WO2017002264A1 - Pile à combustible à oxyde solide et son procédé de fabrication - Google Patents

Pile à combustible à oxyde solide et son procédé de fabrication Download PDF

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Publication number
WO2017002264A1
WO2017002264A1 PCT/JP2015/069152 JP2015069152W WO2017002264A1 WO 2017002264 A1 WO2017002264 A1 WO 2017002264A1 JP 2015069152 W JP2015069152 W JP 2015069152W WO 2017002264 A1 WO2017002264 A1 WO 2017002264A1
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Prior art keywords
current collector
air electrode
fuel cell
electrode
solid oxide
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PCT/JP2015/069152
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English (en)
Japanese (ja)
Inventor
矢島　健太郎
隆夫 和泉
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日産自動車株式会社
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Priority to PCT/JP2015/069152 priority Critical patent/WO2017002264A1/fr
Publication of WO2017002264A1 publication Critical patent/WO2017002264A1/fr

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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
    • H01M8/10—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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a solid oxide fuel cell and a method for manufacturing the same. More specifically, the present invention relates to a solid oxide fuel cell with reduced current collecting resistance between an air electrode and a current collector and a method for producing the solid oxide fuel cell.
  • a fuel cell is a device that converts chemical energy into electrical energy through an electrochemical reaction.
  • SOFC solid oxide fuel cell
  • a solid oxide fuel cell has a three-layer structure in which a fuel electrode, a solid electrolyte layer, and an air electrode are stacked, and this is used as a power generation unit of the fuel cell.
  • a fuel gas such as hydrogen or hydrocarbon is supplied to the fuel electrode, and an oxidant gas such as air is supplied to the air electrode to generate electricity.
  • current collectors are arranged on the air electrode and the fuel electrode, respectively.
  • a solid oxide fuel cell conventionally, a flat unit cell in which a fuel electrode and an air electrode are arranged so as to sandwich a solid electrolyte layer, and a separator are alternately stacked, and a separator and a fuel electrode
  • a flat-type solid electrolyte fuel cell having a heat-resistant wire mesh sandwiched therebetween is disclosed (for example, see Patent Document 1). It is also disclosed that the wire mesh is made of nickel. With such a configuration, the fuel electrode and the wire mesh are in close contact with each other, thereby increasing the current collection efficiency.
  • the present invention has been made in view of such problems of the conventional technology. And the objective of this invention is providing the manufacturing method of the solid oxide fuel cell which can reduce the current collection resistance between an electrode and a collector, and the said solid oxide fuel cell. is there.
  • a solid oxide fuel cell includes a current collector and an air electrode. Further, the fuel cell includes a current collector member that exists between the air electrode and the current collector and has a convex portion formed on the surface on the air electrode side. And between the air electrode and the convex part of the current collector part, a thin metal layer having a yield stress smaller than that of the current collector part and having a plastically deformed plastic region is provided.
  • the metal thin layer is plastically deformed by providing a metal having a low yield stress as a metal thin layer between the convex portion of the current collector and the air electrode. Therefore, even if the pressing load between the current collector part and the air electrode is not excessively increased, the contact rate between them is improved, so that the current collecting resistance can be reduced.
  • FIG. 1 is a perspective view showing an exploded state of a solid oxide fuel cell according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram showing a cross section of the air electrode current collector, the current collector part, the metal thin layer, and the air electrode in the solid oxide fuel cell shown in FIG.
  • FIG. 3 shows the effect of reducing current collection resistance by a structure having a convex portion on the surface.
  • (A) shows a method for measuring electrical resistance between hastelloy rods
  • (b) shows a rod in the case where the hastelloy rods are brought into direct contact with each other and a platinum mesh is interposed between the rods. It is a graph which shows the relationship between the surface pressure in between and current collection resistance.
  • FIG. 1 is a perspective view showing an exploded state of a solid oxide fuel cell according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram showing a cross section of the air electrode current collector, the current collector part, the metal thin layer, and the air electrode in the
  • FIG. 4A is a schematic diagram showing a state of deformation of the structure at the interface between the rod and the structure when a pressing load is applied to the nickel-based alloy structure.
  • FIG. 4B is a schematic view showing a state of deformation of the structure at the interface between the rod and the structure when a pressing load is applied to the platinum structure.
  • FIG. 5 is a graph showing the relationship between the pressing load on the mesh and the contact area between the rod and the mesh in a mesh made of platinum and a mesh made of a nickel-based alloy.
  • FIG. 6 is a graph showing the relationship between the total contact area between the rod and the mesh in the mesh made of platinum and the mesh made of nickel-based alloy and the area of the contact surface of the plastic region in the mesh.
  • FIG. 7 is a schematic cross-sectional view showing a state of deformation of the metal thin layer and the current collector part at the interface between the electrode and the current collector part when a pressing load is applied to the current collector part and the metal thin layer according to the present embodiment.
  • FIG. FIG. 8 is a schematic cross-sectional view showing an arrangement example of the metal thin layer with respect to the current collector portion.
  • FIG. 9 is a schematic diagram illustrating an example of a cross-sectional shape of the current collector portion.
  • FIG. 10 is a schematic diagram for explaining a manufacturing process of the solid oxide fuel cell of Example 1.
  • FIG. 11 is a schematic diagram for explaining a production process of the solid oxide fuel cell of Example 2.
  • FIG. 12 is a schematic diagram for explaining a manufacturing process of the solid oxide fuel cell of Example 3.
  • FIG. 13 is a schematic diagram for explaining a method for evaluating the solid oxide fuel cells of Example 1 and Comparative Example.
  • FIG. 14 is a graph showing measurement results of current collection resistance in the solid oxide fuel cells of Example
  • the solid oxide fuel cell 1 As shown in FIG. 1, the solid oxide fuel cell 1 according to this embodiment includes a single electrode including an air electrode 11 and a fuel electrode 12, and a solid electrolyte layer 13 sandwiched between the air electrode 11 and the fuel electrode 12. It has a cell 10. The single cell 10 is sandwiched between the air electrode current collector 14 and the fuel electrode current collector 15.
  • the air electrode current collector 14 includes a plurality of oxidant gas channels 14a
  • the fuel electrode current collector 15 includes a plurality of fuel gas channels 15a.
  • the oxidant gas flow path 14a and the fuel gas flow path 15a are a large number of linear flow paths (parallel flow paths) arranged in parallel to each other.
  • the cross-sectional shapes of the flow paths (oxidant gas flow path 14a, fuel gas flow path 15a) provided in the fuel electrode current collector 15 and the air electrode current collector 14 are convex portions called ribs, and concave portions called channels. Consists of.
  • the rib of the air electrode current collector 14 is electrically connected to the air electrode 11, whereby electrons are conducted between the air electrode current collector 14 and the air electrode 11. Further, when the rib of the fuel electrode current collector 15 is electrically connected to the fuel electrode 12, electrons are conducted between the fuel electrode current collector 15 and the fuel electrode 12.
  • the solid oxide fuel cell 1 includes a current collector 20 between the air electrode 11 and the air electrode current collector 14 as shown in FIGS. 1 and 2.
  • the current collector member 20 is composed of a structure in which convex portions 23 are formed on a surface such as a metal mesh. By providing such a current collector member 20, it is possible to suppress the current collection resistance between the air electrode 11 and the air electrode current collector 14.
  • a pressing load is usually applied to a contact portion between the current collector (the air electrode current collector 14 and the fuel electrode current collector 15) and the air electrode 11 and the fuel electrode 12 in order to ensure electrical connection. Is added. Further, it is generally known that increasing the pressing load increases the contact interface between the current collector and the electrode and reduces the current collection resistance (ASR). However, in order to increase the pressing load of the current collector and the electrode, it is necessary to employ a large-diameter bolt for increasing the surface pressure during assembly. Therefore, the weight of the fuel cell stack increases due to the increase in the weight of the bolt, and the output per unit volume decreases due to the increase in the volume of the bolt. Therefore, it is necessary to reduce the current collection resistance between the current collector and the electrode without increasing the pressing load on the current collector and the electrode.
  • FIG. 3 shows the effect of reducing current collection resistance by a structure having a convex portion on the surface.
  • FIG. 3A the current and voltage between the rods when the surface pressure between the rods is increased by using a rod made of Hastelloy (registered trademark) which is a nickel-based alloy. Measured and the change in current collecting resistance was measured. At this time, the change in current collecting resistance was measured with and without a platinum mesh between the rods.
  • Hastelloy registered trademark
  • 3B shows the relationship between the surface pressure between the rods and the current collecting resistance when the Hastelloy rods are in direct contact with each other and a platinum mesh is interposed between the rods. As shown in FIG.3 (b), it turns out that current collection resistance falls as the surface pressure between rods increases. And when a platinum mesh is interposed, it turns out that current collection resistance falls compared with the case where a platinum mesh is not interposed.
  • the effect of reducing the current collecting resistance between the rods varies greatly depending on the material of the structure having the convex portions on the surface.
  • such an effect of reducing the current collecting resistance is caused by a contact surface in the plastic region being formed on the convex portion of the structure at the contact surface between the rod and the structure provided with the convex portion on the surface.
  • Hastelloy which is a nickel-based alloy
  • has a high yield stress which is a stress in the vicinity of transition from elastic deformation to plastic deformation. Therefore, when a structure (mesh) made of Hastelloy is used, even if the pressing load on the structure is increased, as shown in FIG. 4A, at the contact interface between the rod and the convex portion 23 of the structure.
  • a large number of elastic contact surfaces 21 formed by elastic deformation of the convex portions 23 of the structure are generated.
  • a plastic contact surface 22 formed by plastic deformation of the convex portion 23 of the structure is generated, but even in that case, the elastic contact surface 21 is dominant.
  • platinum has a low yield stress. Therefore, in the case of using a structure (mesh) made of platinum, by increasing the pressing load on the structure, as shown in FIG. 4B, the structure is formed at the contact interface between the rod and the convex portion 23 of the structure. Many contact surfaces 22 in the plastic region formed by plastic deformation of the convex portions 23 of the body are generated. Thus, when the yield stress of the material which comprises a structure differs, even if the load concerning a structure is the same, the area of the plastic zone produced
  • FIG. 5 shows the relationship between the pressing load on the mesh and the contact area between the rod and the mesh in the mesh made of platinum and the mesh made of nickel-based alloy (Hastelloy).
  • symbol A relates to all contact surfaces of the platinum mesh
  • symbol B relates to the contact surface of the plastic region of the platinum mesh
  • symbol C relates to all the contact surfaces of the nickel base alloy mesh
  • symbol D denotes the nickel base alloy. It relates to the contact surface of the plastic region of the mesh.
  • FIG. 6 shows the relationship between the total contact area between the rod and the mesh in the mesh made of platinum and the mesh made of nickel-based alloy (Hastelloy) and the area of the contact surface of the plastic region in the mesh.
  • symbol E relates to a platinum mesh
  • symbol F relates to a nickel-based alloy mesh.
  • the solid oxide fuel cell 1 of the present embodiment is an application of the effect that the current collection resistance is reduced without increasing the pressing load by increasing the contact surface in such a plastic region.
  • current collection resistance reduction effect in a plastic region is referred to as “current collection resistance reduction effect in a plastic region”.
  • Table 1 shows Young's modulus and yield stress of platinum, nickel, nickel-based alloy (Hastelloy) and ferritic stainless steel (Crofer22APU).
  • platinum or nickel which has a low yield stress
  • the current collection resistance between the current collector and the electrode can be reduced due to the current collection resistance reduction effect in the plastic region. It is estimated that it can be reduced.
  • platinum is very expensive and the cost is greatly increased.
  • nickel base alloys such as Hastelloy and stainless steels such as Crofer 22APU have high oxidation resistance but high yield stress, and therefore it is difficult to obtain the current collecting resistance reduction effect in the plastic region.
  • the metal thin layer 24 which consists of a material whose yield stress is smaller than the current collection material part 20 and the air electrode 11 on the surface of the current collection material part 20 at the air electrode side.
  • a plastic contact surface 22 is formed by the thin metal layer 24 between the current collector 20 and the air electrode 11. Since the metal thin layer 24 has a lower yield stress than the current collector 20 and the air electrode 11, the plastic contact area 22 is generated more than the elastic contact area 21. Therefore, the current collection resistance between the current collector member 20 and the air electrode 11 can be reduced without increasing the pressing load due to the effect of reducing the current collection resistance in the plastic region.
  • the current collector 20 is preferably made of an oxidation-resistant metal as will be described later, and many of such oxidation-resistant metals have a high yield stress. Therefore, in the current collector member 20, more elastic region 25 is generated than plastic region 26.
  • the contact surface 22 in the plastic region is generated by providing the metal thin layer 24, the current collection resistance reduction effect in the plastic region can be achieved without increasing the pressing load of the current collector member 20. Can be obtained.
  • the thickness t1 of the thin metal layer 24 is preferably 0.01 ⁇ m or more. That is, as shown in FIG. 7, it is preferable that the thickness t1 of the thin metal layer 24 after the current collector member 20 provided with the thin metal layer 24 is pressed against the air electrode 11 is 0.01 ⁇ m or more.
  • the thickness t1 of the metal thin layer 24 is 0.01 ⁇ m or more, a large number of contact surfaces 22 in the plastic region are generated, and it becomes possible to further enhance the current collection resistance reduction effect in the plastic region.
  • the metal thin layer 24 can be made thinner to reduce the material cost.
  • the upper limit of the thickness t1 of the thin metal layer 24 is not particularly limited, but can be, for example, 100 ⁇ m or less.
  • the thickness t1 of the thin metal layer 24 can be obtained by observing the cross section of the thin metal layer 24 with a scanning electron microscope (SEM).
  • the material constituting the metal thin layer 24 is not particularly limited as long as it has a lower yield stress than the current collector 20 and the air electrode 11.
  • the metal thin layer 24 is preferably made of at least one selected from the group consisting of silver, platinum and gold.
  • the thin metal layer 24 is preferably made of an alloy containing at least one of silver, platinum and gold and at least one of palladium, ruthenium and cobalt. Since these materials have low yield stress and excellent oxidation resistance at high temperatures, it is possible to reduce electrical resistance even when used on the air electrode side.
  • the current collector member 20 is preferably made of an oxidation resistant metal. Therefore, the current collector member 20 is preferably made of an alloy containing at least one of chromium and iron as a main component. That is, it is preferable to use an alloy containing 50 mass% or more of at least one of chromium and iron for the current collector part 20. By using such an alloy as the current collector 20, it becomes possible to eliminate the influence of oxidation of the current collector 20 and suppress an increase in current collection resistance.
  • At least one of stainless steel and a chromium-based alloy can be used as the alloy constituting the current collector portion 20.
  • the stainless steel include ferritic stainless steel, martensitic stainless steel, and austenitic stainless steel.
  • ferritic stainless steel include SUS430, SUS434, and SUS405.
  • martensitic stainless steel include SUS403, SUS410, and SUS431.
  • austenitic stainless steel include SUS201, SUS301, and SUS305.
  • Examples of the chromium-based alloy include Ducrloy CRF (94Cr5Fe1Y 2 O 3 ), Crofer 22 alloy, and ZMG232L.
  • the current collector 20 is also preferably made of an alloy containing nickel as a main component. That is, it is also preferable to use a nickel-based alloy containing 50 mass% or more of nickel for the current collector member 20.
  • nickel-based alloy examples include Inconel (registered trademark) and Hastelloy (registered trademark).
  • the current collector member 20 it is preferable to use a structure having a convex portion 23 formed on the surface, for example, a structure such as a mesh (metal mesh). That is, the current collector part 20 may be a structure formed by assembling wires made of the above materials, or may be a structure formed by knitting the wires. The method for knitting the wire is not particularly limited, and for example, methods such as plain weaving, twill weaving, and tatami weaving can be employed. Moreover, the convex part 23 formed in the surface of the current collection material part 20 can be formed in dotted line shape, linear form, a grid
  • a mesh metal mesh
  • the thin metal layer 24 only needs to be interposed at least between the electrically conductive surfaces of the air electrode 11 and the air electrode current collector 14. Therefore, as shown in FIG. 8A, the metal thin layer 24 is provided on the entire surface of the air electrode 11, and the convex portion 23 formed on the surface of the current collector 20 is brought into contact with the metal thin layer 24. be able to. Moreover, as shown in FIG.8 (b), it can be set as the structure which provides the metal thin layer 24 only in the surface where the current collection material part 20 and the air electrode 11 oppose. Furthermore, as shown in FIG. 8C, the air electrode 11 and the air electrode current collector 14 can be brought into contact with each other after the metal thin layer 24 is provided over the entire circumference of the current collector member 20. .
  • the thin metal layer 24 can be provided only on the surface where the current collector 20 and the air electrode 11 face each other and the periphery thereof.
  • the metal thin layer 24 only needs to be interposed between the air electrode 11 and the air electrode current collector 14, from the viewpoint of reducing the cost by reducing the number of metals constituting the metal thin layer 24, FIG.
  • the configuration shown in FIG. 8B and FIG. 8D is more preferable.
  • the cross-sectional shape of the wire is not particularly limited. That is, as shown in FIGS. 7 and 8, the current collector member 20 has a substantially circular cross-sectional shape along the stacking direction Y of the air electrode 11, the current collector member 20, and the air electrode current collector 14. it can. However, as shown in FIG. 9, the current collector member 20 has a triangular, semicircular or trapezoidal cross-sectional shape along the stacking direction Y of the air electrode 11, the current collector member 20 and the air electrode current collector 14. Preferably there is.
  • the current collector part 20 has a cross-sectional area (XZ plane) perpendicular to the stacking direction Y that decreases from the air electrode current collector 14 toward the air electrode 11. Since the cross section of the current collector 20 is triangular, semicircular or trapezoidal, when a pressing load is applied to the current collector 20, the tip of the current collector 20 (the convex portion 23 on the surface) is crushed. Thus, the area of the surface facing the air electrode 11 increases. Therefore, the conductivity between the current collector 20 and the air electrode 11 can be increased via the thin metal layer 24.
  • the current collector portion may have an elliptical cross-sectional shape along the stacking direction Y.
  • the solid oxide fuel cell 1 is provided with the air electrode current collector 14 and the fuel electrode current collector 15 that are electrically connected to the air electrode 11 and the fuel electrode 12, respectively.
  • the current collectors (air electrode current collector 14 and fuel electrode current collector 15) function as a separator that separates the current collecting function from the electrodes (air electrode 11 and fuel electrode 12) from the oxidant gas and the fuel gas. It has the function of. In this specification, it is assumed that the current collector member 20 cannot be distinguished from those that are separate from the current collector and those that are part of the structure of the current collector.
  • the materials constituting the air electrode current collector 14 and the fuel electrode current collector 15 are not particularly limited.
  • an alloy material having excellent oxidation resistance and conductivity can be used.
  • ferritic stainless steel, Inconel, Hastelloy, or the like can be used.
  • the flow of the oxidant gas flowing through the oxidant gas flow path 14a and the flow of the fuel gas flowing through the fuel gas flow path 15a are orthogonal flows in which the fuel gas and the oxidant gas flow in directions orthogonal to each other within the plane of the single cell 10.
  • the flow of the fuel gas and the oxidant gas may be a counter flow that flows in the plane of the single cell 10 and flows in the same direction in the plane of the single cell 10 (coflow).
  • the flow of the fuel gas and the oxidant gas may be a return flow that changes the direction of the reaction gas entering from the inlet in the plane of the single cell 10 and flows in the reverse direction.
  • Serpentine flow may be used in which the flow direction of the reaction gas is changed several times in the opposite direction.
  • the air electrode 11 one that is strong in an oxidizing atmosphere, permeates the oxidant gas, has high electrical conductivity, and has a catalytic action for converting oxygen molecules into oxide ions can be suitably used.
  • the air electrode 11 may be made of an electrode catalyst or a cermet of an electrode catalyst and an electrolyte material.
  • a metal such as silver (Ag) or platinum (Pt) may be used as the electrode catalyst, but lanthanum strontium cobaltite (La 1-x Sr x CoO 3 : LSC) or lanthanum strontium cobalt ferrite ( La 1-x Sr x Co 1 -y Fe y O 3: LSCF), samarium strontium cobaltite (Sm x Sr 1-x CoO 3: SSC), lanthanum strontium manganite (La 1-x Sr x MnO 3: LSM It is preferable to apply a perovskite oxide such as However, it is not limited to these, and conventionally known air electrode materials can be applied.
  • examples of the electrolyte material include, but are not limited to, cerium oxide (CeO 2 ), zirconium oxide (ZrO 2 ), titanium oxide (TiO 2 ), and lanthanum oxide (La 2 O 3 ). It is not a thing, but the mixture with oxides, such as various stabilized zirconia and a ceria solid solution, can be used suitably.
  • the fuel electrode 12 one that is strong in a reducing atmosphere, permeates the fuel gas, has high electrical conductivity, and has a catalytic action for converting hydrogen molecules into protons can be suitably used.
  • a constituent material of the fuel electrode for example, metals such as nickel (Ni), cobalt (Co) and platinum (Pt) may be applied alone, but oxygen represented by yttria stabilized zirconia (YSZ) may be used. It is preferable to apply a cermet mixed with an ionic conductor. By using such a material, the reaction area increases and the electrode performance can be improved.
  • a ceria solid solution such as samaria doped ceria (SDC) or gadria doped ceria (GDC) can be applied instead of yttria stabilized zirconia (YSZ).
  • a layer having gas impermeability and a capability of passing oxygen ions without passing electrons can be suitably used.
  • a constituent material of the solid electrolyte layer for example, yttria (Y 2 O 3 ), neodymium oxide (Nd 2 O 3 ), samaria (Sm 2 O 3 ), gadria (Gd 2 O 3 ), scandia (Sc 2 O 3). ) Or the like can be applied as stabilized zirconia.
  • ceria solid solutions such as samaria doped ceria (SDC), yttria doped ceria (YDC), gadria doped ceria (GDC), bismuth oxide (Bi 2 O 3 ), lanthanum gallate (LaGaO 3 ), lanthanum strontium magnesium gallate (La 1-x Sr x Ga 1-y Mg y O 3: LSMG) or the like may be applied.
  • SDC samaria doped ceria
  • YDC yttria doped ceria
  • GDC gadria doped ceria
  • Bi 2 O 3 bismuth oxide
  • LaGaO 3 lanthanum gallate
  • La 1-x Sr x Ga 1-y Mg y O 3: LSMG lanthanum strontium magnesium gallate
  • an oxidant gas such as oxygen or air is introduced into the oxidant gas passage 14a, and hydrogen, hydrocarbons, or various liquid fuels are reformed into the fuel gas passage 15a.
  • Fuel gas such as reformed gas obtained is introduced.
  • oxygen gas molecules are decomposed into oxygen ions and electrons at the three-phase interface serving as an active point, and the oxygen ions are transmitted through the solid electrolyte layer 13 and conducted to the fuel electrode 12.
  • oxygen ions conducted from the solid electrolyte layer 13 react with fuel gas molecules and electrons at the three-phase interface that is also the active point. Electrical energy can be obtained by electrically connecting the air electrode 11 and the fuel electrode 12 through the air electrode current collector 14 and the fuel electrode current collector 15.
  • the solid oxide fuel cell 1 of this embodiment includes a fuel electrode 12 and an air electrode 11, a solid electrolyte layer 13 sandwiched between the fuel electrode 12 and the air electrode 11, and a current collector disposed on the air electrode 11 side. (Air electrode current collector 14). Further, the solid oxide fuel cell 1 includes a current collector member 20 that exists between the air electrode 11 and the current collector and has a convex portion 23 formed on the surface on the air electrode side. And between the air electrode 11 and the convex part 23 of the current collection material part 20, the metal thin layer 24 in which the yield stress was smaller than the current collection material part 20, and the plastic region deformed plastically was formed is provided. .
  • the current collector member 20 can use an oxidation-resistant metal, even when it is used on the air electrode 11 side, it is possible to suppress oxidation at a high temperature and prevent a decrease in current collecting resistance.
  • the thin metal layer 24 is first formed on the surface of the current collector member 20.
  • the formation method of the metal thin layer 24 is not specifically limited, For example, physical vapor deposition method (PVD method), powder jet deposition method (PJD method), thermal spraying method, plating method, electroless plating method, chemical vapor deposition method (CVD method) Etc. can be used.
  • the thin metal layer 24 may be formed on the entire surface of the current collector 20. However, the metal thin layer 24 should just be provided at least between the current collector part 20 and the air electrode 11. For this reason, masking or the like may be performed on portions other than between the current collector member 20 and the air electrode 11 so that the thin metal layer 24 is not formed. Thereby, the material of the metal thin layer 24 can be reduced.
  • the air electrode current collector 14, the current collector member 20 provided with the metal thin layer 24, and the air electrode 11 are laminated in this order, and a pressing load is applied to the metal thin layer 24.
  • the metal thin layer 24 is plastically deformed, and the contact surface 22 in the plastic region is obtained.
  • the air electrode current collector 14, the current collector member 20 provided with the thin metal layer 24, the air electrode 11, the solid electrolyte layer 13, and the fuel electrode 12 are laminated in this order, and a pressing load is collectively applied. May be. In this way, the solid oxide fuel cell 1 can be obtained.
  • a thin metal layer 24 is formed on the surface of the air electrode 11.
  • the formation method of the metal thin layer 24 is not specifically limited, The above-mentioned method can be used.
  • masking or the like may be performed except for between the current collector member 20 and the air electrode 11 so that the thin metal layer 24 is not formed.
  • the air electrode current collector 14, the current collector member 20, and the air electrode 11 provided with the metal thin layer 24 are laminated in this order, and a pressing load is applied to the metal thin layer 24, whereby A solid oxide fuel cell can be obtained.
  • the thin metal layer 24 may be formed after the air electrode current collector 14 and the current collector 20 are welded.
  • the air electrode current collector 14 and the current collector member 20 are welded.
  • the electrical resistance between the air electrode current collector 14 and the current collector member 20 is reduced, and the output of the fuel cell is reduced. It becomes possible to raise more.
  • a current collector was obtained by molding a ferrite plate material (ferritic stainless steel SUS430) having a thickness of 0.01 mm by a pressing method. Further, a mesh (# 100) made of a ferrite material (ferritic stainless steel SUS430) was prepared as a current collector part, and the current collector and the current collector part were previously integrated by welding.
  • a ferrite plate material ferritic stainless steel SUS430
  • a mesh (# 100) made of a ferrite material (ferritic stainless steel SUS430) was prepared as a current collector part, and the current collector and the current collector part were previously integrated by welding.
  • an air electrode (lanthanum strontium cobalt ferrite: LSCF), a solid electrolyte layer (yttria stabilized zirconia: YSZ), a fuel electrode (cermet of Ni and YSZ particles: Ni—YSZ) and a metal support are laminated in this order.
  • a power generation cell was also prepared.
  • the metal support is a support made of a porous metal in contact with the surface of the fuel electrode opposite to the solid electrolyte layer.
  • the surface of the current collector 20 other than the surface in contact with the air electrode 11 was coated with a resin layer.
  • a resin solution in which a polypropylene resin was dissolved in an organic solvent was prepared and sprayed on the Kapton tape 31 by spraying.
  • the resin layer 32 was formed by performing the drying process for 24 hours or more at normal temperature.
  • the resin layer 32 was formed by peeling the Kapton tape 31.
  • a thin metal layer was formed on the obtained resin layer 32.
  • the power generation cell on which the resin layer 32 was formed was installed in a magnetron sputtering apparatus, and an Ag target was installed in the apparatus. Then, the temperature in the apparatus was controlled from room temperature to a predetermined temperature at an output of 1200 W, and film formation was performed for 60 minutes. As a result, as shown in FIG. 10D, a thin metal layer 24 (silver thin film) having a thickness of about 1 to 2 ⁇ m was formed on the air electrode 11 and the resin layer 32.
  • the stack was assembled by pressing the projection 23 of the current collector 20 against the thin metal layer 24 on the air electrode 11.
  • a specified surface pressure about 0.3 MPa
  • the fuel electrode 12 side was sealed with an inert gas, and only the air electrode 11 side was fired at 800 ° C. in the atmosphere.
  • the resin layer 32 disappeared, and the thin metal layer where the current collector 20 and the air electrode 11 were not in contact with each other was peeled off.
  • Example 2 a current collector was obtained by molding a ferrite plate material (ferritic stainless steel SUS430) by a press method in the same manner as in Example 1. Further, a mesh (# 100) made of a ferrite material (ferritic stainless steel SUS430) is prepared as the current collector part, and the air electrode current collector 14 and the current collector part 20 are welded in advance as shown in FIG. And integrated. A power generation cell similar to that in Example 1 was also prepared.
  • the air electrode current collector 14 and the current collector part 20 are previously integrated by welding, and the other parts than the current collector part 20 are covered with a Kapton sheet and masked, and the thin metal layer 24 is formed on the current collector part 20.
  • the masked current collector 20 was installed in a magnetron sputtering apparatus, and an Ag target was installed in the apparatus. Then, the temperature in the apparatus was controlled from room temperature to a predetermined temperature at an output of 1200 W, and film formation was performed for 60 minutes. As a result, as shown in FIG. 11B, a thin metal layer 24 (silver thin film) having a thickness of about 1 to 2 ⁇ m was formed on the current collector 20.
  • the stack was assembled by pressing the convex portion 23 of the current collector 20 onto the air electrode 11. At that time, a specified surface pressure (about 0.3 MPa) was applied so that the convex portion 23 of the current collector member 20 was plastically deformed. Thus, the fuel cell of this embodiment was obtained.
  • Example 3 a current collector was obtained by molding a ferrite plate material (ferritic stainless steel SUS430) by a press method in the same manner as in Example 1. Further, a mesh (# 100) made of a ferrite material (ferritic stainless steel SUS430) is prepared as a current collector portion, and the air electrode current collector 14 and the current collector portion 20 are welded in advance as shown in FIG. And integrated. A power generation cell similar to that in Example 1 was also prepared.
  • a thin metal layer was formed on the current collector part 20 partially masked with the resin layer 32.
  • the masked current collector 20 was installed in a magnetron sputtering apparatus, and an Ag target was installed in the apparatus. Then, the temperature in the apparatus was controlled from room temperature to a predetermined temperature at an output of 1200 W, and film formation was performed for 60 minutes. As a result, as shown in FIG. 12D, a metal thin layer 24 (silver thin film) having a film thickness of about 1 to 2 ⁇ m was formed on the current collector 20 and the resin layer 32.
  • the current collector part 20 on which the thin metal layer 24 was formed and the air electrode current collector 14 were integrated and fired at 800 ° C. in the atmosphere.
  • the resin layer 32 disappeared, and the metal thin layer 24 at the portion masked by the current collector 20 and the resin layer 32 was peeled off.
  • the thin metal layer 24 that has been peeled off is removed by applying an air flow, and the Kapton sheet that covers a portion other than the current collector 20 is further peeled off, thereby forming the thin metal layer 24 as shown in FIG. (Silver thin film) was formed only on the air electrode side of the current collector 20.
  • the stack was assembled by pressing the convex portion 23 of the current collector portion 20 onto the air electrode 11. At that time, a specified surface pressure (about 0.3 MPa) was applied so that the convex portion 23 of the current collector member 20 was plastically deformed. Thus, the fuel cell of this embodiment was obtained.
  • a current collector was obtained by molding a ferrite plate material (ferritic stainless steel SUS430) having a thickness of 0.01 mm by a pressing method. Further, a mesh (# 100) made of a ferrite material (ferritic stainless steel SUS430) was prepared as a current collector part, and the current collector and the current collector part were previously integrated by welding. A power generation cell similar to that in Example 1 was also prepared.
  • the stack was assembled by pressing the convex part of the current collector part onto the air electrode. At that time, a specified surface pressure (about 0.3 MPa) was applied so that the convex portion of the current collector portion was plastically deformed.
  • a specified surface pressure about 0.3 MPa
  • the fuel cell of this embodiment was obtained. That is, the fuel cell of the present embodiment is one in which a thin metal layer is not provided with respect to the fuel cell of Example 1.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention concerne une pile à combustible à oxyde solide (1) comprenant une électrode à combustible (12) et une électrode oxydoréductrice (11), ainsi qu'une couche d'électrolyte solide (13) prise en sandwich entre l'électrode à combustible et l'électrode oxydoréductrice. La pile à combustible à oxyde solide comprend en outre un collecteur de courant (14) placé côté électrode oxydoréductrice et une partie en matériau de collecte de courant (20) qui est disposée entre l'électrode oxydoréductrice et le collecteur de courant et qui présente une saillie (23) formée sur une surface côté électrode oxydoréductrice. Une mince couche métallique (24) sur laquelle est formée une région plastique qui possède une plus basse limite d'élasticité que la partie en matériau de collecte de courant et l'électrode oxydoréductrice et qui a été soumise à une déformation plastique est ensuite disposée entre l'électrode oxydoréductrice et la saillie de la partie en matériau de collecte de courant.
PCT/JP2015/069152 2015-07-02 2015-07-02 Pile à combustible à oxyde solide et son procédé de fabrication WO2017002264A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002216807A (ja) * 2000-11-16 2002-08-02 Mitsubishi Materials Corp 固体電解質型燃料電池の空気極集電体
JP2006012453A (ja) * 2004-06-22 2006-01-12 Nissan Motor Co Ltd 固体酸化物形燃料電池スタック及び固体酸化物形燃料電池
JP2008117737A (ja) * 2006-11-08 2008-05-22 Nippon Telegr & Teleph Corp <Ntt> 平板型固体酸化物形燃料電池
JP2008243394A (ja) * 2007-03-26 2008-10-09 Toyota Motor Corp 燃料電池用セルの製造方法
JP2010073566A (ja) * 2008-09-19 2010-04-02 Nissan Motor Co Ltd 固体電解質型燃料電池及びその製造方法
JP2010236012A (ja) * 2009-03-31 2010-10-21 Nisshin Steel Co Ltd 高温導電部材
JP2013239330A (ja) * 2012-05-15 2013-11-28 Ngk Spark Plug Co Ltd 固体酸化物形燃料電池およびその製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002216807A (ja) * 2000-11-16 2002-08-02 Mitsubishi Materials Corp 固体電解質型燃料電池の空気極集電体
JP2006012453A (ja) * 2004-06-22 2006-01-12 Nissan Motor Co Ltd 固体酸化物形燃料電池スタック及び固体酸化物形燃料電池
JP2008117737A (ja) * 2006-11-08 2008-05-22 Nippon Telegr & Teleph Corp <Ntt> 平板型固体酸化物形燃料電池
JP2008243394A (ja) * 2007-03-26 2008-10-09 Toyota Motor Corp 燃料電池用セルの製造方法
JP2010073566A (ja) * 2008-09-19 2010-04-02 Nissan Motor Co Ltd 固体電解質型燃料電池及びその製造方法
JP2010236012A (ja) * 2009-03-31 2010-10-21 Nisshin Steel Co Ltd 高温導電部材
JP2013239330A (ja) * 2012-05-15 2013-11-28 Ngk Spark Plug Co Ltd 固体酸化物形燃料電池およびその製造方法

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