JP3049267B2 - Composition, electrode and assembly for polymer membrane fuel cell - Google Patents
Composition, electrode and assembly for polymer membrane fuel cellInfo
- Publication number
- JP3049267B2 JP3049267B2 JP5040220A JP4022093A JP3049267B2 JP 3049267 B2 JP3049267 B2 JP 3049267B2 JP 5040220 A JP5040220 A JP 5040220A JP 4022093 A JP4022093 A JP 4022093A JP 3049267 B2 JP3049267 B2 JP 3049267B2
- Authority
- JP
- Japan
- Prior art keywords
- fuel cell
- conductive porous
- cation exchange
- cation
- polymer membrane
- 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
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
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高分子膜型燃料電池用
の組成物、電極及び接合体に関する。これら組成物、電
極及び接合体は、一対の導電性多孔質層と、各導電性多
孔質層の表面に設けられた陽イオン交換樹脂よりなる高
分子電解質層と、各電解質層の表面側に接合された陽イ
オン交換樹脂などからなる固体高分子膜と、各電解質層
及び導電性多孔質層の境界に配置された触媒金属とを有
する高分子膜型燃料電池に用いられる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer membrane fuel cell.
Composition, an electrode and assembly. These compositions,
The pole and the joined body are composed of a pair of conductive porous layers and each conductive layer.
High cation exchange resin provided on the surface of the porous layer
A molecular electrolyte layer, a solid polymer membrane made of a cation exchange resin or the like bonded to the surface side of each electrolyte layer, and each electrolyte layer
And a catalytic metal disposed at the boundary of the conductive porous layer.
Used in the polymer membrane type fuel batteries for.
【０００２】[0002]
【従来の技術】従来、高分子膜型燃料電池に用いる電極
の製造方法として、例えばＵＳＰ４８７６１１５号公報
に記載された方法が知られている。この公報の方法で
は、触媒金属としての白金（粒径２０〜５０Å）を担持
したカーボン粒子の成形体を導電性多孔質層として採用
している。かかる白金担持カーボン成形体は、いわゆる
Ｐｒｏｔｏｔｅｃｈ法により得られ、Ｐｒｏｔｏｔｅｃ
ｈ社（Ｎｅｗｔｏｎ Ｈｉｇｈｌａｎｄｓ Ｍａｓｓａ
ｃｈｕｓｅｔｔｓ）より市販されている。2. Description of the Related Art Conventionally, a method described in US Pat. No. 4,876,115 has been known as a method for manufacturing an electrode used in a polymer membrane fuel cell. In the method of this publication, a formed body of carbon particles supporting platinum (particle diameter: 20 to 50 °) as a catalyst metal is employed as the conductive porous layer. Such a platinum-supported carbon molded body is obtained by a so-called Prototech method,
Company h (Newton Highlands Massa)
commercially available from C. Chutsts).
【０００３】[0003]
【発明が解決しようとする課題】触媒金属量は例えば高
分子膜型燃料電池の発電性能に影響を与えるが、製造コ
ストの低廉化のためには、高分子膜型燃料電池における
電極反応に必要な部位、すなわち導電性多孔質層と電解
質との境界のみに存在することが好ましい。しかし、上
記公報記載の方法では、成形体全体に触媒金属が担持さ
れており、電極反応に不必要な部位にまで触媒金属が存
在することから、高価な触媒金属の利用に無駄がある。The amount of catalytic metal affects, for example, the power generation performance of a polymer membrane fuel cell. However, in order to reduce the production cost, it is necessary for the electrode reaction in the polymer membrane fuel cell. Parts, that is, conductive porous layer and electrolysis
It is preferably present only at the boundary with quality . However, in the method described in the above publication, the catalyst metal is supported on the entire molded body, and the catalyst metal is present even in a portion unnecessary for the electrode reaction.
【０００４】また、白金担持カーボン成形体の厚みを極
めて薄くすることにより、触媒金属量を低減させた高分
子膜型燃料電池を製造せんとすれば、成形体の厚みを薄
くすることが困難であり、かつ成形体の機械的強度が確
保できないため、高分子膜型燃料電池を容易に製造する
ことができず、かつ耐久性が確保できない。本発明は、
発電性能に影響を与えることなく触媒金属を有効に利用
できる高分子膜型燃料電池用の組成物を提供し、もって
高分子膜型燃料電池を安価かつ容易に製造可能な高分子
膜型燃料電池用の電極及び接合体を提供することを目的
とする。[0004] Further, if a polymer membrane fuel cell with a reduced amount of catalyst metal is to be manufactured by making the thickness of the platinum-supported carbon compact extremely small, it is difficult to reduce the thickness of the compact. There, and the mechanical strength of the molded body can not be secured, it is impossible to easily produce a high molecular membrane fuel cell, and can not secure the durability. The present invention
Providing a composition for a polymer membrane fuel cell can be effectively used catalyst metal without affecting the power generation performance, with a polymer membrane-type fuel cell at low cost and easily manufacturable polymeric membrane fuel cell It is an object to provide an electrode and a joined body for use .
【０００５】[0005]
【課題を解決するための手段】本発明者らは、特公昭５
８−４７４７１号公報において電解用接合体を製造する
方法を提案している。この方法では、陽イオン交換膜に
白金族金属のイオンを室温ないし高温下でイオン交換吸
着せしめ、次いで還元剤溶液で処理し、陽イオン交換膜
の表面に金属層を析出させている。本発明者らは、上記
目的を解決すべく、この方法を応用しつつ、特に新しい
触媒担持方法の研究を鋭意重ねた結果、本発明を完成さ
せるに至ったものである。Means for Solving the Problems The present inventors have disclosed Japanese Patent Publication No.
Japanese Patent Application Publication No. 8-47471 proposes a method of manufacturing a joined body for electrolysis. In this method, platinum group metal ions are ion-exchanged and adsorbed on a cation exchange membrane at room temperature or high temperature, and then treated with a reducing agent solution to deposit a metal layer on the surface of the cation exchange membrane. The inventors of the present invention have applied the above-described method to solve the above-mentioned object, and have made intensive studies on a new method for supporting a catalyst. As a result, the present invention has been completed.
【０００６】すなわち、本発明の高分子膜型燃料電池用
の組成物は、一対の導電性多孔質層と、各該導電性多孔
質層の表面に設けられた陽イオン交換樹脂よりなる高分
子電解質層と、各該電解質層の表面側に接合された固体
高分子膜と、各該電解質層及び該導電性多孔質層の境界
に配置された触媒金属とを有する高分子膜型燃料電池を
製造するための組成物であって、 陽イオンの一部として
該触媒金属を含む陽イオンをもつ該陽イオン交換樹脂
と、該陽イオン交換樹脂を溶解した溶媒とからなること
を特徴とする。また、本発明の高分子膜型燃料電池用の
電極は、一対の導電性多孔質層と、各該導電性多孔質層
の表面に設けられた陽イオン交換樹脂よりなる高分子電
解質層と、各該電解質層の表面側に接合された固体高分
子膜と、各該電解質層及び該導電性多孔質層の境界に配
置された触媒金属とを有する高分子膜型燃料電池を製造
するための電極であって、 前記電極は、前記導電性多孔
質層と、該導電性多孔質層の表面に設けられた前記高分
子電解質層と、該電解質層及び該導電性多孔質層の境界
に配置された前記触媒金属とからなり、該触媒金属は、
陽イオンの一部として触媒金属を含む陽イオンをもつ前
記陽イオン交換樹脂と、該陽イオン交換樹脂を溶解した
溶媒とからなる高分子膜型燃料電池用の組成物を該導電
性多孔質層に付着させた後、該触媒金属を含む陽イオン
を還元して形成された該陽イオン交換樹脂の表面に表出
したものであることを特徴とする。さらに、本発明の高
分子膜型燃料電池用の接合体は、一対の導電性多孔質層
と、各該導電性多孔質層の表面に設けられた陽イオン交
換樹脂よりなる高分子電解質層と、各該電解質層の表面
側に接合された固体高分子膜と、各該電解質層及び該導
電性多孔質層の境界に配置された触媒金属とを有する高
分子膜型燃料電池を製造するための接合体であって、前
記接合体は、各前記導電性多孔質層と、各該導電性多孔
質層の表面に設けられた高分子電解質層と、各該電解質
層の表面側に接合された固体高分子膜と、各該電解質層
及び該導電性多孔質層の境界に配置された触媒金属とか
らなり、 該触媒金属は、陽イオンの一部として触媒金属
を含む陽イオンをもつ前記陽イオン交換樹脂と、該陽イ
オン交換樹脂を溶解した溶媒とからなる高分子膜型燃料
電池用の組成物を各該導電性多孔質層に付着させた後、
該触媒金属を含む陽イオンを還元して形成された該陽イ
オン交換樹脂の表面に表出したものであることを特徴と
する。 That is, the present inventionFor polymer membrane fuel cells
ofThe composition isA pair of conductive porous layers and each of the conductive porous layers;
Of cation exchange resin provided on the surface of the porous layer
Solid electrolyte layer and a solid body bonded to the surface side of each electrolyte layer
Boundary between the polymer membrane and each of the electrolyte layer and the conductive porous layer
Membrane Fuel Cell Having a Catalyst Metal Arranged in a CellTo
To manufacturePair ofAn adult, As part of the cation
The cation exchange resin having a cation containing the catalytic metal
And a solvent in which the cation exchange resin is dissolved
It is characterized by. Further, the polymer film type of the present inventionFor fuel cells
The electrodes areA pair of conductive porous layers and each of the conductive porous layers
Polymer composed of a cation exchange resin provided on the surface of
A dissolving layer and a solid electrolyte bonded to a surface side of each of the electrolyte layers.
At the boundary between the electrolyte membrane and each of the electrolyte layer and the conductive porous layer.
A polymer membrane fuel cell having a catalytic metal placed
An electrode for The electrode is the conductive porous
Layer, and the polymer layer provided on the surface of the conductive porous layer.
Electrolyte electrolyte layer, and boundary between the electrolyte layer and the conductive porous layer
And said catalyst metal disposed inThe catalyst metal is
Before having a cation containing a catalytic metal as part of the cation
The cation exchange resin and the cation exchange resin were dissolved
Consisting of solventFor polymer membrane fuel cellsCompositionTheConductive
Cation containing the catalytic metal after being attached to the porous layer
On the surface of the cation exchange resin formed by reducing
It is characterized by having been done.Furthermore, the present invention
The assembly for a molecular membrane fuel cell is composed of a pair of conductive porous layers.
And a cation exchange provided on the surface of each conductive porous layer.
Polymer electrolyte layers made of exchange resin and the surface of each electrolyte layer
A solid polymer membrane bonded to the electrolyte layer,
Having a catalytic metal disposed at the boundary of the conductive porous layer
A conjugate for manufacturing a molecular membrane fuel cell, comprising:
The joined body includes the conductive porous layers and the conductive porous layers.
Polymer electrolyte layer provided on the surface of the electrolyte layer, and each of the electrolytes
A solid polymer membrane bonded to the surface side of the layer and each of the electrolyte layers
And a catalytic metal disposed at the boundary of the conductive porous layer.
, The catalytic metal is a catalytic metal as part of a cation.
Said cation exchange resin having a cation comprising:
Polymer membrane fuel consisting of a solvent in which on-exchange resin is dissolved
After attaching a composition for a battery to each of the conductive porous layers,
The cation formed by reducing the cation containing the catalytic metal
Characterized by being exposed on the surface of the on-exchange resin
I do.
【０００７】本発明の高分子膜型燃料電池用の組成物、
電極及び接合体における陽イオン交換樹脂としては、例
えばフッ素系イオン交換樹脂では、一般式 A composition for a polymer membrane fuel cell according to the present invention ,
As the cation exchange resin in the electrode and the joined body , for example, a fluorine-based ion exchange resin has a general formula
【０００８】[0008]
【化１】 Embedded image
【０００９】のもの、具体的には、一般式において、ｍ
＝１，２，…、ｎ＝２で表される商品名：Ｎａｆｉｏｎ
（登録商標、Ｄｕ Ｐｏｎｔ社）、ｍ＝０，１、ｎ＝１
〜５で表される商品名：Ｆｌｅｍｉｏｎ（登録商標、旭
硝子社）、ｍ＝０，１、ｎ＝３〜５で表される商品名：
Ａｃｉｐｌｅｘ（登録商標、旭硝子社）、ｍ＝０、ｎ＝
２で表されるＤｏｗ Ｃｈｅｍｉｃａｌ社の陽イオン交
換樹脂を採用することができる。また、炭化水素系カチ
オン交換膜では、[0009] Specifically, in the general formula, m
, 1, 2,..., N = 2, product name: Nafion
(Registered trademark, Du Pont), m = 0,1, n = 1
Product names represented by ５-5: Flemion (registered trademark, Asahi Glass Co., Ltd.), product names represented by m = 0, 1, n = 3-5:
Aciplex (registered trademark, Asahi Glass Co., Ltd.), m = 0, n =
The cation exchange resin of Dow Chemical Co. represented by 2 can be employed. Further, in the hydrocarbon-based cation exchange membrane,
【００１０】[0010]
【化２】 Embedded image
【００１１】の商品名：ネオセプタ（登録商標、徳山曹
達社）や商品名：セレミオン（登録商標、旭硝子社）を
採用することができる。陽イオン交換樹脂は、イオン交
換基として一般式のようなスルホン酸基の他にカルボン
酸基をもつものがあるが、これらのうち、スルホン酸基
を有するものであることが好ましい。陽イオン交換樹脂
の陽イオンの一部が触媒金属を含む陽イオンと置換しや
すいことと、電気化学セルに用いた場合、低抵抗である
からである。The trade name: Neosepta (registered trademark, Tokuyama Soda Co., Ltd.) and the trade name: Selemion (registered trademark, Asahi Glass Co., Ltd.) can be adopted. Some cation exchange resins have a carboxylic acid group in addition to a sulfonic acid group as in the general formula as an ion exchange group, and among these, those having a sulfonic acid group are preferable. This is because a part of the cation of the cation exchange resin is easily replaced with a cation containing a catalyst metal, and when used in an electrochemical cell, the resistance is low.
【００１２】本発明の高分子膜型燃料電池用の組成物、
電極及び接合体における触媒金属としては、白金族元
素、すなわちルテニウムＲｕ、ロジウムＲｈ、パラジウ
ムＰｄ、オスニウムＯｓ、イリジウムＩｒ、白金Ｐｔを
採用することができる。触媒金属の陽イオンは、白金族
元素としてＰｔを採用するのであれば、 〔Ｐｔ（ＮＨ3 ）4 〕2+、 〔Ｐｔ（ＮＨ3 ）6 〕4+、 〔ＰｔＣｌ（ＮＨ3 ）5 〕3+ 等のアンミン錯イオン形態であることが好ましい。陽イ
オン交換樹脂の陽イオンの一部が触媒金属を含む陽イオ
ンと置換しやすいからである。 A composition for a polymer membrane fuel cell according to the present invention ,
As a catalytic metal in the electrode and the joined body , a platinum group element, that is, ruthenium Ru, rhodium Rh, palladium Pd, osmium Os, iridium Ir, platinum Pt can be used. As the cation of the catalyst metal, if Pt is adopted as a platinum group element, [Pt (NH 3 ) 4 ] 2+ , [Pt (NH 3 ) 6 ] 4+ , [PtCl (NH 3 ) 5 ] 3 It is preferably in the form of an ammine complex ion such as + . This is because a part of the cation of the cation exchange resin is easily replaced with a cation containing a catalyst metal.
【００１３】本発明の高分子膜型燃料電池用の電極及び
接合体における導電性多孔質層としては、カーボンブラ
ック粒子からなるカーボン成形体、撥水性を付与するＰ
ＴＦＥあるいは他のフッ素樹脂がバインダとされてカー
ボンブラック粒子を成形したカーボンテフロン混合成形
体を採用することができる。また、カーボンブラック粒
子の代わりに黒鉛等の他の炭素粉末やカーボンファイ
バ、貴金属粉末、Ｔｉ粉末などの金属微粒子を採用した
成形体も採用できる。 An electrode for a polymer membrane fuel cell according to the present invention, and
As the conductive porous layer in the joined body, a carbon molded body composed of carbon black particles, P for imparting water repellency is used.
It is possible to employ a carbon-Teflon-mixed molded product in which TFE or another fluororesin is used as a binder to form carbon black particles. Further, instead of carbon black particles, a molded product using other carbon powder such as graphite, or metal fine particles such as carbon fiber, noble metal powder, or Ti powder can also be used.
【００１４】[0014]
【作用】本発明の高分子膜型燃料電池用の組成物では、
陽イオン交換樹脂の陽イオンの一部として触媒金属の陽
イオンが含まれている。この組成物を導電性多孔質層に
付着させた後、触媒金属を含む陽イオンを還元させれ
ば、陽イオン交換樹脂の表面に微細な触媒金属の粒子が
均一に析出する。このため、本発明の高分子膜型燃料電
池用の電極及び接合体において、本発明の高分子膜型燃
料電池用の組成物を導電性多孔質層に付着させる量、陽
イオン交換樹脂において触媒金属の陽イオン含有量、あ
るいは組成物の濃度を制御すれば、陽イオン交換樹脂の
表面に表出する触媒金属量が制御される。このため、電
極反応に必要な部位、すなわち導電性多孔質層と電解質
との境界のみに触媒金属を必要な量だけ析出せしめるこ
とができる。According to the composition for a polymer membrane fuel cell of the present invention,
As a part of the cation of the cation exchange resin, the cation of the catalyst metal is contained. After depositing the this set Narubutsu the conductive porous layer, if reduced cations containing the catalyst metal particles of fine catalyst metal on the surface of the cation exchange resin is uniformly deposited. Therefore, the polymer membrane fuel cell of the present invention
In the electrode and the assembly for the pond, the polymer film type fuel of the present invention is used.
The amount of adhering a composition for charge battery conductive porous layer, the cation content of the catalyst metal in the cation exchange resin, Oh <br/> Rui by controlling the concentration of pairs Narubutsu, cation exchange The amount of catalytic metal exposed on the surface of the resin is controlled. Therefore, site necessary for the electrode reaction, i.e. the conductive porous layer and the electrolyte
It can be allowed to deposit the necessary amount of catalyst metal only at the boundary between.
【００１５】このため、高分子膜型燃料電池を安価かつ
容易に製造することができ、かつ耐久性も確保される。[0015] Therefore, a high molecular membrane fuel cell can be inexpensively and easily manufactured, and durability is ensured.
【００１６】[0016]
【実施例】以下、本発明を具体化した実施例を比較例と
ともに図面を参照しつつ説明する。 ｛実施例｝ １．高分子膜型燃料電池用の組成物の作成 商品名：Ｎａｆｉｏｎ（登録商標、Ｄｕ Ｐｏｎｔ社）
を陽イオン交換樹脂として採用し、この陽イオン交換樹
脂をイソプロパノール：９０重量％及び水：１０重量％
の有機溶媒に溶解させた５重量％の溶液を、室温で放置
することにより乾燥し、固体状の溶質を得る。なお、乾
燥は室温〜１１０℃以下の温度で放置又は加熱すること
により行なうことができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments embodying the present invention will be described below with reference to the drawings together with comparative examples. << Example >> 1. Preparation of composition for polymer membrane fuel cell Product name: Nafion (registered trademark, Du Pont)
Is used as a cation exchange resin. The cation exchange resin is composed of 90% by weight of isopropanol and 10% by weight of water.
A 5 wt% solution in an organic solvent is dried at room temperature to obtain a solid solute. The drying can be performed by leaving or heating at a temperature of room temperature to 110 ° C. or lower.
【００１７】この溶質を〔Ｐｔ（ＮＨ3 ）4 〕2+Ｃｌ2
・Ｈ2 Ｏを含む水溶液に浸漬し、陽イオン交換樹脂の陽
イオンの一部を白金の陽イオンと置換せしめる。これに
アルコールあるいは水との混合液を添加して溶解し、陽
イオン交換樹脂が数％〜数１０％含まれる溶液を得る。
こうして、陽イオンの一部としてＰｔを含む陽イオンを
もつ陽イオン交換樹脂と、この陽イオン交換樹脂を溶解
したアルコール及び水とからなる高分子膜型燃料電池用
の組成物を得る。This solute is converted to [Pt (NH 3 ) 4 ] 2+ Cl 2
Dipping in an aqueous solution containing H 2 O to replace a part of the cation of the cation exchange resin with the cation of platinum; A mixed solution with alcohol or water is added and dissolved to obtain a solution containing several to several tens of percent of the cation exchange resin.
Thus, a polymer membrane fuel cell comprising a cation exchange resin having a cation containing Pt as a part of the cation, and alcohol and water in which the cation exchange resin is dissolved .
To obtain a composition.
【００１８】２．高分子膜型燃料電池用の電極の製造 図１に示すように、カーボンテフロン混合成形体（Φ３
６．５ｍｍ、厚み０．１ｍｍ、気孔率６０％）１を導電
性多孔質層として用意する。この成形体１は、カーボン
ブラック粒子１１と、カーボンブラック粒子１１を結合
させ、同時に成形体１に撥水性を付与するＰＴＦＥ粒子
１２とからなる。図２に示すように、不活性ガス中にお
いて、この成形体１の表面に高分子膜型燃料電池用の組
成物２を０．３２ｍｌ／１０ｃｍ2 塗布する。組成物２
を塗布した成形体１を真空乾燥機内に保持し、７０℃で
２時間程度乾燥させる。これにより、組成物２のアルコ
ール及び水を除去し、Ｐｔの陽イオンをもつ陽イオン交
換樹脂からなる高分子電解質層２２を形成する。2. 1. Production of Electrode for Polymer Membrane Fuel Cell As shown in FIG.
(6.5 mm, thickness 0.1 mm, porosity 60%) 1 is prepared as a conductive porous layer. The molded body 1 is composed of carbon black particles 11 and PTFE particles 12 that bind the carbon black particles 11 and simultaneously impart water repellency to the molded body 1 . As shown in FIG. 2, a composition 2 for a polymer membrane fuel cell is applied to the surface of the molded body 1 in an inert gas at 0.32 ml / 10 cm 2 . Set Narubutsu 2
Is held in a vacuum dryer and dried at 70 ° C. for about 2 hours. Thus, to remove the alcohol and water combination Narubutsu 2, to form the polymer electrolyte layer 22 made of a cation exchange resin having a cation of Pt.
【００１９】高分子電解質層２２が形成された成形体１
を１４５℃、４〜５時間の条件で水素ガスにより還元処
理する。これにより、図３に示すように、高分子膜型燃
料電池用の電極１が得られる。この電極１では高分子電
解質層２２の表面に微細なＰｔ粒子２１が均一に析出す
る。こうして、高分子膜型燃料電池用の組成物２の塗布
量を制御することにより、高分子電解質層２２における
Ｐｔの陽イオン量を０．０５〜０．５ｍｇ／ｃｍ2 の範
囲で一定に制御可能である。The molded article 1 on which the polymer electrolyte layer 22 is formed
Is reduced with hydrogen gas at 145 ° C. for 4 to 5 hours. Thus, as shown in FIG. 3, the polymer film type fuel
An electrode 1 for a fuel cell is obtained. This electrode 1 has a polymer electrode
Fine Pt particles 21 are uniformly deposited on the surface of the decomposition layer 22. In this way, by controlling the coating amount of the composition 2 for a polymer membrane fuel cell, the amount of Pt cations in the polymer electrolyte layer 22 is controlled to be constant in the range of 0.05 to 0.5 mg / cm 2. It is possible.
【００２０】図４に示すように、固体高分子膜たる陽イ
オン交換膜（縦６０ｍｍ、横６０ｍｍ）３として商品
名：Ｎａｆｉｏｎ（登録商標、Ｄｕ Ｐｏｎｔ社）を用
意するとともに、一対の電極基材４１、４２としてＰＴ
ＦＥにより撥水性が付与されたカーボンファイバー集電
体（厚み０．３ｍｍ）を用意する。また、前記還元処理
した一対の高分子膜型燃料電池用の電極１を用意する。As shown in FIG. 4, Nafion (registered trademark, Du Pont) (trade name) is prepared as a cation exchange membrane (length 60 mm, width 60 mm) 3 as a solid polymer membrane , and a pair of electrode base materials is prepared. PT as 41 and 42
A carbon fiber current collector (thickness 0.3 mm) to which water repellency has been imparted by FE is prepared. Further, a pair of electrodes 1 for a polymer membrane fuel cell which has been subjected to the reduction treatment is prepared.
【００２１】固体高分子膜３側にＰｔ２１が対面するよ
うに還元処理した一対の高分子膜型燃料電池用の電極１
を挟持し、さらにこれらの外側に電極基材４１、４２を
挟持する。これらをホットプレスとして、１００℃に加
熱後、１４０℃の下、８０ｋｇ／ｃｍ2 で９０秒間保持
する。この後、Φ６０ｍｍに切断し、高分子膜型燃料電
池用の接合体５を得る。この高分子膜型燃料電池用の接
合体５は、高分子膜型燃料電池用の電極１において高分
子電解質層２２の存在しない部分である一対の導電性多
孔質層５２と、各導電性多孔質層５２の表面に設けられ
た高分子電解質層２２と、各高分子電解質層２２の表面
側に接合された固体高分子膜３と、各高分子電解質層２
２及び導電性多孔質層５２の境界に配置されたＰｔ２１
とを有する。ここで、各高分子電解質層２２及び固体高
分子膜３が電解質５１を構成している。こうして、この
高分子膜型燃料電池用の接合体５では、電極反応に必要
な部位、すなわち電解質５１の高分子電解質層２２及び
導電性多孔質層５２の境界のみにＰｔ２１を必要な量だ
け析出せしめられている。A pair of electrodes 1 for a polymer membrane fuel cell which have been reduced so that Pt 21 faces the solid polymer membrane 3 side.
, And the electrode base materials 41 and 42 are further sandwiched between them. These are hot-pressed, heated to 100 ° C., and kept at 140 ° C. and 80 kg / cm 2 for 90 seconds. After that, it is cut into Φ60mm and the polymer membrane fuel cell
A joint 5 for the pond is obtained. The connection for this polymer membrane fuel cell
The coalescing 5 has a high density in the electrode 1 for the polymer membrane fuel cell.
Pair of conductive multi-layers where the secondary electrolyte layer 22 does not exist.
A porous layer 52 provided on the surface of each conductive porous layer 52;
Polymer electrolyte layers 22 and the surface of each polymer electrolyte layer 22
Solid polymer membrane 3 joined to each side and each polymer electrolyte layer 2
2 and Pt21 disposed at the boundary of the conductive porous layer 52
With the door. Here, each polymer electrolyte layer 22 and the solid height
The molecular film 3 constitutes the electrolyte 51. Thus, in the polymer membrane fuel cell assembly 5, Pt 21 is applied only to the portion necessary for the electrode reaction, that is, only to the boundary between the polymer electrolyte layer 22 of the electrolyte 51 and the conductive porous layer 52. The required amount is deposited.
【００２２】３．燃料電池の製造 図５に示すように、この高分子膜型燃料電池用の接合体
５を電極基材４１、４２側が開口した供給管６１、６２
間に挟持し、一方の供給管６１からは水蒸気と空気とを
供給し、他方の供給管６２からは水蒸気と水素とを供給
させる。こうして、単セル（１枚の高分子膜型燃料電池
用の接合体５）型の燃料電池とする。3. 5. Production of Fuel Cell As shown in FIG. 5, the assembly 5 for a polymer membrane fuel cell is supplied with supply pipes 61 and 62 having electrode bases 41 and 42 open.
The steam is supplied between one supply pipe 61 to supply steam and air, and the other supply pipe 62 is supplied to supply steam and hydrogen. Thus, a single cell (one polymer membrane fuel cell)
The fuel cell assembly 5) type of use.
【００２３】この燃料電池においても、従来の高分子膜
型燃料電池と同様、供給管６２から供給される水素が導
電性多孔質層５２で細孔内拡散し、細孔をもつ電解質５
１である高分子電解質層２２においてＰｔ２１を触媒と
し、電解質５１である固体高分子膜３に存在する供給管
６１から供給された空気中の酸素と反応する。生成した
水は導電性多孔質層５２で細孔内拡散し、供給管６１、
６２に循環する。同時に、電子のやりとりが電極基材４
１、４２で行われるため、発電が行われる。 ｛比較例｝ 比較例として、従来の電極接合体による単セル型の燃料
電池を製造する。In this fuel cell, as in the case of the conventional polymer membrane fuel cell, hydrogen supplied from the supply pipe 62 is diffused in the pores in the conductive porous layer 52, and the electrolyte 5 having pores is formed.
In the polymer electrolyte layer 22 is 1 the Pt21 as a catalyst, reacts with oxygen in the air supplied from the supply pipe 61 present in the solid polymer membrane 3 is an electrolyte 5 1. The generated water diffuses in the pores in the conductive porous layer 52, and the supply pipe 61,
Recirculate to 62. At the same time, the exchange of electrons
Since power generation is performed at steps 1 and 42, power generation is performed. << Comparative Example >> As a comparative example, a single-cell fuel cell using a conventional electrode assembly is manufactured.
【００２４】まず、実施例と同種のカーボンテフロン混
合成形体７１を用意する。そして、塩化白金酸１ｇをエ
タノール１０ｍｌに溶解させ、かかる溶液に成形体７１
を浸漬し、４ｍｇ／ｃｍ2 のＰｔ担持量になるように、
成形体７１に溶液を１．２ｍｌ／１０ｃｍ2 含浸させ
る。溶液を含浸させた成形体７１を１５０℃〜２００
℃、３０〜６０秒間保持し、エタノールを消失させて乾
燥する。これを実施例と同様に還元する。こうして、Ｐ
ｔ２１が担持された一対の成形体７１を得る。なお、カ
ーボンブラック粒子及びＰＴＦＥ粒子は実施例と同一符
号を付す。First, a carbon teflon mixed molded body 71 of the same type as that of the embodiment is prepared. Then, 1 g of chloroplatinic acid is dissolved in 10 ml of ethanol, and the molded body 71 is added to the solution.
And soaked that the Pt carrying amount was 4 mg / cm 2 ,
The molded body 71 is impregnated with the solution at 1.2 ml / 10 cm 2 . The molded body 71 impregnated with the solution is heated at 150 ° C to 200 ° C.
C. for 30 to 60 seconds, and dry by removing ethanol. This is reduced as in the example. Thus, P
A pair of compacts 71 carrying t21 is obtained. The carbon black particles and the PTFE particles are denoted by the same reference numerals as in the examples.
【００２５】商品名：Ｎａｆｉｏｎ（登録商標、Ｄｕ
Ｐｏｎｔ社）を陽イオン交換樹脂として採用し、この陽
イオン交換樹脂をイソプロパノール：９０重量％及び
水：１０重量％の有機溶媒に溶解させ、５重量％の溶液
を得る。還元処理した成形体７１にこの溶液を０．３２
ｍｌ／１０ｃｍ2 塗布し、実施例と同様に乾燥させる。
こうして、Ｐｔ２１が担持されているとともに、高分子
電解質層２２が形成された一対の成形体７１を得る。Trade name: Nafion (registered trademark, Du)
Pont) is used as a cation exchange resin, and the cation exchange resin is dissolved in an organic solvent of 90% by weight of isopropanol and 10% by weight of water to obtain a solution of 5% by weight. This solution was added to the reduced molded body 71 by 0.32%.
ml / 10 cm 2 and dried as in the examples.
Thus, Pt21 is supported and the polymer
A pair of formed bodies 71 on which the electrolyte layer 22 is formed are obtained.
【００２６】また、実施例と同種の固体高分子膜３と、
電極基材４１、４２とを用意する。また、上記Ｐｔ２１
が担持され、かつ高分子電解質層２２が形成された一対
の成形体７１を用意する。図６に示すように、固体高分
子膜３側にＰｔ２１が対面するように一対の成形体７１
を挟持し、これらの外側に電極基材４１、４２を挟持す
る。これらを実施例と同様にホットプレスし、高分子膜
型燃料電池用の接合体８を得る。この高分子膜型燃料電
池用の接合体８により実施例と同様に単セル型の燃料電
池とする。 ｛評価｝ 実施例及び比較例における燃料電池での発電性能を評価
すべく、電極基材４１、４２にリード線を接合して電圧
計を取り付ける。電流密度（Ａ／ｃｍ2 ）と電位（Ｖ）
との関係を図７に示す。Further, the same kind of solid polymer membrane 3 as in the embodiment,
The electrode base materials 41 and 42 are prepared. In addition, the above Pt21
Are prepared, and a pair of molded bodies 71 on which the polymer electrolyte layer 22 is formed are prepared. As shown in FIG. 6, solid high content
A pair of compacts 71 is formed so that Pt21 faces the secondary membrane 3 side.
, And the electrode base materials 41 and 42 are sandwiched between them. These are hot-pressed in the same manner as in the example to obtain a joined body 8 for a polymer membrane fuel cell . This polymer membrane fuel cell
A single-cell fuel cell is formed by using the pond junction 8 as in the embodiment. << Evaluation >> In order to evaluate the power generation performance of the fuel cells in Examples and Comparative Examples, a lead wire is joined to the electrode substrates 41 and 42 and a voltmeter is attached. Current density (A / cm 2 ) and potential (V)
Is shown in FIG.
【００２７】図７より、実施例の燃料電池では、比較例
のものと比較してＰｔ担持量が大幅に低減しているにも
かかわらず、発電性能は従来品と同等あるいはそれ以上
であることがわかる。なお、上記実施例では、水素還元
方法により触媒金属の還元を行ったが、電気化学的還元
法も採用することができる。例えば、まず成形体１に高
分子膜型燃料電池用の組成物２を塗布し、この成形体１
を同様に乾燥した後、水素還元を施さないで同様に高分
子膜型燃料電池用の接合体５を作製する。この後、１．
５〜２．０Ｖの電圧を印加すると、陰極側で電気化学的
に還元が起こる。この処理後、燃料電池に適用する。ま
た、ＮａＢＨ4 等の還元剤を使用する還元法も採用する
ことができる。FIG. 7 shows that the fuel cell of the embodiment has a power generation performance equal to or higher than that of the conventional fuel cell despite the fact that the amount of Pt carried is significantly reduced as compared with that of the comparative fuel cell. I understand. In the above embodiment, the catalytic metal is reduced by the hydrogen reduction method, but an electrochemical reduction method can also be employed. For example, first, high in the molded body 1
The composition 2 for a molecular membrane fuel cell is applied,
Is dried in the same manner, and a joint 5 for a polymer membrane fuel cell is similarly produced without hydrogen reduction. After this, 1.
When a voltage of 5 to 2.0 V is applied, electrochemical reduction occurs on the cathode side. After this processing, it is applied to a fuel cell. Further, a reduction method using a reducing agent such as NaBH 4 can also be adopted.
【００２８】[0028]
【発明の効果】以上詳述したように、本発明の高分子膜
型燃料電池用の組成物は、陽イオン交換樹脂が触媒金属
の陽イオンをもつため、これが電極反応が起こる場所に
還元析出される。このため、発電性能に影響を与えるこ
となく触媒金属を有効に利用できる。また、本発明の高
分子膜型燃料電池用の電極及び接合体は、高分子膜型燃
料電池用の組成物を導電性多孔質層に付着させる量を制
御することにより、高価な白金触媒量を最小にすること
ができるので、高分子膜型燃料電池を安価かつ容易に製
造できる。As described in detail above, the polymer film of the present invention
In the composition for a fuel cell , since the cation exchange resin has a cation of a catalyst metal, the cation exchange resin is reduced and deposited at a place where an electrode reaction occurs. Therefore, the catalytic metal can be effectively used without affecting the power generation performance. The electrode and assembly for polymeric membrane fuel cell of the present invention, the polymer membrane type fuel
Charge composition for a battery by controlling the amount of adhering to the conductive porous layer, it is possible to minimize the expensive platinum catalyst amount, low cost and easily produced polymer membrane fuel cell.
【図１】実施例の高分子膜型燃料電池用の電極に係る成
形体の模式拡大断面図である。FIG. 1 is a schematic enlarged sectional view of a molded article according to an electrode for a polymer membrane fuel cell of an example.
【図２】実施例の高分子膜型燃料電池用の電極に係る成
形体に高分子膜型燃料電池用の組成物を塗布した状態を
示す模式拡大断面図である。FIG. 2 is a schematic enlarged cross-sectional view showing a state in which a composition for a polymer membrane fuel cell is applied to a molded article according to an electrode for a polymer membrane fuel cell of an example.
【図３】実施例の高分子膜型燃料電池用の電極に係る成
形体を還元処理した状態を示す模式拡大断面図である。FIG. 3 is a schematic enlarged cross-sectional view showing a state in which a molded product relating to an electrode for a polymer membrane fuel cell of an example has been subjected to a reduction treatment.
【図４】実施例の高分子膜型燃料電池用の接合体の模式
断面図である。FIG. 4 is a schematic cross-sectional view of an assembly for a polymer membrane fuel cell according to an example.
【図５】実施例の高分子膜型燃料電池用の接合体を用い
た燃料電池の構成図である。FIG. 5 is a configuration diagram of a fuel cell using a joined body for a polymer membrane fuel cell according to an example.
【図６】比較例の高分子膜型燃料電池用の接合体の模式
断面図である。FIG. 6 is a schematic sectional view of a joined body for a polymer membrane fuel cell of a comparative example.
【図７】実施例と比較例との燃料電池の特性を示すグラ
フである。FIG. 7 is a graph showing characteristics of fuel cells of an example and a comparative example.
１…成形体、導電性多孔質層、高分子膜型燃料電池用の
電極 ２…高分子膜型燃料電池用の組成物 ２２…高分子電解質層 ３…固体高分子膜 ５１…電解質 ５２…導電性多孔質層 ２１…Ｐｔ（触媒金属） ５…高分子膜型燃料電池用の接合体 1: molded article , conductive porous layer, polymer membrane fuel cell
Electrode 2: Composition for polymer membrane fuel cell 22 ... Polymer electrolyte layer 3 ... Solid polymer membrane 51 ... Electrolyte 52 ... Conductive porous layer 21 ... Pt (catalytic metal) 5 ... Polymer membrane fuel cell Joint for
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平６−44984（ＪＰ，Ａ) 特公 昭58−47471（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/86 - 4/98 H01M 8/00 - 8/24 C25B 9/00 - 13/08 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-44984 (JP, A) JP-B-58-47471 (JP, B2) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 4/86-4/98 H01M 8/00-8/24 C25B 9/00-13/08
Claims (9)
質層の表面に設けられた陽イオン交換樹脂よりなる高分
子電解質層と、各該電解質層の表面側に接合された固体
高分子膜と、各該電解質層及び該導電性多孔質層の境界
に配置された触媒金属とを有する高分子膜型燃料電池を
製造するための組成物であって、 陽イオンの一部として該触媒金属を含む陽イオンをもつ
該陽イオン交換樹脂と、該陽イオン交換樹脂を溶解した
溶媒とからなることを特徴とする高分子膜型燃料電池用
の組成物。(1)A pair of conductive porous layers and each of the conductive porous layers;
Of cation exchange resin provided on the surface of the porous layer
Solid electrolyte layer and a solid body bonded to the surface side of each electrolyte layer
Boundary between the polymer membrane and each of the electrolyte layer and the conductive porous layer
Membrane Fuel Cell Having a Catalyst Metal Arranged in a CellTo
To manufacturePair ofAn adult, Having a cation containing the catalytic metal as part of the cation
The cation exchange resin and the cation exchange resin were dissolved
Characterized by comprising a solventFor polymer membrane fuel cells
ofComposition.
ことを特徴とする請求項１記載の高分子膜型燃料電池用
の組成物。2. The polymer membrane fuel cell according to claim 1, wherein the cation exchange resin has a sulfonic acid group .
Of the composition.
態であることを特徴とする請求項１又は２記載の高分子
膜型燃料電池用の組成物。3. The polymer according to claim 1, wherein the cation of the catalyst metal is in the form of an ammine complex ion.
A composition for a membrane fuel cell .
質層の表面に設けられた陽イオン交換樹脂よりなる高分
子電解質層と、各該電解質層の表面側に接合された固体
高分子膜と、各該電解質層及び該導電性多孔質層の境界
に配置された触媒金属とを有する高分子膜型燃料電池を
製造するための電極であって、 前記電極は、前記導電性多孔質層と、該導電性多孔質層
の表面に設けられた前記高分子電解質層と、該電解質層
及び該導電性多孔質層の境界に配置された前記触媒金属
とからなり、 該 触媒金属は、陽イオンの一部として触媒金属を含む陽
イオンをもつ前記陽イオン交換樹脂と、該陽イオン交換
樹脂を溶解した溶媒とからなる高分子膜型燃料電池用の
組成物を該導電性多孔質層に付着させた後、該触媒金属
を含む陽イオンを還元して形成された該陽イオン交換樹
脂の表面に表出したものであることを特徴とする高分子
膜型燃料電池用の電極。4. A pair of conductive porous layers and each of said conductive porous layers
Of cation exchange resin provided on the surface of the porous layer
Solid electrolyte layer and a solid body bonded to the surface side of each electrolyte layer
Boundary between the polymer membrane and each of the electrolyte layer and the conductive porous layer
Polymer fuel cell having a catalyst metal disposed in
An electrode for manufacturing, wherein the electrode comprises: the conductive porous layer; and the conductive porous layer.
The polymer electrolyte layer provided on the surface of the, the electrolyte layer
And the catalyst metal disposed at the boundary of the conductive porous layer
Consists of a, the catalyst metal, said cation exchange resin having a cation comprising the catalyst metal as part of the cation, for polymer membrane fuel cell comprising a solvent having dissolved therein cation exchange resin characterized in that the <br/> composition after being attached to the conductive porous layer is obtained by presented on the surface of the cation exchange resin formed by reducing cations containing the catalytic metal For a polymer membrane fuel cell .
ことを特徴とする請求項４記載の高分子膜型燃料電池用
の電極。5. The polymer membrane fuel cell according to claim 4, wherein the cation exchange resin has a sulfonic acid group .
Electrode of.
態であることを特徴とする請求項４又は５記載の高分子
膜型燃料電池用の電極。6. The electrode for a polymer membrane fuel cell according to claim 4, wherein the cation of the catalyst metal is in the form of an ammine complex ion.
質層の表面に設けられProvided on the surface of the た陽イオン交換樹脂よりなる高分High cation exchange resin
子電解質層と、各該電解質層の表面側に接合された固体Solid electrolyte layer and a solid body bonded to the surface side of each electrolyte layer
高分子膜と、各該電解質層及び該導電性多孔質層の境界Boundary between the polymer membrane and each of the electrolyte layer and the conductive porous layer
に配置された触媒金属とを有する高分子膜型燃料電池をPolymer fuel cell having a catalyst metal disposed in
製造するための接合体であって、A joined body for manufacturing, 前記接合体は、各前記導電性多孔質層と、各該導電性多The joined body includes each of the conductive porous layers and each of the conductive layers.
孔質層の表面に設けられた高分子電解質層と、各該電解A polymer electrolyte layer provided on the surface of the porous layer;
質層の表面側に接合された固体高分子膜と、各該電解質Solid polymer membrane bonded to the surface side of the electrolyte layer,
層及び該導電性多孔質層の境界に配置された触媒金属とLayer and a catalytic metal disposed at a boundary of the conductive porous layer.
からなり、Consisting of 該触媒金属は、陽イオンの一部として触媒金属を含む陽The catalyst metal comprises a catalyst containing the catalyst metal as part of the cation.
イオンをもつ前記陽イオン交換樹脂と、該陽イオン交換The cation exchange resin having ions, and the cation exchange
樹脂を溶解した溶媒とからなる高分子膜型燃料電池用のFor polymer membrane fuel cells comprising a solvent in which a resin is dissolved
組成物を各該導電性多孔質層に付着させた後、該触媒金After adhering the composition to each of the conductive porous layers, the catalyst gold
属を含む陽イオンを還元して形成された該陽イオン交換Cation exchange formed by reducing a cation containing a genus
樹脂の表面に表出したものであることを特徴とする高分Characterized by being exposed on the surface of resin
子膜型燃料電池用の接合体。An assembly for a membrane fuel cell.
ことを特徴とする請求項７記載の高分子膜型燃料電池用The polymer membrane fuel cell according to claim 7, characterized in that:
の接合体。Conjugate.
態であることを特徴とする請求項７又は８記載の高分子9. The polymer according to claim 7, wherein the polymer is in a state.
膜型燃料電池用の接合体。Assembly for membrane fuel cells.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5040220A JP3049267B2 (en) | 1993-03-01 | 1993-03-01 | Composition, electrode and assembly for polymer membrane fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5040220A JP3049267B2 (en) | 1993-03-01 | 1993-03-01 | Composition, electrode and assembly for polymer membrane fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06260170A JPH06260170A (en) | 1994-09-16 |
| JP3049267B2 true JP3049267B2 (en) | 2000-06-05 |
Family
ID=12574687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5040220A Expired - Lifetime JP3049267B2 (en) | 1993-03-01 | 1993-03-01 | Composition, electrode and assembly for polymer membrane fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3049267B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69829933T2 (en) | 1997-11-25 | 2005-09-29 | Japan Storage Battery Co. Ltd., Kyoto | Electrode made of solid polymer electrolyte catalyst Composites, electrode for fuel cells and method for producing these electrodes |
| CN1288779C (en) | 2000-07-03 | 2006-12-06 | 松下电器产业株式会社 | Polyelectrolyte fuel cell |
| JP3587199B2 (en) * | 2002-05-29 | 2004-11-10 | 日本電気株式会社 | Fuel cell catalyst-carrying particles, composite electrolytes using the same, catalyst electrodes, fuel cells, and methods for producing them |
| CN102598377B (en) * | 2010-01-07 | 2015-09-30 | 株式会社爱考斯研究 | The manufacture method of the manufacturing installation of catalyst layer, the manufacture method of catalyst layer, polymer electrolyte solution and polymer electrolyte solution |
| JP5565305B2 (en) * | 2010-01-07 | 2014-08-06 | 株式会社エクォス・リサーチ | Fuel cell catalyst layer manufacturing apparatus, fuel cell catalyst layer manufacturing method, polymer electrolyte solution, and polymer electrolyte solution manufacturing method |
| WO2011083842A1 (en) * | 2010-01-07 | 2011-07-14 | 株式会社エクォス・リサーチ | Apparatus for production of catalyst layer for fuel cell, method for production of catalyst layer for fuel cell, polyelectrolyte solution, and process for production of polyelectrolyte solution |
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| JPS5847471A (en) * | 1981-09-14 | 1983-03-19 | Takashi Sato | Satsumaage or kamaboko containing stalk of wasabi and its preparation |
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1993
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| Publication number | Publication date |
|---|---|
| JPH06260170A (en) | 1994-09-16 |
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