WO2012133765A1 - Organe de liaison pour pile à combustible à oxyde solide, pile à combustible à oxyde solide et module de pile à combustible à oxyde solide - Google Patents

Organe de liaison pour pile à combustible à oxyde solide, pile à combustible à oxyde solide et module de pile à combustible à oxyde solide Download PDF

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WO2012133765A1
WO2012133765A1 PCT/JP2012/058579 JP2012058579W WO2012133765A1 WO 2012133765 A1 WO2012133765 A1 WO 2012133765A1 JP 2012058579 W JP2012058579 W JP 2012058579W WO 2012133765 A1 WO2012133765 A1 WO 2012133765A1
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solid oxide
fuel cell
oxide fuel
layer
bonding material
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PCT/JP2012/058579
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English (en)
Japanese (ja)
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喜樹 植田
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株式会社村田製作所
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a solid oxide fuel cell bonding material, a solid oxide fuel cell, and a solid oxide fuel cell module.
  • fuel cells As a new energy source.
  • the fuel cell include a solid oxide fuel cell (SOFC), a molten carbonate fuel cell, a phosphoric acid fuel cell, and a polymer electrolyte fuel cell.
  • SOFC solid oxide fuel cell
  • molten carbonate fuel cell a molten carbonate fuel cell
  • phosphoric acid fuel cell a phosphoric acid fuel cell
  • polymer electrolyte fuel cell a solid oxide fuel cell
  • solid oxide fuel cells do not necessarily require liquid components, and can be reformed internally when using hydrocarbon fuel. For this reason, research and development on solid oxide fuel cells are actively conducted.
  • a joining material is used for joining a power generation element and a separator.
  • this bonding material for example, the following Patent Document 1 describes a bonding material for a solid oxide fuel cell mainly composed of glass.
  • the joining material described in Patent Document 1 has a large shrinkage when heated to join the members. For this reason, for example, when a through hole for forming a part of the flow path is formed in the bonding material, a crack from the through hole to the outer edge of the bonding material occurs at the time of bonding, and the leak hole May be formed.
  • the present invention has been made in view of such points, and an object thereof is a solid oxide fuel cell bonding material having a through-hole, and a crack extending from the through-hole to the outer edge of the bonding material at the time of bonding. It is an object of the present invention to provide a bonding material for a solid oxide fuel cell that is less likely to cause the problem.
  • the solid oxide fuel cell bonding material according to the present invention is a solid oxide fuel cell bonding material having a through hole. A recess is provided around the through hole.
  • the cross-sectional shape of the through hole is rectangular.
  • the recess is provided around the corner of the through hole.
  • a plurality of recesses are provided along the outer periphery of the through hole.
  • the recess penetrates the solid oxide fuel cell bonding material in the thickness direction.
  • a glass ceramic layer is provided.
  • the glass ceramic layer is provided with through holes and recesses.
  • the glass ceramic layer includes glass ceramics.
  • the solid oxide fuel cell bonding material is laminated on the glass ceramic layer and penetrates the glass ceramic layer. It further includes a constraining layer provided with a through hole communicating with the hole.
  • the solid oxide fuel cell according to the present invention includes a bonding layer formed by firing the solid oxide fuel cell bonding material according to the present invention.
  • the solid oxide fuel cell includes a plurality of power generation cells.
  • the power generation cell has an air electrode and a fuel electrode.
  • the air electrode is arranged on the solid oxide electrolyte layer and one main surface of the solid oxide electrolyte layer.
  • the fuel electrode is disposed on the other main surface of the solid oxide electrolyte layer.
  • an oxidant gas supply manifold and a fuel gas supply manifold are formed in the power generation cell.
  • the oxidant gas supply manifold is for supplying oxidant gas to the air electrode.
  • the fuel gas supply manifold is for supplying fuel gas to the fuel electrode.
  • Adjacent power generation cells are joined by a joining layer.
  • the joining layer has a through hole that connects the oxidant gas supply manifolds of the adjacent power generation cells and a through hole that connects the fuel gas supply manifolds of the adjacent power generation cells.
  • the void ratio in the region where the concave portion of the bonding material for the solid oxide fuel cell is provided in the joining layer is provided with the concave portion and the through hole. It is larger than the porosity in the region that was not formed.
  • the bonding layer includes at least air bubbles, concave portions, and through holes in the region where the concave portion of the solid oxide fuel cell bonding material is provided. Have one.
  • the solid oxide fuel cell module according to the present invention includes a bonding layer obtained by firing the solid oxide fuel cell bonding material according to the present invention.
  • the solid oxide fuel cell module includes a fuel cell.
  • the fuel cell includes a plurality of power generation cells.
  • the power generation cell has an air electrode and a fuel electrode.
  • the air electrode is arranged on the solid oxide electrolyte layer and one main surface of the solid oxide electrolyte layer.
  • the fuel electrode is disposed on the other main surface of the solid oxide electrolyte layer.
  • an oxidant gas supply manifold and a fuel gas supply manifold are formed in the power generation cell.
  • the oxidant gas supply manifold is for supplying oxidant gas to the air electrode.
  • the fuel gas supply manifold is for supplying fuel gas to the fuel electrode.
  • Adjacent power generation cells are joined by a joining layer.
  • the joining layer has a through hole that connects the oxidant gas supply manifolds of the adjacent power generation cells and a through hole that connects the fuel gas supply manifolds of the adjacent power generation cells.
  • the solid oxide fuel cell module includes a fuel cell and a casing.
  • the fuel cell has an air electrode and a fuel electrode.
  • the air electrode is arranged on the solid oxide electrolyte layer and one main surface of the solid oxide electrolyte layer.
  • the fuel electrode is disposed on the other main surface of the solid oxide electrolyte layer.
  • the fuel cell is formed with an oxidant gas supply manifold and a fuel gas supply manifold.
  • the oxidant gas supply manifold is for supplying oxidant gas to the air electrode.
  • the fuel gas supply manifold is for supplying fuel gas to the fuel electrode.
  • the casing is a casing for storing the fuel cell, and has a first opening to which the oxidant gas supply manifold is connected and a second opening to which the fuel gas supply manifold is connected.
  • the fuel cell and the casing are joined by a joining layer.
  • the bonding layer has a through hole connecting the oxidant gas supply manifold and the first opening, and a through hole connecting the fuel gas supply manifold and the second opening.
  • the void ratio in the region where the concave portion of the bonding material for the solid oxide fuel cell is provided in the bonding layer includes the concave portion and the through hole. It is larger than the porosity in the area that was not provided.
  • the bonding layer includes bubbles, concave portions, and through holes in the region where the concave portion of the solid oxide fuel cell bonding material is provided.
  • a sheet-shaped solid oxide fuel cell bonding material having a through-hole, and a solid oxide fuel cell bonding that hardly cracks from the through-hole to the outer edge of the bonding material at the time of bonding. Material can be provided.
  • FIG. 1 is a schematic perspective view of a solid oxide fuel cell bonding material according to a first embodiment.
  • FIG. 2 is a schematic perspective view of a solid oxide fuel cell bonding material according to a second embodiment.
  • FIG. 3 is a schematic perspective view of a solid oxide fuel cell bonding material according to a third embodiment.
  • FIG. 4 is a schematic perspective view of a solid oxide fuel cell bonding material according to a fourth embodiment.
  • FIG. 5 is a schematic perspective view of a solid oxide fuel cell bonding material according to a fifth embodiment.
  • FIG. 6 is a schematic side view of a solid oxide fuel cell module according to a sixth embodiment.
  • FIG. 7 is a schematic exploded perspective view of the power generation cell according to the sixth embodiment.
  • FIG. 1 is a schematic perspective view of a solid oxide fuel cell bonding material according to a first embodiment.
  • FIG. 2 is a schematic perspective view of a solid oxide fuel cell bonding material according to a second embodiment.
  • FIG. 3 is a schematic perspective
  • FIG. 8 is a schematic exploded perspective view of a fuel cell according to the sixth embodiment.
  • FIG. 9 is a schematic exploded perspective view of a part of the fuel cell module according to the sixth embodiment.
  • FIG. 10 is a schematic cross-sectional view of a solid oxide fuel cell bonding material according to a seventh embodiment.
  • FIG. 11 is a schematic cross-sectional view of a solid oxide fuel cell bonding material according to an eighth embodiment.
  • FIG. 12 is a schematic cross-sectional view of a solid oxide fuel cell bonding material according to a ninth embodiment.
  • FIG. 13 is a schematic cross-sectional view of a solid oxide fuel cell bonding material according to a tenth embodiment.
  • FIG. 1 is a schematic perspective view of a solid oxide fuel cell bonding material according to a first embodiment.
  • a solid oxide fuel cell bonding material 1 shown in FIG. 1 is a sheet-shaped bonding material used for a solid oxide fuel cell module. Specifically, for example, two members formed with through holes, such as an oxidant gas supply manifold and a fuel gas supply manifold, are members that connect and connect the through holes of both members.
  • the solid oxide fuel cell bonding material 1 can be used, for example, for applications in which power generation cells are bonded to each other, or in which a power generation cell and a solid oxide fuel cell module housing are bonded.
  • the constituent material of the solid oxide fuel cell bonding material 1 is not particularly limited.
  • the solid oxide fuel cell bonding material 1 may be formed of, for example, a material mainly composed of glass.
  • the solid oxide fuel cell bonding material 1 is composed of a laminated body of a glass ceramic layer 10 and a constraining layer 11 will be described.
  • the glass ceramic layer 10 includes glass ceramics.
  • the glass ceramic layer 10 may be made of only glass ceramics, or may contain, for example, amorphous glass in addition to the glass ceramics.
  • glass ceramics is a mixed material of glass and ceramics.
  • the glass ceramic contains silica, barium oxide, and alumina.
  • Si is 48 mass% to 75 mass% in terms of SiO 2
  • Ba is 20 mass% to 40 mass% in terms of BaO
  • Al is 5 mass% to 20 mass% in terms of Al 2 O 3. It is preferable that it is included.
  • Glass ceramics further, in terms of 2 mass% to 10 mass% in terms of Mn to MnO, 0.1 wt% to 10 wt% in terms of Ti to TiO 2, and Fe in the Fe 2 O 3 It may contain 0.1% by mass to 10% by mass.
  • the glass ceramic is preferably substantially free of Cr oxide or B oxide. In this case, for example, glass ceramics that can be fired at a temperature of 1100 ° C. or lower can be obtained.
  • the thickness of the glass ceramic layer 10 is not particularly limited, but is preferably 10 ⁇ m to 150 ⁇ m, for example, and more preferably 20 ⁇ m to 50 ⁇ m.
  • a constraining layer 11 is laminated on the glass ceramic layer 10.
  • the constraining layer 11 and the glass ceramic layer 10 are in direct contact.
  • the constraining layer 11 does not shrink in the plane direction at the firing temperature of the glass ceramic layer 10. That is, the constraining layer 11 has such a property that the glass ceramic layer 10 can be fired in a state where the constraining layer 11 does not substantially contract in the plane direction.
  • the constraining layer 11 can include, for example, alumina and glass.
  • the bonding strength between the constraining layer 11 and the layer formed by firing the glass ceramic layer 10 can be increased.
  • the volume of glass is preferably 10 to 70% with respect to the total volume of alumina and glass. If the ratio of the volume of glass to the total volume of alumina and glass is too small, the amount of glass in the constraining layer may be too small, and the constraining layer may not be sufficiently dense. On the other hand, if the ratio of the volume of glass to the total volume of alumina and glass is too large, the shrinkage suppression effect during firing of the glass ceramic layer may be weakened.
  • the glass contained in the constraining layer 11 may be an amorphous glass or a glass that crystallizes at least partially during firing. Moreover, when the constrained layer 11 contains an alumina and glass, it is preferable that the constrained layer 11 further contains glass ceramics. In this case, the bonding strength between the constraining layer 11 and the glass ceramic layer 10 or the object to be bonded becomes higher.
  • the thickness of the constraining layer 11 is preferably 0.5 ⁇ m to 50 ⁇ m, and more preferably 1 ⁇ m to 10 ⁇ m. If the thickness of the constraining layer 11 is too thin, the shrinkage suppression effect may be reduced. On the other hand, if the thickness of the constraining layer 11 is too thick, it is disadvantageous for the reduction in the height of the solid oxide fuel cell.
  • the thickness of the constraining layer 11 is preferably 0.05 to 0.25 times the thickness of the glass ceramic layer 10.
  • the constraining layer 11 may be constituted by a metal plate in which a plurality of holes are formed.
  • the constraining layer 11 may be made of expanded metal, punching metal, wire mesh, foam metal, or the like. Note that the plurality of holes may penetrate in the thickness direction (z direction).
  • expanded metal refers to a group of cuts having a plurality of linear cuts extending in one direction and arranged at intervals along one direction, and perpendicular to the one direction.
  • “Punching metal” refers to a metal plate having a plurality of openings formed in a matrix at predetermined intervals.
  • Wire mesh means a plurality of first metal lines that extend in one direction and are spaced apart from each other along another direction perpendicular to the one direction, and extend in the other direction.
  • a plurality of second metal lines that are arranged at intervals along one direction and intersect with the plurality of first metal lines, and the plurality of first metal lines and the plurality of first metal lines
  • the second metal wire is a member fixed in the thickness direction perpendicular to one direction and the other direction.
  • wire mesh a member in which a plurality of first metal wires and a plurality of second metal wires are knitted, a plurality of first metal wires, and a plurality of second metal wires are welded, etc. And both non-knitted members are included.
  • “Foamed metal” refers to a metal member having a plurality of pores inside.
  • the foam metal may have a three-dimensional network structure.
  • the pores may be continuous pores or closed pores.
  • the expanded metal preferably has a porosity of 30% to 86%, a line width of 30 ⁇ m to 250 ⁇ m, and a thickness of 30 ⁇ m to 500 ⁇ m.
  • the punching metal preferably has a porosity of 10% to 60%, an opening diameter of 50 ⁇ m to 1000 ⁇ m, and a thickness of 30 ⁇ m to 250 ⁇ m.
  • the wire mesh preferably has a porosity of 50% to 85% and a wire diameter of 50 ⁇ m to 200 ⁇ m.
  • the foam metal preferably has a porosity of 10% to 70%.
  • the constraining layer 11 When the constraining layer 11 is constituted by a metal plate in which a plurality of holes are formed, the constraining layer 11 preferably has a melting point of 900 ° C. or higher and does not melt at the firing temperature of the glass ceramic layer 10. For this reason, it is preferable that the constrained layer 11 consists of high melting point metals, such as stainless steel, silver, gold
  • the melting point of the constraining layer 11 is more preferably 1100 ° C. or higher.
  • the through-hole 1a, 1b is provided in the joining material 1 for solid oxide fuel cells.
  • This through-hole 1a communicates with the manifold of the power generation cell, for example. Accordingly, the through holes 1a and 1b constitute a gas flow path.
  • the recesses 1c and 1d are provided around the through holes 1a and 1b.
  • the recesses 1c and 1d may be bottomed or may penetrate the solid oxide fuel cell bonding material 1 in the thickness direction.
  • the recesses 1c and 1d are preferably formed by cutting the solid oxide fuel cell bonding material 1 using a cutting blade.
  • the through holes 1a and 1b have a rectangular shape, but may have a circular shape.
  • the shape of the through hole is not particularly limited.
  • the recess 1c is provided around the through hole 1a. Specifically, the recess 1c is provided around the corner of the through hole 1a. A plurality of the recesses 1c are provided along the outer periphery of the through hole 1a.
  • the recess 1d is provided around the through hole 1b. Specifically, the recess 1d is provided around the corner of the through hole 1b. A plurality of the recesses 1d are provided along the outer periphery of the through hole 1b.
  • the amount of contraction of the bonding material and the amount of contraction of the power generation cell when the bonding material is heated to join two power generation cells using the bonding material are different.
  • the bonding material contracts more than the power generation cell.
  • stress is applied to the bonding material due to the difference in shrinkage between the bonding material and the power generation cell. This stress may cause cracks in the bonding material.
  • a through hole such as a gas flow path is provided in the bonding material
  • stress is applied in the vicinity of the through hole.
  • the crack grows starting from the through hole.
  • this crack reaches the outer periphery of the bonding material, the crack becomes a leak hole. For this reason, the gas passing through the manifold leaks.
  • the stress applied to the bonding material becomes non-uniform and cracks are likely to occur.
  • the solid oxide fuel cell bonding material 1 of the present embodiment recesses 1c and 1d are provided around the through holes 1a and 1b. For this reason, even if cracks starting from the through holes 1a and 1b are generated in the solid oxide fuel cell bonding material 1, the progress of the cracks stops when the cracks reach the recesses 1c and 1d. Therefore, the crack is difficult to reach the outer edge of the solid oxide fuel cell bonding material 1. Therefore, the formation of leak holes can be effectively suppressed.
  • the recesses 1c and 1d are provided around the corners of the through holes 1a and 1b. Therefore, the formation of leak holes can be more effectively suppressed.
  • FIG. 2 is a schematic perspective view of a solid oxide fuel cell bonding material according to a second embodiment.
  • FIG. 3 is a schematic perspective view of a solid oxide fuel cell bonding material according to a third embodiment.
  • FIG. 4 is a schematic perspective view of a solid oxide fuel cell bonding material according to a fourth embodiment.
  • FIG. 5 is a schematic perspective view of a solid oxide fuel cell bonding material according to a fifth embodiment.
  • elongated corners extending along the direction in which the long sides of the through holes 1a and 1b extend may be provided one by one at each corner of the through holes 1a and 1b.
  • the recesses 1c and 1d may be provided in a substantially U shape so as to surround the ends of the through holes 1a and 1b in the longitudinal direction.
  • the recesses 1c and 1d may be provided in an annular shape so as to surround the through holes 1a and 1b.
  • FIG. 6 is a schematic side view of a solid oxide fuel cell module according to a sixth embodiment.
  • the solid oxide fuel cell module (also referred to as a hot module) 3 includes a housing 3a.
  • a solid oxide fuel cell 2 is disposed inside the housing 3a.
  • the fuel cell 2 has a plurality of power generation cells 20. Specifically, the fuel cell 2 has two power generation cells 20.
  • FIG. 7 is a schematic exploded perspective view of the power generation cell according to the sixth embodiment.
  • the power generation cell 20 includes a first separator 40, a power generation element 46, and a second separator 50.
  • the first separator 40, the power generation element 46, and the second separator 50 are stacked in this order.
  • an oxidant gas supply manifold 44 and a fuel gas supply manifold 45, which are through holes, are formed.
  • the power generation element 46 is a portion where the oxidant gas supplied from the oxidant gas supply manifold 44 reacts with the fuel gas supplied from the fuel gas supply manifold 45 to generate power.
  • the oxidant gas can be composed of, for example, an aerobic gas such as air or oxygen gas.
  • the fuel gas may be a gas containing hydrogen gas or hydrocarbon gas such as methane gas.
  • the power generation element 46 includes a solid oxide electrolyte layer 47. It is preferable that the solid oxide electrolyte layer 47 has high ionic conductivity.
  • the solid oxide electrolyte layer 47 can be formed of, for example, stabilized zirconia or partially stabilized zirconia. Specific examples of the stabilized zirconia include 10 mol% yttria stabilized zirconia (10YSZ), 11 mol% scandia stabilized zirconia (11ScSZ), and the like. Specific examples of the partially stabilized zirconia include 3 mol% yttria partially stabilized zirconia (3YSZ).
  • the solid oxide electrolyte layer 47 is, for example, Sm and Gd or the like ceria oxides doped, a LaGaO 3 as a host, La 0 the part of the La and Ga was substituted with Sr and Mg, respectively. It can also be formed of a perovskite oxide such as 8 Sr 0.2 Ga 0.8 Mg 0.2 O (3- ⁇ ) .
  • the solid oxide electrolyte layer 47 is sandwiched between the air electrode layer 48 and the fuel electrode layer 49. That is, the air electrode layer 48 is formed on one main surface of the solid oxide electrolyte layer 47, and the fuel electrode layer 49 is formed on the other main surface.
  • the air electrode layer 48 has an air electrode 48a.
  • the air electrode 48a is a cathode. In the air electrode 48a, oxygen takes in electrons and oxygen ions are formed.
  • the air electrode 48a is preferably porous, has high electron conductivity, and does not easily cause a solid-solid reaction with the solid oxide electrolyte layer 47 and the like at a high temperature.
  • the air electrode 48a can be formed of, for example, scandia-stabilized zirconia (ScSZ), Sn-doped indium oxide, PrCoO 3 oxide, LaCoO 3 oxide, LaMnO 3 oxide, or the like.
  • LaMnO 3 -based oxide examples include La 0.8 Sr 0.2 MnO 3 (common name: LSM), La 0.6 Ca 0.4 MnO 3 (common name: LCM), and the like.
  • the air electrode 48a may be made of a mixed material obtained by mixing two or more of the above materials.
  • the fuel electrode layer 49 has a fuel electrode 49a.
  • the fuel electrode 49a is an anode. In the fuel electrode 49a, oxygen ions and fuel gas react to emit electrons.
  • the fuel electrode 49a is preferably porous, has high electron conductivity, and does not easily cause a solid-solid reaction with the solid oxide electrolyte layer 47 and the like at a high temperature.
  • the fuel electrode 49a can be composed of, for example, NiO, yttria stabilized zirconia (YSZ) / nickel metal porous cermet, scandia stabilized zirconia (ScSZ) / nickel metal porous cermet, or the like.
  • the fuel electrode layer 49 may be made of a mixed material obtained by mixing two or more of the above materials.
  • the first separator 40 On the air electrode layer 48 of the power generation element 46, the first separator 40 constituted by the first separator body 41 and the first flow path forming member 42 is disposed.
  • the first separator 40 is formed with an oxidant gas passage 43 for supplying an oxidant gas to the air electrode 48a.
  • the oxidant gas flow path 43 extends from the oxidant gas supply manifold 44 toward the x2 side from the x1 side in the x direction.
  • the constituent material of the first separator 40 is not particularly limited.
  • the first separator 40 can be formed of, for example, stabilized zirconia such as yttria stabilized zirconia, partially stabilized zirconia, or the like.
  • a second separator 50 On the fuel electrode layer 49 of the power generation element 46, a second separator 50 constituted by a second separator body 51 and a second flow path forming member 52 is disposed.
  • the second separator 50 is formed with a fuel flow path 53 for supplying fuel gas to the fuel electrode 49a.
  • the fuel flow path 53 extends from the fuel gas supply manifold 45 toward the y2 side from the y1 side in the y direction.
  • the constituent material of the second separator 50 is not particularly limited.
  • the second separator 50 can be formed of, for example, stabilized zirconia, partially stabilized zirconia, or the like.
  • FIG. 8 is a schematic exploded perspective view of the fuel cell according to the sixth embodiment.
  • the two power generation cells 20 are bonded using the bonding material 1 described in the first embodiment.
  • the bonding material 1 is bonded by a first bonding layer 21a formed by firing.
  • the first bonding layer 21 a is obtained by firing the glass ceramic layer 10 in the bonding material 1. That is, the first bonding layer 21 a is configured by a laminate of the fired layer 22 obtained by firing the glass ceramic layer 10 and the constraining layer 11.
  • Through holes 21a1 and 21a2 are formed in the first bonding layer 21a.
  • the oxidant gas supply manifolds 44 of the two power generation cells 20 are connected by a through hole 21a2.
  • the fuel gas supply manifolds 45 of the two power generation cells 20 are connected by a through hole 21a1.
  • the two power generation cells 20 are joined by the first joining layer 21a formed by firing the joining material 1. For this reason, cracks from the through holes 21a1 and 21a2 to the outer edge hardly occur in the bonding layer 21a. Accordingly, leak holes are unlikely to occur in the first bonding layer 21a.
  • joining and electrical connection between power generation cells can be performed by providing the electrical connection part 54 in the joining material 21a.
  • the electrical connection portion 54 can be formed of a conductive material such as a conductive paste.
  • FIG. 9 is a schematic exploded perspective view of a part of the fuel cell module according to the sixth embodiment. In FIG. 9, only a part of the housing 3a is drawn, and other parts are omitted.
  • the fuel cell 2 is joined to the housing 3a by the second joining layer 21b.
  • the second bonding layer 21b is formed by baking the bonding material 1. Therefore, from the through-hole 21a2 which connects the oxidizing gas supply manifold 44 and the opening 3a2 of the housing 3a, and the through-hole 21a1 which connects the fuel gas supply manifold 45 and the opening 3a1 of the housing 3a. Cracks that reach the outer edge are unlikely to occur. Therefore, it is difficult for a leak hole to occur in the second bonding layer 21b.
  • the fuel cell module of the present embodiment is less prone to leak defects and is easy to manufacture stably.
  • the bonding layers 21 a and 21 b may have a recess, a through hole, a void, or the like derived from the recess or the through hole provided in the bonding material 1.
  • the bonding layers 21a and 21b have at least one of a bubble, a recess, and a through hole in a region where the recess and the through hole of the bonding material 1 are provided, and have a larger porosity than the other regions. Has an area.
  • the bonding layers 21 a and 21 b may have a recess and a through hole having substantially the same shape as the recess and the through hole provided in the bonding material 1.
  • the bonding layers 21a and 21b may have voids in a shape in which a concave portion or a part of the through hole provided in the bonding material 1 is filled with a material that is in another portion. That is, it is not always necessary that the concave portions and the through holes provided in the bonding material 1 remain in the bonding layers 21a and 21b with substantially the same shape and size.
  • the bonding layers 21a and 21b may have a plurality of closed cells in a region where the concave portion or the through hole of the bonding material 1 is provided.
  • the bonding layers 21 a and 21 b have at least one of at least one closed cell and a concave portion in the region where the concave portion or the through hole of the bonding material 1 is provided. It may be.
  • FIG. 10 is a schematic cross-sectional view of a solid oxide fuel cell bonding material according to a seventh embodiment.
  • FIG. 11 is a schematic cross-sectional view of a solid oxide fuel cell bonding material according to an eighth embodiment.
  • FIG. 12 is a schematic cross-sectional view of a solid oxide fuel cell bonding material according to a ninth embodiment.
  • FIG. 13 is a schematic cross-sectional view of a solid oxide fuel cell bonding material according to a tenth embodiment.
  • a plurality of at least one of the glass ceramic layer 10 and the constraining layer 11 may be provided.
  • the first glass ceramic layer 10a is provided on one main surface of the constraining layer 11, and the second glass ceramic layer 10b is provided on the other main surface. . Therefore, both surfaces of the bonding material are composed of glass ceramic layers. Accordingly, both the bonding strength between the bonding material to be bonded to one main surface of the bonding material and the bonding material, and the bonding strength between the bonding material to be bonded to the other main surface of the bonding material and the bonding material. Can be increased.
  • constraining layers 11 a and 11 b are provided on both sides of the glass ceramic layer 10. That is, the glass ceramic layer 10 is sandwiched between the constraining layers 11a and 11b. Accordingly, the shrinkage in the surface direction during firing of the glass ceramic layer 10 can be more effectively suppressed.
  • both constraining layers 11a and 11b are arranged between three glass ceramic layers 10a to 10c.
  • both surfaces of the bonding material are composed of glass ceramic layers. Accordingly, both the bonding strength between the bonding material to be bonded to one main surface of the bonding material and the bonding material, and the bonding strength between the bonding material to be bonded to the other main surface of the bonding material and the bonding material. Can be increased. Further, since the number of constraining layers with respect to the number of glass ceramic layers is larger than that of the bonding material shown in FIG. 10, shrinkage during firing of the glass ceramic layers 10a to 10c can be more effectively suppressed.

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  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

La présente invention se rapporte à un organe de liaison pour pile à combustible à oxyde solide et comportant des trous traversants. L'organe de liaison pour pile à combustible à oxyde solide selon l'invention est caractérisé en ce qu'il est très peu sujet à l'apparition de fissures, entre les trous traversants et le bord extérieur de l'organe de liaison, durant la liaison. L'organe de liaison (1) pour une pile à combustible à oxyde solide est un organe de liaison qui est conçu pour une pile à combustible à oxyde solide et qui comporte des trous traversants (1a, 1b). Des concavités (1c, 1d) sont formées dans le voisinage des trous traversants (1a, 1b).
PCT/JP2012/058579 2011-03-30 2012-03-30 Organe de liaison pour pile à combustible à oxyde solide, pile à combustible à oxyde solide et module de pile à combustible à oxyde solide WO2012133765A1 (fr)

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PCT/JP2012/058579 WO2012133765A1 (fr) 2011-03-30 2012-03-30 Organe de liaison pour pile à combustible à oxyde solide, pile à combustible à oxyde solide et module de pile à combustible à oxyde solide

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JP2017220375A (ja) * 2016-06-08 2017-12-14 株式会社村田製作所 燃料電池スタック及び燃料電池セル

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WO2018042480A1 (fr) * 2016-08-29 2018-03-08 ＦＣＯ Ｐｏｗｅｒ株式会社 Empilement de de piles à combustible à oxyde solide et procédé de préparation associé

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JPH07153471A (ja) * 1993-11-25 1995-06-16 Tokyo Gas Co Ltd 内部マニフォールド型固体電解質燃料電池
JPH10312818A (ja) * 1997-05-14 1998-11-24 Fuji Electric Co Ltd 固体電解質型燃料電池
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017220375A (ja) * 2016-06-08 2017-12-14 株式会社村田製作所 燃料電池スタック及び燃料電池セル
JP7032853B2 (ja) 2016-06-08 2022-03-09 株式会社村田製作所 燃料電池スタック及び燃料電池セル

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