JP5162884B2 - Solid polymer electrolyte fuel cell - Google Patents

Solid polymer electrolyte fuel cell Download PDF

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JP5162884B2
JP5162884B2 JP2006315757A JP2006315757A JP5162884B2 JP 5162884 B2 JP5162884 B2 JP 5162884B2 JP 2006315757 A JP2006315757 A JP 2006315757A JP 2006315757 A JP2006315757 A JP 2006315757A JP 5162884 B2 JP5162884 B2 JP 5162884B2
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membrane
electrolyte membrane
solid polymer
polymer electrolyte
electrode
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JP2008130432A (en
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洋 高野
規雄 佐々木
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Fuji Electric Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • 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

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Description

本発明は、燃料ガスおよび酸化剤ガスを供給して発電する固体高分子電解質型燃料電池、特に、固体高分子電解質膜を挟んでその両面に燃料電極および酸化剤電極を配設してなる膜・電極接合体の構成に関する。なお本発明は、上記固体高分子電解質型燃料電池以外に、主に携帯用機器に用いられ燃料としてメタノールを直接用いる直接メタノール型燃料電池にも適用できる。   The present invention relates to a solid polymer electrolyte fuel cell that generates power by supplying a fuel gas and an oxidant gas, and in particular, a membrane in which a fuel electrode and an oxidant electrode are disposed on both sides of a solid polymer electrolyte membrane. -It is related with the structure of an electrode assembly. In addition to the solid polymer electrolyte fuel cell, the present invention can also be applied to a direct methanol fuel cell that is mainly used in portable equipment and directly uses methanol as a fuel.

近年、地球環境問題に鑑みクリーンで発電効率の高い次世代の発電装置が希求されており、その１つとして水素と空気中の酸素を化学反応させる際にその化学エネルギー変化を直接電気エネルギーとして取り出す燃料電池の実用化が大いに期待されている。特に、上記固体高分子電解質型燃料電池や直接メタノール型燃料電池は、一般家庭用としても、次第に普及する傾向が強まっている。   In recent years, there has been a demand for a next-generation power generation device that is clean and has high power generation efficiency in view of global environmental problems. As one of them, when chemical reaction between hydrogen and oxygen in the air is performed, the chemical energy change is directly taken out as electric energy. The practical application of fuel cells is highly expected. In particular, the solid polymer electrolyte fuel cell and the direct methanol fuel cell are becoming increasingly popular for general household use.

前記固体高分子電解質型燃料電池は、一般に、固体高分子電解質膜を挟んでその両面に燃料電極および酸化剤電極を配設してなる膜・電極接合体と、ガス不透過性のセパレ−ト板との積層体からなり、前記膜・電極接合体とセパレ−ト板との間には、その外周部に反応ガスの漏洩防止用のシール手段を備える（特許文献１，２参照）。   The solid polymer electrolyte fuel cell generally includes a membrane / electrode assembly in which a fuel electrode and an oxidant electrode are disposed on both sides of a solid polymer electrolyte membrane, and a gas-impermeable separator. It consists of a laminated body with a plate, and a seal means for preventing leakage of reactive gas is provided on the outer periphery between the membrane / electrode assembly and the separator plate (see Patent Documents 1 and 2).

特許文献１，２においては、いずれも、アノードおよびカソードの一対の電極の面積より大きく形成された固体高分子電解質膜の額縁状の外周部と、セパレ−ト板との間にシール部材を設けて、反応ガスのシールを行なう構成を採用している。   In each of Patent Documents 1 and 2, a seal member is provided between a frame-shaped outer periphery of a solid polymer electrolyte membrane formed larger than the area of a pair of anode and cathode electrodes, and a separator plate. Thus, a configuration for sealing the reaction gas is adopted.

上記のように、固体高分子電解質膜にシール部材を直接当接してシールを行なうもの以外に、電解質膜から張り出して設けた樹脂膜を用いて樹脂膜部でシールするものや、樹脂膜を補強膜として用いてシールする構成の燃料電池も知られている（特許文献３，４参照）。   As described above, in addition to sealing the solid polymer electrolyte membrane by directly contacting the sealing member, sealing with a resin membrane portion using a resin membrane protruding from the electrolyte membrane or reinforcing the resin membrane There is also known a fuel cell configured to be sealed as a membrane (see Patent Documents 3 and 4).

特許文献３は、その要約の記載を引用すると、「電極一体膜におけるイオン交換膜の面積をその主たる機能を損なうことなく縮小した固体高分子電解質型燃料電池を得る。」ことを目的として、図８に示すように「両面に酸化剤電極１３および燃料電極１４が密着して固着したイオン交換膜１２の外周部分が、これと重なりを有する額縁状の樹脂膜，例えばフッ素系モノマ−膜１５の内周部分に熱融着部１６で気密に結合されて一体化するよう電極一体膜を構成し、電極一体膜外周部分のガスシ−ル機能，およびマニホ−ルドなどをイオン交換膜に比べて極めて安価な額縁状の樹脂膜１５に分担させることにより、高価なイオン交換膜の面積を陽イオン交換膜として機能するに必要な一対の電極面積近くにまで縮小する。」構成を備える固体高分子電解質型燃料電池を開示している。   Patent Document 3 refers to the summary description, with the aim of “obtaining a solid polymer electrolyte fuel cell in which the area of the ion-exchange membrane in the electrode-integrated membrane is reduced without impairing its main function”. As shown in FIG. 8, “the outer peripheral portion of the ion exchange membrane 12 having the oxidant electrode 13 and the fuel electrode 14 adhered and fixed on both surfaces is overlapped with a frame-shaped resin film such as a fluorine-based monomer membrane 15. The electrode integral membrane is constructed so that it is hermetically coupled and integrated with the inner peripheral portion by the heat fusion part 16, and the gas seal function and manifold etc. of the electrode integral membrane outer peripheral portion are extremely different from those of the ion exchange membrane. By sharing the inexpensive resin film 15 with a frame shape, the area of the expensive ion exchange membrane is reduced to near the pair of electrode areas necessary to function as a cation exchange membrane. ” It discloses a polymer electrolyte fuel cell.

図８は、特許文献３の図１として開示された膜・電極接合体を示す平面図である（なお、一部の部番を変更している）。   FIG. 8 is a plan view showing the membrane-electrode assembly disclosed as FIG. 1 of Patent Document 3 (note that some part numbers have been changed).

特許文献４は、その要約の記載を引用すると、「固体高分子電解質膜の破損がなく信頼性に優れる固体高分子電解質型燃料電池を得る。」ことを目的として、図９に示すように「固体高分子電解質膜１に外形寸法が前記固体高分子電解質膜の外形寸法より小さい電極２，３を前記膜を介して対向して設けるとともに固体高分子電解質膜１の電極２，３の設けられていない外縁部と前記電極の周縁部に補強膜７，８を被覆して単セルとしこの単セルを前記固体高分子電解質膜の外縁部に設けられたガスシール部を介して反応ガス供給板４により挟持し且つシールする。」構成を備える固体高分子電解質型燃料電池を開示している。   Patent Document 4 quotes the summary description as shown in FIG. 9 for the purpose of “obtaining a solid polymer electrolyte fuel cell with no damage to the solid polymer electrolyte membrane and excellent reliability”. Electrodes 2 and 3 having outer dimensions smaller than the outer dimensions of the solid polymer electrolyte membrane 1 are provided on the solid polymer electrolyte membrane 1 so as to face each other through the membrane, and electrodes 2 and 3 of the solid polymer electrolyte membrane 1 are provided. Reinforcement membranes 7 and 8 are coated on the outer edge portion and the peripheral edge portion of the electrode to form a single cell, and this single cell is provided as a reaction gas supply plate via a gas seal portion provided on the outer edge portion of the solid polymer electrolyte membrane. 4 is disclosed. The solid polymer electrolyte fuel cell having the configuration is disclosed.

図９は、特許文献４の図１として開示された固体高分子電解質型燃料電池の断面図である。なお、図９における上記以外の部番の説明は省略する（詳細は、特許文献４参照）。   FIG. 9 is a cross-sectional view of the solid polymer electrolyte fuel cell disclosed as FIG. In addition, description of part numbers other than the above in FIG.

図７は、前記図８の構成と類似する膜・電極接合体の断面図を示す。図７において、２１は固体高分子電解質膜、２２はカソード触媒層、２３はアノード触媒層、２４はカソード拡散層、２５はアノード拡散層、２６は額縁状の樹脂膜としての補強フィルムを示す。
ここで、カソード触媒層２２とカソード拡散層２４とで一方の電極（カソード）を構成し、アノード触媒層２３とアノード拡散層２５とで他方の電極（アノード）を構成する。 FIG. 7 is a cross-sectional view of a membrane / electrode assembly similar to the structure of FIG. In FIG. 7, 21 is a solid polymer electrolyte membrane, 22 is a cathode catalyst layer, 23 is an anode catalyst layer, 24 is a cathode diffusion layer, 25 is an anode diffusion layer, and 26 is a reinforcing film as a frame-shaped resin film.
Here, the cathode catalyst layer 22 and the cathode diffusion layer 24 constitute one electrode (cathode), and the anode catalyst layer 23 and the anode diffusion layer 25 constitute the other electrode (anode).

ところで、図７と図８との主な相違点は下記のとおりである。即ち、図７の場合、額縁状の樹脂膜２６が、アノード触媒層２３の内方において、固体高分子電解質膜２１の外縁部と重なりを有し、電極外方に張り出した構成を備えている点である。
特開２００４−３３５４５３号公報 特開２００６−１５６０９７号公報 特開平５−２３４６０６号公報 特開平５−２４２８９７号公報 By the way, the main differences between FIG. 7 and FIG. 8 are as follows. That is, in the case of FIG. 7, the frame-shaped resin film 26 has a configuration in which it overlaps with the outer edge portion of the solid polymer electrolyte membrane 21 on the inner side of the anode catalyst layer 23 and protrudes to the outer side of the electrode. Is a point.
JP 2004-335453 A JP 2006-156097 A JP-A-5-234606 JP-A-5-2442897

上記のような従来の固体高分子電解質型燃料電池においては、下記のような問題があった。即ち、特許文献１〜４および図７に記載のいずれの燃料電池においても、固体高分子電解質膜または額縁状の樹脂膜が直線状に構成され、かつ電解質膜または樹脂膜の外周部に反応ガスの漏洩防止用のシール手段があって、電解質膜の面方向の直線状の自由な動きを、前記シール手段が拘束している。   The conventional solid polymer electrolyte fuel cell as described above has the following problems. That is, in any of the fuel cells described in Patent Documents 1 to 4 and FIG. 7, the solid polymer electrolyte membrane or the frame-like resin membrane is formed in a straight line, and the reaction gas is formed on the outer periphery of the electrolyte membrane or resin membrane. There is a sealing means for preventing leakage, and the sealing means restrains linear free movement in the surface direction of the electrolyte membrane.

固体高分子電解質型燃料電池の場合には、通常、電解質膜は加湿状態で運転されるが、燃料電池運転時に好適な加湿状態が維持されずに電解質膜が乾燥状態となった場合には、電解質膜が収縮する。その際、電解質膜または樹脂膜の外周部におけるシール手段の拘束によって、電解質膜には収縮に抗した引っ張り応力が作用し、電解質膜の損傷やクリープが生じ、燃料電池が運転不能となる問題がある。   In the case of a solid polymer electrolyte fuel cell, the electrolyte membrane is usually operated in a humidified state, but when the electrolyte membrane is in a dry state without maintaining a suitable humidified state during fuel cell operation, The electrolyte membrane contracts. At that time, due to the restraint of the sealing means at the outer periphery of the electrolyte membrane or resin membrane, the tensile stress against the shrinkage acts on the electrolyte membrane, resulting in damage or creep of the electrolyte membrane, and the problem that the fuel cell becomes inoperable. is there.

本発明は、上記の問題点に鑑みてなされたもので、この発明の課題は、電解質膜が燃料電池運転時に収縮した際にも、電解質膜に作用する引張り応力が抑制可能な構造を備え、運転寿命の長い固体高分子電解質型燃料電池を提供することにある。   The present invention has been made in view of the above problems, and the object of the present invention is to provide a structure capable of suppressing tensile stress acting on the electrolyte membrane even when the electrolyte membrane contracts during fuel cell operation. An object of the present invention is to provide a solid polymer electrolyte fuel cell having a long operating life.

上記課題は、以下により達成される。即ち、固体高分子電解質膜を挟んでその両面に燃料電極および酸化剤電極を配設してなる膜・電極接合体と、ガス不透過性のセパレ−ト板との積層体からなり、前記膜・電極接合体とセパレ−ト板との間には、その外周部に反応ガスの漏洩防止用のシール手段を備えた固体高分子電解質型燃料電池において、前記膜・電極接合体は、前記一対の電極の面積より大きく形成された固体高分子電解質膜の額縁状の外周部を備え、前記電解質膜の額縁状の外周部は、前記電解質膜が収縮した際の応力緩和手段を備え、この応力緩和手段の外側に前記シール手段を備え、前記応力緩和手段は、前記電解質膜の額縁状の外周部に設けた電解質膜の折り曲げ部であり、前記折り曲げ部は、膜面方向に唯一つの面状の段差を有するＳ字状の折り曲げ部であることを特徴とする（請求項１）。 The above-mentioned subject is achieved by the following. That is, a membrane / electrode assembly in which a fuel electrode and an oxidizer electrode are disposed on both sides of a solid polymer electrolyte membrane and a gas impermeable separator plate, and the membrane In the polymer electrolyte fuel cell having a sealing means for preventing leakage of reaction gas on the outer periphery between the electrode assembly and the separator plate, the membrane / electrode assembly is the pair with the outer peripheral portion frame-like the larger solid polymer electrolyte membrane than the area of the electrode, frame-shaped outer peripheral portion of the electrolyte membrane is provided with a stress relieving means when the electrolyte membrane contracts, the stress The sealing means is provided outside the relaxing means, and the stress relaxing means is a bent portion of the electrolyte membrane provided on a frame-like outer peripheral portion of the electrolyte membrane. bent portions der Ru S-shape having a stepped It characterized the door (claim 1).

前記請求項１の発明の実施態様としては、下記請求項２の発明が好ましい。即ち、前記請求項１に記載のものにおいて、前記Ｓ字状折り曲げ部における折り曲げ部の長さは、０．２〜２ｍｍとする（請求項２）。 As an embodiment of the invention of claim 1, the invention of claim 2 below is preferable. That is, in those described in the claim 1, the length of the bent portion before Symbol S-shaped bent portion, and 0.2 to 2 mm (claim 2).

なお、参考までに、前記課題は、下記の参考構成例１〜８によっても達成される。即ち、固体高分子電解質膜を挟んでその両面に燃料電極および酸化剤電極を配設してなる膜・電極接合体と、ガス不透過性のセパレ−ト板との積層体からなり、前記膜・電極接合体とセパレ−ト板との間には、その外周部に反応ガスの漏洩防止用のシール手段を備えた固体高分子電解質型燃料電池において、前記膜・電極接合体は、前記固体高分子電解質膜の外縁部と重なりを有して接合され電極外方に張り出した額縁状の樹脂膜を備え、前記額縁状の樹脂膜は、前記電解質膜が収縮した際の応力緩和手段を備え、この応力緩和手段の外側に前記シール手段を備えることを特徴とする（参考構成例１）。For reference, the above-described problem is also achieved by the following reference configuration examples 1 to 8. That is, a membrane / electrode assembly in which a fuel electrode and an oxidizer electrode are disposed on both sides of a solid polymer electrolyte membrane and a gas impermeable separator plate, and the membrane In the polymer electrolyte fuel cell having a sealing means for preventing leakage of reaction gas on the outer periphery between the electrode assembly and the separator plate, the membrane / electrode assembly is the solid A frame-shaped resin film that is joined to the outer edge of the polymer electrolyte membrane so as to overlap and protrudes outward from the electrode, and the frame-shaped resin film includes stress relaxation means when the electrolyte membrane contracts. The sealing means is provided outside the stress relaxation means (Reference Configuration Example 1).

前記参考構成例１の実施態様としては、下記参考構成例２ないし８が好ましい。即ち、前記参考構成例１に記載のものにおいて、前記応力緩和手段は、前記電解質膜の額縁状の外周部に設けた電解質膜の折り曲げ部とする（参考構成例２）。また、前記参考構成例１に記載のものにおいて、前記応力緩和手段は、前記額縁状の樹脂膜に設けた樹脂膜の折り曲げ部とする（参考構成例３）。さらに、前記参考構成例２または３に記載のものにおいて、前記折り曲げ部は、Ｓ字状の折り曲げ部とする（参考構成例４）。さらにまた、前記参考構成例４に記載のものにおいて、前記Ｓ字状折り曲げ部における折り曲げ部の長さは、０．２〜２ｍｍとする（参考構成例５）。また、前記参考構成例３に記載のものにおいて、前記折り曲げ部は、Ｕ字状の折り曲げ部とする（参考構成例６）。さらに、前記参考構成例６に記載のものにおいて、前記Ｕ字状折り曲げ部における湾曲部内側半径は、０．２〜２ｍｍとする（参考構成例７）。また、前記参考構成例３または４に記載のものにおいて、前記額縁状の樹脂膜は、固体高分子電解質膜と同程度の融点を有するフッ素系ポリマーからなり、固体高分子電解質膜の周縁部と熱融着により接合されてなるものとする（参考構成例８）。As embodiments of the reference configuration example 1, the following reference configuration examples 2 to 8 are preferable. That is, in the structure described in the reference configuration example 1, the stress relaxation means is a bent portion of the electrolyte membrane provided on the frame-shaped outer peripheral portion of the electrolyte membrane (reference configuration example 2). Moreover, in the thing of the said reference structure example 1, the said stress relaxation means is made into the bending part of the resin film provided in the said frame-shaped resin film (reference structure example 3). Furthermore, in the thing of the said reference structure example 2 or 3, the said bending part is made into a S-shaped bending part (reference structure example 4). Furthermore, in the thing of the said reference structure example 4, the length of the bending part in the said S-shaped bending part shall be 0.2-2 mm (reference structure example 5). Moreover, in the thing of the said reference structural example 3, let the said bending part be a U-shaped bending part (reference structural example 6). Furthermore, in the thing of the said reference structural example 6, the curved part inner side radius in the said U-shaped bending part shall be 0.2-2 mm (reference structural example 7). Further, in the structure described in the reference configuration example 3 or 4, the frame-shaped resin film is made of a fluorine-based polymer having a melting point similar to that of the solid polymer electrolyte membrane, and the peripheral portion of the solid polymer electrolyte membrane is It shall be joined by thermal fusion (Reference Configuration Example 8).

この発明によれば、電解質膜の収縮に伴う応力が緩和されるので、燃料電池運転時に電解質膜の損傷やクリープを生じ難い膜・電極接合体が得られ、運転寿命の長い固体高分子電解質型燃料電池が提供できる。   According to the present invention, the stress associated with the contraction of the electrolyte membrane is relieved, so that a membrane / electrode assembly that hardly causes damage or creep of the electrolyte membrane during operation of the fuel cell can be obtained, and the solid polymer electrolyte type with a long operating life is obtained. A fuel cell can be provided.

次に、この発明の実施形態ならびに参考構成例および比較例に関して、図１ないし図６に基いて説明する。図１および２は、本発明の参考構成例１および２に係る膜・電極接合体の模式的断面図、図３および４は、図１および２の膜・電極接合体の製造治具および製造方法を説明する模式的断面図である。 Next, an embodiment of the present invention, a reference configuration example, and a comparative example will be described with reference to FIGS. 1 and 2 are schematic cross-sectional views of membrane / electrode assemblies according to Reference Configuration Examples 1 and 2 of the present invention, and FIGS. 3 and 4 are manufacturing jigs and manufactures of the membrane / electrode assemblies of FIGS. It is typical sectional drawing explaining a method.

上記、図１〜４は、いずれも電極外方に張り出した額縁状の樹脂膜を有する参考構成例を示すが、これらについて説明する前に、本発明の実施形態に係る膜・電極接合体の模式的断面図を示す図６について述べる。 Above, FIGS. 1-4, an example reference structure having a frame-like resin film both overhanging electrode outward, before describing these, according to the exemplary shape condition of the present invention membrane electrode assembly FIG. 6 showing a schematic cross-sectional view of FIG.

図６の実施形態は、前記図９の膜・電極接合体をベースとし、応力緩和手段として、電解質膜の外周部に電解質膜の折り曲げ部１ａを設けたものであり、シール手段は概念的に部番５６として示す。シール手段の構成としては、図９に開示されたように、フッ素樹脂からなる補強膜を介して反応ガスをシールする構成としてもよいし、また、補強膜を用いずに、固体高分子電解質膜１を直接シールする構成としてもよい。   The embodiment of FIG. 6 is based on the membrane / electrode assembly of FIG. 9 and is provided with a bent portion 1a of the electrolyte membrane on the outer periphery of the electrolyte membrane as stress relaxation means. This is shown as part number 56. As the configuration of the sealing means, as disclosed in FIG. 9, the reactive gas may be sealed through a reinforcing membrane made of a fluororesin, or a solid polymer electrolyte membrane may be used without using the reinforcing membrane. 1 may be directly sealed.

上記図６の構成によれば、電解質膜が燃料電池運転時に収縮した際に、電解質膜の折り曲げ部１ａが容易に追随して電解質膜の面方向に動き得るので、電解質膜に作用する引張り応力が抑制できる。   According to the configuration of FIG. 6, when the electrolyte membrane contracts during fuel cell operation, the bent portion 1a of the electrolyte membrane can easily follow and move in the surface direction of the electrolyte membrane, so that the tensile stress acting on the electrolyte membrane Can be suppressed.

次に、図１および図２の参考構成例について述べる。図１および図２において、図７に示した部材と同一機能部材には、同一番号を付して示す。図１の参考構成例は、固体高分子電解質膜の外縁部と重なりを有して接合され電極外方に張り出した額縁状の樹脂膜２６を備え、応力緩和手段として、前記額縁状の樹脂膜に設けた樹脂膜の折り曲げ部２６ａを設けた態様を示す。この折り曲げ部２６ａは、図１（ｂ）の拡大図に示すように、Ｓ字状折り曲げ部であって、その長さ（図１（ｂ）に示すＬ）は、０．２〜２ｍｍが好ましい。この長さＬは、主に家庭用１ｋＷの固体高分子電解質膜型燃料電池を対象とする電極サイズ：約１５ｃｍ×１５ｃｍの場合に対する所要長さであるが、電極サイズの大小に応じて、適宜、比例的に増減する。 Next, a reference configuration example of FIGS. 1 and 2 will be described. In FIG. 1 and FIG. 2, the same functional members as those shown in FIG. The reference configuration example of FIG. 1 includes a frame-shaped resin film 26 which is joined with an outer edge portion of the solid polymer electrolyte membrane and is projected outward, and the frame-shaped resin film is used as stress relaxation means. The aspect which provided the bending part 26a of the resin film provided in FIG. As shown in the enlarged view of FIG. 1B, the bent portion 26a is an S-shaped bent portion, and its length (L shown in FIG. 1B) is preferably 0.2 to 2 mm. . This length L is a required length for an electrode size of about 15 cm × 15 cm mainly for a 1 kW solid polymer electrolyte membrane fuel cell for home use, but is appropriately selected depending on the size of the electrode. Increase or decrease proportionally.

図２の参考構成例は、額縁状の樹脂膜２６に設けた樹脂膜の折り曲げ部をＵ字状の折り曲げ部２６ｂとした態様を示す。前記Ｕ字状折り曲げ部２６ｂにおける湾曲部内側半径（図２（ｂ）に示すｒ）は、０．２〜２ｍｍとするのが好ましい。このｒの値は、電極サイズの大小に応じて、適宜、比例的に増減する。 The reference configuration example of FIG. 2 shows an aspect in which the bent portion of the resin film provided on the frame-shaped resin film 26 is a U-shaped bent portion 26b. The inside radius of the curved portion (r shown in FIG. 2B) in the U-shaped bent portion 26b is preferably 0.2 to 2 mm. The value of r increases / decreases proportionally as appropriate according to the size of the electrode.

次に、図３および４について述べる。図３および４における部番２７および２８は、後述する実施例１および２において使用したプレス治具を示し、膜・電極接合体の製作に当たっては、固体高分子電解質膜２１を挟む電極部には熱と圧力を加え、所謂熱プレスにより、所定の温度および圧力下で一体化する。
（参考構成の具体例） Next, FIGS. 3 and 4 will be described. Part numbers 27 and 28 in FIGS. 3 and 4 show the pressing jigs used in Examples 1 and 2 to be described later. In manufacturing the membrane / electrode assembly, the electrode parts sandwiching the solid polymer electrolyte membrane 21 are not provided. Heat and pressure are applied, and integration is performed under a predetermined temperature and pressure by a so-called hot press.
(Specific examples of reference configuration)

次に、参考構成の具体例および比較例に関して述べる。 Next, specific examples of the reference configuration and comparative examples will be described.

（参考構成の具体例１）
白金担持量４０質量％の白金担持カーボン１０ｇと、パーフルオロスルホン酸ポリマー５％g/gアルコール溶液１００ｇとを混合して作製した触媒ペーストを拡散層上にダイコーターを用いて白金量が０．３mg/cm2となるように塗布し、空気電極／拡散層接合体を作製した。次に白金担持量３０質量％，ルテニウム担持量１５質量％の白金ルテニウムカーボン１０ｇと、パーフルオロスルホン酸ポリマー５％g/gアルコール溶液１００ｇとを混合して作成した触媒ペーストを電解質膜上にダイコーターを用いて白金量が０．３mg/cm2となるように塗布し、燃料電極／拡散層接合体を作製した。 ( Specific example 1 of the reference configuration )
A catalyst paste prepared by mixing 10 g of platinum-supporting carbon having a platinum-supporting amount of 40% by mass with 100 g of a perfluorosulfonic acid polymer 5% g / g alcohol solution was placed on the diffusion layer using a die coater. The air electrode / diffusion layer assembly was prepared by coating at 3 mg / cm 2 . Next, a catalyst paste prepared by mixing 10 g of platinum ruthenium carbon having a platinum loading of 30% by mass and ruthenium loading of 15% by mass with 100 g of a perfluorosulfonic acid polymer 5% g / g alcohol solution is formed on the electrolyte membrane by Daiko. The fuel electrode / diffusion layer assembly was prepared by applying a platinum so that the amount of platinum was 0.3 mg / cm 2 .

次に、電解質膜および電極を、あらかじめＳ字状折り曲げ部（図１の２６ａ）をつけておいた額縁状補強フィルムと共に図３に示す製作治具にセットし、空気電極／拡散層接合体、燃料電極／拡散層接合体を電解質膜の両面に配置して熱プレスし、温度１４０℃、圧力５ＭＰａで一体化した。   Next, the electrolyte membrane and the electrode are set in the production jig shown in FIG. 3 together with the frame-shaped reinforcing film with the S-shaped bent portion (26a in FIG. 1) attached in advance, and the air electrode / diffusion layer assembly, The fuel electrode / diffusion layer assembly was placed on both sides of the electrolyte membrane and hot-pressed and integrated at a temperature of 140 ° C. and a pressure of 5 MPa.

（参考構成の具体例２）
白金担持量４０質量％の白金担持カーボン１０ｇと、パーフルオロスルホン酸ポリマー５％g/gアルコール溶液１００ｇとを混合して作製した触媒ペーストを拡散層上にダイコーターを用いて白金量が０．３mg/cm2となるように塗布し、空気電極／拡散層を作製した。次に、空気電極／拡散層の空気電極側に電解質膜を温度１４０℃、圧力５ＭＰａで一体化した。次に、白金担持量３０質量％，ルテニウム担持量１５質量％の白金ルテニウムカーボン１０ｇと、パーフルオロスルホン酸ポリマー５％g/gアルコール溶液１００ｇとを混合して作成した触媒ペーストを電解質膜上にダイコーターを用いて白金量が０．３mg/cm2となるように塗布し、燃料電極／拡散層接合体を作製した。 ( Specific example 2 of reference configuration )
A catalyst paste prepared by mixing 10 g of platinum-supporting carbon having a platinum-supporting amount of 40% by mass with 100 g of a perfluorosulfonic acid polymer 5% g / g alcohol solution was placed on the diffusion layer using a die coater. The air electrode / diffusion layer was prepared by coating to 3 mg / cm 2 . Next, an electrolyte membrane was integrated at a temperature of 140 ° C. and a pressure of 5 MPa on the air electrode / diffusion layer side of the air electrode. Next, a catalyst paste prepared by mixing 10 g of platinum ruthenium carbon having a platinum loading amount of 30% by mass and ruthenium loading amount of 15% by mass with 100 g of a perfluorosulfonic acid polymer 5% g / g alcohol solution is formed on the electrolyte membrane. Coating was performed using a die coater so that the amount of platinum was 0.3 mg / cm 2 , thereby preparing a fuel electrode / diffusion layer assembly.

最後に、あらかじめＵ字状折り曲げ部（図２の２６ｂ）をつけておいた額縁状補強フィルムを図４に示す製作治具にセットし、電解質膜／空気電極/拡散層接合体、燃料電極／拡散層接合体を額縁状補強フィルムの両面に配置して、温度１４０℃、圧力５ＭＰａで一体化した。   Finally, a frame-like reinforcing film with a U-shaped bent portion (26b in FIG. 2) attached in advance is set on the production jig shown in FIG. 4, and the electrolyte membrane / air electrode / diffusion layer assembly, fuel electrode / The diffusion layer assembly was disposed on both sides of the frame-shaped reinforcing film and integrated at a temperature of 140 ° C. and a pressure of 5 MPa.

（比較例）
下記により、前記図７に示すような膜・電極接合体を製作した。 (Comparative example)
A membrane / electrode assembly as shown in FIG. 7 was manufactured as follows.

白金担持量４０質量％の白金担持カーボン１０ｇと、パーフルオロスルホン酸ポリマー５％g/gアルコール溶液１００ｇとを混合して作製した触媒ペーストを拡散層上にダイコーターを用いて白金量が０．３mg/cm2となるように塗布し、空気電極／拡散層接合体を作製した。次に白金担持量３０質量％，ルテニウム担持量１５質量％の白金ルテニウムカーボン１０ｇと、パーフルオロスルホン酸ポリマー５％g/gアルコール溶液１００ｇとを混合して作成した触媒ペーストを電解質膜上にダイコーターを用いて白金量が０．３mg/cm2となるように塗布し、燃料電極／拡散層接合体を作製した。 A catalyst paste prepared by mixing 10 g of platinum-supporting carbon having a platinum-supporting amount of 40% by mass with 100 g of a perfluorosulfonic acid polymer 5% g / g alcohol solution was placed on the diffusion layer using a die coater. The air electrode / diffusion layer assembly was prepared by coating at 3 mg / cm 2 . Next, a catalyst paste prepared by mixing 10 g of platinum ruthenium carbon having a platinum loading of 30% by mass and ruthenium loading of 15% by mass with 100 g of a perfluorosulfonic acid polymer 5% g / g alcohol solution is formed on the electrolyte membrane by Daiko. The fuel electrode / diffusion layer assembly was prepared by applying a platinum so that the amount of platinum was 0.3 mg / cm 2 .

最後に、電解質膜を凹凸のない製作治具にセットし、空気電極/拡散層接合体、燃料電極／拡散層接合体を電解質膜の両面に配置して、温度１４０℃、圧力５ＭＰａで一体化した。   Finally, the electrolyte membrane is set in a manufacturing jig without unevenness, and the air electrode / diffusion layer assembly and the fuel electrode / diffusion layer assembly are arranged on both sides of the electrolyte membrane, and integrated at a temperature of 140 ° C. and a pressure of 5 MPa. did.

上記参考構成の具体例１，２及び比較例のセル長期試験結果を図５に示す。図５の横軸は、運転時間（h）を、縦軸は単セル電圧（m V）を示す。比較例で作製した膜・電極接合体では、電解質膜が切れて電池電圧が急低下したのに対し、参考構成の具体例１，２の膜・電極接合体の場合には安定に運転することができた。 FIG. 5 shows the results of the long-term cell tests of specific examples 1 and 2 of the reference configuration and the comparative example. The horizontal axis in FIG. 5 represents the operation time (h), and the vertical axis represents the single cell voltage (mV). In the membrane / electrode assembly produced in the comparative example, the electrolyte membrane was cut and the battery voltage dropped sharply, whereas in the case of the membrane / electrode assembly of specific examples 1 and 2 of the reference configuration , the operation should be stable. I was able to.

本発明の参考構成例１に係る膜・電極接合体の模式的断面図。1 is a schematic cross-sectional view of a membrane / electrode assembly according to Reference Configuration Example 1 of the present invention. 本発明の参考構成例２に係る膜・電極接合体の模式的断面図。The typical sectional view of the membrane electrode assembly concerning reference composition example 2 of the present invention. 図１の膜・電極接合体の製造治具および製造方法を説明する模式的断面図。FIG. 2 is a schematic cross-sectional view illustrating a manufacturing jig and a manufacturing method for the membrane / electrode assembly of FIG. 1. 図２の膜・電極接合体の製造治具および製造方法を説明する模式的断面図。FIG. 3 is a schematic cross-sectional view illustrating a manufacturing jig and a manufacturing method of the membrane / electrode assembly of FIG. 2. 参考構成の具体例１，２および比較例の膜・電極接合体を用いた燃料電池の長期運転結果を示す図。 The figure which shows the long-term driving | running result of the fuel cell using the example 1, 2 of a reference structure, and the membrane electrode assembly of a comparative example. 本発明の実施形態に係る膜・電極接合体の模式的断面図。Schematic cross-sectional view of a membrane electrode assembly according to an exemplary shape condition of the present invention. 従来の膜・電極接合体の断面図（図８の変形例）Sectional view of a conventional membrane / electrode assembly (modified example of FIG. 8) 特許文献３において図１として開示された膜・電極接合体の平面図。FIG. 3 is a plan view of the membrane / electrode assembly disclosed in FIG. 特許文献４において図１として開示された固体高分子電解質型燃料電池の断面図。FIG. 2 is a cross-sectional view of a solid polymer electrolyte fuel cell disclosed in FIG.

１，２１：固体高分子電解質膜、２：アノード、３：カソード、２２：カソード触媒層、２３：アノード触媒層、２４：カソード拡散層、２５：アノード拡散層、２６：額縁状の樹脂膜（補強フィルム）、１ａ：固体高分子電解質膜のＳ字状折り曲げ部、２６ａ：樹脂膜のＳ字状折り曲げ部、２６ｂ：樹脂膜のＵ字状の折り曲げ部、２７，２８：プレス治具、５６：シール手段。
1, 2: 1: solid polymer electrolyte membrane, 2: anode, 3: cathode, 22: cathode catalyst layer, 23: anode catalyst layer, 24: cathode diffusion layer, 25: anode diffusion layer, 26: frame-shaped resin membrane ( Reinforcing film), 1a: S-shaped bent portion of solid polymer electrolyte membrane, 26a: S-shaped bent portion of resin film, 26b: U-shaped bent portion of resin film, 27, 28: Press jig, 56 : Sealing means.

Claims (2)

固体高分子電解質膜を挟んでその両面に燃料電極および酸化剤電極を配設してなる膜・電極接合体と、ガス不透過性のセパレ−ト板との積層体からなり、前記膜・電極接合体とセパレ−ト板との間には、その外周部に反応ガスの漏洩防止用のシール手段を備えた固体高分子電解質型燃料電池において、
前記膜・電極接合体は、前記一対の電極の面積より大きく形成された固体高分子電解質膜の額縁状の外周部を備え、前記電解質膜の額縁状の外周部は、前記電解質膜が収縮した際の応力緩和手段を備え、この応力緩和手段の外側に前記シール手段を備え、前記応力緩和手段は、前記電解質膜の額縁状の外周部に設けた電解質膜の折り曲げ部であり、前記折り曲げ部は、膜面方向に唯一つの面状の段差を有するＳ字状の折り曲げ部であることを特徴とする固体高分子電解質型燃料電池。 A membrane / electrode assembly comprising a fuel electrode and an oxidant electrode disposed on both sides of a solid polymer electrolyte membrane and a gas impermeable separator plate, and the membrane / electrode Between the joined body and the separator plate, in the solid polymer electrolyte fuel cell provided with sealing means for preventing leakage of the reaction gas on the outer periphery thereof,
The membrane electrode assembly includes an outer peripheral portion frame shape of the pair of electrodes solid polymer electrolyte membrane from the larger area of the picture frame-shaped outer peripheral portion of the electrolyte membrane, the electrolyte membrane contracts A stress relaxation means, and the sealing means is provided outside the stress relaxation means. The stress relaxation means is a bent portion of the electrolyte membrane provided on a frame-shaped outer peripheral portion of the electrolyte membrane, and the bent portion a solid polymer electrolyte fuel cell, wherein the bent portion der Rukoto of S-shaped with only one surface of the step in the membrane surface direction. 請求項１に記載のものにおいて、前記Ｓ字状折り曲げ部における折り曲げ部の長さは、０．２〜２ｍｍであることを特徴とする固体高分子電解質型燃料電池。 2. The solid polymer electrolyte fuel cell according to claim 1 , wherein a length of the bent portion in the S-shaped bent portion is 0.2 to 2 mm.
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