JP5734215B2 - Solid oxide fuel cell - Google Patents

Description

  The present invention relates to an insulating film material for a solid oxide fuel cell, a solid electrolyte fuel cell, a solid electrolyte fuel cell, and a method for manufacturing a solid oxide fuel cell.

  A solid oxide fuel cell (SOFC) is a battery that generates power by supplying a fuel gas to a fuel electrode and a fluid (air) containing oxygen to an air electrode (see Patent Document 1).

  The cell of the cylindrical horizontal stripe type SOFC has, for example, a porous base tube, and a single cell membrane in which a fuel electrode, a solid electrolyte, and an air electrode are sequentially laminated on the outer peripheral surface of the base tube. A plurality of unit cell membranes are formed along the longitudinal direction of the base tube, and adjacent unit cell membranes are electrically connected to each other via an interconnector.

  Cylindrical horizontal stripe-type SOFC cells constitute one cartridge in units of plural. In this cartridge, the ends of the plurality of cells are bonded and fixed to holes provided in a metal support member. The cell is fixed and supported while ensuring insulation and airtightness between the support members by adhering the ceramic member.

  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 2, for example. In the fuel cell described in Patent Document 2, 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-A-4-215258 JP 2004-179071 A

  The insulating film material for insulating between the base tube and the element needs to consider the amount of shrinkage and stress at the time of sintering with each functional material constituting the single element of the fuel cell and the base tube material. Unless an optimal material that satisfies both the functionality and productivity of the power generation device is selected, problems arise in the characteristics of the power generation element itself. In addition, when the insulating film is thickened, gaps are easily generated between the layers of the functional film materials of the power generation element, the internal and external denseness of the cell is reduced, gas leaks are likely to occur, and air flows from the outer peripheral surface of the cell. There arises a problem of deterioration of robustness due to gas leakage.

The base tube is made of CaO stabilized ZrO ₂ (CSZ) or the like and has oxygen ion permeability. Therefore, it has been found that the base tube has conductivity in a high temperature state where power is generated as a fuel cell. As a result, in addition to the conduction by the interconnector between the plurality of single cells, a leakage current is generated in the base tube, resulting in a problem of reducing the power generation efficiency of the cell.
The solid electrolyte is made of Y ₂ O ₃ stabilized ZrO ₂ (YSZ). However, a solid electrolyte is disposed between adjacent fuel electrodes in the axial direction of the gas pipe, and leaks through this electrolyte. Electric current is generated.
In addition, the fixed portion of the cell end with the metal support member was fixed and supported by interposing a ceramic member in order to ensure insulation and gas tightness against gas leakage. Attaching to a plurality of cells A problem arises that the attaching operation requires a great deal of time.

  The present invention has been made in view of the above circumstances, and is a solid electrolyte fuel using an insulating film material that can prevent generation of leakage current, suppress reduction in power generation efficiency of a cell, and ensure insulation. An object is to provide a battery.

In order to solve the above-mentioned problem, the present invention includes SrZrO ₃ and Al ₂ O _3, and the content of the Al ₂ O ₃ is 3 mol% or more and 15 mol% or less with respect to the SrZrO ₃ . An insulating film material for an electrolyte fuel cell is provided.

According to the above invention, the SrZrO ₃ insulating material contains Al ₂ O ₃ in the above range, thereby improving the sintering shrinkage behavior of the insulating film as compared with the insulating film composed of SrZrO ₃ alone. The thermal expansion coefficient can be increased. This makes it possible to control the characteristics of the insulating film, such as densification and film thickness control.

The SrZrO _3, when the firing of the insulating film material containing _Al 2 _{O 3} of a predetermined amount, and SrZrO _3, reacts with _{Al 2 O 3, SrAl 12 O} 19 ( magnetoplumbite tight structure) is precipitated. As a result, the composition of the parent phase is shifted to the ZrO ₂ rich side, and the sinterability is improved. When the content of Al ₂ O ₃ is too small, the effect of improving the sintering shrinkage behavior is reduced.
When the content of Al ₂ O ₃ is too large, ZrO ₂ is deposited as a third phase, there is a problem such as degradation and phase transformation in the resistance of the insulating film. Therefore, the content of Al ₂ O ₃ is 3 mol% or more and 5 mol% or less.

  The present invention also provides a base tube made of a porous material, a plurality of unit cell membranes in which a fuel electrode, a solid electrolyte, and an air electrode are sequentially laminated on the outer peripheral surface of the base tube, and adjacent unit cell membranes. A solid oxide fuel cell comprising an interconnector for electrically connecting each other, wherein the solid electrolyte fuel cell according to claim 1 is provided between the base tube and the fuel electrode or between the fuel electrodes. Provided is a solid oxide fuel cell having an insulating film formed by sintering a battery insulating film material.

  By interposing an insulating film between the base tube and the fuel electrode or between the fuel electrodes, leakage current through the base tube and the electrolyte can be prevented. As a result, it is possible to suppress a decrease in power generation efficiency of the solid oxide fuel cells.

In addition, the present invention includes a plurality of the solid oxide fuel cells described above, and at least one end of the plurality of solid electrolyte fuel cells penetrates a metal member, and the metal member includes a plurality of the solid electrolyte fuel cells. A solid oxide fuel cell for fixing and supporting a battery cell, wherein an insulating film formed by sintering the above-described insulating film material for a solid oxide fuel cell is interposed between the solid oxide fuel cell and a metal member. A solid oxide fuel cell in contact with each other.

  By providing an insulating film between the solid oxide fuel cell and the metal member, the conductive lead electrode formed on the solid electrolyte fuel cell and the metal member are electrically insulated from each other, and the solid electrolyte fuel is provided. Since the sealing performance against the air and fuel gas supplied to the inside and outside of the battery cell can be secured, the electricity generated by the solid oxide fuel cell is efficiently collected, and the gas sealing performance is also achieved with a simple structure. As a result, assembly workability is improved.

The present invention also includes a base tube made of a porous material, a plurality of unit cell membranes in which a fuel electrode, a solid electrolyte, and an air electrode are sequentially laminated on the outer peripheral surface of the base tube, and a plurality of adjacent unit cells. a method of manufacturing a solid oxide fuel cell comprising a interconnector for electrically connecting the cell membrane, and SrZrO _3, consists _Al 2 _{O 3} Prefecture, the content of the _Al 2 _{O 3} is, Slurry and apply a solid oxide fuel cell insulating film material of 3 mol% or more and 15 mol% or less with respect to the SrZrO ₃ on a substrate tube; and slurry the fuel electrode material to form the substrate A step of coating on the insulating film material for a solid oxide fuel cell applied on the tube, and a step of co-sintering the insulating film material for the solid oxide fuel cell and the material of the fuel electrode applied to the base tube And comprising To provide a method of manufacturing oxide fuel cell.

According to the above invention, the SrZrO ₃ insulating material contains Al ₂ O ₃ in the above range, thereby improving the sintering shrinkage behavior of the insulating film as compared with the insulating film composed of SrZrO ₃ alone. The thermal expansion coefficient can be increased. This makes it possible to control the characteristics of the insulating film, for example, densification (porosity), film thickness control, and the like.

When the content of Al ₂ O ₃ is too small, the effect of improving the sintering shrinkage behavior is reduced.
When the content of Al ₂ O ₃ is too large, ZrO ₂ is deposited as a third phase, there is a problem such as degradation and phase transformation in the resistance of the insulating film. Therefore, the content of Al ₂ O ₃ is 3 mol% or more and 5 mol% or less.

  By interposing the insulating film obtained by sintering the insulating film material between the base tube and the fuel electrode and between the fuel electrodes, leakage current through the base tube and the electrolyte can be prevented. As a result, it is possible to suppress a decrease in power generation efficiency of the solid oxide fuel cells.

  Further, when an insulating film material is applied to the end portion of the base tube, both end portions of the solid oxide fuel cell can be supported while penetrating the metal member through the insulating film. Thereby, since the solid oxide fuel cell can be electrically isolated from the metal member, it is possible to provide a function of ensuring the insulation of the unit cell membrane.

According to the present invention, by incorporating the Al ₂ O ₃ of a predetermined amount of insulating material SrZrO _3, an excellent insulating film material in the sintering property. By interposing an insulating film formed by sintering the insulating material between the base tube and the fuel electrode, leakage current through the base tube can be prevented, and a decrease in power generation efficiency of the solid oxide fuel cell can be suppressed. . Furthermore, by interposing and fixing the insulating film of the present invention in a fixed portion with the metal member located at the end of the cell, a solid oxide fuel cell capable of ensuring insulation and airtightness can be realized. .

It is a fragmentary sectional view of the cylindrical solid oxide fuel cell concerning this embodiment. It is a fragmentary sectional view of the solid oxide fuel cell concerning this embodiment. FIG. 3 is an enlarged view of an upper end portion of the solid oxide fuel cell cartridge shown in FIG. 2. SrZrO is a scanning electron micrograph of the ₃ + _{0mol% Al} 2 _{O 3} test pieces were used. SrZrO is a scanning electron micrograph of the test piece using the _{3 + 5mol% Al 2 O 3} . It is a figure which shows the sintering shrinkage | contraction behavior of each material.

  The present invention relates to an insulating film material for a solid oxide fuel cell, a solid electrolyte fuel cell, a solid electrolyte fuel cell, and a method for manufacturing a solid oxide fuel cell.

  FIG. 1 is a partial cross-sectional view of a cylindrical solid oxide fuel cell according to the present embodiment. A solid electrolyte fuel cell (hereinafter abbreviated as a cell) 1 is formed with a unit cell membrane 6 in which a fuel electrode 3, a solid electrolyte 4, and an air electrode 5 are laminated on a porous substrate tube 2 in this order from the substrate tube side. Has been. A plurality of unit cell membranes 6 are formed in the central portion of the base tube 2 along the longitudinal direction, and adjacent unit cell membranes are electrically connected in series by an interconnector 7. In the present embodiment, an insulating film 8 is interposed between the base tube 2 and the fuel electrode 3. An insulating film 9 is interposed between adjacent fuel electrodes.

The base tube 2 is made of a porous material such as calcia stabilized zirconia (CSZ). The thermal expansion coefficient of the base tube 2 is 10 ppm / K to 11 ppm / K.
The fuel electrode 3 is composed of a composite material of nickel (Ni) and a zirconia-based electrolyte material. For example, Ni / yttria stabilized zirconia (YSZ) is used as the composite material. The thermal expansion coefficient of the fuel electrode 3 is 11 ppm / K to 12 ppm / K.

The solid electrolyte 4 is electronically insulating and is required to have gas tightness that does not allow gas to pass and high ion permeability at high temperatures. Therefore, YSZ is mainly used for the solid electrolyte 4.
The air electrode 5 is formed of a lanthanum strontium-based material and generates oxygen ions from the air.

The interconnector 7 is composed of a conductive perovskite oxide represented by M _1-x L _x TiO ₃ (M is an alkaline earth metal element, L is a lanthanoid element) such as strontium titanate, and the like. It is a dense film so that it does not mix with air.

The insulating film 8 and the insulating film 9 are films formed by sintering a solid oxide fuel cell insulating film material containing SrZrO ₃ and Al ₂ O ₃ . In the insulating film material for a solid oxide fuel cell, the content of Al ₂ O ₃ is 0.01 mol% or more and 15 mol% or less, preferably 0.5 mol% or more and 5 mol% or less with respect to SrZrO ₃ . The thermal expansion coefficient of the insulating film 8 is 9.5 ppm / K or more and 11.5 ppm / K or less. The resistance value of the insulating film 8 at the use temperature (900 ° C. or higher) is set to 10 ⁴ Ω · cm or higher. The porosity of the insulating film 8 and the insulating film 9 is such that the porosity of the insulating film is in the range of 70% to 100%, but the insulating film 8 is porous so that fuel can permeate, and the insulating film 9 is dense. It is preferable to adjust the amount of Al ₂ O ₃ so as to form a film. The thickness of the insulating film is 10 μm to 500 μm.

  The insulating film 8 is also preferably provided at the end of the cell 1, and the insulating film is formed on the surface of the lead film at the end. The end is defined as an end side with respect to the plurality of unit cell films 6.

FIG. 2 shows a schematic configuration diagram of the solid oxide fuel cell cartridge 10 according to the present embodiment.
In a solid oxide fuel cell (SOFC) cartridge 10, a plurality of cells 1, an upper metal member 11, a lower metal member 12, and heat insulators 13 and 14 are arranged.

  Each end portion of the plurality of cells 1 is fixedly supported while penetrating through the upper metal member 11 and the lower metal member 12, respectively.

  FIG. 3 is an enlarged view of the upper end portion of the solid oxide fuel cell cartridge 10 shown in FIG. The upper end of the solid oxide fuel cell cartridge 10 is hermetically sealed by bonding and fixing the boundary between the cell 1 and the upper metal member 11 with an adhesive via the insulating film 8. As the adhesive, an inorganic adhesive having appropriate heat resistance and adhesive strength is used.

  The upper metal member 11 and the lower metal member 12 are made of a metal such as a steel type mixed with Cr, for example. When the insulating film 8 is provided at the end of the cell 1, the cell 1 is supported by the upper metal member 11 and the lower metal member 12 through the insulating film 8. The upper metal member 11 and the lower metal member 12 have a shape in which a portion to be bonded to the cell 1 is narrowed toward the long axis direction of the cell, and the cell and the metal member (the upper metal member 11 and the lower metal member 12) are The metal member is joined at a portion close to the cell of the narrowed portion of the metal member. The constricted portion of the metal member may be either up or down with respect to the cell.

  The heat insulators 13 and 14 are respectively disposed between the end portions of the plurality of unit cell films 6 connected in series and the upper metal member 11 or the lower metal member 12. The heat insulators 13 and 14 are formed of a material having heat insulating properties. The heat insulators 13 and 14 separate the cell side of the cell from the upper metal member or the lower metal member side so as to allow ventilation. Between the heat insulating material 13 and the heat insulating material 14, a power generation chamber 15 in which a plurality of single cell membranes 6 are accommodated is formed. In FIG. 2, an air supply path 16 capable of supplying air to the outside of the cell 1 is formed between the lower metal member 12 and the heat insulating material 14. An air discharge path 17 is formed between the upper metal member 11 and the heat insulating material 13 so as to be able to discharge the air supplied into the power generation chamber from the power generation chamber to the outside.

  A fuel supply path 18 is formed on the upper end portion side of the upper metal member 11. The fuel supply path 18 can supply a fluid (fuel gas) containing fuel through the cell. A fuel discharge path 19 is formed on the cell lower end side of the lower metal member 12. The fuel discharge path 19 can discharge the fuel gas supplied to the cell 1 in the power generation chamber from the power generation chamber to the outside.

  The upper metal member 11 and the lower metal member 12 also have a function of separating fluid supplied to the inside and outside of the cell. For this purpose, the fixed support portions of the cell 1 and the metal members 11 and 12 are hermetically joined by an adhesive layer disposed at the joint portion between the insulating film and the metal member. Even if this structure is adopted, gas leakage is less likely to occur and the assembly workability is improved compared to conventional bonding using a ceramic member.

Below, the manufacturing method of a cell is demonstrated.
First, a porous material mainly composed of calcia-stabilized zirconia (CSZ) or the like is formed into a tubular shape by an extrusion molding method and dried to obtain a base tube.

Next, a solvent is added to the insulating film material to form a slurry, and the slurry is applied onto the substrate tube by a screen printing method. The place where the insulating film material is applied is the whole surface of the base tube or the place in contact with the fuel electrode. The insulating film material may be further applied to the end of the cell. As the insulating film material, for example, a predetermined amount of SrZrO ₃ and Al ₂ O ₃ are weighed, mixed appropriately by a wet mixing method using a ball mill, and then dried mixed powder.

Next, as a material for the fuel electrode, for example, a solvent is added to a mixed powder obtained by mixing NiO and YSZ at a predetermined mixing ratio, and the mixture is made into a slurry by using three rollers. Moreover, each material is similarly slurried as a material of a solid electrolyte and an interconnector.
Each slurry is sequentially formed on the substrate tube by the screen printing method, dried, and then heat-treated under a predetermined sintering condition using an electric furnace or the like.

  Next, the air electrode material is slurried in the same manner as the fuel electrode material. A slurry for the air electrode is applied so as to cover the solid electrolyte and the interconnector. The application is performed by a screen printing method. After drying the slurry for an air electrode applied as described above, the base tube is heat-treated at a predetermined sintering temperature by an electric furnace.

  Next, the operation of the solid oxide fuel cell module using the cell manufactured by the manufacturing method according to the present embodiment will be described. The power generation chamber of the module body is heated to an operating temperature (about 900 to 1000 ° C.), and fuel gas such as hydrogen is supplied to the fuel supply path and air is supplied to the air supply path. The fuel gas supplied to the fuel supply path flows into the cell from the upper end side of the cell. The air supplied to the air supply path flows into the power generation chamber.

  The fuel gas passes through the porous substrate tube and is supplied to the fuel electrode of the single cell membrane. When the air (oxygen) comes into contact with the air electrode, the cell membrane reacts electrochemically with hydrogen and air (oxygen) to generate electric power, and the electric power is sent to the outside through a current collecting member (not shown). It is supposed to be. According to this embodiment, since the insulating film is interposed between the base tube and the fuel electrode, it is possible to prevent the power generated above from flowing back through the base tube.

  The remaining fuel gas after being used for power generation flows into the fuel discharge path from the lower end of the cell and is discharged to the outside. On the other hand, the remaining air after being subjected to power generation is discharged to the outside through an air discharge path.

  In addition, although it demonstrated using the cylindrical solid electrolyte type fuel battery cell in the said embodiment, the same effect can be acquired also when this invention is applied to a steam electrolysis cell.

(1) Measurement of porosity, resistance, and thermal expansion coefficient SrZrO ₃ and Al ₂ O ₃ were used as starting materials. A predetermined amount of each raw material was weighed, mixed for 10 hours by a wet mixing method using a ball mill, and then dried to obtain an insulating film material. Al ₂ O ₃ was mixed with 0 mol% (not containing Al ₂ O ₃ ), 0.5 mol%, 1 mol%, 3 mol%, 5 mol%, 10 mol%, or 15 mol% with respect to SrZrO ₃ . Each insulating film material was molded and fired in the atmosphere at 1400 ° C. for 4 hours to produce a test piece of the insulating film.

Using the test piece, the porosity, electrical resistance, and thermal expansion coefficient were measured.
The porosity was measured by Archimedes method. The electrical resistance was measured by the 4-terminal method. The thermal expansion coefficient was calculated with a thermal dilatometer. The results are shown in Table 1.

An insulating film on SrZrO ₃ formed by sintering the insulating film material containing _Al 2 _{O 3} had a porosity of decreased than with SrZrO ₃ single insulating film material. In particular, when Al ₂ O ₃ was contained in an amount of 3 mol% or more, the porosity was greatly reduced.

The electrical resistance hardly changed even when Al ₂ O ₃ was contained in an amount of 10 mol%. When the insulating film material containing Al ₂ O ₃ in SrZrO ₃ is sintered, SrAl ₁₂ O _{19 as} the second phase is generated. When the content of Al ₂ O ₃ is too large, the amount of ZrO ₂ is a third layer is increased. Since ZrO ₂ is a conductive phase transformation, an increase in ZrO ₂ as an insulating film is not preferable. Therefore, the content of Al ₂ O ₃ is preferably 15 mol% or less.

The thermal expansion coefficient slightly increased with an increase in the content of Al ₂ O ₃ . Thus, it was confirmed that by containing Al ₂ O ₃ , the thermal expansion coefficient of the insulating film can be approximately the same as that of the base tube and can be suitable for co-sintering with the base tube.

(2) Observation of tissue surface The tissue surface of the test piece prepared above was observed with a scanning electron microscope. FIG. 4 is a scanning electron micrograph (× 10,000) of a test piece using SrZrO ₃ +0 mol% Al ₂ O ₃ as an insulating film material. In the figure, black portions 20 are pores. FIG. 5 is a scanning electron micrograph (× 10,000) of a test piece using SrZrO ₃ +5 mol% Al ₂ O ₃ as an insulating film material. In the figure, the black portion 21 is SrAl ₁₂ O ₁₉ (magnetoplantite structure).

According to FIGS. 4 and 5, pores are reduced by forming Al ₂ O ₃ in SrZrO ₃ and sintering, and a dense insulating film is obtained. Further, according to Table 1 and FIG. 4, by incorporating _Al 2 _{O 3} in SrZrO _3, it was found that sinterability is greatly improved.

(3) Measurement of sintering shrinkage behavior As insulating film materials, SrZrO ₃ +0 mol% Al ₂ O ₃ , SrZrO ₃ +0.5 mol% Al ₂ O ₃ , SrZrO ₃ +1 mol% Al ₂ O ₃ , SrZrO ₃ +3 mol% Al ₂ O ₃ uses _{SrZrO 3 + 5mol% Al 2 O} 3 or _{SrZrO 3 + 15mol% Al 2 O} 3,, was measured sintering shrinkage behavior of each material. For the measurement of the sintering shrinkage behavior, a push rod type thermal dilatometer (for example, a lateral thermal dilatometer TMA8360 manufactured by Rigaku Corporation) was used. The measurement was carried out using a temperature profile in which the temperature was raised from room temperature to 1400 ° C. at 10 ° C./min and then kept at this temperature for 4 hours.

  FIG. 6 shows the sintering shrinkage behavior of each material. In the figure, the horizontal axis represents the temperature and the holding time after the temperature rise, and the vertical axis represents the coefficient of thermal expansion.

According to FIG. 6, by the inclusion of Al ₂ O _3, it showed a tendency to more shrinkage. In particular, the sinterability was greatly improved by containing 3 mol% to 15 mol% of Al ₂ O ₃ . Further, the insulating film material containing Al ₂ O ₃ has a shrinkage behavior close to that of the base tube material, and can be co-sintered.

(4) Film-formability evaluation test SrZrO ₃ and Al ₂ O ₃ were used as starting materials. A predetermined amount of each raw material was weighed, mixed for 10 hours by a wet mixing method using a ball mill, and then dried to obtain an insulating film material. Al ₂ O ₃ was mixed with 0 mol% (not containing Al ₂ O ₃ ), 0.5 mol%, 1 mol%, 3 mol%, or 5 mol% with respect to SrZrO ₃ . Each insulating film material was slurried, and the slurry was applied onto a substrate tube made of CaO-stabilized ZrO ₂ by screen printing. This base tube was co-sintered in the atmosphere at 1400 ° C. for 4 hours to evaluate the film formability. The sintered insulating film was not peeled off visually, and the cross section of the film was observed with an electron microscope. As a result, it was confirmed that there was no problem with the adhesion at the interface.

According to the above test, it was confirmed that the insulating film obtained by sintering the insulating film material containing Al ₂ O ₃ in SrZrO ₃ has good film formability.

1 cell (solid oxide fuel cell)
2 Base tube 3 Fuel electrode 4 Solid electrolyte 5 Air electrode 6 Single cell membrane 7 Interconnector 8 Insulating membrane (between fuel electrode and substrate tube)
9 Insulating film (between fuel electrodes)
DESCRIPTION OF SYMBOLS 10 Solid oxide fuel cell module 11 Upper metal member 12 Lower metal members 13 and 14 Heat insulator 15 Power generation chamber 16 Air supply path 17 Air discharge path 18 Fuel supply path 19 Fuel discharge path 20 Pore 21 SrAl ₁₂ O ₁₉

Claims (5)

Consisting of SrZrO ₃ and Al ₂ O ₃ ,
An insulating film material for a solid oxide fuel cell, wherein the content of Al ₂ O ₃ is ₃ mol% or more and 15 mol% or less with respect to the SrZrO ₃ . A base tube made of a porous material, a plurality of unit cell membranes in which a fuel electrode, a solid electrolyte, and an air electrode are sequentially laminated on the outer peripheral surface of the substrate tube, and adjacent unit cell membranes are electrically connected to each other An interconnector, and a solid oxide fuel cell comprising:
Wherein between the substrate tube and the fuel electrode, the solid electrolyte type fuel cell of the solid oxide fuel cell insulating film material is interposed an insulating film formed by sintering according to claim 1. A base tube made of a porous material, a plurality of unit cell membranes in which a fuel electrode, a solid electrolyte, and an air electrode are sequentially laminated on the outer peripheral surface of the substrate tube, and adjacent unit cell membranes are electrically connected to each other An interconnector, and a solid oxide fuel cell comprising:
A solid oxide fuel cell having an insulating film formed by sintering the insulating film material for a solid oxide fuel cell according to claim 1 interposed between the fuel electrodes. A base tube made of a porous material, a plurality of unit cell membranes in which a fuel electrode, a solid electrolyte, and an air electrode are sequentially laminated on the outer peripheral surface of the substrate tube, and adjacent unit cell membranes are electrically connected to each other with a plurality and the interconnector, the solid oxide fuel cell having a to at least one end of the plurality of the solid oxide fuel cell units through the metal member, wherein the metal member is plural solid oxide fuel A fuel cell for fixing and supporting battery cells,
The solid electrolyte fuel which joined between the said solid oxide fuel cell and the said metal member through the insulating film formed by sintering the insulating film material for solid electrolyte fuel cells of Claim 1 battery. A base tube made of a porous material, a plurality of unit cell membranes in which a fuel electrode, a solid electrolyte, and an air electrode are sequentially laminated on the outer peripheral surface of the base tube, and a plurality of adjacent unit cell membranes electrically An interconnector to be connected, and a manufacturing method of a solid oxide fuel cell comprising:
A solid oxide fuel cell insulating film material comprising SrZrO ₃ and Al ₂ O ₃ and having a content of Al ₂ O ₃ of ₃ mol% or more and 15 mol% or less with respect to SrZrO ₃ is slurried. a step of applying onto the substrate tube,
Applying the slurry of the fuel electrode material onto the insulating film material for a solid oxide fuel cell applied onto the base tube; and
Co-sintering the insulating film material for a solid oxide fuel cell applied to the substrate tube and the fuel electrode material; and
A method for manufacturing a solid oxide fuel cell.

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