JP5955712B2 - Method for producing solid oxide fuel cell - Google Patents

Description

  The present invention relates to a method of manufacturing a solid oxide fuel cell including a single cell formed using a laminate including a plurality of layers.

  Conventionally, a flat-type solid oxide fuel cell (SOFC) is known. A single cell, which is a structural unit of a flat plate-type SOFC, includes a solid electrolyte layer, a fuel electrode layer in contact with the fuel gas, and an air electrode layer in contact with the oxidant gas. In a flat plate type SOFC, each layer constituting a single cell has a flat plate shape and is laminated with the surfaces of the flat plates in close contact with each other. In general, in order to improve the power generation performance of the SOFC, it is desirable to make the contact area between the layers of the electrode portion of the single cell as large as possible. For this reason, various methods have been proposed for widening the contact area by contriving a shape to a specific stack interface of a single cell (see, for example, Patent Documents 1 to 6). For example, if the surface is roughened by adding a fine uneven shape to the surface of a predetermined layer of a single cell, the effective contact area can be expanded, so that an improvement in the power generation area can be expected. In addition, since the adhesion reliability of the roughened laminated interface portion is improved, it is possible to prevent the separation of each layer and improve the durability reliability of the SOFC.

JP 2006-351403 A Japanese Patent Laid-Open No. 9-245811 Japanese Patent Laid-Open No. 9-277226 JP 7-135000 A JP 2007-323899 A JP 2012-9232 A

  However, since a general SOFC single cell has a structure in which, for example, flat ceramic sheets are laminated, a plurality of ceramic sheets are sequentially laminated to form a laminated body. It is necessary to join smooth surfaces together by adhesion or the like. Therefore, in order to give a shape to the lamination interface as described above, a process for forming fine irregularities on the laminated body after forming the laminated body and then performing a separate process is required. Complicated and expensive production facilities are inevitable. Further, as shown in Patent Document 6, even when a method of forming a laminate composed of a plurality of layers without performing adhesion or the like is applied, the step of applying the slurry on the surface of the predetermined layer is a smooth surface. Therefore, in this case as well, a separate process is required for the above-mentioned shape provision. As described above, in order to improve the power generation performance and durability reliability of SOFC, when an appropriate shape is applied to the predetermined laminate interface of the laminate, it is effective without complicating the manufacturing process. No known method is known.

  The present invention has been made in order to solve these problems, and by applying a shape to a predetermined laminate interface of a laminate by a simple method, the solid oxidation that can improve power generation performance and durability reliability can be achieved. An object of the present invention is to provide a method for manufacturing a physical fuel cell.

In order to solve the above problems, a method for producing a solid oxide fuel cell according to the present invention is a solid oxide fuel cell in which a single cell is formed using a laminate including at least a first layer and a second layer. In the production method, a first step of preparing a slurry containing at least a butyral resin to form the first layer, a slurry containing at least a solvent capable of dissolving the butyral resin, and adjusting the first A second step of laminating the second layer on the first surface of the layer, wherein the first step and the second step include a drying step of drying each of the slurries. In the second step, the first layer is a rough surface having a plurality of dimple-shaped recesses on the second surface facing the first surface, which is an interface with the second layer. Characterized by the formation of chemical surfaces

  According to the method for producing a solid oxide fuel cell of the present invention, when forming a laminated body used for forming a single cell, after forming the first layer in the first step, the first step in the second step is performed. When the second layer is laminated on the first surface of the first layer, the solvent component contained in the second layer soaks into the first layer below, so that the butyral resin contained in the first layer is selected. Eroded. At this time, when the solvent component remaining on the second surface of the first layer is removed by drying or the like, the dissolved portion of the second surface is exposed as a plurality of concave portions on the dimple, thereby forming a roughened surface. The Therefore, a laminated body including the first layer and the second layer can form a roughened surface having a plurality of recesses in a state where the other layer is laminated on one surface thereof. When the cell is formed, it is possible to improve the power generation area and contact reliability by expanding the contact area.

  In the present invention, a carrier film is prepared in the first step, and is placed in contact with the second surface of the first layer, and a roughened surface is formed on the second surface in the second step. After that, the carrier film may be removed. As a result, the solvent component soaked from the second layer into the first layer is likely to accumulate at the position of the carrier film, and the formation of a plurality of recesses is facilitated.

  In the present invention, when the green sheet is formed in the first step and the second step, a drying step may be provided. In this case, it is desirable that the time required for each drying step is such that the second step is the same as or longer than the first step, whereby the portion where the solvent component is accumulated is sufficiently dried to form a plurality of recesses. Can be reliably formed.

  In the present invention, there are various choices in the materials and functions of the first layer and the second layer. For example, the first layer and the second layer may be formed of the same material. In this case, the solid electrolyte layer can be constituted by the first layer and the second layer. In addition, for example, the first layer and the second layer may be formed of different materials, or the second layer may be formed by adding a conductive material to the same material as the first layer. . In this case, a solid electrolyte layer can be constituted by the first layer, and an electrode catalyst layer can be constituted by the second layer.

  In the present invention, the amount of the butyral resin in the first layer is preferably in the range of 5% to 8% by weight with respect to the material of the first layer. When the weight ratio of the butyral resin is less than 5%, defects such as wrinkles and cracks are likely to occur during molding of the laminate. When the weight ratio of the butyral resin exceeds 8%, the first due to the solvent component of the second layer This is because the erosion of the butyral resin portion of this layer is suppressed, making it difficult to form a plurality of recesses. In the present invention, the amount of the solvent in the second layer is preferably in the range of 30% to 50% by weight with respect to the inorganic raw material powder in the second layer.

  According to the present invention, when producing a single cell of a solid oxide fuel cell, a roughened surface having a plurality of dimple-shaped recesses can be formed on the surface of a predetermined layer by a simple method. It is possible to improve the power generation performance and durability reliability of the solid oxide fuel cell without requiring complicated processes and introduction of expensive production equipment.

It is a typical cross-section figure of the single cell of the solid oxide fuel cell of this embodiment. It is a figure which expands and shows the cross-section of the lamination | stacking interface of the single cell of FIG. It is a 1st sectional view showing the 1st example of the manufacturing method of a single cell. It is a 2nd sectional view explaining the 1st example of the manufacturing method of a single cell. It is a 3rd sectional view explaining the 1st example of the manufacturing method of a single cell. It is a 1st sectional view explaining a 2nd example of a manufacturing method of a single cell. It is a 2nd sectional view explaining the 2nd example of the manufacturing method of a single cell. It is a 3rd sectional view explaining a 2nd example of a manufacturing method of a single cell. It is a figure which shows the example of the actual photographic image of the roughening surface formed in one surface of the solid electrolyte layer as a 1st sheet layer when applying the manufacturing method of the single cell of this embodiment.

  Preferred embodiments of the present invention will be described below with reference to the drawings. However, the embodiments described below are specific examples to which the present invention is applied, and the present invention is not limited by the contents of the following embodiments.

  First, the basic structure of the solid oxide fuel cell according to this embodiment will be described. FIG. 1 shows a schematic cross-sectional structure of a single cell 10 which is a basic structural unit of the solid oxide fuel cell of the present embodiment. As shown in FIG. 1, in the single cell 10, a fuel electrode layer 11, an electrode catalyst layer 12, a solid electrolyte layer 13, a reaction preventing layer 14, and an air electrode layer 15 are stacked in order from the lower layer side. Has been.

  The fuel electrode layer 11 is in contact with a fuel gas serving as a hydrogen source and functions as an anode of the single cell 10. When the structure of the fuel electrode support type cell is adopted as the single cell 10, the fuel electrode layer 11 needs to have a mechanical strength that can support the entire single cell 10. In this case, it is desirable to form the fuel electrode layer 11 with a sufficient thickness of, for example, about 500 to 2000 μm. As a material of the fuel electrode layer 11, cermet made of metal particles and ceramic particles can be used. As the metal particles of the cermet, Ni is particularly preferably used, but Cu, Fe, Co, Ag, Pt, Pd, W, Mo, or an alloy thereof may be used. As ceramic particles of cermet, for example, ceramic materials such as zirconia and YSZ (yttria stabilized zirconia) can be used.

  The electrode catalyst layer 12 is formed on the surface of the fuel electrode layer 11 and has a role of enhancing electrochemical activity, and has higher conductivity than the fuel electrode layer 11. The film thickness of the electrode catalyst layer 12 is desirably in the range of 5 to 50 μm. As the material of the electrode catalyst layer 12, a cermet made of metal particles and ceramic particles can be adopted as in the fuel electrode layer 11. As the metal particles of the cermet, it is particularly preferable to use Ni, but Cu, Fe, Co or the like may be used. Various ceramic materials similar to the fuel electrode layer 11 can be used for the ceramic particles of the cermet.

  The solid electrolyte layer 13 is made of various solid electrolytes having ionic conductivity with respect to one of the fuel gas guided to the fuel electrode layer 11 and the oxidant gas guided to the air electrode layer 15. The thickness of the solid electrolyte layer 13 is preferably in the range of 3 to 20 μm. The ions in this case are, for example, oxygen ions or hydrogen ions. As a material of the solid electrolyte layer 13, YSZ, ScSZ, SDC, GDC, perovskite oxide, or the like can be used. In addition to the case where these materials are made into a single film, a multilayer film made of two or more kinds of materials may be used.

  The reaction preventing layer 14 is usually laminated after the solid electrolyte layer 13 is fired in order to prevent the reaction between the solid electrolyte layer 13 and the air electrode layer 15. The thickness of the reaction preventing layer 14 can be formed to about 1 to 20 μm, for example. As the material of the reaction preventing layer 14, a material mainly composed of CeO and a rare earth element can be used.

The air electrode layer 15 is in contact with the oxidant gas and functions as the cathode of the single cell 10. As a material for the air electrode layer 15, for example, a metal, a metal oxide, a metal composite oxide, or the like can be used. Among these, examples of the metal include metals such as Pt, Au, Ag, Pd, Ir, Ru, and alloys containing two or more metals. Examples of the metal oxide include oxides such as La, Sr, Ce, Co, Mn ₂ , and Fe. Examples of the metal complex oxide include various complex oxides containing at least one of La, Pr, Sm, Sr, Ba, Co, Fe, Mn, and the like.

  1 shows a structure in which the single cell 10 includes five layers of the fuel electrode layer 11, the electrode catalyst layer 12, the solid electrolyte layer 13, the reaction prevention layer 14, and the air electrode layer 15, but the operation as the SOFC. In order to realize the above, at least the unit cell 10 may have a structure including the fuel electrode layer 11, the solid electrolyte layer 13, and the air electrode layer 15. That is, in the structure of FIG. 1, one or both of the electrode catalyst layer 12 and the reaction preventing layer 14 may be omitted.

  A structural feature of the unit cell 10 of the present embodiment is that a dimple-shaped roughened surface Sr is formed at the interface between the solid electrolyte layer 13 and the reaction preventing layer 14 in the cross-sectional structure of FIG. Here, FIG. 2 shows an enlarged schematic cross-sectional structure of the roughened surface Sr portion of the single cell 10 of FIG. As shown in FIG. 2, a roughened surface Sr having a plurality of dimple-shaped recesses 20 is formed on the surface side of the solid electrolyte layer 13 at the interface between the lower solid electrolyte layer 13 and the upper reaction preventing layer 14. Has been. The material of the upper reaction preventing layer 14 is in the plurality of recesses 20. Therefore, compared with the case where the roughened surface Sr is formed as a smooth surface, the contact area between the solid electrolyte layer 13 and the reaction preventing layer 14 can be increased by providing the plurality of recesses 20. In FIG. 2, the reaction preventing layer 14 may be replaced with the air electrode layer 15.

  In FIG. 2, the size and shape of each recess 20 are actually varied, but are formed in a substantially circular planar shape having a predetermined diameter and a predetermined depth. For example, the diameter of each recess 20 is preferably in the range of 20 μm to 200 μm. If the diameter of the recess 20 is less than 20 μm, a contact area that improves the power generation performance of the SOFC cannot be secured. If the diameter of the recess 20 exceeds 200 μm, the sheet layer for the solid electrolyte layer 13 is manufactured in the manufacturing process described later. This is because the power generation performance deteriorates due to the formation of through holes. Further, for example, the depth of each recess 20 is desirably 2 μm or less. This is because if the depth of the recess 20 exceeds 2 μm, a through hole may be formed in the above-described sheet layer, or cracking may occur during firing. A specific method for forming a plurality of dimple-shaped recesses 20 on the surface of the solid electrolyte layer 13 will be described later.

  Next, a method for manufacturing the SOFC single cell 10 of this embodiment will be described with reference to the drawings. In the following, two embodiments will be sequentially described with respect to a method for manufacturing two unit cells 10 having different structures. In the present embodiment, in view of the structural features described above, the description will focus on the process for forming the roughened surface Sr having the plurality of dimple-shaped recesses 20 shown in FIG.

  The first embodiment of the method for manufacturing the unit cell 10 is an example in which the basic structure of the solid electrolyte layer 13 and the electrode catalyst layer 12 of FIG. 1 is formed by two sheet layers made of different materials. First, with respect to 100 weight ratio of 8Y-ZrO2 powder, 7 weight ratio of butyral resin, 3.5 weight ratio of phthalate ester as plasticizer, 2 weight ratio of dispersant, and 40.5 weight ratio of toluene And 25 weight ratio of ethanol was added and mixed with a ball mill to prepare a slurry. The obtained slurry was defoamed and then cast by a doctor blade method to produce a first sheet layer 31 (first layer of the present invention) on a carrier film 30 as shown in FIG. Step 1). Then, the 1st sheet layer 31 was dried at 60 ° C (drying process), and the 1st sheet layer 31 became thickness 10 micrometers after drying.

  Next, with respect to a mixed powder (100 weight ratio) of NiO powder (60 weight ratio) and 8Y-ZrO2 powder (40 weight ratio), 6.5 weight ratio of butyral resin and 3. phthalic acid ester as a plasticizer are used. A slurry was prepared by adding 25 weight ratio, 2 weight ratio of the dispersant, 40.5 weight ratio of toluene, and 25 weight ratio of ethanol, and mixing with a ball mill. After defoaming the obtained slurry, it was cast on the first sheet layer 31 by the doctor blade method, and as shown in FIG. 4, the upper surface S1 of the first sheet layer 31 (the first surface of the present invention) A second sheet layer 32 (second layer of the present invention) was formed thereon (second step of the present invention). Thereafter, the second sheet layer 32 is dried at 60 ° C. (drying process), and the dried second sheet layer 32 has a thickness of about 22 μm, and the first sheet layer 31 and the second sheet layer 32 are combined. The thickness was about 32 μm. The drying time in the second step is preferably set to be the same as or longer than the drying time in the first step in order to promote the formation of the roughened surface Sr.

  Next, as shown in FIG. 5, the carrier film 30 was removed from the lower surface S <b> 2 (the second surface of the present invention) of the first sheet layer 31. As a result, a plurality of dimple-shaped concave portions 20 (roughened surfaces Sr) exposed on the surface S2 of the first sheet layer 31 were confirmed. Here, the first sheet layer 31 in FIG. 5 corresponds to the solid electrolyte layer 13 in FIG. 1, and the second sheet layer 32 in FIG. 5 corresponds to the electrode catalyst layer 12 in FIG. 1 (FIGS. 5 and 1). Note that the top and bottom are reversed. In the plurality of recesses 20, the solvent component (toluene and ethanol) contained in the second sheet layer 32 oozes out to the first sheet layer 31 below, and accumulates in a part on the surface S <b> 2 at the boundary with the carrier film 30. The layer 31 is formed on the basis of the action of causing the composition concentration (mainly butyral resin) to be eroded selectively. Assuming this action, the above-mentioned solvent component is not limited to toluene and ethanol, but it is necessary to use a solvent having at least solubility in butyral resin.

  Thereafter, a sheet layer to be the fuel electrode layer 11 is laminated on the surface S3 of the second sheet layer 32 in FIG. ) And a laminated body laminated in the order of the solid electrolyte layer 13 (first sheet layer 31). And after degreasing | defatting the obtained laminated body, the sintered compact was obtained by baking at predetermined temperature. Next, a GDC layer is laminated on the roughened surface Sr (surface S2 of the first sheet layer 31) of the obtained sintered body to form the reaction preventing layer 14, and further an LSCF layer is laminated thereon. Thus, the air electrode layer 15 was formed. As a result, a single cell 10 having the structure of FIG. 1 was obtained. As described above, the air electrode layer 15 may be formed directly on the roughened surface Sr of the sintered body without providing the reaction preventing layer 14.

Next, the second embodiment of the method for manufacturing the single cell 10 is an example in which the basic structure of the solid electrolyte layer 13 of FIG. First, with respect to 100 weight ratio of 8Y-ZrO2 powder, 7 weight ratio of butyral resin, 3.5 weight ratio of phthalate ester as plasticizer, 2 weight ratio of dispersant, and 40.5 weight ratio of toluene And 25 weight ratio of ethanol was added and mixed with a ball mill to prepare a slurry. The obtained slurry was defoamed and then cast by a doctor blade method to produce a first sheet layer 41 (first layer of the present invention) on a carrier film 40 as shown in FIG. 6 (first step) ). Thereafter, the first sheet layer 41 and dried at 60 ° C. (drying step of the first step), the first sheet layer 41 was a thickness of 10μm after drying.

Next, 8 weights of 8Y-ZrO2 powder, 7 weight ratio of butyral resin, 3.5 weight ratio of phthalate ester as plasticizer, 2 weight ratio of dispersant, and 40.5 weight of toluene Ratio and 25 weight ratio of ethanol were added and mixed in a ball mill to prepare a slurry. After defoaming the obtained slurry, it was cast on the first sheet layer 41 by the doctor blade method, and as shown in FIG. 7, the upper surface S1 of the first sheet layer 41 (the first surface of the present invention) A second sheet layer 42 (second layer of the present invention) was formed thereon (second step). Thereafter, the second sheet layer 42 is dried at 60 ° C. (drying step of the second step), the second sheet layer 42 is approximately 22μm next thickness after drying, the first sheet layer 41 and the second sheet layer 42 The total thickness of the two layers was about 32 μm.

  Next, as shown in FIG. 8, the carrier film 40 was removed from the roughened surface Sr on the lower side of the first sheet layer 41. As a result, a plurality of dimple-shaped recesses 20 were confirmed on the roughened surface Sr of the first sheet layer 41. Here, the first sheet layer 41 and the second sheet layer 42 in FIG. 8 integrally correspond to the solid electrolyte layer 13 in FIG. 1 (note that the top and bottom are reversed in FIGS. 8 and 1). . In the second embodiment, the operation of forming the plurality of recesses 20 is as described in the first embodiment. Further, the role of the solvent component (toluene, ethanol) and the setting of the drying times in the first step and the second step are as described in the first embodiment.

  Thereafter, the sheet layer to be the electrode catalyst layer 12 and the sheet layer to be the fuel electrode layer 11 are sequentially laminated on the surface S3 of the second sheet layer 42 in FIG. The laminated body laminated | stacked in order of the electrode catalyst layer 12 and the solid electrolyte layer 13 (the 1st sheet layer 41 and the 2nd sheet layer 42) was obtained. And after degreasing | defatting the obtained laminated body, the sintered compact was obtained by baking at predetermined temperature. The method for forming the reaction preventing layer 14 and the air electrode layer 15 on the roughened surface Sr (surface S2 of the first sheet layer 41) of the obtained sintered body is the same as that in the first embodiment. Therefore, the description is omitted.

  Of the above-described two examples relating to the method of manufacturing the single cell 10 according to the present embodiment, the first example is suitable for the support film type single cell 10 and the second example is a self-supporting film type single cell. 10 is suitable. That is, in the first embodiment, since the first sheet layer 31 constitutes the entire solid electrolyte layer 13, the solid electrolyte layer 13 becomes relatively thin and the fuel electrode layer 11 serves as a support base. On the other hand, in the second embodiment, the first sheet layer 41 and the second sheet layer 42 made of the same kind of material respectively constitute a part of the solid electrolyte layer 13, and thus the solid electrolyte layer 13 in which they are integrated. Becomes relatively thick so that the SOFC can be supported. However, the operational effects based on the structural features of the unit cell 10 of the present embodiment are generally the same regardless of which of the first and second examples is applied.

  In the manufacturing method (first and second examples) of the single cell 10 of the present embodiment, the weight ratio of the butyral resin in the slurry of the first sheet layers 31 and 41 is 100 weight ratio of 8Y-ZrO2 powder. It is desirable to set within the range of 5-8%. If the weight ratio of the butyral resin is less than 5%, it becomes a factor in which wrinkles, cracks, pinholes and the like are generated when the laminate is formed. On the other hand, when the weight ratio of the butyral resin exceeds 8%, erosion of the first sheet layers 31 and 41 due to the slurry of the second sheet layers 32 and 42 is suppressed, and it is difficult to form the plurality of dimple-shaped recesses 20. It becomes.

  Moreover, in the manufacturing method (1st and 2nd Example) of the single cell 10 of this embodiment, the solvent component in the slurry of the 2nd sheet layers 32 and 42 is the whole 2nd sheet layers 32 and 42 (inorganic). It is desirable to set within a range of 30 to 50% by weight with respect to the raw material powder). Further, the ratio (weight ratio) occupied by the solvent component in the slurry of the second sheet layers 32, 42 is divided by the ratio (weight ratio) occupied by the butyral resin in the slurry of the first sheet layers 31, 41, It is desirable to be within the range of 9.4 to 12.9. When the above value is less than 9.4, the amount of butyral resin in the slurry of the first sheet layers 31 and 41 is relatively increased, and the butyral resin is eroded by the solvent component in the slurry of the second sheet layers 32 and 42. Becomes weak, and a plurality of dimple-shaped recesses 20 are not formed. On the other hand, when the above value exceeds 12.9, the amount of butyral resin in the slurry of the first sheet layers 31 and 41 is relatively reduced, and the solvent component in the slurry of the second sheet layers 32 and 42 with respect to this butyral resin. Erosion due to the above becomes excessive, and through holes are formed in the first sheet layers 31 and 41, or the amount of butyral resin is insufficient, so that the plurality of dimple-like recesses 20 are not formed.

  FIG. 9 shows an actual photographic image of the roughened surface Sr formed on one surface of the solid electrolyte layer 13 as the first sheet layer 31 (41) when the manufacturing method of the unit cell 10 of the present embodiment is applied. An example of (digital scope photograph) is shown. As shown in FIG. 9, on the roughened surface Sr formed in the solid electrolyte layer 13, a plurality of concave portions 20 distributed in a spot shape can be observed. It can be seen that each recess 20 is formed to have a diameter of approximately 60 to 70 μm in a plan view. In the roughened surface Sr of the solid electrolyte layer 13, it was confirmed that the ratio of the plurality of recesses 20 per unit area is generally in the range of 35 to 50%.

  As described above, by applying the manufacturing method of the unit cell 10 of the present embodiment, the surface is roughened by applying a plurality of dimple-shaped recesses 20 to the surface in a simple process for the laminate. The single cell 10 can be finally produced using the laminate. Therefore, without requiring a complicated manufacturing process such as separate processing, the contact area of the roughened laminated interface portion of the single cell 10 can be expanded, and the power generation performance of the SOFC can be improved. Further, by improving the adhesion reliability of the stack interface portion of the single cell 10, it is possible to effectively prevent peeling of each layer and improve the durability reliability of the SOFC.

  The contents of the present invention have been specifically described above based on the present embodiment, but the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the scope of the present invention. For example, in the present embodiment, the case where the present invention is applied to the SOFC having the cross-sectional structure shown in FIG. 1 has been described. However, the present invention is not limited to the cross-sectional structure of FIG. 1, and a laminate including at least a plurality of layers is used. The present invention can be widely applied to SOFCs having various structures formed in this manner. In addition, the contents of the present invention are not limited by the above-described embodiment with respect to other points, and are appropriately modified without being limited to the contents disclosed in the above-described embodiment as long as the effects of the present invention can be obtained. Is possible.

DESCRIPTION OF SYMBOLS 10 ... Single cell 11 ... Fuel electrode layer 12 ... Electrode catalyst layer 13 ... Solid electrolyte layer 14 ... Reaction prevention layer 15 ... Air electrode layer 20 ... Several recessed part 30, 40 ... Carrier film 31, 41 ... 1st sheet layer (1st) 1 layer)
32, 42 ... second sheet layer (second layer)
Sr ... rough surface

Claims (10)

In a method for producing a solid oxide fuel cell in which a single cell is formed using a laminate including at least a first layer and a second layer,
A first step of adjusting the slurry containing at least a butyral resin to form the first layer;
Preparing a slurry containing at least a solvent capable of dissolving the butyral resin, and laminating the second layer on the first surface of the first layer; and
Including
The first step and the second step include a drying step of drying each of the slurries,
In the second step, a roughened surface having a plurality of dimple-shaped concave portions on a second surface facing the first surface, which is an interface with the second layer, with respect to the first layer. Is formed, and a method for producing a solid oxide fuel cell. In the first step, the first layer is disposed in a state where the second surface is in contact with a carrier film,
In the second step, the carrier film is removed after the roughened surface is formed on the second surface.
The method for producing a solid oxide fuel cell according to claim 1. Before Symbol time required for the drying process of the second step, the solid oxide according to claim 1 or 2, characterized in that identical or longer than the time required for the drying step of the first step Manufacturing method of fuel cell.   4. The method for manufacturing a solid oxide fuel cell according to claim 1, wherein the first layer and the second layer are formed of the same material. 5.   5. The method for producing a solid oxide fuel cell according to claim 4, wherein each of the first layer and the second layer constitutes a solid electrolyte layer. 6.   4. The method for manufacturing a solid oxide fuel cell according to claim 1, wherein the first layer and the second layer are formed of different materials. 5.   The method for manufacturing a solid oxide fuel cell according to claim 6, wherein the second layer is formed by adding a conductive material to the same material as the first layer.   The method for producing a solid oxide fuel cell according to claim 6 or 7, wherein the first layer constitutes a solid electrolyte layer, and the second layer constitutes an electrode catalyst layer.   The amount of the butyral resin in the first layer is in the range of 5% to 8% by weight with respect to the material of the first layer. A method for producing a solid oxide fuel cell as described in the above item.   8. The solid oxidation according to claim 7, wherein the amount of the solvent in the second layer is within a range of 30% to 50% by weight with respect to the inorganic raw material powder of the second layer. A method of manufacturing a physical fuel cell.