JPH0645911B2 - Method for manufacturing gas diffusion electrode - Google Patents

Method for manufacturing gas diffusion electrode

Info

Publication number
JPH0645911B2
JPH0645911B2 JP60294432A JP29443285A JPH0645911B2 JP H0645911 B2 JPH0645911 B2 JP H0645911B2 JP 60294432 A JP60294432 A JP 60294432A JP 29443285 A JP29443285 A JP 29443285A JP H0645911 B2 JPH0645911 B2 JP H0645911B2
Authority
JP
Japan
Prior art keywords
water
carbon black
gas diffusion
hydrophilic
repellent
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.)
Expired - Lifetime
Application number
JP60294432A
Other languages
Japanese (ja)
Other versions
JPS62156286A (en
Inventor
長一 古屋
哲 本尾
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tanaka Kikinzoku Kogyo KK
Original Assignee
Tanaka Kikinzoku Kogyo KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tanaka Kikinzoku Kogyo KK filed Critical Tanaka Kikinzoku Kogyo KK
Priority to JP60294432A priority Critical patent/JPH0645911B2/en
Publication of JPS62156286A publication Critical patent/JPS62156286A/en
Publication of JPH0645911B2 publication Critical patent/JPH0645911B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Inert Electrodes (AREA)

Description

【発明の詳細な説明】 （産業上の利用分野） 本発明は、燃料電池、二次電池、電気化学的リアクタ
ー、めっき用陽極等に用いるガス拡散電極の製造方法の
改良に関する。TECHNICAL FIELD The present invention relates to an improvement in a method for producing a gas diffusion electrode used for a fuel cell, a secondary battery, an electrochemical reactor, an anode for plating, and the like.

（従来の技術） 従来、反応層にガス拡散層の接合されて成るガス拡散電
極を作るには、白金粉末とカーボンブラックと水とポリ
四弗化エチレンとの混合液を濾過してケーキを作成し、
一方撥水性のカーボンブラックと水とポリ四弗化エチレ
ンとの混合液を濾過してケーキを作成し、次に両ケーキ
を圧延した後乾燥して反応層とガス拡散層を作り、次い
で反応層とガス拡散層を所要の寸法に切断した後加熱圧
着して接合していた。(Prior Art) Conventionally, in order to form a gas diffusion electrode in which a gas diffusion layer is joined to a reaction layer, a mixed liquid of platinum powder, carbon black, water and polytetrafluoroethylene is filtered to form a cake. Then
On the other hand, a mixture of water-repellent carbon black, water and polytetrafluoroethylene is filtered to form a cake, and then both cakes are rolled and dried to form a reaction layer and a gas diffusion layer, and then a reaction layer. Then, the gas diffusion layer was cut to a required size and then heated and pressure-bonded.

（発明が解決しようとする問題点） ところで、上記の製造方法で得られたガス拡散電極の反
応層中の白金粉末は、カーボンブラックと撥水性である
ポリ四弗化エチレン粉末との間に介在したり、ポリ四弗
化エチレン粉末間に介在したりしているものが多い為、
燃料電池等に使用した際、電解液が反応層中に浸透して
も全ての白金粉末には接触しない。従って、触媒として
有効に働かない白金が多く、触媒の重さ当り、流せる電
流の少ないものである。また上記の製造方法は、反応層
とガス拡散層の圧延による成形が難しく、さらにこれら
を所要の寸法に切断するので、白金の含有するスクラッ
プが生じるので、白金の回収と手間と費用がかかる。(Problems to be Solved by the Invention) By the way, the platinum powder in the reaction layer of the gas diffusion electrode obtained by the above production method is present between carbon black and water repellent polytetrafluoroethylene powder. Since there are many things that intervene between the polytetrafluoroethylene powder,
When used in a fuel cell or the like, even if the electrolytic solution penetrates into the reaction layer, it does not contact all the platinum powder. Therefore, a large amount of platinum does not work effectively as a catalyst, and the amount of current that can be passed is small per the weight of the catalyst. Further, in the above-mentioned manufacturing method, it is difficult to form the reaction layer and the gas diffusion layer by rolling, and further, since these are cut into a required size, scrap containing platinum is generated, so that platinum recovery, labor and cost are required.

そこで本発明は、電解液が反応層中の全ての白金に接触
して、触媒反応が行われるガス拡散電極を作ることがで
き、また成形が容易で白金の含有するスクラップが生じ
ないようにしたガス拡散電極の製造方法を提供せんとす
るものである。Therefore, the present invention makes it possible to form a gas diffusion electrode in which the electrolytic solution is brought into contact with all platinum in the reaction layer to carry out a catalytic reaction, and which is easy to mold and does not generate scrap containing platinum. It is intended to provide a method for manufacturing a gas diffusion electrode.

（問題点を解決するための手段） 上記問題点を解決するための本発明のガス拡散電極の製
造方法は、親水性と撥水性のカーボンブラックと水とポ
リ四弗化エチレンとの混合液を濾過してケーキを作製
し、一方撥水性のカーボンブラックと水とポリ四弗化エ
チレンとの混合液を濾過してケーキを作製し、次に両ケ
ーキに溶剤を浸透させ夫々圧延して所要の厚さとなし、
次いで夫々加熱し水及び溶剤を除去してシートを作製し
た後、両シートを加熱して加圧接合し、次いで親水性カ
ーボンブラックの含有するシートに白金族化合物溶液を
含浸させ、加熱分解して白金族金属又はその酸化物若し
くはその両方（これらを以下単に白金族という）を親水
性カーボンブラックより成る親水部に付着して、親水性
カーボンブラックより成る親水部及び撥水性カーボンブ
ラックより成る撥水部から成る反応層並びに撥水性のガ
ス拡散層を有するガス拡散電極を作ることを特徴とする
ものである。(Means for Solving the Problems) A method for manufacturing a gas diffusion electrode of the present invention for solving the above problems is to provide a mixed liquid of hydrophilic and water-repellent carbon black, water and polytetrafluoroethylene. A cake is prepared by filtering, while a water-repellent carbon black / water / polytetrafluoroethylene mixed solution is filtered to prepare a cake. Thickness and none,
Then, each sheet was heated to remove water and solvent to produce a sheet, both sheets were heated and pressure-bonded, then the sheet containing hydrophilic carbon black was impregnated with a platinum group compound solution, and thermally decomposed. A platinum group metal or an oxide thereof or both (hereinafter simply referred to as platinum group) is adhered to a hydrophilic part made of hydrophilic carbon black to give a hydrophilic part made of hydrophilic carbon black and a water repellent made of water repellent carbon black. The present invention is characterized in that a gas diffusion electrode having a reaction layer composed of parts and a water-repellent gas diffusion layer is produced.

なお親水性カーボンブラックは表面に−ＣＯＯＨ等の水
と親和性のある活性基を持つもので、水に分散する性質
を有し、撥水性カーボンブラックはグラファイト化が進
行しており、水と親和性のある活性基を持たず、そのま
までは水に分散しないものを使用する。Hydrophilic carbon black has an active group having an affinity for water, such as -COOH, and has a property of dispersing in water. The water-repellent carbon black has been graphitized and has an affinity for water. Use those that do not have active groups with properties and do not disperse in water as they are.

（作用） 上記の本発明のガス拡散電極の製造方法では、ケーキに
溶剤を含浸させるので圧延し易く、所要の厚さに容易に
成形でき、また最終的に所要の寸法に切断した後、親水
性のカーボンブラックの有するシートに白金族化合物溶
液を含浸させ、加熱分解して白金族を親水部に付着させ
ているので、白金族の含有するスクラップは全く生じな
い。さらに電解液が浸透可能な親水性カーボンブラック
より成る親水部にのみ白金族が付着するので、電解液は
反応層中の全ての白金族に接触することとなって、触媒
反応が活発に行われ、単位面積当りに大きい電流の流せ
る電極となる。(Operation) In the method for producing the gas diffusion electrode of the present invention described above, the cake is impregnated with the solvent so that it can be easily rolled, can be easily formed into a desired thickness, and is finally cut into a desired dimension, and then hydrophilic. Since the sheet containing the conductive carbon black is impregnated with the platinum group compound solution and thermally decomposed to adhere the platinum group to the hydrophilic portion, scrap contained in the platinum group does not occur at all. Furthermore, since the platinum group adheres only to the hydrophilic part made of hydrophilic carbon black that can penetrate the electrolytic solution, the electrolytic solution comes into contact with all platinum groups in the reaction layer, and the catalytic reaction is actively performed. , It becomes an electrode through which a large current can flow per unit area.

（実施例） 本発明のガス拡散電極の一実施例を図によって説明す
る。平均粒径420Åの親水性と撥水性のカーボンブラッ
ク（１：１）と水とを50℃でコロイドミル（超音波振動
攪拌機でも良い）で混合攪拌し、更にこの混合液に平均
粒径0.3μのポリ四弗化エチレン粉末をカーボンブラッ
クに対し２：８の割合で混合攪拌した後、この混合液を
第１図に示す如く濾過器３に注入して濾過し、濾過板４
上にケーキ５を作製する。一方平均粒径420Åの撥水性
のカーボンブラックと水とを50℃でコロイドミル（超音
波振動攪拌機でも良い）で混合攪拌し、更にこの混合液
に平均粒径0.3μのポリ四弗化エチレン粉末をカーボン
ブラックに対し７：３の割合で混合攪拌した後、この混
合液を第１図と同様に濾過器に注入して濾過し、濾過板
上にケーキ５′を作製する。次にケーキ５、５′に溶剤
例えばエタノールを浸透させ、夫々ロール圧延して厚さ
0.1mm、0.5mmとなし、次いで夫々280℃で加熱して乾燥
し且つアルコールを除去して第２図に示す如くシート
６、６′を作製し、次に両シート６、６′を夫々幅100m
m、110mm、長さ100mm、110mmに切断した後380℃で600kg
/cm2で加熱加圧して第３図に示す如く接合し、次いで親
水性カーボンブラックの含有するシート６の表面に第４
図に示す如く塩化パラジウム溶液７を塗布して含浸させ
た後、空気中200℃で加熱分解し、H2中200℃で還元して
パラジウムを親水部カーボンブラックに付着して、第５
図に示す如く親水性カーボンブラックより成る親水部及
び撥水性カーボンブラックより成る撥水部から成る反応
槽８と撥水性のガス拡散層９を有するガス拡散電極10を
作った。(Example) An example of the gas diffusion electrode of the present invention will be described with reference to the drawings. Hydrophilic and water-repellent carbon black (1: 1) with an average particle size of 420Å and water are mixed and stirred at 50 ° C with a colloid mill (or ultrasonic vibration stirrer), and this mixed solution has an average particle size of 0.3μ. The polytetrafluoroethylene powder (1) was mixed and stirred in a ratio of 2: 8 with respect to carbon black, and the mixed solution was poured into a filter 3 as shown in FIG.
Make cake 5 on top. On the other hand, water-repellent carbon black having an average particle size of 420Å and water are mixed and stirred at 50 ° C in a colloid mill (it may be an ultrasonic vibration stirrer). Is mixed with carbon black in a ratio of 7: 3 and stirred, and this mixed solution is poured into a filter and filtered in the same manner as in FIG. 1 to prepare a cake 5'on the filter plate. Then, a solvent such as ethanol is infiltrated into the cakes 5 and 5 ', and each is rolled to a thickness.
0.1 mm and 0.5 mm, then heated and dried at 280 ° C. to remove alcohol and form sheets 6 and 6 ′ as shown in FIG. 100m
600kg at 380 ℃ after cutting to m, 110mm, length 100mm, 110mm
Heat and pressurize at a pressure of / cm 2 to bond as shown in FIG. 3, and then make a fourth bond on the surface of the sheet 6 containing hydrophilic carbon black.
As shown in the figure, after applying palladium chloride solution 7 to impregnate it, it is decomposed by heating in air at 200 ° C and reduced in H 2 at 200 ° C to attach palladium to hydrophilic carbon black,
As shown in the figure, a gas diffusion electrode 10 having a reaction tank 8 composed of a hydrophilic portion made of hydrophilic carbon black and a water repellent portion made of water repellent carbon black and a gas repellent gas diffusion layer 9 was prepared.

このように作った本発明のガス拡散電極10を、例えば電
解液がＺｎＣｌ2、ＫＣｌ、ＮａＣｌから成る水溶液の
ハロゲン電池の陽極として使用した処、この水溶液が反
応層８中のパラジウムの付着したカーボンブラックの部
分のみに浸透して、このカーボンブラックに付着した全
てのパラジウムに接触する。従って、触媒反応が活発に
おこなわれ、Ｃｌ2が多量に生成されることとなって短
時間に充電が行われる。When the gas diffusion electrode 10 of the present invention thus produced is used as an anode of a halogen battery of an aqueous solution whose electrolyte is ZnCl 2 , KCl and NaCl, for example, the aqueous solution contains carbon to which palladium is attached in the reaction layer 8. It penetrates only the black part and contacts all the palladium attached to this carbon black. Therefore, the catalytic reaction is actively performed, a large amount of Cl 2 is produced, and the charging is performed in a short time.

尚、上記本発明のガス拡散電極の製造方法の実施例で
は、ケーキ５、５′に浸透させる溶剤にエタノールを用
いたが、ブタノール、イソプロピルアルコール、炭酸ア
ンモニウム溶液、炭酸水素アンモニウム溶液、ソルベン
トナフサ、アセント等でも良いものである。In the embodiment of the method for producing the gas diffusion electrode of the present invention, ethanol was used as the solvent for permeating the cakes 5 and 5 ', butanol, isopropyl alcohol, ammonium carbonate solution, ammonium hydrogen carbonate solution, solvent naphtha, Ascent etc. are also good.

また上記実施例では、カーボンブラックと水とを混合攪
拌した後、この混合液にポリ四弗化エチレン粉末を混合
しているが、当初よりカーボンブラック、水、ポリ四弗
化エチレン粉末を混合攪拌しても良いものである。Further, in the above embodiment, after mixing and stirring carbon black and water, polytetrafluoroethylene powder is mixed in this mixed solution, but from the beginning, carbon black, water, and polytetrafluoroethylene powder are mixed and stirred. It is good to do.

（発明の効果） 以上の説明で判るように本発明のガス拡散電極の製造方
法によれば、反応層中の電解液の浸透可能な親水性カー
ボンブラックより成る親水部にのみ白金族が付着してい
て、電解液が全ての白金族と接触し、触媒反応が活発に
行われ、単位面積当りに大きな電流を流すことができる
という優れた効果がある。(Effect of the Invention) As can be seen from the above description, according to the method for producing a gas diffusion electrode of the present invention, the platinum group adheres only to the hydrophilic portion of the reaction layer, which is made of hydrophilic carbon black and is permeable to the electrolytic solution. However, there is an excellent effect that the electrolytic solution comes into contact with all the platinum group metals, the catalytic reaction is actively performed, and a large current can be passed per unit area.

また本発明のガス拡散電極の製造方法では、反応層とガ
ス拡散層の素材であるケーキに溶剤を含浸させるので圧
延し易く、所要の厚さに容易に成形できる。また最終的
に所要の寸法に切断した後、親水性のカーボンブラック
を有するシートに白金族化合物溶液を含浸させ、加熱分
解して白金族を親水性カーボンブラックより成る親水部
に付着させるので、白金族の含有するスクラップは全く
生ぜず、従って従来のように白金族の回収に手間と費用
がかかることが無い等の利点がある。Further, in the method for producing the gas diffusion electrode of the present invention, the cake, which is the material of the reaction layer and the gas diffusion layer, is impregnated with the solvent, so that it can be easily rolled and can be easily formed into a desired thickness. In addition, after finally cutting to the required size, a sheet having hydrophilic carbon black is impregnated with a platinum group compound solution, and thermally decomposed to adhere the platinum group to the hydrophilic part made of hydrophilic carbon black. The scrap contained in the group does not occur at all, so that there is an advantage that recovery of the platinum group does not take time and cost unlike the conventional case.

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

第１図乃至第５図は本発明のガス拡散電極の製造方法の
一実施例の工程を示す図である。1 to 5 are views showing steps of an embodiment of a method for manufacturing a gas diffusion electrode of the present invention.

Claims (1)

【特許請求の範囲】[Claims] 【請求項１】表面に水と親和性のある活性基を持つ親水
性カーボンブラックと表面に水と親和性のある活性基を
持たない撥水性のカーボンブラックと水とポリ四弗化エ
チレンとの混合物を濾過してケーキを作製し、一方上記
撥水性のカーボンブラックと水とポリ四弗化エチレンの
混合液を濾過してケーキを作製し、次に両ケーキに溶剤
を浸透させ夫々圧延して所要の厚さとなし、次いで夫々
加熱し水及び溶剤を除去してシートを作製した後、両シ
ートを加熱して加圧接合し、次いで上記親水性カーボン
ブラックの含有するシートに白金族化合物溶液を含浸さ
せ、加熱分解して白金族金属又はその酸化物若しくはそ
の両方を上記親水性カーボンブラックより成る親水部に
付着して、上記親水性カーボンブラックより成る親水部
及び上記撥水性カーボンブラックより成る撥水部から成
る反応層並びに撥水性のガス拡散層を有するガス拡散電
極を作ることを特徴とするガス拡散電極の製造方法。1. A hydrophilic carbon black having an active group having an affinity for water on the surface, a water-repellent carbon black having no active group having an affinity for water on the surface, water and polytetrafluoroethylene. The mixture is filtered to form a cake, while the water-repellent carbon black, water and polytetrafluoroethylene mixed solution is filtered to form a cake, and then both solvents are permeated with a solvent and rolled. After obtaining the required thickness, and then heating each to remove water and solvent to prepare a sheet, both sheets are heated and pressure-bonded, and then the platinum group compound solution is applied to the sheet containing the hydrophilic carbon black. It is impregnated and decomposed by heating to adhere the platinum group metal or its oxide or both to the hydrophilic part composed of the hydrophilic carbon black, and the hydrophilic part composed of the hydrophilic carbon black and the water repellent cover. Method for producing a gas diffusion electrode, characterized in that to make a reaction layer and a gas diffusion electrode having a gas diffusion layer of the water-repellent consisting repellent portion made of carbon black.
JP60294432A 1985-12-27 1985-12-27 Method for manufacturing gas diffusion electrode Expired - Lifetime JPH0645911B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP60294432A JPH0645911B2 (en) 1985-12-27 1985-12-27 Method for manufacturing gas diffusion electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60294432A JPH0645911B2 (en) 1985-12-27 1985-12-27 Method for manufacturing gas diffusion electrode

Publications (2)

Publication Number Publication Date
JPS62156286A JPS62156286A (en) 1987-07-11
JPH0645911B2 true JPH0645911B2 (en) 1994-06-15

Family

ID=17807688

Family Applications (1)

Application Number Title Priority Date Filing Date
JP60294432A Expired - Lifetime JPH0645911B2 (en) 1985-12-27 1985-12-27 Method for manufacturing gas diffusion electrode

Country Status (1)

Country Link
JP (1) JPH0645911B2 (en)

Also Published As

Publication number Publication date
JPS62156286A (en) 1987-07-11

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