JP6757434B1 - Electrochemical cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress peeling of a cell main body from a metal support. An electrochemical cell 1 includes a cell body and a metal support 4. The cell body has a first electrode layer 5, a second electrode layer, and an electrolyte layer 7. The electrolyte layer 7 is arranged between the first electrode layer 5 and the second electrode layer. The metal support 4 supports the cell body. The metal support 4 has a support surface 42, a supply hole 41, and a protrusion 43. The support surface 42 supports the cell body. The supply hole 41 opens in the support surface 42. The protrusion 43 protrudes from the corner formed by the support surface 42 and the inner wall surface of the supply hole 41. The protrusion 43 extends inside the cell body. [Selection diagram] Fig. 2

Description

The present invention relates to an electrochemical cell.

In an electrochemical cell such as a fuel cell, a structure in which a cell body is supported by a metal support is known. For example, in the electrochemical cell disclosed in Patent Document 1, an electrode layer, an intermediate layer, an electrolyte layer, a reaction prevention layer, and a counter electrode layer facing each other are laminated in this order on a metal support. The metal support has through holes for supplying gas to the electrode layer.

International Publication No. 2018/181926

Since the metal support has a coefficient of thermal expansion different from that of the cell body, there is a problem that the electrode layer formed on the metal support may be peeled off from the metal support due to repeated operation and stop of the electrochemical cell. is there.

Therefore, an object of the present invention is to suppress peeling of the cell body from the metal support.

The electrochemical cell according to a certain aspect of the present invention includes a cell body and a metal support. The cell body has a first electrode layer, a second electrode layer, and an electrolyte layer. The electrolyte layer is arranged between the first electrode layer and the second electrode layer. The metal support supports the cell body. The metal support has a support surface, supply holes, and protrusions. The support surface supports the cell body. The supply hole opens in the support surface. The protrusion protrudes from the corner formed by the support surface and the inner wall surface of the supply hole. The protrusion extends inside the cell body.

According to this configuration, since the protrusion of the metal support extends inside the cell body, the joint strength between the metal support and the cell body is improved, and the cell body is prevented from peeling off from the metal support. can do. Further, this protrusion protrudes from the corner between the inner wall surface of the supply hole and the support surface. Since the cell main body is easily peeled off from the metal support starting from this corner, the peeling of the cell main body can be further suppressed by the protrusion protruding from the corner.

Preferably, the protrusions extend in the direction the support surface faces.

Preferably, at least a part of the cell body is in the supply hole. According to this configuration, the joint strength between the cell body and the metal support can be further improved.

Preferably, the protrusion extends within the cell body that has entered the supply hole.

Preferably, the first electrode layer is arranged on the support surface of the metal support.

Preferably, the first electrode layer has recesses formed on the surface opposite the surface facing the metal support. The recess overlaps with the supply hole in the thickness direction of the first electrode layer. According to this configuration, the gas supplied from the supply hole tends to spread in the in-plane direction of the first electrode layer.

Preferably, the first electrode layer functions as an anode and the second electrode layer functions as a cathode.

Preferably, the electrolyte layer has oxygen ion conductivity.

Preferably, the electrolyte layer has hydroxide ion conductivity.

According to the present invention, peeling of the cell body from the metal support can be suppressed.

The cross-sectional view which shows the structure of the fuel cell which concerns on 1st Embodiment. An enlarged cross-sectional view showing the details of the fuel cell according to the first embodiment. The figure which shows typically the flow of the gas in the fuel cell which concerns on 1st Embodiment. The cross-sectional view which shows the structure of the fuel cell which concerns on 2nd Embodiment. The enlarged sectional view which shows the detail of the fuel cell which concerns on 2nd Embodiment. The figure which shows typically the flow of the gas in the fuel cell which concerns on 2nd Embodiment. The enlarged sectional view which shows the detail of the fuel cell which concerns on the modification of 1st and 2nd Embodiment. The enlarged sectional view which shows the detail of the fuel cell which concerns on the modification of 1st and 2nd Embodiment. The enlarged sectional view which shows the detail of the fuel cell which concerns on the modification of 1st and 2nd Embodiment. The enlarged sectional view which shows the detail of the fuel cell which concerns on the modification of 1st and 2nd Embodiment. The cross-sectional view which shows the structure of the fuel cell which concerns on the modification of 1st Embodiment.

1. 1. 1st Embodiment [Solid oxide fuel cell]
The solid oxide fuel cell 1 uses O ^2- (oxygen ion) as a carrier. The solid oxide fuel cell 1 is an example of the "electrochemical cell" according to the present invention. In the following description, the solid oxide fuel cell is abbreviated as "cell".

FIG. 1 is a cross-sectional view showing the configuration of the cell 1 according to the first embodiment. The cell 1 includes a cell main body 10 and a metal support 4. Further, the cell 1 further includes a flow path member 3. The cell body 10 has a first electrode layer 5, an intermediate layer 6, an electrolyte layer 7, a reaction prevention layer 8, and a second electrode layer 9.

[Flow path member 3]
The flow path member 3 is joined to the metal support 4. The flow path member 3 has a flow path 31. The flow path 31 is formed on a surface of the flow path member 3 facing the metal support 4. In the present embodiment, the flow path 31 is formed on the upper surface of the flow path member 3. The flow path 31 opens toward the metal support 4. The flow path 31 is connected to a manifold (not shown) or the like. In this embodiment, fuel gas (for example, hydrogen gas) is supplied to the flow path 31.

The flow path member 3 can be made of, for example, an alloy material. The flow path member 3 may be made of the same material as the metal support 4.

[Metal support 4]
The metal support 4 supports the cell body 10. In the present embodiment, the metal support 4 is formed in a plate shape, but the metal support 4 is not limited to this. The metal support 4 may have other shapes such as a tubular shape or a box shape.

The metal support 4 has a plurality of supply holes 41 and a support surface 42. The support surface 42 of the metal support 4 supports the cell body 10. In this embodiment, the upper surface of the metal support 4 is the support surface 42.

The plurality of supply holes 41 are formed in a region of the metal support 4 to be joined to the first electrode layer 5. The supply hole 41 is open to the support surface 42. Specifically, the supply hole 41 penetrates the metal support 4 in the thickness direction. The supply hole 41 communicates with the flow path 31 of the flow path member 3.

The fuel gas flowing through the flow path 31 is supplied to the first electrode layer 5 through the supply hole 41. At least a part of the cell body 10 is inserted into the supply hole 41. Specifically, a part of the first electrode layer 5 of the cell main body 10 has entered the supply hole 41.

The supply hole 41 can be formed by machining (for example, punching), laser processing, or chemical processing (for example, etching). The supply hole 41 has, for example, a circular shape in the thickness direction of the metal support 4. Further, the metal support 4 may use a porous metal in order to have gas permeability.

The metal support 4 is formed in a plate shape. The metal support 4 may have a flat plate shape or a curved plate shape. The thickness of the metal support 4 is not particularly limited as long as it can maintain the strength of the cell 1, but can be, for example, 0.1 mm to 2.0 mm.

The metal support 4 is made of a metal material. For example, the metal support 4 is made of an alloy material containing Cr (chromium). As such a metal material, Fe—Cr based alloy steel (stainless steel or the like), Ni—Cr based alloy steel, or the like can be used. The Cr content in the metal support 4 is not particularly limited, but may be 4 to 30% by mass.

The metal support 4 may contain Ti (titanium) or Al (aluminum). The content of Ti in the metal support 4 is not particularly limited, but 0.01 to 1.0 at. Can be%. The content of Al in the metal support 4 is not particularly limited, but 0.01 to 0.4 at. Can be%. The metal support 4 may contain Ti as TiO ₂ (titania) or Al as Al ₂ O ₃ (alumina).

The metal support 4 may have a chromium oxide film on its surface. The chromium oxide film covers at least a part of the surface of the metal support 4. The chromium oxide film may cover at least a part of the surface of the metal support 4, but may cover substantially the entire surface. Further, the chromium oxide film may cover the inner wall surface of the supply hole 41.

The chromium oxide film contains chromium oxide as a main component. In the present embodiment, the phrase "the composition X contains the substance Y as a main component" means that the substance Y accounts for 70% by weight or more of the entire composition X. The thickness of the chromium oxide film is not particularly limited, but can be, for example, 0.1 to 20 μm.

[First electrode layer 5]
The first electrode layer 5 is supported by the metal support 4. Specifically, the first electrode layer 5 is arranged on the support surface 42 of the metal support 4. The first electrode layer 5 is provided so as to cover a region of the metal support 4 in which a plurality of supply holes 41 are provided.

As shown in FIG. 2, a part of the first electrode layer 5 has entered the supply hole 41. Although not particularly limited, the height h1 of the first electrode layer 5 that has entered the supply hole 41 is about 0.5 to 50 μm. The height h1 of the first electrode layer 5 is a distance from the support surface 42.

The first electrode layer 5 is preferably porous. The porosity of the first electrode layer 5 is not particularly limited, but can be, for example, 20% to 70%. The thickness of the first electrode layer 5 is not particularly limited, but may be, for example, 1 μm to 100 μm.

In the present embodiment, a fuel gas (for example, hydrogen gas) is supplied to the first electrode layer 5, and the first electrode layer 5 functions as an anode (fuel electrode). The first electrode layer 5 is composed of a composite material such as NiO-GDC (gadolinium-doped ceria), Ni-GDC, NiO-YSZ (yttria-stabilized zirconia), Ni-YSZ, CuO-CeO ₂ , and Cu-CeO _2. can do.

The method for forming the first electrode layer 5 is not particularly limited, and is a firing method, a spray coating method (spattering method, aerosol deposition method, aerosol gas deposition method, powder jet deposit method, particle jet deposition method, cold spray method). Etc.), PVD method (sputtering method, pulse laser deposition method, etc.), CVD method, etc. Further, the first electrode layer 5 is formed on the support surface 42 of the metal support 4.

[Mesosphere 6]
As shown in FIG. 1, the intermediate layer 6 is arranged on the first electrode layer 5. The intermediate layer 6 is interposed between the first electrode layer 5 and the electrolyte layer 7. The thickness of the intermediate layer 6 is not particularly limited, but can be, for example, 1 μm to 100 μm.

The intermediate layer 6 preferably has oxide ion (oxygen ion) conductivity. It is more preferable that the intermediate layer 6 has electron conductivity. The intermediate layer 6 can be composed of YSZ, GDC, SSZ (scandium-stabilized zirconia), SDC (samarium-doped ceria), or the like. The method for forming the intermediate layer 6 is not particularly limited, and the intermediate layer 6 can be formed by a firing method, a spray coating method, a PVD method, a CVD method, or the like.

[Electrolyte layer 7]
The electrolyte layer 7 is arranged between the first electrode layer 5 and the second electrode layer 9. In the present embodiment, since the cell body 10 has the intermediate layer 6 and the reaction prevention layer 8, the electrolyte layer 7 is interposed between the intermediate layer 6 and the reaction prevention layer 8.

In the present embodiment, the electrolyte layer 7 is formed so as to cover the entire first electrode layer 5, and the outer edge of the electrolyte layer 7 is joined to the support surface 42 of the metal support 4. As a result, mixing of the fuel gas supplied to the first electrode layer 5 and the oxidant gas supplied to the second electrode layer 9 can be suppressed, so that the metal support 4 and the electrolyte layer 7 are separately sealed. You don't have to.

The electrolyte layer 7 has oxide ion conductivity. Specifically, the electrolyte layer 7 has oxygen ion conductivity. The electrolyte layer 7 has a gas barrier property that can suppress the mixing of the oxidant gas and the fuel gas. The electrolyte layer 7 may have a multi-layer structure, but it is preferable that at least one layer is a dense layer. The porosity of the dense layer is preferably 10% or less, more preferably 5% or less, still more preferably 2% or less. The thickness of the electrolyte layer 7 is not particularly limited, but can be, for example, 1 μm to 10 μm.

The electrolyte layer 7 can be composed of YSZ, GDC, SSZ, SDC, LSGM and the like. The method for forming the electrolyte layer 7 is not particularly limited, and the electrolyte layer 7 can be formed by a firing method, a spray coating method, a PVD method, a CVD method, or the like.

[Reaction prevention layer 8]
The reaction prevention layer 8 is arranged on the electrolyte layer 7. The reaction prevention layer 8 is interposed between the electrolyte layer 7 and the second electrode layer 9. The thickness of the reaction prevention layer 8 is not particularly limited, but can be, for example, 1 μm to 100 μm. The reaction prevention layer 8 suppresses the reaction between the constituent material of the second electrode layer 9 and the constituent material of the electrolyte layer 7 to form a high resistance layer.

The reaction prevention layer 8 can be made of a ceria-based material such as GDC or SDC. The method for forming the reaction prevention layer 8 is not particularly limited, and the reaction prevention layer 8 can be formed by a firing method, a spray coating method, a PVD method, a CVD method, or the like.

[Second electrode layer 9]
The second electrode layer 9 is arranged on the opposite side of the first electrode layer 5 with reference to the electrolyte layer 7. In the present embodiment, since the cell 1 has the reaction prevention layer 8, the second electrode layer 9 is arranged on the reaction prevention layer 8.

The second electrode layer 9 is preferably porous. The porosity of the second electrode layer 9 is not particularly limited, but can be, for example, 20% to 70%. The thickness of the second electrode layer 9 is not particularly limited, but can be, for example, 1 μm to 100 μm.

In the present embodiment, an oxidizing agent gas (for example, air) is supplied to the second electrode layer 9, and the second electrode layer 9 functions as a cathode (air electrode). The second electrode layer 9 can be composed of LSCF, LSF, LSC, LNF, LSM and the like. In particular, the second electrode layer 9 preferably contains a perovskite-type oxide containing two or more kinds of elements selected from the group consisting of La, Sr, Sm, Mn, Co and Fe.

The method for forming the second electrode layer 9 is not particularly limited, and the second electrode layer 9 can be formed by a firing method, a spray coating method, a PVD method, a CVD method, or the like. The method for forming the second electrode layer 9 is not particularly limited, and the second electrode layer 9 can be formed by a firing method, a spray coating method, a PVD method, a CVD method, or the like.

[Detailed configuration around the supply hole of the metal support]
As shown in FIG. 2, the metal support 4 has a plurality of protrusions 43. The protrusion 43 protrudes from a corner formed by the support surface 42 and the inner wall surface of the supply hole 41. The protrusion 43 extends within the cell body 10. Specifically, the protrusion 43 extends within the first electrode layer 5. The protrusion 43 extends in the direction in which the support surface 42 faces. That is, the protrusion 43 extends upward in FIG. The height h2 of the protrusion 43 is not particularly limited, but is, for example, about 1 to 50 μm.

The protrusion 43 may be formed continuously along the outer peripheral edge of the supply hole 41, or may be formed intermittently. The protrusion 43 is formed so as to be tapered toward the tip in the cross-sectional shape. The protrusion 43 can be formed, for example, by pressing with a die having a desired protrusion shape.

The first electrode layer 5 has a first main surface 51 and a second main surface 52. The first main surface 51 is a surface facing the metal support 4. That is, the first main surface 51 is a surface that joins with the support surface 42 of the metal support 4. In the present embodiment, the first main surface 51 is the lower surface of the first electrode layer 5.

The second main surface 52 is a surface opposite to the first main surface 51. That is, the second main surface 52 is a surface facing the electrolyte layer 7. The second main surface 52 is joined to the intermediate layer 6. In the present embodiment, the second main surface 52 is the upper surface of the first electrode layer 5.

The first electrode layer 5 has a plurality of recesses 53. The recess 53 is formed on the second main surface 52 of the first electrode layer 5. The recess 53 overlaps with the supply hole 41 in the thickness direction of the first electrode layer 5 (vertical view in FIG. 2). That is, the recess 53 is arranged directly above the supply hole 41.

The depth d of the recess 53 is not particularly limited, but is, for example, about 0.5 to 50 μm. Further, the recess 53 gradually becomes deeper from the outer peripheral edge toward the central portion. The recess 53 has a slope from the deepest portion toward the outer peripheral edge.

Since the recess 53 is arranged directly above the supply hole 41 in this way, as shown in FIG. 3, the gas (for example, fuel gas) supplied from the supply hole 41 to the first electrode layer 5 enters the recess 53. It is easily guided and spreads in the in-plane direction of the first electrode layer 5. Therefore, the gas is likely to be supplied to the interface of the portion other than directly above the supply hole 41. The arrows in FIG. 3 schematically represent the flow of gas.

[Operation of cell 1]
First, while supplying fuel gas from the flow path 31 to the first electrode layer 5 through each supply hole 41 and supplying the oxidant gas to the second electrode layer 9, the cell 1 is operated at an operating temperature (for example, 600). (° C. to 850 ° C.). Then, in the second electrode layer 9, O ₂ (oxygen) reacts with e ⁻ (electrons) to generate O ^2- (oxygen ions). The generated O ^2- move to the first electrode layer 5 through the electrolyte layer 7. The O ^{2- that} has moved to the first electrode layer 5 reacts with H ₂ (hydrogen) contained in the fuel gas to generate H ₂ O (water) and e ⁻ . By such a reaction, an electromotive force is generated between the first electrode layer 5 and the second electrode layer 9.

2. 2. 2nd Embodiment [Solid alkaline fuel cell]
The solid alkaline fuel cell 1 is a type of alkaline fuel cell (AFC) having OH ⁻ (hydroxide ion) as a carrier. The solid alkaline fuel cell 11 is an example of the "electrochemical cell" according to the present invention. In the following description, the solid alkaline fuel cell is abbreviated as "cell".

FIG. 4 is a cross-sectional view showing the configuration of the cell 11 according to the second embodiment. The cell 11 includes a cell body 110 and a metal support 14. Further, the cell 11 further includes a flow path member 13. The cell body 110 has a first electrode layer 15, an electrolyte layer 17, and a second electrode layer 19.

[Flow path member 13]
The flow path member 13 is joined to the metal support 14. The flow path member 13 has a flow path 131. The flow path 131 is formed on a surface of the flow path member 13 facing the metal support 14. In the present embodiment, the flow path 131 is formed on the upper surface of the flow path member 13. The flow path 131 opens toward the metal support 14. The flow path 131 is connected to a manifold (not shown) or the like. In this embodiment, fuel is supplied to the flow path 131.

The flow path member 13 can be made of, for example, an alloy material. The flow path member 13 may be made of the same material as the metal support 14.

[Metal support 14]
The metal support 14 supports the cell body 110. In the present embodiment, the metal support 14 is formed in a plate shape, but the metal support 14 is not limited to this. The metal support 14 may have other shapes such as a tubular shape or a box shape.

The metal support 14 has a plurality of supply holes 141 and a support surface 142. The support surface 142 of the metal support 14 supports the cell body 110. In this embodiment, the upper surface of the metal support 14 is the support surface 142.

The plurality of supply holes 141 are formed in the region of the metal support 14 to be joined to the first electrode layer 15. The supply hole 141 is open to the support surface 142. Specifically, the supply hole 141 penetrates the metal support 14 in the thickness direction. The supply hole 141 communicates with the flow path 131 of the flow path member 13.

The fuel flowing through the flow path 131 is supplied to the first electrode layer 15 through the supply hole 141. At least a part of the cell main body 110 is inserted in the supply hole 141. Specifically, a part of the first electrode layer 15 of the cell main body 110 has entered the supply hole 141.

The supply hole 141 can be formed by machining (for example, punching), laser processing, or chemical processing (for example, etching). The supply hole 141 has, for example, a circular shape in the thickness direction of the metal support 14. Further, as the metal support 14, a porous metal can also be used.

The metal support 14 is formed in a plate shape. The metal support 14 may have a flat plate shape or a curved plate shape. The thickness of the metal support 14 is not particularly limited as long as it can maintain the strength of the cell 11, but can be, for example, 0.1 mm to 2.0 mm.

The metal support 14 is made of a metal material. For example, the metal support 14 is made of an alloy material containing Cr (chromium). As such a metal material, Fe—Cr based alloy steel (stainless steel or the like), Ni—Cr based alloy steel, or the like can be used. The content of Cr in the metal support 14 is not particularly limited, but may be 4 to 30% by mass.

The metal support 14 may contain Ti (titanium) or Al (aluminum). The content of Ti in the metal support 14 is not particularly limited, but 0.01 to 1.0 at. Can be%. The content of Al in the metal support 14 is not particularly limited, but 0.01 to 0.4 at. Can be%. The metal support 14 may contain Ti as TiO ₂ (titania) or Al as Al ₂ O ₃ (alumina).

The metal support 14 may have a chromium oxide film on its surface. The chromium oxide film covers at least a part of the surface of the metal support 14. The chromium oxide film may cover at least a part of the surface of the metal support 14, but may cover substantially the entire surface. Further, the chromium oxide film may cover the inner wall surface of the supply hole 141.

The chromium oxide film contains chromium oxide as a main component. In the present embodiment, the phrase "the composition X contains the substance Y as a main component" means that the substance Y accounts for 70% by weight or more of the entire composition X. The thickness of the chromium oxide film is not particularly limited, but can be, for example, 0.1 to 20 μm.

[First electrode layer 15]
The first electrode layer 15 is supported by the metal support 14. Specifically, the first electrode layer 15 is arranged on the support surface 142 of the metal support 14. The first electrode layer 15 is provided so as to cover the region of the metal support 14 in which the plurality of supply holes 141 are provided.

As shown in FIG. 5, a part of the first electrode layer 15 has entered the supply hole 141. Although not particularly limited, the height h1 of the first electrode layer 15 that has entered the supply hole 141 is about 0.5 to 50 μm. The height h1 of the first electrode layer 15 is a distance from the support surface 142.

The first electrode layer 15 is preferably porous. The porosity of the first electrode layer 15 is not particularly limited, but can be, for example, 20% to 70%. The thickness of the first electrode layer 15 is not particularly limited, but may be, for example, 1 μm to 100 μm.

The first electrode layer 15 is an anode generally called a fuel electrode. In the present embodiment, the first electrode layer 15 is supplied with fuel containing a hydrogen atom (H). The fuel containing a hydrogen atom may contain a fuel compound capable of reacting with hydroxide ions (OH ⁻ ) in the first electrode layer 15, and may be in the form of either a liquid fuel or a gaseous fuel.

Examples of the fuel compound include (i) hydrazine (NH ₂ NH ₂ ), hydrated hydrazine (NH ₂ NH ₂ · H ₂ O), hydrazine carbonate ((NH ₂ NH ₂ ) ₂ CO ₂ ), and hydrazine sulfate (NH). ₂ NH ₂ · H ₂ SO ₄ ), monomethylhydrazine (CH ₃ NHNH ₂ ), dimethylhydrazine ((CH ₃ ) ₂ NNH ₂ , CH ₃ NHNHCH ₃ ), and hydrazines such as carboxylic hydrazine ((NHNH ₂ ) ₂ CO). Class, (ii) urea (NH ₂ CONH ₂ ), (iii) ammonia (NH ₃ ), (iv) imidazole, 1,3,5-triazine, 3-amino-1,2,4-triazole and other heterocycles. Examples thereof include hydroxylamines such as (v) hydroxylamine (NH ₂ OH) and hydroxylamine sulfate (NH ₂ OH · H ₂ SO ₄ ), and combinations thereof. Of these fuel compounds, carbon-free compounds (ie, hydrazine, hydrated hydrazine, hydrazine sulfate, ammonia, hydroxylamine, hydroxylamine sulfate, etc.) are particularly suitable because they do not have the problem of catalyst poisoning by carbon monoxide. is there.

The fuel compound may be used as it is as a fuel, or may be used as a solution dissolved in water and / or an alcohol (for example, a lower alcohol such as methanol, ethanol, propanol or isopropanol). For example, among the above fuel compounds, hydrazine, hydrated hydrazine, monomethylhydrazine and dimethylhydrazine are liquids and can be used as they are as liquid fuels. In addition, hydrazine carbonate, hydrazine sulfate, carboxylic hydrazine, urea, imidazole, and 3-amino-1,2,4-triazole, and hydroxylamine sulfate are solid but soluble in water. 1,3,5-triazine and hydroxylamine are solid but soluble in alcohol. Ammonia is a gas but soluble in water. As described above, the solid fuel compound can be dissolved in water or alcohol and used as a liquid fuel. When the fuel compound is dissolved in water and / or alcohol and used, the concentration of the fuel compound in the solution is, for example, 30 to 99.9% by weight, preferably 66 to 99.9% by weight.

Further, a hydrocarbon-based liquid fuel containing alcohols such as methanol and ethanol and ethers, a hydrocarbon-based gas such as methane, or pure hydrogen can be used as it is as a fuel. In particular, methanol is suitable as the fuel used in the cell 10 according to the present embodiment. Methanol may be in a gaseous state, a liquid state, or a gas-liquid mixed state.

The first electrode layer 15 may include a known anode catalyst used for AFC, and is not particularly limited. Examples of anode catalysts include metal catalysts such as Pt, Ni, Co, Fe, Ru, Sn, and Pd. The metal catalyst is preferably supported on a carrier such as carbon, but may be in the form of an organic metal complex having a metal atom of the metal catalyst as a central metal, or the organic metal complex may be supported as a carrier. Further, a diffusion layer made of a porous material or the like may be arranged on the surface of the anode catalyst. Preferred examples of the first electrode layer 15 and the catalyst constituting the first electrode layer 15 are nickel, cobalt, silver, platinum-supported carbon (Pt / C), platinum ruthenium-supported carbon (PtRu / C), and palladium-supported carbon (Pd / C). , Rodium-supported carbon (Rh / C), nickel-supported carbon (Ni / C), copper-supported carbon (Cu / C), and silver-supported carbon (Ag / C).

The method for producing the first electrode layer 15 is not particularly limited, but for example, the anode catalyst and, if desired, the carrier are mixed with a binder to form a paste, and the paste-like mixture is applied onto the support surface 142 of the metal support 14. Can be formed by

[Electrolyte layer 17]
As shown in FIG. 4, the electrolyte layer 17 is arranged between the first electrode layer 15 and the second electrode layer 19. The electrolyte layer 17 is connected to each of the first electrode layer 15 and the second electrode layer 19.

In the present embodiment, the electrolyte layer 17 is formed so as to cover the entire first electrode layer 15, and the outer edge of the electrolyte layer 17 is joined to the support surface 142 of the metal support 14. As a result, mixing of the fuel supplied to the first electrode layer 15 and the oxidizing agent supplied to the second electrode layer 19 can be suppressed, so that the metal support 14 and the electrolyte layer 17 need to be separately sealed. There is no.

The electrolyte layer 17 has hydroxide ion conductivity. During power generation in the cell 11, the electrolyte layer 17 conducts hydroxide ions (OH ⁻ ) from the second electrode layer 19 side to the first electrode layer 15 side. The hydroxide ion conductivity of the electrolyte layer 17 is not particularly limited, but is preferably 0.1 mS / cm or more, more preferably 0.5 mS / cm or more, still more preferably 1.0 mS / cm or more. The higher the hydroxide ion conductivity of the electrolyte layer 17, the more preferable it is, and the upper limit thereof is not particularly limited, but is, for example, 10 mS / cm.

The electrolyte layer 17 is preferably dense. The relative density of the electrolyte layer 17 calculated by the Archimedes method is not particularly limited, but is preferably 90% or more, more preferably 92% or more, still more preferably 95% or more. The electrolyte layer 17 can be densified by, for example, hydrothermal treatment.

The electrolyte layer 17 can be made of a ceramic material having hydroxide ion conductivity. As such a ceramic material, well-known ceramics having hydroxide ion conductivity can be used, but layered double hydroxide (LDH) described below is particularly suitable.

LDH is M ²⁺ _1-x M ³⁺ _x (OH) ₂ A ⁿ⁻ x / n · mH ₂ O (in the formula, M ²⁺ is a divalent cation, M ³⁺ is a trivalent cation, and A ⁿ⁻ is an n-valent anion, n is an integer of 1 or more, x is 0.1 to 0.4, and m is an arbitrary integer meaning the number of moles of water). Have. Examples of M ²⁺ include Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ni ²⁺ , Co ²⁺ , Fe ²⁺ , Mn ²⁺ , and Zn ²⁺ , and examples of M ³⁺ include Al ³⁺ , Fe ³⁺ , Ti ³⁺ , ^{Y 3+, Ce 3+, Mo 3+} , and ^{Cr 3+} can be mentioned, An ^- and the like ^- _CO ^{3 2-and} OH examples of. As M ²⁺ and M ³⁺ , one type may be used alone or two or more types may be used in combination.

LDH is composed of a plurality of hydroxide basic layers and an intermediate layer interposed between the plurality of hydroxide basic layers. Intermediate layer is composed of an anion and _{H 2} O. The hydroxide basic layer contains, for example, Ni, Al, Ti and OH groups when the metal M is Ni, Al, Ti. Hereinafter, the case where the hydroxide basic layer of LDH contains Ni, Al, Ti and OH groups will be described.

Ni in LDH can take the form of nickel ions. Nickel ions in LDH are typically considered to be Ni ²⁺ , but are not particularly limited as other valences such as Ni ³⁺ are possible. Al in LDH can take the form of aluminum ions. Aluminum ions in LDH are typically considered to be Al ³⁺ , but are not particularly limited as other valences are possible. Ti in LDH can take the form of titanium ions. Titanium ions in LDH are typically considered to be Ti ⁴⁺ , but are not particularly limited as other valences such as Ti ³⁺ are possible. The hydroxide basic layer preferably contains Ni, Al, Ti and OH groups as main components, but may contain other elements or ions, or may contain unavoidable impurities. The unavoidable impurity is an arbitrary element that can be unavoidably mixed in the production method, and can be mixed in LDH from, for example, a raw material or a base material.

Intermediate layer of LDH is composed of anionic and _{H 2} O. The anion is a monovalent or higher anion, preferably a monovalent or divalent ion. Preferably, the anions in LDH contain OH ⁻ and / or CO ₃ ^2- .

As mentioned above, since the valences of Ni, Al and Ti are not always fixed, it is impractical or impossible to specify LDH strictly by a general formula. Assuming that the basic hydroxide layer is mainly composed of Ni ²⁺ , Al ³⁺ , Ti ⁴⁺ and OH groups, LDH is expressed by the general formula: Ni ²⁺ _1-xy Al ³⁺ _x Ti ⁴⁺ _y (OH). _{^{) 2 a n- (x + 2y}} ) / n · mH 2 O ( ^{wherein, a n-n-valent} anion, n is an integer of 1 or more, preferably 1 or 2, 0 <x <1, preferably 0.01 ≦ x ≦ 0.5, 0 <y <1, preferably 0.01 ≦ y ≦ 0.5, 0 <x + y <1, m is 0 or more, typically more than 0 or 1 or more It can be expressed by the basic composition (which is a real number of). However, the above general formula should be understood as "basic composition" to the extent that elements such as Ni ²⁺ , Al ³⁺ , and Ti ⁴⁺ do not impair the basic characteristics of LDH, and other elements or ions (of the same element). It should be understood as replaceable with elements or ions of other valences or elements or ions that can be unavoidably mixed in the process.

[Second electrode layer 19]
The second electrode layer 19 is arranged on the opposite side of the first electrode layer 15 with reference to the electrolyte layer 17. In this embodiment, the second electrode layer 19 is arranged on the electrolyte layer 17.

The second electrode layer 19 is preferably porous. The porosity of the second electrode layer 19 is not particularly limited, but can be, for example, 20% to 70%. The thickness of the second electrode layer 19 is not particularly limited, but may be, for example, 1 μm to 100 μm.

The second electrode layer 19 is a cathode generally called an air electrode. During power generation in cell 10, an oxidizing agent containing oxygen (O ₂ ) is supplied to the second electrode layer 19. As the oxidizing agent, it is preferable to use air, and it is more preferable that the air is humidified. The second electrode layer 19 is a porous body capable of diffusing an oxidizing agent inside.

The second electrode layer 19 is not particularly limited as long as it contains a known cathode catalyst used for AFC. Examples of cathode catalysts include group 8-10 elements (IUPAC format periodic table) such as group 11 elements (Ru, Rh, Pd, Ir, Pt) and group 11 elements (Fe, Co, Ni). Group 10 elements), Group 11 elements such as Cu, Ag, and Au (elements belonging to Group 11 in the periodic table in the IUPAC format), rhodium phthalocyanine, tetraphenylporphyrin, Co-salen, Ni-salen (salen = N, N'-bis (salicylidene) ethylenediamine), silver nitrate, and any combination thereof. The amount of the catalyst supported on the second electrode layer 19 is not particularly limited, but is preferably 0.05 to 10 mg / cm ² , and more preferably 0.05 to 5 mg / cm ² . The cathode catalyst is preferably supported on carbon. Preferred examples of the second electrode layer 19 or the catalyst constituting the second electrode layer 19 are platinum-supported carbon (Pt / C), platinum-cobalt-supported carbon (PtCo / C), palladium-supported carbon (Pd / C), and rhodium-supported carbon (Rh). / C), nickel-supported carbon (Ni / C), copper-supported carbon (Cu / C), and silver-supported carbon (Ag / C).

The method for producing the second electrode layer 19 is not particularly limited, and for example, the cathode catalyst and, if desired, the carrier may be mixed with a binder to form a paste, and the paste-like mixture may be applied onto the electrolyte layer 17. it can.

[Detailed configuration around the supply hole of the metal support]
As shown in FIG. 5, the metal support 14 has a plurality of protrusions 143. The protrusion 143 projects from a corner formed by the support surface 142 and the inner wall surface of the supply hole 141. The protrusion 143 extends inside the cell body 110. Specifically, the protrusion 143 extends within the first electrode layer 15. The protrusion 143 extends in the direction in which the support surface 142 faces. That is, the protrusion 143 extends upward in FIG. The height h2 of the protrusion 143 is not particularly limited, but is, for example, about 1 to 50 μm.

The protrusion 143 may be formed continuously along the outer peripheral edge of the supply hole 141, or may be formed intermittently. The protrusion 143 is formed so as to be tapered toward the tip in the cross-sectional shape. The protrusion 143 can be formed, for example, by pressing with a die having a desired protrusion shape.

The first electrode layer 15 has a first main surface 151 and a second main surface 152. The first main surface 151 is a surface facing the metal support 14. That is, the first main surface 151 is a surface to be joined to the support surface 142 of the metal support 14. In the present embodiment, the first main surface 151 is the lower surface of the first electrode layer 15.

The second main surface 152 is a surface opposite to the first main surface 151. That is, the second main surface 152 is a surface facing the electrolyte layer 17. The second main surface 152 is joined to the electrolyte layer 17. In the present embodiment, the second main surface 152 is the upper surface of the first electrode layer 15.

The first electrode layer 15 has a plurality of recesses 153. The recess 153 is formed on the second main surface 152 of the first electrode layer 15. The recess 153 overlaps with the supply hole 141 in the thickness direction of the first electrode layer 15 (vertical view in FIG. 5). That is, the recess 153 is arranged directly above the supply hole 141.

The depth d of the recess 153 is not particularly limited, but is, for example, about 0.5 to 50 μm. Further, the recess 153 gradually becomes deeper from the outer peripheral edge toward the central portion. The recess 153 has a slope from the deepest portion toward the outer peripheral edge.

Since the recess 153 is arranged directly above the supply hole 141 in this way, as shown in FIG. 6, the fuel supplied from the supply hole 141 to the first electrode layer 15 is guided by the recess 153 to the first. It easily spreads in the in-plane direction of the electrode layer 15. Therefore, fuel can be easily supplied to the interface of the portion other than directly above the supply hole 141. The arrows in FIG. 6 schematically represent the flow of fuel.

[Operation of cell 11]
First, while supplying fuel from the flow path 131 to the first electrode layer 15 through each supply hole 141 and supplying an oxidizing agent to the second electrode layer 19, the cell 11 is operated at an operating temperature (for example, from 50 ° C. to 50 ° C.). Heat to 250 ° C.). Then, in the second electrode layer 19, O ₂ (oxygen) reacts with water and e ⁻ (electrons) to generate OH ⁻ (hydroxide ion). The generated OH ⁻ moves to the first electrode layer 15 through the electrolyte layer 17. The OH ^{− that} has moved to the first electrode layer 15 reacts with the fuel to generate H ₂ O (water), CO ₂ (carbon dioxide), and e ⁻ . By such a reaction, an electromotive force is generated between the first electrode layer 15 and the second electrode layer 19.

[Modification example]
Although the embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications can be made without departing from the spirit of the present invention.

Modification 1
In the first and second embodiments, as shown in FIG. 7, the protrusions 43 and 143 may extend in the first electrode layers 5 and 15 that have entered the supply holes 41 and 141. That is, the protrusions 43 and 143 may extend in the left-right direction of FIG. Further, as shown in FIG. 8, among the plurality of protrusions 43 and 143, some of the protrusions 43a and 143a extend in the direction of the support surfaces 42 and 142 (upper in FIG. 8), and the other protrusions 43b , 143b may extend in the direction (left-right direction in FIG. 8) toward the first electrode layers 5 and 15 that have entered the supply holes 41 and 141.

Modification 2
In the first and second embodiments, the first electrode layers 5 and 15 enter only a part of the supply holes 41 and 141 of the metal supports 4 and 14, but the configurations of the cells 1 and 11 are limited to this. Not done. For example, as shown in FIG. 9, the first electrode layers 5 and 15 may enter the entire supply holes 41 and 141. Further, the first electrode layers 5 and 15 do not have to enter the supply holes 41 and 141.

Modification 3
In the first and second embodiments, as shown in FIG. 10, the metal supports 4, 14 may have curved surfaces 44, 144. The curved surfaces 44, 144 connect the inner wall surfaces of the supply holes 41, 141 and the exposed surfaces 45, 145. The exposed surfaces 45 and 145 are surfaces opposite to the support surfaces 42 and 142. The exposed surfaces 45 and 145 face the flow path members 3 and 13. The exposed surfaces 45 and 145 are exposed to the flow paths 31 and 131. As described above, the edge portions of the supply holes 41 and 141 on the flow path members 3 and 13 sides are formed by the curved surfaces 44 and 144. The curved surfaces 44 and 144 are curved so as to bulge outward. The cross-sectional shape of the curved surfaces 44 and 144 is an arc shape. The curved surfaces 44 and 144 can be formed by chamfering the corners formed by the inner wall surfaces of the supply holes 41 and 141 and the exposed surfaces 45 and 145. Although not particularly limited, the radius of curvature of the curved surfaces 44 and 144 is, for example, about 20 to 1000 μm.

The surface roughness of the curved surfaces 44, 144 may be smaller than the surface roughness of the inner wall surface of the supply holes 41, 141. Specifically, the arithmetic mean roughness of the curved surfaces 44, 144 may be smaller than the arithmetic mean roughness of the inner walls of the supply holes 41, 141.

Modification 4
In the first and second embodiments, the metal supports 4 and 14 have a chromium oxide film, but the metal supports 4 and 14 may not have a chromium oxide film. Further, the metal supports 4 and 14 may further have a coating film formed on the chromium oxide film. As the material constituting the coating film, a ceramic material, a metal material, or the like can be used. As the ceramic material, for example, a perovskite-type composite oxide containing La and Sr, a spinel-type composite oxide composed of transition metals such as Mn, Co, Ni, Fe, and Cu, and a glass material can be used. .. As the metal material, Ni, Co, Fe, Cu and the like can be used. Since conductivity is not required in the region of the surfaces of the metal supports 4 and 14 where the flow path members 3 and 13 and the first electrode layers 5 and 15 are not connected, the region is made of an insulating material. It may be covered with a coating film to be coated.

Modification 5
In the first embodiment, the cell body 10 has an intermediate layer 6 and a reaction prevention layer 8, but does not have to have at least one of the intermediate layer 6 and the reaction prevention layer 8.

Modification 6
In the first and second embodiments, the first electrode layers 5 and 15 function as anodes and the second electrode layers 9 and 19 function as cathodes, but the first electrode layers 5 and 15 serve as cathodes. The second electrode layers 9 and 19 may function as an anode. In this case, the constituent materials of the first electrode layers 5 and 15 and the second electrode layers 9 and 19 are exchanged, the fuel gas is flowed through the outer surfaces of the first electrode layers 5 and 15, and the oxidants are applied to the flow paths 31 and 131. All you have to do is let the gas flow. Then, in the case of the first embodiment, as shown in FIG. 11, the arrangement of the intermediate layer 6 and the reaction prevention layer 8 may be interchanged.

Modification 7
In the first and second embodiments, the supply holes 4 and 14 are circular in the thickness direction, but the shapes of the supply holes 4 and 14 are not limited to this. For example, the supply holes 4 and 14 may have a slit shape or may have other shapes.

Modification 8
In the first embodiment, as an example of the electrochemical cell, the solid oxide fuel cell 1 having ^O2- (oxygen ion) as a carrier has been described. Further, in the second embodiment, as an example of the electrochemical cell, the solid alkaline fuel cell 11 having OH ⁻ (hydroxide ion) as a carrier has been described. However, an electrochemical cell is an element in which a pair of electrodes are arranged so that an electromotive force is generated from an overall redox reaction in order to convert electric energy into chemical energy, and an element for converting chemical energy into electric energy. It is a general term for. Therefore, the electrochemical cell includes, for example, a fuel cell having a proton as a carrier, an electrolytic cell that produces hydrogen and oxygen from water vapor, and the like.

1, 11 Cell 4, 14 Metal support 41, 141 Supply hole 42, 142 Support surface 43, 143 Protrusions 5, 15 First electrode layer 53, 153 Recesses 7, 17 Electrolyte layer 9, 19 Second electrode layer 10, 110 cell body

Claims (9)

A cell body portion having a first electrode layer, a second electrode layer, and an electrolyte layer arranged between the first electrode layer and the second electrode layer.
A metal support having a support surface for supporting the cell main body and a supply hole opening in the support surface to support the cell main body, and a metal support.
With
The metal support further has a protrusion that protrudes from a corner formed by the support surface and the inner wall surface of the supply hole and extends inside the cell body.
Electrochemical cell.
The protrusion extends in the direction in which the support surface faces.
The electrochemical cell according to claim 1.
At least a part of the cell body has entered the supply hole.
The electrochemical cell according to claim 1 or 2.
The protrusion extends inside the cell body that has entered the supply hole.
The electrochemical cell according to claim 3.
The first electrode layer is arranged on the support surface of the metal support.
The electrochemical cell according to any one of claims 1 to 4.
The first electrode layer has a recess formed on the surface opposite to the surface facing the metal support.
The recess overlaps with the supply hole in the thickness direction of the first electrode layer.
The electrochemical cell according to any one of claims 1 to 5.
The first electrode layer functions as an anode and serves as an anode.
The second electrode layer functions as a cathode.
The electrochemical cell according to any one of claims 1 to 6.
The electrolyte layer has oxygen ion conductivity.
The electrochemical cell according to any one of claims 1 to 7.
The electrolyte layer has hydroxide ion conductivity.
The electrochemical cell according to any one of claims 1 to 7.

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