JPS58129771A - Preparing method of electrode for fuel cell - Google Patents
Preparing method of electrode for fuel cellInfo
- Publication number
- JPS58129771A JPS58129771A JP57011511A JP1151182A JPS58129771A JP S58129771 A JPS58129771 A JP S58129771A JP 57011511 A JP57011511 A JP 57011511A JP 1151182 A JP1151182 A JP 1151182A JP S58129771 A JPS58129771 A JP S58129771A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- metal powder
- lithium
- temperature
- fuel cell
- 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
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
-
- 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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8668—Binders
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inert Electrodes (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は溶融炭酸塩型燃料電池用電極の製作方法に係り
、特にカソード側に使用する電極の製作に好適な方法に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of manufacturing an electrode for a molten carbonate fuel cell, and particularly to a method suitable for manufacturing an electrode used on the cathode side.
溶融炭酸地型燃旧電池の電極として水素還元雰囲気で製
造したＮ１焼結体が主に使用されている。N1 sintered bodies produced in a hydrogen reducing atmosphere are mainly used as electrodes in molten carbonate ground type combustion batteries.
この電極はアノード側に使用する場合は十分に用途に耐
える。しかしカソード側においては、燃料電池の運転時
に電極の崩壊が起こり、電池性能の低下やクロスオーバ
ー等を誘起する危険性があった。This electrode is sufficiently durable when used on the anode side. However, on the cathode side, the electrode collapses during operation of the fuel cell, posing the risk of deteriorating cell performance and inducing crossover.
本発明の目的は、カソード側電極として用いた場合に、
電池の運転時に崩壊することのない電極の製作方法を提
供するにある。The purpose of the present invention is to: when used as a cathode side electrode,
An object of the present invention is to provide a method for manufacturing an electrode that does not collapse during battery operation.
燃料電池のカソード電極としてリチウム化処理したもの
が良好に使用できることは、名古屋大学高傭氏〔電気化
学、３０，７５９ （１９６２）１等の報告にみられる
。本発明はこれらの知見の下に燃料電池用のリチウム化
処理した電極を安価に、しかも信頼性高く製作する方法
についてのものである。The fact that a lithium-treated cathode electrode can be used satisfactorily as a cathode electrode of a fuel cell is seen in a report by Takayuki Takayuki of Nagoya University [Electrochemistry, 30, 759 (1962) 1, etc.]. Based on these findings, the present invention relates to a method for manufacturing lithiated electrodes for fuel cells at low cost and with high reliability.
電極のリチウム化処理は、例えばＮ１粉末をカルボキシ
ルメチルセルロース（’ＣＭＣ）’Ｊの水浴ｉを一次バ
インダとして成型した電極を水素還元雰囲気の下７５０
〜１００ＯＣで焼結したものについて行っていた。リチ
ウム化にはリチウム塩、主として硝酸リチウムまたは水
酸化リチウム全アルコール性溶液あるいは水溶液の形に
し、これを前述のＮｉｉ結体に含授していた。貧浸した
後さらに５００〜８０００前後の温度で加熱して電極の
リチウム化を達成していた。このような方法であると電
極に加えられたリチウム塩の量が正確に把握できないこ
とと、リチウム塩の分散が均一に行えないという問題点
が残る。これに対して本発明の方法は、電極用金属粉末
の一次バインダとしてリチウムイオンを含む有機高分子
水溶液を使用し金属粉□末中に必安量ヲ均一に分散させ
るものである。したがって従来技術の問題点の改善は容
易である。これを電極の形に成型後、室温または約１８
０Ｃまでの高温好丑しくは約１００Ｃ前後の温度で乾燥
する。次いで水素還元雰囲気、真空中あるいは不活性雰
囲気で焼結する。この工程において金属粉末の焼結とそ
の中へのリチウムの拡散がなされ、リチウム拡散電極を
得ることができる。The lithium treatment of the electrode is carried out, for example, by molding an electrode made of N1 powder in a water bath of carboxymethyl cellulose ('CMC)' J as a primary binder and subjecting it to 750°C under a hydrogen-reducing atmosphere.
This was done for those sintered at ~100OC. For lithiation, a lithium salt, mainly lithium nitrate or lithium hydroxide, was prepared in the form of an all-alcoholic solution or an aqueous solution, and this was impregnated into the above-mentioned Nii aggregate. After immersion, the electrode was further heated at a temperature of about 500 to 8,000 ℃ to achieve lithiation of the electrode. This method leaves problems in that the amount of lithium salt added to the electrode cannot be accurately determined and the lithium salt cannot be uniformly dispersed. In contrast, the method of the present invention uses an organic polymer aqueous solution containing lithium ions as the primary binder of the metal powder for electrodes, and uniformly disperses the required amount in the metal powder. Therefore, it is easy to improve the problems of the prior art. After molding this into an electrode shape, it is heated at room temperature or about 18
Dry at a high temperature of up to 0C, preferably around 100C. It is then sintered in a hydrogen reducing atmosphere, in vacuum or in an inert atmosphere. In this step, the metal powder is sintered and lithium is diffused into it, thereby making it possible to obtain a lithium diffusion electrode.
この電極はこのままの状態でも使用できるが、好ましく
は空気または酸素の存在下、５００〜８００Ｃ（Ｄ温度
、好丘しくは約６５０Ｃの１ＩｌｉＡ度で加熱して電極
に酸化物被覆を形成する。Although the electrode can be used as is, it is preferably heated in the presence of air or oxygen at 500 to 800 degrees Celsius, preferably about 650 degrees Celsius, to form an oxide coating on the electrode.
本発明で使用する電極用金属粉末はＮｉが主体であるが
、これに限定するものではない。′またリチウムイオン
を含む有機高分子水溶液としてはポリアクリル酸のリチ
ウム塩、イソブチレン−無水マレイン酸共重合体のリチ
ウム塩が特に好捷しいが前記畠分子のように分子中にリ
チウムイオンが付いているものでなくとも、リチウム塩
と共存して安定ならば有機高分子水溶液とリチウム塩の
混合液であっても差し支えない。The metal powder for electrodes used in the present invention is mainly composed of Ni, but is not limited to this. 'In addition, as organic polymer aqueous solutions containing lithium ions, lithium salts of polyacrylic acid and lithium salts of isobutylene-maleic anhydride copolymer are particularly preferred; Even if the organic polymer aqueous solution and the lithium salt are not present, a mixed solution of the organic polymer aqueous solution and the lithium salt may be used as long as it is stable in coexistence with the lithium salt.
以上述べた方法により製作した電極は溶融炭酸塩型燃料
電池、用の電極、特にカソード電極としてその特性を発
揮することが認められた。以下本発明を実施世」によっ
てさらに詳しく説明する。なお実施例は本発明の一例で
あり、これによって本発明を限定するものではない。It has been found that the electrode produced by the method described above exhibits its characteristics as an electrode for molten carbonate fuel cells, especially as a cathode electrode. Hereinafter, the present invention will be explained in more detail with reference to the embodiments. Note that the examples are only examples of the present invention, and the present invention is not limited thereby.
実施例１ □
Ｎ１粉末１００重量部に対して一次バインダーとしてイ
ンブチレン−無水マレイン酸共ｍ合体’）チウム塩水溶
液〔組成割合：イソブチレンー無水マレイン酸共重合体
；５％＋Ｌ’ＯＨ；１５％。Example 1 □ An aqueous solution of inbutylene-maleic anhydride copolymer') tium salt as a primary binder for 100 parts by weight of N1 powder [composition ratio: isobutylene-maleic anhydride copolymer; 5% + L'OH; 15%.
水；８０％〕を４０重量部添加混合して電極を成型した
。この成型体をｗ碑で乾燥し、次いで１００Ｃで乾燥し
た。その後水素還元雰囲気のもと、８００Ｃで２Ｈ焼結
処理した。こうして製作した′電極を７０００で３０分
間、空気中加熱して最終電極製品を作った。本実施例で
作った電極をカソード側に使用し溶融炭酸塩型燃料電池
の性能試験を行った。作動温度は６５０Ｃであった。こ
の電池は電極構造に劣化を与えることなく、２００時間
にわたって電流密度２００ｍＡ／ｌｙｎ” 、電圧０．
６５Ｖを
で作動。継続した。40 parts by weight of water (80%) was added and mixed to form an electrode. This molded body was dried in a dryer and then at 100C. Thereafter, 2H sintering treatment was performed at 800C in a hydrogen reducing atmosphere. The 'electrode thus produced was heated in air at 7000C for 30 minutes to produce a final electrode product. A performance test of a molten carbonate fuel cell was conducted using the electrode made in this example on the cathode side. The operating temperature was 650C. This battery can be operated at a current density of 200 mA/lyn'' and a voltage of 0.5 mA for 200 hours without any deterioration of the electrode structure.
Operates on 65V. Continued.
実施例２〜５
Ｎｉ粉末１００重１゛部に対して実施例１において使用
した一次バインダの添加量を表１に示す範囲で変えた。Examples 2 to 5 The amount of the primary binder used in Example 1 relative to 100 parts by weight of Ni powder was varied within the range shown in Table 1.
最終電極製品を得るまでの他の工程は実施例１と同じで
ある。表１にはまた作動温度６５０Ｃにおける溶融地型
燃料電池のカソード側に本実施例の電極を使用した時の
性能試験結果も９Ｆ Ｍ己した。The other steps up to obtaining the final electrode product are the same as in Example 1. Table 1 also shows the performance test results when the electrode of this example was used on the cathode side of a molten ground fuel cell at an operating temperature of 650C.
表 １
■
量
比較例は、−次バインダとして２％ＣＭＣ水溶液４０電
量部を添加している。水素還元雰囲気のもと８０００で
２時間焼結させたものである。Table 1 (1) Amount Comparative Example has 40 parts of a 2% CMC aqueous solution added as a secondary binder. It was sintered at 8000C for 2 hours in a hydrogen reducing atmosphere.
本発明によるものは、比較例にくらべて電極の劣化が少
なく、かつ電池性能がすぐれていることが確認された。It was confirmed that the battery according to the present invention had less electrode deterioration and better battery performance than the comparative example.
なお、本発明によれば以下の効果も得られる。In addition, according to the present invention, the following effects can also be obtained.
（１） 電極のリチウム化処理が均一に行える。(1) The lithium treatment of the electrode can be performed uniformly.
（２）電極にリチウムを一定量含ませることができるた
め品質の信頼性が向上する。(2) Since the electrode can contain a certain amount of lithium, quality reliability is improved.
（３）従来行っている電極のリチウム化処理にくら″＋
？↑グ１′：ｒ
＝３２５−(3) Difficulty with conventional electrode lithium treatment
? ↑G1': r = 325-
Claims (1)
含む有機尚分子水溶液を使用し、電極を成型し次いで焼
結したことを特徴とする燃料電池用電極の製作方法。 ２、特許請求の範囲第１項において、前記Ｌｉイオンを
含む有機高分子がポリアクリル酸リチウム、α−オレフ
ィン−無水マレイン酸のリチウム塩であることを特徴と
する燃料電池用電極の製作方法。 ３、特許請求の範囲第１項において、前記電極用金属粉
末がＮｉであることを特徴とする燃料電池用電極の製作
方法。[Scope of Claims] 1. A method for producing an electrode for a fuel cell, characterized in that an organic molecule aqueous solution containing Li ions is used as a primary binder of metal powder for the electrode, and the electrode is molded and then sintered. 2. A method for producing an electrode for a fuel cell according to claim 1, wherein the organic polymer containing Li ions is lithium polyacrylate or a lithium salt of α-olefin-maleic anhydride. 3. The method of manufacturing an electrode for a fuel cell according to claim 1, wherein the metal powder for the electrode is Ni.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57011511A JPS58129771A (en) | 1982-01-29 | 1982-01-29 | Preparing method of electrode for fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57011511A JPS58129771A (en) | 1982-01-29 | 1982-01-29 | Preparing method of electrode for fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58129771A true JPS58129771A (en) | 1983-08-02 |
Family
ID=11780033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57011511A Pending JPS58129771A (en) | 1982-01-29 | 1982-01-29 | Preparing method of electrode for fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58129771A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0473236A2 (en) * | 1990-08-30 | 1992-03-04 | Stichting Energieonderzoek Centrum Nederland(ECN) | Tape suitable for use in fuel cells, electrode suitable for use in a fuel cell, method for sintering an electrode of this type and a fuel cell provided with an electrode of this type |
-
1982
- 1982-01-29 JP JP57011511A patent/JPS58129771A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0473236A2 (en) * | 1990-08-30 | 1992-03-04 | Stichting Energieonderzoek Centrum Nederland(ECN) | Tape suitable for use in fuel cells, electrode suitable for use in a fuel cell, method for sintering an electrode of this type and a fuel cell provided with an electrode of this type |
| US5356731A (en) * | 1990-08-30 | 1994-10-18 | Stichting Energieonderzoek Centrum Nederland | Molten cabonate fuel cell with sintered LiCoO2 electrode |
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