Electrochemical cell, electrochemical cell device, module, and module storage device

Abstract

This electrochemical cell is provided with a solid electrolyte layer, a first electrode, and a second electrode. The solid electrolyte layer has a first surface and a second surface that is positioned on the opposite side of the first surface. The first electrode contains metal particles and faces the first surface. The second electrode contains inorganic oxide particles and faces the second surface. The solid electrolyte layer has a first portion in which the distance from the first surface is smaller than the distance from the second surface, and a second portion in which the distance from the first surface is larger than the distance of the first portion. In a cross section along the thickness direction of the solid electrolyte layer, when the number of pores located in the first portion per unit area is defined as P1 and the number of pores located in the second portion per unit area is defined as P2, P2 is greater than P1.

Description

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

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

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

[0003] JP 2022-119219 A International Publication No. 2013 / 031961 JP 2015-46365 A

[0004] An electrochemical cell according to one aspect of the embodiment includes a solid electrolyte layer, a first electrode, and a second electrode. The solid electrolyte layer has a first surface and a second surface opposite the first surface. The first electrode includes metal particles and faces the first surface. The second electrode includes inorganic oxide particles and faces the second surface. The solid electrolyte layer has a first region that is closer to the first surface than the second surface, and a second region that is closer to the first surface than the first region. In a cross section of the solid electrolyte layer taken along the thickness direction, when the number of pores per unit area located in the first region is P1 and the number of pores per unit area located in the second region is P2, P2 is greater than P1.

[0005] The electrochemical cell device of the present disclosure also includes a cell stack including the electrochemical cell described above.

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

[0007] The module housing device of the present disclosure also includes the module described above, an accessory configured to operate the module, and an exterior case housing the module and the accessory.

[0008] FIG. 1A is a cross-sectional view showing an example of an electrochemical cell according to the first embodiment. FIG. 1B is a side view of an example of an electrochemical cell according to the first embodiment, viewed from the air electrode side. FIG. 1C is a side view of an example of an electrochemical cell according to the first embodiment, viewed from the interconnector side. FIG. 2 is a cross-sectional view showing an enlarged region R1 shown in FIG. 1A. FIG. 3A is a perspective view showing an example of an electrochemical cell device according to the first 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 an electrochemical cell device according to the first embodiment. FIG. 4 is an external perspective view showing an example of a module according to the first embodiment. FIG. 5 is an exploded perspective view schematically showing an example of a module housing device according to the first embodiment. FIG. 6A is a cross-sectional view showing an example of an electrochemical cell device according to the second embodiment. FIG. 6B is a cross-sectional view showing an electrochemical cell according to the second embodiment. FIG. 7 is a cross-sectional view showing an enlarged region R2 shown in FIG. 6B. FIG. 8A is a perspective view showing an example of an electrochemical cell according to a third embodiment. FIG. 8B is a partial cross-sectional view of the electrochemical cell shown in FIG. 8A. Fig. 9 is an enlarged cross-sectional view of region R3 shown in Fig. 8B. Fig. 10A is a cross-sectional view showing an example of an electrochemical cell according to the fourth embodiment. Fig. 10B is a cross-sectional view showing another example of an electrochemical cell according to the fourth embodiment. Fig. 10C is a cross-sectional view showing another example of an electrochemical cell according to the fourth embodiment. Fig. 11 is an enlarged cross-sectional view of region R4 shown in Fig. 10A. Fig. 12 is a diagram showing the evaluation results of Samples No. 1 to 6.

[0009] The above-described fuel cell stack device has room for improvement in terms of power generation performance.

[0010] Therefore, there is a need to provide an electrochemical cell, an electrochemical cell device, a module, and a module housing device that can improve cell performance.

[0011] 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. However, the disclosure is not limited to the embodiments described below.

[0012] It should also be noted that the drawings are schematic and that the dimensional relationships and ratios of elements may differ from reality. Furthermore, the drawings may contain parts whose dimensional relationships and ratios differ from one another.

[0013] 1A to 1C, an electrochemical cell according to a first embodiment will be described using an example of a solid oxide fuel cell. The electrochemical cell device may include a cell stack having a plurality of electrochemical cells. An electrochemical cell device having a plurality of electrochemical cells will be simply referred to as a cell stack device.

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

[0015] 1A to 1C, the cell 1 is a hollow, flat, elongated plate. As shown in Fig. 1B, the shape of the entire cell 1 as viewed from the side may be, for example, a rectangle with a side length in the length direction L of 5 cm to 50 cm and a width direction W perpendicular to the length direction L of 1 cm to 10 cm. The thickness of the entire cell 1 in the thickness direction T may be, for example, 1 mm to 5 mm.

[0016] 1A, the cell 1 includes a conductive support substrate 2, an element portion 3, and an interconnector 4. The support substrate 2 may be columnar, having a pair of opposing flat surfaces, that is, surfaces n1 and n2, and a pair of arc-shaped side surfaces m connecting the surfaces n1 and n2.

[0017] The element section 3 is located on the surface n1 of the support substrate 2. The element section 3 includes a fuel electrode 5, a solid electrolyte layer 6, and a cathode 8.

[0018] 1B, the air electrode 8 does not extend to the lower end of the cell 1. At the lower end of the cell 1, only the solid electrolyte layer 6 is exposed on the surface of face n1. As shown in FIG. 1C, the interconnector 4 may extend to the lower end of the cell 1. At the lower end of the cell 1, the interconnector 4 and the solid electrolyte layer 6 are exposed on the surface. As shown in FIG. 1A, the solid electrolyte layer 6 is exposed on the surface of a pair of arc-shaped side faces m of the cell 1. The interconnector 4 does not have to extend to the lower end of the cell 1.

[0019] Each of the components constituting the cell 1 will be described below.

[0020] The support substrate 2 has gas flow channels 2a therein through which gas flows. The example of the support substrate 2 shown in FIG. 1A has six gas flow channels 2a. The support substrate 2 has gas permeability, and allows the fuel gas flowing in the gas flow channels 2a to permeate to the anode 5. The support substrate 2 may be conductive. The conductive support substrate 2 collects electricity generated in the element section 3 to the interconnector 4.

[0021] The material of the support substrate 2 includes, for example, an iron-group metal component and an inorganic oxide. The iron-group metal component may be, for example, Ni (nickel) and / or NiO. The inorganic oxide may be, for example, a specific rare earth element oxide. The rare earth element oxide may include, for example, one or more rare earth elements selected from Sc (scandium), Y (yttrium), La (lanthanum), Nd (neodymium), Sm (samarium), Gd (gadolinium), Dy (dysprosium), and Yb (ytterbium).

[0022] The anode 5 is a first electrode that comes into contact with a reducing fuel gas. The anode 5 has gas permeability. The open porosity of the anode 5 may be, for example, 30% to 50%, and particularly 35% to 45%. The open porosity of the anode 5 may also be referred to as the porosity or void ratio of the anode 5.

[0023] The fuel electrode 5 includes metal particles. The metal particles may be, for example, Ni. The fuel electrode 5 is made of a porous conductive ceramic, for example, calcium oxide, magnesium oxide, or ZrO in which a rare earth element oxide is solid-solved. 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, Ce, Nd, Sm, Gd, Dy, and Yb. Calcium oxide, magnesium oxide, or ZrO in which a rare earth element oxide is solid-solved. ２ The stabilized zirconia may contain partially stabilized zirconia. The anode 5 is a CeO in which Y, La, Nd, Gd, Sm, or Yb is solid-solved. ２ may include:

[0024] The solid electrolyte layer 6 is a solid oxide electrolyte. The solid electrolyte layer 6 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, making it difficult for leakage of fuel gas and oxygen-containing gas to occur.

[0025] The material of the solid electrolyte layer 6 is, for example, ZrO in which 3 mol % to 15 mol % of rare earth element oxide is dissolved. ２ The rare earth element oxide may contain, for example, one or more rare earth elements selected from Sc, Y, La, Ce, Nd, Sm, Gd, Dy, and Yb. The solid electrolyte layer 6 may be, for example, ZrO in which Y, Yb, Sc, or Gd is solid-solved. ２ and BaZrO in which Sc, Y or Yb is solid-solved. ３ The solid electrolyte layer 6 will be described in detail later.

[0026] The air electrode 8 is a second electrode that comes into contact with an oxygen-containing gas. The air electrode 8 has gas permeability. The open porosity of the air electrode 8 may be, for example, 20% to 50%, and 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.

[0027] The air electrode 8 contains inorganic oxide particles. There are no particular limitations 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 The material may be a conductive ceramic such as a perovskite-type oxide.

[0028] 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 Here, x is 0<x<1, and y is 0<y<1.

[0029] Furthermore, the interconnector 4 is dense and makes it difficult for leakage of the fuel gas flowing through the gas flow passage 2a located inside the support substrate 2 and the oxygen-containing gas flowing outside the support substrate 2 to occur. The interconnector 4 may have a relative density of 93% or more, particularly 95% or more.

[0030] The material of the interconnector 4 is a lanthanum chromite-based perovskite oxide (LaCrO ３ -based oxides), lanthanum strontium titanium-based perovskite-type oxides (LaSrTiO ３ These materials are electrically conductive and are not easily reduced or oxidized even when in contact with fuel gases such as hydrogen-containing gases and oxygen-containing gases such as air.

[0031] The element unit 3 may further include an intermediate layer 7 located between the solid electrolyte layer 6 and the air electrode 8. When the element unit 3 includes the intermediate layer 7, the intermediate layer 7 makes it difficult for a specific element to diffuse. For example, when a specific element such as Sr (strontium) contained in the air electrode 8 diffuses into the solid electrolyte layer 6, the solid electrolyte layer 6 becomes a layer of SrZrO ３ The intermediate layer 7 is formed as a resistive layer by making it difficult for specific elements such as Sr to diffuse. ３ This makes it difficult for compounds such as

[0032] The material of the intermediate layer 7 is not particularly limited as long as it generally prevents diffusion of elements between the air electrode 8 and the solid electrolyte layer 6. The material of the intermediate layer 7 is, for example, cerium oxide (CeO) in which rare earth elements other than Ce (cerium) are dissolved. ２ ) may be included. As such a rare earth element, Gd (gadolinium), Sm (samarium), etc. may be used.

[0033] <Details of Electrochemical Cell> Next, details of the electrochemical cell according to this embodiment will be further described with reference to Fig. 2. Fig. 2 is an enlarged cross-sectional view of region R1 shown in Fig. 1A.

[0034] The electrochemical cell according to this embodiment has an element section 3. The element section 3 has a solid electrolyte layer 6, a fuel electrode 5, and a cathode 8.

[0035] The solid electrolyte layer 6 has a first surface 601 and a second surface 602 located on the opposite side of the first surface 601. The solid electrolyte layer 6 may include an oxide containing Zr.

[0036] The fuel electrode 5 contains metal particles and is a first electrode facing the first surface 601 .

[0037] The cathode 8 contains inorganic oxide particles. The cathode 8 is a second electrode facing the second surface 602. The cathode 8 may contain La and / or Sr.

[0038] The solid electrolyte layer 6 has a first portion 61 and a second portion 62. The first portion 61 is a portion whose distance to the first surface 601 is smaller than the distance to the second surface 602. The first portion 61 may include the first surface 601. The porosity of the first portion 61 may be 5% or less.

[0039] The second portion 62 is a portion that is farther from the first surface 601 than the first portion 61. The second portion 62 may include the second surface 602. The porosity of the second portion 62 may be 1% or more and 9% or less.

[0040] 2 , in a cross section of the solid electrolyte layer 6 taken along the thickness direction, when the number per unit area of ​​the first pores 61a, which are the pores 6a located in the first portion 61, is P1 and the number per unit area of ​​the second pores 62a, which are the pores 6a located in the second portion 62, is P2, P2 is greater than P1.

[0041] For example, the second region 62, which is closer to the air electrode 8 than the first region 61, has a larger number of pores 6a per unit area than the first region 61. As a result, in the second region 62, the second pores 62a tend to prevent the diffusion of specific elements contained in the air electrode 8, such as La and / or Sr, into the solid electrolyte layer 6. Therefore, even if a specific element diffuses into the solid electrolyte layer 6, a high-resistance phase, which is a reaction product between the specific element and an oxide contained in the solid electrolyte layer 6, is less likely to form inside the solid electrolyte layer 6. Therefore, the solid electrolyte layer 6 as a whole maintains electrical conductivity.

[0042] Furthermore, the first region 61, which is farther from the air electrode 8 than the second region 62, has fewer pores 6a per unit area than the second region 62. This gives the first region 61 a higher gas barrier property than the second region 62, ensuring the gas barrier property of the solid electrolyte layer 6 as a whole.

[0043] Thus, the solid electrolyte layer 6 has a first region 61 and a second region 62 in which the numbers of pores 6a per unit area are different in a cross section intersecting the first surface 601 and the second surface 602, i.e., in a cross section along the thickness direction. This makes it possible to achieve both the electrical conductivity and gas barrier properties required of the solid electrolyte layer 6. Therefore, an electrochemical cell including such a solid electrolyte layer 6 has improved cell performance.

[0044] The pores 6a located in the solid electrolyte layer 6 may have an average pore diameter of 1.3 μm or less, particularly 1 μm or less, which makes it easier to achieve both the desired electrical conductivity and gas barrier properties required for the solid electrolyte layer 6.

[0045] Furthermore, the average pore diameter of the second pores 62a, which are the pores 6a located in the second region 62, may be smaller than the average pore diameter of the first pores 61a, which are the pores 6a located in the first region 61. This makes it easier to ensure a conductive path in the second region 62.

[0046] The element unit 3 may further include an intermediate layer 7 located between the second surface 602 of the solid electrolyte layer 6 and the air electrode 8. The intermediate layer 7 may contain Ce. In this case, for example, in the second portion 62, the second pores 62a tend to prevent the diffusion of Ce contained in the intermediate layer 7 into the interior. Therefore, even if Ce is diffused into the solid electrolyte layer 6, a high-resistance phase, which is a reaction product between the Ce and the oxide contained in the solid electrolyte layer 6, is less likely to be formed inside the solid electrolyte layer 6. Therefore, the solid electrolyte layer 6 as a whole is able to maintain electrical conductivity.

[0047] Here, the number of pores 6 a per unit area located in the first portion 61 and the second portion 62 of the solid electrolyte layer 6 can be confirmed, for example, by observing a cross section of the solid electrolyte layer 6 with a scanning electron microscope (SEM). Specifically, the cross sections of the first portion 61 and the second portion 62 are observed with an SEM, the pores 6 a contained in each portion are identified and counted, and the number of pores 6 a per unit area in each portion is calculated.

[0048] The porosity of the first portion 61 and the second portion 62 can be confirmed, for example, by image processing an SEM image of a cross section of the solid electrolyte layer 6. Specifically, the cross sections of the first portion 61 and the second portion 62 are photographed, the pores 6 a contained in each portion of the obtained SEM image are identified, and then the area fraction of the pores 6 a in each portion is calculated by image processing.

[0049] The average pore diameters of the first pores 61a located in the first region 61 and the second pores 62a located in the second region 62 can be confirmed, for example, by image processing of SEM images of a cross section of the solid electrolyte layer 6. Specifically, cross sections of the first region 61 and the second region 62 are photographed, and the first pores 61a located in the first region 61 and the second pores 62a located in the second region 62 are identified in the obtained SEM image. Then, the circle-equivalent diameters of each pore are calculated from the area of ​​each pore by image processing. The calculated circle-equivalent diameters are used to calculate the average circle-equivalent diameters of the first pores 61a and the second pores 62a, which is then used as the average pore diameter. The average pore diameter of the pores 6a located in the solid electrolyte layer 6 can be calculated as the average of the average pore diameters of the first pores 61a and the second pores 62a.

[0050] <Configuration of Electrochemical Cell Device> Next, an electrochemical cell device according to this embodiment using the above-described cell 1 will be described with reference to FIGS. 3A to 3C. FIG. 3A is a perspective view showing an example of an electrochemical cell device according to the first 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 an electrochemical cell device according to the first embodiment.

[0051] As shown in FIG. 3A, the cell stack device 10 includes a cell stack 11 having a plurality of cells 1 arranged (stacked) in the thickness direction T of the cells 1 (see FIG. 1A), and a fixing member 12.

[0052] The fixing member 12 has a fixing material 13 and a support member 14. The support member 14 supports the cell 1. The fixing material 13 fixes the cell 1 to the support member 14. The support member 14 also has a support 15 and a gas tank 16. The support 15 and the gas tank 16, which are the support member 14, are made of, for example, metal.

[0053] 3B, the support body 15 has insertion holes 15a into which the lower ends of the plurality of cells 1 are inserted. The lower ends of the plurality of cells 1 and the inner wall of the insertion holes 15a are joined with fixing material 13.

[0054] The gas tank 16 has an opening for supplying a reaction gas to the cells 1 through the insertion holes 15a, and a recessed groove 16a located around the opening. The outer peripheral edge of the support 15 is joined to the gas tank 16 by a bonding material 21 filled in the recessed groove 16a of the gas tank 16.

[0055] In the example shown in Fig. 3A, fuel gas is stored in an internal space 22 (see Fig. 3B) formed by a support 15, which is the support member 14, and a gas tank 16. A gas circulation pipe 20 is connected to the gas tank 16. The fuel gas is supplied to the gas tank 16 through this gas circulation pipe 20, and is supplied from the gas tank 16 to a gas flow path 2a (see Fig. 1A) inside the cell 1. The fuel gas supplied to the gas tank 16 is generated in a reformer 102 (see Fig. 4), which will be described later.

[0056] The hydrogen-rich fuel gas can be produced by steam reforming the raw fuel, etc. When the fuel gas is produced by steam reforming, the fuel gas contains water vapor.

[0057] The example shown in Fig. 3A includes two rows of cell stacks 11, two supports 15, and a gas tank 16. Each of the two rows of cell stacks 11 has a plurality of cells 1. Each cell stack 11 is fixed to a corresponding support 15. The gas tank 16 may have two through-holes on its top surface. A support 15 is disposed in each through-hole. The internal space 22 may be formed by one gas tank 16 and two supports 15.

[0058] The shape of the insertion hole 15a may be, for example, an oval shape when viewed from above. For example, the length of the insertion hole 15a in the arrangement direction of the cells 1, i.e., the thickness direction T, may be greater than the distance between the two end current collecting members 17 located at both ends of the cell stack 11. For example, the width of the insertion hole 15a may be greater than the length of the cell 1 in the width direction W (see FIG. 1A ).

[0059] 3B , the joint between the inner wall of the insertion hole 15a and the lower end of the cell 1 is filled with a fixing material 13 and solidified. As a result, the inner wall of the insertion hole 15a and the lower end of each of the cells 1 may be joined and fixed. Alternatively, the lower ends of the cells 1 may be joined and fixed to each other. The gas flow path 2a of each cell 1 may communicate with the internal space 22 of the support member 14 at its lower end.

[0060] A material with 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.

[0061] Examples of the crystallized glass include SiO ２ -CaO system, MgO-B ２ O ３ System, La ２ O ３ -B ２ O ３ -MgO system, La ２ O ３ -B ２ O ３ -ZnO-based, SiO ２ -CaO-ZnO system materials, etc., may be used, and in particular SiO ２ - MgO-based materials may also be used.

[0062] 3B , a connecting member 18 may be interposed between adjacent cells 1 among the plurality of cells 1. The connecting member 18 can electrically connect the anode 5 of one adjacent cell 1 to the cathode 8 of the other cell 1 in series. More specifically, the connecting member 18 may connect the interconnector 4 electrically connected to the anode 5 of one adjacent cell 1 to the cathode 8 of the other cell 1.

[0063] 3B, an end current collecting member 17 may be 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 may be connected to a conductive portion 19 that protrudes to the outside of the cell stack 11. The conductive portion 19 collects electricity generated by power generation in the cells 1 and extracts it to the outside. Note that the end current collecting member 17 is not shown in FIG. 3A.

[0064] 3C, the cell stack device 10 may be a single battery in which two cell stacks 11A, 11B are connected in series. In such a case, 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.

[0065] The positive electrode terminal 19A is a positive electrode when the power generated by the cell stack 11 is output to the outside. The positive electrode terminal 19A is electrically connected to the end current collector 17 on the positive electrode side of the cell stack 11A. The negative electrode terminal 19B is a negative electrode when the power generated by the cell stack 11 is output to the outside. The negative electrode terminal 19B is electrically connected to the end current collector 17 on the negative electrode side of the cell stack 11B.

[0066] The connection terminal 19C electrically connects the end current collecting member 17 on the negative electrode side of the cell stack 11A to the end current collecting member 17 on the positive electrode side of the cell stack 11B.

[0067] <Module> Next, a module according to an embodiment of the present disclosure using the electrochemical cell device described above will be described with reference to Fig. 4. Fig. 4 is an external perspective view showing an example of a module according to the first embodiment. Fig. 4 shows a state in which the front and rear surfaces, which are parts 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.

[0068] 4, the module 100 includes a cell stack device 10 and a storage container 101 that stores the cell stack device 10. A reformer 102 may be disposed above the cell stack device 10.

[0069] The reformer 102 reforms raw fuel such as natural gas or kerosene to generate fuel gas, which is then supplied to the cell 1. The raw fuel is supplied to the reformer 102 through a raw fuel supply pipe 103. The reformer 102 may include a vaporizer 102a that vaporizes water, and a reformer 102b. The reformer 102b includes a reforming catalyst (not shown) and reforms the raw fuel into fuel gas. Such a reformer 102 can perform steam reforming, a highly efficient reforming reaction.

[0070] The fuel gas produced in the reformer 102 is supplied to the gas flow channel 2 a of the cell 1 (see FIG. 1A) through the gas distribution pipe 20 , the gas tank 16 , and the support member 14 .

[0071] Furthermore, in the module 100 having the above-described configuration, the temperature inside the module 100 during normal power generation reaches approximately 500°C to 1000°C due to the combustion of gas and the power generation of the cells 1.

[0072] In such a module 100, as described above, the module 100 can be configured to house the cell stack device 10 having the cells 1 with improved performance, thereby making it possible to make the module 100 with improved performance.

[0073] <Module Enclosure Device> Fig. 5 is an exploded perspective view schematically illustrating an example of a module enclosure device according to the first embodiment. The module enclosure device 110 according to this embodiment includes an outer case 111, the module 100 shown in Fig. 4, and auxiliary equipment (not shown). The auxiliary equipment operates the module 100. The outer case 111 accommodates the module 100 and the auxiliary equipment. Note that some components are omitted in Fig. 5.

[0074] An exterior case 111 of a module accommodating device 110 shown in Fig. 5 has support columns 112 and an exterior plate 113. A partition plate 114 divides the interior of the exterior case 111 into upper and lower sections. The space above the partition plate 114 in the exterior case 111 is a module accommodating chamber 115 that accommodates the module 100. The space below the partition plate 114 in the exterior case 111 is an accessory accommodating chamber 116 that accommodates accessory equipment configured to operate the module 100. Note that in Fig. 5, the accessory equipment accommodated in the accessory accommodating chamber 116 is omitted from the illustration.

[0075] The partition plate 114 also has an air flow port 117 for allowing air from the auxiliary equipment housing chamber 116 to flow toward the module housing chamber 115. The exterior plate 113 that constitutes the module housing chamber 115 has an exhaust port 118 for exhausting air from within the module housing chamber 115.

[0076] In such a module accommodating device 110, as described above, the module 100 with improved cell performance is provided in the module accommodating chamber 115, thereby making it possible to provide a module accommodating device 110 with improved cell performance.

[0077] In the above embodiment, a case where a hollow flat plate-type support substrate is used is exemplified, but the present invention can also be applied to a cell stack device that uses a cylindrical support substrate.

[0078] Second Embodiment Next, an electrochemical cell and an electrochemical cell device according to a second embodiment will be described with reference to FIGS. 6A to 7. FIG.

[0079] In the above-described embodiment, a vertically striped electrochemical cell device is illustrated in which so-called "vertically striped" electrochemical cells, each having only one element unit including a fuel electrode, a solid electrolyte layer, and an air electrode, are arranged on the surface of a support substrate. However, the present invention can also be applied to a horizontally striped electrochemical cell device in which so-called "horizontally striped" electrochemical cells are arranged. A "horizontally striped" electrochemical cell is an electrochemical cell in which element units are provided at multiple locations spaced apart from each other on the surface of a support substrate, and adjacent element units are electrically connected.

[0080] Fig. 6A is a cross-sectional view showing an example of an electrochemical cell device according to a second embodiment, Fig. 6B is a transverse cross-sectional view showing an electrochemical cell according to a second embodiment, and Fig. 7 is an enlarged cross-sectional view of a region R2 shown in Fig. 6B.

[0081] 6A, in the cell stack device 10A, a plurality of cells 1 extend in a longitudinal direction L from a pipe 22a through which fuel gas flows. Each cell 1 has a plurality of element portions 3A on a support substrate 2. A gas flow path 2a through which fuel gas flows from the pipe 22a is provided inside the support substrate 2.

[0082] The cells 1 are electrically connected to one another via connection members 31. The connection members 31 are located between the element portions 3A of the cells 1, and connect the adjacent cells 1 to one another.

[0083] 6B, the cell 1 according to this embodiment includes a support substrate 2, a pair of element portions 3A, and a sealing portion 32. The support substrate 2 is columnar and has a pair of opposing flat surfaces, that is, surfaces n1 and n2, and a pair of arc-shaped side surfaces m connecting the surfaces n1 and n2.

[0084] The pair of element portions 3A are located on the surface n1 and the surface n2 of the support substrate 2, respectively. The pair of element portions 3A may be located so as to face each other across the support substrate 2. In addition, the sealing portion 32 is located so as to cover the side surface m of the support substrate 2.

[0085] 7, the electrochemical cell according to this embodiment has an element part 3 A. The element part 3 A has a solid electrolyte layer 6 , a fuel electrode 5 , and a cathode 8 .

[0086] The solid electrolyte layer 6 has a first surface 601 and a second surface 602 located on the opposite side of the first surface 601. The solid electrolyte layer 6 may include an oxide containing Zr.

[0087] The fuel electrode 5 contains metal particles and is a first electrode facing the first surface 601 .

[0088] The cathode 8 contains inorganic oxide particles. The cathode 8 is a second electrode facing the second surface 602. The cathode 8 may contain La and / or Sr.

[0089] The solid electrolyte layer 6 has a first portion 61 and a second portion 62. The first portion 61 is a portion whose distance to the first surface 601 is smaller than the distance to the second surface 602. The first portion 61 may include the first surface 601.

[0090] The second portion 62 is a portion that is located at a greater distance from the first surface 601 than the first portion 61. The second portion 62 may include the second surface 602.

[0091] 7 , in a cross section of the solid electrolyte layer 6 taken along the thickness direction, when the number per unit area of ​​the first pores 61a, which are the pores 6a located in the first portion 61, is P1 and the number per unit area of ​​the second pores 62a, which are the pores 6a located in the second portion 62, is P2, P2 is greater than P1.

[0092] For example, the second region 62 has a larger number of pores 6 a per unit area than the first region 61, which makes it difficult for a high-resistance phase containing components of the air electrode 8, such as La or Sr, to form inside the solid electrolyte layer 6, thereby contributing primarily to ensuring electrical conductivity. On the other hand, the first region 61 has a smaller number of pores 6 a per unit area than the second region 62, which contributes primarily to ensuring gas barrier properties. This makes it possible to achieve both the electrical conductivity and gas barrier properties required of the solid electrolyte layer 6. Therefore, the electrochemical cell according to this embodiment improves cell performance.

[0093] The element unit 3A may further include an intermediate layer 7 located between the second surface 602 of the solid electrolyte layer 6 and the air electrode 8. The intermediate layer 7 may contain Ce. In this case, for example, in the second portion 62, the second pores 62a tend to prevent the diffusion of Ce contained in the intermediate layer 7 into the interior. Therefore, even if Ce diffuses into the solid electrolyte layer 6, a high-resistance phase, which is a reaction product between the Ce and the oxide contained in the solid electrolyte layer 6, is less likely to form inside the solid electrolyte layer 6. Therefore, the solid electrolyte layer 6 as a whole has sufficient conductivity. Therefore, the electrochemical cell according to this embodiment improves cell performance.

[0094] [Third Embodiment] Fig. 8A is a perspective view showing an example of an electrochemical cell according to a third embodiment, and Fig. 8B is a partial cross-sectional view of the electrochemical cell shown in Fig. 8A.

[0095] 8A and 8B , the cell 1 includes an element section 3B in which an anode 5, a solid electrolyte layer 6, and an air electrode 8 are stacked in this order, and conductive members 91 and 92 positioned on either side of the element section 3B. In an electrochemical cell device in which a plurality of flat cells are stacked, for example, the plurality of cells 1 are electrically connected by conductive members 91 and 92, which are adjacent metal layers. The conductive members 91 and 92 electrically connect adjacent cells 1 to each other and have gas flow paths for supplying gas to the anode 5 or the air electrode 8.

[0096] 8B, the cell 1 has a sealing material that hermetically seals the fuel gas flow path and the oxygen-containing gas flow path of the flat cell stack. The sealing material is a fixing member 96 for the cell 1. The fixing member 96 has a bonding material 93 and support members 94 and 95 that serve as a frame. The bonding material 93 may be glass or a metal material such as silver solder.

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

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

[0099] Fig. 9 is an enlarged cross-sectional view of region R3 shown in Fig. 8B. As shown in Fig. 9, the electrochemical cell according to this embodiment has an element section 3B. The element section 3B has a solid electrolyte layer 6, an anode 5, and an cathode 8.

[0100] The solid electrolyte layer 6 has a first surface 601 and a second surface 602 located on the opposite side of the first surface 601. The solid electrolyte layer 6 may include an oxide containing Zr.

[0101] The fuel electrode 5 contains metal particles and is a first electrode facing the first surface 601 .

[0102] The cathode 8 contains inorganic oxide particles. The cathode 8 is a second electrode facing the second surface 602. The cathode 8 may contain La and / or Sr.

[0103] The solid electrolyte layer 6 has a first portion 61 and a second portion 62. The first portion 61 is a portion whose distance to the first surface 601 is smaller than the distance to the second surface 602. The first portion 61 may include the first surface 601.

[0104] The second portion 62 is a portion that is located at a greater distance from the first surface 601 than the first portion 61. The second portion 62 may include the second surface 602.

[0105] 9 , in a cross section of the solid electrolyte layer 6 taken along the thickness direction, when the number per unit area of ​​the first pores 61a, which are the pores 6a located in the first portion 61, is P1 and the number per unit area of ​​the second pores 62a, which are the pores 6a located in the second portion 62, is P2, P2 is greater than P1.

[0106] For example, the second region 62 has a larger number of pores 6 a per unit area than the first region 61, which makes it difficult for a high-resistance phase containing components of the air electrode 8, such as La or Sr, to form inside the solid electrolyte layer 6, thereby contributing primarily to ensuring electrical conductivity. On the other hand, the first region 61 has a smaller number of pores 6 a per unit area than the second region 62, which contributes primarily to ensuring gas barrier properties. This makes it possible to achieve both the electrical conductivity and gas barrier properties required of the solid electrolyte layer 6. Therefore, the electrochemical cell according to this embodiment improves cell performance.

[0107] The element unit 3B may further include an intermediate layer 7 located between the second surface 602 of the solid electrolyte layer 6 and the air electrode 8. The intermediate layer 7 may contain Ce. In this case, for example, in the second portion 62, the second pores 62a tend to prevent the diffusion of Ce contained in the intermediate layer 7 into the interior. Therefore, even if Ce diffuses into the solid electrolyte layer 6, a high-resistance phase, which is a reaction product between the Ce and the oxide contained in the solid electrolyte layer 6, is less likely to form inside the solid electrolyte layer 6. Therefore, the solid electrolyte layer 6 as a whole has sufficient conductivity. Therefore, the electrochemical cell according to this embodiment improves cell performance.

[0108] [Fourth embodiment] Fig. 10A is a cross-sectional view showing an example of an electrochemical cell according to a fourth embodiment. Figs. 10B and 10C are cross-sectional views showing another example of an electrochemical cell according to the fourth embodiment. Fig. 11 is an enlarged cross-sectional view of region R4 shown in Fig. 10A. Note that Fig. 11 can also be applied to the electrochemical cells shown in Figs. 10B and 10C.

[0109] As shown in FIGS. 10A to 10C, the cell 1 has an element portion 3C and a support substrate 2. The support substrate 2 has through-holes or pores in the area in contact with the element portion 3C. The support substrate 2 further has a member 120 located outside the gas flow path 2a. The support substrate 2 allows gas to flow between the gas flow path 2a and the element portion 3C. The support substrate 2 may be composed of, for example, one or more metal plates. The material of the metal plate may contain chromium. The metal plate may have a conductive coating layer. The support substrate 2 electrically connects adjacent cells 1 to each other. The element portion 3C may be formed directly on the support substrate 2, or may be bonded to the support substrate 2 with a bonding material.

[0110] The cell 1 may also have an adhesive (not shown) located between the fuel electrode 5 and the support substrate 2. The adhesive bonds the element portion 3C and the support substrate 2 and fixes the element portion 3C to the support substrate 2.

[0111] The adhesive may be conductive. For example, the adhesive may be a mixture 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 adhesive may contain inorganic oxides such as titanium dioxide, copper dioxide, copper oxide, and the like. The adhesive may contain metal particles and conductive oxide particles.

[0112] The adhesive may be gas permeable. When the adhesive is gas permeable, the adhesive may be positioned so as to cover the through-holes or pores of the support substrate 2.

[0113] The adhesive may be formed as a single layer using a single material, or may be formed as a laminate of multiple materials.

[0114] The cell 1 may further include a constraining layer (not shown). The constraining layer may be located between the element portion 3C and the adhesive. The constraining layer cooperates with the solid electrolyte layer 6 to make the element portion 3C less susceptible to warping, bending, and the like.

[0115] The material of the constraining layer may exhibit a shrinkage rate similar to that of the material of the solid electrolyte layer 6 during firing. The material of the constraining layer may be the same as the material of the solid electrolyte layer 6. The element unit 3C obtained by sandwiching the material of the anode 5 of the element unit 3C between the material of the solid electrolyte layer 6 and the material of the constraining layer and firing the resulting element unit 3C has little warping or deformation.

[0116] The constraining layer may or may not be gas permeable. When the constraining layer has gas barrier properties comparable to those of the solid electrolyte layer 6, the constraining layer can be partially disposed so as not to obstruct the inflow of fuel gas to the anode 5.

[0117] The cell 1 may further include a gas diffusion layer (not shown). The gas diffusion layer may be located between the fuel electrode 5 and the support substrate 2. The gas diffusion layer has gas permeability and allows the fuel gas flowing through the gas flow channel 2a to pass through 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%.

[0118] The material of the gas diffusion layer may be a porous conductive ceramic, such as a ceramic containing calcium oxide, magnesium oxide, or stabilized zirconia or partially stabilized zirconia in which a rare earth element oxide is solid-solved, and Ni and / or NiO. The rare earth element oxide may contain a plurality of rare earth elements selected from, for example, Sc, Y, La, Nd, Sm, Gd, Dy, and Yb.

[0119] In the example shown in Fig. 10A, the side surface of the anode 5 is covered with a solid electrolyte layer 6, which airtightly seals a gas flow channel 2a through which the fuel gas flows. As shown in Fig. 10B, the side surface of the anode 5 may be covered and sealed with a dense glass or ceramic sealant 9. The sealant 9 covering the side surface of the anode 5 may have electrical insulating properties.

[0120] Furthermore, the gas flow path 2a of the support substrate 2 may be formed by a member 120 having projections and recesses as shown in FIG. 10C.

[0121] The electrochemical cell according to this embodiment includes an element section 3 C. The element section 3 C includes a solid electrolyte layer 6 , a fuel electrode 5 , and a cathode 8 .

[0122] The solid electrolyte layer 6 has a first surface 601 and a second surface 602 located on the opposite side of the first surface 601. The solid electrolyte layer 6 may include an oxide containing Zr.

[0123] The fuel electrode 5 contains metal particles and is a first electrode facing the first surface 601 .

[0124] The cathode 8 contains inorganic oxide particles. The cathode 8 is a second electrode facing the second surface 602. The cathode 8 may contain La and / or Sr.

[0125] The solid electrolyte layer 6 has a first portion 61 and a second portion 62. The first portion 61 is a portion whose distance to the first surface 601 is smaller than the distance to the second surface 602. The first portion 61 may include the first surface 601.

[0126] The second portion 62 is a portion that is located at a greater distance from the first surface 601 than the first portion 61. The second portion 62 may include the second surface 602.

[0127] 11 , in a cross section of the solid electrolyte layer 6 taken along the thickness direction, when the number per unit area of ​​the first pores 61a, which are the pores 6a located in the first portion 61, is P1 and the number per unit area of ​​the second pores 62a, which are the pores 6a located in the second portion 62, is P2, P2 is greater than P1.

[0128] For example, the second region 62 has a larger number of pores 6 a per unit area than the first region 61, which makes it difficult for a high-resistance phase containing components of the air electrode 8, such as La or Sr, to form inside the solid electrolyte layer 6, thereby contributing primarily to ensuring electrical conductivity. On the other hand, the first region 61 has a smaller number of pores 6 a per unit area than the second region 62, which contributes primarily to ensuring gas barrier properties. This makes it possible to achieve both the electrical conductivity and gas barrier properties required of the solid electrolyte layer 6. Therefore, the electrochemical cell according to this embodiment improves cell performance.

[0129] The element unit 3C may further include an intermediate layer 7 located between the second surface 602 of the solid electrolyte layer 6 and the air electrode 8. The intermediate layer 7 may contain Ce. In this case, for example, in the second portion 62, the second pores 62a tend to prevent the diffusion of Ce contained in the intermediate layer 7 into the interior. Therefore, even if Ce diffuses into the solid electrolyte layer 6, a high-resistance phase, which is a reaction product between the Ce and the oxide contained in the solid electrolyte layer 6, is less likely to form inside the solid electrolyte layer 6. Therefore, the solid electrolyte layer 6 as a whole has sufficient conductivity. Therefore, the electrochemical cell according to this embodiment improves cell performance.

[0130] Other Embodiments Next, electrochemical cell devices according to other embodiments will be described.

[0131] In the above-described embodiments, a fuel cell, a fuel cell stack device, a fuel cell module, and a fuel cell device are shown as examples of an "electrochemical cell," "electrochemical cell device," "module," and "module housing device." However, other examples may be an electrolysis cell, an electrolysis cell stack device, an electrolysis module, and an electrolysis device, respectively. The electrolysis cell has a first electrode and a second electrode, and decomposes water vapor into hydrogen and oxygen, or decomposes carbon dioxide into carbon monoxide and oxygen, when supplied with electric power. Furthermore, in the above-described embodiments, an oxide ion conductor or a hydrogen ion conductor is shown as an example of the electrolyte material of the electrochemical cell, but a hydroxide ion conductor may also be used. Such an electrolysis cell, an electrolysis cell stack device, an electrolysis module, and an electrolysis device can improve cell performance.

[0132] Samples Nos. 1 to 6 were prepared with different porosities and average pore diameters in the solid electrolyte layer 6, and the resistance was evaluated.

[0133] (Preparation of Samples No. 1 to 6) As Samples No. 1 to 6, single cells were prepared as element parts having a solid electrolyte layer 6, a fuel electrode 5, an intermediate layer 7, and an air electrode 8. ２ O ３ ZrO in which 8 mol % is dissolved ２A powder (YSZ powder) was prepared. A solid electrolyte precursor slurry was prepared by mixing the YSZ powder, a pore-forming agent, a binder, and a solvent. The solid electrolyte precursor slurry was formed into a sheet to obtain a solid electrolyte precursor sheet. The obtained solid electrolyte precursor sheet was overlaid on a previously prepared anode precursor molded sheet (anode precursor sheet) to obtain a first laminate. The obtained first laminate was degreased and then fired in air at approximately 1500°C to obtain a first sintered laminate. An intermediate layer precursor slurry was further printed on the solid electrolyte layer of the obtained first sintered laminate to obtain a second laminate. The second laminate was degreased and then fired in air at 1350°C to obtain a second sintered laminate. An air electrode precursor slurry was further printed on the intermediate layer of the second sintered laminate to obtain a third laminate. The third laminate was degreased and then fired in air at 1150°C to obtain a single cell. Six types of solid electrolyte precursor slurries were prepared, each with a different ratio of YSZ powder to pore-forming agent. Using these slurries, single cells (samples 1 to 6) were fabricated, each with a different porosity and average pore diameter of the solid electrolyte layer 6.

[0134] (Evaluation of Samples No. 1 to 6) The resistance of the single cells of Samples No. 1 to 6 was measured. In addition, cross sections including the solid electrolyte layer 6 of Samples No. 1 to 6 were observed using an SEM, and the numbers P1 and P2 of pores per unit area of ​​the first region 61 and the second region 62, the porosity of the second region 62, and the average pore diameter of the pores 6a were calculated by image analysis. The resistance was an ohmic resistance measured by an AC impedance method.

[0135] FIG. 12 shows the evaluation results for Samples No. 1 to 6. As shown in FIG. 12, Samples No. 2 to 5 had a larger number of pores per unit area (P2) in the second region 62 than the number of pores in the first region 61 (P1), resulting in lower resistance than Sample No. 1, in which the number of pores per unit area in the first region 61 and the second region 62 were the same. The porosity of the second region 62 in Samples No. 2 to 5 was in the range of 1% to 9%. The average pore diameter of the solid electrolyte layer 6 in Samples No. 2 to 4 was 1.3 μm or less, resulting in lower resistance than Samples No. 1 and 5. Note that Sample No. 6 had an average pore diameter of the solid electrolyte layer 6 of 2 μm or more, and accurate resistance measurement was not possible due to voltage oscillations associated with gas leakage.

[0136] Although the present disclosure has been described in detail above, the present disclosure is not limited to the above-described embodiments, and various modifications, improvements, etc. are possible within the scope that does not deviate from the gist of the present disclosure.

[0137] In one embodiment, (1) an electrochemical cell includes: a solid electrolyte layer having a first surface and a second surface located opposite to the first surface; a first electrode including metal particles and facing the first surface; and a second electrode including inorganic oxide particles and facing the second surface, wherein the solid electrolyte layer has a first region whose distance from the first surface is smaller than that from the second surface, and a second region whose distance from the first surface is larger than that from the first region, and in a cross section along the thickness direction of the solid electrolyte layer, when the number of pores located per unit area in the first region is P1 and the number of pores per unit area in the second region is P2, P2 is greater than P1.

[0138] (2) In the electrochemical cell of (1), the porosity of the second region may be 1% or more and 9% or less.

[0139] (3) In the electrochemical cell of (1) or (2) above, the porosity of the first region may be 5% or less.

[0140] (4) In the electrochemical cell of any one of (1) to (3) above, the pores located in the solid electrolyte layer may have an average pore diameter of 1.3 μm or less.

[0141] (5) In the electrochemical cell of any one of (1) to (4) above, the average pore diameter of the pores located in the second region may be smaller than the average pore diameter of the pores located in the first region.

[0142] (6) In the electrochemical cell of any one of (1) to (5) above, the solid electrolyte layer may contain an oxide containing Zr.

[0143] (7) The electrochemical cell of (6) above may further include an intermediate layer located between the second surface and the second electrode and containing Ce.

[0144] (8) In the electrochemical cell of any one of (1) to (7) above, the second electrode may contain La and / or Sr.

[0145] In one embodiment, (9) an electrochemical cell device has a cell stack including any one of the electrochemical cells (1) to (8) above.

[0146] In one embodiment, a module (10) includes the electrochemical cell device (9) described above, and a container that houses the electrochemical cell device.

[0147] In one embodiment, (11) a module housing device includes the module of (10) above, an auxiliary device configured to operate the module, and an outer case housing the module and the auxiliary device.

[0148] The disclosed embodiments should be considered in all respects as illustrative and not restrictive. Indeed, the above-described embodiments may be embodied in various forms. Furthermore, the above-described embodiments may be omitted, substituted, or modified in various ways without departing from the scope and spirit of the appended claims.

[0149] REFERENCE SIGNS LIST 1 cell 2 support substrate 3, 3A to 3C element portion 4 interconnector 5 fuel electrode 6 solid electrolyte layer 6a pores 7 intermediate layer 8 air electrode 10 cell stack device 11 cell stack 12 fixing member 13 fixing material 14 support member 15 support body 16 gas tank 17 end current collecting member 18 connection member 61 first portion 61a first pores 62 second portion 62a second pores 100 module 110 module accommodating device

Claims

1. An electrochemical cell comprising: a solid electrolyte layer having a first surface and a second surface located opposite the first surface; a first electrode containing metal particles and facing the first surface; and a second electrode containing inorganic oxide particles and facing the second surface, wherein the solid electrolyte layer has a first region whose distance from the first surface is smaller than the distance from the second surface, and a second region whose distance from the first surface is larger than the first region, wherein, in a cross section along the thickness direction of the solid electrolyte layer, when the number of pores per unit area located in the first region is P1 and the number of pores per unit area located in the second region is P2, P2 is greater than P1.

2. The electrochemical cell according to claim 1, wherein the porosity of the second region is 1% or more and 9% or less.

3. An electrochemical cell according to claim 1 or 2, wherein the porosity of the first portion is 5% or less.

4. The electrochemical cell according to any one of claims 1 to 3, wherein the pores located in the solid electrolyte layer have an average pore diameter of 1.3 µm or less.

5. An electrochemical cell according to any one of claims 1 to 4, wherein the average pore diameter of the pores located in the second region is smaller than the average pore diameter of the pores located in the first region.

6. The electrochemical cell according to any one of claims 1 to 5, wherein the solid electrolyte layer contains an oxide containing Zr.

7. The electrochemical cell of claim 6, further comprising an intermediate layer located between said second surface and said second electrode and comprising Ce.

8. An electrochemical cell according to any one of claims 1 to 7, wherein the second electrode contains La and / or Sr.

9. An electrochemical cell device having a cell stack comprising an electrochemical cell according to any one of claims 1 to 8.

10. A module comprising the electrochemical cell device according to claim 9 and a container housing the electrochemical cell device.

11. A module housing device comprising: a module according to claim 10; an accessory configured to operate said module; and an outer case housing said module and said accessory.

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