JP2013171754A - Solid oxide fuel cell and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high performance solid oxide fuel cell of metal support type in which an electrode can be formed smoothly without damaging gas permeability or electrical conductivity of a substrate, even if a gas permeable metal substrate having a large cavity functioning as a passage of gas is used as a support substrate.SOLUTION: A fuel electrode 4, an electrolyte 5, and an air electrode 6 are formed on a gas permeable metal substrate 2 having a smooth surface state obtained by filling the cavity 2a with at least one kind of material 3 out of acicular nickel oxalate, acicular nickel oxide and fibrous nickel, or by coating the surface with a layer composed of the material 3.

Description

  The present invention relates to a solid oxide fuel cell and a method for manufacturing the same, and in particular, without sacrificing gas diffusivity even when a gas-permeable metal used as a support substrate has a large diameter or opening of a ventilation gap. The present invention relates to a fuel cell in which a fuel electrode can be formed without hindrance.

  A solid oxide fuel cell (SOFC) has a structure in which a solid electrolyte made of an oxide such as YSZ (yttria stabilized zirconia) is used as an electrolyte, and electrodes having gas permeability are arranged on both sides thereof. And operate at a high temperature close to 1000 ° C.

As a laminated structure of such a solid oxide fuel cell, an anode support type and an electrolyte support type are known. In these types of fuel cells, a support substrate made of a ceramic material should be used. Therefore, when it becomes thin, the strength of the substrate cannot be obtained, and it is difficult to ensure the flexibility.
Furthermore, considering the convenience of stacking cells in addition to the viewpoint of substrate strength and flexibility, porous metal with gas permeability compared to the above electrode support type and electrolyte support type Therefore, a metal support type cell using as a support substrate is desirable.

Such a support substrate is required to have sufficient strength as a support member, electrical conductivity, and gas permeability sufficient to supply fuel gas to the fuel cell. Specifically, For example, a punching metal, an etching metal, a metal mesh (wire net), an expanded metal, a foam metal, a metal nonwoven fabric, etc. are used.
And in order to form the battery element which consists of a fuel electrode, an electrolyte, and an air electrode on the metal substrate which consists of such a material, the smoothness of the surface is calculated | required. For example, some punching metals have a hole diameter exceeding 100 μm, and when an electrode is formed on the surface of such a punching metal, the electrode material enters the hole, resulting in a smooth electrode. You will not be able to get.

For example, Patent Document 1 discloses a support substrate having a through hole, one electrode disposed so as to close the through hole, an electrolyte on the electrode, the other electrode on the electrolyte, A solid oxide fuel cell comprising a conductive porous current collector filled in a through hole of a support substrate is described.
In the column of [Best Mode for Carrying Out the Invention] in Patent Document 1, the current collector paste containing a foaming agent resin is used for filling the conductive porous current collector. It is disclosed to sinter in a state where it is buried inside.

JP 2008-251383 A

Therefore, when the punching metal as described above is applied as the metal support substrate, the through hole is filled with the current collector paste as described above and then sintered, so that the through hole is made of a porous conductor. It can be buried and a smooth electrode can be formed thereon.
However, the packing composed of the porous conductor formed in this way is porous during the operation (power generation) at a high temperature, although it has porosity for the time being and exhibits good gas permeability. May be gradually lost, resulting in a problem that gas permeability is impaired.

  The present invention has been made to solve the above-mentioned problems in conventional metal-supported cells, and its object is to provide gas diffusibility even on a support substrate having a large gap that functions as a gas ventilation path. It is another object of the present invention to provide a high-performance solid oxide fuel cell that can form an electrode without impairing electrical conductivity.

  As a result of intensive studies to achieve the above object, the present inventors have filled fibrous nickel into voids of a gas permeable metal used as a support substrate, or formed a multilayer of fibrous nickel on the surface thereof. The present inventors have found that the above object can be achieved by forming the present invention, and have completed the present invention.

The present invention is based on the above knowledge, and the solid oxide fuel cell of the present invention has a void, and at least the surface side of the void has acicular nickel oxalate, acicular nickel oxide, and fibrous nickel. A fuel electrode, an electrolyte, and an air electrode are laminated in this order on the surface of a gas permeable metal substrate filled with at least one material selected from the group consisting of:
Further, the solid oxide fuel cell of the present invention is provided with acicular nickel oxalate, acicular nickel oxide, and fibrous material on the surface of a gas-permeable metal substrate having voids or in the voids of such a gas-permeable metal substrate. On the surface of the gas permeable metal substrate filled with at least one material selected from the group consisting of nickel, the fuel electrode, the electrolyte and the air electrode are laminated in this order via the coating layer made of at least one material. It is characterized by being.

And, in the method for producing a solid oxide fuel cell of the present invention, when filling the above-mentioned material into the gap or forming a multi-layer, from the group consisting of coating, deep coating, screen printing, green sheet pressure bonding, press It is characterized by being applied by at least one selected method.
In addition, after filling the above-mentioned material into the voids or forming a multi-layer, heating is performed at a temperature of 300 to 1200 ° C. in the air, or in an inert atmosphere or an atmosphere containing hydrogen.

  According to the present invention, the fuel electrode is formed on the gas permeable metal substrate in a state where the surface is smoothed by filling the gap with the predetermined material or covering the surface with the layer of the predetermined material. Therefore, the stacking of the fuel electrode, the subsequent electrolyte, and the air electrode is not hindered. And the acicular nickel oxalate and acicular nickel oxide contained in the material in the void and in the coating layer are reduced by the fuel gas at the time of treatment after the filling or power generation, and finally the fibrous nickel (metal) Therefore, gas permeability and electrical conductivity as the support substrate are ensured, and excellent battery performance is exhibited.

(A)-(d) is each sectional drawing which shows the embodiment of the solid oxide fuel cell of this invention. It is a scanning electron microscope image which shows the shape of the acicular nickel oxalate used for this invention. It is a scanning electron microscope image which shows the shape of the acicular nickel particle obtained by heat-processing the acicular nickel oxalate shown in FIG. 2 in inert atmosphere.

  Hereinafter, the solid oxide fuel cell of the present invention will be described more specifically together with embodiments and manufacturing methods thereof.

In the solid oxide fuel cell of the present invention, at least one material selected from the group consisting of acicular nickel oxalate, acicular nickel oxide, and fibrous nickel is filled in at least the surface side of the void. A gas permeable metal substrate is used as a support substrate, and a fuel electrode, an electrolyte, and an air electrode are laminated on the surface in this order.
Alternatively, a gas permeable metal substrate whose surface is coated with a layer made of the above material is used, and a fuel electrode, an electrolyte, and an air electrode are laminated in this order on the coating layer. At this time, there is no problem even if a part or the whole of the gap in the substrate is filled with the material.

  In the present invention, the “air gap” of the gas permeable metal substrate refers to a space functioning as a ventilation path of the gas permeable metal substrate. Specifically, the gas permeable metal substrate is a punching metal or an expanded metal. In the case of dead metal, etching metal, etc., through holes, in the case of foam metal (sponge metal, porous metal), open cells, in the case of metal mesh, the openings between the strands, and in the case of metal nonwoven fabric, the metal It means each gap between fibers.

  In the present invention, “needle” means a particle shape having an average diameter of 50 to 500 nm and a length of 10 times or more.

FIG. 1 shows an example of a solid oxide fuel cell according to the present invention, and FIG. 1 (a) is a cross-sectional view as a first embodiment.
The solid oxide fuel cell 1 shown in the figure has at least one selected from the group consisting of acicular nickel oxalate, acicular nickel oxide, and fibrous nickel on the surface side in the gap 2a of the gas permeable metal substrate 2. The material 3 (hereinafter, the materials are collectively referred to as “needle-like nickel material” for convenience) is filled, and the fuel electrode 4, the electrolyte 5, and the air electrode 6 are laminated in this order. .

The gas permeable metal substrate 2 is made of a corrosion-resistant alloy, corrosion-resistant steel, stainless steel, or the like containing Ni or Cr, and has a plate-like shape having a large number of voids 2a (holes, openings, gaps), for example, as described above. Such punching metal, etching metal, metal mesh (wire mesh), expanded metal, metal foam, metal nonwoven fabric, and the like can be used.
In addition, as long as the said acicular nickel material 3 plugs up the space | gap 2a of the said board | substrate 2, and the board | substrate surface is smoothed, as shown to Fig.1 (a), it should be filled only into the surface side of the space | gap 2a. However, there is no problem even if the entire gap 2a is filled, and it can be said that this is preferable from the viewpoint of strength and filling method.

As the fuel electrode 4, nickel alone functions, but it is desirable to use a cermet mixed with an oxygen ion conductor typified by YSZ, thereby increasing the reaction area and improving the electrode performance. At this time, it is also possible to use SDC (Samaria doped ceria) or GDC (Gadolinium doped ceria) instead of YSZ.
Moreover, as the electrolyte 5, solid oxides, such as YSZ, SDC, SSZ (scandia stabilization zirconia), LSGM (lanthanum strontium magnesium gallate), can be used, for example.

As the material of the air electrode 6, for example, _{LSCF (La 1-x Sr x} Co 1-y Fe y O 3), SSC (Sm x Sr 1-x CoO 3), LSM (La 1-x Sr x MnO 3) Perovskite materials such as are used.

At this time, in order to prevent a reaction between the air electrode 6 and the electrolyte 5, an intermediate layer can be provided between them as necessary.
For example, when YSZ is used as the electrolyte and LSCF is used as the air electrode, La and Zr react to form an insulating layer. For this reason, doped ceria systems such as SDC, YDC (yttria doped ceria), and GDC are used. It is desirable to form an intermediate layer made of these materials.

  For the fuel electrode 4, electrolyte 5, air electrode 6, and intermediate layer described above, a wet method such as screen printing using a paste containing a binder and a dispersant is used together with the respective materials, as well as a sputtering method and a gas deposition method. It can also be formed by a PVD method (physical vapor deposition) such as a position method.

FIG. 1 (b) shows a second embodiment of the solid oxide fuel cell of the present invention. The solid oxide fuel cell 1 shown in the drawing is a gas-permeable metal having a gap 2a. On the substrate 2, a coating layer made of the acicular nickel material 3 is formed so as to cover the entire surface of the substrate 2. Then, the fuel electrode 4, the electrolyte 5, and the air electrode 6 are similarly laminated on the substrate 2 through the multilayer.
In this embodiment, as compared with the first embodiment, which is an intermittent surface between the metal surface of the substrate 2 and the surface made of the acicular nickel material 3, all the film formation surfaces of the fuel electrode 4 are acicular nickel material. Therefore, the battery elements including the fuel electrode 4 can be formed more uniformly.

  In the second embodiment, the needle-like nickel material 3 is not filled in the gap 2a of the gas permeable metal substrate 2, but as shown in FIG. 1 (c) or (d), the gap 2a Even if the needle-like nickel material 3 enters a part or the whole of the inside, there is no problem, and such an embodiment is not excluded.

  In the solid oxide fuel cell of the present invention, the particles constituting the acicular nickel material 3, that is, the acicular nickel oxalate, acicular nickel oxide, and fibrous nickel particles may be used alone or in a mixed state of two or more. It is desirable that the gas permeable metal substrate 2 is oriented in a direction substantially parallel to the surface. As a result, the particles are folded on each other, and the gap 2a of the metal substrate 2 can be easily sealed.

  In the solid oxide fuel cell of the present invention, as described above, the acicular nickel material 3, that is, acicular nickel oxalate, acicular nickel oxide, is formed inside the gap 2 a in the gas permeable metal substrate 2 or on the surface of the substrate. And at least one material selected from the group consisting of fibrous nickel is interposed.

Among these materials, acicular nickel oxalate (NiC ₂ O ₄ ), as will be described later, is oxidized by heating in the air at the time of the single process or electrode formation in the subsequent process, and becomes acicular nickel oxide. Moreover, it reduces by heating in an inert atmosphere or the atmosphere containing hydrogen, and turns into fibrous metallic nickel.
Also, acicular nickel oxide is reduced by the fuel gas simultaneously with the start of operation as a fuel cell, and becomes fibrous metallic nickel.

Therefore, even if acicular nickel material in the form of nickel oxalate or nickel oxide is present in the gas permeable metal substrate surface or void in the completed fuel cell, these are immediately after the start of operation of the fuel cell, Both are reduced and finally become fibrous metallic nickel.
Since such fibrous nickel has a structure in which the connection between the particles is firmly formed and the fibrous particles intersect each other, the connection between the particles is more reliable than the conventional spherical one. Thus, the electron conductivity is increased and the gas permeability is excellent.

A scanning electron microscope image of such acicular nickel oxalate is shown in FIG. Further, FIG. 3 shows a scanning electron microscope image of fibrous nickel obtained by heating the acicular nickel oxalate as it is in an inert atmosphere. According to this, it turns out that fibrous nickel particles are connected in a chain form.
The above-mentioned acicular nickel oxalate can be synthesized, for example, from commercially available sodium oxalate and nickel chloride hydrate by a method as described later.

In the method for producing a solid oxide fuel cell according to the present invention, the needle-shaped nickel material made of at least one material selected from the group consisting of needle-shaped nickel oxalate, needle-shaped nickel oxide and fibrous nickel is inserted into the gap. Various methods can be applied to the filling and covering of the substrate surface.
These methods are not particularly limited, but any of coating, deep coating, screen printing, green sheet pressure bonding, powder pressing method, or a combination of two or more of these methods can be used for filling efficiency and It is desirable from the viewpoint of workability. In addition to these, other wet coating methods such as a spin coating method and a spray method can also be applied.

In the production of the solid oxide fuel cell of the present invention, after filling the gaps of the gas-permeable metal base material with the acicular nickel material and coating the surface of the base material, 300 in the atmosphere. It can be heated to a temperature of ˜1200 ° C., whereby acicular nickel oxalate in the gap or on the surface of the substrate becomes acicular nickel oxide.
In addition, although this heating process can also be performed by the board | substrate alone, it can also be performed simultaneously with baking of a fuel electrode.

In addition, the gas-permeable metal base material that has been filled into the gaps of the acicular nickel material and the surface is covered with the acicular nickel material is heated to 300 to 1200 ° C. in an inert atmosphere or in an atmosphere containing hydrogen. It can also be heated to a temperature, whereby acicular nickel oxalate in the gap or on the surface of the substrate becomes fibrous metallic nickel.
In this case, it is desirable to form a battery element composed of a fuel electrode, an electrolyte, and an air electrode, which is a subsequent process, in an oxygen-free atmosphere, thereby oxidizing the fibrous nickel and the resulting fibrous structure. Can be prevented.

  In the method for producing a solid oxide fuel cell of the present invention, as described above, the needle-shaped nickel material is heated in each atmosphere as described above by heating the base material that has been filled and coated with the needle-shaped nickel material. After the acicular nickel oxalate contained in the material is changed to acicular nickel oxide or fibrous nickel, the battery element is basically formed on the substrate.

However, as described above, acicular nickel oxalate or acicular nickel oxide is reduced by the fuel gas simultaneously with the start of operation as a fuel cell to become fibrous nickel in a metallic state.
Therefore, even if the above heat treatment is omitted and the acicular nickel oxalate is left as it is, or even if the heat treatment is insufficient and remains in the state of acicular nickel oxalate, there is no problem. By forming a battery element on the surface of a simple substrate, the solid oxide fuel cell of the present invention can be obtained.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, it cannot be overemphasized that this invention is not limited at all by such an Example. In the present specification, “%” means mass percentage unless otherwise specified.

  Prior to the production of each solid oxide fuel cell according to Examples and Comparative Examples, acicular nickel oxalate was synthesized according to the following procedure, and acicular nickel oxalate paste, acicular nickel oxalate green sheet, acicular nickel oxalate A deep coating solution, a fuel electrode paste, and an air electrode paste were prepared.

[Synthesis of acicular nickel oxalate]
First, nickel chloride hexahydrate (NiCl ₂ .6H ₂ O) and sodium oxalate (Na ₂ C ₂ O ₄ ) were prepared, and each was dissolved in distilled water.
Next, after mixing the nickel chloride aqueous solution and aqueous ammonia (28% NH ₃ ), using the aqueous solution of hydrochloric acid (HCl) or caustic soda (NaOH), the above mixed solution and the previously obtained sodium oxalate aqueous solution are mixed. The pH was adjusted (pH = 9.5).

Then, the pH-adjusted mixed solution and the sodium oxalate aqueous solution were dropped simultaneously (temperature: 363 K, dropping rate: 1.6 dm ³ / s) in a solution in which the pH value of distilled water was adjusted to 9.5 with NaOH. Then, acicular nickel oxalate was produced and grown by stirring (ripening time: 4 hours). Thereafter, the filtered precipitate was washed with distilled water and dried at room temperature in the air for 1 day to obtain acicular nickel oxalate.
The obtained acicular nickel oxalate particles had an average diameter of about 100 nm, and the length of the acicular particles was about 50 to 100 times the diameter.

(Preparation of acicular nickel oxalate paste)
An acicular nickel oxalate paste was prepared by adding and mixing 85% acicular nickel oxalate synthesized above, 5% ethyl cellulose (binder), and 10% butyl acetate (dispersant).

[Preparation of green sheet containing acicular nickel oxalate]
Acicular nickel oxalate synthesized as described above, water-soluble acrylic binder, PEG (polyethylene glycol: pore former) and organic dispersant are mixed, and 80% acicular nickel oxalate is mixed by a tape casting method. A green sheet was prepared.

[Preparation of deep coating solution containing acicular nickel oxalate]
A needle-like nickel oxalate deep coating solution was prepared by dispersing 5 g of needle-like nickel oxalate synthesized as described above in 150 mL of dilute nitric acid (0.05 M) and further mixing PVA (polyvinyl alcohol).

[Preparation of fuel electrode paste]
A commercially available NiO powder and YSZ were blended so as to have a mass ratio of 70:30, and ethyl cellulose and butyl acetate were added thereto and mixed to prepare a fuel electrode paste that became Ni-YSZ cermet during power generation. .

(Preparation of air electrode paste)
Ethyl cellulose and butyl acetate were added to LSCF (La _0.7 Sr _0.3 Co _0.8 Fe _0.2 O ₃ ) and mixed to prepare an air electrode paste containing 85% of the LSCF.

Example 1
As a gas permeable metal substrate, by using photo-etching on a nickel plate having a plate thickness of 200 μm, a disc-shaped etching metal having a diameter of 200 μm and an infinite number of voids having a diameter of 200 μm is used, and on one surface of this substrate, The acicular nickel oxalate paste prepared as described above was applied. And after drying at 150 degreeC, it heated at 900 degreeC in air | atmosphere for 2 hours.
Next, the fuel electrode paste prepared as described above is applied onto the paste application surface of the substrate and baked in the atmosphere at 1100 ° C. for 2 hours, so that the fuel electrode containing NiO powder and YSZ has a thickness of 30 μm. Formed.

On the fuel electrode, an electrolyte composed of YSZ was deposited to a thickness of 5 μm by sputtering, and an intermediate layer composed of SDC was further deposited to a thickness of 3 μm by sputtering.
Then, the air electrode paste prepared as described above is applied onto the intermediate layer and baked at 1050 ° C. to form an air electrode made of LSCF to form a fuel cell. As a first embodiment of the present invention, A solid oxide fuel cell as shown in FIG. 1C was obtained.

Example 2
A needle-shaped nickel oxalate paste prepared as described above was used from both sides of this substrate, which was made of austenitic stainless steel SUS316, a square wire mesh with a side of 50 mm having a thickness of 150 μm and a mesh opening of 50 μm was used as a gas-permeable metal substrate. Applied. And similarly, it dried at 150 degreeC and baked at 900 degreeC for 2 hours.
Then, a fuel electrode, an electrolyte, an intermediate layer, and an air electrode are formed in this order on one surface of the substrate thus obtained by repeating the same operation as above, and the second embodiment of the present invention. As a result, a solid oxide fuel cell as shown in FIG.

Example 3
A 30 mm diameter disk-shaped expanded metal made of ferritic stainless steel SUS430, having a thickness of 150 μm and a gap size of 0.7 mm × 0.4 mm, is used as a gas permeable metal substrate. The acicular nickel oxalate paste prepared by the above was applied. Subsequently, after drying at 150 degreeC, it heated at 1000 degreeC in inert atmosphere for 2 hours.
And on one side of the substrate thus obtained, using the same material, a fuel electrode, an electrolyte, an intermediate layer and an air electrode are formed in this order, and as a third embodiment of the present invention, A solid oxide fuel cell as shown in FIG. 1 (d) was obtained. However, in this case, the formation of the battery element was performed under an inert atmosphere to prevent oxidation of the fibrous nickel filled in the voids of the base material.

Example 4
As the gas permeable metal substrate, a 30 mm diameter disk-shaped punching metal made of ferritic stainless steel SUS430 and having an infinite number of circular voids having a thickness of 200 μm and a diameter of 300 μm is used as the gas permeable metal substrate. The needle-shaped nickel oxalate sheet prepared as described above was overlaid and thermocompression bonded at 400 ° C.
Then, the fuel electrode, the electrolyte, the intermediate layer, and the air electrode are formed in this order by repeating the same operation as above, and as shown in FIG. 1B as the fourth embodiment of the present invention. A solid oxide fuel cell was obtained.

Example 5
The gas-permeable metal substrate is made of ferritic stainless steel SUS430, has a disk shape with a thickness of 300 μm and a diameter of 30 mm, and a metal nonwoven fabric having a space (void) between metal fibers of 50 μm. The needle-shaped nickel oxalate powder synthesized by the above method was uniformly coated and pressed by a press.
Then, a fuel electrode, an electrolyte, an intermediate layer, and an air electrode are formed in this order by the same operation as described above, and as a fifth embodiment of the present invention, a solid as shown in FIG. An oxide fuel cell was obtained.

Example 6
As a gas-permeable metal substrate, a ferritic stainless steel SUS430 is subjected to photoetching, and a plate-like etching metal having a plate thickness of 100 μm and a diameter of 30 mm having an infinite number of voids having a diameter of 100 μm is used. After dipping in the needle-like nickel oxalate deep coating solution prepared by the above, the coating solution was impregnated into the voids of the substrate by repeating the operation of slowly lifting 10 times. And after drying at 150 degreeC, it heated at 1000 degreeC for 2 hours in the atmosphere containing 15% (volume ratio) of hydrogen.
And on one surface of the substrate thus obtained, using the same material, a fuel electrode, an electrolyte, an intermediate layer and an air electrode are formed in this order, and as a sixth embodiment of the present invention, A solid oxide fuel cell as shown in FIG. 1A (however, fibrous nickel was filled in the entire area of the voids of the substrate) was obtained. In this example, the battery element was formed in an inert atmosphere until the fuel electrode was manufactured. The electrolyte was formed by sputtering, and the air electrode was formed by a gas deposition method.

Comparison of Gas Permeability The nickel disk-shaped etching metal used in Example 1 was used as a gas permeable metal substrate, and the acicular nickel oxalate paste prepared above was applied to both sides of the substrate, and 150 After drying at 0 ° C., it was heated to 1300 ° C. in the atmosphere.
Then, the gas permeability of the substrate thus obtained was investigated by a He leak test, and a similar substrate was coated with a nickel oxide paste replaced with a commercially available nickel oxide in the form of acicular nickel oxalate, Similarly, comparison was made with a comparative substrate obtained by drying and heating.

  As a result, it was found that the leak rate of He was increased by 20% in the porosity of the base material using acicular nickel oxalate compared to the base material using granular nickel oxide, and excellent in gas permeability. It was confirmed that

DESCRIPTION OF SYMBOLS 1 Solid oxide fuel cell 2 Gas-permeable metal base material 2a Air gap 3 Acicular nickel material (at least 1 type of acicular nickel oxalate, acicular nickel oxide, fibrous nickel)
4 Fuel electrode 5 Electrolyte 6 Air electrode

Claims (6)

  On the surface of the gas permeable metal substrate having voids and filled with at least one material selected from the group consisting of acicular nickel oxalate, acicular nickel oxide and fibrous nickel at least on the surface side in the voids A solid oxide fuel cell, wherein a fuel electrode, an electrolyte, and an air electrode are laminated in this order.   At least one material selected from the group consisting of acicular nickel oxalate, acicular nickel oxide, and fibrous nickel is filled in the surface of the gas permeable metal substrate having voids or in the voids of the gas permeable metal substrate. A solid oxide fuel cell, wherein a fuel electrode, an electrolyte, and an air electrode are laminated in this order on the surface of a gas-permeable metal substrate with a coating layer made of the above-described material interposed therebetween.   3. The solid oxide fuel cell according to claim 1, wherein the material is oriented in a direction substantially parallel to the surface of the metal substrate. In producing the solid oxide fuel cell according to any one of claims 1 to 3,
Filling at least one of the above-mentioned materials into the voids and / or forming a multi-layer by at least one method selected from the group consisting of coating, deep coating, screen printing, green sheet pressure bonding and powder pressing. A method for producing a solid oxide fuel cell.   In producing the solid oxide fuel cell according to any one of claims 1 to 3, after filling the material into the voids and / or forming a multi-layer, 300 to 1200 in the atmosphere. A method for producing a solid oxide fuel cell, characterized by heating to a temperature of ° C.   In producing the solid oxide fuel cell according to any one of claims 1 to 3, after filling the voids in the material and / or forming a multi-layer, an inert atmosphere or hydrogen is added. A method for producing a solid oxide fuel cell, comprising heating to a temperature of 300 to 1200 ° C. in an atmosphere containing the solid oxide fuel cell.

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