JP2003203651A - Support member for electrochemical cell, support structure for electrochemical cell and electrochemical device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a structure in which aggregation of electrochemical cells can be made relatively easily and gas leakage possibility due to repetition of a heat cycle of temperature-rise and temperature-drop is made little, and thereby degradation of the efficiency of the cells can be prevented. <P>SOLUTION: The electrochemical cell 9 made of a plate-shape ceramic having a through hole 9a is supported by a support member 1. The support member 1 is made of ceramics and comprises a flat plate-shape main body 1a and a protruded part 1b that protrudes from the main body 1a and is to be inserted into the through hole 9a. One of the support holes 2A for supplying one of the gas and the other support hole 2B for supplying the other gas are provided at the support member 1. A flat first seal face 1c for one of the main faces 9a of the electrochemical cell 9, while the protruded part 1b is inserted into the through hole 9a, is provided at the main body 1a. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a holding member for an electrochemical cell, a holding structure for an electrochemical cell, and an electrochemical device.

[0002]

2. Description of the Related Art Solid oxide fuel cells are roughly classified into so-called flat plate type and cylindrical type. In a flat plate type solid oxide fuel cell, a so-called separator and a power generation layer are alternately laminated to form a power generation stack.
When stacking flat plate type single cells to form an assembled battery, a structure suitable for separating the reducing gas and the oxidizing gas is required. It is also necessary to reduce the thermal stress between the materials of the unit cell, gas manifold, and separator (interconnector).

In the solid oxide fuel cell described in JP-A-6-290798, an annular shape (ring shape) is used.
A plurality of ceramic single cells of (1) are stacked to form an assembled battery. Then, each unit cell is held by each metal separator. The separator includes a disc-shaped gas manifold and a flange portion that surrounds the gas manifold. The gas manifold has
Two through holes for oxidizing gas and through holes for reducing gas are provided. Further, the flange portion is provided with a groove for oxidizing gas and a groove for reducing gas. Then, the flange portion is interposed between the unit cells that are vertically adjacent to each other. When the oxidizing gas is supplied from the through hole for the oxidizing gas of the gas manifold portion, the oxidizing gas flows through the groove of the flange portion and comes into contact with the air electrode of the unit cell. Further, when the reducing gas is supplied from the through hole for reducing gas of the gas manifold portion, the reducing gas flows through the groove of the flange portion, comes into contact with the fuel electrode of the unit cell, and power is generated. An insulating plate is sandwiched between adjacent separators to prevent a short circuit between the separators.

Further, in the conventional flat plate solid oxide fuel cell, the gas seal portion is located at the outer peripheral portion of the cell. For example, FIG. 12 of JP-A-6-290798 shows an exploded perspective view of a flat plate type solid oxide fuel cell. According to this, a flat unit cell is manufactured by the solid electrolyte plate made of ceramics, the fuel electrode and the air electrode.
Then, a stack is formed by alternately stacking the ceramic single cells and the ceramic separator plates. At this time, the groove for flowing the oxidizing gas and the groove for flowing the reducing gas are made to intersect three-dimensionally at right angles.

[0005]

However, Japanese Unexamined Patent Publication (Kokai) No. 6-2
In the solid oxide fuel cell described in Japanese Patent No. 90798, the difference in thermal expansion between the electrochemical cell, which is a ceramic, and the separator, which is a metal, is large, and when the thermal cycle of temperature increase / decrease is repeated, the electrochemical cell and the separator are separated. A crack is generated at the boundary due to the difference in thermal expansion, and the amount of gas leak tends to increase.

Further, in the conventional flat plate type solid electrolyte fuel cell, gas sealing is performed at the outer peripheral portion of the flat plate type fuel cell structure, so that the thermal stress generated in the central portion of the cell cannot be released and the cell is It tends to crack.

An object of the present invention is to make it possible to assemble electrochemical cells relatively easily when stacking so-called flat-plate type electrochemical cells to form an aggregate cell, and to increase / decrease the temperature of the cells. The purpose of this is to reduce the possibility of gas leakage when the cycle is repeated and to prevent the decrease in the operating efficiency of the cell due to this.

[0008]

SUMMARY OF THE INVENTION The present invention is a holding member for holding a plate-shaped electrochemical cell having a through hole, which is made of ceramics and has a flat plate-like main body portion, and a protruding body protruding from the main body portion. A protrusion to be inserted into the hole is provided, one supply hole for supplying one gas and the other supply hole for supplying the other gas are provided, and the protrusion is provided on the main body portion. The electrochemical cell holding member is characterized in that a sealing surface for one main surface of the electrochemical cell is provided in a state where the portion is inserted into the through hole.

Further, the present invention is an electrochemical device comprising a plurality of electrochemical cells, which comprises a holding member and an interconnector for electrically connecting adjacent electrochemical cells. The present invention relates to an electrochemical device, wherein the cell is held by a holding member, and the electrochemical cell and the interconnector are alternately arranged.

In the present invention, each electrochemical cell is held by a holding member made of ceramics. Along with this, the holding member is provided with a protruding portion to be inserted into the through hole of the electrochemical cell, the electrochemical cell is held around the protruding portion, and the main body portion is provided with respect to the main surface of the electrochemical cell. It was decided to provide a sealing surface.

With such a holding structure, since the ceramic main body and the ceramic electrochemical cell are both ceramics, the difference in thermal expansion is smaller than when the holding member is made of metal. Therefore, adverse effects due to the stress due to the difference in thermal expansion between the electrochemical cell and the holding member are less likely to occur, and gas leakage from the electrochemical cell and the seal portion is unlikely to occur for a long period of time. In addition, since the seal portion of the interconnector is in the central holding member and the outer peripheral portion of the cell is not fixed, the thermal stress generated in the cell can be released in the outer peripheral direction, and cracks are less likely to occur inside the cell.

The advantages and effects of the present invention, and further preferred embodiments will be further described with reference to the drawings.

FIG. 1 is a sectional view schematically showing a holding member 1 according to an embodiment of the present invention. FIG. 2A is a plan view of the holding member 1 viewed from the main surface 5 side, and FIG.
[FIG. 6] is a plan view of the holding member 1 as viewed from the main surface 6 side.

The planar shape of the holding member 1 is, for example, a substantially perfect circle as shown in FIG. 2, but is not limited to this and may be an elliptical shape or a polygonal shape. From the viewpoint of minimizing the thermal stress in the unit cell, a substantially perfect circle is preferable. The holding member 1 includes a main body portion 1a having a relatively large diameter and a protruding portion 1b having a relatively small diameter. Body part 1
A pair of through holes 2A and 2B are formed between the main surfaces 5 and 6 so as to penetrate the a and the protruding portion 1b. The through hole 2A is a supply hole for one gas, and the through hole 2B is a supply hole for the other gas. 5 and 6, as described later,
It is a sealing surface with an adjacent interconnector and is a flat surface in this example. Reference numerals 1c and 4 are sealing surfaces with the electrochemical cell as described later.

One gas flow path 7 is formed on the main surface 5 side of the main body portion 1a, and on the main surface 6 side of the protruding portion 1b.
The other gas flow path 8 is formed. The flow path 7 is shown in FIG.
As shown in (a), it is a groove formed on the main surface 5 side and communicates with one supply hole 2A. The flow path 8 is shown in FIG.
The groove is formed on the main surface 6 side as shown in (3) and communicates with the other supply hole 2B.

FIG. 3 shows a holding structure 20 in which the electrochemical cell 9 is held by the holding member 1. The electrochemical cell 9
For example, it has a three-layer structure of one electrode 11, a solid electrolyte layer 12, and the other electrode 13. Through hole 9a of the electrochemical cell 9
The protruding portion 1b is inserted therein. A sealing material 10B is interposed between the outer peripheral surface 4 of the protruding portion 1b and the electrochemical cell 9. One main surface 9b of the electrochemical cell 9 and the main body portion 1
The sealing material 10 is provided between the sealing surface 1c of the flange portion a of FIG.
A is present.

FIG. 4 is a sectional view showing a state in which flat plate-shaped interconnectors 15 are laminated on the holding structure 20 of FIG. Further, FIG. 5 shows the holding structure 20 shown in FIG.
It is a schematic sectional drawing which shows the electrochemical device obtained by stacking and the interconnector 15. However, in FIG. 5, only the three layers of electrochemical cells and the three layers of interconnectors are shown due to space limitations, but the number of electrochemical cells and interconnectors can be freely changed.

In this example, the interconnector 15 has a flat plate shape and is made of a conductive material such as metal. The interconnector 15 has a pair of through holes 16A and 16B formed at positions that match the through holes 2A and 2B.
The main surface 15a of the interconnector 15 is pressed against the sealing surface 5 of the holding member 1 via the sealing material 17 in the direction of arrow A to be sealed. Interconnector 15
The main surface 15b is pressed against the flat sealing surface 6 of the holding member 1 through the sealing material 17 in the direction of arrow A to be sealed.

The plurality of gas supply holes 2A and 16A communicate with each other to form a gas supply hole 21A that covers the entire electrochemical device. The plurality of gas supply holes 2B and 16B communicate with each other to form a gas supply hole 21B extending over the entire electrochemical device. When one gas is supplied to the gas supply hole 21A as shown by an arrow B, this gas becomes as shown by an arrow C,
The gas flows through the gas flow path 7 substantially parallel to the main surface 9b, flows into the space 19, and contributes to the electrochemical reaction. When the other gas is supplied to the gas supply hole 21B as indicated by the arrow D, this gas flows through the gas flow path 8 substantially parallel to the main surface 9b and flows into the space 29 as indicated by the arrow E, and the electrochemical Contribute to the reaction. Although not shown here, the spaces 19 and 29 have interconnectors.
A conductive connecting member for electrically connecting 15 and the electrochemical cell 9 is inserted.

According to the holding structure of the present invention, each of the electrochemical cells 9 is held by the holding member 1 made of ceramics, and the holding member 1 has the protruding portion 1b to be inserted into the through hole 9a of the electrochemical cell 9. Is provided to hold the electrochemical cell 9 around the protruding portion 1b, and the main body portion 1a is provided with a flat sealing surface 1c with respect to the main surface of the electrochemical cell.

With such a holding structure, the holding member 1
Since both the electrochemical cell 9 and the electrochemical cell 9 are made of ceramics, it is difficult for the seal portion to be adversely affected by the stress due to the difference in thermal expansion between the electrochemical cell and the holding member, and gas leakage from the seal portion is unlikely to occur for a long period of time.

In a preferred embodiment, as shown in FIGS. 1 to 5, the main body portion 1a of the holding member communicates with one of the supply holes 2A and the space 19 above the electrochemical cell 9 and one of the gas flows. The road 7 is provided. It is most preferable that the gas passage 7 is a groove or a recess that is recessed from the surface on the main surface 5 side as in the above-mentioned example, but it may be a cavity inside the main body portion 1a.

In the preferred embodiment, as in the above-mentioned example, the projecting portion 1b of the holding member is provided with the other gas passage 8 communicating with the other supply hole 2B and the space 29 above the electrochemical cell 9. ing. By providing one gas flow path on one main surface 5 side of the holding member and the other gas flow path on the other main surface 6 side of the holding member, both gases can be efficiently separated. . It is most preferable that the gas passage 8 is a groove or a recess that is recessed from the surface on the main surface 6 side as in the above-mentioned example, but it may be a cavity inside the protrusion 1b.

In the preferred embodiment, as in the previous example, the channels 7, 8 each extend substantially parallel to one major surface 9a of the electrochemical cell 9. Thereby, the thickness of the holding member 1 can be minimized. However, the passages 7 and 8 "extend substantially in parallel with one main surface 9a of the electrochemical cell 9" are not parallel in a strict geometric sense, and are not manufactured at the time of assembly. The purpose is to allow margins and errors in time.

In the preferred embodiment, as in the previous example, the retaining member 1 comprises a flat second sealing surface 5, 6 to be pressed against the interconnector 15. Particularly preferably, the body part 1a comprises a flat second sealing surface 5 to be pressed against the interconnector 15 and / or the protrusion 1b is pressed against the interconnector 15. With a flat second sealing surface 6 to be applied. By performing pressure sealing using such a sealing surface, it is possible to form a seal in which gas leakage is unlikely to occur due to a heat cycle.

In particular, the sealing surfaces 5 and 6 are preferably substantially perpendicular to the pressing direction A. Here, the fact that the sealing surface is substantially perpendicular to the pressing direction does not mean vertical in a strict geometrical sense, but means that a margin or error during assembly or manufacturing is allowed.

In a preferred embodiment, the interconnector is provided with one recess for receiving one seal and the other recess for receiving the other seal. This makes it difficult for the interconnectors to be laterally displaced during pressurization.

The gas passage may be provided on the interconnector side. That is, instead of flattening the main surfaces 5 and 6 of the holding member, the main surface 5 and 6 of
The gas flow paths as shown in (a) and (b) may be provided.

More specifically, the present inventor has found that when a ceramic holding member is provided with a gas flow path, defects such as cracks may occur in the holding member during heating and pressurization. It was The reason for this is considered as follows. For example, referring to FIG. 4, the gas flow paths 7 and 8 are opened to the sealing surfaces 5 and 6 of the holding member. As a result, it is considered that the strength of the holding member tends to decrease around the sealing surface. Further, since the holding member needs to perform the function of holding the electrochemical cell, there is little space margin in design when the gas flow path is provided, which reduces the strength near the sealing surface. Design that can be prevented is difficult.

Therefore, it is possible to transfer at least a part of the gas supply function to the interconnector side by providing the gas supply passage on the interconnector side, thereby improving the stability of the ceramic holding member under heating and pressure. It is useful for securing.

Therefore, in a preferred embodiment, the interconnector is provided with one supply hole communicating with one supply hole of the holding member and the space above the electrochemical cell. In this case, since one gas supply function is transferred to the interconnector side, one gas flow path on the holding member side can be made small or unnecessary. This improves the stability of the holding member near the sealing surface. Particularly preferably, the holding member is not provided with one gas flow path.

Further, in a preferred embodiment, the interconnector is provided with the other supply passage communicating with the other supply hole and the space above the electrochemical cell. Also in this case,
The other gas passage on the holding member side can be made smaller or unnecessary. Particularly preferably, the holding member is not provided with the other gas passage.

The material of the interconnector is not particularly limited as long as it is a material that is durable against the gas used at the operating temperature. For example, a perovskite complex oxide containing lanthanum is preferable, and lanthanum chromite is more preferable.

In a preferred embodiment, the interconnector is made of metal such as stainless steel, nickel base alloy, cobalt base alloy, iron base alloy and the like. In this case, gas supply passages of various shapes can be formed in the interconnector, and defects such as breakage of the interconnector are unlikely to occur under heating and pressure.

6 to 8 show an electrochemical device according to such an embodiment. FIG. 6 is a sectional view showing the interconnector 15A. The interconnector 15A has a substantially flat plate shape as a whole. In the interconnector 15A,
Gas supply holes 15c, 15 communicating with each supply hole of the holding member
d is provided, and gas supply paths 15e and 15f are provided. Each of the gas supply paths 15e and 15f has a portion that extends substantially horizontally and a portion that extends substantially vertically with respect to the direction of arrow A, and is bent. In addition, the interconnector 15A is provided with recesses 15h and 15g that are configured to receive the respective sealing materials.

In a preferred embodiment, the supply passage formed in the interconnector is bent. As a result, the gas spreads in the circumferential direction on the outside of the holding member,
Then enter the power generation room of the cell. By doing so, it is possible to efficiently supply gas to the entire surface of the cell.

As shown in FIG. 7, each holding structure 20A, interconnector 15A and sealing material 17 are laminated,
Stack it. In this example, the holding member 1A has a space 1
No gas supply path communicating with 9, 29 is provided. Each sealing material 17 is housed and fixed in the recesses 15g and 15h of the interconnector. One of the gases flows through the supply hole 16A as indicated by arrow B, bends along the supply passage 15e in the interconnector 15A as indicated by arrow E, and is supplied into the space 19. The other gas flows through the gas supply hole 16B as indicated by an arrow D, bends along the gas supply passage 15f in the interconnector 15A as indicated by an arrow F, and is supplied into the space 29. At this time, the gas flowing out from the gas supply paths 15e, 15f to the spaces 19, 29 is directed in the direction perpendicular to the cells, and therefore, at the same time as the gas exits the spaces 19, 29, the gas once spreads in the circumferential direction and the space 1
It is evenly distributed over the entire surface of 9,29. This improves the gas utilization efficiency. Also, the gas supply paths 15e and 15f may be made to meander. Further, gas flow paths having irregularities may be formed on the interconnector surfaces 15a and 15b in contact with the spaces 19 and 29. As a result, the gas flowing in the spaces 19, 29 can be rectified and the gas can be spread over the entire surfaces of the spaces 19, 29.

In a preferred embodiment, an assembled battery is constituted by a plurality of interconnectors, electrochemical cells and holding members, and a holding mechanism for holding the assembled battery under pressure is provided. This pressurizing mechanism is not particularly limited. For example, a fastening member such as a bolt or a biasing mechanism such as a spring may be used.

FIG. 8 is a schematic view showing the assembled battery according to this embodiment. Interconnector 1 as described above
5 A, the holding member 1 A, the electrochemical cell 9, and the conductive connecting member are laminated and assembled to form an assembled battery (stack) 28. Pressurization plates 23A and 23B are installed at the upper end and the lower end of the assembled battery 28, respectively, and the assembled battery 28 is sandwiched thereby. The pressure plates 23A and 23B are fastened by a fastening mechanism 24, and pressure in the direction of arrow A is applied by the bolts of the fastening mechanism. External gas pipes 26 and 25 are connected to the gas supply holes 16A and 16B, respectively, so that gas can be supplied. It is also possible to supply gas from both directions by providing gas pipes at both ends of the stack to the gas supply holes 16A and 16B. This has the effect of making the gas supply uniform between the cells stacked above and below.

In a preferred embodiment, one gas is an oxidizing gas and the other gas is a reducing gas.

The oxidizing gas is not particularly limited as long as it is a gas capable of supplying oxygen ions to the solid electrolyte membrane, and examples thereof include air, diluted air, oxygen and diluted oxygen.

As the reducing gas, hydrogen, carbon monoxide,
Examples are methane and a mixed gas thereof.

The electrochemical cell targeted by the present invention means a general cell for causing an electrochemical reaction.

For example, the electrochemical cell can be used as an oxygen pump or a high temperature steam electrolysis cell. The high temperature steam electrolysis cell can be used in a hydrogen production device and also in a steam removal device. In addition, the electrochemical cell is set to NOx, SO
It can be used as a decomposition cell of x. This decomposition cell can be used as a device for purifying exhaust gas from automobiles and power generators. In this case, oxygen in exhaust gas can be removed through the solid electrolyte membrane, and NOx can be electrolyzed to decompose into nitrogen and oxygen, and oxygen generated by this decomposition can also be removed. Further, along with this process, steam in the exhaust gas is electrolyzed to generate hydrogen and oxygen, and this hydrogen turns NOx into N2.
Reduce to. Further, in a preferred embodiment, the electrochemical cell is a solid oxide fuel cell.

The one electrode and the other electrode may be an anode or a cathode, respectively.

The material of the solid electrolyte layer is not particularly limited, and any oxygen ion conductor can be used. For example, it may be yttria-stabilized zirconia or yttria partially-stabilized zirconia, and in the case of NOx decomposition cells, cerium oxide is also preferred.

The material of the anode is preferably a perovskite type complex oxide containing lanthanum, more preferably lanthanum manganite or lanthanum cobaltite, and further preferably lanthanum manganite. The lanthanum cobaltite and lanthanum manganite may be doped with strontium, calcium, chromium, cobalt (in the case of lanthanum manganite), iron, nickel, aluminum and the like. Further, it may be palladium, platinum, ruthenium, platinum-zirconia cermet, palladium-zirconia cermet, ruthenium-zirconia cermet, platinum-cerium oxide cermet, palladium-cerium oxide cermet, or ruthenium-cerium oxide cermet.

As the material of the cathode, nickel, palladium, platinum, nickel-zirconia cermet, platinum-zirconia cermet, palladium-zirconia cermet, nickel-cerium oxide cermet, platinum-cerium oxide cermet, palladium-cerium oxide cermet, ruthenium, Ruthenium-zirconia cermet and the like are preferable.

The type of ceramic forming the holding member is not particularly limited. However, if the holding member is made of conductive ceramics, the holding member 1 may cause a short circuit between the anode and the cathode of the cell. Therefore, it is preferable that the ceramics be insulative. When using an oxidizing gas and a reducing gas, a material resistant to the oxidizing gas and the reducing gas at the operating temperature of the cell is preferable. From this point of view, magnesia-alumina spinel,
Zirconia is preferred. Also, a ceramic having a thermal expansion coefficient equal to that of the cell is preferable, and MgO / Al2 is preferable.
A magnesia-alumina spinel with O3 = 1 to 2.3 (weight ratio) is desirable.

The material of the sealing material between the cell and the holding member is not particularly limited, but again, a material resistant to an oxidizing gas or a reducing gas at the operating temperature of the cell is preferable, and a material having a thermal expansion close to that of the cell. Is preferred. From this viewpoint, a glass seal is preferable. A mechanical seal is preferably provided between the interconnector and the holding member with a gasket or the like.

The form of the electrochemical cell is not particularly limited.
The electrochemical cell, in the above example, has three layers, two electrodes and a solid electrolyte layer. However, the electrochemical cell
A porous support plate may be provided in addition to the electrodes and the solid electrolyte layer.

5 and 7, members for electrically connecting the adjacent interconnector 15A and the electrochemical cell 9 are not shown, but a breathable conductive connecting member is arranged in the spaces 19, 29. By doing so, the adjacent electrochemical cells 9 are electrically connected. For example, in the schematic diagram of FIG. 8, electrochemical cells are connected in series by sandwiching a gas-permeable conductive connecting member 30 between adjacent electrochemical cells 9. Examples of such an air-permeable conductive connecting member include felt, mesh, needle-shaped body, and sponge-shaped material.

In a preferred embodiment, the electrochemical device comprises an electrically conductive connecting member in contact with the electrochemical cell, the electrically conductive connecting member comprising a breathable material. And
This breathable material has an embossed shape imparting portion.
In addition, the breathable material preferably has a plate shape.

In this embodiment, since the conductive connecting member made of a gas permeable material is used, the gas can be efficiently supplied into the spaces 19 and 29. Furthermore, by providing the embossed shape imparting portion protruding from the surface of the breathable material, the area of the region of the electrode surface of the electrochemical cell that does not come into contact with gas can be reduced. Further, the deformation of the embossed shape imparting portion makes it possible to equalize the pressing load on the electrochemical cell, allow a slight deformation of the electrochemical cell, and prevent uneven contact. Further, it is possible to absorb a slight inclination of the electrochemical cell 9 and the interconnector 15A which occurs at the time of assembling the stack and prevent the cell from being cracked due to an unbalanced load.

FIG. 9 is a plan view showing a conductive connecting member 31 according to this embodiment, and FIG. 10 is a member 31 of FIG.
It is sectional drawing which expands and shows a part of. FIG. 11 shows the member 3
1 using interconnector 37 and electrochemical cell 3
FIG. 12 shows a state in which the separator 37 and the electrochemical cell 38 are electrically connected by using a net-like conductive connecting member 41 which is not embossed. Shows the state.

The conductive connecting member 31 is made of a mesh. The net 31 has a circular plane shape, but the plane shape is not particularly limited. The mesh 31 is obtained by braiding a large number of conductive wires 32, and a large number of meshes (gap) 33, 33A are formed between the large numbers of conductive wires 32. The cross-sectional shape of the conductive wire 32 of the net 31 is circular, but the shape is not particularly limited, and it may be a perfect circle, an ellipse, a triangle,
It may be a quadrangle or a hexagon. The braid of FIG. 9 is plain weave, but twill weave, tatami weave, clamp weave,
It may be net woven. The net 31 has a flat shape before the embossed shape is applied. J shown in FIGS. 10 and 11
Shows the center plane of the mesh before embossing, and the conductive wire 32 is braided along this center plane J. Net 3
1, an embossed shape imparting portion 31b is formed at a predetermined position. 31a is a non-embossed shape imparting portion,
It retains the form before embossing. In this example,
The embossed shape imparting portion 31b has a substantially circular shape in a plan view. 33A is a mesh in the embossed shape imparting portion 31b. The shape of the mesh 33A is slightly curved as compared with the shape of the mesh 33.

The embossed shape imparting portion 31b has one surface 31 of the net 31 as viewed from the center plane J before the embossed shape is imparted.
Since it projects toward the c side, the embossed shape imparting portion 31b
A space 35 is generated on the back side (the other surface 31d side) of the. The shape and depth of the space 35 are the same as those of the embossed shape imparting portion 31.
Determined by the shape and height of b. Space 36
It is a space surrounded by the embossed shape imparting portion 31b.

In the example shown in FIG. 11, the mesh 31 is sandwiched in one gas flow path between the grooved interconnector 37 and the electrochemical cell 38. That is, the interconnector 37 has an elongated groove 37a for supplying one gas.
Are formed, and the inside of the groove 37a functions as a gas passage 43A. Elongated projections 37c are formed between the grooves 37a. The electrochemical cell 38 includes, for example, a solid electrolyte membrane 40.
And one electrode 39 and the other electrode 42, and has a flat plate shape as a whole. One of the electrochemical cells 38 is a grooved interconnector 37, especially a protrusion 37.
It faces the surface 37b of c. A conductive connecting member made of a mesh 31 is interposed between the protruding surface 37b of the grooved interconnector 37 and the one electrode 39. One surface 31c of the net 31 faces the interconnector 37, and the other surface 31d of the net 31 contacts one electrode 39. The other gas flow path 44 is formed on the other electrode 42 side.

In this example, the net 31 has one surface 31
An embossed shape imparting portion 31b protruding toward the c side is formed, and an upper end portion of the embossed shape imparting portion 31b is in contact with the protruding surface 37c of the interconnector 37. As a result, as shown in FIG.
B and 43C are generated, and the spaces 43B and 43C function as one gas passage. The height H of the space 43B is as shown in FIG.
As shown in, it is the sum of the width d of the non-embossed shape imparting portion 31a and the height h of the embossed shape imparting portion 31b.

With such a structure, one of the gases flows in the flow passage 43A and also in the flow passage 43B formed by the net 31 and the interconnector 37 as shown by an arrow K. Then, it flows from the space 43B as shown by an arrow M, and comes into contact with the one electrode 39 from the mesh 33 of the non-embossed shape imparting portion 31a. At the same time, space 4
The gas flowing through 3B passes through the mesh 33A of the embossed shape imparting portion 31b as indicated by the arrow L, and flows into the flow channel 43C (space 35) between the embossed shape imparting portion 31b and the one electrode 39, It contacts one electrode 39 in the flow channel 43C.

On the other hand, in the case where the net is not provided with the embossed portion, the flatly braided net 41 is sandwiched between the interconnector 37 and the electrochemical cell 38, as shown in FIG. One surface 41c of the net 41 contacts the protruding surface 37b of the interconnector 37. The other surface 41d of the net 41 contacts the surface of the one electrode 39. When gas is supplied to the flow path 43A in this state, the gas comes into contact with one electrode 39 from the flow path 43A as indicated by an arrow N. However, the mesh 4 between the protruding surface 37b and the electrode 39 is
3D is surrounded by a conductive wire 42. That is, the conductive wire 42 prevents the gas from flowing from the flow path 43A into the gap 43D between the protruding surface 37b and the electrode 39. Therefore, the gas can be supplied to the electrode of the electrochemical cell in the channel 43A (groove 37a) portion, but the gas can hardly be supplied to the electrode in the region of the protruding surface 37b.

The material of the conductive connecting member of the present invention must be a material that is stable to the gas to which this member is exposed at the operating temperature of the electrochemical cell. Specifically, as stable materials against oxidizing gas, platinum, silver, gold, precious metals such as palladium, stainless steel, nickel-based alloy,
Examples include cobalt-based alloys and iron-based alloys. Materials that are stable to reducing gas include nickel and nickel-based alloys.

The breathable material is not particularly limited as long as it has breathability, but it is preferably a material that is elastically deformable when pressurized. Preferably, the breathable material is any of the following: (1) Net (mesh) (2) Metal plate having a large number of air holes formed regularly: Preferably, punching metal, etching metal, expanded metal (expanding)

The embossed shape imparting portion means a portion which gives an arbitrary shape by performing plastic deformation such as embossing. The embossing shape imparting may be such a shape imparting that a partial area of the net is pressed and deformed to form the projecting portion (embossing imparting portion) and the concave portion 35 as described above. Not limited.
Typically, there is a deep drawing shape processing method in which a net is pressed by a mold.

In the plate-like body which constitutes the conductive connecting member, for example, the net, the height h (see FIG. 10) from the non-embossed shape imparted portion of the embossed shape imparting portion is not particularly limited, but improves gas flow. From this point of view, 0.3 mm or more is preferable, and 0.5 mm or more is more preferable. However, if the height h becomes too large, the volume of the gas circulation space becomes large, so there is a possibility that the volume of wasteful gas that passes through without being used by the cell will increase, and the operation of the cell per unit volume will increase. Efficiency may be reduced. From this viewpoint, h is preferably 5 mm or less, more preferably 3 mm or less.

The planar shape of the embossed shape imparting portion is not particularly limited, and may be a perfect circle, an ellipse, a triangle, a quadrangle, or a hexagon.

In a preferred embodiment, the embossing shape imparting portion has a first embossing shape imparting portion projecting to one surface side of the net and a second embossing shape imparting portion projecting to the other surface side of the mesh. It has and. This can further reduce the pressure loss with respect to the flow of gas. 13 and 14 relate to this embodiment. FIG.
FIG. 14 is a cross-sectional view of a part of the conductive connecting member 51 formed of a mesh, and FIG. 14 shows a state where the mesh 51 is sandwiched between the electrochemical cell 38 and the interconnector 37.

The plane shape of the net 51 is, for example, a circle. The mesh 51 is obtained by braiding a large number of conductive wires 32, and a large number of meshes (gap) 33, 33A, 33B are formed between the large numbers of conductive wires 32. Net 5
No. 1 has a flat shape before embossing,
In the non-embossed shape imparting portion 51a, the conductive wire 32
Are braided along the center plane J.

The net 51 is provided with embossed shape imparting portions 51b and 51e at predetermined positions. The embossed shape imparting portion 51b protrudes to the one surface 51c side of the net 51 when viewed from the center plane J before embossing shape impartation, and the space 35A is provided on the back side (the other surface 51d side) of the embossed shape imparting portion 51b. Is generating. The shape and depth of the space 35A are determined by the shape and depth of the embossed shape imparting portion 51b. The space 36A is a space surrounded by the embossed shape imparting portion 51b and the non-embossed shape imparting portion 51a.

The embossed shape imparting portion 51e is the other surface 51 of the net 51 when viewed from the center plane J before the embossed shape is imparted.
The space 35B is projected on the d side, and a space 35B is formed on the back side (the one surface 51c side) of the embossed shape imparting portion 51e.
The shape and depth of the space 35B are determined by the shape and depth of the embossed shape imparting portion 51e. Space 36
B is a space surrounded by the embossed shape imparting portion 51e and the non-embossed shape imparting portion 51a.

In the example shown in FIG. 14, a mesh 5 is formed between the surface 37d of the interconnector 37 and one electrode 39.
A conductive connecting member made of 1 is interposed. One surface 51c of the net 51 faces the interconnector 37, and the other surface 51d of the net 51 contacts the one electrode 39.

In this example, the net 51 has one surface 51
The embossed shape imparting portion 51b protruding toward the c side is formed, and the upper end of the embossed shape imparting portion 51b is in contact with the interconnector 37d. As a result, as shown in FIG. 14, the space 43B is generated and the space 4B is generated.
3B functions as a gas flow path. In addition, the net 51 has an embossed shape imparting portion 51 protruding toward the other surface 51d.
e is formed, and the embossed shape imparting portion 51e is in contact with the surface of the one electrode 39. As a result,
The space 43E is generated, and the space 43E functions as a gas flow path.

The gas is the net 51 and the interconnector 37.
Flows in the flow path 43B formed by and as shown by an arrow K. Then, from the space 43B, as shown by the arrow L, it passes through the mesh 33A of the embossed shape imparting portion 51b, flows into the flow channel 43C formed by the space 35A, further flows into the flow channel 43E, and the surface of the electrode 39. Is supplied to. In addition, the gas flows from the space 43B into the mesh 3 as indicated by the arrow Q.
3, 33B, enters the flow path 43E, flows in the flow path 43E as indicated by an arrow P, and comes into contact with the surface of the electrode 39.

As shown in FIG. 14, when the interconnector 37 is pressed toward the electrochemical cell 38 in order to improve the electrical connection, the connection between the points A and B is improved. When the interconnector 37 is further strongly pressed toward the electrochemical cell 38, the conductive connecting member is deformed, and the electrochemical cell 38 is not subjected to a predetermined load or more, so the cell is not damaged.

As can be understood from the above gas flow,
There is almost no part that hinders the contact between the gas and the one electrode 39. Furthermore, good electrical connection is made to prevent cell damage.

The conductive connecting member 61 of FIG. 15 is made of punching metal. The punching metal 61 has a plate-shaped portion 61a provided with a large number of ventilation holes 61b. Then, from the flat plate portion 61a to the plurality of embossed shape imparting portions 61c
Are projected and are regularly arranged. 61d is a recess on the back surface side of the embossed shape imparting portion 61c.

The conductive connecting member 71 of FIG. 16 is made of so-called expanded metal. The expand 71 is composed of a metal wire 71a formed in a lattice shape, and a large number of ventilation holes 71b are formed between the metal wires 71a. Reference numeral 72 is an embossed shape imparting portion.

17 to 21 show a preferred interconnector provided with a gas supply passage.

FIG. 17A shows an interconnector 65.
17B is a plan view showing A, and FIG. 17B is a sectional view of the interconnector 65A taken along line XVIIb-XVIIb. The gas supply hole 65 is provided in the interconnector 65A.
c and 65d are provided, and each gas supply hole communicates with a gas supply hole of an electrochemical cell (not shown) as described above. Each gas supply hole communicates with a substantially circular recess 65e, and the recess 65e functions as a seal member receiving portion. In addition, the gas supply hole 65c has an elongated gas distribution groove 6
5g and 65h are provided as a gas supply path. A recess 65f is formed on the main surface 65b side of the interconnector 65A over substantially the entire surface of the interconnector, and each gas distribution groove 65 is formed in the recess 65f.
g and 65h communicate. The concave portion 65f functions as a receiving portion for the conductive connecting member and has an effect of spreading the gas over the entire surface.

One gas or the other gas flows through the gas supply hole 65c, passes through the gas distribution grooves 65g and 65h,
It flows over the entire surface of the ring-shaped gas distribution recess 65f. A gas passage may be formed in the recess 65f. The main surface 65b of the interconnector 65A faces the electrode of the electrochemical cell as described above.

FIG. 18A shows an interconnector 65.
18B is a plan view showing B, and FIG. 18B is a cross-sectional view of the interconnector 65B taken along line XVIIIb-XVIIIb. The interconnector 65B is further provided with an elongated gas distribution groove 65j communicating with the gas supply hole 65c.

FIG. 19A shows an interconnector 65.
FIG. 19B is a plan view showing C, and FIG. 19B is a sectional view of the interconnector 65C taken along line XIXb-XIXb. In the interconnector 65C, the elongated gas distribution groove is not provided in the recess 65e, but instead, the arc-shaped gas distribution groove 65k is provided.

In each of the interconnectors of FIGS. 17 to 19, a gas distribution groove for one gas or the other gas is formed in the interconnector. However, a gas distribution groove for each gas may be provided on the front and back of the interconnector. 20 and 21 relate to this embodiment.

FIG. 20A shows an interconnector 65.
FIG. 20B is a plan view of D viewed from the main surface 65b side, and FIG.
FIG. 21 is a cross-sectional view of the interconnector 65D taken along the line XXb-XXb, and FIG. 21 is a plan view of the interconnector 65D seen from the main surface 65a side.

The interconnector 65D is provided with gas supply holes 65c and 65d, and each gas supply hole is
It communicates with the gas supply hole of the electrochemical cell (not shown) as described above. Each gas supply hole communicates with a substantially circular recess 65e on the main surface 65b side and also communicates with a substantially circular recess 65p on the main surface 65a side. The recesses 65e and 65p are
Each functions as a receiving part for the sealing material. Also,
Elongated gas distribution grooves 65g and 65h are provided as gas supply passages in the recess 65e. In the recess 65p,
Elongated gas distribution grooves 65m and 65n are provided as gas supply paths.

One gas flows through the gas supply hole 65c,
It passes through the gas distribution grooves 65g and 65h and flows in the space between the interconnector 65D and the electrochemical cell. The other gas flows through the gas supply hole 65d, the gas distribution groove 65m,
It passes through 65n and flows in the space between the interconnector 65D and the electrochemical cell.

[0087]

As described above, according to the present invention, it is possible to assemble electrochemical cells relatively easily, and to prevent the possibility of gas leak when the heat cycle of temperature increase-temperature decrease is repeated. It is possible to reduce the number of cells, and to prevent a decrease in cell operating efficiency due to this.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a holding member 1 according to an embodiment of the present invention.

2A is a plan view of the holding member 1 as viewed from the main surface 5 side, and FIG. 2B is a plan view of the holding member 1 as viewed from the main surface 6 side.

FIG. 3 is a cross-sectional view showing a holding structure 20 obtained by holding the electrochemical cell 9 on the holding member 1.

FIG. 4 is a view showing the holding structure 20 and the interconnector 15 of FIG.
It is sectional drawing which shows the state which laminated | stacked.

FIG. 5 shows an aggregate cell obtained by stacking a plurality of holding structures 20 and interconnectors 15.

FIG. 6 is an interconnector 15A according to another embodiment.
FIG.

FIG. 7 shows a laminated structure of an interconnector 15A and a holding structure 20A.

FIG. 8 is a schematic view showing a pressing mechanism of an assembled battery including an interconnector 15A, an electrochemical cell 9 and a holding member 1A.

FIG. 9 is a plan view showing a net 31 used as a conductive connecting member in an embodiment of the present invention.

10 is an enlarged sectional view showing a part of the net 31 of FIG.

FIG. 11: Interconnector 37 and electrochemical cell 38
It is an important section sectional view showing the state where net 31 was inserted between and.

FIG. 12 is a cross-sectional view of essential parts showing a state in which a net 41 having no embossed shape is interposed between a separator 37 and an electrochemical cell 38.

FIG. 13 is a cross-sectional view showing a part of a net 51 according to another embodiment of the present invention.

FIG. 14: Interconnector 37 and electrochemical cell 38
It is an important section sectional view showing the state where net 51 was inserted between and.

FIG. 15 is a conductive connecting member 6 made of punching metal.
It is a perspective view showing 1.

FIG. 16 is a perspective view showing a conductive connecting member 71 made of expanded.

17A is a plan view showing an interconnector 65A, and FIG. 17B is a sectional view taken along line XVIIb-XVIIb of the interconnector 65A.

18A is a plan view showing an interconnector 65B, and FIG. 18B is a sectional view of the interconnector 65B taken along line XVIIIb-XVIIIb.

19A is a plan view showing an interconnector 65C, and FIG. 19B is a sectional view of the interconnector 65C taken along line XIXb-XIXb.

20A is a plan view of the interconnector 65D seen from the main surface 65b side, and FIG. 20B is a sectional view of the interconnector 65D taken along line XXb-XXb.

FIG. 21 is a plan view of the interconnector 65D as viewed from the main surface 65a side.

[Explanation of symbols]

1 Holding Member 1a Body Part 1b Projection 1c Sealing Surface 2A One Supply Hole 2
B Other supply hole 4 Sealing surface 5 Main surface on main body part 1a side (sealing surface for interconnector 15) 6 Main surface on protrusion 1b side (sealing surface for interconnector 15) 7 One gas flow path 8 Other gas Channel 9 Electrochemical cell 9a Through hole 9b
One main surface of electrochemical cell 11 One electrode
12 solid electrolyte layer 13 other electrode
15,15A Interconnector 15
a, 15b Main surface of interconnector 16A
Flow path 16B for one gas Flow path 20B for the other gas 20A Holding structure 21A, 21
B gas supply hole 31, 51 mesh provided with embossed shape imparting portion 32 conductive wire 33 mesh of non-embossed shape imparting portion 31a 33A, 3
3B Embossed shape imparting mesh 35, 35
A, 35B Space formed on the back surface side of the embossed portion 36, 36A, 36B Space formed by the non-embossed portion and the embossed portion 37 Interconnector 37a Groove (gas channel) 37b Projection surface 37c Protrusion 3
7d surface 38 electrochemical cell 39 one electrode 40 solid electrolyte membrane
42 Other electrode 43A Flow path 43B, 4 formed by groove
3E Channels formed by spaces 36, 36A, 36B 43C, 13D Channel formed on the back surface side of the embossed shape imparting portion 44 Channel for the other gas 61 Conductive connecting member 71 made of punching metal 71 Conductivity made of expanded Sex connection member

Continued front page    (72) Inventor Sota Shimizu             2-56, Sudacho, Mizuho-ku, Nagoya-shi, Aichi             Inside Hon insulator Co., Ltd. (72) Inventor Kiyoshi Okumura             2-56, Sudacho, Mizuho-ku, Nagoya-shi, Aichi             Inside Hon insulator Co., Ltd. (72) Inventor Mitsuru Hattori             2-56, Sudacho, Mizuho-ku, Nagoya-shi, Aichi             Inside Hon insulator Co., Ltd. F-term (reference) 5H026 AA06 CC03 CV01 EE11

Claims (21)

[Claims] 1. A holding member for holding a plate-shaped ceramic electrochemical cell having a through hole, which is made of ceramics, has a flat plate-like main body portion, and protrudes from the main body portion and is inserted into the through hole. It is provided with a protrusion to be provided, one supply hole for supplying one gas and the other supply hole for supplying the other gas are provided, and the protrusion is provided on the main body portion. A holding member for an electrochemical cell, wherein a sealing surface for one main surface of the electrochemical cell is provided in a state of being inserted into the through hole. 2. The member according to claim 1, wherein the main body portion is provided with one gas flow passage communicating with the one supply hole and the space above the electrochemical cell. 3. The member according to claim 1, wherein the projecting portion is provided with the other gas passage that communicates with the other supply hole and the space above the electrochemical cell. 4. The member according to claim 1, further comprising another sealing surface for an interconnector connecting a plurality of the electrochemical cells. 5. An electrochemical device comprising a plurality of electrochemical cells, wherein the holding member according to any one of claims 1 to 4 and the adjacent electrochemical cells are electrically connected to each other. An electrochemical device comprising an interconnector for connection, wherein the electrochemical cell is held by the holding member, and the electrochemical cell and the interconnector are alternately arranged. 6. One sealing material is sandwiched between the sealing surface of the main body portion and the one main surface of the electrochemical cell, and the other sealing surface of the holding member and the interconnector. The device according to claim 5, wherein another sealing material is sandwiched between the two. 7. The apparatus according to claim 5, wherein the pressure is applied in a direction substantially perpendicular to the one main surface. 8. The device according to claim 5, wherein a gasket is provided as a sealing material between the interconnector and the holding member. 9. The interconnector is provided with one supply path communicating with the one supply hole and the space above the electrochemical cell.
The device according to claim 8. 10. The apparatus according to claim 9, wherein the holding member is not provided with a gas flow path communicating with the one supply hole and the space above the electrochemical cell. 11. The interconnector is provided with the other supply path communicating with the other supply hole and the space above the electrochemical cell.
10. A device according to any one of claims 10 to 10. 12. The apparatus according to claim 11, wherein the holding member is not provided with a gas flow path communicating with the other supply hole and the space above the electrochemical cell. 13. The interconnector is provided with one recess for receiving the one sealing material and another recess for receiving the other sealing material. 13. A device according to any one of claims 12. 14. A breathable and deformable electrically conductive connecting member is arranged between the interconnector and the electrochemical cell, as claimed in any one of claims 5 to 13. The device according to one claim. 15. The device according to claim 14, wherein the conductive connecting member includes an embossed portion. 16. The device according to claim 14, wherein the conductive connecting member comprises a mesh. 17. A holding structure for holding a plate-shaped ceramic electrochemical cell having a through hole, comprising the electrochemical cell and a holding member for holding the electrochemical cell. The holding member Is made of ceramics and has a flat plate-shaped main body portion, and a protruding portion that protrudes from the main body portion and is to be inserted into the through hole. One supply hole for supplying one gas and the other gas The other supply hole for supplying the electric field is provided, and the main body part is provided with a sealing surface for one main surface of the electrochemical cell in a state where the projecting portion is inserted into the through hole. A holding structure for an electrochemical cell, which is characterized in that 18. The structure according to claim 17, wherein the main body portion is provided with one gas flow passage communicating with the one supply hole and the space above the electrochemical cell. 19. The structure according to claim 17, wherein the projecting portion is provided with another gas passage communicating with the other supply hole and the space above the electrochemical cell. 20. The method according to claim 17, wherein the holding member has another sealing surface for an interconnector connecting the plurality of electrochemical cells. Structure. 21. A sealant according to claim 17, wherein a sealant is sandwiched between the seal surface of the main body portion and the one main surface of the electrochemical cell. Structure described in paragraph.