JP2696916B2 - Method for producing matrix layer for phosphoric acid type fuel cell - Google Patents
Method for producing matrix layer for phosphoric acid type fuel cellInfo
- Publication number
- JP2696916B2 JP2696916B2 JP63110823A JP11082388A JP2696916B2 JP 2696916 B2 JP2696916 B2 JP 2696916B2 JP 63110823 A JP63110823 A JP 63110823A JP 11082388 A JP11082388 A JP 11082388A JP 2696916 B2 JP2696916 B2 JP 2696916B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphoric acid
- matrix layer
- matrix
- fuel cell
- catalyst layer
- 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 - Fee Related
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
- H01M8/02—Details
- H01M8/0289—Means for holding the electrolyte
- H01M8/0293—Matrices for immobilising electrolyte solutions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for 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
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Fuel Cell (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明は、リン酸型燃料電池用マトリツクス層の製
造方法に関するものである。Description: TECHNICAL FIELD The present invention relates to a method for producing a matrix layer for a phosphoric acid type fuel cell.
従来、リン酸型燃料電池用マトリツクス層の製造方法
としては、特開昭60-151968号公報に開示されているよ
うに、リバースロールコーターによりマトリツクスペー
ストを触媒層表面に塗布する方法があつた。この他、ス
クリーン印刷法、スプレー法、カーテンフローコーター
法なども用いられている。いずれの方法においても、水
などの溶媒、バインダーや増粘剤などを含むマトリツク
スペーストを触媒層表面に塗布して乾燥する。この後、
熱処理で増粘剤を除去し、さらに330℃前後で、PTFE
（ポリテトユフルオロエチレン）などのバインダーを溶
融してSiCなどの微粒子を結着して形状を保つている。
マトリツクスペーストの組成については、例えば特公昭
58-31472号公報、特公昭58-156号公報や特公昭59-16393
号公報に詳しく記載されている。Conventionally, as a method for producing a matrix layer for a phosphoric acid type fuel cell, there is a method of applying a matrix paste to the surface of a catalyst layer using a reverse roll coater, as disclosed in JP-A-60-151968. . In addition, a screen printing method, a spray method, a curtain flow coater method, and the like are also used. In either method, a matrix paste containing a solvent such as water, a binder, a thickener and the like is applied to the surface of the catalyst layer and dried. After this,
The thickener is removed by heat treatment.
It melts a binder such as (polytetrafluoroethylene) and binds fine particles such as SiC to maintain its shape.
Regarding the composition of the matrix paste, for example,
JP-B-58-31472, JP-B-58-156 and JP-B-59-16393
This is described in detail in the official gazette.
上記に示した従来のリン酸型燃料電池用マトリツクス
の製造方法はいずれも溶媒を用いてマトリツクスペース
トを作るために、気泡が入りやすい。この気泡が乾燥の
際にピンホールとなつてマトリツクスを介してのクロス
オーバー（反応ガスのリーク）の原因となつていた。ま
た、いかに触媒層従属させているとはいえ取扱い上、形
状を保つためにPTFE（ポリテトラフルオロエチレン）を
バインダーとして用いざるを得ない。このPTFEは強い撥
水性を有するため、マトリツクスのリン酸保持性が著し
く低下するという問題点があつた。また、マトリツクス
に使用するSiCなどの無機化合物微粒子の大きさはでき
るだけ小さい方が好ましい。これは無機化合物微粒子が
小さいと、マトリツクスを形成した際にできる空孔の大
きさが小さくなつて毛細管吸引力が増し、リン酸の保持
性が良くなるためである。ところが、小さい微粒子ほど
乾燥の際にマツドクラツクが入りやすく、また形状を保
ために大量のPTFEを必要とするため、使用できる微粒子
の粒径の下限は１μｍ程度であつた。In any of the conventional methods for producing a matrix for a phosphoric acid type fuel cell described above, since a matrix paste is prepared using a solvent, bubbles are likely to enter. These bubbles formed pinholes during drying and caused crossover (reaction gas leakage) via the matrix. In addition, PTFE (polytetrafluoroethylene) must be used as a binder in order to maintain the shape in handling, though it depends on the catalyst layer. Since this PTFE has strong water repellency, there is a problem that the phosphate retention of matrix is significantly reduced. Further, the size of the inorganic compound fine particles such as SiC used in the matrix is preferably as small as possible. This is because, when the inorganic compound fine particles are small, the size of the pores formed when the matrix is formed is reduced, so that the capillary suction force is increased, and the retention of phosphoric acid is improved. However, the smaller the fine particles, the more easily the pine crack occurs during drying, and a large amount of PTFE is required to maintain the shape. Therefore, the lower limit of the usable fine particles is about 1 μm.
この発明は上記のような問題点を解消するためになさ
れたもので、PTFEなどのバインダーを用いずに形状を保
つことができ、リン酸保持性に優れたマトリツクス層を
簡単に形成できるリン酸型燃料電池用マトリツクス層の
製造方法を得ることを目的とする。The present invention has been made in order to solve the above problems, and can maintain a shape without using a binder such as PTFE, and can easily form a matrix layer having excellent phosphoric acid retention properties. It is an object of the present invention to obtain a method of manufacturing a matrix layer for a fuel cell.
この発明に係るリン酸型燃料電池用マトリツクス層の
製造方法は、電極触媒層にリン酸を含浸する工程、及び
リン酸を含浸した電極触媒層表面に重機化合物の微粒子
を粉体の状態で接触させて付着する工程を施すものであ
る。The method for producing a matrix layer for a phosphoric acid type fuel cell according to the present invention includes a step of impregnating the electrode catalyst layer with phosphoric acid, and contacting the surface of the electrode catalyst layer impregnated with phosphoric acid with fine particles of a heavy equipment compound in a powder state. In this case, a step of attaching the substrate is performed.
この発明における触媒層は、あらかじめリン酸を含浸
させ、無機化合物の微粒子を粉体の状態で触媒層表面に
接触させて付着させることによつて、リン酸を接着剤と
してマトリツクス層が形成される。これは触媒層に含浸
させたリン酸が粘着性を有するためである。従って、製
造が簡単にでき、PTFEなどのバインダーを用いずに形状
を保つている。In the present invention, the catalyst layer is preliminarily impregnated with phosphoric acid, and fine particles of an inorganic compound are brought into contact with the surface of the catalyst layer in the form of powder to adhere thereto, whereby a matrix layer is formed using phosphoric acid as an adhesive. . This is because phosphoric acid impregnated in the catalyst layer has tackiness. Therefore, it can be manufactured easily and keeps its shape without using a binder such as PTFE.
以下、この発明の一実施例を図について説明する。第
１図において、（１）はふるい、（２）は無機化合物例
えばSiCの微粒子、（３）はあらかじめリン酸を含浸さ
せた電磁触媒層、（４）は電極基材である。リン酸を含
む電極触媒層（３）は粘着性を有しており、第１図のよ
うにSiCの微粒子（２）を粉体の状態でふりかけるだけ
で、これを電極触媒層（３）に付着させることができ
る。第２図はSiCの微粒子（２）をふりかけた後、電極
を逆さにして余分なSiCをはらい落した後の電極を示す
側面図である。（５）は電極触媒層（３）に付着したSi
Cの微粒子で形成されたマトリツクス層を示す。何度も
テストを繰り返した結果、電極触媒層（３）にむらなく
リン酸が含浸されており、かつ表面に余分のリン酸が付
着していなければ、電極触媒層（３）に付着しうるSiC
の微粒子（５）の厚さは25μｍ程度となる。An embodiment of the present invention will be described below with reference to the drawings. In FIG. 1, (1) is a sieve, (2) is fine particles of an inorganic compound such as SiC, (3) is an electromagnetic catalyst layer previously impregnated with phosphoric acid, and (4) is an electrode substrate. The phosphoric acid-containing electrocatalyst layer (3) has adhesiveness, and as shown in FIG. 1, simply sprinkling SiC fine particles (2) in a powder state, and this is applied to the electrocatalyst layer (3). Can be attached. FIG. 2 is a side view showing the electrode after sprinkling fine particles (2) of SiC, turning the electrode upside down, and scraping off excess SiC. (5) is the Si adhered to the electrode catalyst layer (3)
2 shows a matrix layer formed of fine particles of C. As a result of repeating the test many times, if the electrode catalyst layer (3) is uniformly impregnated with phosphoric acid and no extra phosphoric acid adheres to the surface, the electrode catalyst layer (3) may adhere to the electrode catalyst layer (3). SiC
The thickness of the fine particles (5) is about 25 μm.
さらに、極めて均一の厚さで、しかもピンホールなど
の欠陥もなく、マトリツクス層が形成されることがわか
つた。Furthermore, it was found that a matrix layer was formed with a very uniform thickness and without defects such as pinholes.
そこで、空気極触媒層、燃料極触媒層の両方に対し
て、この発明の一実施例と同様のマトリツクス層の製造
方法により製造した。すなわち、平均粒径0.06μｍのSi
Cを用いて厚さをそれぞれ25μｍ程度のマトリツクス層
を形成し、単セルによるマトリツクスとしての機能テス
トを行なつた。単セルは２台組立て、そのうち１台はマ
トリツクス層（５）にさらにリン酸を塗布して組み立
て、もう１台はマトリツクス層（５）にはリン酸を塗布
せずその分のリン酸をセル内の電解質リザーバに貯蔵し
ておいた。PTFEなどのバインダーを全く用いていないの
にもかかわらず、SiCは電極触媒層（３）の表面に強固
に接着されており、リン酸を塗布してもむらは生じなか
つた。マトリツクス層（５）にリン酸を塗布したセルは
初期から高い開放電圧を示し、マトリツクス層（５）が
充分にガスシール性能を有していることを示唆したが、
マトリツクス層（５）にリン酸を塗布しなかつたセルは
初期に著しいクロスオーバーを示した。しかしこのセル
も約100時間後には高い開放電圧を示すようになつた。
これは0.06μｍという超微粒子の小さな空孔により生じ
る強力な毛管吸引力によりセル内の電解質リザーバから
リン酸を吸収したためと考えられる。これらのセルのマ
トリツクス厚みはいずれも50μｍに相当し、オーム損は
10mv/100mA/cm2と極めて低い値となり、その分セル特性
が向上した。この厚さは従来のマトリツクス層の製造方
法では実現困難な厚さである。また、0.06μｍという無
機化合物の超微粒子についてももちろん、従来の方法で
は使いこなすことはできなかつたものである。この２台
のセルは長時間にわたり、開放電圧の低下もなく、安定
に動作した。Therefore, both the air electrode catalyst layer and the fuel electrode catalyst layer were manufactured by the same matrix layer manufacturing method as in the embodiment of the present invention. In other words, Si with an average particle size of 0.06 μm
Matrix layers each having a thickness of about 25 μm were formed using C, and a function test as a matrix using a single cell was performed. Two single cells were assembled. One of them was assembled by further applying phosphoric acid to the matrix layer (5), and the other was to apply phosphoric acid to the matrix layer (5) without applying phosphoric acid. It was stored in the electrolyte reservoir inside. Although no binder such as PTFE was used at all, SiC was firmly adhered to the surface of the electrode catalyst layer (3), and even when phosphoric acid was applied, no unevenness occurred. The cell in which phosphoric acid was applied to the matrix layer (5) showed a high open-circuit voltage from the beginning, suggesting that the matrix layer (5) had sufficient gas sealing performance.
Cells without phosphoric acid applied to the matrix layer (5) showed a significant crossover initially. However, this cell also showed a high open circuit voltage after about 100 hours.
This is probably because phosphoric acid was absorbed from the electrolyte reservoir in the cell by the strong capillary suction force generated by the small pores of the ultrafine particles of 0.06 μm. The matrix thickness of each of these cells is equivalent to 50 μm, and the ohmic loss is
The value was as extremely low as 10 mv / 100 mA / cm 2, and the cell characteristics were improved accordingly. This thickness is a thickness that is difficult to achieve with a conventional method for manufacturing a matrix layer. In addition, ultrafine particles of an inorganic compound having a particle size of 0.06 μm cannot be used with conventional methods. These two cells operated stably for a long time without a decrease in open-circuit voltage.
なお、この発明によるマトリツクス層の製造方法によ
れば、マトリツクス層を形成した後の熱処理工程などが
不要であり、もちろんマトリツクスペーストを作成する
必要もないので、工程が極めて簡単になる。According to the method of manufacturing a matrix layer according to the present invention, a heat treatment step or the like after forming the matrix layer is unnecessary, and, of course, there is no need to prepare a matrix paste, so that the process is extremely simplified.
また、無機化合物の微粒子の粉体はSiCに限るもので
はなく、他の材料でも同様の効果を奏する。Further, the powder of the fine particles of the inorganic compound is not limited to SiC, and similar effects can be obtained with other materials.
以上のように、この発明はよれば、電極触媒層にリン
酸を含浸する工程、及びリン酸を含浸した電極触媒層表
面に無機化合物の微粒子を粉体の状態で接触させて付着
させたので、OTFEなどのバインダーを用いることなく形
状を保つことができ、リン酸保持性に優れたリン酸型燃
料電池用マトリツクス層を簡単に製造する方法が得られ
る効果がある。As described above, according to the present invention, the step of impregnating the electrode catalyst layer with phosphoric acid, and the step of impregnating the fine particles of the inorganic compound on the surface of the electrode catalyst layer impregnated with phosphoric acid by contacting them in powder form, The shape can be maintained without using a binder such as OTFE or the like, and there is an effect that a method for easily producing a matrix layer for a phosphoric acid type fuel cell having excellent phosphoric acid retention can be obtained.
第１図はこの発明の一実施例によるリン酸型燃料電池用
マトリツクス層の製造方法に係る一工程を示す説明図、
第２図はこの発明の一実施例により製造されたマトリツ
クス層を示す側面図である。 （２）……無機化合物の微粒子、（３）……電極触媒
層、（５）……マトリツクス層。 なお、図中、同一符号は同一、又は相当部分を示す。FIG. 1 is an explanatory view showing one step of a method for producing a matrix layer for a phosphoric acid type fuel cell according to one embodiment of the present invention,
FIG. 2 is a side view showing a matrix layer manufactured according to an embodiment of the present invention. (2) ... fine particles of an inorganic compound, (3) ... an electrode catalyst layer, (5) ... a matrix layer. In the drawings, the same reference numerals indicate the same or corresponding parts.
Claims (1)
リン酸を含浸した上記電極触媒層の表面に無機化合物の
微粒子を粉体の状態で接触させて付着する工程を施すこ
とを特徴とするリン酸型燃料電池用マトリツクス層の製
造方法。1. A step of impregnating phosphoric acid into an electrode catalyst layer and a step of bringing inorganic compound fine particles into contact with and adhering to the surface of the electrode catalyst layer impregnated with phosphoric acid in a powdery state. Of manufacturing a matrix layer for a phosphoric acid type fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63110823A JP2696916B2 (en) | 1988-05-07 | 1988-05-07 | Method for producing matrix layer for phosphoric acid type fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63110823A JP2696916B2 (en) | 1988-05-07 | 1988-05-07 | Method for producing matrix layer for phosphoric acid type fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01281680A JPH01281680A (en) | 1989-11-13 |
| JP2696916B2 true JP2696916B2 (en) | 1998-01-14 |
Family
ID=14545564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63110823A Expired - Fee Related JP2696916B2 (en) | 1988-05-07 | 1988-05-07 | Method for producing matrix layer for phosphoric acid type fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2696916B2 (en) |
-
1988
- 1988-05-07 JP JP63110823A patent/JP2696916B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01281680A (en) | 1989-11-13 |
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