JP5110345B2 - Stack structure of solid oxide fuel cell - Google Patents

Description

    The present invention relates to a stack structure of a fuel cell, and more particularly to a stack structure of a solid oxide fuel cell operating at a high temperature.

  Examples of the stack structure of a solid oxide fuel cell that operates at a high temperature include a stack structure including a cell plate holding a single cell, a separator plate, and a component such as a flange. In the case of such a stack structure of a solid oxide fuel cell, a large number of components such as between a cell plate and a separator plate, and between a separator plate and a flange are exposed to high temperature and low temperature environments, and oxidizable. In a reducing atmosphere, gas sealing properties that prevent leakage of gases such as hydrogen, natural gas, and air, and sufficient bonding strength and electrical insulation are required.

In recent years, with the improvement of the low temperature performance of solid oxide fuel cells, there is a tendency to use metal materials, such as ferritic stainless steel, for separator plates and flanges. A large tensile or compressive force is applied to the joint between the two due to thermal deformation of the metal material that occurs as the temperature rises and falls. Development is underway.
JP 2003-238201 A JP 2002-203581 A JP 2003-311743 A

  However, when a gas seal part for a fuel cell made of a glass-based bonding material is used at a bonded portion of a conventional fuel cell stack structure, the glass-based bonding material is a brittle material, although the bonding force is excellent. Therefore, the tensile and compressive forces generated by the thermal deformation of the metal material are directly applied to the glass-based bonding material because of its excellent bonding force, and the glass-based bonding material itself is cracked. It was.

  Moreover, in the gas seal part for a fuel cell described above, for example, when it is used for joining a separator plate and a flange, a large amount of both is used for the convenience of increasing the plane accuracy or absorbing the variation in parallelism. It is necessary to fill a glass-based bonding material to form a thick glass layer. Thus, when a thick glass layer is formed, there is a problem that the risk of cracking increases. It has been a conventional problem to solve the problem.

  The present invention has been made by paying attention to the above-described conventional problems, and maintains excellent gas sealability and bondability even when a tensile force or a compressive force generated by thermal deformation of a component is loaded. It is an object of the present invention to provide a stack structure of a solid oxide fuel cell.

  A stack structure of a solid oxide fuel cell according to the present invention is a metal cell having a thin plate shape that holds a single cell and has a fuel gas introduction hole, a fuel gas discharge hole, an oxidizing gas introduction hole, and an oxidizing gas discharge hole In a stack structure of a solid oxide fuel cell comprising a plate and a metal separator plate having a thin plate shape having a fuel gas introduction hole, a fuel gas discharge hole, an oxidant gas introduction hole, and an oxidant gas discharge hole In addition, a frame formed by covering and connecting a plurality of blocks arranged at appropriate intervals with a metal foil is provided on the outer edge portion of one of the cell plate and the separator plate, and the cell plate and the separator plate are provided via this frame. The structure of the stack structure of the solid oxide fuel cell is used as a means for solving the above-described conventional problems.

  In the stack structure of the solid oxide fuel cell of the present invention, the cell plate and the separator plate are both made of a thin plate-like metal, and a plurality of blocks are made of a deformable metal foil that does not transmit gas. Since the cell plate and the separator plate are joined via the covering frame, the whole can be deformed by heat.

  When the cell plate or separator plate is thermally deformed and a tensile force or compressive force is applied to the frame, the frame also deforms and absorbs the tensile force or compressive force. There is little possibility that a defect will occur, and therefore, excellent gas sealability and bondability between the cell plate and the separator plate will be ensured.

  According to the present invention, since it has the above-described configuration, it is needless to say that excellent gas sealability and bondability between the cell plate and the separator plate can be ensured, and tensile force and compression generated by thermal deformation of both. Even when a force is applied, it is possible to maintain an excellent gas sealing property and bonding property, which is very excellent.

  In the solid oxide fuel cell stack structure of the present invention, by adopting a thin plate-like metal for the cell plate and the separator plate, it is possible to impart a flexible property to heat to these components. Ferritic stainless steel (SUS430) or the like can be suitably used as the metal employed in these cell plates and separator plates, but is not necessarily limited.

  At this time, if the thickness of both plates is less than 0.03 mm, it becomes difficult in terms of strength to support the single cell or to counter the pressing pressure of the current collector disposed between both plates. If the thickness of the plate is thicker than 0.1 mm, the thermal deformation as a whole increases so that the gas sealing property and the bonding property are hindered. Therefore, the thickness of the cell plate and the separator plate is set to 0.03 to 0.1 mm. Is desirable.

  Further, in the solid oxide fuel cell stack structure of the present invention, the frame is formed by covering a plurality of blocks with a deformable metal foil that does not transmit gas, so that the frame is flexible to heat. In addition, since the gaps between the plurality of blocks are closed by the metal foil, it can function as a partition for ensuring gas tightness.

  In this case, ferritic stainless steel (SUS430) or the like can be suitably used for the block, but it is not necessarily limited. For joining the metal foil and the plurality of blocks, a glass-based bonding material described later is used. Can be used.

  Furthermore, in the stack structure of the solid oxide fuel cell of the present invention, the metal foil of the frame may be made of, for example, a stainless steel metal foil, and the thickness thereof is from the viewpoint of economy and durability. 10 to 50 μm is desirable. Since such a metal foil is thin and easily deformed, it flexibly follows the thermal deformation of the cell plate and the separator plate. The metal foil also has a function of forming a bonding interface and a function of a partition wall that ensures gas tightness.

  Furthermore, in the stack structure of the solid oxide fuel cell according to the present invention, the fuel gas introduction holes communicated with the fuel gas introduction holes, the fuel gas discharge holes, the oxidizing gas introduction holes, and the oxidizing gas discharge holes of the cell plate and the separator plate. The fuel gas discharge hole, the oxidation gas introduction hole, and the oxidation gas discharge hole can be provided in the frame. Adjacent blocks are arranged close to each other at positions near the holes, and adjacent blocks are arranged at positions between the fuel gas introduction hole, the fuel gas discharge hole, the oxidizing gas introduction hole, and the oxidizing gas discharge hole. It is possible to employ a configuration in which the gaps between them are arranged sparsely.

  As described above, the fuel gas introduction hole, the fuel gas discharge hole, the oxidant gas introduction hole, and the oxidant gas discharge hole in the vicinity of the frame are arranged close to each other at close positions. If the gaps between adjacent blocks are arranged sparsely at positions between the holes, the fuel gas discharge holes, the oxidizing gas introduction holes, and the oxidizing gas discharge holes, the side portions with large deformation amounts, that is, the fuel gas introduction holes , Fuel gas discharge holes, oxidant gas introduction holes, and oxidant gas discharge holes can be provided with more flexibility. As a result, the fuel gas introduction hole, the fuel gas discharge hole, the oxidation gas, Bonding at each hole portion of the gas introduction hole and the oxidizing gas discharge hole is made even stronger.

  Furthermore, in the stack structure of the solid oxide fuel cell of the present invention, the block located between each of the fuel gas introduction hole, the fuel gas discharge hole, the oxidizing gas introduction hole and the oxidizing gas discharge hole in the frame is arranged on the single cell side. It is possible to adopt a configuration in which the functions of the reinforcing ribs are provided by being arranged close to each other. In this case, a plurality of blocks having the function of the reinforcing ribs prevent the gap between the cell plate and the separator plate from being crushed. Therefore, the gas flow path is secured, and in addition, since the plurality of blocks are arranged close to the single cell side, it also functions as a rectifying plate, so that the fuel gas introduced from the fuel gas introduction hole is a single cell. Will be evenly distributed.

  Furthermore, in the stack structure of the solid oxide fuel cell of the present invention, the block of the frame has a circular or elliptical cross section, and the block of the frame is placed on the outer edge portion of either the cell plate or the separator plate. It is possible to adopt a configuration in which a concave portion to be engaged is provided. With this configuration, the bonding area of the frame with respect to either the cell plate or the separator plate is increased as compared with the case where the block of the frame has a prismatic shape. It becomes.

  Furthermore, in the stack structure of the solid oxide fuel cell according to the present invention, the block of the frame is formed in a pipe shape, and a concave portion that engages with the block of the frame is formed on one outer edge portion of the cell plate or the separator plate. This configuration increases the bonding area of the frame to either the cell plate or the separator plate as in the case where the frame block has a circular or elliptical cross section. In addition, flexibility in the stacking direction of the cell plate and the separator plate can be imparted.

  Furthermore, in the stack structure of the solid oxide fuel cell of the present invention, a glass layer made of a glass-based bonding material is formed on the metal foil surface of the frame provided on the outer edge part of either the cell plate or the separator plate, This glass layer can be configured as a bonding layer with the other outer edge portion of the cell plate and the separator plate.

At this time, the difference in thermal expansion coefficient between the glass layer made of the glass-based bonding material and the metal foil of the frame, and the glass layer made of the glass-based bonding material, and the other plate of the cell plate and the separator plate are configured. The difference in thermal expansion coefficient between the glass layer made of glass-based bonding material and the metal foil of the frame is that if there is a large difference in the thermal expansion coefficient with the thin metal plate, the glass layer interface may crack. In addition, the difference in thermal expansion coefficient between the glass layer made of the glass-based bonding material and the metal thin plate constituting either one of the cell plate and the separator plate is 2.0 × 10 ⁻⁶ (1 / K) or less, preferably 1.5 × 10 ⁻⁶ (1 / K) or less.

  The glass layer is firmly bonded to the metal foil of the frame and the other outer edge portion of the cell plate and the separator plate, respectively. Follow flexibly.

  And as mentioned above, if the glass layer made of glass-based bonding material is thin and easily deformed, it will flexibly follow the thermal deformation of the cell plate and separator plate, but cracking will occur beyond the limit that can be followed, for example. Even if it is a case, since the crack direction is local to the layer thickness of the glass layer, it has little influence on the bonding force and gas seal performance.

  In this case, even if the material of the cell plate and the separator plate is a metal material such as stainless steel, the frame has a glass layer made of a glass-based bonding material having excellent electrical insulation on the surface. Electrical insulation between the cell plate and the separator plate can also be secured, and sufficient bonding strength and insulation can be secured by setting the thickness of the glass layer to 10 to 50 μm.

The glass-based bonding material used for the glass layer can be selected within the range of the above-mentioned coefficient of thermal expansion. However, when the metal foil of the cell plate, the separator plate, and the frame is ferritic stainless steel, It is possible to select and use barium oxide / alumina / silica / calcia glass as the glass contained within the range of the expansion coefficient, specifically, 52% BaO-3% Al ₂ O ₃ − _{33SiO 2 -12% CaO, 42%} BaO-Al 2 O 3 -35SiO 2 -9% CaO-B 2 O 3 -ZnO-PbO-V 2 O 5, 43% BaO-Al 2 O 3 -35SiO 2 -9 % CaO—B ₂ O ₃ —PbO—V ₂ O ₅ can be selected and used.

  In addition to the bonding of the cell plate and the separator plate, the glass layer is bonded between each block of the frame and the metal foil, between each block of the frame and the cell plate and the separator plate, or between the metal foils of the frame. It can also be used for bonding.

  In a preferred embodiment of the stack structure of a solid oxide fuel cell according to the present invention, a ferrite stainless steel plate of 120 mm × 120 mm × 0.05 mm is used as a cell plate, and the same is made of ferrite stainless steel of 120 mm × 120 mm × 0.05 mm. The plate material is a separator plate, and a 70 mm × 70 mm × 0.6 mm fuel electrode supporting cell is placed in the center of the cell plate.

  Then, a plurality of blocks (5 mm × 5 mm × 1.0 mm ferritic stainless steel blocks) arranged at 1 mm intervals on the outer edge portion of the cell plate are covered with a metal foil (ferritic stainless steel foil having a thickness of 0.03 mm). It is possible to adopt a configuration in which a frame is formed by connecting and a cell plate and a separator plate are bonded to each other through a glass layer made of a glass-based bonding material formed on the metal foil surface of the frame to form a stack structure.

In the above-described stack structure of the solid oxide fuel cell of the present invention, when joining the fuel electrode supporting cell to the cell plate, first, glass particles having a particle size of 10 μm are mixed in a 50 weight ratio, ethyl cellulose in a 30 weight ratio, and The glass-based bonding material is adjusted by mixing 20 weight ratio of butyl acetate, and then the glass-based bonding material is applied to the cell mounting portion of the cell plate to form a glass layer, and then an electrolyte is formed on the glass layer. The fuel electrode supporting cell is arranged so that the membrane becomes an adhesive surface, and the glass layer is melted by heating at 850 ° C. for 15 minutes in the atmosphere while applying a load (10 g / mm ² ) to the adhesive surface. The fuel electrode supporting cell is joined to the cell plate by softening.

  In the above-described stack structure of a solid oxide fuel cell according to the present invention, when manufacturing a frame, first, as shown in FIG. 3, a metal foil 12 is bonded to the outer edge portion of the cell plate 3, and thereafter As shown in FIG. 4, the plurality of blocks 11 are arranged on the outer edge portion of the cell plate 3 and bonded, and then, as shown in FIG. The metal foil 12 is folded and bonded.

When manufacturing the above-described stack structure of the solid oxide fuel cell according to the present invention, as shown in FIG. 1, the glass-based bonding material is applied to the surface of the metal foil 12 of the frame 10 to form a glass layer. After the separator plate 4 is placed on the glass layer, the glass layer is heated in the atmosphere at 850 ° C. for 15 minutes while applying a load (20 g / mm ² ) to the bonding surface. It is possible to employ a configuration in which the cell plate 3 and the separator plate 4 are joined by melting and softening.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example.

[Example 1]
1 to 6 show an embodiment of a stack structure of a solid oxide fuel cell according to the present invention. As shown in FIGS. 1 and 2, the stack structure 1 of the solid oxide fuel cell includes: A metal cell plate 3 having a thin plate shape and holding a single cell 2 and having a fuel gas introduction hole 3fi, a fuel gas discharge hole 3fo, an oxidation gas introduction hole 3ai, and an oxidation gas discharge hole 3ao; And a metal separator plate 4 having a thin plate shape having a fuel gas introduction hole 4fi, a fuel gas discharge hole 4fo, an oxidant gas introduction hole 4ai, and an oxidant gas discharge hole 4ao. (Only one layer (one unit) is shown in FIG. 1).

  On the outer edge portions of the front and back surfaces of the cell plate 3, there are provided frames 10 formed by covering and connecting a plurality of blocks 11 arranged at appropriate intervals with a metal foil 12, and the cell plate 3 and the separator plate 4. Are bonded via a glass layer 6 made of a glass-based bonding material formed on the surface of the metal foil 12 of the frame 10. In this case, in the portions located at the four corners of the cell plate 3 in the frame 10, the fuel gas introduction holes 3fi and 4fi, the fuel gas discharge holes 3fo and 4fo, the oxidation gas introduction holes 3ai and 4ai of the cell plate 3 and the separator plate 4 and The oxidizing gas discharge holes 3ao and 4ao can communicate with each other.

  In this example, a 120 mm × 120 mm square and 0.05 mm thick ferritic stainless steel plate is used as the cell plate 3, and a 120 mm × 120 mm square and 0.05 mm thick ferritic stainless steel plate is also used as the separator plate 4. In the center of the cell plate 3, a 70 mm × 70 mm square fuel electrode supporting cell (Ni + YSZ; fuel electrode / YSZ; electrolyte membrane / LSCF; air electrode) as a single cell 2 is arranged. At the same time, nickel wool as the current collector 5 was disposed in the center of the separator plate 4 to form an anode side separator plate 4 (4A) and a cathode side separator plate 4 (4B).

The plurality of blocks 11 of the frame 10 are 5 mm × 5 mm × 1.0 mm ferritic stainless steel blocks, and these blocks 11 arranged at 1 mm intervals are made of 0.03 mm thick ferritic stainless steel foil. with connecting covered with a metal foil 12, the glass layer 6 formed on the surface of the metal foil 12 of the frame _10, with _{52% BaO-3% Al 2} O 3 -33SiO 2 -12% CaO -based glass.

  In producing the above-described stack structure 1 of the solid oxide fuel cell of the present invention, first, as shown in FIG. 3, after bonding the metal foil 12 to each outer edge portion on the front and back surfaces of the cell plate 3, As shown in FIG. 4, after the plurality of blocks 11 are arranged on the outer edge portion of the cell plate 3 at 1 mm intervals and bonded, the plurality of blocks 11 are wrapped as shown in FIG. Then, the metal foil 12 is folded back and bonded, whereby the frames 10 are respectively installed on the outer edge portions of the front and back surfaces of the cell plate 3.

Next, as shown in FIG. 1, an electrolyte membrane 2a is formed on a glass layer formed by applying 52% BaO-3% Al ₂ O ₃ -33SiO ₂ -12% CaO-based glass to the cell mounting portion of the cell plate 3. The single cell 2 is arranged so that becomes a bonding surface, and the glass layer is melted and softened by heating at 850 ° C. for 15 minutes in the atmosphere while applying a load (10 g / mm ² ) to the bonding surface. The single cell 2 is joined to the cell plate 3.

Then, on the surfaces of the metal foil 12 of the frame 10 located on the front and back surfaces of the cell plate 3, the glass layer 6 by applying the _{52% BaO-3% Al 2} O 3 -33SiO 2 -12% CaO based glass After forming each, the anode-side separator plate 4A and the cathode-side separator plate 4B are placed on the glass layer 6 so as to overlap each other, and a load (20 g / mm ² ) is applied to the bonding surface in the atmosphere. By heating at 850 ° C. for 15 minutes to melt and soften the glass layer, the cell plate 3 and the separator plates 4A and 4B are joined to each other.

  Therefore, as shown in FIG. 6, one unit of the stack structure 1 is set as a test piece in a cylinder 7 equipped with a hydrogen detector 8 and filled with nitrogen gas. In the test, a test was performed in which hydrogen gas was supplied to the stack structure 1 and hydrogen gas permeation (leakage) was detected by the hydrogen detector 8. As a result, hydrogen permeation was not detected in both the room temperature and 700 ° C. environments. Further, even after this test was repeated 50 times, there was no permeation of hydrogen and no cracking occurred in the glass layer.

  As described above, in the stack structure 1 described above, the cell plate 3 and the separator plate 4 are each made of a thin plate-like metal, and in addition, a plurality of blocks are formed with a deformable metal foil 12 that does not transmit gas. Since the cell plate 3 and the separator plate 4 are joined via the frame 10 that covers 11, the entire plate can be deformed by heat.

  Even if the cell plate 3 or the separator plate 4 is thermally deformed and a tensile force or a compressive force is applied to the frame 10, the frame 10 is also deformed and absorbs the tensile force or compressive force. Therefore, there is little possibility that defects such as cracks occur in the joint portion, and therefore, excellent gas sealability and bondability between the cell plate 3 and the separator plate 4 are ensured.

  In the above-described embodiment, the case where the frame 10 is provided on the cell plate 3 is shown. However, as shown in FIG. 7, it is naturally possible to adopt a configuration in which the frame 10 is provided on the separator plate 4.

[Example 2]
FIG. 8 shows another embodiment of the stack structure of the solid oxide fuel cell of the present invention. As shown in FIG. 8, the stack structure 21 of the solid oxide fuel cell is the same as that of the previous embodiment. The difference from the stack structure 1 is that the block 11A of the frame 10 located between the fuel gas introduction hole 3fi, the fuel gas discharge hole 3fo, the oxidation gas introduction hole 3ai, and the oxidation gas discharge hole 3ao of the metal cell plate 3. Is arranged close to the single cell 2 side to have the function of a reinforcing rib, and the other configuration is the same as the stack structure 1 in the previous embodiment.

  In the stack structure 21 of this embodiment, the plurality of blocks 11A having the function of reinforcing ribs prevent the gap between the cell plate 3 and the separator plate 4 from being crushed, so that a gas flow path is secured. Since the plurality of blocks 11A are arranged close to the single cell 2 to function as a rectifying plate, the fuel gas introduced from the fuel gas introduction hole 3fi is evenly distributed to the single cells 2.

[Example 3]
FIG. 9 shows still another embodiment of the stack structure of the solid oxide fuel cell of the present invention. As shown in FIG. 9, the stack structure 31 of the solid oxide fuel cell is the previous embodiment. The stack structure 1 is different from the stack structure 1 in that each of the frames 10 in the vicinity of the fuel gas introduction hole 3fi, the fuel gas discharge hole 3fo, the oxidation gas introduction hole 3ai, and the oxidation gas discharge hole 3ao of the metal cell plate 3 is mutually different. The adjacent blocks 11 are arranged close to each other, and the frames 10 are adjacent to each other at positions between the fuel gas introduction hole 3fi, the fuel gas discharge hole 3fo, the oxidation gas introduction hole 3ai, and the oxidation gas discharge hole 3ao. The other blocks are the same as the stack structure 1 in the previous embodiment.

  In the stack structure 31 of this embodiment, the block 11 of the frame 10 is located at a position close to and away from the fuel gas introduction hole 3fi, the fuel gas discharge hole 3fo, the oxidation gas introduction hole 3ai, and the oxidation gas discharge hole 3ao. Since the arrangement specifications are changed, the portion with a large deformation amount, that is, the portion between each of the fuel gas introduction hole 3fi, the fuel gas discharge hole 3fo, the oxidation gas introduction hole 3ai, and the oxidation gas discharge hole 3ao As a result, it is possible to provide more flexibility, and as a result, the bonding at each of the portions of the fuel gas introduction hole 3fi, the fuel gas discharge hole 3fo, the oxidation gas introduction hole 3ai, and the oxidation gas discharge hole 3ao is all performed. It will be made even stronger.

[Example 4]
FIG. 10 shows still another embodiment of the stack structure of the solid oxide fuel cell according to the present invention. As shown in FIG. 10, the stack structure 41 of the solid oxide fuel cell is the previous embodiment. The difference from the stack structure 1 is that the block 11B of the frame 10 has a circular cross section, that is, the block 11B has a cylindrical shape with a diameter of 2 mm and a length of 5 mm. 3 is provided with a concave portion 3a that engages with the block 11B of the frame 10, and the other configuration is the same as that of the stack structure 1 in the previous embodiment.

  In the stack structure 41 of this embodiment, the block 11B of the frame 10 has a circular cross section, and the recess 3a that engages with the block 11B is provided in the outer edge portion of the cell plate 3. Compared with the case where the ten blocks 11 are in the shape of a prism, the bonding area of the frame 10 to the cell plate 3 is increased.

  At this time, as shown in FIG. 11, the block 11C of the frame 10 is formed into a pipe shape having an outer diameter of 2 mm, an inner diameter of 1 mm, and a length of 5 mm, and the outer edge portion of the cell plate 3 is engaged with the block 11C. A configuration in which the concave portion 3a is provided may be adopted, and when this configuration is adopted, the bonding area of the frame 10 to the cell plate 3 is increased as in the case where the block 11B of the frame 10 has a circular cross section. In addition, flexibility in the stacking direction of the cell plate 3 and the separator plate 4 can be imparted.

[Example 5]
FIG. 12 shows still another embodiment of the stack structure of the solid oxide fuel cell according to the present invention. As shown in FIG. 12, the stack structure 51 of the solid oxide fuel cell has a cylindrical shape as a whole. A ferrite stainless steel plate having a diameter of 120 mm and a thickness of 0.05 mm is used as the cell plate 53, and a ferrite stainless steel plate having a diameter of 120 mm and a thickness of 0.05 mm is used as the separator plate 34. A fuel electrode supporting cell (Ni + YSZ; fuel electrode / YSZ; electrolyte membrane / LSCF; air electrode) having a diameter of 100 mm and a thickness of 0.6 mm as a single cell 52 is arranged in the center of the plate 53 and a separator plate 54. The separator plate 54 was made of nickel wool as a current collector (not shown) at the center of the plate.

A plurality of ferritic stainless steel pipes having an outer diameter of 2 mm, an inner diameter of 1 mm, and a length of 5 mm are used for the plurality of blocks 61 of the frame 60, and the outer edge portion of the cell plate 53 is associated with the block 61 of the frame 60. The glass 61 formed on the surface of the metal foil 62 of the frame 60 is provided with a concave portion 53a to be joined, and the blocks 61 arranged at intervals of 1 mm are connected by being covered with a metal foil 62 made of a ferritic stainless steel foil having a thickness of 0.03 mm. the layer (not _shown), was used _{52% BaO-3% Al 2} O 3 -33SiO 2 -12% CaO -based glass.

  Also in the stack structure 51 of this embodiment, in addition to the cell plate 53 and the separator plate 54 both being made of a thin metal, a plurality of blocks 61 are made of deformable metal foils 62 that do not transmit gas. Since the cell plate 53 and the separator plate 54 are joined via the frame 60 covering the, the whole can be deformed with respect to heat.

  Even if the cell plate 53 or the separator plate 54 is thermally deformed and a tensile force or a compressive force is applied to the frame 60, the frame 60 is also deformed to absorb the tensile force or the compressive force. Therefore, there is little possibility that a defect such as a crack will occur in the joint portion. Therefore, excellent gas sealability and bondability between the cell plate 5 and the separator plate 5 are secured, and in addition, the block of the frame 60 61 is formed in a pipe shape, and the concave portion 53a that engages with the block 61 is provided at the outer edge portion of the cell plate 53, so that the area of joining the frame 60 to the cell plate 53 is increased, and the cell Flexibility in the stacking direction of the plate 53 and the separator plate 54 can also be imparted.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an exploded explanatory view (a) and a cross-sectional explanatory view (b) of one layer (one unit) showing an embodiment of a stack structure of a solid oxide fuel cell of the present invention. Example 1 FIG. 1 is an explanatory plan view (a) of the cell plate of the stack structure viewed from the fuel electrode side of the single cell, an explanatory plan view (b) of the cell plate viewed from the air electrode side of the single cell, and the fuel electrode side separator plate. It is a plane explanatory view (c) of FIG. 2 and a plane explanatory view (d) of the air electrode side separator plate. Example 1 It is the plane explanatory view (a) and the side surface explanatory view (b) which show the state which affixed metal foil on the cell board at the time of manufacturing the flame | frame of the stack structure body in FIG. Example 1 It is plane explanatory drawing (a) and the side explanatory drawing (b) which show the state which attached the block to the cell board at the time of manufacturing the flame | frame of the stack structure body in FIG. Example 1 It is the plane explanatory view (a) and side surface explanatory view (b) which show the state which wrapped the block with the metal foil at the time of manufacturing the flame | frame of the stack structure in FIG. Example 1 FIG. 1 is a perspective explanatory view (a) of one layer (one unit) of the stack structure in FIG. 1 and a cross-sectional explanatory view of one layer (one unit) of this stack structure set in a hydrogen permeation tester ( b). Example 1 FIG. 6 is a perspective explanatory view of a separator plate provided with a frame showing another configuration example of the stack structure in FIG. 1. The plane explanatory view (a) which looked at the cell board which shows other examples of the stack structure of the solid oxide fuel cell of the present invention from the fuel electrode side of the single cell, and the cell board which looked from the air electrode side of the single cell It is plane explanatory drawing (b). (Example 2) It is a plane explanatory view of a cell board showing other examples of a stack structure of a solid oxide fuel cell of the present invention. (Example 3) It is the perspective explanatory drawing (a) of the cell board which shows the further another Example of the stack structure of the solid oxide fuel cell of this invention, and the cross-sectional explanatory drawing (b) of a cell board. Example 4 FIG. 11 is a cross-sectional explanatory view of a cell plate showing another configuration example of the stack structure in FIG. 10. It is the whole perspective explanatory view (a) which shows further another Example of the stack structure of a solid oxide fuel cell of the present invention, the perspective explanatory view (b) of a cell board, and the perspective explanatory view (c) of a separator board. (Example 5)

Explanation of symbols

1, 21, 31, 41, 51 Stack structure of solid oxide fuel cell 2,52 Single cell 3,53 Cell plate 3fi, 4fi Fuel gas introduction hole 3fo, 4fo Fuel gas discharge hole 3ai, 4ai Oxidation gas introduction hole 3ao , 4ao Oxidizing gas discharge holes 4, 54 Separator plate 6 Glass layer 10, 60 Frame 11, 11A, 11B, 11C, 61 Block 12, 62 Metal foil

Claims (8)

  A thin metal plate having a single cell and having a fuel gas introduction hole, a fuel gas discharge hole, an oxidation gas introduction hole, and an oxidation gas discharge hole, and a fuel gas introduction hole, a fuel gas discharge hole, an oxidation In a stack structure of a solid oxide fuel cell in which thin metal separator plates having gas introduction holes and oxidant gas discharge holes are alternately stacked, on the outer edge portion of one of the cell plates and the separator plates Provided with a frame formed by covering and connecting a plurality of blocks arranged at appropriate intervals with a metal foil, and a cell plate and a separator plate are joined via the frame. Battery stack structure.   Each fuel gas introduction hole, fuel gas discharge hole, oxidation gas introduction hole, and oxidation gas discharge hole communicating with the cell plate and separator plate, a fuel gas discharge hole, an oxidation gas introduction hole, and an oxidation gas discharge hole are framed. The stack structure of the solid oxide fuel cell according to claim 1, which is provided in the structure.   In the vicinity of the fuel gas introduction hole, the fuel gas discharge hole, the oxidizing gas introduction hole, and the oxidizing gas discharge hole in the frame, the adjacent blocks are closely spaced, and the fuel gas introduction hole and the fuel gas discharge hole are arranged. 3. The stack structure of a solid oxide fuel cell according to claim 2, wherein the adjacent blocks are arranged with a small spacing between the oxidant gas introduction hole and the oxidant gas discharge hole. Fuel gas introduction hole in the frame, a fuel gas discharge hole, oxidizing gas inlet and claim 2 and the block positioned in arranged close to the single cell side to have the function of reinforcing ribs during each of the oxidizing gas discharge hole or 4. A stack structure of a solid oxide fuel cell according to 3 .   The block of the frame has a circular or elliptical cross section, and a concave portion that engages with the block of the frame is provided on one of the outer edge portions of the cell plate and the separator plate. A stack structure for a solid oxide fuel cell according to Item.   The solid block according to any one of claims 1 to 4, wherein the block of the frame is formed in a pipe shape, and a concave portion that engages with the block of the frame is provided at one of the outer edge portions of the cell plate and the separator plate. Stack structure of an electrolyte fuel cell.   A glass layer made of a glass-based bonding material is formed on the metal foil surface of the frame provided on the outer edge portion of either the cell plate or the separator plate, and this glass layer is connected to the other outer edge portion of the cell plate or the separator plate. The stack structure of a solid oxide fuel cell according to any one of claims 1 to 6, wherein the bonding layer is a bonding layer. The difference in thermal expansion coefficient between the glass layer made of glass-based bonding material and the metal foil of the frame, and the glass layer made of glass-based bonding material and the metal that constitutes the other plate of the cell plate and separator plate The stack structure of a solid oxide fuel cell according to claim 7, wherein the difference in thermal expansion coefficient with respect to the thin plate is 2 × 10 ⁻⁶ (1 / K) or less.

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