JPH10330979A - Electrode membrane assembly and method of manufacturing the same - Google Patents
Electrode membrane assembly and method of manufacturing the sameInfo
- Publication number
- JPH10330979A JPH10330979A JP9147394A JP14739497A JPH10330979A JP H10330979 A JPH10330979 A JP H10330979A JP 9147394 A JP9147394 A JP 9147394A JP 14739497 A JP14739497 A JP 14739497A JP H10330979 A JPH10330979 A JP H10330979A
- Authority
- JP
- Japan
- Prior art keywords
- platinum
- iridium
- metal layer
- membrane
- electrode
- 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
-
- 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
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Fuel Cell (AREA)
Abstract
(57)【要約】
【解決手段】 カチオン交換樹脂膜に白金イオンをイオ
ン交換吸着させ、次いで還元剤を用いて該膜表面に白金
金属層を析出させた後、膜表面の少なくとも片方の面上
に電解めっき法によりイリジウム又は、白金−イリジウ
ム合金からなる金属層を成長させる。
【効果】 過電圧が低く、より高い性能を有する電極膜
接合体が得られる。しかも、電解めっき液自体の寿命が
長いため、めっき液中のイリジウム成分を有効利用でき
る上、反応速度が早いため、製造時間が短くなり、結果
的に量産性が増す。
(57) Abstract: Platinum ions are ion-exchanged and adsorbed on a cation exchange resin membrane, and then a platinum metal layer is deposited on the membrane surface using a reducing agent, and then on at least one surface of the membrane surface. Then, a metal layer made of iridium or a platinum-iridium alloy is grown by electrolytic plating. [Effect] An electrode membrane assembly having low overvoltage and higher performance can be obtained. In addition, since the life of the electrolytic plating solution itself is long, the iridium component in the plating solution can be effectively used, and the reaction speed is high, so that the production time is shortened, and as a result, mass productivity is increased.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、固体高分子型燃料
電池や固体高分子水電解装置等に用いられる電極膜接合
体及びその製造方法に関するものであり、特にイオン交
換膜とりわけＮａｆｉｏｎ( 登録商標) 等に代表される
カチオン交換膜上に触媒層となる白金族金属をコーティ
ングしてなる電極膜接合体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 an electrode membrane assembly for use in a polymer electrolyte fuel cell, a polymer water electrolysis apparatus and the like, and a method for producing the same. The present invention relates to an electrode membrane assembly formed by coating a platinum group metal to be a catalyst layer on a cation exchange membrane represented by, for example) and a method for producing the same.
【０００２】[0002]
【従来の技術】フルオロカーボンを基材とするカチオン
交換膜に直接電極を形成して、電極反応を行わせる固体
高分子水電解や固体高分子型燃料電池の研究開発が進め
られている。これらに用いられる電極−膜接合体の製造
方法としては、一般的に電極の金属または金属酸化物の
粒子をイオン交換膜の基材にホットプレスにより物理的
に接着するホットプレス法や、上記金属またはその化合
物を含むめっき液を用いてイオン交換膜の表面に化学め
っきすなわち無電解めっきにより電極膜を形成する化学
めっき法などが検討されている。特に化学めっき法の場
合、形成された電極層は、導電性に優れている上に、電
極としての大きな有効面積を有しているため、過電圧の
低い電極となる利点がある。2. Description of the Related Art Research and development of solid polymer water electrolysis and polymer electrolyte fuel cells in which an electrode is formed by directly forming an electrode on a cation exchange membrane containing fluorocarbon as a base material have been advanced. As a method for producing an electrode-membrane assembly used for these, generally, a hot press method of physically bonding metal or metal oxide particles of an electrode to a base material of an ion exchange membrane by hot press, Alternatively, a chemical plating method of forming an electrode film by chemical plating, ie, electroless plating, on the surface of an ion exchange membrane using a plating solution containing the compound has been studied. In particular, in the case of the chemical plating method, the formed electrode layer is excellent in conductivity and has a large effective area as an electrode, and thus has an advantage of being an electrode having a low overvoltage.
【０００３】また固体高分子水電解においては、現在上
記過電圧の低減のために、特に陽極サイド（酸素発生
極）に白金層だけではなく、触媒として過電圧の低いイ
リジウムなどの金属を白金層上に化学めっきにより形成
する方法が提唱されている。例えば特公昭５８−４７４
７１号公報に記載されているように、カチオン交換樹脂
膜に白金族の金属イオンをイオン交換で吸着させてから
水素化硼素塩水溶液で処理して膜の表面に金属層を析出
させ、更にこの膜を金属塩とジアルキルアミンボランと
を含有するアルカリ性水溶液と接触させて膜表面の金属
層を成長させることが知られている。[0003] In the solid polymer water electrolysis, in order to reduce the above-mentioned overvoltage, not only a platinum layer on the anode side (oxygen generating electrode) but also a metal such as iridium having a low overvoltage as a catalyst is formed on the platinum layer. A method of forming by chemical plating has been proposed. For example, Japanese Patent Publication No. 58-474
As described in Japanese Patent No. 71, a metal ion of the platinum group is adsorbed on a cation exchange resin membrane by ion exchange and then treated with an aqueous borohydride solution to precipitate a metal layer on the surface of the membrane. It is known that a film is brought into contact with an alkaline aqueous solution containing a metal salt and dialkylamine borane to grow a metal layer on the film surface.
【０００４】この場合、イリジウム層は電気化学的に酸
素発生を行う直接の触媒として寄与し、白金層は陰極で
発生した水素ガスと、陽極サイドで発生し逆拡散した酸
素ガスとを再酸化反応を行わせる触媒として寄与してい
る。従って、この白金層の存在により、陰極側で発生し
た水素、並びに陽極側で発生した酸素が共に高い純度を
維持できることになる。In this case, the iridium layer serves as a direct catalyst for electrochemically generating oxygen, and the platinum layer reoxidizes hydrogen gas generated at the cathode and oxygen gas generated at the anode side and back-diffused. It contributes as a catalyst for performing Therefore, due to the presence of this platinum layer, both the hydrogen generated on the cathode side and the oxygen generated on the anode side can maintain high purity.
【０００５】上記におけるイリジウム無電解めっきは、
特公昭６１−３６５９３、特公平０２−２０７０９、特
開平０８−１５８０５９などに代表される様々な浴が提
唱されているが、イオン交換膜上への触媒層形成の目的
で製造する上では、下記のような問題を発生する。 １）イリジウムの無電解反応自体が非常に不安定である
ため、イリジウムの析出量の制御が非常に困難である。 ２）上記１の理由により、白金層以外の部分にもイリジ
ウムが析出してしまう。（金属イリジウムは、王水など
の酸にも溶解しないため、除去が困難である。） ３）無電解めっき液自体の寿命が非常に短いため、めっ
き液中のイリジウム成分を有効利用できない。 ４）無電解めっき反応は、反応速度が非常に遅いため、
製造に時間がかかり、結果的に量産性が悪くなる。[0005] The iridium electroless plating in the above,
Various baths, such as Japanese Patent Publication No. 61-36593, Japanese Patent Publication No. 02-20709, and Japanese Patent Application Laid-Open No. 08-158059, have been proposed. However, in the production for the purpose of forming a catalyst layer on an ion exchange membrane, Problem like this. 1) Since the electroless reaction of iridium itself is very unstable, it is very difficult to control the amount of iridium deposited. 2) Iridium is deposited on portions other than the platinum layer for the first reason. (It is difficult to remove metal iridium because it does not dissolve in acids such as aqua regia.) 3) Since the life of the electroless plating solution itself is very short, the iridium component in the plating solution cannot be effectively used. 4) Since the rate of the electroless plating reaction is very slow,
Manufacturing takes time, resulting in poor mass productivity.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、これらの問
題を解消できる電極膜接合体及びその製造方法を提供す
ることを目的としている。SUMMARY OF THE INVENTION An object of the present invention is to provide an electrode membrane assembly which can solve these problems and a method for manufacturing the same.
【０００７】[0007]
【課題を解決するための手段】本発明の電極膜接合体
は、カチオン交換樹脂膜表面に金属層が形成されてなる
電極膜接合体において、樹脂膜表面の少なくとも片方の
面に白金の金属層とイリジウムまたは白金−イリジウム
合金の金属層が積層して形成されており、白金の金属層
は無電解めっきによって形成されたものであり、イリジ
ウム又は白金−イリジウム合金の金属層は電解めっきに
よって形成されたものであることを特徴とする。According to the present invention, there is provided an electrode membrane assembly having a metal layer formed on the surface of a cation exchange resin membrane, wherein at least one surface of the resin membrane surface has a metal layer of platinum. And a metal layer of iridium or a platinum-iridium alloy are formed by lamination, the metal layer of platinum is formed by electroless plating, and the metal layer of iridium or a platinum-iridium alloy is formed by electrolytic plating. It is characterized in that it is.
【０００８】また、本発明の電極膜接合体を製造する方
法は、カチオン交換樹脂膜に白金イオンをイオン交換吸
着させ、次いで還元剤を用いて該膜表面に白金金属層を
析出させた後、膜表面の少なくとも片方の面上に別の白
金族金属からなる金属層を成長させる電極膜接合体の製
造方法において、白金族金属からなる金属層の形成方法
を従来の無電解めっき法にかえ、電解めっき法を採用し
たことを特徴とする。The method for producing an electrode membrane assembly according to the present invention is characterized in that platinum ions are ion-exchanged and adsorbed on a cation exchange resin membrane, and then a platinum metal layer is deposited on the membrane surface using a reducing agent. In a method for manufacturing an electrode membrane assembly in which a metal layer made of another platinum group metal is grown on at least one surface of the film surface, the method of forming a metal layer made of a platinum group metal is changed to a conventional electroless plating method, It is characterized by employing an electrolytic plating method.
【０００９】[0009]
【発明の実施の形態】以下、本発明の実施の形態を説明
する。Embodiments of the present invention will be described below.
【００１０】本発明の電極膜接合体においては、カチオ
ン交換樹脂膜表面の両方の面を無電解めっきによって形
成された白金の金属層と該白金金属層上に電解めっきに
よって形成されたイリジウム又は白金−イリジウム合金
の金属層とからなる積層構造としてもよいが、実用上は
陽極側の面の金属層を無電解めっきによって形成された
白金の金属層と該白金金属層上に電解めっきによって形
成されたイリジウム又は白金−イリジウム合金の金属層
とからなるものとし、他方の面の金属層は無電解めっき
によって形成された白金の金属層からなるものとすれば
よい。In the electrode membrane assembly of the present invention, both surfaces of the cation exchange resin membrane surface are formed of a platinum metal layer formed by electroless plating, and iridium or platinum formed on the platinum metal layer by electrolytic plating. Although it may be a laminated structure composed of a metal layer of an iridium alloy, in practice, the metal layer on the anode side is formed by electroless plating on a platinum metal layer formed by electroless plating and the platinum metal layer. And a metal layer of iridium or a platinum-iridium alloy, and the metal layer on the other surface may be a metal layer of platinum formed by electroless plating.
【００１１】カチオン交換樹脂膜としてはスルホン酸基
またはカルボン酸基を有する過フッ化炭化水素樹脂膜、
例えばナフィオン膜（米国デュポン社の商品名）が用い
られる。本発明の電極膜接合体を製造するには、カチオ
ン交換樹脂膜、例えばナフィオン膜を用意し、２Ｎ−Ｈ
Ｃｌ中での煮沸と水での煮沸を行ってナフィオン膜をナ
トリウム型からプロトン型に変換する。ついで、この膜
を白金イオン供給源の白金錯塩溶液に浸漬する。こうし
て所望量の白金イオンを吸着させたカチオン交換樹脂膜
を水素化硼素塩水溶液をはじめとする還元剤含有液に浸
漬処理すると、樹脂膜表面付近で白金金属の析出が起こ
り、電解用白金電極膜接合体が形成出来る。還元剤とし
ては、水素化硼素塩、例えばナトリウムボロハイドライ
ドもしくはカリウムボロハイドライド等が好ましく用い
られる。As the cation exchange resin membrane, a fluorocarbon resin membrane having a sulfonic acid group or a carboxylic acid group,
For example, a Nafion membrane (trade name of DuPont, USA) is used. To manufacture the electrode membrane assembly of the present invention, a cation exchange resin membrane, for example, a Nafion membrane is prepared and 2N-H
The Nafion membrane is converted from sodium form to proton form by boiling in Cl and boiling in water. Next, this membrane is immersed in a platinum complex salt solution of a platinum ion supply source. When the cation exchange resin membrane adsorbing the desired amount of platinum ions is immersed in a reducing agent-containing liquid such as an aqueous borohydride solution, platinum metal is deposited near the resin film surface, and the platinum electrode membrane for electrolysis is used. A joined body can be formed. As the reducing agent, a borohydride salt such as sodium borohydride or potassium borohydride is preferably used.
【００１２】なお、白金錯塩溶液への浸漬に先立ち、膜
表面をサンドブラスト法や電子線エッチングにより粗化
することにより電解性能を著しく向上させることが可能
となる。膜表面を粗化してから白金を析出させると、適
度な粒子径と細孔を有する白金層が得られる結果、作動
面積の大きい触媒電極層をもたらす所となり、後工程で
イリジウム又は白金−イリジウム合金を電解めっきさせ
る際、膜内部までイリジウム又は白金−イリジウム合金
で被覆出来るからと考えられる。The electrolytic performance can be significantly improved by roughening the film surface by sandblasting or electron beam etching prior to immersion in the platinum complex salt solution. When platinum is deposited after roughening the membrane surface, a platinum layer having an appropriate particle size and pores is obtained, resulting in a catalyst electrode layer having a large working area, and iridium or a platinum-iridium alloy in a later step. It can be considered that when electrolytic plating is performed, the inside of the film can be coated with iridium or a platinum-iridium alloy.
【００１３】吸着によって消費された白金イオンを補充
するため、必要量の上記白金錯塩を適時供給することが
望ましい。イオン交換反応過程で、液中の白金濃度は0.
0001〜0.1mol/lとする事が望ましい。また、反応温度は
室温〜90℃の範囲で行う事が望ましい。室温以下では交
換反応の進行が遅く、90℃以上ではアンモニア等の蒸発
が起こりやすくなり、液濃度が変化しやすいからであ
る。To replenish the platinum ions consumed by the adsorption, it is desirable to supply a required amount of the above platinum complex salt in a timely manner. During the ion exchange reaction process, the platinum concentration in the solution was 0.
It is desirable to be 0001-0.1 mol / l. The reaction temperature is preferably in the range of room temperature to 90 ° C. If the temperature is lower than room temperature, the progress of the exchange reaction is slow, and if the temperature is higher than 90 ° C., evaporation of ammonia or the like is liable to occur, and the liquid concentration tends to change.
【００１４】続いて、上記の電極接合体上に電解めっき
によってイリジウムまたは白金−イリジウム合金の金属
層を成長させる。イリジウム電解めっき浴としては、例
えば、ヘキサブロモイリジウム酸ナトリウム、ホウ酸及
びシュウ酸ナトリウムとからなるものを用いることが出
来る。また、白金−イリジウム合金電解めっき浴として
は、前記のイリジウム電解めっき浴にテトラニトロ白金
酸ナトリウム等の白金化合物を加えたものを使用でき
る。Subsequently, a metal layer of iridium or a platinum-iridium alloy is grown on the electrode assembly by electrolytic plating. As the iridium electrolytic plating bath, for example, a bath composed of sodium hexabromoiridate, boric acid, and sodium oxalate can be used. Further, as the platinum-iridium alloy electroplating bath, a bath obtained by adding a platinum compound such as sodium tetranitroplatinate to the above-mentioned iridium electroplating bath can be used.
【００１５】[0015]
【実施例】次に、実施例をあげて本発明を具体的に説明
する。Next, the present invention will be described specifically with reference to examples.
【００１６】[0016]
【実施例１】カチオン交換樹脂膜ナフィオン 117（米国
デュポン社の商品名）の膜をサンドブラストにより表面
粗化した後、２Ｎ−ＨＣｌで30分煮沸し、ついで水洗後
さらに水で30分煮沸してからテトラアンミン白金ジハイ
ドロオキサイド水溶液（白金濃度0.05mol/l ）に浸漬
し、30℃で120 分間保持した。次にこの膜を水素化硼素
ナトリウム水溶液に浸漬し、室温から昇温し90℃で10分
間保持し無電解めっき反応をさせた。両面に白金が析出
したナフィオン膜（以下この膜を白金接合膜という。）
を水洗し、乾燥後重量測定から換算したところ白金膜の
厚さは約0.25μｍであった。該白金接合膜を、内部に給
電部を設けた樹脂製ホルダー（片面のみが液に接触す
る。）にはさみ込み、それをヘキサブロモイリジウム酸
ナトリウム（イリジウム濃度で１０ｇ／ｌ）、ホウ酸
４０ｇ／ｌ、シュウ酸ナトリウム ０．２ｍｏｌ／ｌか
らなるめっき浴中に浸漬し、ｐＨ５、85℃、電流密度
０．１５Ａ／ｄｍ2 で１８分間電解めっきを行い、電極
の片面に０．４５μｍ（イリジウム量で１ｍｇ／ｃ
ｍ2 ）のイリジウム層を形成させた。これを水洗した接
合膜を以後接合膜１という。Example 1 A cation exchange resin membrane Nafion 117 (trade name of DuPont, USA) was roughened by sandblasting, boiled with 2N-HCl for 30 minutes, washed with water and further boiled with water for 30 minutes. Was then immersed in an aqueous solution of tetraammineplatinum dihydroxide (platinum concentration 0.05 mol / l) and kept at 30 ° C. for 120 minutes. Next, the film was immersed in an aqueous solution of sodium borohydride, heated from room temperature and held at 90 ° C. for 10 minutes to cause an electroless plating reaction. Nafion film with platinum deposited on both sides (this film is hereinafter referred to as a platinum bonding film)
Was washed with water, dried and converted from weight measurement to find that the thickness of the platinum film was about 0.25 μm. The platinum bonding film is sandwiched between resin holders (only one side of which is in contact with the liquid) provided with a power supply unit therein, and the resultant is sandwiched between sodium hexabromoiridate (iridium concentration: 10 g / l) and boric acid.
It was immersed in a plating bath composed of 40 g / l and 0.2 mol / l of sodium oxalate, and electroplated at pH 5, 85 ° C. and a current density of 0.15 A / dm 2 for 18 minutes. 1 mg / c iridium
m 2 ) of an iridium layer was formed. The bonding film washed with water is hereinafter referred to as a bonding film 1.
【００１７】[0017]
【実施例２】専用の樹脂ホルダーを両面タイプにしたも
のを用いること以外は、実施例１と同様な手法にて、白
金接合膜の両面に０．４５μｍ（イリジウム量で１ｍｇ
／ｃｍ2 ）のイリジウム層を形成させた。これを水洗し
た接合膜を以後接合膜２という。Example 2 The same procedure as in Example 1 was repeated except that a dedicated resin holder having a double-sided resin holder was used, and 0.45 μm (1 mg in iridium amount) was applied to both sides of the platinum bonding film.
/ Cm 2 ) of an iridium layer. The bonding film washed with water is hereinafter referred to as a bonding film 2.
【００１８】[0018]
【実施例３】イリジウム電解めっき浴に市販品（ＥＥＪ
Ａ製イリデックス１００）を用いた事以外は、実施例１
と同様な手法にて、白金接合膜の両面に０．４５μｍ
（イリジウム量で１ｍｇ／ｃｍ2 ）のイリジウム層を形
成させた。これを水洗した接合膜を以後接合膜３とい
う。Example 3 A commercially available product (EEJ) was used for an iridium electrolytic plating bath.
Example 1 except that A-made Iridex 100) was used.
0.45 μm on both sides of the platinum bonding film
An iridium layer (1 mg / cm 2 in iridium amount) was formed. The bonding film washed with water is hereinafter referred to as a bonding film 3.
【００１９】[0019]
【実施例４】専用の樹脂ホルダーを両面タイプにしたも
のを用いること以外は、実施例３と同様な手法にて、白
金接合膜の両面に０．４５μｍ（イリジウム量で１ｍｇ
／ｃｍ2 ）のイリジウム層を形成させた。これを水洗し
た接合膜を以後接合膜４という。Example 4 The same procedure as in Example 3 was repeated except that a dedicated resin holder of a double-sided type was used, and 0.45 μm (1 mg in iridium amount) was applied to both sides of the platinum bonding film.
/ Cm 2 ) of an iridium layer. The bonding film washed with water is hereinafter referred to as a bonding film 4.
【００２０】[0020]
【実施例５】白金接合膜を、内部に給電部を設けた樹脂
製ホルダー（片面のみが液に接触する。）にはさみ込
み、それをヘキサブロモイリジウム酸ナトリウム（イリ
ジウム濃度で１０ｇ／ｌ）、テトラニトロ白金酸ナトリ
ウム（白金濃度で１．５ｇ／ｌ）、ホウ酸 ４０ｇ／
ｌ、シュウ酸ナトリウム ０．２ｍｏｌ／ｌからなるメ
ッキ浴中に浸漬し、ｐＨ５、85℃、電流密度０．１５Ａ
／ｄｍ2 で１８分間電解めっきを行い、電極の片面に
０．４５μｍ（白金とイリジウム量でそれぞれ０．５ｍ
ｇ／ｃｍ2 ）の白金−イリジウム合金層を形成させた。
これを水洗した接合膜を以後接合膜５という。Fifth Embodiment A platinum bonding film is sandwiched between resin holders (only one side of which is in contact with a liquid) provided with a power feeding portion therein, and sodium hexabromoiridate (10 g / l in iridium concentration) is inserted. Sodium tetranitroplatinate (1.5g / l platinum concentration), 40g boric acid /
l, immersion in a plating bath consisting of sodium oxalate 0.2 mol / l, pH 5, 85 ° C, current density 0.15 A
/ Dm 2 for 18 minutes, and 0.45 μm on one side of the electrode (0.5 m each for platinum and iridium)
g / cm 2 ) of a platinum-iridium alloy layer.
The bonding film washed with water is hereinafter referred to as a bonding film 5.
【００２１】[0021]
【従来例１】白金接合膜を、塩化イリジウム酸カリウム
（イリジウム濃度で０．５ｇ／ｌ）、５％ＮＨ2 ＯＨ・
ＨＣｌ ４０ｍｌ／ｌ、２０％Ｎ2 Ｈ4 ・Ｈ2 Ｏ １５
ｍｌ／ｌからなるイリジウム無電解めっき浴に浸漬し、
ｐＨ ７．２（調整剤苛性ソーダ）液温７０℃で４時間
かけて白金接合膜の両面にイリジウム無電解めっきを行
った。上記膜を水洗した後、乾燥し重量を確認したとこ
ろ、１ｍｇ／ｃｍ2 のイリジウムが析出していた。以降
この膜を比較膜１という。Conventional Example 1 A platinum bonding film was formed by using potassium iridate (0.5 g / l in iridium concentration), 5% NH 2 OH.
HCl 40 ml / l, 20% N 2 H 4 .H 2 O 15
immersion in an iridium electroless plating bath consisting of
Iridium electroless plating was performed on both surfaces of the platinum bonding film at a liquid temperature of 70 ° C. for 4 hours at a pH of 7.2 (adjusting agent caustic soda). After the above-mentioned film was washed with water and dried to check the weight, 1 mg / cm 2 of iridium was deposited. Hereinafter, this film is referred to as comparative film 1.
【００２２】[0022]
【従来例２】めっき前に白金接合膜の片面にマスクを施
し、めっきが付かないようにした事以外は、比較例１と
同様な手法にて、無電解めっきによるイリジウム層を形
成させた。上記膜を水洗した後、乾燥し重量を確認した
ところ、１ｍｇ／ｃｍ2 のイリジウムが析出していた。
以降この膜を比較膜２という。Conventional Example 2 An iridium layer was formed by electroless plating in the same manner as in Comparative Example 1, except that one side of the platinum bonding film was masked before plating to prevent plating. After the above-mentioned film was washed with water and dried to check the weight, 1 mg / cm 2 of iridium was deposited.
Hereinafter, this film is referred to as a comparative film 2.
【００２３】（評価）接合膜１と比較膜１を電解セルに
設置し、電解性能を測定した。（図１） 結果として、イリジウム又は白金−イリジウム合金から
なるイリジウム含有触媒層を付与した接合膜１は比較膜
１に比べ低い電解電圧を示し、高い性能を持つことがわ
かった。接合膜２〜５についても同様な測定を行った
が、接合膜１とほぼ同等の性能を持っていた。（接合膜
と比較膜間の性能差は、主に析出したイリジウムの表面
積＝イリジウム結晶粒の大きさに寄与するのではないか
と考えられる。）(Evaluation) The bonding film 1 and the comparative film 1 were placed in an electrolytic cell, and the electrolytic performance was measured. (FIG. 1) As a result, it was found that the bonding film 1 provided with the iridium-containing catalyst layer made of iridium or a platinum-iridium alloy showed a lower electrolysis voltage than the comparative film 1 and had high performance. The same measurement was performed for the bonding films 2 to 5, but the performance was almost the same as that of the bonding film 1. (It is considered that the performance difference between the bonding film and the comparative film mainly contributes to the surface area of iridium precipitated = the size of iridium crystal grains.)
【００２４】[0024]
【発明の効果】以上詳述した通り、 本発明による電極膜
接合体は、イリジウム含有触媒層を持たない白金接合膜
に比べ、過電圧が低く、無電解めっきによるイリジウム
含有触媒層を持つ膜に比べても、より高い性能（低い過
電圧）を示す。また、本発明による電極膜接合体の製造
方法によれば、イリジウムの電解反応が安定に行われる
ため、イリジウムの析出量の制御が容易となる。そのた
め、所望の部位のみにイリジウムを析出させることが可
能となる。更には、電解めっき液自体の寿命が長いた
め、めっき液中のイリジウム成分を有効利用できる上、
電解めっき反応は、反応速度が早いため、製造時間が短
くなり、結果的に量産性が増すという利点を有する。As described in detail above, the electrode membrane assembly according to the present invention has a lower overvoltage than a platinum bonding membrane having no iridium-containing catalyst layer, and has a lower overvoltage than a membrane having an iridium-containing catalyst layer formed by electroless plating. However, it shows higher performance (low overvoltage). Further, according to the method for producing an electrode membrane assembly according to the present invention, since the iridium electrolytic reaction is performed stably, the amount of iridium deposited can be easily controlled. Therefore, it becomes possible to deposit iridium only at a desired site. Furthermore, since the life of the electrolytic plating solution itself is long, the iridium component in the plating solution can be effectively used.
The electroplating reaction has an advantage that the reaction time is high, so that the production time is short, and as a result, mass productivity is increased.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成９年８月１１日[Submission date] August 11, 1997
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】図面の簡単な説明[Correction target item name] Brief description of drawings
【補正方法】追加[Correction method] Added
【補正内容】[Correction contents]
【図面の簡単な説明】[Brief description of the drawings]
【図１】本発明の実施例及び従来例について電解性能を
比較評価した図である。FIG. 1 is a diagram showing comparative evaluation of electrolytic performance of an example of the present invention and a conventional example.
Claims (8)
されてなる電極膜接合体において、樹脂膜表面の少なく
とも片方の面に白金の金属層とイリジウムまたは白金−
イリジウム合金の金属層が積層して形成されており、白
金の金属層は無電解めっきによって形成されたものであ
り、イリジウムまたは白金−イリジウム合金の金属層は
電解めっきによって形成されたものであることを特徴と
する電極膜接合体。An electrode membrane assembly comprising a cation exchange resin membrane having a metal layer formed on the surface thereof, wherein at least one surface of the resin membrane surface has a platinum metal layer and iridium or platinum-
The iridium alloy metal layer is formed by lamination, the platinum metal layer is formed by electroless plating, and the iridium or platinum-iridium alloy metal layer is formed by electrolytic plating. An electrode membrane assembly characterized by the above-mentioned.
されてなる電極膜接合体において、樹脂膜表面の片方の
面の金属層は無電解めっきによって形成された白金の金
属層と該白金金属層上に電解めっきによって形成された
イリジウムまたは白金−イリジウム合金の金属層とから
なり、他方の面の金属層は無電解めっきによって形成さ
れた白金の金属層からなることを特徴とする電極膜接合
体。2. In an electrode membrane assembly having a metal layer formed on the surface of a cation exchange resin film, the metal layer on one surface of the resin film surface is formed of a platinum metal layer formed by electroless plating and the platinum metal layer. Electrode film bonding characterized by comprising a metal layer of iridium or a platinum-iridium alloy formed on the layer by electrolytic plating, and a metal layer on the other surface comprising a metal layer of platinum formed by electroless plating. body.
たはカルボン酸基を有する過フッ化炭化水素樹脂膜であ
る請求項１または２に記載の電極膜接合体。3. The electrode membrane assembly according to claim 1, wherein the cation exchange resin membrane is a fluorocarbon resin membrane having a sulfonic acid group or a carboxylic acid group.
ン交換吸着させ、次いで還元剤を用いて該膜表面に白金
金属層を析出させた後、膜表面の少なくとも片方の面上
に別の白金族金属からなる金属層を成長させる電極膜接
合体の製造方法において、白金族金属からなる金属層を
電解めっきによって成長させることを特徴とする電極膜
接合体の製造方法。4. After ion-exchange adsorption of platinum ions on the cation exchange resin membrane, and then depositing a platinum metal layer on the membrane surface using a reducing agent, another platinum group is formed on at least one of the membrane surfaces. What is claimed is: 1. A method for manufacturing an electrode membrane assembly, comprising: growing a metal layer made of a platinum group metal by electrolytic plating.
る際に、事前にカチオン交換樹脂膜表面を粗化する事を
特徴とする請求項４に記載の電極膜接合体の製造方法。5. The method according to claim 4, wherein the surface of the cation exchange resin membrane is roughened before depositing the platinum metal layer by electroless plating.
イリジウム合金である請求項４または５に記載の電極膜
接合体の製造方法。6. The method according to claim 1, wherein the platinum group metal is iridium or platinum-.
The method for producing an electrode membrane assembly according to claim 4, wherein the method is an iridium alloy.
たはカルボン酸基を有する過フッ化炭化水素樹脂膜であ
る請求項４乃至６に記載の電極膜接合体の製造方法。7. The method for producing an electrode membrane assembly according to claim 4, wherein the cation exchange resin membrane is a fluorocarbon resin membrane having a sulfonic acid group or a carboxylic acid group.
解めっき液中のイリジウムイオンの供給源が、ヘキサブ
ロモイリジウム酸ナトリウムまたはヘキサクロロイリジ
ウム酸ナトリウムである請求項６乃至７に記載の電極膜
接合体の製造方法。8. The method for manufacturing an electrode membrane assembly according to claim 6, wherein the source of iridium ions in the iridium or platinum-iridium electrolytic plating solution is sodium hexabromoiridate or sodium hexachloroiridate. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9147394A JPH10330979A (en) | 1997-06-05 | 1997-06-05 | Electrode membrane assembly and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9147394A JPH10330979A (en) | 1997-06-05 | 1997-06-05 | Electrode membrane assembly and method of manufacturing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10330979A true JPH10330979A (en) | 1998-12-15 |
Family
ID=15429289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9147394A Pending JPH10330979A (en) | 1997-06-05 | 1997-06-05 | Electrode membrane assembly and method of manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10330979A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003221691A (en) * | 2002-01-31 | 2003-08-08 | Permelec Electrode Ltd | Electrolytic cathode and electrolytic cell using this |
| WO2004070865A1 (en) * | 2003-02-10 | 2004-08-19 | Matsushita Electric Industrial Co. Ltd. | Fuel cell system |
| JP2008041411A (en) * | 2006-08-04 | 2008-02-21 | Nissan Motor Co Ltd | Fuel cell electrode |
-
1997
- 1997-06-05 JP JP9147394A patent/JPH10330979A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003221691A (en) * | 2002-01-31 | 2003-08-08 | Permelec Electrode Ltd | Electrolytic cathode and electrolytic cell using this |
| WO2004070865A1 (en) * | 2003-02-10 | 2004-08-19 | Matsushita Electric Industrial Co. Ltd. | Fuel cell system |
| US8557456B2 (en) | 2003-02-10 | 2013-10-15 | Panasonic Corporation | Fuel cell system |
| JP2008041411A (en) * | 2006-08-04 | 2008-02-21 | Nissan Motor Co Ltd | Fuel cell electrode |
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