JP5255327B2 - Reactor - Google Patents

Description

  The present invention relates to a reaction apparatus such as a solid oxide fuel cell (SOFC), and in particular, a thin plate and a supporting member that supports the thin plate are alternately stacked one by one ( Flat plate) relating to a stack structure.

Conventionally, a solid oxide fuel cell having the above-described stack structure is known (see, for example, Patent Document 1). In this case, as a thin plate (also referred to as “single cell”), a solid electrolyte layer made of zirconia, a fuel electrode layer formed on the upper surface of the solid electrolyte layer, and a lower surface of the solid electrolyte layer A fired body formed by laminating the formed air electrode layer may be used. Hereinafter, for each thin plate member, the support members (also referred to as “interconnectors”) adjacent to the upper and lower portions of the thin plate member are also referred to as “upper support member” and “lower support member”, respectively.
JP 2004-342584 A

  About each thin plate body, the peripheral part of a thin plate body is pinched | interposed between the lower surface of the peripheral part of an upper supporting member, and the upper surface of the peripheral part of a lower supporting member, and is located inside the peripheral part of an upper supporting member. A fuel flow path for supplying fuel gas is defined and formed in a space between the lower surface of the planar portion and the upper surface of the fuel electrode layer of the thin plate member, and the planar portion is located on the inner side of the peripheral edge of the lower support member An air flow path through which oxygen-containing gas (air) is supplied can be defined and formed in a space between the upper surface of the thin plate member and the lower surface of the air electrode layer of the thin plate member.

  With such a configuration, fuel is supplied to the fuel channel and the air channel while the thin plate member is heated to the operating temperature of the solid oxide fuel cell (for example, 800 ° C., hereinafter simply referred to as “operating temperature”). By supplying gas and air, respectively, the fuel gas and air come into contact with the upper and lower surfaces of each thin plate member, and as a result, a power generation reaction occurs in each thin plate member.

  By the way, in the solid oxide fuel cell having the above-described stack structure, the fuel gas in the fuel flow channel and the air in the air flow channel are not mixed and leaked to the outside. In order to maintain the shape, generally, for each thin plate member, the peripheral portion of the thin plate member, the peripheral portion of the upper support member, and the peripheral portion of the lower support member are sealed and fixed to each other by a sealing material.

  The support member is generally made of metal, and the thermal expansion coefficient of the support member is often larger than the thermal expansion coefficient of the thin plate member. For example, when the thermal expansion coefficient of the support member is larger than the thermal expansion coefficient of the thin plate body, when the thin plate body is heated from room temperature to the operating temperature, the support member extends more in the direction along the plane direction than the thin plate body. try to. However, as described above, the thin plate member is fixed to the peripheral portion of the upper and lower support members at the peripheral portion thereof by the sealing material. As a result, the thin plate body receives tensile force (thermal stress) in the direction along the plane direction from the upper and lower support members at the peripheral edge portion. Further, even when a temperature difference locally occurs inside the fuel cell, such as when the fuel cell is rapidly activated, the thin plate member can be subjected to thermal stress as described above due to this temperature difference.

  Here, when the fixing by the sealing material is made completely impossible to move relative to each other, the tensile force (thermal stress) received by the thin plate body becomes excessive, and the thin plate body is cracked. obtain. Such a problem is more likely to occur as the thickness of the thin plate member is smaller.

  In view of the above, an object of the present invention is to increase the temperature of a thin plate from a normal temperature to a high operating temperature in a small reactor having a (flat) stack structure in which thin plates and support members are alternately stacked one by one. An object of the present invention is to provide a material that can suppress the occurrence of cracks in the thin plate due to the thermal stress in the case of being applied.

  In order to achieve the above object, a reaction apparatus according to the present invention includes one or more thin plate bodies that perform a chemical reaction at an operating temperature higher than room temperature, and a plurality of support members that support the one or more thin plate bodies. Are alternately stacked one by one. The thermal expansion coefficient of the support member may be larger or smaller than the thermal expansion coefficient of the thin plate member. Here, from the viewpoint of reducing the size of the entire reaction apparatus, the thickness of each thin plate member is preferably 20 μm or more and 500 μm or less, and is preferably uniform over the entire thin plate member.

  Further, for each of the thin plate bodies, the peripheral edge portion of the thin plate body is sandwiched between the lower surface of the peripheral edge portion of the upper support member and the upper surface of the peripheral edge portion of the lower support member. The peripheral portion of the upper support member and the peripheral portion of the lower support member are sealed with each other by a sealing material.

  The characteristic of the reactor according to the present invention is that the material of the sealing material differs depending on the position in the region occupied by the sealing material. That is, the sealing material seals the upper surface of the peripheral portion of the thin plate member and the lower surface of the peripheral portion of the upper support member, and the lower surface of the peripheral portion of the thin plate member and the upper surface of the peripheral portion of the lower support member. 1 seal part, and the 2nd seal part which seals the lower end of the peripheral part of the above-mentioned upper support member, and the upper end of the peripheral part of the above-mentioned lower support member, and at least the above-mentioned thin board object in the above-mentioned 1st seal part The portions contacting the upper and lower surfaces of the peripheral portion are made of glass having a first softening point lower than the operating temperature, and at least the lower end of the peripheral portion of the upper support member and the lower support in the second seal portion The part between the upper end of the peripheral part of a member consists of glass or ceramics which has a 2nd softening point higher than the said 1st softening point.

  Specifically, for example, the sealing material can be configured as follows. That is, the first seal portion and the second seal portion are separated, and the entire first seal portion is made of glass having the first softening point, and the entire second seal portion is the second seal portion. It consists of glass or ceramics having a softening point. The second seal portion is connected to the entry portion entering the space between the lower surface of the peripheral edge portion of the upper support member and the upper surface of the peripheral edge portion of the lower support member, and is connected to the entry portion, and the upper support member A covering portion that covers a side surface of the peripheral edge portion and a side surface of the peripheral edge portion of the lower support member. Alternatively, the entire first seal portion is made of glass having the first softening point, and the entire second seal portion is made of glass or ceramic having the second softening point, and the second seal portion. Is an entry portion that enters a space between the lower surface of the peripheral portion of the upper support member and the upper surface of the peripheral portion of the lower support member, and the side surface of the peripheral portion of the upper support member that is connected to the entry portion. And a covering portion that covers a side surface of the peripheral edge of the lower support member, and the first seal portion is in contact with the entry portion of the second seal portion.

  According to this, the 1st seal part which consists of glass which has the 1st softening point, the peripheral part upper surface of a thin plate body, and the peripheral part lower surface (space between and a boundary part) of an upper support member, and the peripheral part of a thin plate body The function of sealing the lower surface and the upper surface of the peripheral portion of the lower support member (the space between and the boundary portion) is exhibited. Further, when the temperature of the first seal portion is lower than the first softening point, the peripheral portion of the thin plate member and the peripheral portions of the upper and lower support members can be completely fixed so as not to be relatively movable. On the other hand, when the temperature of the first seal portion is equal to or higher than the first softening point, the peripheral portion of the thin plate member moves relative to the peripheral portion of the upper and lower support members by softening the first seal portion. Allow. In addition, the first softening point is lower than the operating temperature of the thin plate member.

  Therefore, the peripheral portion of the thin plate member can be moved relative to the peripheral portion of the upper and lower support members at a stage where the thin plate member (and hence the first seal portion) is heated from room temperature to the operating temperature. As a result, when the thin plate member is heated to the operating temperature, it is possible to prevent the tensile force (thermal stress) received by the thin plate member from the upper and lower support members from being excessive, and the thin plate member is cracked. The occurrence of such problems can be suppressed.

  On the other hand, the second seal portion made of glass or ceramic having the second softening point seals the lower end of the peripheral portion of the upper support member and the upper end (the space, gap) of the peripheral portion of the lower support member. Demonstrate the function to do. The second softening point is higher than the first softening point, for example, the second softening point is higher than the operating temperature. In this case, even when the temperature of the thin plate member is raised to the operating temperature, the second seal portion can completely fix the peripheral portions of the upper and lower support members so that they cannot move relative to each other.

  Further, when the glass constituting the second seal portion has a crystallization temperature (> second softening point), even if the second softening point is lower than the operating temperature, After the second seal part is heated at least once to a temperature higher than the crystallization temperature in the operating state of the reaction apparatus or the like, a part or all of the second seal part is crystallized. As a result, the second seal portion can completely fix the peripheral portions of the upper and lower support members so that they cannot move relative to each other. From the above, the overall shape of the reaction apparatus can be maintained.

  As described above, in the sealing material according to the present invention, the first seal portion has a function of allowing relative movement of the peripheral portion of the thin plate member relative to the peripheral portion of the upper and lower support members in addition to the sealing function. In addition to the sealing function, the second seal part has a function of maintaining the shape of the entire reaction apparatus. Thus, by making the material of the sealing material different depending on the position in the region occupied by the sealing material, the sealing function and the function of maintaining the overall shape of the reaction apparatus are stably exhibited, and the thin plate body is brought to the operating temperature. Generation of cracks in the thin plate member when the temperature is raised can be suppressed.

  In addition, in the (flat plate) stack structure of the reaction apparatus according to the present invention, for example, when the reaction apparatus (for example, a solid oxide fuel cell) is rapidly started, the stacking direction (the thickness of each thin plate body) is set inside the apparatus. A large temperature distribution can occur temporarily in the vertical direction). Even in this case, the thermal stress is released by the softening of the corresponding first seal portion in order from the one where the temperature has reached the first softening point among the plurality of thin plate members. In other words, the thermal stress can be released individually for each thin plate member. Therefore, since accumulation of thermal stress in the stacking direction cannot occur in the stack structure, good durability against thermal stress can be obtained.

  The reaction apparatus according to the present invention is preferably, for example, a solid oxide fuel cell. That is, in this case, each thin plate member is formed by laminating and firing a solid electrolyte layer, a fuel electrode layer formed on the upper surface of the solid electrolyte layer, and an air electrode layer formed on the lower surface of the solid electrolyte layer. In each of the thin plate bodies, the fuel gas is supplied to the space between the lower surface of the flat portion located inside the peripheral edge portion of the upper support member and the upper surface of the fuel electrode layer of the thin plate body. A flow path is defined and formed, and a gas containing oxygen is supplied to a space between the upper surface of the flat portion located inside the peripheral edge portion of the lower support member and the lower surface of the air electrode layer of the thin plate member. An air flow path is defined and formed.

  In the case of a solid oxide fuel cell, the operating temperature is generally 600 ° C. or higher and 900 ° C. or lower. In this case, it is preferable that the first softening point is 400 ° C. or higher and 700 ° C. or lower, and the second softening point is 600 ° C. or higher and 900 ° C. or lower. According to this, it has been found that the occurrence of cracking of the thin plate can be effectively suppressed when the temperature of the thin plate is raised to the operating temperature while the function of maintaining the shape of the entire reactor is stably exerted. did.

  In the reaction apparatus according to the present invention, for each of the thin plate bodies, a space between the lower surface of the flat portion located inside the peripheral edge portion of the upper support member and the upper surface of the thin plate body, and Current collecting that secures electrical connection between the support member and the thin plate member in each of the spaces between the upper surface of the flat portion located on the inner side of the peripheral portion of the lower support member and the lower surface of the thin plate member Each of the current collecting members has elasticity in the stacking direction, and is mounted so as to generate an elastic force in a direction that separates the support member and the thin plate member from each other in the stacking direction. Is preferred.

  The electrical connection between the adjacent supporting member and the thin plate member can be ensured by the interior of the current collecting member. Further, in addition to the softening action of the first seal portion described above, the action of the elastic force that each thin plate member receives from the upper and lower current collecting members respectively causes the rapid reaction of the reaction apparatus (eg, solid oxide fuel cell). It has been found that cracking of the thin plate member is less likely to occur at the time of start-up and the like.

  In this case (particularly, in the case of the above-described solid oxide fuel cell and the thickness of each thin plate member is not less than 20 μm and not more than 500 μm), the elastic coefficient relating to the elasticity of each current collecting member is 0.1 It is preferably ˜8 N / μm.

  According to the study, when the elastic coefficient of each current collecting member is larger than 8 N / μm, the thin plate body is easily cracked at the time of rapid start-up of the reaction apparatus (for example, solid oxide fuel cell). (It will be described later in detail). On the other hand, when the elastic coefficient of each current collecting member is smaller than 0.1 N / μm, it has been found that poor contact is likely to occur at the contact point between the current collecting member and the support member or thin plate (details will be described later). ).

  As described above, when the elastic coefficient of each current collecting member is 0.1 to 8 N / μm, electrical connection between the adjacent support member and the thin plate member can be reliably ensured, and the reaction apparatus (for example, a solid member) When the oxide fuel cell or the like is rapidly started, it is possible to make it difficult for the thin plate to crack.

  Hereinafter, a solid oxide fuel cell (reactor) according to an embodiment of the present invention will be described with reference to the drawings.

(Overall structure of fuel cell)
FIG. 1 is a cutaway perspective view of a solid oxide fuel cell (hereinafter simply referred to as “fuel cell”) 10 which is a device according to an embodiment of the present invention. FIG. 2 is a partially exploded perspective view of the fuel cell 10. The fuel cell 10 is formed by alternately laminating thin plate members 11 and support members 12. That is, the fuel cell 10 has a flat stack structure. The thin plate member 11 is also referred to as a “single cell” of the fuel cell 10. The support member 12 is also referred to as an “interconnector”.

  As shown in an enlarged circle A in FIG. 2, the thin plate member 11 includes an electrolyte layer (solid electrolyte layer) 11a, a fuel electrode layer 11b formed on the upper surface (upper surface), and an electrolyte layer. And an air electrode layer 11c formed on a surface (lower surface) opposite to the fuel electrode layer 11b on 11a. The planar shape of the thin plate member 11 is a square (length of one side = A ′) having sides along the x-axis and y-axis directions orthogonal to each other. The thin plate member 11 is a plate member having a thickness direction in the z-axis direction orthogonal to the x-axis and the y-axis.

  In this example, the electrolyte layer 11a is a dense fired body of YSZ (yttria stabilized zirconia). The fuel electrode layer 11b is a fired body made of Ni—YSZ and is a porous electrode layer. The air electrode layer 11c is a fired body made of LSM (La (Sr) MnO3: lanthanum strontium manganite) -YSZ, and is a porous electrode layer. The average thermal expansion coefficients of the electrolyte layer 11a, the fuel electrode layer 11b, and the air electrode layer 11c from room temperature to 1000 ° C. are approximately 10.8 ppm / K, 12.5 ppm / K, and 11 (10.8) ppm, respectively. / K. The air electrode layer 11c may be a fired body made of LSCF (lanthanum strontium cobalt ferrite). In this case, the average thermal expansion coefficient of the air electrode layer 11c from room temperature to 1000 ° C. is 12 ppm / K.

  The thin plate member 11 includes a pair of cell through holes 11d and 11d. Each cell through hole 11d passes through the electrolyte layer 11a, the fuel electrode layer 11b, and the air electrode layer 11c. The pair of cell through holes 11d and 11d are formed in the vicinity of one side of the thin plate member 11 and in the vicinity of both ends of the side.

  FIG. 3 is a cross-sectional view of the support member 12 taken along the plane including the 1-1 line parallel to the x axis and parallel to the xz plane in FIG. 2.

  As shown in FIGS. 2 and 3, the support member 12 includes a flat surface portion 12 a, an upper frame portion 12 b, and a lower frame portion 12 c. The planar shape of the support member 12 is a square (side length = A, A is slightly larger than A ′) having sides along the x-axis and y-axis directions orthogonal to each other.

  The support member 12 is made of a Ni-based heat-resistant alloy (for example, ferrite-based SUS, Inconel 600, Hastelloy, etc.). For example, in the case of SUS430, which is a ferrite SUS, the average thermal expansion coefficient of the support member 12 from room temperature to 1000 ° C. is approximately 12.5 ppm / K. Therefore, the thermal expansion coefficient of the support member 12 is larger than the average thermal expansion coefficient of the thin plate member 11. Accordingly, when the temperature of the fuel cell 10 changes, a difference in expansion and contraction occurs between the thin plate member 11 and the support member 12.

  The flat surface portion 12a is a thin flat plate having a thickness direction in the z-axis direction. The planar shape of the flat surface portion 12a is a square (length of one side = L (<A)) having sides along the x-axis and y-axis directions.

  The upper frame body portion 12b is a frame body erected upward in the periphery of the flat surface portion 12a (a region near four sides, that is, a region near the outer periphery). The upper frame body portion 12b includes an outer peripheral frame portion 12b1 and a step forming portion 12b2.

  The outer peripheral frame portion 12 b 1 is located on the outermost peripheral side of the support member 12. The shape of the longitudinal section of the outer peripheral frame portion 12b1 (for example, a cross section obtained by cutting the outer peripheral frame portion 12b1 having a longitudinal direction in the y-axis direction along a plane parallel to the xz plane) is a rectangle (or a square).

  The step forming portion 12b2 is a portion that extends from the inner peripheral surface of the outer peripheral frame portion 12b1 toward the center of the support member 12 at one of the four corners of the flat surface portion 12a. The lower surface of the step forming portion 12b2 is connected to the flat portion 12a. The shape of the step forming portion 12b2 in plan view is substantially square. The upper surface (plane) of the step forming portion 12b2 is continuous with the upper surface (plane) of the outer peripheral frame portion 12b1. A through hole TH is formed in the step forming portion 12b2. The through hole TH also penetrates the flat surface portion 12a located below the step forming portion 12b2.

  The lower frame body portion 12c is a frame body erected downward around the flat surface portion 12a (a region near the four sides, that is, a region near the outer periphery). The lower frame part 12c has a symmetrical shape with the upper frame part 12b with respect to the center line CL in the thickness direction of the plane part 12a. Accordingly, the lower frame body portion 12c includes an outer peripheral frame portion 12c1 and a step forming portion 12c2 that have the same shape as the outer peripheral frame portion 12b1 and the step forming portion 12b2, respectively. However, the step forming portion 12c2 is arranged and formed at one corner portion of two corner portions adjacent to the corner portion where the step forming portion 12b2 is formed among the four corner portions of the flat surface portion 12a. .

  4 shows the thin plate body 11 and the pair of support members 12 in a state of supporting (holding) the thin plate body 11 in a plane that includes a 2-2 line parallel to the y axis in FIG. 2 and is parallel to the yz plane. It is the longitudinal cross-sectional view cut | disconnected along. As described above, the fuel cell 10 is formed by alternately laminating the thin plate members 11 and the support members 12.

  Here, of the pair of support members 12, those adjacent to the thin plate member 11 below and above are respectively referred to as a lower support member 121 and an upper support member 122 for convenience. As shown in FIG. 4, the lower support member 121 and the upper support member 122 are coaxial with each other so that the lower frame body portion 12 c of the upper support member 122 faces the upper frame body portion 12 b of the lower support member 121. Placed in.

  The entire periphery of the thin plate member 11 is sandwiched between the upper surface of the upper frame portion 12b (peripheral portion) of the lower support member 121 and the lower surface of the lower frame portion 12c (peripheral portion) of the upper support member 122. Is done. At this time, the thin plate member 11 is disposed so that the air electrode layer 11 c faces the upper surface of the flat portion 12 a of the lower support member 121, and the fuel electrode layer 11 b faces the lower surface of the flat portion 12 a of the upper support member 122. Placed in.

  The entire periphery of the thin plate member 11, the upper frame portion 12 b of the lower support member 121, and the lower frame portion 12 c of the upper support member 122 are sealed with each other by the sealing material 13. The sealing material 13 will be described later.

  The length A of one side of the planar shape (= square) of the support member 12 is 5 mm or more and 200 mm or less in this example. In this example, the length L of one side of the planar shape (= square) of the planar portion 12a of the support member 12 is 4 mm or more and 190 mm or less. The thickness t of the thin plate member 11 is uniform throughout, and is 20 μm or more and 500 μm or less in this example. The thicknesses of the electrolyte layer 11a, the fuel electrode layer 11b, and the air electrode layer 11c are, for example, 1 μm to 50 μm, 5 μm to 500 μm, and 5 μm to 200 μm, respectively.

  As described above, as shown in FIG. 4, the upper surface of the flat portion 12a of the lower support member 121, the inner wall surface of the upper frame body portion 12b (the outer peripheral frame portion 12b1 and the step forming portion 12b2) of the lower support member 121, and the thin plate An air flow path 21 to which a gas containing oxygen is supplied is formed by the lower surface of the air electrode layer 11 c of the body 11. The gas containing oxygen flows into the air flow path 21 through the through hole TH of the upper support member 122 and the cell through hole 11d of the thin plate member 11 as indicated by the dashed arrows in FIG.

  Further, the lower surface of the flat portion 12 a of the upper support member 122, the inner wall surface of the lower frame portion 12 c (the outer peripheral frame portion 12 c 1 and the step forming portion 12 c 2) of the upper support member 122, and the upper surface of the fuel electrode layer 11 b of the thin plate member 11. Thus, a fuel flow path 22 to which a fuel containing hydrogen is supplied is formed. The fuel flows into the fuel flow path 22 through the through hole TH of the lower support member 121 and the cell through hole 11d of the thin plate member 11 as indicated by the solid arrow in FIG.

  As shown in FIG. 4, a current collecting metal mesh (for example, a metal mesh having an embossed structure) is internally provided in the air flow path 21 and the fuel flow path 22. Each metal mesh has elasticity in the stacking direction. In addition, each metal mesh is internally provided so as to generate an elastic force in a direction in which the corresponding support member 12 and the thin plate member 11 are separated from each other in the stacking direction (that is, a preload is generated).

  Thereby, the electrical connection between the lower support member 121 and the thin plate member 11 and the electrical connection between the upper support member 122 and the thin plate member 11 are ensured. In addition, the gas distribution path is regulated by the interior of the metal mesh. As a result, in the air flow path 21 and the fuel flow path 22, the area (flow area) in which the power generation reaction can substantially occur due to the gas flow in a plan view can be expanded. The reaction can occur effectively.

The fuel cell 10 configured as described above includes, for example, a fuel flow path formed between the fuel electrode layer 11b of the thin plate member 11 and the lower surface of the flat surface portion 12a of the support member 12, as shown in FIG. The fuel is supplied to 22 and air is supplied to the air flow path 21 formed between the air electrode layer 11c of the thin plate member 11 and the upper surface of the flat surface portion 12a of the support member 12, and the following is shown. Power generation based on chemical reaction formulas (1) and (2) is performed.
(1/2) · O ₂ +2 ^e− → O ²⁻ (at: air electrode layer 11c) (1)
H ₂ + O ²⁻ → H ₂ O + 2 ^e− (in the fuel electrode layer 11b) (2)

  Since the fuel cell (SOFC) 10 generates power using the oxygen conductivity of the solid electrolyte layer 11a, the operating temperature of the fuel cell 10 is generally at least 600 ° C. or higher. For this reason, the fuel cell 10 has an external heating mechanism (for example, a resistance heater type heating mechanism or a heating mechanism that uses heat obtained by burning fuel gas) from normal temperature to an operating temperature (for example, 800 ° C.). ) Is used in a heated state.

(Sealing material 13)
Next, the sealing material 13 will be described. 6 shows the thin plate member 11 and the pair of support members 12 in a state of supporting (holding) the thin plate member 11 at room temperature, including a 3-3 line parallel to the x axis in FIG. 2 and parallel to the xz plane. It is a schematic diagram of the longitudinal cross-section cut | disconnected along the flat plane. A line 3-3 is a line passing through the center of the planar shape (= square) of the support member 12 (= center of the planar shape (= square) of the thin plate member 11). In FIG. 6, in order to make the shape of the sealing material 13 easy to see, the shape of the sealing material 13 (particularly the thickness) is exaggerated. Moreover, in FIG. 6, the description of the above metal mesh is omitted.

  As shown in FIG. 6, the sealing material 13 includes a space (boundary portion) between the upper surface of the peripheral portion of the thin plate member 11 and the lower surface of the lower frame portion 12 c of the upper support member 122, and the peripheral portion of the thin plate member 11. 1st seal | sticker part 13a which seals the space (boundary part) between the lower surface of a part and the upper surface of the upper frame part 12b of the lower support member 121, respectively. Hereinafter, these spaces are also referred to as “first spaces”.

  The sealing material 13 is a space between the lower end (lower end of the side surface) of the lower frame body portion 12 c of the upper support member 122 and the upper end (upper end of the side surface) of the upper frame body portion 12 b of the lower support member 121. It has the 2nd seal part 13b separated from the 1st seal part 13a which seals (gap). Hereinafter, this space is also referred to as “second space”. Specifically, the second seal portion 13b includes an entry portion 13b1 that enters a space between the lower surface of the lower frame portion 12c of the upper support member 122 and the upper surface of the upper frame portion 12b of the lower support member 121. The cover portion 13b2 is connected to the entry portion 13b1 and covers the (outer) side surface of the lower frame portion 12c of the upper support member 122 and the (outer) side surface of the upper frame portion 12b of the lower support member 121. The covering portion 13b2 is continuous over the entire side surface of the fuel cell 10 having a stack structure.

  The 1st seal | sticker part 13a consists of glass which has the 1st softening point whose whole is lower than the said operating temperature. The second seal portion 13b includes a crystalline material such as glass or ceramics (specifically, crystallized glass, glass ceramics, etc.) having a softening point (= second softening point) higher than the first softening point. Material, amorphous and crystalline may be mixed). The first and second softening points will be described later.

  As described above, the first seal portion 13a exhibits a function of sealing the first space. In addition, when the temperature of the fuel cell 10 (specifically, the temperature of the first seal portion 13a) is lower than the first softening point, the first seal portion 13a and the upper support member 122 The lower frame body portion 12c and the upper frame body portion 12b of the lower support member 121 (hereinafter also referred to as “a pair of frame body portions”) are fixed so as not to be relatively movable.

  On the other hand, when the temperature of the fuel cell 10 (specifically, the temperature of the first seal portion 13a) is equal to or higher than the first softening point, the first seal portion 13a is caused by the softening of the first seal portion 13a. The peripheral portion of the thin plate member 11 is allowed to move relative to the “pair of frame portions”. That is, the peripheral portion of the thin plate member 11 can be moved relative to the “pair of frame portions” while the fuel cell 10 (and hence the first seal portion 13a) is being heated from the normal temperature to the operating temperature.

  As described above, the thermal expansion coefficient of the support member 12 is larger than the average thermal expansion coefficient of the thin plate member 11. Therefore, as the fuel cell 10 is heated from normal temperature to the operating temperature, the support member 12 tends to extend more than the thin plate member 11 in the direction along the plane direction. Here, assuming that the peripheral portion of the thin plate member 11 continues to be fixed to the “pair of frame portions” so as not to be relatively movable, the thin plate member 11 extends from the “pair of frame portions” in the planar direction at the peripheral portion. There is a possibility of receiving an excessive tensile force (thermal stress) in the direction along the direction. Further, even when a temperature difference locally occurs inside the fuel cell 10 such as when the fuel cell 10 is rapidly activated, the thin plate member 11 can receive the same thermal stress as described above due to this temperature difference.

  On the other hand, in this example, the peripheral portion of the thin plate member 11 can move relative to the “pair of frame portions” toward the center in the middle of the temperature of the fuel cell 10 reaching the operating temperature. (See black arrow in FIG. 6). Therefore, when the temperature of the fuel cell 10 is raised to the operating temperature, it can be suppressed that the tensile force (thermal stress) received by the thin plate member 11 from the “pair of frame portions” is excessive. As a result, the occurrence of problems such as the occurrence of cracks due to thermal stress in the thin plate member 11 can be suppressed.

  On the other hand, the 2nd seal | sticker part 13b exhibits the function to seal the said 2nd space. Further, when the second softening point is higher than the operating temperature, the second seal portion 13b does not soften between the normal temperature and the operating temperature. Further, when the glass constituting the second seal portion 13b has a crystallization temperature (> second softening point), the second seal portion 13b has a crystallization temperature even when the second softening point is lower than the operating temperature. After the temperature is raised at least once to a higher temperature, part or all of the second seal portion 13b is crystallized. Therefore, even if the temperature of the fuel cell 10 reaches the operating temperature, the second seal portion 13b can completely fix the “pair of frame portions” so as not to move relative to each other. That is, the overall shape of the fuel cell 10 (the shape having a stack structure) can be maintained.

  As described above, in the sealing material 13, the first seal portion 13 a has a function of allowing relative movement of the peripheral portion of the thin plate member with respect to the “pair of frame portions” in addition to the sealing function of the first space. . The second seal portion 13b has a function of maintaining the shape of the entire fuel cell 10 in addition to the sealing function of the second space.

  Thus, the material of glass changes with the position in the area | region which the sealing material 13 which consists of glass occupies. As a result, the sealing function (specifically, the function of preventing mixing of the fuel gas in the fuel flow path 22 and the air in the air flow path 21 and leakage to the outside) and the overall shape of the fuel cell 10 are maintained. The generation of cracks in the thin plate member 11 when the temperature of the fuel cell 10 is raised to the operating temperature can be suppressed while the function to perform is stably exhibited.

  Next, a preferable relationship among the operating temperature of the fuel cell 10, the first softening point, and the second softening point will be described. When the operating temperature of the fuel cell 10 is 600 ° C. or higher and 900 ° C. or lower, the first softening point is preferably 400 ° C. or higher and 700 ° C. or lower, and the second softening point is preferably 600 ° C. or higher and 900 ° C. or lower. According to this, the generation of cracks in the thin plate member 11 when the temperature of the fuel cell 10 is raised to the operating temperature can be effectively suppressed while the function of maintaining the shape of the entire fuel cell 10 is stably exhibited. It has been found.

  Tables 1 and 2 show the results of tests confirming these. In these tests, the thin plate has a square shape with a side length of 30 mm in plan view, an electrolyte layer made of 8YSZ (thickness: 3 μm), and a fuel electrode layer made of NiO-8YSZ (thickness). : 150 μm), and a fuel electrode support type (support substrate is the fuel electrode layer) in which an air electrode layer (thickness: 15 μm) made of LSCF was laminated. Then, a three-layer stack was prepared using this thin plate, and a test was performed using this three-layer stack.

  Table 1 shows a test in which the temperature of the fuel cell 10 is rapidly raised from room temperature to 800 ° C., which is its operating temperature, in 10 minutes. The first softening point is obtained by sequentially changing the components of the glass constituting the first seal portion 13a. The result when it is repeated while changing is shown. The decrease in the output of the stack is evaluated by measuring the electromotive force of each thin plate while keeping the current constant at a predetermined value, and whether the thin plate is damaged is measured by the balance of the gas flow rate to the stack. It was evaluated by doing.

  As shown in Table 1, when the first softening point was less than 400 ° C., the scattering (poisoning) of the glass component constituting the first seal portion 13a to the thin plate member 11 became significant. As a result, the area that can contribute to the reaction on the surface of the thin plate member 11 is reduced, so that the output of the fuel cell 10 is greatly reduced. In this experiment, in order to lower the first softening point, the blending ratio of PbO having a low melting point in the material of the first seal portion 13a is increased. As a result, it is considered that the poisoning of the thin plate member 11 by PbO became remarkable.

  On the other hand, when the first softening point exceeded 700 ° C., damage (crack) due to thermal stress occurred in the thin plate member 11 during the temperature rising process. This is considered to be due to the delay in the start of stress release due to the delay in the softening start timing of the first seal portion 13a.

  On the other hand, when the first softening point is 400 ° C. or more and 700 ° C. or less, the poisoning of the thin plate member 11 is not significant, and the thin plate member 11 can be appropriately relieved of stress so that the thin plate member 11 is not damaged. . From the above, when the operating temperature of the fuel cell 10 is 800 ° C., the first softening point is preferably 400 ° C. or more and 700 ° C. or less.

  Table 2 shows a test in which the temperature of the fuel cell 10 is rapidly raised from room temperature to 800 ° C., which is the operating temperature, using the same three-layer stack as described above, and the materials constituting the second seal portion 13b are sequentially changed. (The second softening point and the crystallization temperature are changed). As a material constituting the second seal portion 13b, a crystallized glass having a softening point higher than the first softening point (one in which a glass phase is crystallized. Although crystalline and amorphous are mixed, In a broad sense, it can be said to be ceramics).

  As shown in Table 2, when the second softening point was less than 600 ° C., the sealing performance of the second seal portion 13b was insufficient. That is, when the flow rate of gas supplied to the fuel cell 10 is increased at an operating temperature of 800 ° C. to increase the pressure difference between the inside and outside of the gas flow path, the seal portion (specifically, the second seal portion 13b) Further, gas leakage occurred from a boundary portion between the side surface of the support member 12 and the covering portion 13b2. In this example, the gas leakage from the seal portion of the second seal portion 13b may occur on the premise that the gas leak has occurred from the seal portion of the first seal portion 13a.

  On the other hand, when the second softening point exceeds 900 ° C., the cover portion 13b2 of the second seal portion 13b is damaged when the temperature of the fuel cell 10 is repeatedly reciprocated between the normal temperature and the operating temperature (= 800 ° C.) ( Cracks) occurred. Thereby, like the case where the 2nd softening point is less than 600 degreeC, the sealing performance of the 2nd seal part 13b became inadequate.

  On the other hand, when the second softening point is 600 ° C. or higher and 900 ° C. or lower, the situation in which the sealing performance of the second seal portion 13b does not occur does not occur, and the stack shape is well maintained. From the above, when the operating temperature of the fuel cell 10 is 800 ° C., the second softening point (which is higher than the first softening point) is preferably 600 ° C. or more and 900 ° C. or less.

  The above two test results show only the case where the operating temperature of the fuel cell 10 is 800 ° C., but the case where the operating temperature of the fuel cell 10 is 600 ° C., 700 ° C., and 900 ° C. However, for the same reason as described above, it is confirmed that “the first softening point is preferably 400 ° C. or higher and 700 ° C. or lower and the second softening point is preferably 600 ° C. or higher and 900 ° C. or lower”. From the above, when the operating temperature of the fuel cell 10 is 600 ° C. or higher and 900 ° C. or lower, the first softening point is 400 ° C. or higher and 700 ° C. or lower, and the second softening point is 600 ° C. or higher and 900 ° C. or lower. It can be said that it is preferable.

  Hereinafter, it adds about the metal mesh mentioned above. So far, the case where the thin plate 11 is not deformed has been described. However, due to the fact that the thin plate member 11 is extremely thin and that the thermal expansion coefficients of the three layers constituting the thin plate member 11 are different, actually, as shown in FIG. The central portion of the thin plate member 11 tends to warp downward (that is, in the direction in which the surface on the fuel electrode layer 11b side becomes concave). The amount of warpage (warpage height) decreases as the temperature of the fuel cell 10 is raised from room temperature (see the black arrow in FIG. 7).

  That is, in the process of raising the temperature from room temperature (that is, in the process of decreasing the amount of warpage), the height in the stacking direction of the metal meshes mounted on the upper and lower sides of the thin plate body 11 decreases the warpage amount of the thin plate body 11. Each changes as you follow. Due to this, the magnitude of the load (see the white arrow in FIG. 7) received by the thin plate member 11 from the contact portion with the upper and lower metal meshes changes. In such a situation, the thin plate member 11 is more cracked when the fuel cell 10 is rapidly started, etc., when the metal mesh is installed as described above than when the metal mesh is not provided. It turned out to be difficult. This is considered to be due to a synergistic effect of the above-described softening action of the first seal portion 13a and the elastic force change action that each thin plate member 11 receives from the upper and lower metal meshes.

  Next, a preferable range of the elastic coefficient in the stacking direction of the metal mesh described above (the rate of change in elastic force with respect to the change in the height of the metal mesh in the stacking direction in the elastic region) will be described. In the fuel cell 10 described above (when the thickness of the thin plate member 11 is 20 μm or more and 500 μm or less), the elastic modulus of the metal mesh is preferably 0.1 to 8 N / μm. According to this, the electrical connection between the adjacent support member 12 and the thin plate body 11 can be ensured reliably, and cracking of the thin plate body 11 is less likely to occur at the time of rapid start-up of the fuel cell 10. found.

  The results of tests that confirmed these are shown in Table 3. This test was also performed using the same three-layer stack as described above. The elastic modulus of the metal mesh can be arbitrarily adjusted according to the mesh specifications (for example, the wire diameter of the mesh material, the shape of the embossed portion, the arrangement pitch of the embossed portion, etc.). The assembly of the three-layer stack described above was performed in a state where the metal mesh provided with the shape was joined to the support member side (by diffusion bonding, spot welding, or the like).

  Table 3 shows the results when the test of rapidly raising the temperature of the fuel cell 10 from normal temperature to 800 ° C., which is its operating temperature, in 5 minutes is repeated while changing the elastic modulus of the metal mesh. . The elastic modulus of the metal mesh was the same on the fuel electrode side and the air electrode side. The elastic modulus of the metal mesh can be individually optimized for the fuel side and the air side.

  As shown in Table 3, it was found that when the elastic modulus of the metal mesh is larger than 8 N / μm, the thin plate member 11 is easily cracked. This is because when the elastic coefficient is large, the amount of change in the elastic force of the metal mesh in the process of decreasing the amount of warpage increases, and as a result, there is a portion where the stress is locally excessive inside the thin plate member 11. This is considered to be caused by the tendency to occur.

  On the other hand, when the elastic modulus of the metal mesh is smaller than 0.1 N / μm, it has been found that the output density of the fuel cell 10 decreases. This is because when the elastic modulus is small, the preload of the metal mesh is reduced, and as a result, contact failure is likely to occur at the contact portion (contact point) between the metal mesh and the support member 12 or the thin plate member 11. It is considered a thing.

  On the other hand, when the elastic modulus of the metal mesh is 0.1 to 8 N / μm, the output density of the fuel cell 10 does not decrease and the thin plate 11 does not crack. From the above, in the above-described fuel cell 10 (when the thickness of the thin plate member 11 is 20 μm or more and 500 μm or less), the elastic coefficient of the metal mesh is preferably 0.1 to 8 N / μm.

  Next, an example of a method for manufacturing the fuel cell 10 will be briefly described. First, for example, in the case of an electrolyte support type (the support substrate is an electrolyte layer), the thin plate member 11 is printed with a sheet (a layer serving as the fuel electrode layer 11b) on the upper surface of a ceramic sheet (YSZ tape) prepared by the green sheet method. After being formed by the method, it is fired at 1400 ° C. for 1 hour, and further, a sheet (layer that becomes the air electrode layer 11c) is formed on the lower surface of the fired body by the same printing method, and then 1200 ° C. for 1 hour. It is formed by firing.

  In the case of the fuel electrode support type (support substrate is the fuel electrode layer), the thin plate member 11 is formed by laminating a ceramic sheet (YSZ tape) prepared by the green sheet method on the lower surface of the sheet (layer that becomes the fuel electrode layer 11b). And then firing at 1400 ° C. for 1 hour, and further forming a sheet (a layer that becomes the air electrode layer 11c) on the lower surface of the fired body by a printing method and firing at 850 ° C. for 1 hour. It is formed. In this case, the thin plate member 11 is fired at 1400 ° C. for one hour after the ceramic sheet is formed on the lower surface of the sheet (the layer serving as the fuel electrode layer 11b) by a printing method, and further, the sheet is formed on the lower surface of the fired member. It may be formed by firing at 850 ° C. for 1 hour after forming the layer that becomes the air electrode layer 11c by a printing method.

  The support member 12 can be formed by etching, cutting, or the like.

  Next, a glass material that constitutes the first seal portion 13a in the portion (that is, the lower surface of the lower frame portion 12c and the upper surface of the upper frame portion 12b) that sandwiches the thin plate member 11 in the outer peripheral portion of each support member 12 ( (Boric silica glass) is applied by a printing method. Next, the support members 12 and the thin plate members 11 are alternately laminated, and heat treatment (800 ° C./1 hr) is performed to integrate the stack structure. Thereafter, the outer peripheral portion of the stack is reinforced by applying a material constituting the second seal portion 13b (silicic acid borate crystallized glass or the like) and heat-treating (for example, 850 ° C./1 hr). Thereby, the fuel cell 10 is completed.

  As described above, in the solid oxide fuel cell 10 having the stack structure according to the embodiment of the present invention, for each thin plate body 11, the entire circumference of the thin plate body 10 and the “pair of frame body portions” Are sealed together by a sealing material 13 made of glass. In the sealing material 13, the softening point of the first seal portion 13 a is set lower than the operating temperature of the fuel cell 10, and the softening point of the second seal portion 13 b is set higher than the operating temperature of the fuel cell 10. As a result, the sealing function (specifically, the function of preventing mixing of the fuel gas in the fuel flow path 22 and the air in the air flow path 21 and leakage to the outside) and the overall shape of the fuel cell 10 are maintained. The generation of cracks in the thin plate member 11 when the temperature of the fuel cell 10 is raised to the operating temperature can be suppressed while the function to perform is stably exhibited.

  In addition, in the air flow path 21 and the fuel flow path 22, the metal mesh generates an elastic force in a direction in which the corresponding support member 12 and the thin plate body 11 are separated from each other in the stacking direction (that is, the preload is applied). It has been decorated). The elastic modulus in the stacking direction of the metal mesh is set to 0.1 to 8 N / μm. Thereby, the electrical connection between the adjacent support member 12 and the thin plate body 11 can be ensured reliably, and the thin plate body 11 is hardly cracked when the fuel cell 10 is rapidly started.

  In addition, this invention is not limited to the said embodiment, A various modified example is employable within the scope of the present invention. For example, in the above-described embodiment, the second seal portion 13b is formed of glass having a second softening point and a crystallization temperature, but is made of an inorganic substance (that is, ceramic) that does not soften below the operating temperature. It may be configured.

  Moreover, in the said embodiment, although 1st, 2nd seal part 13a, 13b is isolate | separated, as shown in FIG. 8, 1st, 2nd seal part 13a, 13b may be connected. In FIG. 8, in the first seal portion 13 a that seals the “first space”, the portions that come into contact with the upper surface and the lower surface of the peripheral portion of the thin plate member 11 are made of glass having a first softening point. The portion of the lower frame portion 12c that contacts the lower surface of the lower frame portion 12c and the upper surface of the upper frame portion 12b of the lower support member 121 is made of glass having a second softening point. Further, the entry portion 13b1 of the second seal portion 13b made of glass having the second softening point is connected to a portion made of glass having the second softening point in the first seal portion 13a.

  Moreover, in the said embodiment, although the coating | coated part 13b2 of the 2nd seal | sticker part 13b is continuing over the side surface whole region of the fuel cell 10 which has a stack structure, as shown in FIG. 9, the coating | coated part 13b2 is a thin plate body. 11 may be separated.

  Moreover, in the said embodiment, although the thing of a different composition is used as a material of 1st, 2nd seal part 13a, 13b, the material of the same composition type | system | group can also be used. Specifically, by providing a difference in the particle size of the glass in the same composition system, or providing a difference in a minute amount of additive or the like in the same composition system, the degree of progress of crystallization can be made different so that both the seal portions 13a and 13b Different functions.

  For example, a glass material having a large particle size (for example, about 1 μm) is used as the material for the first seal portion 13a, and a glass material having a small particle size (for example, 0.3 μm or less) is used as the material for the second seal portion 13b. Thereby, it is possible to make a difference in the progress of crystallization at the heat treatment temperature (for example, 850 ° C.) for glass bonding during stack assembly. That is, in the first seal portion 13a having a large particle size, crystallization does not proceed completely and a semi-crystalline state in which a part of the amorphous layer remains is maintained, and in the second seal portion 13b having a small particle size, crystallization is performed. Can be completed. Accordingly, the first seal portion 13a in the semi-crystalline state can have a thermal stress buffer function, and the second seal portion 13b that has been crystallized can have a gas seal function.

  As described above, when materials of the same composition system are used as the materials of the first and second seal portions 13a and 13b, when the materials having different composition systems are used, the first is caused by the thermal history during the SOFC operation. The deterioration of the sealing material at the contact portion generated when the second seal portions 13a and 13b come into contact with each other can be suppressed. As a result, as shown in FIG. 10, the first seal portion 13a and the entry portion 13b1 of the second seal portion 13b can be brought into contact in advance.

  In the above embodiment, the fuel electrode layer 11b can be composed of platinum, platinum-zirconia cermet, platinum-cerium oxide cermet, ruthenium, ruthenium-zirconia cermet, or the like.

  The air electrode layer 11c can be made of, for example, a perovskite complex oxide containing lanthanum (for example, lanthanum cobaltite in addition to the lanthanum manganite described above). 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.

  Moreover, in the said embodiment, although the planar shape of the thin plate body 11 and the supporting member 12 is a square, a rectangle, circular, an ellipse, etc. may be sufficient.

  In the above embodiment, a solid oxide fuel cell (SOFC) is employed as the reaction device, but a ceramic reactor, for example, an exhaust gas purification reactor, may be employed.

1 is a cutaway perspective view of a solid oxide fuel cell according to an embodiment of the present invention. FIG. 2 is a partially exploded perspective view of the fuel cell shown in FIG. 1. It is sectional drawing of the supporting member which cut | disconnected the supporting member along the plane parallel to an xz plane while including the 1-1 line | wire shown in FIG. It is the longitudinal cross-sectional view which cut | disconnected the support member in the state which supported the thin plate body shown in FIG. 1 and a thin plate body along the 2-2 plane shown in FIG. 2, and parallel to a yz plane. It is a figure explaining the distribution | circulation of the fuel and air in the fuel cell shown in FIG. FIG. 5 is a schematic view corresponding to FIG. 4 in which the periphery of the seal material of the fuel cell shown in FIG. 1 is exaggerated. It is the figure which showed a mode that the metal mesh built in the fuel flow path and the air flow path gave an elastic force to a thin-plate body. FIG. 5 is a schematic view corresponding to FIG. 4 exaggeratingly showing the periphery of a sealing material of a solid oxide fuel cell according to a modification of the embodiment of the present invention. FIG. 6 is a schematic view corresponding to FIG. 4 exaggeratingly showing the periphery of a sealing material of a solid oxide fuel cell according to another modification of the embodiment of the present invention. FIG. 6 is a schematic view corresponding to FIG. 4 exaggeratingly showing the periphery of a sealing material of a solid oxide fuel cell according to another modification of the embodiment of the present invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... Fuel cell, 11 ... Thin plate body, 11a ... Zirconia solid electrolyte layer, 11b ... Fuel electrode layer, 11c ... Air electrode layer, 12 ... Support member, 12a ... Planar part, 12b ... Upper frame part, 12c ... Lower frame Body part, 13 ... sealing material, 13a ... first sealing part, 13b ... second sealing part, 13b1 ... entry part, 13b2 ... covering part, 21 ... air flow path, 22 ... fuel flow path, 121 ... lower support member, 122. Upper support member

Claims (6)

One or more thin plates that undergo a chemical reaction at an operating temperature higher than room temperature;
A plurality of support members that support the one or more thin plate members;
In the reaction apparatus in which the thin plate member and the support member are alternately stacked one by one,
For each of the thin plate bodies, the peripheral portion of the thin plate member is the lower support of the upper support member that is the support member adjacent to the upper portion of the thin plate member, and the lower support that is the support member adjacent to the lower portion of the thin plate member. The peripheral portion of the thin plate member, the peripheral portion of the upper support member, and the peripheral portion of the lower support member are sealed with each other by a sealing material so as to be sandwiched between the upper surface of the peripheral portion of the member,
The seal material seals the upper surface of the peripheral portion of the thin plate member and the lower surface of the peripheral portion of the upper support member, and the lower surface of the peripheral portion of the thin plate member and the upper surface of the peripheral portion of the lower support member. A second seal portion that seals the lower end of the peripheral portion of the upper support member and the upper end of the peripheral portion of the lower support member,
In the first seal portion, at least portions that contact the upper and lower surfaces of the peripheral edge of the thin plate member are made of glass having a first softening point lower than the operating temperature, and at least the upper support member in the second seal portion. The part between the lower end of the peripheral edge of the lower support member and the upper end of the peripheral edge of the lower support member is a reaction device made of glass or ceramics having a second softening point higher than the first softening point ,
Each thin plate body is formed by laminating and firing a solid electrolyte layer, a fuel electrode layer formed on the upper surface of the solid electrolyte layer, and an air electrode layer formed on the lower surface of the solid electrolyte layer,
For each of the thin plate bodies, a fuel flow path for supplying fuel gas is defined in a space between the lower surface of the flat portion located inside the peripheral edge portion of the upper support member and the upper surface of the fuel electrode layer of the thin plate body. An air flow path in which oxygen-containing gas is supplied to a space formed between the upper surface of the flat portion located inside the peripheral edge portion of the lower support member and the lower surface of the air electrode layer of the thin plate member Is a reactor that functions as a solid oxide fuel cell . The reactor according to claim 1,
The thickness of each said thin-plate body is a reactor which is 20 micrometers or more and 500 micrometers or less. In the reaction apparatus according to claim 1 or 2 ,
The reactor in which the operating temperature is from 600 ° C. to 900 ° C., the first softening point is from 400 ° C. to 700 ° C., and the second softening point is from 600 ° C. to 900 ° C. In the reaction apparatus according to any one of claims 1 to 3 ,
The first seal portion and the second seal portion are separated from each other, and the entire first seal portion is made of glass having the first softening point, and the entire second seal portion is the second softening point. Made of glass or ceramics having
The second seal portion is connected to the entry portion entering the space between the lower surface of the peripheral edge portion of the upper support member and the upper surface of the peripheral edge portion of the lower support member, and is connected to the entry portion, and the upper support member The reaction apparatus which has a coating | coated part which covers the side surface of the peripheral part of this, and the side surface of the peripheral part of the said lower side support member. In the reaction apparatus according to any one of claims 1 to 3 ,
The entire first seal portion is made of glass having the first softening point, and the entire second seal portion is made of glass having the second softening point, or ceramics,
The second seal portion is connected to the entry portion entering the space between the lower surface of the peripheral edge portion of the upper support member and the upper surface of the peripheral edge portion of the lower support member, and is connected to the entry portion, and the upper support member A covering portion that covers a side surface of the peripheral edge portion and a side surface of the peripheral edge portion of the lower support member,
The reaction device in which the first seal portion is in contact with the entry portion of the second seal portion. The reaction apparatus according to any one of claims 1 to 5 ,
About each said thin-plate body, it is located inside the space between the lower surface of the plane part located inside the peripheral part of the said upper support member, and the upper surface of the said thin plate body, and the peripheral part of the said lower support member. In each of the spaces between the upper surface of the flat portion and the lower surface of the thin plate body, a current collecting member that secures electrical connection between the support member and the thin plate body is provided,
Each of the current collecting members has elasticity in the stacking direction, and is provided so as to generate an elastic force in a direction of separating the support member and the thin plate member from each other in the stacking direction,
A reactor having an elasticity coefficient of 0.1 to 8 N / μm for each of the current collecting members.

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