JP4027836B2 - Method for producing solid oxide fuel cell - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a supported membrane solid oxide fuel cell.
[0002]
[Prior art]
A solid oxide fuel cell (SOFC (= Solid Oxide Fuel Cell): hereinafter abbreviated as SOFC as appropriate) has an operating temperature as high as about 800 to 1000 ° C., usually about 1000 ° C. An SOFC single cell, ie, a single cell, has a fuel electrode and an air electrode (an oxygen electrode when oxygen is used as an oxidant) sandwiching an electrolyte (solid oxide electrolyte), and has three layers: fuel electrode / electrolyte / air electrode. Consists of units. FIG. 1 is a diagram showing the SOFC in principle.
[0003]
Oxygen in the air introduced into the air electrode becomes oxide ions (O ²⁻ ) at the air electrode, and reaches the fuel electrode through the electrolyte. Here, the fuel introduced into the fuel electrode (hydrogen, carbon monoxide. Note that methane is steam reformed by the catalytic action of a metal that is a component of the fuel electrode, such as nickel, to form hydrogen and carbon monoxide and used as fuel. To emit electrons and produce reaction products such as electricity, water, and carbon dioxide. Used air at the air electrode is discharged as an air electrode off gas, and used fuel at the fuel electrode is discharged as a fuel electrode off gas. Since the voltage of one single cell (single cell) is low, the SOFC is usually configured by stacking a plurality of single cells in series.
[0004]
As the electrolyte material, for example, a sheet-like sintered body such as yttria stabilized zirconia (YSZ) is used, and as the fuel electrode, for example, a sintered body of a mixture of nickel and yttria stabilized zirconia (Ni / YSZ cermet) or the like. A porous body is used, and as the air electrode, for example, a porous body such as Sr-doped LaMnO ₃ is used. These usually constitute a unit cell by baking a fuel electrode and an air electrode on both surfaces of an electrolyte material.
[0005]
The SOFC includes a flat plate method, a cylindrical method, and an integral lamination method, and these are the same in principle. A flat-plate type SOFC generally retains its structure with the electrolyte membrane itself, and is called a self-supporting membrane type. The thickness of the electrolyte membrane is usually as thick as about 100 μm. At the same time as the adjacent unit cells are electrically connected, separators and unit cells are alternately stacked for the purpose of appropriately distributing, supplying, and discharging fuel and air to the fuel electrode and the air electrode, respectively.
[0006]
By the way, in such a SOFC, the fuel, air, fuel electrode off-gas, and air electrode off-gas that are distributed are all gases, and the operating temperature is as high as about 1000 ° C. If it is insufficient, gas leaks and becomes fatal as a battery.
[0007]
A conventional SOFC has a high operating temperature of about 800 to 1000 ° C., but recently, an SOFC operating at a temperature of about 800 ° C. or lower, for example, about 750 ° C. is being developed. 2 to 4 are diagrams for explaining an example of the SOFC mode. 2A and 2B are configuration examples of the unit cell, FIG. 2A is a side view, and FIG. 2B is a perspective view. FIG. 3 is a configuration example of a SOFC stack incorporating a single battery, and FIG. 4 is a cross-sectional view taken along line XX in FIG. As shown in FIG. 2, the unit cell is configured by disposing an electrolyte membrane on the fuel electrode and an air electrode on the electrolyte membrane. The unit cell is assembled as shown in FIGS. Is configured.
[0008]
The electrolyte membrane is made of, for example, a zirconia-based material such as yttria-stabilized zirconia or LaGaO ₃ -based material, and the thickness thereof is reduced to about 10 μm, for example, and this is supported by a thick fuel electrode. It is common to do this and is called a support membrane type. The support membrane type can be operated at a lower temperature than the self-supporting membrane type because the thickness of the electrolyte membrane can be reduced. For this reason, it has various advantages such as enabling the use of an inexpensive material such as ferritic stainless steel as a constituent material of the separator and the like, and miniaturization.
[0009]
As shown in FIGS. 3 to 4, in the support membrane type SOFC stack, the separator A, the separator B, the separator C, the bonding material, the single cell, and the separator D are sequentially arranged from the upper part to the lower part. A current collector plate or the like is disposed above the separator A and below the separator D. FIG. 4 shows a part thereof, but it is omitted in FIG. Moreover, metals (including alloys) are used as the constituent materials of the separators A to D, and examples thereof include stainless steel.
[0010]
[Problems to be solved by the invention]
By the way, even in the low temperature operation SOFC as described above, the circulating fuel, air, fuel electrode off-gas, and air electrode off-gas are all gases, and the operating temperature is about 650 to 800 ° C., which is still high. If the sealing between the separator and the battery is insufficient, gas leakage occurs and the battery becomes fatal. In addition, since the SOFC is repeatedly used, the SOFC cannot be put into practical use as a SOFC unless the problem of sealing is solved for the low-temperature operation SOFC.
[0011]
Among these seals, in particular, the seal between the cell and the separator (the separator corresponding to the separator C in FIGS. 3 to 4 and also referred to as a cell support foil, hereinafter referred to as a cell support foil) is between the electrolyte membrane and the cell support foil. It is necessary to incorporate it in an alloy manifold that performs gas flow through a cell support foil. That is, it joins and seals by joining between the peripheral upper surface of an electrolyte membrane, and a cell support foil with a glass-type sealing material. FIG. 5 is a diagram showing an example of a conventional manufacturing process.
[0012]
As shown in FIG. 5, (1) an electrolyte membrane is placed on the fuel electrode and fired to produce a fuel electrode-electrolyte membrane co-sintered body. (2) Screen printing is performed on the electrolyte membrane using a slurry containing an air electrode component. (3) Bake the air electrode (up to 1200 ° C in air). (4) A metal cell support foil is pasted with a glass bonding material interposed. (5) Join by heat treatment [900 to 1000 ° C. in an electric furnace (atmosphere)]. Among these, heat treatment is required in the steps (1), (3) and (5), but the heating temperature is lowered in the order of the steps.
[0013]
The glass-based sealing material is brittle at a temperature below the softening point, and when the temperature is lowered from the battery operating temperature, cracking or peeling is particularly likely to occur at the joint between the single cell and the cell support foil. Since the bonded body once cracked or peeled loses gas tightness at that portion, even if the temperature is raised again, equivalent performance cannot be obtained. Therefore, SOFCs with glass seals do not have sufficient thermal cycle characteristics, which is a major obstacle to putting SOFCs into practical use.
[0014]
The present inventors have paid attention to a metal brazing material as a bonding material instead of a glass bonding material, and have obtained some results for bonding between a cell and a cell support foil using the metal brazing material. Bonding with a metal brazing material has the advantage that high bonding strength can be obtained and thermal cycle characteristics can be improved. However, on the other hand, it has been found that the conventional manufacturing process needs to be reexamined, for example, in order to obtain a strong joint, the joining with the metal brazing material requires a process such as preliminary reduction of the fuel electrode.
[0015]
The present invention improves the conventional manufacturing process when applying the joining with a metal brazing material to a part of the manufacturing process of the support membrane type SOFC, and it is airtight even if it is used repeatedly such as start-up → run-down → start-up. It is an object of the present invention to provide a method for producing a support membrane type SOFC having sufficient thermal cycle characteristics and capable of operating stably over a long period of time without losing properties.
[0016]
[Means for Solving the Problems]
The present invention provides a support membrane solid oxide in which a single cell is formed by sequentially laminating an electrolyte membrane and an air electrode on a fuel electrode made of a ceramic material containing a metal, and a cell support foil is disposed in the single cell. A fuel cell manufacturing method comprising: (1) a fuel electrode-electrolyte membrane co-sintered body manufacturing process; (2) a brazing process of a single cell and a cell support foil using a metal brazing material; (3 And (4) a cell support foil and manifold joining step in this order, and a support membrane solid oxide fuel cell manufacturing method.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a support membrane type solid oxidation in which a single cell is formed by sequentially laminating an electrolyte membrane and an air electrode on a fuel electrode made of a ceramic material containing metal, and a cell support foil is arranged in the single cell. This is a method of manufacturing a physical fuel cell. Then, the production is performed by (1) a production process of a fuel electrode-electrolyte membrane co-sintered body, (2) a brazing process of a single cell and a cell support foil with a metal brazing material, and (3) an air electrode on the electrolyte. A baking process and (4) a cell support foil and manifold joining process are performed in this order.
[0018]
According to the present invention, the cell part is sufficiently joined with the metal brazing material through the above-described steps, and sufficient heat cycle characteristics are obtained without losing hermeticity even when used repeatedly such as start-up-operation-stop-start-up. A supported membrane solid oxide fuel cell having the following structure can be produced. 6-8 is a figure explaining the preparation methods of the support membrane type solid oxide fuel cell of this invention. Hereinafter, it demonstrates in order of a process. Each step (1) to (8) corresponds to (1) to (8) in FIG.
[0019]
<(1) Manufacturing process of fuel electrode-electrolyte membrane co-sintered body>
An electrolyte is placed on the fuel electrode by screen printing using an electrolyte slurry and fired to produce a fuel electrode-electrolyte membrane co-sintered body, that is, a fuel electrode-electrolyte film co-sintered body. Here, before the sintering in the production process of the fuel electrode-electrolyte membrane co-sintered body, the electrolyte membrane may be formed on the upper surface of the fuel electrode so that the peripheral upper surface of the fuel electrode is exposed. The method of forming the exposed surface is not particularly limited, but for example, it can be formed as follows (1) to (3).
[0020]
(1) From the electrolyte membrane formed on the entire surface of the fuel electrode, the electrolyte membrane on the peripheral upper surface is removed. When the formation of the electrolyte membrane on the fuel electrode is performed by, for example, dipping treatment (that is, immersion treatment of the fuel electrode with electrolyte slurry or wash coating), the electrolyte membrane is formed on the entire surface of the fuel electrode. Further, an electrolyte membrane may be screen-printed on the entire upper surface of the fuel electrode. Of the electrolyte membrane thus formed, the peripheral upper surface is removed by polishing or the like. (2) The peripheral upper surface is masked during the dipping process of the fuel electrode by the electrolyte. (3) During screen printing of the electrolyte membrane on the upper surface of the fuel electrode, printing is performed while leaving the peripheral upper surface of the entire upper surface of the fuel electrode. 6 to 7 show the exposed state of the peripheral upper surface of the fuel electrode formed in this way. 6 is a perspective view, and FIG. 7 is a cross-sectional view.
[0021]
As a constituent material of the fuel electrode in the present invention, a ceramic material containing a metal is used. Among these, as the ceramic material, for example, yttria stabilized zirconia [YSZ: (Y ₂ O ₃ ) _X (ZrO ₂ ) _1-X (where x = 0.05 to 0.15) is used, At least one metal selected from Ni, Cu, Fe, Ru and Pd is used. A preferable example of the material constituting the fuel electrode is a mixture of nickel and yttria-stabilized zirconia. As a constituent material of the electrolyte membrane, for example, a zirconia-based material such as yttria-stabilized zirconia, a LaGaO ₃ -based material, or the like is used.
[0022]
<▲ 2> Fuel electrode reduction process>
Reduce the anode. This reduction treatment is effective in improving the joining effect by the subsequent metal brazing material. Although the fuel electrode and the cell support foil are joined without going through a reduction process, the fuel electrode and the cell support foil can be joined more firmly by reducing the fuel electrode. The reduction treatment is performed in an electric furnace or the like in a reducing atmosphere at 800 to 1200 ° C. for 1 to 10 hours. The reducing atmosphere may be any atmosphere that can reduce the surface of the fuel electrode in the fuel electrode-electrolyte membrane co-sintered body, and preferably a hydrogen-nitrogen (nitrogen gas containing hydrogen) atmosphere, hydrogen-argon (hydrogen). Containing argon gas) atmosphere. As a constituent material of the cell support foil, for example, a heat resistant alloy such as stainless steel is used.
[0023]
<▲ 3> Placement process of metal brazing material at the joint of fuel electrode with cell support foil>
A metal brazing material is disposed at the joint of the fuel electrode reduced by the reduction treatment of the fuel electrode with the cell support foil. In this case, as shown in FIGS. 6 to 7, in the aspect in which the peripheral upper surface of the fuel electrode is exposed, the metal brazing material may be disposed on the peripheral upper surface of the fuel electrode or on the side peripheral surface of the fuel electrode. Alternatively, they may be disposed on the peripheral upper surface of the fuel electrode and the side peripheral surface of the fuel electrode. FIG. 8 shows a case where the fuel electrode is disposed on the peripheral upper surface of the fuel electrode and the side peripheral surface of the fuel electrode. Further, in a mode in which the peripheral upper surface of the fuel electrode is not exposed and the electrolyte membrane covers the entire upper surface of the fuel electrode, the metal brazing material is disposed between the side peripheral surface of the fuel electrode and the lower surface of the cell support foil.
[0024]
The usage form of the metal brazing material is not particularly limited, and can be used in the form of powder, slurry, sol, paste, sheet, wire or the like. The slurry, sol, or paste is produced, for example, by dispersing metal brazing powder in a solvent such as water or an organic solvent together with a binder such as PVA. A sheet | seat and a wire are produced by rolling the lump of metal brazing, for example. If the metal brazing is used in the form of a slurry, a sol or a paste, it is advantageous for the operation. In FIG. 8, (3) shows the case of using in the form of sol or paste.
[0025]
Any metal brazing material can be used as long as it contains at least one metal among Ag, Cu, Ti, Ni, Au, Al, and Pd. However, the metal brazing material contains Ag or Ni. Is preferred. Examples thereof include an Ag—Cu alloy (eg, Ag 71.0 to 73.0%, remaining Cu: 780 to 900 ° C.) (% is wt%, temperature is brazing temperature, the same shall apply hereinafter), Ag—Cu—. Zn-based alloys (for example, Ag 44.0 to 46.0%, Cu 29.0 to 31.0%, Zn 23.0 to 27.0%: 745 to 845 ° C.), Ag—Cu—Zn—Cd based alloys (for example, Ag 34) 0.0 to 36.0%, Cu 25.0 to 27.0%, Zn 19.0 to 23.0%, Cd 17.0 to 19.0%: 700 to 845 ° C), Ag-Cu-Zn-Sn alloy (For example, Ag 33.0 to 35.0%, Cu 35.0 to 37.0%, Zn 25.0 to 29.0%, Sn 2.5 to 3.5%: 730 to 820 ° C), Ag-Cu-Zn- Ni-based alloys (for example, Ag 39.0 to 41.0%, Cu 29.0 to 31 0%, Zn26.0~30.0%, Ni1.5~2.5%: 780~900 ℃), and the like.
[0026]
<(4) Brazing process>
As described above, after placing the metal brazing material on the peripheral upper surface of the fuel electrode, the side peripheral surface of the fuel electrode, or on the peripheral upper surface of the fuel electrode and the side peripheral surface of the fuel electrode, the cell support foil is placed on the metal brazing material. Braze. This treatment is performed in an electric furnace or the like in a vacuum or an inert atmosphere at a brazing temperature peculiar to a metal brazing material [for example, the metal brazing material is Ag 71.0 to 73.0 wt% and the remainder is Cu (JIS: BAg-8). In some cases, the brazing temperature is 780-900 ° C.] 5-10 minutes. The inert atmosphere may be an atmosphere that does not become an oxidizing atmosphere, and an argon atmosphere is preferably used.
[0027]
<(5) Air electrode printing process on electrolyte>
As described above, a metal brazing material is disposed on the peripheral upper surface of the fuel electrode and brazed, and then the air electrode is printed on the electrolyte membrane. Printing can be performed by an appropriate method such as screen printing using a slurry of an air electrode material. As a constituent material of the air electrode, for example, a porous body such as Sr, Fe-doped LaCoO ₃ , Sr-doped LaMnO ₃ is used.
[0028]
<(6) Air electrode baking process>
As described above, after the air electrode is printed on the electrolyte membrane, the air electrode is baked. This treatment is carried out in an air atmosphere at 800 to 900 ° C. for 2 to 10 hours with an electric furnace or the like. As described above, in the conventional method, the air electrode is first baked on the electrolyte membrane at a maximum temperature of 1200 ° C., and then the fuel electrode and the cell support foil are joined at 900 to 1000 ° C. On the other hand, according to the present invention, as a result of experiments and studies, it has been found that even if the air electrode baking temperature is lowered, the cell performance is not affected.
[0029]
In the present invention, based on this knowledge, the baking process of the air electrode on the electrolyte membrane is performed at a low temperature of 800 to 900 ° C. after the bonding process of the fuel electrode and the cell support foil. This point is one of the features of the present invention, and can be made the same as the bonding temperature in the next heating step (8) the bonding step with the glass bonding material, which is very advantageous for cell production. .
[0030]
<7> Glass bonding material sticking process to cell support foil>
The lower peripheral edge of the cell support foil portion of the structure in which the cell support foil is joined to the cell via the metal brazing material, with the glass joining material interposed, is arranged as described above. 3-4 corresponds to the separator D). This process is the same as the conventional method.
[0031]
<(8) Bonding process with glass bonding material>
The cell support foil is bonded to the manifold with the glass bonding material adhered. This treatment is performed at about 750 to 900 ° C. for 1 to 2 hours in an air atmosphere. According to the present invention, even if this temperature is higher than the brazing temperature in the above-mentioned (4) brazing step, the surface is somewhat oxidized, and the brazing part may not be melted or peeled off. I understood.
[0032]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, of course, this invention is not limited to these Examples.
[0033]
ZrO ₂ doped with Y ₂ O ₃ was used as a solid oxide electrolyte material, and a sintered body of a mixture of nickel and yttria stabilized zirconia (= Ni / YSZ cermet. Weight ratio of Ni and YSZ = 6: 4. Porosity = 60%), and LaCoO ₃ [(La, Sr) (Co, Fe) O ₃ )] doped with Sr and Fe was used as the air electrode. First, the electrolyte was screen-printed on the entire surface of the fuel electrode using the aqueous slurry, and then fired. Next, the electrolyte membrane on the peripheral upper surface of the upper surface of the fuel electrode was ground and polished by a polishing machine to expose the fuel electrode.
[0034]
Thereafter, the fuel electrode was reduced. The reduction treatment was performed in an electric furnace in a hydrogen-nitrogen (H ₂ = 4 vol%) atmosphere at 1000 ° C. for 5 hours. Next, a paste of silver brazing (composition: Ag 72 wt% -Cu 28 wt%, melting point: 780 ° C.) was applied to the exposed portion of the fuel electrode, and a cell support foil (manufactured by SUS430) was overlaid thereon. In this state, it was placed in a vacuum atmosphere furnace, a weight was placed so that a load was applied to the joint, and the inside of the furnace was depressurized to a degree of vacuum of 10 ⁻² to 10 ⁻³ Pa. The temperature in the furnace was increased to 850 ° C., brazed for 5 minutes, and then cooled.
[0035]
In this way, a plurality of assemblies of the half battery and the cell support foil were produced, and the air electrode [(La, Sr) (Co, Fe) O ₃ )] was baked on the electrolyte membrane surface. Baking was performed in an electric furnace in an air atmosphere at 900 ° C. for 2 hours. Next, a manifold (manufactured by SUS430) was attached to the cell support foil via a glass bonding material, followed by heat treatment at 900 ° C. for 2 hours in an electric furnace to produce a battery.
[0036]
<Power generation test>
A power generation test was performed using the battery. The battery temperature is 750 ° C., hydrogen is used as the fuel, air is used as the oxidant, the open circuit voltage (OCV: abbreviated as V ₀ ), and the voltage at the current density of 0.2 A / cm ² (abbreviated as V _0.2 ). It was measured. After the temperature was lowered to room temperature at a rate of 200 ° C./h, a thermal cycle was repeated to raise the temperature to 750 ° C. at the same rate, and V ₀ and V _0.2 after each temperature rise were measured. As a result, the initial characteristics of V ₀ and V _0.2 were 1.12 V and 0.91 V, respectively, and 1.11 V, 0.87 V after one thermal cycle and 1.08 V, 0.78 V after 5 cycles. After that, the performance became stable after that. 1.10V and 0.80V were shown after 10 thermal cycles.
[0037]
【The invention's effect】
According to the present invention, when applying a metal brazing material as a bonding material in place of a glass bonding material, the conventional manufacturing process using the glass bonding material is improved, and repeated use such as start-up-operation-stop-start-up Without losing hermeticity, a support membrane SOFC having sufficient thermal cycle characteristics and capable of operating stably over a long period can be manufactured.
[Brief description of the drawings]
FIG. 1 is a diagram showing the configuration of a solid oxide fuel cell in principle. FIG. 2 is a diagram for explaining an example of a supported membrane solid oxide fuel cell. FIG. FIG. 4 is a cross-sectional view taken along the line XX in FIG. 3. FIG. 5 is a diagram showing an example of a manufacturing process of a conventional supported membrane solid oxide fuel cell. 6 is a view (perspective view) showing the exposed state of the upper surface of the periphery of the fuel electrode.
FIG. 7 is a view (cross-sectional view) showing an exposed state of a peripheral upper surface of a fuel electrode.
FIG. 8 is a diagram showing a manufacturing process of a support membrane type solid oxide fuel cell of the present invention.

Claims (18)

A single cell in which an electrolyte membrane and an air electrode are sequentially laminated on a fuel electrode made of a ceramic material containing a metal, and a cell support foil is arranged on the single cell, is a support membrane type solid oxide fuel cell. A production method comprising the following steps: (1) production process of fuel electrode-electrolyte membrane co-sintered body, (2) brazing step of single cell and cell support foil with metal brazing material, (3) on electrolyte membrane A method for producing a support membrane type solid oxide fuel cell, which is performed in the order of a step of baking an air electrode on the substrate and (4) a step of joining a cell support foil and a manifold. 2. The support membrane type solid oxide fuel cell manufacturing method according to claim 1, wherein in the single cell, an electrolyte membrane is formed on the upper surface of the fuel electrode so that the peripheral upper surface of the fuel electrode is exposed. A method for producing a membrane solid oxide fuel cell. 3. The manufacturing method of a support membrane type solid oxide fuel cell according to claim 2, wherein an exposed membrane on the upper peripheral surface of the fuel electrode is an electrolyte membrane formed on the entire upper surface of the fuel electrode. A method for producing a support membrane type solid oxide fuel cell, characterized in that it is formed by removing the catalyst. 4. The method of manufacturing a support membrane type solid oxide fuel cell according to claim 3, wherein the removal of the electrolyte membrane on the peripheral upper surface of the fuel electrode is performed by polishing. Manufacturing method. 3. The method of manufacturing a support membrane type solid oxide fuel cell according to claim 2, wherein the exposed surface of the peripheral upper surface on the fuel electrode is formed by masking the peripheral upper surface during slurry coating of the fuel electrode with an electrolyte. A method for producing a support membrane type solid oxide fuel cell. 6. The method for producing a supported membrane solid oxide fuel cell according to claim 1, wherein the fuel electrode is reduced after the step (1) of producing the fuel electrode-electrolyte membrane co-sintered body. A method for producing a support membrane type solid oxide fuel cell. The method for producing a support membrane solid oxide fuel cell according to claim 6, wherein the reduction of the fuel electrode is performed in a reducing atmosphere at a temperature of 800 to 1200 ° C. A method for manufacturing a fuel cell. In the manufacturing method of the support membrane type solid oxide fuel cell of any one of Claims 1-7, this metal in the fuel electrode comprised with the ceramic material containing the said metal is Ni, Cu, Fe, A method for producing a supported membrane solid oxide fuel cell, characterized in that it is at least one metal selected from Ru and Pd. 8. The method for producing a supported membrane solid oxide fuel cell according to claim 1, wherein the constituent material of the fuel electrode made of the ceramic material containing the metal is Ni and yttria-stabilized zirconia. A method for producing a supported membrane solid oxide fuel cell, which is a mixture of 10. The method for producing a supported membrane solid oxide fuel cell according to claim 1, wherein the constituent material of the electrolyte membrane is yttria stabilized zirconia. A method of manufacturing a physical fuel cell. The method for producing a supported membrane solid oxide fuel cell according to any one of claims 1 to 10, wherein the constituent material of the air electrode is porous of Sr, Fe-doped LaCoO ₃ or Sr-doped LaMnO ₃ . A method for producing a support membrane type solid oxide fuel cell, characterized by comprising: The method for producing a supported membrane solid oxide fuel cell according to any one of claims 1 to 11, wherein the metal brazing is performed in the step (2) of brazing the single cell and the cell support foil with a metal brazing material. A method for producing a support membrane type solid oxide fuel cell, wherein the material is disposed between the exposed surface of the fuel electrode on the peripheral upper surface of the single cell and the lower surface of the cell support foil. The method for producing a supported membrane solid oxide fuel cell according to any one of claims 1 to 11, wherein the metal brazing is performed in the step (2) of brazing the single cell and the cell support foil with a metal brazing material. A method for producing a support membrane type solid oxide fuel cell, wherein the material is disposed between the side peripheral surface of the fuel electrode and the lower surface of the cell support foil. The method for producing a supported membrane solid oxide fuel cell according to any one of claims 1 to 11, wherein the metal brazing is performed in the step (2) of brazing the single cell and the cell support foil with a metal brazing material. The support membrane type solid oxide fuel cell is characterized in that the material is disposed between the exposed surface of the fuel electrode on the peripheral upper surface of the unit cell and the side peripheral surface of the fuel electrode and the lower surface of the cell support foil. Manufacturing method. The method for producing a supported membrane solid oxide fuel cell according to any one of claims 1 to 14, wherein the metal brazing is performed in the step (2) of brazing the single cell and the cell support foil with a metal brazing material. A method for producing a supported membrane solid oxide fuel cell, characterized in that the material is a metal brazing material containing at least one metal of Ag, Cu, Ti, Ni, Au, Al and Pd. The method for producing a supported membrane solid oxide fuel cell according to any one of claims 1 to 15, wherein the single cell and the cell support foil are brazed with a metal brazing material in the step (2). Is performed at a temperature of 780 to 900 ° C., A method for producing a supported membrane solid oxide fuel cell. The method for producing a support membrane solid oxide fuel cell according to any one of claims 1 to 16, wherein the air electrode is baked in the air in the step of baking the air electrode on the electrolyte membrane in the step (3). A method for producing a supported membrane solid oxide fuel cell, which is performed in an atmosphere at a temperature of 800 to 900 ° C. In the manufacturing method of the support membrane type solid oxide fuel cell of any one of Claims 1-17, joining in the joining process of the cell support foil and manifold of the said process (4) is carried out using a glass bonding material. A method for producing a support membrane type solid oxide fuel cell, which is performed in an air atmosphere at a temperature of 750 to 900 ° C.

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