JP2016213145A - Manufacturing system of solid oxide fuel battery cell, and manufacturing method arranged to use the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing system by which a solid oxide fuel battery cell with a high degree of integration of power-generation elements can be manufactured efficiently even if a porous supporting body is low in dimensional precision.SOLUTION: A manufacturing system according to the present invention is a manufacturing system of a solid oxide fuel battery cell (16) having a plurality of power-generation elements (16a) formed therein and each having, on a porous supporting body (97), a fuel electrode layer (98), an electrolyte layer (100) and an air electrode layer (101) which are functional layers. The manufacturing system comprises: a plane film deposition device (130) for forming the first functional layers of the plurality of power-generation elements on a surface of the porous supporting body at a time; a dot film deposition device (110) for forming the outermost second functional layers by uninterruptedly spraying drops of slurry to form dots of the slurry and integrating the dots; and an extrusion film deposition device (140) with a nozzle for uninterruptedly extruding a masking-formation agent in rod-like form to deposit the masking-formation agent onto a portion on which the two-dimensional film deposition is not performed by the plane film deposition device.SELECTED DRAWING: Figure 11

Description

  TECHNICAL FIELD The present invention relates to a solid oxide fuel cell manufacturing system, and in particular, a plurality of power generating elements including a fuel electrode layer, an electrolyte layer, and an air electrode layer as functional layers on an electrically insulating porous support. And a manufacturing system of a solid oxide fuel cell in which these power generation elements are connected by an interconnector, and a manufacturing method using the same.

  A solid oxide fuel cell (hereinafter also referred to as “SOFC”) uses an oxide ion conductive solid electrolyte as an electrolyte, has electrodes attached to both sides thereof, and supplies fuel gas to one side. The fuel cell operates at a relatively high temperature by supplying an oxidant gas (air, oxygen, etc.) to the other side.

  Japanese Patent Laying-Open No. 2013-175305 (Patent Document 1) describes a method for manufacturing a solid oxide fuel cell. In the solid oxide fuel cell described here, a plurality of power generation elements each including a fuel electrode, a solid electrolyte membrane, and an air electrode are formed on a base tube, and these power generation elements are electrically connected by an interconnector. Is connected to. In this fuel cell manufacturing method, a fuel electrode is formed on a substrate tube by a screen printing method, and then a solid electrolyte membrane and an interconnector are sequentially formed by a screen printing method. The base tube in which each layer is thus formed is co-sintered in the atmosphere, and then an air electrode is formed on the sintered solid electrolyte membrane using a dispenser. That is, the slurry in which the powder of the material forming the air electrode is suspended is discharged onto the solid electrolyte membrane and the interconnector, and the air electrode slurry film is formed at the position where the air electrode is to be formed. Finally, the base tube on which the air electrode is formed is sintered in the atmosphere.

JP 2013-175305 A

  However, the solid oxide fuel cell manufacturing method described in JP 2013-175305 A has a problem that the thickness of each layer such as the fuel electrode layer cannot be sufficiently managed. That is, when the fuel electrode layer is formed on the substrate tube by the screen printing method, the mask from which the portion where the fuel electrode is to be formed is abutted against the substrate tube, and the slurry for the fuel electrode is supplied thereon, The supplied slurry is applied to the substrate tube by a squeegee. However, if the cylindrical base tube is bent, the gap between the squeegee and the base tube is different in each part of the base tube, making it difficult to make the thickness of the slurry to be applied uniform. If the film thickness of the formed fuel electrode layer or the like is nonuniform, the gas permeability and ion permeability are uneven, and the performance of the constructed fuel cell element is degraded.

  Further, since the support body such as the base tube is generally a porous body obtained by firing a formed body formed by extrusion molding or the like, it is difficult to form the support body with high dimensional accuracy. If the support is machined to ensure the dimensional accuracy of the support, there is a problem in that the manufacturing cost is remarkably increased.

  Further, in a solid oxide fuel cell of the type in which a plurality of power generation elements are formed on a single porous support and these are connected by an interconnector, the gap between the power generation elements and the power generation elements should be narrowed. Is important for improving the degree of integration. That is, since the portion between adjacent power generation elements does not contribute to power generation, it is possible to provide a large number of power generation elements on a single porous support by forming it as small as possible. Power can be increased. However, when the position accuracy and dimensional accuracy of the power generation elements formed on the porous support are not sufficient, there is a possibility that adjacent power generation elements may be short-circuited if the interval between the power generation elements is designed to be narrow.

  Therefore, the present invention provides a manufacturing system capable of efficiently manufacturing a solid oxide fuel cell having a high integration density of power generation elements even when the dimensional accuracy of the porous support is low, and manufacturing using the same. It aims to provide a method.

  In order to solve the above-described problem, the present invention forms a plurality of power generation elements including a fuel electrode layer, an electrolyte layer, and an air electrode layer, which are functional layers, on an electrically insulating porous support, A production system for a solid oxide fuel cell in which these power generation elements are connected by an interconnector, wherein a first functional layer among the functional layers of a plurality of power generation elements is simultaneously formed on the surface of a porous support. The first surface film forming apparatus to be formed and the second functional layer that is the outermost layer of the functional layers are continuously formed in the form of droplets of slurry for forming the second functional layer. A dot forming device that forms dots of slurry by spraying, and forms a second functional layer by the accumulation of the dots, and a mask forming agent on a portion that is not subjected to surface film formation by the first surface film forming device A nozzle that sticks the stick Is characterized by having, an extrusion film forming apparatus was e.

  In the present invention configured as above, the first functional layer is simultaneously formed on the surface of the porous support by the first surface film forming apparatus, while the second outermost layer is the second layer. The functional layer is formed by a dot film forming apparatus that continuously ejects slurry into droplets. Further, the mask forming agent is continuously extruded and attached in a rod shape by the extrusion film forming apparatus to the portion where the surface film forming by the first surface film forming apparatus is not performed.

As a film forming method for forming each functional layer on a porous support, a screen printing method is known in which a mask is applied to the support and a slurry for forming the functional layer is applied to the opening of the mask with a squeegee.
However, in general, the support on which the functional layer is formed has a manufacturing error, and it is difficult to ensure the flatness and linearity of the surface serving as a base for film formation. Therefore, in the screen printing method in which slurry is applied with a squeegee, it is difficult to maintain a constant gap between the base surface on which the film is formed and the squeegee, and the thickness of the formed functional layer becomes uneven. This is inevitable, and the yield of manufactured fuel cells decreases. Further, if the support is machined in order to improve the dimensional accuracy of the support in order to improve the yield, the manufacturing cost is remarkably increased. Furthermore, in recent years, there has been a demand for miniaturization of fuel cells. When the power generation element formed on the fuel cells is miniaturized, the dimensional accuracy required for the functional layer formed by film formation becomes higher and higher. Becomes difficult. That is, in order to form a plurality of small power generation elements on the support, it is necessary to accurately align the functional layers sequentially stacked on the support, and each functional layer to be formed has high positional accuracy. Required.

  In particular, in a solid oxide fuel cell of a type in which a plurality of power generation elements are formed on a single porous support and these are connected by an interconnector, between the power generation elements and the power generation elements that do not contribute to power generation In order to improve the degree of integration, it is necessary to form this portion narrowly. On the other hand, since an electrically insulating porous support only needs a function of mechanically supporting each functional layer, a material with a high porosity is desirable, but it is applied to a porous support with a high porosity. The liquid is easy to penetrate.

In the present invention configured as described above, the first functional layer is surface-deposited on the porous support by the first surface deposition apparatus. In the surface film formation, a plurality of functional layers having a large area can be formed in a short time, and the surface of the formed functional layer is smooth. It is suitable for forming the first functional layer without adversely affecting the smoothness.
The extrusion film forming apparatus has a larger amount of liquid material that can be applied per unit time than the dot film forming apparatus, and is suitable for efficiently forming a masking layer with high positional accuracy. Further, although the layer formed by the extrusion film forming apparatus has a relatively low surface smoothness, the masking layer is removed after the surface film forming is completed, and therefore the surface smoothness is not a problem.

  The dot film forming apparatus can form the functional layer with high positional accuracy and can strictly manage the thickness of the functional layer. The dot film forming apparatus has a small amount of liquid material that can be applied per unit time, but the second functional layer has a smaller area than the first functional layer, and the second functional layer has Since the surface to be formed is a denser surface than the porous support and the liquid material hardly penetrates, the film formation time of the second functional layer does not become remarkably long. Furthermore, although the functional layer formed by the dot film forming apparatus has a relatively low surface smoothness, the second functional layer is the outermost layer and thus does not adversely affect other functional layers. According to the manufacturing system of the present invention configured as described above, the fuel cell is manufactured by utilizing the characteristics of the first surface film forming apparatus, the dot film forming apparatus, and the extrusion film forming apparatus. Even when the dimensional accuracy of the quality support is low, it is possible to efficiently manufacture a solid oxide fuel cell having a high degree of integration of power generation elements.

  In the present invention, preferably, the first functional layer is a fuel electrode layer, the second functional layer is an air electrode layer, and the extrusion film forming apparatus forms a fuel electrode layer on the surface of the porous support. A mask forming agent is attached to the part not to be formed, and a masking layer is formed.

  According to the present invention configured as described above, the extrusion film forming apparatus continuously extrudes the mask forming agent in a rod shape and attaches it to a portion where the fuel electrode layer on the porous support is not required to be formed. The extrusion film forming device has a higher amount of liquid material that can be applied per unit time than the dot film forming device, so that the masking layer is positioned higher on the porous support that allows the liquid material to easily penetrate. It can be formed with accuracy. Further, since the air electrode layer is formed by the dot film forming apparatus, the air electrode layer requiring a thick film can be formed thick. Further, since the air electrode layer is formed by the dot film forming apparatus, micro cracks can be generated in the air electrode layer, and thermal stress acting on the thick air electrode layer can be released by the micro cracks.

  In the present invention, it is preferable to further include a second surface film forming apparatus that simultaneously forms the electrolyte layers of the plurality of power generating elements on the porous support from which the fuel electrode layer is formed and the masking layer is removed.

  According to the present invention configured as described above, since the electrolyte layer is formed on the porous support having the fuel electrode layer formed thereon by the second surface film forming apparatus, the electrolyte layer having a large area can be formed in a short time. Can be formed. Further, since the electrolyte layer formed by the second surface film forming apparatus has high smoothness, the air electrode layer formed on the electrolyte layer is not adversely affected. Furthermore, by configuring the electrolyte layer smoothly, the oxygen permeability of the electrolyte layer can be made uniform in each part, and unevenness in power generation performance in each part can be suppressed.

  In the present invention, preferably, the porous support has a cylindrical shape, and further includes a rotation support device that supports the porous support so as to be rotatable about the rotation center line. The second surface film forming apparatus, the dot film forming apparatus, and the extrusion film forming apparatus perform film formation while rotating the porous support by the rotation support device.

  According to the present invention configured as described above, since the film is formed while rotating the cylindrical porous support by the rotation support device, even when the porous support is curved due to a manufacturing error, the functional layer is formed. And the like can be formed in a ring shape orthogonal to the rotation center line with high accuracy.

  In this invention, Preferably, it further has an interconnector formation apparatus which forms an interconnector, and this interconnector formation apparatus sprays the slurry for forming an interconnector layer in the form of a droplet continuously. The nozzle is provided with a dispenser device that forms dots of the slurry by forming the interconnector layer by accumulating the dots, or a nozzle that continuously extrudes and adheres the slurry for forming the interconnector layer in a rod shape. The dispenser device includes a nozzle driving device that moves the nozzle so that the distance between the tip of the connector and the surface on which the interconnector layer is to be formed is substantially constant.

  Since the interconnector is generally small, high positional accuracy and dimensional accuracy are required, and it is necessary to be securely connected to the functional layer. Moreover, in order to make the electrical resistance uniform in each part, it is necessary to set the film thickness of the interconnector strictly. According to the present invention configured as described above, the interconnector forming device uses a dispenser device that continuously ejects slurry into droplets and forms an interconnector layer by accumulating dots. An interconnector layer can be formed on a porous support with low accuracy with high accuracy. In addition, in the film formation by dot accumulation, the area that can be formed per unit time is small, but since the interconnector is generally small, the film formation time does not become remarkably long.

  On the other hand, a dispenser device of a type that continuously extrudes and adheres slurry in a rod shape has a larger area that can be formed per unit time than a dispenser device that accumulates dots, so that an interconnector layer can be formed in a shorter time. it can. In addition, in a dispenser device that continuously extrudes slurry in a rod shape, the dimensional accuracy and shape accuracy of the layer to be formed tend to decrease if the dimensional accuracy of the porous support is low. Since the distance between the surface where the connector layer is to be formed is made substantially constant, the interconnector layer can be formed with sufficient accuracy.

  Moreover, this invention is a manufacturing method of the solid oxide fuel cell using the manufacturing system of this invention, Comprising: An extrusion film-forming apparatus is provided with the rotating roller contact | abutted to a porous support body, and a nozzle is a rotating roller. The distance between the tip of the nozzle and the surface of the porous support is maintained substantially constant by being moved together with the porous film. A fuel electrode layer that forms a fuel electrode layer on the surface of the porous support by using a first masking formation process in which a mask forming agent is attached to the surface to form a masking layer, and a first surface film forming apparatus Forming the fuel electrode layer formed in the fuel electrode layer forming step by heating, hardening the fuel electrode layer, and disappearing the masking layer; and forming slurry for forming the interconnector into droplets Continuous The dots of the slurry are formed by spraying, and by the accumulation of the dots, an interconnector forming process for forming an interconnector layer on the fuel electrode layer, and a rotating roller of the extrusion film forming apparatus are connected to the fuel electrode layer. The second masking forming step of attaching a masking forming agent on the interconnector layer in a state where the connector layer is not formed and the second surface film forming apparatus are used to attach the electrolyte layer. An electrolyte layer forming step of simultaneously forming a plurality of power generating element electrolyte layers by attaching a slurry for forming, and a second masking forming step while heating and curing the electrolyte layer formed by this electrolyte layer forming step A slurry for forming an air electrode layer using a second preliminary firing step for eliminating the masking layer formed in step 1 and a dot film forming apparatus. An air electrode layer forming step for forming slurry dots by continuously spraying in the form of droplets, and forming the air electrode layer so as to be connected to the interconnector layer by the accumulation of the dots, and forming the air electrode layer And a firing step of heating and firing the air electrode layer formed in the step.

  According to the present invention configured as described above, the first masking formation process and the second masking formation process are performed using the extrusion film forming apparatus, and the fuel electrode layer forming process is performed using the first surface film forming apparatus. Since the interconnector is formed by the accumulation of the dots of the slurry, the electrolyte layer forming step is executed using the second surface film forming device, and the air electrode layer forming step is executed using the dot film forming device. The characteristics of each film forming method can be utilized, and even when the dimensional accuracy of the porous support is low, highly accurate functional layers and interconnectors can be efficiently formed.

  According to the solid oxide fuel cell manufacturing system and the manufacturing method of the present invention, a solid oxide fuel cell having a high integration density of power generation elements can be efficiently obtained even when the dimensional accuracy of the porous support is low. Can be manufactured.

1 is an overall configuration diagram showing a solid oxide fuel cell system incorporating a solid oxide fuel cell according to a first embodiment of the present invention. It is sectional drawing of the storage container of the solid oxide fuel cell by 1st Embodiment of this invention. 1 is a perspective view showing an entire solid oxide fuel cell according to a first embodiment of the present invention. It is sectional drawing which expanded and showed the functional layer formed in the porous support body surface of the solid oxide fuel cell by 1st Embodiment of this invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic front view showing an entire dot film forming apparatus that is a fuel cell manufacturing apparatus according to a first embodiment of the present invention. It is a schematic sectional drawing which shows the front-end | tip part of the jet dispenser with which the dot film-forming apparatus was equipped. 1 is a schematic front view showing an entire surface film forming apparatus which is a fuel cell manufacturing apparatus according to a first embodiment of the present invention. It is a flow which shows the operation | movement procedure of a surface film-forming apparatus. It is a schematic front view which shows the whole extrusion film-forming apparatus. It is a figure which expands and shows the part of the nozzle of the head part with which the extrusion film-forming apparatus was equipped. It is a flowchart which shows the procedure of the manufacturing method of the fuel cell by 1st Embodiment of this invention. In the fuel battery cell by 1st Embodiment of this invention, it is a schematic diagram which shows the lamination | stacking procedures, such as a functional layer, on a porous support body. It is a figure which shows typically the state at the time of a masking layer being formed on a porous support body. It is a figure which shows typically the state which has formed the masking layer on the 1st interconnector layer by the extrusion film-forming apparatus. It is a figure which shows the surface state of the air electrode layer after completion | finish of a 2nd baking process. It is an electron micrograph of each part of the fuel cell according to the first embodiment of the present invention. It is sectional drawing which expanded and showed the functional layer formed in the porous support body surface of the fuel cell by 2nd Embodiment of this invention.

Next, a solid oxide fuel cell (SOFC) according to an embodiment of the present invention will be described with reference to the accompanying drawings.
First, a solid oxide fuel cell according to a first embodiment of the present invention will be described with reference to FIGS.
FIG. 1 is an overall configuration diagram showing a solid oxide fuel cell system incorporating a solid oxide fuel cell according to a first embodiment of the present invention. As shown in FIG. 1, the solid oxide fuel cell system 1 includes a fuel cell module 2 and an auxiliary unit 4.

  The fuel cell module 2 includes a housing 6, and a fuel cell storage container 8 is disposed inside the housing 6 via a heat insulating material 7. A power generation chamber 10 is formed inside the fuel cell storage container 8, and a plurality of fuel cell cells 16 (solid oxide fuel cell cells) are concentrically arranged in the power generation chamber 10. These fuel battery cells 16 perform a power generation reaction of air that is fuel gas and oxidant gas.

  An exhaust collecting chamber 18 is attached to the upper end of each fuel cell 16. The remaining fuel (off-gas) that is not used in the power generation reaction in each fuel cell 16 is collected in the exhaust collection chamber 18 attached to the upper end, and a plurality of fuel cells 16 provided on the ceiling surface of the exhaust collection chamber 18 are provided. It is discharged from the spout. The fuel that has flowed out is burned by the air remaining in the power generation chamber 10 without being used for power generation, and exhaust gas is generated.

  Next, the auxiliary unit 4 stores a water from a water supply source 24 such as a tap water and uses a filter to obtain pure water, and a water for adjusting the flow rate of the water supplied from the pure water tank. A water flow rate adjustment unit 28 (such as a “water pump” driven by a motor) as a supply device is provided. The auxiliary unit 4 also has a fuel blower 38 (a “fuel pump” driven by a motor) that is a fuel supply device that adjusts the flow rate of a hydrocarbon-based raw fuel gas supplied from a fuel supply source 30 such as city gas. Etc.).

  The raw fuel gas that has passed through the fuel blower 38 is introduced into the fuel cell storage container 8 via the desulfurizer 36 disposed in the fuel cell module 2, the heat exchanger 34, and the electromagnetic valve 35. . The desulfurizer 36 is annularly arranged around the fuel cell storage container 8 and removes sulfur from the raw fuel gas. The heat exchanger 34 is provided to prevent the high temperature raw fuel gas whose temperature has risen in the desulfurizer 36 from flowing directly into the electromagnetic valve 35 and degrading the electromagnetic valve 35. The electromagnetic valve 35 is provided to stop the supply of the raw fuel gas into the fuel cell storage container 8.

  The accessory unit 4 includes an air flow rate adjustment unit 45 (such as an “air blower” driven by a motor) that is an oxidant gas supply device that adjusts the flow rate of air supplied from the air supply source 40.

Further, the auxiliary unit 4 is provided with a hot water production device 50 for recovering the heat of the exhaust gas from the fuel cell module 2. The hot water production apparatus 50 is supplied with tap water, and the tap water is heated by the heat of the exhaust gas and supplied to a hot water storage tank of an external hot water heater (not shown).
Furthermore, the fuel cell module 2 is connected to an inverter 54 that is a power extraction unit (power conversion unit) for supplying the power generated by the fuel cell module 2 to the outside.

Next, the internal structure of the fuel cell storage container 8 will be described with reference to FIG. FIG. 2 is a cross-sectional view of the fuel cell storage container.
As shown in FIG. 2, a plurality of fuel cells 16 are concentrically arranged in a space in the fuel cell storage container 8, and a fuel gas supply channel 20 that is a fuel channel so as to surround the periphery thereof. An exhaust gas discharge passage 21 and an oxidant gas supply passage 22 are formed concentrically in order.

  First, as shown in FIG. 2, the fuel cell storage container 8 is a substantially cylindrical hermetic container, and an oxidant gas introduction pipe serving as an oxidant gas inlet for supplying air for power generation is provided on the side surface thereof. 56 and an exhaust gas exhaust pipe 58 for exhaust gas exhaust are connected. Further, an ignition heater 62 for igniting the remaining fuel that has flowed out of the exhaust collecting chamber 18 protrudes from the upper end surface of the fuel cell storage container 8.

  As shown in FIG. 2, inside the fuel cell storage container 8, an inner cylindrical member 64, which is a power generation chamber constituting member, an outer cylindrical member 66, an inner side in order from the inner side so as to surround the periphery of the fuel cell 16. A cylindrical container 68 and an outer cylindrical container 70 are arranged. The above-described fuel gas supply flow path 20, exhaust gas discharge flow path 21, and oxidant gas supply flow path 22 are flow paths configured between these cylindrical members and cylindrical containers, respectively, and between adjacent flow paths. Heat exchange takes place at. Further, the open space on the lower end side of the fuel cell storage container 8 is closed by a substantially circular dispersion chamber bottom member 72 that constitutes the bottom surface of the fuel gas dispersion chamber 76 that disperses the fuel into each fuel cell 16. .

A combustion catalyst 60 and a sheath heater 61 for heating the combustion catalyst 60 are disposed below the exhaust gas discharge passage 21.
The combustion catalyst 60 is a catalyst filled in an annular space between the outer peripheral surface of the outer cylindrical member 66 and the inner peripheral surface of the inner cylindrical container 68 above the exhaust gas discharge pipe 58. Exhaust gas descending the exhaust gas discharge passage 21 passes through the combustion catalyst 60 to remove carbon monoxide and is discharged from the exhaust gas discharge pipe 58.
The sheath heater 61 is an electric heater attached so as to surround the outer peripheral surface of the outer cylindrical member 66 below the combustion catalyst 60. When the solid oxide fuel cell device 1 is started, the combustion catalyst 60 is heated to the activation temperature by energizing the sheath heater 61.

  An annular space between the outer peripheral surface of the inner cylindrical container 68 and the inner peripheral surface of the outer cylindrical container 70 functions as the oxidant gas supply channel 22. Further, an oxidant gas introduction pipe 56 is connected to the lower side surface of the outer cylindrical container 70, and the oxidant gas supply flow path 22 communicates with the oxidant gas introduction pipe 56.

  A fuel gas dispersion chamber 76 is configured between the first fixing member 63 and the dispersion chamber bottom member 72. In addition, an insertion tube 72 a for inserting the bus bar 80 (FIG. 2) is provided at the center of the dispersion chamber bottom member 72. The bus bar 80 electrically connected to each fuel cell 16 is drawn out of the fuel cell storage container 8 through the insertion tube 72a.

  An oxidant gas injection pipe 74 having a circular cross section for injecting air for power generation is attached so as to hang down from the ceiling surface of the inner cylindrical container 68. The oxidant gas injection pipe 74 extends in the vertical direction on the central axis of the inner cylindrical container 68, and each fuel cell 16 is disposed on a concentric circle around it. The air supplied through the oxidant gas supply channel 22 is injected downward from the tip of the oxidant gas injection pipe 74, hits the upper surface of the first fixing member 63, and spreads throughout the power generation chamber 10.

  The fuel gas dispersion chamber 76 is a cylindrical airtight chamber formed between the first fixing member 63 and the dispersion chamber bottom member 72, and each fuel cell 16 is forested on the upper surface thereof. Each fuel cell 16 attached to the upper surface of the first fixing member 63 has an inner fuel electrode communicating with the inside of the fuel gas dispersion chamber 76. The lower end portion of each fuel cell 16 penetrates the insertion hole of the first fixing member 63 and protrudes into the fuel gas dispersion chamber 76, and each fuel cell 16 is fixed to the first fixing member 63 by bonding. Yes.

  As shown in FIG. 2, the supplied fuel once rises in the space between the inner periphery of the outer cylindrical member 66 and the outer periphery of the intermediate cylindrical member 65, and then the outer periphery of the inner cylindrical member 64 and the inner cylindrical member 65. The space between the circumferences descends and flows into the fuel gas dispersion chamber 76 through the plurality of small holes 64b. The fuel that has flowed into the fuel gas dispersion chamber 76 is distributed to the fuel electrode of each fuel cell 16 attached to the ceiling surface (first fixing member 63) of the fuel gas dispersion chamber 76.

  Further, the lower end portion of each fuel cell 16 projecting into the fuel gas dispersion chamber 76 is electrically connected to the bus bar 80 in the fuel gas dispersion chamber 76, and electric power is drawn out through the insertion tube 72a. The bus bar 80 is electrically connected to a current collector 82 attached to each fuel cell 16 inside the fuel gas dispersion chamber 76. The bus bar 80 is connected to the inverter 54 (FIG. 1) outside the fuel cell storage container 8. The current collector 82 is also attached to the upper end portion of each fuel cell 16 projecting into the exhaust collection chamber 18. The current collectors 82 at the upper end and the lower end connect the plurality of fuel cells 16 in parallel electrically, and connect the plurality of sets of fuel cells 16 connected in parallel electrically in series. The both ends of this series connection are connected to the bus bar 80, respectively.

  Next, the configuration of the exhaust collection chamber 18 will be described. The exhaust concentration chamber 18 is a donut-shaped cross-section chamber attached to the upper end of each fuel cell 16, and an oxidant gas injection pipe 74 extends through the center of the exhaust concentration chamber 18. . A plurality of circular insertion holes are provided on the bottom surface of the aggregation chamber 18. The upper end portions of the fuel cells 16 are inserted into the respective insertion holes. On the other hand, a plurality of jet outlets for jetting the aggregated fuel gas are provided on the ceiling surface of the exhaust aggregation chamber 18. The remaining fuel that is not used for power generation flows into the exhaust collecting chamber 18 from the upper end of each fuel battery cell 16, and the fuel collected in the exhaust collecting chamber 18 flows out from each jet port and burns there. .

Next, a configuration for reforming the raw fuel gas supplied from the fuel supply source 30 will be described with reference to FIG.
First, an evaporating portion 86 for evaporating water for steam reforming is provided at the lower portion of the fuel gas supply flow path 20. The evaporation unit 86 includes a ring-shaped inclined plate 86 a attached to the lower inner periphery of the outer cylindrical member 66 and a water supply pipe 88. The inclined plate 86 a is a metal thin plate formed in a ring shape, and its outer peripheral edge is attached to the inner wall surface of the outer cylindrical member 66. On the other hand, the inner peripheral edge of the inclined plate 86 a is positioned above the outer peripheral edge, and a gap is provided between the inner peripheral edge of the inclined plate 86 a and the outer wall surface of the inner cylindrical member 64.

  The water supply pipe 88 is a pipe that extends in the vertical direction from the lower end of the inner cylindrical member 64 into the fuel gas supply flow path 20, and the water supplied to the upper surface side of the inclined plate 86a is the upper surface of the inclined plate 86a and the outer cylindrical member. It stays between 66 inner walls. The water supplied to the upper surface side of the inclined plate 86a is evaporated there to generate water vapor.

  A fuel gas introduction part for introducing the raw fuel gas into the fuel gas supply channel 20 is provided below the evaporation part 86. The raw fuel gas sent from the fuel blower 38 is introduced into the fuel gas supply channel 20 via the fuel gas supply pipe 90. The raw fuel gas sent from the fuel blower 38 is introduced to the lower side of the inclined plate 86a and rises to the upper side of the inclined plate 86a while the flow path is restricted by the inclination of the inclined plate 86a. The raw fuel gas that has risen to the upper side of the inclined plate 86 a rises together with the water vapor generated in the evaporation section 86.

  A fuel gas supply channel partition wall 92 is provided above the evaporation portion 86 in the fuel gas supply channel 20. A plurality of injection ports 92 a are provided at equal intervals on the circumference of the fuel gas supply channel partition wall 92. The raw fuel gas introduced from the fuel gas supply pipe 90 and the water vapor generated in the evaporation portion 86 once stay in the space below the fuel gas supply flow path partition wall 92 and then pass through each injection port 92a to become fuel. The gas is injected into the space above the gas supply flow path partition wall 92 and mixed sufficiently here.

Further, a reforming portion 94 is provided in the upper part of the annular space between the inner periphery of the intermediate cylindrical member 65 and the outer periphery of the inner cylindrical member 64. The reforming unit 94 includes a catalyst holding plate (not shown) attached to the outer wall surface of the inner cylindrical member 64 and a reforming catalyst 96 held thereby. When the raw fuel gas and steam mixed in the space above the fuel gas supply flow path partition wall 92 come into contact with the reforming catalyst 96, the steam reforming reaction SR shown in Formula (1) is performed in the reforming unit 94. proceed.
C _m H _n + xH ₂ O → aCO ₂ + bCO + cH ₂ (1)

  The fuel gas reformed in the reforming section 94 flows downward in the space between the inner periphery of the intermediate cylindrical member 65 and the outer periphery of the inner cylindrical member 64, flows into the fuel gas dispersion chamber 76, and each fuel cell. 16 is supplied. Although the steam reforming reaction SR is an endothermic reaction, the heat required for the reaction is supplied by the combustion heat of the offgas flowing out from the exhaust collecting chamber 18 and the heat generated in each fuel cell 16.

Next, the structure of the fuel cell according to the first embodiment of the present invention will be described with reference to FIGS. 3 and 4.
FIG. 3 is a perspective view showing the whole fuel cell, and FIG. 4 is an enlarged cross-sectional view showing a functional layer formed on the surface of the porous support of the fuel cell.
As shown in FIG. 3, the fuel cell 16 (solid oxide fuel cell) of this embodiment is a cylindrical horizontal stripe cell using a solid oxide. On each fuel cell 16, a plurality of power generation elements 16 a are formed in a horizontal stripe shape, and one fuel cell 16 is configured by electrically connecting them in series. Each fuel cell 16 is configured such that one end thereof is an anode (anode) and the other end is a cathode (cathode), and half of the plurality of fuel cells 16 has an upper end as an anode and a lower end as a cathode. The other half are arranged so that the upper end is a cathode and the lower end is an anode.

  As shown in FIG. 4, the fuel battery cell 16 of the present embodiment includes a cylindrical porous support 97, a fuel electrode layer 98 that is three functional layers formed thereon, an electrolyte layer 100, and air. It has a polar layer 101. In the fuel cell 16, a plurality of power generation elements 16 a are formed by sequentially forming a fuel electrode layer 98, an electrolyte layer 100, and an air electrode layer 101 on a porous support 97. The fuel electrode layer 98 of each power generation element 16a functions as an anode, and the air electrode layer 101 functions as a cathode. Each of these power generating elements 16 a is electrically connected in series by the interconnector layer 102. In the present embodiment, twelve power generating elements 16 a are formed on one fuel battery cell 16, and these are connected by the interconnector layer 102.

  Specifically, as shown in FIG. 4, one end portion of the fuel electrode layer 98 constituting each power generation element 16 a and the opposite end portion of the air electrode layer 101 are extended. The extended end portion of the fuel electrode layer 98 that is the anode of the power generation element 16a is connected to the extended end portion of the air electrode layer 101 that is the cathode of the power generation element 16a that is disposed adjacently by the interconnector layer 102. ing.

Next, the structure of the porous support body 97 and each functional layer is demonstrated.
In this embodiment, the porous support 97 is formed by extruding a cylindrical mixture of a forsterite powder, which is an electrically insulating material, and adding a binder into a cylindrical shape, followed by sintering.
In this embodiment, the fuel electrode layer 98 is a conductive thin film composed of a mixture of NiO powder and 10YSZ (10 mol% Y ₂ O ₃ -90 mol% ZrO ₂ ) powder.

In the present embodiment, the solid electrolyte layer 100 is a thin film made of LSGM powder having a composition of La _0.9 Sr _0.1 Ga _0.8 Mg _0.2 O ₃ . Electric energy is generated by the reaction between oxide ions and hydrogen or carbon monoxide through the solid electrolyte layer 100.

In this embodiment, the air electrode layer 101 is a conductive thin film composed of LSCF powder having a composition of La _0.6 Sr _0.4 Co _0.8 Fe _0.2 O ₃ .
The interconnector layer 102, in this embodiment, SLT (lanthanum doped strontium titanate) and _{La 1-x Sr x Ti 1} -yz Nb y Fe z O 3 (LSTNF, 0.1 ≦ x ≦ 0.8,0.1 ≦ y ≦ 0.3 , 0.3 ≦ z ≦ 0.6).

Next, the fuel cell manufacturing apparatus according to the first embodiment of the present invention will be described.
First, a dot film forming apparatus used in a dot film forming process for forming a functional layer and the like will be described with reference to FIGS. FIG. 5 is a schematic front view showing the entire dot film forming apparatus, and FIG. 6 is a schematic cross-sectional view showing a tip portion of a jet dispenser provided in the dot film forming apparatus.

Each functional layer described above is formed by attaching a slurry in which a powder of a material constituting each functional layer is suspended to the porous support 97 and firing the slurry.
In each manufacturing process of the fuel battery cell 16, the dot film forming apparatus 110 forms each slurry for forming the interconnector and the air electrode layer in the form of droplets, and selectively selects only a predetermined portion where the dot film should be formed. In addition, it is configured to inject continuously. Further, the dot film forming apparatus 110 has a positioning function for forming an interconnector or an air electrode layer at a predetermined position.

  As shown in FIG. 5, the dot film forming apparatus 110 includes a pedestal 112, a motor 114 for rotating the porous support 97 on which the dot film is to be formed, and a fixing jig 116 that rotatably holds the porous support 97. A head portion 118 that ejects droplets, and a guide rail 120 that guides the head portion 118.

A motor 114 and a fixing jig 116 are installed on the pedestal 112.
The fixing jig 116 serving as a rotation support device is configured to rotatably hold the porous support 97 on which the dot film is to be formed. That is, the fixing jig 116 holds the porous support 97 horizontally so as to sandwich the porous support 97 from both ends by inserting conical tailstocks 116a into both ends of the cylindrical porous support 97, respectively. Each mandrel 116a is configured to be rotatable about a horizontal rotation center line A, and the porous support body 97 held thereby is held to be rotatable about the rotation center line A. The motor 114 is configured to rotate the porous support 97 held by each tailstock 116a around the rotation center line A.

  Here, by supporting the cylindrical porous support body 97 sandwiched from both sides by the conical tailstock 116a, the porous support body 97 has its central axis and the rotational centerline A of the tailstock 116a. Hold to match. However, since the porous support body 97 is not completely cylindrical due to manufacturing errors, the rotation center line A and the central axis line of the porous support body 97 are slightly shifted in practice.

The head unit 118 includes a jet dispenser 122 that ejects slurry and the like in the form of droplets, a slurry container 124 that supplies the jet dispenser 122 with slurry and the like, and a camera 126 that captures an image of the porous support 97 on which dots are to be formed. And having.
The guide rail 120 is configured to move the head portion 118 in parallel with the rotation center line A. At the time of dot film formation, the porous support 97 is rotated while jetting droplet-like slurry from the jet dispenser 122, and the head portion 118 is sent along the guide rail 120 at a predetermined speed, thereby making the porous A belt-like slurry film can be formed around the support 97.

As shown in FIG. 6, the jet dispenser 122 includes a nozzle portion 128 that ejects slurry and the like, and an ejection actuator 129 that controls ejection.
The nozzle portion 128 is provided with an injection nozzle hole 128a oriented in the vertical direction, and a concave portion 128b wider than the injection nozzle hole 128a is formed at the upper end of the injection nozzle hole 128a. Further, a horizontal slurry supply passage 128c is formed in the nozzle portion 128 so as to communicate with the injection nozzle hole 128a. The slurry to be injected is injected from the slurry container 124 into the slurry supply passage 128c. The slurry or the like supplied from the slurry supply passage 128c flows into the injection nozzle hole 128a and is injected from the tip (lower end) of the injection nozzle hole 128a.

The ejection actuator 129 includes a flexible plate 129a and a protrusion 129b attached to the flexible plate 129a.
The flexible plate 129 a is a flexible rubber plate, and is attached so as to cover the recess 128 b provided in the nozzle portion 128. The protrusion 129 b is a metal protrusion attached to the central portion of the flexible plate 129 a and is received in the recess 128 b of the nozzle portion 128. A pulsating air pressure is applied to the back side of the flexible plate 129a (the opposite side of the recess 128b), and the flexible plate 129a bends due to the fluctuation of the air pressure, and a protrusion attached to the flexible plate 129a. 129b moves up and down.

  When the projection 129b is moved downward, the volume in the recess 128b that accommodates the projection 129b decreases, so that the slurry filled in the injection nozzle hole 128a and the recess 128b is made into droplets. Sprayed from the tip of the spray nozzle hole 128a. When the air pressure on the back side of the flexible plate 129a pulsates at a predetermined cycle, the protrusion 129b moves up and down, and droplets and the like are continuously ejected at a predetermined cycle. The ejected slurry droplets form dots on the porous support 97, and a slurry film is formed by the accumulation of the dots.

  The porous support body 97 is rotated by driving the motor 114, and the jet dispenser 122 is sent along the guide rail 120 at a predetermined speed, whereby the dots of the slurry are accumulated in horizontal stripes at desired positions on the porous support body 97. Can be made. The thickness of the layer formed by the dot film formation depends on the number of rotations of the motor 114, the feed speed of the jet dispenser 122, the size of droplets ejected from the jet dispenser 122, the viscosity of the slurry to be ejected, and the like. Can be controlled.

  The camera 126 is configured to take an image of the fuel electrode layer, the interconnector layer, and the like formed on the porous support 97, and specify the position of the boundary line by image analysis. Further, the horizontal distance L between the position on the image captured by the camera 126 and the ejection nozzle hole 128a from which the droplet is ejected is stored in advance in a memory (not shown). For this reason, the injection nozzle hole 128a can be moved to the position specified on the image by sending the head portion 118 by the distance L along the guide rail 120 from the position specified on the captured image. .

Next, a surface film forming apparatus used in the surface film forming process for forming the functional layer will be described with reference to FIGS. FIG. 7 is a schematic front view showing the entire surface film forming apparatus, and FIG. 8 is a flow showing an operation procedure of the surface film forming apparatus.
As shown in FIG. 7, the surface film forming apparatus 130 includes a pedestal 131, a fixing jig 132 provided on the pedestal 131, a motor 134 for rotating the fixing jig 132, and a surface component for discharging slurry. A film nozzle 136, a pump 138 that pumps slurry to the surface film forming nozzle 136, and a slurry container 139 that contains slurry to be supplied are provided.

  A fixing jig 132 is provided on the base 131. The fixing jig 132 which is a rotation support device supports the both ends of the porous support body 97 so that the porous support body 97 is directed horizontally. The motor 134 is connected to the fixing jig 132 so that the fixing jig 132 and the porous support 97 supported by the fixing jig 132 are rotated at a predetermined rotational speed around the central axis of the porous support 97. It is configured.

The surface film forming nozzle 136 is disposed immediately below the porous support 97 supported by the fixing jig 132, and is configured to discharge the slurry upward toward the porous support 97.
The pump 138 is configured to suck up the slurry in the slurry container 139 and discharge the slurry from the surface film forming nozzle 136 at a predetermined flow rate.

  The surface film forming nozzle 136 is provided with slit-like elongated nozzle holes (not shown) so that the slurry is uniformly discharged over the entire surface of the porous support 97 to be formed. ing. The slurry discharged from the surface film forming nozzle 136 is attached to the porous support 97 disposed in the horizontal direction immediately above, and each functional layer of the plurality of power generating elements 16a formed on the porous support 97 is simultaneously formed. A film is formed. Note that a portion on the porous support 97 that does not require surface film formation is masked in advance by a dot film formation apparatus 110 as described later. Slurry remaining without adhering to the porous support 97 flows down around the surface film forming nozzle 136 and is collected.

Next, with reference to FIG. 8, a surface film forming procedure will be described.
First, in step S <b> 101 of FIG. 8, the porous support 97 to be surface-formed is fixed to the fixing jig 132. Note that masking is performed in advance on a portion on the porous support 97 where surface film formation is unnecessary. Next, in step S102, the motor 134 is activated, and the porous support 97 is rotated at a predetermined rotational speed around its central axis. Further, in step S103, the pump 138 is operated. Thereby, the slurry is sucked up from the slurry container 139, and the slurry is pumped toward the surface film-forming nozzle 136 (step S104). The slurry fed under pressure is discharged upward from the surface film forming nozzle 136 (step S105). The slurry discharged from the surface film forming nozzle 136 is applied to the surface of the porous support 97 rotating above the surface film forming nozzle 136 (step S106).

The slurry remaining without adhering to the porous support 97 flows down around the surface film forming nozzle 136. Further, excess slurry adhering to the porous support 97 flows down by the centrifugal force of the rotating porous support 97, and a slurry film having a predetermined thickness is formed on the porous support 97. . Accordingly, the thickness of the layer formed on the porous support 97 can be controlled by the number of rotations of the porous support 97, the discharge flow rate from the surface film forming nozzle 136, the viscosity of the slurry, and the like.
Next, the pump 138 is stopped in step S107, and the motor 134 is stopped in step S108. Further, in step S109, the formed porous support body 97 is removed from the fixing jig 132, and the surface film forming step is completed.

  Next, an extrusion film forming apparatus used in an extrusion film forming process for forming a masking layer and the like will be described with reference to FIGS. 9 and 10. FIG. 9 is a schematic front view showing the entire extrusion film forming apparatus, and FIG. 10 is an enlarged view showing a nozzle portion of a head portion provided in the extrusion film forming apparatus.

The dot film forming apparatus 110 described above is a device for forming dots at predetermined positions by continuously ejecting slurry for forming each functional layer in the form of droplets. On the other hand, the extrusion film forming apparatus 140 applies the liquid material to a predetermined position by continuously extruding the liquid material from the tip of the nozzle in a rod shape. Each of these dot film forming apparatus 110 and extrusion film forming apparatus 140 is a dispenser apparatus that applies a liquid material only to a predetermined position on the surface to be applied, and has a narrower range than the above-described surface film forming apparatus 130. A liquid material is discharged and applied.
As described above, the extrusion film forming apparatus 140 has a function of applying an arbitrary liquid material to a predetermined position. In the present embodiment, this is applied to the application of a masking agent, that is, formation of a masking layer. It is used for.

  As shown in FIG. 9, the extrusion film forming apparatus 140 includes a pedestal 142, a motor 144 that rotates the porous support 97 to be formed by extrusion, and a fixing jig 146 that holds the porous support 97 rotatably. And a head portion 148 for applying a liquid material, and a guide rail 150 for guiding the head portion 148.

A motor 144 and a fixing jig 146 are installed on the pedestal 142.
The fixing jig 146 which is a rotation support device is configured to rotatably hold the porous support 97 to be extruded. That is, the fixing jig 146 holds the porous support body 97 horizontally so as to sandwich the porous support body 97 from both ends by inserting conical tailstocks 146a into both ends of the cylindrical porous support body 97, respectively. Each tailstock 146a is configured to be rotatable about a horizontal rotation center line A, and the porous support body 97 held thereby is held to be rotatable about the rotation center line A. The motor 144 is configured to rotate the porous support 97 held by each tailstock 146a around the rotation center line A.

  Here, by supporting the cylindrical porous support body 97 by sandwiching it from both sides by the conical tailstock 146a, the porous support body 97 has its central axis and the rotational centerline A of the tailstock 146a. Hold to match. However, as described above, actually, the rotation center line A and the center axis of the porous support 97 are slightly shifted.

The head unit 148 includes a nozzle 152 that continuously discharges a masking agent, a tank 154 that stores a masking agent supplied to the nozzle 152, a nozzle driving device 156 that drives the nozzle 152, and a liquid material. And a camera 158 that images the porous support 97 to be coated.
The nozzle 152 is an elongated cylindrical nozzle that extends vertically downward in a plane including the rotation center line A of the porous support 97, and continuously forms a liquid material in a rod shape from the lower end vertically downward. It is comprised so that it may discharge to.
The tank 154 is configured to store a liquid material to be supplied to the nozzle 152, such as a masking agent. The tank 154 is fixed to the head portion 148, and is connected to the nozzle 152 via a flexible pipe 154a. The liquid material is pushed out from the tank 154 at a constant pressure, is formed into a rod shape at a constant flow rate from the tip of the nozzle 152, and is continuously discharged.

  The camera 158 is configured to take an image of the fuel electrode layer, the interconnector layer, and the like formed on the porous support member 97, and specify the position of the boundary line by image analysis. Further, the horizontal distance L between the position on the image captured by the camera 158 and the nozzle 152 from which the liquid material is pushed out is stored in advance in a memory (not shown). Therefore, the nozzle 152 can be moved to the position specified on the image by sending the head portion 148 from the position specified on the captured image by the distance L along the guide rail 150.

  The guide rail 150 is configured to move the head portion 148 in parallel with the rotation center line A. The head portion 148 is fed along the guide rail 150 to a position on the porous support 97 where extrusion film formation is to be performed. During extrusion film formation, a belt-like slurry film can be formed around the porous support 97 by rotating the porous support 97 while discharging a liquid from the nozzle 152. Further, depending on the form of the layer to be extruded, the head portion 148 can be sent along the guide rail 150 at a predetermined speed during the extrusion film formation.

  As shown in FIG. 10, the nozzle driving device 156 is provided below the head portion 148. The nozzle driving device 156 includes an arm portion 156a that is movably attached to the head portion 148, and a rotating roller 156b that is provided at the tip of the arm portion 156a.

  The rotating roller 156b is provided only on one side of the nozzle 152, and is configured to passively rotate by contacting the surface of the rotating porous support body 97. Here, in the present embodiment, the rotating roller 156b is pressed against the surface of the porous support 97 by its own weight of the nozzle driving device 156, and is always in contact with the surface of the rotating porous support 97. ing. For this reason, the rotating roller 156b is moved in the vertical direction (vertical direction), which is the liquid material discharge direction, along with the movement of the surface of the porous support 97. Further, the porous support body 97 supported by the fixing jig 146 is slightly curved due to a manufacturing error or the like. For this reason, the position of the surface of the porous support body 97 rotating around the rotation center line A (FIG. 9) moves slightly in the vertical direction in FIG. 10 along with the rotation. As a result, the rotating roller 156b that is in contact with the surface of the porous support body 97, and the arm portion 156a to which the rotating roller 156b is attached follow the “runout” of the surface of the porous support body 97. It is moved in the vertical direction in FIG.

  Here, since the nozzle driving device 156 is configured to move the nozzle 152 in conjunction with the movement of the rotating roller 156b, the nozzle 152 also follows the “shake” of the surface of the porous support 97. It is moved in the discharge direction of the liquid material. For this reason, even when the surface of the rotating porous support 97 moves due to manufacturing errors of the porous support 97, the distance D between the tip P of the nozzle 152 and the surface of the porous support 97 is substantially constant. Maintained. In the present embodiment, the contact point C between the rotating roller 156b and the surface of the porous support 97 and the tip P of the nozzle 152 are both positioned vertically above the rotation center line A of the porous support 97. Yes. In addition, the vertical projection of the straight line connecting the contact point C and the tip 152 of the nozzle 152 should be positioned parallel to the rotation center line A. In this embodiment, the straight line connecting the contact point C and the tip P is a straight line. The projection in the vertical direction coincides with the rotation center line A. Accordingly, the nozzle 152 is substantially orthogonal to the plane that contacts the cylindrical porous support 97 through the point where the liquid on the porous support 97 is applied (a point directly below the tip P). Is directed. In the present embodiment, the rotating roller 156b is pressed against the surface of the porous support 97 by the weight of the nozzle driving device 156, and the nozzle 152 is moved in the vertical direction in conjunction with the rotating roller 156b. On the other hand, the tank 154 for supplying the liquid material is fixed to the head portion 148 and is connected to the nozzle 152 via a flexible pipe 154a. Therefore, the tank 154 is interlocked with the rotating roller 156b and the nozzle 152. do not do. For this reason, irrespective of the weight of the liquid material accommodated in the tank 154, the pressing force of the rotating roller 156b can be made constant. Further, even when a large amount of liquid material is accommodated and the weight of the tank 154 increases, the rotating roller 156b is pressed by the weight, so that the fragile porous support 97 is not burdened.

  Further, in the present embodiment, the distance S between the contact point C and the tip P in the direction of the rotation center line A (horizontal direction) is set to about 10 mm. Further, the distance D between the tip P of the nozzle 152 and the surface of the porous support 97 is determined when there is no manufacturing error in the porous support 97 (when the surface of the porous support 97 is oriented horizontally). Is set to be about 0.3 mm. Thus, since the tip P of the nozzle 152 is positioned in the vicinity of the surface of the porous support 97, the gap between the tip P and the surface of the porous support 97 is pushed out from the nozzle 152 by the liquid material formed into a rod shape. While being applied, a liquid material is applied.

  Here, since the liquid material is continuously pushed out from the tip of the nozzle 152 at a constant flow rate, if the distance D between the tip P of the nozzle 152 and the surface of the porous support 97 changes greatly, the porous support The liquid material layer applied on the body 97 snakes or the layer width becomes non-uniform. In this embodiment, since the distance D between the tip P of the nozzle 152 and the surface of the porous support 97 is maintained substantially constant by the nozzle driving device 156, a sufficiently uniform layer can be formed. it can. However, in actuality, in FIG. 10, the height of the contact point C is different from the height of the surface of the porous support body 97 just below the nozzle 152 (the surface of the porous support body 97 is inclined). Changes slightly. Here, in this embodiment, since the porous support 97 is a sintered product containing forsterite powder as a main component, almost all of the shape errors that occur during the manufacturing process are moderate in the entire porous support 97. It is of the type that curves in an arc. The inclination generated by this bending is at most about 2% (maximum deflection of 2 mm with respect to 100 mm in the longitudinal direction of the porous support). Therefore, in this embodiment, since the distance S between the contact point C and the tip P is 10 mm, the height difference D1 at the position of the contact point C and the nozzle 152 is 0.2 mm (10 mm × 0) at the maximum. 0.02) and a sufficiently uniform layer can be formed. As described above, in order to keep the distance D between the tip P of the nozzle 152 and the surface of the porous support 97 constant, the shorter the distance S between the contact point C and the tip P, the more advantageous. However, in order to mechanically configure the nozzle driving device 156, the distance S requires a certain length.

  The dot film forming apparatus 110, the surface film forming apparatus 130, the extrusion film forming apparatus 140, and the heating furnace for firing the formed functional layer described above constitute a solid oxide fuel cell manufacturing system.

Next, with reference to FIG.11 and FIG.12, the manufacturing method of the solid oxide fuel cell by 1st Embodiment of this invention is demonstrated.
FIG. 11 is a flowchart showing a procedure of the manufacturing method of the present embodiment, and FIG. 12 is a schematic diagram showing a procedure for stacking functional layers and the like on the porous support. FIG. 12 schematically shows the overlap of the functional layers and the like, and does not show the specific cross-sectional shape and dimensions of each layer.

First, in step S1 of FIG. 11, a forsterite porous support 97 is formed as a support forming process. Specifically, a clay-like material obtained by adding a binder to forsterite powder is extruded into a cylindrical shape by an extruder (not shown).
Next, in step S2, the porous support body 97 extruded in step S1 is heated in a heating furnace (not shown) and temporarily fired as a temporary firing step. In this embodiment, the molded body of the porous support body 97 is heated in a heating furnace at about 1000 ° C. for about 2 hours and pre-baked. This temporarily fired porous support body 97 made of forsterite is a generally white electrical insulator.

  Next, in step S3, as a first masking formation step, a masking agent is applied to the porous support 97 that has been pre-fired in step S2, and the masking layer 104 is formed. Specifically, in the first masking formation step, the masking layer 104 is formed by extrusion using the extrusion film formation apparatus 140 that is a dispenser apparatus. That is, in the first masking formation step, the porous mask is formed by continuously extruding the liquid masking forming agent to the region where the masking layer 104 is to be formed by the nozzle 152 (FIG. 9) of the extrusion film forming apparatus 140. In this step, a masking agent is applied onto 97 and a masking layer 104 is formed by extrusion. Therefore, in the first masking forming step, the extrusion film forming apparatus 140 functions as a masking layer forming apparatus. Moreover, a 1st masking formation process is implemented as a liquid substance application | coating process by which the masking formation agent which is a liquid substance is apply | coated with a dispenser apparatus.

  As shown in FIG. 12A, the masking layer 104 is formed on the porous support 97 where the fuel electrode layer 98 is not required to be formed. Since the mask forming agent has a relatively low viscosity, it penetrates to some extent inside the porous support 97 which is a superporous material. For this reason, when the fuel electrode layer 98 is surface-formed in a later process (step S5), the slurry for forming the fuel electrode layer 98 penetrates into the porous support 97 and is provided adjacent thereto. It is possible to prevent the fuel electrode layer 98 from being short-circuited in the porous support body 97. Further, since the amount of liquid material discharged per unit time is larger in the extrusion film forming apparatus 140 than in the dot film forming apparatus 110, even if the mask forming agent permeates the inside of the porous support body 97, it takes a relatively short time. Thus, the masking layer 104 having a predetermined thickness can be formed. On the other hand, when the viscosity of the mask forming agent is too high, the smoothness of the surface of the formed masking layer 104 becomes insufficient. In this case, when the surface film is formed in the next step, the slurry is accumulated on the masking layer 104, and this slurry remains in an unnecessary part of the film formation. In this embodiment, the masking agent is adjusted to an appropriate viscosity.

FIG. 13 is a diagram schematically showing a state when the masking layer 104 is formed on the porous support 97.
First, as shown in FIG. 13A, the masking agent continuously extruded at a constant flow rate from the tip of the nozzle 152 is sticked to the rotating porous support body 97 in a rod shape. The coating is continuously applied while bridging between the tip of the substrate and the surface of the porous support 97. However, after the masking agent is applied, the masking layer 104 is narrow and slightly meandering until the porous support 97 rotates once (FIG. 13A). . When entering the second rotation after the start of application, as shown in FIG. 13B, the applied mask forming agent spreads from the center of the nozzle 152 to both sides and becomes wider, and the applied mask forming agent The masking layer 104 is gradually thickened by the tip of the nozzle 152, and has a convex shape with a thick central portion. Further, when entering the third rotation after the start of coating, as shown in FIG. 13C, the width of the masking layer 104 reaches a predetermined value and becomes substantially uniform. In this embodiment, during the formation of one masking layer 104, the nozzle 152 is not sent in the direction of the rotation center line A of the porous support 97, and the position of the nozzle 152 is fixed.

  Thus, the number of rotations necessary to obtain the convex masking layer 104 having a uniform width and a thick central portion is adjusted by the viscosity of the masking agent, the flow rate, the rotation speed of the porous support 97, and the like. can do. Further, when the masking layer 104 having a wider width is formed, a nozzle having a larger diameter can be used, or a nozzle having a wider width can be used. In this embodiment, fluorosurfing (trademark) FS-1000 series or FG-3020 series manufactured by Fluoro Technology, Inc., which is a fluororesin-based mask forming agent, is used as the mask forming agent.

  In the first masking formation step, the position where the masking layer 104 is formed is determined based on the fixing jig 146 provided in the extrusion film forming apparatus 140. That is, the extrusion film forming apparatus 140 moves the head unit 148 from the position of the fixing jig 146 stored in advance, and the masking layer 104 is formed by extrusion while rotating the porous support 97 from the position. To start. All the masking layers 104 formed in the first masking formation process are positioned by the feed amount of the head portion 148 with the position of the fixing jig 146 as a reference.

  For this reason, the masking layer 104 formed in the first masking forming step is formed in an annular shape orthogonal to the rotation center line A of the extrusion film forming apparatus 140. Therefore, when the porous support body 97 is bent due to a manufacturing error or the like, the masking layer 104 is not accurately orthogonal to the central axis of the porous support body 97. However, such an error does not cause a problem in the fuel battery cell 16, and the masking layer 104 is formed so as to be orthogonal to the rotation center line A of the extrusion film forming apparatus 140, thereby responding to the bending of the porous support 97. Therefore, it is not necessary to perform position correction or the like, and film formation can be performed easily. Further, in the present embodiment, the nozzle driving device 156 maintains the distance D between the tip of the nozzle 152 and the surface of the porous support 97 substantially constant, so that the position of the surface of the porous support 97 is deformed by the bending. Even if it shakes, the thickness of the formed layer is not easily affected. For this reason, even when there is a manufacturing error in the porous support member 97, the masking layer 104 can be formed with an accurate thickness.

  In this embodiment, when the extrusion film forming apparatus 140 forms one masking layer 104 and then moves the head part 148 to a position where another masking layer 104 is formed, the arm part 156a is lifted up. The That is, the head portion 148 is moved along the guide rail 150 to the position where the masking layer 104 is next formed in a state where the rotating roller 156 b and the nozzle 152 are separated from the porous support body 97. Thereby, it is possible to prevent the porous support 97 from being damaged or the masking layer 104 and the like already formed from being damaged by rubbing the surface of the rotating roller 156b.

  Further, as described above, the central portion of the masking layer 104 is formed in a high and convex shape, so that the slurry contacted from above the masking layer 104 in the next fuel electrode layer forming step can be quickly removed from the masking layer 104. Flow down. As a result, it is possible to suppress a large amount of slurry from being deposited on the masking layer 104 and forming a fuel electrode layer in unnecessary portions.

  Next, in step S4, a masking drying process for drying the masking agent applied in the first masking formation process of step S3 is performed. In the present embodiment, in the masking drying process, the porous support body 97 coated with the mask forming agent is heated in a drying furnace to evaporate and remove the solvent in the mask forming agent. This masking drying step is performed at a relatively low temperature so that the resin-based mask forming agent itself is not incinerated or lost. Alternatively, the porous support 97 coated with the mask forming agent can be allowed to stand for a predetermined time and the mask forming agent can be naturally dried.

  Next, in step S5, as a fuel electrode layer forming step, the fuel electrode layer 98, which is one of the functional layers of the power generation element 16a, is formed on the porous support 97 on which the masking layer 104 is formed in step S3. A film is formed. Specifically, in the fuel electrode layer forming step which is the first surface film forming step, the slurry for forming the fuel electrode is brought into contact with the porous support 97 from above the masking layer 104, The fuel electrode layer 98 is formed on the surface where there is not. That is, in step S3, the porous support body 97 on which the masking layer 104 is formed is fixed to the fixing jig 132 of the surface film forming apparatus 130, and the porous support body 97 is rotated and discharged from the lower surface film forming nozzle 136. The slurry to be applied is applied from above the masking layer 104. Therefore, in the fuel electrode layer forming step, the surface film forming device 130 functions as the first surface film forming device or the fuel electrode layer forming device.

  This fuel electrode layer forming step is a lower layer surface film forming step in which surface film formation is performed on the lowermost side, and each fuel electrode layer 98 of all the power generating elements 16a formed on one porous support 97 is formed. This is a surface film forming step in which surface film formation is performed simultaneously. Thus, in the fuel electrode layer forming step, the fuel electrode layer 98 is formed by surface film formation, so that the surface of the fuel electrode layer 98 can be formed more smoothly than by extrusion film formation or dot film formation. Further, since the mask forming agent applied in step S3 penetrates to the inside of the porous support 97 under the masking layer 104, the slurry applied in the surface film-forming process is applied to the inside of the porous support 97. It is possible to prevent the adjacent fuel electrode from being short-circuited.

  In the present embodiment, the slurry used in the fuel electrode layer forming step is a liquid in which a mixture of NiO powder and 10YSZ powder is suspended in an alcohol-based solvent, while the masking layer 104 is formed. The agent is oil repellent. For this reason, the slurry is brought into contact with the entire porous support 97 from above the masking layer 104, but the slurry on the masking layer 104 is repelled by the masking agent and does not deposit on the masking layer 104. . As a result, as shown in FIG. 12 (b), the fuel electrode layer film is formed only in the portion without the masking layer 104. At this time, since the masking layer 104 is formed in a convex shape having a thick center, the attached slurry quickly flows out of the masking layer 104 and does not deposit on the masking layer 104. Furthermore, as shown in FIG. 4, since the slurry deposited on the porous support 97 is repelled by the oil repellent mask forming agent and does not adhere to the masking layer 104, the edges are rounded by the surface tension of the slurry. Is deposited. In this embodiment, an oil-repellent material is used as the mask forming agent. However, depending on the slurry used, a water-repellent mask forming agent may be used.

  Further, since the solvent in the mask forming agent has been sufficiently removed in the masking drying step of Step S4, the attached slurry is not taken into the masking layer 104. That is, if the solvent in the mask forming agent is not sufficiently removed, the applied slurry and the mask forming agent are partially mixed, or the mask forming agent and the slurry cause a chemical reaction, so that the slurry becomes the masking layer 104. May be taken in. The slurry taken into the masking layer 104 may remain on the porous support 97 even after the subsequent pre-baking step (step S6), and the adjacent fuel electrode layer 98 may be short-circuited.

  Further, in the fuel electrode layer forming step, after the fuel electrode layer film is formed on the porous support 97, a drying step (not shown) for drying the deposited slurry is performed. In the present embodiment, in the drying step, the slurry is dried at about 100 ° C. for about 5 minutes. Note that the masking layer 104 formed on the porous support 97 is maintained as it is even after the drying step.

  Next, in step S6, a temporary baking process is performed. In the pre-baking step, the porous support 97 on which the fuel electrode layer film is formed in step S5 is heated by a heating furnace (not shown) and pre-baked. As shown in FIG. 12 (c), the masking layer 104 formed on the porous support 97 is evaporated and disappears by the pre-baking step, and the porous support 97 under the masking layer 104 is exposed. Is done. In the present embodiment, the fuel electrode layer 98 is heated and cured at about 1000 ° C. for about 2 hours in a heating furnace. The color of the temporarily fired NiO / YSZ fuel electrode layer 98 is generally light green.

  Next, in step S7, as a first interconnector forming step, an interconnector layer is formed by the dot film forming apparatus 110 on the fuel electrode layer 98 that has been temporarily fired in step S6. Specifically, in the first interconnector forming step, the first interconnector layer 102a that is a part of the interconnector layer 102 is formed by dot film formation. That is, in the first interconnector forming step, the slurry for forming the first interconnector layer 102a is continuously sprayed in the form of droplets onto the region where the first interconnector layer 102a is to be formed. This is a dot film forming step in which dots of slurry are formed in a predetermined region on the fuel electrode layer 98, and the first interconnector layer 102a is formed by collecting the dots. Accordingly, in the first interconnector forming step, the dot film forming device 110 functions as an interconnector forming device. Moreover, the extrusion film-forming apparatus 140 can also be used as a dispenser apparatus for forming the 1st interconnector layer 102a. In this case, the extrusion film forming apparatus 140 functions as an interconnector forming apparatus. In the present embodiment, a liquid in which LSTNF powder is suspended in an alcohol solvent can be used as the slurry for forming the first interconnector layer 102a.

  As shown in FIG. 12 (d), the first interconnector layer 102 a is formed on one end of each fuel electrode layer 98. The positioning of the part forming the first interconnector layer 102a is executed based on image analysis. That is, the porous support 97 fixed to the fixing jig 116 of the dot film forming apparatus 110 is imaged by the camera 126, and the portion where the fuel electrode layer 98 is formed on the porous support 97 is formed. The boundary line of the missing part is identified by image analysis. Based on the position of the specified boundary line, the first interconnector layer 102a is formed in a dot pattern in a predetermined region on the fuel electrode layer 98. This boundary line is specified for each fuel electrode layer 98 formed on the porous support 97.

  In the first masking formation process of step S3 in FIG. 11, positioning is performed with reference to the fixing jig 116. In the first interconnector forming process, image analysis is used as the first positioning process. Then, positioning is performed based on the position of each fuel electrode layer 98. For this reason, the first interconnector layer 102a can be accurately aligned with each fuel electrode layer 98 regardless of the shrinkage of the porous support 97 due to pre-baking or the change in the attachment position of the porous support 97. . Further, the masking layer 104 for forming the fuel electrode layer 98 is formed so as to be orthogonal to the rotation center line A of the porous support 97. For this reason, the edge of the fuel electrode layer 98 is formed so as to be orthogonal to the rotation center line A, and the fuel electrode layer 98 and the porous support body 97 are positioned at any rotational position. The position of the boundary line is constant, and the formation position of the first interconnector layer 102a can be uniquely determined. In the present embodiment, since the porous support 97 is substantially white and the fuel electrode layer 98 is light green, the brightness contrast is high, and image analysis can be performed accurately even with a monochrome captured image. it can. Further, by performing image analysis based on a monochrome image, the processing time required for image analysis can be shortened.

  Further, in the first interconnector forming step, after the film of the first interconnector layer 102a is formed, a drying step (not shown) for drying the deposited slurry is performed. In the present embodiment, in the drying step, the slurry is dried at about 100 ° C. for about 10 minutes.

  Next, in step S8, a temporary baking process is performed. In the pre-baking step, the porous support 97 on which the film of the first interconnector layer 102a is formed in step S7 is heated by a heating furnace (not shown) and pre-baked. By this temporary firing step, the film of the first interconnector layer 102a formed on each fuel electrode layer 98 is cured. In the present embodiment, the first interconnector layer 102a is heated in a heating furnace at about 1000 ° C. for about 2 hours. The color of the pre-fired LSTNF first interconnector layer 102a is generally brown.

  Next, in step S9, as a second masking formation process, a masking agent is applied to the first interconnector layer 102a preliminarily baked in step S8 by the extrusion film forming apparatus 140, and the masking layer 106 is formed. That is, in the second masking formation step, the masking layer 106 is formed by applying the masking agent onto the first interconnector layer 102a by continuously extruding the masking agent to the region where the masking layer 106 is to be formed. This is an extrusion film forming process. Moreover, a 2nd masking formation process is implemented as a liquid substance application | coating process by which the masking formation agent which is a liquid substance is apply | coated by a dispenser apparatus.

FIG. 14 is a diagram schematically showing a state in which a masking layer is formed on the first interconnector layer by the extrusion film forming apparatus.
As shown in FIG. 14, in the second masking formation step, a masking agent is applied onto the first interconnector layer 102 a from the nozzle 152 of the extrusion film forming apparatus 140. Here, the first interconnector layer 102a to which the mask forming agent is applied is formed on one fuel electrode layer 98, but when applying, the rotating roller 156b of the extrusion film forming apparatus 140 is It abuts on another adjacent fuel electrode layer 98. Since each fuel electrode layer 98 formed on the porous support 97 is formed at the same time in the fuel electrode formation step, it is formed to have the same thickness and has a very smooth surface. For this reason, by performing extrusion film formation while bringing the rotating roller 156b into contact with the adjacent fuel electrode layer 98, the surface to be coated with the masking agent (the surface of the first interconnector layer 102a) and the tip of the nozzle 152 The distance between can be maintained almost constant. In the second masking formation step, the surface on which the masking agent is applied (the surface of the first interconnector layer 102a) is positioned higher than the surface on which the rotating roller 156b abuts (the surface of the fuel electrode layer 98). is there. For this reason, the position of the tip P of the nozzle 152 with respect to the contact point C of the rotating roller 156b is set higher than that in the first masking forming step by this height (the thickness of the first interconnector layer 102a).

As shown in FIG. 12 (e), the masking layer 106 is formed on the first interconnector layer 102a so as to cover the first interconnector layer 102a, leaving the end portions on both sides thereof. The positioning of the position where the masking layer 106 is formed is executed by image analysis using the camera 158 of the extrusion film forming apparatus 140 as the second positioning process. Since the first interconnector layer 102a is brown, the porous support body 97 is substantially white, and the fuel electrode layer 98 is light green, the brightness contrast is high, and it can be accurately positioned by the captured image. The mask forming agent used in the second mask forming step is the same as the mask forming agent used in the first mask forming step.
Next, in step S10, a masking drying process is performed in which the masking agent applied in the second masking formation process in step S9 is dried. In the masking drying step, the porous support 97 coated with the mask forming agent is heated in a drying furnace to evaporate and remove the solvent in the mask forming agent.

  Next, in step S11, as an electrolyte layer forming step, the electrolyte layer 100, which is one of the functional layers of the power generation element 16a, is formed on the porous support 97 on which the masking layer 106 is formed in step S9. Is done. Specifically, in the electrolyte layer forming step which is the second surface film forming step, the slurry for forming the electrolyte layer is brought into contact with the porous support 97 from above the masking layer 106 by the surface film forming apparatus 130. The electrolyte layer 100 is formed on the surface where the masking layer 106 is absent. Therefore, in the electrolyte layer forming step, the surface film forming apparatus 130 functions as an electrolyte layer forming apparatus or a second surface film forming apparatus. The surface film forming apparatus 130 may be the same apparatus as the first surface film forming apparatus used in the fuel electrode layer forming process in step S5, or a dedicated apparatus may be prepared for each. This electrolyte layer forming step is an upper surface film forming step in which surface film formation is performed on the fuel electrode layer 98 having a surface film formed, and all the power generation elements 16a formed on one porous support 97 are formed. This is a surface film forming step in which the respective electrolyte layers 100 are formed simultaneously.

  In the present embodiment, the slurry used in the electrolyte layer forming step is a liquid in which LSGM powder is suspended in an alcohol solvent. This slurry is brought into contact with the entire porous support 97 from above the masking layer 106, but the slurry is repelled by the masking layer 106 and does not deposit on the masking layer 106. As a result, as shown in FIG. 12F, the film of the electrolyte layer 100 is formed only in a portion where the masking layer 106 is not present. That is, all exposed portions of the porous support 97 and the fuel electrode layer 98 and the edge portions on both sides not covered with the masking layer 106 of the first interconnector layer 102a are covered with the membrane of the electrolyte layer 100.

  Also, as shown in FIG. 4, since the edge of the fuel electrode layer 98 is formed in a round shape, the slurry of the electrolyte layer 100 laminated thereon is the boundary between the fuel electrode layer 98 and the porous support 97. It is possible to prevent the formation of voids under the electrolyte layer 100 without entering the gap. Furthermore, since the slurry to form the electrolyte layer 100 is repelled by the masking layer 106 and does not adhere to the masking layer 106, the edges are deposited rounded by the surface tension. In the electrolyte layer forming step, since the electrolyte layer 100 is formed by surface film formation, no dot marks are generated, and a smooth surface can be obtained. In addition, since the electrolyte layer 100 is formed on the fuel electrode layer 98 that is surface-formed, the smoothness is not impaired by the unevenness of the surface of the lower layer.

  Further, in the electrolyte layer forming step, after the membrane of the electrolyte layer 100 is formed on the porous support 97, a drying step (not shown) for drying the deposited slurry is performed. In the present embodiment, in the drying step, the slurry is dried at about 100 ° C. for about 5 minutes. Note that the masking layer 106 formed on the porous support 97 is maintained as it is even after the drying step.

  Next, in step S12, a temporary baking process is performed. In the pre-baking step, the porous support 97 on which the electrolyte layer 100 film is formed in step S11 is heated by a heating furnace (not shown) and pre-baked. As shown in FIG. 12G, the masking layer 106 formed on the first interconnector layer 102a evaporates and disappears by the temporary firing step. As a result, the portion of the first interconnector layer 102a that was covered with the masking layer 106 is exposed. In this embodiment, the electrolyte layer 100 is heated and cured at about 1000 ° C. for about 2 hours in a heating furnace. The color of the calcified electrolyte layer 100 made of LSGM is generally skin color.

  Next, in step S13, as a second interconnector forming step, a second interconnector layer is formed so as to be electrically connected to the first interconnector layer 102a exposed by the preliminary firing in step S12. Specifically, as shown in FIG. 12 (h), in the second interconnector forming step, the exposed first interconnector layer 102a and the edge of the electrolyte layer 100 adjacent to the exposed portion are covered. The second interconnector layer 102 b is formed by the dot film forming apparatus 110. That is, in the second interconnector forming step, the slurry for forming the second interconnector layer 102b is continuously ejected in the form of droplets onto the region where the second interconnector layer 102b is to be formed. This is a dot film forming process in which dots of slurry are formed in a predetermined region and the second interconnector layer 102b is formed by accumulation of the dots. Accordingly, in the second interconnector forming step, the dot film forming device 110 functions as an interconnector forming device.

  In the present embodiment, as a slurry for forming the second interconnector layer 102b, a liquid in which SLT powder is suspended in an alcohol-based solvent can be used. Thus, in this embodiment, the 1st interconnector layer 102a and the 2nd interconnector layer 102b are formed with a different material. Furthermore, in the second interconnector forming step, after the film of the second interconnector layer 102b is formed, a drying step (not shown) for drying the deposited slurry is performed. In the present embodiment, in the drying step, the slurry is dried at about 100 ° C. for about 10 minutes. In the second interconnector forming step, the positioning of the portion forming the second interconnector layer 102b is executed using image analysis as the third positioning step. In the third positioning step, the boundary lines are specified based on the color difference between the first interconnector layer 102a and the electrolyte layer 100 that have been pre-fired.

  Next, in step S14, a first firing process is performed. In the first firing step, the porous support 97, the fuel electrode layer 98, the electrolyte layer 100, the first interconnector layer 102a, and the second interconnector layer 102b formed up to step S13 are heated in a heating furnace (not shown). ) And fired. Thereby, the porous support body 97 and each functional layer formed on it are integrated. In this embodiment, in a 1st baking process, it heats with a heating furnace at about 1300 degreeC for about 2 hours. In the present embodiment, after the first firing step, the electrolyte layer 100 is generally black and the second interconnector layer 102b is also black, but the end of the second interconnector layer 102b that overlaps the electrolyte layer 100 is approximately It is white.

  Next, in step S15, as an air electrode layer forming step, an air electrode layer which is the outermost functional layer is formed on the electrolyte layer 100 baked in step S14. Specifically, as shown in FIG. 12 (i), in the air electrode layer forming process, which is the outermost layer film forming process, dot formation is performed so as to cover the second interconnector layer 102 b and a part of the electrolyte layer 100. The air electrode layer 101 is formed by the membrane device 110. That is, in the air electrode layer forming step, the slurry for forming the air electrode layer 101 is continuously sprayed in the form of liquid droplets onto the area where the air electrode layer 101 is to be formed, so that the slurry is applied to a predetermined area. This is a dot film forming process in which the air electrode layer 101 is formed by collecting the dots. Accordingly, in the air electrode layer forming step, the dot film forming device 110 functions as an air electrode layer forming device.

  Further, in the air electrode layer forming step, as shown in FIG. 4, the feed of the dot film forming apparatus 110 is adjusted so that the thickness of the edge of the air electrode layer 101 is thinner than the thickness of the central part. . That is, at the start of the formation of each air electrode layer 101, the amount of overlap in the axial direction of the formed dots is reduced by increasing the feed amount in the axial direction of the jet dispenser 122 of the dot film forming apparatus 110. The air electrode layer 101 is thinned. Thereafter, by gradually reducing the feed amount of the jet dispenser 122, the overlapping amount of dots to be formed is increased and the air electrode layer 101 is made thicker. At the end of the formation of one air electrode layer 101, the amount of overlap of the jet dispenser 122 in the axial direction is gradually increased to reduce the overlapping amount of dots in the axial direction, thereby making the air electrode layer 101 thinner. Thus, by forming the edge of the air electrode layer 101 thin, it is possible to prevent the air electrode layer 101 that is the outermost functional layer from being peeled after firing.

  In the present embodiment, a liquid in which LSCF powder is suspended in an alcohol solvent can be used as a slurry for forming the air electrode layer 101. In the air electrode layer forming process, the positioning of the portion where the air electrode layer 101 is formed is executed using image analysis as the fourth positioning process. In the fourth positioning step, the boundary line is specified based on the color difference between the end of the second interconnector layer 102b and the electrolyte layer 100 after the first firing step. Further, in the air electrode layer forming step, after the film of the air electrode layer 101 is formed, a drying step (not shown) for drying the deposited slurry is performed. In the present embodiment, in the drying step, the slurry is dried at about 100 ° C. for about 10 minutes.

  Next, in step S16, a second baking process is performed. In the second firing step, the air electrode layer 101 formed in step S15 is heated and fired by a heating furnace (not shown). Thereby, the air electrode layer 101 is integrated with the electrolyte layer 100 and the second interconnector layer 102b formed on the lower side thereof. In the present embodiment, in the second firing step, heating is performed at about 1000 ° C. for about 2 hours in a heating furnace.

The fuel cell 16 of this embodiment is completed by this second firing step.
FIG. 15 is a view showing the surface state of the air electrode layer 101 after the second firing step, FIG. 15 (a) is an enlarged photograph of the air electrode layer 101 surface, and FIG. 15 (b) corresponds to the enlarged photograph. It is a figure which shows typically each dot formed in the part to do.

  As shown in FIG. 15A, a minute crack is generated at the position corresponding to the edge of the dot on the surface of the fired air electrode layer 101. This is because the air electrode layer 101 on which the dot film is formed shrinks in the second baking step, and a minute crack is generated on the surface. Here, in the air electrode layer formation step (step S15), while rotating the porous support body 97 on which the layers up to the second interconnector layer 102b are rotated, the jet dispenser 122 is moved along the guide rail 120. , Slurry droplets are continuously ejected. For this reason, each dot formed when each droplet adheres is arranged so as to draw a spiral while overlapping each other in the circumferential direction and the axial direction.

In the present embodiment, the dots formed by one droplet discharged from the jet dispenser 122 are generally circular with a diameter of about 500 μm, and the dot traces remain on the surface appropriately. By forming the air electrode layer 101 in this way, a minute crack is generated on the surface of the air electrode layer 101, and the surface shape can absorb the shrinkage caused by firing. Preferably, the diameter of the injection nozzle hole 128a of the jet dispenser 122, the viscosity of the slurry, and the like are adjusted so that dots having a diameter of about 200 μm to 1000 μm are formed.
In addition, as a modification, the dot film forming apparatus 110 can be configured so that substantially oval dots are formed. In this case, the length of the long axis of the dots is about 200 μm to 1000 μm. good. The shape of the dots can be appropriately set according to the shape of the ejection nozzle hole 128a, the rotational speed (rpm) of the porous support 97, the interval at which droplets are ejected, the viscosity of the slurry, and the like. Thus, by making each dot of the slurry collected in the air electrode layer forming step into an oval shape, it is possible to increase the overlap at the time of accumulation and enhance the effect of suppressing peeling. In addition, by setting the major axis length of the oval dot to about 200 μm to 1000 μm, it is possible to sufficiently absorb the influence of the thermal expansion of the air electrode layer 101 and prevent peeling, and the air electrode The time required for the layer forming process can also be shortened.

  FIG. 15B schematically shows the arrangement of the dots thus formed. In FIG. 15B, first, the dots I are formed, and then the dots II are formed so as to partially overlap the dots I with the porous support 97 slightly rotated. Subsequently, the dots III and IV are sequentially formed so as to partially overlap. As described above, when the dots are sequentially arranged and the porous support member 97 rotates once and returns to the position of the dot I, the jet dispenser 122 is sent to the position of the dot V in the axial direction, and the dot V is It is formed so as to partially overlap the dot I in the direction. Subsequently, the dots VI and VII are sequentially formed so as to partially overlap.

  Since the dots are arranged in this way, for example, the boundary line exposed on the surface of the air electrode layer 101 in the dot II is only the portion indicated by B in FIG. This part is covered with other dots and is not exposed on the surface. For this reason, even if a crack occurs in the exposed boundary line, the other part of the boundary line is pressed by another dot, so that the dot does not fall off due to the crack. Further, by generating minute cracks on the surface of the air electrode layer 101, the strain caused by the difference in thermal expansion coefficient during firing is dispersed and the stress can be absorbed. For this reason, large peeling does not occur in the air electrode layer 101.

  An electron micrograph of each part of the fuel cell 16 thus completed is shown in FIG. 16A shows an electron micrograph of the porous support 97, FIG. 16B shows a fuel electrode layer 98, FIG. 16C shows an electrolyte layer 100, and FIG. 16D shows an electron micrograph of the air electrode layer 101. FIG.

  As shown in FIG. 16A, the porous support 97 is a structure for supporting each functional layer, and the higher the fuel gas permeability is, the more preferable it is, and it has a superporous structure. As shown in FIG. 16 (b), the fuel electrode layer 98 functions as a conductor that carries the charge generated by the power generation reaction as well as the function of allowing the hydrogen molecules of the fuel gas to permeate. It is porous with few voids. Similarly, as shown in FIG. 16 (d), the air electrode layer 101 also functions as a conductor that carries the charge generated by the power generation reaction, as well as the function of transmitting oxygen molecules in the air. The porosity is less than 97. Further, as shown in FIG. 16C, the electrolyte layer 100 is densely configured to generate a power generation reaction and to ensure airtightness on the fuel electrode side and the air electrode side.

  In FIG. 12 (i), a portion where the fuel electrode layer 98, the electrolyte layer 100, and the air electrode layer 101 are sequentially laminated on the porous support 97 is a power generation unit formed on the fuel cell 16. It functions as each power generating element 16a. The electric charges generated in these power generation elements 16a are transported through the air electrode layer 101 of the current collector (the portion where only the electrolyte layer 100 and the air electrode layer 101 are laminated on the porous support 97), The adjacent power generation element 16a is connected via a connecting portion (a portion in which the fuel electrode layer 98, the first interconnector layer 102a, the second interconnector layer 102b, and the air electrode layer 101 are sequentially laminated on the porous support 97). Connected to the anode. In addition, the portion where the second interconnector layer 102b and the air electrode layer 101 are not formed on the electrolyte layer 100 (the portion where the electrolyte layer 100 is exposed) is between the air electrode layers 101 of the adjacent power generation elements 16a. Functions as an insulating part for insulation.

According to the solid oxide fuel cell manufacturing system of the first embodiment of the present invention, the surface film forming apparatus 130 (FIG. 7), the dot film forming apparatus 110 (FIG. 5), and the extrusion film forming apparatus 140 (FIG. 9). ) Since the fuel cells are manufactured by utilizing the respective characteristics, even when the dimensional accuracy of the porous support 97 is low, the solid oxide fuel cells 16 having a high degree of integration of the power generation elements 16a are efficiently manufactured. can do. That is, the fuel electrode layer 98 is formed on the surface of the porous support 97 by the surface film forming apparatus 130. In the surface film formation, a plurality of fuel electrode layers 98 having a large area can be formed in a short time, and the surface of the formed layer is smooth. It does not adversely affect the smoothness of the air electrode layer 101 and is suitable for forming the lowermost layer.
The extrusion film forming apparatus 140 has a larger amount of liquid material that can be applied per unit time than the dot film forming apparatus 110, and is suitable for efficiently forming the masking layer 104 with high positional accuracy. Further, the layer formed by the extrusion film forming apparatus 140 has a relatively low surface smoothness, but the masking layer 104 is removed after the surface film formation is finished, so the surface smoothness is not a problem. Don't be.
The dot film forming apparatus 110 can form the air electrode layer 101 with high positional accuracy and can strictly manage the film thickness of the air electrode layer 101. The dot film forming apparatus 110 has a small amount of liquid material that can be applied per unit time, but the air electrode layer 101 has a smaller area than the fuel electrode layer 98 and the air electrode layer 101 is formed. Since the surface of the electrolyte layer 100 is denser than the porous support 97 and the liquid material is less likely to permeate, the film formation time of the air electrode layer 101 is not significantly increased. Furthermore, although the layer formed by the dot film forming apparatus 110 has a relatively low surface smoothness, the air electrode layer 101 is the outermost layer, and thus does not adversely affect other functional layers.

  Further, according to the solid oxide fuel cell manufacturing system of the present embodiment, the extrusion film forming apparatus 140 applies the mask forming agent to the rod-like portion on the porous support 97 where the film formation of the fuel electrode layer 98 is unnecessary. Extrude continuously to adhere. Since the extrusion film forming apparatus 140 has a larger amount of liquid material that can be applied per unit time than the dot film forming apparatus 110, the masking layer 104 is efficiently formed on the porous support body 97 through which the liquid material easily penetrates. Therefore, it can be formed with high positional accuracy. Further, since the air electrode layer 101 is formed by the dot film forming apparatus 110, the air electrode layer 101 requiring a thick film can be formed thick. Further, since the air electrode layer 101 is formed by the dot film forming apparatus 110, a minute crack (FIG. 15A) can be generated in the air electrode layer 101, and the thick air electrode layer 101 is generated by the minute crack. The thermal stress acting on can be released.

  Furthermore, according to the solid oxide fuel cell manufacturing system of the present embodiment, the electrolyte layer 100 is formed by the surface film forming apparatus 130 on the porous support body 97 on which the fuel electrode layer 98 is formed. The wide electrolyte layer 100 can be formed in a short time. Further, since the electrolyte layer 100 formed by the surface film forming apparatus 130 has high smoothness, the air electrode layer 101 formed on the electrolyte layer 100 is not adversely affected. Furthermore, by configuring the electrolyte layer 100 smoothly, the oxygen permeability of the electrolyte layer 100 can be made uniform in each part, and unevenness in power generation performance in each part can be suppressed.

  Further, according to the solid oxide fuel cell manufacturing system of this embodiment, the cylindrical porous support 97 is fixed to the fixing jigs 116 (FIG. 5), 132 (FIG. 7), and 146 (rotation support devices). Since film formation is performed while rotating according to FIG. 9), even when the porous support 97 is curved due to a manufacturing error, the functional layer or the like is formed in an annular shape perpendicular to the rotation center line A with high accuracy. Can do.

  Furthermore, according to the solid oxide fuel cell manufacturing system of this embodiment, the interconnector layers 102a and 102b are formed by the dot film forming device 110 that is a dispenser device. For this reason, the interconnector layers 102a and 102b can be formed on the porous support 97 having low dimensional accuracy with high accuracy. In addition, the film formation by dot accumulation has a small area that can be formed per unit time. However, since the interconnector 102 is generally small, the film formation time does not become remarkably long.

Next, a solid oxide fuel cell according to a second embodiment of the present invention will be described with reference to FIG.
The fuel cell according to the second embodiment of the present invention is different from the first embodiment described above in that the fuel electrode layer, the electrolyte layer, and the air electrode layer, which are three functional layers, are each formed of two layers. Is different. Accordingly, here, only the points of the second embodiment of the present invention that are different from the first embodiment will be described, and descriptions of similar configurations, operations, and effects will be omitted.

FIG. 17 is an enlarged cross-sectional view of the functional layer formed on the porous support surface of the fuel cell according to the second embodiment of the present invention.
As shown in FIG. 17, the fuel cell 200 of the present embodiment includes a cylindrical porous support 202, a fuel electrode layer 204, an electrolyte layer 206, and air, which are three functional layers formed thereon. It has a polar layer 208. In the fuel cell 200, a plurality of power generation elements 200 a are formed by sequentially forming a fuel electrode layer 204, an electrolyte layer 206, and an air electrode layer 208 on a porous support 202. Each of these power generating elements 200a is electrically connected in series by an interconnector layer 210. In the present embodiment, twelve power generating elements 200 a are formed on one fuel battery cell 200, and these are connected by an interconnector layer 210.

Next, the structure of the porous support body 202 and each functional layer will be described.
In the present embodiment, the porous support 202 is formed by extruding and sintering a mixture containing forsterite powder as a main component and adding a binder into a cylindrical shape, as in the first embodiment. Yes.
In the present embodiment, the fuel electrode layer 204 is formed of two layers, a lower fuel electrode layer 204a and an upper fuel electrode layer 204b formed thereon. The lower fuel electrode layer 204a of these two layers is a conductive thin film composed of a mixture of NiO powder and 10YSZ (10 mol% Y ₂ O ₃ -90 mol% ZrO ₂ ) powder, as in the first embodiment. It is. On the other hand, the upper fuel electrode layer 204b is a conductive thin film composed of a mixture of NiO powder and GDC (10 mol% Gd ₂ O ₃ -90 mol% CeO ₂ ) powder.

  Here, the fuel electrode layer generally needs to have a catalytic function for reacting hydrogen and oxygen ions and a function for transporting charges (electrons) generated by the reaction. In the fuel cell 200 of the present embodiment, the lower fuel electrode layer 204a is made of a material having higher conductivity than the upper fuel electrode layer 204b, while the upper fuel electrode layer 204b is more catalytically active than the lower fuel electrode layer 204a. Made of high material. As a result, charges generated in the upper fuel electrode layer 204b immediately below the electrolyte layer 206 can be efficiently carried by the lower fuel electrode layer 204a, and a high-performance fuel electrode layer 204 can be configured.

In the present embodiment, the solid electrolyte layer 206 includes a lower electrolyte layer 206a and an upper electrolyte layer 206b formed thereon. Lower electrolyte layer 206a of these two layers, cerium complex oxide (LDC40. I.e., CeO ₂ of 40 mol% of La ₂ O ₃ -60mol%) is a thin film constituted by a powder or the like. On the other hand, the upper electrolyte layer 206b is a thin film made of LSGM powder having a composition of La _0.9 Sr _0.1 Ga _0.8 Mg _0.2 O ₃ , as in the first embodiment.

The lower electrolyte layer 206a functions as a reaction suppression layer, and a chemical reaction between the upper fuel electrode layer 204b and the upper electrolyte layer 206b is suppressed by the lower electrolyte layer 206a.
Similar to the electrolyte layer in the first embodiment, the upper electrolyte layer 206b generates electrical energy through the reaction between oxide ions and hydrogen or carbon monoxide.

In this embodiment, the air electrode layer 208 is composed of a lower air electrode layer 208a and an upper air electrode layer 208b formed thereon. Of these two layers, the lower air electrode layer 208a is a conductive thin film made of LSCF powder having a composition of La _0.6 Sr _0.4 Co _0.2 Fe _0.2 O ₃ . The upper air electrode layer 208b is a conductive thin film made of LSCF powder having a composition of La _0.6 Sr _0.4 Co _0.8 Fe _0.2 O ₃ .

  Here, the air electrode layer generally needs to have a catalytic function of ionizing oxygen in the air and a function of transporting electrons to be reacted with oxygen. In the fuel cell 200 of the present embodiment, the lower air electrode layer 208a is made of a material having higher catalytic activity than the upper air electrode layer 208b (a material having higher oxygen ion conversion performance), while the upper air electrode layer 208b is made lower It is made of a material having higher electron conductivity than the air electrode layer 208a. Thereby, oxygen can be efficiently ionized in the lower air electrode layer 208a adjacent to the electrolyte layer 206 by the electrons carried by the upper air electrode layer 208b, and the high-performance air electrode layer 208 is formed. be able to.

  Similarly to the first embodiment, the interconnector layer 210 includes a first interconnector layer 210a and a second interconnector layer 210b provided thereon.

A method for manufacturing a fuel cell according to the second embodiment of the present invention will be described.
Here, only the changes to the manufacturing process in the first embodiment described with reference to FIG. 11 will be described.
First, steps S1 to S4 in FIG. 11 are the same as those in the first embodiment.

  Next, in the first embodiment, after the fuel electrode layer is surface-formed by the surface film forming apparatus 130 in step S5 of FIG. 11, the deposited slurry is dried by a drying process. In the second embodiment, first, the lower fuel electrode layer 204a is formed by the surface film forming apparatus 130, dried by the drying process, and then the upper fuel electrode layer 204b is formed again by the surface film forming apparatus 130. dry. As a result, the lower fuel electrode layer 204a is formed on the porous support 202 where the masking layer is not formed, and the upper fuel electrode layer 204b is formed on the lower fuel electrode layer 204a.

  Here, the viscosity of the slurry used to form the lower fuel electrode layer 204a is higher than the viscosity of the slurry used to form the upper fuel electrode layer 204b. That is, excessive penetration of the slurry into the porous support 202 can be prevented by increasing the viscosity of the slurry for the lower fuel electrode layer 204a formed directly on the porous support 202. it can. Further, by reducing the viscosity of the slurry for the upper fuel electrode layer 204b, the deposited slurry can be easily spread, and the smoothness of the surface of the deposited upper fuel electrode layer 204b can be increased. The viscosity of the slurry can be appropriately set depending on the ratio of the powder of the material constituting the fuel electrode layer and the solvent in which it is suspended, the particle size of the suspended powder, the type of solvent to be suspended, and the like. .

  When the smoothness of the upper fuel electrode layer 204b is low and the layer thickness becomes nonuniform, the power generation reaction occurring in the fuel electrode layer becomes nonuniform in each part on the fuel electrode layer. When the power generation reaction becomes non-uniform, the current concentrates on the portion where the power generation reaction is strong, and the power generation operation in the fuel cell 200 becomes unstable. According to the present embodiment, such current concentration can be suppressed. Furthermore, by increasing the smoothness of the surface of the upper fuel electrode layer 204b, it is possible to prevent adverse effects on the smoothness of the electrolyte layer 206 and the air electrode layer 208 deposited on the upper fuel electrode layer 204b. it can.

Furthermore, steps S6 to S10 in FIG. 11 are the same as those in the first embodiment.
Next, in the first embodiment, in step S11 of FIG. 11, after the electrolyte layer is surface-formed by the surface film forming apparatus 130, the deposited slurry is dried by a drying process. In the second embodiment, first, the lower electrolyte layer 206a is formed by the surface film forming apparatus 130, dried by the drying process, and then the upper electrolyte layer 206b is formed again by the surface film forming apparatus 130 and dried. . As a result, the lower electrolyte layer 206a is formed on the first interconnector layer 210a where the masking layer is not formed, and the upper electrolyte layer 206b is formed on the lower electrolyte layer 206a.

Furthermore, steps S12 to S14 in FIG. 11 are the same as those in the first embodiment.
Next, in the first embodiment, after the air electrode layer is formed by the dot film forming apparatus 110 in step S15 of FIG. 11, the deposited slurry is dried by a drying process. In the second embodiment, first, the lower air electrode layer 208a is formed by the dot film forming apparatus 110, dried by the drying process, and then the upper air electrode layer 208b is formed again by the dot film forming apparatus 110, dry. Thereby, the lower air electrode layer 208a and the upper air electrode layer 208b are formed so as to cover a part of the second interconnector layer 210b and the upper electrolyte layer 206b.

Here, the viscosity of the slurry used to form the lower air electrode layer 208a is lower than the viscosity of the slurry used to form the upper air electrode layer 208b. That is, by lowering the viscosity of the slurry for the lower air electrode layer 208a, the droplets of the slurry sprayed by the jet dispenser 122 and adhered to the upper electrolyte layer 206b spread thinly, so that the dot traces hardly remain and are smooth. The lower air electrode layer 208a can be formed. On the other hand, by increasing the viscosity of the slurry for the upper air electrode layer 208b, the droplets of the slurry sprayed and adhered to the lower air electrode layer 208a do not spread so much, and the formed upper air electrode layer 208b becomes thicker. . As described above, by smoothly configuring the lower air electrode layer 208a having high catalytic activity, the catalytic reaction in the air electrode layer can be made uniform, and current concentration due to non-uniformity of the catalytic reaction can be suppressed. Can do. Further, since the upper air electrode layer 208b is formed thick, it is possible to reduce the electric resistance of the air electrode layer and to strengthen the upper air electrode layer 208b, which is the outermost functional layer that is most likely to be peeled off. it can.
Finally, the solid oxide fuel cell 200 of the present embodiment is completed by the second firing step of Step S16 in FIG. 11 similar to the first embodiment.

  As mentioned above, although preferable embodiment of this invention was described, a various change can be added to embodiment mentioned above. In particular, in the above-described embodiment, the surface film formation apparatus shown in FIG. 7 is used to contact the masked porous support by discharging the slurry from below to perform surface film formation. However, as a modification, the slurry can be contacted in various directions. For example, the slurry can be contacted by allowing the slurry to flow down from above the masked porous support. Moreover, a slurry can also be contacted by spraying a slurry on the porous support body which gave masking. Further, the slurry can be contacted by immersing the masked porous support in a tank containing the slurry.

In the above-described embodiment, the functional layers are laminated in the order of the fuel electrode layer, the electrolyte layer, and the air electrode layer on the porous support. However, the function layer functions in the order of the air electrode layer, the electrolyte layer, and the fuel electrode layer. Layers can also be formed. The solid oxide fuel cell configured as described above generates electric power by flowing air inside the porous support and flowing fuel gas outside.
Further, in the above-described embodiment, the porous support is cylindrical, but the present invention can be applied to various forms of solid oxide fuel cells such as an elliptical type and a flat type.

In the above-described embodiment, an extrusion film forming apparatus and a dot film forming apparatus are used as the dispenser apparatus, and an extrusion film forming apparatus is used in the first and second masking forming processes. Although the dot film forming apparatus is used in the connector forming process and the air electrode layer forming process, an extrusion film forming apparatus can also be used in the first and second interconnector forming processes and the air electrode layer forming process.
Further, in the above-described embodiment, the extrusion film forming apparatus is provided with the mechanical nozzle driving device provided with the rotating roller, but the nozzle driving device may be an electric type. In this case, for example, the position of the surface on which the liquid material is to be applied is measured using a laser beam or the like, and control for making the distance between the surface and the nozzle tip substantially constant is performed based on the measured position. A nozzle drive device can also be configured.
In the above-described embodiment, the dot film forming apparatus is not provided with a nozzle driving apparatus. However, the dot film forming apparatus is provided with a nozzle driving apparatus to form the tip of a nozzle that ejects droplets and dots. It is also possible to control the distance between the surfaces almost constant.

DESCRIPTION OF SYMBOLS 1 Solid oxide fuel cell system 2 Fuel cell module 4 Auxiliary machine unit 6 Housing 8 Fuel cell storage container 10 Power generation chamber 16 Fuel cell of embodiment of this invention (solid oxide fuel cell)
16a Power generation element 18 Exhaust gas collection chamber 20 Fuel gas supply flow path 21 Exhaust gas discharge flow path 22 Oxidant gas supply flow path 24 Water supply source 26 Pure water tank 28 Water flow rate adjustment unit 30 Fuel supply source 34 Heat exchanger 35 Electromagnetic valve 36 Desulfurizer 38 Fuel blower 40 Air supply source 45 Air flow rate adjustment unit 50 Hot water production device 54 Inverter 56 Oxidant gas introduction pipe 58 Exhaust gas discharge pipe 60 Combustion catalyst 61 Sheath heater 62 Ignition heater 63 First fixed member 64 Inner cylindrical member 64b Small hole 65 Intermediate cylindrical member 66 Outer cylindrical member 68 Inner cylindrical container 70 Outer cylindrical container 72 Dispersion chamber bottom member 72a Insertion pipe 74 Oxidant gas injection pipe 76 Fuel gas dispersion chamber 80 Bus bar 82 Current collector 86 Evaporating part 86a Inclined plate 88 Water Supply pipe 90 Fuel gas supply pipe 2 Fuel gas supply channel partition wall 92a injection port 94 reforming part 96 reforming catalyst 97 porous support 98 fuel electrode layer 100 electrolyte layer 101 air electrode layer 102 interconnector layer 102a first interconnector layer 102b second interconnector layer 104 Masking layer 106 Masking layer 110 Dot deposition device (dispenser device)
112 Pedestal 114 Motor 116 Fixing jig (Rotation support device)
116a Tailstock 118 Head 120 Guide rail 122 Jet dispenser 124 Slurry container 126 Camera 128 Nozzle 128a Injection nozzle hole 128b Recess 128c Slurry supply passage 129 Injection actuator 129a Flexible plate 129b Protrusion 130 Surface film forming device 131 Base 132 Fixing jig (rotary support device)
134 Motor 136 Surface film forming nozzle 138 Pump 139 Slurry container 140 Extrusion film forming apparatus (dispenser apparatus)
142 Base 144 Motor 146 Fixing jig (rotation support device)
146a Tailstock 148 Head 150 Guide rail 152 Nozzle 154 Tank 154a Pipe 156 Nozzle drive device 156a Arm 156b Rotating roller 158 Camera 200 Fuel cell (solid oxide fuel cell) of the second embodiment of the present invention
200a Power generation element 202 Porous support 204 Fuel electrode layer 204a Lower fuel electrode layer 204b Upper fuel electrode layer 206 Electrolyte layer 206a Lower electrolyte layer 206b Upper electrolyte layer 208 Air electrode layer 208a Lower air electrode layer 208b Upper air electrode layer 210 Interconnector Layer 210a First interconnector layer 210b Second interconnector layer

Claims (6)

A solid oxide in which a plurality of power generation elements including a fuel electrode layer, an electrolyte layer, and an air electrode layer, which are functional layers, are formed on an electrically insulating porous support, and these power generation elements are connected by an interconnector A fuel cell manufacturing system comprising:
A first surface deposition apparatus that simultaneously forms a first functional layer of the functional layers of the plurality of power generation elements on the surface of the porous support;
The second functional layer, which is the outermost layer of the functional layers, is continuously ejected in the form of droplets of slurry for forming the second functional layer, thereby forming slurry dots. A dot film forming apparatus for forming the second functional layer by collecting the dots;
An extrusion film forming apparatus provided with a nozzle for continuously extruding and adhering a mask forming agent in a rod shape to a portion where surface film formation by the first surface film forming apparatus is not performed;
A solid oxide fuel cell manufacturing system comprising:   The first functional layer is a fuel electrode layer, the second functional layer is an air electrode layer, and the extrusion film forming apparatus is a portion of the surface of the porous support that does not form the fuel electrode layer. 2. The solid oxide fuel cell manufacturing system according to claim 1, wherein a mask forming agent is attached to the substrate to form a masking layer.   The apparatus further comprises a second surface deposition apparatus for simultaneously forming the electrolyte layers of the plurality of power generating elements on the porous support from which the fuel electrode layer has been formed and from which the masking layer has been removed. The solid oxide fuel cell manufacturing system described.   The porous support has a cylindrical shape, and further includes a rotation support device that rotatably supports the porous support about a rotation center line, the first surface film forming device, and the second surface deposition device. 4. The solid oxide fuel cell manufacturing method according to claim 3, wherein the surface film forming apparatus, the dot film forming apparatus, and the extrusion film forming apparatus perform film formation while rotating the porous support by the rotation support device. system.   Furthermore, it has an interconnector forming device for forming the interconnector, and this interconnector forming device forms slurry dots by continuously ejecting slurry for forming an interconnector layer into droplets. And a dispenser device for forming the interconnector layer by the accumulation of the dots, or a nozzle for continuously extruding and adhering slurry for forming the interconnector layer in a rod shape, and the tip of the nozzle and the interconnector. 5. The solid oxide fuel cell manufacturing system according to claim 4, which is a dispenser device including a nozzle driving device that moves the nozzle so that a distance from a surface on which a connector layer is to be formed is substantially constant. A method for producing a solid oxide fuel cell using the production system according to any one of claims 1 to 5,
The extrusion film forming apparatus includes a rotating roller that is brought into contact with the porous support, and the nozzle is moved together with the rotating roller so that a distance between the tip of the nozzle and the surface of the porous support is reached. Is formed so as to be maintained substantially constant, and using the extrusion film forming apparatus, a mask forming agent is attached to the surface of the porous support to form a masking layer; ,
A fuel electrode layer forming step of forming the fuel electrode layer on the surface of the porous support using the first surface deposition apparatus;
A first calcination step of heating and curing the fuel electrode layer formed by the fuel electrode layer forming step and erasing the masking layer;
The interconnector for forming the interconnector layer on the fuel electrode layer by forming dots of the slurry by continuously spraying the slurry for forming the interconnector in the form of droplets, and collecting the dots Forming process;
Second masking for attaching a masking forming agent on the interconnector layer in a state where the rotating roller of the extrusion film forming apparatus is in contact with a portion of the fuel electrode layer where the interconnector layer is not formed. Forming process;
An electrolyte layer forming step in which a slurry for forming the electrolyte layer is attached using a second surface film forming apparatus, and the electrolyte layers of the plurality of power generation elements are formed simultaneously;
A second preliminary firing step for heating and curing the electrolyte layer formed by the electrolyte layer formation step and for eliminating the masking layer formed in the second masking formation step;
Using the dot deposition apparatus, slurry for forming the air electrode layer is formed into droplets and continuously ejected to form dots of the slurry, and the accumulation of the dots forms the air electrode layer. , An air electrode layer forming step for connecting to the interconnector layer,
A firing step of heating and firing the air electrode layer formed in the air electrode layer forming step;
A method for producing a solid oxide fuel cell, comprising: