JPH05166530A - Battery member for solid electrolyte fuel cell - Google Patents

Abstract

(57) [Summary] [Objective] To provide a unit cell member for a solid oxide fuel cell. [Structure] (1) An electrolyte membrane and another side porous electrode membrane are sequentially laminated on one side porous electrode substrate formed in a flat plate shape, and one side porous electrode substrate and the electrolyte membrane are laminated surfaces. A cell member for a solid oxide fuel cell, which is formed so as to be exposed on one side. (2) On the porous support substrate formed in a flat plate shape, one side electrode film, an electrolyte film, the other side electrode film is sequentially laminated, and the one side electrode film, the electrolyte film is on one side of the laminated surface. A solid electrolyte fuel cell member, which is formed so as to be exposed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flat unit cell member for a solid electrolyte fuel cell (hereinafter, simply referred to as SOFC) in which an electrochemical reaction is performed and electric energy is taken out.

[0002]

2. Description of the Related Art Conventionally, as this type of SOFC, a battery composed of a fuel electrode, an electrolyte and an air electrode is formed on the surface of an elongated porous cylindrical support tube, and these are connected in series as a single cell. A cylindrical type is known (Japanese Patent Laid-Open No. 57-130381).

However, the above SOFC has problems in strength and assembling of the support tube, and the present inventors solved these drawbacks in the previous application (Japanese Patent Application No. 2-106610). SOFC was proposed.

That is, in the prior application, a porous substrate is used on the surface of the substrate, or it is not used, and the inner electrode is provided with a hollow portion, and the electrolyte and the outer electrode are sequentially deposited on the inner electrode. The battery unit is formed by stacking by means, and these single cells are connected in series and in parallel by a conductive connecting member.

[0005]

However, in the above method, since the battery section is formed integrally on the substrate simultaneously on the spot, if one of the battery sections is inconvenient, the cell There is a risk that the stack or the entire battery unit assembly may be defective.

Further, since the battery part is formed on the substrate, there is a problem that the substrate is affected by heat when the film of each element of the battery part is formed.

[0007] Therefore, it is an object of the present invention to provide a suitable unit battery member for SOFC which can eliminate such inconvenience in SOFC manufacture.

[0008]

Means for Solving the Problems As a result of earnest studies, the present inventor can solve the problems by using a unit battery member having a flat plate shape in which each lower layer portion is exposed on one side of the stacking surface. The inventors have found out that, and have reached the present invention.

That is, the present invention is as follows: (1) An electrolyte membrane and a porous electrode film on the other side are sequentially laminated on a porous electrode substrate on the one side formed in a flat plate shape, and a porous electrode substrate on the one side and A cell member for a solid electrolyte fuel cell, wherein the electrolyte membrane is formed so as to be exposed on one side of the laminated surface, (2) a one-sided electrode membrane on a porous support substrate formed in a flat plate shape. The solid electrolyte fuel cell member is characterized in that the electrolyte membrane and the electrode film on the other side are sequentially laminated, and the electrode film on the one side and the electrolyte film are formed so as to be exposed on one side of the laminated surface. ..

The first type of battery member used in the present invention is, as shown in FIGS. 1 and 2, a porous member made of either an electrode material of a porous air electrode substrate 3 or a porous fuel electrode substrate 11. The electrolyte membrane 4 and the other electrode membrane, that is, the fuel electrode membrane 5 or the air electrode membrane 12 are laminated in this order on the quality substrate, and the second type is a support as shown in FIGS. 3 and 4. The air electrode film 12 (or the fuel electrode film 5), the electrolyte film 4, and the fuel electrode film 5 (or the air electrode film 12) are laminated in this order on the porous substrate 13 to be a body. Then, as is clear from FIGS. 1 to 4, in any type, the lower layer surface is exposed on one side of the laminated surface. By configuring the battery member in this way,
When the respective battery members are integrated on the substrate and then connected by the conductive member, it is possible to prevent the electrodes in the same battery member from contacting each other.

When used as an SOFC, the battery member of the present invention is integrated on a substrate, for example, a hollow dense substrate 1 provided with holes 10 for mounting a battery member as shown in FIG. (However, some internal structures are omitted).

In this case, the adhesive 6 is applied to the inner wall of the mounting hole 10.
It is preferable to fix it via a holding member, or it is also possible to fix it via a holding member having a gas permeable structure at the bottom as shown in FIG.

In the above, the hollow dense substrate 1 is preferably a ceramic material that is an electrical insulator, and for example, alumina, magnesia, or a mixture thereof is suitable. The electrolyte membrane 4 is preferably yttria-stabilized zirconia (hereinafter referred to as YSZ), and the porous electrode substrate and the electrode membrane are preferably LaMnO ₃ or LaCoO ₃ to which an alkaline earth metal is added for the air electrode. And
Ni-zirconia cermet or the like is suitable for the fuel electrode.

The porous substrate 13 serving as a support is preferably a porous ceramic material, for example, alumina, magnesia, a mixture thereof, or stabilized zirconia, but it is more preferable if it can impart electronic conductivity. ..

As described above, the battery part 2 of the present invention is preferably fitted and installed in the predetermined hole position 10 of the dense substrate, and then,
Electrodes of adjacent battery parts are connected in series and in parallel by a conductive member. At this time, if the dense substrate and the battery part are fixed to each other with an adhesive and a conductive member is formed, an SOFC excellent in gas sealing property can be manufactured.

Alternatively, when the conductive member is formed after forming the gas seal film on the fitting portion, or when the battery portion is fixed with an adhesive and the gas seal film is further formed, the conductive member is formed. If S is used, S that is more excellent in gas sealability
An OFC can be manufactured.

The conductive member is a material having electronic conductivity and stable in a redox atmosphere, and for example, a perovskite type oxide obtained by adding an alkaline earth metal to LaCrO ₃ is suitable.

The adhesive is preferably made of a ceramic material such as alumina, silica or zirconia which is stable and densified in an oxidation-reduction atmosphere, and the holding member is made of Ni.
It is composed of a heat resistant metal material such as a base super heat resistant alloy. The gas seal film is preferably an electrically insulating material such as alumina.

Among the above SOFC components, the hollow dense substrate is produced by extrusion molding, and the porous electrode substrate and the porous supporting substrate are produced by the doctor blade method, powder pressing method, or the like.

Further, an electrode film in the battery member of the present invention,
The electrolyte membrane, the conductive member, and the gas seal membrane are produced by a film forming technique such as a plasma spraying method, a gas flame spraying method, a dry method such as CVD or PVD, or a wet method such as a screen printing method or a dipping method.

[0021]

In the SOFC of the present invention, the case where the porous electrode substrate of the battery part is the air electrode will be described. By keeping SOFC at about 1000 ° C., supplying oxygen to the hollow portion of the dense substrate and supplying hydrogen to the outside of the dense substrate on the fuel electrode side, an electrochemical reaction occurs and electric energy is generated.

[0022]

EXAMPLE A method for manufacturing the battery member 2 of the present invention will be described. First, using La _0.8 Sr _0.2 MnO ₃ as a raw material, a green film is formed by a doctor blade method, cut with a cutter, and then fired at 1200 ° C to 1500 ° C. Then, the porous air electrode substrate 3 is obtained.

Next, the porous air electrode substrate 3 is masked at the current extraction portion, and yttria-stabilized zirconia is sprayed by the plasma spraying method to form the electrolyte membrane 4.

Finally, masking is applied to the electrolyte membrane 4, and NiO-YSZ is sprayed by the gas flame spraying method,
The fuel electrode film 5 is formed to complete the battery unit 2 shown in FIG.

The battery member thus prepared is integrated on a substrate to prepare an SOFC.

FIG. 6 is a plan view showing the outline of the SOFC as a whole, and FIGS. 7 and 8 are sectional views taken along the line YY and XX, respectively.

The dense substrate 1 is extruded from alumina as a raw material, and then a battery part mounting hole is appropriately opened
It was made by firing at 1400 ° C to 1700 ° C.

The plurality of battery parts 2 thus prepared are provided with the alumina-based adhesive 6 in the holes 10 for mounting the battery parts of the dense substrate 1.
It is fixed by. In the case of the present embodiment, 25 battery parts are fixed to one surface of the dense substrate 1, masking is applied to the dense substrate, and LaMgCrO ₃ is sprayed by the plasma spraying method or the gas flame spraying method to obtain the conductive property. The elastic member 7 is formed, and the battery units 2 are connected in series and in parallel.

After the completion of one surface, the other surface of the dense substrate 1 is subjected to the same operation as described above to manufacture the SOFC.

Next, another SO using the battery member of the present invention
An example of creating an FC will be described.

FIG. 9 is a plan view showing the outline of the entire SOFC, and FIGS. 10 and 11 are a sectional view taken along the line YY and a sectional view taken along the line XX, respectively. The gas seal film 8 in the figure is produced by spraying alumina by a plasma spraying method after fixing the battery part 2 to the dense substrate 1 and before forming the conductive member 7, and other materials used. The manufacturing method and the like are similar to those of the SOFC production example.

Power generation can be performed by keeping the completed SOFC at about 1000 ° C., supplying oxygen to the hollow portion 9 of the dense substrate 1 and supplying hydrogen to the fuel electrode side.

The shapes of the dense substrate 1, the battery portion 2, the masking, etc. are not limited to those in the above embodiment, and other shapes may be used, and a porous support substrate is used for the battery portion 2. Even with SOFC, the fuel electrode is hollow 9
Even if it is on the side, the effect of the above manufacturing method is the same.

[0034]

As described above in detail, the battery member of the present invention is structured such that the lower layer is exposed on one side of the laminated surface. Therefore, after the battery members are integrated on the substrate, they are connected. When forming a conductive member for this, the exposed surface can be used to make a reliable connection while avoiding contact with the electrodes of the same battery, and the influence of processing heat on the dense substrate is reduced. Therefore, the yield and reliability of SOFC can be improved.

The structure of the battery section is very simple,
Moreover, since it can be easily attached to the dense substrate, the manufacturing cost can be reduced.

[Brief description of drawings]

FIG. 1 is a perspective view of a battery member of the present invention.

FIG. 2 is a perspective view of another battery member of the present invention.

FIG. 3 is a perspective view of still another battery member of the present invention.

FIG. 4 is a perspective view of still another battery member of the present invention.

FIG. 5 is a perspective view of a hollow dense substrate having a battery portion mounting hole.

FIG. 6 SOFC prepared by using the battery member of the present invention
FIG.

FIG. 7 is a sectional view taken along line YY of FIG. 1;

FIG. 8 is a sectional view taken along line XX of FIG.

FIG. 9 is another SO prepared by using the battery member of the present invention.
The top view which shows the outline of FC.

FIG. 10 is a sectional view taken along line YY of FIG. 9;

FIG. 11 is a sectional view taken along the line XX-X of FIG.

FIG. 12 is a perspective view of a holding member for mounting the battery member of the present invention in a board mounting hole.

FIG. 13 is a perspective view of another holding member.

[Explanation of symbols]

 1 ... Dense substrate, 2 ... Battery part, 3 ... Porous air electrode substrate, 4 ... Electrolyte film, 5 ... Fuel electrode film, 6 ... Adhesive agent, 7 ... Conductive member, 8 ... Gas seal film, 9 ... Hollow Part, 10 ... Battery part mounting hole, 11 ... Porous fuel electrode substrate, 12 ... Air electrode film, 13 ... Porous support substrate

Claims (2)

[Claims] 1. An electrolyte membrane and a porous membrane on the other side are successively laminated on a flat porous electrode substrate on the one side, and the porous electrode substrate on the one side and the electrolyte membrane are laminated on the one surface. A cell member for a solid electrolyte fuel cell, which is formed so as to be exposed on one side. 2. A one-sided electrode film, an electrolyte film, and the other-sided electrode film are sequentially laminated on a porous support substrate formed in a flat plate shape, and the one-sided electrode film and the electrolyte film are one of the laminated surfaces. A solid electrolyte fuel cell member, which is formed so as to be exposed on the side.