Electrochemical Cell

Abstract

The electrolysis cell (1) includes a metal support (10) having a plurality of communication holes (11) formed in a first main surface (12), and a cell main body (20). The cell main body (20) includes a gas diffusion layer (5) disposed on the first main surface (12) of the metal support (10), and a hydrogen electrode layer (6) disposed on the gas diffusion layer (5). The gas diffusion layer (5) has a through hole (51) communicating with the communication hole (11). The through hole (51) has a gap space (51a) that enters into the gap between the first main surface (12) and the hydrogen electrode layer (6).

Description

[Technical field]

[0001] The present invention relates to electrochemical cells. [Background technology]

[0002] Patent Document 1 discloses an electrochemical cell (electrolysis cell, fuel cell, etc.) having a cell body disposed on a metal support. The metal support has a plurality of communication holes formed on a main surface. The cell body has a gas diffusion layer formed on the main surface of the metal support, a first electrode layer and a second electrode layer disposed on the gas diffusion layer, and an electrolyte layer disposed between the first electrode layer and the second electrode layer.

[0003] Patent Document 1 describes that in order to facilitate smooth gas supply and exhaust between the communication holes of the metal support and the first electrode layer, through holes communicating with the communication holes are formed in the gas diffusion layer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2020-079189 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, in the electrochemical cell disclosed in Patent Document 1, damage (cracks and peeling) may occur in the gas diffusion layer due to dimensional changes in the first electrode layer accompanying oxidation and reduction.

[0006] An object of the present invention is to provide an electrochemical cell capable of suppressing damage to a gas diffusion layer. [Means for solving the problem]

[0007] An electrochemical cell according to a first aspect of the present invention comprises a metal support having a plurality of through holes formed in a main surface, and a cell body portion disposed on the main surface. The cell body portion has a gas diffusion layer disposed on the main surface, a first electrode layer disposed on the gas diffusion layer, a second electrode layer, and an electrolyte layer disposed between the first electrode layer and the second electrode layer. The gas diffusion layer has through holes communicating with the through holes. The through holes have a gap space that penetrates into the gap between the main surface and the first electrode layer.

[0008] An electrochemical cell according to a second aspect of the present invention is related to the first aspect, wherein the gap space is tapered toward the deepest part of the gap space in a planar direction perpendicular to a thickness direction of the gas diffusion layer.

[0009] The electrochemical cell according to a third aspect of the present invention is related to the second aspect, wherein the gas diffusion layer has an exposed surface exposed to the gap space, and the exposed surface is curved.

[0010] An electrochemical cell according to a fourth aspect of the present invention is related to any one of the first to third aspects, wherein the gas diffusion layer has a first extension portion sandwiched between the gap space and the first electrode layer in the thickness direction.

[0011] An electrochemical cell according to a fifth aspect of the present invention is related to any one of the first to fourth aspects, wherein the gas diffusion layer has a second extension portion sandwiched between the gap space and the metal support in the thickness direction.

[0012] An electrochemical cell according to a sixth aspect of the present invention is related to any one of the first to second aspects, wherein a width of the gap space in the planar direction is greater than a thickness of the gas diffusion layer in the thickness direction.

[0013] An electrochemical cell according to a seventh aspect of the present invention is related to any one of the first to sixth aspects, wherein the width of the gap space in the planar direction is 10 μm or more.

[0014] An electrochemical cell according to an eighth aspect of the present invention is related to any one of the first to ninth aspects above, wherein the metal support has a substrate and an oxide film covering a surface of the substrate, and a thickness of a first portion of the oxide film exposed to the communicating hole is thicker than a thickness of a second portion of the oxide film facing the first electrode layer.

[0015] An electrochemical cell according to a ninth aspect of the present invention is related to any one of the first to eighth aspects, wherein an average pore diameter of the plurality of first pores in the gas diffusion layer is smaller than an average pore diameter of the plurality of second pores in the first electrode layer.

[0016] An electrochemical cell according to a tenth aspect of the present invention is related to the above ninth aspect, wherein the porosity of the gas diffusion layer is greater than the porosity of the first electrode layer. Effect of the Invention

[0017] According to the present invention, it is possible to provide an electrochemical cell capable of suppressing damage to a gas diffusion layer. [Brief description of the drawings]

[0018] [Figure 1] FIG. 1 is a plan view of an electrolysis cell according to an embodiment. [Diagram 2] FIG. 2 is a cross-sectional view taken along line AA of FIG. [Diagram 3] FIG. 3 is a partially enlarged view of FIG. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] (Electrolysis cell 1) Fig. 1 is a plan view of an electrolysis cell 1 according to an embodiment of the present invention, and Fig. 2 is a cross-sectional view taken along line AA in Fig. 1.

[0020] The electrolysis cell 1 is an example of an "electrochemical cell" according to the present invention. The electrolysis cell 1 is a so-called metal-supported electrolysis cell.

[0021] The electrolysis cell 1 is formed in a plate shape extending in the X-axis and Y-axis directions. In this embodiment, the electrolysis cell 1 is formed in a rectangular shape extending in the Y-axis direction when viewed in a plan view from the Z-axis direction perpendicular to the X-axis and Y-axis directions. However, the planar shape of the electrolysis cell 1 is not particularly limited, and may be a polygon other than a rectangle, an ellipse, a circle, or the like.

[0022] As shown in FIG. 2, the electrolysis cell 1 includes a metal support 10, a cell main body 20, and a flow path member 30.

[0023] [Metal support 10] The metal support 10 supports the cell main body 20. The metal support 10 is formed in a plate shape. The metal support 10 may be in the shape of a flat plate or a curved plate.

[0024] The metal support 10 is only required to be able to support the cell main body 20, and its thickness is not particularly limited, but can be, for example, 0.1 mm or more and 2.0 mm or less.

[0025] As shown in FIG. 2, the metal support 10 has a plurality of communicating holes 11, a first main surface 12 and a second main surface 13.

[0026] Each communication hole 11 penetrates the metal support 10 in the Z-axis direction from the first main surface 12 to the second main surface 13. Each communication hole 11 opens to each of the first main surface 12 and the second main surface 13. In this embodiment, the opening of each communication hole 11 on the first main surface 12 side is covered by the cell main body 20 (specifically, the hydrogen electrode layer 6 described later). The opening of each communication hole 11 on the second main surface 13 side is connected to a flow path 30a described later.

[0027] Each communication hole 11 can be formed by mechanical processing (for example, punching), laser processing, chemical processing (for example, etching), or the like.

[0028] In this embodiment, each communication hole 11 is formed linearly along the Z-axis direction. However, each communication hole 11 may be inclined with respect to the Z-axis direction, and may not be linear. Furthermore, the communication holes 11 may be connected to each other.

[0029] The first main surface 12 is provided on the opposite side to the second main surface 13. A cell main body 20 is disposed on the first main surface 12. A flow path member 30 is bonded to the second main surface 13.

[0030] The metal support 10 is made of a metal material. For example, the metal support 10 is made of an alloy material containing Cr (chromium). Examples of such metal materials include Fe-Cr alloy steel (stainless steel, etc.) and Ni-Cr alloy steel. The Cr content of the metal support 10 is not particularly limited, but can be set to 4% by mass or more and 30% by mass or less.

[0031] The metal support 10 may contain Ti (titanium) and Zr (zirconium). The Ti content in the metal support 10 is not particularly limited, but may be 0.01 mol% or more and 1.0 mol% or less. The Zr content in the metal support 10 is not particularly limited, but may be 0.01 mol% or more and 0.4 mol% or less. The metal support 10 may contain Ti as TiO2 (titania) or Zr as ZrO2 (zirconia).

[0032] [Cell body 20] The cell body 20 is disposed on the metal support 10. The cell body 20 is supported by the metal support 10. The cell body 20 has a gas diffusion layer 5, a hydrogen electrode layer 6 (cathode), an electrolyte layer 7, a reaction prevention layer 8, and an oxygen electrode layer 9 (anode).

[0033] The gas diffusion layer 5, hydrogen electrode layer 6, electrolyte layer 7, reaction prevention layer 8, and oxygen electrode layer 9 are laminated in this order in the Z-axis direction from the metal support 10 side. The gas diffusion layer 5, hydrogen electrode layer 6, electrolyte layer 7, and oxygen electrode layer 9 are essential components, while the reaction prevention layer 8 is optional.

[0034] [Gas diffusion layer 5] The gas diffusion layer 5 is disposed on the first main surface 12 of the metal support 10. The gas diffusion layer 5 is interposed between the metal support 10 and the hydrogen electrode layer 6. The gas diffusion layer 5 is in direct contact with both the metal support 10 and the hydrogen electrode layer 6.

[0035] The gas diffusion layer 5 has a plurality of through holes 51 , a first connection surface 52 and a second connection surface 53 .

[0036] Each through hole 51 penetrates the gas diffusion layer 5 in the Z-axis direction from the first connection surface 52 to the second connection surface 53. Each through hole 51 opens to the first connection surface 52 and the second connection surface 53. In this embodiment, the opening of each through hole 51 on the first connection surface 52 side is covered by the hydrogen electrode layer 6. The opening of each through hole 51 on the second connection surface 53 side communicates with each communication hole 11 of the metal support 10. Therefore, the gas diffusion layer 5 does not cover each communication hole 11 of the metal support 10.

[0037] The first connection surface 52 is connected to the first main surface 12 of the metal support 10. The first connection surface 52 is provided on the opposite side to the second connection surface 53. The second connection surface 53 is connected to the hydrogen electrode layer 6.

[0038] The gas diffusion layer 5 is a porous body having electrical conductivity. The gas diffusion layer 5 electrically connects the metal support 10 and the hydrogen electrode layer 6. The gas diffusion layer 5 also supplies and exhausts gas between each communication hole 11 and the hydrogen electrode layer 6. Specifically, the gas diffusion layer 5 supplies the source gas supplied from each communication hole 11 to the hydrogen electrode layer 6, and exhausts the product gas generated in the hydrogen electrode layer 6 to each communication hole 11.

[0039] The gas diffusion layer 5 includes a conductive material. The gas diffusion layer 5 may include a substrate for supporting the conductive material. The conductive material may be a metal material such as Ni (nickel) or Fe (iron), or a conductive ceramic material. The substrate may be YSZ, CSZ, ScSZ, GDC, SDC, (La,Sr)(Cr,Mn)O3, (La,Sr)TiO3, Sr2(Fe,Mo)2O6, (La,Sr)VO3, (La,Sr)FeO3, LDC (lanthanum doped ceria), LSGM (lanthanum gallate), or a mixed material of two or more of these. The substrate may be insulating.

[0040] The method for forming the gas diffusion layer 5 is not particularly limited, and may be a firing method, a spray coating method (such as a thermal spray method, an aerosol deposition method, an aerosol gas deposition method, a powder jet deposition method, a particle jet deposition method, or a cold spray method), a PVD method (such as a sputtering method or a pulsed laser deposition method), or a CVD method.

[0041] [Hydrogen electrode layer 6] The hydrogen electrode layer 6 is an example of a "first electrode layer" according to the present invention. The hydrogen electrode layer 6 is disposed on the gas diffusion layer 5. The hydrogen electrode layer 6 is sandwiched between the gas diffusion layer 5 and the electrolyte layer .

[0042] A source gas is supplied to the hydrogen electrode layer 6 via each of the communication holes 11 and each of the through holes 51. The source gas contains at least H2O.

[0043] When the raw material gas contains only H2O, the hydrogen electrode layer 6 produces H2 from the raw material gas in accordance with the electrochemical reaction of water electrolysis shown in the following formula (1).

[0044] Hydrogen electrode layer 6: H2O+2e - →H2+O 2- (1)

[0045] When the raw gas contains CO in addition to H2O, the hydrogen electrode layer 6 converts H2, CO, and O2 from the raw gas in accordance with the electrochemical reactions of co-electrolysis shown in the following formulas (2), (3), and (4). 2- Generate.

[0046] Hydrogen electrode layer 6: CO2+H2O+4e - →CO+H2+2O 2- (2) Electrochemical reaction of H2O: H2O+2e - →H2+O 2- (3) Electrochemical reaction of CO2: CO2+2e - →CO+O 2- (4)

[0047] The hydrogen electrode layer 6 is a porous body having electrical conductivity. The hydrogen electrode layer 6 has gas diffusibility. A raw material gas is supplied to the hydrogen electrode layer 6 from the gas diffusion layer 5. The product gas generated in the hydrogen electrode layer 6 is discharged to the flow path 30a via each of the communication holes 11 and each of the through holes 51.

[0048] The hydrogen electrode layer 6 includes a conductive material. Examples of the conductive material that can be used include metal materials such as Ni (nickel) and Fe (iron), and conductive ceramic materials. In the case of co-electrolysis, Ni also functions as a thermal catalyst that promotes the thermal reaction between the generated H2 and the CO2 contained in the raw gas to maintain an appropriate gas composition for methanation, reverse water gas shift reaction, and the like.

[0049] When the conductive material is made of a metal material, the conductive material exists in an oxide state (e.g., NiO) in an oxidizing atmosphere and exists in a metal state (e.g., Ni) in a reducing atmosphere. The hydrogen electrode layer 6 undergoes a dimensional change accompanying oxidation and reduction.

[0050] The hydrogen electrode layer 6 includes an oxide ion conductive material. The oxide ion conductive material is an example of the "ion conductive material" according to the present invention. As the oxide ion conductive material, YSZ, CSZ, ScSZ, GDC, SDC, (La,Sr)(Cr,Mn)O3, (La,Sr)TiO3, Sr2(Fe,Mo)2O6, (La,Sr)VO3, (La,Sr)FeO3, LDC, LSGM, and a mixed material of two or more of these materials can be used.

[0051] In this embodiment, the hydrogen electrode layer 6 has a single-layer structure made of a single composition, but may have a multi-layer structure made of different compositions.

[0052] The thickness of the hydrogen electrode layer 6 is not particularly limited, but may be, for example, 1 μm or more and 500 μm or less.

[0053] In this specification, the term "thickness" refers to the size in the thickness direction. The thickness direction is a direction perpendicular to a plane direction parallel to the hydrogen electrode layer side surface 71 of the electrolyte layer 7. The plane direction is a direction parallel to an approximation line of the hydrogen electrode layer side surface 71 obtained by the least squares method in a cross section of the electrolyte layer 7. The thickness direction may coincide with the Z-axis direction shown in FIGS. 1 and 2.

[0054] The method for forming the hydrogen electrode layer 6 is not particularly limited, and a firing method, a spray coating method, a PVD method, a CVD method, or the like can be used.

[0055] [Electrolyte layer 7] The electrolyte layer 7 is disposed between the hydrogen electrode layer 6 and the oxygen electrode layer 9. In this embodiment, the reaction prevention layer 8 is disposed between the electrolyte layer 7 and the oxygen electrode layer 9, and therefore the electrolyte layer 7 is sandwiched between the hydrogen electrode layer 6 and the reaction prevention layer 8. The electrolyte layer 7 has a hydrogen electrode layer side surface 71 connected to the hydrogen electrode layer 6.

[0056] The electrolyte layer 7 covers the hydrogen electrode layer 6 and also covers the region of the first main surface 12 of the metal support 10 that is exposed from the gas diffusion layer 5 .

[0057] The electrolyte layer 7 is formed by discharging the O 2- to the oxygen electrode layer 9. The electrolyte layer 7 is made of a dense material having oxide ion conductivity. The electrolyte layer 7 can be made of, for example, YSZ (yttria-stabilized zirconia, e.g., 8YSZ), GDC (gadolinium-doped ceria), ScSZ (scandia-stabilized zirconia), SDC (samarium-doped ceria), LSGM (lanthanum gallate), or the like.

[0058] The porosity of the electrolyte layer 7 is not particularly limited, but may be, for example, 0.1% to 7%. The thickness of the electrolyte layer 7 is not particularly limited, but may be, for example, 1 μm to 100 μm.

[0059] The method for forming the electrolyte layer 7 is not particularly limited, and a baking method, a spray coating method, a PVD method, a CVD method, or the like can be used.

[0060] [Reaction prevention layer 8] The reaction prevention layer 8 is disposed between the electrolyte layer 7 and the oxygen electrode layer 9. The reaction prevention layer 8 is disposed on the opposite side of the electrolyte layer 7 to the hydrogen electrode layer 6. The reaction prevention layer 8 prevents the constituent elements of the electrolyte layer 7 from reacting with the constituent elements of the oxygen electrode layer 9 to form a layer with high electrical resistance.

[0061] The reaction prevention layer 8 is made of an oxide ion conductive material, and may be made of GDC, SDC, or the like.

[0062] The porosity of the reaction prevention layer 8 is not particularly limited, but may be, for example, 0.1% to 50%. The thickness of the reaction prevention layer 8 is not particularly limited, but may be, for example, 1 μm to 50 μm.

[0063] The method for forming the reaction prevention layer 8 is not particularly limited, and a baking method, a spray coating method, a PVD method, a CVD method, or the like can be used.

[0064] [Oxygen electrode layer 9] The oxygen electrode layer 9 is an example of a "second electrode layer" according to the present invention. The oxygen electrode layer 9 is disposed on the opposite side of the hydrogen electrode layer 6 with respect to the electrolyte layer 7. In this embodiment, the reaction prevention layer 8 is disposed between the electrolyte layer 7 and the oxygen electrode layer 9, and therefore the oxygen electrode layer 9 is connected to the reaction prevention layer 8. If the reaction prevention layer 8 is not disposed between the electrolyte layer 7 and the oxygen electrode layer 9, the oxygen electrode layer 9 is connected to the electrolyte layer 7.

[0065] The oxygen electrode layer 9 reacts with O 2 transferred from the hydrogen electrode layer 6 through the electrolyte layer 7 in accordance with the chemical reaction of the following formula (5): 2- produces O2 from

[0066] Oxygen electrode layer 9:2O 2- →O2+4e - (5)

[0067] The oxygen electrode layer 9 is a porous body having oxide ion conductivity and electrical conductivity. The oxygen electrode layer 9 can be made of a composite material of one or more of (La,Sr)(Co,Fe)O3, (La,Sr)FeO3, La(Ni,Fe)O3, (La,Sr)CoO3, and (Sm,Sr)CoO3 and an oxide ion conductive material (such as GDC).

[0068] The porosity of the oxygen electrode layer 9 is not particularly limited, but may be, for example, 20% to 60%. The thickness of the oxygen electrode layer 9 is not particularly limited, but may be, for example, 1 μm to 100 μm.

[0069] The method for forming the oxygen electrode layer 9 is not particularly limited, and a baking method, a spray coating method, a PVD method, a CVD method, or the like can be used.

[0070] [Flow path member 30] The flow path member 30 is joined to the second main surface 13 of the metal support 10. The flow path member 30 forms a flow path 30a between itself and the metal support 10. A source gas is supplied to the flow path 30a. The source gas supplied to the flow path 30a is supplied to the hydrogen electrode layer 6 of the cell main body 20 through each communication hole 11 of the metal support 10.

[0071] The flow path member 30 can be made of, for example, an alloy material. The flow path member 30 may be formed of the same material as the metal support 10. In this case, the flow path member 30 may be substantially integral with the metal support 10.

[0072] The flow path member 30 has a frame 31 and an interconnector 32. The frame 31 is an annular member that surrounds the side of the flow path 30a. The frame 31 is joined to the second main surface 13 of the metal support 10. The interconnector 32 is a plate-like member for electrically connecting an external power source or another electrolysis cell to the electrolysis cell 1 in series. The interconnector 32 is joined to the frame 31.

[0073] In this embodiment, the frame 31 and the interconnector 32 are separate members, but the frame 31 and the interconnector 32 may be an integrated member.

[0074] (Detailed configuration of gas diffusion layer 5) The detailed configuration of the gas diffusion layer 5 will be described with reference to Fig. 3. Fig. 3 is a partially enlarged view of Fig. 2.

[0075] The through holes 51 of the gas diffusion layer 5 have gap spaces 51a that penetrate between the first main surface 12 of the metal support 10 and the hydrogen electrode layer 6. This provides flexibility to the metal support 10, and therefore suppresses stress concentration on the gas diffusion layer 5 when the hydrogen electrode layer 6 undergoes a dimensional change due to oxidation-reduction. This suppresses damage to the gas diffusion layer 5 (peeling from the metal support 10 and the hydrogen electrode layer 6, and cracks in the gas diffusion layer 5). Furthermore, because the through holes 51 have gap spaces 51a, gas can be smoothly supplied and discharged between the through holes 51 and the hydrogen electrode layer 6.

[0076] The gap space 51a is preferably formed in an annular shape. That is, in Fig. 3, a pair of gap spaces 51a formed on both sides in the planar direction of the through hole 51 are preferably integrally connected. This can further suppress the concentration of stress on the gas diffusion layer 5, and therefore can further suppress the occurrence of damage to the gas diffusion layer 5.

[0077] The gap space 51a is preferably tapered in the surface direction toward the deepest part P1 of the gap space 51a. This increases the area of ​​the exposed surface 54 of the hydrogen electrode layer 6 that is exposed in the gap space 51a, making it possible to more smoothly supply and exhaust gas between the through hole 51 and the gas diffusion layer 5. The deepest part P1 is the tip of the gap space 51a in the surface direction and indicates the position that is deepest in the gas diffusion layer 5 in the surface direction.

[0078] It is preferable that the exposed surface 54 of the hydrogen electrode layer 6 is curved. This allows the curved exposed surface 54 to absorb the stress applied to the gas diffusion layer 5, thereby further preventing damage to the gas diffusion layer 5.

[0079] The gas diffusion layer 5 preferably has a first extension portion 5a sandwiched in the thickness direction between the gap space 51a and the hydrogen electrode layer 6. This makes it possible to increase the contact area between the gas diffusion layer 5 and the hydrogen electrode layer 6, thereby improving the bonding between the gas diffusion layer 5 and the hydrogen electrode layer 6.

[0080] The first extension portion 5a is preferably tapered in a direction away from the deepest portion P1 of the gap space 51a in the planar direction, thereby making it possible to prevent cracks from occurring in the gas diffusion layer 5 starting from the tip of the first extension portion 5a.

[0081] The gas diffusion layer 5 preferably has a second extension portion 5b sandwiched in the thickness direction between the gap space 51a and the metal support 10. This makes it possible to increase the contact area between the gas diffusion layer 5 and the metal support 10, thereby improving the bonding between the gas diffusion layer 5 and the metal support 10.

[0082] The second extension portion 5b is preferably tapered in a direction away from the deepest portion P1 of the gap space 51a in the planar direction, thereby making it possible to prevent cracks from occurring in the gas diffusion layer 5 starting from the tip of the second extension portion 5b.

[0083] The width W of the gap space 51a in the planar direction is preferably larger than the thickness T of the gas diffusion layer 5 in the thickness direction. This can further suppress the concentration of stress on the gas diffusion layer 5, thereby further suppressing damage to the gas diffusion layer 5. From this viewpoint, it is particularly preferable that the width W of the gap space 51a is 10 μm or more.

[0084] The width W of the gap space 51a is the distance in the planar direction between the deepest part P1 of the gap space 51a and an inner end Q1 of the metal support 10. When the regions of the metal support 10 facing each other across the communication hole 11 are defined as the inner circumferential surface 14, the inner end Q1 of the metal support 10 is the position on the inner circumferential surface 14 that is closest to the hydrogen electrode layer 6 in a cross section along the thickness direction.

[0085] The thickness T of the gas diffusion layer 5 is calculated by the following method. First, a cross section of the gas diffusion layer 5 along the thickness direction is exposed. Next, a backscattered electron image of the cross section is obtained at 3000 times magnification using an SEM device (FE-SEM JSM-7900F manufactured by JEOL Ltd.). Next, the thickness of the gas diffusion layer 5 is measured at three points on the backscattered electron image that divides the region of the gas diffusion layer 5 in which the gap space 51a does not exist into four equal parts in the surface direction. Then, the thickness T of the gas diffusion layer 5 is calculated by arithmetically averaging the three measured values. The thickness T of the gas diffusion layer 5 can be, for example, 1 μm or more and 50 μm or less.

[0086] As shown in FIG. 3, the metal support 10 may have a base material 10a and an oxide film 10b.

[0087] The substrate 10a is made of the above-mentioned metal material (such as Fe-Cr alloy steel or Ni-Cr alloy steel).

[0088] The oxide film 10b covers the surface of the base material 10a. The oxide film 10b can be made of an oxide of a constituent element of the base material 10a. A representative example of such an oxide is chromium oxide.

[0089] The thickness of the first portion b1 of the oxide film 10b exposed in the communicating hole 11 of the metal support 10 is preferably greater than the thickness of the second portion b2 of the oxide film 10b facing the hydrogen electrode layer 6. This can improve the strength of the region of the metal support 10 surrounding the communicating hole 11, thereby preventing the communicating hole 11 from being distorted.

[0090] The thickness of the first portion b1 is determined by arithmetically averaging the thicknesses of the first portion b1 measured at three locations that divide the first portion b1 into four equal parts in the thickness direction on a backscattered electron image at 3000 magnification, similar to the thickness T of the gas diffusion layer 5 described above. Similarly, the thickness of the second portion b2 is determined by arithmetically averaging the thicknesses of the second portion b2 measured at three locations that divide the second portion b2 into four equal parts in the surface direction on a backscattered electron image at 3000 magnification.

[0091] Here, each of the gas diffusion layer 5 and the hydrogen electrode layer 6 has a plurality of pores therein. The average pore diameter of the plurality of pores in the gas diffusion layer 5 is preferably smaller than the average pore diameter of the plurality of pores in the hydrogen electrode layer 6. In other words, the gas diffusion layer 5 preferably contains more small-diameter pores than the hydrogen electrode layer 6. This can improve the gas diffusibility of the gas diffusion layer 5, thereby making it possible to more smoothly supply and discharge gas between the through-holes 51 and the hydrogen electrode layer 6 via the gas diffusion layer 5.

[0092] The porosity of the gas diffusion layer 5 is preferably larger than the porosity of the hydrogen electrode layer 6. That is, the volume ratio of the gas flow paths in the gas diffusion layer 5 is preferably larger than the volume ratio of the gas flow paths in the hydrogen electrode layer 6. This can further improve the gas diffusibility of the gas diffusion layer 5, thereby making it possible to more smoothly supply and discharge gas between the through-holes 51 and the hydrogen electrode layer 6 via the gas diffusion layer 5.

[0093] The average pore size and porosity in the gas diffusion layer 5 can be obtained as follows. First, hydrogen is supplied to the gas diffusion layer 5 and the hydrogen electrode layer 6 while the electrolytic cell 1 is heated to 750°C, thereby reducing the gas diffusion layer 5 and the hydrogen electrode layer 6. Next, the electrolytic cell 1 is cooled in a reducing atmosphere, and the electrolytic cell 1 is cut along the thickness direction to expose the cross sections of the gas diffusion layer 5 and the hydrogen electrode layer 6. Next, the cross sections are precision machine polished, and then ion milling processing is performed using an IM4000 manufactured by Hitachi High-Technologies Corporation. Next, an SEM image is obtained by using an FE-SEM (Field Emission Scanning Electron Microscope) using an in-lens secondary electron detector, at a magnification (for example, 5000 to 30000 times) at which the pores can be confirmed. Next, an analysis image is obtained in which the parts displayed in black on the SEM image (corresponding to the pores) are highlighted by performing image analysis using image analysis software HALCON manufactured by MVTec (Germany). Next, the circle equivalent diameters of each pore (diameter of a circle having the same area as the area of ​​the pore) are arithmetically averaged to calculate the average pore diameter in the gas diffusion layer 5. In addition, the porosity of the gas diffusion layer 5 is calculated by dividing the total area of ​​the pores (gas phase) by the area of ​​the entire analysis image (solid phase).

[0094] The average pore size and porosity of the hydrogen electrode layer 6 can be calculated in the same manner as for the gas diffusion layer 5.

[0095] The gas diffusion layer 5 can be formed as follows. First, the base material 10a of the metal support 10 is prepared, and a paste containing a desired oxide is applied to the surface of the base material 10a. In this case, the thickness of the applied paste may be increased in the area of ​​the surface of the base material 10a that is exposed to the through holes 11. Next, a pore-forming material having a desired shape and size is arranged on the first main surface 12 of the metal support 10 so as to surround the opening of the through hole 11. Next, a paste containing a constituent material of the gas diffusion layer 5 is applied to the area of ​​the first main surface 12 of the metal support 10 where the pore-forming material is not arranged, thereby forming a compact of the gas diffusion layer 5. Next, the hydrogen electrode layer 6 is arranged on the compact of the gas diffusion layer 5 and sintered (800 to 1500°C, 1 to 5 hours), thereby forming the gas diffusion layer 5 having the through holes 51 including the gap spaces 51a.

[0096] (Modification of the embodiment) Although the embodiments of the present invention have been described above, the present invention is not limited to these, and various modifications are possible without departing from the spirit of the present invention.

[0097] For example, in the above embodiment, the electrolysis cell 1 has been described as an example of an electrochemical cell, but the electrochemical cell is not limited to an electrolysis cell. An electrochemical cell is a general term for an element in which a pair of electrodes are arranged so that an electromotive force is generated from an overall oxidation-reduction reaction in order to convert electrical energy into chemical energy, and an element for converting chemical energy into electrical energy. Therefore, the electrochemical cell includes, for example, a fuel cell that uses oxide ions or protons as a carrier. [Explanation of symbols]

[0098] 1 Electrolysis cell 10 Metal support 11 Communication hole 12 First main surface 13 Second main surface 20 Cell body 5 Gas diffusion layer 51 Through hole 51a Interstitial space 52 First connection surface 53 Second connection surface 54 Exposed surface 6 Hydrogen electrode layer 7 Electrolyte layer 8. Reaction prevention layer 9 Oxygen Polar Layer 30 Flow path member 30a Flow path

Claims

1. a metal support having a first main surface, a second main surface provided on an opposite side to the first main surface, and a plurality of communication holes opening into the first main surface and the second main surface; A cell main body portion disposed on the first main surface; Equipped with each of the plurality of communication holes penetrates the metal support in a thickness direction from the first main surface to the second main surface; The cell body portion is a gas diffusion layer disposed on the first main surface; a first electrode layer disposed on the gas diffusion layer; A second electrode layer; an electrolyte layer disposed between the first electrode layer and the second electrode layer; having the gas diffusion layer has through holes communicating with the communication holes, The through hole has a gap space extending into a gap between the first main surface and the first electrode layer. Electrochemical cell.

2. The gap space is tapered toward the deepest portion of the gap space in a plane direction perpendicular to the thickness direction of the gas diffusion layer.

10. The electrochemical cell of claim 1.

3. the gas diffusion layer has an exposed surface exposed to the gap space, The exposed surface is curved.

3. The electrochemical cell of claim 2.

4. the gas diffusion layer has a first extension portion sandwiched between the gap space and the first electrode layer in a thickness direction of the gas diffusion layer; 10. The electrochemical cell of claim 1.

5. The gas diffusion layer has a second extension portion sandwiched between the gap space and the metal support in a thickness direction of the gas diffusion layer.

10. The electrochemical cell of claim 1.

6. The width of the gap space in a surface direction perpendicular to the thickness direction of the gas diffusion layer is greater than the thickness of the gas diffusion layer in the thickness direction.

10. The electrochemical cell of claim 1.

7. The width of the gap space in a plane direction perpendicular to the thickness direction of the gas diffusion layer is 10 μm or more.

10. The electrochemical cell of claim 1.

8. The metal support has a substrate and an oxide film covering a surface of the substrate, a thickness of a first portion of the oxide film exposed in the communicating hole is greater than a thickness of a second portion of the oxide film facing the first electrode layer; 10. The electrochemical cell of claim 1.

9. an average pore diameter of the first pores of the gas diffusion layer is smaller than an average pore diameter of the second pores of the first electrode layer; 10. The electrochemical cell of claim 1.

10. The porosity of the gas diffusion layer is greater than the porosity of the first electrode layer.

10. The electrochemical cell of claim 9.

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