WO2018042480A1 - Empilement de de piles à combustible à oxyde solide et procédé de préparation associé - Google Patents

Empilement de de piles à combustible à oxyde solide et procédé de préparation associé Download PDF

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Publication number
WO2018042480A1
WO2018042480A1 PCT/JP2016/075128 JP2016075128W WO2018042480A1 WO 2018042480 A1 WO2018042480 A1 WO 2018042480A1 JP 2016075128 W JP2016075128 W JP 2016075128W WO 2018042480 A1 WO2018042480 A1 WO 2018042480A1
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Prior art keywords
layer
fuel electrode
stack
interconnector
air electrode
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PCT/JP2016/075128
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English (en)
Japanese (ja)
Inventor
周 島田
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ＦＣＯ Ｐｏｗｅｒ株式会社
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Priority to PCT/JP2016/075128 priority Critical patent/WO2018042480A1/fr
Priority to JP2017525434A priority patent/JP6378436B2/ja
Publication of WO2018042480A1 publication Critical patent/WO2018042480A1/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
    • H01M8/10—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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of 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
    • 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 specification relates to a solid oxide fuel cell stack and a manufacturing method thereof.
  • Two or more cells having a fuel electrode layer, a solid electrolyte layer, and an air electrode layer as a stack structure used in a stacked solid oxide fuel cell have a separator layer interposed therebetween.
  • a stacked structure is disclosed (Patent Document 1).
  • shrinkage due to firing occurs. Such shrinkage does not occur uniformly throughout the cell, and therefore causes deformation in the cell surface direction. In addition, unintended deformation or distortion may occur in the gas flow path. Furthermore, in the manifestation element, a crack may occur or a cell may be cracked.
  • Patent Document 2 At the time of manufacturing a multilayer ceramic substrate (circuit board), a so-called non-shrinkage method is employed in order to suppress shrinkage in the surface direction in the firing process (Patent Document 2). According to this construction method, it is described that a constraining layer can be laminated on a substrate with good integrity and shrinkage can be effectively suppressed by the constraining layer.
  • the constraining layer includes glass or the like and is configured so as not to sinter or difficult to sinter when the ceramic material is sintered.
  • the sintering temperature is limited, and it may be difficult to control the sintering behavior of the material.
  • a separate sintered ceramic single plate may be used as a constraint, there is a problem that the manufacturing process of the stack becomes complicated.
  • This specification provides an integrally sintered SOFC stack excellent in ability to adjust firing behavior and a method for manufacturing the same.
  • the present inventors use a non-porous layer containing a conductive ceramic material and an oxide material of an element contained in a solid electrolyte as a constraining layer, thereby controlling the firing behavior of the stack during stack production, After that, it was found that the stack can be provided as it is, which can control the heating behavior at the start of the stack and contribute to the improvement of the mechanical strength and current collecting performance of the stack. According to the present specification, the following means are provided based on these findings and the like.
  • a solid oxide fuel cell stack comprising a single cell having a fuel electrode, a solid electrolyte, and an air electrode via an interconnector, A stack comprising a constraining layer including a non-porous layer including a conductive ceramic material and an oxide material of an element contained in the solid electrolyte.
  • the constraining layer further includes a porous layer including the conductive ceramic material and an oxide material of an element included in the solid electrolyte.
  • the constraining layer has a stacked structure of two or more non-porous layers and two or more porous layers.
  • the stack according to (3), wherein the non-porous layer and the porous layer are alternately laminated.
  • the oxide material of the element contained in the solid electrolyte is an oxygen ion conductive material.
  • a method for producing a solid oxide fuel cell stack including a plurality of single cells each including a fuel electrode, a solid electrolyte, and an air electrode In obtaining a stack in which at least a first single cell and a second single cell are stacked via an interconnector, A fuel electrode material layer including a material of the fuel electrode of the first single cell, an interconnector material layer including a material of the interconnector, and an air electrode material including a material of the air electrode of the second single cell. And integrating the precursor of the stack including at least a layer by firing, With The said precursor equips at least one part of the said precursor with the constrained layer material layer which can form the non-porous layer containing a conductive ceramic material and an oxygen ion conductive material.
  • This specification relates to an interconnector used for SOFC, SOFC using the interconnector, and the like.
  • the interconnector disclosed in the present specification includes a first layer and a second layer having electrical characteristics suitable for the fuel electrode and the air electrode adjacent to the interconnector, different flow gas resistances, and the like. Therefore, it is possible to maintain the excellent conductivity and gas resistance as a whole and to exhibit the connection ability.
  • the interconnector since the interconnector includes the first layer in contact with the fuel electrode and the second layer in contact with the air electrode, it is possible to easily control the adhesion between the fuel electrode and the air electrode. In the production of the stacked SOFC stack, it is also convenient to integrally sinter the single cells with each material layer of the interconnector.
  • the reducing atmosphere refers to a gas having a composition containing one or more reducing gases.
  • the reducing atmosphere is also a gas characterized by a reducing gas, and preferably contains a reducing gas as a main component.
  • a reducing atmosphere substantially consists of 1 type, or 2 or more types of reducing gas, or is a gas of the composition containing inert gas other than reducing gas.
  • the reducing gas include hydrogen, carbon monoxide, and hydrogen sulfide.
  • the reducing gas includes a gas that includes a reducing gas by reforming a gas that is not a reducing gas (for example, a hydrocarbon gas such as methane and water vapor) in a cell.
  • the oxidizing atmosphere refers to a gas having a composition containing one or more oxidizing gases.
  • the oxidizing atmosphere is a gas characterized by an oxidizing gas, and preferably contains an oxidizing gas as a main component.
  • the oxidizing atmosphere is substantially composed of one or more oxidizing gases, or is a gas having a composition containing an inert gas other than the oxidizing gas.
  • the oxidizing gas include oxygen, ozone, nitrous oxide, nitric oxide, and nitrogen dioxide.
  • the interconnector is an interconnector used for SOFC, which includes a fuel electrode, a solid electrolyte, and an air electrode.
  • SOFC SOFC
  • FIGS. 1 and 2 the reducing gas channel 22 and the oxidizing gas channel 24 are explicitly shown so as to be parallel to each other.
  • the interconnector 10 includes at least a first layer 12.
  • the first layer 12 is located on the fuel electrode 2 side in the interconnector 10.
  • the first layer 12 may be on the side of the interconnector 10 that is scheduled to be the fuel electrode 2 side or the fuel electrode 2 side (hereinafter simply referred to as the fuel electrode side). It is not limited to be positioned on the fuel electrode 2 side. Moreover, what is necessary is just to join to the fuel electrode 2 directly or indirectly.
  • the first layer 12 preferably has a high electrical conductivity and a reducing gas barrier property in a reducing atmosphere. More specifically, the first layer 12 can have higher electrical conductivity and gas barrier properties than the second layer described later in a reducing atmosphere. By providing such a first layer, the fuel electrode 2 can be connected with high conductivity, and reducing gas such as hydrogen can be reliably shut off. On the other hand, the first layer 12 may have low electrical conductivity or substantially no electrical conductivity in an oxidizing atmosphere such as oxygen, and may not have resistance to the oxidizing atmosphere. As a result, the gas barrier property in the oxidizing atmosphere may be low or substantially absent.
  • the first layer 12 in the interconnector only has to exhibit the integral sinterability with the air electrode 4, the electrical connectivity with the air electrode 4, and the resistance to oxidizing gas in the second layer 14 described later. Conventionally known interconnector materials can be easily applied.
  • a conductive ceramic material used as a conventionally known ceramic interconnector material used for SOFC can be appropriately selected and used.
  • the conductive ceramic material include various known ABO 3 perovskite oxides.
  • M 1 represents an alkaline earth metal, and examples thereof include calcium (Ca), strontium (Sr), and barium (Ba), and one or more of them can be used.
  • M 2 is one or two selected from transition elements such as titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), etc. More than a seed. Is mentioned. Preferably, it is 1 type, or 2 or more types selected from Ti, Cr, Mn, Fe, and Co.
  • Examples of such conductive ceramic materials include LaCoO 3 oxides, LaMnO 3 oxides, La (CoFe) O 3 oxides, LaCrO 3 oxides in which La and Sr or Ca coexist at the A site, Examples include LaTiO 3 acid compounds.
  • LaSr MnO 3
  • LaSr CoO 3
  • LaSr CoFe
  • LaSr TiO 3
  • LaCrMgO 3 and the like can be mentioned.
  • the first layer 12 can contain one or more conductive ceramic materials.
  • the first layer 12 includes such a ceramic material in part so that it can exhibit the characteristics as an interconnector, and may be substantially composed of the material, or only composed of the material. There may be.
  • the first layer 12 does not include a metal conductive material such as a metal or metal alloy.
  • substantially composed of a certain material means that the material to be used does not include other materials that may greatly affect the characteristics imparted to the interconnector. ing.
  • the material used for the first layer 12 is appropriately selected in consideration of, for example, the material of the fuel electrode 2 of the SOFC to which the interconnector is applied, the material of the air electrode 4, the operating temperature, the sintering temperature of the stack 30, and the like.
  • the for the first layer it is preferable to use a LaTiO 3 -based oxide exhibiting high conductivity in a reducing atmosphere, in particular, a (LaSr) TiO 3 -based oxide such as La 0.3 Sr 0.7 TiO 3 .
  • the first layer 12 may be configured by laminating two or more first layers having different compositions.
  • the two or more first layers 12 may contain a similar ceramic material, or may contain different ceramic materials. Moreover, you may have a continuous or intermittent gradient composition.
  • the first layer 12 has the denseness that is generally provided in an interconnector.
  • the relative density (according to Archimedes method) of the first layer 12 is preferably 93% or more, and more preferably 95% or more.
  • the thickness of the first layer 12 is not particularly limited, but can be set to 1 ⁇ m or more and 50 ⁇ m or less in consideration of the size and conductivity of the entire stack, for example. Moreover, Preferably it is also 1 micrometer or more and 30 micrometers or less. Furthermore, it can also be 1 ⁇ m or more and 20 ⁇ m or less.
  • the interconnector 10 includes at least a second layer 14.
  • the second layer 14 is located on the air electrode 4 side in the interconnector 10.
  • the second layer 14 may be on the air electrode 4 side or the air electrode 4 side (hereinafter simply referred to as the air electrode side) in the interconnector. It is not limited to be positioned on the pole 4 side. Moreover, what is necessary is just to join to the air electrode 4 directly or indirectly.
  • the second layer 14 can have higher electrical conductivity and gas barrier properties than the first layer 12 in an oxidizing atmosphere.
  • the air electrode 4 can be connected with high conductivity, and an oxidizing gas such as air can be reliably blocked.
  • the second layer 14 may have low or substantially no electrical conductivity in a reducing atmosphere containing hydrogen gas or the like, and does not have resistance to the reducing atmosphere.
  • the gas barrier property in a reducing atmosphere may be low or substantially absent.
  • the second layer 14 preferably contains a conductive ceramic material and an oxide material of an element contained in the solid electrolyte.
  • the second layer 14 exhibits high conductivity and resistance in an oxidizing atmosphere by using a conductive ceramic material, and integrity with respect to the air electrode 4, and includes an oxide material included in the solid electrolyte.
  • the coefficient of thermal expansion of 6 can be adapted. According to such a configuration, it is possible to ensure the integrity with the air electrode 4, the compatibility of the thermal expansion coefficient, the resistance against the oxidizing gas, and the blocking property.
  • the second layer 14 can include a conductive ceramic material and an oxide material of an element included in the solid electrolyte.
  • the second layer 14 includes these ceramic materials in part so that the characteristics as an interconnector can be exhibited, and may be substantially composed of the material, or only composed of the material. It may be.
  • the second layer 14 does not include a metal conductive material such as a metal or metal alloy.
  • the conductive ceramic material used for the second layer 14 can be appropriately selected from known air electrode materials used as SOFC air electrode materials.
  • an ABO 3 type perovskite oxide containing La or La and Sr can be mentioned.
  • perovskite oxides include transition metal perovskite oxides such as LaCoO 3 oxides, LaMnO 3 oxides, LaFeO 3 oxides in which La or La and Sr or Ca coexist at the A site. Can be mentioned.
  • LaTiO 3 based oxide or the like to coexist with La or La and Sr or Ca in the A site and the like.
  • Co, Mn, and Ti may contain Cr, Fe, Mg, and the like as other elements at the B sites of various oxides.
  • the air electrode material used in the second layer 14 may be the same as or common to the material of the air electrode 4 in the single cell in which the interconnector is interposed, but may be different.
  • the oxide material of the element contained in the solid electrolyte is not particularly limited, and a known material can be appropriately selected and used.
  • ZrO 2 zirconia
  • rare earth elements such as Y, Sc, Yb, CeO 2 (ceria) doped with rare earth elements such as Gd, Sm, alkaline earth such as Sr and Mg
  • LaGaO 3 lanthanum gallate in which a part of La and Ga is substituted with a similar metal.
  • the ionic conductivity of the oxide material of the element contained in the solid electrolyte used for the second layer 14 is reduced as compared with the oxygen ion conductive material used for the solid electrolyte. This is because the ionic conductivity in the interconnector may prevent the performance of the interconnector from being limited.
  • the rare earth element oxide as the stabilizing material used for the second layer 14 is preferably added in an amount of about 1.5 mol% to 5 mol% with respect to an oxide material such as zirconia. More preferably, it is about 2 mol% or more and 4 mol% or less.
  • the oxide materials of the elements contained in the conductive ceramic material and the solid electrolyte are, for example, the material of the fuel electrode 2 of the SOFC to which the interconnector 10 is applied, the material of the air electrode 4, the operating temperature, and the sintering temperature of the stack, respectively. Etc. are selected as appropriate.
  • the mixing ratio of the conductive ceramic material and the air electrode material is not particularly limited.
  • the conductive ceramic material and the oxide material of the element contained in the solid electrolyte are 30:70 to 70 by mass ratio. : 30 or the like, or 40:60 to 60:40.
  • the second layer 14 may be configured by stacking two or more second layers having different compositions.
  • the two or more second layers may contain a similar ceramic material, or may contain different ceramic materials. Moreover, you may have a continuous or stepwise gradient composition.
  • the first layer 12 and the second layer 14 may be directly integrated with each other, and one or more other third layers are interposed between these layers. May be.
  • the first layer 12 and the second layer 14 are preferably integrated by sintering. More preferably, they are integrated by direct sintering without a special intervening layer.
  • the second layer 14 has the denseness that is generally included in an interconnector.
  • the relative density (according to Archimedes method) of the second layer 14 is preferably 93% or more, and more preferably 95% or more.
  • the thickness of the second layer 14 is not particularly limited.
  • the thinnest portion of the second layer 14 is 1 ⁇ m or more and 50 ⁇ m or less. It can be.
  • Preferably it is also 1 micrometer or more and 30 micrometers or less.
  • it can also be 1 ⁇ m or more and 20 ⁇ m or less.
  • the lamination form of the first layer 12 and the second layer 14 in the interconnector 10 is not particularly limited, and is appropriately determined depending on the single cell structure in the SOFC to which the interconnector 10 is applied. Various forms of the interconnector will be described in detail later.
  • the interconnector 10 is preferably manufactured at the same time as the single cell stack is manufactured by interposing between the single cells in the manufacturing process of the SOFC stack 30.
  • a green laminate appropriately including the material layer of the first layer 12 and the material layer of the second layer 14 may be prepared as an interconnector precursor and used for the manufacturing process of the SOFC stack 30.
  • the material layer of the first layer 12 and the material layer of the second layer 14 may be laminated in a necessary order and used for the manufacturing process of the SOFC stack 30.
  • the SOFC and its manufacturing method will be described in detail later.
  • the form of the interconnector 10 as a whole is not particularly limited, but can adopt a form corresponding to the SOFC stack 30 to be applied. For example, when applied to a flat plate type SOFC, a flat plate or the like is obtained.
  • the whole thickness of the interconnector 10 is not specifically limited, For example, in the thinnest part, it can be set as 1 micrometer or more and 100 micrometers or less. Preferably, it can be 2 ⁇ m or more and 60 ⁇ m or less, and more preferably 2 ⁇ m or more and 40 ⁇ m or less.
  • the thermal expansion coefficient (20 ° C. to 1000 ° C.) of each of the first layer 12 and the second layer 14 of the interconnector is 8 ⁇ 10 ⁇ 6 K ⁇ 1 or more and 12 ⁇ 10 ⁇ 6 K ⁇ 1 or less. It is preferable. This is because peeling within the air electrode layer or the fuel electrode layer can be suppressed within this range. Considering the residual stress of the stack structure, it is more preferably 9.5 ⁇ 10 ⁇ 6 K ⁇ 1 or more and 11.5 ⁇ 10 ⁇ 6 K ⁇ 1 or less.
  • the interconnector 10 described above has interconnect characteristics suitable for the fuel electrode 2 of one single cell to be connected and the air electrode 4 of the other single cell, that is, conductivity, gas resistance, and shut-off property, Therefore, it is possible to provide a thin layer and sufficient interconnector characteristics as a whole. Further, in the manufacture of the integrally sintered metal material-free (in other words, all ceramics) SOFC stack 30, the ceramic material layer corresponding to the fuel electrode and the ceramic material material corresponding to the air electrode are used. By applying each material layer of the material layer of the second layer 14, the first layer 12 and the second layer 14 are integrally sintered to the fuel electrode 2 and the air electrode 4, respectively. Layer 12 and second layer 14 are also integrally sintered together. Therefore, excellent conductivity and gas barrier properties can be reliably realized, the stacking process of the stack 30 can be simplified and made efficient, and the integral sinterability of the stack 20 can be improved.
  • the SOFC stack disclosed herein can include an interconnector between at least two single cells. According to such an SOFC stack, these single cells are connected and separated with high electrical conductivity and gas barrier properties, and when integrally sintered to the cells, the electrical conductivity and In addition to improved gas barrier properties, the SOFC stack manufacturing process is simplified.
  • SOFC stack in which SOFC single cells are stacked with an interconnector will be described with reference to FIGS.
  • a cell (power generation element) C in the SOFC includes a fuel electrode 2, a solid electrolyte 6, and an air electrode 4. More specifically, it has a structure in which the fuel electrode 2 and the air electrode 4 are laminated via a solid electrolyte 6.
  • the fuel electrode 2 is not particularly limited, and can be a porous body made of one or more conductive ceramic materials applied to the SOFC fuel electrode.
  • the fuel electrode material can include zirconia or ceria in which a rare earth element is dissolved, and Ni / NiO.
  • the rare earth element for example, yttrium (Y), scandium (Sc), samarium (Sm), gadolinium (Gd), or the like can be used.
  • the fuel electrode 2 is porous, and its porosity is appropriately set, but is preferably 15% or more, more preferably about 20% or more and 40% or less.
  • the porosity can be measured from the area ratio of the pore portion and the dense portion of a cross-sectional image obtained by scanning a plurality of cross-sections created by mechanical cutting and polishing with a scanning electron beam microscope. .
  • the pores and dense portions of the layer are binarized by image processing in a field of view of 500 ⁇ m ⁇ 500 ⁇ m including the layer, and the area ratio is obtained, and the average of all cut surfaces is taken. Can determine the porosity.
  • the pore shape in the fuel electrode 2 can be any shape such as an indefinite shape, a fiber shape, or a spherical shape.
  • the average pore diameter is preferably 1 ⁇ m or more and 10 ⁇ m or less. More preferably, it is 2 ⁇ m or more and 5 ⁇ m or less.
  • the average pore diameter is assumed to be obtained by connecting a plurality of spherical pores to a pore portion of a cross-sectional image photographed by a scanning electron microscope with a plurality of cross sections created by mechanical cutting and polishing. It can be measured from the average diameter.
  • the pores and dense portions of the layer are binarized by image processing in a 500 ⁇ m ⁇ 500 ⁇ m visual field including the layer, and circular approximation is performed for all pores included in the visual field
  • the average pore diameter can be obtained by obtaining the diameter of the cut and taking the average of all the cut surfaces.
  • the anode 2 may have a substantially single porosity and / or average pore diameter, but may have a different distribution with respect to these. For example, as shown in FIG. 2, in the portion of the fuel electrode 2 that is distal from the solid electrolyte 6 or proximal to the first layer 12 of the interconnector 10, the porosity and / or the average pore diameter is set as the solid electrolyte 6.
  • the anode buffer layer 2a can be provided smaller than the portion proximal to the first layer 12 of the interconnector 10 or distal to the distal portion thereof.
  • the adhesion between the fuel electrode 2 and the interconnector (first layer) 10 can be enhanced, and the integrity can be improved and peeling can be suppressed.
  • the fuel electrode buffer layer 2a is formed on the convex portion 26.
  • the gas flow path (disappearing member for forming the gas flow path in the SOFC manufacturing process) 22 can be surely included in the fuel electrode 2 even if it is a thin layer by following well. Thereby, it is possible to avoid the direct contact of the top surface of the gas flow path 22 with the first layer 12 of the interconnector 10, and to reduce the resistance of the conductive path of the fuel electrode 2.
  • the thickness of the fuel electrode 2 itself can be reduced, and the fuel electrode that is generated when the SOFC stack 30 is started and stopped. 2 can suppress fluctuations in the deposition of the fuel electrode 2 due to oxidation / reduction of Ni contained in 2, and can suppress separation, deformation and destruction in the SOFC stack 30.
  • the fuel electrode buffer layer 2a is also, for example, 40% of the average pore diameter of the solid electrolyte 6 side of the fuel electrode 2 (a layer in contact with the solid electrolyte 6 side of the fuel electrode 2, hereinafter also referred to as the fuel electrode main layer 2b). It is preferably 90% or less. By such a small average pore diameter, the followability to the curved surface / deformed surface such as the convex portion 26 of the fuel electrode buffer layer 2a is improved. More preferably, it is about 50% or more and 80% or less.
  • the average pore diameter is smaller than that of the fuel electrode main layer 2b and should be about 1 ⁇ m or more and 5 ⁇ m or less. it can.
  • the pore size distribution (pore size distribution) when the pores of the fuel electrode buffer layer 2a are spherical is preferably more polydisperse than the fuel electrode main layer 2b.
  • the pore size distribution of the fuel electrode buffer layer 2a is preferably a distribution in which 50% or less of the pores exist in the average value ⁇ 0.2 ⁇ .
  • the pore size distribution is based on the assumption that a plurality of spherical pores are connected to the pores of a cross-sectional image taken with a scanning electron microscope for a plurality of cross sections created by mechanical cutting and polishing. It can be measured from the average diameter.
  • the porosity of the fuel electrode buffer layer 2a can be made smaller than the porosity of the fuel electrode main layer 2b. In addition to improving the followability to a deformed surface such as a curve, it is possible to improve the adhesion of the interconnector 10 to the first layer 12.
  • the porosity of the fuel electrode buffer layer 2a is preferably 40% or more and 80% or less, more preferably 60% or more and 80% or less of the porosity of the fuel electrode main layer 2b.
  • the fuel electrode buffer layer 2a can have one or more of the above three characteristics related to pores, average pore diameter, pore diameter distribution, and porosity. Preferably, three can be provided.
  • the gradient composition related to the pores may be continuous or stepwise.
  • the pores can be formed by using a pore-forming agent that forms pores reflecting the shape of carbon or a high-molecular material such as starch or acrylic after being burned down.
  • a pore-forming agent that forms pores reflecting the shape of carbon or a high-molecular material such as starch or acrylic after being burned down.
  • spherical pore formers having different particle sizes and / or particle size distributions can be used.
  • the usage-amount of arbitrary pore forming agents can be changed.
  • the fuel electrode main layer 2b is formed from a fuel electrode material containing a spherical pore former having a larger average particle size and / or a smaller particle size distribution, and the fuel electrode buffer layer 2a has a smaller average particle size. And / or a fuel electrode material containing a spherical pore former having a large particle size distribution.
  • a method for controlling pores in ceramics is a method well known to those skilled in the art.
  • the thickness of the fuel electrode 2 is not particularly limited, and may be, for example, 15 ⁇ m or more and 500 ⁇ m or less, although it varies depending on the presence or absence of the gas flow path 22 and the flow path form. More preferably, it can be 20 ⁇ m or more and 500 ⁇ m or less. More preferably, it can be 50 ⁇ m or more and 400 ⁇ m or less, and preferably 50 ⁇ m or more and 300 ⁇ m or less. As will be described later, the thicknesses of the fuel electrode 2 and the air electrode 4 are not necessarily constant in one layer. Therefore, the description regarding the thickness of the fuel electrode 2 and the air electrode 4 means that one layer exists in the range of such thickness unless it mentions especially.
  • the thickness of the fuel electrode buffer layer 2a is not particularly limited, but may be, for example, 5 ⁇ m or more and 50 ⁇ m or less, and may be, for example, 5 ⁇ m or more and 20 ⁇ m or less.
  • the air electrode 4 is not particularly limited, and may be a porous body made of one or more conductive ceramic materials applied to the SOFC air electrode 4.
  • examples of the air electrode material include the conductive ceramic materials already exemplified as the material of the second layer 14 of the interconnector 10.
  • the air electrode 4 is porous, and its porosity is appropriately set, but is preferably 15% or more, more preferably about 20% or more and 40% or less.
  • the average pore diameter is preferably 1 ⁇ m or more and 10 ⁇ m or less. More preferably, it is 2 ⁇ m or more and 5 ⁇ m or less.
  • the thickness of the air electrode 4 is not particularly limited, and varies depending on the presence or absence of the oxidizing gas flow path 24 and the flow path form.
  • the thickness can be 15 ⁇ m or more and 500 ⁇ m or less, and for example, 20 ⁇ m or more and 500 ⁇ m. It can be as follows. More preferably, it can be 50 ⁇ m or more and 400 ⁇ m or less.
  • the solid electrolyte 6 is not particularly limited, and can be a dense body made of one or more oxygen ion conductive materials applied to the SOFC solid electrolyte.
  • oxygen ion conductive materials applied to the SOFC solid electrolyte.
  • the solid electrolyte material already exemplified oxygen ion conductive materials can be mentioned.
  • the solid electrolyte 6 is dense and preferably has the same relative density as the interconnector 10 from the viewpoint of blocking gas permeability. Further, the thickness of the solid electrolyte 6 is not particularly limited, but can be set to, for example, 1 ⁇ m or more and 100 ⁇ m or less. More preferably, it can be 3 ⁇ m or more and 40 ⁇ m or less, and further preferably 5 ⁇ m or more and 30 ⁇ m or less.
  • the single cell C of the SOFC includes gas flow paths 22 and 24 for a reducing gas containing hydrogen supplied to the fuel electrode 2 and an oxidizing gas containing oxygen supplied to the air electrode 4, respectively. .
  • the gas flow paths 22 and 24 can be formed over one or two layers constituting a single cell. That is, the gas flow paths 22 and 24 may be provided in the fuel electrode 2 and the air electrode 4, respectively, or may be provided in the interconnector 10, and may be provided across the fuel electrode 2 and the interconnector 10. It may be provided over the air electrode 4 and the interconnector 10.
  • these gas flow paths 22 and 24 can be included so as to be completely embedded in the thickness range of the fuel electrode 2 and the air electrode 4.
  • the increase in the volume of an interconnector with high resistance can be controlled, and the fall of power generation performance can be controlled.
  • connects the fuel electrode 2 and the air electrode 4 it can also provide so that it may open to the fuel electrode 2 side and the air electrode 4 side.
  • At least the gas flow path 22 can be provided in the fuel electrode 2. That is, the fuel electrode 2 is included so as to cover the gas flow path 22, but only a part of the thickness of the gas flow path 22 is provided.
  • the fuel electrode 2 has one or more convex portions 26 that protrude outward from the single cell C based on the outer shape, arrangement pattern, and the like of the gas flow path 22. Can be provided. By doing so, the layer thickness of the fuel electrode 2 can be reduced, and the volume fluctuation of the fuel electrode 2 due to the oxidation / reduction of Ni (according to the start and stop of SOFC) due to the increase in the volume of the fuel electrode 2 can be suppressed. it can.
  • the fuel electrode 2 having the convex portion 26 based on the gas flow path 22 to be present has a thickness that does not satisfy the thickness (thickness or height in the stacking direction) of the gas flow path 22 in a region where the gas flow path 22 is not formed. It is formed by providing the fuel electrode 2. That is, the fuel electrode 2 is provided with a thickness of less than 100% of the thickness of the gas flow path 22. By carrying out like this, the thickness of the fuel electrode 2 can be reduced effectively and oxidation-reduction tolerance can be improved. In addition, the thickness of the first layer 12 of the interconnector 10 can be appropriately reduced, and the electrical resistance can be reduced.
  • the fuel electrode 2 can be 90% or less, for example, 80% or less, further, for example, 70% or less, further, for example, 60% or less, etc.
  • the fuel electrode 2 is 1% or more of the thickness of the gas flow path 22, for example, 10% or more, for example, 20% or more, and further, for example, 30% or more.
  • the thickness of the fuel electrode 2 can be not less than 30% and not more than 70% of the thickness of the gas channel 22 in the gas channel non-formation region.
  • the fuel electrode 2 is 90% or less of the maximum height of the gas flow path 22 in the fuel electrode 2, for example, 80% or less, further, for example, 70% or less, and further, for example, 60% or less, For example, it can be 50% or less, moreover, for example, 40%, further, for example, 30%, or, for example, 20% or less.
  • the fuel electrode 2 is 1% or more of the thickness of the gas flow path 22, for example, 5% or more, for example, 10% or more. As a typical rule, the thickness of the fuel electrode 2 can be 5% or more and 50% or less of the maximum height of the gas passage 22 in the gas passage non-formation region.
  • the fuel electrode 2 is formed of the fuel electrode main layer 2 b and the fuel electrode buffer layer 2 a, so that the convex portion 26 based on the gas flow path 22 is formed. It is possible to easily form the fuel electrode 2 that is in close contact with and encloses or covers the gas flow path 22. Although not particularly limited, it is preferable to mainly include the fuel electrode buffer layer 2 a in the upper part of the gas flow path 22.
  • the first layer 12 of the interconnector 10 having suitable characteristics for the fuel electrode 2 having the surface form including the convex portion 26 corresponding to one or two or more gas flow paths 22, the reduction is achieved.
  • the electrical conductivity and gas barrier property in a neutral atmosphere and further comprising the second layer 14, the electrical conductivity and gas barrier property in an oxidizing atmosphere derived from the air electrode 4 of the adjacent single cell C Can be secured.
  • the ceramic two-layer containing structure of the interconnector 10 in accordance with not only the characteristics of the adjacent electrodes but also the surface form having changes, the surface that has changed in this way exhibits excellent followability and adhesion.
  • the SOFC stack 30 having good integrity, moldability, and shape can be constructed by buffering the form.
  • the thickness of the gas flow paths 22 and 24 (that is, the thickness or flow path height along the stacking direction of the elements in the cell C) is determined depending on the portion where the gas flow paths 22 and 24 are provided (in the interconnector or the electrode) or the gas flow. Although it varies depending on the road pattern and the like and is not particularly limited, for example, it can be 50 ⁇ m or more and 400 ⁇ m or less.
  • the thickness of the gas flow path 22 in the fuel electrode 2 is preferably 100 ⁇ m or more and 200 ⁇ m or less
  • the thickness of the gas flow path 24 in the air electrode 4 is preferably 150 ⁇ m or more and 300 ⁇ m or less.
  • each gas flow path 22 and 24 of reducing gas and oxidizing gas is not particularly limited, and various patterns can be adopted. Although it depends on the form of the SOFC, for example, in the case of a flat plate type SOFC, in a plan view, a pattern in which a plurality of linear flow paths are arranged at regular intervals, and a plurality of U-shaped flow paths having different sizes are provided. Examples include a pattern arranged on the inner side in order of decreasing size, a pattern in which one or more continuous flow paths are arranged.
  • the thickness of the single cell (fuel electrode, air electrode, solid electrolyte) C configured in this way is not particularly limited, and can be, for example, 100 ⁇ m or more and 1000 ⁇ m or less. Moreover, it is preferably 150 ⁇ m or more and 1000 ⁇ m or less. Furthermore, it can be preferably 200 ⁇ m or more and 1000 ⁇ m or less. Further, it can be preferably 300 ⁇ m or more and 600 ⁇ m or less.
  • the surface of the fuel electrode 2 and / or the air electrode 4 of the single cell C can be provided with a convex portion 26 or the like based on the external form and arrangement pattern of the gas flow paths 22 and 24 that are included.
  • the SOFC single cell C and the SOFC stack 30 can appropriately include a seal portion 20 for sealing each gas supplied to the fuel electrode 2 and the air electrode 4.
  • a seal portion 20 for sealing each gas supplied to the fuel electrode 2 and the air electrode 4.
  • the form of the seal part 20 is not specifically limited,
  • a well-known seal structure can be suitably employ
  • the SOFC disclosed in this specification may include the interconnector 10 or a part thereof with respect to the single cell C, and the SOFC stack 30 includes at least two single cells C connected via the interconnector 10.
  • the unit cell C in which the fuel electrode 2, the air electrode 4 and the solid electrolyte 6 are stacked is connected to another unit cell C through an interconnector 10 to form a SOFC stack 30.
  • the first layer 12 and the second layer 14 of the interconnector 10 can take various laminated forms depending on the mode of each power generation element in the SOFC.
  • FIG. 3A shows a form in which the first layer 12 and the second layer 14 are flat layers.
  • each gas flow path 22, 24 may be in the interconnector or in the electrode.
  • the gas flow path is included in the layer thickness of the electrode. Thus, the convex portion due to the gas flow path does not appear on the electrode surface.
  • the 3B is a layer having one or more curved portions 12a corresponding to one or more convex portions 26 based on the gas flow path 22 in which the first layer 12 is inherent in the fuel electrode 2.
  • the second layer 14 is a layer having a filling portion 14b that fills the portion of the first layer 12 that is not the curved portion 12a, that is, the bottom portion 12b and has a substantially uniform thickness as the entire interconnector 10. The form is shown.
  • the first layer 12 is a wavy or corrugated layer having a substantially uniform thickness.
  • the second layer 14 includes a covering portion 14a having a relatively thin layer thickness in the curved portion 12a corresponding to or around the reducing gas flow path 22, and corresponds to the space between the reducing gas flow paths 22.
  • the bottom portion 12b is provided with a relatively thick filling portion 14b.
  • the first layer 12 can be applied to the fuel electrode 2 in a necessary and sufficient form while ensuring a uniform thickness as a whole.
  • the second layer 14 allows the interconnector 10 to have a substantially flat and uniform thickness as a whole.
  • FIG. 3C differs from FIG. 3B in that the second layer 14 for the air electrode 4 has a curved portion 14c and a bottom portion 14d following a surface form having a convex portion 28 based on the gas flow path 24 of the air electrode 4.
  • the first layer 12 has a filling portion 12d that fills the bottom portion 14d of the second layer 14 and has a covering portion that thinly covers the curved portion 14c.
  • the form provided with the part 12c is shown.
  • the first layer 12 is relatively thin in the curved portion 14 c corresponding to or around the oxidizing gas flow channel 24, and the first layer is formed in the bottom portion 14 d between the oxidizing gas flow channels 24. 12 is relatively thick.
  • the second layer can be applied to the air electrode 4 in a necessary and sufficient form.
  • the second layer 12 allows the interconnector 10 to have a substantially flat and uniform thickness as a whole.
  • the SOFC single cell C or SOFC stack 30 may comprise at least one constraining layer 40 in the stack.
  • the constraining layer 40 can include at least a non-porous layer 42 including a conductive ceramic material and an oxide material of an element included in the solid electrolyte.
  • the conductive ceramic material used for the constraining layer 40 the conductive ceramic material suitable for the air electrode 4 described above can be used.
  • an oxide material of the element contained in the solid electrolyte an oxygen ion conductive material suitable for the solid electrolyte 6 described above can be used.
  • the thermal expansion coefficient (20 ° C. to 1000 ° C.) of the constraining layer 40 is preferably 10 ⁇ 10 ⁇ 6 K ⁇ 1 or more and 15 ⁇ 10 ⁇ 6 K ⁇ 1 or less.
  • the constraining layer 40 includes at least a non-porous layer 42.
  • the non-porous layer 42 can have the same denseness as the solid electrolyte 6 and the interconnector 10. Moreover, as a porosity, it is preferable that it is 10% or less, More preferably, it is 5% or less.
  • the thickness of the non-porous layer 42 is not particularly limited, but may be, for example, 10 ⁇ m to 200 ⁇ m, preferably 50 ⁇ m to 100 ⁇ m.
  • the constraining layer 40 can further include a porous layer 44 that is porous including the conductive ceramic material and an oxide of an element contained in the solid electrolyte, like the non-porous layer 42.
  • the provision of the non-porous layer 42 and the porous layer 44 makes it easier to adjust the firing behavior.
  • the porosity of the porous layer 44 is not particularly limited as long as it is larger than that of the non-porous layer 42.
  • the porosity can be 10% or more and 50% or less. This is because within this range, it is easy to adjust the firing behavior by the combination with the non-porous layer 42.
  • the thickness of the porous layer 44 is not particularly limited, but may be, for example, 10 ⁇ m or more and 200 ⁇ m or less, preferably 50 ⁇ m or more and 100 ⁇ m or less.
  • non-porous layer 42 can also function as the interconnector 10 with respect to the air electrode 4 when disposed at the terminal end of the SOFC single cell C and the SOFC stack 30 on the air electrode 4 side. Therefore, for example, in that case, the second layer 14 of the interconnector 10 can be omitted.
  • the stacked form is not particularly limited, but the non-porous layer 42 and the porous layer 44 can be alternately provided. .
  • the number and thickness of each layer may be different or the same, but from the viewpoint of adjusting the firing behavior, the number of layers of the non-porous layer 42 and the porous layer 44 is the same. Are the same number and / or the total thickness of each layer is preferably the same.
  • the non-porous layer 42 and the porous layer 44 as the constraining layer 40 can each include a conductive ceramic material and an oxide material of an element contained in the solid electrolyte.
  • the same type of conductive ceramic material and the oxide material of the element contained in the solid electrolyte may be used, or at least one of them may be different.
  • these two types of layers 42 and 44 may have the same composition (formulation) but may be the same, but use the same type of material.
  • a plurality of non-porous layers 42 are provided, the same aspect as described above is applied to the non-porous layers 42 with respect to the oxide material of the element contained in the conductive ceramic material and the solid electrolyte.
  • the same aspects as described above are applied to the porous layers 44 with respect to the conductive ceramic material and the oxide material of the element contained in the solid electrolyte.
  • the mixing ratio of the conductive ceramic material and the oxide material of the element contained in the solid electrolyte in these two types of layers 42 and 44 is not particularly limited.
  • it is included in the conductive ceramic material: solid electrolyte.
  • the oxide material of the element can be 30:70 to 70:30 or the like, or 40:60 to 60:40 by mass ratio.
  • each of the layers 42 and 44 can appropriately contain an additive in order to enhance the sinterability or to improve the heat resistance during high-temperature firing.
  • an additive in addition to the various additives described above, ceria and the like can be added from the viewpoint of heat resistance.
  • a high-temperature heat-resistant additive such as ceria is not particularly limited, but is preferably added to the porous layer 44.
  • the content of these additives is not particularly limited, and can be, for example, 0.5% by mass or more and 10% by mass or less based on the total ceramic materials (including additives) in each layer 42 and 44. Preferably, it can be 2 mass% or more and 8 mass% or less.
  • the pore shape in the porous layer 44 is not particularly limited, but spherical pores can be formed.
  • the average pore diameter is not particularly limited, but can be, for example, 0.5 ⁇ m or more and 5 ⁇ m or less. This is because if the thickness is less than 0.5 ⁇ m and more than 5 ⁇ m, it is difficult to sufficiently adjust the firing behavior.
  • Adjustment of the porosity and average pore diameter in ceramic materials is well known to those skilled in the art, and a person skilled in the art can appropriately produce a ceramic layer having an intended porosity and average pore diameter.
  • the constraining layer 40 can be provided at any site in the SOFC. That is, the constraining layer can be provided on one or both of the fuel electrode 2 side and the air electrode 4 side in the single cell C, and also constrains at least a part of the plurality of single cells C included in the stack 30.
  • a layer 40 may be provided. It can also be provided on one or both of the outermost sides of the stack 30.
  • the first layer 12 of the interconnector 10 applied to the single cell C that is, the first layer
  • the constraining layer 40 can be provided so as to be located outside the cell C rather than 12.
  • the air electrode 4 is provided with a constraining layer 40 so as to be located on the outside of the cell C with respect to the air electrode 4. be able to.
  • the lamination form of the non-porous layer 42 and the porous layer 44 as the constraining layer 40 is not particularly limited.
  • the non-porous layer 42 is provided with respect to the first layer 12 and the air electrode 4.
  • the porous layer 44 can be further provided on the outer side as required.
  • the outermost layer includes a porous layer 44.
  • the non-porous layer 42 and the porous layer 44 are arranged symmetrically with the solid electrolyte 6 in between from the viewpoint of controlling the firing behavior.
  • the end portion on the fuel electrode 2 side (one end portion along the stacking direction of the stack 30) and / or the end portion on the air electrode 4 side (of the stack 30 The other end along the stacking direction) can be provided.
  • the interconnector 10 exhibits conductivity and resistance to reducing gas and oxidizing gas applied to the SOFC, and is suitable for integral sintering with the cell C. It has become. As a result, according to the interconnector 10, it is possible to obtain a SOFC and SOFC stack excellent in power generation characteristics and integrity without complicating the manufacturing process.
  • the anode of the first single cell is used.
  • the interconnector material layer includes a first layer located on the fuel electrode material layer side, and a second layer located on the air electrode material layer side.
  • the second layer has higher electrical conductivity and gas barrier properties than the second layer in a reducing atmosphere, and the second layer has higher electrical conductivity and gas barrier properties than the first layer in an oxidizing atmosphere. be able to.
  • a layer having suitable interconnector characteristics can be applied to each of the fuel electrode and the air electrode, and excellent conductivity and integrity can be exhibited. it can.
  • the first layer and the second layer are suitable for integral sintering with the cell elements, the stack can be integrally sintered without complicating the manufacturing process.
  • the first layer and the second layer can exhibit independent characteristics, the thickness and pattern can be appropriately set according to various aspects of the fuel electrode and the air electrode.
  • the manufacturing method of the SOFC stack in the present specification can generally conform to the manufacturing method of a known sintered integrated SOFC stack.
  • a person skilled in the art can implement this production method by appropriately referring to, for example, the method disclosed in International Publication WO2009 / 119971.
  • the manufacturing method of the SOFC stack is not particularly limited, but generally, a green sheet containing a material of a single cell and one or more elements constituting the stack is prepared in advance and laminated, or such a material is appropriately selected. While directly laminating the layers as a slurry, they are laminated in the required order and fired integrally. A person skilled in the art can appropriately determine and implement what kind of elements the green sheet is prepared or supplied as a slurry, and further the order of lamination and the like within a range where an SOFC stack can be obtained.
  • the firing method of the layered body (stack precursor) of the material layers of each element of the SOFC stack can generally conform to a known method for manufacturing a sintered integrated SOFC stack. That is, the stack precursor is fired so that a ceramic material constituting the precursor is at least partially sintered to obtain a dense or porous desired fired body. Preferably, all elements are co-sintered.
  • the heat treatment can be performed at a temperature of 1250 ° C. to 1550 ° C., and preferably 1250 ° C. to 1500 ° C. More preferably, it is 1250 degreeC or more and 1400 degrees C or less. It can be fired in air.
  • the firing time at the above firing temperature is not particularly limited, and can be, for example, about 1 to several hours.
  • the stack precursor Prior to firing, the stack precursor was pressed by cold isostatic pressing (CIP) as necessary at a temperature of about 60 ° C. to 120 ° C.
  • CIP cold isostatic pressing
  • This pressure-bonded body can be degreased at a temperature in the range of 300 ° C to 500 ° C.
  • the slurry for each layer can be prepared by adding appropriate amounts of a binder resin, an organic solvent, etc., with the material of each element as the main component.
  • the green sheet is a green sheet precursor obtained by casting the prepared slurry using a casting method such as a tape casting method using a coating apparatus such as a knife coater or a doctor blade, or using a screen printing method or a spray method. Can be obtained.
  • a green sheet unfired ceramic green sheet
  • a fuel electrode, an air electrode, and a porous layer of a constraining layer are well known to those skilled in the art.
  • a person skilled in the art can include a desired average pore diameter, porosity, pore size distribution, etc. and appropriate porosity by including a particulate disappearance material in the formulation of the slurry according to a known method or by including a pore-forming agent. It is possible to produce a green sheet that can express the quality by firing.
  • the disappearing material itself is well known, and various materials are commercially available.
  • the method of forming gas flow paths in the fuel electrode, air electrode and interconnector is also well known to those skilled in the art. If it is a person skilled in the art, according to a known method, disposing a disappearing material capable of forming a desired gas flow path pattern on a green sheet of a fuel electrode material, and further laminating a green sheet of a fuel electrode material, etc. can do.
  • an electrode green sheet including a sealing material layer that becomes a seal portion adjacent to the fuel electrode material layer and the air electrode material layer can be manufactured as appropriate.
  • a solid electrolyte green sheet was prepared from a slurry containing a solid electrolyte material.
  • a fuel electrode green sheet is prepared from a fuel electrode slurry containing a fuel electrode material and a pore former and a seal slurry containing a seal material, and a flow path forming material made of a lost material is formed thereon by screen printing or the like. Further, the fuel electrode slurry and the sealing slurry are applied in a predetermined pattern until, for example, the height is about 30% to 70% of the height of the flow path forming material.
  • the slurry for the first layer of the interconnector is applied with a substantially uniform thickness along the surface form including the convex portion of the fuel electrode material layer. Further, after that, the slurry for the second layer of the interconnector is applied to the surface of the first layer slurry so as to cover the convex portion of the fuel electrode material layer and become a substantially flat layer surface. Prepare a green sheet containing layers.
  • the fuel electrode buffer slurry containing the fuel electrode buffer material can be further added as a separate fuel electrode slurry.
  • a green sheet for an air electrode is produced from an air electrode slurry containing an air electrode material and a pore former and a sealing slurry containing a seal material, and a flow path forming material made of a disappearing material is screen printed thereon. Further, the air electrode slurry and the sealing slurry were applied in a predetermined pattern to produce a green sheet including the air electrode material layer. Also, a non-porous constraining layer material slurry and a sealing slurry are applied to the green sheet including the air electrode material layer to prepare an air electrode side termination green sheet.
  • a non-porous constrained layer green sheet and a fuel electrode side end green sheet are prepared using a non-porous constrained layer slurry and a sealing slurry. Further, a porous constraining layer green sheet is prepared using the porous constraining layer slurry and the sealing material.
  • SOFC stack precursors can be prepared by laminating these green sheets so as to include an appropriate number, for example, 2 to 30 or less, for example, 5 to 20 or less. This precursor is fired at a predetermined temperature after pressure bonding and degreasing treatment.
  • an SOFC stack including an interconnector can be obtained by the manufacturing process as described above. It is also possible to manufacture an SOFC stack having an interconnector structure corresponding to a specially shaped fuel electrode. Furthermore, an SOFC stack that also includes an anode buffer layer can be manufactured. Furthermore, an SOFC stack with a constraining layer can also be provided.
  • the SOFC stack described above is further connected to a current collector or the like as necessary, to which a reducing gas and an oxidizing gas supply source are appropriately connected, and further provided with a heating device, so that a SOFC is provided. You can build a system.
  • SOFC stack manufacturing method described above is merely an example of the SOFC stack manufacturing method disclosed in this specification. Therefore, according to a conventionally known SOFC manufacturing method, an appropriate combination of a stack of green sheets including at least one layer constituting a SOFC single cell or a SOFC stack, or a laminate by directly applying a slurry to a constituent layer, etc. SOFC single cells and SOFC stacks can be manufactured.
  • This example is an example of manufacturing an SOFC stack.
  • the ceramic material of each element in the SOFC stack will be shown, and then the manufacturing process of the stack shown in FIGS. 5A to 5D will be described.
  • Green sheet for fuel electrode 20 parts by mass of acrylic particles in which 50% or more of the particles are distributed in an average particle diameter of 10 ⁇ m and an average particle diameter of ⁇ 0.1 ⁇ with respect to 100 parts by mass of the fuel electrode raw material, and this mixed powder and polyvinyl butyral binder And a solvent were mixed to obtain a slurry for a fuel electrode. Also, 20 parts by mass of acrylic particles having an average particle diameter of 5 ⁇ m smaller than the previous acrylic particles and 50% or less of particles distributed within ⁇ 0.1 ⁇ of the average particle diameter are added to 100 parts by mass of the fuel electrode raw material. The mixed powder, polyvinyl butyral binder, and mixed liquid were mixed to obtain a first slurry for the fuel electrode buffer. A second fuel electrode buffer slurry was prepared in the same manner except that 12 parts by mass of acrylic particles used in the fuel electrode slurry (corresponding to 60% of the fuel electrode slurry) were used.
  • a seal portion slurry, a polyvinyl butyral binder, and a solvent were mixed to obtain a seal portion slurry.
  • the fuel electrode slurry and the seal portion slurry are sealed at the center of the green sheet using a doctor blade having a plurality of coating ports, and sealed at both ends.
  • the fuel electrode green sheet 102 was prepared so as to include the portion 102b.
  • a pattern of the space-shaped flow path forming material 103 was produced by a screen printing method.
  • the slurry for the fuel electrode is flown by the doctor blade method until the height becomes about 60% of the height of the flow path forming material.
  • the fuel electrode material layer 104a was formed by directly laminating between the path forming materials 103.
  • the seal part 104b was simultaneously formed in the both ends of the fuel electrode material layer 104a using the slurry for seal parts.
  • the layer including the fuel electrode material layer 104 a is also referred to as a fuel electrode material layer 104.
  • the first fuel electrode buffer slurry is laminated with a constant thickness so as to cover the whole including the flow path forming material 103 by the doctor blade method.
  • 1 fuel electrode buffer material layer 105a was formed.
  • seal portions 105b were formed at both ends at the same time.
  • the corrugated layer including the first fuel electrode buffer material layer 105 a is also referred to as a first fuel electrode buffer material layer 105.
  • the fuel electrode side interconnector material layer 106 is formed by applying a slurry for the fuel electrode side interconnector in a corrugated shape following the first fuel electrode buffer material layer 105 by the doctor blade method. Formed.
  • the air electrode side interconnector slurry is laminated so as to fill the space between the convex portions due to the flow path forming material 103 and cover the fuel electrode side interconnector material layer 106.
  • a green sheet 110 including the air electrode side interconnector material layer 107 was produced.
  • Green sheet for air electrode 20 parts by mass of acrylic particles in which 50% or more of the particles are distributed in an average particle diameter of 10 ⁇ m and an average particle diameter of ⁇ 0.1 ⁇ with respect to 100 parts by mass of the air electrode raw material, and this mixed powder, a polyvinyl butyral binder, Then, a solvent was mixed to prepare an air electrode slurry. Thereafter, as shown in FIG. 5D (a), the air electrode slurry and the seal portion slurry are sealed at the center of the green sheet with the air electrode material layer 112a and at both ends, using a doctor blade having a plurality of coating ports. The air electrode green sheet 112 was prepared so as to include the portion 112b.
  • FIG. 5D (b) a line and space in which a plurality of linear flow path forming materials are arranged at regular intervals using an acrylic resin composition on the air electrode green sheet 112.
  • a pattern of the flow path forming material 113 was created by screen printing.
  • the slurry for the air electrode is formed by the doctor blade method, and the entire height of the flow path forming material 113 and the flow path shape material 113 are formed.
  • the air electrode material layer 114a was formed by directly stacking so as to cover the top surface. Also at this time, the seal portion 114b was formed at both ends at the same time to produce the green sheet 115 for the air electrode.
  • Green sheet for constraining layer As shown in FIG. 5A (b), a constrained layer raw material, a polyvinyl butyral binder, and a solvent are mixed to obtain a slurry for a nonporous constrained layer, and a green sheet 120 for a nonporous constrained layer is obtained by a doctor blade method. Was made.
  • a slurry obtained by adding 10 parts by mass of acrylic particles to 100 parts by mass of the raw material of the constraining layer, a polyvinyl butyral binder, and a solvent are mixed to obtain a slurry for the porous constraining layer.
  • a green sheet 121 for a porous constrained layer was produced by a doctor blade method.
  • the air electrode green sheet 115, the solid electrolyte green sheet 101, and the fuel electrode green sheet with respect to the air electrode side interconnector material layer 107 of the fuel electrode green sheet 110. 110 was stacked to form a second cell precursor 202. Further, as shown in FIG. 6B (e), similarly, green sheets are laminated to form the third cell precursor 203, and the non-porous constraining layer is formed on the air electrode side interconnector material layer 107.
  • a green sheet 120 for a stack was laminated, and a green sheet 121 for a porous constrained layer was further laminated to obtain a stack precursor 130 of this example.
  • the stack precursor 130 was subjected to pressure bonding by cold isostatic pressing (CIP) at a temperature of 100 MPa and 80 ° C. for 2 minutes.
  • CIP cold isostatic pressing
  • the pressure-bonded body was degreased at a temperature of 400 ° C., and then held at a temperature of 1400 ° C. for 2 hours to be fired to obtain a stack of examples.
  • a stack of another example was obtained in the same manner as described above, except that the second fuel electrode buffer layer slurry was used instead of the first fuel electrode buffer layer slurry.
  • the thickness of the solid electrolyte 6 is about 20 ⁇ m
  • the thickness of the fuel electrode 2 between the reducing gas flow paths 22 is about 50 ⁇ m
  • the reducing gas flow The thickness of the passage 22 is about 100 ⁇ m
  • the thickness of the air electrode 4 between the oxidizing gas passages 24 is about 50 ⁇ m
  • the thickness of the oxidizing gas passage 24 is about 200 ⁇ m
  • the fuel electrode side interconnector (first Layer) 12 was about 10 ⁇ m
  • the air electrode side interconnector (second layer) 14 was about 10 to 100 ⁇ m (minimum portion to maximum portion).
  • an SOFC stack of the following mode was also produced at the same time. That is, the second layer material of the interconnector is changed to a mixture of La 0.8 Sr 0.2 MnO 3 50% by mass, “3YSZ” 45% by mass and ceria 5% by mass, La 0.8 Sr 0.2 MnO 3 50% by mass,
  • a SOFC stack of Comparative Example 1 was produced by the same production process as the SOFC stack described above except that a mixture of 45% by mass of “8YSZ” and 5% by mass of ceria was used.
  • the first fuel electrode buffer slurry is applied in such a thickness as to cover the entire height of the flow path forming member 103 to flatten the surface of the fuel electrode material layer as described above.
  • a SOFC stack of Comparative Example 2 was produced in the same manufacturing process as the SOFC stack.
  • a SOFC stack of Comparative Example 3 was manufactured by the same manufacturing process as the SOFC stack described above except that the first fuel electrode buffer layer was not provided.
  • the stack of this example was provided with a stack having excellent integrity and electrical conductivity by including the first layer and the second layer as interconnectors.
  • the air electrode / air electrode side interconnector / fuel electrode side interconnector / fuel electrode The electric resistance value was 0.13 ⁇ ⁇ cm 2 , whereas in Comparative Example 1 using 8YSZ instead of 3YSZ, it was 0.54 ⁇ ⁇ cm 2 .
  • the stack of the present embodiment has a corrugated fuel electrode side interconnect by causing the fuel electrode side interconnector (first layer) to follow an electrode (fuel electrode) having a convex portion based on the gas flow path.
  • the volume of the fuel electrode could be suppressed by providing the air electrode side interconnector (second layer) so as to fill the non-convex portion of the fuel electrode interconnector as a connector.
  • the fuel electrode and hence the stack volume fluctuation due to the oxidation and reduction accompanying the start and stop of the SOFC For example, assuming that the total amount of Ni used in the stack of Comparative Example 2 is 100, the amount of Ni used in the stack of this example was 40%.
  • the stack of this embodiment has a fuel electrode buffer layer, so that the adhesion and integrity between the fuel electrode and the fuel electrode side interconnector (first layer) are improved, and the fuel electrode has a convex shape.
  • the top surface of the reducing gas channel was well covered.
  • the fuel electrode side interconnector No. 1
  • the stack of another embodiment including the second fuel electrode buffer layer having a porosity lower than that of the fuel electrode is also the adhesion and integrity between the fuel electrode and the fuel electrode side interconnector (first layer).
  • the cell without the constraining layer was greatly deformed, the cell with the constraining layer could be sintered flat.

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Abstract

La présente invention concerne un empilement de SOFC fritté intégralement et son procédé de fabrication. L'invention concerne un empilement de piles à combustible à oxyde solide comprenant des cellules uniques C avec des inter-connecteurs entre celles-ci, les cellules uniques C ayant chacune une électrode de combustible 2, un électrolyte solide 6, et une électrode à air 4, l'empilement étant pourvu d'une couche contrainte qui comprend une couche non poreuse contenant un matériau céramique conducteur et un matériau d'oxyde d'un élément contenu dans l'électrolyte solide.
PCT/JP2016/075128 2016-08-29 2016-08-29 Empilement de de piles à combustible à oxyde solide et procédé de préparation associé WO2018042480A1 (fr)

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PCT/JP2016/075128 WO2018042480A1 (fr) 2016-08-29 2016-08-29 Empilement de de piles à combustible à oxyde solide et procédé de préparation associé
JP2017525434A JP6378436B2 (ja) 2016-08-29 2016-08-29 固体酸化物形燃料電池スタック及びその製造方法

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010199055A (ja) * 2009-01-28 2010-09-09 Kyocera Corp 固体酸化物形燃料電池セルおよびその製法、ならびに燃料電池セルスタック装置、燃料電池モジュール、燃料電池装置
WO2012133087A1 (fr) * 2011-03-30 2012-10-04 株式会社村田製作所 Élément liant pour pile à combustible à oxyde solide, pile à combustible à oxyde solide, et module de pile à combustible à oxyde solide
JP2014518434A (ja) * 2011-06-15 2014-07-28 エルジー フューエル セル システムズ インク 相互接続部を有する燃料電池システム
WO2015045986A1 (fr) * 2013-09-24 2015-04-02 株式会社村田製作所 Empilement de piles à oxyde solide et son procédé de fabrication
WO2016009542A1 (fr) * 2014-07-17 2016-01-21 ＦＣＯ Ｐｏｗｅｒ株式会社 Structure empilée de pile à combustible à oxyde solide de type plaque et système de pile à combustible à oxyde solide

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2006016628A1 (ja) * 2004-08-10 2008-05-01 財団法人電力中央研究所 成膜物
JPWO2015056320A1 (ja) * 2013-10-17 2017-03-09 ＦＣＯ Ｐｏｗｅｒ株式会社 固体酸化物形燃料電池スタックアレイ

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010199055A (ja) * 2009-01-28 2010-09-09 Kyocera Corp 固体酸化物形燃料電池セルおよびその製法、ならびに燃料電池セルスタック装置、燃料電池モジュール、燃料電池装置
WO2012133087A1 (fr) * 2011-03-30 2012-10-04 株式会社村田製作所 Élément liant pour pile à combustible à oxyde solide, pile à combustible à oxyde solide, et module de pile à combustible à oxyde solide
JP2014518434A (ja) * 2011-06-15 2014-07-28 エルジー フューエル セル システムズ インク 相互接続部を有する燃料電池システム
WO2015045986A1 (fr) * 2013-09-24 2015-04-02 株式会社村田製作所 Empilement de piles à oxyde solide et son procédé de fabrication
WO2016009542A1 (fr) * 2014-07-17 2016-01-21 ＦＣＯ Ｐｏｗｅｒ株式会社 Structure empilée de pile à combustible à oxyde solide de type plaque et système de pile à combustible à oxyde solide

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