Patent Application
20150004517
This application claims priority under 35 U.S.C. §119 to Japanese Patent Application Nos. 2013-135084 filed on Jun. 27, 2013 and 2013-135085 filed on Jun. 27, 2013, the entire contents of which are hereby incorporated by reference.
1. Technical Field
The present invention pertains to a solid oxide fuel cell system, and more particularly to a solid oxide fuel cell system for generating electricity by supplying fuel and oxidant gas to multiple fuel cells housed in a fuel cell module.
2. Background Art
Solid oxide fuel cells (“SOFCs” below) are fuel cells which operate at a relatively high temperature in which, using an oxide ion-conducting solid electrolyte as electrolyte, with electrodes attached to both sides thereof, fuel gas is supplied to one side thereof and oxidant gas (air, oxygen, or the like) is supplied to the other side thereof.
Generally a large number of fuel cells are housed in a fuel cell module forming a solid oxide fuel cell system, and fuel gas is distributed to each of this large number of fuel cells. The fuel gas distributed to each of the fuel cells is supplied first to what is referred to as a fuel gas dispersion chamber, then flows from this fuel gas dispersion chamber into each of the respective fuel cells. Therefore each of the large number of fuel cells is affixed to a fuel gas dispersion chamber so as to communicate with the interior of the fuel gas dispersion chamber. Since solid oxide fuel cells generally operate at high temperatures of 600 to 1000° C., each of the fuel cells must be affixed so as to withstand such high temperatures. In addition, the connecting portion between each of the fuel cells and the fuel gas dispersion chamber must be airtight.
Therefore to join each of the fuel cells to the fuel gas dispersion chamber, such methods as mechanically affixing the fuel cells to the fuel gas dispersion chamber via a metal part, then flowing glass in paste form into the joining portion, have been used to assure airtightness.
In the fuel cells set forth in Japanese Patent JP3894860B (Patent Document 1) and Japanese Published Unexamined Patent Application JPH6-215782A (Patent Document 2), adhesion of the joining portions of the constituent parts of the interior of the fuel cell module is accomplished using a ceramic adhesive.
Japanese Patent JP3894860B
Japanese Published Unexamined Patent Application JPH6-215782A
The problem, however, has been that when airtightness is accomplished by flowing glass in a paste form into joining portions after mechanically affixing fuel cells, two steps are required for each joining location, and since these steps are required for all of the large number of fuel cells, manufacturing costs mounted.
In addition, when fuel cells are affixed via metal parts inside a fuel cell module, chrome components vaporize from the metal parts when exposed to high temperatures, and this causes chrome poisoning of the fuel cells leading to degradation of the cells. The problem can also arise that when sealing is done using glass in order to achieve airtightness at joining portions, boron vaporizes from the glass and causes degradation of the fuel cells by adhering thereto.
On the other hand, the aforementioned type of degradation to fuel cells can be avoided by adhering using the ceramic adhesive set forth in Japanese Patent JP3894860B and Japanese Published Unexamined Patent Application JPH6-215782A. The problem for conventional joints using ceramic adhesive, however, has been the difficulty of obtaining reliable seals in the affixing portions while simultaneously affixing the fuel cells.
That is, water or other solvents in the ceramic adhesive evaporate during hardening after application causing volumetric shrinkage, peeling, or excessive cracking associated with that shrinkage can occur in the ceramic adhesive layer after hardening unless that shrinkage is skillfully controlled. When such peeling or cracking does occur in the ceramic adhesive layer, sufficient sealing properties cannot be secured in those joint portions even though sufficient adhesion strength may be obtained between constituent parts.
If fuel gas leaks out from the affixing portions of the fuel cells, the leaked fuel gas combusts in inappropriate locations on the air electrode side, leading to a high probability of fuel cell damage. Also, leakage of fuel gas presents the risk of increased running costs associated with reduced fuel utilization, and fuel depletion caused by insufficient supply of fuel gas to the fuel electrode side.
In order to compensate for these sealing deficiencies, it has been proposed to coat the top of the ceramic adhesive layer with glass after adhesion (Japanese Patent JP3894860B, Paragraph [0035]). However, when a ceramic adhesive layer is coated with glass, the number of manufacturing steps increases and the problem of boron evaporation from the glass occurs, so there is no advantage to using the ceramic adhesive.
Peeling and cracking in the ceramic adhesive layer is prone to occur when adhered ceramic adhesive is suddenly dried. It is therefore possible to substantially avoid peeling or cracking by slow, natural drying of adhered ceramic adhesive at room temperature. However, when ceramic adhesive is dried naturally, an extremely long period of time is required until sufficient adhesion strength can be obtained at the joint portion, and during that time material cannot be moved to the next manufacturing step. Therefore natural drying is completely unsuited for practical industrial use, particularly in the production of solid oxide fuel cell system, as these require a large number of joint portions and multiple manufacturing steps.
That is, when assembled pieces coated with adhesive are dried in a drying oven or the like, as is generally done to promote the drying of adhesive, excessive cracking occurs in the hardened ceramic adhesive layer. Of the various ceramic adhesives applied by coating, it is areas such as parts receiving large amounts of drying heat, locations where it is difficult for heat to diffuse and therefore temperatures rise, or parts easily subject to humidity gradients upon contact with the atmosphere which are first dried and hardened. Therefore hardening begins at specific parts of the surface layer, and even within the surface layer hardening does not start uniformly nor is the hardened state even, so uniformly hardening of all portions is not possible. Next, when adhesive on the interior of a hardened surface portion or surrounding a hardened surface is dried, stress concentrates with shrinkage of weak portions where drying is still not sufficiently completed in areas surrounding ceramic adhesive which has already hardened, and cracks form in these weak portions so that airtightness is compromised. Although the use of ceramic adhesives in the assembly of solid oxide fuel cell system is set forth in patent documents, the fact that there are problems with airtightness and they have not been put to practical use is believed to result from these causes.
Furthermore, the inventors have discovered a new technical problem in that when ceramic adhesive is used in the assembly of a solid oxide fuel cell system, then even if the ceramic adhesive is sufficiently hardened to withstand practical strength requirements and sealing properties able to withstand practical use are obtained, airtightness in the adhered parts is lost when the solid oxide fuel cell system is first operated and the parts are exposed to high temperatures. That is, even in a state whereby adhered ceramic adhesive is hardened and sufficient airtightness and adhesive strength are obtained, small amounts of moisture or other evaporable solvents remain within the hardened ceramic adhesive layer. In particular, when residual moisture or solvents remain in large amounts in a concentrated form internally, the hardened ceramic adhesive layer is heated at an extremely high speed to temperatures which are far higher than the temperatures at the time of drying and hardening, therefore the residual moisture or solvent expands volumetrically and evaporates, at which point this expansion, etc. works to cut open the weak portions of the surface part of the already hardened ceramic adhesive layer, creating new cracks. The cause of such losses in airtightness occurring during practical use was ascertained by the inventors.
That is, when ceramic adhesive is used for the assembly of solid oxide fuel cell system, it is not able to withstand the rise in temperature which occurs during the fuel cell startup step given the drying and hardening state found in general use. To reduce residual moisture or solvents in the interior of the ceramic adhesive layer to a state such that it can withstand the temperature rise during the startup step requires additional time for slow and sufficient drying to occur. Given these causes, extremely long times are required for the assembly of solid oxide fuel cell system in which ceramic adhesives are used, making their practical use extremely difficult.
Therefore the invention has the object of providing a solid oxide fuel cell system in which fuel cells within a fuel cell module are connected in an airtight manner using ceramic adhesive.
In order to resolve the above described problem, the invention is a solid oxide fuel cell system for generating electricity by reacting fuel and oxidant gas, comprising: a fuel cell module comprising plurality of fuel cells, and a fuel gas dispersion chamber that distributes and supplies fuel to each of the fuel cells, wherein each of the fuel cells is affixed in an airtight manner using a ceramic adhesive to an affixing member constituting the fuel gas dispersion chamber, and a gas leak suppression portion that suppresses the occurrence of cracks caused by shrinkage when the ceramic adhesive hardens is formed around the periphery of each of the fuel cells by a layer of the ceramic adhesive.
In the invention thus constituted, multiple fuel cells housed within a fuel cell module are affixed in an airtight manner by ceramic adhesive to an affixing member constituting the fuel gas dispersion chamber. A gas leak suppression portion for suppressing the occurrence of cracks caused by shrinkage when ceramic adhesive hardens is formed around each of the fuel cells by a layer of ceramic adhesive. Supplied fuel is distributed to each of the fuel cells through the fuel gas dispersion chamber.
In the invention thus constituted, a gas leak suppression portion is formed by ceramic adhesive around each of the fuel cells, therefore leakage of fuel gas can be reliably suppressed in the parts surrounding the fuel cells where gas leakage is most likely to occur and where the effects of leakage are most serious. The occurrence of fuel depletion caused by fuel gas leakage at the joining portions between fuel cells and affixing members, as well as problems such anomalous combustion of fuel leaking to the oxidant gas electrode side, can thus be suppressed.
In the invention, an outer circumferential surface of each of the fuel cells is preferably adhered to the affixing member using the ceramic adhesive, and the gas leak suppression portion is constituted by forming the layer of the ceramic adhesive in a surrounding part of each of the fuel cells more thickly than in other parts.
In the invention thus constituted, by forming and hardening ceramic adhesive pools in the surrounding area of fuel cells when the ceramic adhesive is being adhered, the ceramic adhesive layer in the gas leak suppression area is formed to be thicker than in other parts so as to compensate for the shrinkage portion. By this means, even if the adhered ceramic adhesive shrinks during hardening and this shrinkage concentrates around slow-hardening cell units, gaps associated with cracking or peeling between fuel cells are reliably avoided, and airtightness in joint portions can be obtained. Also, because the ceramic adhesive layer is thicker, cracks in the ceramic adhesive layer can be reliably suppressed in the area surrounding the cell units, and more reliable airtightness can be secured.
In the invention, a passage through which gas passes is preferably formed inside each of the fuel cells, and the outer circumferential surface of the fuel cell surrounding the passage is affixed to the affixing member via the gas leak suppression portion, so that when the ceramic adhesive is hardened, the hardening of the ceramic adhesive is more gradual in a surrounding part of each of the fuel cells than in other parts, and cracking in the gas leakage suppression portion is suppressed.
In general, the volume of ceramic adhesives shrinks during hardening. Therefore the border portion, which is the part of the coated ceramic adhesive which hardens first, cracks by being pulled by the shrinkage of adhesive surrounding the later-hardening portion. In the invention thus constituted, passages are formed inside the fuel cells, and material with a low coefficient of thermal conductivity forms the fuel cells, therefore the surrounding area of each of the fuel cells is unlikely to reach high temperatures when the ceramic adhesive is being dried. As a result, hardening of the ceramic adhesive in the area surrounding each of the fuel cells is made gradual, and adhesive in the gas leak prevention portion hardens later, so that cracking is less likely to occur in the gas leak suppression portion, and fuel gas leaks can be suppressed.
In the invention, each of the fuel cells is preferably cylindrical, and the gas leak suppression portion is formed on the outer circumferential surface of each of the fuel cells.
In the invention, because each of the fuel cells is cylindrical and the gas leak suppression portion on the outer perimeter thereof is ring-shaped, hardening of the ceramic adhesive in this portion proceeds essentially uniformly. This reduces the likelihood of stress concentration caused by the shrinkage associated with hardening of ceramic adhesive, so that the occurrence of cracks in the gas suppression portion, and fuel gas leaks, can be suppressed.
The invention preferably further comprises a plate covering the part of the ceramic adhesive away from the surrounding part of each of the fuel cells, wherein the plate makes hardening of the ceramic adhesive in the surrounding parts of the fuel cells more gradual.
In the invention thus constituted, the portion away from the surrounding part of the fuel cells is covered by a plate, therefore localized drying of the covered portion of the ceramic adhesive surface can be prevented and the occurrence of cracking suppressed.
In the invention, the plate is preferably formed of a material with a higher coefficient of thermal conductivity than the fuel cells.
In the invention thus constituted, the plate is formed of a material having a higher coefficient of thermal conductivity than the fuel cells, therefore the covered part of the plate dries essentially uniformly, and the occurrence of cracking can be suppressed. In contrast, ceramic adhesive on the surrounding portion of each of the fuel cells not covered by the plate is positioned close to the low-coefficient of thermal conductivity fuel cells, therefore drying is relatively gradual and the occurrence of cracking is suppressed.
In the invention the gas leak suppression portion is preferably formed by mounting the plate onto the ceramic adhesive adhered to the affixing member when each of the fuel cells is being adhered, so the ceramic adhesive prior to hardening is pressed into the surrounding part of each of the fuel cells.
In the invention thus constituted, the plate is mounted on ceramic adhesive prior to hardening, and the ceramic adhesive is pressed into the surrounding portion of the fuel cells, thereby forming a gas leak suppression portion. Ceramic adhesive pools can thus be formed on the surrounding portions of fuel cells using a simple structure, thereby forming a gas leak suppression portion.
In the present invention, the affixing member and the plate preferably respectively have insertion holes at a predetermined spacing for the insertion of the fuel cells, and perimeter walls are formed to surround the insertion holes on the edge portions of each insertion hole disposed on the affixing member or the plate.
In the invention thus constituted, perimeter walls are formed on the edge portion of each insertion hole disposed on the affixing members or the plate, therefore ceramic adhesive pushed out by the mounting of the plate can be held well at the perimeter portion of a greater number of fuel cells, and airtightness can be more reliably obtained.
In the invention, a plate is preferably disposed on the ceramic adhesive adhering to each of the fuel cells so as to cover the filled-in ceramic adhesive, thereby suppressing the occurrence of cracking during hardening of the ceramic adhesive.
In the invention thus constituted, a ceramic adhesive is filled into the joint portion at which fuel cells are adhered, and a plate is disposed so as to cover this ceramic adhesive. This plate suppresses the occurrence of cracks when the filled in ceramic adhesive hardens.
In the invention thus constituted, a plate is disposed so as to cover filled-in ceramic adhesive, therefore vaporization of moisture or solvent from the portion covered by the plate on the filled-in ceramic adhesive surface is suppressed. As a result, the occurrence of cracking caused by the earlier hardening of the surface part of the ceramic adhesive and later vaporization of internal moisture or solvents can be suppressed. Thus ceramic adhesive can be used to mutually join members in an airtight manner.
In the invention, the ceramic adhesive is preferably hardened by a dehydration condensation reaction, and the plate is mounted on the filled-in ceramic adhesive so as to expose the vicinity of a surrounding part of the fuel cells being adhered, so that at the time of ceramic adhesive hardening, the ceramic adhesive prior to hardening is pressed out to the vicinity of the surfaces of the fuel cells being adhered from the parts on which the plate is mounted, and the amount of ceramic adhesive increases close to the surface of fuel cells being adhered.
In the invention thus constituted, ceramic adhesive prior to hardening is pressed out to the vicinity of the surfaces of the adhered fuel cells from the parts on which the plate is mounted, and the amount of ceramic adhesive increases close to the surface of fuel cells. As a result, even if the volume contracts and so-called “shrinking” occurs when the ceramic adhesive is hardened, the occurrence of gaps can be prevented at the joining portions where the ceramic adhesive is filled in. Also, the plate is mounted in such a way that vicinity of the surface of each of the fuel cells is exposed. As a result, moisture contained in the part of the ceramic adhesive covered by the plate evaporates through the exposed portion of the surface vicinity of each fuel cell. Drying and hardening of the ceramic adhesive in the portion at the surface region of each fuel cell thus is made gradual, and the occurrence of cracking is suppressed.
In the invention, plurality of the fuel cells are preferably affixed by ceramic adhesive to the affixing member, and by injecting ceramic adhesive onto the affixing member with the fuel cells inserted into insertion holes formed in the affixing member, and gaps between the outer circumferential surface of the fuel cells and the insertion holes are filled in by ceramic adhesive, and the fuel cells are affixed to the affixing member.
In the invention thus constituted, multiple fuel cells are affixed by the injection of ceramic adhesive while inserted into each of insertion holes on affixing members, therefore multiple fuel cells can be affixed in a single step, thereby enabling productivity to be improved. Since fuel cells generally have a low coefficient of thermal conductivity, the temperature of ceramic adhesive in the vicinity of the fuel cells is low when the ceramic adhesive he is dried and hardened by heating. As a result, drying and hardening of the ceramic adhesive in the portion at the surface region of each fuel cell is made gradual, and the occurrence of cracking is suppressed.
In the present invention the plate preferably has plurality of insertion holes for the insertion of the fuel cells; the plate is disposed on the ceramic adhesive which has been injected onto the affixing members, and a generally uniform gap is formed between the insertion holes in the plate and the outer perimeter surface of the fuel cells.
In the invention thus constituted, a gap is formed between each of the insertion holes on the plate and the outer circumferential surface of the fuel cells, therefore ceramic adhesive in the region of the outer circumferential surface of the fuel cells is exposed. As a result, moisture contained in the part of the ceramic adhesive covered by the plate evaporates through the exposed portion of the outer circumferential surface vicinity of each fuel cell. Drying and hardening of the ceramic adhesive in the portion at the surface region of each fuel cell thus is made gradual, and the occurrence of cracking is suppressed, and the fuel cells can be affixed while securing airtightness.
In the invention, at the time of hardening, the ceramic adhesive pressed out prior to hardening from beneath the plate by the weight of the plate is filled into the gap between each of the insertion holes in the plate and the outer perimeter surface of the fuel cells.
In the invention thus constituted, ceramic adhesive pressed out from beneath the plate is filled into the gap between the insertion holes in the plate and the fuel cells, so that adhesive pools can be formed around the fuel cells using a simple structure. As result, even in cases where “shrinkage” has occurred during hardening of the ceramic adhesive, gaps can be prevented from occurring around the fuel cells.
In the present invention, perimeter walls are preferably formed to surround the insertion holes on the edge portions of each insertion hole disposed on the plate.
In the invention thus constituted, perimeter walls are formed on the edge portions of each insertion hole disposed on a plate, therefore it is difficult for ceramic adhesive filled into the gap between the plate insertion holes and the fuel cells to flow out from the insertion holes in the plate. As a result, large amounts of ceramic adhesive can be pooled in adhesive pools around the fuel cells, and the occurrence of gaps caused by “shrinkage” can be reliably prevented.
With the solid oxide fuel cell system of the invention, fuel cells inside the fuel cell module can be joined in an airtight manner using ceramic adhesive.
a) is a cross-section showing an expanded view of the bottom end portion of fuel cells on which the bottom end is a cathode;
Next, referring to the attached drawings, we discuss a solid oxide fuel cell (SOFC) system according to an embodiment of the present invention.
Fuel cell module 2 comprises a fuel cell housing container 8; is formed within this housing 6, mediated by thermal insulation 7. A generating chamber 10 is formed on the interior of this fuel cell housing container 8; multiple fuel cells 16 are concentrically disposed within this generating chamber 10, and the generating reaction between fuel gas and air, which is the oxidizing gas, is carried out by these fuel cells 16.
An exhaust collection chamber 18 is attached to the top end portion of each fuel cell 16. Residual fuel (off-gas), unused for the generating reaction and remaining in each fuel cell 16, is collected in the exhaust collection chamber 18 attached to the top end portion and flows out of the multiple jet openings placed in the ceiling surface of exhaust collection chamber 18. Out flowing fuel is combusted in generating chamber 10 using remaining air not used for generation, thereby producing exhaust gas.
Next, auxiliary unit 4 comprises pure water tank 26, which stores water from water supply source 24 and uses a filter to produce pure water, and water flow volume regulator unit 28 (a motor-driven “water pump” or the like), being a water supply apparatus, which regulates the flow volume of water supplied from this pure water tank. Also, auxiliary unit 4 comprises a fuel blower 38 (a motor-driven “fuel pump” or the like), being a fuel supply apparatus, for regulating the flow volume of hydrocarbon raw fuel gas supplied from fuel supply source 30, such as municipal gas.
Note that raw fuel gas which is passed through fuel blower 38 is introduced into the interior of fuel cell housing container 8 through the desulfurizer 36, heat exchanger 34, and electromagnetic valve 35 in fuel cell module 2. The desulfurizer 36 is disposed in a ring shape around fuel cell housing container 8, and operates to remove sulfur from raw fuel gas. Heat exchanger 34 is provided to prevent degradation of electromagnetic valve 35 when high-temperature raw fuel gas heated in desulfurizer 36 flows directly into electromagnetic valve 35. Electromagnetic valve 35 is provided in order to stop the supply of raw fuel gas into fuel cell housing container 8.
Auxiliary unit 4 comprises a generating air flow regulator unit 45 (a motor driven “air blower” or the like), being an oxidant gas supply apparatus, for regulating the flow volume of air supplied from air supply source 40.
In addition, auxiliary unit 4 is equipped with a hot water production device 50 for recovering the heat in exhaust gas from fuel cell module 2. Tap water is supplied to hot water production device 50; this tap water is converted to hot water by the heat from exhaust gas, and is supplied to an external hot water tank, not show.
In addition, connected to fuel cell module 2 is an inverter 54, being a power extraction section (power conversion section) for supplying electricity generated by fuel cell module 2 to the outside.
Next, referring to
As shown in
First, as shown in
As shown in
The inside cylindrical member 64 is an approximately cylindrical hollow body, the top and bottom ends of which are open. First affixing member 63, being a dispersion chamber-forming plate, is welded in an airtight manner to the interior wall surface of inside cylindrical member 64. A fuel gas dispersion chamber 76 is defined by the bottom surface of this first affixing member 63, the inside wall surface of inside cylindrical member 64, and the top surface of dispersion chamber bottom member 72. Multiple insertion holes 63a, into which fuel cells 16 are inserted, are formed on first affixing member 63, and each fuel cell 16 is adhered to first affixing member 63 by ceramic adhesive, with the fuel cells 16 inserted into each of the insertion holes 63a. Thus in a solid oxide fuel cell system 1 of the embodiment, ceramic adhesive is filled into the mutual joining portions between members constituting fuel cell module 2, and with hardening, each of the members is mutually joined in an airtight manner.
External cylindrical member 66 is a cylindrical pipe disposed on the periphery of inside cylindrical member 64, formed in an approximately analogous shape to inside cylindrical member 64 so that a ring-shaped flow path is formed between external cylindrical member 66 and inside cylindrical member 64. In addition, an intermediate cylindrical member 65 is disposed between inside cylindrical member 64 and external cylindrical member 66. Intermediate cylindrical member 65 is a cylindrical pipe disposed between inside cylindrical member 64 and external cylindrical member 66, and a reforming section 94 is constituted between the outside circumferential surface of inside cylindrical member 64 and the inside circumferential surface of intermediate cylindrical member 65. Also, the ring-shaped space between the outer circumferential surface of intermediate cylindrical member 65 and the inner circumferential surface of external cylindrical member 66 functions as a fuel gas supply flow path 20. Therefore reforming section 94 and fuel gas supply flow path 20 receive the heat from combustion of residual fuel at the top end of exhaust collection chamber 18 in the fuel cells 16. The top end portion of inside cylindrical member 64 and top end portion of external cylindrical member 66 are joined in an airtight manner by welding, while the top end of fuel gas supply flow path 20 is closed off. Also, the bottom end of intermediate cylindrical member 65 and the outer peripheral surface of inside cylindrical member 64 are joined in an airtight manner by welding.
Inside cylindrical container 68 is a cup-shaped member with a circular cross section disposed on the periphery of external cylindrical member 66, the side surface of which is formed in an approximately analogous shape to external cylindrical member 66, so that a ring-shaped flow path of an essentially fixed width is formed between inside cylindrical container 68 and external cylindrical member 66. This inside cylindrical container 68 is disposed so as to cover the open portion at the top end of inside cylindrical member 64. The ring-shaped space between the outer circumferential surface of external cylindrical member 66 and the inner circumferential surface of inside cylindrical container 68 functions as exhaust gas discharge flow path 21 (
A combustion catalyst 60 and sheath heater 61 for heating same is disposed at the bottom portion of exhaust gas discharge flow path 21.
Combustion catalyst 60 is a catalyst filled into the ring-shaped space between the outer circumferential surface of external cylindrical member 66 and the inner circumferential surface of inside cylindrical container 68, above exhaust gas exhaust pipe 58. By passing through combustion catalyst 60, carbon monoxide is removed from exhaust gas descending the exhaust gas discharge flow path 21 and discharged from exhaust gas exhaust pipe 58.
Sheath heater 61 using electrical heater attached so as to surround the outer circumferential surface of external cylindrical member 66 underneath combustion catalyst 60. When solid oxide fuel cell system 1 is started, combustion catalyst 60 is heated to an activation temperature by turning on electricity to sheath heater 61.
External cylindrical container 70 is a cup-shaped member with a circular cross section disposed on the periphery of inside cylindrical container 68, the side surface of which is formed in an approximately analogous shape to inside cylindrical container 68, so that a ring-shaped flow path of an essentially fixed width is formed between external cylindrical container 70 and inside cylindrical container 68. The ring-shaped space between the outer circumferential surface of inside cylindrical container 68 and the inner circumferential surface of external cylindrical container 70 functions as oxidant gas supply flow path 22. Oxidant gas introducing pipe 56 is connected to the bottom end surface of external cylindrical container 70, and oxidant gas supply flow path 22 communicates with oxidant gas introducing pipe 56.
Dispersion chamber bottom member 72 is an approximately plate-shaped member, affixed in an airtight manner with ceramic adhesive to the inside wall surface of inside cylindrical member 64. A fuel gas dispersion chamber 76 is thus constituted between first affixing member 63 and dispersion chamber bottom member 72. Also, insertion pipe 72a for the insertion of bus bars 80 (
A circular cross section oxidant gas jetting pipe 74 for jetting generating air is attached so as to hang down from the ceiling surface of inside cylindrical container 68. This oxidant gas jetting pipe 74 the extends in the vertical direction on the center axial line of inside cylindrical container 68, and each fuel cell 16 is disposed on concentric circles around oxidant gas jetting pipe 74. By attaching the top end of oxidant gas jetting pipe 74 to the ceiling surface of inside cylindrical container 68, oxidant gas supply flow path 22, formed between inside cylindrical container 68 and external cylindrical container 70, is made to communicate with oxidant gas jetting pipe 74. Air supplied via oxidant gas supply flow path 22 is jetted downward from the tip of oxidant gas jetting pipe 74, hitting the top surface of first affixing member 63 and spreading to the entire interior of generating chamber 10.
Fuel gas dispersion chamber 76 is a cylindrical airtight chamber, constituted between first affixing member 63 and dispersion chamber bottom member 72, on the top surface of which each fuel cell 16 is closely arrayed. The inside fuel electrode of each fuel cell 16 attached to the top surface of first affixing member 63 communicates with the interior of fuel gas dispersion chamber 76. The bottom end portion of each fuel cell 16 penetrates the insertion holes 63a in first affixing member 63 and protrudes into fuel gas dispersion chamber 76, so that each fuel cell 16 is affixed by adhesion to first affixing member 63.
As shown in
In addition, the bottom end portions of each fuel cell 16 protruding into fuel gas dispersion chamber 76 are electrically connected to bus bars 80 inside fuel gas dispersion chamber 76, and electoral power is extracted to the outside through insertion pipe 72a. Bus bars 80 are elongated metal conductors for extracting power produced by each fuel cell 16 to the outside of fuel cell housing container 8, affixed to dispersion chamber bottom member 72 insertion pipe 72a through insulator 78. Bus bars 80 are electrically connected to a power collector 82 attached to each fuel cell 16 on the interior of fuel gas dispersion chamber 76. Bus bars 80 are connected to inverter 54 (
Next, referring to
As shown in
As shown in
Exhaust collection chamber 18 is constituted by joining collection chamber upper member 18a and collection chamber lower member 18b in an airtight manner.
Collection chamber lower member 18b is a round plate shaped member open at the top, at the center of which a cylindrical portion is provided to permit the penetration of oxidant gas jetting pipe 74.
Collection chamber upper member 18a is a round plate shaped member open at the bottom, at the center of which an opening is provided to permit the penetration of oxidant gas jetting pipe 74. Collection chamber upper member 18a has a shape capable of insertion into the doughnut shaped cross-sectional region which opens at the top of collection chamber lower member 18b.
Ceramic adhesive is filled into and hardened in the gap between the inner circumferential surface of the wall surrounding collection chamber lower member 18b and the outer circumferential surface of collection chamber upper member 18a, assuring airtightness in this joining portion. A large diameter seal 19a is disposed on the ceramic adhesive layer formed by the ceramic adhesive filled into this joint portion, covering the ceramic adhesive layer. The large diameter seal 19a is a ring-shaped thin plate, disposed to cover the filled-in ceramic adhesive layer after the ceramic adhesive is filled, and affixed to exhaust collection chamber 18 by the hardening of the adhesive.
On the other hand, ceramic adhesive is also filled in and hardened between the outside circumferential surface of the cylindrical portion at the center of collection chamber lower member 18b and the edge of the opening portion at the center of collection chamber upper member 18a, assuring the airtightness of this joint portion. A small diameter seal 19b is disposed on the ceramic adhesive layer formed by the ceramic adhesive filled into this joint portion, covering the ceramic adhesive layer. The small diameter seal 19b is a ring-shaped thin plate, disposed to cover the filled-in ceramic adhesive layer after the ceramic adhesive is filled, and affixed to exhaust collection chamber 18 by the hardening of the adhesive.
Multiple insertion holes 18c are formed on the bottom surface of collection chamber lower member 18b. The top end portions of each fuel cell 16 respectively penetrate each of the insertion holes 18c, and each fuel cell 16 penetrate each of the insertion holes 18c. Ceramic adhesive is flowed onto the bottom surface of collection chamber lower member 18b, which is penetrated by fuel cells 16; hardening of the adhesive fills in the gap between the outer perimeter of each fuel cell 16 and the insertion holes 18c in an airtight manner and results in the affixing of each fuel cell 16 to collection chamber lower member 18b.
Furthermore, round, thin plate cover member 19c is disposed on the ceramic adhesive flowed into the bottom surface of collection chamber lower member 18b and affixed to collection chamber lower member 18b by the hardening of the ceramic adhesive. Multiple insertion holes are formed in cover member 19c at the same positions as each of the insertion holes 18c in collection chamber lower member 18b, and the top end portion of each fuel cell 16 penetrate and extend through these ceramic adhesive layer and cover member 19c.
At the same time, multiple jet openings 18d for jetting collected fuel gas are formed in the ceiling surface of exhaust collection chamber 18 (
Next, referring to
First, vaporization section 86 for vaporizing water for use in steam reforming is provided at the bottom portion of fuel gas supply flow path 20 formed between inside cylindrical member 64 and external cylindrical member 66. Vaporization section 86 comprises ring-shaped inclined plate 86a attached to the lower inside perimeter of external cylindrical member 66, and fuel gas flow path 88. Also, vaporization section 86 is disposed below oxidant gas introducing pipe 56 for introducing generating air, and above exhaust gas exhaust pipe 58 for discharging exhaust gas. Ring-shaped inclined plate 86a is a metal thin plate formed a ring shape, the outer circumferential edge of which is attached to the inside wall surface of external cylindrical member 66. At the same time, the inside perimeter edge of ring-shaped inclined plate 86a is positioned above the outside perimeter edge thereof, and a gap is provided between the inside perimeter edge of inclined plate 86a and the outside wall surface of inside cylindrical member 64.
Water supply pipe 88 is a pipe extending vertically within fuel gas supply flow path 20 from the bottom end of inside cylindrical member 64; water for steam reforming supplied from water flow volume regulator unit 28 is supplied to vaporization section 86 through water supply pipe 88. The top end of water supply pipe 88 extends to the top surface side of inclined plate 86a, penetrating inclined plate 86a, and water supplied to the top surface side of inclined plate 86a pools between the top surface of inclined plate 86a and the inside wall surface of external cylindrical member 66. Water supplied to the top surface of inclined plate 86a is vaporized there, producing steam.
A combustion gas introducing portion for introducing raw fuel gas into fuel gas supply flow path 20 is erected under vaporization section 86. Raw fuel gas fed from fuel blower 38 is introduced into fuel gas supply flow path 20 through fuel gas supply pipe 90. Fuel gas supply pipe 90 is a type extending vertically inside fuel gas supply flow path 20 from the bottom end of inside cylindrical member 64. The top end of fuel gas supply pipe 90 is positioned beneath inclined plate 86a. Raw fuel gas fed from fuel blower 38 is introduced at the bottom side of inclined plate 86a and rises to the top side of inclined plate 86a as its flow path is restricted by the slope of inclined plate 86a. Raw fuel gas rising to the top side of inclined plate 86a rises together with the steam produced by vaporization section 86.
A fuel gas supply flow path partition 92 is erected above vaporization section 86 in fuel gas supply flow path 20. Fuel gas supply flow path partition 92 is a ring-shaped metal plate disposed to separate into top and bottom portions the ring-shaped space between the inside perimeter of external cylindrical member 66 and the outside perimeter of intermediate cylindrical member 65. Multiple equally spaced jet openings 92a are provided in a circle on fuel gas supply flow path partition 92, and the spaces above and below fuel gas supply flow path partition 92 communicate through these jet openings 92a. Raw fuel gas introduced from fuel gas supply pipe 90 and steam produced by vaporization section 86 are first pooled in the space on the bottom side of fuel gas supply flow path partition 92, then passed through each of the jet openings 92a and jetted into the space on the top side of fuel gas supply flow path partition 92. When jetted into the wide space on the top side of fuel gas supply flow path partition 92 from each of the jet openings 92a, the raw fuel gas and steam suddenly decelerate and sufficiently mix here.
In addition, a reforming section 94 is erected on the top portion of the ring shaped space between the inside perimeter of intermediate cylindrical member 65 and the outside perimeter of inside cylindrical member 64. Reforming section 94 is disposed so as to surround the top portion of each fuel cell 16 and the perimeter of the exhaust collection chamber 18 at the top thereof. Reforming section 94 comprises a catalyst holding plate (not shown) attached to the outer wall surface of inside cylindrical member 64, and a reforming catalyst 96 held in place thereby.
Thus when raw fuel gas and steam, mixed in the space over fuel gas supply flow path partition 92, makes contact with the reforming catalyst 96 filled into reforming section 94, the steam reforming reaction shown by Eq. (1) proceeds inside reforming section 94.
CmHn+xH2O→aCO2+bCO2+cH2 (1)
Fuel gas reformed in reforming section 94 flows downward in the space between the inside perimeter of intermediate cylindrical member 65 and the outside perimeter of inside cylindrical member 64, flowing into fuel gas dispersion chamber 76 to be supplied to each fuel cell 16. The steam reforming reaction is an endothermic reaction, however the heat required for the reaction is supplied by the combustion heat of off-gas flowing out from exhaust collection chamber 18 and the emitted heat produced in each fuel cell 16.
Next, referring to
In the solid oxide fuel cell system 1 of the embodiment, cylindrical crossbar cells using solid oxides are adopted as the fuel cells 16. Multiple single cells 16a are arranged in crossbar form on each fuel cell 16, and a fuel cell 16 is constituted by electrically connecting these together in series. Each fuel cell 16 comprises an anode (positive electrode) at one end and a cathode (negative electrode) at the other end; of the multiple fuel cells 16, half are disposed so that the top end is an anode and the bottom end is a cathode, and the other half are disposed so that the top end is a cathode and the bottom end is an anode.
As shown in
As shown in
As shown in
In
Next we explain the constitution of porous support body 97, and of each layer.
The porous support body 97 in the embodiment is formed by extruding and sintering a mixture of forsterite powder and the binder.
In the embodiment, fuel electrode 98 is an electrically conductive thin film comprised of a mixture of NiO powder and 10YSZ (10 mol % Y2O3-90 mol % ZrO2) powder.
In the embodiment, reaction suppression layer 99 is a thin film comprising cerium compound oxide (LDC 40; i.e., 40 mol % La2O3-60 mol % CeO2) or the like, by which chemical reactions between fuel electrode 98 and solid electrolyte layer 100 are suppressed. That is, it is a thin film constituted of 40 mol % La2O3-60 mol % CeO2.
In the embodiment, solid electrolyte layer 100 is a thin film comprising an LSGM powder composition of La0.9Sr0.1Ga0.8Mg0.2O3. Electrical energy is produced by the reaction between oxide ions and hydrogen or carbon monoxide through this solid electrolyte layer 100.
In the embodiment, air electrode 101 is an electrically conductive thin film comprising a powder composition of La0.6Sr0.4CO0.8Fe0.2O3.
In the embodiment, interconnector layer 102 is an electrically conductive thin film comprising SLT (lanthanum doped strontium titanate). Adjacent single cells 16a on fuel cells 16 are connected via interconnector layer 102.
In the embodiment, electrode layers 103a and 103b are formed of the same material as fuel electrode 98.
In the embodiment, lead film layers 104a and 104b are formed of the same material as solid electrolyte layer 100.
Next, referring to
First, in the startup step of solid oxide fuel cell system 1, fuel blower 38 is started, and power to the sheath heater 61 is started at the same time as the supply of fuel is started. By starting the power to sheath heater 61, the combustion catalyst 60 disposed above sheath heater 61 is heated, and vaporization section 86 disposed on the inside thereof is also heated. Fuel supplied by fuel blower 38 flows from fuel gas supply pipe 90 via desulfurizer 36, heat exchanger 34, and electromagnetic valve 35 into the interior of fuel cell housing container 8. In-flowing fuel, after rising up to the top end within fuel gas supply flow path 20, drops down within reforming section 94, then through small holes 64b placed on the bottom portion of inside cylindrical member 64, and into fuel gas dispersion chamber 76 Note that immediately after the of solid oxide fuel cell system 1 startup step, because the temperature of reforming catalyst 96 in reforming section 94 has not risen sufficiently, no fuel reforming is performed.
Fuel gas which has flowed into fuel gas dispersion chamber 76 flows through the inside (the fuel electrode side) of each of the fuel cells 16 attached to first affixing member 63 of fuel gas dispersion chamber 76 and into exhaust collection chamber 18. Note that immediately after startup of solid oxide fuel cell system 1, the temperature of each of the solid oxide fuel cell system 1 has not risen sufficiently, or power is not being extracted to inverter 54, therefore no electrical generating reaction is occurring.
Fuel flowing into exhaust collection chamber 18 is jetted from exhaust collection chamber 18 jet openings 18d. Fuel jetted from jet openings 18d is ignited by ignition heater 62 and combusted. Reforming section 94, disposed around exhaust collection chamber 18, is heated by this combustion. Exhaust gas produced by combustion flows into exhaust gas discharge flow path 21 through small holes 64a formed in the top portion of inside cylindrical member 64. High temperature exhaust gas descends the interior of exhaust gas discharge flow path 21, heating fuel flowing in the fuel gas supply flow path 20 disposed on the inside thereof and generating air flowing in the oxidant gas supply flow path 22 disposed on the outside thereof. In addition, exhaust gas passes through the combustion catalyst 60 disposed within exhaust gas discharge flow path 21, whereby carbon monoxide is removed, then passes through exhaust gas exhaust pipe 58 to be discharged from fuel cell housing container 8.
When vaporization section 86 is heated by exhaust gas and sheath heater 61, water for steam reforming supplied to vaporization section 86 is vaporized and steam is produced. Water for steam reforming is supplied by water flow volume regulator unit 28 to vaporization section 86 in fuel cell housing container 8 via water supply pipe 88. When steam is produced by vaporization section 86, fuel supplied through fuel gas supply pipe 90 is first held in the space on the bottom side of fuel gas supply flow path partition 92 inside fuel gas supply flow path 20, then jetted from multiple jet openings 92a formed in fuel gas supply flow path partition 92. Fuel and steam jetted with high force from jet openings 92a are well blended by being decelerated in the space on the top side of fuel gas supply flow path partition 92.
Blended fuel and steam rise up within fuel gas supply flow path 20 and flow into reforming section 94. In a state whereby the reforming section 94 reforming catalyst 96 has risen to a temperature at which reforming is possible, a steam reforming reaction occurs when the mixed gas of fuel and steam passes through reforming section 94, and the mixed gas is reformed into a hydrogen-rich fuel. Reformed fuel passes through small holes 64b and flows into fuel gas dispersion chamber 76. A large number of small holes 64b are formed around fuel gas dispersion chamber 76, and sufficient capacity is thus assured for fuel gas dispersion chamber 76, therefore reformed fuel flows in uniformly to the fuel cells 16 with which it collides in the fuel gas dispersion chamber 76.
At the same time air, which is the oxidant gas supplied by generating air flow regulator unit 45, flows into oxidant gas supply flow path 22 via oxidant gas introducing pipe 56. Air flowing into oxidant gas supply flow path 22 rises up in oxidant gas supply flow path 22 as it is heated by the exhaust gas flowing on the inside thereof. Air rising in oxidant gas supply flow path 22 is gathered at the center of the top end portion in fuel cell housing container 8 and flows into the oxidant gas jetting pipe 74 which communicates with oxidant gas supply flow path 22. Air flowing into oxidant gas jetting pipe 74 is jetted from the bottom end thereof into generating chamber 10; the jetted air then hits the top surface of first affixing member 63 and spreads throughout the entire generating chamber 10. Air flowing into generating chamber 10 rises up through the gap between the outer perimeter wall of exhaust collection chamber 18 and the inner perimeter wall of inside cylindrical member 64, and through the gap between the inside perimeter wall of exhaust collection chamber 18 and the outside circumferential surface of oxidant gas jetting pipe 74.
At this point, a portion of the air passing over the exteriors (air electrode side) of each fuel cell 16 is used for the generating reaction. In addition, a portion of the air rising above exhaust collection chamber 18 is used to combust the fuel jetted from exhaust collection chamber 18 jet openings 18d. Exhaust gas produced by combustion and air not used for electrical generation or combustion passes through small holes 64a and flows into exhaust gas discharge flow path 21. Exhaust gas and air flowing into exhaust gas discharge flow path 21 is discharged after carbon monoxide is removed by combustion catalyst 60.
Thus when each fuel cell 16 rises to approximately 650° C. at which generation is possible, and reformed fuel flows into the interior (fuel electrode side) of each fuel cell 16 and air flows on the outside (air electrode side) thereof, a starting power is generated by chemical reaction. In this state, when inverter 54 is connected to bus bars 80 drawn out from fuel cell housing container 8, power is extracted from each fuel cell 16 and electrical generation is implemented.
In solid oxide fuel cell system 1 of the embodiment, generating air is jetted from the oxidant gas jetting pipe 74 disposed at the center of generating chamber 10 and rises up through generating chamber 10 in the uniform gap between exhaust collection chamber 18 and inside cylindrical member 64 and in the uniform gap between exhaust collection chamber 18 and oxidant gas jetting pipe 74. Therefore the flow of air inside generating chamber 10 is an essentially completely axially symmetrical flow, and air flows homogeneously around each fuel cell 16. Temperature differences between fuel cells 16 are thereby suppressed, and a uniform starting power can be produced by each fuel cell 16.
Next, referring to
First, as shown in
Next, as shown in
By the insertion of positioning shafts 110a into fuel cells 16, one end portion of fuel cells 16 is positioned relative to positioning shafts 110a. Since lower fixture 110 is positioned relative to inside cylindrical member 64, one end of fuel cell 16 is accurately positioned relative to inside cylindrical member 64, a constituent of fuel cell module 2. Moreover, because the bottom end of each fuel cell 16 contacts the base end surface 110b of positioning shafts 110a, the bottom ends of all fuel cells 16 are positioned in the same plane. That is, the projection length of each fuel cell 16 from first affixing member 63 is fixed. On the other hand, because there is variability in the lengths of fuel cells 16 due to manufacturing tolerances, the heights of the top ends of the fuel cells 16 are not perfectly uniform.
Therefore in this step, the one end of each fuel cell 16 inserted into each of the insertion holes 63a is positioned relative to the inside cylindrical member 64 that makes up fuel cell module 2.
Next, as shown in
In addition, as shown in
Therefore in this step, the other end of the fuel cells 16 inserted into insertion holes 18c of collection chamber lower member 18b is registered by upper fixture 112 relative to the inside cylindrical member 64, which constitutes fuel cell module 2.
Thus the top end portion and bottom portion of each of the fuel cells 16 are accurately positioned relative to inside cylindrical member 64. In this state, an essentially fixed gap is formed between the outer circumferential surface of each fuel cell 16 and the insertion holes 18c in collection chamber lower member 18b, as well as the insertion holes 63a in first affixing member 63. That is, each fuel cell 16 is positioned at a predetermined position relative to fuel cell module 2 (inside cylindrical member 64), in a state whereby each insertion hole 18c in collection chamber lower member 18b is separated by a predetermined distance from the edge portion of insertion hole 63a on first affixing member 63. A small curve is present in the fuel cells 16 due to manufacturing tolerances, however since fuel cells 16 are correctly positioned relative to fuel cell module 2 at the top and bottom ends, the gap between the outer circumferential surface of fuel cells 16 and each of the insertion holes can be made essentially uniform.
Thus in a state whereby each of the fuel cells 16 is positioned, an adhesive applying step is implemented in which ceramic adhesive is injected onto collection chamber lower member 18b by an adhesive injection apparatus, being an adhesive application apparatus. An adhesive filling frame 18e extending in a ring shape to surround all of insertion holes 18c is disposed on collection chamber lower member 18b (
As shown in
As shown in
Next we explain the dry hardening step for dry hardening ceramic adhesive. The dry hardening step has a workable hardening step for hardening the ceramic adhesive to a state in which the next manufacturing step can be executed, and a solvent elimination step for hardening the ceramic adhesive to a state in which it can withstand the temperature rise in start up step of solid oxide fuel cell system 1. Below we explain the workable hardening step.
In the embodiment, ceramic adhesives containing aluminum oxide, quartz, alkali metal silicates, silicon dioxide, and water are used as ceramic adhesive in the embodiment, and these ceramic adhesives are hardened by a dehydration condensation reaction. That is, ceramic adhesives are hardened by the evaporation of included water, and of moisture produced by the condensation reaction. Therefore an extremely long time period is required to dry and harden ceramic adhesives at room temperature, so it is common in industry to harden using a drying oven or the like. However, because moisture is evaporated and volume shrinks when ceramic adhesive is hardened, cracks form in the ceramic adhesive layer with normal drying and hardening.
Cover member 19c is a circular metal plate; a large circular opening for inserting the cylindrical portion of collection chamber lower member 18b is formed at the middle thereof, and multiple insertion holes for inserting each of the fuel cells 16 are formed in the periphery thereof. In the embodiment, the position and size of the insertion holes is constituted to be the same as that of insertion holes 18c in collection chamber lower member 18b.
As shown in
Note that each of fuel cells 16 is adhered with ceramic adhesive to the lead film layer 104a, 104b parts thereof (
As shown in
In the workable hardening step shown in
Thus by gradually raising the temperature, moisture in the ceramic adhesive layer 118 vaporizes slowly. However, because ceramic adhesive layer 118 is covered by cover member 19c, moisture does not directly vaporize from the part covered by cover member 19c. Therefore moisture in ceramic adhesive layer 118 is vaporized slowly through prominence 118a or hanging portion 118b on the periphery of fuel cells 16. Because of this concentration of moisture in prominence 118a and hanging portion 118b, which are exposed to outside air, it is difficult for these parts to dry. Since cover member 19c and collection chamber lower member 18b are made of metal with a high coefficient of thermal conductivity, heating of ceramic adhesive layer 118 is averaged even in cases where there is localized heating due to temperature unevenness, etc. within drying oven 116. This enables the suppression of cracks caused by sudden localized drying of the ceramic adhesive layer 118. On the other hand, because each of the fuel cells 16 is made of ceramic with a low coefficient of thermal conductivity, it is difficult for heat to transfer to the prominence 118a and hanging portion 118b around the fuel cells 16, and the drying and hardening of these parts is thus more gradual than other parts.
Thus in the embodiment, because drying of the prominence 118a and hanging portion 118b on each of the fuel cells 16 is gradual, what is important for securing airtightness is to prevent cracking in the periphery of each of the fuel cells 16. Vaporization of moisture from the ceramic adhesive also results in reduction in the volume of the ceramic adhesive layer 118, producing “shrinkage.” However in the peripheral part of each of the fuel cells 16, because of the formation of prominence 118a and hanging portion 118b, the ceramic adhesive layer is thicker than in other parts, therefore gaps between fuel cells 16 and the ceramic adhesive layer caused by the occurrence of shrinkage can be prevented. Thus airtightness can be secured in the adhered portion between each of the fuel cells 16 and each of the insertion holes 18c. Cover member 19c, which is disposed to cover the parts filled with ceramic adhesive, suppresses the occurrence of cracks when the ceramic adhesive hardens.
Because of the formation of prominence 118a and hanging portion 118b, there is little through-puncturing of the ceramic adhesive by cracks even if a few cracks do occur in these parts, so airtightness can be reliably secured. Therefore prominence 118a and hanging portion 118b function as gas leak prevention portions for suppressing the occurrence of cracks caused by shrinkage when the ceramic adhesive hardens. Note that hardened ceramic adhesive is porous, and although airtightness relative to hydrogen or air is not total, a ceramic adhesive filled and hardened without gaps provides sufficient airtightness for practical use. In this Specification, the term “securing airtightness” means there are no leaks of moisture or air at a practical level.
In the workable hardening step shown in
Next, after performing the workable hardening step, lower fixture 110 and upper fixture 112 are removed. Furthermore, as shown in
Furthermore, as shown in
In this state, assembly is placed in drying oven 116, and the second workable hardening step is implemented. In this workable hardening step, as well, the temperature inside drying oven 116 is controlled as shown by the solid line in
Next, as shown in
Furthermore, as shown in
Next, as shown in
In addition, a dispersion chamber seal 126, being a circular thin plate on the ceramic adhesive layer 124 filled into the circular gap between the outer circumferential surface of dispersion chamber bottom member 72 and the inner circumferential surface of inside cylindrical member 64, is disposed as shown in
When these ceramic adhesives are dried, dispersion chamber seal 126 and center seal plate 130 prevent the sudden drying out of the surfaces of each of the adhesive layers, thereby suppressing the occurrence of cracks in ceramic adhesive layers 124 and 128. Also, ceramic adhesive layer 124, which is filled into the gap between inside cylindrical member 64 and dispersion chamber bottom member 72, is heated and hardened uniformly because of its circular shape, and the occurrence of cracking is thereby suppressed. For example, if the ceramic adhesive layer is formed in a rectangular shape, the speed of hardening differs between the corner portions and other parts, therefore the parts which dry and harden first are stretched by shrinkage of the ceramic adhesive and therefore tend to crack more easily. Stress is also more easily concentrated at the corner portions due to shrinkage of the ceramic adhesive such that cracks can easily occur. By contrast, because ceramic adhesive layer 124 in the embodiment is circular in shape, stress caused by shrinkage of the adhesive is not concentrated as drying and hardening proceed, therefore the occurrence of cracking associated with hardening of the ceramic adhesive can be suppressed. As a variant example, ceramic adhesive layer 124 can be constituted in an oval shape.
After completion of the third workable hardening step, the top and bottom of the assembly are inverted, and as shown in
Note that as a variant example, the invention can be constituted in such a way that the members are formed so the gap between collection chamber upper member 18a and collection chamber lower member 18b is oval in shape, and exhaust collection chamber 18 is formed by filling this gap with ceramic adhesive. Note that as a variant example, the invention can be constituted in such a way that the members are formed so the gap between the cylindrical portion of collection chamber lower member 18b and the opening portion of collection chamber upper member 18a is oval in shape, and exhaust collection chamber 18 is formed by filling this gap with ceramic adhesive.
In the state, the assembly is again placed into drying oven 116 (not shown in
Next, as shown in
Note that as a variant example, the invention can be constituted so that inside cylindrical container 68 and external cylindrical container 70 are adhered using ceramic adhesive. In this case, ceramic adhesive is filled into the circular gap between inside cylindrical container 68 and external cylindrical container 70, affixing these members in an airtight manner. Alternatively, the invention can be constituted in such a way that these members are configured so the gap between the inside cylindrical container and the outside cylindrical container has an oval shape, and ceramic adhesive is filled into this oval shaped gap to affix these members in an airtight manner.
As shown in
A circular exhaust passage seal 134 is disposed to cover filled-in ceramic adhesive layer 132. This exhaust passage seal 134 functions as a cover member for suppressing the occurrence of cracks when the ceramic adhesive hardens. In the state, the assembly is placed into drying oven 116 (not shown in
In this workable hardening step, as shown in
That is, by implementing a fifth workable hardening step, the newly filled ceramic adhesive layer 132 is heated and hardened, and external cylindrical member 66 and inside cylindrical container 68 are adhered in an airtight manner. Thus the joint portion between external cylindrical member 66, which is a constituent part of the flow path guiding oxidant gas, and inside cylindrical container 68, is joined in an airtight manner by ceramic adhesive. At this time, the operation of exhaust passage seal 134 and the effect from the circular ceramic adhesive layer 132 are the same as for the above-described dispersion chamber seal 126 and ceramic adhesive layer 124. Also, the ceramic adhesive layers hardened in first through fourth workable hardening steps have respectively been subjected to multiple workable hardening steps, therefore gradual drying has been repeatedly applied, and a stable state of the ceramic adhesive layers is obtained while avoiding the risk of cracking.
In particular, the workable hardening steps applied to the cell joining portion between each of the fuel cells 16 and collection chamber lower member 18b is executed in the first of the five implemented workable hardening steps. Also, after the last implemented workable hardening step applied to the cell joining portion, that is, the workable hardening step applied to the joint portion between each of the fuel cells 16 and first affixing member 63 (the second workable hardening step), three iterations of workable hardening steps are implemented on constituent parts other than the fuel cells 16. Therefore four or more workable hardening steps are implemented on each of the cell joint portions, and an extremely stable state is obtained for the ceramic adhesive layers in each of the cell joint portions. A major problem results if airtightness is compromised in the cell joint portions, but airtightness can be reliably secured by repeatedly applying these workable hardening steps.
The workable hardening steps applied between external cylindrical member 66 and inside cylindrical container 68 after the workable hardening steps applied to the cell joint portion have the purpose of securing airtightness in the exhaust gas discharge flow path 21 which conducts exhaust; even if by some chance airtightness is compromised here, the resulting negative effects would be less than when airtightness is compromised at the joint portion. In addition, as shown in the variant example described above, when inside cylindrical container 68 and external cylindrical container 70 are joined by ceramic adhesive, the workable hardening step applied to this joint portion is implemented after the workable hardening step applied to the cell joint portion. The joint portion between inside cylindrical container 68 and external cylindrical container 70 has the purpose of securing the airtightness of oxidant gas supply flow path 22, and even if by some chance airtightness is compromised here, the resulting negative effects would be less than when airtightness is compromised at the cell joint portion.
Continuing after implementing the fifth workable hardening step, which is the last workable hardening step, a solvent elimination and hardening step is implemented (
It is thus desirable to execute the solvent elimination and hardening step at a temperature higher than the workable hardening step and lower then during the electrical generation operation by solid oxide fuel cell system 1. The ceramic adhesive used in the embodiment can be dried at a temperature of 200° C. or below to a state capable of withstanding the temperature rise at the start up step, and the solvent elimination and hardening step is preferably executed at a temperature equal to or greater than 100° C. and less than or equal to 200° C. The ceramic adhesive used in the embodiment can be dried at a temperature of 200° C. or below to a state capable of withstanding the temperature rise at the start up step, and the solvent elimination and hardening step is preferably executed at a temperature equal to or greater than 100° C. and less than or equal to 200° C.
Ceramic adhesive filled in during the adhesive application step then passes through at least one workable hardening step, therefore even if the temperature of the drying oven 116 is raised to approximately 150° C. in the solvent elimination and hardening step, no large cracks will occur in the ceramic adhesive layer. Note that even after completion of the solvent elimination and hardening step, there is moisture remaining in each of the ceramic adhesive layers, but since this is a minute amount, problems such as cracking do not occur even if the temperature inside fuel cell module 2 climbs to the electrical generation temperature level. Also, in the embodiment the solvent elimination and hardening step is carried out only once after multiple repetitions of the adhesive application step and the workable hardening step, and then a final workable hardening step, are executed, but it is also possible to implement the solvent elimination and hardening step multiple times during the manufacturing process.
As a variant example, a solvent elimination and hardening step can also be added between the workable hardening step S1 and step S16 in
First, when implementing the manufacturing method of this variant example, the heating in the first half of
Next, the second solvent elimination and hardening step shown in
The temperature of air introduced into generating chamber 10 through heated air introduction pipe 136 is raised a little at a time over a long period of time up to the temperature at which solid oxide fuel cell system 1 can generate electricity. In this variant example, as shown by the solid line in
By thus gradually raising the temperature, the solvent remaining in the ceramic adhesive layer is heated a little at a time and vaporized. The occurrence of excessive cracks due to sudden volumetric expansion and vaporization of the solvent is thus suppressed. Also, in the second solvent elimination and hardening step the temperature of each of the ceramic adhesive layers in the generating chamber 10 is raised up to the actual temperature during electrical generation operation. As a result, even if the temperature of a finished solid oxide fuel cell system 1 is suddenly raised during the startup step, the absence of excessive cracking in the ceramic adhesive layer can be more reliably assured.
Also the second solvent elimination and hardening step, in which the temperature inside the generating chamber 10 is raised to approximately 650° C., can be implemented at the end of step S15 rather than at the end of the assembly process (after
On the other hand in the second solvent elimination and hardening step inert gas is introduced from fuel gas supply pipe 90 in parallel with the introduction of heated air from heated air introduction pipe 136. As indicated by the dotted arrow in
In this variant example, nitrogen gas is used as the inert gas. The introduced nitrogen gas is heated so as to be able to heat the interior of each of the fuel cells 16. In this way, inert gas is introduced into each of the fuel cells 16, and the oxidant gas (air) in each of the fuel cells 16 and the reforming section 94 is thereby discharged. Oxidation of the fuel electrodes in each of the fuel cells 16 and oxidation of the reforming catalyst in reforming section 94 when the temperature is raised during the electrical generation operation can thus be prevented. Also, in the second solvent elimination and hardening step, hydrogen gas maybe supplied from the fuel gas supply pipe 90 instead of inert gas. In such cases, the hydrogen gas passes over the fuel electrode side in each of the fuel cells 16, which have been raised to a high-temperature, therefore the fuel electrodes can be reduced. Note that in the second solvent elimination and hardening step, inert gas is supplied until the temperature in each of the fuel cells 16 has risen sufficiently, and after the temperature has risen, inert gas is switched over to hydrogen gas.
Note that in this variant example it is possible after the first solvent elimination and hardening step to raise the temperature up to the temperature of the second solvent elimination and hardening step without reducing the temperature. In this case as well it is necessary to supply inner gas from fuel gas supply pipe 90. Of the first and second solvent elimination and hardening steps, it is possible to eliminate the first solvent elimination and hardening step. In such cases, the rise in the temperature of supplied heated air is made even more gradual during the second solvent elimination and hardening step; it is desirable to raise the temperature over 4 or more hours.
In a state in which oxidant gas is supplied to the air electrode side of each of the fuel cells 16, hydrogen gas is supplied to the fuel efficiency side, and the temperature of each of the fuel cells 16 is sufficiently raised, a voltage is generated between the two bus bars 80 connected to fuel cells 16. By measuring the voltage between these bus bars 80, a determination can be made as to the go/no go status of the joint portions of each of the fuel cells 16 and the assembly. The measurement of voltage is carried out with no current flowing between the bus bars 80. When there is a problem in the fuel cells 16 themselves, the voltage produced between bus bars 80 drops. Also, if a large fuel leak occurs at the joint portion between each of the fuel cells 16 and the first affixing member 63, or at the joint portion between each of the fuel cells 16 and the collection chamber lower member 18b, sufficient fuel gas is not supplied to the fuel electrode, so the voltage drops. Thus in the second solvent elimination and hardening step, reduction of the fuel electrodes on each of the fuel cells 16 and inspection of the semi-finished solid oxide fuel cell system 1 product can be accomplished simultaneously.
It is also possible to change the time for the workable hardening step set in this embodiment. For example the time for the initially implemented workable hardening step could be made shorter than the time for subsequently performed workable hardening steps. The joint portion on which the workable hardening step is performed at the beginning is treated to a greater number of iterations of workable hardening steps than subsequently treated joint portions, therefore the risk of cracking can be sufficiently reduced while shortening the time required for the workable hardening step.
After fuel cell housing container 8 is completed by the above-described manufacturing processes, various parts are attached to complete a solid oxide fuel cell system 1. The lower fixture 110 (first positioning apparatus), upper fixture 112 (second positioning apparatus), adhesive injection apparatus 114, drying oven 116 (adhesive hardening apparatus), and heating controller 116a constitute the manufacturing equipment for a solid oxide fuel apparatus used in the above-described manufacturing method for solid oxide fuel cell system 1.
In the solid oxide fuel cell system 1 of the present embodiment of the invention, prominence 118a and hanging portion 118b, being gas leak suppression portions, are formed by ceramic adhesive layers around the periphery of each of the fuel cells 16 on the joint portions between each of the fuel cells 16 and collection chamber lower member 18b (
Also, in the solid oxide fuel cell system 1 of the present embodiment, when adhering ceramic adhesive, a pool of the ceramic adhesive is formed in the surrounding part of fuel cells 16, and by hardening this pool, prominence 118a and hanging portion 118b are formed and the ceramic adhesive is made thicker (
In addition, in solid oxide fuel cell system 1 of the present embodiment, hardening of the ceramic adhesive in the periphery portion of each of the fuel cells 16 is made gradual, so adhesive in prominence 118a and hanging portion 118b hardens later, reducing the likelihood of cracking in these parts and enabling the suppression of fuel gas leaks.
Also, in solid oxide fuel cell system 1 of the present embodiment, the portion away from the surrounding part of each of the fuel cells 16 is covered by a cover member 19c, 67 (
In addition, in the solid oxide fuel cell system 1 of the present embodiment, ceramic adhesive prior to hardening is covered by cover members 19c and 67, and prominence 118a and hanging portion 118b are formed by the pressing out of ceramic adhesive at the peripheral parts of each of the fuel cells 16. Ceramic adhesive pools can thus be formed on the surrounding portions of fuel cells 16 using a simple structure, thereby forming prominence 118a and hanging portion 118b.
We have described above a preferred embodiment of the present invention, but various changes may be added to the above-described embodiments.
In particular, in the above-described embodiment the workable hardening step applied to each joint portion is applied to the joint portion between collection chamber lower member 18b and fuel cells 16, the joint portion between fuel cells 16 and first affixing member 63, the joint portion between collection chamber upper member 18a and collection chamber lower member 18b, the joint portion between dispersion chamber bottom member 72 and inside cylindrical member 64, and the joint portion between external cylindrical member 66 and inside cylindrical container 68, in that order, but as a variant example it is also possible to constitute the invention by joining fuel cells from the bottom end portion.
In this case, the workable hardening step is applied to the joint portion between the fuel cells 16 and first affixing member 63 the first time, the joint portion between collection chamber lower member 18b and fuel cells 16 the second time, the joint portion between collection chamber upper member 18a and collection chamber lower member 18b the third time, the joint portion between dispersion chamber bottom member 72 and inside cylindrical member 64 the fourth time, and the joint portion between external cylindrical member 66 and inside cylindrical container 68 the fifth time. In this variant example, the workable hardening step applied to the joint portion joining fuel cells with other constituent parts is carried out during the first half of the five iterations of the workable hardening step, that is, in the first and second iterations. Thus the largest number of workable hardening steps is performed on the cell joint portions which have particular need to secure airtightness, and airtightness can be secured in the cell joint portions.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2013-135084 | Jun 2013 | JP | national |
| 2013-135085 | Jun 2013 | JP | national |
