prepared. In addition to this, a conductive functional layer paste is prepared. A reinforcing layer member is prepared.

図６は導電機能層用ペーストを作製する方法について示す説明図である。図２に示すように、導電機能層用ペースト２５ｐは、カーボン粒子とＰＴＦＥ粒子とフッ素溶媒とを混合し、超音波ホモジナイザーの超音波による分散工法でカーボンを解すと同時にＰＴＦＥの繊維化を進めてペースト状態とすることにより作製することができる。なお、分散工法としては、ボールミル等によってもよい。また、分散時に、他のフッ素系バインダー（ＰＶＤＦやＰＦＡ、Ｆ型アイオノマ等）を混合してもよい。   FIG. 6 is an explanatory view showing a method for producing a conductive functional layer paste. As shown in FIG. 2, the conductive functional layer paste 25p is obtained by mixing carbon particles, PTFE particles, and a fluorine solvent, dissolving carbon by ultrasonic dispersion using an ultrasonic homogenizer, and at the same time, promoting the fiberization of PTFE. It can produce by making it a paste state. The dispersion method may be a ball mill or the like. Moreover, you may mix other fluorine-type binders (PVDF, PFA, F-type ionomer, etc.) at the time of dispersion | distribution.

［１］まず、第１実施例の工程［１］と同様に、Ｆ型電解質層用部材をＦ型電解質層１０として用い、Ｆ型電解質層１０の一方の面上に、Ｆ型触媒層用インク２０ｐを塗工して、第１のＦ型触媒層２０ａを形成する。なお、このとき、Ｆ型触媒層用インク２０ｐに含まれるフッ素溶液により、Ｆ型電解質層１０の表面が溶けてＦ型電解質層１０と第１のＦ型触媒層２０ａとが一体化形成されるともに、その境界において界面を持たず連続的に形成された構造となる。 [1] First, similarly to the step [1] of the first embodiment, the F-type electrolyte layer member is used as the F-type electrolyte layer 10, and the F-type catalyst layer 10 is formed on one surface of the F-type electrolyte layer 10. The ink 20p is applied to form the first F-type catalyst layer 20a. At this time, the surface of the F-type electrolyte layer 10 is melted by the fluorine solution contained in the F-type catalyst layer ink 20p, and the F-type electrolyte layer 10 and the first F-type catalyst layer 20a are integrally formed. Both have a structure formed continuously without an interface at the boundary.

［２］次に、Ｆ型触媒層用インク２０ｐの塗工後、これに含まれるフッ素溶媒が蒸散乾燥する前に、形成された第１のＦ型触媒層２０ａの上面に、導電機能層用ペースト２５ｐを塗工して、第１の導電機能層２５ａを形成する。 [2] Next, after the application of the F-type catalyst layer ink 20p, before the fluorine solvent contained therein is evaporated and dried, the conductive functional layer layer is formed on the upper surface of the first F-type catalyst layer 20a. The paste 25p is applied to form the first conductive functional layer 25a.

［３］そして、導電機能層用ペースト２５ｐの塗工後、これに含まれるフッ素溶媒が蒸散乾燥する前に、形成された第１の導電機能層２５ａの上面に、拡散層部材により構成される第１の拡散層３０ａを貼り合わせる。このとき、第１の拡散層３０ａの表面の凹凸が軟化状態の第１の導電機能層２５ａに食い込みながら、第１の導電機能層２５ａに含まれる分散繊維化したＰＴＦＥと第１の拡散層３０ａとが、フッ素溶媒を介して、互いの疎水性部材の親和性および毛細管現象により定着する。 [3] Then, after the conductive functional layer paste 25p is applied, before the fluorine solvent contained therein is evaporated and dried, the upper surface of the formed first conductive functional layer 25a is constituted by a diffusion layer member. The first diffusion layer 30a is bonded. At this time, while the unevenness of the surface of the first diffusion layer 30a bites into the softened first conductive function layer 25a, the dispersed fiberized PTFE and the first diffusion layer 30a included in the first conductive function layer 25a. Are fixed by the affinity of the hydrophobic members and capillary action through the fluorine solvent.

［４］そして、フッ素溶媒の短時間（１分以内）での蒸散乾燥により、第１のＦ型触媒層２０ａと第１の導電機能層２５ａと第１の拡散層３０ａとが固着して一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された構造となる。この結果、Ｆ型電解質層１０と第１のＦ型触媒層２０ａと第１の導電機能層２５ａと第１の拡散層３０ａとが一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された構造となる。 [4] Then, the first F-type catalyst layer 20a, the first conductive functional layer 25a, and the first diffusion layer 30a are fixed and integrated by evaporating and drying the fluorine solvent in a short time (within 1 minute). In addition, the structure is formed continuously without any interface at each boundary. As a result, the F-type electrolyte layer 10, the first F-type catalyst layer 20a, the first conductive functional layer 25a, and the first diffusion layer 30a are integrally formed, and have no interface at each boundary. It becomes the structure formed automatically.

［５］次に、Ｆ型電解質層１０の他方の面上に、Ｆ型触媒層用インク２０ｐを塗工して、第２のＦ型触媒層２０ｂを形成する。［１］と同様に、Ｆ型触媒層用インク２０ｐに含まれるフッ素溶液により、Ｆ型電解質層１０の表面が溶けてＦ型電解質層１０と第２のＦ型触媒層２０ｂとが一体化形成されるともに、その境界において界面を持たず連続的に形成された構造となる。この結果、第１の拡散層３０ａと第１の導電機能層２５ａと第１のＦ型触媒層２０ａとＦ型電解質層１０と第２のＦ型触媒層２０ｂとが一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された積層体の構造となる。 [5] Next, the F-type catalyst layer ink 20p is applied to the other surface of the F-type electrolyte layer 10 to form a second F-type catalyst layer 20b. Similarly to [1], the surface of the F-type electrolyte layer 10 is melted by the fluorine solution contained in the F-type catalyst layer ink 20p, and the F-type electrolyte layer 10 and the second F-type catalyst layer 20b are integrally formed. At the same time, the structure is formed continuously without an interface at the boundary. As a result, the first diffusion layer 30a, the first conductive functional layer 25a, the first F-type catalyst layer 20a, the F-type electrolyte layer 10, and the second F-type catalyst layer 20b are integrally formed, It becomes the structure of the laminated body which did not have an interface in each boundary and was formed continuously.

［６］次に、形成した積層体の第２のＦ型触媒層２０ｂが形成されている側から加水分解処理をすることにより、第１のＦ型触媒層２０ａ、Ｆ型電解質層１０、および、第２のＦ型触媒層２０ｂと、第１の導電機能層２５ａおよび第１の拡散層３０ａに含まれるＦ型アイオノマのＳＯ２Ｆ基を、イオン交換機能を示すスルホン酸基（ＳＯ３Ｈ基）化させる。これにより、第１のＦ型触媒層２０ａおよびＦ型電解質層１０は、イオン交換基能を備える電解質を有するＨ型の第１の触媒層２０ａＨおよび電解質層１０Ｈに変性される。また、第２のＦ型触媒層２０ｂの表面は、加水分解処理により、親水物性を有する状態（ＳＯ３Ｈ基を含む状態）と疎水物性を有する状態（ＣＦ２基を含む状態）が混在する第２の触媒層２０ｂＦＨとなる。この結果、片側に拡散層を備え、各層が一体化形成されるとともに、各層の境界において界面を持たず連続的に形成された構造を有する膜電極拡散層接合体（ＭＥＧＡ）を形成することができる。 [6] Next, the first F-type catalyst layer 20a, the F-type electrolyte layer 10, and the first F-type catalyst layer 20b are subjected to hydrolysis treatment from the side where the second F-type catalyst layer 20b is formed. The SO2F group of the F-type ionomer contained in the second F-type catalyst layer 20b, the first conductive functional layer 25a, and the first diffusion layer 30a is converted into a sulfonic acid group (SO3H group) having an ion exchange function. . As a result, the first F-type catalyst layer 20a and the F-type electrolyte layer 10 are modified into an H-type first catalyst layer 20aH and an electrolyte layer 10H having an electrolyte having an ion exchange basic ability. In addition, the surface of the second F-type catalyst layer 20b is subjected to hydrolysis treatment in which a state having a hydrophilic property (a state including an SO3H group) and a state having a hydrophobic property (a state including a CF2 group) are mixed. The catalyst layer becomes 20bFH. As a result, a diffusion layer is provided on one side, each layer is integrally formed, and a membrane electrode diffusion layer assembly (MEGA) having a structure formed continuously without an interface at the boundary of each layer can be formed. it can.

［７］次に、第２の触媒層２０ｂＦＨの面上に、導電機能層用ペースト２５ｐを塗工して、第２の導電機能層２５ｂを形成する。上記したように、第２の触媒層２０ｂＦＨは、疎水物性を有する状態が混在している。そして、導電機能層２５ａを形成する導電機能層用ペースト２５ｐにもカーボンやＰＴＦＥ、フッ素溶媒等が含まれており、疎水性を有している。これにより、第２の触媒層２０ｂＦＨと導電機能層用ペースト２５ｐとは親和性が確保されるので、導電機能層用ペースト２５ｐの塗工時において、第２の触媒層２０ｂＦＨの上面に第２の導電機能層２５ｂの定着化が可能となる。そして、導電機能層用ペースト２５ｐに含まれるフッ素溶媒の蒸散乾燥時において、第２の触媒層２０ｂＨと第２の導電機能層２５ｂとが密着して一体化形成されるとともに、その境界において界面を持たず連続的に形成された構造となる。 [7] Next, the conductive functional layer paste 25p is applied on the surface of the second catalyst layer 20bFH to form the second conductive functional layer 25b. As described above, the second catalyst layer 20bFH has a mixture of hydrophobic properties. The conductive functional layer paste 25p forming the conductive functional layer 25a also contains carbon, PTFE, a fluorine solvent, etc., and has hydrophobicity. Thereby, the affinity between the second catalyst layer 20bFH and the conductive functional layer paste 25p is ensured. Therefore, when the conductive functional layer paste 25p is applied, the second catalyst layer 20bFH is formed on the upper surface of the second catalyst layer 20bFH. The conductive functional layer 25b can be fixed. The second catalyst layer 20bH and the second conductive functional layer 25b are formed in close contact with each other at the time of evaporating and drying the fluorine solvent contained in the conductive functional layer paste 25p, and an interface is formed at the boundary. It has a structure formed continuously without it.

［８］そして、工程［３］と同様に、第２の導電機能層２５ｂに含まれるフッ素溶媒が蒸散乾燥する前に、第２の拡散層３０ｂを貼り合わせる。このとき、工程［３］と同様に、第２の拡散層３０ｂの表面の凹凸が軟化状態の第２の導電機能層２５ｂに食い込みながら、第２の導電機能層２５ｂに含まれる分散繊維化したＰＴＦＥと第２の拡散層３０ｂとが、フッ素溶媒を介して、互いの疎水性部材の親和性および毛細管現象により定着する。 [8] Then, similarly to the step [3], the second diffusion layer 30b is bonded before the fluorine solvent contained in the second conductive functional layer 25b is evaporated and dried. At this time, in the same manner as in the step [3], the surface of the second diffusion layer 30b was distorted into the softened second conductive function layer 25b, and dispersed into fibers contained in the second conductive function layer 25b. PTFE and the second diffusion layer 30b are fixed by the affinity of each other hydrophobic member and capillary action through the fluorine solvent.

［９］そして、工程［４］と同様に、フッ素溶媒の短時間（１分以内）での蒸散乾燥により、第２の触媒層２０ｂＦＨと第２の導電機能層２５ｂと第２の拡散層３０ｂとが固着して一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された構造となる。この結果、第１の拡散層３０ａ、第１の導電機能層２５ａ、第１の触媒層２０ａＨ、電解質層１０Ｈ、第２の触媒層２０ｂＦＨ、第２の導電機能層２５ｂ、および、第２の拡散層３０ｂが一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された構造を有する膜電極拡散層接合体（ＭＥＧＡ）を形成することができる。 [9] Similarly to the step [4], the second catalyst layer 20bFH, the second conductive functional layer 25b, and the second diffusion layer 30b are obtained by evaporating and drying the fluorine solvent in a short time (within 1 minute). And are integrally formed and have a structure in which each interface is continuously formed without an interface. As a result, the first diffusion layer 30a, the first conductive functional layer 25a, the first catalyst layer 20aH, the electrolyte layer 10H, the second catalyst layer 20bFH, the second conductive functional layer 25b, and the second diffusion The layer 30b is integrally formed, and a membrane electrode diffusion layer assembly (MEGA) having a structure formed continuously without having an interface at each boundary can be formed.

図７は、図５により示した作製方法により作製されたＭＥＧＡを用いたセル性能と、比較例として従来の作製方法により作製されたＭＥＧＡを用いたセル性能について示す説明図である。セル性能としては、カソード（Ｃａ）側に無加湿でガスを供給する場合において、負荷電流１．２Ａ／ｃｍ2とした場合のセル電圧とセル抵抗の温度特性を示している。なお、比較例としての従来の作製方法は、イオン交換基能を備える電解質を有する電解質層（膜）の両面に、電解質を含む触媒インクを塗工することにより、触媒層を形成してＭＥＡを作製し、そのＭＥＡの両面に拡散層を熱圧着あるいは接着層を介して貼り合わせてＭＥＧＡを形成するものである。ここでは、ＭＥＡに拡散層を１３０℃で熱圧着してＭＥＧＡを形成したものを用いる。また、膜厚は２０μｍとする。 FIG. 7 is an explanatory diagram showing cell performance using MEGA manufactured by the manufacturing method shown in FIG. 5 and cell performance using MEGA manufactured by a conventional manufacturing method as a comparative example. As the cell performance, the temperature characteristics of the cell voltage and the cell resistance when the load current is 1.2 A / cm 2 in the case of supplying gas to the cathode (Ca) without humidification are shown. In addition, the conventional production method as a comparative example is that the catalyst layer containing the electrolyte is applied to both surfaces of the electrolyte layer (membrane) having the electrolyte having the ion exchange base ability, thereby forming the catalyst layer to form the MEA. The MEGA is formed by bonding the diffusion layers to both sides of the MEA through thermocompression bonding or an adhesive layer. Here, a MEGA formed by thermocompression bonding of the diffusion layer to the MEA at 130 ° C. is used. The film thickness is 20 μm.

図７からわかるように、本実施例により作製されたＭＥＧＡは、比較例としての従来のＭＥＧＡに比べて、セル電圧特性およびセル抵抗特性の両方とも向上していることがわかる。特に、７０℃以下の中温域以下の出力（セル電圧）が向上し、発電により発生する生成水のマネジメント能力が向上していることがわかる。   As can be seen from FIG. 7, the MEGA fabricated according to this example is improved in both cell voltage characteristics and cell resistance characteristics as compared with the conventional MEGA as a comparative example. In particular, it can be seen that the output (cell voltage) below the middle temperature range of 70 ° C. or less is improved, and the management ability of the generated water generated by power generation is improved.

以上のように、上記第４実施例の膜電極拡散層接合体の作製方法によれば、作製された膜電極拡散層接合体において、第１の拡散層、第１の触媒層、電解質層、第２の触媒層、および、第２の拡散層の各層間を一体化して形成することができるとともに、各層の境界に界面を持たず連続するように形成することができる。これにより、従来例で説明した問題点、拡散層の剥離強度や、抵抗成分の増加等の問題を改善することができる。また、導電機能層を介して拡散層を形成することにより、加熱圧着や焼成工程を設けることなく膜電極拡散層接合体を作製することができる。   As described above, according to the method for manufacturing the membrane electrode diffusion layer assembly of the fourth embodiment, in the manufactured membrane electrode diffusion layer assembly, the first diffusion layer, the first catalyst layer, the electrolyte layer, The layers of the second catalyst layer and the second diffusion layer can be formed integrally, and can be formed so as not to have an interface at the boundary between the layers. Thereby, problems such as the problems described in the conventional example, the peel strength of the diffusion layer, and the increase in resistance component can be improved. In addition, by forming the diffusion layer via the conductive functional layer, it is possible to produce a membrane electrode diffusion layer assembly without providing a thermocompression bonding or firing process.

図８は、従来の膜電極接合体に導電機能層を介して拡散層を一体化形成することによる膜電極拡散層接合体の作製方法について示す説明図である。この作製方法は、以下で説明するように、イオン交換基能を有する電解質で構成された電解質層（膜）の両面にイオン交換基能を有する電解質を含む触媒層を塗工や転写、スプレー等で形成することによりＭＥＡを作製し、その両面上に導電機能層を介して拡散層を一体化形成するものである。   FIG. 8 is an explanatory view showing a method for producing a membrane / electrode diffusion layer assembly by integrally forming a diffusion layer via a conductive functional layer on a conventional membrane / electrode assembly. As will be described below, this production method is performed by applying, transferring, spraying, etc. a catalyst layer containing an electrolyte having an ion exchange base ability on both surfaces of an electrolyte layer (membrane) composed of an electrolyte having an ion exchange base ability. The MEA is produced by forming the diffusion layer on both sides of the MEA via the conductive functional layer.

まず、この作製方法の実行に先立って、イオン交換基能を有するＨ型の従来の電解質層（膜）用部材、触媒層用インク、および、拡散層用部材と、導電機能層用ペーストと、を準備する。なお、Ｈ型の触媒層用インクは、水・アルコール類を溶媒とした触媒担時カーボンおよび電解質の分散溶液を用いることができる。   First, prior to the execution of this production method, an H-type conventional electrolyte layer (membrane) member having ion exchange base ability, a catalyst layer ink, a diffusion layer member, a conductive functional layer paste, Prepare. The H-type catalyst layer ink may be a catalyst-supported carbon and electrolyte dispersion using water / alcohol as a solvent.

［１］まず、電解質層用部材を従来のＨ型の電解質層１０Ｈとして用い、電解質層１０Ｈの両面に従来のＨ型の触媒層用インク２０ｐＨを塗工して、従来のＨ型の第１の触媒層２０ａＨおよび第２の触媒層２０ｂＨを形成する。 [1] First, a member for an electrolyte layer is used as a conventional H-type electrolyte layer 10H, and the conventional H-type catalyst layer ink 20pH is applied to both surfaces of the electrolyte layer 10H. The catalyst layer 20aH and the second catalyst layer 20bH are formed.

［２］次に、触媒層用インク２０ｐＨの塗工乾燥後、形成された第１の触媒層２０ａＨの上面に、導電機能層用ペースト２５ｐを塗工して、第１の導電機能層２５ａを形成する。ここで、第１の触媒層２０ａＨの表面は、イオン交換樹脂（電解質）の分子構造よりＳＯ３Ｈ基による親水性とＣＦ２基による疎水性とが混在する親疎水状態となっている。また、触媒担時カーボンもカーボン自体が疎水性を有している。そして、導電機能層２５ａを形成する導電機能層用ペースト２５ｐにもカーボンやＰＴＦＥ、フッ素溶媒等が含まれており、疎水性を有している。これにより、第１の触媒層２０ａＨと導電機能層用ペースト２５ｐとは親和性が確保されるので、導電機能層用ペースト２５ｐの塗工時において、第１の触媒層２０ａＨの上面に第１の導電機能層２５ａの定着化が可能となる。そして、導電機能層用ペースト２５ｐに含まれるフッ素溶媒の蒸散乾燥時において、第１の触媒層２０ａＨと第１の導電機能層２５ａとが密着して一体化形成される。 [2] Next, after applying and drying the catalyst layer ink 20pH, the conductive functional layer paste 25p is applied to the upper surface of the formed first catalyst layer 20aH, and the first conductive functional layer 25a is applied. Form. Here, the surface of the first catalyst layer 20aH is in a hydrophilic / hydrophobic state in which hydrophilicity due to SO3H groups and hydrophobicity due to CF2 groups are mixed due to the molecular structure of the ion exchange resin (electrolyte). In addition, the catalyst-supporting carbon is also hydrophobic. The conductive functional layer paste 25p forming the conductive functional layer 25a also contains carbon, PTFE, a fluorine solvent, etc., and has hydrophobicity. Thereby, the affinity between the first catalyst layer 20aH and the conductive functional layer paste 25p is ensured, and therefore, when the conductive functional layer paste 25p is applied, the first catalyst layer 20aH is formed on the upper surface of the first catalyst layer 20aH. The conductive functional layer 25a can be fixed. When the fluorine solvent contained in the conductive functional layer paste 25p is evaporated and dried, the first catalyst layer 20aH and the first conductive functional layer 25a are in close contact and integrally formed.

［３］そして、導電機能層用ペースト２５ｐの塗工後、これに含まれるフッ素溶媒が蒸散乾燥する前に、形成された第１の導電機能層２５ａの上面に、拡散層部材により構成される第１の拡散層３０ａを貼り合わせる。 [3] Then, after the conductive functional layer paste 25p is applied, before the fluorine solvent contained therein is evaporated and dried, the upper surface of the formed first conductive functional layer 25a is constituted by a diffusion layer member. The first diffusion layer 30a is bonded.

［４］このとき、第１の拡散層３０ａの表面の凹凸が軟化状態の第１の導電機能層２５ａに食い込みながら、第１の導電機能層２５ａに含まれる分散繊維化したＰＴＦＥと第１の拡散層３０ａとが、フッ素溶媒を介して、互いの疎水性部材の親和性および毛細管現象により定着し、フッ素溶媒の蒸散乾燥で固着して一体化形成される。 [4] At this time, while the irregularities on the surface of the first diffusion layer 30a bite into the soft first conductive functional layer 25a, the dispersed fiberized PTFE contained in the first conductive functional layer 25a and the first conductive layer 25a The diffusion layer 30a is fixed by the affinity of each other hydrophobic member and the capillary phenomenon through the fluorine solvent, and is fixed and integrally formed by evaporation drying of the fluorine solvent.

［５］次に、工程［２］と同様に、第２の触媒層２０ｂＨの上面に、導電機能層用ペースト２５ｐを塗工して、導電機能層用ペースト２５ｐに含まれるフッ素溶媒の蒸散乾燥時において、第２の触媒層２０ｂＨと第２の導電機能層２５ｂとが密着して一体化形成される。 [5] Next, in the same manner as in the step [2], the conductive functional layer paste 25p is applied to the upper surface of the second catalyst layer 20bH, and the fluoric solvent contained in the conductive functional layer paste 25p is evaporated and dried. In some cases, the second catalyst layer 20bH and the second conductive functional layer 25b are in close contact and integrally formed.

［６］そして、工程［３］と同様に、導電機能層用ペースト２５ｐの塗工後、これに含まれるフッ素溶媒が蒸散乾燥する前に、形成された第２の導電機能層２５ｂの上面に、拡散層部材により構成される第２の拡散層３０ｂを貼り合わせる。 [6] And, similar to the step [3], after the conductive functional layer paste 25p is applied, before the fluorine solvent contained therein is evaporated and dried, the upper surface of the formed second conductive functional layer 25b is formed. Then, the second diffusion layer 30b composed of the diffusion layer member is bonded.

［７］このとき、工程［４］と同様に、第２の拡散層３０ｂの表面の凹凸が軟化状態の第２の導電機能層２５ｂに食い込みながら、第２の導電機能層２５ｂに含まれる分散繊維化したＰＴＦＥと第２の拡散層３０ｂとが、フッ素溶媒を介して、互いの疎水性部材の親和性および毛細管現象により定着し、フッ素溶媒の蒸散乾燥で固着して一体化形成される。 [7] At this time, as in the step [4], the unevenness on the surface of the second diffusion layer 30b bites into the softened second conductive functional layer 25b, and the dispersion contained in the second conductive functional layer 25b. The fiberized PTFE and the second diffusion layer 30b are fixed by the affinity of each other hydrophobic member and the capillary phenomenon through the fluorine solvent, and are fixed and integrally formed by evaporation drying of the fluorine solvent.

上記作製方法においても、導電機能層を介して拡散層を形成することにより、加熱圧着や焼成工程を設けることなく従来の膜電極接合体に拡散層を一体化形成した膜電極拡散層接合体を作製することができる。これにより、従来のように膜電極接合体に加熱圧着や焼成工程により拡散層を接合して膜電極拡散層接合体を作製する場合に比べて、発電時や低温時において膜の膨潤／収縮によって発生する剥離による性能低下を抑制することが可能である。しかしながら、電解質層に対して触媒層が形成された状態、すなわち、膜電極接合体に対して、導電機能層を介して拡散層を形成するため、電解質層と触媒層との間や触媒層と導電機能層との間の境界に界面ができ易く、膜電極拡散層接合体における抵抗成分は、上記実施例に比べて大きくなってしまうため、上記実施例により作製された膜電極拡散層接合体は、この点においても有利である。   Also in the above production method, by forming a diffusion layer via a conductive functional layer, a membrane electrode diffusion layer assembly in which a diffusion layer is integrally formed with a conventional membrane electrode assembly without providing a thermocompression bonding or firing step is provided. Can be produced. As a result, the membrane electrode diffusion layer assembly can be produced at the time of power generation or at a low temperature, compared with the conventional case where the diffusion layer is joined to the membrane electrode assembly by a thermocompression bonding or firing process. It is possible to suppress performance degradation due to the generated peeling. However, a state in which a catalyst layer is formed on the electrolyte layer, that is, a diffusion layer is formed on the membrane / electrode assembly via the conductive functional layer. The interface between the conductive functional layer is likely to form an interface, and the resistance component in the membrane electrode diffusion layer assembly is larger than that in the above example. Therefore, the membrane electrode diffusion layer assembly produced in the above example Is also advantageous in this respect.

Ｅ．第５実施例：
図９は、第５実施例の膜電極拡散層接合体の作製方法について示す説明図である。この第５実施例は、膜電極拡散層接合体の剛性を高めるために、補強層が加えられており、以下で説明するように、これに応じた作製方法となっている点が第４実施例と異なっている。 E. Example 5:
FIG. 9 is an explanatory view showing a method for producing the membrane / electrode diffusion layer assembly of the fifth embodiment. In the fifth embodiment, a reinforcing layer is added in order to increase the rigidity of the membrane electrode diffusion layer assembly, and as described below, the fourth embodiment is a manufacturing method according to this. It is different from the example.

まず、第５実施例の膜電極拡散層接合体の作製方法の実行に先立って、第４実施例と同様に、Ｆ型電解質層用部材、Ｆ型触媒層用インク、拡散層用部材、および、導電機能装用ペーストを準備するのに加えて、第２実施例と同様に、補強層部材を準備する。   First, prior to execution of the manufacturing method of the membrane electrode diffusion layer assembly of the fifth example, as in the fourth example, the F-type electrolyte layer member, the F-type catalyst layer ink, the diffusion layer member, and In addition to preparing the conductive functional wearing paste, a reinforcing layer member is prepared as in the second embodiment.

［１］まず、第２実施例の工程［１］と同様に、補強層部材を補強層（補強膜）１５として用い、補強層１５の一方の面上に、Ｆ型触媒層用インク２０ｐを塗工して、第１のＦ型触媒層２０ａを形成する。 [1] First, similarly to the step [1] of the second embodiment, the reinforcing layer member is used as the reinforcing layer (reinforcing film) 15, and the F-type catalyst layer ink 20 p is applied on one surface of the reinforcing layer 15. The first F-type catalyst layer 20a is formed by coating.

［２］次に、Ｆ型触媒層用インク２０ｐの塗工後、これに含まれるフッ素溶媒が蒸散乾燥する前に、形成された第１のＦ型触媒層２０ａの上面に、導電機能層用ペースト２５ｐを塗工して、第１の導電機能層２５ａを形成する。 [2] Next, after the application of the F-type catalyst layer ink 20p, before the fluorine solvent contained therein is evaporated and dried, the conductive functional layer layer is formed on the upper surface of the first F-type catalyst layer 20a. The paste 25p is applied to form the first conductive functional layer 25a.

［３］また、導電機能層用ペースト２５ｐの塗工後、これに含まれるフッ素溶媒が蒸散乾燥する前に、形成された第１の導電機能層２５ａの上面に、拡散層部材により構成される第１の拡散層３０ａを貼り合わせる。このとき、第１の拡散層３０ａの表面の凹凸が軟化状態の第１の導電機能層２５ａに食い込みながら、第１の導電機能層２５ａに含まれる分散繊維化したＰＴＦＥと第１の拡散層３０ａとが、フッ素溶媒を介して、互いの疎水性部材の親和性および毛細管現象により定着する。 [3] Further, after the conductive functional layer paste 25p is applied, before the fluorine solvent contained therein is evaporated and dried, the upper surface of the formed first conductive functional layer 25a is constituted by a diffusion layer member. The first diffusion layer 30a is bonded. At this time, while the unevenness of the surface of the first diffusion layer 30a bites into the softened first conductive function layer 25a, the dispersed fiberized PTFE and the first diffusion layer 30a included in the first conductive function layer 25a. Are fixed by the affinity of the hydrophobic members and capillary action through the fluorine solvent.

［４］そして、フッ素溶媒の短時間（１分以内）での蒸散乾燥により、第１のＦ型触媒層２０ａと第１の導電機能層２５ａと第１の拡散層３０ａとが固着して一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された構造となる。 [4] Then, the first F-type catalyst layer 20a, the first conductive functional layer 25a, and the first diffusion layer 30a are fixed and integrated by evaporating and drying the fluorine solvent in a short time (within 1 minute). In addition, the structure is formed continuously without any interface at each boundary.

［５］また、補強層１５の他方の面上に、Ｆ型電解質層用部材をＦ型電解質層１０として貼り合わせる。 [5] Further, an F-type electrolyte layer member is bonded as the F-type electrolyte layer 10 on the other surface of the reinforcing layer 15.

［６］そして、全体を加熱することにより、Ｆ型電解質層１０を溶融させて補強層１５内に含浸させるとともに、第１のＦ型触媒層２０ａに含まれるＦ型アイオノマも軟化することで、毛細管現象により補強層１５内への含浸が促進され、補強層１５を介してＦ型電解質層１０と第１のＦ型触媒層２０ａとが一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された構造となる。この結果、Ｆ型電解質層１０と第１のＦ型触媒層２０ａと拡散層３０とが一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された構造となる。 [6] By heating the whole, the F-type electrolyte layer 10 is melted and impregnated in the reinforcing layer 15, and the F-type ionomer contained in the first F-type catalyst layer 20a is also softened. The impregnation into the reinforcing layer 15 is promoted by the capillary phenomenon, and the F-type electrolyte layer 10 and the first F-type catalyst layer 20a are integrally formed through the reinforcing layer 15 and have an interface at each boundary. Therefore, the structure is formed continuously. As a result, the F-type electrolyte layer 10, the first F-type catalyst layer 20 a, and the diffusion layer 30 are integrally formed, and the structure is formed continuously without having an interface at each boundary.

また、第４実施例の工程［５］と同様に、Ｆ型電解質層１０の他方の面上に、Ｆ型触媒層用インク２０ｐを塗工して、第２のＦ型触媒層２０ｂを形成する。このとき、第４実施例の工程［１］と同様に、Ｆ型触媒層用インク２０ｐに含まれるフッ素溶液により、Ｆ型電解質層１０の表面が溶けてＦ型電解質層１０と第２のＦ型触媒層２０ｂとが一体化形成されるともに、その境界において界面を持たず連続的に形成された構造となる。この結果、第１の拡散層３０ａと第１の導電機能層２５ａと第１のＦ型触媒層２０ａとＦ型電解質層１０と第２のＦ型触媒層２０ｂとが一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された積層体の構造となる。   Similarly to the step [5] of the fourth embodiment, the F-type catalyst layer ink 20p is applied to the other surface of the F-type electrolyte layer 10 to form the second F-type catalyst layer 20b. To do. At this time, similarly to the step [1] of the fourth embodiment, the surface of the F-type electrolyte layer 10 is dissolved by the fluorine solution contained in the F-type catalyst layer ink 20p, and the F-type electrolyte layer 10 and the second F The type catalyst layer 20b is integrally formed and has a structure in which the boundary is not continuously formed at the boundary. As a result, the first diffusion layer 30a, the first conductive functional layer 25a, the first F-type catalyst layer 20a, the F-type electrolyte layer 10, and the second F-type catalyst layer 20b are integrally formed, It becomes the structure of the laminated body which did not have an interface in each boundary and was formed continuously.

［７］次に、第４実施例の工程［６］と同様に、形成された積層体の第２のＦ型触媒層２０ｂが形成されている側から加水分解処理をすることにより、第１のＦ型触媒層２０ａ、Ｆ型電解質層１０、および、第２のＦ型触媒層２０ｂと、第１の導電機能層２５ａおよび第１の拡散層３０ａに含まれるＦ型アイオノマのＳＯ２Ｆ基を、イオン交換機能を示すスルホン酸基（ＳＯ３Ｈ基）化させる。これにより、第１のＦ型触媒層２０ａ、Ｆ型電解質層１０は、イオン交換基能を備える電解質を有するＨ型の第１の触媒層２０ａＨ、電解質層１０Ｈに変性される。また、第２のＦ型触媒層２０ｂの表面は、加水分解処理により、親水物性を有する状態（ＳＯ３Ｈ基を含む状態）と疎水物性を有する状態（ＣＦ２基を含む状態）が混在する第２の触媒層２０ｂＦＨとなる。この結果、片側に拡散層を備え、各層が一体化形成されるとともに、各層の境界において界面を持たず連続的に形成された構造を有する膜電極拡散層接合体（ＭＥＧＡ）を形成することができる。 [7] Next, in the same manner as in the step [6] of the fourth embodiment, the first laminated body is hydrolyzed from the side on which the second F-type catalyst layer 20b is formed. The F-type catalyst layer 20a, the F-type electrolyte layer 10, the second F-type catalyst layer 20b, the SO2F group of the F-type ionomer contained in the first conductive functional layer 25a and the first diffusion layer 30a, A sulfonic acid group (SO3H group) having an ion exchange function is formed. As a result, the first F-type catalyst layer 20a and the F-type electrolyte layer 10 are modified into an H-type first catalyst layer 20aH and an electrolyte layer 10H having an electrolyte having ion exchange basic ability. In addition, the surface of the second F-type catalyst layer 20b is subjected to hydrolysis treatment in which a state having a hydrophilic property (a state including an SO3H group) and a state having a hydrophobic property (a state including a CF2 group) are mixed. The catalyst layer becomes 20bFH. As a result, a diffusion layer is provided on one side, each layer is integrally formed, and a membrane electrode diffusion layer assembly (MEGA) having a structure formed continuously without an interface at the boundary of each layer can be formed. it can.

［８］次に、第４実施例の工程［７］と同様に、第２の触媒層２０ｂＦＨの面上に、導電機能層用ペースト２５ｐを塗工して、第２の導電機能層２５ｂを形成する。上記したように、第２の触媒層２０ｂＦＨは、疎水物性を有する状態が混在している。そして、導電機能層２５ａを形成する導電機能層用ペースト２５ｐにもカーボンやＰＴＦＥ、フッ素溶媒等が含まれており、疎水性を有している。これにより、第２の触媒層２０ｂＦＨと導電機能層用ペースト２５ｐとは親和性が確保されるので、導電機能層用ペースト２５ｐの塗工時において、第２の触媒層２０ｂＦＨの上面に第２の導電機能層２５ｂの定着化が可能となる。そして、導電機能層用ペースト２５ｐに含まれるフッ素溶媒の蒸散乾燥時において、第２の触媒層２０ｂＨと第２の導電機能層２５ｂとが密着して一体化形成されるとともに、その境界において界面を持たず連続的に形成された構造となる。 [8] Next, as in the step [7] of the fourth embodiment, the conductive functional layer paste 25p is applied on the surface of the second catalyst layer 20bFH, and the second conductive functional layer 25b is formed. Form. As described above, the second catalyst layer 20bFH has a mixture of hydrophobic properties. The conductive functional layer paste 25p forming the conductive functional layer 25a also contains carbon, PTFE, a fluorine solvent, etc., and has hydrophobicity. Thereby, the affinity between the second catalyst layer 20bFH and the conductive functional layer paste 25p is ensured. Therefore, when the conductive functional layer paste 25p is applied, the second catalyst layer 20bFH is formed on the upper surface of the second catalyst layer 20bFH. The conductive functional layer 25b can be fixed. The second catalyst layer 20bH and the second conductive functional layer 25b are formed in close contact with each other at the time of evaporating and drying the fluorine solvent contained in the conductive functional layer paste 25p, and an interface is formed at the boundary. It has a structure formed continuously without it.

［９］そして、工程［３］と同様に、第２の導電機能層２５ｂに含まれるフッ素溶媒が蒸散乾燥する前に、第２の拡散層３０ｂを貼り合わせる。このとき、工程［３］と同様に、第２の拡散層３０ｂの表面の凹凸が軟化状態の第２の導電機能層２５ｂに食い込みながら、第２の導電機能層２５ｂに含まれる分散繊維化したＰＴＦＥと第２の拡散層３０ｂとが、フッ素溶媒を介して、互いの疎水性部材の親和性および毛細管現象により定着する。 [9] Similarly to the step [3], the second diffusion layer 30b is bonded before the fluorine solvent contained in the second conductive functional layer 25b is evaporated and dried. At this time, in the same manner as in the step [3], the surface of the second diffusion layer 30b was distorted into the softened second conductive function layer 25b, and dispersed into fibers contained in the second conductive function layer 25b. PTFE and the second diffusion layer 30b are fixed by the affinity of each other hydrophobic member and capillary action through the fluorine solvent.

［１０］そして、工程［４］と同様に、フッ素溶媒の短時間（１分以内）での蒸散乾燥により、第２の触媒層２０ｂＦＨと第２の導電機能層２５ｂと第２の拡散層３０ｂとが固着して一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された構造となる。この結果、第１の拡散層３０ａ、第１の導電機能層２５ａ、第１の触媒層２０ａＨ、電解質層１０、第２の触媒層２０ｂＦＨ、第２の導電機能層２５ｂ、および、第２の拡散層３０ｂが一体化形成されるとともに、それぞれの境界において界面を持たず連続的に形成された構造を有する膜電極拡散層接合体（ＭＥＧＡ）を形成することができる。 [10] Similarly to the step [4], the second catalyst layer 20bFH, the second conductive function layer 25b, and the second diffusion layer 30b are obtained by evaporating and drying the fluorine solvent in a short time (within 1 minute). And are integrally formed and have a structure in which each interface is continuously formed without an interface. As a result, the first diffusion layer 30a, the first conductive functional layer 25a, the first catalyst layer 20aH, the electrolyte layer 10, the second catalyst layer 20bFH, the second conductive functional layer 25b, and the second diffusion The layer 30b is integrally formed, and a membrane electrode diffusion layer assembly (MEGA) having a structure formed continuously without having an interface at each boundary can be formed.

以上のように、上記第５実施例の膜電極拡散層接合体の作製方法によっても、第４実施例と同様に、作製された膜電極拡散層接合体において、第１の拡散層、第１の触媒層、電解質層、第２の触媒層、および、第２の拡散層の各層間を一体化して形成することができるとともに、各層の境界に界面を持たず連続するように形成することができる。これにより、従来例で説明した問題点、拡散層の剥離強度や、抵抗成分の増加等の問題を改善することができる。また、導電機能層を介して拡散層を形成することにより、加熱圧着や焼成工程を設けることなく膜電極拡散層接合体を作製することができる。さらに、第５実施例においては、補強層１５により電解質層の剛性を第４実施例に比べて高めることができる。   As described above, also by the method for manufacturing the membrane electrode diffusion layer assembly of the fifth embodiment, in the same manner as in the fourth embodiment, in the manufactured membrane electrode diffusion layer assembly, The catalyst layer, the electrolyte layer, the second catalyst layer, and the second diffusion layer can be integrally formed, and can be formed continuously without having an interface at the boundary between the layers. it can. Thereby, problems such as the problems described in the conventional example, the peel strength of the diffusion layer, and the increase of the resistance component can be improved. In addition, by forming the diffusion layer via the conductive functional layer, it is possible to produce a membrane electrode diffusion layer assembly without providing a thermocompression bonding or firing process. Furthermore, in the fifth embodiment, the rigidity of the electrolyte layer can be increased by the reinforcing layer 15 as compared with the fourth embodiment.

なお、この発明は上記の実施例や実施形態に限られるものではなく、その要旨を逸脱しない範囲において種々の態様において実施することが可能である。   In addition, this invention is not restricted to said Example and embodiment, In the range which does not deviate from the summary, it is possible to implement in various aspects.

１０…Ｆ型電解質層
１０Ｈ…電解質層
１５…補強層
２０ａ…第１のＦ型触媒層
２０ｂ…第２のＦ型触媒層
２０ｂＦＨ…第２の触媒層
２０ａＨ…第１の触媒層
２０ｂＨ…第２の触媒層
２０ｐ…Ｆ型触媒層用インク
２０ｐＨ…触媒層用インク
２５ａ…第１の導電機能層
２５ｂ…第２の導電機能層
２５ｐ…導電機能層用ペースト
３０…拡散層
３０ａ…第１の拡散層
３０ｂ…第２の拡散層 DESCRIPTION OF SYMBOLS 10 ... F type electrolyte layer 10H ... Electrolyte layer 15 ... Reinforcement layer 20a ... 1st F type catalyst layer 20b ... 2nd F type catalyst layer 20b FH ... 2nd catalyst layer 20aH ... 1st catalyst layer 20bH ... 2nd Catalyst layer 20p ... F type catalyst layer ink 20pH ... catalyst layer ink 25a ... first conductive functional layer 25b ... second conductive functional layer 25p ... conductive functional layer paste 30 ... diffusion layer 30a ... first diffusion Layer 30b ... second diffusion layer

Claims (6)

膜電極拡散層接合体の作製方法であって
ＳＯ２Ｆ基を有する電解質前駆体により構成されたイオン交換基能を備えない電解質前駆体膜を準備する工程と、
ＳＯ２Ｆ基を有するアイオノマをフッ素溶媒に溶融分散させたアイオノマ溶液と、疎水物性を有する触媒反応物質と、を混合した触媒層部材を準備する工程と、
疎水物性を有する拡散層部材を準備する工程と、
前記電解質前駆体膜の一方の面に前記触媒層部材を塗工して第１の触媒前駆体層を形成し、前記触媒層部材に含まれる前記フッ素溶媒により前記電解質前駆体膜の表面を溶融させることにより、前記電解質前駆体膜と前記第１の触媒前駆体層とを一体化する工程と、
前記触媒層部材の塗工後前記フッ素溶媒が乾燥する前に、前記第１の触媒前駆体層上面に前記拡散層部材を貼り合わせて、前記触媒層部材の一部を前記拡散層部材内に浸透させることにより、前記第１の触媒前駆体層と前記拡散層部材とを一体化する工程と、
前記電解質前駆体膜の他方の面に前記触媒層部材を塗工して第２の触媒前駆体層を形成し、前記触媒層部材に含まれる前記フッ素溶媒により前記電解質前駆体膜の表面を溶融させることにより、前記電解質前駆体膜と前記第２の触媒前駆体層とを一体化する工程と、
前記拡散層部材と前記第１の触媒前駆体層と前記電解質前駆体膜と前記第２の触媒前駆体層とが一体化された積層体を、前記第２の触媒前駆体層側から加水分解処理して、前記第１の触媒前駆体層、前記第２の触媒前駆体層、前記電解質前駆体膜、および、前記拡散層部材内に浸透した前記アイオノマをスルホン化させることにより、前記第１の触媒前駆体層、前記第２の触媒前駆体層、および、前記電解質前駆体膜を、イオン交換基能を備える電解質を有する第１の触媒層、第２の触媒層、および、電解質膜に変成させる工程と、
を備えることを特徴とする膜電極拡散層接合体の作製方法。 A method for preparing a membrane electrode diffusion layer assembly, the step of preparing an electrolyte precursor membrane that does not have an ion-exchange base ability and is constituted by an electrolyte precursor having an SO2F group;
Preparing a catalyst layer member in which an ionomer solution in which an ionomer having an SO2F group is melt-dispersed in a fluorine solvent and a catalytic reactant having hydrophobic properties are mixed;
Preparing a diffusion layer member having hydrophobic properties;
The catalyst layer member is applied to one surface of the electrolyte precursor film to form a first catalyst precursor layer, and the surface of the electrolyte precursor film is melted by the fluorine solvent contained in the catalyst layer member By integrating the electrolyte precursor film and the first catalyst precursor layer,
After the application of the catalyst layer member and before the fluorine solvent is dried, the diffusion layer member is bonded to the upper surface of the first catalyst precursor layer, and a part of the catalyst layer member is placed in the diffusion layer member. Integrating the first catalyst precursor layer and the diffusion layer member by infiltrating;
The catalyst layer member is applied to the other surface of the electrolyte precursor film to form a second catalyst precursor layer, and the surface of the electrolyte precursor film is melted by the fluorine solvent contained in the catalyst layer member. By integrating the electrolyte precursor film and the second catalyst precursor layer,
The laminated body in which the diffusion layer member, the first catalyst precursor layer, the electrolyte precursor film, and the second catalyst precursor layer are integrated is hydrolyzed from the second catalyst precursor layer side. The first catalyst precursor layer, the second catalyst precursor layer, the electrolyte precursor film, and the ionomer that has penetrated into the diffusion layer member are sulfonated by the treatment. The catalyst precursor layer, the second catalyst precursor layer, and the electrolyte precursor film are used as the first catalyst layer, the second catalyst layer, and the electrolyte film having an electrolyte having an ion exchange group ability. A transformation process;
A method for producing a membrane electrode diffusion layer assembly, comprising: 膜電極拡散層接合体の作製方法であって
多孔部材で構成される補強層部材を準備する工程と、
ＳＯ２Ｆ基を有する電解質前駆体により構成されたイオン交換基能を備えない電解質前駆体膜を準備する工程と、
ＳＯ２Ｆ基を有するアイオノマをフッ素溶媒に溶融分散させたアイオノマ溶液と、疎水物性を有する触媒反応物質と、を混合した触媒層部材を準備する工程と、
疎水物性を有する拡散層部材を準備する工程と、
前記補強層部材の一方の面に前記触媒層部材を塗工して第１の触媒前駆体層を形成し、前記補強層部材内に前記触媒層部材の一部を浸透させることにより、前記補強層部材と前記第１の触媒前駆体層とを一体化する工程と、
前記触媒層部材の塗工後前記フッ素溶媒が乾燥する前に、前記第１の触媒前駆体層上面に前記拡散層部材を貼り合わせて、前記触媒層部材の一部を前記拡散層部材内に浸透させることにより、前記第１の触媒前駆体層と前記拡散層部材とを一体化する工程と、
前記補強層部材の他方の面に前記電解質前駆体膜の一方の面を貼り合わせて加熱することにより、前記電解質前駆体膜中の前記電解質前駆体を溶融させて、前記補強層部材内に浸透させるとともに、前記第１の触媒前駆体層中の前記アイオノマを軟化させることにより、前記電解質前駆体膜と前記第１の触媒前駆体層とを一体化させる工程と、
前記電解質前駆体膜の他方の面上に前記触媒層部材を塗工して第２の触媒前駆体層を形成し、前記触媒層部材に含まれる前記フッ素溶媒により前記電解質前駆体膜の表面を溶融させることにより、前記電解質前駆体膜と前記第２の触媒前駆体層とを一体化する工程と、
前記拡散層部材と前記第１の触媒前駆体層と前記電解質前駆体膜と前記第２の触媒前駆体層とが一体化された積層体を、前記第２の触媒前駆体層側から加水分解処理して、前記第１の触媒前駆体層、前記第２の触媒前駆体層、前記電解質前駆体膜、および、前記拡散層部材内に浸透した前記アイオノマをスルホン化させることにより、前記第１の触媒前駆体層、前記第２の触媒前駆体層、および、前記電解質前駆体膜を、イオン交換基能を備える電解質を有する第１の触媒層、第２の触媒層、および、電解質膜に変成させる工程と、
を備えることを特徴とする膜電極拡散層接合体の作製方法。 A method for producing a membrane electrode diffusion layer assembly, the step of preparing a reinforcing layer member composed of a porous member,
Preparing an electrolyte precursor film that does not have an ion-exchange group ability and is constituted by an electrolyte precursor having a SO2F group;
Preparing a catalyst layer member in which an ionomer solution in which an ionomer having an SO2F group is melt-dispersed in a fluorine solvent and a catalytic reactant having hydrophobic properties are mixed;
Preparing a diffusion layer member having hydrophobic properties;
The catalyst layer member is coated on one surface of the reinforcement layer member to form a first catalyst precursor layer, and a part of the catalyst layer member is infiltrated into the reinforcement layer member, whereby the reinforcement Integrating a layer member and the first catalyst precursor layer;
After the application of the catalyst layer member and before the fluorine solvent is dried, the diffusion layer member is bonded to the upper surface of the first catalyst precursor layer, and a part of the catalyst layer member is placed in the diffusion layer member. Integrating the first catalyst precursor layer and the diffusion layer member by infiltrating;
By bonding one surface of the electrolyte precursor film to the other surface of the reinforcing layer member and heating, the electrolyte precursor in the electrolyte precursor film is melted and penetrated into the reinforcing layer member And integrating the electrolyte precursor film and the first catalyst precursor layer by softening the ionomer in the first catalyst precursor layer;
The catalyst layer member is coated on the other surface of the electrolyte precursor film to form a second catalyst precursor layer, and the surface of the electrolyte precursor film is covered with the fluorine solvent contained in the catalyst layer member. Integrating the electrolyte precursor film and the second catalyst precursor layer by melting,
The laminated body in which the diffusion layer member, the first catalyst precursor layer, the electrolyte precursor film, and the second catalyst precursor layer are integrated is hydrolyzed from the second catalyst precursor layer side. The first catalyst precursor layer, the second catalyst precursor layer, the electrolyte precursor film, and the ionomer that has penetrated into the diffusion layer member are sulfonated by the treatment. The catalyst precursor layer, the second catalyst precursor layer, and the electrolyte precursor film are used as the first catalyst layer, the second catalyst layer, and the electrolyte film having an electrolyte having an ion exchange group ability. A transformation process;
A method for producing a membrane electrode diffusion layer assembly, comprising: 膜電極拡散層接合体の作製方法であって
多孔部材で構成される２つの補強層部材を準備する工程と、
ＳＯ２Ｆ基を有する電解質前駆体により構成されたイオン交換基能を備えない電解質前駆体膜を準備する工程と、
ＳＯ２Ｆ基を有するアイオノマをフッ素溶媒に溶融分散させたアイオノマ溶液と、疎水物性を有する触媒反応物質と、を混合した触媒層部材を準備する工程と、
疎水物性を有する拡散層部材を準備する工程と、
それぞれの前記補強層部材の一方の面に前記触媒層部材を塗工して第１と第２の触媒前駆体層を形成し、前記補強層部材内に前記触媒層部材の一部を浸透させることにより、前記補強層部材と前記第１と第２の触媒前駆体層とを一体化する工程と、
前記第１の触媒前駆体層の形成後前記触媒層部材中の前記フッ素溶媒が乾燥する前に、前記第１の触媒前駆体層上面に前記拡散層部材を貼り合わせて、前記触媒層部材の一部を前記拡散層部材内に浸透させることにより、前記第１の触媒前駆体層と前記拡散層部材とを一体化する工程と、
前記第１の触媒前駆体層が形成された前記補強層部材の他方の面に前記電解質前駆体膜の一方の面を貼り合わせるとともに、前記電解質前駆体膜の他方の面上に前記第２の触媒前駆体層が形成された前記補強層部材の他方の面を貼り合わせて加熱することにより、前記電解質前駆体膜中の前記電解質前駆体を溶融させて、前記第１と第２の触媒前駆体層が形成されたそれぞれの前記補強層部材内に浸透させるとともに、前記第１と第２の触媒前駆体層中の前記アイオノマを軟化させることにより、前記電解質前駆体膜と前記第１と第２の触媒前駆体層とを一体化させる工程と、
前記拡散層部材と前記第１の触媒前駆体層と前記電解質前駆体膜と前記第２の触媒前駆体層とが一体化された積層体を、前記第２の触媒前駆体層側から加水分解処理して、前記第１の触媒前駆体層、前記第２の触媒前駆体層、前記電解質前駆体膜、および、前記拡散層部材内に浸透した前記アイオノマをスルホン化させることにより、前記第１の触媒前駆体層、前記第２の触媒前駆体層、および、前記電解質前駆体膜を、イオン交換基能を備える電解質を有する第１の触媒層、第２の触媒層、および、電解質膜に変成させる工程と、
を備えることを特徴とする膜電極拡散層接合体の作製方法。 A method for producing a membrane electrode diffusion layer assembly, comprising preparing two reinforcing layer members composed of porous members;
Preparing an electrolyte precursor film that does not have an ion-exchange group ability and is constituted by an electrolyte precursor having a SO2F group;
Preparing a catalyst layer member in which an ionomer solution in which an ionomer having an SO2F group is melt-dispersed in a fluorine solvent and a catalytic reactant having hydrophobic properties are mixed;
Preparing a diffusion layer member having hydrophobic properties;
The catalyst layer member is applied to one surface of each of the reinforcing layer members to form first and second catalyst precursor layers, and a part of the catalyst layer member is infiltrated into the reinforcing layer member. A step of integrating the reinforcing layer member and the first and second catalyst precursor layers;
Before the fluorine solvent in the catalyst layer member is dried after the formation of the first catalyst precursor layer, the diffusion layer member is bonded to the upper surface of the first catalyst precursor layer, and the catalyst layer member Integrating the first catalyst precursor layer and the diffusion layer member by infiltrating a portion thereof into the diffusion layer member;
The one surface of the electrolyte precursor film is bonded to the other surface of the reinforcing layer member on which the first catalyst precursor layer is formed, and the second surface is formed on the other surface of the electrolyte precursor film. The first and second catalyst precursors are melted by laminating and heating the other surface of the reinforcing layer member on which the catalyst precursor layer is formed, thereby melting the electrolyte precursor in the electrolyte precursor film. The electrolyte precursor film and the first and second electrolyte layers are infiltrated into each of the reinforcing layer members on which the body layer is formed, and the ionomer in the first and second catalyst precursor layers is softened. Integrating the two catalyst precursor layers;
The laminated body in which the diffusion layer member, the first catalyst precursor layer, the electrolyte precursor film, and the second catalyst precursor layer are integrated is hydrolyzed from the second catalyst precursor layer side. The first catalyst precursor layer, the second catalyst precursor layer, the electrolyte precursor film, and the ionomer that has penetrated into the diffusion layer member are sulfonated by the treatment. The catalyst precursor layer, the second catalyst precursor layer, and the electrolyte precursor film are used as the first catalyst layer, the second catalyst layer, and the electrolyte film having an electrolyte having an ion exchange group ability. A transformation process;
A method for producing a membrane electrode diffusion layer assembly, comprising: 膜電極接合体の作製方法であって
ＳＯ２Ｆ基を有する電解質前駆体により構成されたイオン交換基能を備えない電解質前駆体膜を準備する工程と、
ＳＯ２Ｆ基を有するアイオノマをフッ素溶媒に溶融分散させたアイオノマ溶液と、疎水物性を有する触媒反応物質と、を混合した触媒層部材を準備する工程と、
カーボンと撥水部材とフッ素溶媒とを混合した導電機能層用ペーストを準備する工程と、
疎水物性を有する拡散層部材を準備する工程と、
前記電解質前駆体膜の一方の面に前記触媒層部材を塗工して第１の触媒前駆体層を形成し、前記触媒層部材に含まれる前記フッ素溶媒により前記電解質前駆体膜の表面を溶融させることにより、前記電解質前駆体膜と前記第１の触媒前駆体層とを一体化する工程と、
前記触媒層部材の塗工後前記フッ素溶媒が乾燥する前に、前記第１の触媒前駆体層上面に前記導電機能層用ペーストを塗工して導電機能層を形成することにより、前記第１の触媒電駆体と前記導電機能層とを一体化する工程と、
前記導電機能層用ペーストの塗工後前記フッ素溶媒が乾燥する前に、前記導電機能層上面に前記拡散層部材を貼り合わせて、前記拡散層部材の表面の凹凸面を前記導電機能層中に食い込ませ、前記フッ素溶媒の乾燥により前記導電機能層と前記拡散層部材とを一体化する工程と、
前記電解質前駆体膜の他方の面に前記触媒層部材を塗工して第２の触媒前駆体層を形成し、前記触媒層部材に含まれる前記フッ素溶媒により前記電解質前駆体膜の表面を溶融させることにより、前記電解質前駆体膜と前記第２の触媒前駆体層とを一体化する工程と、
前記拡散層部材と前記第１の触媒前駆体層と前記電解質前駆体膜と前記第２の触媒前駆体層とが一体化された積層体を、前記第２の触媒前駆体層側から加水分解処理して、前記第１の触媒前駆体層、前記第２の触媒前駆体層、前記電解質前駆体膜、および、前記拡散層部材内に浸透した前記アイオノマをスルホン化させることにより、前記第１の触媒前駆体層、前記第２の触媒前駆体層、および、前記電解質前駆体膜を、イオン交換基能を備える電解質を有する第１の触媒層、第２の触媒層、および、電解質膜に変成させる工程と、
を備えることを特徴とする膜電極拡散層接合体の作製方法。 A method for preparing a membrane electrode assembly, the step of preparing an electrolyte precursor membrane that does not have an ion exchange group ability and is constituted by an electrolyte precursor having an SO2F group;
Preparing a catalyst layer member in which an ionomer solution in which an ionomer having an SO2F group is melt-dispersed in a fluorine solvent and a catalytic reactant having hydrophobic properties are mixed;
Preparing a conductive functional layer paste in which carbon, a water repellent member, and a fluorine solvent are mixed;
Preparing a diffusion layer member having hydrophobic properties;
The catalyst layer member is applied to one surface of the electrolyte precursor film to form a first catalyst precursor layer, and the surface of the electrolyte precursor film is melted by the fluorine solvent contained in the catalyst layer member By integrating the electrolyte precursor film and the first catalyst precursor layer,
By applying the conductive functional layer paste on the upper surface of the first catalyst precursor layer to form the conductive functional layer after the application of the catalyst layer member and before the fluorine solvent is dried, A step of integrating the catalytic conductor of the above and the conductive functional layer,
After the application of the conductive functional layer paste and before the fluorine solvent is dried, the diffusion layer member is bonded to the upper surface of the conductive functional layer so that the uneven surface on the surface of the diffusion layer member is in the conductive functional layer. Biting and integrating the conductive functional layer and the diffusion layer member by drying the fluorine solvent;
The catalyst layer member is applied to the other surface of the electrolyte precursor film to form a second catalyst precursor layer, and the surface of the electrolyte precursor film is melted by the fluorine solvent contained in the catalyst layer member. By integrating the electrolyte precursor film and the second catalyst precursor layer,
The laminated body in which the diffusion layer member, the first catalyst precursor layer, the electrolyte precursor film, and the second catalyst precursor layer are integrated is hydrolyzed from the second catalyst precursor layer side. The first catalyst precursor layer, the second catalyst precursor layer, the electrolyte precursor film, and the ionomer that has penetrated into the diffusion layer member are sulfonated by the treatment. The catalyst precursor layer, the second catalyst precursor layer, and the electrolyte precursor film are used as the first catalyst layer, the second catalyst layer, and the electrolyte film having an electrolyte having an ion exchange group ability. A transformation process;
A method for producing a membrane electrode diffusion layer assembly, comprising: 膜電極拡散層接合体の作製方法であって
多孔部材で構成される補強層部材を準備する工程と、
ＳＯ２Ｆ基を有する電解質前駆体により構成されたイオン交換基能を備えない電解質前駆体膜を準備する工程と、
ＳＯ２Ｆ基を有するアイオノマをフッ素溶媒に溶融分散させた前駆体アイオノマ溶液と、疎水物性を有する触媒反応物質と、を混合した触媒層部材を準備する工程と、
カーボンと撥水部材とフッ素溶媒とを混合した導電機能層用ペーストを準備する工程と、
疎水物性を有する拡散層部材を準備する工程と、
前記補強層部材の一方の面に前記触媒層部材を塗工して第１の触媒前駆体層を形成し、前記補強層部材内に前記触媒層部材の一部を浸透させることにより、前記補強層部材と前記第１の触媒前駆体層を一体化する工程と、
前記触媒層部材の塗工後前記フッ素溶媒が乾燥する前に、前記第１の触媒前駆体層上面に前記導電機能層用ペーストを塗工して導電機能層を形成することにより、前記第１の触媒前駆体層と前記導電機能層とを一体化する工程と、
前記導電機能層用ペーストの塗工後前記フッ素溶媒が乾燥する前に、前記導電機能層上面に前記拡散層部材を貼り合わせて、前記拡散層部材の表面の凹凸面を前記導電機能層中に食い込ませ、前記フッ素溶媒の乾燥により前記導電機能層と前記拡散層部材とを一体化する工程と、
前記補強層部材の他方の面に前記電解質前駆体膜の一方の面を貼り合わせて加熱することにより、前記電解質前駆体膜中の前記電解質前駆体を溶融させて、前記補強層部材内に浸透させるとともに、前記第１の触媒前駆体層中の前記アイオノマを軟化させることにより、前記電解質前駆体膜と前記第１の触媒前駆体層とを一体化させる工程と、
前記電解質前駆体膜の他方の面上に前記触媒層部材を塗工して第２の触媒前駆体層を形成し、前記触媒層部材に含まれる前記フッ素溶媒により前記電解質前駆体膜の表面を溶融させることにより、前記電解質前駆体膜と前記第２の触媒前駆体層とを一体化する工程と、
前記拡散層部材と前記第１の触媒前駆体層と前記電解質前駆体膜と前記第２の触媒前駆体層とが一体化された積層体を、前記第２の触媒前駆体層側から加水分解処理して、前記第１の触媒前駆体層、前記第２の触媒前駆体層、前記電解質前駆体膜、および、前記拡散層部材内に浸透した前記アイオノマをスルホン化させることにより、前記第１の触媒前駆体層、前記第２の触媒前駆体層、および、前記電解質前駆体膜を、イオン交換基能を備える電解質を有する第１の触媒層、第２の触媒層、および、電解質膜に変成させる工程と、
を備えることを特徴とする膜電極拡散層接合体の作製方法。 A method for producing a membrane electrode diffusion layer assembly, the step of preparing a reinforcing layer member composed of a porous member,
Preparing an electrolyte precursor film that does not have an ion-exchange group ability and is constituted by an electrolyte precursor having a SO2F group;
Preparing a catalyst layer member in which a precursor ionomer solution in which an ionomer having an SO2F group is melt-dispersed in a fluorine solvent and a catalytic reactant having hydrophobic properties are mixed;
Preparing a conductive functional layer paste in which carbon, a water repellent member, and a fluorine solvent are mixed;
Preparing a diffusion layer member having hydrophobic properties;
The catalyst layer member is coated on one surface of the reinforcement layer member to form a first catalyst precursor layer, and a part of the catalyst layer member is infiltrated into the reinforcement layer member, whereby the reinforcement Integrating a layer member and the first catalyst precursor layer;
By applying the conductive functional layer paste on the upper surface of the first catalyst precursor layer to form the conductive functional layer after the application of the catalyst layer member and before the fluorine solvent is dried, The step of integrating the catalyst precursor layer and the conductive functional layer,
After the application of the conductive functional layer paste and before the fluorine solvent is dried, the diffusion layer member is bonded to the upper surface of the conductive functional layer so that the uneven surface on the surface of the diffusion layer member is in the conductive functional layer. Biting and integrating the conductive functional layer and the diffusion layer member by drying the fluorine solvent;
By bonding one surface of the electrolyte precursor film to the other surface of the reinforcing layer member and heating, the electrolyte precursor in the electrolyte precursor film is melted and penetrated into the reinforcing layer member And integrating the electrolyte precursor film and the first catalyst precursor layer by softening the ionomer in the first catalyst precursor layer;
The catalyst layer member is coated on the other surface of the electrolyte precursor film to form a second catalyst precursor layer, and the surface of the electrolyte precursor film is covered with the fluorine solvent contained in the catalyst layer member. Integrating the electrolyte precursor film and the second catalyst precursor layer by melting,
The laminated body in which the diffusion layer member, the first catalyst precursor layer, the electrolyte precursor film, and the second catalyst precursor layer are integrated is hydrolyzed from the second catalyst precursor layer side. The first catalyst precursor layer, the second catalyst precursor layer, the electrolyte precursor film, and the ionomer that has penetrated into the diffusion layer member are sulfonated by the treatment. The catalyst precursor layer, the second catalyst precursor layer, and the electrolyte precursor film are used as the first catalyst layer, the second catalyst layer, and the electrolyte film having an electrolyte having an ion exchange group ability. A transformation process;
A method for producing a membrane electrode diffusion layer assembly, comprising: 請求項１ないし請求項５のいずれか一項に記載の膜電極拡散層接合体の作製方法により作製された膜電極拡散層接合体。   A membrane / electrode diffusion layer assembly produced by the method for producing a membrane / electrode diffusion layer assembly according to claim 1.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014186959A (en) * 2013-03-25 2014-10-02 Toppan Printing Co Ltd Electrode for fuel battery, manufacturing method thereof, film electrode assembly for fuel battery, manufacturing method thereof, and solid polymer fuel battery
JP2014192019A (en) * 2013-03-27 2014-10-06 Toppan Printing Co Ltd Method for manufacturing electrode for fuel cell, electrode for fuel cell, method for manufacturing membrane electrode assembly for fuel cell, membrane electrode assembly for fuel cell, and polymer electrolyte fuel cell

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002231267A (en) * 2001-02-06 2002-08-16 Permelec Electrode Ltd Bonding laminate of electrode and membrane and its manufacturing method
JP2007525802A (en) * 2004-01-23 2007-09-06 ザ ユニバーシティ オブ ノース カロライナ アット チャペル ヒル Liquid material for use in electrochemical cells
JP2008166202A (en) * 2006-12-28 2008-07-17 Toyota Motor Corp Manufacturing method of membrane-electrode assembly for fuel cell
JP2009152166A (en) * 2007-11-26 2009-07-09 Toyota Motor Corp Composite electrolyte membrane, membrane-electrode assembly, fuel cell, and method for manufacturing the same
JP2009289463A (en) * 2008-05-27 2009-12-10 Toyota Motor Corp Method of manufacturing membrane-electrode assembly for polymer electrolyte fuel cell, and polymer electrolyte fuel cell

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002231267A (en) * 2001-02-06 2002-08-16 Permelec Electrode Ltd Bonding laminate of electrode and membrane and its manufacturing method
JP2007525802A (en) * 2004-01-23 2007-09-06 ザ ユニバーシティ オブ ノース カロライナ アット チャペル ヒル Liquid material for use in electrochemical cells
JP2008166202A (en) * 2006-12-28 2008-07-17 Toyota Motor Corp Manufacturing method of membrane-electrode assembly for fuel cell
JP2009152166A (en) * 2007-11-26 2009-07-09 Toyota Motor Corp Composite electrolyte membrane, membrane-electrode assembly, fuel cell, and method for manufacturing the same
JP2009289463A (en) * 2008-05-27 2009-12-10 Toyota Motor Corp Method of manufacturing membrane-electrode assembly for polymer electrolyte fuel cell, and polymer electrolyte fuel cell

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014186959A (en) * 2013-03-25 2014-10-02 Toppan Printing Co Ltd Electrode for fuel battery, manufacturing method thereof, film electrode assembly for fuel battery, manufacturing method thereof, and solid polymer fuel battery
JP2014192019A (en) * 2013-03-27 2014-10-06 Toppan Printing Co Ltd Method for manufacturing electrode for fuel cell, electrode for fuel cell, method for manufacturing membrane electrode assembly for fuel cell, membrane electrode assembly for fuel cell, and polymer electrolyte fuel cell

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