JP2022156333A - Annular spacer, electrochemical element, electrochemical module, electrochemical device, energy system, solid oxide fuel cell, and solid oxide electrolysis cell - Google Patents

Abstract

To provide means for facilitating fabrication of an electrochemical module in which electrochemical elements are stacked.SOLUTION: A plate-like annular spacer 91 having a through hole 91a extending over the front and back includes a channel 91b that allows gas to flow from a space SI inside the through hole 91a to a space SO outside the annular spacer 91 in a state of being sandwiched between other members.SELECTED DRAWING: Figure 17

Description

The present invention relates to annular spacers, electrochemical elements, electrochemical modules, electrochemical devices, energy systems, solid oxide fuel cells and solid oxide electrolysis cells.

Conventionally, an electrochemical element laminate constituting an electrochemical device such as a fuel cell (electrochemical power generation cell) or an electrolysis cell includes a gas permeable region and covers the gas permeable region to generate electricity, as shown in Patent Document 1. A number of substrates including metal substrates on which chemical reaction parts are formed and metal substrates functioning as spacers and separators are airtightly laminated. An air flow path for air (oxidizing component gas) and a fuel gas flow path for fuel gas (reducing component gas) are defined along both sides of the metal substrate (electrochemical element) provided with the electrochemical reaction portion. , circulating air and fuel gas in the respective channels. That is, a plurality of electrochemical elements are stacked to form an electrochemical module integrally. As a result, an electrochemical output such as electric power is generated from the reaction between the air and the fuel gas in the electrochemical reaction section.

Japanese Patent Publication No. 2017-508254

However, since an electrochemical module is formed by stacking a large number of substrates to form an air channel and a fuel gas channel, it is necessary to securely seal and fix a large number of metal substrates. Therefore, the fabrication of such an electrochemical module requires a great deal of man-hours and great care in order to fix it reliably and reliably. As a result, the production cost for producing such an electrochemical module increases significantly, and the reliability of the produced electrochemical module (airtightness between metal substrates, certainty of electrical connection, etc.) decreases. was becoming

Therefore, in view of the above-mentioned actual situation, the present invention provides a means for facilitating the production of an electrochemical module in which a plurality of electrochemical elements are arranged in an aggregated state, and also provides a means for facilitating handling in producing the electrochemical module. An object of the present invention is to provide an electrochemical device having a structure that is A further object of the present invention is to provide an electrochemical device, an energy system, a solid oxide fuel cell, and a solid oxide electrolysis cell using the electrochemical module at a low cost.

As a means for solving the above-described problems, the annular spacer of the present invention is a plate-like annular spacer provided with a through hole extending from front to back, wherein the annular spacer is sandwiched between other members from the space inside the through hole to the annular spacer. It is characterized by having a channel for allowing gas to flow to a space outside the spacer.

According to this configuration, when the annular spacer is sandwiched between other members, gas can flow from the space inside the through hole to the space outside the annular spacer. Such an annular spacer can be suitably applied to the plate-shaped support of the electrochemical device. For example, there is a case in which the plate-like support is configured by opposing two plate-like bodies, and the space between the two plate-like bodies is used as a gas flow path (internal flow path). In this case, arranging the annular spacer sandwiched between the two plate-like bodies provides various advantages. First, the rigidity of the plate-like support can be increased. When making an electrochemical module, a plurality of electrochemical elements are assembled and a force is applied in the assembly direction. Due to the presence of the annular spacer, deformation of the plate-like body can be suppressed and the shape of the internal flow path can be maintained. Also, the through-holes and channels of the annular spacer can be used to supply gas to the internal channels of the plate-like support. Therefore, the annular spacer facilitates fabrication of an electrochemical module in which a plurality of electrochemical elements are arranged in an aggregated state. In other words, the annular spacer makes it possible to provide an electrochemical element having a structure that is easy to handle in fabricating an electrochemical module.

In the present invention, it is preferable that at least one of the front surface and the back surface is provided with a projecting portion projecting in the front and back direction more than the surroundings, and the space around the projecting portion functions as the flow path.

According to this configuration, the channel of the annular spacer can be realized with a simple configuration.

In the present invention, it is preferable that a plurality of first parts arranged with gaps in the circumferential direction and a second part connecting the first parts are provided, and the gaps function as the flow paths.

According to this configuration, the channel of the annular spacer can be realized with a simple configuration.

In the present invention, it is suitable to be formed of a material having electrical conductivity.

According to this configuration, when the annular spacer is sandwiched between two other members, the two members can be electrically connected through the annular spacer. That is, when the annular spacer is used for the plate-like support of the electrochemical device, the electrical conductivity of the plate-like support can be improved.

In the present invention, the material preferably contains at least one of ferritic stainless steel, austenitic stainless steel, inconel, copper and invar.

According to this configuration, the annular spacer can be manufactured at low cost using readily available materials.

As means for solving the above-described problems, the electrochemical device of the present invention comprises an electrolyte layer, first and second electrodes respectively arranged on both sides of the electrolyte layer, and the electrolyte layer and the first electrode. a plate-like support that supports the second electrode, wherein the plate-like support includes a conductive first plate-like body, a conductive second plate-like body, an internal flow path formed between opposing surfaces of the first plate-shaped body and the second plate-shaped body, wherein the annular spacer is disposed between the first plate-shaped body and the second plate-shaped body. It is characterized in that it is arranged in between.

According to this configuration, since the annular spacer is arranged between the first plate-shaped body and the second plate-shaped body, deformation of the first plate-shaped body and the second plate-shaped body is suppressed, and the internal flow path is It can keep its shape. In other words, the rigidity of the plate-like support can be increased. Also, the through-holes and channels of the annular spacer can be used to supply gas to the internal channels of the plate-like support. Therefore, an electrochemical module in which a plurality of electrochemical elements are assembled can be easily produced. In other words, the annular spacer makes it possible to provide an electrochemical element having a structure that is easy to handle in fabricating an electrochemical module.

In the present invention, at least one of the first plate-like body and the second plate-like body has a through portion forming a gas supply path to the internal flow path, and the thickness direction of the plate-like support is It is preferable that the annular spacer is arranged such that the through portion and the through hole of the annular spacer overlap when viewed.

According to this configuration, the gas from the through portion can be supplied to the internal channel between the first plate-shaped body and the second plate-shaped body through the through hole and the channel of the annular spacer.

As a means for solving the above-described problems, an electrochemical module of the present invention is characterized in that a plurality of the above-described electrochemical elements are arranged in an aggregated state.

According to this configuration, since a plurality of the above-described electrochemical elements are arranged in an aggregated state, it is possible to obtain a compact, high-performance electrochemical module excellent in strength and reliability while suppressing material costs and processing costs. be able to.

As a means for solving the above-described problems, the electrochemical device of the present invention generates the above-described electrochemical element or the above-described electrochemical module, and a reducing component to be supplied to the electrochemical element or the electrochemical module, or and a fuel converter for converting a gas containing reducing components generated in the electrochemical element or the electrochemical module.

According to this configuration, when the electrochemical element or the electrochemical module is operated as a fuel cell, fuel such as a reformer is used based on natural gas or the like supplied using the existing raw fuel supply infrastructure such as city gas. It is possible to realize an electrochemical device having an electrochemical element or an electrochemical module that can be configured to generate hydrogen using a converter and has excellent durability, reliability, and performance. In addition, since it becomes easy to construct a system for recycling unused fuel gas distributed from the electrochemical module, a highly efficient electrochemical device can be realized.
On the other hand, when operating the electrochemical element or electrochemical module as an electrolytic cell, a gas containing water vapor or carbon dioxide is passed through the electrode layer, and a voltage is applied between the electrode layer and the counter electrode layer. Then, the electron e ⁻ reacts with the water molecule H ₂ O and the carbon dioxide molecule CO ₂ in the electrode layer to form the hydrogen molecule H ₂ , the carbon monoxide CO and the oxygen ion O ²⁻ . The generated oxygen ions O ²⁻ move to the counter electrode layer through the electrolyte layer. Then, in the counter electrode layer, the oxygen ions O ²⁻ emit electrons and become oxygen molecules O ₂ . By the above reaction, when a gas containing water vapor flows, water molecules H ₂ O are decomposed into hydrogen H ₂ and oxygen O ₂ , and when a gas containing carbon dioxide molecules CO ₂ flows, , is electrolyzed into carbon monoxide CO and oxygen _O2 .
Therefore, when a gas containing water vapor and carbon dioxide molecules _CO2 is circulated, various compounds such as hydrocarbons are produced from the hydrogen and carbon monoxide produced in the electrochemical element or electrochemical module by the above electrolysis. A synthesizing fuel converter may be provided. As a result, hydrocarbons and the like generated by the fuel converter can be distributed to the electrochemical element or the electrochemical module, or taken out of the present system/apparatus and used separately as fuel or chemical raw materials.

As a means for solving the above problems, the electrochemical device of the present invention comprises the above-described electrochemical element or the above-described electrochemical module, and the electrochemical element or the electrochemical module for extracting electric power or and a power converter for supplying power to the electrochemical module.

According to this configuration, the power converter takes out power generated by the electrochemical element or the electrochemical module, or distributes power to the electrochemical element or the electrochemical module. Thereby, the electrochemical element or electrochemical module as described above acts as a fuel cell or as an electrolysis cell. Therefore, according to the above configuration, it is possible to provide an electrochemical device or the like capable of improving the efficiency of converting chemical energy such as fuel into electrical energy or converting electrical energy into chemical energy such as fuel.
For example, when an inverter is used as a power converter, the electrical output obtained from an electrochemical element or electrochemical module with excellent durability, reliability, and performance can be boosted by the inverter or converted from direct current to alternating current. Therefore, the electric output obtained from the electrochemical element or the electrochemical module can be easily used, which is preferable. Further, when electrolysis is performed, it is possible to obtain a direct current from an alternating current power supply and construct an electrochemical device capable of supplying direct current power to an electrochemical element or an electrochemical module, which is preferable.

As a means for solving the above-described problems, an energy system of the present invention is characterized by having the above-described electrochemical device and a waste heat utilization unit that reuses heat discharged from the electrochemical device.

According to this configuration, the energy system has excellent durability, reliability, and performance, as well as excellent energy efficiency, because it has the electrochemical device and the waste heat utilization section that reuses the heat discharged from the electrochemical device. can be realized. It is also possible to realize a hybrid system with excellent energy efficiency in combination with a power generation system that generates power using combustion heat of unused fuel gas discharged from an electrochemical device.

As a means for solving the above-described problems, the solid oxide fuel cell of the present invention is characterized by comprising the above-described electrochemical element and causing a power generation reaction in the electrochemical element.

According to this configuration, a solid oxide fuel cell having an electrochemical element with excellent durability, reliability, and performance can perform a power generation reaction, so a highly durable and high-performance solid oxide fuel cell. can be obtained. If the solid oxide fuel cell is capable of operating in a temperature range of 650°C or higher during rated operation, the raw fuel is converted to hydrogen in a fuel cell system that uses a hydrocarbon gas such as city gas as a raw fuel. It is possible to construct a system in which the exhaust heat of the fuel cell can cover the heat that is actually required, so that the power generation efficiency of the fuel cell system can be increased. Further, it is more preferable that the solid oxide fuel cell is operated in a temperature range of 900° C. or less during rated operation because the effect of suppressing Cr volatilization from the metal-supported electrochemical device is enhanced. A solid oxide fuel cell operated in the following temperature range is more preferable because the effect of suppressing Cr volatilization can be further enhanced.

As a means for solving the above-described problems, the solid oxide electrolytic cell of the present invention is characterized by comprising the above-described electrochemical element and causing an electrolytic reaction in the electrochemical element.

According to this configuration, gas can be generated by an electrolytic reaction as a solid oxide electrolytic cell equipped with an electrochemical element excellent in durability, reliability, and performance. A physical electrolytic cell can be obtained.

Schematic diagram of the electrochemical device II-II sectional view in FIG. III-III plane view in FIG. IV-IV cross-sectional view in FIG. VV sectional view in FIG. VI-VI cross-sectional view in FIG. VII-VII cross-sectional view in FIG. VIII-VIII cross-sectional view in FIG. IX-IX cross-sectional view in FIG. Enlarged view of the main part of the electrochemical reaction part Schematic diagram of the electrochemical module Schematic diagram of the energy system Explanatory drawing of an electrochemical module according to another embodiment Schematic diagram of another energy system Perspective view of annular spacer Top view of annular spacer Cross-sectional view of an electrochemical device Perspective view of annular spacer Top view of annular spacer Cross-sectional view of an electrochemical device

The annular spacer, electrochemical element, electrochemical device, energy system, solid oxide fuel cell and solid oxide electrolytic cell of the present invention are described below. Although preferred examples are described below, each of these examples is described in order to illustrate the present invention more specifically, and various changes can be made without departing from the scope of the present invention. and the present invention is not limited to the following description. When describing the positional relationship of the layers, for example, the side of the electrolyte layer viewed from the electrode layer is called "upper" or "upper", and the side of the first plate-like body is called "lower" or "lower".

(Electrochemical element)
As shown in FIGS. 1 to 9, the electrochemical device A has an internal channel A1 formed between the facing surfaces of a conductive first plate-like body 1 and a conductive second plate-like body 2. A plate-like support 10 is provided, and the plate-like support 10 is configured such that at least a part of the first plate-like body 1 and the second plate-like body 2 constituting the plate-like support 10 is A gas flow-permitting portion 1A that allows gas to pass through the internal channel A1 on the inside and the outside, and a film-like electrode layer 31 and a film-like electrode layer 31 in a state of covering all or part of the gas flow-permitting portion 1A. and an electrochemical reaction section 3 having an electrolyte layer 32 in the form of a film and a counter electrode layer 33 in the form of a film in the order of description (see FIGS. 5 to 9). A first gas, which is one of a reducing component gas such as a fuel gas and an oxidizing component gas such as air, flows through the plate-like support 10 from the outside in the surface penetrating direction into the internal flow channel A1. A first through portion 41 forming a supply passage 4 is provided on one end side, and a discharge passage 5 is formed through which the first gas that has flowed through the internal flow passage A1 flows outward in the surface penetrating direction of the plate-like support 10. (See FIGS. 1, 3, 8, and 9.) The supply channel 4 and the discharge channel 5 are symmetrical and have the same structure. is also understood).

(plate-like support)
The first plate-like body 1 supports the electrochemical reaction section 3 having the electrode layer 31 , the electrolyte layer 32 and the counter electrode layer 33 to maintain the strength of the electrochemical element A. As a material for the first plate-like body 1, a material having excellent electronic conductivity, heat resistance, oxidation resistance and corrosion resistance is used. For example, ferritic stainless steel, austenitic stainless steel, nickel-based alloy, etc. are used. In particular, alloys containing chromium are preferably used. In the present embodiment, the first plate-like body 1 uses an Fe—Cr alloy containing 18% by mass or more and 25% by mass or less of Cr. alloy, Fe--Cr alloy containing 0.15% by mass or more and 1.0% by mass or less of Ti, Fe--Cr-based alloy containing 0.15% by mass or more and 1.0% by mass or less of Zr, Ti and Zr Fe--Cr alloy containing 0.15% by mass or more and 1.0% by mass or less of total Ti and Zr, Fe- containing 0.10% by mass or more and 1.0% by mass or less of Cu A Cr-based alloy is particularly suitable.

The second plate-like body 2 is superimposed on the first plate-like body 1, and the peripheral edge portion 1a thereof is welded to form a plate-like support 10 (see FIGS. 2 to 9). The second plate-shaped body 2 may be divided into a plurality of parts with respect to the first plate-shaped body 1, or conversely, the first plate-shaped body 1 may be divided into a plurality of parts with respect to the second plate-shaped body 2. may be In addition, when integrating, other means such as adhesion or fitting can be adopted instead of welding, and if the internal flow path can be separated from the outside and can be formed, integration can be performed at a portion other than the peripheral edge portion 1a. may

The first plate-like body 1 is plate-like as a whole. It has a gas flow permitting portion 1A having a plurality of through holes 11 penetrating through the front side surface and the back side surface (see FIGS. 5 to 9). For example, the through holes 11 can be provided in the first plate-like body 1 by laser processing or the like. The through holes 11 have the function of allowing gas to permeate from the back surface of the first plate-like body 1 to the front surface thereof. It is preferable that the gas flow permitting portion 1A be provided in a region smaller than the region in which the electrode layer 31 of the first plate-like body 1 is provided.

A metal oxide layer 12 (described later, see FIG. 10) is provided on the surface of the first plate-like body 1 as a diffusion suppressing layer. That is, a diffusion suppression layer is formed between the first plate-like body 1 and an electrode layer 31, which will be described later. The metal oxide layer 12 is provided not only on the surface exposed to the outside of the first plate-like body 1 but also on the contact surface (interface) with the electrode layer 31 . It can also be provided on the inner surface of the through hole 11 . This metal oxide layer 12 can suppress element interdiffusion between the first plate-like body 1 and the electrode layer 31 . For example, when ferritic stainless steel containing chromium is used as the first plate-like body 1, the metal oxide layer 12 is mainly chromium oxide. The metal oxide layer 12 containing chromium oxide as a main component prevents the chromium atoms and the like of the first plate-like body 1 from diffusing 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 anti-diffusion performance and low electrical resistance.

Although the metal oxide layer 12 can be formed by various methods, a method of oxidizing the surface of the first plate-like body 1 to form a metal oxide is preferably used. In addition, the metal oxide layer 12 is applied to the surface of the first plate-like body 1 by a spray coating method (a thermal spraying method, an aerosol deposition method, an aerosol gas deposition method, a powder jet deposition method, a particle jet deposition method, a cold spray method). method), a sputtering method, a PVD method such as a PLD method, a CVD method, or the like, or may be formed by plating and oxidation treatment. Furthermore, the metal oxide layer 12 may contain a highly conductive spinel phase or the like.

When a ferritic stainless steel material is used as the first plate-like body 1, YSZ (yttria-stabilized zirconia), GDC (gadolin-doped ceria, also called CGO), etc., which are materials of the electrode layer 31 and the electrolyte layer 32, and the like are combined with heat. Expansion coefficients are close. Therefore, the electrochemical element A is less likely to be damaged even when the temperature cycle of low temperature and high temperature is repeated. Therefore, it is possible to realize an electrochemical device A having excellent long-term durability, which is preferable. In addition, the first plate-like body 1 has a plurality of through holes 11 provided through the front side surface and the back side surface. For example, the through-holes 11 can be provided in the first plate-like body 1 by mechanical, chemical, or optical drilling. The through holes 11 have the function of allowing gas to permeate from the back surface of the first plate-like body 1 to the front surface thereof. A porous metal can be used to make the first plate-like body 1 gas-permeable. For example, the first plate-like body 1 may be made of sintered metal, foamed metal, or the like.

The second plate-like body 2 has a plurality of sub-flow passages A11, A11 . It is formed in a corrugated plate shape forming an internal flow path A1 (see FIGS. 1 and 5). Both the front and back surfaces of the second plate-like body 2 are corrugated, and the surface opposite to the surface defining the internal flow path A1 is electrically A passage formed in the vicinity of the portion where the corrugated second plate-like body 2 contacts the first plate-like body 1 functions as a flow passage A2. A plurality of sub-channels A11 are provided parallel to each other along the long side of the plate-shaped support 10 formed in a rectangular shape, and from the supply channel 4 provided at one end to the discharge channel 5 provided at the other end. An internal flow path A1 is constructed. Further, the connecting portion between the first through portion 41 and the internal flow path A1 is formed by bulging downward from the contact portion with the first plate-like body 1, and the first gas flowing through the first through portion 41 is bulged. A distribution portion A12 is provided for distributing to each of the sub-channels A11 (see FIG. 1), and the connecting portion between the second through portion 51 and the internal channel A1 bulges downward from the contact portion with the first plate-like body 1. A confluence portion A13 is provided, which collects the first gas flowing through each of the sub-flow passages A11 and guides it to the second penetration portion 51 (see FIGS. 1, 3, 4, 6 to 9, It is also understood that the supply channel 4 and the like and the discharge channel 5 and the like are symmetrical and have the same structure). In addition, the material of the second plate-shaped body 2 is preferably a heat-resistant metal, from the viewpoint of reducing the difference in thermal expansion with the first plate-shaped body 1 and ensuring the reliability of bonding such as welding. , the same material as the first plate-like body 1 is more preferable.

(Electrochemical reaction part)
(electrode layer)
As shown in FIGS. 5 to 10, the electrode layer 31 can be provided in the form of a thin layer on the surface of the front side of the first plate-like body 1 in an area larger than the area where the through holes 11 are provided. In the case of a thin layer, the thickness can be, for example, about 1 μm to 100 μm, preferably 5 μm to 50 μm. With such a thickness, it is possible to secure sufficient electrode performance while reducing costs by reducing the amount of expensive electrode layer material used. The entire area 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 of the first plate-like body 1 where the electrode layer 31 is formed. In other words, all the through holes 11 are provided facing the electrode layer 31 .

The electrode layer 31 has a plurality of pores inside and on its surface in order to provide gas permeability.
That is, the electrode layer 31 is formed as a porous layer. The electrode layer 31 is formed, for example, so that its denseness is 30% or more and less than 80%. The size of the pores can be appropriately selected so that the electrochemical reaction proceeds smoothly. The denseness is the ratio of the space occupied by the material constituting the layer, and can be expressed as (1-porosity), and is equivalent to the relative density.

As the material of the electrode layer 31, composite materials such as NiO-GDC, Ni-GDC, NiO-YSZ, Ni-YSZ, CuO _-- CeO ₂ and Cu _-- CeO ₂ can be used. _In these examples, GDC, YSZ, CeO2 can be referred to as composite aggregates. The electrode layer 31 is formed by a low-temperature baking method (for example, a wet method using baking treatment in a low-temperature region without baking treatment in a high-temperature region higher than 1100 ° C.) or a spray coating method (thermal spraying method, aerosol deposition method, aerosol gas deposition method, powder jet deposition method, particle jet deposition method, cold spray method, etc.), PVD method (sputtering method, pulse laser deposition method, etc.), CVD method, or the like. These processes, which can be used in the low temperature range, provide a good electrode layer 31 without using high temperature firing, e.g., higher than 1100°C. Therefore, the first plate-like body 1 is not damaged, element mutual diffusion between the first plate-like body 1 and the electrode layer 31 can be suppressed, and an electrochemical device A having excellent durability can be realized. preferable. Furthermore, it is more preferable to use the low-temperature firing method because the handling of the raw material is facilitated.

(middle layer)
The intermediate layer 34 can be formed in a thin layer state on the electrode layer 31 while covering the electrode layer 31 . In the case of a thin layer, the thickness can be, for example, about 1 μm to 100 μm, preferably about 2 μm to 50 μm, more preferably about 4 μm to 25 μm. With such a thickness, it is possible to reduce costs by reducing the amount of material used for the expensive intermediate layer 34, while ensuring sufficient performance. Examples of materials for the intermediate layer 34 include YSZ (yttria-stabilized zirconia), SSZ (scandium-stabilized zirconia), GDC (gadolin-doped ceria), YDC (yttrium-doped ceria), and SDC (samarium-doped ceria). ceria) and the like can be used. In particular, ceria-based ceramics are preferably used.

The intermediate layer 34 is formed by a low-temperature firing method (for example, a wet method using a firing process in a low-temperature range without firing in a high-temperature range higher than 1100 ° C.) or a spray coating method (thermal spraying method, aerosol deposition method, aerosol gas deposition method, etc.). method, powder jet deposition method, particle jet deposition method, cold spray method, etc.), PVD method (sputtering method, pulse laser deposition method, etc.), CVD method, or the like. These low-temperature deposition processes provide the intermediate layer 34 without firing at high temperatures, eg, greater than 1100.degree. Therefore, element mutual diffusion between the first plate-like body 1 and the electrode layer 31 can be suppressed without damaging the first plate-like body 1, and an electrochemical device A excellent in durability can be realized. Moreover, it is more preferable to use the low-temperature firing method because the raw material can be easily handled.

The intermediate layer 34 preferably has oxygen ion (oxide ion) conductivity. Further, it is more preferable to have mixed conductivity of oxygen ions (oxide ions) and electrons. An intermediate layer having these properties is suitable for application to the electrochemical device A.

In addition, in the electrode layer 31 , the aggregate content ratio, compactness, and strength of the cermet material may be configured to increase continuously from the lower side to the upper side of the electrode layer 31 . In this case, the electrode layer 31 may not have a clearly distinguishable region as a layer. However, even in this case, the content ratio of the aggregate of the cermet material in the portion (upper portion) adjacent to the electrolyte layer 32 compared to the portion (lower portion) adjacent to the first plate-like body 1 in the electrode layer 31, It is also possible to increase density, strength, and the like.

(Electrolyte layer)
As shown in FIGS. 5 to 10, the electrolyte layer 32 is formed in a thin layer on the intermediate layer 34 while covering the electrode layer 31 and the intermediate layer 34 . It can also be formed in the form of a thin film with a thickness of 10 μm or less. Specifically, the electrolyte layer 32 is provided over (straddles) the intermediate layer 34 and the first plate-like body 1 . By configuring in this way and bonding the electrolyte layer 32 to the first plate-like body 1, the electrochemical device as a whole can be made excellent in robustness.

Further, as shown in FIG. 5, the electrolyte layer 32 is provided on the front side surface of the first plate-like body 1 in an area larger than the area in which the through holes 11 are provided. That is, the through holes 11 are formed inside the region of the first plate-like body 1 where the electrolyte layer 32 is formed.

Further, around the electrolyte layer 32, leakage of gas from the electrode layer 31 and the intermediate layer (not shown) can be suppressed. Specifically, when the electrochemical device A is used as a component of an SOFC, gas is supplied from the back side of the first plate-like body 1 through the through holes 11 to the electrode layer 31 during operation of the SOFC. In the region where the electrolyte layer 32 is in contact with the first plate-like body 1, gas leakage can be suppressed without providing a separate member such as a gasket. In this embodiment, the electrolyte layer 32 entirely covers the electrode layer 31, but the electrolyte layer 32 may be provided above the electrode layer 31 and the intermediate layer, and a gasket or the like may be provided around the electrolyte layer 32.

Materials for the electrolyte layer 32 include YSZ (yttria-stabilized zirconia), SSZ (scandium-stabilized zirconia), GDC (gadolin-doped ceria), YDC (yttrium-doped ceria), and SDC (samarium-doped ceria). , LSGM (strontium-magnesium added lanthanum gallate) and other electrolyte materials that conduct oxygen ions, and perovskite-type oxides and other electrolyte materials that conduct hydrogen ions can be used. In particular, zirconia-based ceramics are preferably used. When the electrolyte layer 32 is made of zirconia-based ceramics, the operating temperature of the SOFC using the electrochemical element A can be made higher than that of ceria-based ceramics and various hydrogen ion conductive materials. For example, when the electrochemical element A is used in an SOFC, a material such as YSZ that can exhibit high electrolyte performance even in a high temperature range of about 650° C. or higher is used as the material of the electrolyte layer 32, and city gas, LPG, or the like is used as the raw fuel of the system. If a hydrocarbon-based raw fuel is used, and the raw fuel is used as the anode gas for the SOFC by steam reforming, etc., a highly efficient SOFC system that uses the heat generated in the SOFC cell stack for reforming the raw fuel gas is constructed. can be built.

The electrolyte layer 32 is formed by a low-temperature firing method (for example, a wet method using firing treatment in a low-temperature region without firing in a high-temperature region exceeding 1100° C.) or a spray coating method (thermal spraying method, aerosol deposition method, aerosol gas deposition method, etc.). method, powder jet deposition method, particle jet deposition method, cold spray method, etc.), PVD method (sputtering method, pulse laser deposition method, etc.), CVD (chemical vapor deposition) method, etc. preferable. These film forming processes that can be used in a low temperature range provide the electrolyte layer 32 that is dense, has high airtightness, and has high gas barrier properties, without using sintering in a high temperature range exceeding 1100° C., for example. Therefore, damage to the first plate-like body 1 can be suppressed, and element interdiffusion between the first plate-like body 1 and the electrode layer 31 can be suppressed, and the electrochemical element A excellent in performance and durability can be obtained. realizable. In particular, it is preferable to use a low-temperature baking method, a spray coating method, or the like, since a low-cost device can be realized. Furthermore, it is more preferable to use the spray coating method because the electrolyte layer 32 that is dense, airtight, and has high gas barrier properties can be easily obtained in a low temperature range.

The electrolyte layer 32 is densely structured in order 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 higher, more preferably 95% or higher, and even more preferably 98% or higher. When the electrolyte layer 32 is a uniform layer, it preferably has a denseness of 95% or more, more preferably 98% or more. Further, when the electrolyte layer 32 is composed of a plurality of layers, it is preferable that at least a part of them include a layer (dense electrolyte layer) having a density of 98% or more, such as 99%. It is more preferable to include the above layer (dense electrolyte layer). When such a dense electrolyte layer is included in a part of the electrolyte layer 32, even if the electrolyte layer 32 is composed of a plurality of layers, the electrolyte layer 32 is dense and has high airtightness and gas barrier properties. This is because it is easy to form

(Reaction prevention layer)
The reaction prevention layer 35 can be formed in a thin layer state on the electrolyte layer 32 . In the case of a thin layer, the thickness can be, for example, about 1 μm to 100 μm, preferably about 2 μm to 50 μm, more preferably about 3 μm to 15 μm. With such a thickness, it is possible to reduce costs by reducing the amount of the expensive reaction-preventing layer material used, while ensuring sufficient performance. As the material for the reaction prevention layer, any material that can prevent reaction between the components of the electrolyte layer 32 and the components of the counter electrode layer 33 can be used. For example, a ceria-based material is used. A material containing at least one element selected from the group consisting of Sm, Gd and Y is preferably used as the material of the reaction prevention layer 35 . At least one element selected from the group consisting of Sm, Gd and Y is contained, and the total content of these elements is preferably 1.0% by mass or more and 10% by mass or less. By introducing the reaction prevention 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 electrochemical element A can improve the long-term stability of the performance of If the reaction prevention layer 35 is formed by appropriately using a method that can be formed at a processing temperature of 1100° C. or less, damage to the first plate-like body 1 can be suppressed, and the first plate-like body 1 and the electrode layer 31 can be prevented from being damaged. element interdiffusion can be suppressed, and an electrochemical device A having excellent performance and durability can be realized. For example, low-temperature firing method (for example, wet method using firing treatment in low temperature range without firing treatment in high temperature range exceeding 1100 ° C.), spray coating method (thermal spraying method, aerosol deposition method, aerosol gas deposition method, powder jet deposition method, particle jet deposition method, cold spray method, etc.), PVD method (sputtering method, pulse laser deposition method, etc.), CVD method, etc. can be used as appropriate. In particular, it is preferable to use a low-temperature baking method, a spray coating method, or the like, since a low-cost device can be realized. Furthermore, it is more preferable to use the low-temperature firing method because the handling of the raw material is facilitated.

(Counter electrode layer)
As shown in FIGS. 5 to 10, the counter electrode layer 33 can be formed as a thin layer on the electrolyte layer 32 or the reaction prevention layer 35 . In the case of a thin layer, the thickness can be, for example, about 1 μm to 100 μm, preferably 5 μm to 50 μm. With such a thickness, it is possible to secure sufficient electrode performance while reducing costs by reducing the amount of the expensive counter electrode layer material used. As a material for the counter electrode layer 33, for example, composite oxides such as LSCF and LSM, ceria-based oxides, and mixtures thereof can be used. In particular, counter electrode layer 33 preferably contains a perovskite oxide containing two or more elements selected from the group consisting of La, Sr, Sm, Mn, Co and Fe. The counter electrode layer 33 made of the above materials functions as a cathode.

In addition, if the counter electrode layer 33 is formed by appropriately using a method that can be formed at a processing temperature of 1100° C. or less, damage to the first plate-like body 1 can be suppressed and the first plate-like body 1 and the electrode layer can be formed. 31 can be suppressed, and an electrochemical device A having excellent performance and durability can be realized. For example, low-temperature firing method (for example, wet method using firing treatment in low temperature range without firing treatment in high temperature range exceeding 1100 ° C.), spray coating method (thermal spraying method, aerosol deposition method, aerosol gas deposition method, powder jet deposition method, particle jet deposition method, cold spray method, etc.), PDV method (sputtering method, pulse laser deposition method, etc.), CVD method, etc. can be used as appropriate. In particular, it is preferable to use a low-temperature baking method, a spray coating method, or the like, since a low-cost device can be realized. Furthermore, it is more preferable to use the low-temperature firing method because the handling of the raw material is facilitated.

By configuring the electrochemical reaction section 3 as described above, for example, the fuel gas containing hydrogen as the first gas flows from the back surface of the first plate-like body 1 through the through holes 11 to the electrode layer 31, and the electrode Air as the second gas is circulated to the counter electrode layer 33 that serves as the counter electrode of the layer 31, and is maintained at an operating temperature of, for example, 500° C. or higher and 900° C. or lower. Then, when an electrolyte material that conducts oxygen ions is used for the electrolyte layer 32, oxygen O ₂ contained in the air reacts with electrons e ⁻ in the counter electrode layer 33 to generate oxygen ions O ²⁻ . The oxygen ions O ²⁻ move through the electrolyte layer 32 to the electrode layer 31 . In the electrode layer 31, hydrogen H ₂ contained in the flowed fuel gas reacts with oxygen ions O ²⁻ to produce water H ₂ O and electrons e ⁻ . When an electrolyte material that conducts hydrogen ions is used for the electrolyte layer 32, the hydrogen H ₂ contained in the fuel gas circulated in the electrode layer 31 releases electrons e ⁻ to generate hydrogen ions H ^{2 +} . The hydrogen ions H ⁺ move through the electrolyte layer 32 to the counter electrode layer 33 . Oxygen O ₂ contained in the air reacts with hydrogen ions H ⁺ and electrons e ⁻ in the counter electrode layer 33 to generate water H ₂ O. Due to the above reaction, an electromotive force is generated as an electrochemical output between the electrode layer 31 and the counter electrode layer 33 . In this case, 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 omitted in FIGS. 5 to 9, as shown in FIG. 10, the electrochemical reaction section 3 includes an intermediate layer 34 between the electrode layer 31 and the electrolyte layer 32 in this embodiment. Furthermore, a reaction prevention layer 35 is provided between the electrolyte layer 32 and the counter electrode layer 33 .

(Manufacturing method of electrochemical reaction part)
Next, a method for manufacturing the electrochemical reaction section 3 will be described. 5 to 9 omit the description of the intermediate layer 34 and the reaction prevention layer 35, so the description will be made mainly with reference to FIG.

(Electrode layer forming step)
In the electrode layer forming step, the electrode layer 31 is formed in the form of a thin film in a region wider than the region where the through holes 11 are provided on the front surface of the first plate-like body 1 . The through holes 11 of the first plate-like body 1 can 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 is performed in a low temperature range of 1100° C. or less), a spray coating method (a thermal spraying method, an aerosol deposition method, an aerosol gas deposition method, a methods such as powder jet deposition method, particle jet deposition method, cold spray method, etc.), PVD method (sputtering method, pulse laser deposition method, etc.), CVD method, etc. can be used. Whichever method is used, it is desirable to use a temperature of 1100° C. or less in order to suppress deterioration of the first plate-like body 1 .

When the electrode layer forming step is performed by the low-temperature firing method, it is specifically performed as in the following example. First, material powder of the electrode layer 31 and a solvent (dispersion medium) are mixed to prepare a material paste, which is applied to the front surface of the first plate-like body 1 and fired at 800°C to 1100°C.

(Diffusion suppression layer forming step)
A metal oxide layer 12 (diffusion suppression layer) is formed on the surface of the first plate-like body 1 during the firing process in the electrode layer forming step described above. In addition, if the firing process includes a firing process in which the firing atmosphere is an atmosphere condition with a low oxygen partial pressure, the mutual diffusion suppression effect of elements is high, and the high-quality metal oxide layer 12 with a low resistance value (diffusion suppression layer) is formed. A separate step of forming a diffusion suppressing layer may be included, including the case where the electrode layer forming step is a coating method that does not involve baking. In any case, it is desirable to carry out the treatment at a treatment temperature of 1100° C. or lower, which is capable of suppressing damage to the first plate-like body 1 .

(Intermediate layer forming step)
In the intermediate layer forming step, a thin intermediate layer 34 is formed 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 is performed in a low temperature range of 1100° C. or less), a spray coating method (a thermal spraying method, an aerosol deposition method, an aerosol gas deposition method, a methods such as powder jet deposition method, particle jet deposition method, cold spray method, etc.), PVD method (sputtering method, pulse laser deposition method, etc.), CVD method, etc. can be used. Whichever method is used, it is desirable to use a temperature of 1100° C. or less in order to suppress deterioration of the first plate-like body 1 .

When the intermediate layer forming step is performed by the low-temperature firing method, it is specifically performed as in the following example.
First, material powder for the intermediate layer 34 and a solvent (dispersion medium) are mixed to prepare a material paste, which is applied to the front surface of the first plate-like body 1 . Then, the intermediate layer 34 is compression-molded (intermediate layer smoothing step) and fired at 1100° C. or less (intermediate layer firing step). The intermediate layer 34 can be rolled by, for example, CIP (Cold Isostatic Pressing) molding, roll pressing, RIP (Rubber Isostatic Pressing) molding, or the like. Moreover, it is preferable to bake the intermediate layer 34 at a temperature of 800° C. or more and 1100° C. or less. This is because at such a temperature, the intermediate layer 34 with high strength can be formed while suppressing damage and deterioration of the first plate-like body 1 . It is more preferable to bake the intermediate layer 34 at 1050° C. or lower, and more preferably 1000° C. or lower. This is because the lower the baking temperature of the intermediate layer 34 is, the more the electrochemical element A can be formed while suppressing damage and deterioration of the first plate-like body 1 . Also, the order of the intermediate layer smoothing process and the intermediate layer baking process can be changed.
The intermediate layer smoothing step can also be performed by lapping, leveling treatment, surface cutting/polishing treatment, or the like.

(Electrolyte layer forming step)
In the electrolyte layer forming step, the electrolyte layer 32 is formed in a thin layer state on the intermediate layer 34 while covering the electrode layer 31 and the intermediate layer 34 . Alternatively, it may be formed in the form of a thin film 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 in a low temperature range of 1100° C. or less), a spray coating method (thermal spraying method, aerosol deposition method, aerosol gas deposition method, methods such as powder jet deposition method, particle jet deposition method, cold spray method, etc.), PVD method (sputtering method, pulse laser deposition method, etc.), CVD method, etc. can be used. Whichever method is used, it is desirable to use a temperature of 1100° C. or less in order to suppress deterioration of the first plate-like body 1 .

In order to form a high-quality electrolyte layer 32 that is dense, airtight, and gas-barrier in a temperature range of 1100° C. or less, it is desirable to perform the electrolyte layer forming step by a spray coating method. In that case, the material for the electrolyte layer 32 is sprayed toward the intermediate layer 34 on the first plate-like body 1 to form the electrolyte layer 32 .

(Reaction prevention layer forming step)
In the reaction-preventing layer forming step, the reaction-preventing layer 35 is formed in a thin layer state on the electrolyte layer 32 . As described above, the reaction prevention layer 35 is formed by a low-temperature firing method (a wet method in which firing is performed in a low temperature range of 1100 ° C. or less), a spray coating method (a thermal spraying method, an aerosol deposition method, an aerosol gas deposition method). , powder jet deposition method, particle jet deposition method, cold spray method, etc.), PVD method (sputtering method, pulse laser deposition method, etc.), CVD method, and the like can be used. Whichever method is used, it is desirable to use a temperature of 1100° C. or less in order to suppress deterioration of the first plate-like body 1 . In order to flatten the upper surface of the anti-reaction layer 35, for example, after the anti-reaction layer 35 is formed, the surface may be subjected to leveling treatment or cutting/polishing treatment, or press working may be performed after wet formation and before firing. good.

(Counter electrode layer forming step)
In the counter electrode layer forming step, the counter electrode layer 33 is formed as a thin layer on the reaction prevention layer 35 . As described above, the counter electrode layer 33 can be formed by a low-temperature firing method (a wet method in which firing is performed in a low temperature range of 1100° C. or less), a spray coating method (a thermal spraying method, an aerosol deposition method, or an aerosol gas deposition method). , powder jet deposition method, particle jet deposition method, cold spray method, etc.), PVD method (sputtering method, pulse laser deposition method, etc.), CVD method, and the like can be used. Whichever method is used, it is desirable to use a temperature of 1100° C. or less in order to suppress deterioration of the first plate-like body 1 .

As described above, the electrochemical reaction section 3 can be manufactured.

In the electrochemical reaction section 3, the intermediate layer 34 and the reaction prevention layer 35 may be provided without either one or both of them. That is, a form in which the electrode layer 31 and the electrolyte layer 32 are in contact with each other, or a form in which the electrolyte layer 32 and the counter electrode layer 33 are in contact with each other are also possible. In this case, the intermediate layer forming step and the reaction prevention layer forming step are omitted in the manufacturing method described above. It is also possible to add a step of forming other layers or to laminate a plurality of layers of the same type, but in any case, it is desirable to carry out at a temperature of 1100° C. or less.

(Electrochemical device laminate)
As shown in FIG. 11 , an electrochemical element stack S (electrochemical element assembly) has a plurality of electrochemical elements A, and adjacent electrochemical elements A are plate-like elements constituting one electrochemical element A. The support 10 and the plate-like support 10 constituting another electrochemical element A face each other, and the electrochemical reaction part 3 in the plate-like support 10 constituting one electrochemical element A and the outer surface of the second plate-like body 2 different from the first plate-like body 1 on which are electrically connected to each other, and a flow section A2 is formed between the two outer surfaces adjacent to each other, through which the second gas flows along the two outer surfaces, a plurality of electrochemical elements A is arranged in a stacked manner (aggregated arrangement). In order to establish an electrical connection, in addition to simply bringing the electrically conductive surfaces into contact with each other, methods such as applying surface pressure to the contact surface and interposing a highly electrically conductive material to lower the contact resistance are adopted. It is possible. Specifically, each rectangular electrochemical element has the first through portion 41 at one end and the second through portion 51 at the other end aligned, and the electrochemical reaction portion 3 of each electrochemical element A are aligned in a state in which they face upward, and the first annular seal portion 42 and the second annular seal portion 52 are interposed between the first through portion 41 and the second through portion 51 to stack (assemble) As a result, the above configuration is obtained.

In the plate-like support 10, a first penetration portion forming a supply channel 4 for circulating a first gas, which is one of a reducing component gas and an oxidizing component gas, from the outside in the surface penetration direction to the internal channel A1. 41 are provided at one end in the longitudinal direction of the rectangular plate-like support 10, and in the flow-through portion A2, first through portions 41 respectively formed on both outer surfaces of the plate-like support 10 and the flow-through portion A2. A first annular seal portion 42 is provided as a partitioning annular seal portion, and the first penetrating portion 41 and the first annular seal portion 42 form a supply passage 4 through which the first gas flows to the internal flow passage A1. In addition, an annular bulging portion a is provided on the side surface of the first plate-like body 1 opposite to the internal flow path A1 around the portion of the first plate-like body 1 with which the first annular seal portion 42 abuts. Positioning of the first annular seal portion 42 along the surface of the first plate-like body 1 is facilitated.

In addition, the plate-like support 10 has a second through portion 51 forming a discharge passage 5 through which the first gas flowing through the internal flow path A1 flows outward in the surface penetration direction of the plate-like support 10 at the other end. On the side, the second through portion 51 is configured to allow the first gas to flow while being separated from the second gas. A second annular seal portion 52 as an annular seal portion that separates the second through portion 51 from the flow portion A2, and the second through portion 51 and the second annular seal portion 52 allow the internal flow path A1 to flow. A discharge passage 5 is formed through which the first gas flows.

The first and second annular seal portions 42 and 52 are made of an insulating ceramic material such as alumina, a metal coated with this material, or a material such as mica fiber or glass, and electrically insulate adjacent electrochemical elements from each other. functions as an insulating seal.

(Electrochemical module)
As shown in FIG. 11 , the electrochemical module M includes a housing B made of an insulator in which the electrochemical element stack S is installed, and a first flow path A1 from the outside of the housing B through the supply path 4 to the internal flow path A1. A first gas supply part 61 for circulating the gas, a first gas discharge part 62 for circulating the first gas after the reaction, and a second gas supply for circulating the second gas from the outside of the housing B to the flow part A2. part 71, a second gas discharge part 72 for circulating the second gas after the reaction, and an output part 8 for obtaining an output associated with the electrochemical reaction in the electrochemical reaction part 3; A distribution chamber 9 is provided for distributing and circulating the second gas circulated from the gas supply portion 71 to the circulating portion A2.
The distribution chamber 9 is a space located on the side (lateral side) of the electrochemical element stack S, which is the inlet and outlet of the flow section of the electrochemical element stack S. The flow section A2 is located on the space side. is formed to communicate with the space.

The electrochemical element laminate S is contained in the housing B in a state of being sandwiched between a pair of current collectors 81 and 82, and the output section 8 extends from the current collectors 81 and 82, The current collectors 81 and 82 airtightly accommodate the electrochemical element laminate S with respect to the housing B, and the current collectors 81 and 82 is provided to function as a buffer material for each electrochemical element A.

As a result, the electrochemical module M is circulated with fuel gas from the first gas supply unit 61 and air from the second gas supply unit 71, so that the fuel gas enters as indicated by the dashed arrow in FIG. Air enters as indicated by the arrow. The fuel gas circulated from the first gas supply portion 61 is guided to the supply path 4 through the first through portion 41 of the electrochemical element A at the top of the electrochemical element stack S, and partitioned by the first annular seal portion 42. The internal flow paths A1 of all of the electrochemical elements A are supplied from the supply path 4 to the electrochemical element A. Also, the air circulated from the second gas supply portion 71 temporarily flows into the distribution chamber 9 and then flows through the circulating portion A2 formed between the electrochemical elements A. As shown in FIG.
By the way, when the second plate-like body 2 is used as a reference, the first plate-like body 1 and the second plate-like body 2 are formed at the portion where the corrugated second plate-like body 2 protrudes from the first plate-like body 1 . An internal flow path A1 is formed between the two and contacts the electrochemical reaction portion 3 of the adjacent electrochemical element A to enable electrical connection. On the other hand, the portion of the corrugated second plate-shaped body 2 that contacts the first plate-shaped body 1 is electrically connected to the first plate-shaped body 1, and the electrochemical element A adjacent to the second plate-shaped body 2 is electrically connected to the first plate-shaped body 1. A flow section A2 is formed between the chemical reaction section 3 and the chemical reaction section 3.
A part of FIG. 10 shows an electrochemical element A with a cross section including the internal flow path A1 and an electrochemical element A with a cross section including the flow passage A2 side by side for convenience. The fuel gas circulated from the portion 61 reaches the distribution portion A12 (see FIGS. 1, 4, and 7), spreads along the width direction of one end side through the distribution portion A12, and flows out of the internal flow path A1. Each sub-channel A11 is reached (see FIGS. 1, 3 and 7). Then, the fuel gas entering the internal flow path A1 can enter the electrode layer 31 via the gas flow permitting portion 1A. In addition, the fuel gas, together with the electrochemically reacted fuel gas, further advances through the internal flow path A1, passes through the junction A13 and the second through portion 51, and enters the discharge path 5 formed by the second annular seal portion 52. It advances and flows outside the housing B from the first gas discharge part 62 together with the fuel gas that has completed the electrochemical reaction from the other electrochemical element A. On the other hand, the air circulated from the second gas supply part 71 can enter the circulating part A<b>2 through the distribution chamber 9 and enter the counter electrode layer 33 . In addition, the air, along with the electrochemically reacted air, further advances along the electrochemical reaction section 3 through the circulation section A2 and is circulated outside the housing B from the second gas discharge section 72 .

The electric power generated in the electrochemical reaction section 3 according to the flow of the fuel gas and air is transferred between the current collectors 81 and 82 due to the contact between the electrochemical reaction section 3 of the adjacent electrochemical element A and the second plate-like body 2. are connected in series between them, and the synthesized output is taken out from the output section 8. FIG.

The electrochemical device 100 and the energy system Z can be constructed using the electrochemical module M described above.

In addition, in the electrochemical module M, the electrochemical element A may not be laminated. In other words, in the electrochemical module M, a plurality of electrochemical elements A may be arranged in a grouped state.

(annular spacer)
As shown in FIGS. 3, 8, 9, and 11, in each electrochemical device A, an annular spacer 91 is arranged between the first plate-like body 1 and the second plate-like body 2. . The annular spacer 91 is arranged on the one end side (first through portion 41 ) and the other end side (second through portion 51 ) of the plate-like support 10 .

(First example of annular spacer)
A first example of the annular spacer 91 will be described with reference to FIGS. 15, 16 and 17. FIG. 17, the cross section of the annular spacer 91 is drawn as a cross section along the plane CS1 shown in FIG.

The ring-shaped spacer 91 is a plate-like member having through holes 91a on the front and back. The annular spacer 91 allows gas to pass from the space SI inside the through-hole 91a to the space SO outside the annular spacer 91 while being sandwiched between other members (the first plate-like body 1 and the second plate-like body 2). A flow path 91b is provided for flowing the liquid.

Specifically, the annular spacer 91 is a disk-shaped member having a through hole 91a in the center. The annular spacer 91 can be integrally formed by pressing. The annular spacer 91 may be made of an electrically conductive material. For example, annular spacer 91 is made of metal. The material of the annular spacer 91 preferably contains at least one of ferritic stainless steel, austenitic stainless steel, Inconel, copper, and Invar. The material of the annular spacer 91 may be an insulator.

The annular spacer 91 of the first example includes a base portion 92 , a projecting portion 93 and a flange portion 94 .

The base portion 92 is a portion extending in a flat plate shape.

The protruding portion 93 is a portion of the base portion 92 that protrudes in the front and back directions (vertical direction in FIG. 17, vertical direction in the electrochemical device) from the surroundings. In the illustrated example, the annular spacer 91 has eight projecting portions 93 that are evenly arranged in the circumferential direction. The upper surface of the projecting portion 93 is flat. The upper surfaces of all protrusions 93 are substantially the same height. The annular spacer 91 may have protrusions on both the front and back surfaces. The number of protrusions 93 is not limited to eight, and may be one to seven, or may be nine or more.

The flange portion 94 is a flange-like portion that protrudes in the front and back direction at the central portion of the base portion 92 . The flange portion 94 is a peripheral wall of the through hole 91a. In the illustrated example, the flange portion 94 protrudes to the side opposite to the protruding portion 93 in the front-back direction. The flange portion 94 is formed in an annular shape. The flange portion 94 has a continuous annular shape. A part of the flange portion 94 may be cut out. In other words, the flange portion 94 may have a discontinuous annular shape.

FIG. 17 shows a state in which the annular spacer 91 of the first example is arranged between the first plate-like body 1 and the second plate-like body 2 . The flange portion 94 is inserted into the second through portion 51 (through hole 2 b ) of the second plate-like body 2 . The annular spacer 91 is positioned with respect to the second plate-like body 2 by the flange portion 94 . The upper surface of the annular spacer 91 , that is, the upper surface of the projecting portion 93 contacts the lower surface of the first plate-like body 1 . The bottom surface of the base portion 92 contacts the top surface of the second plate-like body 2 . The first plate-like body 1 and the second plate-like body 2 can be electrically connected through the annular spacer 91 . Electrical conductivity between the first plate-like body 1 and the second plate-like body 2 is improved as compared with the case without the annular spacer 91 .

A space P is created between the base 92 and the first plate-like body 1 due to the presence of the projecting portion 93 . A space P is a space around the protrusion 93 . The space P connects the internal flow path A1 (the space SO outside the annular spacer 91 ) of the plate-like support 10 and the space SI inside the through hole 91 a of the annular spacer 91 . A space P is formed between the two protrusions 93 . Since the annular spacer 91 has eight protruding portions 93, eight spaces P are arranged in the circumferential direction around the through hole 91a.

As shown in FIG. 17 , the annular spacer 91 is arranged with its central axis (the central axis of the through hole 91 a ) aligned with the central axis of the second through portion 51 . Specifically, the central axis of the annular spacer 91 (the central axis of the through hole 91a) is the central axis of the through hole 1b formed in the first plate-like body 1 and the through hole formed in the second plate-like body 2. 2 b and the central axis of the second annular seal portion 52 . Therefore, the annular spacer 91 is arranged so that the second through portion 51 (through hole 2b) and the through hole 91a of the annular spacer 91 overlap when viewed in the thickness direction of the plate-like support 10 . In this embodiment, the annular spacer 91 is arranged so that the second through portion 51 (through hole 2b) and the entire through hole 91a overlap. The annular spacer 91 may be arranged so that the second through-hole 51 (through-hole 2b) and a part of the through-hole 91a overlap.

FIG. 17 shows a state in which the annular spacer 91 is arranged on the other end side (second through portion 51) of the plate-like support 10. FIG. The annular spacer 91 disposed on the one end side (the first through portion 41) of the plate-like support 10 also has the same shape as the example shown in FIG.

When fuel gas (first gas; an example of “gas”) is supplied to the first through portion 41, the fuel gas flows from the through hole 91a of the annular spacer 91 through the space P into the internal flow path A1. The fuel gas that has flowed through the internal flow path A<b>1 passes through the space P of the annular spacer 91 on the second through portion 51 side, flows into the through hole 91 a , and flows out to the second through portion 51 . Thus, the space P functions as the flow path 91b.

The annular spacer 91 has eight flow paths 91b corresponding to the eight spaces P. As shown in FIG. The eight flow paths 91b radially extend from the through holes 91a. The eight flow paths 91b are arranged side by side in the circumferential direction. Therefore, the first gas from the first penetration portion 41 can be effectively diffused into the internal flow path A1 (distribution portion A12). That is, the annular spacer 91 can uniformly supply the first gas to the plurality of sub-flow paths A11.

(Second example of annular spacer)
A second example of the annular spacer 91 will be described with reference to FIGS. 18, 19 and 20. FIG. In addition, in the cross-sectional view of FIG. 20, the cross-section of the annular spacer 91 is drawn as a cross-section along the plane CS2 shown in FIG.

The annular spacer 91 of the second example is a plate-like member provided with through holes 91a extending over the front and back, as in the first example. The annular spacer 91 allows gas to pass from the space SI inside the through-hole 91a to the space SO outside the annular spacer 91 while being sandwiched between other members (the first plate-like body 1 and the second plate-like body 2). A flow path 91b is provided for flowing the liquid.

Specifically, the annular spacer 91 is a disk-shaped member having a through hole 91a in the center. The annular spacer 91 can be integrally formed by pressing. The annular spacer 91 may be made of an electrically conductive material. For example, annular spacer 91 is made of metal. The material of the annular spacer 91 preferably contains at least one of ferritic stainless steel, austenitic stainless steel, Inconel, copper, and Invar. The material of the annular spacer 91 may be an insulator.

The annular spacer 91 of the second example includes a first portion 95 and a second portion 96 .

The first portion 95 is a portion extending in a flat plate shape. In the illustrated example, the annular spacer 91 includes eight first portions 95 arranged with a gap T in the circumferential direction. The upper and lower surfaces of the first portion 95 are flat. The top and bottom surfaces of all the first portions 95 are approximately the same height. In other words, all the first parts 95 are arranged on the same plane. The height of the top surface, the height of the bottom surface, and the thickness of the first portion 95 may be different among the first portions 95 . The number of first parts 95 is not limited to eight, and may be two to seven, or nine or more.

The gap T extends from the outer peripheral edge of the annular spacer 91 to the through hole 91a. Since the annular spacer 91 has eight first portions 95, eight gaps T are arranged in the circumferential direction around the through hole 91a. In the illustrated example, the eight gaps T have the same width. The width of the gap T may be different.

The second portion 96 is a portion that connects the plurality of first portions 95 . The second portion 96 is a flange-like portion that protrudes in the front and back directions at the central portion of the annular spacer 91 . The second portion 96 is the peripheral wall of the through hole 91a. The second portion 96 is connected to the lower surface of the first portion 95 and protrudes downward from the first portion 95 . In the illustrated example, the second portion 96 is formed in an annular shape. A part of the second part 96 may be cut out. In other words, the second portion 96 may have a discontinuous annular shape.

FIG. 20 shows a state in which the annular spacer 91 of the second example is arranged between the first plate-like body 1 and the second plate-like body 2 . The second portion 96 enters the second through portion 51 (through hole 2 b ) of the second plate-like body 2 . The second portion 96 positions the annular spacer 91 with respect to the second plate-like body 2 . The upper surface of the annular spacer 91 , that is, the upper surface of the first portion 95 contacts the lower surface of the first plate-like body 1 . The lower surface of the first portion 95 contacts the upper surface of the second plate-like body 2 . The first plate-like body 1 and the second plate-like body 2 can be electrically connected through the annular spacer 91 . Electrical conductivity between the first plate-like body 1 and the second plate-like body 2 is improved as compared with the case without the annular spacer 91 .

In the state of FIG. 20, the gap T is surrounded by the two first parts 95, the first plate-like body 1, and the second plate-like body 2. As shown in FIG. The gap T connects the internal flow path A1 (the space SO outside the annular spacer 91 ) of the plate-like support 10 and the space SI inside the through hole 91 a of the annular spacer 91 .

As shown in FIG. 20 and similarly to the first example, the annular spacer 91 is arranged with its central axis (the central axis of the through-hole 91 a ) aligned with the central axis of the second through-hole 51 . Specifically, the central axis of the annular spacer 91 (the central axis of the through hole 91a) is the central axis of the through hole 1b formed in the first plate-like body 1 and the through hole formed in the second plate-like body 2. 2 b and the central axis of the second annular seal portion 52 . Therefore, the annular spacer 91 is arranged so that the second through portion 51 (through hole 2b) and the through hole 91a of the annular spacer 91 overlap when viewed in the thickness direction of the plate-like support 10 . In this embodiment, the annular spacer 91 is arranged so that the second through portion 51 (through hole 2b) and the entire through hole 91a overlap. The annular spacer 91 may be arranged so that the second through-hole 51 (through-hole 2b) and a part of the through-hole 91a overlap.

FIG. 20 shows a state in which the annular spacer 91 is arranged on the other end side (second through portion 51) of the plate-like support 10. FIG. The annular spacer 91 arranged on the one end side (the first through portion 41) of the plate-like support 10 also has the same shape as the illustrated example of FIG.

When fuel gas (first gas; an example of “gas”) is supplied to the first through portion 41, the fuel gas flows from the through hole 91a of the annular spacer 91 through the gap T into the internal flow path A1. Then, the fuel gas that has flowed through the internal flow path A1 flows into the through hole 91 a through the gap T of the annular spacer 91 on the second through portion 51 side, and then flows out to the second through portion 51 . Thus, the gap T functions as the flow path 91b.

The annular spacer 91 has eight flow paths 91b corresponding to the eight gaps T. As shown in FIG. The eight flow paths 91b radially extend from the through holes 91a. The eight flow paths 91b are arranged side by side in the circumferential direction. Therefore, the first gas from the first penetration portion 41 can be effectively diffused into the internal flow path A1 (distribution portion A12). That is, the annular spacer 91 can uniformly supply the first gas to the plurality of sub-flow paths A11.

Advantages of the annular spacer 91 common to the first and second examples will be described. In the electrochemical module M, a plurality of electrochemical elements A are stacked. A plurality of electrochemical elements A are pressure-welded in the stacking direction. Then, force acts on the plate-like support 10 from the first annular seal portion 42 and the second annular seal portion 52 . That is, a compressive force acts on the plate-like support 10 in the thickness direction. Due to the presence of the annular spacer 91, deformation of the plate-like support 10 (in particular, deformation in the thickness direction) is suppressed. In addition, the reaction force from the plate-like support 10 to the first annular seal portion 42 and the second annular seal portion 52 increases. The first annular seal portion 42 and the second annular seal portion 52 are strongly pressed against the plate-like support 10 . Airtightness is improved at the contact portion between the first annular seal portion 42 and the plate-shaped support body 10 and the contact portion between the second annular seal portion 52 and the plate-shaped support body 10 .

The annular spacer 91 may be arranged in an upside down posture compared to the illustrated examples of FIGS. 17 and 20 . In other words, the annular spacer 91 may be arranged in a posture opposite to that shown in FIGS. 17 and 20 .

The annular spacers 91 of the first and second examples are circular annular. Annular spacer 91 may be an annular shape of any shape, such as elliptical, square, polygonal, or the like.

(energy system, electrochemical device)
An overview of the energy system Z and the electrochemical device 100 is shown in FIG.
The energy system Z has an electrochemical device 100 and a heat exchanger 200 as a waste heat utilization section that reuses the heat circulated from the electrochemical device 100 .
The electrochemical device 100 has an electrochemical module M, a desulfurizer 101, and a reformer 102 which is a type of fuel converter, and circulates a fuel gas containing a reducing component to the electrochemical module M. It has a fuel supply unit 103 and an inverter 104, which is a type of power converter, as an output unit 8 for extracting electric power from the electrochemical module M. FIG.

Specifically, the electrochemical device 100 has a desulfurizer 101, a reformed 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 city gas. If the raw fuel contains sulfur compounds, the provision of the desulfurizer 101 can suppress adverse effects of the sulfur compounds on the reformer 102 or the electrochemical element A. FIG. The vaporizer 106 generates steam from the reformed water flowing from the reformed water 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 reformed gas containing hydrogen.

The electrochemical module M uses the reformed gas circulated from the reformer 102 and the air circulated from the blower 107 to cause an electrochemical reaction to generate power. The combustion unit 108 mixes the reaction exhaust gas flowing from the electrochemical module M with air to burn the combustible components in the reaction exhaust gas.

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

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

The raw fuel is circulated to the desulfurizer 101 through the raw fuel supply passage 112 by the operation of the booster pump 111 . The reformed water in the reformed water tank 105 is circulated to the vaporizer 106 through the reformed water supply passage 114 by the operation of the reformed water pump 113 . The raw fuel supply passage 112 joins the reformed water supply passage 114 at a portion downstream of the desulfurizer 101, and the reformed water and the raw fuel joined outside the housing B are vaporized. 106.

The reformed water is vaporized in the vaporizer 106 and becomes water vapor. The raw fuel containing steam generated in the vaporizer 106 is circulated to the reformer 102 through the steam-containing raw fuel supply passage 115 . The raw fuel is steam-reformed in the reformer 102 to generate a reformed gas (first gas having a reducing component) containing hydrogen gas as a main component. The reformed gas produced by the reformer 102 is distributed to the electrochemical module M through the fuel supply section 103 .

The reaction exhaust gas is combusted in the combustion section 108 to become combustion exhaust gas and sent to the heat exchanger 200 through the combustion exhaust gas discharge passage 116 . A combustion catalyst portion 117 (for example, a platinum-based catalyst) is arranged in the combustion exhaust gas discharge passage 116 to burn and remove reducing components such as carbon monoxide and hydrogen contained in the combustion exhaust gas.

The heat exchanger 200 exchanges heat between flue gas generated by combustion in the combustion section 108 and the flowing cold water to generate hot water. That is, the heat exchanger 200 operates as a waste heat utilization unit that reuses heat discharged from the electrochemical device 100 .

Instead of the exhaust heat utilization unit, a reaction exhaust gas utilization unit that utilizes the reaction exhaust gas that flows (without being burned) from the electrochemical module M may be provided. Also, at least a part of the reaction exhaust gas circulated outside the housing B from the first gas discharge part 62 is joined to any part of 100, 101, 103, 106, 112, 113, 115 in FIG. 12 for recycling. You can Remaining hydrogen gas not used in the reaction in the electrochemical device A is included in the reaction exhaust gas. In the reaction exhaust gas utilization unit, the remaining hydrogen gas is used for heat utilization by combustion and power generation by a fuel cell or the like, thereby effectively utilizing energy.

FIG. 14 shows an example of an energy system Z and an electrochemical device 100 when operating the electrochemical reaction section 3 as an electrolytic cell. In this system, supplied water and carbon dioxide are electrolyzed in the electrochemical reaction section 3 to produce hydrogen, carbon monoxide, and the like. Furthermore, hydrocarbons and the like are synthesized in the fuel converter 25 . The heat exchanger 24 in FIG. 14 is operated as an exhaust heat utilization unit for heat exchange and vaporization of reaction heat generated by the reaction occurring in the fuel converter 25 and water, and the heat exchanger 23 in FIG. Energy efficiency can be improved by configuring the chemical element A to operate as an exhaust heat utilization unit for preheating by exchanging the exhaust heat generated by the chemical element A with water vapor and carbon dioxide.
Also, the power converter 104 (converter) distributes power to the electrochemical device A. FIG. Thereby, the electrochemical device A acts as an electrolytic cell as described above.
Therefore, according to the above configuration, it is possible to provide the electrochemical device 100, the energy system Z, and the like that can improve the efficiency of converting electrical energy into chemical energy such as fuel.

(Other embodiments)
(1) In the above embodiment, the electrochemical element A is used in the solid oxide fuel cell as the electrochemical device 100, but the electrochemical element A uses a solid oxide electrolytic cell or a solid oxide. It can also be used as an oxygen sensor or the like. Moreover, the electrochemical element A is not limited to being used in combination as an electrochemical element laminate S or an electrochemical module M, and may be used alone.

(2) In the above embodiment, composite materials such as NiO _- GDC, Ni _- GDC, NiO _- YSZ, Ni _- YSZ, CuO _- CeO ₂ and Cu _- CeO ₂ are used as the material of the electrode layer 31, and the counter electrode A composite oxide such as LSCF or LSM is used as the material of the layer 33 . In the electrochemical element A thus constructed, hydrogen gas is circulated through the electrode layer 31 to form a fuel electrode (anode), air is circulated through the counter electrode layer 33 to form an air electrode (cathode), and solid oxide type It can be used as a fuel cell. By changing this configuration, the electrochemical device A can be configured so that the electrode layer 31 can be used as an air electrode and the counter electrode layer 33 can be used as a fuel electrode. That is, as the material of the electrode layer 31, for example, a complex oxide such as LSCF or LSM is used, and as the material of the counter electrode layer 33, for example, NiO _- GDC, Ni _- GDC, NiO _- YSZ, Ni _- YSZ, CuO _-- CeO ₂ , Cu _- Using composites such as _CeO2 . In the electrochemical element A thus constructed, air is circulated through the electrode layer 31 to form an air electrode, hydrogen gas is circulated through the counter electrode layer 33 to form a fuel electrode, and the electrochemical element A is a solid oxide type. It can be used as a fuel cell.

(3) In the above embodiment, the electrode layer 31 is arranged between the first plate-like body 1 and the electrolyte layer 32, and the counter electrode layer 33 is arranged on the side opposite to the first plate-like body 1 when viewed from the electrolyte layer 32. placed. A configuration in which the electrode layer 31 and the counter electrode layer 33 are reversely arranged is also possible. That is, it is also possible to arrange the counter electrode layer 33 between the first plate-like body 1 and the electrolyte layer 32 and arrange the electrode layer 31 on the side opposite to the first plate-like body 1 when viewed from the electrolyte layer 32. . In this case, the flow 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 whether the first gas or the second gas is one or the other of the reducing component gas and the oxidizing component gas depend on the order of the electrode layer 31 and the counter electrode layer 33. Various forms can be adopted as long as the arrangement is such that the first gas and the second gas are circulated in a form that reacts appropriately with respect to the gas.

(4) In the above-described embodiment, the electrochemical reaction section 3 is provided on the opposite side of the first plate-shaped body 1 from the second plate-shaped body 2, covering the gas flow-permitting section 1A. It may be provided on the second plate-like body 2 side of the first plate-like body 1 . That is, the present invention is realized even if the electrochemical reaction section 3 is arranged in the internal flow path A1.

(5) In the above embodiment, a pair of the first penetrating portion 41 and the second penetrating portion 51 are provided at both ends of the rectangular plate-like support 10. , may be provided in two or more pairs. Also, the first through portion 41 and the second through portion 51 need not be provided in pairs. Therefore, one or more of each of the first through portion 41 and the second through portion 51 can be provided.
Furthermore, the plate-shaped support 10 is not limited to a rectangular shape, and various shapes such as a square shape and a circular shape can be adopted.

(6) The shape of the first and second annular seal portions 42 and 52 does not matter as long as the first and second through portions 41 and 51 are communicated with each other to prevent gas leakage. In other words, the first and second annular seal portions 42 and 52 may have an endless configuration having an opening communicating with the through portion, and may have a configuration that seals between the adjacent electrochemical elements A. As shown in FIG. The first and second annular seal portions 42, 52 are, for example, annular. The annular shape may be circular, elliptical, square, polygonal, or any other shape.

(7) In the above description, the plate-shaped support 10 is composed of the first plate-shaped body 1 and the second plate-shaped body 2 . Here, the first plate-like body 1 and the second plate-like body 2 may be composed of separate plate-like bodies, or may be composed of one plate-like body as shown in FIG. good too. In the case of FIG. 13, for example, by bending one plate-like body, the first plate-like body 1 and the second plate-like body 2 are overlapped. Then, the first plate-like body 1 and the second plate-like body 2 are integrated by welding or the like of the peripheral portion 1a. It should be noted that the first plate-like body 1 and the second plate-like body 2 may be composed of a series of seamless plate-like bodies, and the series of plate-like bodies are bent to be molded as shown in FIG. may
Further, as will be described later, the second plate-like body 2 may be composed of one member, or may be composed of two or more members. Similarly, the first plate-like body 1 may be composed of one member, or may be composed of two or more members.

(8) The second plate-like body 2 and the first plate-like body 1 form an internal flow path A1. The internal channel A1 has a distribution portion A12, a plurality of sub-channels A11, and a confluence portion A13. As shown in FIG. 1, the first gas supplied to the distribution section A12 is distributed and supplied to each of the plurality of sub-flow paths A11, and joins at the confluence section A13 at the outlet of the plurality of sub-flow paths A11. Therefore, the first gas flows along the gas flow direction from the distribution portion A12 to the confluence portion A13.
The plurality of sub-flow paths A11 are formed by forming the portion of the second plate-like body 2 other than the distribution portion A12 to the confluence portion A13 into a corrugated plate shape. Then, as shown in FIG. 5, the plurality of sub-flow paths A11 are configured in a corrugated plate shape in a cross-sectional view in a flow crossing direction crossing the gas flow direction of the first gas. Such a plurality of sub-flow paths A11 are formed by extending corrugated plates along the gas flow direction shown in FIG. The plurality of sub-channels A11 may be formed of a series of wavy plate-like bodies between the distribution portion A12 and the confluence portion A13, or may be formed of two or more wavy plate-like bodies. . The plurality of sub-channels A11 may be composed of, for example, two or more wavy plate-like bodies separated along the direction along the gas flow direction, or two or more separated along the direction along the cross-flow direction. It may be composed of the wavy plate-like body described above.

Moreover, as shown in FIG. 5, the plurality of sub-flow paths A11 are configured in a wave shape by repeatedly forming peaks and valleys of the same shape. However, the second plate-shaped body 2 may have a plate-shaped portion in the region where the plurality of sub-channels A11 are formed. For example, the plurality of sub-channels A11 may be configured by alternately forming plate-like portions and projecting portions. The projecting portion can be a portion through which a fluid such as the first gas flows.

(9) The portion of the second plate-like body 2 corresponding to the plurality of sub-flow paths A11 need not be entirely corrugated, and at least a portion thereof may be corrugated. Just do it. For example, between the distribution portion A12 and the confluence portion A13, the second plate-like body 2 may have a plate-like portion in the gas flow direction and a corrugated plate-like portion in the remaining portion. Further, the second plate-like body 2 may have a plate-like shape in part in the cross-flow direction and a corrugated plate-like shape in the rest.

(10) In the above embodiment, the electrochemical device comprises an electrochemical module M comprising a plurality of electrochemical elements A; However, the electrochemical device of the above embodiment can also be applied to a configuration provided with one electrochemical element.

Note that the configurations disclosed in the above embodiments can be applied in combination with configurations disclosed in other embodiments as long as there is no contradiction. Moreover, the embodiments disclosed in this specification are exemplifications, and the embodiments of the present invention are not limited to these, and can be modified as appropriate without departing from the object of the present invention.

INDUSTRIAL APPLICABILITY The present invention is applicable to annular spacers, electrochemical elements, electrochemical modules, electrochemical devices, energy systems, solid oxide fuel cells and solid oxide electrolysis cells.

Reference Signs List 1: first plate-like body 2: second plate-like body 10: plate-like support 25: fuel converter 31: electrode layer (first electrode, second electrode)
32: electrolyte layer 33: counter electrode layer (first electrode, second electrode)
41: First penetration part (penetration part)
51: Second penetration part (penetration part)
91 : Annular spacer 91a : Through hole 91b : Flow path 93 : Projection 95 : First part 96 : Second part 100 : Electrochemical device 104 : Electric power converter 200 : Heat exchanger (exhaust heat utilization part)
A: Electrochemical element A1: Internal channel CS1: Surface CS2: Surface M: Electrochemical module P: Space SI: Space SO: Space T: Gap Z: Energy system

Claims (13)

A plate-shaped annular spacer provided with through-holes extending over the front and back, wherein the annular spacer is sandwiched between other members and provided with a channel for allowing gas to flow from the space inside the through-hole to the space outside the annular spacer. Spacer. 2. The annular spacer according to claim 1, wherein at least one of the front surface and the rear surface has a protrusion projecting in the front and back directions from the periphery, and the space around the protrusion functions as the flow path. 2. The annular spacer according to claim 1, comprising a plurality of first parts arranged with gaps therebetween and a second part connecting said first parts, said gaps functioning as said flow paths. 4. The annular spacer according to any one of claims 1 to 3, which is made of an electrically conductive material. 5. The annular spacer according to claim 4, wherein the material includes at least one of ferritic stainless steel, austenitic stainless steel, Inconel, copper and Invar. An electric field comprising: an electrolyte layer; a first electrode and a second electrode respectively arranged on both sides of the electrolyte layer; and a plate-like support supporting the electrolyte layer, the first electrode, and the second electrode a chemical element,
The plate-shaped support includes a conductive first plate-shaped body, a conductive second plate-shaped body, and an inner portion formed between opposing surfaces of the first plate-shaped body and the second plate-shaped body. a flow path;
6. An electrochemical device, wherein the annular spacer according to any one of claims 1 to 5 is arranged between said first plate-like body and said second plate-like body. At least one of the first plate-shaped body and the second plate-shaped body has a through-hole forming a gas supply path to the internal flow path, and the through-hole when viewed in the thickness direction of the plate-shaped support. 7. The electrochemical device according to claim 6, wherein the annular spacer is arranged such that the portion overlaps the through hole of the annular spacer. An electrochemical module in which a plurality of the electrochemical devices according to claim 6 or 7 are arranged in an aggregate state. 8. The electrochemical device according to claim 6 or 7 or the electrochemical module according to claim 8, and generating a reducing component to be supplied to the electrochemical device or the electrochemical module, or the electrochemical device or the electrochemical module. an electrochemical device comprising at least a fuel converter for converting a gas containing reducing components produced in the electrochemical module. The electrochemical element according to claim 6 or 7 or the electrochemical module according to claim 8, and extracting electric power from the electrochemical element or the electrochemical module or supplying electric power to the electrochemical element or the electrochemical module. An electrochemical device comprising at least a power converter that 11. An energy system comprising the electrochemical device according to claim 9 or 10, and a waste heat utilization unit that reuses heat discharged from the electrochemical device. A solid oxide fuel cell comprising the electrochemical device according to claim 6 or 7, wherein the electrochemical device causes a power generation reaction. A solid oxide electrolytic cell comprising the electrochemical element according to claim 6 or 7, wherein the electrochemical element causes an electrolytic reaction.

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