JPH07282821A - Solid electrolyte fuel cell and manufacture thereof - Google Patents
Solid electrolyte fuel cell and manufacture thereofInfo
- Publication number
- JPH07282821A JPH07282821A JP6069404A JP6940494A JPH07282821A JP H07282821 A JPH07282821 A JP H07282821A JP 6069404 A JP6069404 A JP 6069404A JP 6940494 A JP6940494 A JP 6940494A JP H07282821 A JPH07282821 A JP H07282821A
- Authority
- JP
- Japan
- Prior art keywords
- separator
- film
- current collector
- fuel cell
- contact resistance
- 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
- 239000000446 fuel Substances 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 239000007784 solid electrolyte Substances 0.000 title description 4
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000007650 screen-printing Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims description 9
- 230000008646 thermal stress Effects 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 40
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 238000010248 power generation Methods 0.000 description 5
- 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 3
- 239000012528 membrane Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 2
- 229910017563 LaCrO Inorganic materials 0.000 description 1
- 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 description 1
- 239000011195 cermet Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002966 varnish Substances 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
-
- 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
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、固体電解質型燃料電池
とその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid oxide fuel cell and a manufacturing method thereof.
【０００２】[0002]
【従来の技術】燃料の化学的なエネルギーを電気化学的
な手段によって、直接電気エネルギーに変換するものと
して固体電解質型燃料電池がある。2. Description of the Related Art There is a solid oxide fuel cell that directly converts chemical energy of fuel into electrical energy by an electrochemical means.
【０００３】図１は、例えば３セルで構成されたスタッ
クを有する平板型の固体電解質型燃料電池の分解斜視図
である。FIG. 1 is an exploded perspective view of a flat plate type solid oxide fuel cell having a stack composed of, for example, three cells.
【０００４】セル１は燃料電池の反応を起こさせて電気
を発生させる最小単位であり、発電部２、集電体３及び
セパレータ４から構成され、このうち、発電部２は空気
極５、固体電解質膜６及び燃料極７の３層からなってい
る。そして、このようなセル１を複数個積層したものを
スタック１０とよんでいる。A cell 1 is a minimum unit for causing a reaction of a fuel cell to generate electricity, and is composed of a power generation section 2, a current collector 3 and a separator 4, of which the power generation section 2 is an air electrode 5, a solid body. It is composed of three layers, an electrolyte membrane 6 and a fuel electrode 7. A stack 10 is formed by laminating a plurality of such cells 1.
【０００５】固体電解質膜６はその材料として、例えば
イットリア安定化ジルコニア（ＹＳＺ）が用いられてい
る。また、空気極５の材料には、例えばランタンマンガ
ナイト（ＬａＭｎＯ3 ）が用いられ、燃料極７の材料に
は、例えばニッケル（Ｎｉ）と安定化ジルコニア（ＹＳ
Ｚ）を混合したサーメットが用いられている。The solid electrolyte membrane 6 is made of, for example, yttria-stabilized zirconia (YSZ). Lanthanum manganite (LaMnO 3 ) is used as the material of the air electrode 5, and nickel (Ni) and stabilized zirconia (YS) are used as the material of the fuel electrode 7.
A cermet mixed with Z) is used.
【０００６】発電部２の燃料極７とセパレータ４の間に
は、Ｎｉ等の集電体３が設けられ、燃料極７の集電性能
を向上させている。A current collector 3 made of Ni or the like is provided between the fuel electrode 7 of the power generation section 2 and the separator 4 to improve the current collecting performance of the fuel electrode 7.
【０００７】そしてセパレータ４には、例えばランタン
クロマイト（ＬａＣｒＯ3 ）が用いられ、このセパレ−
タ４はその溝８を通じて、発電部２の空気極５と燃料極
７にそれぞれ空気または燃料ガスが行き渡るようにする
とともに、セル１とセル１が電気的に接続するように機
能する。For the separator 4, for example, lanthanum chromite (LaCrO 3 ) is used.
Through the groove 8, the battery 4 spreads air or fuel gas to the air electrode 5 and the fuel electrode 7 of the power generation unit 2, respectively, and also functions to electrically connect the cells 1 to the cells 1.
【０００８】このような平板型の固体電解質型燃料電池
の利点として、単位体積当たりの出力が大きいことがあ
げられる。これは固体電解質膜６やセパレータ４の厚み
を薄くすることにより、単位厚み当たりのセル１の数を
多くでき、加えて、電流が平面に対し直角方向に流れる
ので、内部抵抗を小さくすることができるためである。An advantage of such a plate type solid oxide fuel cell is that it has a large output per unit volume. This is because the number of cells 1 per unit thickness can be increased by reducing the thickness of the solid electrolyte membrane 6 and the separator 4, and the current flows in the direction perpendicular to the plane, so that the internal resistance can be reduced. Because you can.
【０００９】そして、この構造においては、セパレータ
４とＮｉ等の集電体３の間の接触抵抗を低減して電池の
出力を高めるため、集電体３と接合されるセパレータ４
の面９に、Ｎｉ等の金属膜を形成することが一般に行わ
れている。In this structure, in order to reduce the contact resistance between the separator 4 and the current collector 3 such as Ni to increase the output of the battery, the separator 4 joined to the current collector 3 is used.
It is generally practiced to form a metal film of Ni or the like on the surface 9 of.
【００１０】[0010]
【発明が解決しようとする課題】しかし、セパレ−タ４
の材質に用いられるランタンクロマイト（ＬａＣｒ
Ｏ3）等と、接触抵抗を低減するために用いる金属膜の
Ｎｉ等は、熱膨張係数が大きく異なるため、燃料電池の
昇温中あるいは作動中に、金属膜の膜厚が厚いと強い熱
応力が働いて、金属膜が集電体３と接合されるセパレ−
タ４の面９から剥離し、接触抵抗が高くなってしまうと
いう問題があった。DISCLOSURE OF THE INVENTION Problem to be Solved by the Invention
Lanthanum chromite (LaCr)
O 3 ), etc., and Ni, etc. of the metal film used to reduce the contact resistance have large thermal expansion coefficients, so that if the thickness of the metal film is large during heating or operation of the fuel cell, a strong heat will be generated. A separator that separates the metal film and the current collector 3 by the action of stress.
There is a problem that the contact resistance is increased due to peeling from the surface 9 of the tape 4.
【００１１】また、集電体３と接合されるセパレ−タ４
の面９にＮｉ等の金属膜を形成するためには、金属ペ−
ストを筆やローラーを用いて塗布し焼き付ける方法やメ
ッキする方法があるが、前者は膜厚が数十μｍになるな
ど、薄く均一に形成することが困難であり、後者はメッ
キコストが高いという問題があった。Further, a separator 4 joined to the collector 3
To form a metal film such as Ni on the surface 9 of the
Although there is a method of applying a strike with a brush or a roller and baking or a method of plating, the former is difficult to form thinly and evenly with a film thickness of several tens of μm, and the latter has a high plating cost. There was a problem.
【００１２】そこで本発明の目的は、固体電解質型燃料
電池において、昇温中あるいは作動中に、集電体と接合
されるセパレータの面からＮｉ等の金属膜が剥離せず、
これにより、セパレータと集電体の接触抵抗を低減でき
る電池を提供すること、また、集電体と接合されるセパ
レータの面に、Ｎｉ等の金属膜を薄く均一に、かつ、安
価に形成することができる方法を提供することにある。Therefore, an object of the present invention is to prevent the metal film of Ni or the like from peeling off from the surface of the separator joined to the current collector during temperature rise or operation in the solid oxide fuel cell.
This provides a battery in which the contact resistance between the separator and the current collector can be reduced, and a metal film such as Ni is thinly and uniformly formed on the surface of the separator joined to the current collector at low cost. Is to provide a method that can.
【００１３】[0013]
【課題を解決するための手段】本発明は、請求項１にお
いて、集電体と接合されるセパレータの面に、厚さが１
０μｍ以下のＮｉ膜を形成したことを特徴とするもので
ある。According to a first aspect of the present invention, the surface of the separator joined to the current collector has a thickness of 1
The feature is that a Ni film having a thickness of 0 μm or less is formed.
【００１４】また、請求項２において、集電体と接合さ
れるセパレータの面に、スクリーン印刷法によりＮｉペ
ーストを塗布し、焼き付けてＮｉ膜を形成することを特
徴とするものである。Further, in a second aspect of the present invention, the surface of the separator joined to the current collector is coated with Ni paste by a screen printing method and baked to form a Ni film.
【００１５】[0015]
【作用】本発明の請求項１によれば、集電体と接合され
るセパレータの面に、厚さが１０μｍ以下のＮｉ膜を形
成したことにより、膜厚が薄いために熱応力が弱めら
れ、電池の昇温中あるいは作動中に、Ｎｉ膜がセパレー
タの表面から剥離せず、セパレータと集電体の接触抵抗
を低減することができる。According to the first aspect of the present invention, since the Ni film having a thickness of 10 μm or less is formed on the surface of the separator joined to the current collector, the thermal stress is weakened because the film thickness is thin. The Ni film does not peel off from the surface of the separator during the temperature rise or operation of the battery, and the contact resistance between the separator and the current collector can be reduced.
【００１６】また、本発明の請求項２によれば、集電体
と接合されるセパレータの面に、スクリーン印刷法によ
りＮｉペーストを塗布し、焼き付けてＮｉ膜を形成する
ことにより、薄く均一にかつ安価にＮｉ膜を形成するこ
とができる。According to a second aspect of the present invention, a Ni paste is applied to the surface of the separator to be joined to the current collector by a screen printing method and baked to form a Ni film, thereby forming a thin and uniform film. Moreover, the Ni film can be formed at low cost.
【００１７】[0017]
【実施例】以下、本発明に係わる実施例及び比較例につ
いて説明する。EXAMPLES Examples and comparative examples according to the present invention will be described below.
【００１８】集電体と接合されるセパレ−タの面にＮｉ
膜を以下のように形成した。Ni is formed on the surface of the separator to be joined to the current collector.
The film was formed as follows.
【００１９】まず、粒径０．５μｍのＮｉ粉末４０ｗｔ
％に、グリコール系ワニスを６０ｗｔ％加え、十分に混
合してＮｉペーストを作製した。これを３２５メッシュ
のスクリーン印刷版を用いて、集電体と接合されるセパ
レータの面に塗布し、６０℃の温風で強制乾燥した。そ
の後、この印刷と乾燥を交互に２回繰り返した。First, 40 wt of Ni powder having a particle size of 0.5 μm
%, A glycol-based varnish was added to 60% by weight and mixed sufficiently to prepare a Ni paste. This was applied to the surface of the separator joined to the current collector using a 325-mesh screen printing plate, and forcedly dried with hot air at 60 ° C. After that, this printing and drying were alternately repeated twice.
【００２０】次に、このセパレータ上のＮｉペースト
を、３％のＨ2 と９７％のＮ2 の還元雰囲気中において
１０００℃で焼き付け、セパレータの表面に膜厚が約１
０μｍのＮｉ膜を形成した。なお、膜厚は技術的に可能
な限り、１０μｍ以下で薄ければ薄いほどよい。Next, the Ni paste on this separator was baked at 1000 ° C. in a reducing atmosphere of 3% H 2 and 97% N 2 , so that the surface of the separator had a thickness of about 1 μm.
A Ni film of 0 μm was formed. The thickness of the film is preferably as thin as 10 μm or less as far as technically possible.
【００２１】このようにして得られた試料で３セルのス
タックを構成し、燃料極には３０℃の水中を通して加湿
したＨ2 を、また、空気極には空気を供給して、１００
０℃にて発電を行った。そして、運転中にセパレータと
Ｎｉ集電体の間の接触抵抗を測定した。A three-cell stack was constructed with the sample thus obtained, and H 2 which was humidified by passing water at 30 ° C. was supplied to the fuel electrode and air was supplied to the air electrode to obtain 100
Power was generated at 0 ° C. Then, the contact resistance between the separator and the Ni current collector was measured during the operation.
【００２２】また、比較例１として、Ｎｉ膜の厚みが１
５μｍのものを実施例と同じ方法を用いて作製し、３セ
ルのスタックを構成して、実施例と同様に、燃料極には
３０℃の水中を通して加湿したＨ2 を、また、空気極に
は空気を供給して、１０００℃で発電を行った。そし
て、運転中にセパレータとＮｉ集電体の間の接触抵抗を
測定した。As Comparative Example 1, the Ni film has a thickness of 1
5 μm one was manufactured using the same method as in the example to construct a stack of 3 cells, and in the same manner as in the example, H 2 which was humidified by passing water at 30 ° C. into the fuel electrode and to the air electrode Supplied air to generate electricity at 1000 ° C. Then, the contact resistance between the separator and the Ni current collector was measured during the operation.
【００２３】また、比較例２として、Ｎｉ膜を全く形成
していないものを作製し、３セルのスタックを構成し
て、実施例と同様に、燃料極には３０℃の水中を通して
加湿したＨ2 を、また、空気極には空気を供給して、１
０００℃で発電を行った。そして、運転中にセパレータ
とＮｉ集電体の間の接触抵抗を測定した。Further, as Comparative Example 2, one in which no Ni film was formed was prepared, and a stack of 3 cells was formed. 2 and supply air to the cathode,
Power was generated at 000 ° C. Then, the contact resistance between the separator and the Ni current collector was measured during the operation.
【００２４】これらの実施例、比較例１及び２につい
て、測定した接触抵抗をそれぞれ表１に示す。Table 1 shows the measured contact resistances of these Examples and Comparative Examples 1 and 2, respectively.
【００２５】そして、実施例については、Ｎｉ膜の剥離
が起こらなかったことを、また、比較例１については、
Ｎｉ膜の剥離が起こったことを、それぞれ運転後に目視
で確認した。In the example, the peeling of the Ni film did not occur, and in the comparative example 1,
The fact that the Ni film was peeled off was visually confirmed after each operation.
【００２６】[0026]
【表１】 [Table 1]
【００２７】実施例はＮｉの膜厚が１０μｍと薄いた
め、熱応力が弱められ、Ｎｉがセパレータの表面から剥
離せず、接触抵抗が低く抑えられていた。In the examples, since the Ni film thickness was as thin as 10 μm, the thermal stress was weakened, Ni did not separate from the surface of the separator, and the contact resistance was kept low.
【００２８】しかし、比較例１は実施例に対し、Ｎｉの
厚みが厚く形成されていたため、昇温中、あるいは運転
中に熱応力が強く働いて、セパレータの表面からＮｉ膜
が剥離し、接触抵抗が増加した。However, in Comparative Example 1, since the thickness of Ni was formed thicker than that of Example, thermal stress strongly acted during the temperature rise or during operation, and the Ni film was peeled off from the surface of the separator and contacted. Resistance increased.
【００２９】また、比較例２はＮｉ膜が全く形成されて
いないために、Ｎｉ膜の剥離が起こった比較例１よりも
更に高い接触抵抗を示した。Further, Comparative Example 2 showed a higher contact resistance than Comparative Example 1 in which the Ni film was peeled off because the Ni film was not formed at all.
【００３０】[0030]
【発明の効果】本発明によれば、集電体と接合されるセ
パレータの面に、厚さが１０μｍ以下のＮｉ膜を形成し
たことで、セパレータと集電体の間の接触抵抗を低減で
きるため、燃料電池の出力を向上させることができる。
また、集電体と接合されるセパレータの面に、スクリー
ン印刷法によりＮｉペーストを塗布し、焼き付けてＮｉ
膜を形成することで、Ｎｉ膜を薄く均一に形成でき、安
価に製造できるようになる。According to the present invention, the contact resistance between the separator and the current collector can be reduced by forming the Ni film having a thickness of 10 μm or less on the surface of the separator joined to the current collector. Therefore, the output of the fuel cell can be improved.
In addition, a Ni paste is applied to the surface of the separator to be joined to the current collector by a screen printing method and baked to form Ni
By forming the film, the Ni film can be thinly and uniformly formed and can be manufactured at low cost.
【図１】平板型の固体電解質型燃料電池の分解斜視図。FIG. 1 is an exploded perspective view of a flat plate solid oxide fuel cell.
１ セル ２ 発電部 ３ 集電体 ４ セパレータ ５ 空気極 ６ 固体電解質 ７ 燃料極 ８ 溝 ９ 集電体と接合されるセパレータの面 １０ スタック 1 Cell 2 Power Generation Section 3 Current Collector 4 Separator 5 Air Electrode 6 Solid Electrolyte 7 Fuel Electrode 8 Groove 9 Surface of Separator Joined with Current Collector 10 Stack
Claims (2)
厚さが１０μｍ以下のＮｉ膜を形成したことを特徴とす
る固体電解質型燃料電池。1. A surface of a separator to be joined to a current collector,
A solid oxide fuel cell, characterized in that a Ni film having a thickness of 10 μm or less is formed.
スクリーン印刷法によりＮｉペーストを塗布し、焼き付
けてＮｉ膜を形成することを特徴とする固体電解質型燃
料電池の製造方法。2. The surface of the separator joined to the current collector,
A method for producing a solid oxide fuel cell, which comprises applying a Ni paste by a screen printing method and baking it to form a Ni film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6069404A JPH07282821A (en) | 1994-04-07 | 1994-04-07 | Solid electrolyte fuel cell and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6069404A JPH07282821A (en) | 1994-04-07 | 1994-04-07 | Solid electrolyte fuel cell and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07282821A true JPH07282821A (en) | 1995-10-27 |
Family
ID=13401640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6069404A Pending JPH07282821A (en) | 1994-04-07 | 1994-04-07 | Solid electrolyte fuel cell and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07282821A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6291094B1 (en) | 1998-05-07 | 2001-09-18 | Toyota Jidosha Kabushiki Kaisha | Separator for fuel cell, fuel cell incorporating the same, and method of production of the same |
| WO2002093671A1 (en) * | 2001-05-14 | 2002-11-21 | Tokyo Gas Company Limited | Laminated structure of flat plate type solid oxide fuel cell |
| EP1407504A4 (en) * | 2001-07-13 | 2007-12-05 | Ceramic Fuel Cells Ltd | A fuel cell gas separator plate |
-
1994
- 1994-04-07 JP JP6069404A patent/JPH07282821A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6291094B1 (en) | 1998-05-07 | 2001-09-18 | Toyota Jidosha Kabushiki Kaisha | Separator for fuel cell, fuel cell incorporating the same, and method of production of the same |
| WO2002093671A1 (en) * | 2001-05-14 | 2002-11-21 | Tokyo Gas Company Limited | Laminated structure of flat plate type solid oxide fuel cell |
| US7223492B2 (en) | 2001-05-14 | 2007-05-29 | Tokyo Gas Co., Ltd. | Laminated structure of flat plate type solid oxide fuel cell |
| EP1407504A4 (en) * | 2001-07-13 | 2007-12-05 | Ceramic Fuel Cells Ltd | A fuel cell gas separator plate |
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