JPS62154575A - Manufacture of fuel electrode for molten carbonate fuel cell - Google Patents
Manufacture of fuel electrode for molten carbonate fuel cellInfo
- Publication number
- JPS62154575A JPS62154575A JP60295422A JP29542285A JPS62154575A JP S62154575 A JPS62154575 A JP S62154575A JP 60295422 A JP60295422 A JP 60295422A JP 29542285 A JP29542285 A JP 29542285A JP S62154575 A JPS62154575 A JP S62154575A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- fuel cell
- powder
- wood pulp
- molten carbonate
- 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.)
- Granted
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
- H01M4/8878—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
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- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の属する技術分野〕
この発明は、溶融炭酸塩を電解質と１〜で作動する燃料
電池に係り、特にこの燃料電池に組み込まれる燃料極（
アノード）の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical field to which the invention pertains] The present invention relates to a fuel cell that operates using molten carbonate and an electrolyte, and particularly relates to a fuel electrode (
(Anode) manufacturing method.
浴融炭酸塩燃料電池（以下の本文ではＭＣＦＣという）
は動作温度が高く、腐食性の旨い溶融炭酸塩を使用して
いるため、燃料極（以下、アノードという）と酸化極（
以下、カソードという）に用いる電極材料にも種々の要
求性能が課せられている。ア７ノード電極に対する要求
特性をまとめると以下のようになる。Bath molten carbonate fuel cell (referred to as MCFC in the following text)
Since the operating temperature is high and corrosive molten carbonate is used, the fuel electrode (hereinafter referred to as anode) and oxidation electrode (
Various required performances are also imposed on the electrode materials used for the cathodes (hereinafter referred to as cathodes). The characteristics required for the anode electrode are summarized as follows.
（１）ガス雰囲気に対して安定であること。(1) It must be stable in a gas atmosphere.
（２）耐熱性とくにクリープｇ１１扶が高いこと。(2) High heat resistance, especially creep g11.
（３）急激な電解質流人がなく、ガスと反応できること
。(3) Ability to react with gas without rapid electrolyte drift.
ｆ４）Ｎ気伝端、性が高いこと。f4) N Qi transmission end, high quality.
（５）安価であること。(5) It should be inexpensive.
従来、ｈ、ｉ ＣＦ Ｃのアノードには多孔質のＮｌ框
極板が広く使用されている。これはＮｉが耐食性と導電
性をバランスよく共像し、かつ良質の粉末か入手しや−
「く、多孔質電極板の製造も比較的容易なためである。Conventionally, a porous Nl frame electrode plate has been widely used for the anode of h,i CF C. This is because Ni has a well-balanced combination of corrosion resistance and conductivity, and it is easy to obtain high-quality powder.
This is because manufacturing of porous electrode plates is relatively easy.
通常、多孔１Ｎｉ１！を極板は粒径が３〜７μｍのカー
ダニルニッケル扮末を用い、これを所望の寸法。Usually porous 1Ni1! The electrode plate uses cardanyl nickel powder with a particle size of 3 to 7 μm, and is adjusted to the desired size.
形状をイイする黒鉛型などに充填し、還元性雰囲気中で
約６５０°〜１０００℃の温度範囲で焼結することによ
って製造される。ＭＣＦＣのアノード電（へとして望し
い細孔容積（空孔率）、平均空孔径または空孔径分布な
どは実験的に決定されるが、これらは主に電解質板の多
孔度および電池の動作条件に依存する。良好な′電池特
性を得るためには、反応を行うのに十分なだけの電解質
が１ｉＬＷ４′ホ板から電極に流入し、かつ反応ガスの
１を極内の迅速な拡散を妨げるほどには′電解質が電極
に流入しないような空孔率、空孔径などをもつことが＊
’ｋ ｆこは要求される。一般的に言えば、前記条件
を満たすための多孔質電極板の空孔率は６０〜８０％、
平均空孔径は１〜１０μｍ（望ましきは４〜７μｆｒＬ
）とされ、多孔質Ｎｉ電極板はこれら要求をほぼ満足し
ている。しかし、多孔質Ｎｉ＠極板はクリープ強度が小
さいため、！池の運転下において滉結が経時的に進行し
て空孔率および表面積などが減少してＭＣＦＣの電池性
能を低下させるという欠点をもっている。It is manufactured by filling a graphite mold with a suitable shape and sintering it in a reducing atmosphere at a temperature in the range of about 650° to 1000°C. The desired pore volume (porosity), average pore diameter, pore diameter distribution, etc. for the anode electrode of MCFC are determined experimentally, but these mainly depend on the porosity of the electrolyte plate and the operating conditions of the battery. In order to obtain good 'cell properties, enough electrolyte flows from the 1iLW4' plate into the electrode to carry out the reaction, and enough electrolyte flows into the electrode from the 1iLW4' plate to prevent rapid diffusion of the reactant gas into the electrode. The electrode must have a porosity, pore diameter, etc. that prevents the electrolyte from flowing into the electrode.
'kf is requested. Generally speaking, the porosity of the porous electrode plate to satisfy the above conditions is 60 to 80%,
The average pore diameter is 1 to 10 μm (preferably 4 to 7 μfrL)
), and the porous Ni electrode plate almost satisfies these requirements. However, since the porous Ni@electrode plate has low creep strength,! During operation of the pond, condensation progresses over time and porosity and surface area decrease, resulting in a deterioration of MCFC battery performance.
本発明の目的は、耐焼結性に富みかつ電極大型化の容易
なＭ ＣＦ Ｃ用アノード電極の腸造方法を提供するこ
とである。An object of the present invention is to provide a method for making an anode electrode for M CF C that is highly sintering resistant and easy to increase the size of the electrode.
この目的は本発明によれは、Ｎｉ粉末と木材パルプを水
中で混合して抄造に適する水性スラリーとし、これに凝
集剤を添加１２て粉末をパルプに吸着凝集させ、抄造す
ることで得た板状の成形物に金属メ、シェをプレス成型
によって圧着せしめた後、酸化性雰囲気で加熱１〜で木
材パルプを焼失飛散するし、続いて前記加熱で生じた金
属酸化物の還元と、Ｎ１粉末の焼結を行うために制減の
還ノじ性雰囲気で加熱することにより達成される。According to the present invention, Ni powder and wood pulp are mixed in water to form an aqueous slurry suitable for papermaking, a flocculant is added to this, the powder is adsorbed and agglomerated by the pulp, and a board obtained by papermaking is obtained. After press-molding the metal shell onto the molded product, the wood pulp is burned and scattered by heating in an oxidizing atmosphere, followed by reduction of the metal oxides generated by the heating, and N1 powder. This is accomplished by heating in a reduced reflux atmosphere to effect sintering.
本発明で用いるＮｉ粉末は一般１こ市販されている電解
粉やカーボニルニッケル粉末などのいずれでも良いが、
電極としたときの電気化学的性質を向上させるにはより
微細な粉末（粒径１〜１０μｆｎ）の方が好ましい。ま
た、粉末な吸着・城集させるために用いるパルプには種
々のものがあるが、本発明では繊維径が細く、繊維同志
の絡みも多くかつ安価であると、いう観点から木材パル
プを選定した。The Ni powder used in the present invention may be any commercially available electrolytic powder or carbonyl nickel powder, but
In order to improve electrochemical properties when used as an electrode, finer powder (particle size 1 to 10 μfn) is preferable. In addition, there are various types of pulp used for adsorbing and collecting powder, but in the present invention, wood pulp was selected from the viewpoints that the fiber diameter is small, the fibers are often entwined with each other, and it is inexpensive. .
この木材パルプの癌加量は所望するアノードの空孔率に
応じて任意に選択可能であるが、本発明で意図するアノ
ードの製造に当っては焼結前の成形物の全′Ｍ量に対し
て３〜１５％が好ましい範囲であった。The porosity of this wood pulp can be arbitrarily selected depending on the desired porosity of the anode, but in producing the anode intended in the present invention, the total amount of M in the molded product before sintering is The preferable range was 3 to 15%.
板状の成形物１こ圧着させ、かつ焼結後に電極の補強材
としての役割を発揮する金属メツシュの材質は、強度、
耐熱性および耐食性を兼備したニッケル、ステンレス、
カンタルなどが適しており、′メツシュ形状としては１
０〜８ｔＪメ、シュでその線径が０．１〜Ｑ、 ３ ｍ
ｍ ′の範囲が本発明の目的に合致していた。The material of the metal mesh, which is pressed together with a plate-shaped molded object and acts as a reinforcing material for the electrode after sintering, has a high strength,
Nickel, stainless steel, which has both heat resistance and corrosion resistance.
Kanthal etc. are suitable, and the mesh shape is 1.
0~8tJ, wire diameter is 0.1~Q, 3m
The range of m' was consistent with the objectives of the present invention.
一方、板状の成形物に金１属メ、シュを圧着するには、
両者を積層した後プレス機で徐々に圧を上げる方法を用
いる。圧力は５０〜２００ψｔｙｔｒｔｔｖ範囲で行な
うと良い。この際、必要ならば、プレス成型時にプレス
機を加温する。例えば、ω〜１５０℃の温度範囲で徐々
に温度を上昇させるとか、３０’・６００・９０’・１
２０℃という具合に段階的ｌ・こ温良を上昇させても良
好な結果が得られろ。ηｉお、ブ）／ス成型工程は金属
メツシーを成形物に圧着させるとともに、抄造した成形
物は水分が非常に多いので、それを脱水して表面性状を
フラットで均一に保てる乾燥法としての効果も有してい
る。On the other hand, in order to press a metal metal mesh onto a plate-shaped molded product,
A method is used in which after laminating both layers, the pressure is gradually increased using a press machine. The pressure is preferably in the range of 50 to 200 ψtytrttv. At this time, if necessary, the press machine is heated during press molding. For example, gradually increasing the temperature in the temperature range of ω ~ 150℃, 30', 600, 90', 1
Even if the temperature is increased stepwise to 20°C, good results can be obtained. The molding process presses the metal mesh onto the molded product, and since the molded product contains a lot of moisture, it is effective as a drying method that dehydrates the water and keeps the surface texture flat and uniform. It also has
以上のプレス成型工程を経た後、金属メツシー付き成形
物を電気炉に入れて酸１じ性写囲気中で、必要ならば空
気を流しながら常温から１００℃／１１前後の速度で加
熱すると、４００°Ｃ近辺から成形物に含まれる木材パ
ルプ、凝集剤は焼失気イじを開始し、これらはほぼ５０
０℃で完全に焼失しで１−よう。したがって、酸化性雰
囲気での加熱漏曳は４５０°〜６００°Ｃで、その保持
時間は１〜３時間が好ましい範囲であるが、最も望まし
いのは５００’Ｃで１〜２時間保持する条件である。こ
れは温良か６００°Ｃ前後になると、粉末、メツシュの
酸化物生成か多くなって、電極の導電性に悪影響をもた
らＴ恐れがあるためである。After going through the above press molding process, the molded product with the metal mesh is placed in an electric furnace and heated at a rate of around 100°C/11°C from room temperature in an acidic atmosphere, with air flowing if necessary. The wood pulp and flocculant contained in the molded product begin to burn out at around 50°C, and these
Completely burned out at 0°C. Therefore, the heating leakage in an oxidizing atmosphere is preferably 450° to 600°C for 1 to 3 hours, but the most desirable condition is 500°C for 1 to 2 hours. be. This is because when the temperature is around 600°C, more oxides are produced in the powder and mesh, which may adversely affect the conductivity of the electrode.
木材パルプ、凝集剤を焼失、気化させた際に生じた酸化
物の還元、Ｎｉ粉末の焼結およびＮｉ粉末と金属メツシ
ュの拡散結合を目的として実施する還元性殉囲気中での
加熱処理条件は次の通りである。（１）温度＝６５０°
〜１０００℃ （２）保持時間二〇、５〜３時間 ＋３
） ｉ’囲気：水素、窒素２アルゴン、真空（１０ｔｏ
ｒｒ以下）。The heat treatment conditions in a reducing atmosphere are as follows: It is as follows. (1) Temperature = 650°
~1000℃ (2) Holding time 20, 5 to 3 hours +3
) i' Surroundings: hydrogen, nitrogen 2 argon, vacuum (10 to
rr or less).
この加熱処理条件の範囲であるならば、本発明で所望す
るアノード電極の空孔率、空孔径、壁孔径分布および比
表面積などを任意に設定することが可能であった。Within this range of heat treatment conditions, it was possible to arbitrarily set the porosity, pore diameter, wall pore diameter distribution, specific surface area, etc. of the anode electrode desired in the present invention.
（実施例１） この実施例では電極の製造方法について述べる。(Example 1) In this example, a method for manufacturing an electrode will be described.
（入試料の調整
（Ｂ）凝集剤
２１部程度の容器に水１０００部と木材パルプ５部を入
れ、１０〜２０分はど攪拌して水に十分分散させて、そ
こヘカーボニルニッケル粉末を４５部を加えて５〜１０
分はど攪拌して水性スラリーを作る。その中へあらかじ
め作っておいたポリアクリルアンド系アニオン凝集剤（
０，１％水溶ｇ）を３０部添加し、１分はど攪拌し、さ
らにあらかじめ作っておいたボ１１アクリルアンド系カ
チオン凝集剤（０，１％水溶液）を２０部添加し、１分
はど攪拌して凝秦フロックを作る。前記工程で凝集した
試料を抄造機で抄造して３０部１ｍｉ角で厚み１，２１
１１１の成形物を得た。次に線径Ｑ、 ｌ 酩で頒メ、
シュのＮｉメ、シュを成形物に積層し、プレス機で８５
にβの圧力にてＮ１メ、シ、を成形物に圧着せしめた。(Preparation of input sample (B) Put 1,000 parts of water and 5 parts of wood pulp into a container containing about 21 parts of flocculant, stir for 10 to 20 minutes to thoroughly disperse it in the water, and add 45 parts of carbonyl nickel powder to it. 5 to 10 parts
Mix thoroughly to make an aqueous slurry. A polyacrylic anionic flocculant (pre-prepared therein)
Add 30 parts of 0.1% aqueous solution g), stir for 1 minute, then add 20 parts of Bo11 acrylic and type cation flocculant (0.1% aqueous solution) prepared in advance, and stir for 1 minute. Stir to form a floc. The sample agglomerated in the above step was made into paper using a paper making machine, and 30 parts, 1 mm square, and 1.21 mm thick were made.
No. 111 molded products were obtained. Next, distribute the wire diameter Q and l,
Laminate the Ni film on the molded product and use a press machine to
The N1 pieces were crimped onto the molded product at a pressure of β.
これを電気炉に装入し、大気中において常温より１５０
℃ハの速度で５００°Ｃまで加熱し、この温度で２時間
保持して成形物に含まれる木材パルプ、凝集剤を焼失飛
散させた後、室温まで冷却した。その後、水系炉にて水
系を流しながら常温より３００℃、用の速度で６００°
Ｃまでに昇温し、これ以降は１５０’Ｃハの速度で８０
０℃まで昇温させ、８００℃で１時間保持することでＮ
ｉメ。This was charged into an electric furnace and heated to 150°C from room temperature in the atmosphere.
The molded article was heated to 500° C. at a rate of 500° C., held at this temperature for 2 hours to burn off and scatter the wood pulp and flocculant contained in the molded product, and then cooled to room temperature. After that, in a water-based furnace, the water system is heated to 300°C from room temperature and 600° at the specified speed.
The temperature was raised to 80°C, and from then on, the temperature was increased to 80°C at a rate of 150°C.
By raising the temperature to 0℃ and holding it at 800℃ for 1 hour, N
i-mail.
シーを補強材とした多孔質Ｎｉ電極板を得た。本条件で
得られた多孔質Ｎｉ＠、［板の厚さは０．８３ｍｍ。A porous Ni electrode plate using shea as a reinforcing material was obtained. Porous Ni@ obtained under these conditions [plate thickness: 0.83 mm].
空孔率は６７％２平均空孔半径は５．５μｍそして比表
面積は０．１５ｍ’／？であった。The porosity is 67%2, the average pore radius is 5.5 μm, and the specific surface area is 0.15 m'/? Met.
（実施例２）
この実施例では、実施例１で得た多孔質Ｎｉ電極板のク
リープ強度を検討した。クリープ強度は、温度：６５０
℃、雰囲気：真空、荷重８２．５ＫＶゴの条件で圧縮ク
リープ試験を行い、その時の圧縮クリープひずみの大小
によって判断した。(Example 2) In this example, the creep strength of the porous Ni electrode plate obtained in Example 1 was examined. Creep strength is temperature: 650
A compression creep test was conducted under the conditions of ℃, atmosphere: vacuum, and a load of 82.5 KV, and judgment was made based on the magnitude of the compression creep strain at that time.
比較品としては、平均粒径４．７μｍのカーボニルニッ
ケル粉末を深さ１．０！Ｉ１１の黒鉛鋳型に充填し、こ
れを水素雰囲気中７８０°Ｃ×ＩＨの焼結を行って製造
したＮｉ電極板を用いた。この比較品の空孔率は７３．
３％、平均仝孔半径は６．１μｍおよび比表面積は０．
１８ｍ／２であった。第１図に圧相白クリープ試験で得
られたクリープひずみと試験時間の関係を示す。実線１
で示す本発明品のクリープひずみは１０００時間で工）
５％前後であるのにλ・↑し、実＠２の比４品は短時間
側でも大きなりリープひずみを呈し、 １０００時間で
は５５％にもなっている。また、クリープ試験前とｉ
ｏｏｏ時間クリりプ後の空孔率、平均空孔半径および比
表面積の変化は第１表のようになる。As a comparison product, carbonyl nickel powder with an average particle size of 4.7 μm was used at a depth of 1.0! A Ni electrode plate manufactured by filling a graphite mold of I11 and sintering it at 780°C x IH in a hydrogen atmosphere was used. The porosity of this comparative product is 73.
3%, average hole radius is 6.1 μm and specific surface area is 0.
It was 18m/2. Figure 1 shows the relationship between the creep strain and test time obtained in the pressure white creep test. solid line 1
The creep strain of the product of the present invention is expressed in 1000 hours)
Even though it is around 5%, λ↑ increases, and the 4 products with actual @2 ratio exhibit large leap strain even on the short time side, reaching 55% at 1000 hours. In addition, before the creep test and i
Changes in porosity, average pore radius and specific surface area after ooo time clipping are as shown in Table 1.
第 １ 表
第１図および第１表１こ示す結果より、この実施？Ｉｌ
による電極は金属メ、シーの補修効果によりクリープ強
度が顕著に増加Ｉ−１かつ多孔質電極板の空孔特性も変
化の少ないこと？：播１２できた。1 From the results shown in Table 1 and Table 1, this implementation? Il
The creep strength of the electrode significantly increases due to the repair effect of the metal sheet I-1, and the pore characteristics of the porous electrode plate do not change much. : I was able to spread 12.
（実施例３）
この実施例では、ｉＭ径がよ）１で厚さが０．８５１！
ＩＩ前後の実施泗ＩＩ極および実施し１］２で説明１７
た比較の多孔）ＸＮｉ電極板をアノードに用いて〜１ｃ
Ｆ（コを嘴成し、その電池性能′？：ｄ〜べ１こ。なお
、電油試験はクリープ試験前と１０００時間の圧縮クリ
ープ試験を行っ１このちの′電極板の両者について実施
した。(Example 3) In this example, the iM diameter is 1 and the thickness is 0.851!
Implementation before and after II II and implementation 1] Explained in 2 17
Using a comparative porous) XNi electrode plate as an anode ~1c
The battery performance'?: d~be1.The electrohydraulic test was carried out on both the electrode plates before the creep test and after the 1000 hour compressive creep test.
八ＩＣＥ’Ｃは、リチウムアルミネートを′ＹＩＬＩ！
４質保持材として共晶組成電解質成分（４７，５本量％
炭酸リチウムー５２．５厘ｔ％炭酸カリウム）を５５重
建物倉有する５Ｑ ＩＡａ Ｘ ２ｍ１１厚の邂ｍ實板
をアノードとカソード間ｌこ配置し、燃料室２よび酸化
剤室を備え、かつ簗電子を水ね１こハウジングで電極板
と電解質板を両面から押しつけ１こ構造の単電池を構成
した。Eight ICE'C 'YILI' Lithium Aluminate!
A eutectic composition electrolyte component (47.5% by weight) is used as a quaternary retention material.
A 5Q IAa x 2m11-thick steel plate with 55 heavy-duty buildings containing lithium carbonate (52.5 t% potassium carbonate) was placed between the anode and cathode, and equipped with a fuel chamber 2 and an oxidizer chamber, and The electrode plate and electrolyte plate were pressed together from both sides in a single housing to form a unit cell with a single cell structure.
かかる構成の単電池に、燃料ガス組成はＨ２＋２０％Ｃ
０２，酸化剤カスＩ！ｌ成はＡｉｒ＋（資）％ＣＯ２か
らなるガス）ｉ ０．５ 、、ｅ／−の流量で供給し６
５０℃で電流−電圧特性の関係を測定した。In a cell with such a configuration, the fuel gas composition is H2 + 20%C.
02, Oxidizer scum I! The gas is supplied at a flow rate of 0.5, e/-6.
The relationship between current and voltage characteristics was measured at 50°C.
第２図に電流密度１０００時間で測定したアノード分極
値を示す。クリープ試験前の電極板をアノード′ｄＬ＃
に用いたときは、不実施例品と比較品で優劣は認められ
ない。１０００時間クリープ試験後の電極板のアノード
分極値をみると、本発明品はクリープ試験前の値とほぼ
同等であるのに対して、比較品のアノード分極値は極め
て大きな値となり、ＭＣＦＣの特性上好しくないことを
示（−でいる。１−またがって、金漬メ、シュで補強し
た′Ａ元四品の方が寿命特性の面で有利であることが明
らかである。FIG. 2 shows anode polarization values measured at a current density of 1000 hours. The electrode plate before the creep test is anode 'dL#
When used for this purpose, no superiority or inferiority was observed between the non-example product and the comparative product. Looking at the anode polarization value of the electrode plate after the 1000 hour creep test, the inventive product is almost the same as the value before the creep test, while the anode polarization value of the comparative product is extremely large, indicating that the characteristics of MCFC It is clear that the original four products of 'A', which are reinforced with gold pickled mesh and mesh, are more advantageous in terms of life characteristics.
以上の説明から明らかなように本発明によれば、Ｎｉ粉
末と木材パルプを水中で混合して水性スラ；１−とし、
これに凝集剤を加えて粉末をパルプに吸着凝集せしめ、
抄造によって板状の成形物を得、この成形物と金属メ、
シ、をブレス成型で１１合化した後、酸化性雰囲気と還
元性雰囲気の二つの工程で加熱処理を行うことによって
多孔負電極板？形成しているため、金属メツシーか補強
効果を発揮して耐焼結性に梗れた電極となる。そしてこ
れをＭＣＦＣのアノードに組み込むことにより、ＭＣＦ
Ｃの長期にわたる電池性能を維持することが可能となる
。As is clear from the above description, according to the present invention, Ni powder and wood pulp are mixed in water to form an aqueous slurry;
A flocculant is added to this to adsorb and agglomerate the powder into the pulp.
A plate-shaped molded product is obtained by papermaking, and this molded product and metal
After combining 11 with breath molding, heat treatment is performed in two steps in an oxidizing atmosphere and a reducing atmosphere to create a porous negative electrode plate. Because of this, the metal mesh exhibits a reinforcing effect, resulting in an electrode with excellent sintering resistance. By incorporating this into the anode of the MCFC, the MCF
It becomes possible to maintain the long-term battery performance of C.
第１図は１１Ｌ極板の圧縮クリープ試験におけるクリー
プひずみと試験時間の関係を示すグラフ、第２図はＭＣ
ＦＣの単電池でクリープ試験前と１０００時間クリープ
試験後の電極板について測定したアノード分極値の結果
を示すグラフである。
０２４ ム ε ｌＯＢ’＋
ｆｖｌ （Ｈ，ｙ、ｔｏｏ 、）第１ 図Figure 1 is a graph showing the relationship between creep strain and test time in a compression creep test of 11L electrode plate, Figure 2 is a graph showing the relationship between MC
It is a graph showing the results of anode polarization values measured for electrode plates before and after a 1000-hour creep test in a single FC cell. 024 Mu ε lOB'+
fvl (H, y, too,) Fig. 1
Claims (1)
る水性スラリーとなし、凝集剤を添加して粉末をパルプ
に吸着凝集し抄造することで得た板状の成形物に金属メ
ッシュをプレス成型によって圧着せしめた後、該成形物
を酸化性雰囲気で加熱して木材パルプを焼失飛散し、続
いて高温の還元性雰囲気で加熱して前記酸化で生じた金
属酸化物を還元するとともにＮｉ粉末を焼結することを
特徴とする溶融炭酸塩燃料電池用燃料極の製造方法。1) Mix Ni powder and wood pulp in water to make an aqueous slurry suitable for papermaking, add a flocculant, adsorb the powder to the pulp, coagulate it, and press a metal mesh onto a plate-shaped product obtained by making paper. After being compressed by molding, the molded product is heated in an oxidizing atmosphere to burn off and scatter the wood pulp, and then heated in a high-temperature reducing atmosphere to reduce metal oxides produced by the oxidation and to form Ni powder. A method for producing a fuel electrode for a molten carbonate fuel cell, the method comprising: sintering a fuel electrode for a molten carbonate fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60295422A JPS62154575A (en) | 1985-12-27 | 1985-12-27 | Manufacture of fuel electrode for molten carbonate fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60295422A JPS62154575A (en) | 1985-12-27 | 1985-12-27 | Manufacture of fuel electrode for molten carbonate fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62154575A true JPS62154575A (en) | 1987-07-09 |
| JPH0520871B2 JPH0520871B2 (en) | 1993-03-22 |
Family
ID=17820400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60295422A Granted JPS62154575A (en) | 1985-12-27 | 1985-12-27 | Manufacture of fuel electrode for molten carbonate fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62154575A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7470480B2 (en) | 2003-08-11 | 2008-12-30 | Shinko Electric Industries Co., Ltd. | Solid electrolyte fuel-cell device |
-
1985
- 1985-12-27 JP JP60295422A patent/JPS62154575A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7470480B2 (en) | 2003-08-11 | 2008-12-30 | Shinko Electric Industries Co., Ltd. | Solid electrolyte fuel-cell device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0520871B2 (en) | 1993-03-22 |
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