JP2014162703A - Perovskite type compound oxide and method for producing the same - Google Patents

Perovskite type compound oxide and method for producing the same Download PDF

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JP2014162703A
JP2014162703A JP2013037456A JP2013037456A JP2014162703A JP 2014162703 A JP2014162703 A JP 2014162703A JP 2013037456 A JP2013037456 A JP 2013037456A JP 2013037456 A JP2013037456 A JP 2013037456A JP 2014162703 A JP2014162703 A JP 2014162703A
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perovskite
complex oxide
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JP6181940B2 (en
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Shin Hamada
心 濱田
Takuma Honda
琢磨 本田
Akira Nagatomi
晶 永富
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Dowa Electronics Materials Co Ltd
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    • 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
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Abstract

PROBLEM TO BE SOLVED: To provide a perovskite type compound oxide of uniform composition and a method for producing the same.SOLUTION: The method for producing a perovskite type compound oxide represented by a composition formula of LaSrCoFeO(0<x<1,0<y<1,0<z<1) is provided. The method includes: wet blending the respective nitrates of lanthanum (La), strontium (Sr), cobalt (Co) and iron (Fe) as the starting material to obtain mixed solution; followed by neutralizing the obtained mixed solution to precipitate a precursor of perovskite type compound oxide and obtain a wet cake of the precursor of perovskite type compound oxide; molding the wet cake into a pellet-form; drying the pellet-form molded product of this wet cake at 200 to 400°C for 1 to 3 hours to obtain an amorphous perovskite type compound oxide precursor that does not exhibit peaks of impurities on diffraction lines according to powder X-ray diffraction method; and calcinating the dried powder of the amorphous perovskite type compound oxide precursor at 600 to 1,000°C.

Description

本発明は、ペロブスカイト型複合酸化物およびその製造方法に関し、特に、固体酸化物型燃料電池の空気極の材料に適したペロブスカイト型複合酸化物およびその製造方法に関する。   The present invention relates to a perovskite complex oxide and a method for producing the same, and more particularly to a perovskite complex oxide suitable for a material for an air electrode of a solid oxide fuel cell and a method for producing the same.

固体酸化物型燃料電池（ＳＯＦＣ（Ｓｏｌｉｄ Ｏｘｉｄｅ Ｆｕｅｌ Ｃｅｌｌ））は、一般に、酸化物からなる空気極と固体電解質と燃料極とからなる単セルをインターコネクタによって接続したスタック構造を採っている。このような固体酸化物型燃料電池の動作温度は、通常１０００℃程度である。近年、固体酸化物型燃料電池の動作温度が低温化されているが、実用化されている固体酸化物型燃料電池の最低温度は６００℃以上と依然として高温である。   2. Description of the Related Art A solid oxide fuel cell (SOFC) generally has a stack structure in which single cells made of an oxide air electrode, a solid electrolyte, and a fuel electrode are connected by an interconnector. The operating temperature of such a solid oxide fuel cell is usually about 1000 ° C. In recent years, the operating temperature of solid oxide fuel cells has been lowered, but the minimum temperature of solid oxide fuel cells in practical use is still as high as 600 ° C. or higher.

このようなセル構造と高い動作温度のため、固体酸化物型燃料電池の空気極の材料は、基本的に、酸素イオン導電性が高く、電子伝導性が高く、熱膨張が電解質と同等あるいは近似し、化学的な安定性が高く、他の構成材料との適合性が良好であり、焼結体が多孔質であり、一定の強度を有することなどの特性が要求される。   Because of this cell structure and high operating temperature, the material of the air electrode of the solid oxide fuel cell basically has high oxygen ion conductivity, high electron conductivity, and thermal expansion is equivalent or close to that of the electrolyte. However, characteristics such as high chemical stability, good compatibility with other constituent materials, a porous sintered body, and a certain strength are required.

このような固体酸化物型燃料電池の空気極の材料として、組成式（Ｌ１−ｘＡＥｘ）１−ｙ（ＦｅｚＭ１−ｚ）Ｏ３＋δで表され、Ｌはスカンジウム（Ｓｃ）、イットリウム（Ｙ）および希土類元素からなる群より選ばれた一種または二種以上の元素であり、ＡＥはカルシウム（Ｃａ）およびストロンチウム（Ｓｒ）の群からなる一種または二種の元素であり、Ｍはマグネシウム（Ｍｇ）、スカンジウム（Ｓｃ）、チタン（Ｔｉ）、バナジウム（Ｖ）、クロム（Ｃｒ）、コバルト（Ｃｏ）およびニッケル（Ｎｉ）からなる群より選ばれた一種または二種以上の元素であり、０＜ｘ＜０．５、０＜ｙ≦０．０４、０≦ｚ＜１であるランタンフェライト系ペロブスカイト酸化物を主成分とするセラミックス粉体が提案されている（例えば、特許文献１参照）。 As a material of the air electrode of such a solid oxide fuel cell, it is represented by a composition formula (L 1-x AE x ) 1-y (Fe z M 1-z ) O 3 + δ , and L is scandium (Sc), One or more elements selected from the group consisting of yttrium (Y) and rare earth elements, AE is one or two elements selected from the group of calcium (Ca) and strontium (Sr), and M is One or more elements selected from the group consisting of magnesium (Mg), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), cobalt (Co) and nickel (Ni) , 0 <x <0.5, 0 <y ≦ 0.04, 0 ≦ z <1, ceramic powders mainly composed of lanthanum ferrite-based perovskite oxides have been proposed (for example, Patent Document 1).

また、固体電解質型燃料電池の空気極の材料として、一般式ＡＢＯ３で表され、ＡがＬａおよび希土類元素の群から選ばれる１つ以上の元素と、Ｓｒ、ＣａおよびＢａの群から選ばれる１つ以上の元素からなり、ＢがＭｎ、Ｃｏ、Ｆｅ、ＮｉおよびＣｕの群から選ばれる１つ以上の元素からなるペロブスカイト複合酸化物粉体であって、平均粒子径が１μｍ以下であり、且つ粒度分布の所定範囲内に制限された固体電解質型燃料電池の空気極原料粉体が提案されている（例えば、特許文献２参照）。 Further, the material of the air electrode of the solid oxide fuel cell is represented by the general formula ABO 3 , and A is selected from one or more elements selected from the group of La and rare earth elements, and from the group of Sr, Ca and Ba. A perovskite composite oxide powder comprising one or more elements and B comprising one or more elements selected from the group consisting of Mn, Co, Fe, Ni and Cu, having an average particle size of 1 μm or less; In addition, an air electrode raw material powder for a solid oxide fuel cell limited to a predetermined range of particle size distribution has been proposed (see, for example, Patent Document 2).

特開２００９−３５４４７号公報（段落番号０００７）JP 2009-35447 A (paragraph number 0007) 特開２００６−３２１３２号公報（段落番号０００９）JP 2006-32132 A (paragraph number 0009)

しかし、特許文献１のランタンフェライト系ペロブスカイト酸化物を主成分とするセラミックス粉体は、ランタンフェライト系ペロブスカイト酸化物の組成式の組成比で出発原料として構成元素の酸化物、炭酸塩、硝酸塩などをエタノールなどの有機溶媒を用いて湿式混合などにより混合し、乾燥して溶媒を揮発させた後、空気中において８００〜１２００℃で５〜２０時間仮焼して得られるが、焼結後の複合酸化物の組成の均一性が不十分で、酸素イオン導電性が高い空気極材料として不十分な場合があった。特に、特許文献１の実施例のように、原料として酸化ランタン、炭酸ストロンチウム、酸化コバルトおよび酸化鉄を乳鉢で混合し、加圧成形した後、仮焼する方法（乾式混合による固相法）では、原料を均一に混合するのが難しく、焼結後の複合酸化物の組成の均一性が不十分で、酸素イオン導電性が高い空気極材料として不十分であった。   However, the ceramic powder containing lanthanum ferrite-based perovskite oxide as a main component in Patent Document 1 contains oxides, carbonates, nitrates, and the like as constituent elements as starting materials at the composition ratio of the composition formula of lanthanum ferrite-based perovskite oxide. After mixing by wet mixing using an organic solvent such as ethanol, drying and volatilizing the solvent, it is obtained by calcining in air at 800 to 1200 ° C. for 5 to 20 hours. In some cases, the uniformity of the oxide composition is insufficient and the air electrode material has high oxygen ion conductivity. In particular, as in the example of Patent Document 1, lanthanum oxide, strontium carbonate, cobalt oxide and iron oxide as raw materials are mixed in a mortar, pressed and then calcined (solid phase method by dry mixing) It was difficult to uniformly mix the raw materials, the uniformity of the composite oxide composition after sintering was insufficient, and it was insufficient as an air electrode material having high oxygen ion conductivity.

また、特許文献２の固体電解質型燃料電池の空気極原料粉体は、Ｌａ、Ｓｒ、ＣｏおよびＦｅの硝酸塩を出発原料として所定の割合で水に溶解させ、この溶液に中和剤としてＮＨ４ＯＨを添加して各元素を含む塩を共沈させ、得られた共沈塩を水洗し、乾燥し、仮焼して得られるが、この湿式混合による共沈法でも、中和や乾燥の条件によって、焼結後の複合酸化物の組成の均一性が不十分で、酸素イオン導電性が高い空気極材料として不十分であった。 Further, the air electrode raw material powder of the solid oxide fuel cell of Patent Document 2 is dissolved in water at a predetermined ratio using nitrates of La, Sr, Co and Fe as starting materials, and NH 4 as a neutralizing agent is added to this solution. OH is added to coprecipitate the salt containing each element, and the resulting coprecipitated salt is washed with water, dried, and calcined. Depending on the conditions, the composition uniformity of the composite oxide after sintering was insufficient, and it was insufficient as an air electrode material having high oxygen ion conductivity.

したがって、本発明は、このような従来の問題点に鑑み、均一な組成のペロブスカイト型複合酸化物およびその製造方法を提供することを目的とする。   Accordingly, an object of the present invention is to provide a perovskite complex oxide having a uniform composition and a method for producing the same, in view of such conventional problems.

本発明者らは、上記課題を解決するために鋭意研究した結果、ペロブスカイト型複合酸化物の出発原料を湿式混合した後、ペロブスカイト型複合酸化物の前駆体を析出させ、この前駆体を乾燥させて得られた粉末Ｘ線回折法による回折線上に不純物のピークを含まない非晶質のペロブスカイト型複合酸化物の前駆体の乾燥粉末を焼成することにより、均一な組成のペロブスカイト型複合酸化物を製造することができることを見出し、本発明を完成するに至った。   As a result of diligent research to solve the above-mentioned problems, the present inventors have wet-mixed the perovskite-type composite oxide starting material, and then precipitated the perovskite-type composite oxide precursor, and dried the precursor. The amorphous perovskite complex oxide precursor powder containing no impurity peak on the diffraction line obtained by the powder X-ray diffraction method is calcined to obtain a uniform composition of the perovskite complex oxide. The inventors have found that it can be manufactured and have completed the present invention.

すなわち、本発明によるペロブスカイト型複合酸化物の製造方法は、ペロブスカイト型複合酸化物の出発原料を湿式混合した後、ペロブスカイト型複合酸化物の前駆体を析出させ、この前駆体を乾燥させて得られた粉末Ｘ線回折法による回折線上に不純物のピークを含まない非晶質のペロブスカイト型複合酸化物の前駆体の乾燥粉末を焼成することを特徴とする。   That is, the method for producing a perovskite complex oxide according to the present invention is obtained by wet-mixing a perovskite complex oxide starting material, then precipitating a perovskite complex oxide precursor, and drying the precursor. A dry powder of an amorphous perovskite complex oxide precursor that does not contain an impurity peak on a diffraction line obtained by powder X-ray diffraction is calcined.

このペロブスカイト型複合酸化物の製造方法において、ペロブスカイト型複合酸化物が、組成式Ｌａ１−ｘＳｒｘＣｏ１−ｙＦｅｙＯ３−ｚ（０＜ｘ＜１、０＜ｙ＜１、０＜ｚ＜１）で示されるペロブスカイト型複合酸化物であるのが好ましい。この場合、出発原料が、ランタン（Ｌａ）とストロンチウム（Ｓｒ）とコバルト（Ｃｏ）と鉄（Ｆｅ）の各々の硝酸塩であるのが好ましい。この場合、ペロブスカイト型複合酸化物の前駆体の析出が、ペロブスカイト型複合酸化物の出発原料を湿式混合して得られた混合溶液を中和することによって行われるのが好ましい。 In the method for producing the perovskite complex oxide, the perovskite complex oxide has a composition formula La 1-x Sr x Co 1-y Fe y O 3-z (0 <x <1, 0 <y <1, 0 A perovskite complex oxide represented by <z <1) is preferred. In this case, the starting material is preferably a nitrate of each of lanthanum (La), strontium (Sr), cobalt (Co), and iron (Fe). In this case, the precipitation of the perovskite complex oxide precursor is preferably carried out by neutralizing a mixed solution obtained by wet mixing the starting materials of the perovskite complex oxide.

また、ペロブスカイト型複合酸化物の前駆体を析出させた後、乾燥させる前に、ペロブスカイト型複合酸化物の前駆体のウエットケーキを得て、このウエットケーキをペレット状に成形するのが好ましい。この場合、ペロブスカイト型複合酸化物の前駆体の乾燥が、ペロブスカイト型複合酸化物の前駆体のウエットケーキのペレット状の成形体を２００〜４００℃で１〜３時間乾燥させることによって行われるのが好ましい。   In addition, it is preferable to obtain a wet cake of the perovskite-type composite oxide precursor after forming the perovskite-type composite oxide precursor and then form the wet cake into pellets before drying. In this case, drying of the perovskite complex oxide precursor is performed by drying a pellet-shaped compact of the wet cake of the perovskite complex oxide precursor at 200 to 400 ° C. for 1 to 3 hours. preferable.

さらに、ペロブスカイト型複合酸化物の前駆体の乾燥粉末の水分値が５％以下であるのが好ましい。また、ペロブスカイト型複合酸化物の前駆体の乾燥粉末の焼成が、ペロブスカイト型複合酸化物の前駆体の乾燥粉末を６００〜１０００℃で焼成することによって行われるのが好ましい。   Further, the moisture value of the dry powder of the perovskite complex oxide precursor is preferably 5% or less. Moreover, it is preferable that the dry powder of the perovskite-type composite oxide precursor is fired by baking the dry powder of the perovskite-type composite oxide precursor at 600 to 1000 ° C.

また、本発明によるペロブスカイト型複合酸化物は、酸素放出速度が０．０５μｍｏｌ／ｇ・分以上であることを特徴とする。このペロブスカイト型複合酸化物が、組成式Ｌａ１−ｘＳｒｘＣｏ１−ｙＦｅｙＯ３−ｚ（０＜ｘ＜１、０＜ｙ＜１、０＜ｚ＜１）で示されるペロブスカイト型複合酸化物であるのが好ましい。 The perovskite complex oxide according to the present invention is characterized in that the oxygen release rate is 0.05 μmol / g · min or more. The perovskite-type composite oxide, a perovskite type represented by the composition formula La 1-x Sr x Co 1 -y Fe y O 3-z (0 <x <1,0 <y <1,0 <z <1) A composite oxide is preferred.

本発明によれば、固体酸化物型燃料電池の空気極の材料に適した均一な組成で酸素放出速度が高いペロブスカイト型複合酸化物およびその製造方法を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the perovskite type complex oxide with a uniform composition suitable for the material of the air electrode of a solid oxide fuel cell and a high oxygen release rate and its manufacturing method can be provided.

実施例１〜３および比較例１〜６で得られたペロブスカイト型複合酸化物の前駆体の乾燥粉末についての粉末Ｘ線回折法（ＸＲＤ）による測定結果を示す図である。It is a figure which shows the measurement result by the powder X-ray-diffraction method (XRD) about the dry powder of the precursor of the perovskite type complex oxide obtained in Examples 1-3 and Comparative Examples 1-6. 実施例３および比較例３で得られた焼成後のペロブスカイト型複合酸化物についてのＸＲＤによる測定結果を示す図である。It is a figure which shows the measurement result by XRD about the perovskite type complex oxide after baking obtained in Example 3 and Comparative Example 3. 図２の一部を拡大して示す図である。It is a figure which expands and shows a part of FIG.

本発明によるペロブスカイト型複合酸化物の製造方法の実施の形態では、ペロブスカイト型複合酸化物の出発原料を湿式混合した後、ペロブスカイト型複合酸化物の前駆体を析出させ、この前駆体を乾燥させて得られた粉末Ｘ線回折法による回折線上に不純物のピークを含まない非晶質のペロブスカイト型複合酸化物の前駆体の乾燥粉末を焼成する。   In the embodiment of the method for producing a perovskite complex oxide according to the present invention, the starting material of the perovskite complex oxide is wet mixed, and then the precursor of the perovskite complex oxide is precipitated, and the precursor is dried. The obtained dry powder of the amorphous perovskite complex oxide precursor containing no impurity peak on the diffraction line by the powder X-ray diffraction method is fired.

このペロブスカイト型複合酸化物の製造方法の実施の形態において、ペロブスカイト型複合酸化物は、組成式Ｌａ１−ｘＳｒｘＣｏ１−ｙＦｅｙＯ３−ｚ（０＜ｘ＜１、０＜ｙ＜１、０＜ｚ＜１）で示されるペロブスカイト型複合酸化物（ＬＳＣＦ）であるのが好ましい。この場合、出発原料として、ランタン（Ｌａ）とストロンチウム（Ｓｒ）とコバルト（Ｃｏ）と鉄（Ｆｅ）の各々の硝酸塩、炭酸塩または酸化物を使用することができるが、ランタン（Ｌａ）とストロンチウム（Ｓｒ）とコバルト（Ｃｏ）と鉄（Ｆｅ）の各々の硝酸塩を使用するのが好ましい。この場合、ペロブスカイト型複合酸化物の前駆体の析出が、ペロブスカイト型複合酸化物の出発原料を湿式混合して得られた混合溶液に炭酸アンモニウムなどのアルカリを添加して、混合溶液を中和することによって行われるのが好ましい。 In the embodiment of the method for producing the perovskite complex oxide, the perovskite complex oxide has a composition formula La 1-x Sr x Co 1-y Fe y O 3-z (0 <x <1, 0 <y A perovskite complex oxide (LSCF) represented by <1, 0 <z <1) is preferable. In this case, as starting materials, nitrates, carbonates or oxides of lanthanum (La), strontium (Sr), cobalt (Co) and iron (Fe) can be used, but lanthanum (La) and strontium. It is preferable to use nitrates of (Sr), cobalt (Co) and iron (Fe). In this case, the precipitation of the perovskite complex oxide precursor is performed by adding an alkali such as ammonium carbonate to the mixed solution obtained by wet mixing the starting material of the perovskite complex oxide to neutralize the mixed solution. Is preferably carried out.

ペロブスカイト型複合酸化物の前駆体を析出させた後、ペロブスカイト型複合酸化物の前駆体のウエットケーキを得て、このウエットケーキを素早く乾燥させるのが好ましく、ウエットケーキを乾燥させ易くするために、例えば、ウエットケーキを円柱形または角柱形のペレット状（棒状）に成形するのが好ましく、直径２〜１０ｍｍのペレット状に形成するのが好ましい。この場合、ペロブスカイト型複合酸化物の前駆体の乾燥が、ペロブスカイト型複合酸化物の前駆体のウエットケーキのペレット状の成形体を２００〜４００℃で１〜３時間乾燥させることによって行われるのが好ましい。   After precipitating the perovskite-type composite oxide precursor, it is preferable to obtain a wet cake of the perovskite-type composite oxide precursor, and to quickly dry this wet cake, in order to facilitate the drying of the wet cake, For example, the wet cake is preferably formed into a cylindrical or prismatic pellet (bar shape), and preferably formed into a pellet having a diameter of 2 to 10 mm. In this case, drying of the perovskite complex oxide precursor is performed by drying a pellet-shaped compact of the wet cake of the perovskite complex oxide precursor at 200 to 400 ° C. for 1 to 3 hours. preferable.

この乾燥後のペロブスカイト型複合酸化物の前駆体の乾燥粉末の水分値は５％以下であるのが好ましい。また、ペロブスカイト型複合酸化物の前駆体の乾燥粉末は、６００〜１３００℃で焼成するのが好ましく、６００〜１０００℃で焼成するのがさらに好ましい。   The moisture value of the dried dry powder of the perovskite complex oxide precursor after drying is preferably 5% or less. The dry powder of the perovskite complex oxide precursor is preferably fired at 600 to 1300 ° C., more preferably 600 to 1000 ° C.

なお、ペロブスカイト型複合酸化物の前駆体を析出させた後に前駆体のウエットケーキを乾燥させるまでの経過時間が長く、乾燥が不十分であると、前駆体に含まれるストロンチウムが水分中または空気中の炭酸ガスと反応して炭酸ストロンチウムが結晶化して析出し、不均一な状態の前駆体になり易い。この不均一な状態の前駆体を焼成してペロブスカイト型複合酸化物を得ても、ペロブスカイト型複合酸化物の組成の均一性が不十分であるため、酸素放出速度が低く、酸素イオン導電性が低くなる。   It should be noted that the elapsed time until the wet cake of the precursor is dried after the perovskite-type composite oxide precursor is deposited is insufficient, and if the drying is insufficient, the strontium contained in the precursor is contained in moisture or in the air. It reacts with the carbon dioxide gas and strontium carbonate crystallizes and precipitates, and tends to be a non-uniform precursor. Even if the perovskite-type composite oxide is obtained by firing this non-uniform precursor, the composition of the perovskite-type composite oxide is insufficiently uniform, so the oxygen release rate is low and the oxygen ion conductivity is low. Lower.

また、本発明によるペロブスカイト型複合酸化物の実施の形態は、酸素放出速度が０．０５μｍｏｌ／ｇ・分以上であり、好ましくは０．１μｍｏｌ／ｇ・分以上である。このペロブスカイト型複合酸化物が、組成式Ｌａ１−ｘＳｒｘＣｏ１−ｙＦｅｙＯ３−ｚ（０＜ｘ＜１、０＜ｙ＜１、０＜ｚ＜１）で示されるペロブスカイト型複合酸化物であるのが好ましい。 In the embodiment of the perovskite complex oxide according to the present invention, the oxygen release rate is 0.05 μmol / g · min or more, preferably 0.1 μmol / g · min or more. The perovskite-type composite oxide, a perovskite type represented by the composition formula La 1-x Sr x Co 1 -y Fe y O 3-z (0 <x <1,0 <y <1,0 <z <1) A composite oxide is preferred.

以下、本発明によるペロブスカイト型複合酸化物およびその製造方法の実施例について詳細に説明する。   Hereinafter, examples of the perovskite complex oxide and the manufacturing method thereof according to the present invention will be described in detail.

［実施例１〜３］
硝酸ランタン六水和物（Ｌａ（ＮＯ３）３・６Ｈ２Ｏ）４．４７ｋｇと、硝酸ストロンチウム（Ｓｒ（ＮＯ３）２）１．６１ｋｇと、硝酸鉄九水和物（Ｆｅ（ＮＯ３）３・９Ｈ２Ｏ）５．５８ｋｇと、硝酸コバルト六水和物（Ｃｏ（ＮＯ３）２・６Ｈ２Ｏ）１．１２ｋｇをそれぞれイオン交換水１０２．２ｋｇに溶解させ、これらの溶液の濃度を溶解種の合計で約０．２０ｍｏｌ／Ｌとして混合し、硝酸塩の混合溶液Ａを作成した。 [Examples 1 to 3]
Lanthanum nitrate hexahydrate (La (NO 3) 3 · 6H 2 O) 4.47kg and strontium nitrate (Sr (NO 3) 2) and 1.61 kg, iron nitrate nonahydrate (Fe (NO 3) and 3 · 9H 2 O) 5.58kg, cobalt nitrate hexahydrate (Co (NO 3) 2 · 6H 2 O) 1.12kg each dissolved in deionized water 102.2Kg, the concentration of these solutions The total dissolved species was mixed as about 0.20 mol / L to prepare a mixed solution A of nitrate.

また、イオン交換水３６．６ｋｇと炭酸アンモニウム８．３３ｋｇを溶解槽に入れ、攪拌しながら水温を１５℃になるよう調整した。この炭酸アンモニウム溶液を、硝酸塩の混合溶液Ａに徐々に加えて中和反応を行い、ペロブスカイト型複合酸化物の前駆体を析出させた後、この前駆体を３０分間熟成させて反応を完了させた。   Moreover, 36.6 kg of ion-exchanged water and 8.33 kg of ammonium carbonate were placed in a dissolution tank, and the water temperature was adjusted to 15 ° C. while stirring. The ammonium carbonate solution was gradually added to the mixed solution A of nitrate to carry out a neutralization reaction to precipitate a perovskite complex oxide precursor, and then the precursor was aged for 30 minutes to complete the reaction. .

このようにして得られた前駆体を濾過した後に水洗し、得られたウエットケーキを直径５ｍｍの細長い円柱形のペレット状に成形した。この成形後直ぐにペレット状の成形体に空気を通風しながら２５０℃で２時間加熱して乾燥させ、黒色の乾燥粉末を得た。このようにして得られたペロブスカイト型複合酸化物の前駆体の乾燥粉末について、粉末Ｘ線回折法（ＸＲＤ）による測定を行ったところ、図１の下側の回折線に示すように、非晶質（アモルファス）の結晶構造であった。また、前駆体の乾燥粉末中の水分値をＪＩＳ Ｋ００６８（２００１年）のカールフィッシャー滴定法に準拠して測定したところ、４％であった。   The precursor thus obtained was filtered and then washed with water, and the resulting wet cake was formed into an elongated cylindrical pellet having a diameter of 5 mm. Immediately after this molding, the pellet-shaped molded body was dried by heating at 250 ° C. for 2 hours while ventilating air to obtain a black dry powder. The dry powder of the perovskite complex oxide precursor thus obtained was measured by powder X-ray diffraction (XRD). As shown in the lower diffraction line of FIG. It was a quality (amorphous) crystal structure. The moisture value in the dry powder of the precursor was measured according to the Karl Fischer titration method of JIS K0068 (2001) and found to be 4%.

次に、このペロブスカイト型複合酸化物の前駆体の乾燥粉末を大気中においてそれぞれ６００℃（実施例１）、８００℃（実施例２）、１０００℃（実施例３）で２時間焼成した後、乾式粉砕処理を行って、結晶性のペロブスカイト型複合酸化物であるＬａ０．６Ｓｒ０．４Ｃｏ０．２Ｆｅ０．８Ｏ３粉末を得た。なお、実施例３で得られた焼成後のペロブスカイト型複合酸化物について、ＸＲＤによる測定を行ったところ、図２および図３の下側の回折線に示すように、ＬＳＣＦの単一相であった。 Next, the perovskite complex oxide precursor dry powder was calcined at 600 ° C. (Example 1), 800 ° C. (Example 2), and 1000 ° C. (Example 3) for 2 hours in the air, respectively. Dry pulverization treatment was performed to obtain a La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 powder which is a crystalline perovskite complex oxide. The perovskite composite oxide after firing obtained in Example 3 was measured by XRD. As shown in the lower diffraction lines of FIGS. 2 and 3, it was a single phase of LSCF. It was.

また、実施例３で得られたペロブスカイト型複合酸化物２０ｍｇを採取して、アルミナ製の測定セル中に装填した後、このセルを示差熱熱重量同時測定装置（ＴＧ／ＤＴＡ測定装置）（セイコーインスツルメンツ株式会社製）にセットして、Ｎ２を５００ｍＬ／分の流量で流しながらＮ２雰囲気中において６００℃まで昇温した。温度が安定した後、Ｎ２を流すのを止めて６００℃に保持したまま、１体積％のＨ２と９体積％のＨｅと９０体積％のＮ２の混合ガスを５００ｍＬ／分の流量で流しながら複合酸化物の重量減少がなくなるまで還元処理を行った。この還元処理による複合酸化物の重量減少を測定して、重量減少曲線の傾きから酸素放出速度を算出したところ、０．２０μｍｏｌ／ｇ・分であった。 Further, 20 mg of the perovskite complex oxide obtained in Example 3 was collected and loaded into an alumina measurement cell, and this cell was then subjected to a differential thermothermal gravimetric simultaneous measurement device (TG / DTA measurement device) (Seiko). is set to Instruments Co., Ltd.), the temperature was raised to 600 ° C. in N 2 atmosphere under a stream of N 2 at 500 mL / min flow rate. After the temperature is stabilized, the flow of N 2 is stopped and kept at 600 ° C. A mixed gas of 1% by volume H 2 , 9% by volume He and 90% by volume N 2 at a flow rate of 500 mL / min. While flowing, reduction treatment was performed until the weight loss of the composite oxide disappeared. The reduction in the weight of the composite oxide due to this reduction treatment was measured, and the oxygen release rate was calculated from the slope of the weight reduction curve, which was 0.20 μmol / g · min.

また、実施例１〜３で得られたペロブスカイト型複合酸化物について、ＢＥＴ測定装置（カンタクロム社製のＭＯＮＯＳＯＲＢ）を用いてＢＥＴ比表面積を測定したところ、それぞれ３１．１ｍ２／ｇ（実施例１）、１６．１ｍ２／ｇ（実施例２）、３．６ｍ２／ｇ（実施例３）であった。 Moreover, when the BET specific surface area was measured about the perovskite type complex oxide obtained in Examples 1 to 3 using a BET measuring apparatus (MONOSORB manufactured by Cantachrome), 31.1 m 2 / g (Example 1) was obtained. ), 16.1 m 2 / g (Example 2), 3.6 m 2 / g (Example 3).

［比較例１〜３］
ペロブスカイト型複合酸化物の前駆体のウエットケーキを厚さ５ｍｍ、幅２〜３ｃｍのブロック状に形成し、１５０℃で２時間加熱して乾燥した以外は、実施例１と同様の方法により、ペロブスカイト型複合酸化物の前駆体の乾燥粉末を得た。このようにして得られたペロブスカイト型複合酸化物の前駆体の乾燥粉末について、ＸＲＤによる測定を行ったところ、アモルファスの回折線（図１の上側の回折線）上に僅かに炭酸Ｓｒ（ＳｒＣＯ３）のピークが確認された。また、前駆体の乾燥粉末中の水分値を実施例１と同様の方法により測定したところ、５％であった。 [Comparative Examples 1-3]
A perovskite compound oxide was prepared in the same manner as in Example 1 except that the wet cake of the precursor of the perovskite complex oxide was formed into a block shape having a thickness of 5 mm and a width of 2 to 3 cm, and dried by heating at 150 ° C. for 2 hours. A dry powder of a precursor of type complex oxide was obtained. When the dried powder of the perovskite complex oxide precursor obtained in this way was measured by XRD, Sr carbonate (SrCO 3 ) was slightly present on the amorphous diffraction line (the upper diffraction line in FIG. 1). ) Was confirmed. The moisture value in the dry powder of the precursor was measured by the same method as in Example 1 and found to be 5%.

次に、このペロブスカイト型複合酸化物の前駆体の乾燥粉末を大気中においてそれぞれ６００℃（比較例１）、８００℃（比較例２）、１０００℃（比較例３）で２時間焼成した後、乾式粉砕処理を行って、結晶性のペロブスカイト型複合酸化物であるＬａ０．６Ｓｒ０．４Ｃｏ０．２Ｆｅ０．８Ｏ３粉末を得た。なお、比較例３で得られた焼成後のペロブスカイト型複合酸化物について、ＸＲＤによる測定を行ったところ、図２および図３の上側の回折線に示すように、ＬＳＣＦのピークと共に僅かにＳｒＦｅＯ３のピークが確認された。 Next, after the dried powder of the perovskite complex oxide precursor was baked at 600 ° C. (Comparative Example 1), 800 ° C. (Comparative Example 2), and 1000 ° C. (Comparative Example 3) for 2 hours in the air, Dry pulverization treatment was performed to obtain a La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 powder which is a crystalline perovskite complex oxide. The perovskite composite oxide after firing obtained in Comparative Example 3 was measured by XRD. As shown in the upper diffraction lines of FIGS. 2 and 3, SrFeO 3 was slightly added together with the LSCF peak. The peak of was confirmed.

また、比較例３で得られたペロブスカイト型複合酸化物について、実施例１と同様の方法により酸素放出速度を算出したところ、０．０３μｍｏｌ／ｇ・分であった。   Further, the oxygen release rate of the perovskite complex oxide obtained in Comparative Example 3 was calculated by the same method as in Example 1. As a result, it was 0.03 μmol / g · min.

また、比較例１〜３で得られたペロブスカイト型複合酸化物について、実施例１と同様の方法によりＢＥＴ比表面積を測定したところ、それぞれ３９．７ｍ２／ｇ（比較例１）、１６．２ｍ２／ｇ（比較例２）、３．６ｍ２／ｇ（比較例３）であった。 Moreover, when the BET specific surface area was measured by the method similar to Example 1 about the perovskite type complex oxide obtained in Comparative Examples 1-3, it was 39.7 m < 2 > / g (Comparative Example 1) and 16.2 m, respectively. 2 / g (Comparative Example 2) and 3.6 m 2 / g (Comparative Example 3).

［比較例４〜６］
ペロブスカイト型複合酸化物の前駆体のウエットケーキを８０℃で２４時間加熱して乾燥した以外は、実施例１と同様の方法により、ペロブスカイト型複合酸化物の前駆体の薄赤色の乾燥粉末を得た。このようにして得られたペロブスカイト型複合酸化物の前駆体の乾燥粉末について、ＸＲＤによる測定を行ったところ、アモルファスの回折線（図１の上側の回折線）上に僅かに炭酸Ｓｒ（ＳｒＣＯ３）のピークが確認された。また、前駆体の乾燥粉末中の水分値を実施例１と同様の方法により測定したところ、４％であった。 [Comparative Examples 4 to 6]
A pale red dry powder of the perovskite complex oxide precursor was obtained in the same manner as in Example 1 except that the wet cake of the perovskite complex oxide precursor was dried by heating at 80 ° C. for 24 hours. It was. When the dried powder of the perovskite complex oxide precursor obtained in this way was measured by XRD, Sr carbonate (SrCO 3 ) was slightly present on the amorphous diffraction line (the upper diffraction line in FIG. 1). ) Was confirmed. The moisture value in the precursor dry powder was measured by the same method as in Example 1 and found to be 4%.

次に、このペロブスカイト型複合酸化物の前駆体の乾燥粉末を大気中においてそれぞれ６００℃（比較例４）、８００℃（比較例５）、１０００℃（比較例６）で２時間焼成した後、乾式粉砕処理を行って、結晶性のペロブスカイト型複合酸化物であるＬａ０．６Ｓｒ０．４Ｃｏ０．２Ｆｅ０．８Ｏ３粉末を得た。 Next, after the dried powder of the perovskite complex oxide precursor was baked at 600 ° C. (Comparative Example 4), 800 ° C. (Comparative Example 5), and 1000 ° C. (Comparative Example 6) for 2 hours in the air, Dry pulverization treatment was performed to obtain a La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 powder which is a crystalline perovskite complex oxide.

また、比較例５〜６で得られたペロブスカイト型複合酸化物について、実施例１と同様の方法によりＢＥＴ比表面積を測定したところ、それぞれ１７．１ｍ２／ｇ（比較例５）、３．９ｍ２／ｇ（比較例６）であった。 Moreover, when the BET specific surface area was measured by the method similar to Example 1 about the perovskite type complex oxide obtained in Comparative Examples 5-6, it was 17.1 m < 2 > / g (Comparative Example 5) and 3.9 m, respectively. 2 / g (Comparative Example 6).

［比較例７〜８］
酸化ランタン（Ｌａ２Ｏ３）２．１３ｋｇと、四酸化三コバルト（Ｃｏ３Ｏ４）０．３６ｋｇと、三酸化二鉄（Ｆｅ２Ｏ３）１．４１ｇと、炭酸ストロンチウム（ＳｒＣＯ３）１．４４ｇとを原料としてサンプルミルで２分間粉砕して混合し、混合粉末を得た。この混合粉末についてＸＲＤ測定したところ、各原料の結晶構造が重なった回折線が得られた。 [Comparative Examples 7-8]
Lanthanum oxide (La 2 O 3 ) 2.13 kg, tricobalt tetroxide (Co 3 O 4 ) 0.36 kg, diiron trioxide (Fe 2 O 3 ) 1.41 g, strontium carbonate (SrCO 3 ) 1 .44 g as a raw material was pulverized for 2 minutes in a sample mill and mixed to obtain a mixed powder. When this mixed powder was measured by XRD, diffraction lines in which the crystal structures of the respective raw materials overlapped were obtained.

次に、この混合粉末を大気中においてそれぞれ８００℃（比較例７）、１０００℃（比較例８）で２時間焼成した後、乾式粉砕処理を行って、複合酸化物を得た。この複合酸化物について、ＸＲＤによる測定を行ったところ、不純物ピークと共に結晶性のペロブスカイト型複合酸化物Ｌａ０．６Ｓｒ０．４Ｃｏ０．２Ｆｅ０．８Ｏ３のピークが確認された。 Next, this mixed powder was fired at 800 ° C. (Comparative Example 7) and 1000 ° C. (Comparative Example 8) for 2 hours in the air, and then subjected to dry pulverization treatment to obtain a composite oxide. When this composite oxide was measured by XRD, the peak of the crystalline perovskite complex oxide La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 was confirmed together with the impurity peak.

また、比較例８で得られたペロブスカイト型複合酸化物について、実施例１と同様の方法により酸素放出速度を算出したところ、０．０２μｍｏｌ／ｇ・分であった。   Further, with respect to the perovskite complex oxide obtained in Comparative Example 8, the oxygen release rate was calculated by the same method as in Example 1. As a result, it was 0.02 μmol / g · min.

また、比較例７〜８で得られたペロブスカイト型複合酸化物について、実施例１と同様の方法によりＢＥＴ比表面積を測定したところ、それぞれ４．５ｍ２／ｇ（比較例７）、１．８ｍ２／ｇ（比較例８）であった。 Moreover, when the BET specific surface area was measured by the method similar to Example 1 about the perovskite type complex oxide obtained in Comparative Examples 7-8, it was 4.5 m < 2 > / g (Comparative Example 7) and 1.8 m, respectively. 2 / g (Comparative Example 8).

これらの実施例および比較例のペロブスカイト型複合酸化物の製造条件および特性を表１および表２に示す。   Tables 1 and 2 show the production conditions and characteristics of the perovskite complex oxides of these examples and comparative examples.

Figure 2014162703
Figure 2014162703

Figure 2014162703
Figure 2014162703

ペロブスカイト型複合酸化物の前駆体を１０００℃より高い温度で焼成すると、ペロブスカイト型複合酸化物のＸＲＤ測定において単一相になる。表１および表２からわかるように、比較例１〜８のペロブスカイト型複合酸化物の前駆体を６００〜１０００℃の低い温度で焼成すると、複数相になるか、ほぼ単一相になっても（図２および図３の上側の回折線に示すようにペロブスカイト型複合酸化物Ｌａ０．６Ｓｒ０．４Ｃｏ０．２Ｆｅ０．８Ｏ３の主相ピークに対して２％以上の強度比のＳｒＦｅＯ３相のピークが不純物相として確認され、）僅かにＳｒＦｅＯ３を含んでいるが、実施例１〜３のペロブスカイト型複合酸化物の前駆体のように、粉末Ｘ線回折法による回折線上に不純物のピークを含まない非晶質（アモルファス）の結晶構造の前駆体を６００〜１０００℃の低い温度で焼成すると（ペロブスカイト型複合酸化物Ｌａ０．６Ｓｒ０．４Ｃｏ０．２Ｆｅ０．８Ｏ３の主相ピークに対する不純物相のピークの強度比が２％未満の）単一相になる。 When the precursor of the perovskite complex oxide is fired at a temperature higher than 1000 ° C., a single phase is obtained in the XRD measurement of the perovskite complex oxide. As can be seen from Tables 1 and 2, when the precursors of the perovskite complex oxides of Comparative Examples 1 to 8 are fired at a low temperature of 600 to 1000 ° C., even if they become multiple phases or almost single phases (Intensity of 2% or more with respect to the main phase peak of the perovskite complex oxide La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 as shown by the upper diffraction lines in FIGS. The SrFeO 3 phase peak of the ratio is confirmed as an impurity phase), and slightly contains SrFeO 3 , but diffraction by the powder X-ray diffraction method like the perovskite complex oxide precursors of Examples 1 to 3 When a precursor having an amorphous crystal structure that does not contain an impurity peak on a line is fired at a low temperature of 600 to 1000 ° C. (perovskite complex oxide La 0.6 Sr 0.4 Co 0.2 Fe 0. Peak intensity ratio of the impurity phase to the main phase peak of O 3 is less than 2%) into a single phase.

表２からわかるように、実施例３のペロブスカイト型複合酸化物は、比較例３および８のペロブスカイト型複合酸化物に比べて、酸素放出速度が極めて速く（Ｏ２のモビリティーが高く）、固体酸化物型燃料電池の空気極に使用する酸化物イオン伝導物質として有効である。 As can be seen from Table 2, the perovskite complex oxide of Example 3 has an extremely high oxygen release rate (higher O 2 mobility) than the perovskite complex oxides of Comparative Examples 3 and 8, and solid oxidation. It is effective as an oxide ion conductive material used in the air electrode of a physical fuel cell.

また、固体酸素の放出は粒子表面で進行するため、粒子内部（バルク）の酸素は、結晶構造の欠陥を通って表面まで移動する必要があるが、実施例１〜３のＬａ１−ｘＳｒｘＣｏ１−ｙＦｅｙＯ３−ｚの（ＬＳＣＦ）系のペロブスカイト型複合酸化物は、完全酸素放出時間が短いため、バルク内の酸化物イオンの移動がスムーズに進行できる材料であると考えられる。 Further, since the release of solid oxygen proceeds on the particle surface, oxygen inside the particle (bulk) needs to move to the surface through defects in the crystal structure, but La 1-x Sr in Examples 1-3. The (LSCF) -based perovskite complex oxide of x Co 1-y Fe y O 3-z is considered to be a material in which the movement of oxide ions in the bulk can proceed smoothly because the complete oxygen release time is short. It is done.

また、バルク内の酸化物イオンの移動は、ペロブスカイト構造の組成の均一性に影響を受けると考えられるため、実施例１〜３のＬＳＣＦは、組成の均一性が高いと考えられる。   Moreover, since the movement of oxide ions in the bulk is considered to be influenced by the uniformity of the composition of the perovskite structure, the LSCFs of Examples 1 to 3 are considered to have high composition uniformity.

さらに、実施例３のペロブスカイト型複合酸化物は、比較例３および８のペロブスカイト型複合酸化物と比較すると、同程度の比表面積でも酸素放出速度が非常に高くなっているので、より均一な組成によって酸素移動度が高くなると考えられる。   Furthermore, the perovskite complex oxide of Example 3 has a more uniform composition because the oxygen release rate is very high even at a specific surface area comparable to that of Comparative Examples 3 and 8, compared with the perovskite complex oxides of Comparative Examples 3 and 8. It is considered that the oxygen mobility increases.

本発明によるペロブスカイト型複合酸化物は、均一な組成で酸素放出速度が極めて速く、固体酸化物型燃料電池の空気極の材料として使用することができる。   The perovskite complex oxide according to the present invention has a uniform composition and an extremely high oxygen release rate, and can be used as a material for an air electrode of a solid oxide fuel cell.

Claims (10)

ペロブスカイト型複合酸化物の出発原料を湿式混合した後、ペロブスカイト型複合酸化物の前駆体を析出させ、この前駆体を乾燥させて得られた粉末Ｘ線回折法による回折線上に不純物のピークを含まない非晶質のペロブスカイト型複合酸化物の前駆体の乾燥粉末を焼成することを特徴とする、ペロブスカイト型複合酸化物の製造方法。 After wet mixing the starting material of the perovskite type complex oxide, the precursor of the perovskite type complex oxide is precipitated, and the precursor is dried, and the impurity peak is included on the diffraction line obtained by the powder X-ray diffraction method. A method for producing a perovskite complex oxide, comprising firing a dry powder of a non-amorphous perovskite complex oxide precursor. 前記ペロブスカイト型複合酸化物が、組成式Ｌａ１−ｘＳｒｘＣｏ１−ｙＦｅｙＯ３−ｚ（０＜ｘ＜１、０＜ｙ＜１、０＜ｚ＜１）で示されるペロブスカイト型複合酸化物であることを特徴とする、請求項1に記載のペロブスカイト型複合酸化物の製造方法。 The perovskite-type composite oxide, a perovskite type represented by the composition formula La 1-x Sr x Co 1 -y Fe y O 3-z (0 <x <1,0 <y <1,0 <z <1) 2. The method for producing a perovskite complex oxide according to claim 1, wherein the perovskite complex oxide is a complex oxide. 前記出発原料が、ランタン（Ｌａ）とストロンチウム（Ｓｒ）とコバルト（Ｃｏ）と鉄（Ｆｅ）の各々の硝酸塩であることを特徴とする、請求項２に記載のペロブスカイト型複合酸化物の製造方法。 3. The method for producing a perovskite complex oxide according to claim 2, wherein the starting material is a nitrate of each of lanthanum (La), strontium (Sr), cobalt (Co), and iron (Fe). . 前記ペロブスカイト型複合酸化物の前駆体の析出が、前記ペロブスカイト型複合酸化物の出発原料を湿式混合して得られた混合溶液を中和することによって行われることを特徴とする、請求項３に記載のペロブスカイト型複合酸化物の製造方法。 The precipitation of the perovskite complex oxide precursor is performed by neutralizing a mixed solution obtained by wet mixing the starting material of the perovskite complex oxide. The manufacturing method of perovskite type complex oxide as described. 前記ペロブスカイト型複合酸化物の前駆体を析出させた後、乾燥させる前に、前記ペロブスカイト型複合酸化物の前駆体のウエットケーキを得て、このウエットケーキをペレット状に成形することを特徴とする、請求項１乃至４のいずれかに記載のペロブスカイト型複合酸化物の製造方法。 After depositing the perovskite-type composite oxide precursor and before drying, obtain a wet cake of the perovskite-type composite oxide precursor, and shape the wet cake into pellets. A method for producing a perovskite complex oxide according to any one of claims 1 to 4. 前記ペロブスカイト型複合酸化物の前駆体の乾燥が、前記ペロブスカイト型複合酸化物の前駆体のウエットケーキのペレット状の成形体を２００〜４００℃で１〜３時間乾燥させることによって行われることを特徴とする、請求項５に記載のペロブスカイト型複合酸化物の製造方法。 The drying of the perovskite complex oxide precursor is performed by drying the pellet-shaped compact of the perovskite complex oxide precursor at 200 to 400 ° C. for 1 to 3 hours. The method for producing a perovskite complex oxide according to claim 5. 前記ペロブスカイト型複合酸化物の前駆体の乾燥粉末の水分値が５％以下であることを特徴とする、請求項１乃至６のいずれかに記載のペロブスカイト型複合酸化物の製造方法。 The method for producing a perovskite complex oxide according to any one of claims 1 to 6, wherein the moisture value of the dry powder of the precursor of the perovskite complex oxide is 5% or less. 前記ペロブスカイト型複合酸化物の前駆体の乾燥粉末の焼成が、前記ペロブスカイト型複合酸化物の前駆体の乾燥粉末を６００〜１０００℃で焼成することによって行われることを特徴とする、請求項１乃至７のいずれかに記載のペロブスカイト型複合酸化物の製造方法。 The dry powder of the perovskite-type composite oxide precursor is fired by baking the dry powder of the perovskite-type composite oxide precursor at 600 to 1000 ° C. 8. A method for producing a perovskite complex oxide according to any one of 7 above. 酸素放出速度が０．０５μｍｏｌ／ｇ・分以上であることを特徴とする、ペロブスカイト型複合酸化物。 A perovskite complex oxide characterized by having an oxygen release rate of 0.05 μmol / g · min or more. 前記ペロブスカイト型複合酸化物が、組成式Ｌａ１−ｘＳｒｘＣｏ１−ｙＦｅｙＯ３−ｚ（０＜ｘ＜１、０＜ｙ＜１、０＜ｚ＜１）で示されるペロブスカイト型複合酸化物であることを特徴とする、請求項９に記載のペロブスカイト型複合酸化物。 The perovskite-type composite oxide, a perovskite type represented by the composition formula La 1-x Sr x Co 1 -y Fe y O 3-z (0 <x <1,0 <y <1,0 <z <1) The perovskite complex oxide according to claim 9, which is a complex oxide.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113661144A (en) * 2019-03-25 2021-11-16 堺化学工业株式会社 Metal composite oxide, method for producing same, and electrode for solid oxide fuel cell

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02502180A (en) * 1987-11-17 1990-07-19 フェバ・エール・アクチェンゲゼルシャフト Metal oxide powders, mixtures thereof, metal mixed oxide powders, mixtures thereof and their use in the catalytic dehydrogenation of hydrocarbons
JPH054044A (en) * 1990-10-29 1993-01-14 Osaka Gas Co Ltd Treatment of oxygen-containing gas and treating material for oxygen-containing gas used for this method
JP2000302445A (en) * 1999-04-19 2000-10-31 Toda Kogyo Corp Fusiform goethite particle powder, fusiform hematite particle powder, and fusiform metallic magnetic particle powder consisting mainly of iron, and their production
JP2003117362A (en) * 2001-10-16 2003-04-22 Taiheiyo Cement Corp Oxygen separating apparatus
US20040247511A1 (en) * 2003-03-28 2004-12-09 Shuichi Mafune Method of producing perovskite complex oxide and precursor substance used in the method
JP2005187311A (en) * 2003-03-28 2005-07-14 Dowa Mining Co Ltd Method of producing perovskite compound oxide and precursor substance used in the method
JP2005216774A (en) * 2004-01-30 2005-08-11 Chiyoda Corp Hydrogen supplying device of fuel cell for working machine
JP2012138256A (en) * 2010-12-27 2012-07-19 Agc Seimi Chemical Co Ltd Air electrode material powder for solid oxide type fuel battery, and method of manufacturing the same
WO2013094516A1 (en) * 2011-12-19 2013-06-27 日本碍子株式会社 Solid oxide fuel cell

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02502180A (en) * 1987-11-17 1990-07-19 フェバ・エール・アクチェンゲゼルシャフト Metal oxide powders, mixtures thereof, metal mixed oxide powders, mixtures thereof and their use in the catalytic dehydrogenation of hydrocarbons
JPH054044A (en) * 1990-10-29 1993-01-14 Osaka Gas Co Ltd Treatment of oxygen-containing gas and treating material for oxygen-containing gas used for this method
JP2000302445A (en) * 1999-04-19 2000-10-31 Toda Kogyo Corp Fusiform goethite particle powder, fusiform hematite particle powder, and fusiform metallic magnetic particle powder consisting mainly of iron, and their production
JP2003117362A (en) * 2001-10-16 2003-04-22 Taiheiyo Cement Corp Oxygen separating apparatus
US20040247511A1 (en) * 2003-03-28 2004-12-09 Shuichi Mafune Method of producing perovskite complex oxide and precursor substance used in the method
JP2005187311A (en) * 2003-03-28 2005-07-14 Dowa Mining Co Ltd Method of producing perovskite compound oxide and precursor substance used in the method
JP2005216774A (en) * 2004-01-30 2005-08-11 Chiyoda Corp Hydrogen supplying device of fuel cell for working machine
JP2012138256A (en) * 2010-12-27 2012-07-19 Agc Seimi Chemical Co Ltd Air electrode material powder for solid oxide type fuel battery, and method of manufacturing the same
WO2013094516A1 (en) * 2011-12-19 2013-06-27 日本碍子株式会社 Solid oxide fuel cell

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113661144A (en) * 2019-03-25 2021-11-16 堺化学工业株式会社 Metal composite oxide, method for producing same, and electrode for solid oxide fuel cell
CN113661144B (en) * 2019-03-25 2023-11-07 堺化学工业株式会社 Metal composite oxide, method for producing same, and electrode for solid oxide fuel cell

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