Metal member, electrochemical cell device, module, and module housing apparatus

Abstract

This metal member comprises a metal sheet and a coating layer. The metal sheet has recesses and / or protrusions on a first surface. The coating layer is positioned on the first surface. The coating layer has a first portion and a second portion having a higher porosity than the first portion.

Description

Metal components, electrochemical cell devices, modules, and module housings.

[0001] This disclosure relates to metal components, electrochemical cell devices, modules, and module housing devices.

[0002] In recent years, various fuel cell cell stack devices, which have multiple fuel cell 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 hydrogen-containing gas and an oxygen-containing gas such as air.

[0003] Japanese Patent Publication No. 2023-93447

[0004] A metal member according to one embodiment comprises a metal plate and a coating layer. The metal plate has a recess and / or protrusion on a first surface. The coating layer is located on the first surface. The coating layer has a first portion and a second portion having a higher porosity than the first portion.

[0005] Furthermore, the electrochemical cell apparatus of this disclosure comprises an electrochemical cell and the metal member described above. The electrochemical cell comprises a first electrode, a second electrode containing metal particles, and a solid electrolyte layer located between the first electrode and the second electrode. The coating layer covering the protrusion is bonded to the first electrode.

[0006] Furthermore, the module of this disclosure comprises the electrochemical cell apparatus described above and a housing container that houses the electrochemical cell apparatus.

[0007] Furthermore, the module housing device of this disclosure comprises the module described above, an auxiliary device configured to operate the module, and an outer casing housing the module and the auxiliary device.

[0008] FIG. 1A is a cross-sectional view showing an example of an electrochemical cell device according to an embodiment. FIG. 1B is a plan view of an example of an electrochemical cell according to the embodiment as viewed from the air electrode side. FIG. 1C is a plan view showing an example of a metal member according to the embodiment. FIG. 1D is a cross-sectional view showing another example of the electrochemical cell device according to the embodiment. FIG. 2A is an enlarged plan view of a part of the metal member shown in FIG. 1C. FIG. 2B is a cross-sectional view taken along line A-A shown in FIG. 2A. FIG. 3A is a perspective view showing an example of the electrochemical cell device according to the embodiment. FIG. 3B is a cross-sectional view taken along line X-X shown in FIG. 3A. FIG. 3C is a top view showing an example of the electrochemical cell device according to the embodiment. FIG. 4 is an external perspective view showing an example of a module according to the embodiment. FIG. 5 is an exploded perspective view schematically showing an example of a module housing device according to the embodiment.

[0009] In the above fuel cell stack device, there was room for improvement in terms of improving durability.

[0010] Therefore, there is an expectation for providing a metal member, an electrochemical cell device, a module, and a module housing device that can improve durability.

[0011] Hereinafter, embodiments of the metal member, the electrochemical cell device, the module, and the module housing device disclosed in the present application will be described in detail with reference to the accompanying drawings. Note that this disclosure is not limited by the embodiments shown below.

[0012] Also, note that the drawings are schematic, and it is necessary to be aware that the dimensional relationships between elements, the ratios of the elements, etc. may be different from reality. Furthermore, there may be parts where the dimensional relationships and ratios between the drawings are different from each other.

[0013] [Embodiment] <Configuration of Electrochemical Cell> First, with reference to FIGS. 1A to 1C, an electrochemical cell connected to a metal member according to an embodiment will be described using an example of a solid oxide type 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 is simply referred to as a cell stack device.

[0014] Figure 1A is a cross-sectional view showing an example of an electrochemical cell apparatus according to the embodiment. Figure 1B is a plan view of an example of an electrochemical cell according to the embodiment, viewed from the air electrode side. Figure 1C is a plan view showing an example of a metal member according to the embodiment. Figures 1A to 1C show enlarged views of some of the components of the electrochemical cell. Hereinafter, the electrochemical cell may simply be referred to as a cell.

[0015] For the sake of clarity, Figures 1A to 1C illustrate a three-dimensional Cartesian coordinate system including the Z-axis, where the vertically upward direction is positive and the vertically downward direction is negative. This Cartesian coordinate system may also be shown in other drawings used in later explanations. Furthermore, components with the same reference numerals as those in the electrochemical cells shown in Figures 1A to 1C are used, and their explanations are omitted or simplified.

[0016] The cell stack device 10 according to this embodiment comprises a cell 1 and a metal member 30. The cell 1 comprises a support member 2 and an element portion 3.

[0017] The support member 2 is electrically conductive. The support member 2 may also be, for example, a plate-shaped metal member containing chromium. The support member 2 may also be, for example, a stainless steel such as a ferritic stainless steel or austenitic stainless steel with high heat resistance. The support member 2 may also be, for example, a nickel-chromium alloy or an iron-chromium alloy. The support member 2 may also contain, for example, a metal oxide. Furthermore, the support member 2 may have a coating covering its surface. The support member 2 does not necessarily have a coating on its surface.

[0018] Furthermore, the support member 2 may have an opening that penetrates in the thickness direction (Y-axis direction). The fuel gas flowing through the 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 or more and 0.5 mm or less, and particularly 0.3 mm or more and 0.4 mm or less. The opening ratio in the region where the opening is formed may be, for example, 10% or more. The support member 2 may have a coating that covers the wall surface of the opening. The support member 2 does not have to have a coating on the wall surface of the opening.

[0019] The support member 2 may, for example, be gas permeable. In this case, the support member 2 does not need to have an opening that penetrates in the thickness direction (Y-axis direction).

[0020] The element section 3 includes a fuel electrode 5, a solid electrolyte layer 6, and an air electrode 8. The fuel electrode 5 is a second electrode in contact with the fuel gas, which is a reducing gas. The fuel electrode 5 contains metal particles. The fuel electrode 5 is gas permeable. The open porosity of the fuel electrode 5 may be, for example, 30% or more and 50% or less, and particularly 35% or more and 45% or less. The open porosity of the fuel electrode 5 is sometimes referred to as the porosity or void ratio of the fuel electrode 5.

[0021] The fuel electrode 5 can be made of a material that is generally known. The fuel electrode 5 can be made of porous conductive ceramics, such as calcium oxide, magnesium oxide, or ZrO2 in which rare earth element oxides are in solid solution. ２ Furthermore, ceramics containing elemental Ni, namely metallic Ni and / or NiO, may be used. This rare earth element oxide may include, for example, multiple rare earth elements selected from Sc, Y, La, Nd, Sm, Gd, Dy, and Yb. Calcium oxide, magnesium oxide, or ZrO containing a solid solution of rare earth element oxides may also be used. ２ This is sometimes referred to as stabilized zirconia. Stabilized zirconia may include partially stabilized zirconia. The fuel electrode 5 is CeO in which La, Nd or Yb is in solid solution. ２ It may include.

[0022] The solid electrolyte layer 6 is an electrolyte that facilitates the transfer of ions between the fuel electrode 5 and the air electrode 8. At the same time, the solid electrolyte layer 6 has gas barrier properties, making it difficult for leakage between the fuel gas and the oxygen-containing gas to occur.

[0023] The material of the solid electrolyte layer 6 is, for example, ZrO2 in which 3 mol% to 15 mol% of rare earth element oxides are solid-dissolved. ２ 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 be, for example, ZrO in which Yb, Sc, or Gd is solid-solved. ２may be included. The solid electrolyte layer 6 may contain, for example, CeO in which La, Nd or Yb is dissolved. ２ may be included. The solid electrolyte layer 6 may contain, for example, BaZrO in which Sc or Yb is dissolved. ３ may be included. The solid electrolyte layer 6 may contain, for example, BaCeO in which Sc or Yb is dissolved. ３ may be included.

[0024] The air electrode 8 is a first electrode in 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, 20% or more and 50% or less, particularly 30% or more and 50% or less. The open porosity of the air electrode 8 may also be referred to as the porosity of the air electrode 8.

[0025] The material of the air electrode 8 is not particularly limited as long as it 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 ABO ３ type perovskite oxide.

[0026] 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 ｘ Sr １－ｘ CoO ３ and the like. Here, x is 0 < x < 1 and y is 0 < y < 1.

[0027] Further, the element part 3 may have an intermediate layer (not shown) located between the solid electrolyte layer 6 and the air electrode 8. When the element part 3 has an intermediate layer, the intermediate layer has a function as a diffusion suppression layer that, for example, makes it difficult for specific elements to diffuse. When a specific element such as Sr (strontium) contained in the air electrode 8 diffuses into the solid electrolyte layer 6, SrZrO with a high electrical resistance is formed in the solid electrolyte layer 6. ３Resistive phases such as Sr are more likely to form. The intermediate layer makes it difficult for elements such as Sr to diffuse, resulting in SrZrO ３ This makes it difficult for high-resistance compounds such as these to form.

[0028] The material of the intermediate layer is not particularly limited as long as it generally prevents the diffusion of elements between the air electrode 8 and the solid electrolyte layer 6. The material of the intermediate layer may be, for example, cerium oxide (CeO2) in which rare earth elements other than Ce (cerium) are solid-solved. ２ ) may also be included. Examples of such rare earth elements include Gd (gadolinium) and Sm (samarium).

[0029] Furthermore, cell 1 may have a restraining layer (not shown). The restraining layer may be located between the element portion 3 and the support member 2. Such a restraining layer cooperates with the solid electrolyte layer 6 to make it difficult for the element portion 3 to warp, bend, etc.

[0030] The material of the constraining layer may exhibit a shrinkage rate similar to that of the solid electrolyte layer 6 during firing. The material of the constraining layer may have a similar or identical composition to that of the solid electrolyte layer 6. The element 3 obtained by sandwiching the fuel electrode 5 material of the element 3 between the solid electrolyte layer 6 material and the constraining layer material and firing it will have reduced warping or deformation.

[0031] The restraining layer may or may not be gas permeable. If the restraining layer has gas barrier properties similar to those of the solid electrolyte layer 6, the restraining layer can be partially positioned so as not to obstruct the inflow of fuel gas to the fuel electrode 5.

[0032] Furthermore, cell 1 may have a gas diffusion layer, which is not shown. The gas diffusion layer may be located between the fuel electrode 5 and the support member 2. Such a gas diffusion layer may be gas permeable so as to allow the fuel gas flowing through the flow path 2a (described later) to permeate to the fuel electrode 5. The open porosity of the gas diffusion layer may be, for example, 30% to 50%, and particularly 35% to 45%.

[0033] The material for the gas diffusion layer may be a porous conductive ceramic, such as a ceramic containing stabilized or partially stabilized zirconia in which calcium oxide, magnesium oxide, or rare earth element oxides are solid-solved, and metallic Ni and / or NiO. These rare earth element oxides may include, for example, a plurality of rare earth elements selected from Sc, Y, La, Nd, Sm, Gd, Dy, and Yb.

[0034] Cell 1 may also have an adhesive (not shown). The adhesive may be located between the element portion 3 and the support member 2. Such adhesive joins the element portion 3 and the support member 2, fixing the element portion 3 to the support member 2.

[0035] The adhesive may be conductive. The adhesive may, for example, contain conductive particles such as Ni and TiO ２ , rare earth element oxides (Y ２ O ３ , CEO ２ etc.), transition metal oxides (Fe ２ O ３ It may also contain inorganic oxides such as CuO.

[0036] The adhesive may be gas permeable. Furthermore, the solid electrolyte layer 6 may be positioned to cover the sides of the adhesive.

[0037] The metal member 30 is located between the first element portion 3A and the second element portion 3B of a cell 1 that is different from the first element portion 3A. The metal member 30 is located between the fuel electrode 5 of the first element portion 3A and the air electrode 8 of the second element portion 3B. The metal member 30 has a surface 31 and a surface 32. The metal member 30 makes it difficult for oxygen-containing gas flowing on the surface 31 side and fuel gas flowing on the surface 32 side to leak.

[0038] The metal member 30 may be fixed to the support member 2 by welding or the like at the contact point and electrically joined. The metal member 30 may be fixed to the support member 2 by a conductive sealing material or brazing material and electrically joined. A flow path 2a through which fuel gas flows is located between the surface 32 of the metal member 30 and the support member 2. The fuel gas flowing through the flow path 2a is supplied to the fuel electrode 5 by passing through the support member 2.

[0039] Surface 31 is fixed to the air electrode 8, for example, via a conductive adhesive, and electrically joined. A space through which oxygen-containing gas flows is located between the metal member 30 and the air electrode 8.

[0040] The surface 31 of the metal member 30 facing the fuel electrode 5 with the support member 2 in between may have a first portion P1 and a second portion P2, as shown in Figure 1C. The first portion P1 is located in the central part in the X-axis direction facing the air electrode 8. The second portion P2 is located at both ends in the X-axis direction adjacent to the first portion P1.

[0041] The metal member 30 has a first end 41 and a second end 42 located at both ends in the Z-axis direction. The oxygen-containing gas may flow through the space between the surface 31 located at the first portion P1 and the air electrode 8, for example, from the first end 41 side to the second end 42 side. Details of the metal member 30 will be described later.

[0042] Figure 1D is a cross-sectional view showing another example of an electrochemical cell apparatus according to the embodiment. As shown in Figure 1D, a sealant 9 different from the solid electrolyte layer 6 may be located on the side surfaces of the fuel electrode 5 and the solid electrolyte layer 6. 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 a crystallized glass, for example, 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 system, SiO ２ Any of the following materials may be used, particularly SiO ２ -MgO-based materials may be used. The sealing material 9 may also have electrical insulating properties.

[0043] <Details of the Metal Member> Next, the details of the metal member 30 will be further explained with reference to Figures 1C, 2A, and 2B. Figure 2A is an enlarged plan view of a part of the metal member shown in Figure 1C. Figure 2B is a cross-sectional view taken along line A-A shown in Figure 2A.

[0044] The metal member 30 has a flat portion 30a, a convex portion 30b, and a recessed portion 30c in the first portion P1. The flat portion 30a, the convex portion 30b, and the recessed portion 30c are surfaces 31 that face the air electrode 8 when the metal member 30 is positioned between the air electrode 8 of the second element portion 3B and the support member 2, as shown in Figure 2B.

[0045] The protrusion 30b is positioned to project from the flat portion 30a toward the air electrode 8 of the second element portion 3B. The surface 31 of the protrusion 30b may be in contact with the air electrode 8.

[0046] The recess 30c is positioned to recede from the flat portion 30a toward the support member 2. The recess 30c may have a surface 32 opposite to surface 31 that is in contact with the support member 2.

[0047] The metal member 30 comprises a metal plate 300 and a coating layer 301. The metal plate 300 has a first surface 300a. The metal plate 300 may have a protrusion 300b and a recess 300c on the first surface 300a. The protrusion 300b is the portion of the first surface 300a that protrudes toward the air electrode 8 of the second element portion 3B. The protrusion 300b has a top portion 300b1, a first corner portion 300b2, and an outer portion 300b3.

[0048] The top portion 300b1 is the part of the convex portion 300b that has a small distance from the air pole 8. The surface of the top portion 300b1 may be flat or curved. The surface of the top portion 300b1 may have irregularities.

[0049] Furthermore, the top portion 300b1 may be joined to the air electrode 8 via the coating layer 301. In other words, the coating layer 301 covering the protrusion 300b may be joined to the air electrode 8. This improves the conductivity between the cells 1 via the metal member 30.

[0050] The first corner portion 300b2 is the portion of the protrusion 300b that is widely spaced from the air electrode 8. The first corner portion 300b2 is the corner portion of the protrusion 300b that forms the outline of the protrusion 300b when viewed from the second element portion 3B side in a plan view.

[0051] The outer portion 300b3 is the part that connects the top portion 300b1 and the first corner portion 300b2. The surface of the outer portion 300b3 may be inclined with respect to the Y-axis direction, or it may be aligned with the Y-axis direction.

[0052] The recess 300c is the portion of the first surface 300a that is recessed toward the support member 2. The recess 300c has a bottom portion 300c1, a second corner portion 300c2, and an inner portion 300c3.

[0053] The bottom portion 300c1 is the part of the recess 300c that has a large gap from the air electrode 8. The bottom portion 300c1 may have a flat surface or a curved surface. The bottom portion 300c1 may have irregularities on its surface.

[0054] The second corner 300c2 is a corner that forms the periphery of the bottom 300c1. The second corner 300c2 is located between the bottom 300c1 and the inner part 300c3.

[0055] The inner portion 300c3 is the part of the recess 300c that has a small gap from the air electrode 8. The surface of the inner portion 300c3 may be inclined with respect to the Y-axis direction, or it may be aligned with the Y-axis direction.

[0056] The metal plate 300 is electrically conductive. The metal plate 300 may also contain, for example, chromium. The metal plate 300 may be made of, for example, heat-resistant stainless steel such as ferritic stainless steel or austenitic stainless steel. The metal plate 300 may also be made of, for example, a nickel-chromium alloy or an iron-chromium alloy. The metal plate 300 may also contain, for example, a metal oxide.

[0057] The coating layer 301 is located on the first surface 300a of the metal plate 300. The coating layer 301 may be an oxide containing, for example, at least one of Zn, Mn, and Co. An example of a composite oxide having such a structure is ZnMnCoO ４ Zn(Coｘ Mn １－ｘ ) ２ O ４ (0<x<1), Mn １．５ Co １．５ O ４ MnCo ２ O ４ CoMn ２ O ４ The following may also be used. Having such a coating layer 301 makes it less likely for the oxygen-containing gas flowing through the channel 40 to come into contact with the metal plate 300, thereby improving the durability of the metal member 30.

[0058] Furthermore, the coating layer 301 may contain elements other than Zn, Mn, and Co, such as Al. Such oxides may be composite oxides having a spinel structure.

[0059] The coating layer 301 has a first portion 301a and a second portion 301b which has a higher porosity than the first portion 301a. Because the coating layer 301 has a first portion 301a and a second portion 301b, even if the metal member 30 is thermally deformed, for example, the coating layer 301 is less likely to peel off from the metal plate 300, and the durability of the metal member 30 is improved.

[0060] The first portion 301a may have a porosity of 18% or less. This makes it less likely for the oxygen-containing gas flowing through the channel 40 to come into contact with the metal plate 300, thereby improving the durability of the metal member 30.

[0061] The second portion 301b may be located at the second corner 300c2 of the recess 300c. This makes it less likely for the coating layer 301 to peel off from the second corner 300c2 even if the metal member 30 is thermally deformed, thereby improving the durability of the metal member 30. Here, "located at the second corner 300c2" means that the second portion 301b is in contact with the second corner 300c2 and covers the entire circumference of the second corner 300c2. The second portion 301b may be located so as to cover a part of the bottom 300c1 and / or a part of the inner part 300c3 from the second corner 300c2. Alternatively, the second portion 301b may be located so as to cover the entire bottom 300c1.

[0062] The second portion 301b may be located at the first corner 300b2 of the protrusion 300b. This makes it less likely for the coating layer 301 to peel off from the first corner 300b2 even if the metal member 30 is thermally deformed, thereby improving the durability of the metal member 30. Here, "located at the first corner 300b2" means that the second portion 301b contacts the first corner 300b2 and covers the entire circumference of the first corner 300b2. The second portion 301b may also be positioned to cover a part of the first corner 300b2 and / or a part of the outer portion 300b3 from the first corner 300b2.

[0063] The second portion 301b may have a porosity of 20% to 50%. This makes it less likely for the coating layer 301 to peel off from the metal plate 300 even if the metal member 30 is thermally deformed, and also improves high-temperature durability. As a result, the durability of the metal member 30 is further improved.

[0064] Here, the positions and porosity of the first portion 301a and the second portion 301b of the coating layer 301 can be evaluated as follows. A cross-section of the metal member 30 having the coating layer 301 on the first surface 300a, including the convex portion 30b and / or concave portion 30c, is observed using, for example, a digital microscope or SEM (scanning electron microscope) to distinguish between the convex portion 300b and / or concave portion 300c of the metal plate 300 and the coating layer 301. The cross-section may be prepared by fracturing the metal member 30 or by CP (chemical polishing) processing. A cross-sectional image including the convex portion 300b and / or concave portion 300c and the coating layer 301 is taken, for example, at a magnification of 2000x, and the coating layer 301 and the pores in the coating layer 301 are distinguished from the obtained cross-sectional image. Furthermore, the porosity of the coating layer 301 located on the flat portion 30a, the porosity of the coating layer 301 covering the top portion 300b1, the first corner portion 300b2, the outer portion 300b3, etc. of the convex portion 300b, and / or the bottom portion 300c1, the second corner portion 300c2, the inner portion 300c3, etc. of the concave portion 300c can be calculated by image analysis.

[0065] Table 1 shows the relationship between the porosity of the second section 301b and the durability of the metal member 30. As shown in Table 1, five samples with different porosity levels of the second section 301b were prepared, and their peel resistance and high-temperature durability were compared. The porosity of the first section 301a was 18% in all cases. The test methods for peel resistance and high-temperature durability are as follows.

[0066] <Peel Resistance Test> In the peel resistance test, after heat treatment of the metal member 30, the presence or absence of peeling of the coating layer 301 from the metal plate 300 was checked. The heat treatment conditions were 1000°C for 2 hours. After heat treatment, the metal member 30 was processed to obtain a cross section including a convex portion 30b and a concave portion 30c. The obtained cross section was observed with a digital microscope to check whether or not the coating layer 301 had peeled from the metal plate 300 or its oxide film. In Table 1, "×" indicates that peeling of the coating layer 301 was observed, and "○" indicates that peeling of the coating layer 301 was not observed.

[0067] <High Temperature Durability Test> In the high temperature durability test, the metal component 30 was heat-treated at a high temperature, and then visually inspected for abnormal oxidation, scale peeling, etc. The heat treatment temperature for the high temperature durability test was 1000°C for 500 hours. In Table 1, "×" indicates that abnormal oxidation, scale peeling, etc. were observed, and "○" indicates that no abnormal oxidation, scale peeling, etc. were observed.

[0068] Table 1 shows the overall evaluation based on the results of the peel resistance test and the high-temperature durability test. In Table 1, materials with particularly good durability are marked with "◎", materials with good durability are marked with "○", and materials that can withstand actual use but do not have good durability are marked with "△". Of the three evaluation levels described above, "◎" and "○" indicate that the material meets the standards for metal component 30.

[0069]

[0070] The metal member 30 may be manufactured, for example, by positioning the materials for the first portion 301a and the second portion 301b on a part of the first surface 300a of a metal plate 300 processed into a predetermined shape, and then firing it. Alternatively, the metal member 30 may be manufactured by firing the materials for the first portion 301a and the second portion 301b separately. The thicknesses of the first portion 301a and the second portion 301b may be the same or different. The compositions of the first portion 301a and the second portion 301b may be the same or different. Furthermore, a portion of the coating layer 301 may have a part in which the first portion 301a and the second portion 301b are laminated.

[0071] Furthermore, the metal member 30 does not have to have recesses 30c and recesses 300c. Also, the metal member 30 does not have to have protrusions 30b and protrusions 300b.

[0072] <Configuration of the Electrochemical Cell Apparatus> Next, the electrochemical cell apparatus according to this embodiment, using the electrochemical cell described above, will be explained with reference to Figures 3A to 3C. Figure 3A is a perspective view showing an example of the electrochemical cell apparatus according to the embodiment. Figure 3B is a cross-sectional view taken along the line X-X shown in Figure 3A. Figure 3C is a top view showing an example of the electrochemical cell apparatus according to the embodiment.

[0073] As shown in Figure 3A, the cell stacking device 10 comprises a cell stack 11 having a plurality of cells 1 arranged (stacked) in the thickness direction of the cell 1 (the Y-axis direction shown in Figure 1A), and a fixing member 12.

[0074] The fixing member 12 includes 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 includes a support body 15 and a gas tank 16. The support body 15 and the gas tank 16, which make up the support member 14, are made of metal and are electrically conductive.

[0075] As shown in Figure 3B, the support 15 has an insertion hole 15a into which the lower ends of the multiple cells 1 are inserted. The lower ends of the multiple cells 1 and the inner wall of the insertion hole 15a are joined together by a fixing member 13.

[0076] The gas tank 16 has an opening that supplies reaction gas to a plurality of cells 1 through an insertion hole 15a, and a groove 16a located around the opening. The outer end of the support 15 is joined to the gas tank 16 by a bonding material 21 that is filled into the groove 16a of the gas tank 16.

[0077] In the example shown in Figure 3A, fuel gas is stored in an internal space 22 (see Figure 3B) formed by the support member 14, which is the support 15, and the gas tank 16. A gas flow pipe 20 is connected to the gas tank 16. Fuel gas is supplied to the gas tank 16 through this gas flow pipe 20 and then supplied from the gas tank 16 to the flow path 2a (see Figure 1A) inside the cell 1. The fuel gas supplied to the gas tank 16 may be generated in a reformer 104 (see Figure 4), which will be described later.

[0078] Hydrogen-rich fuel gas can be produced by steam reforming of the raw fuel. When fuel gas is produced by steam reforming, the fuel gas contains water vapor.

[0079] The example shown in Figure 3A includes two rows of cell stacks 11, two support structures 15, and a gas tank 16. Each of the two rows of cell stacks 11 has multiple cells 1. Each cell stack 11 is fixed to each support structure 15. The gas tank 16 has two through holes on its upper surface. Each support structure 15 is placed in each through hole. The internal space 22 is formed by one gas tank 16 and two support structures 15. The cell stack device 10 may have only one cell stack 11, or it may have three or more cell stacks 11.

[0080] The shape of the insertion hole 15a may be, for example, an oval shape when viewed from above. The oval shape includes ellipses and rectangles with rounded corners. The length of the insertion hole 15a may be, for example, greater than the distance between the two end current collectors 17 located at both ends of the cell stack 11, in the direction of cell arrangement 1, i.e., the thickness direction (Y-axis direction: see Figure 1A). The width of the insertion hole 15a may be, for example, greater than the length of the cell 1 in the width direction (X-axis direction: see Figure 1A).

[0081] As shown in Figure 3B, the joint between the inner wall of the insertion hole 15a and the lower end of the cell 1 is filled with and solidified with fixing material 13. As a result, the inner wall of the insertion hole 15a is joined and fixed to the lower ends of the multiple cells 1, and the lower ends of the cells 1 are also joined and fixed 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.

[0082] The fixing material 13 and the bonding material 21 can be made of materials with low conductivity, such as glass. Specific materials for the fixing material 13 and the bonding material 21 may include amorphous glass, and in particular, crystallized glass may be used.

[0083] Examples of 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 system, SiO ２ Any of the following materials may be used, particularly SiO ２ -MgO-based materials may also be used.

[0084] Furthermore, as shown in Figure 3B, a conductive member 18 is interposed between adjacent cells 1 among the multiple cells 1. The conductive member 18 electrically connects one adjacent cell 1 and the other cell 1 in series. More specifically, the conductive member 18 connects the fuel electrode 5 of one cell 1 and the air electrode 8 of the other cell 1. The conductive member 18 may be integrated with the metal member 30 shown in Figure 1A. The metal member 30 may also serve as the conductive member 18. The conductive member 18 may be a separate member from the metal member 30. The conductive member 18 may be fixed to the air electrode 8 of the other cell 1 via a conductive adhesive and electrically joined.

[0085] Furthermore, as shown in Figure 3B, the end current collector 17 is electrically connected to the outermost cell 1 in the arrangement direction of the multiple cells 1. The end current collector 17 is connected to a conductive portion 19 that protrudes to the outside of the cell stack 11. The conductive portion 19 collects the electricity generated by the cell 1 and draws it out to the outside. Note that the end current collector 17 is not shown in Figure 3A.

[0086] Furthermore, as shown in Figure 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.

[0087] The positive terminal 19A is the positive terminal when the power generated by the cell stack 11 is output to the outside. The positive terminal 19A is electrically connected to the positive terminal end current collector 17 of the cell stack 11A. The negative terminal 19B is the negative terminal when the power generated by the cell stack 11 is output to the outside. The negative terminal 19B is electrically connected to the negative terminal end current collector 17 of the cell stack 11B.

[0088] The connection terminal 19C electrically connects the negative terminal end current collector 17 of the cell stack 11A to the positive terminal end current collector 17 of the cell stack 11B.

[0089] Although not shown in Figures 3A to 3C, the cell stack device 10 may also include a second gas tank at the top of the cell stack 11, which fixes the upper ends of multiple cells 1 and recovers the gas discharged from the flow path 2a (see Figure 1A) inside the cells 1.

[0090] <Module> Next, a module according to the embodiment of this disclosure using the cell stack device 10 described above will be explained with reference to Figure 4. Figure 4 is an external perspective view showing an example of a module according to the embodiment. Figure 4 shows the 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 housed inside has been taken out to the rear.

[0091] As shown in Figure 4, the module 100 comprises a cell stacking device 10 and a storage container 101 that houses the cell stacking device 10. A reformer 102 may also be positioned above the cell stacking device 10.

[0092] The reformer 102 reforms raw fuels such as natural gas and kerosene to produce fuel gas, which is then supplied to cell 1. The raw fuels are supplied to the reformer 102 through a raw fuel supply pipe 103. The reformer 102 may also include a vaporization section 102a for vaporizing water and a reforming section 102b. The reforming section 102b is equipped with a reforming catalyst (not shown) and reforms the raw fuels into fuel gas. Such a reformer 102 can perform steam reforming, which is a highly efficient reforming reaction.

[0093] The fuel gas generated in the reformer 102 is then supplied to the flow path 2a of the cell 1 (see Figure 1A) through the gas flow pipe 20, the gas tank 16, and the support member 14.

[0094] If the cell stack device 10 is equipped with a second gas tank on top of the cell stack 11, the reformer 102 may be located in a place other than above the cell stack device 10. The raw fuel supply pipe 103, gas flow pipe 20, etc., may be appropriately arranged according to the arrangement of the cell stack device 10 and the reformer 102.

[0095] Furthermore, in the module 100 with the above configuration, the temperature inside the module 100 during normal power generation is approximately 500°C to 1000°C due to the combustion of gas and the power generation of cell 1.

[0096] In such a module 100, as described above, the module 100 can be made more durable by housing a cell stack device 10 that has improved durability.

[0097] <Module Housing Device> Next, a fuel cell device, which is an example of a module housing device according to the present disclosure using the module 100 described above, will be explained with reference to Figure 5. Figure 5 is an exploded perspective view schematically showing an example of a module housing device according to the embodiment. The module housing device 110 according to this embodiment comprises an outer case 111, the module 100 shown in Figure 4, and auxiliary equipment (not shown). The auxiliary equipment operates the module 100. The outer case 111 houses the module 100 and the auxiliary equipment. Note that some components are omitted in Figure 5.

[0098] The outer casing 111 of the module housing device 110 shown in Figure 5 has support columns 112 and outer panels 113. Partition plates 114 divide the inside of the outer casing 111 into upper and lower sections. The space above the partition plates 114 inside the outer casing 111 is the module housing chamber 115 for housing the modules 100. The space below the partition plates 114 inside the outer casing 111 is the auxiliary equipment housing chamber 116 for housing auxiliary equipment configured to operate the modules 100. Note that in Figure 5, the auxiliary equipment housed in the auxiliary equipment housing chamber 116 is omitted from the illustration.

[0099] Furthermore, the partition plate 114 has an air circulation port 117 for allowing air from the auxiliary equipment storage room 116 to flow towards the module storage room 115. The outer panel 113 that constitutes the module storage room 115 has an exhaust port 118 for exhausting air from inside the module storage room 115.

[0100] In such a module housing device 110, as described above, by providing a module 100 with improved durability in the module housing chamber 115, the module housing device 110 can be made more durable.

[0101] [Other Embodiments] In the embodiments described above, a fuel cell cell, fuel cell stack device, fuel cell module, and fuel cell device were shown as examples of "electrochemical cell," "electrochemical cell device," "module," and "module housing device." Other examples include an electrolytic cell, electrolytic cell stack device, electrolytic module, and 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 carbon dioxide into carbon monoxide and oxygen, by supplying electricity. In the embodiments described above, an oxide ion conductor or a hydrogen ion conductor was shown as an example of the electrolyte material for the electrochemical cell, but a hydroxide ion conductor may also be used. Such electrolytic cells, electrolytic cell stack devices, electrolytic modules, and electrolytic devices can improve durability. Solid oxide type fuel cell cells and electrolytic cells are collectively referred to as solid oxide type electrochemical cells.

[0102] Although the present disclosure has been described in detail above, this disclosure is not limited to the embodiments described above, and various modifications and improvements are possible without departing from the gist of this disclosure.

[0103] In one embodiment, (1) the metal member comprises a metal plate having a recess and / or protrusion on a first surface, and a coating layer located on the first surface, wherein the coating layer has a first portion and a second portion having a higher porosity than the first portion.

[0104] (2) In the metal member described in (1) above, the second portion may be located at the corner of the recess and / or the corner of the protrusion.

[0105] (3) In the metal member of (1) or (2) above, the second portion may have a porosity of 20% or more and 50% or less.

[0106] (4) In any one of the metal members described in (1) to (3) above, the first portion may have a porosity of 18% or less.

[0107] (5) In any one of the metal members described in (1) to (4) above, the coating layer may be an oxide containing at least one of Zn, Mn, and Co.

[0108] In one embodiment, (6) the electrochemical cell device comprises an electrochemical cell having a first electrode, a second electrode containing metal particles, and a solid electrolyte layer located between the first electrode and the second electrode, and one of the metal members described in (1) to (5) above, wherein the coating layer covering the protrusion is bonded to the first electrode.

[0109] In one embodiment, module (7) comprises the electrochemical cell device described in (6) above and a storage container that houses the electrochemical cell device.

[0110] In one embodiment, the module housing device (8) comprises the module described in (7), an auxiliary device configured to operate the module, and an outer case housing the module and the auxiliary device.

[0111] The embodiments disclosed herein should be considered in all respects to be illustrative and not restrictive. Indeed, the embodiments described above can be embodied in a variety of forms. Furthermore, the embodiments described above may be omitted, replaced, or modified in various ways without departing from the scope and spirit of the appended claims.

[0112] 1 Cell 2 Support member 3 Element part 5 Fuel electrode 6 Solid electrolyte layer 8 Air electrode 10 Cell stack device 30 Metal member 100 Module 110 Module housing device 300 Metal plate 300a First surface 300b Convex part 300b1 Top part 300b2 First corner part 300b3 Outer part 300c Recessed part 300c1 Bottom part 300c2 Second corner part 300c3 Inner part 301 Coating layer 301a First part 301b Second part

Claims

1. A metal member comprising a metal plate having a recess and / or protrusion on a first surface, and a coating layer located on the first surface, wherein the coating layer has a first portion and a second portion having a higher porosity than the first portion.

2. The metal member according to claim 1, wherein the second portion is located at the corner of the recess and / or the corner of the protrusion.

3. The metal member according to claim 1 or 2, wherein the second portion has a porosity of 20% or more and 50% or less.

4. The first portion is a metal member according to any one of claims 1 to 3, having a porosity of 18% or less.

5. The metal member according to any one of claims 1 to 4, wherein the coating layer is an oxide containing at least one of Zn, Mn, and Co.

6. An electrochemical cell apparatus comprising an electrochemical cell having a first electrode, a second electrode containing metal particles, and a solid electrolyte layer located between the first electrode and the second electrode, and a metal member according to any one of claims 1 to 5, wherein the coating layer covering the protrusion is bonded to the first electrode.

7. A module comprising an electrochemical cell apparatus as described in claim 6, and a storage container housing the electrochemical cell apparatus.

8. A module housing device comprising: a module according to claim 7; an auxiliary device configured to operate the module; and an outer case housing the module and the auxiliary device.

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