WO2018199095A1 - Pile à combustible à oxyde solide - Google Patents

Pile à combustible à oxyde solide Download PDF

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Publication number
WO2018199095A1
WO2018199095A1 PCT/JP2018/016617 JP2018016617W WO2018199095A1 WO 2018199095 A1 WO2018199095 A1 WO 2018199095A1 JP 2018016617 W JP2018016617 W JP 2018016617W WO 2018199095 A1 WO2018199095 A1 WO 2018199095A1
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WIPO (PCT)
Prior art keywords
power generation
region
generation element
support substrate
gas flow
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Application number
PCT/JP2018/016617
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English (en)
Japanese (ja)
Inventor
雄一 堀
真 兒井
岡本　高明
Original Assignee
京セラ株式会社
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Publication date
Application filed by 京セラ株式会社 filed Critical 京セラ株式会社
Priority to JP2019514535A priority Critical patent/JPWO2018199095A1/ja
Publication of WO2018199095A1 publication Critical patent/WO2018199095A1/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
    • 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
    • H01M8/0265—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant the reactant or coolant channels having varying cross sections
    • 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
    • H01M8/1213—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
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/2483—Details of groupings of fuel cells characterised by internal manifolds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a solid oxide fuel cell.
  • a porous support substrate having no electron conductivity with a gas flow path provided therein and "a plurality of locations separated from each other on the surface of the support substrate, a fuel electrode, a solid electrolyte, And a plurality of power generation element portions formed by laminating air electrodes ”and“ one fuel electrode and the other air electrode of the adjacent power generation element portions, each provided between one or a plurality of adjacent power generation element portions ”.
  • a solid oxide fuel cell hereinafter also referred to as a cell
  • Such a configuration is also called a “horizontal stripe type”.
  • the cell can generate power by flowing one of fuel or air (oxygen-containing gas) through an internal gas flow path and flowing the other gas outside.
  • the solid oxide fuel cell of the present disclosure includes a support substrate, a plurality of power generation element units, and a plurality of electrical connection units.
  • the support substrate is columnar and flat porous.
  • the power generation element portion is provided at each of a plurality of locations separated from each other on at least one main surface of the support substrate, and is a portion where at least a fuel electrode, a solid electrolyte, and an air electrode are stacked.
  • the electrical connection portion is a portion that is provided between the adjacent power generation element portions and electrically connects the fuel electrode of one power generation element portion and the air electrode of the other power generation element portion.
  • the support substrate is configured to support the gas passage in a cross-sectional view including a gas passage formed of a gas passage wall surface extending along a longitudinal direction therein, the gas passage, the power generation element portion, and the electrical connection portion.
  • a first region located between the power generating element portion and the gas flow path in the substrate; and a second region located between the electrical connection portion and the gas flow path in the support substrate; Including.
  • the gas permeability of the first region is different from the gas permeability of the second region.
  • FIG. 2 is a cross-sectional view of the solid oxide fuel cell shown in FIG. It is sectional drawing in the modification of the solid oxide fuel cell shown in Fig.1 (a). It is a figure for demonstrating the operating state of the solid oxide fuel cell shown in FIG. It is a perspective view which shows the support substrate of FIG. (A) is sectional drawing of FIG. 5, (b) is sectional drawing which shows the state which formed each layer in the 1st recessed part. It is sectional drawing of the solid oxide fuel cell in other embodiment. It is sectional drawing of the solid oxide fuel cell in the modification of embodiment in FIG.
  • FIG. 1A shows a solid oxide fuel cell according to this embodiment.
  • the cells are electrically connected in series to the upper and lower surfaces (main surfaces (planes) on both sides parallel to each other) of the columnar and flat support substrate 10 having a longitudinal direction (x-axis direction).
  • four) power generating element portions A having the same shape are arranged at predetermined intervals in the longitudinal direction.
  • This cell is a so-called “horizontal stripe type”.
  • This cell viewed from above is, for example, a rectangle having a length of 5 to 50 cm in the longitudinal direction and a length of 1 to 10 cm in the width direction (y-axis direction) perpendicular to the longitudinal direction.
  • the thickness of this cell is 1-5 mm.
  • This cell has a vertically symmetrical shape with respect to a plane passing through the center in the thickness direction and parallel to the main surface of the support substrate 10.
  • FIG. 2 is a cross-sectional view of the cell in the longitudinal direction shown in FIG. 1A.
  • FIG. 2 is a partial cross-sectional view in the longitudinal direction of the solid oxide fuel cell shown in FIG. In other words, it is a part of a cross-sectional view including the gas flow path 11, the power generation element part A, and the electrical connection part B.
  • the support substrate 10 is a columnar and flat plate-like fired body made of a porous material having no electronic conductivity (insulating property). Inside the support substrate 10, a plurality (six in this embodiment) of gas flow paths 11 (through holes) extending in the longitudinal direction are located at predetermined intervals in the width direction.
  • first recesses 12 at a plurality of locations on the main surface of the support substrate 10, respectively.
  • Each of the first recesses 12 includes a bottom wall made of the material of the support substrate 10 and a side wall closed in the circumferential direction made of the material of the support substrate 10 over the entire circumference (two side walls along the longitudinal direction and 2 along the width direction). And a rectangular parallelepiped depression defined by two side walls.
  • the support substrate 10 includes “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 a reforming reaction of the fuel gas (hydrocarbon-based gas reforming catalyst).
  • the insulating ceramic may be MgO (magnesium oxide) or “a mixture of MgAl 2 O 4 (magnesia alumina spinel) and MgO (magnesium oxide)”. Further, CSZ (calcia stabilized zirconia), YSZ (8YSZ) (yttria stabilized zirconia), Y 2 O 3 (yttria) may be used as the insulating ceramic.
  • the gas containing the residual gas component before reforming can promote reforming of the residual gas component before reforming by the catalytic action.
  • the insulating property of the support substrate 10 can be ensured by the support substrate 10 containing insulating ceramics. As a result, insulation between adjacent fuel electrodes can be ensured.
  • the thickness of the support substrate 10 is 1 to 5 mm.
  • the configuration on the upper surface side of the support substrate 10 will be described in consideration of the fact that the shape of the structure is vertically symmetrical. The same applies to the configuration of the lower surface side of the support substrate 10.
  • each fuel electrode current collector 21 has a rectangular parallelepiped shape.
  • each fuel electrode current collector 21 has a second recess 21 a on the upper surface (outer surface) of each fuel electrode current collector 21.
  • each of the second recesses 21a has a bottom wall made of the material of the fuel electrode current collector 21, a side wall closed in the circumferential direction (two side walls along the longitudinal direction, and a width direction).
  • a rectangular parallelepiped depression defined by two side walls).
  • two side walls along the longitudinal direction are part of the support substrate 10
  • the two side walls along the width direction (y-axis direction) are the fuel electrode current collector 21. Is part of.
  • the fuel electrode active part 22 is embedded (filled) in each second recess 21a.
  • Each fuel electrode active portion 22 has a rectangular parallelepiped shape.
  • the fuel electrode 20 includes a fuel electrode current collector 21 and a fuel electrode active part 22.
  • the fuel electrode 20 (the fuel electrode current collector 21 and the fuel electrode active part 22) is a porous fired body having electronic conductivity. Two side surfaces and a bottom surface along the width direction (y-axis direction) of each anode active portion 22 are in contact with the anode current collecting portion 21 in the second recess 21a.
  • each fuel electrode current collector 21 excluding the second recess 21a has a third recess 21b.
  • Each of the third recesses 21b has a rectangular parallelepiped shape defined by a bottom wall that is the fuel electrode current collector 21 and side walls that are closed in the circumferential direction (two side walls along the longitudinal direction and two side walls along the width direction). It is a depression.
  • two side walls along the longitudinal direction (x-axis direction) are part of the support substrate 10
  • the two side walls along the width direction (y-axis direction) are the fuel electrode current collector 21. Is part of.
  • each interconnector 30 In each third recess 21b, an interconnector (conductive dense body) 30 is embedded (filled). Each interconnector 30 has a rectangular parallelepiped shape. The interconnector 30 is a dense fired body having electronic conductivity. The two side surfaces and the bottom surface along the width direction of each interconnector 30 are in contact with the fuel electrode current collector 21 in the third recess 21b.
  • the upper surface (outer surface) of the fuel electrode 20 (the fuel electrode current collector 21 and the fuel electrode active unit 22), the upper surface (outer surface) of the interconnector 30, and the main surface of the support substrate 10 form one plane (recessed portion). The same plane as the main surface of the support substrate 10 when 12 is not formed) is formed.
  • the fuel electrode active part 22 may include, for example, NiO (nickel oxide) and YSZ (yttria stabilized zirconia). Alternatively, NiO (nickel oxide) and GDC (gadolinium-doped ceria) may be included.
  • the fuel electrode current collector 21 may include, for example, NiO (nickel oxide) and YSZ (yttria stabilized zirconia). Alternatively, it may be composed of 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 is 5 to 30 ⁇ m.
  • the thickness of the fuel electrode current collector 21 (ie, the depth of the first recess 12) is 50 to 500 ⁇ m.
  • the fuel electrode current collector 21 is electronically conductive.
  • the fuel electrode active part 22 has electronic conductivity and oxidizing ion (oxygen ion) conductivity.
  • the “volume ratio of the substance having oxidative ion conductivity relative to the total volume excluding the pore portion” in the anode active portion 22 is “the oxidative ion conductivity relative to the entire volume excluding the pore portion” in the anode current collecting portion 21. More than the volume fraction of the 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 is 10 to 100 ⁇ m. The porosity is 10% or less.
  • the solid electrolyte membrane 40 is a dense fired body having ionic conductivity and no electronic conductivity.
  • the solid electrolyte membrane 40 may contain, for example, YSZ (yttria stabilized zirconia). Alternatively, LSGM (lanthanum gallate) may be included.
  • the thickness of the solid electrolyte membrane 40 is 3 to 50 ⁇ m.
  • the entire outer peripheral surface extending in the longitudinal direction of the support substrate 10 is covered with a dense layer composed of the interconnector 30 and the solid electrolyte membrane 40.
  • This dense layer exhibits a gas seal function that suppresses mixing of the fuel gas flowing in the space inside the dense layer and the air flowing in the space outside the dense layer.
  • the solid electrolyte membrane 40 is configured so that the upper surface of the fuel electrode 20 (the fuel electrode current collector 21 + the fuel electrode active unit 22), both end portions in the longitudinal direction on the upper surface of the interconnector 30, The main surface of the support substrate 10 is covered.
  • the air electrode 60 is positioned on the upper surface of the solid electrolyte membrane 40 where the fuel electrode active portions 22 are in contact with each other via the reaction preventing membrane 50.
  • the reaction preventing film 50 is a dense fired body.
  • the air electrode 60 is a porous fired body having electronic conductivity.
  • the shape of the reaction preventing film 50 and the air electrode 60 viewed from above is substantially the same rectangle as the fuel electrode active part 22.
  • the air electrode 60 may have two layers of a first layer (inner layer) made of LSCF and a second layer (outer layer) made of LSC. The thickness of the air electrode 60 is 10 to 100 ⁇ m.
  • the reaction preventing film 50 is interposed when the YSZ in the solid electrolyte film 40 and Sr in the air electrode 60 react with each other in the cell at the time of manufacturing the cell or in operation. This is to suppress the occurrence of a phenomenon in which a reaction layer having a large electric resistance is formed at the interface.
  • the laminated body formed by laminating the fuel electrode 20, the solid electrolyte membrane 40, and the air electrode 60 corresponds to the “power generation element portion A” (see FIG. 2).
  • the power generation element part A may include a reaction preventing film 50.
  • Adjacent power generation element parts A straddle the air electrode 60 of the other power generation element part A (on the left side in FIG. 2) and the interconnector 30 of one power generation element part A (on the right side in FIG. 2). Further, the air electrode current collector 70 is located on the upper surfaces of the air electrode 60, the solid electrolyte membrane 40, and the interconnector 30.
  • the air electrode current collector 70 is a porous fired body having electronic conductivity. The shape of the air electrode current collector 70 viewed from above is a rectangle.
  • Each air electrode current collector 70 electrically connects adjacent power generating element parts A via “air electrode current collector 70 and interconnector 30” having electronic conductivity.
  • a plurality (four in this embodiment) of power generation element portions A arranged on the upper surface of the support substrate 10 are electrically connected in series.
  • Parts other than the “power generation element part A” including the “air electrode current collector part 70 and the interconnector 30” having electron conductivity are referred to as “electrical connection parts B”.
  • the region located between the power generation element part A and the gas flow path 11 in the support substrate 10 is defined as a first region 10A.
  • a region located between the electrical connection portion B and the gas flow path 11 in the support substrate 10 is defined as a second region 10B.
  • the gas flow path 11 side of the support substrate 10 is “inside” and the surface side of the support substrate 10 on which the power generation element portion is disposed is “outside”.
  • a fuel gas (hydrogen gas or the like) is caused to flow through the gas flow path 11 of the support substrate 10, and the upper and lower surfaces of the support substrate 10 (in particular, each air electrode current collector 70) ”(Air or the like) generates an electromotive force due to a difference in oxygen partial pressure generated between both side surfaces of the solid electrolyte membrane 40.
  • this structure is connected to an external load, chemical reactions shown in the following formulas (1) and (2) occur, and current flows (power generation state).
  • the current flows as indicated by the arrows in the adjacent power generation element portion A.
  • electric power is extracted from the entire cell (specifically, via the interconnector 30 of the power generating element part A on the frontmost side and the air electrode 60 of the power generating element part A on the farthest side in FIG. 4).
  • a current collecting member (not shown) for electrically connecting the front side and the back side in series may be provided.
  • the gas permeability of the first region and the gas permeability of the second region are different.
  • a fuel gas is distributed to the downstream side of the gas flow path 11 by providing a region having a low gas permeability. be able to. That is, since it is possible to suppress the occurrence of fuel depletion on the downstream side in the fuel gas flow direction, the durability of the cell can be improved.
  • the gas permeability can be measured with a gas permeability measuring device or the like manufactured by Toyo Rika Co., Ltd. by cutting out the measurement target part from the cell support substrate 10 or by producing a test piece that reproduces the measurement target part. .
  • the porosity of the first region 10A and the second region 10B is different.
  • fuel gas can be distributed to the downstream side of the gas flow path 11 by providing a region having a low porosity in the direction along the gas flow path 11 (longitudinal direction of the support substrate). Can do. That is, since it is possible to suppress the occurrence of fuel depletion on the downstream side in the fuel gas flow direction, the durability of the cell can be improved.
  • the porosity of the first region 10A means the average porosity of the entire first region 10A.
  • region 10B means the average porosity of 2nd area
  • the porosity can be analyzed by the following method. First, as shown in FIG. 2, an image in a cross section of the support substrate 10 including the gas flow path 11, the power generation element part A, and the electrical connection part B is acquired with a scanning electron microscope. Next, binarization processing is performed so that the pore portion H and other portions other than the pore portion H in the acquired image can be distinguished. Finally, the ratio of the pores in the target region is calculated.
  • the porosity of the first region 10A may be higher than the porosity of the second region 10B.
  • the porosity of the first surface region 10AS that is the surface region on the power generation element portion A side in the first region 10A is higher than the porosity of the second surface region 10BS that is the surface region of the electrical connection portion B in the second region 10B. It may be high.
  • the fuel gas can be further intensively supplied to the first region 10A. And it can control that fuel gas flows out from electric connection part B.
  • the first surface region 10AS is a support substrate in a direction perpendicular to the arrangement direction of the power generation element part A and the electrical connection part B in the cross section including the gas flow path 11, the power generation element part A, and the electrical connection part B. It means the region closest to the power generating element part A when 10 is divided into three equal parts.
  • the second surface region 10BS is a support substrate in a direction perpendicular to the arrangement direction of the power generation element part A and the electrical connection part B in the cross section including the gas flow path 11, the power generation element part A, and the electrical connection part B. It means the region on the most electrical connection part B side when 10 is divided into three equal parts.
  • the porosity in the third region which is a region close to the interconnector 30 may be lower than the porosity of the other second region 10B and the first region 10A.
  • the portion adjacent to the interconnector 30 in the second region 10 ⁇ / b> B includes the gas flow path 11 and the electrical connection portion B in the region located between the interconnector 30 and the gas flow path 11 in the support substrate 10. In the cross section, it means a region closest to the interconnector 30 when the third region is equally divided into three in the direction orthogonal to the arrangement direction of the power generating element part A and the electrical connection part B.
  • FIG. 3 is a cross-sectional view of a modification in the longitudinal direction of the cell shown in FIG.
  • the support substrate 10 may have a curved portion W where the interface between the power generation element portion A and the support substrate 10 is curved. Good. With this configuration, since the surface area of the interface between the power generation element part A and the support substrate 10 can be increased, the fuel gas can be supplied to the power generation element part A more efficiently.
  • the curved portion W may have a wave shape or may have a convex shape on either side. As shown in FIG. 3, the convex shape which becomes convex toward the gas flow path 11 side may be sufficient.
  • the fuel gas can be supplied to a desired position by controlling the position of the convex portion because the fuel gas can be intensively supplied to the convex portion by the configuration of FIG.
  • the value of the arithmetic surface roughness of the surface of the gas flow path wall surface corresponding to the power generation element portion is the electrical adjacent to the power generation element portion. It may be higher than the value of the arithmetic surface roughness of the surface of the gas flow path wall surface corresponding to the connecting portion.
  • the arithmetic average roughness value of each part is the value of the arithmetic average roughness of the two-dimensional surface in each part in any cross section (cross section in FIG. 2) including the gas flow path, the power generation element part and the electrical connection part. It can be calculated by measuring.
  • a plurality of first recesses 12 may be formed on the upper and lower surfaces of the flat support substrate 10 in a vertically asymmetric manner, and a plurality of power generation element portions A may be provided. That is, the first power generation element portion A1 and the second power generation element portion A2 described above may not be provided at vertically symmetrical positions.
  • a support substrate molded body 10g having the shape shown in FIG. 5 is prepared.
  • the molded body 10g of the support substrate can be produced by using a method such as extrusion molding or cutting using a slurry obtained by adding a binder or the like to the material of the support substrate 10 (for example, NiO + MgO).
  • region can be varied by apply
  • region can also be varied by adjusting locally the calcination temperature of the molded object 10g, or adjusting the material of the support body 10g locally.
  • the roughness of the surface of the gas channel wall surface can be adjusted by inserting a rod-like member into the channel of the molded body 10g of the support substrate and roughening the specific channel wall surface.
  • the molded body 21g of the fuel electrode current collector is disposed in each first recess formed on the upper and lower surfaces of the molded body 10g of the support substrate.
  • the molded body 22g of the fuel electrode active part is disposed in each second recess formed on the outer surface of the molded body 21g of each fuel electrode current collector.
  • the molded body 21g of each fuel electrode current collector and each fuel electrode active part 22g use, for example, a slurry obtained by adding a binder or the like to the powder of the material of the fuel electrode 20 (for example, Ni and YSZ). And arrange using the printing method.
  • the interconnector is molded in each third recess formed in the “surface portion excluding the portion where the molded body 22g of the fuel electrode active portion is embedded” on the outer surface of the molded body 21g of each fuel electrode current collector.
  • Each body 30g is arranged.
  • the molded body 30g of each interconnector is disposed by using a slurry obtained by adding a binder or the like to the material of the interconnector 30 (for example, LaCrO 3 ) using a printing method or the like.
  • a solid electrolyte membrane molded film is provided on the entire surface excluding the central portion of each portion where the plurality of interconnector molded bodies 30g are arranged on the outer peripheral surface extending in the longitudinal direction of the molded body 10g of the support substrate.
  • the solid electrolyte membrane is formed by using, for example, a printing method, a dipping method, or the like, using a slurry obtained by adding a binder or the like to the powder of the material of the solid electrolyte membrane 40 (for example, YSZ).
  • a molded film of a reaction preventing film is provided on the outer surface of the portion of the solid electrolyte membrane that is in contact with the molded body of each fuel electrode.
  • a printing method or the like is used by using a slurry obtained by adding a binder or the like to the material of the reaction preventing film 50 (for example, GDC).
  • the support substrate molded body 10g in a state in which various molded films are provided in this way is baked at 1500 ° C. for 3 hours in air, for example. Thereby, the structure in a state where the air electrode 60 and the air electrode current collector 70 are not provided in the cell shown in FIG. 1 is obtained.
  • a molded film of an air electrode is formed on the outer surface of each reaction preventing film 50.
  • the molded film of each air electrode is provided by using a slurry obtained by adding a binder or the like to the powder of the material of the air electrode 60 (for example, LSCF) using a printing method or the like.
  • the air electrode molding film, the solid so as to straddle the air electrode molding film of the other power generation element part A and the interconnector 30 of one power generation element part A
  • a molded membrane for the air electrode current collector is provided on the outer surface of the electrolyte membrane 40 and the interconnector 30, a molded membrane for the air electrode current collector is provided.
  • the molded film of each air electrode current collector is provided by using a slurry obtained by adding a binder or the like to the powder of the material of the air electrode current collector 70 (for example, LSCF), using a printing method or the like. .
  • the support substrate 10 with the formed film formed in this way is baked at, for example, 1050 ° C. for 3 hours in air. As a result, the cell shown in FIG. 1 is obtained.
  • the planar shape of the recess 12 formed in the support substrate 10 is a rectangle.
  • it may be, for example, a square, a circle, an ellipse, or a long hole shape.
  • the entire interconnector 30 is embedded in each first recess 12, but only a part of the interconnector 30 is embedded in each first recess 12, and the remaining interconnector 30 is left.
  • the portion may protrude outside the first recess 12 (that is, protrude from the main surface of the support substrate 10).
  • a plurality of first recesses 12 are formed on each of the upper and lower surfaces of the flat support substrate 10 and a plurality of power generating element portions A are provided, but only one side of the support substrate 10 is provided.
  • a plurality of first recesses 12 may be formed and a plurality of power generation element portions A may be provided.
  • the fuel electrode 20 is composed of two layers of the fuel electrode current collector 21 and the fuel electrode active portion 22, but the fuel electrode 20 is a single layer corresponding to the fuel electrode active portion 22. It may be configured.
  • the support substrate 10 includes a first position 13A1P and a second position 13B1P.
  • the first position 13A1P is a gas flow corresponding to the first power generation element part A1 that is any one power generation element part A in a cross-sectional view including the first gas flow path 11, the power generation element part A, and the electrical connection part B. It is the position of the first gas flow path wall surface 13 ⁇ / b> A ⁇ b> 1 on the first power generation element part A ⁇ b> 1 side in the road wall surface 13.
  • the second position 13B1P is a first electrical connection that is an electrical connection portion B adjacent to the first power generation element portion A1 in a cross-sectional view including the first gas flow path 11, the power generation element portion A, and the electrical connection portion B. This is the position of the second gas passage wall surface 13B1 on the first electrical connection portion B1 side among the gas passage wall surfaces 13 located inside corresponding to the portion B1.
  • the first position 13A1P and the second position 13B1P are different in a direction orthogonal to the longitudinal direction of the support substrate 10.
  • a fuel gas is distributed to the downstream side of the gas flow path 11 by providing a region having a low gas permeability. That is, since it is possible to suppress the occurrence of fuel depletion on the downstream side in the fuel gas flow direction, the durability of the cell can be improved.
  • first gas flow path wall surface 13A1 or the second gas flow path wall surface 13B1 a height difference may be provided in the longitudinal direction of the support substrate.
  • first position 13A1P or the second position 13B1P is an intermediate position between the innermost point and the outermost point in the direction orthogonal to the longitudinal direction of the gas flow path 11. To do.
  • FIG. 3 is a cross-sectional view in the longitudinal direction of a cell in the present embodiment.
  • the first gas passage wall surface 13A1 and the second gas passage wall surface 13B1 may be curved surfaces.
  • the second position 13B1P may be located outside the first position 13A1P.
  • FIG. 8 is a cross-sectional view in the longitudinal direction of the cell in a modification of the present embodiment.
  • the support substrate 10 further includes a third position 13A2P and a fourth position 13B2P.
  • the third position 13A2P is a gas corresponding to the second power generation element part A2 closest to the first power generation element part A1 among the power generation element parts A provided on the main surface on the side where the first power generation element part A1 is not provided. It is the position of the third gas channel wall surface 13A2 on the second power generation element part A2 side in the channel wall surface 13.
  • the fourth position 13B2P is a second electrical connection portion B2 that is closest to the first electrical connection portion B1 among the electrical connection portions B provided on the main surface on the side where the first electrical connection portion B1 is not provided. Is the position of the fourth gas flow path wall surface 13B2 on the second electrical connection portion B2 side.
  • the third position 13A2P and the fourth position 13B2P may be different in a direction orthogonal to the longitudinal direction of the gas flow path 11.
  • the difference between the first position 13A1P and the second position 13B1P and the difference between the third position 13A2P and the fourth position 13B2P may be different.
  • the flow of the reaction gas in the gas flow channel 11 can be made turbulent, or the total length of the gas flow channel 11 can be made longer.
  • the reactive gas can be taken in from the gas flow path wall surface 13. That is, more reactive gas can be taken into the support substrate 10.
  • the width of the gas flow path 11 located inside corresponding to the first power generation element part A1, and the width of the gas flow path 11 located inside corresponding to the second power generation element part B1 May be different.
  • the width of the gas flow path means the length of the gas flow path 11 in a direction orthogonal to the longitudinal direction of the cell in a cross-sectional view including the gas flow path 11, the power generation element portion A and the electrical connection portion B.
  • the opening area of the inlet of the gas channel 11 and the opening area of the outlet of the gas channel 11 may be different. Moreover, the axial direction of the gas flow path 11 may be inclined compared with the longitudinal direction of the cell. These structures can be adopted even in embodiments other than the present embodiment.
  • the innermost value located in the innermost side may be present at the end of the cell in the longitudinal direction of the gas flow path wall surface 13 corresponding to the second power generation element portion B1.
  • the difference between the outermost value of the gas flow path wall surface 13 located inside corresponding to the first power generation element part A1 and the innermost value located on the innermost side, and the gas flow corresponding to the second power generation element part B1 The difference between the outermost value located on the outermost side of the road wall surface 13 and the innermost value may be different.
  • a plurality of first recesses 12 are formed on each of the upper and lower surfaces of the flat support substrate 10 and a plurality of power generation element portions A are provided, but a plurality of only one side surface of the support substrate 10 is provided. 1st recessed part 12 may be formed, and the several electric power generation element part A may be provided.
  • a plurality of first recesses 12 may be formed on the upper and lower surfaces of the flat support substrate 10 in a vertically asymmetric manner, and a plurality of power generation element portions A may be provided. That is, the first power generation element portion A1 and the second power generation element portion A2 described above may not be provided at vertically symmetrical positions.
  • the fuel electrode 20 is composed of two layers of the fuel electrode current collector 21 and the fuel electrode active portion 22, but the fuel electrode 20 is a single layer corresponding to the fuel electrode active portion 22. It may be configured.
  • the support substrate molded body 10g is produced by using a method such as extrusion molding or cutting using a slurry obtained by adding a binder or the like to the material of the support substrate 10 (for example, NiO + MgO). be able to.
  • the support substrate having the desired gas flow path of the present disclosure can be produced by periodically changing the extrusion speed at the time of extrusion molding. That is, when the extrusion speed at the time of extrusion molding is slowed down, the density of the molded body 10g of the support substrate can be increased. However, since the portion where the density is high is relatively easy to sinter, the portion is more directed toward the inside. The gas flow path wall surface 13 of the gas flow path is closer to the inner side.
  • the portion can be realized by slowing the extrusion speed at the time of extrusion molding.
  • a support substrate having the gas flow path of the present disclosure can be produced by charging and extruding the material of the support substrate molded body 10g having a desired density difference.

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

Abstract

La présente invention concerne une pile à combustible à oxyde solide comprenant un substrat de support, une pluralité d'unités d'élément de production d'énergie, et une pluralité de parties de connexion électriques. Le substrat de support comprend : un canal de gaz comprenant une surface de paroi de canal de gaz s'étendant le long de la direction longitudinale à l'intérieur ; et une première région située dans le substrat de support entre les unités d'élément de génération d'énergie et le canal de gaz, et une seconde région située dans le substrat de support entre les parties de connexion électriques et le canal de gaz, vue dans une section transversale comprenant les unités d'élément de génération d'énergie et les parties de connexion électriques. La perméabilité aux gaz de la première région et la perméabilité aux gaz de la seconde région diffèrent.
PCT/JP2018/016617 2017-04-25 2018-04-24 Pile à combustible à oxyde solide WO2018199095A1 (fr)

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WO2020203897A1 (fr) * 2019-03-29 2020-10-08 大阪瓦斯株式会社 Élément électrochimique, corps empilé d'élément électrochimique, module électrochimique, dispositif électrochimique et système d'énergie

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JPWO2020022489A1 (ja) * 2018-07-27 2021-08-02 京セラ株式会社 燃料電池セル及びセルスタック装置
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