JPH0766824B2 - Materials for molten carbonate fuel cells - Google Patents
Materials for molten carbonate fuel cellsInfo
- Publication number
- JPH0766824B2 JPH0766824B2 JP62067623A JP6762387A JPH0766824B2 JP H0766824 B2 JPH0766824 B2 JP H0766824B2 JP 62067623 A JP62067623 A JP 62067623A JP 6762387 A JP6762387 A JP 6762387A JP H0766824 B2 JPH0766824 B2 JP H0766824B2
- Authority
- JP
- Japan
- Prior art keywords
- molten carbonate
- carbonate fuel
- materials
- corrosion resistance
- 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.)
- 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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
-
- 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
- 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
-
- 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)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Fuel Cell (AREA)
- Inert Electrodes (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は強度および耐食性に優れ、かつ市場性、加工
性、経済性に優れた溶融炭酸塩型燃料電池構成材料に関
するものである。TECHNICAL FIELD The present invention relates to a molten carbonate fuel cell constituent material which is excellent in strength and corrosion resistance, and is excellent in marketability, processability and economy.
［従来の技術］ 溶融炭酸塩型燃料電池は、エネルギー変換効率が高く、
公害発生がなく、かつ高価な触媒を必要としない等の利
点があることから、次世代の電源として有望視されてお
り、現在は小規模な電池を組んで耐久性の検討を行うと
共に積層技術の開発や、大規模化のための検討および電
池の電極材料やその他の構成材料の開発が進められてい
る。[Prior Art] A molten carbonate fuel cell has high energy conversion efficiency,
It is promising as a next-generation power source because it has advantages such as no pollution and no need for expensive catalysts. Currently, small-scale batteries are assembled to study durability and stacking technology. , Development for large scale, and development of battery electrode materials and other constituent materials.
［発明が解決しようとする問題点］ 現状での問題として、溶融炭酸塩型燃料電池の電極やセ
パレーターなどの電池構成材料は一般に腐食を受け易く
長期の耐久性を有しないという問題やニッケルカソード
電極が溶解し、アノード近傍で析出して電池寿命を短く
するという問題がある。[Problems to be Solved by the Invention] As a current problem, battery constituent materials such as electrodes and separators of molten carbonate fuel cells are generally susceptible to corrosion and do not have long-term durability, and nickel cathode electrodes. Is dissolved and deposited near the anode, shortening the battery life.
これらの問題を解決するための種々の検討（たとえば、
アルミナ酸化被膜形成による防食：特開昭58−217677、
フェロアロイ電極：特開昭58−155662、電解質保持体に
関するもの：特開昭56−82583、特開昭58−117656、リ
チウム添加金属酸化物粉末電極：特開昭58−165253、リ
チウムコバルトオキサイド微粒子焼結体を電極とする燃
料電池：特開昭60−117566、高耐食性金属材料と複合酸
化物より成る集電体：特開昭59−230263、電気化学的に
活性な金属で被覆したセラミック粒子からなる電極材
料：特開昭57−92753）が行われているが、いずれも市
場性、加工性および経済性の観点から好ましくない。Various studies to solve these problems (eg,
Corrosion protection by forming alumina oxide film: JP-A-58-217677,
Ferroalloy electrode: JP-A-58-155662, electrolyte holder: JP-A-56-82583, JP-A-58-117656, lithium-added metal oxide powder electrode: JP-A-58-165253, lithium cobalt oxide fine particle firing Fuel cell using binder as electrode: JP-A-60-117566, current collector consisting of highly corrosion resistant metal material and complex oxide: JP-A-59-230263, from ceramic particles coated with electrochemically active metal Electrode material: JP-A-57-92753) has been carried out, but all of them are not preferable from the viewpoint of marketability, processability and economic efficiency.
上記した問題点に鑑み、本発明においては強度および耐
食性に優れ、かつ市場性、加工性および経済性の良好な
溶融炭酸塩型燃料電池構成材料を提供することを目的と
している。In view of the above-mentioned problems, it is an object of the present invention to provide a molten carbonate fuel cell constituent material which is excellent in strength and corrosion resistance and has good marketability, processability and economical efficiency.
［問題点を解決する為の手段］ 上記問題点を解決することのできた本発明の溶融炭酸塩
型燃料電池構成材料とは Cr:0.5〜20％（重量％、以下同じ意味） Al:0.5〜10％ Co:1.0〜７％および／またはNi:0.5〜７％未満 残部Feおよび不可避不純物からなることを構成要旨と
し、必要によりこれらにSiを含有させることにより溶融
炭酸塩環境下とくにその気相および気液界面部での耐食
性を向上させることができ、またCrを0.5〜10％に限定
すると特にσ脆性に優れたものとなる。[Means for Solving Problems] The molten carbonate fuel cell constituent material of the present invention, which was able to solve the above problems, is Cr: 0.5 to 20% (weight%, hereinafter the same meaning) Al: 0.5 to 10% Co: 1.0 to 7% and / or Ni: 0.5 to less than 7% The main point of the constitution is to consist of the balance Fe and unavoidable impurities. If necessary, Si is contained in the molten carbonate environment, especially in the vapor phase. Also, the corrosion resistance at the gas-liquid interface can be improved, and if Cr is limited to 0.5 to 10%, the σ brittleness becomes particularly excellent.
［作用］ 本発明者等は溶融炭酸塩型燃料電池構成材料について種
々検討した結果、強度に優れ、かつ市場性、加工性およ
び経済性の良好な鉄系材料を基材とし、耐食性に優れた
酸化物被膜を形成させるために必要な後述の合金元素を
見い出し本発明を完成した。即ちCr,AlはLi2CO3およびK
2CO3よりなる溶融炭酸塩環境下で耐食性に優れたリチウ
ムクロメート被膜及びリチウムアルミネート被膜をそれ
ぞれ形成する。またCoおよび／またはNiはこれらの被膜
と素材間の密着性を強固にする働きを有する。また、特
にSiは粒界を安定化させ気液界面部での耐食性を向上さ
せCrの添加量を限定するとσ脆性（硬くて脆いσ相析出
による脆化）の改善を可能とする。この溶融炭酸塩型燃
料電池構成材料は使用中に若干のLi及びＫがドーピング
されるが、その後は長時間腐食環境に曝されても変質せ
ず、鉄系材料を防食する効果を持つ。[Function] As a result of various studies on the molten carbonate fuel cell constituent materials, the present inventors have found that the base material is an iron-based material having excellent strength and good marketability, processability, and economic efficiency, and has excellent corrosion resistance. The present invention has been completed by finding the alloying elements described below necessary for forming an oxide film. That is, Cr and Al are Li 2 CO 3 and K
A lithium chromate film and a lithium aluminate film having excellent corrosion resistance are formed in a molten carbonate environment of 2 CO 3 , respectively. Further, Co and / or Ni has a function of strengthening the adhesion between these coatings and the material. Further, particularly, Si stabilizes the grain boundary, improves the corrosion resistance at the gas-liquid interface portion, and limits the addition amount of Cr, it is possible to improve σ brittleness (brittleness due to hard and brittle σ phase precipitation). Although this molten carbonate fuel cell constituent material is doped with a little Li and K during use, it does not deteriorate even after being exposed to a corrosive environment for a long period of time, and has an effect of preventing corrosion of the iron-based material.
次に各合金元素の添加限定量および限定理由について述
べる。Next, the limited amount of addition of each alloying element and the reason for limitation will be described.
Cr: Crは溶融炭酸塩浴中で安定なリチウムクロメート被膜を
形成する元素であり、その効果を有効に発揮させるには
0.5〜20％の含有量が必要である。ただCr単独ではフェ
ロクロム程度のCrが含有されていないと素材の防食効果
を十分に発揮する程度のリチウムクロメートが生成され
ず、Al,Ni,Coなど他の金属元素あるいは酸化物と共存す
ることによって、低Cr含有量でも耐食性の良好な被膜を
形成する。またσ相の析出は高Crのときに起りやすいた
め、σ脆性を考慮すると0.5〜10％が良い。Cr: Cr is an element that forms a stable lithium chromate film in a molten carbonate bath, and in order to exert its effect effectively
A content of 0.5-20% is required. However, Cr alone does not generate lithium chromate to the extent that it sufficiently exhibits the anticorrosive effect of the material unless it contains Cr, which is about the level of ferrochrome, and it coexists with other metal elements or oxides such as Al, Ni, and Co. It forms a film with good corrosion resistance even with a low Cr content. Further, the precipitation of the σ phase is likely to occur when the content of Cr is high, so 0.5 to 10% is preferable in consideration of σ brittleness.
Al: Alは溶融炭酸塩浴中で単独で安定なリチウムアルミネー
ト被膜を形成し、電極材料の耐食性を著しく向上させ
る。0.5％未満では耐食性改善効果が小さく、10％を超
えると被膜の密着性が低下し、耐食性が低下する。Al: Al alone forms a stable lithium aluminate film in the molten carbonate bath, and significantly improves the corrosion resistance of the electrode material. If it is less than 0.5%, the effect of improving the corrosion resistance is small, and if it exceeds 10%, the adhesion of the coating film is deteriorated and the corrosion resistance is deteriorated.
Co: Coは鉄系素材と被膜、すなわちリチウムクロメート被膜
やリチウムアルミネート被膜の密着性改善に有効な元素
であり、鉄系材料の表面に生成するスピネル酸化物をア
モルファス化することにより密着性を改善する効果があ
る。また、高Crの場合に生成しやすいσ相の析出を抑制
する効果も有する。但し1.0％未満では顕著な効果が認
められない。一方Co含有量が多過ぎると溶出したCoがア
ノード近傍に析出して電池性能低下の原因となるので７
％を上限とした。Co: Co is an element that is effective for improving the adhesion between iron-based materials and coatings, that is, lithium chromate coatings and lithium aluminate coatings, and improves adhesion by amorphizing the spinel oxide that forms on the surface of iron-based materials. There is an improving effect. It also has the effect of suppressing the precipitation of the σ phase, which tends to be generated in the case of high Cr. However, if it is less than 1.0%, no remarkable effect is observed. On the other hand, if the Co content is too high, the eluted Co will be deposited near the anode and cause deterioration of battery performance.
% Was set as the upper limit.
Ni: NiはCoと同様の効果があり、またCr酸化物やAl酸化物中
に共存すると、被膜の防食性能を向上させる効果があ
る。0.5％未満では顕著な効果が認められず、Ni含有量
が多過ぎると溶出したNiがアノード近傍に析出して電池
性能低下の原因となるので７％未満とした。Ni: Ni has the same effect as Co, and when coexisting in Cr oxide or Al oxide, it has the effect of improving the anticorrosion performance of the coating. If it is less than 0.5%, no remarkable effect is observed, and if the Ni content is too large, the eluted Ni is deposited in the vicinity of the anode and causes deterioration of battery performance.
Si: Siは溶融炭酸塩環境化特に気液界面部での材料表層部の
結晶粒界を安定化させ耐食性向上に効果がある。しかし
0.5％未満ではその効果が著しく低下し、一方10％を超
えるとSiO2が大量に生成して耐食性を低下させる。Si: Si has an effect of improving the corrosion resistance by stabilizing the crystal grain boundary of the material surface layer at the gas-liquid interface, especially in the environment of molten carbonate. However
If it is less than 0.5%, the effect is remarkably reduced, while if it exceeds 10%, a large amount of SiO 2 is produced and the corrosion resistance is lowered.
［実施例］ 第１表に示す組成の合金を650℃、62mol％Li2CO3＋38mo
l％K2CO3浴中に浸漬し１カ月後の腐食率およびσ相析出
の有無を調べた結果を第１表に示す（成分係数は重量％
を意味し残りはFeおよび不可避不純物である）。[Example] An alloy having the composition shown in Table 1 was used at 650 ° C and 62 mol% Li 2 CO 3 + 38mo.
Table 1 shows the results of examining the corrosion rate and the presence or absence of σ phase precipitation one month after immersion in a l% K 2 CO 3 bath.
Means the rest is Fe and inevitable impurities).
No.1〜６は本発明で限定した成分組成の合金、No.7〜14
は比較例である。Nos. 1 to 6 are alloys of the composition limited by the present invention, Nos. 7 to 14
Is a comparative example.
No.1〜６は腐食率が優れており、Cr10％以下のものは本
発明例，比較例ともにσ脆性にすぐれている。Nos. 1 to 6 are excellent in corrosion rate, and those having Cr of 10% or less are excellent in σ brittleness in both the present invention and comparative examples.
［発明の効果］ 以上のように本発明の溶融炭酸塩型燃料電池構成材料は
強度および耐食性に優れ、かつ市場性、加工性、経済性
に優れたものである。 [Advantages of the Invention] As described above, the molten carbonate fuel cell constituent material of the present invention is excellent in strength and corrosion resistance, and is excellent in marketability, processability, and economy.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 藤原 和雄 兵庫県神戸市北区松が枝町３−４−６ (72)発明者 鳥井 康司 兵庫県加古川市米田町平津580 (72)発明者 中山 武典 兵庫県神戸市東灘区魚崎中町１−３−１− 604 審判の合議体 審判長 西 義之 審判官 小野 秀幸 審判官 相沢 旭 (56)参考文献 特開 昭54−3236（ＪＰ，Ａ) 特開 昭61−216256（ＪＰ，Ａ) 特公 平４−13825（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuo Fujiwara 3-4-6 Matsugaeda-cho, Kita-ku, Kobe-shi, Hyogo (72) Inventor Koji Torii Hiraizu 580, Yoneda-cho, Kakogawa-shi, Hyogo (72) Inventor Takenori Nakayama Hyogo 1-3-1 -604, Uozaki Naka-cho, Higashinada-ku, Kobe-shi, Japan Judgment Panel Judge Yoshiyuki Nishi Judge Hideyuki Ono Judge Asahi Aizawa (56) Reference JP 54-3236 (JP, A) JP 61 -216256 (JP, A) Japanese Patent Publication 4-13825 (JP, B2)
Claims (4)
料。1. Cr: 0.5 to 20% (weight%, the same meaning hereinafter) Al: 0.5 to 10% Co: 1.0 to 7% and / or Ni: less than 0.5 to 7% The balance consists of Fe and unavoidable impurities. Characteristic molten carbonate fuel cell constituent material.
10％とした溶融炭酸塩型電池構成材料。2. In the claim 1, Cr: 0.5 to
10% molten carbonate type battery constituent material.
料。3. Cr: 0.5 to 20% Al: 0.5 to 10% Co: 1.0 to 7% and / or Ni: 0.5 to less than 7% Si: 0.5 to 10% The balance consists of Fe and inevitable impurities. Molten carbonate fuel cell constituent material.
10％とした溶融炭酸塩型電池構成材料。4. In claim 3, Cr: 0.5-
10% molten carbonate type battery constituent material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62067623A JPH0766824B2 (en) | 1987-03-20 | 1987-03-20 | Materials for molten carbonate fuel cells |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62067623A JPH0766824B2 (en) | 1987-03-20 | 1987-03-20 | Materials for molten carbonate fuel cells |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63236267A JPS63236267A (en) | 1988-10-03 |
| JPH0766824B2 true JPH0766824B2 (en) | 1995-07-19 |
Family
ID=13350287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62067623A Expired - Lifetime JPH0766824B2 (en) | 1987-03-20 | 1987-03-20 | Materials for molten carbonate fuel cells |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0766824B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AUPQ078999A0 (en) * | 1999-06-04 | 1999-06-24 | Ceramic Fuel Cells Limited | Air-side solid oxide fuel cell components |
| AU778950B2 (en) * | 1999-06-04 | 2004-12-23 | Ceramic Fuel Cells Limited | Air-side solid oxide fuel cell components |
| NL1012823C2 (en) * | 1999-08-13 | 2001-02-19 | Stichting Energie | Corrosion resistant separator plate. |
| CN104018030B (en) * | 2014-05-23 | 2016-04-13 | 大连理工大学 | High-strength and high-plastic seawater corrosion-resistant alloy, its preparation method and application |
-
1987
- 1987-03-20 JP JP62067623A patent/JPH0766824B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63236267A (en) | 1988-10-03 |
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