WO2021186916A1 - Module de pile à combustible et système de pile à combustible équipé de celui-ci - Google Patents

Module de pile à combustible et système de pile à combustible équipé de celui-ci Download PDF

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Publication number
WO2021186916A1
WO2021186916A1 PCT/JP2021/003518 JP2021003518W WO2021186916A1 WO 2021186916 A1 WO2021186916 A1 WO 2021186916A1 JP 2021003518 W JP2021003518 W JP 2021003518W WO 2021186916 A1 WO2021186916 A1 WO 2021186916A1
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WIPO (PCT)
Prior art keywords
unit
fuel
fuel cell
power generation
cell module
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PCT/JP2021/003518
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English (en)
Japanese (ja)
Inventor
重徳 末森
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三菱重工業株式会社
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Publication of WO2021186916A1 publication Critical patent/WO2021186916A1/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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • H01M8/0208—Alloys
    • H01M8/021—Alloys based on iron
    • 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
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0215—Glass; Ceramic materials
    • H01M8/0217—Complex oxides, optionally doped, of the type AMO3, A being an alkaline earth metal or rare earth metal and M being a metal, e.g. perovskites
    • 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
    • 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
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/247—Arrangements for tightening a stack, for accommodation of a stack in a tank or for assembling different tanks
    • H01M8/2475—Enclosures, casings or containers of fuel cell stacks
    • 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 disclosure relates to a fuel cell module having a cell stack and a fuel cell system having the cell stack.
  • the fuel cell module mounted on the fuel cell system has a plurality of cell stacks, which are an aggregate of fuel cell cells. By arranging a large number of fuel cell cells in one cell stack and connecting them in series, the output voltage can be increased.
  • a cell having a fuel electrode, a solid electrolyte membrane, and an air electrode is formed on the substrate tube in the circumferential direction of the substrate tube, and a plurality of cells are arranged along the axial direction of the substrate tube. Solid oxide fuel cells with stacks are described. Further, Patent Document 1 describes that the material of the air electrode is made of a different material depending on the temperature at the position of the cell.
  • the fuel cell module of the present disclosure includes a container, a cell stack arranged inside the container, extending in a first direction, and having a plurality of fuel cell cells arranged in the first direction, and the cell stack.
  • the cell stack includes a laminated fuel electrode, an electrolyte, an air electrode, and an interconnector connected to an adjacent fuel cell, and the cell stack includes a first unit in which the fuel cell is arranged and the first unit.
  • the second unit includes, in the second unit, at least one element of the fuel electrode, electrolyte and interconnector of the fuel cell, the first unit. It is made of a material different from the corresponding element of the fuel cell.
  • the fuel cell system of the present disclosure includes the above-mentioned fuel cell module, an oxidation gas supply means for supplying the oxidation gas to the pressure vessel, and a fuel gas supply means for supplying the fuel gas inside the cell stack.
  • the cell stack at each position of the fuel cell module can be formed of an appropriate material, the deterioration of power generation performance can be suppressed, and power generation can be performed with high efficiency. As a result, the amount of power generation per unit volume can be further increased.
  • FIG. 1 is a schematic configuration diagram schematically showing the fuel cell system of the present embodiment.
  • FIG. 2 is a schematic configuration diagram schematically showing a fuel cell module.
  • FIG. 3 is a schematic configuration diagram schematically showing a cell stack.
  • FIG. 4 is a cross-sectional view schematically showing a part of the cell stack.
  • FIG. 5 is a cross-sectional view showing an example of the arrangement of cell stacks inside the pressure vessel.
  • FIG. 6 is an enlarged cross-sectional view showing the vicinity of the connection mechanism in an enlarged manner.
  • FIG. 7 is a schematic configuration diagram schematically showing a cell stack of another embodiment.
  • FIG. 8 is a schematic configuration diagram schematically showing a fuel cell module of another embodiment.
  • FIG. 1 is a schematic configuration diagram schematically showing the fuel cell system of the present embodiment.
  • FIG. 2 is a schematic configuration diagram schematically showing a fuel cell module.
  • FIG. 3 is a schematic configuration diagram schematically showing a cell stack.
  • FIG. 4 is a
  • FIG. 9 is a perspective view schematically showing the cell stack of the fuel cell module shown in FIG.
  • FIG. 10 is a schematic configuration diagram schematically showing a fuel cell module of another embodiment.
  • FIG. 11 is a perspective view schematically showing the cell stack of the fuel cell module shown in FIG.
  • FIG. 12 is a schematic configuration diagram schematically showing a fuel cell module of another embodiment.
  • FIG. 13 is a perspective view schematically showing the cell stack of the fuel cell module shown in FIG.
  • FIG. 1 is a schematic configuration diagram schematically showing the fuel cell system of the present embodiment.
  • the fuel cell system 10 of the present embodiment includes a solid oxide fuel cell module, a so-called SOFC (Solid Oxide Fuel Cell), and operates while controlling the fuel cell module.
  • the fuel cell system may supply a part of the fuel gas and air (oxidant gas) that have passed through the fuel cell module to the combustor of the gas turbine. That is, the fuel cell system 10 may be a part of a combined system connected to another power generation device.
  • SOFC Solid Oxide Fuel Cell
  • the fuel cell system 10 includes a fuel cell module 12, an air supply device (oxidizer gas supply unit) 14 for supplying air (oxidant gas), and air (exhaust) that has passed through the fuel cell module 12.
  • a control device 18 for controlling the operation of each unit, a voltmeter 19, a current meter 20, and a thermometer 21 are provided.
  • air is used as the oxidant gas
  • any oxidant that oxidizes a fuel gas such as an oxygen-containing gas may be used.
  • the fuel cell module 12 generates electricity by reacting the supplied air with the fuel gas.
  • the fuel cell module will be described later.
  • the air supply device (oxidizing gas supply means) 14 supplies air to the fuel cell module 12.
  • the air supply device 14 has an air supply source 22 and an air supply pipe 24.
  • the air supply source 22 is a device that sends air, such as a scavenging fan or a pump.
  • the air supply pipe 24 connects the air supply source 22 and the fuel cell module 12. The air supply pipe 24 supplies the air sent by the air supply source 22 to the fuel cell module 12.
  • the fuel supply device (fuel supply means) 16 supplies fuel gas to the fuel supply chamber 84.
  • the fuel supply device 16 has a fuel supply source 26 and a fuel supply pipe 28.
  • the fuel supply source 26 includes a tank for storing the fuel gas, a control valve for controlling the flow rate of the fuel gas supplied from the tank, and the like.
  • the fuel supply pipe 28 connects the fuel supply source 26 and the fuel cell module 12. The fuel supply pipe 28 supplies the fuel gas sent by the fuel supply source 26 to the fuel cell module 12.
  • the fuel cell system 10 is provided in the voltmeter 19 for measuring the voltage value output from the fuel cell module 12, the ammeter 20 for measuring the current value output from the fuel cell module 12, and the fuel cell module 12. It is equipped with a voltmeter 21.
  • the ammeter 20 measures the current obtained by the power generation of the fuel cell module 12.
  • the thermometer 21 measures the temperature of the power generation chamber 82, which will be described later, of the fuel cell module 12.
  • the control device 18 controls the fuel cell module 12 during the start-up operation and controls the fuel cell module 12 during the power generation operation.
  • the control device 18 determines the amount of air supplied from the air supply device 14 and the fuel gas supplied from the fuel supply device 16 based on the measurement results of the voltmeter 19, the ammeter 20, and the thermometer 21 and the input instructions. The amount and the electric power taken out from the fuel cell module 12 are controlled.
  • FIG. 2 is a perspective view schematically showing the fuel cell module.
  • FIG. 2 is a schematic configuration diagram schematically showing a fuel cell module.
  • FIG. 3 is a schematic configuration diagram schematically showing a cell stack.
  • FIG. 4 is a cross-sectional view schematically showing a part of the cell stack.
  • FIG. 5 is a cross-sectional view showing an example of the arrangement of cell stacks inside the pressure vessel.
  • FIG. 6 is an enlarged cross-sectional view showing the vicinity of the connection mechanism in an enlarged manner.
  • the fuel cell module 12 includes a container 40, a cell assembly 42, a pipe support plate (upper pipe support plate) 44, a pipe support plate (lower pipe support plate) 46, and a heat insulating body. It has a (upper heat insulating body) 48, a heat insulating body (lower heat insulating body) 50, a circumferential heat insulating body 52, and a partition plate 54.
  • the container 40 has, for example, a cylindrical portion 60, and an upper hemisphere portion 62 and a lower hemisphere portion 64 provided at both ends of the cylindrical portion 60.
  • the structure is a combination of a cylinder and a hemisphere, but the structure is not limited to this.
  • the container 40 is installed in a direction in which the Z-axis direction (first direction), which is a direction parallel to the vertical direction, is the longitudinal direction. That is, the upper hemisphere portion 62 is arranged on the upper side of the lower hemisphere portion 64 in the vertical direction, and the central axis of the cylindrical portion 60 is oriented parallel to the Z-axis direction.
  • the fuel cell module 12 is preferably arranged so that the central axis of the cylindrical portion 60 is parallel to the Z-axis direction, but the fuel cell module 12 is not limited to this.
  • the container 40 is formed with two air inflow pipes 66, two air discharge pipes 68, a fuel gas inflow pipe, and a fuel gas discharge pipe.
  • the two air inflow pipes 66 are formed on the near side of the lower hemisphere portion 64 of the cylindrical portion 60.
  • the air inflow pipe 66 is connected to the air supply pipe 24, and the air supplied from the air supply pipe 24 flows into the inside of the container 40.
  • the two air discharge pipes 68 are formed on the vicinity side of the upper hemisphere portion 62 of the cylindrical portion 60.
  • the air discharge pipe 68 is connected to the air discharge pipe 15 and discharges the air inside the container 40 to the air discharge pipe 15.
  • the fuel gas inflow pipe 70 is formed in the upper hemisphere portion 62.
  • the fuel gas inflow pipe is connected to the fuel supply pipe 28, and the fuel gas supplied from the fuel supply pipe 28 flows into the inside of the container 40.
  • the fuel gas discharge pipe is formed in the lower hemisphere portion 64.
  • the fuel gas discharge pipe is connected to the fuel discharge pipe 17, and the fuel gas inside the container 40 is discharged to the fuel discharge pipe 17.
  • the container 40 is a sealed container except for the portion where the two air inflow pipes 66, the two air discharge pipes 68, the fuel gas inflow pipe, and the fuel gas discharge pipe are provided.
  • the container 40 includes a cell assembly 42, a pipe support plate (upper pipe support plate) 44, a pipe support plate (lower pipe support plate) 46, a heat insulating body (upper heat insulating body) 48, and a heat insulating body (lower side).
  • the heat insulating body) 50, the circumferential heat insulating body 52, and the partition plate 54 are housed inside.
  • a large number of cell stacks 56 are arranged in parallel.
  • the plurality of cell stacks 56 have a cylindrical shape in space inside, and are arranged in a direction in which the central axis is in the Z-axis direction, that is, in a direction in which the central axis is parallel to the central axis of the cylindrical portion 60.
  • the cell stack 56 has a plurality of fuel cell 100s arranged in a row in the Z-axis direction. The cell stack 56 will be described later.
  • the pipe support plate 44 and the pipe support plate 46 support both ends of the cell stack 56.
  • the pipe support plate 44 is a plate-shaped member arranged on one side (upper side) of the container 40 in the axial direction.
  • the pipe support plate 46 is a plate-shaped member arranged on the other side (lower side) of the container 40 in the axial direction.
  • the tube support plate 46 is inserted with the other end of the cell stack 56 arranged in the container 40.
  • One end of the cell stack 56 arranged in the container 40 is inserted into the pipe support plate 44.
  • All the cell stacks 56 arranged in the container 40 are inserted into the pipe support plates 44 and 46, respectively.
  • the pipe support plates 44 and 46 are sealed at the connection portion with the cell stack 56. Further, the outer edges of the pipe support plates 44 and 46 are in contact with the container 40 or the circumferential heat insulating body 52, and the contact portions are sealed. As a result, the pipe support plate 44 partitions the internal space of the container 40.
  • the space (divided space) surrounded by the upper hemisphere portion 62 of the container 40 and the pipe support plate 44 is connected to the fuel gas inflow pipe, and the fuel supply chamber to which the fuel gas is supplied from the fuel gas inflow pipe. It becomes 74.
  • a space partitioned by the lower hemisphere portion 64 of the container 40 and the pipe support plate 46 is connected to a fuel gas discharge pipe, and serves as a fuel discharge chamber 76 for discharging fuel gas from the fuel gas discharge pipe.
  • the fuel supply chamber 74 is connected to one open end of the cell stack 56 inserted into the pipe support plate 44.
  • the fuel discharge chamber 76 is connected to the other open end of the cell stack 56 inserted into the pipe support plate 44.
  • the heat insulating body 48 and the heat insulating body 50 are arranged between the pipe support plate 44 and the pipe support plate 46.
  • the heat insulating body 48 is arranged on one side (upper side) of the container 40 in the axial direction, and is formed in a blanket shape or a board shape by using a heat insulating material.
  • the heat insulating body 50 is arranged on the other side (lower side) of the container 40 in the axial direction, and is formed in a blanket shape or a board shape by using a heat insulating material.
  • Holes 51a and 51b through which the cell stack 56 is inserted are formed in the heat insulating bodies 48 and 50, respectively. The diameters of the holes 51a and 51b are larger than the diameter of the cell stack 56.
  • the space sandwiched between the heat insulating body 48 and the heat insulating body 50 becomes the power generation chamber 72. Further, the space between the pipe support plate 46 and the lower heat insulating body 50 is connected to the air inflow pipe 66 and becomes an air supply chamber 78. The space between the pipe support plate 44 and the upper heat insulating body 48 is connected to the air discharge pipe 78 and becomes the air discharge chamber 79. As a result, air is supplied to the outer peripheral surface of the cell stack 56, which is a space between the pipe support plate 46 and the lower heat insulating body 50 and is arranged in the power generation chamber 72.
  • the circumferential heat insulating body 52 is attached to the inner circumference of the cylindrical portion 60 of the container 40.
  • the circumferential heat insulating body 52 suppresses heat transfer between the inside and the outside of the container 40.
  • the partition plate 54 is a plate member arranged inside the cylindrical portion 60 of the container 40 and extending in the extending direction of the cell stack 56. The partition plate 54 is inserted between the cell stacks 56 of the cell assembly 42 to divide the cell assembly 42 into a plurality of regions.
  • the fuel cell 100 is arranged only in the power generation chamber 72.
  • the cell stack 56 includes a lead unit 80, a power generation unit 82, a power generation unit 84, a power generation unit 86, and a lead unit 88.
  • the fuel gas 90 flows inside the reed unit 80, the power generation unit 82, the power generation unit 84, the power generation unit 86, and the lead unit 88, and the reed unit 80, the power generation unit 82, the power generation unit 84, and the cell stack 56.
  • Air 92 flows around the power generation unit 86 and the lead unit 88.
  • the power generation unit 82 and the power generation unit 84 are connected by a connection unit 89. Further, the power generation unit 86 and the power generation unit 86 are connected by a connection unit 89.
  • the cell stack 56 is a cylindrical member in which each part is connected, and the lead part 80, the power generation part 82, the connection part 89, the power generation part 84, the connection part 89, and the power generation part 86 from the fuel supply position to the fuel discharge position. ,
  • the lead portion 88 is connected in this order.
  • the lead portions 80 and 88 are portions where the fuel cell 100 is not arranged.
  • the power generation units 82, 84, and 86 are areas in which the fuel cell 100 is arranged.
  • the lead portion 80 is a portion where the fuel cell 100 on the upper side in the Z-axis direction of the power generation unit 82 is not arranged.
  • the lead portion 88 is a portion where the fuel cell 100 below the power generation unit 86 in the Z-axis direction is not arranged.
  • the lead portion 80 includes a portion in contact with the pipe support plate 44 and a portion facing the heat insulating body 48.
  • the lead portion 88 includes a portion in contact with the pipe support plate 46 and a portion facing the heat insulating body 50.
  • the power generation units 82, 84, and 86 are arranged in the power generation chamber 72.
  • a plurality of fuel cell cells 100 are arranged in each of the power generation units 82, 84, and 86 in the Z-axis direction.
  • the power generation unit 84 is made of a material different from that of the power generation units 82 and 86.
  • the power generation unit 84 is the first unit, and the power generation unit 82 and the power generation unit 86 are the second units.
  • the power generation units 82, 84, and 86 include a tubular base tube 101 and a fuel cell 100 serving as a power generation element provided on the outer peripheral surface of the base tube 101.
  • the base tube 101 is a cylindrical ceramic tube that becomes porous, and fuel gas flows inside the base tube 101, that is, in a region surrounded by a cylindrical inner peripheral surface. Since the base pipe 101 is porous, the fuel gas flowing inside is guided to the outer peripheral surface side of the base pipe 101.
  • the lead portions 80 and 88 are not provided with the fuel cell 100, and are formed only of the substrate pipe 101.
  • the fuel cell 100 is configured by laminating a fuel electrode 103, a solid electrolyte 104, and an air electrode 105, and the fuel electrode 103 and the air electrode 105 are provided on both sides of the solid electrolyte 104.
  • the air electrode 105 contains an active metal, and the air electrode 105 has a function of contributing to a combustion reaction by the contained active metal (combustion by catalysis).
  • the fuel poles 103 are in contact with the outer peripheral surface of the base pipe 101, and a plurality of fuel cells 103 are arranged in the axial direction of the base pipe 101.
  • the fuel pole 103 of one adjacent fuel cell 100 and the air pole 105 of the other adjacent fuel cell 100 are connected by an interconnector 106.
  • the fuel cell 100 configured in this way generates power at a high temperature of, for example, 800 ° C. to 950 ° C. in the region where the power generation unit 84 is arranged during the power generation operation of the fuel cell system 10.
  • a protective film 118 is formed at the end where the connection portion 89 is installed.
  • the protective film 118 is formed on the axially outer end surface (outer peripheral surface) of the base tube 101, the end face of the base tube 101, and the end face on the adjacent battery cell unit 60 side.
  • the protective film 118 of the present embodiment is made of the same material as the interconnector (dense film having electrical conductivity).
  • the surface portion of the base tube 101 of the protective film 118 is integrally formed with the interconnector (dense film having electrical conductivity) 106.
  • the end face portion of the protective film 118 is formed by applying a material using an interconnector.
  • the fuel pole 103 is formed of Ni-zirconia electrolyte, and in the power generation units (second unit) 82 and 86, the fuel pole 103 is from the fuel pole 103 of the first unit.
  • the heat resistance refers to the stability (sinterability) of the material in a temperature environment, the durability due to the reactivity, and the change in the movement characteristics of ions and electrons required for the power generation of the SOFC cell (transport number). It also includes the characteristics and durability of catalytic activity such as adsorption and reaction of electrodes.
  • ceria-based electrolytes SDC, GDC
  • zirconia electrolyte examples include YSZ, ScSZ, and CaSZ.
  • YSZ is Y 2 O 3 doped ZrO 2 .
  • ScSZ is Sc 2 O 3 doped ZrO 2 .
  • CaSZ is Ca 2 O 3 doped ZrO 2 .
  • the solid electrolyte 104 is formed of zirconia electrolyte, and in the power generation units (second unit) 82 and 86, the solid electrolyte 104 is more heat resistant than the fuel electrode 103 of the first unit. It is formed of a low-grade zirconia electrolyte.
  • Power generating unit of the present embodiment (first unit) 84, the interconnector 106 is formed in one of LaCrO 3, LaSrCrO 3, LaSrTiO 3 , the power generation unit (second unit) 82 and 86, interconnector 106 is a It is formed of LaCrO 3 , LaSrCrO 3 , and LaSrTIO 3, which have lower heat resistance than the fuel electrode 103 of one unit.
  • the air electrode 105 is formed of any of LSM, LCM, and LSCM, and in the power generation units (second unit) 82 and 86, the interconnector 106 is the first unit. It is made of LSCF, LSF, LNF, and BSCF, which have lower heat resistance than the fuel electrode 103.
  • the LSM is (La, Sr) MnO 3 .
  • the LCM is Ca-toppedLaMnO 3 .
  • the LSCM is (La, Sr, Ca) MnO 3 .
  • LSCF is (La, Sr) (Co, Fe) O 3.
  • the LSF is (La, Sr) FeO 3 .
  • LNF is LaNi (Fe) O 3.
  • BSCF is Ba (Sr) Co (Fe) O 3.
  • the connecting portion 89 has a connecting jig 112, an adhesive layer 114, and a connecting portion air electrode 115.
  • the connecting jig 112 is arranged between the two battery cell units 60 to be connected, and is adhered to the two battery cell units 60 by the adhesive layer 114.
  • the connecting jig 112 is formed of a dense material having a thermal expansion similar to that of the solid electrolyte 104, for example, zirconia-based ceramic, specifically, zirconia (ZrO2), yttria-stabilized zirconia (YSZ), or the like.
  • the connecting jig 112 is preferably made of a material having a coefficient of thermal expansion similar to that of the substrate tube 101.
  • the connecting jig 112 has a cylindrical portion 122 and a convex portion 124.
  • the cylindrical portion 122 and the convex portion 124 are integrally formed.
  • the cylindrical portion 122 is a cylindrical member, and has a shape in which the inner peripheral diameter is larger than the outer peripheral diameter of the battery cell unit 60.
  • the convex portion 124 has a ring shape that is arranged on the inner peripheral surface of the cylindrical portion 122 and is convex inward in the radial direction. That is, the convex portion 124 is formed on the entire circumference of the cylindrical portion 122 in the circumferential direction.
  • the convex portion 124 is arranged near the center of the cylindrical portion 122 in the axial direction of the cylindrical portion 122.
  • the boundary 126 between the cylindrical portion 122 and the convex portion 124 has an R shape. That is, the boundary 126 between the cylindrical portion 122 and the convex portion 124 is a curved surface.
  • connection jig 112 is inserted at the end of the two power generation units 82, 84, 86 to be connected on the connected side. That is, the connecting jig 112 is a pipeline having a diameter larger than that of the power generation units 82, 84, 86, and one power generation unit is inserted into one end and the other power generation unit is inserted into the other end. There is.
  • the power generation units 82, 84, and 86 are inserted inside the cylinder of the connecting jig 112, and the outer peripheral surface is in contact with the inner peripheral surface of the connecting jig 112 via the adhesive layer 114. Further, in the battery cell unit 60, the end portion in the axial direction is in contact with the protrusion 124 of the connecting jig 112 via the adhesive layer 114.
  • the adhesive layer 114 is formed between the connecting jig 112 and the power generation unit, more specifically, the inner peripheral surface and the convex portion 124 of the cylindrical portion 122 of the connecting jig 112, the interconnector 106 of the power generation unit, and the protective layer 118. Is formed between.
  • the adhesive layer 114 uses a material that is dense and has a thermal expansion similar to that of the solid electrolyte 104.
  • As the adhesive layer 114 for example, a material obtained by adding fine alumina powder to coarse zirconia powder can be used.
  • the adhesive layer 114 can be formed by applying it in a slurry state and then firing it.
  • the connecting portion air pole 115 is formed on the outer circumference of the connecting jig 112 and the outer circumference of the two power generation portions.
  • the connecting air electrode 115 is made of the same material as the air electrode 105, and can be formed at the same time as the air electrode 105.
  • one end of the connecting air electrode 115 is in contact with the interconnector 106 of one power generation unit, and the other end is of the other power generation unit. It contacts the interconnector 106. Both ends of the connecting air electrode 115 are in contact with the interconnector 106 of the power generation unit, so that the interconnector 106 at the end of the power generation unit is made conductive.
  • the fuel cell module 12 performs a start-up operation for raising the fuel cell 100 to a predetermined temperature, and then performs a power generation operation for generating power in the fuel cell 100.
  • air flows into the air supply chamber 88 of the fuel cell module 12.
  • the air is supplied into the power generation chamber 82 through the gap between the hole 51b of the heat insulating body 50 and the cell stack 56.
  • fuel gas flows into the fuel supply chamber 84.
  • the fuel gas is supplied into the power generation chamber 82 through the inside of the base pipe 101 of the cell stack 56. At this time, the air and the fuel gas flow in opposite directions on the inner peripheral surface and the outer peripheral surface of the cell stack 56.
  • the fuel gas flowing inside the base pipe 101 passes through the pores of the base pipe 101 and reaches the fuel electrode 103.
  • This fuel gas is steam reformed using the active metal contained in the fuel electrode 103 as a catalyst.
  • Hydrogen produced by steam reforming passes through the pores of the fuel electrode 103 and reaches the solid electrolyte 104.
  • air flows outside the substrate tube 101 (air electrode 105).
  • Oxygen in the air receives electrons and is ionized while passing through the pores of the air electrode 105 or reaching the solid electrolyte 104.
  • the ionized oxygen passes through the solid electrolyte 104 and reaches the fuel electrode 103.
  • the oxygen ions that have passed through the solid electrolyte 104 react with the fuel gas, and the fuel gas emits electrons, which move from the fuel electrode to the air electrode via an external circuit.
  • the fuel cell module 12 generates electricity by such a battery reaction.
  • the fuel gas that has become hot and used for power generation is heat-exchanged with the air before being used for power generation in the air supply chamber 78 via the cell stack 56.
  • the high temperature air used for power generation is heat-exchanged with the fuel gas before being used for power generation in the air discharge chamber 79 via the cell stack 56.
  • the fuel gas flows into the fuel discharge chamber 86 and is discharged from the fuel discharge chamber 86 to the outside of the fuel cell module 12, and the air is discharged from the air discharge chamber 89 to the fuel cell module 12 It is discharged to the outside of.
  • the material of the fuel cell 100 of the power generation unit 84 which is the first unit of the cell stack 56, has higher heat resistance than the material of the fuel cell 100 of the power generation units 82, 86, which is the second unit. Formed from material.
  • the fuel cell module 12 can form the fuel cell 100 with a material suitable for each temperature range.
  • each of the power generation units 82, 84, and 86 can generate power with high efficiency.
  • the selectivity of the material can be increased. Further, since the range in which a highly durable material is used can be reduced, it can be easily manufactured.
  • the fuel electrode 103, the solid electrolyte 104, the air electrode 105, and the interconnector 106 are formed of different materials in the power generation unit 84 and the power generation units 82 and 86, but the present invention is limited to this. Not done.
  • the fuel cell module 12 may be made of a material in which at least one element of the fuel electrode 103, the solid electrolyte 104, and the interconnector 106 is different between the power generation unit 84 and the power generation units 82 and 86.
  • At least one element of the fuel electrode 103, the solid electrolyte 104, and the interconnector 106 of the power generation unit 84 may be a material different from the corresponding elements of the power generation units 82 and 86. It is more preferable that the power generation unit 84 and the power generation units 82 and 86 use materials corresponding to each of the fuel electrode 103, the solid electrolyte 104, the air electrode 105, and the interconnector 106.
  • the cell stack 56 is the length in the flow direction of the fuel gas of the power generation unit (second unit) 82 on the inlet side of the fuel gas, assuming that the total length of the power generation units 82, 84, 86 is 100%. Is preferably 5% to 12.5%. Assuming that the total length of the power generation units 82, 84, and 86 is 100%, the cell stack 56 has a length of the power generation unit (first unit) 84 in the flow direction of the fuel gas from 65.0% to 80. It is preferably 0%. When the total length of the power generation units 82, 84, and 86 is 100%, the cell stack 56 has a length of the fuel gas flow direction of the power generation unit (second unit) 86 on the fuel gas outlet side. It is preferably 0.0% to 22.5%.
  • the power generation units 82, 84, and 86 are arranged so as to be in the above range, and in particular, the length of the power generation unit 84 of the first unit is set in the above range to efficiently generate power. Can be done.
  • the fuel cell module 12 of the present embodiment is a cylindrical cell stack in which the fuel having fuel internal reforming and air are countercurrent, and the vicinity of the fuel gas inlet is a region where heat is exchanged to reform the fuel gas. Become. Therefore, the length of the power generation unit 82 is made shorter than that of the power generation unit 86, and the fuel gas can reach the arrangement region of the power generation unit 84 earlier, so that the cell temperature on the fuel inlet side is made higher than the fuel outlet cell temperature. Therefore, the reforming of the fuel can be preferably performed.
  • the first unit and the second unit are connected by using the connection unit 89, but the connection method is not limited to this.
  • the first unit and the second unit may be manufactured continuously by switching the material at the time of manufacturing.
  • the fuel cell module 12 of the present embodiment has a structure in which the fuel gas 90 and the air 92 flow in correspondence with each other, and in the fuel gas flow, the temperature on the outlet side of the fuel gas is lower than that in the central portion. 86 was used as the second unit.
  • the fuel cell 100 corresponding to the temperature can be arranged, and the performance can be improved.
  • the present invention is not limited to this, and the outlet side of the fuel gas does not have to have a second unit. That is, in the flow direction of the fuel gas, the upstream side may be the second unit and the downstream side may be the first unit.
  • the reaction temperature in the first unit is assumed to be 800 ° C. or higher and 950 ° C. or lower (high temperature specification), but the reaction temperature in the first unit is 600 ° C. or higher and lower than 800 ° C. (medium temperature specification). In the case of, each of them may be used as the following materials. Specifically, the reaction temperature of the first unit is 600 ° C. or higher and lower than 800 ° C. (medium temperature specification), and the reaction temperature of the second unit is 400 ° C. or higher and lower than 600 ° C. (low temperature specification).
  • the fuel electrode 103 is formed of a Ni-lanthanum-based electrolyte, and in the power generation units (second unit) 82 and 86, the fuel electrode 103 is more heat resistant than the fuel electrode 103 of the first unit. It is formed of a Ni-ceria electrolyte with low properties.
  • the lanthanum-based electrolyte is, for example, LSGM (La (Sr) Ga (Mg) O 3 ).
  • Examples of the ceria-based electrolyte include GDC (Gd-doped CeO 2 ) and SDC (Sm-doped CeO 2 ).
  • the solid electrolyte 104 is formed of lanthanum electrolyte, and in the power generation units (second unit) 82 and 86, the solid electrolyte 104 has lower heat resistance than the fuel electrode 103 of the first unit. Formed of electrolyte.
  • the interconnector 106 is formed in one of LaCrO 3, LaSrCrO 3, LaSrTiO 3 , the power generation unit (second unit) 82 and 86, the fuel of the interconnector 106 is the first unit It is made of ferritic stainless steel or stainless alloy, which has lower heat resistance than pole 103.
  • the air electrode 105 is formed of any of LSCF, LSF, LNF, and BSCF, and in the power generation units (second unit) 82 and 86, the interconnector 106 is the fuel electrode of the first unit. It is formed of LSCF, LSF, LNF, and BSCF, which have lower heat resistance than 103.
  • the fuel cell module 12 can be used in order to combine a plurality of units according to the temperature distribution.
  • the second unit of the medium temperature specification may be further arranged on the downstream side in the fuel gas flow direction of the second unit of the high temperature specification. That is, the second unit of the medium temperature specification is arranged downstream of the first unit of the high temperature specification described above, and the second unit of the low temperature specification (which may be the third unit) is arranged downstream of the second unit of the medium temperature specification. You may.
  • the second unit of the medium temperature specification may be arranged on the downstream side in the fuel gas flow direction of the first unit of the high temperature specification.
  • the cell stack is arranged in a region where the temperature of the first unit is higher than that of the second unit during power generation. As a result, the power generation performance of the cell stack can be further improved.
  • FIG. 7 is a schematic configuration diagram schematically showing a cell stack of another embodiment.
  • the cell stack 56 of the fuel cell module 12 of the above embodiment is a case where the fuel gas is reformed inside the cell stack 56, but the present invention is not limited to this.
  • the cell stack 56a shown in FIG. 7 includes a lead unit 80a, a power generation unit 82a, a power generation unit 84a, a power generation unit 86a, and a lead unit 88a.
  • the fuel gas 90 flows inside the reed unit 80a, the power generation unit 82a, the power generation unit 84a, the power generation unit 86a, and the lead unit 88a, and the reed unit 80a, the power generation unit 82a, the power generation unit 84a, and the cell stack 56a.
  • Air 92 flows around the power generation unit 86a and the lead unit 88a.
  • the power generation unit 82a and the power generation unit 84a are connected by a connection unit 89. Further, the power generation unit 86a and the power generation unit 86a are connected by a connection unit 89.
  • the cell stack 56a is a cylindrical member in which each part is connected, and is a lead part 80a, a power generation part 82a, a connection part 89, a power generation part 84a, a connection part 89, and a power generation part 86a from a fuel supply position to a fuel discharge position.
  • the lead portion 88a is connected in this order.
  • the cell stack 56a is the length in the flow direction of the fuel gas of the power generation unit (second unit) 82 on the inlet side of the fuel gas, assuming that the total length of the power generation units 82a, 84a, 86a is 100%. Is preferably 7.5% to 15.0%.
  • the cell stack 56 has a length of the fuel gas flow direction of the power generation unit (first unit) 84 from 70.0% to 85. It is preferably 0%.
  • the cell stack 56 has a length of 7 in the fuel gas flow direction of the power generation unit (second unit) 86 on the fuel gas outlet side. It is preferably 5.5% to 15.0%.
  • the cell stack 56a is a mechanism that does not internally reform the fuel gas, it is possible to efficiently generate power by setting the lengths of the power generation unit 82a and the power generation unit 86a to be the same. Further, in this case as well, by making the length of the first unit 84a longer than that of the other parts, it is possible to efficiently generate power.
  • the fuel cell module of the above embodiment has a structure in which the cell stack has a cylindrical shape and the fuel cell cells are arranged in a row, but the present invention is not limited to this, and can be used for various cell structures.
  • FIG. 8 is a schematic configuration diagram schematically showing a fuel cell module of another embodiment.
  • FIG. 9 is a perspective view schematically showing the cell stack of the fuel cell module shown in FIG.
  • a plurality of fuel cell cells 210 have a flat plate shape and are laminated in a direction orthogonal to the plane having the largest plate area.
  • the fuel cell 210 includes a fuel electrode 203, a solid electrolyte 204, and an air electrode 205.
  • the fuel cell module 200 is provided with separators 212 and 214 between the stacked fuel cell cells 210.
  • a flat fuel electrode 203, a solid electrolyte 204, and an air electrode 205 are laminated in this order.
  • the fuel electrode 203 faces the separator 212.
  • the air electrode 205 faces the separator 214.
  • the fuel 90 flows between the fuel electrode 203 and the separator 312, and the air 92 flows between the air electrode 205 and the separator 214.
  • the fuel cell module 200 is supplied in a direction in which the fuel gas 90 and the air 92 are orthogonal to each other. As shown in FIG.
  • the fuel cell module 200 divides the plane region of the fuel cell into the first unit 282 and the second unit 284, and uses different materials for the fuel cell.
  • the first unit 282 is a region downstream of the second unit 284 in the flow direction of the fuel gas 90 and downstream in the flow direction of the air 92.
  • the diagonal line of the rectangular fuel cell 210 is the boundary line. The position of the boundary line is not particularly limited, and may be on the upstream side in the fuel gas flow direction.
  • FIG. 10 is a schematic configuration diagram schematically showing a fuel cell module of another embodiment.
  • FIG. 11 is a perspective view schematically showing the cell stack of the fuel cell module shown in FIG.
  • the fuel cell 310 includes a fuel electrode 303, a solid electrolyte 304, an air electrode 305, and an interconnector 306.
  • a cylindrical fuel electrode 303, a solid electrolyte 304, and an air electrode 305 are laminated in this order from the outside to the inside.
  • the interconnector 306 is laminated on the surface of the fuel electrode 303 arranged on the outer periphery.
  • the fuel cell module 300 divides the power generation unit into a first unit 382 and a second unit 384 in the flow direction of the fuel gas of the fuel cell, and uses different materials for the fuel cell. It is supposed to be.
  • the first unit 382 is a region downstream of the second unit 384 in the flow direction of the fuel gas 90 and downstream in the flow direction of the air 92.
  • the efficiency can be achieved by using different materials for the fuel cell depending on the position in the flow direction of the fuel gas. It can generate electricity well.
  • FIG. 12 is a schematic configuration diagram schematically showing a fuel cell module of another embodiment.
  • FIG. 13 is a perspective view schematically showing the cell stack of the fuel cell module shown in FIG.
  • the fuel cell 410 includes a base 202, a fuel electrode 403, a solid electrolyte 404, an air electrode 405, and an interconnector 406.
  • the base 402 has an oval shape, and a plurality of passages through which fuel passes are formed in parallel inside the fuel cell cell 410.
  • the fuel electrode 403, the solid electrolyte 404, and the air electrode 405 are laminated in this order on the surface of the substrate 402.
  • the interconnector 406 is connected to an air electrode 405 arranged on the outer periphery.
  • the fuel cell module 400 of the present embodiment the fuel gas 90 flows inside the substrate 402, and the air 92 flows outside the cylinder. Further, the fuel gas 90 and the air 92 are parallel flows flowing in the same direction.
  • the fuel cell module 400 divides the power generation unit into a first unit 482 and a second unit 484 in the flow direction of the fuel gas of the fuel cell, and uses different materials for the fuel cell. It is supposed to be.
  • the first unit 482 is a region downstream of the second unit 384 in the flow direction of the fuel gas 90 and downstream in the flow direction of the air 92.
  • the efficiency can be achieved by using different materials for the fuel cell depending on the position in the flow direction of the fuel gas. It can generate electricity well.
  • Fuel cell system 12 Fuel cell module 14 Air supply device 15 Air discharge pipe 16 Fuel supply device 17 Fuel discharge pipe 18 Control device 20 Current meter 21 Thermometer 22 Air supply source 24 Air supply pipe 26 Fuel supply source 28 Fuel supply pipe 40 , 40a Pressure vessel 42 Cell assembly 44, 46 Pipe support plate 48, 50 Insulation body 51a, 51b Hole 52 Circumferential insulation 54 Partition plate 56 Cell stack 60 Cylindrical part 62 Upper hemisphere part 64 Lower hemisphere part 66 Air inflow pipe 68 Air discharge pipe 72 Power generation room 74 Fuel supply room 76 Fuel discharge room 78 Air supply room 79 Air discharge room 80, 88 Leads 82, 86 Second unit 84 First unit 89 Connection 90 Fuel gas 92 Air 100 Fuel cell 101 Base tube 103 Fuel pole 104 Solid electrolyte 105 Air pole 106 Interconnector 112 Connection jig 114 Adhesive layer 115 Connection part Air pole 118 Protective film 122 Cylindrical part 124 Convex part 132, 140 Arrow

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Abstract

La présente invention comprend : un récipient; un empilement de cellules qui est placé à l'intérieur du récipient, et dans lequel une pluralité de piles à combustible sont agencées; une unité d'alimentation en gaz oxydant qui fournit un gaz oxydant à l'empilement de cellules dans une première direction; et une unité d'alimentation en combustible qui fournit un combustible à l'empilement de cellules. Chacune des piles à combustible comprend : un substrat; une électrode à combustible qui est superposée sur le substrat; un électrolyte; une électrode à air; et un interconnecteur qui est relié à une pile à combustible adjacente. L'empilement de cellules comprend : une première unité dans laquelle une pile à combustible est placée; et une seconde unité qui est connectée à la première unité, et dans laquelle une pile à combustible est placée. Par rapport à la seconde unité, au moins un élément parmi l'électrode à combustible, l'électrolyte et l'interconnecteur de la pile à combustible étant constitués d'un matériau qui est différent du matériau de l'élément correspondant de la pile à combustible dans la première unité.
PCT/JP2021/003518 2020-03-16 2021-02-01 Module de pile à combustible et système de pile à combustible équipé de celui-ci WO2021186916A1 (fr)

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JP2020045341A JP7386111B2 (ja) 2020-03-16 2020-03-16 燃料電池モジュール及びこれを有する燃料電池システム
JP2020-045341 2020-03-16

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004030972A (ja) * 2002-06-21 2004-01-29 Aisin Seiki Co Ltd 固体酸化物形燃料電池システム
JP2010086830A (ja) * 2008-09-30 2010-04-15 Dainippon Printing Co Ltd 単室型固体酸化物形燃料電池
JP2012003934A (ja) * 2010-06-16 2012-01-05 Honda Motor Co Ltd 固体酸化物型燃料電池

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004030972A (ja) * 2002-06-21 2004-01-29 Aisin Seiki Co Ltd 固体酸化物形燃料電池システム
JP2010086830A (ja) * 2008-09-30 2010-04-15 Dainippon Printing Co Ltd 単室型固体酸化物形燃料電池
JP2012003934A (ja) * 2010-06-16 2012-01-05 Honda Motor Co Ltd 固体酸化物型燃料電池

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