JPH04193701A - Production of perovskite type oxide powder - Google Patents
Production of perovskite type oxide powderInfo
- Publication number
- JPH04193701A JPH04193701A JP2322168A JP32216890A JPH04193701A JP H04193701 A JPH04193701 A JP H04193701A JP 2322168 A JP2322168 A JP 2322168A JP 32216890 A JP32216890 A JP 32216890A JP H04193701 A JPH04193701 A JP H04193701A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- perovskite
- type oxide
- oxide
- particle size
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- -1 acetate Chemical class 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 35
- 239000002994 raw material Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 7
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- 239000000446 fuel Substances 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000007784 solid electrolyte Substances 0.000 description 22
- 238000010304 firing Methods 0.000 description 16
- 239000010409 thin film Substances 0.000 description 16
- 239000000758 substrate Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Classifications
-
- 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
【発明の詳細な説明】
Ａ、産業上の利用分野
本発明は、ペロブスカイト型酸化物の製造方法に関する
。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a method for producing perovskite-type oxides.
Ｂ０発明の概要
本発明は、ペロブスカイト型酸化物を構成する原料金属
を有機酸塩または炭酸塩化合物の形で供給して夫々処理
を行うことにより粒径の揃ったペロブスカイト型酸化物
の粉体を得るものである。B0 Summary of the Invention The present invention provides a method for producing perovskite oxide powder with uniform particle size by supplying the raw material metal constituting the perovskite oxide in the form of an organic acid salt or a carbonate compound and treating each of them. It's something you get.
Ｃ０従来の技術
一般に燃料電池本体は、固体電解質の両側に陽極と陰極
の電極板を配置して単位電池を構成し、この単セルを複
数個直列に接続するよう積層して構成されている。C0 Prior Art In general, a fuel cell main body is constructed by arranging anode and cathode electrode plates on both sides of a solid electrolyte to form a unit cell, and stacking a plurality of these unit cells so as to connect them in series.
この電池の単セル構造は水素等の燃料ガスを適宜に貫流
する多孔質基板を支持構造部制として用いるともにこの
多孔質基板の表面に薄膜陰極、薄膜の固体電解質、簿膜
の陽極を順次積層構造に形成したものである。そして、
上記単セルの薄膜陰極側には燃料として水素ガス（水素
）を供給し、薄膜の陽極側には酸化剤として空気（酸素
）を供給して水素と酸素とを反応させて電気を発生させ
るとともに水が生成される。The single cell structure of this battery uses a porous substrate as a support structure through which fuel gas such as hydrogen flows appropriately, and a thin film cathode, a thin film solid electrolyte, and a thin film anode are sequentially laminated on the surface of this porous substrate. It is formed into a structure. and,
Hydrogen gas (hydrogen) is supplied as a fuel to the thin film cathode side of the single cell, and air (oxygen) is supplied as an oxidizing agent to the thin film anode side to cause the hydrogen and oxygen to react and generate electricity. water is produced.
このような電池の単セルでは薄膜の固体電解質自身の抵
抗骨による電圧降下を小さくするために、固体電解質の
厚さは薄いほうが良い。In a single cell of such a battery, the thickness of the solid electrolyte should be thinner in order to reduce the voltage drop due to the resistance bones of the thin film solid electrolyte itself.
これは薄膜の固体電解質に流れる電流をｉ （Ａ）、固
体電解質の抵抗をＲ（Ωａｍ）とし、固体電解質の厚さ
をｔ（μｍ）とすると、固体電解質中の電圧降下Ｖｄは
、
Ｖｄ＝ ｉ−Ｒ−ｔＸ １０−’と表すことができ、」
１記式から薄膜の固体電解質の厚さは、より薄いほうが
電圧降下が少なくてすむことがわかる。If the current flowing through the thin film solid electrolyte is i (A), the resistance of the solid electrolyte is R (Ωam), and the thickness of the solid electrolyte is t (μm), then the voltage drop Vd in the solid electrolyte is: Vd= It can be expressed as i-R-tX 10-',
From Equation 1, it can be seen that the thinner the thin film solid electrolyte is, the less the voltage drop will be.
一方、この薄膜の固体電解質は多孔質基板上に形成され
ることから、その薄膜のカバレッジ性を考慮すると無条
件に簿く構成することはできす、結局１０μｍ〜５０７
１ｍ程度の厚さに形成するのが良いことが解っている。On the other hand, since the solid electrolyte of this thin film is formed on a porous substrate, considering the coverage of the thin film, it is not possible to configure it unconditionally.
It has been found that it is best to form the film to a thickness of about 1 m.
一般に入手できる多孔質基板は、その孔径に、例えば０
．５〜４０μｍとばらつきがあり、この多孔質基板の表
面に電極、薄膜の固体電解質を積層形成した場合、大き
な孔径の」二部で、薄膜の固体電解質にピンホールがで
き易いという問題点があった。Generally available porous substrates have a pore diameter of, for example, 0.
．． When electrodes and thin film solid electrolyte are laminated on the surface of this porous substrate, there is a problem that pinholes are likely to form in the thin film solid electrolyte in the two parts with large pore diameters. Ta.
燃料電池は薄膜の固体電解質を挟んでの酸素分圧が異な
ると、一種の酸素濃淡電池が構成され、薄膜の固体電解
質の両端に起電力を発生するものであり、このときの起
電力Ｅ。は次式で表される。A fuel cell forms a type of oxygen concentration cell when the oxygen partial pressure across the thin film solid electrolyte is different, and an electromotive force is generated at both ends of the thin film solid electrolyte.The electromotive force E at this time. is expressed by the following formula.
Ｅｏ＝（ＲＴ／４ Ｆ）ＸＩｎ（Ｐ＋／Ｐ２）上記式か
ら起電力Ｅ。は酸素分圧の比に比例して増加する。なお
。式において、Ｒは気体定数、Ｔは絶対温度、Ｆはファ
ラデ一定数、Ｐ、、Ｐ２は各々固体電解質を挟んでの酸
素分圧である。Eo=(RT/4F)XIn(P+/P2) From the above formula, the electromotive force E. increases in proportion to the ratio of oxygen partial pressures. In addition. In the formula, R is a gas constant, T is an absolute temperature, F is a Faraday constant, and P, P2 are oxygen partial pressures across the solid electrolyte.
上記のように薄膜の固体電解質にピンホールができると
、酸素分圧の比は小さくなるため、このような単セルを
用いた燃料電池では起電力の低下や最悪の場合には起電
力が発生しなくなってしまう不都合があった。As mentioned above, if a pinhole is formed in the thin film solid electrolyte, the oxygen partial pressure ratio will decrease, so in a fuel cell using such a single cell, the electromotive force will decrease, or in the worst case, an electromotive force will occur. There was an inconvenience that it stopped working.
そこで、二種の粒径のペロブスカイト型酸化物粉体を製
造して多孔質ステンレス基板上を被覆し、表面粗さが、
固体電解質の膜厚の１７１０程度で、かつガスを十分通
すだけの多孔性を有する酸素極を形成した。Therefore, perovskite-type oxide powders with two different particle sizes were manufactured and coated on a porous stainless steel substrate, and the surface roughness was
An oxygen electrode was formed that had a film thickness of about 1710 mm that of the solid electrolyte and had enough porosity to allow gas to pass through.
上記二種の粒径は多孔質ステンレス基板の孔径の大きい
穴を埋めて表面をならす粒径５〜１０１１ｍのものと、
電極表面を覆いその表面の起伏を固体電解質の膜厚の１
７１０程度に抑え、かつ表面積を大きくして触媒能を高
める粒径１μｍ以下のものとの二種類であり、この二種
の粒径のペロブスカイト型酸化物粉体を用いて酸素極を
形成したことにより、多孔質ステンレス基板２上に厚さ
１１０ｌ１程度の薄くかつガスタイトな固体電解質薄膜
を形成することができた。The two types of particle sizes mentioned above are those with a particle size of 5 to 1011 m that fills the large pores of the porous stainless steel substrate and smoothes the surface;
Cover the electrode surface and make the undulations of the surface 1 of the solid electrolyte film thickness.
There are two types of perovskite-type oxide powders: one with a particle size of 1 μm or less, which suppresses the particle size to about 710, and increases the surface area and increases the catalytic ability. As a result, a thin and gas-tight solid electrolyte thin film having a thickness of about 110 l1 could be formed on the porous stainless steel substrate 2.
Ｄ８発明が解決しようとする課題
しかし、上記のように粒径の揃ったペロブスカイト型酸
化物粉体を得るためには分級を繰り返し行うことが必要
である。D8 Problems to be Solved by the Invention However, in order to obtain perovskite-type oxide powder with uniform particle size as described above, it is necessary to perform classification repeatedly.
特に粒径１μｍ以下のペロブスカイト型酸化物粉体を得
る為にはボットミルの等のようなバッチ方式で数日間に
わたって粉砕を行わねばならず、このため粉砕の際にボ
ールやポットから不純物が入り易いうえ、大量の電極材
を得るには非常に時間と手間がかかる。In particular, in order to obtain perovskite-type oxide powder with a particle size of 1 μm or less, it is necessary to grind the powder over several days using a batch method such as a bot mill, which makes it easy for impurities to enter from balls or pots during grinding. Moreover, it takes a lot of time and effort to obtain a large amount of electrode material.
また、粒径５〜１０μｍの粉体を製造する場合には焼成
中に酸素が不足するため焼成時間が長くなってしまい、
更に、焼成時間を短くするために焼成温度を高くすると
異常な粒成長が起きてしまうという問題点があった。In addition, when producing powder with a particle size of 5 to 10 μm, the firing time becomes longer due to the lack of oxygen during firing.
Furthermore, there is a problem in that when the firing temperature is increased to shorten the firing time, abnormal grain growth occurs.
本発明はこのような背景の下になされたものであり、上
記のように粒径の揃った二種のペロブスカイト型酸化物
粉体を簡単かつ大量に製造することを目的とする。The present invention was made against this background, and it is an object of the present invention to easily and mass-produce two types of perovskite-type oxide powders having uniform particle sizes as described above.
Ｅ９課題を解決するための手段
上記課題を解決するため、本発明はペロブスカイト型酸
化物を構成する金属元素の有機酸塩を混合した溶液を作
製し、この溶液を乾燥させて得られる生成物を粉砕、混
合して焼成を行い、この焼成物を粉砕して粉体を得るよ
うにしたことを特徴とする。E9 Means for Solving Problems In order to solve the above problems, the present invention prepares a solution containing a mixture of organic acid salts of metal elements constituting a perovskite type oxide, and dries the solution to produce a product. It is characterized in that it is ground, mixed and fired, and the fired product is ground to obtain a powder.
更に、ペロブスカイト型酸化物を構成する金属元素の内
少なくとも一つを炭酸塩とし、他のペロブスカイト型酸
化物を構成する金属元素を単体もしくは酸化物として、
上記原料の粒径を目的とするペロブスカイト型酸化物の
粒径よりも小径としてこれらの粉体を混合し、この粉体
内に直接酸素を供給しながら焼成して粉体を得るように
したことを特徴とする。Furthermore, at least one of the metal elements constituting the perovskite-type oxide is carbonate, and other metal elements constituting the perovskite-type oxide are used alone or as oxides,
The particle size of the above-mentioned raw materials is smaller than the particle size of the target perovskite oxide, and these powders are mixed and fired while supplying oxygen directly into the powder to obtain the powder. Features.
Ｆ１作用
本発明において、ペロブスカイト型酸化物の原料金属を
例えば酢酸塩等の有機酸塩として供給することにより焼
成物が多孔質となり、また原料金属を炭酸塩とすること
により焼成中に炭酸が分解されて酸素が発生する。F1 action In the present invention, by supplying the raw material metal of perovskite type oxide as an organic acid salt such as acetate, the fired product becomes porous, and by using carbonate as the raw material metal, carbonic acid decomposes during firing. oxygen is generated.
従って焼成時の酸素量が増加して焼成が良好に進行し、
この生成物を粉砕することにより粒径が小さく、しかも
均一である粉体が得られる。Therefore, the amount of oxygen during firing increases, and firing progresses smoothly.
By pulverizing this product, a powder with small and uniform particle size can be obtained.
Ｇ、実施例
通常、燃料電池に用いられる酸素電極材とじてはＡ Ｂ
０３ペロブスカイト型酸化物が知られており、主にＬ
ａ１−ｘＡ’ｘＭＯ３系において、ＭをＣｏ、ＣｒＸＭ
ｎ−、’ Ｎ １％ Ｆ ｅ等の単独もしくは混合とし
、Ａ′をＳｒ、Ｂａ等としてＡサイトを置換したものが
用いられる。G. Examples Oxygen electrode materials usually used in fuel cells are A B
03 perovskite type oxides are known, mainly L
In the a1-xA'xMO3 system, M is Co, CrXM
n-, 'N 1% Fe, etc. alone or as a mixture, and those in which A' is replaced with Sr, Ba, etc. at the A site are used.
本実施例では、ペロブスカイト型酸化物としてＬａｏ６
ｓｒＯ，４ｃ００．９１１ＮｉＯ，［１２ｏ３を用いる
が、他のペロブスカイト型酸化物についても同様な手法
で作成することができる。In this example, Lao6 is used as the perovskite oxide.
Although srO, 4c00.911NiO, and [12o3 are used, other perovskite-type oxides can also be produced using a similar method.
更に、本実施例においては粒径が１μｍ以下のペロブス
カイト型酸化物の粉体を得るための出発原料として各金
属の酢酸塩を用いるが、ナフラン酸塩やオフチル酸塩等
の他の有機酸塩を、夫々の原料が可溶であるブタノール
、エタノール、水等の溶媒に溶解して用いても同様な手
法で粉体を容易に得ることかできる。Furthermore, in this example, acetate of each metal is used as a starting material to obtain perovskite oxide powder with a particle size of 1 μm or less, but other organic acid salts such as napfranate and ophthalate may also be used. Powders can be easily obtained in the same manner by dissolving each raw material in a solvent such as butanol, ethanol, or water in which it is soluble.
まず、粒径が１．ｔｔｍ以下のＬａｏ、ａＳ ｒｏ、４
ｃｏ０．９１１Ｎｊｏｏ２０３の粉体を得るために、（
ＣＨ３ＣＯ０）２Ｃｏ・４Ｈ２０、（ＣＨ３ＣＯＯ）２
ｓｒ”ｏ、５Ｈ２０、Ｌ ａ（ＣＨ３Ｃ００） ３・１
，５Ｈ２０，（ＣＨ３ＣＯＯ）２Ｎｉ・４Ｈ２０を、Ｌ
ａ：Ｓｒ：Ｃｏ：Ｎ１＝０．６＋０．４＋０．０９８：
０．０２となるよう秤量してビンもしくはカップに入れ
、混合粉体１５０ｇに対し５００ｃｃの比率でイオン交
換水を加えてシェイカーミキザーにより乳化させて溶液
を作製する。First, the particle size is 1. Lao below ttm, aS ro, 4
To obtain a powder of co0.911Njoo203, (
CH3COO)2Co・4H20, (CH3COO)2
sr”o, 5H20, L a (CH3C00) 3・1
,5H20,(CH3COO)2Ni・4H20,L
a:Sr:Co:N1=0.6+0.4+0.098:
0.02, put it in a bottle or cup, add ion-exchanged water at a ratio of 500 cc to 150 g of mixed powder, and emulsify with a shaker mixer to prepare a solution.
この溶液を乾燥し易いよううに浅底で面積の大きいバッ
トに入れ、乾燥器内で２５０℃前後で突沸しないようフ
ァンを回転させながら乾燥・分解を行い、中間生成物を
得る。This solution is placed in a vat with a shallow bottom and a large area to facilitate drying, and is dried and decomposed in a dryer at around 250° C. while rotating a fan to prevent bumping, thereby obtaining an intermediate product.
これをらいかい器で粉砕、混合し、成形を行わずに大気
中もしくは酸素気流中でマツフル炉等を用いて７００〜
１０００℃にて１０時間程度焼成を行う。This is crushed and mixed in a miller, and then heated in the atmosphere or in an oxygen stream using a Matsufuru furnace, etc.
Firing is performed at 1000°C for about 10 hours.
こうして得られる生成物は反応ガス放出により多孔質と
なっており、これをらいかい器にて軽く粉砕するだけで
第２図及び第３図のＳＥＭ像に示すような粒径１μｍ以
下の粉体か得られる。The product thus obtained becomes porous due to the release of the reaction gas, and by simply pulverizing it with a sieve, it becomes a powder with a particle size of 1 μm or less as shown in the SEM images in Figures 2 and 3. or can be obtained.
第６図（ａ） 、（ｂ）にこの粉体のＸ線回折結果を示
す。これにより７００〜１０００℃という低温での焼成
ニより単一組成のペロブスカイト型酸化物が得られるこ
とが確認される。Figures 6(a) and 6(b) show the results of X-ray diffraction of this powder. This confirms that a perovskite oxide having a single composition can be obtained by firing at a low temperature of 700 to 1000°C.
また、第７図（ａ）、（ｂ）、（Ｃ）に示される蛍光Ｘ
線回折により、Ｌａ、 Ｓｒ、 Ｃｏ、Ｎｉの各金属が
ともに組成比に従って含有されていることがわかる。In addition, the fluorescence X shown in FIGS. 7(a), (b), and (C)
Linear diffraction reveals that each of the metals La, Sr, Co, and Ni is contained according to the composition ratio.
次に、粒径５〜１０ｍｍの粉体を得る方法を以下に示す
。Next, a method for obtaining powder having a particle size of 5 to 10 mm will be shown below.
本実施例においては、粒径３〜７μｍのＮｉパウダー及
び５ｒＣＯｈパウダーと、粒径１１−２ｔｔのＬａ２０
．。In this example, Ni powder and 5rCOh powder with a particle size of 3 to 7 μm and La20 powder with a particle size of 11-2tt were used.
．． .
パウダー及びＣｏパウダーを原料とする。Powder and Co powder are used as raw materials.
」１記の原料を、目的生成物であるＬａｏ、６Ｓｒｏ、
４Ｃｏ（、９１１ＮｉＯ０２０３を生成するよう、Ｌａ
：Ｓｒ：Ｃ。” 1. The raw materials listed in item 1 are converted into the target products Lao, 6Sro,
4Co(,911NiO0203)
:Sr:C.
：Ｎ１＝０．６＋０．４＋０．０９８：０．０２となる
比率に秤量し、この混合粉体］、ｋ ｇに対してイオン
交換水を］、ｋ ｇ加えた後、ボールミルを用いて１０
時間以上混合を行う。:N1=0.6+0.4+0.098:0.02, and after adding ion-exchanged water to 1 kg of this mixed powder], 1 kg of ion-exchanged water was added using a ball mill for 10
Mix for at least an hour.
このスラリーを乾燥し易いよう浅底で面積の大きいバッ
トに入れ、乾燥器内でファンを使用して１２０℃程度の
温度で突沸しないよう乾燥させてケーキを得る。This slurry is placed in a vat with a shallow bottom and a large area to facilitate drying, and is dried in a dryer using a fan at a temperature of about 120° C. without bumping to obtain a cake.
これをポートに入れてマツフル炉で１２００〜１３００
°Ｃにおいて１０時間程度焼成する。Put this in the port and use the Matsufuru furnace for 1200~1300
Bake at °C for about 10 hours.
この際、アルミナ管等を混合粉体内に挿入し、酸素ガス
を直接粉体に供給する。At this time, an alumina tube or the like is inserted into the mixed powder to supply oxygen gas directly to the powder.
これにより反応が促進され、比較的低温かつ短時間で反
応を完全に終了させ、かつ異常な粒成長を抑制すること
ができる。This accelerates the reaction, completes the reaction at a relatively low temperature and in a short period of time, and suppresses abnormal grain growth.
第４図及び第５図は上記のように作製した粉体をらいか
いした後のＳＥＭ解析像で、この回折像により、下記第
１表に示す粒度分布が得られ、粉体の粒径が４〜１０μ
ｍの範囲に収まっていることが解る。Figures 4 and 5 are SEM analysis images of the powder produced as described above. From these diffraction images, the particle size distribution shown in Table 1 below was obtained, and the particle size of the powder was determined. 4~10μ
It can be seen that it falls within the range of m.
以下余白
また、第８図（ａ） 、（ｂ）はこれのＸ線解析結果で
あり、単一組成のペロブスカイト・型酸化物が得られて
いることが示される。The following margins and FIGS. 8(a) and 8(b) show the results of X-ray analysis, showing that a perovskite type oxide of a single composition was obtained.
上記の出発原料において、本実施例でのＣ０１Ｌａ２０
３のように、ペロブスカイトの主成分となる原料は焼成
中に粒子が成長して粒径が大きくなるため、予め粒径５
μｍ以下程度の小粒径の粉体を゛ 用いることが好ま
しい。In the above starting materials, C01La20 in this example
3, the raw material that is the main component of perovskite grows during firing and the particle size increases, so the particle size is 5.
It is preferable to use powder with a small particle size of about μm or less.
また、焼成温度を低下さぜるためにＳｒＣＯ３のような
炭酸塩を用いても良い。Furthermore, a carbonate such as SrCO3 may be used to lower the firing temperature.
これに対して、焼成途中で分解する炭酸塩及び含有量の
少ない原料は上記の主成分となる原料に比して粒径の大
きい粉体を用いても良く、本実施例においても炭酸塩の
ＳｒＣＯ３及び含有量の少ないＮｉは、共に粒径が３〜
７μｍ程度と、上記主原料に比して大きくなっている。On the other hand, for carbonate that decomposes during firing and raw materials with a small content, powder with a larger particle size than the above-mentioned main component raw materials may be used, and in this example, carbonate SrCO3 and Ni with a small content both have particle sizes of 3 to 3.
It is approximately 7 μm, which is larger than that of the main raw material.
また、上記の形成方法によりペロブスカイト型酸化物粉
体が簡単かつ大量に得られるようになり、上記の多孔質
基板上に酸素極、固体電解質、燃料極をこの順で積層し
た水抜けの良い燃料電池を容易に構成出来るようになっ
ている。In addition, perovskite-type oxide powder can be obtained easily and in large quantities using the above-mentioned formation method, and a fuel with good water drainage in which an oxygen electrode, a solid electrolyte, and a fuel electrode are laminated in this order on the above-mentioned porous substrate is also available. The battery can be easily configured.
■９発明の効果
本発明によれば、粒径が１μｍ以下のベロブスカイト型
酸化物の粉体を製造する際に、ペロブスカイト型酸化物
の原料となる金属元素の有機酸塩を用いているため、焼
成中に反応ガス放出が起き、このため生成物が多孔質な
ものとなる。■9 Effects of the invention According to the invention, when producing a powder of a perovskite-type oxide with a particle size of 1 μm or less, an organic acid salt of a metal element, which is a raw material for the perovskite-type oxide, is used. , reactive gas evolution occurs during calcination, which makes the product porous.
従って、この生成物の粉砕を行うと通常の生成物を粉砕
したときに比して粉体の粒径が小さくなり、この製造方
法により粒径１μｍ以下の粉体が簡単かつ大量に得られ
、従来の製造方法に比して製造時間が大幅に短縮され、
また不純物の混合が生じる危険性も非常に小さくなって
いる。Therefore, when this product is pulverized, the particle size of the powder becomes smaller than when a normal product is pulverized, and this production method allows powder with a particle size of 1 μm or less to be obtained easily and in large quantities. Manufacturing time is significantly reduced compared to traditional manufacturing methods,
Also, the risk of contamination with impurities is extremely reduced.
また、粒径５〜１０μｍのペロブスカイト型酸化物の粉
体を製造する際に原料の粒径を目的とする粒径よりも小
さくしており、またペロブスカイト型酸化物の構成金属
元素の内少なくとも一つを焼成中に分解して酸素を発生
する炭酸塩として更にアルミナ管等を粉体内に挿入して
焼成中に酸素を粉体中に直接供給している。In addition, when manufacturing perovskite oxide powder with a particle size of 5 to 10 μm, the particle size of the raw material is made smaller than the target particle size, and at least one of the constituent metal elements of the perovskite oxide is In addition, an alumina tube or the like is inserted into the powder to supply oxygen directly into the powder during firing.
」１記の方法により、焼成中に酸素が十分に供給されて
反応が促進されて焼成時間の短縮及び焼成温度を低く抑
えることができる。By the method described in item 1, oxygen is sufficiently supplied during firing to promote the reaction, thereby making it possible to shorten the firing time and keep the firing temperature low.
従って、原料の粒成長が抑制されて目的とする粒径のペ
ロブスカイト型酸化物が得られる。Therefore, the grain growth of the raw material is suppressed, and a perovskite oxide having the desired grain size can be obtained.
第１図〜第５図は本実施例にかかる粉体の粒子構造を示
す写真、第６図（ａ）、（ｂ）、第７図（ａ）、（ｂ）
、（ｃ）、第８図（ａ）、（ｂ）は本実施例にかかる粉
体のＸ線回折グラフ、第９図は燃料電池の構成図である
。
１・・・ステンレスパイプ、２・・・多孔質ステンレス
基板、３・・・電極、４・・・固体電解質、５・・・電
極、第１図
第２図
第３図
第４図
ＰＡ 目
−牽
萌郵
ｅｂ
嶌
００圃
縫
１ □
ガスＢ
ステンレスパイプ
・・多孔質ステンレス基板
・電極
・・固体電解質
・電極
−１４＝Figures 1 to 5 are photographs showing the particle structure of the powder according to this example, Figures 6 (a), (b), and Figure 7 (a), (b).
, (c), FIGS. 8(a) and (b) are X-ray diffraction graphs of the powder according to this example, and FIG. 9 is a configuration diagram of the fuel cell. 1... Stainless steel pipe, 2... Porous stainless steel substrate, 3... Electrode, 4... Solid electrolyte, 5... Electrode, Figure 1 Figure 2 Figure 3 Figure 4 PA Eye- Kenmoe mail eb Shima 00 farm stitch 1 □ Gas B Stainless steel pipe...Porous stainless steel substrate/Electrode...Solid electrolyte/Electrode-14=
Claims (2)
機酸塩を混合した溶液を作製し、この溶液を乾燥させて
得られる生成物を粉砕、混合して焼成を行い、この焼成
物を粉砕して粉体を得るようにしたことを特徴とするペ
ロブスカイト型酸化物粉体の製造方法。(1) Prepare a solution in which organic acid salts of metal elements constituting the perovskite oxide are mixed, dry this solution, crush the resulting product, mix and sinter, and pulverize this sintered product. A method for producing perovskite-type oxide powder, characterized in that the powder is obtained by
少なくとも一つを炭酸塩とし、他のペロブスカイト型酸
化物を構成する金属元素を単体もしくは酸化物として、
上記原料の粒径を目的とするペロブスカイト型酸化物の
粒径よりも小径としてこれらの粉体を混合し、この粉体
内に直接酸素を供給しながら焼成して粉体を得るように
したことを特徴とするペロブスカイト型酸化物の製造方
法。(2) At least one of the metal elements constituting the perovskite-type oxide is carbonate, and the other metal elements constituting the perovskite-type oxide are used alone or as oxides,
The particle size of the above-mentioned raw materials is smaller than the particle size of the target perovskite oxide, and these powders are mixed and fired while supplying oxygen directly into the powder to obtain the powder. Characteristic method for producing perovskite-type oxides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2322168A JPH04193701A (en) | 1990-11-26 | 1990-11-26 | Production of perovskite type oxide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2322168A JPH04193701A (en) | 1990-11-26 | 1990-11-26 | Production of perovskite type oxide powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04193701A true JPH04193701A (en) | 1992-07-13 |
Family
ID=18140698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2322168A Pending JPH04193701A (en) | 1990-11-26 | 1990-11-26 | Production of perovskite type oxide powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04193701A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07237905A (en) * | 1994-02-23 | 1995-09-12 | Samsung Electron Co Ltd | Preparation of combined metallic oxide, preparation of electrode for fuel cell and electrode for fuel cell |
| JP2005216760A (en) * | 2004-01-30 | 2005-08-11 | Kyocera Corp | Fuel cell and its manufacturing method |
| JP2013004455A (en) * | 2011-06-21 | 2013-01-07 | Toto Ltd | Electrode material of solid oxide fuel cell and manufacturing method thereof |
| JP2015111534A (en) * | 2013-12-06 | 2015-06-18 | 株式会社ノリタケカンパニーリミテド | Electrode material for solid oxide fuel cell and use thereof |
| JP2015111533A (en) * | 2013-12-06 | 2015-06-18 | 株式会社ノリタケカンパニーリミテド | Electrode material for solid oxide fuel cell and use thereof |
| WO2022029992A1 (en) * | 2020-08-07 | 2022-02-10 | Ｄｏｗａエレクトロニクス株式会社 | Composite oxide powder |
| WO2023090413A1 (en) * | 2021-11-18 | 2023-05-25 | Ｄｏｗａエレクトロニクス株式会社 | Composite oxide powder and production method thereof |
-
1990
- 1990-11-26 JP JP2322168A patent/JPH04193701A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07237905A (en) * | 1994-02-23 | 1995-09-12 | Samsung Electron Co Ltd | Preparation of combined metallic oxide, preparation of electrode for fuel cell and electrode for fuel cell |
| JP2005216760A (en) * | 2004-01-30 | 2005-08-11 | Kyocera Corp | Fuel cell and its manufacturing method |
| JP2013004455A (en) * | 2011-06-21 | 2013-01-07 | Toto Ltd | Electrode material of solid oxide fuel cell and manufacturing method thereof |
| JP2015111534A (en) * | 2013-12-06 | 2015-06-18 | 株式会社ノリタケカンパニーリミテド | Electrode material for solid oxide fuel cell and use thereof |
| JP2015111533A (en) * | 2013-12-06 | 2015-06-18 | 株式会社ノリタケカンパニーリミテド | Electrode material for solid oxide fuel cell and use thereof |
| WO2022029992A1 (en) * | 2020-08-07 | 2022-02-10 | Ｄｏｗａエレクトロニクス株式会社 | Composite oxide powder |
| JPWO2022029992A1 (en) * | 2020-08-07 | 2022-02-10 | ||
| US11866346B2 (en) | 2020-08-07 | 2024-01-09 | Dowa Electronics Materials Co., Ltd. | Composite oxide powder |
| WO2023090413A1 (en) * | 2021-11-18 | 2023-05-25 | Ｄｏｗａエレクトロニクス株式会社 | Composite oxide powder and production method thereof |
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