JPH10270050A - Fuel cell electrode and its manufacture - Google Patents
Fuel cell electrode and its manufactureInfo
- Publication number
- JPH10270050A JPH10270050A JP9093093A JP9309397A JPH10270050A JP H10270050 A JPH10270050 A JP H10270050A JP 9093093 A JP9093093 A JP 9093093A JP 9309397 A JP9309397 A JP 9309397A JP H10270050 A JPH10270050 A JP H10270050A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- fuel cell
- layer
- electrode
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、燃料電池用電極及
びその製造方法に関し、より具体的にはガス拡散層上に
触媒粒子、電解質及び撥水化剤を含む触媒層を形成した
燃料電池用電極及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel cell electrode and a method of manufacturing the same, and more particularly, to a fuel cell electrode having a catalyst layer containing catalyst particles, an electrolyte and a water repellent formed on a gas diffusion layer. The present invention relates to an electrode and a method for manufacturing the electrode.
【０００２】[0002]
【従来の技術】燃料電池、例えば固体高分子型燃料電池
はイオン伝導体すなわち電解質が固体で且つ高分子であ
る点に特徴を有するものであるが、その固体高分子電解
質としては具体的にはイオン交換樹脂等の膜が使用さ
れ、この高分子電解質膜を挟んで負極（アノード）及び
正極（カソード）の両電極を配置し、例えば負極側に燃
料としての水素ガスを、また正極側には酸素又は空気を
供給して電気化学反応を起こさせることにより電気を発
生させるものである。2. Description of the Related Art A fuel cell, for example, a polymer electrolyte fuel cell, is characterized in that the ionic conductor, that is, the electrolyte is a solid and a polymer. A membrane such as an ion-exchange resin is used, and a negative electrode (anode) and a positive electrode (cathode) are arranged with the polymer electrolyte membrane interposed therebetween. For example, hydrogen gas as a fuel is provided on the negative electrode side, and hydrogen gas is provided on the positive electrode side. It generates electricity by supplying oxygen or air to cause an electrochemical reaction.
【０００３】燃料電池にはこれまで各種態様のものがあ
るが、図１は、そのうち固体高分子型燃料電池の一態様
を説明するための概略図である。図１中、１は高分子電
解質膜、２はカソード電極（正極）、３はアノード電極
（負極）であり、高分子電解質膜１は相対するこの正負
両電極２、３間に当接して配置されている。また４はカ
ソード電極側集電体、５はアノード電極側集電体であ
り、それぞれ正負の電極２及び３に当接されている。There are various types of fuel cells so far, and FIG. 1 is a schematic diagram for explaining one mode of a polymer electrolyte fuel cell. In FIG. 1, 1 is a polymer electrolyte membrane, 2 is a cathode electrode (positive electrode), 3 is an anode electrode (negative electrode), and the polymer electrolyte membrane 1 is disposed in contact between the opposite positive and negative electrodes 2, 3. Have been. Reference numeral 4 denotes a cathode-side current collector, and reference numeral 5 denotes an anode-side current collector, which are in contact with the positive and negative electrodes 2 and 3, respectively.
【０００４】カソード電極側集電体４の電極２側には酸
素又は空気供給用の溝が設けられ、同じくアノード電極
側集電体５の電極３側には水素供給用の溝が設けられ
る。正極側集電体４の溝は酸素又は空気供給管６に、負
極側集電体５の溝は水素供給管７に連通している。また
８は正極側集電体４に当接して設けられたカソード端子
板、９は負極側集電体５に当接して設けられたアノード
端子板であり、電池の作動中にこれらを通して電力が取
り出される。さらに１０は左部枠体（左部フレーム）、
１１は右部枠体（右部フレーム）であり、これら左右両
枠体１０、１１により高分子電解質膜１からカソード端
子板８及びアノード端子板９までの電池本体を被って固
定されている。[0004] A groove for supplying oxygen or air is provided on the electrode 2 side of the cathode-side current collector 4, and a groove for supplying hydrogen is provided on the electrode 3 side of the anode-side current collector 5. The groove of the positive electrode side current collector 4 communicates with the oxygen or air supply pipe 6, and the groove of the negative electrode side current collector 5 communicates with the hydrogen supply pipe 7. Reference numeral 8 denotes a cathode terminal plate provided in contact with the positive-side current collector 4, and 9 denotes an anode terminal plate provided in contact with the negative-side current collector 5, through which power is supplied during operation of the battery. Taken out. 10 is a left frame (left frame),
Reference numeral 11 denotes a right frame (right frame). The right and left frames 10 and 11 cover and fix the battery body from the polymer electrolyte membrane 1 to the cathode terminal plate 8 and the anode terminal plate 9.
【０００５】これら左右両枠体１０、１１間には、高分
子電解質膜１からカソード端子板８及びアノード端子板
９までの電池本体の周縁部を囲ってパッキン（ガスケッ
ト）１２が設けられ、これによってその電池本体の周縁
部を密に固定してシールし、特に高分子電解質膜１及び
正負両電極２、３に対してガスシールされている。なお
図１中、１３及び１４は冷却水供給管であり、これらは
それぞれ左部枠体１０及び右部枠体１１の内面に設けら
れた溝（閉通路）に連通し、カソード端子板８の背面及
びアノード端子板９の背面から冷却するようになってい
る。A packing (gasket) 12 is provided between the left and right frames 10 and 11 so as to surround the periphery of the battery body from the polymer electrolyte membrane 1 to the cathode terminal plate 8 and the anode terminal plate 9. Thus, the peripheral portion of the battery body is tightly fixed and sealed, and in particular, gas is sealed to the polymer electrolyte membrane 1 and the positive and negative electrodes 2 and 3. In FIG. 1, reference numerals 13 and 14 denote cooling water supply pipes, which communicate with grooves (closed passages) provided on the inner surfaces of the left frame 10 and the right frame 11, respectively. Cooling is performed from the back surface and the back surface of the anode terminal plate 9.
【０００６】以上は、電池本体が単一の場合であるが、
この電池本体を二つ以上積み重ねて構成することも行わ
れる。この場合には二つ以上の各電池本体間にセパレー
タを介在させ、必要に応じてこれにも冷却水用の溝等を
設ける必要はあるが、電池本体の周縁部を囲ってパッキ
ンを設け、その電池本体の周縁部を密に固定してシール
し、高分子電解質膜１及び正負両電極２、３に対してガ
スシールをすること等を含めて、基本的には上述単一の
電池本体の場合と同じである。この場合にはパッキン１
２等の締め付けはセパレータをも介して行われる。[0006] The above is the case of a single battery body,
In some cases, two or more battery bodies are stacked. In this case, a separator is interposed between two or more battery bodies, and it is necessary to provide a groove for cooling water and the like as necessary, but a packing is provided around the periphery of the battery body, Basically, the peripheral portion of the battery body is tightly fixed and sealed, and gas sealing is performed on the polymer electrolyte membrane 1 and the positive and negative electrodes 2 and 3. Is the same as In this case packing 1
Tightening such as 2 is also performed via a separator.
【０００７】この種の燃料電池における反応は、高分子
電解質膜が水素イオン導電体としてのカチオン交換膜で
ある場合、高分子電解質膜１とカソード電極（正極）２
の間では下記式（１）の反応、高分子電解質膜とアノー
ド電極（負極）３の間では下記式（２）の反応をし、全
体としては下記式（３）の反応が進行する。In a fuel cell of this type, when the polymer electrolyte membrane is a cation exchange membrane as a hydrogen ion conductor, the polymer electrolyte membrane 1 and the cathode electrode (positive electrode) 2
The reaction of the following formula (1) takes place between the polymer electrolyte membrane and the anode electrode (negative electrode) 3, and the reaction of the following formula (2) proceeds as a whole.
【化 １】 カソード（負極）：１／２Ｏ2 ＋ ２Ｈ+ ＋ ２ｅ- → Ｈ2Ｏ （１） アノード（正極）：Ｈ2 → ２Ｈ+ ＋ ２ｅ- （２） 全 反 応：１／２Ｏ2 ＋ Ｈ2 → Ｈ2Ｏ （３）Embedded image Cathode (negative electrode): 1 / 2O 2 + 2H + + 2e − → H 2 O (1) Anode (positive electrode): H 2 → 2H + + 2e − (2) Total reaction: 1 / 2O 2 + H 2 → H 2 O (3)
【０００８】ところで、上記のような形式の燃料電池に
おける燃料は水素である。水素は水の電解等によっても
得られるが、化石燃料である都市ガス（天然ガス）等を
改質して製造される。その際ＣＯ（一酸化炭素）の生成
は可及的に回避するようにされ、必要に応じてさらに除
去されるが、それでも例えば１００ｐｐｍ以下というよ
うな微量のＣＯ（一酸化炭素）が含まれている。このた
め燃料電池の燃料極側の触媒層としてはＣＯに被毒しに
くい触媒、例えば白金ールテニウム系の触媒を使用する
必要がある。しかし白金ールテニウム系触媒はＣＯによ
る被毒を受けにくい触媒であるが、白金触媒に比べて触
媒活性が劣る。このためＣＯを含まない水素を燃料とし
た時の白金触媒を用いた電池ほどの性能はどうしても得
られなかった。[0008] The fuel in a fuel cell of the type described above is hydrogen. Hydrogen can also be obtained by electrolysis of water or the like, but is produced by reforming fossil fuel such as city gas (natural gas). At this time, the generation of CO (carbon monoxide) is avoided as much as possible, and it is further removed as necessary. However, a small amount of CO (carbon monoxide) such as 100 ppm or less is still contained. I have. For this reason, it is necessary to use a catalyst hardly poisoned by CO, for example, a platinum-ruthenium-based catalyst, as the catalyst layer on the fuel electrode side of the fuel cell. However, platinum-ruthenium-based catalysts are less susceptible to poisoning by CO, but have lower catalytic activity than platinum catalysts. For this reason, the performance of a battery using a platinum catalyst when using hydrogen containing no CO as a fuel could not be obtained.
【０００９】[0009]
【発明が解決しようとする課題】本発明者は、上記問題
点を改善、解決するため各種多方面から研究検討を続け
たところ、その触媒層として、ＣＯによる被毒を受けに
くい触媒と活性に優れた触媒とを特定の手法で併用する
ことにより解決できることを見い出し、本発明に到達す
るに至ったものである。SUMMARY OF THE INVENTION The present inventor has been conducting research and studies from various aspects to improve and solve the above-mentioned problems. The inventors have found that the problem can be solved by using an excellent catalyst in combination with a specific method, and have reached the present invention.
【００１０】すなわち本発明は、ガス拡散層上に触媒粒
子、電解質、撥水化剤を含む触媒層を形成した燃料電池
用電極において、ガス拡散層上に形成する触媒層とし
て、活性の高い触媒の層とともに、耐ＣＯ性に優れる触
媒の層を特定の順序で積層形成することにより、活性の
高い触媒のＣＯによる被毒を防止するようにしてなる燃
料電池用電極及びその製造方法を提供することを目的と
する。That is, according to the present invention, in a fuel cell electrode in which a catalyst layer containing catalyst particles, an electrolyte and a water repellent is formed on a gas diffusion layer, a highly active catalyst is formed as a catalyst layer formed on the gas diffusion layer. The present invention provides an electrode for a fuel cell and a method for manufacturing the same, which prevents the poisoning of a highly active catalyst by CO by forming a layer of a catalyst having excellent CO resistance in a specific order together with a layer of The purpose is to:
【００１１】[0011]
【課題を解決するための手段】本発明は、ガス拡散層上
に触媒粒子、電解質、撥水化剤を含む触媒層を形成した
燃料電池用電極であって、該ガス拡散層上に耐ＣＯ性に
優れる触媒を第１層とし、触媒活性に優れる触媒層を第
２層として積層形成してなることを特徴とする燃料電池
用電極を提供する。SUMMARY OF THE INVENTION The present invention is an electrode for a fuel cell in which a catalyst layer containing catalyst particles, an electrolyte and a water repellent is formed on a gas diffusion layer. The present invention provides an electrode for a fuel cell, wherein a catalyst having excellent catalytic properties is formed as a first layer and a catalyst layer having excellent catalytic activity is formed as a second layer.
【００１２】また、本発明は、ガス拡散層上に触媒粒
子、電解質、撥水化剤を含む触媒層を形成した燃料電池
用電極の製造法において、該ガス拡散層上に耐ＣＯ性に
優れる触媒からなる第１層を形成し、その上に触媒活性
に優れる触媒層からなる第２層を積層形成することを特
徴とする燃料電池用電極の製造方法を提供する。Further, the present invention provides a method for producing an electrode for a fuel cell in which a catalyst layer containing catalyst particles, an electrolyte and a water repellent is formed on a gas diffusion layer, and the gas diffusion layer has excellent CO resistance. A method for producing an electrode for a fuel cell, comprising: forming a first layer made of a catalyst, and forming a second layer made of a catalyst layer having excellent catalytic activity on the first layer.
【００１３】[0013]
【発明の実施の形態】燃料電池には、りん酸型、アルカ
リ型、固体高分子型等各種あるが、本発明の電極及びそ
の製造方法はそれらの何れの燃料電池用の電極としても
適用される。本発明の電極は触媒粒子、電解質及び撥水
化剤を含むが、本発明においては、その触媒粒子として
（１）触媒活性に優れる触媒粒子と（２）耐ＣＯ性に優
れる触媒粒子との二種類の触媒粒子が用いられる。DESCRIPTION OF THE PREFERRED EMBODIMENTS There are various types of fuel cells, such as a phosphoric acid type, an alkaline type, and a solid polymer type. The electrode of the present invention and the method for producing the same are applied as electrodes for any of those fuel cells. You. The electrode of the present invention contains catalyst particles, an electrolyte and a water repellent. In the present invention, the catalyst particles include (1) catalyst particles having excellent catalytic activity and (2) catalyst particles having excellent CO resistance. Different types of catalyst particles are used.
【００１４】このうち（１）触媒活性に優れる触媒粒子
を構成する触媒としては、燃料電池電極用触媒として、
触媒活性に優れ、使用し得るものであれば特に限定はな
く、その例としては白金ブラック粉末、白金合金粉末、
パラジウムブラック粉末、パラジウム合金粉末等の活性
金属粉末を挙げることができる。これらの触媒粉末はそ
れ自体としても触媒粒子として使用されるが、好ましく
は担体粒子に担持させて触媒粒子とされる。担体粒子と
しては特に限定はないが、好ましくはカーボンブラック
等のカーボン粒子が用いられ、この場合には白金担持の
カーボン粒子、白金合金担持のカーボン粒子、パラジウ
ム担持のカーボン粒子、パラジウム合金担持のカーボン
粒子等として構成されるが、これら活性金属は担体粒子
に一種又は二種以上が担持される。Among them, (1) The catalyst constituting the catalyst particles having excellent catalytic activity is as follows:
There is no particular limitation as long as it has excellent catalytic activity and can be used, and examples thereof include platinum black powder, platinum alloy powder,
Active metal powders such as palladium black powder and palladium alloy powder can be mentioned. These catalyst powders are used as catalyst particles themselves, but are preferably supported on carrier particles to form catalyst particles. The carrier particles are not particularly limited, but carbon particles such as carbon black are preferably used.In this case, platinum-supported carbon particles, platinum-alloy-supported carbon particles, palladium-supported carbon particles, and palladium-alloy-supported carbon particles are used. Although these active metals are constituted as particles or the like, one or more of these active metals are supported on carrier particles.
【００１５】また（２）耐ＣＯ性に優れた触媒粒子とし
ては、耐ＣＯ性に優れた金属であれば使用されるが、そ
の例としては白金ールテニウム系の触媒等が挙げられ
る。これらの触媒はそれ自体粉末とし触媒粒子として使
用されるが、好ましくは担体粒子に担持させて触媒粒子
とされ、担体粒子に一種又は二種以上が担持される。担
体粒子としては特に限定はないが、好ましくはカーボン
ブラック等のカーボン粒子が用いられる。なお、上記白
金ールテニウム系の触媒は白金とルテニウムを含む合金
又は両金属を含む混合物として用いられるが、その各成
分の比率は所望の耐ＣＯ性、触媒活性等に応じて適宜設
定される。[0015] As (2) catalyst particles having excellent CO resistance, any metal having excellent CO resistance can be used, and examples thereof include platinum-ruthenium catalysts. These catalysts are themselves used as powders and used as catalyst particles. Preferably, the catalyst particles are supported on carrier particles, and one or two or more types are supported on the carrier particles. The carrier particles are not particularly limited, but carbon particles such as carbon black are preferably used. The platinum-ruthenium-based catalyst is used as an alloy containing platinum and ruthenium or as a mixture containing both metals, and the ratio of each component is appropriately set according to desired CO resistance, catalytic activity and the like.
【００１６】本発明ではそれら（１）触媒活性に優れた
触媒、好ましくは担体粒子に活性金属を担持した触媒と
（２）耐ＣＯ性に優れた触媒、好ましくは担体粒子に耐
ＣＯ性に優れた金属を担持した触媒とを、多孔性の基材
上に、まず（２）の層を形成し、次いで（１）の層を形
成して積層する。多孔性の基材は電極中でガス拡散層と
なるもので、材料としては各種材質からなる多孔性のペ
ーパー又はシート（本明細書中、両者を含めて適宜「シ
ート」と指称している）、或いはこれらを適宜撥水化し
て使用することができるが、好ましくはカーボンペーパ
ーや撥水化カーボンペーパーを用いることができ、この
うちその優れた特性から特に撥水化カーボンペーパーを
用いるのが特に有効である。In the present invention, (1) a catalyst having excellent catalytic activity, preferably a catalyst having an active metal supported on carrier particles, and (2) a catalyst having excellent CO resistance, preferably having excellent CO resistance. First, a layer of (2) is formed on a porous substrate, and then a layer of (1) is formed and laminated on a porous substrate. The porous base material serves as a gas diffusion layer in the electrode, and is made of a porous paper or sheet made of various materials (in this specification, both are referred to as "sheets" as appropriate). Alternatively, these can be used by appropriately making them water-repellent. Preferably, carbon paper or water-repellent carbon paper can be used, and among them, it is particularly preferable to use water-repellent carbon paper because of its excellent properties. It is valid.
【００１７】上記撥水化カーボンペーパーは、所定の気
孔率及び厚さを有するカーボンペーパーを用い、これに
対して撥水化剤、好ましくはポリテトラフルオロエチレ
ン系ポリマーのディスパージョンを含浸させた後、熱処
理をして撥水化したものである。ここでポリテトラフル
オロエチレン系ポリマーとはポリテトラフルオロエチレ
ン（ＰＴＦＥ）のほか、テトラフルオロエチレンーヘキ
サフルオロプロピレン共重合体等の共重合体、その他そ
の誘導体を含む意味である。As the water-repellent carbon paper, a carbon paper having a predetermined porosity and thickness is used, and after impregnated with a water-repellent agent, preferably a dispersion of a polytetrafluoroethylene polymer. And heat treated to make it water repellent. Here, the polytetrafluoroethylene-based polymer is meant to include not only polytetrafluoroethylene (PTFE) but also a copolymer such as a tetrafluoroethylene-hexafluoropropylene copolymer and other derivatives thereof.
【００１８】図２は多孔性の基材上へ上記両触媒の層を
積層形成した電極シートの状態を示す図である。図２
中、１５は多孔性の基材（ガス拡散層となる）、１６は
耐ＣＯ性に優れた触媒の層、１７は触媒活性に優れた触
媒の層である。この電極シートを燃料電池に組み込むと
きは、電解質（例えば高分子電解質膜）に対して触媒活
性に優れる触媒の層１７が第１層（すなわち電解質
側）、耐ＣＯ性に優れる触媒の層１６が第２層となるよ
うに配置される。FIG. 2 is a diagram showing a state of an electrode sheet in which the above-mentioned catalyst layers are laminated on a porous substrate. FIG.
Among them, 15 is a porous base material (to be a gas diffusion layer), 16 is a catalyst layer having excellent CO resistance, and 17 is a catalyst layer having excellent catalytic activity. When this electrode sheet is incorporated into a fuel cell, the catalyst layer 17 having excellent catalytic activity with respect to an electrolyte (for example, a polymer electrolyte membrane) is composed of a first layer (that is, the electrolyte side) and the catalyst layer 16 having excellent CO resistance. It is arranged to be the second layer.
【００１９】これら両触媒の多孔性の基材すなわちガス
拡散層上への積層の仕方としては、（１）各触媒粒子を
含む混練物を順次積層する、（２）各触媒粒子を粉末と
して散布積層し、加熱下、プレスする、（３）各触媒粒
子を含む懸濁液を順次積層する等、特に限定はないが、
好ましくは（４）各触媒粒子を含む懸濁液を順次濾過法
により積層する、（５）各触媒粒子を含む懸濁液又は粘
性懸濁液を順次塗工法又は印刷法により積層する態様が
使用される。このうち（４）の濾過法による場合には、
特に好ましくは加圧濾過法が用いられる。The method of laminating these two catalysts on a porous substrate, that is, a gas diffusion layer, is as follows: (1) kneaded material containing each catalyst particle is sequentially laminated; (2) each catalyst particle is dispersed as powder. There is no particular limitation such as laminating and pressing under heating, and (3) laminating a suspension containing each catalyst particle sequentially.
Preferably, (4) the suspension containing each catalyst particle is sequentially laminated by a filtration method, and (5) the suspension or the viscous suspension containing each catalyst particle is sequentially laminated by a coating method or a printing method. Is done. In the case of the filtration method (4),
Particularly preferably, a pressure filtration method is used.
【００２０】上記の態様における活性金属担持の触媒粒
子を含む懸濁液としては、活性金属担持のカーボンブ
ラック粒子と電解質の溶液とを混合して得た懸濁液、
、の懸濁液に結合剤（撥水化剤としての役目も有す
る）として例えばポリテトラフルオロエチレン系ポリマ
ーを混合してなる懸濁液等が用いられる。これらの点は
耐ＣＯ性に優れた金属を担持した触媒粒子を含む懸濁液
の場合についても同様である。この場合、例えば特願平
５ー２９７２８０号のように、その懸濁液を希硫酸水溶
液に分散させたものも使用することにより、これによる
効果（電極としての特性を向上させ、これを用いた電池
の性能を格段に改善させる）に加え、本発明による効果
も得ることができる。The suspension containing the active metal-supported catalyst particles in the above embodiment includes a suspension obtained by mixing an active metal-supported carbon black particle and an electrolyte solution.
For example, a suspension or the like obtained by mixing a polytetrafluoroethylene-based polymer as a binder (also having a role as a water-repellent agent) to the suspension is used. These points are the same as in the case of a suspension containing catalyst particles carrying a metal having excellent CO resistance. In this case, for example, as disclosed in Japanese Patent Application No. 5-297280, a suspension obtained by dispersing the suspension in a dilute sulfuric acid aqueous solution is used, thereby obtaining the effect (improving the characteristics as an electrode and using the same). In addition to significantly improving the performance of the battery), the effect of the present invention can be obtained.
【００２１】図３は、上記（４）の態様のうち、加圧濾
過法を適用する場合の態様例を示す図である（特開平８
ー１４８１５４号公報）。図３中１８は中空筒状体であ
り、これは図示のとおり竪型に配置されるが、材質とし
てはガラス製、金属製等適宜のものが使用できる。１９
は上板、２０は下板、２１、２２はそれぞれ上方及び下
方のパッキン、２３は触媒層が堆積されるシート（ガス
拡散板）である。このうちパッキン２１及び２２は、中
空筒状体の上下縁部の形状に合わせた形状に構成され、
例えば中空筒状体が円筒状である場合には、その縁部に
対応して円環状に構成される。FIG. 3 is a diagram showing an example of the case (4) in which the pressure filtration method is applied (Japanese Unexamined Patent Publication No.
-148154). In FIG. 3, reference numeral 18 denotes a hollow cylindrical body, which is arranged vertically as shown in the figure, but may be made of any suitable material such as glass or metal. 19
Is an upper plate, 20 is a lower plate, 21 and 22 are upper and lower packings, respectively, and 23 is a sheet (gas diffusion plate) on which a catalyst layer is deposited. Of these, the packings 21 and 22 are formed in a shape corresponding to the shape of the upper and lower edges of the hollow cylindrical body,
For example, when the hollow cylindrical body is cylindrical, it is formed in an annular shape corresponding to the edge.
【００２２】上板１９は、濾過する溶液を導入する管
（バルブ付）２４、過剰圧時に空気を放出する管（バル
ブ付）２５を備え、容器内内圧を上昇させるコンプレッ
サー２７からの圧縮空気を導入する管２６が連結され
る。２８は下板２０の中央部に設けられた溶媒排出口、
２９は下板２０に一体に取付けられた脚部である。ガス
拡散板２３は、中空円筒体１８の下部開口縁部とパッキ
ン２２の間に挟持され、これをフィルターとしてその上
面に溶液中の溶質すなわち触媒粒子が堆積されることに
なる。The upper plate 19 is provided with a pipe (with a valve) 24 for introducing a solution to be filtered and a pipe (with a valve) 25 for releasing air when excessive pressure is applied. The compressed air from a compressor 27 for increasing the internal pressure in the container is provided. The pipe 26 to be introduced is connected. 28 is a solvent outlet provided at the center of the lower plate 20,
Reference numeral 29 denotes a leg integrally attached to the lower plate 20. The gas diffusion plate 23 is sandwiched between the lower opening edge of the hollow cylindrical body 18 and the packing 22, and a solute in a solution, that is, catalyst particles is deposited on the upper surface of the gas diffusion plate 23 as a filter.
【００２３】下板２０は、好ましくは図中点線で示すと
おりロート状に構成され、これにより濾過後の溶媒がス
ムーズに流れるようになっている。下板の上面をこのよ
うにロート状に構成することにより、中空筒状体１８等
の他の構成とも相まち、濾過後の溶媒が溶媒排出口に向
かってスムーズに流れ、また仮りに堆積物の厚みに分布
が生じても厚い部分は流れが悪くなり、堆積速度が落ち
るため全体として均一な層とすることができる。その傾
斜はこのような効果を得る上で必要な限度で適宜設定さ
れる。The lower plate 20 is preferably formed in a funnel shape as shown by a dotted line in the figure, so that the solvent after filtration flows smoothly. By configuring the upper surface of the lower plate in a funnel shape in this manner, the solvent after filtration flows smoothly toward the solvent outlet, as well as with other configurations such as the hollow cylindrical body 18. Even if there is a distribution in the thickness of the film, the flow becomes poor in the thick portion, and the deposition rate is reduced, so that a uniform layer can be obtained as a whole. The inclination is appropriately set to the extent necessary for obtaining such an effect.
【００２４】その概略、以上の装置を操作するに際して
は、組立作業後、中空円筒体１８に触媒粒子を含む溶液
をその収容容器から導管２４を介して供給し、コンプレ
ッサー２７により圧縮空気を導入して中空円筒体１８内
を加圧状態として操作する。この場合、その加圧の程度
は装置の規模（中空筒状体の径、高さ等）、触媒粒子を
含む溶液の流動性（濃度、粘度等）、ガス拡散板２３自
体の強度等の性質、下板上面のロート状傾斜の程度等如
何により適宜選定できるが、通常、例えば中空円筒体の
直径が３０ｃｍ、高さ５ｃｍ程度の場合には０．１ｋｇ
／ｃｍ2 Ｇ（ゲージ圧）以下で十分である。In general, when operating the above apparatus, after assembling, a solution containing catalyst particles is supplied to the hollow cylindrical body 18 from the container via the conduit 24, and compressed air is introduced by the compressor 27. The inside of the hollow cylindrical body 18 is operated in a pressurized state. In this case, the degree of the pressurization depends on the scale of the apparatus (diameter and height of the hollow cylindrical body, etc.), the fluidity (concentration, viscosity, etc.) of the solution containing the catalyst particles, and the properties such as the strength of the gas diffusion plate 23 itself. It can be appropriately selected depending on the degree of the funnel-like inclination of the lower plate upper surface, but usually, for example, when the diameter of the hollow cylindrical body is about 30 cm and the height is about 5 cm, 0.1 kg is used.
/ Cm 2 G (gauge pressure) or less is sufficient.
【００２５】また、前記（５）各触媒粒子を含む懸濁液
又は粘性懸濁液を順次塗工法又は印刷法により積層する
態様については、塗工形式又は印刷形式で形成する態様
であれば特に限定はないが、その数例を示すと下記のと
おりである。なお、これらのうち（ａ）〜（ｃ）はその
特徴から印刷形式とも云えるものである。 （ａ）ガス拡散層上に（Ａ）触媒粒子及び電解質を含む
触媒層、または（Ｂ）触媒粒子、電解質及び撥水化剤を
含む触媒層を担持させてなる燃料電池用電極を製造する
に当たり、触媒粒子を含む粘度の高いスラリーまたは触
媒粒子及び撥水化剤を含む粘度の高いスラリーを膜厚を
制御しながらガス拡散層に塗布した後、その塗布面に電
解質を含浸させる（特願平７ー３５３４５３号）。The above-mentioned (5) embodiment in which the suspension or viscous suspension containing each catalyst particle is successively laminated by a coating method or a printing method is particularly applicable as long as it is formed in a coating or printing form. Although not limited, the following are some examples. Incidentally, of these, (a) to (c) can also be referred to as a printing format due to their characteristics. In producing a fuel cell electrode comprising (a) a catalyst layer containing (A) catalyst particles and an electrolyte or (B) a catalyst layer containing catalyst particles, an electrolyte and a water repellent on a gas diffusion layer. A high-viscosity slurry containing catalyst particles or a high-viscosity slurry containing catalyst particles and a water-repellent agent is applied to the gas diffusion layer while controlling the film thickness, and then the coated surface is impregnated with an electrolyte (Japanese Patent Application No. Hei 10-26139). No. 7-353453).
【００２６】（ｂ）ガス拡散層上に（Ａ）触媒粒子及び
電解質を含む触媒層、または（Ｂ）触媒粒子、電解質及
び撥水化剤を含む触媒層を担持させてなる燃料電池用電
極を製造するに当り、触媒粒子及び非イオン界面活性剤
を含む粘度の高いスラリー、または触媒粒子、撥水化剤
及び非イオン界面活性剤を含む粘度の高いスラリーを膜
厚を制御しながらガス拡散層に塗布した後、熱処理を
し、次いでその塗布面に電解質を含浸させる（特願平７
ー３５３４５４号）。(B) a fuel cell electrode comprising (A) a catalyst layer containing catalyst particles and an electrolyte or (B) a catalyst layer containing catalyst particles, an electrolyte and a water repellent on a gas diffusion layer. In producing, the gas diffusion layer is formed by controlling a film thickness of a high-viscosity slurry containing catalyst particles and a nonionic surfactant or a high-viscosity slurry containing catalyst particles, a water-repellent agent and a nonionic surfactant. , Heat-treated and then impregnated with an electrolyte on the coated surface (Japanese Patent Application No. Hei 7
-353454).
【００２７】（ｃ）ガス拡散層上に触媒粒子、ポリテト
ラフルオロエチレン系ポリマー及び高分子電解質を含む
触媒層を有する燃料電池用電極の製造方法において、該
触媒層を触媒粒子とポリテトラフルオロエチレン系ポリ
マーのディスパージョンとの混合液に増粘剤を混合した
後、熱処理をし、次いで高分子電解質によりコーティン
グすることにより形成する（特願平７ー３５３４５５
号）。 （ｄ）ガス拡散層上に（Ａ）触媒粒子及び電解質を含む
触媒層、または（Ｂ）触媒粒子、電解質及び撥水化剤含
む触媒層を担持させてなる燃料電池用電極を製造するに
当たり、触媒粒子及び電解質を含む粘度の高い有機溶媒
系の印刷液または触媒粒子、電解質及び撥水化剤を含む
粘度の高い有機溶媒系の印刷液をスクリーン印刷により
ガス拡散層に塗布する（特願平７ー３５３４５６号）。(C) In a method for producing an electrode for a fuel cell having a catalyst layer containing a catalyst particle, a polytetrafluoroethylene-based polymer and a polymer electrolyte on a gas diffusion layer, the catalyst layer is formed of a catalyst particle and a polytetrafluoroethylene. After mixing the thickener with the mixture of the polymer and the dispersion, the mixture is heat-treated, and then coated with a polymer electrolyte to form a mixture (Japanese Patent Application No. 7-353455).
issue). In producing a fuel cell electrode comprising (D) a catalyst layer containing (A) catalyst particles and an electrolyte or (B) a catalyst layer containing catalyst particles, an electrolyte and a water repellent on a gas diffusion layer, A high-viscosity organic solvent-based printing liquid containing catalyst particles and an electrolyte or a high-viscosity organic solvent-based printing liquid containing catalyst particles, an electrolyte, and a water repellent is applied to the gas diffusion layer by screen printing (Japanese Patent Application No. Hei 10-26139). No. 7-353456).
【００２８】図４は、上記例示の態様のうち（ｄ）の態
様を実施する場合に好適に用いられる装置である。図４
中、３０は触媒層が印刷されるガス拡散層、３１はスク
リーン、３２はスキージ、３３は印刷塗布後の触媒層、
３４は触媒層用原料を含む印刷液であり、図４（ａ）中
の矢印（→）はスキージ３２の操作による印刷方向を示
している。また図４（ｂ）はスクリーン３１の平面図で
あり、図４（ｂ）中、３５は版膜すなわちマスキングさ
れたスクリーン、Ｓは露出したスクリーンであり、印刷
液３４により印刷された触媒層はこの露出空間部分Ｓに
形成される。この空間部分Ｓの形状は図４（ｂ）では長
方形に示しているが、正方形、円形、その他触媒層の所
望形状に応じた形状に構成される。FIG. 4 shows an apparatus suitably used in carrying out the embodiment (d) of the above-mentioned embodiments. FIG.
Inside, 30 is a gas diffusion layer on which a catalyst layer is printed, 31 is a screen, 32 is a squeegee, 33 is a catalyst layer after printing and coating,
Reference numeral 34 denotes a printing liquid containing a catalyst layer raw material, and an arrow (→) in FIG. 4A indicates a printing direction by operating the squeegee 32. 4B is a plan view of the screen 31. In FIG. 4B, 35 is a plate film, ie, a masked screen, S is an exposed screen, and the catalyst layer printed by the printing liquid 34 is It is formed in this exposed space portion S. Although the shape of the space portion S is shown as a rectangle in FIG. 4B, it is formed in a square, a circle, or any other shape according to the desired shape of the catalyst layer.
【００２９】この装置の操作態様としては、図示のとお
りスクリーン３１とスキージ３２との間に印刷液３４を
供給し、スキージ３２を図４（ａ）中の矢印（→）の方
向に移動させる。これによって拡散層３０上に所定厚の
触媒層３３が均一に印刷、形成される。印刷液３４は、
このようにして拡散層３０上に印刷され触媒層３３とな
るが、このためには所定粘度である必要があり、この粘
度は例えば１０００〜１００００ｃｐ（センチポイズ）
程度の粘度で適用することができる。また本態様によれ
ばスクリーン３１の厚さを選定することにより所望厚さ
の触媒層を自由に形成することができる。As an operation mode of this apparatus, a printing liquid 34 is supplied between the screen 31 and the squeegee 32 as shown in the figure, and the squeegee 32 is moved in the direction of the arrow (→) in FIG. As a result, the catalyst layer 33 having a predetermined thickness is uniformly printed and formed on the diffusion layer 30. The printing liquid 34 is
In this way, the catalyst layer 33 is printed on the diffusion layer 30. For this purpose, the catalyst layer 33 needs to have a predetermined viscosity, which is, for example, 1000 to 10000 cp (centipoise).
It can be applied with a degree of viscosity. Further, according to this aspect, by selecting the thickness of the screen 31, a catalyst layer having a desired thickness can be freely formed.
【００３０】次に本発明の具体的手順の一態様について
述べると以下（１）〜（４）のとおりである。（１）例
えばカーボン粒子に白金を担持した触媒粒子に対して電
解質を混合して減圧加熱処理により溶媒を除去する。
（２）同様にして、例えばカーボン粒子に白金ールテニ
ウム合金を担持した触媒粒子に対して電解質を混合して
減圧加熱処理により溶媒を除去する。（３）、（１）〜
（２）で得られた各触媒粒子のそれぞれと例えばポリテ
トラフルオロエチレンデンスパージョンとをモジナイザ
ーで混合する。（４）、（３）で得られた各懸濁液を、
例えば撥水化カーボンペーパー上に、白金ールテニウム
合金触媒、白金のみの触媒の順に過圧濾過法、印刷法等
により積層し電極とする。（５）作製した電極の間に固
体高分子電解質膜を挟みプレスして電池とする。Next, one embodiment of the specific procedure of the present invention will be described as follows (1) to (4). (1) For example, an electrolyte is mixed with catalyst particles having platinum supported on carbon particles, and the solvent is removed by heat treatment under reduced pressure.
(2) Similarly, for example, an electrolyte is mixed with catalyst particles in which a platinum-ruthenium alloy is supported on carbon particles, and the solvent is removed by heat treatment under reduced pressure. (3), (1)-
Each of the catalyst particles obtained in (2) and, for example, polytetrafluoroethylene dispersion are mixed with a modifier. Each of the suspensions obtained in (4) and (3) is
For example, electrodes are formed by laminating a platinum-ruthenium alloy catalyst and a platinum-only catalyst in this order on a water-repellent carbon paper by an overpressure filtration method, a printing method, or the like. (5) A solid polymer electrolyte membrane is sandwiched between the produced electrodes and pressed to form a battery.
【００３１】[0031]
【実施例】以下、本発明の方法及び装置の実施例を説明
するが、本発明がこの実施例に限定されないことは勿論
である。本実施例での使用装置としては図３に示すよう
な加圧濾過装置を使用した。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the method and apparatus according to the present invention will be described below, but it goes without saying that the present invention is not limited to these embodiments. In this example, a pressure filtration device as shown in FIG. 3 was used.
【００３２】（１）カーボン粒子に５０％白金を担持し
た触媒粒子と電解質としてのＮＡＦＩＯＮ（パーフルオ
ロカーボンスルホン酸樹脂、Ｄｕ Ｐｏｎｔ社製、商品
名）のアルコール溶液を水とイソプロパノールの混合溶
媒に加えて均一に混合し、減圧加熱により溶媒を除去し
た。このとき触媒２ｇに対して電解質が１．５ｇとなる
ようにした。（２）、（１）で得られた電解質コーティ
ング触媒粒子とポリフロン（ポリテトラフルオロエチレ
ン、ダイキン工業社製、登録商標）のディスパージョン
を触媒２ｇに対してポリフロンが１．５ｇになるように
加えてホモジナイザーで混合した。(1) An alcohol solution of catalyst particles in which 50% platinum is supported on carbon particles and NAFION (perfluorocarbon sulfonic acid resin, manufactured by Du Pont) as an electrolyte is added to a mixed solvent of water and isopropanol. The mixture was mixed uniformly, and the solvent was removed by heating under reduced pressure. At this time, the amount of the electrolyte was 1.5 g with respect to 2 g of the catalyst. (2) The dispersion of the electrolyte coated catalyst particles obtained in (1) and polyflon (polytetrafluoroethylene, manufactured by Daikin Industries, Ltd.) was added so that 1.5 g of polyflon was added to 2 g of the catalyst. And mixed with a homogenizer.
【００３３】（１）′上記と同様にして、カーボン粒子
に５０％白金ールテニウム合金（白金とルテニウムの重
量比＝１：１）を担持した触媒粒子と上記と同じ電解質
を触媒２ｇに対して電解質が１．５ｇとなるように混合
して減圧加熱処理により溶媒を除去した。（２）′、
（１）′で得られた電解質コーティング触媒粒子とポリ
フロンのディスパージョンを各触媒粒子２ｇに対してポ
リフロンが１．５ｇになるようにホモジナイザーで混合
した。(1) 'In the same manner as above, catalyst particles in which 50% platinum-ruthenium alloy (weight ratio of platinum to ruthenium = 1: 1) is supported on carbon particles, and the same electrolyte as described above are added to 2 g of the catalyst. Was adjusted to 1.5 g, and the solvent was removed by heat treatment under reduced pressure. (2) ',
The electrolyte-coated catalyst particles obtained in (1) ′ and a dispersion of polyflon were mixed with a homogenizer such that 1.5 g of polyflon was added to 2 g of each catalyst particle.
【００３４】（３）、次に図３に示す装置を使用し、上
記で得た各懸濁液を用いて触媒層を積層した。中空筒状
体としては内径１５ｃｍ、高さ８ｃｍのガラス製の中空
円筒状体を用いた。ガラス製中空円筒状体の下部とパッ
キンの間に気孔率８０％、厚さ０．４ｍｍの撥水化処理
したカーボンペーパー（表面積＝１７５ｃｍ2 ）を挟
み、該撥水化カーボンペーパー上に、まず（１）′〜
（２）′で得られた白金ールテニウム合金を含む触媒の
懸濁液を過圧濾過法で成層し、次いでその層上に（１）
〜（２）で得られた白金のみを含む触媒の懸濁液を過圧
濾過法で成層した。このとき上記両触媒層の触媒量はと
もに０．５ｍｇ／ｃｍ2 となるようにし、全体として
１．０ｍｇ／ｃｍ2 となるようにした。(3) Next, using the apparatus shown in FIG. 3, a catalyst layer was laminated using each suspension obtained above. As the hollow cylindrical body, a glass hollow cylindrical body having an inner diameter of 15 cm and a height of 8 cm was used. A water-repellent carbon paper (surface area = 175 cm 2 ) having a porosity of 80% and a thickness of 0.4 mm is sandwiched between the lower portion of the glass hollow cylindrical body and the packing. (1) '~
The suspension of the catalyst containing the platinum-ruthenium alloy obtained in (2) ′ is stratified by an overpressure filtration method, and then (1)
The suspension of the catalyst containing only platinum obtained in (2) was layered by an overpressure filtration method. At this time, the catalyst amounts of both the catalyst layers were set to 0.5 mg / cm 2, and the total amount was set to 1.0 mg / cm 2 .
【００３５】上記撥水化カーボンペーパーはカーボンペ
ーパーに対してネオフロン（テトラフルオロエチレンー
ヘキサフルオロプロピレン共重合体、ダイキン工業社
製、登録商標）のディスパージョンを含浸させた後熱処
理をして作製したものである。こうして得た電極シート
を実施例電極シートとし、その２枚の電極シート間に固
体高分子電解質膜としてのパーフルオロカーボンスルホ
ン酸系樹脂膜を、両電極シートの触媒層側を膜面に当接
させて挟み、温度１４０℃、圧力１００ｋｇｆ／ｃｍ2
の加圧下、６０秒間プレスした後、これを燃料電池用枠
内に組み込んでセットし、導線、ガス管等を接続して実
施例供試用電池とした。The water-repellent carbon paper was prepared by impregnating a carbon paper with a dispersion of neoflon (tetrafluoroethylene-hexafluoropropylene copolymer, manufactured by Daikin Industries, Ltd.) and then heat-treating the carbon paper. Things. The electrode sheet thus obtained was used as an example electrode sheet, and a perfluorocarbon sulfonic acid resin film as a solid polymer electrolyte membrane was brought into contact between the two electrode sheets with the catalyst layer side of both electrode sheets in contact with the membrane surface. At a temperature of 140 ° C. and a pressure of 100 kgf / cm 2
After pressurizing for 60 seconds under the above pressure, this was assembled and set in a fuel cell frame, and a lead wire, a gas pipe and the like were connected to obtain a test sample battery of Example.
【００３６】他方、比較例として、前記（１）′〜
（２）′と同様にして得られたカーボン粒子に担持した
５０％白金ールテニウム合金（白金とルテニウムの重量
比＝７：３）触媒粒子の懸濁液を上記と同じ撥水化カー
ボンペーパー上に過圧濾過法で成層して電極シートを作
製した。この場合撥水化剤及び電解質の材料としては実
施例で用いたものと同じ材料を使用し、触媒層の触媒量
についても１．０ｍｇ／ｃｍ2 となるようにした。こう
して得られた電極シートを比較例電極シートとし、この
２枚の電極シートの触媒層側間に固体高分子電解質膜と
して上記と同じパーフルオロカーボンスルホン酸系樹脂
膜を挟み実施例の場合と同様に構成して比較例供試用電
池とした。On the other hand, as a comparative example, the above (1) ′-
(2) A suspension of 50% platinum-ruthenium alloy (weight ratio of platinum to ruthenium = 7: 3) catalyst particles supported on carbon particles obtained in the same manner as in '2 ′ was placed on the same water-repellent carbon paper as above. An electrode sheet was prepared by layering by an overpressure filtration method. In this case, the same materials as those used in the examples were used as the materials for the water repellent and the electrolyte, and the amount of the catalyst in the catalyst layer was adjusted to 1.0 mg / cm 2 . The electrode sheet thus obtained was used as a comparative example electrode sheet, and the same perfluorocarbon sulfonic acid resin film as the above was sandwiched between the catalyst layers of the two electrode sheets as a solid polymer electrolyte membrane in the same manner as in the example. It constituted and it was set as the battery for a comparative example test.
【００３７】以上のとおり製作した各種供試用電池を用
い、燃料としてＣＯを８０ｐｐｍ含む水素を使用し、こ
れをアノード（燃料極）側に供給する一方、カソード
（酸素極）側には空気を供給した。この両ガスの供給圧
力はともに２ａｔｍとし、水素は９５℃で、空気につい
ては８０℃で加湿し、また電池の温度を８０℃に保って
操作して測定した。図５は以上の各供試電池について測
定した電流密度とセル電圧との関係を示すものである。Using the various test batteries manufactured as described above, hydrogen containing 80 ppm of CO was used as fuel, and this was supplied to the anode (fuel electrode) side, while air was supplied to the cathode (oxygen electrode) side. did. The supply pressure of both gases was set to 2 atm, hydrogen was humidified at 95 ° C., air was humidified at 80 ° C., and the measurement was performed while maintaining the battery temperature at 80 ° C. FIG. 5 shows the relationship between the current density measured for each of the test batteries and the cell voltage.
【００３８】図５のとおり、比較例供試電池の場合、セ
ル電圧は電流密度の増加に伴い徐々に低下するが、実施
例供試電池においては、得られるセル電圧はさらに高
く、電流密度の増加に伴うその低下傾向も緩慢で有効に
改善されていることが分かる。このように本発明によれ
ば、電極を構成する触媒層として耐ＣＯ性に優れる触媒
と触媒活性に優れる触媒とを併用することにより、電池
特性をさらに有効に改善することができる。As shown in FIG. 5, in the case of the test battery of the comparative example, the cell voltage gradually decreases with an increase in the current density. It can be seen that the decreasing tendency with the increase is slow and effectively improved. As described above, according to the present invention, battery characteristics can be more effectively improved by using a catalyst having excellent CO resistance and a catalyst having excellent catalytic activity together as a catalyst layer constituting an electrode.
【００３９】[0039]
【発明の効果】以上のとおり、本発明によれば、燃料電
池における電解質（例えば高分子電解質膜）から離れた
領域において、耐ＣＯ性に優れる触媒が燃料ガス中のＣ
Ｏを吸着、還元するため、電解質に接し又は近接した領
域の活性の高い触媒がＣＯに被毒することなく、高性能
の燃料電池が得られる。As described above, according to the present invention, in a region away from the electrolyte (for example, a polymer electrolyte membrane) in a fuel cell, a catalyst excellent in CO resistance is used as a catalyst in the fuel gas.
Since O is adsorbed and reduced, a highly active catalyst in a region in contact with or close to the electrolyte is not poisoned by CO, and a high-performance fuel cell can be obtained.
【図１】燃料電池の一例として固体高分子型燃料電池の
一態様を説明するための概略図。FIG. 1 is a schematic view illustrating one embodiment of a polymer electrolyte fuel cell as an example of a fuel cell.
【図２】本発明における多孔性の基材上に形成された耐
ＣＯ性に優れる触媒層と触媒活性に優れる触媒層との状
態を模式的に示す図。FIG. 2 is a view schematically showing a state of a catalyst layer having excellent CO resistance and a catalyst layer having excellent catalytic activity formed on a porous substrate in the present invention.
【図３】本発明で好適に使用される電極作製装置の一態
様を示す図。FIG. 3 is a diagram showing one embodiment of an electrode manufacturing apparatus suitably used in the present invention.
【図４】本発明で好適に使用される他の電極作製装置の
一態様を示す図。FIG. 4 is a diagram showing one embodiment of another electrode manufacturing apparatus suitably used in the present invention.
【図５】実施例及び比較例で製作した各供試電池につい
て測定した電流密度とセル電圧との関係を示す図。FIG. 5 is a diagram showing a relationship between a current density and a cell voltage measured for each test battery manufactured in Examples and Comparative Examples.
１ 高分子電解質膜 ２ カソード電極（正極） ３ アノード電極（負極） ４、５ 集電体 ６ 空気（酸素）供給管 ７ 燃料（水素）供給管 ８、９ 端子板 １０、１１ 枠体（フレーム） １２、２１ パッキン １３、１４ 冷却水供給管 １５ 多孔性の基材 １６ 担体粒子に耐ＣＯ性に優れた金属を担持した触媒
の層 １７ 担体粒子に活性金属を担持した触媒層 １８ 中空筒状体 １９ 上板 ２０ 下板 ２１、２２ パッキン ２３ 触媒層が堆積されるシート（ガス拡散板） ２４ 濾過する溶液を導入する管（バルブ付） ２５ 過剰圧時に空気を放出する管（バルブ付） ２６ 圧縮空気導入管 ２７ コンプレッサー ２８ 溶媒排出口 ２９ 脚部 ３０ 触媒層が印刷されるガス拡散層 ３１ スクリーン ３２ スキージ ３３ 印刷塗布後の触媒層 ３４ 触媒層とする印刷液 ３５ スクリーン（版膜：マスキングされたスクリー
ン） Ｓ 露出したスクリーン（スクリーンの露出空間部分）DESCRIPTION OF SYMBOLS 1 Polymer electrolyte membrane 2 Cathode electrode (positive electrode) 3 Anode electrode (negative electrode) 4, 5 Current collector 6 Air (oxygen) supply pipe 7 Fuel (hydrogen) supply pipe 8, 9 Terminal plate 10, 11 Frame (frame) 12, 21 Packing 13, 14 Cooling water supply pipe 15 Porous base material 16 Catalyst layer in which carrier particles carry metal excellent in CO resistance 17 Catalyst layer in which carrier particles carry active metal 18 Hollow cylindrical body Reference Signs List 19 upper plate 20 lower plate 21, 22 packing 23 sheet (gas diffusion plate) on which catalyst layer is deposited 24 pipe for introducing solution to be filtered (with valve) 25 pipe for releasing air at excessive pressure (with valve) 26 compression Air inlet tube 27 Compressor 28 Solvent outlet 29 Leg 30 Gas diffusion layer on which catalyst layer is printed 31 Screen 32 Squeegee 33 Catalyst layer after printing and coating 34 Printing liquid to be used as catalyst layer 35 Screen (plate: masked screen) S Exposed screen (exposed space of screen)
Claims (18)
剤を含む触媒層を形成した燃料電池用電極であって、ガ
ス拡散層上に耐ＣＯ性に優れる触媒を第１層とし、触媒
活性に優れる触媒層を第２層として積層形成してなるこ
とを特徴とする燃料電池用電極。1. A fuel cell electrode having a catalyst layer containing catalyst particles, an electrolyte and a water repellent formed on a gas diffusion layer, wherein a catalyst having excellent CO resistance is used as a first layer on the gas diffusion layer. An electrode for a fuel cell, wherein a catalyst layer having excellent catalytic activity is laminated as a second layer.
水化カーボンペーパーである請求項１記載の燃料電池用
電極。2. The fuel cell electrode according to claim 1, wherein said gas diffusion layer is carbon paper or water-repellent carbon paper.
ポリテトラフルオロエチレン系のポリマーである請求項
２記載の燃料電池用電極。3. The fuel cell electrode according to claim 2, wherein the water-repellent agent of the water-repellent carbon paper is a polytetrafluoroethylene-based polymer.
金、白金を含む合金、パラジウム及びパラジウムを含む
合金から選ばれた１種又は２種以上の金属が担持された
触媒粒子からなる触媒である請求項１記載の燃料電池用
電極。4. The catalyst having excellent catalytic activity is a catalyst comprising catalyst particles in which one or more metals selected from platinum, an alloy containing platinum, palladium and an alloy containing palladium are supported on carrier particles. The electrode for a fuel cell according to claim 1.
金ールテニウム系触媒が担持された触媒粒子からなる触
媒である請求項１記載の燃料電池用電極。5. The electrode for a fuel cell according to claim 1, wherein the catalyst having excellent CO resistance is a catalyst comprising catalyst particles in which a platinum-ruthenium-based catalyst is supported on carrier particles.
４又は５記載の燃料電池用電極。6. The fuel cell electrode according to claim 4, wherein said carrier particles are carbon particles.
ン酸系の樹脂である請求項１記載の燃料電池用電極。7. The fuel cell electrode according to claim 1, wherein said electrolyte is a perfluorocarbon sulfonic acid resin.
チレン系のポリマーである請求項１記載の燃料電池用電
極。8. The fuel cell electrode according to claim 1, wherein said water repellent is a polytetrafluoroethylene-based polymer.
池用の電極である請求項１記載の燃料電池用電極。9. The fuel cell electrode according to claim 1, wherein said fuel cell electrode is an electrode for a polymer electrolyte fuel cell.
化剤を含む触媒層を形成した燃料電池用電極の製造法に
おいて、該ガス拡散層上に耐ＣＯ性に優れる触媒からな
る層を形成し、次いで触媒活性に優れる触媒からなる層
を積層形成することを特徴とする燃料電池用電極の製造
方法。10. A method for producing a fuel cell electrode comprising a catalyst layer containing catalyst particles, an electrolyte and a water repellent formed on a gas diffusion layer, wherein a layer comprising a catalyst having excellent CO resistance is formed on the gas diffusion layer. And then forming a layer comprising a catalyst having excellent catalytic activity in a laminated manner.
化剤を含む触媒層を形成した燃料電池用電極の製造法に
おいて、該ガス拡散層上に耐ＣＯ性に優れる触媒からな
る層を濾過法により形成し、次いで触媒活性に優れる触
媒からなる層を濾過法により積層形成することを特徴と
する燃料電池用電極の製造方法。11. A method for producing a fuel cell electrode comprising a catalyst layer containing catalyst particles, an electrolyte, and a water repellent formed on a gas diffusion layer, wherein a layer comprising a catalyst having excellent CO resistance is formed on the gas diffusion layer. Is formed by a filtration method, and then a layer made of a catalyst having excellent catalytic activity is formed by lamination by a filtration method.
化剤を含む触媒層を形成した燃料電池用電極の製造法に
おいて、該ガス拡散層上に耐ＣＯ性に優れる触媒からな
る層を塗工法又は印刷法により形成し、次いで触媒活性
に優れる触媒からなる層を塗工法又は印刷法により積層
形成することを特徴とする燃料電池用電極の製造方法。12. A method for producing a fuel cell electrode comprising a catalyst layer containing catalyst particles, an electrolyte and a water repellent formed on a gas diffusion layer, wherein a layer comprising a catalyst having excellent CO resistance is formed on the gas diffusion layer. Is formed by a coating method or a printing method, and then a layer made of a catalyst having excellent catalytic activity is laminated and formed by a coating method or a printing method.
撥水化カーボンペーパーである請求項１０乃至１２の何
れかに記載の燃料電池用電極の製造方法。13. The method for producing an electrode for a fuel cell according to claim 10, wherein the gas diffusion layer is carbon paper or water-repellent carbon paper.
がポリテトラフルオロエチレン系のポリマーである請求
項１３記載の燃料電池用電極の製造方法。14. The method for producing an electrode for a fuel cell according to claim 13, wherein the water-repellent agent of the water-repellent carbon paper is a polytetrafluoroethylene-based polymer.
白金、白金を含む合金、パラジウム又はパラジウムを含
む合金から選ばれた１種又は２種以上の金属が担持され
た触媒粒子からなる触媒である請求項１０乃至１２の何
れかに記載の燃料電池用電極の製造方法。15. The catalyst having excellent catalytic activity is a catalyst comprising catalyst particles in which one or two or more metals selected from platinum, an alloy containing platinum, palladium and an alloy containing palladium are supported on carrier particles. A method for producing an electrode for a fuel cell according to any one of claims 10 to 12.
白金ールテニウム系触媒が担持された触媒粒子からなる
触媒である請求項１０乃至１２の何れかに記載の燃料電
池用電極の製造方法。16. The method for producing an electrode for a fuel cell according to claim 10, wherein the catalyst having excellent CO resistance is a catalyst comprising catalyst particles in which a platinum-ruthenium-based catalyst is supported on carrier particles.
項１５又は１６記載の燃料電池用電極の製造方法。17. The method for producing an electrode for a fuel cell according to claim 15, wherein the carrier particles are carbon particles.
ホン酸系の樹脂であり、上記撥水化剤がポリテトラフル
オロエチレン系のポリマーである請求項１０乃至１２の
何れかに記載の燃料電池用電極の製造方法。18. The fuel cell electrode according to claim 10, wherein the electrolyte is a perfluorocarbon sulfonic acid resin, and the water repellent is a polytetrafluoroethylene polymer. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9093093A JPH10270050A (en) | 1997-03-26 | 1997-03-26 | Fuel cell electrode and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9093093A JPH10270050A (en) | 1997-03-26 | 1997-03-26 | Fuel cell electrode and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10270050A true JPH10270050A (en) | 1998-10-09 |
Family
ID=14072916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9093093A Pending JPH10270050A (en) | 1997-03-26 | 1997-03-26 | Fuel cell electrode and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10270050A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002003489A1 (en) * | 2000-07-03 | 2002-01-10 | Matsushita Electric Industrial Co., Ltd. | Polyelectrolyte fuel cell |
| JP2002025561A (en) * | 2000-07-03 | 2002-01-25 | Matsushita Electric Ind Co Ltd | High polymer molecule electrolyte fuel cell and its manufacturing method |
| KR100423843B1 (en) * | 2001-09-25 | 2004-03-22 | 한국과학기술연구원 | Manufacturing method of electrode for fuel cell and electrode using the same |
| JP2007257970A (en) * | 2006-03-23 | 2007-10-04 | Sanyo Electric Co Ltd | Fuel cell |
| JP2008091102A (en) * | 2006-09-29 | 2008-04-17 | Sanyo Electric Co Ltd | Fuel electrode catalyst for fuel cell, electrode/membrane assembly, fuel cell equipped with electrode/membrane assembly, and fuel cell system |
| US7419740B2 (en) | 2000-07-29 | 2008-09-02 | Unicore Ag & Co. Kg | Membrane electrode unit for polymer electrolyte fuel cells and a process for the production thereof |
| KR101255237B1 (en) * | 2006-02-07 | 2013-04-16 | 삼성에스디아이 주식회사 | Supported catalyst for fuel cell, method for preparing the same, electrode for fuel cell comprising the same, and fuel cell comprising the electrode |
-
1997
- 1997-03-26 JP JP9093093A patent/JPH10270050A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002003489A1 (en) * | 2000-07-03 | 2002-01-10 | Matsushita Electric Industrial Co., Ltd. | Polyelectrolyte fuel cell |
| JP2002025561A (en) * | 2000-07-03 | 2002-01-25 | Matsushita Electric Ind Co Ltd | High polymer molecule electrolyte fuel cell and its manufacturing method |
| EP1304753A1 (en) * | 2000-07-03 | 2003-04-23 | Matsushita Electric Industrial Co., Ltd. | Polyelectrolyte fuel cell |
| EP1304753A4 (en) * | 2000-07-03 | 2006-12-13 | Matsushita Electric Ind Co Ltd | Polyelectrolyte fuel cell |
| US7220514B2 (en) | 2000-07-03 | 2007-05-22 | Matsushita Electric Industrial Co., Ltd. | Polymer electrolyte fuel cell |
| US7419740B2 (en) | 2000-07-29 | 2008-09-02 | Unicore Ag & Co. Kg | Membrane electrode unit for polymer electrolyte fuel cells and a process for the production thereof |
| KR100423843B1 (en) * | 2001-09-25 | 2004-03-22 | 한국과학기술연구원 | Manufacturing method of electrode for fuel cell and electrode using the same |
| KR101255237B1 (en) * | 2006-02-07 | 2013-04-16 | 삼성에스디아이 주식회사 | Supported catalyst for fuel cell, method for preparing the same, electrode for fuel cell comprising the same, and fuel cell comprising the electrode |
| JP2007257970A (en) * | 2006-03-23 | 2007-10-04 | Sanyo Electric Co Ltd | Fuel cell |
| JP4610505B2 (en) * | 2006-03-23 | 2011-01-12 | 三洋電機株式会社 | Fuel cell and fuel cell system |
| JP2008091102A (en) * | 2006-09-29 | 2008-04-17 | Sanyo Electric Co Ltd | Fuel electrode catalyst for fuel cell, electrode/membrane assembly, fuel cell equipped with electrode/membrane assembly, and fuel cell system |
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