JP4581702B2 - Fuel cell - Google Patents

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JP4581702B2
JP4581702B2 JP2005017580A JP2005017580A JP4581702B2 JP 4581702 B2 JP4581702 B2 JP 4581702B2 JP 2005017580 A JP2005017580 A JP 2005017580A JP 2005017580 A JP2005017580 A JP 2005017580A JP 4581702 B2 JP4581702 B2 JP 4581702B2
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diffusion layer
membrane
fuel cell
electrode
electrode assembly
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JP2006210027A (en
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和則 柴田
学 高橋
勉 越智
大雄 吉川
稔幸 鈴木
千智 加藤
宏弥 中路
恒政 西田
康之 浅井
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Toyota Motor Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Description

本発明は、燃料電池に関し、とくに触媒層端縁部位での膜の耐久性を向上できる燃料電池に関する。 The present invention relates to fuel cells, especially relates to fuel cells which can improve the durability of the film at the catalyst layer edges site.

燃料電池、たとえば固体高分子電解質型燃料電池は、膜−電極アッセンブリ（Membrane-Electrode Assembly 、ＭＥＡ）に拡散層を接合して膜−電極−拡散層アッセンブリ（Membrane-Electrode-Gas Diffusion Layer Assembly 、ＭＥＧＡ）を形成し、ＭＥＧＡを一対のセパレータで挟んだものから構成される。少なくとも１つの単位燃料電池からモジュールを構成し、モジュールを複数積層して（積層方向は任意）燃料電池スタックが構成される。
一般に電極（触媒層）の平面形状は、電解質膜より一回り小さくされている（たとえば、特開２００４−１１９０６５号公報）。この種のＭＥＡでは、ＭＥＡはその端縁に沿った部位で膜のみの厚みとなって、それより内側の、膜とその両面に触媒層がある部分に比べて、厚みが薄い。このＭＥＡに従来の手法で拡散層を圧着すると、図１０に示すように、触媒層１２（１５）の端縁に電解質膜１１と拡散層１３（１６）の間に空間１ができ、その近傍の拡散層の密度が局所的に薄くなる。
特開２００４−１１９０６５号公報 2. Description of the Related Art A fuel cell, for example, a solid polymer electrolyte fuel cell, is formed by bonding a diffusion layer to a membrane-electrode assembly (MEA) to form a membrane-electrode-gas diffusion layer assembly (MEGA). ), And MEGA is sandwiched between a pair of separators. A module is composed of at least one unit fuel cell, and a plurality of modules are stacked (arbitrary stacking direction is arbitrary) to form a fuel cell stack.
In general, the planar shape of an electrode (catalyst layer) is made slightly smaller than that of an electrolyte membrane (for example, Japanese Patent Application Laid-Open No. 2004-119065). In this type of MEA, the MEA has a thickness only at the portion along the edge thereof, and is thinner than the inner portion of the MEA and the portion having the catalyst layers on both sides thereof. When the diffusion layer is pressure-bonded to this MEA by a conventional method, a space 1 is formed between the electrolyte membrane 11 and the diffusion layer 13 (16) at the edge of the catalyst layer 12 (15) as shown in FIG. The density of the diffusion layer is locally reduced.
JP 2004-1119065 A

触媒層端縁に空間ができること、あるいは触媒層端縁の近傍の拡散層密度が局所的に小さくなることによって、空間または拡散層の局所的な密度低下部分に発電の結果生成される生成水が溜まりやすくなり、生成水に含まれる、水生成の過程で中間生成物として一時的にできる過酸化水素とそれと共存するラジカルも溜まりやすくなる。その結果、空間または拡散層の局所的な密度低下部分の近傍で電解質膜が攻撃されて、電解質膜が局所的に徐々に痩せ、その結果その部位でクロスリークが生じやすくなるなど、膜の耐久性が局所的に低下する。   Due to the space at the edge of the catalyst layer or the local density of the diffusion layer near the edge of the catalyst layer being locally reduced, the generated water generated as a result of power generation is generated at the local density-decreasing portion of the space or diffusion layer. It becomes easy to accumulate, and hydrogen peroxide that is temporarily formed as an intermediate product in the water generation process and radicals coexisting with it are also likely to accumulate. As a result, the electrolyte membrane is attacked in the vicinity of the local density-decreasing portion of the space or the diffusion layer, and the electrolyte membrane gradually fades locally. Sexually decreases.

本発明の目的は、触媒層端縁での膜の耐久性の低下を抑制することができる燃料電池を提供することにある。 An object of the present invention is to provide a fuel cells that can suppress the deterioration of the durability of the film at the catalyst layer edges.

上記目的を達成する本発明はつぎの通りである。
（１） 膜−電極アッセンブリに拡散層を接合した膜−電極−拡散層アッセンブリと、該膜−電極−拡散層アッセンブリを挟む一対のセパレータとを備えた燃料電池であって、膜−電極アッセンブリは互いに厚みが異なる第１の部分と第２の部分を有し第１の部分の厚みは第２の部分の厚みより小であり、拡散層は膜−電極アッセンブリの第１の部分に接合される第１の拡散層部分と膜−電極アッセンブリの第２の部分に接合される第２の拡散層部分とを有し第１の拡散層部分の密度は第２の拡散層部分の密度以上であり、
セパレータは膜−電極アッセンブリの第１の部分に対応する第１のセパレータ部分と膜−電極アッセンブリの第２の部分に対応する第２のセパレータ部分とを有し第１のセパレータ部分は第２のセパレータ部分よりも拡散層側に突出しており、
膜−電極アッセンブリの第１の部分は燃料電池の外周部に位置し、膜−電極アッセンブリの第２の部分は燃料電池の内周部に位置している、
燃料電池。 The present invention for achieving the above object is as follows.
(1) A fuel cell comprising a membrane-electrode-diffusion layer assembly in which a diffusion layer is joined to a membrane-electrode assembly and a pair of separators sandwiching the membrane-electrode-diffusion layer assembly, wherein the membrane-electrode assembly is The first portion has a thickness different from the thickness of the second portion, and the diffusion layer is bonded to the first portion of the membrane-electrode assembly. A first diffusion layer portion and a second diffusion layer portion joined to the second portion of the membrane-electrode assembly, the density of the first diffusion layer portion being equal to or higher than the density of the second diffusion layer portion; The
The separator has a first separator portion corresponding to the first portion of the membrane-electrode assembly and a second separator portion corresponding to the second portion of the membrane-electrode assembly, the first separator portion being a second separator portion. It protrudes to the diffusion layer side from the separator part,
A first portion of the membrane-electrode assembly is located on the outer periphery of the fuel cell, and a second portion of the membrane-electrode assembly is located on the inner periphery of the fuel cell;
Fuel cell.

上記（１）の燃料電池によれば、第１の拡散層部分の密度は第２の拡散層部分の密度以上であるので、触媒層端縁の第１の拡散層部分に生成水が溜まりにくく、膜攻撃物質も溜まりにくく、膜の耐久性が向上する。 According to the fuel cell of (1 ), since the density of the first diffusion layer portion is equal to or higher than the density of the second diffusion layer portion, the generated water is unlikely to accumulate in the first diffusion layer portion at the edge of the catalyst layer. In addition, membrane attack substances are less likely to accumulate, and the durability of the membrane is improved.

また、第１のセパレータ部分は第２のセパレータ部分よりも拡散層側に突出しているので、一対のセパレータで挟まれた際に、第１の拡散層部分の厚みが圧縮される。その結果、触媒層端縁の空間が小さくなるとともに第１の拡散層部分の密度が高くなり、触媒層端縁の空間および触媒層端縁の第１の拡散層部分に生成水が溜まりにくく、膜攻撃物質も溜まりにくく、膜の耐久性が向上する。Moreover, since the 1st separator part protrudes in the diffused layer side rather than the 2nd separator part, when sandwiched between a pair of separators, the thickness of the 1st diffused layer part is compressed. As a result, the catalyst layer edge space is reduced and the density of the first diffusion layer portion is increased, and the generated water is less likely to accumulate in the catalyst layer edge space and the first diffusion layer portion of the catalyst layer edge, Membrane attack substances are also difficult to accumulate, and the durability of the membrane is improved.

以下に、本発明の燃料電池を、参考例とともに、図１〜図９を参照して説明する。
〔燃料電池の一般構成〕
本発明の燃料電池セパレータが組み付けられる燃料電池１０は、低温型燃料電池であり、たとえば、固体高分子電解質型燃料電池１０である。該燃料電池１０は、たとえば燃料電池自動車に搭載される。ただし、自動車以外に用いられてもよい。
図７〜図９に示すように、固体高分子電解質型燃料電池１０は、膜−電極アッセンブリ１２（ＭＥＡ：Membrane-Electrode Assembly ）とセパレータ１８とを重ねたものからなる。 Hereinafter, the fuel cells of the present invention, together with reference examples will be described with reference to FIGS. 1-9.
[General configuration of fuel cell]
The fuel cell 10 to which the fuel cell separator of the present invention is assembled is a low temperature fuel cell, for example, a solid polymer electrolyte fuel cell 10. The fuel cell 10 is mounted on, for example, a fuel cell vehicle. However, it may be used other than an automobile.
As shown in FIGS. 7 to 9, the solid polymer electrolyte fuel cell 10 is formed by stacking a membrane-electrode assembly 12 (MEA: Membrane-Electrode Assembly) and a separator 18.

膜−電極アッセンブリ１２は、イオン交換膜からなる電解質膜１１とこの電解質膜の一面に配置された触媒層からなる電極（アノード、燃料極）１４および電解質膜の他面に配置された触媒層からなる電極（カソード、空気極）１７とからなる。膜−電極アッセンブリとセパレータ１８との間には、アノード側、カソード側にそれぞれ拡散層１３、１６が設けられる。拡散層１３、１６は膜−電極アッセンブリ１２に圧着（熱圧着である場合を含む）されてもよく、その場合は、膜−電極アッセンブリ１２とそれに圧着された拡散層１３、１６は膜−電極−拡散層アッセンブリ１５（ＭＥＧＡ：Membrane-Electrode-Gas Diffusion Layer Assembly)を構成する。   The membrane-electrode assembly 12 includes an electrolyte membrane 11 made of an ion exchange membrane, an electrode (anode, fuel electrode) 14 made of a catalyst layer disposed on one surface of the electrolyte membrane, and a catalyst layer disposed on the other surface of the electrolyte membrane. Electrode (cathode, air electrode) 17. Between the membrane-electrode assembly and the separator 18, diffusion layers 13 and 16 are provided on the anode side and the cathode side, respectively. The diffusion layers 13 and 16 may be pressure-bonded to the membrane-electrode assembly 12 (including the case of thermocompression bonding). In this case, the membrane-electrode assembly 12 and the diffusion layers 13 and 16 pressure-bonded to the membrane-electrode assembly 12 -The diffusion layer assembly 15 (MEGA: Membrane-Electrode-Gas Diffusion Layer Assembly) is comprised.

セパレータ１８には、中央部に、アノード１４、カソード１７に燃料ガス（水素）および酸化ガス（酸素、通常は空気）を供給するための反応ガス流路２７、２８（燃料ガス流路２７、酸化ガス流路２８）と、その裏面に冷媒（通常、冷却水）を流すための冷媒流路２６が形成されている。
また、セパレータ１８には、外周部に、燃料ガス流路２７に燃料ガスを供給、排出するための燃料ガスマニホールド３０、酸化ガス流路２８に酸化ガスを供給、排出するための酸化ガスマニホールド３１、冷媒流路２６に冷媒を供給、排出するための冷媒マニホールド２９が形成されている。 The separator 18 has reaction gas channels 27 and 28 (fuel gas channel 27, oxidation gas) for supplying fuel gas (hydrogen) and oxidizing gas (oxygen, usually air) to the anode 14 and cathode 17 at the center. A gas flow path 28) and a refrigerant flow path 26 for flowing a refrigerant (usually cooling water) are formed on the back surface thereof.
The separator 18 has a fuel gas manifold 30 for supplying and discharging a fuel gas to a fuel gas channel 27 and an oxidizing gas manifold 31 for supplying and discharging an oxidizing gas to an oxidizing gas channel 28 at the outer periphery. A refrigerant manifold 29 for supplying and discharging the refrigerant to and from the refrigerant flow path 26 is formed.

膜−電極アッセンブリ１２とセパレータ１８を重ねて単位燃料電池（「単セル」ともいう）１０を構成し、セルを１つ以上積層してモジュール１９とし、モジュール積層体（セル積層体ともいう）のセル積層方向両端に、ターミナル２０、インシュレータ２１、エンドプレート２２を配置し、エンドプレート２２をセル積層体の外側でセル積層方向に延びる締結部材（たとえば、テンションプレート２４）に、ボルト・ナット２５により固定し、セル積層体をセル積層方向に締め付け、燃料電池スタック２３を構成する。   A unit fuel cell (also referred to as “single cell”) 10 is formed by stacking the membrane-electrode assembly 12 and the separator 18, and one or more cells are stacked to form a module 19, which is a module stack (also referred to as a cell stack). Terminals 20, insulators 21 and end plates 22 are arranged at both ends of the cell stacking direction, and the end plates 22 are fastened to fastening members (for example, tension plates 24) extending in the cell stacking direction outside the cell stack by bolts and nuts 25. The fuel cell stack 23 is configured by fixing and clamping the cell stack in the cell stacking direction.

流体流路２６、２７、２８、２９、３０、３１、３４をシールするために、ガス側のシール材３３および冷媒側のシール３２が設けられる。図示例では、ガス側シール材３３が接着剤からなり、冷媒側シール材３２がゴムガスケットからなる場合を示している。ただし、ガス側シール材３３も冷媒側シール材３２も、接着剤とゴムガスケットの何れから構成されてもよい。   In order to seal the fluid flow paths 26, 27, 28, 29, 30, 31, 34, a gas-side sealing material 33 and a refrigerant-side seal 32 are provided. In the illustrated example, the gas side sealing material 33 is made of an adhesive, and the refrigerant side sealing material 32 is made of a rubber gasket. However, both the gas side sealing material 33 and the refrigerant side sealing material 32 may be composed of either an adhesive or a rubber gasket.

各セル１９の、アノード側１４では、水素を水素イオン（プロトン）と電子に電離する電離反応が行われ、水素イオンは電解質膜１１中をカソード側に移動し、カソード１７側では酸素と水素イオンおよび電子（隣りのＭＥＡのアノードで生成した電子がセパレータを通してくる、またはセル積層方向一端のセルのアノードで生成した電子が外部回路を通して他端のセルのカソードにくる）から水を生成する反応が行われ、かくして発電が行われる。
アノード側：Ｈ2 →２Ｈ+ ＋２ｅ-
カソード側：２Ｈ+ ＋２ｅ- ＋（１／２）Ｏ2 →Ｈ2 Ｏ On the anode side 14 of each cell 19, an ionization reaction is performed to ionize hydrogen into hydrogen ions (protons) and electrons, and the hydrogen ions move to the cathode side through the electrolyte membrane 11, and oxygen and hydrogen ions on the cathode 17 side. And water (electrons generated at the anode of the adjacent MEA come through the separator, or electrons generated at the anode of the cell at one end of the cell stacking direction come to the cathode of the other end cell through an external circuit) This is how it generates electricity.
Anode side: H 2 → 2H + + 2e −
Cathode side: 2H + + 2e − + (1/2) O 2 → H 2 O

一般に触媒層１４、１７（アノード触媒層はアノード電極１４と同じであるため符号を１４とし、カソード触媒層はカソード電極１７と同じであるため符号を１７とする）の平面形状は電解質膜１１の平面形状より一回り小さいため、ＭＥＡ１２のうち、膜１１のみからなる第１の部分（外周部）１２ａと、膜１１と触媒層１４、１７とからなる第２の部分１２ｂ（内周部、発電領域部）とは、厚さが互いに異なり、ＭＥＡ１２の第１の部分１２ａの厚さはＭＥＡ１２の第２の部分１２ｂの厚さより小である。このため、ＭＥＡ１２に拡散層１３、１６を圧着してＭＥＧＡ１５を製作した場合、従来は、図１０に示すように、触媒層１２（１５）の端縁に電解質膜１１と拡散層１３（１６）の間に空間１ができ、その近傍の拡散層の密度が局所的に薄くなって、空間または拡散層の密度が局所的に薄くなった部位に生成水、過酸化水素、ラジカルが溜まりやすくなり、膜１１の比較的早期の劣化につながるという問題があることは前述した通りである。
これを抑制するための、本発明の燃料電池１０は、以下の通りである。 In general, the planar shape of the catalyst layers 14 and 17 (the anode catalyst layer is the same as the anode electrode 14 so that the reference numeral is 14 and the cathode catalyst layer is the same as the cathode electrode 17 and the reference numeral is 17) is the planar shape of the electrolyte membrane 11. Since it is slightly smaller than the planar shape, the MEA 12 includes a first portion (outer peripheral portion) 12a consisting only of the membrane 11 and a second portion 12b consisting of the membrane 11 and the catalyst layers 14 and 17 (inner peripheral portion, power generation). The thickness of the first portion 12a of the MEA 12 is smaller than the thickness of the second portion 12b of the MEA 12. For this reason, when the MEGA 15 is manufactured by press-bonding the diffusion layers 13 and 16 to the MEA 12, conventionally, as shown in FIG. 10, the electrolyte membrane 11 and the diffusion layer 13 (16) are formed on the edge of the catalyst layer 12 (15). A space 1 is formed in between, and the density of the diffusion layer in the vicinity of the space 1 is locally reduced, so that generated water, hydrogen peroxide, and radicals are likely to accumulate in a portion where the density of the space or the diffusion layer is locally reduced. As described above, there is a problem that the film 11 is relatively early deteriorated.
In order to suppress this, the fuel cell 10 of the present invention is as follows.

〔燃料電池１０の生成水溜まり抑制のため参考例１、２と実施例１の共通構成〕
図４〜６に示すように、燃料電池１０は、膜−電極アッセンブリ１２が互いに厚みが異なる第１の部分１２ａと第２の部分１２ｂを有し第１の部分１２ａの厚みは第２の部分の厚み１２ｂより小であり、拡散層１３、１６は膜−電極アッセンブリ１２の第１の部分１２ａに接合（圧着）される第１の拡散層部分１３ａ、１６ａと膜−電極アッセンブリ１２の第２の部分１２ｂに接合される第２の拡散層部分１３ｂ、１６ｂとを有する。
第１の拡散層部分１３ａ、１６ａの密度は第２の拡散層部分１３ｂ、１６ｂの密度以上である。また、触媒層１４、１７の端縁に沿って、第１の拡散層部分１３ａ、１６ａと膜１１との間に形成される空間２は、空間２に対応する従来の空間１に比べて小さいか、あるいは空間２が形成されていない。
膜−電極アッセンブリ１２の電極触媒層１４、１７は膜の一面に形成されたアノード触媒層１４と膜の他面に形成されたカソード触媒層１７を含み、カソード触媒層１７の縁がアノード触媒層１４の縁とセル面内方向において同じ位置に位置する。ただし、カソード触媒層１７の縁がアノード触媒層１４の縁よりセル面内において内側に位置していてもよい。
第１の拡散層部分１３ａ、１６ａの密度を第２の拡散層部分１３ｂ、１６ｂの密度以上とする構成は以下の参考例１、２と実施例１の何れかによる。 [Common configuration of Reference Examples 1 and 2 and Example 1 for suppressing water pool of fuel cell 10]
As shown in FIGS. 4 to 6, the fuel cell 10 includes a membrane electrode assembly 12 having a first portion 12 a and a second portion 12 b having different thicknesses. The thickness of the first portion 12 a is the second portion. The diffusion layers 13 and 16 are joined (crimped) to the first portion 12a of the membrane-electrode assembly 12 and the second diffusion layer portions 13a and 16a and the second of the membrane-electrode assembly 12 are bonded to each other. The second diffusion layer portions 13b and 16b are joined to the portion 12b.
The density of the first diffusion layer portions 13a and 16a is equal to or higher than the density of the second diffusion layer portions 13b and 16b. Further, the space 2 formed between the first diffusion layer portions 13a and 16a and the membrane 11 along the edges of the catalyst layers 14 and 17 is smaller than the conventional space 1 corresponding to the space 2. Alternatively, the space 2 is not formed.
The electrode catalyst layers 14 and 17 of the membrane-electrode assembly 12 include an anode catalyst layer 14 formed on one surface of the membrane and a cathode catalyst layer 17 formed on the other surface of the membrane, and the edge of the cathode catalyst layer 17 is the anode catalyst layer. 14 and the same position in the cell in-plane direction. However, the edge of the cathode catalyst layer 17 may be located inside the cell surface from the edge of the anode catalyst layer 14.
The configuration in which the density of the first diffusion layer portions 13a and 16a is equal to or higher than the density of the second diffusion layer portions 13b and 16b depends on any of the following Reference Examples 1 and 2 and Example 1 .

〔燃料電池１０の生成水溜まり抑制のための参考例１の構成〕
参考例１では、図４に示すように、拡散層１３、１６が膜−電極アッセンブリ１２にホットプレスされる際に拡散層１３、１６の外周部である第１の部分１３ａ、１６ａに拡散層１３、１６の内周部である第２の部分１３ｂ、１６ｂより高い面圧をかけることにより、拡散層１３、１６の第１の部分１３ａ、１６ａの圧縮率を拡散層１３、１６の第２の部分１３ｂ、１６ｂの圧縮率より上げ、第１の拡散層部分１３ａ、１６ａの密度を第２の拡散層部分１３ｂ、１６ｂの密度以上とする。 [Configuration of Reference Example 1 for Suppressing Generated Water Pool of Fuel Cell 10]
In Reference Example 1, as shown in FIG. 4, when the diffusion layers 13 and 16 are hot-pressed to the membrane-electrode assembly 12, the diffusion layers are formed on the first portions 13 a and 16 a that are the outer peripheral portions of the diffusion layers 13 and 16. By applying a higher surface pressure than the second portions 13b and 16b, which are the inner peripheral portions of the diffusion layers 13 and 16, the compressibility of the first portions 13a and 16a of the diffusion layers 13 and 16 can be reduced. The density of the first diffusion layer portions 13a and 16a is set to be equal to or higher than the density of the second diffusion layer portions 13b and 16b.

〔燃料電池１０の生成水溜まり抑制のための参考例２の構成〕
参考例２では、図６に示すように、膜−電極−拡散層アッセンブリ１５が一対のセパレータ１８で挟まれる前の、第１の拡散層部分１３ａの密度と第２の拡散層部分１６ｂの密度が同じ状態では、第１の拡散層部分１３ａの厚みが第２の拡散層部分１６ｂの厚みより大とする。こうすることによって、膜−電極−拡散層アッセンブリ１５が一対のセパレータ１８で挟まれた後には、第１の拡散層部分１３ａ、１６ａがセパレータ１８で圧縮されて、第１の拡散層部分１３ａ、１６ａの密度は第２の拡散層部分１３ｂ、１６ｂの密度以上となる。 [Configuration of Reference Example 2 for Suppressing Generated Water Pool of Fuel Cell 10]
In Reference Example 2, as shown in FIG. 6 , the density of the first diffusion layer portion 13 a and the density of the second diffusion layer portion 16 b before the membrane-electrode-diffusion layer assembly 15 is sandwiched between the pair of separators 18. In the same state, the thickness of the first diffusion layer portion 13a is larger than the thickness of the second diffusion layer portion 16b. In this way, after the membrane-electrode-diffusion layer assembly 15 is sandwiched between the pair of separators 18, the first diffusion layer portions 13a, 16a are compressed by the separator 18, and the first diffusion layer portions 13a, The density of 16a is equal to or higher than the density of the second diffusion layer portions 13b and 16b.

〔燃料電池１０の生成水溜まり抑制のための実施例１の構成〕
本発明の実施例１では、図５に示すように、セパレータ１８が膜−電極アッセンブリ１２の第１の部分１２ａに対応する第１のセパレータ部分１８ａと膜−電極アッセンブリ１２の第２の部分１２ｂに対応する第２のセパレータ部分１８ｂとを有し、第１のセパレータ部分１８ａは第２のセパレータ部分１８ｂよりも拡散層１３、１６側に突出している。こうすることによって、膜−電極−拡散層アッセンブリ１５が一対のセパレータ１８で挟まれた後には、第１の拡散層部分１３ａ、１６ａがセパレータ１８の第１の部分１８ａで圧縮されて、第１の拡散層部分１３ａ、１６ａの密度は第２の拡散層部分１３ｂ、１６ｂの密度以上となる。参考例１と実施例１の違いは、実施例１では、第１の拡散層部分１３ａの密度と第２の拡散層部分１６ｂの密度が同じ状態では、第１の拡散層部分１３ａの厚みが第２の拡散層部分１６ｂの厚みより大であるのに対し、参考例１では、第１の拡散層部分１３ａの密度と第２の拡散層部分１６ｂの密度が同じ状態では、第１の拡散層部分１３ａの厚みと第２の拡散層部分１６ｂの厚みとが同じであってもよく、ホットプレスの際に拡散層１３、１６の第１の部分１３ａ、１６ａの面圧を上げて圧縮率を高くした点である。 [Configuration of Embodiment 1 for Suppressing Generated Water Pool of Fuel Cell 10]
In the first embodiment of the present invention, as shown in FIG. 5 , the separator 18 corresponds to the first portion 12 a of the membrane-electrode assembly 12 and the second portion 12 b of the membrane-electrode assembly 12. The first separator portion 18a protrudes closer to the diffusion layers 13 and 16 than the second separator portion 18b. Thus, after the membrane-electrode-diffusion layer assembly 15 is sandwiched between the pair of separators 18, the first diffusion layer portions 13 a and 16 a are compressed by the first portion 18 a of the separator 18, and the first The density of the diffusion layer portions 13a and 16a is equal to or higher than the density of the second diffusion layer portions 13b and 16b. The difference between Reference Example 1 and Example 1 is that in Example 1 , when the density of the first diffusion layer portion 13a and the density of the second diffusion layer portion 16b are the same, the thickness of the first diffusion layer portion 13a is the same. Whereas the thickness of the second diffusion layer portion 16b is larger than that of the second diffusion layer portion 16b, the first diffusion is performed in Reference Example 1 when the density of the first diffusion layer portion 13a and the density of the second diffusion layer portion 16b are the same. The thickness of the layer portion 13a may be the same as the thickness of the second diffusion layer portion 16b, and the compression ratio is increased by increasing the surface pressure of the first portions 13a, 16a of the diffusion layers 13, 16 during hot pressing. It is a point that raised.

〔燃料電池１０の参考例１、２、実施例１の共通構成による作用・効果〕
第１の拡散層部分１３ａ、１６ａの密度が第２の拡散層部分１３ｂ、１６ｂの密度より高いので、触媒層１２、１５端縁の第１の拡散層部分１３ａ、１６ａに生成水が溜まりにくく、膜攻撃物質（過酸化水素、ラジカル）も溜まりにくく、電解質膜１１の耐久性が向上する。 [Operation / Effects of Common Configurations of Reference Examples 1 and 2 and Example 1 of Fuel Cell 10]
Since the density of the first diffusion layer portions 13a and 16a is higher than the density of the second diffusion layer portions 13b and 16b, the generated water hardly accumulates in the first diffusion layer portions 13a and 16a at the edges of the catalyst layers 12 and 15. Further, membrane attack substances (hydrogen peroxide, radicals) are also difficult to accumulate, and the durability of the electrolyte membrane 11 is improved.

〔燃料電池１０の参考例１の構成による作用・効果〕
本発明の参考例１の燃料電池では、拡散層１３、１６が膜−電極アッセンブリ１２にホットプレスされる際に、第１の拡散層部分１３ａ、１６ａが第２の拡散層部分１３ｂ、１６ｂより高い面圧で圧縮され圧縮率が上げられているので、触媒層端縁の空間２が小さくなるとともに第１の拡散層部分１３ａ、１６ａの密度が高くなり、触媒層端縁の空間２および触媒層端縁の第１の拡散層部分１３ａ、１６ａに生成水が溜まりにくく、膜攻撃物質（過酸化水素、およびそれと共存するラジカル）も溜まりにくく、膜１１の耐久性が向上する。 [Operation / Effects of Configuration of Reference Example 1 of Fuel Cell 10]
In the fuel cell of Reference Example 1 of the present invention, when the diffusion layers 13 and 16 are hot pressed to the membrane-electrode assembly 12, the first diffusion layer portions 13a and 16a are more than the second diffusion layer portions 13b and 16b. Since the compression ratio is increased by compressing at a high surface pressure, the space 2 at the edge of the catalyst layer is reduced and the density of the first diffusion layer portions 13a and 16a is increased, and the space 2 at the edge of the catalyst layer and the catalyst are increased. The generated water hardly accumulates in the first diffusion layer portions 13a and 16a at the edge of the layer, and the membrane attack substance (hydrogen peroxide and radicals coexisting with it) hardly accumulates, so that the durability of the membrane 11 is improved.

〔燃料電池１０の参考例２の構成による作用・効果〕
本発明の参考例２の燃料電池では、膜−電極−拡散層アッセンブリ１５が一対のセパレータ１８で挟まれる前の、第１の拡散層部分１３ａ、１６ａの密度と第２の拡散層部分１３ｂ、１６ｂの密度が同じ状態では、第１の拡散層部分１３ａ、１６ａの厚みが第２の拡散層部分１３ｂ、１６ｂの厚みより大とされた場合は、膜−電極−拡散層アッセンブリ１５が一対のセパレータ１８で挟まれた際に、第１の拡散層部分１３ａ、１６ａの厚みが圧縮される。その結果、触媒層１４、１７端縁の空間２が小さくなるとともに、第１の拡散層部分１３ａ、１６ａの密度が高くなり、触媒層端縁の空間２および触媒層端縁の第１の拡散層部分１３ａ、１６ａに生成水が溜まりにくく、膜攻撃物質も溜まりにくく、膜１１の耐久性が向上する。 [Operation / Effects of Configuration of Reference Example 2 of Fuel Cell 10]
In the fuel cell of Reference Example 2 of the present invention, the density of the first diffusion layer portions 13a and 16a and the second diffusion layer portion 13b before the membrane-electrode-diffusion layer assembly 15 is sandwiched between the pair of separators 18, If the thickness of the first diffusion layer portions 13a and 16a is larger than the thickness of the second diffusion layer portions 13b and 16b, the membrane-electrode-diffusion layer assembly 15 is paired with the same density of 16b. When sandwiched between the separators 18, the thicknesses of the first diffusion layer portions 13a and 16a are compressed. As a result, the space 2 at the edges of the catalyst layers 14 and 17 is reduced and the density of the first diffusion layer portions 13a and 16a is increased, and the first diffusion at the space 2 at the catalyst layer edges and the edge of the catalyst layer is performed. The generated water does not easily accumulate in the layer portions 13a and 16a, and the membrane attack substance does not easily accumulate, so that the durability of the membrane 11 is improved.

〔燃料電池１０の実施例１の構成による作用・効果〕
本発明の実施例２の燃料電池では、第１のセパレータ部分１８ａが第２のセパレータ部分１８ｂよりも拡散層１３、１６側に突出しているので、一対のセパレータ１８で挟まれた際に、第１の拡散層部分１３ａ、１６ａの厚みが縮小され、第１の拡散層部分１３ａ、１６ａが圧縮される。その結果、触媒層端縁の空間２が小さくなる（あるいは、なくなる）とともに第１の拡散層部分１３ａ、１６ａの密度が高くなり、触媒層端縁の空間２および触媒層端縁の第１の拡散層部分１３ａ、１６ａに生成水が溜まりにくく、膜攻撃物質（過酸化水素、およびそれと共存するラジカル）も空間２または第１の拡散層部分１３ａ、１６ａに溜まりにくく、膜１１の耐久性が向上する。 [Operation / Effect of Configuration of Fuel Cell 10 in Example 1 ]
In the fuel cell of Example 2 of the present invention, the first separator portion 18a protrudes toward the diffusion layers 13 and 16 with respect to the second separator portion 18b. The thickness of one diffusion layer portion 13a, 16a is reduced, and the first diffusion layer portion 13a, 16a is compressed. As a result, the space 2 at the edge of the catalyst layer becomes smaller (or disappears) and the density of the first diffusion layer portions 13a and 16a becomes higher, and the space 2 at the edge of the catalyst layer and the first at the edge of the catalyst layer. The generated water is unlikely to accumulate in the diffusion layer portions 13a and 16a, and the membrane attack substance (hydrogen peroxide and radicals coexisting with it) is also difficult to accumulate in the space 2 or the first diffusion layer portions 13a and 16a. improves.

〔燃料電池１０の製造方法の生成水溜まり抑制のための参考例１、２、実施例１の共通構成〕
本発明の燃料電池１０の製造方法は、膜−電極アッセンブリ１２は互いに厚みが異なる第１の部分１２ａと第２の部分１２ｂを有し第１の部分１２ａの厚みは第２の部分１２ｂの厚みより小である膜−電極アッセンブリ１２に、膜−電極アッセンブリの第１の部分に圧着される第１の拡散層部分１３ａ、１６ａと膜−電極アッセンブリの第２の部分１２ｂに接合される第２の拡散層部分１３ｂ、１６ｂとを有する拡散層１３、１６を接合して膜−電極−拡散層アッセンブリ１５を形成する工程を有する燃料電池の製造方法であって、膜−電極アッセンブリ１２の厚みに応じて異なる条件にて拡散層１３、１６を膜−電極アッセンブリ１２に圧着する方法からなる。
第１の拡散層部分１３ａ、１６ａの密度は第２の拡散層部分１３ｂ、１６ｂの密度以上である。また、触媒層１４、１７の端縁に沿って、第１の拡散層部分１３ａ、１６ａと膜１１との間に形成される空間２は、空間２に対応する従来の空間１に比べて小さいか、あるいは空間２が形成されていない。 [Common configurations of Reference Examples 1 and 2 and Example 1 for suppressing a pool of generated water in the manufacturing method of the fuel cell 10]
In the manufacturing method of the fuel cell 10 of the present invention, the membrane-electrode assembly 12 has a first portion 12a and a second portion 12b having different thicknesses, and the thickness of the first portion 12a is the thickness of the second portion 12b. A second diffusion layer portion 13a, 16a that is crimped to the first portion of the membrane-electrode assembly and a second portion 12b of the membrane-electrode assembly that is bonded to the smaller membrane-electrode assembly 12 The fuel cell manufacturing method includes the step of forming the membrane-electrode-diffusion layer assembly 15 by joining the diffusion layers 13 and 16 having the diffusion layer portions 13b and 16b. Accordingly, the diffusion layers 13 and 16 are pressure-bonded to the membrane-electrode assembly 12 under different conditions.
The density of the first diffusion layer portions 13a and 16a is equal to or higher than the density of the second diffusion layer portions 13b and 16b. Further, the space 2 formed between the first diffusion layer portions 13a and 16a and the membrane 11 along the edges of the catalyst layers 14 and 17 is smaller than the conventional space 1 corresponding to the space 2. Alternatively, the space 2 is not formed.

膜−電極アッセンブリ１２の第１の部分１２ａは膜１１のみからなる部分であり、膜−電極アッセンブリ１２の第２の部分１２ｂは膜１１と電極触媒層１４、１７を含む部分である。
膜−電極アッセンブリ１２の電極触媒層１４、１７は膜の一面に形成されたアノード触媒層１４と膜の他面に形成されたカソード触媒層１７を含み、カソード触媒層１７の縁がアノード触媒層１４の縁とセル面内方向において同じ位置に位置する。ただし、カソード触媒層１７の縁がアノード触媒層１４の縁よりセル面内において内側に位置していてもよい。
膜−電極アッセンブリ１２の厚みに応じて異なる条件にて拡散層１３、１６を膜−電極アッセンブリ１２に圧着する方法は以下の方法の参考例１、２、実施例１の何れかによる。 The first portion 12 a of the membrane-electrode assembly 12 is a portion consisting only of the membrane 11, and the second portion 12 b of the membrane-electrode assembly 12 is a portion including the membrane 11 and the electrode catalyst layers 14, 17.
The electrode catalyst layers 14 and 17 of the membrane-electrode assembly 12 include an anode catalyst layer 14 formed on one surface of the membrane and a cathode catalyst layer 17 formed on the other surface of the membrane, and the edge of the cathode catalyst layer 17 is the anode catalyst layer. 14 and the same position in the cell in-plane direction. However, the edge of the cathode catalyst layer 17 may be located inside the cell surface from the edge of the anode catalyst layer 14.
The method of pressure-bonding the diffusion layers 13 and 16 to the membrane-electrode assembly 12 under different conditions depending on the thickness of the membrane-electrode assembly 12 depends on any of the following Reference Examples 1, 2 and Example 1 .

〔燃料電池１０の製造方法の、生成水溜まり抑制のための参考例１の構成〕
燃料電池１０の製造方法の参考例１は第１、第２、第３の方法を含む。
製造方法の参考例１の第１の方法では、図１に示すように、膜−電極アッセンブリ１２の厚みに応じて異なる条件が圧力であり、第１の拡散層部分１３ａ、１６ａを第２の拡散層部分１３ｂ、１６ｂより高い圧力にて膜−電極アッセンブリ１２に圧着する。図１では、同一工程内で、プレス機５０の、触媒端部を接合する部位の高さを変更する。プレス機５０の、膜−電極アッセンブリ１２の第１の部分１２ａを押す第１の部分５０ａと、膜−電極アッセンブリ１２の第２の部分１２ｂを押す第２の部分５０ｂとの高さを変え、第１の部分５０ａが第２の部分５０ｂより膜−電極アッセンブリ１２側に突出するようにする。このプレス機５０を用いてプレスすることにより、第１の拡散層部分１３ａ、１６ａの密度を第２の拡散層部分１３ｂ、１６ｂの密度以上にする。 [Configuration of Reference Example 1 for Suppressing Generated Water Pool in Manufacturing Method of Fuel Cell 10]
Reference example 1 of the method for manufacturing the fuel cell 10 includes first, second, and third methods.
In the first method of Reference Example 1 of the manufacturing method, as shown in FIG. 1, the pressure is a different condition depending on the thickness of the membrane-electrode assembly 12, and the first diffusion layer portions 13 a and 16 a are connected to the second method. The membrane electrode assembly 12 is pressure-bonded at a pressure higher than that of the diffusion layer portions 13b and 16b. In FIG. 1, the height of the site | part which joins the catalyst edge part of the press machine 50 is changed within the same process. The height of the first portion 50a for pushing the first portion 12a of the membrane-electrode assembly 12 and the second portion 50b for pushing the second portion 12b of the membrane-electrode assembly 12 of the press machine 50 is changed, The first part 50a protrudes from the second part 50b to the membrane-electrode assembly 12 side. By pressing using the press machine 50, the density of the first diffusion layer portions 13a and 16a is set to be equal to or higher than the density of the second diffusion layer portions 13b and 16b.

燃料電池１０の製造方法の参考例１の第２の方法では、図２に示すように、膜−電極アッセンブリ１２の厚みに応じて異なる条件が温度であり、第１の拡散層部分１３ａ、１６ａを第２の拡散層部分１３ｂ、１６ｂより高い温度にて膜−電極アッセンブリ１２に圧着する。たとえば、プレス機５０の第２の拡散層部分１３ｂ、１６ｂを押す部分５０ｂの温度が１００℃とすると、第１の拡散層部分１３ａ、１６ａを押す部分５０ａの温度が、それより所定温度（たとえば、２０℃）以上高くされて、１２０℃以上といった具合である。このプレス機５０を用いてプレスすることにより、第１の拡散層部分１３ａ、１６ａの密度を第２の拡散層部分１３ｂ、１６ｂの密度以上にする。
温度と圧力を同時にかけてもよい。すなわち、参考例１の第１の方法と第２の方法とを同時に実行してもよい。 In the second method of Reference Example 1 of the manufacturing method of the fuel cell 10 , as shown in FIG. 2, the temperature varies depending on the thickness of the membrane-electrode assembly 12, and the first diffusion layer portions 13 a, 16 a Is pressure-bonded to the membrane-electrode assembly 12 at a temperature higher than that of the second diffusion layer portions 13b and 16b. For example, when the temperature of the portion 50b that presses the second diffusion layer portions 13b and 16b of the press machine 50 is 100 ° C., the temperature of the portion 50a that presses the first diffusion layer portions 13a and 16a is set to a predetermined temperature (for example, , 20 ° C.) or higher, and 120 ° C. or higher. By pressing using the press machine 50, the density of the first diffusion layer portions 13a and 16a is set to be equal to or higher than the density of the second diffusion layer portions 13b and 16b.
You may apply temperature and pressure simultaneously. That is , the first method and the second method of Reference Example 1 may be executed simultaneously.

燃料電池１０の製造方法の参考例１の第３の方法では、図３に示すように、膜−電極アッセンブリ１２の厚みに応じて異なる条件が時間であり、第１の拡散層部分１３ａ、１６ａを第２の拡散層部分１３ｂ、１６ｂより長時間膜−電極アッセンブリ１２に圧着する。
長時間の圧着は再プレスの時間を含んでもよい。図３は、第１の拡散層部分１３ａ、１６ａを第２の拡散層部分１３ｂ、１６ｂを一体型で押圧した後、第１の拡散層部分１３ａ、１６ａのみを再プレス型５０ａで再プレスする場合を示している。第１の拡散層部分１３ａ、１６ａを第２の拡散層部分１３ｂ、１６ｂより長時間膜−電極アッセンブリ１２に圧着することにより、第１の拡散層部分１３ａ、１６ａの密度を第２の拡散層部分１３ｂ、１６ｂの密度以上にする。 In the third method of Reference Example 1 of the manufacturing method of the fuel cell 10 , as shown in FIG. 3, the different condition depending on the thickness of the membrane-electrode assembly 12 is time, and the first diffusion layer portions 13 a and 16 a Is pressed to the membrane-electrode assembly 12 for a longer time than the second diffusion layer portions 13b, 16b.
Long-time crimping may include re-pressing time. In FIG. 3, after the first diffusion layer portions 13a and 16a are pressed together with the second diffusion layer portions 13b and 16b, only the first diffusion layer portions 13a and 16a are re-pressed by the re-press die 50a. Shows the case. By pressing the first diffusion layer portions 13a and 16a to the membrane-electrode assembly 12 for a longer time than the second diffusion layer portions 13b and 16b, the density of the first diffusion layer portions 13a and 16a is reduced to the second diffusion layer. The density of the portions 13b and 16b is set to be equal to or higher.

本発明の製造方法の参考例１の第４の方法では、図６に示すように、膜−電極アッセンブリ１２の厚みに応じて異なる条件が拡散層の材料および撥水剤の何れか少なくとも一方の量であり、第１の拡散層部分１３ａ、１６ａの材料および撥水剤の何れか少なくとも一方の量を第２の拡散層部分１３ｂ、１６ｂの材料および撥水剤の何れか少なくとも一方の量より増やして拡散層１３、１６を膜−電極アッセンブリ１２にプレス機にて圧着する。プレスによる圧着後は、一対のセパレータ１８で挟む前の段階で、第１の拡散層部分１３ａ、１６ａと第２の拡散層部分１３ｂ、１６ｂの厚さが同じで、かつ、第１の拡散層部分１３ａ、１６ａの密度が第２の拡散層部分１３ｂ、１６ｂの密度以上となる。
参考例１の第４の方法と実施例１との違いは、実施例１ではＭＥＧＡの段階で第１の部分と第２の部分とが異なり、セパレータで挟まれてスタックの荷重がかかることにより第１の部分と第２の部分とが同じ厚さになるのに対し、参考例１の第４の方法では、ＭＥＧＡの段階では第１の部分と第２の部分とが同じ厚さであり、プレス機でプレスされて第１の部分と第２の部分とが同じ厚さになることである。 In the fourth method of Reference Example 1 of the manufacturing method of the present invention, as shown in FIG. 6, different conditions depending on the thickness of the membrane-electrode assembly 12 are different from at least one of the material of the diffusion layer and the water repellent. The amount of at least one of the material of the first diffusion layer portions 13a and 16a and the water repellent is greater than the amount of at least one of the material of the second diffusion layer portions 13b and 16b and the water repellent. The diffusion layers 13 and 16 are increased and pressure-bonded to the membrane-electrode assembly 12 by a press machine. After the press bonding, the first diffusion layer portions 13a and 16a and the second diffusion layer portions 13b and 16b have the same thickness before being sandwiched between the pair of separators 18 and the first diffusion layer. The density of the portions 13a and 16a is equal to or higher than the density of the second diffusion layer portions 13b and 16b.
The difference between the fourth method of Reference Example 1 and Example 1 is that in Example 1 , the first part and the second part are different in the MEGA stage, and the stack load is applied between the separators. Whereas the first part and the second part have the same thickness, in the fourth method of Reference Example 1, the first part and the second part have the same thickness at the MEGA stage. The first part and the second part have the same thickness when pressed by a press.

〔燃料電池１０の製造方法の、生成水溜まり抑制のための参考例２の構成〕[Configuration of Reference Example 2 for Suppressing Generated Water Pool in Manufacturing Method of Fuel Cell 10]
燃料電池１０の参考例２の製造方法は、図６に示すように、膜−電極−拡散層アッセンブリ１５を形成する工程と、一対のセパレータ１８にて膜−電極−拡散層アッセンブリ１５を挟んでセル１０を形成する工程と、を有する燃料電池の製造方法であって、一対のセパレータ１８で膜−電極−拡散層アッセンブリ１５を挟む前は第１の拡散層部分１３ａ、１６ａの厚みを第２の拡散層部分１３ｂ、１６ｂの厚みより大にしておくことにより、一対のセパレータ１８で膜−電極−拡散層アッセンブリ１５を挟んだ時に第１の拡散層部分１３ａ、１６ａを第２の拡散層部分１３ｂ、１６ｂより強く圧縮して第１の拡散層部分１３ａ、１６ａの密度を第２の拡散層部分１３ｂ、１６ｂの密度以上とする方法からなる。参考例２の製造方法では、一対のセパレータ１８で膜−電極−拡散層アッセンブリ１５を挟み、セル１０を積層してスタック化する時にスタック締結荷重をかけて第１の拡散層部分１３ａ、１６ａを第２の拡散層部分１３ｂ、１６ｂより強く圧縮する（プレス機で第１の拡散層部分１３ａ、１６ａを圧縮するのではない）。As shown in FIG. 6, the manufacturing method of Reference Example 2 of the fuel cell 10 includes a step of forming a membrane-electrode-diffusion layer assembly 15 and a pair of separators 18 sandwiching the membrane-electrode-diffusion layer assembly 15. A step of forming a cell 10, wherein the thickness of the first diffusion layer portions 13 a and 16 a is set to the second thickness before the membrane-electrode-diffusion layer assembly 15 is sandwiched between the pair of separators 18. By making the thickness of the diffusion layer portions 13b and 16b larger than that of the first diffusion layer portions 13a and 16a when the membrane-electrode-diffusion layer assembly 15 is sandwiched between the pair of separators 18, This is a method of compressing more strongly than 13b and 16b so that the density of the first diffusion layer portions 13a and 16a is equal to or higher than the density of the second diffusion layer portions 13b and 16b. In the manufacturing method of Reference Example 2, the membrane-electrode-diffusion layer assembly 15 is sandwiched between a pair of separators 18, and when the cells 10 are stacked and stacked, a stack fastening load is applied so that the first diffusion layer portions 13a and 16a are attached. Compress more strongly than the second diffusion layer portions 13b and 16b (not compressing the first diffusion layer portions 13a and 16a with a press).

〔燃料電池１０の製造方法の、生成水溜まり抑制のための実施例１の構成〕
本発明の実施例１の製造方法は、図５に示すように、膜−電極−拡散層アッセンブリ１５を形成する工程と、膜−電極アッセンブリの第１の部分に対応する第１のセパレータ部分１８ａと膜−電極アッセンブリの第２の部分に対応する第２のセパレータ部分１８ｂとを有する一対のセパレータ１８にて膜−電極−拡散層アッセンブリ１５を挟んでセル１０を形成する工程と、を有する燃料電池の製造方法であって、セパレータ１８の第１のセパレータ部分１８ａを第２のセパレータ部分１８ｂよりも拡散層１３、１６側に突出させておくことにより、一対のセパレータ１８で膜−電極−拡散層アッセンブリ１５を挟んだ時に第１の拡散層部分１３ａ、１６ａを第２の拡散層部分１３ｂ、１６ｂより強く圧縮して第１の拡散層部分１３ａ、１６ａの密度を第２の拡散層部分１３ｂ、１６ｂの密度以上とする方法からなる。実施例２ではセパレータ１８にリブ（第１のセパレータ部分１８ａで拡散層１３、１６側に突出させた部分）を形成しておいてリブで第１の拡散層部分１３ａ、１６ａを強く圧縮する。 [Configuration of Example 1 for Controlling Generated Water Puddle in Manufacturing Method of Fuel Cell 10]
As shown in FIG. 5, the manufacturing method according to the first embodiment of the present invention includes a step of forming a membrane-electrode-diffusion layer assembly 15 and a first separator portion 18a corresponding to the first portion of the membrane-electrode assembly. And forming a cell 10 by sandwiching the membrane-electrode-diffusion layer assembly 15 between a pair of separators 18 having a second separator portion 18b corresponding to the second portion of the membrane-electrode assembly. In the battery manufacturing method, the first separator portion 18a of the separator 18 protrudes toward the diffusion layers 13 and 16 with respect to the second separator portion 18b. When the layer assembly 15 is sandwiched, the first diffusion layer portions 13a and 16a are compressed more strongly than the second diffusion layer portions 13b and 16b, so that the first diffusion layer portions 13a and 16a are compressed. Density second diffusion layer portion 13b of the comprises a method to 16b density more. In Example 2, ribs (portions protruding toward the diffusion layers 13 and 16 by the first separator portion 18a) are formed on the separator 18, and the first diffusion layer portions 13a and 16a are strongly compressed by the ribs.

〔燃料電池１０の製造方法の参考例１、２、実施例１に共通の作用・効果〕
参考例１、２、実施例１の製造方法では、膜−電極アッセンブリ１２の厚みに応じて異なる条件にて拡散層１３、１６を膜−電極アッセンブリ１２に圧着するので、第１の拡散層部分１３ａ、１６ａの圧着条件を第２の拡散層部分１３ｂ、１６ｂの圧着条件より厳しくすることにより、触媒層１４、１７端縁の空間２を小さくするか、または、第１の拡散層部分１３ａ、１６ａの密度を高くすることができる。その結果、触媒層端縁の第１の拡散層部分１３ａ、１６ａに生成水が溜まりにくく、膜攻撃物質も溜まりにくく、膜１１の耐久性が向上する。 [Operations and effects common to Reference Examples 1 and 2 and Example 1 of manufacturing method of fuel cell 10]
In the manufacturing methods of Reference Examples 1 and 2 and Example 1, the diffusion layers 13 and 16 are pressure-bonded to the membrane-electrode assembly 12 under different conditions depending on the thickness of the membrane-electrode assembly 12, so that the first diffusion layer portion The space 2 at the edges of the catalyst layers 14 and 17 is made smaller by making the pressure bonding conditions of 13a and 16a stricter than the pressure bonding conditions of the second diffusion layer portions 13b and 16b, or the first diffusion layer portions 13a, The density of 16a can be increased. As a result, the generated water hardly accumulates in the first diffusion layer portions 13a and 16a at the edge of the catalyst layer, and the membrane attack substance hardly accumulates, so that the durability of the membrane 11 is improved.

〔燃料電池１０の製造方法の参考例１の作用・効果〕
参考例１の第１の方法では、第１の拡散層部分１３ａ、１６ａを第２の拡散層部分１３ｂ、１６ｂより高い圧力にて膜−電極アッセンブリ１２に圧着するので、触媒層１４、１７の端縁の空間２を小さくするか、または、第１の拡散層部分１３ａ、１６ａの密度を高くすることができる。その結果、触媒層端縁の第１の拡散層部分１３ａ、１６ａに生成水が溜まりにくく、膜攻撃物質も溜まりにくく、膜１１の耐久性が向上する。 [Operation / Effect of Reference Example 1 of Manufacturing Method of Fuel Cell 10]
In the first method of Reference Example 1, the first diffusion layer portions 13a and 16a are pressure-bonded to the membrane-electrode assembly 12 at a pressure higher than that of the second diffusion layer portions 13b and 16b. The edge space 2 can be reduced, or the density of the first diffusion layer portions 13a and 16a can be increased. As a result, the generated water hardly accumulates in the first diffusion layer portions 13a and 16a at the edge of the catalyst layer, and the membrane attack substance hardly accumulates, so that the durability of the membrane 11 is improved.

参考例１の第２の方法では、第１の拡散層部分１３ａ、１６ａを第２の拡散層部分１３ｂ、１６ｂより高い温度にて膜−電極アッセンブリ１２に圧着するので、第１の拡散層部分１３ａ、１６ａをそのほとんど全域で膜１１に密着させるとともに溶着でき、触媒層１４、１７の端縁の空間２を小さくすることができる。その結果、触媒層端縁の空間に生成水が溜まりにくく、膜攻撃物質も溜まりにくく、膜１１の耐久性が向上する。第２の拡散層部分１３ｂ、１６ｂを高温で圧着しないため、膜１１の変質と発電性能低下は発生しない。 In the second method of Reference Example 1, the first diffusion layer portions 13a and 16a are pressure-bonded to the membrane-electrode assembly 12 at a higher temperature than the second diffusion layer portions 13b and 16b. 13a and 16a can be in close contact with the film 11 and welded to almost the entire area, and the space 2 at the edges of the catalyst layers 14 and 17 can be reduced. As a result, the generated water hardly accumulates in the space at the edge of the catalyst layer, and the membrane attack substance hardly accumulates, so that the durability of the membrane 11 is improved. Since the second diffusion layer portions 13b and 16b are not pressure-bonded at a high temperature, the film 11 is not deteriorated and the power generation performance is not reduced.

参考例１の第３の方法では、第１の拡散層部分１３ａ、１６ａを第２の拡散層部分１３ｂ、１６ｂより長時間、膜−電極アッセンブリ１２に圧着するので、第１の拡散層部分１３ａ、１６ａをそのほとんど全域で膜１１に密着させるとともに溶着でき、触媒層端縁の空間２を小さくすることができる。その結果、触媒層端縁の空間２に生成水が溜まりにくく、膜攻撃物質も溜まりにくく、膜の耐久性が向上する。 In the third method of Reference Example 1, the first diffusion layer portions 13a and 16a are pressure-bonded to the membrane-electrode assembly 12 for a longer time than the second diffusion layer portions 13b and 16b. , 16a can be adhered to and welded to the membrane 11 over almost the entire area, and the space 2 at the edge of the catalyst layer can be reduced. As a result, the generated water hardly accumulates in the space 2 at the edge of the catalyst layer, and the membrane attack substance hardly accumulates, so that the durability of the membrane is improved.

参考例１の第３の方法における、長時間は再プレスの時間を含み、第１の拡散層部分１３ａ、１６ａを条件を変えて再プレスすることにより、第１の拡散層部分１３ａ、１６ａをそのほとんど全域で膜１１に密着させるとともに溶着でき、触媒層端縁の空間２を小さくすることができる。その結果、触媒層端縁の空間２に生成水が溜まりにくく、膜攻撃物質も溜まりにくく、膜の耐久性が向上する。発電領域に対応する第２の拡散層部分１３ｂ、１６ｂは長時間プレスせずガス拡散性、電極へのガス供給性を良好なままとする。 In the third method of Reference Example 1, the long time includes the re-pressing time, and the first diffusion layer portions 13a and 16a are re-pressed by changing the conditions under different conditions. Almost the entire region can be adhered and welded to the membrane 11, and the space 2 at the edge of the catalyst layer can be reduced. As a result, the generated water hardly accumulates in the space 2 at the edge of the catalyst layer, and the membrane attack substance hardly accumulates, so that the durability of the membrane is improved. The second diffusion layer portions 13b and 16b corresponding to the power generation region do not press for a long time, and the gas diffusibility and the gas supply property to the electrode remain good.

参考例１の第４の方法では、第１の拡散層部分１３ａ、１６ａの材料および撥水剤の何れか少なくとも一方の量を第２の拡散層部分１３ｂ、１６ｂの材料および撥水剤の何れか少なくとも一方の量より増やして拡散層を膜−電極アッセンブリに圧着するので、第１の拡散層部分１３ａ、１６ａの密度を第２の拡散層部分１３ｂ、１６ｂの密度に比べて高くすることができる。その結果、触媒層端縁の第１の拡散層部分１３ａ、１６ａに生成水が溜まりにくく、膜攻撃物質も溜まりにくく、膜１１の耐久性が向上する。 In the fourth method of Reference Example 1, at least one of the material of the first diffusion layer portions 13a and 16a and the water repellent agent is used as the amount of at least one of the material of the second diffusion layer portions 13b and 16b and the water repellent agent. Since the diffusion layer is pressure-bonded to at least one of the membrane-electrode assemblies, the density of the first diffusion layer portions 13a and 16a may be made higher than the density of the second diffusion layer portions 13b and 16b. it can. As a result, the generated water hardly accumulates in the first diffusion layer portions 13a and 16a at the edge of the catalyst layer, and the membrane attack substance hardly accumulates, so that the durability of the membrane 11 is improved.

〔燃料電池１０の製造方法の参考例２の作用・効果〕[Operation / Effect of Reference Example 2 of Manufacturing Method of Fuel Cell 10]
参考例２の方法では、一対のセパレータ１８で膜−電極−拡散層アッセンブリ１５を挟む前は第１の拡散層部分１３ａ、１６ａの厚みを第２の拡散層部分１３ｂ、１６ｂの厚みより大にしておくので、セル化、スタック化時に、一対のセパレータ１８で膜−電極−拡散層アッセンブリ１５を挟んだ時に第１の拡散層部分１３ａ、１６ａを第２の拡散層部分１３ｂ、１６ｂより強く圧縮して第１の拡散層部分１３ａ、１６ａの密度を第２の拡散層部分１３ｂ、１６ｂの密度以上とするとともに、触媒層端縁の空間２を縮小することができる。その結果、触媒層端縁の第１の拡散層部分１３ａ、１６ａおよび空間２に生成水が溜まりにくく、膜攻撃物質も溜まりにくく、膜１１の耐久性が向上する。In the method of Reference Example 2, before the membrane-electrode-diffusion layer assembly 15 is sandwiched between the pair of separators 18, the thickness of the first diffusion layer portions 13a and 16a is made larger than the thickness of the second diffusion layer portions 13b and 16b. Therefore, the first diffusion layer portions 13a and 16a are compressed more strongly than the second diffusion layer portions 13b and 16b when the membrane-electrode-diffusion layer assembly 15 is sandwiched between the pair of separators 18 in the cell formation and stacking. Thus, the density of the first diffusion layer portions 13a and 16a can be made higher than the density of the second diffusion layer portions 13b and 16b, and the space 2 at the edge of the catalyst layer can be reduced. As a result, the generated water hardly accumulates in the first diffusion layer portions 13a, 16a and the space 2 at the edge of the catalyst layer, and the membrane attack substance hardly accumulates, so that the durability of the membrane 11 is improved.

〔燃料電池１０の製造方法の実施例１の作用・効果〕
本発明の実施例１の方法では、セパレータ１８の第１のセパレータ部分１８ａを第２のセパレータ部分１８ｂよりも拡散層１３、１６側に突出させておくので、一対のセパレータ１８で膜−電極−拡散層アッセンブリ１５を挟んでスタック締結荷重をかけた時に第１の拡散層部分１３ａ、１６ａを第２の拡散層部分１３ｂ、１６ｂより強く圧縮して第１の拡散層部分１３ａ、１６ａの密度を第２の拡散層部分１３ｂ、１６ｂの密度以上とするとともに、触媒層端縁の空間２を縮小することができる。その結果、触媒層端縁の第１の拡散層部分１３ａ、１６ａおよび空間２に生成水が溜まりにくく、膜攻撃物質も溜まりにくく、膜１１の耐久性が向上する。 [Operation / Effect of Example 1 of Manufacturing Method of Fuel Cell 10]
In the method according to the first embodiment of the present invention, the first separator portion 18a of the separator 18 is protruded toward the diffusion layers 13 and 16 with respect to the second separator portion 18b. When a stack fastening load is applied across the diffusion layer assembly 15, the first diffusion layer portions 13a and 16a are compressed more strongly than the second diffusion layer portions 13b and 16b, thereby reducing the density of the first diffusion layer portions 13a and 16a. The density of the second diffusion layer portions 13b and 16b can be increased or more, and the space 2 at the edge of the catalyst layer can be reduced. As a result, the generated water hardly accumulates in the first diffusion layer portions 13a, 16a and the space 2 at the edge of the catalyst layer, and the membrane attack substance hardly accumulates, so that the durability of the membrane 11 is improved.

参考例１の燃料電池の製造方法の第１の方法を実施している途中の膜−電極−拡散層アッセンブリとプレス機の一部の断面図である。It is sectional drawing of a part of membrane-electrode-diffusion layer assembly in the middle of implementing the 1st method of the manufacturing method of the fuel cell of the reference example 1, and a press. 参考例１の燃料電池の製造方法の第２の方法を実施している途中の膜−電極−拡散層アッセンブリとプレス機の一部の断面図である。It is sectional drawing of a part of membrane-electrode-diffusion layer assembly in the middle of implementing the 2nd method of the manufacturing method of the fuel cell of the reference example 1, and a press machine. 参考例１の燃料電池の製造方法の第３の方法を実施している途中の膜−電極−拡散層アッセンブリとプレス機の斜視図である。It is a perspective view of the membrane-electrode-diffusion layer assembly and press machine in the middle of implementing the 3rd method of the manufacturing method of the fuel cell of the reference example 1. FIG. 参考例１の燃料電池の膜−電極−拡散層アッセンブリとセパレータの正面図である。 2 is a front view of a membrane-electrode-diffusion layer assembly and separator of a fuel cell of Reference Example 1. FIG. 本発明の実施例１の燃料電池の一部の断面図である。 1 is a partial cross-sectional view of a fuel cell according to Example 1 of the present invention. 参考例２の燃料電池の膜−電極−拡散層アッセンブリの一部の（セパレータで挟む前の）断面図である。6 is a cross-sectional view of a part of a membrane-electrode-diffusion layer assembly (before being sandwiched by a separator) of a fuel cell of Reference Example 2. FIG. 本発明の燃料電池のスタックの側面図である。It is a side view of the stack of the fuel cell of the present invention. 図７の一部の拡大断面図である。FIG. 8 is an enlarged sectional view of a part of FIG. 7. 図７のセルの正面図である。It is a front view of the cell of FIG. 従来の燃料電池の一部の断面図である。It is sectional drawing of a part of conventional fuel cell.

１０ 燃料電池
１１ 電解質膜
１２ 膜−電極アッセンブリ（ＭＥＡ）
１２ａ 第１の部分
１２ｂ 第２の部分
１３ 拡散層
１３ａ 第１の拡散層部分
１３ｂ 第２の拡散層部分
１４ 電極（アノード、燃料極）
１５ 膜−電極−拡散層アッセンブリ（ＭＥＧＡ）
１６ 拡散層
１６ａ 第１の拡散層部分
１６ｂ 第２の拡散層部分
１７ 電極（カソード、空気極）
１８ セパレータ
１８ａ 第１のセパレータ部分
１８ｂ 第２のセパレータ部分
１９ モジュール
２０ ターミナル
２１ インシュレータ
２２ エンドプレート
２３ スタック
２４ 締結部材（テンションプレート）
２５ ボルト
２６ 冷媒流路
２７ 燃料ガス流路
２８ 酸化ガス流路
２９ 冷媒マニホールド
３０ 燃料ガスマニホールド
３１ 酸化ガスマニホールド
３２ 冷媒側シール材（たとえば、ゴムガスケット）
３３ ガス側シール材（たとえば、接着剤）
５０ プレス機
５０ａ プレス機の第１の部分
５０ｂ プレス機の第２の部分 10 Fuel Cell 11 Electrolyte Membrane 12 Membrane-Electrode Assembly (MEA)
12a First portion 12b Second portion 13 Diffusion layer 13a First diffusion layer portion 13b Second diffusion layer portion 14 Electrode (anode, fuel electrode)
15 Membrane-electrode-diffusion layer assembly (MEGA)
16 Diffusion layer 16a First diffusion layer portion 16b Second diffusion layer portion 17 Electrode (cathode, air electrode)
18 Separator 18a First separator portion 18b Second separator portion 19 Module 20 Terminal 21 Insulator 22 End plate 23 Stack 24 Fastening member (tension plate)
25 Bolt 26 Refrigerant flow path 27 Fuel gas flow path 28 Oxidizing gas flow path 29 Refrigerant manifold 30 Fuel gas manifold 31 Oxidizing gas manifold 32 Refrigerant side sealing material (for example, rubber gasket)
33 Gas side sealing material (for example, adhesive)
50 Press machine 50a First part of press machine 50b Second part of press machine

Claims (1)

膜−電極アッセンブリに拡散層を接合した膜−電極−拡散層アッセンブリと、該膜−電極−拡散層アッセンブリを挟む一対のセパレータとを備えた燃料電池であって、膜−電極アッセンブリは互いに厚みが異なる第１の部分と第２の部分を有し第１の部分の厚みは第２の部分の厚みより小であり、拡散層は膜−電極アッセンブリの第１の部分に接合される第１の拡散層部分と膜−電極アッセンブリの第２の部分に接合される第２の拡散層部分とを有し第１の拡散層部分の密度は第２の拡散層部分の密度以上であり、
セパレータは膜−電極アッセンブリの第１の部分に対応する第１のセパレータ部分と膜−電極アッセンブリの第２の部分に対応する第２のセパレータ部分とを有し第１のセパレータ部分は第２のセパレータ部分よりも拡散層側に突出しており、
膜−電極アッセンブリの第１の部分は燃料電池の外周部に位置し、膜−電極アッセンブリの第２の部分は燃料電池の内周部に位置している、
燃料電池。 A fuel cell comprising a membrane-electrode-diffusion layer assembly in which a diffusion layer is joined to a membrane-electrode assembly and a pair of separators sandwiching the membrane-electrode-diffusion layer assembly, wherein the membrane-electrode assembly has a thickness of each other The first portion has a different first portion and a second portion, the thickness of the first portion being less than the thickness of the second portion, and the diffusion layer is bonded to the first portion of the membrane-electrode assembly. diffusion layer section and the membrane - the density of the first diffusion layer portion and a second diffusion layer portion bonded to the second portion of the electrode assembly Ri der than the density of the second diffusion layer portion,
The separator has a first separator portion corresponding to the first portion of the membrane-electrode assembly and a second separator portion corresponding to the second portion of the membrane-electrode assembly, the first separator portion being a second separator portion. It protrudes to the diffusion layer side from the separator part,
A first portion of the membrane-electrode assembly is located on the outer periphery of the fuel cell, and a second portion of the membrane-electrode assembly is located on the inner periphery of the fuel cell;
Fuel cell.
JP2005017580A 2005-01-26 2005-01-26 Fuel cell Expired - Fee Related JP4581702B2 (en)

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JPH10154521A (en) * 1996-09-24 1998-06-09 Matsushita Electric Ind Co Ltd Solid high polymer type fuel cell
WO2002023655A1 (en) * 2000-09-18 2002-03-21 Mitsubishi Heavy Industries, Ltd. Solid polymer type fuel battery

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JPH10154521A (en) * 1996-09-24 1998-06-09 Matsushita Electric Ind Co Ltd Solid high polymer type fuel cell
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