JP2002289207A - Manufacturing method for hydrogen ion conductive polymer membrane with catalyst layer for fuel cell - Google Patents

Manufacturing method for hydrogen ion conductive polymer membrane with catalyst layer for fuel cell

Info

Publication number
JP2002289207A
JP2002289207A JP2001088676A JP2001088676A JP2002289207A JP 2002289207 A JP2002289207 A JP 2002289207A JP 2001088676 A JP2001088676 A JP 2001088676A JP 2001088676 A JP2001088676 A JP 2001088676A JP 2002289207 A JP2002289207 A JP 2002289207A
Authority
JP
Japan
Prior art keywords
conductive polymer
hydrogen ion
ion conductive
catalyst layer
polymer membrane
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
Application number
JP2001088676A
Other languages
Japanese (ja)
Inventor
Hiroaki Matsuoka
広彰 松岡
Susumu Kobayashi
晋 小林
Yoshihiro Hori
堀　　喜博
Kazuhito Hado
一仁 羽藤
Masato Hosaka
正人 保坂
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Priority to JP2001088676A priority Critical patent/JP2002289207A/en
Priority to PCT/JP2002/002321 priority patent/WO2002075834A1/en
Priority to US10/296,426 priority patent/US20030078157A1/en
Priority to KR10-2002-7014726A priority patent/KR100443107B1/en
Priority to EP02702919A priority patent/EP1357620A4/en
Publication of JP2002289207A publication Critical patent/JP2002289207A/en
Pending legal-status Critical Current

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

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method for a hydrogen ion conductive polymer membrane with a catalyst layer for a fuel cell without causing a wrinkle or looseness of the hydrogen ion conductive polymer membrane in a machining process or in handling, damage such as a pin hole or micro-crack thereof, or a crack, wear or pollution of the catalyst layer. SOLUTION: This manufacturing method comprises: a process for laminating the hydrogen ion conductive polymer membrane on a first shape keeping film; a process for forming a first catalyst layer on the hydrogen ion conductive polymer membrane; a process for laminating a second shape keeping film on the hydrogen ion conductive polymer membrane with the first catalyst layer formed; a process for peeling the first shape keeping film from the hydrogen ion conductive polymer membrane; and a process for forming a second catalyst layer on the hydrogen ion conductive polymer membrane exposed by the peeling.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、燃料電池に用いる
触媒層付き水素イオン伝導性高分子膜の製造方法に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydrogen ion conductive polymer membrane with a catalyst layer for use in a fuel cell.

【０００２】[0002]

【従来の技術】燃料電池に使用される水素イオン伝導性
高分子膜は、非常に膜厚が薄いために、単体の水素イオ
ン伝導性高分子膜上に触媒層を形成することは極めて困
難である。通常、触媒層は水素イオン伝導性高分子膜の
中央部分に触媒と水または有機溶剤などの溶剤を含有す
る触媒ペーストを塗布し乾燥することにより形成され
る。この場合、水素イオン伝導性高分子膜は、溶剤の付
着と揮発により膨潤と収縮を生じる性質があるために、
寸法および形状の変化を引き起こす問題がある。すなわ
ち、水素イオン伝導性高分子膜に溶剤が付着した直後は
若干膨潤し、その溶剤が揮発すると著しく収縮する。そ
の結果、触媒層が形成された時には、水素イオン伝導性
高分子膜に５〜１０％程度の大きな収縮が起こる。2. Description of the Related Art It is extremely difficult to form a catalyst layer on a single hydrogen ion conductive polymer membrane because the hydrogen ion conductive polymer membrane used in a fuel cell is very thin. is there. Usually, the catalyst layer is formed by applying a catalyst paste containing a catalyst and a solvent such as water or an organic solvent to the central portion of the proton conductive polymer membrane and drying the paste. In this case, because the hydrogen ion conductive polymer membrane has the property of swelling and shrinking due to the adhesion and volatilization of the solvent,
There is a problem that causes a change in size and shape. That is, the solvent slightly swells immediately after the solvent adheres to the proton conductive polymer membrane, and contracts significantly when the solvent volatilizes. As a result, when the catalyst layer is formed, the hydrogen ion conductive polymer membrane undergoes a large shrinkage of about 5 to 10%.

【０００３】この現象により、触媒層が形成された水素
イオン伝導性高分子膜の中央部分は著しく収縮し、触媒
層が形成されていない周縁部分は全く収縮しないため、
結果的に水素イオン伝導性高分子膜の周縁部分には大き
な皺あるいは弛みが発生することになる。この皺あるい
は弛みは、燃料電池製造のための後の工程、すなわち触
媒層付き水素イオン伝導性高分子膜、カーボンペーパー
およびガスケットを加熱状態で加圧により結合して電解
質膜電極接合体を作製する工程において、ガスケットの
シールが不完全になったり、皺が折れ曲がって重なり、
水素イオン伝導性高分子膜自体にマイクロクラックが発
生したりする。そのような電解質膜電極接合体を用いる
と、供給ガスのリークが発生して、電池特性の劣化を招
くなどの問題がある。[0003] Due to this phenomenon, the central portion of the proton conductive polymer membrane on which the catalyst layer is formed contracts significantly, and the peripheral portion where the catalyst layer is not formed does not contract at all.
As a result, large wrinkles or slacks occur at the peripheral portion of the hydrogen ion conductive polymer membrane. This wrinkle or looseness is produced in a later step for manufacturing the fuel cell, that is, the hydrogen ion conductive polymer membrane with the catalyst layer, the carbon paper and the gasket are bonded under pressure in a heated state to produce an electrolyte membrane electrode assembly. In the process, the gasket seal is incomplete, wrinkles are bent and overlapped,
Microcracks are generated in the proton conductive polymer membrane itself. When such an electrolyte membrane electrode assembly is used, there is a problem that a leak of supply gas occurs, which causes deterioration of battery characteristics.

【０００４】この水素イオン伝導性高分子膜は、通常２
０〜５０μｍ程度の薄い膜であり、しかも膜自体の機械
的強度も不十分なため、単体で機械的加工を行うことは
困難である。水素イオン伝導性高分子膜は、機械的加工
時の引張り荷重により伸びたり、不用意な折り曲げによ
りマイクロクラックあるいはピンホールが発生したり、
さらにはせん断応力により簡単に切断されるなどの問題
がある。これらの問題を回避するためには、取り扱いに
厳重な注意をはらうことが必要とされ、作業効率の大幅
な低下を余儀なくされる。従って、事実上は工程中での
水素イオン伝導性高分子膜の何らかの損傷なしに、触媒
層付き水素イオン伝導性高分子膜を作製することは至難
である。[0004] This hydrogen ion conductive polymer membrane is usually 2
Since the film is a thin film having a thickness of about 0 to 50 μm and the mechanical strength of the film itself is insufficient, it is difficult to perform mechanical processing by itself. The hydrogen ion conductive polymer membrane expands due to tensile load during mechanical processing, generates microcracks or pinholes due to careless bending,
In addition, there is a problem that the sheet is easily cut by shear stress. In order to avoid these problems, strict attention must be paid to handling, and the working efficiency must be greatly reduced. Therefore, it is practically difficult to produce a hydrogen ion conductive polymer membrane with a catalyst layer without any damage to the hydrogen ion conductive polymer membrane during the process.

【０００５】特開平１０−６４５７４号公報には、予め
別のフィルム上に形成した２つの触媒層を、水素イオン
伝導性高分子膜の両面に重ね合わせてローラーで加熱し
ながら加圧して両面に触媒層を転写する方法が開示され
ている。この方法によれば、前記の溶剤による水素イオ
ン伝導性高分子膜の膨潤および収縮を防ぐことができ、
優れた量産性も得られる。しかし、水素イオン伝導性高
分子膜を単体で取り扱いながらロールで搬送する点に大
きな問題がある。すなわち使用する水素イオン伝導性高
分子膜の機械的強度が不十分なために、ロール搬送のと
きにかかるテンションにより水素イオン伝導性高分子膜
にマイクロクラックが発生したり、場合によっては破断
することもある。これを防止するために、水素イオン伝
導性高分子膜自体に搬送用のガイド穴を設けるなどの機
械加工を施しても、膜が薄いためにこの穴が歪んだり、
あるいは破れてしまってガイド穴の役目を十分に果たす
ことができない。Japanese Patent Application Laid-Open No. H10-64574 discloses that two catalyst layers previously formed on another film are superposed on both surfaces of a hydrogen ion conductive polymer membrane and pressurized while being heated with a roller to be applied to both surfaces. A method for transferring a catalyst layer is disclosed. According to this method, it is possible to prevent the swelling and shrinkage of the proton conductive polymer membrane due to the solvent,
Excellent mass productivity is also obtained. However, there is a major problem in that the hydrogen ion conductive polymer membrane is transported by a roll while being handled alone. In other words, due to insufficient mechanical strength of the hydrogen ion conductive polymer membrane used, micro-cracks may occur in the hydrogen ion conductive polymer membrane due to the tension applied during roll conveyance, and in some cases, the membrane may break. There is also. In order to prevent this, even if mechanical processing such as providing a guide hole for transport in the proton conductive polymer membrane itself is performed, this hole is distorted because the membrane is thin,
Or, it is broken and cannot fully fulfill the role of the guide hole.

【０００６】さらにこの方法では、加熱されたローラー
で水素イオン伝導性高分子膜を挟んで触媒層を転写する
ので、局部的な熱ストレスにより皺や弛みなどが発生
し、さらにはテンションと熱の影響により、水素イオン
伝導性高分子膜が伸びて位置ずれを起こし易い。また、
両面に触媒層を転写した後の水素イオン伝導性高分子膜
をロール状に巻き取る際に、触媒層にクラックや磨耗が
発生したり、アノード用とカソード用の異なる仕様の触
媒層同士が接触して双方の触媒層が汚染する問題が発生
する。これらの問題により、従来の製造方法による触媒
層付き水素イオン伝導性高分子膜を用いた燃料電池で
は、満足すべき電池特性を得ることはできなかった。Further, in this method, since the catalyst layer is transferred with the hydrogen ion conductive polymer membrane sandwiched between heated rollers, wrinkles and looseness are generated due to local thermal stress, and furthermore, tension and heat are not generated. Due to the influence, the proton conductive polymer membrane is likely to be stretched to cause positional displacement. Also,
When the hydrogen ion conductive polymer membrane after transferring the catalyst layer on both sides is wound into a roll, cracks and wear occur on the catalyst layer, and catalyst layers of different specifications for anode and cathode contact each other. As a result, there is a problem that both catalyst layers are contaminated. Due to these problems, satisfactory fuel cell characteristics cannot be obtained in a fuel cell using a hydrogen ion conductive polymer membrane with a catalyst layer by a conventional manufacturing method.

【０００７】[0007]

【発明が解決しようとする課題】本発明は、上記の問題
を解決し、加工工程や取扱い中における水素イオン伝導
性高分子膜の皺や弛みなどの損傷、および触媒層のクラ
ックや摩耗などが発生しない燃料電池用触媒層付き水素
イオン伝導性高分子膜の製造方法を提供することを目的
とする。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems and reduces damage such as wrinkling and loosening of the hydrogen ion conductive polymer membrane during processing and handling, and cracks and abrasion of the catalyst layer. An object of the present invention is to provide a method for producing a hydrogen ion conductive polymer membrane with a catalyst layer for a fuel cell, which does not generate any fuel cell.

【０００８】[0008]

【課題を解決するための手段】本発明の燃料電池用触媒
層付き水素イオン伝導性高分子膜の製造方法は、第１の
形状保持フィルムの一方の面に水素イオン伝導性高分子
膜を積層する工程（１）、前記第１の形状保持フィルム
に積層された水素イオン伝導性高分子膜上に第１の触媒
層を形成する工程（２）、前記第１の触媒層を形成した
水素イオン伝導性高分子膜の第１の触媒層側の面に第２
の形状保持フィルムを結合する工程（３）、前記第２の
形状保持フィルムと結合した水素イオン伝導性高分子膜
から前記第１の形状保持フィルムを剥離する工程
（４）、および前記第１の形状保持フィルムを剥離して
露出させた水素イオン伝導性高分子膜上に第２の触媒層
を形成する工程（５）を有することを特徴とするもので
ある。The method for producing a hydrogen ion conductive polymer membrane with a catalyst layer for a fuel cell according to the present invention is characterized in that a hydrogen ion conductive polymer membrane is laminated on one surface of a first shape retention film. (1) forming a first catalyst layer on a hydrogen ion conductive polymer film laminated on the first shape retention film (2); and forming hydrogen ions on the first catalyst layer. The second surface of the conductive polymer membrane on the side of the first catalyst layer
(3) bonding the shape maintaining film, (4) separating the first shape maintaining film from the hydrogen ion conductive polymer membrane bonded to the second shape maintaining film, and (1) The method is characterized by comprising a step (5) of forming a second catalyst layer on the hydrogen ion conductive polymer membrane exposed by peeling off the shape retaining film.

【０００９】[0009]

【発明の実施の形態】本発明の燃料電池用触媒層付き水
素イオン伝導性高分子膜の製造方法において、第１の形
状保持フィルムの一方の面に水素イオン伝導性高分子膜
を積層する工程（１）は、第１の形状保持フィルムと水
素イオン伝導性高分子膜を重ね合わせ、これを熱板ある
いは加熱されたローラーで加圧して結合する工法をとる
ことができる。例えば、第１の形状保持フィルムと、予
めキャスト法などで水素イオン伝導性高分子膜が形成さ
れた支持フィルムの水素イオン伝導性高分子膜側の面と
を加熱状態で加圧して結合させた後、支持フィルムを剥
離するいわゆる転写法を採ることが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION In the method for producing a hydrogen ion conductive polymer membrane with a catalyst layer for a fuel cell according to the present invention, a step of laminating a hydrogen ion conductive polymer membrane on one surface of a first shape retaining film. In (1), a method can be adopted in which the first shape-retaining film and the hydrogen ion conductive polymer film are superimposed and bonded together by pressing with a hot plate or a heated roller. For example, the first shape retention film and the surface of the support film on which the hydrogen ion conductive polymer membrane was formed in advance by a casting method or the like on the side of the hydrogen ion conductive polymer membrane were pressurized and bonded in a heated state. Thereafter, it is preferable to employ a so-called transfer method of peeling the support film.

【００１０】本発明において使用する水素イオン伝導性
高分子膜は、例えば、パーフルオロカーボンスルホン酸
などの水素イオン伝導性高分子電解質からなる膜であ
る。燃料電池用水素イオン伝導性高分子膜としては、膜
厚２０〜５０μｍ前後と非常に薄い膜が支持フィルムに
接合されたものが、すでに市販され、使用されている。
今後さらに水素イオン伝導性高分子膜のイオン伝導性を
高めて電池特性を向上させるために、水素イオン伝導性
高分子膜は一層薄膜化する傾向がある。The hydrogen ion conductive polymer membrane used in the present invention is, for example, a membrane made of a hydrogen ion conductive polymer electrolyte such as perfluorocarbon sulfonic acid. As a hydrogen ion conductive polymer membrane for a fuel cell, a membrane in which a very thin membrane having a thickness of about 20 to 50 μm is bonded to a support film has already been marketed and used.
In the future, in order to further enhance the ion conductivity of the hydrogen ion conductive polymer membrane to improve the battery characteristics, the hydrogen ion conductive polymer membrane tends to be thinner.

【００１１】また前記工程（１）は、水素イオン伝導性
高分子電解質を含む液を第１の形状保持フィルム上に塗
布した後、乾燥して水素イオン伝導性高分子膜を形成す
るいわゆるキャスト法を採っても良い。水素イオン伝導
性高分子電解質を含む液は、水素イオン伝導性高分子膜
と同じ成分の高分子電解質を所定の溶剤に分散あるいは
溶解させたものであり、塗膜中の溶剤を揮発させて除去
することにより水素イオン伝導性高分子膜を得ることが
できる。In the step (1), a so-called casting method for forming a hydrogen ion conductive polymer film by applying a liquid containing a hydrogen ion conductive polymer electrolyte on a first shape-retaining film and then drying the solution is dried. May be taken. The solution containing the hydrogen ion conductive polymer electrolyte is obtained by dispersing or dissolving a polymer electrolyte of the same component as the hydrogen ion conductive polymer membrane in a predetermined solvent, and removing the solvent in the coating by volatilizing it. By doing so, a proton conductive polymer membrane can be obtained.

【００１２】本発明の燃料電池用触媒層付き水素イオン
伝導性高分子膜の製造方法において、水素イオン伝導性
高分子膜上に第１あるいは第２の触媒層を形成する工程
（２）および（５）は、触媒ペーストを水素イオン伝導
性高分子膜上に印刷あるいは塗布した後、乾燥して触媒
層を形成する工程であることが好ましい。触媒ペースト
は、触媒の他に水素イオン伝導性高分子膜と同じ成分の
水素イオン伝導性高分子電解質を溶剤に分散あるいは溶
解させ、必要に応じて界面活性剤などの添加剤の少量を
混合して調製することができる。In the method for producing a hydrogen ion conductive polymer membrane with a catalyst layer for a fuel cell according to the present invention, steps (2) and (2) of forming a first or second catalyst layer on the hydrogen ion conductive polymer membrane Step 5) is preferably a step of forming a catalyst layer by printing or applying the catalyst paste on the hydrogen ion conductive polymer film and then drying the catalyst paste. For the catalyst paste, besides the catalyst, a hydrogen ion conductive polymer electrolyte of the same component as the hydrogen ion conductive polymer membrane is dispersed or dissolved in a solvent, and if necessary, a small amount of an additive such as a surfactant is mixed. Can be prepared.

【００１３】触媒層に含まれる触媒は電極反応を円滑に
行わせるためのもので、貴金属触媒をカーボン微粒子の
表面に担持したものである。通常、アノード側の触媒に
はＰｔ−Ｒｕ合金が表面に担持されたカーボン微粒子が
用いられる。Ｐｔ−Ｒｕ合金を用いることにより、燃料
ガスに含まれる微量の一酸化炭素ガスによる触媒被毒を
防止することができる。カソード側の触媒にはＰｔが表
面に担持されたカーボン微粒子が用いられる。The catalyst contained in the catalyst layer is for making the electrode reaction proceed smoothly, and is a catalyst in which a noble metal catalyst is supported on the surface of carbon fine particles. Usually, carbon fine particles having a Pt—Ru alloy supported on the surface are used as the catalyst on the anode side. By using the Pt-Ru alloy, catalyst poisoning by a trace amount of carbon monoxide gas contained in the fuel gas can be prevented. For the catalyst on the cathode side, carbon fine particles having Pt supported on the surface are used.

【００１４】触媒層に含まれる水素イオン伝導性高分子
電解質は、触媒微粒子間および水素イオン伝導性高分子
膜と触媒微粒子の間に介在させて、電極反応をより円滑
に行わせるために添加するものである。所定の溶剤に水
素イオン伝導性高分子電解質を予め分散あるいは溶解さ
せた液体がすでに市販されている。触媒ペーストの溶剤
には、通常の塗布用あるいは印刷用のペーストに用いら
れる比較的低沸点あるいは低分子量の溶剤、例えば、水
（望ましくはイオン交換水あるいは純水）、エタノー
ル、ｎ−プロパノール、イソプロピルアルコール、ｎ−
ブタノール、２−ブタノール、ｔｅｒｔ−ブタノールな
どの第１級〜第３級アルコール、それらの誘導体、およ
びエーテル系、エステル系、フッ素系などの有機溶剤よ
りなる群から選ばれた少なくとも一種を使用することが
できる。The hydrogen ion conductive polymer electrolyte contained in the catalyst layer is interposed between the catalyst fine particles and between the hydrogen ion conductive polymer membrane and the catalyst fine particles, and is added for smoother electrode reaction. Things. Liquids in which a hydrogen ion conductive polymer electrolyte is dispersed or dissolved in a predetermined solvent in advance are already commercially available. As the solvent for the catalyst paste, a solvent having a relatively low boiling point or a low molecular weight, such as water (preferably ion-exchanged water or pure water), ethanol, n-propanol, or isopropyl, which is used for ordinary coating or printing pastes, is used. Alcohol, n-
Use of at least one selected from the group consisting of primary to tertiary alcohols such as butanol, 2-butanol, and tert-butanol, derivatives thereof, and organic solvents such as ethers, esters, and fluorines. Can be.

【００１５】上記の溶剤は、水素イオン伝導性高分子電
解質の析出や分散状態の低下がないように十分な溶解度
が必要である。また、短時間で効率よく触媒層を形成さ
せるためには適切な沸点および蒸気圧を有する溶剤を選
定する必要がある。溶剤の沸点が低くかつ蒸気圧が高い
場合には、速く乾燥し過ぎて触媒ペーストの連続的な印
刷や塗布が困難となり、沸点が高くかつ蒸気圧が低い場
合には、塗膜の乾燥に長時間を要する。The above-mentioned solvent needs to have a sufficient solubility so as not to cause precipitation of the proton conductive polymer electrolyte or decrease in the dispersion state. Further, in order to efficiently form a catalyst layer in a short time, it is necessary to select a solvent having an appropriate boiling point and vapor pressure. If the solvent has a low boiling point and the vapor pressure is high, the catalyst paste will dry too quickly, making continuous printing and application of the catalyst paste difficult.If the solvent has a high boiling point and a low vapor pressure, it will take a long time to dry the coating film. Takes time.

【００１６】水素イオン伝導性高分子膜上に触媒ペース
トの塗膜を形成する方法としては、スクリーン印刷、グ
ラビア印刷、凸版印刷、平版印刷などの印刷法、あるい
はドクターブレード塗工、ロールコーター塗工、キャス
トコータ、スプレー塗工、カーテンコータ、静電塗工な
どの塗布法を採ることができる。これらの印刷法および
塗布法は、形状保持フィルムに結合された一枚一枚の水
素イオン伝導性高分子膜に個別の触媒層を形成する場
合、および形状保持フィルムに結合された水素イオン伝
導性高分子膜をロール方式で供給しながら、触媒層を水
素イオン伝導性高分子膜上に連続的に形成して巻き取る
場合の双方に適用することができる。As a method of forming a coating film of the catalyst paste on the hydrogen ion conductive polymer membrane, printing methods such as screen printing, gravure printing, letterpress printing, lithographic printing, doctor blade coating, roll coater coating are used. , A coat coater, a spray coater, a curtain coater, an electrostatic coater and the like. These printing methods and coating methods are used for forming individual catalyst layers on each hydrogen ion conductive polymer membrane bonded to the shape retention film, and for hydrogen ion conductivity bonding to the shape retention film. The present invention can be applied to both the case where the catalyst layer is continuously formed on the proton conductive polymer membrane while the polymer membrane is supplied by a roll method and the film is wound.

【００１７】触媒層中に含まれるカーボン微粒子に付着
した貴金属（ＰｔあるいはＰｔ−Ｒｕ合金）の量は、通
常０．２〜０．４ｍｇ／ｃｍ2程度に管理する必要があ
る。上記の印刷法あるいは塗布法を用いれば、この付着
量の管理を容易に行うことができる。例えばスクリーン
印刷では印刷版のメッシュ、乳剤の厚み、印刷用のスキ
ージ、印刷時の加圧力などの最適化により管理すること
ができる。前記触媒ペースト中の触媒の粒子径、触媒の
添加量、溶剤組成などの最適化、および触媒ペーストの
粘度の調整などを行うことにより、さらに高精度な触媒
付着量の制御と管理ができる。The amount of the noble metal (Pt or Pt-Ru alloy) adhering to the fine carbon particles contained in the catalyst layer usually needs to be controlled to about 0.2 to 0.4 mg / cm 2 . If the above-mentioned printing method or coating method is used, it is possible to easily control the amount of adhesion. For example, in screen printing, it can be managed by optimizing the mesh of the printing plate, the thickness of the emulsion, the squeegee for printing, the pressing force during printing, and the like. By optimizing the particle size of the catalyst in the catalyst paste, the amount of the catalyst added, the composition of the solvent, and the like, and adjusting the viscosity of the catalyst paste, control and management of the catalyst adhesion amount with higher accuracy can be performed.

【００１８】本発明の燃料電池用触媒層付き水素イオン
伝導性高分子膜の製造方法における形状保持フィルムと
しては、例えば、ポリエチレンテレフタレート、ポリプ
ロピレン、ポリエーテルイミド、ポリイミド、フッ素樹
脂など、ラミネート加工時に熱変形しない耐熱性を有す
るフィルムであれば特に限定することなく用いることが
できる。これらの形状保持フィルムの中でも、熱可塑性
樹脂からなる膜厚５０〜５００μｍのフィルム、とりわ
け膜厚１００〜３００μｍのフィルムを用いることが好
ましい。Examples of the shape-retaining film in the method for producing a hydrogen ion conductive polymer membrane with a catalyst layer for a fuel cell of the present invention include, for example, polyethylene terephthalate, polypropylene, polyetherimide, polyimide, fluororesin, etc. Any film having heat resistance that does not deform can be used without particular limitation. Among these shape maintaining films, it is preferable to use a film made of a thermoplastic resin and having a thickness of 50 to 500 μm, particularly a film having a thickness of 100 to 300 μm.

【００１９】形状保持フィルムの膜厚が５０μｍより薄
いと機械的強度が不十分なため工程中で水素イオン伝導
性高分子膜を保持する能力が不足し、膜厚が５００μｍ
より厚いとロール巻き取りが困難になり量産性が低下す
る。形状保持フィルムには、必要に応じて印刷あるいは
塗布部位の位置精度を高めるための位置決め用あるいは
ロール搬送用のガイド穴を設けても良い。さらに形状保
持フィルムとして、熱的、化学的な安定性が比較的優れ
たものを使用すれば、加工工程中に損傷を受けることが
ないので再利用することができる。If the thickness of the shape-retaining film is less than 50 μm, the mechanical strength is insufficient and the ability to hold the hydrogen ion conductive polymer film in the process is insufficient, and the thickness is 500 μm.
If it is thicker, it becomes difficult to wind up the roll, and mass productivity is reduced. The shape retaining film may be provided with a guide hole for positioning or roll conveyance for improving the positional accuracy of the printing or application site as needed. Further, if a film having relatively excellent thermal and chemical stability is used as the shape retaining film, the film is not damaged during the processing step and can be reused.

【００２０】以上の本発明の製造方法における各工程を
図１〜６によって説明する。まず、第１の形状保持フィ
ルム２の一方の面に水素イオン伝導性高分子膜１を積層
する工程（１）により、図１に示す中間体３を形成す
る。中間体３を形成する方法として、第１の形状保持フ
ィルムと、予め形成された水素イオン伝導性高分子膜を
重ね合わせ、これを熱板あるいは加熱されたローラーで
加圧して結合する工法、あるいは水素イオン伝導性高分
子電解質と溶剤を含む液を第１の形状保持フィルムの片
面に塗布し乾燥して水素イオン伝導性高分子膜を形成す
る工法を採ることができる。次に前記中間体３の水素イ
オン伝導性高分子膜１上に、第１の触媒層用の触媒ペー
ストを塗布し乾燥して第１の触媒層４ａを形成する工程
（２）により、図２に示す中間体５を形成する。Each step in the above-described manufacturing method of the present invention will be described with reference to FIGS. First, the intermediate 3 shown in FIG. 1 is formed by the step (1) of laminating the hydrogen ion conductive polymer membrane 1 on one surface of the first shape retention film 2. As a method of forming the intermediate 3, a first shape maintaining film and a preformed hydrogen ion conductive polymer film are superimposed, and a method of bonding them by pressing with a hot plate or a heated roller, or A method of forming a hydrogen ion conductive polymer membrane by applying a liquid containing a hydrogen ion conductive polymer electrolyte and a solvent to one surface of the first shape maintaining film and drying the liquid is used. Next, a step (2) of applying a catalyst paste for a first catalyst layer on the hydrogen ion conductive polymer membrane 1 of the intermediate 3 and drying it to form a first catalyst layer 4a is performed, as shown in FIG. To form Intermediate 5.

【００２１】次いで、中間体５の水素イオン伝導性高分
子膜１の第１の触媒層４ａ側の面と第２の形状保持フィ
ルム６を重ね合わせ、これを熱板あるいは加熱されたロ
ーラーで加熱するいわゆるホットプレス工法により、中
間体５と第２の形状保持フィルム６を結合する。この工
程（３）により図３に示す中間体７が形成される。次に
中間体７の水素イオン伝導性高分子膜１から第１の形状
保持フィルム２を剥離する工程（４）により水素イオン
伝導性高分子膜１を露出させる。露出させた水素イオン
伝導性高分子膜１上に第２の触媒層用の触媒ペーストを
塗布し、乾燥して第２の触媒層４ｂを形成する。この工
程（５）により、図４に示すような、第２の形状保持フ
ィルム６と結合された触媒層付き水素イオン伝導性高分
子膜８が構成される。Next, the surface of the hydrogen ion conductive polymer membrane 1 of the intermediate 5 on the first catalyst layer 4a side and the second shape retention film 6 are overlapped, and this is heated by a hot plate or a heated roller. The intermediate 5 and the second shape maintaining film 6 are joined by a so-called hot press method. By this step (3), the intermediate 7 shown in FIG. 3 is formed. Next, the hydrogen ion conductive polymer film 1 is exposed in the step (4) of peeling the first shape retention film 2 from the hydrogen ion conductive polymer film 1 of the intermediate 7. The catalyst paste for the second catalyst layer is applied on the exposed proton conductive polymer membrane 1 and dried to form the second catalyst layer 4b. By this step (5), a hydrogen ion conductive polymer membrane 8 with a catalyst layer bonded to the second shape maintaining film 6 is formed as shown in FIG.

【００２２】以上の本発明により、形状保持フィルムで
保持された水素イオン伝導性高分子膜上に触媒層を形成
することで、触媒ペーストに含まれる溶剤が触媒層形成
時に水素イオン伝導性高分子膜に付着しても、水素イオ
ン伝導性高分子膜が形状保持フィルムで固定されている
ために膨潤および収縮がほとんど発生することはなく、
水素イオン伝導性高分子膜の中央部の収縮、周縁部の
皺、弛みピンホールおよびマイクロクラックなどの損傷
を効果的に防止できる。According to the present invention, the catalyst layer is formed on the hydrogen ion conductive polymer film held by the shape holding film, so that the solvent contained in the catalyst paste can be used when forming the catalyst layer. Even if attached to the membrane, swelling and shrinkage hardly occur because the proton conductive polymer membrane is fixed with the shape retention film,
Damage such as shrinkage at the center of the proton conductive polymer membrane, wrinkles at the peripheral edge, loose pinholes, and microcracks can be effectively prevented.

【００２３】さらに、前記の各工程（１）〜（５）で
は、常に第１および第２の触媒層および水素イオン伝導
性高分子膜は直接的あるいは間接的に第１あるいは第２
の形状保持フィルムで保持されている。これによって、
各工程での引っ張り荷重などによる各触媒層および水素
イオン伝導性高分子膜の伸び、ピンホール、クラックな
どの損傷を防止できる。さらに、工程間の搬送あるいは
保管のために各中間体あるいは触媒層付き水素イオン伝
導性高分子膜などの仕掛品をロール状に巻き取る場合に
は、水素イオン伝導性高分子膜相互間および触媒層相互
間には第１あるいは第２の形状保持フィルムが必ず介在
した状態で巻き取ることができる。これにより、工程間
の搬送および保管中に発生する触媒層と水素イオン伝導
性高分子膜のクラック、剥離、磨耗などの損傷防止、お
よびアノード側とカソード側の触媒層の接触による双方
の触媒層の汚染なども効果的に防止できる。Further, in each of the above steps (1) to (5), the first and second catalyst layers and the hydrogen ion conductive polymer membrane are always directly or indirectly connected to the first or second catalyst layer.
Is held by the shape holding film. by this,
Damage such as elongation, pinholes, cracks, etc. of each catalyst layer and hydrogen ion conductive polymer membrane due to a tensile load in each step can be prevented. In addition, when winding up a work-in-progress such as a hydrogen ion conductive polymer membrane with a catalyst layer for transport or storage between processes, the intermediate between the hydrogen ion conductive polymer membranes and the catalyst are required. The film can be wound up with the first or second shape-retaining film always interposed between the layers. This prevents damage such as cracking, peeling, and abrasion of the catalyst layer and the hydrogen ion conductive polymer film generated during transportation and storage between processes, and both catalyst layers by contact between the anode and cathode catalyst layers Pollution can be effectively prevented.

【００２４】上記の第２の形状保持フィルム６と結合し
た触媒層付き水素イオン伝導性高分子膜８は、後の工程
で電解質層電極接合体を作製する場合に、第２の触媒層
側にカーボンペーパー製の拡散層とガスケットを加熱状
態で加圧するなどにより接合する際などに、第２の形状
保持フィルムが触媒層付き水素イオン伝導性高分子膜を
保持して変形や破損を防ぐ役割を果たすことができる。
このような特徴を有するので、触媒層付き水素イオン伝
導性高分子膜８は、本発明により作製される触媒層付き
水素イオン伝導性高分子膜としての好ましい形態の一つ
である。The hydrogen ion-conductive polymer membrane with a catalyst layer 8 bonded to the second shape maintaining film 6 is provided on the side of the second catalyst layer when an electrolyte layer electrode assembly is manufactured in a later step. When joining the diffusion layer made of carbon paper and the gasket by applying pressure in a heated state, the second shape-retaining film serves to hold the hydrogen ion conductive polymer membrane with the catalyst layer and prevent deformation and breakage. Can be fulfilled.
Because of these features, the hydrogen ion conductive polymer membrane with a catalyst layer 8 is one of the preferred forms as the hydrogen ion conductive polymer membrane with a catalyst layer produced according to the present invention.

【００２５】また、本発明における工程（１）〜（５）
を終えた後、上記の第２の形状保持フィルム６と結合し
た触媒層付き水素イオン伝導性高分子膜８から第２の形
状保持フィルム６を剥離する工程（６）をさらに設ける
ことにより、図５に示す触媒層付き水素イオン伝導性高
分子膜９を作製することができる。この触媒層付き水素
イオン伝導性高分子膜９を後の電解質層電極接合体を作
製する工程に用いた場合には、第１および第２の触媒層
４ａおよび４ｂのそれぞれの側にそれぞれの拡散層をホ
ットプレスにより同時に結合させることができる。この
ように、触媒層付き水素イオン伝導性高分子膜９は、ア
ノードとカソードを単一操作で同時に形成するために好
都合なので、本発明により作製される触媒層付き水素イ
オン伝導性高分子膜としての好ましい形態の一つであ
る。Further, the steps (1) to (5) in the present invention.
After the step is completed, a step (6) of peeling the second shape holding film 6 from the hydrogen ion conductive polymer membrane with a catalyst layer 8 bonded to the second shape holding film 6 is further provided, whereby 5 can be produced. When the hydrogen ion conductive polymer membrane with a catalyst layer 9 is used in the later step of fabricating the electrolyte layer electrode assembly, the respective diffusion layers are formed on the respective sides of the first and second catalyst layers 4a and 4b. The layers can be bonded together by hot pressing. As described above, the hydrogen ion conductive polymer membrane with a catalyst layer 9 is convenient for simultaneously forming the anode and the cathode in a single operation, so that the hydrogen ion conductive polymer membrane with a catalyst layer produced according to the present invention is used. This is one of preferred embodiments.

【００２６】また、上記の第２の形状保持フィルム６と
結合した触媒層付き水素イオン伝導性高分子膜８の第１
の触媒層４ａ側の面に第３の形状保持フィルム１０を結
合させる工程（７）により、図６に示すような、第２の
形状保持フィルム６および第３の形状保持フィルム１０
と結合した触媒層付き水素イオン伝導性高分子膜１１が
得られる。前記工程（７）では、触媒層付き水素イオン
伝導性高分子膜８の第１の触媒層４ａ側の面に第３の形
状保持フィルム１０を重ね合わせ、これを熱板あるいは
加熱されたローラーで加圧するいわゆるホットプレス法
を採ることが好ましい。第３の形状保持フィルム１０
は、第２の形状保持フィルム６と目視あるいは触覚で識
別できる程度に異なった仕様のものであることが好まし
い。Also, the first hydrogen ion conductive polymer membrane 8 with a catalyst layer bonded to the second shape maintaining film 6
In the step (7) of bonding the third shape holding film 10 to the surface on the side of the catalyst layer 4a, the second shape holding film 6 and the third shape holding film 10 as shown in FIG.
Thus, a hydrogen ion conductive polymer membrane 11 with a catalyst layer bonded to the above is obtained. In the step (7), the third shape retention film 10 is superimposed on the surface of the hydrogen ion conductive polymer membrane with catalyst layer 8 on the side of the first catalyst layer 4a, and this is placed on a hot plate or a heated roller. It is preferable to employ a so-called hot press method in which pressure is applied. Third shape retaining film 10
Is preferably different from the second shape retention film 6 to such an extent that it can be identified visually or tactilely.

【００２７】このように第１の触媒層４ａ側に第２の形
状保持フィルム６、第２の触媒層４ｂ側に第３の形状保
持フィルム１０をそれぞれ結合させた触媒層付き水素イ
オン伝導性高分子膜１１では、水素イオン伝導性高分子
膜１や触媒層４ａおよび４ｂが形状保持フィルム６およ
び１０で表面が保護されている。従って、この触媒層付
き水素イオン伝導性高分子膜１１は、触媒層付き水素イ
オン伝導性高分子膜の保管中や取扱中の変質、破損、汚
染などの様々な損傷の発生を防止できる。特にこの触媒
層付き水素イオン伝導性高分子膜１１は、長期間保管、
他の場所への輸送、あるいは梱包などの場合の損傷防止
には極めて有効なので、本発明により作製される触媒層
付き水素イオン伝導性高分子膜としての好ましい形態の
一つである。As described above, the second shape holding film 6 is bonded to the first catalyst layer 4a side, and the third shape holding film 10 is bonded to the second catalyst layer 4b side. In the molecular film 11, the surfaces of the hydrogen ion conductive polymer film 1 and the catalyst layers 4a and 4b are protected by the shape maintaining films 6 and 10. Therefore, the hydrogen ion conductive polymer membrane with a catalyst layer 11 can prevent various damages such as deterioration, breakage, and contamination during storage and handling of the hydrogen ion conductive polymer membrane with a catalyst layer. In particular, the hydrogen ion conductive polymer membrane 11 with a catalyst layer can be stored for a long time,
Since it is extremely effective in preventing damage in the case of transportation to another place or in the case of packing, it is one of the preferable forms as the hydrogen ion conductive polymer membrane with a catalyst layer produced according to the present invention.

【００２８】触媒層４ａおよび４ｂは、貴金属触媒の種
類などの仕様が異なるに拘わらず、外観上は同じ黒色で
殆ど同質なので目視や触覚では識別できない場合が多
い。そのため燃料電池を作製する過程でアノード側触媒
層とカソード側触媒層とを取り違えて扱われる懸念があ
る。この懸念を解消するために、形状保持フィルム６と
形状保持フィルム１０とが目視や触覚で識別できる程度
に異なったものであることは極めて効果的である。その
ためには、例えば、色彩、膜厚、表面の凹凸状態などが
相違した形状保持フィルムや、識別符号を付与した形状
保持フィルムを用いればよい。この場合、先の工程
（４）で剥離した第１の形状保持フィルム２を工程
（７）での第３の形状保持フィルム１０として、再利用
することもできる。Although the catalyst layers 4a and 4b have different specifications such as the type of the noble metal catalyst, the appearance is almost the same black and almost the same, so that it is often impossible to identify them visually or by touch. Therefore, there is a concern that the anode-side catalyst layer and the cathode-side catalyst layer may be interchanged in the process of manufacturing the fuel cell. In order to solve this concern, it is extremely effective that the shape holding film 6 and the shape holding film 10 are different from each other to the extent that they can be visually and tactually distinguished. For this purpose, for example, a shape holding film having different colors, film thicknesses, surface irregularities, or the like, or a shape holding film provided with an identification code may be used. In this case, the first shape retaining film 2 peeled in the previous step (4) can be reused as the third shape retaining film 10 in the step (7).

【００２９】[0029]

【実施例】以下、本発明の燃料電池用触媒層付き水素イ
オン伝導性高分子膜の製造方法を実施例により具体的に
説明する。EXAMPLES The method for producing a hydrogen ion conductive polymer membrane with a catalyst layer for a fuel cell according to the present invention will be specifically described below with reference to examples.

【００３０】《実施例１》図１〜５に示した手順で燃料
電池用触媒層付き水素イオン伝導性高分子膜を作製し
た。まず、次式においてｘ＝５〜１３．５、ｙ≒１００
０、ｍ＝１、ｎ＝２であるパーフルオロカーボンスルホ
ン酸からなる膜厚３０μｍの水素イオン伝導性高分子膜
１を、膜厚１９０μｍのポリエチレンテレフタレートフ
ィルムからなる第１の形状保持フィルム２上に積層して
図１の中間体３を作製した。Example 1 A hydrogen ion conductive polymer membrane with a catalyst layer for a fuel cell was prepared according to the procedure shown in FIGS. First, in the following equation, x = 5-13.5, y ≒ 100
A 30 μm-thick hydrogen ion conductive polymer membrane 1 made of perfluorocarbon sulfonic acid with 0, m = 1 and n = 2 is laminated on a first shape retention film 2 made of a polyethylene terephthalate film having a thickness of 190 μm. Thus, an intermediate 3 of FIG. 1 was produced.

【００３１】[0031]

【化１】 Embedded image

【００３２】上記水素イオン伝導性高分子膜１は、予め
キャスト法により支持フィルム上に形成された水素イオ
ン伝導性高分子膜１と、第１の形状保持フィルム２を重
ね合わせ、これをシリコンゴムでコートされた２本の加
熱ローラーの間で加圧した後、支持フィルムを剥離する
いわゆる転写法により、第１の形状保持フィルム２上に
積層した。ローラーの表面温度１１０℃、搬送速度約１
０ｍｍ／ｓ、加圧力約１ＭＰａとした。The hydrogen ion conductive polymer membrane 1 is formed by laminating a hydrogen ion conductive polymer membrane 1 formed on a support film in advance by a casting method and a first shape maintaining film 2, and forming a silicone rubber. After being pressed between the two heating rollers coated with, the support film was peeled off, and the support film was laminated on the first shape holding film 2 by a so-called transfer method. Roller surface temperature 110 ° C, transport speed about 1
The pressure was 0 mm / s and the pressure was about 1 MPa.

【００３３】中間体３には、そりあるいは変形はほとん
どなく、水素イオン伝導性高分子膜１自体にもマイクロ
クラックあるいはピンホールなどの損傷も観測されなか
った。また水素イオン伝導性高分子膜１と第１の形状保
持フィルム２は、曲率半径（Ｒ）５０ｍｍ程度の折り曲
げに対しても剥がれることはなく、適度に密着してい
た。The intermediate 3 was hardly warped or deformed, and no damage such as microcracks or pinholes was observed on the proton conductive polymer membrane 1 itself. In addition, the hydrogen ion conductive polymer membrane 1 and the first shape retention film 2 did not peel off even when bent with a radius of curvature (R) of about 50 mm, and were in close contact with each other.

【００３４】次にアノード用の触媒ペーストを水素イオ
ン伝導性高分子膜１上にスクリーン印刷し、室温で放置
して溶剤を揮発させることで第１の触媒層４ａ（アノー
ド側触媒層）を形成し、図２に示す中間体５を作製し
た。触媒層４ａ中のカーボン微粒子に付着したＰｔ−Ｒ
ｕ合金の量は０．３ｍｇ／ｃｍ2で、膜厚は約１０μｍ
であった。アノード用の触媒ペーストは、平均粒径２〜
３ｎｍのＰｔ−Ｒｕ合金を５０重量％担持させた平均粒
径５０〜６０ｎｍのカーボンブラック５ｇを触媒として
用い、これにイオン交換水１５ｇを添加して混合した
後、さらにパーフルオロカーボンスルホン酸を９１重量
％含むエタノール溶液３０ｇと溶剤としてイソプロピル
アルコール１０ｇを添加して超音波振動を加えながら混
合して調製した。スクリーン印刷にはステンレス鋼製の
２００メッシュの版とウレタンスキージを使用した。Next, the anode catalyst paste is screen-printed on the hydrogen ion conductive polymer membrane 1 and left at room temperature to evaporate the solvent to form the first catalyst layer 4a (anode-side catalyst layer). Then, Intermediate 5 shown in FIG. 2 was produced. Pt-R adhering to carbon fine particles in catalyst layer 4a
The amount of the u alloy is 0.3 mg / cm 2 and the film thickness is about 10 μm.
Met. The catalyst paste for the anode has an average particle size of 2
After using 5 g of carbon black having an average particle size of 50 to 60 nm carrying 50 wt% of a 3 nm Pt-Ru alloy as a catalyst, adding and mixing 15 g of ion-exchanged water, and further adding 91 wt% of perfluorocarbon sulfonic acid % Of an ethanol solution containing 10% and 10 g of isopropyl alcohol as a solvent were added and mixed while applying ultrasonic vibration. For screen printing, a stainless steel 200 mesh plate and a urethane squeegee were used.

【００３５】次いで、中間体５と第２の形状保持フィル
ム６を重ね合わせ、これをシリコンゴムでコートされた
二本の加熱ローラー間に挿入して加圧し、図３に示す中
間体７を形成した。第２の形状保持フィルム６は、片面
に粗面化処理を施した膜厚１９０μｍのポリエチレンテ
レフタレートフィルムを使用し、粗面化処理されていな
い面を水素イオン伝導性高分子膜１および触媒層４ａと
結合させた。ローラーの表面温度１１０℃、中間体５と
第２の形状保持フィルム６の搬送速度約１０ｍｍ／ｓ、
加圧力約１ＭＰａとした。Next, the intermediate 5 and the second shape-retaining film 6 are superposed, inserted between two heating rollers coated with silicone rubber, and pressed to form the intermediate 7 shown in FIG. did. The second shape maintaining film 6 is a 190 μm-thick polyethylene terephthalate film having one surface subjected to a surface roughening treatment, and the surface not subjected to the surface roughening treatment is used as the hydrogen ion conductive polymer film 1 and the catalyst layer 4a. And combined. The surface temperature of the roller is 110 ° C., the conveyance speed of the intermediate 5 and the second shape maintaining film 6 is about 10 mm / s,
The pressure was about 1 MPa.

【００３６】中間体７には、そりあるいは変形はほとん
どなく、水素イオン伝導性高分子膜１自体にもマイクロ
クラックあるいはピンホールなどの損傷も観測されなか
った。また水素イオン伝導性高分子膜１と第１および第
２の形状保持フィルム２および６は、Ｒ５０ｍｍ程度の
折り曲げに対しても剥がれることなく、適度に密着して
いた。The intermediate 7 was hardly warped or deformed, and no damage such as microcracks or pinholes was observed on the proton conductive polymer membrane 1 itself. Further, the hydrogen ion conductive polymer membrane 1 and the first and second shape maintaining films 2 and 6 did not peel off even when bent about R50 mm, and were in close contact with each other.

【００３７】次いで中間体７から第１の形状保持フィル
ム２を剥離した後に、剥離により露出した水素イオン伝
導性高分子膜１にカソード用の触媒ペーストをスクリー
ン印刷し、室温で放置して溶剤を揮発させた。これによ
り、第２の触媒層４ｂ（カソード側触媒層）を形成し、
図４に示す第２の形状保持フィルム６と結合した触媒層
付き水素イオン伝導性高分子膜８を構成した。スクリー
ン印刷はステンレス鋼製の２００メッシュの版とウレタ
ンスキージを使用して行った。第２の触媒層４ｂ中のカ
ーボン微粒子に付着したＰｔの量は０．３ｍｇ／ｃｍ2
で、膜厚は約１０μｍであった。Next, after the first shape retaining film 2 is peeled off from the intermediate body 7, a catalyst paste for a cathode is screen-printed on the hydrogen ion conductive polymer membrane 1 exposed by the peeling, and the solvent is left at room temperature to remove the solvent. Volatilized. Thereby, the second catalyst layer 4b (cathode side catalyst layer) is formed,
The hydrogen ion conductive polymer membrane 8 with the catalyst layer bonded to the second shape retention film 6 shown in FIG. 4 was formed. Screen printing was performed using a stainless steel 200 mesh plate and a urethane squeegee. The amount of Pt attached to the carbon fine particles in the second catalyst layer 4b is 0.3 mg / cm 2
And the film thickness was about 10 μm.

【００３８】カソード用の触媒ペーストは、触媒として
平均粒径３ｎｍのＰｔを５０重量％担持した平均粒径５
０〜６０ｎｍのカーボンブラック５ｇを用い、これにイ
オン交換水１５ｇを添加混合した後、パーフルオロカー
ボンスルホン酸を９１重量％含むエタノール溶液３０ｇ
と有機溶剤としてイソプロピルアルコール１０ｇを添加
して超音波振動を加えながら混合して調製した。The catalyst paste for the cathode has an average particle size of 5 wt.
After using 5 g of carbon black of 0 to 60 nm and adding and mixing 15 g of ion-exchanged water, 30 g of an ethanol solution containing 91% by weight of perfluorocarbon sulfonic acid was added.
And isopropyl alcohol (10 g) as an organic solvent were added and mixed while applying ultrasonic vibration.

【００３９】次いで第２の形状保持フィルム６と結合し
た触媒層付き水素イオン伝導性高分子膜８から第２の形
状保持フィルム６を剥離して、触媒層付き水素イオン伝
導性高分子膜９を作製した。次に、この触媒層付き水素
イオン伝導性高分子膜９を使用し燃料電池を作製した。
図７はその縦断面図である。触媒層付き水素イオン伝導
性高分子膜９の水素イオン伝導性高分子膜１の両側に形
成した触媒層４ａおよび４ｂの外側に、それぞれガス透
過のための気孔を有するカーボンペーパーからなるアノ
ード用拡散層１３ａおよびカソード用拡散層１３ｂを接
合して、アノード１４ａおよびカソード１４ｂを形成し
た。さらに水素イオン伝導性高分子膜１の周縁部の両側
にガスケット２３を接着して電解質膜電極接合体を形成
した。拡散層１３ａおよび１３ｂのそれぞれの外側に
は、ガス流路１６ａを有するアノード側の導電性セパレ
ータ板１７ａおよびガス流路１６ｂを有するカソード側
の導電性セパレータ板１７を配置した。導電性セパレー
タ板１７ａおよび１７ｂのそれぞれの外側には、冷却水
の流路１８を有する冷却板１９を配置した。Next, the second shape-retaining film 6 is peeled off from the hydrogen ion-conducting polymer film with a catalyst layer 8 bonded to the second shape-retaining film 6, and the hydrogen ion-conducting polymer film with a catalyst layer 9 is removed. Produced. Next, a fuel cell was manufactured using the hydrogen ion conductive polymer membrane 9 with the catalyst layer.
FIG. 7 is a longitudinal sectional view thereof. An anode diffusion made of carbon paper having pores for gas permeation outside the catalyst layers 4a and 4b formed on both sides of the hydrogen ion conductive polymer membrane 1 of the hydrogen ion conductive polymer membrane 9 with a catalyst layer. The anode 13a and the cathode 14b were formed by joining the layer 13a and the cathode diffusion layer 13b. Further, gaskets 23 were bonded to both sides of the periphery of the hydrogen ion conductive polymer membrane 1 to form an electrolyte membrane electrode assembly. Outside each of the diffusion layers 13a and 13b, an anode-side conductive separator plate 17a having a gas passage 16a and a cathode-side conductive separator plate 17 having a gas passage 16b were arranged. Outside each of the conductive separator plates 17a and 17b, a cooling plate 19 having a cooling water channel 18 was arranged.

【００４０】このようにして作製した燃料電池の電池温
度を７５℃に保持し、アノード側に７５℃の露点となる
ように加湿・加温した水素ガスを、またカソード側に６
５℃の露点となるように加湿・加温した空気をそれぞれ
供給した。この電池について水素ガス利用率７０％、空
気利用率４０％、電流密度０．７Ａ／ｃｍ2の条件で放
電を行った。その結果、０．６８Ｖという良好な出力電
圧が得られた。The temperature of the fuel cell thus manufactured was maintained at 75 ° C., and hydrogen gas humidified and heated to a dew point of 75 ° C. was supplied to the anode side, and 6 μm was supplied to the cathode side.
Air humidified and heated to a dew point of 5 ° C. was supplied. The battery was discharged under the conditions of a hydrogen gas utilization rate of 70%, an air utilization rate of 40%, and a current density of 0.7 A / cm 2 . As a result, a favorable output voltage of 0.68 V was obtained.

【００４１】《実施例２》パーフルオロカーボンスルホ
ン酸を９１重量％含むエタノール溶液を第１の形状保持
フィルム２の上に塗布し乾燥するキャスト法により、膜
厚５０μｍのポリプロピレンフィルムからなる第１の形
状保持フィルム２の上に膜厚３０μｍの水素イオン伝導
性高分子膜１を形成し、図１に示す中間体３を作製し
た。キャスト工法は第１の形状保持フィルムの搬送速度
０．７ｍ／ｍｉｎ、刃高さ０．１６ｍｍで３回の重ね塗
りの後、室温放置で乾燥する方法で行った。Example 2 A first shape composed of a 50 μm-thick polypropylene film was formed by a casting method in which an ethanol solution containing 91% by weight of perfluorocarbon sulfonic acid was applied onto the first shape maintaining film 2 and dried. A hydrogen ion conductive polymer membrane 1 having a thickness of 30 μm was formed on the holding film 2 to produce an intermediate 3 shown in FIG. The casting method was a method in which the first shape-retaining film was conveyed three times at a conveying speed of 0.7 m / min and a blade height of 0.16 mm three times, and then dried at room temperature.

【００４２】中間体３はそりあるいは変形はほとんどな
く、水素イオン伝導性高分子膜１自体にもマイクロクラ
ックあるいはピンホールなどの損傷もなかった。また水
素イオン伝導性高分子膜１と第１の形状保持フィルム２
とは、Ｒ５０ｍｍ程度の折り曲げに対しても剥がれるこ
とはなく適度に密着していた。The intermediate 3 hardly warped or deformed, and the hydrogen ion conductive polymer membrane 1 itself did not suffer damage such as microcracks or pinholes. In addition, the hydrogen ion conductive polymer membrane 1 and the first shape maintaining film 2
Means that it did not come off even when bent about R50 mm and was in close contact with it.

【００４３】次に中間体３の水素イオン伝導性高分子膜
１上に、アノード用の触媒ペーストを実施例１と同様の
方法でスクリーン印刷し乾燥することによりアノード側
の触媒層４ａを形成し、図２に示す中間体５を作製し
た。形成した触媒層４ａ中のカーボン微粒子に付着して
いるＰｔ−Ｒｕ合金の量は０．３ｍｇ／ｃｍ2で、膜厚
は約１０μｍであった。アノード用の触媒ペーストは、
イソプロピルアルコールの代わりにｎ−プロパノールを
溶剤として用いた以外は実施例１と同様にして調製し
た。Next, an anode catalyst paste was screen-printed and dried on the hydrogen ion conductive polymer membrane 1 of the intermediate 3 in the same manner as in Example 1 to form an anode-side catalyst layer 4a. The intermediate 5 shown in FIG. 2 was produced. The amount of the Pt—Ru alloy adhering to the carbon fine particles in the formed catalyst layer 4a was 0.3 mg / cm 2 , and the film thickness was about 10 μm. The catalyst paste for the anode is
It was prepared in the same manner as in Example 1 except that n-propanol was used as a solvent instead of isopropyl alcohol.

【００４４】次いで、第２の形状保持フィルム６に膜厚
１００μｍのポリイミドフィルムを使用し、熱板の表面
温度１３０℃、加圧力約５ＭＰａとした以外は実施例１
と同じ方法で図３に示す中間体７を形成した。中間体７
はそりあるいは変形はほとんどなく、また水素イオン伝
導性高分子膜１自体にもマイクロクラックあるいはピン
ホールなどの損傷がなかった。また水素イオン伝導性高
分子膜１と第１および第２の形状保持フィルム２および
６は、Ｒ５０ｍｍ程度の折り曲げに対しても剥がれるこ
とはなく適度に密着していた。Next, Example 1 was repeated except that a polyimide film having a thickness of 100 μm was used as the second shape retaining film 6 and the surface temperature of the hot plate was 130 ° C. and the pressure was about 5 MPa.
Intermediate 7 shown in FIG. 3 was formed in the same manner as described above. Intermediate 7
There was almost no warping or deformation, and there was no damage such as microcracks or pinholes on the proton conductive polymer membrane 1 itself. Further, the hydrogen ion conductive polymer membrane 1 and the first and second shape maintaining films 2 and 6 did not peel off even when bent about R50 mm, and were in close contact with each other.

【００４５】次に、中間体７から第１の形状保持フィル
ム２を剥離して露出した水素イオン伝導性高分子膜１上
にカソード用の触媒ペーストを実施例１と同様にしてス
クリーン印刷し、室温で乾燥して第２の触媒層４ｂを形
成して、図４に示す第２の形状保持フィルム２と結合し
た触媒層付き水素イオン伝導性高分子膜８を作製した。
形成した第２の触媒層４ｂ中のカーボン微粒子に付着し
ているＰｔ量は０．３ｍｇ／ｃｍ2で、膜厚は約１０μ
ｍであった。カソード用の触媒ペーストは、イソプロピ
ルアルコールの代わりにｎ−プロパノールを溶剤として
用いた以外は実施例１と同様にして調製した。Next, the catalyst paste for the cathode was screen-printed on the hydrogen ion conductive polymer membrane 1 exposed by peeling the first shape retaining film 2 from the intermediate body 7 in the same manner as in Example 1. By drying at room temperature to form a second catalyst layer 4b, a hydrogen ion conductive polymer membrane with a catalyst layer 8 bonded to the second shape maintaining film 2 shown in FIG. 4 was produced.
The amount of Pt adhering to the carbon fine particles in the formed second catalyst layer 4b was 0.3 mg / cm 2 , and the film thickness was about 10 μm.
m. The catalyst paste for the cathode was prepared in the same manner as in Example 1 except that n-propanol was used as a solvent instead of isopropyl alcohol.

【００４６】次いで第２の形状保持フィルム２と結合し
た触媒層付き水素イオン伝導性高分子膜８から第２の形
状保持フィルム６を剥離して触媒層付き水素イオン伝導
性高分子膜９を作製した。この触媒層付き水素イオン伝
導性高分子膜９を使用して実施例１と同様の方法で作製
した燃料電池について、実施例１と同様の方法で放電特
性を評価した。その結果、０．６８Ｖという良好な出力
電圧が得られた。Next, the second shape-retaining film 6 is peeled off from the hydrogen ion-conducting polymer film with a catalyst layer 8 bonded to the second shape-retaining film 2 to produce a hydrogen ion-conducting polymer film 9 with a catalyst layer. did. Using the hydrogen ion conductive polymer membrane 9 with the catalyst layer, the discharge characteristics of a fuel cell manufactured in the same manner as in Example 1 were evaluated in the same manner as in Example 1. As a result, a favorable output voltage of 0.68 V was obtained.

【００４７】なお、上記実施例１および２において、第
２の形状保持フィルムと結合した触媒層付き水素イオン
伝導性高分子膜８の触媒層４ｂ側の水素イオン伝導性高
分子膜１上に、第２の形状保持フィルム６と目視や触覚
で識別できる第３の形状保持フィルム１０を結合するこ
とにより、図６に示す第２および第３の形状保持フィル
ムと結合した触媒層付き水素イオン伝導性高分子膜１１
が得られる。この場合、先の工程で一旦剥離した第１の
形状保持フィルム２を第３の形状保持フィルム１０とし
て再利用することもできる。例えば、実施例２では第１
の形状保持フィルム２には無色透明なポリプロピレンフ
ィルム、第２の形状保持フィルム６には茶色で透明なポ
リイミドフィルムという色彩が異なるものを用いたの
で、第１の形状保持フィルム２を第３の形状保持フィル
ム１０として再利用できる。In the above Examples 1 and 2, on the hydrogen ion conductive polymer membrane 1 on the catalyst layer 4b side of the hydrogen ion conductive polymer membrane with a catalyst layer 8 bonded to the second shape retaining film, By connecting the second shape holding film 6 and the third shape holding film 10 that can be visually and tactilely distinguished, the hydrogen ion conductivity with the catalyst layer combined with the second and third shape holding films shown in FIG. Polymer film 11
Is obtained. In this case, the first shape maintaining film 2 once peeled in the previous step can be reused as the third shape maintaining film 10. For example, in the second embodiment, the first
And a transparent polyimide film having a different color, such as a transparent and colorless polypropylene film, was used as the shape maintaining film 2 of the first embodiment. It can be reused as the holding film 10.

【発明の効果】本発明により、水素イオン伝導性高分子
膜に皺、弛み、マイクロクラック、ピンホールなどの損
傷を与えず、さらに触媒層にクラック、摩耗、汚染など
の損傷を与えることなく、燃料電池用触媒層付き水素イ
オン伝導性高分子膜を良好な作業性で製造することがで
きる。According to the present invention, the hydrogen ion conductive polymer membrane is not damaged such as wrinkles, looseness, micro cracks, pinholes, etc., and the catalyst layer is not damaged such as cracks, abrasion, contamination, etc. A hydrogen ion conductive polymer membrane with a catalyst layer for a fuel cell can be manufactured with good workability.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明の実施例における燃料電池用触媒層付き
水素イオン伝導性高分子膜の製造過程の第１の中間体の
縦断面図である。FIG. 1 is a longitudinal sectional view of a first intermediate in a production process of a hydrogen ion conductive polymer membrane with a catalyst layer for a fuel cell in an example of the present invention.

【図２】本発明の実施例における燃料電池用触媒層付き
水素イオン伝導性高分子膜の製造過程の第２の中間体の
縦断面図である。FIG. 2 is a longitudinal sectional view of a second intermediate in the process of producing the hydrogen ion conductive polymer membrane with a catalyst layer for a fuel cell according to an example of the present invention.

【図３】本発明の実施例における燃料電池用触媒層付き
水素イオン伝導性高分子膜の製造過程の第３の中間体の
縦断面図である。FIG. 3 is a longitudinal sectional view of a third intermediate in the process of producing the hydrogen ion conductive polymer membrane with a catalyst layer for a fuel cell in an example of the present invention.

【図４】本発明の実施例における第２の形状保持フィル
ムと結合した燃料電池用触媒層付き水素イオン伝導性高
分子膜の縦断面図である。FIG. 4 is a longitudinal sectional view of a hydrogen ion conductive polymer membrane with a catalyst layer for a fuel cell combined with a second shape retention film in an example of the present invention.

【図５】本発明の実施例における燃料電池用触媒層付き
水素イオン伝導性高分子膜の縦断面図である。FIG. 5 is a longitudinal sectional view of a hydrogen ion conductive polymer membrane with a catalyst layer for a fuel cell in an example of the present invention.

【図６】本発明の実施例における第２および第３の形状
保持フィルムと結合した燃料電池用触媒層付き水素イオ
ン伝導性高分子膜の縦断面図である。FIG. 6 is a longitudinal sectional view of a hydrogen ion conductive polymer membrane with a catalyst layer for a fuel cell combined with second and third shape retention films in an example of the present invention.

【図７】本発明の実施例の燃料電池用触媒層付き水素イ
オン伝導性高分子膜を用いた燃料電池の縦断面図であるFIG. 7 is a longitudinal sectional view of a fuel cell using a hydrogen ion conductive polymer membrane with a catalyst layer for a fuel cell according to an example of the present invention.

【符号の説明】[Explanation of symbols]

１ 水素イオン伝導性高分子膜 ２ 第１の形状保持フィルム ３、５、７ 中間体 ４ａ、４ｂ 触媒層 ６ 第２の形状保持フィルム ８ ６と結合した触媒層付き水素イオン伝導性高分子膜 ９ 触媒層付き水素イオン伝導性高分子膜 １０ 第３の形状保持フィルム １１ ６および１０と結合した触媒層付き水素イオン伝
導性高分子膜 １３ａ、１３ｂ 拡散層 １４ａ アノード １４ｂ カソード １６ａ、１６ｂ ガス流路 １７ａ、１７ｂ 導電性セパレータ板 １８ 冷却水の流路 １９ 冷却板 ２３ ガスケットDESCRIPTION OF SYMBOLS 1 Hydrogen ion conductive polymer membrane 2 1st shape retention film 3, 5, 7 Intermediate 4a, 4b Catalyst layer 6 2nd shape retention film 8 Hydrogen ion conductive polymer film with a catalyst layer combined with 6 9 Hydrogen ion conductive polymer membrane with catalyst layer 10 Third shape retention film 11 Hydrogen ion conductive polymer membrane with catalyst layer 13a, 13b combined with 6 and 10 Diffusion layer 14a Anode 14b Cathode 16a, 16b Gas flow path 17a , 17b conductive separator plate 18 cooling water flow path 19 cooling plate 23 gasket

───────────────────────────────────────────────────── フロントページの続き (72)発明者 堀 喜博 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 羽藤 一仁 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 保坂 正人 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 Ｆターム(参考） 5H018 AA06 AS02 AS03 BB00 BB08 DD08 HH03 5H026 AA06 BB00 BB04 HH03  ──────────────────────────────────────────────────の Continued on the front page (72) Yoshihiro Hori 1006 Kadoma Kadoma, Kadoma, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. (72) Kazuhito Hato 1006 Kadoma Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd. (72) Inventor Masato Hosaka 1006 Kazuma Kadoma, Kazuma, Osaka Prefecture F-term in Matsushita Electric Industrial Co., Ltd. 5H018 AA06 AS02 AS03 BB00 BB08 DD08 HH03 5H026 AA06 BB00 BB04 HH03

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】 第１の形状保持フィルムの一方の面に水
素イオン伝導性高分子膜を積層する工程（１）、前記第
１の形状保持フィルムに積層された水素イオン伝導性高
分子膜上に第１の触媒層を形成する工程（２）、前記第
１の触媒層を形成した水素イオン伝導性高分子膜の第１
の触媒層側の面に第２の形状保持フィルムを結合する工
程（３）、前記第２の形状保持フィルムと結合した水素
イオン伝導性高分子膜から前記第１の形状保持フィルム
を剥離する工程（４）、および前記第１の形状保持フィ
ルムを剥離して露出させた水素イオン伝導性高分子膜上
に第２の触媒層を形成する工程（５）を有することを特
徴とする燃料電池用触媒層付き水素イオン伝導性高分子
膜の製造方法。1. A step of laminating a hydrogen ion conductive polymer film on one surface of a first shape retaining film (1), on the hydrogen ion conductive polymer film laminated on the first shape retaining film. Forming a first catalyst layer (2), the first of the hydrogen ion conductive polymer membrane having the first catalyst layer formed thereon.
Bonding a second shape-retaining film to the surface of the catalyst layer side (3), and peeling the first shape-retaining film from the hydrogen ion conductive polymer film bonded to the second shape-retaining film (4) and a step (5) of forming a second catalyst layer on the hydrogen ion conductive polymer membrane which has been peeled off and exposed to the first shape retaining film. A method for producing a hydrogen ion conductive polymer membrane with a catalyst layer. 【請求項２】 さらに、前記第２の触媒層を形成した水
素イオン伝導性高分子膜から前記第２の形状保持フィル
ムを剥離する工程（６）を有する請求項１に記載の燃料
電池用触媒層付き水素イオン伝導性高分子膜の製造方
法。2. The fuel cell catalyst according to claim 1, further comprising a step (6) of peeling off the second shape retaining film from the hydrogen ion conductive polymer membrane on which the second catalyst layer is formed. A method for producing a layered proton conductive polymer membrane. 【請求項３】 さらに、前記第２の触媒層を形成した水
素イオン伝導性高分子膜の第２の触媒層側の面に、前記
第２の形状保持フィルムと目視あるいは触覚で識別でき
る程度に異なる第３の形状保持フィルムを結合する工程
（７）を有する請求項１に記載の燃料電池用触媒層付き
水素イオン伝導性高分子膜の製造方法。3. The hydrogen ion conductive polymer membrane on which the second catalyst layer is formed, on the surface on the second catalyst layer side, in such a degree that it can be visually or tactilely distinguished from the second shape retention film. The method for producing a hydrogen ion conductive polymer membrane with a catalyst layer for a fuel cell according to claim 1, further comprising a step (7) of combining different third shape retaining films. 【請求項４】 前記触媒層を形成する工程（２）および
（５）が、触媒と溶剤を含む触媒ペーストを前記水素イ
オン伝導性高分子膜上に印刷あるいは塗布した後、乾燥
して触媒層を形成する工程である請求項１〜３のいずれ
かに記載の燃料電池用触媒層付き水素イオン伝導性高分
子膜の製造方法。4. The step (2) and step (5) of forming the catalyst layer comprises printing or coating a catalyst paste containing a catalyst and a solvent on the hydrogen ion conductive polymer membrane, followed by drying and drying. The method for producing a hydrogen ion conductive polymer membrane provided with a catalyst layer for a fuel cell according to any one of claims 1 to 3, which is a step of forming 【請求項５】 前記水素イオン伝導性高分子膜の触媒層
側の面に前記形状保持フィルムを結合する工程（３）ま
たは（７）が、前記水素イオン伝導性高分子膜の触媒層
側の面と前記形状保持フィルムを重ね合わせて加熱状態
で加圧する工程である請求項１〜４のいずれかに記載の
燃料電池用触媒層付き水素イオン伝導性高分子膜の製造
方法。5. The step (3) or (7) of bonding the shape retaining film to the surface of the hydrogen ion conductive polymer membrane on the catalyst layer side, wherein the step (3) or (7) is performed on the catalyst layer side of the hydrogen ion conductive polymer membrane. The method for producing a hydrogen ion conductive polymer membrane with a catalyst layer for a fuel cell according to any one of claims 1 to 4, wherein said step is a step of superposing a surface and said shape maintaining film and applying pressure in a heated state. 【請求項６】 前記形状保持フィルムが、膜厚５０〜５
００μｍの熱可塑性樹脂フィルムからなる請求項１〜５
のいずれかに記載の燃料電池用触媒層付き水素イオン伝
導性高分子膜の製造方法。6. The method according to claim 1, wherein the shape maintaining film has a thickness of 50 to 5
6. A thermoplastic resin film having a thickness of 00 [mu] m.
The method for producing a hydrogen ion conductive polymer membrane provided with a catalyst layer for a fuel cell according to any one of the above.
JP2001088676A 2001-03-15 2001-03-26 Manufacturing method for hydrogen ion conductive polymer membrane with catalyst layer for fuel cell Pending JP2002289207A (en)

Priority Applications (5)

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JP2001088676A JP2002289207A (en) 2001-03-26 2001-03-26 Manufacturing method for hydrogen ion conductive polymer membrane with catalyst layer for fuel cell
PCT/JP2002/002321 WO2002075834A1 (en) 2001-03-15 2002-03-12 Method of manufacturing electrolytic film electrode connection body for fuel cell
US10/296,426 US20030078157A1 (en) 2001-03-15 2002-03-12 Method of manufacturing electrolytic film electrode connection body for fuel cell
KR10-2002-7014726A KR100443107B1 (en) 2001-03-15 2002-03-12 Method of manufacturing elect rolytic film electrode connection body for fuel cell
EP02702919A EP1357620A4 (en) 2001-03-15 2002-03-12 Method of manufacturing electrolytic film electrode connection body for fuel cell

Applications Claiming Priority (1)

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