JP2007126734A - Electrochemical reaction apparatus, oxygen enrichment device and hydrogen enrichment device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrochemical reaction apparatus such as an oxygen enrichment device, which prevents an electrochemical cell such as an oxygen permeable cell from being damaged, and also prevents a gas such as oxygen obtained from an electrochemical cell such as an oxygen permeable cell, which gives and receives electrons, from leaking to the outside of the oxygen enrichment device. <P>SOLUTION: The electrochemical reaction cell has: a tabular cell (1) which gives and receives electrons; a substrate (2) which has an opening formed at a position facing to a central portion of the cell and is made from a material having a heat expansion coefficient different from that of the above cell; and an interjacent member (3) arranged between the cell and the substrate. The interjacent member is prepared by stacking a plurality of sheet materials having an opening formed in the central portion so as to communicate with the above opening, and by integrating the sheet materials by bonding them at different positions in a plane direction so that each space between them keeps airtight. The sheet material in one end side in a stacked direction is bonded to the whole circumference of the cell, and the sheet material in the other end side is bonded to the whole circumference of the substrate. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an electrochemical reaction device equipped with an electrochemical cell for transferring electrons, and in particular, an oxygen enricher and a hydrogen permeable cell using an oxygen permeable cell which is a kind of the electrochemical cell. It relates to the hydrogen enricher used.

  In an oxygen permeable cell using a conventional electrochemical cell, as shown in FIG. 5, a cathode 91 is provided on one side of a thin plate-like solid electrolyte 90 having oxygen ion conductivity, and an anode is provided on the other side. A pole 92 is provided. When a DC power source V is connected between the electrodes 91 and 92 at a predetermined temperature, oxygen ions permeate from the cathode 91 side toward the anode 92 side.

  Further, a plate-like separator 93 in which an air passage 93a is formed is disposed outside the oxygen permeable cell on the cathode electrode 91 side, and oxygen on the outside on the anode electrode 92 side. A plate-like separator 94 in which a passage 94a is formed is disposed, and the oxygen permeable cell is sandwiched between the separators 93 and 94 to constitute an oxygen enricher.

  Each of the separators 93 and 94 is a central portion, and a discharge port of the air passage 93a or a supply port of the oxygen passage 94a is formed on the opposing surface of the oxygen permeable cell. A punching plate 95 is disposed at the discharge port of the air passage 93a and the supply port of the oxygen passage 94a, and a current collector 96 is disposed on the surface of the punching plate 95. An electric body 96 is disposed so as to face the cathode electrode 91 or the anode electrode 92, respectively.

According to the oxygen enricher described above, air is sent from the air passage 93a of the separator 93 disposed on the cathode electrode 91 side, so that oxygen molecules (O ₂ ) receive electrons at the cathode electrode 91, It is ionized to oxygen ions (O ²⁻ ). Then, the ions move as a current in the solid electrolyte 90 to the anode 92 where positive voltage is applied, discharge electrons on the anode 92 and return to oxygen molecules, so that oxygen is returned to the anode 92 side. Is supplied to an oxygen passage 94a of a separator 94 disposed in

  By the way, the above-described oxygen enricher needs to be in a high temperature atmosphere of 400 ° C. to 800 ° C. in order to start the above-described reaction in the oxygen permeable cell, and is heated.

  However, since the solid electrolyte 90 is generally made of a fragile material such as ceramics, the solid electrolyte 90 and the separators 93 and 94 expand in the thickness direction and the surface direction, respectively, in the process of raising the temperature from room temperature to the reaction temperature. Then, the solid electrolyte 90 and the separators 93 and 94 come into close contact with each other, and the thermal expansion in the surface direction is restrained. For this reason, there is a problem that thermal distortion occurs between the solid electrolyte 90 and the separator 2, and the solid electrolyte 90 is damaged.

  Furthermore, since the gap between the oxygen permeable cell and the separator 94 is not sealed, some of the oxygen molecules that have moved to the anode 92 side due to the electrochemical reaction are between the oxygen permeable cell and the separator 94. There was a problem of leaking out of the oxygen enricher.

  The present invention has been made in view of such circumstances, and prevents damage to electrochemical cells such as the oxygen permeable cells, and oxygen obtained from electrochemical cells that exchange electrons such as oxygen permeable cells. It is an object of the present invention to provide an electrochemical reaction device such as an oxygen enricher that prevents gas from leaking out of the oxygen enricher.

  In order to solve the above-mentioned problem, the invention described in claim 1 includes a plate-like electrochemical cell for transferring electrons, and an opening formed at a position facing a central portion of the electrochemical cell, and the electrochemical A base material made of a material having a coefficient of thermal expansion different from that of the cell, and an interposition member interposed between the electrochemical cell and the base material, and the interposition member has the opening at the center. A plurality of layers of sheet materials each having an opening that communicates with each other are laminated in the thickness direction, and are integrated at different positions in the plane direction so as to have airtightness between the laminations. An electrochemical reaction apparatus in which the sheet material on one end side is joined to the cell over the entire circumference and the sheet material on the other end side is joined to the electrochemical cell over the entire circumference.

  Here, the electrochemical cell means a cell that undergoes a chemical reaction with the exchange of electrons. In addition to an oxygen permeable cell, a power generation cell that generates power using an oxidant gas and a fuel gas, or electrolyzes water. It includes an electrolytic cell. Therefore, the electrochemical reaction device means a device having the above-described electrochemical cell, and is used as a fuel cell, a water electrolysis device, or the like in addition to the oxygen enricher.

  The invention according to claim 2 is the electrochemical reaction device according to claim 1, wherein the interposition member is configured such that an inner peripheral end and an outer peripheral end of the sheet material are alternately directed in the stacking direction. It is characterized by being joined to and integrated with each other.

According to a third aspect of the present invention, there is provided the electrochemical reaction device according to the first or second aspect, wherein the electrochemical cell is paired with a plate-shaped solid electrolyte made of lanthanum gallate and a central portion of the front and back surfaces of the solid electrolyte. The sheet material at one end in the stacking direction is joined to the solid electrolyte by crystallized glass containing at least La, and the thermal expansion coefficient of the crystallized glass is 10 × 10. ^-6 / K or more and 12 × 10 ^-6 / K or less.

  Furthermore, the oxygen enricher according to the invention of claim 4 uses an oxygen permeable cell as the electrochemical cell of the electrochemical reaction device of any one of claims 1 to 3, An anode electrode is provided at the center of the substrate and on the opposite surface of the substrate, and a cathode electrode is provided at the center of the substrate and on the opposite surface of the substrate. Thus, the base material is formed with a passage through which oxygen released from the anode electrode of the oxygen permeable cell is circulated.

  Furthermore, in the hydrogen enricher according to the invention described in claim 5, a hydrogen permeable cell is used as the electrochemical cell of the electrochemical reaction device described in claim 1 or 2. A cathode electrode is provided on the opposite surface of the base material in the central portion, and an anode electrode is provided on the opposite surface of the base material in the central portion of the base material. The base material is characterized in that a passage through which hydrogen released from the cathode electrode of the hydrogen permeable cell flows is formed.

  According to invention of Claim 1 or 2, the interposition member interposed between the base material and the electrochemical cell laminates a plurality of layers of sheet material, and is provided on one end side in the laminating direction. Since the sheet material is joined to the electrochemical cell over the entire circumference, and the sheet material on the other end side is joined to the base material over the entire circumference, the surface generated by thermal expansion of the electrochemical cell and the base material, respectively. The thermal strain in the direction can be absorbed by the interposition member to prevent the electrochemical cell from being damaged, and airtightness between the electrochemical cell and the substrate can be ensured.

  In particular, according to the invention described in claim 2, since the inner peripheral edge and the outer peripheral edge of the sheet material are alternately joined in the laminating direction, more thermal strain generated in the surface direction is absorbed. can do. Therefore, damage to the electrochemical cell due to thermal stress can be prevented more reliably.

  Furthermore, according to the invention described in claim 3, the solid electrolyte is made of a lanthanum gallate material, and the sheet material on one end side in the stacking direction is joined to the solid electrolyte by crystallized glass containing at least La. Therefore, La contained in the solid electrolyte and the crystallized glass can serve as a buffer to improve the adhesion of the crystallized glass to the solid electrolyte. As a result, the solid electrolyte and the sheet material at one end in the stacking direction can be firmly bonded.

Furthermore, since the thermal expansion coefficient of the crystallized glass is 10 × 10 ⁻⁶ / K or more and 12 × 10 ⁻⁶ / K or less, the solid electrolyte (thermal expansion coefficient of lanthanum gallate 10.8 × 10 ^{− 6} / K) and the thermal expansion coefficient are close to each other. For this reason, when the temperature is raised from room temperature to the reaction temperature of the electrochemical cell, it is possible to prevent the solid electrolyte from being damaged due to thermal strain generated between the solid electrolyte and the crystallized glass in the process.

  On the other hand, according to the invention described in claim 4, since the electrochemical cell is an oxygen permeable cell, by connecting a direct current power source to an anode electrode and a cathode electrode provided at the center of the oxygen permeable cell, Oxygen in the air supplied from the central part of the base material becomes oxygen ions at the cathode electrode, and the oxygen ions move to the anode electrode side to release electrons and supply them as passages in the base material as oxygen molecules. Is done. As a result, the electrochemical cell can be used to separate oxygen from the air and supply it to the desired location.

  On the other hand, according to the invention described in claim 5, since the electrochemical cell is a hydrogen permeable cell, a direct current power source is connected to a cathode electrode and an anode electrode provided at the center of the hydrogen permeable cell, The hydrogen in the water vapor releases electrons at the anode electrode to form hydrogen ions, and the oxygen ions move to the cathode electrode side to receive the electrons and serve as hydrogen molecules. It is supplied to the passage in the material. As a result, the electrochemical cell can be used to separate hydrogen from the water vapor and supply it to the desired location.

  Hereinafter, an oxygen enricher will be described as a first embodiment of an electrochemical reaction device according to the present invention.

  As shown in FIGS. 1 and 2, the oxygen enricher in this embodiment includes a plate-like oxygen permeable cell (electrochemical cell) 1 and a separator 2 disposed in parallel with the oxygen permeable cell 1. And an interposed member 3 provided between the separator 2 and the oxygen permeable cell 1.

  The oxygen permeable cell 1 is disposed on a solid electrolyte 10 made of a rectangular (including a square, the same applies hereinafter) thin film material and a central portion of the solid electrolyte 10 facing the separator 2. The anode 12 and the cathode 11 disposed on the opposite surface of the separator 2 at the center of the solid electrolyte 10.

Examples of the solid electrolyte 10 include (La _0.8 · Sr _0.2 ) (Ga _0.8 · Mg _0.1 · Co _0.1 ) O ₃ or (La _0.8 · Sr _0.2 ) (Ga _0.8 · Mg _0.1 · Ni _0.1 ) O ₃ . A lanthanum gallate material having a perovskite crystal structure is used. Moreover, the film thickness of the solid electrolyte 10 is determined according to the temperature conditions at the time of use and the oxygen permeation amount required at that time, and is set in the range of 30 to 200 μm in this embodiment. Yes.

The cathode electrode 11 and the anode electrode 12 are respectively SSC: (Sm _0.5 Sr _0.5 ) CoO ₃ , BLC: (Ba _0.6 La _0.4 ) CoO ₃ , LSC: (La _0.6 Sr _0.4 ) CoO ₃ , LSM: (La _0.85 Sr _0.15 ) MnO ₃ , LSCF6428: (La _0.6 Sr _0.4 ) (Fe _0.2 Co _0.8 ) O ₃ , LSCF6482: (La _0.6 Sr _0.4 ) (Fe _0.8 Co _0.2 ) O _3, etc. Has been.

  The separator 2 is a rectangular base material 20 made of a conductive member such as SUS430, and a concave portion (opening portion) having a shape corresponding to the anode electrode 12 at the center of the surface facing the oxygen permeable cell 1. 21 is formed. A plurality of columnar members 22 projecting from the bottom toward the oxygen permeable cell 1 are equally disposed in the recess 21.

  In the recess 21, a plate-like current collector 4 is provided on the opposing surface of the oxygen permeable cell 1, and a punching plate 5 is interposed between the current collector 4 and the columnar member 22. ing. The current collector 4 and the punching plate 5 are disposed in parallel with the oxygen permeable cell 1, and the outer periphery thereof is formed to be approximately the same size as the inner periphery of the recess 21. The current collector 4 is made of a stainless steel material such as SUS430, and the punching plate 5 is made of the same material as the current collector 4 and has a plurality of holes.

  In the separator 2, a gas passage 24 penetrating from the outer peripheral portion of the substrate 20 to the space surrounded by the punching plate 5 in the recess 21 is formed. A pipe 25 is provided integrally with the side wall of the base material 20 and extends outward from the base material 20 and communicates with the passage 24. An oxygen exhaust path B is formed by the passage 24 and the pipe 25 communicating therewith.

The interposition member 3 is configured by laminating two rectangular annular sheet materials 31 each having an opening 3a corresponding to the anode electrode 12, and each sheet material 31 is made of SUS430 or the like. Made of ferritic stainless steel foil.
Among these, the sheet material 31 a disposed on the surface facing the separator 2 is formed so that the outer periphery thereof is substantially the same size as the outer periphery of the separator 2, and the outer periphery thereof is welded to the outer periphery of the separator 2. It is welded.

  On the other hand, the sheet material 31b disposed on the opposite surface side of the oxygen permeable cell 1 has an opening 3a formed in substantially the same size as the opening 3a of the sheet material 31a, and an inner peripheral portion thereof. The sheet material 31a is integrated by welding or welding to the inner peripheral portion. The outer periphery of the oxygen permeable cell 1 is formed to be substantially the same size as the outer periphery of the oxygen permeable cell 1, and the outer peripheral portion is glass bonded to the outer peripheral portion of the oxygen permeable cell 1.

In this glass bonding, crystallized glass 30 containing 0.3 to 5% by mass of La ₂ O ₃ and 0.5 to 5% by mass of Al ₂ O ₃ is screen-printed on the solid electrolyte 10 and the sheet material 3b. After drying, the solid electrolyte 10 and the sheet material 3b are bonded together and then heat-treated. Since this crystallized glass 30 contains La ₂ O ₃ and Al ₂ O ₃ , the adhesion with the solid electrolyte 10 made of a lanthanum gallate material is improved.

  Further, in the oxygen enricher of the present embodiment configured as described above, an insulating sheet 6 made of an alumina fiber sheet is disposed so as to surround the outside of the oxygen permeable cell 1. .

  A separator 7 disposed in parallel with the oxygen permeable cell 1 is provided on the opposite side of the separator 2 with respect to the oxygen permeable cell 1. Like the separator 2 described above, the separator 7 is composed of a rectangular base material 70, and a recess 71 is formed at the center. The recess 71 is provided with a columnar member 72 and a current collector 8 and a punching plate 9.

  The separator 7 has an even number (two in the figure) of gas passages 74 penetrating from the outer peripheral portion of the base material 70 into the space surrounded by the punching plate 9 of the concave portion 71 with respect to the center of the base material 70. And are formed in pairs so as to be point-symmetric. An even number (two in the figure) of pipes 75 that are provided integrally with the side wall of the base material 70 and extend outward from the base material 70 and communicate with the passage 74 form a pair. Are provided. An air intake path A is formed by the one passage 74 and the pipe 75 communicating therewith, and a gas exhaust path C is formed by the other passage 74 and the pipe 75 communicating therewith. The path A and the exhaust path C are arranged in pairs.

  The separator 7 thus configured is arranged so as to sandwich the oxygen permeable cell 1 and the insulating sheet 6 together with the separator 2. The separators 2 and 7 are connected to an electric circuit (not shown) so that a negative voltage is applied to the cathode electrode 11 and a positive voltage is applied to the anode electrode 12.

Next, another embodiment will be described with reference to FIG.
The electrochemical reaction device of the present embodiment is configured in the same manner as the electrochemical reaction device of the above-described embodiment except that three sheet materials 31 are stacked as the interposition member 3.

  In the interposing member 3, the sheet material 31a disposed on the surface facing the separator 2 is provided in the same manner as the above-described electrochemical reaction device, but the sheet material 31a and the oxygen permeable cell 1 are opposed to each other. The sheet material 31c is provided between the sheet material 31b and the sheet material 31b disposed on the surface, which is different from the above-described electrochemical reaction device. In the sheet material 31c, the inner peripheral portion and the inner peripheral portion of the sheet material 31a are integrated by welding or welding, and the outer peripheral portion and the outer peripheral portion of the sheet material 31b are integrated by welding or welding. ing. The inner periphery of the sheet material 31 b is glass bonded to the outer periphery of the solid electrolyte 10.

  In the electrochemical reaction apparatus described above, two sheet materials 31 are stacked as the interposing member 3, whereas in the electrochemical reaction apparatuses in other embodiments, three sheet materials 31 are stacked. . Thereby, the electrochemical reaction apparatus in other embodiments not only has a large amount of thermal strain absorbed by the interposing member 3, but also has a large thermal expansion due to the solid electrolyte 10 or a large thermal expansion due to the separator 2. Even in this case, it is excellent in that the thermal strain generated between the two by the interposed member 3 is efficiently absorbed.

The operation when the above-described oxygen enricher is used will be described.
First, a negative voltage is applied to the cathode electrode 11 and a positive voltage is applied to the anode electrode 12 through the separators 2 and 7 and the interposition member 3. Then, air is supplied from the intake passage A to the recess 71, while colliding with the columnar member 72, moving toward the center of the recess 71, passing through the hole of the punching plate 9, and supplied to the vicinity of the cathode electrode 11. The In this way, air is uniformly supplied from the entire recess 71 to the vicinity of the cathode electrode 11.

Then, oxygen in the air receives electrons at the cathode electrode 11 and becomes oxygen ions (O ²⁻ ). The oxygen ions move as current in the solid electrolyte 10 toward the anode electrode 12, and at the anode electrode 12. Electrons are released into oxygen molecules. At that time, since the oxygen enricher is heated to 400 to 800 at the time of start-up, the thermal expansion is caused by the thermal expansion of the solid electrolyte 10 and the base material 20 of the separator 2, respectively. The intervening member 3 absorbs.

Next, oxygen passes from the anode electrode 12 through the current collector 4 and the hole of the punching plate 5, is supplied into the recess 21, and is then discharged from the exhaust path B.
On the other hand, components other than air pass through the hole of the punching plate 9 again, are discharged to the recess 71 of the separator 7, and are discharged from the exhaust path C.
For this reason, it becomes possible to take out only oxygen from air.

  As described above, the oxygen enricher according to this embodiment includes the anode electrode 12 as the interposition member 3 interposed between the oxygen permeable cell 1 including the cathode electrode 11 and the anode electrode 12 and the separator 2. Two rectangular annular sheet materials 31 each having an opening 3a corresponding to the above are laminated, and the inner peripheral ends of the sheet materials 31 are welded or welded so as to have airtightness. Further, the outer peripheral portion of the sheet material 31 a is welded or welded to the separator 2, and the outer peripheral portion of the sheet material 31 b is glass-bonded to the oxygen permeable cell 1. For this reason, the interposition member 3 made of the sheet material 31 has flexibility with respect to the surface direction of the sheet material, and when the oxygen-permeable cell 1 and the separator 2 are thermally expanded, respectively, Thermal strain can be absorbed.

Furthermore, the crystallized glass 30 containing La ₂ O ₃ and 0.5 to 5% by mass of Al ₂ O ₃ of 0.3 to 5 wt%, solids comprised of sheet material 31b and lanthanum gallate comprising a ferritic stainless steel foil The outer periphery of the electrolyte 10 is firmly joined. Further, since the thermal expansion coefficient of the crystallized glass 30 is 10 × 10 ⁻⁶ / K or more and 12 × 10 ⁻⁶ / K or less, the crystallized glass 30 and the solid electrolyte 10 are subjected to thermal strain. The solid electrolyte 10 can be prevented from cracking.

  As a result, it is possible to prevent the crystallized glass 30 and the interposing member 3 from being peeled off from the solid electrolyte 10 even when the solid electrolyte 10 and the crystallized glass 30 are thermally expanded by heating at the time of startup. At the same time, the solid electrolyte 10 can be prevented from cracking due to thermal strain between the two. Moreover, the airtightness between the oxygen permeable cell 1 and the separator 2 can be reliably ensured on the anode electrode 12 side.

  Furthermore, since the separators 2 and 7 and the interposition member 3 are conductive members, it is not necessary to directly connect a direct current power source to the cathode electrode 11 and the anode electrode 12 provided in the central portion of the oxygen permeable cell 1. By indirect connection via the separators 2 and 7, oxygen in the air supplied from the air intake path A of the separator 7 becomes oxygen ions at the cathode electrode 11. Next, the oxygen ions move to the anode electrode 12 side, release electrons, are supplied to the passage in the separator 2 as oxygen molecules, and are discharged from the oxygen exhaust passage B. On the other hand, components other than oxygen in the air are discharged from the exhaust passage C as they are. For this reason, oxygen can be separated from the air and supplied by a simple oxygen enricher having a wiring structure.

  In addition, this invention is not restricted to the said embodiment, For example, the oxygen permeable cell 1, the base material 20 of the separator 2, and the interposition member 3 may be a cross-sectional circular shape. In addition, the interposition member 3 is not one in which a plurality of sheet materials such as two or three are joined and integrated in the thickness direction, but one sheet material is bent and formed in the thickness direction. It may be what was done.

Hereinafter, a hydrogen enricher will be described as a second embodiment of the electrochemical reaction apparatus according to the present invention.
As shown in FIG. 4, the hydrogen enricher in the present embodiment is obtained by replacing the oxygen permeable cell 1 of the first embodiment with a hydrogen permeable cell 15.

The hydrogen permeable cell 15 is composed of a solid electrolyte 16 made of SrCeO ₃ , a cathode electrode 17 disposed on the surface facing the separator, and an anode electrode 18 disposed on the opposite surface of the separator 2. Has been. The cathode electrode 17 and the anode electrode 18 are made of a material such as Pt—ZrO ₂ or Pt.

The operation when the above-described hydrogen enricher is used will be described.
Similar to the operation of the oxygen enricher in the first embodiment, a power source is connected to the cathode electrode 17 and the anode electrode 18 through the separators 2 and 7 and the interposing member 3 to pass a current.

  Then, water vapor in the air is supplied from the intake passage A to the recess 71, passes through the hole of the punching plate 9, emits electrons at the anode 18, and becomes hydrogen ions. The hydrogen ions move as current in the solid electrolyte 16 toward the cathode electrode 17, receive electrons at the cathode electrode 17, and become hydrogen molecules. At this time, the interposition member 3 absorbs thermal strain as in the oxygen enricher of the first embodiment.

  Next, hydrogen passes from the cathode electrode 17 through the current collector 4 and the hole of the punching plate, is supplied into the recess 21, and then discharged from the exhaust path B. On the other hand, components other than hydrogen are discharged from the exhaust path C. For this reason, it becomes possible to take out only hydrogen from the water vapor in the air.

  As described above, in the hydrogen enricher of the present embodiment, the interposing member 3 absorbs the thermal strain between the hydrogen permeable cell 15 and the separator 2 as in the oxygen enricher of the first embodiment. Therefore, it is possible to prevent the hydrogen permeable cell 15 from being cracked. Further, on the cathode electrode 17 side, airtightness between the hydrogen permeable cell 15 and the separator 2 can be ensured by the interposition member 3.

  Furthermore, since the separators 2 and 7 and the interposition member 3 are conductive members, hydrogen can be separated from water vapor and supplied by a hydrogen enricher with a simple wiring structure.

  In addition, this invention is not restricted to the said embodiment, For example, like the oxygen enricher of 1st embodiment, the interposition member 3 joins and integrates three sheet | seat materials toward the thickness direction. Even if it was made, one sheet material may be bent and formed in the thickness direction.

It is sectional drawing which shows the oxygen enricher which is 1st embodiment of the electrochemical reaction apparatus which concerns on this invention. It is a perspective view of the oxygen enricher shown in FIG. It is sectional drawing which shows the oxygen enricher of other embodiment of the oxygen enricher of 1st embodiment. It is sectional drawing which shows the hydrogen enricher which is 1st embodiment of the electrochemical reaction apparatus which concerns on this invention. It is sectional drawing which shows the conventional oxygen enricher.

Explanation of symbols

1 Oxygen permeable cell (electrochemical cell)
2 Separator 3 Intervention member

Claims (5)

A plate-like electrochemical cell for transferring electrons, a base material made of a material having a coefficient of thermal expansion different from that of the electrochemical cell, the opening being formed at a position facing the central portion of the electrochemical cell, and the electrochemical Comprising an interposed member interposed between the cell and the substrate,
The interposition member is laminated in the thickness direction with a plurality of layers of sheet materials in which an opening communicating with the opening is formed in the central portion, and the surface direction is different so that each of the laminations has airtightness. The sheet material on one end side in the stacking direction is joined to the electrochemical cell over the entire circumference, and the sheet material on the other end side is joined to the base material over the entire circumference. An electrochemical reaction device characterized by that.   2. The electrochemical reaction according to claim 1, wherein the interposition member is formed by alternately joining and integrating the inner peripheral end and the outer peripheral end of the sheet material in the stacking direction. apparatus. The electrochemical cell is composed of a plate-like solid electrolyte made of lanthanum gallate and electrodes provided in pairs at the center of the front and back surfaces of the solid electrolyte,
The sheet material on one end side in the laminating direction is joined to the solid electrolyte by crystallized glass containing at least La, and
3. The electrochemical reaction apparatus according to claim 1, wherein the crystallized glass has a thermal expansion coefficient of 10 × 10 ⁻⁶ / K or more and 12 × 10 ⁻⁶ / K or less. . An oxygen permeable cell is used as the electrochemical cell of the electrochemical reaction device according to any one of claims 1 to 3, wherein the oxygen permeable cell is a central portion of the substrate and is opposed to the substrate. An anode electrode is provided on the surface, a central portion of the substrate, and a cathode electrode is provided on the opposite surface of the substrate;
An oxygen enricher characterized in that a passage for circulating oxygen released from the anode electrode of the oxygen permeable cell is formed in the base material. A hydrogen permeable cell is used as the electrochemical cell of the electrochemical reaction device according to claim 1, wherein a cathode electrode is provided at a central portion of the base material and on a facing surface of the base material. And provided with an anode electrode in the center of the base material and on the opposite surface of the base material,
A hydrogen enricher characterized in that a passage for allowing hydrogen released from the cathode electrode of the hydrogen permeable cell to flow therethrough is formed in the base material.

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