JP6237983B2 - Manufacturing method and manufacturing apparatus for solid oxide fuel cell device - Google Patents

Description

  The present invention relates to a solid oxide fuel cell device, and in particular, a method for manufacturing a solid oxide fuel cell device that generates power by supplying fuel and an oxidant gas to a plurality of fuel cells housed in a fuel cell module, And a manufacturing apparatus.

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

  Solid oxide fuel cell devices, particularly fuel cell modules containing fuel cells, fuel flow paths for supplying fuel to the fuel cells, oxidant gas for supplying oxidant gas such as air A flow path and the like are incorporated. Usually, these flow paths are constituted by a plurality of components, and the flow paths are formed by joining the respective components. Further, since the solid oxide fuel cell generally operates at a high temperature of 600 to 1000 ° C., it is necessary to join the respective components so as to withstand such a high temperature. In addition, airtightness must be ensured at the joints of the components constituting the fuel flow path, the oxidant gas flow path, and the like.

For this reason, in the fuel cell module, after the components are mechanically fixed with bolts or the like to the joints that require airtightness between the component parts, the paste-like glass is poured into the joint parts so that the airtightness is achieved. For example, a method of ensuring the above has been adopted.
Further, in the fuel cells described in Japanese Patent No. 3894860 (Patent Document 1) and Japanese Patent Application Laid-Open No. 6-215784 (Patent Document 2), the joints of the components in the fuel cell module can be bonded with a ceramic adhesive. Have been described.

Japanese Patent No. 3894860 JP-A-6-215784

However, after securing the component parts mechanically with bolts and the like, and in order to ensure airtightness by pouring paste-like glass into the joint, two steps are required for joining at one location, which increases the number of manufacturing steps. There is a problem that the manufacturing cost increases.
In addition, when the components in the fuel cell module are fixed with bolts, when exposed to high temperatures, the chromium component is evaporated from the bolts, which causes chromium poisoning to the fuel cell and causes deterioration of the cell. . In addition, when sealing with glass to ensure the airtightness of the joint, there is a problem that when exposed to high temperatures, boron evaporates from the glass and adheres to the cell, thereby deteriorating the fuel cell. .

  On the other hand, according to the adhesion using the ceramic adhesive described in Japanese Patent No. 3894860 and JP-A-6-215784, the deterioration of the fuel cell as described above can be avoided. However, in the conventional joining using a ceramic adhesive, there is a problem in that the component parts cannot be reliably sealed simultaneously with the fixing of the component parts.

  That is, when a ceramic adhesive is cured after application, a solvent such as water evaporates and the volume shrinks.If this shrinkage is not controlled well, the cured ceramic adhesive layer will shrink. Accompanying peeling and excessive cracks occur. When such peeling or cracking occurs in the ceramic adhesive layer, even if sufficient adhesive strength between the components is obtained, sufficient airtightness at the joint cannot be ensured. In order to compensate for this lack of airtightness, it has also been proposed that the ceramic adhesive layer after bonding is coated with glass (Japanese Patent No. 3894860, paragraph 0029). However, when the ceramic adhesive layer is coated with glass, the manufacturing process is increased, and the problem of evaporation of boron from the glass occurs. Therefore, there is no merit in using the ceramic adhesive.

  Further, cracks in the ceramic adhesive layer are likely to occur when the attached ceramic adhesive is dried rapidly. Therefore, if the adhered ceramic adhesive is naturally dried at room temperature, it is possible to avoid the occurrence of cracks. However, when the ceramic adhesive is naturally dried, an extremely long time is required until sufficient adhesive strength is obtained at the joint, and during that time, it is not possible to proceed to the next manufacturing process. In general, the assembly of a solid oxide fuel cell device requires a great number of manufacturing processes, and therefore, the bonding with a ceramic adhesive cannot be practically used industrially. Although it is described in the patent literature that a ceramic adhesive is used in the assembly of a solid oxide fuel cell device, it is considered that it has not been put into practical use for these reasons.

  Furthermore, when the solid oxide fuel cell device is assembled using a ceramic adhesive, the present inventor can ensure that the ceramic adhesive is sufficiently hardened to withstand practical strength and the airtightness can withstand practical use. Even if it was, the new technical problem that the airtightness of the bonded portion was impaired when the fuel cell device was first operated and exposed to high temperature was found. That is, even if the adhered ceramic adhesive is cured and sufficient airtightness and adhesive strength are obtained, a small amount of moisture or other evaporative property is present inside the cured ceramic adhesive layer. The solvent remains. In particular, in the state where the amount of residual moisture and solvent remains intensively in the interior, when the fuel cell device is first operated, the cured ceramic adhesive layer has a temperature higher than that at the time of drying and curing. Ceramic adhesive that has already hardened due to sudden volume expansion and evaporation of residual moisture and solvent due to sudden heating to a much higher temperature within a very fast time It acts to open a weak portion in the surface layer portion of the layer and cause a new crack. The cause of the loss of airtightness that occurs during actual use has been identified by the present inventors.

  That is, when a ceramic adhesive is used for assembling a solid oxide fuel cell device, it cannot withstand the temperature rise in the start-up process of the fuel cell device in a dry / cured state in general use of the ceramic adhesive. . In order to reduce the moisture and solvent remaining in the ceramic adhesive layer to a state that can withstand the temperature rise in the startup process, it is necessary to slowly and sufficiently dry the ceramic adhesive layer over a longer time. For these reasons, it takes a very long time to assemble a solid oxide fuel cell device using a ceramic adhesive, and it is extremely difficult to put it to practical use.

  Accordingly, an object of the present invention is to provide a manufacturing method and a manufacturing apparatus for a solid oxide fuel cell device in which components in a fuel cell module are hermetically bonded using a ceramic adhesive.

In order to solve the above-described problems, the present invention is a method of manufacturing a solid oxide fuel cell device that generates power by supplying fuel and an oxidant gas to a plurality of fuel cells accommodated in a fuel cell module. An adhesive attaching step of attaching a ceramic adhesive to the joint of the component parts, and an attached ceramic adhesive so that the flow path for guiding the fuel or oxidant gas in the fuel cell module is hermetically configured a drying curing step of drying and curing, drying and curing process, after which the work curable step of hardening the deposited ceramic adhesive, the adhesive adhering step and workable curing step are repeated a plurality of times, repeated more than once Ru is further cured by was further remove the solvent remaining in the ceramic adhesive from ceramic adhesive that is cured in working curable step, higher than the workable hardening step It is characterized by having a solvent removal curing step of drying the ceramic adhesive at a temperature and.

  In the present invention configured as described above, in order to airtightly configure the flow path for guiding the fuel or oxidant gas in the fuel cell module, in the adhesive attaching step, the ceramic adhesive is applied to the joint portion of the component parts. Adhere. Next, in the workable curing process, the attached ceramic adhesive is cured to a state where the next manufacturing process can be performed. For each joint, the adhesive attaching step and the workable curing step are repeated a plurality of times. Furthermore, in the solvent removal curing step, the ceramic adhesive cured in each workable curing step is dried to a state that can withstand the temperature during power generation.

  According to the present invention configured as described above, the ceramic adhesive attached in the adhesive attaching step is cured in the workable curing step. The ceramic adhesive after completion of the workable curing process is cured to a state where the next manufacturing process can be carried out. However, when the assembled solid oxide fuel cell device is operated, cracks may occur. State. In this way, in the workable curing process, the next manufacturing process can be carried out, but the temperature was raised over a general power generation temperature of 600 ° C. or more over about 2 hours at the start-up process stage to shift to power generation operation. In some cases, there is a large amount of residual solvent.In this state, the solvent expands rapidly due to a rapid heating increase in the start-up process and evaporates rapidly, generating cracks. Therefore, the drying and curing time can be shortened and the process can be shifted to the next step in a short time. Further, because of such drying and curing, there is no danger of cracking due to slow evaporation of the solvent. This takes advantage of the properties of ceramic adhesives. Specifically, ceramic adhesives can be made in a very short time as long as a solid state sufficient to perform the work of a solid oxide fuel cell is obtained, while preventing cracks in addition to ensuring strength. In order to ensure hermeticity, this is a device based on the finding that it is necessary to extremely increase the drying and curing time.

Further, the adhesive attaching process and the workable curing process are repeated a plurality of times. For this reason, the workable curing step is performed a plurality of times on the ceramic adhesive attached in the initial adhesive attaching step. As a result, moisture or solvent inside the hardened ceramic adhesive is gradually evaporated over a long period of time in the process of proceeding with the next process, and the hardened ceramic adhesive can withstand the temperature during power generation. Close to. As a result, it is possible to reliably avoid the occurrence of cracks that cause poor airtightness while improving work efficiency. Further, after the adhesive attaching step and the workable curing step are repeated a plurality of times, the plurality of joint portions cured by each workable curing step are further dried by the solvent removal curing step. Moisture or solvent remaining inside the cured ceramic adhesive becomes extremely small by the solvent removal and curing process, and the cured ceramic adhesive is in a state that can withstand the temperature during power generation. According to the present invention, a plurality of joints cured by a plurality of workable curing processes are simultaneously dried until they can withstand the temperature rise in the startup process until power generation is started, thereby reducing the time required for manufacturing. However, the components can be joined in an airtight manner.
In addition, according to the present invention configured as described above, the solvent removal curing step dries the ceramic adhesive at a higher temperature than the workable curing step, so that the temperature of the remaining water or solvent can be increased. The remaining water and solvent can be reliably evaporated from the ceramic adhesive. Therefore, the ceramic adhesive can be dried to a state where cracks are not generated even in the starting step of raising the temperature to the power generation temperature in a short time. Since the adhered ceramic adhesive has undergone at least one workable curing process, the risk of cracking is sufficiently reduced even when the ceramic adhesive is dried at a higher temperature than the workable curing process. can do.

In the present invention, the solvent removal curing step is preferably performed at the end of all steps of the dry curing step.
According to the present invention configured as described above, since the solvent removal and curing process is surely performed at the end of all the steps of the drying and curing process, all the joints are started in one solvent removal and curing process. It is possible to dry to a state that can withstand the temperature rise, and the time required for the solvent removal and curing process can be reduced, and the time required for the production can be greatly shortened.

In the present invention, preferably, the solvent removal curing step dries the ceramic adhesive at a temperature higher than the temperature of the workable curing step and lower than the temperature at which the fuel cell can generate power .
According to the present invention configured as described above, workability can be improved by the workable curing process on the premise that a large amount of water and solvent remain even if the ceramic adhesive has sufficient strength. At the same time, by performing the solvent removal and curing process at a temperature lower than the power generation temperature, it is possible to join the ceramic adhesive so that excessive cracks are not generated even in the sudden temperature change due to the first start-up process. A method can be provided.

In this invention, Preferably, a solvent removal hardening process dries a ceramic adhesive at the temperature of 100 to 200 degreeC.
According to the present invention configured as described above, even if there are a large amount of residual water and solvent, the solvent removal and curing process is low in temperature, so that rapid volume expansion can be suppressed and the curing performance can be ensured without generating cracks. Airtightness can be secured. Further, since the solvent removal and curing step is performed at a temperature that does not oxidize the reforming catalyst, the solvent removal and curing step can be performed even on the assembly of the fuel cell device in which the reforming catalyst is incorporated, It can be performed in the final process and work efficiency can be ensured.

In the present invention, preferably, the solvent removal curing step dries the ceramic adhesive at a first temperature higher than the workable curing step, and increases the temperature in the fuel cell module in the startup step of the solid oxide fuel cell device. The temperature is raised to the first temperature more slowly .
In the solvent removal and curing step, it is also desirable to increase the temperature to the power generation chamber temperature during power generation operation over a long period of time spent in the normal startup step. According to the present invention configured as described above, the water and solvent remaining at the first start-up are rapidly expanded and rapidly evaporated by raising the temperature to the temperature range of the first temperature in the manufacturing process. It is possible to reliably avoid the situation that occurs.
Further, according to the present invention configured as described above, when the temperature is raised to the high temperature of the power generation temperature, the drying is performed over a long time while slowly increasing the temperature. Even if many remain, it is possible to reliably evaporate without generating cracks, and to reliably solve the problem of generating cracks in the initial startup process at the time of power generation transition.

In the present invention, preferably, in the solvent removal and curing step, when the temperature is raised to the first temperature, the inert gas or the hydrogen gas is put into the flow path of the fuel gas system.
According to the present invention configured as described above, in the solvent removal and curing process, the oxidation temperature may be exceeded, which may oxidize the catalyst and the like present in the fuel electrode system, resulting in performance degradation. While avoiding risks, the effects of oxidation can be solved simultaneously. In addition, since the oxidized state is reduced by the introduction of hydrogen gas at high temperature, the catalyst and fuel electrode in the fuel gas system are surely reduced at the same time when the ceramic adhesive is hardened. Street performance can be achieved.

In the present invention, preferably, the solvent removal curing step performs a first solvent removal curing step of drying the ceramic adhesive for a predetermined time at a temperature of 100 ° C. or higher and 200 ° C. or lower, and then raises the temperature to the first temperature . It is comprised so that a 2 solvent removal hardening process may be performed.
According to the present invention configured as described above, there is no loss of airtightness that causes excessive cracks in the initial start-up process and hinders performance. Specifically, even if a large amount of water or solvent remains in the workable process, a large amount of water or solvent is used in an environment where the temperature is increased only slowly while suppressing volume expansion in the low temperature first solvent removal process. Can be evaporated, and generation of cracks can be prevented. Even if a minute amount of water or solvent remaining in this state is raised to a high temperature during power generation, the volume expansion can be reduced and the evaporation rate can be reduced, so that cracks can be reliably suppressed. Further, by taking this step, it is possible to suppress the degree of slowing the speed of raising to the power generation temperature, and it is possible to increase production efficiency while reducing the risk of seeing cracks.

In the present invention, preferably, the ceramic adhesive is subjected to a dehydration condensation reaction at 200 ° C. or less in the solvent removal curing step.
According to the present invention configured as described above, since the temperature is low, residual water can be removed while suppressing the generation of cracks. In addition, since it is water that evaporates by curing in the dehydration condensation reaction, evaporation can be performed reliably even at this low temperature, and water that evaporates inside even in the process of building the module is water. Therefore, it is possible to cure and dry the ceramic adhesive at the stage of the module construction process because it does not affect the inside of the module, the catalyst, the cell, and the like. Since it is not necessary to protect the evaporated material, production efficiency can be greatly improved.

In the present invention, preferably, among the workable curing steps that are performed a plurality of times, the workable curing step that is performed first is shorter than the last workable curing step that is performed.
In the present invention, the joint that is initially subjected to the workable curing process is subjected to the workable curing process more times than the joint that is subsequently applied. Therefore, according to the present invention configured as described above, it is possible to secure the time for drying and curing for a longer time than necessary even if the drying time is initially shortened, so the time required for the entire drying and curing is shortened. However, the risk of cracking can be sufficiently reduced.

The present invention also relates to an apparatus for manufacturing a solid oxide fuel cell device that generates power by supplying fuel and an oxidant gas to a plurality of fuel cells accommodated in the fuel cell module. Alternatively, an adhesive adhering device for adhering the ceramic adhesive to the joints of the components and heating the adhering ceramic adhesive at a predetermined temperature for a predetermined time so that the flow path for guiding the oxidant gas is hermetically configured. a heating device for working curable step of hardening the deposited ceramic adhesive, and, after the deposition and workable curing process of ceramic adhesive multiple runs, the cured ceramic adhesive, work curable And a heating control device that controls the heating device so as to execute a solvent removal curing step of drying at a temperature higher than that of the step .

  According to the present invention configured as described above, a solid oxide fuel cell device can be manufactured in a relatively short time while sufficiently reducing the risk of occurrence of cracks.

  According to the method and apparatus for producing a solid oxide fuel cell device of the present invention, components in the fuel cell module can be hermetically joined using a ceramic adhesive.

1 is an overall configuration diagram showing a solid oxide fuel cell apparatus (SOFC) according to an embodiment of the present invention. It is sectional drawing of the fuel cell storage container incorporated in the solid oxide fuel cell apparatus by one Embodiment of this invention. It is sectional drawing which decomposed | disassembled and showed the main member of the fuel cell storage container incorporated in the solid oxide fuel cell apparatus by one Embodiment of this invention. It is sectional drawing which expands and shows the part of the exhaust concentration chamber incorporated in the solid oxide fuel cell apparatus by one Embodiment of this invention. It is a VV cross section in FIG. (A) It is sectional drawing which expands and shows the lower end part of the fuel cell by which the lower end is made into the cathode, (b) It is sectional drawing which expands and shows the lower end part of the fuel cell by which the lower end is made into the anode is there. It is the schematic diagram which showed the manufacturing procedure of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is the schematic diagram which showed the manufacturing procedure of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is the schematic diagram which showed the manufacturing procedure of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is the schematic diagram which showed the manufacturing procedure of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is the schematic diagram which showed the manufacturing procedure of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is the schematic diagram which showed the manufacturing procedure of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is the schematic diagram which showed the manufacturing procedure of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is the schematic diagram which showed the manufacturing procedure of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is the schematic diagram which showed the manufacturing procedure of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is the schematic diagram which showed the manufacturing procedure of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is the schematic diagram which showed the manufacturing procedure of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is the schematic diagram which showed the manufacturing procedure of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is the schematic diagram which showed the manufacturing procedure of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is the schematic diagram which showed the manufacturing procedure of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is the schematic diagram which showed the manufacturing procedure of the solid oxide fuel cell apparatus by one Embodiment of this invention. 1 is a plan view of a cover member disposed on a poured ceramic adhesive in a solid oxide fuel cell device according to an embodiment of the present invention. 1 is a perspective view showing a state where a cover member is arranged on a poured ceramic adhesive in a solid oxide fuel cell device according to an embodiment of the present invention. 3 is a flowchart showing a manufacturing procedure of a solid oxide fuel cell device according to an embodiment of the present invention. In the solid oxide fuel cell device according to one embodiment of the present invention, it is a cross-sectional view showing an enlargement of the adhesion portion of the fuel cell to the aggregation chamber lower member. It is a graph which shows an example of the temperature control in the drying furnace in the workable hardening process and the solvent removal hardening process in the manufacturing method of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is a photograph which shows an example at the time of adhere | attaching a fuel battery cell with a ceramic adhesive agent by the normal adhesion | attachment method. It is a figure showing the 1st solvent removal hardening process in the modification of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is a figure showing the 2nd solvent removal hardening process in the modification of the solid oxide fuel cell apparatus by one Embodiment of this invention. It is a figure explaining the heating method in a 2nd solvent removal hardening process.

Next, a solid oxide fuel cell apparatus (SOFC) according to an embodiment of the present invention will be described with reference to the accompanying drawings.
FIG. 1 is an overall configuration diagram showing a solid oxide fuel cell apparatus (SOFC) according to an embodiment of the present invention. As shown in FIG. 1, a solid oxide fuel cell apparatus (SOFC) 1 according to an embodiment of the present invention 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 configured inside the fuel cell storage container 8, and a plurality of fuel cell cells 16 are concentrically arranged in the power generation chamber 10. With these fuel cell cells 16, A power generation reaction of air, which is fuel gas and oxidant gas, is performed.

  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 built in the fuel cell module of the solid oxide fuel cell device (SOFC) according to the embodiment of the present invention will be described with reference to FIGS. FIG. 2 is a cross-sectional view of the fuel cell storage container, and FIG. 3 is an exploded cross-sectional view of the main members 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. Here, the exhaust gas discharge channel 21 and the oxidant gas supply channel 22 function as an oxidant gas channel that supplies / discharges the oxidant gas.

  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 FIGS. 2 and 3, inside the fuel cell storage container 8, an inner cylindrical member 64, which is a power generation chamber constituting member, and an outer cylindrical member in order from the inside so as to surround the periphery of the fuel cell 16. 66, an inner 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. That is, the exhaust gas discharge passage 21 is disposed so as to surround the fuel gas supply passage 20, and the oxidant gas supply passage 22 is disposed so as to surround the exhaust gas discharge passage 21. 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. .

  The inner cylindrical member 64 is a substantially cylindrical hollow body, and its upper end and lower end are open. A circular first fixing member 63 that is a dispersion chamber forming plate is airtightly welded to the inner wall surface of the inner cylindrical member 64. A fuel gas dispersion chamber 76 is defined by the lower surface of the first fixing member 63, the inner wall surface of the inner cylindrical member 64, and the upper surface of the dispersion chamber bottom member 72. The first fixing member 63 is formed with a plurality of insertion holes 63a through which the fuel battery cells 16 are inserted, and each fuel battery cell 16 is inserted into each insertion hole 63a in the ceramic adhesive. Is bonded to the first fixing member 63. As described above, in the solid oxide fuel cell device 1 of the present embodiment, each member constituting the fuel cell module 2 is filled with the ceramic adhesive in the joint portion between the members constituting the fuel cell module 2 and cured. Are hermetically joined to each other.

  The outer cylindrical member 66 is a cylindrical tube disposed around the inner cylindrical member 64, and is generally similar to the inner cylindrical member 64 so that an annular flow path is formed between the outer cylindrical member 66 and the inner cylindrical member 64. It is formed into a shape. Further, an intermediate cylindrical member 65 is disposed between the inner cylindrical member 64 and the outer cylindrical member 66. The intermediate cylindrical member 65 is a cylindrical tube disposed between the inner cylindrical member 64 and the outer cylindrical member 66, and is modified between the outer peripheral surface of the inner cylindrical member 64 and the inner peripheral surface of the intermediate cylindrical member 65. A portion 94 is configured. An annular space between the outer peripheral surface of the intermediate cylindrical member 65 and the inner peripheral surface of the outer cylindrical member 66 functions as the fuel gas supply channel 20. Therefore, the reforming unit 94 and the fuel gas supply channel 20 receive heat due to heat generation in the fuel cell 16 and combustion of residual fuel at the upper end of the exhaust collecting chamber 18. Further, the upper end portion of the inner cylindrical member 64 and the upper end portion of the outer cylindrical member 66 are hermetically joined by welding, and the upper end of the fuel gas supply channel 20 is closed. Furthermore, the lower end of the intermediate cylindrical member 65 and the outer peripheral surface of the inner cylindrical member 64 are hermetically joined by welding.

  The inner cylindrical container 68 is a cup-shaped member having a circular cross section disposed around the outer cylindrical member 66, and an annular flow path having a substantially constant width is formed between the inner cylindrical container 68 and the outer cylindrical member 66. The side surface is formed in a generally similar shape to the outer cylindrical member 66. The inner cylindrical container 68 is disposed so as to cover the open portion at the upper end of the inner cylindrical member 64. 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 functions as the exhaust gas discharge passage 21 (FIG. 2). The exhaust gas discharge passage 21 communicates with the space inside the inner cylindrical member 64 through a plurality of small holes 64 a provided in the upper end portion of the inner cylindrical member 64. Further, an exhaust gas discharge pipe 58 that is an exhaust gas outlet is connected to the lower side surface of the inner cylindrical container 68, and the exhaust gas discharge passage 21 is communicated with the exhaust gas discharge pipe 58.

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.

  The outer cylindrical container 70 is a cup-shaped member having a circular cross section disposed around the inner cylindrical container 68, and an annular channel having a substantially constant width is formed between the outer cylindrical container 70 and the inner cylindrical container 68. The side surface is formed in a substantially similar shape to the inner cylindrical container 68. 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.

  The dispersion chamber bottom member 72 is a substantially circular dish-like member, and is hermetically fixed to the inner wall surface of the inner cylindrical member 64 with a ceramic adhesive. Thereby, a fuel gas dispersion chamber 76 is formed 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. Further, the insertion tube 72 a is filled with a ceramic adhesive, and the airtightness of the fuel gas dispersion chamber 78 is ensured. Further, a heat insulating material 72b (FIG. 2) is disposed around 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. By attaching the upper end of the oxidant gas injection pipe 74 to the ceiling surface of the inner cylindrical container 68, the oxidant gas supply flow path 22 and the oxidant gas formed between the inner cylindrical container 68 and the outer cylindrical container 70 are formed. An injection pipe 74 is communicated. 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 63a 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 adhesion. ing.

  As shown in FIG. 2, the inner cylindrical member 64 is provided with a plurality of small holes 64 b below the first fixing member 63. A space between the outer periphery of the inner cylindrical member 64 and the inner periphery of the intermediate cylindrical member 65 is communicated with the fuel gas dispersion chamber 76 through a plurality of small holes 64b. The supplied fuel once rises in the space between the inner circumference of the outer cylindrical member 66 and the outer circumference of the intermediate cylindrical member 65, and then descends in the space between the outer circumference of the inner cylindrical member 64 and the inner circumference of the intermediate cylindrical member 65. Then, it 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 an elongated metal conductor for taking out the electric power generated by each fuel battery cell 16 to the outside of the fuel battery cell container 8, and is fixed to the insertion pipe 72 a of the dispersion chamber bottom member 72 via the insulator 78. Has been. 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 (FIG. 4). 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 gas collecting chamber will be described with reference to FIGS. 4 and 5.
4 is an enlarged cross-sectional view showing a portion of the exhaust gas collecting chamber, and FIG. 5 is a VV cross section in FIG.
As shown in FIG. 4, 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 is provided at the center of the exhaust concentration chamber 18. Extends through.

  As shown in FIG. 5, three stays 64 c for supporting the exhaust collecting chamber 18 are attached to the inner wall surface of the inner cylindrical member 64 at equal intervals. As shown in FIG. 4, each stay 64 c is a small piece obtained by bending a thin metal plate. By placing the exhaust collection chamber 18 on each stay 64 c, the exhaust collection chamber 18 is concentric with the inner cylindrical member 64. Positioned above. As a result, the gap between the outer peripheral surface of the exhaust collecting chamber 18 and the inner peripheral surface of the inner cylindrical member 64 and the gap between the inner peripheral surface of the exhaust collecting chamber 18 and the outer peripheral surface of the oxidizing gas injection pipe 74 are as follows. , Uniform over the entire circumference (FIG. 5).

The exhaust collecting chamber 18 is configured by hermetically joining the collecting chamber upper member 18a and the collecting chamber lower member 18b.
The aggregation chamber lower member 18b is a circular dish-shaped member opened upward, and a cylindrical portion for allowing the oxidant gas injection pipe 74 to pass therethrough is provided at the center thereof.
The aggregation chamber upper member 18a is a circular dish-shaped member that is open at the bottom, and an opening for allowing the oxidant gas injection pipe 74 to pass therethrough is provided at the center thereof. The aggregation chamber upper member 18a is configured to be fitted into a donut-shaped cross-sectional area opened above the aggregation chamber lower member 18b.

  The gap between the inner peripheral surface of the wall around the aggregation chamber lower member 18b and the outer peripheral surface of the aggregation chamber upper member 18a is filled with a ceramic adhesive and cured, so that the airtightness of the joint is ensured. Yes. Further, a large-diameter seal ring 19a is disposed on the ceramic adhesive layer formed of the ceramic adhesive filled in the joint portion, and covers the ceramic adhesive layer. The large-diameter seal ring 19a is an annular thin plate, is disposed so as to cover the filled ceramic adhesive after being filled with the ceramic adhesive, and is fixed to the exhaust collecting chamber 18 by curing of the adhesive.

  On the other hand, the ceramic adhesive is also filled and hardened between the outer peripheral surface of the cylindrical portion at the center of the aggregation chamber lower member 18b and the edge of the opening at the center of the aggregation chamber upper member 18a. It is secured. Further, a small-diameter seal ring 19b is disposed on the ceramic adhesive layer formed of the ceramic adhesive filled in the joint portion, and covers the ceramic adhesive layer. The small-diameter seal ring 19b is an annular thin plate, is disposed so as to cover the filled ceramic adhesive after being filled with the ceramic adhesive, and is fixed to the exhaust collecting chamber 18 by curing of the adhesive.

  A plurality of circular insertion holes 18c are provided on the bottom surface of the aggregation chamber lower member 18b. The upper end portions of the fuel cells 16 are respectively inserted into the insertion holes 18c, and the fuel cells 16 extend through the insertion holes 18c. A ceramic adhesive is poured onto the bottom surface of the aggregation chamber lower member 18b through which each fuel cell 16 penetrates, and is cured, whereby a gap between the outer periphery of each fuel cell 16 and each insertion hole 18c. Are hermetically filled, and each fuel cell 16 is fixed to the aggregation chamber lower member 18b.

  Further, a circular thin plate-like cover member 19c is disposed on the ceramic adhesive poured on the bottom surface of the aggregation chamber lower member 18b, and is fixed to the aggregation chamber lower member 18b by hardening of the ceramic adhesive. The cover member 19c is provided with a plurality of insertion holes at positions similar to the insertion holes 18c of the aggregation chamber lower member 18b, and the upper end portion of each fuel cell 16 has a ceramic adhesive layer and the cover member 19c. It extends through.

  On the other hand, a plurality of jet outlets 18d for jetting the collected fuel gas are provided on the ceiling surface of the exhaust collecting chamber 18 (FIG. 5). Each ejection port 18d is arranged on the circumference of the aggregation chamber upper member 18a. 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 outlet 18d, where it is burned. The

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 in the lower portion of the fuel gas supply flow path 20 configured by a space between the inner cylindrical member 64 and the outer cylindrical member 66. . 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 evaporator 86 is disposed below the oxidant gas introduction pipe 56 for introducing power generation air and above the exhaust gas discharge pipe 58 that discharges exhaust gas. 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 for steam reforming supplied from the water flow rate adjustment unit 28 passes through the water supply pipe 88. To the evaporation unit 86. The upper end of the water supply pipe 88 passes through the inclined plate 86a and extends to the upper surface side of the inclined plate 86a, 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 inner wall surface of the outer cylindrical member 66. Stay between. 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 fuel gas supply pipe 90 is a pipe extending vertically from the lower end of the inner cylindrical member 64 into the fuel gas supply flow path 20. Further, the upper end of the fuel gas supply pipe 90 is positioned below the inclined plate 86a. 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. The fuel gas supply channel partition wall 92 is an annular metal plate provided so as to vertically separate an annular space between the inner periphery of the outer cylindrical member 66 and the outer periphery of the intermediate cylindrical member 65. A plurality of injection ports 92a are provided at equal intervals on the circumference of the fuel gas supply channel partition wall 92, and the upper space and the lower space of the fuel gas supply channel partition wall 92 are formed by these injection ports 92a. Is communicated. 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. It is injected into the space above the gas supply channel partition wall 92. When injected from each injection port 92a into a wide space above the fuel gas supply flow path partition wall 92, the raw fuel gas and water vapor are rapidly decelerated 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 part 94 is arranged so as to surround the upper part of each fuel battery cell 16 and the periphery of the exhaust collecting chamber 18 above it. 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.

As described above, when the raw fuel gas and water vapor mixed in the space above the fuel gas supply passage partition wall 92 come into contact with the reforming catalyst 96 filled in the reforming unit 94, The steam reforming reaction SR shown in the formula (1) proceeds.
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 fuel battery cell 16 will be described with reference to FIG.
In the solid oxide fuel cell device 1 according to the embodiment of the present invention, a cylindrical horizontal stripe cell using a solid oxide is adopted as the fuel cell 16. On each fuel cell 16, a plurality of single cells 16a 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.

  FIG. 6A is an enlarged cross-sectional view showing a lower end portion of the fuel battery cell 16 whose lower end is a cathode, and FIG. 6B is a cross-sectional view of the fuel battery cell 16 whose lower end is an anode. It is sectional drawing which expands and shows a lower end part.

  As shown in FIG. 6, the fuel cell 16 is formed of an elongated cylindrical porous support body 97 and a plurality of layers formed in a horizontal stripe pattern on the outside of the porous support body 97. Around the porous support 97, a fuel electrode layer 98, a reaction suppression layer 99, a solid electrolyte layer 100, and an air electrode layer 101 are formed in a horizontal stripe shape in order from the inside. For this reason, the fuel gas supplied through the fuel gas dispersion chamber 76 flows inside the porous support body 97 of each fuel battery cell 16, and the air injected from the oxidant gas injection pipe 74 is the air electrode. It flows outside the layer 101. Each single cell 16 a formed on the fuel cell 16 is composed of a set of fuel electrode layer 98, reaction suppression layer 99, solid electrolyte layer 100, and air electrode layer 101. The fuel electrode layer 98 of one single cell 16 a is electrically connected to the air electrode layer 101 of the adjacent single cell 16 a via the interconnector layer 102. Thereby, the several single cell 16a formed on the one fuel cell 16 is electrically connected in series.

  As shown in FIG. 6A, an electrode layer 103a is formed on the outer periphery of the porous support 97 at the cathode side end of the fuel battery cell 16, and a lead film layer 104a is formed outside the electrode layer 103a. Has been. At the cathode side end, the air electrode layer 101 and the electrode layer 103a of the single cell 16a located at the end are electrically connected by the interconnector layer 102. The electrode layer 103 a and the lead film layer 104 a are formed so as to penetrate the first fixing member 63 at the end portion of the fuel cell 16 and protrude downward from the first fixing member 63. The electrode layer 103a is formed below the lead film layer 104a, and the current collector 82 is electrically connected to the electrode layer 103a exposed to the outside. As a result, the air electrode layer 101 of the single cell 16a located at the end is connected to the current collector 82 via the interconnector layer 102 and the electrode layer 103a, and current flows as shown by the arrows in the figure. Further, a gap between the edge of the insertion hole 63a of the first fixing member 63 and the lead film layer 104a is filled with a ceramic adhesive, and the fuel cell 16 is fixed first on the outer periphery of the lead film layer 104a. It is fixed to the member 63.

  As shown in FIG. 6B, at the anode side end of the fuel battery cell 16, the fuel electrode layer 98 of the single cell 16a located at the end is extended, and the extension of the fuel electrode layer 98 is the electrode. It functions as the layer 103b. A lead film layer 104b is formed outside the electrode layer 103b. The electrode layer 103 b and the lead film layer 104 b are formed so as to penetrate the first fixing member 63 at the end portion of the fuel cell 16 and protrude downward from the first fixing member 63. The electrode layer 103b is formed below the lead film layer 104b, and the current collector 82 is electrically connected to the electrode layer 103b exposed to the outside. As a result, the fuel electrode layer 98 of the single cell 16a located at the end is connected to the current collector 82 via the electrode layer 103b formed integrally, and a current flows as shown by an arrow in the figure. Further, a gap between the edge of the insertion hole 63a of the first fixing member 63 and the lead film layer 104b is filled with a ceramic adhesive, and the fuel cell 16 is first fixed on the outer periphery of the lead film layer 104b. It is fixed to the member 63.

  6A and 6B, the configuration of the lower end portion of each fuel cell 16 has been described, but the configuration of the upper end portion of each fuel cell 16 is also the same. In the upper end portion, each fuel cell 16 is fixed to the aggregation chamber lower member 18b of the exhaust aggregation chamber 18, but the configuration of the fixed portion is the same as the fixing to the first fixing member 63 in the lower end portion. .

Next, the structure of the porous support body 97 and each layer is demonstrated.
In the present embodiment, the porous support body 97 is formed by extruding and sintering a mixture of forsterite powder and a binder.
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 reaction suppression layer 99 is a thin film composed of a cerium-based composite oxide (LDC 40, that is, 40 mol% La ₂ O ₃ -60 mol% CeO ₂ ). The chemical reaction between the layer 98 and the solid electrolyte layer 100 is suppressed.
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 made of powder having a composition of La _0.6 Sr _0.4 Co _0.8 Fe _0.2 O ₃ .
In this embodiment, the interconnector layer 102 is a conductive thin film made of SLT (lanthanum-doped strontium titanate). Adjacent single cells 16 a on the fuel cell 16 are connected via the interconnector layer 102.
The electrode layers 103a and 103b are formed of the same material as the fuel electrode layer 98 in the present embodiment.
In this embodiment, the lead film layers 104a and 104b are made of the same material as that of the solid electrolyte layer 100.

Next, with reference to FIG.1 and FIG.2, the effect | action of the solid oxide fuel cell apparatus 1 is demonstrated.
First, in the starting process of the solid oxide fuel cell device 1, the fuel blower 38 is started, fuel supply is started, and energization to the sheath heater 61 is started. When energization of the sheath heater 61 is started, the combustion catalyst 60 disposed above the sheath heater 61 is heated, and the evaporator 86 disposed inside is also heated. The fuel supplied by the fuel blower 38 flows from the fuel gas supply pipe 90 into the fuel cell storage container 8 through the desulfurizer 36, the heat exchanger 34, and the electromagnetic valve 35. The inflowed fuel rises to the upper end in the fuel gas supply flow path 20, then descends in the reforming portion 94, and flows into the fuel gas dispersion chamber 76 through the small hole 64 b provided in the lower part of the inner cylindrical member 64. To do. Immediately after the solid oxide fuel cell device 1 is started, the temperature of the reforming catalyst 96 in the reforming unit 94 has not risen sufficiently, so that fuel reforming is not performed.

  The fuel gas that has flowed into the fuel gas dispersion chamber 76 flows into the exhaust collection chamber 18 through the inside (fuel electrode side) of each fuel cell 16 attached to the first fixing member 63 of the fuel gas dispersion chamber 76. Immediately after the start of the solid oxide fuel cell device 1, the temperature of each fuel cell 16 has not risen sufficiently, and power is not taken out to the inverter 54. Does not occur.

  The fuel that has flowed into the exhaust aggregation chamber 18 is ejected from the ejection port 18 d of the exhaust aggregation chamber 18. The fuel ejected from the ejection port 18d is ignited by the ignition heater 62 and burned there. Due to this combustion, the reforming section 94 disposed around the exhaust aggregation chamber 18 is heated. Further, the exhaust gas generated by the combustion flows into the exhaust gas discharge passage 21 through the small hole 64 a provided in the upper part of the inner cylindrical member 64. The high-temperature exhaust gas descends in the exhaust gas discharge passage 21 and is used for power generation that flows in the fuel gas supply passage 20 provided on the inside and the oxidant gas supply passage 22 provided on the outside. Heat the air. Further, the exhaust gas passes through the combustion catalyst 60 disposed in the exhaust gas discharge passage 21 to remove carbon monoxide and is discharged from the fuel cell storage container 8 through the exhaust gas discharge pipe 58.

  When the evaporation section 86 is heated by the exhaust gas and the sheath heater 61, the water for steam reforming supplied to the evaporation section 86 is evaporated and steam is generated. The water for steam reforming is supplied by the water flow rate adjusting unit 28 to the evaporation unit 86 in the fuel cell storage container 8 through the water supply pipe 88. The water vapor generated in the evaporation unit 86 and the fuel supplied via the fuel gas supply pipe 90 are temporarily retained in the space below the fuel gas supply flow path partition wall 92 in the fuel gas supply flow path 20. The fuel gas is supplied from a plurality of injection ports 92 a provided in the fuel gas supply channel partition wall 92. The fuel and water vapor that are vigorously injected from the injection port 92 a are sufficiently mixed by being decelerated in the space above the fuel gas supply flow path partition wall 92.

  The mixed fuel and water vapor rise in the fuel gas supply channel 20 and flow into the reforming unit 94. In a state where the reforming catalyst 96 of the reforming unit 94 has risen to a temperature at which reforming can be performed, when the fuel / steam mixture passes through the reforming unit 94, a steam reforming reaction occurs, and the mixture Is reformed into a fuel rich in hydrogen. The reformed fuel flows into the fuel gas dispersion chamber 76 through the small hole 64b. A large number of small holes 64 b are provided around the fuel gas dispersion chamber 76, and a sufficient volume is secured as the fuel gas dispersion chamber 76, so that the reformed fuel protrudes into the fuel gas dispersion chamber 76. Evenly flows into the battery cells 16.

  On the other hand, the air, which is the oxidant gas supplied by the air flow rate adjusting unit 45, flows into the oxidant gas supply passage 22 through the oxidant gas introduction pipe 56. The air flowing into the oxidant gas supply channel 22 rises in the oxidant gas supply channel 22 while being heated by the exhaust gas flowing inside. The air rising in the oxidant gas supply passage 22 is collected at the center at the upper end portion in the fuel cell storage container 8 and flows into the oxidant gas injection pipe 74 communicated with the oxidant gas supply passage 22. To do. The air flowing into the oxidant gas injection pipe 74 is injected into the power generation chamber 10 from the lower end, and the injected air hits the upper surface of the first fixing member 63 and spreads throughout the power generation chamber 10. The air that has flowed into the power generation chamber 10 flows into the gap between the outer peripheral wall of the exhaust collecting chamber 18 and the inner peripheral wall of the inner cylindrical member 64, and between the inner peripheral wall of the exhaust collecting chamber 18 and the outer peripheral surface of the oxidizing gas injection pipe 74. Ascend through the gaps in between.

  At this time, a part of the air flowing through the outside (air electrode side) of each fuel cell 16 is used for the power generation reaction. Further, a part of the air that has risen above the exhaust aggregation chamber 18 is used for the combustion of fuel ejected from the ejection port 18d of the exhaust aggregation chamber 18. Exhaust gas generated by the combustion and air remaining without being used for power generation and combustion flow into the exhaust gas discharge passage 21 through the small hole 64a. The exhaust gas and air that have flowed into the exhaust gas discharge passage 21 are discharged after carbon monoxide is removed by the combustion catalyst 60.

  In this way, the temperature rises to about 650 ° C., which is the temperature at which each fuel cell 16 can generate electricity, and the reformed fuel flows inside each fuel cell 16 (fuel electrode side) and outside (air electrode side). When air flows through the chamber, an electromotive force is generated by a chemical reaction. In this state, when the inverter 54 is connected to the bus bar 80 drawn out from the fuel cell storage container 8, electric power is taken out from each fuel cell 16 to generate power.

  Further, in the solid oxide fuel cell device 1 of the present embodiment, the power generation air is injected from the oxidant gas injection pipe 74 disposed in the center of the power generation chamber 10, and the inside of the power generation chamber 10 is exhausted. Ascending through the uniform gap between the chamber 18 and the inner cylindrical member 64 and the uniform gap between the exhaust collecting chamber 18 and the oxidant gas injection pipe 74. For this reason, the air flow in the power generation chamber 10 is almost completely axisymmetric, and the air flows uniformly around each fuel cell 16. Thereby, the temperature difference between each fuel cell 16 is suppressed, and an equal electromotive force can be generated in each fuel cell 16.

Next, a method for manufacturing the solid oxide fuel cell device 1 according to the embodiment of the present invention will be described with reference to FIGS.
7 to 21 are schematic views showing the manufacturing procedure of the solid oxide fuel cell device 1, and the detailed configuration is omitted for explanation. FIG. 24 is a flowchart showing a manufacturing procedure of the solid oxide fuel cell device 1.

  First, as shown in FIG. 7, the inner cylindrical member 64, the intermediate cylindrical member 65, the outer cylindrical member 66, and the first fixing member 63 are assembled by welding (step S1 in FIG. 24). Here, the first fixing member 63 is disposed so as to be orthogonal to the central axis of the inner cylindrical member 64, and the outer peripheral edge thereof is hermetically welded to the inner wall surface of the inner cylindrical member 64. In addition, the reforming portion 94 provided between the inner cylindrical member 64 and the intermediate cylindrical member 65 is filled with the reforming catalyst 96. Furthermore, the water supply pipe 88 and the fuel gas supply pipe 90 are also attached by welding.

  Next, as shown in FIG. 8, the lower jig 110 as the first positioning device is accurately positioned with respect to the inner cylindrical member 64 (step S2 in FIG. 24). The lower jig 110 includes a plurality of positioning shafts 110 a extending upward in parallel with the inner cylindrical member 64, and these positioning shafts 110 a are respectively inserted through holes provided in the first fixing member 63. It arrange | positions so that it may each penetrate 63a. Further, the fuel cell 16 is disposed on each positioning shaft 110a extending through each insertion hole 63a. In this step, each fuel cell 16 is inserted into each insertion hole 63 a of the first fixing member 63.

When the positioning shaft 110a is inserted into the fuel battery cell 16, one end of the fuel battery cell 16 is positioned with respect to the positioning shaft 110a. Further, since the lower jig 110 is positioned with respect to the inner cylindrical member 64, one end portion of the fuel cell 16 is accurately positioned with respect to the inner cylindrical member 64 constituting the fuel cell module 2. Furthermore, since the lower end of each fuel cell 16 is in contact with the base end face 110b of each positioning shaft 110a, the lower ends of all the fuel cells 16 are positioned on the same plane. That is, the protruding length of each fuel cell 16 from the first fixing member 63 is constant. On the other hand, since the length of each fuel cell 16 varies due to manufacturing errors, the height of the upper end of each fuel cell 16 is not completely constant.
Therefore, in this step, one end portion of each fuel cell 16 inserted into each insertion hole 63 a is positioned with respect to the inner cylindrical member 64 constituting the fuel cell module 2.

  Next, as shown in FIG. 9, an aggregation chamber lower member 18b that is a second fixing member and constitutes a part of the exhaust aggregation chamber 18 is disposed at the upper end of the fuel cell 16 (step S3 in FIG. 24). ). Three stays 64c, which are positioning members, are welded to the inner wall surface of the inner cylindrical member 64. Each stay 64c includes an inclined portion extending in an inclined manner and a parallel portion extending in parallel with the first fixing member 63, and is disposed on the inner wall surface of the inner cylindrical member 64 at equal intervals. When the aggregation chamber lower member 18b is arranged on each stay 64c, the aggregation chamber lower member 18b is dropped to the parallel portion of each stay 64c, and is against the inner cylindrical member 64 constituting the inner wall surface of the power generation chamber 10. Accurate positioning. In this state, a uniform gap is formed between the inner peripheral surface of the inner cylindrical member 64 and the outer peripheral surface of the aggregation chamber lower member 18b. Further, in this step, the upper end portion of each fuel cell 16 is inserted into each insertion hole 18c of the aggregation chamber lower member 18b, which is the second fixing member, and protrudes upward.

Further, as shown in FIG. 10, the upper jig 112 as the second positioning device is arranged on the upper part of the inner cylindrical member 64 (step S <b> 4 in FIG. 24). The upper jig 112 includes a plurality of truncated cones 112 a extending downward in parallel with the inner cylindrical member 64. The tip of each truncated cone 112 a is inserted into each fuel cell 16 extending from below, and the side surface of each truncated cone 112 a abuts on the upper end of each fuel cell 16. Since the upper jig 112 is accurately positioned with respect to the inner cylindrical member 64, the upper end portion of each fuel cell 16 is also accurately positioned with respect to the inner cylindrical member 64.
Therefore, in this step, the other end portion of each fuel cell 16 inserted into each insertion hole 18c of the aggregation chamber lower member 18b is connected to the inner cylindrical member 64 constituting the fuel cell module 2 by the upper jig 112. Positioned.

  In this way, the upper end portion and the lower end portion of each fuel cell 16 are accurately positioned with respect to the inner cylindrical member 64. In this state, a substantially constant gap is formed between the outer peripheral surface of each fuel cell 16 and each insertion hole 18c of the aggregation chamber lower member 18b through which they are inserted and the insertion hole 63a of the first fixing member 63. Is formed. That is, each fuel battery cell 16 is in a state of being separated from the edge of each insertion hole 18c of the aggregation chamber lower member 18b and the insertion hole 63a of the first fixing member 63 by a predetermined distance, and the fuel cell module 2 (inner cylindrical member 64). Is positioned at a predetermined position. Each fuel cell 16 has a slight curvature due to manufacturing errors, but each fuel cell 16 is accurately positioned with respect to the fuel cell module 2 (inner cylindrical member 64) at the upper end and the lower end. Therefore, the gap between the outer peripheral surface of each fuel cell 16 and each insertion hole can be made substantially constant.

  In this manner, with each fuel cell 16 positioned, an adhesive attaching step of injecting a ceramic adhesive onto the aggregation chamber lower member 18b is performed by the adhesive injection device 114, which is an adhesive attaching device. . The aggregation chamber lower member 18b is provided with an adhesive filling frame 18e extending in an annular shape so as to surround all the insertion holes 18c (FIG. 4). The adhesive injection device 114 pours a ceramic adhesive inside the adhesive filling frame 18e surrounding each insertion hole 18c, and attaches the ceramic adhesive to the joint. A region surrounded by the adhesive filling frame 18e on the aggregation chamber lower member 18b functions as an adhesive receiving portion. The ceramic adhesive is a viscous liquid, and when poured, the ceramic adhesive flows on the lower member 18b of the collecting chamber, and a ceramic adhesive layer 118 having a uniform thickness is formed inside the adhesive filling frame 18e. The viscosity is adjusted. The poured ceramic adhesive also flows into the gap between the outer peripheral surface of each fuel cell 16 and each insertion hole 18c to fill the gap, but has a viscosity that does not flow down from this gap. .

  As shown in FIG. 11, after a predetermined amount of ceramic adhesive is poured and the ceramic adhesive layer 118 spreads uniformly inside the adhesive filling frame 18e on the aggregation chamber lower member 18b, the upper jig 112 is temporarily Removed. In this state, the cover member 19c is disposed on the poured ceramic adhesive layer 118 (step S5 in FIG. 24).

  As shown in FIG. 12, after the cover member 19c is disposed, the upper jig 112 is attached again, and in this state, the upper jig 112 is placed in a drying furnace 116 as a heating device, the ceramic adhesive layer 118 is cured, and each fuel cell is cured. The outer peripheral surface of the cell 16 is fixed to the aggregation chamber lower member 18b (step S6 in FIG. 24). Therefore, the drying furnace 116 functions as an adhesive curing device. In this way, the cell joint portion between the fuel cell 16 which is a component part of the flow path for guiding the fuel and the aggregation chamber lower member 18b is airtightly joined by the ceramic adhesive layer 118.

Next, a drying and curing process for drying and curing the ceramic adhesive will be described. The dry curing process includes a workable curing process for curing the ceramic adhesive until the next manufacturing process can be performed, and a ceramic adhesive until it can withstand the temperature rise in the starting process of the solid oxide fuel cell device 1. And a solvent removal curing step for curing. Hereinafter, the workable curing process will be described.
In this embodiment, a ceramic adhesive containing aluminum oxide, quartz, alkali metal silicate, silicon dioxide, and water is used for adhesion, and the ceramic adhesive is cured by a dehydration condensation reaction. That is, the ceramic adhesive is cured by evaporating the water contained therein and the water generated by the condensation reaction. Accordingly, since it takes a very long time to dry and cure the ceramic adhesive at room temperature, it is generally industrially cured using a drying furnace or the like. However, since the moisture of the ceramic adhesive evaporates at the time of curing and the volume shrinks, a crack is generated in the layer of the ceramic adhesive in a normal drying / curing process.

  FIG. 27 is a photograph showing an example when the fuel battery cell is bonded by a normal bonding method using a ceramic adhesive. As shown in FIG. 27, a number of cracks have occurred in the cured ceramic adhesive layer. This is because when the ceramic adhesive is cured, the moisture on the surface of the adhesive layer evaporates first and hardens, and when the internal moisture evaporates later, the surface of the adhesive layer that has been cured earlier cracks. It is thought to occur. Even in such a state, the fuel cell is bonded with sufficient strength, but a gap is partially generated between the fuel cell and the ceramic adhesive layer, and sufficient airtightness can be secured. Can not. That is, when a ceramic adhesive is used in the conventional method, it is difficult to ensure airtightness at the same time as adhesion, and this is the reason why there are a number of documents that proposed the use of ceramic adhesives in the technical field of solid oxide fuel cells. Although it exists, it is thought that this is a cause that has not yet been put into practical use.

FIG. 22 is a plan view of the cover member 19c disposed on the poured ceramic adhesive in the present embodiment.
The cover member 19c is a circular metal plate, and a large circular opening is formed in the center for inserting the cylindrical portion of the aggregation chamber lower member 18b, and a plurality of insertion holes for inserting each fuel cell 16 are formed around the cover member 19c. ing. In the present embodiment, the position and size of each insertion hole are configured to be the same as the insertion hole 18c of the aggregation chamber lower member 18b.

FIG. 23 is a perspective view showing a state in which the cover member 19c is arranged on the poured ceramic adhesive.
As shown in FIG. 23, when the cover member 19c is disposed on the poured ceramic adhesive, the ceramic adhesive under the cover member 19c is pushed out by the weight of the cover member 19c. The extruded ceramic adhesive is filled in a gap between the insertion hole of the cover member 19 c and the outer peripheral surface of the fuel cell 16, and rises around each fuel cell 16. As a modification, a peripheral wall can be formed at the edge of each insertion hole of the cover member 19c so as to surround the insertion hole. Thereby, even when many ceramic adhesives are extruded around each fuel battery cell 16, it can suppress that an adhesive flows on cover member 19c.

  Each fuel cell 16 is bonded to the lead film layers 104a and 104b with a ceramic adhesive (FIG. 6). Since the lead film layers 104a and 104b are the same dense layers as the solid electrolyte layer 100, the ceramic adhesive permeates into the porous layer such as the porous support 97 and the air permeability is not impaired.

FIG. 25 is an enlarged cross-sectional view showing an adhesion portion of the fuel battery cell 16 to the aggregation chamber lower member 18b.
As shown in FIG. 25, the fuel cell 16 is inserted into the insertion hole 18c of the aggregation chamber lower member 18b, and a ceramic adhesive is poured onto the aggregation chamber lower member 18b. A cover member 19c is disposed on the poured ceramic adhesive. The cover member 19c is also provided with an insertion hole at the same position as the aggregation chamber lower member 18b, and the fuel cell 16 extends upward through the insertion hole. Since there is a predetermined gap between the insertion hole of the cover member 19c and the outer peripheral surface of the fuel cell 16, the cover member 19c is a ceramic adhesive so that the vicinity of the surface of the fuel cell 16 to be joined is exposed. Placed on the top. As a result, the ceramic adhesive layer 118 is formed between the aggregation chamber lower member 18b and the cover member 19c. Further, a part of the ceramic adhesive is pushed out from under the cover member 19 c to the vicinity of the surface of the fuel cell 16, and this portion of the ceramic adhesive increases to form a raised portion 118 a around the fuel cell 16. . The extruded ceramic adhesive also forms a hanging portion 118b between the lower insertion hole 18c and the fuel cell 16, but the ceramic adhesive does not flow down due to viscosity. The assembly in which the cover member 19c is arranged is put in the drying furnace 116 in this state (FIG. 12).

FIG. 26 is a graph showing an example of temperature control in the drying furnace 116.
In the workable curing process shown in FIG. 12, the temperature in the drying furnace 116 is controlled by the heating controller 116a as shown by the solid line in FIG. First, after putting an assembly in the drying furnace 116, the temperature in the drying furnace 116 is raised from room temperature to about 60 ° C. in about 120 minutes. The temperature in the drying oven 116 is then raised to about 80 ° C. in about 20 minutes and then maintained at about 80 ° C. for about 60 minutes. After maintaining the temperature of about 80 ° C., the temperature in the drying furnace 116 is returned to room temperature in about 30 minutes.

  In this way, by gradually raising the temperature, the moisture in the ceramic adhesive layer 118 is evaporated little by little. However, since the ceramic adhesive layer 118 is covered with the cover member 19c, moisture does not evaporate directly from the portion covered with the cover member 19c. For this reason, the moisture in the ceramic adhesive layer 118 is gradually evaporated through the raised portion 118 a or the hanging portion 118 b around the fuel cell 16. As a result, moisture collects in the raised portions 118a and the hanging portions 118b exposed to the outside air, and these portions are not easily dried. Further, since the cover member 19c and the aggregation chamber lower member 18b are made of a metal having high thermal conductivity, even if the cover member 19c and the aggregation chamber lower member 18b are locally heated due to temperature unevenness in the drying furnace 116, the ceramic adhesive layer 118 is formed. The heating is made uniform. For this reason, generation | occurrence | production of the crack by the ceramic adhesive bond layer 118 drying rapidly locally can be suppressed. On the other hand, since each fuel cell 16 is made of a ceramic having low thermal conductivity, heat is not easily transmitted to the raised portion 118a and the drooping portion 118b around the fuel cell 16, and drying and hardening of these portions are not possible. Be gentler than the part.

  As described above, in the present embodiment, the raised portions 118a and the drooping portions 118b around each fuel battery cell 16 are gently dried. Therefore, the peripheral part of each fuel battery cell 16 that is important for ensuring airtightness is used. The occurrence of cracks in is prevented. Further, when water is evaporated from the ceramic adhesive, the volume of the ceramic adhesive layer 118 contracts, and so-called “sink” is generated. However, since the raised portion 118a and the drooping portion 118b are formed in the peripheral portion of each fuel cell 16 and the ceramic adhesive layer is thicker than the other portions, the fuel cell 16 and the ceramic are caused by the occurrence of sink marks. Generation | occurrence | production of the clearance gap between adhesive bond layers can be prevented. Thus, the airtightness of the adhesion part between each fuel cell 16 and each insertion hole 18c is ensured. The cover member 19c arranged to cover the filled portion of the ceramic adhesive suppresses the generation of cracks when the ceramic adhesive is cured.

  In addition, since the raised portion 118a and the hanging portion 118b are formed, even if a slight crack occurs in this portion, the crack rarely penetrates the ceramic adhesive layer, so that airtightness can be reliably ensured. it can. Therefore, the raised portion 118a and the hanging portion 118b function as a gas leakage suppressing portion that suppresses the generation of cracks due to shrinkage when the ceramic adhesive is cured. The cured ceramic adhesive layer is porous and does not have complete hermeticity against hydrogen or air, but the ceramic adhesive layer that has been filled and cured without any gaps has practically sufficient hermeticity. I have. In the present specification, “securing airtightness” means that there is no leakage to hydrogen or air to a practically sufficient level.

  Through the workable curing process shown in FIG. 12, the ceramic adhesive is cured to a state where the subsequent manufacturing process after step S <b> 7 in FIG. 24 can be performed. In this state, the adhesive strength by the ceramic adhesive is sufficiently high, and the use of a general ceramic adhesive can be regarded as the completion of the bonding process. However, when the ceramic adhesive is used for assembling the solid oxide fuel cell device 1, the state is insufficient. When the solid oxide fuel cell device 1 is operated in this state, the inside of the ceramic adhesive layer Moisture remaining in the film evaporates abruptly and a large crack is generated in the adhesive layer. In the present embodiment, the manufacturing process shown in FIG.

  Next, after the workable curing process is performed, the lower jig 110 and the upper jig 112 are removed. Further, as shown in FIG. 13, the ceramic adhesive is applied on the first fixing member 63 (the lower side surface when not turned upside down) where the assembly is turned upside down and the tip of each fuel cell 16 protrudes. Is injected (step S7 in FIG. 24). Thereby, the outer peripheral surface of each fuel battery cell 16 having a circular cross section is fixed to the edge of each circular insertion hole 63 a provided in the first fixing member 63 by the ceramic adhesive. Here, the first fixing member 63 is provided with an adhesive filling frame 63b extending in an annular shape so as to surround all the insertion holes 63a (FIG. 3). As an adhesive attaching step, a ceramic adhesive is poured into the inside of the adhesive filling frame 63b surrounding each insertion hole 63a by the adhesive injection device 114. The adhesion of each fuel cell 16 to the first fixing member 63 in this step is the same as the adhesion to the aggregation chamber lower member 18b described above. Further, in this step, since each fuel cell 16 is fixed to the aggregation chamber lower member 18b, each fuel cell 16 is held at an appropriate position without using the upper jig 112.

  Further, as shown in FIG. 14, the cover member 67 is disposed on the poured ceramic adhesive, and the ceramic adhesive layer 122 is formed between the first fixing member 63 and the cover member 67 (FIG. 24). Step S8). The cover member 67 is configured in the same manner as the cover member 19c (FIG. 22) except that the central circular opening is not provided, and suppresses the generation of cracks when the ceramic adhesive is cured. By disposing the cover member 67, the raised portions and hanging portions similar to those in FIG. 25 are formed around each fuel cell 16, and the surrounding portion of each fuel cell 16 of the ceramic adhesive layer 122 is Functions as a gas leakage suppression unit.

  In this state, the assembly is placed in the drying furnace 116, and a second workable curing process is performed. Also in this workable curing process, the temperature in the drying furnace 116 is controlled as shown by the solid line in FIG. In the present embodiment, in the second workable curing step, the time for maintaining the temperature in the drying furnace 116 at about 80 ° C. is set to about 50 minutes. In the second workable curing step, the ceramic adhesive layer 122 on the first fixing member 63 is cured, and each fuel cell 16 is fixed to the first fixing member 63. Thus, the fuel cell 16 which is a component part of the flow path for guiding the fuel and the cell joint portion of the first fixing member 63 are hermetically joined by the ceramic adhesive. The action of the cover member 67 at this time is the same as that in the first workable curing step. In addition, the ceramic adhesive layer 118 on the aggregation chamber lower member 18b is subjected to two workable curing steps, so that the ceramic adhesive layer 118 becomes more stable.

  Next, as shown in FIG. 15, a current collector 82 is attached to the tip end portion (lower end portion when not vertically inverted) of each fuel cell 16 projecting from the first fixing member 63. The body 82 is connected to the bus bar 80 (step S9 in FIG. 24).

  Further, as shown in FIG. 16, the dispersion chamber bottom member 72 is inserted from the opening below the inner cylindrical member 64 (upper in FIG. 16). The dispersion chamber bottom member 72 is inserted and positioned at a position where the outer peripheral flange portion 72c and the annular shelf member 64d welded to the inner wall surface of the inner cylindrical member 64 abut (FIG. 24). Step S10).

  Next, as shown in FIG. 17, the ceramic adhesive is filled in the annular gap between the outer peripheral surface of the dispersion chamber bottom member 72 and the inner peripheral surface of the inner cylindrical member 64 by the adhesive injection device 114. In addition, an insulator 78 is disposed in an insertion tube 72 a that is a conductor passage provided in the center of the dispersion chamber bottom member 72, and each bus bar 80 extending from the current collector 82 passes through the insulator 78. . Further, as the adhesive attaching step, the ceramic adhesive is filled into the insertion tube 72a in which the insulator 78 is disposed by the adhesive injection device 114. Each bus bar 80 extends to the outside through the insertion tube 72a, and a space around each bus bar 80 in the insertion tube 72a is filled with a ceramic adhesive (step S11 in FIG. 24).

  Further, as shown in FIG. 18, the dispersion chamber which is an annular thin plate on the ceramic adhesive layer 124 filled in the gap between the outer peripheral surface of the dispersion chamber bottom member 72 and the inner peripheral surface of the inner cylindrical member 64. A seal ring 126 is disposed. Further, the central seal plate 130 is disposed on the ceramic adhesive layer 128 filled in the insertion tube 72a (step S12 in FIG. 24). Each bus bar 80 passes through a hole provided in the central seal plate 130. The dispersion chamber seal ring 126 and the central seal plate 130 function as a cover member that suppresses the generation of cracks when the ceramic adhesive is cured. In this state, the assembly is placed in a drying furnace 116 (not shown in FIG. 18), and a third workable curing process is performed (step S13 in FIG. 24). Also in this workable curing process, the temperature in the drying furnace 116 is controlled as shown by the solid line in FIG. In the present embodiment, in the third workable curing step, the time for maintaining the temperature in the drying furnace 116 at about 80 ° C. is set to about 45 minutes. In the third workable curing step, the ceramic adhesive layer 124 is cured, and the dispersion chamber bottom member 72 and the inner cylindrical member 64 are hermetically bonded and fixed. In this way, the joint between the dispersion chamber bottom member 72 and the inner cylindrical member 64, which are components of the flow path for guiding the fuel, is hermetically joined by the ceramic adhesive. The ceramic adhesive layer 128 is also cured, and the insertion tube 72a through which each bus bar 80 passes is hermetically closed.

  When these ceramic adhesives are cured, the dispersion chamber seal ring 126 and the central seal plate 130 prevent the surface of each adhesive layer from drying out rapidly, and cracks in the ceramic adhesive layers 124 and 128 are prevented. Suppresses the occurrence. Further, since the ceramic adhesive layer 124 filled in the gap between the inner cylindrical member 64 and the dispersion chamber bottom member 72 has an annular shape, the ceramic adhesive layer 124 is cured while being heated evenly and the generation of cracks is suppressed. For example, when the ceramic adhesive layer is formed in a rectangular shape, the speed at which the adhesive hardens is different between the corner and other parts, so the part that has been dried and hardened first is pulled by contraction of the ceramic adhesive. Cracks are likely to occur. Further, the corner portion tends to concentrate stress generated by the shrinkage of the ceramic adhesive, and easily cracks when cured. On the other hand, in this embodiment, since the ceramic adhesive layer 124 has an annular shape, drying and curing proceed uniformly, and stress generated by the shrinkage of the adhesive is not concentrated. Generation of cracks accompanying curing can be suppressed. As a modification, the ceramic adhesive layer 124 may be configured in an elliptical ring shape.

  After completion of the third workable curing step, the assembly is turned upside down, and as shown in FIG. 19, the current collector is attached to the tip of each fuel cell 16 fixed so as to protrude from the aggregation chamber lower member 18b. 82 is attached (step S14 in FIG. 24). By this current collector 82, the tip end portion of each fuel cell 16 is electrically connected. Further, the aggregation chamber upper member 18a is disposed in the opening above the aggregation chamber lower member 18b. There is a cylindrical (annular) gap (FIG. 4) between the outer peripheral surface of the arranged aggregation chamber upper member 18a and the inner peripheral surface of the outer peripheral wall of the aggregation chamber lower member 18b. Next, an adhesive attaching step for filling the ceramic adhesive layer 120a is performed in the gap by an adhesive injection device 114 (not shown in FIG. 19). An annular large-diameter seal ring 19a is disposed on the ceramic adhesive layer 120a so as to cover the filled adhesive. There is also an annular gap between the outer peripheral surface of the cylindrical portion of the aggregation chamber lower member 18b and the central opening of the aggregation chamber upper member 18a, and an adhesive injection device 114 (not shown in FIG. 19). Thus, this gap is also filled with the ceramic adhesive layer 120b. An annular small-diameter seal ring 19b is disposed on the ceramic adhesive layer 120b so as to cover the filled adhesive. The large-diameter seal ring 19a and the small-diameter seal ring 19b function as cover members that suppress the generation of cracks when the ceramic adhesive is cured.

  As a modification, by forming these members so that the gap between the aggregation chamber upper member 18a and the aggregation chamber lower member 18b is elliptical, and filling this gap with a ceramic adhesive, The present invention can also be configured such that the exhaust collection chamber 18 is configured. As a modification, these members are formed so that the gap between the cylindrical portion of the aggregation chamber lower member 18b and the opening of the aggregation chamber upper member 18a is an elliptical ring, and a ceramic adhesive is applied to the gap. The present invention can also be configured such that the exhaust collecting chamber 18 is configured by filling.

  In this state, the assembly is again put in the drying furnace 116 (not shown in FIG. 19), and a fourth workable curing process is performed (step S15 in FIG. 24). Also in this workable curing process, the temperature in the drying furnace 116 is controlled as shown by the solid line in FIG. In the present embodiment, in the fourth workable curing step, the time for maintaining the temperature in the drying furnace 116 at about 80 ° C. is set to about 45 minutes. By the fourth workable curing step, the ceramic adhesive layer 120a around the exhaust aggregation chamber 18 and the ceramic adhesive layer 120b at the center of the exhaust aggregation chamber 18 are cured. At this time, the large-diameter seal ring 19a disposed on the ceramic adhesive layer 120a and the small-diameter seal ring 19b disposed on the ceramic adhesive layer 120b are formed in each workable curing process. Prevents surface moisture from evaporating rapidly. Thereby, generation | occurrence | production of the crack in ceramic adhesive bond layers 120a and 120b can be suppressed, and the airtightness of a junction part can be ensured. In this way, the joint portion between the aggregation chamber upper member 18a and the aggregation chamber lower member 18b, which are components of the flow path for guiding the fuel, is airtightly joined by the ceramic adhesive. In addition, since each ceramic adhesive layer hardened | cured by the workable hardening process of 3 times is heated gently again in the workable hardening process of the 4th time, it remains, avoiding the danger of a crack generation | occurrence | production. Moisture is evaporated and the state becomes more stable.

  Next, as shown in FIG. 20, an inner cylindrical container 68 as an exhaust passage constituting member and an outer cylindrical container 70 as a supply passage constituting member are placed over the assembly assembled up to FIG. 19 (FIG. 24). Step S16). The inner cylindrical container 68 and the outer cylindrical container 70 are attached to the assembly while being joined together by welding. An exhaust gas discharge pipe 58 is attached to the lower part of the outer wall surface of the inner cylindrical container 68, and an oxidant gas injection pipe 74 is attached to the inner ceiling surface. An oxidant gas introduction pipe 56 is attached to the lower part of the outer wall surface of the outer cylindrical container 70. An ignition heater 62 is attached so as to penetrate the inner cylindrical container 68 and the outer cylindrical container 70. By covering the inner cylindrical container 68 on the assembly, the exhaust gas discharge passage 21 (FIG. 2) is formed between the outer peripheral surface of the outer cylindrical member 66 and the inner peripheral surface of the inner cylindrical container 68. The oxidant gas injection pipe 74 attached to the inner cylindrical container 68 passes through the central opening of the exhaust gas collecting chamber 18 of the assembly.

  As a modification, the present invention can be configured such that the inner cylindrical container 68 and the outer cylindrical container 70 are bonded by a ceramic adhesive. In this case, the annular gap between the inner cylindrical container 68 and the outer cylindrical container 70 is filled with a ceramic adhesive, and these members are fixed in an airtight manner. Alternatively, these members are configured so that the gap between the inner cylindrical container and the outer cylindrical container becomes an elliptical annular shape, and the elliptical annular gap is filled with a ceramic adhesive to fix these members in an airtight manner. Thus, the present invention can also be configured.

  As shown in FIG. 21, the assembly covered with the inner cylindrical container 68 and the outer cylindrical container 70 is turned upside down again. Here, an annular shelf member 66 a is welded to the lower part of the outer wall surface of the outer cylindrical member 66 (upper part in FIG. 21). The shelf member 66 a is connected to the outer peripheral surface of the outer cylindrical member 66 and the inner cylindrical container 68. The annular gap between the inner peripheral surfaces is closed. A ceramic adhesive is filled into the annular space surrounded by the outer peripheral surface of the outer cylindrical member 66, the inner peripheral surface of the inner cylindrical container 68, and the shelf member 66a by the adhesive injection device 114 as an adhesive application step. (Step S17 in FIG. 24). As a modification, the outer cylindrical member and the inner cylindrical container can be configured so that the gap between the outer cylindrical member filled with the ceramic adhesive and the inner cylindrical container is an elliptical ring.

  An exhaust passage seal ring 134 which is an annular thin plate is disposed so as to cover the filled ceramic adhesive layer 132. The exhaust passage seal ring 134 functions as a cover member that suppresses the generation of cracks when the ceramic adhesive is cured. In this state, the assembly is placed in a drying furnace 116 (not shown in FIG. 21), and a fifth workable curing process is performed (step S18 in FIG. 24).

  In this workable curing process, as shown in FIG. 26, the temperature in the drying furnace 116 is first raised from room temperature to about 60 ° C. in about 120 minutes by the heating controller 116a, and then in about 20 minutes. The temperature is raised to about 80 ° C. and then maintained at about 80 ° C. for about 60 minutes. After the temperature of about 80 ° C. is maintained, the temperature in the drying furnace 116 is raised to about 150 ° C. in about 70 minutes as shown by the broken line in FIG. Furthermore, after the temperature of about 150 ° C. is maintained for about 60 minutes, the temperature is returned to room temperature in about 60 minutes.

  That is, by performing the fifth workable curing step, the newly filled ceramic adhesive layer 132 is heated and cured, and the outer cylindrical member 66 and the inner cylindrical container 68 are hermetically bonded. In this way, the joint between the outer cylindrical member 66 and the inner cylindrical container 68 that are components of the flow path for guiding the oxidant gas is hermetically joined by the ceramic adhesive. The action of the exhaust passage seal ring 134 and the effect of the annular ceramic adhesive layer 132 at this time are the same as those of the dispersion chamber seal ring 126 and the ceramic adhesive layer 124 described above. In addition, the ceramic adhesive layer cured in the first to fourth workable curing processes is subjected to multiple workable curing processes, so that gentle drying is repeated repeatedly to avoid the risk of cracking. However, the ceramic adhesive layer is in a stable state.

  In particular, the workable curing process for the cell junction between each fuel cell 16 and the aggregation chamber lower member 18b is performed first in the workable curing process performed five times. In addition, after the last workable curing step for the cell joint portion, that is, the workable hardening step for the joint portion between each fuel cell 16 and the first fixing member 63 (second workable hardening step). The workable curing process for the joints of the components other than the fuel battery cell 16 is performed three times. For this reason, the workable curing step is performed four or more times for each cell joint, and the ceramic adhesive layer of each cell joint is in a very stable state. These cell joints cause a serious problem when the airtightness is impaired, but the airtightness can be surely ensured by repeatedly performing the workable curing step.

  In addition, the workable curing process for the joint between the outer cylindrical member 66 and the inner cylindrical container 68, which is performed after the workable curing process for the cell joint part, improves the airtightness of the exhaust gas discharge passage 21 that leads the exhaust. Even if the airtightness is impaired, the adverse effect is less than when the airtightness of the cell junction is impaired. Furthermore, when the inner cylindrical container 68 and the outer cylindrical container 70 are joined with a ceramic adhesive as in the above-described modification, the workable curing process for the joint is performed after the workable curing process for the cell joint. Is done. The joint part between the inner cylindrical container 68 and the outer cylindrical container 70 is for ensuring the airtightness of the oxidant gas supply flow path 22, and even if the airtightness is impaired, the airtightness of the cell joint part The adverse effect is less than when damage is lost.

  After the fifth workable curing process, which is the last workable curing process, is performed, the solvent removal curing process is subsequently performed (step S19 in FIG. 24). Thus, after an adhesive agent adhesion process and a workable curing process are repeated a plurality of times, a solvent removal curing process is performed. In the solvent removal and curing step, the dehydration condensation reaction is performed by the workable curing step, and the remaining moisture is further evaporated from the fully cured ceramic adhesive layer, so that the solid oxide fuel cell device 1 is started. It is dried until it can withstand the temperature rise. In the present embodiment, the solvent removal curing step is performed by setting the temperature in the drying furnace 116 to about 150 ° C. and maintaining this for about 180 minutes. By carrying out the solvent removal curing process at a temperature higher than the workable curing process, the ceramic adhesive layer can be dried in a short time to a state that can withstand the temperature rise in the startup process.

  As described above, the solvent removal curing step is preferably performed at a temperature higher than the temperature of the workable curing step and lower than the temperature during the power generation operation of the solid oxide fuel cell device 1. The ceramic adhesive used in the present embodiment can be dried at a temperature of 200 ° C. or lower until it can withstand the temperature increase in the startup process. Preferably, the solvent removal curing step is performed at 100 ° C. or higher and 200 ° C. Run at the following temperature. Alternatively, as a modification, the solvent removal curing process is performed at a temperature similar to the workable curing process for a longer time than the workable curing process, so that the ceramic adhesive layer can withstand the temperature rise in the startup process. It can also be dried.

  Since the ceramic adhesive filled in the adhesive attaching step has undergone at least one workable curing step, the ceramic adhesive layer can be obtained even if the temperature of the drying furnace 116 is increased to about 150 ° C. in the solvent removal curing step. No large cracks occur. In addition, although moisture remains in each ceramic adhesive layer even after the solvent removal and curing process is completed, even if the inside of the fuel cell module 2 is raised to the temperature at the time of power generation, the occurrence of cracks, etc. Trouble does not occur. Further, in the present embodiment, the solvent removal curing process is performed only once after the adhesive adhesion process and the workable curing process are repeated a plurality of times, and finally the workable curing process is executed. In the production process, the solvent removal and curing process can be carried out a plurality of times.

As a modification, a solvent removal curing process may be added between the workable curing process in step S15 of FIG. 24 and step S16. In this modification, the added solvent removal / curing step is performed in two steps: a first solvent removal / curing step and a second solvent removal / curing step.
FIG. 28 to FIG. 30 are diagrams for explaining the solvent removal curing process according to this modification. FIG. 28 is a diagram illustrating a first solvent removal curing step in the present modification, and FIG. 29 is a diagram illustrating a second solvent removal curing step. Moreover, FIG. 30 is a figure explaining the heating method in a 2nd solvent removal hardening process.

  First, when the manufacturing method according to the present modification is performed, the first half of FIG. 28 is heated as the fourth workable curing step in step S15 of FIG. That is, the assembly assembled up to step S14 is put into the drying furnace 116, and the temperature in the drying furnace 116 is maintained at about 80 ° C. for about 60 minutes. Next, as shown in FIG. 28, as the first solvent removal curing step, the temperature in the drying furnace 116 is raised to about 150 ° C. in about 70 minutes, and after maintaining this temperature for about 30 minutes, the temperature is lowered. In this first solvent removal and curing step, the temperature is raised to about 150 ° C., but since each ceramic adhesive layer has undergone at least one workable curing step, this heating causes large cracks in the ceramic adhesive layer. It does not occur.

  Next, the second solvent removal curing step shown in FIG. 29 is performed. In the second solvent removal and curing step, the temperature of the power generation chamber 10 and the fuel cell 16 is increased to the temperature at the time of power generation operation or a temperature in the vicinity thereof. Further, in the second solvent removal and curing step, the entire assembly is not heated in the drying furnace 116, but is heated by feeding heated air into the power generation chamber 10 as shown in FIG. The inner and fuel cell 16 are heated. That is, in the second solvent removal and curing step, the heated air introduction pipe 136 is inserted into the power generation chamber 10 through the opening at the center of the exhaust concentration chamber 18. In the second solvent removal and curing step, heated air is introduced into the power generation chamber 10 via the heated air introduction pipe 136. The introduced air is heated between the outer periphery of the exhaust collecting chamber 18 and the inner wall surface of the inner cylindrical member 64 after each fuel cell 16 in the power generation chamber 10 is heated, as indicated by solid arrows in FIG. It flows out of the assembly through the gap. Thereby, the junction part of the fuel cell 16 and the first fixing member 63, the junction part of the aggregation chamber lower member 18b and the fuel cell 16, the junction part of the aggregation chamber upper member 18a and the aggregation chamber lower member 18b, and the bottom of the dispersion chamber Each ceramic adhesive layer at the joint between the material 72 and the inner cylindrical member 64 is heated, and the solvent remaining inside the cured ceramic adhesive is further evaporated.

  In addition, the temperature of the air introduced into the power generation chamber 10 via the heated air introduction pipe 136 is gradually increased over a long time to the temperature during the power generation operation of the solid oxide fuel cell device 1. In this modification, as shown by a solid line in FIG. 29, the temperature of the heating air introduced from the heated air introduction pipe 136 is raised to about 650 ° C. over about 3 hours from the start of introduction. This temperature rise is made more gradual than the temperature rise in the power generation chamber 10 in the starting process of the solid oxide fuel cell device 1 shown by a one-dot chain line in FIG. In the example shown in FIG. 29, in the starting process of the solid oxide fuel cell device 1, the temperature in the power generation chamber 10 is increased to about 650 ° C. in about 2 hours, whereas the second solvent removal curing process , The temperature of the supplied air is raised to about 650 ° C. over about 3 hours.

  By gradually raising the temperature in this way, the solvent remaining in the ceramic adhesive layer is gradually heated and evaporated. Thereby, generation | occurrence | production of the excessive crack by rapid volume expansion and evaporation of a solvent is suppressed. Moreover, the temperature of the ceramic adhesive layer of each part in the power generation chamber 10 is raised to the temperature during the actual power generation operation by the second solvent removal and curing step. Thereby, even when the temperature is rapidly increased in the actual start-up process of the completed solid oxide fuel cell device 1, it is more reliably guaranteed that excessive cracks do not occur in the ceramic adhesive layer. be able to.

  In addition, the second solvent removal curing process for raising the temperature in the power generation chamber 10 to about 650 ° C. is not performed at the end of the assembly process (after step S18 in FIG. 24), but is performed after step S15. As a result, the assembly process can be simplified. That is, devices such as a combustion catalyst 60, an ignition heater 62, a sheath heater 61, and a sensor are attached in advance to the inner cylindrical container 68 and the outer cylindrical container 70 assembled in step S16. And the outer cylindrical container 70 can be attached to the assembly at the same time. However, these devices cannot withstand a temperature of about 650 ° C. (In the actual power generation operation of the solid oxide fuel cell device 1, the temperature at which these devices are attached rises up to about 650 ° C. do not do). Therefore, if the second solvent removal curing process is performed after the inner cylindrical container 68 and the outer cylindrical container 70 have been attached (after step S18 in FIG. 24), the devices such as the ignition heater 62 will be installed later. It is necessary to install them separately, which complicates the manufacturing process.

  On the other hand, in the second solvent removal curing step, the inert gas is supplied from the fuel gas supply pipe 90 in parallel with the introduction of the heating air from the heated air introduction pipe 136. As indicated by the wavy arrow in FIG. 29, the inert gas supplied from the fuel gas supply pipe 90 rises to the upper end in the fuel gas supply flow path 20 and then descends in the reforming portion 94 to become the inner cylinder. It flows into the fuel gas dispersion chamber 76 through a small hole 64 b provided in the lower part of the member 64. The inert gas that has flowed into the fuel gas dispersion chamber 76 flows into the exhaust collecting chamber 18 through the inside (fuel electrode side) of each fuel cell 16 attached to the first fixing member 63 of the fuel gas dispersion chamber 76. . The inert gas that has flowed into the exhaust aggregation chamber 18 is ejected from the ejection port 18d of the exhaust aggregation chamber 18 and flows out of the assembly.

  In this modification, nitrogen gas is used as the inert gas. Further, the introduced nitrogen gas is heated so that each fuel cell 16 can also be heated from the inside. As described above, the inert gas is introduced into each fuel cell 16, and the oxidant gas (air) in each fuel cell 16 and the reforming unit 94 is discharged. Thereby, the oxidation of the fuel electrode of each fuel cell 16 and the oxidation of the reforming catalyst of the reforming unit 94 when the temperature is raised to the temperature during the power generation operation can be prevented. In the second solvent removal curing step, hydrogen gas can be supplied from the fuel gas supply pipe 90 instead of the inert gas. In this case, hydrogen gas passes through the fuel electrode side of each fuel cell 16 that has been heated to high temperature, so that the fuel electrode can be reduced. In the second solvent removal curing step, an inert gas may be supplied until the temperature of each fuel battery cell 16 is sufficiently increased, and after the temperature has increased, the inert gas may be switched to hydrogen gas. it can.

  In this modification, the temperature can also be increased to the temperature of the second solvent removal and curing step after the first solvent removal and curing step without reducing the temperature. Also in this case, it is necessary to supply the inert gas from the fuel gas supply pipe 90. Moreover, a 1st solvent removal hardening process can also be abbreviate | omitted among a 1st, 2nd solvent removal hardening process. In this case, in the second solvent removal curing step, it is preferable to further moderate the temperature rise of the supplied heated air and raise the temperature over 4 hours or more.

  Further, in the state where the oxidant gas is supplied to the air electrode side of each fuel battery cell 16 and the hydrogen gas is supplied to the fuel electrode side, and the temperature of each fuel battery cell 16 is sufficiently raised, the fuel battery cell A voltage is generated between the two bus bars 80 connected to 16. By measuring the voltage between the bus bars 80, it is possible to determine the quality of each fuel cell 16 and each joint portion of the assembly. The voltage is measured in a state where no current flows between the bus bars 80. When each fuel cell 16 itself has a problem, the voltage generated between the bus bars 80 decreases. In addition, even when a large fuel leak occurs at the joint between each fuel battery cell 16 and the first fixing member 63 or the joint between each fuel battery cell 16 and the aggregation chamber lower member 18b, the fuel Since sufficient fuel gas is not supplied to the pole, the voltage decreases. Thus, in the second solvent removal and curing step, the reduction of the fuel electrode of each fuel cell 16 and the inspection of the semi-finished product of the solid oxide fuel cell device 1 can be performed simultaneously.

  Moreover, the time of the workable curing process set in the present embodiment can be changed. For example, the time of the workable curing process performed initially can be made shorter than the time of the workable curing process performed later. A joint that is initially subjected to a workable curing process is subjected to a workable curing process more times than a joint that is subsequently applied, so cracks occur while reducing the time required for the workable curing process. Risk can be sufficiently reduced.

  After the fuel cell storage container 8 is completed by the above manufacturing process, various components are attached, and the solid oxide fuel cell device 1 is completed. Further, the lower jig 110 (first positioning device), the upper jig 112 (second positioning device), the adhesive injection device 114, and the drying furnace 116 used in the manufacturing method of the solid oxide fuel cell device 1 described above. The (adhesive curing device) and the heating control device 116a constitute an apparatus for manufacturing a solid oxide fuel cell device.

  According to the method for manufacturing the solid oxide fuel cell device 1 of the embodiment of the present invention, the adhesive attaching step (steps S4, S7, S11, S14 in FIGS. 10, 13, 17, 21, and 24, FIG. The ceramic adhesive adhered in S17) is cured in the workable curing process (Steps S6, S8, S13, S15, and S18 in FIGS. 12, 14, and 24). The ceramic adhesive after completion of each workable curing process is cured to a state where the next manufacturing process can be performed, but when the assembled solid oxide fuel cell device 1 is operated, there is a possibility that a crack may occur. There is a state of. As described above, the workable curing process is in a state in which the next manufacturing process can be performed. However, since the curing is performed to such an extent that cracks can be generated by the operation, the time required for the process can be shortened. Further, after the adhesive attaching process and the workable curing process are repeated a plurality of times, the plurality of joints cured by the plurality of workable curing processes are removed from the solvent removal curing process (step S19 in FIG. 24, FIG. 26). The broken lines) allow the components to be dried at the same time until they can withstand the temperature rise in the start-up process, so that the components can be joined in an airtight manner while reducing the time required for manufacturing.

  Further, according to the method for manufacturing the solid oxide fuel cell device 1 of the present embodiment, after the last workable curing step (step S18 in FIG. 24), the solvent removal curing step (step S19 in FIG. 24). ) Is performed only once, so that all the joints (ceramic adhesive layers 118, 120a, 120b, 122, 124, 128, 132) can withstand the temperature during power generation in one solvent removal curing process. The time required for production can be greatly shortened.

  Furthermore, according to the method for manufacturing the solid oxide fuel cell device 1 of the present embodiment, the solvent removal curing step (step S19 in FIG. 24) dries the ceramic adhesive at a higher temperature than the workable curing step. (FIG. 26) The ceramic adhesive can be dried in a short time until it can withstand the temperature rise in the startup process.

  Moreover, according to the manufacturing method of the solid oxide fuel cell device 1 of the present embodiment, the solvent removal curing process (step S19 in FIG. 24) is changed to the workable curing process (steps S6, S8, S13, S15 in FIG. 24). , S18) and lower than the temperature during power generation (FIG. 26), the time required for the solvent removal and curing process is shortened while sufficiently reducing the risk of crack generation in the solvent removal and curing process. be able to.

  Furthermore, according to the method for manufacturing the solid oxide fuel cell device 1 of the present embodiment, the ceramic adhesive is dried at 150 ° C. (FIG. 26) in the solvent removal and curing step (step S19 in FIG. 24), so that the solvent is removed. Also in the curing step, the reforming catalyst 96 is not oxidized, and the solvent removal curing step can be performed on the assembly of the fuel cell device 1 in which the reforming catalyst 96 is incorporated.

  Further, according to the method for manufacturing the solid oxide fuel cell device 1 of the present embodiment, since the ceramic adhesive that undergoes the dehydration condensation reaction at 200 ° C. or lower is used, the reforming catalyst is incorporated. In addition, a solvent removal curing step (step S19 in FIG. 24) can be performed on the ceramic adhesive.

  According to the apparatus for manufacturing the solid oxide fuel cell device 1 of the embodiment of the present invention, the solid oxide fuel cell device can be produced in a relatively short time while sufficiently reducing the risk of cracks in the ceramic adhesive layer. Can be manufactured.

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 workable curing process for each joint includes the joint between the aggregation chamber lower member 18b and the fuel cell 16, the joint between the fuel cell 16 and the first fixing member 63, and the aggregation chamber. It is carried out in the order of the joint portion between the member 18a and the aggregation chamber lower member 18b, the joint portion between the dispersion chamber bottom member 72 and the inner cylindrical member 64, and the joint portion between the outer cylindrical member 66 and the inner cylindrical container 68. The present invention can also be configured so that the fuel cells are joined from the lower end.

  In this case, the junction between the fuel cell 16 and the first fixing member 63 for the first time, the junction between the aggregation chamber lower member 18b and the fuel cell 16 for the second time, and the aggregation chamber upper member 18a and the aggregation chamber for the third time. The workable curing process is performed on the joint of the lower member 18b and the joint of the dispersion chamber bottom member 72 and the inner cylindrical member 64 for the fourth time, and the joint of the outer cylindrical member 66 and the inner cylindrical container 68 for the fifth time. According to this modification, the workable curing process for the cell joint that joins the fuel cell and other components is performed in the first and second times which are the first half of the five workable curing processes. It will be. As a result, the workable curing step is performed the most number of times for the cell joint portion that particularly needs to ensure airtightness, and the airtightness in the cell joint portion can be reliably ensured.

DESCRIPTION OF SYMBOLS 1 Solid oxide type fuel cell apparatus 2 Fuel cell module 4 Auxiliary machine unit 7 Heat insulating material 8 Fuel cell storage container 10 Power generation chamber 16 Fuel cell 16a Single cell 18 Exhaust concentration chamber 18a Aggregation chamber upper member 18b Aggregation chamber lower member ( Second fixing member)
18c Insertion hole 18d Spout 18e Adhesive filling frame 19a Large diameter seal ring 19b Small diameter seal ring 19c Cover member 20 Fuel gas supply channel (fuel channel)
21 Exhaust gas discharge passage 22 Oxidant gas supply passage 24 Water supply source 26 Pure water tank 28 Water flow rate adjustment unit (water supply device)
30 Fuel Supply Source 34 Heat Exchanger 35 Solenoid Valve 36 Desulfurizer 38 Fuel Blower (Fuel Supply Device)
40 Air supply source 45 Air flow rate adjustment unit (oxidant gas supply device)
50 Hot water production equipment 54 Inverter 56 Oxidant gas introduction pipe (oxidant gas inlet)
58 Exhaust gas exhaust pipe (exhaust gas outlet)
60 Combustion catalyst 61 Sheath heater 62 Ignition heater 63 First fixing member (dispersion chamber forming plate)
63a Insertion hole 63b Adhesive filling frame 64 Inner cylindrical member (power generation chamber constituting member)
64a Small hole 64b Small hole 64c Stay (positioning member)
64d Shelf member 65 Intermediate cylindrical member 66 Outer cylindrical member 66a Shelf member 67 Cover member 68 Inner cylindrical container (exhaust passage constituting member)
70 Outer cylindrical container (supply passage component)
72 Dispersion chamber bottom member 72a Insertion pipe (conductor passage)
72b Heat insulating material 72c Flange portion 74 Oxidant gas injection pipe 76 Fuel gas dispersion chamber 78 Insulator 80 Bus bar 82 Current collector 86 Evaporating portion 86a Inclined plate 88 Water supply pipe 90 Fuel gas supply pipe 92 Fuel gas supply flow path partition wall 92a Injection Port 94 Reforming part 96 Reforming catalyst 97 Porous support 98 Fuel electrode layer 99 Reaction suppression layer 100 Solid electrolyte layer 101 Air electrode layer 102 Interconnector layer 103a Electrode layer 103b Electrode layer 104a Lead film layer 104b Lead film layer 110 Below Side jig (first positioning device)
110a Positioning shaft 110b Base end face 112 Upper jig (second positioning device)
112a Frustum 114 Adhesive injection device (adhesive attachment device)
116 Drying furnace (heating device, adhesive curing device)
116a Heat control device 118 Ceramic adhesive layer 118a Raised portion 118b Hanging portion 120a Ceramic adhesive layer 120b Ceramic adhesive layer 122 Ceramic adhesive layer 124 Ceramic adhesive layer 126 Dispersion chamber seal ring 128 Ceramic adhesive layer 130 Central seal plate 132 Ceramic adhesive layer 134 Exhaust passage seal ring 136 Heated air introduction pipe

Claims (7)

A method of manufacturing a solid oxide fuel cell device that generates power by supplying fuel and an oxidant gas to a plurality of fuel cells accommodated in a fuel cell module,
An adhesive attachment step of attaching a ceramic adhesive to the joints of the component parts so that a flow path for guiding the fuel or oxidant gas in the fuel cell module is hermetically configured;
Provided with a drying and curing process to dry and cure the adhered ceramic adhesive,
The drying and curing step is
Workable curing process to cure the attached ceramic adhesive;
After the adhesive attaching step and the workable curing step are repeated a plurality of times, the solvent remaining inside the ceramic adhesive is further removed from the ceramic adhesive cured in the workable curing step repeated a plurality of times. Further curing, a solvent removal curing step of drying the ceramic adhesive at a temperature higher than the workable curing step, and
A method for producing a solid oxide fuel cell device, comprising:   The said solvent removal hardening process is a manufacturing method of Claim 1 implemented at the end of all the processes of the said dry hardening process.   The manufacturing method according to claim 1, wherein the solvent removal curing step dries the ceramic adhesive at a temperature higher than the temperature of the workable curing step and lower than a temperature at which the fuel cell can generate power.   The said solvent removal hardening process is a manufacturing method of Claim 3 which dries a ceramic adhesive at the temperature of 100 to 200 degreeC. The manufacturing method according to claim 4 , wherein the ceramic adhesive is subjected to a dehydration condensation reaction at 200 ° C. or less in the solvent removal curing step.   The manufacturing method according to claim 1, wherein among the workable curing steps performed a plurality of times, at least the first workable curing step is shorter than the last workable curing step. An apparatus for manufacturing a solid oxide fuel cell device for generating power by supplying fuel and an oxidant gas to a plurality of fuel cells accommodated in a fuel cell module,
An adhesive attachment device that attaches a ceramic adhesive to the joints of the component parts so that the flow path for guiding the fuel or oxidant gas in the fuel cell module is hermetically configured;
A heating device for heating the adhered ceramic adhesive at a predetermined temperature for a predetermined time;
A workable curing process for curing the adhered ceramic adhesive, and after performing the adhesion of the ceramic adhesive and the workable curing process multiple times, the cured ceramic adhesive is higher than the workable curing process. A heating control device that controls the heating device so as to perform a solvent removal curing step that is dried at a temperature;
An apparatus for producing a solid oxide fuel cell device, comprising: