JP2000299119A - Manufacture of catalyst layer - Google Patents
Manufacture of catalyst layerInfo
- Publication number
- JP2000299119A JP2000299119A JP11109413A JP10941399A JP2000299119A JP 2000299119 A JP2000299119 A JP 2000299119A JP 11109413 A JP11109413 A JP 11109413A JP 10941399 A JP10941399 A JP 10941399A JP 2000299119 A JP2000299119 A JP 2000299119A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- electrolyte
- electrolyte membrane
- catalyst layer
- frame
- 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.)
- Withdrawn
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
Landscapes
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】電解質膜を有する電気化学装
置、たとえば燃料電池、とくに固体高分子電解質型燃料
電池および直接メタノール燃料電池の電極の触媒体に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochemical device having an electrolyte membrane, for example, a fuel cell, and more particularly to a catalyst for an electrode of a solid polymer electrolyte fuel cell and a direct methanol fuel cell.
【0002】[0002]
【従来の技術】電解質膜を備える電気化学装置には、た
とえば固体高分子電解質型燃料電池、直接メタノール燃
料電池、水電解装置、食塩電解槽、オゾン発生装置、酸
素分離装置、水素分離装置あるいは酸素センサーなどが
ある。これらの電気化学装置は、電解質膜の片面にカソ
ード、他面にアノードを配した構造である。2. Description of the Related Art Electrochemical devices provided with an electrolyte membrane include, for example, solid polymer electrolyte fuel cells, direct methanol fuel cells, water electrolyzers, salt electrolyzers, ozone generators, oxygen separators, hydrogen separators and oxygen separators. There are sensors and so on. These electrochemical devices have a structure in which a cathode is arranged on one side of an electrolyte membrane and an anode is arranged on the other side.
【0003】電解質膜はとしては、スルホン酸基やカル
ボン酸基などのイオン交換基を有するイオン交換膜が用
いられ、例えばパーフロロスルホン酸樹脂膜、パーフロ
ロカルボン酸膜やビニルベンゼンスルホン酸樹脂膜など
がある。これら膜は水を含んだ状態で良好なプロトン伝
導性を示し電解質として機能する。As the electrolyte membrane, an ion exchange membrane having an ion exchange group such as a sulfonic acid group or a carboxylic acid group is used. For example, a perfluorosulfonic acid resin membrane, a perfluorocarboxylic acid membrane, a vinylbenzenesulfonic acid resin membrane, or the like is used. and so on. These membranes show good proton conductivity in a state containing water and function as an electrolyte.
【0004】固体高分子電解質型燃料電池は、アノード
に燃料として例えば水素およびカソードに酸化剤として
例えば酸素とを供給して電気化学的に反応させて、電力
を得る電気化学装置である。アノードおよびカソードは
ガス拡散電極であり、電解質膜の片面にアノードを、他
面にカソードを接合してガス拡散電極−電解質膜接合体
を構成する。A solid polymer electrolyte fuel cell is an electrochemical device that supplies electric power, for example, hydrogen to the anode, and oxygen, for example, to the cathode as an oxidant, and reacts electrochemically to obtain electric power. The anode and the cathode are gas diffusion electrodes, and the anode is joined to one side of the electrolyte membrane and the cathode is joined to the other side to form a gas diffusion electrode-electrolyte membrane assembly.
【0005】ガス拡散電極はガス拡散層と触媒層とから
なり、アノードおよびカソードの触媒層は白金族金属の
金属粒子あるいはこれらの粒子を担持したカーボン粒子
などを触媒として備えており、ガス拡散層は撥水性を有
する多孔質なカーボンペーパーなどが用いられる。The gas diffusion electrode comprises a gas diffusion layer and a catalyst layer. The catalyst layers of the anode and the cathode are provided with platinum group metal particles or carbon particles carrying these particles as catalysts. For example, porous carbon paper having water repellency is used.
【0006】このガス拡散電極−電解質膜接合体をガス
供給流路が形成されたガス不透過性の一対のセパレータ
で挟持して基本単位となる単電池を構成する。この単電
池を複数個積層して固体高分子電解質型燃料電池を構成
する。The gas diffusion electrode-electrolyte membrane assembly is sandwiched between a pair of gas-impermeable separators having a gas supply passage formed therein to form a unit cell as a basic unit. A plurality of such unit cells are stacked to form a solid polymer electrolyte fuel cell.
【0007】固体高分子電解質型燃料電池を作動させる
と、 アノードでは、 2H2 → 4H+ + 4e- カソードでは、 O2 + 4H+ + 4e- → 2
H2O の電気化学反応が進行する。[0007] Activating the solid polymer electrolyte fuel cell, the anode, 2H 2 → 4H + + 4e - At the cathode, O 2 + 4H + + 4e - → 2
The electrochemical reaction of H 2 O proceeds.
【0008】直接メタノール燃料電池は、酸化剤として
例えば酸素をカソードに、燃料として例えばメタノール
と水の混合物をアノードに供給して電気化学的に反応さ
せて、電力を得る電気化学装置である。電解質膜の一方
の面にカソード電極が、他方の面にアノード電極が配さ
れる。カソード電極およびアノード電極は、たとえば白
金族金属の粒子やその合金の粒子あるいはそれらの粒子
を担持したカーボン粒子などを触媒として備えた触媒層
を有する。A direct methanol fuel cell is an electrochemical device that supplies electric power by supplying, for example, oxygen as an oxidizing agent to a cathode and, for example, a mixture of methanol and water as a fuel to an anode to cause an electrochemical reaction. A cathode electrode is provided on one surface of the electrolyte membrane, and an anode electrode is provided on the other surface. The cathode electrode and the anode electrode have a catalyst layer provided with, for example, platinum group metal particles, alloy particles thereof, or carbon particles carrying these particles as a catalyst.
【0009】直接メタノール型燃料電池を作動させる
と、 アノードでは、 CH3OH + H2O → CO2 + 6
H+ + 6e- カソードでは、 3/2O2 + 6H+ + 6e- → 3
H2O の電気化学反応が進行する。When a direct methanol fuel cell is operated, CH 3 OH + H 2 O → CO 2 +6
At the H + + 6e − cathode, 3 / 2O 2 + 6H + + 6e − → 3
The electrochemical reaction of H 2 O proceeds.
【0010】電気化学反応が進行する触媒層は、少なく
とも電解質の溶液と触媒とを含むペースト状あるいはス
ラリー状の触媒分散物から作製される。例えば、USP
5211984号では触媒分散物から離型紙に触媒層を
形成した後、電解質膜に触媒層を加熱圧接により転写す
る方法が提案されている。The catalyst layer in which the electrochemical reaction proceeds is made from a paste or slurry catalyst dispersion containing at least an electrolyte solution and a catalyst. For example, USP
No. 5211984 proposes a method in which a catalyst layer is formed on a release paper from a catalyst dispersion, and then the catalyst layer is transferred to an electrolyte membrane by heating and pressing.
【0011】また、特公平2−7398号では、触媒分
散物からシート状の触媒層を形成し、それを電解質膜の
一体に加熱圧接する方法が提案されている。このほかに
も、電子伝導性の基板に触媒分散物を塗布して触媒層を
形成し、電解質膜に一体に加熱圧接する方法あるいは、
触媒分散物を電解質膜に塗布して触媒層を形成する方法
が種々提案されている。Japanese Patent Publication No. 2-7398 proposes a method in which a sheet-like catalyst layer is formed from a catalyst dispersion and is heated and pressed integrally with an electrolyte membrane. In addition, a method in which a catalyst dispersion is applied to an electron conductive substrate to form a catalyst layer, and then heated and pressed integrally with the electrolyte membrane, or
Various methods have been proposed for forming a catalyst layer by applying a catalyst dispersion to an electrolyte membrane.
【0012】この他には、例えば特公昭59−4207
8号や特公平2−43830号には電解質膜の表面に白
金族金属の無電解メッキを施す方法が提案されている。Other than the above, for example, Japanese Patent Publication No. 59-4207
No. 8 and Japanese Patent Publication No. 2-43830 propose a method of performing electroless plating of a platinum group metal on the surface of an electrolyte membrane.
【0013】[0013]
【発明が解決しようとする課題】上記のような、あらか
じめ触媒層を作製してから転写や加熱圧接により電解質
膜と一体にする、触媒層−電解質接合体の製造方法の場
合は、電解質膜と触媒層との良好な接合体を作製するこ
とは困難であることが多い。As described above, in the case of a method for manufacturing a catalyst layer-electrolyte assembly in which a catalyst layer is prepared in advance and then integrated with an electrolyte membrane by transfer or heat pressure welding, the electrolyte membrane and the electrolyte membrane are combined. It is often difficult to produce a good joined body with the catalyst layer.
【0014】その原因の一つは、電解質膜は水の含量に
よって寸法変化することに起因する。乾燥状態の電解質
膜に触媒層を接合する場合は、接合した後に水を含ませ
る必要がある。しかしながら、乾燥状態の電解質膜に水
を含ませるとその寸法は10〜20%も増大する。この
ために、形成した触媒層−電解質接合体の触媒層の剥
離、脱落、ひび割れが発生して均一性が低下する。一
方、水を含んだ状態の電解質膜に触媒層を接合する場合
は、加熱圧接のときに電解質膜の含水量および温度の急
激な変化のために電解質膜が変形し、触媒層および電解
質膜の均一性が低下する。One of the causes is that the electrolyte membrane changes its size depending on the water content. When joining the catalyst layer to the electrolyte membrane in a dry state, it is necessary to include water after joining. However, when water is included in the electrolyte membrane in a dry state, its size increases by 10 to 20%. As a result, the catalyst layer of the formed catalyst layer-electrolyte assembly is peeled, dropped, and cracked, and the uniformity is reduced. On the other hand, when the catalyst layer is bonded to the electrolyte membrane containing water, the electrolyte membrane is deformed due to a sudden change in the water content and the temperature of the electrolyte membrane during heating and pressing, and the catalyst layer and the electrolyte membrane are deformed. Uniformity decreases.
【0015】また、これらの製法は、少なくとも触媒層
の形成工程と電解質膜との接合工程と多段階工程にな
り、また上記の均一性の低下を回避するために種々の対
策を必要とし、その作製工程が煩雑になる。Further, these production methods include at least a step of forming a catalyst layer, a step of bonding with an electrolyte membrane, and a multi-step step, and various measures are required to avoid the above-mentioned reduction in uniformity. The manufacturing process becomes complicated.
【0016】上述のような触媒層を電解質膜に接合する
方法に対して、触媒分散物を電解質膜に直接塗布する方
法がある。乾燥状態の電解質膜に触媒分散物を直接塗布
する場合は、触媒分散物に含まれる水やアルコール類が
電解質膜に吸収されてその寸法が著しく変化する。この
ために電解質膜に均一な触媒層の形成が困難である。一
方、水を含んだ状態の電解質膜に触媒分散物を直接塗布
する場合は、前述の触媒分散物に含まれる水やアルコー
ル類の吸収による電解質膜の寸法変化への影響は比較的
少ないが、それでも均一な触媒層を形成するためには対
策が必要である。また、電解質膜と触媒分散物との親和
性が乏しいために、塗布方法によっては均一に触媒分散
物を塗布できず、均一な触媒層の形成が困難である。As a method of bonding the catalyst layer to the electrolyte membrane as described above, there is a method of directly applying the catalyst dispersion to the electrolyte membrane. When the catalyst dispersion is directly applied to the electrolyte membrane in a dry state, water and alcohols contained in the catalyst dispersion are absorbed by the electrolyte membrane and the dimensions thereof are significantly changed. For this reason, it is difficult to form a uniform catalyst layer on the electrolyte membrane. On the other hand, when the catalyst dispersion is directly applied to the electrolyte membrane containing water, the influence on the dimensional change of the electrolyte membrane due to the absorption of water or alcohol contained in the above-described catalyst dispersion is relatively small, Nevertheless, countermeasures are required to form a uniform catalyst layer. Further, since the affinity between the electrolyte membrane and the catalyst dispersion is poor, the catalyst dispersion cannot be uniformly applied depending on the application method, and it is difficult to form a uniform catalyst layer.
【0017】本発明は上記の課題を解決するものであ
り、その目的とするところは、均一な触媒層を電解質膜
に直接形成する、簡素な触媒層−電解質接合体の作製方
法を提供するものであり、その均一な触媒層を有する触
媒層−電解質接合体を用いて高性能な電気化学装置を提
供するものであり、とくに高出力な固体高分子電解質型
燃料電池および直接メタノール燃料電池を提供するもの
である。An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide a simple method for producing a catalyst layer-electrolyte assembly in which a uniform catalyst layer is directly formed on an electrolyte membrane. The present invention provides a high-performance electrochemical device using the catalyst layer-electrolyte assembly having the uniform catalyst layer, and particularly provides a high-output solid polymer electrolyte fuel cell and a direct methanol fuel cell. Is what you do.
【0018】[0018]
【課題を解決するための手段】少なくとも触媒と電解質
の溶液を含む触媒混合物を電解質膜に直接塗布する簡素
な触媒層の製造方法において、電解質膜にアルコール類
を含浸させることにより、電解質膜と触媒分散物との親
和性を向上させ、かつ電解質膜の含水量の変化に起因す
る電解質膜の寸法変化を抑制することができる。さら
に、電解質膜を平板に固定することおよび額縁状シート
で覆うことにより、電解質膜の含水量の変化に起因する
寸法変化を抑制し、触媒分散物を均一に塗布することを
可能とし、これによって均一な触媒層を備えた触媒層−
電解質接合体を製造する方法を提供する。In a simple method for producing a catalyst layer, in which a catalyst mixture containing at least a solution of a catalyst and an electrolyte is directly applied to the electrolyte membrane, the electrolyte membrane is impregnated with an alcohol by impregnating the electrolyte membrane with an alcohol. The affinity with the dispersion can be improved, and the dimensional change of the electrolyte membrane due to the change in the water content of the electrolyte membrane can be suppressed. Further, by fixing the electrolyte membrane to a flat plate and covering it with a frame-shaped sheet, it is possible to suppress a dimensional change due to a change in the water content of the electrolyte membrane, and to uniformly apply the catalyst dispersion, thereby enabling Catalyst layer with uniform catalyst layer
A method for manufacturing an electrolyte conjugate is provided.
【0019】第一の発明は、炭素数が4以下のアルコー
ルを含む電解質膜の片面もしくは両面に、触媒と電解質
を含む触媒層を形成することを特徴とする触媒層−電解
質接合体の製造方法である。According to a first aspect of the present invention, there is provided a method for producing a catalyst layer-electrolyte assembly, wherein a catalyst layer containing a catalyst and an electrolyte is formed on one or both sides of an electrolyte membrane containing an alcohol having 4 or less carbon atoms. It is.
【0020】第二の発明は、電解質膜に炭素数が4以下
のアルコール類を含浸し、次いで前記電解質膜を平板上
に配置して、次いで前記電解質膜の上面に開口部を有す
る額縁状シートを配し、次いで前記額縁状シートその開
口部から電解質膜に触媒と電解質を含む触媒分散物を塗
布することを特徴とする触媒層−電解質接合体の製造方
法である。According to a second aspect of the present invention, there is provided a frame-like sheet having an electrolyte membrane impregnated with an alcohol having 4 or less carbon atoms, then arranging the electrolyte membrane on a flat plate, and then having an opening on the upper surface of the electrolyte membrane. And then applying a catalyst dispersion containing a catalyst and an electrolyte to the electrolyte membrane from the opening of the frame-shaped sheet, thereby producing a catalyst layer-electrolyte assembly.
【0021】第三の発明は、開口部を有する額縁状シー
トの厚みにより、触媒層の厚みを制御することを特徴と
する触媒層−電解質接合体の製造方法である。The third invention is a method for manufacturing a catalyst layer-electrolyte assembly, wherein the thickness of the catalyst layer is controlled by the thickness of the frame-shaped sheet having the opening.
【0022】第四の発明は、上記の製造方法で作製され
た触媒層−電解質接合体を備えたことを特徴とする電気
化学装置である。According to a fourth aspect of the present invention, there is provided an electrochemical device including the catalyst layer-electrolyte assembly manufactured by the above-described manufacturing method.
【0023】第五の発明は、前記電気化学装置が固体高
分子電解質型燃料電池もしくは直接メタノール燃料電池
であることを特徴とする。A fifth invention is characterized in that the electrochemical device is a solid polymer electrolyte fuel cell or a direct methanol fuel cell.
【0024】[0024]
【発明の実施の形態】本発明による触媒層−電解質接合
体は、少なくとも触媒と電解質の溶液とを含む触媒分散
物を調製して、水やアルコール類あるいはそれらの混合
物を含んだ状態の電解質膜に触媒分散物を直接塗布する
ことにより形成される。また、水やアルコール類あるい
はそれらの混合物を含んだ状態の電解質膜を平板に配置
し、さらにその上面に開口部を有する額縁状のシートを
配してその開口部から触媒分散物を直接塗布することに
より形成される。BEST MODE FOR CARRYING OUT THE INVENTION A catalyst layer-electrolyte assembly according to the present invention is a method for preparing a catalyst dispersion containing at least a catalyst and an electrolyte solution to prepare an electrolyte membrane containing water, alcohols or a mixture thereof. It is formed by directly applying the catalyst dispersion to the catalyst. Further, an electrolyte membrane containing water, alcohols or a mixture thereof is arranged on a flat plate, and a frame-shaped sheet having an opening on the upper surface thereof is further arranged, and the catalyst dispersion is directly applied from the opening. It is formed by this.
【0025】触媒は、白金族金属やその合金の粒子ある
いはそれらを担持したカーボンを用いることができる。As the catalyst, particles of a platinum group metal or an alloy thereof or carbon carrying them can be used.
【0026】電解質の溶液は、たとえばパーフロロスル
ホン酸樹脂、パーフロロカルボン酸樹脂あるいはビニル
ベンゼンスルホン酸樹脂を水とアルコール類の混合溶媒
に溶解したものを用いることができ、たとえば市販され
ているパーフロロスルホン酸樹脂の溶液としてナフィオ
ンの5wt%溶液を用いることができる。As the electrolyte solution, for example, a solution prepared by dissolving a perfluorosulfonic acid resin, a perfluorocarboxylic acid resin, or a vinylbenzenesulfonic acid resin in a mixed solvent of water and an alcohol can be used. As a solution of the fluorosulfonic acid resin, a 5 wt% solution of Nafion can be used.
【0027】電解質の溶液の溶媒は、は炭素数が4つ以
下のアルコール、たとえばメタノール、エタノール、1
−プロパノール、2−プロパノール、1−ブタノールや
2−ブタノールやこれらの混合物あるいはそれらと水と
の混合物を用いることができる。The solvent of the electrolyte solution is an alcohol having 4 or less carbon atoms, such as methanol, ethanol,
-Propanol, 2-propanol, 1-butanol, 2-butanol, a mixture thereof, or a mixture thereof with water can be used.
【0028】触媒分散物は、少なくとも触媒と電解質の
溶液とを含んでおり、分散媒に少なくとも触媒と電解質
の溶液が分散されている。その分散媒は炭素数が4つ以
下のアルコール、たとえばメタノール、エタノール、1
−プロパノール、2−プロパノール、1−ブタノールや
2−ブタノールやこれらの混合物あるいはそれらと水と
の混合物を用いることができる。分散媒に少なくとも触
媒と電解質の溶液を加えて攪拌し、分散媒の量を帰るこ
とによりその粘度を調節してスラリー状あるいはペース
ト状の触媒分散物を調製する。The catalyst dispersion contains at least a solution of a catalyst and an electrolyte, and at least a solution of the catalyst and the electrolyte is dispersed in a dispersion medium. The dispersion medium is an alcohol having 4 or less carbon atoms, such as methanol, ethanol,
-Propanol, 2-propanol, 1-butanol, 2-butanol, a mixture thereof, or a mixture thereof with water can be used. At least a solution of a catalyst and an electrolyte is added to the dispersion medium and stirred, and the viscosity of the dispersion medium is adjusted by returning the amount of the dispersion medium to prepare a slurry or paste catalyst dispersion.
【0029】電解質膜は、スルホン酸基やカルボン酸基
などのイオン交換基を有するイオン交換膜が用いられ、
例えばパーフロロスルホン酸樹脂膜、パーフロロカルボ
ン酸膜やビニルベンゼンスルホン酸樹脂膜などがある。
これらのイオン交換膜は、水を含む状態でプロトン伝導
性を示し、電解質膜として機能する。As the electrolyte membrane, an ion exchange membrane having an ion exchange group such as a sulfonic acid group or a carboxylic acid group is used.
For example, there are a perfluorosulfonic acid resin film, a perfluorocarboxylic acid film, and a vinylbenzenesulfonic acid resin film.
These ion exchange membranes exhibit proton conductivity in a state containing water and function as an electrolyte membrane.
【0030】これらの電解質膜に触媒分散物を直接塗布
して触媒層−電解質接合体を形成する。このとき、電解
質膜に洗浄およびプロトン化処理を施した後、水やアル
コール類を含ませて触媒分散物を塗布することを特徴と
する。たとえば、市販の電解質膜を精製水で数回洗浄し
た後、過酸化水素水溶液で煮沸して脱脂処理を施し、さ
らに精製水で数回洗浄する。つぎに、希硫酸などの酸性
水溶液で煮沸して電解質膜の対イオンをプロトン型に置
換した後、精製水で数回洗浄してプロトン化処理を施
す。A catalyst dispersion is directly applied to these electrolyte membranes to form a catalyst layer-electrolyte assembly. At this time, after the electrolyte membrane is washed and protonated, the catalyst dispersion is applied by incorporating water and alcohols. For example, a commercially available electrolyte membrane is washed several times with purified water, boiled with an aqueous hydrogen peroxide solution to perform a degreasing treatment, and further washed several times with purified water. Next, after boiling with an acidic aqueous solution such as dilute sulfuric acid to replace the counter ion of the electrolyte membrane with a proton type, the electrolyte membrane is washed several times with purified water and subjected to a protonation treatment.
【0031】さらに、電解質膜をアルコール類に浸漬し
てアルコール類を含ませるアルコール処理を施す。その
アルコール類は炭素数が4つ以下のアルコールであり、
たとえばメタノール、エタノール、1−プロパノール、
2−プロパノール、1−ブタノールや2−ブタノールな
どを用いることができる。アルコール処理は浸漬の他
に、電解質膜にアルコール類を散布するなど方法を用い
てもよく、要は電解質膜にアルコールを含ませればよ
い。Further, the electrolyte membrane is immersed in alcohols and subjected to alcohol treatment for containing alcohols. The alcohols are alcohols having 4 or less carbon atoms,
For example, methanol, ethanol, 1-propanol,
2-propanol, 1-butanol, 2-butanol and the like can be used. The alcohol treatment may be performed by, for example, spraying alcohols on the electrolyte membrane in addition to immersion. In short, alcohol may be contained in the electrolyte membrane.
【0032】電解質膜にアルコール類を含ませることに
より、アルコール類を含む触媒分散物との親和性が良く
なるともに、触媒分散物からの水やアルコール類の吸収
による電解質膜の形状変化を抑制することができる。な
お、脱脂処理やプロトン化処理を施さずに、アルコール
処理だけを施した電解質膜を用いることもできる。By including alcohols in the electrolyte membrane, the affinity for the catalyst dispersion containing alcohols is improved, and the shape change of the electrolyte membrane due to absorption of water or alcohols from the catalyst dispersion is suppressed. be able to. Note that an electrolyte membrane that has been subjected to only alcohol treatment without performing degreasing treatment or protonation treatment can also be used.
【0033】アルコール処理を施した電解質膜を平板に
配置し、好ましくはそれらを密着させ、さらに電解質膜
を覆うように開口部を有する額縁状のシートを配置し、
好ましくはそれらを密着させ、触媒分散物を開口部から
塗布する。An electrolyte membrane subjected to alcohol treatment is arranged on a flat plate, preferably adhered to each other, and a frame-shaped sheet having an opening is further arranged so as to cover the electrolyte membrane.
Preferably, they are brought into close contact, and the catalyst dispersion is applied from the opening.
【0034】その状態の一例を図1、図2および図3に
示す。図3は、本発明の触媒分散物の塗布方法に必要な
構成材を示したものである。図3において、1はアルコ
ール処理を施した電解質膜、2は平板、3は開口部を有
する額縁状のシートで、4は開口部を有する額縁状のシ
ート3の開口部、5は開口部を有する額縁状のシート3
の額縁部を示す。それぞれの大きさは、開口部4、アル
コール処理を施した電解質膜1、開口部を有する額縁状
のシート3および平板2の順に大きくなる。FIGS. 1, 2 and 3 show an example of this state. FIG. 3 shows components necessary for the method for applying a catalyst dispersion of the present invention. In FIG. 3, 1 is an electrolyte membrane subjected to alcohol treatment, 2 is a flat plate, 3 is a frame-shaped sheet having an opening, 4 is an opening of the frame-shaped sheet 3 having an opening, and 5 is an opening. Framed sheet 3 having
Shows the frame part. Each size increases in the order of the opening 4, the electrolyte membrane 1 subjected to alcohol treatment, the frame-shaped sheet 3 having the opening, and the flat plate 2.
【0035】図1は、アルコール処理を施した電解質膜
1、平板2および開口部を有する額縁状のシート3を配
置した状態を上方からみた様子を示す図である。アルコ
ール処理を施した電解質膜1は平板2からはみでること
なく、額縁部5のどの辺も少なくとも一部がアルコール
処理を施した電解質膜1と重なる状態に配置される。FIG. 1 is a diagram showing a state in which an electrolyte membrane 1, a flat plate 2, and a frame-shaped sheet 3 having openings are disposed from the upper side when alcohol treatment is performed. The alcohol-treated electrolyte membrane 1 is arranged so as not to protrude from the flat plate 2 and at least a part of any side of the frame portion 5 overlaps the alcohol-treated electrolyte membrane 1.
【0036】図2は、アルコール処理を施した電解質膜
1、平板2および開口部を有する額縁状のシート3を配
置した状態の断面図である。アルコール処理を施した電
解質膜1と平板2、アルコール処理を施した電解質膜1
と額縁部5、平板2と額縁部5はそれぞれ密着してい
る。FIG. 2 is a cross-sectional view showing a state in which an electrolyte membrane 1, a flat plate 2, and a frame-shaped sheet 3 having an opening are disposed after alcohol treatment. Electrolyte-treated electrolyte membrane 1 and flat plate 2, alcohol-treated electrolyte membrane 1
And the frame 5, and the flat plate 2 and the frame 5 are in close contact with each other.
【0037】平板1は、アルコール処理を施した電解質
膜より大きく、水とアルコール類を含んだ状態の電解質
膜が密着する程度の滑らかであればよく、例えばガラ
ス、金属あるいはプラスチックなどその材質はいずれで
も構わない。The flat plate 1 has only to be larger than the electrolyte membrane subjected to the alcohol treatment and has a smoothness such that the electrolyte membrane containing water and alcohol adheres to each other. For example, any material such as glass, metal or plastic can be used. But it doesn't matter.
【0038】開口部4の形状は、正方形や長方形などの
多角形あるいは円形、楕円形などその形状は任意であ
り、必要な触媒層の形状と大きさにより選択される。こ
の額縁部の外周部の大きさは、アルコール処理を施した
電解質膜より大きいことが好ましく、その開口部以外に
位置するアルコール処理を施した電解質膜はこの額縁部
5で覆われていることが望ましい。The shape of the opening 4 may be any shape such as a polygon such as a square or a rectangle, a circle, an ellipse, or the like, and is selected according to the required shape and size of the catalyst layer. It is preferable that the size of the outer peripheral portion of the frame portion is larger than the electrolyte membrane subjected to the alcohol treatment, and that the electrolyte membrane subjected to the alcohol treatment located outside the opening is covered with the frame portion 5. desirable.
【0039】この開口部を有する額縁状のシート3に
は、水やアルコール類を透過し難く、それらを吸収する
ことにより膨潤などの寸法変化が起こらない材質のもの
を用いることができる。たとえば、ポリエチレン、ポリ
塩化ビニルやポリテトラフロロエチレンなどの高分子あ
るいはアルミ箔や銅箔などの金属を使用することができ
る。The frame-shaped sheet 3 having the openings can be made of a material that hardly permeates water or alcohol and does not cause dimensional changes such as swelling by absorbing them. For example, polymers such as polyethylene, polyvinyl chloride and polytetrafluoroethylene, or metals such as aluminum foil and copper foil can be used.
【0040】つぎに、上述のアルコール処理を施した電
解質膜1、平板2および額縁部5が密着した状態を形成
する方法の一例を述べる。アルコール処理を施した電解
質膜を平板に配置して、例えばスキージブレードを用い
て平板とアルコール処理を施した電解質膜との間に存在
する余剰の水やアルコールを扱き出して、アルコール処
理を施した電解質膜を平板に密着させることができる。
スキージブレードの他にローラーなど用いることも可能
であり、要は余剰の水やアルコールを除いてアルコール
処理を施した電解質膜を平板に密着させればよい。Next, an example of a method for forming a state in which the electrolyte membrane 1, the flat plate 2, and the frame portion 5 which have been subjected to the above-described alcohol treatment are in close contact with each other will be described. The alcohol-treated electrolyte membrane was arranged on a flat plate, and excess water or alcohol existing between the flat plate and the alcohol-treated electrolyte membrane was handled using, for example, a squeegee blade, and the alcohol treatment was performed. The electrolyte membrane can be adhered to the flat plate.
In addition to a squeegee blade, it is also possible to use a roller or the like. In short, it is sufficient to remove the excess water or alcohol and bring the electrolyte membrane subjected to alcohol treatment into close contact with the flat plate.
【0041】つぎに、そのアルコール処理を施した電解
質膜に、開口部を有する額縁状シートを配置して、例え
ばスキージブレードを用いて額縁状シートと電解質膜と
の間に存在する余剰の水やアルコールを扱き出して、額
縁状シートを電解質膜に密着させる。このようにして、
図1および図2に示すようなエタノール処理を施した電
解質膜の片面に平板に配し、他面に開口部を有する額縁
状シートで覆って、固定状態の電解質膜を形成する。Next, a frame-shaped sheet having an opening is disposed on the alcohol-treated electrolyte membrane, and excess water existing between the frame-shaped sheet and the electrolyte membrane is removed using, for example, a squeegee blade. Alcohol is taken out and the frame sheet is brought into close contact with the electrolyte membrane. In this way,
The electrolyte membrane treated with ethanol as shown in FIGS. 1 and 2 is arranged on a flat surface on one side and covered with a frame-shaped sheet having an opening on the other side to form a fixed electrolyte membrane.
【0042】つぎに、固定状態の電解質膜に、開口部か
ら触媒分散物を塗布し、乾燥して触媒層−電解質接合体
を形成する。その塗布方法は、たとえば開口部に位置す
る電解質膜にペースト状の触媒分散物を、スキージブレ
ードを掃引して、均一に引き延ばして塗布することがで
きる。Next, a catalyst dispersion is applied to the fixed electrolyte membrane from the opening and dried to form a catalyst layer-electrolyte assembly. In the application method, for example, the paste-like catalyst dispersion can be uniformly applied to the electrolyte membrane located at the opening by sweeping the squeegee blade.
【0043】その触媒分散物の塗布の一例を図4および
図5に示す。図4は、本発明の触媒分散物の塗布方法お
いて、触媒分散物を配置した状態を示す模式図である。
平板2と開口部を有する額縁状のシート3とで挟持して
固定されたアルコール処理を施した電解質膜1におい
て、その額縁部5に適量の触媒分散物6を配置する。One example of the application of the catalyst dispersion is shown in FIGS. FIG. 4 is a schematic diagram showing a state in which the catalyst dispersion is disposed in the method for applying a catalyst dispersion of the present invention.
In the electrolyte membrane 1 subjected to alcohol treatment, which is fixed by being sandwiched between the flat plate 2 and the frame-shaped sheet 3 having an opening, an appropriate amount of the catalyst dispersion 6 is disposed in the frame 5.
【0044】図5は、本発明の触媒分散物の塗布方法お
いて、触媒分散物をスキージブレードで引き延ばしてい
る状態を示す模式図である。7はスキージブレードであ
り、8は塗布された触媒分散物であり、9はスキージブ
レードを掃引する方向を示す。開口部を有する額縁状の
シート3の厚みに応じて開口部4に位置するアルコール
処理を施した電解質膜1に触媒分散物6が塗布される。FIG. 5 is a schematic view showing a state in which the catalyst dispersion is stretched by a squeegee blade in the method of applying the catalyst dispersion of the present invention. Reference numeral 7 denotes a squeegee blade, 8 denotes a coated catalyst dispersion, and 9 denotes a direction in which the squeegee blade is swept. The catalyst dispersion 6 is applied to the alcohol-treated electrolyte membrane 1 located at the opening 4 according to the thickness of the frame-shaped sheet 3 having the opening.
【0045】図6は、本発明の触媒分散物の塗布方法お
いて、触媒分散物をスキージブレードで掃引して塗布し
た状態を示す模式図である。触媒分散物を塗布した後、
室温で乾燥する。すると、塗布した触媒分散物が電解質
膜に固定され、この部分が触媒層になる。この乾燥の工
程の間、電解質膜が直接外気に触れることがないので、
乾燥に起因する電解質膜の寸法変化は最小限にとどめる
ことができる。FIG. 6 is a schematic diagram showing a state where the catalyst dispersion is applied by sweeping with a squeegee blade in the method of applying the catalyst dispersion of the present invention. After applying the catalyst dispersion,
Dry at room temperature. Then, the applied catalyst dispersion is fixed to the electrolyte membrane, and this portion becomes a catalyst layer. During this drying process, the electrolyte membrane does not directly contact the outside air,
The dimensional change of the electrolyte membrane due to drying can be minimized.
【0046】乾燥後、開口部を有する額縁状のシート3
を取り除くと、電解質膜1の表面に触媒層10が形成さ
れた触媒層−電解質接合体が得られる。この触媒層10
は、電解質膜の寸法変化に起因する剥離、脱落やひび割
れの形成の影響を受けず均一なものである。After drying, a frame-shaped sheet 3 having an opening
Is removed, a catalyst layer-electrolyte assembly having the catalyst layer 10 formed on the surface of the electrolyte membrane 1 is obtained. This catalyst layer 10
Is uniform without being affected by peeling, falling off, or formation of cracks due to dimensional change of the electrolyte membrane.
【0047】触媒分散物を塗布には、スキージブレード
以外にも、金属製、プラスチック製やガラス製に棒状の
ものや板状のものを用いることができ、要は触媒分散物
を均一に引き延ばすことができればよい。In addition to the squeegee blade, a rod-shaped or plate-shaped metal, plastic, or glass material can be used for coating the catalyst dispersion. I just want to be able.
【0048】このとき、開口部を有する額縁状のシート
の厚みを種々調節すること、および触媒分散物の溶媒量
を調節することにより、任意の厚み触媒層を形成でき、
典型的には3〜50μm、好ましくは5μm〜15μm
の厚みの触媒層を形成することができる。At this time, by adjusting the thickness of the frame-shaped sheet having openings, and adjusting the amount of the solvent of the catalyst dispersion, a catalyst layer having an arbitrary thickness can be formed.
Typically 3 to 50 μm, preferably 5 to 15 μm
Can be formed.
【0049】あるいは、触媒分散物を引き延ばして塗布
する方法の他に、たとえば触媒分散物をスプレー塗布や
スクリーン塗布の方法を用いて、塗布することも可能で
ある。Alternatively, in addition to the method of spreading and applying the catalyst dispersion, it is also possible to apply the catalyst dispersion by, for example, a spray coating or screen coating method.
【0050】塗布された触媒分散物は、室温で数分間放
置して乾燥されるが、電解質膜は平板に密着されて額縁
状のシートに覆われているので、過剰に乾燥することは
なく、電解質膜の面方向の寸法変化はみられない。The applied catalyst dispersion is left to dry at room temperature for several minutes. However, since the electrolyte membrane is adhered to a flat plate and covered with a frame-shaped sheet, it does not dry excessively. No dimensional change in the surface direction of the electrolyte membrane is observed.
【0051】塗布した触媒分散物を乾燥して触媒層を形
成した後、額縁状シートを取り去り、平板から触媒層−
電解質接合体を取って精製水に浸漬して保管する。精製
水に浸漬しても形成した触媒層が脱落したりひび割れが
生じるような電解質膜の寸法変化はない。また、この触
媒層の形成した電解質膜はアルコールを含んだ状態であ
るが、精製水に浸漬することにより含まれるアルコール
が電解質膜から除かれる。After the applied catalyst dispersion was dried to form a catalyst layer, the frame-shaped sheet was removed and the catalyst layer was removed from the flat plate.
Take the electrolyte conjugate and store it immersed in purified water. Even when immersed in purified water, there is no dimensional change of the electrolyte membrane such that the formed catalyst layer falls off or cracks occur. The electrolyte membrane on which the catalyst layer is formed contains alcohol, but the alcohol contained is removed from the electrolyte membrane by immersion in purified water.
【0052】[0052]
【実施例】[実施例1]本発明の触媒層を用いた固体高
分子電解質型燃料電池の作製方法の実施例を具体的に説
明する。[Example 1] An example of a method for manufacturing a solid polymer electrolyte fuel cell using the catalyst layer of the present invention will be specifically described.
【0053】まず、触媒と電解質の溶液からなる触媒分
散物を調製した。触媒は白金を30wt%担持したカー
ボン粉末を用い、電解質の溶液は市販の5wt%ナフィ
オン溶液を用いた。1.5gの触媒を5wt%ナフィオ
ン溶液13mlに添加して30分間攪拌して触媒を分散
させた後、攪拌しながら60℃に加熱し、分散媒に対し
てナフィオンの固形分の重量が15wt%になるまで濃
縮した。これを触媒分散物Aとした。First, a catalyst dispersion comprising a solution of a catalyst and an electrolyte was prepared. The catalyst used was a carbon powder carrying 30 wt% of platinum, and the electrolyte solution used was a commercially available 5 wt% Nafion solution. 1.5 g of the catalyst was added to 13 ml of a 5 wt% Nafion solution and stirred for 30 minutes to disperse the catalyst, and then heated to 60 ° C. with stirring, so that the weight of the solid content of Nafion was 15 wt% with respect to the dispersion medium. And concentrated to. This was designated as catalyst dispersion A.
【0054】つぎに、電解質膜の洗浄、プロトン化処理
およびアルコールに浸漬する処理を施した。電解質膜
は、市販のナフィオン115膜を使用した。ナフィオン
115膜を精製水で3回洗浄した後、脱脂処理として3
%過酸化水素水で1時間煮沸してから精製水で数回洗浄
し、さらに、プロトン化処理として0.5Mの硫酸で1
時間煮沸し、精製水で数回洗浄したあと精製水中に保管
した。つづいて、電解質膜にエタノールを含ませる処理
として、このナフィオン115膜をエタノールに10分
間浸漬した。Next, the electrolyte membrane was washed, protonated, and immersed in alcohol. As the electrolyte membrane, a commercially available Nafion 115 membrane was used. After washing the Nafion 115 membrane three times with purified water, 3 g
Boiling for 1 hour in water, washed several times with purified water, and further treated with 0.5 M sulfuric acid for protonation.
The mixture was boiled for an hour, washed several times with purified water, and stored in purified water. Subsequently, the Nafion 115 membrane was immersed in ethanol for 10 minutes as a process for including ethanol in the electrolyte membrane.
【0055】つぎに、厚さ12.5μmのテトラフロロ
エチレンーヘキサフロロプロピレン共重合体シートに5
cm×5cmの開口部を有する額縁状シートを作製し
た。プロトン化処理およびアルコール処理を施したナフ
ィオン115膜をガラス板上に配置し、開口部を有する
額縁状シートを配置した後、スキージブレードを用い
て、ガラス板とナフィオン115膜の間およびナフィオ
ン115膜と額縁状のシートとの間の余剰の水とエタノ
ールとを扱きとり、ナフィオン115膜をガラス板に密
着させるとともに額縁状のシートをナフィオン115膜
に密着させた。このとき額縁状のシートの開口部に位置
するナフィオン115膜表面の余剰の水とエタノールも
取り除いた。Next, 52.5 μm thick tetrafluoroethylene-hexafluoropropylene copolymer sheet was added
A frame-shaped sheet having an opening of cm × 5 cm was prepared. The Nafion 115 film subjected to the protonation treatment and the alcohol treatment is placed on a glass plate, and a frame-shaped sheet having an opening is placed. Then, using a squeegee blade, the Nafion 115 film is placed between the glass plate and the Nafion 115 film. Excess water and ethanol between the sheet and the frame-like sheet were taken, and the Nafion 115 film was brought into close contact with the glass plate, and the frame-like sheet was brought into close contact with the Nafion 115 film. At this time, excess water and ethanol on the surface of the Nafion 115 film located at the opening of the frame-shaped sheet were also removed.
【0056】開口部に位置するナフィオン115膜に触
媒分散物Aを塗布した。開口部の近傍の額縁部に適量の
触媒分散物Aをとり、スキージブレードを掃引して開口
部に位置するナフィオン115膜に塗布した。その後、
室温で放置して触媒分散物Aを乾燥してナフィオン11
5膜に約8μm厚の触媒層を形成し、精製水中に保存し
た。The catalyst dispersion A was applied to the Nafion 115 film located at the opening. An appropriate amount of the catalyst dispersion A was taken in the frame near the opening, and was applied to the Nafion 115 film located in the opening by sweeping with a squeegee blade. afterwards,
The catalyst dispersion A was dried by leaving it at room temperature to dry Nafion 11
A catalyst layer having a thickness of about 8 μm was formed on the five membranes and stored in purified water.
【0057】片面に触媒層を形成したナフィオン115
膜を精製水から取り出して、触媒層の形成されている面
がガラス板と向かい合うように設置し、スキージブレー
ドを用いて片面に触媒層を形成したナフィオン115膜
とガラス板との間に存在する水を扱き取り、それらを密
着させた。Nafion 115 having a catalyst layer formed on one side
The membrane is taken out of the purified water, installed so that the surface on which the catalyst layer is formed faces the glass plate, and is present between the glass plate and the Nafion 115 film having the catalyst layer formed on one surface using a squeegee blade. The water was taken and they were brought into close contact.
【0058】つぎに、そのナフィオン115膜の他方の
面にエタノールを噴霧した後、前述のものと同様の開口
部を有する額縁状のシートを配置し、スキージブレード
を用いて片面に触媒層を形成したナフィオン115膜と
額縁状シートとの間に存在するエタノールを扱き取り、
それらを密着させた。このとき額縁状シートの開口部に
位置するナフィオン115膜表面の余剰のアルコールも
取り除いた。なお、片面に形成した触媒層と他方の面に
配置する額縁状のシートの開口部とは膜を介して重なり
合うように配置した。Next, after spraying ethanol on the other surface of the Nafion 115 film, a frame-shaped sheet having an opening similar to that described above is arranged, and a catalyst layer is formed on one surface using a squeegee blade. Handle the ethanol present between the Nafion 115 membrane and the framed sheet,
They adhered. At this time, excess alcohol on the surface of the Nafion 115 film located at the opening of the frame-shaped sheet was also removed. The catalyst layer formed on one side and the opening of the frame-shaped sheet disposed on the other side were arranged so as to overlap with each other via a membrane.
【0059】つぎに、上述の方法と同様に開口部の近傍
の額縁部に適量の触媒分散物Aをとり、スキージブレー
ドを掃引して開口部のナフィオン115膜に塗布した。
その後、室温で放置して触媒分散物Aを乾燥してナフィ
オン115膜の他方の面にも約8μm厚の触媒層を形成
した触媒層−電解質接合体を作製し、精製水中に保存し
た。Next, an appropriate amount of the catalyst dispersion A was taken in the frame near the opening in the same manner as described above, and the squeegee blade was swept to apply the catalyst dispersion A to the Nafion 115 film in the opening.
Thereafter, the catalyst dispersion A was dried at room temperature to prepare a catalyst layer-electrolyte assembly having a catalyst layer having a thickness of about 8 μm also formed on the other surface of the Nafion 115 membrane, and stored in purified water.
【0060】上述のナフィオン115膜に形成した触媒
層のそれぞれに、厚み0.2mm、大きさ5cm×5c
mの撥水性を有するカーボンペーパーを120kg/c
m2、130℃,5分間、加熱圧接することにより接合
にして電極−電解質膜接合体を作製した。これを電極−
電解質膜接合体Aとした。Each of the catalyst layers formed on the above-mentioned Nafion 115 film has a thickness of 0.2 mm and a size of 5 cm × 5c.
120 kg / c of carbon paper having water repellency of
The electrode-electrolyte membrane assembly was produced by bonding by heating and pressing for 5 minutes at 130 ° C. for 5 minutes. This is the electrode
An electrolyte membrane assembly A was obtained.
【0061】この電極−電解質膜接合体Aをガス流路が
加工された一対の金属製セパレータに挟持して固体高分
子電解質型燃料電池Aを構成した。The polymer electrolyte fuel cell A was constituted by sandwiching the electrode-electrolyte membrane assembly A between a pair of metal separators having gas channels formed therein.
【0062】[比較例]比較のために従来の転写法で触
媒層を用いて、固体高分子電解質型燃料電池を作製し
た。まず、実施例1で調製した触媒分散物Aを300メ
ッシュを用いたスクリーン印刷でアルミ箔に塗布した
後、乾燥して厚み約8μmの触媒層を形成し、5cm×
5cmの大きさに裁断した。Comparative Example For comparison, a solid polymer electrolyte fuel cell was manufactured using a catalyst layer by a conventional transfer method. First, the catalyst dispersion A prepared in Example 1 was applied to an aluminum foil by screen printing using 300 mesh, and then dried to form a catalyst layer having a thickness of about 8 μm.
It was cut into a size of 5 cm.
【0063】つぎに,実施例1と同様に洗浄およびプロ
トン化処理を施したナフィオン115膜の両面に上述の
アルミ箔上に形成した触媒層を設置して、120kg/
cm 2、90℃、90秒間、加熱圧接して触媒層をナフ
ィオン115膜に転写して、触媒層−電解質接合体を得
た。このときアルミ薄に形成した触媒層はナフィオン1
15膜と向かい合う方向に、かつ膜を介して片面の触媒
層と他面の触媒層との位置が一致するように配置した。Next, cleaning and cleaning were performed in the same manner as in Example 1.
On both sides of the tonified Nafion 115 membrane,
The catalyst layer formed on the aluminum foil was installed, and 120 kg /
cm Two90 ° C, 90 seconds for heating and pressure contact to nap the catalyst layer
To a catalyst layer-electrolyte assembly
Was. At this time, the catalyst layer formed into a thin aluminum layer is Nafion 1
15 catalyst on one side facing the membrane and through the membrane
The layers were arranged such that the positions of the layers and the catalyst layer on the other side coincided with each other.
【0064】実施例1と同様に、上述のナフィオン11
5膜に形成した触媒層のそれぞれに、厚み0.2mm、
大きさ5cm×5cmの撥水性を有するカーボンペーパ
ーを120kg/cm2、130℃、5分間、加熱圧接
することにより接合にして電極−電解質膜接合体を作製
した。これを電極−電解質膜接合体Bとした。As in the first embodiment, the above-mentioned Nafion 11
Each of the catalyst layers formed in the five films has a thickness of 0.2 mm,
A 5 cm × 5 cm water-repellent carbon paper was heated and pressed at 120 kg / cm 2 at 130 ° C. for 5 minutes to form an electrode-electrolyte membrane assembly. This was designated as electrode-electrolyte membrane assembly B.
【0065】この電極−電解質膜接合体Bをガス流路が
加工された一対の金属製セパレータに挟持して固体高分
子電解質型燃料電池Bを構成した。The polymer electrolyte fuel cell B was constituted by sandwiching the electrode-electrolyte membrane assembly B between a pair of metal separators having gas channels formed therein.
【0066】実施例1で作製した固体高分子電解質型燃
料電池Aと比較例で作製した固体高分子電解質型燃料電
池Bとの電流−電圧特性を測定した。これらの固体高分
子電解質型燃料電池は同じ条件で作動させた。すなわ
ち、燃料ガスには純水素を用いて60℃に設定したバブ
ラー式の加湿器で加湿した後、利用率が70%になる流
量で電池に供給した。酸化ガスには純酸素を用いて60
℃に設定したバブラー式の加湿器で加湿した後、利用率
が50%になる流量で電池に供給した。反応ガスは、そ
れぞれ大気圧で供給した。電池には65℃のクーラント
を循環して、電池温度を一定に保った。The current-voltage characteristics of the solid polymer electrolyte fuel cell A manufactured in Example 1 and the solid polymer electrolyte fuel cell B manufactured in Comparative Example were measured. These solid polymer electrolyte fuel cells were operated under the same conditions. That is, pure hydrogen was used as the fuel gas, and the fuel gas was humidified by a bubbler humidifier set at 60 ° C., and then supplied to the battery at a flow rate at which the utilization factor became 70%. Using pure oxygen as the oxidizing gas, 60
After humidification with a bubbler humidifier set to ° C., the battery was supplied to the battery at a flow rate at which the utilization factor became 50%. The reaction gases were each supplied at atmospheric pressure. Coolant at 65 ° C. was circulated through the battery to keep the battery temperature constant.
【0067】実施例1で作製した固体高分子電解質型燃
料電池Aと比較例で作製した固体高分子電解質型燃料電
池Bの電流−電圧特性を図7に示す。図7から明らかな
ように、電解質膜(実施例ではナフィオン115膜)に
触媒分散物を直接塗布する方法により形成した触媒層
は、高い電流密度での電池電圧の低下が少なく、優れた
特性を示した。本発明の触媒層は、その作製方法が簡素
であることに加えて固体高分子電解質型燃料電池の高出
力化に効果があることが示された。FIG. 7 shows the current-voltage characteristics of the solid polymer electrolyte fuel cell A manufactured in Example 1 and the solid polymer electrolyte fuel cell B manufactured in the comparative example. As is clear from FIG. 7, the catalyst layer formed by the method of directly applying the catalyst dispersion to the electrolyte membrane (the Nafion 115 membrane in the example) has a small decrease in the battery voltage at a high current density and has excellent characteristics. Indicated. It has been shown that the catalyst layer of the present invention is effective in increasing the output of a solid polymer electrolyte fuel cell in addition to the simple manufacturing method.
【0068】[実施例2]本発明の触媒層−電解質接合
体を用いた直接メタノール燃料電池の作製方法の一例を
具体的に説明する。Example 2 An example of a method for manufacturing a direct methanol fuel cell using the catalyst layer-electrolyte assembly of the present invention will be specifically described.
【0069】実施例1と同様にして、触媒と電解質の溶
液からなる触媒分散物を調製した。触媒は白金を20w
t%およびルテニウムを20wt%担持したカーボン粉
末を用いて、電解質の溶液は市販の5wt%ナフィオン
溶液を用いた。1.5gの触媒を5wt%ナフィオン溶
液11.2mlに添加して30分間攪拌して触媒を分散
させた後、攪拌しながら60℃に加熱し、分散媒に対し
てナフィオンの固形分の重量が15wt%になるまで濃
縮した。これを触媒分散物Cとした。In the same manner as in Example 1, a catalyst dispersion comprising a solution of a catalyst and an electrolyte was prepared. The catalyst is platinum 20w
Using a carbon powder carrying 20% by weight of t% and ruthenium, a commercially available 5% by weight Nafion solution was used as the electrolyte solution. After adding 1.5 g of the catalyst to 11.2 ml of a 5 wt% Nafion solution and stirring for 30 minutes to disperse the catalyst, the mixture was heated to 60 ° C. with stirring, and the weight of the solid content of Nafion with respect to the dispersion medium was reduced. It was concentrated to 15 wt%. This was designated as catalyst dispersion C.
【0070】実施例1同様にして、洗浄、プロトン化処
理およびエタノール処理を施したナフィオン115膜を
ガラス板状に配置し、開口部を有する額縁状シートを配
置した後、スキージブレードを用いて、余剰の水とエタ
ノールとを扱きとり、ナフィオン115膜、ガラス板お
よび額縁状シートそれぞれを密着させた。この額縁状の
シートは、実施例1で使用したものと同様に12.5μ
mのテトラフロロエチレンーヘキサフロロプロピレン共
重合体シートに5cm×5cmの開口部を形成したもの
を用いた。このとき額縁状シートの開口部に位置するナ
フィオン115膜表面の余剰の水とエタノールも取り除
いた。In the same manner as in Example 1, a Nafion 115 membrane subjected to washing, protonation, and ethanol treatment was arranged in a glass plate shape, and a frame-shaped sheet having an opening was arranged. Then, using a squeegee blade, Excess water and ethanol were handled, and the Nafion 115 film, the glass plate, and the frame-shaped sheet were brought into close contact with each other. This frame-shaped sheet was 12.5 μm in the same manner as used in Example 1.
m having a 5 cm × 5 cm opening in a tetrafluoroethylene-hexafluoropropylene copolymer sheet was used. At this time, excess water and ethanol on the surface of the Nafion 115 film located at the opening of the frame-shaped sheet were also removed.
【0071】実施例1と同様の方法で、ナフィオン11
5膜に触媒分散物Cを塗布して、触媒層を形成した。す
なわち、開口部の近傍の額縁部に適量の触媒分散物Cを
とり、スキージブレードを掃引して開口部のナフィオン
115膜に塗布した。その後、室温で放置して触媒分散
物Cを乾燥してナフィオン115膜に約8μm厚の触媒
層を形成し、精製水中に保存した。つぎに、この片面に
触媒層を形成したナフィオン115膜を精製水から取り
出して、触媒層の形成されている面がガラス板と向かい
合うように設置し、スキージブレードを用いて片面に触
媒層を形成したナフィオン115膜とガラス板との間に
存在する水を扱き取り、それらを密着させた。In the same manner as in Example 1, Nafion 11
Catalyst dispersion C was applied to five films to form a catalyst layer. That is, an appropriate amount of the catalyst dispersion C was taken in a frame portion near the opening, and was applied to the Nafion 115 film in the opening by sweeping with a squeegee blade. Thereafter, the catalyst dispersion C was dried at room temperature to form a catalyst layer having a thickness of about 8 μm on a Nafion 115 membrane, and stored in purified water. Next, the Nafion 115 film having the catalyst layer formed on one side is taken out of the purified water, and placed so that the surface on which the catalyst layer is formed faces the glass plate, and the catalyst layer is formed on one side using a squeegee blade. The water present between the Nafion 115 film and the glass plate was removed and brought into close contact.
【0072】つぎに、そのナフィオン115膜の他方の
面にエタノールを噴霧した後、前述のものと同様の開口
部を有する額縁状シートを配置し、スキージブレードを
用いて片面に触媒層を形成したナフィオン115膜と額
縁状シートとの間に存在するエタノールを扱き取り、そ
れらを密着させた。このとき額縁状シートの開口部に位
置するナフィオン115膜表面の余剰のエタノールも取
り除いた。なお、片面に形成した触媒層と他方の面に配
置する額縁状のシートの開口部とは膜を介して重なり合
うように配置した。Next, after spraying ethanol on the other surface of the Nafion 115 film, a frame-like sheet having the same opening as that described above was arranged, and a catalyst layer was formed on one surface using a squeegee blade. Ethanol existing between the Nafion 115 film and the frame-shaped sheet was handled and brought into close contact. At this time, excess ethanol on the surface of the Nafion 115 film located at the opening of the frame-shaped sheet was also removed. The catalyst layer formed on one side and the opening of the frame-shaped sheet disposed on the other side were arranged so as to overlap with each other via a membrane.
【0073】つぎに、前述の方法と同様に開口部の近傍
の額縁部に適量の触媒分散物Aをとり、スキージブレー
ドを掃引して開口部のナフィオン115膜に塗布した。
その後、室温で放置して触媒分散物Aを乾燥してナフィ
オン115膜の他方の面にも約8μm厚の触媒層を形成
して、触媒層−電解質接合体を作製し、精製水中に保存
した。Next, in the same manner as described above, an appropriate amount of the catalyst dispersion A was taken in the frame near the opening, and the squeegee blade was swept to apply it to the Nafion 115 film in the opening.
After that, the catalyst dispersion A was dried at room temperature to form a catalyst layer having a thickness of about 8 μm on the other surface of the Nafion 115 membrane, and a catalyst layer-electrolyte assembly was prepared and stored in purified water. .
【0074】上述のナフィオン115膜の一方の面に形
成した触媒分散物Cからなる触媒層に、厚み0.2m
m、大きさ5cm×5cmのカーボンペーパーを、他方
の面に形成した触媒分散物Aからなる触媒層に撥水性を
有するカーボンペーパーを120kg/cm2、130
℃、5分間、加熱圧接することによりそれぞれを接合に
して、電極−電解質膜接合体を作製した。これを電極−
電解質膜接合体Cとした。The catalyst layer composed of the catalyst dispersion C formed on one surface of the above-mentioned Nafion 115 membrane was added with a thickness of 0.2 m.
m, a carbon paper having a size of 5 cm × 5 cm, and a water-repellent carbon paper in a catalyst layer made of the catalyst dispersion A formed on the other surface were applied at 120 kg / cm 2, 130
Each was joined by heating and pressure welding at a temperature of 5 ° C. for 5 minutes to produce an electrode-electrolyte membrane assembly. This is the electrode
An electrolyte membrane assembly C was obtained.
【0075】この電極−電解質膜接合体Cをガス流路が
加工された一対の金属製セパレータに挟持して直接メタ
ノール燃料電池Cを構成した。この直接メタノール燃料
電池Cの燃料極(アノード)には白金とルテニウムとを
担持したカーボン触媒を含む触媒分散物Cから作製され
た触媒層を、空気極(カソード)には白金を担持したカ
ーボン触媒を含む触媒分散物Aから作製した触媒層をそ
れぞれ配した。[0075] The electrode-electrolyte membrane assembly C was sandwiched between a pair of metal separators in which gas channels were processed, to directly construct a methanol fuel cell C. The fuel layer (anode) of the direct methanol fuel cell C has a catalyst layer made of a catalyst dispersion C containing a carbon catalyst supporting platinum and ruthenium, and the air electrode (cathode) has a carbon catalyst supporting platinum. Each of the catalyst layers produced from the catalyst dispersion A containing
【0076】この直接メタノール燃料電池を、つぎの条
件で作動させて、電流−電圧特性を測定した。カソード
に3気圧に加圧した酸素を供給し、アノードに2気圧に
加圧した1Mのメタノール/水を供給した。電池には1
10℃のクーラントを循環して、電池温度を一定に保っ
た。This direct methanol fuel cell was operated under the following conditions, and the current-voltage characteristics were measured. Oxygen pressurized to 3 atm was supplied to the cathode, and 1 M methanol / water pressurized to 2 atm was supplied to the anode. 1 for battery
A 10 ° C. coolant was circulated to keep the cell temperature constant.
【0077】実施例2で作製した直接メタノール燃料電
池Cの電流−電圧特性を図8に示す。本発明の触媒層の
製造方法は、直接メタノール燃料電池にも有効であるこ
とが確かめられた。FIG. 8 shows the current-voltage characteristics of the direct methanol fuel cell C manufactured in Example 2. It was confirmed that the method for producing a catalyst layer of the present invention is also effective for a direct methanol fuel cell.
【0078】[0078]
【発明の効果】本発明は、電解質膜に均一な触媒層を形
成した触媒層−電解質接合体の製造方法を提供し、本発
明の製造方法で作製した触媒層−電解質接合体の触媒層
は、電解質膜の寸法変化に起因する剥離、脱落やひび割
れの影響を受けず、均一なものとなり、均一な触媒層を
有する触媒層−電解質接合体を使用した電気化学装置、
とくに固体高分子電解質型燃料電池および直接メタノー
ル燃料電池を高出力にすることができる。The present invention provides a method for producing a catalyst layer-electrolyte assembly in which a uniform catalyst layer is formed on an electrolyte membrane, and the catalyst layer of the catalyst layer-electrolyte assembly produced by the production method of the present invention comprises: An electrochemical device using a catalyst layer-electrolyte assembly having a uniform catalyst layer without being affected by peeling, falling off or cracking caused by a dimensional change of the electrolyte membrane,
In particular, the solid polymer electrolyte fuel cell and the direct methanol fuel cell can have high output.
【図1】アルコール処理を施した電解質膜、平板および
は開口部を有する額縁状のシートを配置した状態を上方
からみた様子を示す図である。FIG. 1 is a diagram showing a state in which an electrolyte membrane, a flat plate, and a frame-shaped sheet having an opening are disposed after alcohol treatment, as viewed from above.
【図2】アルコール処理を施した電解質膜1、平板2お
よびは開口部を有する額縁状のシート3を配置した状態
を断面方向からみた様子を示す図である。FIG. 2 is a diagram showing a state in which an electrolyte membrane 1, a flat plate 2, and a frame-shaped sheet 3 having openings are arranged in an alcohol treatment, as viewed from a cross-sectional direction.
【図3】本発明の触媒分散物の塗布方法に必要な構成材
を示す。FIG. 3 shows components necessary for the method for applying a catalyst dispersion of the present invention.
【図4】本発明の触媒分散物の塗布方法おいて、触媒分
散物を配置した状態を示す模式図。FIG. 4 is a schematic diagram showing a state in which the catalyst dispersion is arranged in the method for applying the catalyst dispersion of the present invention.
【図5】本発明の触媒分散物の塗布方法おいて、触媒分
散物をスキージブレードで引き延ばしている状態を示す
模式図。FIG. 5 is a schematic view showing a state in which the catalyst dispersion is stretched by a squeegee blade in the method for applying the catalyst dispersion of the present invention.
【図6】本発明の触媒分散物の塗布方法おいて、触媒分
散物をスキージブレードで掃引して塗布した状態を示す
模式図。FIG. 6 is a schematic view showing a state where the catalyst dispersion is applied by sweeping with a squeegee blade in the method for applying the catalyst dispersion of the present invention.
【図7】本発明の触媒層を備えた電極−電解質膜接合体
を用いて構成した固体高分子電解質型燃料電池Aおよび
従来法で作製した触媒層を備えた電極−電解質膜接合体
を用いて構成した固体高分子電解質型燃料電池Bの電流
−電圧特性を示す図。FIG. 7 shows a solid polymer electrolyte fuel cell A constructed using an electrode-electrolyte membrane assembly provided with a catalyst layer of the present invention and an electrode-electrolyte membrane assembly provided with a catalyst layer produced by a conventional method. FIG. 4 is a diagram showing current-voltage characteristics of a solid polymer electrolyte fuel cell B configured as described above.
【図8】本発明の触媒層を備えた電極−電解質膜接合体
を用いて構成した直接メタノール燃料電池Cの電流−電
圧特性を示す図。FIG. 8 is a view showing current-voltage characteristics of a direct methanol fuel cell C constituted by using an electrode-electrolyte membrane assembly provided with a catalyst layer of the present invention.
1 アルコール処理を施した電解質膜 2 平板 3 開口部を有する額縁状シート 4 開口部を有する額縁状シート3の開口部 5 開口部を有する額縁状シート3の額縁部 6 触媒分散物 7 スキージブレード 8 塗布された触媒分散物 9 スキージブレードの掃引方向 10 触媒層 Reference Signs List 1 electrolyte membrane subjected to alcohol treatment 2 flat plate 3 frame-shaped sheet having opening 4 opening of frame-shaped sheet 3 having opening 5 frame of frame-shaped sheet 3 having opening 6 catalyst dispersion 7 squeegee blade 8 Applied catalyst dispersion 9 sweep direction of squeegee blade 10 catalyst layer
Claims (5)
を含浸し、次いで前記電解質膜の片面もしくは両面に、
触媒と電解質を含む触媒層を形成することを特徴とす
る、触媒層−電解質接合体の製造方法。1. An electrolyte membrane impregnated with an alcohol having 4 or less carbon atoms, and then, on one or both sides of the electrolyte membrane,
A method for producing a catalyst layer-electrolyte assembly, comprising forming a catalyst layer containing a catalyst and an electrolyte.
類を含浸し、次いで前記電解質膜を平板上に配置して、
次いで前記電解質膜の上面に開口部を有する額縁状シー
トを配し、次いで前記額縁状シートその開口部から電解
質膜に触媒と電解質を含む触媒分散物を塗布することを
特徴とする、請求項1記載の触媒層−電解質接合体の製
造方法。2. An electrolyte membrane is impregnated with an alcohol having 4 or less carbon atoms, and then the electrolyte membrane is arranged on a flat plate.
2. A frame-shaped sheet having an opening on the upper surface of the electrolyte membrane, and a catalyst dispersion containing a catalyst and an electrolyte is applied to the electrolyte membrane from the opening of the frame-shaped sheet. The method for producing a catalyst layer-electrolyte assembly according to the above.
り、触媒層の厚みを制御することを特徴とする、請求項
2記載の触媒層−電解質接合体の製造方法。3. The method for producing a catalyst layer-electrolyte assembly according to claim 2, wherein the thickness of the catalyst layer is controlled by the thickness of the frame-shaped sheet having openings.
た触媒層−電解質接合体を備えたことを特徴とする電気
化学装置。4. An electrochemical device comprising a catalyst layer-electrolyte assembly produced by the production method according to claim 1. Description:
電池もしくは直接メタノール燃料電池であることを特徴
とする、請求項4記載の電気化学装置。5. The electrochemical device according to claim 4, wherein the electrochemical device is a solid polymer electrolyte fuel cell or a direct methanol fuel cell.
Priority Applications (1)
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JP11109413A JP2000299119A (en) | 1999-04-16 | 1999-04-16 | Manufacture of catalyst layer |
Applications Claiming Priority (1)
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JP11109413A JP2000299119A (en) | 1999-04-16 | 1999-04-16 | Manufacture of catalyst layer |
Publications (2)
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JP2000299119A true JP2000299119A (en) | 2000-10-24 |
JP2000299119A5 JP2000299119A5 (en) | 2006-06-08 |
Family
ID=14509627
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JP11109413A Withdrawn JP2000299119A (en) | 1999-04-16 | 1999-04-16 | Manufacture of catalyst layer |
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JP (1) | JP2000299119A (en) |
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JP2003086200A (en) * | 2001-09-14 | 2003-03-20 | Matsushita Electric Ind Co Ltd | Method of manufacturing electrolyte membrane/ electrode assembly, and polymer electrolyte fuel cell |
JP2003175340A (en) * | 2001-09-04 | 2003-06-24 | Korea Inst Of Science & Technology | Composite hydrogen ion exchange membrane having separation capacity, composite solution, its production method, and fuel cell containing it |
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