Composite member, electrochemical cell, electrochemical cell device, module, and module storage device

Abstract

This composite member comprises a metal substrate, a coating layer, a sealing material, and an intermediate layer. The coating layer is positioned on the metal substrate and contains Zn and Mn. The sealing material is positioned on the coating layer and contains Ba. The intermediate layer is positioned between the coating layer and the sealing material, includes all of the main metal elements included in the sealing material, and has a Zn content greater than half the Ba content.

Description

Composite member, electrochemical cell, electrochemical cell device, module, and module housing device

[0001] The present disclosure relates to composite members, electrochemical cells, electrochemical cell devices, modules and module housing devices.

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

[0003] Japanese Patent Application Laid-Open No. 2018-170109

[0004] A composite member according to one aspect of the embodiment includes a metal substrate, a coating layer, a sealing material, and an intermediate layer. The coating layer is located on the metal substrate and contains Zn and Mn. The sealing material is located on the coating layer and contains Ba. The intermediate layer is located between the coating layer and the sealing material and contains all of the main metal elements contained in the sealing material, with the Zn content being greater than half the Ba content.

[0005] Also, an electrochemical cell according to one aspect of the embodiment includes a metal substrate, an element unit, a covering layer, a sealing material, and an intermediate layer. The element unit is located on the metal substrate. The covering layer is located on a portion of the metal substrate where the element unit is not located, and contains Zn and Mn. The sealing material is located on at least a portion of the element unit and at least a portion of the covering layer, and contains Ba. The intermediate layer is located between the covering layer and the sealing material, and contains all of the main metal elements contained in the sealing material, with the Zn content being greater than half the Ba content.

[0006] An electrochemical cell device according to one aspect of the embodiment includes a cell stack including the electrochemical cell described above.

[0007] The module of the present disclosure includes the electrochemical cell device described above and a container that houses the electrochemical cell device.

[0008] The module housing device of the present disclosure includes the module described above, an auxiliary device for operating the module, and an exterior case for housing the module and the auxiliary device.

[0009] FIG. 1A is a plan view of an example of an electrochemical cell according to an embodiment, viewed from the air electrode side. FIG. 1B is a cross-sectional view taken along line A-A in FIG. 1A. FIG. 2 is an enlarged view of region B in FIG. 1B. FIG. 3A is a perspective view showing an example of an electrochemical cell device according to an embodiment. FIG. 3B is a cross-sectional view taken along line X-X in FIG. 3A. FIG. 3C is a top view showing an example of an electrochemical cell device according to an embodiment. FIG. 4 is an external perspective view showing an example of a module according to an embodiment. FIG. 5 is an exploded perspective view schematically showing an example of a module housing device according to an embodiment.

[0010] The above-described fuel cell stack device has room for improvement in terms of durability.

[0011] Therefore, it is desired to provide a composite member, an electrochemical cell, an electrochemical cell device, a module, and a module housing device that can improve durability.

[0012] Hereinafter, embodiments of a composite member, an electrochemical cell, an electrochemical cell device, a module, and a module housing device disclosed in the present application will be described in detail with reference to the accompanying drawings. Note that the disclosure is not limited to the embodiments described below.

[0013] It should also be noted that the drawings are schematic and that the dimensional relationships and ratios of elements may differ from reality. Furthermore, the drawings may contain parts whose dimensional relationships and ratios differ from one another.

[0014] 1A and 1B, an electrochemical cell according to an embodiment will be described using an example of a solid oxide fuel cell. The electrochemical cell device may include a cell stack having a plurality of electrochemical cells. An electrochemical cell device having a plurality of electrochemical cells will be simply referred to as a cell stack device.

[0015] Fig. 1A is a plan view of an example of an electrochemical cell according to an embodiment, viewed from the air electrode side. Fig. 1B is a cross-sectional view taken along line A-A in Fig. 1A. Figs. 1A and 1B show enlarged views of parts of each component of the electrochemical cell. Hereinafter, the electrochemical cell may be simply referred to as a cell.

[0016] For ease of understanding, Figures 1A and 1B illustrate a three-dimensional Cartesian coordinate system including a Z axis, with the vertical upward direction as the positive direction and the vertical downward direction as the negative direction. This Cartesian coordinate system may also be shown in other drawings used in the following description. Furthermore, components similar to those in the electrochemical cells shown in Figures 1A and 1B are denoted by the same reference numerals, and their description will be omitted or simplified.

[0017] 1A and 1B, a cell 1 according to this embodiment includes an element section 3, a sealing material 9, a metal substrate 2, and a flow path member 30. The element section 3 includes an anode 5, a solid electrolyte layer 6, and an cathode 8. In the example of FIG. 1A, one element section 3 is located on the metal substrate 2, but two or more element sections 3 may be located thereon.

[0018] The anode 5 is a first electrode that comes into contact with the fuel gas, which is a reducing gas. The anode 5 has gas permeability. The open porosity of the anode 5 may be, for example, in the range of 30% to 50%, particularly 35% to 45%. The open porosity of the anode 5 may also be referred to as the porosity or void ratio of the anode 5.

[0019] A generally known material can be used for the fuel electrode 5. The fuel electrode 5 is made of a porous conductive ceramic, such as calcium oxide, magnesium oxide, or ZrO in which a rare earth element oxide is solid-solved. ２ and Ni and / or NiO may be used. The rare earth element oxide may contain, for example, a plurality of rare earth elements selected from Sc, Y, La, Nd, Sm, Gd, Dy, and Yb. Calcium oxide, magnesium oxide, or ZrO in which a rare earth element oxide is solid-solved may be used. ２ The stabilized zirconia may contain partially stabilized zirconia. The anode 5 is made of CeO in which La, Nd, or Yb is solid-solved. ２may include:

[0020] The solid electrolyte layer 6 is an electrolyte and transfers ions between the fuel electrode 5 and the air electrode 8. At the same time, the solid electrolyte layer 6 has gas barrier properties and makes it difficult for leakage of fuel gas and oxygen-containing gas to occur.

[0021] The material of the solid electrolyte layer 6 is, for example, ZrO in which 3 mol % to 15 mol % of rare earth element oxide is dissolved. ２ The rare earth element oxide may contain, 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 be, for example, ZrO in which Yb, Sc, or Gd is solid-solved. ２ and CeO in which La, Nd or Yb is solid-solved. ２ and BaZrO in which Sc or Yb is solid-solved. ３ and BaCeO in which Sc or Yb is solid-solved. ３ may include:

[0022] The air electrode 8 is a second electrode that comes into contact with an oxygen-containing gas. The air electrode 8 has gas permeability. The open porosity of the air electrode 8 may be, for example, in the range of 20% to 50%, particularly 30% to 50%. The open porosity of the air electrode 8 may also be referred to as the porosity of the air electrode 8.

[0023] There are no particular limitations on the material of the air electrode 8 as long as it is a material that is generally used for air electrodes. ３ Conductive ceramics such as perovskite oxides may also be used.

[0024] 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 composite oxides include La ｘ Sr １－ｘ Co ｙ Fe １－ｙ O ３ , La ｘ Sr １－ｘ MnO ３ , La ｘ Sr １－ｘ FeO ３ , La ｘSr １－ｘ CoO ３ Here, x is 0<x<1, and y is 0<y<1.

[0025] The element section 3 may also have a diffusion suppression layer (not shown) located between the solid electrolyte layer 6 and the air electrode 8. When elements such as Sr (strontium) contained in the air electrode 8 diffuse into the solid electrolyte layer 6, the solid electrolyte layer 6 becomes covered with SrZrO ３ The diffusion suppression layer makes it difficult for specific elements such as Sr to diffuse, resulting in a resistance layer such as SrZrO ３ This makes it difficult for compounds such as

[0026] The material of the diffusion-preventing layer is not particularly limited as long as it is generally Sr or the like and makes it difficult for a specific element to diffuse between the air electrode 8 and the solid electrolyte layer 6. The material of the diffusion-preventing layer is, for example, cerium oxide (CeO) in which a rare earth element other than Ce (cerium) is dissolved. ２ ) may be included. Examples of such rare earth elements include Gd (gadolinium) and Sm (samarium).

[0027] The sealing material 9 is located on at least a portion of the element unit 3 and on the side surfaces of the element unit 3. The sealing material 9 is in contact with the solid electrolyte layer 6 and the anode 5 of the element unit 3, and is a sealing material that makes it difficult for fuel gas to leak from the anode 5. The sealing material 9 may be separated from the cathode 8 or may be in contact with the cathode 8.

[0028] The material of the sealing material 9 may be a crystallized glass containing Ba. Examples of the crystallized glass include SiO ２ -CaO system, MgO-B ２ O ３ System, La ２ O ３ -B ２ O ３ -MgO system, La ２ O ３ -B ２ O ３ -ZnO-based, SiO ２ -CaO-ZnO system materials, etc., may be used, and in particular SiO ２A -MgO-based material may also be used. By including Ba in these crystallized glasses, the softening temperature of the crystallized glasses becomes relatively high, and the thermal expansion coefficient of the crystallized glasses becomes relatively large. The crystallized glasses may contain Ba as an oxide represented as BaO. The sealing material 9 may have electrical insulation properties.

[0029] The metal base 2 has a surface 201 and a surface 202 located at both ends in the thickness direction (Y-axis direction). The metal base 2 may be, for example, a metal plate in which the distance between the surface 201 and the surface 202 is approximately constant.

[0030] The metal substrate 2 is electrically conductive. The metal substrate 2 may be, for example, a member made of a metal containing chromium. The metal substrate 2 may be, for example, a stainless steel such as a ferritic stainless steel or an austenitic stainless steel having high heat resistance. The metal substrate 2 may be, for example, a nickel-chromium alloy or an iron-chromium alloy. The metal substrate 2 may contain, for example, a metal oxide. The metal substrate 2 may have a coating covering the surface. The metal substrate 2 may not have a coating on the surface.

[0031] Furthermore, the metal substrate 2 may have an opening penetrating between the surface 201 and the surface 202. The fuel gas flowing through a flow path 2a, which will be described later, is supplied to the fuel electrode 5 of the element section 3 through this opening. The diameter of the opening may be, for example, 0.1 mm to 0.5 mm, particularly 0.3 mm to 0.4 mm. In a plan view of the metal substrate 2 along the Y-axis direction, the opening ratio in the region where the opening is formed may be, for example, 10% or more. The metal substrate 2 may have a coating that covers the wall surface of the opening. The metal substrate 2 does not need to have a coating on the wall surface of the opening.

[0032] The metal base 2 may be gas permeable, for example. In such a case, the metal base 2 does not need to have an opening penetrating in the thickness direction (Y-axis direction).

[0033] The flow path member 30 is located between the element units 3 of adjacent cells 1. The flow path member 30 is located between the fuel electrode 5 of one element unit 3 and the air electrode 8 of the other element unit 3. The material of the flow path member 30 is a dense metal or alloy. The flow path member 30 has a surface 31 and a surface 32 located opposite to the surface 31. The flow path member 30 makes it difficult for the fuel gas flowing on the surface 31 side and the oxygen-containing gas flowing on the surface 32 side to leak. The flow path member 30 may have a coating. For example, the flow path member 30 may have a reduction-resistant coating on the surface 31. The flow path member 30 may also have an oxidation-resistant coating on the surface 32. These coatings may be conductive.

[0034] The flow path member 30 may be fixed and electrically joined to the metal substrate 2 by, for example, welding or the like at the contact portion. The flow path member 30 may be fixed and electrically joined to the metal substrate 2 by a conductive sealing material, brazing material, or the like. A flow path 2a through which the fuel gas flows is located between a surface 31 of the flow path member 30 and the metal substrate 2. The fuel gas flowing through the flow path 2a permeates the metal substrate 2 and is supplied to the anode 5.

[0035] The surface 32 may be fixed to the air electrode 8 via, for example, a conductive adhesive and electrically joined thereto. A space through which an oxygen-containing gas flows is located between the flow path member 30 and the air electrode 8.

[0036] The cell 1 may further include a constraining layer (not shown). The constraining layer may be located between the element portion 3 and the metal substrate 2. The constraining layer cooperates with the solid electrolyte layer 6 to make the element portion 3 less susceptible to warping, bending, and the like.

[0037] The material of the constraining layer may exhibit a shrinkage rate similar to that of the material of the solid electrolyte layer 6 during firing. The material of the constraining layer may be the same as the material of the solid electrolyte layer 6. The element unit 3 obtained by sandwiching the material of the anode 5 of the element unit 3 between the material of the solid electrolyte layer 6 and the material of the constraining layer and firing the resulting element unit 3 has little warping or deformation.

[0038] The constraining layer may or may not be gas permeable. When the constraining layer has gas barrier properties comparable to those of the solid electrolyte layer 6, the constraining layer can be partially disposed so as not to obstruct the inflow of fuel gas to the anode 5.

[0039] The cell 1 may further include a gas diffusion layer (not shown). The gas diffusion layer may be located between the fuel electrode 5 and the metal substrate 2. The gas diffusion layer has gas permeability and allows the fuel gas flowing through the flow path 2a to pass through to the fuel electrode 5. The open porosity of the gas diffusion layer may be in the range of, for example, 30% to 50%, particularly 35% to 45%.

[0040] The material of the gas diffusion layer may be a porous conductive ceramic, such as a ceramic containing calcium oxide, magnesium oxide, or stabilized zirconia or partially stabilized zirconia in which a rare earth element oxide is solid-solved, and Ni and / or NiO. The rare earth element oxide may contain a plurality of rare earth elements selected from, for example, Sc, Y, La, Nd, Sm, Gd, Dy, and Yb.

[0041] 1B , the shape of the flow path member 30 is not limited to that shown in Fig. 1B. The flow path member 30 may have any shape as long as it electrically connects adjacent cells 1 and makes it difficult for the fuel gas and oxygen-containing gas to leak.

[0042] <Details of Main Parts of Electrochemical Cell> Next, the main parts of the cell 1 according to the embodiment will be further described with reference to Fig. 2. Fig. 2 is an enlarged view of region B shown in Fig. 1B.

[0043] 2 , the cell 1 includes a metal substrate 2 and a sealing material 9. The cell 1 also has a coating layer 4 and an intermediate layer 7. The sealing material 9 is located on at least a portion of the coating layer 4.

[0044] The coating layer 4 is located on the metal substrate 2. The coating layer 4 has a surface 4a serving as a first surface facing the metal substrate 2 and a surface 4b serving as a second surface facing the intermediate layer 7. The coating layer 4 is located on a portion of the metal substrate 2 where the element section 3 is not located. The coating layer 4 contains Zn and Mn, which improves the adhesion between the metal substrate 2 and the sealing material 9. This makes it less likely for the sealing material 9 to peel off from the metal substrate 2, and the durability of the cell 1 according to this embodiment is improved.

[0045] The coating layer 4 may have a portion 42 located near the surface 4b, which has a lower Zn content than the portion near the surface 4a. This improves adhesion between the coating layer 4 and the intermediate layer 7. This makes it less likely that the sealing material 9 will peel off from the metal substrate 2, improving the durability of the cell 1 according to this embodiment. The portion 42 may be located in a layer along the surface 4b, or may be located partially at one or more locations near the surface 4b.

[0046] Furthermore, the coating layer 4 may have a region 41 located near the surface 4a and having a higher Mn content than near the surface 4b. This improves adhesion between the coating layer 4 and the metal substrate 2. This makes it less likely that the sealing material 9 will peel off from the metal substrate 2, improving the durability of the cell 1 according to this embodiment. The region 41 may be located in a layer along the surface 4a, or may be located partially at one or more locations near the surface 4a. The region 41 and the region 42 may be separated from each other or may partially overlap each other.

[0047] Furthermore, the coating layer 4 may have a portion located near the surface 4a where the Mn content is greater than the Zn content. This improves the adhesion between the intermediate layer 7 and the metal substrate 2 via the coating layer 4. This makes it less likely that the sealing material 9 will peel off from the metal substrate 2, improving the durability of the cell 1 according to this embodiment. Note that the portion where the Mn content is greater than the Zn content may or may not coincide with the portion 41.

[0048] The intermediate layer 7 is located between the coating layer 4 and the sealing material 9. The intermediate layer 7 contains all of the major metal elements contained in the sealing material 9, and the Zn content is greater than half the Ba content. As a result, the intermediate layer 7 has a thermal expansion coefficient intermediate between that of the coating layer 4 and the sealing material 9. This makes it less likely for the sealing material 9 to crack and / or peel off from the metal substrate 2, thereby improving the durability of the cell 1 according to this embodiment. Here, "major metal elements contained in the sealing material 9" refers to metal elements contained in the sealing material 9 at a ratio of 1 atomic % or more relative to the total amount of metal elements contained in the sealing material 9. Furthermore, "containing all of the major metal elements contained in the sealing material 9" refers to all of the major metal elements contained in the sealing material 9 being contained at 1 atomic % or more relative to the total amount of metal elements. For example, when a cross section of the element portion 3 is subjected to elemental analysis using energy dispersive X-ray spectroscopy (EDS), all of the major metal elements contained in the sealing material 9 may be detected in the intermediate layer 7 at 1 atomic % or more. For example, the metal substrate 2 made of ferritic stainless steel has a thickness of 12 × 10 －６ / ℃~13×10 －６ The coating layer 4 (ZMC) has a linear thermal expansion coefficient of about 9×10 －６ / ℃~10×10 －６ The sealing material 9 (Ba glass) has a linear thermal expansion coefficient of, for example, 10×10 －６ / ℃~11×10 －６ The intermediate layer 7 has a linear thermal expansion coefficient of about 1 / ° C. / ° C. The intermediate layer 7 contains Zn in addition to the metal elements contained in the sealing material 9, and therefore has a linear thermal expansion coefficient that is slightly smaller than that of the sealing material 9.

[0049] As described above, the cell 1 has the coating layer 4 and intermediate layer 7 located between the metal substrate 2 and the sealing material 9. Therefore, cracks in the sealing material 9 and / or peeling of the sealing material 9 from the metal substrate 2 caused by the difference in thermal expansion between the metal substrate 2 and the sealing material 9 are less likely to occur, and therefore the durability of the cell 1 according to this embodiment is improved.

[0050] The compositions of the coating layer 4, intermediate layer 7, and sealing material 9, and the presence or absence of each portion of the coating layer 4, can be confirmed as follows. A portion including the coating layer 4, intermediate layer 7, and sealing material 9 is embedded in resin and mirror-polished to obtain a cross section. The presence or absence of each layer can be confirmed by observing the obtained cross section, for example, using a scanning electron microscope (SEM). The composition of each layer can be confirmed by performing elemental analysis of each layer on the obtained cross section using EDS.

[0051] 2 has been described above as a part of the cell 1, it may also be produced as a composite member in which the element portion 3 is removed from the configuration of the cell 1. Such a composite member can be used, for example, as a flow path member, a separator, etc.

[0052] <Configuration of Electrochemical Cell Device> Next, an electrochemical cell device according to this embodiment using the above-described cell 1 will be described with reference to Figures 3A to 3C. Figure 3A is a perspective view showing an example of an electrochemical cell device according to an embodiment. Figure 3B is a cross-sectional view taken along line XX shown in Figure 3A. Figure 3C is a top view showing an example of an electrochemical cell device according to an embodiment.

[0053] As shown in Figure 3A, the cell stack device 10 includes a cell stack 11 having multiple cells 1 arranged (stacked) in the thickness direction of the cells 1 (the Y-axis direction shown in Figure 1B), and a fixing member 12.

[0054] The fixing member 12 has a fixing material 13 and a support member 14. The support member 14 supports the cell 1. The fixing material 13 fixes the cell 1 to the support member 14. The support member 14 also has a support 15 and a gas tank 16. The support 15 and the gas tank 16, which are the support member 14, are made of metal and are electrically conductive.

[0055] 3B, the support body 15 has insertion holes 15a into which the lower ends of the plurality of cells 1 are inserted. The lower ends of the plurality of cells 1 and the inner wall of the insertion holes 15a are joined with fixing material 13.

[0056] The gas tank 16 has an opening for supplying a reaction gas to the cells 1 through the insertion holes 15a, and a recessed groove 16a located around the opening. The outer peripheral edge of the support 15 is joined to the gas tank 16 by a bonding material 21 filled in the recessed groove 16a of the gas tank 16.

[0057] In the example shown in Fig. 3A, fuel gas is stored in an internal space 22 (see Fig. 3B) formed by a support body 15, which is the support member 14, and a gas tank 16. A gas circulation pipe 20 is connected to the gas tank 16. The fuel gas is supplied to the gas tank 16 through this gas circulation pipe 20, and is supplied from the gas tank 16 to a flow path 2a (see Fig. 1B) inside the cell 1. The fuel gas supplied to the gas tank 16 is generated in a reformer 102 (see Fig. 4), which will be described later. The internal space 22 may also be referred to as a space containing a reducing atmosphere and fuel gas.

[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 contains water vapor.

[0059] The example shown in FIG. 3A includes two rows of cell stacks 11, two supports 15, and a gas tank 16. Each of the two rows of cell stacks 11 includes a plurality of cells 1. Each cell stack 11 is fixed to a corresponding support 15. The gas tank 16 has two through-holes on its top surface. A support 15 is disposed in each through-hole. The internal space 22 is formed by the one gas tank 16 and the two supports 15. The cell stack device 10 may include only one cell stack 11, or may include three or more cell stacks 11.

[0060] The shape of the insertion hole 15a is, for example, an oval shape when viewed from above. For example, the length of the insertion hole 15a in the arrangement direction of the cells 1, i.e., the thickness direction (Y-axis direction shown in FIG. 1B ), is greater than the distance between the two end current collecting members 17 located at both ends of the cell stack 11. For example, the width of the insertion hole 15a is greater than the length of the cell 1 in the width direction (X-axis direction shown in FIG. 1B ).

[0061] 3B, a fixing material 13 is filled and solidified at the joint between the inner wall of the insertion hole 15a and the lower end of the cell 1. This bonds and fixes the inner wall of the insertion hole 15a to the lower end of each of the multiple cells 1, and also bonds and fixes the lower ends of the cells 1 to each other. The flow path 2a of each cell 1 communicates with the internal space 22 of the support member 14 at its lower end.

[0062] A material with low conductivity, such as glass, can be used for the fixing material 13 and the bonding material 21. Specific materials for the fixing material 13 and the bonding material 21 include amorphous glass, and in particular, crystallized glass.

[0063] Examples of the crystallized glass include SiO ２ -CaO system, MgO-B ２ O ３ System, La ２ O ３ -B ２ O ３ -MgO system, La ２ O ３ -B ２ O ３ -ZnO-based, SiO ２ -CaO-ZnO system materials, etc., may be used, and in particular SiO ２ - MgO-based materials may also be used.

[0064] 3B, a conductive member 18 may be interposed between adjacent cells 1 among the plurality of cells 1. The conductive member 18 electrically connects one adjacent cell 1 to the other adjacent cell 1 in series. More specifically, the conductive member 18 connects the fuel electrode 5 of one cell 1 to the air electrode 8 of the other cell 1. The conductive member 18 may be the flow path member 30 shown in FIG. 1B, or may be a member separate from the flow path member 30.

[0065] 3B, an end current collecting member 17 is electrically connected to the cell 1 positioned outermost in the arrangement direction of the multiple cells 1. The end current collecting member 17 is connected to a conductive portion 19 that protrudes outside the cell stack 11. The conductive portion 19 collects electricity generated by power generation in the cells 1 and extracts it to the outside. Note that the end current collecting member 17 is not shown in FIG. 3A.

[0066] 3C, the cell stack device 10 has two cell stacks 11A and 11B connected in series to function as a single 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 electrode terminal 19A is a positive electrode when the power generated by the cell stack 11 is output to the outside. The positive electrode terminal 19A is electrically connected to the end current collector 17 on the positive electrode side of the cell stack 11A. The negative electrode terminal 19B is a negative electrode when the power generated by the cell stack 11 is output to the outside. The negative electrode terminal 19B is electrically connected to the end current collector 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 of the cell stack 11A to the end current collecting member 17 on the positive electrode side of the cell stack 11B.

[0069] <Module> Next, a module according to this embodiment using the above-described cell stack device 10 will be described with reference to Fig. 4. Fig. 4 is an external perspective view showing an example of a module according to this embodiment. Fig. 4 shows a state in which the front and rear surfaces, which are part of the storage container 101, have been removed and the cell stack device 10 of the fuel cell stored inside has been taken out to the rear.

[0070] 4, the module 100 includes a storage container 101 and a cell stack device 10 housed in the storage container 101. A reformer 102 may be disposed above the cell stack device 10.

[0071] The reformer 102 reforms raw fuel such as natural gas or kerosene to generate fuel gas, which is then supplied to the cell 1. The raw fuel is supplied to the reformer 102 through a raw fuel supply pipe 103. The reformer 102 may include a vaporizer 102a that vaporizes water, and a reformer 102b. The reformer 102b includes a reforming catalyst (not shown) and reforms the raw fuel into fuel gas. Such a reformer 102 can perform steam reforming, a highly efficient reforming reaction.

[0072] The fuel gas produced in the reformer 102 is supplied to the flow path 2 a of the cell 1 (see FIG. 1B) through the gas distribution pipe 20 , the gas tank 16 , and the support member 14 .

[0073] Furthermore, in the module 100 having the above-described configuration, the temperature inside the module 100 during normal power generation reaches approximately 500°C to 1000°C due to the combustion of gas and the power generation of the cells 1.

[0074] In such a module 100, as described above, the module 100 is configured to house the cell stack device 10 having a plurality of highly durable cells 1, thereby making it possible to make the module 100 highly durable.

[0075] <Module Enclosure Device> Fig. 5 is an exploded perspective view schematically illustrating an example of a module enclosure device according to an embodiment. The module enclosure device 110 according to this embodiment includes an outer case 111, the module 100 shown in Fig. 4, and auxiliary equipment (not shown). The auxiliary equipment operates the module 100. The module 100 and the auxiliary equipment are housed in the outer case 111. Note that some components are omitted in Fig. 5.

[0076] An exterior case 111 of a module accommodating device 110 shown in Fig. 5 has support columns 112 and an exterior plate 113. A partition plate 114 divides the interior of the exterior case 111 into upper and lower sections. The space above the partition plate 114 in the exterior case 111 is a module accommodating chamber 115 that accommodates the module 100, and the space below the partition plate 114 in the exterior case 111 is an auxiliary equipment accommodating chamber 116 that accommodates auxiliary equipment for operating the module 100. Note that in Fig. 5, the auxiliary equipment accommodated in the auxiliary equipment accommodating chamber 116 is omitted from the illustration.

[0077] The partition plate 114 also has an air flow port 117 for allowing air from the auxiliary equipment housing chamber 116 to flow toward the module housing chamber 115. The exterior plate 113 that constitutes the module housing chamber 115 has an exhaust port 118 for exhausting air from within the module housing chamber 115.

[0078] In such a module accommodating device 110, as described above, highly durable modules 100 are provided in the module accommodating chamber 115, so that the module accommodating device 110 can be made highly durable.

[0079] [Other Embodiments] In the above-described embodiments, a fuel cell, a fuel cell stack device, a fuel cell module, and a fuel cell device are shown as examples of an "electrochemical cell," "electrochemical cell device," "module," and "module housing device." However, other examples may be an electrolysis cell, an electrolysis cell stack device, an electrolysis module, and an electrolysis device, respectively. An electrolysis cell has a first electrode and a second electrode, and decomposes water vapor into hydrogen and oxygen, or decomposes carbon dioxide into carbon monoxide and oxygen, when supplied with electric power. Furthermore, in the above-described embodiments, an oxide ion conductor or a hydrogen ion conductor is shown as an example of the electrolyte material of the electrochemical cell, but a hydroxide ion conductor may also be used. Such electrolysis cells, electrolysis cell stack devices, electrolysis modules, and electrolysis devices can improve electrolysis performance and durability. Solid oxide fuel cells and electrolysis cells are collectively referred to as solid oxide electrochemical cells.

[0080] The present disclosure has been described in detail above, but the present disclosure is not limited to the above-described embodiments, and various modifications, improvements, etc. are possible within the scope that does not deviate from the gist of the present disclosure.

[0081] In one embodiment, (1) a composite member includes a metal substrate, a coating layer located on the metal substrate and containing Zn and Mn, a sealing material located on the coating layer and containing Ba, and an intermediate layer located between the coating layer and the sealing material, the intermediate layer containing all of the main metal elements contained in the sealing material and having a Zn content that is greater than half the Ba content.

[0082] In one embodiment, (2) the electrochemical cell comprises: a metal substrate; an element portion located on the metal substrate; a coating layer containing Zn and Mn and located on the metal substrate where the element portion is not located; a sealing material containing Ba and located on at least a portion of the element portion and at least a portion of the coating layer; and an intermediate layer located between the coating layer and the sealing material, containing all of the main metal elements contained in the sealing material and having a Zn content that is greater than half the Ba content.

[0083] (3) In the electrochemical cell of (2) above, the coating layer may have a first surface facing the metal substrate and a second surface facing the intermediate layer, and may have a portion located near the second surface that has a lower Zn content than the portion near the first surface.

[0084] (4) In the electrochemical cell of (2) or (3) above, the coating layer may have a first surface facing the metal substrate and a second surface facing the intermediate layer, and may have a portion located near the first surface that has a higher Mn content than a portion near the second surface.

[0085] (5) The electrochemical cell of any one of (2) to (4) above may have a first surface facing the metal substrate and a second surface facing the intermediate layer, and may have a portion located near the first surface in which the Mn content is greater than the Zn content.

[0086] (6) In the electrochemical cell of any one of (2) to (5) above, the sealing material may contain crystallized glass containing Ba.

[0087] In one embodiment, (7) the electrochemical cell device has a cell stack including any one of the electrochemical cells (2) to (6) above.

[0088] In one embodiment, (8) a module includes the electrochemical cell device of (7) above, and a container that houses the electrochemical cell device.

[0089] In one embodiment, (9) a module housing device includes the module of (8) above, an auxiliary device for operating the module, and an exterior case for housing the module and the auxiliary device.

[0090] The disclosed embodiments should be considered in all respects as illustrative and not restrictive. Indeed, the above-described embodiments may be embodied in various forms. Furthermore, the above-described embodiments may be omitted, substituted, or modified in various ways without departing from the scope and spirit of the appended claims.

[0091] REFERENCE SIGNS LIST 1 cell 2 metal substrate 3 element portion 4 coating layer 5 fuel electrode 6 solid electrolyte layer 7 intermediate layer 8 air electrode 9 sealing material 10 cell stack device 30 flow path member 100 module 110 module housing device

Claims

1. A composite member comprising: a metal substrate; a coating layer located on the metal substrate and containing Zn and Mn; a sealing material located on the coating layer and containing Ba; and an intermediate layer located between the coating layer and the sealing material, containing all of the main metal elements contained in the sealing material and having a Zn content greater than half the Ba content.

2. An electrochemical cell comprising: a metal substrate; an element portion located on the metal substrate; a coating layer containing Zn and Mn and located on the metal substrate where the element portion is not located; a sealing material containing Ba and located on at least a portion of the element portion and at least a portion of the coating layer; and an intermediate layer located between the coating layer and the sealing material, containing all of the main metal elements contained in the sealing material and having a Zn content greater than half the Ba content.

3. The electrochemical cell according to claim 2, wherein the coating layer has a first surface facing the metal element and a second surface facing the intermediate layer, and has a portion located near the second surface that has a lower Zn content than the portion near the first surface.

4. The electrochemical cell according to claim 2 or 3, wherein the coating layer has a first surface facing the metal element and a second surface facing the intermediate layer, and has a portion located near the first surface that has a higher Mn content than near the second surface.

5. The electrochemical cell according to any one of claims 2 to 4, wherein the coating layer has a first surface facing the metal element and a second surface facing the intermediate layer, and has a portion located near the first surface where the Mn content is greater than the Zn content.

6. The electrochemical cell according to any one of claims 2 to 5, wherein the sealing material comprises crystallized glass containing Ba.

7. An electrochemical cell device having a cell stack including the electrochemical cell according to any one of claims 2 to 6.

8. A module comprising the electrochemical cell device according to claim 7 and a container for housing the electrochemical cell device.

9. A module housing device comprising: the module according to claim 8; an auxiliary device for operating said module; and an exterior case for housing said module and said auxiliary device.

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