Embodiments of the present invention relate to an electrochemical device and a manufacturing method thereof.
An electrochemical device is a device related to hydrogen energy and has an electrochemical cell configured in a manner that a hydrogen electrode (fuel electrode) and an oxygen electrode (air electrode) sandwich an electrolyte membrane.
The electrochemical cell is classified into a solid polymer type, a phosphoric acid type, a molten carbonate type, a solid oxide type, and other types, according to an operating temperature range, a composing material, and a kind of fuel. Among these, a solid oxide electrochemical cell is attracting attention in terms of efficiency and the like.
The solid oxide electrochemical cell uses a solid oxide as an electrolyte membrane, and it can be used as a solid oxide fuel cell (SOFC) or a solid oxide electrolysis cell (SOEC).
In a case where the solid oxide electrochemical cell is used as the SOFC, for example, hydrogen supplied to a hydrogen electrode and oxygen (including oxygen in the air) supplied to an oxygen electrode react through an electrolyte membrane under a high-temperature condition, to thereby obtain electric energy. In contrast to this, in a case where the solid oxide electrochemical cell is used as the SOEC, for example, water (water vapor) is subjected to electrolysis under a high-temperature condition, resulting in that hydrogen is generated at a hydrogen electrode, and oxygen is generated at an oxygen electrode.
Generally, an electrochemical device is configured by an electrochemical cell stack in which a plurality of electrochemical cells are stacked to be electrically connected in series for the purpose of improving output. The electrochemical cell stack includes a plurality of separators. For example, a hydrogen flow path and an oxygen flow path are formed in the separator. The separator is conductive, for example, and electrically connects the plurality of stacked electrochemical cells.
[A] Configuration
As illustrated in
The electrochemical device 1J is a flat-type electrochemical cell stack though it is not illustrated, and
The following is a detailed description of various parts that make up the electrochemical device 1J.
[A-1] Electrochemical Cell 10
As illustrated in
In the electrochemical cell 10, the support 11 is composed of a porous electrical conductor.
The hydrogen electrode 12 is composed of a porous electrical conductor. The hydrogen electrode 12 is formed of Ni—YSZ (yttria-stabilized zirconia) or the like, for example.
The electrolyte membrane 13 is denser than the hydrogen electrode 12 and the oxygen electrode 14, composed of an ion conductor that does not conduct electricity but conducts ions. The electrolyte membrane 13 is formed of, for example, stabilized zirconia or the like, which is a solid oxide through which oxygen ions (O2−) permeate at an operating temperature.
The oxygen electrode 14 is composed of a porous electrical conductor. The oxygen electrode 14 is formed of perovskite-type oxide or the like, for example.
[A-2] Separators 21, 22, 23, and 24
The separators 21, 22, 23, and 24 are stacked as illustrated in
Among the plurality of separators 21, 22, 23, and 24, the separator 21 is a flat plate and the electrochemical cell 10 is disposed at a center part of an upper surface thereof. The separator 22 is a flat plate including an inner space SP22, which penetrates in a stack direction, at a center part thereof, and the inner space SP22 houses a portion at which the support 11, the hydrogen electrode 12, and the electrolyte membrane 13 are stacked in the electrochemical cell 10. The separator 23 is a flat plate (partition plate) including an inner space SP23, which penetrates in the stack direction, at a center part thereof, and the inner space SP23 houses the oxygen electrode 14 of the electrochemical cell 10. The separator 24 is a flat plate including a portion where a lower surface of the separator 24 faces the upper surface of the separator 21 through the inner space SP22 of the separator 22 and the inner space SP23 of the separator 23.
The respective surfaces of the plurality of separators 21, 22, 23, and 24 are coated with diffusion-preventing coatings 211, 221, 231, and 241. Here, the diffusion-preventing coatings 211, 221, 231, and 241 are provided to cover all exposed surfaces of the separators 21, 22, 23, and 24 in terms of workability.
The diffusion-preventing coatings 211, 221, 231, and 241 are provided to prevent metal elements (such as Cr) in the metal material composing the separators 21, 22, 23, and 24 from diffusing and adversely affecting the electrochemical cell 10. Concretely, the diffusion-preventing coatings 211, 221, 231, and 241 prevent the metal elements (such as Cr) in the metal material composing the separators 21, 22, 23, and 24 from evaporating from a metal surface and deteriorating performance of the electrochemical cell 10.
The diffusion-preventing coatings 211, 221, and 231 are formed, for example, using a material containing at least one of oxides of Co, Mn, Cu, Ni, and Fe. Here, the diffusion-preventing coatings 211, 221, and 231 are formed using oxides such as spinel and perovskite.
[A-3] Gas-Sealing Materials 31, 32, and 33
The gas-sealing materials 31, 32, and 33 have plate-shaped bodies as illustrated in
Here, the gas-sealing materials 31, 32, and 33 are interposed between each of the stacked plurality of separators 21, 22, 23, and 24. Concretely, the gas-sealing material 31 is interposed between the separator 21 and separator 22, the gas-sealing material 32 is interposed between the separator 22 and separator 23, and the gas-sealing material 33 is interposed between the separator 23 and separator 24. The gas-sealing material 32 is interposed between a lower surface of the separator 23 and an upper surface of the electrolyte membrane 13 of the electrochemical cell 10. The gas-sealing materials 31, 32, and 33 seal between each of the plurality of separators 21, 22, 23, and 24 and provide electrical insulation therebetween.
[A-4] Gas Flow Path 40
As illustrated in
The gas flow path 40 is a flow path of hydrogen electrode gas that flows through the hydrogen electrode 12 of the electrochemical cell 10 or a flow path of oxygen electrode gas that flows through the oxygen electrode 14 of the electrochemical cell 10. The hydrogen electrode gas is gas used for reaction at the hydrogen electrode 12 and gas generated in the reaction at the hydrogen electrode 12. The oxygen electrode gas is gas used for reaction at the oxygen electrode 14 and gas generated in the reaction at the oxygen electrode 14.
[B] Problems
As described above, the respective surfaces of the plurality of separators 21, 22, 23, and 24 are coated with the diffusion-preventing coatings 211, 221, 231, and 241. The diffusion-preventing coatings 211, 221, 231, and 241 include portions in contact with the gas-sealing materials 31, 32, and 33, as illustrated in
Reactions may occur between a material composing the diffusion-preventing coatings 211, 221, 231, and 241 and a material composing the gas-sealing materials 31, 32, and 33. For example, reactions may occur in the case of the following materials.
When a reaction occurs between the material composing the diffusion-preventing coatings 211, 221, 231, and 241 and the material composing the gas-sealing materials 31, 32, and 33, numerous bubbles may occur. As a result, the gas-sealing materials 31, 32, and 33 may deteriorate, making it difficult to ensure sufficient sealing performance. In addition, the diffusion-preventing coatings 211, 221, 231, and 241 may deteriorate, making it difficult to sufficiently prevent diffusion of metal elements (such as Cr) in the metal material composing the separators 21, 22, 23, and 24.
Therefore, the problem to be solved by the present invention is to provide an electrochemical device capable of sufficiently ensuring sealing performance, and the like, and a manufacturing method thereof.
An electrochemical device of this embodiment has an electrochemical cell with an electrolyte membrane interposed between a hydrogen electrode and an oxygen electrode, a plurality of separators formed of a metal material, and gas-sealing materials that seal at least one of between the electrochemical cell and the separator and between the plurality of separators. In the electrochemical device, diffusion-preventing coatings, which prevent diffusion of metal elements in the metal material composing the separators, cover surfaces of the separators. The diffusion-preventing coating is formed of a material that reacts with a material composing the gas-sealing material. There are portions where the separators are in direct contact with the gas-sealing materials.
[A] Configuration
As illustrated in
In this embodiment, the separators 21, 22, and 23 include portions in direct contact with the gas-sealing materials 31, 32 without the interposing diffusion-preventing coatings 211, 221, and 231, which is different from the case of the related art (see
Concretely, the separator 21 includes a portion in direct contact with the gas-sealing material 31 without the interposing diffusion-preventing coating 211. The separator 22 includes portions in direct contact with the gas-sealing materials 31, 32 without the interposing diffusion-preventing coating 221. The separator 23 includes a portion in direct contact with the gas-sealing material 32 without the interposing diffusion-preventing coating 231.
This configuration is made, for example, by carrying out a process of coating the diffusion-preventing coatings 211, 221, and 231 on the separators 21, 22, and 23 with masking treatment applied to the portions, which are in direct contact with the gas-sealing materials 31, 32.
The gas-sealing material 33a is formed of a material that does not react with the material composing the diffusion-preventing coatings 231, 241 different from the case of the related art. For example, the gas-sealing material 33a is formed of the following materials.
[B] Summary
As described above, in this embodiment, the separators 21, 22, and 23 include the portions in direct contact with the gas-sealing materials 31, 32 without the interposing diffusion-preventing coatings 211, 221, and 231. Therefore, in this embodiment, bubbles are not generated because no reaction occurs between the material composing the diffusion-preventing coatings 211, 221, and 231 and the material composing the gas-sealing materials 31, 32. As a result, in this embodiment, the sealing performance is sufficiently ensured without deteriorating the gas-sealing materials 31, 32, and the diffusion of metal elements (such as Cr) in the metal material composing the separators 21, 22, 23, and 24 can be sufficiently prevented without deteriorating the diffusion-preventing coatings 211, 221, and 231.
The diffusion-preventing coatings 211, 221, and 231 contain at least one of oxides of Co, Mn, Cu, Ni, and Fe. This allows a high Cr diffusion control effect to be achieved.
In this embodiment, the gas-sealing material 33a is made of the above material, which is difficult to make thin because thinning is not necessary. However, when the gas-sealing material 33a is formed of the same material as the other gas-sealing materials 31, 32 because thinning of the gas-sealing material 33a is necessary, the separator 24 is preferably configured to include a portion in direct contact with the gas-sealing material 33a without the interposing diffusion-preventing coatings 211, 221, and 231.
[A] Configuration
As illustrated in
The reaction-preventing layers 311, 321, and 331 are interposed between the diffusion-preventing coatings 211, 221, 231, and 241 and the gas-sealing materials 31, 32, and 33.
Concretely, the reaction-preventing layer 311 is interposed between the diffusion-preventing coating 211 and the gas-sealing material 31, as well as between the diffusion-preventing coating 221 and the gas-sealing material 31. The reaction-preventing layer 321 is interposed between the diffusion-preventing coating 221 and the gas-sealing material 32, as well as between the diffusion-preventing coating 231 and the gas-sealing material 32. The reaction-preventing layer 331 is interposed between the diffusion-preventing coating 231 and the gas-sealing material 33, as well as between the diffusion-preventing coating 241 and the gas-sealing material 33.
The reaction-preventing layers 311, 321, and 331 are formed of alumina, for example, to prevent reactions between the diffusion-preventing coatings 211, 221, and 231 and the gas-sealing materials 31, 32, and 33.
A deposition method of the reaction-preventing layers 311, 321, and 331 is, for example, calorizing, PVD, or other methods.
A thickness of the reaction-preventing layers 311, 321, and 331 is, for example, several hundred nm to several tens of μm.
[B] Summary
As described above, the reaction-preventing layers 311, 321, and 331 are interposed between the diffusion-preventing coatings 211, 221, 231, and 241 and the gas-sealing materials 31, 32, and 33 in this embodiment. Therefore, in this embodiment, bubbles are not generated because no reaction occurs between the material composing the diffusion-preventing coatings 211, 221, 231, and 241 and the material composing the gas-sealing materials 31, 32, and 33. As a result, in this embodiment, the sealing performance can be sufficiently ensured because the gas-sealing materials 31, 32, and 33 do not deteriorate, and the diffusion of metal elements (such as Cr) in the metal material composing the separators 21, 22, 23, and 24 can be sufficiently prevented because the diffusion-preventing coatings 211, 221, 231, and 241 do not deteriorate.
[A] Configuration
As illustrated in
As illustrated in
A through opening K211 (first through opening), which penetrates the diffusion-preventing coating 211 in a stack direction (longitudinal direction in
Similarly, a through opening K221 (second through opening), which penetrates the diffusion-preventing coating 211 in the stack direction where the separator 21 and separator 22 are stacked, is formed in the diffusion-preventing coating 221. The through opening K221 is formed to be opposite to the through opening K211 in the stack direction where the separator 21 and separator 22 are stacked.
In this embodiment, the gas-sealing material 31 is provided inside the through openings K211 and K221. A surface of the gas-sealing material 31 on the separator 21 side (lower surface in
[B] Manufacturing Method
[B-1] Mask Layer Formation Process
First, mask layers M211 and M221 are formed as illustrated in
Here, the mask layer M211 (first mask layer) is formed on the surface of the separator 21 in the region where the through opening K211 (see
The mask layers M211, M221 are made by applying a coated film formed by a material of the mask layers M211, M221 to the region where the mask layers M211, M221 are to be formed.
In this embodiment, the mask layers M211, M221 are formed at a center part of the surface where the separator 21 and separator 22 overlap when the separator 21 and separator 22 are stacked. The mask layers M211, M221 are formed so that a width H2 is narrower than a width H1 of the surface where the separator 21 and separator 22 overlap when the separator 21 and separator 22 are stacked.
[B-2] Diffusion-Preventing Coating Formation Process
Next, the diffusion-preventing coatings 211, 221 are formed as illustrated in
Here, the diffusion-preventing coating 211 is formed on the surface of the separator 21 where the mask layer M211 is formed. The diffusion-preventing coating 211 is formed to cover a portion of the surface of the separator 21 other than the portion where the mask layer M211 is formed. The diffusion-preventing coating 221 is also formed on the surface of the separator 22 where the mask layer M221 is formed. The diffusion-preventing coating 221 is formed to cover the portion other than the portion where the mask layer M221 is formed on the surface of the separator 22.
[B-3] Mask Layer Removal Process
Next, the mask layers M211, M221 (see
Here, the through opening K211 is formed by removing the mask layer M211 (see
The removal of the mask layers M211, M221 is performed using agents that dissolve the material of the mask layers M211, M221.
[B-4] Gas-Sealing Material Formation Process
Next, the gas-sealing material 31 is formed as illustrated in
Here, the gas-sealing material 31 is formed inside the through opening K211 so that the gas-sealing material 31 includes a portion protruding from the surface of the diffusion-preventing coating 211. The gas-sealing material 31 is formed so that a thickness TH is the sum of a depth DP1 of the through opening K211 and a depth DP2 of the through opening K221 (TH=DP1+DP2).
[B-5] Separator Stacking Process
Next, the separators 21, 22 are stacked as illustrated in
The separator 22 is stacked on the separator 21 so that the gas-sealing material 31 formed inside the through opening K211 is housed in the through opening K211.
After the above processes, the electrochemical device 1c of this embodiment is completed.
[C] Summary
As described above, in the electrochemical device 1c of this embodiment, the gas-sealing material 31 is formed to be in direct contact with the surface of the separator 21 and the surface of the separator 22 inside the through openings K211 and K221. In this embodiment, the gas-sealing material 31 is entirely housed in a sealed space made up of the through openings K211 and K221, which is different from the case of the first embodiment. Even when a reaction occurs between the material composing the gas-sealing material 31 and the material composing the diffusion-preventing coatings 211, 221, and even when a part of the diffusion-preventing coatings 211, 221 peels off, the structure is such that a reacted portion is not exposed to the outside air so that diffusion of metal elements (such as Cr) in the metal material composing the separators 21, 22 can be suppressed.
As a result, even when the gas-sealing material 31 deteriorates, the sealing performance can be sufficiently ensured, so the performance of the electrochemical cell 10 (power generation performance and electrolysis performance) can be exhibited even more efficiently in this embodiment than in the above embodiments. In addition, even when the diffusion-preventing coatings 211, 221 deteriorate due to reaction, the diffusion of metal elements (such as Cr) in the metal material composing the separators 21, 22 can be sufficiently prevented. Therefore, the deterioration of the performance of the electrochemical cell 10 due to diffusion of metal elements (such as Cr) can be suppressed more effectively in this embodiment than in the case of the above embodiments.
In this embodiment, the above effects can be fully obtained even when the gas-sealing material 31 cannot be fabricated in an ideal shape as illustrated in
As illustrated in
As illustrated in
Although a detailed explanation is omitted, the above effect can be obtained in the portion where the gas-sealing material 32 is formed as well as in the portion where the gas-sealing material 31 is formed.
<Others>
Although some embodiments of the present invention have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. Indeed, the novel embodiments described herein may be embodied in a variety of other forms; furthermore, various omissions, substitutions, and changes in the form of the embodiments described herein may be made without departing from the spirit of the inventions. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the inventions.
1: electrochemical device, 1J: electrochemical device, 1b: electrochemical device, 1c: electrochemical device, 10: electrochemical cell, 11: support, 12: hydrogen electrode, 13: electrolyte membrane, 14: oxygen electrode, 21: separator, 22: separator, 23: separator, 24: separator, 31: gas-sealing material, 32: gas-sealing material, 33: gas-sealing material, 33a: gas-sealing material, 211: diffusion-preventing coating, 221: diffusion-preventing coating, 231: diffusion-preventing coating, 241: diffusion-preventing coating, 311: reaction-preventing layer, 321: reaction-preventing layer, 331: reaction-preventing layer, K211: through opening, K221: through opening, M211: mask layer, M221: mask layer, SP22: inner space, SP23: inner space
Number | Date | Country | Kind |
---|---|---|---|
2021-016421 | Feb 2021 | JP | national |
The present application is a continuation application of International Application No. PCT/JP2022/3379, filed Jan. 28, 2022, which is based upon and claims the benefit of priority from Japanese Patent Application No. 2021-016421, filed Feb. 4, 2021; the entire contents of all of which are incorporated herein by reference.
Number | Date | Country | |
---|---|---|---|
Parent | PCT/JP2022/003379 | Jan 2022 | US |
Child | 18334926 | US |