JPH0520869B2 - - Google Patents
Info
- Publication number
- JPH0520869B2 JPH0520869B2 JP61209453A JP20945386A JPH0520869B2 JP H0520869 B2 JPH0520869 B2 JP H0520869B2 JP 61209453 A JP61209453 A JP 61209453A JP 20945386 A JP20945386 A JP 20945386A JP H0520869 B2 JPH0520869 B2 JP H0520869B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- perovskite
- current collector
- type composite
- composite oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000010409 thin film Substances 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000002131 composite material Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- -1 organic acid salts Chemical class 0.000 claims description 5
- 150000002902 organometallic compounds Chemical class 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 150000002484 inorganic compounds Chemical class 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910016063 BaPb Inorganic materials 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910018921 CoO 3 Inorganic materials 0.000 description 1
- 229910017563 LaCrO Inorganic materials 0.000 description 1
- 241000877463 Lanio Species 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011533 mixed conductor Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8846—Impregnation
- H01M4/885—Impregnation followed by reduction of the catalyst salt precursor
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inert Electrodes (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はペロブスカイト型複合酸化物薄膜電
極、又は、薄膜電極触媒の製造法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a perovskite-type composite oxide thin film electrode or a thin film electrode catalyst.
良導電性のペロブスカイト型複合酸化物は高い
電子伝導性のみならず、触媒としての高い酸化活
性等により電極や電極触媒として優れた性質を有
している。また耐熱性に優れ、高温においてはイ
オン伝導性をも示すため、高温型燃料電池の電極
触媒やガス透過用電極及び電極触媒として広く注
目されている。これらの目的のために電極として
使用するにあたつては、実際には薄膜化できるこ
とが望ましく、また電極触媒としては、複雑形状
を持つ集電体電極表面を薄く被覆することが必要
である。
Perovskite-type composite oxides with good conductivity have excellent properties as electrodes and electrocatalysts due to not only high electronic conductivity but also high oxidation activity as a catalyst. Furthermore, since it has excellent heat resistance and exhibits ionic conductivity at high temperatures, it has attracted wide attention as an electrode catalyst for high-temperature fuel cells, a gas permeation electrode, and an electrode catalyst. When used as an electrode for these purposes, it is actually desirable to be able to form a thin film, and as an electrode catalyst, it is necessary to thinly coat the surface of the current collector electrode, which has a complex shape.
酸化物薄膜の合成法としては、気相法、テープ
キヤスト粉末焼結法が従来から一般に広く用いら
れているが、気相法は設備が大がかりとなる上に
大面積のものは製造が困難であり、生産性も高く
ない。また、テープキヤスト粉末焼結法は薄さに
限界（20〜30μ）があると同時に、均一な薄膜を
合成することは難しく、また高い焼結温度が必要
である。 The gas phase method and tape cast powder sintering method have been widely used as methods for synthesizing oxide thin films, but the gas phase method requires large-scale equipment and is difficult to manufacture large-area products. Yes, and productivity is not high. In addition, the tape cast powder sintering method has a thinness limit (20 to 30 microns), is difficult to synthesize a uniform thin film, and requires a high sintering temperature.
本発明は、電気伝導性ペロブスカイト型複合酸
化物を形成する金属イオンを含む金属有機酸塩或
いは金属アルコキシドを複数混合し、必要に応じ
て適当な有機溶剤で希釈した混合溶液を、或いは
また本溶液に適時、触媒の感度及び選択性を高め
る働きをする金属或いはその無機化合物を添加し
た混合溶液を電解質膜上或いは集電体上に滴下す
るか、塗布するか或いは該溶液に電解質膜或いは
集電体を浸漬し、引き上げ、乾燥して有機金属化
合物の薄膜を電解質膜或いは集電体表面上に作
り、これを焼成することにより、ペロブスカイト
型複合酸化物薄膜電極又は薄膜電極触媒を製造す
る方法である。
The present invention provides a mixed solution prepared by mixing a plurality of metal organic acid salts or metal alkoxides containing metal ions to form an electrically conductive perovskite-type composite oxide, and diluting the mixture with an appropriate organic solvent as necessary, or the present solution. At appropriate times, a mixed solution containing a metal or an inorganic compound thereof that serves to enhance the sensitivity and selectivity of the catalyst is dropped or applied onto the electrolyte membrane or current collector, or the solution is coated with the electrolyte membrane or current collector. A method for producing a perovskite-type composite oxide thin film electrode or thin film electrode catalyst by immersing the body, pulling it up, drying it to form a thin film of an organometallic compound on the surface of an electrolyte membrane or current collector, and firing this. be.
本発明の有機金属化合物の塗布熱分解法は、上
記の欠点を含まず、1000℃以下の低温で簡便に
1μ以下の薄膜を合成することができるものであ
り、上記の２つの従来の方法にとつて代わるべき
ものである。 The coating pyrolysis method of organometallic compounds of the present invention does not have the above drawbacks and can be easily performed at a low temperature of 1000°C or less.
It is possible to synthesize thin films with a thickness of 1μ or less, and should replace the above two conventional methods.
これまで、固体電解質薄膜やガスセンサーを目
的として、有機金属化合物を用いる薄膜の合成法
は報告されているものの、３種ないし４種類以上
の金属成分を含むペロブスカイト型複合酸化物に
よつて、薄膜電極及び薄膜電極触媒としての有効
性を確かめたのは初めてであり、これは発明者ら
の長年の努力の成果である。この方法により、複
雑な形状の表面や、多孔体細孔中にも、ペロブス
カイト型複合酸化物の形成が可能となり、電極効
率を高めることが期待できる。 Until now, methods for synthesizing thin films using organometallic compounds have been reported for the purpose of solid electrolyte thin films and gas sensors. This is the first time that its effectiveness as an electrode and thin film electrocatalyst has been confirmed, and this is the result of many years of efforts by the inventors. This method enables the formation of perovskite-type composite oxides even on surfaces with complex shapes and in the pores of porous materials, and is expected to improve electrode efficiency.
さらに本発明によれば、ペロブスカイト型複合
酸化物薄膜電極及び電極触媒に対して、別個の触
媒機能を有する。貴金属や他の酸化物触媒を、均
一性、分散性良く添加することも可能であり、二
元、三元機能性薄膜電極、薄膜電極触媒を合成す
ることができる。 Furthermore, according to the present invention, the perovskite composite oxide thin film electrode and the electrode catalyst have separate catalytic functions. It is also possible to add noble metals or other oxide catalysts with good uniformity and dispersibility, and binary or ternary functional thin film electrodes and thin film electrode catalysts can be synthesized.
金属有機酸塩及び金属アルコキシドは焼成する
ことにより有機成分が分解・酸化・除去され、均
一な酸化物薄膜が生成される。有機物の分解・燃
焼は200〜500℃で終了し、その後酸化物の生成、
結晶化が生じるため焼成温度は400〜800℃という
低い温度でも充分である。また薄膜の厚みは有機
溶剤で希釈したものを用いることにより、数十オ
ングストロームから数万オングストロームまで調
節することができる。 By firing the metal organic acid salt and metal alkoxide, the organic components are decomposed, oxidized, and removed, and a uniform oxide thin film is produced. The decomposition and combustion of organic matter ends at 200 to 500℃, after which oxides are produced,
Since crystallization occurs, a firing temperature as low as 400 to 800°C is sufficient. Further, the thickness of the thin film can be adjusted from several tens of angstroms to tens of thousands of angstroms by using a thin film diluted with an organic solvent.
基板は電解質膜や集電体であるが、平面球面を
とわず、また緻密体、多孔体、繊維状のものであ
つても被覆可能である。 The substrate is an electrolyte membrane or a current collector, but it does not have to be a flat spherical surface, and even dense, porous, or fibrous materials can be coated.
電気伝導性のペロブスカイト型複合酸化物は
ABO3が基本組成であるが、特性を高めるために
Ａ側、Ｂ側とも数種の元素で一部を置換すること
が良く行なわれるが、これらの含有量の調整は気
相法や粉末焼結法では非常に困難なものとなつて
いるのに対し、本方法では、添加すべき元素の有
機化合物をその組成に合せただけ添加した混合液
を調製するたけで達成できることは大きな利点で
ある。又、貴金属等の添加に於いても同様に、均
一に分散した触媒の担持が容易に行える。 Electrically conductive perovskite-type composite oxide
The basic composition is ABO 3 , but in order to improve the properties, parts of both the A and B sides are often replaced with several types of elements, but these contents can be adjusted using the vapor phase method or powder sintering. While this method is extremely difficult to achieve, this method has the great advantage of being able to achieve this by simply preparing a mixed solution in which the organic compounds of the elements to be added are added in amounts that match the composition. . Similarly, when adding noble metals, etc., it is easy to support a uniformly dispersed catalyst.
本発明方法では、ほとんどすべてのペロブスカ
イト型複合酸化物が合成され得るが、例を上げれ
ば、La1-xSrxCoO3、LaCrO3、La1-xSrxMnO3、
LaNiO3、La1-xCaxCo1-yFeyO3、CaVO3、
SrFeO3、CaRuO3、BaPb1-xBixO3、SrCeO3、
LaCuO3、CaTi1-xAlxO3等があり、金属の有機酸
塩としては、ナフテン酸、オクチル酸、カプリル
酸等との金属塩が好ましく、また金属アルコキシ
ドとしては、エトキシド、プロピオキシド、ブト
キシド等が用いられる。 Almost all perovskite-type composite oxides can be synthesized by the method of the present invention, but examples include La 1-x Sr x CoO 3 , LaCrO 3 , La 1-x Sr x MnO 3 ,
LaNiO 3 , La 1-x Ca x Co 1-y Fe y O 3 , CaVO 3 ,
SrFeO 3 , CaRuO 3 , BaPb 1-x Bi x O 3 , SrCeO 3 ,
Examples of metal organic acid salts include metal salts with naphthenic acid, octylic acid, caprylic acid , etc. , and metal alkoxides include ethoxide, propioxide, Butoxide etc. are used.
一般に電池に用いられる電極は、高い電子伝導
性を示すだけでは不充分であり、電極上での電気
化学反応に対する高い活性も要求される。 In general, it is not sufficient for electrodes used in batteries to simply exhibit high electronic conductivity; high activity for electrochemical reactions on the electrodes is also required.
ペロブスカイト型複合酸化物は、陰極における
酸素の還元反応に対する活性が高いことが知られ
ているが、室温付近では、電子伝導性が充分に高
くないため、黒鉛粒子等と混合し、電極として使
用することが広く行われる。しかし、炭素繊維、
炭素板などの集電体表面を薄く被覆することがで
きれば、電子伝導性の不足に伴なう内部抵抗は無
視できる程度となる。そこで、本発明方法で示し
た薄膜の合成によれば広い電極面積を有する効率
の高い電極の製造が可能となる。 Perovskite-type composite oxides are known to have high activity for oxygen reduction reactions at the cathode, but their electronic conductivity is not high enough near room temperature, so they are mixed with graphite particles and used as electrodes. It is widely practiced. However, carbon fiber,
If the surface of a current collector such as a carbon plate can be thinly coated, internal resistance due to insufficient electron conductivity will be negligible. Therefore, by synthesizing a thin film according to the method of the present invention, it becomes possible to manufacture highly efficient electrodes having a wide electrode area.
また、高温においては一部のペロブスカイト型
複合酸化物は、電子とイオンの混合導伝性を示
す。通常の電子伝導性のみを持つ電極を使用した
場合、電子の授受は、電解質、電極及びガスの３
者共存点のみでしか起こらず、有効電極面積が極
めて小さいのに対し、この混合導伝体では、ガス
と電極或いは、ガスと電解質の２者の接点で反応
が進行するため、有効電極面積は大幅に増加す
る。ここにおいても、イオン及び電子の透過速度
を高めるために薄膜化が重要な技術課題であり、
高温型燃料電池等の電極製造技術として、本発明
方法の使用が有効である。また、白金電極等の高
温下の使用で問題となる揮発、焼結などによる電
極特性の劣化の心配もなく、優れた特性が持続す
る。 Further, at high temperatures, some perovskite-type composite oxides exhibit mixed conductivity of electrons and ions. When using electrodes that have only normal electron conductivity, electrons are exchanged between the electrolyte, the electrode, and the gas.
However, in this mixed conductor, the reaction proceeds at the contact point between the gas and the electrode or the gas and the electrolyte, so the effective electrode area is very small. Significant increase. Here too, thinning the film is an important technical issue in order to increase the transmission rate of ions and electrons.
The method of the present invention is effective as an electrode manufacturing technology for high-temperature fuel cells and the like. In addition, there is no concern about deterioration of electrode properties due to volatilization, sintering, etc., which is a problem when using platinum electrodes at high temperatures, and excellent properties are maintained.
さらに、このペロブスカイト型複合酸化物の触
媒に他の触媒機能を持つ貴金属等の触媒の均一、
分散担持が簡便に伝え、多機能性電極触媒として
の利用が期待できる。 Furthermore, this perovskite-type composite oxide catalyst is uniformly coated with catalysts such as noble metals that have other catalytic functions.
Dispersed support allows easy transfer, and it can be expected to be used as a multifunctional electrode catalyst.
実施例 １
有機金属化合物として、ランタン、ストロンチ
ウム、鉄、コバルトのナフテン酸塩を用い、La、
Sr、Co、Feのモル比が５；１；５；１となるよ
う混合し、ブタノールで希釈して20wt％ブタノ
ール溶液とした。本溶液をAl2O3基板上に塗布
し、乾燥後1000℃で焼成して、薄膜を焼成した。
Ｘ線分析の結果、ペロブスカイト型の
LaSrCoFeO3-〓が生成していることが確認され
た。本薄膜上に約10mmの間隔で白金ペーストを塗
布・焼付けして電極とし、薄膜の表面導電度を室
温より900℃まで測定した。導伝特性は高温にな
るにつれて増加する半導体的挙動を示し、400℃
〜900℃では10-3〜10-2Ω−cmであり、導伝性が
充分に高いことを確認した。Example 1 Naphthenates of lanthanum, strontium, iron, and cobalt were used as organometallic compounds, and La,
Sr, Co, and Fe were mixed in a molar ratio of 5:1;5:1, and diluted with butanol to obtain a 20 wt % butanol solution. This solution was applied onto an Al 2 O 3 substrate, dried and then fired at 1000°C to create a thin film.
As a result of X-ray analysis, perovskite-type
It was confirmed that LaSrCoFeO 3- 〓 was generated. Platinum paste was coated and baked on this thin film at intervals of about 10 mm to form electrodes, and the surface conductivity of the thin film was measured from room temperature to 900°C. The conductive properties exhibit semiconducting behavior that increases as the temperature increases, and at 400℃
The conductivity was 10 -3 -10 -2 Ω-cm at -900°C, confirming that the conductivity was sufficiently high.
実施例 ２
実施例１で用いた混合溶液をY2O3安定化ZrO2
の緻密焼結体円板の両側に塗布、乾燥、焼成し
LaSrCoFeO3-〓の電極をとりつけた後、白金ペー
ストで固定することにより、白金リード線を円板
両端面より取り出した。このZrO2円板を隔壁と
して、両側に気密室を設け、一方をアルゴン、他
方を空気とし700℃にてアルゴン側に、空気側
にの直流電源を印加した所、アルゴンガス側の
酸素濃度の増加がみられた。Example 2 The mixed solution used in Example 1 was converted into Y 2 O 3 stabilized ZrO 2
Coated on both sides of a dense sintered disk, dried, and fired.
After attaching LaSrCoFeO 3- electrodes, they were fixed with platinum paste, and the platinum lead wires were taken out from both ends of the disk. Using this ZrO 2 disk as a partition wall, airtight chambers were provided on both sides, argon was placed on one side, and air was placed on the other side. When DC power was applied to the argon side and the air side at 700℃, the oxygen concentration on the argon gas side was An increase was seen.
また、この時の電圧−電流特性は、白金電極の
それと比べて、同電位であり高い電流密度が得ら
れることが確認された。 Further, it was confirmed that the voltage-current characteristics at this time were the same potential as those of the platinum electrode, and a high current density was obtained.
Claims (1)
成する金属イオンを含む金属有機酸塩或いは金属
アルコキシドを複数混合し必要に応じて適当な有
機溶剤で希釈し、その混合溶液を電解質膜上或い
は集電体上に滴下するか、塗布するか、或いは該
溶液に電解質膜或いは集電体を浸漬し、引き上げ
た後、乾燥して有機金属化合物の薄膜を電解質膜
表面上或いは集電体表面上に作り、これを加熱・
焼成する事を特徴とするペロブスカイト型複合酸
化物薄膜電極又は薄膜電極触媒の製造法。 ２ 更に触媒の感度及び／又は選択性を高める働
きをする金属或いはその無機化合物を、分散或い
は溶解させた混合溶液を使用する特許請求範囲第
１項記載のペロブスカイト型複合酸化物薄膜電極
触媒の製造法。[Claims] 1. Mix a plurality of metal organic acid salts or metal alkoxides containing metal ions to form an electrically conductive perovskite-type composite oxide, dilute with an appropriate organic solvent as necessary, and use the mixed solution as an electrolyte. The electrolyte membrane or current collector is dropped or applied onto the membrane or current collector, or the electrolyte membrane or current collector is immersed in the solution, pulled up, and dried to form a thin film of the organometallic compound on the surface of the electrolyte membrane or current collector. produced on the body surface, heated and
A method for producing a perovskite-type composite oxide thin film electrode or thin film electrode catalyst, which comprises firing. 2. Production of a perovskite-type composite oxide thin film electrode catalyst according to claim 1, using a mixed solution in which a metal or an inorganic compound thereof is dispersed or dissolved, and which functions to further enhance the sensitivity and/or selectivity of the catalyst. Law.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61209453A JPS6366859A (en) | 1986-09-08 | 1986-09-08 | Manufacture of perovskite type composite oxide thin film electrode or thin film electrode catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61209453A JPS6366859A (en) | 1986-09-08 | 1986-09-08 | Manufacture of perovskite type composite oxide thin film electrode or thin film electrode catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6366859A JPS6366859A (en) | 1988-03-25 |
| JPH0520869B2 true JPH0520869B2 (en) | 1993-03-22 |
Family
ID=16573122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61209453A Granted JPS6366859A (en) | 1986-09-08 | 1986-09-08 | Manufacture of perovskite type composite oxide thin film electrode or thin film electrode catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6366859A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5231074A (en) * | 1990-04-17 | 1993-07-27 | Massachusetts Institute Of Technology | Preparation of highly textured oxide superconducting films from mod precursor solutions |
| JPH06317555A (en) * | 1993-05-07 | 1994-11-15 | Fujikura Ltd | Manufacture of ceramic oxygen sensor |
| US5705601A (en) * | 1995-07-07 | 1998-01-06 | Nippon Ester Co., Ltd. | Process for producing polyester film |
| DK0902493T3 (en) | 1997-09-11 | 2001-02-05 | Sulzer Hexis Ag | Electrochemically active element for a solid oxide fuel cell |
| JP5269711B2 (en) * | 2009-07-09 | 2013-08-21 | 株式会社ノリタケカンパニーリミテド | Oxygen separation membrane element and manufacturing method thereof |
| JP5634433B2 (en) | 2012-04-27 | 2014-12-03 | 株式会社日本自動車部品総合研究所 | Particulate matter detection element, manufacturing method thereof, and particulate matter detection sensor |
| JP5709808B2 (en) * | 2012-08-02 | 2015-04-30 | 株式会社日本自動車部品総合研究所 | Particulate matter detection element manufacturing method and particulate matter detection sensor |
-
1986
- 1986-09-08 JP JP61209453A patent/JPS6366859A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6366859A (en) | 1988-03-25 |
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