JP2018041558A - Fuel cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fuel cell having a structure for suppressing occurrence of crack at the proximal end of a support substrate.SOLUTION: A fuel cell 301 includes a support substrate 20, at least one power generation element 10 (10a), and a reinforcement film 8, where the support substrate 20 has a gas flow path 21 extending from the proximal end side 24 toward the tip side. The support substrate 20 is porous, the power generation element 10 is supported by the support substrate 20, and the reinforcement film 8 covers the internal surface defining the gas flow path, on the side closer to the proximal end than the proximal end side power generation element 10a. The reinforcement film 8 is more dense than the support substrate 20.SELECTED DRAWING: Figure 6

Description

  The present invention relates to a fuel battery cell.

  The fuel cell includes a porous support substrate having a gas flow path, and a power generation element unit supported on the support substrate. The power generation element unit includes an inner electrode (for example, a fuel electrode), an electrolyte, and an outer electrode (for example, an air electrode). The power generation element unit generates power by supplying fuel gas to the fuel electrode and supplying air to the air electrode. When the gas is supplied into the gas flow path, the gas flowing through the gas flow path is supplied to the inner electrode of the power generation element portion through the support substrate.

Japanese Patent Laying-Open No. 2015-76339

  In the fuel cell configured as described above, a crack may occur at the base end portion of the support substrate. Therefore, an object of the present invention is to suppress the occurrence of cracks at the base end portion of the support substrate.

  The present inventor believes that the base end portion of the support substrate is rapidly cooled by supplying the gas with insufficient residual heat from the base end portion side of the support substrate to the gas flow path, and cracks may occur in the inner wall surface defining the gas flow path. Found that there is. Therefore, the fuel battery cell according to an aspect of the present invention is configured as follows. That is, a fuel cell according to an aspect of the present invention includes a support substrate, at least one power generation element portion, and a reinforcing film. The support substrate has a gas flow path extending from the proximal end side toward the distal end side. The support substrate is porous. The power generation element portion is supported by the support substrate. The reinforcing film covers the inner wall surface that defines the gas flow path on the proximal end side with respect to the power generation element portion. The reinforcing film is denser than the support substrate.

  According to this configuration, as described above, the reinforcing film that is denser than the support substrate covers the inner wall surface of the gas flow path, so that even if a gas with insufficient residual heat is supplied to the gas flow path, the support film is supported. It can suppress that a crack arises in the base end part of a substrate.

  Preferably, the power generation element unit includes a plurality of power generation element units. Among the plurality of power generation element portions, the reinforcing film covers the inner wall surface on the base end side with respect to the base end side power generation element portion that is the power generation element portion disposed on the most base end side.

  Preferably, the reinforcing film is made of a dense material. According to this configuration, the gas supplied to the gas flow path can be prevented from penetrating into the support substrate from the portion covered with the reinforcing film.

  Preferably, the reinforcing film has the same main component as the support substrate. According to this configuration, the reinforcing film has a coefficient of thermal expansion that is close to that of the support substrate, so that the generation of cracks can be further suppressed.

  According to this invention, it can suppress that a crack arises in the base end part of a support substrate.

The perspective view of a fuel cell stack. Sectional drawing of a fuel cell stack. The perspective view of a fuel manifold. The perspective view of a fuel cell. Sectional drawing of a fuel cell. Sectional drawing of the base end side of a fuel cell. The figure which shows joining of a fuel battery cell and a fuel manifold. The figure which shows the supply method of air. The figure which shows the electric current which flows through the inside of a fuel cell. The figure which shows the manufacturing method of a fuel cell. The figure which shows the manufacturing method of a fuel cell. The figure which shows the manufacturing method of a fuel cell. The figure which shows the manufacturing method of a fuel cell. The figure which shows the manufacturing method of a fuel cell. The figure which shows the manufacturing method of a fuel cell. The figure which shows the manufacturing method of a fuel cell.

  Hereinafter, embodiments of a fuel cell stack using fuel cells according to the present invention will be described with reference to the drawings.

  As shown in FIGS. 1 and 2, the fuel cell stack 100 includes a fuel manifold 200 and a plurality of fuel cells 301.

[Fuel manifold]
As shown in FIG. 3, the fuel manifold 200 is configured to distribute the fuel gas to the fuel cells 301. The fuel manifold 200 is hollow and has an internal space. Fuel gas is supplied to the internal space of the fuel manifold 200 through the introduction pipe 201. The fuel manifold 200 has a plurality of through holes 202 arranged at intervals. Each through hole 202 is formed in the top plate 203 of the fuel manifold 200. Each through hole 202 communicates the internal space of the fuel manifold 200 with the outside.

[Fuel battery cell]
As shown in FIG. 2, each fuel cell 301 extends from the fuel manifold 200. Specifically, each fuel cell 301 extends upward (x-axis direction) from the top plate 203 of the fuel manifold 200. That is, the longitudinal direction (x-axis direction) of each fuel cell 301 extends upward. The base end portion of the fuel cell 301 is inserted into the through hole 202. As shown in FIG. 4, the fuel battery cell 301 includes a plurality of power generation element units 10 and a support substrate 20.

[Support substrate]
The support substrate 20 has a plurality of gas passages 21 extending along the longitudinal direction (x-axis direction) of the support substrate 20. Each gas flow path 21 extends from the proximal end side of the support substrate 20 toward the distal end side. Each gas channel 21 extends substantially parallel to each other. The base end side means the gas supply side of the gas flow path. Specifically, when the fuel battery cell 301 is attached to the fuel manifold 200, it means the side close to the fuel manifold 200. Further, the tip side means the side opposite to the gas supply side of the gas flow path. Specifically, when the fuel cell 301 is attached to the fuel manifold 200, it means the side far from the fuel manifold 200. For example, in FIG. 2 of the present embodiment, the lower side is the proximal end side, and the upper side is the distal end side.

  As shown in FIG. 5, the support substrate 20 has a plurality of first recesses 22. Each first recess 22 is formed on a pair of main surfaces 23 of the support substrate 20. The first recesses 22 are arranged at intervals in the longitudinal direction of the support substrate 20. Each first recess 22 is not formed at both ends of the support substrate 20 in the width direction (y-axis direction).

The support substrate 20 is made of a porous material that does not have electronic conductivity. The support substrate 20 can be made of, for example, CSZ (calcia stabilized zirconia). Alternatively, the support substrate 20 may be made of NiO (nickel oxide) and YSZ (8YSZ) (yttria-stabilized zirconia), or made of NiO (nickel oxide) and Y ₂ O ₃ (yttria). Alternatively, MgO (magnesium oxide) and MgAl ₂ O ₄ (magnesia alumina spinel) may be used. The porosity of the support substrate 20 is, for example, about 20 to 60%.

[Power generation element]
Each power generating element unit 10 is supported on each main surface 23 of the support substrate 20. Each power generation element unit 10 may be supported only on one main surface 23 of the support substrate 20. The power generation element units 10 are arranged at intervals in the longitudinal direction of the support substrate 20. That is, the fuel cell 301 according to the present embodiment is a so-called horizontal stripe fuel cell. The power generating element portions 10 adjacent in the longitudinal direction are electrically connected to each other by an interconnector 31.

  The power generation element unit 10 includes a fuel electrode 4, an electrolyte 5, and an air electrode 6. In addition, the power generation element unit 10 further includes a reaction preventing film 7.

[Fuel electrode]
The fuel electrode 4 is a fired body made of a porous material having electron conductivity. The fuel electrode 4 includes a fuel electrode current collector 41 and a fuel electrode active part 42.

[Fuel electrode current collector]
The fuel electrode current collector 41 is disposed in the first recess 22. Specifically, the fuel electrode current collector 41 is filled in the first recess 22 and has the same outer shape as the first recess 22. The fuel electrode current collector 41 has a second recess 411 and a third recess 412. A fuel electrode active portion 42 is disposed in the second recess 411. Further, the interconnector 31 is disposed in the third recess 412.

  The fuel electrode current collector 41 has electronic conductivity. The fuel electrode current collector 41 preferably has higher electron conductivity than the fuel electrode active part 42. The fuel electrode current collector 41 may or may not have oxygen ion conductivity.

The fuel electrode current collector 41 can be composed of, for example, NiO (nickel oxide) and YSZ (8YSZ) (yttria stabilized zirconia). Alternatively, the fuel electrode current collector 41 may be composed of NiO (nickel oxide) and Y ₂ O ₃ (yttria), or composed of NiO (nickel oxide) and CSZ (calcia stabilized zirconia). Also good. The thickness of the fuel electrode current collector 41 and the depth of the first recess 22 are about 50 to 500 μm.

[Fuel electrode active part]
The fuel electrode active portion 42 has oxygen ion conductivity and electronic conductivity. The anode active part 42 has a higher content of oxygen ion conductive material than the anode current collector 41. Specifically, the volume ratio of the substance having oxygen ion conductivity with respect to the total volume excluding the pore portion in the fuel electrode active portion 42 is determined by the oxygen ion conduction in the total volume excluding the pore portion in the fuel electrode current collector 41. It is larger than the volume ratio of the substance having the property.

  The fuel electrode active part 42 may be composed of, for example, NiO (nickel oxide) and YSZ (8YSZ) (yttria stabilized zirconia). Alternatively, the fuel electrode active part 42 may be composed of NiO (nickel oxide) and GDC (gadolinium-doped ceria). The thickness of the fuel electrode active part 42 is 5 to 30 μm.

[Electrolytes]
The electrolyte 5 is disposed so as to cover the fuel electrode 4. Specifically, the electrolyte 5 extends in the longitudinal direction from one interconnector 31 to the adjacent interconnector 31. That is, the electrolyte 5 and the interconnector 31 are alternately and continuously arranged in the longitudinal direction (x-axis direction) of the support substrate 20. The electrolyte 5 is configured to cover each main surface 23 of the support substrate 20.

  The electrolyte 5 is a fired body made of a dense material that has ionic conductivity and no electronic conductivity. The electrolyte 5 can be made of, for example, YSZ (8YSZ) (yttria stabilized zirconia). Or the electrolyte 5 may be comprised from LSGM (lanthanum gallate). The thickness of the electrolyte 5 is, for example, about 3 to 50 μm.

[Reaction prevention film]
The reaction preventing film 7 is a fired body composed of a dense material. The reaction preventing film 7 is disposed between the electrolyte 5 and the air electrode active part 61. The reaction preventing film 7 suppresses occurrence of a phenomenon in which YSZ in the electrolyte 5 and Sr in the air electrode 6 react to form a reaction layer having a large electric resistance at the interface between the electrolyte 5 and the air electrode 6. Is provided.

The reaction preventing film 7 is made of a material containing ceria containing a rare earth element. The reaction preventing film 7 can be made of, for example, GDC = (Ce, Gd) O ₂ (gadolinium-doped ceria). The thickness of the reaction preventing film 7 is, for example, about 3 to 50 μm.

[Air electrode]
The air electrode 6 is a fired body composed of a porous material having electron conductivity. The air electrode 6 is disposed on the opposite side of the fuel electrode 4 with the electrolyte 5 interposed therebetween. The air electrode 6 includes an air electrode active part 61 and an air electrode current collector 62.

[Air electrode active part]
The air electrode active part 61 is disposed on the reaction preventing film 7. The air electrode active part 61 has oxygen ion conductivity and electron conductivity. The air electrode active part 61 has a higher content of a substance having oxygen ion conductivity than the air electrode current collecting part 62. Specifically, the volume ratio of the substance having oxygen ion conductivity with respect to the total volume excluding the pore portion in the air electrode active portion 61 is determined by the oxygen ion conductivity in the air electrode current collector 62 with respect to the total volume excluding the pore portion. It is larger than the volume ratio of the substance having properties.

The air electrode active part 61 can be composed of, for example, LSCF = (La, Sr) (Co, Fe) O ₃ (lanthanum strontium cobalt ferrite). Alternatively, the air electrode active part 61 may have LSF = (La, Sr) FeO ₃ (lanthanum strontium ferrite), LNF = La (Ni, Fe) O ₃ (lanthanum nickel ferrite), or LSC = (La, Sr) CoO. ₃ (lanthanum strontium cobaltite) or the like. The air electrode active part 61 may be configured by two layers of a first layer (inner layer) composed of LSCF and a second layer (outer layer) composed of LSC. The thickness of the air electrode active part 61 is, for example, 10 to 100 μm.

[Air electrode current collector]
The air electrode current collector 62 is disposed on the air electrode active part 61. The air electrode current collector 62 extends from the air electrode active part 61 toward the adjacent power generation element part. The fuel electrode current collector 41 and the air electrode current collector 62 extend from the power generation region to opposite sides. The power generation region is a region where the fuel electrode active part 42, the electrolyte 5, and the air electrode active part 61 overlap.

  The air electrode current collector 62 is a fired body made of a porous material having electronic conductivity. The air electrode current collector 62 preferably has higher electron conductivity than the air electrode active part 61. The air electrode current collector 62 may or may not have oxygen ion conductivity.

The air electrode current collector 62 can be made of, for example, LSCF = (La, Sr) (Co, Fe) O ₃ (lanthanum strontium cobalt ferrite). Alternatively, the air electrode current collector 62 may be made of LSC = (La, Sr) CoO ₃ (lanthanum strontium cobaltite). Or the air electrode current collection part 62 may be comprised from Ag (silver) and Ag-Pd (silver palladium alloy). The thickness of the air electrode current collector 62 is, for example, about 50 to 500 μm.

[Interconnector]
The interconnector 31 is configured to electrically connect the power generating element portions 10 adjacent in the longitudinal direction (x-axis direction) of the support substrate 20. Specifically, the air electrode current collector 62 of one power generation element unit 10 extends toward the other power generation element unit 10. Further, the fuel electrode current collector 41 of the other power generating element unit 10 extends toward the one power generating element unit 10. The interconnector 31 electrically connects the air electrode current collector 62 of one power generating element unit 10 and the fuel electrode current collector 41 of the other power generating element unit 10. The interconnector 31 is disposed in the third recess 412 of the fuel electrode current collector 41. Specifically, the interconnector 31 is embedded in the third recess 412.

The interconnector 31 is a fired body composed of a dense material having electronic conductivity. The interconnector 31 can be made of, for example, LaCrO ₃ (lanthanum chromite). Alternatively, the interconnector 31 may be made of (Sr, La) TiO ₃ (strontium titanate). The thickness of the interconnector 31 is, for example, 10 to 100 μm.

[Reinforcing membrane]
As shown in FIG. 6, the reinforcing film 8 covers the inner wall surface of the gas flow path 21 at the base end side with respect to the base end side power generation element portion 10 a. In addition, the base end side power generation element part 10a means the power generation element part 10 disposed on the most base end side (the leftmost side in FIG. 6) among the plurality of power generation element parts 10 supported by each main surface 23. .

  In the longitudinal direction (x-axis direction) of the support substrate 20, the reinforcing film 8 extends from the base end surface 24 of the support substrate 20, preferably to the extent that it does not reach the fuel electrode active portion 42 of the base end side power generation element portion 10 a. More preferably, it extends so as not to reach the fuel electrode current collector 41. That is, the distal end of the reinforcing membrane 8 is preferably located on the base end side in the longitudinal direction (x-axis direction) of the support substrate 20 with respect to the base end of the fuel electrode active portion 42 of the base end side power generation element portion 10a. More preferably, it is located on the base end side of the base end of the fuel electrode current collector 41 of the base end side power generation element portion 10a.

  Further, although not particularly limited, the length of the reinforcing film 8 from the base end face 24 in the longitudinal direction (x-axis direction) of the support substrate 20 can be about 5 to 50 mm. Further, the thickness of the reinforcing film 8 can be about 10 to 200 μm.

  The reinforcing film 8 may cover not only the inner wall surface that defines the gas flow path 21 but also the base end surface 24 of the support substrate 20 and the pair of main surfaces 23 of the support substrate 20. In addition, the distal end of the reinforcing film 8 covering each main surface 23 of the support substrate 20 is preferably in the longitudinal direction (x-axis direction) of the support substrate 20, preferably the proximal end of the fuel electrode active portion 42 of the proximal end power generation element portion 10a. It is located in the base end side more, More preferably, it is located in the base end side rather than the base end of the fuel electrode current collection part 41 of the base end side electric power generation element part 10a. For example, the tip of the reinforcing film 8 that covers the inner wall surface that defines the gas flow path 21 and the tip of the reinforcing film 8 that covers the pair of main surfaces 23 of the support substrate 20 are the longitudinal direction (x-axis direction) of the support substrate 20. In FIG. Note that the distal end portion of the reinforcing film 8 covering each main surface 23 of the support substrate may cover the proximal end portion of the electrolyte 5.

The reinforcing film 8 is denser than the support substrate 20. Preferably, the reinforcing film 8 is made of a dense material. For example, the porosity of the reinforcing membrane 8 can be about 10% or less. The reinforcing film 8 preferably has the same main component as the support substrate 20. The reinforcing film 8 can be made of, for example, MgO—MgAl ₂ O ₄ , MgO—Y ₂ O ₃ , CaZrO ₃ , or the like.

[Current collecting member]
The fuel cell 301 configured as described above is electrically connected to the adjacent fuel cell 301 by the current collecting member 302. As shown in FIG. 2, the current collecting member 302 is disposed between the pair of fuel cells 301. And the current collection member 302 has electroconductivity so that the fuel cell 301 adjacent in the thickness direction (z-axis direction) may be electrically connected. Specifically, the current collecting member 302 connects adjacent fuel cells 301 on the base end side of the fuel cells 301. The current collecting member 302 is disposed on the base end side with respect to the base end side power generation element portion 10a. Specifically, as shown in FIG. 6, the current collecting member 302 is disposed on the air electrode current collecting portion 62 extending from the proximal end side power generation element portion 10 a.

The current collecting member 302 has, for example, a block shape such as a rectangular parallelepiped shape or a cylindrical shape. The current collecting member 302 is made of, for example, a fired body of oxide ceramics. Examples of such oxide ceramics include perovskite oxide and spinel oxide. Examples of the perovskite oxide include (La, Sr) MnO ₃ , (La, Sr) (Co, Fe) O _{3, and the} like. Examples of the spinel oxide include (Mn, Co) ₃ O ₄ , (Mn, Fe) ₃ O _{4, and the} like. For example, the current collecting member 302 does not have flexibility. The current collecting member 302 may be formed of a metal plate or the like.

The current collecting member 302 is joined to each fuel cell 301 by the first joining material 101. That is, the first bonding material 101 joins each current collecting member 302 and each fuel cell 301. The first bonding material 101 is, for example, at least one selected from the group consisting of (Mn, Co) ₃ O ₄ , (La, Sr) MnO _3, (La, Sr) (Co, Fe) O _{3, and the} like. .

  As shown in FIG. 2, each fuel cell 301 is supported by the fuel manifold 200. Specifically, each fuel cell 301 is fixed to the top plate 203 of the fuel manifold 200 by the second bonding material 102. More specifically, as shown in FIG. 7, the base end portion of each fuel cell 301 is inserted into the through hole 202 of the fuel manifold 200. The fuel cell 301 is fixed to the fuel manifold 200 by the second bonding material 102 in a state of being inserted into the through hole 202.

The second bonding material 102 is filled in the through hole 202 in a state where the fuel battery cell 301 is inserted. That is, the second bonding material 102 is filled in a gap between the outer peripheral surface of the fuel cell 301 and the wall surface that defines the through hole 202. The second bonding material 102 is, for example, crystallized glass. As the crystallized glass, for example, a SiO ₂ —B ₂ O ₃ system, a SiO ₂ —CaO system, or a SiO ₂ —MgO system may be employed. In this specification, crystallized glass means that the ratio (crystallinity) of “volume occupied by crystal phase” to the total volume is 60% or more, and “volume occupied by amorphous phase and impurities relative to the total volume”. "Indicates a glass having a ratio of less than 40%. As the material of the second bonding material 102, amorphous glass, brazing material, ceramics, or the like may be employed. Specifically, the second bonding material 102 is at least one selected from the group consisting of SiO ₂ —MgO—B ₂ O ₅ —Al ₂ O ₃ and SiO ₂ —MgO—Al ₂ O ₃ —ZnO. .

  The length of each fuel cell 301 protruding from the fuel manifold 200 in the longitudinal direction (x-axis direction) can be about 100 to 300 mm. The fuel cells 301 are arranged at intervals in the thickness direction (z-axis direction) of the fuel cells 301. The interval between the fuel cells 301 can be about 1 to 5 mm.

[Power generation method]
The fuel cell stack 100 configured as described above generates power as follows. A fuel gas (hydrogen gas or the like) is caused to flow into the gas flow path 21 of each fuel cell 301 through the fuel manifold 200, and both surfaces of the support substrate 20 are exposed to a gas (air or the like) containing oxygen.

  For example, as shown in FIG. 8, the oxygen-containing gas is supplied to the base end side from the base end side power generation element portion 10 a so as to flow along the width direction (y-axis direction) of the support substrate 20. Specifically, the fuel cell stack 100 further includes a gas supply member 400. The gas supply member 400 is configured to supply a gas such as air between the fuel cells 301. Note that the guide plate 401 may be installed on the opposite side of the gas supply member 400 so that the gas supplied from the gas supply member 400 efficiently flows upward. The guide plate 401 has a flat plate shape and extends in the longitudinal direction of the fuel cell 301 and also extends in the thickness direction of the fuel cell 301.

As described above, in each power generation element unit 10 supplied with the fuel gas and the gas containing oxygen, an electromotive force is generated due to an oxygen partial pressure difference generated between both side surfaces of the electrolyte 5. When this fuel cell stack 100 is connected to an external load, an electrochemical reaction represented by the following formula (1) occurs in the air electrode 6, and an electrochemical reaction represented by the following formula (2) occurs in the fuel electrode 4, causing a current to flow. .
(1/2) · O ₂ + 2e ⁻ → O ₂ ⁻ (1)
H ₂ + O ₂ ⁻ → H ₂ O + 2e ⁻ (2)
In the power generation state, current flows as shown by arrows in FIG. In the interconnector 31 and the power generation element unit 10, a current flows in the thickness direction.

[Production method]
Next, a method for manufacturing the fuel battery cell configured as described above will be described. 10 to 16, “g” at the end of the reference numeral of each member indicates that the member is not fired.

  First, as shown in FIG. 10, a support substrate molded body 20g is prepared. The support substrate molded body 20g is produced by using a method such as extrusion molding or cutting using a slurry obtained by adding a binder or the like to the material of the support substrate 20 (for example, CSZ). Can be done.

  When the support substrate molded body 20g is manufactured, next, as shown in FIG. 11, the first electrode 22 is formed in each main surface 23 of the support substrate molded body 20g. The compact 41g is filled. The molded body 41g of the fuel electrode current collector is produced by, for example, a printing method using a slurry obtained by adding a binder or the like to the powder of the material of the fuel electrode current collector 41 described above.

  Next, as shown in FIG. 12, a molded film 42 g of the fuel electrode active portion is formed in each second recess 411 of the molded body 41 g of the fuel electrode current collector. The formed film 42g is formed by, for example, a printing method using a slurry obtained by adding a binder or the like to the powder of the material for the fuel electrode active portion 42 described above.

  Also, an interconnector molded film 31g is formed in each third recess 412 of the molded body 41g of each fuel electrode current collector. The molded film 31g of each interconnector is formed by, for example, a printing method using a slurry obtained by adding a binder or the like to the powder of the material of the interconnector 31 described above.

  Next, as shown in FIG. 13, an electrolyte molding film 5g is formed on the molding film 42g of the fuel electrode active portion. Specifically, the tip of the electrolyte molding film 5g is disposed on the interconnector molding film 31g. The base end portion of another electrolyte molding film 5g is also disposed on the molding film 31g of the same interconnector. As a result, each main surface 23 of the molded body 20g of the support substrate in a state where the molded body 41g of the fuel electrode current collector and the molded film 42g of the fuel electrode active part are formed are formed on the molded film 31g of the interconnector and the electrolyte. Is covered with 5 g of the molding film. The electrolyte molded film 5g is formed by, for example, a printing method or a dipping method using a slurry obtained by adding a binder or the like to the powder of the material of the electrolyte 5 described above.

  Next, as shown in FIG. 14, a reaction preventive film 7g is formed on the electrolyte film 5g. The molded film 7g of each reaction preventing film is formed by, for example, a printing method using a slurry obtained by adding a binder or the like to the powder of the material of the reaction preventing film 7 described above.

  Further, a reinforcing membrane 8 g is formed so as to cover the inner wall surface that defines the gas flow path 21. Specifically, the reinforcing membrane molding film 8g is formed so as to cover the inner wall surface of the gas flow path 21 on the base end side of the base end side power generation element portion 10a. Further, a molding film 8g of a reinforcing film is formed so as to cover the base end surface 24 and each main surface 23 of the molded body 20g of the support substrate. On each main surface 23, the distal end portion of the reinforcing membrane molding film 8g may be formed on the proximal end portion of the electrolyte molding membrane 5g.

  Then, 20 g of the support substrate molded body in which various molded films are thus formed is fired in air at about 1200 to 1600 ° C. for about 1 to 10 hours. Thereby, the fuel battery cell in the state where the air electrode 6 is not formed is obtained.

  Next, as shown in FIG. 15, a forming film 61 g of the air electrode active portion is formed on each reaction preventing film 7. The molded film 61g of each air electrode active portion is formed by a printing method or the like using a slurry obtained by adding a binder or the like to the powder of the material of the air electrode active portion 61 described above.

  Next, as shown in FIG. 16, a forming film 62g of the air electrode current collector is formed on the forming film 61g of the air electrode active part. Specifically, the molding film 62g of the air electrode current collector is formed to extend from the molding film 61g of the air electrode active part toward the adjacent power generation element part. Further, the molding film 62g of the air electrode current collector of the base end side power generation element unit 10a extends from the molding film 61g of the air electrode active part toward the base end side. The molded film 62g of each air electrode current collector is formed by, for example, a printing method using a slurry obtained by adding a binder or the like to the powder of the material of the air electrode current collector 62 described above.

  The support substrate 20 in which the air electrode forming films 61g and 62g are thus formed is fired in air at about 900 to 1200 ° C. for about 1 to 10 hours. Thereby, the fuel cell 301 is completed.

[Modification]
As mentioned above, although embodiment of this invention was described, this invention is not limited to these, A various change is possible unless it deviates from the meaning of this invention.

Modification 1
In the above embodiment, the support substrate 20 has a flat plate shape, but may have a cylindrical shape. That is, the fuel battery cell 301 may be cylindrical.

Modification 2
In the above embodiment, the fuel electrode current collector 41 has the second recess 411 and the third recess 412, but the configuration of the fuel electrode current collector 41 is not limited to this. For example, the fuel electrode current collector 41 may not have concave portions such as the second concave portion 411 and the third concave portion 412. In this case, the anode active portion 42 is formed on the anode current collector 41 and is not embedded in the anode current collector 41. The interconnector 31 is formed on the anode current collector 41 and is not embedded in the anode current collector 41.

8: Reinforcing membrane 10: Support substrate 10: Power generation element portion 10a: Base end side power generation element portion 20: Support substrate 21: Gas flow path 301: Fuel cell

Claims (4)

A porous support substrate having a gas flow path extending from the proximal side toward the distal side;
At least one power generation element portion supported by the support substrate;
Covering the inner wall surface defining the gas flow path on the base end side from the power generation element portion, a reinforcing film denser than the support substrate;
A fuel cell.
The power generation element unit includes a plurality of the power generation element units,
Among the plurality of power generating element portions, the reinforcing film covers the inner wall surface on the base end side relative to the base end side power generating element portion which is the power generating element portion disposed on the most base end side.
The fuel battery cell according to claim 1.
The reinforcing film is composed of a dense material.
The fuel battery cell according to claim 1 or 2.
The reinforcing film has the same main component as the support substrate,
The fuel cell according to any one of claims 1 to 3.

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