Electrochemical cell

Abstract

This electrochemical cell comprises a metal plate, a cell body, a first oxide protrusion and a first non-oxide protrusion. The metal plate has a first main surface, a second main surface, a first through-hole and a second through-hole. The cell body is positioned on the first main surface of the metal plate. The cell body has a first electrode layer, a second electrode layer and an electrolyte layer. The electrolyte later is positioned between the first electrode layer and the second electrode layer. The first oxide protrusion is formed of a material containing an oxide. The first oxide protrusion is located on an inner wall surface of the first through-hole. The first non-oxide protrusion is formed of a material containing a non-oxide. The first non-oxide protrusion is located on an inner wall surface of the second through-hole.

Description

electrochemical cell

[0001] The present invention relates to electrochemical cells.

[0002] In electrochemical cells such as electrolysis cells or fuel cells, a structure in which a cell body is supported by a metal plate is known. For example, an electrochemical cell disclosed in Patent Document 1 has an electrode layer, an electrolyte layer, and a counter electrode layer stacked in this order on a metal plate. The metal plate has through holes for supplying a raw material gas to the electrode layer.

[0003] International Publication No. 2018 / 181926

[0004] In the electrochemical cell configured as described above, a source gas such as water vapor or fuel gas is supplied to the cell main body through through-holes formed in the metal plate. It is preferable to improve the diffusibility of the source gas supplied to the cell main body through the through-holes. Therefore, an object of the present invention is to improve the diffusibility of the source gas supplied to the cell main body.

[0005] The electrochemical cell according to the first aspect comprises a metal plate, a cell main body, first oxide protrusions, and first non-oxide protrusions. The metal plate has a first main surface, a second main surface, a first through hole, and a second through hole. The cell main body is disposed on the first main surface of the metal plate. The cell main body has a first electrode layer, a second electrode layer, and an electrolyte layer. The electrolyte layer is disposed between the first electrode layer and the second electrode layer. The first oxide protrusions are made of a material containing an oxide. The first oxide protrusions are disposed on the inner wall surface of the first through hole. The first non-oxide protrusions are made of a material containing a non-oxide. The first non-oxide protrusions are disposed on the inner wall surface of the second through hole.

[0006] According to this configuration, the raw material gas flowing through each through-hole collides with the first oxide protrusions or the first non-oxide protrusions, generating a turbulent flow. As a result, the diffusibility of the raw material gas supplied to the cell main body through each through-hole can be improved. Even if the inside of the flow path through which the raw material gas flows becomes an oxidizing atmosphere, the first oxide protrusions are made of a material containing an oxide and do not undergo phase transformation, so a turbulent flow can be generated stably. Even if the inside of the flow path becomes a reducing atmosphere, the first non-oxide protrusions are made of a material containing a non-oxide and do not undergo phase transformation, so a turbulent flow can be generated stably.

[0007] The electrochemical cell according to the second aspect is the electrochemical cell according to the first aspect, but is configured as follows: At least one of the first oxide protrusions and the first non-oxide protrusions is annular and extends circumferentially on the inner wall surface. With this configuration, making at least one of the first oxide protrusions and the first non-oxide protrusions annular increases symmetry and improves mechanical reliability against thermal stress generated between each protrusion and the metal plate.

[0008] The electrochemical cell according to the third aspect is the electrochemical cell according to the first or second aspect, but is configured as follows: At least one of the first oxide protrusions and the first non-oxide protrusions is made of a material having a higher Young's modulus than the metal plate. This configuration prevents deformation of each protrusion due to thermal stress and maintains the effect of improving gas diffusion.

[0009] The electrochemical cell according to a fourth aspect is the electrochemical cell according to any one of the first to third aspects, and is configured as follows: The first oxide protrusions and the first non-oxide protrusions are arranged on the inner wall surface at the end on the second main surface side. With this configuration, the source gas flowing through the source gas flow channels formed on the second main surface side can be efficiently introduced into each of the through holes in the metal plate.

[0010] An electrochemical cell according to a fifth aspect is the electrochemical cell according to any one of the first to fourth aspects, further comprising second oxide protrusions. The second oxide protrusions are made of a material containing oxide. The second oxide protrusions are arranged on the inner wall surface of the first through hole closer to the first main surface than the first oxide protrusions. According to this configuration, providing the second oxide protrusions in addition to the first oxide protrusions makes it easier to generate turbulence, thereby improving gas diffusion.

[0011] An electrochemical cell according to a sixth aspect is the electrochemical cell according to any one of the first to fifth aspects, further comprising second non-oxide protrusions. The second non-oxide protrusions are made of a material containing a non-oxide. The second non-oxide protrusions are arranged on the inner wall surface of the second through hole closer to the first main surface than the first non-oxide protrusions. With this configuration, providing the second non-oxide protrusions in addition to the first non-oxide protrusions makes it easier to generate turbulence, thereby improving gas diffusion.

[0012] An electrochemical cell according to a seventh aspect is the electrochemical cell according to any one of the first to sixth aspects, further comprising second oxide protrusions. The second oxide protrusions are made of a material containing an oxide. The second oxide protrusions are arranged on the inner wall surface of the second through hole closer to the first main surface than the first non-oxide protrusions. With this configuration, even if one protrusion is destroyed by a change in the atmosphere, the other protrusion remains, thereby ensuring the generation of turbulence.

[0013] An electrochemical cell according to an eighth aspect is the electrochemical cell according to any one of the first to seventh aspects, further comprising second non-oxide protrusions. The second non-oxide protrusions are made of a material containing a non-oxide. The second non-oxide protrusions are arranged on the inner wall surface of the first through hole closer to the first main surface than the first oxide protrusions. With this configuration, even if one protrusion is destroyed due to a change in the atmosphere, the other protrusion remains, thereby ensuring the generation of turbulence.

[0014] An electrochemical cell according to a ninth aspect is the electrochemical cell according to any one of the first to eighth aspects, configured as follows: The first oxide protrusions are made of ceramic.

[0015] An electrochemical cell according to a tenth aspect is the electrochemical cell according to any one of the first to ninth aspects, configured as follows: The first non-oxide protrusions are made of metal.

[0016] An electrochemical cell according to an eleventh aspect is the electrochemical cell according to any one of the first to tenth aspects, and is configured as follows. The electrochemical cell includes a plurality of first through holes in which first oxide protrusions are formed, and a plurality of second through holes in which first non-oxide protrusions are formed. The metal plate has a supply port side region and an outlet port side region. The supply port side region is located on the supply port side of a flow path for a source gas supplied to the cell main body through the first through holes and the second through holes. The outlet port side region is located on the outlet port side of the flow path. The ratio of the first through holes to the second through holes is higher in the supply port side region than in the outlet port side region. In this case, the electrochemical cell is preferably an electrolytic cell. In cases where the supply port side of the source gas has a higher oxygen partial pressure than the outlet side of the source gas, such as in an electrolytic cell, providing more first oxide protrusions on the supply port side and more first non-oxide protrusions on the outlet port side can suppress phase transformation of the protrusions, thereby achieving a stable gas diffusion effect.

[0017] An electrochemical cell according to a twelfth aspect is the electrochemical cell according to any one of the first to tenth aspects, and is configured as follows. The electrochemical cell includes a plurality of first through holes in which first oxide protrusions are formed, and a plurality of second through holes in which first non-oxide protrusions are formed. The metal plate has a supply port side region and an outlet port side region. The supply port side region is located on the supply port side of a flow path for a raw material gas supplied to the cell main body through the first and second through holes. The outlet port side region is located on the outlet side of the flow path. The ratio of the first through holes to the second through holes is smaller in the supply port side region than in the outlet port side region. In this case, the electrochemical cell is preferably a fuel cell. In cases where the raw material gas outlet side has a higher oxygen partial pressure than the raw material gas supply side, such as a fuel cell, providing more first oxide protrusions on the outlet port side and more first non-oxide protrusions on the supply port side can suppress phase transformation of the protrusions, thereby achieving a stable gas diffusion effect.

[0018] According to the present invention, the diffusibility of the source gas supplied to the cell main body can be improved.

[0019] 1 is a cross-sectional view showing an electrolytic cell; a plan view of a metal plate; an enlarged cross-sectional view showing the periphery of a first through hole; an enlarged bottom view showing the periphery of the first through hole; a plan view of a metal plate for illustrating each region; an enlarged cross-sectional view showing the periphery of a second through hole; an enlarged bottom view showing the periphery of the second through hole; a cross-sectional view showing an electrolytic cell according to a modified example; an enlarged cross-sectional view showing the periphery of a first through hole of an electrolytic cell according to a modified example; an enlarged cross-sectional view showing the periphery of a second through hole of an electrolytic cell according to a modified example; an enlarged cross-sectional view showing the periphery of a second through hole of an electrolytic cell according to a modified example; an enlarged cross-sectional view showing the periphery of a first through hole of an electrolytic cell according to a modified example; an enlarged cross-sectional view showing the periphery of a through hole of an electrolytic cell according to a modified example; an enlarged cross-sectional view showing the periphery of a through hole of an electrolytic cell according to a modified example; an enlarged cross-sectional view showing the periphery of a through hole of an electrolytic cell according to a modified example.

[0020] An electrolytic cell (an example of an electrochemical cell) according to this embodiment will be described below with reference to the drawings. In this embodiment, a solid oxide electrolytic cell (SOEC) will be used as an example of the electrolytic cell. FIG. 1 is a cross-sectional view showing the electrolytic cell. In the following description, the solid oxide electrolytic cell may be abbreviated as "cell."

[0021] 1, the cell 100 includes a metal plate 2, a cell body 3, first oxide protrusions 4, and first non-oxide protrusions 5. The cell 100 further includes a flow path member 6.

[0022] [Flow Channel Member] The flow channel member 6 is joined to the metal plate 2. The flow channel member 6 has a flow channel 61. The flow channel 61 is formed on the surface of the flow channel member 6 that faces the metal plate 2. In this embodiment, the flow channel 61 is formed on the upper surface of the flow channel member 6. The flow channel 61 opens toward the metal plate 2. The flow channel 61 is connected to a manifold or the like (not shown). In this embodiment, for example, a source gas is supplied from left to right through the flow channel 61.

[0023] The flow path member 6 may be made of the same material as the metal plate 2, for example.

[0024] The flow path member 6 has a frame 62 and an interconnector 63. The frame 62 is an annular member that surrounds the side of the flow path 61. The frame 62 is joined to the metal plate 2. The interconnector 63 is a plate-like member that electrically connects the electrolytic cell 100 to an external power source or another electrolytic cell in series. The interconnector 63 is joined to the frame 62.

[0025] In the flow path member 6 according to this embodiment, the frame body 62 and the interconnector 63 are separate members, but the frame body 62 and the interconnector 63 may be configured as a single member.

[0026] [Metal Plate] The metal plate 2 supports the cell main body 3. In this embodiment, the metal plate 2 is formed in a plate shape. The metal plate 2 may be flat or curved. The metal plate 2 may have any thickness as long as it can maintain the strength of the cell 100, and the thickness is not particularly limited, but may be, for example, 0.1 mm or more and 2.0 mm or less.

[0027] The metal plate 2 has a first main surface 21, a second main surface 22, and a plurality of through holes 23. The first main surface 21 of the metal plate 2 supports the cell main body 3. The second main surface 22 of the metal plate 2 faces the flow path 61. In this embodiment, the upper surface of the metal plate 2 is the first main surface 21, and the lower surface of the metal plate 2 is the second main surface 22. A frame 62 of the flow path member 6 is connected to the second main surface 22 of the metal plate 2.

[0028] As shown in FIG. 2 , the metal plate 2 has a rectangular shape in a plan view. However, the metal plate 2 may have another shape, such as a circular shape. The plurality of through holes 23 are arranged along the longitudinal and lateral directions of the metal plate 2. The plurality of through holes 23 are formed in a region of the metal plate 2 that is bonded to a hydrogen electrode layer 31 (described later). The through holes 23 are open to the first main surface 21. The through holes 23 are also open to the second main surface 22. That is, the through holes 23 extend from the first main surface 21 to the second main surface 22 of the metal plate 2 in the thickness direction of the metal plate 2. The through holes 23 penetrate the metal plate 2 in the thickness direction. The through holes 23 are in communication with the flow paths 61 of the flow path member 6. The source gas flowing through the flow paths 61 is supplied to the hydrogen electrode layer 31 via the through holes 23.

[0029] The through-hole 23 has a substantially circular shape in a plan view. The area of ​​the through-hole 23 in a plan view is, for example, 0.00005 mm ２ More than 1 mm ２ The diameter of the through-hole 23 can be, for example, 10 μm or more and 1000 μm or less. The through-hole 23 may be rectangular in plan view. The height of the through-hole 23 is greater than the thickness of the hydrogen electrode layer 31. The height of the through-hole 23 can be, for example, 100 μm or more and 2000 μm or less. The height of the through-hole 23 refers to the dimension in the vertical direction in FIG. 1 .

[0030] The through holes 23 can be formed by mechanical processing (for example, punching), laser processing, chemical processing (for example, etching), etc. The metal plate 2 can also be made of porous metal to provide gas permeability.

[0031] The plurality of through holes 23 includes a plurality of first through holes 23 a and a plurality of second through holes 23 b. The first through holes 23 a are through holes among the plurality of through holes 23 that have first oxide protrusions 4 formed on their inner wall surfaces. The second through holes 23 b are through holes among the plurality of through holes 23 that have first non-oxide protrusions 5 formed on their inner wall surfaces.

[0032] The metal plate 2 is made of a metal material. For example, the metal plate 2 is made of an alloy material containing Cr (chromium). Examples of such a metal material include Fe-Cr alloy steel (stainless steel, etc.) and Ni-Cr alloy steel. The Cr content in the metal plate 2 is not particularly limited, but can be set to 4% by mass or more and 30% by mass or less.

[0033] The metal plate 2 may contain Ti (titanium) and Zr (zirconium). The Ti content in the metal plate 2 is not particularly limited, but may be 0.01 mol % or more and 1.0 mol % or less. The Zr content in the metal plate 2 is not particularly limited, but may be 0.01 mol % or more and 0.4 mol % or less. The metal plate 2 may contain Ti in the form of TiO ２ (titania), or Zr may be contained as ZrO ２ It may be contained as (zirconia).

[0034] The metal plate 2 may have an oxide film on its surface. Specifically, the metal plate 2 may have a chromium oxide film on its surface. The oxide film covers at least a portion of the surface of the metal plate 2. The oxide film may cover at least a portion of the surface of the metal plate 2, but may also cover substantially the entire surface. The oxide film may also cover the inner wall surfaces of the through holes 23. The thickness of the oxide film is not particularly limited, but may be, for example, 0.1 μm or more and 20 μm or less.

[0035] [Cell Body] As shown in Fig. 1 , the cell body 3 is disposed on the first main surface 21 of the metal plate 2. The cell body 3 has a hydrogen electrode layer 31 (cathode), an electrolyte layer 32, a reaction prevention layer 33, and an oxygen electrode layer 34 (anode). The hydrogen electrode layer 31, the electrolyte layer 32, the reaction prevention layer 33, and the oxygen electrode layer 34 are stacked in this order from the metal plate 2 side. Note that the cell body 3 does not necessarily have to have the reaction prevention layer 33. The hydrogen electrode layer 31 is an example of a first electrode layer of the present invention, and the oxygen electrode layer 34 is an example of a second electrode layer of the present invention.

[0036] [Hydrogen Electrode Layer] The hydrogen electrode layer 31 is supported by the metal plate 2. Specifically, the hydrogen electrode layer 31 is disposed on the first main surface 21 of the metal plate 2. The thickness t of the hydrogen electrode layer 31 can be, for example, 1 μm or more and 100 μm or less. The hydrogen electrode layer 31 is thinner than the metal plate 2. As shown in FIG. 2 , the hydrogen electrode layer 31 is provided so as to cover the region of the metal plate 2 where the plurality of through holes 23 are provided.

[0037] The hydrogen electrode layer 31 is preferably porous. There are no particular restrictions on the porosity of the hydrogen electrode layer 31, but it can be set to, for example, 20% or more and 70% or less.

[0038] The hydrogen electrode layer 31 is made of a porous material having electron conductivity. The hydrogen electrode layer 31 may have oxide ion conductivity. For example, the hydrogen electrode layer 31 may be made of 8 mol % yttria-stabilized zirconia (8YSZ), calcia-stabilized zirconia (CSZ), scandia-stabilized zirconia (ScSZ), gadolinium-doped ceria (GDC), samarium-doped ceria (SDC), (La,Sr)(Cr,Mn)O ３ , (La,Sr)TiO ３ , Sr ２ (Fe, Mo) ２ O ６ , (La, Sr)VO ３ , (La,Sr)FeO ３ , a mixed material of two or more of these, or a composite of one or more of these with NiO.

[0039] The method for forming the hydrogen electrode layer 31 is not particularly limited, and it can be formed by a baking method, a spray coating method, a PVD method, a CVD method, or the like.

[0040] The hydrogen electrode layer 31 is configured to generate hydrogen by an electrolytic reaction. A source gas is supplied to the hydrogen electrode layer 31 through the through-holes 23. The source gas contains at least H ２ Contains O.

[0041] The raw material gas is H ２ When only O is contained, the hydrogen electrode layer 31 converts H from the raw material gas according to the electrochemical reaction of water electrolysis shown in the following formula (1): ２Hydrogen electrode layer 31: H ２ O + 2e － →H ２ +O ２－ ...(1)

[0042] The raw material gas is H ２ O plus CO ２ In this case, the hydrogen electrode layer 31 converts the source gas into H according to the co-electrolytic electrochemical reactions shown in the following formulas (2), (3), and (4). ２ , CO and O ２－ Hydrogen electrode layer 31: CO ２ +H ２ O+4e － →CO+H ２ +20 ２－ ... (2) H ２ Electrochemical reaction of O: H ２ O + 2e － →H ２ +O ２－ ... (3) CO ２ Electrochemical reaction of: CO ２ +2e － →CO+O ２－ ...(4)

[0043] 1, the electrolyte layer 32 is disposed between the hydrogen electrode layer 31 and the oxygen electrode layer 34. In this embodiment, since the cell body 3 has the reaction prevention layer 33, the electrolyte layer 32 is interposed between the hydrogen electrode layer 31 and the reaction prevention layer 33. There are no particular limitations on the thickness of the electrolyte layer 32, but it can be, for example, 3 μm or more and 50 μm or less.

[0044] In this embodiment, the electrolyte layer 32 is disposed so as to cover the entire hydrogen electrode layer 31. The outer periphery of the electrolyte layer 32 is joined to the first main surface 21 of the metal plate 2. This ensures airtightness between the hydrogen electrode layer 31 side and the oxygen electrode layer 34 side, eliminating the need for a separate seal between the metal plate 2 and the electrolyte layer 32.

[0045] The electrolyte layer 32 absorbs the O generated in the hydrogen electrode layer 31. ２－to the oxygen electrode layer 34. The electrolyte layer 32 has oxide ion conductivity. The electrolyte layer 32 is made of a dense material. The porosity of the electrolyte layer 32 is approximately 0% or more and 7% or less. The electrolyte layer 32 is a sintered body made of a dense material that has ion conductivity but no electronic conductivity. The electrolyte layer 32 can be made of, for example, 8YSZ, GDC, ScSZ, SDC, LSGM (lanthanum gallate), or the like.

[0046] The method for forming the electrolyte layer 32 is not particularly limited, and it can be formed by a baking method, a spray coating method, a PVD method, a CVD method, or the like.

[0047] [Reaction Prevention Layer] The reaction prevention layer 33 is disposed on the electrolyte layer 32. The reaction prevention layer 33 is interposed between the electrolyte layer 32 and the oxygen electrode layer 34. There are no particular limitations on the thickness of the reaction prevention layer 33, but it can be, for example, 1 μm or more and 50 μm or less. The reaction prevention layer 33 prevents the constituent materials of the oxygen electrode layer 34 and the electrolyte layer 32 from reacting with each other to form a reaction layer with high electrical resistance.

[0048] The reaction prevention layer 33 is made of a material having oxide ion conductivity. The reaction prevention layer 33 can be made of a ceria-based material such as GDC or SDC. The porosity of the reaction prevention layer 33 is not particularly limited, but can be, for example, 0.1% or more and 50% or less. The method for forming the reaction prevention layer 33 is not particularly limited, and the layer can be formed by a baking method, a spray coating method, a PVD method, a CVD method, or the like.

[0049] [Oxygen Electrode Layer] The oxygen electrode layer 34 is disposed on the opposite side of the electrolyte layer 32 from the hydrogen electrode layer 31. In this embodiment, since the cell 100 has the reaction prevention layer 33, the oxygen electrode layer 34 is disposed on the reaction prevention layer 33.

[0050] The oxygen electrode layer 34 is preferably porous. The porosity of the oxygen electrode layer 34 is not particularly limited, but may be, for example, 20% to 70%. The thickness of the oxygen electrode layer 34 is not particularly limited, but may be, for example, 1 μm to 100 μm.

[0051] The oxygen electrode layer 34 is made of a porous material having oxide ion conductivity and electron conductivity, such as (La, Sr)(Co, Fe)O. ３ , (La,Sr)FeO ３ , La(Ni,Fe)O ３ , (La,Sr)CoO ３ , and (Sm,Sr)CoO ３ The insulating layer may be formed of a composite of one or more of the above and an oxide ion conducting material (such as GDC).

[0052] The method for forming the oxygen electrode layer 34 is not particularly limited, and it can be formed by a baking method, a spray coating method, a PVD method, a CVD method, or the like.

[0053] The oxygen electrode layer 34 reacts with O 2 transferred from the hydrogen electrode layer 31 via the electrolyte layer 32 in accordance with the chemical reaction of the following formula (5): ２－ From O ２ Oxygen electrode layer 34: 2O ２－ →O ２ +4e － ...(5)

[0054] [First Oxide Protrusions] FIG. 3 is a cross-sectional view showing details of the first through hole 23a and its surroundings, in which the first oxide protrusions 4 are formed, and FIG. 4 is a bottom view of the first through hole 23a as viewed from the second main surface. As shown in FIGS. 3 and 4 , the first oxide protrusions 4 are disposed on the inner wall surface of the first through hole 23a. The first oxide protrusions 4 are annular and extend circumferentially on the inner wall surface of the first through hole 23a. That is, the first oxide protrusions 4 extend continuously in the circumferential direction. The first oxide protrusions 4 may also extend intermittently in the circumferential direction. The first oxide protrusions 4 do not necessarily have to extend circumferentially. The first oxide protrusions 4 do not have to be formed directly on the inner wall surface of the first through hole 23a. For example, if an oxide film is formed on the inner wall surface of the first through hole 23a, the first oxide protrusions 4 are formed on the oxide film.

[0055] The first oxide protrusions 4 are arranged on the inner wall surface of the first through hole 23a at the end on the second main surface 22 side. Specifically, the first through hole 23a has an end on the first main surface 21 side and an end on the second main surface 22 side in the axial direction. Of both axial end portions of the first through hole 23a, the first oxide protrusions 4 are not formed on the end on the first main surface 21 side, but are formed on the end on the second main surface 22 side. Note that the first oxide protrusions 4 may be arranged on the first main surface 21 side.

[0056] The first oxide protrusions 4 protrude from the inner wall surface of the first through hole 23 a toward the center. The height of the first oxide protrusions 4 is, for example, 1 μm or more and 100 μm or less. The height of the first oxide protrusions 4 is the dimension from the inner wall surface of the first through hole 23 a toward the center.

[0057] The first oxide protrusions 4 are made of a material having a higher Young's modulus than the metal plate 2. The first oxide protrusions 4 are made of a material containing oxide. More specifically, the first oxide protrusions 4 are made of a material consisting of only oxide. For example, the first oxide protrusions 4 are made of oxide ceramics. More specifically, the first oxide protrusions 4 are made of Cr ２ O ３ , (Mn, Cr) ３ O ４ , (Mn, Cr, Fe) ３ O ４ , (Cr, Fe) ２ O ３ , Fe ２ O ３ , Fe ３ O ４ , Al ２ O ３ , ZrO ２ , or CeO ２ It can be configured by the following.

[0058] The first oxide protrusions 4 may be made of the same material as the oxide film formed on the inner wall surface of the first through hole 23a. In this case, the first oxide protrusions 4 are the parts that protrude relative to other parts. In other words, the height of the first oxide protrusions 4 is greater than the thickness of the oxide film. In this case, the height of the first oxide protrusions 4 refers to the height from the inner wall surface of the first through hole 23a.

[0059] The first oxide protrusions 4 can be formed by applying an oxide paste to the inner wall surface of the first through hole 23 a in the circumferential direction using a precision nozzle dispenser and then firing the oxide paste. Alternatively, the first oxide protrusions 4 can be formed by locally laser-heating the inner wall surface of the first through hole 23 a in the circumferential direction to form a thick oxide film.

[0060] As shown in Fig. 5, the first oxide protrusions 4 are preferably formed in the through holes 23 arranged in the supply port side region A1. For example, the region A in the metal plate 2 in which the through holes 23 are formed is divided into three equal parts along the direction in which the source gas flows (the supply direction). For example, in Fig. 5, the source gas flows from left to right, so the region A is divided into three equal parts along the left-right direction. The region close to the source gas supply port (the region on the left in Fig. 5) is defined as the supply port side region A1. The region close to the source gas exhaust port (the region on the right in Fig. 5) is defined as the exhaust port side region A2, and the region between the supply port side region A1 and the exhaust port side region A2 is defined as the central region A3.

[0061] The first oxide protrusions 4 are preferably formed in all of the through holes 23 in the supply port side region A1, but do not necessarily have to be formed in all of the through holes 23 in the supply port side region A1. For example, the first oxide protrusions 4 are preferably formed in 50% or more of the through holes 23 in the supply port side region A1. It is preferable that the first oxide protrusions 4 are formed in at least 10% of the through holes 23 in the supply port side region A1. It is also possible that the first oxide protrusions 4 are formed in the through holes 23 in the discharge port side region A2 or the central region A3.

[0062] [First non-oxide protrusion] Figure 6 is a cross-sectional view showing details around the second through hole 23b in which the first non-oxide protrusion 5 is formed, and Figure 7 is a bottom view of the second through hole 23b in which the first non-oxide protrusion 5 is formed, viewed from the second main surface side.

[0063] As shown in Figures 6 and 7, the first non-oxide protrusions 5 are disposed on the inner wall surface of the second through hole 23b. The first non-oxide protrusions 5 are annular and extend circumferentially on the inner wall surface of the second through hole 23b. That is, the first non-oxide protrusions 5 extend continuously in the circumferential direction. The first non-oxide protrusions 5 may also extend intermittently in the circumferential direction. The first non-oxide protrusions 5 do not have to extend in the circumferential direction. The first non-oxide protrusions 5 do not have to be formed directly on the inner wall surface of the second through hole 23b. For example, if an oxide film is formed on the inner wall surface of the second through hole 23b, the first non-oxide protrusions 5 are formed on the oxide film.

[0064] The first non-oxide protrusions 5 are arranged on the inner wall surface of the second through hole 23b at the end on the second main surface 22 side. Specifically, the second through hole 23b has an end on the first main surface 21 side and an end on the second main surface 22 side in the axial direction. Of both axial end portions of the second through hole 23b, the first non-oxide protrusions 5 are not formed on the end on the first main surface 21 side, but are formed on the end on the second main surface 22 side. Note that the first non-oxide protrusions 5 may be arranged on the first main surface 21 side.

[0065] The first non-oxide protrusions 5 protrude from the inner wall surface of the second through-hole 23b toward the center. The height of the first non-oxide protrusions 5 is, for example, 1 μm or more and 100 μm or less. The height of the first non-oxide protrusions 5 refers to the dimension from the inner wall surface of the second through-hole 23b toward the center.

[0066] The first non-oxide protrusions 5 are made of a material containing a non-oxide. More specifically, the first non-oxide protrusions 5 are made of a material containing a metal. For example, the first non-oxide protrusions 5 are made of a metal. The first non-oxide protrusions 5 may contain an oxide in addition to the metal. More specifically, the first non-oxide protrusions 5 may be made such that the surface of an oxide is covered with a metal. Specifically, examples of the metal contained in the first non-oxide protrusions 5 include Fe, Co, Ni, and Cu. Examples of the oxide contained in the first non-oxide protrusions 5 include Cr. ２ O ３ , (Mn, Cr) ３ O４ , (Mn, Cr, Fe) ３ O ４ , (Cr, Fe) ２ O ３ , Fe ３ O ４ , Al ２ O ３ , ZrO ２ , and CeO ２ The first non-oxide protrusions 5 may be made of a material having a higher Young's modulus than the metal plate 2 .

[0067] The first non-oxide protrusions 5 can be formed by applying a non-oxide paste to the inner wall surface of the second through hole 23b in the circumferential direction using a precision nozzle dispenser and firing the paste in a controlled atmosphere to prevent oxidation of the non-oxide. Alternatively, the first non-oxide protrusions 5 can be formed by selectively laser sintering the non-oxide paste applied to the inner wall surface of the second through hole 23b.

[0068] As shown in Fig. 5, the first non-oxide protrusions 5 are preferably formed in the through holes 23 located in the outlet side region A2. The first non-oxide protrusions 5 are preferably formed in all of the through holes 23 in the outlet side region A2, but do not necessarily have to be formed in all of the through holes 23 in the outlet side region A2. For example, the first non-oxide protrusions 5 are preferably formed in 50% or more of the through holes 23 in the outlet side region A2. It is preferable that the first non-oxide protrusions 5 are formed in at least 10% of the through holes 23 in the outlet side region A2. The first non-oxide protrusions 5 may also be formed in the through holes 23 in the supply port side region A1 or the central region A3.

[0069] The number of first through holes 23a is greater than the number of second through holes 23b in the supply port side region A1 and less than the number of second through holes 23b in the exhaust port side region A2. That is, the ratio of the first through holes 23a to the second through holes 23b in the supply port side region A1 is greater than the ratio of the first through holes 23a to the second through holes 23b in the exhaust port side region A2. This ratio can be calculated, for example, on a cut surface obtained by cutting the metal plate 2 along the arrangement direction of the multiple through holes 23 and the supply direction of the source gas, as shown by the dashed dotted line in FIG. 5 . Note that the second through holes 23b may not be formed in the supply port side region A1. Furthermore, the first through holes 23a may not be formed in the exhaust port side region A2.

[0070] [Modifications] 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.

[0071] (a) In the above embodiment, the hydrogen electrode layer 31 is disposed on the metal plate 2, but the configuration of the cell body 3 is not limited to this. For example, as shown in FIG. 8 , the oxygen electrode layer 34 may be disposed on the metal plate 2. In this case, the oxygen electrode layer 34, the reaction prevention layer 33, the electrolyte layer 32, and the hydrogen electrode layer 31 are disposed in this order from the metal plate 2 side. The electrolyte layer 32 is formed so as to cover the oxygen electrode layer 34 and the reaction prevention layer 33. The reaction prevention layer 33 does not necessarily have to be formed.

[0072] (b) As shown in Figure 9, the electrolysis cell 100 may further include second oxide protrusions 7. The second oxide protrusions 7 are arranged on the inner wall surfaces of the first through holes 23a closer to the first main surface 21 than the first oxide protrusions 4. For example, the second oxide protrusions 7 are arranged in the axial center of the first through holes 23a. The second oxide protrusions 7 are arranged at a distance from the hydrogen electrode layers 31. The second oxide protrusions 7 are also arranged at a distance from the first oxide protrusions 4.

[0073] The second oxide protrusions 7 are formed on the inner wall surfaces of the first through holes 23a, similar to the first oxide protrusions 4. The height of the second oxide protrusions 7 may be formed to be lower than the height of the first oxide protrusions 4. The second oxide protrusions 7 are made of a material containing an oxide. The second oxide protrusions 7 are made of a material having a higher Young's modulus than the metal plate 2. The second oxide protrusions 7 can be made of the same material as the first oxide protrusions 4. Furthermore, the second oxide protrusions 7 can be formed by the same method as the first oxide protrusions 4.

[0074] 10 , the second oxide protrusions 7 may be disposed on the inner wall surface of the second through-hole 23b closer to the first main surface 21 than the first non-oxide protrusions 5. For example, the second oxide protrusions 7 are disposed in the axial center of the second through-hole 23b. The second oxide protrusions 7 are disposed at a distance from the hydrogen electrode layer 31. The second oxide protrusions 7 are also disposed at a distance from the first non-oxide protrusions 5.

[0075] (c) As shown in Figure 11, the electrolysis cell 100 may further include second non-oxide protrusions 8. The second non-oxide protrusions 8 are arranged on the inner wall surface of the second through-hole 23b closer to the first main surface 21 than the first non-oxide protrusions 5. For example, the second non-oxide protrusions 8 are arranged in the axial center of the second through-hole 23b. The second non-oxide protrusions 8 are arranged at a distance from the hydrogen electrode layer 31. The second non-oxide protrusions 8 are also arranged at a distance from the first non-oxide protrusions 5.

[0076] The second non-oxide protrusions 8 are formed on the inner wall surface of the second through-hole 23b, similar to the first non-oxide protrusions 5. The height of the second non-oxide protrusions 8 may be formed to be lower than the height of the first non-oxide protrusions 5. The second non-oxide protrusions 8 are made of a material containing a non-oxide. The second non-oxide protrusions 8 can be made of the same material as the first non-oxide protrusions 5. Furthermore, the second non-oxide protrusions 8 can be formed by the same method as the first non-oxide protrusions 5.

[0077] 12 , the second non-oxide protrusions 8 may be disposed on the inner wall surface of the first through-hole 23 a closer to the first main surface 21 than the first oxide protrusions 4. For example, the second non-oxide protrusions 8 are disposed in the axial center of the first through-hole 23 a. The second non-oxide protrusions 8 are disposed at a distance from the hydrogen electrode layer 31. The second non-oxide protrusions 8 are also disposed at a distance from the first oxide protrusions 4.

[0078] (d) The first oxide protrusions 4 and the first non-oxide protrusions 5 are not limited to the shapes described above. For example, the first oxide protrusions 4 and the first non-oxide protrusions 5 may have a triangular cross section as shown in FIG. 13 or another shape. Furthermore, the second oxide protrusions 7 and the second non-oxide protrusions 8 are not limited to the shapes described above. They may have a triangular cross section as shown in FIG. 14 or another shape.

[0079] (e) As shown in Fig. 15 , the hydrogen electrode layer 31 may extend into the through-hole 23. In this case, the hydrogen electrode layer 31 may fill only a portion of the through-hole 23 as shown in Fig. 15 , may fill the entire through-hole 23, or may protrude from the through-hole 23 onto the second main surface 22 side.

[0080] (f) In the above embodiment, the first oxide protrusions 4 and the first non-oxide protrusions 5 are arranged at the end of the through hole 23 on the second main surface 22 side, but the positions of the first oxide protrusions 4 and the first non-oxide protrusions 5 are not limited to this. For example, the first oxide protrusions 4 and the first non-oxide protrusions 5 may be arranged in the axial center of the through hole 23, or may be arranged in other positions.

[0081] (g) In the above embodiment, the first oxide protrusions 4 and the first non-oxide protrusions 5 are not disposed on the second main surface 22 of the metal plate 2, but the configuration of the first oxide protrusions 4 is not limited to this. For example, as shown in Figure 16, the first oxide protrusions 4 and the first non-oxide protrusions 5 may be formed on the inner wall surface of the through hole 23 and also on the second main surface 22. In this case, the first oxide protrusions 4 and the first non-oxide protrusions 5 are disposed so as to cover corners 221 formed by the inner wall surface of the through hole 23 and the second main surface 22.

[0082] (h) In the above embodiment, the electrolysis cell 100 has been described as an example of an electrochemical cell, but the electrochemical cell may be a cell other than an electrolysis cell. For example, it may be a fuel cell such as a solid oxide fuel cell. In this case, the first electrode layer may be a fuel electrode (anode), and the second electrode layer may be an air electrode (cathode).

[0083] In this case, the first oxide protrusions 4 are preferably formed in the through holes 23 arranged in the outlet-side region A2. Furthermore, the first non-oxide protrusions 5 are preferably formed in the through holes 23 arranged in the supply-side region A1. Specifically, the number of first through holes 23a is preferably smaller than the number of second through holes 23b in the supply-side region A1 and greater than the number of second through holes 23b in the outlet-side region A2. That is, the ratio of the first through holes 23a to the second through holes 23b in the supply-side region A1 is preferably smaller than the ratio of the first through holes 23a to the second through holes 23b in the outlet-side region A2.

[0084] (i) In the electrolysis cell 100 of the above embodiment, more first through holes 23a than second through holes 23b are formed in the supply port side region A1, and more second through holes 23b than first through holes 23a are formed in the discharge port side region A2, but the configuration of the electrolysis cell 100 is not limited to this. For example, more second through holes 23b than first through holes 23a may be formed in the supply port side region A1, and more first through holes 23a than second through holes 23b may be formed in the discharge port side region A2.

[0085] 2: Metal plate 21: First main surface 22: Second main surface 23: Through hole 23a: First through hole 23b: Second through hole 3: Cell main body 31: Hydrogen electrode layer 32: Electrolyte layer 34: Oxygen electrode layer 4: First oxide protrusion 5: First non-oxide protrusion 7: Second oxide protrusion 8: Second non-oxide protrusion 61: Flow path 100: Electrolytic cell A1: Supply port side region A2: Discharge port side region

Claims

1. a metal plate having a first main surface, a second main surface, a first through hole, and a second through hole; a cell main body portion having a first electrode layer, a second electrode layer, and an electrolyte layer disposed between the first electrode layer and the second electrode layer, the cell main body portion being disposed on the first main surface of the metal plate; a first oxide protrusion that is made of a material containing an oxide and that is disposed on an inner wall surface of the first through hole; a first non-oxide protrusion that is made of a material containing a non-oxide and that is disposed on an inner wall surface of the second through hole; Equipped with At least one of the first oxide protrusion and the first non-oxide protrusion is annular and extends circumferentially on the inner wall surface. Electrochemical cell.

2. At least one of the first oxide protrusions and the first non-oxide protrusions is made of a material having a higher Young's modulus than the metal plate.

10. The electrochemical cell of claim 1.

3. At least one of the first oxide protrusion and the first non-oxide protrusion is disposed on an end of the inner wall surface on the second main surface side.

10. The electrochemical cell of claim 1.

4. a second oxide protrusion made of a material containing an oxide and disposed on an inner wall surface of the first through hole closer to the first main surface than the first oxide protrusion; 10. The electrochemical cell of claim 1.

5. a second non-oxide protrusion made of a material containing a non-oxide and disposed on an inner wall surface of the second through hole closer to the first main surface than the first non-oxide protrusion; 10. The electrochemical cell of claim 1.

6. a second oxide protrusion made of a material containing an oxide and disposed on an inner wall surface of the second through hole closer to the first main surface than the first non-oxide protrusion; 10. The electrochemical cell of claim 1.

7. a second non-oxide protrusion made of a material containing a non-oxide and disposed on an inner wall surface of the first through hole closer to the first main surface than the first oxide protrusion; 10. The electrochemical cell of claim 1.

8. the first oxide protrusion is made of a material including ceramics; 10. The electrochemical cell of claim 1.

9. the first non-oxide protrusion is made of a material containing a metal; 10. The electrochemical cell of claim 1.

10. a plurality of the first through holes in which the first oxide protrusions are formed; a plurality of the second through holes in which the first non-oxide protrusions are formed; Equipped with the metal plate has a supply port side region arranged on a supply port side of a flow path for a source gas supplied to the cell main body portion through the first through hole and the second through hole, and an exhaust port side region arranged on an exhaust port side of the flow path, a ratio of the first through holes to the second through holes is larger in the supply port side region than in the discharge port side region; 10. The electrochemical cell of claim 1.

11. a plurality of the first through holes in which the first oxide protrusions are formed; a plurality of the second through holes in which the first non-oxide protrusions are formed; Equipped with the metal plate has a supply port side region arranged on a supply port side of a flow path for a source gas supplied to the cell main body portion through the first through hole and the second through hole, and an exhaust port side region arranged on an exhaust port side of the flow path, a ratio of the first through holes to the second through holes is smaller in the supply port side region than in the discharge port side region; 10. The electrochemical cell of claim 1.

12. A metal plate having a first main surface, a second main surface, a first through hole, and a second through hole; a cell main body portion having a first electrode layer, a second electrode layer, and an electrolyte layer disposed between the first electrode layer and the second electrode layer, the cell main body portion being disposed on the first main surface of the metal plate; a first oxide protrusion that is made of a material containing an oxide and that is disposed on an inner wall surface of the first through hole; a first non-oxide protrusion that is made of a material containing a non-oxide and that is disposed on an inner wall surface of the second through hole; Equipped with At least one of the first oxide protrusions and the first non-oxide protrusions is made of a material having a higher Young's modulus than the metal plate. Electrochemical cell.

13. A metal plate having a first main surface, a second main surface, a plurality of first through holes, and a plurality of second through holes; a cell main body portion having a first electrode layer, a second electrode layer, and an electrolyte layer disposed between the first electrode layer and the second electrode layer, the cell main body portion being disposed on the first main surface of the metal plate; a first oxide protrusion that is made of a material containing an oxide and that is disposed on an inner wall surface of the first through hole; a first non-oxide protrusion that is made of a material containing a non-oxide and that is disposed on an inner wall surface of the second through hole; Equipped with the metal plate has a supply port side region arranged on a supply port side of a flow path for a source gas supplied to the cell main body portion through the first through hole and the second through hole, and an exhaust port side region arranged on an exhaust port side of the flow path, a ratio of the first through holes to the second through holes is larger in the supply port side region than in the discharge port side region; Electrochemical cell.

14. A metal plate having a first main surface, a second main surface, a plurality of first through holes, and a plurality of second through holes; a cell main body portion having a first electrode layer, a second electrode layer, and an electrolyte layer disposed between the first electrode layer and the second electrode layer, the cell main body portion being disposed on the first main surface of the metal plate; a first oxide protrusion that is made of a material containing an oxide and that is disposed on an inner wall surface of the first through hole; a first non-oxide protrusion that is made of a material containing a non-oxide and that is disposed on an inner wall surface of the second through hole; Equipped with the metal plate has a supply port side region arranged on a supply port side of a flow path for a source gas supplied to the cell main body portion through the first through hole and the second through hole, and an exhaust port side region arranged on an exhaust port side of the flow path, a ratio of the first through holes to the second through holes is smaller in the supply port side region than in the discharge port side region; Electrochemical cell.