JPH0129878B2 - - Google Patents
Info
- Publication number
- JPH0129878B2 JPH0129878B2 JP60066248A JP6624885A JPH0129878B2 JP H0129878 B2 JPH0129878 B2 JP H0129878B2 JP 60066248 A JP60066248 A JP 60066248A JP 6624885 A JP6624885 A JP 6624885A JP H0129878 B2 JPH0129878 B2 JP H0129878B2
- Authority
- JP
- Japan
- Prior art keywords
- exchange membrane
- metal
- ion exchange
- contact
- ion
- 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
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明はイオン交換膜に触媒電極を接合する方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for joining a catalyst electrode to an ion exchange membrane.
従来の技術
イオン交換膜を電解質とし、且つ該イオン交換
膜に触媒電極を一体に接合した電気化学装置に
は、水電解装置、ハロゲン化アルカリ電解装置、
酸素分離装置、燃料電池等がある。イオン交換膜
と触媒電極との接合方法には、無電解メツキ法と
特公昭58−15544号に記載されている電極材料粉
末と結着剤との混合物からなる触媒電極をイオン
交換膜に加熱圧着する方法とがある。Prior Art Electrochemical devices in which an ion exchange membrane is used as an electrolyte and a catalyst electrode is integrally bonded to the ion exchange membrane include water electrolysis devices, alkali halide electrolysis devices,
There are oxygen separators, fuel cells, etc. The ion-exchange membrane and the catalyst electrode are joined together by the electroless plating method and by heating and pressing the catalyst electrode, which is made of a mixture of electrode material powder and a binder, onto the ion-exchange membrane, as described in Japanese Patent Publication No. 15544/1983. There is a way to do this.
無電解メツキ法を大別すると浸透法（特開昭55
−38934号）と吸着還元成長法（特開昭57−
134586号）とに分類することができるが、本発明
は吸着還元成長法の改良を図らんとするものであ
る。 The electroless plating method can be roughly divided into the penetration method (Japanese Patent Application Laid-Open No.
-38934) and the adsorption-reduction growth method (Japanese Patent Application Laid-open No. 1983-
134586), but the present invention aims to improve the adsorption-reduction growth method.
吸着還元成長法によつてイオン交換膜の両面に
触媒電極を接合する場合、イオン交換膜の両面に
同種の触媒電極を接合することは容易である。し
かしながら両面に異種の触媒電極を接合する場合
や、片面に吸着還元成長法によつて触媒電極を接
合し、他面に加熱圧着法によつて触媒電極を接合
する場合には、片面にのみ吸着還元成長法によつ
て触媒電極を接合する必要がある。その際、従来
はイオン交換膜のメツキしない面を樹脂板等に密
着させてマスキングし、他面をメツキ浴に接触さ
せて触媒電極を接合していた。 When bonding catalyst electrodes to both sides of an ion exchange membrane by the adsorption-reduction growth method, it is easy to bond the same type of catalyst electrodes to both sides of the ion exchange membrane. However, when bonding different types of catalyst electrodes on both sides, or when bonding catalyst electrodes on one side by adsorption-reduction growth method and the other side by heat-pressing method, adsorption occurs only on one side. It is necessary to bond the catalytic electrodes by a reductive growth method. At that time, conventionally, the unplated surface of the ion exchange membrane was masked by bringing it into close contact with a resin plate, etc., and the other surface was brought into contact with a plating bath to join the catalyst electrode.
発明が解決しようとする問題点
しかし、イオン交換膜のメツキしない面を樹脂
板等に密着させた場合には、しばしば樹脂板とイ
オン交換膜との間に気泡が発生し、そのために均
質なメツキ層が得られないことが多かつた。Problems to be Solved by the Invention However, when the unplated surface of an ion exchange membrane is brought into close contact with a resin plate, etc., air bubbles often occur between the resin plate and the ion exchange membrane, resulting in a uniform plating. In many cases, a layer could not be obtained.
問題点を解決するための手段
本発明は吸着還元成長法によつてイオン交換膜
の片面に触媒電極を接合する際、イオン交換膜の
片面のみメツキ浴に接触させ、他面を水に接触さ
せることによつて、上述の如き問題点を解決する
ものである。Means for Solving the Problems The present invention, when bonding a catalyst electrode to one side of an ion exchange membrane by an adsorption-reduction growth method, only one side of the ion exchange membrane is brought into contact with a plating bath and the other side is brought into contact with water. This solves the above-mentioned problems.
作 用
吸着還元成長法は、吸着過程と還元過程と成長
過程からなつている。吸着過程においては、触媒
金属の化合物の水溶液をイオン交換膜に接触さ
せ、イオン交換膜中の水素イオンと金属イオンあ
るいは金属錯体イオンとの置換を行なう。還元過
程においては、水素化ホウ素ナトリウムの如き還
元剤によつて、上述の金属イオンあるいは金属錯
体イオンが還元されて、金属が析出する。この析
出した金属が次の成長過程における成長核とな
る。成長過程では、触媒金属の化合物と還元剤と
の混合水溶液から触媒金属が上述の成長核の上に
成長していく。これらのすべての過程で、水がイ
オン交換膜の内部に充分含浸されている必要があ
る。ところが従来のようにイオン交換膜と樹脂板
との間に気泡が発生すると、イオン交換膜の気泡
に接触している部分の含水量が少なくなり、した
がつて上述の吸着還元成長法の各過程において金
属イオンあるいは還元剤が充分浸透しなくなり、
金属イオンあるいは還元剤が浸透しない部分では
最終的に触媒金属の析出量も少なくなる。Effect The adsorption-reduction growth method consists of an adsorption process, a reduction process, and a growth process. In the adsorption process, an aqueous solution of a catalytic metal compound is brought into contact with an ion exchange membrane to replace hydrogen ions in the ion exchange membrane with metal ions or metal complex ions. In the reduction process, the metal ions or metal complex ions mentioned above are reduced by a reducing agent such as sodium borohydride, and the metal is precipitated. This precipitated metal becomes a growth nucleus in the next growth process. In the growth process, a catalytic metal grows on the above-mentioned growth nucleus from a mixed aqueous solution of a catalytic metal compound and a reducing agent. In all of these processes, the ion exchange membrane must be sufficiently impregnated with water. However, when air bubbles occur between the ion exchange membrane and the resin plate as in the conventional method, the water content of the portion of the ion exchange membrane that is in contact with the air bubbles decreases, and therefore each process of the adsorption-reduction growth method described above decreases. metal ions or reducing agents cannot penetrate sufficiently,
In areas where metal ions or reducing agents do not permeate, the amount of catalytic metal deposited ultimately decreases.
これに対して本発明のように、イオン交換膜の
触媒電極を接合しない面に水を接触させておけ
ば、気泡の生成が防止できるので、金属イオンも
還元剤もイオン交換膜の全面に均等に行きわた
り、その結果として触媒金属の均質な接合が可能
となる。 On the other hand, as in the present invention, if water is brought into contact with the surface of the ion-exchange membrane that is not bonded to the catalyst electrode, the formation of bubbles can be prevented, so that metal ions and reducing agents are distributed evenly over the entire surface of the ion-exchange membrane. As a result, homogeneous bonding of the catalytic metal becomes possible.
実施例 以下、本発明の実施例について詳述する。Example Examples of the present invention will be described in detail below.
本発明の一実施例にかかる無電解メツキ槽の縦
断面構造を図に示す。該図に示すように、イオン
交換膜１をパツキン２を介してホルダー３に装着
する。イオン交換膜１のメツキしない側のホルダ
ー３内に注液口から水を注入し、水浴５とする。
次にイオン交換膜１のメツキする側のホルダー３
内に注液口７から白金アンミン錯体（［PtCl2
（NH3）2］Cl2）の水溶液を注入してメツキ浴６と
し、その状態で約１時間放置した後、残つた白金
アンミン錯体水溶液を排出して充分水洗した。次
に水素化ホウ素ナトリウム水溶液を注入し、約１
時間放置した。この段階で、メツキ浴６と接触し
ているイオン交換膜１の表面には、メツキ核とな
る白金が析出してくる。次に水素化ホウ素ナトリ
ウム水溶液を排出し、充分水洗した後、塩化白金
酸水溶液を注入し、さらに塩酸ヒドラジン水溶液
を注入して約５時間放置すると、イオン交換膜１
の片面の表面に白金が均一に析出した。なお、図
において、８は攪拌器である。 The longitudinal cross-sectional structure of an electroless plating tank according to an embodiment of the present invention is shown in the figure. As shown in the figure, the ion exchange membrane 1 is attached to the holder 3 via the packing 2. Water is injected into the holder 3 on the non-plated side of the ion exchange membrane 1 from the liquid injection port to form a water bath 5.
Next, the holder 3 on the side of the ion exchange membrane 1 to be plated
Platinum ammine complex ([PtCl 2
An aqueous solution of (NH 3 ) 2 ]Cl 2 ) was injected to form a plating bath 6, and after leaving the bath in that state for about 1 hour, the remaining platinum ammine complex aqueous solution was discharged and thoroughly washed with water. Next, inject a sodium borohydride aqueous solution and
I left it for a while. At this stage, platinum, which serves as plating nuclei, is deposited on the surface of the ion exchange membrane 1 that is in contact with the plating bath 6. Next, after discharging the sodium borohydride aqueous solution and thoroughly washing with water, a chloroplatinic acid aqueous solution was injected, and then a hydrazine hydrochloride aqueous solution was injected and left for about 5 hours.
Platinum was deposited uniformly on one side of the surface. In addition, in the figure, 8 is a stirrer.
比較のために、従来の方法であるイオン交換膜
のメツキを施さない面にアクリル樹脂板を密着さ
せる方法を用いて上記本発明実施例と同様の白金
メツキを施したところ、イオン交換膜とアクリル
樹脂板との間の上部に気泡が生成し、この部分の
白金の析出量が異常に少なかつた。 For comparison, platinum plating was applied in the same manner as in the above-mentioned embodiment of the present invention using the conventional method of adhering an acrylic resin plate to the unplated surface of the ion exchange membrane. Air bubbles were generated in the upper part between the resin plate and the amount of platinum deposited in this area was abnormally small.
発明の効果
以上詳述したように本発明によれば、吸着還元
成長法によつてイオン交換膜の特に片面だけに触
媒電極を接合する際、均質な触媒電極の接合状態
が得られ、本発明の工業的価値極めて大である。Effects of the Invention As detailed above, according to the present invention, when a catalyst electrode is bonded to only one side of an ion exchange membrane by the adsorption-reduction growth method, a homogeneous bonded state of the catalyst electrode can be obtained, and the present invention Its industrial value is extremely large.
図は本発明の一実施例にかかる無電解メツキ槽
の縦断面構造図である。
１……イオン交換膜、２……パツキン、３……
ホルダー、４……注液口、５……水浴、６……メ
ツキ浴、７……注液口、８……攪拌器。
The figure is a longitudinal cross-sectional structural diagram of an electroless plating tank according to an embodiment of the present invention. 1...Ion exchange membrane, 2...Packkin, 3...
Holder, 4...liquid inlet, 5...water bath, 6...metallic bath, 7...liquid inlet, 8...stirrer.
Claims (1)
際、イオン交換膜の触媒電極を接合しない面に水
を、他面には触媒金属化合物の水溶液を接触さ
せ、イオン交換膜の水素イオンと金属イオンある
いは金属錯体イオンとの置換を行い、次に還元剤
によつて金属イオンあるいは金属錯体イオンを還
元して成長核となる金属を析出させ、最後に触媒
金属化合物と還元剤との混合水溶液に接触させて
触媒金属を前記成長核の上に析出成長させること
を特徴とするイオン交換膜に触媒電極を接合する
方法。1. When bonding a catalyst electrode to one side of an ion-exchange membrane, the surface of the ion-exchange membrane on which the catalyst electrode is not bonded is brought into contact with water, and the other side is brought into contact with an aqueous solution of a catalytic metal compound, so that the hydrogen ions and metal ions of the ion-exchange membrane are brought into contact with water. Alternatively, the metal complex ions are replaced with metal complex ions, and then the metal ions or metal complex ions are reduced with a reducing agent to precipitate the metal that will serve as a growth nucleus, and finally brought into contact with a mixed aqueous solution of a catalytic metal compound and a reducing agent. A method for joining a catalytic electrode to an ion exchange membrane, characterized in that a catalytic metal is precipitated and grown on the growth nuclei.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60066248A JPS61223191A (en) | 1985-03-28 | 1985-03-28 | Method for joining catalytic electrode to ion exchange membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60066248A JPS61223191A (en) | 1985-03-28 | 1985-03-28 | Method for joining catalytic electrode to ion exchange membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61223191A JPS61223191A (en) | 1986-10-03 |
| JPH0129878B2 true JPH0129878B2 (en) | 1989-06-14 |
Family
ID=13310373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60066248A Granted JPS61223191A (en) | 1985-03-28 | 1985-03-28 | Method for joining catalytic electrode to ion exchange membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61223191A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2624885B1 (en) * | 1987-12-17 | 1991-01-04 | Commissariat Energie Atomique | SOLID POLYMER ELECTRODE-ELECTROLYTE ASSEMBLY USED FOR EXAMPLE FOR THE ELECTROLYSIS OF WATER, AND ITS MANUFACTURING METHOD |
| US4959132A (en) * | 1988-05-18 | 1990-09-25 | North Carolina State University | Preparing in situ electrocatalytic films in solid polymer electrolyte membranes, composite microelectrode structures produced thereby and chloralkali process utilizing the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1130955B (en) * | 1980-03-11 | 1986-06-18 | Oronzio De Nora Impianti | PROCEDURE FOR THE FORMATION OF ELECTROCES ON THE SURFACES OF SEMI-PERMEABLE MEMBRANES AND ELECTRODE-MEMBRANE SYSTEMS SO PRODUCED |
-
1985
- 1985-03-28 JP JP60066248A patent/JPS61223191A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61223191A (en) | 1986-10-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |