JPH04149023A - Calcium-doped lanthanum manganite and solid electrolyte fuel cell using the same - Google Patents
Calcium-doped lanthanum manganite and solid electrolyte fuel cell using the sameInfo
- Publication number
- JPH04149023A JPH04149023A JP2273173A JP27317390A JPH04149023A JP H04149023 A JPH04149023 A JP H04149023A JP 2273173 A JP2273173 A JP 2273173A JP 27317390 A JP27317390 A JP 27317390A JP H04149023 A JPH04149023 A JP H04149023A
- Authority
- JP
- Japan
- Prior art keywords
- calcium
- solid electrolyte
- lanthanum manganite
- doped lanthanum
- 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.)
- Granted
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 41
- BQENXCOZCUHKRE-UHFFFAOYSA-N [La+3].[La+3].[O-][Mn]([O-])=O.[O-][Mn]([O-])=O.[O-][Mn]([O-])=O Chemical compound [La+3].[La+3].[O-][Mn]([O-])=O.[O-][Mn]([O-])=O.[O-][Mn]([O-])=O BQENXCOZCUHKRE-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 7
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract description 6
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 5
- 239000000567 combustion gas Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 2
- 125000006850 spacer group Chemical group 0.000 abstract description 2
- 235000010216 calcium carbonate Nutrition 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 36
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 20
- 239000013078 crystal Substances 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- 229910052746 lanthanum Inorganic materials 0.000 description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- AUFVVJFBLFWLJX-UHFFFAOYSA-N [Mn].[La] Chemical compound [Mn].[La] AUFVVJFBLFWLJX-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NFYLSJDPENHSBT-UHFFFAOYSA-N chromium(3+);lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+3].[La+3] NFYLSJDPENHSBT-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- -1 lanthanum zirconate Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000004448 titration Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Inert Electrodes (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はカルシウムドープランタンマンガナイトとそれ
を利用する固体電解質燃料電池に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to calcium-doped lanthanum manganite and a solid electrolyte fuel cell using the same.
更に上述すると、本発明はジルコニアと反応して電解質
の電気抵抗を高めることのないカルシウムドープランタ
ンマンガナイト及びそれを空気極として用いた固体電解
質燃料電池に関するものである。More specifically, the present invention relates to calcium-doped lanthanum manganite that does not react with zirconia to increase the electrical resistance of the electrolyte, and to a solid electrolyte fuel cell using the calcium-doped lanthanum manganite as an air electrode.
（従来技術とその問題点）
ランタンマンガナイト系酸化物は、固体電解質燃料電池
の空気極材料として長い間研究されてきた。その理由は
、固体電解質燃料電池の空気極材料として要求される高
い触媒活性（酸素の還元能力）有するからである。(Prior art and its problems) Lanthanum manganite-based oxides have been studied for a long time as air electrode materials for solid electrolyte fuel cells. The reason is that it has high catalytic activity (oxygen reduction ability) required as an air electrode material for solid electrolyte fuel cells.
しかし、このランタンマンガナイト（ＬａＭｎ０３−ｚ
）系酸化物は、室温ではほとんど絶縁体に近く、１００
０℃の高温でも導電率が低い半導体であることから固体
電解質燃料電池の空気極としては不向きであった。特に
、空気極か内部抵抗の６５°６を占める円筒型の燃料電
池には間穎かあった。However, this lantern manganite (LaMn03-z
)-based oxides are almost insulators at room temperature, with 100
Since it is a semiconductor with low conductivity even at a high temperature of 0°C, it was not suitable as an air electrode for a solid electrolyte fuel cell. In particular, the cylindrical fuel cell, which occupies 65°6 of internal resistance between the air electrode and the internal resistance, had some problems.
そこでこれらを解決するなめにカルシウムをランタンと
！換り高温での導電率を高くしたカルシウムドープラン
タンマンガナイト（Ｌａｄ−ｘＣａｘ Ｍ ｎ ０３−
□）を考えた。このカルシウムドープランタンマンガナ
イト系酸化物は、固体電解質燃料電池の空気極として必
要な高い触媒活性（ｉ１！素の還元能力）と高い導Ｓ率
を併せ持ち、更に固体電解質燃料電池に用いて好適と思
われた。So, to solve these problems, use calcium and lanthanum! Calcium-doped lanthanum manganite (Lad-xCax M n 03-
I thought about □). This calcium-doped lanthanum manganite-based oxide has both high catalytic activity (i1! elementary reduction ability) and high S conductivity necessary for the air electrode of solid electrolyte fuel cells, and is also suitable for use in solid electrolyte fuel cells. It seemed to me.
（発明が解決しようとする課題）
しかしながら、空気極として使用されるランタンマンガ
ナイトは、上述の如く触媒活性や電子伝導性に優れるの
みでなく、酸化雰囲気などにおけるジルコニアとの高い
熱力学的安定性をもつこと仁、要求される。(Problems to be Solved by the Invention) However, lanthanum manganite used as an air electrode not only has excellent catalytic activity and electronic conductivity as described above, but also has high thermodynamic stability with zirconia in an oxidizing atmosphere. It is required to have jin.
しかし、カルシウムドープランタンマンカナイ１＝ （
（Ｌａ、−ｘ Ｃａｘ ）ｌ−ｙ ＭｎＯ，−ｚ ）系
酸化物は、定片（ｙ＝ｏ）にすると、電池作製時の高温
処理や作動温度における電池の長時間使用により、電解
質のジルコニアと反応して電気抵抗の高い（約１００倍
）ランタンシ゛ルコネート（Ｌａ２Ｚｒｑ ０７ ）等
の化合物を電極と電解質の界面に生成することが明らか
にな−）てきた。However, calcium-doped lantern mankanai 1 = (
(La, -x Cax ) ly MnO, -z ) system oxide, when made into a constant piece (y = o), will lose zirconia in the electrolyte due to high-temperature treatment during battery fabrication or long-term use of the battery at operating temperature. It has become clear that compounds such as lanthanum silconate (La2Zrq07) with high electrical resistance (approximately 100 times higher) are produced at the interface between the electrode and the electrolyte.
また、ランタンやカルシウムを少なくした不定比のカル
シウムドープランタンマンカナイトは、（１）焼結性か
高くなり触媒活性か劣化し易くなる、
（２）不定比１によってはＭｎ５Ｏ４か析出し、電解質
のジルコニアと反応し、ジ
ルコニアの電気抵抗を高くする
という２つの問題がでてきた。Calcium-doped lanthanum mancanite with a non-stoichiometric ratio containing less lanthanum and calcium has the following effects: (1) sinterability becomes high and catalytic activity easily deteriorates; (2) Mn5O4 precipitates depending on the non-stoichiometric ratio (1), and electrolyte Two problems have arisen: it reacts with zirconia and increases the electrical resistance of zirconia.
これらの問題は燃料電池を作製するとき高い温度で焼成
することができなくなり、燃料電池としての期待された
性能を得られなくなるという問題を生ずる。These problems cause the problem that when producing a fuel cell, it is no longer possible to sinter it at a high temperature, making it impossible to obtain the expected performance as a fuel cell.
本発明は、高温例えば燃料電池の作動温度で長時間使用
されても、ジルコニアと反応しないカルシウムドープラ
ンタンマンガナイトを提供し、固体電解質燃料電池の長
寿命化、高性能化に寄与できるようにしたものである。The present invention provides calcium-doped lanthanum manganite that does not react with zirconia even when used for a long time at high temperatures, such as the operating temperature of a fuel cell, and can contribute to extending the lifespan and improving the performance of solid electrolyte fuel cells. It is something.
（間趙点を解決するための手段）
かかる目的を達成するため、本発明のカルシウムドープ
ランタンマンガナイト系酸化物は、その主成分の各々の
元素が
（Ｌａｄ−７Ｃａ ｘ ） ｔ −ｙ Ｍ ｎ Ｏｓ−
ｚであり、かつｘ、ｙの値が
０＜ｘ＜０．２かつ０．０２５＜ｙ＜０．７５を満足す
るようにしている。(Means for Solving the Intercontinental Point) In order to achieve this object, the calcium-doped lanthanum manganite-based oxide of the present invention has the following properties: (Lad-7Cax)t-yMn Os-
z, and the values of x and y satisfy 0<x<0.2 and 0.025<y<0.75.
また、本発明のカルシウムドープランタンマンガナイト
は、その主成分の各々の元素が（Ｌ ａ ｌ−Ｋ Ｃａ
ｘ ） ＋ −ｙ Ｍ ｎ ０３−であり、かつｘ、ｙ
の値が
０．２≦ｘ＜０．４かつ
０．０２５＜ｙ＜０．０５
を満足するようにしている。In addition, the calcium-doped lanthanum manganite of the present invention has each of its main components (L a l-K Ca
x ) + -y M n 03-, and x, y
The value of is made to satisfy 0.2≦x<0.4 and 0.025<y<0.05.
更に上述の本発明のカルシウムドープランタンマンガナ
イト粉体を焼成し、空気極として使用することによって
固体電解質燃料電池は得られている。Furthermore, a solid electrolyte fuel cell is obtained by firing the above-described calcium-doped lanthanum manganite powder of the present invention and using it as an air electrode.
（作用）
（Ｌ ａ ｌ −Ｋ Ｃａｔ ） ｌ−ｙ Ｍ ｎ ０
ｉ−ｚで表されるカルシウムドープランタンマンカナイ
ト系酸化物は、ｙ＝Ｑの定片だと高温下で酸化マンガン
（Ｍｎ３０４やＭｎ２０３）が析出された混合相となり
、カルシウムドープランタンマンガナイト中のランタン
とジルコニアが反応し電解質の電気抵抗を高くしてしま
うし、燃料電池の作動温度で結晶＃Ｉ遣が変化して熱膨
張率が異常に高くなり、固体電解質の空気極とし、て使
用する場合には機械的に不安定となる。(Action) (L a l -K Cat ) ly M n 0
Calcium-doped lanthanum mancanite-based oxide represented by i-z becomes a mixed phase in which manganese oxide (Mn304 and Mn203) is precipitated at high temperature when y = Q, and the Lanthanum and zirconia react, increasing the electrical resistance of the electrolyte, and the crystal #I ratio changes at the operating temperature of the fuel cell, resulting in an abnormally high coefficient of thermal expansion, making it difficult to use as an air electrode for the solid electrolyte. In some cases, it becomes mechanically unstable.
しかし、ｙ＞ｏの不定比となると、高温下で酸化マンガ
ン（Ｍｎ３０４やＭｎ２０３）が析出されない単相とな
り、ジルコニアと反応することがないか、ｙ≦０．０２
５の範囲であると燃ｆ１電池の作動温度付近で結晶構造
が変化して熱膨張率が異常に高くなり、固体電解質の空
気極として使用する場合には機械的強度に対し不安定と
なる１反面、ｙ＞ｏ、０２５の範囲であると、燃料電池
の作動温度付近で結晶構造が変化することがなく熱膨張
率が変化しないので、固体電解質の空気極として使用す
る場合には機械的強度が安定となる。However, when the non-stoichiometric ratio of y>o exists, manganese oxide (Mn304 and Mn203) becomes a single phase in which it does not precipitate at high temperatures and may react with zirconia.
If it is in the range of 5, the crystal structure will change near the operating temperature of the fuel F1 battery and the coefficient of thermal expansion will become abnormally high, making it unstable with respect to mechanical strength when used as an air electrode for a solid electrolyte. On the other hand, if y>o is in the range of 025, the crystal structure will not change near the operating temperature of the fuel cell and the coefficient of thermal expansion will not change, so when used as an air electrode of a solid electrolyte, the mechanical strength is low. becomes stable.
また、Ｏ＜ｘ＜０．２でかつｙ≧０．７５の不定比にな
ると、酸化マンガン（Ｍｎｓ ０７１やＭｎ２０３）が
析出された混合相となり、ジルコニア電解質と反応して
ランタンジルコネートを生成する。In addition, when O<x<0.2 and y>=0.75, which is a non-stoichiometric ratio, a mixed phase in which manganese oxide (Mns071 and Mn203) is precipitated is formed, which reacts with the zirconia electrolyte to produce lanthanum zirconate. .
また、０．２＜ｘ＜０．４でかつｙ≧０．０５の不定比
になると、酸化マンガン（Ｍｎ３０４やＭｎ２０ｓ ）
が析出された混合相となり、ジルコニア電解質と反応し
て導電率が低いマンガンドープジルコニアを生成する。In addition, when 0.2<x<0.4 and y≧0.05, which is a non-stoichiometric ratio, manganese oxide (Mn304 and Mn20s)
becomes a precipitated mixed phase that reacts with the zirconia electrolyte to produce manganese-doped zirconia with low conductivity.
（実施例）
以下、本発明の構成を図面に示す実施例に基づいて詳細
に説明する。(Example) Hereinafter, the configuration of the present invention will be described in detail based on an example shown in the drawings.
本発明のランタンマンガナイトは、主成分の各々の元素
が（Ｌ ａ １−ｘ Ｃａｘ ） ＋ −ｙ Ｍ ｎ
０ｊ−ｚであり、ｘ、ｙの値がＯ＜ｘ＜０．２でかつ０
．０２５＜ｙ＜０．７５を満足したものである。In the lanthanum manganite of the present invention, each element of the main component is (L a 1-x Cax ) + -y M n
0j-z, and the values of x and y are O<x<0.2 and 0
．． 025<y<0.75.
また、本発明のカルシウムドープランタンマンガナイ１
〜は、ｘ、ｙの値が０．２≦ｘ＜０．４でかつ０．０２
５＜ｙ＜０．０５を満足したものである。ここで２は、
通常約±０．１程度である。Moreover, the calcium-doped lanthanum manganese 1 of the present invention
~ means that the values of x and y are 0.2≦x<0.4 and 0.02
5<y<0.05. Here, 2 is
It is usually about ±0.1.
しかしながら、このＺの値は温度、時間、置換比Ｘ、不
定比量ｙによって変化することから、その値を正確に規
定することは余り意味がないのでここでは特に説明しな
い。However, since the value of Z changes depending on temperature, time, substitution ratio X, and nonstoichiometric amount y, it is meaningless to define the value accurately, so it will not be particularly explained here.
このランタンマンガナイト粉体の合成は、粉混ぜ法、ゾ
ルゲル法、共沈法等の製法により準備可能である０例え
ば、このランタンマンガナイトが粉混ぜ法によってり作
られる場合について具体的に説明すると、以下の通りと
なる。。This lanthanum manganite powder can be synthesized by methods such as the powder mixing method, sol-gel method, and coprecipitation method. , is as follows. .
（１）酸化ランタン（Ｌａ２０３）と、炭酸カルシウム
（ＣａＣＯａ ）と、酸化マンガン（Ｍｎ２０３）とを
所定モル比で、例えばＬａ２０ｓｌＯＯ，Ｏｇ、ＣａＣ
Ｏ５１５，４ｇ、Ｍｎ２０ｓ １２７．８ｇを混合し、
（Ｌａｏ、ｓ Ｃａｏｙｚ ） ｏ、＊ｓＭ ｎ Ｏｓ
−ｚの組成の混合粉末を得な、このとき、酸化ランタ
ンは吸湿性であるため、１５００℃、１時間で焼成して
乾燥させてから混合した。酸化マンガンは化学滴定分析
法を用いてＭｎ２０．。２と明らかに分っているものを
用いた。また、炭酸カルシウムは不純物が多いため、市
販で最も不純物か少ない特級試薬（和光純薬社製商品名
炭酸カルシウム、９つ。９％）を用いた。(1) Lanthanum oxide (La203), calcium carbonate (CaCOa), and manganese oxide (Mn203) are mixed in a predetermined molar ratio, for example, La20slOO, Og, CaC
Mix 15.4 g of O5 and 127.8 g of Mn20s,
(Lao, s Caoyz) o, *sM n Os
A mixed powder having the composition -z was obtained. At this time, since lanthanum oxide is hygroscopic, it was baked and dried at 1500° C. for 1 hour and then mixed. Manganese oxide was determined to be Mn20. using chemical titration analysis. . I used one that was clearly known to be 2. In addition, since calcium carbonate has many impurities, a commercially available special grade reagent with the least impurities (trade name: calcium carbonate, manufactured by Wako Pure Chemical Industries, Ltd., 9, 9%) was used.
（２）次にこれら粉末を乳鉢で混合した後、１１００℃
、１２時間焼成しな。(2) Next, after mixing these powders in a mortar,
, Bake for 12 hours.
（３）この試料を粉砕混合しベレットに成型後、１３５
０°Ｃで１２時間焼成した。(3) After pulverizing and mixing this sample and forming it into a pellet, 135
It was baked at 0°C for 12 hours.
（４）さらに、この試料を粉砕混合しベレットに成型後
、１４５０℃で３時間焼成した。(4) Furthermore, this sample was pulverized and mixed, formed into a pellet, and then fired at 1450° C. for 3 hours.
以上のようにして得られた（ Ｌ ａ ｌ −！ Ｃａ
工）１−ｙ Ｍ ｎ、 Ｏｓ−ｘ系カルシウムドープラ
ンタンマンガナイトの結晶系をＸ線粉末解析法を用いて
解析した６その結果を第３図に示す。解析は、フィリッ
プス社製Ｘ線解析装置（商品名：ＰＷ１８００）を用い
て、上述の合成法で作製した試料をベレットに成型して
、８００℃、１０００℃、１３００℃の各温度で焼成し
た。その後、液体チッ素中で急冷して、高温でのカルシ
ウムドープランタンマンガナイトの状態を低温で観察で
きるようにしな。Obtained as above (L a l -! Ca
The crystal system of 1-yMn,Os-x calcium-doped lanthanum manganite was analyzed using an X-ray powder analysis method6. The results are shown in FIG. For the analysis, the sample prepared by the above synthesis method was molded into a pellet using an X-ray analyzer manufactured by Philips (trade name: PW1800), and the pellet was fired at temperatures of 800°C, 1000°C, and 1300°C. After that, it was rapidly cooled in liquid nitrogen so that the state of calcium-doped lanthanum manganite at high temperatures could be observed at low temperatures.
この図からこれらは全てへロブスカイト型構造をもつこ
とが分かっな６しかし、その結晶構造は、８００℃では
菱面体晶系（以下Ａ型）、１０００℃では見掛けは正方
晶系の斜方晶系（以下Ｂ型）、１３００℃では斜方晶系
（以下Ｃ型）をとり、温度によって興なることがわかる
。From this figure, it can be seen that all of these have a herovskite structure.6 However, the crystal structure is rhombohedral (hereinafter referred to as type A) at 800°C, and orthorhombic with an apparent tetragonal system at 1000°C. (hereinafter referred to as type B), and at 1300° C., it becomes an orthorhombic system (hereinafter referred to as type C), and it can be seen that the change occurs depending on the temperature.
また、Ａサイト欠損の不定比カルシウムドープランタン
マンガナイト（（Ｌａ＋ −１１Ｃａｘ ） Ｉ−ｙＭ
ｎ Ｏｓ−ｓ ）の置換比（ｘ＞と不定比（ｙ）の値
との関係において単相領域を求めた。その結果を第４図
に示す、該図においてはムがＭｎＯ４析出を、○が単相
を示す、定片（（ｙ＝ｏ）ではランタンが電解質のジル
コニアと反応してランタンジルコネート等の化合物を生
成することは既に説明しているが、不定比にしても、Ｏ
＜ｘ＜０．２でかつｙ≧０，７５の不定比になると、酸
化マンガン（Ｍｎｓ ＯａやＭｎ２０ｓ ）が析出され
た混合相となり、ジルコニア電解質と反応して導電率の
低いマンガンドーグジルコニアを生成する。また、０．
２＜ｘ＜０．４でかつｙ≧０．０５の不定比になると、
酸化マンガン（Ｍｎａ Ｏ，ｉやＭｎ２０３）が析出さ
れた混合相となり、ジルコニア電解質と反応してマンガ
ンドープジルコニアを生成する。これから、カルシウム
ドープランタンマンガナイト（（Ｌａｌ−ｘ Ｃａｗ
）ｒ−ｙ Ｍｎ０ｊ−ｓ ）の電解質・ジルコニアと反
応しない安定な領域は、Ｘ＋３’の値がＯ＜ｘ＜０．２
でかつ０くｙく０７５の範囲、あるいは０．２≦ｘ＜０
．４でかつ０＜ｙ＜０．０５の範囲であることが分る。In addition, A-site-deficient nonstoichiometric calcium-doped lanthanum manganite ((La+ -11Cax) I-yM
The single-phase region was determined based on the relationship between the substitution ratio (x> of nOs-s) and the value of the nonstoichiometric ratio (y).The results are shown in Figure 4. In this figure, MnO4 precipitation is It has already been explained that in a constant piece ((y=o) where lanthanum shows a single phase, lanthanum reacts with zirconia in the electrolyte to produce compounds such as lanthanum zirconate, but even in a non-stoichiometric ratio, O
When <x<0.2 and y>=0.75 non-stoichiometric ratio, a mixed phase in which manganese oxide (MnsOa or Mn20s) is precipitated becomes a mixed phase, which reacts with the zirconia electrolyte to produce manganese dawg zirconia with low conductivity. do. Also, 0.
When 2<x<0.4 and y≧0.05 nonstoichiometric ratio,
A mixed phase is formed in which manganese oxide (MnaO,i and Mn203) is precipitated, and reacts with the zirconia electrolyte to produce manganese-doped zirconia. From now on, calcium-doped lanthanum manganite ((Lal-x Caw
)ry Mn0j-s) The stable region that does not react with the electrolyte/zirconia has a value of X+3' of O<x<0.2
and 0 x y x 075 range, or 0.2≦x<0
．． 4 and is in the range of 0<y<0.05.
また、不定比カルシウムドープランタンマンガナイト（
（Ｌａｌ−ｘ Ｃａｗ ）ｌ−ｙ Ｍｎ０ｓ−ｓ ）の
温度域における結晶構造を不定比の値との関係において
求めた。その結果を第５図に示す、これは８００℃から
１４００℃の範囲において各温度で４８時間焼成したと
きの不定比カルシウムドープランタンマンガナイト（（
Ｌ ａ ｒ−ｔ Ｃａｘ ） 、−２Ｍ ｎ Ｏｊ−ｘ
ンのものである。Ｏ＜ｙ≦０．０２５の範囲では、第４
図からも明らかなように単相ではあるものの、燃料電池
の作動温度付近たる１０００℃で結晶構造がＡ型からＢ
型へと変化している。このことは、後述するように、熱
膨張率の変化を招き、異常な伸びによって固体電解質の
空気極として使用する場合には機械的強度が不安定とな
る。即ち、不定比のカルシウムドープランタンマンガナ
イトの結晶系は電比のものと比較し、燃料電池の作動温
度における結晶系が安定し、体積膨張を含まず熱応力が
発生しないことが分つな。In addition, non-stoichiometric calcium-doped lanthanum manganite (
The crystal structure of (Lal-x Caw)ly Mn0s-s) in the temperature range was determined in relation to the nonstoichiometric value. The results are shown in Figure 5, which shows the non-stoichiometric calcium-doped lanthanum manganite ((
L a r-t Cax ) , -2M n Oj-x
It belongs to N. In the range O<y≦0.025, the fourth
As is clear from the figure, although it is a single phase, the crystal structure changes from type A to type B at 1000℃, which is around the operating temperature of fuel cells.
It is changing into a type. As will be described later, this causes a change in the coefficient of thermal expansion, and the abnormal elongation makes the mechanical strength unstable when used as an air electrode for a solid electrolyte. In other words, it can be seen that the crystal system of non-stoichiometric calcium-doped lanthanum manganite is more stable at the operating temperature of the fuel cell than that of electric ratio, and does not include volumetric expansion and does not generate thermal stress.
特に、０．０２５＜ｙ＜０．７５の範囲では結晶構造は
燃料電池の作動温度付近で安定しており、熱膨張率の異
常な変動などは招く虞がない。尚、この領域では最も変
化が生じ易い昇温後４８時間において安定していること
から、その後も安定していると推測できる。In particular, in the range of 0.025<y<0.75, the crystal structure is stable near the operating temperature of the fuel cell, and there is no risk of abnormal fluctuations in the coefficient of thermal expansion. In addition, since it is stable in this region for 48 hours after temperature rise, when changes are most likely to occur, it can be inferred that it is stable even after that.
したがって、不定比カルシウムドープランタンマンガナ
イト（（Ｌａｌ−＋ｃ Ｃａｍ ） ｌ−ｙ ＭｎＣ）
ｓ８）はその置換比（ｘ＞と不定比（ｙ）の値を、０＜
ｘ＜０．２でかつ０．０２５＜ｙ＜０．７５の範囲、あ
るいは０．２≦ｘ＜０．４でかつ０゜０２５＜ｙ＜０．
０５の範囲にとることが最も好ましい、このように、熱
力学的に安定な組成は非常に微小な領域であることがわ
かった。Therefore, nonstoichiometric calcium-doped lanthanum manganite ((Lal-+c Cam ) ly MnC)
s8) is the value of the substitution ratio (x> and non-stoichiometric ratio (y)), 0<
x<0.2 and 0.025<y<0.75, or 0.2≦x<0.4 and 0°025<y<0.
It has been found that the thermodynamically stable composition is most preferably in the range of 0.05 and is in a very small range.
次にＡサイト欠損の不定比ランタンマンガナイトの導電
率（を気抵抗の逆数）と不定比の値との関係を求めた。Next, the relationship between the electrical conductivity (the reciprocal of the air resistance) and the nonstoichiometric value of the A-site-deficient nonstoichiometric lanthanum manganite was determined.
その結果を第６図に示す、この測定は不定比（ｙ＝０）
のもの（○）と、不定比（ｙ＝０．０２５＞のもの（・
）と、不定比（ｙ＝０．０５）のもの（Δ）とについて
行なった。The results are shown in Figure 6. This measurement is non-stoichiometric (y = 0).
(○) and non-stoichiometric (y=0.025>) (・
) and a non-stoichiometric (y=0.05) one (Δ).
測定した試料は上述の３種類のカルシウムドープランタ
ンマンガナイトを１４５０℃、３時間焼成したベレット
をダイヤモンドカッターで長方体に切り、４端子法によ
り空気中で室温から１０００℃まで測定した。その結果
、不定比カルシウムドープランタンマンガナイトは定片
カルシウムドープランタンマンガナイトよりも導電率が
良いことが分る。The samples to be measured were pellets made of the above-mentioned three types of calcium-doped lanthanum manganite fired at 1450°C for 3 hours, cut into rectangular bodies using a diamond cutter, and measured in air from room temperature to 1000°C using the four-terminal method. The results show that nonstoichiometric calcium-doped lanthanum manganite has better electrical conductivity than fixed-piece calcium-doped lanthanum manganite.
これらの実験から、本発明の組成領域をとる不定比のカ
ルシウムドープランタンマンガナイトは、固体電解質燃
料電池の空気極として安定であり、かつ導電率も良いこ
とが明らかである。From these experiments, it is clear that non-stoichiometric calcium-doped lanthanum manganite having the composition range of the present invention is stable as an air electrode of a solid electrolyte fuel cell and has good conductivity.
したがって本発明の不定比のカルシウムドープランタン
クロマイト粉体を焼成した焼結体を、例えば第１図ある
いは第２図に示すような固体電解質燃料電池の空気極と
して利用する場合、寿命が長く安定的に作動する固体電
解質燃料電池が得られると共に燃料電池の他の構成部材
と共焼結法等により一度に製造することができる。Therefore, when the sintered body obtained by firing the non-stoichiometric calcium-doped lanthanum chromite powder of the present invention is used as an air electrode of a solid electrolyte fuel cell as shown in FIG. 1 or 2, it has a long life and is stable. A solid electrolyte fuel cell that operates efficiently can be obtained, and it can be manufactured at once with other constituent members of the fuel cell by a co-sintering method or the like.
例えば第１図に平板型固体電解質燃料電池の空気極とし
て構成した一例を分解斜視図で示す。この燃料電池は、
平板の単電池１とセパレータ４をスペーサ２，３を介し
て交互に積重ね、単電池１とセパレータ４とによって形
成される空気供給用空間５と燃焼ガス供給用空間６とに
燃焼ガスと空気が燃料ガス供給パイプ７と空気供給パイ
プ８を介して夫々供給される。更に、単電池１は固＃電
解質９の表面側と裏面側に空気極１０と燃料極１１を形
成して成る。For example, FIG. 1 shows an exploded perspective view of an example configured as an air electrode of a flat solid electrolyte fuel cell. This fuel cell is
Flat cell cells 1 and separators 4 are alternately stacked with spacers 2 and 3 interposed between them, and combustion gas and air are supplied to air supply space 5 and combustion gas supply space 6 formed by cell cells 1 and separators 4. The fuel gas is supplied via a fuel gas supply pipe 7 and an air supply pipe 8, respectively. Further, the unit cell 1 is formed by forming an air electrode 10 and a fuel electrode 11 on the front and back sides of a solid electrolyte 9.
更に、第２図に円筒型の固体電解質燃料電池の空気極と
して構成しな一実施例を示す、この円筒型固体電解質燃
料電池は円筒型の支持体２０の周りに空気極２１と固体
電解質２２と燃料極２３とを同心状に形成し、固体電解
質２２と燃料極２３とを分断するように空気極２１上に
形成されたインターコネクタ２４によって空気極２１側
の電流が取り出されるように設けられている。インター
コネクタ２４と燃料極２３との間には電気的絶縁のため
に清２５が設けられている。空気は支持体２０の内側を
流れ、多孔質の支持体２０を通って空気極２１に供給さ
れる。Furthermore, FIG. 2 shows an embodiment of a cylindrical solid electrolyte fuel cell configured as an air electrode. This cylindrical solid electrolyte fuel cell has an air electrode 21 and a solid electrolyte 22 arranged around a cylindrical support 20. and the fuel electrode 23 are formed concentrically, and the interconnector 24 is formed on the air electrode 21 so as to separate the solid electrolyte 22 and the fuel electrode 23, and the current on the air electrode 21 side is taken out. ing. A gap 25 is provided between the interconnector 24 and the fuel electrode 23 for electrical insulation. Air flows inside the support 20 and is supplied to the air electrode 21 through the porous support 20 .
（発明の効果）
以上の説明から明らかなように、本発明の不定比カルシ
ウムドープランタンマンガナイトによると、燃料電池の
作動温度付近で結晶構造が変化せず、熱膨張係数の変化
が起らないので、燃料電池構成材料間における熱膨張の
差に起因する破壊などを招くことがない。しかも、燃料
電池の作動温度付近においても単相構造であるため、化
学的に安定であり、電解質材料のジルコニアと反応する
ことがないし、導電率にも優れる。このことから、本発
明の不定比カルシウムドーブンタンマンガナイトは高温
での化学的安定性に優れかつ電気の良導体であることが
要求されるもの、例えば固体電解質燃料電池の空気極材
料に適している。(Effects of the Invention) As is clear from the above explanation, according to the non-stoichiometric calcium-doped lanthanum manganite of the present invention, the crystal structure does not change near the operating temperature of the fuel cell, and the coefficient of thermal expansion does not change. Therefore, damage caused by differences in thermal expansion between fuel cell constituent materials does not occur. Furthermore, since it has a single-phase structure even near the operating temperature of a fuel cell, it is chemically stable, does not react with zirconia as an electrolyte material, and has excellent electrical conductivity. Therefore, the non-stoichiometric calcium-doped tanmanganite of the present invention is suitable for materials that are required to have excellent chemical stability at high temperatures and to be a good conductor of electricity, such as air electrode materials for solid electrolyte fuel cells. .
第１図は本発明の不定比カルシウムドープランタンマン
ガナイトを空気極として利用した平板型固体電解質燃料
電池の分解斜視図である。
第２図は本発明の不定比カルシウムドープランタンマン
ガナイトを空気極として利用した円筒型固体電解質燃料
電池の斜視図である。
第３図は不定カルシウムドープランタンマンガナイトの
３つの結晶系の変化を示すＸ線回折パターンである。
第４図はＡサイト欠損の不定比カルシウムドープランタ
ンマンガナイトの単相領域を不定比と置換比との関係で
示すグラフである。
第５図はＡサイト欠損の不定比カルシウムドープランタ
ンマンガナイトの各温度の安定相を示すグラフである。
第６図はＡサイト欠損の不定比ランタンマンガナイトの
導電率を示すグラフである。
１０・・・空気極、２１・・・空気極。
特許出願人 財団法人 電力中央研究所代 理 人
弁理士 村 瀬 −美「
図
第
図
第
図
○
単
相
ム
ｎ ３
Ｏ４析出
０゜
０゜
（Ｌａ。
Ｃａｘ）
ｙＭｎｏｌＺ中のＸ
第
図
ＯＡ型
■
Ｂ型
○
Ｃ型
（Ｌａｏ９
Ｃａ 。
ｙＭｎ０３ ｙ中のｙ
第
図
Ｔ／’Ｃ
温度（Ｔ／に一’）FIG. 1 is an exploded perspective view of a flat solid electrolyte fuel cell using the non-stoichiometric calcium-doped lanthanum manganite of the present invention as an air electrode. FIG. 2 is a perspective view of a cylindrical solid electrolyte fuel cell using the non-stoichiometric calcium-doped lanthanum manganite of the present invention as an air electrode. FIG. 3 is an X-ray diffraction pattern showing changes in three crystal systems of indefinite calcium-doped lanthanum manganite. FIG. 4 is a graph showing the single-phase region of non-stoichiometric calcium-doped lanthanide manganite with A-site defects in relation to non-stoichiometric ratio and substitution ratio. FIG. 5 is a graph showing stable phases at various temperatures of non-stoichiometric calcium-doped lanthanum manganite with A-site defects. FIG. 6 is a graph showing the electrical conductivity of non-stoichiometric lanthanum manganite lacking the A site. 10... air electrode, 21... air electrode. Patent applicant Agent: Central Research Institute of Electric Power Industry
Patent Attorney Murase-mi " Figure Figure Figure Figure ○ Single-phase Mu n 3 O4 precipitation 0゜0゜ (La. Cax) Figure T/'C Temperature (T/')
Claims (1)
分の各々の元素が（Ｌａ＿１＿−＿ｘＣａ＿ｘ）＿１＿
−＿ｙＭｎＯ＿３＿−＿ｚであり、かつｘ，ｙの値が０
＜ｘ＜０．２かつ０．０２５＜ｙ＜０．７５を満足する
カルシウムドープランタンマンガナイト粉体。 （２） カルシウムドープランタンマンガナイトの主成
分の各々の元素が（Ｌａ＿１＿−＿ｘＣａ＿ｘ）＿１＿
−＿ｙＭｎＯ＿３＿−＿ｚであり、かつｘ，ｙの値が０
．２≦ｘ＜０．４かつ ０．０２５＜ｙ＜０．０５ を満足するカルシウムドープランタンマンガナイト粉体
。 （３） 請求項１または２記載のカルシウムドープラン
タンマンガナイト粉体を焼成し、空気極として使用する
ことを特徴とする固体電解質燃料電池。[Claims] (1) Each element of the main component of calcium-doped lanthanum manganite is (La_1_-_xCa_x)_1_
−_yMnO_3_-_z, and the values of x and y are 0
Calcium-doped lanthanum manganite powder satisfying <x<0.2 and 0.025<y<0.75. (2) Each element of the main component of calcium-doped lanthanum manganite is (La_1_-_xCa_x)_1_
−_yMnO_3_-_z, and the values of x and y are 0
．． Calcium-doped lanthanum manganite powder satisfying 2≦x<0.4 and 0.025<y<0.05. (3) A solid electrolyte fuel cell characterized in that the calcium-doped lanthanum manganite powder according to claim 1 or 2 is fired and used as an air electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2273173A JP2968326B2 (en) | 1990-10-15 | 1990-10-15 | Calcium D-Plantan Manganite and Solid Electrolyte Fuel Cell Using It |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2273173A JP2968326B2 (en) | 1990-10-15 | 1990-10-15 | Calcium D-Plantan Manganite and Solid Electrolyte Fuel Cell Using It |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04149023A true JPH04149023A (en) | 1992-05-22 |
| JP2968326B2 JP2968326B2 (en) | 1999-10-25 |
Family
ID=17524120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2273173A Expired - Lifetime JP2968326B2 (en) | 1990-10-15 | 1990-10-15 | Calcium D-Plantan Manganite and Solid Electrolyte Fuel Cell Using It |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2968326B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0633619A1 (en) * | 1992-01-13 | 1995-01-11 | Ngk Insulators, Ltd. | Air electrode bodies for solid oxide fuel cells, a process for the production thereof, and a production of solid oxide fuel cells |
| WO2019106994A1 (en) * | 2017-11-29 | 2019-06-06 | 株式会社村田製作所 | Ceramic member |
| WO2020008731A1 (en) * | 2018-07-05 | 2020-01-09 | 株式会社村田製作所 | Ceramic member and electronic element |
| CN113644282A (en) * | 2021-07-07 | 2021-11-12 | 湖北文理学院 | Preparation method of carbon composite catalytic electrode and aluminum-air battery device |
-
1990
- 1990-10-15 JP JP2273173A patent/JP2968326B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0633619A1 (en) * | 1992-01-13 | 1995-01-11 | Ngk Insulators, Ltd. | Air electrode bodies for solid oxide fuel cells, a process for the production thereof, and a production of solid oxide fuel cells |
| US5453330A (en) * | 1992-01-13 | 1995-09-26 | Ngk Insulators, Ltd. | Air electrode bodies for solid oxide fuel cells, a process for the production thereof, and a production of solid oxide fuel cells |
| WO2019106994A1 (en) * | 2017-11-29 | 2019-06-06 | 株式会社村田製作所 | Ceramic member |
| JPWO2019106994A1 (en) * | 2017-11-29 | 2020-11-19 | 株式会社村田製作所 | Ceramic member |
| US10886043B2 (en) | 2017-11-29 | 2021-01-05 | Murata Manufacturing Co., Ltd. | Ceramic member |
| WO2020008731A1 (en) * | 2018-07-05 | 2020-01-09 | 株式会社村田製作所 | Ceramic member and electronic element |
| JPWO2020008731A1 (en) * | 2018-07-05 | 2021-06-03 | 株式会社村田製作所 | Ceramic members and electronic devices |
| US11776717B2 (en) | 2018-07-05 | 2023-10-03 | Murata Manufacturing Co., Ltd. | Ceramic member and electronic device |
| CN113644282A (en) * | 2021-07-07 | 2021-11-12 | 湖北文理学院 | Preparation method of carbon composite catalytic electrode and aluminum-air battery device |
| CN113644282B (en) * | 2021-07-07 | 2022-12-20 | 湖北文理学院 | Preparation method of carbon composite catalytic electrode and aluminum-air battery device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2968326B2 (en) | 1999-10-25 |
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