Single cell stack device, module, module receiving device and metal component

Abstract

A single cell stack device (10) includes a single cell stack (11) and an end current collecting member (17). The single cell stack (11) is provided with a plurality of single cells (1) arranged therein. The end current collecting member (17) is located at the end of the single cell stack (11) in the arrangement direction of the plurality of single cells (1). In addition, the surface of the end current collecting member (17) exposed in an oxidizing atmosphere is covered with a covering material (17b) including manganese, and the surface of the end current collecting member (17) exposed in a reducing atmosphere is covered with a film different from the covering material (17b).

Description

Technical Field

[0001] The present disclosure relates to a single cell stack device, a module, a module receiving device and a metal component. Background Art

[0002] In recent years, various fuel cell stack devices composed of a plurality of arranged fuel cells have been proposed as next-generation energy sources. The fuel cell is a type of cell capable of generating electric power using a fuel gas such as hydrogen-containing gas and an oxygen-containing gas such as air.

[0003] In this fuel cell stack device, for example, an end current collecting member made of a metal material is located at an end of the cell stack in the direction in which the plurality of fuel cells are arranged (see Patent Document 1).

[0004] Prior Art Literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2015-162357 Summary of the invention

[0007] A single cell stack device according to one embodiment of the present invention comprises a single cell stack and an end current collecting member. The single cell stack is provided with a plurality of single cells arranged therein. The end current collecting member is located at an end of the single cell stack in the arrangement direction of the plurality of single cells. Moreover, the surface of the end current collecting member exposed in an oxidizing atmosphere is covered with a covering material including manganese, and the surface of the end current collecting member exposed in a reducing atmosphere is covered with a film different from the covering material. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1A It is a cross-sectional view showing an example of a single cell according to the embodiment.

[0009] Figure 1B This is a side view of an example of a unit cell according to the embodiment as viewed from the air electrode side.

[0010] Figure 1C This is a side view of an example of a unit cell according to the embodiment as viewed from the interconnector side.

[0011] Figure 2A It is a perspective view showing an example of a cell stack device according to the embodiment.

[0012] Figure 2B yes Figure 2A A cross-sectional view along line XX is shown.

[0013] Figure 2C It is a plan view showing an example of a cell stack device according to the embodiment.

[0014] Figure 3 It is a cross-sectional view showing an end current collecting member according to the embodiment.

[0015] Figure 4 It is a cross-sectional view showing an end current collecting member according to Modification 1 of the embodiment.

[0016] Figure 5 It is a cross-sectional view showing an end current collecting member according to Modification 2 of the embodiment.

[0017] Figure 6 It is a cross-sectional view showing an end current collecting member according to Modification 3 of the embodiment.

[0018] Figure 7 It is an enlarged cross-sectional view showing an end current collecting member according to Modification 4 of the embodiment.

[0019] Figure 8 It is an enlarged cross-sectional view showing an end current collecting member according to Modification 5 of the embodiment.

[0020] Fig. 9 It is an enlarged cross-sectional view showing an end current collecting member according to Modification 6 of the embodiment.

[0021] Fig.10 It is a cross-sectional view showing an end current collecting member according to Modification 7 of the embodiment.

[0022] Fig.11 It is a cross-sectional view showing an end current collecting member according to Modification 8 of the embodiment.

[0023] Fig.12 It is a cross-sectional view showing an end current collecting member according to Modification 9 of the embodiment.

[0024] Fig.13 It is an external perspective view showing an example of a module according to the embodiment.

[0025] Fig.14 It is an exploded perspective view schematically showing an example of the module housing device according to the embodiment. DETAILED DESCRIPTION

[0026] Hereinafter, embodiments of the cell stack device, module, module housing device, and metal member disclosed in the present application will be described in detail with reference to the accompanying drawings. Note that the present disclosure is not limited to the embodiments described below.

[0027] In addition, the drawings are schematic, and it should be noted that the relationship between the dimensions of each element, the ratio of each element, etc. may be different from the actual. Furthermore, the drawings may also include portions where the relationship between the dimensions, the ratio, etc. are different from each other.

[0028] In recent years, various fuel cell stack devices composed of a plurality of arranged fuel cells have been proposed as next-generation energy sources. The fuel cell is a type of cell capable of generating electric power using a fuel gas such as hydrogen-containing gas and an oxygen-containing gas such as air.

[0029] In this fuel cell stack device, for example, an end current collecting member made of a metal material is located at an end of the fuel cell stack in the direction in which the plurality of fuel cells are arranged.

[0030] However, the end current collecting member is exposed to both an oxidizing atmosphere such as air and a reducing atmosphere such as a hydrogen-containing gas at different locations. Therefore, even if the surface has aging resistance to one atmosphere, it may be inferior to aging resistance to the other atmosphere.

[0031] Therefore, it is desired to realize a technology that can overcome the above-mentioned problems and improve the degradation resistance of the fuel cell stack device.

[0032] <Structure of single cell>

[0033] First, refer to Figure 1A to Figure 1C , an example will be described using a solid oxide fuel cell as a cell constituting the cell stack device according to the embodiment.

[0034] Figure 1A is a cross-sectional view showing an example of a single cell 1 according to the embodiment, Figure 1B is a side view of an example of a unit cell 1 according to the embodiment as viewed from the air electrode 5 side. Figure 1C This is a side view of an example of the unit cell 1 according to the embodiment as viewed from the interconnector 6 side. Figure 1A to Figure 1C Part of each structure of the unit cell 1 is shown in an enlarged manner.

[0035] exist Figure 1A to Figure 1C In the example shown, the single cell 1 is a hollow flat plate type, and is in the shape of an elongated plate. Figure 1B As shown, the overall shape of the cell 1 when viewed from the side is, for example, a rectangle with a side length of 5 to 50 cm in the longitudinal direction L and a length of 1 to 10 cm in the width direction W perpendicular to the longitudinal direction L. The overall thickness of the cell 1 (thickness direction T) is 1 to 5 mm.

[0036] like Figure 1A As shown, the cell 1 includes a conductive support substrate 2, an element portion, and an interconnector 6. The support substrate 2 is a columnar structure having a pair of opposing first flat surfaces n1, a second flat surface n2, and a pair of arc-shaped side surfaces m connecting the first flat surface n1 and the second flat surface n2.

[0037] The element portion is located on the first flat surface n1 of the support substrate 2. The element portion includes a fuel electrode 3, a solid electrolyte layer 4, and an air electrode 5. Figure 1A In the example shown, the interconnector 6 is located on the second flat surface n2 of the cell 1 .

[0038] In addition, if Figure 1B As shown in FIG. 1 , the air electrode 5 does not extend to the lower end of the cell 1. At the lower end of the cell 1, only the solid electrolyte layer 4 is exposed on the surface of the first flat surface n1. Figure 1C As shown in FIG. 1 , the interconnector 6 may also extend to the lower end of the cell 1. At the lower end of the cell 1, the interconnector 6 and the solid electrolyte layer 4 are exposed on the surface. Figure 1A As shown, the solid electrolyte layer 4 is exposed on the surfaces of the pair of arc-shaped side surfaces m of the unit cell 1. The interconnector 6 does not necessarily need to extend to the lower end of the unit cell 1.

[0039] Hereinafter, each component constituting the cell 1 will be described.

[0040] The support substrate 2 has a gas flow path 2a inside for gas flow. Figure 1A , an example is shown in which six gas flow paths 2 a extending in the longitudinal direction are provided. The support substrate 2 has gas permeability and allows the fuel gas to permeate to the fuel electrode 3 . Figure 1A The support substrate 2 shown has conductivity and collects electricity generated by the element portion via the interconnector 6 .

[0041] The material of the support substrate 2 includes, for example, an iron group metal component and an inorganic oxide. The iron group metal component in the material of the support substrate 2 may be, for example, Ni and / or NiO. The inorganic oxide in the material of the support substrate 2 may be, for example, a specific rare earth element oxide.

[0042] The material of the fuel electrode 3 can be a generally known material. The material of the fuel electrode 3 can be a porous conductive ceramic, such as calcium oxide, magnesium oxide, or a ceramic containing ZrO2 and Ni and / or NiO in which a rare earth element oxide is solid-dissolved. As the rare earth element oxide, for example, Y2O3 can be used.

[0043] Hereinafter, ZrO2 in which calcium oxide, magnesium oxide, or a rare earth element oxide is solid-dissolved is referred to as stabilized zirconium oxide. In the present disclosure, stabilized zirconium oxide also includes partially stabilized zirconium oxide.

[0044] The solid electrolyte layer 4 is an electrolyte and bridges ions between the fuel electrode 3 and the air electrode 5. The solid electrolyte layer 4 has a gas barrier property and is unlikely to cause leakage of the fuel gas and the oxygen-containing gas.

[0045] The material of the solid electrolyte layer 4 is, for example, ZrO2 in which 3 to 15 mol% of a rare earth element oxide is dissolved. As the rare earth element oxide, Y2O3 or the like can be used, for example. In addition, as long as it has the above characteristics, other materials or the like can also be used as the material of the solid electrolyte layer 4.

[0046] The material of the air electrode 5 is not particularly limited as long as it is a material commonly used for air electrodes. The material of the air electrode 5 can also be a conductive ceramic such as a perovskite-type oxide of the so-called ABO3 type, for example.

[0047] The material of the air electrode 5 can be, for example, a composite oxide in which Sr and La coexist at the A site. As an example of such a composite oxide, La x Sr 1-x Co y Fe 1-y O3, La x Sr 1-x MnO3, La x Sr 1-x FeO3, La x Sr 1-x CoO3 and the like. In addition, x is 0 < x < 1 and y is 0 < y < 1.

[0048] In addition, the air electrode 5 has gas permeability. The open pore rate of the air electrode 5 can be 20% or more, particularly in the range of 30% to 50%.

[0049] As the material of the interconnect 6, a perovskite-type oxide of the lanthanum chromate series (LaCrO3-based oxide), a perovskite-type oxide of the lanthanum strontium titanium series (LaSrTiO3-based oxide), or the like can be used. These materials have conductivity and are neither reduced nor oxidized even when in contact with a fuel gas such as a hydrogen-containing gas and an oxygen-containing gas such as air.

[0050] In addition, the interconnect 6 is dense and it is difficult for the fuel gas flowing in the gas flow path 2a inside the support substrate 2 and the oxygen-containing gas flowing outside the support substrate 2 to leak. The interconnect 6 can also have a relative density of 93% or more, particularly 95% or more.

[0051] <Structure of the single cell stack device>

[0052] Next, with reference to Figure 2A to Figure 2C the single cell stack device 10 according to the present embodiment using the above single cell 1 will be described. Figure 2A is a perspective view showing an example of the single cell stack device 10 according to the embodiment, Figure 2B is Figure 2A a cross-sectional view taken along the line X-X shown, Figure 2CIt is a plan view showing an example of the cell stack device 10 according to the embodiment.

[0053] like Figure 2A As shown, the cell stack device 10 includes: a cell stack 11 having a thickness direction T (see Figure 1A ) a plurality of single cells 1 arranged (stacked) on the top; and a fixing member 12.

[0054] The fixing member 12 includes a fixing material 13 and a support member 14. The support member 14 supports the single cell 1. The fixing material 13 fixes the single cell 1 to the support member 14. In addition, the support member 14 includes a support body 15 and a gas tank 16. The support body 15 and the gas tank 16 as the support member 14 are made of metal and have conductivity.

[0055] like Figure 2B As shown, the support body 15 has an insertion hole 15a into which the lower end portions of the plurality of cells 1 are inserted. The lower end portions of the plurality of cells 1 are bonded to the inner wall of the insertion hole 15a by a fixing material 13.

[0056] The gas tank 16 has an opening for supplying reaction gas to the plurality of cells 1 through the insertion hole 15a and a groove 16a around the opening. The outer peripheral end of the support 15 is joined to the gas tank 16 by a joining material 21 filling the groove 16a of the gas tank 16.

[0057] exist Figure 2A In the example shown, in the internal space 22 (see Figure 2B ) stores fuel gas. A gas flow pipe 20 is connected to the gas tank 16. The fuel gas is supplied to the gas tank 16 through the gas flow pipe 20, and the fuel gas flows from the gas tank 16 to the gas flow path 2a (see Figure 1A The fuel gas supplied to the gas tank 16 is supplied by the reformer 82 (see Fig.13 )generate.

[0058] The hydrogen-rich fuel gas can be produced by steam reforming the raw fuel, etc. When the fuel gas is produced by steam reforming, the fuel gas includes water vapor.

[0059] Figure 2A The example shown has two rows of single cell stacks 11, two supports 15, and a gas tank 16. The two rows of single cell stacks 11 each have a plurality of single cells 1. Each single cell stack 11 is fixed to each support 15. The gas tank 16 has two through holes on the upper surface. Each support 15 is arranged in each through hole. The internal space 22 is formed by one gas tank 16 and two supports 15.

[0060] The shape of the insertion hole 15a is, for example, an oval shape in a plan view. The length of the insertion hole 15a in the thickness direction T, which is the arrangement direction of the cells 1, is greater than the distance between the two end current collecting members 17 located at both ends of the cell stack 11. The width of the insertion hole 15a is, for example, greater than the width direction W of the cell 1 (see Figure 1A ) is long.

[0061] like Figure 2B As shown, the fixing material 13 is filled and cured in the joint between the inner wall of the insertion hole 15a and the lower end of the single cell 1. As a result, the inner wall of the insertion hole 15a is respectively joined / fixed to the lower ends of the plurality of single cells 1, and the lower ends of the single cells 1 are joined / fixed to each other. The gas flow path 2a of each single cell 1 communicates with the internal space 22 of the support member 14 at the lower end.

[0062] A material with low conductivity can be used for the fixing material 13 and the bonding material 21. As specific materials for the fixing material 13 and the bonding material 21, amorphous glass or the like can be used, and in particular, crystallized glass or the like can also be used.

[0063] As crystallized glass, for example, any of the materials such as SiO2-CaO system, MgO-B2O3 system, La2O3-B2O3-MgO system, La2O3-B2O3-ZnO system, SiO2-CaO-ZnO system can be used, and in particular, SiO2-MgO system materials can also be used.

[0064] In addition, if Figure 2B As shown, between adjacent single cells 1, there is a conductive member 18 that electrically connects the adjacent single cells 1 (more specifically, the fuel electrode 3 of one single cell 1 and the air electrode 5 of the other single cell 1) in series. More specifically, between adjacent single cells 1 is between the fuel electrode 3 of one adjacent single cell 1 and the air electrode 5 of the other adjacent single cell 1.

[0065] In addition, if Figure 2B As shown in FIG. 1 , an end current collecting member 17 is connected to the outermost single cell 1 in the arrangement direction of the plurality of single cells 1. The end current collecting member 17 is connected to a conductive portion 19 protruding to the outside of the single cell stack 11. The conductive portion 19 has the function of collecting electricity generated by the single cell 1 and leading it to the outside. Figure 2A In the figure, the end current collecting member 17, the conductive member 18 and the conductive portion 19 are omitted.

[0066] In addition, if Figure 2CAs shown, in the cell stack device 10, two cell stacks 11A and 11B are connected in series and function as one battery. Therefore, the conductive portion 19 of the cell stack device 10 is divided into a positive terminal 19A, a negative terminal 19B, and a connection terminal 19C.

[0067] The positive terminal 19A functions as a positive electrode when the power generated by the cell stack 11 is output to the outside, and is electrically connected to the end current collecting member 17 on the positive electrode side of the cell stack 11A. The negative terminal 19B functions as a negative electrode when the power generated by the cell stack 11 is output to the outside, and is electrically connected to the end current collecting member 17 on the negative electrode side of the cell stack 11B.

[0068] The connection terminal 19C electrically connects the end current collecting member 17 on the negative electrode side in the cell stack 11A and the end current collecting member 17 on the positive electrode side in the cell stack 11B.

[0069] <Details of End Current Collecting Member>

[0070] Next, for details of the end current collecting member 17 according to the embodiment, refer to Figure 3 Provide explanation. Figure 3 1 is a cross-sectional view showing an end current collecting member 17 according to the embodiment. The end current collecting member 17 is an example of a metal member.

[0071] like Figure 3 As shown, one end (the lower end in the figure) of the end current collecting member 17 is connected to the plurality of cells 1 (see Figure 2B ) are inserted into the insertion hole 15a and fixed in the insertion hole 15a by the fixing material 13. That is, the side surface of one end (lower end) of the end current collecting member 17 is in contact with the fixing material 13.

[0072] In addition, a part of the surface (for example, the bottom surface) of one end (lower end) of the end current collecting member 17 is formed by the support member 14 (see Figure 2B ) is exposed. As described above, the internal space 22 is a space where the fuel electrode 3 of the single cell 1 is connected through the support substrate 2, and is filled with a fuel gas such as a hydrogen-containing gas. That is, the internal space 22 is a reducing atmosphere.

[0073] On the other hand, the surface other than one end (lower end) of the end current collecting member 17 is exposed to the external space 23. The external space 23 is a space where the air electrode 5 of the cell 1 is exposed and is filled with oxygen-containing gas such as air. That is, the external space 23 is an oxidizing atmosphere.

[0074] like Figure 3As shown, the surface of the end current collecting member 17 used in such an environment that is exposed to the oxidizing atmosphere (external space 23) may be covered with a covering material 17b. The material of the covering material 17b is, for example, a conductive oxide containing manganese (Mn) (for example, ZnMnCoO4). The covering material 17b is formed on the surface of the base material 17a by, for example, electrodeposition coating. In addition, in the embodiment, the material of the base material 17a of the end current collecting member 17 is, for example, stainless steel.

[0075] Furthermore, by covering the surface of the end current collecting member 17 with the covering material 17 b , chromium (Cr) included in the base material 17 a can be prevented from being released into the oxidizing atmosphere (external space 23 ) during high temperature operation, thereby improving the aging resistance of the end current collecting member 17 .

[0076] On the other hand, when the covering material 17b is exposed to a reducing atmosphere (eg, the internal space 22), manganese, which is a constituent element of the covering material 17b, is reduced and separated from the covering material 17b, and thus the aging resistance of the end current collecting member 17 may be reduced.

[0077] Therefore, in the embodiment, the surface (bottom surface in the figure) exposed to the reducing atmosphere (internal space 22) of the end current collecting member 17 is covered with a film different from the covering material 17b. For example, in the embodiment, the surface exposed to the reducing atmosphere is covered with the natural oxide film 17a1 of the base material 17a.

[0078] The material of the natural oxide film 17a1 is, for example, chromium oxide (Cr2O3). The constituent elements of the natural oxide film 17a1 hardly cause a reduction reaction even in a reducing atmosphere.

[0079] This can suppress the desorption of constituent elements from the surface exposed to the reducing atmosphere (internal space 22 ). Therefore, according to the embodiment, the aging resistance of the end current collecting member 17 can be improved, and thus the aging resistance of the cell stack device 10 can be improved.

[0080] The natural oxide film 17a1 can be formed, for example, by forming the covering material 17b on the entire surface of the base material 17a, etching a predetermined portion (here, the bottom surface) using sulfuric acid or the like, and subjecting the exposed surface of the base material 17a to high-temperature treatment in an oxidizing atmosphere.

[0081] Furthermore, in the embodiment, the end current collecting member 17 can be manufactured at low cost by covering the surface exposed to the reducing atmosphere with the natural oxide film 17 a 1 which can be easily formed.

[0082] <Various Modifications>

[0083] Next, the end current collecting member 17 according to various modified examples of the embodiment will be described with reference to FIG. Figures 4 to 12 Provide explanation. Figure 4 It is a cross-sectional view showing an end current collecting member 17 according to Modification 1 of the embodiment.

[0084] In the above embodiment, the surface of the end current collecting member 17 exposed to the reducing atmosphere (internal space 22) is covered with the natural oxide film 17a1. However, the film covering the surface exposed to the reducing atmosphere is not limited to the natural oxide film 17a1.

[0085] For example, Figure 4 As shown, the surface exposed to the reducing atmosphere (internal space 22) may also be covered with a reduction preventing film 17c. The material of the reduction preventing film 17c is a material whose constituent elements hardly undergo reduction reaction even in a reducing atmosphere, such as forsterite, alumina (A12O3), etc.

[0086] By covering the bottom surface with the reduction preventing film 17c, it is possible to suppress the constituent elements from being separated from the surface exposed to the reducing atmosphere (internal space 22). Therefore, according to Modification 1, the aging resistance of the end current collecting member 17 can be improved, and thus the aging resistance of the cell stack device 10 can be improved.

[0087] Furthermore, in Modification 1, since a material other than stainless steel can be used for the base material 17 a of the end current collecting member 17 , it is possible to achieve improved performance of the end current collecting member 17 (for example, improvement in electrical conductivity).

[0088] Figure 5 FIG. 2 is a cross-sectional view showing an end current collecting member 17 according to a second modification of the embodiment. Figure 5 As shown, the end current collecting member 17 according to Modification 2 is covered with a film different from the covering material 17 b in addition to the surface exposed to the reducing atmosphere (internal space 22 ) and the surface in contact with the fixing material 13 .

[0089] For example, in Figure 5 In the example of FIG. 1 , the surface exposed in the reducing atmosphere and the surface in contact with the fixing material 13 are covered with the natural oxide film 17 a 1 of the base material 17 a .

[0090] By covering the surface in contact with the fixing material 13 with a film different from the covering material 17b, it is possible to suppress the diffusion of manganese, a constituent element of the covering material 17b, into the fixing material 13, a glass material, during high temperature operation, thereby preventing cracks from occurring in the covering material 17b.

[0091] Therefore, according to Modification 2, the aging resistance of the end current collecting member 17 can be further improved, and thus the aging resistance of the cell stack device 10 can be further improved.

[0092] In Modification 2, the surface exposed to the reducing atmosphere and the surface in contact with the fixing material 13 can be covered with the easily formed natural oxide film 17 a 1 , so the end current collecting member 17 can be manufactured at low cost.

[0093] Figure 6 2 is a cross-sectional view showing an end current collecting member 17 according to a third modification of the embodiment. Figure 5 In the example shown, the surface exposed in the reducing atmosphere and the surface in contact with the fixing material 13 are covered with the natural oxide film 17a1, but the film covering these surfaces is not limited to the natural oxide film 17a1.

[0094] For example, Figure 6 As shown, the surface exposed to the reducing atmosphere and the surface in contact with the fixing material 13 may be covered with the reduction preventing film 17c. This can prevent the constituent elements from being separated from the surface exposed to the reducing atmosphere and the surface in contact with the fixing material 13.

[0095] Therefore, according to Modification 3, the degradation resistance of the end current collecting member 17 can be improved, and thus the degradation resistance of the cell stack device 10 can be further improved.

[0096] In addition, Figure 5 as well as Figure 6 In the example, the natural oxide film 17a1 or the reduction prevention film 17c is located on the entire surface of the end current collecting member 17 in contact with the fixing material 13. On the other hand, in the present disclosure, the natural oxide film 17a1 or the reduction prevention film 17c may be located only in a portion close to the reducing atmosphere on the surface in contact with the fixing material 13, and the covering material 17b may be located in a portion close to the air.

[0097] For example, Figure 7 As shown, the natural oxide film 17 a 1 may be located on the surface of the end current collecting member 17 that contacts the fixing material 13 and is located on the surface on the inner space 22 side, and the covering material 17 b may be located on the surface on the outer space 23 side. Figure 7 It is an enlarged cross-sectional view showing an end current collecting member 17 according to Modification 4 of the embodiment.

[0098] In addition, Figure 7 In the fourth modification shown, the surface roughness Ra of the surface 17a2 of the natural oxide film 17a1 in contact with the fixing material 13 may be greater than the surface roughness Ra of the surface 17b1 of the covering material 17b in contact with the fixing material 13.

[0099] In this way, by increasing the surface roughness Ra of the surface 17a2 of the natural oxide film 17a1 in contact with the fixing material 13, the adhesion between the end current collecting member 17 and the fixing material 13 can be improved on the reducing atmosphere side (i.e., the internal space 22 side) where peeling is likely to occur.

[0100] Furthermore, by reducing the surface roughness Ra of the surface 17b1 of the covering material 17b in contact with the fixing material 13, diffusion of Cr from the base material 17a to the fixing material 13 on the oxidizing atmosphere side (ie, the external space 23 side) where Cr easily diffuses can be suppressed.

[0101] Therefore, according to Modification 4, the degradation resistance of the end current collecting member 17 can be improved, and thus the degradation resistance of the cell stack device 10 can be improved.

[0102] In the fourth modification, the area S1 of the surface 17a2 of the natural oxide film 17a1 in contact with the anchoring material 13 may be smaller than the area S2 of the surface 17b1 of the cover material 17b in contact with the anchoring material 13 .

[0103] This can prevent Cr included in the base material 17a from being released into the oxidizing atmosphere (external space 23) through the covering material 17b during high temperature operation, and prevent the end current collecting member 17 from peeling off from the fixing material 13 to cause leakage of fuel gas.

[0104] Therefore, according to Modification 4, the degradation resistance of the end current collecting member 17 can be improved, and thus the degradation resistance of the cell stack device 10 can be improved.

[0105] Figure 8 FIG. 2 is an enlarged cross-sectional view showing an end current collecting member 17 according to a fifth modification of the embodiment. Figure 8 As shown, in Modification 5, the covering material 17b may be located on the side of one end (lower end) 1762 of the covering material 17b and may have a surface 1763 connecting the surface 17a2 of the natural oxide film 17a1 and the surface 17b1 of the covering material 17b. The surface 1763 is, for example, a tapered surface inclined relative to the surface 17b1 of the covering material 17b.

[0106] Thus, the covering material 17b has the surface 1763, thereby increasing the contact area between the covering material 17b and the fixing material 13. This can improve the aging resistance of the end current collecting member 17, and can improve the aging resistance of the cell stack device 10.

[0107] Fig. 9 FIG. 2 is an enlarged cross-sectional view showing an end current collecting member 17 according to a sixth modification of the embodiment. Fig. 9As shown, in Modification 6, the covering material 17b may have a protrusion 1764 located at one end (lower end) 1762 of the covering material 17b and protruding in a direction away from the end current collecting member 17 and facing the fixing material 13.

[0108] Thus, since the covering material 17b has the protruding portion 1764, the contact area between the covering material 17b and the fixing material 13 is increased. This can improve the aging resistance of the end current collecting member 17, and thus improve the aging resistance of the cell stack device 10.

[0109] In addition, Figure 8 as well as Fig. 9 In the figure, the covering material 17b is shown to have the surface 1763 or the protrusion 1764, but the covering material 17b may have the surface 1763 and the protrusion 1764.

[0110] Fig.10 1 is a cross-sectional view showing end current collecting member 17 according to Modification 7 of the embodiment. In the above-described embodiment and Modifications 1 to 6, part of end current collecting member 17 is exposed in internal space 22, but end current collecting member 17 need not be exposed in internal space 22.

[0111] exist Fig.10 , the entire surface of the end current collecting member 17 is covered by the covering material 17 b , and one end (the lower end in the figure) of the end current collecting member 17 remains inside the fixing material 13 and does not protrude from the fixing material 13 into the internal space 22 .

[0112] Thus, by preventing the end current collector member 17 from being exposed in the reducing atmosphere (internal space 22), it is possible to suppress the reduction of manganese, a structural element of the covering material 17b, and its separation from the covering material 17b. Therefore, according to Modification 7, the aging resistance of the end current collector member 17 can be improved, and thus the aging resistance of the single cell stack device 10 can be improved.

[0113] Furthermore, in Modification 7, after the coating material 17 b is formed on the entire surface of the base material 17 a , there is no need to perform etching or the like, and thus the end current collecting member 17 can be manufactured at low cost.

[0114] Fig.11 FIG. 2 is a cross-sectional view showing an end current collecting member 17 according to a modification example 8 of the embodiment. Fig.11 As shown in FIG. 1 , the surface of the end current collecting member 17 according to the modification 8 that contacts the fixing material 13 is covered with a film different from the covering material 17b. Fig.11 In the example of FIG. 1 , the surface in contact with the fixing material 13 is covered with the natural oxide film 17 a 1 of the base material 17 a .

[0115] By covering the surface in contact with the fixing material 13 with a film different from the covering material 17b, it is possible to suppress the diffusion of manganese, a constituent element of the covering material 17b, into the fixing material 13, a glass material, during high temperature operation, thereby preventing cracks from occurring in the covering material 17b.

[0116] Therefore, according to Modification 8, the degradation resistance of the end current collecting member 17 can be further improved, and thus the degradation resistance of the cell stack device 10 can be further improved.

[0117] Fig.12 2 is a cross-sectional view showing an end current collecting member 17 according to a ninth modification of the embodiment. Fig.11 In the example shown, the surface in contact with the fixing material 13 is covered with the natural oxide film 17a1, but the film covering the surface in contact with the fixing material 13 is not limited to the natural oxide film 17a1.

[0118] For example, Fig.12 As shown, the surface in contact with the fixing material 13 may be covered with the reduction preventing film 17c. This can prevent manganese, which is a structural element of the covering material 17b, from diffusing into the fixing material 13, which is a glass material, and causing cracks in the covering material 17b during high temperature operation.

[0119] Therefore, according to Modification 9, the degradation resistance of the end current collecting member 17 can be further improved, and thus the degradation resistance of the cell stack device 10 can be further improved.

[0120] <Module>

[0121] Next, use Fig.13 A module 80 according to an embodiment of the present disclosure using the above-described cell stack device 10 will be described. Fig.13 It is a perspective view showing the appearance of a module 80 according to the embodiment, showing a state in which the front surface and the rear surface as a part of the storage container 81 are removed and the single cell stack device 10 of the fuel cell stored inside is taken out to the rear.

[0122] like Fig.13 As shown, the module 80 includes a storage container 81 and the cell stack device 10 stored in the storage container 81. Above the cell stack device 10, a reformer 82 is arranged.

[0123] The reformer 82 reforms a raw fuel such as natural gas or kerosene to generate fuel gas, and supplies the fuel gas to the cell 1. The raw fuel is supplied to the reformer 82 through a raw fuel supply pipe 83. The reformer 82 may include a vaporizing section 82a for vaporizing water and a reforming section 82b.

[0124] The reforming unit 82b includes a reforming catalyst (not shown) and reforms the raw fuel into a fuel gas. Such a reformer 82 can perform a highly efficient reforming reaction, namely, steam reforming.

[0125] The fuel gas generated by the reformer 82 is supplied to the gas flow path 2a of the cell 1 through the gas flow pipe 20, the gas tank 16, and the fixing member 12 (see Figure 1A ).

[0126] In the module 80 having the above structure, the temperature inside the module 80 during power generation is generally about 500 to 1000° C. as the gas is combusted and the unit cells 1 generate power.

[0127] In such a module 80 , as described above, by accommodating the cell stack device 10 having high deterioration resistance, it is possible to obtain a module 80 having high deterioration resistance.

[0128] <Module Storage Device>

[0129] Fig.14 1 is an exploded perspective view showing an example of a module storage device 90 according to the embodiment. The module storage device 90 according to the embodiment includes an outer casing 91, Fig.13 The module 80 shown in the figure and the auxiliary equipment not shown in the figure. The auxiliary equipment operates the module 80. The module 80 and the auxiliary equipment are accommodated in the outer casing 91. Fig.14 A part of the structure is omitted to indicate the above.

[0130] Fig.14 The outer casing 91 of the module storage device 90 shown in the figure has a support 92 and an outer plate 93. The partition plate 94 divides the outer casing 91 into upper and lower parts. The space above the partition plate 94 in the outer casing 91 is a module storage chamber 95 for storing the module 80, and the space below the partition plate 94 in the outer casing 91 is an auxiliary equipment storage chamber 96 for storing auxiliary equipment for the operation module 80. Fig.14 In the figure, the auxiliary equipment accommodated in the auxiliary equipment accommodation chamber 96 is omitted.

[0131] The partition plate 94 has an air flow port 97 for allowing air in the auxiliary equipment storage chamber 96 to flow toward the module storage chamber 95. The exterior plate 93 constituting the module storage chamber 95 has an exhaust port 98 for exhausting air in the module storage chamber 95.

[0132] In such a module housing device 90 , as described above, by providing the module 80 having high aging resistance in the module housing chamber 95 , it is possible to achieve a module housing device 90 having high aging resistance.

[0133] As mentioned above, although this disclosure was demonstrated in detail, this disclosure is not limited to the said embodiment, Various changes, improvements, etc. can be made within the range which does not deviate from the summary of this disclosure.

[0134] In this embodiment, a vertical stripe type single cell stack device is exemplified in which a so-called "vertical stripe type" single cell having only one power generation element portion is arranged on the surface of a support substrate, and the power generation element portion includes a fuel electrode, a solid electrolyte layer, and an air electrode. The present disclosure can be applied to a so-called "horizontal stripe type" single cell stack device in which power generation elements are respectively provided at a plurality of mutually separated portions on the surface of a support substrate, and adjacent power generation elements are electrically connected.

[0135] In addition, in the present embodiment, the case of using a hollow flat support substrate is exemplified. The present disclosure can also be applied to a single cell stack device using a cylindrical support substrate. In addition, the present disclosure can also be applied to a flat-type single cell stack device in which so-called "flat-type" single cells are arranged in the thickness direction.

[0136] In addition, the above embodiments show an example in which a fuel electrode is provided on a support substrate and an air electrode is arranged on the surface of a single cell. The present disclosure can also be applied to a single cell stack device having the opposite configuration, that is, an air electrode is provided on a support substrate and a fuel electrode is arranged on the surface of a single cell.

[0137] In addition, in the above-mentioned embodiments, a fuel cell, a fuel cell stack device, a fuel cell module, and a fuel cell device are shown as an example of a "single cell", a "single cell stack device", a "module", and a "module housing device", but as other examples, they may also be an electrolysis cell, an electrolysis cell stack device, an electrolysis module, and an electrolysis device, respectively.

[0138] As described above, the cell stack device 10 according to the embodiment includes a cell stack 11 and an end current collecting member 17. The cell stack 11 is provided with a plurality of cells 1 arranged therein. The end current collecting member 17 is located at the end of the cell stack 11 in the arrangement direction of the plurality of cells 1. Moreover, the surface of the end current collecting member 17 exposed to the oxidizing atmosphere (external space 23) is covered with a covering material 17b including manganese, and the surface of the end current collecting member 17 exposed to the reducing atmosphere (internal space 22) is covered with a film different from the covering material 17b. Thus, the aging resistance of the cell stack device 10 can be improved.

[0139] In addition, the cell stack device 10 according to the embodiment further includes a fixing material 13 for fixing the cell 1 and the end current collecting member 17. Furthermore, the surface of the end current collecting member 17 in contact with the fixing material 13 is covered with a film different from the covering material 17b. Thus, the aging resistance of the cell stack device 10 can be further improved.

[0140] In addition, the cell stack device 10 according to the embodiment further includes a fixing material 13 for fixing the cell 1 and the end current collecting member 17. Furthermore, the covering material 17b and a film different from the covering material are located on the surface of the end current collecting member 17 that is in contact with the fixing material 13. Thus, the aging resistance of the cell stack device 10 can be improved.

[0141] Furthermore, in the single cell stack device 10 according to the embodiment, the surface roughness of the film different from the covering material 17b located on the surface of the end current collecting member 17 in contact with the fixing material 13 is greater than the surface roughness of the covering material 17b located on the surface of the end current collecting member 17 in contact with the fixing material 13. Thus, the aging resistance of the single cell stack device 10 can be improved.

[0142] Furthermore, in the single cell stack device 10 according to the embodiment, the area S1 of the film different from the covering material 17b located on the surface of the end current collecting member 17 in contact with the fixing material 13 is smaller than the area S2 of the covering material 17b located on the surface of the end current collecting member 17 in contact with the fixing material 13. Thus, the aging resistance of the single cell stack device 10 can be improved.

[0143] In the cell stack device 10 according to the embodiment, the end current collector member 17 is made of stainless steel, and the film different from the covering material 17b is a natural oxide film 17a1 located on the surface of the stainless steel. This can improve the aging resistance of the cell stack device 10 and can manufacture the end current collector member 17 at low cost.

[0144] In the cell stack device 10 according to the embodiment, the film different from the covering material 17 b is the reduction prevention film 17 c . This can improve the aging resistance of the cell stack device 10 and improve the performance of the end current collecting member 17 .

[0145] In addition, the cell stack device 10 according to the embodiment includes a cell stack 11 and an end current collecting member 17. The cell stack 11 is provided with a plurality of cells 1 arranged therein. The end current collecting member 17 is located at the end of the cell stack 11 in the arrangement direction of the plurality of cells 1. Moreover, the end current collecting member 17 is not exposed in the reducing atmosphere (internal space 22). Thus, the aging resistance of the cell stack device 10 can be improved.

[0146] In the cell stack device 10 according to the embodiment, the entire surface of the end current collecting member 17 is covered with the covering material 17b containing manganese. This can improve the aging resistance of the cell stack device 10 and can manufacture the end current collecting member 17 at low cost.

[0147] In addition, the cell stack device 10 according to the embodiment further includes a fixing material 13 for fixing the cell 1 and the end current collecting member 17. Furthermore, the surface of the end current collecting member 17 exposed to the oxidizing atmosphere (external space 23) is covered with a covering material 17b including manganese, and the surface of the end current collecting member 17 in contact with the fixing material 13 is covered with a film different from the covering material 17b. Thus, the aging resistance of the cell stack device 10 can be further improved.

[0148] Furthermore, the module 80 according to the embodiment is configured by storing the above-described cell stack device 10 in a storage container 81. This allows the module 80 to have high deterioration resistance.

[0149] Furthermore, the module housing device 90 according to the embodiment is configured to house the module 80 described above and auxiliary equipment for operating the module 80 in an outer casing 91. Thus, the module housing device 90 can be highly resistant to aging.

[0150] In addition, the metal member (end current collecting member 17) according to the embodiment has a surface exposed in an oxidizing atmosphere (external space 23) and a surface exposed in a reducing atmosphere (internal space 22). Moreover, the surface exposed in the oxidizing atmosphere (external space 23) is covered with a covering material 17b containing manganese, and the surface exposed in the reducing atmosphere (internal space 22) is covered with a film different from the covering material 17b. Thus, the aging resistance of the end current collecting member 17 can be improved.

[0151] The embodiments disclosed herein should be considered to be illustrative and not restrictive in all aspects. In fact, the above embodiments can be implemented in many ways. In addition, the above embodiments can be omitted, replaced, and changed in various ways without departing from the attached claims and their gist.

[0152] -Explanation of symbols-

[0153] 1 single battery

[0154] 10 Single Cell Stack Device

[0155] 11 Single Cell Stack

[0156] 12 Fixed components

[0157] 13. Fixing material

[0158] 14 Supporting member

[0159] 15 Support

[0160] 16 Gas tank

[0161] 17 End current collecting member

[0162] 17a base material

[0163] 17a1 Natural oxide film

[0164] 17b Covering material

[0165] 17c Piyuan anti-corrosion film

[0166] 80 modules

[0167] 90 Module Containment Device

[0168] 91 External shell

[0169] Area of ​​S1 and S2.

Claims

1. A single cell stack device, comprising: A single cell stack, in which a plurality of single cells are arranged; and an end current collecting member located at an end of the cell stack in the arrangement direction of the plurality of cells, The surface of the end current collecting member exposed to the oxidizing atmosphere is covered with a covering material including manganese, The surface of the end current collecting member exposed in the reducing atmosphere is covered with a film different from the covering material, and the constituent elements of the film are unlikely to cause a reduction reaction even in the reducing atmosphere.

2. The single cell stack device according to claim 1, wherein: A fixing material for fixing the single cell and the end current collecting member is also provided. The surface of the end current collecting member in contact with the fixing material is covered with the film.

3. The single cell stack device according to claim 1, wherein: A fixing material for fixing the single cell and the end current collecting member is also provided. The covering material and the film are located on a surface of the end current collecting member that is in contact with the fixing material.

4. The single cell stack device according to claim 3, wherein: The surface roughness of the film located on a surface of the end current collecting member in contact with the fixing material is greater than the surface roughness of the covering material located on a surface of the end current collecting member in contact with the fixing material.

5. The single cell stack device according to claim 3 or 4, wherein: The area of ​​the film located on the surface of the end current collecting member in contact with the fixing material is smaller than the area of ​​the covering material located on the surface of the end current collecting member in contact with the fixing material.

6. The single cell stack device according to any one of claims 1 to 4, wherein: The end current collecting member is made of stainless steel, The film is a natural oxide film located on the surface of stainless steel.

7. The single cell stack device according to any one of claims 1 to 4, wherein: The film is a reduction preventing film.

8. A module, The single cell stack device according to any one of claims 1 to 7 is accommodated in a storage container.

9. A module receiving device, The module according to claim 8 and auxiliary equipment for operating the module are housed in an outer casing.

10. A metal component, having a surface exposed in an oxidizing atmosphere and a surface exposed in a reducing atmosphere, The surface exposed in the oxidizing atmosphere is covered with a covering material including manganese, The surface exposed in the reducing atmosphere is covered with a film different from the covering material, and the constituent elements of the film are unlikely to cause a reduction reaction even in a reducing atmosphere.

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