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

Abstract

To provide an electrochemical cell, an electrochemical cell device, a module, and a module housing device capable of improving durability.SOLUTION: An electrochemical cell includes a metal plate, an element portion, a porous portion, a sealing material, and a first intermediate portion. The porous portion is located between the metal plate and the element portion. The sealing material is in contact with the metal plate. The first intermediate portion is located between the porous portion and the sealing material. The porous portion includes first particles having a first material. The sealing material includes a second material different from the first material. The first intermediate portion includes the first particles and a second material positioned between the first particles.SELECTED DRAWING: Figure 3

Description

[Technical field]

[0001] The present disclosure relates to electrochemical cells, electrochemical cell devices, modules and module containment devices. [Background technology]

[0002] In recent years, various fuel cell stack devices having a plurality of fuel cells have been proposed as next-generation energy sources. A fuel cell is a type of electrochemical cell that can obtain 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] JP 2020-72002 A Summary of the Invention [Problem to be solved by the invention]

[0004] Conventional fuel cell stack devices have room for improvement in terms of durability.

[0005] An object of one aspect of the embodiment is to provide an electrochemical cell, an electrochemical cell device, a module, and a module housing device that can improve durability. [Means for solving the problem]

[0006] An electrochemical cell according to one aspect of the embodiment includes a metal plate, an element portion, a porous portion, a sealing material, and a first intermediate portion. The porous portion is located between the metal plate and the element portion. The sealing material contacts the metal plate. The first intermediate portion is located between the porous portion and the sealing material. The porous portion includes first particles having a first material. The sealing material includes a second material different from the first material. The first intermediate portion includes the first particles and the second material located between the first particles.

[0007] An electrochemical cell device according to one aspect of the embodiment includes a cell stack including the electrochemical cell described above.

[0008] The module of the present disclosure includes the electrochemical cell device described above and a container for housing the electrochemical cell device.

[0009] The module housing device of the present disclosure includes the above-described module, an auxiliary device for operating the module, and an exterior case for housing the module and the auxiliary device. Effect of the Invention

[0010] According to one aspect of the embodiment, it is possible to provide an electrochemical cell, an electrochemical cell device, a module, and a module housing device that can improve durability. [Brief description of the drawings]

[0011] [Figure 1A] FIG. 1A is a cross-sectional view illustrating an example of an electrochemical cell according to an embodiment. [Figure 1B] FIG. 1B is a plan view of an example of an electrochemical cell according to an embodiment, as viewed from the air electrode side. [Diagram 2] FIG. 2 is a cross-sectional view showing another example of an electrochemical cell according to an embodiment. [Diagram 3] FIG. 3 is a cross-sectional view taken along line AA shown in FIG. 1B. [Figure 4A] FIG. 4A is a cross-sectional view showing another example of an electrochemical cell according to an embodiment. [Figure 4B] FIG. 4B is a cross-sectional view showing another example of an electrochemical cell according to an embodiment. [Figure 4C] FIG. 4C is a cross-sectional view showing another example of an electrochemical cell according to an embodiment. [Figure 4D] FIG. 4D is a cross-sectional view showing another example of an electrochemical cell according to an embodiment. [Figure 5A]FIG. 5A is a perspective view showing an example of an electrochemical cell device according to an embodiment. [Figure 5B] FIG. 5B is a cross-sectional view taken along line XX shown in FIG. 5A. [Figure 5C] FIG. 5C is a top view showing an example of an electrochemical cell device according to an embodiment. [Figure 6] FIG. 6 is an external perspective view illustrating an example of a module according to the embodiment. [Figure 7] FIG. 7 is an exploded perspective view illustrating an example of a module housing device according to an embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0013] In addition, it should be noted that the drawings are schematic, and that the dimensional relationships, ratios, etc. of the elements may differ from the reality. Furthermore, the drawings may include parts whose dimensional relationships, ratios, etc. differ from one another.

[0014] [Embodiment] <Electrochemical cell configuration> First, referring to Figures 1A and 1B, an electrochemical cell according to an embodiment will be described using an example of a solid oxide fuel cell. The electrochemical cell device may include a cell stack having a plurality of electrochemical cells. The electrochemical cell device having a plurality of electrochemical cells is simply referred to as a cell stack device.

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

[0016] For ease of understanding, Fig. 1A illustrates 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. Such a Cartesian coordinate system may also be illustrated in other drawings used in the following description. In addition, the same reference numerals are used to designate the same components as those of the electrochemical cell illustrated in Fig. 1A, and the description thereof will be omitted or simplified.

[0017] 1A, the cell 1 according to this embodiment includes an element portion 3, a porous portion 4, a first intermediate portion 41, a metal plate 32, and a flow path member 34. The element portion 3 includes a fuel electrode 5, a solid electrolyte layer 6, and a cathode 8.

[0018] 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%, 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.

[0019] A generally known material can be used for the fuel electrode 5. The fuel electrode 5 is made of a porous conductive ceramic, such as calcium oxide, magnesium oxide, or ZrO 2 and ceramics containing 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. Calcium oxide, magnesium oxide, or ZrO in which a rare earth element oxide is solid-dissolved may be used. 2 The anode 5 may be a CeO in which La, Nd or Yb is solid-dissolved. 2 may include:

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

[0021] The material of the solid electrolyte layer 6 is, for example, ZrO 2 The rare earth element oxide may contain, for example, one or more rare earth elements selected from Sc, Y, La, Nd, Sm, Gd, Dy, and Yb. The solid electrolyte layer 6 may be, for example, ZrO in which Yb, Sc, or Gd is solid-dissolved. 2 and La, Nd or Yb may be solid-dissolved in CeO. 2 BaZrO 3 BaCeO 3 may include:

[0022] The air electrode 8 is a second 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, in the range of 20% to 50%, particularly 30% to 50%. The open porosity of the air electrode 8 may also be referred to as the porosity of the air electrode 8.

[0023] There is no particular limitation on the material of the air electrode 8 as long as it is a material generally used for air electrodes. The material of the air electrode 8 is, for example, so-called ABO 3 Conductive ceramics such as perovskite oxides may also be used.

[0024] The material of the air electrode 8 may be, for example, a composite oxide in which Sr (strontium) and La (lanthanum) coexist at the A site. 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 Chief of Staff 3 In addition, x is 0 <x<1、yは0<y<1である。

[0025] The element section 3 may also have an intermediate layer (not shown) located between the solid electrolyte layer 6 and the air electrode 8. When the element section 3 has an intermediate layer, the intermediate layer functions as a diffusion suppression layer. When Sr (strontium) contained in the air electrode 8 diffuses into the solid electrolyte layer 6, SrZrO 3 The intermediate layer is made of SrZrO by making it difficult for Sr to diffuse. 3 This makes it difficult for

[0026] The material of the intermediate layer is not particularly limited as long as it is generally difficult for Sr to diffuse. The material of the intermediate layer is, for example, cerium oxide (CeO 2 ) As such a rare earth element, for example, Gd (gadolinium), Sm (samarium), etc. may be used.

[0027] The porous portion 4 is located between the first surface 321 of the metal plate 32 and the element portion 3. The porous portion 4 joins the element portion 3 and the metal plate 32, and fixes the element portion 3 to the metal plate 32.

[0028] The porous portion 4 is conductive. For example, the porous portion 4 is made of 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 The material may contain inorganic oxides such as CuO.

[0029] The porous portion 4 has gas permeability. The porous portion 4 may be located so as to cover an opening 32a, which will be described later.

[0030] The porous portion 4 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 layered on top of each other.

[0031] A sealing material 9 different from the solid electrolyte layer 6 is located on the side surfaces of the porous portion 4 and the element portion 3. The material of the sealing material 9 may be dense glass or ceramic. The material of the sealing material 9 may be, for example, amorphous glass or crystallized glass. Examples of crystallized glass include SiO 2 -CaO series, MgO-B 2 O 3 System, La 2 O 3 -B 2 O 3 -MgO, La 2 O 3 -B 2 O 3 -ZnO, SiO 2 -CaO-ZnO system, etc., may be used, particularly SiO 2 The sealing material 9 may be made of the same material as the solid electrolyte layer 6. For example, a -MgO-based material may be used. The sealing material 9 may have electrical insulation properties. The material of the sealing material 9 may be the same as the material of the solid electrolyte layer 6.

[0032] The first intermediate portion 41 is located between the porous portion 4 and the plug 9. The first intermediate portion 41 contains a material common to the adjacent porous portion 4 and / or the plug 9. This makes it difficult for the porous portion 4 and the plug 9 to peel off from each other, improving the durability of the cell 1. The detailed configuration of the first intermediate portion 41 and its vicinity will be described later.

[0033] 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).

[0034] The metal plate 32 has electrical conductivity. The metal plate 32 may be, for example, a metal member containing chromium. The metal plate 32 may be, for example, stainless steel such as ferritic stainless steel or austenitic stainless steel having 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 covering the surface. The metal plate 32 may not have a coating on the surface.

[0035] Moreover, the metal plate 32 has an opening 32a. The opening 32a is a through hole penetrating between the first surface 321 and the second surface 322. The fuel gas flowing through the flow passage 33 described later is supplied to the fuel electrode 5 of the element section 3 through the opening 32a. The diameter of the opening 32a may be, for example, 0.1 mm to 0.5 mm, particularly 0.3 mm to 0.4 mm. In the metal plate 32, the aperture ratio in the region where the opening 32a is formed in the plan view along the Y-axis direction may be, for example, 10% or more. The metal plate 32 may have a coating covering the wall surface of the opening 32a. The metal plate 32 may not have a coating on the wall surface of the opening 32a.

[0036] The metal plate 32 may be, for example, gas permeable. In such a case, the metal plate 32 does not need to have the opening 32a.

[0037] 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 joined by, for example, welding at a contact portion with the second surface 322. The flow path member 34 may be fixed and electrically joined to the metal plate 32 by a conductive seal material, brazing material, or the like. The space located between the metal plate 32 and the flow path member 34 is a flow path 33 through which the fuel gas flows. The fuel gas flowing through the flow path 33 permeates the metal plate 32 and is supplied to the fuel electrode 5. The metal plate 32 may have one or more protrusions protruding toward the flow path member 34.

[0038] 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 seal material, brazing material, or the like. The current collecting member 36 may be fixed and electrically joined to the air electrode 8 of the adjacent cell 1 via an adhesive material not shown. The space located between the current collecting member 36 and the flow path member 34 is a flow path 35 through which an oxygen-containing gas flows. The oxygen-containing gas flowing through the flow path 35 passes through the adhesive material from the slits of the current collecting member 36 and is supplied to the air electrode 8 of the adjacent cell 1.

[0039] The flow path member 34 and the current collecting member 36 are made of a dense metal or alloy. The flow path member 34 makes it difficult for the fuel gas flowing through the flow path 33 and the oxygen-containing gas flowing through the flow path 35 to leak. 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 33 may have a coating layer having reduction resistance, and the surface of the flow path member 34 facing the flow path 35 may have a coating layer having oxidation resistance. These coating layers may be conductive.

[0040] The shapes of the flow path member 34 and the current collecting member 36 are not limited to those shown in Fig. 1A. They may have any shape as long as they can electrically connect adjacent cells 1 and prevent leakage of the fuel gas and the oxygen-containing gas.

[0041] Fig. 2 is a cross-sectional view showing another example of an electrochemical cell according to an embodiment. As shown in Fig. 2, for example, a flow path member 34 may be integrated with a current collecting member 36 and have a first convex portion protruding toward an adjacent cell 1 along the Y-axis direction and a second convex portion protruding toward the opposite side to the first convex portion.

[0042] The cell 1 may further include a constraining layer. The constraining layer is located between the element section 3 and the metal plate 32. The constraining layer cooperates with the solid electrolyte layer 6 to prevent the element section 3 from warping or bending.

[0043] The material of the constraining layer exhibits a similar shrinkage rate during firing as the material of the solid electrolyte layer 6. The material of the constraining layer may be the same as the material of the solid electrolyte layer 6. The element unit 3 obtained by sandwiching the material of the fuel electrode 5 of the element unit 3 between the material of the solid electrolyte layer 6 and the material of the constraining layer and firing the resulting element unit 3 has little warping or deformation.

[0044] The constraining layer may or may not have gas permeability. When the constraining layer has gas barrier properties comparable to those of the solid electrolyte layer 6, the constraining layer may be partially disposed so as not to impede the inflow of fuel gas to the anode 5.

[0045] <Layout and structure of the first intermediate section and its vicinity> Next, the arrangement and structure of the first intermediate portion and its vicinity will be described with reference to Fig. 3. Fig. 3 is a cross-sectional view taken along line AA shown in Fig. 1B.

[0046] As shown in FIG. 3, the cell 1 includes a metal plate 32, an element portion 3, a porous portion 4, a sealing material 9, and a first intermediate portion 41.

[0047] The element unit 3 includes a solid electrolyte layer 6, a fuel electrode 5 as a first electrode, and a cathode 8 as a second electrode. The solid electrolyte layer 6 has a first surface 61 facing the metal plate 32 and a second surface 62 located on the opposite side to the first surface 61.

[0048] The fuel electrode 5 is located between the first surface 61 of the solid electrolyte layer 6 and the metal plate 32. The air electrode 8 is located to face the second surface 62. The fuel electrode 5 may have an active portion 5a located on the first surface 61 side, and a diffusion portion 5b located between the active portion 5a and the porous portion 4.

[0049] The porous portion 4 is located between the metal plate 32 and the element portion 3. The porous portion 4 includes first particles P1 having a first material m1. The first material m1 may be, for example, nickel and / or titania. The first material m1 may include at least one of metals such as Ni (nickel), Cu (copper), Co (cobalt), Fe (iron), and Ti (titanium), or alloys containing one or more of these metals, oxides such as Ti, Zr (zirconium), Al (aluminum), Si (silicon), Mg (magnesium), Ca (calcium), Sr (strontium), and Ba (barium), and oxides of rare earth elements such as Y (yttrium), Yb (ytterbium), Ce (cerium), and Gd (gadolinium). The first particles P1 may include at least one of metal particles and conductive oxide particles. The metal particles may be, for example, at least one of metals such as Ni (nickel), Cu (copper), Co (cobalt), Fe (iron) and Ti (titanium) or alloys containing one or more of these metals. The conductive oxide particles may be, for example, titania or ceria.

[0050] The porosity of the porous portion 4 may be greater than the porosity of the fuel electrode 5. This reduces the stress generated between the porous portion 4 and the fuel electrode 5, making it difficult for the element portion 3 to peel off from the metal plate 32. This improves the durability of the cell 1 according to this embodiment.

[0051] The sealing material 9 is in contact with the metal plate 32. The sealing material 9 is in contact with the solid electrolyte layer 6 and the fuel electrode 5 of the element unit 3. The sealing material 9 may be separated from the air electrode 8 or may be in contact with the air electrode 8. The sealing material 9 contains a second material m2 different from the first material m1. The second material m2 may be, for example, glass such as crystallized glass or amorphous glass, or a brazing material.

[0052] The first intermediate portion 41 is located between the porous portion 4 and the sealing material 9. The first intermediate portion 41 is in contact with the porous portion 4 and the sealing material 9. The first intermediate portion 41 includes first particles P1 and a second material m2 located between the first particles P1.

[0053] In this manner, the first intermediate portion 41 located between the porous portion 4 and the plugging material 9 has both the first particles P1 contained in the porous portion 4 and the second material m2 contained in the plugging material 9. As a result, cracks in the plugging material 9 and / or peeling of the plugging material 9 from the metal plate 32 caused by the difference in thermal expansion between the porous portion 4 and the plugging material 9 are less likely to occur, and the durability of the cell 1 according to this embodiment is improved.

[0054] Next, another example of the cell 1 according to the embodiment will be described with reference to Figures 4A to 4D. Figures 4A to 4D are cross-sectional views showing another example of the electrochemical cell according to the embodiment. Figures 4A to 4D correspond to the cross section AA shown in Figure 1B.

[0055] 4A, the encapsulant 9 may include second particles P2 having a second material m2. The second particles P2 are included in a portion 91 of the encapsulant 9 that contacts the first intermediate portion 41. Here, the portion 91 refers to a region where the distance d from the first intermediate portion 41 is equal to or less than 1 / 2L, where L is the length from the first intermediate portion 41 to the end of the encapsulant 9 located on the opposite side of the first intermediate portion 41. The encapsulant 9 may include the second particles P2 in a portion other than the portion 91.

[0056] The second particles P2 contained in the portion 91 may include particles having a particle diameter larger than the average particle diameter of the first particles P1 located in the first intermediate portion 41. This makes it even more difficult for the plug 9 to crack and / or peel off from the metal plate 32 due to the difference in thermal expansion between the porous portion 4 and the plug 9. This further improves the durability of the cell 1 according to this embodiment.

[0057] As shown in FIG. 4B, the portion 91 of the plug 9 in contact with the first intermediate portion 41 may include second particles P2 having the second material m2. The first intermediate portion 41 may include third particles P3 having the second material m2. The second particles P2 may include particles having a particle diameter larger than the average particle diameter of the third particles P3. This makes it even more difficult for the plug 9 to crack and / or peel off from the metal plate 32 due to the difference in thermal expansion between the porous portion 4 and the plug 9. Therefore, the durability of the cell 1 according to this embodiment is further improved.

[0058] The average particle size of the second particles P2 may be larger than the average particle size of the first particles P1 located in the first intermediate portion 41. This makes it even more difficult for the plug 9 to crack and / or peel off from the metal plate 32 due to the difference in thermal expansion between the porous portion 4 and the plug 9, and therefore the durability of the cell 1 according to this embodiment is further improved.

[0059] The average particle size of the second particles P2 may be larger than the average particle size of the third particles P3. This makes it more difficult for the plug 9 to crack and / or peel off from the metal plate 32 due to the difference in thermal expansion between the porous portion 4 and the plug 9, and therefore the durability of the cell 1 according to this embodiment is further improved.

[0060] 4C, in plan view from the air electrode 8 side, the contour 4a of the porous portion 4 may be located inside the contour 3a of the fuel electrode 5. This makes it even less likely that the sealing material 9 will crack and / or peel off from the metal plate 32 due to the difference in thermal expansion between the porous portion 4 and the sealing material 9 will occur, thereby further improving the durability of the cell 1 according to this embodiment.

[0061] Furthermore, in a plan view from the air electrode 8 side, the contour 41a of the first intermediate portion 41 may be located inside the contour 3a of the fuel electrode 5. This makes it even more unlikely that the sealing material 9 will crack and / or peel off from the metal plate 32 due to the difference in thermal expansion between the porous portion 4 and the sealing material 9 will occur, thereby further improving the durability of the cell 1 according to this embodiment.

[0062] 4D, the diffusion portion 5b may include a third material m3 different from the first material m1 and the second material m2. The third material m3 may be, for example, ZrO 2 and / or rare earth element oxide. The third material m3 may include at least one of the following metals not included in the first material m1 and the second material m2: metals such as Ni (nickel), Cu (copper), Co (cobalt), Fe (iron), and Ti (titanium), or alloys containing at least one of these metals, oxides of Ti, Zr (zirconium), Al (aluminum), Si (silicon), Mg (magnesium), Ca (calcium), Sr (strontium), and Ba (barium), and oxides of rare earth elements such as Y (yttrium), Yb (ytterbium), Ce (cerium), and Gd (gadolinium). The third material m3 may include at least one of the above materials included in the first material m1 and at least one of the above materials not included in the first material m1 and the second material m2.

[0063] The cell 1 may further include a second intermediate portion 5b1 located between the diffusion portion 5b and the plug 9. The second intermediate portion 5b1 may include fourth particles P4 having a third material m3, and a second material m2 located between the fourth particles P4. This makes it difficult for the plug 9 to crack and / or peel off from the metal plate 32 due to the difference in thermal expansion between the porous portion 4 and the plug 9, thereby improving the durability of the cell 1 according to this embodiment.

[0064] Here, the arrangement of the first material m1 to the third material m3, the shapes of the first intermediate portion 41 and the second intermediate portion 5b1, and the particle sizes and average particle sizes of the first particle P1 to the fourth particle P4 are obtained as follows. For example, a polished cross section of the cell 1 including the porous portion 4, the fuel electrode 5, and the sealing material 9 can be measured by image analysis of a reflected electron image using a SEM (scanning electron microscope) or a TEM (transmission electron microscope) and an EDX (energy dispersive X-ray analyzer). Specifically, the first material m1 to the third material m3 are identified in the reflected electron image of the cross section by the structural morphology and elemental analysis. By checking the arrangement or distribution of the identified first material m1 to the third material m3, the presence or absence and shape of the first intermediate portion 41 including both the first material m1 and the second material m2 and the second intermediate portion 5b1 including both the third material m3 and the second material m2 can be confirmed. In addition, in the backscattered electron image of the cross section, the first particle P1 to the fourth particle P4 can be identified by the arrangement or distribution of the first material m1 to the third material m3 and elemental analysis, and the particle sizes (circle equivalent diameters) and average particle size of the first particle P1 to the fourth particle P4 can be calculated by image analysis.

[0065] The first particles P1 contained in the porous portion 4 may have an average particle size (equivalent circle diameter) of 0.1 μm to 3.0 μm. The second particles P2 may have an average particle size (equivalent circle diameter) of 0.1 μm to 30 μm. The third particles P3 may have an average particle size (equivalent circle diameter) of 0.1 μm to 3.0 μm. The fourth particles P4 may have an average particle size (equivalent circle diameter) of 0.1 μm to 3.0 μm.

[0066] <Configuration of electrochemical cell device> Next, an electrochemical cell device according to the present embodiment using the above-mentioned cell 1 will be described with reference to Figs. 5A to 5C. Fig. 5A is a perspective view showing an example of the electrochemical cell device according to the embodiment. Fig. 5B is a cross-sectional view taken along line XX shown in Fig. 5A. Fig. 5C is a top view showing an example of the electrochemical cell device according to the embodiment.

[0067] As shown in FIG. 5A, the cell stack device 10 includes 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 FIG. 1A), and a fixing member 12.

[0068] The fixing member 12 has a fixing material 13 and a support member 14. The support member 14 supports the cell 1. The fixing material 13 fixes the cell 1 to the support member 14. The support member 14 also has a support body 15 and a gas tank 16. The support body 15 and the gas tank 16, which are the support member 14, are made of metal and are conductive.

[0069] 5B, the support 15 has insertion holes 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 holes 15a are joined with a fixing material 13.

[0070] The gas tank 16 has an opening for supplying a reaction gas to the cells 1 through the insertion holes 15a, and a groove 16a located around the opening. The outer peripheral edge of the support 15 is joined to the gas tank 16 by a joining material 21 filled in the groove 16a of the gas tank 16.

[0071] In the example shown in FIG. 5A, fuel gas is stored in an internal space 22 formed by a support body 15, which is the support member 14, and a gas tank 16. A gas circulation pipe 20 is connected to the gas tank 16. The fuel gas is supplied to the gas tank 16 through this gas circulation pipe 20, and is supplied from the gas tank 16 to a flow path 33 (see FIG. 1A) inside the cell 1. The fuel gas supplied to the gas tank 16 is generated in a reformer 102 (see FIG. 6), which will be described later. The internal space 22 may be rephrased as a space of a reducing atmosphere containing the fuel gas.

[0072] The hydrogen-rich fuel gas can be produced by steam reforming of the raw fuel, etc. When the fuel gas is produced by steam reforming, the fuel gas contains water vapor.

[0073] The example shown in FIG. 5A 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 1. Each cell stack 11 is fixed to each of the supports 15. The gas tank 16 has two through holes on the upper surface. Each of the supports 15 is disposed in each of the through holes. An internal space 22 is formed by one gas tank 16 and two supports 15.

[0074] The shape of the insertion hole 15a is, for example, an oval shape when viewed from above. For example, the length of the insertion hole 15a in the arrangement direction of the cells 1, i.e., in 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. The width of the insertion hole 15a is, for example, greater than the length of the cell 1 in the width direction (X-axis direction shown in FIG. 1A).

[0075] 5B, the joints between the inner walls of the insertion holes 15a and the lower ends of the cells 1 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 cells 1, respectively, and also bonds and fixes the lower ends of the cells 1 to each other. The gas flow paths 2a of each cell 1 communicate with the internal space 22 of the support member 14 at their lower ends.

[0076] A material having low electrical 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.

[0077] Examples of the crystallized glass include SiO 2 -CaO series, MgO-B 2 O 3 System, La 2 O 3 -B 2 O 3 -MgO, La 2 O 3 -B 2 O 3 -ZnO, SiO 2 -CaO-ZnO system, etc., may be used, particularly SiO2 -MgO-based materials may also be used.

[0078] 5B, 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 to the other adjacent cell 1 in series. More specifically, the conductive member 18 connects the fuel electrode 5 of one cell 1 to the air electrode 8 of the other cell 1. The conductive member 18 may be the flow path member 34 or the current collecting member 36 shown in FIG. 1A, or may be a member different from the flow path member 34 and the current collecting member 36.

[0079] As shown in Fig. 5B, an end current collecting member 17 is electrically connected to the cell 1 located at the outermost position in the arrangement direction of the multiple cells 1. The end current collecting member 17 is connected to a conductive part 19 protruding outward from the cell stack 11. The conductive part 19 collects electricity generated by power generation in the cells 1 and draws it outward. Note that the end current collecting member 17 is not shown in Fig. 5A.

[0080] 5C, the cell stack device 10 has two cell stacks 11A and 11B connected in series and functions as one battery. Therefore, the conductive portion 19 of the cell stack device 10 is divided into a positive terminal 19A, a negative terminal 19B, and a connection terminal 19C.

[0081] The positive electrode terminal 19A is a positive electrode when the electric power generated by the cell stack 11 is output to the outside, and is electrically connected to the end current collecting member 17 on the positive electrode side of the cell stack 11A. The negative electrode terminal 19B is a negative electrode when the electric power generated by the cell stack 11 is output to the outside, and is electrically connected to the end current collecting member 17 on the negative electrode side of the cell stack 11B.

[0082] The connection terminal 19C electrically connects the end current collecting member 17 on the negative electrode side in the cell stack 11A and the end current collecting member 17 on the positive electrode side in the cell stack 11B.

[0083] <module> Next, a module according to this embodiment using the above-mentioned cell stack device 10 will be described with reference to Fig. 6. Fig. 6 is an external perspective view showing the module according to this embodiment. Fig. 6 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 removed to the rear.

[0084] 6, the module 100 includes a storage container 101 and a cell stack device 10 housed in the storage container 101. In addition, above the cell stack device 10, a reformer 102 is disposed.

[0085] The reformer 102 reforms raw fuel such as natural gas or kerosene to generate fuel gas and supplies it to the cell 1. The raw fuel is supplied to the reformer 102 through a raw fuel supply pipe 103. 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, which is a highly efficient reforming reaction.

[0086] The fuel gas generated in the reformer 102 is supplied to the flow path 33 of the cell 1 (see FIG. 1A) through the gas distribution pipe 20, the gas tank 16, and the support member 14.

[0087] Furthermore, in the module 100 having the above-mentioned configuration, the temperature inside the module 100 during normal power generation becomes approximately 500°C to 1000°C as the gas is combusted and the cells 1 generate power.

[0088] In such a module 100, as described above, by accommodating the cell stack device 10 including a plurality of highly durable cells 1, the module 100 can be made highly durable.

[0089] <Module storage device> Fig. 7 is an exploded perspective view showing an example of a module housing device according to an embodiment. A module housing device 110 according to this embodiment includes an exterior case 111, the module 100 shown in Fig. 6, and auxiliary equipment (not shown). The auxiliary equipment operates the module 100. The module 100 and the auxiliary equipment are housed in the exterior case 111. Note that some components are omitted in Fig. 7.

[0090] An exterior case 111 of a module accommodating device 110 shown in Fig. 7 has support columns 112 and an exterior plate 113. A partition plate 114 divides the interior of the exterior case 111 into upper and lower sections. The space above the partition plate 114 in the exterior case 111 is a module accommodating chamber 115 that accommodates the module 100, and the space below the partition plate 114 in the exterior case 111 is an auxiliary equipment accommodating chamber 116 that accommodates auxiliary equipment that operates the module 100. Note that in Fig. 7, the auxiliary equipment accommodated in the auxiliary equipment accommodating chamber 116 is omitted.

[0091] In addition, the partition plate 114 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 constituting 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 housing device 110, as described above, the highly durable module 100 is provided in the module housing chamber 115, and thus the module housing device 110 can have high durability.

[0093] [Other embodiments] In the above-mentioned embodiments, a fuel cell, a fuel cell stack device, a fuel cell module, and a fuel cell device are shown as examples of an "electrochemical cell", an "electrochemical cell device", a "module", and a "module housing device", but 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 decomposes carbon dioxide into carbon monoxide and oxygen, when supplied with electric power. In addition, in each of the above-mentioned embodiments, an oxide ion conductor or a hydrogen ion conductor is shown as an example of an electrolyte material of the electrochemical cell, but a hydroxide ion conductor may also be used. According to such an electrolysis cell, an electrolysis cell stack device, an electrolysis module, and an electrolysis device, it is possible to improve the electrolysis performance and the durability.

[0094] 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 without departing from the gist of the present disclosure.

[0095] In one embodiment, (1) an electrochemical cell includes a metal plate and An element portion; a porous portion located between the metal plate and the element portion; A sealing material in contact with the metal plate; a first intermediate portion located between the porous portion and the sealing material; Equipped with the porous portion includes first particles having a first material; the encapsulant includes a second material different from the first material; The first intermediate portion includes the first particles and a second material located between the first particles.

[0096] (2) In the electrochemical cell according to (1), the sealing material in contact with the first intermediate portion includes second particles having the second material, The second particles may include particles having a particle size larger than an average particle size of the first particles located in the first intermediate portion.

[0097] (3) In the electrochemical cell according to (1) or (2), the sealing material in contact with the first intermediate portion includes second particles having the second material, the first intermediate portion includes third particles having the second material; The second particles may include particles having a particle size larger than an average particle size of the third particles.

[0098] (4) In the electrochemical cell according to any one of (1) to (3), the sealing material in contact with the first intermediate portion includes second particles having the second material, The second particles may have an average particle size greater than an average particle size of the first particles located in the first intermediate portion.

[0099] (5) In the electrochemical cell according to any one of (1) to (4), the sealing material in contact with the first intermediate portion includes second particles having the second material, the first intermediate portion includes third particles having the second material; The second particles may have an average particle size greater than the average particle size of the third particles.

[0100] (6) In the electrochemical cell according to any one of (1) to (5) above, the element portion comprises: a solid electrolyte layer having a first surface facing the first intermediate portion and a second surface located on the opposite side to the first surface; a first electrode located between the first surface and the porous portion; a second electrode facing the second surface; Equipped with When viewed from above on the second electrode side, the contour of the porous portion may be located inside the contour of the first electrode.

[0101] (7) In the electrochemical cell of (6) above, when viewed in a plan view from the second electrode side, a contour of the first intermediate portion may be located inside a contour of the first electrode.

[0102] (8) In the electrochemical cell of any one of the above (1) to (7), the first particles may include metal particles and / or conductive oxide particles.

[0103] (9) In the electrochemical cell of (6) or (7) above, the porosity of the porous portion may be greater than the porosity of the first electrode.

[0104] (10) In the electrochemical cell according to (6) or (7), the first electrode has an active portion located on the first surface side, and a diffusion portion located on the porous portion side and including a third material different from the first material and the second material; The semiconductor device may further include a second intermediate portion located between the diffusion portion and the encapsulant, the second intermediate portion including fourth particles having the third material, and a second material located between the fourth particles.

[0105] In one embodiment, (11) an electrochemical cell device has a cell stack including any one of the electrochemical cells (1) to (10) above.

[0106] In one embodiment, the module (12) comprises the electrochemical cell device (11) described above, and a container for housing the electrochemical cell device.

[0107] In one embodiment, the module housing device (13) includes the module (12) and Auxiliary equipment for operating the module; and an exterior case that houses the module and the auxiliary equipment.

[0108] The disclosed embodiments should be considered to be illustrative and not restrictive in all respects. Indeed, the above-described embodiments may be embodied in various forms. Furthermore, the above-described embodiments may be omitted, substituted, or modified in various forms without departing from the scope and spirit of the appended claims. [Explanation of symbols]

[0109] 1 cell 3. Element section 4 Porous part 5 Fuel electrode 6 Solid electrolyte layer 8 Air electrode 9. Encapsulating materials 10 Cell stack device 32 Metal plate 41 First Intermediate Section 100 Modules 110 Module storage device

Claims

1. A metal plate; An element portion; a porous portion located between the metal plate and the element portion; A sealing material in contact with the metal plate; a first intermediate portion located between the porous portion and the sealing material; Equipped with the porous portion includes first particles having a first material; the encapsulant includes a second material different from the first material; The first intermediate portion includes the first particles and a second material located between the first particles. Electrochemical cell.

2. the sealing material in contact with the first intermediate portion includes second particles having the second material; The second particles include particles having a particle size larger than the average particle size of the first particles located in the first intermediate portion.

10. The electrochemical cell of claim 1.

3. the sealing material in contact with the first intermediate portion includes second particles having the second material; the first intermediate portion includes third particles having the second material; The second particles include particles having a particle size larger than an average particle size of the third particles.

10. The electrochemical cell of claim 1.

4. the sealing material in contact with the first intermediate portion includes second particles having the second material; The average particle size of the second particles is larger than the average particle size of the first particles located in the first intermediate portion.

10. The electrochemical cell of claim 1.

5. the sealing material in contact with the first intermediate portion includes second particles having the second material; the first intermediate portion includes third particles having the second material; The average particle size of the second particles is larger than the average particle size of the third particles.

10. The electrochemical cell of claim 1.

6. The element portion is a solid electrolyte layer having a first surface facing the first intermediate portion and a second surface located on the opposite side to the first surface; a first electrode located between the first surface and the porous portion; a second electrode facing the second surface; Equipped with When viewed from above from the second electrode side, the contour of the porous portion is located inside the contour of the first electrode.

6. The electrochemical cell of claim 5.

7. When viewed from above from the second electrode side, a contour of the first intermediate portion is located inside a contour of the first electrode.

7. The electrochemical cell of claim 6.

8. The first particles include metal particles and / or conductive oxide particles.

10. The electrochemical cell of claim 1.

9. The porosity of the porous portion is greater than the porosity of the first electrode.

7. The electrochemical cell of claim 6.

10. the first electrode has an active portion located on the first surface side and a diffusion portion located on the porous portion side and including a third material different from the first material and the second material; a second intermediate portion located between the diffusion portion and the encapsulant, the second intermediate portion including fourth particles having the third material and a second material located between the fourth particles.

7. The electrochemical cell of claim 6.

11. A cell stack comprising an electrochemical cell according to any one of claims 1 to 10. Electrochemical cell setup.

12. The electrochemical cell device according to claim 11 ; A container for housing the electrochemical cell device; A module comprising:

13. A module according to claim 12; 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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