JP2000223134A - Manufacture of solid polymer electrolyte film/electrode junction body, and fuel cell - Google Patents
Manufacture of solid polymer electrolyte film/electrode junction body, and fuel cellInfo
- Publication number
- JP2000223134A JP2000223134A JP11018316A JP1831699A JP2000223134A JP 2000223134 A JP2000223134 A JP 2000223134A JP 11018316 A JP11018316 A JP 11018316A JP 1831699 A JP1831699 A JP 1831699A JP 2000223134 A JP2000223134 A JP 2000223134A
- Authority
- JP
- Japan
- Prior art keywords
- polymer electrolyte
- solid polymer
- electrolyte membrane
- electrodes
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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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- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は固体高分子電解質膜
・電極接合体の製造方法および燃料電池に関する。The present invention relates to a method for producing a solid polymer electrolyte membrane / electrode assembly and a fuel cell.
【０００２】[0002]
【従来の技術】大気汚染防止のためのＣＯ２排出規制お
よび石油資源枯渇といった地球規模での環境・資源問題
に対処するため、クリーンでエネルギー密度が高く、充
電時間が不要である燃料電池は最も脚光を浴び、日本を
始め世界中で急ピッチに研究開発が進められている。特
に、自動車等車載用電力源としては固体高分子電解質型
燃料電池が低温作動性や小型で高出力密度であることか
ら研究開発が活発に進められている。2. Description of the Related Art In order to cope with global environmental and resource issues such as CO 2 emission regulations for preventing air pollution and depletion of petroleum resources, fuel cells which are clean, have high energy density and do not require recharging time are the most common. In the limelight, R & D is being carried out rapidly in Japan and around the world. In particular, research and development are being actively pursued as solid polymer electrolyte fuel cells as power sources for vehicles such as automobiles because of their low-temperature operability, small size, and high power density.
【０００３】燃料電池は、一般的に多数のセルが積層さ
れており、該セルは、二つの電極（燃料極と酸化剤極）
と電解質の接合体をセパレータで挟んだ構造をしてい
る。[0003] A fuel cell generally has a number of stacked cells, and the cell has two electrodes (a fuel electrode and an oxidant electrode).
And electrolyte are sandwiched between separators.
【０００４】前記燃料極では燃料ガス中の水素が触媒に
接触することにより下記の反応が生ずる。At the fuel electrode, the following reaction occurs when hydrogen in the fuel gas comes into contact with the catalyst.
【０００５】２Ｈ２ → ４Ｈ＋ ＋４ｅ− Ｈ＋は、電解質中を移動し酸化剤極触媒に達し酸化剤ガ
ス中の酸素と反応して水となる。[0005] 2H 2 → 4H + + 4e − H + moves through the electrolyte, reaches the oxidant electrode catalyst, and reacts with oxygen in the oxidant gas to form water.
【０００６】４Ｈ＋ ＋４ｅ− ＋Ｏ２ → ２Ｈ２Ｏ 上記の反応により水素と酸素を使用して電気分解の逆反
応で発電し、水以外の排出物がなくクリーンな発電装置
として注目されている。[0006] 4H + + 4e - + O 2 → 2H 2 O using hydrogen and oxygen by the reaction generated by the reverse reaction of the electrolysis, emissions other than water are attracting attention as a clean power generation device without.
【０００７】前記固体高分子電解質型燃料電池の固体高
分子電解質膜・電極接合体は、湿潤状態の固体高分子電
解質膜を電極で挟持してホットプレスする方法で製造さ
れる。図６はホットプレス時の固体高分子電解質膜・電
極接合体の断面図であり、図７はホットプレス時の固体
高分子電解質膜・電極接合体の正面図である。電解質で
ある固体高分子電解質膜１を二つの電極２ａ、２ｂで挟
んで加熱して上下から圧力をかけて接合する。[0007] The solid polymer electrolyte membrane / electrode assembly of the solid polymer electrolyte fuel cell is manufactured by a method in which a wet solid polymer electrolyte membrane is sandwiched between electrodes and hot-pressed. FIG. 6 is a sectional view of the solid polymer electrolyte membrane / electrode assembly during hot pressing, and FIG. 7 is a front view of the solid polymer electrolyte membrane / electrode assembly during hot pressing. The solid polymer electrolyte membrane 1, which is an electrolyte, is sandwiched between the two electrodes 2a and 2b, and heated to apply pressure from above and below to join.
【０００８】固体高分子電解質膜・電極接合体の接合強
度を大きくするためにホットプレス前の前記固体高分子
電解質膜１は湿潤状態にしておく。該固体高分子電解質
膜１はホットプレス時の加熱により乾燥して収縮する。
図６、７の矢印は前記固体高分子電解質膜１の収縮方向
を表している。電極２ａ，２ｂ部分の固体高分子電解質
膜は、電極２ａ，２ｂにより面方向には収縮しない。前
記電極２ａ，２ｂの周辺部の固体高分子電解質膜だけが
収縮するので、固体高分子電解質膜１にしわ４が発生す
る。In order to increase the bonding strength of the solid polymer electrolyte membrane / electrode assembly, the solid polymer electrolyte membrane 1 before hot pressing is kept wet. The solid polymer electrolyte membrane 1 is dried and shrunk by heating during hot pressing.
The arrows in FIGS. 6 and 7 indicate the contraction direction of the solid polymer electrolyte membrane 1. The solid polymer electrolyte membranes at the electrodes 2a and 2b do not contract in the plane direction due to the electrodes 2a and 2b. Since only the solid polymer electrolyte membrane around the electrodes 2a and 2b contracts, wrinkles 4 occur in the solid polymer electrolyte membrane 1.
【０００９】前記固体高分子電解質膜１の周辺部は、固
体高分子電解質膜・電極接合体を燃料ガスまたは酸化剤
ガスの流路を有するセパレータに挟持して製造するセル
のガスシールの役割がある。前記しわ４があると、セパ
レータで挟んでセルを製造し、該セルを多数積層して燃
料電池を製造したときに、前記固体高分子電解質膜１が
破れたりガスシールの不具合が起こりやすくなり、燃料
電池の性能が低下する。The periphery of the solid polymer electrolyte membrane 1 serves as a gas seal for a cell manufactured by sandwiching the solid polymer electrolyte membrane / electrode assembly between separators having a flow path for fuel gas or oxidizing gas. is there. When the wrinkles 4 are present, a cell is manufactured by sandwiching the separator, and when the fuel cell is manufactured by stacking a large number of the cells, the solid polymer electrolyte membrane 1 is easily broken or a problem of gas sealing easily occurs. The performance of the fuel cell decreases.
【００１０】従来技術として、特開平３−２９５１７１
号公報には、固体高分子電解質膜の周縁部を電極よりも
厚い弾性体で挟持してホットプレスする固体高分子電解
質膜・電極接合体の製造方法が開示されている。The prior art is disclosed in Japanese Patent Application Laid-Open No. 3-295171.
Japanese Patent Application Laid-Open Publication No. H11-139,086 discloses a method for producing a solid polymer electrolyte membrane-electrode assembly in which a peripheral portion of a solid polymer electrolyte membrane is sandwiched between elastic bodies thicker than electrodes and hot-pressed.
【００１１】[0011]
【発明が解決しようとする課題】しかしながら、従来技
術は、弾性体と固体高分子電解質膜との密着強度が弱い
ため、ホットプレス後の前記固体高分子電解質膜にしわ
の発生が完全にはなくなっていない。However, in the prior art, since the adhesion strength between the elastic body and the solid polymer electrolyte membrane is weak, wrinkling of the solid polymer electrolyte membrane after hot pressing is completely eliminated. Not.
【００１２】本発明は上記課題を解決したもので、ホッ
トプレス時に固体高分子電解質膜にしわが発生する問題
を解決し、耐久性に優れた固体高分子電解質膜・電極接
合体の製造方法および燃料電池を提供する。The present invention solves the above-mentioned problems, and solves the problem of wrinkling of a solid polymer electrolyte membrane during hot pressing, and provides a method for manufacturing a solid polymer electrolyte membrane-electrode assembly having excellent durability and a fuel. Provide batteries.
【００１３】[0013]
【課題を解決するための手段】上記技術的課題を解決す
るために、本発明の請求項１において講じた技術的手段
（以下、第１の技術的手段と称する。）は、固体高分子
電解質膜を電極で挟持して接合した固体高分子電解質膜
・電極接合体の製造方法において、前記電極より大きな
前記固体高分子電解質膜を前記電極で挟持し、該固体高
分子電解質膜の前記電極の周辺部を面粗度が１０μｍＲ
ｚ以上の平板で挟持してホットプレスすることを特徴と
する固体高分子電解質膜・電極接合体の製造方法であ
る。Means for Solving the Problems In order to solve the above technical problems, the technical means (hereinafter referred to as first technical means) taken in claim 1 of the present invention is a solid polymer electrolyte. In a method for producing a solid polymer electrolyte membrane / electrode assembly in which a membrane is sandwiched and joined by electrodes, the solid polymer electrolyte membrane larger than the electrodes is sandwiched by the electrodes, and the electrodes of the solid polymer electrolyte membrane are Surface roughness of the peripheral part is 10μmR
A method for producing a solid polymer electrolyte membrane / electrode assembly, comprising hot-pressing while sandwiching between z or more flat plates.
【００１４】上記第１の技術的手段による効果は、以下
のようである。The effects of the first technical means are as follows.
【００１５】すなわち、前記平板は面粗度が大きいの
で、ホットプレス時に固体高分子電解質膜が該平板に食
い込み、固体高分子電解質膜と平板の密着強度を大きく
することができるので、平板で挟持されている部分の固
体高分子電解質膜が拘束され、該部分が平面方向に収縮
するのを防止するためしわが全く発生しない効果を有す
る。That is, since the flat plate has a large surface roughness, the solid polymer electrolyte membrane bites into the flat plate during hot pressing, and the adhesion strength between the solid polymer electrolyte membrane and the flat plate can be increased. Since the solid polymer electrolyte membrane in the portion where the portion is cut is restrained and the portion is prevented from contracting in the plane direction, there is an effect that no wrinkles are generated.
【００１６】上記技術的課題を解決するために、本発明
の請求項２において講じた技術的手段（以下、第２の技
術的手段と称する。）は、前記平板がカーボンペーパ
ー、カーボンクロス、前記電極材料の少なくとも一つで
あることを特徴とする請求項１記載の固体高分子電解質
膜・電極接合体の製造方法である。In order to solve the above technical problem, the technical means (hereinafter referred to as the second technical means) taken in claim 2 of the present invention is that the flat plate is made of carbon paper, carbon cloth, The method for producing a solid polymer electrolyte membrane-electrode assembly according to claim 1, wherein the method is at least one of electrode materials.
【００１７】上記第２の技術的手段による効果は、以下
のようである。The effects of the second technical means are as follows.
【００１８】すなわち、電極と同じ材料であるので、固
体高分子電解質膜が汚染されることがなく、かつ電極と
して利用されなかった部分を利用できるので、燃料電池
の耐久性を向上し、かつ低コスト化できる。That is, since the material is the same as that of the electrode, the solid polymer electrolyte membrane is not contaminated, and a portion not used as an electrode can be used. Cost can be reduced.
【００１９】上記技術的課題を解決するために、本発明
の請求項３において講じた技術的手段（以下、第３の技
術的手段と称する。）は、請求項１記載の固体高分子電
解質膜・電極接合体の製造方法で製造された固体高分子
電解質膜・電極接合体をセパレータで挟持したことを特
徴とする燃料電池である。In order to solve the above-mentioned technical problem, the technical means (hereinafter referred to as the third technical means) of the present invention is the solid polymer electrolyte membrane according to the present invention. -A fuel cell characterized in that a solid polymer electrolyte membrane / electrode assembly produced by a method for producing an electrode assembly is sandwiched between separators.
【００２０】上記第３の技術的手段による効果は、以下
のようである。The effects of the third technical means are as follows.
【００２１】すなわち、固体高分子電解質膜にしわがな
い固体高分子電解質膜・電極接合体を用いているので、
前記固体高分子電解質膜が破れたり、ガスシールに不具
合が生ずることがなく、信頼性に優れた燃料電池ができ
る。That is, since a solid polymer electrolyte membrane / electrode assembly having no wrinkles in the solid polymer electrolyte membrane is used,
There is no breakage of the solid polymer electrolyte membrane and no problem in gas sealing, and a highly reliable fuel cell can be obtained.
【００２２】[0022]
【発明の実施の形態】以下、本発明の実施例について説
明する。Embodiments of the present invention will be described below.
【００２３】＜固体高分子電解質膜の作製＞本実施例お
よび比較例で使用した固体高分子電解質膜は、炭化フッ
素系ビニールモノマーと炭化水素系ビニールモノマーの
共重合体を主鎖とし、スルホン酸基を有する炭化水素系
側鎖からなる陽イオン交換膜である。<Preparation of Solid Polymer Electrolyte Membrane> The solid polymer electrolyte membrane used in the present examples and comparative examples has a copolymer of a fluorocarbon vinyl monomer and a hydrocarbon vinyl monomer as a main chain, and a sulfonic acid. It is a cation exchange membrane comprising a hydrocarbon-based side chain having a group.
【００２４】具体的には、エチレン−四フッ化エチレン
共重合体フィルム（膜厚５０μｍ）に２０ｋＧｙの線量
のγ線を窒素中、常温下で照射した後、前記フィルムを
スチレンモノマ中に６０℃で３時間浸すことにより、エ
チレン−四フッ化エチレン共重合体にスチレン鎖をグラ
フトした。Specifically, after irradiating an ethylene-tetrafluoroethylene copolymer film (film thickness 50 μm) with γ-rays at a dose of 20 kGy at room temperature in nitrogen, the film was immersed in styrene monomer at 60 ° C. For 3 hours to graft a styrene chain onto the ethylene-tetrafluoroethylene copolymer.
【００２５】前記フィルムを乾燥後、クロルスルホン酸
１容積部と１，２−ジクロロエタン１００容積部の混合
液中に、グラフトスチレンに対するクロルスルホン酸の
濃度が５モル倍になるようにし、５０℃、１時間浸し
た。After the film is dried, a mixture of 1 part by volume of chlorosulfonic acid and 100 parts by volume of 1,2-dichloroethane is adjusted so that the concentration of chlorosulfonic acid with respect to the grafted styrene becomes 5 mol times at 50 ° C. Soaked for 1 hour.
【００２６】前記フィルムを乾燥後、９０℃のイオン交
換水中に１時間浸漬し、更に９０℃の新しいイオン交換
水で２時間洗浄し、固体高分子電解質膜を得た。After drying the film, the film was immersed in ion-exchanged water at 90 ° C. for 1 hour and further washed with fresh ion-exchanged water at 90 ° C. for 2 hours to obtain a solid polymer electrolyte membrane.
【００２７】＜電極の作製＞本実施例および比較例で使
用した電極の電極基材シートとして市販の厚さ０．２３
ｍｍのカーボンペーパー（東レ社製、ＴＧＰ−Ｈ−０６
０）を用いた。該カーボンペーパーを１６０ｍｍ×１６
０ｍｍに切断して電極基材シートを作製する。<Preparation of Electrode> A commercially available electrode base sheet for the electrodes used in the present Examples and Comparative Examples having a thickness of 0.23
mm carbon paper (TGP-H-06 manufactured by Toray Industries, Inc.)
0) was used. 160mm × 16
Cut to 0 mm to produce an electrode substrate sheet.
【００２８】テトラフルオロエチレン粒子分散液（ダイ
キン工業社製、Ｄ−１グレード、テトラフルオロエチレ
ン粒子６０ｗｔ％含有）をテトラフルオロエチレン粒子
濃度が１５ｗｔ％になるように水で希釈したテトラフル
オロエチレン粒子希釈溶液に前記電極基材シートを２分
間浸漬した。前記電極基材シートは多孔質であるので内
部に前記テトラフルオロエチレン粒子希釈溶液が浸透し
含浸する。A tetrafluoroethylene particle dispersion (D-1 grade, manufactured by Daikin Industries, containing 60% by weight of tetrafluoroethylene particles) was diluted with water so that the tetrafluoroethylene particle concentration became 15% by weight. The electrode substrate sheet was immersed in the solution for 2 minutes. Since the electrode substrate sheet is porous, the tetrafluoroethylene particle dilute solution permeates and impregnates the inside.
【００２９】前記電極基材シートを約８０℃で水分を蒸
発させた後、大気中３９０℃で６０分保持してテトラフ
ルオロエチレン粒子をカーボン繊維の表面に固着させ
る。白金担持カーボン（白金含有量４０ｗｔ％）と水と
イオン交換溶液（旭化成社製、アシプレックス溶液ＳＳ
−１０８０）及びイソプロピルアルコールを１：１．
５：１５：１．５の重量比で十分混合して触媒ペースト
を作製し、ドクターブレード法により前記電極基材シー
トの一方の面に約３００μｍの厚さで塗布した。After evaporating the water at about 80 ° C., the electrode base sheet is held at 390 ° C. in the atmosphere for 60 minutes to fix the tetrafluoroethylene particles on the surface of the carbon fiber. Platinum-supported carbon (platinum content 40 wt%), water and ion exchange solution (Aciplex solution SS, manufactured by Asahi Kasei Corporation)
-1080) and isopropyl alcohol in a ratio of 1: 1.
A catalyst paste was prepared by sufficiently mixing at a weight ratio of 5: 15: 1.5, and was applied to one surface of the electrode substrate sheet at a thickness of about 300 μm by a doctor blade method.
【００３０】該電極基材シートを乾燥してイソプロピル
アルコールを除去すると電極シートができる。該電極シ
ートの中心部１２０ｍｍ×１２０ｍｍを切り取ると電極
が完成する。該電極シートの中心部を使用する理由は、
ドクターブレード法による触媒ペーストの塗布が該電極
シートの周辺部で不均一になるからである。When the electrode base sheet is dried to remove isopropyl alcohol, an electrode sheet is formed. The electrode is completed when 120 mm x 120 mm is cut out from the center of the electrode sheet. The reason for using the center of the electrode sheet is
This is because the application of the catalyst paste by the doctor blade method becomes non-uniform around the electrode sheet.
【００３１】（実施例１）図１は、実施例１のホットプ
レス時の固体高分子電解質膜、電極、平板の配置を示す
図である。２００ｍｍ×２００ｍｍに切断した固体高分
子電解質膜１１の中央部を電極２１で挟持し、幅２０ｍ
ｍの平板であるカーボンペーパー３１で前記電極２１を
囲んで前記固体高分子電解質膜１１を挟持する。(Example 1) FIG. 1 is a diagram showing the arrangement of a solid polymer electrolyte membrane, electrodes and flat plates during hot pressing in Example 1. The central portion of the solid polymer electrolyte membrane 11 cut into 200 mm × 200 mm was sandwiched between electrodes 21 and the width was 20 m.
The solid polymer electrolyte membrane 11 is sandwiched between the electrodes 21 by carbon paper 31 which is a flat plate of m.
【００３２】これを、圧力１０ｋｇ／ｃｍ２、温度１２
０℃、時間１５ｍｉｎの条件でホットプレスした。ホッ
トプレス後、カーボンペーパーをはがし前記電極２１を
中心として１４０ｍｍ×１４０ｍｍの大きさに固体高分
子電解質膜を切断すると固体高分子電解質膜・電極接合
体が完成する。This was carried out at a pressure of 10 kg / cm 2 and a temperature of 12 kg / cm 2.
Hot pressing was performed at 0 ° C. for 15 minutes. After hot pressing, the carbon paper is peeled off, and the solid polymer electrolyte membrane is cut into a size of 140 mm × 140 mm around the electrode 21 to complete a solid polymer electrolyte membrane / electrode assembly.
【００３３】前記固体高分子電解質膜１１のカーボンペ
ーパー３１で挟持された部分にしわは全く見られなかっ
たので、前記固体高分子電解質膜・電極接合体の固体高
分子電解質膜にはしわは全く見られない。Since no wrinkles were observed in the portion of the solid polymer electrolyte membrane 11 sandwiched between the carbon papers 31, no wrinkles were formed in the solid polymer electrolyte membrane of the solid polymer electrolyte membrane / electrode assembly. can not see.
【００３４】前記カーボンペーパー３１は東レ社製のＴ
ＧＰ−Ｈ−０６０を用いた。該カーボンペーパー３１の
面粗度を東京精密社製サーフコム２００Ｃ、測定距離１
０ｍｍで測定した結果、５２．５μｍＲｚであった。The carbon paper 31 is made of T
GP-H-060 was used. The surface roughness of the carbon paper 31 was measured using Surfcom 200C manufactured by Tokyo Seimitsu Co.,
As a result of measurement at 0 mm, it was 52.5 μmRz.
【００３５】製造された固体高分子電解質膜・電極接合
体をセパレータで挟持してセルを製造し、該セルを１０
０個積層して燃料電池を製造した。電極の酸化剤極に酸
化剤ガスである空気を供給し、燃料極に燃料ガスを供給
して発電試験を１００時間実施した。固体高分子電解質
膜が損傷する不具合は発生しなかった。A cell is manufactured by sandwiching the manufactured solid polymer electrolyte membrane / electrode assembly with a separator, and the cell is
Zero fuel cells were stacked to produce a fuel cell. Air as an oxidant gas was supplied to the oxidant electrode of the electrode, and fuel gas was supplied to the fuel electrode, and a power generation test was performed for 100 hours. No problem that the solid polymer electrolyte membrane was damaged occurred.
【００３６】（実施例２）図２は、実施例２のホットプ
レス時の固体高分子電解質膜、電極、平板の配置を示す
図である。この配置の仕方以外は実施例１と同じであ
る。(Example 2) FIG. 2 is a view showing the arrangement of the solid polymer electrolyte membrane, electrodes and flat plates during hot pressing in Example 2. Other than this arrangement, the arrangement is the same as that of the first embodiment.
【００３７】２４０ｍｍ×２４０ｍｍに切断した固体高
分子電解質膜１２を電極２２で挟持し、該電極２２の周
縁から２０ｍｍ離れた部分を幅２０ｍｍの平板であるカ
ーボンペーパー３２で挟持する。これを実施例１と同じ
条件でホットプレスし、その後カーボンペーパー３２を
はがし前記電極２２を中心として１４０ｍｍ×１４０ｍ
ｍの大きさに固体高分子電解質膜を切断すると固体高分
子電解質膜・電極接合体が完成する。The solid polymer electrolyte membrane 12 cut into a size of 240 mm × 240 mm is sandwiched between the electrodes 22, and a portion 20 mm away from the periphery of the electrode 22 is sandwiched between carbon paper 32 which is a flat plate having a width of 20 mm. This was hot-pressed under the same conditions as in Example 1, and then the carbon paper 32 was peeled off and the electrode 22 was centered at 140 mm × 140 m.
When the solid polymer electrolyte membrane is cut to a size of m, the solid polymer electrolyte membrane / electrode assembly is completed.
【００３８】前記固体高分子電解質膜１２のカーボンペ
ーパー３２で挟持された部分および前記電極２２と前記
カーボンペーパー３２の間の固体高分子電解質膜にしわ
は全く見られなかったので、前記固体高分子電解質膜・
電極接合体の固体高分子電解質膜にはしわは全く見られ
ない。Since no wrinkles were observed in the portion of the solid polymer electrolyte membrane 12 sandwiched between the carbon papers 32 and between the electrode 22 and the carbon paper 32, no wrinkles were observed. Electrolyte membrane
No wrinkles are observed in the solid polymer electrolyte membrane of the electrode assembly.
【００３９】（実施例３）図３は、実施例３のホットプ
レス時の固体高分子電解質膜、電極、平板の配置を示す
図である。この配置の仕方以外は実施例１と同じであ
る。Example 3 FIG. 3 is a diagram showing the arrangement of the solid polymer electrolyte membrane, electrodes and flat plates during hot pressing in Example 3. Other than this arrangement, the arrangement is the same as that of the first embodiment.
【００４０】２００ｍｍ×２００ｍｍに切断した固体高
分子電解質膜１３の中央部を電極２３で挟持し、該電極
２３の周縁に接触させて２０ｍｍ×１２０ｍｍ の平板
であるカーボンペーパー３３で、該カーボンペーパー３
３の長手方向が前記電極２３の周縁に沿うように前記固
体高分子電解質膜１３を挟持する。これを実施例１と同
じ条件でホットプレスし、その後カーボンペーパーをは
がし前記電極２３を中心として１４０ｍｍ×１４０ｍｍ
の大きさに固体高分子電解質膜を切断すると固体高分子
電解質膜・電極接合体が完成する。The central portion of the solid polymer electrolyte membrane 13 cut into 200 mm × 200 mm is sandwiched between the electrodes 23, and is brought into contact with the periphery of the electrode 23 so that the carbon paper 33 is a flat plate of 20 mm × 120 mm.
The solid polymer electrolyte membrane 13 is sandwiched between the electrodes 3 so that the longitudinal direction thereof is along the periphery of the electrode 23. This was hot-pressed under the same conditions as in Example 1, then the carbon paper was peeled off, and the electrode 23 was centered on 140 mm × 140 mm.
The solid polymer electrolyte membrane-electrode assembly is completed by cutting the solid polymer electrolyte membrane into a size of.
【００４１】前記固体高分子電解質膜１３のカーボンペ
ーパー３３で挟持された部分および前記電極２３の角周
辺部の固体高分子電解質膜にしわは全く見られなかった
ので、前記固体高分子電解質膜・電極接合体の固体高分
子電解質膜にはしわは全く見られない。Since no wrinkles were observed in the portion of the solid polymer electrolyte membrane 13 sandwiched between the carbon papers 33 and the corners of the electrodes 23, no wrinkles were observed. No wrinkles are observed in the solid polymer electrolyte membrane of the electrode assembly.
【００４２】（実施例４）図４は、実施例４のホットプ
レス時の固体高分子電解質膜、電極、平板の配置を示す
図である。この配置の仕方以外は実施例１と同じであ
る。(Example 4) FIG. 4 is a view showing the arrangement of a solid polymer electrolyte membrane, electrodes and flat plates during hot pressing in Example 4. Other than this arrangement, the arrangement is the same as that of the first embodiment.
【００４３】２４０ｍｍ×２４０ｍｍに切断した固体高
分子電解質膜１４の中央部を電極２４で挟持し、該電極
２４の周縁から２０ｍｍ離れた部分を２０ｍｍ×１２０
ｍｍの平板であるカーボンペーパー３４で、該カーボン
ペーパー３４の長手方向が前記電極２４の周縁に平行に
なるように挟持する。これを実施例１と同じ条件でホッ
トプレスし、その後カーボンペーパーをはがし前記電極
２４を中心として１４０ｍｍ×１４０ｍｍの大きさに固
体高分子電解質膜を切断すると固体高分子電解質膜・電
極接合体が完成する。The central portion of the solid polymer electrolyte membrane 14 cut into 240 mm × 240 mm is sandwiched between electrodes 24, and a portion 20 mm away from the periphery of the electrode 24 is 20 mm × 120 mm.
The length of the carbon paper 34 is held in parallel with the periphery of the electrode 24 by a flat carbon paper 34 mm. This was hot-pressed under the same conditions as in Example 1, then the carbon paper was peeled off, and the solid polymer electrolyte membrane was cut into a size of 140 mm × 140 mm centering on the electrode 24 to complete the solid polymer electrolyte membrane-electrode assembly. I do.
【００４４】前記固体高分子電解質膜１４のカーボンペ
ーパー３４で挟持された部分および前記電極２４と前記
カーボンペーパー３４の間の固体高分子電解質膜にしわ
は全く見られなかったので、前記固体高分子電解質膜・
電極接合体の固体高分子電解質膜にはしわは全く見られ
ない。Since no wrinkles were observed in the portion of the solid polymer electrolyte membrane 14 sandwiched between the carbon papers 34 and in the solid polymer electrolyte membrane between the electrode 24 and the carbon paper 34, Electrolyte membrane
No wrinkles are observed in the solid polymer electrolyte membrane of the electrode assembly.
【００４５】（実施例５）平板としてカーボンペーパー
に変えて電極を製造するときに切り離した電極シートを
必要な大きさに切断して使用した以外実施例１〜４と同
じ固体高分子電解質膜、電極、平板の配置と同じ条件で
固体高分子電解質膜・電極接合体を作製した。前記電極
シートは電極と同じものである。この場合も、いずれも
固体高分子電解質膜・電極接合体の固体高分子電解質膜
にしわは全く見られなかった。前記電極シートの面粗度
は２４．５μｍＲｚであった。(Example 5) The same solid polymer electrolyte membrane as in Examples 1 to 4 except that the electrode sheet which was cut off when producing the electrode instead of carbon paper as a flat plate was cut into a required size and used. A solid polymer electrolyte membrane / electrode assembly was produced under the same conditions as the arrangement of the electrodes and the flat plate. The electrode sheet is the same as the electrode. Also in this case, no wrinkles were observed in the solid polymer electrolyte membrane / electrode assembly of the solid polymer electrolyte membrane. The surface roughness of the electrode sheet was 24.5 μmRz.
【００４６】（比較例）平板としてカーボンペーパーに
変えて弾性体であるフッ化ビニリデンゴムを使用した以
外実施例１と同じである。前記フッ化ビニリデンゴムの
厚さは０．３ｍｍであった。作製された固体高分子電解
質膜・電極接合体の固体高分子電解質膜の電極周辺に
は、平板が全くないときにほどではないが、しわが発生
していた。前記フッ化ビニリデンゴムの面粗度は６．５
μｍＲｚであった。(Comparative Example) The same operation as in Example 1 except that vinylidene fluoride rubber as an elastic body was used instead of carbon paper as the flat plate. The thickness of the vinylidene fluoride rubber was 0.3 mm. Wrinkles were formed around the electrodes of the solid polymer electrolyte membrane / electrode assembly of the fabricated solid polymer electrolyte membrane / electrode assembly, though not so much as when there were no flat plates at all. The surface roughness of the vinylidene fluoride rubber is 6.5.
μmRz.
【００４７】以上のように、表面の面粗度が大きい平板
を使用した実施例ではしわの発生はないが、面粗度が小
さい比較例ではしわが発生した。電極の周辺に置かれた
平板の面粗度が大きいと、湿潤状態の固体高分子電解質
膜は柔軟になっているので、該固体高分子電解質膜が平
板に食い込み密着強度を向上させる。前記固体高分子電
解質膜と平板の密着強度が大きいと、平板で挟持されて
いる部分の固体高分子電解質膜は固定され、固体高分子
電解質膜が乾燥状態になっても面内方向の収縮は抑えら
れるのでしわの発生が防止できた。ホットプレス後、実
施例の平板は固体高分子電解質膜に密着しており力を加
えないとはがれないが、比較例の平板は密着していな
い。As described above, wrinkles did not occur in the example using the flat plate having a large surface roughness, but wrinkles occurred in the comparative example having a small surface roughness. If the surface roughness of the flat plate placed around the electrode is large, the solid polymer electrolyte membrane in a wet state becomes flexible, so that the solid polymer electrolyte membrane bites into the flat plate to improve the adhesion strength. When the adhesion strength between the solid polymer electrolyte membrane and the flat plate is large, the portion of the solid polymer electrolyte membrane sandwiched between the flat plates is fixed, and even when the solid polymer electrolyte membrane is in a dry state, shrinkage in the in-plane direction is reduced. Because it was suppressed, the occurrence of wrinkles could be prevented. After hot pressing, the flat plate of the example is in close contact with the solid polymer electrolyte membrane and cannot be removed without applying force, but the flat plate of the comparative example is not in close contact.
【００４８】本発明を応用して、複数個の固体高分子電
解質膜・電極接合体を１回のホットプレスで製造するこ
とができる。By applying the present invention, a plurality of solid polymer electrolyte membrane / electrode assemblies can be manufactured by one hot press.
【００４９】図５は本発明の応用例のホットプレス時の
固体高分子電解質膜、電極、平板の配置を示す図であ
る。３４０ｍｍ×３４０ｍｍに切断した固体高分子電解
質膜１５の中心部を４組の電極２５で挟持する。該電極
２５同士は２０ｍｍ離れて対称に置く。該電極２５の周
縁から前記固体高分子電解質膜１５の周縁方向に２０ｍ
ｍ離れた部分を２０ｍｍ×１２０ｍｍ の平板であるカ
ーボンペーパー３５で、該カーボンペーパー３５の長手
方向が前記電極２５の周縁に平行になるように前記固体
高分子電解質膜１５を挟持する。FIG. 5 is a view showing the arrangement of the solid polymer electrolyte membrane, the electrodes and the flat plate at the time of hot pressing according to an application example of the present invention. The central portion of the solid polymer electrolyte membrane 15 cut into a size of 340 mm × 340 mm is sandwiched between four sets of electrodes 25. The electrodes 25 are symmetrically placed 20 mm apart. 20 m from the periphery of the electrode 25 to the periphery of the solid polymer electrolyte membrane 15
The solid polymer electrolyte membrane 15 is sandwiched by a carbon paper 35 which is a flat plate of 20 mm × 120 mm at a distance of m so that the longitudinal direction of the carbon paper 35 is parallel to the periphery of the electrode 25.
【００５０】こうしてホットプレス後、前記カーボンペ
ーパー３５をはがし、前記電極２５の周縁部から１０ｍ
ｍ離れた位置で切断すると４個の固体高分子電解質膜・
電極接合体ができる。電極２５が互いに、しわの発生を
防止する平板の役割を果たしているので、平板を節約で
きる。また一度のホットプレスで多数の固体高分子電解
質膜・電極接合体ができるので低コスト化することがで
きる。After the hot pressing, the carbon paper 35 was peeled off and 10 m from the periphery of the electrode 25.
When cut at a distance of 4 m, four solid polymer electrolyte membranes
An electrode assembly is formed. Since the electrodes 25 play a role of a flat plate for preventing wrinkles from occurring, the flat plate can be saved. Further, since a large number of solid polymer electrolyte membrane / electrode assemblies can be formed by one hot press, the cost can be reduced.
【００５１】なお、ホットプレス条件は固体高分子電解
質膜と電極の接合ができればよく、実施例の条件に限定
されない。The hot pressing condition is not limited to the condition of the embodiment as long as the solid polymer electrolyte membrane and the electrode can be joined.
【００５２】[0052]
【発明の効果】以上のように、本発明は、固体高分子電
解質膜を電極で挟持して接合した固体高分子電解質膜・
電極接合体の製造方法において、前記電極より大きな前
記固体高分子電解質膜を前記電極で挟持し、該固体高分
子電解質膜の前記電極の周辺部を面粗度が１０μｍＲｚ
以上の平板で挟持してホットプレスすることを特徴とす
る固体高分子電解質膜・電極接合体の製造方法および該
製造方法で製造された固体高分子電解質膜・電極接合体
をセパレータで挟持したことを特徴とする燃料電池であ
るので、ホットプレス時に固体高分子電解質膜にしわが
発生する問題を解決し、耐久性に優れた固体高分子電解
質膜・電極接合体の製造方法および燃料電池ができる。As described above, the present invention provides a solid polymer electrolyte membrane in which a solid polymer electrolyte membrane is sandwiched between electrodes and joined.
In the method for manufacturing an electrode assembly, the solid polymer electrolyte membrane larger than the electrode is sandwiched between the electrodes, and a peripheral portion of the solid polymer electrolyte membrane around the electrode has a surface roughness of 10 μmRz.
A method for manufacturing a solid polymer electrolyte membrane / electrode assembly, characterized in that the solid polymer electrolyte membrane / electrode assembly is sandwiched between the flat plates and hot pressed, and the solid polymer electrolyte membrane / electrode assembly manufactured by the manufacturing method is sandwiched between separators. Therefore, the problem of wrinkling of the solid polymer electrolyte membrane during hot pressing can be solved, and a method for producing a solid polymer electrolyte membrane-electrode assembly having excellent durability and a fuel cell can be obtained.
【図１】実施例１のホットプレス時の固体高分子電解質
膜、電極、平板の配置を示す図FIG. 1 is a diagram showing the arrangement of a solid polymer electrolyte membrane, electrodes, and a flat plate during hot pressing in Example 1.
【図２】実施例２のホットプレス時の固体高分子電解質
膜、電極、平板の配置を示す図FIG. 2 is a view showing the arrangement of a solid polymer electrolyte membrane, electrodes, and a flat plate during hot pressing in Example 2.
【図３】実施例３のホットプレス時の固体高分子電解質
膜、電極、平板の配置を示す図FIG. 3 is a diagram showing the arrangement of a solid polymer electrolyte membrane, electrodes, and a flat plate during hot pressing in Example 3.
【図４】実施例４のホットプレス時の固体高分子電解質
膜、電極、平板の配置を示す図FIG. 4 is a view showing the arrangement of a solid polymer electrolyte membrane, electrodes, and a flat plate during hot pressing in Example 4.
【図５】本発明の応用例のホットプレス時の固体高分子
電解質膜、電極、平板の配置を示す図FIG. 5 is a diagram showing an arrangement of a solid polymer electrolyte membrane, electrodes, and a flat plate during hot pressing according to an application example of the present invention.
【図６】ホットプレス時の固体高分子電解質膜・電極接
合体の断面図FIG. 6 is a cross-sectional view of the solid polymer electrolyte membrane / electrode assembly during hot pressing.
【図７】ホットプレス時の固体高分子電解質膜・電極接
合体の正面図FIG. 7 is a front view of the solid polymer electrolyte membrane / electrode assembly during hot pressing.
１、１１〜１５…固体高分子電解質膜 ２ａ、２ｂ、２１〜２５…電極 ３…平板 ４…しわ ３１〜３５…カーボンペーパー（平板） Reference numerals 1, 11 to 15: solid polymer electrolyte membranes 2a, 2b, 21 to 25: electrodes 3: flat plates 4: wrinkles 31 to 35: carbon paper (flat plates)
───────────────────────────────────────────────────── フロントページの続き (72)発明者 伊藤 直樹 愛知県刈谷市八軒町５丁目50番地 株式会 社イムラ材料開発研究所内 Ｆターム(参考） 5H026 AA06 BB01 BB02 CX04 EE05 EE17 HH00 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Naoki Ito 5-50, Hachigen-cho, Kariya-shi, Aichi F-term in Imura Materials Development Laboratory Co., Ltd. 5H026 AA06 BB01 BB02 CX04 EE05 EE17 HH00
Claims (3)
合した固体高分子電解質膜・電極接合体の製造方法にお
いて、前記電極より大きな前記固体高分子電解質膜を前
記電極で挟持し、該固体高分子電解質膜の前記電極の周
辺部を面粗度が１０μｍＲｚ以上の平板で挟持してホッ
トプレスすることを特徴とする固体高分子電解質膜・電
極接合体の製造方法。1. A method for producing a solid polymer electrolyte membrane / electrode assembly in which a solid polymer electrolyte membrane is sandwiched and joined by electrodes, wherein the solid polymer electrolyte membrane larger than the electrodes is sandwiched by the electrodes. A method for producing a solid polymer electrolyte membrane-electrode assembly, comprising sandwiching a peripheral portion of the solid polymer electrolyte membrane around the electrode with a flat plate having a surface roughness of 10 μmRz or more and hot pressing.
クロス、前記電極材料の少なくとも一つであることを特
徴とする請求項１記載の固体高分子電解質膜・電極接合
体の製造方法。2. The method for producing a solid polymer electrolyte membrane / electrode assembly according to claim 1, wherein the flat plate is at least one of carbon paper, carbon cloth, and the electrode material.
極接合体の製造方法で製造された固体高分子電解質膜・
電極接合体をセパレータで挟持したことを特徴とする燃
料電池。3. A solid polymer electrolyte membrane manufactured by the method for manufacturing a solid polymer electrolyte membrane-electrode assembly according to claim 1.
A fuel cell comprising an electrode assembly sandwiched between separators.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11018316A JP2000223134A (en) | 1999-01-27 | 1999-01-27 | Manufacture of solid polymer electrolyte film/electrode junction body, and fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11018316A JP2000223134A (en) | 1999-01-27 | 1999-01-27 | Manufacture of solid polymer electrolyte film/electrode junction body, and fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000223134A true JP2000223134A (en) | 2000-08-11 |
Family
ID=11968220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11018316A Pending JP2000223134A (en) | 1999-01-27 | 1999-01-27 | Manufacture of solid polymer electrolyte film/electrode junction body, and fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000223134A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1341249A1 (en) * | 2000-11-21 | 2003-09-03 | Nok Corporation | Constituent part for fuel cell |
| JP2006156036A (en) * | 2004-11-26 | 2006-06-15 | Nissan Motor Co Ltd | Assembly apparatus for membrane electrode assembly, and assembly method of membrane electrode assembly |
| JP2010504618A (en) * | 2006-09-22 | 2010-02-12 | キャボット コーポレイション | Method for forming catalyst coating membrane and membrane electrode assembly, membrane mounted on a frame and mask |
-
1999
- 1999-01-27 JP JP11018316A patent/JP2000223134A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1341249A1 (en) * | 2000-11-21 | 2003-09-03 | Nok Corporation | Constituent part for fuel cell |
| US7226685B2 (en) | 2000-11-21 | 2007-06-05 | Nok Corporation | Constituent part for fuel cell |
| EP1341249A4 (en) * | 2000-11-21 | 2007-08-29 | Nok Corp | Constituent part for fuel cell |
| JP2006156036A (en) * | 2004-11-26 | 2006-06-15 | Nissan Motor Co Ltd | Assembly apparatus for membrane electrode assembly, and assembly method of membrane electrode assembly |
| JP2010504618A (en) * | 2006-09-22 | 2010-02-12 | キャボット コーポレイション | Method for forming catalyst coating membrane and membrane electrode assembly, membrane mounted on a frame and mask |
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