JP5198758B2 - Electrochemical reactor stack and electrochemical reactor system - Google Patents

Description

The present invention, electrical and electrical chemical reactor stack with a reactor cell support, the solid oxide fuel cell stack consists of electrochemical reactors such as a stack for stacking the tubular electrochemical reactor cell It relates to a chemical reactor system.

  Conventionally, a solid oxide fuel cell (hereinafter also referred to as SOFC) is known as a typical electrochemical reactor. The SOFC is a fuel cell using a solid oxide electrolyte having ionic conductivity as an electrolyte.

  The basic structure of the SOFC is usually composed of three layers of a cathode (air electrode), a solid oxide electrolyte, and an anode (fuel electrode), and is usually used in a temperature range of 800 to 1000 ° C.

  In this SOFC, when fuel gas (hydrogen, carbon monoxide, hydrocarbon, etc.) is supplied to the anode and air, oxygen, etc. are supplied to the cathode, the oxygen partial pressure on the cathode side and the oxygen content on the anode side are supplied. Since a difference arises between the two electrodes, a voltage according to the Nernst equation is generated. Oxygen becomes ions at the cathode and moves to the anode side through the solid electrolyte, and the oxygen ions reaching the anode react with the fuel gas and release electrons. Therefore, if a load is connected between the anode and the cathode, electricity can be directly taken out from the fuel cell.

  In order to further commercialize the SOFC, it is essential to lower the operating temperature of the SOFC. For this purpose, it is effective to use a material having a thin electrolyte and high ionic conductivity. Among these, since the electrode can be used as a support, it is possible to reduce the thickness of the electrolyte. Therefore, particularly anode-supported cells have been widely studied.

In addition, by lowering the operating temperature to 500 to 600 ° C., it is expected that the use of inexpensive materials and the reduction of the operating cost can be expected, and the versatility of SOFC is expected to increase. Up to now, by developing new anode and cathode materials, a flat plate type SOFC having a high power output of 0.8 to 1 W / cm ² has been proposed even in a low temperature region (600 ° C.) (non- (See Patent Documents 1 and 2).

  However, since the anode support type SOFC capable of high power output described above is a flat plate type, there has been a problem that it is likely to cause cell destruction under conditions of an abrupt operation cycle. The reason for this is that nickel cermet that is generally used causes a large volume change due to an operation cycle in an oxidation-reduction atmosphere or a temperature change, so that the cell is distorted and destroyed. Therefore, there is a very big technical problem in increasing the size and stacking while maintaining the performance of the flat cell.

  In addition, reducing the electrode structure and thickness of the anode support cell is important in terms of performance improvement, but it is also difficult to increase the porosity by reducing the thickness with a flat plate type. As an alternative to a flat plate cell, an SOFC structure composed of a tubular cell has been studied (see Patent Document 1).

In other words, the tube cell stacks proposed so far have a structure in which the tube cell is stably held by the cathode material, and current collection from the anode and the cathode is performed using an electrode current collector sheet or the like. It was a thing.
JP 2004-335277 A Z.Shao and SMHaile.Nature431 170-173 (2004) T. Hibino, A. Hashimoto, K. Asano, M. Yano, M. Suzuki and M. Sano. Electrochem. Solid-Sate Lett, 5 (11) A242-A244 (2002)

However, in the current design, even if the stack structures are overlapped, the electrical connection between the stacks is not easy, and no specific proposal has been made to solve it.
In particular, in the conventional structure, it is difficult to connect in series in the stack, which contributes to a decrease in current collection efficiency, and a stack in which highly efficient small tubular cells are efficiently integrated, that is, in series connection. However, there has been no report on a stack that can easily obtain a high voltage (integrated small tubular cells).

The present invention has been made to solve the problems described above, and its object is case, readily conductive capable series gas chemical reactor stack及 beauty electrochemical in the stack using a tube type cell It is to provide a reactor system.

As a result of intensive studies aimed at solving the above-mentioned problems, the present inventors have lowered the operating temperature by using a reactor cell support that can efficiently arrange tube-type cells having fine diameters. In addition, the inventions of an electrochemical reactor stack and an electrochemical reactor system capable of easily obtaining a high voltage in spite of a compact configuration have been completed.

In other words, configuration by using a reactor cell support in the invention, the (cold the having a cell structure capable of realizing the operating temperature) tube electrochemical reactor cell can integrated efficiently, also easily stack by lamination can do. Furthermore, in the electrochemical reactor stack and the electrochemical reactor system using the reactor cell support, an electric series is formed by a simple stack of the electrochemical reactor cell and the reactor cell support by a current collector of the reactor cell support. Connection can be easily realized, thereby increasing the generated voltage.

Hereinafter, each claim will be described.
(1) According to the first aspect of the present invention, a plurality of tube-type electrochemical reactor cells having a multilayer structure in which a first electrode layer and a second electrode layer are laminated with an electrolyte layer interposed therebetween; First electrode current collector, second electrode current collector electrically connected to the second electrode layer, first electrode current collector and second electrode current collector, A reactor cell support integrally formed with a separator disposed between and separating the first electrode current collector and the second electrode current collector; and an electrochemical reactor stack, the reactor cell support is for a plurality of grooves on a surface which is shaped like a flat plate provided in parallel, each of the plurality of grooves of the reactor cell support, each electrochemical reactor of the plurality of electrochemical reactor cell Each cell is fitted with the reactor cell With cell layer portion layered plurality of electrochemical reactor cell is placed in parallel with the lifting body is configured, the cell layer portion has a plurality of layers laminated stack structure, further, the first electrode The layer is formed inside the electrolyte layer of the electrochemical reactor cell, and is exposed from the electrolyte layer at a part in the axial direction of the electrolyte layer, and the second electrode layer is outside the electrolyte layer. The first electrode current collector is electrically connected at an exposed portion of the first electrode layer, and the second electrode current collector is formed on the second electrode layer. It is electrically connected at the outer surface of the.

In the present invention, by using the reactor cell support, and supported by arranging a plurality of tubular electrochemical reactor cell (sometimes hereinafter referred to as tubular electrochemical reactor cell), they (the cell layer portion) By stacking, an electrochemical reactor stack having an electrical series connection can be easily configured.

  In other words, in the present invention, a high-performance electrochemical reactor stack in which a plurality of small-diameter tube-type (microtube-type) electrochemical reactor cells can be efficiently arranged and the output per unit volume is dramatically increased with a compact configuration. Can be obtained. It is easy to obtain an arbitrary voltage output by adjusting the stacking state of the cell layered portion.

  In addition, with this configuration, even when conventional materials are used, it is possible to reduce the operating temperature to a low temperature of, for example, 600 ° C. or less, and a compact, high voltage can be obtained. (Solid oxide fuel cell stack etc.) and electrochemical reactor system can be produced.

In other words, by using the reactor cell support that can achieve the efficient arrangement of the tube-type electrochemical reactor cell and the compactness of the current collector at the same time, the industrial process can be simplified and the high-performance electrochemical reactor Manufacturing costs for stacks and electrochemical reactor systems can be greatly reduced.
In the present invention, the first electrode current collector is electrically connected at the exposed portion of the first electrode layer, and the second electrode current collector is electrically connected at the outer surface of the second electrode layer. It is connected to the. Thereby, the structure of an electrical connection part can be made compact. Moreover, the structure of the electrical connection part with another cell layer part can also be simplified.

As the tubular electrochemical reactor cell, conventionally, in diameter it is known ones 5mm~ number cm, in the present invention, Ru can adopt it as from small diameter.

( 2 ) The invention of claim 2 is characterized in that at least the second electrode current collector has air permeability and a porosity of 10% or more.
Therefore, in the present invention, the fuel gas and the oxidant gas can be suitably supplied to the second electrode layer via the second electrode current collector.

( 3 ) In the invention of claim 3 , when the first electrode layer or the second electrode layer is a fuel electrode, the current collector of the first electrode current collector or the second electrode current collector on the fuel electrode side is provided. body _{material, La 1-x A x Cr} 1-y B y O 3 (A = Sr, Ca, Mg) (B = Ni, Co, Mn, Fe) (x, y = 0~1), stainless steel It is characterized by being composed of any one of metal alloy and metal / oxide cermet.

The present invention exemplifies a material on the fuel electrode side, and by using this material, high conductivity can be maintained even in a reducing atmosphere.
( 4 ) In the invention of claim 4 , when the first electrode layer or the second electrode layer is an air electrode, the current collector of the first electrode current collector or the second electrode current collector on the air electrode side is provided. The body material is any of Ag, La, Sr, Mn, Co, Fe, Sm, Ce, Pr, Nd, Ca, Ba, Ni, Mg, and an oxide compound containing one or more of these elements. It is configured.

The present invention exemplifies a material on the air electrode side, and by using this material, high conductivity can be maintained even in an oxidizing atmosphere.
( 5 ) The invention of claim 5 is characterized in that the material of the separator is glass or ceramics having electrical insulation.

The present invention exemplifies the material of the separator.
(6) The invention of claim 6, wherein the reactor cell support each other, while sandwiching the partially insulating member, characterized in that it is electrically connected in series.

According to the present invention, the reactor cell support (and hence the cell layered portion) can be laminated to make the electrochemical reactor stack compact.
( 7 ) According to the invention of claim 7 , in the adjacent reactor cell support, the first electrode current collector of one reactor cell support and the second electrode current collector of the other reactor cell support are electrically connected. It is characterized by being connected.

  Thereby, when the reactor cell support (and thus the cell layer portion) is stacked, electrical connection (series connection) in the stacking direction can be easily realized, and the electrochemical reactor stack can be configured compactly.

( 8 ) The invention of claim 8 is characterized in that the reactor cell support has a hexahedron structure, and both ends of the electrochemical reactor cell protrude and are fixed from both sides of the hexahedron facing each other.

The present invention illustrates an electrochemical reactor stack. Thus, Ru can increase the degree of integration of the cell.

(9) The invention of claim 9, wherein an electrochemical reactor system using an electrochemical reactor stack according to any one of claims 1 to 8, the operating temperature is at 650 ° C. or less, electrochemical It is characterized by taking out an electric current by reaction.

The present invention can be operated at a low temperature by using the electrochemical reactor stack described above.
( 10 ) The invention of claim 10 is an electrochemical reactor system using the electrochemical reactor stack according to any one of claims 1 to 8, wherein the electrochemical reactor system is in a solid oxide form. It is used for any one of a fuel cell, an exhaust gas purification device, a hydrogen production device, and a synthesis gas production device.

  The present invention illustrates the use of an electrochemical reactor system.

As described above, the following effects can be obtained by the present invention.
Conventionally, it has been difficult to realize a stack in which high-performance cells having a tube diameter of several millimeters or less are efficiently integrated. However, by using the reactor cell support of the present invention, the current collector parts are connected in series at the time of stacking. Connection becomes easy and the optimum design according to the purpose of use becomes possible. Therefore, a small electrochemical reactor stack and a small electrochemical reactor system with an increased output voltage per volume can be constructed.

  In other words, by efficiently arranging tube-type electrochemical reactor cells on the reactor cell support, it is possible to easily stack the structure, and an electrochemical reactor stack having a very high power output can be obtained even at a low volume. .

  That is, by using this reactor cell support, series connection between supports (and hence between cells) can be easily achieved, and the module voltage per volume can be increased.

-A high-performance electrochemical reactor stack that can simplify the industrial manufacturing process and reduce manufacturing costs can be provided.
-By reducing the thickness of the electrolyte and reducing the tube size, the surface area per unit volume can be greatly increased, thereby further lowering the operating temperature.

An electrochemical reactor system such as a solid oxide fuel cell stack that can be operated at 650 ° C. or lower using an electrochemical reactor stack can be provided.
The electrochemical reactor system can be suitably used as a clean energy source or an environmental purification device.

Hereinafter, embodiments of the present invention will be described.
[First Embodiment]
a) FIG. 1 shows a reactor cell support 1 and a cell layer portion 2 of the present embodiment.

  As shown in FIG. 1 (a), the reactor cell support 1 is disposed between the first and second electrode current collectors 3 and 5 and both current collectors 3 and 5. The separator 7 has insulating properties, and has a structure that can hold a plurality of electrochemical reactor cells 9 arranged in parallel. In addition, what the electrochemical reactor cell 9 was supported by the reactor cell support body 1 is called the cell layer part 2. FIG.

  In the first electrode current collector 3, the second electrode current collector 5, and the separator 7, an electric side is disposed on one side (above FIG. 1A), that is, on one side of the reactor cell support 1. A storage groove 11 having a U-shaped cross section into which the chemical reactor cell 9 is fitted is formed in parallel.

  As shown in FIG. 2, the electrochemical reactor cell 9 is a tube type, and a first electrode layer (inner electrode layer) 13 serving as a support for supporting the cell itself is formed inside the electrochemical reactor cell 9. An electrolyte layer 15 is formed on the surface, and a second electrode layer (outer electrode layer) 17 is formed on the surface of the electrolyte layer 15.

  The first electrode layer 13 is exposed from the electrolyte layer 15 at one end in the axial direction of the cell 9, and the electrolyte layer 15 is exposed from the second electrode layer 17 on both sides in the axial direction of the cell 9. The exposed portion 13 a functions as an external lead electrode of the first electrode layer 13.

  Accordingly, as shown in FIGS. 1B and 1C, the first electrode layer 13 is electrically connected to the first electrode current collector 3 through the exposed portion 13, and the second electrode layer 17 is The two-electrode current collector 5 is electrically connected.

b) Details will be described below.
The size of the reactor cell support 1 is not particularly limited, and may be determined as appropriate depending on the length, diameter, and number of electrochemical reactor cells 9 to be used. The width of the reactor cell support 1 can be determined by the number of electrochemical reactor cells 9 to be stored. Usually, it is preferable to arrange 3 to 20 electrochemical reactor cells 9 per row, and 5 to 10 cells per row are particularly suitable. At that time, the interval between the electrochemical reactor cells 9 is preferably 0.4 mm or more. Note that the interval between the electrochemical reactor cells 9 may not be constant.

  The length of the reactor cell support 1 is preferably equal to the length of the electrochemical reactor cell 9 used. The length of the electrochemical reactor cell 9 is preferably 0.5 to 10 cm, and preferably 1 to 5 cm. This is because the first electrode layer 13 collects current from the terminal of the electrochemical reactor cell 9, so that the current collection resistance increases and the energy conversion efficiency decreases at a tube length longer than this. is there. In addition, when the tube length is less than this, it is difficult to obtain necessary and sufficient electrodes in the case of a stack.

  FIG. 3 shows a simulation result of the efficiency loss when the length of the tubular electrochemical reactor cell 9 having a diameter of 1.6 mm and a diameter of 0.8 mm is changed. As can be seen in the figure, by reducing the length of the electrochemical reactor cell 9, resistance (and hence efficiency loss) can be reduced. That is, it can be seen that a low-efficiency loss can be realized in the above-described range.

  The height of the reactor cell support 1 needs to have a thickness that can accommodate the electrochemical reactor cell 9 in consideration of the tube diameter of the tube-type electrochemical reactor cell 9. In that case, it is preferable that the electrochemical reactor cell 9 has a diameter of +0.5 to 20 mm. If it is less than this, the current collection efficiency is lowered, and if it is more than this, the arrangement efficiency of the electrochemical reactor cell 9 is lowered, and it becomes difficult to obtain necessary and sufficient power per volume.

As described above, the size of the reactor cell support 1 can be appropriately determined depending on the length, diameter, and number of the electrochemical reactor cells 9 to be used.
Next, each member of the reactor cell support 1 will be described.

First, the storage groove 11 in which the electrochemical reactor cell 9 can be stored is formed in the first electrode current collector 3.
The first electrode current collector 3 needs to have a thickness that can hold the first electrode layer 13 in consideration of the exposed portion 13 a of the first electrode layer 13 of the electrochemical reactor cell 9. Further, the thickness of the portion holding the first electrode layer 13 needs to have a thickness determined by the performance of the electrochemical reactor cell 9, the length and number of the storage portions, and the electric resistance of the first electrode layer 13. . This is because the current collection current increases as the number and length of the electrochemical reactor cells 9 increase. Therefore, the first electrode current collector 3 has a thickness necessary for minimizing current collection loss. This is because it is necessary to have

The second electrode current collector 5 is also formed with a storage groove 11 in which the electrochemical reactor cell 9 can be stored.
Since the second electrode current collector 5 has a function of supplying a circulating gas, the porosity of the structure is preferably 10% or more. The length of the second electrode current collector 5 in the cell axis direction may be long enough to cover the second electrode layer 17.

  -Moreover, it is preferable that the diameter of the electrochemical reactor cell 9 stored in the reactor cell support body 1 is 3 mm or less, and 2 mm or less is more suitable. By reducing the diameter of the electrochemical reactor cell 9, the number of tubes to be stored can be increased, and the cell output per unit volume can be improved.

  As shown in FIG. 2, the axial length of the exposed portion 13 a exposed from the electrolyte layer 15 at one end of the electrochemical reactor cell 9 is appropriately determined in consideration of the thickness of the first electrode current collector 3. Can be adjusted.

  As the structure of this electrochemical reactor cell 9, the first electrode layer 13 and the second electrode layer 17 are respectively an air electrode and a fuel electrode, or the first electrode layer 13 and the second electrode layer 17 are respectively Examples include a fuel electrode and an air electrode.

  The tube thickness of the electrochemical reactor cell 9 depends on the tube diameter, but is preferably 0.1 to 1 mm, and most preferably 0.3 to 0.8 mm. A tube having an electrode structure with a high porosity and a necessary strength while collecting current from the tube terminal while obtaining optimum electrode performance by setting the tube thickness to 0.3 to 0.8 mm. A structure can be realized.

Further, the porosity of the tube is preferably 10% or more in order to promote high-speed gas diffusion and reduction reaction.
FIG. 4 shows a simulation result of the efficiency loss when the thickness of the first electrode layer 13 of the electrochemical reactor cell 9 having a length of 1 cm is changed. As can be seen from the figure, the efficiency loss increases by decreasing the diameter of the electrochemical reactor cell 9. That is, it can be seen that a low-efficiency loss can be realized in the above-described range.

・ Preferable examples of the main material constituting the current collector on the fuel electrode side include conductive ceramics such as lanthanum chromite (LaCrO ₃ ), noble metals such as gold, silver and platinum, stainless steel, and nickel. It is done.

In particular, when the second electrode layer is used as a fuel electrode, it is also preferable to use a composite composed of a mixture of the following fuel electrode material and electrolyte material.
The fuel electrode material is a metal selected from Ni, Cu, Pt, Pd, Au, Ru, Co, La, Sr, Ti and / or an oxide composed of one or more of these elements, and serves as a catalyst. You can adopt something that works. Specifically, Ni, Co, Ru, etc. are suitable. Among these, Ni is preferable because it is less expensive than other metals and has a sufficiently high reactivity with fuel gas such as hydrogen. It is also possible to use a composite in which these elements and oxides are mixed.

  Here, when a composite of an anode material and an electrolyte material is used, the mixing ratio of the former and the latter is preferably in the range of 90:10 to 40:60 (in weight percent). This is because it is excellent in balance such as electrode activity and thermal expansion coefficient matching, and more preferably in the range of 80:20 to 45:55.

  As the material for the current collector on the air electrode side, a material having high conductivity is preferable, and a material having high activity for ionization of oxygen, particularly Ag, La, Sr, Mn, Co, Fe, Sm, Ce Of these, Pr, Nd, Ca, Ba, Ni, Mg elements and oxide compounds thereof are preferably used.

  Among them, for example, transition metal perovskite oxides and composites of transition metal perovskite oxides and electrolyte materials can be preferably used. In the case of using a composite, oxygen ion conductivity is improved among the electron conductivity and oxygen ion conductivity, which are characteristics required for the air electrode, so that oxygen ions generated at the air electrode migrate to the electrolyte layer. It becomes easy and there exists an advantage which the electrode activity as an air electrode improves.

  Here, when a composite of a transition metal perovskite oxide and a solid electrolyte material is used, the mixing ratio of the former and the latter is preferably in the range of 90:10 to 60:40 (in weight percent). This is because it is excellent in balance such as electrode activity and thermal expansion coefficient matching, and more preferably in the range of 90:10 to 80:20.

Specific examples of the transition metal perovskite oxide include LaSrMnO ₃ , LaCaMnO ₃ , LaMgMnO ₃ , LaSrCoO ₃ , LaCaCoO ₃ , LaSrFeO ₃ , LaSrCoFeO ₃ , LaSrNiO ₃ , and oxides such as SmSrCoO ₃ .

  As the solid electrolyte material, it is necessary to use a material that realizes high ion conduction, and as materials used for these, Zr, Ce, Mg, Sc, Ti, Al, Y, Ca, Gd, Sm , Ba, La, Sr, Ga, Bi, Nb and W are preferably oxide compounds containing two or more elements.

Among them, stabilizers such as yttria (Y ₂ O ₃ ), calcia (CaO), scandia (Sc ₂ O ₃ ), magnesia (MgO), ytterbia (Yb ₂ O ₃ ), erbia (Er ₂ O ₃ ), etc. Stabilized zirconia, yttria (Y ₂ O ₃ ), gadolinia (Gd ₂ O ₃ ), ceria (CeO) doped with Samaria (Sm ₂ O ₃ ), and the like are suitable. The stabilized zirconia is preferably stabilized by one or more stabilizers.

  Specifically, yttria-stabilized zirconia (YSZ) added with 5 to 15 mol% yttria as a stabilizer, gadolinia doped ceria (GDC) added with 5 to 30 mol% gadolinia as a dopant, and the like are suitable. . For example, in the case of YSZ, it is not preferable that the yttria content is less than 5 mol% because the oxygen ion conductivity of the anode is lowered. On the other hand, if the yttria content exceeds 15 mol%, the oxygen ion conductivity of the anode similarly decreases, which is not preferable. The same applies to GDC.

Next, the separator 7 will be described.
The separator 7 electrically insulates the first electrode current collector 3 and the second electrode current collector 5, and a material having high electrical insulation is preferable. Among them, a material composed of one or more kinds of glass or oxide compounds composed of elements such as Al, Mg, Si, Ca, and Ba is preferable. The separator 7 can be formed at the above-described position by a method of applying a paste made of these materials to the electrode layer current collector and sintering.

  The first electrode current collector 3 and the second electrode current collector 5 can be bonded by the separator 7, but the bonding method is not particularly limited. For example, using an inorganic adhesive or the like May be combined.

Moreover, although the electrochemical reactor cell 9 is stored in the storage groove 11 of the reactor cell support body 1, it is attached by the material which has electroconductivity in that case.
When the electrochemical reactor cell 9 is stored in the storage groove 11 of the reactor cell support 1, the current collector on the air electrode side is preferably connected by a paste made of an air electrode material. Further, the current collector on the fuel electrode side is preferably connected by a metal paste or the like.

Specifically, as the main material, air electrode materials, conductive ceramics such as lanthanum chromite, noble metals such as gold, silver, and platinum can be employed on the air electrode side. On the fuel electrode side, conductive ceramics such as lanthanum chromite, noble metals such as gold, silver and platinum, stainless steel, nickel and the like can be adopted. These materials can be attached by applying and sintering a paste.
[Second Embodiment]
Next, although the reactor support body of 2nd Embodiment is demonstrated, description of the same content, such as a material, is abbreviate | omitted.

  As shown in FIG. 5, the reactor support 21 of the present embodiment is disposed between the conductive first and second electrode current collectors 23 and 25, and both the current collectors 23 and 25. And a separator 27 having insulating properties, and has a structure that can hold a plurality of electrochemical reactor cells 29 arranged in parallel. In addition, the one in which the electrochemical reactor cell 29 is supported on the reactor cell support 21 is referred to as a cell layer portion 22.

  The first electrode current collector 23, the second electrode current collector 25, and the separator 27, and thus the reactor cell support 21, has a storage hole 31 through which the electrochemical reactor cell 29 is inserted, in the cell layer portion 22. It is formed in parallel with the thickness direction.

The electrochemical reactor cell 29 includes a first electrode layer 33, an electrolyte layer 35, and a second electrode layer 37, as in the first embodiment.
Next, a method for constructing an electrochemical reactor stack will be described by taking the reactor support 21 of the second embodiment as an example.

  As shown in FIG. 6, the electrochemical reactor cell 29 is inserted into the storage hole 31 of the reactor cell support 21 to constitute the cell layer portion 22. At this time, it is important to arrange the exposed portion 33 a of the first electrode layer 33 so as to overlap the first electrode current collector 23 of the reactor cell support 21.

Next, an insulating plate (sheet) 39 is disposed in the thickness direction of the cell layer portion 22 so as to cover the second electrode current collector 25 and the separator 27.
And when laminating | stacking the cell layer part 22 to which this insulating board 39 was stuck in the thickness direction, it laminates | stacks so that the direction of the (adjacent) cell layer part 22 may be reverse. That is, the first electrode current collector 23 of one cell layer portion 22 and the second electrode current collector 25 of the other cell layer portion 22 are sequentially stacked so as to contact each other in the stacking direction.

  As a result, as shown in FIG. 7, an electrochemical reactor stack 41 is obtained in which the adjacent cell layer portions 22 (and hence the reactor cell support 21) are electrically connected in series. For example, the current flows from the outer second electrode layer 37 of the upper electrochemical reactor cell 29 to the inner first electrode layer 33, and from the exposed portion 33 a of the first electrode layer 33 of the lower electrochemical reactor cell 29. It flows to the outer second electrode layer 37.

As shown in FIG. 8, the electrochemical reactor stack 41 generates air as an electrochemical reactor system of a solid oxide fuel cell stack by supplying air from the X direction and fuel gas from the Y direction. . In this electrochemical reactor system, it is possible to output a voltage of about 1 V × the number of stacked cell layer portions 22.
[Third Embodiment]
Next, a third embodiment will be described.

  As shown in FIGS. 9A and 9B, in the third embodiment, a rectangular parallelepiped (hexahedron) reactor cell support 51 is used. In this reactor cell support 51, a large number of tube-type electrochemical reactor cells 53 similar to those in the first embodiment are arranged so as to penetrate through two opposite faces of a hexahedron.

The reactor cell support 51 includes a plate-like first electrode current collector 55, a rectangular parallelepiped second electrode current collector 57, and a plate-like separator 59 disposed therebetween.
As shown in FIG. 9 (c), even in the case of this embodiment, a high performance can be achieved by stacking and connecting in series with the direction of the adjacent reactor cell support 51 reversed through the insulating plate 61. An electrochemical reactor stack 63 can be obtained.

This integration method can be designed with a desired voltage output while minimizing the volume used, and is therefore optimal for small power consumption equipment applications.
In the above description, the method of operating the tube type electrochemical reactor stack according to the present invention alone as SOFC has been described. However, the method is not limited to the above operating method. Moreover, various designs can be considered as the reactor cell support in the present invention, and the reactor cell support is not limited to the above-described shape as long as it has the above-described function.

  Next, although it demonstrates based on the more concrete Example of this invention, this invention is not limited to a following example.

Here, an electrochemical reactor stack and a manufacturing method thereof will be described.
a) First, the structure of the electrochemical reactor stack of this example will be described.
As shown in FIG. 10, an electrochemical reactor stack (specifically, a solid oxide fuel cell stack) 71 of this example includes a cell layer portion 77 including a reactor cell support 73 and an electrochemical reactor cell 75. A plurality of layers are stacked in the vertical direction in FIG.

  The cell layer portion 77 is a structure in which a large number of cylindrical electrochemical reactor cells 75 are supported by a reactor cell support 73, arranged parallel to the axial direction of the cells, and arranged in a line in the left-right direction. The cell layer portion 77 is in a state where the electrochemical reactor cell 75 is sandwiched between the reactor cell support 73 and the insulator 79 from above and below.

The electrochemical reactor cell 75 is cylindrical and has a three-layer structure in which an electrolyte layer 83 is formed on the surface of the first electrode layer 81 and a second electrode layer (not shown) is formed on the electrolyte layer 83. is there.
Specifically, the electrochemical reactor cell 75 is a cylinder having an outer diameter of 3 mm or less. Of the outer surface of the cylindrical first electrode layer 81 having a thickness of, for example, 50 to 400 μm, excluding one end, the electrochemical reactor cell 75 has a thickness of, for example, 2 to 20 μm. The second electrode layer is covered with the electrolyte layer 83, and is formed so as to fill and connect between the reactor cell support 73 and the electrolyte layer 83.

  The reactor cell support 73 has a three-layer structure of a first electrode current collector 85, a separator 87, and a second electrode current collector 89 in the axial direction of the cell. The first electrode current collector 85 is an electrochemical cell. The exposed portion 81 a of the first electrode layer 81 of the reactor cell 75 is electrically connected.

  Specifically, as shown in FIG. 1, the reactor cell support 73 has a storage groove 91 into which a electrochemical reactor cell 75 is fitted in one side of a flat plate, and is formed in parallel with the axial direction of the cell. A one-electrode current collector 85, a separator 87, and a second electrode current collector 89 are stacked. The separator 87 may be any thickness within the range of 1 μm to 2 mm as long as the first electrode current collector 85 and the second electrode current collector 89 are electrically insulated.

The second electrode current collector 89 is electrically connected to the second electrode layer, and has a porous structure with a porosity of 10% or more.
In this electrochemical reactor stack 71, the first electrode current collector 85 and the second electrode current collector 89 of adjacent cell layer portions 77 are connected in series via an insulating plate 79. Electricity can be extracted from the vertical direction (stacking direction).

  Here, the second electrode layer is disposed, for example, between the electrolyte layer 83 of the electrochemical reactor cell precursor and the reactor cell support 73 before the formation of the second electrode layer, and ensures conduction. At the same time, each electrochemical reactor cell 75 and the reactor cell support 73 are connected (coupled).

  In the solid oxide fuel cell system (electrochemical reactor system) using the electrochemical reactor stack 71 described above, air flows in the X direction and fuel gas flows in the Y direction via the reactor cell support 73. Therefore, power generation can be performed. In addition, the generated electricity can be extracted, for example, from the current collector on the positive electrode side from the lower surface and the current collector on the negative electrode side from the upper surface.

b) A method of manufacturing the electrochemical reactor stack 71 of the next embodiment will be described.
For example, NiO: 50% by weight with an average particle size of 0.1 to 2 μm (preferably 0.1 to 1 μm, more preferably 0.3 to 0.8 μm), an average particle size of 0.1 to 2 μm (preferably 0.1 Gd _0.2 Ce _0.8 O _1.9 : 39% by weight and cellulose binder: 7% by weight in a dry mixer for 1 hour after mixing for 1 hour with water, and then adding water to the powder. The external weight% was added and mixed for another 30 minutes.

After passing this mixture through three rolls, the prepared substrate was left overnight. Thereafter, the substrate was extruded with a uniaxial hydraulic cylinder type extruder.
The first electrode layer formed by the extrusion molding in Gr _0.2 Ce _0.8 O _1.9 was added with 4% by weight of butyral binder 4 and 100% by weight of methyl ethyl ketone and mixed for 24 hours. The molded body was immersed. As a result, an electrolyte layer coating was formed on the surface of the first electrode layer molded body.

Then, the 1st electrode layer molded object (namely, 1st electrode layer precursor) in which the film was formed was simultaneously baked at 1400 degreeC for 1 hour in air | atmosphere, and the electrochemical reactor cell precursor was manufactured.
On the other hand, 93% by weight of La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O ₃ (LSCF powder) having an average particle size of 10 to 60 μm (desirably 20 to 50 μm, more desirably 30 to 50 μm), cellulose binder: 7% by weight, After mixing for 1 hour with a dry mixer, 14% by weight of water was added to the powder and mixed for another 30 minutes.

  In addition, as a method of obtaining coarse particles such as LSCF powder, after calcination of LSCF powder (about 0.1 to 2 μm), the particle size is adjusted, or LSCF powder (about 0.1 to 2 μm) is used. ) Is formed into spherical particles using a rolling granulator, spray drying, or the like, and used after temporary firing.

Next, after passing this mixture through three rolls, the prepared substrate was left overnight. Thereafter, the substrate was extruded with a uniaxial hydraulic cylinder type extruder.
Next, this molded body (that is, the precursor of the second electrode current collector 89) is fired in the atmosphere at 1200 to 1500 ° C. for 1 to 3 hours, and then cut into an appropriate length to thereby form a reactor cell. A second electrode current collector 89 of the support 73 was obtained.

Further, in accordance with the outer dimensions (width, thickness, groove shape, etc.) of the second electrode current collector 89 of the reactor cell support 73 obtained by the above method, for example, La _0.69 having an average particle diameter of about 0.1 to 1 μm. Using Ca _0.31 Cr _0.98 O ₃ (lanthanum chromite powder), the first electrode current collector 85 of the reactor cell support 73 could be obtained by the same method as the production of the second electrode current collector 89.

  Furthermore, the separator 87 of the reactor cell support 73 uses, for example, magnesia powder having an average particle size of 0.1 to 2 μm in accordance with the outer dimensions of the first electrode current collector 85 and the second electrode current collector 89. The first electrode current collector 85 and the second electrode current collector 89 can be obtained by the same method.

  Further, for example, butyral binder 4% by weight and methyl ethyl ketone 100% by weight are added to magnesia powder having an average particle size of 0.1 to 2 μm, mixed for 24 hours to form a slurry, and molded by tape casting. The sheet-like insulating plate 79 could be obtained by holding at 1400 ° C. for 1 hour.

The electrochemical reactor stack 71 can be obtained by assembling these members in the following procedure.
First, with respect to LSCF powder having an average particle diameter of 0.1 to 2 μm (preferably 0.1 to 1 μm, more preferably 0.3 to 0.8 μm), ethyl cellulose as a binder: 5% by weight, dispersant: 1 Weight%, butyl carbitol: 13 wt% was added, and a paste (conductive paste) mixed by three rolls was applied by screen printing so that the storage groove 91 of the second electrode current collector 89 was filled. . This paste is baked to form the second electrode layer.

  Moreover, ethyl cellulose: 5% by weight, dispersant: 1% by weight, and butyl carbitol: 13% by weight are added as binders to the glass powder that becomes a gas sealant by applying heat, and mixed by three rolls. The paste (insulating paste) was applied by screen printing so that the storage groove 91 of the separator 87 was filled.

  Furthermore, a paste (conductive paste) mixed with three rolls with ethyl cellulose: 5% by weight, dispersant: 1% by weight, butyl carbitol: 13% by weight as a binder to pure silver powder, It applied so that the storage groove | channel 91 of the 1st electrode electrical power collector 85 might be filled by printing.

  The storage groove filled with each paste in a state where the three parts (first electrode current collector 85, separator 87, second electrode current collector 89) to be the reactor cell support 73 are arranged in contact with each other. 91, the first electrode layer 81 of the electrochemical reactor cell 75 is connected to the first electrode current collector 85 and the second electrode layer is connected to the second electrode current collector 89. The reactor cell 75 precursor is embedded.

  Further, a glass paste is screen-printed so as to cover the second electrode current collector 89 and the separator 87, and the insulating plate 79 is pasted with this glass paste so as to cover the second electrode current collector 89 and the separator 87. Thereby, the cell layer portion 77 is formed.

  Then, when the first electrode current collector 85 and the second electrode current collector 89 of the adjacent cell layer portions 77 are connected to each other, the first electrode that is not covered with the insulator 79 is covered with the pure silver paste. Each cell layer 77 was applied to the surface of the current collector, laminated, and held at 1000 ° C. for 1 hour, thereby completing the electrochemical reactor stack 71.

  The second electrode layer of the electrochemical reactor cell 75 is previously formed on the cell side (the surface of the electrolyte layer 83) before the electrochemical reactor cell 75 is fitted into the storage groove 91 of the reactor cell support 73. May be. For example, a film of an electrolyte layer is formed on the surface of the first electrode layer molded body, a paste of the second electrode layer material is further applied on the film, and then fired to form the electrochemical reactor cell 75. Good.

Next, the electrochemical reactor stack of Example 2 and the manufacturing method thereof will be described, but the description of the same contents as in Example 1 will be omitted.
a) First, the structure of the electrochemical reactor stack of this example will be described.

  The electrochemical reactor stack of this example is obtained by changing the connection method of the electrochemical reactor cell. That is, in Example 1, the electrochemical reactor cell in the cell layer portion was only arranged in parallel with one plane, but in this embodiment, the cell layer portion in which the electrochemical reactor cells were arranged three-dimensionally. Is used. Details will be described below.

  In the present embodiment, as shown in FIG. 11, a large number of cylindrical electrochemical reactor cells 101 have storage grooves 103 (similar to the second electrode current collector of the reactor cell support of the first embodiment). A second electrode current collector layered portion 107 is formed on the second electrode current collector 105 so as to be parallel to the axial direction and aligned in the left-right direction, and this second electrode current collector layered portion 107 is further formed. Are stacked in parallel in the vertical direction to form a second electrode current collector layered portion laminate 109.

  In the axial direction of the cell of the second electrode current collector layered portion laminate 109, a plate-shaped separator 111 through which a large number of electrochemical reactor cells 101 pass is disposed. On the outside (in the axial direction), a plate-like first electrode current collector 113 through which a number of electrochemical reactor cells 101 pass is disposed.

  Accordingly, the second electrode current collector layered portion laminate 109, the separator 111, and the first electrode current collector 113 constitute a cell layer portion 115 having a three-layer structure. In this case, the reactor cell support is obtained by removing the electrochemical reactor cell 101 from the cell layer portion 115.

In the present embodiment, the cell layer portion 115 is laminated in the vertical direction of the figure while being insulated by the insulating plate 117 to constitute an electrochemical reactor stack 119.
Specifically, in the electrochemical reactor stack 119, the first electrode current collector 113 and the second electrode current collector layered body laminate 109 of the adjacent cell layered parts 115 are connected in series via an insulating plate 117, and Electricity can be taken out from the vertical direction (stacking direction) of the electrochemical reactor stack 119.

b) A method for producing the electrochemical reactor stack of the following embodiment will be described.
The materials used, the manufacturing equipment, the manufacturing procedure, and the like are the same as those in the first embodiment, and a description thereof will be omitted.

  In particular, in this example, the second electrode current collector 105 used for the second electrode current collector layered portion laminate 109 is the same as that in the first example, but the separator 111 is the second electrode current collector. The layered portion 109 is formed in a flat plate shape in accordance with the shape of the cell in the axial direction, and a large number of storage holes 121 through which the electrochemical reactor cell 109 passes are formed. The first electrode current collector 113 is also formed in a flat plate shape like the separator 111, and a large number of storage holes 123 through which the electrochemical reactor cell 101 passes are formed.

The electrochemical reactor stack 119 can be obtained by assembling these members in the following procedure.
First, a paste mainly composed of LSCF as in Example 1 was applied so that the storage groove 103 of the second electrode current collector 105 was filled. The precursor of the electrochemical reactor cell 101 is embedded in the second electrode current collector so that a second electrode layer (not shown) of the electrochemical reactor cell 101 is connected to the second electrode current collector 105. The layered portion 107 is used. The second electrode current collector layered portion 107 is laminated to obtain a second electrode current collector layered portion laminate 109.

  Next, a glass-based paste similar to that in Example 1 is applied to the separator 111 having a large number of storage holes 121, and the separator 111 is inserted into the storage holes 121 of the separator 111 through the electrochemical reactor cell 101. Affixed to the two-electrode current collector layered portion laminate 109.

  Similarly, a paste mainly composed of pure silver as in the first embodiment is applied to the first electrode current collector 113 having a large number of storage holes 123, and the storage holes 123 of the first electrode current collector 113 are electrically charged. The first electrode current collector 113 is attached to the separator 111 through the chemical reactor cell 101. Thereby, the cell layer portion 115 is formed.

  When the first electrode current collector 113 and the second electrode current collector layered portion laminate 109 of the adjacent cell layered portions 115 are arranged so as to be electrically connected in series, the pure silver paste is used. Each cell layer 115 was applied to the surface of the first electrode current collector that was not covered with the insulator, and was held at 1000 ° C. for 1 hour, thereby completing the electrochemical reactor stack 119.

Next, the electrochemical reactor stack and the manufacturing method thereof according to Example 3 will be described, but the description of the same contents as in Example 1 will be omitted.
a) First, the structure of the electrochemical reactor stack of this example will be described.

  In the electrochemical reactor stack 131 of this embodiment shown in FIG. 12, the cell layered portion 133 includes a support 137 for supporting the electrochemical reactor cell 135 from the lower side of the same figure, as shown in FIG. A cover 139 that covers the tip side of the cell 135 (on the right side in FIG. 13) from above is used.

  Specifically, in the tubular electrochemical reactor cell 135, the electrolyte layer 143 is laminated on the outer surface of the first electrode layer 141, and the first electrode layer 141 is disposed at the axial end of the electrolyte layer 143 (from the electrolyte layer 143). ) Exposed.

  The electrochemical reactor cell 135 is supported from one side in a state where a plurality of the electrochemical reactor cells 135 are arranged by a support 137 (for example, made of ceramics such as alumina) made of a porous insulator having air permeability.

  In addition, the electrochemical reactor cell 135 is covered with a second electrode current collector 145 from above in the figure, and this second electrode current collector 145 is made of a breathable material that is coated with a conductive paste and sintered. It is a member which has. As the material of the conductive paste, LSCF powder can be used mainly in the same manner as the material used as the second electrode layer in Examples 1 and 2.

On the other hand, the exposed portion 141a of the first electrode layer 141 is covered with a cover 139 having a dense insulating property (for example, made of insulating glass), for example, from above in the drawing.
In addition, the exposed portion 141a of the first electrode layer 141 is covered with a first electrode current collector 147 from below in the figure, and the first electrode current collector 147 is coated with a conductive paste and baked. It is a dense member. In addition, as a material of this conductive paste, pure silver powder can be mainly used in the same manner as the material used for connecting the first electrode layer and the first electrode layer current collector in Examples 1 and 2.

  Further, the first electrode current collector 147 and the second electrode current collector 145 are electrically insulated by a separator 149 having an insulating property. The separator 149 is a member sintered after applying an insulating paste such as ceramics or glass. The separator 149 can be omitted if the current collectors 145 and 147 can be insulated.

b) A method for manufacturing the electrochemical reactor stack 131 of this embodiment will be described.
The materials used are the same as those in the first embodiment, and the description thereof is omitted.
In the present embodiment, as shown in FIG. 12, the storage groove 151 of the support 137 (the storage groove similar to that of the first embodiment) 151 is placed on the side opposite to the exposed portion 141a of the electrochemical reactor cell 135 from the upper side of the same figure. Fit the (cover side).

  Further, the cover 139 is fitted into the exposed portion 141 a of the electrochemical reactor cell 135. That is, since the storage groove 153 similar to the above is formed also in the cover 139, each exposed portion 141a is fitted to each storage groove 153. Note that the storage groove 151 of the support 137 and the storage groove 153 of the cover 139 are also used so as to face each other (however, they are shifted in the axial direction).

Then, the coated side of the electrochemical reactor cell 135 is covered with a conductive paste, and the exposed portion 141a of the electrochemical reactor cell 135 is also covered with the conductive paste.
Note that the insulating paste (which becomes the separator 149) is preferably applied before applying both conductive pastes, but may be applied whenever insulation is possible.

  Next, the cell layer portions 133 obtained in this way are stacked in the opposite direction so that the adjacent cell layer portions 133 are electrically connected in series as in the first embodiment. And the electrochemical reactor stack 131 of the present Example was obtained by baking at the same baking temperature.

In the present embodiment, there is an advantage that the structure can be further simplified compared to the above embodiment.
In this embodiment, the second electrode current collector 145 also functions as the second electrode layer. However, separately from this, a second electrode layer (not shown) is provided on the outer surface of the electrolyte layer 143 in advance. The second electrode current collector 145 may be formed so as to cover the second electrode layer (that is, on the outer surface of the second electrode layer). As a method for forming the second electrode layer, for example, similarly to the first and second embodiments, the conductive paste can be applied and baked.

Next, although Example 4 is demonstrated, description of the content similar to the said Examples 1-3 is abbreviate | omitted.
Unlike the electrochemical reactor stack used as the solid oxide fuel cell stack of Examples 1 to 3, the present example is also referred to as a solid oxide (solid electrolyte type) reactor (hereinafter simply referred to as a reactor (reactor)). The structure is basically the same as that of the solid oxide fuel cell stack, and the materials and applications are mainly different.

  The electrochemical reactor stack (ceramic reactor) in the present embodiment is a solid oxide having a characteristic of passing a specific element, and promotes a reaction using a permeated gas or a mixture of a plurality of gas species. It is intended to separate specific elements from the reaction or to react.

  With regard to this electrochemical reactor stack (and thus an electrochemical reactor system using the electrochemical reactor stack), the electrochemical reactor stack may be energized to forcibly react and separate. Moreover, even if it does not supply with electricity, what can react and isolate | separate by the catalytic ability and ion selectivity which material itself has may be sufficient.

In any of these, since it is important that the gas diffuses efficiently inside the reactor, the reaction or separation method, the type of reaction, or the type of separation is not selected.
The electrochemical reactor stack can be applied to NOx purification technology, hydrogen production technology, and the like as described below.

  a) For example, when exhaust gas from a diesel engine vehicle is introduced into an inner electrode of an electrochemical reactor stack (for example, a fuel electrode similar to a solid oxide fuel cell stack) and forcibly energized, NOx contained in the exhaust gas is deposited on the electrode. In order to release oxygen atoms, it can be purified.

  In this case, the material structure of the electrochemical reactor stack may be Ni, Pt, etc. as the NOx introduction side electrode, and any solid oxide having oxygen ion conductivity may be used. Zirconia-based electrolyte, ceria Either a system electrolyte or a lanthanum garade electrolyte may be used. The counter electrode may be any electrode that can oxygenate oxygen ions. In addition to Pt and Ag, combinations such as an air electrode (for example, an outer electrode) used in the solid oxide fuel cell stack can be considered.

  Therefore, in this embodiment, when the reactor stack similar to that in FIG. 8 is used and exhaust gas is supplied in the X direction of FIG. 8, for example, the gas containing NOx is decomposed into nitrogen and oxygen by the inner electrode of the reactor, At the gas outlet in the direction, the amount of NOx decreases and a gas containing decomposed nitrogen can be taken out.

  b) For example, when a catalyst capable of hydrogenating a gas such as methane at a high temperature (for example, an inner electrode) is used and a membrane having hydrogen ion conductivity is used for the solid oxide layer (membrane), the methane side and the hydrogen extraction side It can be used as an electrochemical reactor stack (and hence an electrochemical reactor system) that can extract hydrogen by applying a differential pressure to the gas.

In this electrochemical reactor stack, metals such as Ni, Cu, and Pt can be considered as catalysts for reforming methane (and thus electrodes), and palladium oxide as a thin film of solid oxide having hydrogen permeability. A metal film, an alloy of palladium and at least one element of Pt, Au, Ag, Cu, Ni, or the like, or an electrolyte having a BaCeO ₃ -based perovskite structure can be employed. Furthermore, any one of alumina, zirconia, magnesia, titania, a mixture thereof, and a compound can be adopted as the porous plate-like body.

  In this case, since the hydrogen can be taken out by the differential pressure, there is no counter electrode, and any material can be used as long as the shape of the electrochemical reactor stack can be maintained with a gas permeable structure.

  c) Further, in the present embodiment, as in the above-described NOx purification and hydrogen production technology, a method (synthesis gas production technology) in which a target product is obtained by forcibly applying an electric current to the electrochemical reactor stack, Applicable. This is mainly a technology for synthesizing an organic fuel while utilizing the reverse reaction of a solid oxide fuel cell stack.

  Needless to say, the present invention is not limited to the above-described embodiments and the like, and can be implemented in various modes without departing from the scope of the present invention.

(A) is a perspective view which shows the reactor cell support body of 1st Embodiment, (b) is a perspective view which shows the cell layer part, (c) is a top view which shows the cell layer part. It is a perspective view which shows the electrochemical reactor cell of 1st Embodiment. It is a graph which shows tube length and efficiency loss. It is a graph which shows the 1st electrode layer thickness and efficiency loss. (A) is a perspective view showing a reactor cell support according to the second embodiment, (b) is a perspective view showing the cell layered portion, and (c) is a fracture of the internal structure of the cell layered portion along a plane. It is explanatory drawing shown. It is explanatory drawing which shows the manufacturing procedure of the electrochemical reactor stack using the reactor cell support body of 2nd Embodiment. FIG. 7 is an explanatory view showing the flow of electricity in the electrochemical reactor stack in the A-A ′ cross section (cell portion shows the outer periphery) in FIG. 6. It is a perspective view which shows an electrochemical reactor stack. (A) is explanatory drawing which shows the 2nd electrode electrical power collector of the reactor cell support body of 3rd Embodiment, (b) is a perspective view which shows the cell layer part, (c) is a perspective view which shows an electrochemical reactor stack. It is. 2 is an explanatory view showing a method for producing the electrochemical reactor stack of Example 1. FIG. 6 is an explanatory view showing a method for producing the electrochemical reactor stack of Example 2. FIG. 6 is an explanatory view showing a method for producing the electrochemical reactor stack of Example 3. FIG. FIG. 13 is a cross-sectional view of the electrochemical reactor stack of Example 3 taken along the line B-B ′ of FIG. 12.

Explanation of symbols

1, 21, 51, 73, 137 ... Reactor cell support (support)
2, 22, 77, 115, 133 ... cell layered portion 3, 23, 55, 85, 113, 147 ... first electrode current collector 5, 25, 57, 89, 105, 145 ... second electrode current collector 7 27, 59, 87, 111, 149 ... Separator 9, 29, 53, 75, 101, 135 ... Electrochemical reactor cell 11, 91, 103, 151, 153 ... Storage groove 13, 33, 81, 141 ... First Electrode layer 15, 35, 83, 143 ... Electrolyte layer 17, 37 ... Second electrode layer 31, 121, 123 ... Storage hole 39, 61, 79, 117 ... Insulating plate 41, 63, 71, 119, 131 ... Electrochemical Reactor stack 107 ... Second electrode current collector layered portion 139 ... Cover

Claims (10)

A plurality of tube-type electrochemical reactor cells having a multilayer structure in which a first electrode layer and a second electrode layer are laminated with an electrolyte layer interposed therebetween;
A first electrode current collector electrically connected to the first electrode layer; a second electrode current collector electrically connected to the second electrode layer; the first electrode current collector; A reactor cell support in which a separator disposed between a two-electrode current collector and insulating the first electrode current collector and the second electrode current collector is configured integrally;
An electrochemical reactor stack comprising:
The reactor cell support is for a plurality of grooves on a surface which is shaped like a flat plate provided in parallel,
The electrochemical reactor cells of the plurality of electrochemical reactor cells are respectively fitted into the plurality of grooves of the reactor cell support, and the plurality of electrochemical reactor cells are arranged in parallel on the reactor cell support. A layered cell layered portion is formed,
The cell layer portion has a stack structure in which a plurality of layers are stacked,
Furthermore, the first electrode layer is formed inside the electrolyte layer of the electrochemical reactor cell, is exposed from the electrolyte layer at a part of the electrolyte layer in the axial direction, and the second electrode layer is , Formed on the outer surface of the electrolyte layer,
In addition, the first electrode current collector is electrically connected at the exposed portion of the first electrode layer, and the second electrode current collector is electrically connected at the outer surface of the second electrode layer. Electrochemical reactor stack characterized by being connected to The electrochemical reactor stack according to claim 1 , wherein at least the second electrode current collector has air permeability and has a porosity of 10% or more. When the first electrode layer or the second electrode layer is a fuel electrode, the current collector material of the first electrode current collector or the second electrode current collector on the fuel electrode side is La _1-x A _{x. cr 1-y B y O 3} (a = Sr, Ca, Mg) (B = Ni, Co, Mn, Fe) (x, y = 0~1), stainless steel, metal alloys, metal-oxide cermet electrochemical reactor stack according be configured to 請 Motomeko 1 or 2 you characterized by either. When the first electrode layer or the second electrode layer is an air electrode, the current collector material of the first electrode current collector or the second electrode current collector on the air electrode side is Ag, La, Sr, you Mn, Co, Fe, Sm, Ce, Pr, Nd, Ca, Ba, Ni, elements Mg, and characterized by being constituted by any of an oxide compound containing at least one of these elements electrical chemical reactor stack according to any one of 請 Motomeko 1-3. Electrochemical reactor stack according to any one of the claims 1-4, wherein the material of the separator is a glass or ceramic having electrical insulating properties. The reactor cell support each other, while sandwiching the partially insulating member, electrochemical reactor of electrically according to any one of 請 Motomeko 1-5 you characterized in that it is connected in series stack. In the adjacent reactor cell support, the first electrode current collector of one reactor cell support and the second electrode current collector of the other reactor cell support are electrically connected. electrochemical reactor stack according to 請 Motomeko 6 you. The reactor cell support is a hexahedral structure, any one of 請 Motomeko 1-7 characterized in that both ends of the electrochemical reactor cell is fixed to protrude from both surfaces of opposing this hexahedron Electrochemical reactor stack as described in 1. Wherein an electrochemical reactor system using an electrochemical reactor stack according to any one of claims 1-8,
An electrochemical reactor system having an operating temperature of 650 ° C. or lower and taking out an electric current by an electrochemical reaction. An electrochemical reactor system using the electrochemical reactor stack according to any one of claims 1 to 8,
The electrochemical reactor system, the solid oxide fuel cell, the exhaust gas purifying apparatus, the hydrogen production apparatus, and synthetic gas chemistry reactor system electrostatic you characterized in that for use in any of the gas production system.