JP2012009232A - Method of manufacturing solid oxide fuel battery cell, solid oxide fuel battery cell and solid oxide fuel battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a solid oxide fuel battery cell in which both quality and mass productivity can be enhanced when the solid oxide fuel battery cell consisting of a plurality of layers is manufactured.SOLUTION: A solid oxide fuel battery cell (single cell) 10 includes a fuel electrode layer 11, an active layer 12, a solid electrolyte layer 13, a reaction prevention layer 14, and an air electrode layer 15. In the manufacturing process of the single cell 10, a multiple laminate sheet (unburnt multiple laminate) laminating two or more adjoining layers is formed, and the single cell 10 is formed by integrating this multiple laminate sheet with other layers. Consequently, power generation performance can be enhanced by bonding respective layers constituting the multiple laminate sheet with high adhesion, and occurrence of defects can be reduced while enhancing mass productivity by simplifying the manufacturing process.

Description

  The present invention relates to a method of manufacturing a flat plate type solid oxide fuel cell having a fuel electrode layer, a solid electrolyte layer, and an air electrode layer.

  Conventionally, a flat-type solid oxide fuel cell (SOFC) is known. In general, in a flat type SOFC, a fuel electrode layer in contact with a fuel gas is disposed on one side of a solid electrolyte layer, and an air electrode layer in contact with air is disposed on the other side, whereby a solid oxide fuel cell ( Single cell), and a stack is formed by stacking a plurality of single cells. As the structure of the single cell, a mechanical strength can be secured by adopting a support membrane type cell in which a specific layer (for example, a fuel electrode layer) is formed with a thick film. In this case, an active layer having high electrochemical activity can be provided between the fuel electrode layer and the solid electrolyte layer. As a method for producing a flat plate-type SOFC, for example, a method in which a solid electrolyte green sheet, an active layer green sheet, and a fuel electrode green sheet are separately produced and pressure-bonded and laminated is proposed ( For example, see Patent Document 1).

JP 2007-165143 A

  In order to maintain good power generation performance in a flat plate type SOFC, it is necessary to suppress contact resistance between different layers as much as possible. In particular, the bonding state at the interface between the solid electrolyte layer and the active layer is an important factor for further improving the power generation performance. However, in the above conventional flat plate type SOFC manufacturing method, the green sheets of each layer are pressure-bonded and laminated, so that different layers including the interface between the solid electrolyte layer and the active layer are sufficiently bonded together. It is not always done. For example, if the interface between the solid electrolyte layer and the active layer is in an insufficiently bonded state, bubbles may remain as voids. Therefore, there is a problem that the power generation performance of the SOFC deteriorates due to an increase in contact resistance. Further, in the above conventional flat plate-type SOFC manufacturing method, a crimping step is required every time the green sheets are sequentially laminated, so that the number of crimping increases according to the number of layers. Accordingly, there is a problem that defects such as delamination of the green sheet are likely to occur in the crimping process, and the mass productivity of the manufacturing process is reduced.

  The present invention has been made to solve these problems. In a flat plate type SOFC composed of a large number of layers, different layers are bonded with high adhesion to ensure good power generation performance, and sheet bonding is achieved. An object of the present invention is to realize a method of manufacturing a solid oxide fuel cell capable of preventing the occurrence of defects during the process and improving the manufacturing yield.

  In order to solve the above-mentioned problems, the present invention provides a solid comprising a support base layer serving as a support base, a solid electrolyte layer, an air electrode layer, and an active layer between the support base layer and the solid electrolyte layer. A method for manufacturing an oxide fuel cell, wherein a plurality of laminates are formed by laminating an unsintered active layer on a surface of an unsintered solid electrolyte layer, and the plurality of laminates and the unsintered support base layer are integrated. To form an intermediate laminate, and the intermediate laminate and the unfired air electrode layer are integrated to form a solid oxide fuel cell laminate.

  According to the method for producing a solid oxide fuel cell of the present invention, another layer is formed on a multi-layered body (a multi-layered sheet or a material after firing the multi-layered sheet) composed of two or more unfired layers. The intermediate laminate is integrated to form a solid oxide fuel cell (single cell) laminate, and the layers constituting the multiple laminate are joined with high adhesion, reducing contact resistance. As a result, the power generation performance can be improved. Also, when forming the intermediate laminate, assuming that it is integrated by, for example, press molding or pressure bonding, the number of times of press molding or the like can be reduced compared to the case where all the layers are composed of a single layer sheet, It is possible to prevent the occurrence of defects during manufacturing and improve the manufacturing yield.

  In the present invention, the “multiple laminate” (multiple laminate sheet or one after firing of the multiple laminate sheet) is formed by sequentially laminating a plurality of layers (sheets), and adjacent layers. Are different in material or composition ratio. In addition, the multi-layered body includes those that have been fired after being stacked.

  In contrast to the “multi-layered product”, the “single-layer sheet” includes a sheet formed by sequentially laminating a plurality of layers having the same material or composition ratio in addition to a sheet composed of a single layer. Note that a multilayer sheet formed by alternately laminating layers of two kinds of materials or composition ratios corresponds to a “multiple laminate”.

  For example, when an unsintered solid electrolyte layer is formed on the surface of the unsintered fuel electrode layer, it corresponds to a multi-layered body as long as the materials and composition ratios of the two are different. In this case, the method of forming the multi-layered body is not limited. As an example, a slurry of the fuel electrode layer is cast on a support member (carrier sheet), and a slurry of the solid electrolyte layer is further cast thereon. Can be employed. Moreover, it can replace with casting and can employ | adopt the method of producing a ceramic film | membrane etc. by using a coater method or a printing coating method or a spray coating method. Then, a solid oxide fuel cell laminated body can be obtained by integrating a multiple laminated body and another single layer sheet | seat, for example by press molding. In the case of forming a plurality of laminated bodies by other combinations, generally the same method can be applied. In addition, when integrating another single layer sheet | seat with a several laminated body, you may integrate, after baking a multiple laminated body beforehand.

  The multi-layered product of the present invention may be formed of various combinations of two layers as follows. For example, the plurality of laminates can be formed by sequentially laminating an unfired fuel electrode layer, an unfired solid electrolyte layer, and an unfired air electrode layer. Further, for example, the unfired fuel electrode layer is constituted by an unfired support substrate layer serving as a support substrate, and an unfired active layer between the unfired support substrate layer and the unfired solid electrolyte layer, and the unfired solid The plurality of laminates can be formed by sequentially laminating the unfired active layer on the surface of the electrolyte layer. In this case, the plurality of laminates and the unfired support base layer are integrated to form an intermediate laminate, and the intermediate laminate and the unfired air electrode layer are integrated to form a solid oxide fuel cell. A laminated body (single cell laminated body) is formed. The intermediate laminate may be integrated with the air electrode layer after firing in advance.

  Also, for example, the plurality of laminates can be formed by sequentially laminating the unsintered active layer on the surface of the unsintered support base layer. In this case, the intermediate laminate and the unfired solid electrolyte layer are integrated to form an intermediate laminate, and the intermediate laminate and the unfired air electrode layer are integrated to form a single cell laminate. Is done. The intermediate laminate may be integrated with the air electrode layer after firing in advance.

  Moreover, you may form the said multiple laminated body of this invention by the combination of 3 or more layers as follows. For example, the multiple laminate can be formed by sequentially laminating an unsintered solid electrolyte layer, an unsintered active layer, and an unsintered support base layer. In this case, the plurality of laminates and the unfired air electrode layer are integrated to form a single cell laminate. In addition, after laminating | stacking a multiple laminated body in advance, you may integrate with an air electrode layer.

  In addition, for example, it is also possible to form a plurality of laminates by sequentially laminating an unsintered solid electrolyte layer, an unsintered active layer, an unsintered support base layer, and an unsintered air electrode layer, thereby forming a single cell laminate. It is.

  As each sheet constituting the solid oxide fuel cell of the present invention, for example, a ceramic green sheet can be adopted. In this case, a plurality of ceramic green sheets constituting the laminate can be fired simultaneously.

  The thickness of the solid electrolyte layer is preferably in the range of 3 to 20 μm. Moreover, it is preferable that the film thickness of the said active layer exists in the range of 5-50 micrometers.

  The present invention can be applied not only to a solid oxide fuel cell stack that is a single cell, but also to a solid oxide fuel cell stack configured by stacking a plurality of single cells. It is.

  As described above, according to the present invention, since a solid oxide fuel cell is formed using a plurality of stacked bodies in which two or more layers are stacked, each layer included in the plurality of stacked bodies is firmly bonded, The power generation performance can be improved by reducing the contact resistance of the interface. In particular, it is possible to reliably prevent deterioration in power generation performance due to voids remaining as bubbles at the interface between the solid electrolyte layer and the active layer. In addition, the effects of defects such as delamination can be suppressed by reducing operations such as press molding and crimping to integrate the laminate during the manufacture of solid oxide fuel cells, and mass productivity in the manufacturing process Can be improved.

It is a typical section structure figure of the solid oxide form fuel cell of this embodiment. 1 is a schematic cross-sectional structure diagram of a solid oxide fuel cell stack according to an embodiment. FIG. 3 is a first cross-sectional structure diagram illustrating a manufacturing method in Example 1. FIG. 6 is a second cross-sectional structure diagram illustrating the manufacturing method according to the first embodiment. FIG. 6 is a third cross-sectional structure diagram for explaining the manufacturing method according to the first embodiment. 6 is a cross-sectional structure diagram illustrating a manufacturing method according to Embodiment 2. FIG. 6 is a cross-sectional structure diagram illustrating a manufacturing method of Example 4. FIG.

  Preferred embodiments of the present invention will be described below with reference to the drawings. However, the embodiment described below is an example of a form to which the technical idea of the present invention is applied, and the present invention is not limited by the content of the present embodiment.

  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 solid oxide fuel cell 10 (hereinafter referred to as “single cell 10”) which is a basic structural unit of the solid oxide fuel cell of the present embodiment. Yes. As shown in FIG. 1, in the single cell 10, a fuel electrode layer 11, an active 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. ing.

  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. Further, the fuel electrode layer 11 serves as a support base layer that supports the entire single cell 10. Therefore, in order to ensure the mechanical strength of the single cell 10, the fuel electrode layer 11 is desirably formed with a sufficient thickness of, for example, about 500 to 2000 μm. As the 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. Examples of cermet ceramic particles include zirconia, YSZ (yttria stabilized zirconia), ScSZ (scandia stabilized zirconia), SDC (samarium doped ceria), GDC (gadria doped ceria), alumina, silica, and titania. A ceramic material such as can be used.

  The active layer 12 is formed on the surface of the fuel electrode layer 11 and has a role of increasing electrochemical activity, and has higher conductivity than the fuel electrode layer 11. The film thickness of the active layer 12 is desirably in the range of 5 to 50 μm. That is, when the active layer 12 is formed to have a film thickness of less than 5 μm, holes are likely to be generated in the solid electrolyte layer 13, whereas when the active layer 12 is formed to have a film thickness of more than 50 μm, the air permeability of the fuel electrode layer 11 cannot be secured. It is because it leads to the fall of. As the material of the active layer 12, as with the fuel electrode layer 11, cermet made of metal particles and ceramic particles can be adopted. 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. The thickness of the solid electrolyte layer 13 is preferably in the range of 3 to 20 μm. That is, it is difficult to form the solid electrolyte layer 13 with a film thickness of less than 3 μm from the limit of thinning, but when it is formed with a film pressure of more than 20 μm, the power generation efficiency deteriorates. 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 a combustion-supporting gas serving as an oxygen source and functions as a 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, 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 (for example, La ₂ O ₃ , SrO, Ce ₂ O ₃ , Co ₂ O ₃ , MnO ₂ , FeO, etc. ). In addition, 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 (for example, La _1-x Sr _x CoO ₃ based composite _{oxide, La 1-x Sr x FeO} 3 -based composite _{oxide, La 1-x Sr x Co} 1-y Fe y O 3 composite _{oxide, La 1-x Sr x MnO} 3 composite oxide , Pr _1-x Ba _x CoO ₃ composite oxide, Sm _1-x Sr _x CoO ₃ composite oxide, and the like.

  When the unit cell 10 according to the present embodiment is manufactured, when the fuel electrode layer 11, the active layer 12, the solid electrolyte layer 13, the reaction preventing layer 14, and the air electrode layer 15 are sequentially stacked, the adjacent two of these layers are adjacent to each other. It is characteristic that a multi-layered sheet (multi-layered product of the present invention) including more than one layer is formed, and the multi-layered sheet and other layers are integrated to obtain a single cell 10. The definition of the multi-layered sheet is as already described as the definition of the “multi-layered body” including the difference from the single-layer sheet. For example, a multi-layered sheet (two-layer laminated sheet) composed of two adjacent layers is composed of an active layer 12 (unfired active layer of the present invention) and a solid electrolyte layer 13 (unfired solid electrolyte layer of the present invention). Examples thereof include a multi-layered sheet and a multi-layered sheet composed of the fuel electrode layer 11 (the unfired fuel electrode layer (unfired support base layer) of the present invention) and the active layer 12. In addition, as a multi-layered sheet composed of three or more adjacent layers, a multi-layered sheet composed of a fuel electrode layer 11, an active layer 12, and a solid electrolyte layer 13, in addition to these, a reaction preventing layer 14 and an air electrode layer 15 (this And an unfired air electrode layer of the present invention). A specific manufacturing method and characteristics of the single cell 10 including these multiple laminated sheets will be described later (see Examples 1 to 4).

  Note that the active layer 12 and the reaction prevention layer 14 can be operated as a solid oxide fuel cell if at least the fuel electrode layer 11, the solid electrolyte layer 13, and the air electrode layer 15 are provided. A single cell 10 that does not include one or both of them can be configured.

  Next, a solid oxide fuel cell stack in which a plurality of single cells 10 of FIG. 1 are stacked will be described. FIG. 2 shows a schematic cross-sectional structure of a solid oxide fuel cell stack 20 (hereinafter referred to as “stack 20”). In the example of FIG. 2, a stack 20 is configured by three unit cells 10 stacked in the vertical direction. In addition, only the fuel electrode layer 11, the solid electrolyte layer 13, and the air electrode layer 15 of each unit cell 10 are shown, and the active layer 12 and the reaction preventing layer 14 are omitted. An interconnector 21 is provided between the adjacent single cells 10. The interconnector 21 is formed using a heat-resistant alloy such as stainless steel, a nickel-base alloy, or a chromium-base alloy as a metal material having conductivity and heat resistance.

  A fuel electrode side current collector 22 is provided on the bottom surface side of the fuel electrode layer 11 of each unit cell 10, and an air electrode side current collector 23 is provided on the surface side of the air electrode layer 15 of each unit cell 10. It has been. The fuel electrode side current collector 22 is formed using, for example, Ni or a Ni-based alloy, and the air electrode side current collector 23 is formed using, for example, a metal and a conductive ceramic.

  Each interconnector 21 is joined to the air electrode side current collector 23 of the lower unit cell 10 and the fuel electrode side current collector 22 of the upper unit cell 10. The fuel electrode side current collector 22 of the lowermost single cell 10 is joined to the lower bottom member 24, and the air electrode side current collector 23 of the uppermost single cell 10 is joined to the upper lid member 25.

  On the other hand, an isolation separator 26 is provided in each single cell 10. The role of the separation separator 26 is to isolate the fuel gas flow path 27 and the air flow path 28 and prevent air containing combustion-supporting oxygen or the like from mixing with the fuel gas. A frame 29 made of an insulator such as ceramic is formed around the plurality of single cells 10.

  Specific examples relating to the solid oxide fuel cell according to the present embodiment will be described with reference to the drawings. Below, four Examples 1-4 from which a manufacturing procedure differs are described one by one.

[Example 1]
A butyral resin, DOP which is a plasticizer, a dispersant, and a toluene / ethanol mixed solvent were added to 100 parts by weight of YSZ powder, and mixed with a ball mill to prepare a slurry. The obtained slurry was cast by a doctor blade method to produce a solid electrolyte green sheet 13a having a thickness of 10 μm on a carrier sheet 40 as a support member of the present invention, as shown in FIG. Next, with respect to 100 parts by weight of the mixed powder of 60 parts by weight of NiO powder and 40 parts by weight of YSZ powder, butyral resin, DOP which is a plasticizer, a dispersant, and a toluene and ethanol mixed solvent are added to a ball mill. To prepare a slurry. The obtained slurry was further cast on the solid electrolyte green sheet 13a by a doctor blade method to form an active layer 12 having a thickness of 10 μm on the solid electrolyte green sheet 13a. As a result, as shown in FIG. 3, a 20 μm thick two-layer laminated sheet 30 composed of a solid electrolyte green sheet 13a having a thickness of 10 μm and an active layer 12 having a thickness of 10 μm was obtained.

  On the other hand, with respect to 100 parts by weight of mixed powder of 60 parts by weight of NiO powder and 40 parts by weight of YSZ powder, organic beads (10% by weight with respect to the mixed powder), butyral resin, and plasticizer are used as pore formers. A DOP, a dispersant, and a toluene / ethanol mixed solvent were added and mixed with a ball mill to prepare a slurry. The obtained slurry was cast by a doctor blade method to produce a fuel electrode green sheet 11a (single layer sheet) having a thickness of 250 μm on a carrier sheet 41 as shown in FIG.

  Subsequently, the obtained two-layer laminated sheet 30 and the fuel electrode green sheet 11a (single-layer sheet) were each cut into a size of 150 × 150 mm. The two-layer laminated sheet 30 after the cut and the fuel electrode green sheet 11a after the cut are press-molded in a stacked state, the carrier sheet 40 of the two-layer laminated sheet 30, and the fuel electrode green sheet 11a Each of the carrier sheets 41 was removed. As a result, as shown in FIG. 5, a laminated body 31 (an intermediate laminated body of the single cell 10) in which the fuel electrode layer 11, the active layer 12, and the solid electrolyte layer 13 were laminated in this order was obtained. The laminate 31 was degreased at 250 ° C. in a degreasing furnace, and then fired at 1350 ° C. As a result, a sintered body having a size of 120 × 120 mm was obtained.

  Next, as shown in FIG. 1, a reaction prevention layer 14 was formed by laminating a GDC layer having a thickness of 5 μm on the surface of the solid electrolyte layer 13 of the sintered body. Further, an air electrode layer 15 was formed by laminating an LSCF layer having a thickness of 40 μm and a size of 100 × 100 mm on the surface of the reaction preventing layer 14 on the sintered body, whereby the single cell 10 was obtained.

  In Example 1, the example of the unit cell 10 including the reaction preventing layer 14 of FIG. 1 has been described. However, the unit cell having a structure in which the reaction preventing layer 14 is not provided between the solid electrolyte layer 13 and the air electrode layer 15. 10 may be formed. The same applies to the following embodiments.

[Example 2]
The slurry of the fuel electrode layer 11 was prepared by the same method as in Example 1, and the obtained slurry was cast by the doctor blade method, and the active layer 12 of the two-layer laminated sheet 30 of FIG. The fuel electrode layer 11 was laminated to obtain a plurality of laminated sheets 32 composed of the fuel electrode layer 11, the active layer 12, and the solid electrolyte green sheet 13a as shown in FIG. Next, as in Example 1, the obtained multi-layered sheet 32 was cut into a size of 150 × 150 mm to obtain a laminated body, and then degreased and fired in the same manner as in Example 1 to obtain a sintered body. It was. The reaction preventing layer 14 and the air electrode layer 15 were formed on the surface of the solid electrolyte layer 13 of the obtained sintered body in the same manner as in Example 1 to obtain a single cell 10.

[Example 3]
The reaction preventing layer 14 and the air electrode layer 15 were sequentially laminated on the solid electrolyte layer 13 of the multi-layered sheet 32 (FIG. 6) obtained in Example 2 to obtain a multi-layered sheet (not shown). Next, a laminated body is obtained by cutting a multi-layered sheet composed of five layers of a fuel electrode layer 11, an active layer 12, a solid electrolyte layer 13, a reaction preventing layer 14, and an air electrode layer 15 in order from the lower layer into a size of 150 × 150 mm. After that, degreasing and firing were performed in the same manner as in Examples 1 and 2 to obtain a single cell 10.

[Example 4]
A fuel electrode green sheet 11a (FIG. 4) was produced in the same manner as in Example 1. Next, the slurry of the active layer 12 is prepared in the same manner as in Example 1, and the obtained slurry is cast by the doctor blade method, and on the surface of the fuel electrode green sheet 11a on the carrier sheet 42 as shown in FIG. The active layer 12 was laminated to obtain a two-layer laminated sheet 33. On the other hand, the solid electrolyte green sheet 13a (FIG. 3) was obtained from the slurry produced by the same method as in Example 1. Thereafter, the two-layer laminated sheet 33 and the solid electrolyte green sheet 13a of FIG. 7 were laminated in the order of the fuel electrode layer 11, the active layer 12, and the solid electrolyte layer 13 by press molding after cutting in the same manner as in Example 1. The single cell 10 was obtained by producing a laminated body and performing degreasing and baking of this laminated body.

[Single cell structure and performance evaluation]
Table 1 shows the structure of each unit cell 10 of Examples 1 to 4 obtained as described above and the evaluation results of the power generation performance, and shows a case of a unit cell based on the conventional structure as a comparative example. It was. As shown in Table 1, in Examples 1 to 4, a two-layer laminated sheet or a plurality of laminated layers by different combinations of the fuel electrode layer 11, the active layer 12, the solid electrolyte layer 13, the reaction preventing layer 14, and the air electrode layer 15 are used. It can be seen that the sheet is included and the other layers are included as a single layer sheet, whereas the comparative example includes all these layers as a single layer sheet.

Evaluation of power generation performance is as follows: the temperature of the single cell 10 is 700 ° C., the fuel gas flow rate is 2 L / min for humidified hydrogen, and the air flow rate is 6 L / min, and the output voltage of the single cell 10 is 0.7 V. We compared the power generation when As a result, as shown in Table 1, a power generation amount of 1.09 (W / cm ² ) was obtained for the comparative example, whereas 1.14 to 1.15 (W for Examples 1 to 4). / Cm ² ), a power generation amount within the range was obtained, and the power generation amount increased by about 5% or more compared to the comparative example.

  As described above, the improvement in the power generation performance of the single cell 10 obtained by the manufacturing methods of Examples 1 to 4 is due to the improved adhesion of the interface at the portion of the multi-layered sheet (including the two-layered sheet). It is an effect. That is, taking Example 1 as an example, the two-layer laminated sheet 30 (FIG. 3) is formed by forming the active layer 12 on the solid electrolyte green sheet 13a, so that the adhesiveness between the two is high. In the comparative example, since the single-layer sheet of the solid electrolyte layer 13 and the single-layer sheet of the active layer 12 are integrated by press molding or the like, the adhesiveness becomes relatively low. For this reason, the contact resistance between the solid electrolyte layer 13 and the active layer 12 of Example 1 is reduced, and thus the effect of improving the power generation performance as compared with the comparative example is obtained. The same applies to the case of the multi-layered sheet 32 of Example 2 (FIG. 6), the multi-layered sheet of Example 3 (not shown), and the double-layered sheet 33 of Example 4 (FIG. 7). There was an effect of improving power generation performance due to high adhesion. Moreover, since defects such as delamination are reduced by improving the adhesion in each of the plural (two-layer) laminated sheets, the production yield can be improved. Furthermore, since the number of times of press molding or the like when manufacturing the single cell 10 is reduced, the manufacturing process can be rationalized.

  The content of the present invention has been specifically described above based on the present embodiment, but the present invention is not limited to the content of the above-described embodiment, and various modifications can be made without departing from the scope of the present invention. it can. For example, the structure, shape, material, formation method, and the like of the unit cell 10 and the stack 20 can be appropriately changed as long as the effects of the present invention can be obtained.

10. Solid oxide fuel cell (single cell)
DESCRIPTION OF SYMBOLS 11 ... Fuel electrode layer 12 ... Active layer 13 ... Solid electrolyte layer 14 ... Reaction prevention layer 15 ... Air electrode layer 20 ... Solid oxide fuel cell stack (stack)
DESCRIPTION OF SYMBOLS 21 ... Interconnector 22 ... Fuel electrode side collector 23 ... Air electrode side collector 24 ... Bottom member 25 ... Lid member 26 ... Isolation separator 27, 28 ... Channel 29 ... Frame body 30, 33 ... Two-layer laminated sheet 31 ... Laminated body 32 ... Multiple laminated sheets 40, 41, 42 ... Carrier sheet

Claims (13)

A method for producing a solid oxide fuel cell comprising: a support substrate layer to be a support substrate; a solid electrolyte layer; an air electrode layer; and an active layer between the support substrate layer and the solid electrolyte layer. And
A plurality of laminates are formed by laminating an unsintered active layer on the surface of the unsintered solid electrolyte layer,
Integrating the plurality of laminates and the unfired support base layer to form an intermediate laminate,
The intermediate laminate and the unfired air electrode layer are integrated to form a solid oxide fuel cell stack,
A method for producing a solid oxide fuel cell. A method for producing a solid oxide fuel cell comprising: a support substrate layer to be a support substrate; a solid electrolyte layer; an air electrode layer; and an active layer between the support substrate layer and the solid electrolyte layer. And
A plurality of laminates are formed by sequentially laminating an unsintered solid electrolyte layer, unsintered active layer, and unsintered support base layer on the surface of the support member
The plurality of laminates and the unfired air electrode layer are integrated to form a solid oxide fuel cell stack.
A method for producing a solid oxide fuel cell. A method for producing a solid oxide fuel cell comprising: a support substrate layer to be a support substrate; a solid electrolyte layer; an air electrode layer; and an active layer between the support substrate layer and the solid electrolyte layer. And
A plurality of laminates are formed by laminating an unsintered active layer on the surface of the unsintered support substrate layer,
The multilayer laminate and the unfired solid electrolyte layer are integrated to form an intermediate laminate,
The intermediate laminate and the unfired air electrode layer are integrated to form a solid oxide fuel cell stack,
A method for producing a solid oxide fuel cell. A method for producing a solid oxide fuel cell comprising: a support substrate layer to be a support substrate; a solid electrolyte layer; an air electrode layer; and an active layer between the support substrate layer and the solid electrolyte layer. And
A plurality of laminates are formed by sequentially laminating an unsintered solid electrolyte layer, unsintered active layer, unsintered support base layer, unsintered air electrode layer on the surface of the support member,
Forming a solid oxide fuel cell stack using the plurality of stacks;
A method for producing a solid oxide fuel cell.   5. The method for producing a solid oxide fuel cell according to claim 1, wherein the thickness of the active layer is in the range of 5 to 50 μm. A method for producing a solid oxide fuel cell comprising a fuel electrode layer, a solid electrolyte layer, and an air electrode layer,
A plurality of laminates are formed by laminating an unsintered solid electrolyte layer on the surface of the unsintered air electrode layer,
The plurality of laminates and the unfired fuel electrode layer are integrated to form a solid oxide fuel cell stack.
A method for producing a solid oxide fuel cell.   7. The method for producing a solid oxide fuel cell according to claim 1, wherein the thickness of the solid electrolyte layer is in the range of 3 to 20 μm.   Each layer included in the plurality of laminated bodies is a ceramic green sheet produced by a doctor blade method or a coater method, and the intermediate laminated body or the solid oxide fuel cell laminated body is co-fired. Item 8. A method for producing a solid oxide fuel cell according to any one of Items 1 to 7.   Each layer included in the plurality of laminates is a ceramic film prepared by a printing coating method or a spray coating method, and the intermediate laminate or the solid oxide fuel cell stack is simultaneously fired. Item 8. A method for producing a solid oxide fuel cell according to any one of Items 1 to 7. A method for producing a solid oxide fuel cell comprising a fuel electrode layer, a solid electrolyte layer, and an air electrode layer,
A ceramic green sheet constituting the unfired fuel electrode layer and a ceramic green sheet constituting the unfired solid electrolyte layer are sequentially laminated on the surface of the support member to form a plurality of laminates,
The plurality of laminates and the unfired air electrode layer are integrated to form a solid oxide fuel cell stack,
A method for producing a solid oxide fuel cell. A method for producing a solid oxide fuel cell comprising a fuel electrode layer, a solid electrolyte layer, and an air electrode layer,
A plurality of laminates in which a ceramic green sheet constituting an unfired fuel electrode layer, a ceramic green sheet constituting an unfired solid electrolyte layer, and a ceramic green sheet constituting an unfired air electrode layer are sequentially laminated on the surface of the support member Form the
Forming a solid oxide fuel cell stack using the plurality of stacks;
A method for producing a solid oxide fuel cell.   It manufactures with the manufacturing method of the solid oxide fuel cell of Claims 1-11, The solid oxide fuel cell characterized by the above-mentioned. A solid oxide fuel cell comprising the solid oxide fuel cell according to claim 12.

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