JP2012022856A - Solid oxide fuel cell and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid oxide fuel cell and method for manufacturing the same, capable of attaining high generation efficiency by suppressing generation of a leak current.SOLUTION: On an external surface of a substrate tube 11 in a tubular shape, a fuel battery cell (power generation element) 210 is formed by stacking a fuel electrode 12, a solid electrolyte 13, and an air electrode 14. The plurality of fuel battery cells (power generation elements) 210 are disposed at predetermined intervals in the axial direction of the substrate tube 11 and are connected with each other in series by through an inter-connector 15. Also, an electrical resistance value of 1000 Ω or more is set between the fuel electrodes 12.

Description

  The present invention relates to a solid oxide fuel cell having a cylindrical shape and a method for manufacturing the same.

  A solid oxide fuel cell (SOFC) is a fuel cell that generates electric power by an electrochemical reaction between a fuel gas reformed by reacting a hydrocarbon or oxygen-containing hydrocarbon with water vapor and oxygen. During this power generation, water is generated. When the reverse reaction of the fuel cell is performed, hydrogen and oxygen are generated from water. Such an apparatus is called a water electrolysis apparatus.

  A cylindrical solid oxide fuel cell is known as one embodiment of the solid oxide fuel cell. In this cylindrical solid oxide fuel cell, a power generation element is formed by laminating a fuel electrode, a solid oxide electrolyte, and an air electrode on the outer peripheral surface of a cylindrical base tube. A plurality of power generating elements are connected in series by an interconnector.

  Therefore, when fuel gas is supplied into the base tube and oxygen is supplied to the air electrode, the oxygen supplied to the air electrode is ionized and permeates the electrolyte membrane and reaches the fuel electrode. A potential difference is generated between the fuel electrode and the air electrode due to an electrochemical reaction between oxygen and fuel gas that has reached the fuel electrode, and electricity is generated by taking out the generated potential difference to the outside.

  By the way, it is desirable that the base tube be an insulator from the viewpoint of suppressing leakage current. However, the base tube needs to have the same or lower thermal expansion coefficient as that of the fuel electrode for the purpose of preventing the occurrence of cracks during sintering. In addition, since the fuel gas and oxygen need to pass through the base tube, it is necessary to ensure a predetermined porosity. Therefore, it is necessary to contain an iron group metal oxide (for example, nickel oxide) as the sintered material, and as a result, the base tube has conductivity. As a result, in the conventional solid oxide fuel cell, a leakage current flowing from the power generation element to the base tube is generated, resulting in consumption of fuel during non-energization and an increase in fuel consumption during energization, resulting in a decrease in power generation efficiency. It was thought that there was a problem of doing.

  As what solves such a problem, there exists a thing described in the following patent document 1, for example. In the fuel cell described in Patent Document 1, a power generation element in which a fuel electrode, a solid electrolyte, and an air electrode are stacked on the surface of a columnar support body in which a fuel gas flow path is formed in the axial direction is axially long. A plurality of power generating elements are connected in series by interconnectors, and the support is made of an iron group metal and / or an iron group metal oxide and an inorganic powder. A porous insulating layer that electrically insulates the support base from the power generating element is provided on the surface of the porous support base as a main component.

JP 2004-179071 A

  In the conventional fuel cell described above, a porous insulating layer that is electrically insulated from the power generation element is provided on the surface of the support, thereby suppressing the occurrence of leakage current between the power generation element and the base tube. ing. By the way, the fuel cell is configured such that a fuel electrode, a solid electrolyte, and an air electrode are laminated on the outside of a base tube, and a plurality of them are arranged in the axial direction and connected in series by an interconnector. In this case, a solid electrolyte is disposed between the fuel electrodes adjacent to each other in the axial direction of the base tube, and since this solid electrolyte has very low electronic conductivity, almost no leakage current is generated. It was thought. However, although the solid electrolyte has a low electronic conductivity as described above, the ionic conductivity is not small, and the leakage current through the solid electrolyte is more problematic than the leakage current through the substrate tube described above. It turns out that there is a possibility.

  Further, in the future, it is necessary to increase the number of elements in order to increase the output by reducing the ohmic overvoltage by increasing the voltage or reducing the current of the fuel cell. On the other hand, in order to reduce the size of the fuel cell, it is necessary to reduce the element spacing as much as possible while securing the effective power generation unit in the process of increasing the number of elements. With such a configuration, there is a problem that the energization distance between the elements is shortened and the above-described leakage current is increased. Furthermore, in a solid oxide fuel cell equipped with a solid electrolyte membrane having high ionic conductivity at high temperatures, power generation efficiency can be improved as the reaction temperature in the power generation element is increased. Since the electrical resistance between the power generation elements is reduced, there is also a problem that the above-described leakage current is increased.

  The present invention solves the above-described problems, and an object of the present invention is to provide a solid oxide fuel cell that suppresses generation of leakage current and improves power generation efficiency and a method for manufacturing the same.

  In order to achieve the above object, a solid oxide fuel cell of the present invention includes a base tube having a cylindrical shape, and a plurality of fuel cells arranged on the outer peripheral surface of the base tube along the axial direction of the base tube. It has a power generation element in which an electrolyte and an air electrode are laminated, and an interconnector that connects adjacent power generation elements in series, and an electrical resistance value between the adjacent fuel electrodes is 1000Ω or more. It is a feature.

  Therefore, by setting an electric resistance value of 1000Ω or more between the fuel electrodes, it is possible to suppress the occurrence of leakage current through the solid electrolyte between the fuel electrodes. For this reason, it is possible to prevent a decrease in the element voltage, and as a result, it is possible to improve the power generation efficiency.

  The solid oxide fuel cell of the present invention is characterized in that an insulating portion that suppresses movement of electrons and ions is provided between the adjacent power generation elements.

  Therefore, by providing an insulating portion between the power generation elements, the generation of leakage current can be suppressed, so that the element voltage can be prevented from being lowered, and the power generation efficiency can be improved with a simple configuration.

  In the solid oxide fuel cell according to the aspect of the invention, the insulating portion may be disposed between the fuel electrode of one of the power generation elements and the fuel electrode of the other power generation element in the adjacent power generation elements. The power generating element is provided between the solid electrolyte and the base tube.

  Therefore, by providing an insulating portion between the base electrode and the solid electrolyte between the fuel electrodes, it is possible to suppress the generation of leakage current and prevent a decrease in device voltage, and to improve power generation efficiency with a simple configuration. be able to.

  In the solid oxide fuel cell according to the aspect of the invention, the insulating portion may be disposed between the fuel electrode of one of the power generation elements and the fuel electrode of the other power generation element in the adjacent power generation elements. The power generating element is provided between the solid electrolyte and the interconnector.

  Therefore, by providing an insulating portion between the solid electrolyte and the interconnector between the fuel electrodes, it is possible to suppress the occurrence of leakage current and prevent a decrease in element voltage, and to improve power generation efficiency with a simple configuration. be able to.

  The solid oxide fuel cell according to the present invention is characterized in that a reaction preventing portion is provided between the power generating element and the insulating portion.

  Therefore, the reaction prevention unit prevents a reaction between the power generation element and the insulating unit, thereby preventing formation of a non-insulating layer and preventing element diffusion and lowering of power generation efficiency. can do.

  In the solid oxide fuel cell of the present invention, the insulating part is an electrolyte reaction part formed by a chemical reaction with the solid electrolyte.

  Therefore, it is possible to reduce the thickness of the insulating portion, thereby enabling a reduction in the size of the device and reducing the manufacturing cost.

  The solid oxide fuel cell manufacturing method of the present invention includes a step of forming a base tube, and a plurality of fuel electrode material films are formed on the outer peripheral surface of the base tube along the axial direction of the base tube. A step of sequentially laminating a solid electrolyte material film and an interconnector material film on the upper surface of the fuel electrode material film, and a plurality of outer peripheral surfaces of the base tube along the axial direction of the base tube. A step of forming an insulating part material film, sintering the insulating part material film, the fuel electrode material film, the solid electrolyte material film, and the interconnector material film; And a step of forming a solid electrolyte and an interconnector, and an electrical resistance value between adjacent fuel electrodes is 1000Ω or more.

  Therefore, by laminating and sintering the fuel electrode material film, the solid electrolyte material film, the interconnector material film, and the insulating material film on the base tube, the fuel electrode, solid electrolyte, and interconnector are formed on the base tube. Insulating portions can be formed, and the manufacturing process can be simplified. Moreover, by setting an electric resistance value of 1000Ω or more between the fuel electrodes by the insulating portion, it is possible to suppress the occurrence of a leakage current that dissolves the solid electrolyte between the fuel electrodes. Thereby, the fall of element voltage can be prevented and, as a result, improvement in power generation efficiency can be aimed at.

  In the method for manufacturing a solid oxide fuel cell according to the present invention, after forming the insulating material film, the fuel electrode material film is formed, and then the solid electrolyte material film and the interconnector material film are formed. It is characterized by being sequentially laminated.

  Therefore, since the insulating part is covered with the fuel electrode or the solid electrolyte, it is not necessary to form the insulating part densely, it is not necessary to consider the sinterability, and the manufacturing cost can be reduced.

  In the method for producing a solid oxide fuel cell according to the present invention, after forming the fuel electrode material film, the insulating material film is formed, and then the solid electrolyte material film and the interconnector material film are formed. It is characterized by being sequentially laminated.

  Therefore, since the insulating part is covered with the fuel electrode or the solid electrolyte, it is not necessary to form the insulating part densely, it is not necessary to consider the sinterability, and the manufacturing cost can be reduced.

  In the solid oxide fuel cell manufacturing method of the present invention, the insulating material film is formed after the solid electrolyte material film and the interconnector material film are sequentially laminated.

  Therefore, by interposing an insulating part between the fuel electrodes or between the solid electrolytes, high insulation can be ensured, and the manufacturing cost can be reduced.

  The method for producing a solid oxide fuel cell according to the present invention is characterized in that after the insulating part material film is formed, a reaction preventing part material film is formed on the outer surface of the insulating part material film.

  Therefore, reaction between the power generating element and the insulating part during sintering is prevented by the reaction preventing part, and generation of a layer having no insulating property can be prevented. In addition, the reaction preventing unit can prevent the element from diffusing between the power generation element and the insulating unit. Thereby, the fall of power generation efficiency can be prevented.

  In the method for producing a solid oxide fuel cell according to the present invention, after forming the fuel electrode material film, an electrolyte reaction part is applied to the opposing surface of the fuel electrode material film adjacent in the axial direction of the base tube. The fuel electrode material film, the electrolyte reaction part, the solid electrolyte material film, and the interconnector material film are sintered, and the fuel electrode, the insulating part, The solid electrolyte and the interconnector are formed.

  Therefore, by forming the electrolyte reaction part into an insulating part by sintering, the insulating part can be made thin, and the apparatus can be miniaturized and the manufacturing cost can be reduced.

  According to the solid oxide fuel cell and the method for manufacturing the same of the present invention, an electric resistance value of 1000Ω or more is set between the power generation elements, so that a decrease in the element voltage is prevented and leakage current is generated. As a result, the power generation efficiency can be improved.

FIG. 1 is a schematic configuration diagram illustrating a fuel cell according to Embodiment 1 of the present invention. FIG. 2 is a graph showing the element voltage and the leakage current with respect to the element unit resistance. FIG. 3 is a schematic view illustrating a method for manufacturing the fuel cell of Example 1. FIG. 4 is a schematic configuration diagram illustrating a fuel cell module according to the first embodiment. FIG. 5 is a schematic diagram showing a fuel cell and a manufacturing method thereof according to Example 2 of the present invention. FIG. 6 is a schematic diagram showing a fuel cell and a manufacturing method thereof according to Example 3 of the present invention. FIG. 7 is a schematic diagram showing a fuel cell and a manufacturing method thereof according to Example 4 of the present invention. FIG. 8 is a schematic view showing a fuel cell and a manufacturing method thereof according to Example 5 of the present invention. FIG. 9 is a schematic view showing a fuel cell and a manufacturing method thereof according to Example 6 of the present invention. FIG. 10 is a table showing appropriate materials for the insulating portions in the fuel cells of Examples 1 to 6.

  Exemplary embodiments of a fuel cell and a method for manufacturing the same according to the present invention will be described below in detail with reference to the accompanying drawings. In addition, this invention is not limited by this Example.

  1 is a schematic configuration diagram showing a fuel cell according to a first embodiment of the present invention, FIG. 2 is a graph showing an element voltage and a leakage current with respect to an element portion resistance, and FIG. 3 is a method for manufacturing the fuel cell of the first embodiment. FIG. 4 is a schematic configuration diagram illustrating a fuel cell module in the fuel cell system according to the first embodiment.

  As shown in FIG. 4, the fuel cell module 101 according to the first embodiment includes a casing 201, a plurality of cell tubes 202 formed in a substantially cylindrical shape, and upper and lower tube plates that support both ends of the cell tubes 202 (first Partition members) 203a and 203b and upper and lower heat insulators 204a and 204b disposed between the upper and lower tube plates 203a and 203b.

  A power generation chamber 205 is formed in a space between the upper and lower heat insulators 204a and 204b. A fuel supply chamber 206 is formed between the casing 201 and the upper tube plate 203a. A fuel discharge chamber 207 is formed between the casing 201 and the lower tube plate 203b. An air supply chamber 208 is formed between the lower tube sheet 203b and the lower heat insulator 204b. An air discharge chamber 209 is formed between the upper tube sheet 203a and the upper heat insulator 204a.

  The upper tube plate 203a is a plate-like member arranged on one side (upper side) of the casing 201 in the longitudinal direction (vertical direction in FIG. 4), and the lower tube plate 203b is the other of the casing 201 in the longitudinal direction (lower side) ) Is a plate-shaped member. The cell tube 202 is a substantially cylindrical tube made of porous ceramics, and is provided with a plurality of fuel cells 210 that generate power at the center in the longitudinal direction (vertical direction in FIG. 5). The cell tube 202 is supported by the upper and lower tube plates 203a and 203b so that one open end opens into the fuel supply chamber 206 and the other open end opens into the fuel discharge chamber 207. Further, the cell tube 202 is arranged so that the fuel battery cell (power generation element) 210 is located only in the power generation chamber 205.

  The upper heat insulator 204a is a member that is disposed on one side (upper side) of the casing 201 in the longitudinal direction and is formed into a blanket shape or a board shape using a heat insulating material. The lower heat insulating material 204b is a member that is disposed on the other side (lower side) of the casing 201 in the longitudinal direction and formed in a blanket shape or a board shape using a heat insulating material. The heat insulators 204a and 204b are formed with holes 211a and 211b through which the cell tube 202 is inserted. The diameters of the holes 211a and 211b are larger than the diameter of the cell tube 202.

  The inner peripheral surfaces of the holes 211a and 211b may be formed in a substantially cylindrical shape, or may be formed with a spiral or linear concave portion (groove) or convex portion (a ridge-like projection), There is no particular limitation. With such a configuration, the heat of the lower heat insulator 204b is easily transferred to the air flowing into the power generation chamber 205 through the space between the cell tube 202 and the holes 211a and 211b, and the temperature of the power generation chamber 205 is reduced. It can be easily maintained at a high temperature.

  Here, the outline | summary of operation | movement of the fuel cell module 101 which consists of the said structure is demonstrated using FIG.

  Air flows into the air supply chamber 208 of the fuel cell module 101. The air is supplied into the power generation chamber 205 through a gap between the hole 211 b of the lower heat insulating material 204 b and the cell tube 202. On the other hand, fuel gas flows into the fuel supply chamber 206. The fuel gas is supplied into the power generation chamber 205 through the inside of the base tube of the cell tube 202. Air and fuel gas are used for power generation in the fuel battery cell 210. Thereafter, air flows into the air discharge chamber 209, and fuel flows into the fuel discharge chamber 208, and is discharged to the outside of the fuel cell module 101, respectively.

  At this time, the air and the fuel gas flow in opposite directions on the inner surface or outer surface of the cell tube 202. As a result, the fuel gas and air that have been used for power generation and have reached a high temperature are each subjected to heat exchange with the air and fuel gas before being used for power generation. That is, heat is exchanged between the fuel and air in the region where the fuel cell 202 is not formed at both ends in the axial direction of the cell tube 202.

  As described above, in the fuel cell module 101, the fuel gas and air that have been used for the reaction and become high temperature are cooled by heat exchange, and then supplied to the fuel discharge chamber 208 and the air discharge chamber 209. This can prevent the upper tube plate 203a and the lower tube plate 203b having metal members from being exposed to a high temperature atmosphere. As a result, in the fuel cell module 101, the operating temperature of the fuel cell 210 can be increased, for example, from 800 ° C. to 950 ° C.

  Next, the cell tube (fuel cell) 202 used in the fuel cell module 101 of the fuel cell system described above will be described in detail.

  As shown in FIG. 1, the cell tube (fuel cell) 202 of Example 1 has a fuel electrode 12, a solid electrolyte 13, and an air electrode 14 laminated on the outer surface of a cylindrical base tube 11 facing outward. A power generation element, that is, a fuel cell 210 is formed, a plurality of fuel cells 210 are arranged in the axial direction of the base tube 11, and a plurality of fuel cells 210 are connected in series by an interconnector 15. . In this embodiment, the electric resistance value between the fuel electrodes 12 adjacent in the axial direction of the base tube 11 is set to 1000Ω or more. Specifically, an insulating film (insulating portion) 16 that insulates electricity and ions is provided between the plurality of fuel cells 210.

  Here, the electric resistance value between the fuel electrodes 12 is defined as an electric resistance value of a leakage current path (leakage current path through the solid electrolyte) between the fuel electrodes 12.

The cell tube 202 of Example 1 will be specifically described. The base tube 11 is a ceramic cylinder and contains an iron group metal (for example, Ni), an iron group metal oxide (for example, NiO) having an internal reforming ability, an alloy or an alloy oxide thereof. Yes, for example, a mixture of Ni and CSZ (calcia stabilized zirconia-CaO stabilized ZrO ₂ ). A fuel passage is formed by the inner peripheral surface of the base tube 11. In this case, since the base tube 11 needs to pass the fuel gas flowing through the fuel passage to the fuel electrode 12, it must be made porous, and the particle diameter of the mixture can be adjusted or the pore material can be mixed. It is necessary.

The fuel electrode 12 is, for example, a mixture of Ni and YSZ (yttrium stabilized zirconia-Y ₂ O ₃ stabilized ZrO ₂ ), has conductivity, and is a porous material. A solid electrolyte 13 is laminated on the surface of the fuel electrode 12 opposite to the base tube 11, and is formed so as to exist between the fuel electrode 12 adjacent in the axial direction of the base tube 11. The solid electrolyte 13 is, for example, YSZ (yttrium stabilized zirconia-Y ₂ O ₃ stabilized ZrO ₂ ), and is nonporous in order to avoid contact between the fuel electrode gas and the air electrode gas. The air electrode 14 is made of, for example, at least one kind of porous conductive ceramics such as a LaMnO ₃ -based material, a LaFeO ₃ -based material, and a LaCoO ₃ -based material.

In order to configure the cell tube 202, in the fuel cell 210 adjacent in the axial direction of the base tube 11, the fuel electrode 12 of one fuel cell 210 and the air electrode 14 of the other fuel cell 210 are Connected by an interconnector 15. A part of the fuel electrode 12 is covered with a solid electrolyte, and a part thereof is covered with an interconnector 15. The interconnector 15 is made of, for example, a perovskite oxide such as SrTiO ₃ , a LaCrO ₃ -based material, or the like, and is non-porous to prevent gas leakage. Thus, since the interconnector is not a metal material, it does not deteriorate due to oxidation or the like at high temperatures. Accordingly, the operating temperature of the fuel battery cell 210 can be increased, for example, 800 ° C. to 950 ° C.

  The insulating film 16 is disposed between the plurality of fuel cells 210 in the axial direction of the base tube 11, specifically, between the adjacent fuel electrodes 12, and between the base tube 11 and the solid electrolyte 13. Is provided. In this case, it is desirable that the insulating film 16 has substantially the same thermal expansion coefficient (thermal expansion coefficient) as that of the fuel electrode 12, the solid electrolyte 13, and the air electrode 14.

  In addition, since the cell tube 202 of the present embodiment is formed by laminating the insulating film 16, the fuel electrode 12, the solid electrolyte 13, the interconnector 15, and the air electrode 14 on the outer surface of the base tube 11, this sintering is performed. It is necessary to be careful of cracks in time. Therefore, the material composition of the insulating film 16 is set so that the thermal expansion coefficient is substantially the same as that of the base tube 11, the fuel electrode 12, the solid electrolyte 13, the interconnector 15, and the air electrode 14.

  The insulating film 16 needs to have an insulating function between the adjacent fuel electrodes 12, and is set to a resistance value that does not lower the power generation efficiency due to the consumption of fuel when not energized and the increase in the amount of fuel used when energized. ing. In this case, the insulating film 16 is set to have a low electronic conductivity and low ionic conductivity so that not only electrons but also ions cannot pass through.

  In the graph of FIG. 2, the element voltage and leakage current with respect to element part resistance (resistance between fuel electrodes) in a general cell tube are shown. As can be seen from the graph of FIG. 2, when the element portion resistance (resistance between fuel electrodes) decreases, the leakage current A increases from the predetermined element portion resistance value. When the element section resistance (resistance between fuel electrodes) decreases, both the element voltage V1 when 50 fuel cell units 210 are provided and the element voltage V2 when 100 fuel cell units 210 are provided are predetermined elements. The resistance value has decreased. The element voltage V is an element voltage when no current flows, and the theoretical electromotive force is 1.2 V under 900 ° C., fuel electrode dry hydrogen, and air electrode air conditions.

  That is, when the electric resistance (insulation resistance) value between the fuel electrodes 12 becomes smaller than 1000Ω, the leakage current A increases, and the element voltages V1 and V2 decrease when the element portion resistance value becomes smaller from 1000Ω. . From this, it can be seen that by setting the electric resistance value between the fuel cells 210 to 1000Ω or more, the generation of the leakage current A can be suppressed and the decrease of the element voltage V can be prevented.

Hereinafter, a method of setting the electric resistance value between the fuel electrodes 12 to 1000Ω or more will be described. The electric resistance value R can be calculated by the following mathematical formula.
R = (1 / σ) × (L / SF)

Here, σ is the conductivity (S / cm) between the fuel electrodes 12 adjacent in the axial direction of the base tube 11. SF is an opposing area in the axial direction of the base tube 11 between the fuel electrodes 16 adjacent in the axial direction of the base tube 11. Further, as shown in FIG. 1, L is an average length (an average distance in the axial direction of the base tube 11) between the fuel electrodes 12 adjacent in the axial direction of the base tube 11, and is calculated as follows. Can do.
L = (Lmax−Lmin) / 2
Lmax is the maximum length of the interval between the fuel electrodes 12 adjacent in the axial direction of the base tube 11, and Lmin is the minimum length of the interval between the fuel electrodes 12 adjacent in the axial direction of the base tube 11.

Therefore, the electrical conductivity σ between the fuel electrodes 12 that satisfies the following formula, the average length L of the interval between the fuel electrodes 12, and the opposing area SF in the axial direction of the base tube 11 between the adjacent fuel electrodes 16 may be set. .
R = (L / σ · SF) ≧ 1000
In general, in order to maintain the performance of the cell tube 202, it is difficult to change the average length L of the interval between the fuel electrodes 12. Therefore, by providing the insulating film 16 having a conductivity close to zero between the fuel electrodes 12 and reducing the facing area between the fuel electrodes 12, the electric resistance value between the fuel electrodes 12 satisfying the above formula is set. .

  However, the electrical resistance value between the fuel cells 210 is set to 1000Ω or more by increasing the average length L of the interval between the fuel electrodes 12 as much as possible or by reducing the thickness of the fuel electrode 12. It may be.

  Here, the manufacturing method of the cell tube (fuel cell) 202 of Example 1 mentioned above is demonstrated.

  As shown in FIG. 3, the manufacturing method of the cell tube (fuel cell) 202 according to the first embodiment includes a step of forming the base tube 11, and a plurality of steps along the axial direction of the base tube 11 on the outer peripheral surface of the base tube 11. A step of forming the fuel electrode material film 22; a step of sequentially laminating the solid electrolyte material film 23 and the interconnector material film 25 on the upper surface of the fuel electrode material film 22; A step of forming a plurality of insulating part material films 26 along the axial direction of the base tube 11, the insulating part material film 26, the fuel electrode material film 22, the solid electrolyte material film 23, and the interconnector. A step of sintering the material film 25 to form the insulating film 16, the fuel electrode 12, the solid electrolyte 13, and the interconnector 15, so that the electric resistance value between the adjacent fuel electrodes 12 is 1000Ω or more. Is set.

  More specifically, the base tube 11 is formed on a cylindrical mandrel (not shown), and the insulating film material film 26 is first formed on the surface of the base tube 11 at predetermined intervals in the axial direction of the base tube 11. Form. Next, the fuel electrode material film 22, the solid electrolyte material film 23, and the interconnector material film 25 are laminated on the surfaces of the base tube 11 and the insulating film material film 26. In this case, the insulating film material film 26, the fuel electrode material film 22, the solid electrolyte material film 23, and the interconnector material film 25 were mixed uniformly by mixing the above-described powder material with an organic solvent. A slurry is formed, and a predetermined material is applied to a predetermined position by a screen printing method.

Then, in a state where the insulating film material film 26, the fuel electrode material film 22, the solid electrolyte material film 23, and the interconnector material film 25 are laminated on the base tube 11, sintering (for example, at 1350 ° C., 1 Hold time).
The air electrode material film 24 is laminated on the cell tube fired in the above-described process, and sintered (for example, held at 1300 ° C. for 1 hour).

  The cell tube (fuel cell) 202 of Example 1 described above performs a battery reaction by the following operation. That is, as shown in FIG. 1, the fuel gas serving as the fuel for the cell reaction flows inside the base tube 11, passes through the pores of the base tube 11, and reaches the fuel electrode 12. This fuel gas is steam reformed by the active metal contained in the fuel electrode 12. Hydrogen generated by steam reforming passes through the pores of the fuel electrode 12 and reaches the solid electrolyte 13. On the other hand, the air flows outside the base tube 11 (air electrode 14). The oxygen in the air is ionized while passing through the pores of the air electrode 14 or reaches the solid electrolyte 13. The ionized oxygen passes through the solid electrolyte 13 and reaches the fuel electrode 12. The oxygen ions that have passed through the solid electrolyte 13 react with the fuel gas. The potential difference generated by such a cell reaction is extracted from the fuel electrode 12 and the air electrode 14 to be generated.

  In the first embodiment, since the insulating film 16 is provided between the fuel electrodes 12 on the outer surface of the base tube 11, leakage current flowing between the fuel electrodes 12 (fuel cell 210) is generated during power generation. It is suppressed. That is, since the insulating film 16 prevents the movement of electrons and ions between the fuel electrodes 12, the device voltage is prevented from being lowered and the leakage current is reduced. As a result, the oxygen permeation amount due to the leakage current is reduced, and the fuel consumption due to the oxygen permeation amount is reduced, thereby suppressing the reduction in power generation efficiency.

  In this case, when the oxygen permeation amount due to the leakage current increases, fuel consumption due to the oxygen permeation amount occurs and the fuel utilization rate increases, so that the average voltage at the adjacent fuel electrode 12 (hereinafter, the inter-element average voltage) decreases. However, since the power generation efficiency decreases, it is necessary to maintain the average voltage between elements higher than a predetermined value.

  As described above, in the fuel cell (cell tube 202) of the first embodiment, the fuel electrode 12, the solid electrolyte 13, and the air electrode 14 are laminated on the outer surface of the cylindrical base tube 11, and the fuel cell (power generation) Element) 210, a plurality of power generation elements 210 are arranged at predetermined intervals in the axial direction of the base tube 11, and a plurality of fuel cells 210 are connected in series by the interconnector 15, and the fuel electrode 12 is formed. An electric resistance value of 1000Ω or more is set between them.

  Therefore, by setting an electric resistance value of 1000Ω or more between the fuel electrodes 12, it is possible to suppress the generation of leakage current in this region as much as possible, and prevent a decrease in element voltage during energization and non-energization. As a result, the power generation efficiency can be improved.

  In the fuel cell of Example 1, the insulating film 16 that prevents the movement of electrons and ions is provided between the plurality of fuel cells 210. Therefore, by providing the insulating film 16 between the fuel cells 210, it is possible to suppress the occurrence of leakage current and prevent a decrease in the element voltage, and improve the power generation efficiency with a simple configuration in which the insulating film 16 is provided. Can be achieved.

  Further, in the fuel cell of Example 1, the insulating film 16 is provided between the plurality of fuel electrodes 12 and between the base tube 11 and the solid electrolyte 13. Accordingly, by providing the insulating film 16 between the base tube 11 and the solid electrolyte 13 between the fuel electrodes 12, it is possible to suppress the occurrence of leakage current and prevent a decrease in the element voltage, and the power generation efficiency with a simple configuration. Can be improved. In this case, the insulating film 16 is covered with the densely formed fuel electrode 12 and the solid electrolyte 13, thereby suppressing the leakage of fuel gas or air electrode gas through the insulating film 16 and the base tube 11. . This eliminates the need to form the insulating film 16 densely, eliminates the need to consider sinterability, and reduces manufacturing costs.

  Further, in the method of manufacturing the fuel cell of Example 1, the step of forming the base tube 11, the fuel electrode material film 22, the solid electrolyte material film 23, and the air electrode material film on the outer surface of the base tube 11. 24. A step of forming the power generation element material film by sequentially laminating the interconnector material film 25 and forming the power generation element material film at a predetermined interval in the axial direction of the base tube 11; A step of forming an insulating film material film 26 for insulating the power generating element material films on the outer surface, a fuel electrode material film 22, a solid electrolyte material film 23, an air electrode material film 24, and an interconnector material film 25. The insulating film material film 26 is sintered, and the fuel electrode 12, the solid electrolyte 13, the air electrode 14, the interconnector 15, and the insulating film 16 are formed on the base tube 11. The electrical resistance value is 1000Ω or more It is set to be.

  In this case, after forming the insulating film material film 26 on the outer surface of the base tube 11, the fuel electrode material film 22, the solid electrolyte material film 23, the interconnector material film 25, and the air electrode material film 24 are sequentially laminated. is doing.

  Therefore, by laminating and sintering the fuel electrode material film 22, the solid electrolyte material film 23, the air electrode material film 24, the interconnector material film 25, and the insulating film material film 26 on the base tube 11, The fuel electrode 12, the solid electrolyte 13, the air electrode 14, the interconnector 15, and the insulating film 16 can be formed on the base tube 11, and the manufacturing process can be simplified. By setting the electrical resistance value between the adjacent fuel electrodes 12 to 1000Ω or more, the generation of leakage current in this region can be suppressed as much as possible, and the device voltage can be reduced during energization or non-energization. As a result, the power generation efficiency can be improved. Further, since the insulating film 16 is covered with the fuel electrode 12 and the solid electrolyte 13, it is not necessary to form the insulating film 16 densely, it is not necessary to consider sinterability, and the manufacturing cost can be reduced. .

  FIG. 5 is a schematic diagram showing a fuel cell and a manufacturing method thereof according to Example 2 of the present invention. In addition, the same code | symbol is attached | subjected to the member which has the function similar to the Example mentioned above, and detailed description is abbreviate | omitted.

  As shown in FIG. 5, the cell tube (fuel cell) of Example 2 is formed by stacking a fuel electrode 12, a solid electrolyte 13, and an air electrode 14 on the outer surface of the base tube 11 toward the outside. A plurality of fuel cells are arranged in the axial direction of the base tube 11 and are connected in series by an interconnector 15. An insulating film 16 is provided between the fuel electrodes 12 so that the electrical resistance value between the fuel electrodes 12 adjacent in the axial direction of the base tube 11 is set to 1000Ω or more.

  In this embodiment, first, the fuel electrode material film 22 is formed on the surface of the base tube 11 at a predetermined interval in the axial direction of the base tube 11. Next, an insulating film material film 26 is formed on the surface of the base tube 11 between the fuel electrode material films 22. Subsequently, the solid electrolyte material film 23 and the interconnector material film 25 are laminated on the surfaces of the fuel electrode material film 22 and the insulating film material film 26. Then, sintering is performed in a state in which the fuel electrode material film 22, the insulating film material film 26, the solid electrolyte material film 23, and the interconnector material film 25 are laminated on the base tube 11 (for example, at 1350 ° C. for 1 hour) Hold. The air electrode material film 24 is laminated on the cell tube fired in the above-described process, and sintered (for example, held at 1300 ° C. for 1 hour) to form the air electrode 14.

  As described above, in the fuel cell (cell tube) of Example 2 and the manufacturing method thereof, the fuel electrode 12, the insulating film 16, the solid electrolyte 13, the interconnector 15, and the air electrode 14 are laminated on the base tube 11, and the fuel An insulating film 16 is provided between the plurality of fuel electrodes 12 and between the base tube 11 and the solid electrolyte 13 in order to set an electric resistance value of 1000Ω or more between the electrodes 12.

  Therefore, the generation of leakage current between the fuel electrodes 12 can be suppressed as much as possible, and a decrease in element voltage when energized or not energized can be prevented. As a result, power generation efficiency can be improved. . Further, since the insulating film 16 is covered with the densely formed solid electrolyte 13, leakage of fuel gas or air electrode gas through the insulating film 16 and the base tube 11 is suppressed. This eliminates the need to form the insulating film 16 densely, eliminates the need to consider sinterability, and reduces manufacturing costs.

  FIG. 6 is a schematic diagram showing a fuel cell and a manufacturing method thereof according to Example 3 of the present invention. In addition, the same code | symbol is attached | subjected to the member which has the function similar to the Example mentioned above, and detailed description is abbreviate | omitted.

  As shown in FIG. 6, the cell tube (fuel cell) of Example 3 is formed by stacking a fuel electrode 12, a solid electrolyte 13, and an air electrode 14 on the outer surface of the base tube 11 toward the outside. A plurality of fuel cells are arranged in the axial direction of the base tube 11 and are connected in series by an interconnector 15. An insulating film 16 is provided between the fuel electrodes 12 so that the electric resistance value between the adjacent fuel electrodes 12 is set to 1000Ω or more.

  In this embodiment, first, the fuel electrode material film 22 is formed on the surface of the base tube 11 at a predetermined interval in the axial direction of the base tube 11. Next, a solid electrolyte material film 23 and an interconnector material film 25 are laminated on the surface of the fuel electrode material film 22. Subsequently, an insulating film material film 26 is laminated between the fuel electrode material films 22 and between the solid electrolyte material film 23 and the interconnector material film 25. Then, sintering is performed in a state in which the fuel electrode material film 22, the solid electrolyte material film 23, the interconnector material film 25, and the insulating film material film 26 are laminated on the base tube 11 (for example, at 1350 ° C. for 1 hour) Hold. The air electrode material film 24 is laminated on the cell tube fired in the above-described process, and sintered (for example, held at 1300 ° C. for 1 hour) to form the air electrode 14.

  As described above, in the fuel cell (cell tube) and the manufacturing method thereof according to the third embodiment, the fuel electrode 12, the solid electrolyte 13, the interconnector 15, the insulating film 16, and the air electrode 14 are laminated on the base tube 11, An insulating film 16 is provided between the plurality of fuel electrodes 12 and between the solid electrolyte 13 and the interconnector 15 in order to set an electric resistance value of 1000Ω or more between the electrodes 12.

  Therefore, the generation of leakage current between the fuel electrodes 12 can be suppressed as much as possible, and a decrease in element voltage when energized or not energized can be prevented. As a result, power generation efficiency can be improved. . Further, since the insulating film 16 is interposed between the fuel electrodes 12 and between the solid electrolytes 13, high insulation between elements can be ensured, and the manufacturing cost can be reduced.

  FIG. 7 is a schematic diagram showing a fuel cell and a manufacturing method thereof according to Example 4 of the present invention. In addition, the same code | symbol is attached | subjected to the member which has the function similar to the Example mentioned above, and detailed description is abbreviate | omitted.

  As shown in FIG. 7, the cell tube (fuel cell) of Example 4 is formed by stacking a fuel electrode 12, a solid electrolyte 13, and an air electrode 14 on the outer surface of the base tube 11 toward the outside. A plurality of fuel cells are arranged in the axial direction of the base tube 11 and are connected in series by an interconnector 15. An insulating film 16 is provided between the fuel electrodes 12 so that the electric resistance value between the adjacent fuel electrodes 12 is set to 1000Ω or more.

  In this embodiment, first, the insulating film material film 26 is formed on the surface of the base tube 11 at a predetermined interval in the axial direction of the base tube 11. In this case, the insulating film material film 26 is formed to a thickness approximately equal to the laminated thickness of the fuel electrode material film 22, the solid electrolyte material film 23, and the interconnector material film 25. Next, a fuel electrode material film 22, a solid electrolyte material film 23, and an interconnector material film 25 are laminated on the surface of the base tube 11 between the insulating film material films 26. Then, the insulating material film 26, the fuel electrode material film 22, the solid electrolyte material film 23, and the interconnector material film 25 are laminated on the base tube 11 and sintered (for example, at 1350 ° C. for 1 hour). Hold. The air electrode material film 24 is laminated on the cell tube fired in the above process, and sintered (for example, held at 1300 ° C. for 1 hour) to form the air electrode 14.

  As described above, in the fuel cell (cell tube) and the manufacturing method thereof according to the fourth embodiment, the insulating film 16, the fuel electrode 12, the solid electrolyte 13, the interconnector 15, and the air electrode 14 are laminated on the base tube 11, and the fuel is produced. An insulating film 16 is provided between the plurality of fuel electrodes 12 and between the solid electrolyte 13 and the interconnector 15 in order to set an electric resistance value of 1000Ω or more between the electrodes 12.

  Therefore, the generation of leakage current between the fuel electrodes 12 can be suppressed as much as possible, and a decrease in element voltage when energized or not energized can be prevented. As a result, power generation efficiency can be improved. . Further, since the insulating film 16 is interposed between the fuel electrodes 12 and between the solid electrolytes 13, high insulation between elements can be ensured, and the manufacturing cost can be reduced.

  FIG. 8 is a schematic view showing a fuel cell and a manufacturing method thereof according to Example 5 of the present invention. In addition, the same code | symbol is attached | subjected to the member which has the function similar to the Example mentioned above, and detailed description is abbreviate | omitted.

  As shown in FIG. 8, the cell tube (fuel cell) of Example 5 is formed by stacking a fuel electrode 12, a solid electrolyte 13, and an air electrode 14 on the outer surface of the base tube 11 toward the outside. A plurality of fuel cells are arranged in the axial direction of the base tube 11 and are connected in series by an interconnector 15. An insulating film 16 is provided between the fuel electrodes 12 so that the electric resistance value between the fuel cells is set to 1000Ω or more, and a reaction preventing film (reaction preventing portion) 17 is provided on the surface of the insulating film 16. Is provided.

  In this embodiment, first, the insulating film material film 26 is formed on the surface of the base tube 11 at a predetermined interval in the axial direction of the base tube 11. Next, a reaction preventing film material film 27 is laminated on the surface of the insulating film material film 26. Subsequently, the fuel electrode material film 22, the solid electrolyte material film 23, and the interconnector material film 25 are laminated. Then, sintering is performed in a state in which the insulating film material film 26, the reaction preventing film material film 27, the fuel electrode material film 22, the solid electrolyte material film 23, and the interconnector material film 25 are laminated on the base tube 11 (for example, 1 hour at 1350 ° C.). The air electrode material film 24 is laminated on the cell tube fired in the above process, and sintered (for example, held at 1300 ° C. for 1 hour) to form the air electrode 14.

In this case, for example, Al ₂ (OH) ₃ (alumina) is used for the reaction preventing film 17 as a material.

  As described above, in the fuel cell (cell tube) and the manufacturing method thereof according to the fifth embodiment, the insulating film 16, the reaction preventing film 17, the fuel electrode 12, the solid electrolyte 13, the interconnector 15, and the air electrode 14 are formed on the base tube 11. In order to set an electric resistance value of 1000Ω or more between the fuel electrodes 12, an insulating film 16 is provided between the plurality of fuel electrodes 12 and between the base tube 11 and the solid electrolyte 13, and insulation is performed. A reaction preventing film 17 is provided between the film 16 and the fuel electrode 12 and the solid electrolyte 13.

  Therefore, the generation of leakage current between the fuel electrodes 12 can be suppressed as much as possible, and a decrease in element voltage when energized or not energized can be prevented. As a result, power generation efficiency can be improved. . Further, the reaction preventing film 17 prevents reactions between the insulating film 16 and the fuel electrode 12, and the insulating film 16 and the solid electrolyte 13, thereby preventing formation of a layer having no insulating property. Can be prevented by preventing the power generation efficiency from decreasing. By providing the reaction preventing film 17, the same effect as described above can be obtained for the cell tube having the structure in which the insulating film 16 is adjacent to the fuel electrode 12 or the solid electrolyte 13. That is, in the cell tubes according to the second to fourth embodiments, the same effect as described above can be obtained by providing the reaction preventing layer 17 between the insulating film 16, the fuel electrode 12, and the solid electrolyte 13.

  FIG. 9 is a schematic view showing a fuel cell and a manufacturing method thereof according to Example 6 of the present invention. In addition, the same code | symbol is attached | subjected to the member which has the function similar to the Example mentioned above, and detailed description is abbreviate | omitted.

  As shown in FIG. 9, the cell tube (fuel cell) of Example 6 is formed by laminating a fuel electrode 12, a solid electrolyte 13, and an air electrode 14 on the outer surface of the base tube 11 so as to face the outside. A plurality of fuel cells are arranged in the axial direction of the base tube 11 and are connected in series by an interconnector 15. An insulating film 16 is provided between the fuel electrodes 12 so that the electric resistance value between the fuel cells is set to 1000Ω or more. In this case, the insulating film 16 is provided as an electrolyte reaction film 28 formed by a chemical reaction with the solid electrolyte 13.

  In this embodiment, first, the fuel electrode material film 22 is formed on the surface of the base tube 11 at a predetermined interval in the axial direction of the base tube 11. Next, the electrolyte reaction film 28 is applied to the surface of the fuel electrode material film 22 and the surface of the base tube 11 which face each other. Subsequently, the solid electrolyte material film 23 and the interconnector material film 25 are laminated on the surfaces of the fuel electrode material film 22 and the electrolyte reaction film 28. Then, sintering is performed in a state in which the fuel electrode material film 22, the electrolyte reaction film 28, the solid electrolyte material film 23, and the interconnector material film 25 are laminated on the base tube 11 (for example, maintained at 1350 ° C. for 1 hour). To do. By this sintering, the electrolyte reaction film 28 reacts with the solid electrolyte material film 23 to become the insulating film 16. The air electrode material film 24 is laminated on the cell tube fired in the above process, and sintered (for example, held at 1300 ° C. for 1 hour) to form the air electrode 14.

In this case, for example, La (OH) ₃ is used as the material of the electrolyte reaction film 28. Then, after sintering, the electrolyte reaction film 28 reacts with the solid electrolyte material film 23 to become the insulating film 16. When the solid electrolyte material film 23 is YSZ, the insulating film 16 is made of La ₂ Zr ₂ O. ₃

  As described above, in the fuel cell (cell tube) and the manufacturing method thereof according to the sixth embodiment, the fuel electrode 12, the solid electrolyte 13, the interconnector 15, and the air electrode 14 are stacked on the base tube 11, and In order to set an electric resistance value of 1000Ω or more, an insulating film 16 is provided between the plurality of fuel electrodes 12. Therefore, the generation of leakage current between the fuel electrodes 12 can be suppressed as much as possible, and a decrease in element voltage when energized or not energized can be prevented. As a result, power generation efficiency can be improved. .

  Further, a fuel electrode material film 22 is formed on the surface of the base tube 11, and an electrolyte reaction film 28 is applied on the surface of the fuel electrode material film 22 and the surface of the base tube 11 that are opposed to each other. By laminating and sintering the interconnector material film 25 and the air electrode material film 24, the electrolyte reaction film 28 reacts with the solid electrolyte material film 23 to form the insulating film 16. Therefore, it is possible to reduce the thickness of the insulating film 16 and to reduce the size of the device, and to reduce the manufacturing cost.

  Hereinafter, specific materials of the insulating film 16 or the electrolyte reaction film 28 applied in the above-described Examples 1 to 6 will be described. FIG. 10 is a table showing appropriate materials for the insulating portions in the fuel cells of Examples 1 to 6.

In Examples 1 to 6, for example, La ₂ Zr ₂ O ₇ , Y ₃ Zr ₅ O ₁₂ , SrTi _{1 + X} O ₃ (+ Al ₂ O ₃ ), MgO + MgAl ₂ O ₄ can be presented. However, in forming the insulating film 16 on the fuel cell (cell tube), the linear expansion coefficient α, the sinterability, the insulating properties, and the presence or absence of reactivity are important. Here, the appropriate range of the linear expansion coefficient α is 9.5 to 11 × 10 ⁻⁶ / ° C. As for the sinterability, the porosity is 10% or less, preferably 3 to 5% in consideration of gas permeability. As described above, the appropriate insulating property is that the electric resistance value between the fuel electrodes 12 is 1000Ω or more. Reactivity is an appropriate requirement that it does not react with the contacting member to form a second layer that does not have insulation, and does not adversely affect power generation performance due to element diffusion under high-temperature power generation. .

When the above contents are combined, they can be summarized in the graph shown in FIG. As the insulating film 16 applied to the fuel cells of Examples 1 and ₂ , La ₂ Zr ₂ O ₇ is optimal because there is no need to consider the sinterability on the structure. Moreover, since it is necessary to consider all items for the insulating film 16 applied to the fuel cells of Examples 3 and 4, SrTi _1-X O ₃ (+ Al ₂ O ₃ ) is optimal. Also, MgO + MgAl ₂ O ₄ is optimal for the insulating film 16 applied to the fuel cell of Example 5 because there is no need to consider reactivity in terms of structure. Also, La (OH) ₃ is optimal for the electrolyte reaction membrane 28 applied to the fuel cell of Example 6.

  However, in the graph shown in FIG. 10, the notation “◯” is optimal, but even the notation “Δ” satisfies the criteria of linear expansion coefficient α, sinterability, insulation, and reactivity. . The insulating film 16 or the electrolyte reaction film 28 applied in the fuel cell of the present invention is not limited to the materials described above.

  The fuel cell and the manufacturing method thereof according to the present invention are intended to improve the power generation efficiency by setting the electric resistance value of 1000Ω or more between the adjacent fuel electrodes 12 to suppress the generation of leakage current. It can be applied to any fuel cell.

11 Base tube 12 Fuel electrode 13 Solid electrolyte 14 Air electrode 15 Interconnector 16 Insulating film (insulating part)
17 Reaction prevention membrane (reaction prevention part)
28 Electrolyte reaction membrane 101 Fuel cell module 202 Cell tube (fuel cell)
210 Fuel cell (power generation element)

Claims (12)

A base tube having a cylindrical shape;
A plurality of power generation elements that are arranged on the outer peripheral surface of the base tube along the axial direction of the base tube and in which a fuel electrode, an electrolyte, and an air electrode are laminated
An interconnector for connecting adjacent power generation elements in series;
A solid oxide fuel cell, wherein an electrical resistance value between adjacent fuel electrodes is 1000Ω or more.   The solid oxide fuel cell according to claim 1, further comprising an insulating portion that suppresses movement of electrons and ions between the adjacent power generation elements.   In the adjacent power generation elements, the insulating portion is between the fuel electrode of one of the power generation elements and the fuel electrode of the other power generation element, and the solid electrolyte and the base body of one of the power generation elements The solid oxide fuel cell according to claim 2, wherein the solid oxide fuel cell is provided between the pipe and the pipe.   In the adjacent power generation elements, the insulating portion is disposed between the fuel electrode of one of the power generation elements and the fuel electrode of the other power generation element and between the solid electrolyte of the one power generation element and the interface. The solid oxide fuel cell according to claim 2, wherein the solid oxide fuel cell is provided between the connector and the connector.   The solid oxide fuel cell according to any one of claims 2 to 4, wherein a reaction preventing portion is provided between the power generation element and the insulating portion.   5. The solid oxide fuel cell according to claim 2, wherein the insulating portion is an electrolyte reaction portion formed by a chemical reaction with the solid electrolyte. 6. Forming a substrate tube;
Forming a plurality of fuel electrode material films on the outer peripheral surface of the base tube along the axial direction of the base tube;
A step of sequentially laminating a solid electrolyte material film and an interconnector material film on the upper surface of the fuel electrode material film;
Forming a plurality of insulating portion material films on the outer peripheral surface of the base tube along the axial direction of the base tube;
Sintering the insulating part material film, the fuel electrode material film, the solid electrolyte material film, and the interconnector material film to form an insulating part, a fuel electrode, a solid electrolyte, and an interconnector; Have
A method for producing a solid oxide fuel cell, wherein an electrical resistance value between adjacent fuel electrodes is 1000Ω or more.   8. The fuel electrode material film is formed after the insulating part material film is formed, and then the solid electrolyte material film and the interconnector material film are sequentially laminated. A method for producing a solid oxide fuel cell.   The material film for an insulating part is formed after forming the material film for the fuel electrode, and then the material film for the solid electrolyte and the material film for the interconnector are sequentially laminated. A method for producing a solid oxide fuel cell.   8. The method for manufacturing a solid oxide fuel cell according to claim 7, wherein the insulating material film is formed after sequentially laminating the solid electrolyte material film and the interconnector material film.   11. The solid oxide fuel cell according to claim 8, wherein after forming the insulating part material film, a reaction preventing part material film is formed on an outer surface of the insulating part material film. Manufacturing method. After forming the fuel electrode material film, the method includes a step of applying an electrolyte reaction part to the opposing surface of the fuel electrode material film adjacent in the axial direction of the base tube,
The fuel electrode material film, the electrolyte reaction part, the solid electrolyte material film, and the interconnector material film are sintered, and the fuel electrode, the insulating part, the solid electrolyte, The interconnector is formed, The manufacturing method of the solid oxide fuel cell of Claim 7 characterized by the above-mentioned.

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