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

Abstract

To provide a conductive member capable of improving performance, an electrochemical cell device, a module, and a module housing device.SOLUTION: A conductive member includes a metal plate, a first porous layer, and a second porous layer. The metal plate has a first surface and a second surface located on an opposite side of the first surface, allowing gas to flow between the first surface and the second surface. The first porous layer is located on the first surface. The second porous layer is located on the second surface. When a thermal expansion coefficient of the metal plate is α0, a thermal expansion coefficient of the first porous layer is α1, and a thermal expansion coefficient of the second porous layer is α2, a relationship of α1<α0 and α2<α0, or α1>α0 and α2>α0 is satisfied.SELECTED DRAWING: Figure 1A

Description

[Technical Field]

[0001] The present disclosure relates to an electrically conductive member, an electrochemical cell device, a module, and a module housing device. [Background technology]

[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. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-273213 [Patent Document 2] Japanese Patent Application Publication No. 2019-179755 [Patent Document 3] Japanese Patent Application Laid-Open No. 2013-41717 Summary of the Invention

[0004] A conductive member according to one embodiment includes a metal plate, a first porous layer, and a second porous layer. The metal plate has a first surface and a second surface opposite the first surface, and gas can flow between the first surface and the second surface. The first porous layer is located on the first surface. The second porous layer is located on the second surface. When the thermal expansion coefficient of the metal plate is α0, the thermal expansion coefficient of the first porous layer is α1, and the thermal expansion coefficient of the second porous layer is α2, these have a relationship of α1<α0 and α2<α0, or α1>α0 and α2>α0.

[0005] The electrochemical cell device of the present disclosure includes two or more electrochemical cells each having an element portion, and the conductive member described above.

[0006] The module of the present disclosure includes the electrochemical cell device described above and a container that houses the electrochemical cell device.

[0007] 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. [Brief explanation of the drawings]

[0008] [Figure 1A] FIG. 1A is a cross-sectional view showing an example of an electrochemical cell device according to a first embodiment. [Figure 1B] FIG. 1B is a plan view of an example of an electrochemical cell included in the electrochemical cell device according to the first embodiment, viewed from the air electrode side. [Figure 1C] FIG. 1C is an enlarged cross-sectional view of a region R shown in FIG. 1A. [Figure 2A] FIG. 2A is a cross-sectional view showing another example of the electrochemical cell device according to the first embodiment. [Figure 2B] FIG. 2B is a cross-sectional view showing another example of the electrochemical cell device according to the first embodiment. [Figure 3A] FIG. 3A is a perspective view showing an example of an electrochemical cell device according to the first embodiment. [Figure 3B] FIG. 3B is a cross-sectional view taken along line XX shown in FIG. 3A. [Figure 3C] FIG. 3C is a top view showing an example of the electrochemical cell device according to the first embodiment. [Figure 4] FIG. 4 is an external perspective view illustrating an example of the module according to the first embodiment. [Figure 5] FIG. 5 is an exploded perspective view schematically illustrating an example of a module housing device according to the first embodiment. [Figure 6] FIG. 6 is a perspective view showing an example of an electrochemical cell according to the second embodiment. [Figure 7] FIG. 7 is a partial cross-sectional view of the electrochemical cell shown in FIG. DETAILED DESCRIPTION OF THE INVENTION

[0009] The above-described fuel cell stack device has room for improvement in performance, such as power generation performance and electrolysis performance.

[0010] Therefore, it is desired to provide a conductive member, an electrochemical cell device, a module, and a module housing device that can improve performance.

[0011] Hereinafter, embodiments of the conductive member, electrochemical cell device, module, and 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.

[0012] 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.

[0013] [First embodiment] <Electrochemical cell configuration> First, with reference to Figures 1A to 1C, an electrochemical cell according to a first 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.

[0014] FIG. 1A is a cross-sectional view showing an example of an electrochemical cell device according to a first embodiment. FIG. 1B is a plan view showing an example of an electrochemical cell included in the electrochemical cell device according to the first embodiment, viewed from the air electrode side. FIG. 1C is an enlarged cross-sectional view of region R shown in FIG. 1A. Note that FIGS. 1A to 1C show enlarged views of parts of each component of the electrochemical cell. Hereinafter, the electrochemical cell may also be simply referred to as a cell.

[0015] For ease of understanding, Figures 1A and 1B show 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 explanation. Furthermore, the same reference numerals are used to designate components similar to those of the electrochemical cells shown in Figures 1A to 1C, and their explanations will be omitted or simplified.

[0016] 1A, the electrochemical cell device according to this embodiment includes a cell 1A. The cell 1A includes an element section 4A, a conductive member 30, and a flow path member 34. The element section 4A includes a fuel electrode 5, a solid electrolyte layer 6, and a cathode 8.

[0017] The fuel electrode 5 is a first electrode that comes into contact with the fuel gas, which is a reducing gas. The fuel electrode 5 has gas permeability. The open porosity of the fuel electrode 5 may be, for example, in the range of 30% to 50%, and particularly 35% to 45%. The open porosity of the fuel electrode 5 may also be referred to as the porosity or void ratio of the fuel electrode 5.

[0018] The anode 5 may be made of a generally known material. The anode 5 may be made of porous conductive ceramics, such as ceramics containing calcium oxide, magnesium oxide, or ZrO2 solid-solubilized with rare earth element oxides, and Ni and / or NiO. 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 ZrO2 solid-solubilized with rare earth element oxides is sometimes referred to as stabilized zirconia. Stabilized zirconia may include partially stabilized zirconia. The anode 5 may also include CeO2 solid-solubilized with La, Nd, or Yb.

[0019] The fuel electrode 5 has a thickness of, for example, 12×10 -6 The thermal expansion coefficient (linear expansion coefficient) may be about 1 / K.

[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 the fuel gas and oxygen-containing gas to leak.

[0021] The material of the solid electrolyte layer 6 may be, for example, ZrO2 with 3 mol % to 15 mol % of a rare earth element oxide dissolved therein. The rare earth element oxide 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 with Yb, Sc, or Gd dissolved therein, CeO2 with La, Nd, or Yb dissolved therein, BaZrO3 with Sc or Yb dissolved therein, or BaCeO3 with Sc or Yb dissolved therein.

[0022] The solid electrolyte layer 6 has a thickness of, for example, 10×10 -6 The thermal expansion coefficient (linear expansion coefficient) may be about 1 / K.

[0023] 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%, and particularly in the range of 30% to 50%. The open porosity of the air electrode 8 may also be referred to as the porosity of the air electrode 8.

[0024] There are no particular restrictions on the material of the air electrode 8 as long as it is one that is generally 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.

[0025] 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 O3, La x Sr 1-x MnO3, La x Sr 1-x FeO3, La x Sr1-x CoO3, etc. Note that x is 0 <x<1、yは0<y<1である。

[0026] The air electrode 8 has a thickness of, for example, 15×10 -6 The thermal expansion coefficient (linear expansion coefficient) may be about 1 / K.

[0027] The element unit 4A may also have an intermediate layer (not shown) located between the solid electrolyte layer 6 and the air electrode 8. When the element unit 4A has an intermediate layer, the intermediate layer functions, for example, as a diffusion suppression layer. When Sr (strontium) contained in the air electrode 8 diffuses into the solid electrolyte layer 6, a resistive 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 be formed.

[0028] The material of the intermediate layer is not particularly limited as long as it generally prevents diffusion of elements 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 dissolved. Examples of such rare earth elements that may be used include Gd (gadolinium) and Sm (samarium).

[0029] The middle layer is, for example, 12 × 10 -6 The thermal expansion coefficient (linear expansion coefficient) may be about 1 / K.

[0030] The cell 1A may further include a constraining layer. The constraining layer may be located between the element portion 4A and the conductive member 30. The constraining layer cooperates with the solid electrolyte layer 6 to make the element portion 4A less susceptible to warping, bending, and the like.

[0031] The material of the constraining layer exhibits 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 4A obtained by sandwiching the material of the fuel electrode 5 (described later) of the element unit 4A between the material of the solid electrolyte layer 6 and the material of the constraining layer and firing the resulting element unit 4A has little warping or deformation.

[0032] 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.

[0033] The constrained layer is, for example, 10 to 12 × 10 -6 The thermal expansion coefficient (linear expansion coefficient) may be about 1 / K.

[0034] The cell 1A may further include a gas diffusion layer. The gas diffusion layer may be located between the fuel electrode 5 and the conductive member 30. The gas diffusion layer has gas permeability and allows the fuel gas flowing through a flow path 35 (described later) 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%.

[0035] 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.

[0036] The gas diffusion layer may be, for example, 12×10 -6 The thermal expansion coefficient (linear expansion coefficient) may be about 1 / K.

[0037] The conductive member 30 has an adhesive 31 as a first porous layer, a metal plate 32, and a deformation suppression layer 33 as a second porous layer.

[0038] The adhesive material 31 is located between the element portion 4A and the first surface 321 of the metal plate 32. The adhesive material 31 bonds the element portion 4A and the metal plate 32 together, and fixes the element portion 4A to the metal plate 32.

[0039] The adhesive 31 may be conductive. The adhesive 31 may contain, for example, conductive particles such as Ni, and inorganic oxides such as TiO, rare earth element oxides (YO, CeO, etc.), and transition metal oxides (FeO, CuO, etc.).

[0040] The adhesive 31 may be gas permeable. When the adhesive 31 is gas permeable, the adhesive 31 may be positioned so as to cover an opening 32a described later. Furthermore, the solid electrolyte layer 6 may be positioned so as to cover the side surface of the adhesive 31.

[0041] As shown in FIG. 2A, a sealant 9 different from the solid electrolyte layer 6 may be positioned on the side surfaces of the adhesive 31 and the anode 5. The material of the sealant 9 may be dense glass or ceramic. The material of the sealant 9 may be, for example, amorphous glass or crystallized glass. As the crystallized glass, for example, any of SiO2-CaO-based, MgO-B2O3-based, La2O3-B2O3-MgO-based, La2O3-B2O3-ZnO-based, and SiO2-CaO-ZnO-based materials may be used, and in particular, SiO2-MgO-based materials may be used. The sealant 9 may have electrical insulating properties.

[0042] The material of the adhesive 31 may also have gas sealing properties. When the material of the adhesive 31 has gas sealing properties, the adhesive 31 may be positioned so as to contact the first surface 321 of the metal plate 32 where the openings 32a described below are not positioned. In this case, the adhesive 31 may be a dense body having through holes at the positions of the openings 32a.

[0043] The adhesive 31 may be formed as a single layer using a single material, or may be formed as a laminate of multiple materials. The adhesive 31 may be integrated with the anode 5. In other words, the anode 5 may be the first porous layer that also serves as the adhesive 31. The first porous layer may include the gas diffusion layer described above.

[0044] The metal plate 32 has a first surface 321 and a second surface 322 located at both ends in the thickness direction (Y-axis direction).

[0045] The metal plate 32 is electrically conductive. The metal plate 32 may be, for example, a member made of a metal containing chromium. The metal plate 32 may be, for example, a stainless steel such as a ferritic stainless steel or an austenitic stainless steel, which has high heat resistance. The metal plate 32 may be, for example, a nickel-chromium alloy or an iron-chromium alloy. The metal plate 32 may contain, for example, a metal oxide. The metal plate 32 may have a coating 320 covering the surface, as shown in FIG. 1C. The metal plate 32 does not have to have a coating 320 on the surface.

[0046] The metal plate 32 also has an opening 32a. The opening 32a is a through-hole that penetrates between the first surface 321 and the second surface 322. The fuel gas flowing through a flow path 35, which will be described later, is supplied to the fuel electrode 5 of the element section 4A through the opening 32a. The diameter of the opening 32a may be, for example, 0.1 mm to 0.5 mm, and particularly 0.3 mm to 0.4 mm. The aperture ratio in the region where the opening 32a is formed may be, for example, 10% or more. The metal plate 32 may have a coating 320 that covers the wall surface of the opening 32a. The metal plate 32 does not need to have the coating 320 on the wall surface of the opening 32a.

[0047] The metal plate 32 is, for example, 13×10 -6 The thermal expansion coefficient (linear expansion coefficient) may be about 1 / K.

[0048] The metal plate 32 may be gas permeable, for example, and in such a case, the metal plate 32 does not need to have the opening 32a.

[0049] The deformation suppression layer 33 is located so as to contact the second surface 322 of the metal plate 32. The deformation suppression layer 33 is located between the metal plate 32 and the flow path member 34. The deformation suppression layer 33 cooperates with the adhesive 31 to make the metal plate 32 less susceptible to warping, bending, and the like.

[0050] The deformation suppression layer 33 may be electrically conductive. The electrical conductivity of the deformation suppression layer 33 may be, for example, 10 to 1000 S / m.

[0051] The material of the deformation suppression layer 33 may be, for example, ZrO2 with a solid solution of Y. The deformation suppression layer 33 may also contain, for example, TiO2 with a solid solution of Sr or Ni. The material of the deformation suppression layer 33 may be the same as the material of the adhesive 31.

[0052] The deformation suppression layer 33 may be gas permeable. When the deformation suppression layer 33 is gas permeable, the deformation suppression layer 33 may be positioned so as to cover the opening 32a.

[0053] The material of the deformation suppression layer 33 may also have gas sealing properties. When the material of the deformation suppression layer 33 has gas sealing properties, the deformation suppression layer 33 may be positioned so as to contact the second surface 322 of the metal plate 32 where the openings 32a are not located. In this case, the deformation suppression layer 33 may be a dense body having through holes at the positions of the openings 32a.

[0054] The deformation suppression layer 33 may be configured as a single layer using a single material, or may be configured as a laminated layer in which a plurality of materials are superimposed.

[0055] The deformation suppression layer 33 has, for example, a thermal expansion coefficient (linear expansion coefficient) closer to that of the adhesive 31 than to that of the metal plate 32. By sandwiching the metal plate 32 between the adhesive 31 and the deformation suppression layer 33, which have similar thermal expansion coefficients (linear expansion coefficients), the conductive member 30 makes the metal plate 32 less likely to warp or bend.

[0056] Here, if the thermal expansion coefficient of the metal plate 32 is α0, the thermal expansion coefficient of the adhesive 31, which is the first porous layer, is α1, and the thermal expansion coefficient of the deformation suppression layer 33, which is the second porous layer, is α2, the conductive member 30 may have the relationship α1<α0 and α2<α0, for example. This makes it less likely for the metal plate 32 to warp or bend, thereby improving the adhesion between the metal plate 32 and the element section 4A. Therefore, a cell stack device 10 having such a conductive member 30 can improve power generation performance. In this case, α1 and α2 may be, for example, 10 to 12×10 -6 / K may be sufficient.

[0057] Furthermore, the conductive member 30 may have a metal plate 32, adhesive 31, and deformation suppression layer 33, which satisfy the relationships α1>α0 and α2>α0. Even in this case, warping and deflection of the metal plate 32 are less likely to occur, and the adhesion between the metal plate 32 and the element section 4A is improved. Therefore, a cell stack device 10 having such a conductive member 30 can improve power generation performance. The values ​​of α0, α1, and α2 can be adjusted, for example, by changing the composition of the conductive member 30.

[0058] Furthermore, |α1-α2| may be smaller than both |α0-α1| and |α0-α2|. This further reduces the risk of warping or bending of the metal plate 32, thereby enabling a cell stack device 10 including such a conductive member 30 to further improve power generation performance. The material of the deformation suppression layer 33, which is the second porous layer, may be the same as or different from the material of the adhesive 31, which is the first porous layer, as long as the relationship between α1, α2, and α3 is satisfied.

[0059] The thermal expansion coefficient of each component of the conductive member 30 can be obtained, for example, by analyzing the composition of the conductive member 30, preparing a test piece based on the analyzed composition, and measuring the coefficient using thermomechanical analysis (TMA) in accordance with JIS R 1618-1994.

[0060] The flow path member 34 is located on the second surface 322 side of the metal plate 32. The flow path member 34 is fixed and electrically connected to the second surface 322, for example, by welding or the like. The flow path member 34 may be fixed and electrically connected to the metal plate 32 using a conductive sealing material, brazing material, or the like. The space located between the deformation suppression layer 33 and the flow path member 34 is a flow path 35 through which the fuel gas flows. The fuel gas flowing through the flow path 35 permeates the conductive member 30 and is supplied to the anode 5. The flow path member 34 may have one or more protrusions protruding toward the deformation suppression layer 33.

[0061] The flow path member 34 is further fixed and electrically joined to the current collecting member 36 by welding or the like. The current collecting member 36 may be fixed and electrically joined to the flow path member 34 by a conductive sealing material, brazing material, or the like. The current collecting member 36 is fixed and electrically joined to the air electrode 8 of the adjacent cell 1A via an adhesive 40. The space located between the current collecting member 36 and the flow path member 34 is a flow path 37 through which an oxygen-containing gas flows. The oxygen-containing gas flowing through the flow path 37 passes through the slits in the current collecting member 36 and the adhesive 40, and is supplied to the air electrode 8 of the adjacent cell 1A.

[0062] The flow path member 34 and the current collecting member 36 are made of a dense metal or alloy. The flow path member 34 prevents leakage of the fuel gas flowing through the flow path 35 and the oxygen-containing gas flowing through the flow path 37. The flow path member 34 and the current collecting member 36 may have a coating layer. For example, the surface of the flow path member 34 facing the flow path 35 may have a coating layer that is resistant to reduction. Furthermore, the surface of the flow path member 34 facing the flow path 37 may have a coating layer that is resistant to oxidation. These coating layers may be electrically conductive.

[0063] The shapes of the flow path member 34 and the current collecting member 36 are not limited to those shown in Fig. 1A. The flow path member 34 and the current collecting member 36 may have any shape as long as they electrically connect adjacent cells 1A and prevent leakage of fuel gas and oxygen-containing gas. For example, as shown in Fig. 2B, the flow path member 34 may be integrated with the current collecting member 36 and have a first convex portion that protrudes toward the deformation suppression layer 33 and a second convex portion that protrudes toward the opposite side from the first convex portion.

[0064] <Configuration of cell stack device> Next, an electrochemical cell device according to this embodiment using the above-described cell 1A will be described with reference to Figs. 3A to 3C. Fig. 3A is a perspective view showing an example of the electrochemical cell device according to the first embodiment. Fig. 3B is a cross-sectional view taken along line XX shown in Fig. 3A. Fig. 3C is a top view showing an example of the electrochemical cell device according to the first embodiment.

[0065] As shown in FIG. 3A, the cell stack device 10 includes a cell stack 11 having a plurality of cells 1A arranged (stacked) in the thickness direction of the element section 4A (the Y-axis direction shown in FIG. 1A), and a fixing member 12.

[0066] The fixing member 12 has a fixing material 13 and a support member 14. The support member 14 supports the cell 1A. The fixing material 13 fixes the cell 1A to the support member 14. The support member 14 also has a support 15 and a gas tank 16. The support 15 and gas tank 16, which are the support member 14, are made of metal and are electrically conductive.

[0067] 3B, the support body 15 has insertion holes 15a into which the lower ends of the cells 1A are inserted. The lower ends of the cells 1A and the inner wall of the insertion holes 15a are joined with fixing material 13.

[0068] The gas tank 16 has an opening for supplying a reaction gas to the cells 1A 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.

[0069] In the example shown in FIG. 3A, fuel gas is stored in an internal space 22 (see FIG. 3B) formed by a support 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 35 (see FIG. 1A) inside the cell 1A. The fuel gas supplied to the gas tank 16 is generated in a reformer 102 (see FIG. 4), which will be described later.

[0070] 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.

[0071] 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 has a plurality of cells 1A. 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. An internal space 22 is formed by the one gas tank 16 and the two supports 15.

[0072] 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 1A, i.e., the thickness direction (Y-axis direction shown in FIG. 1A), 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 1A in the width direction (X-axis direction shown in FIG. 1A).

[0073] 3B, the joints between the inner walls of the insertion holes 15a and the lower ends of the cells 1A are filled with a fixing material 13 and solidified. This bonds and fixes the inner walls of the insertion holes 15a to the lower ends of the multiple cells 1A, respectively, and also bonds and fixes the lower ends of the cells 1A to each other. The gas flow paths 2a of each cell 1A communicate with the internal space 22 of the support member 14 at their lower ends.

[0074] 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.

[0075] As the crystallized glass, for example, any of materials such as SiO2-CaO, MgO-B2O3, La2O3-B2O3-MgO, La2O3-B2O3-ZnO, and SiO2-CaO-ZnO may be used, and in particular, SiO2-MgO materials may be used.

[0076] 3B, a conductive member 18 is interposed between adjacent cells 1A among the plurality of cells 1A. The conductive member 18 electrically connects one adjacent cell 1A to the other adjacent cell 1A in series. More specifically, the conductive member 18 connects the fuel electrode 5 of one cell 1A to the air electrode 8 of the other cell 1A. The conductive member 18 may be the conductive member 30 shown in FIG. 1A or may be a member separate from the conductive member 30.

[0077] As shown in Fig. 3B, an end current collecting member 17 is electrically connected to the cell 1A located outermost in the arrangement direction of the multiple cells 1A. The end current collecting member 17 is connected to a conductive part 19 that protrudes outward from the cell stack 11. The conductive part 19 collects electricity generated by power generation in the cells 1A and extracts it to the outside. Note that the end current collecting member 17 is not shown in Fig. 3A.

[0078] 3C, the cell stack device 10 may be a single battery in which two cell stacks 11A and 11B are connected in series. In this case, the conductive part 19 of the cell stack device 10 may have a positive terminal 19A, a negative terminal 19B, and a connection terminal 19C.

[0079] The positive electrode terminal 19A is a positive electrode when the power generated by the cell stack 11 is output to the outside, and is electrically connected to the positive electrode side end current collecting member 17 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, and is electrically connected to the negative electrode side end current collecting member 17 of the cell stack 11B.

[0080] The connection terminal 19C electrically connects the end current collecting member 17 on the negative electrode side of the cell stack 11A and the end current collecting member 17 on the positive electrode side of the cell stack 11B.

[0081] Although not shown in Figures 3A to 3C, the cell stack device 10 may also be provided with a second gas tank at the top of the cell stack 11, which fixes the upper ends of multiple cells 1A and collects gas discharged from the flow path 35 inside the cells 1A.

[0082] <module> Next, a module according to an embodiment of the present disclosure 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 the first 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 pulled out to the rear.

[0083] 4, the module 100 includes a storage container 101 and a cell stack device 10 housed in the storage container 101. A reformer 102 is disposed above the cell stack device 10.

[0084] The reformer 102 reforms raw fuel such as natural gas or kerosene to generate fuel gas, which is then supplied to the cell 1A. 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.

[0085] The fuel gas produced in the reformer 102 is supplied to the flow path 35 of the cell 1A (see FIG. 1A) through the gas distribution pipe 20, the gas tank 16, and the support member 14.

[0086] When the cell stack device 10 includes a second gas tank above the cell stack 11, the reformer 102 may be disposed in a location other than above the cell stack device 10. The raw fuel supply pipe 103, the gas circulation pipe 20, etc. may be disposed appropriately depending on the arrangement of the cell stack device 10 and the reformer 102.

[0087] Furthermore, in the module 100 having the above-described configuration, the temperature inside the module 100 during normal power generation becomes approximately 500°C to 1000°C due to power generation by the cells 1A and the like.

[0088] In such a module 100, as described above, by accommodating the cell stack device 10 that improves power generation performance, the module 100 can be made to have improved power generation performance.

[0089] <Module storage device> Fig. 5 is an exploded perspective view schematically illustrating an example of a module housing device according to the first embodiment. The module housing 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.

[0090] 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 accessory accommodating chamber 116 that accommodates accessory equipment for operating the module 100. Note that in Fig. 5, the accessory equipment accommodated in the accessory accommodating chamber 116 is omitted.

[0091] 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.

[0092] In such a module accommodating device 110, as described above, by accommodating the module 100 with improved power generation performance in the module accommodating chamber 115, the module accommodating device 110 can be made to have improved power generation performance.

[0093] [Second embodiment] Fig. 6 is a perspective view showing an example of an electrochemical cell according to the second embodiment, and Fig. 7 is a partial cross-sectional view of the electrochemical cell shown in Fig. 6.

[0094] As shown in FIGS. 6 and 7, cell 1B has an element section 4B, a conductive member 30, and flow path members 91 and 92. Element section 4B has an anode 5, a solid electrolyte layer 6, and a cathode 8. The materials of the anode 5, the solid electrolyte layer 6, and the cathode 8 may be the same as the materials of the anode 5, the solid electrolyte layer 6, and the cathode 8 of cell 1A described above. Element section 4B may also have an intermediate layer 7 located between the solid electrolyte layer 6 and the cathode 8. The material of this intermediate layer 7 may be the same as the material of any intermediate layer that cell 1A described above has.

[0095] The flow path members 91, 92 have gas flow paths that supply gas to the fuel electrode 5 or the air electrode 8, and also electrically connect adjacent cells 1B. In an electrochemical cell device in which a plurality of flat plate-type cells are stacked, for example, a plurality of cells 1B are electrically connected by the flow path members 91, 92, which are adjacent metal layers.

[0096] 7, cell 1B has a sealing material that airtightly seals the fuel gas flow path and the oxygen-containing gas flow path of the flat cell stack. The sealing material is a cell fixing member 96, and has a bonding material 93 and support members 94 and 95 that serve as a frame. The bonding material 93 may be glass or a metal material such as silver solder.

[0097] The support member 94 may be a so-called separator that separates the fuel gas flow path from the oxygen-containing gas flow path. The material of the support members 94, 95 may be, for example, a conductive metal or an insulating ceramic. Either or both of the support members 94, 95 may be made of an insulating material. If the support member 94 is made of metal, the support member 94 may be integrated with the flow path member 92. If the support member 95 is made of metal, the support member 95 may be integrated with the flow path member 91.

[0098] Either one of the support members 94, 95 is insulating, and electrically insulates the two flow path members 91, 92 that sandwich the flat cell from each other.

[0099] In the cell 1B shown in FIG. 7, the conductive member 30 is located between the element unit 4B and the flow path member 91. The conductive member 30 has a first porous layer and a deformation suppression layer 33 as a second porous layer. In the cell 1B shown in FIG. 7, the first porous layer of the conductive member 30 is the fuel electrode 5 that contacts the first surface 321 of the metal plate 32. The conductive member 30 of the cell 1B may have an adhesive material as the first porous layer between it and the fuel electrode 5. The adhesive material bonds the element unit 4B and the metal plate 32 and fixes the element unit 4B to the metal plate 32. The first porous layer may include the gas diffusion layer described above.

[0100] The metal plate 32 may be made of the same material as the metal plate 32 of the electrochemical cell according to the first embodiment. The metal plate 32 may be, for example, a conductive metal member and may contain chromium. The metal plate 32 may contain, for example, a metal oxide. Furthermore, the metal plate 32 may or may not have a coating covering the surface.

[0101] The metal plate 32 also has an opening 32a. The opening 32a is a through-hole that penetrates between the first surface 321 and the second surface 322. The metal plate 32 may or may not have a coating that covers the wall surface of the opening 32a.

[0102] The metal plate 32 is, for example, 13×10 -6The thermal expansion coefficient (linear expansion coefficient) may be about 1 / K.

[0103] The metal plate 32 may be, for example, gas permeable, and in such a case, the metal plate 32 may not have the opening 32a.

[0104] The deformation suppression layer 33 is located so as to contact the second surface 322 of the metal plate 32. The deformation suppression layer 33 is located between the metal plate 32 and the flow path member 91. In the cell 1B shown in FIG. 7, the deformation suppression layer 33 cooperates with the fuel electrode 5, which is the first porous layer, to make the metal plate 32 less susceptible to warping, bending, and the like.

[0105] In the cell 1B, the deformation suppression layer 33 of the conductive member 30 is conductive. The deformation suppression layer 33 electrically connects the flow path member 91 and the element section 4B. The material of the deformation suppression layer 33 may be the same as the material of the fuel electrode 5.

[0106] The deformation suppression layer 33 may be gas permeable. If the deformation suppression layer 33 is gas permeable, the deformation suppression layer 33 may be positioned so as to cover the opening 32a. The material of the deformation suppression layer 33 may also have gas sealing properties. If the material of the deformation suppression layer 33 has gas sealing properties, the deformation suppression layer 33 may be positioned so as to contact the second surface 322 of the metal plate 32 where the opening 32a is not located. In this case, the deformation suppression layer 33 may be a dense body having through holes at the positions of the openings 32a.

[0107] The deformation suppression layer 33 may be configured as a single layer using a single material, or may be configured as a laminated layer in which a plurality of materials are superimposed.

[0108] The deformation suppression layer 33 has, for example, a thermal expansion coefficient (linear expansion coefficient) closer to that of the adhesive 31 than to that of the metal plate 32. By sandwiching the metal plate 32 between the adhesive 31 and the deformation suppression layer 33, which have similar thermal expansion coefficients (linear expansion coefficients), the conductive member 30 makes the metal plate 32 less likely to warp or bend.

[0109] If the thermal expansion coefficient of the metal plate 32 is α0, the thermal expansion coefficient of the fuel electrode 5 (first porous layer) is α1, and the thermal expansion coefficient of the deformation suppression layer 33 (second porous layer) is α2, the conductive member 30 may have the relationship α1<α0 and α2<α0, for example. This makes it less likely for the metal plate 32 to warp or bend, thereby improving the adhesion between the metal plate 32 and the element section 4B. Therefore, a cell stack device including such a conductive member 30 can improve power generation performance. In this case, α1 and α2 may be, for example, 10 to 12×10 -6 / K may be sufficient.

[0110] Furthermore, the conductive member 30 may have a metal plate 32, an anode 5, and a deformation suppression layer 33 that satisfy the relationships α1>α0 and α2>α0. Even in this case, warping or deflection of the metal plate 32 is less likely to occur, which improves adhesion between the metal plate 32 and the element section 4B, and a cell stack device that includes such a conductive member 30 can improve power generation performance. The values ​​of α0, α1, and α2 can be adjusted, for example, by changing the composition of the conductive member 30.

[0111] Furthermore, |α1-α2| may be smaller than both |α0-α1| and |α0-α2|. This further reduces the risk of warping or bending of the metal plate 32, thereby enabling a cell stack device including such a conductive member 30 to further improve power generation performance. The material of the deformation suppression layer 33, which is the second porous layer, may be the same as or different from the material of the fuel electrode 5, which is the first porous layer, as long as the relationship between α1, α2, and α3 is satisfied.

[0112] [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. The electrolysis cell has a first electrode and a second electrode, and decomposes water vapor into hydrogen and oxygen, or 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 an electrolysis cell, an electrolysis cell stack device, an electrolysis module, and an electrolysis device can improve electrolysis performance.

[0113] Although the present disclosure has been described in detail above, 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.

[0114] In one embodiment, (1) the conductive member includes a metal plate having a first surface and a second surface located opposite to the first surface, and allowing gas to flow between the first surface and the second surface; a first porous layer in contact with the first surface; a second porous layer in contact with the second surface; and Equipped with When the thermal expansion coefficient of the metal plate is α0, the thermal expansion coefficient of the first porous layer is α1, and the thermal expansion coefficient of the second porous layer is α2, The relationship is α1<α0 and α2<α0, or α1>α0 and α2>α0.

[0115] (2) In the conductive member of (1) above, the metal plate may have a plurality of openings that penetrate the first surface and the second surface.

[0116] (3) In the conductive member of (1) or (2) above, the first porous layer and the second porous layer may be conductive.

[0117] (4) In the conductive member of any one of (1) to (3) above, the first porous layer, the second porous layer, and the metal plate are The relationship may be α1<α0 and α2<α0.

[0118] (5) In any one of the conductive members (1) to (4) above, |α1-α2| may be smaller than both |α0-α1| and |α0-α2|.

[0119] In one embodiment, (6) the electrochemical cell device includes two or more electrochemical cells having element parts, Any one of the conductive members (1) to (5) above Equipped with.

[0120] In one embodiment, the module (7) comprises the electrochemical cell device (6) described above, and a container for housing the electrochemical cell device.

[0121] In one embodiment, the module storage device (8) includes the module (7) and Auxiliary equipment for operating the module; and an exterior case that houses the module and the auxiliary equipment.

[0122] 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. [Explanation of symbols]

[0123] 1A, 1B cells 4A, 4B element section 9. Encapsulating materials 10 Cell stack device 30 Conductive material 31 Adhesive 32 Metal plate 33 Deformation suppression layer 100 modules 110 Module storage device

Claims

1. a metal plate having a first surface and a second surface located opposite to the first surface, and allowing gas to flow between the first surface and the second surface; a first porous layer in contact with the first surface; a second porous layer in contact with the second surface; Equipped with When the thermal expansion coefficient of the metal plate is α0, the thermal expansion coefficient of the first porous layer is α1, and the thermal expansion coefficient of the second porous layer is α2, The relationship is α1<α0 and α2<α0, or α1>α0 and α2>α0. Conductive material.

2. The metal plate has a plurality of openings penetrating the first surface and the second surface. The conductive member according to claim 1 .

3. The first porous layer and the second porous layer are electrically conductive. The conductive member according to claim 1 .

4. The first porous layer, the second porous layer, and the metal plate are The relationship is α1<α0 and α2<α0. The conductive member according to claim 1 .

5. |α1-α2| is smaller than both |α0-α1| and |α0-α2| The conductive member according to claim 1 .

6. two or more electrochemical cells each having an element portion; The conductive member according to any one of claims 1 to 5. An electrochemical cell device comprising:

7. The electrochemical cell device according to claim 6 ; a container for housing the electrochemical cell device; A module comprising:

8. A module according to claim 7; Auxiliary equipment for operating the module; an exterior case that houses the module and the auxiliary equipment; A module housing device comprising:

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