WO2014050124A1 - Feuille d'électrolyte destinée à une pile à combustible à oxyde solide, pile supportant un électrolyte, pile unique destinée à une pile à combustible à oxyde solide, et pile à combustible à oxyde solide - Google Patents

Feuille d'électrolyte destinée à une pile à combustible à oxyde solide, pile supportant un électrolyte, pile unique destinée à une pile à combustible à oxyde solide, et pile à combustible à oxyde solide Download PDF

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WO2014050124A1
WO2014050124A1 PCT/JP2013/005745 JP2013005745W WO2014050124A1 WO 2014050124 A1 WO2014050124 A1 WO 2014050124A1 JP 2013005745 W JP2013005745 W JP 2013005745W WO 2014050124 A1 WO2014050124 A1 WO 2014050124A1
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oxide
mol
zirconia
electrolyte
rare earth
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PCT/JP2013/005745
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English (en)
Japanese (ja)
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秦　和男
西川　洋平
相川　規一
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株式会社日本触媒
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Priority to CN201380049722.XA priority Critical patent/CN104685684B/zh
Priority to JP2014538196A priority patent/JP5890908B2/ja
Publication of WO2014050124A1 publication Critical patent/WO2014050124A1/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
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/126—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing cerium oxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium oxides or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/762—Cubic symmetry, e.g. beta-SiC
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • 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
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H01M2300/0074—Ion conductive at high temperature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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 an electrolyte sheet for a solid oxide fuel cell, an electrolyte supporting cell using the same, a single cell for a solid oxide fuel cell, and the electrolyte supporting cell or the solid oxide fuel cell.
  • the present invention relates to a solid oxide fuel cell including a single cell.
  • SOFC solid oxide fuel cells
  • the SOFC has a structure in which a solid electrolyte layer made of ceramic is disposed between an air electrode and a fuel electrode as a basic structure.
  • oxygen in the air introduced into the air electrode receives electrons and becomes oxygen ions (O 2 ⁇ ), and the oxygen ions move through the solid electrolyte layer and reach the fuel electrode. Electrons are released when oxygen ions that have reached the fuel electrode react electrochemically with hydrogen at the fuel electrode, and an electrical output is obtained.
  • the solid electrolyte layer is required to have characteristics such as high oxygen ion conductivity and high material strength. Therefore, the solid electrolyte layer generally includes zirconia (yttria stabilized zirconia (YSZ)) to which yttria (Y 2 O 3 ) is added and zirconia (scandia stabilization to which scandia (Sc 2 O 3 ) is added).
  • YSZ zirconia
  • a sintered body such as a zirconia-based oxide such as zirconia (ScSZ) is used.
  • Patent Document 1 proposes various materials for a solid electrolyte layer that can realize a stable crystal phase in addition to high oxygen ion conductivity and high material strength.
  • an object of the present invention is to provide an SOFC electrolyte sheet that can suppress a change with time in oxygen ion conductivity even when exposed to an atmosphere containing a sulfur component. Furthermore, the present invention also provides an electrolyte-supported cell, a single cell for SOFC, and a SOFC that can suppress a decrease in durability even when fuel containing a sulfur component is supplied to the fuel electrode. Objective.
  • the first aspect of the present invention is: Including electrolyte components,
  • the electrolyte component is a zirconia-based oxide that is stabilized with scandium oxide (Sc 2 O 3 ) and cerium oxide (CeO 2 ) and contains a rare earth oxide of 0.003 mol% or more and less than 0.5 mol%.
  • the rare earth oxide is an oxide of at least one element selected from rare earth elements excluding Sc and Ce.
  • An electrolyte sheet for SOFC is provided.
  • the second aspect of the present invention is: Including electrolyte components,
  • the electrolyte component is composed of a zirconia-based oxide that is stabilized with scandium oxide (Sc 2 O 3 ) and contains a rare earth oxide of 0.003 mol% or more and less than 0.5 mol%,
  • the rare earth oxide is an oxide of at least one element selected from rare earth elements excluding Sc.
  • An electrolyte sheet for SOFC is provided.
  • the third aspect of the present invention is: Provided is an electrolyte-supporting cell comprising a fuel electrode, an air electrode, and the SOFC electrolyte sheet according to the first aspect or the second aspect disposed between the fuel electrode and the air electrode.
  • the fourth aspect of the present invention is: A fuel electrode, an air electrode, and a solid electrolyte layer disposed between the fuel electrode and the air electrode, At least one selected from the fuel electrode, the air electrode, and the solid electrolyte layer is stabilized with scandium oxide (Sc 2 O 3 ) and cerium oxide (CeO 2 ), and is 0.003 mol% or more and 0 A zirconia-based oxide containing less than 5 mol% rare earth oxide as an electrolyte component;
  • the rare earth oxide is an oxide of at least one element selected from rare earth elements excluding Sc and Ce.
  • a single cell for SOFC is provided.
  • a zirconia oxide containing oxide is included as an electrolyte component, The rare earth oxide is an oxide of at least one element selected from rare earth elements excluding Sc.
  • a single cell for SOFC is provided.
  • the sixth aspect of the present invention is: An SOFC comprising the electrolyte-supporting cell according to the third aspect, the SOFC single cell according to the fourth aspect, or the SOFC single cell according to the fifth aspect is provided.
  • the SOFC electrolyte sheet according to the first and second aspects of the present invention can suppress changes in oxygen ion conductivity over time even when exposed to an atmosphere containing a sulfur component.
  • the electrolyte supporting cell according to the third aspect of the present invention includes such an electrolyte sheet for SOFC, durability is ensured even when a fuel containing a sulfur component is supplied to the fuel electrode. Can be kept small.
  • the SOFC single cell according to the fourth and fifth aspects of the present invention is exposed to an atmosphere containing a sulfur component, the oxygen ion conductivity of the solid electrolyte layer changes with time, or the electrode. Since the change with time of the activity can be suppressed to a small level, it is possible to suppress a decrease in durability.
  • the SOFC according to the sixth aspect of the present invention includes the electrolyte-supporting cell according to the third aspect, the SOFC single cell according to the fourth aspect, or the SOFC single cell according to the fifth aspect, Even when exposed to an atmosphere containing a sulfur component, a decrease in durability can be minimized.
  • the electrolyte sheet of the present embodiment includes an electrolyte component, and the electrolyte component is It is stabilized with scandium oxide (Sc 2 O 3 ) and cerium oxide (CeO 2 ), and is rare earth oxide (hereinafter referred to as rare earth oxide A) of 0.003 mol% or more and less than 0.5 mol%. ) Containing at least one element selected from rare earth elements excluding Sc and Ce.
  • rare earth oxide B a rare earth oxide of 0.003 mol% or more and less than 0.5 mol%
  • the rare earth oxide B is an oxide of at least one element selected from rare earth elements excluding Sc.
  • 0.003 mol% or more and less than 0.5 mol% rare earth oxide A means that the total amount of rare earth oxide A is 0.003 mol% or more and less than 0.5 mol%. means.
  • the rare earth oxide B of 0.003 mol% or more and less than 0.5 mol% means that the total amount of the rare earth oxide B is 0.003 mol% or more and less than 0.5 mol%. . The same applies to the subsequent steps.
  • the electrolyte sheet of the present embodiment includes an electrolyte component, and the electrolyte component is a trace amount of 0.003 mol% or more and less than 0.5 mol% in zirconia stabilized with scandium oxide (Sc 2 O 3 ).
  • cerium oxide (CeO 2 ) functions as a stabilizer for zirconia
  • other rare earth element oxides other than Ce are 0.003 mol% or more and 0.5 mol%. It is characterized by being a zirconia-based oxide (scandiaceria-stabilized zirconia-based oxide) added in a range of less than%.
  • the electrolyte sheet of the present embodiment having the above-described configuration can suppress a decrease in oxygen ion conductivity even when exposed to an atmosphere containing a sulfur component. Therefore, even when hydrogen generated by reforming city gas is used as a fuel and the fuel may contain a sulfur component, the electrolyte sheet of this embodiment is used as the SOFC. It can be suitably used as a solid electrolyte layer.
  • a desulfurization device is often provided along with the reformer.
  • a desulfurization apparatus may not be provided in a system in which an internal reforming SOFC that directly reforms city gas in the SOFC is used. Therefore, the electrolyte sheet of the present embodiment exhibits excellent effects particularly when applied to an internal reforming SOFC solid electrolyte layer.
  • the electrolyte component contained in the electrolyte sheet of the present embodiment is a form that is the scandiaceria-stabilized zirconia-based oxide (form 1-A) and a form that is the scandia-stabilized zirconia-based oxide (form 1). -B) will be described respectively.
  • Form 1-A sinandiaceria-stabilized zirconia oxide
  • the electrolyte component contained as the main component of the electrolyte sheet according to Form 1-A is stabilized with scandium oxide (Sc 2 O 3 ) and cerium oxide (CeO 2 ), and is 0.003 mol% or more and 0.5 mol It is comprised with the zirconia-type oxide containing the rare earth oxide A of less than%.
  • the rare earth oxide A is an oxide of at least one element selected from rare earth elements excluding Sc and Ce.
  • the rare earth oxide A is at least one selected from the group consisting of Y, La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. It is an oxide of an element.
  • 0.003 mol% or more and less than 0.5 mol% of rare earth oxide A is further dissolved in zirconia in which scandium oxide and cerium oxide are dissolved as stabilizers.
  • the zirconia-based oxide sintered body is formed.
  • the total amount of rare earth oxide A in the zirconia-based oxide is preferably 0.005 mol% or more and 0.4 mol% or less, and more preferably 0.01 mol% or more and 0.3 mol% or less.
  • Rare earth oxide A contained in a trace amount in the range of 0.003 mol% or more and less than 0.5 mol% in a zirconia-based oxide stabilized with scandium oxide (Sc 2 O 3 ) and cerium oxide (CeO 2 ) Has the effect of suppressing the formation of a compound of an electrolyte component and a sulfur component, deposition and adhesion of the sulfur component to the electrolyte surface, and the like.
  • the content of the rare earth oxide A is less than 0.003 mol%, the effect of suppressing the adverse effect of the sulfur component due to the rare earth oxide A on the electrolyte component is not sufficiently exhibited, and the electrolyte sheet is in an atmosphere containing the sulfur component. When exposed, it is difficult to keep the oxygen ion conductivity change with time small.
  • the content of the rare earth oxide A is 0.5 mol% or more, it is expected that the sulfur component is likely to be deposited and adhered to the surface of the electrolyte, or to react easily with the electrolyte component. As a result, the conductivity of the electrolyte sheet gradually deteriorates as the inflow of fuel proceeds. Therefore, if the zirconia-based oxide constituting the electrolyte component contains the rare earth oxide A excessively, the change with time of the conductivity of the electrolyte sheet becomes large.
  • the rare earth oxide A contained as a trace component is selected from the group consisting of Y, La, Pr, Nd, Sm, Gd and Yb in order to more reliably suppress the temporal change in oxygen ion conductivity caused by the sulfur component. It is preferably an oxide of at least one element selected from the group consisting of Y, Sm, Gd, and Yb, and more preferably an oxide of at least one element selected from the group consisting of Y, Sm, Gd, and Yb.
  • the rare earth oxide A is gadolinium oxide (Gd 2 O 3 ).
  • gadolinium oxide (Gd 2 O 3 ) is contained as the rare earth oxide A in the zirconia-based oxide in Form 1-A, among other rare earth oxides, formation of a compound of an electrolyte component and a sulfur component, Highly effective in suppressing the deposition and adhesion of sulfur components to the electrolyte surface. Therefore, when the zirconia-based oxide in Form 1-A contains gadolinium oxide (Gd 2 O 3 ) as the rare earth oxide A, the change over time in the oxygen ion conductivity caused by the sulfur component can be further suppressed to be small. Can do.
  • zirconia oxide in Embodiment 1-A contains gadolinium oxide (Gd 2 O 3), content is 0.2 mol% or less than 0.003 mole percent gadolinium oxide (Gd 2 O 3) It is preferable. This is because when the content of gadolinium oxide (Gd 2 O 3 ) exceeds 0.2 mol%, the effect cannot be enhanced to the extent that it matches the content of gadolinium oxide.
  • the zirconia-based oxide in Form 1-A contains gadolinium oxide (Gd 2 O 3 ), it is preferable that yttrium oxide (Y 2 O 3 ) is further added as the rare earth oxide A.
  • the electrolyte component of the electrolyte sheet of Form 1-A is composed of a zirconia-based oxide containing both gadolinium oxide (Gd 2 O 3 ) and yttrium oxide (Y 2 O 3 ) as the rare earth oxide A, The effect of suppressing the adverse effect of the sulfur component on the electrolyte component can be further improved.
  • the content of yttrium oxide (Y 2 O 3 ) is 0.003. A particularly excellent effect can be obtained when the content is in the range of from mol% to 0.2 mol%.
  • the zirconia-based oxide in Form 1-A preferably contains scandium oxide (Sc 2 O 3 ) in an amount of 8 mol% to 15 mol%, and contains 8.5 mol% to 12 mol%. It is more preferable that it is contained in an amount of 9 mol% or more and 11 mol% or less.
  • the zirconia-based oxide in Form 1-A preferably has a cubic crystal structure. When the crystal structure includes cubic crystals, the zirconia-based oxide in Form 1-A preferably contains scandium oxide (Sc 2 O 3 ) in an amount of 9.5 mol% to 12 mol%. More preferably, it is contained in an amount of 10 mol% to 11.5 mol%.
  • the zirconia-based oxide in Form 1-A preferably contains cerium oxide (CeO 2 ) in an amount of 0.5 mol% or more and 2.5 mol% or less, and contains 0.6 mol% or more and 2 mol% or less. It is more preferable that it is contained in an amount of 0.7 mol% or more and 1.5 mol% or less.
  • CeO 2 cerium oxide
  • Form 1-B sinandia-stabilized zirconia oxide
  • the electrolyte component contained as a main component of the electrolyte sheet according to Form 1-B is stabilized with scandium oxide (Sc 2 O 3 ), and is rare earth oxide B having a content of 0.003 mol% or more and less than 0.5 mol%. It is comprised with the zirconia-type oxide containing.
  • the rare earth oxide B is an oxide of at least one element selected from rare earth elements excluding Sc. That is, the rare earth oxide B is at least one selected from the group consisting of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
  • 0.003 mol% or more and less than 0.5 mol% of rare earth oxide B is further dissolved in zirconia in which scandium oxide is dissolved as a stabilizer. It is formed of a sintered body of zirconia oxide.
  • the total amount of rare earth oxide B in the zirconia-based oxide is preferably 0.005 mol% to 0.4 mol%, and more preferably 0.01 mol% to 0.3 mol%.
  • the decrease in the electrical conductivity of the electrolyte sheet that occurs in an atmosphere containing a sulfur component occurs due to the electrolyte component forming a compound with the sulfur component, or the sulfur component being deposited on or attached to the electrolyte surface.
  • the rare earth oxide B contained in a trace amount within the range of 0.003 mol% to less than 0.5 mol% is composed of an electrolyte component and a sulfur component. It has the effect of suppressing the formation of the compound and the deposition and adhesion of sulfur components to the electrolyte surface.
  • the content of the rare earth oxide B is less than 0.003 mol%, the effect of suppressing the adverse effect of the sulfur component due to the rare earth oxide B on the electrolyte component is not sufficiently exhibited, and the electrolyte sheet is in an atmosphere containing the sulfur component. When exposed, it is difficult to keep the oxygen ion conductivity change with time small. Further, when the content of the rare earth oxide B is 0.5 mol% or more, it is expected that the sulfur component easily deposits and adheres to the surface of the electrolyte or reacts easily with the electrolyte component. As a result, the conductivity of the electrolyte sheet gradually deteriorates as the inflow of fuel proceeds. Accordingly, when the zirconia-based oxide constituting the electrolyte component contains the rare earth oxide B excessively, the change with time of the conductivity of the electrolyte sheet becomes large.
  • the rare earth oxide B contained as a trace component is a group consisting of Y, La, Ce, Pr, Nd, Sm, Gd, and Yb in order to more reliably suppress the temporal change in oxygen ion conductivity caused by the sulfur component.
  • the oxide is an oxide of at least one element selected from the group consisting of Y, Ce, Sm, Gd, and Yb. More preferred.
  • the rare earth oxide B is cerium oxide (CeO 2 ).
  • cerium oxide (CeO 2 ) is contained as rare earth oxide B in the zirconia-based oxide in Form 1-B, among other rare earth oxides, formation of a compound of an electrolyte component and a sulfur component, Highly effective in suppressing deposition and adhesion of sulfur components. Therefore, when the zirconia-based oxide in Form 1-B contains cerium oxide (CeO 2 ) as the rare earth oxide B, the change over time in the oxygen ion conductivity caused by the sulfur component can be more reliably suppressed. .
  • the zirconia-based oxide in Form 1-B contains cerium oxide (CeO 2 )
  • its content is preferably 0.1 mol% or more, more preferably 0.2 mol% or more.
  • its content is preferably 0.48 mol% or less, and more preferably 0.45 mol% or less.
  • the zirconia-based oxide in Form 1-B when the rare earth oxide B is gadolinium oxide (Gd 2 O 3 ), a high effect of suppressing change with time in oxygen ion conductivity can be obtained.
  • the zirconia-based oxide in Form 1-B contains gadolinium oxide (Gd 2 O 3 ), its content is preferably 0.003 mol% or more and 0.2 mol% or less, and 0.005 mol% or more 0.1 mol% or less is more preferable.
  • the zirconia-based oxide in Form 1-B when the rare earth oxide B is yttrium oxide (Y 2 O 3 ), a high effect of suppressing the change in oxygen ion conductivity with time can be obtained.
  • the zirconia-based oxide in Form 1-B contains yttrium oxide (Y 2 O 3 )
  • its content is preferably 0.003 mol% or more and 0.2 mol% or less, and 0.005 mol% or more 0.1 mol% or less is more preferable.
  • the zirconia-based oxide in Form 1-B may contain both gadolinium oxide (Gd 2 O 3 ) and yttrium oxide (Y 2 O 3 ) as rare earth oxide B.
  • the electrolyte component of the electrolyte sheet of Form 1-B is composed of a zirconia-based oxide containing both gadolinium oxide (Gd 2 O 3 ) and yttrium oxide (Y 2 O 3 ) as rare earth oxide B. The effect of suppressing the adverse effect of the sulfur component on the electrolyte component can be further improved.
  • gadolinium oxide (Gd 2 O 3 ) and yttrium oxide (Y 2 O 3 ) are not clear, but gadolinium oxide (Gd 2 O 3 ) and yttrium oxide (Y 2 O). 3 ) is preferably from 0.003 mol% to 0.2 mol%, more preferably from 0.005 mol% to 0.1 mol%.
  • the zirconia-based oxide in Form 1-B preferably contains scandium oxide (Sc 2 O 3 ) in an amount of 4 mol% to 15 mol%.
  • the zirconia-based oxide contains scandium oxide (Sc 2 O 3 ) in an amount of 4 mol% to 6.5 mol%. Is preferred.
  • the zirconia-based oxide preferably contains scandium oxide (Sc 2 O 3 ) in an amount of 9 mol% to 13 mol%. 9.5 mol% or more and 12 mol% or less, more preferably 10 mol% or more and 11.5 mol% or less.
  • the cubic system means stabilized zirconia whose crystal structure is mainly composed of cubic crystals. Specifically, each peak intensity is obtained from the X-ray diffraction pattern of the zirconia crystal in the solid electrolyte sheet, and the cubic ratio (%) obtained from each intensity value and the following formula is 50% or more.
  • the cubic stabilized zirconia preferably has a cubic ratio of 90% or more, more preferably 95% or more, and still more preferably 97% or more.
  • Cubic crystal ratio (%) (100 ⁇ monoclinic crystal ratio) ⁇ [c (400)] ⁇ [t (400) + t (004) + c (400)] [Wherein c (400) represents the peak intensity of the cubic (400) plane, t (400) represents the peak intensity of the tetragonal (400) plane, and t (004) represents the tetragonal (004) plane. Shows peak intensity]
  • the tetragonal system means stabilized zirconia whose crystal structure is mainly tetragonal. Specifically, each peak intensity is obtained from the X-ray diffraction pattern of the zirconia crystal in the solid electrolyte sheet, and the tetragonal crystal ratio (%) obtained from each intensity value and the following formula is 50% or more.
  • Tetragonal stabilized zirconia Tetragonal crystal ratio (%) (100 ⁇ monoclinic crystal ratio) ⁇ [t (400) + t (004)] ⁇ [t (400) + t (004) + c (400)] [Where t (400) represents the peak intensity of the tetragonal (400) plane, t (004) represents the peak intensity of the tetragonal (004) plane, and c (400) represents the cubic (400) plane. Shows peak intensity]
  • the electrolyte sheet of the present embodiment refers to both the electrolyte sheet of Form 1-A and the electrolyte sheet of Form 1-B), for example, hafnium oxide other than the above components And oxides such as aluminum oxide, titanium oxide, niobium oxide, tantalum oxide, and manganese oxide, and composite oxides such as LaAlO 3 , MgAl 2 O 4 , Al 2 TiO 5, and LaGaO 3 in a total amount of 5% by mass or less. It may be further included in the range.
  • Li, Na, K, Mg, Ca, Sr, Ba, La, Pr, Nd, Yb, Cr, W, Fe, Co, Ni, Cu, Zn, B, Ga, Si, Ge, P, etc. are included. It may be. In that case, the total content of these components is preferably 1.0% by mass or less in terms of oxide.
  • the form of the electrolyte sheet of the present embodiment is not particularly limited, and examples thereof include a flat plate shape, a curved shape, a film shape, a cylindrical shape, a cylindrical flat plate shape, and a honeycomb shape.
  • the thickness of the electrolyte sheet of the present embodiment can be, for example, 10 ⁇ m or more and 400 ⁇ m or less.
  • the thickness of the electrolyte sheet is preferably, for example, 80 ⁇ m or more and 400 ⁇ m or less, and more preferably 90 ⁇ m or more and 300 ⁇ m or less.
  • Electrolytes size of the sheet of the present embodiment is not particularly limited, for example, 50 cm 2 or more 900 cm 2 or less, preferably electrolyte sheet having a planar area of 70cm 2 or more 500 cm 2 or less are preferably used.
  • the shape of the sheet may be any of a circle, an ellipse, and a square with R (R).
  • These sheets may have one or two or more holes such as a similar circular shape, an elliptical shape, and a rectangular shape having R (R).
  • the said plane area means the area (area determined by sheet
  • the electrolyte sheet of this embodiment a general method for manufacturing an electrolyte sheet for SOFC can be used. That is, the electrolyte sheet of this embodiment can be obtained by preparing a green sheet for an electrolyte sheet and firing the green sheet.
  • a zirconia-based oxide raw material powder used as a raw material for the electrolyte component of the electrolyte sheet of the present embodiment is prepared.
  • any method can be used as long as it is a method capable of producing a powder, but in this embodiment, a coprecipitation method which is a liquid phase process is preferably used.
  • the raw material powder of the electrolyte sheet of the present embodiment includes a solution containing a zirconium compound and a scandium compound, and a rare earth element compound such as a cerium compound, a gadolinium compound, and an yttrium compound, which are appropriately selected as necessary, and a precipitant. It can be obtained by mixing and coprecipitating, and baking the obtained precipitate in an oxidizing atmosphere.
  • the raw material of each component used in the present embodiment is not particularly limited, and examples thereof include inorganic acid salts such as nitrates, carbonates, sulfates, chlorides and oxychlorides, and organic acid salts such as acetates and oxalates.
  • inorganic acid salts such as nitrates, carbonates, sulfates, chlorides and oxychlorides
  • organic acid salts such as acetates and oxalates.
  • nitrates, chlorides and oxychlorides are preferably used.
  • dissolving each raw material in a solvent and obtaining a solution should just be a method which can melt
  • the solvent include water and alcohols.
  • the precipitating agent to be added is not particularly limited, and examples thereof include bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium carbonate and ammonia. Among these, it is particularly preferable to use ammonia. These precipitating agents are usually preferably added as a solution.
  • the mixing method of the solution containing the raw materials of each component and the precipitant is not particularly limited. Examples thereof include a method of dropping a precipitant solution into a solution containing the raw materials of each component, a method of dropping a solution containing the raw materials of each component into the precipitant solution, and the like.
  • the precipitate produced by the above method can be recovered by solid-liquid separation by washing with water and filtering.
  • the obtained precipitate is usually baked after drying to become an oxide.
  • This firing may be performed in an oxidizing atmosphere, and is preferably performed in the air.
  • the firing temperature is not particularly limited, but is usually about 500 to 1300 ° C., preferably about 600 to 1200 ° C. When the firing temperature is less than 500 ° C., the precipitate may not be sufficiently oxidized. When the firing temperature exceeds 1300 ° C., strong aggregation may occur due to grain growth.
  • the obtained oxide may be pulverized as necessary.
  • the method of pulverization is not particularly limited, and examples thereof include wet pulverization and dry pulverization.
  • the crystal structure of the zirconia-based oxide of the present embodiment is preferably a cubic phase single phase or a tetragonal single phase.
  • the crystal structure of the electrolyte material may be a mixed phase of a cubic phase and a rhombohedral phase (R phase) that includes a slight amount of rhombohedral phase as long as there is no problem in strength and oxygen ion conductivity.
  • the crystal structure of the electrolyte material has a monoclinic phase, a cubic phase, and a tetragonal phase, with a slight monoclinic phase and cubic phase, as long as there is no problem in strength and oxygen ion conductivity. It may be a mixed phase.
  • a green sheet for an electrolyte sheet is produced using the obtained raw material powder.
  • a tape forming method is preferably used, and in particular, a doctor blade method and a calendar method are preferably used.
  • a binder and an additive are added to the zirconia-based oxide raw material powder obtained by the above method, and a dispersion medium or the like is further added as necessary to prepare a slurry. This slurry is spread on a support plate or a carrier film and formed into a sheet shape, which is dried to volatilize the dispersion medium to obtain a green sheet.
  • the green sheet is made into an appropriate size by cutting and / or punching or the like to produce a green sheet for an electrolyte sheet.
  • the binder, the solvent, the dispersant, and the like used for the preparation of the slurry a known binder, a solvent, a dispersant, and the like that are used for manufacturing the SOFC electrolyte sheet can be used.
  • the green sheet for the electrolyte sheet is fired.
  • the green sheet for an electrolyte sheet obtained as described above is placed on a porous setter on a shelf board.
  • the porous setter and the green sheet for the electrolyte sheet produced as described above are alternately stacked on the shelf so that the porous setter is disposed in the lowermost layer and the uppermost layer, You may arrange
  • the green sheet thus arranged is heated and fired at a temperature of about 1200 to 1500 ° C., preferably about 1250 to 1425 ° C. for about 1 to 5 hours.
  • the firing temperature exceeds 1500 ° C.
  • rhombohedral crystals and monoclinic crystals are formed in the sintered body, and both the strength at normal temperature (room temperature strength) and high-temperature durability of the electrolyte sheet may deteriorate.
  • the firing temperature is less than 1200 ° C.
  • firing in the above temperature range suppresses the formation of monoclinic crystals and rhombohedrons, and the relative density of the obtained sheet can be 97% or more, preferably 99% or more.
  • the relative density is a relative value of density measured by Archimedes method with respect to theoretical density (density measured by Archimedes method / theoretical density).
  • the well-known porous setter used for manufacture of the electrolyte sheet for SOFC can be used for the porous setter used for baking of a green sheet.
  • zirconia powder stabilized with scandium oxide (Sc 2 O 3 ) and cerium oxide (CeO 2 ), or zirconia powder stabilized with scandium oxide (Sc 2 O 3 ), a rare earth oxide, and a rare earth element It is also possible to sequentially prepare a slurry, a green sheet, and an electrolyte sheet using a metal-containing metal or a compound containing a rare earth element as a raw material powder.
  • zirconia powder previously stabilized with scandium oxide (Sc 2 O 3 ) and cerium oxide (CeO 2 ) containing rare earth elements, or stabilized with scandium oxide (Sc 2 O 3 ). It is also possible to use a zirconia powder made.
  • FIG. 1 is a cross-sectional view showing an example of the configuration of the electrolyte-supporting cell of the present embodiment.
  • the electrolyte support cell 1 of the present embodiment includes a fuel electrode 11, an air electrode 12, and an SOFC electrolyte sheet 13 disposed between the fuel electrode 11 and the air electrode 12.
  • the electrolyte sheet 13 the SOFC electrolyte sheet described in Embodiment 1 (the electrolyte sheet of Form 1-A or Form 1-B) is used.
  • the fuel electrode 11 and the air electrode 12 a fuel electrode and an air electrode used in a known SOFC can be applied, respectively.
  • the fuel electrode 11 is formed on one main surface of the electrolyte sheet obtained by the method described in the first embodiment, and the air electrode 12 is formed on the other main surface.
  • a binder and a solvent are added to the powder of the material constituting the fuel electrode 11 or the air electrode 12, and a dispersant is added as necessary to prepare a slurry.
  • This slurry is applied to one or the other main surface of the electrolyte sheet 13 with a predetermined thickness, and the coating layer is dried to form a green layer for the fuel electrode 11 or the air electrode 12. By firing the green layer, the fuel electrode 11 or the air electrode 12 is obtained.
  • the firing conditions such as the firing temperature may be appropriately determined according to the type of each material used for the fuel electrode 11 and the air electrode 12.
  • materials constituting the fuel electrode 11 and the air electrode 12 materials used for a known SOFC fuel electrode and air electrode can be used, respectively.
  • binders and solvents used in the preparation of the slurry for the fuel electrode 11 and the air electrode 12 and binders and solvents known in the SOFC fuel electrode and air electrode manufacturing methods are known. Can be selected as appropriate.
  • the electrolyte-supporting cell 1 of the present embodiment is a solid-state electrolyte sheet for SOFC that can suppress a decrease in oxygen ion conductivity even when exposed to an atmosphere containing a sulfur component. It is provided as an electrolyte layer. Therefore, the electrolyte-supporting cell 1 of the present embodiment can suppress a decrease in durability even when fuel containing a sulfur component is supplied to the fuel electrode.
  • the single cell for SOFC of the present embodiment includes a fuel electrode, an air electrode, and a solid electrolyte layer disposed between the fuel electrode and the air electrode. At least one selected from the fuel electrode, the air electrode, and the solid electrolyte layer, It is stabilized with scandium oxide (Sc 2 O 3 ) and cerium oxide (CeO 2 ), and is rare earth oxide (hereinafter referred to as rare earth oxide C) of 0.003 mol% or more and less than 0.5 mol%.
  • rare earth oxide C is an oxide of at least one element selected from rare earth elements excluding Sc and Ce Is, Or Zirconia-based oxide stabilized with scandium oxide (Sc 2 O 3 ) and containing rare earth oxide (hereinafter sometimes referred to as rare earth oxide D) in an amount of 0.003 mol% to less than 0.5 mol% (Scandia-stabilized zirconia-based oxide) as an electrolyte component, and the rare earth oxide D is an oxide of at least one element selected from rare earth elements excluding Sc.
  • 0.003 mol% or more and less than 0.5 mol% rare earth oxide C means that the total amount of rare earth oxide C is 0.003 mol% or more and less than 0.5 mol%. means.
  • 0.003 mol% or more and less than 0.5 mol% rare earth oxide D means that the total amount of rare earth oxide D is 0.003 mol% or more and less than 0.5 mol%. . The same applies to the subsequent steps.
  • the SOFC single cell of this embodiment is made of zirconia in which at least one selected from the fuel electrode, the air electrode, and the solid electrolyte layer is stabilized with scandium oxide (Sc 2 O 3 ) as an electrolyte component. It contains a zirconia-based oxide (scandia-stabilized zirconia-based oxide) to which a trace amount of rare-earth oxide of 0.003 mol% or more and less than 0.5 mol% is added.
  • cerium oxide (CeO 2 ) added as an oxide is 0.5 mol% or more
  • cerium oxide (CeO 2 ) functions as a zirconia stabilizer
  • other rare earth elements other than Ce Zirconia-based oxides scandiaceria-stabilized zirconia-based oxides
  • scandiaceria-stabilized zirconia-based oxides added in an amount of 0.003 mol% or more and less than 0.5 mol%
  • zirconia-based oxide (the scandiaceria-stabilized zirconia-based oxide and the scandia-stabilized zirconia-based oxide) may be referred to as “zirconia-based oxide of this embodiment”.
  • the solid electrolyte layer contains the zirconia-based oxide of the present embodiment
  • the solid electrolyte layer can suppress a decrease in oxygen ion conductivity even when it is exposed to an atmosphere containing a sulfur component. Therefore, the SOFC single cell provided with such a solid electrolyte layer is a case where hydrogen generated by reforming city gas is used as a fuel, and the fuel may contain a sulfur component. Even in some cases, the decrease in durability can be kept small.
  • a desulfurization device is often provided along with the reformer.
  • the configuration of the single cell for SOFC of the present embodiment has an excellent effect particularly when applied to an internal reforming SOFC.
  • the zirconia-based oxide of the present embodiment may be included in the fuel electrode and / or the air electrode as part of the electrode composition.
  • the fuel electrode generally includes a conductive component for imparting conductivity and an electrolyte component as a skeleton component as main constituent materials. Therefore, even when a fuel containing a sulfur component is supplied to the fuel electrode by including the zirconia-based oxide of the present embodiment as an electrolyte component in the fuel electrode, the electrolyte component and the sulfur component in the fuel electrode The formation of this compound and the deposition and adhesion of sulfur components on the electrolyte surface are suppressed.
  • the SOFC single cell of the present embodiment includes the scandiaceria-stabilized zirconia-based oxide as an electrolyte component in at least one selected from a fuel electrode, an air electrode, and a solid electrolyte layer (form) 3-A) and a form (form 3-B) in which at least one selected from a fuel electrode, an air electrode, and a solid electrolyte layer contains the scandia-stabilized zirconia-based oxide as an electrolyte component, respectively explain.
  • the zirconia-based oxide contained as an electrolyte component in at least one selected from the fuel electrode, the air electrode, and the solid electrolyte layer is scandium oxide (Sc 2 O 3 ) and
  • the rare earth oxide C is stabilized with cerium oxide (CeO 2 ) and contains 0.003 mol% or more and less than 0.5 mol%.
  • the rare earth oxide C is an oxide of at least one element selected from rare earth elements excluding Sc and Ce.
  • the rare earth oxide C is at least one selected from the group consisting of Y, La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. It is an oxide of an element.
  • an electrolyte component contained as a main component in the solid electrolyte layer may be composed of this zirconia-based oxide.
  • the solid electrolyte layer is zirconia in which 0.003 mol% or more and less than 0.5 mol% of rare earth oxide C is further solid-dissolved in zirconia in which scandium oxide and cerium oxide are dissolved as stabilizers.
  • the total amount of rare earth oxide C in the zirconia-based oxide is preferably 0.005 mol% to 0.4 mol%, and more preferably 0.01 mol% to 0.3 mol%.
  • the decrease in the conductivity of the solid electrolyte layer that occurs in an atmosphere containing a sulfur component causes the electrolyte component to form a compound with the sulfur component, or the sulfur component to deposit and adhere to the electrolyte surface. It is thought that it happens by doing.
  • rare earth oxide C contained in a trace amount within a range of 0.003 mol% to less than 0.5 mol% Has the effect of suppressing the formation of a compound of an electrolyte component and a sulfur component, deposition and adhesion of the sulfur component to the electrolyte surface, and the like.
  • the content of the rare earth oxide C is less than 0.003 mol%, the effect of suppressing the adverse effect of the sulfur component due to the rare earth oxide C on the electrolyte component is not sufficiently exhibited, and the atmosphere in which the solid electrolyte layer contains the sulfur component When exposed to oxygen, it is difficult to keep the oxygen ion conductivity change with time small.
  • the content of the rare earth oxide C is 0.5 mol% or more, it is expected that the sulfur component easily deposits and adheres to the surface of the electrolyte or reacts easily with the electrolyte component. As a result, as the inflow of fuel proceeds, the conductivity of the solid electrolyte layer gradually deteriorates. Accordingly, when the zirconia-based oxide constituting the electrolyte component contains the rare earth oxide C excessively, the change with time of the conductivity of the solid electrolyte layer becomes large.
  • the rare earth oxide C contained as a trace component is selected from the group consisting of Y, La, Pr, Nd, Sm, Gd, and Yb in order to more reliably suppress the temporal change in oxygen ion conductivity caused by the sulfur component. It is preferably an oxide of at least one element selected from the group consisting of Y, Sm, Gd, and Yb, and more preferably an oxide of at least one element selected from the group consisting of Y, Sm, Gd, and Yb.
  • the rare earth oxide C is gadolinium oxide (Gd 2 O 3 ).
  • gadolinium oxide (Gd 2 O 3 ) is contained in the zirconia-based oxide in Form 3-A as rare earth oxide C, among other rare earth oxides, formation of a compound of an electrolyte component and a sulfur component, Highly effective in suppressing the deposition and adhesion of sulfur components to the electrolyte surface. Therefore, when the zirconia-based oxide in Form 3-A contains gadolinium oxide (Gd 2 O 3 ) as the rare earth oxide C, the change over time in the oxygen ion conductivity caused by the sulfur component can be more reliably suppressed. Can do.
  • the zirconia-based oxide in Form 3-A contains gadolinium oxide (Gd 2 O 3 ), the content is preferably 0.003 mol% or more and 0.2 mol% or less. This is because when the content of gadolinium oxide (Gd 2 O 3 ) exceeds 0.2 mol%, the effect cannot be enhanced to the extent that it matches the content of gadolinium oxide (Gd 2 O 3 ).
  • the zirconia-based oxide in Form 3-A contains gadolinium oxide (Gd 2 O 3 ), it is preferable that yttrium oxide (Y 2 O 3 ) is further added as rare earth oxide C.
  • the sulfur component is an electrolyte. The effect of suppressing adverse effects on the components can be further improved.
  • the content of yttrium oxide (Y 2 O 3 ) is 0.003. A particularly excellent effect can be obtained when the content is in the range of from mol% to 0.2 mol%.
  • the zirconia-based oxide in Form 3-A preferably contains scandium oxide (Sc 2 O 3 ) in an amount of 8 mol% to 15 mol%, and contains 8.5 mol% to 12 mol%. It is more preferable that it is contained in an amount of 9 mol% or more and 11 mol% or less.
  • Sc 2 O 3 scandium oxide
  • the zirconia-based oxide in Form 3-A preferably contains cerium oxide (CeO 2 ) in an amount of 0.5 mol% to 2.5 mol%, preferably 0.6 mol% to 2 mol%. It is more preferable that it is contained in an amount of 0.7 mol% or more and 1.5 mol% or less.
  • CeO 2 cerium oxide
  • the zirconia-based oxide in Form 3-A may be included in the fuel electrode and / or the air electrode as part of the electrode composition.
  • the effects obtained when this zirconia-based oxide is contained in the fuel electrode and / or the air electrode are as described above.
  • the zirconia-based oxide contained as an electrolyte component in at least one selected from the fuel electrode, the air electrode, and the solid electrolyte layer is scandium oxide (Sc 2 O 3 ). It is stabilized and is composed of a zirconia-based oxide containing rare earth oxide D of 0.003 mol% or more and less than 0.5 mol%.
  • the rare earth oxide D is an oxide of at least one element selected from rare earth elements excluding Sc.
  • the rare earth oxide D is at least one selected from the group consisting of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. It is an oxide of a seed element.
  • an electrolyte component contained as a main component in the solid electrolyte layer may be composed of this zirconia-based oxide.
  • the solid electrolyte layer is a zirconia oxide in which 0.003 mol% or more and less than 0.5 mol% of rare earth oxide D is further dissolved in zirconia in which scandium oxide is dissolved as a stabilizer.
  • the sintered body may be formed.
  • the total amount of rare earth oxide D in the zirconia-based oxide is preferably 0.005 mol% or more and 0.4 mol% or less, and more preferably 0.01 mol% or more and 0.3 mol% or less.
  • the decrease in the conductivity of the solid electrolyte layer that occurs in an atmosphere containing a sulfur component occurs due to the electrolyte component forming a compound with the sulfur component, or the sulfur component being deposited or adhered to the electrolyte surface.
  • the rare earth oxide D contained in a trace amount within the range of 0.003 mol% or more and less than 0.5 mol% includes an electrolyte component and a sulfur component. It has the effect of suppressing the formation of the compound and the deposition and adhesion of sulfur components to the electrolyte surface.
  • the content of the rare earth oxide D is less than 0.003 mol%, the effect of suppressing the adverse effect of the sulfur component due to the rare earth oxide D on the electrolyte component is not sufficiently exhibited, and the atmosphere in which the solid electrolyte layer contains the sulfur component When exposed to oxygen, it is difficult to keep the oxygen ion conductivity change with time small.
  • the content of the rare earth oxide D is 0.5 mol% or more, it is expected that the sulfur component is likely to be deposited and adhered to the surface of the electrolyte, or to react with the electrolyte component. As a result, as the inflow of fuel proceeds, the conductivity of the solid electrolyte layer gradually deteriorates. Therefore, when the zirconia-based oxide constituting the electrolyte component contains the rare earth oxide D excessively, the change with time of the conductivity of the solid electrolyte layer becomes large.
  • the rare earth oxide D contained as a trace component is a group consisting of Y, La, Ce, Pr, Nd, Sm, Gd, and Yb in order to more reliably suppress the temporal change in oxygen ion conductivity caused by the sulfur component.
  • the oxide is an oxide of at least one element selected from the group consisting of Y, Ce, Sm, Gd, and Yb. More preferred.
  • the rare earth oxide D is cerium oxide (CeO 2 ).
  • cerium oxide (CeO 2 ) is contained as the rare earth oxide D in the zirconia-based oxide in Form 3-B, particularly among rare earth oxides, formation of a compound of an electrolyte component and a sulfur component, Highly effective in suppressing deposition and adhesion of sulfur components. Therefore, when the zirconia-based oxide in Form 3-B contains cerium oxide (CeO 2 ) as the rare earth oxide D, the change over time in the oxygen ion conductivity caused by the sulfur component can be more reliably suppressed. .
  • the zirconia-based oxide in Form 3-B contains cerium oxide (CeO 2 )
  • its content is preferably 0.1 mol% or more, and more preferably 0.2 mol% or more.
  • its content is preferably 0.48 mol% or less, and more preferably 0.45 mol% or less.
  • the zirconia-based oxide in Form 3-B when the rare earth oxide D is gadolinium oxide (Gd 2 O 3 ), a high effect of suppressing change with time in oxygen ion conductivity can be obtained.
  • the zirconia-based oxide in Form 3-B contains gadolinium oxide (Gd 2 O 3 )
  • its content is preferably 0.003 mol% or more and 0.2 mol% or less, and 0.005 mol% or more 0.1 mol% or less is more preferable.
  • the zirconia-based oxide in Form 3-B when the rare earth oxide D is yttrium oxide (Y 2 O 3 ), a high effect of suppressing change with time in oxygen ion conductivity can be obtained.
  • the zirconia-based oxide in Form 3-B contains yttrium oxide (Y 2 O 3 )
  • its content is preferably 0.003 mol% or more and 0.2 mol% or less, and 0.005 mol% or more 0.1 mol% or less is more preferable.
  • the zirconia-based oxide in Form 3-B may contain both gadolinium oxide (Gd 2 O 3 ) and yttrium oxide (Y 2 O 3 ) as rare earth oxide D.
  • the electrolyte component of the solid electrolyte layer of Form 3-B is composed of a zirconia-based oxide containing both gadolinium oxide (Gd 2 O 3 ) and yttrium oxide (Y 2 O 3 ) as rare earth oxide D. The effect of suppressing the adverse effect of the sulfur component on the electrolyte component can be further improved.
  • gadolinium oxide (Gd 2 O 3 ) and yttrium oxide (Y 2 O 3 ) are not clear, but gadolinium oxide (Gd 2 O 3 ) and yttrium oxide (Y 2 O). 3 ) is preferably from 0.003 mol% to 0.2 mol%, more preferably from 0.005 mol% to 0.1 mol%.
  • the zirconia-based oxide in Form 3-B preferably contains scandium oxide (Sc 2 O 3 ) in an amount of 4 mol% to 15 mol%.
  • the zirconia-based oxide contains scandium oxide (Sc 2 O 3 ) in an amount of 4 mol% to 6.5 mol%. Is preferred.
  • the zirconia-based oxide preferably contains scandium oxide (Sc 2 O 3 ) in an amount of 9 mol% to 13 mol%. 9.5 mol% or more and 12 mol% or less, more preferably 10 mol% or more and 11.5 mol% or less.
  • the type of the SOFC single cell of the present embodiment refers to both the single cell for SOFC of form 3-A and the single cell for SOFC of form 3-B).
  • the configuration of the single cell for SOFC of this embodiment is an electrolyte support cell (hereinafter sometimes referred to as “ESC”) and a fuel electrode support cell (hereinafter sometimes referred to as “ASC”). It can be applied to any of an air electrode support cell (hereinafter sometimes referred to as “CSC”) and a metal support cell (hereinafter sometimes referred to as “MSC”).
  • ESC electrolyte support cell
  • ASC fuel electrode support cell
  • CSC air electrode support cell
  • MSC metal support cell
  • the single cell for SOFC of this embodiment is a fuel electrode support type cell
  • the SOFC single cell 2 of the present embodiment is disposed between the fuel electrode active layer (fuel electrode) 21, the air electrode 22, and the fuel electrode active layer 21 and the air electrode 22.
  • a solid electrolyte layer 23 and a fuel electrode support substrate 24 provided on the surface of the fuel electrode active layer 21 opposite to the solid electrolyte layer 23 and supporting the fuel electrode active layer 21, solid electrolyte layer 23, and air electrode 22.
  • the fuel electrode support substrate 24 and the fuel electrode active layer 21 are formed of a material containing a conductive component and a skeleton component.
  • the conductive component is a component for imparting conductivity to the fuel electrode support substrate 24 and the fuel electrode active layer 21.
  • the skeletal component is a component that forms the skeleton of the fuel electrode support substrate 24 and the fuel electrode active layer 21, and is an important component in securing necessary strength.
  • As the conductive component a known material used for the fuel electrode of the single cell for SOFC can be used. It is desirable that the skeletal component contains the zirconia-based oxide of this embodiment.
  • the skeleton component may be a combination of the zirconia-based oxide of this embodiment and another material known as a skeleton component of the fuel electrode.
  • the thickness of the fuel electrode active layer 21 is not particularly limited, but is preferably 5 ⁇ m or more, more preferably 7 ⁇ m or more, and further preferably 10 ⁇ m or more.
  • the thickness of the anode active layer 11 is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and further preferably 30 ⁇ m or less. If the thickness of the fuel electrode active layer 21 is within the above range, the electrode reaction is efficiently performed, and the power generation performance becomes better when the fuel electrode support cell is used.
  • the thickness of the fuel electrode support substrate 24 is not particularly limited, but is preferably, for example, 100 ⁇ m or more, more preferably 120 ⁇ m or more, and further preferably 150 ⁇ m or more. Further, the thickness of the fuel electrode support substrate 14 is preferably 3 mm or less, more preferably 2 mm or less, further preferably 1 mm or less, and particularly preferably 500 ⁇ m or less. If the thickness of the fuel electrode support substrate 34 is within the above range, the mechanical strength and gas permeability of the fuel electrode support substrate 24 can be easily balanced.
  • the solid electrolyte layer 23 desirably contains the zirconia-based oxide of the present embodiment.
  • the solid electrolyte layer 23 may be formed of the sintered body of the zirconia-based oxide of the present embodiment. That is, the electrolyte component contained in the solid electrolyte layer 23 may be made of the zirconia-based oxide of the present embodiment.
  • the solid electrolyte layer 23 may be a sintered body of a mixture of the zirconia-based oxide of the present embodiment and another material known as a material for the solid electrolyte layer for SOFC.
  • the electrolyte component contained in the solid electrolyte layer 23 may be a mixture of the zirconia-based oxide of this embodiment and another material known as a material for the solid electrolyte layer for SOFC.
  • the zirconia-based oxide of the present embodiment is desirably contained in an amount of 50% by mass or more, and more desirably 70% by mass or more.
  • the thickness of the solid electrolyte layer 23 is not particularly limited, but is preferably 3 ⁇ m or more, more preferably 4 ⁇ m or more, and further preferably 5 ⁇ m or more, for example. Further, the thickness of the solid electrolyte layer 23 is desirably 50 ⁇ m or less, more desirably 30 ⁇ m or less, and further desirably 20 ⁇ m or less. When the thickness of the solid electrolyte layer 23 is within the above range, when the fuel electrode support cell is used, the power generation performance is improved while preventing gas cross-leakage.
  • the air electrode 22 is generally made of a perovskite oxide that has excellent electron conductivity and is stable even in an oxidizing atmosphere. Specifically, La 0.8 Sr 0.2 MnO 3 , La 0.6 Sr 0.4 CoO 3 , La 0.6 Sr 0.4 FeO 3 and La 0.6 Sr 0.4 Co 0.2 Lanthanum manganite, lanthanum ferrite, lanthanum cobaltite, etc. in which a part of lanthanum such as Fe 0.8 O 3 is substituted with strontium are preferably used. Moreover, the air electrode 22 may contain the zirconia-type oxide of this embodiment.
  • the thickness of the air electrode 22 is not particularly limited, but is preferably 5 ⁇ m or more, more preferably 7 ⁇ m or more, and further preferably 10 ⁇ m or more. Further, the thickness of the air electrode 12 is desirably 80 ⁇ m or less, more desirably 70 ⁇ m or less, and further desirably 60 ⁇ m or less. When the thickness of the air electrode 22 is within the above range, the electrode reaction is efficiently performed, and the power generation performance is improved when the fuel electrode support cell is used. *
  • a raw material powder of the zirconia-based oxide of the present embodiment is prepared. Since this raw material powder can be manufactured using the same method as the raw material powder of the zirconia-based oxide contained in the electrolyte sheet of Embodiment 1, detailed description is omitted here.
  • An example of a method for manufacturing the single cell 2 for SOFC includes a step of producing a multilayer fired body including the fuel electrode support substrate 24, the fuel electrode active layer 21, and the solid electrolyte layer 23, and the obtained multilayer fired body is formed into a predetermined shape. And the step of producing the air electrode 22 on the surface opposite to the fuel electrode active layer 21 in the multilayer fired body cut into a predetermined shape.
  • the multilayer fired body (1) On a green sheet for the anode support substrate 24, a layer formed by screen printing for the anode active layer 21, a green layer such as a green sheet layer, and screen printing for the solid electrolyte layer 23, etc. A method of firing the whole or all at once after forming a laminate in which green layers such as formed layers and green sheet layers are sequentially stacked, Or (2) The green sheet for the fuel electrode support substrate 24 is fired to produce the fuel electrode support substrate 24, and the green layer for the fuel electrode active layer 21 and the green layer for the solid electrolyte layer 23 are sequentially formed thereon. A method of firing these after forming stacked laminates, Can be used.
  • the method for producing a multilayer fired body will be described by taking the method (1) as an example.
  • a green sheet for the fuel electrode support substrate 24 is prepared.
  • the green sheet for the fuel electrode support substrate 24 is a mixture of raw material powder (conductive component powder and skeletal component powder), a binder and a solvent, and further, if necessary, a pore forming agent, a dispersing agent, a plasticizer and the like.
  • the materials that can be used as the conductive component and the skeleton component are as described above.
  • the pore-forming agent, binder, solvent, dispersant, plasticizer, and the like can be selected from pore-forming agents, binders, solvents, dispersants, plasticizers, and the like that are known in the manufacturing method of the SOFC fuel electrode support substrate. It can be selected as appropriate.
  • the green layer for the fuel electrode active layer 21 is formed on the green sheet for the fuel electrode support substrate 24 using the paste for the fuel electrode active layer 21.
  • the paste for the anode active layer 21 is a mixture of raw material powder (conductive component powder and skeletal component powder), a binder and a solvent, and further, a pore forming agent, a dispersing agent, a plasticizer and the like are added as necessary. To be prepared. This paste is applied on a green sheet for the fuel electrode support substrate 24 by using a method such as screen printing, and dried to form a green layer for the fuel electrode active layer 21.
  • the materials that can be used as the conductive component and the skeleton component are as described above.
  • the pore-forming agent, binder, solvent, dispersant, plasticizer, etc. are selected from among pore-forming agents, binders, solvents, dispersants, plasticizers, etc. known in the SOFC fuel electrode active layer manufacturing method. It can be selected as appropriate.
  • the green layer for the solid electrolyte layer 23 is formed on the green layer for the fuel electrode active layer 21 using the paste for the solid electrolyte layer 23.
  • the paste for the solid electrolyte layer 23 is prepared by mixing at least a powder that is a raw material for the electrolyte component and a solvent.
  • the materials that can be used as the electrolyte component are as described above.
  • As the solvent used for the paste for the solid electrolyte layer 23 a known material used in preparing a solid electrolyte layer paste of SOFC can be used.
  • a binder, a dispersant, a plasticizer, a surfactant, an antifoaming agent, and the like may be added to the paste for the solid electrolyte layer 23 in addition to the powder and solvent that are the raw materials for the electrolyte component.
  • Binders, dispersants, plasticizers, surfactants, antifoaming agents, etc. are among the binders, dispersants, plasticizers, surfactants, antifoaming agents, etc. known in the SOFC solid electrolyte layer manufacturing method. Can be selected as appropriate.
  • a green layer for a barrier layer may be formed on the green layer for the solid electrolyte layer 23.
  • the green layer for the barrier layer is prepared by preparing a paste containing the raw material powder constituting the barrier layer and applying it to the green layer for the solid electrolyte layer 23. It can be formed by drying.
  • Laminates formed by sequentially stacking are fired collectively or sequentially.
  • the firing temperature of the laminate is not particularly limited, but is preferably 1100 ° C. or higher, more preferably 1200 ° C. or higher, and further preferably 1250 ° C. or higher.
  • the firing temperature is preferably 1500 ° C. or lower, more preferably 1400 ° C. or lower, and further preferably 1350 ° C. or lower.
  • the firing time during firing is not particularly limited, but is preferably 0.1 hours or longer, more preferably 0.5 hours or longer, and even more preferably 1 hour or longer.
  • the firing time is preferably 10 hours or less, more preferably 7 hours or less, and even more preferably 5 hours or less.
  • a multilayer fired body is obtained by the method as described above. Next, the obtained multilayer fired body is cut and / or punched into a predetermined shape.
  • the air electrode 22 is produced on the surface opposite to the fuel electrode support substrate 24.
  • a green layer for the air electrode 22 is formed using the paste for the air electrode 22, and the air electrode 22 is produced by firing the green layer.
  • the paste for the air electrode 22 is prepared by uniformly mixing together the raw material powder, the binder, and the solvent that constitute the air electrode 22 and, if necessary, the dispersant, the plasticizer, and the like.
  • the materials that can be used as the material constituting the air electrode 22 are as described above.
  • the binder, solvent, dispersant, plasticizer, and the like can be appropriately selected from binders, solvents, dispersants, plasticizers, and the like that are known in the SOFC air electrode manufacturing method.
  • the prepared paste is applied on the multilayer fired body by screen printing or the like and dried to form a green layer for the air electrode 22. By baking this, the air electrode 22 is produced.
  • a calcination temperature is not specifically limited, 800 degreeC or more is desirable, 850 degreeC or more is more desirable, and 950 degreeC or more is still more desirable.
  • the firing temperature is preferably 1400 ° C. or lower, more preferably 1350 ° C. or lower, and further preferably 1300 ° C. or lower.
  • the firing time during firing is not particularly limited, but is preferably 0.1 hours or longer, more preferably 0.5 hours or longer, and even more preferably 1 hour or longer.
  • the firing time is preferably 10 hours or less, more preferably 7 hours or less, and even more preferably 5 hours or less.
  • the SOFC single cell 2 can be manufactured by the method as described above.
  • the fuel electrode support type cell has been described as an example. However, even in the case of an electrolyte support type cell, an air electrode support type cell, and a metal support type cell, the zirconia-based oxidation of the present embodiment is similarly applied. It is possible to use the object for the fuel electrode, the air electrode and / or the solid electrolyte layer.
  • the SOFC of this embodiment includes the electrolyte-supported cell described in Embodiment 2 or the SOFC single cell described in Embodiment 3.
  • the SOFC of this embodiment includes, for example, a plurality of single cells that are stacked and connected in series (stacked). At this time, the adjacent single cells are electrically connected to each other, and at the same time, the fuel gas and the oxidant gas are properly distributed to the fuel electrode and the air electrode through the manifold, respectively.
  • a separator is arranged. The separator is also called an interconnector.
  • the single cell used in the SOFC of the present embodiment is less likely to be deteriorated in durability even when exposed to an atmosphere containing a sulfur component. Therefore, the durability of the SOFC of the present embodiment is not easily lowered even when exposed to an atmosphere containing a sulfur component.
  • the SOFC of the present embodiment is a case where hydrogen generated by reforming city gas is used as a fuel, and even if the fuel may contain a sulfur component, A decrease in durability can be kept small.
  • a desulfurization device is often provided along with the reformer.
  • the configuration of the SOFC of the present embodiment has an excellent effect particularly when an internal reforming SOFC is used.
  • xSc yCe zGd SZ refers to x mol% scandium oxide (Sc 2 O 3 ), y mol% cerium oxide (CeO 2 ), and z mol% gadolinium oxide ( Gd 2 O 3 ) and the remaining zirconium oxide (ZrO 2 ) means stabilized zirconia.
  • a neutralization coprecipitation reaction was carried out while finely adjusting the liquid speed of the mixed aqueous solution and aqueous ammonia so that the pH was in the range of 8.5 ⁇ 0.2 during the reaction.
  • the hydroxide in the effluent was separated from the mother liquor by filtration and then the ammonium chloride was removed by repeated washing with water.
  • the obtained hydroxide was dispersed in n-butanol and dehydrated by performing atmospheric distillation until the solution temperature reached 105 ° C.
  • the n-butanol dispersion containing the dehydrated hydroxide was spray-dried to obtain a powder with good fluidity. This powder was fired at 1000 ° C. for 1 hour to obtain a 10Sc1Ce0.1Gd0.05YSZ powder (sample 1 in Table 1) having a specific surface area of 9 m 2 / g and no agglomerates.
  • a predetermined amount of zirconium oxychloride, scandium chloride, cerium chloride, and a rare earth oxide were prepared so as to have the compositions of Samples 2 to 16 shown in Table 1.
  • the zirconia-based oxide powders of Samples 17 to 31 have a predetermined amount of zirconium oxychloride, scandium chloride, and a trace amount of rare earth oxide so as to have the compositions of Samples 17 to 31 shown in Table 2.
  • Al 2 O 3 , SiO 2 , TiO 2 , Fe 2 O 3 , Na 2 O, CaO 2 and Cl are also detected as impurities.
  • the amount of SiO 2 is in the zirconia powder. 0.005 mass% for less impurities excluding SiO 2 was 0.001 mass% as trace amount, respectively.
  • the composition calculation method of each zirconia-based oxide powder will be described below.
  • the obtained slurry was transferred to a jacketed round bottom cylindrical vacuum degassing vessel having an internal volume of 50 L equipped with a bowl-shaped stirrer, and the jacket temperature was adjusted to 40 ° C. while rotating the stirrer at a speed of 30 rpm.
  • the slurry was concentrated and degassed under a pressure of ⁇ 21 kPa, and the viscosity at 25 ° C. was adjusted to 3 Pa ⁇ s to obtain a slurry for coating.
  • This coating slurry was continuously coated on a polyethylene terephthalate (PET) film by a doctor blade method.
  • PET polyethylene terephthalate
  • a long green tape was obtained by drying at 40 ° C., 80 ° C., and 110 ° C. This green tape was cut into a circular shape of about 38 mm ⁇ with a punching blade (manufactured by Nakayama Paper Equipment Co., Ltd.) and further peeled from the PET film to prepare each zirconia green sheet
  • a fuel electrode paste containing 65 parts by mass and 35 parts by mass of commercially available 8YSZ-based powder (manufactured by Daiichi Rare Element Co., Ltd., HSY-8.0) was applied by screen printing and dried. I let you.
  • each electrolyte sheet On the other side of each electrolyte sheet, a commercially available strontium-doped lanthanum manganese composite oxide powder (manufactured by AGC Seimi Chemical Co., Ltd .: La 0.6 An air electrode paste containing 80 parts by mass of Sr 0.4 MnO 3 ) and 20 parts by mass of a commercially available 20 mol% gadolinia dope ceria powder (manufactured by AGC Seimi Chemical Co., Ltd .: GDC20) was applied by screen printing and dried. Next, each electrolyte sheet coated with electrodes on both sides was baked at 1300 ° C. for 3 hours to form a 30-mm ⁇ 30-mm ⁇ three-layer structure in which a fuel electrode layer having a thickness of 40 ⁇ m and an air electrode layer having a thickness of 30 ⁇ m were formed. Each ESC shown in Tables 3 and 4 was prepared.
  • a slurry was prepared. This slurry is put in a vacuum degassing machine, and the vertical stirring blade immersed in the slurry is concentrated and degassed while rotating at a rotation speed of 10 rpm for 24 hours, and the viscosity at 25 ° C. is adjusted to 8 Pa ⁇ s.
  • a slurry for coating was obtained. This coating slurry was continuously applied onto a PET film by a doctor blade method, and then dried at 40 ° C., 80 ° C., and 110 ° C. to obtain a long green tape. This green tape was cut to about 38 mm ⁇ with a punching blade, and further peeled from the PET film to produce a 3YSZ / NiO green sheet.
  • This green sheet is sandwiched between 99.5% nickel aluminate porous plates (porosity: 30%) with a maximum ridge height of 10 ⁇ m so that the peripheral edge of the green sheets does not protrude, and a shelf plate with a thickness of 20 mm (
  • the product was placed on a product name “Dialite DC-M” manufactured by Tokai Koetsu Kogyo Co., Ltd. and fired at 1350 ° C.
  • a fuel electrode support substrate having a circular shape of 30 mm ⁇ and a thickness of 0.5 mm was produced.
  • the fuel electrode paste used in (5) (i) above was applied to the obtained fuel electrode support substrate by screen printing except for the 3 mm wide periphery from the periphery of the fuel electrode support substrate, dried, and then 1300 A fuel electrode supporting substrate with a fuel electrode active layer was produced by firing at 0 ° C.
  • Each slurry for electrolyte membrane was apply
  • 10Sc1CeSZ powders (samples 15 and 16)) obtained in step 1) were formed to a thickness of 5 ⁇ m to form an electrolyte layer, on which a commercially available strontium-doped lanthanum iron cobalt complex oxide was formed.
  • An air electrode layer was formed by laminating powder of (La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 ) to a thickness of 30 ⁇ m by thermal spraying, and two types of MSCs shown in Table 6 were formed. Produced.
  • the obtained strip-shaped electrolyte sheet was used as a test piece, and in an electric furnace maintained at 800 ° C., air containing 10 ppm of tertiary butyl mercaptan (sulfur compound) (hereinafter, sulfur component-containing air) was circulated for 100 hours. Thereafter, the oxygen ion conductivity of the test piece was measured after 1000 hours and 2000 hours, and for Samples 1, 2, 15, 20, 28, and 31 after 3000 hours had elapsed.
  • sulfur compound sulfur compound
  • gold wires 32 a to 32 d having a diameter of 0.2 mm are wound around 4 pieces at 1 cm intervals around a test piece 31, coated with gold paste, dried and fixed at 100 ° C.
  • a current / voltage terminal is used, and both ends of the test piece 31 wound with the gold wires 32a and 32d are sandwiched between alumina plates 33 so that the gold wires 32a and 32d are in close contact with the test piece 31, and a load 34 of about 500 g is applied from above.
  • the temperature is kept at 800 ° C., a constant current of 0.1 mA is applied to the outer two terminals (gold wires 32a and 32d), and the voltage of the inner two terminals (gold wires 32b and 32c) is changed to a digital multimeter (Advantest). (Trade name “TR6845 type”) (not shown) was used, and the measurement was performed by the direct current four-terminal method. Also, a gold wire was used for a lead wire (not shown).
  • test piece was disposed so as to be located at the center of the glass tube placed on the tubular electric furnace. By continuously circulating the sulfur component-containing air from one end of the glass tube to the other, the test piece was always exposed to the sulfur component-containing air.
  • Tables 1 and 2 show the results of the decrease rate of the conductivity of each electrolyte sheet.
  • the result of the rate of decrease in conductivity for the electrolyte sheet of Sample 16 was prepared using the same green sheet as Sample 15 as a reference example for confirming that the conductivity is decreased by the sulfur component-containing air. It is a result at the time of changing the air which a test piece is exposed in the said evaluation test method from the sulfur component containing air to the air which does not contain a sulfur component using a test piece.
  • the rate of decrease in conductivity after 100 hours is 2% or more in the 10Sc1Ce1AlSZ electrolyte sheet (sample 14) and the 9Sc1AlSZ electrolyte sheet (sample 30), but in other electrolyte sheets, A large difference was not confirmed at 1.7% or less.
  • the electrolyte sheet satisfying the requirements of the electrolyte sheet of the present invention that is, stabilized with Sc 2 O 3 and CeO 2 shown in Table 1, and 0.003 mol% or more and 0.5
  • An electrolyte sheet composed of zirconia-based oxides containing less than mol% rare earth oxide A electrolyte sheets of Examples 1 to 11 (Examples)
  • Sc 2 O 3 shown in Table 2
  • the decrease rate was less than 8%
  • the decrease rate of the conductivity of the electrolyte sheets (Comparative Examples) of Samples 12 to 15 and 28 to 31 that did not satisfy the requirements of the electrolyte sheet of the present invention was Less than 8% It was on.
  • the electrolyte sheet satisfying the requirements of the electrolyte sheet of the present invention has a small decrease in conductivity after 2000 hours, and further has a larger difference in decrease in conductivity after 3000 hours. From this result, it was confirmed that the electrolyte sheet of the present invention has a small change with time in the oxygen ion conductivity in an atmosphere containing a sulfur component.
  • 41 is an electric furnace
  • 42 is a zirconia outer tube
  • 43 is a zirconia inner tube
  • 44 is a gold lead wire
  • 45 is a solid electrolyte layer
  • 46 is a sealing material
  • 48 is an air electrode
  • 47 is a fuel. Show poles.
  • the operating temperature was 850 ° C.
  • the operating temperature was 750 ° C.
  • the operating temperature was 700 ° C.
  • the product name “TR6845” manufactured by Advantest Corporation was used as the voltage measuring device
  • the product name “GPO16-20R” manufactured by Takasago Seisakusho was used as the current voltage generator.
  • a constant current of 0.3 A / cm 2 was applied to the fuel electrode side under a flow of 1 liter / min of hydrogen containing 10 ppm of tertiary butyl mercaptan as a fuel gas and air as an oxidant on the air electrode side. While driving.
  • Table 3 shows the rate of decrease in power generation characteristics of ESCs (ESC-1 to ESC-7 (Examples)) in which electrolyte sheets composed of zirconia-based oxides including rare earth oxide A are used. Thus, even after 2000 hours, it was less than 14%.
  • the rate of decrease in power generation characteristics was 16% or more. The difference in the rate of decrease in power generation characteristics between cells that satisfy the requirements of the single cell of the present invention and cells that do not satisfy the requirement became larger after 3000 hours, and the rate of decrease in power generation characteristics reached 5% or more.
  • a cell satisfying the requirements of the single cell of the present invention shown in Table 4, that is, a rare earth oxide of 0.003 mol% or more and less than 0.5 mol% that is stabilized with Sc 2 O 3 in the solid electrolyte layer ESCs (ESC-11 to ESC-17 (examples)) in which an electrolyte sheet composed of a zirconia-based oxide containing B is used are shown in Table 4. Even after 2000 hours, it was less than 15%. In contrast, in ESC-19 and ESC20 (comparative examples) that do not satisfy the requirements of the single cell of the present invention, the rate of decrease in power generation characteristics was 15% or more. In ESC-18, the rate of decrease in power generation characteristics after 2000 hours is kept low.
  • the ESC using the electrolyte sheet of the present invention that is, the electrolyte-supported cell of the present invention, suppresses the rate of decrease in power generation characteristics. I understand that.
  • the rate of decrease in the power generation characteristics of the ASC shown in Table 5 and the MSC shown in Table 6 is also the difference in the rate of decrease in the power generation characteristics between the cells that satisfy the requirements of the single cell of the present invention and the cells that do not satisfy the requirements. It became 5% or more.
  • the single cell of the present invention exhibits excellent durability in a sulfur component-containing atmosphere.
  • the SOFC electrolyte sheet of the present invention can suppress a decrease in durability even when a fuel containing a sulfur compound such as city gas is used. Therefore, the electrolyte sheet for SOFC of the present invention can be suitably used as an electrolyte layer for household SOFC that uses city gas or the like as fuel.
  • the SOFC single cell and SOFC of the present invention can be used as a SOFC that uses city gas or the like as the fuel, for example, because it can suppress a decrease in durability even when the fuel contains a sulfur compound.

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Abstract

La présente invention a trait à une feuille d'électrolyte destinée à une pile à combustible à oxyde solide et qui contient un composant d'électrolyte. Le composant d'électrolyte est constitué d'un oxyde à base de zircone stabilisé par un oxyde de scandium (Sc2O3) et un oxyde de cérium (CeO2) et contenant une quantité supérieure ou égale à 0,003 % en moles et inférieure à 0,5 % en moles d'un oxyde de terres rares (l'oxyde d'au moins un élément choisi parmi les éléments de terres rares à l'exclusion de Sc et Ce), ou est constitué d'un oxyde à base de zircone stabilisé par un oxyde de scandium (Sc2O3) et contenant une quantité supérieure ou égale à 0,003 % en moles et inférieure à 0,5 % en moles d'un oxyde de terres rares (l'oxyde d'au moins un élément choisi parmi les éléments de terres rares à l'exclusion de Sc).
PCT/JP2013/005745 2012-09-26 2013-09-26 Feuille d'électrolyte destinée à une pile à combustible à oxyde solide, pile supportant un électrolyte, pile unique destinée à une pile à combustible à oxyde solide, et pile à combustible à oxyde solide WO2014050124A1 (fr)

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CN104685684A (zh) 2015-06-03

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