This application is based upon and claims the benefit of priority from Japanese Patent Application No. 2022-147282, filed on Sep. 15, 2022, and Japanese Patent Application No. 2023-86031, filed on May 25, 2023; the entire contents of which are incorporated herein by reference.
Embodiments of the present invention relate to an electrochemical device.
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 one, a phosphoric acid one, a molten carbonate one, a solid oxide one, and so on, according to an operating temperature range, a composing material, and a fuel type. 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 via 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 includes a cell stack in which a plurality of electrochemical cells are arranged in a stack direction for the purpose of improving an output, and in the cell stack, it is configured that the plurality of electrochemical cells are electrically connected in series.
In
As illustrated in
In the electrochemical device 1, the cell stack 2 is a stack including separators 20 and insulating sealing members 40, as illustrated in
Each of
In the cell stack 2, an electrochemical cell 10 is housed inside the separator 20, as illustrated in
The electrochemical cell 10 is of a flat type having a quadrangular shape, and has a support 11, a hydrogen electrode 12, an electrolyte membrane 13, and an oxygen electrode 14. The electrochemical cell 10 is configured in a manner that the electrolyte membrane 13 is interposed between the hydrogen electrode 12 and the oxygen electrode 14, on an upper surface of the support 11. The electrochemical cell 10 is of a hydrogen electrode support type (fuel electrode support type), and is formed by sequentially stacking the hydrogen electrode 12, the electrolyte membrane 13, and the oxygen electrode 14 on the upper surface of the support 11.
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, and 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, and formed of, for example, stabilized zirconia or the like being a solid oxide through which oxygen ions (O2-) permeate at an operating temperature. The oxygen electrode 14 is composed of a porous electrical conductor, and is formed of a perovskite-type oxide or the like, for example.
In the cell stack 2, the separator 20 includes a first separator composing member 21, a second separator composing member 22, and a third separator composing member 23, as illustrated in
The separator 20 is configured by stacking the second separator composing member 22 above the first separator composing member 21, and stacking the third separator composing member 23 above the second separator composing member 22. The first separator composing member 21, the second separator composing member 22, and the third separator composing member 23 are formed of metal materials, for example. A shape of a horizontal plane of the separator 20 is a cross shape, as illustrated in
As illustrated in
As illustrated in
In the cell stack 2, the insulating sealing member 40 includes an inner space SP40 penetrating in the stack direction, at a center part thereof, as illustrated in
The insulating sealing member 40 is formed of an insulating material, and is provided for electrically insulating and for sealing between a pair of separators 20 adjacently arranged in the stack direction, and between the end plate 60 and the separator 20 arranged adjacent to the end plate 60 in the stack direction (refer to
In the cell stack 2, a gas flow path F2 is formed, as illustrated in
Although an illustration is omitted, the gas flow path F2 is formed to penetrate the cell stack 2 in the stack direction, and functions as a flow path of a hydrogen electrode gas that flows through the hydrogen electrode 12 of the electrochemical cell 10 or a flow path of an 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, and 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.
The gas flow path F2 that functions as the flow path of the hydrogen electrode gas, is communicated with the inner space SP23 of the separator 20 via a communication path (illustration is omitted) formed in the separator 20, for example. Similarly, the gas flow path F2 that functions as the flow path of the oxygen electrode gas, is communicated with the inner space SP23 of the separator 20 via a communication path (illustration is omitted) formed in the separator 20, for example.
In the electrochemical device 1, the end plates 60 are provided as a pair, and the pair of end plates 60 are disposed so as to sandwich the cell stack 2, as illustrated in
In the electrochemical device 1, the number of the coupling members 70 is plural as illustrated in
The coupling members 70 include male screw members (bolts or the like) being bar-shaped fastening members, for example, and fasten between the pair of end plates 60 by using the fastening members. At corner parts of the pair of end plates 60, holes (illustration is omitted) are formed, and the male screw members being the coupling members 70 are disposed to penetrate the holes formed on the pair of end plates 60. Further, to the male screw members being the coupling members 70, female screw members (illustration is omitted) such as nuts are attached, to thereby fasten between the pair of end plates 60.
Note that the coupling members 70 are not necessarily fastening members, and in that case, the pair of end plates 60 are fastened by being pressed, for example. Further, the coupling members 70 may also employ a configuration of penetrating the cell stack 2, other than the configuration of penetrating the pair of end plates 60.
The insulating sealing member 40 that composes the cell stack 2 in the electrochemical device 1 is required to sufficiently keep the insulating state between the separators 20 adjacently arranged in the stack direction, and the like. At the same time, the insulating sealing member 40 is required to have a thickness that is necessary for sufficiently securing the spaces (the inner space SP40 and the inner space SP23) that function as the flow paths of the oxygen electrode gas.
In order to fulfill these requirements, a compressive sealing member made of mica or the like is used as the insulating sealing member 40. However, in order to obtain a sufficient sealing function when using the compressive sealing member as the insulating sealing member 40, it is required to apply a large load to the compressive sealing member. Consequently, a cost is increased in some cases.
In recent years, it has been proposed to use a glass sheet as the insulating sealing member 40. The glass sheet is a sheet containing a glass component and an organic binder component. In a case where the glass sheet is used as the insulating sealing member 40, a load required to obtain a sufficient sealing function is smaller (about 1/10000) than that in a case where the compressive sealing member is used as the insulating sealing member 40. For this reason, it is possible to achieve an advantage such as a reduction in cost.
However, when using the glass sheet as the insulating sealing member 40, the thickness of the insulating sealing member 40 is sometimes reduced according to operation execution of the electrochemical device 1. Concretely, when the insulating sealing member 40 of the glass sheet is subjected to initial baking processing executed by initial operation of the electrochemical device 1, the glass component in the glass sheet is baked, and the organic binder component in the glass sheet is burned to be removed. Further, at this time, the insulating sealing member 40 of the glass sheet is softened. As a result of this, the thickness of the insulating sealing member 40 formed by using the glass sheet is greatly reduced after starting the operation of the electrochemical device 1, when compared to the thickness before executing the operation (before the initial baking processing). After that, the thickness of the insulating sealing member 40 formed by using the glass sheet is gradually reduced as the operation continues.
When the thickness of the insulating sealing member 40 is reduced, the insulating state between the separators 20 adjacently arranged in the stack direction in the cell stack 2 may become insufficient, and at the same time, it becomes sometimes difficult to sufficiently secure the spaces (the inner space SP40 and the inner space SP23) that function as the flow paths of the oxygen electrode gas. Consequently, in the electrochemical device 1, a reduction in efficiency (power generation efficiency, electrolysis efficiency, and the like) is caused in some cases. In particular, when the stack direction of the cell stack 2 is along the vertical direction, a large load is applied to a lower part of the cell stack 2, and the insulating sealing member 40 is likely to become thin, so that problems as described above are likely to occur.
Also in a case where the insulating sealing member 40 is formed of a material whose thickness is reduced when the operation of the electrochemical device 1 is executed, other than the glass sheet, similar problems occur in some cases.
As described above, in the electrochemical device 1, the reduction in efficiency (power generation efficiency, electrolysis efficiency, and the like) is caused in some cases due to the reduction in thickness of the insulating sealing member 40 when the operation of the electrochemical device 1 is executed.
Therefore, the problem to be solved by the present invention is to provide an electrochemical device capable of effectively preventing the reduction in efficiency (power generation efficiency, electrolysis efficiency, and the like).
An electrochemical device of an embodiment includes: a cell stack; a pair of end plates; and coupling members. The cell stack includes a separator that houses an electrochemical cell in which an electrolyte membrane is interposed between a hydrogen electrode and an oxygen electrode, and an insulating sealing member formed of an insulating material, in which the separator and the insulating sealing member are alternately stacked in a stack direction in a manner that the insulating sealing members sandwich the separator. The pair of end plates are disposed to sandwich the cell stack in the stack direction. The coupling members are provided for coupling between the pair of end plates. The insulating sealing member is formed by using a material whose thickness is reduced when an operation of the electrochemical device is executed. The cell stack has a spacer disposed to be arranged next to the insulating sealing member in a direction orthogonal to the stack direction. A plurality of the spacers are arranged in the stack direction between the pair of end plates, and the spacer is interposed between the end plate and the separator that is arranged adjacent to the end plate in the stack direction, or between a pair of separators adjacently arranged in the stack direction. The spacer is formed of a material whose thickness reduction ratio when the operation of the electrochemical device is executed is smaller than that of the insulating sealing member. Before the execution of the operation of the electrochemical device, the thickness of the spacer is thinner than the thickness of the insulating sealing member. Further, it is configured that the thickness of the spacer keeps a state of being equal to or less than the thickness of the insulating sealing member when the operation of the electrochemical device is executed.
As illustrated in
In the cell stack 2 in the electrochemical device 1, a separator 20 and the insulating sealing member 40 are alternately stacked in a stack direction (the vertical direction z in this case) in a manner that the insulating sealing members 40 sandwich the separator 20, as illustrated in
In the cell stack 2, the separator 20 is configured in the same manner as in the related art, and an electrochemical cell 10 is housed inside the separator 20 (refer to
As illustrated in
The insulating sealing member 40 is formed of an insulating material. In the present embodiment, the insulating sealing member 40 is formed by using a glass sheet being a material whose thickness is reduced when an operation of the electrochemical device 1 is executed.
In the present embodiment, a horizontal plane of the insulating sealing member 40 is formed in a shape different from that of the separator 20 but a shape to expose a part of an upper surface of the separator 20, as illustrated in
In the cell stack 2, a plurality of the spacers 50 are arranged in a line in the stack direction (the vertical direction z in
Concretely, the spacer 50 is interposed between the end plate 60 and the separator arranged adjacent to the end plate 60 in the stack direction. Further, the spacer 50 is interposed between a pair of separators 20 adjacently arranged in the stack direction.
As illustrated in
In the present embodiment, the spacer 50 is formed by using a material whose thickness reduction ratio when the operation of the electrochemical device 1 is executed is smaller than that of the insulating sealing member 40 formed of the glass sheet, and a material having high strength and high insulating property. For example, the spacer 50 is formed by using an insulating material such as mica, alumina, or the like. In the spacer 50, a part that is not brought into contact with the separator 20 may use a conductive material such as a metal material.
In the present embodiment, before the execution of the operation of the electrochemical device 1 (in an unused state; before initial baking processing), a thickness H1a of the spacer 50 is thinner than a thickness H2a of the insulating sealing member 40 (H1a<H2a), as illustrated in
Accordingly, in the present embodiment, even in a case where the insulating sealing member 40 is formed of a material whose thickness becomes thin in the cell stack 2, it is possible to keep a state of being equal to or more than the thickness H1b of the spacer 50 at a portion between the end plate 60 and the separator 20 adjacently arranged in the stack direction and at a portion between a pair of separators 20 adjacently arranged in the stack direction.
In the present embodiment, the thickness H1b of the spacer 50 when the operation of the electrochemical device 1 is executed (after the initial baking processing) is preferably 90% or less, for example, of the thickness H2b of the insulating sealing member 40 when the operation of the electrochemical device 1 is executed (after the initial baking processing) (namely, H1b≤0.9·H2b). For example, when the thickness H2a of the insulating sealing member 40 before the initial baking processing is 1 mm, and the thickness H2b of the insulating sealing member 40 after the initial baking processing is 0.5 mm, the thickness H1b of the spacer 50 after the initial baking processing is preferably 0.45 mm or less.
When the spacer 50 is excessively thick, a load to be applied to the insulating sealing member 40 is sometimes reduced in accordance with the reduction in thickness of the insulating sealing member 40, which may cause a reduction in the sealing property of the insulating sealing member 40. When the spacer 50 is excessively thin, the insulating property of the insulating sealing member 40 is sometimes reduced and it becomes sometimes difficult to sufficiently secure the spaces (the inner space SP40 and the inner space SP23) that function as the flow paths of the oxygen electrode gas, in accordance with the reduction in thickness of the insulating sealing member 40. For this reason, the spacer 50 is set to have a thickness that satisfies the specification of the electrochemical device 1.
In the present embodiment, the above-described relationship between the insulating sealing member 40 and the spacer 50 is satisfied in all combinations between the insulating sealing members 40 and the spacers 50 arranged in the direction orthogonal to the stack direction (the direction along the xy plane in
As described above, the cell stack 2 that configures the electrochemical device 1 of the present embodiment has the spacers 50. In the present embodiment, even in a case where the insulating sealing member 40 is formed of a material whose thickness becomes thin (glass sheet), the state of being equal to or more than the thickness H1b of the spacer 50 is kept at the portion between the end plate 60 and the separator 20 adjacently arranged in the stack direction and at the portion between the pair of separators 20 adjacently arranged in the stack direction, as described above. Specifically, in the present embodiment, the change in thickness of the insulating sealing member 40 is suppressed by the spacer 50. Therefore, in the present embodiment, it is possible to prevent, by the spacer 50, the sealing property and the insulating property from being reduced in the insulating sealing member 40. Consequently, in the present embodiment, it is possible to effectively prevent the occurrence of reduction in efficiency (power generation efficiency, electrolysis efficiency, and the like) in the electrochemical device 1.
Further, in the present embodiment, the spacer 50 has the through hole K50, and the bar-shaped coupling member 70 penetrates the through hole K50. Accordingly, in the present embodiment, it is easy to perform alignment of the spacer 50 when assembling the electrochemical device 1, and thus it is possible to efficiently assemble the electrochemical device 1. After assembling the electrochemical device 1, a positional displacement of the spacer 50 is unlikely to occur, so that it is possible to sufficiently secure the reliability of the electrochemical device 1.
Hereinafter, modified examples of the above-described embodiment will be described.
As illustrated in
Also in the present modified example, each of a plurality of spacers 50 is arranged between a pair of end plates 60 so as to correspond to each of a plurality of insulating sealing members 40 arranged in the stack direction, as illustrated in
However, in the present modified example, the spacer 50 is a frame body configured to surround the insulating sealing member 40, as illustrated in
As illustrated in
In the cell stack 2, a separator 20 and the insulating sealing member 40 are alternately stacked in a stack direction (the vertical direction z in this case) in a manner that the insulating sealing members 40 sandwich the separator 20, as illustrated in
In the cell stack 2, the separator 20 is configured in the same manner as in the first embodiment, and an electrochemical cell 10 is housed inside the separator 20 (refer to
As illustrated in
The insulating sealing member 40 is formed by using a glass sheet being a material whose thickness is reduced when an operation of the electrochemical device 1 is executed, in the same manner as in the first embodiment. In the present embodiment, a horizontal plane of the insulating sealing member 40 is configured in the same shape as that of the separator 20, as illustrated in
In the cell stack 2, the spacer 50 is arranged between the pair of end plates 60, as illustrated in
As illustrated in
The spacer 50 is supported on an upper surface of the end plate 60 positioned on the lower side in the stack direction, between the pair of end plates 60, as illustrated in
In the same manner as in the first embodiment, the spacer 50 is formed of a material whose thickness reduction ratio when the operation of the electrochemical device 1 is executed is smaller than that of the insulating sealing member 40. For example, the spacer 50 is formed by using an insulating material such as mica, alumina, or the like.
In the present embodiment, before the execution of the operation of the electrochemical device 1 (in an unused state; before initial baking processing), a thickness H1a of the spacer 50 is thinner than a thickness H3a of the cell stack 2 (namely, H1a<H3a), as illustrated in
Accordingly, in the present embodiment, even in a case where the insulating sealing member 40 is formed of a material whose thickness becomes thin, the thickness H3b of the cell stack 2 can keep a state of being equal to or more than the thickness H1b of the spacer 50. As a result of this, also in the present embodiment, it is possible to keep a state of being equal to or more than the thickness H1b of the spacer 50 at a portion between the end plate 60 and the separator 20 adjacently arranged in the stack direction and at a portion between a pair of separators 20 adjacently arranged in the stack direction in the cell stack 2.
Note that in the present embodiment, the thickness H1b of the spacer 50 when the operation of the electrochemical device 1 is executed (after the initial baking processing) preferably satisfies a relationship represented by the following equation. In the following equation, H32b indicates a value of thickness of a plurality of insulating sealing members 40, and H31b indicates a value of thickness of a part other than the plurality of insulating sealing members 40 in the cell stack 2 when the operation of the electrochemical device 1 is executed (after the initial baking processing).
H1b≤0.9·H32b+H31b
As described above, in the cell stack 2 that configures the electrochemical device 1 of the present embodiment, the insulating sealing member 40 is formed of the material whose thickness becomes thin (glass sheet), in the same manner as in the first embodiment. In the present embodiment, also in this case, the state of being equal to or more than the thickness H1b of the spacer 50 is kept at the portion between the end plate 60 and the separator 20 adjacently arranged in the stack direction and at the portion between the pair of separators 20 adjacently arranged in the stack direction. Specifically, in the present embodiment, the change in thickness of the insulating sealing member 40 is suppressed by the spacer 50. Therefore, in the present embodiment, it is possible to prevent, by the spacer 50, the sealing property and the insulating property from being reduced in the insulating sealing member 40. Consequently, in the present embodiment, it is possible to effectively prevent the occurrence of reduction in efficiency (power generation efficiency, electrolysis efficiency, and the like) in the electrochemical device 1.
Further, in the present embodiment, the spacer 50 has the through hole K50, and the bar-shaped coupling member 70 penetrates the through hole K50, in the same manner as in the first embodiment. Accordingly, it is easy to perform alignment of the spacer 50 when assembling the electrochemical device 1. Besides, in the present embodiment, each of a plurality of spacers 50 is not disposed in the stack direction with respect to each of a plurality of insulating sealing members 40, unlike the first embodiment. The number of the spacer 50 to be disposed in the stack direction is the singular number. Therefore, in the present embodiment, it is possible to assemble the electrochemical device 1 more efficiently than the first embodiment.
Hereinafter, modified examples of the above-described embodiment will be described.
Also in the present modified example, between a pair of end plates 60, a plurality of spacers 50 are arranged in a direction orthogonal to the stack direction (a direction along the xy plane), but in the stack direction (the vertical direction z), not a plurality of the spacers 50 but one spacer 50 is arranged, as illustrated in
However, in the present modified example, the spacer 50 is a bar-shaped body that extends in the stack direction, as illustrated in
In the present modified example, one spacer 50 is arranged between a pair of end plates 60, as illustrated in
In the present modified example, the spacer 50 is a frame body configured to surround both the insulating sealing member 40 and bar-shaped coupling members 70. As above, a shape of the spacer 50 can employ various shapes. Also in this case, the same effect as that of the above-described embodiment can be achieved.
<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, 2: cell stack, 10: electrochemical cell, 11: support, 12: hydrogen electrode, 13: electrolyte membrane, 14: oxygen electrode, 20: separator, 21: first separator composing member, 22: second separator composing member, 23: third separator composing member, 40: insulating sealing member, 50: spacer, 60: end plate, 70: coupling member, 210: sealing material layer, 220: sealing material layer, F2: gas flow path, K50: through hole, SP22: inner space, SP23: inner space, SP40: inner space
Number | Date | Country | Kind |
---|---|---|---|
2022-147282 | Sep 2022 | JP | national |
2023-086031 | May 2023 | JP | national |