JP5448382B2 - Method for producing power generation membrane of solid oxide fuel cell - Google Patents

Description

  The present invention relates to a power generation membrane for a solid oxide fuel cell, a solid electrolyte fuel cell including the power generation membrane, and a method for producing a power generation membrane for a solid oxide fuel cell.

As a general configuration of a solid oxide fuel cell (SOFC), the one shown in FIG. 1 is known.
The power generation membrane 10 includes a solid electrolyte 1, a fuel side electrode 2 and an air side electrode 3 formed on both surfaces thereof. An electrode connecting corrugated plate 4 and an interconnector 6 are formed on the fuel side electrode 2 side, and an electrode connecting corrugated plate 5 and an interconnector 7 are formed on the air side electrode 3 side.

As the solid electrolyte 1, it has been proposed to use yttria stabilized zirconia (YSZ). As the air side electrode 3, since excellent power density and high durability can be obtained, lanthanum strontium manganese oxide (LSM) represented by the composition formula (La _(1-x) Sr _x ) _y MnO ₃ and A composite with YSZ is used. The fuel side electrode 2 is required to have excellent electron conductivity, electrode reactivity, and stability in a hydrogen atmosphere. As a material for the fuel side electrode 2, a mixture of nickel oxide (NiO) and YSZ (NiO / YSZ cermet) is generally used.

  The operating temperature of a solid oxide fuel cell is generally about 1000 ° C., but a solid oxide fuel cell that operates at a lower temperature (for example, about 800 ° C. or less) is desired. However, the conventional solid oxide fuel cell has a problem that when the operating temperature of the solid oxide fuel cell is lowered from 1000 ° C. to 800 ° C. or less, the polarization of the fuel-side electrode increases and the power generation performance decreases. Therefore, in order to operate at a relatively low temperature of about 800 ° C., a fuel side electrode that operates sufficiently even at 800 ° C. is required.

In Patent Document 1, the ratio of YSZ, which is a material having a high oxygen ion conductivity on the solid electrolyte side, is high, and the ratio of Ni, which is a material having a high electron conductivity, on the side opposite to the solid electrolyte is high. A fuel-side electrode having a stacked configuration in which the ratio of (CeO ₂ ) _0.8 (SrO _1.5 ) _0.2 or PrO _{x to} the material is high on the solid electrolyte side and low on the opposite side of the solid electrolyte is disclosed. . By forming the fuel-side electrode having the above-described configuration, the occurrence of polarization is suppressed and the power generation capability of the solid oxide fuel cell is improved.
Japanese Patent No. 3330198

In the fuel-side electrode described in Patent Document 1, (CeO ₂ ) _0.8 (SrO _1.5 ) _0.2 or PrO _x is added to suppress polarization and achieve an improvement in power generation capacity. However, an increase in the constituent components of the fuel side electrode tends to cause variation in composition, which adversely affects power generation characteristics. For this reason, it has been a problem that management in the production process becomes complicated. In addition, there is a disadvantage that the raw material cost increases.

  The present invention has been made in view of such circumstances, and has a power generation film and a power generation film for a solid oxide fuel cell that have good electrical characteristics and suppress the occurrence of polarization of a fuel-side electrode even at a low operating temperature. A manufacturing method is provided.

  As a result of the study by the present inventors, even when the fuel side electrode is a two-component system of YSZ and NiO, the laminated structure of the mixed layer made of a mixture of YSZ and NiO and the film thickness of the mixed layer should be optimized. Thus, it has been found that the electric characteristics of the fuel side electrode are improved and the occurrence of polarization can be suppressed even at a low temperature operation of about 800 ° C.

That is, as a reference example of the present invention , a power generation film of a solid oxide fuel cell having a solid electrolyte, an air-side electrode provided on one side of the solid electrolyte, and a fuel-side electrode provided on the other side The fuel side electrode is configured by laminating a plurality of mixed layers of nickel oxide and yttria-stabilized zirconia, and the mixing ratio of nickel oxide and yttria-stabilized zirconia is determined by the plurality of mixed layers. The plurality of mixed layers are stacked such that the ratio of the yttria-stabilized zirconia contained in the mixed layer decreases from the solid electrolyte side toward the opposite side of the solid electrolyte. Provided is a power generation film for a solid oxide fuel cell, wherein the thickness of each of the mixed layers is 10 μm or more and 30 μm or less.

  In this way, a plurality of mixed layers having different mixing ratios of nickel oxide and yttria-stabilized zirconia are laminated so that the content ratio of yttria-stabilized zirconia decreases from the solid electrolyte side to the opposite side of the solid electrolyte. With this structure, the thickness of each mixed layer is set to 10 μm or more and 30 μm or less, whereby a fuel-side electrode that has good electrical characteristics and suppresses the occurrence of polarization even at low temperature operation can be obtained. If the thickness of each mixed layer is less than 10 μm, a region sufficient for electrode reaction cannot be obtained. When the thickness exceeds 30 μm, particularly in a mixed layer having a low nickel oxide ratio, the electron conductivity is lowered and the IR resistance (insulation resistance) is increased. Since the power generation membrane of the present invention has a small number of components on the fuel side electrode and is easy to manage the composition, variations in composition can be reduced. For this reason, a solid oxide fuel cell having stable power generation characteristics can be obtained.

  In the above invention, it is preferable that the fuel-side electrode is configured by laminating three or more of the mixed layers.

  The thermal expansion coefficient of nickel oxide is larger than that of yttria stabilized zirconia. The thermal expansion coefficient of the mixed layer corresponds to the mixing ratio of nickel oxide and yttria stabilized zirconia, the mixed layer having a high ratio of nickel oxide has a large thermal expansion coefficient, and the mixed layer having a high ratio of yttria stabilized zirconia Small expansion coefficient. When the mixed layers having greatly different mixing ratios of nickel oxide and yttria-stabilized zirconia are brought into contact with each other to be laminated, delamination occurs due to a difference in thermal expansion coefficient, and power generation performance is reduced. When three or more mixed layers are stacked, a stacked structure in which the difference in thermal expansion between the mixed layers in contact with each other can be reduced, so that delamination in the fuel-side electrode can be prevented. As a result, it is possible to prevent a decrease in power generation performance of the solid oxide fuel cell.

  In the above invention, the mixed layer is preferably formed from a raw material powder obtained by heat-treating a mixed powder of nickel oxide and yttria-stabilized zirconia.

  In the heat-treated raw material powder, nickel oxide and zirconia are bonded. In the mixed layer formed from such raw material powder, the fuel side electrode has a small increase in polarization resistance when operated for a long time. As a result, deterioration with time of the power generation characteristics of the solid oxide fuel cell can be reduced.

  In this case, the heat treatment is preferably a heat treatment at a temperature of 1300 ° C. or higher and lower than 1500 ° C. for 1 hour or longer and 10 hours or shorter.

When the temperature of the heat treatment is lower than 1300 ° C., nickel oxide and zirconia are not bonded to each other, so that the effect of the heat treatment cannot be obtained. On the other hand, when heat treatment is performed at 1500 ° C. or higher, the nickel oxide aggregates and forms a lump due to the initial sintering and is difficult to pulverize. In addition, when the fuel side electrode is formed using the raw material powder obtained by pulverizing the lump, the power generation characteristics of the solid oxide fuel cell are greatly deteriorated.
When the heat treatment time is less than 1 hour, the bond between nickel oxide and zirconia is insufficient, and the effect of the heat treatment cannot be obtained. When the heat treatment time exceeds 10 hours, the grain growth becomes remarkable and power generation characteristics are deteriorated. In particular, when heat treatment is performed at a high temperature even within the above heat treatment temperature range, the nickel oxide agglomerates and becomes difficult to grind, and the power generation characteristics of the fuel cell are greatly reduced.

  The solid oxide fuel cell provided with the above power generation membrane has good electric characteristics of the fuel side electrode, and the occurrence of polarization resistance is suppressed, so that the fuel cell exhibits high power generation capability.

  The present invention is a method for producing a power generation membrane of a solid oxide fuel cell comprising a step of providing an air side electrode on one surface of a solid electrolyte and a step of providing a fuel side electrode on the other surface of the solid electrolyte. The step of providing the fuel side electrode includes a step of producing a plurality of raw material powders having different mixing ratios of the nickel oxide powder and the yttria stabilized zirconia powder, and a raw material powder having a high proportion of the yttria stabilized zirconia powder. Applying the plurality of raw material powders on the surface of the solid electrolyte in the order of the raw material powder having a low proportion of yttria-stabilized zirconia powder, and forming a plurality of mixed layers of nickel oxide and yttria-stabilized zirconia; A step of sintering the plurality of mixed layers, wherein the original thickness is 10 μm or more and 30 μm or less. A method for producing a power generation membrane for a solid oxide fuel cell, characterized in that a coating powder is applied onto the surface of the solid electrolyte.

  Producing a plurality of raw material powders with different mixing ratios of nickel oxide powder and yttria stabilized zirconia powder, from raw material powder with a high ratio of yttria stabilized zirconia powder, to a raw material powder with a low ratio of yttria stabilized zirconia powder, The raw material powder is applied onto the solid electrolyte. By this step, a plurality of mixed layers made of a mixture of nickel oxide and yttria stabilized zirconia are formed on the solid electrolyte so that the proportion of yttria stabilized zirconia in the mixed layer decreases from the solid electrolyte side to the opposite side of the solid electrolyte. Formed to be. Next, the mixed layer is sintered to provide a fuel side electrode on the surface of the solid electrolyte. In the above step, the raw material powder is applied on the solid electrolyte so that the thickness of each mixed layer after sintering is 10 μm or more and 30 μm or less. According to the manufacturing method of the present invention, since a mixed layer having a predetermined thickness can be stacked and variation in composition can be suppressed, a power generation film having a fuel-side electrode with good electrical characteristics and low polarization can be obtained. Can do.

  In the above invention, it is preferable to stack three or more of the mixed layers. Thereby, delamination in the fuel side electrode can be prevented. As a result, a solid oxide fuel cell exhibiting high power generation performance can be obtained.

In the above invention, the raw material powder is produced by heat-treating a mixed powder obtained by mixing the nickel oxide powder and the yttria-stabilized zirconia powder , bonding nickel oxide and zirconia, and pulverizing the heat-treated mixed powder. It is preferred that In this case, the heat treatment is preferably performed at a temperature of 1300 ° C. or higher and lower than 1500 ° C. for a processing time of 1 hour or longer and 10 hours or shorter.

  The mixed powder of nickel oxide powder and yttria zirconia powder is heat-treated under the above conditions, whereby nickel oxide and zirconia are bonded. By forming the fuel side electrode using the raw material powder in which nickel oxide and zirconia are combined by heat treatment, an increase in polarization resistance at the fuel side electrode when operated for a long time can be suppressed. As a result, a solid oxide fuel cell with little deterioration over time can be obtained.

  The power generation membrane of the solid oxide fuel cell of the present invention has a mixed layer of nickel oxide and yttria stabilized zirconia so that the content ratio of yttria stabilized zirconia decreases from the solid electrolyte side to the opposite side of the solid electrolyte. A fuel-side electrode having a structure in which a plurality of layers are stacked and the thickness of one mixed layer is 10 μm or more and 30 μm or less is provided. Such a fuel-side electrode has good electrical characteristics and can suppress the occurrence of polarization even at low temperature operation of about 800 ° C. Therefore, a solid oxide fuel cell exhibiting high power generation characteristics can be obtained.

  In addition, the mixed layer constituting the fuel-side electrode is formed using a raw material powder obtained by heat-treating a mixed powder of nickel oxide powder and yttria-stabilized zirconia powder, thereby reducing the polarization resistance when operated for a long time. Increase can be suppressed. For this reason, a solid oxide fuel cell with little deterioration over time can be obtained.

Hereinafter, embodiments of the present invention will be described.
FIG. 2 is a cross-sectional view of the power generation membrane of the solid oxide fuel cell according to this embodiment. In the power generation membrane 10 of FIG. 2, a fuel-side electrode 2 is formed on one surface of a flat solid electrolyte 1 made of yttria-stabilized zirconia (YSZ). On the other surface of the solid electrolyte 1, an air-side electrode 3 made of a composite of lanthanum strontium manganese oxide (La _(1-x) Sr _x ) _y MnO ₃ (LSM) and YSZ is formed.

The fuel-side electrode 2 has a five-layer structure in which the first to fifth layers 2a, 2b, 2c, 2d, and 2e are laminated in order from the solid electrolyte 1 side. The first to fifth layers are a mixture of nickel oxide (NiO) and YSZ. The mixing ratios of NiO and YSZ in the first layer to the fifth layer are different from each other, and are within the range of compositions A to E having the mass ratio described below.
First layer A: NiO: YSZ = 0: 100 to 20:80 (however, 0: 100 is not included)
Second layer B ... NiO: YSZ = 20: 80 to 40:60
Third layer C: NiO: YSZ = 40: 60 to 60:40
Fourth layer D ... NiO: YSZ = 60: 40 to 80:20
5th layer E ... NiO: YSZ = 80: 20 to 100: 0 (however, 100: 0 is not included)
That is, the ratio of YSZ gradually decreases from the first layer 2a on the solid electrolyte 1 side toward the fifth layer 2e, and the ratio of NiO increases. By increasing the proportion of YSZ that contributes to the electrode reaction in the first layer 2a that is in the vicinity of the interface between the solid electrolyte and the fuel-side electrode, and increasing the proportion of NiO that is excellent in electronic conductivity at a portion away from the interface, electrical characteristics are obtained. And the occurrence of polarization in a low temperature operation of about 800 ° C. is suppressed.

The thermal expansion coefficient of NiO is about 14 × 10 ⁻⁶ / K to 15 × 10 ⁻⁶ / K, and the thermal expansion coefficient of YSZ is 10.2 × 10 ⁻⁶ / K. The thermal expansion coefficient when NiO and YSZ are mixed corresponds to the mixing ratio. That is, when the proportion of NiO is large, the thermal expansion coefficient is large, and when the proportion of YSZ is large, the thermal expansion coefficient is small. In this embodiment, since the fuel side electrode has a five-layer structure, the difference in thermal expansion between the mixed layers in contact with each other can be reduced, so that delamination in the fuel side electrode can be prevented. If the fuel side electrode has a configuration in which three or more mixed layers are laminated, it is sufficient to prevent delamination.

  In addition, since the fuel side electrode of the present embodiment has a high YSZ ratio in the first layer 2a and can reduce the difference in thermal expansion coefficient from the solid electrolyte 1 made of YSZ, the fuel side electrode can be prevented from peeling off from the solid electrolyte. I can do it.

  The film thicknesses of the first to fifth layers 2a, 2b, 2c, 2d, and 2e are 10 μm or more and 30 μm or less, respectively. If the thickness of each layer is less than 10 μm, a region sufficient for electrode reaction cannot be obtained. When the thickness exceeds 30 μm, the first to third layers having a small NiO ratio have a low electron conductivity and an IR resistance (insulation resistance) increases.

  The power generation membrane of the present embodiment has good electrical characteristics of the fuel side electrode, and the occurrence of polarization is suppressed. Therefore, when the power generation membrane of the present embodiment is used as a solid oxide fuel cell, high power generation characteristics are obtained. Can be obtained.

Below, the process of forming the fuel side electrode in the power generation film of this embodiment will be described.
NiO powder and YSZ powder are weighed and mixed so as to have the composition ratio of A to E described above to produce a raw material powder. When mixed using a ball mill or roll mill, the NiO powder and the YSZ powder can be mixed uniformly.

  In the present embodiment, even if NiO powder and YSZ powder are weighed and mixed so as to have a composition ratio of A to E, heat treatment is performed, and a powder pulverized again using a ball mill or roll mill is used as a raw material powder. Good. In this case, the heat treatment is performed at a temperature of 1300 ° C. or higher and lower than 1500 ° C. for 1 hour or longer and 10 hours or shorter. Producing a fuel-side electrode from heat-treated raw material powder can suppress an increase in polarization resistance when operated for a long time. For this reason, deterioration with time of the power generation characteristics of the solid oxide fuel cell can be suppressed.

As the first layer 2 a of the fuel side electrode 2, a raw material powder of composition A is applied on the solid electrolyte 1. For example, a screen printing method is applied as the coating method.
The paste in which the vehicle is added to the raw material powder is uniformly transferred and applied onto the solid electrolyte with a screen having holes. Examples of the vehicle include butyl carbitol, turpentine oil, butanol and the like, and preferably butyl carbitol. The film thickness at the time of application is adjusted according to the thickness of the screen so that the film thickness after sintering in the post-process becomes 10 μm or more and 30 μm or less. After drying the first layer 2a, the raw material powder of the composition B is applied as the second layer 2b in the same manner as the first layer coating method. The above process is repeated for the third to fifth layers 2c, 2d, and 2e, and the raw material powders having the compositions C to E are sequentially applied. When the raw material powder is applied by the screen printing method, the adhesion between the solid electrolyte and the fuel side electrode is improved.

  After the first to fifth layers 2a, 2b, 2c, 2d, and 2e are formed on the solid electrolyte 1, the fuel side electrode 2 is formed by sintering.

  Although the case where the fuel side electrode has a five-layer structure has been described in the above embodiment, the present invention is not limited to this. For example, a two-layer structure or a three-layer structure can provide a fuel-side electrode having good electrical characteristics and suppressed polarization. In order to improve the power generation characteristics of the solid oxide fuel cell more effectively, it is preferable to have a structure in which three or more fuel side electrodes are laminated.

( Reference Example 1)
An 8 mol% YSZ flat plate (diameter 30 mm, thickness 200 μm) was prepared as the solid electrolyte. An LSM / YSZ composite in which La _0.8 Sr _0.2 MnO ₃ powder and 8 mol% YSZ powder were mixed at a ratio of 70:30 was applied to one surface of the solid electrolyte with a size of 10 mmφ and a thickness of 100 μm. Sintering was performed at 1300 ° C. for 4 hours to form an air side electrode.

As raw material powder, NiO powder and 8 mol% YSZ powder were weighed so as to have the following compositions A to E (mass ratio) and uniformly mixed by a ball mill. Butyl carbitol was added to the mixed powder to prepare a paste.
A ... NiO: YSZ = 10: 90
B ... NiO: YSZ = 30: 70
C ... NiO: YSZ = 50: 50
D ... NiO: YSZ = 70: 30
E ... NiO: YSZ = 90: 10

  A first layer to a fifth layer were formed on the surface opposite to the surface on which the air-side electrode of the solid electrolyte was formed, using a screen printing method. The pastes of the compositions A to E were applied in order from the composition A at a size of 10 mmφ to form the first layer 2a to the fifth layer 2e. After forming the 5th layer 2e, it sintered on 1300 degreeC and the conditions for 4 hours, the fuel side electrode 2 of 5 layer structure was formed, and the electric power generation film was obtained. The film thickness of each layer after sintering was 15 μm (the film thickness of the fuel side electrode 2 was 75 μm).

( Reference Example 2)
An air side electrode similar to that of Reference Example 1 was formed on one surface of an 8 mol% YSZ flat plate (diameter 30 mm, thickness 200 μm) as a solid electrolyte.
On the surface opposite to the surface on which the air-side electrode was formed, pastes of compositions A, C, and E were applied in order from the composition A in a size of 10 mmφ to form the first to third layers. Thereafter, sintering was performed under the same conditions as in Reference Example 1, and a fuel-side electrode having a three-layer structure was formed to obtain a power generation film. The thickness of each layer after sintering was 20 μm (the thickness of the fuel side electrode was 60 μm).

(Comparative Example 1)
An air side electrode similar to that of Reference Example 1 was formed on one surface of an 8 mol% YSZ flat plate (diameter 30 mm, thickness 200 μm) as a solid electrolyte.
The paste of the composition D was apply | coated by the magnitude | size of 10 mm diameter to the surface on the opposite side to the surface in which the air side electrode was formed. Thereafter, sintering was performed under the same conditions as in Reference Example 1, and a fuel-side electrode having a single layer structure was formed to obtain a power generation film. The film thickness of the fuel side electrode after sintering was 60 μm.

A power generation test of the power generation films of Comparative Example 1 and Reference Examples 1 and 2 was performed. Using the current interrupt method, IR resistance and polarization resistance of the fuel side electrode at 1000 ° C. and 800 ° C. were measured. Table 1 shows the IR resistance and polarization resistance at 0.7V.

Polarization resistance at 800 ° C. Reference Example 1 and Reference Example 2 were reduced to about 1 / 4-1 / 6 of Comparative Example 1. As described above, the fuel electrode has a three-layer structure and a five-layer structure, so that a decrease in polarization resistance at 800 ° C. can be suppressed.

( Reference Examples 3 to 5)
An air side electrode similar to that of Reference Example 1 was formed on one surface of an 8 mol% YSZ flat plate (diameter 30 mm, thickness 200 μm) as a solid electrolyte.
A fuel-side electrode having a two-layer structure was formed on the surface opposite to the surface on which the air-side electrode was formed. As the first layer and the second layer, in the case of the reference example 3, the pastes of the compositions A and E, respectively, in the case of the reference example 4, the pastes of the compositions B and E, respectively, in the case of the reference example 5, the compositions C and E paste was used. Each paste was applied in the order of the first layer and the second layer with a size of 10 mmφ. Thereafter, sintering was performed under the same conditions as in Reference Example 1, and a fuel-side electrode was formed to obtain a power generation film. The thickness of each layer after sintering was 30 μm (the thickness of the fuel side electrode was 60 μm).

A power generation test of the power generation films of Reference Examples 3 to 5 was performed. Using the current interrupt method, the IR resistance and polarization resistance of the fuel side electrode at 800 ° C. were measured. Table 2 shows the IR resistance and polarization resistance at 0.7V.

  Even when the fuel-side electrode has a two-layer structure, the polarization resistance was 1/2 or less that of Comparative Example 1 having a one-layer structure, and a decrease in the polarization resistance could be suppressed.

(Example 1 )
An air side electrode similar to that of Reference Example 1 was formed on one surface of an 8 mol% YSZ flat plate (diameter 30 mm, thickness 200 μm) as a solid electrolyte.

  NiO powder and 8 mol% YSZ powder were mixed by a ball mill so as to have compositions A to E, thereby obtaining a mixed powder. Thereafter, the mixed powder was heat-treated at 1400 ° C. for 1 hour. After the heat treatment, the paste was pulverized and mixed again with a ball mill, and butyl carbitol was added to prepare a paste.

  A fuel-side electrode having a five-layer structure was formed on the surface opposite to the surface on which the air-side electrode was formed using a screen printing method. The pastes of compositions A to E were applied in order from composition A at a size of 10 mmφ. Thereafter, sintering was performed at 1300 ° C. for 4 hours to form a fuel-side electrode having a five-layer structure to obtain a power generation film. The thickness of each layer after sintering was 15 μm (the thickness of the fuel side electrode was 75 μm).

(Example 2 )
A fuel-side electrode having a five-layer structure was formed in the same manner as in Example 1 except that a mixed powder of NiO powders of compositions A to E and 8 mol% YSZ powder was subjected to heat treatment at 1400 ° C. for 10 hours. A power generation membrane was obtained.

(Comparative Example 2)
An air side electrode similar to that of Reference Example 1 was formed on one surface of an 8 mol% YSZ flat plate (diameter 30 mm, thickness 200 μm) as a solid electrolyte.
Except it subjected for 20 hours at 1400 ° C. The heat treatment after mixing the NiO powder and YSZ powder, in the same manner as in Example 1 and Example 1 to obtain a power generation film to form a fuel-side electrode of the five-layer structure .

Regarding the power generation membranes of Reference Example 1, Example 1 , 2 and Comparative Example 2, the IR resistance of the fuel side electrode at the initial stage (before the test), after 3000 hours of power generation at 800 ° C. and after 5000 hours of power generation at 800 ° C. And the polarization resistance was measured by the current interrupt method. Table 3 shows the IR resistance and polarization resistance at 0.7V.

With the power generation films of Example 1 and Example 2 , it was possible to suppress a decrease in IR resistance when operated for a long time. On the other hand, although the power generation film of Comparative Example 2 was able to prevent deterioration with the passage of time, the initial IR resistance was high because the grain growth of the raw material powder became prominent by heat treatment for a long time.

It is the schematic which shows an example of a solid oxide fuel cell. It is the schematic which shows an example of a structure of the electric power generation film | membrane of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Solid electrolyte 2 Fuel side electrode 2a-2e Mixed layer 3 Air side electrode 4,5 Corrugated plate 6,7 for electrode connection Interconnector 10 Electric power generation film

Claims (2)

A method for producing a power generation membrane of a solid oxide fuel cell, comprising: providing an air side electrode on one surface of a solid electrolyte; and providing a fuel side electrode on the other surface of the solid electrolyte, The step of providing the electrode
Producing a plurality of raw material powders having different mixing ratios of nickel oxide powder and yttria-stabilized zirconia powder;
The raw material powder having a high proportion of the yttria-stabilized zirconia powder and the raw material powder having a low proportion of the yttria-stabilized zirconia powder are coated on the surface of the solid electrolyte in the order of the raw material powder. Forming a plurality of mixed layers with stabilized zirconia;
Sintering the plurality of mixed layers,
Nickel oxide and zirconia are prepared by heat-treating a mixed powder obtained by mixing the nickel oxide powder and the yttria-stabilized zirconia powder at a temperature of 1300 ° C. or higher and lower than 1500 ° C. for a processing time of 1 hour or longer and 10 hours or shorter. And pulverizing the heat-treated mixed powder,
A method for producing a power generation membrane for a solid oxide fuel cell, characterized in that the raw material powder is applied onto the surface of a solid electrolyte so that the thickness of each of the sintered mixed layers is 10 μm or more and 30 μm or less. . The method for producing a power generation membrane for a solid oxide fuel cell according to claim 1 , wherein three or more of the mixed layers are stacked.

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