WO2019159276A1 - Metal-supported cell - Google Patents

Metal-supported cell Download PDF

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Publication number
WO2019159276A1
WO2019159276A1 PCT/JP2018/005222 JP2018005222W WO2019159276A1 WO 2019159276 A1 WO2019159276 A1 WO 2019159276A1 JP 2018005222 W JP2018005222 W JP 2018005222W WO 2019159276 A1 WO2019159276 A1 WO 2019159276A1
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WO
WIPO (PCT)
Prior art keywords
layer
metal support
metal
anode layer
anode
Prior art date
Application number
PCT/JP2018/005222
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French (fr)
Japanese (ja)
Inventor
柴田　雅史
宋　東
佐藤　和之
大剛 岩▲崎▼
寛晃 吉富
Original Assignee
日産自動車株式会社
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Application filed by 日産自動車株式会社 filed Critical 日産自動車株式会社
Priority to PCT/JP2018/005222 priority Critical patent/WO2019159276A1/en
Publication of WO2019159276A1 publication Critical patent/WO2019159276A1/en

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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • 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
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0232—Metals or alloys
    • 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 metal support cell.
  • a metal support cell (MSC: Metal-Supported Cell) excellent in mechanical strength, rapid startability, and the like has been applied to a solid oxide fuel cell (SOFC).
  • the metal support cell is configured by sequentially laminating a cathode layer, an electrolyte layer formed of ceramic, an anode layer formed of ceramic containing a catalyst, and a metal metal support layer supporting the anode layer.
  • the coefficient of thermal expansion is different between metal and ceramic. Also, the metal expands due to oxidation. For this reason, there is a problem that peeling is likely to occur at the interface between the anode layer and the metal support layer due to a difference in thermal expansion coefficient between the anode layer and the metal support layer and expansion due to metal oxidation of the metal support layer. It was.
  • Patent Document 1 discloses a metal support cell in which the anode layer is mixed with the same metal as the metal support layer forming material. Thereby, the difference in thermal expansion coefficient between the anode layer and the metal support layer can be reduced.
  • An object of the present invention is to provide a metal support cell capable of maintaining ion conductivity while suppressing peeling at the interface between the anode layer and the metal support layer.
  • the metal support cell of the present invention includes ceramic particles and metal particles, and has an anode layer having a catalytic function, an electrolyte layer disposed on one side of the anode layer and formed of ceramic, And a metal support layer formed on the other side of the anode layer and made of metal.
  • the ratio of the metal particle content to the ceramic particle content in the anode layer is formed such that the metal support layer side is larger than the electrolyte layer side.
  • FIG. 1 is an exploded perspective view showing a fuel cell stack according to an embodiment of the present invention. It is a disassembled perspective view of the cell unit shown in FIG.
  • FIG. 3 is an exploded perspective view of the metal support cell assembly shown in FIG. 2.
  • FIG. 3 is a partial cross-sectional view of the metal support cell assembly taken along line AA in FIG. 2. It is sectional drawing of the metal support cell which concerns on embodiment of this invention. It is a schematic sectional drawing for demonstrating the magnitude
  • 2 is a cross-sectional view of a metal support cell according to Comparative Example 1.
  • FIG. 10 is an enlarged cross-sectional view of a portion surrounded by a broken line part B in FIG. 9. 6 is a cross-sectional view of a metal support cell according to Comparative Example 3.
  • FIG. 10 is a cross-sectional view of a metal support cell according to Modification 1.
  • FIG. It is sectional drawing of the metal support cell which concerns on the modification 2.
  • FIG. It is sectional drawing of the metal support cell which concerns on the modification 3.
  • a metal support cell (MSC) 10 according to an embodiment of the present invention will be described with reference to FIGS.
  • the metal support cell 10 of this embodiment is used for a solid oxide fuel cell (SOFC).
  • SOFC solid oxide fuel cell
  • an XYZ rectangular coordinate system is shown in the figure.
  • the X-axis and Y-axis are horizontal directions, and the Z-axis is an axis parallel to the vertical direction.
  • FIG. 1 is an exploded perspective view showing a fuel cell stack 1 configured by stacking a plurality of cell units 1U according to the first embodiment in the vertical direction.
  • the vertical direction of the fuel cell stack 1 indicated by the Z axis in the drawing is also referred to as “stacking direction”.
  • FIG. 2 is an exploded perspective view of the cell unit 1U.
  • the cell unit 1U is configured by laminating a metal support cell assembly 1A, a separator 120 including a flow channel 121 that forms a gas flow channel, and a current collecting auxiliary layer 130.
  • a contact material may be disposed between the metal support cell assembly 1 ⁇ / b> A and the current collection auxiliary layer 130 so that they are in conductive contact with each other.
  • FIG. 3 is an exploded perspective view of the metal support cell assembly 1A
  • FIG. 4 is a partial cross-sectional view thereof.
  • the metal support cell assembly 1 ⁇ / b> A includes a metal support cell 10 and a cell frame 113 that holds the outer periphery of the metal support cell 10.
  • FIG. 5 is a cross-sectional view of the metal support cell 10.
  • the metal support cell 10 includes a power generation cell 20 and a metal support layer 60 made of metal that supports the power generation cell 20.
  • the metal support cell 10 is superior in mechanical strength, quick startability, and the like as compared with the electrolyte support cell and the electrode support cell.
  • the power generation cell 20 is configured by laminating a cathode layer 30 and an anode layer 50, which are a pair of electrodes, on both sides of the electrolyte layer 40.
  • the anode layer 50 is disposed between the electrolyte layer 40 and the metal support layer 60.
  • the electrolyte layer 40 is disposed on one side of the anode layer 50
  • the metal support layer 60 is disposed on the other side of the anode layer 50.
  • the cathode layer 30 is an oxidizer electrode, and reacts cathode gas (for example, oxygen contained in air) with electrons to convert oxygen molecules into oxide ions.
  • cathode gas for example, oxygen contained in air
  • the cathode layer 30 is resistant to an oxidizing atmosphere, and has high gas permeability and electrical conductivity for allowing the cathode gas to permeate. Further, the cathode layer 30 has a catalytic function for converting oxygen molecules into oxygen ions.
  • Examples of the material for forming the cathode layer 30 include oxides such as lanthanum, strontium, manganese, and cobalt.
  • the electrolyte layer 40 has the property of not allowing gas and electrons to pass while conducting oxide ions from the cathode layer 30 toward the anode layer 50.
  • oxygen ions are a power generation conductor
  • the electrolyte layer 40 is preferably formed from a material having high oxygen ion conductivity.
  • the electrolyte layer 40 is formed from ceramic.
  • the ceramic forming the electrolyte layer 40 is, for example, a rare earth oxide (for example, Y 2 O 3 , Sc 2 O 3 , Gd 2 O 3 , Sm 2 O 3 , Yb 2 O 3 , Nd 2 O 3, etc.).
  • Solid oxide ceramics such as stabilized zirconia, ceria-based solid solution, perovskite oxide (for example, SrCeO 3 , BaCeO 3 , CaZrO 3 , SrZrO 3, etc.) in which the selected one or two or more are dissolved.
  • ceramic broadly means an inorganic sintered body, and is not limited to a non-metallic oxide but also includes a metal oxide.
  • the anode layer 50 is a fuel electrode, and reacts an anode gas (for example, hydrogen) with oxide ions to generate an oxide of the anode gas and take out electrons.
  • the anode layer 50 is resistant to a reducing atmosphere, and has high gas permeability and electrical conductivity that allow the anode gas to pass therethrough. Furthermore, the anode layer 50 has a catalytic function for reacting the anode gas with oxide ions.
  • the anode layer 50 includes ceramic particles 210 and metal particles 220.
  • the anode layer 50 according to this embodiment includes a first anode layer 51 disposed adjacent to the electrolyte layer 40 and a second anode layer 52 disposed adjacent to the metal support layer 60.
  • the first anode layer 51 is formed from ceramic particles 210.
  • the second anode layer 52 is formed from ceramic particles 210 and metal particles 220.
  • metal / ceramic ratio the ratio of the content of the metal particles 220 to the content of the ceramic particles 210 in the anode layer 50 (hereinafter referred to as “metal / ceramic ratio”) is larger on the metal support layer 60 side than on the electrolyte layer 40 side. It is formed as follows.
  • the first anode layer 51 disposed on the electrolyte layer 40 side has a high ceramic content. For this reason, ionic conductivity at the interface between the anode layer 50 and the electrolyte layer can be maintained.
  • metal and ceramic have different coefficients of thermal expansion. Also, the metal expands due to oxidation. As described above, the second anode layer 52 disposed on the metal support layer 60 side has a relatively high metal / ceramic ratio. For this reason, the difference in the coefficient of thermal expansion between the metal and the ceramic and the difference in volume change between the anode layer 50 and the metal support layer 60 due to the oxidation of the metal are reduced at the interface. Thereby, peeling of the interface between the anode layer 50 and the metal support layer 60 can be suppressed.
  • the metal / ceramic ratio in the second anode layer 52 is not particularly limited, but can be set to about 70% / 30%, for example.
  • the ceramic particles 210 preferably have the same lattice constant and the same thermal expansion coefficient as the ceramic forming the electrolyte layer 40. Thereby, the bondability at the interface between the anode layer 50 and the electrolyte layer 40 can be improved.
  • the “similar lattice constant” means that at least the crystal structure at the interface has consistency so that the bonding strength at the interface between the electrolyte layer 40 and the anode layer 50 can be secured.
  • the lattice constant includes an interstitial distance, an interstitial angle, and the like.
  • the “same thermal expansion coefficient” is not limited to the case where the thermal expansion coefficient of the ceramic particles 210 and the ceramic forming the electrolyte layer 40 is the same, and the interface peeling between the anode layer 50 and the electrolyte layer 40 is performed. Is included to the extent that is suppressed.
  • the tolerance of the coefficient of thermal expansion is preferably 5% or less, and more preferably 1% or less.
  • the same material as the ceramic forming the electrolyte layer 40 can be used.
  • the metal particles 220 preferably have a thermal expansion coefficient comparable to that of the metal forming the metal support layer 60. Thereby, peeling due to the difference in coefficient of thermal expansion at the interface between the anode layer 50 and the metal support layer 60 is suppressed.
  • “the same degree of thermal expansion coefficient” is not limited to the case where the thermal expansion coefficient of the metal particles 220 and the metal forming the metal support layer 60 is the same, and is between the anode layer 50 and the metal support layer 60. It means that a tolerance is included to such an extent that interfacial peeling is suppressed.
  • the tolerance of the coefficient of thermal expansion is preferably 5% or less, and more preferably 1% or less.
  • the constituent material of the metal particles 220 the same material as the metal forming the metal support layer 60 can be used.
  • the “metal particles 220” means a main component constituting the anode layer 50, and does not include the metal catalyst of the anode layer 50. Further, “metal forming the metal particles 220” and “metal forming the metal support layer 60” do not include ceramics such as metal oxides.
  • the anode layer 50 is a porous body in which a plurality of holes H are formed.
  • FIG. 6 is a schematic cross-sectional view for explaining the size of the holes H of the anode layer 50.
  • the average diameter of the holes H included in the unit volume in the anode layer 50 is such that the metal support layer 60 side (lower side in FIG. 6) is on the electrolyte layer 40 side (upper side in FIG. 6). It is formed so as to be larger.
  • the anode layer 50 has large holes H on the metal support layer 60 side, so that the gas diffusibility is improved, and the anode gas is efficiently supplied to the vicinity of the electrolyte layer 40 as indicated by the arrows in FIG. be able to.
  • the anode layer 50 has small holes H on the electrolyte layer 40 side, the contact area between the electrolyte layer 40 and the anode layer 50 increases. Thereby, the ion conductivity can be improved at the interface between the electrolyte layer 40 and the anode layer 50, and the supply amount of ions can be increased.
  • the “average diameter of the holes H” is, for example, on the outline of the hole wall surface that forms the holes H observed using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or the like. It means the maximum distance among any two points.
  • the pores H in the anode layer 50 are impregnated with a catalyst.
  • the catalyst is impregnated into the anode layer 50 from the metal support layer 60 side after the holes H are formed.
  • the catalyst can be impregnated to the vicinity of the electrolyte layer 40 by impregnating the catalyst from the metal support layer 60 side where the average diameter of the holes H is larger than that of the electrolyte layer 40 side.
  • a metal catalyst such as nickel (Ni) can be used.
  • Metal support layer 60 As shown in FIGS. 3 and 4, the metal support layer 60 supports the power generation cell 20 from the anode layer 50 side. By supporting the power generation cell 20 with the metal support layer 60, the mechanical strength of the power generation cell 20 can be improved and damage can be suppressed.
  • the metal support layer 60 is formed from a porous metal having gas permeability and electrical conductivity.
  • metal that forms the metal support layer 60 for example, a corrosion-resistant alloy, corrosion-resistant steel, stainless steel, or the like containing nickel (Ni) or chromium (Cr) can be used.
  • the cell frame 113 holds the metal support cell 10 from the periphery. As shown in FIG. 3, the cell frame 113 has an opening 113H. The metal support cell 10 is disposed in the opening 113H of the cell frame 113. The outer periphery of the metal support cell 10 is joined to the inner edge of the opening 113H of the cell frame 113.
  • the cell frame 113 has an anode gas inlet 113a and an anode gas outlet 113b through which the anode gas flows, and a cathode gas inlet 113c and a cathode gas outlet 113d through which the cathode gas flows.
  • the flow path portion 121 of the separator 120 is formed in a substantially linear shape so that the concavo-convex shape extends in the longitudinal direction Y. Thereby, the flow direction of the gas flowing along the flow path part 121 is the longitudinal direction Y.
  • the separator 120 has an anode gas inlet 125a and an anode gas outlet 125b through which anode gas flows, and a cathode gas inlet 125c and cathode gas outlet 125d through which cathode gas flows. ing.
  • the current collecting auxiliary layer 130 forms a space through which gas passes and makes the surface pressure uniform to assist the electrical contact between the metal support cell 10 and the separator 120.
  • the current collection auxiliary layer 130 can be formed of, for example, a wire mesh expanded metal.
  • FIG. 7 is a schematic view for explaining a method for manufacturing the metal support cell 10.
  • the manufacturing method of the half cell comprised from the electrolyte layer 40 which is a precursor of the metal support cell 10, the anode layer 50, and the metal support layer 60 is demonstrated, and the manufacturing method of the cathode layer 30 is abbreviate
  • the manufacturing method of the metal support cell 10 has a slurry preparation process, a coating process, a lamination process, and a sintering process.
  • the slurry raw materials are mixed to prepare an electrolyte slurry, a first anode electrode slurry, a second anode electrode slurry, and a metal support slurry.
  • a known stirring device can be appropriately selected and used.
  • the electrolyte slurry is formed by mixing a slurry raw material containing ceramic powder as a main component and containing a solvent and a binder.
  • the first anode electrode slurry is formed by mixing a slurry raw material containing ceramic particles 210 as a main component and containing a solvent and a binder.
  • the second anode electrode slurry is formed by mixing slurry raw materials containing ceramic particles 210 and metal particles 220 as main components and containing a solvent and a binder.
  • the metal support slurry is formed by mixing a slurry raw material containing a metal powder as a main component and containing a solvent and a binder.
  • the solvent for the slurry, for example, is not particularly limited, but water and / or alcohol solvents such as methanol, ethanol, 1-propanol (NPA), 2-propanol, ethylene glycol, propylene glycol, An organic solvent such as N-methyl-2-pyrrolidone (NMP) can be mentioned. These solvents may be used alone or in combination of two or more. The amount of the solvent used is preferably adjusted so that the viscosity is suitable for molding when the slurry is molded into a sheet.
  • a known organic binder can be appropriately selected and used.
  • the organic binder include an ethylene copolymer, a styrene copolymer, an acrylate copolymer, a methacrylate copolymer, a vinyl butyral resin, a vinyl acetal resin, a vinyl formal resin, and a vinyl alcohol resin.
  • celluloses such as ethyl cellulose.
  • each slurry prepared in the slurry preparation step is formed into a sheet using a sheet forming method such as a tape casting method using a coating device such as a knife coater or a doctor blade.
  • the obtained sheet is dried and then heat-treated as necessary to obtain an electrolyte sheet, a first anode electrode sheet, a second anode electrode sheet, and a metal support sheet.
  • an electrolyte sheet, a first anode electrode sheet, a second anode electrode sheet, and a metal support sheet are sequentially laminated and bonded to form a laminated body.
  • the laminate in the sintering step, can be degreased and sintered to obtain a half cell that is a precursor of the metal support cell 10.
  • the firing conditions are not particularly limited and can be set to known conditions.
  • anode layer 50 has a two-layer structure
  • a multilayer structure of three or more layers see Modification 2 described later
  • a single-layer structure see Modification 3 described later
  • the kind of slurry to be prepared can be changed according to the number.
  • FIG. 8 is a cross-sectional view of the metal support cell according to the comparative example 1.
  • FIG. 9 is a cross-sectional view of the metal support cell according to the comparative 2.
  • 10 is an enlarged cross-sectional view of a portion surrounded by a broken line portion B in FIG. Note that the arrows in FIG. 10 indicate the flow of ions.
  • FIG. 11 is a cross-sectional view of a metal support cell according to Comparative Example 3.
  • the metal support cell according to the comparative example 1 shown in FIG. Therefore, the volume change between the anode layer 50a and the metal support layer 60 due to the difference in thermal expansion coefficient between the anode layer 50a and the metal support layer 60 or the expansion of the metal of the metal support layer 60 due to oxidation. The difference will occur.
  • the operating temperature of the solid oxide fuel cell is as high as about 700 to 1000 ° C.
  • a difference in volume change is more likely to occur between the anode layer 50a and the metal support layer 60.
  • peeling tends to occur at the interface between the anode layer 50a and the metal support layer 60.
  • the metal support cell according to Comparative Example 3 shown in FIG. 11 includes an anode layer 50c formed from the ceramic particles 210, and a surface layer 61c in which the ceramic particles 210 are embedded in a part of the holes adjacent to the anode layer 50c.
  • a metal support layer 60c is provided.
  • the difference of the volume change of the interface between the anode layer 50c and the surface layer 61c of the metal support layer 60c can be reduced.
  • the anode layer 50c can be formed from the ceramic particles 210, ion conductivity can be maintained.
  • the reaction area is reduced, so that the battery performance is deteriorated. Therefore, a configuration in which the ceramic particles 210 are embedded in a part of the metal support layer 60c as in the comparative example 3 is not preferable.
  • the metal support cell 10 includes the ceramic particles 210 and the metal particles 220, is disposed on one side of the anode layer 50 having a catalytic function, and is formed of ceramic. And an electrolyte layer 40 and a metal support layer 60 disposed on the other side of the anode layer 50 and made of metal.
  • the ratio of the content of the metal particles 220 to the content of the ceramic particles 210 in the anode layer 50 is formed so that the metal support layer 60 side is larger than the electrolyte layer 40 side.
  • the metal / ceramic ratio is relatively high on the metal support layer 60 side in the anode layer 50. For this reason, the difference in the coefficient of thermal expansion between the metal and the ceramic and the difference in volume change between the anode layer 50 and the metal support layer 60 due to the oxidation of the metal are reduced at the interface. Thereby, peeling of the interface between the anode layer 50 and the metal support layer 60 can be suppressed. Further, the metal / ceramic ratio is relatively low on the electrolyte layer 40 side in the anode layer 50, that is, the content of the ceramic particles 210 is relatively high. For this reason, the ionic conductivity at the interface between the anode layer 50 and the electrolyte layer 40 can be maintained.
  • the anode layer 50 is a porous body having a plurality of pores H, and the average diameter of the pores H included in the unit volume in the anode layer 50 is larger on the metal support layer 60 side than on the electrolyte layer 40 side. Is formed. Thereby, since the anode layer 50 has large holes H on the metal support layer 60 side, the gas diffusibility is improved, and the anode gas can be efficiently supplied to the vicinity of the electrolyte layer 40. In addition, since the anode layer 50 has small holes H on the electrolyte layer 40 side, the contact area between the electrolyte layer 40 and the anode layer 50 increases. Thereby, since the supply amount of ions increases at the interface between the electrolyte layer 40 and the anode layer 50, the ion conductivity can be improved.
  • the anode layer 50 further has a catalyst impregnated in the holes H.
  • the catalyst is impregnated into the anode layer 50 from the metal support layer 60 side after the holes H are formed.
  • the catalyst can be impregnated to the vicinity of the electrolyte layer 40 by impregnating the catalyst from the metal support layer 60 side where the average diameter of the holes H is larger than that of the electrolyte layer 40 side.
  • the metal particles 220 in the anode layer 50 have a thermal expansion coefficient similar to that of the metal forming the metal support layer 60. Thereby, peeling due to the difference in coefficient of thermal expansion at the interface between the anode layer 50 and the metal support layer 60 is suppressed.
  • the ceramic particles 210 in the anode layer 50 have the same lattice constant and the same thermal expansion coefficient as the ceramic forming the electrolyte layer 40. Thereby, the bondability at the interface between the anode layer 50 and the electrolyte layer 40 can be improved.
  • the anode layer 50 has a multilayer structure composed of two or more layers including the first anode layer 51 and the second anode layer 52. This makes it easy to control the metal / ceramic ratio, the particle diameter of the metal particles 220, the particle diameter of the ceramic particles 210, the pore diameter, and the like for each layer.
  • FIG. 12 is a cross-sectional view of a metal support cell according to the first modification.
  • the anode layer 150 of the metal support cell according to the first modification has an average particle size of the ceramic particles 210 included in the unit volume and an average particle size of the metal particles 220 included in the unit volume. This is different from the above-described embodiment in that the layer 60 side (the lower side in FIG. 12) is configured to be larger than the electrolyte layer 40 side.
  • the anode layer 150 may have a multilayer structure as in the above-described embodiment, or may be configured by a single layer.
  • the “particle diameter” is, for example, the maximum of the distance between any two points on the contour line of a particle observed using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or the like. Means distance.
  • the metal support cell according to Modification 1 is formed such that the average particle diameter of the metal particles 220 included in the unit volume in the anode layer 150 is larger on the metal support layer 60 side than on the electrolyte layer 40 side. Has been.
  • the average particle diameter of the metal particles 220 By increasing the average particle diameter of the metal particles 220, the total surface area of the metal particles 220 included in the unit volume can be reduced. For this reason, the anode layer 150 can suppress expansion due to metal oxidation on the metal support layer 60 side.
  • the average particle diameter of the ceramic particles 210 contained in the unit volume in the anode layer 150 is formed so that the metal support layer 60 side is larger than the electrolyte layer 40 side.
  • the average particle diameter of the ceramic particles 210 contained in the unit volume in the anode layer 150 is formed so that the electrolyte layer 40 side is smaller than the metal support layer 60 side.
  • FIG. 13 is a cross-sectional view of a metal support cell according to Modification 2.
  • the anode layer 250 of the metal support cell according to the modification 2 is different from the above-described embodiment in that it has a multilayer structure composed of three or more layers as shown in FIG.
  • the layer closer to the metal support layer 60 is formed so that the metal / ceramic ratio and the pore diameter are larger than the layer closer to the electrolyte layer 40.
  • the particle diameters of the ceramic particles 210 are the same, but the layer closer to the electrolyte layer 40 has a particle diameter of the ceramic particles 210 than the layer closer to the metal support layer 60. You may form so that it may become small.
  • the particle diameter of the metal particles 220 is illustrated with the same size, but the particle diameter of the metal particles 220 is larger in the layer closer to the metal support layer 60 than in the layer closer to the electrolyte layer 40. You may form in.
  • the anode layer 250 of the metal support cell according to the modified example 2 has a multilayer structure including three or more layers. As the number of layers in the multilayer structure increases, the distribution of the metal / ceramic ratio in the anode layer 250, the particle diameter of the ceramic particles 210, the particle diameter of the metal particles 220, the pore diameter, and the like becomes easier to control with higher accuracy.
  • the effects obtained by forming the metal / ceramic ratio, the particle diameter of the ceramic particles 210, the particle diameter of the metal particles 220, and the pore diameter so that the metal support layer 60 side is larger than the electrolyte layer 40 side are the same as in the above embodiment and As described in the first modification.
  • FIG. 14 is a cross-sectional view of a metal support cell according to Modification 3.
  • the anode layer 350 of the metal support cell according to the modification 3 is different from the above-described embodiment in that it is composed of one layer (single layer) as shown in FIG.
  • the anode layer 350 is formed so that the metal support layer 60 side has a larger metal / ceramic ratio and pore diameter than the electrolyte layer 40 side.
  • the particle diameter of the ceramic particles 210 is shown as the same size, but the ceramic particles 210 may be formed so that the particle diameter of the ceramic particles 210 is smaller on the electrolyte layer 40 side than on the metal support layer 60 side. .
  • the particle diameter of the metal particle 220 is illustrated with the same size, the metal particle 220 may be formed so that the metal particle 220 has a larger particle diameter than the electrolyte layer 40 side.
  • the anode layer 350 of the metal support cell according to the modified example 2 has a single layer structure.
  • the distribution of the metal / ceramic ratio, the particle diameter of the ceramic particles 210, the particle diameter of the metal particles 220, and the pore diameter can be changed in one layer. For this reason, since the kind of slurry to prepare decreases, manufacturing cost can be reduced.
  • FIG. 15 is a cross-sectional view of a metal support cell according to Modification 4.
  • the anode layer 450 of the metal support cell according to the modification 4 is different from the above-described embodiment in that the anode layer 450 includes a plurality of plate-like members 451 as shown in FIG.
  • a gas flow path can be formed using gaps between the plurality of plate-like members 451.
  • the plate-like member 451 is not porous.
  • each plate-like member 451 is formed so that the metal support layer 60 side is larger than the electrolyte layer 40 side. Thereby, the metal support cell which concerns on the modification 4 has an effect similar to embodiment mentioned above.
  • the metal support cell according to the present invention has been described through the embodiment and the modification.
  • the present invention is not limited only to the content described in the embodiment, and may be appropriately changed based on the description of the claims. It is possible.
  • the metal support cell may be configured by appropriately combining the specifications of the embodiment and the modification described above.
  • the distribution of metal / ceramic ratio, ceramic particle particle size, metal particle particle size and pore size in the anode layer is limited to the case where the distribution increases from the electrolyte layer side to the metal support layer side in a linear or curved shape. Not including the case of increasing stepwise.
  • the metal / ceramic ratio, the particle diameter of the ceramic particles, the particle diameter of the metal particles, and the pore diameter are increased stepwise for each layer. Can do.
  • the average particle diameter of the ceramic particles contained in the unit volume in the anode layer and the average particle diameter of the metal particles contained in the unit volume are set so that the metal support layer side is larger than the electrolyte layer side.
  • the example to form was demonstrated.
  • the present invention is not limited to this, and only one of the average particle diameter of the ceramic particles contained in the unit volume or the average particle diameter of the metal particles contained in the unit volume is formed so that the metal support layer side is larger than the electrolyte layer side. May be.
  • Fuel cell stack 1U cell unit, 1A Metal support cell assembly, 10 Metal support cell, 20 power generation cells, 30 cathode layer, 40 electrolyte layer, 50, 150, 250, 350, 450 anode layer, 51 a first anode layer, 52 second anode layer, 60, 60c metal support layer, 113 cell frames, 120 separator, 130 Current collection auxiliary layer, 210 ceramic particles, 220 metal particles, H Hole X (Fuel cell stack) short direction, Y longitudinal direction (of the fuel cell stack), Z (Fuel cell stack) stacking direction.

Abstract

[Problem] To provide a metal-supported cell with which it is possible to maintain ion conductivity while suppressing peeling at the boundary between an anode layer and a metal support layer. [Solution] A metal-supported cell 10 includes ceramic particles 210 and metal particles 220, and has an anode layer 50 provided with a catalyst function, an electrolyte layer 40 disposed on one side of the anode layer and formed from a ceramic, and a metal support layer 60 disposed on the other side of the anode layer and formed from a metal. The present invention is formed so that the ratio of the amount of metal particles to the amount of ceramic particles contained in the anode layer is greater on the metal support layer side than on the electrolyte layer side.

Description

メタルサポートセルMetal support cell
　本発明は、メタルサポートセルに関する。 The present invention relates to a metal support cell.
　従来から、機械的強度、急速起動性等に優れるメタルサポートセル（ＭＳＣ：Ｍｅｔａｌ－Ｓｕｐｐｏｒｔｅｄ　Ｃｅｌｌ）が固体酸化物形燃料電池（ＳＯＦＣ：Ｓｏｌｉｄ　Ｏｘｉｄｅ　Ｆｕｅｌ　Ｃｅｌｌ）に適用されている。メタルサポートセルは、カソード層と、セラミックから形成された電解質層と、触媒を含むセラミックから形成されたアノード層と、アノード層を支持する金属製のメタルサポート層と、を順に積層して構成される。 Conventionally, a metal support cell (MSC: Metal-Supported Cell) excellent in mechanical strength, rapid startability, and the like has been applied to a solid oxide fuel cell (SOFC). The metal support cell is configured by sequentially laminating a cathode layer, an electrolyte layer formed of ceramic, an anode layer formed of ceramic containing a catalyst, and a metal metal support layer supporting the anode layer. The
　一般的に、金属とセラミックとは、熱膨張率が異なる。また、金属は、酸化によって膨張する。このため、アノード層とメタルサポート層との間の熱膨張率の差やメタルサポート層の金属の酸化による膨張によって、アノード層とメタルサポート層との間の界面に剥離が生じやすいという問題があった。 Generally, the coefficient of thermal expansion is different between metal and ceramic. Also, the metal expands due to oxidation. For this reason, there is a problem that peeling is likely to occur at the interface between the anode layer and the metal support layer due to a difference in thermal expansion coefficient between the anode layer and the metal support layer and expansion due to metal oxidation of the metal support layer. It was.
　上記課題に対して、例えば、下記特許文献１には、アノード層にメタルサポート層の形成材料と同じ金属を混合したメタルサポートセルが開示されている。これにより、アノード層とメタルサポート層との間の熱膨張率の差を低減することができる。 In response to the above problem, for example, Patent Document 1 below discloses a metal support cell in which the anode layer is mixed with the same metal as the metal support layer forming material. Thereby, the difference in thermal expansion coefficient between the anode layer and the metal support layer can be reduced.
欧州特許第２０３１６７５号公報European Patent No. 20316675
　しかしながら、上記特許文献１のメタルサポートセルでは、電解質層とアノード層との間の界面にセラミックに比べてイオン伝導性の低い金属粒子が多く存在する。このため、メタルサポートセルのイオン伝導性が低下し、発電性能が低下してしまう。 However, in the metal support cell of Patent Document 1 described above, there are many metal particles having lower ion conductivity than the ceramic at the interface between the electrolyte layer and the anode layer. For this reason, the ion conductivity of a metal support cell falls and power generation performance will fall.
　本発明の目的は、アノード層とメタルサポート層との間の界面での剥離を抑制しつつ、イオン伝導性を維持することのできるメタルサポートセルを提供することである。 An object of the present invention is to provide a metal support cell capable of maintaining ion conductivity while suppressing peeling at the interface between the anode layer and the metal support layer.
　上記目的を達成するための本発明のメタルサポートセルは、セラミック粒子と金属粒子とを含み、触媒機能を備えるアノード層と、アノード層の一方側に配置され、セラミックから形成された電解質層と、アノード層の他方側に配置され、金属から形成されたメタルサポート層と、を有する。アノード層中のセラミック粒子の含有量に対する金属粒子の含有量の比率は、メタルサポート層側が電解質層側よりも大きくなるように形成される。 To achieve the above object, the metal support cell of the present invention includes ceramic particles and metal particles, and has an anode layer having a catalytic function, an electrolyte layer disposed on one side of the anode layer and formed of ceramic, And a metal support layer formed on the other side of the anode layer and made of metal. The ratio of the metal particle content to the ceramic particle content in the anode layer is formed such that the metal support layer side is larger than the electrolyte layer side.
本発明の実施形態に係る燃料電池スタックを示す分解斜視図である。1 is an exploded perspective view showing a fuel cell stack according to an embodiment of the present invention. 図１に示すセルユニットの分解斜視図である。It is a disassembled perspective view of the cell unit shown in FIG. 図２に示すメタルサポートセルアッセンブリーの分解斜視図である。FIG. 3 is an exploded perspective view of the metal support cell assembly shown in FIG. 2. 図２のＡ－Ａ線に沿うメタルサポートセルアッセンブリーの部分断面図である。FIG. 3 is a partial cross-sectional view of the metal support cell assembly taken along line AA in FIG. 2. 本発明の実施形態に係るメタルサポートセルの断面図である。It is sectional drawing of the metal support cell which concerns on embodiment of this invention. 本発明の実施形態に係るアノード層の空孔の大きさを説明するための概略断面図である。It is a schematic sectional drawing for demonstrating the magnitude | size of the void | hole of the anode layer which concerns on embodiment of this invention. 本発明の実施形態に係るメタルサポートセルの製造方法を説明するための概略図である。It is the schematic for demonstrating the manufacturing method of the metal support cell which concerns on embodiment of this invention. 対比例１に係るメタルサポートセルの断面図である。2 is a cross-sectional view of a metal support cell according to Comparative Example 1. FIG. 対比例２に係るメタルサポートセルの断面図である。It is sectional drawing of the metal support cell which concerns on the contrast 2. 図９の破線部Ｂによって囲まれる部分の拡大断面図である。FIG. 10 is an enlarged cross-sectional view of a portion surrounded by a broken line part B in FIG. 9. 対比例３に係るメタルサポートセルの断面図である。6 is a cross-sectional view of a metal support cell according to Comparative Example 3. FIG. 変形例１に係るメタルサポートセルの断面図である。10 is a cross-sectional view of a metal support cell according to Modification 1. FIG. 変形例２に係るメタルサポートセルの断面図である。It is sectional drawing of the metal support cell which concerns on the modification 2. FIG. 変形例３に係るメタルサポートセルの断面図である。It is sectional drawing of the metal support cell which concerns on the modification 3. 変形例４に係るメタルサポートセルの断面図である。It is sectional drawing of the metal support cell which concerns on the modification 4.
　以下、添付した図面を参照しながら、本発明の実施形態を説明する。なお、以下の説明は特許請求の範囲に記載される技術的範囲や用語の意義を限定するものではない。また、図面の寸法比率は説明の都合上誇張されており、実際の比率とは異なる場合がある。例えば、図中に示す各層の構成粒子（セラミック粒子や金属粒子）の寸法比率や形状は、特に言及しない限り、実際のものとは異なる場合がある。 Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In addition, the following description does not limit the meaning of the technical scope and terms described in the claims. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may differ from actual ratios. For example, the dimensional ratio and shape of the constituent particles (ceramic particles and metal particles) of each layer shown in the figure may be different from actual ones unless otherwise specified.
　図１～図６を参照して、本発明の実施形態に係るメタルサポートセル（ＭＳＣ）１０について説明する。本実施形態のメタルサポートセル１０は、固体酸化物形燃料電池（ＳＯＦＣ）に用いられる。 A metal support cell (MSC) 10 according to an embodiment of the present invention will be described with reference to FIGS. The metal support cell 10 of this embodiment is used for a solid oxide fuel cell (SOFC).
　以下の説明の便宜のため、ＸＹＺ直交座標系を図中に示す。Ｘ軸およびＹ軸は水平方向、Ｚ軸は上下方向にそれぞれ平行な軸を示す。 For convenience of the following explanation, an XYZ rectangular coordinate system is shown in the figure. The X-axis and Y-axis are horizontal directions, and the Z-axis is an axis parallel to the vertical direction.
　図１は、第１実施形態に係る複数のセルユニット１Ｕを上下方向に積層して構成した燃料電池スタック１を示す分解斜視図である。以下、図中にＺ軸で示す燃料電池スタック１の上下方向を「積層方向」とも称する。 FIG. 1 is an exploded perspective view showing a fuel cell stack 1 configured by stacking a plurality of cell units 1U according to the first embodiment in the vertical direction. Hereinafter, the vertical direction of the fuel cell stack 1 indicated by the Z axis in the drawing is also referred to as “stacking direction”.
　（セルユニット１Ｕ）
　図２は、セルユニット１Ｕの分解斜視図である。図２に示すように、セルユニット１Ｕは、メタルサポートセルアッセンブリー１Ａと、ガスの流路を区画形成する流路部１２１を備えるセパレータ１２０と、集電補助層１３０と、を積層して構成される。なお、メタルサポートセルアッセンブリー１Ａと集電補助層１３０との間に両者を導通接触させる接点材を配置してもよい。 (Cell unit 1U)
FIG. 2 is an exploded perspective view of the cell unit 1U. As shown in FIG. 2, the cell unit 1U is configured by laminating a metal support cell assembly 1A, a separator 120 including a flow channel 121 that forms a gas flow channel, and a current collecting auxiliary layer 130. The Note that a contact material may be disposed between the metal support cell assembly 1 </ b> A and the current collection auxiliary layer 130 so that they are in conductive contact with each other.
　図３は、メタルサポートセルアッセンブリー１Ａの分解斜視図であり、図４は、その部分断面図である。図３および図４に示すように、メタルサポートセルアッセンブリー１Ａは、メタルサポートセル１０と、メタルサポートセル１０の外周を保持するセルフレーム１１３と、を有する。 FIG. 3 is an exploded perspective view of the metal support cell assembly 1A, and FIG. 4 is a partial cross-sectional view thereof. As shown in FIGS. 3 and 4, the metal support cell assembly 1 </ b> A includes a metal support cell 10 and a cell frame 113 that holds the outer periphery of the metal support cell 10.
　（メタルサポートセル１０）
　図５は、メタルサポートセル１０の断面図である。図３～図５に示すように、メタルサポートセル１０は、発電セル２０と、発電セル２０を支持する金属製のメタルサポート層６０と、を有する。メタルサポートセル１０は、電解質支持型セルや電極支持型セルに比べて機械的強度、急速起動性等に優れる。 (Metal support cell 10)
FIG. 5 is a cross-sectional view of the metal support cell 10. As shown in FIGS. 3 to 5, the metal support cell 10 includes a power generation cell 20 and a metal support layer 60 made of metal that supports the power generation cell 20. The metal support cell 10 is superior in mechanical strength, quick startability, and the like as compared with the electrolyte support cell and the electrode support cell.
　（発電セル２０）
　図３～図５に示すように、発電セル２０は、電解質層４０の両側に一対の電極であるカソード層３０およびアノード層５０を積層して構成される。アノード層５０は、電解質層４０とメタルサポート層６０との間に配置される。換言すると、アノード層５０の一方側には、電解質層４０が配置され、アノード層５０の他方側には、メタルサポート層６０が配置される。 (Power generation cell 20)
As shown in FIGS. 3 to 5, the power generation cell 20 is configured by laminating a cathode layer 30 and an anode layer 50, which are a pair of electrodes, on both sides of the electrolyte layer 40. The anode layer 50 is disposed between the electrolyte layer 40 and the metal support layer 60. In other words, the electrolyte layer 40 is disposed on one side of the anode layer 50, and the metal support layer 60 is disposed on the other side of the anode layer 50.
　（カソード層３０）
　カソード層３０は、酸化剤極であって、カソードガス（例えば空気に含まれる酸素）と電子を反応させて、酸素分子を酸化物イオンに変換する。カソード層３０は、酸化雰囲気に耐性を有し、カソードガスを透過させるガス透過性および電気伝導度が高い。さらに、カソード層３０は、酸素分子を酸素イオンに変換する触媒機能を有する。 (Cathode layer 30)
The cathode layer 30 is an oxidizer electrode, and reacts cathode gas (for example, oxygen contained in air) with electrons to convert oxygen molecules into oxide ions. The cathode layer 30 is resistant to an oxidizing atmosphere, and has high gas permeability and electrical conductivity for allowing the cathode gas to permeate. Further, the cathode layer 30 has a catalytic function for converting oxygen molecules into oxygen ions.
　カソード層３０の形成材料は、例えば、ランタン、ストロンチウム、マンガン、コバルト等の酸化物が挙げられる。 Examples of the material for forming the cathode layer 30 include oxides such as lanthanum, strontium, manganese, and cobalt.
　（電解質層４０）
　電解質層４０は、カソード層３０からアノード層５０に向かって酸化物イオンを伝導させつつ、ガスと電子を通過させない性質を有する。酸素イオンが発電の伝導体である場合には、電解質層４０は、酸素イオンの伝導性が高い材料から形成されることが好ましい。 (Electrolyte layer 40)
The electrolyte layer 40 has the property of not allowing gas and electrons to pass while conducting oxide ions from the cathode layer 30 toward the anode layer 50. When oxygen ions are a power generation conductor, the electrolyte layer 40 is preferably formed from a material having high oxygen ion conductivity.
　電解質層４０は、セラミックから形成される。電解質層４０を形成するセラミックは、例えば、例えば、希土類酸化物（例えば、Ｙ２Ｏ３、Ｓｃ２Ｏ３、Ｇｄ２Ｏ３、Ｓｍ２Ｏ３、Ｙｂ２Ｏ３、Ｎｄ２Ｏ３等から選択される１種または２種以上）を固溶した安定化ジルコニア、セリア系固溶体、ペロブスカイト型酸化物（例えば、ＳｒＣｅＯ３、ＢａＣｅＯ３、ＣａＺｒＯ３、ＳｒＺｒＯ３等）等の固体酸化物セラミックなどが挙げられる。なお、本明細書中において、「セラミック」とは、無機物の焼結体を広く意味し、非金属の酸化物に限られず金属の酸化物も含まれるものとする。 The electrolyte layer 40 is formed from ceramic. The ceramic forming the electrolyte layer 40 is, for example, a rare earth oxide (for example, Y 2 O 3 , Sc 2 O 3 , Gd 2 O 3 , Sm 2 O 3 , Yb 2 O 3 , Nd 2 O 3, etc.). Solid oxide ceramics such as stabilized zirconia, ceria-based solid solution, perovskite oxide (for example, SrCeO 3 , BaCeO 3 , CaZrO 3 , SrZrO 3, etc.) in which the selected one or two or more are dissolved. Can be mentioned. Note that in this specification, “ceramic” broadly means an inorganic sintered body, and is not limited to a non-metallic oxide but also includes a metal oxide.
　（アノード層５０）
　アノード層５０は、燃料極であって、アノードガス（例えば水素）と酸化物イオンを反応させて、アノードガスの酸化物を生成するとともに電子を取り出す。アノード層５０は、還元雰囲気に耐性を有し、アノードガスを透過させるガス透過性および電気伝導度が高い。さらに、アノード層５０は、アノードガスを酸化物イオンと反応させる触媒機能を有する。 (Anode layer 50)
The anode layer 50 is a fuel electrode, and reacts an anode gas (for example, hydrogen) with oxide ions to generate an oxide of the anode gas and take out electrons. The anode layer 50 is resistant to a reducing atmosphere, and has high gas permeability and electrical conductivity that allow the anode gas to pass therethrough. Furthermore, the anode layer 50 has a catalytic function for reacting the anode gas with oxide ions.
　図５に示すように、アノード層５０は、セラミック粒子２１０と金属粒子２２０とを含む。本実施形態に係るアノード層５０は、電解質層４０に隣接して配置される第１アノード層５１と、メタルサポート層６０に隣接して配置される第２アノード層５２と、を有する。 As shown in FIG. 5, the anode layer 50 includes ceramic particles 210 and metal particles 220. The anode layer 50 according to this embodiment includes a first anode layer 51 disposed adjacent to the electrolyte layer 40 and a second anode layer 52 disposed adjacent to the metal support layer 60.
　第１アノード層５１は、セラミック粒子２１０から形成される。第２アノード層５２は、セラミック粒子２１０および金属粒子２２０から形成される。これにより、アノード層５０中のセラミック粒子２１０の含有量に対する金属粒子２２０の含有量の比率（以下、「金属／セラミック比」と称する）は、メタルサポート層６０側が電解質層４０側よりも大きくなるように形成されている。 The first anode layer 51 is formed from ceramic particles 210. The second anode layer 52 is formed from ceramic particles 210 and metal particles 220. Thereby, the ratio of the content of the metal particles 220 to the content of the ceramic particles 210 in the anode layer 50 (hereinafter referred to as “metal / ceramic ratio”) is larger on the metal support layer 60 side than on the electrolyte layer 40 side. It is formed as follows.
　上記のように、電解質層４０側に配置される第１アノード層５１では、セラミックの含有量が高い。このため、アノード層５０と電解質層との間の界面でのイオン伝導性を維持することができる。 As described above, the first anode layer 51 disposed on the electrolyte layer 40 side has a high ceramic content. For this reason, ionic conductivity at the interface between the anode layer 50 and the electrolyte layer can be maintained.
　また、一般的に、金属とセラミックとは、熱膨張率が異なる。また、金属は、酸化によって膨張する。上記のように、メタルサポート層６０側に配置される第２アノード層５２では、金属／セラミック比が比較的高い。このため、金属とセラミックとの間の熱膨張率の差や金属の酸化によるアノード層５０とメタルサポート層６０との間の体積変化の差が界面で小さくなる。これにより、アノード層５０とメタルサポート層６０との間の界面の剥離を抑制することができる。 In general, metal and ceramic have different coefficients of thermal expansion. Also, the metal expands due to oxidation. As described above, the second anode layer 52 disposed on the metal support layer 60 side has a relatively high metal / ceramic ratio. For this reason, the difference in the coefficient of thermal expansion between the metal and the ceramic and the difference in volume change between the anode layer 50 and the metal support layer 60 due to the oxidation of the metal are reduced at the interface. Thereby, peeling of the interface between the anode layer 50 and the metal support layer 60 can be suppressed.
　第２アノード層５２内の金属／セラミック比は、特に限定されないが、例えば、７０％／３０％程度に設定することができる。 The metal / ceramic ratio in the second anode layer 52 is not particularly limited, but can be set to about 70% / 30%, for example.
　セラミック粒子２１０は、電解質層４０を形成するセラミックと同程度の格子定数および同程度の熱膨張率を有することが好ましい。これにより、アノード層５０と電解質層４０との間の界面での接合性を向上させることができる。ここで、「同程度の格子定数」とは、電解質層４０とアノード層５０との間の界面での接合強度を確保することができる程度に、少なくとも界面における結晶構造が整合性を有していることを意味する。なお、格子定数には、格子間距離および格子間角度などを含むものとする。 The ceramic particles 210 preferably have the same lattice constant and the same thermal expansion coefficient as the ceramic forming the electrolyte layer 40. Thereby, the bondability at the interface between the anode layer 50 and the electrolyte layer 40 can be improved. Here, the “similar lattice constant” means that at least the crystal structure at the interface has consistency so that the bonding strength at the interface between the electrolyte layer 40 and the anode layer 50 can be secured. Means that The lattice constant includes an interstitial distance, an interstitial angle, and the like.
　また、「同程度の熱膨張率」とは、セラミック粒子２１０と電解質層４０を形成するセラミックとの熱膨張率が同じ場合に限定されず、アノード層５０と電解質層４０との間の界面剥離が抑制される程度の許容差を含むことを意味する。熱膨張率の許容差は、例えば、５％以下が好ましく、１％以下がより好ましい。 Further, the “same thermal expansion coefficient” is not limited to the case where the thermal expansion coefficient of the ceramic particles 210 and the ceramic forming the electrolyte layer 40 is the same, and the interface peeling between the anode layer 50 and the electrolyte layer 40 is performed. Is included to the extent that is suppressed. For example, the tolerance of the coefficient of thermal expansion is preferably 5% or less, and more preferably 1% or less.
　セラミック粒子２１０の構成材料としては、電解質層４０を形成するセラミックと同様の材料を用いることができる。 As the constituent material of the ceramic particles 210, the same material as the ceramic forming the electrolyte layer 40 can be used.
　金属粒子２２０は、メタルサポート層６０を形成する金属と同程度の熱膨張率を有することが好ましい。これにより、アノード層５０とメタルサポート層６０との間の界面での熱膨張率の差による剥離が抑制される。ここで、「同程度の熱膨張率」とは、金属粒子２２０とメタルサポート層６０を形成する金属との熱膨張率が同じ場合に限定されず、アノード層５０とメタルサポート層６０との間の界面剥離が抑制される程度の許容差を含むことを意味する。熱膨張率の許容差は、例えば、５％以下が好ましく、１％以下がより好ましい。 The metal particles 220 preferably have a thermal expansion coefficient comparable to that of the metal forming the metal support layer 60. Thereby, peeling due to the difference in coefficient of thermal expansion at the interface between the anode layer 50 and the metal support layer 60 is suppressed. Here, “the same degree of thermal expansion coefficient” is not limited to the case where the thermal expansion coefficient of the metal particles 220 and the metal forming the metal support layer 60 is the same, and is between the anode layer 50 and the metal support layer 60. It means that a tolerance is included to such an extent that interfacial peeling is suppressed. For example, the tolerance of the coefficient of thermal expansion is preferably 5% or less, and more preferably 1% or less.
　金属粒子２２０の構成材料としては、メタルサポート層６０を形成する金属と同様の材料を用いることができる。なお、本明細書中において、「金属粒子２２０」は、アノード層５０を構成する主成分を意味し、アノード層５０の金属触媒は含まないものとする。また、「金属粒子２２０を形成する金属」および「メタルサポート層６０を形成する金属」には、金属の酸化物などのセラミックは含まれないものとする。 As the constituent material of the metal particles 220, the same material as the metal forming the metal support layer 60 can be used. In the present specification, the “metal particles 220” means a main component constituting the anode layer 50, and does not include the metal catalyst of the anode layer 50. Further, “metal forming the metal particles 220” and “metal forming the metal support layer 60” do not include ceramics such as metal oxides.
　アノード層５０は、複数の空孔Ｈが形成された多孔体である。図６は、アノード層５０の空孔Ｈの大きさを説明するための概略断面図である。図６に示すように、アノード層５０内の単位体積に含まれる空孔Ｈの平均径は、メタルサポート層６０側（図６中の下側）が電解質層４０側（図６中の上側）よりも大きくなるように形成されている。これにより、アノード層５０は、メタルサポート層６０側で空孔Ｈが大きいため、ガス拡散性が向上し、図６中の矢印で示すように効率的に電解質層４０付近までアノードガスを供給することができる。また、アノード層５０は、電解質層４０側で空孔Ｈが小さいため、電解質層４０とアノード層５０と接触面積が増加する。これにより、電解質層４０とアノード層５０との間の界面でイオン伝導性を向上させてイオンの供給量を増加させることができる。 The anode layer 50 is a porous body in which a plurality of holes H are formed. FIG. 6 is a schematic cross-sectional view for explaining the size of the holes H of the anode layer 50. As shown in FIG. 6, the average diameter of the holes H included in the unit volume in the anode layer 50 is such that the metal support layer 60 side (lower side in FIG. 6) is on the electrolyte layer 40 side (upper side in FIG. 6). It is formed so as to be larger. As a result, the anode layer 50 has large holes H on the metal support layer 60 side, so that the gas diffusibility is improved, and the anode gas is efficiently supplied to the vicinity of the electrolyte layer 40 as indicated by the arrows in FIG. be able to. Further, since the anode layer 50 has small holes H on the electrolyte layer 40 side, the contact area between the electrolyte layer 40 and the anode layer 50 increases. Thereby, the ion conductivity can be improved at the interface between the electrolyte layer 40 and the anode layer 50, and the supply amount of ions can be increased.
　ここで、「空孔Ｈの平均径」とは、例えば、走査型電子顕微鏡（ＳＥＭ）や透過型電子顕微鏡（ＴＥＭ）などを用いて観察される空孔Ｈを形成する孔壁面の輪郭線上の任意の２点間の距離のうち、最大の距離を意味する。 Here, the “average diameter of the holes H” is, for example, on the outline of the hole wall surface that forms the holes H observed using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or the like. It means the maximum distance among any two points.
　アノード層５０内の空孔Ｈには、触媒が含浸される。メタルサポートセル１０の製造においては、触媒は、空孔Ｈが形成された後に、メタルサポート層６０側からアノード層５０内に含浸される。この際、空孔Ｈの平均径が電解質層４０側よりも大きいメタルサポート層６０側から触媒を含浸させることによって、触媒を電解質層４０付近まで含浸させることができる。 The pores H in the anode layer 50 are impregnated with a catalyst. In the manufacture of the metal support cell 10, the catalyst is impregnated into the anode layer 50 from the metal support layer 60 side after the holes H are formed. At this time, the catalyst can be impregnated to the vicinity of the electrolyte layer 40 by impregnating the catalyst from the metal support layer 60 side where the average diameter of the holes H is larger than that of the electrolyte layer 40 side.
　アノード層５０の触媒としては、例えば、ニッケル（Ｎｉ）等の金属触媒を用いることができる。 As the catalyst for the anode layer 50, for example, a metal catalyst such as nickel (Ni) can be used.
　（メタルサポート層６０）
　メタルサポート層６０は、図３および図４に示すように、発電セル２０をアノード層５０の側から支持するものである。メタルサポート層６０によって発電セル２０を支持することにより、発電セル２０の機械的強度を向上させて破損を抑制することができる。メタルサポート層６０は、ガス透過性および電気伝導性を有する多孔質の金属から形成される。 (Metal support layer 60)
As shown in FIGS. 3 and 4, the metal support layer 60 supports the power generation cell 20 from the anode layer 50 side. By supporting the power generation cell 20 with the metal support layer 60, the mechanical strength of the power generation cell 20 can be improved and damage can be suppressed. The metal support layer 60 is formed from a porous metal having gas permeability and electrical conductivity.
　メタルサポート層６０を形成する金属としては、例えば、ニッケル（Ｎｉ）やクロム（Ｃｒ）を含有する耐食合金や耐食鋼、ステンレス鋼などを用いることができる。 As the metal that forms the metal support layer 60, for example, a corrosion-resistant alloy, corrosion-resistant steel, stainless steel, or the like containing nickel (Ni) or chromium (Cr) can be used.
　（セルフレーム１１３）
　セルフレーム１１３は、図３および図４に示すように、メタルサポートセル１０を周囲から保持するものである。図３に示すように、セルフレーム１１３は、開口部１１３Ｈを有する。セルフレーム１１３の開口部１１３Ｈには、メタルサポートセル１０が配置される。メタルサポートセル１０の外周は、セルフレーム１１３の開口部１１３Ｈの内縁に接合される。 (Cell frame 113)
As shown in FIGS. 3 and 4, the cell frame 113 holds the metal support cell 10 from the periphery. As shown in FIG. 3, the cell frame 113 has an opening 113H. The metal support cell 10 is disposed in the opening 113H of the cell frame 113. The outer periphery of the metal support cell 10 is joined to the inner edge of the opening 113H of the cell frame 113.
　セルフレーム１１３は、図３に示すように、アノードガスが流通するアノードガス流入口１１３ａおよびアノードガス流出口１１３ｂと、カソードガスが流通するカソードガス流入口１１３ｃおよびカソードガス流出口１１３ｄと、を有している。 As shown in FIG. 3, the cell frame 113 has an anode gas inlet 113a and an anode gas outlet 113b through which the anode gas flows, and a cathode gas inlet 113c and a cathode gas outlet 113d through which the cathode gas flows. doing.
　（セパレータ１２０）
　図２に示すように、セパレータ１２０の流路部１２１は、凹凸形状が長手方向Ｙに延在するように略直線状に形成されている。これにより、流路部１２１に沿って流れるガスの流れ方向は、長手方向Ｙである。 (Separator 120)
As shown in FIG. 2, the flow path portion 121 of the separator 120 is formed in a substantially linear shape so that the concavo-convex shape extends in the longitudinal direction Y. Thereby, the flow direction of the gas flowing along the flow path part 121 is the longitudinal direction Y.
　図２に示すように、セパレータ１２０は、アノードガスが流通するアノードガス流入口１２５ａおよびアノードガス流出口１２５ｂと、カソードガスが流通するカソードガス流入口１２５ｃおよびカソードガス流出口１２５ｄと、を有している。 As shown in FIG. 2, the separator 120 has an anode gas inlet 125a and an anode gas outlet 125b through which anode gas flows, and a cathode gas inlet 125c and cathode gas outlet 125d through which cathode gas flows. ing.
　（集電補助層１３０）
　集電補助層１３０は、ガスを通す空間を形成しつつ面圧を均等にして、メタルサポートセル１０とセパレータ１２０との電気的な接触を補助する。集電補助層１３０は、例えば、金網状のエキスパンドメタルによって形成することができる。 (Current collection auxiliary layer 130)
The current collecting auxiliary layer 130 forms a space through which gas passes and makes the surface pressure uniform to assist the electrical contact between the metal support cell 10 and the separator 120. The current collection auxiliary layer 130 can be formed of, for example, a wire mesh expanded metal.
　［メタルサポートセル１０の製造方法］
　次に、図７を参照して、メタルサポートセル１０の製造方法について説明する。図７は、メタルサポートセル１０の製造方法を説明するための概略図である。なお、メタルサポートセル１０の前駆体である電解質層４０、アノード層５０およびメタルサポート層６０から構成されるハーフセルの製造方法について説明し、カソード層３０の製造方法については省略する。 [Method for Manufacturing Metal Support Cell 10]
Next, with reference to FIG. 7, the manufacturing method of the metal support cell 10 is demonstrated. FIG. 7 is a schematic view for explaining a method for manufacturing the metal support cell 10. In addition, the manufacturing method of the half cell comprised from the electrolyte layer 40 which is a precursor of the metal support cell 10, the anode layer 50, and the metal support layer 60 is demonstrated, and the manufacturing method of the cathode layer 30 is abbreviate | omitted.
　メタルサポートセル１０の製造方法は、スラリー調製工程と、塗工工程と、積層工程と、焼結工程と、と有する。 The manufacturing method of the metal support cell 10 has a slurry preparation process, a coating process, a lamination process, and a sintering process.
　まず、スラリー調製工程では、スラリー原料を混合して電解質スラリー、第１アノード電極スラリー、第２アノード電極スラリー、およびメタルサポートスラリーを調製する。スラリー原料の混合には、公知の攪拌装置を適宜選択して使用することができる。 First, in the slurry preparation step, the slurry raw materials are mixed to prepare an electrolyte slurry, a first anode electrode slurry, a second anode electrode slurry, and a metal support slurry. For mixing the slurry raw materials, a known stirring device can be appropriately selected and used.
　電解質スラリーは、セラミック粉末を主成分とし、溶媒およびバインダーを含むスラリー原料を混合して形成される。 The electrolyte slurry is formed by mixing a slurry raw material containing ceramic powder as a main component and containing a solvent and a binder.
　第１アノード電極スラリーは、セラミック粒子２１０を主成分とし、溶媒およびバインダーを含むスラリー原料を混合して形成される。第２アノード電極スラリーは、セラミック粒子２１０および金属粒子２２０を主成分とし、溶媒およびバインダーを含むスラリー原料を混合して形成される。 The first anode electrode slurry is formed by mixing a slurry raw material containing ceramic particles 210 as a main component and containing a solvent and a binder. The second anode electrode slurry is formed by mixing slurry raw materials containing ceramic particles 210 and metal particles 220 as main components and containing a solvent and a binder.
　メタルサポートスラリーは、金属粉末を主成分とし、溶媒およびバインダーを含むスラリー原料を混合して形成される。 The metal support slurry is formed by mixing a slurry raw material containing a metal powder as a main component and containing a solvent and a binder.
　スラリー用の溶媒としては、例えば、溶媒としては、特に制限されないが、水、および／または、メタノール、エタノール、１－プロパノール（ＮＰＡ）、２－プロパノール、エチレングリコール、プロピレングリコールなどのアルコール系溶媒、Ｎメチル－２ピロリドン（ＮＭＰ）など有機溶媒が挙げられる。これら溶媒は、一種のみを用いてもよいし、二種以上を混合して用いてもよい。溶媒の使用量は、スラリーをシート状に成形する際において、その粘度が成形に適したものとなるように調整することが好ましい。 As the solvent for the slurry, for example, the solvent is not particularly limited, but water and / or alcohol solvents such as methanol, ethanol, 1-propanol (NPA), 2-propanol, ethylene glycol, propylene glycol, An organic solvent such as N-methyl-2-pyrrolidone (NMP) can be mentioned. These solvents may be used alone or in combination of two or more. The amount of the solvent used is preferably adjusted so that the viscosity is suitable for molding when the slurry is molded into a sheet.
　スラリーに添加するバインダーは、公知の有機バインダーを適宜選択して使用することができる。有機バインダーとしては、例えば、エチレン系共重合体、スチレン系共重合体、アクリレート系共重合体、メタクリレート系共重合体、ビニルブチラール系樹脂、ビニルアセタール系樹脂、ビニルホルマール系樹脂、ビニルアルコール系樹脂、エチルセルロースなどのセルロース類が挙げられる。 As the binder to be added to the slurry, a known organic binder can be appropriately selected and used. Examples of the organic binder include an ethylene copolymer, a styrene copolymer, an acrylate copolymer, a methacrylate copolymer, a vinyl butyral resin, a vinyl acetal resin, a vinyl formal resin, and a vinyl alcohol resin. And celluloses such as ethyl cellulose.
　なお、各スラリーには、必要に応じて可塑剤や分散剤などを添加してもよい。 In addition, you may add a plasticizer, a dispersing agent, etc. to each slurry as needed.
　次に、塗工工程では、ナイフコート、ドクターブレードなどの塗工装置を用いたテープキャスト法などのシート成形法を用いて上記スラリー調製工程で調製した各スラリーをシート状に成形する。得られたシートを、乾燥後、必要に応じて加熱処理することによって電解質シート、第１アノード電極シート、第２アノード電極シートおよびメタルサポートシートを得ることができる。 Next, in the coating step, each slurry prepared in the slurry preparation step is formed into a sheet using a sheet forming method such as a tape casting method using a coating device such as a knife coater or a doctor blade. The obtained sheet is dried and then heat-treated as necessary to obtain an electrolyte sheet, a first anode electrode sheet, a second anode electrode sheet, and a metal support sheet.
　次に、積層工程では、電解質シート、第１アノード電極シート、第２アノード電極シートおよびメタルサポートシートを順に積層して貼り合わせて積層体を形成する。 Next, in the laminating step, an electrolyte sheet, a first anode electrode sheet, a second anode electrode sheet, and a metal support sheet are sequentially laminated and bonded to form a laminated body.
　最後に、焼結工程では、上記積層体を脱脂および焼結して、メタルサポートセル１０の前駆体であるハーフセルを得ることができる。なお、焼成条件は特に制限されず、公知の条件に設定することができる。 Finally, in the sintering step, the laminate can be degreased and sintered to obtain a half cell that is a precursor of the metal support cell 10. The firing conditions are not particularly limited and can be set to known conditions.
　なお、アノード層５０が２層構造の場合を説明したが、３層以上の多層構造（後述する変形例２を参照）または単層構造（後述する変形例３を参照）の場合は、層の数に応じて調製するスラリーの種類を変更することができる。 In addition, although the case where the anode layer 50 has a two-layer structure has been described, in the case of a multilayer structure of three or more layers (see Modification 2 described later) or a single-layer structure (see Modification 3 described later), The kind of slurry to be prepared can be changed according to the number.
　以下、図８～図１１を参照して、本実施形態に係るメタルサポートセル１０の作用効果について対比例に係るメタルサポートセルと比較して説明する。図８は、対比例１に係るメタルサポートセルの断面図である。図９は、対比例２に係るメタルサポートセルの断面図である。図１０は、図９の破線部Ｂによって囲まれる部分の拡大断面図である。なお、図１０中の矢印は、イオンの流れを示す。図１１は、対比例３に係るメタルサポートセルの断面図である。 Hereinafter, the operation and effect of the metal support cell 10 according to this embodiment will be described with reference to FIGS. FIG. 8 is a cross-sectional view of the metal support cell according to the comparative example 1. FIG. 9 is a cross-sectional view of the metal support cell according to the comparative 2. 10 is an enlarged cross-sectional view of a portion surrounded by a broken line portion B in FIG. Note that the arrows in FIG. 10 indicate the flow of ions. FIG. 11 is a cross-sectional view of a metal support cell according to Comparative Example 3.
　図８に示す対比例１に係るメタルサポートセルは、セラミック粒子２１０から形成されたアノード層５０ａを有する。このため、アノード層５０ａとメタルサポート層６０との間の熱膨張率の差やメタルサポート層６０の金属が酸化して膨張することによって、アノード層５０ａとメタルサポート層６０との間に体積変化の差が生じてしまう。特に、固体酸化物形燃料電池の作動温度は、約７００～１０００°Ｃと高温であるため、アノード層５０ａとメタルサポート層６０との間に体積変化の差がより一層生じやすい。これにより、アノード層５０ａとメタルサポート層６０との間の界面に剥離が生じやすくなってしまう。 8 has a anode layer 50a formed from ceramic particles 210. The metal support cell according to the comparative example 1 shown in FIG. Therefore, the volume change between the anode layer 50a and the metal support layer 60 due to the difference in thermal expansion coefficient between the anode layer 50a and the metal support layer 60 or the expansion of the metal of the metal support layer 60 due to oxidation. The difference will occur. In particular, since the operating temperature of the solid oxide fuel cell is as high as about 700 to 1000 ° C., a difference in volume change is more likely to occur between the anode layer 50a and the metal support layer 60. Thereby, peeling tends to occur at the interface between the anode layer 50a and the metal support layer 60.
　図９に示す対比例２に係るメタルサポートセルは、セラミック粒子２１０および金属粒子２２０を含むアノード層５０ｂを有する。これにより、アノード層５０ｂとメタルサポート層６０との間の体積変化の差を低減することができる。しかしながら、図１０に示すように、電解質層４０とアノード層５０ｂとの間の界面にイオン伝導性の低い金属粒子２２０が存在するため、イオンの伝導パスが減少してしまう。これにより、メタルサポートセルの発電性能が低下してしまう。 9 has an anode layer 50b including ceramic particles 210 and metal particles 220. The metal support cell according to Comparative Example 2 shown in FIG. Thereby, the difference in volume change between the anode layer 50b and the metal support layer 60 can be reduced. However, as shown in FIG. 10, since the metal particles 220 having low ion conductivity exist at the interface between the electrolyte layer 40 and the anode layer 50b, the ion conduction path decreases. Thereby, the power generation performance of a metal support cell will fall.
　図１１に示す対比例３に係るメタルサポートセルは、セラミック粒子２１０から形成されたアノード層５０ｃと、アノード層５０ｃと隣接する側の空孔の一部にセラミック粒子２１０を埋め込んだ表面層６１ｃを備えるメタルサポート層６０ｃと、を有する。これにより、アノード層５０ｃとメタルサポート層６０ｃの表面層６１ｃとの間の界面の体積変化の差を低減することができる。さらに、アノード層５０ｃをセラミック粒子２１０から形成することができるため、イオン伝導性を維持することができる。しかしながら、メタルサポート層６０ｃの強度を維持するためには、メタルサポート層６０ｃの厚みを増加させる必要があるため、メタルサポートセルの厚みが増加してしまう。一方で、メタルサポートセルの厚みを低減するためにアノード層５０ｃの厚みを低減すると、反応面積が減るため、電池性能が低下してしまう。したがって、対比例３のようにメタルサポート層６０ｃの一部にセラミック粒子２１０を埋め込んだ形態は好ましくない。 The metal support cell according to Comparative Example 3 shown in FIG. 11 includes an anode layer 50c formed from the ceramic particles 210, and a surface layer 61c in which the ceramic particles 210 are embedded in a part of the holes adjacent to the anode layer 50c. A metal support layer 60c. Thereby, the difference of the volume change of the interface between the anode layer 50c and the surface layer 61c of the metal support layer 60c can be reduced. Furthermore, since the anode layer 50c can be formed from the ceramic particles 210, ion conductivity can be maintained. However, in order to maintain the strength of the metal support layer 60c, it is necessary to increase the thickness of the metal support layer 60c, which increases the thickness of the metal support cell. On the other hand, when the thickness of the anode layer 50c is reduced in order to reduce the thickness of the metal support cell, the reaction area is reduced, so that the battery performance is deteriorated. Therefore, a configuration in which the ceramic particles 210 are embedded in a part of the metal support layer 60c as in the comparative example 3 is not preferable.
　これに対して、本実施形態に係るメタルサポートセル１０は、セラミック粒子２１０と金属粒子２２０とを含み、触媒機能を備えるアノード層５０と、アノード層５０の一方側に配置され、セラミックから形成された電解質層４０と、アノード層５０の他方側に配置され、金属から形成されたメタルサポート層６０と、を有する。アノード層５０中のセラミック粒子２１０の含有量に対する金属粒子２２０の含有量の比率（金属／セラミック比）は、メタルサポート層６０側が電解質層４０側よりも大きくなるように形成されている。 On the other hand, the metal support cell 10 according to the present embodiment includes the ceramic particles 210 and the metal particles 220, is disposed on one side of the anode layer 50 having a catalytic function, and is formed of ceramic. And an electrolyte layer 40 and a metal support layer 60 disposed on the other side of the anode layer 50 and made of metal. The ratio of the content of the metal particles 220 to the content of the ceramic particles 210 in the anode layer 50 (metal / ceramic ratio) is formed so that the metal support layer 60 side is larger than the electrolyte layer 40 side.
　上記メタルサポートセル１０によれば、アノード層５０中のメタルサポート層６０側において金属／セラミック比が比較的高い。このため、金属とセラミックとの間の熱膨張率の差や金属の酸化によるアノード層５０とメタルサポート層６０との間の体積変化の差が界面で小さくなる。これにより、アノード層５０とメタルサポート層６０との間の界面の剥離を抑制することができる。また、アノード層５０中の電解質層４０側において金属／セラミック比が比較的低い、すなわち、セラミック粒子２１０の含有量が比較的高い。このため、アノード層５０と電解質層４０との間の界面でのイオン伝導性を維持することができる。 According to the metal support cell 10, the metal / ceramic ratio is relatively high on the metal support layer 60 side in the anode layer 50. For this reason, the difference in the coefficient of thermal expansion between the metal and the ceramic and the difference in volume change between the anode layer 50 and the metal support layer 60 due to the oxidation of the metal are reduced at the interface. Thereby, peeling of the interface between the anode layer 50 and the metal support layer 60 can be suppressed. Further, the metal / ceramic ratio is relatively low on the electrolyte layer 40 side in the anode layer 50, that is, the content of the ceramic particles 210 is relatively high. For this reason, the ionic conductivity at the interface between the anode layer 50 and the electrolyte layer 40 can be maintained.
　また、アノード層５０は複数の空孔Ｈを有する多孔体であり、アノード層５０内の単位体積に含まれる空孔Ｈの平均径は、メタルサポート層６０側が電解質層４０側よりも大きくなるように形成されている。これにより、アノード層５０は、メタルサポート層６０側で空孔Ｈが大きいため、ガス拡散性が向上し、効率的に電解質層４０付近までアノードガスを供給することができる。また、アノード層５０は、電解質層４０側で空孔Ｈが小さいため、電解質層４０とアノード層５０との接触面積が増加する。これにより、電解質層４０とアノード層５０との間の界面でイオンの供給量が増えるため、イオン伝導性を向上させることができる。 The anode layer 50 is a porous body having a plurality of pores H, and the average diameter of the pores H included in the unit volume in the anode layer 50 is larger on the metal support layer 60 side than on the electrolyte layer 40 side. Is formed. Thereby, since the anode layer 50 has large holes H on the metal support layer 60 side, the gas diffusibility is improved, and the anode gas can be efficiently supplied to the vicinity of the electrolyte layer 40. In addition, since the anode layer 50 has small holes H on the electrolyte layer 40 side, the contact area between the electrolyte layer 40 and the anode layer 50 increases. Thereby, since the supply amount of ions increases at the interface between the electrolyte layer 40 and the anode layer 50, the ion conductivity can be improved.
　また、アノード層５０は、空孔Ｈに含浸した触媒をさらに有する。メタルサポートセル１０の製造においては、触媒は、空孔Ｈが形成された後に、メタルサポート層６０側からアノード層５０内に含浸される。この際、空孔Ｈの平均径が電解質層４０側よりも大きいメタルサポート層６０側から触媒を含浸させることによって、触媒を電解質層４０付近まで含浸させることができる。 The anode layer 50 further has a catalyst impregnated in the holes H. In the manufacture of the metal support cell 10, the catalyst is impregnated into the anode layer 50 from the metal support layer 60 side after the holes H are formed. At this time, the catalyst can be impregnated to the vicinity of the electrolyte layer 40 by impregnating the catalyst from the metal support layer 60 side where the average diameter of the holes H is larger than that of the electrolyte layer 40 side.
　また、アノード層５０内の金属粒子２２０は、メタルサポート層６０を形成する金属と同程度の熱膨張率を有する。これにより、アノード層５０とメタルサポート層６０との間の界面での熱膨張率の差による剥離が抑制される。 Further, the metal particles 220 in the anode layer 50 have a thermal expansion coefficient similar to that of the metal forming the metal support layer 60. Thereby, peeling due to the difference in coefficient of thermal expansion at the interface between the anode layer 50 and the metal support layer 60 is suppressed.
　また、アノード層５０内のセラミック粒子２１０は、電解質層４０を形成するセラミックと同程度の格子定数および同程度の熱膨張率を有する。これにより、アノード層５０と電解質層４０との間の界面での接合性を向上させることができる。 Moreover, the ceramic particles 210 in the anode layer 50 have the same lattice constant and the same thermal expansion coefficient as the ceramic forming the electrolyte layer 40. Thereby, the bondability at the interface between the anode layer 50 and the electrolyte layer 40 can be improved.
　また、アノード層５０は、第１アノード層５１と第２アノード層５２を含む２層以上の層から構成される多層構造を有する。これにより、各層ごとに、金属／セラミック比、金属粒子２２０の粒子径、セラミック粒子２１０の粒子径および空孔径などを制御しやすくなる。 The anode layer 50 has a multilayer structure composed of two or more layers including the first anode layer 51 and the second anode layer 52. This makes it easy to control the metal / ceramic ratio, the particle diameter of the metal particles 220, the particle diameter of the ceramic particles 210, the pore diameter, and the like for each layer.
　以下、本実施形態の変形例について説明する。なお、前述した実施形態と同様の構成については、同一の符号を付してその説明を省略する。 Hereinafter, modifications of the present embodiment will be described. In addition, about the structure similar to embodiment mentioned above, the same code | symbol is attached | subjected and the description is abbreviate | omitted.
　＜変形例１＞
　図１２は、変形例１に係るメタルサポートセルの断面図である。変形例１に係るメタルサポートセルのアノード層１５０は、図１２に示すように、単位体積に含まれるセラミック粒子２１０の平均粒子径および単位体積に含まれる金属粒子２２０の平均粒子径が、メタルサポート層６０側（図１２の下側）が電解質層４０側よりも大きくなるように構成されている点で前述した実施形態と異なる。なお、アノード層１５０は、前述した実施形態のように多層構造としてもよいし、単層により構成してもよい。 <Modification 1>
FIG. 12 is a cross-sectional view of a metal support cell according to the first modification. As shown in FIG. 12, the anode layer 150 of the metal support cell according to the first modification has an average particle size of the ceramic particles 210 included in the unit volume and an average particle size of the metal particles 220 included in the unit volume. This is different from the above-described embodiment in that the layer 60 side (the lower side in FIG. 12) is configured to be larger than the electrolyte layer 40 side. The anode layer 150 may have a multilayer structure as in the above-described embodiment, or may be configured by a single layer.
　ここで、「粒子径」とは、例えば、走査型電子顕微鏡（ＳＥＭ）や透過型電子顕微鏡（ＴＥＭ）などを用いて観察される粒子の輪郭線上の任意の２点間の距離のうち、最大の距離を意味する。 Here, the “particle diameter” is, for example, the maximum of the distance between any two points on the contour line of a particle observed using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or the like. Means distance.
　上述したように、変形例１に係るメタルサポートセルは、アノード層１５０内の単位体積に含まれる金属粒子２２０の平均粒子径は、メタルサポート層６０側が電解質層４０側よりも大きくなるように形成されている。金属粒子２２０の平均粒子径を大きくすることによって、単位体積に含まれる金属粒子２２０の合計の表面積を小さくすることができる。このため、アノード層１５０は、メタルサポート層６０側において金属の酸化による膨張を抑えることができる。 As described above, the metal support cell according to Modification 1 is formed such that the average particle diameter of the metal particles 220 included in the unit volume in the anode layer 150 is larger on the metal support layer 60 side than on the electrolyte layer 40 side. Has been. By increasing the average particle diameter of the metal particles 220, the total surface area of the metal particles 220 included in the unit volume can be reduced. For this reason, the anode layer 150 can suppress expansion due to metal oxidation on the metal support layer 60 side.
　また、アノード層１５０内の単位体積に含まれるセラミック粒子２１０の平均粒子径は、メタルサポート層６０側が電解質層４０側よりも大きくなるように形成されている。換言すると、アノード層１５０内の単位体積に含まれるセラミック粒子２１０の平均粒子径は、電解質層４０側がメタルサポート層６０側よりも小さくなるように形成されている。これにより、電解質層４０とアノード層５０との間の界面の接触面積が増加するため、イオン伝導性を向上させることができる。 Also, the average particle diameter of the ceramic particles 210 contained in the unit volume in the anode layer 150 is formed so that the metal support layer 60 side is larger than the electrolyte layer 40 side. In other words, the average particle diameter of the ceramic particles 210 contained in the unit volume in the anode layer 150 is formed so that the electrolyte layer 40 side is smaller than the metal support layer 60 side. Thereby, since the contact area of the interface between the electrolyte layer 40 and the anode layer 50 increases, ion conductivity can be improved.
　＜変形例２＞
　図１３は、変形例２に係るメタルサポートセルの断面図である。変形例２に係るメタルサポートセルのアノード層２５０は、図１３に示すように、３層以上の層から構成される多層構造を有する点で前述した実施形態と異なる。 <Modification 2>
FIG. 13 is a cross-sectional view of a metal support cell according to Modification 2. The anode layer 250 of the metal support cell according to the modification 2 is different from the above-described embodiment in that it has a multilayer structure composed of three or more layers as shown in FIG.
　アノード層２５０のうち、メタルサポート層６０に近い側の層は、電解質層４０に近い側の層よりも金属／セラミック比および空孔径が大きくなるように形成されている。なお、図１３では、セラミック粒子２１０の粒子径は同じ大きさで図示しているが、電解質層４０に近い側の層がメタルサポート層６０に近い側の層よりもセラミック粒子２１０の粒子径が小さくなるように形成してもよい。同様に、金属粒子２２０の粒子径は同じ大きさで図示しているが、メタルサポート層６０に近い側の層が電解質層４０に近い側の層よりも金属粒子２２０の粒子径が大きくなるように形成してもよい。 Of the anode layer 250, the layer closer to the metal support layer 60 is formed so that the metal / ceramic ratio and the pore diameter are larger than the layer closer to the electrolyte layer 40. In FIG. 13, the particle diameters of the ceramic particles 210 are the same, but the layer closer to the electrolyte layer 40 has a particle diameter of the ceramic particles 210 than the layer closer to the metal support layer 60. You may form so that it may become small. Similarly, the particle diameter of the metal particles 220 is illustrated with the same size, but the particle diameter of the metal particles 220 is larger in the layer closer to the metal support layer 60 than in the layer closer to the electrolyte layer 40. You may form in.
　上述したように、変形例２に係るメタルサポートセルのアノード層２５０は、３層以上の層から構成される多層構造を有する。多層構造の層の数が増加する程、アノード層２５０内の金属／セラミック比、セラミック粒子２１０の粒子径、金属粒子２２０の粒子径、空孔径などの分布をより高い精度で制御しやすくなる。金属／セラミック比、セラミック粒子２１０の粒子径、金属粒子２２０の粒子径および空孔径を、それぞれメタルサポート層６０側が電解質層４０側よりも大きくなるように形成することによる効果は、上記実施形態および変形例１において述べた通りである。 As described above, the anode layer 250 of the metal support cell according to the modified example 2 has a multilayer structure including three or more layers. As the number of layers in the multilayer structure increases, the distribution of the metal / ceramic ratio in the anode layer 250, the particle diameter of the ceramic particles 210, the particle diameter of the metal particles 220, the pore diameter, and the like becomes easier to control with higher accuracy. The effects obtained by forming the metal / ceramic ratio, the particle diameter of the ceramic particles 210, the particle diameter of the metal particles 220, and the pore diameter so that the metal support layer 60 side is larger than the electrolyte layer 40 side are the same as in the above embodiment and As described in the first modification.
　＜変形例３＞
　図１４は、変形例３に係るメタルサポートセルの断面図である。変形例３に係るメタルサポートセルのアノード層３５０は、図１４に示すように、１層（単層）から構成される点で前述した実施形態と異なる。 <Modification 3>
FIG. 14 is a cross-sectional view of a metal support cell according to Modification 3. The anode layer 350 of the metal support cell according to the modification 3 is different from the above-described embodiment in that it is composed of one layer (single layer) as shown in FIG.
　アノード層３５０は、メタルサポート層６０側が電解質層４０側よりも金属／セラミック比および空孔径が大きくなるように形成されている。なお、図１４では、セラミック粒子２１０の粒子径は同じ大きさで図示しているが、電解質層４０側がメタルサポート層６０側よりもセラミック粒子２１０の粒子径が小さくなるように形成してもよい。同様に、金属粒子２２０の粒子径は同じ大きさで図示しているが、メタルサポート層６０側が電解質層４０側よりも金属粒子２２０の粒子径が大きくなるように形成してもよい。 The anode layer 350 is formed so that the metal support layer 60 side has a larger metal / ceramic ratio and pore diameter than the electrolyte layer 40 side. In FIG. 14, the particle diameter of the ceramic particles 210 is shown as the same size, but the ceramic particles 210 may be formed so that the particle diameter of the ceramic particles 210 is smaller on the electrolyte layer 40 side than on the metal support layer 60 side. . Similarly, although the particle diameter of the metal particle 220 is illustrated with the same size, the metal particle 220 may be formed so that the metal particle 220 has a larger particle diameter than the electrolyte layer 40 side.
　上述したように、変形例２に係るメタルサポートセルのアノード層３５０は、単層構造を有する。１層の中で金属／セラミック比、セラミック粒子２１０の粒子径、金属粒子２２０の粒子径および空孔径の分布を変化させることができる。このため、調製するスラリーの種類が減るため、製造コストを削減することができる。 As described above, the anode layer 350 of the metal support cell according to the modified example 2 has a single layer structure. The distribution of the metal / ceramic ratio, the particle diameter of the ceramic particles 210, the particle diameter of the metal particles 220, and the pore diameter can be changed in one layer. For this reason, since the kind of slurry to prepare decreases, manufacturing cost can be reduced.
　＜変形例４＞
　図１５は、変形例４に係るメタルサポートセルの断面図である。変形例４に係るメタルサポートセルのアノード層４５０は、図１５に示すように、複数の板状部材４５１から構成される点で前述した実施形態と異なる。複数の板状部材４５１間の隙間を利用してガスの流路を形成することができる。板状部材４５１は、多孔質ではない。 <Modification 4>
FIG. 15 is a cross-sectional view of a metal support cell according to Modification 4. The anode layer 450 of the metal support cell according to the modification 4 is different from the above-described embodiment in that the anode layer 450 includes a plurality of plate-like members 451 as shown in FIG. A gas flow path can be formed using gaps between the plurality of plate-like members 451. The plate-like member 451 is not porous.
　各々の板状部材４５１中の金属／セラミック比は、メタルサポート層６０側が電解質層４０側よりも大きくなるように形成されている。これにより、変形例４に係るメタルサポートセルは、前述した実施形態と同様の効果を奏する。 The metal / ceramic ratio in each plate-like member 451 is formed so that the metal support layer 60 side is larger than the electrolyte layer 40 side. Thereby, the metal support cell which concerns on the modification 4 has an effect similar to embodiment mentioned above.
　以上、実施形態および変形例を通じて本発明に係るメタルサポートセルを説明したが、本発明は実施形態において説明した内容のみに限定されることはなく、特許請求の範囲の記載に基づいて適宜変更することが可能である。 As described above, the metal support cell according to the present invention has been described through the embodiment and the modification. However, the present invention is not limited only to the content described in the embodiment, and may be appropriately changed based on the description of the claims. It is possible.
　例えば、メタルサポートセルは、前述した実施形態および変形例の仕様を適宜組み合わせて構成してもよい。 For example, the metal support cell may be configured by appropriately combining the specifications of the embodiment and the modification described above.
　また、アノード層内の金属／セラミック比、セラミック粒子の粒子径、金属粒子の粒子径および空孔径の分布は、電解質層側からメタルサポート層側に向かって線型または曲線型に増加する場合に限定されず、階段状に増加する場合も含むものとする。例えば、実施形態や変形例２のように多層構造の場合は、層ごとに金属／セラミック比、セラミック粒子の粒子径、金属粒子の粒子径および空孔径を変化させることによって階段状に増加させることができる。 Also, the distribution of metal / ceramic ratio, ceramic particle particle size, metal particle particle size and pore size in the anode layer is limited to the case where the distribution increases from the electrolyte layer side to the metal support layer side in a linear or curved shape. Not including the case of increasing stepwise. For example, in the case of a multi-layer structure as in the embodiment or the modification 2, the metal / ceramic ratio, the particle diameter of the ceramic particles, the particle diameter of the metal particles, and the pore diameter are increased stepwise for each layer. Can do.
　また、前述した変形例１では、アノード層内の単位体積に含まれるセラミック粒子の平均粒子径および単位体積に含まれる金属粒子の平均粒子径を、メタルサポート層側が電解質層側より大きくなるように形成する例について説明した。しかしながら、これに限定されず、単位体積に含まれるセラミック粒子の平均粒子径または単位体積に含まれる金属粒子の平均粒子径のいずれか一方のみをメタルサポート層側が電解質層側より大きくなるように形成してもよい。 Further, in the above-described modification 1, the average particle diameter of the ceramic particles contained in the unit volume in the anode layer and the average particle diameter of the metal particles contained in the unit volume are set so that the metal support layer side is larger than the electrolyte layer side. The example to form was demonstrated. However, the present invention is not limited to this, and only one of the average particle diameter of the ceramic particles contained in the unit volume or the average particle diameter of the metal particles contained in the unit volume is formed so that the metal support layer side is larger than the electrolyte layer side. May be.
１　　　燃料電池スタック、
１Ｕ　　セルユニット、
１Ａ　　メタルサポートセルアッセンブリー、
１０　　メタルサポートセル、
２０　　　発電セル、
３０　　　カソード層、
４０　　　電解質層、
５０、１５０、２５０、３５０、４５０　アノード層、
５１　　　第１アノード層、
５２　　　第２アノード層、
６０、６０ｃ　メタルサポート層、
１１３　　セルフレーム、
１２０　　セパレータ、
１３０　　集電補助層、
２１０　　セラミック粒子、
２２０　　金属粒子、
Ｈ　　　　空孔
Ｘ　　　　（燃料電池スタックの）短手方向、
Ｙ　　　　（燃料電池スタックの）長手方向、
Ｚ　　　　（燃料電池スタックの）積層方向。 1 Fuel cell stack,
1U cell unit,
1A Metal support cell assembly,
10 Metal support cell,
20 power generation cells,
30 cathode layer,
40 electrolyte layer,
50, 150, 250, 350, 450 anode layer,
51 a first anode layer,
52 second anode layer,
60, 60c metal support layer,
113 cell frames,
120 separator,
130 Current collection auxiliary layer,
210 ceramic particles,
220 metal particles,
H Hole X (Fuel cell stack) short direction,
Y longitudinal direction (of the fuel cell stack),
Z (Fuel cell stack) stacking direction.

Claims (8)

  1. 　セラミック粒子と金属粒子とを含み、触媒機能を備えるアノード層と、
    　前記アノード層の一方側に配置され、セラミックから形成された電解質層と、
    　前記アノード層の他方側に配置され、金属から形成されたメタルサポート層と、を有し、
    　前記アノード層中の前記セラミック粒子の含有量に対する前記金属粒子の含有量の比率は、前記メタルサポート層側が前記電解質層側よりも大きい、メタルサポートセル。     An anode layer comprising ceramic particles and metal particles and having a catalytic function;
    An electrolyte layer disposed on one side of the anode layer and formed from ceramic;
    A metal support layer disposed on the other side of the anode layer and made of metal,
    The ratio of the content of the metal particles to the content of the ceramic particles in the anode layer is a metal support cell in which the metal support layer side is larger than the electrolyte layer side.
  2. 　前記アノード層内の単位体積に含まれる前記金属粒子の平均粒子径は、前記メタルサポート層側が前記電解質層側よりも大きい、請求項１に記載のメタルサポートセル。 The metal support cell according to claim 1, wherein an average particle diameter of the metal particles contained in a unit volume in the anode layer is larger on the metal support layer side than on the electrolyte layer side.
  3. 　前記アノード層内の単位体積に含まれる前記セラミック粒子の平均粒子径は、前記電解質層側が前記メタルサポート層側よりも小さい、請求項１または請求項２に記載のメタルサポートセル。 The metal support cell according to claim 1 or 2, wherein an average particle diameter of the ceramic particles contained in a unit volume in the anode layer is smaller on the electrolyte layer side than on the metal support layer side.
  4. 　前記アノード層は複数の空孔が形成された多孔体であり、
    　前記アノード層内の単位体積に含まれる前記空孔の平均径は、前記メタルサポート層側が前記電解質層側よりも大きい、請求項１～３のいずれか１項に記載のメタルサポートセル。     The anode layer is a porous body in which a plurality of pores are formed,
    The metal support cell according to any one of claims 1 to 3, wherein an average diameter of the pores contained in a unit volume in the anode layer is larger on the metal support layer side than on the electrolyte layer side.
  5. 　前記アノード層は、前記空孔に含浸した触媒をさらに有する、請求項４に記載のメタルサポートセル。 The metal support cell according to claim 4, wherein the anode layer further includes a catalyst impregnated in the pores.
  6. 　前記アノード層内の前記金属粒子は、前記メタルサポート層を形成する金属と同程度の熱膨張率を有する、請求項１～５のいずれか１項に記載のメタルサポートセル。 The metal support cell according to any one of claims 1 to 5, wherein the metal particles in the anode layer have a thermal expansion coefficient comparable to a metal forming the metal support layer.
  7. 　前記アノード層内の前記セラミック粒子は、前記電解質層を形成するセラミックと同程度の格子定数および同程度の熱膨張率を有する、請求項１～６のいずれか１項に記載のメタルサポートセル。 The metal support cell according to any one of claims 1 to 6, wherein the ceramic particles in the anode layer have the same lattice constant and the same thermal expansion coefficient as the ceramic forming the electrolyte layer.
  8. 　前記アノード層は、２層以上の層から構成される多層構造を有する、請求項１～７のいずれか１項に記載のメタルサポートセル。 The metal support cell according to any one of claims 1 to 7, wherein the anode layer has a multilayer structure including two or more layers.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08138690A (en) * 1994-11-07 1996-05-31 Tonen Corp Solid electrolyte fuel cell
JP2004055194A (en) * 2002-07-17 2004-02-19 Mitsubishi Materials Corp Electrode of solid oxide type fuel cell
JP2008502113A (en) * 2004-06-10 2008-01-24 テクニカル ユニバーシティ オブ デンマーク Solid oxide fuel cell
JP2009302010A (en) * 2008-06-17 2009-12-24 Showa Shell Sekiyu Kk Fuel cell cogeneration system
JP2013511795A (en) * 2009-11-18 2013-04-04 フォルシュングスツェントルム・ユーリッヒ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング Anode for high temperature fuel cell and its manufacture
JP2013145671A (en) * 2012-01-13 2013-07-25 Kikusui Chemical Industries Co Ltd Single cell for direct flame fuel cell

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08138690A (en) * 1994-11-07 1996-05-31 Tonen Corp Solid electrolyte fuel cell
JP2004055194A (en) * 2002-07-17 2004-02-19 Mitsubishi Materials Corp Electrode of solid oxide type fuel cell
JP2008502113A (en) * 2004-06-10 2008-01-24 テクニカル ユニバーシティ オブ デンマーク Solid oxide fuel cell
JP2009302010A (en) * 2008-06-17 2009-12-24 Showa Shell Sekiyu Kk Fuel cell cogeneration system
JP2013511795A (en) * 2009-11-18 2013-04-04 フォルシュングスツェントルム・ユーリッヒ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング Anode for high temperature fuel cell and its manufacture
JP2013145671A (en) * 2012-01-13 2013-07-25 Kikusui Chemical Industries Co Ltd Single cell for direct flame fuel cell

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