JP5222503B2 - Device comprising a ceramic thin plate and a metal thin plate - Google Patents

Description

  The present invention relates to a device including a ceramic thin plate body including a fired ceramic sheet and a metal thin plate body supporting the ceramic thin plate body, and used for, for example, a solid oxide fuel cell.

  Conventionally, a thin plate body including a fired ceramic sheet (hereinafter also referred to as a “ceramic thin plate body”) includes various sensors, actuators, solid oxide fuel cells (SOFC), and the like. It has been used for the device. For example, when a ceramic thin plate is applied to SOFC, the ceramic thin plate is formed on a solid electrolyte zirconia, a fuel electrode layer formed on one surface of the solid electrolyte zirconia, and on the other surface of the solid electrolyte zirconia. And an air electrode layer. Further, the fuel flow path is formed in a portion facing the fuel electrode layer, and the air flow path is formed in a portion facing the air electrode layer. The ceramic thin plate for SOFC is bonded to a holding thin plate frame (hereinafter also referred to as “metal thin plate”) made of metal around the SOFC, and is held by the thin metal plate. The outer peripheral portion of the thin metal plate is further supported by a support member.

This thin metal plate has a curved portion formed by press working or the like. The curved portion is formed so as to surround the ceramic thin plate body. In other words, the bending portion is formed in the metal thin plate body so that the ridge portion formed by continuously extending the top portion surrounds the ceramic thin plate body (the outer periphery thereof) (see, for example, Patent Document 1). )
Japanese Patent No. 3466960 (FIG. 6)

  By the way, when the SOFC tries to start power generation rapidly, the temperature of the device (ceramic thin plate and metal thin plate) changes rapidly. As a result, a difference in thermal expansion occurs between the ceramic thin plate and the metal thin plate. The thermal stress generated by the difference in the thermal expansion amount is mainly applied to the joint portion between the ceramic thin plate and the metal thin plate and / or the ceramic thin plate. Although the conventional thin metal plate body has a curved portion, the top portion (ridge portion) of the curved portion is formed so as to surround the ceramic thin plate body, and therefore, thermal stress applied to the joint portion and / or the ceramic thin plate body. It cannot be deformed so as to relax sufficiently. For this reason, the joint part of a ceramic thin plate body and a metal thin plate body and / or a ceramic thin plate body may be damaged.

  Furthermore, since the conventional curved portion is formed so as to surround the ceramic thin plate, it is difficult to function to improve the rigidity of the thin metal plate in the direction perpendicular to the plane of the ceramic thin plate. For this reason, when the thermal expansion is performed so as to relieve the thermal stress, the curved portion is deformed not only in the direction in the plane of the ceramic thin plate but also in the direction orthogonal to the plane of the ceramic thin plate. As a result, the curved portion easily moves the ceramic thin plate in a direction perpendicular to the plane of the ceramic thin plate when thermally expanded. Therefore, even when the joint and / or the ceramic thin plate member is not damaged, there is a problem that the ceramic thin plate member moves or deforms in a direction orthogonal to the plane to close the fuel flow path or the air flow path. There is a fear. In addition, even when the ceramic thin plate moves or deforms to such an extent that the fuel flow path or the air flow path is not closed, the pressure loss when a fluid such as fuel and / or air flows through these flow paths is reduced. There is a problem that it increases due to movement or deformation of the body.

  As described above, when the joint portion is damaged or the ceramic thin plate is deformed, the performance or reliability of the apparatus is lowered. Accordingly, one of the objects of the present invention is to stabilize the expected performance of the device to which the device is applied even when the temperature of the device having a structure in which the ceramic thin plate is held by the metal thin plate is changed. It is to provide a device that can be exhibited.

To achieve the above object, a device according to the present invention comprises:
A ceramic sheet including a fired ceramic sheet;
A metal thin plate made of a metal having an outer shape larger than the outer shape of the ceramic thin plate, and
In a device comprising:
The outer peripheral portion of the ceramic thin plate is joined to the metal thin plate, and the metal thin plate is along the direction from the joint between the ceramic thin plate and the metal thin plate toward the outer peripheral of the metal thin plate. A plurality of wrinkle portions having a ridge portion whose top portion continuously extends are formed.

  That is, in this device, the wrinkled portion (swelled portion or curved portion) of the thin metal plate is formed so that the ridge portion of the wrinkled portion is substantially radially in plan view. Accordingly, the wrinkle portion effectively relaxes the thermal stress applied to the joint portion and the ceramic thin plate member due to the difference in thermal expansion. Furthermore, the plurality of wrinkle portions also function as ribs (reinforcing portions) that increase the rigidity of the metal thin plate body (and the ceramic thin plate body) in the direction orthogonal to the plane formed by the ceramic thin plate body and the metal thin plate body. . Therefore, breakage of the joint between the ceramic thin plate and the metal thin plate can be avoided, and the above-described movement or deformation of the ceramic thin plate can be suppressed. As a result, an apparatus to which the device is applied can stably exhibit the expected performance. In addition, the outer peripheral part of the said ceramic thin plate body used as a junction part may include the outer periphery of the ceramic thin plate body, and does not need to include it.

  The metal thin plate member may include one through hole in a region inside a joint portion between the ceramic thin plate member and the metal thin plate member. The single through hole may be a large hole formed along the inner peripheral side of the joint. In this case, the thin metal plate can be substantially called a thin metal frame. Further, a member having a mesh structure or a member having a plurality of through holes, which is a member different from the metal thin plate body, is disposed in the one through hole portion, and the member is held by the metal thin plate body. May be.

  Moreover, the said metal thin plate body may be provided with the some through-hole in the area | region inside the junction part of the said ceramic thin plate body and the said metal thin plate body. The plurality of through holes is a concept including a plurality of meshes of a mesh structure formed in a region inside the joint portion of the thin metal plate. By providing a plurality of through holes in the metal thin plate body in this manner, the fluid required for the ceramic thin plate body is sufficiently supplied through the plurality of through holes, and electrons are generated by portions other than the plurality of through holes of the metal thin plate body. Etc. can be collected more efficiently.

  Furthermore, according to experiments, it has been found that the above-described device has the characteristics described below, whereby the above-described movement or deformation of the ceramic thin plate is effectively suppressed.

(1) The ridge portion of the wrinkle portion extends in a direction having an angle of 45 degrees or more and 135 degrees or less with respect to a tangent line of the outer peripheral edge of the ceramic thin plate member. In other words, the angle at which the ridge portion of the wrinkle portion extends is within ± 45 degrees with respect to the normal line of the outer peripheral edge of the ceramic thin plate member. In addition, the wrinkle part of the direction along angles other than this angle may be formed.
(2) The thickness of the ceramic sheet is 20 μm or more and 200 μm or less, and the thickness of the metal sheet is 20 μm or more and 80 μm or less.

(3) The height of the said wrinkle part which is the distance of the upper side top part of the said wrinkle part and a lower side top part is 10 micrometers or more and 70 micrometers or less.
(4) The distance between the tops of two adjacent wrinkle portions measured at a position 0.5 mm away from the end of the ceramic thin plate body toward the outer peripheral portion of the metal thin plate body is 1 mm or more and 4 mm or less. .

  In one aspect of the device according to the present invention, it is desirable that the metal thin plate member and the outer peripheral portion of the ceramic thin plate member are joined by glass or a metal brazing material.

  When joining a thin metal plate and a ceramic thin plate using glass or metal brazing material, the thin metal plate and the thin ceramic plate are heated to a predetermined high temperature and stretched by an amount corresponding to the respective coefficient of thermal expansion. To do. The metal thin plate and the ceramic thin plate are joined by solidifying the glass or metal brazing material when the temperature is lowered from this extended state. Since the amount of shrinkage of the metal thin plate and the amount of shrinkage of the ceramic thin plate during the temperature drop are different from each other, thermal stress is mainly generated at the joint between the two. As a result, the metal thin plate body that is relatively easily deformed is deformed more greatly, and the plurality of wrinkle portions are formed in the metal thin plate body by the deformation. Therefore, when a device composed of a thin metal plate body and a ceramic thin plate body having a plurality of wrinkle portions formed in this way is heated from room temperature, a part of the wrinkle portion is caused by the thermal stress generated by the temperature increase. Relaxed by stretching. That is, the thin metal plate is deformed so as to return to a heated state before joining. As a result, even if the temperature rise and fall of the device is repeated, excessive thermal stress is not repeatedly applied to the joint and / or the ceramic thin plate, so that the durability of the device becomes extremely high.

  The ceramic thin plate member may be a single thin plate member or a laminate in which a plurality of thin plate members are stacked. When the ceramic thin plate is a laminate in which a plurality of thin plates is laminated, the ceramic thin plate may be a laminate of the ceramic sheet and a sheet made of a material having a different coefficient of thermal expansion from the ceramic sheet. Good.

Furthermore, in this case, in order to configure the SOFC,
The ceramic thin plate is
A solid electrolyte layer as the ceramic sheet;
A fuel electrode layer as a sheet made of a material having a different coefficient of thermal expansion formed on one surface of the solid electrolyte layer;
An air electrode layer as a sheet made of a material having a different coefficient of thermal expansion formed on the other surface of the solid electrolyte layer;
Can be provided.
The fuel electrode layer and / or the air electrode layer may be formed integrally with the ceramic sheet by firing, or may be formed on the ceramic sheet by other film forming techniques.

In addition, when the ceramic thin plate body includes a solid electrolyte layer, a fuel electrode layer, and an air electrode layer, the device is
A first support member having a flat part and an upper frame part that is erected toward the upper part of the flat part and a lower frame part that is erected downward of the flat part;
A second support member having a planar part and an upper frame part erected toward the upper part of the planar part and a lower frame part erected to the lower part of the planar part around the planar part;
With
The first support member and the second support member are coaxially arranged on the upper frame portion of the first support member so that the lower frame portion of the second support member faces each other,
The metal thin plate is sandwiched between the upper frame portion of the first support member and the lower frame portion of the second support member, whereby the ceramic thin plate member is placed on the upper surface of the flat portion of the first support member. Are arranged so that the air electrode layers of the ceramic thin plate body are opposed to the lower surface of the flat portion of the second support member,
The upper surface of the flat portion of the first support member, the inner wall surface of the upper frame body portion of the first support member, and the air electrode layer of the thin plate body form an air flow path to which a gas containing oxygen is supplied,
It is desirable that a fuel flow path for supplying fuel is formed by the lower surface of the flat portion of the second support member, the inner wall surface of the lower frame portion of the second support member, and the fuel electrode layer of the thin plate member.

  By stacking such devices, a flat stack type miniaturized SOFC is provided. At this time, since the ceramic thin plate body is difficult to move or deform due to the presence of the wrinkled portion of the metal thin plate described above, a small SOFC in which the fuel flow path and the air flow path are not narrowed by the movement or deformation of the ceramic thin plate body is provided. Can be provided.

More specifically, for example, SOFC performs power generation based on chemical reaction formulas (1) and (2) shown below.
(1/2) · O ₂ +2 ^e− → O ²⁻ (in the air electrode layer) (1)
H ₂ + O ²⁻ → H ₂ O + 2 ^e− (in the fuel electrode layer) (2)
That is, in this reaction, 0.5 mol of oxygen is required for 1 mol of hydrogen. On the other hand, since oxygen is supplied by air, when the amount of oxygen in the air is taken into consideration, when the amount of hydrogen is 1, the amount of air necessary for power generation is 2.5. That is, the amount of hydrogen and the amount of air required for power generation differ greatly from each other with respect to a single ceramic sheet having a fuel electrode layer and an air electrode layer. Furthermore, since oxygen molecules are larger than hydrogen molecules, the rate at which oxygen molecules diffuse through the air electrode layer (and hence the reaction efficiency) is smaller than the rate at which hydrogen molecules diffuse through the fuel electrode layer. For this reason, it is necessary to supply more oxygen (and therefore air) to the space (air flow path) on the air electrode layer side. From the above, there is a large difference between the pressure in the space on the fuel electrode layer side (fuel flow path or hydrogen flow path) and the pressure in the space on the air electrode layer side (air flow path) with respect to a single ceramic sheet. There are many cases. Therefore, since the ceramic thin plate used in the SOFC always receives a force in a direction perpendicular to the plane, if the device according to the present invention in which the ceramic thin plate is difficult to move or deform is applied to the SOFC, the durability of the SOFC is reduced. It becomes possible to remarkably improve the nature.

  The outer peripheral shape of the ceramic thin plate in the present invention in a plan view is an arbitrary shape such as a circle, an ellipse, an oval, a polygon such as a square or a hexagon, and a shape in which an arc is added to each corner of the polygon. It may be. The outer peripheral shape of the metal thin plate in plan view is a circle, an ellipse, an oval, a polygon such as a square or a hexagon, and a polygon, regardless of the shape of the outer periphery of the ceramic thin plate. Arbitrary shapes, such as the shape which gave the circular arc to the corner | angular part, may be sufficient.

  Hereinafter, a device according to an embodiment of the present invention will be described with reference to the drawings. This device is applied to various apparatuses such as sensors, actuators, and solid oxide fuel cells. In the following examples, this device is applied to a solid oxide fuel cell (hereinafter also simply referred to as “fuel cell”).

(Configuration of fuel cell)
FIG. 1 is a partially exploded perspective view of a solid oxide fuel cell (fuel cell) 10 to which a device according to an embodiment of the present invention is applied. The fuel cell 10 includes a plurality of support members 11, a plurality of metal thin plate bodies 12, and a plurality of ceramic thin plate bodies 13. As shown in FIG. 1 and FIG. 2 which is a partial cross-sectional view of the fuel cell 10, the support member 11 and the metal thin plate 12 that holds the ceramic thin plate 13 on the upper surface side are alternately laminated. It is formed by. That is, the fuel cell 10 has a stack structure.

  The support member 11 is made of a ferrite-based SUS (stainless steel) or a Ni-based heat-resistant alloy (for example, Inconel 600 and Hastelloy). The support member 11 is also referred to as an “interconnector”. The support member 11 is shown in FIGS. 4 to 6 which are cross-sectional views taken along planes 4-4, 5-5 and 6-6 of FIG. 3 and FIG. 3 which are plan views. As shown, the flat part 11a, the upper frame part 11b, and the lower frame part 11c are provided.

  The flat surface portion 11a is a thin flat plate having a thickness direction in the Z-axis direction. The planar shape of the planar portion 11a is a square having sides along the X-axis and Y-axis directions orthogonal to each other. The Z axis is orthogonal to the plane including the X axis and the Y axis.

  The upper frame body portion 11b is a frame body standing upright above the flat surface portion 11a around the flat surface portion 11a (a region near the four sides, that is, a region near the outer periphery). The height of the upper frame portion 11b from the upper surface of the flat portion 11a is H1 as shown in FIG.

  As shown in FIGS. 3 and 5, the cross-sectional shape of the portion extending along the X axis of the upper frame portion 11b is a rectangle having sides parallel to the Y axis and the Z axis, respectively. A slit 11b1 extending along the X axis (slit 11b1 whose longitudinal direction is the X axis direction) is formed in a portion extending along the X axis of the upper frame portion 11b.

  As shown in FIGS. 3 and 6, the cross-sectional shape of the portion extending along the Y axis of the upper frame body portion 11b is a rectangle having sides parallel to the X axis and the Z axis, respectively. The portion extending along the Y axis of the upper frame portion 11b is the same as the portion of the portion extending along the X axis of the upper frame portion 11b from which the vertical wall on the inner peripheral side forming the slit 11b1 is deleted. It has the shape of

  The lower frame body portion 11c is a frame body that is erected toward the lower side of the flat surface portion 11a around the flat surface portion 11a (a region near four sides, that is, a region near the outer periphery). The height from the lower surface of the plane part 11a of the lower frame part 11c is H2, as shown in FIG. The height H2 is higher than the height H1.

  As shown in FIGS. 3 and 6, the cross-sectional shape of the portion extending along the Y axis of the lower frame body portion 11 c is a rectangle having sides parallel to the X axis and the Z axis, respectively. A slit 11c1 (slit 11c1 whose longitudinal direction is the Y-axis direction) extending along the Y axis is formed in a portion extending along the Y axis of the lower frame portion 11c. The shape of the slit 11c1 in plan view is the same as the shape of the slit 11b1 in plan view except for the direction in the longitudinal direction.

  As shown in FIGS. 3 and 5, the cross-sectional shape of the portion of the lower frame portion 11c extending along the X axis is a rectangle having sides parallel to the Y axis and the Z axis. The portion extending along the X axis of the lower frame portion 11c is the same as the portion of the portion extending along the Y axis of the lower frame portion 11c from which the inner peripheral vertical wall forming the slit 11c1 is deleted. It has the shape of

  As a result, the slit 11b1 communicates with the space below the flat portion 11a. The slit 11c1 communicates with the space above the flat portion 11a.

  When the support member 11 rotates 90 degrees clockwise or counterclockwise around the center of gravity G (see FIG. 3) of the support member 11 in plan view, the support member 11 follows the Y axis of the upper frame body portion 11b before the rotation. The portion extending in this manner coincides with the portion where the outer vertical wall constituting the slit 11b1 of the portion extending along the X axis of the upper frame portion 11b existed before the rotation. Further, when the support member 11 rotates 90 degrees clockwise or counterclockwise about the center of gravity G of the support member 11 in plan view, the portion extending along the X axis of the upper frame body portion 11b before the rotation The outer vertical wall constituting the slit 11b1 coincides with a portion where a portion extending along the Y axis of the upper frame portion 11b existed before the rotation.

  Similarly, when the support member 11 rotates 90 degrees clockwise or counterclockwise about the center of gravity G of the support member 11 in plan view, the support member 11 extends along the Y axis of the lower frame portion 11c before the rotation. The outer vertical wall constituting the slit 11c1 of the lower frame body portion 11c before the rotation coincides with the portion where the portion extending along the X axis was present. Further, when the support member 11 is rotated 90 degrees clockwise or counterclockwise around the center of gravity G of the support member 11 in plan view, a portion extending along the X axis of the lower frame body portion 11c before the rotation is Before the rotation, the outer vertical wall constituting the slit 11c1 of the portion extending along the Y axis of the lower frame body portion 11c coincides with the portion.

  The thin metal plate 12 is made of stainless steel (for example, SUS430). The thin metal plate 12 is also referred to as a “metal support plate”. The outer shape of the thin metal plate 12 in plan view is a square having sides along the X-axis and Y-axis directions, as shown in FIG. 7 which is a plan view. The size of the thin metal plate 12 in plan view is the same as the size of the support member 11 in plan view. That is, the outer shape of the thin metal plate 12 in plan view is the same as the outer shape of the support member 11 in plan view. The thickness direction of the thin metal plate 12 is the Z-axis direction. The thickness of the thin metal plate 12 is 20 μm or more and 80 μm or less.

  In the thin metal plate 12, a slit 12a having the same shape as the slit 11b1 is formed at a position corresponding to the slit 11b1 of the support member 11 (a position coincident in plan view). Further, the thin metal plate 12 is formed with a slit 12b having the same shape as the slit 11c1 at a position corresponding to the slit 11c1 of the support member 11 (a position coincident in plan view). The thin metal plate 12 has a plurality of through holes 12c formed in a matrix at the center. When the metal thin plate 12 is rotated 90, 180, and 270 degrees around the center of gravity of the metal thin plate 12 in a plan view, the metal thin plate 12 has a shape that matches the state before each rotation.

  The ceramic thin plate 13 is an electrolyte layer (solid electrolyte layer) 13a as shown in FIG. 9 in which a portion surrounded by a circle A in FIG. 8 which is a cross-sectional view of the metal thin plate 12 and the ceramic thin plate 13 is enlarged. The fuel electrode layer 13b formed on the electrolyte layer 13a (upper surface, one surface) and the air electrode layer 13c formed on the surface (lower surface, other surface) opposite to the fuel electrode layer 13b on the electrolyte layer 13a. And have. The ceramic thin plate 13 is also referred to as a “single cell” of the fuel cell 10. The shape of the ceramic thin plate 13 in plan view is a square having sides along the X-axis and Y-axis directions as shown in FIG. The size of the ceramic thin plate 13 in plan view is slightly smaller than the size of the metal thin plate 12 in plan view (that is, the shape of the ceramic thin plate 13 in plan view is defined by the inner sides of the slits 12a and 12b. A square that is slightly smaller than a square.) The thickness direction of the ceramic thin plate 13 is the Z-axis direction. The thickness of the ceramic thin plate 13 is 20 μm or more and 200 μm or less.

  The lower surface of the outer peripheral portion of the ceramic thin plate member 13 is joined to the upper surface of the metal thin plate member 12 by glass or a metal brazing material. The width of the joint is a constant width W as shown in FIG. In a state where the ceramic thin plate member 13 is joined to the metal thin plate member 12, all of the plurality of through holes 12 c of the metal thin plate member 12 are positioned below the ceramic thin plate member 13.

  In this example, the electrolyte layer 13a is a dense fired body of YSZ (yttria stabilized zirconia) as a ceramic sheet. The fuel electrode layer 13b is a fired body made of Ni-YSZ and is a porous electrode layer. The air electrode layer 13c is a fired body made of LSM (La (Sr) MnO3: lanthanum strontium manganite) -YSZ, and is a porous electrode layer. The electrolyte layer 13a, the fuel electrode layer 13b, and the air electrode layer 13c have different coefficients of thermal expansion. Further, the thermal expansion coefficient of the ceramic thin plate body 13 is different from the thermal expansion coefficient of the metal thin plate body 12. The specific coefficient of thermal expansion is as follows. Electrolyte (YSZ): 10.8 ppm / K, Fuel electrode (Ni-YSZ): 11.4 ppm / K, Air electrode (LSM-YSZ): 10.6 ppm / K, Metal thin plate (SUS430): 12.1 ppm / K.

  A plurality of wrinkle portions 12 d are formed on the metal thin plate 12. The wrinkle portion 12d includes a joint portion between the ceramic thin plate body 13 and the metal thin plate body 12, and an outer peripheral portion of the metal thin plate body 12 (more specifically, the slit 12a or 12b, and further inward from the slit 12a or 12b. (Refer to a region B surrounded by an ellipse in FIG. 2). The wrinkle portion 12 d has a top portion (ridge portion) that continuously extends along the direction from the joint portion between the ceramic thin plate body 13 and the metal thin plate body 12 toward the outer peripheral portion of the metal thin plate body 12. That is, the ridge portion of the wrinkle portion 12d is in a direction having an angle of 45 degrees or more and 135 degrees or less with respect to a tangent line of the outer peripheral edge of the ceramic thin plate member 13 (in this example, a straight line along the X axis or the Y axis). It is growing. Measured at a position 0.5 mm away from the end of the ceramic thin plate 13 toward the outer periphery of the metal thin plate 12, the distance L between the tops of two adjacent wrinkle portions (between adjacent upper ridge portions 12d1). The distance L, see FIG. 10) ”is 1 mm or more and 4 mm or less. Furthermore, the height Hd of the wrinkle portion 12d, which is the distance between the upper top portion (upper ridge portion) 12d1 and the lower top portion (lower ridge portion) 12d2 of the wrinkle portion shown in FIG. 10, is 10 μm or more and 70 μm or less. . Note that FIG. 10 shows the metal between the portion extending in the X-axis direction of the joint between the metal thin plate 12 and the ceramic thin plate 13 and the slit 12a of the metal thin plate 12 adjacent to the joint. It is the fragmentary sectional view which cut | disconnected the thin plate body 12 in the plane along XZ plane.

  Here, a method of forming the plurality of wrinkle portions 12d will be described. The plurality of wrinkle portions 12d are formed when the metal thin plate body 12 and the ceramic thin plate body 13 are joined using glass or a metal brazing material. More specifically, first, glass (or metal brazing material) is disposed at the joint between the metal thin plate 12 and the ceramic thin plate 13, and the metal thin plate 12, ceramic thin plate 13 and glass (or glass (or The metal brazing material is heated to a predetermined high temperature (for example, 980 ° C., which is higher than the melting point of the glass). At this time, the metal thin plate 12 and the ceramic thin plate 13 extend by an amount corresponding to their respective thermal expansion coefficients.

  The metal thin plate member 12 and the ceramic thin plate member 13 are joined by the glass (or metal brazing material) solidifying when the temperature is lowered from this extended state. Since the amount of shrinkage of the metal thin plate 12 and the amount of shrinkage of the ceramic thin plate 13 are different from each other during this temperature drop, thermal stress is mainly generated at the joint between the two. As a result, the thin metal plate 12 that is relatively easily deformed is deformed more greatly, and the plurality of wrinkle portions 12d are formed in the thin metal plate 12 due to the deformation. It is clear from the change in Young's modulus shown in FIG. 11 that the metal thin plate 12 (for example, SUS430) is more easily deformed in the high temperature region than the ceramic thin plate 13 (for example, zirconia).

  Therefore, when a device composed of the thin metal plate 12 and the ceramic thin plate 13 having a plurality of wrinkle portions 12d formed in this manner is heated from room temperature, the thermal stress generated along with the temperature rise is the wrinkle portion 12d. It is alleviated by part of the growth. That is, the thin metal plate 12 is deformed so as to return to a heated state before joining. As a result, even if the temperature rise and fall of the device is repeated, excessive thermal stress is not repeatedly applied to the joint portion and / or the ceramic thin plate member 13, so that the durability of the device becomes extremely high. As is apparent from FIG. 11, the metal thin plate 12 is substantially deformed when the device including the metal thin plate 12 and the ceramic thin plate 13 is heated to 400 ° C. or higher. (A part of the wrinkle portion 12d extends).

  As described above, the support member 11 and the metal thin plate body 12 to which the ceramic thin plate body 13 is bonded (held) are alternately laminated (see FIGS. 1 and 2). More specifically, the outer peripheral portion of the thin metal plate 12 (the outer peripheral portion including the slits 12a and 12b) is an upper frame of one support member 11 (for convenience, this is referred to as “first support member”). The upper surface of the body portion 11b and another support member 11 (another support member having the same shape as the first support member and disposed above the first support member. Between the lower frame body portion 11c and the lower surface of the lower frame body portion 11c. At this time, the thin metal plate 12 is fixed to the support member 11 (first support member and second support member) via glass. Accordingly, the thin metal plate 12 and the support member 11 are maintained in an insulated state. As an alternative, after forming an insulating film such as a silica film and an alumina film on the surface of the metal thin plate 12 by sputtering, for example, the metal thin plate 12 and the support member 11 may be joined with a metal brazing material.

  In the fuel cell 10 configured as described above, the fuel electrode layer 13b of one ceramic thin plate member 13 is disposed so as to face the lower surface of the flat portion 11a of the second support member, and the air electrode of the ceramic thin plate member 13 is disposed. The layer 13c is disposed so as to face the upper surface of the flat portion 11a of the first support member via the metal thin plate member 12 (through hole 12c). The through holes 12c are provided in the thin metal plate 12 so that the thin metal plate 12 does not obstruct the supply of air (oxygen) to the air electrode layer 13c, and the portions other than the through holes 12c of the thin metal plate 12 are provided. This is to collect electrons more efficiently. That is, the central portion of the thin metal plate 12 constitutes current collecting means.

  As shown by the solid line arrows in FIGS. 1 and 2, the air flows through the slits 11 c 1 of the respective support members 11 and above the flat portion 11 a of the support members. Therefore, an air flow path CAir is formed between the upper surface of the flat portion 11a of each support member and the lower surface of the thin metal plate 12. As a result, the air electrode layer 13c is always exposed to fresh air (oxygen) through the through hole 12c. On the other hand, the fuel flows through the slit 11b1 of each support member 11 and below the flat portion 11a of the support member. Therefore, the fuel flow path CFuel is formed between the lower surface of the flat portion 11 a of each support member and the upper surface of the ceramic thin plate member 13. As a result, new fuel is supplied to the fuel electrode layer 13b. The fuel cell 10 generates power according to the above-described reaction formula (1) and reaction formula (2).

(Examination to prevent deformation of ceramic thin plate)
Next, various experimental results (results of the first experiment and the second experiment) performed in order to appropriately form the wrinkle portion 12d in the vicinity of the outer peripheral portion of the thin metal plate 12 will be described. In these experiments, the support member 11 having a square planar shape, and the metal thin plate 12 and the ceramic thin plate 13 each having a square planar shape shown in FIG. 12 were used. The width W of the joint between the metal thin plate 12 and the ceramic thin plate 13 was 1 mm. The width a of the region where the metal thin plate 12 can be deformed was 2 mm. Glass was used for joining the metal sheet 12 and the ceramic sheet 13. At this time, the metal thin plate 12, the ceramic thin plate 13 and the bonding glass are heated to 980 ° C. in the air atmosphere and left in that state for 30 minutes, after which they are cooled to lower the metal thin plate 12. And the ceramic thin plate 13 were joined. The glass used for bonding is a material mainly composed of Li ₂ O, SiO ₂ and Al ₂ O ₃ , its glass transition temperature is 560 ° C., and its thermal expansion coefficient is 10.5 ppm / K.

A first experimental result for examining an optimum value of the thickness (plate thickness) of the ceramic thin plate member 13 will be described.

From this first experiment, the following conclusions were drawn.
(1) A single ceramic thin plate 13 has the same thickness as the single ceramic thin plate 13 "a ceramic thin plate made of a laminate in which a fuel electrode layer 13b and an air electrode layer 13c are provided on a solid electrolyte layer 13a". It has a higher Young's modulus (high rigidity) and is difficult to deform. Specifically, the Young's modulus of zirconia, which is a ceramic, is about 200 GPa, whereas the Young's modulus of the fuel electrode layer and the air electrode layer is 50-100 GPa. Therefore, it is considered that the Young's modulus of the entire laminate is lower depending on the thickness of each layer than the Young's modulus of zirconia alone. As a result, the deformation amount of the metal thin plate body 12 in the device in which the single ceramic thin plate body 13 is bonded to the metal thin plate body 12 is larger than the deformation amount of the metal thin plate body 12 in the device in which the laminated body is bonded to the metal thin plate body 12. Is also getting bigger. However, when the thickness of the ceramic thin plate body 13 is smaller than 10 μm, cracks occurred in the ceramic thin plate body 13. This is presumed to be a result of the fact that even if the ceramic thin plate 13 is a single piece of ceramic, the thickness is excessively thin, so that the strength is reduced and the ceramic stress plate cannot withstand the above-described thermal stress.
(2) When the thickness of the ceramic thin plate 13 was 20 μm or more and 200 μm or less, the ceramic thin plate 13 maintained a normal shape, and the wrinkle portion 12d was also appropriately formed.
(3) When the thickness of the ceramic thin plate 13 was 250 μm or more, the metal thin plate 12 was greatly deformed, and an excessive wrinkle portion (an excessive wrinkle portion) was formed in the metal thin plate 12.

Next, Table 2 shows the second experimental result for examining the optimum value of the thickness (plate thickness) of the thin metal plate 12. The thickness of the ceramic thin plate 13 was constant (30 μm).

From this second experiment, the following conclusions were drawn.
(3) When the thickness of the metal thin plate 12 is 20 μm or more, the metal thin plate 12 and the ceramic thin plate 13 are satisfactorily bonded, and the shape of the metal thin plate 12 is also preferable. Although not shown in Table 2, when the thickness of the metal thin plate 12 is 10 μm, it is difficult to handle the metal thin plate 12 at the time of manufacture, and the ceramic thin plate 13 cannot be joined to the metal thin plate 12. It was. Furthermore, in those that could be joined, poor joining occurred, and the sealing property between the metal thin plate 12 and the ceramic thin plate 13 was not good. This is because the strength of the metal thin plate 12 having a thickness of 10 μm or less decreases as the self-supporting becomes difficult, so that the joint surface of the metal thin plate 12 with the ceramic thin plate 13 is not kept smooth. It is estimated that a defect occurred.

(4) If the thickness of the metal thin plate 12 is 100 μm or more, the height of the wrinkled portion of the metal thin plate 12 becomes too small, and it becomes difficult to suppress deformation of the ceramic thin plate 13 due to thermal stress. This is considered to be because the rigidity of the metal thin plate 12 is excessive because the metal thin plate 12 is thick.

Furthermore, the following knowledge was obtained through the first and second experiments.
(5) In the metal thin plate 12 in which the good wrinkle portion 12d (the wrinkle portion 12d capable of suppressing deformation due to the thermal stress of the ceramic thin plate 13) is formed, the height of the wrinkle portion 12d is 70 μm ( More preferably, it was 65 μm or less. Furthermore, when the height of the wrinkle portion 12d is 10 μm or less, the effect of suppressing the deformation of the ceramic thin plate member 13 described above could not be confirmed.
(6) In the metal thin plate 12 having the good wrinkle portion 12d formed, a position 0.5 mm away from the end of the ceramic thin plate 13 toward the outer periphery of the metal thin plate 12 (that is, the ceramic thin plate 13 or “A distance L between the tops 12d1 and 12d1 of the two adjacent wrinkle portions (see FIG. 10) measured at a position 0.5 mm away from the outer peripheral edge along the normal direction of the outer peripheral edge of the joint. ”Was 1 mm or more and 4 mm or less.
(7) In the thin metal plate 12 with the good wrinkle portion 12d formed, the direction in which the top of the wrinkle portion 12d extends (the direction of the ridge portion) is the side of the ceramic thin plate body 13 (tangent to the outer peripheral edge of the ceramic thin plate body) ) At an angle of 45 degrees or more and 135 degrees or less (except for the joint, the ceramic thin plate body 13 and the region near the corner of the metal thin plate body 12).

(Effect confirmation)
The inventor further performed the following test in order to confirm the effect of the embodiment.
<Effect confirmation test 1>
Zirconia (fuel electrode layer thickness = 5 μm, zirconia thickness = 20 μm, air electrode layer thickness = 5 μm) in which a fuel electrode layer and an air electrode layer are respectively formed on the front and back surfaces of a ceramic thin plate body is a support member 11 made of SUS430 A fuel cell directly sandwiched without using the metal thin plate 12 (interconnector) was manufactured as a comparative example. As a result, the ceramic thin plate body was subjected to various stresses during production, and its central portion was deformed into a convex shape. The amount of deformation was 350 μm to 400 μm. The planar shape of the ceramic thin plate was a square, and the shape of the support member was the same as that of the support member 11 shown in FIG. 16 described later (the planar shape was a square).

  On the other hand, the fuel cell 10 was created using a device to which the present invention was applied (a thin metal plate having the above-described wrinkle portion). The planar shape of the thin metal plate 12 in this production example was the above-described square as shown in FIG. As the ceramic thin plate, a ceramic thin plate 13-1 made of zirconia having a thickness of 30 μm and having a circular planar shape shown in FIG. 13 was used. The support member was the same as that of the comparative example described above. In the fuel cell manufactured in this manner, it was confirmed that the ceramic thin plate 13-1 maintained a substantially flat shape. From the above, it has been confirmed that in the device to which the present invention is applied, the ceramic thin plate 13 is hardly deformed.

<Effect confirmation test 2>
The fuel cell of the above comparative example was heated from room temperature to 800 ° C. for 1 minute with an infrared lamp and then heated to room temperature for 1 minute. As a result, cracks occurred in the ceramic thin plate.

  On the other hand, what prepared the device of embodiment mentioned above (the square metal thin plate body 12 and the square ceramic thin plate body 13) to the support member similar to a comparative example was prepared, and this was the same conditions as the said comparative example. The temperature was raised and lowered. As a result, no cracks were observed in the ceramic thin plate 13 even after 10 cycles of temperature increase and decrease. That is, the ceramic thin plate 13 was not damaged and maintained its normal shape. Further, a similar temperature increase / decrease test was performed on a device using the metal thin plate 12 having a square planar shape and the ceramic thin plate 13-1 having a circular planar shape as shown in FIG. As a result, no cracks were found in the ceramic thin plate 13-1 even after 10 cycles of temperature increase and decrease. From this, it was confirmed that the device to which the present invention is applied has excellent durability even when used in a usage environment such as the fuel cell 10 that repeatedly increases and decreases temperature. .

  The device according to the embodiment of the present invention has been described above. According to this, even if a thermal stress is generated in the ceramic thin plate member 13 and / or the joint portion, the stress is relieved by the wrinkle portion 12 d of the metal thin plate member 12. Furthermore, the wrinkle portion 12d also functions as a rib that prevents the ceramic thin plate body 13d from moving or deforming (curving) in a direction orthogonal to the plane portion. As a result, since deformation in the direction perpendicular to the plane of the ceramic thin plate member 13 is suppressed, the fuel cell 10 that can stably exhibit the desired performance is provided.

  In addition, this invention is not limited to said each embodiment, A various modification can be employ | adopted within the scope of the present invention. For example, the outer peripheral shape in a plan view of the ceramic thin plate body may be an ellipse, an oval, a polygon such as a square or a hexagon, and a shape obtained by adding an arc to each corner of the polygon, in addition to the above-described square and circle. Any shape may be used.

  In addition, as shown in FIG. 14, a support member 11-1 having a circular shape in plan view may be used instead of the support member 11. Furthermore, the outer peripheral shape of the thin metal plate in plan view is a polygon such as a square, a circle, an ellipse, an oval, a hexagon, an octagon, etc., regardless of the shape of the outer periphery of the ceramic thin plate. And arbitrary shapes, such as the shape which gave the circular arc to each corner | angular part of a polygon, may be sufficient. The support member 11 should just have the planar shape according to the planar shape of the metal thin plate body.

  Moreover, the metal thin plate body 12 may be provided with one large through hole in a region inside the joint portion between the ceramic thin plate body 13 and the metal thin plate body 12. In this case, the metal thin plate 12 can also be called a metal thin plate frame. Further, a member different from the metal thin plate member 12 (preferably a conductive member such as metal) and having a mesh structure or a member having a plurality of through holes is disposed in the one through hole portion, You may comprise so that the member may be hold | maintained at the metal thin plate body 12. FIG.

  Furthermore, as shown in FIG. 15, a plurality of protrusions 11 d may be formed on the upper surface and / or the lower surface of the flat portion 11 a of the support member 11. The protruding portion 11d is configured to stand upward from the flat surface portion 11a so as to contact the lower surface of the thin metal plate body 12. Alternatively, the protruding portion 11d is configured to stand downward from the flat surface portion 11a so as to contact the upper surface of the ceramic thin plate member 13. The protrusion 11d functions as a current collecting terminal (current collecting means) that collects electrons.

  Further, as shown in FIG. 15, the metal mesh 20 may be inserted between the lower surface of the flat portion 11 a and the upper surface of the ceramic thin plate body 13, and the upper surface of the flat portion 11 a and the lower surface of the metal thin plate body 12 You may insert between. The metal mesh 20 is also a current collecting means that exhibits a current collecting function. Furthermore, the present invention can be applied to the support member 11, the metal thin plate body 12, and the ceramic thin plate body 13 which are deformed as shown in FIG. In addition, the ceramic thin plate member 13 may have its fuel electrode layer 13 b bonded to the surface of the metal thin plate member 12, and the air electrode layer 13 c may be bonded to the surface of the metal thin plate member 12.

  The fuel electrode layer 13b can be composed of platinum, platinum-zirconia cermet, platinum-cerium oxide cermet, ruthenium, ruthenium-zirconia cermet, or the like.

  Furthermore, the air electrode layer 13c can be composed of, for example, a perovskite complex oxide containing lanthanum (for example, lanthanum cobaltite in addition to the above-mentioned lanthanum manganite). Lanthanum cobaltite and lanthanum manganite may be doped with strontium, calcium, chromium, cobalt (in the case of lanthanum manganite), iron, nickel, aluminum or the like. Further, palladium, platinum, ruthenium, platinum-zirconia cermet, palladium-zirconia cermet, ruthenium-zirconia cermet, platinum-cerium oxide cermet, palladium-cerium oxide cermet, ruthenium-cerium oxide cermet may be used. Furthermore, although the ceramic thin plate 13 is a three-layer laminate, it may be composed of a ceramic single-layer, and may be a laminate of two layers or four layers or more (for example, four to seven layers). May be.

  In addition, the device of the above embodiment is applied to the fuel cell 10, but may be applied to a sensor, an actuator, or the like. That is, for example, the device according to the present invention may be used in a thermoelectric gas sensor described below.

  The thermoelectric gas sensor 50 whose longitudinal sectional view is shown in FIG. 17 includes a metal base 51, a metal thin plate 52, a glass 53, a ceramic thin plate 54, a thermoelectric film 55, a first electrode 56a, a second electrode 56b, and a protective film. 57 and a catalyst 58 are provided.

  Although the metal base 51 is not particularly limited, it is made of stainless steel (for example, SUS430). The metal base 51 is a frame having a predetermined thickness t1. The outer shape of the metal base 51 in a plan view is a rectangle. In other words, a rectangular through hole 51 a that is smaller than the outer shape of the metal base 51 in a plan view by a certain distance is formed at the center of the metal base 51. The outer shape of the metal base 51 and the through hole 51a in plan view may be other shapes such as a square and a circle.

  Although the metal thin plate 52 is not particularly limited, it is made of stainless steel (for example, SUS430). The thin metal plate 52 is fixed to the upper surface of the metal base 51 by an adhesive (glass or metal brazing material or the like). The metal thin plate 52 is a thin plate having a predetermined thickness t2. The thickness t2 is smaller than the thickness t1. The outer shape of the thin metal plate 52 in plan view is the same rectangle as that of the metal base 51. In the center of the thin metal plate 52, a rectangular through-hole 52a that is smaller than the outer shape of the thin metal plate 52 by a certain distance in plan view is formed. The through hole 52a is smaller than the through hole 51a. Therefore, the thin metal plate 52 is supported and fixed by the metal base 51 on the outer peripheral side, and is free on the inner peripheral side. In addition, the external shape in planar view of the metal thin plate body 52 and the through hole 52a may be other shapes such as a square and a circle according to the external shape in the planar view of the metal base portion 51 and the through hole 51a. A plurality of wrinkle portions 52b similar to the plurality of wrinkle portions 12d shown in FIG. The ridge portion of the wrinkle portion 52b is formed radially so as to have a component in a direction from the center of gravity of the thin metal plate 52 toward the outside thereof.

  The ceramic thin plate 54 is not particularly limited, but is a flat plate (zirconia substrate) made of zirconia. The ceramic thin plate 54 has a thickness equivalent to that of the metal thin plate 52. The outer shape of the ceramic thin plate 54 is a rectangle similar to the outer shape of the metal base 51 and the thin metal plate 52. Each side forming the outer shape of the ceramic thin plate member 54 is located between the side defining the through hole 51a and the side defining the through hole 52a in plan view. In other words, in plan view, the outer peripheral portion of the ceramic thin plate member 54 overlaps the inner peripheral portion of the metal thin plate member 52 by a fixed distance W from the outer edge toward the inside. This overlapped portion is called a junction. The ceramic thin plate member 54 is bonded at its bonding portion by a glass 53 disposed between the upper surface of the metal thin plate member 52 and the lower surface of the ceramic thin plate member 54. Accordingly, the ridge portion of the wrinkle portion 52b of the thin metal plate 52 extends (radially) in a direction having an angle of 45 degrees or more and 135 degrees or less with respect to the tangent to the outer edge of the ceramic thin plate body 54. Note that the outer shape of the ceramic thin plate 54 in a plan view may be other shapes such as a square and a circle according to the outer shapes of the metal base 51 and the metal thin plate 52.

The thermoelectric film 55 is a thin film having a function of converting a temperature difference generated in the thermoelectric film 55 by heat transmitted to the thermoelectric film 55 into a voltage signal by a “thermoelectric conversion effect”. The thermoelectric film 55 is not particularly limited, but is, for example, cobalt oxide (NaCO ₂ O ₄ ). The thermoelectric film 55 is desirably an oxide that exhibits a thermoelectric conversion effect. The thermoelectric film 55 can also be made of SiGe, Bi ₂ Te ₃ and FeSi. Further, the thermoelectric film 55 may be highly functionalized by crystal orientation.

The first electrode 56 a is formed on the upper surface of the ceramic thin plate 54 and the upper surface of the region near one end of the thermoelectric film 55. The first electrode 56a is a thin film made of platinum (or an alloy of platinum and titanium). The first electrode 56 a is electrically connected to the thermoelectric film 55.
The second electrode 56 b is formed on the upper surface of the ceramic thin plate body 54 and the upper surface of the region near the other end of the thermoelectric film 55. The second electrode 56b is a thin film made of platinum (or an alloy of platinum and titanium). The second electrode 56b is electrically connected to the thermoelectric film 55. In other words, the first electrode 56 a and the second electrode 56 b are formed in the vicinity of opposite ends of the thermoelectric film 55 so that the voltage generated in the thermoelectric film 55 can be acquired.

The protective film 57 is not particularly limited, and is made of a silicon oxide film (SiO ₂ ). The protective film 57 covers the portion of the upper surface of the thermoelectric film 55 that is not covered by the “first electrode 56 a and the second electrode 56 b”.

  The catalyst 58 is a film made of a catalyst material that generates a catalytic reaction by contact with a combustible gas and generates heat by the catalytic reaction. In this example, in order to constitute the thermoelectric gas sensor 50 that detects hydrogen, a noble metal-based porous material (for example, platinum) that generates a catalytic reaction with hydrogen is used as the catalyst 58. The material of the catalyst 58 is appropriately selected according to the combustible gas whose concentration is to be detected. The catalyst 58 is formed at a predetermined location immediately above the thermoelectric film 55. More specifically, the catalyst 58 is formed at one location other than the central portion of the thermoelectric film 55 in a plan view and closer to the first electrode 56a than the second electrode 56b.

  In the thermoelectric gas sensor 50 configured as described above, heat generated by the catalytic reaction between the catalyst 58 and the combustible gas (hydrogen in this example) is transmitted to the thermoelectric film 55. As a result, a “temperature difference (temperature distribution)” is generated in the thermoelectric film 55 such that the temperature of the first electrode 56 a is higher than the temperature of the second electrode 56 b. Since the amount of heat generated by the catalyst 58 increases as the concentration of the combustible gas contacting the catalyst 58 increases, the “temperature difference” also increases as the concentration of the combustible gas increases. This temperature difference is converted into a voltage by the thermovoltage conversion effect of the thermoelectric film 55. The voltage converted by the thermal voltage conversion effect of the thermoelectric film 55 increases as the temperature difference of the thermoelectric film 55 increases. As a result, the thermoelectric film 55 generates a larger voltage as the concentration of the combustible gas increases. This voltage is taken out from the first electrode 56a and the second electrode 56b as a detection output of the thermoelectric gas sensor 50.

As described above, in the thermoelectric gas sensor 50, the thermoelectric film 55 is formed on the upper surface of the ceramic thin plate body 54. The lower surface of the ceramic thin plate member 54 is opened through the through hole 52a and the through hole 51a. Therefore, the heat dissipation at the lower surface of the ceramic thin plate member 54 is good, and the ceramic thin plate member 54 does not receive heat from other portions of the thermoelectric gas sensor 50. Further, the ceramic thin plate 54 is made of a zirconia (ZrO ₂ ) substrate. A zirconia substrate has a very low thermal conductivity as compared to silicon nitride (Si ₃ N ₄ ) applied when, for example, a MEMS process is used. That is, the thermal conductivity of Si ₃ N ₄ is 29.3 W / mK, while the thermal conductivity of ZrO ₂ is 1.7 W / mK. From the above, a large temperature difference (a temperature difference that changes sensitively to the combustible gas concentration) according to the combustible gas concentration can be generated inside the thermoelectric film 55. Accordingly, the sensitivity of the thermoelectric gas sensor 50 is increased. Can be significantly improved.

  Further, when the thermoelectric film 55 is made of the above-described oxide material such as cobalt oxide, a film before firing that becomes the thermoelectric film 55 is formed on the plate body before firing that becomes the ceramic thin plate body 54. It is also possible to form the electrode 56a, the second electrode 56b, etc., and fire them simultaneously. Therefore, the reliability of the thermoelectric gas sensor 50 can be improved.

  Thus, the device according to the present invention can be suitably used for the thermoelectric gas sensor 50. A metal brazing material may be used as an alternative to the glass 53 used as the joining member. In this case, it is desirable to form an insulating film such as a silica film and an alumina film on the surface of the metal thin plate 52 by sputtering, for example, and then join the metal thin plate 52 and the ceramic thin plate 54 with a metal brazing material. Further, although the thin metal plate 52 has the wrinkle portion 52b, the wrinkle portion 52b may not be provided depending on the performance required for the thermoelectric gas sensor 50. Furthermore, a heater (for example, a platinum heater) in which insulation from the first electrode 56a and the second electrode 56b is secured is formed on the lower surface of the catalyst 58, and the temperature of the catalyst 58 can be maintained at an appropriate activation temperature. desirable.

1 is a partially exploded perspective view of a solid oxide fuel cell to which a device according to an embodiment of the present invention is applied. FIG. 2 is a partial longitudinal sectional view of the fuel cell shown in FIG. 1. It is a top view of the supporting member shown in FIG. It is sectional drawing which cut | disconnected the supporting member in the plane along line 4-4 of FIG. It is sectional drawing which cut | disconnected the supporting member in the plane along 5-5 line of FIG. FIG. 6 is a cross-sectional view of the support member cut along a plane along line 6-6 in FIG. 3. It is a top view of the metal thin plate body and ceramic thin plate body which were shown in FIG. It is sectional drawing of the metal thin plate body and ceramic thin plate body which were shown in FIG. It is a partial expanded sectional view of the metal thin plate body and ceramic thin plate body shown in FIG. The metal thin plate body between the joint portion of the metal thin plate body having the longitudinal direction in the X-axis direction and the ceramic thin plate body and the slit of the metal thin plate body adjacent to the joint portion is formed in a plane along the XZ plane. FIG. It is the graph which showed the Young's modulus with respect to the temperature of zirconia and SUS430. It is a top view of the metal thin plate body and ceramic thin plate body shown in FIG. 1 for demonstrating the content of experiment. It is a top view of the metal thin plate body and ceramic thin plate body which concern on the modification of embodiment of this invention. It is a top view of a support member concerning a modification of an embodiment of the present invention. FIG. 5 is a partial vertical cross-sectional view of a fuel cell that is a modification of the fuel cell shown in FIG. 1 and includes current collecting means. FIG. 5 is a partially exploded perspective view of another solid oxide fuel cell to which a device according to an embodiment of the present invention is applied. 1 is a longitudinal sectional view of a thermoelectric gas sensor to which a device according to an embodiment of the present invention is applied.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... Fuel cell, 11 ... Support member, 11a ... Plane part, 11b ... Upper frame part, 11b1 ... Slit, 11c ... Lower frame part, 11c1 ... Slit, 11d ... Projection part, 12 ... Metal thin plate, 12a ... Slit, 12b ... Slit, 12c ... Through hole, 12d ... Wrinkle part, 12d1 ... Upper ridge part, 12d2 ... Lower ridge part, 13 ... Ceramic thin plate, 13a ... Solid electrolyte layer, 13b ... Fuel electrode layer, 13c ... Air Electrode layer, 20 ... metal mesh, CAir ... air flow path, Cuel ... fuel flow path, 50 ... thermoelectric gas sensor, 51 ... metal base, 51a ... through hole, 52 ... metal thin plate, 52a ... through hole, 53 Glass, 54 ... Ceramic thin plate, 55 ... Thermoelectric film, 56a ... First electrode, 56b ... Second electrode, 57 ... Protective film, 58 ... Catalyst.

Claims (13)

A ceramic sheet including a fired ceramic sheet;
A metal thin plate made of a metal having an outer shape larger than the outer shape of the ceramic thin plate, and
In a device comprising:
The outer peripheral portion of the ceramic thin plate is joined to the metal thin plate, and the metal thin plate is along the direction from the joint between the ceramic thin plate and the metal thin plate toward the outer peripheral of the metal thin plate. A device in which a plurality of wrinkle portions having a ridge portion having a continuously extending top portion are formed. The device of claim 1, wherein
The device is deformed so that when the temperature of the device is increased, a part of the wrinkle portion extends so that the metal thin plate is returned to a heated state before being joined to the ceramic thin plate. A device characterized by that. The device of claim 2, wherein
The device is configured such that when the temperature of the device is raised to 400 ° C. or higher, the metal thin plate body causes the deformation. The device according to any one of claims 1 to 3,
The said metal thin plate body is equipped with one or several through-holes in the area | region inside the junction part of the said ceramic thin plate body and the said metal thin plate body. The device according to any one of claims 1 to 3,
The ridge portion of the wrinkle portion is a device extending in a direction having an angle of 45 degrees or more and 135 degrees or less with respect to a tangent to the outer peripheral edge of the ceramic thin plate member. The device of claim 5, wherein
The ceramic thin plate has a thickness of 20 μm or more and 200 μm or less,
The thickness of the said metal thin plate body is 20 micrometers or more and 80 micrometers or less. The device of claim 6, wherein
A device in which the height of the wrinkle portion, which is the distance between the upper top portion and the lower top portion of the wrinkle portion, is 10 μm or more and 70 μm or less. The device of claim 7, wherein
A device in which the distance between the tops of two adjacent wrinkle portions measured at a position 0.5 mm away from the end of the ceramic thin plate body toward the outer peripheral portion of the metal thin plate body is 1 mm or more and 4 mm or less. The device according to any one of claims 1 to 8,
A device in which the metal thin plate member and the outer peripheral portion of the ceramic thin plate member are joined together by glass or a metal brazing material. The device according to any one of claims 1 to 8,
The ceramic thin plate body is a device that is a single thin plate body or a laminated body in which a plurality of thin plate bodies are laminated. The device according to any one of claims 1 to 8,
The ceramic thin plate is a laminated body of the ceramic sheet and a sheet made of a material having a coefficient of thermal expansion different from that of the ceramic sheet. The device of claim 11, wherein
The ceramic thin plate is
A solid electrolyte layer as the ceramic sheet;
A fuel electrode layer as a sheet made of a material having a different coefficient of thermal expansion formed on one surface of the solid electrolyte layer;
An air electrode layer as a sheet made of a material having a different coefficient of thermal expansion formed on the other surface of the solid electrolyte layer;
A device comprising: A device according to claim 12, comprising:
A first support member having a flat part and an upper frame part that is erected toward the upper part of the flat part and a lower frame part that is erected downward of the flat part;
A second support member having a planar part and an upper frame part erected toward the upper part of the planar part and a lower frame part erected to the lower part of the planar part around the planar part;
With
The first support member and the second support member are coaxially arranged on the upper frame portion of the first support member so that the lower frame portion of the second support member faces each other,
The metal thin plate is sandwiched between the upper frame portion of the first support member and the lower frame portion of the second support member, whereby the ceramic thin plate member is placed on the upper surface of the flat portion of the first support member. Are arranged so that the air electrode layers of the ceramic thin plate body are opposed to the lower surface of the flat portion of the second support member,
The upper surface of the flat portion of the first support member, the inner wall surface of the upper frame body portion of the first support member, and the air electrode layer of the thin plate body form an air flow path to which a gas containing oxygen is supplied,
A device in which a fuel flow path for supplying fuel is formed by the lower surface of the flat portion of the second support member, the inner wall surface of the lower frame portion of the second support member, and the fuel electrode layer of the thin plate member.

Images