JPH04303565A - Cathode material for high-temperature fuel cell and manufacture thereof - Google Patents
Cathode material for high-temperature fuel cell and manufacture thereofInfo
- Publication number
- JPH04303565A JPH04303565A JP3089370A JP8937091A JPH04303565A JP H04303565 A JPH04303565 A JP H04303565A JP 3089370 A JP3089370 A JP 3089370A JP 8937091 A JP8937091 A JP 8937091A JP H04303565 A JPH04303565 A JP H04303565A
- Authority
- JP
- Japan
- Prior art keywords
- cathode material
- temperature
- temperature fuel
- fuel cell
- oxidizing atmosphere
- 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
- 239000000446 fuel Substances 0.000 title claims abstract description 23
- 239000010406 cathode material Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims 3
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 238000010304 firing Methods 0.000 claims abstract description 6
- 229910052788 barium Inorganic materials 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- HBAGRTDVSXKKDO-UHFFFAOYSA-N dioxido(dioxo)manganese lanthanum(3+) Chemical group [La+3].[La+3].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O HBAGRTDVSXKKDO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 2
- 230000008859 change Effects 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000007812 deficiency Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910002328 LaMnO3 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002230 La2Zr2O7 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910009567 YMnO3 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
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
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
-
- 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
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、新規な高温型燃料電池
用カソード材料に関するものである。さらに詳しくいえ
ば、本発明は、特に安定化ジルコニアを固体電解質とす
る高温型燃料電池に適した、高温安定性等に優れた改良
された高温型燃料電池用カソード材料に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cathode material for high-temperature fuel cells. More specifically, the present invention relates to an improved cathode material for high-temperature fuel cells that is particularly suitable for high-temperature fuel cells using stabilized zirconia as a solid electrolyte and has excellent high-temperature stability.
【０００２】0002
【従来の技術】燃料電池は、水素、一酸化炭素、炭化水
素等の燃焼性化学物質やそれを含有する燃料を活物質に
用い、該化学物質や燃料の酸化反応を電気化学的に行わ
せ、酸化過程におけるエネルギー変化を直接的に電気エ
ネルギーに変換させる電池であって、高いエネルギー変
換効率を期待しうるものである。[Prior Art] Fuel cells use combustible chemicals such as hydrogen, carbon monoxide, and hydrocarbons and fuel containing them as active materials, and electrochemically carry out oxidation reactions of the chemicals and fuel. , a battery that directly converts the energy change during the oxidation process into electrical energy, and can be expected to have high energy conversion efficiency.
【０００３】中でも特に高い効率を期待しうるものとし
て、近年、第一世代のリン酸型、第二世代の溶融炭酸塩
型に続く第三世代の高温型燃料電池、特に固体電解質型
燃料電池、例えばチューブラー型、コルゲート型の他、
集積度の高い平板型のものなどが注目されている。[0003] Among these, in recent years, third generation high-temperature fuel cells following the first generation phosphoric acid type and second generation molten carbonate type fuel cells, particularly solid oxide type fuel cells, have been developed as ones that can be expected to have particularly high efficiency. For example, tubular type, corrugated type, etc.
Flat plate type devices with a high degree of integration are attracting attention.
【０００４】この高温型燃料電池の開発における重要な
課題に電極の改良がある。この電極のうち、カソード材
料には種々の特性、例えば酸化還元に対する過電圧が小
さい、イットリア安定化ジルコニア（ＹＳＺ）等の固体
電解質との整合性（例えば熱膨張係数など）に優れてい
る、電子及びイオン導電性が高いなどの性質を備えるこ
とが要求される。このような特性をもつカソード材料と
して、これまで常温以下での多種多様な電気的、磁気的
特性のために固体物理化学的研究がなされ、特にセンサ
ーや触媒分野での応用研究のめざましい、アルカリ土類
金属をドープしたＬａ１−ｘＭＸＭｎＯ３（ＭはＣａ、
Ｓｒ又はＢａである）系化合物が近年注目されるように
なった。[0004] An important issue in the development of this high-temperature fuel cell is the improvement of electrodes. Among these electrodes, the cathode material has various properties, such as low redox overvoltage, excellent compatibility with solid electrolytes (e.g. thermal expansion coefficient, etc.) such as yttria-stabilized zirconia (YSZ), and electronic and It is required to have properties such as high ionic conductivity. As a cathode material with such characteristics, solid-state physical and chemical research has been conducted for its various electrical and magnetic properties below room temperature. La1-xMXMnO3 doped with similar metals (M is Ca,
In recent years, Sr or Ba) type compounds have attracted attention.
【０００５】しかしながら、この材料は高温では電解質
のＹＳＺ等と化学的に反応してしまうという問題を有し
、非化学量論組成の（Ｌａ，Ｓｒ）１−ＹＭｎＯ３の方
が化学量論組成のものよりＹＳＺ等との反応性に乏しい
ことが報告されているが、高温での相関係や、結晶学的
、電気的、熱的性質についての基礎的なデータは極めて
少ないのが現状である。However, this material has the problem of chemically reacting with the electrolyte YSZ etc. at high temperatures, and (La,Sr)1-YMnO3, which has a non-stoichiometric composition, has a stoichiometric composition. Although it has been reported that it has poor reactivity with YSZ and the like, there is currently very little basic data on phase relationships at high temperatures, crystallographic, electrical, and thermal properties.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、このような
従来のカソード材料のもつ欠点を克服し、電気伝導度を
維持しつつ、高温型燃料電池の作動温度付近の高温域に
おいても同じ結晶構造の安定な相状態を示し、熱膨張係
数の変化も認められない、高温での耐酸化性や安定性に
優れる高温型燃料電池用カソード材料を提供することを
目的としてなされたものである。[Problems to be Solved by the Invention] The present invention overcomes the drawbacks of conventional cathode materials, maintains electrical conductivity, and maintains the same crystalline structure even in the high temperature range near the operating temperature of high-temperature fuel cells. The purpose of this invention was to provide a cathode material for high-temperature fuel cells that exhibits a stable phase state of structure, shows no change in thermal expansion coefficient, and has excellent oxidation resistance and stability at high temperatures.
【０００７】[0007]
【課題を解決するための手段】本発明者は、前記の好ま
しい性質を有するカソード材料を開発するために種々研
究を重ねた結果、特定組成のランタンマンガネート系化
合物がその目的に適合することを見出し、この知見に基
づいて本発明を完成するに至った。[Means for Solving the Problem] As a result of various studies to develop a cathode material having the above-mentioned preferable properties, the present inventor has found that a lanthanum manganate-based compound with a specific composition is suitable for the purpose. Based on this finding, we have completed the present invention.
【０００８】すなわち、本発明は、一般式（Ｉ）That is, the present invention provides general formula (I)
【式２
】〔式中のＭはＳｒ、Ｃａ又はＢａ、０≦ｘ≦０．４、
０＜ｙ≦０．１５、ｚ＞（ｘｙ−ｘ−３ｙ＋６）／２で
ある〕で表わされる組成を有し、かつ相当する焼成物の
酸化性雰囲気下で少なくとも６００℃でのアニーリング
処理物で構成されることを特徴とする高温型燃料電池用
カソード材料を提供するものである。[Formula 2
] [M in the formula is Sr, Ca or Ba, 0≦x≦0.4,
0<y≦0.15, z>(xy-x-3y+6)/2], and is an annealed product at least 600°C in an oxidizing atmosphere of the corresponding fired product. The present invention provides a cathode material for a high-temperature fuel cell characterized by the following structure.
【０００９】本発明の式（Ｉ）の化合物の特徴はＡサイ
トに欠陥を有し、かつ酸素量が全構成金属原子に対する
化学量論量よりも大きい組成を有し、しかも所要焼成物
の所定条件下でのアニーリング処理物であることである
。前記酸素量の化学量論量ｚ′は次の式により表わされ
る。The compound of formula (I) of the present invention is characterized by having a defect at the A site, having a composition in which the amount of oxygen is larger than the stoichiometric amount with respect to all the constituent metal atoms, and moreover, It is an annealed product under certain conditions. The stoichiometric amount z' of the oxygen amount is expressed by the following formula.
【数１】[Math 1]
【００１０】この式（Ｉ）の化合物は高温型燃料電池の
作動温度付近の高温域、例えば８００〜１０００℃、か
つ空気中などの酸化性雰囲気下で菱面体構造の安定相状
態を保持することができる上に、固体電解質として多用
されているジルコニアとの反応が抑制され、それを組み
込んだ燃料電池の出力低下を伴うことがない。従って式
（Ｉ）の化合物は高温型燃料電池用カソード材料となる
。[0010] The compound of formula (I) maintains a stable phase state of a rhombohedral structure in a high temperature range near the operating temperature of a high-temperature fuel cell, for example 800 to 1000°C, and in an oxidizing atmosphere such as air. In addition, the reaction with zirconia, which is often used as a solid electrolyte, is suppressed, and there is no reduction in the output of fuel cells incorporating it. Therefore, the compound of formula (I) serves as a cathode material for high temperature fuel cells.
【００１１】前記した反応の抑制はＡサイトのＬａやＳ
ｒやＣａやＢａの量や総量が化学量論的に不足している
ことに起因し、この不足量が多い程反応抑制効果は大き
いが、導電率も低下するので、式（Ｉ）中のｘは０．２
以下であるのが好ましい。[0011] The above reaction can be suppressed by La or S at the A site.
This is due to a stoichiometric deficiency in the amount and total amount of r, Ca, and Ba, and the greater the amount of deficiency, the greater the reaction suppression effect, but the electrical conductivity also decreases. x is 0.2
It is preferable that it is below.
【００１２】これに対し、従来のものでは酸素雰囲気な
どの酸化性雰囲気下で接触しているカソード材料である
ランタン系酸化物と常用の電解質であるジルコニアが前
記高温域では反応してＬａ２Ｚｒ２Ｏ７やＭｎ２Ｏ３を
生じやすく、これらの反応生成物は導電率が低いため、
電池の出力低下は免れなかった。On the other hand, in the conventional method, lanthanum-based oxide, which is a cathode material, and zirconia, which is a commonly used electrolyte, are in contact with each other in an oxidizing atmosphere such as an oxygen atmosphere, and in the high temperature range, they react to form La2Zr2O7 and Mn2O3. These reaction products have low conductivity, so
A drop in battery output was inevitable.
【００１３】本発明のカソード材料は、通常の焼成法で
得た、アルカリ土類金属化合物を含有していてもよいラ
ンタンマンガネート系材料をさらに所要のアニーリング
を施すことによって製造される。The cathode material of the present invention is produced by further subjecting a lanthanum manganate-based material, which may contain an alkaline earth metal compound, obtained by a conventional calcination method to the necessary annealing.
【００１４】すなわち、原料は、あらかじめ乾燥した粉
粒状のものが好ましく、所要金属成分に相当する酸化物
や、焼成により酸化物を形成しうる化合物、例えば炭酸
塩などが挙げられる。焼成法としては、これらの原料を
所要の組成になるように混合し、通常８００〜１２００
℃で１〜２０時間仮焼し、この仮焼物を粉砕し、板状等
所要形状に成形したのち、通常１２００〜１７００℃で
１〜２０時間焼成するなどの一般的な方法が用いられる
。[0014] That is, the raw material is preferably in the form of powder and granules that have been dried in advance, and examples thereof include oxides corresponding to the required metal components and compounds that can form oxides upon firing, such as carbonates. In the firing method, these raw materials are mixed to have the required composition, and the composition is usually 800 to 1200.
A common method is used, such as calcining at 1 to 20 hours at 1200 to 1700C, pulverizing the calcined product, forming it into a desired shape such as a plate, and then firing at 1200 to 1700C for 1 to 20 hours.
【００１５】次いで、このようにして得た焼成物は、酸
化性雰囲気下、例えば空気中で少なくとも６００℃、好
ましくは８００〜１４００℃で、少なくとも２時間、好
ましくは３〜６０時間アニーリングされる。[0015] The fired product thus obtained is then annealed in an oxidizing atmosphere, for example in air, at a temperature of at least 600°C, preferably from 800 to 1400°C, for at least 2 hours, preferably from 3 to 60 hours.
【００１６】本発明のカソード材料を図面により詳述す
ると、図１の（ａ）、（ｂ）、（ｃ）はｙの値とアニー
リング温度による結晶構造の変化を示すグラフであり、
これより、ｙの値が大きくなり、Ａサイトの欠損量が増
大するとともに菱面体構造から斜方晶構造に変わるアニ
ーリング温度が高温側へシフトすることが分る。一方、
Ｘ線回折により、ｙの値が０．１５を超えるとＭｎ３Ｏ
４が不純物相として析出しやすくなるので、結晶構造と
して好適な単一相を維持するにはＬａ欠損量を０．１以
下とするのが好ましい。このことは、例えば図２にグラ
フで示した式Ｌａ１−ｙＭｎＯｚの化合物の所定温度に
おけるｙの値と格子定数との関係から明らかなように、
ｙが０．１以上では格子定数がほぼ一定になっているこ
とからも裏付けられる。To explain the cathode material of the present invention in detail with reference to drawings, FIGS. 1(a), (b), and (c) are graphs showing changes in crystal structure depending on the value of y and annealing temperature.
From this, it can be seen that as the value of y increases and the amount of defects at the A site increases, the annealing temperature at which the rhombohedral structure changes to the orthorhombic structure shifts to the higher temperature side. on the other hand,
By X-ray diffraction, when the value of y exceeds 0.15, Mn3O
4 tends to precipitate as an impurity phase, so in order to maintain a suitable single phase crystal structure, it is preferable that the amount of La vacancies be 0.1 or less. This is clear, for example, from the relationship between the value of y and the lattice constant at a given temperature for the compound of the formula La1-yMnOz shown graphically in FIG.
This is supported by the fact that the lattice constant is almost constant when y is 0.1 or more.
【００１７】次に、図３は、式Ｌａ１−ｙＭｎＯｚで表
わされる本発明の材料について、Ｌａ欠損量ｙと酸素量
ｚの関係を示すグラフであって、これよりＭｎの酸化状
態は同じ温度でアニーリングされたものであればＬａ欠
損量にかかわらずほぼ一定であることが分る。同様のこ
とは本発明のアルカリ土類金属をドープさせた材料につ
いても認められる。Next, FIG. 3 is a graph showing the relationship between the amount of La deficiency y and the amount of oxygen z for the material of the present invention expressed by the formula La1-yMnOz. From this, it can be seen that the oxidation state of Mn is the same at the same temperature. It can be seen that if it is annealed, it is almost constant regardless of the amount of La deficiency. The same holds true for the alkaline earth metal-doped materials of the present invention.
【００１８】次に、図４は、８００℃でアニーリングさ
れた本発明材料及び比較のためのＬａＭｎＯ３について
、加熱温度と熱膨張係数との関係を示すグラフであって
、これより比較試料では８５０℃付近で熱膨張係数が大
きく変化しこの変化は菱面体構造から斜方晶構造への相
変化を反映していると推測されるのに対し、本発明材料
は１０００℃までこのような変化は認められず安定した
相が保持されていることは図１の（ａ）からも支持され
る。同様のことは本発明のアルカリ土類金属をドープさ
せた材料についても認められる。Next, FIG. 4 is a graph showing the relationship between heating temperature and thermal expansion coefficient for the present invention material annealed at 800°C and LaMnO3 for comparison. The coefficient of thermal expansion changes significantly near the center, and this change is presumed to reflect a phase change from a rhombohedral structure to an orthorhombic structure, whereas the material of the present invention shows no such change up to 1000°C. The fact that a stable phase is maintained without any turbulence is also supported by FIG. 1(a). The same holds true for the alkaline earth metal-doped materials of the present invention.
【００１９】[0019]
【発明の効果】本発明のカソード材料は、電気伝導度を
維持しつつ、高温型燃料電池の作動温度付近の高温域に
おいても同じ結晶構造の安定な相状態を示し、熱膨張係
数の変化も認められず、高温での耐酸化性や安定性に優
れるという顕著な効果を奏する。[Effects of the Invention] The cathode material of the present invention exhibits a stable phase state of the same crystal structure even in a high temperature range near the operating temperature of high-temperature fuel cells while maintaining electrical conductivity, and exhibits no change in thermal expansion coefficient. It has remarkable effects of excellent oxidation resistance and stability at high temperatures.
【００２０】したがって、本発明のカソード材料は高温
型燃料電池、特にイットリア安定化ジルコニアのような
安定化ジルコニアを固体電解質とする高温型燃料電池に
用いて好適である。Therefore, the cathode material of the present invention is suitable for use in high-temperature fuel cells, particularly high-temperature fuel cells using stabilized zirconia such as yttria-stabilized zirconia as a solid electrolyte.
【図１】 ｙの値とアニーリング温度による結晶構造
の変化を示すグラフ。FIG. 1 is a graph showing changes in crystal structure depending on the value of y and annealing temperature.
【図２】 式Ｌａ１−ｙＭｎＯｚの化合物の所定温度
におけるｙの値と格子定数との関係を示すグラフ。FIG. 2 is a graph showing the relationship between the value of y and the lattice constant at a predetermined temperature for a compound of the formula La1-yMnOz.
【図３】 式Ｌａ１−ｙＭｎＯｚで表わされる本発明
の材料について、Ｌａ欠損量ｙと酸素量ｚの関係を示す
グラフ。FIG. 3 is a graph showing the relationship between the amount of La deficiency y and the amount of oxygen z for the material of the present invention expressed by the formula La1-yMnOz.
【図４】 ８００℃でアニーリングされた本発明材料
及び比較のためのＬａＭｎＯ３について、加熱温度と熱
膨張係数との関係を示すグラフ。FIG. 4 is a graph showing the relationship between heating temperature and thermal expansion coefficient for the present invention material annealed at 800°C and LaMnO3 for comparison.
【化２】[Case 2]
Claims (3)
＜ｙ≦０．１５、ｚ＞（ｘｙ−ｘ−３ｙ＋６）／２であ
る〕で表わされる組成を有し、かつ相当する焼成物の酸
化性雰囲気下で少なくとも６００℃でのアニーリング処
理物で構成されることを特徴とする高温型燃料電池用カ
ソード材料。Claim 1: General formula [Formula 1] [M in the formula is Sr, Ca or Ba, 0≦x≦0.4, 0
<y≦0.15, z>(xy-x-3y+6)/2] and consists of a corresponding fired product annealed at at least 600°C in an oxidizing atmosphere A cathode material for high-temperature fuel cells characterized by:
てもよいランタンマンガネート系材料を焼成により形成
したのち、酸化性雰囲気下少なくとも６００℃でアニー
リング処理することを特徴とする請求項１記載の材料の
製造方法。2. The material according to claim 1, wherein the lanthanum manganate-based material which may contain an alkaline earth metal compound is formed by firing and then annealed at at least 600° C. in an oxidizing atmosphere. Method of manufacturing the material.
時間アニーリング処理することを特徴とする請求項２記
載の製造方法。Claim 3: 3-60 at 800-1400°C in air
3. The manufacturing method according to claim 2, further comprising a time annealing process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3089370A JPH04303565A (en) | 1991-03-29 | 1991-03-29 | Cathode material for high-temperature fuel cell and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3089370A JPH04303565A (en) | 1991-03-29 | 1991-03-29 | Cathode material for high-temperature fuel cell and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04303565A true JPH04303565A (en) | 1992-10-27 |
Family
ID=13968810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3089370A Pending JPH04303565A (en) | 1991-03-29 | 1991-03-29 | Cathode material for high-temperature fuel cell and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04303565A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120009505A1 (en) * | 2009-12-31 | 2012-01-12 | Saint-Gobain Ceramics & Plastics, Inc. | Anisotropic cte lsm for sofc cathode |
-
1991
- 1991-03-29 JP JP3089370A patent/JPH04303565A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120009505A1 (en) * | 2009-12-31 | 2012-01-12 | Saint-Gobain Ceramics & Plastics, Inc. | Anisotropic cte lsm for sofc cathode |
| CN102763261A (en) * | 2009-12-31 | 2012-10-31 | 圣戈本陶瓷及塑料股份有限公司 | Anisotropic cte lsm for sofc cathode |
| US8580461B2 (en) * | 2009-12-31 | 2013-11-12 | Saint-Gobain Ceramics & Plastics, Inc. | Anisotropic coefficient of thermal expansion lanthanum strontium manganite for solid oxide fuel cell cathode |
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