JPH04306563A - Manufacture of unit cell for solid electrolyte type fuel cell - Google Patents
Manufacture of unit cell for solid electrolyte type fuel cellInfo
- Publication number
- JPH04306563A JPH04306563A JP3070011A JP7001191A JPH04306563A JP H04306563 A JPH04306563 A JP H04306563A JP 3070011 A JP3070011 A JP 3070011A JP 7001191 A JP7001191 A JP 7001191A JP H04306563 A JPH04306563 A JP H04306563A
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- electrode
- membrane
- electrolyte membrane
- 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.)
- Pending
Links
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 57
- 239000000446 fuel Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000012528 membrane Substances 0.000 claims description 82
- 239000007787 solid Substances 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims 1
- 230000002093 peripheral effect Effects 0.000 abstract description 8
- 239000002002 slurry Substances 0.000 abstract description 8
- 239000007772 electrode material Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 230000000873 masking effect Effects 0.000 abstract description 5
- 239000007921 spray Substances 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000008646 thermal stress Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 229910002254 LaCoO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229910002182 La0.7Sr0.3MnO3 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- -1 for example 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
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000035882 stress Effects 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
- 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
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
-
- 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
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
- 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
の単電池製造方法に係り、特に単電池全体としての機械
的強度を向上させた固体電解質型燃料電池の単電池製造
方法に関するものである。[Field of Industrial Application] The present invention relates to a method for manufacturing a solid oxide fuel cell, and more particularly to a method for manufacturing a solid oxide fuel cell that improves the mechanical strength of the entire cell. be.
【０００２】0002
【従来の技術】低公害のエネルギー源として注目を集め
ている燃料電池の中で、特に電解質の漏洩のおそれがな
く、反応速度が大きいとして期待されているのが固体電
解質型燃料電池である。このような固体電解質型燃料電
池は、電池の最小単位である単電池を多数積層し、これ
を電気的に直列または並列に連結して構成されており、
各単電池は、固体電解質膜に酸素極膜および燃料極膜を
積層して構成される。BACKGROUND OF THE INVENTION Among fuel cells that are attracting attention as a low-pollution energy source, solid oxide fuel cells are particularly promising because they have no risk of electrolyte leakage and have a high reaction rate. Such solid oxide fuel cells are constructed by stacking a large number of single cells, which are the smallest unit of the battery, and electrically connecting them in series or parallel.
Each unit cell is constructed by laminating an oxygen electrode membrane and a fuel electrode membrane on a solid electrolyte membrane.
【０００３】単電池を構成する固体電解質膜には緻密度
が要求される一方、電極膜には多孔質性が要求される。
緻密度が要求される固体電解質膜上に、多孔質性が要求
される電極膜を積層する方法として、従来より、固体電
解質膜にシートまたはフィルム状の電極膜を積層して焼
成する方法が採用されており、また本発明者が提案した
未公知の、固体電解質膜に粉末状の電極材を薄層状に付
着させた後、焼成する方法もある。[0003] While the solid electrolyte membrane constituting a cell is required to be dense, the electrode membrane is required to be porous. Conventionally, the method of laminating an electrode membrane that requires porosity on a solid electrolyte membrane that requires density is to laminate a sheet or film-like electrode membrane on a solid electrolyte membrane and then sinter it. There is also an unknown method proposed by the present inventor in which a powdered electrode material is deposited in a thin layer on a solid electrolyte membrane and then fired.
【０００４】しかしながら上記先行技術は、固体電解質
膜上に、数百μｍ程度の比較的厚い電極膜を形成させる
場合、各電極膜自身の機械的強度が向上することにより
電極膜と固体電解質膜とが剥離し易くなり、また、固体
電解質膜の両面にそれぞれ酸素極膜および燃料極膜を形
成した後焼成する、三層膜一体焼結時に固体電解質膜の
焼結が阻害されて緻密な固体電解質の作製が困難になる
など、固体電解質膜をはじめ、単電池全体の機械的強度
が低下するという問題がある。一方、最近では燃料電池
の出力電流を増大させるために、単電池の大面積化が図
られるようになり、これに伴って焼結時の各部材の熱応
力が大きくなり、これによって電極膜と固体電解質膜と
が剥離し易くなったり、単電池自身にソリが生じるとい
う問題も発生している。However, in the above-mentioned prior art, when a relatively thick electrode film of several hundred μm is formed on a solid electrolyte membrane, the mechanical strength of each electrode film itself improves, so that the electrode film and the solid electrolyte film are separated. Also, when the three-layer membrane is sintered after forming the oxygen electrode membrane and fuel electrode membrane on both sides of the solid electrolyte membrane, the sintering of the solid electrolyte membrane is inhibited, resulting in a dense solid electrolyte. There is a problem that the mechanical strength of the solid electrolyte membrane and the entire unit cell decreases, such as making it difficult to fabricate. On the other hand, in recent years, in order to increase the output current of fuel cells, the area of single cells has been increased, and as a result, the thermal stress of each member during sintering has increased, causing the electrode film to Problems have also arisen in that the solid electrolyte membrane tends to separate, and the cells themselves warp.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、上記
先行技術の問題点を解決し、固体電解質膜に比較的厚膜
の電極膜を積層した場合にも、固体電解質膜および電極
膜の強度をそれぞれ有効に保持し、各部材の接触強度を
向上させて単電池全体としての機械的強度を向上させる
ことができる固体電解質型燃料電池の単電池製造方法を
提供することにある。[Problems to be Solved by the Invention] An object of the present invention is to solve the problems of the prior art described above, and to solve the problems of the solid electrolyte membrane and the electrode membrane even when a relatively thick electrode membrane is laminated on the solid electrolyte membrane. It is an object of the present invention to provide a method for manufacturing a unit cell of a solid oxide fuel cell, which can effectively maintain the strength of each member, improve the contact strength of each member, and improve the mechanical strength of the unit cell as a whole.
【０００６】[0006]
【課題を解決するための手段】本発明者は、固体電解質
膜と電極膜との熱膨張係数および焼き締まり率（シュリ
ンケージ）の違いによって生じる熱応力を抑えて単電池
の機械的強度を向上させるためには、発生する熱応力を
分散させて小さくすることが有効であることに着目し、
鋭意研究した結果、固体電解質膜上に不連続で、しかも
中央部分が厚くて周辺部分が薄い、複数の電極膜の集合
体を付着させた後、焼結することにより、発生する熱応
力が分散され、結果的に機械的強度が大きな単電池が得
られることを見出し、本発明に到達した。[Means for Solving the Problem] The present inventor has improved the mechanical strength of a single cell by suppressing thermal stress caused by the difference in thermal expansion coefficient and shrinkage between a solid electrolyte membrane and an electrode membrane. Focusing on the fact that it is effective to disperse and reduce the thermal stress that occurs,
As a result of extensive research, we discovered that by attaching an aggregate of multiple discontinuous electrode films, thick in the center and thin in the periphery, on a solid electrolyte membrane and then sintering, the generated thermal stress was dispersed. As a result, it was discovered that a single cell with high mechanical strength could be obtained, and the present invention was achieved.
【０００７】すなわち本発明は、固体電解質膜の片面ま
たは両面に電極膜を積層する固体電解質型燃料電池の単
電池製造方法であって、前記固体電解質膜の電極膜形成
部分に、不連続で、かつ中央部分が厚くて周辺部分が薄
い、複数の電極膜を付着させた後、焼成することを特徴
とする。That is, the present invention provides a method for manufacturing a unit cell of a solid oxide fuel cell in which an electrode film is laminated on one or both sides of a solid electrolyte membrane, the method comprising: discontinuously discontinuously disposing the electrode film forming portion of the solid electrolyte membrane; The method is characterized in that a plurality of electrode films, which are thick in the center and thin in the peripheral parts, are deposited and then fired.
【０００８】[0008]
【作用】固体電解質膜上に積層する電極膜の形状を従来
のように均一な膜としないで、不連続な多数の電極膜の
集合体とし、かつ各電極膜の膜厚を中心部ほど厚くし、
周辺部ほど薄くしたことにより、電極膜と固体電解質膜
の熱膨張係数や焼き締まり率の違いによって生じる熱応
力を小さく抑えることができ、単電池の機械的強度が向
上する。また、形状の効果だけでは吸収できないほどの
大きな応力が発生しても、電極膜周辺部（電極膜の薄い
部分）のひび割れによって吸収することができるので、
電解質の機械的強度の低下を最小限に抑えることができ
る。さらに、電極膜を小型電極膜の集合体としたことに
より、固体電解質膜は、電極膜が積層されたことによる
悪影響を受けることなく良好に焼結されて固体電解質本
来の機械的強度を有するようになる。すなわち固体電解
質膜上に形成される小型電極膜相互間の電極膜は非常に
薄いか、または電極膜が形成されていない部分が存在す
ることになり、固体電解質膜が単独膜として焼結される
部分が連続して形成されるので、固体電解質膜の機械的
強度が充分に発揮され、単電池のソリが生ずることがな
くなる。[Function] The shape of the electrode film stacked on the solid electrolyte membrane is not a uniform film as in the past, but an aggregate of many discontinuous electrode films, and the film thickness of each electrode film is thicker toward the center. death,
By making the peripheral portion thinner, the thermal stress caused by the difference in thermal expansion coefficient and compaction rate between the electrode film and the solid electrolyte film can be suppressed, and the mechanical strength of the unit cell is improved. In addition, even if a large stress occurs that cannot be absorbed by the shape effect alone, it can be absorbed by cracks in the peripheral area of the electrode film (thin part of the electrode film).
Decrease in mechanical strength of the electrolyte can be minimized. Furthermore, by forming the electrode film into an assembly of small electrode films, the solid electrolyte film can be sintered well without being adversely affected by the stacking of electrode films, and has the mechanical strength inherent to a solid electrolyte. become. In other words, the electrode film between the small electrode films formed on the solid electrolyte membrane is very thin, or there are parts where no electrode film is formed, and the solid electrolyte film is sintered as a single film. Since the portions are formed continuously, the mechanical strength of the solid electrolyte membrane is fully exerted, and warpage of the unit cell is prevented.
【０００９】本発明において、固体電解質としては、例
えばＺｒＯ２ −Ｙ２ Ｏ３ （ＹＳＺ）、ＣｅＯ２
−ＣａＯ、ＣｅＯ２ −Ｙ２ Ｏ３ 系のもの等が使用
され、ドクターブレード法等によって、例えば３００〜
７００μｍの厚さの膜に成形されることが好ましい。酸
素極材としては、例えばランタン系のＬａＣｏＯ３ 、
Ｌａ０．７ Ｓｒ０．３ ＭｎＯ３ 、Ｌａ０．７ Ｃ
ａ０．３ ＭｎＯ３ 、Ｌａ０．６ Ｂａ０．４ Ｃｏ
０．８ Ｃｕ０．２ Ｏ３ 等が、一方、燃料極材とし
ては、例えばニッケル系のＮｉＯ−ＺｒＯ２ −Ｙ２
Ｏ３ 等が使用される。このような電極材は、例えば０
．１μｍ〜１０μｍに粉砕され、スラリとして、または
そのまま粉末として使用される。スラリとして使用する
場合、溶媒としては、例えばエタノール、トルエン等を
用いることが好ましく、また電極材粉末の成形性を確保
するためのバインダーとして、例えばポリビニルブチラ
ール等を添加することが好ましい。[0009] In the present invention, solid electrolytes include, for example, ZrO2-Y2O3 (YSZ), CeO2
-CaO, CeO2 -Y2 O3 type, etc. are used, and by the doctor blade method etc., for example, 300~
Preferably, the film is formed into a 700 μm thick film. As the oxygen electrode material, for example, lanthanum-based LaCoO3,
La0.7 Sr0.3 MnO3, La0.7 C
a0.3 MnO3, La0.6 Ba0.4 Co
0.8 Cu0.2 O3 etc., on the other hand, as a fuel electrode material, for example, nickel-based NiO-ZrO2 -Y2
O3 etc. are used. Such an electrode material is, for example, 0
．． It is ground to 1 μm to 10 μm and used as a slurry or as it is as a powder. When used as a slurry, it is preferable to use, for example, ethanol, toluene, etc. as a solvent, and it is preferable to add, for example, polyvinyl butyral, etc. as a binder to ensure moldability of the electrode material powder.
【００１０】本発明において、電極材のスラリまたは粉
末は、任意の形状、例えば格子状、メッシュ状、短冊状
等に刳り抜かれたマスキング材を載置した固体電解質膜
上にスプレー法またはスクリーン印刷法等によって噴霧
、または塗布され、前記固体電解質膜上に不連続な電極
膜集合体が形成される。不連続な電極膜は、その中央部
分の膜厚が、例えば１００〜３００μｍであることが好
ましく、その周辺部分は順次薄く構成されることが好ま
しい。In the present invention, the slurry or powder of the electrode material is sprayed or screen printed onto a solid electrolyte membrane on which a masking material hollowed out in an arbitrary shape, such as a grid, mesh, or strip, is placed. A discontinuous electrode membrane assembly is formed on the solid electrolyte membrane by spraying or coating the solid electrolyte membrane. Preferably, the discontinuous electrode film has a thickness of, for example, 100 to 300 μm at the central portion, and the peripheral portions thereof are preferably configured to be successively thinner.
【００１１】電極膜集合体が付着された固体電解質膜は
、焼結されて単電池とされるが、その焼成温度は、例え
ば１２００〜１６００℃が好ましく、焼成時間は３〜１
０時間であることが好ましい。本発明において、固体電
解質膜の両面にそれぞれ酸素極膜および燃料極膜を付着
させた後焼成する、三層膜一体焼結法によって単電池を
製造する場合、固体電解質膜の一方面に形成される酸素
極膜の数、形状および大きさは、他方面に形成される燃
料極膜と必ずしも同じである必要はない。しかし、いう
までもなく、小型の燃料極膜と小型の酸素極膜とは固体
電解質膜を介して他方の面積を一方が必ずカバーしてお
く必要がある。[0011] The solid electrolyte membrane to which the electrode membrane assembly is attached is sintered to form a cell. The firing temperature is preferably 1200 to 1600°C, and the firing time is 3 to 1.
Preferably it is 0 hours. In the present invention, when a unit cell is manufactured by a three-layer membrane integral sintering method in which an oxygen electrode membrane and a fuel electrode membrane are attached to both sides of a solid electrolyte membrane and then fired, a single cell is formed on one side of the solid electrolyte membrane. The number, shape and size of the oxygen electrode films do not necessarily have to be the same as the fuel electrode film formed on the other side. However, it goes without saying that one of the small fuel electrode membranes and the small oxygen electrode membrane must cover the area of the other through the solid electrolyte membrane.
【００１２】0012
【実施例】次に本発明を実施例によりさらに詳細に説明
する。図１は、本発明の一実施例によって作製された単
セルの斜視図、図２は図１のＩＩ−ＩＩ線矢視方向断面
図である。固体電解質膜１は、ＺｒＯ２ −Ｙ２ Ｏ３
を用いてドクターブレード法によって５００μｍ厚に
成形した。
また、酸素極膜材としてＬａＣｏＯ３ を用い、これを
０．１〜１０μｍに粉砕して得られた粉末とエタノール
、トルエンとの混合物に全重量基準で５％のポリビニル
ブチラールをバインダーとして添加し、混練してスラリ
とした。一方、燃料極膜材としてはＮｉＯ−ＺｒＯ２
−Ｙ２ Ｏ３ を用い、これを粉砕した０．１〜１０μ
ｍの粉末とエタノール、トルエンとの混合物に全重量基
準で５％のポリビニルブチラールを添加して混練してス
ラリとした。EXAMPLES Next, the present invention will be explained in more detail with reference to examples. FIG. 1 is a perspective view of a single cell manufactured according to an embodiment of the present invention, and FIG. 2 is a sectional view taken along the line II--II in FIG. The solid electrolyte membrane 1 is made of ZrO2-Y2O3
It was molded to a thickness of 500 μm using a doctor blade method. In addition, LaCoO3 was used as the oxygen electrode membrane material, and 5% polyvinyl butyral (based on the total weight) was added as a binder to a mixture of the powder obtained by pulverizing it to 0.1 to 10 μm, ethanol, and toluene, and the mixture was kneaded. It became slurry. On the other hand, NiO-ZrO2 is used as the fuel electrode membrane material.
-0.1 to 10μ crushed using Y2O3
Polyvinyl butyral was added in an amount of 5% based on the total weight to a mixture of the powder, ethanol, and toluene, and the mixture was kneaded to form a slurry.
【００１３】次いで前記固体電解質膜１の表面に、格子
状のメッシュからなるマスキング材を載置し、その上方
から前記酸素極膜２用のスラリをスプレー法によって噴
霧し、各電極膜の中心部分の膜厚が２００μｍになるよ
うに付着させた。一方、前記固体電解質膜１の他方面に
も同様の格子状のマスキング材を載置し、前記燃料極膜
３用のスラリを同様に付着させた。このようにして表裏
両面に不連続で、かつ中央部分が２００μｍと厚く、周
辺部分が薄い酸素極膜および燃料極膜がそれぞれ付着さ
れた固体電解質膜１を三層膜一体焼結法により約１５０
０℃で１０時間焼成し、一工程で単電池を形成した。[0013] Next, a masking material consisting of a grid-like mesh is placed on the surface of the solid electrolyte membrane 1, and the slurry for the oxygen electrode membrane 2 is sprayed from above by a spray method, so that the central part of each electrode membrane is sprayed. It was deposited so that the film thickness was 200 μm. On the other hand, a similar grid-shaped masking material was placed on the other side of the solid electrolyte membrane 1, and the slurry for the fuel electrode membrane 3 was similarly deposited thereon. In this way, the solid electrolyte membrane 1, which is discontinuous on both the front and back surfaces, has a thick oxygen electrode membrane of 200 μm at the center, and a thin oxygen electrode membrane and fuel electrode membrane at the peripheral portions, is formed by the three-layer membrane integral sintering method.
It was baked at 0° C. for 10 hours to form a single cell in one step.
【００１４】本実施例によって製造された単電池の固体
電解質膜１の強度は、固体電解質膜のみを同条件で焼成
したものに比べて全く低下していなかった。また、固体
電解質膜１と両電極膜２および３の接触状態は良好であ
り、１０００℃における固体電解質膜１と、空気極膜２
および燃料極膜３の電気的接触抵抗はそれぞれ、０．０
１５、０．００７オーム・ｃｍ２ であった。また、こ
の電池を１０００℃で７００時間使用しても電極膜の剥
離は生じなかった。[0014] The strength of the solid electrolyte membrane 1 of the unit cell manufactured according to this example was not decreased at all compared to that of a solid electrolyte membrane alone fired under the same conditions. Further, the contact state between the solid electrolyte membrane 1 and both electrode membranes 2 and 3 was good, and the solid electrolyte membrane 1 and the air electrode membrane 2 at 1000°C were in good condition.
and the electrical contact resistance of the fuel electrode membrane 3 is 0.0, respectively.
15, 0.007 ohm·cm2. Furthermore, even when this battery was used at 1000° C. for 700 hours, no peeling of the electrode film occurred.
【００１５】本実施例によれば、固体電解質膜１の表面
にその中央部分が厚く、周辺部分が薄くなった複数の不
連続な空気極膜２および燃料極膜３をそれぞれ形成した
のち焼成したことにより、固体電解質膜１と酸素極膜２
および燃料極膜３との間にはたらく熱応力が小さくなり
、また固体電解質膜１は前記電極膜２および３に妨害さ
れることなく緻密に焼結された部分が連続して存在し、
強度が保持されるので、全体として機械的強度の大きな
単電池が得られる。また、固体電解質膜１が緻密性を有
するとともに酸素極膜２および燃料極膜３が多孔性を有
し、各膜部材が緊密に接触するので電気的接触抵抗が大
幅に小さくなる。According to this embodiment, a plurality of discontinuous air electrode films 2 and fuel electrode films 3 each having a thick central portion and a thin peripheral portion are formed on the surface of a solid electrolyte membrane 1, and then fired. By this, the solid electrolyte membrane 1 and the oxygen electrode membrane 2
The thermal stress acting between the solid electrolyte membrane 1 and the fuel electrode membrane 3 is reduced, and a densely sintered portion of the solid electrolyte membrane 1 is continuously present without being obstructed by the electrode membranes 2 and 3.
Since the strength is maintained, a unit cell with high mechanical strength as a whole can be obtained. In addition, the solid electrolyte membrane 1 is dense, and the oxygen electrode membrane 2 and fuel electrode membrane 3 are porous, and each membrane member is in close contact with each other, so that the electrical contact resistance is significantly reduced.
【００１６】図３、図４および図５は、それぞれ本発明
の他の実施例によって製造された単電池の斜視図であり
、各単電池は電極膜を形成する際に、形状が異なるマス
キング材を使用した以外は図１の単電池と同様にして製
造されたものである。すなわち図３は、各電極膜の形状
を短冊型としたもの、図４は、図３よりも短い短冊状と
して２列に配列したもの、および図５は、各電極膜の形
状を円形としたものである。これらの単電池においても
電極膜の中央部分が厚く、周辺部分が薄く構成されてお
り、前記実施例と同様、固体電解質膜と各電極膜との熱
膨張係数および焼き締まり率の相違に起因する熱応力が
小さくなり、結果的に機械的強度が大きい単電池が得ら
れる。FIGS. 3, 4, and 5 are perspective views of unit cells manufactured according to other embodiments of the present invention, and each unit cell is coated with masking materials having different shapes when forming an electrode film. The unit cell was manufactured in the same manner as the unit cell shown in FIG. 1 except that . That is, FIG. 3 shows a case in which each electrode film has a rectangular shape, FIG. 4 shows a case in which each electrode film has a rectangular shape and is arranged in two rows, and FIG. 5 shows a case in which each electrode film has a circular shape. It is something. In these cells, the central part of the electrode film is thick and the peripheral part is thin, and as in the above example, this is due to the difference in thermal expansion coefficient and compaction rate between the solid electrolyte film and each electrode film. Thermal stress is reduced, resulting in a cell with high mechanical strength.
【００１７】[0017]
【発明の効果】本発明によれば、固体電解質膜に積層さ
れる電極膜を不連続で、しかも中央部分が厚くて周辺部
分が薄い、複数の小型電極膜の集合体としたことにより
、各構成膜相互間にはたらく熱応力が小さくなるので、
単電池全体としての機械的強度が向上する。したがって
、例えば３００〜７００μｍの固体電解質膜に１００〜
３００μｍ程度の比較的厚い電極膜を形成しても、剥離
等による強度低下を生じることなく、機械的強度の大き
な単電池が得られる。[Effects of the Invention] According to the present invention, the electrode film laminated on the solid electrolyte membrane is discontinuous, and is an aggregate of a plurality of small electrode films that are thick at the center and thin at the periphery. Since the thermal stress acting between the constituent films is reduced,
The mechanical strength of the cell as a whole is improved. Therefore, for example, in a solid electrolyte membrane of 300 to 700 μm,
Even if a relatively thick electrode film of about 300 μm is formed, a cell with high mechanical strength can be obtained without deterioration in strength due to peeling or the like.
【図面の簡単な説明】[Brief explanation of drawings]
【図１】本発明の一実施例によって製造された単電池の
斜視図である。FIG. 1 is a perspective view of a cell manufactured according to an embodiment of the present invention.
【図２】図１のＩＩ−ＩＩ線矢視方向断面図である。FIG. 2 is a sectional view taken along the line II-II in FIG. 1;
【図３】、[Figure 3]
【図４】および[Figure 4] and
【図５】それぞれ本発明の他の実施例によって製造され
た単電池の斜視図である。FIG. 5 is a perspective view of a unit cell manufactured according to another embodiment of the present invention.
１…固体電解質膜、２…酸素側電極膜、３…燃料側電極
膜。1...Solid electrolyte membrane, 2...Oxygen side electrode membrane, 3...Fuel side electrode membrane.
Claims (1)
膜を積層する固体電解質型燃料電池の単電池製造方法で
あって、前記固体電解質膜の電極膜形成部分に、不連続
で、かつ中央部分が厚くて周辺部分が薄い、複数の電極
膜を付着させた後、焼成することを特徴とする固体電解
質型燃料電池の単電池製造方法。1. A method for manufacturing a single cell of a solid electrolyte fuel cell, in which an electrode film is laminated on one or both sides of a solid electrolyte membrane, the solid electrolyte membrane having a discontinuous and central portion in which the electrode film is formed. 1. A method for producing a single cell of a solid oxide fuel cell, which comprises depositing a plurality of electrode films, each of which is thick at the periphery and thin at the periphery, and then fired.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3070011A JPH04306563A (en) | 1991-04-02 | 1991-04-02 | Manufacture of unit cell for solid electrolyte type fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3070011A JPH04306563A (en) | 1991-04-02 | 1991-04-02 | Manufacture of unit cell for solid electrolyte type fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04306563A true JPH04306563A (en) | 1992-10-29 |
Family
ID=13419236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3070011A Pending JPH04306563A (en) | 1991-04-02 | 1991-04-02 | Manufacture of unit cell for solid electrolyte type fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04306563A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001095405A3 (en) * | 2000-05-08 | 2003-03-13 | Honda Motor Co Ltd | Fuel cell assembly |
| KR20040003654A (en) * | 2002-07-03 | 2004-01-13 | 엘지전자 주식회사 | Generator of fuel cell |
| US7008718B2 (en) * | 2000-05-08 | 2006-03-07 | Honda Giken Kogyo Kabushiki Kaisha | Fuel cell assembly |
| JP2006344486A (en) * | 2005-06-08 | 2006-12-21 | Japan Fine Ceramics Center | Solid oxide fuel cell and its manufacturing method |
| JP2018133165A (en) * | 2017-02-14 | 2018-08-23 | 日本特殊陶業株式会社 | Electrochemical reaction single cell, and electrochemical reaction cell stack |
-
1991
- 1991-04-02 JP JP3070011A patent/JPH04306563A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001095405A3 (en) * | 2000-05-08 | 2003-03-13 | Honda Motor Co Ltd | Fuel cell assembly |
| JP2004504689A (en) * | 2000-05-08 | 2004-02-12 | 本田技研工業株式会社 | Fuel cell |
| US7008718B2 (en) * | 2000-05-08 | 2006-03-07 | Honda Giken Kogyo Kabushiki Kaisha | Fuel cell assembly |
| KR20040003654A (en) * | 2002-07-03 | 2004-01-13 | 엘지전자 주식회사 | Generator of fuel cell |
| JP2006344486A (en) * | 2005-06-08 | 2006-12-21 | Japan Fine Ceramics Center | Solid oxide fuel cell and its manufacturing method |
| JP2018133165A (en) * | 2017-02-14 | 2018-08-23 | 日本特殊陶業株式会社 | Electrochemical reaction single cell, and electrochemical reaction cell stack |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101045168B1 (en) | Ceramic membranes with integral seals and support, and electrochemical cells and electrochemical cell stacks including the same | |
| US8192888B2 (en) | Two layer electrolyte supported fuel cell stack | |
| US4883497A (en) | Formation of thin walled ceramic solid oxide fuel cells | |
| JP2001196069A (en) | Fuel cell | |
| US20080206618A1 (en) | Electrochemical devices and electrochemical apparatus | |
| JP4781823B2 (en) | Cylindrical horizontal stripe fuel cell | |
| JPH04306563A (en) | Manufacture of unit cell for solid electrolyte type fuel cell | |
| JP3347561B2 (en) | Solid oxide fuel cell | |
| JPH0668885A (en) | Manufacture of solid electrolytic fuel cell | |
| JP3722927B2 (en) | Method for manufacturing solid electrolyte fuel cell assembly unit and solid electrolyte fuel cell assembly | |
| JPH07220730A (en) | Solid electrolyte type fuel cell | |
| JPH10106608A (en) | Solid electrolyte fuel cell and manufacture thereof | |
| JPH02276166A (en) | Solid electrolyte fuel cell | |
| JP2704071B2 (en) | Method for manufacturing single cell of solid oxide fuel cell | |
| JPH02273465A (en) | Manufacture of solid electrolyte fuel cell | |
| JPH09306514A (en) | Manufacture of solid electrolyte fuel cell | |
| JPH07130385A (en) | Cylindrical lateral band type solid electrolyte electrolytic cell | |
| JPH06310156A (en) | Flat solid electrolyte type fuel cell | |
| JP2505565B2 (en) | Solid electrolyte fuel cell | |
| JPH05151982A (en) | Solid electrolyte fuel cell | |
| JPH0562694A (en) | Solid electrolyte type fuel cell | |
| JP3151872B2 (en) | Solid oxide fuel cell | |
| JPH08236137A (en) | Manufacture of solid electrolyte fuel cell | |
| JPH09147887A (en) | Flat solid electrolyte fuel cell | |
| JPH0562693A (en) | Solid electrolyte type fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20010419 |