JP5905293B2 - Method for producing solid oxide fuel cell and film forming apparatus - Google Patents

Description

The present invention relates to a film forming apparatus for forming a manufacturing method及Beauty solid body oxide fuel cell membrane for a solid oxide fuel cell cylindrical in which a plurality of cells are formed on the substrate tube.

  A cylindrical solid oxide fuel cell (SOFC) accommodates a plurality of cell stacks inside a power generation chamber. The cell stack has a power generation section at the center and non-power generation sections at both ends with the power generation section interposed therebetween. In the power generation section of the cell stack, a plurality of cells in which the fuel electrode, the solid electrolyte membrane, and the air electrode are stacked are formed in the circumferential direction of the base tube. A plurality of cells are arranged in the axial direction of the base tube, and adjacent cells are electrically connected in series with an interconnector.

  In the production of the solid oxide fuel cell, first, the fuel electrode, the solid electrolyte membrane and the interconnector are usually formed on the substrate tube by screen printing. Thereafter, the fuel electrode, the solid electrolyte membrane, and the interconnector are co-sintered together with the base tube. An air electrode is formed on the solid electrolyte membrane after co-sintering.

  The air electrode of the solid oxide fuel cell is generally formed by a screen printing method as described in Patent Document 1, for example. Patent Document 2 discloses a plasma spraying method as a method for forming an electrode of a fuel cell. In Patent Document 2, in a cylindrical fuel cell including a cathode electrode (air electrode), a solid electrolyte membrane, and an anode electrode (fuel electrode) in order from the inside, the anode electrode is formed by low-pressure plasma spraying (LLPS).

Japanese Patent No. 3310867 (Claim 1, paragraphs [0005] and [0020]) US Pat. No. 7,141,271 (column 7, lines 57-60)

The surface of the base tube co-sintered as described above is uneven due to the fuel electrode, the solid electrolyte membrane, and the interconnector. Further, the base tube may be bent in the axial direction by co-sintering. In the screen printing method, the air electrode slurry is applied by applying the squeegee to the co-sintered substrate tube surface, but the pressure distribution is caused by the unevenness, and the squeegee is bent partially between the squeegee and the substrate tube. A gap is created. For this reason, dispersion | variation generate | occur | produces in the film thickness and adhesiveness of the air electrode slurry apply | coated.
In the screen printing method, when the squeegee is applied, the screen and the cell may be displaced from each other, so that the film forming accuracy is low. Further, since the slurry supplied onto the screen is larger than the film formation region, the raw material yield is low.

  In plasma spraying, it is difficult to finely control the deposition position. When providing a plurality of cells as in the above solid oxide fuel cell, it is necessary to mask and provide an air electrode at a predetermined position, but the process becomes complicated. In addition, the raw material yield is a problem.

The present invention has been made in view of the above problems, an excellent film formation for forming the manufacturing method及beauty those spatial Kikyoku of the solid oxide fuel cell that can form an air electrode with positional accuracy An object is to provide an apparatus.

  In order to solve the above problems, the present invention provides a solid comprising a plurality of cells including a fuel electrode, a solid electrolyte membrane, and an air electrode, and an interconnector that electrically connects the adjacent cells on a base tube. A method for manufacturing an oxide fuel cell, wherein the fuel electrode and the solid electrolyte membrane are formed on an outer peripheral surface of the base tube, and the fuel electrode and the solid electrolyte membrane are disposed at positions corresponding to the plurality of cells. Forming the interconnector on a solid electrolyte membrane; sintering the fuel electrode, the solid electrolyte membrane, and the interconnector together with the base tube; and the sintered solid electrolyte membrane and interconnect Forming the air electrode at a predetermined position on the connector and sintering the air electrode, wherein the air electrode forming step includes rotating the base tube in a circumferential direction from the dispenser to the empty electrode. The slurry containing the electrode material is discharged, and the slurry film located at the boundary between the cell in which the air electrode is formed and the cell adjacent to the cell and in which the air electrode is formed is dried. And a method for producing a solid oxide fuel cell.

  The present invention provides the air in a solid oxide fuel cell comprising a plurality of cells each including a fuel electrode, a solid electrolyte membrane, and an air electrode on a base tube, and an interconnector that electrically connects the adjacent cells. A film forming apparatus for forming an electrode, wherein the work in which the fuel electrode, the solid electrolyte membrane, and the interconnector are formed on the substrate tube is supported, and the work is disposed in a circumferential direction of the work. A workpiece holder for rotating the workpiece, a camera for photographing the surface of the workpiece, a dispenser for discharging slurry containing the material of the air electrode at a predetermined position on the solid electrolyte membrane and interconnector on the workpiece, and the air A drying section for drying the slurry located at a boundary portion between a cell in which an electrode is formed, and a cell adjacent to the cell and in which the air electrode is formed; And a controller that moves the dispenser and the drying unit in the axial direction of the workpiece, and the controller detects the position of each cell based on the image of the camera. And determining a film forming range based on the position of the cell, moving the dispenser by the moving unit based on the position of the cell and the film forming range, and a predetermined amount from the dispenser within the film forming range. The slurry is discharged, and the drying unit is moved by the moving unit based on the position of the cell and the film formation range, and the film of the slurry located at the end of the film formation range is dried. A film forming apparatus for drying using the unit is provided.

  In the present invention, a dispenser is used to form the air electrode. The dispenser can form an air electrode with a uniform film thickness on a base tube in which a fuel electrode or the like is laminated and an uneven surface is formed. The dispenser can finely adjust the discharge position, and can improve the film forming accuracy. In addition, since the slurry is discharged only to the film forming portion, the raw material yield can be improved.

In recent years, attempts have been made to increase the number of cells in order to increase the amount of power generation in one cell stack. When increasing the number of cells, the distance between the cells is reduced in order to increase the effective power generation area. Thus, when the distance between cells is short, there exists a possibility that the apply | coated air electrode slurry film may spread with surface tension and may be connected with the air electrode slurry film of an adjacent cell. When the slurry film is dried in a connected state, the air electrodes of adjacent cells are electrically connected to each other, so that a short circuit occurs.
Therefore, in the present invention, only both ends of the slurry film of the air electrode formed in the region corresponding to one cell are dried. This drying is performed at the same time as the film formation. Thereafter, the base tube on which the air electrode is formed is sintered. By carrying out like this, it can prevent that a slurry film spreads and can prevent that adjacent cells short-circuit.

In the method of manufacturing a solid oxide fuel cell, it is preferable that warm air is circulated inside the base tube while the slurry film located at the boundary portion is dried.
By carrying out like this, drying of the slurry located in a boundary part can be promoted.

  In the method for producing a solid oxide fuel cell, it is preferable that the dispenser is displaced so that a distance between the dispenser and the solid electrolyte membrane or the interconnector is constant while the slurry is being discharged. .

When the base tube is extruded or when the fuel electrode, the solid electrolyte membrane and the interconnector are co-sintered with the base tube, the base tube (work) is warped. If this warpage is large, the eccentric width becomes large when the workpiece is rotated in the circumferential direction. If the dispenser is fixed, the distance between the workpiece and the dispenser fluctuates due to eccentricity, and the film thickness and adhesion of the formed air electrode vary.
In this way, by forming a film while maintaining a constant distance between the dispenser and the workpiece (solid electrolyte membrane or interconnector) by installing a displacement meter, an air electrode having a uniform thickness and adhesion can be formed. Can do.

  In the method of manufacturing a solid oxide fuel cell, in the step of forming the air electrode, a plurality of types of the slurry having different materials are used to form a film of the slurry, and then the slurry of the slurry is formed. Before the surface of the membrane dries, another slurry film may be formed on the one slurry film to form the air electrode in which the plurality of types of slurry films are laminated.

  By doing so, an air electrode whose composition continuously changes in the film thickness direction can be formed. By changing the composition, the characteristics can be changed in the film thickness direction. For example, by laminating the solid electrolyte slurry and the air electrode slurry as described above, a region where the electrolyte and the electrode material are mixed is formed at the boundary portion. The electrode reaction of the fuel cell occurs at the boundary between the electrolyte and the electrode. When the mixed region of the electrode component and the electrolyte component is formed as described above, the region where the electrode reaction occurs is widened. As a result, the output of the solid oxide fuel cell can be increased.

A reference example of the present invention is a solid oxide fuel comprising a plurality of cells each provided with a fuel electrode, a solid electrolyte membrane, and an air electrode on a base tube, and an interconnector that electrically connects the adjacent cells. Provided is a solid oxide fuel cell, wherein the surface of the air electrode opposite to the solid electrolyte membrane has a plurality of hemispherical convex portions.

  Providing the convex portion on the surface of the air electrode increases the surface area of the air electrode and disturbs the flow of the oxidizing gas on the surface of the air electrode to facilitate the adsorption of the oxidizing gas. Thereby, the performance of the air electrode is improved.

  In the present invention, since the air electrode is formed using the dispenser, the positional accuracy can be improved and the raw material yield can be improved. Furthermore, simultaneously with the formation of the air electrode, the film of the air electrode slurry is partially dried at the boundary between the cell in which the air electrode is formed and the adjacent cell in which the air electrode has already been formed. Thereby, the short circuit by an air electrode slurry film | membrane can be prevented.

It is the cross-sectional schematic of the electric power generation part of the cell stack in a cylindrical solid oxide fuel cell. It is the schematic of the film-forming apparatus which concerns on 1st Embodiment. It is an example of the nozzle shape of a dispenser. It is an example of the nozzle shape of a dispenser. It is an example of the nozzle shape of a dispenser. It is the cross-sectional schematic of the electric power generation part of the solid oxide fuel cell which has the air electrode formed with the film-forming apparatus of 1st Embodiment. It is the schematic of the air electrode surface formed with the film-forming apparatus of 1st Embodiment. It is the schematic of the film-forming apparatus which concerns on 2nd Embodiment. It is the schematic of the film-forming apparatus which concerns on 3rd Embodiment. It is the schematic of the film-forming apparatus which concerns on 4th Embodiment.

  FIG. 1 is a schematic cross-sectional view of a power generation section of a cell stack in a cylindrical solid oxide fuel cell. FIG. 1 shows a cross section along the axial direction of the substrate tube. In the cell stack 1 of FIG. 1, a cell 3 in which a fuel electrode 4, a solid electrolyte membrane 5, and an air electrode 6 are laminated in this order from the substrate tube 2 side is formed on the outer peripheral surface of a cylindrical substrate tube 2. In the cell stack 1, fuel (hydrogen gas or the like) flows inside the base tube 2 and air flows outside the base tube 2.

  One cell 3 is formed in the circumferential direction of the base tube 2, and a plurality of cells 3 are arranged in parallel in the axial direction of the base tube 2. A part of the solid electrolyte membrane 5 is in contact with the substrate tube 2 at one end of the cell 3 in the axial direction of the substrate tube 2. However, the solid electrolyte membrane 5 of one cell 3 is not in contact with the fuel electrode 4 of the adjacent cell 3. An interconnector 7 that connects adjacent cells is formed between each of the plurality of cells 3. The interconnector 7 is in contact with the base tube 2 between the solid electrolyte membrane 5 of one cell 3 and the fuel electrode 4 of the adjacent cell 3. The air electrode 6 is provided in contact with the solid electrolyte membrane 5 and the interconnector 7.

  The process for forming the solid oxide fuel cell will be described below. The materials of the base tube 2, the fuel electrode 4, the solid electrolyte membrane 5, the air electrode 6, and the interconnector 7 listed below are examples, and are not limited to these materials.

  The base tube 2 is made of a porous material mainly composed of calcia-stabilized zirconia (CSZ) or a mixture of CSZ and nickel oxide (NiO) (CSZ + NiO). The diameter of the base tube 2 is substantially uniform in the axial direction. The base tube 2 is porous, and hydrogen gas used as fuel can flow from the inside of the base tube 2 toward the outside (the fuel electrode 4 side). The base tube 2 is formed by, for example, an extrusion method.

A fuel electrode 4 is formed on the base tube 2 by a screen printing method. The fuel electrode 4 is divided into a plurality of areas corresponding to the number of cells.
The fuel electrode 4 is made of, for example, a composite material of nickel oxide (NiO) and a zirconia-based electrolyte material. As the composite material, for example, a mixture of NiO and yttria stabilized zirconia (YSZ) is used. For example, a mixed powder of Ni + YSZ and an aqueous vehicle (water added with a dispersant, a binder, and an antifoaming agent) are mixed to produce a fuel electrode slurry. The fuel electrode slurry is applied in the circumferential direction on the outer peripheral surface of the base tube 2. The mixing ratio of Ni and YSZ is appropriately selected depending on the performance required for the fuel electrode 4. The mixing ratio of the mixed powder and the aqueous vehicle is appropriately selected in consideration of the thickness of the fuel electrode 4, the state of the fuel electrode film after slurry application, and the like.

After the fuel electrode 4 is formed, a solid electrolyte membrane 5 is formed on the base tube 2 by screen printing. The solid electrolyte membrane 5 is formed by being divided into a plurality of areas corresponding to the number of cells.
The solid electrolyte membrane 5 is made of, for example, Y ₂ O ₃ stabilized ZrO ₂ (YSZ). The YSZ powder and the water-based vehicle are mixed to produce a solid electrolyte membrane slurry. The mixing ratio is appropriately selected in consideration of the thickness of the solid electrolyte membrane 5 and the state and thickness of the solid electrolyte membrane after slurry application.

An interconnector 7 is formed on the base tube 2 by screen printing.
The interconnector material is LaCrO ₃ , (La, Sr) CrO ₃ , La (Cr, Mg) O ₃ , (La, Ca) CrO ₃ , (Sr, La) TiO ₃ or the like. The interconnector material powder and water-based vehicle are mixed to produce an interconnector slurry. The interconnector slurry is applied in the circumferential direction of the outer peripheral surface of the base tube 2 at a position corresponding to between adjacent cells. The composition of the powder is appropriately selected according to the performance required for the interconnector. The mixing ratio of the powder and the water-based vehicle is appropriately selected in consideration of the state of the interconnector after applying the slurry.

  The base tube 2 on which the fuel electrode 4, the solid electrolyte membrane 5 and the interconnector 7 are formed is co-sintered in the atmosphere. The sintering temperature is specifically 1350 ° C. to 1450 ° C.

An air electrode 6 is formed on the co-sintered solid electrolyte membrane 5 and interconnector 7. In forming the air electrode 6, the film thickness of the air electrode 6 is specifically in the range of 100 μm to 1000 μm. The air electrode 6 includes, for example, (La, Sr) MnO ₃ , (La, Ca) MnO ₃ , (La, Sr, Ca) MnO ₃ and other LaMnO ₃ based materials, (La, Sr) FeO ₃ , (La, Sr). , Ca) FeO ₃ and other LaFeO ₃ based materials, and (La, Sr) CoO ₃ and LaCoO ₃ based materials such as (La, Sr, Ca) CoO ₃ and other perovskite type oxides as main components.
The air electrode 6 is formed using a dispenser. (La, Sr, Ca) MnO ₃ powder, which is the main component, and an aqueous vehicle are mixed to prepare an air electrode slurry. The mixing ratio of the powder and the water-based vehicle is appropriately selected in consideration of the state of the air electrode and the film thickness after slurry application. The air electrode slurry is discharged from the dispenser onto the solid electrolyte membrane 5 and the interconnector to form a film of the air electrode slurry.

The base tube 2 on which the air electrode 6 is formed is sintered in the atmosphere. The sintering temperature is specifically 1100 ° C. to 1250 ° C. The sintering temperature here is lower than the co-sintering temperature after forming the base tube to the interconnector.
Hereinafter, a method for forming the air electrode will be described in detail.

<First Embodiment>
FIG. 2 is a schematic view of the film forming apparatus according to the first embodiment. In the film forming apparatus 10 of the first embodiment, a work holder 12 is installed on a support base 11. The work holder 12 has a pair of support portions 13 that are spaced apart. A workpiece (base tube after co-sintering) 20 is disposed between the pair of support portions 13, and both ends of the workpiece 20 are supported by the support portions 13. One support portion 13 is provided with a servo motor 14 to allow the workpiece 20 to rotate in the circumferential direction. The servo motor 14 is connected to the control unit 21. The control unit 21 is a computer, for example.

A linear actuator (moving unit) 15 is installed on the support base 11. A plurality of carriages 16 a to 16 d are installed on the linear actuator 15. The linear actuator 15 is disposed such that the carriages 16 a to 16 d move substantially parallel to the axial direction of the workpiece 20. In the film forming apparatus 10 of the first embodiment, the carriage 16 moves to the right in the drawing. In the initial state, the carriage 16a that is the head in the traveling direction of the carriage is located on the left side of the work 20 with respect to the region where the cells (fuel electrode to interconnector) are formed. After film formation, the carriage 16d, which is the last in the carriage traveling direction, is located on the right side of the work 20 with respect to the area where the cell is formed.
A rotary encoder (not shown) is installed at one end of the linear actuator 15. The rotary encoder acquires position information of each carriage 16. The carriage 16 and the rotary encoder are connected to the control unit 21.

  The camera 17 and the dispenser 18 are placed in order from the top in the traveling direction on the rightmost carriage 16a. A dispenser 18 is placed on the carriage 16c. The drying unit 19 is placed on the carriages 16b and 16d.

  The camera 17 is a CCD camera, for example. The camera 17 photographs the surface of the work 20. The camera 17 is connected to the control unit 21.

The dispenser 18 is a jet dispenser, for example. The dispenser 18 communicates with a tank (not shown) that stores the slurry for the air electrode. The slurry is appropriately supplied from the tank so that a predetermined amount of slurry is stored in the nozzle of the dispenser 18.
One or a plurality of dispensers 18 are installed. FIG. 2 shows an example in which two dispensers 18 are installed. Each jet dispenser 18 is connected to the control unit 21.

  3 to 5 show examples of the nozzle shape of the dispenser. 3 to 5, (a) is a longitudinal sectional view of the nozzle, and (b) is a transverse sectional view of the nozzle tip.

  The nozzle 30 of FIG. 3 is provided with a needle 31 at the center of the interior. One end of the needle 31 is pointed and reaches the vicinity of the tip 32 (slurry discharge portion) of the nozzle 30. The needle 31 is movable in the vertical direction by a cylinder (not shown) provided in the upper part of the nozzle 30. The air electrode slurry 33 is stored in the nozzle 30. As the needle 31 moves, a predetermined amount of slurry for the air electrode slurry is ejected from the tip 32. In FIG. 3, the tip 32 of the nozzle is circular. For this reason, the discharged liquid droplet becomes a substantially spherical shape.

The nozzle 40 of FIG. 4 is provided with a needle 41 at the center of the interior as in FIG. The air electrode slurry 43 is stored in the nozzle 40. One end of the needle 41 has a flat shape. The tip 42 of the nozzle 40 has an elliptical shape. In the nozzle 40 of FIG. 4, the discharged liquid droplet has an elliptic sphere shape.
The nozzle 40 in FIG. 4 is arranged so that the major axis of the ellipse at the tip 42 is substantially parallel to the axial direction of the workpiece. By doing so, it is possible to enlarge the application area in one discharge.

The nozzle 50 of FIG. 5 is provided with a needle 51 at the center of the interior. The air electrode slurry 55 is stored in the nozzle 50. The tip 52 of the nozzle 50 has an elliptical shape and has a plurality of circular holes 53. One end of the needle 51 has a comb shape, and the same number of pins 54 as the holes 53 are provided. The pin 54 is installed at a position corresponding to the hole 53 of the nozzle 50. As the needle 51 moves, a plurality of air electrode slurry droplets are ejected from the hole 53 of the tip 52. The discharged liquid droplet has a substantially spherical shape.
The nozzle 50 in FIG. 5 is preferably arranged so that the major axis of the ellipse at the tip 52 is substantially parallel to the axial direction of the workpiece.

  In this embodiment, one or a plurality of nozzles are installed for one dispenser. When a plurality of nozzles are installed, the nozzles are arranged along the axial direction of the workpiece 20. In this embodiment, each nozzle communicates with the same tank.

The nozzle tip of the dispenser 18 is provided on the upper side of the workpiece 20, and the nozzle tip is installed facing downward. When viewed from the circumferential direction of the workpiece 20, the nozzle tip does not necessarily have to be placed on the vertex of the workpiece 20, and may be displaced from the vertex of the workpiece 20. For example, if the nozzle tip is installed within a range of ± 45 ° from the apex of the work 20, the slurry discharged from the nozzle can adhere to the work 20.
The dispenser 18 is arranged at a predetermined distance from the surface of the workpiece 20, preferably with a value in the range of 0.1 mm to 10 mm.

The drying unit 19 is for drying the air electrode slurry formed on the workpiece 20. The drying unit 19 is a hot air machine or an ultraviolet ray generator. When the warm air machine is adopted, warm air of about 50 ° C. to 100 ° C. is fed from the drying unit 19 toward the work 20. When the ultraviolet ray generator is employed, for example, ultraviolet rays having a wavelength of 200 nm to 400 nm are irradiated toward the workpiece 20.
Each of the drying units 19 is connected to the control unit 21.

One drying unit 19 is installed for each 181 dispensers. The drying unit 19 is installed behind the dispenser 18 with respect to the traveling direction of the carriage 16 during film formation. When providing the some dispenser 18 like the film-forming apparatus 10 of 1st Embodiment, the dispenser 18 and the drying part 19 are alternately mounted in each trolley | bogie 16a-d.
When viewed from the circumferential direction of the workpiece 20, the dispenser 18 and the drying unit 19 may be installed in the same manner. Alternatively, for example, when the cell interval is narrow, the installation position of the drying unit 19 may be shifted from the installation position of the dispenser 18 in the circumferential direction.

In the film forming apparatus 10 of the first embodiment, the hot air supply unit 22 may be installed. In this case, the hot air supply unit 22 is in communication with the support unit 13 of the work holder 12 on which the servo motor 14 is not installed. Hot air is supplied from the hot air supply unit 22 to the inside of the base tube of the workpiece 20. The warm air flowing inside the base tube is set to about 50 to 100 ° C.
The warm air supply unit 22 may heat the air with a heater or the like in order to produce warm air, or may heat the air using the exhaust heat of the motor used in the film forming apparatus 10. good.

A process of forming an air electrode on the workpiece 20 using the film forming apparatus 10 of the first embodiment will be described below.
First, the workpiece 20 is attached to the workpiece holder 12.

The control unit 21 acquires the position and size of the cell on the workpiece 20.
The control unit 21 moves the carriage 16a in the direction of the workpiece 20 axis. In FIG. 2, the carriage 16a moves to the right in the drawing. The camera 17 photographs the surface of the workpiece 20 while moving along the axial direction of the workpiece 20 by the carriage 16a. In the initial state, the carriage 16a on which the camera 17 is placed is disposed on the end side with respect to the film forming portion on the workpiece (the region where the fuel electrode and the like are formed). For this reason, the camera 17 starts photographing from a non-film forming portion (base tube) on the workpiece 20. The carriage 16a moves to a position where the camera 17 can photograph all the film forming portions on the surface of the workpiece 20. After shooting, the carriage 16a is returned to the initial position.

  The camera 17 transmits the captured image to the control unit 21 while shooting. The rotary encoder transmits position information of the carriage 16a to the control unit 21.

  The control unit 21 receives a camera image. The control unit 21 processes the camera image simultaneously with shooting. The control unit 21 detects a boundary where the color tone of the surface of the work 20 in the processed image changes. The control unit 21 associates the camera image (processed image) with the position information of the carriage 16a from the rotary encoder.

  The control unit 21 determines that the boundary first detected in the camera (trolley) movement direction is the origin. The origin is the boundary between the fuel electrode on the workpiece 20 and the solid electrolyte, and is a place represented by the symbol O when taken from the left to the right in FIG. The control unit 21 acquires the origin position data based on the position information from the rotary encoder.

  The number of cells N of the attached workpiece 20 is input in advance to the control unit 21. The control unit 21 determines that the even-numbered boundary detected in the moving direction of the camera is the boundary A that changes from the solid electrolyte membrane to the interconnector. The control unit 21 determines the boundary detected in the third and subsequent odd directions in the moving direction of the camera as the boundary B changing from the interconnector to the solid electrolyte membrane or from the interconnector to the base tube. The control unit 21 acquires position data of a plurality of boundaries A and B based on position information from the rotary encoder.

  The control unit 21 recognizes from the origin to the first detected boundary B as the first cell. Next, the control unit 21 recognizes the interval between two adjacent boundaries B as the second to Nth cells. The control unit 21 acquires the position data of each cell from the position data of each boundary B. The control unit 21 acquires the dimension data of each cell based on the acquired cell position data. The control unit 21 determines the film forming range of the slurry for the air electrode based on the position data of the boundary A and the acquired dimension data.

  The control unit 21 stores the acquired origin position data, cell position data, and film formation range data in the memory of the control unit 21.

Next, the control unit 21 forms a slurry for the air electrode on the work 20.
The control unit 21 calls the origin position data, cell position data, and film formation range data from the memory. The control unit 21 moves the carriage 16a along the workpiece 20 axial direction in the right direction in FIG.

  The camera 17 captures the surface of the workpiece 20 and transmits the captured image to the control unit 21. The rotary encoder transmits position information of the carriage 16a to the control unit 21.

  The control unit 21 receives a camera image and processes the camera image simultaneously with shooting. With the above method, the control unit 21 detects the origin and obtains position data. The control unit 21 compares the origin position data acquired here with the origin position data called from the memory. The control unit 21 calculates a difference when the acquired position data is different from the called position data. Based on the acquired difference, the control unit 21 corrects the cell position data and the film formation range data.

Based on the cell position data and the film formation range data, the control unit 21 moves the carriages 16a and 16c on which the dispenser 18 is placed to the film formation start position of the cell to be formed first. In the film forming apparatus 10 of FIG. 2, the carriage 16a moves to the film formation start position of the second cell from the left, and the carriage 16c moves to the film formation start position of the leftmost cell.
The control unit 21 operates the servo motor 14 to rotate the workpiece 20 in the circumferential direction. The controller 21 discharges the air electrode slurry from the dispenser 18 onto the workpiece 20. Thereby, the film | membrane of the slurry for air electrodes is formed in the circumferential direction of the workpiece | work 20 in a predetermined film-forming position.

  The adhesion between the air electrode slurry film and the work 20 has a correlation with the rotation speed of the work 20 during film formation. In order to obtain good adhesion, for example, if the diameter of the workpiece 20 is in the range of 10 to 30 mm, the rotation speed of the workpiece is preferably in the range of 1 to 70 rpm.

  The film of the air electrode slurry is formed while the workpiece 20 is rotated approximately once. The controller 21 adjusts the slurry discharge amount (droplet diameter), the discharge time, the discharge interval, and the like from the dispenser 18 so as to form a continuous film and a uniform film thickness. For example, the discharge amount becomes relatively small immediately after the start of discharge and immediately before the stop of discharge. Therefore, by synchronizing the rotation speed of the workpiece 20 and the discharge timing, the film immediately after the discharge is disclosed and the film immediately before the discharge stop are overlapped to make the film thickness uniform.

  After the first row of slurry films is formed in the circumferential direction of the workpiece 20, the control unit 21 moves the carriages 16a and 16c to predetermined positions. The controller 21 discharges the air electrode slurry from the dispenser 18 to form a second row of slurry films in the circumferential direction of the workpiece 20. The movement of the carriages 16a and 16c and the discharge from the dispenser 18 are repeated to form the air electrode slurry at a predetermined position on the cell. At this time, the interval between the vertices of the droplets ejected to adjacent rows is made smaller than the droplet diameter. The interval between the droplets corresponds to the moving distance of the carriages 16a and 16c when forming the slurry film in the next row. By doing so, droplets in adjacent rows overlap, and the film thickness of the air electrode slurry film in one cell can be made uniform. For example, the interval between the droplets is preferably in the range of 30 to 75% of the droplet diameter. Since the droplet diameter has a corresponding relationship with the weight (discharge amount) of the slurry to be discharged, it is managed by the discharge amount.

  Based on the cell position data and the film formation range data, the control unit 21 moves the carriage 16b on which the drying unit 19 is placed to the film formation start position of the cell currently formed by the dispenser 18.

  When the dispenser 18 forms the air electrode slurry to the predetermined position, the control unit 21 activates the drying unit 19 placed on the carriage 16b. The actuated drying unit 19 applies hot air or ultraviolet rays to a region including the boundary between the air electrode slurry film and the solid electrolyte film at the film formation start position for a predetermined time. As a result, the air electrode slurry film in the region exposed to hot air or ultraviolet rays is dried. That is, the air electrode slurry film end at the film formation start position is dried. The drying time may be appropriately set according to the rotation speed of the workpiece 20, the composition of the air electrode slurry, the film thickness of the air electrode slurry, and the like. After a predetermined time has elapsed, the control unit 21 stops the operation of the drying unit 19.

  The drying of the air electrode slurry film by the drying unit 19 is performed while the dispenser 18 forms another region in the same cell. Warm air or ultraviolet light strikes the nozzle tip of the dispenser 18 so that the slurry at the nozzle tip is dried and the discharge of the slurry is not hindered. For example, after the dispenser 18 and the drying unit 19 are sufficiently separated from each other in the workpiece 20 axial direction, the drying unit 19 is operated, or the flow rate of the warm air supplied from the drying unit 19 is adjusted.

  Note that at the film formation start position of the first cell (the cell located at the end of the power generation unit), since there is no adjacent cell, the slurry film is not connected to the slurry film of the adjacent cell. Accordingly, the film formation start position of the first cell is not necessarily dried. Therefore, it is not necessary to move the carriage 16d at this time.

  When the hot air supply unit 22 is installed in the film forming apparatus 10, the control unit 21 operates the hot air supply unit 22 simultaneously with operating the drying unit 19. The hot air supply unit 22 supplies hot air of about 50 to 100 ° C. to the inside of the base tube of the workpiece 20. Thereby, the workpiece | work 20 is heated and drying of the slurry film | membrane for air electrodes by the drying part 19 is accelerated | stimulated.

When film formation is completed in the entire film formation range in one cell, the control unit 21 moves the carriages 16b and 16d to the film formation end position. Since it is not necessary to dry except for the edge part of a slurry film | membrane, the drying part 19 has stopped at the time of this movement.
The control unit 21 operates the drying unit 19. The drying unit 19 applies hot air or ultraviolet rays to a region including the boundary between the air electrode slurry film and the interconnector at the film formation end position for a predetermined time. Thereby, the slurry film | membrane edge part for air electrodes in the film-forming completion position dries.

When the drying of the air electrode slurry film at the film formation end position is completed, the control unit 21 moves the carriages 16a and 16c to the film formation start position of the next cell to be formed. When two dispensers 18 are provided as shown in FIG. 2, the control unit 21 moves the carriages 16a and 16c to the next cell. Simultaneously with the movement of the carriages 16a and 16c, the control unit 21 moves the carriages 16b and 16d to predetermined positions.
Next, the control unit 21 causes the dispenser 18 to form a slurry for the air electrode in a predetermined film formation range, and causes the drying unit 19 to use the air electrode at the film formation start position and the film formation end position in the same process as described above. The slurry membrane edge is dried. It is not necessary to dry the end of the slurry film for the air electrode at the film formation end position of the Nth cell.

  The above steps are repeated until film formation in the Nth cell is completed. After film formation in all cells is completed, the control unit 21 stops the servo motor 14 and stops the rotation of the workpiece 20. The workpiece 20 is removed from the workpiece holder 12. Thereafter, the workpiece 20 is sintered as described above to form a cell stack.

  In the present embodiment, as described above, the position / dimension measurement and film formation may be performed continuously with one workpiece, or the position / dimension measurement may be performed with a plurality of workpieces. In the latter case, the workpiece is removed between the position / dimension measurement and the film formation. However, since the origin position is corrected by the camera before the film formation, the film can be formed at a desired position.

FIG. 6 is a schematic cross-sectional view of a power generation unit of a solid oxide fuel cell in which an air electrode is formed by the film forming apparatus of this embodiment.
The air electrode 6 has a plurality of hemispherical convex portions 8 on the surface. The air electrode 6 is formed on the solid electrolyte membrane 5 and the interconnector 7 having a macroscopic smooth surface. Since the air electrode 6 is thicker than the fuel electrode 4, the solid electrolyte membrane 5, and the interconnector 7 formed in the lower layer, the top of the convex portion 8 is affected by the step of each layer provided in the lower layer. I do not receive it. For this reason, the convex portion 8 has substantially the same height from the surface of the base tube 2.

The plurality of convex portions 8 are provided so as to be connected to the adjacent convex portions 8. The bottom portion 8a of the convex portion 8 is a line connecting the connecting portions 8b of the adjacent convex portions 8. The contact angle of the convex portion 8 with respect to the bottom portion 8a is adjusted to 10 ° to 45 °. When the adjacent convex part 8 is adjoining, the convex part 8 is high and a contact angle becomes large, and a trough part is formed in the connection part 8b between the convex parts 8. FIG. On the other hand, when the space | interval of the adjacent convex part 8 is spreading, the convex part 8 is low and a contact angle becomes small. The shape of the convex portion 8 and the connecting portion 8b is controlled by the film forming pitch by the dispenser, the slurry discharge amount, and the sintered state. The height of the convex portion 8 measured from the bottom portion 8a is preferably 100 to 300 μm, and the width of the bottom portion 8a is preferably adjusted to 300 to 600 μm.
In addition, the connection part 8b can also be made not to overlap between the adjacent convex parts 8 by expanding the discharge pitch of the slurry by a dispenser. In this case, the convex portion 8 formed on the surface of the air electrode 6 has a gentle gradient, the height of the convex portion 8 is reduced, and the air electrode 6 having a smooth surface is formed.

  The present invention increases the surface area of the air electrode 6 by providing the hemispherical convex portion 8 on the surface of the air electrode 6 and disturbs the flow of the oxidizing gas on the surface of the air electrode 6 so that the oxidizing gas is easily adsorbed. To do. Thereby, the performance of the air electrode 6 is improved.

  FIG. 7 is a schematic view of the air electrode surface formed by the film forming apparatus of this embodiment. A hemispherical convex portion 8 formed on the air electrode surface is indicated by a circle. The convex portions 8 are formed to be arranged vertically and horizontally on the surface of the air electrode.

  FIG. 7A shows a case where the convex portions 8 are aligned in the horizontal direction and the vertical direction of the paper. In this case, since the interval between the connecting portions 8b of the convex portion 8 is narrowed, the convex portion becomes high on average and the contact angle tends to increase. Moreover, the height of each adjacent convex part 8 is substantially constant. The difference in height between adjacent convex portions is adjusted to 0.3 μm or less.

  FIG. 7B shows a case in which the convex portions 8 adjacent in the horizontal direction on the paper surface are formed with their positions shifted in the vertical direction on the paper surface. In this case, there are a portion where the interval between the connecting portions 8b of the convex portion 8 is narrow and a portion where the interval is widened. For this reason, the height of the convex portion 8 is not constant, and the difference in height between the adjacent convex portions 8 is greater than 0.3 μm.

  The convex part 8 of the air electrode is formed by discharging a dot-like slurry for the air electrode with a dispenser, drying it, and baking it. By adjusting the discharge position of the slurry by the dispenser, the arrangement of the surface, the height of the convex portion, and the contact angle can be controlled.

Second Embodiment
FIG. 8 is a schematic view of a film forming apparatus according to the second embodiment. In the film forming apparatus 60 of FIG. 8, one dispenser 68 and one drying unit 69 are installed, but a plurality of apparatuses may be installed as shown in FIG. In FIG. 8, the hot air supply unit is omitted.
In the film forming apparatus 60 of the second embodiment, a displacement meter (height sensor) 72 is added to the film forming apparatus of the first embodiment. The displacement meter 72 is connected to the control unit 71. The film forming apparatus 60 of the second embodiment is effective when an air electrode is formed on a workpiece with a large warp.

  The displacement meter 72 is placed on the same cart 66a as the dispenser. When a plurality of dispensers are provided, one displacement meter is placed on each cart. When viewing the axial direction of the workpiece 70, the camera 67, the displacement meter 72, and the dispenser 68 are placed in this order from the top in the traveling direction of the carriage 66a.

  When the workpiece 70 is warped, the track range of the workpiece 70 becomes larger than the outer diameter of the workpiece 70 by the amount of eccentricity. For this reason, when viewed from the circumferential direction of the work 70, the camera 67, the displacement meter 72, the dispenser 68, and the drying unit 69 are installed away from the trajectory range of the work 70. The displacement meter 72 is installed so as to face the center of rotation of the workpiece 70. As in the first embodiment, the nozzle tip of the dispenser 68 is provided on the upper side of the work 70. The displacement meter 72 may be installed at the same position as the dispenser 68 when viewed from the circumferential direction of the work 70 or may be installed shifted in the circumferential direction. In the case of being displaced in the circumferential direction, the displacement meter 72 is installed on the side opposite to the rotation direction of the work 70 by a predetermined angle with respect to the dispenser 68. The predetermined angle is appropriately set in consideration of the rotation speed of the work 70 and a movement delay of a dispenser described later. Specifically, an angle greater than 0 ° and less than 45 ° is desirable.

  In the film forming apparatus 60 of the second embodiment, the dispenser 68 is provided with a dispenser height adjusting unit (not shown) that makes the distance between the dispenser 68 and the workpiece 70 variable. The dispenser 68 is disposed at a predetermined distance from the surface of the workpiece 70 by the dispenser height adjustment unit. The dispenser height adjustment unit is connected to the control unit 71.

A process of forming an air electrode on the work 70 using the film forming apparatus 60 of the second embodiment will be described below.
In the same process as in the first embodiment, the control unit 71 obtains origin position data, cell position data, and film formation range data. The control unit 71 stores the acquired data in the memory.

Next, the control unit 71 forms a slurry for the air electrode on the work 70.
The control unit 71 acquires the position data of the origin using the camera 67 in the same process as in the first embodiment. The obtained origin position data is compared with the origin position data retrieved from the memory, and the cell position data and the film formation range data are corrected as necessary.

  Based on the cell position data and the film formation range data, the control unit 71 moves the carriages 66a and 66b on which the dispenser 68 is placed to the film formation start position of the cell to be formed first. The controller 71 operates the servo motor 64 to rotate the workpiece 70 in the circumferential direction.

The displacement meter 72 measures the distance d ₁ between the workpiece 70 and the displacement meter 72 in the circumferential direction at the cell deposition start position. The displacement meter 72 transmits data regarding the distance d ₁ to the control unit 71. Next, the control unit 71 moves the carriages 66a and 66b to the next measurement position. This movement distance is equivalent to the application area | region of the axial direction by one discharge. Displacement meter 72, in the measurement position, to measure the distance d ₂ between the workpiece 70 and the displacement meter 72 in the circumferential direction. The displacement meter transmits data regarding the distance d ₂ to the control unit 71. The above measurement and data transmission are performed for the entire film formation range.

In the control unit 71, the distance between the rotation center of the workpiece 70 and the displacement meter 72 and the outer radius (average value) of the attached workpiece 70 are input in advance.
Control unit 71, based on the data acquisition interval in the rotational speed displacement meter, associating the d _i obtained with the circumferential direction of the measurement position.

The control unit 71 calculates a distance d ₀ between the workpiece 70 and the displacement meter when there is no warpage from the distance between the rotation center and the displacement meter 72 and the outer radius of the workpiece 70. The control unit 71 receives data of distances d _i (i = 1, 2,...) In the circumferential direction at each measurement position of the displacement meter. The control unit 71 compares the distance d _i with the calculated d ₀ and obtains data of the change amount Δd _i (Δd _i = d _i −d ₀ ) with respect to d ₀ of the distance d _i . Since d _i is associated with the measurement position in the circumferential direction, the data of Δd _i is also associated with the measurement position in the circumferential direction.

  The distance in the axial direction of the workpiece 70 between the displacement meter 72 and the dispenser 68 is input in the control unit 71 in advance. When the nozzle tip of the dispenser 68 reaches the position, the control unit 71 discharges the air electrode slurry from the dispenser 68 onto the work 70. As a result, a film of slurry for the air electrode in the i-th row is formed in the circumferential direction of the work 70.

At this time, the control unit 71, while discharging the air electrode slurry dispenser 68, to actuate the dispenser height adjustment unit based on the data of the [Delta] d _i, holds the distance between the dispenser 68 tip and the workpiece 70 surface to a certain . Specifically, when Δd _i <0 (when the workpiece approaches the displacement meter), the control unit 71 moves the dispenser 68 away from the workpiece 70. When Δd _i > 0 (when the workpiece moves away from the displacement meter), the control unit 71 brings the dispenser 68 closer to the workpiece 70. The distance between the tip of the dispenser and the workpiece surface is desirably maintained at a predetermined value within a range of 0.1 mm to 10 mm.

Specifically, when the dispenser 68 reaches the film formation start position, the control unit 71 keeps the distance between the dispenser 68 and the surface of the work 70 constant based on the data of Δd ₁ as described above. The air electrode slurry is discharged onto the work 70 to form a first row of air electrode slurry films. Thereafter, the control unit 71 moves the carriages 66a and 66c to the next film formation position. The controller 71 discharges the air electrode slurry from the dispenser 68 to form a second row of slurry films in the circumferential direction of the work 70. At this time, the controller 71 discharges the slurry for the air electrode from the dispenser 68 onto the work 70 while keeping the distance between the dispenser 68 and the surface of the work 70 constant based on the data of Δd ₂ as described above. A slurry film for air electrode in a row is formed. The controller 71 repeats the above operation to form an air electrode slurry film in a predetermined film formation range.

  At the same time as the film formation by the dispenser 68, the control unit 71 dries both ends of the air electrode slurry film by the drying unit 69 in the same manner as in the first embodiment. When the hot air supply unit is installed, the hot air supply unit supplies hot air to the inside of the base tube simultaneously with the drying by the drying unit.

  When the film formation in one cell is completed, the controller 71 moves the carriages 66a and 66b to the film formation range of the next cell. And the slurry film for air electrodes is formed in the following cell by the process similar to the above. The above process is repeated until film formation in the Nth cell is completed. After film formation in all cells is completed, the control unit 71 stops the servo motor 64 and stops the rotation of the work 70. The work 70 is removed from the work holder 62. Thereafter, the workpiece 70 is sintered as described above to form a cell stack.

<Third Embodiment>
FIG. 9 is a schematic view of a film forming apparatus according to the third embodiment. The film forming apparatus 80 of the third embodiment is different from that of the first embodiment in that a plurality of dispensers 88 are installed for one drying unit 89. Although one drying unit and two dispensers 88a and 88b are installed in FIG. 9, three or more dispensers may be installed for one drying unit. Two or more sets of drying units and dispensers may be installed.

In the film forming apparatus 80 of FIG. 9, a camera 87 and a dispenser 88a are placed on a carriage 86a. The dispenser 88b is placed on the carriage 86b. The drying unit 89c is placed on the carriage 86c.
The dispenser 88a and the dispenser 88b communicate with different tanks (not shown). Each tank accommodates slurry having different materials. For example, the solid electrolyte membrane slurry, the interconnector slurry, or the air electrode material-containing slurry is accommodated in the tank connected to the dispenser 88a. The tank for communicating with the dispenser 88b contains the above-described slurry for the air electrode. The slurry for the solid electrolyte membrane is a slurry containing the above-described solid electrolyte membrane material, and is used for improving the adhesion between the solid electrolyte membrane and the air electrode. The interconnector slurry is a slurry containing the interconnector material described above, and is used to improve the adhesion between the interconnector and the air electrode. The air electrode material-containing slurry here is the same material as the above-described air electrode material (LaMnO ₃ -based material, LaFeO ₃ -based material, LaCoO ₃ -based material), and a powder having a smaller particle diameter than the above-mentioned slurry for air electrode Containing. The powder contained in the air electrode slurry has a particle size of 1 to 50 μm, whereas the powder contained in the air electrode material-containing slurry has a particle size of 1 μm or less.

A process of forming an air electrode on the work 90 using the film forming apparatus 80 of the third embodiment will be described below.
In the same process as in the first embodiment, the control unit 91 obtains origin position data, cell position data, and film formation range data. The control unit 91 stores the acquired data in the memory.

  The control unit 91 acquires the position data of the origin using the camera 87 in the same process as in the first embodiment. The obtained origin position data is compared with the origin position data retrieved from the memory, and the cell position data and the film formation range data are corrected as necessary.

  Based on the cell position data and the film formation range data, the controller 91 moves the carriage 86a on which the dispenser 88a is placed to the film formation start position of the cell in which the film is formed first. The control unit 91 operates the servo motor 84 to rotate the workpiece 90 in the circumferential direction. The controller 91 discharges the slurry A from the dispenser 88a to a predetermined film forming range in the same process as in the first embodiment. As a result, a film of slurry A is formed in the circumferential direction of the workpiece 90.

  Based on the cell position data and the film formation range data, the control unit 91 moves the carriage 86b on which the dispenser 88b is placed to the film formation start position of the cell to be formed first. The controller 91 discharges the slurry B from the dispenser 88b onto the slurry A film before the surface of the slurry A film formed by the dispenser 88a is dried. As a result, a film of slurry B is formed in the circumferential direction of the workpiece 90.

  Since the slurry B is formed before the surface of the film of the slurry A is dried, the slurry A and the slurry B are mixed in the vicinity of the boundary of the film. That is, the composition of the air electrode formed by the film forming apparatus 80 changes continuously. For example, when a solid electrolyte membrane slurry is used as the slurry A and an air electrode slurry is used as the slurry B, the electrolyte and the electrode material are mixed in the vicinity of the boundary.

  At the same time as the film formation by the dispensers 88a and 88b, the control unit 91 dries both ends of the laminated film of the slurry A and the slurry B by the drying unit 89 as in the first embodiment. When the hot air supply unit is installed, the hot air supply unit supplies hot air to the inside of the base tube simultaneously with the drying by the drying unit.

  When film formation in one cell is completed, the controller 91 moves the carriages 86a to 86c to the film formation range of the next cell. And the slurry film for air electrodes is formed in the following cell by the process similar to the above. The above process is repeated until film formation in the Nth cell is completed. After film formation in all the cells is completed, the control unit 91 stops the servo motor 84 and stops the rotation of the work 90. The workpiece 90 is removed from the workpiece holder ▽. Thereafter, the workpiece 90 is sintered as described above to form a cell stack.

  The electrode reaction in the fuel cell occurs at the boundary between the solid electrolyte membrane and the electrode (air electrode and fuel electrode). Thus, when the area | region where electrolyte and electrode material were mixed is formed, an electrode reaction generation | occurrence | production area will spread and an output can be increased.

  In the third embodiment, a displacement meter may be provided as in the second embodiment, and the dispenser may be moved based on data from the displacement meter.

<Fourth embodiment>
FIG. 10 is a schematic view of a film forming apparatus according to the fourth embodiment. The film forming apparatus 100 of the fourth embodiment is the same as FIG. 2 except that a plurality of nozzles 112 a to 112 c are installed for one dispenser 108.

  A nozzle 112a, a nozzle 112b, and a nozzle 112c are installed in order from the top in the traveling direction of the carriage. The nozzles 112 a to 112 c are aligned along the axial direction of the workpiece 110. The nozzle interval in one dispenser 108 is appropriately set in consideration of the size of the droplet and the film thickness. The nozzles 112a to 112c communicate with different tanks (not shown). Each tank accommodates slurry having different materials. The nozzles 112a to 112c are connected to the control unit 111, respectively.

A process of forming an air electrode on the work 110 using the film forming apparatus 100 of the fourth embodiment will be described below.
In the same process as in the first embodiment, the control unit 111 acquires the origin position data, the cell position data, and the film formation range data. The control unit 111 stores the acquired data in the memory.

  The control unit 111 acquires the position data of the origin using the camera 107 in the same process as in the first embodiment. The obtained origin position data is compared with the origin position data retrieved from the memory, and the cell position data and the film formation range data are corrected as necessary.

  The control unit 111 moves the carriages 106a and 106c on which the dispenser 108 is placed until the nozzle 112a reaches the film formation start position of the cell in which the film is formed first, based on the cell position data and the film formation range data. Let The control unit 111 operates the servo motor 104 to rotate the workpiece 110 in the circumferential direction. The controller 111 discharges the slurry A from the nozzle 112a of the dispenser 108 to a predetermined film forming range in the same manner as in the first embodiment. As a result, a film of slurry A is formed in the circumferential direction of the workpiece 110.

When the nozzle 112 b reaches the cell film formation start position, the control unit 111 discharges the slurry B from the nozzle 112 b to a predetermined film formation range, and forms a film of the slurry B in the circumferential direction of the workpiece 110. Similarly, the controller 111 discharges the slurry C from the nozzle 112 c to a predetermined film formation range, and forms a film of the slurry C in the circumferential direction of the work 110.
Slurry B and C are formed before the surface of the lower layer is dried. For this reason, the slurry is mixed in the vicinity of the boundary of the film.

  At the same time as the film formation by the dispenser 108, the control unit 111 uses the drying unit 109 to dry both end portions of the slurry laminated film in the same manner as in the first embodiment. When the hot air supply unit is installed, the hot air supply unit supplies hot air to the inside of the base tube simultaneously with the drying by the drying unit.

  When film formation in one cell is completed, the controller 111 moves the carriages 106a to 106d to the film formation range of the next cell. And the slurry film for air electrodes is formed in the following cell by the process similar to the above. The above process is repeated until film formation in the Nth cell is completed. After film formation in all the cells is completed, the control unit 111 stops the servo motor 104 and stops the rotation of the work 110. The workpiece 110 is removed from the workpiece holder 102. Thereafter, the workpiece 110 is sintered as described above to form a cell stack.

  In the fourth embodiment, a displacement meter may be provided as in the second embodiment, and the dispenser may be moved based on data from the displacement meter.

DESCRIPTION OF SYMBOLS 1 Cell stack 2 Base tube 3 Cell 4 Fuel electrode 5 Solid electrolyte membrane 6 Air electrode 7 Interconnector 8 Convex part 8a Bottom part 8b Connection part 10,60,80,100 Film-forming apparatus 11,61,81,101 Support stand 12, 62, 82, 102 Work holder 13, 63, 83, 103 Support part 14, 64, 84, 104 Servo motor 15, 65, 85, 105 Linear actuator (moving part)
16a, 16b, 16c, 16d, 66a, 66b, 86a, 86b, 86c, 106a, 106b, 106c, 106d Dolly 17, 67, 87, 107 Camera 18, 68, 88a, 88b, 108 Dispenser 19, 69, 89, 109 Drying unit 20, 70, 90, 110 Work piece 21, 71, 91, 111 Control unit 22 Hot air supply unit 30, 40, 50 Nozzle 31, 41, 51 Needle 32, 42, 52 Tip of nozzle (slurry discharge unit )
33, 43, 55 Slurry for air electrode 53 hole 54 pin 72 Displacement meter O Origin

Claims (5)

A method for producing a solid oxide fuel cell comprising a plurality of cells comprising a fuel electrode, a solid electrolyte membrane, and an air electrode on a base tube, and an interconnector for electrically connecting the adjacent cells,
Forming the fuel electrode and the solid electrolyte membrane on the outer peripheral surface of the base tube, and forming the interconnector on the fuel electrode and the solid electrolyte membrane at a position corresponding to the plurality of cells; When,
Sintering the fuel electrode, the solid electrolyte membrane, and the interconnector together with the base tube;
Forming the air electrode at a predetermined position on the sintered solid electrolyte membrane and the interconnector, and sintering the air electrode.
Forming the air electrode comprises:
While discharging the slurry containing the material of the air electrode from the dispenser while rotating the base tube in the circumferential direction,
A solid oxide fuel cell comprising a step of drying a film of the slurry positioned at a boundary portion between a cell in which the air electrode is formed and a cell adjacent to the cell and in which the air electrode is formed Production method.   2. The method for producing a solid oxide fuel cell according to claim 1, wherein hot air is circulated inside the base tube while the slurry film located at the boundary portion is dried. 3.   The solid oxide fuel according to claim 1 or 2, wherein the dispenser is displaced so that a distance between the dispenser and the solid electrolyte membrane or the interconnector is constant while the slurry is being discharged. Battery manufacturing method.   In the step of forming the air electrode, after forming a film of the one slurry using a plurality of types of the slurry having different materials, the slurry of the one slurry is dried before the surface of the film of the one slurry is dried. 4. The solid oxide according to claim 1, wherein another film of the slurry is formed on the film to form the air electrode in which the plurality of types of films of the slurry are stacked. 5. Of manufacturing a fuel cell. Forming the air electrode in a solid oxide fuel cell comprising a plurality of cells including a fuel electrode, a solid electrolyte membrane, and an air electrode and an interconnector for electrically connecting the adjacent cells on a substrate tube A film forming apparatus for performing
A work holder for supporting the work on which the fuel electrode, the solid electrolyte membrane, and the interconnector are formed on the base tube, and rotating the work in a circumferential direction of the work;
A camera for photographing the surface of the workpiece;
A dispenser that discharges slurry containing the material of the air electrode to a predetermined position on the solid electrolyte membrane and interconnector on the workpiece;
A drying unit that dries the slurry located at a boundary between the cell in which the air electrode is formed and the cell adjacent to the cell and in which the air electrode is formed;
A moving unit that moves the camera, the dispenser, and the drying unit in the axial direction of the workpiece;
A control unit,
The control unit detects the position of each cell based on the image of the camera, determines a film formation range based on the cell position, and based on the cell position and the film formation range, While moving the dispenser by the moving unit, and discharging a predetermined amount of the slurry from the dispenser in the film formation range,
Film formation for moving the drying unit by the moving unit based on the position of the cell and the film forming range, and drying the film of the slurry located at the end of the film forming range using the drying unit apparatus.

Images