JPH07130375A - Manufacture of solid polymer fuel cell electrode - Google Patents
Manufacture of solid polymer fuel cell electrodeInfo
- Publication number
- JPH07130375A JPH07130375A JP5272129A JP27212993A JPH07130375A JP H07130375 A JPH07130375 A JP H07130375A JP 5272129 A JP5272129 A JP 5272129A JP 27212993 A JP27212993 A JP 27212993A JP H07130375 A JPH07130375 A JP H07130375A
- Authority
- JP
- Japan
- Prior art keywords
- ion
- alcohol
- exchanger
- catalyst
- layer sheet
- 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.)
- Granted
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]
【産業上の利用分野】本発明は、固体高分子型燃料電池
に用いられる電極の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an electrode used in a polymer electrolyte fuel cell.
【０００２】[0002]
【従来の技術】固体高分子型燃料電池は、電解質として
高分子イオン交換膜を用い、このイオン交換膜の両面に
一対の電極を接合した構造である。この固体高分子型燃
料電池の電極は、白金又は白金担持カーボン等の触媒粒
子と、撥水性及び結着能のあるＰＴＦＥ（ポリテトラフ
ルオロエチレン）とから成るガス電極である。従来、固
体高分子型燃料電池の作製方法としては、米国特許第
４，８７６，１１５号明細書及び特開平４−１６２３６
５号公報に記載されている方法が知られている。 米国特許第４，８７６，１１５号の方法 白金担持カーボンとＰＴＦＥ粒子とを混合し、次に圧延
ローラで電極触媒層シートを成型し、このシートの一方
の面（即ち、イオン交換膜との接合面側）にイオン交換
体のアルコール溶液（例えば、ナフィオン１１７の５％
アルコール溶液）を塗布し、ホットプレスを行って、シ
ートをイオン交換膜に接合する方法。 特開平４−１６２３６５号の方法 触媒微粒子をイオン交換樹脂溶液に浸積し、５０℃で真
空乾燥させて、その表面にイオン交換樹脂薄膜を形成
し、次に別途用意した無触媒微粒子をイオン交換樹脂溶
液に浸積し、５０℃で真空乾燥させて、その表面にイオ
ン交換樹脂厚膜を形成し、次いで前記のイオン交換樹脂
を被覆した２種類の微粒子を撥水性バインダーと混合し
た後、冷間プレス又はホットプレスによりシート状触媒
層を形成し、このシート状触媒層をイオン交換膜に熱圧
着する方法。2. Description of the Related Art A polymer electrolyte fuel cell has a structure in which a polymer ion exchange membrane is used as an electrolyte, and a pair of electrodes are bonded to both sides of the ion exchange membrane. The electrode of this polymer electrolyte fuel cell is a gas electrode composed of catalyst particles such as platinum or platinum-supporting carbon and PTFE (polytetrafluoroethylene) having water repellency and binding ability. Conventionally, as a method for producing a polymer electrolyte fuel cell, US Pat. No. 4,876,115 and JP-A-4-16236 are known.
The method described in Japanese Patent No. 5 is known. Method of US Pat. No. 4,876,115 Platinum-supporting carbon and PTFE particles are mixed, and then an electrode catalyst layer sheet is molded with a rolling roller, and one surface of this sheet (that is, bonding with an ion exchange membrane). Alcohol solution of ion exchanger (for example, 5% of Nafion 117 on the surface side)
Alcohol solution) is applied and hot pressing is performed to join the sheet to the ion exchange membrane. Method of JP-A-4-162365 The catalyst fine particles are immersed in an ion exchange resin solution and vacuum dried at 50 ° C. to form an ion exchange resin thin film on the surface, and then separately prepared non-catalyst fine particles are ion exchanged. It is dipped in a resin solution and vacuum dried at 50 ° C. to form an ion exchange resin thick film on its surface, and then the two types of fine particles coated with the above ion exchange resin are mixed with a water repellent binder, and then cooled. A method in which a sheet-shaped catalyst layer is formed by hot pressing or hot pressing, and the sheet-shaped catalyst layer is thermocompression-bonded to an ion exchange membrane.
【０００３】[0003]
【発明が解決しようとする課題】ところが、上記の方
法では、電極触媒層シート内でのイオン交換体の分布
が、イオン交換体を塗布した接合面側に局在し、接合面
と反対側の面にはほとんど分布していないため、電極触
媒層シート内にイオン交換体の３次元ネットワークを構
築することができない。また、前記電極触媒層シートの
接合面近傍に存在するＰＴＦＥ粒子に前記イオン交換体
が付着し、ＰＴＦＥ粒子の撥水性が低下するため、電池
発電時に発生する水によってガス拡散経路が塞がれ、ガ
スの流通が悪くなるという課題もある。However, in the above method, the distribution of the ion exchanger in the electrode catalyst layer sheet is localized on the side of the joint surface coated with the ion exchanger, and Since it is hardly distributed on the surface, a three-dimensional network of ion exchangers cannot be constructed in the electrode catalyst layer sheet. Further, since the ion exchanger adheres to the PTFE particles existing in the vicinity of the bonding surface of the electrode catalyst layer sheet and the water repellency of the PTFE particles is reduced, the gas diffusion path is blocked by water generated during battery power generation, There is also a problem that gas distribution becomes poor.
【０００４】また、上記の方法では、ガスの流通を損
なうことなく、電極触媒層シート内にイオン交換体の３
次元ネットワークを構築することはできるものの、以下
のような課題がある。即ち、この方法では、触媒微粒子
又は無触媒微粒子の表面にイオン交換樹脂膜を形成する
際に乾燥を行っているが、この乾燥は真空乾燥であるた
め、粒子の表面に形成されるイオン交換膜が完全に乾燥
し、完全な固体となる。そのため、その後の工程でホッ
トプレスを行ったとしても、微粒子同士の結着性が悪く
なり、微粒子間の接触抵抗が増大するので、イオン伝導
性が悪くなる。Further, according to the above-mentioned method, the ion-exchanger 3 is contained in the electrode catalyst layer sheet without impairing the gas flow.
Although it is possible to construct a dimensional network, there are the following problems. That is, in this method, drying is performed when the ion exchange resin membrane is formed on the surface of the catalyst fine particles or the non-catalyst fine particles. Since this drying is vacuum drying, the ion exchange membrane formed on the surface of the particles is dried. Is completely dried and becomes a completely solid. Therefore, even if hot pressing is performed in the subsequent step, the binding property between the fine particles deteriorates, and the contact resistance between the fine particles increases, so that the ion conductivity deteriorates.
【０００５】本発明は、かかる現状に鑑みてなされたも
のであり、電極触媒層シート内にイオン交換体の３次元
ネットワークを構築することができると共に、電極触媒
粒子同士の結着性が良く、イオン伝導性に優れた固体高
分子型燃料電池用電極の製造方法を提供することを目的
としている。The present invention has been made in view of the above circumstances, and it is possible to construct a three-dimensional network of ion exchangers in the electrode catalyst layer sheet, and at the same time, the binding property between the electrode catalyst particles is good. It is an object of the present invention to provide a method for producing an electrode for a polymer electrolyte fuel cell having excellent ionic conductivity.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
に、本請求項１の発明は、触媒粒子とイオン交換体溶液
とを混合する第１ステップと、前記触媒粒子の表面にイ
オン交換体膜を形成でき、且つ、このイオン交換体膜が
アルコールに対して易溶解性となる程度に前記混合物を
乾燥する第２ステップと、前記イオン交換体膜を形成し
た触媒粒子を圧延又は加圧して、触媒層シートを作成す
る第３ステップと、前記触媒層シートにアルコール水溶
液を含浸して、前記触媒粒子の表面に形成したイオン交
換体膜を溶解させる第４ステップと、前記触媒層シート
を乾燥して、前記アルコール水溶液を除去する第５ステ
ップと、を有することを特徴としている。In order to achieve the above object, the invention of claim 1 comprises the first step of mixing catalyst particles with an ion exchanger solution, and an ion exchanger on the surface of the catalyst particles. A second step of drying the mixture to the extent that a membrane can be formed and the ion exchanger membrane is readily soluble in alcohol; and rolling or pressing the catalyst particles with the ion exchanger membrane formed. A third step of preparing a catalyst layer sheet, a fourth step of impregnating the catalyst layer sheet with an aqueous alcohol solution to dissolve the ion exchanger membrane formed on the surface of the catalyst particles, and drying the catalyst layer sheet And a fifth step of removing the alcohol aqueous solution.
【０００７】また、本請求項２の発明は、触媒粒子とイ
オン交換体溶液とを混合する第１ステップと、前記触媒
粒子の表面にイオン交換体膜を形成でき、且つ、このイ
オン交換体膜がアルコールに対して難溶解性となる程度
に前記混合物を乾燥する第２ステップと、前記イオン交
換体膜を形成した触媒粒子とイオン交換体溶液とを混合
する第３ステップと、前記アルコール難溶解性のイオン
交換体膜の表面にイオン交換体膜を形成でき、且つ、こ
のイオン交換体膜がアルコールに対して易溶解性となる
程度に前記混合物を乾燥する第４ステップと、前記イオ
ン交換体膜を形成した触媒粒子を圧延又は加圧して、触
媒層シートを作成する第５ステップと、前記触媒層シー
トにアルコール水溶液を含浸して、前記アルコール難溶
解性のイオン交換体膜の表面に形成したイオン交換体膜
を溶解させる第６ステップと、前記触媒層シートを乾燥
して、前記アルコール水溶液を除去する第７ステップ
と、を有することを特徴としている。Further, the invention of claim 2 is such that the first step of mixing the catalyst particles and the ion-exchanger solution, and the ion-exchanger membrane can be formed on the surface of the catalyst particles, and the ion-exchanger membrane is formed. A second step of drying the mixture to such an extent that it becomes hardly soluble in alcohol, a third step of mixing the catalyst particles having the ion-exchanger membrane formed with the ion-exchanger solution, and the hardly-soluble alcohol. Ion-exchanger membrane can be formed on the surface of a water-soluble ion-exchanger membrane, and the fourth step of drying the mixture to such an extent that the ion-exchanger membrane is easily soluble in alcohol, and the ion-exchanger A fifth step of rolling or pressurizing the membrane-formed catalyst particles to form a catalyst layer sheet, and impregnating the catalyst layer sheet with an aqueous alcohol solution to obtain the sparingly soluble alcohol ion exchange. A sixth step of dissolving the ion-exchange membrane formed on the surface of the membrane, and drying the catalyst layer sheet is characterized by having a seventh step of removing the aqueous alcohol solution.
【０００８】[0008]
【作用】上記本請求項１の発明方法によれば、第２ステ
ップによって、触媒粒子の表面にアルコールに対して易
溶解性のイオン交換体膜を形成できる。このイオン交換
体膜は、第４ステップによって添加されたアルコール水
溶液によって、一部が溶解して、ゲル状になる。このゲ
ル状のイオン交換体膜は、他の触媒粒子を結着する接着
剤となるので、触媒粒子同士の結着性が向上する。最後
に、第５ステップによって前記含浸させたアルコール水
溶液が除去され、電極触媒層シートの最終完成品を得る
ことができる。以上の第１〜第５ステップによって製造
した電極触媒層シートは、シート内にイオン交換体の３
次元ネットワークを構築することができると共に、電極
触媒粒子同士の結着性が良く、イオン伝導性に優れてい
る。According to the method of the first aspect of the present invention, the second step allows the formation of an ion-exchange membrane that is easily soluble in alcohol on the surface of the catalyst particles. A part of this ion exchanger membrane is dissolved by the aqueous alcohol solution added in the fourth step and becomes a gel. This gel-like ion-exchange membrane serves as an adhesive for binding other catalyst particles, so that the binding property between the catalyst particles is improved. Finally, in the fifth step, the impregnated alcohol aqueous solution is removed to obtain a final finished electrode catalyst layer sheet. The electrode catalyst layer sheet manufactured by the above first to fifth steps has 3 of ion exchangers in the sheet.
A dimensional network can be constructed, and the electrode catalyst particles are well bound to each other and have excellent ionic conductivity.
【０００９】また、本請求項２の発明方法によれば、第
２ステップによって、触媒粒子の表面にアルコールに対
して難溶解性のイオン交換体膜を形成できる。このイオ
ン交換体膜は略完全固体状態であり、アルコールに対し
て難溶解性であるため、圧延又は加圧しても触媒粒子同
士の結着性が悪い。本発明では、第４ステップによっ
て、アルコール難溶解性のイオン交換体膜の表面に、ア
ルコール易溶解性のイオン交換体膜を形成したので、第
６ステップによって添加されたアルコール水溶液によっ
て、一部が溶解して、ゲル状になり、触媒粒子同士の結
着性が向上する。Further, according to the method of the second aspect of the present invention, the second step allows the formation of the ion-exchange membrane which is hardly soluble in alcohol on the surface of the catalyst particles. Since this ion exchanger membrane is in a substantially completely solid state and hardly soluble in alcohol, the binding property between catalyst particles is poor even when rolled or pressed. In the present invention, since the easily-dissolved alcohol ion-exchange membrane is formed on the surface of the slightly-alcohol-dissolved ion-exchange membrane in the fourth step, the alcohol aqueous solution added in the sixth step partially It dissolves and becomes a gel, and the binding property between catalyst particles is improved.
【００１０】[0010]
〔実施例〕以下、本発明の固体高分子型燃料電池用電極
の製造方法の一実施例について具体的に説明する。先
ず、２０ｗｔ％の白金を担持したカーボンブラック（以
下、単に「Ｐｔ／Ｃ」と略称する）１０ｇにイオン交換
水８ｃｃを添加して、Ｐｔ／Ｃを湿潤させる。次に、ナ
フィオン１１７（商品名，デュポン社）の５％溶液６ｇ
を加えてよく攪拌した後、５０℃で１２時間真空乾燥を
行い、Ｐｔ／Ｃの表面にアルコール難溶解性のナフィオ
ン膜を形成した。ここで、アルコールに対して難溶解性
とは、ナフィオン膜が略完全な固体となっているような
状態をいい、アルコールに対して全く溶解しないか、或
いは極くわずかに溶け出す程度をいう。そして、この難
溶解性のナフィオン膜を形成させる際の乾燥状態の一例
として、ここでは５０℃で１２時間の真空乾燥を行っ
た。続いて、このＰｔ／Ｃを粉砕し、ナフィオン１１７
の２％溶液６ｇを加えて攪拌した後、窒素気流中、６０
℃で２時間乾燥を行ない、前記アルコール難溶解性のナ
フィオン膜の表面に、アルコール易溶解性のナフィオン
膜を形成した。ここで、アルコールに対して易溶解性と
は、完全な固体状態ではない程度をいい、具体的にはア
ルコールを添加した場合にナフィオン膜の表面の一部が
溶け出しゲル状になるような状態をいう。そして、この
易溶解性のナフィオン膜を形成させる際の乾燥状態の一
例として、ここでは、窒素気流中、６０℃で２時間乾燥
を行った。そして、このＰｔ／Ｃを再度粉砕し、所定量
（約３０％）のＰＴＦＥ−６Ｃ（三井・デュポンフロロ
ケミカル社）を混合した後、圧延ローラを用いて圧延
し、シート状触媒層（0.２mm厚）を得た。次いで、この
シート状触媒層に、水とイソプロピルアルコールの１：
１（体積比）の混合液を含浸させた後、この混合液が含
浸されたままの状態でシート状触媒層の厚みが0.０８mm
になるまで圧延ローラを用いて圧延した。この場合、前
記アルコール溶液によって、Ｐｔ／Ｃの最外層に形成さ
れた不完全乾燥状態のナフィオン膜の一部がゲル状に溶
解し、Ｐｔ／Ｃ同士を結着する接着剤のような役目を果
たすので、Ｐｔ／Ｃ同士の結着性が向上する。最後に、
このシート状触媒層を５０℃で２時間真空乾燥して前記
混合液を除去し、シート状触媒層の最終完成品を得た。[Examples] Hereinafter, one example of the method for producing an electrode for a polymer electrolyte fuel cell of the present invention will be specifically described. First, 8 cc of ion-exchanged water is added to 10 g of carbon black (hereinafter, simply referred to as “Pt / C”) supporting 20 wt% of platinum to wet Pt / C. Next, 6 g of a 5% solution of Nafion 117 (trade name, DuPont)
Was added and well stirred, and then vacuum dried at 50 ° C. for 12 hours to form a poorly soluble alcohol Nafion film on the surface of Pt / C. Here, the term "insoluble in alcohol" refers to a state in which the Nafion film is a substantially completely solid state, which means that the Nafion film does not dissolve in alcohol at all or only slightly dissolves in it. Then, as an example of a dried state when forming the hardly soluble Nafion film, here, vacuum drying was performed at 50 ° C. for 12 hours. Subsequently, this Pt / C was crushed and Nafion 117
After adding 6 g of a 2% solution of the above and stirring, in a nitrogen stream, 60
Drying was carried out at 0 ° C. for 2 hours to form an easily soluble alcohol Nafion film on the surface of the hardly soluble alcohol Nafion film. Here, the term “easy-dissolved in alcohol” refers to a degree of not being in a completely solid state, and specifically, a state in which a part of the surface of the Nafion film is dissolved and becomes a gel when alcohol is added. Say. Then, as an example of a dried state when forming the easily soluble Nafion film, here, drying was performed at 60 ° C. for 2 hours in a nitrogen stream. Then, this Pt / C was pulverized again, and a predetermined amount (about 30%) of PTFE-6C (Mitsui DuPont Fluorochemical Co., Ltd.) was mixed, followed by rolling using a rolling roller to obtain a sheet-like catalyst layer (0. 2 mm thick) was obtained. Then, the sheet-shaped catalyst layer was mixed with water and isopropyl alcohol 1:
After impregnating the mixed solution of 1 (volume ratio), the thickness of the sheet-like catalyst layer is 0.08 mm while the mixed solution is still impregnated.
It rolled using the rolling roller until it became. In this case, the alcohol solution dissolves a part of the incompletely dried Nafion film formed in the outermost layer of Pt / C in a gel state, and acts as an adhesive for binding Pt / C to each other. Since this is achieved, the binding property between Pt / C is improved. Finally,
The sheet-shaped catalyst layer was vacuum dried at 50 ° C. for 2 hours to remove the mixed solution, and a final finished product of the sheet-shaped catalyst layer was obtained.
【００１１】このようにして作成した電極を以下、
（ａ）電極と称する。最後に、上記本発明方法にて製造
した（ａ）電極を、イオン交換膜としてのナフィオン１
１７の両面に２００kg／cm2 、１２５℃でホットプレス
を行うことにより接合して電池を作成した。このように
して作成した固体高分子型燃料電池を以下、（Ａ）電池
と称する。 〔比較例〕Ｐｔ／Ｃとナフィオン１１７との混合物を上
記実施例と同様にして真空乾燥を行ない、Ｐｔ／Ｃの表
面にアルコール難溶解性のナフィオン膜を形成した。次
に、この膜の表面にアルコール易溶解性の膜を形成させ
ることなく、前記アルコール難溶解性のナフィオン膜の
みを形成したＰｔ／Ｃ同士を結着して電極触媒層シート
を作成した。最後に、上記実施例と同様にして電池を作
成した。The electrode thus prepared will be described below.
(A) It is called an electrode. Finally, the electrode (a) produced by the method of the present invention is used as Nafion 1 as an ion exchange membrane.
Both sides of No. 17 were joined by performing hot pressing at 125 kg at 200 kg / cm 2 , to prepare a battery. The polymer electrolyte fuel cell thus produced is hereinafter referred to as (A) cell. [Comparative Example] A mixture of Pt / C and Nafion 117 was vacuum dried in the same manner as in the above Examples to form a poorly soluble alcohol Nafion film on the surface of Pt / C. Next, an electrode catalyst layer sheet was prepared by binding Pt / Cs formed with only the Nafion film having a poor alcohol solubility to each other without forming a film having an alcohol easily soluble on the surface of the film. Finally, a battery was prepared in the same manner as in the above example.
【００１２】このようにして作成した固体高分子型燃料
電池を以下、（Ｘ）電池と称する。 〔実験〕上記本発明方法にて作成した（ａ）電極を用い
た（Ａ）電池と、比較例方法にて作成した（Ｘ）電池と
を用いて、それぞれの電池特性（電流密度とセル電圧と
の関係）について調べたので、その結果を図１に示す。
尚、実験条件は、セル温度を７０℃で行った。The polymer electrolyte fuel cell thus prepared is hereinafter referred to as (X) cell. [Experiment] Using the (A) battery using the (a) electrode prepared by the method of the present invention and the (X) battery prepared by the comparative method, the respective battery characteristics (current density and cell voltage) were measured. Relationship) with the results are shown in FIG.
The experimental condition was that the cell temperature was 70 ° C.
【００１３】図１から明らかなように、本発明方法にて
作成した（ａ）電極を用いた（Ａ）電池は比較例方法に
て作成した（Ｘ）電池に比べて、電池特性がはるかに向
上していることが認められる。これは、本発明方法で
は、アルコール難溶解性のイオン交換体膜の表面に、ア
ルコール溶解性のイオン交換体膜が形成されるため、こ
のイオン交換体膜がアルコールによってゲル状になり、
接着剤の役目をなす。そのため、触媒粒子同士の結着性
が向上し、イオン伝導性が向上する。これに対して、比
較例方法にて作成した電極は、アルコールを加えてもイ
オン交換体膜が溶解しないため、触媒粒子同士の結着が
悪く、イオン伝導性が悪い。 〔その他の事項〕上記実施例方法では、触媒粒子の表面
にアルコール難溶性のイオン交換体膜を形成し、このイ
オン交換膜の表面にアルコール易溶解性のイオン交換体
膜を形成したが、触媒粒子の表面にアルコール難溶解性
のイオン交換膜を形成する工程を省略し、アルコール易
溶解性のイオン交換体膜を触媒粒子の表面に直接形成し
た後、前記方法と同様にして電極を作成することも勿論
可能である。As is apparent from FIG. 1, the (A) battery using the electrode (a) prepared by the method of the present invention has far more battery characteristics than the battery (X) prepared by the comparative method. It is recognized that it has improved. This is because in the method of the present invention, the alcohol-soluble ion exchanger membrane is formed on the surface of the poorly soluble alcohol ion-exchange membrane, so that the ion-exchange membrane becomes a gel by alcohol.
Serves as an adhesive. Therefore, the binding property between the catalyst particles is improved, and the ionic conductivity is improved. On the other hand, in the electrode prepared by the comparative example method, the ion exchanger membrane does not dissolve even when alcohol is added, so that the binding between the catalyst particles is poor and the ion conductivity is poor. [Other Matters] In the above-mentioned example method, an alcohol-insoluble ion-exchange membrane was formed on the surface of catalyst particles, and an alcohol-soluble ion-exchange membrane was formed on the surface of this ion-exchange membrane. By omitting the step of forming an alcohol-insoluble ion-exchange membrane on the surface of the particle, and forming an alcohol-soluble ion-exchange membrane directly on the surface of the catalyst particle, an electrode is prepared in the same manner as the above method. Of course, it is possible.
【００１４】[0014]
【発明の効果】以上説明した如く本発明方法によれば、
触媒粒子の表面に、アルコールで溶解しゲル状になるイ
オン交換体膜を形成させることができるので、触媒粒子
同士の結着性が向上し、イオン伝導性が良くなる。As described above, according to the method of the present invention,
Since it is possible to form an ion-exchange membrane that dissolves in alcohol to form a gel on the surface of the catalyst particles, the binding property between the catalyst particles is improved and the ion conductivity is improved.
【図１】本発明方法にて作成した（ａ）電極を用いた
（Ａ）電池と、比較例方法にて作成した（Ｘ）電池とを
用いた場合における、電池特性（電流密度とセル電圧と
の関係）を示すグラフである。FIG. 1 shows the battery characteristics (current density and cell voltage) in the case of using the battery (A) using the electrode (a) prepared by the method of the present invention and the battery (X) prepared by the comparative example method. (Relationship with).
Claims (2)
る第１ステップと、 前記触媒粒子の表面にイオン交換体膜を形成でき、且
つ、このイオン交換体膜がアルコールに対して易溶解性
となる程度に前記混合物を乾燥する第２ステップと、 前記イオン交換体膜を形成した触媒粒子を圧延又は加圧
して、触媒層シートを作成する第３ステップと、 前記触媒層シートにアルコール水溶液を含浸して、前記
触媒粒子の表面に形成したイオン交換体膜を溶解させる
第４ステップと、 前記触媒層シートを乾燥して、前記アルコール水溶液を
除去する第５ステップと、 を有することを特徴とする固体高分子型燃料電池用電極
の製造方法。1. A first step of mixing catalyst particles and an ion-exchanger solution; an ion-exchanger membrane can be formed on the surface of the catalyst particles, and the ion-exchanger membrane is easily soluble in alcohol. The second step of drying the mixture to such an extent, the third step of rolling or pressurizing the catalyst particles having the ion exchanger membrane formed thereon to form a catalyst layer sheet, and an aqueous alcohol solution on the catalyst layer sheet. A fourth step of impregnating and dissolving the ion exchanger membrane formed on the surface of the catalyst particles; and a fifth step of drying the catalyst layer sheet to remove the aqueous alcohol solution. A method for producing a solid polymer fuel cell electrode.
る第１ステップと、 前記触媒粒子の表面にイオン交換体膜を形成でき、且
つ、このイオン交換体膜がアルコールに対して難溶解性
となる程度に前記混合物を乾燥する第２ステップと、 前記イオン交換体膜を形成した触媒粒子とイオン交換体
溶液とを混合する第３ステップと、 前記アルコール難溶解性のイオン交換体膜の表面にイオ
ン交換体膜を形成でき、且つ、このイオン交換体膜がア
ルコールに対して易溶解性となる程度に前記混合物を乾
燥する第４ステップと、 前記イオン交換体膜を形成した触媒粒子を圧延又は加圧
して、触媒層シートを作成する第５ステップと、 前記触媒層シートにアルコール水溶液を含浸して、前記
アルコール難溶解性のイオン交換体膜の表面に形成した
イオン交換体膜を溶解させる第６ステップと、 前記触媒層シートを乾燥して、前記アルコール水溶液を
除去する第７ステップと、 を有することを特徴とする固体高分子型燃料電池用電極
の製造方法。2. A first step of mixing catalyst particles and an ion exchanger solution; an ion exchanger film can be formed on the surface of the catalyst particles, and the ion exchanger film is hardly soluble in alcohol. The second step of drying the mixture to such an extent that the above-mentioned is satisfied, the third step of mixing the catalyst particles forming the ion-exchanger membrane and the ion-exchanger solution, and the surface of the poorly soluble alcohol ion-exchanger membrane. A step of drying the mixture to such an extent that an ion-exchange membrane can be formed on the ion-exchange membrane, and the ion-exchange membrane is easily soluble in alcohol; and rolling the catalyst particles on which the ion-exchange membrane is formed. Alternatively, the step of forming a catalyst layer sheet by pressurizing is performed, and the catalyst layer sheet is impregnated with an aqueous alcohol solution to form an ion exchange membrane on the surface of the hardly soluble alcohol ion exchange membrane. A sixth step of dissolving the hydrogen exchange membrane, and a seventh step of drying the catalyst layer sheet to remove the alcohol aqueous solution, and a method for producing an electrode for a polymer electrolyte fuel cell. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27212993A JP3182265B2 (en) | 1993-10-29 | 1993-10-29 | Method for producing electrode for polymer electrolyte fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27212993A JP3182265B2 (en) | 1993-10-29 | 1993-10-29 | Method for producing electrode for polymer electrolyte fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07130375A true JPH07130375A (en) | 1995-05-19 |
| JP3182265B2 JP3182265B2 (en) | 2001-07-03 |
Family
ID=17509499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27212993A Expired - Fee Related JP3182265B2 (en) | 1993-10-29 | 1993-10-29 | Method for producing electrode for polymer electrolyte fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3182265B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001300324A (en) * | 2000-04-26 | 2001-10-30 | Japan Storage Battery Co Ltd | Composite catalyst and manufacturing method and method of manufacturing electrode for fuel cell using the same |
| EP1294034A1 (en) * | 2000-06-22 | 2003-03-19 | Matsushita Electric Industrial Co., Ltd. | Polymer electrolyte fuel cell, method for manufacturing electrode thereof, and manufacturing apparatus |
| JP2011009226A (en) * | 2010-07-20 | 2011-01-13 | Gs Yuasa Corp | Composite catalyst, its manufacturing method, and method of electrode for manufacturing fuel cell using the composite catalyst |
| JP2013020816A (en) * | 2011-07-11 | 2013-01-31 | Jx Nippon Oil & Energy Corp | Membrane electrode assembly and manufacturing method therefor, and fuel cell |
| KR20190081380A (en) * | 2017-12-29 | 2019-07-09 | 현대자동차주식회사 | Method of manufacturing membrane electrode assembly for fuel cell |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5181469B2 (en) * | 2006-11-22 | 2013-04-10 | トヨタ自動車株式会社 | Manufacturing method of membrane electrode assembly |
-
1993
- 1993-10-29 JP JP27212993A patent/JP3182265B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001300324A (en) * | 2000-04-26 | 2001-10-30 | Japan Storage Battery Co Ltd | Composite catalyst and manufacturing method and method of manufacturing electrode for fuel cell using the same |
| EP1294034A1 (en) * | 2000-06-22 | 2003-03-19 | Matsushita Electric Industrial Co., Ltd. | Polymer electrolyte fuel cell, method for manufacturing electrode thereof, and manufacturing apparatus |
| US7029785B2 (en) | 2000-06-22 | 2006-04-18 | Matsushita Electric Industrial Co., Ltd. | Polymer electrolyte fuel cells, methods of manufacturing electrodes therefor , and apparatuses for making the same |
| CN1310358C (en) * | 2000-06-22 | 2007-04-11 | 松下电器产业株式会社 | Polymer electrolyte fuel cell, and method for manufacturing electrode thereof, and manufacturing apparatus |
| EP1294034A4 (en) * | 2000-06-22 | 2007-12-05 | Matsushita Electric Ind Co Ltd | Polymer electrolyte fuel cell, method for manufacturing electrode thereof, and manufacturing apparatus |
| US7544630B2 (en) | 2000-06-22 | 2009-06-09 | Panasonic Corporation | Methods of manufacturing electrodes for polymer electrolyte fuel cells |
| EP2124275A1 (en) * | 2000-06-22 | 2009-11-25 | Panasonic Corporation | Apparatus for manufacturing electrode for polymer electrolyte fuel cell, and method of manufacturing the same |
| JP2011009226A (en) * | 2010-07-20 | 2011-01-13 | Gs Yuasa Corp | Composite catalyst, its manufacturing method, and method of electrode for manufacturing fuel cell using the composite catalyst |
| JP2013020816A (en) * | 2011-07-11 | 2013-01-31 | Jx Nippon Oil & Energy Corp | Membrane electrode assembly and manufacturing method therefor, and fuel cell |
| KR20190081380A (en) * | 2017-12-29 | 2019-07-09 | 현대자동차주식회사 | Method of manufacturing membrane electrode assembly for fuel cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3182265B2 (en) | 2001-07-03 |
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