阅读说明：本技术 电化学元件、电化学模块、电化学装置和能源系统 (Electrochemical element, electrochemical module, electrochemical device, and energy system ) 是由 大西久男 森哲哉 越后满秋 于 2020-03-27 设计创作，主要内容包括：本发明的目的在于提供能够提高发电效率的电化学元件。电化学元件中,板状支撑体具有第1气体流通的内部流路A1、气体流通允许部、以及至少膜状电极层、膜状电解质层与膜状对电极层以被覆气体流通允许部的全部或一部分的状态依次层叠而成的电化学反应部；内部流路A1具有使第1气体在规定的流通方向上流通的多个副流路A11和在第1气体的流通方向上设置在多个副流路A11的上游侧的分配部A12；板状支撑体在流通方向上的分配部A12与多个副流路A11之间具有供给结构体140,其将第1气体暂时存储于分配部A12,限制第1气体从分配部A12向多个副流路A11供给。(The purpose of the present invention is to provide an electrochemical element capable of improving power generation efficiency. In the electrochemical element, the plate-shaped support has an internal flow path A1 through which a1 st gas flows, a gas flow-allowing section, and an electrochemical reaction section in which at least a film-shaped electrode layer, a film-shaped electrolyte layer, and a film-shaped counter electrode layer are sequentially laminated in a state of covering all or a part of the gas flow-allowing section; the internal flow path a1 includes a plurality of sub-flow paths a11 for circulating the 1 st gas in a predetermined flow direction, and a distribution portion a12 provided upstream of the plurality of sub-flow paths a11 in the flow direction of the 1 st gas; the plate-shaped support has a supply structure 140 between the distribution portion a12 and the plurality of sub-channels a11 in the flow direction, and temporarily stores the 1 st gas in the distribution portion a12 to restrict the supply of the 1 st gas from the distribution portion a12 to the plurality of sub-channels a 11.)

1. An electrochemical element having a conductive plate-shaped support body having an internal flow path on the inside thereof through which a1 st gas, which is one of a reducing component gas and an oxidizing component gas, flows;

the plate-like support body has:

a gas flow-permitting portion capable of allowing gas to pass through the inner flow path and the outer side of the plate-like support, and

an electrochemical reaction section formed by sequentially laminating at least a film-shaped electrode layer, a film-shaped electrolyte layer, and a film-shaped counter electrode layer in a predetermined lamination direction so as to cover all or a part of the gas flow-allowing section;

the internal flow path has:

a plurality of sub-channels for circulating the 1 st gas in a predetermined circulating direction, and

a distribution portion provided upstream of the plurality of sub-channels in the flow direction of the 1 st gas;

the plate-shaped support has a supply structure between the distribution portion and the plurality of sub-channels in the flow direction, the supply structure temporarily storing the 1 st gas in the distribution portion and restricting supply of the 1 st gas from the distribution portion to the plurality of sub-channels.

2. The electrochemical element according to claim 1, wherein the supply structure has: a supply passage portion that allows the 1 st gas to pass from the distribution portion to the plurality of sub flow paths, and a supply blocking portion that blocks the 1 st gas from passing from the distribution portion to the plurality of sub flow paths.

3. The electrochemical element according to claim 2, wherein the plate-like support has: a plurality of sub-flow passage forming portions that form the respective sub-flow passages, and a plurality of partition portions that are provided between adjacent sub-flow passage forming portions and partition the respective adjacent sub-flow passages;

any one of the plurality of partitions is disposed in correspondence with the supply passage portion in the flow direction.

4. The electrochemical element according to claim 3, wherein at least 1 of the plurality of sub-channels formed by the plurality of sub-channel forming units is arranged in correspondence with the supply blocking unit in the flow direction.

5. The electrochemical element according to claim 3 or 4, wherein the supply-blocking section is located at a position different from the distribution section and the supply-passing section in the stacking direction.

6. The electrochemical element according to claim 5, wherein the spacer section and the secondary flow path forming section are different in position in the stacking direction.

7. The electrochemical element according to any one of claims 1 to 6, wherein the internal flow path has a junction provided downstream of the plurality of sub-flow paths in the flow direction of the 1 st gas,

the plate-shaped support has a discharge structure between the plurality of sub-channels and the junction in the flow direction, and restricts discharge of the 1 st gas from the plurality of sub-channels to the junction.

8. The electrochemical element according to claim 7, wherein the discharge structure has: a discharge passage section that passes the 1 st gas from the plurality of sub flow paths to the merging section, and a discharge blocking section that blocks the 1 st gas from passing from the plurality of sub flow paths to the merging section.

9. The electrochemical element according to claim 8, wherein the plate-like support has: a plurality of sub-flow path forming portions that constitute the plurality of sub-flow paths, and a plurality of partition portions that are provided between adjacent sub-flow path forming portions and partition the adjacent sub-flow paths;

at least 1 of the plurality of sub-flow passages formed by the plurality of sub-flow passage forming units is arranged to correspond to the discharge preventing unit in the flow direction.

10. The electrochemical element according to claim 9, wherein any one of the plurality of spacers is disposed to correspond to the discharge passage portion in the flow direction.

11. An electrochemical module, wherein a plurality of the electrochemical devices according to any one of claims 1 to 10 are stacked in the predetermined stacking direction via an annular seal portion through which the 1 st gas flows.

12. The electrochemical module according to claim 11, wherein the 1 st gas is introduced into the internal flow path via the annular seal portion,

a flow passage for passing a2 nd gas, which is the other of the reducing component gas and the oxidizing component gas, is formed between the electrochemical elements adjacent to each other in the stacking direction.

13. The electrochemical module according to claim 11 or 12, wherein among the plurality of electrochemical elements, a1 st electrochemical element and a2 nd electrochemical element are stacked adjacent to each other,

the 1 st gas is introduced into the internal flow path of the plate-like support via the annular seal portion,

the plate-shaped support constituting the 1 st electrochemical element and the plate-shaped support constituting the 2 nd electrochemical element are opposed to each other, and an outer surface of the plate-shaped support constituting the 1 st electrochemical element on which the electrochemical reaction section is disposed is electrically connected to an outer surface of the plate-shaped support constituting the 2 nd electrochemical element on a side different from the side on which the electrochemical reaction section is disposed, and a flow section through which the 2 nd gas, which is the other of the reducing component gas and the oxidizing component gas, flows along the outer surfaces is formed between the outer surfaces adjacent to each other.

14. The electrochemical module according to claim 13, wherein the plate-shaped support of each electrochemical element has a1 st penetration portion forming a supply path through which the 1 st gas flows,

the 1 st penetration portion of each electrochemical element communicates with an annular hole of an annular seal portion existing between adjacent electrochemical elements.

15. The electrochemical module of claim 14,

the flow portion has therein a1 st annular seal portion as the annular seal portion, which separates the 1 st penetration portion and the flow portion, which are formed on the two outer surfaces, respectively;

the 1 st penetration portion and the 1 st annular seal portion form the supply path through which the 1 st gas flows between the internal flow path and the supply path.

16. The electrochemical module according to claim 14 or 15, wherein the plate-shaped support has a2 nd penetrating portion that forms a discharge path through which the 1 st gas flowing through the internal flow path flows to an outside in a penetrating direction of a surface of the plate-shaped support;

a2 nd annular seal portion as the annular seal portion, which partitions the 2 nd penetrating portion and the flow portion, which are formed on the two outer surfaces, respectively, is provided in the flow portion;

the 2 nd penetration portion and the 2 nd annular seal portion form the discharge path through which the 1 st gas flowing through the internal flow path flows.

17. An electrochemical device having at least:

the electrochemical element according to any one of claims 1 to 10 or the electrochemical module according to any one of claims 11 to 16, and

and a fuel converter for passing a gas containing a reducing component to the electrochemical element or the electrochemical module, or a fuel converter for converting a gas containing a reducing component generated in the electrochemical element or the electrochemical module.

18. An electrochemical device comprising the electrochemical element according to any one of claims 1 to 10 or the electrochemical module according to any one of claims 11 to 16, and a power converter for extracting electric power or circulating electric power from the electrochemical element or the electrochemical module.

19. An energy system comprising the electrochemical device according to any one of claims 1 to 10 or the electrochemical device according to claim 17 or 18, and an exhaust heat utilization unit for reusing heat exhausted from the electrochemical device, or a fuel converter.

Technical Field

The invention relates to an electrochemical element, an electrochemical module, an electrochemical device, and an energy system.

Background

Patent document 1 discloses a fuel cell stack in which fuel cells and separators made of a porous material are alternately stacked. The fuel cell unit is configured to have an electrolyte membrane, an oxidant electrode, and a fuel electrode. An oxidant electrode is formed on one surface of the electrolyte membrane, and a fuel electrode is formed on the other surface. An oxidant gas flow path is formed in the separator facing the oxidant electrode along the planar direction, and the oxidant gas flows through the oxidant gas flow path. Similarly, a fuel gas flow path through which the fuel gas flows is formed in the planar direction in the membrane facing the fuel electrode. The stack thus formed generates electricity by an electrochemical reaction of a fuel gas containing hydrogen and an oxidant gas containing oxygen.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2017-188224.

Disclosure of Invention

Problems to be solved by the invention

In the fuel cell described in patent document 1, an electrolyte membrane, an oxidant electrode, and a fuel electrode are stacked in this order, and an oxidant gas and a fuel gas flow in the planar direction. However, the fuel cell of patent document 1 does not consider the flow distribution of the fuel gas in each sub-flow passage. For example, when a certain position in the flow direction is observed with respect to the flow of the fuel gas flowing through each sub-flow passage, the flow velocity of the fuel gas flowing through each sub-flow passage may not be constant in the intersecting direction intersecting the position. That is, in the intersecting direction at this position, the flow velocity of the fuel gas flowing through one sub-flow passage is higher than the flow velocity of the fuel gas flowing through the other sub-flow passage. Therefore, even if the fuel gas is sufficiently supplied to the electrode layer at a position where the flow rate of the fuel gas is low, the fuel gas may not be sufficiently supplied to the electrode layer at a position where the flow rate of the fuel gas is high. As a result, the electrochemical reaction in the fuel cell does not proceed sufficiently, and the power generation efficiency is lowered.

The present invention has been made in view of the above problems, and an object thereof is to provide a technique capable of improving power generation efficiency.

Means for solving the problems

[ constitution ]

The electrochemical device according to the present invention is characterized in that,

the gas supply device is provided with a conductive plate-shaped support body, wherein the conductive plate-shaped support body is provided with an internal flow path which is used for circulating a1 st gas as one of a reducing component gas and an oxidizing component gas on the inner side;

the plate-like support has:

a gas flow-permitting part capable of allowing gas to pass through the inner flow path and the outer side of the plate-like support, and

an electrochemical reaction section formed by sequentially laminating at least a film-shaped electrode layer, a film-shaped electrolyte layer, and a film-shaped counter electrode layer in a predetermined lamination direction so as to cover all or a part of the gas flow-allowing section;

the internal flow path includes: a plurality of sub-channels for circulating the 1 st gas in a predetermined flow direction, and a distribution portion provided upstream of the plurality of sub-channels in the flow direction of the 1 st gas;

the plate-like support has a supply structure between the distribution portion and the plurality of sub-flow passages in the flow direction, the supply structure temporarily storing the 1 st gas in the distribution portion and restricting the supply of the 1 st gas from the distribution portion to the plurality of sub-flow passages.

According to the above feature, the plate-like support has an internal flow path through which the 1 st gas flows. The internal flow path has a distribution portion and a plurality of sub-flow paths from the upstream side along the flow direction of the 1 st gas. The plate-like support has a supply structure between the distribution section and the plurality of sub-channels in the flow direction. The supply structure temporarily stores the 1 st gas in the distribution portion and distributes the 1 st gas from the distribution portion to the plurality of sub-channels. By providing such a supply structure, the 1 st gas can be supplied from the distribution portion to the respective sub-channels substantially uniformly. Therefore, the reaction efficiency of the electrochemical device can be improved.

More specifically, the supply structure having the above-described configuration is provided between the distribution portion and the plurality of sub-flow passages, and serves as a barrier to the flow of the 1 st gas from the distribution portion to the plurality of sub-flow passages. Therefore, the pressure loss of the 1 st gas when the gas flows from the distribution portion to the plurality of sub-channels becomes high, and the 1 st gas introduced into the distribution portion is distributed over the distribution portion so as to be filled and temporarily stored. Therefore, the pressure in the entire distribution portion becomes substantially uniform (pressure equalization). That is, the pressure difference between the distribution portion and each of the plurality of sub-channels is substantially the same. Further, since the 1 st gas is supplied from the distribution portion to the plurality of sub-passages, the 1 st gas is supplied to the respective sub-passages in a substantially pressure-equalized state. Thus, the flow distribution (flow velocity, flow rate, pressure, etc.) of the 1 st gas along the flow direction is substantially uniform among the sub-flow paths.

Further, the 1 st gas flows from the distribution portion into the plurality of sub flow paths. By utilizing the rectifying action of the divided flows to the plurality of flow paths in this manner, the flow distribution (flow velocity, flow rate, pressure, and the like) of the 1 st gas is substantially constant as compared with the case where the gas flows through the internal flow path in which the plurality of flow paths are not formed.

[ constitution ]

The electrochemical element according to the present invention is further characterized in that,

the supply structure includes: a supply passage portion for allowing the 1 st gas to pass from the distribution portion to the plurality of sub-flow paths, and a supply blocking portion for blocking the 1 st gas from passing from the distribution portion to the plurality of sub-flow paths.

In the supply structure configured as described above, the supply blocking section serves as a barrier to the flow of the 1 st gas from the distribution section to the plurality of sub-flow passages, and blocks the passage of the 1 st gas from the distribution section to the plurality of sub-flow passages. On the other hand, the supply passage section introduces the 1 st gas from the distribution section into the plurality of sub-channels. Therefore, the 1 st gas introduced into the distribution portion does not immediately flow to the plurality of sub-flow paths, but is distributed over the distribution portion so as to be filled with the gas, and temporarily stored, with the supply blocking portion serving as a barrier to increase the pressure loss. Further, the 1 st gas is supplied from the distribution portion to the plurality of sub-channels via the supply passage portion. Therefore, the 1 st gas is supplied from the distribution portion to the respective sub-flow passages in a substantially pressure-equalized state, and the flow distribution (flow velocity, flow rate, pressure, and the like) of the 1 st gas along the flow direction is substantially uniform between the respective sub-flow passages.

[ constitution ]

The electrochemical element according to the present invention is further characterized in that,

the plate-like support has: a plurality of sub-flow passage forming portions that form the respective sub-flow passages, and a plurality of partition portions that are provided between the adjacent sub-flow passage forming portions and partition the adjacent sub-flow passages;

any one of the plurality of partitions is disposed in correspondence with the supply passage portion in the flow direction.

The 1 st gas is introduced from the distribution portion into the plurality of sub-channels via the supply passage portion. According to the above configuration, since any of the partition portions is disposed in the flow direction in correspondence with the supply passage portion, the 1 st gas pushed out from the distribution portion to the supply passage portion advances in the flow direction and collides with the partition portion. The 1 st gas advances in the intersecting direction intersecting the flow direction due to the collision with the spacer. That is, the 1 st gas flowing from the distribution portion through the supply passage portion is not immediately introduced into the plurality of sub-flow paths, but collides with the partition portion before the sub-flow paths and advances in the intersecting direction. Then, the 1 st gas is introduced into the plurality of sub-channels formed by the plurality of sub-channel forming portions along the extrusion from the distribution portion. By temporarily storing the 1 st gas extruded from the supply passage portion between the supply structure and the plurality of sub-channels in this manner, the flow distribution (flow velocity, flow rate, pressure, and the like) of the 1 st gas along the flow direction can be made substantially uniform among the sub-channels.

[ constitution ]

The electrochemical element according to the present invention is further characterized in that,

at least 1 of the plurality of sub flow paths formed by the plurality of sub flow path forming portions is arranged to correspond to the supply blocking portion in the flow direction.

The 1 st gas extruded from the distribution portion to the supply passage portion collides with the partition portion by advancing in the flow direction. The 1 st gas that advances in the intersecting direction intersecting the flow direction due to the collision with the spacer is temporarily stored between the supply structure and the plurality of sub-flow paths and introduced into the plurality of sub-flow paths without returning to the distribution unit by the supply blocking unit. This makes it possible to substantially equalize the flow distribution (flow velocity, flow rate, pressure, etc.) of the 1 st gas along the flow direction between the sub-flow paths.

[ constitution ]

The electrochemical element according to the present invention is further characterized in that,

the supply blocking section is located at a position different from the positions of the distribution section and the supply passage section in the stacking direction.

For example, in the plate-shaped support, the supply blocking portion is formed so as to protrude upward in the stacking direction from the distribution portion and the supply passage portion. On the other hand, the distribution portion and the supply passage portion are formed so as to be recessed downward in the stacking direction with respect to the supply blocking portion. Thus, the 1 st gas introduced into the distribution portion is prevented from being discharged from the distribution portion by the supply blocking portion protruding upward in the stacking direction, and is temporarily stored in the distribution portion formed by the concave portion. Then, the 1 st gas in the distribution portion is introduced into the plurality of sub-channels via the supply passage portion formed by the concave portion.

[ constitution ]

The electrochemical element according to the present invention is further characterized in that,

the spacer and the sub-flow path forming portion are different in position in the stacking direction.

For example, in the plate-like support, the partition portion is formed so as to protrude upward in the stacking direction than the sub-flow path forming portion. Therefore, the 1 st gas extruded from the distribution portion to the supply passage portion collides with the spacer portion protruding upward in the stacking direction by traveling in the flow direction. The 1 st gas advancing in the cross direction due to the collision is temporarily stored between the supply structure and the plurality of sub-flow paths and introduced into the plurality of sub-flow paths without returning to the distribution unit by the supply blocking unit protruding upward in the stacking direction. This makes it possible to substantially equalize the flow distribution (flow velocity, flow rate, pressure, etc.) of the 1 st gas along the flow direction between the sub-flow paths.

[ constitution ]

The electrochemical element according to the present invention is further characterized in that,

the internal flow path has a junction provided downstream of the plurality of sub flow paths in the flow direction of the 1 st gas,

the plate-like support has a discharge structure between the plurality of sub-channels and the merging portion in the flow direction, and restricts discharge of the 1 st gas from the plurality of sub-channels to the merging portion.

According to the above configuration, not only the supply structure for supplying the 1 st gas from the distribution section to the plurality of sub-flow paths with a substantially uniform flow distribution but also the discharge structure is provided in a portion where the 1 st gas merges from the plurality of sub-flow paths at the merging section. Since the plurality of sub-channels are sandwiched between the supply structure and the discharge structure, the flow distribution (flow velocity, flow rate, pressure, and the like) of the 1 st gas in the plurality of sub-channels can be made substantially uniform, and the reaction efficiency of the electrochemical reaction can be improved.

More specifically, the discharge structure having the above-described configuration is provided between the plurality of sub-channels and the junction, and serves as a barrier for the 1 st gas to flow from the sub-channels to the junction. Therefore, the pressure loss of the 1 st gas when flowing from the plurality of sub-flow paths to the merging portion becomes high. Therefore, it is difficult for the 1 st gas introduced into the plurality of sub-channels to be immediately introduced from the plurality of sub-channels into the junction and spread over the plurality of sub-channels so as to fill the plurality of sub-channels. This makes it possible to substantially equalize the flow distribution (flow velocity, flow rate, pressure, etc.) of the 1 st gas along the flow direction between the sub-flow paths. Further, since the 1 st gas is distributed over the plurality of sub-flow paths so as to be filled, the electrochemical reaction is sufficiently performed in the plurality of sub-flow paths. Thereby, the reaction efficiency of the electrochemical reaction can be improved.

[ constitution ]

The electrochemical element according to the present invention is further characterized in that,

the discharge structure includes: a discharge passage section for allowing the 1 st gas to pass from the plurality of sub-flow paths to the merging section, and a discharge blocking section for blocking the 1 st gas from passing from the plurality of sub-flow paths to the merging section.

In the discharge structure configured as described above, the discharge prevention section serves as a barrier for the 1 st gas to flow from the plurality of sub-flow paths to the merging section, and prevents the 1 st gas from flowing from the plurality of sub-flow paths to the merging section. On the other hand, the discharge passage section introduces the 1 st gas from the plurality of sub-channels to the merging section. Therefore, the 1 st gas introduced into the plurality of sub-flow paths does not flow into the merging portion immediately, but spreads over the plurality of sub-flow paths so as to fill the sub-flow paths with the discharge preventing portion serving as a barrier and increasing the pressure loss. Further, the 1 st gas is supplied from the plurality of sub-channels to the merging section via the discharge passage section. Thus, the flow distribution (flow velocity, flow rate, pressure, etc.) of the 1 st gas along the flow direction is substantially uniform among the sub-flow paths.

[ constitution ]

The electrochemical element according to the present invention is further characterized in that,

the plate-like support has: a plurality of sub-flow path forming portions that constitute the plurality of sub-flow paths, and a plurality of partition portions that are provided between adjacent sub-flow path forming portions and partition the adjacent sub-flow paths;

at least 1 of the plurality of sub flow paths formed by the plurality of sub flow path forming portions is arranged to correspond to the discharge preventing portion in the flow direction.

According to the above configuration, the 1 st gas pushed out from the plurality of sub-channels travels in the flow direction and collides with the discharge prevention section. The 1 st gas advances in a cross direction crossing the flow direction due to collision with the discharge preventing portion. That is, the 1 st gas flowing from the plurality of sub-channels does not immediately flow into the merging portion, but collides with the discharge blocking portion before the merging portion and advances in the intersecting direction. Then, the 1 st gas is extruded from the plurality of sub-channels, passes through the discharge passage, and is introduced into the merging portion. By temporarily storing the 1 st gas pushed out from the plurality of sub-channels between the plurality of sub-channels and the merging portion in this manner, the flow distribution (flow velocity, flow rate, pressure, and the like) of the 1 st gas along the flow direction can be made substantially uniform between the respective sub-channels.

[ constitution ]

The electrochemical element according to the present invention is further characterized in that,

any one of the plurality of partitions is disposed in correspondence with the discharge passage in the flow direction.

[ constitution ]

The electrochemical element according to the present invention is further characterized in that,

the electrochemical element is stacked in the predetermined stacking direction via an annular seal portion for allowing the 1 st gas to flow therethrough.

According to the above configuration, since the plurality of electrochemical elements are stacked in the predetermined stacking direction via the annular seal portion, the 1 st gas can be prevented from leaking between the plurality of electrochemical elements.

[ constitution ]

The electrochemical element according to the present invention is further characterized in that,

the 1 st gas is introduced into the internal flow path through the annular seal portion,

a flow passage for passing a2 nd gas, which is the other of the reducing component gas and the oxidizing component gas, is formed between the electrochemical elements adjacent to each other in the stacking direction.

With the above-described characteristic configuration, each electrochemical element has an internal flow path through which the 1 st gas flows formed inside the plate-shaped support, and a flow portion through which the 2 nd gas flows is formed between adjacent electrochemical elements. Therefore, each electrochemical element can cause an electrochemical reaction between the 1 st gas supplied from the internal flow path and the 2 nd gas supplied from the flow portion.

More specifically, when the electrochemical element is caused to function as a fuel cell (electrochemical power generation unit) "converting chemical energy of fuel or the like into electric energy", the 1 st gas is one of a reducing component gas such as hydrogen and an oxidizing component gas such as air consumed by the electrochemical reaction, and the 2 nd gas is the other.

In the case where the electrochemical element is caused to function as an "electrolysis cell that converts electric energy into chemical energy such as fuel", the 1 st gas is one of a reducing component gas such as hydrogen and an oxidizing component gas such as oxygen generated by an electrochemical reaction, and the 2 nd gas is the other.

Further, the plate-like support body has: a gas flow-allowing part which can permeate gas across the inner flow path and the outer flow path of the plate-shaped support, and an electrochemical reaction part which is provided with an electrode layer, an electrolyte layer and a counter electrode layer in a state of covering all or part of the gas flow-allowing part. Therefore, in the case where the electrochemical element is caused to function as a fuel cell (electrochemical power generation unit), the 1 st gas and the 2 nd gas reach the electrochemical reaction section from the passage from the outside of the substrate and the passage from the internal flow path to the gas flow-allowing section of the plate-shaped support, and react with each other in the electrode layer and the counter electrode layer, whereby an electrochemical reaction such as generation of electricity can be caused.

In the case where the electrochemical element is caused to function as an electrolytic cell, the 1 st gas and the 2 nd gas can be generated by an electrolytic reaction of water or the like by supplying electricity to the electrochemical reaction section, and discharged from the passages outside the plate-shaped support and the passages leading from the gas flow-allowing sections of the plate-shaped support to the internal flow channels.

[ constitution ]

The electrochemical element according to the present invention is further characterized in that,

among the plurality of electrochemical elements, the 1 st electrochemical element and the 2 nd electrochemical element are stacked adjacent to each other,

the 1 st gas is introduced into the internal flow path of the plate-like support via the annular seal portion,

the plate-like support constituting the 1 st electrochemical element and the plate-like support constituting the 2 nd electrochemical element are opposed to each other, and an outer surface of the plate-like support constituting the 1 st electrochemical element, on which the electrochemical reaction part is disposed, is electrically connected to an outer surface of the plate-like support constituting the 2 nd electrochemical element, which is different from the side on which the electrochemical reaction part is disposed, and a flow section through which the 2 nd gas, which is the other of the reducing component gas and the oxidizing component gas, flows along the outer surfaces is formed between the outer surfaces adjacent to each other.

According to the above feature configuration, the electrochemical device has the internal flow path inside the plate-shaped support, and the 1 st gas flows into the internal flow path through the annular seal portion. The internal flow path has a distribution portion and a plurality of sub-flow paths. Therefore, the 1 st gas introduced into the internal flow path through the annular seal portion is introduced into the distribution portion and then introduced into the plurality of sub-flow paths. In this case, the 1 st gas can be equally distributed from the distribution portion to the plurality of sub-channels, and the electrochemical output can be equally generated in each electrochemical element. On the other hand, the 2 nd gas flows to a flow portion separated from the internal flow path. Therefore, the 1 st gas and the 2 nd gas can be distributed and circulated.

[ constitution ]

The electrochemical element according to the present invention is further characterized in that,

the plate-like support body of each electrochemical element has a1 st penetration portion forming a supply path through which the 1 st gas flows,

the 1 st penetration portion of each electrochemical element communicates with an annular hole of an annular seal portion existing between adjacent electrochemical elements.

According to the above characteristic configuration, the 1 st gas is supplied to the stacked body in which the plurality of electrochemical elements are stacked, through the 1 st penetration portion and the annular seal portion of each electrochemical element. More specifically, the 1 st gas is introduced into the internal flow path through the 1 st penetrating portion of the plate-shaped support and the annular seal portion provided between the electrochemical elements adjacent in the stacking direction. Then, the 1 st gas introduced into the internal flow path is introduced into the distribution portion and then introduced into the plurality of sub-flow paths.

[ constitution ]

The electrochemical module according to the present invention is characterized in that,

the circulation part is internally provided with a1 st annular sealing part as the annular sealing part, which separates the 1 st penetrating part and the circulation part which are respectively formed on the two outer surfaces;

the 1 st penetration portion and the 1 st annular seal portion form the supply path through which the 1 st gas flows between the internal flow path and the gas supply path.

By providing the 1 st annular seal portion, the 1 st penetration portions of the electrochemical elements stacked on each other in the stacked body can be connected to and communicated with each other while being spaced apart from the flow portion. Therefore, with a very simple configuration in which only the 1 st penetration portions of adjacent electrochemical elements are tightly connected to each other, the electrochemical elements can be connected in a form in which the electrochemical elements can be appropriately operated by the 1 st gas and the 2 nd gas, and an electrochemical module with high reliability and easy handling during the production of the electrochemical module can be provided.

The annular seal portion is not limited in shape as long as it is configured to prevent gas leakage by allowing the through portions to communicate with each other. That is, the annular sealing portion may have an endless configuration having an opening portion therein communicating with the penetration portion, and may seal the adjacent electrochemical elements. The annular seal portion is, for example, annular. The ring shape may be any shape such as a circle, an ellipse, a square, or a polygon.

[ constitution ]

The electrochemical module according to the present invention is further characterized in that,

the plate-like support has a2 nd penetrating part which forms a discharge path for allowing the 1 st gas flowing through the internal flow path to flow outside in a penetrating direction with respect to the surface of the plate-like support;

a2 nd annular seal portion as the annular seal portion provided in the flow portion, the 2 nd annular seal portion separating the 2 nd penetrating portion and the flow portion, the penetrating portions being formed on the two outer surfaces, respectively;

the 2 nd penetration portion and the 2 nd annular seal portion form the discharge path through which the 1 st gas flowing through the internal flow path flows.

That is, for example, when the electrochemical element is caused to function as a fuel cell (electrochemical power generation unit), the 1 st gas that has entered the internal flow path from the 1 st penetration portion passes through the internal flow path, flows to the electrochemical reaction portion via the gas flow-allowing portion, and the remaining portion flows to the 2 nd penetration portion that forms the discharge path. Since the 2 nd penetration portion is formed in a state of being separated from the 2 nd gas, the 1 st gas can be recovered from the discharge path in a state of being distinguished from the 2 nd gas. Since the discharge path is constituted by the sealing portion in the same manner as the supply path in the 1 st penetration portion, the flow portions can be connected in a spaced state by a very simple configuration in which only the 2 nd penetration portions of adjacent electrochemical elements are tightly connected to each other, and the electrochemical elements can be connected in a form in which the electrochemical elements can be operated appropriately by the 1 st gas and the 2 nd gas, thereby providing an electrochemical module which is easy to manufacture and reliable, and which has a structure that is easy to handle when manufacturing the electrochemical module.

[ constitution ]

The electrochemical device according to the present invention is characterized by comprising at least the electrochemical element or the electrochemical module, and a fuel converter for flowing a gas containing a reducing component to the electrochemical element or the electrochemical module, or a fuel converter for converting a gas containing a reducing component generated in the electrochemical element or the electrochemical module.

The fuel cell system according to the above feature configuration includes an electrochemical element or an electrochemical module, and a fuel converter configured to flow a gas containing a reducing component to the electrochemical element or the electrochemical module. Therefore, when the electrochemical module is operated as a fuel cell, if a configuration is adopted in which hydrogen is generated from a natural gas or the like supplied using a conventional raw fuel supply infrastructure such as a city gas by a fuel converter such as a reformer and is circulated through the fuel cell, an electrochemical device having an electrochemical module with excellent durability, seeding reliability and performance can be realized. In addition, since it is easy to construct a system for recycling unused fuel gas discharged from the electrochemical module, it is possible to realize a highly efficient electrochemical device.

Further, according to the above characteristic configuration, the fuel cell system includes an electrochemical element or an electrochemical module, and a fuel converter that converts a gas containing a reducing component generated in the electrochemical element or the electrochemical module. Therefore, when the electrochemical module is operated as an electrolytic cell, for example, an electrochemical device in which hydrogen generated by the electrolytic reaction of water is reacted with carbon monoxide and carbon dioxide in a fuel converter to convert the hydrogen into methane or the like can be used, and when such a configuration is used, an electrochemical device having an electrochemical module with excellent durability, seed reliability, and performance can be realized.

[ constitution ]

The electrochemical device according to the present invention is characterized in that,

the electrochemical device includes the electrochemical element or the electrochemical module, and a power converter for extracting electric power or flowing electric power from the electrochemical element or the electrochemical module.

With the above-described characteristic configuration, the power converter extracts electric power generated by the electrochemical module or supplies electric power to the electrochemical module. As a result, the electrochemical module functions as a fuel cell or an electrolysis unit as described above. Therefore, according to the above configuration, it is possible to provide an electrochemical element or the like capable of improving the efficiency of converting chemical energy of fuel or the like into electric energy or converting electric energy into chemical energy of fuel or the like.

For example, in the case of using an inverter as a power converter, it is preferable to use an inverter because the electric output obtained from an electrochemical module having excellent durability, seeding reliability, and performance can be boosted by the inverter or converted from direct current to alternating current, and therefore the electric output obtained from the electrochemical module can be easily used.

[ constitution ]

The energy system according to the present invention is characterized by the following aspects:

the fuel cell system includes the electrochemical element or the electrochemical device, and an exhaust heat utilization unit for reusing heat exhausted from the electrochemical element, the electrochemical device, or the fuel converter.

According to the above characteristic configuration, since the electrochemical device or the electrochemical device and the exhaust heat utilization portion for reusing the heat exhausted from the electrochemical device, the electrochemical device or the fuel converter are provided, an energy system having excellent durability, seeding reliability and performance and excellent energy efficiency can be realized. In addition, a hybrid system having excellent energy efficiency can be realized by combining the power generation system that generates power by using the combustion heat of the unused fuel gas discharged from the electrochemical element, the electrochemical device, or the fuel converter.

Drawings

FIG. 1: is a cross-sectional view of an electrochemical module.

FIG. 2: is a top view of the electrochemical module.

FIG. 3: is a side view of an electrochemical module.

FIG. 4: is a schematic of an electrochemical module.

FIG. 5: is a schematic view of an electrochemical element.

FIG. 6: is a sectional view VI-VI in fig. 5.

FIG. 7: is a view from VII to VII in FIG. 5.

FIG. 8: is a sectional view VIII-VIII in fig. 5.

FIG. 9: is a cross-sectional view IX-IX in fig. 5.

FIG. 10: is an X-X sectional view in fig. 5.

FIG. 11: is a cross-sectional view XI-XI in fig. 5.

FIG. 12: is a sectional view XII-XII in fig. 5.

FIG. 13: is a cross-sectional view XIII-XIII in FIG. 5.

FIG. 14: is a cross-sectional view XIV-XIV in FIG. 5.

FIG. 15: is an XV-XV sectional view in fig. 5.

FIG. 16: is a cross-sectional view of XVI-XVI in fig. 5.

FIG. 17: is a cross-sectional view of XVII-XVII in FIG. 5.

FIG. 18: is a cross-sectional view of XVIII-XVIII in FIG. 5.

FIG. 19: is a cross-sectional view XIX-XIX in FIG. 5.

FIG. 20: is a sectional view XX-XX in fig. 5.

FIG. 21: is an enlarged view of a main part of the electrochemical reaction part.

FIG. 22: the drawings are for explaining the supply structure and the discharge structure.

FIG. 23: is a schematic diagram of an energy system.

FIG. 24: is an explanatory view of an electrochemical module according to another embodiment.

FIG. 25: is a schematic diagram of other energy systems.

Detailed Description

[ embodiment ]

The electrochemical module M according to the embodiment of the present invention and the method of assembling the electrochemical module M will be described below. In the case of representing the positional relationship of the layers, for example, the electrolyte layer side is referred to as "upper" and the 1 st plate body side is referred to as "lower" and "lower" in the view of the electrode layer. In the present invention, since the same effect can be obtained even when the electrochemical module M is disposed in the vertical or horizontal direction, "up" and "down" can be read as "left" and "right", respectively.

(1) Integral construction of electrochemical Module M

The overall structure of the electrochemical module M will be described below. As shown in fig. 1, the electrochemical module M includes an electrochemical element stack (stack) S and a substantially rectangular parallelepiped container (casing, 1 st holder, 2 nd holder) 200 in which the electrochemical element stack S is housed. The electrochemical element a (fig. 4) is an element that generates electricity, and is formed in a plate shape extending from the front of the sheet to the depth of the sheet in the cross-sectional view of fig. 1. The electrochemical element laminate S is formed by laminating a plurality of flat plate-like electrochemical elements a in the vertical laminating direction (the + Z direction and the-Z direction (Z direction) described later) in the cross-sectional view of fig. 1. In the present embodiment, an SOFC (Solid Oxide Fuel Cell) is described as an example of the electrochemical element a.

Further, the electrochemical module M has: a1 st gas supply unit 61 for supplying a1 st gas to the electrochemical element stack S from the outside of the container 200, and a1 st gas discharge unit 62 for discharging the 1 st gas after the reaction in the electrochemical element stack S.

As shown in fig. 1 to 3, the container 200 is provided with a2 nd gas supply unit 71, and the 2 nd gas is supplied to the electrochemical element stack S from the outside of the container 200. In the electrochemical element stack S, the 2 nd gas after the reaction is discharged to the outside from the 2 nd gas discharge unit 72 provided in the container 200.

Here, the 1 st gas is a reducing component gas such as a fuel gas, and the 2 nd gas is an oxidizing component gas such as air.

In the cross-sectional view of fig. 1, the electrochemical module M has plate members 240 with openings on both side surfaces of the electrochemical element stack S. The plate member 240 with openings is a plate-shaped member extending in the stacking direction of the electrochemical element a corresponding to both side surfaces of the electrochemical element stack S, and is preferably made of an insulating material such as mica in order to prevent electrical short (short) in the electrochemical module M. The plate member with openings 240 has a plurality of openings 240a formed therein, which penetrate along the planar direction of the electrochemical element stack S.

Therefore, the electrochemical cell stack S receives the supply of the fuel gas from the 1 st gas supply unit 61, and receives the supply of the air from the 2 nd gas supply unit 71 through the opening 240a of the plate member 240 with openings, and electrochemically reacts the fuel gas and the oxygen in the air to generate electricity. The fuel gas after the electrochemical reaction is discharged to the outside from the 1 st gas discharge portion 62. The air after the electrochemical reaction is introduced into the 2 nd gas discharge portion 72 through the opening 240a of the plate member 240 with an opening, and is discharged to the outside from the 2 nd gas discharge portion 72.

In this embodiment, the plate members 240 with openings are provided adjacent to both side surfaces of the electrochemical element laminate S, but it is not essential that either one of them be provided, or both of them be omitted.

The electrochemical module M includes an upper insulator 210T and an upper plate (1 st holder) 230T in this order from the electrochemical element stack S side toward the outside in the upper portion of the electrochemical element stack S. Similarly, the electrochemical module M includes a lower insulator 210B and a lower plate (2 nd holder) 230B in this order from the electrochemical element stack S side toward the outside in the lower portion of the electrochemical element stack S.

The electrochemical element laminate S is described in detail below.

(2) Insulator, plate and container

Hereinafter, the insulators (upper and lower insulators 210T and 210B) 210, the plates (upper and lower plates 230T and 230B) 230, and the container 200 will be further described.

The upper insulator 210T is a plate-like member and is disposed so as to cover the upper plane (1 st plane) of the electrochemical element stack S. The upper insulator 210T is made of, for example, hard mica, and electrically insulates the electrochemical element stack S from the outside.

The upper plate 230T is a plate-shaped member, is disposed above the upper insulator 210T, and is formed of a ceramic material having high bending strength at high temperatures, for example, 99 alumina.

The upper plate 230T receives a predetermined fastening pressure from the container 200 together with the lower plate 230B, and sandwiches the electrochemical element stack S and the pair of upper and lower insulators 210T and 210B. Herein, the fastening pressure means, for example, every 1mm²And the pressure per unit area of the like.

The lower insulator 210B is disposed so as to cover the lower plane (the 2 nd plane) of the electrochemical element stacked body S. The lower plate 230B is disposed below the lower insulator 210B. The lower insulator 210B and the lower plate 230B are identical to the upper insulator 210T and the upper plate 230T, respectively.

The container 200 in which the electrochemical element stack S is built is a substantially rectangular parallelepiped container as shown in fig. 1 to 3. The container 200 includes a box-shaped upper cover (1 st holder) 201 having a lower opening and a lower cover (2 nd holder) 203 having an upper opening. A connection portion 202 is provided on an end surface of the upper cover 201 facing the lower cover 203, and a connection portion 205 is provided on an end surface of the lower cover 203 facing the upper cover 201. The connection portion 202 and the connection portion 205 connect the upper cover 201 and the lower cover 203 by, for example, welding, and form a rectangular parallelepiped space inside.

In the present embodiment, as shown in fig. 1, the lower cover 203 has a depth in the vertical direction (stacking direction of the electrochemical elements a) that is deeper than the upper cover 201. However, the upper cover 201 and the lower cover 203 are not limited to this depth relationship as long as they can form a space integrally inside. For example, the upper cover 201 may be deeper than the lower cover 203.

As shown in fig. 1 to 3, a2 nd gas supply portion 71 and a2 nd gas discharge portion 72 are formed on a pair of side walls of the lower cover 203 facing each other in the center portion in the vertical direction of the container 200.

Here, the lower cover 203 is formed with a2 nd gas supply portion 71 and a2 nd gas discharge portion 72. However, the positions of forming the 2 nd gas supply portion 71 and the 2 nd gas discharge portion 72 are not limited to this, and may be formed at any position of the container 200. The 2 nd gas supply part 71 and the 2 nd gas discharge part 72 may also be formed on, for example, the upper cover 201.

As shown in fig. 1 and 2, the upper cover 201 has an opening 201c that is smaller than the outer edge of the upper cover 201. Next, in the cross-sectional view of fig. 1, the end portion facing the inside of the electrochemical element stacked body S, adjacent to the opening 201c, branches into a1 st end portion 201a and a2 nd end portion 201 b. Then, the 1 st end 201a extends in the planar direction by a predetermined length toward the inside of the container 200, and the 2 nd end 201b branches from the 1 st end 201a and extends below the container 200 by a predetermined length. The 1 st end 201a and the 2 nd end 201b form substantially 90 ° in a cross-sectional view, and form an L-shaped corner. The corner of the L-shape is formed along the outer edge inside the outer edge of the top view of the upper cover 201 shown in fig. 2. Thus, as shown in fig. 1 and 2, an opening 201c which is smaller than the outer edge of the upper cover 201 by one turn is formed in the upper surface of the upper cover 201 by the terminal end of the 1 st end 201 a.

The lower cover 203 has a1 st end 203a and a2 nd end 203b constituting L-shaped corners of substantially 90 ° in the cross-sectional view shown in fig. 1, similarly to the upper cover 201. Then, as shown in fig. 1, an opening 203c which is smaller than the outer edge of the lower cover 203 by one turn is formed by the terminal end of the 1 st end portion 203 a.

As shown in fig. 1, the upper ends of a pair of plate members 240 with openings, an upper insulator 210T, and an upper plate 230T are fitted into the corners of the L-shape formed by the 1 st end 201a and the 2 nd end 201b of the upper cover 201. Specifically, the upper plate 230T along the planar direction of the electrochemical element stacked body S is supported such that the upper surface of the outer peripheral end thereof is in contact with the lower surface of the 1 st end 201a (a part of the inner surface of the corner of the L-shape). The plate member 240 with an opening along the side surface of the electrochemical element laminate S is supported by the outer surface of the upper end thereof contacting the inner surface (a part of the inner surface of the corner of the L) of the 2 nd end 201 b. The upper insulator 210T is supported by the corner of the L formed by the 1 st end 201a and the 2 nd end 203b via the upper plate 230T and the plate member 240 with an opening.

Similarly, the lower ends of the pair of plate members 240 with openings, the lower insulator 210B, and the lower plate 230B are fitted into the corners of the pair of L-shapes facing each other in the planar direction of the lower cover 203.

Then, the upper surface of the electrochemical element stack S is supported by the upper cover 201 via the upper plate 230T and the upper insulator 210T. The lower surface of the electrochemical element stack S is supported by the lower cover 203 via the lower plate 230B and the lower insulator 210B.

With such a configuration, the upper cover 201 and the lower cover 203 are connected to the connection portion 202 and the connection portion 205 by, for example, welding, while sandwiching the electrochemical element stacked body S, the upper and lower insulators 210T and 210B, the upper and lower plates 230T and 230B, and the like between the upper and lower portions. At this time of connection, the upper cover 201 and the lower cover 203 are connected to each other by applying a predetermined fastening pressure to the electrochemical element stack S and the like. That is, in a state where the upper cover 201 and the lower cover 203 are connected, a predetermined fastening pressure is applied to the electrochemical element laminated body S, the upper and lower insulators 210T and 210B, and the upper and lower plates 230T and 230B.

As shown in fig. 3, an opening 203e is formed in a side surface of the lower cover 203. Therefore, a part of the side surface of the electrochemical element laminate S is exposed through the opening 203 e. Then, by forming the openings 201c, 203c and the opening 203e in the container 200, the container 200 can be reduced in weight, and the material required for the container 200 can be reduced. In the case where an electrical short (short) may occur due to the side surface of the electrochemical element laminate S coming into contact with the upper lid 201 or the lower lid 203 or both, a side surface insulator 245 made of a material such as mica is provided between the electrochemical element laminate S and the side surface of the upper lid 201 or the lower lid 203.

The lower cover 203 and the upper cover 201 of the container 200 apply a tightening pressure to the electrochemical element stacked body S by their combination. Examples of the material of the container 200 include ferritic stainless steel, martensitic stainless steel, and a composite of these with ceramics. These materials have a smaller thermal expansion coefficient than austenitic stainless steel, and among the thermal expansion coefficients of ferritic stainless steel, SUS430 is about 11X 10^-6/℃。

Further, of the thermal expansion coefficients of the martensitic stainless steel, SUS403 and SUS420J1 were about 10.4X 10^-6SUS410 and SUS440C were about 10.1X 10/° C^-6V. C. Further, the container 200 is preferably made of a material excellent in corrosion resistance.

The material of the electrochemical element stack S is preferably the same as that of the container 200. In other words, the materials of the electrochemical element stack S and the container 200 preferably have the same thermal expansion coefficient as that of the container 200. At this time, the substrate of the electrochemical element laminate S and the container 200 thermally expand to the same extent when the electrochemical element a generates electricity at a high temperature, for example. Therefore, for example, the difference in thermal expansion between the substrate of the electrochemical element a and the container 200 can be reduced, and damage to the substrate and the like can be suppressed.

(3) Method for assembling electrochemical module M

Next, a method of assembling the electrochemical module M will be described.

A plurality of electrochemical elements a are stacked to prepare an electrochemical element stack S. The constitution and the manufacturing method of the electrochemical element laminate S are as described later.

Further, a container 200 for housing the electrochemical element stack S is prepared. The container 200 is not limited to this, and may be manufactured by, for example, a lost wax casting method. When the lost wax casting method is used, a cavity mold corresponding to the outer shape of the container 200 is manufactured by using a thermoplastic material containing beeswax, rosin, or the like, for example. The mold is coated with a refractory material containing silica sand, lime powder, or the like. The refractory-coated mold is then heated and the mold made of the thermoplastic material is melted out. Thereby, a cavity corresponding to the mold for molding the shape of the container 200 is formed inside the refractory. After the material of the vessel 200 is injected into the cavity and allowed to solidify, the refractory material is removed. Thus, the container 200 having the upper cap 201 and the lower cap 203 is manufactured by a lost wax casting method. Note that the upper cover 201 and the lower cover 203 may be manufactured separately.

Next, for example, a pair of plate members 240 with openings are disposed on both side surfaces of the electrochemical element stack S, and the insulator 210 and the plate 230 are accommodated in the lower cover 203 in a state of being disposed in order on the upper plane and the lower plane of the electrochemical element stack S. The lower cover 203 is covered with the upper cover 201, and the position of the electrochemical element laminate S is adjusted so as to apply a predetermined fastening pressure, and the lower cover 203 and the upper cover 201 are welded and joined to each other. Thereby, the electrochemical module M is assembled.

As described above, when the container 200 is manufactured by the lost wax casting method, cost reduction can be achieved by thinning, precision reduction, and mass production.

Further, by forming the box-shaped container 200, in the present embodiment, a space for a manifold of air to be supplied from the 2 nd gas supply portion 71 to the electrochemical element stacked body S can be provided.

(4) Specific constitution of electrochemical Module M

Next, a specific structure of the electrochemical module M will be described with reference to fig. 1, 4, 5, and the like. Fig. 1 shows the electrochemical element laminate S of fig. 1 in detail.

Here, as shown in fig. 4 to 21, etc., the stacking direction of the electrochemical element stack S is the + Z direction and the-Z direction (Z direction). Further, the direction in which the 1 st gas flows from the 1 st gas supply portion 61 side to the 1 st gas discharge portion 62 side between the 1 st plate-like body 1 and the 2 nd plate-like body 2, and the direction in which the 2 nd gas flows from the 2 nd gas supply portion 71 side to the 2 nd gas discharge portion 72 side between the 1 st plate-like body 1 and the 2 nd plate-like body 2 are the + X direction and the-X direction (X direction) intersecting the + Z direction and the-Z direction (Z direction). In addition, directions intersecting the + Z direction and the-Z direction (Z direction) and the + X direction and the-X direction (X direction) are the + Y direction and the-Y direction (Y direction). Then, the XZ plane, the XY plane, and the YZ plane are substantially orthogonal to each other.

As shown in fig. 1 and 4, the electrochemical module M includes: a container 200 (an upper lid 201 and a lower lid 203) in which the electrochemical element stack S is built, a1 st gas supply unit 61 that supplies a1 st gas from the outside of the container 200 to an internal flow path a1 via a supply path 4, a1 st gas discharge unit 62 that discharges the 1 st gas after reaction, a2 nd gas supply unit 71 that supplies a2 nd gas from the outside of the container 200 to a flow unit a2, a2 nd gas discharge unit 72 that discharges the 2 nd gas after reaction, and an output unit 8 that obtains an output accompanying an electrochemical reaction in the electrochemical reaction unit 3; the container 200 includes a distribution chamber 9 for distributing and supplying the 2 nd gas supplied from the 2 nd gas supply unit 71 to the flow portion a 2.

The distribution chamber 9 is a space located on the side of the electrochemical element stack S where the 2 nd gas is supplied to the electrochemical element stack S,

the flow portion a2 is formed with an opening on the space side and communicates with the space.

The electrochemical element laminate S is placed in the container 200 in a state sandwiched between a pair of current collectors 81 and 82, the output unit 8 is extended from the current collectors 81 and 82, and is connected to a power supply target outside the container 200 so as to be able to supply power, and the current collectors 81 and 82 are electrically insulated from at least one of the containers 200, and the 1 st gas is contained in the container 200 in an airtight manner.

Thereby, the electrochemical module M is supplied with the fuel gas (sometimes referred to as a1 st gas) from the 1 st gas supply part 61 and simultaneously with the air (sometimes referred to as a2 nd gas) from the 2 nd gas supply part 71, whereby the fuel gas enters as indicated by a broken line arrow in fig. 1, 4, 5, and the like, and the air enters as indicated by a solid line arrow.

The fuel gas supplied from the 1 st gas supply unit 61 is guided to the supply passage 4 through the 1 st penetration portion 41 of the uppermost electrochemical element a of the electrochemical element stack S, passes through the supply passage 4 partitioned by the 1 st annular seal portion 42, and flows to the internal flow passages a1 of all the electrochemical elements a. The air supplied from the 2 nd gas supply portion 71 once flows into the distribution chamber 9, and then flows to the flow portion a2 formed between the electrochemical elements a. In the present embodiment, the flow direction of the fuel gas flowing along the plane of the plate-like support 10 in the internal flow path a1 is a direction from the + X direction toward the-X direction. Similarly, the flow direction of the air flowing along the plane of the plate-like support 10 in the flow portion a2 is a direction from the + X direction toward the-X direction.

In addition, when the 2 nd plate-like body 2 (a part of the plate-like support 10) is used as a reference, the internal flow path a1 is formed between the 1 st plate-like body 1 and the 2 nd plate-like body 2 at a portion where the 2 nd plate-like body 2 portion of the wave plate-like shape bulges out from the 1 st plate-like body 1 (a part of the plate-like support 10), and the internal flow path can be in contact with and electrically connected to the electrochemical reaction portion 3 of the adjacent electrochemical element a. On the other hand, the portion of the 2 nd plate-like body 2 in the wave plate-like shape in contact with the 1 st plate-like body 1 is electrically connected to the 1 st plate-like body 1, and a flow portion a2 is formed between the electrochemical reaction portion 3 of the electrochemical element a adjacent to the 2 nd plate-like body 2.

For convenience, some of fig. 21 and the like show the electrochemical element a having a cross section including the internal flow path a1 and the electrochemical element a having a cross section including the flow portion a2 in parallel, and the fuel gas supplied from the 1 st gas supply unit 61 reaches the distribution portion a12 (see fig. 5 to 8 and the like), flows through the distribution portion a12 so as to diffuse in the width direction of one end side, and reaches each sub-flow path a11 (see fig. 5 to 9 and the like) in the internal flow path a 1. At this time, the 1 st gas can be equally distributed from the distribution portion a12 to the plurality of sub flow paths a11, and electrochemical outputs can be equally generated in the respective electrochemical elements.

Here, as shown in fig. 5 and the like, the internal flow path a1 has a distribution portion a12, a plurality of sub flow paths a11, and a merging portion a13 described later. The internal flow path a1 includes a supply buffer section 144 between the distribution section a12 and the plurality of sub-flow paths a11, and a discharge buffer section 154 between the plurality of sub-flow paths a11 and the junction a 13.

The internal flow path a1 is formed by a space where the 1 st plate-like body 1 and the 2 nd plate-like body 2 face each other. In the present embodiment, the 1 st plate-like body 1 is a flat plate-like body, and a gas flow allowing portion 1A described later is formed. The 2 nd plate-like body 2 has a portion protruding in the upward direction and a portion recessed in the downward direction with respect to the stacking direction. Therefore, the 1 st plate-like member 1 and the 2 nd plate-like member 2 are combined to face each other, and the portion of the 2 nd plate-like member 2 protruding in the upward direction abuts on the 1 st plate-like member 1. Then, the portion of the 2 nd plate-like body 2 recessed downward and the 1 st plate-like body 1 form a space that separates the distribution portion a12, the supply buffer portion 144, the plurality of sub flow paths a11, the discharge buffer portion 154, and the confluence portion a 13.

As described below in detail, the supply structure 140 is provided between the distribution portion a12 and the plurality of sub-channels a11 in the direction (+ X direction and-X direction (X direction)) along the flow direction of the fuel gas. The supply structure 140 temporarily stores the fuel gas in the distribution portion a12, and restricts the supply of the fuel gas from the distribution portion a12 to the plurality of sub-channels a 11.

Further, the discharge structure 150 is provided between the plurality of sub-channels a11 and the junction a13 in the direction along the flow direction of the fuel gas. The discharge structure 150 restricts discharge of the fuel gas from the plurality of sub-channels a11 to the junction a 13.

The fuel gas flows through the 1 st gas supply portion 61, the 1 st annular seal portion 42, the 1 st penetration portion 41, and the like, and is supplied to the distribution portion a12 of each electrochemical element a. The fuel gas supplied to distribution portion a12 is temporarily stored in distribution portion a12 by supply structure 140. Then, the fuel gas is introduced from the distribution portion a12 into the plurality of sub flow paths a 11.

The fuel gas introduced into each sub-passage a11 flows through each sub-passage a11 and enters the electrode layer 31 and the electrolyte layer 32 through the gas flow-allowing portion 1A. In addition, the fuel gas further enters the sub-passage a11 together with the electrochemically reacted fuel gas. The fuel gas that has reached the end of the plurality of sub-channels a11 in the flow direction advances toward the junction a13 while the flow to the junction a13 is partially restricted by the discharge structure 150. The fuel gas entering the joining portion a13 flows through the joining portion a13, the 2 nd penetration portion 51, the 2 nd annular seal portion 52, and the like. Then, the fuel gas is discharged from the container 200 through the 1 st gas discharge portion 62 together with the electrochemically reacted fuel gas from the other electrochemical element a.

On the other hand, the air supplied from the 2 nd gas supply unit 71 can enter the flow portion a2 through the distribution chamber 9, and enter the counter electrode layer 33 and the electrolyte layer 32. The air further flows along the electrochemical reaction unit 3 together with the electrochemically reacted air into the flow portion a2, and is discharged from the container 200 through the 2 nd gas discharge portion 72.

The electric power generated in the electrochemical reaction section 3 by the flow of the fuel gas and the air is connected in series between the collectors 81 and 82 by the contact between the electrochemical reaction section 3 of the adjacent electrochemical element a and the 2 nd plate-like body 2, and the combined output is taken out from the output section 8.

The structure of the electrochemical element laminate S is described in detail below.

(5) Specific constitution of electrochemical element laminate S

Next, a specific structure of the electrochemical element laminate S will be described. The electrochemical element laminate S is formed by laminating a plurality of electrochemical elements a.

The electrochemical element a will be described with reference to fig. 4 to 22.

(electrochemical element)

As shown in fig. 5 to 22, the electrochemical element a includes a plate-like support 10 having an internal flow path a1 formed between facing surfaces of a conductive 1 st plate-like body 1 and a conductive 2 nd plate-like body 2.

The plate-like support 10 includes: a gas flow-permitting portion 1A capable of allowing gas to pass through at least a part of the 1 st plate-like body 1 and the 2 nd plate-like body 2 constituting the plate-like support 10 across an inner passage a1 which is an inner side of the plate-like support 10 and an outer side thereof; and an electrochemical reaction part 3 (see fig. 9 to 13, 17 to 21, and the like) having a film-like electrode layer 31, a film-like electrolyte layer 32, and a film-like counter electrode layer 33 in this order in a state of being covered with all or a part of the gas flow-allowing part 1A.

The plate-like support 10 has a1 st penetration portion 41 on one end side, which forms a1 st gas supply path 4 (see fig. 5, 14 to 20, and the like) for supplying a reducing component gas such as a fuel gas or the like or an oxidizing component gas such as air or the like to the internal flow path a1 from the outside in the surface penetration direction, and a2 nd penetration portion 51 on the other end side, which forms a discharge path 5 for discharging the 1 st gas flowing through the internal flow path a1 to the outside in the surface penetration direction of the plate-like support (see fig. 5 to 13 and the like, it should be understood that the supply path 4 and the discharge path 5 and the like have the same configuration by symmetrical shapes).

(plate-shaped support)

(a) Constitution of plate-like support

(a1) Constitution and Material of 1 st plate-like body and 2 nd plate-like body as a whole

The 1 st plate-like body 1 supports the electrochemical reaction part 3 having the electrode layer 31, the electrolyte layer 32, and the counter electrode layer 33, and functions to maintain the strength of the electrochemical element a. As the material of the 1 st plate-like body 1, a material excellent in electron conductivity, heat resistance, oxidation resistance and corrosion resistance is used. For example, ferritic stainless steel, austenitic stainless steel, nickel-based alloy, and the like are used.

In particular, chromium-containing alloys are suitably used. In the present embodiment, it is particularly preferable to use an Fe — Cr alloy containing 18 mass% or more and 25 mass% or less of Cr for the 1 st plate-like body 1, and to use an Fe — Cr alloy containing 0.05 mass% or more of Mn, an Fe — Cr alloy containing 0.15 mass% or more and 1.0 mass% or less of Ti, an Fe — Cr alloy containing 0.15 mass% or more and 1.0 mass% or less of Zr, an Fe — Cr alloy containing Ti and Zr and having a total content of Ti and Zr of 0.15 mass% or more and 1.0 mass% or less of Cu, and an Fe — Cr alloy containing 0.10 mass% or more and 1.0 mass% or less of Cu.

The 2 nd plate-like body 2 is welded and integrated with the 1 st plate-like body 1 at the peripheral edge portion 1a to form a plate-like support 10 (see fig. 6 to 20, etc.). The 2 nd plate-like body 2 may be divided into a plurality of pieces with respect to the 1 st plate-like body 1, and conversely, the 1 st plate-like body 1 may be divided into a plurality of pieces with respect to the 2 nd plate-like body 2. In addition, in the case of integration, other means such as adhesion or fitting may be used instead of welding, and integration may be performed at a portion other than the peripheral edge portion 1a as long as the internal flow path can be formed to be separated from the outside.

The 1 st plate-like body 1 has a gas flow allowing portion 1A, and the gas flow allowing portion 1A is provided with a plurality of through holes 11 (see fig. 9 to 13, 17 to 20, and the like) provided through a front surface and a back surface. For example, the through-hole 11 may be formed in the 1 st plate-like body 1 by laser processing or the like. The through-holes 11 have a function of allowing gas to pass through from the back surface to the front surface of the 1 st plate-like body 1. The gas flow-allowing portion 1A is preferably provided in a region of the 1 st plate-like body 1 smaller than the region where the electrode layer 31 is provided.

The 1 st plate-like body 1 has a metal oxide layer 12 (see fig. 21 and the like described later) as a diffusion suppression layer provided on the surface thereof. That is, a diffusion suppression layer is formed between the 1 st plate-like body 1 and the electrode layer 31 described later. The metal oxide layer 12 is provided not only on the surface of the 1 st plate-like body 1 exposed to the outside but also on the contact surface (interface) with the electrode layer 31. Further, the through-hole 11 may be provided on an inner surface thereof. The metal oxide layer 12 can suppress mutual diffusion of elements between the 1 st plate-like body 1 and the electrode layer 31. For example, in the case of using a chromium-containing ferritic stainless steel as the 1 st plate-like body 1, the metal oxide layer 12 is mainly a chromium oxide. Then, the metal oxide layer 12 containing chromium oxide as a main component suppresses diffusion of chromium atoms and the like of the 1 st plate-like body 1 into the electrode layer 31 and the electrolyte layer 32. The thickness of the metal oxide layer 12 may be any thickness that can achieve both high diffusion prevention performance and resistance.

The metal oxide layer 12 can be formed by various methods, and a method of forming a metal oxide by oxidizing the surface of the 1 st plate-like body 1 is suitably used. The metal oxide layer 12 may be formed on the surface of the 1 st plate-like body 1 by a spray method (a method such as a thermal spray method, an aerosol deposition method, an aerosol vapor deposition method, a powder spray deposition method, a particle spray deposition method, or a cold spray method), a PVD method such as a sputtering method or a PLD method, a CVD method, or the like, or may be formed by plating or an oxidation treatment. Further, the metal oxide layer 12 may also contain a spinel phase having a high conductivity.

When a ferritic stainless steel material is used as the 1 st plate-like member 1, the thermal expansion coefficient is close to that of YSZ (yttria-stabilized zirconia) or GDC (gadolinium-doped ceria, also referred to as CGO) which is a material of the electrode layer 31 or the electrolyte layer 32. Therefore, the electrochemical element a is also less likely to be damaged when temperature cycles of low and high temperatures are repeated. Therefore, the electrochemical device a having excellent long-term durability can be realized, which is preferable. The 1 st plate-like body 1 has a plurality of through holes 11 provided through the front surface and the back surface. For example, the through-hole 11 may be formed in the 1 st plate-like body 1 by mechanical, chemical, or optical piercing. The through-holes 11 have a function of allowing gas to pass through from the back surface to the front surface of the 1 st plate-like body 1. In order to impart gas permeability to the 1 st plate-like body 1, a porous metal may be used. For example, sintered metal, foamed metal, or the like may be used for the 1 st plate-like body 1.

Both the front and back surfaces of the 2 nd plate-like body 2 are formed in a corrugated plate shape, and the surface opposite to the surface forming the internal flow path a1 is electrically connected to the electrochemical reaction parts 3 of the adjacent electrochemical element a.

Then, the passage formed in the vicinity of the portion where the 2 nd plate-like body 2 in the wave-like shape contacts the 1 st plate-like body 1 functions as the flow portion a 2.

To explain further, the sub-flow paths a11 are provided in parallel along the long sides of the plate-like support 10 formed in a rectangular shape, and constitute an internal flow path a1 extending from the supply path 4 provided at one end to the discharge path 5 provided at the other end. The connection position between the 1 st penetration portion 41 and the internal flow path a1 is expanded downward from the contact portion with the 1 st plate-like body 1, the distribution portion a12 (see fig. 5, 14 to 20, and the like) for distributing the 1 st gas supplied from the 1 st penetration portion 41 to each of the sub flow paths a11 is provided, the connection position between the 2 nd penetration portion 51 and the internal flow path a1 is expanded downward from the contact portion with the 1 st plate-like body 1, and the joining portion a13 (see fig. 5 to 13 and the like, and it should be understood that the supply path 4 and the like are the same as the discharge path 5 and the like by symmetrical shapes) for joining the 1 st gas flowing through each of the sub flow paths a11 and guiding to the 2 nd penetration portion 51 is provided.

The material of the 2 nd plate-like body 2 is preferably a heat-resistant metal, and from the viewpoint of reducing the difference in thermal expansion between the plate-like body 1 and the 1 st plate-like body 1 and ensuring reliability of adhesiveness such as welding, it is more preferable to use the same material as the 1 st plate-like body 1.

In the plate-like support 10 including the 1 st plate-like body 1 and the 2 nd plate-like body 2 as described above, the electrode layer 31, the electrolyte layer 32, the counter electrode layer 33, and the like are formed thereon. That is, the electrode layer 31, the electrolyte layer 32, the counter electrode layer 33, and the like are supported by the plate-like support 10, and the electrochemical element a having high strength and excellent seed and seed durability can be realized. Further, the metallic plate-like support 10 is preferable because it is excellent in workability. Further, since the plate-like support 10 having high strength can be obtained even when an inexpensive metal is used for the plate-like support 10, it is possible to make the expensive electrode layer 31, electrolyte layer 32, and the like into thin layers, and it is possible to realize the low-cost electrochemical element a in which the material cost and the processing cost are suppressed, which is preferable.

(a2) Internal flow passage and No. 2 plate-like body constitution

The structure of the internal flow path a1 formed by the 1 st plate-like body 1 and the 2 nd plate-like body 2 facing each other will be described further.

In the present embodiment, the internal flow path a1 is formed on the inner surface of the combination of the 1 st plate-like body 1 in a flat plate shape and the 2 nd plate-like body 2 formed to be convex and concave in the upward (+ Z direction) in the stacking direction or in the downward (-Z direction) in the stacking direction. The internal flow path a1 includes a distribution portion a12, a supply buffer portion 144, a plurality of sub-flow paths a11, a discharge buffer portion 154, and a junction portion a 13. The internal flow path a1 also includes a supply passage 141 (a part of the supply structure 140) through which the 1 st gas passes and a discharge passage 151 (a part of the discharge structure 150).

The side of the supply path 4 where the 1 st gas supply portion 61, the 1 st annular seal portion 42, the 1 st penetration portion 41, and the like are provided is symmetrical to the side of the discharge path 5 where the 1 st gas discharge portion 62, the 2 nd annular seal portion 52, the 2 nd penetration portion 51, and the like are provided. Fig. 6 to 8, 10 to 13 and the like show cross-sectional views of the discharge path 5 side where the 1 st gas discharge portion 62, the 2 nd annular seal portion 52, the 2 nd penetration portion 51 and the like are provided. On the other hand, fig. 14 to 20 and the like show cross-sectional views of the supply path 4 side where the 1 st gas supply portion 61, the 1 st annular seal portion 42, the 1 st penetration portion 41 and the like are provided. Then, in the cross-sectional views on the side of the discharge path 5 such as fig. 6 to 8 and 10 to 13, the 1 st gas flows in the direction of being discharged from the plurality of sub-flow paths a11 to the 2 nd penetration portion 51 and the like via the merging portion a 13. On the other hand, in the cross-sectional views on the supply path 4 side in fig. 14 to 20 and the like, the 1 st gas flows in the direction of being supplied from the distribution portion a12 to the plurality of sub-flow paths a11 through the 1 st penetration portion 41 and the like.

The distribution portion a12 is provided corresponding to each electrochemical element a. The distribution portion a12 is a buffer portion provided on the supply path 4 side for supplying the 1 st gas to each electrochemical element a. The distribution portion a12 is provided upstream of the plurality of sub-passages a11 in the internal passage a1 in the flow direction of the 1 st gas (+ X direction toward the-X direction). As shown in fig. 5, 22, and the like, the distribution portion a12 has a1 st penetration portion 41 penetrating the 2 nd plate-like body 2 formed substantially in the center of the crossing direction (+ Y direction and-Y direction (Y direction)) and the flow direction (+ X direction and-X direction (X direction)) of the flow direction. The 1 st gas flows through the 1 st gas supply portion 61, the 1 st annular seal portion 42, the 1 st penetration portion 41, and the like, and is supplied to the distribution portion a12 of each electrochemical element a.

As shown in fig. 6 to 20, the 1 st plate-like body 1 and the 2 nd plate-like body 2 are integrated by welding the edge portion of the 1 st plate-like body 1 and the edge portion of the 2 nd plate-like body 2 at the peripheral edge portion 1 a. The distribution portion a12 is formed by processing the 2 nd plate-like body 2 so as to be recessed downward in the stacking direction (-Z direction) from the peripheral edge portion 1 a. In short, the distribution portion a12 is formed in the supply blocking portion 142 (a part of the supply structure 140) so as to be positioned differently in the stacking direction.

That is, as shown in fig. 17 and the like, the upper surface of the dispensing portion a12 is positioned below the upper surface of the supply blocking portion 142 in the stacking direction. Then, the upper surface of the supply blocking portion 142 abuts against the lower surface of the 1 st plate-like body 1. Thus, the 1 st gas introduced into the distribution portion a12 is restricted from being discharged from the distribution portion a12 by the supply blocking portion 142 protruding upward in the stacking direction, and is temporarily stored in the distribution portion a12 formed in a concave shape.

In addition, the dispensing portion a12 is long in the + Y direction and the-Y direction (Y direction) as shown in fig. 5 and the like in a top view. The Y-direction length of the distribution portion a12 corresponds to the Y-direction length of the region of the plurality of sub flow paths a11 arranged in parallel at intervals in the Y-direction に.

As shown in fig. 5 to 22, the plurality of sub-passages a11 through which the 1 st gas flows extend in the flow direction, i.e., in the + X direction and the-X direction (X direction). Then, the plurality of sub flow paths a11 are arranged in parallel at intervals in the Y direction as described above. As shown in fig. 5 to 22, the 2 nd plate-like body 2 includes a plurality of sub-flow passage forming portions 160 forming a plurality of sub-flow passages a11, respectively, and a plurality of partition portions 161 provided between adjacent sub-flow passage forming portions 160 and partitioning adjacent sub-flow passages a11, respectively. As shown in fig. 21 and the like, the secondary flow path forming portion 160 is formed in a concave shape having a bottom surface, and the upper surface of the spacer 161 is positioned above the bottom surface of the secondary flow path forming portion 160 in the stacking direction. Then, the upper surface of the spacer 161 abuts against the lower surface of the 1 st plate-like body 1. Thereby, the sub-passages a11 are separated, and the 1 st gas flows through the sub-passages a11 in the flow direction.

In fig. 5 and the like, the sub-flow path a11 extends in the flow direction from the vicinity of the supply structure 140 to the vicinity of the discharge structure 150. However, the present invention is not limited to this, and the sub-flow path a11 may be formed only in a part from the vicinity of the supply structure 140 to the vicinity of the discharge structure 150. That is, the sub-flow path forming portion 160 forming the sub-flow path a11 may be disposed only in a part from the vicinity of the supply structure 140 to the vicinity of the discharge structure 150.

As shown in fig. 21 and 22, the length L3 of the spacer 161 is smaller than the length L4 of the sub-channel forming portion 160 in the + Y direction and the-Y direction (Y direction, intersecting direction with the flow direction) (L3 < L4). In the case of L3 < L4, as shown in fig. 21 and the like, the contact area between the upper surface of the spacer 161 and the lower surface of the 1 st plate-like body 1 can be reduced. That is, the space facing the sub-flow path a11 of the 1 st plate-like body 1 in which the gas flow permission portion 1A is formed can be increased, and the amount of the 1 st gas flowing from the sub-flow path a11 to the electrochemical reaction portion 3 can be increased.

As shown in fig. 5, 14 to 22, and the like, the 2 nd plate-like body 2 has the supply structure 140 between the distribution portion a12 and the plurality of sub-channels a11 in the direction along the flow direction (+ X direction and-X direction (X direction)). The supply structure 140 temporarily stores the 1 st gas in the distribution portion a12, and restricts the supply of the 1 st gas from the distribution portion a12 to the plurality of sub-passages a 11.

The supply structure 140 includes a plurality of supply passage portions 141 and a plurality of supply blocking portions 142. The supply passage section 141 allows the 1 st gas to pass from the distribution section a12 to the plurality of sub flow paths a 11. The supply blocking unit 142 blocks the passage of the 1 st gas from the distribution unit a12 to the plurality of sub flow paths a 11. As shown in fig. 16, the upper surface of the supply blocking portion 142 is positioned above the upper surface of the supply passage portion 141 in the stacking direction, and abuts against the lower surface of the 1 st plate-like body 1. Therefore, the 1 st gas in the distribution portion a12 is prevented from flowing in the flow direction by the supply blocking portion 142, flows in the flow direction through the supply passing portion 141, and flows into the plurality of sub-flow paths a 11.

In the present embodiment, each supply blocking portion 142 is formed in a substantially rectangular shape, as shown in fig. 5, 22, and the like, for example. Then, the rectangular supply blocking portions 142 are arranged in the Y direction so that the long sides thereof extend in the + Y direction and the-Y direction (Y direction). The supply passage portion 141 is provided between the adjacent supply blocking portions 142. That is, the supply passage portion 141 is provided in a section where the short sides of the adjacent supply blocking portions 142 face each other.

As shown in fig. 22, the length L2 of the supply blocking portion 142 is greater than the length L1 of the supply passage portion 141 in the + Y direction and the-Y direction (Y direction, cross direction intersecting the flow direction) (L2 > L1). The length L1 of the supply passage section 141 is preferably smaller than the length L3 of the spacer 161 (L1 < L3). This makes it possible to cause the 1 st gas extruded from the distribution portion a12 through the supply passage portion 141 to collide with the end portion on the + X direction side of the partition 161, and to temporarily store the gas in the supply buffer portion 144 described later.

The relationship between L1 and L2 depends on, for example, the amount of the 1 st gas to be supplied to the distribution portion a12 per unit time, the amount of the 1 st gas to be supplied to the plurality of sub flow paths a11 per unit time, the number of supply blocking portions 142, the length L3 of the partition portion 161 in the Y direction, the length L4 of the sub flow path a11 in the Y direction, and the like.

As described above, the sub passages a11 are separated by the spacers 161. In the flow direction (+ X direction and-X direction (X direction)), any one of the plurality of spacers 161 is disposed to correspond to the supply passage portion 141.

In the flow direction, at least 1 sub-flow passage a11 among the plurality of sub-flow passages a11 is disposed to correspond to the supply blocking unit 142.

Here, the 1 st gas is guided from the distribution portion a12 to the plurality of sub flow paths a11 via the supply passage portion 141. According to the above configuration, since any of the spacers 161 is disposed in the flow direction in correspondence with the supply passage portion 141, the 1 st gas pushed out to the supply passage portion 141 by the distribution portion a12 advances in the flow direction and collides with the spacer 161 protruding upward in the stacking direction. The 1 st gas advances in the intersecting direction intersecting the flow direction due to the collision with the spacer 161. That is, the 1 st gas flowing from the distribution portion a12 through the supply passage portion 141 does not immediately flow into the plurality of sub-passages a11, but collides with the partition 161 immediately before the sub-passage a11 and advances in the intersecting direction. Further, the 1 st gas advancing in the cross direction is not returned to the distribution portion a12 by the supply blocking portion 142 protruding upward in the stacking direction, and is temporarily stored between the supply structure 140 and the plurality of sub flow paths a 11. Then, the 1 st gas is introduced into the plurality of sub flow paths a11 formed in the plurality of sub flow path forming portions 160 along the extrusion from the distribution portion a 12.

The region where the 1 st gas is temporarily stored between the supply structure 140 and the plurality of sub-channels a11 is the supply buffer 144.

In the present embodiment, 1 spacer 161 is disposed corresponding to 1 supply passage 141 in the flow direction. However, the present invention is not limited to this, and a plurality of spacers 161 may be arranged corresponding to 1 supply passage portion 141. In addition, the spacer 161 may not be arranged corresponding to 1 supply passage portion 141, and the spacer 161 may be arranged corresponding to another 1 supply passage portion 141.

Further, a supply blocking portion 142 is provided corresponding to the 1 st penetration portion 41 in the flow direction. This can prevent the 1 st gas introduced from the 1 st penetration portion 41 to the distribution portion a12 from immediately flowing to the plurality of sub flow paths a 11. Therefore, the 1 st gas can be temporarily stored in the distribution portion a 12.

The number of supply blocking portions 142 is not limited to this, and is, for example, 2 or more. The number of the supply blocking portions 142 is preferably set according to the number of the plurality of sub flow paths a 11.

In the above, the supply blocking portions 142 are arranged in a row in the direction intersecting the flow direction.

However, the arrangement is not limited to this as long as the 1 st gas can be temporarily stored in the distribution portion a12 and the 1 st gas can be supplied substantially uniformly to the plurality of sub-passages a 11. For example, the plurality of supply blocking portions 142 may be arranged offset from the crossing direction. The plurality of supply blocking portions 142 may be arranged in the intersecting direction or in a direction away from the intersecting direction.

In the above, the supply blocking unit 142 has a rectangular shape. However, the shape of the supply blocking unit 142 is not limited to this as long as the gas can be uniformly supplied from the distribution unit a12 to the plurality of sub flow paths a 11. For example, the supply blocking portion 142 may be formed in various shapes such as a square, a circle, an oval, and a triangle.

Further, as shown in the above-described embodiments such as fig. 5 and 22, it is preferable that 2 of the plurality of supply blocking portions 142 are provided at positions corresponding to the + Y direction end and the-Y direction end of the dispensing portion a 12. The 1 st gas spreads over the distribution portion a12 so as to spread from the 1 st penetration portion 41 of the distribution portion a12 into the space of the distribution portion a12, and collides with the end face of the distribution portion a 12. Therefore, the 1 st gas colliding with the end surface of the distribution portion a12 may change its direction at the end surface and flow toward the plurality of sub flow paths a 11. Therefore, by providing the supply blocking portion 142 at a position corresponding to the end of the distribution portion a12, the 1 st gas can be inhibited from flowing out to the plurality of sub flow paths a11 immediately from the distribution portion a 12. As a result, as will be described later, the 1 st gas can be supplied from the distribution portion a12 to each of the sub flow paths a11 substantially uniformly.

Next, the flow path portion a13 and the discharge structure 150 will be described. The merging section a13 and the discharge structure 150 have the same configuration as the distribution section a12 and the supply structure 140, respectively.

The merging portion a13 is a buffer portion provided on the discharge path 5 side for discharging the 1 st gas flowing through the plurality of sub-flow paths a 11. The merging portion a13 is provided on the downstream side of the plurality of sub flow paths a11 in the internal flow path a1 in the flow direction of the 1 st gas. As shown in fig. 5, 22, and the like, the 2 nd penetrating portion 51 penetrating the 2 nd plate-like body 2 is formed at a substantially central portion in the flow direction and the intersecting direction thereof in the joining portion a 13. The 1 st gas passing through the plurality of sub-channels a11 is introduced into the junction a13 and discharged to the outside through the 2 nd penetration portion 51, the 2 nd annular seal portion 52, the 1 st gas discharge portion 62, and the like.

The merging portion a13 is formed in the discharge blocking portion 152 (a part of the discharge structure 150) so as to be positioned differently in the stacking direction. That is, as shown in fig. 10 and the like, the upper surface of the merging portion a13 is positioned below the upper surface of the discharge preventing portion 152 in the stacking direction. Then, the upper surface of the discharge preventing portion 152 abuts against the lower surface of the 1 st plate-like body 1. Thus, the 1 st gas that has passed from the plurality of sub-channels a11 to the junction a13 is restricted from being discharged to the junction a13 by the discharge blocking portion 152 that protrudes upward in the stacking direction, and is temporarily stored in the plurality of sub-channels a 11.

In addition, the joining portion a13 is long in the + Y direction and the-Y direction (Y direction) as shown in fig. 5 and the like in a top view. The Y-direction length of the junction a13 corresponds to the Y-direction length of the region of the plurality of sub flow paths a11 arranged in parallel at intervals in the Y-direction.

As shown in fig. 5, 9 to 13, 22, and the like, the 2 nd plate-like body 2 has the discharge structure 150 between the plurality of sub-channels a11 and the junction a13 in the direction along the flow direction (+ X direction and-X direction (X direction)). The discharge structure 150 restricts discharge of the 1 st gas from the plurality of sub-channels a11 to the junction a 13.

The discharge structure 150 includes a plurality of discharge passing portions 151 and a plurality of discharge blocking portions 152. The discharge passage 151 allows the 1 st gas to pass from the plurality of sub-channels a11 to the junction a 13. The discharge preventing portion 152 prevents the 1 st gas from passing from the plurality of sub-channels a11 to the merging portion a 13. As shown in fig. 10 and the like, the upper surface of the discharge preventing portion 152 is positioned above the upper surface of the discharge passing portion 151 in the stacking direction, and abuts against the lower surface of the 1 st plate-like body 1. Therefore, the 1 st gas in the plurality of sub-channels a11 is blocked from flowing in the flow direction by the discharge blocking section 152, flows in the flow direction through the discharge passage section 151, and flows into the junction a 13.

In the present embodiment, the discharge preventing portion 152 is formed in a substantially rectangular shape, as shown in fig. 5, 22, and the like, for example, similarly to the supply preventing portion 142. Then, the rectangular discharge preventing portions 152 are arranged in the Y direction so that the long sides thereof extend in the + Y direction and the-Y direction (Y direction). The discharge passage 151 is provided between adjacent discharge preventing portions 152. That is, the discharge passing portion 151 is provided in a section where short sides of adjacent discharge preventing portions 152 face each other.

As shown in fig. 22, the length L12 of the discharge preventing section 152 is greater than the length L11 of the discharge passing section 151 in the + Y direction and the-Y direction (Y direction, cross direction intersecting the flow direction) (L12 > L11). The length L12 of the discharge preventing section 152 is preferably longer than the length L4 of the sub-flow-path forming section 160 (L12 > L3). This makes it possible to cause the 1 st gas, which has passed from the plurality of sub-flow paths a11 to the joining portion a13, to collide with the discharge blocking portion 152, and to temporarily store the gas in the discharge buffer portion 154, which will be described later.

The relationship between L11 and L12 depends on, for example, the amount of the 1 st gas supplied to the plurality of sub flow paths a11 per unit time, the amount of the 1 st gas to be discharged from the junction a13 per unit time, the number of discharge stoppers 152, the length L3 of the partition 161 in the Y direction, the length L4 of the sub flow path a11 in the Y direction, and the like.

In the flow direction, at least 1 sub-flow passage a11 among the plurality of sub-flow passages a11 is provided corresponding to the discharge preventing portion 152.

In the flow direction, any one of the plurality of spacers 161 is provided corresponding to the discharge passage 151.

According to the above configuration, the 1 st gas pushed out from the plurality of sub-passages a11 travels in the flow direction and collides with the discharge preventing portion 152 protruding upward in the stacking direction. The 1 st gas advances in the intersecting direction intersecting the flow direction due to the collision with the discharge preventing portion 152. That is, the 1 st gas flowing from the plurality of sub-channels a11 does not immediately flow into the merging portion a13, but collides with the discharge blocking portion 152 before the merging portion a13 and advances in the intersecting direction. Then, the 1 st gas is pushed out from the plurality of sub-channels a11, passes through the discharge passage 151, and is introduced into the junction a 13.

The region where the 1 st gas is temporarily stored between the plurality of sub-channels a11 and the discharge structure 150 is the discharge buffer 154.

In addition, a discharge preventing portion 152 is provided corresponding to the 2 nd penetration portion 51 in the flow direction. This can prevent the 1 st gas flowing through the plurality of sub-channels a11 from being immediately introduced into the junction a13 and discharged from the 2 nd penetration portion 51. Therefore, the 1 st gas can be temporarily stored in the plurality of sub-passages a 11.

The shapes, sizes, arrangements, numbers, and the like of the discharge passage portion 151 and the discharge blocking portion 152 are the same as those of the supply passage portion 141 and the supply blocking portion 142. For example, in fig. 22, the length L12 of the discharge preventing portion 152 and the length L11 of the discharge passage portion 151 in the + Y direction and the-Y direction (Y direction, cross direction intersecting the flow direction) are the same as the length L1 of the supply preventing portion 142 and the length L2 of the supply passage portion 141.

The shapes, sizes, arrangements, numbers, and the like of the discharge passage portion 151 and the discharge blocking portion 152 may be different from those of the supply passage portion 141 and the supply blocking portion 142. For example, the discharge passage 151 may be larger than the supply passage 141. Thus, the discharge pressure from the plurality of sub-passages a11 to the junction a13 can be reduced as compared with the supply pressure when the 1 st gas is supplied from the distribution portion a12 to the plurality of sub-passages a 11. The 1 st gas is supplied from the distribution portion a12 to the plurality of sub-passages a11 at a certain supply pressure, so that the flow distribution between the plurality of sub-passages a11 is constant, and the 1 st gas can be smoothly introduced into the merging portion a13 at the time of discharge.

(b) Effects of supply structure and discharge structure

(b1) Function of supply structure

Next, the operation of the supply structure 140 will be described.

The supply blocking unit 142 of the supply structure 140 configured as described above is provided between the distribution unit a12 and the plurality of sub flow paths a11, and serves as a barrier to the flow of the 1 st gas from the distribution unit a12 to the plurality of sub flow paths a 11. Therefore, the pressure loss of the 1 st gas flowing from the distribution portion a12 to the plurality of sub flow paths a11 becomes high, and the 1 st gas introduced into the distribution portion a12 is distributed and temporarily stored so as to fill the distribution portion a 12. Therefore, the pressure in the distribution portion a12 is substantially uniform (pressure equalization) as a whole. That is, the pressure difference between the distribution portion a12 and each of the plurality of sub flow paths a11 is substantially the same. Further, since the 1 st gas is supplied from the distribution portion a12 to the plurality of sub-passages a11 through the supply passage portion 141, the 1 st gas is supplied to each of the sub-passages a11 in a substantially pressure-equalized state. Thus, the flow distribution (flow velocity, flow rate, pressure, and the like) of the 1 st gas along the flow direction is substantially uniform among the sub-flow paths a 11.

Further, the 1 st gas is branched from the distribution portion a12 to the plurality of sub flow paths a 11. By utilizing the rectifying action of the divided flows to the plurality of flow paths in this manner, the flow distribution (flow velocity, flow rate, pressure, and the like) of the 1 st gas is substantially constant as compared with the case where the gas flows through the internal flow path in which the plurality of flow paths are not formed.

As described above, the flow distribution of the 1 st gas along the flow direction is substantially uniform between the sub-flow paths a 11. For example, when a certain position in the flow direction is observed between the sub-passages a11, the flow velocity, flow rate, pressure, and the like of the 1 st gas in each sub-passage a11 are substantially constant in the intersecting direction intersecting the certain position. Thus, in the electrochemical reaction section 3, the difference between the 1 st gas-deficient portion and the 1 st gas-excessive flow portion can be reduced, the utilization rate of the 1 st gas in the entire electrochemical element a can be improved, and the reaction efficiency of the electrochemical reaction can be improved.

When the distribution portion a12, the plurality of sub-passages a11, the supply structure 140, and the like are not employed, the flow distribution of the 1 st gas in each sub-passage a11 is different, and the flow velocity of the 1 st gas in some sub-passages a11 is increased and the flow velocity of the 1 st gas in the other sub-passages a11 is decreased. In the sub-channel a11 in which the flow rate of the 1 st gas is low, the 1 st gas is consumed by the electrochemical reaction, and the 1 st gas is insufficient. This reduces the concentration of the 1 st gas, and the electrode layer of the electrochemical reaction section 3 is oxidized and deteriorated, thereby possibly reducing the electrode performance and mechanical strength. On the other hand, in the sub-channel a11 in which the flow rate of the 1 st gas is high, the 1 st gas is discharged before being consumed in the electrochemical reaction. That is, in the case where the 1 st gas is a fuel gas such as hydrogen, the 1 st gas in a high concentration state is discharged, and the fuel utilization rate is lowered. Here, it is also considered to increase the supply amount of the 1 st gas to each sub-passage a11, relative to the shortage of the 1 st gas in the sub-passage a11 in which the flow rate of the 1 st gas is slow. However, in the sub-passage a11 in which the flow rate of the 1 st gas is high, the amount of the 1 st gas discharged before being consumed in the electrochemical reaction further increases, and the fuel utilization rate further decreases. Therefore, when the flow distribution of the 1 st gas in each sub-passage a11 is different, the reaction efficiency of the electrochemical reaction is reduced, and the power generation efficiency is reduced.

(b2) Function of discharge structure

Next, the operation of the discharge structure 150 will be described.

According to the above configuration, not only the supply structure 140 for supplying the 1 st gas from the distribution portion a12 to the plurality of sub-flow paths a11 with a substantially uniform flow distribution, but also the discharge structure 150 is provided in a portion where the 1 st gas merges from the plurality of sub-flow paths a11 at the merging portion a 13. Since the plurality of sub-channels a11 are sandwiched between the supply structure 140 and the discharge structure 150, the flow distribution (flow velocity, flow rate, pressure, and the like) of the 1 st gas in the plurality of sub-channels a11 can be made substantially uniform, and the reaction efficiency of the electrochemical reaction can be improved.

More specifically, the discharge blocking unit 152 of the discharge structure 150 configured as described above is provided between the plurality of sub-flow paths a11 and the junction a13, and serves as a barrier to the flow of the 1 st gas from the sub-flow path a11 to the junction a 13. Therefore, the pressure loss of the 1 st gas flowing from the plurality of sub-channels a11 to the joining portion a13 becomes high. Therefore, the 1 st gas introduced into the plurality of sub-passages a11 is difficult to be immediately introduced into the junction a13 from the plurality of sub-passages a11, and spreads so as to fill the plurality of sub-passages a 11. This makes it possible to substantially equalize the flow distribution (flow velocity, flow rate, pressure, etc.) of the 1 st gas along the flow direction among the sub-flow paths a 11. Further, since the 1 st gas is distributed so as to fill the plurality of sub-channels a11, the electrochemical reaction is sufficiently performed in the plurality of sub-channels a 11. Thereby, the reaction efficiency of the electrochemical reaction can be improved.

(electrochemical reaction section)

(electrode layer)

As shown in fig. 9 to 13, 17 to 20, and the like, the electrode layer 31 may be provided in a thin layer on the front surface of the 1 st plate-like body 1 in a region larger than the region in which the through-holes 11 are provided. When the thickness is thin, the thickness may be, for example, about 1 to 100 μm, preferably about 5 to 50 μm. If the thickness is set to such a value, the amount of expensive electrode layer material used can be reduced, cost reduction can be achieved, and sufficient electrode performance can be ensured.

The entire region where the through-hole 11 is provided is covered with the electrode layer 31. That is, the through-hole 11 is formed inside the region in which the electrode layer 31 is formed in the 1 st plate-like body 1. In other words, all the through-holes 11 are provided facing the electrode layer 31.

The electrode layer 31 has a plurality of pores in its inner portion and surface so as to have gas permeability.

That is, the electrode layer 31 is formed as a porous layer. The electrode layer 31 is formed, for example, so that the density thereof is 30% or more and less than 80%. The size of the pores can be appropriately selected to be suitable for the smoothing reaction when the electrochemical reaction is performed. The density is a ratio of a material constituting a layer in space, and can be expressed as (1-porosity), and is the same as the relative density.

As the material of the electrode layer 31, for example, NiO-GDC, Ni-GDC, NiO-YSZ, Ni-YSZ, CuO-CeO, etc. can be used₂、Cu-CeO₂And the like. In these examples, GDC, YSZ, CeO may be used₂Referred to as aggregate of the composite. The electrode layer 31 is preferably formed by a low-temperature firing method (for example, a wet method using a firing treatment in a low-temperature region in which a firing treatment in a high-temperature region higher than 1100 ℃ is not performed), a spray method (a method such as a thermal spray method, an aerosol deposition method, an aerosol vapor deposition method, a powder spray deposition method, a particle spray deposition method, or a cold spray method), a PVD method (a sputtering method, a pulsed laser deposition method, or the like), a CVD method, or the like. By these processes that can be used in a low temperature region, for example, a good electrode layer 31 can be obtained without using firing in a high temperature region higher than 1100 ℃. Therefore, the 1 st plate-like body 1 is not damaged, and the interdiffusion of the elements of the 1 st plate-like body 1 and the electrode layer 31 can be suppressed, and the electrochemical element a having excellent durability can be realized, which is preferable. Further, if a low-temperature firing method is used, thenHandling of the raw material is easy, and therefore, is more preferable.

(intermediate layer)

The intermediate layer 34 may be formed in a thin layer on the electrode layer 31 in a state of covering the electrode layer 31. When the thickness is thin, the thickness may be, for example, about 1 to 100 μm, preferably about 2 to 50 μm, and more preferably about 4 to 25 μm. If the thickness is set to such a value, the amount of the material used for the expensive intermediate layer 34 can be reduced, cost reduction can be achieved, and sufficient performance can be ensured. As a material of the intermediate layer 34, for example, YSZ (yttria-stabilized zirconia), SSZ (scandium-stabilized zirconia), GDC (gadolinium-doped ceria), YDC (yttrium-doped ceria), SDC (samarium-doped ceria), or the like can be used. Cerium oxide-based ceramics are particularly suitable.

The intermediate layer 34 is preferably formed by a low-temperature firing method (for example, a wet method using a firing treatment in a low-temperature region that does not perform a firing treatment in a high-temperature region higher than 1100 ℃), a spray method (methods such as a thermal spray method, an aerosol deposition method, an aerosol vapor deposition method, a powder spray deposition method, a particle spray deposition method, a cold spray method, and the like), a PVD method (a sputtering method, a pulsed laser deposition method, and the like), a CVD method, and the like. By these film formation processes that can be used in the low temperature region, the intermediate layer 34 can be obtained without using firing in the high temperature region higher than 1100 ℃. Therefore, mutual diffusion of the elements of the 1 st plate-like body 1 and the electrode layer 31 can be suppressed without damaging the 1 st plate-like body 1, and an electrochemical element a having excellent durability can be realized. Further, the use of the low-temperature firing method is more preferable because the treatment of the raw material becomes easy.

The intermediate layer 34 preferably has oxygen ion (oxide ion) conductivity. It is further preferable that the mixed conductivity of oxygen ions (oxide ions) and electrons be present. The intermediate layer 34 having these properties is suitable for application to the electrochemical element a.

(electrolyte layer)

As shown in fig. 9 to 13, 17 to 20, and the like, the electrolyte layer 32 is formed in a thin layer on the intermediate layer 34 so as to cover the electrode layer 31 and the intermediate layer 34. The film may be formed in a thin film having a thickness of 10 μm or less. Specifically, the electrolyte layer 32 is provided across the intermediate layer 34 and the 1 st plate-like body 1 (spanning). With this configuration, the electrolyte layer 32 is bonded to the 1 st plate-like body 1, whereby the electrochemical device as a whole can be made excellent in robustness.

As shown in fig. 9 and the like, the electrolyte layer 32 is provided on the front surface of the 1 st plate-like body 1 over a region larger than the region where the through-hole 11 is provided. That is, the through-hole 11 is formed inside the region in which the electrolyte layer 32 is formed in the 1 st plate-like body 1.

Further, the gas can be prevented from leaking from the electrode layer 31 and the intermediate layer (not shown) around the electrolyte layer 32. When electrochemical element a is used as a component of the SOFC, gas is supplied to electrode layer 31 through holes 11 from the back side of first plate-shaped body 1 during operation of the SOFC. At the portion where the electrolyte layer 32 contacts the 1 st plate-like body 1, gas leakage can be suppressed without providing any other member such as a gasket.

In the present embodiment, the periphery of the electrode layer 31 is completely covered with the electrolyte layer 32, but a configuration may be adopted in which the electrolyte layer 32 is provided on the upper portions of the electrode layer 31 and the intermediate layer 34, and a gasket or the like is provided around the electrolyte layer.

As the material of the electrolyte layer 32, an oxygen ion conducting electrolyte material such as YSZ (yttria-stabilized zirconia), SSZ (scandium-stabilized zirconia), GDC (gadolinium-doped ceria), YDC (yttrium-doped ceria), SDC (samarium-doped ceria), LSGM (strontium-doped, magnesium-doped lanthanum gallate), or a hydrogen ion conducting electrolyte material such as a perovskite-type oxide can be used. Zirconia ceramics are particularly suitable. If the electrolyte layer 32 is made of zirconia-based ceramic, the operation temperature of the SOFC using the electrochemical element a can be set higher than that of cerium oxide-based ceramic or various hydrogen ion conductive materials. For example, when the electrochemical element a is used for an SOFC, if a system is configured such that a material that can exhibit high electrolyte performance even in a high-temperature region of about 650 ℃ or higher, such as YSZ, is used as the material of the electrolyte layer 32, a hydrocarbon-based raw fuel such as city gas or LPG is used as the raw fuel of the system, and the raw fuel is reformed into the anode gas of the SOFC by steam reforming or the like, it is possible to construct a high-efficiency SOFC system that uses the heat generated in the cell stack of the SOFC as the reforming of the raw fuel gas.

The electrolyte layer 32 is preferably formed by a low-temperature firing method (for example, a wet method using a firing treatment in a low-temperature region that does not perform a firing treatment in a high-temperature region higher than 1100 ℃), a spray method (methods such as a thermal spray method, an aerosol deposition method, an aerosol vapor deposition method, a powder spray deposition method, a particle spray deposition method, a cold spray method, and the like), a PVD method (sputtering method, a pulsed laser deposition method, and the like), a CVD (chemical vapor growth) method, and the like. By these film forming processes that can be used in a low temperature region, for example, the electrolyte layer 32 that is dense and high in airtightness and gas barrier properties can be obtained without using firing in a high temperature region higher than 1100 ℃. Therefore, damage to the 1 st plate-like body 1 can be suppressed, interdiffusion of elements of the 1 st plate-like body 1 and the electrode layer 31 can be suppressed, and an electrochemical element a having excellent performance, seeding and durability can be realized. In particular, if a low-temperature firing method, a spray method, or the like is used, it is preferable because a low-cost device can be realized. Further, if the spray coating method is used, a dense electrolyte layer having high air-tightness and gas-barrier properties can be easily obtained in a low temperature region, which is more preferable.

The electrolyte layer 32 is densely formed to block gas leakage of the anode gas and the cathode gas and to exhibit high ion conductivity. The density of the electrolyte layer 32 is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more. When the electrolyte layer 32 is a uniform layer, the compactness thereof is preferably 95% or more, more preferably 98% or more. In the case where the electrolyte layer 32 is formed in a plurality of layered forms, at least a portion thereof is preferably included in a layer having a density of 98% or more (dense electrolyte layer), and more preferably included in a layer having a density of 99% or more (dense electrolyte layer). This is because if such a dense electrolyte layer is included in a part of the electrolyte layer, even when the electrolyte layer is formed in a plurality of layers, the electrolyte layer can be easily formed to be dense and to have high gas tightness and gas barrier properties.

(reaction preventing layer)

The reaction-preventing layer 35 may be formed in a thin layer on the electrolyte layer 32. When the thickness is thin, the thickness may be, for example, about 1 to 100 μm, preferably about 2 to 50 μm, and more preferably about 3 to 15 μm. If the thickness is set to such a value, the amount of the expensive reaction-preventing layer material to be used can be reduced, cost reduction can be achieved, and sufficient performance can be ensured. As the material of the reaction preventing layer, any material may be used as long as it can prevent the reaction between the components of the electrolyte layer 32 and the components of the counter electrode layer 33, and for example, a cerium oxide-based material or the like can be used. As the material of the reaction-preventing layer 35, a material containing at least 1 kind of element selected from Sm, Gd, and Y is suitably used. At least 1 element selected from the group consisting of Sm, Gd, and Y may be contained, and the total content of these elements is 1.0 mass% or more and 10 mass% or less. By introducing the reaction-preventing layer 35 between the electrolyte layer 32 and the counter electrode layer 33, the reaction between the constituent material of the counter electrode layer 33 and the constituent material of the electrolyte layer 32 is effectively suppressed, and the long-term stability of the performance of the electrochemical element a can be improved. If the formation of the reaction-preventing layer 35 is carried out by a method capable of forming at a treatment temperature of 1100 ℃ or lower as appropriate, damage to the 1 st plate-like body 1 can be suppressed, interdiffusion of elements of the 1 st plate-like body 1 and the electrode layer 31 can be suppressed, and an electrochemical element a having excellent properties, seeding and durability can be realized, and therefore, such a method is preferable. It can be suitably carried out using, for example, a low-temperature firing method (for example, a wet method using a firing treatment in a low-temperature region in which a firing treatment in a high-temperature region higher than 1100 ℃ is not carried out), a spray method (a method such as a thermal spray method, an aerosol deposition method, an aerosol vapor deposition method, a powder spray deposition method, a particle spray deposition method, a cold spray method), a PVD method (a sputtering method, a pulsed laser deposition method, or the like), a CVD method, or the like. In particular, if a low-temperature firing method, a spray method, or the like is used, it is preferable because a low-cost device can be realized. Further, if the low-temperature firing method is used, the processing of the raw material becomes easy, and therefore, it is more preferable.

(counter electrode layer)

As shown in fig. 9 to 13, 17 to 20, and the like, the counter electrode layer 33 may be formed in a thin layer on the electrolyte layer 32 or the reaction-preventing layer 35. When the thickness is thin, the thickness may be, for example, about 1 to 100 μm, preferably about 5 to 50 μm. If the thickness is set to such a value, the amount of expensive counter electrode layer material to be used can be reduced, cost reduction can be achieved, and sufficient electrode performance can be ensured. As the material of the counter electrode layer 33, for example, a composite oxide such as LSCF or LSM, a cerium oxide-based oxide, and a mixture thereof can be used. In particular, the counter electrode layer 33 preferably contains a perovskite type oxide containing 2 or more elements selected from La, Sr, Sm, Mn, Co, and Fe. The counter electrode layer 33 formed using the above-described material functions as a cathode.

Note that if the formation of the electrode layer 33 is carried out by a method capable of forming at a treatment temperature of 1100 ℃ or lower as appropriate, damage to the 1 st plate-like body 1 can be suppressed, and interdiffusion of elements of the 1 st plate-like body 1 and the electrode layer 31 can be suppressed, whereby an electrochemical element a having excellent properties, seeding and durability can be realized, which is preferable. It can be suitably carried out using, for example, a low-temperature firing method (for example, a wet method using a firing treatment in a low-temperature region in which a firing treatment in a high-temperature region higher than 1100 ℃ is not carried out), a spray method (a method such as a thermal spray method, an aerosol deposition method, an aerosol vapor deposition method, a powder spray deposition method, a particle spray deposition method, a cold spray method), a PDV method (a sputtering method, a pulsed laser deposition method, or the like), a CVD method, or the like. In particular, if a low-temperature firing method, a spray method, or the like is used, it is preferable because a low-cost device can be realized. Further, if the low-temperature firing method is used, the processing of the raw material becomes easy, and therefore, it is more preferable.

By configuring the electrochemical reaction section 3 in this manner, the electrochemical element a can be used as a power generation cell of a solid oxide fuel cell when the electrochemical reaction section 3 is caused to function as a fuel cell (electrochemical power generation cell). For example, a fuel gas containing hydrogen as a1 st gas is supplied to the electrode layer 31 from the surface on the back side of the 1 st plate-like body 1 through the through-holes 11, and air as a2 nd gas is supplied to the counter electrode layer 33 as the counter electrode of the electrode layer 31, and the operating temperature is maintained at, for example, about 700 ℃. Thus, in the counter electrode layer 33, oxygen O contained in the air₂And an electron e^-React to generate oxygen ions O^2-. The oxygen ion O^2-Moves to the electrode layer 31 through the electrolyte layer 32. In the electrode layer 31, hydrogen H contained in the supplied fuel gas₂With oxygen ions O^2-React to form water H₂O and an electron e^-。

In the case where an electrolyte material that conducts hydrogen ions to the electrolyte layer 32 is used, hydrogen H contained in the fuel gas flowing through the electrode layer 31₂Discharge of electrons e^-To generate hydrogen ions H^＋. The hydrogen ion H^＋Moves to the counter electrode layer 33 through the electrolyte layer 32. Oxygen O contained in the air in the counter electrode layer 33₂With hydrogen ions H^＋Electron e^-React to form water H₂O。

Through the above reaction, an electromotive force as an electrochemical output is generated between the electrode layer 31 and the counter electrode layer 33. At this time, the electrode layer 31 functions as a fuel electrode (anode) of the fuel cell, and the counter electrode layer 33 functions as an air electrode (cathode).

Although not shown in fig. 9 to 13, 17 to 20, and the like, in the present embodiment, the electrochemical reaction section 3 has an intermediate layer 34 between the electrode layer 31 and the electrolyte layer 32 as shown in fig. 21. Further, a reaction preventing layer 35 is provided between the electrolyte layer 32 and the counter electrode layer 33.

(method of manufacturing electrochemical reaction part)

Next, a method for producing the electrochemical reaction part 3 will be described. Since the following description of the intermediate layer 34 and the reaction-preventing layer 35 is omitted in fig. 9 to 13, 17 to 20, and the like, the description will be mainly given using fig. 21.

(electrode layer Forming step)

In the electrode layer forming step, the electrode layer 31 is formed in a thin film state in a wider region than the region of the front surface of the 1 st plate-like body 1 in which the through-holes 11 are provided. The through-hole 11 of the 1 st plate-like body 1 may be provided by laser processing or the like. As described above, the electrode layer 31 can be formed by a low-temperature firing method (a wet method in which firing treatment is performed in a low-temperature region of 1100 ℃ or lower), a spraying method (a method such as a thermal spraying method, an aerosol deposition method, an aerosol vapor deposition method, a powder spray deposition method, a particle spray deposition method, or a cold spraying method), a PVD method (a sputtering method, a pulsed laser deposition method, or the like), a CVD method, or the like. In the case of using either method, it is desirable to perform at a temperature of 1100 ℃ or less in order to suppress deterioration of the 1 st plate-like body 1.

In the case where the electrode layer formation step is performed by the low-temperature firing method, the electrode layer formation step is specifically performed as in the following example.

First, a material paste is prepared by mixing a material powder of the electrode layer 31 with a solvent (dispersion medium), and the material paste is applied to the surface of the 1 st plate-like body 1 and fired at 800 to 1100 ℃.

(diffusion suppressing layer formation step)

In the firing step in the electrode layer forming step, the metal oxide layer 12 (diffusion suppression layer) is formed on the surface of the 1 st plate-like body 1. In the above-described firing step, if a firing step is included in which the firing atmosphere is set to an atmosphere condition in which the oxygen partial pressure is low, it is preferable to form a metal oxide layer 12 (diffusion suppression layer) having a high interdiffusion suppression effect of the elements and a high quality with a low resistance value. The diffusion-suppressing layer forming step may be separately included, including the case where the electrode layer forming step is a coating method without firing. In any case, it is desirable to carry out the treatment at a treatment temperature of 1100 ℃ or less at which damage to the 1 st plate-like body 1 can be suppressed.

(intermediate layer formation step)

In the intermediate layer forming step, the intermediate layer 34 is formed in a thin layer on the electrode layer 31 so as to cover the electrode layer 31. As described above, the intermediate layer 34 can be formed by a low-temperature firing method (a wet method in which firing treatment is performed in a low-temperature region of 1100 ℃ or lower), a spraying method (a method such as a thermal spraying method, an aerosol deposition method, an aerosol vapor deposition method, a powder spray deposition method, a particle spray deposition method, or a cold spraying method), a PVD method (a sputtering method, a pulsed laser deposition method, or the like), a CVD method, or the like. In the case of using either method, it is desirable to perform at a temperature of 1100 ℃ or less in order to suppress deterioration of the 1 st plate-like body 1.

In the case where the intermediate layer formation step is performed by the low-temperature firing method, the intermediate layer formation step is specifically performed as in the following example.

First, a material paste is prepared by mixing the material powder of the intermediate layer 34 with a solvent (dispersion medium), and is applied to the front surface of the 1 st plate-like body 1. Then, the intermediate layer 34 is compression-molded (intermediate layer smoothing step) and fired at 1100 ℃ or lower (intermediate layer firing step). The calendering of the intermediate layer 34 can be performed by, for example, CIP (Cold Isostatic Pressing) molding, roll press molding, RIP (Rubber Isostatic Pressing) molding, or the like. It is preferable that the intermediate layer 34 is fired at a temperature of 800 ℃ to 1100 ℃. This is because, at such a temperature, damage and seed deterioration of the 1 st plate-like body 1 can be suppressed, and an intermediate layer 34 having high strength can be formed. Further, it is more preferable if the firing of the intermediate layer 34 is performed at 1050 ℃ or lower, and it is still more preferable if it is performed at 1000 ℃ or lower. This is because the firing temperature of the intermediate layer 34 is lowered, damage and seed deterioration of the 1 st plate-like body 1 can be further suppressed, and the electrochemical element a can be formed. In addition, the order of the intermediate layer smoothing step and the intermediate layer firing step may be replaced.

The intermediate layer smoothing step may be performed by performing stretch forming, leveling treatment, surface cutting, seed grinding treatment, and the like.

(electrolyte layer formation step)

In the electrolyte layer forming step, the electrolyte layer 32 is formed in a thin layer state on the intermediate layer 34 in a state of covering the electrode layer 31 and the intermediate layer 34. Further, the film may be formed in a thin film state having a thickness of 10 μm or less. As described above, the electrolyte layer 32 can be formed by a low-temperature firing method (a wet method in which firing is performed at a low temperature of 1100 ℃ or lower), a spray method (a method such as a thermal spray method, an aerosol deposition method, an aerosol vapor deposition method, a powder spray deposition method, a particle spray deposition method, or a cold spray method), a PVD method (a sputtering method, a pulsed laser deposition method, or the like), a CVD method, or the like. In the case of using either method, it is desirable to perform at a temperature of 1100 ℃ or less in order to suppress deterioration of the 1 st plate-like body 1.

In order to form the electrolyte layer 32 having a high quality, which is dense and has high gas tightness and gas barrier performance in a temperature region of 1100 ℃ or less, it is desirable to perform the electrolyte layer forming step by a spray coating method. At this time, the material of the electrolyte layer 32 is ejected toward the intermediate layer 34 on the 1 st plate-like body 1 to form the electrolyte layer 32.

(reaction-preventing layer formation step)

In the reaction-preventing layer formation step, the reaction-preventing layer 35 is formed in a thin layer on the electrolyte layer 32. As described above, the formation of the reaction preventing layer 35 can be performed by a low-temperature firing method (a wet method in which firing treatment is performed in a low-temperature region of 1100 ℃ or lower), a spraying method (a method such as a thermal spraying method, an aerosol deposition method, an aerosol vapor deposition method, a powder spray deposition method, a particle spray deposition method, or a cold spraying method), a PVD method (a sputtering method, a pulsed laser deposition method, or the like), a CVD method, or the like. In the case of using either method, it is desirable to perform at a temperature of 1100 ℃ or less in order to suppress deterioration of the 1 st plate-like body 1. In order to flatten the upper surface of the reaction-preventing layer 35, for example, a leveling treatment, a cutting or seed polishing treatment may be performed after the formation of the reaction-preventing layer 35, or a press working may be performed after the wet formation and before the firing.

(counter electrode layer formation step)

In the counter electrode layer forming step, the counter electrode layer 33 is formed in a thin layer on the reaction preventing layer 35. As described above, the electrode layer 33 can be formed by a low-temperature firing method (a wet method in which firing treatment is performed in a low-temperature region of 1100 ℃ or lower), a spraying method (a method such as a thermal spraying method, an aerosol deposition method, an aerosol vapor deposition method, a powder spray deposition method, a particle spray deposition method, or a cold spraying method), a PVD method (a sputtering method, a pulsed laser deposition method, or the like), a CVD method, or the like. In the case of using either method, it is desirable to perform at a temperature of 1100 ℃ or less in order to suppress deterioration of the 1 st plate-like body 1.

By performing the above process, the electrochemical reaction part 3 can be manufactured.

The electrochemical reaction section 3 may be provided without one or both of the intermediate layer 34 and the reaction-preventing layer 35. That is, the electrode layer 31 may be formed in contact with the electrolyte layer 32, or the electrolyte layer 32 may be formed in contact with the counter electrode layer 33. In this case, in the above-described manufacturing method, the intermediate layer forming step and the reaction-preventing layer forming step are omitted. In addition, a step of forming another layer or a plurality of layers of the same kind may be added, but in any case, it is desirable to perform the forming at a temperature of 1100 ℃.

(electrochemical element laminate)

As shown in fig. 4, the electrochemical element laminate S is configured by laminating a plurality of electrochemical elements a in a predetermined lamination direction. The plate-shaped support 10 constituting one electrochemical element a (1 st electrochemical element a) and the plate-shaped support 10 constituting the other electrochemical element a (2 nd electrochemical element a) are arranged to face each other in the adjacent electrochemical element a.

For example, one electrochemical element a (1 st electrochemical element a) has a plate-like support 10, and the plate-like support 10 has the 1 st plate-like body 1 and the 2 nd plate-like body 2 in which the electrochemical reaction parts 3 are arranged. Similarly, the plate-shaped support 10 of the 2 nd electrochemical element a adjacent to the 1 st electrochemical element a in the lower direction (1 st direction) and the upper direction (2 nd direction) has the plate-shaped support 10, and the plate-shaped support 10 has the 1 st plate-shaped body 1 and the 2 nd plate-shaped body 2 in which the electrochemical reaction parts 3 are arranged.

The outer surface of the 2 nd plate-like body 2 of the 1 st electrochemical element a is electrically connected to the outer surface of the 1 st plate-like body 1 of the 2 nd electrochemical element a adjacent in the upper direction. Further, a flow portion a2 through which the 2 nd gas flows along the outer surfaces of the 2 nd plate-like body 2 of the 1 st electrochemical element a and the outer surface of the 1 st plate-like body 1 of the 2 nd electrochemical element a adjacent in the upper direction is formed between the outer surfaces.

Further, the outer surface of the 1 st plate-like body 1 of the 1 st electrochemical element a is electrically connected to the outer surface of the 2 nd plate-like body 2 of the 2 nd electrochemical element a adjacent in the lower direction. For the electrical connection, a method of simply bringing the conductive surface portions into contact with each other, applying surface pressure to the contact surfaces, or reducing contact resistance by allowing a highly conductive material to exist therebetween, or the like can be employed. A sub-flow path a11 (a part of the internal flow path a 1) through which the 1 st gas flows along the outer surface of the 1 st plate-like body 1 of the 1 st electrochemical element a and the outer surface of the 2 nd plate-like body 2 of the 2 nd electrochemical element a adjacent in the downward direction is formed between the outer surfaces.

The plurality of electrochemical elements a are stacked. Specifically, the rectangular electrochemical elements are arranged and stacked with the electrochemical reaction parts of the electrochemical elements facing upward, with the 1 st penetration part 41 at one end aligned with the 2 nd penetration part 51 at the other end. Then, the 1 st annular seal portion 42 is sandwiched between the 1 st penetration portions 41, and the 2 nd annular seal portion 52 is sandwiched between the 2 nd penetration portions 51.

The plate-like support 10 has a1 st penetration portion 41 on one end side in the longitudinal direction of the rectangular plate-like support 10, and the 1 st gas supply passage 4 for supplying one of the reducing component gas and the oxidizing component gas to the internal flow path a1 from the outside in the surface penetration direction is formed. The flow portion a2 has a1 st annular seal 42 as an annular seal for separating the 1 st penetration portion 41 and the flow portion a2 formed on both outer surfaces of the plate-like support 10. Further, the 1 st penetration portion 41 and the 1 st annular seal portion 42 form the supply path 4 for supplying the 1 st gas to the internal flow path a 1. In addition, an annular bulging portion a is provided on the opposite side surface of the 1 st plate-like body 1 from the internal flow path a1 around the portion of the 1 st plate-like body 1 where the 1 st annular seal portion 42 abuts, so that the 1 st annular seal portion 42 can be easily positioned in the direction along the surface of the 1 st plate-like body 1.

The plate-like support 10 has a2 nd penetration portion 51 on the other end side, and forms a discharge path 5 for discharging the 1 st gas flowing through the internal flow path a1 to the outside in the surface penetration direction of the plate-like support 10. The 2 nd penetration portion 51 is configured to allow the 1 st gas to flow therethrough in a state of being separated from the 2 nd gas. The 2 nd penetrating portion 51 includes a2 nd annular seal portion 52 as an annular seal portion in the flow portion a2, and separates the 2 nd penetrating portion 51 and the flow portion a2 formed on both outer surfaces of the plate-shaped support 10. The 2 nd penetration portion 51 and the 2 nd annular seal portion 52 form a discharge path 5 for discharging the 1 st gas flowing through the internal flow path a 1.

The 1 st and 2 nd annular seal portions 42 and 52 are formed of a ceramic material such as alumina, mica, or an insulating material such as a metal covering these, and function as insulating seal portions for electrically insulating adjacent electrochemical elements from each other.

(6) Energy system and electrochemical device

Next, an energy system and an electrochemical device will be described with reference to fig. 23.

The energy system Z includes the electrochemical device 100 and a heat exchanger 190 as an exhaust heat utilization unit that reuses heat exhausted from the electrochemical device 100.

The electrochemical device 100 includes an electrochemical module M, a fuel supply module, and an inverter (an example of a power converter) 104 as an output unit 8 that takes out electric power from the electrochemical module M. The fuel supply module is formed by a desulfurizer 101, a gasifier 106, and a reformer 102, and has a fuel supply unit 103 that supplies a fuel gas containing a reducing component to the electrochemical module M. At this time, the reformer 102 serves as a fuel converter.

Specifically, the electrochemical device 100 includes: a desulfurizer 101, a reforming water tank 105, a vaporizer 106, a reformer 102, a blower 107, a combustion section 108, an inverter 104, a control section 110, and an electrochemical module M.

The desulfurizer 101 removes (desulfurizes) sulfur compound components contained in a hydrocarbon-based raw fuel such as a city gas. When the raw fuel contains sulfur compounds, the desulfurizer 101 can suppress adverse effects of the sulfur compounds on the reformer 102 and the electrochemical element a. The vaporizer 106 generates water vapor from the reformate supplied from the reformate tank 105. The reformer 102 steam-reforms the raw fuel desulfurized by the desulfurizer 101 using the steam generated by the vaporizer 106 to generate a reformed gas containing hydrogen.

The electrochemical module M generates electricity by performing an electrochemical reaction using the reformed gas supplied from the reformer 102 and the air supplied from the blower 107. The combustion section 108 mixes the reaction exhaust gas discharged from the electrochemical module M with air, and combusts combustible components in the reaction exhaust gas.

The inverter 104 adjusts the output power of the electrochemical module M to have the same voltage and the same frequency as the power received from a commercial system (not shown). The control unit 110 controls the operation of the electrochemical device 100 and the energy system Z.

The reformer 102 performs reforming processing of the raw fuel using combustion heat generated by combustion of the reaction exhaust gas in the combustion section 108.

The raw fuel is supplied to the desulfurizer 101 through a raw fuel supply path 112 by the operation of the booster pump 111. The reformed water of the reformed water tank 105 is supplied to the gasifier 106 through the reformed water supply path 114 by the operation of the reformed water pump 113. Then, the raw fuel supply path 112 is merged with the reformed water supply path 114 at a position downstream of the desulfurizer 101, and the reformed water merged outside the vessel 200 and the raw fuel are supplied to the gasifier 106.

The reforming water is vaporized by the vaporizer 106 to form water vapor. The raw fuel containing the steam generated by the gasifier 106 is supplied to the reformer 102 through a raw fuel supply path 115 containing the steam. The raw fuel is steam-reformed in the reformer 102 to generate a reformed gas (1 st gas having a reducing component) containing hydrogen as a main component. The reformed gas generated by the reformer 102 is supplied to the electrochemical module M through the fuel supply unit 103.

The reaction exhaust gas is combusted in the combustion section 108 to form combustion exhaust gas, and the combustion exhaust gas is sent to the heat exchanger 190 through the combustion exhaust gas discharge path 116. A combustion catalyst section 117 (for example, a platinum catalyst) is disposed in the combustion exhaust gas discharge path 116, and combusts and removes reducing components such as carbon monoxide and hydrogen contained in the combustion exhaust gas.

The heat exchanger 190 generates warm water by exchanging heat between the combustion exhaust gas generated by combustion in the combustion unit 108 and the supplied cold water. That is, the heat exchanger 190 functions as an exhaust heat utilization unit that reuses heat exhausted from the electrochemical device 100.

Instead of the exhaust heat utilization portion, a reaction exhaust gas utilization portion may be provided that utilizes reaction exhaust gas (unburned) discharged from the electrochemical module M. Further, at least a part of the reaction off-gas flowing from the 1 st gas discharge part 62 to the outside of the container 200 may be merged and recirculated at any position of 100, 101, 103, 106, 112, 113, and 115 in fig. 23. The reaction exhaust gas contains residual hydrogen that is not used for the reaction in the electrochemical element a. The reaction exhaust gas utilization unit utilizes residual hydrogen gas, utilizes heat generated by combustion, generates electricity by a fuel cell or the like, and effectively utilizes energy.

[ other embodiments ]

The configurations disclosed in the above embodiments (including other embodiments, the same applies hereinafter) may be used in combination with the configurations disclosed in the other embodiments as long as no contradiction occurs, and the embodiments disclosed in the present specification are examples, and the embodiments of the present invention are not limited thereto, and may be appropriately changed within a range not departing from the object of the present invention.

(1) In the above embodiment, the 2 nd plate-like body 2 having the uneven shape formed along the stacking direction is opposed to the 1 st plate-like body 1, thereby forming the internal flow path a1 having the distribution portion a12, the plurality of sub-flow paths a11, the junction portion a13, the supply buffer portion 144, and the discharge buffer portion 154. However, as long as the internal flow path a1 can be formed, the 1 st plate-like body 1 having the uneven shape formed along the stacking direction may be opposed to the 2 nd plate-like body 2. Further, the 1 st plate-like body 1 partially formed with the concave-convex shape may be opposed to the 2 nd plate-like body 2 partially formed with the concave-convex shape.

(2) In the above embodiment, the 2 nd plate-like body 2 is provided with the supply structure 140 and the discharge structure 150. However, any one of the supply structure 140 and the discharge structure 150 may be provided in the 2 nd plate-like body 2. For example, the 2 nd plate-like body 2 may have only the supply structure 140 without the discharge structure 150. Even in the case where only the supply structure 140 is provided, the gas can be supplied to the plurality of sub-passages a11 from the distribution portion a12, and the flow distribution (flow velocity, flow rate, pressure, and the like) of the 1 st gas in the flow direction in each sub-passage a11 can be made substantially uniform.

(3) In the above embodiment, the electrochemical element a is used in a solid oxide fuel cell as the electrochemical device 100, but the electrochemical element a may be used in a solid oxide electrolytic cell, an oxygen sensor using a solid oxide, or the like. The electrochemical element a is not limited to a combination of a plurality of electrochemical elements and may be used as the electrochemical element laminate S or the electrochemical module M, or may be used alone.

That is, in the above embodiment, a configuration capable of improving the efficiency of converting chemical energy such as fuel into electric energy has been described.

That is, in the above embodiment, the electrochemical element a and the electrochemical module M are operated as a fuel cell, and hydrogen gas is flowed to the electrode layer 31 and oxygen gas is flowed to the counter electrode layer 33. Thus, in the counter electrode layer 33, oxygen molecules O₂And an electron e^-React to generate oxygen ions O^2-. The oxygen ion O^2-Moves to the electrode layer 31 through the electrolyte layer 32. In the electrode layer 31, hydrogen molecules H₂With oxygen ions O^2-Reacting to form water H₂O and an electron e^-. By the above reaction, electromotive force is generated between the electrode layer 31 and the counter electrode layer 33 to generate power.

On the other hand, when the electrochemical element a and the electrochemical module M are operated as an electrolytic cell, a gas containing water vapor and carbon dioxide flows through the counter electrode layer 31, and a voltage is applied between the electrode layer 31 and the counter electrode layer 33. Thus, in the electrode layer 31, electrons e^-And water molecule H₂O, carbon dioxide molecule CO₂Reaction takes placeForm hydrogen molecules H₂Carbon monoxide CO and oxygen ion O^2-. Oxygen ion O^2-Moves to the counter electrode layer 33 through the electrolyte layer 32. In the counter electrode layer 33, oxygen ions O^2-Giving off electrons to form oxygen molecules O₂. By the above reaction, water molecule H₂O is electrolyzed to hydrogen H₂With oxygen O₂And in flow communication with carbon dioxide molecules CO₂Is electrolyzed into carbon monoxide CO and oxygen O₂。

Circulating the carbon dioxide containing water vapor and carbon dioxide molecules CO₂In the case of the gas of (2), a fuel converter 25 (fig. 25) may be provided, which synthesizes various compounds such as hydrocarbons from hydrogen, carbon monoxide, and the like generated in the electrochemical element a and the electrochemical module M by the above-described electrolysis. Hydrocarbons and the like generated by the fuel converter 25 can be taken out of the present system and used as a seed and a seed device as a fuel by a fuel supply unit (not shown). Further, the fuel converter 25 may convert hydrogen and carbon monoxide into chemical raw materials for use.

Fig. 25 shows an example of the energy system Z and the electrochemical device 100 when the electrochemical reaction unit 3 is operated as an electrolytic cell. The water and carbon dioxide supplied in this system are electrolyzed in the electrochemical reaction section 3 to generate hydrogen, carbon monoxide, and the like. Further, hydrocarbons and the like are synthesized in the fuel converter 25. The above configuration, in which the heat exchanger 24 in fig. 25 is operated as an exhaust heat utilization unit for vaporizing the reaction heat generated by the reaction of the fuel converter 25 by exchanging heat with water, and the heat exchanger 23 in fig. 25 is operated as an exhaust heat utilization unit for preheating the exhaust heat generated by the electrochemical element a by exchanging heat with steam and carbon dioxide, can improve energy efficiency.

The power converter 93 supplies electric power to the electrochemical element a. Thus, as described above, the electrochemical element a functions as an electrolytic cell.

Therefore, according to the above configuration, it is possible to provide the electrochemical device 100, the energy system Z, and the like, which can improve the efficiency of converting electric energy into chemical energy such as fuel.

(4) The above-mentioned fruitIn the embodiment, NiO, for example, is used as the material of the electrode layer 31_-GDC、Ni_-GDC、NiO_-YSZ、Ni_-YSZ、CuO_-CeO₂、Cu_-CeO₂And the like, and as a material of the counter electrode layer 33, for example, a composite oxide such as LSCF, LSM, and the like is used. The electrochemical element a configured as described above can be used as a solid oxide fuel cell in which a fuel electrode (anode) is formed by supplying hydrogen gas to the electrode layer 31, and an air electrode (cathode) is formed by supplying air to the counter electrode layer 33. The electrochemical element a may be configured so that the electrode layer 31 can be an air electrode and the counter electrode layer 33 can be a fuel electrode, by changing the configuration. That is, for example, a composite oxide such as LSCF or LSM is used as the material of the electrode layer 31, and for example, NiO is used as the material of the counter electrode layer 33_-GDC、Ni_-GDC、NiO_-YSZ、Ni_-YSZ、CuO_-CeO₂、Cu_-CeO₂And the like. In the electrochemical element a having such a configuration, air is supplied to the electrode layer 31 to form an air electrode, and hydrogen is supplied to the counter electrode layer 33 to form a fuel electrode, so that the electrochemical element a can be used as a solid oxide fuel cell.

(5) In the above embodiment, the electrode layer 31 is disposed between the 1 st plate-like body 1 and the electrolyte layer 32, and the counter electrode layer 33 is disposed on the opposite side of the 1 st plate-like body 1 as viewed from the electrolyte layer 32. The electrode layer 31 and the counter electrode layer 33 may be arranged in reverse. That is, the counter electrode layer 33 may be disposed between the 1 st plate-like body 1 and the electrolyte layer 32, and the electrode layer 31 may be disposed on the opposite side of the 1 st plate-like body 1 as viewed from the electrolyte layer 32. In this case, the supply of gas to the electrochemical element a also needs to be changed.

That is, the order of the electrode layer 31 and the counter electrode layer 33, and the 1 st gas and the 2 nd gas are either one or the other of the reducing component gas and the oxidizing component gas, and various forms can be adopted as long as the 1 st gas and the 2 nd gas are supplied in a form in which they react appropriately with respect to the electrode layer 31 and the counter electrode layer 33.

(6) In the above embodiment, the electrochemical reaction section 3 is provided on the opposite side of the 1 st plate-like body 1 from the 2 nd plate-like body 2 so as to cover the gas flow-allowing section 1A, but may be provided on the 2 nd plate-like body 2 side of the 1 st plate-like body 1. That is, the present invention is also true even if the electrochemical reaction section 3 is disposed in the internal flow path a 1.

(7) In the above embodiment, the 1 st penetration portion 41 and the 2 nd penetration portion 51 are provided as a pair at both ends of the rectangular plate-like support, but the present invention is not limited to the form provided at both ends, and may be provided as 2 or more pairs. The 1 st penetration portion 41 and the 2 nd penetration portion 51 do not need to be provided in a pair. Therefore, 1 or more of the 1 st penetration portions 41 and the 2 nd penetration portions 51 may be provided.

Further, the plate-like support is not limited to a rectangular shape, and various shapes such as a square shape and a circular shape may be adopted.

(8) In the above, the electrochemical module M is provided with a functional layer such as an insulating insulator 210. The electrochemical module M may be provided with further functional layers in addition to or instead of the functional layers shown above.

(9) In the above, the lower cover 203 and the upper cover 201 are joined by welding. However, the lower cover 203 and the upper cover 201 may be joined by, for example, bolts or the like without being limited to fusion.

(10) In the above, the upper cover 201 is formed with the opening 201, and the lower cover 203 is formed with the opening 203 c. However, the opening 201c and the opening 203c may not be formed. Among them, the 1 st gas supply part 61 and the 1 st gas discharge part 62 are formed on the upper cover 201 with openings that can communicate with the outside. Since the opening 201c and the opening 203c are not provided, the electrochemical element stack S is housed in the container 200 configured by the upper lid 201 and the lower lid 203, and the 1 st gas is caused to flow through the electrochemical element stack S via the 1 st gas supply unit 61 and the 1 st gas discharge unit 62, and the 2 nd gas is caused to flow through the electrochemical element stack S via the 2 nd gas supply unit 71 and the 2 nd gas discharge unit 72.

At this time, a supply protrusion communicating with the 1 st gas supply unit 61 and protruding from the upper lid 201 may be formed. Similarly, a discharge protrusion may be formed to communicate with the 1 st gas discharge portion 62 and protrude from the upper cover 201.

(11) In the above, the electrochemical element laminate S is held by the container (1 st holder, 2 nd holder) 200. However, the container 200 is not necessarily used as long as the electrochemical element stack S can be sandwiched. For example, the electrochemical element laminate S may be sandwiched between end plates (1 st and 2 nd holders) or the like.

(12) The 1 st and 2 nd annular seal portions 42 and 52 may have any shape as long as they are configured to prevent gas leakage by allowing the 1 st and 2 nd penetrating portions 41 and 51 to communicate with each other. That is, the 1 st and 2 nd annular seal portions 42 and 52 may be configured to seal the adjacent electrochemical elements a by an endless configuration having an opening portion communicating with the penetration portion therein. The 1 st and 2 nd annular seal portions 42 and 52 are, for example, annular. The ring shape may be any shape such as a circle, an ellipse, a square, or a polygon.

(13) In the above, the plate-like support 10 is constituted by the 1 st plate-like body 1 and the 2 nd plate-like body 2. Here, the 1 st plate-like body 1 and the 2 nd plate-like body 2 may be formed of separate plate-like bodies, or may be formed of one plate-like body as shown in fig. 24. In the case of fig. 24, the 1 st plate-like body 1 overlaps the 2 nd plate-like body 2 by bending one plate-like body. Then, the 1 st plate-like body 1 and the 2 nd plate-like body 2 are integrated by welding or the like of the peripheral edge portion 1 a. The 1 st plate-like body 1 and the 2 nd plate-like body 2 may be formed of a series of seamless plate-like bodies, or may be formed by bending a series of plate-like bodies as shown in fig. 24.

As described later, the 2 nd plate-like body 2 may be constituted by one member, or may be constituted by 2 or more members. Similarly, the 1 st plate-like body 1 may be constituted by one member, or may be constituted by 2 or more members.

(14) The 2 nd plate-like body 2 forms an internal flow path a1 together with the 1 st plate-like body 1. The internal flow path a1 includes a distribution portion a12, a plurality of sub-flow paths a11, and a junction a 13. The 1 st gas supplied to the distribution portion a12 is distributed and supplied to the plurality of sub-channels a11, respectively, as shown in fig. 5 and the like, and merges at the merging portion a13 at the outlets of the plurality of sub-channels a 11. Therefore, the 1 st gas flows in the gas flow direction from the distribution portion a12 toward the joining portion a 13.

The plurality of sub-flow paths a11 are formed by forming the 2 nd plate-like body 2 into a corrugated plate shape in the portion from the distribution portion a12 to the portion other than the confluence portion a 13. Then, as shown in fig. 9, the plurality of sub-channels a11 are formed in a wave plate shape in a cross-sectional view in a flow intersecting direction intersecting with the gas flow direction of the 1 st gas. The plurality of sub-channels a11 are formed such that the wave plates extend in the gas flow direction shown in fig. 5 and the like. The plurality of sub-flow paths a11 may be formed of a series of corrugated plate-like bodies between the distribution portion a12 and the junction a13, or may be formed of 2 or more corrugated plate-like bodies. The plurality of sub-channels a11 may be formed of, for example, 2 or more corrugated plate-like bodies separated in the direction along the gas flow direction, or 2 or more corrugated plate-like bodies separated in the direction along the flow cross direction.

As shown in fig. 9 and the like, the plurality of sub-channels a11 are formed in a waveform in which peaks and valleys having the same shape are repeatedly formed. However, the 2 nd plate-like body 2 may have a plate-like portion in a region where the plurality of sub flow paths a11 are formed. For example, the plurality of sub flow paths a11 may be formed by alternately forming plate-like portions and protruding portions. Then, the protruding portion may be a portion through which a fluid such as the 1 st gas flows.

(15) In the above-described 2 nd plate-like body 2, the portions corresponding to the plurality of sub-channels a11 need not be formed in a corrugated plate shape over the entire surface, but at least a part thereof may be formed in a corrugated plate shape. For example, between the distribution portion a12 and the confluence portion a13, the 2 nd plate-like body 2 has a flat plate-like portion in the gas flow direction and a corrugated plate-like portion in the remainder. Further, a part of the 2 nd plate-like body 2 in the cross flow direction may be flat plate-like, and the remainder may be corrugated plate-like.

(16) In the above embodiment, the electrochemical device includes the electrochemical module M having the plurality of electrochemical elements a. However, the electrochemical device according to the above embodiment can be applied to a configuration having 1 electrochemical element.

Description of the symbols

1: 1 st plate-like body

1A: gas flow-through allowing unit

2: 2 nd plate-like body

3: electrochemical reaction part

4: supply path

5: discharge path

9: distribution chamber

10: plate-shaped support

31: electrode layer

32: electrolyte layer

33: counter electrode layer

41: 1 st penetration part

42: no. 1 annular seal part

51: 2 nd penetration part

52: 2 nd annular seal part

61: 1 st gas supply part

62: no. 1 gas discharge part

71: 2 nd gas supply part

72: 2 nd gas discharge part

100: electrochemical device

140: supply structure

141: supply passage part

142: supply stopping part

144: supply buffer part

150: discharge structure

151: discharge passage part

152: discharge preventing part

154: discharge buffer

160: sub flow path forming part

161: spacer section

200: container with a lid

201: upper cover

203: lower cover

210: insulator

230: board

A: electrochemical element

A1: internal flow path

A11: secondary flow path

A12: distribution part

A13: confluence part

A2: circulation part

M: electrochemical module

S: electrochemical element laminate

Z: an energy system.