WO2020022489A1 - 燃料電池セル及びセルスタック装置 - Google Patents

燃料電池セル及びセルスタック装置 Download PDF

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Publication number
WO2020022489A1
WO2020022489A1 PCT/JP2019/029460 JP2019029460W WO2020022489A1 WO 2020022489 A1 WO2020022489 A1 WO 2020022489A1 JP 2019029460 W JP2019029460 W JP 2019029460W WO 2020022489 A1 WO2020022489 A1 WO 2020022489A1
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WIPO (PCT)
Prior art keywords
main surface
cell
support substrate
gas flow
flow path
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/029460
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English (en)
French (fr)
Japanese (ja)
Inventor
崇大 新地
渓 内林
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Kyocera Corp
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Kyocera Corp
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Filing date
Publication date
Application filed by Kyocera Corp filed Critical Kyocera Corp
Priority to US17/262,393 priority Critical patent/US11495820B2/en
Priority to EP19840411.3A priority patent/EP3832765A4/en
Priority to CN201980048871.1A priority patent/CN112470314B/zh
Priority to JP2020532504A priority patent/JP7019817B2/ja
Publication of WO2020022489A1 publication Critical patent/WO2020022489A1/ja
Anticipated expiration legal-status Critical
Priority to JP2022015174A priority patent/JP7256309B2/ja
Ceased legal-status Critical Current

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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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H01M8/2425—High-temperature cells with solid electrolytes
    • H01M8/2428—Grouping by arranging unit cells on a surface of any form, e.g. planar or tubular
    • 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
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • H01M8/026—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant characterised by grooves, e.g. their pitch or depth
    • 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
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • 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
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H01M8/1226—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material characterised by the supporting layer
    • 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
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H01M8/2425—High-temperature cells with solid electrolytes
    • H01M8/2432—Grouping of unit cells of planar configuration
    • 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
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H01M8/2425—High-temperature cells with solid electrolytes
    • H01M8/2435—High-temperature cells with solid electrolytes with monolithic core structure, e.g. honeycombs
    • 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
    • H01M8/2457—Grouping of fuel cells, e.g. stacking of fuel cells with both reactants being gaseous or vaporised
    • 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
    • H01M8/2483—Details of groupings of fuel cells characterised by internal manifolds
    • 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
    • H01M8/2484—Details of groupings of fuel cells characterised by external manifolds
    • 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
    • H01M8/249—Grouping of fuel cells, e.g. stacking of fuel cells comprising two or more groupings of fuel cells, e.g. modular assemblies
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a fuel cell unit and a cell stack device.
  • a ⁇ porous support substrate having no electron conductivity in which a gas flow path is provided inside '' and ⁇ a plurality of portions provided on a surface of the support substrate at a plurality of locations apart from each other, a fuel electrode, a solid electrolyte, And a plurality of power generating element sections in which air electrodes are stacked "and" a fuel electrode and another air electrode provided between one or more sets of adjacent power generating element sections, respectively.
  • one or a plurality of electrical connecting portions for electrically connecting the fuel cell and the fuel cell see, for example, Patent Document 1).
  • the fuel cell may be simply referred to as a cell.
  • Such a configuration is also called “horizontal stripe type”. Power generation can be performed by introducing a fuel gas from one end of the gas flow path inside the cell and flowing a gas containing oxygen from one end outside the cell.
  • the cell stack device includes a manifold and a cell stack that is a plurality of cells (for example, see Patent Document 2). Each cell is supported by the manifold so as to extend upward from the manifold. Gas is distributed to each gas flow path of each cell via a manifold.
  • the cell of the present disclosure is a flat plate having a first main surface and a second main surface opposite to the first main surface and a columnar shape having a longitudinal direction, a support substrate having a gas flow path therein, And a plurality of element parts on at least one of a fuel electrode, a solid electrolyte, and an air electrode, which are arranged on one main surface and the second main surface so as to be separated from each other.
  • FIG. 1B is one example of a cross-sectional view of the cell shown in FIG. 1A.
  • FIG. 1B is a diagram for explaining one example of an operation state of the fuel cell unit shown in FIG. 1A.
  • FIG. 1B is one example of a cross-sectional view of the cell shown in FIG. 1A.
  • FIG. 1B is a perspective view showing one example of the support substrate of FIG. 1A.
  • FIG. 6B is a cross-sectional view showing one example of a state where each layer is formed in the first concave portion of FIG. 6A.
  • It is a perspective view which shows one example of a cell. It is one schematic explanatory drawing of the example of a cell stack apparatus.
  • FIG. 1A shows a fuel cell 1 according to this embodiment.
  • the cell 1 includes a plurality of columnar and flat supporting substrates 10 having a longitudinal direction in the x-axis direction, and a plurality of identical power generating element portions A electrically connected in series at predetermined intervals in the longitudinal direction. It is arranged in.
  • the upper and lower surfaces of the support substrate 10 are the main surfaces (planes) on both sides parallel to each other.
  • FIG. 1A shows an example having four power generation element sections A on one main surface. One main surface is defined as a first main surface, and the other main surface is defined as a second main surface.
  • This cell 1 is a so-called "horizontal stripe type".
  • the shape of the cell 1 as viewed from above is, for example, a rectangle having a length in the longitudinal direction of 5 cm to 50 cm and a length in the y-axis direction, which is a width direction perpendicular to the longitudinal direction, of 1 cm to 10 cm.
  • the thickness of the cell 1 is 1 mm to 5 mm.
  • FIG. 2 is a cross-sectional view in the longitudinal direction of the cell 1 shown in FIG. 1A in addition to FIG. 1A.
  • FIG. 2 is a part of a cross-sectional view in the longitudinal direction of the fuel cell 1 shown in FIG. 1A. In other words, it is a part of a cross-sectional view along the gas flow path 11.
  • the support substrate 10 is a columnar and flat fired body having no electron conductivity, that is, made of an insulating porous material. Inside the support substrate 10, a plurality of gas passages 11, which are a plurality of through holes extending in the longitudinal direction, are located at predetermined intervals in the width direction.
  • the support substrate 10 shown in FIG. 2 has six gas channels 11. The surface exposed to the gas flowing inside the support substrate 10 is referred to as a gas channel wall W.
  • the support substrate 10 has the first concave portions 12 at a plurality of locations on the main surface.
  • Each first concave portion 12 is a rectangular parallelepiped depression defined by a bottom wall made of the material of the support substrate 10 and a circumferentially closed side wall made of the material of the support substrate 10 over the entire circumference.
  • the side walls closed in the circumferential direction are two side walls along the longitudinal direction and two side walls along the width direction.
  • the lower main surface in FIG. 2 is the first main surface 101, and the upper main surface is the second main surface 102.
  • the support substrate 10 contains “transition metal oxide or transition metal” and insulating ceramics.
  • the “transition metal oxide or transition metal” may be NiO (nickel oxide) or Ni (nickel).
  • the transition metal can function as a catalyst for promoting the reforming reaction of the fuel gas, in other words, as a catalyst for reforming the hydrocarbon-based gas.
  • the insulating ceramic may be MgO (magnesium oxide) or “a mixture of MgAl 2 O 4 (magnesia alumina spinel) and MgO (magnesium oxide)”. Further, as insulating ceramics, CSZ (calcia-stabilized zirconia), YSZ (yttria-stabilized zirconia, sometimes 8YSZ), and Y 2 O 3 (yttria) may be used.
  • the supporting substrate 10 contains “transition metal oxide or transition metal”, the gas containing the residual gas component before reforming can promote the reforming of the residual gas component before reforming by the above-described catalytic action.
  • the support substrate 10 contains insulating ceramics, the insulation of the support substrate 10 can be ensured. As a result, insulation between adjacent fuel electrodes can be ensured.
  • the thickness of the support substrate 10 may be 1 mm to 5 mm.
  • this structure is substantially vertically symmetrical, only the configuration on the upper surface side of the support substrate 10 will be described for simplicity of description.
  • the lower surface side of the support substrate 10 also has a similar configuration although the shape is partially different.
  • each fuel electrode current collector 21 has a rectangular parallelepiped shape.
  • a second concave portion 21a on the outer surface, which is the upper surface of each anode current collector 21.
  • each of the second recesses 21a is a rectangular parallelepiped depression defined by a bottom wall made of the material of the anode current collector 21 and a side wall closed in the circumferential direction.
  • two side walls along the x-axis direction which is the longitudinal direction, are a part of the support substrate 10
  • the two side walls along the y-axis direction, which is the width direction are fuel electrode current collectors 21. Part of.
  • the fuel electrode active part 22 is filled and buried in each second concave part 21a.
  • Each fuel electrode active portion 22 has a rectangular parallelepiped shape.
  • the anode 20 includes an anode current collector 21 and an anode active unit 22.
  • the fuel electrode 20, ie, the fuel electrode current collector 21 and the fuel electrode active part 22, are porous fired bodies having electron conductivity.
  • the two side surfaces and the bottom surface along the y-axis direction, which is the width direction of each anode active portion 22, are in contact with the anode current collector 21 in the second recess 21a.
  • 3A third concave portion 21b is provided on the outer surface, which is the upper surface of each anode current collector 21, except for the second concave portion 21a.
  • Each of the third recesses 21b is a rectangular parallelepiped depression defined by a bottom wall serving as the anode current collector 21 and a side wall closed in the circumferential direction.
  • a bottom wall serving as the anode current collector 21
  • a side wall closed in the circumferential direction Of the side walls closed in the circumferential direction, two side walls along the x-axis direction, which is the longitudinal direction, are a part of the support substrate 10, and the two side walls along the y-axis direction, which is the width direction, are fuel electrode current collectors 21. Part of.
  • Each third concave portion 21b is filled and buried with an interconnector 30 which is a conductive dense body.
  • Each interconnector 30 has a rectangular parallelepiped shape.
  • the interconnector 30 is a dense fired body having electron conductivity. The two side surfaces and the bottom surface along the width direction of each interconnector 30 are in contact with the anode current collector 21 in the third recess 21b.
  • the outer surface that is the upper surface of the fuel electrode 20, that is, the anode current collector 21 and the fuel electrode active unit 22, the outer surface that is the upper surface of the interconnector 30, and the second main surface 102 of the support substrate 10 have respective surfaces. Is flush.
  • the fuel electrode active portion 22 may include, for example, NiO (nickel oxide) and YSZ (yttria stabilized zirconia). Alternatively, it may include NiO (nickel oxide) and GDC (gadolinium-doped ceria).
  • the fuel electrode current collector 21 may include, for example, NiO (nickel oxide) and YSZ (yttria stabilized zirconia). Alternatively, it may contain NiO (nickel oxide) and Y 2 O 3 (yttria), or may contain NiO (nickel oxide) and CSZ (calcia-stabilized zirconia).
  • the thickness of the anode active portion 22 may be 5 ⁇ m to 30 ⁇ m.
  • the thickness of the anode current collector 21, that is, the depth of the first recess 12 may be 50 ⁇ m to 500 ⁇ m.
  • the anode current collector 21 is electron conductive.
  • the fuel electrode active part 22 has electron conductivity and oxidizing ion (oxygen ion) conductivity.
  • the “volume ratio of the substance having oxidative ion conductivity to the total volume excluding the pore portion” in the anode active portion 22 is defined as “the oxidative ion conductivity to the total volume excluding the pore portion” in the anode current collector 21. Volume ratio of a substance having
  • the interconnector 30 may include, for example, LaCrO 3 (lanthanum chromite). Alternatively, (Sr, La) TiO 3 (strontium titanate) may be included. The thickness of the interconnector 30 may be between 10 ⁇ m and 100 ⁇ m. The porosity may be 10% or less.
  • the solid electrolyte membrane 40 is a dense fired body having ion conductivity and no electron conductivity.
  • the solid electrolyte membrane 40 may include, for example, YSZ (yttria-stabilized zirconia). Alternatively, LSGM (lanthanum gallate) may be included.
  • the thickness of the solid electrolyte membrane 40 may be 3 ⁇ m to 50 ⁇ m.
  • the entire outer peripheral surface of the support substrate 10 extending in the longitudinal direction may be covered with a dense layer composed of the interconnector 30 and the solid electrolyte membrane 40.
  • This dense layer has a gas sealing function that makes it difficult for fuel gas flowing in the space inside the dense layer to mix with air flowing in the space outside the dense layer.
  • the solid electrolyte membrane 40 is formed on the upper surface of the anode 20, which is the anode current collector 21 and the anode active unit 22, and on both ends in the longitudinal direction of the upper surface of the interconnector 30. , And the main surface of the support substrate 10.
  • the air electrode 60 is located on the upper surface of the solid electrolyte membrane 40 in contact with each fuel electrode active part 22 via a reaction prevention film (not shown).
  • the reaction prevention film is a dense fired body.
  • the air electrode 60 is a porous fired body having electron conductivity.
  • the shape of the reaction prevention film and the air electrode 60 as viewed from above is a rectangle substantially the same as the fuel electrode active portion 22.
  • the reaction preventing film may include, for example, (Ce, Gd) O 2 (gadolinium-doped ceria, GDC).
  • the thickness of the reaction prevention film may be 3 ⁇ m to 50 ⁇ m.
  • the air electrode 60 may include, for example, (La, Sr) (Co, Fe) O 3 (lanthanum strontium cobalt ferrite, LSCF).
  • the air electrode 60 is made of (La, Sr) FeO 3 (lanthanum strontium ferrite, LSF), La (Ni, Fe) O 3 (lanthanum nickel ferrite, LNF), (La, Sr) CoO 3 (lanthanum strontium cobaltite, LSC) ) May be included.
  • the air electrode 60 may have a two-layer structure of a first layer which is an inner layer made of LSCF and a second layer which is an outer layer made of LSC.
  • the thickness of the air electrode 60 may be 10 ⁇ m to 100 ⁇ m.
  • the reaction prevention film When the reaction prevention film is interposed, the YSZ in the solid electrolyte membrane 40 and the Sr in the air electrode 60 hardly react with each other during cell production or in a cell during operation, and the solid electrolyte membrane 40 and the air electrode 60 It becomes difficult to form a reaction layer having a large electric resistance at the interface.
  • the stacked body in which the fuel electrode 20, the solid electrolyte membrane 40, and the air electrode 60 are stacked corresponds to the “power generation element portion A”.
  • the power generation element part A may include a reaction prevention film.
  • the air electrode 60 is a porous fired body having electron conductivity.
  • the shape of the air electrode current collector 70 as viewed from above is a rectangle.
  • the air electrode current collector 70 may include, for example, (La, Sr) (Co, Fe) O 3 (lanthanum strontium cobalt ferrite, LSCF) or (La, Sr) CoO 3 (lanthanum strontium cobaltite, LSC) ) May be included. Further, the air electrode current collector 70 may include Ag (silver) and Ag-Pd (silver-palladium alloy). The thickness of the air electrode current collector 70 may be 50 ⁇ m to 500 ⁇ m. The porosity of the air electrode current collector 70 may be 20 to 60%.
  • Adjacent power generating element units A are electrically connected via the “electrode current collector 70 and the interconnector 30” having electron conductivity.
  • a plurality (four in this embodiment) of power generation element units A arranged on the upper surface of the support substrate 10 are electrically connected in series. Portions other than the “power generation element portion A” including the “electrode collection portion 70 and the interconnector 30” having electronic conductivity are referred to as “electrical connection portions B”.
  • the gas flow path 11 side of the support substrate 10 may be referred to as “inside”, and the surface of the support substrate 10 on which the power generation element unit A is disposed may be referred to as “outside”.
  • a fuel gas such as a hydrogen gas flows from the first end which is one end in the longitudinal direction of the support substrate 10 to the second end which is the other end in the gas passage 11 of the support substrate 10,
  • an “oxygen-containing gas” such as air from the first end to the second end on the upper and lower surfaces of the support substrate 10, particularly on each air electrode current collector 70, between the two side surfaces of the solid electrolyte membrane 40.
  • An electromotive force is generated due to the difference between the generated oxygen partial pressures.
  • a chemical reaction represented by the following formulas (1) and (2) occurs, and a current flows to enter a power generation state. (1/2) ⁇ O 2 + 2e - ⁇ O 2- ( at air electrode 60) (1) H 2 + O 2- ⁇ H 2 O + 2e ⁇ (at fuel electrode 20) (2)
  • the temperature environment may be different on both sides of the cell 1.
  • the degradation is likely to progress locally because the reaction speed is different between the one main surface side and the other main surface side. That is, the durability of the cell 1 might be reduced.
  • the cell 1 of the present disclosure has a first portion 1a located on the first main surface 101 side of the gas flow channel 11 and a second portion 1b located on the second main surface 102 side of the gas flow channel 11,
  • the structure of the first part 1a and the second part 1b is asymmetric.
  • the entire length of W may be different between the first portion 1a on the first main surface 101 located on the lower side in FIG. 2 and the second portion 1b on the second main surface 102 located on the upper side in FIG. .
  • the entire length of the gas passage wall W2 on the second main surface 102 side is smaller than the entire length of the gas passage wall W1 on the first main surface 101 side.
  • the second main surface 102 having a small overall length of the gas flow path wall W2 faces the high temperature side, and the total length of the gas flow path wall W1 is large toward the low temperature side.
  • the cells 1 can be arranged so that the first main surface 101 faces each other.
  • the probability that the fuel gas collides with the gas flow path wall W1 on the first main surface 101 side can be increased by making the first main surface 101 face the side where the temperature is low and the above reaction does not easily occur. Is easily taken into the supporting substrate 10, and the above-mentioned reaction is likely to occur on the side where the temperature is low.
  • the probability that the fuel gas collides with the gas flow path wall W2 on the second main surface 102 side can be reduced, so that the fuel gas It is hard to be taken into the supporting substrate, and the above reaction hardly occurs on the side where the temperature is high. Therefore, a portion where deterioration easily progresses locally hardly occurs, and the durability of the entire cell hardly decreases.
  • the gas flow path wall W on the first main surface 101 side is wavy in the above-described cross-sectional view.
  • the probability that the fuel gas collides with the gas flow path wall W1 on the first main surface 101 side can be increased, so that the fuel gas is easily taken into the support substrate 10, and the above-described reaction occurs on the low temperature side. Is more likely to occur.
  • the gas flow path wall W2 on the second main surface 102 side may be similarly wavy as in the present embodiment.
  • the wavy shape means that the gas flow path wall W has a meandering shape in the cross-sectional view described above.
  • the total length of the gas passage wall W can be calculated by measuring the length of the gas passage wall W in a cross-sectional photograph along the gas passage 11 as shown in FIG.
  • the entire length of the gas flow path wall W means not the linear length in the direction in which the gas flow path 11 extends, but the length along the gas flow path wall W.
  • the gas flow path wall W1 on the first main surface 101 side has a wavy shape meandering more than the gas flow path wall W2 on the second main surface 102 side. Is longer than the entire length of the gas passage wall W2 on the second main surface 102 side.
  • the gas flow path wall W1 on the first main surface 101 side is wavy, but may be, for example, arcuate.
  • the total length of the gas flow path wall W1 on the first main surface 101 side may be larger than the total length of the gas flow path wall W located between the first main surface 101 and the second main surface 102. With this configuration, a large amount of fuel gas can be taken in from the gas flow path wall W1 close to the first main surface 101, and the above-described reaction easily occurs on the first main surface 101 side.
  • the total length of the gas flow path wall W located between the first main surface 101 and the second main surface 102 is a cross section along the gas flow path 11 in a direction orthogonal to the cross section in FIG. 2 (parallel to each main surface and (A cross section along the gas flow path 11).
  • the total length of the gas flow path wall W2 on the second main surface 102 side may be larger than the total length of the gas flow path wall W located between the first main surface 101 and the second main surface 102.
  • the length of the interface between the fuel electrode 20 and the solid electrolyte 40 in each power generation element portion A on the first main surface 101 side is determined.
  • the sum may be different from the sum of the lengths of the interfaces between the fuel electrode 20 and the solid electrolyte 40 in each power generating element portion A on the second main surface 102 side.
  • the sum of the lengths of the interfaces between the fuel electrode 20 and the solid electrolyte 40 in each of the power generating element portions A on the second main surface 102 side is equal to the fuel in each of the power generating element portions A on the first main surface 101 side. It is smaller than the sum of the lengths of the interface between the pole 20 and the solid electrolyte 40.
  • the second main surface 102 having a small sum of the lengths of the interfaces between the fuel electrode 20 and the solid electrolyte 40 faces the high temperature side, and the fuel The cell 1 can be arranged so that the first main surface 101 having a large sum of the lengths of the interfaces between the pole 20 and the solid electrolyte 40 faces each other. Also according to this configuration, a portion where deterioration easily progresses locally hardly occurs, and the durability of the entire cell 1 hardly decreases.
  • the sum of the lengths of the interface between the fuel electrode 20 and the solid electrolyte 40 on the first main surface 101 side is based on the cross-sectional photograph along the gas flow path 11 as shown in FIG. This is a value obtained by measuring the length of the interface between the fuel electrode 20 and the solid electrolyte 40 in each power generating element section A, and adding the respective lengths. The same applies to the sum of the lengths of the interfaces between the fuel electrode 20 and the solid electrolyte 40 on the second main surface 102 side.
  • the length of the interface between the fuel electrode 20 and the solid electrolyte 40 means not the length of a straight line in the direction in which the gas flow path 11 extends, but the length along the interface. In the embodiment of FIG.
  • the length of the interface on the first main surface 101 side is It is larger than the length of the interface on the second main surface 102 side.
  • the total length of the gas passage wall W1 of the first portion 1a is different from the total length of the gas passage wall W2 of the second portion 1b, and the fuel electrode 20 and the solid electrolyte 40 on the first main surface 101 side are different.
  • the sum of the length of the interface between the fuel electrode 20 and the solid electrolyte 40 on the second main surface 102 side is different from the sum of the length of the interface between the fuel electrode 20 and the solid electrolyte 40. Only one of the sums of the lengths of the interfaces between 20 and the solid electrolyte 40 may be different between the first portion 1a and the second portion 1b.
  • the porosity of the support substrate 10 in the first portion 1a and the support substrate in the second portion 1b may be different.
  • the porosity of the support substrate 10 in the second portion 1b located on the lower side of FIG. 4 is lower than the porosity of the support substrate 10 in the first portion 1a located on the upper side of FIG.
  • the first main surface 101 of the support substrate 10 is located on the upper side
  • the second main surface 102 of the support substrate 10 is located on the lower side.
  • FIG. 4 shows pores 10 c inside the support substrate 10.
  • the second main surface 102 having a low porosity faces the high temperature side
  • the first main surface 102 having a high porosity side has a low temperature.
  • Cell 1 can be arranged so that 101 faces each other. Since the porosity of the support substrate 10 on the first main surface 101 side is higher than the porosity of the support substrate 10 on the second main surface 102 side, the fuel gas passes through the support substrate 10 and the fuel electrode on the first main surface 101 side. Thus, the above-described reaction in the power generating element portion A on the first main surface 101 side is likely to occur.
  • the above-described reaction is likely to occur when the first main surface 101 of the support substrate 10 faces the side where the temperature is low and the reaction hardly occurs.
  • the second main surface 102 face the side where the temperature is high and the reaction is likely to occur, the above-described reaction is less likely to occur on the side where the temperature is high. Therefore, a portion where deterioration easily progresses locally hardly occurs, and the durability of the entire cell hardly decreases.
  • the porosity of the supporting substrate 10 can be analyzed by the following method. First, three dividing lines are drawn along the longitudinal direction of the support substrate 10, that is, along the gas flow path 11 so as to divide the length of the support substrate 10 in the width direction into four equal parts. Next, the gas flow paths 11 closest to the respective dividing lines in the width direction are specified. Next, three cross sections of the support substrate 10 including the three specified gas channels 11 are obtained. Next, an image in the obtained cross section is acquired with a scanning electron microscope. Next, a binarization process is performed so that a portion having the pores 10c and a portion other than the pores 10c in the acquired image can be distinguished.
  • the ratio of the pores 10c in the region of the support substrate 10 on the first main surface 101 side and the ratio of the pores 10c in the region of the support substrate 10 on the second main surface 102 side are calculated.
  • the average porosity of the support substrate 10 in the first portion 1a and the average porosity of the support substrate 10 in the second portion 1b are calculated from the ratio occupied by the pores 10c calculated in each section.
  • a method of adjusting the porosity of the first main surface 101 side and the second main surface 102 side of the support substrate 10 will be described. As one method, it can be realized by applying a sintering aid to the surface of the second main surface 102 of the molded body 10g of the supporting substrate, and then firing.
  • the support substrate 10 on the second main surface 102 side becomes denser than the first main surface 101 side, that is, the porosity of the support substrate 10 on the second main surface 102 side can be made lower than the support substrate 10 on the first main surface 101 side.
  • the length from the gas flow path 11 to the first main surface 101 of the support substrate 10 may be different from the length from the gas flow path 11 to the second main surface 102.
  • the length from the gas flow channel 11 to the second main surface 102 of the support substrate 10 is larger than the length from the gas flow channel 11 to the first main surface 101.
  • the cells 1 are arranged so that the second main surface 102 faces the higher temperature side and the first main surface 101 faces the lower temperature side.
  • the fuel gas passes through the support substrate 10. It becomes easier to reach the fuel electrode 20 on the first main surface 101 side, and thus the above-described reaction is more likely to occur in the power generation element portion A on the first main surface 101 side. In other words, the above-described reaction is likely to occur when the first main surface 101 of the support substrate 10 faces the side where the temperature is low and the reaction hardly occurs.
  • the second main surface 102 By making the second main surface 102 face the side where the temperature is high and the reaction is likely to occur, the above-described reaction is less likely to occur on the side where the temperature is high. Therefore, a portion where deterioration easily progresses locally hardly occurs, and the durability of the entire cell hardly decreases.
  • the length from the gas passage 11 to the first main surface 101 and the length from the gas passage 11 to the second main surface 102 can be analyzed by the following method.
  • three dividing lines are drawn along the longitudinal direction of the support substrate 10, that is, along the gas flow path 11 so as to divide the length of the support substrate 10 in the width direction into four equal parts.
  • the gas flow paths 11 closest to the respective dividing lines in the width direction are specified.
  • three cross sections of the support substrate 10 including the three specified gas channels 11 are obtained.
  • an image in the obtained cross section is acquired with a scanning electron microscope.
  • an area of the support substrate 10 including the pores 10c in the acquired image is specified.
  • the value of the area of the region of the support substrate 10 on the first main surface 101 side and the value of the area of the region of the support substrate 10 on the second main surface 102 side in each cross section are calculated.
  • the average area value of the support substrate 10 in the first portion 1a and the average area value of the support substrate 10 in the second portion 1b are calculated from the values calculated in each section.
  • the ratio between the average area value of the support substrate 10 in the first portion 1a and the average area value of the support substrate 10 in the second portion 1b is determined by the length from the gas passage 11 of the support substrate 10 to the respective main surfaces. Consider as a ratio.
  • the porosity of the support substrate 10 at the first portion 1a is different from the porosity of the support substrate 10 at the second portion 1b, and the length from the gas flow path 11 to the first main surface 101 and the gas flow rate are different.
  • the example in which the length from the path 11 to the second main surface 102 is different is shown, only one of the porosity of the support substrate 10 and the length from the gas flow path 11 to the main surface is the first portion 1a.
  • the second part 1b may be different.
  • the first power generation element portion A1 and the second power generation element portion A2 may be arranged at asymmetric positions. That is, the first power generation element A1 and the second power generation element A2 do not have to be arranged at symmetric positions.
  • FIG. 5 FIG. 6A, and FIG. 6B
  • “g” at the end of the reference numeral of each member indicates that the member is “before firing”.
  • a support substrate molded body 10g having the shape shown in FIG. 5 is prepared.
  • the molded body 10g of the support substrate is formed by extrusion molding, cutting, or the like using a slurry obtained by adding a binder or the like to a powder of the material of the support substrate 10, for example, NiO and MgO. Can be manufactured.
  • the molded bodies 21g of the anode current collector are respectively disposed in the first concave portions formed on the upper and lower surfaces of the molded body 10g of the support substrate.
  • the formed body 22g of the anode active portion is disposed in each second concave portion formed on the outer surface of the formed body 21g of the anode current collector.
  • the molded body 21g of each anode current collector and the anode active section 22g are formed, for example, by using a slurry obtained by adding a binder or the like to a material of the anode 20, for example, a powder containing Ni and YSZ. And using a printing method or the like.
  • an interconnector is formed in each of the third recesses formed in the “excluding the portion where the formed body 22g of the anode active part is embedded” on the outer surface of the formed body 21g of each anode current collector.
  • 30 g of bodies are arranged.
  • the molded product 30g of each interconnector is disposed by using a printing method or the like, for example, using a slurry obtained by adding a binder or the like to the material of the interconnector 30, for example, LaCrO 3 powder.
  • a molded membrane of a solid electrolyte membrane is provided on the entire surface except for the center of each of the plurality of interconnector molded bodies 30g.
  • the molded film of the solid electrolyte membrane uses, for example, a printing method, a dipping method, or the like, using a material obtained by adding a binder or the like to the material of the solid electrolyte membrane 40, for example, a YSZ powder.
  • a molded film of a reaction prevention film is provided on the outer surface of the solid electrolyte membrane molded body at a position in contact with the molded body of each fuel electrode.
  • the molded film of each reaction prevention film is formed by, for example, a printing method using a slurry obtained by adding a binder or the like to a material of the reaction prevention film, for example, GDC powder.
  • the first main surface 101 side is set to 1500 ° C.
  • the second main surface 102 side is set to 1450 ° C. for 3 hours.
  • a part of the interface between the fuel electrode 20 and the solid electrolyte 40 also protrudes toward the gas flow path 11 following the shape deformation due to the sintering of the support substrate 10.
  • the interface between the fuel electrode 20 and the solid electrolyte 40 has a shape in which a part thereof protrudes toward the gas flow path, it can be realized by manufacturing a molded body having the shape.
  • an air electrode forming film is formed on the outer surface of each reaction preventing film.
  • the formed film of each air electrode is provided, for example, using a printing method or the like using a slurry obtained by adding a binder or the like to the material of the air electrode 60, for example, LSCF powder.
  • the air electrode forming film, the solid electrolyte membrane 40, and the air electrode forming film of one of the power generating element portions A are provided on the outer surface of the interconnector 30, and the other. Is formed so as to straddle the interconnector 30 of the power generation element section A.
  • a formed film of the air electrode current collector having a desired shape (thickness) is formed by a printing method or the like. It can be provided on the outer surface of the air electrode forming film or the like.
  • the support substrate 10 on which the formed film is formed is fired, for example, in air at 1050 ° C. for 3 hours. Thus, the cell shown in FIG. 1 is obtained.
  • At least one of the first main surface 101 and the second main surface 102 at least one of the plurality of power generation element units A arranged in the longitudinal direction, that is, the x-axis direction.
  • One power generating element part A may be arranged at a position different from other power generating element parts A in a direction orthogonal to the direction in which the plurality of power generating element parts A are arranged on the main surface.
  • the position in the width direction, that is, the y-axis direction of at least one power generation element portion A of the plurality of power generation element portions A is It may be shifted from other power generation element parts A.
  • the positions of the plurality of power generation elements A in the y-axis direction may be different from each other.
  • the temperature of the power generation element portion A where the above-described reaction occurs is relatively high. Therefore, when the power generating element portions A are arranged along the central portion in the width direction of the support substrate 10, the temperature of the central portion in the width direction of the cell 1 becomes particularly high. Since the position of at least one power generating element portion A in the width direction is shifted from the other power generating element portions A, the temperature distribution is less likely to be biased in the width direction. As a result, a portion where deterioration easily progresses locally hardly occurs, and the durability of the entire cell 1 hardly decreases.
  • FIG. 8 is a schematic explanatory diagram of the cell stack device.
  • the cell stack device 80 of FIG. 8 includes a cell stack 81 and a fixing member 82.
  • the cell stack 81 has a plurality of cells 1 and a plurality of cells 1 are arranged in a direction in which the main surfaces of the support substrate 10 face each other.
  • the fixing member 82 is a member for fixing one end side of the cell 1 in the longitudinal direction.
  • the fixing member 82 has a gas storage space for storing fuel gas to be supplied to the gas passage 11 of the cell 1 therein.
  • the cell stack device 80 includes a fuel gas supply pipe 83 that supplies fuel gas to the gas storage space.
  • a comb-like connecting member 84 is arranged between the cells 1.
  • all the arranged cells 1 can be electrically connected in series by the connection members 84, and a desired power generation amount can be obtained efficiently.
  • the number of cells 1 may be appropriately adjusted according to a desired power generation amount.
  • Each cell 1 is fixed to the fixing member 82 by, for example, an insulating adhesive such as glass.
  • the fixing member 82 may be made of a material having heat resistance, such as a metal such as silicon, iron, titanium oxide, or aluminum oxide, or a material such as ceramic having heat resistance.
  • the second main surface 102 of the cell 1 located on the leftmost side of the cell stack 81 faces the side where the cell stack center 81C is located.
  • the second main surface 102 of the cell 1 One main surface 101 faces the side opposite to the side where the cell stack center 81C is located.
  • the fuel cell module of the present invention is configured by storing the above-described cell stack device 80 in a storage container. Thereby, a highly durable fuel cell module can be obtained.
  • a fuel cell, a fuel cell stack device, a fuel cell module, and a fuel cell device are one of examples of a “cell”, a “cell stack device”, a “module”, and a “module storage device”.
  • other examples may be an electrolysis cell, an electrolysis cell stack device, an electrolysis module, and an electrolysis device, respectively.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Sustainable Energy (AREA)
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PCT/JP2019/029460 2018-07-27 2019-07-26 燃料電池セル及びセルスタック装置 Ceased WO2020022489A1 (ja)

Priority Applications (5)

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US17/262,393 US11495820B2 (en) 2018-07-27 2019-07-26 Fuel battery cell and cell stack device
EP19840411.3A EP3832765A4 (en) 2018-07-27 2019-07-26 FUEL BATTERY CELL AND CELL STACK
CN201980048871.1A CN112470314B (zh) 2018-07-27 2019-07-26 燃料电池单元及电池单元堆装置
JP2020532504A JP7019817B2 (ja) 2018-07-27 2019-07-26 燃料電池セル及びセルスタック装置
JP2022015174A JP7256309B2 (ja) 2018-07-27 2022-02-02 セル及びセルスタック装置

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JP2018-141502 2018-07-27
JP2018-201989 2018-10-26
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CN112470314B (zh) 2024-10-29
CN112470314A (zh) 2021-03-09
JP7019817B2 (ja) 2022-02-15
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JPWO2020022489A1 (ja) 2021-08-02
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