Electrochemical cell, electrochemical cell device, module, and module housing device

Abstract

An electrochemical cell is provided with an element part, a metal support body, and an oxide layer. The element part has a solid electrolyte layer, and a first electrode and a second electrode disposed so as to sandwich the solid electrolyte layer. The support body contains chromium and supports the element part. The oxide layer is located between the first electrode and the support and has a metal component. A porosity of the oxide layer is smaller than a porosity of the first electrode.

Description

Technical Field

[0001] The present disclosure relates to an electrochemical cell, an electrochemical cell device, a module, and a module receiving device. Background Art

[0002] In recent years, various fuel cell stack devices including a plurality of fuel cells have been proposed as next-generation energy sources. A fuel cell is a type of electrochemical cell that can generate electricity using a fuel gas such as a hydrogen-containing gas and an oxygen-containing gas such as air.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: International Publication No. 2020 / 218431 Summary of the invention

[0006] An electrochemical cell according to one embodiment of the present invention comprises an element unit, a metal support, and an oxide layer. The element unit comprises a solid electrolyte layer and a first electrode and a second electrode disposed between the solid electrolyte layer. The support comprises chromium and supports the element unit. The oxide layer is located between the first electrode and the support and has a metal component. The porosity of the oxide layer is smaller than the porosity of the first electrode.

[0007] An electrochemical cell according to one embodiment of the present invention comprises an element portion, a metal support, an adhesive layer, and an oxide layer. The support contains chromium and supports the element portion. The adhesive layer is located between the element portion and the support. The oxide layer is located between the adhesive layer and the support and has a metal component. The porosity of the oxide layer is smaller than the porosity of the adhesive layer.

[0008] Furthermore, an electrochemical cell device of the present disclosure includes a cell stack, and the cell stack includes the electrochemical cell described above.

[0009] In addition, a module of the present disclosure includes: the electrochemical cell device described above; and a storage container that stores the electrochemical cell device.

[0010] In addition, the module housing device of the present disclosure includes: the module described above; an auxiliary machine for operating the module; and an outer casing that houses the module and the auxiliary machine. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1A This is a cross-sectional view showing an example of the electrochemical cell according to the first embodiment.

[0012] Figure 1B This is a side view of an example of the electrochemical cell according to the first embodiment as viewed from the air electrode side.

[0013] Figure 1C Yes Figure 1A An enlarged cross-sectional view of area A is shown.

[0014] Figure 1D This is a cross-sectional view showing another example of the electrochemical cell according to the first embodiment.

[0015] Figure 1E This is a cross-sectional view showing another example of the electrochemical cell according to the first embodiment.

[0016] Figure 2A This is a perspective view showing an example of the battery stack device according to the first embodiment.

[0017] Figure 2B yes Figure 2A A cross-sectional view along line XX is shown.

[0018] Figure 2C This is a plan view showing an example of the battery stack device according to the first embodiment.

[0019] Figure 3 This is an external perspective view showing an example of the module according to the first embodiment.

[0020] Figure 4 This is an exploded perspective view schematically showing an example of the module housing device according to the first embodiment.

[0021] Figure 5A It is a perspective view showing an example of a flat plate type electrochemical cell.

[0022] Figure 5B yes Figure 5A A partial cross-sectional view of an electrochemical cell is shown.

[0023] Figure 6 This is a cross-sectional view showing still another example of the electrochemical cell according to the first embodiment.

[0024] Figure 7 This is a cross-sectional view showing an example of the electrochemical cell according to the second embodiment.

[0025] Fig. 8A This is a cross-sectional view showing another example of the electrochemical cell according to the second embodiment.

[0026] Figure 8B This is a cross-sectional view showing another example of the electrochemical cell according to the second embodiment.

[0027] Fig. 9A This is a cross-sectional view showing an example of an electrochemical cell according to a third embodiment.

[0028] Fig. 9B This is a cross-sectional view showing another example of the electrochemical cell according to the third embodiment. DETAILED DESCRIPTION

[0029] In the above-mentioned fuel cell stack device, there is room for improvement in terms of enhancing cell performance.

[0030] Therefore, it is desired to provide an electrochemical cell, an electrochemical cell device, a module, and a module housing device that can improve performance.

[0031] Hereinafter, embodiments of the electrochemical cell, electrochemical cell device, module, and module storage device disclosed in the present application will be described in detail with reference to the accompanying drawings. It should be noted that the present invention is not limited to the embodiments described below.

[0032] In addition, it should be noted that the drawings are schematic, and 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 and the ratio are different.

[0033] [First embodiment]

[0034] <Structure of electrochemical cell>

[0035] First, refer to Figure 1A to Figure 1C As the electrochemical cell of the first embodiment, a solid oxide fuel cell monomer is used for explanation. The electrochemical cell device may also include a cell stack having a plurality of electrochemical cells. The electrochemical cell device having a plurality of electrochemical cells is referred to as a cell stack device.

[0036] Figure 1A This is a cross-sectional view showing an example of the electrochemical cell according to the first embodiment. Figure 1B This is a side view of an example of the electrochemical cell according to the first embodiment as viewed from the air electrode side. Figure 1C Yes Figure 1A The cross-sectional view of the area A shown is enlarged. It should be noted that Figure 1A to Figure 1C A portion of each structure of an electrochemical cell is shown in an enlarged manner. Hereinafter, an electrochemical cell may also be simply referred to as a battery.

[0037] like Figure 1A to Figure 1C As shown, the battery 1 includes an element portion 3 in which a fuel electrode 5 as a first electrode, a solid electrolyte layer 6 and an air electrode 8 as a second electrode are stacked, a support 2 , and an oxide layer 9 .

[0038] The support 2 is a metal member containing chromium. In addition, the support 2 has electrical conductivity. The support 2 may be, for example, a stainless steel with high heat resistance such as ferrite stainless steel or austenite stainless steel. The support 2 may also be, for example, a nickel-chromium alloy or an iron-chromium alloy. The support 2 may contain, for example, a metal oxide. The support 2 may also be composed of, for example, one or more metal plates. The support 2 electrically connects the batteries 1 adjacent to each other in the X-axis direction.

[0039] The support body 2 has a first surface n1 and a second surface n2 located on the opposite side of the first surface n1. The support body 2 has an opening 2b located at a position opposite to the element part 3, specifically, a position in contact with the oxide layer 9. The opening 2b penetrates between the first surface n1 and the second surface n2 in the X-axis direction. In addition, the support body 2 has a component 32 located outside the gas flow path 2a extending in the Z-axis direction. The support body 2 allows the fuel gas flowing in the gas flow path 2a to flow to the element part 3. The diameter of the opening 2b can be, for example, 0.1 mm to 0.5 mm, in particular 0.3 mm to 0.4 mm. The opening ratio in the area where the opening 2b is formed can be, for example, 10% or more.

[0040] The support 2 may also include a substrate 201 and a covering portion 202. The covering portion 202 is located on the surface of the substrate 201. The covering portion 202 may have, for example, insulating properties. The covering portion 202 may contain, for example, chromium oxide (Cr2O3). The covering portion 202 may contain, for example, a larger chromium content than the substrate 201. By having the covering portion 202 in this way, the durability of the support 2 is improved. The covering portion 202 may also contain, for example, a metal component different from chromium, such as manganese. It should be noted that the support 2 may also partially include the covering portion 202. In addition, the support 2 may also have a further laminated structure.

[0041] The element portion 3 is located on the first surface n1 side of the support 2. The element portion 3 is fixed to the support 2 via an oxide layer 9. The element portion 3 includes a fuel electrode 5, a solid electrolyte layer 6, and an air electrode 8.

[0042] The fuel electrode 5 is a first electrode in contact with the fuel gas as a reducing gas. The fuel electrode 5 has gas permeability. The open porosity of the fuel electrode 5 can be, for example, in the range of 30% to 50%, particularly 35% to 45%. The open porosity of the fuel electrode 5 is sometimes referred to as the porosity or void ratio of the fuel electrode 5.

[0043] The material of the fuel electrode 5 can use a generally known material. The fuel electrode 5 can also use a porous conductive ceramic, such as a ceramic containing ZrO2, Ni and / or NiO in which calcium oxide, magnesium oxide or rare earth element oxide is solid-dissolved. The rare earth element oxide can contain, for example, a plurality of rare earth elements selected from Sc, Y, La, Nd, Sm, Gd, Dy and Yb. ZrO2 in which calcium oxide, magnesium oxide or rare earth element oxide is solid-dissolved is sometimes referred to as stabilized zirconium oxide. Stabilized zirconium oxide can include partially stabilized zirconium oxide.

[0044] The solid electrolyte layer 6 is an electrolyte, and transfers ions between the fuel electrode 5 and the air electrode 8. The solid electrolyte layer 6 has gas barrier properties, and thus the fuel gas and the oxygen-containing gas are unlikely to leak.

[0045] The material of the solid electrolyte layer 6 may be, for example, ZrO2 in which 3 mol% to 15 mol% of rare earth element oxides are solid-dissolved. The rare earth element oxides may include, for example, one or more rare earth elements selected from Sc, Y, La, Nd, Sm, Gd, Dy, and Yb. The solid electrolyte layer 6 may include, for example, ZrO2 in which Yb, Sc, or Gd is solid-dissolved, CeO2 in which La, Nd, or Yb is solid-dissolved, BaZrO3 in which Sc or Yb is solid-dissolved, or BaCeO3 in which Sc or Yb is solid-dissolved.

[0046] The air electrode 8 is a second electrode in contact with the oxygen-containing gas. The air electrode 8 has air permeability. The open porosity of the air electrode 8 may be, for example, in the range of 20% to 50%, particularly in the range of 30% to 50%.

[0047] The material of the air electrode 8 is not particularly limited as long as it is a material commonly used for air electrodes. The material of the air electrode 8 may be, for example, a conductive ceramic such as a so-called ABO3 type perovskite oxide.

[0048] The material of the air electrode 8 may be, for example, a composite oxide in which Sr (strontium) and La (lanthanum) coexist at the A site. Examples of such a composite oxide include 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, etc. It should be noted that x is 0<x<1, and y is 0<y<1.

[0049] In addition, the element portion 3 may also include an intermediate layer located between the solid electrolyte layer 6 and the air electrode 8. When the element portion 3 includes the intermediate layer, the intermediate layer has a function as, for example, a diffusion suppression layer. When Sr (strontium) contained in the air electrode 8 diffuses into the solid electrolyte layer 6, a resistance layer of SrZrO3 is formed in the solid electrolyte layer 6. The intermediate layer makes it difficult for Sr to diffuse, thereby making it difficult for SrZrO3 to form.

[0050] The material of the intermediate layer is generally not particularly limited as long as it is a material that makes it difficult for elements to diffuse between the air electrode 8 and the solid electrolyte layer 6. The material of the intermediate layer may include, for example, cerium oxide (CeO2) in which a rare earth element other than Ce (cerium) is solid-dissolved. As the rare earth element, for example, Gd (gadolinium), Sm (samarium), etc. may be used.

[0051] In addition, the oxide layer 9 is located between the support 2 and the element portion 3. The oxide layer 9 is located between the first surface n1 of the support 2 and the fuel electrode 5, and joins the support 2 and the element portion 3. The oxide layer 9 has, for example, electrical conductivity.

[0052] The porosity of the oxide layer 9 is smaller than that of the fuel electrode 5. The porosity of the oxide layer 9 can be, for example, in the range of 1% to 10%, particularly 3% to 8%. By making the porosity of the oxide layer 9 smaller than that of the fuel electrode 5, the interface strength between the oxide layer 9 and the fuel electrode 5, that is, the bonding strength at the boundary between the oxide layer 9 and the fuel electrode 5 is improved, and it is difficult to peel off. As a result, the durability of the battery 1 is improved, so the battery performance can be improved. The porosity of the oxide layer 9, the fuel electrode 5, etc. is, for example, observed by observing the cross section of each part with a SEM (scanning electron microscope), and taking a photo, for example, at 3000 times. The photo is subjected to image processing to identify the pores, and the porosity can be obtained by calculating the total area of ​​the pores relative to the area of ​​the entire image. For comparison of the porosity of the oxide layer 9 and the fuel electrode 5, for example, the average porosity calculated from the cross-sectional photos of any three places is compared for each part.

[0053] Furthermore, the porosity of the oxide layer 9 may be less than 5%. When the porosity of the oxide layer 9 is less than 5%, it is difficult for metals such as Cr and Mn contained in the support 2 to diffuse into the fuel electrode 5. As a result, the durability of the fuel electrode 5 is improved. In addition, if the oxide layer 9 having a porosity of less than 5% is arranged on the support 2, Cr is difficult to evaporate from the support 2. As a result, the durability of the battery 1 is improved.

[0054] The oxide layer 9 has a metal component other than Cr. The oxide layer 9 has, for example, an oxide of a first metal and a second metal different from the first metal. The first metal is, for example, Ti (titanium). The second metal is, for example, Ni (nickel). The second metal is dispersed in the interior of the oxide layer 9. The second metal can be dispersed, for example, as metal particles or oxide particles. The first metal can also be a metal other than Ti, such as Al (aluminum) or Si (silicon). The first metal is not prone to volume change even when in contact with a reducing atmosphere, and it is easy to maintain a porosity of less than 5%. The second metal can also be a metal other than Ni, such as Cu (copper), Co (cobalt) or Zn (zinc). The second metal has high electronic conductivity and is easy to maintain electronic conduction between the fuel electrode 5 and the support 2. The oxide layer 9 can also contain a trace amount of Cr.

[0055] In addition, the covering portion 202 of the support 2 may have a metal component contained in the oxide layer 9. The metal component may be, for example, a second metal. By having the same metal component as the oxide layer 9 as the covering portion 202 in contact with the oxide layer 9, the interface strength between the oxide layer 9 and the support 2 is improved. As a result, the durability of the battery 1 is improved, thereby improving the battery performance. In addition, by having the covering portion 202 having a second metal contained in the oxide layer 9 and having high electronic conductivity, the insulation of the covering portion 202 can be reduced, and it is easy to maintain electronic conduction between the fuel electrode 5 and the support 2.

[0056] In addition, the oxide layer 9 may be arranged so as to overlap with the support body 2 when viewed from above. That is, the portion of the support body 2 opposite to the opening 2b may not have the oxide layer 9, but may be provided with a through hole that penetrates the oxide layer 9 in the thickness direction. The through hole is connected to the opening 2b, and the fuel gas flowing in the gas flow path 2a is easily circulated to the element part 3. In addition, since the oxide layer 9 is located on the surface of the covering part 202, the covering part 202 is difficult to grow. In addition, since Cr in the support body 2 is difficult to diffuse, the durability of the battery 1 is improved. As a result, the battery performance can be improved.

[0057] Figure 1D and Figure 1E This is a cross-sectional view showing another example of the electrochemical cell according to the first embodiment.

[0058] exist Figure 1A In the example shown, the side surface of the fuel electrode 5 and the side surface of the oxide layer 9 are covered with the solid electrolyte layer 6, and the gas flow path 2a through which the fuel gas flows is hermetically sealed. Figure 1D As shown, the side of the fuel electrode 5 and the side of the oxide layer 9 may be covered and sealed by a dense sealing material 7. The sealing material 7 covering the side of the fuel electrode 5 and the side of the oxide layer 9 may have electrical insulation. The material of the sealing material 7 may be glass or ceramic, for example.

[0059] In addition, if Figure 1E As shown, the gas flow path 2a of the support body 2 may also be formed by a member 32 having projections and depressions.

[0060] <Structure of electrochemical battery device>

[0061] Next, refer to Figure 2A to Figure 2C The electrochemical cell device of this embodiment using the above-mentioned electrochemical cell will be described. Figure 2A This is a perspective view showing an example of the electrochemical cell device according to the first embodiment. Figure 2B yes Figure 2A A cross-sectional view along line XX is shown. Figure 2C This is a plan view showing an example of the electrochemical cell device according to the first embodiment.

[0062] like Figure 2A As shown, the battery stack device 10 includes a battery stack 11 having a plurality of batteries 1 arranged (stacked) in the thickness direction (X-axis direction) of the batteries 1 , and a fixing member 12 .

[0063] The fixing member 12 includes a fixing material 13 and a support member 14. The support member 14 supports the battery 1. The fixing material 13 fixes the battery 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.

[0064] like Figure 2B As shown, the support body 15 has an insertion hole 15a into which the lower end portions of the plurality of batteries 1 are inserted. The lower end portions of the plurality of batteries 1 are joined to the inner wall of the insertion hole 15a via a fixing material 13.

[0065] 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.

[0066] exist Figure 2A In the example shown, fuel gas is stored in an internal space 22 formed by a support body 15 as a support member 14 and a gas tank 16. 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 FIG. 2 ) inside the battery 1. Figure 1A ) is supplied. The fuel gas supplied to the gas tank 16 is supplied by the reformer 102 (see Figure 3 )generate.

[0067] The hydrogen-rich fuel gas can be produced by steam reforming a raw fuel, etc. When the fuel gas is produced by steam reforming, the fuel gas contains water vapor.

[0068] exist Figure 2A In the example shown, there are two rows of battery stacks 11, two supports 15, and a gas tank 16. The two rows of battery stacks 11 each have a plurality of batteries 1. Each battery 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.

[0069] The shape of the insertion hole 15a is, for example, an oblong shape when viewed from above. The length of the insertion hole 15a in the thickness direction T, which is the arrangement direction of the battery 1, is greater than the distance between the two end current collecting members 17 located at both ends of the battery stack 11. The width of the insertion hole 15a is, for example, greater than the width direction W of the battery 1 (see Figure 1A ) is long.

[0070] like Figure 2B As shown, the joint between the inner wall of the insertion hole 15a and the lower end of the battery 1 is filled and cured with the fixing material 13. As a result, the inner wall of the insertion hole 15a is joined and fixed to the lower ends of the plurality of batteries 1, respectively, and the lower ends of the batteries 1 are joined and fixed to each other. The gas flow path 2a of each battery 1 communicates with the internal space 22 of the support member 14 at the lower end.

[0071] A material with low conductivity such as glass can be used for the fixing material 13 and the bonding material 21. As specific materials of the fixing material 13 and the bonding material 21, amorphous glass and the like can be used, and in particular, crystallized glass and the like can be used.

[0072] 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 be used.

[0073] In addition, if Figure 2B As shown, a conductive member 18 is interposed between adjacent cells 1 among the plurality of cells 1. The conductive member 18 electrically connects one adjacent cell 1 in series with another adjacent cell 1. More specifically, the conductive member 18 connects the fuel electrode 5 of one cell 1 with the air electrode 8 of another cell 1.

[0074] In addition, if Figure 2BAs shown in FIG. 1 , the outermost battery 1 in the arrangement direction of the plurality of batteries 1 is electrically connected to an end current collecting member 17. The end current collecting member 17 is connected to a conductive portion 19 protruding to the outside of the battery stack 11. The conductive portion 19 collects the power generated by the battery 1 and leads it to the outside. Figure 2A In the figure, the end current collecting member 17 is omitted.

[0075] In addition, if Figure 2C As shown, the battery stack device 10 may be a single battery in which two battery stacks 11A and 11B are connected in series. In this case, the conductive portion 19 of the battery stack device 10 may include a positive terminal 19A, a negative terminal 19B, and a connection terminal 19C.

[0076] The positive terminal 19A is the positive electrode when the power generated by the battery 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 battery stack 11A. The negative terminal 19B is the negative electrode when the power generated by the battery 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 battery stack 11B.

[0077] The connection terminal 19C electrically connects the end current collecting member 17 on the negative electrode side in the battery stack 11A and the end current collecting member 17 on the positive electrode side in the battery stack 11B.

[0078] <Module>

[0079] Next, use Figure 3 A module according to an embodiment of the present disclosure using the above-described battery stack device 10 will be described. Figure 3 It is a perspective view showing the appearance of the module according to the first embodiment. Figure 3 The diagram shows a state in which the front surface and the rear surface as a part of the storage container 101 are removed and the cell stack device 10 of the fuel cell stored inside is taken out to the rear.

[0080] like Figure 3 As shown, the module 100 includes a storage container 101 and a battery stack device 10 stored in the storage container 101. In addition, a reformer 102 is arranged above the battery stack device 10.

[0081] The reformer 102 reforms a raw fuel such as natural gas or kerosene to generate a fuel gas, and supplies it to the cell 1. The raw fuel is supplied to the reformer 102 through a raw fuel supply pipe 103. It should be noted that the reformer 102 may include a gasification unit 102a for gasifying water, and a reforming unit 102b. The reforming unit 102b includes a reforming catalyst (not shown) to reform the raw fuel into a fuel gas. Such a reformer 102 can perform steam reforming as a highly efficient reforming reaction.

[0082] The fuel gas generated in the reformer 102 is then discharged into the gas flow path 2a (see FIG. 1 ) of the cell 1 through the gas flow pipe 20, the gas tank 16, and the support member 14. Figure 1A )supply.

[0083] In the module 100 having the above structure, the temperature inside the module 100 during power generation usually reaches about 500° C. to 1000° C. as the gas is combusted and the battery 1 generates power.

[0084] Such a module 100 can be configured to have improved performance by accommodating the battery stack device 10 with improved battery performance as described above.

[0085] <Module storage device>

[0086] Figure 4 1 is an exploded perspective view showing an example of a module storage device according to the first embodiment. The module storage device 110 of this embodiment includes an outer casing 111, Figure 3 The module 100 shown in the figure and the auxiliary machine not shown in the figure. The auxiliary machine operates the module 100. The module 100 and the auxiliary machine are accommodated in the outer casing 111. It should be noted that Figure 4 In the figure, part of the structure is omitted.

[0087] Figure 4 The outer casing 111 of the module housing device 110 shown in the figure has a support 112 and an outer panel 113. The partition plate 114 divides the outer casing 111 into upper and lower parts. The space above the partition plate 114 in the outer casing 111 is a module housing chamber 115 for housing the module 100, and the space below the partition plate 114 in the outer casing 111 is an auxiliary machine housing chamber 116 for housing auxiliary machines for operating the module 100. It should be noted that Figure 4 In the figure, the auxiliary machines accommodated in the auxiliary machine accommodation chamber 116 are omitted.

[0088] The partition plate 114 has an air flow port 117 for allowing air in the auxiliary machine accommodation chamber 116 to flow toward the module accommodation chamber 115. The exterior plate 113 constituting the module accommodation chamber 115 has an exhaust port 118 for exhausting air in the module accommodation chamber 115.

[0089] In such a module housing device 110 , as described above, by providing the module 100 with improved battery performance in the module housing chamber 115 , it is possible to achieve a module housing device 110 with improved performance.

[0090] Figure 5A and Figure 5B Another example of the electrochemical cell according to the first embodiment is shown. Figure 5AIt is a perspective view showing an example of a flat plate type electrochemical cell. Figure 5B It is shown Figure 5A A partial cross-sectional view of an electrochemical cell is shown.

[0091] like Figure 5A , Figure 5B As shown, the battery 1 includes an element portion 3 in which a fuel electrode 5, a solid electrolyte layer 6, and an air electrode 8 are stacked, a support 2, an oxide layer 9, and conductive members 91 and 92. In an electrochemical battery device in which a plurality of flat-plate type batteries are stacked, for example, a plurality of batteries 1 are electrically connected by conductive members 91 and 92, which are metal layers adjacent to each other. The conductive members 91 and 92 electrically connect adjacent batteries 1 to each other and have a flow path for supplying gas to the fuel electrode 5 or the air electrode 8.

[0092] like Figure 5B As shown, the cell 1 has a sealing material for hermetically sealing the fuel gas flow path 98 and the oxygen-containing gas flow path 97 of the flat cell stack. The sealing material is a fixing member 96 of the cell 1, and has a bonding material 93 and supporting members 94 and 95 as a frame. The bonding material 93 can be glass or a metal material such as silver solder.

[0093] The support member 94 may also be a so-called partition that divides the flow path 98 of the fuel gas and the flow path 97 of the oxygen-containing gas. The material of the support members 94 and 95 may be, for example, a conductive metal or an insulating ceramic. The support members 94 and 95 may also be made of insulating materials on both sides or on either side. When the support member 94 is made of metal, the support member 94 may be integrated with the conductive member 91. When the support member 95 is made of metal, the support member 95 may be integrated with the conductive member 92.

[0094] One of the support members 94 and 95 is insulating, and electrically insulates the two conductive members 91 and 92 sandwiching the flat battery from each other.

[0095] The oxide layer 9 is located between the support 2 and the element portion 3. The oxide layer 9 is located between the support 2 and the fuel electrode 5, and joins the support 2 and the element portion 3. The oxide layer 9 has, for example, electrical conductivity.

[0096] Figure 6 FIG. 2 is a cross-sectional view showing another example of the electrochemical cell of the first embodiment. Figure 6 As shown, the fuel electrode 5 may have a portion 5a protruding toward the opening 2b into the oxide layer 9. By having this portion 5a, for example, the bonding strength between the fuel electrode 5 and the oxide layer 9 is improved, and the durability of the battery 1 is improved. In addition, the fuel electrode 5 may also have a portion 5b located at a position away from the opening 2b.

[0097] [Second Embodiment]

[0098] Figure 7 1 is a cross-sectional view showing an example of an electrochemical cell according to the second embodiment. The battery 1 according to this embodiment has an adhesive layer 34 located between the element portion 3 and the oxide layer 9. The adhesive layer 34 bonds the element portion 3 to the oxide layer 9. The adhesive layer 34 has, for example, air permeability. The adhesive layer 34 may have, for example, electrical conductivity.

[0099] The adhesive material layer 34 includes, for example, conductive particles such as Ni, Cu, Co, and Zn, inorganic oxides such as TiO2, Al2O3, SiO2, rare earth element oxides (Y2O3, CeO2, etc.), and transition metal oxides (Fe2O3, CuO, etc.). The adhesive material layer 34 may also be located at the portion where the opening 2b is located, with the surface exposed.

[0100] The porosity (open porosity) of the oxide layer 9 is smaller than that of the adhesive layer 34. The open porosity of the adhesive layer 34 may be, for example, in the range of 20% to 40%, particularly 25% to 35%. By making the porosity of the oxide layer 9 smaller than that of the adhesive layer 34, the interface strength between the oxide layer 9 and the adhesive layer 34 is improved, and it is difficult to peel off. As a result, the durability of the battery 1 is improved, and thus the battery performance can be improved. The porosity of the oxide layer 9, the adhesive layer 34, etc. is determined by, for example, observing the cross section of each part with a SEM (scanning electron microscope) and taking, for example, a 3000-fold photograph. The photo is subjected to image processing to identify the pores, and the porosity can be obtained by calculating the total area of ​​the pores relative to the area of ​​the entire image. For comparison of the porosity of the oxide layer 9 and the adhesive layer 34, for example, the average porosity calculated from the cross-sectional photographs of any three places is compared for each part.

[0101] Fig. 8A , Figure 8B FIG. 2 is a cross-sectional view showing another example of the electrochemical cell according to the second embodiment. Fig. 8A As shown, the adhesive material layer 34 may have a portion 34a protruding toward the inside of the oxide layer 9 toward the opening 2b. By having this portion 34a, for example, the bonding strength between the adhesive material layer 34 and the oxide layer 9 is improved, and the durability of the battery 1 is further improved. It should be noted that the oxide layer 9 may have a space 35 located between the portion 34a and the opening 2b. In addition, although not shown in the figure, the adhesive material layer 34 may also have a portion located away from the opening 2b.

[0102] In addition, if Figure 8B As shown, the oxide layer 9 may have a portion 9a protruding toward the inside of the opening 2b. By having the portion 9a, for example, the bonding strength between the oxide layer 9 and the support 2 is improved, and the durability of the battery 1 is further improved.

[0103] In addition, the portion 34a of the adhesive material layer 34 may extend through the oxide layer 9 to the opening 2b. In this case, the front end portions of the portion 34a and the portion 9a may be located at approximately the same height (for example, refer to portion P1), the portion 9a may protrude more than the portion 34a (for example, refer to portion P2), and the portion 34a may protrude more than the portion 9a (for example, refer to portion P3). It should be noted that the oxide layer 9 and the adhesive material layer 34 may be considered together as a bonding layer located between the support body 2 and the element portion 3. In this case, the oxide layer 9 may be considered as a low porosity portion of the bonding layer, and the adhesive material layer 34 may be considered as a high porosity portion of the bonding layer.

[0104] [Third Embodiment]

[0105] Fig. 9A This is a cross-sectional view showing an example of an electrochemical cell according to a third embodiment. Fig. 9B 1 is a cross-sectional view showing another example of the electrochemical cell of the third embodiment. The battery 1 of this embodiment is different from the electrochemical cells of the above embodiments in that it has a constraining layer 36 located between the element portion 3 and the oxide layer 9 or between the element portion 3 and the adhesive layer 34 .

[0106] The material of the constrained layer 36 shows a similar shrinkage rate during firing as the material of the solid electrolyte layer 6. The warping or deformation of the element portion 3 obtained by sandwiching the material of the fuel electrode 5 between the material of the solid electrolyte layer 6 and the material of the constrained layer 36 and firing is reduced, thereby improving the battery performance.

[0107] It should be noted that, when the material of the constrained layer 36 is the same as that of the solid electrolyte layer 6, or when the permeability of the constrained layer 36 is low, a plurality of through holes may be provided in the thickness direction (X-axis direction) that penetrate the constrained layer 36. The position and shape of the through hole may be the same as or different from that of the opening 2b.

[0108] [Other embodiments]

[0109] In the above-mentioned embodiment, as an example of "electrochemical cell", "electrochemical cell device", "module" and "module housing device", a fuel cell monomer, a fuel cell stack device, a fuel cell module and a fuel cell device are shown, but as another example, they may be an electrolytic cell, an electrolytic cell stack device, an electrolytic module and an electrolytic device, respectively. The electrolytic cell has a hydrogen electrode as a first electrode and an oxygen electrode as a second electrode, and decomposes water vapor into hydrogen and oxygen or decomposes carbon dioxide into carbon monoxide and oxygen by supplying electricity. In addition, in the above-mentioned embodiment, as an example of an electrolyte material of an electrochemical cell, an oxide ion conductor or a hydrogen ion conductor is shown, but it may also be a hydroxide ion conductor. According to such an electrolytic cell, an electrolytic cell stack device, an electrolytic module and an electrolytic device, the performance can be improved.

[0110] 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.

[0111] As described above, the electrochemical cell (battery 1) of the embodiment includes an element portion 3, a metal support 2, and an oxide layer 9. The element portion 3 includes a solid electrolyte layer 6, and a first electrode (fuel electrode 5) and a second electrode (air electrode 8) disposed with the solid electrolyte layer 6 interposed therebetween. The support 2 contains chromium and supports the element portion 3. The oxide layer 9 is located between the first electrode and the support 2 and has a metal component. The porosity of the oxide layer 9 is smaller than that of the first electrode. Thus, the performance of the battery 1 can be improved.

[0112] In addition, the electrochemical cell (battery 1) of the embodiment includes an element portion 3, a metal support 2, an adhesive layer 34, and an oxide layer 9. The support 2 contains chromium and supports the element portion 3. The adhesive layer 34 is located between the element portion 3 and the support 2. The oxide layer 9 is located between the adhesive layer 34 and the support 2 and has a metal component. The porosity of the oxide layer 9 is smaller than the porosity of the adhesive layer 34. As a result, the performance of the battery 1 can be improved.

[0113] Furthermore, the electrochemical cell device (cell stack device 10 ) of the embodiment includes a cell stack 11 including the electrochemical cells described above. This can improve the performance of the cell stack device 10 .

[0114] In addition, the module 100 of the embodiment includes the electrochemical cell device described above and the storage container 101 for storing the electrochemical cell device. Thus, the performance of the module 100 can be improved.

[0115] The module storage device 110 of the embodiment includes the module 100 described above, an auxiliary machine for operating the module 100, and an outer casing for storing the module 100 and the auxiliary machine. Thus, the performance of the module storage device 110 can be improved.

[0116] It should be considered that the embodiments disclosed this time are illustrative and non-restrictive in all aspects. In fact, the above-mentioned embodiments can be implemented in many ways. In addition, the above-mentioned embodiments can also be omitted, replaced, and changed in various ways without departing from the additional technical solutions and their main purpose.

[0117] Description of reference numerals:

[0118] 1 Battery

[0119] 2 Support body

[0120] 3 Components

[0121] 5 Fuel electrode

[0122] 6 Solid electrolyte layer

[0123] 8 Air electrode

[0124] 9 Oxide layer

[0125] 10 Battery stack device

[0126] 34 Adhesive material layer

[0127] 100 modules

[0128] 110 Module containment device.

Claims

1. An electrochemical cell, wherein: The electrochemical cell comprises: an element portion including a solid electrolyte layer and a first electrode and a second electrode disposed so as to sandwich the solid electrolyte layer; a metal support body containing chromium and supporting the element portion; as well as an oxide layer, which is located between the first electrode and the support and has a metal component, The porosity of the oxide layer is smaller than the porosity of the first electrode.

2. The electrochemical cell according to claim 1, wherein The oxide layer includes an oxide of a first metal and a second metal different from the first metal.

3. The electrochemical cell according to claim 1 or 2, wherein: The support body has a covering portion located at a boundary portion with the oxide layer, The covering portion includes the metal component.

4. The electrochemical cell according to any one of claims 1 to 3, wherein The oxide layer is arranged so as to overlap with the support body in a plan view.

5. The electrochemical cell according to any one of claims 1 to 4, wherein The oxide layer contains nickel.

6. An electrochemical cell, wherein: The electrochemical cell comprises: Components Department; a metal support body containing chromium and supporting the element portion; an adhesive material layer located between the element portion and the support body; and an oxide layer, which is located between the adhesive material layer and the support body and has a metal component, The porosity of the oxide layer is smaller than the porosity of the adhesive material layer.

7. An electrochemical cell device, wherein: The electrochemical cell device comprises a cell stack, and the cell stack includes the electrochemical cell according to any one of claims 1 to 6.

8. A module, wherein: The module has: The electrochemical cell device of claim 7; and A storage container stores the electrochemical battery device.

9. A module receiving device, wherein: The module receiving device comprises: The module according to claim 8; Auxiliary machines, used to operate the modules; and An outer casing houses the module and the auxiliary machine.

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