JPH07190988A - Method for manufacturing ion-conductive thin film - Google Patents
Method for manufacturing ion-conductive thin filmInfo
- Publication number
- JPH07190988A JPH07190988A JP5328742A JP32874293A JPH07190988A JP H07190988 A JPH07190988 A JP H07190988A JP 5328742 A JP5328742 A JP 5328742A JP 32874293 A JP32874293 A JP 32874293A JP H07190988 A JPH07190988 A JP H07190988A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- conductive thin
- ion
- compound
- aqueous solution
- 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
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
-
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、限界電流式酸素セン
サ、燃料電池及び酸素濃淡電池等に使用されるイオン伝
導性薄膜の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an ion conductive thin film used in a limiting current type oxygen sensor, a fuel cell, an oxygen concentration cell and the like.
【０００２】[0002]
【従来の技術】従来、限界電流式酸素センサ、燃料電池
及び酸素濃淡電池等には、イオン伝導性部材として、安
定化ジルコニウムが使用されている。例えば、酸素濃淡
電池は、安定化ジルコニア基板と、この基板に密着して
形成された多孔質の白金電極とにより構成されている
（特公昭６０−１１４２８号，特公平２−１１８６１
号）。これらの酸素濃淡電池には、粉末状原料をプレス
成形して形成された厚さが約１ｍｍの安定化ジルコニア
板が使用されている。2. Description of the Related Art Conventionally, stabilized zirconium has been used as an ion conductive member in limiting current type oxygen sensors, fuel cells, oxygen concentration cells and the like. For example, an oxygen concentration cell is composed of a stabilized zirconia substrate and a porous platinum electrode formed in close contact with the substrate (Japanese Patent Publication No. 60-11428, Japanese Patent Publication No. 2-11861).
issue). For these oxygen concentration batteries, a stabilized zirconia plate having a thickness of about 1 mm formed by press molding a powdery raw material is used.
【０００３】ところで、イオン伝導性膜を薄膜化するこ
とにより、酸素センサの小型化、材料コストの低減及び
作動温度の低温化が可能であると共に、応答性が向上す
るという利点がある。このため、限界電流式酸素センサ
に使用されるイオン伝導性膜の薄膜化が促進されてい
る。従来、イオン伝導性薄膜の製造方法としては、スパ
ッタ装置を使用してドライプロセスにより製造する方法
と、スラリー状にした原料をドクターブレード法により
フィルム上に塗布しその後乾燥させることにより製造す
る方法とがある。By reducing the thickness of the ion conductive film, the oxygen sensor can be downsized, the material cost can be reduced, the operating temperature can be lowered, and the responsiveness can be improved. Therefore, thinning of the ion conductive film used in the limiting current type oxygen sensor is promoted. Conventionally, as a method for producing an ion conductive thin film, a method of producing by a dry process using a sputtering device, and a method of producing a slurry-like raw material by applying it on a film by a doctor blade method and then drying it. There is.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上述し
た従来のイオン伝導性薄膜の製造方法には、以下に示す
問題点がある。即ち、スパッタ装置を使用する方法にお
いては、チャンバ内を高真空にするための真空装置が必
要であるため、装置コストが高く、また製造が煩雑であ
るという欠点がある。一方、ドクターブレード法におい
ては、イオン伝導性膜の膜厚を約３０μｍ以下に薄膜化
することが困難である。However, the above-mentioned conventional method for producing an ion conductive thin film has the following problems. That is, the method using the sputtering apparatus has the disadvantages that the apparatus cost is high and the manufacturing is complicated because a vacuum apparatus for making the inside of the chamber a high vacuum is required. On the other hand, in the doctor blade method, it is difficult to reduce the thickness of the ion conductive film to about 30 μm or less.
【０００５】本発明はかかる問題点に鑑みてなされたも
のであって、高価な装置を必要とせず、容易にμｍオー
ダーのイオン伝導性薄膜を製造できるイオン伝導性薄膜
の製造方法を提供することを目的とする。The present invention has been made in view of the above problems, and provides a method for producing an ion-conductive thin film that does not require an expensive apparatus and can easily produce an ion-conductive thin film of the order of μm. With the goal.
【０００６】[0006]
【課題を解決するための手段】本発明に係るイオン伝導
性薄膜の製造方法は、ジルコニウム化合物の酸性水溶液
とイットリウム化合物の酸性水溶液との混合溶液を支持
部材上に塗布して塗布膜を得る工程と、前記塗布膜を乾
燥させる工程とを有することを特徴とする。A method for producing an ion conductive thin film according to the present invention comprises a step of applying a mixed solution of an acidic aqueous solution of a zirconium compound and an acidic aqueous solution of a yttrium compound onto a support member to obtain a coating film. And a step of drying the coating film.
【０００７】[0007]
【作用】本願発明者等は、真空装置等の高価な装置を必
要とせず、容易にμｍオーダーのイオン伝導性薄膜を製
造できる方法を開発すべく、種々実験研究を行った。そ
の結果、ジルコニウム化合物の酸性水溶液にイットリウ
ム化合物の酸性水溶液を添加して得た混合溶液を使用
し、この混合溶液をガラス板又はアルミナ板等の支持部
材上に塗布した後、乾燥させることにより、イオン伝導
性が優れた薄膜を得ることができることが判明した。本
願発明は、このような実験結果に基づいてなされたもの
である。The present inventors have conducted various experimental studies in order to develop a method capable of easily producing an ion conductive thin film on the order of μm without requiring an expensive apparatus such as a vacuum apparatus. As a result, the mixed solution obtained by adding the acidic aqueous solution of the yttrium compound to the acidic aqueous solution of the zirconium compound is used, and the mixed solution is applied on a supporting member such as a glass plate or an alumina plate, and then dried. It was found that a thin film having excellent ionic conductivity can be obtained. The present invention has been made based on such experimental results.
【０００８】即ち、本発明においては、先ず、ジルコニ
ウム化合物の酸性水溶液とイットリウム化合物の酸性水
溶液との混合溶液をガラス板等の支持部材上に塗布す
る。次いで、前記支持部材上の塗布膜を乾燥させる。こ
のようにして、膜厚が1000Å〜数μｍであり、ピンホー
ル等の欠陥がないイオン伝導性薄膜を容易に製造するこ
とができる。本発明においては、真空装置等のように高
価な装置を使用する必要がないため、イオン伝導性薄膜
を容易に且つ低コストで製造できる。That is, in the present invention, first, a mixed solution of an acidic aqueous solution of a zirconium compound and an acidic aqueous solution of a yttrium compound is applied on a supporting member such as a glass plate. Then, the coating film on the support member is dried. In this way, an ion conductive thin film having a film thickness of 1000Å to several μm and having no defects such as pinholes can be easily manufactured. In the present invention, since it is not necessary to use an expensive device such as a vacuum device, the ion conductive thin film can be easily manufactured at low cost.
【０００９】[0009]
【実施例】以下、本発明に係るイオン伝導性薄膜の製造
方法について、より一層詳細に説明する。本発明におい
ては、先ず、ジルコニウム化合物の酸性水溶液とイット
リウム化合物の酸性水溶液との混合溶液を用意する。ジ
ルコニウム化合物及びイットリウム化合物としては、硝
酸塩、硫酸塩、炭酸塩、酢酸塩、オクチル酸塩及びステ
アリン酸塩（これらの化合物の水和物を含む）等があ
る。EXAMPLES The method for producing an ion conductive thin film according to the present invention will be described in more detail below. In the present invention, first, a mixed solution of an acidic aqueous solution of a zirconium compound and an acidic aqueous solution of a yttrium compound is prepared. Examples of zirconium compounds and yttrium compounds include nitrates, sulfates, carbonates, acetates, octylates and stearates (including hydrates of these compounds).
【００１０】また、混合溶液中のジルコニウム化合物の
酸性水溶液とイットリウム化合物の酸性水溶液との割合
は特に限定するものではないが、イオン伝導性薄膜の機
械的強度とイオン伝導性との双方を考慮して決定する。
例えば、ジルコニアを基準とした場合、薄膜の機械的強
度は、イットリウム化合物の含有量が約３モル％のとき
に最大となり、これよりも多くすると機械的強度は低下
する。そして、イットリウム化合物の含有量が約４．５
モル％のときには膜が脆くなり、８モル％を超えると機
械的強度は著しく低下する。一方、薄膜のイオン伝導性
は、イットリウム化合物の含有量が約８モル％のときに
最大となり、これより多くても少なくてもイオン伝導性
は減少する。従って、機械的特性を重視する場合はイッ
トリウム化合物の酸性水溶液の含有量を例えば３モル％
とし、イオン伝導性を重視する場合はイットリウム化合
物の酸性水溶液の含有量を例えば８モル％とし、両方の
特性を適度に必要な場合にはイットリウム化合物の酸性
水溶液の含有量を６モル％とするというように、イット
リウム化合物の酸性水溶液の含有量を３乃至８モル％の
範囲で用途に応じて設定することが好ましい。Further, the ratio of the acidic aqueous solution of the zirconium compound and the acidic aqueous solution of the yttrium compound in the mixed solution is not particularly limited, but in consideration of both the mechanical strength and the ionic conductivity of the ion conductive thin film. To decide.
For example, on the basis of zirconia, the mechanical strength of the thin film becomes maximum when the content of the yttrium compound is about 3 mol%, and when it is more than this, the mechanical strength decreases. And the yttrium compound content is about 4.5.
When the content is 8 mol%, the film becomes brittle, and when it exceeds 8 mol%, the mechanical strength is significantly reduced. On the other hand, the ionic conductivity of the thin film is maximized when the content of the yttrium compound is about 8 mol%, and the ionic conductivity decreases when the content of the yttrium compound is more or less than this. Therefore, when importance is attached to mechanical properties, the content of the acidic aqueous solution of the yttrium compound is, for example, 3 mol%.
The content of the acidic aqueous solution of the yttrium compound is, for example, 8 mol% when the ionic conductivity is important, and the content of the acidic aqueous solution of the yttrium compound is 6 mol% when both properties are appropriately required. Thus, it is preferable to set the content of the acidic aqueous solution of the yttrium compound in the range of 3 to 8 mol% according to the application.
【００１１】次いで、この混合溶液をガラス板又はアル
ミナ板等の支持部材上に塗布する。この場合に、ジルコ
ニウム化合物及びイットリウム化合物はいずれも酸性水
溶液中に均一に溶解しているため、支持部材上に均一に
且つ薄く塗布することができる。また、混合溶液の塗布
は、例えば、キャスティング法、ディッピング法又は印
刷法等のウエットプロセスにより行う。その後、塗布膜
を乾燥させることにより、イオン伝導性が優れたμｍオ
ーダーの薄膜を得ることができる。Next, this mixed solution is applied onto a supporting member such as a glass plate or an alumina plate. In this case, since both the zirconium compound and the yttrium compound are uniformly dissolved in the acidic aqueous solution, the support member can be uniformly and thinly applied. The application of the mixed solution is performed by a wet process such as casting, dipping, or printing. After that, by drying the coating film, it is possible to obtain a thin film of the order of μm having excellent ion conductivity.
【００１２】次に、本発明の実施例について説明する。
先ず、ジルコニウム化合物の酸性水溶液及びイットリウ
ム化合物の酸性水溶液として、夫々｛ＺｒＯ（ＮＯ3 ）
2・ｎＨ2Ｏ｝（硝酸ジルコニール）及び｛ＹＯ（ＮＯ
3 ）3・ｎＨ2Ｏ｝を用意した。Next, an embodiment of the present invention will be described.
First, as an acidic aqueous solution of a zirconium compound and an acidic aqueous solution of a yttrium compound, {ZrO (NO 3 ) 2
2 · nH 2 O} (zirconyl nitrate) and {YO (NO
3 ) 3 · nH 2 O} was prepared.
【００１３】次に、｛ＺｒＯ（ＮＯ3 ）2・ｎＨ2Ｏ｝に
対し８モル％の割合で｛ＹＯ（ＮＯ3 ）3・ｎＨ2Ｏ｝を
添加し、原料混合溶液とした。そして、この混合溶液を
ガラス基板上に塗布し、自然乾燥させた後、約２００℃
の温度で３０分間加熱して焼成した。これにより、イオ
ン伝導性薄膜（ＺｒＯ2−８モル％Ｙ2Ｏ3）を得た。Next, {YO (NO 3 ) 3 .nH 2 O} was added at a ratio of 8 mol% to {ZrO (NO 3 ) 2 .nH 2 O} to obtain a raw material mixed solution. Then, the mixed solution is applied on a glass substrate and naturally dried, and then heated to about 200 ° C.
It was baked by heating at the temperature of 30 minutes. Thereby, an ion conductive thin film (ZrO 2 -8 mol% Y 2 O 3 ) was obtained.
【００１４】このようにして製造したイオン伝導性薄膜
の厚さを測定したところ、約０．５μｍであった。ま
た、このイオン伝導性薄膜のイオン伝導性を調べたとこ
ろ、極めて良好であった。The thickness of the ion conductive thin film thus produced was measured and found to be about 0.5 μm. The ionic conductivity of this ion-conductive thin film was examined, and it was found to be extremely good.
【００１５】[0015]
【発明の効果】以上説明したように本発明によれば、ジ
ルコニウム化合物の酸性水溶液とイットリウム化合物の
酸性水溶液との混合溶液をガラス板等の支持部材上に塗
布し、その後塗布膜を乾燥させることによりイオン伝導
性薄膜を製造するから、真空装置等が不要であり、容易
に且つ安価にイオン伝導性薄膜を製造できる。As described above, according to the present invention, a mixed solution of an acidic aqueous solution of a zirconium compound and an acidic aqueous solution of a yttrium compound is coated on a supporting member such as a glass plate, and then the coating film is dried. Since the ion conductive thin film is manufactured by the method, a vacuum device or the like is not necessary, and the ion conductive thin film can be easily manufactured at low cost.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 石橋 功成 東京都江東区木場１丁目５番１号 株式会 社フジクラ内 (72)発明者 加藤 嘉則 東京都江東区木場１丁目５番１号 株式会 社フジクラ内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Issei Ishibashi 1-5-1 Kiba, Koto-ku, Tokyo Fujikura Ltd. (72) Inventor Yoshinori Kato 1-1-5 Kiba, Koto-ku, Tokyo Shares Inside Fujikura
Claims (1)
トリウム化合物の酸性水溶液との混合溶液を支持部材上
に塗布して塗布膜を得る工程と、前記塗布膜を乾燥させ
る工程とを有することを特徴とするイオン伝導性薄膜の
製造方法。1. A step of applying a mixed solution of an acidic aqueous solution of a zirconium compound and an acidic aqueous solution of a yttrium compound onto a support member to obtain a coating film, and a step of drying the coating film. Method for producing ion conductive thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5328742A JPH07190988A (en) | 1993-12-24 | 1993-12-24 | Method for manufacturing ion-conductive thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5328742A JPH07190988A (en) | 1993-12-24 | 1993-12-24 | Method for manufacturing ion-conductive thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07190988A true JPH07190988A (en) | 1995-07-28 |
Family
ID=18213670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5328742A Pending JPH07190988A (en) | 1993-12-24 | 1993-12-24 | Method for manufacturing ion-conductive thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07190988A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005062184A (en) * | 2003-08-14 | 2005-03-10 | Robert Bosch Gmbh | Flat laminar sensor element |
| JP2009120872A (en) * | 2007-11-12 | 2009-06-04 | Dainippon Printing Co Ltd | Method for producing metal oxide film |
-
1993
- 1993-12-24 JP JP5328742A patent/JPH07190988A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005062184A (en) * | 2003-08-14 | 2005-03-10 | Robert Bosch Gmbh | Flat laminar sensor element |
| JP2009120872A (en) * | 2007-11-12 | 2009-06-04 | Dainippon Printing Co Ltd | Method for producing metal oxide film |
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