JPH0261533B2 - - Google Patents
Info
- Publication number
- JPH0261533B2 JPH0261533B2 JP61220306A JP22030686A JPH0261533B2 JP H0261533 B2 JPH0261533 B2 JP H0261533B2 JP 61220306 A JP61220306 A JP 61220306A JP 22030686 A JP22030686 A JP 22030686A JP H0261533 B2 JPH0261533 B2 JP H0261533B2
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- plate
- porous
- thin plate
- powder
- 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
-
- 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
- H01M4/8605—Porous electrodes
- H01M4/8621—Porous electrodes containing only metallic or ceramic material, e.g. made by sintering or sputtering
-
- 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
-
- 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
-
- 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
- H01M8/14—Fuel cells with fused electrolytes
- H01M2008/147—Fuel cells with molten carbonates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0048—Molten electrolytes used at high temperature
- H01M2300/0051—Carbonates
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Inert Electrodes (AREA)
Description
〔産業上の利用分野〕
この発明は、NiまたはNi合金製のものと同等
のクリープ強度を有し、かつこれと同等の電池特
性を示し、したがつて長期に亘つてすぐれた性能
を発揮する溶融炭酸塩型燃料電池のアノード電極
用多孔質Cu合金焼結薄板の製造法に関するもの
である。
〔従来の技術〕
従来、溶融炭酸塩型燃料電池のアノード電極と
して、Niや、Ni−Co系合金、Ni−Ag系合金、
またはNi−Cr系合金などのNi合金からなる多孔
質焼結薄板が用いられ、この多孔質NiまたはNi
合金焼結薄板が、
原料粉末として、Ni粉末や、上記の各種のNi
合金粉末を用い、
これらのNiまたはNi合金粉末よりドクターブ
レード法により板状成形体を形成し、脱バインダ
して固化した後、
上記板状成形体を、真空、あるいは水素雰囲気
中、900〜1000℃の温度で焼結することによつて
製造されることもよく知られている。
〔発明が解決しようとする問題点〕
一方、上記の多孔質NiまたはNi合金焼結薄板
は、原料粉末として用いるNi粉末またはNi合金
粉末が高価であるため、これをCu合金粉末を用
いてコスト低減をはかる試みもなされたが、Cu
合金粉末は、真空あるいは水素などの還元性雰囲
気中での焼結性が著しく悪く、十分に実用に供す
ることができる多孔質Cu合金焼結薄板を製造す
ることはきわめて困難であるのが現状である。
〔問題点を解決するための手段〕
そこで、本発明者等は、上述のような観点か
ら、多孔質NiまたはNi合金焼結薄板と同等の高
いクリープ強度を有し、かつ溶融炭酸塩燃料電池
のアノード電極として用いた場合に、同じくこれ
と同等のすぐれた電池特性を長期に亘つて発揮す
る多孔質NCu合金焼結薄板を製造すべく研究を
行なつた結果、原料粉末として、Crを含有する
Cu合金粉末を用いてドクターブレード法により
形成した板状成形体は、真空雰囲気や、還元性雰
囲気中では十分に焼結しないが、これを空気など
の酸化性雰囲気中、所定温度に加熱すると、板状
酸化焼結体となり、ついでこの板状酸化焼結体
を、水素を含む還元性雰囲気中で加熱還元し、主
としてCuを還元してやると、CuまたはCu−Cr系
合金の素地中に微細なCr酸化物粒子が均一に分
散した組織を有する多孔質Cu合金焼結薄板とな
り、この多孔質Cu合金焼結薄板においては、前
記素地によつて、燃料電池運転で、すぐれた耐食
および耐浸炭性を発揮し、かつ高い導電性が確保
されることから、高電流密度での発電が可能とな
り、さらに前記Cr酸化物粒子によつて、同じく
燃料電池運転下ですぐれたクリープ強度を発揮す
るようになるという知見を得たのである。
この発明は、上記知見にもとづいてなされたも
のであつて、
原料粉末として、２〜30μｍの平均粒径を有
し、かつCrを0.1〜30重量％含有するCu合金粉末
を用い、
このCu合金粉末からドクターブレード法によ
り板状成形体を形成し、脱バインダして固化した
後、
上記板状成形体を、酸化性雰囲気中で400〜600
℃の温度に加熱して、酸化および焼結し、
ついで、この板状酸化焼結体を、水素を含む還
元性雰囲気中で650〜900℃の温度に加熱して、主
としてCuを還元することによつて、CuまたはCu
−Cr系合金の素地中に微細なCr酸化物粒子が均
一に分散した組織を有し、かつ溶融炭酸塩型燃料
電池のアノード電極として用いるのに適した多孔
Cu合金焼結薄板を製造する方法に特徴を有する
ものである。
つぎに、この発明の方法において、製造条件を
上記の通りに限定した理由を説明する。
(a) 原料粉末の平均粒径
アノード電極として用いるためには、焼結薄
板は50〜80％の気孔率をもつことが必要であ
り、したがつて、原料粉末の平均粒径が2μｍ
未満では、焼結薄板の気孔率が50％未満になつ
てしまい、所望の電池特性を確保することがで
きず、一方その平均粒径が30μｍを越えると、
焼結薄板は80％を越えた気孔率をもつようにな
つて所望の強度を確保することが困難となるこ
とから、その平均粒径を２〜30μｍと定めた。
(b) Cu合金粉末のCr含有量
Cr成分には、主として焼結薄板の素地に微
細に分散析出するCr酸化物粒子を形成してク
リープ強度を向上させる作用があるが、その含
有量が0.1重量％未満では前記作用に所望の効
果が得られず、一方その含有量が30重量％を越
えると、焼結薄板中に粗大な酸化物粒子として
存在するようになつてクリープ強度に低下傾向
が現われるようになるばかりでなく、板状酸化
焼結体の加熱還元時に割れが発生し易くなるこ
とから、その含有量を0.1〜30重量％と定めた。
(c) 酸化焼結温度
例えば温度：300℃では10時間程度を必要と
するように、その温度が400℃未満では板状成
形体の酸化焼結に長時間を要して生産者が悪
く、一方その温度が800℃を越えると、緻密化
して所望の気孔率をもつた焼結薄板を製造する
ことが困難になることから、その温度を400〜
800℃と定めた。
(d) 環元温度
その温度が650℃未満では所定の環元に長時
間を要して能率的でなく、一方その温度が900
℃を越えるとCr酸化物も還元されるようにな
つて所望のクリープ強度を確保することができ
なくなることから、その温度を650〜900℃と定
めた。
〔実施例〕
つぎに、この発明の方法を実施例により具体的
に説明する。
原料粉末として、それぞれ第１表に示される
Cr含有量および平均粒径のCu合金粉末を用意し、
これに別途用意意した有機バインダとしてのポリ
ビニルブチラール（PVB）、溶剤としてのトルエ
ンとエタノールの重量比で１：１の混合液、可塑
剤としてのポリエチレングリコール、および解膠
剤としてのオレイン酸メチルを、重量比で、原料
粉末：有機バインダ：溶剤：可塑剤：解膠剤＝
90：２：10：２：１の割合で配合し、混合撹拌し
てスラリーとし、このスラリーをドクターブレー
ドを用いてキヤリヤ−テープ上に１mmの厚さに塗
布し、赤外線乾燥機にて溶剤を揮発させて板状成
形体とし、ついでこれら板状成形体を、空気中で
温度：350℃に30分間加熱保持し、脱バインダし
て固化した後、同じく空気中で、温度：500℃に
２時間加熱保持して酸化および焼結し、なお、こ
の場合Cu合金粉末の酸化の進行とともに焼結は
進行するが、粉末の表面が一様に酸化されると焼
結の進行は著しく緩慢になるため、焼結体の緻密
化は進行せず、この結果多孔質体が形成されるよ
うになり、引続いてこの結果の板状酸化焼結体
を、水素気流中で、温度：800℃に２時間加熱保
持して、主としてCuを還元することによつて本
発明法１〜６および比較法１〜４をそれぞれ実施
し、
[Industrial Application Field] This invention has a creep strength equivalent to that made of Ni or Ni alloy, and exhibits the same battery characteristics as those made of Ni or Ni alloy, and therefore exhibits excellent performance over a long period of time. This invention relates to a method for manufacturing a porous Cu alloy sintered thin plate for an anode electrode of a molten carbonate fuel cell. [Prior art] Conventionally, Ni, Ni-Co alloys, Ni-Ag alloys,
Alternatively, a porous sintered thin plate made of Ni alloy such as Ni-Cr alloy is used, and this porous Ni or Ni
The alloy sintered thin plate is made of Ni powder or the various types of Ni mentioned above as raw material powder.
Using the alloy powder, a plate-shaped compact is formed from these Ni or Ni alloy powders by a doctor blade method, the binder is removed and the plate-shaped compact is solidified, and then the plate-shaped compact is heated in a vacuum or in a hydrogen atmosphere at It is also well known that they can be produced by sintering at temperatures of .degree. [Problems to be Solved by the Invention] On the other hand, since the Ni powder or Ni alloy powder used as the raw material powder is expensive, the above-mentioned porous Ni or Ni alloy sintered thin plate is made by using Cu alloy powder to reduce the cost. Although attempts have been made to reduce Cu
Alloy powder has extremely poor sinterability in a vacuum or a reducing atmosphere such as hydrogen, and it is currently extremely difficult to produce porous Cu alloy sintered thin sheets that can be used in practical applications. be. [Means for Solving the Problems] Therefore, from the above-mentioned viewpoint, the present inventors have developed a molten carbonate fuel cell that has a high creep strength equivalent to that of a porous Ni or Ni alloy sintered thin plate. As a result of conducting research to produce a porous NCu alloy sintered thin plate that exhibits the same excellent battery characteristics over a long period of time when used as an anode electrode, we found that the raw material powder contains Cr. do
A plate-shaped compact formed by the doctor blade method using Cu alloy powder does not sinter sufficiently in a vacuum atmosphere or a reducing atmosphere, but if it is heated to a predetermined temperature in an oxidizing atmosphere such as air, A plate-shaped oxidized sintered body is formed, and this plate-shaped oxidized sintered body is then heated and reduced in a reducing atmosphere containing hydrogen to mainly reduce Cu. The porous Cu alloy sintered thin plate has a structure in which Cr oxide particles are uniformly dispersed, and the porous Cu alloy sintered thin plate has excellent corrosion resistance and carburization resistance during fuel cell operation due to the substrate. It also exhibits high electrical conductivity, making it possible to generate electricity at high current density.Furthermore, due to the Cr oxide particles, it also exhibits excellent creep strength under fuel cell operation. We have obtained the knowledge that this will be the case. The present invention was made based on the above findings, and uses a Cu alloy powder having an average particle size of 2 to 30 μm and containing 0.1 to 30% by weight of Cr as a raw material powder. A plate-shaped molded body is formed from the powder by a doctor blade method, the binder is removed, and the plate-shaped molded body is solidified.
℃ to oxidize and sinter the plate-shaped oxidized sintered body to a temperature of 650 to 900℃ in a reducing atmosphere containing hydrogen to mainly reduce Cu. Depending on Cu or Cu
-Has a structure in which fine Cr oxide particles are uniformly dispersed in the Cr-based alloy matrix, and is porous and suitable for use as an anode electrode for molten carbonate fuel cells.
This method is characterized by a method for producing a Cu alloy sintered thin plate. Next, the reason why the manufacturing conditions are limited as described above in the method of the present invention will be explained. (a) Average particle size of the raw material powder In order to use it as an anode electrode, the sintered thin plate must have a porosity of 50 to 80%, so the average particle size of the raw material powder is 2 μm.
If the average particle size exceeds 30 μm, the porosity of the sintered thin plate will be less than 50%, making it impossible to secure the desired battery characteristics.
Since the sintered thin plate has a porosity exceeding 80%, making it difficult to secure the desired strength, the average particle size was determined to be 2 to 30 μm. (b) Cr content of Cu alloy powder The Cr component mainly has the effect of forming Cr oxide particles that are finely dispersed and precipitated in the base material of the sintered thin plate to improve creep strength. If the content is less than 30% by weight, the desired effect cannot be obtained, while if the content exceeds 30% by weight, the oxide particles will exist as coarse oxide particles in the sintered thin plate, and the creep strength will tend to decrease. The content was determined to be 0.1 to 30% by weight because not only do they appear, but also cracks are likely to occur when the plate-shaped oxidized sintered body is heated and reduced. (c) Oxidation sintering temperature For example, at a temperature of 300°C, it takes about 10 hours, and if the temperature is less than 400°C, it takes a long time to oxidize the plate-shaped compact, which is bad for producers. On the other hand, if the temperature exceeds 800℃, it becomes difficult to produce a sintered thin plate with the desired porosity due to densification.
The temperature was set at 800℃. (d) Ring element temperature If the temperature is less than 650°C, it will take a long time to process a given ring element, making it inefficient.
If the temperature exceeds 650 to 900°C, Cr oxides will also be reduced, making it impossible to secure the desired creep strength. Therefore, the temperature was set at 650 to 900°C. [Example] Next, the method of the present invention will be specifically explained with reference to Examples. Each of the raw material powders is shown in Table 1.
Prepare Cu alloy powder with Cr content and average particle size,
To this, separately prepared polyvinyl butyral (PVB) as an organic binder, a mixture of toluene and ethanol in a weight ratio of 1:1 as a solvent, polyethylene glycol as a plasticizer, and methyl oleate as a peptizer were added. , in weight ratio, raw material powder: organic binder: solvent: plasticizer: deflocculant =
Blend in a ratio of 90:2:10:2:1, mix and stir to form a slurry, apply this slurry to a thickness of 1 mm on a carrier tape using a doctor blade, and remove the solvent using an infrared dryer. This plate-shaped molded body is volatilized to form a plate-shaped molded body, and then heated and held in the air at a temperature of 350°C for 30 minutes to remove the binder and solidify. Oxidation and sintering are carried out by heating and holding for a period of time. In this case, sintering progresses as the oxidation of the Cu alloy powder progresses, but if the surface of the powder is uniformly oxidized, the sintering progresses significantly. Therefore, the densification of the sintered body does not proceed, and as a result, a porous body is formed.Subsequently, the resulting plate-shaped oxidized sintered body is heated to 800℃ in a hydrogen stream. Methods 1 to 6 of the present invention and comparative methods 1 to 4 were carried out by heating and holding for 2 hours to mainly reduce Cu, and
第１表に示される結果から、本発明法１〜６に
よつて製造されたアノード電極は、いずれも従来
法によつて製造されたアノード電極と同等の高い
クリープ強度をもつので、経時的厚み変化が小さ
く、長期に亘つてすぐれた電池特性を発揮するの
に対して、比較法１〜４で製造されたアノード電
極に見られるように、原料粉末としてのCu合金
粉末の平均粒径およびCr含有量のいずれかでも
この発明の範囲から外れると、クリープ強度不足
が原因して厚み変化率が大きくなり、電池特性の
経時的低下が著しいことが明らかである。
上述のように、この発明の方法によれば、高い
クリープ強度を有する多孔質Cu合金焼結薄板を
低コストで製造することができ、したがつてこの
多孔質Cu合金焼結薄板を溶融炭酸塩型燃料電池
のアノード電極として用いた場合には、従来多孔
質NiまたはNi合金焼結薄板を用いた場合と同様
に著しく長期に亘つてすぐれた電池特性を発揮す
るなど工業上有用な効果がもたらされるのであ
る。
From the results shown in Table 1, the anode electrodes manufactured by methods 1 to 6 of the present invention all have high creep strength equivalent to that of anode electrodes manufactured by the conventional method, so the thickness changes over time. On the other hand, as seen in the anode electrodes manufactured by Comparative Methods 1 to 4, the average particle size of the Cu alloy powder as the raw material powder and the Cr It is clear that if any of the contents deviates from the range of the present invention, the rate of change in thickness increases due to insufficient creep strength, and the battery characteristics deteriorate significantly over time. As described above, according to the method of the present invention, a porous Cu alloy sintered thin plate having high creep strength can be produced at low cost, and the porous Cu alloy sintered thin plate can be prepared by molten carbonate. When used as an anode electrode in a type fuel cell, it has industrially useful effects such as exhibiting excellent cell characteristics over a long period of time, similar to when using conventional porous Ni or Ni alloy sintered thin plates. It is possible.
Claims (1)
し、かつCrを0.1〜30重量％含有するCu合金粉末
を用い、 このCu合金粉末からドクターブレード法によ
り板状成形体を形成し、脱バインダして固化した
後、 上記板状成形体を、酸化性雰囲気中で400〜800
℃の温度に加熱して、酸化および焼結し、 ついで、この板状酸化焼結体を、水素を含む還
元性雰囲気中で650〜900℃の温度に加熱し、主と
してCuを還元して、CuまたはCu−Cr系合金の素
地中に微細なCr酸化物粒子が均一に分散した組
織を有する多孔質Cu合金焼結薄板を製造するこ
とを特徴とする溶融炭酸塩型燃料電池のアノード
電極用多孔質Cu合金焼結薄板の製造法。[Claims] 1. A Cu alloy powder having an average particle size of 2 to 30 μm and containing 0.1 to 30% by weight of Cr is used as a raw material powder, and this Cu alloy powder is formed into a plate shape by a doctor blade method. After forming a body, removing the binder and solidifying it, the plate-shaped molded body is heated to 400 to 800
℃ to oxidize and sinter the plate-like oxidized sintered body, and then heat the plate-shaped oxidized sintered body to a temperature of 650 to 900℃ in a reducing atmosphere containing hydrogen to mainly reduce Cu. For an anode electrode of a molten carbonate fuel cell characterized by manufacturing a porous Cu alloy sintered thin plate having a structure in which fine Cr oxide particles are uniformly dispersed in a base of Cu or Cu-Cr alloy. Manufacturing method of porous Cu alloy sintered thin plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61220306A JPS6376833A (en) | 1986-09-18 | 1986-09-18 | Manufacture of porous cu-alloy sintered sheet for anode of fused carbonate fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61220306A JPS6376833A (en) | 1986-09-18 | 1986-09-18 | Manufacture of porous cu-alloy sintered sheet for anode of fused carbonate fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6376833A JPS6376833A (en) | 1988-04-07 |
| JPH0261533B2 true JPH0261533B2 (en) | 1990-12-20 |
Family
ID=16749076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61220306A Granted JPS6376833A (en) | 1986-09-18 | 1986-09-18 | Manufacture of porous cu-alloy sintered sheet for anode of fused carbonate fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6376833A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7829012B2 (en) * | 2005-12-19 | 2010-11-09 | Worldwide Energy, Inc. Of Delaware | Enhancement of thermal stability of porous bodies comprised of stainless steel or an alloy |
| WO2017221500A1 (en) * | 2016-06-23 | 2017-12-28 | 本田技研工業株式会社 | Method for producing porous metal body and method for producing electrode catalyst |
| CN112048635A (en) * | 2020-08-25 | 2020-12-08 | 西安理工大学 | A kind of micro-nano graded porous copper and preparation method thereof |
-
1986
- 1986-09-18 JP JP61220306A patent/JPS6376833A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6376833A (en) | 1988-04-07 |
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