KR100352099B1 - 혼합이온 전도체 및 이것을 이용한 장치 - Google Patents

혼합이온 전도체 및 이것을 이용한 장치 Download PDF

Info

Publication number
KR100352099B1
KR100352099B1 KR1020000007509A KR20000007509A KR100352099B1 KR 100352099 B1 KR100352099 B1 KR 100352099B1 KR 1020000007509 A KR1020000007509 A KR 1020000007509A KR 20000007509 A KR20000007509 A KR 20000007509A KR 100352099 B1 KR100352099 B1 KR 100352099B1
Authority
KR
South Korea
Prior art keywords
ion conductor
mixed ion
less
present
mixed
Prior art date
Application number
KR1020000007509A
Other languages
English (en)
Other versions
KR20010014488A (ko
Inventor
다니구치노보루
Original Assignee
마쯔시다덴기산교 가부시키가이샤
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 마쯔시다덴기산교 가부시키가이샤 filed Critical 마쯔시다덴기산교 가부시키가이샤
Publication of KR20010014488A publication Critical patent/KR20010014488A/ko
Application granted granted Critical
Publication of KR100352099B1 publication Critical patent/KR100352099B1/ko

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4073—Composition or fabrication of the solid electrolyte
    • G01N27/4074—Composition or fabrication of the solid electrolyte for detection of gases other than oxygen
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B35/46—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 titanium oxides or titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6261—Milling
    • C04B35/62615—High energy or reactive ball milling
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6261—Milling
    • C04B35/6262—Milling of calcined, sintered clinker or ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • C04B35/6264—Mixing media, e.g. organic solvents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/6268—Thermal treatment of powders or mixtures thereof other than sintering characterised by the applied pressure or type of atmosphere, e.g. in vacuum, hydrogen or a specific oxygen pressure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215—Barium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3239—Vanadium oxides, vanadates or oxide forming salts thereof, e.g. magnesium vanadate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3241—Chromium oxides, chromates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3256—Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3258—Tungsten oxides, tungstates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3289—Noble metal oxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3289—Noble metal oxides
    • C04B2235/3291—Silver oxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3294—Antimony oxides, antimonates, antimonites or oxide forming salts thereof, indium antimonate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3296—Lead oxides, plumbates or oxide forming salts thereof, e.g. silver plumbate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/768—Perovskite structure ABO3
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Composite Materials (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • Thermal Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Conductive Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Fuel Cell (AREA)

Abstract

본 발명은 연료전지 등에서의 사용환경을 고려하여, 페로브스카이트(perovskite)형 산화물 혼합이온 전도체의 화학적 안정성을 더욱 더 개선하고자 한 것이다.
식 Baa(Ce1-bM1 b)LcO3-r(M1은 Ce를 제외한 3가 희토류 원소, L은 Zr, Ti, V, Nb, Cr, Mo, W, Fe, Co, Ni, Cu, Ag, Au, Pd, Pt, Bi, Sb, Sn, Pb 및 Ga 중에서 선택된 적어도 한 종류의 원소, a는 0. 9이상 1이하, b는 0.16이상 0.26이하, c는 0.01이상 0.1이하, r은 (2+b-2a)/2이상 1.5미만)으로 나타낸 페로브스카이트형 산화물로 이루어진 혼합이온 전도체로 한다. 또는 바륨 지르코늄계 또는 바륨 지르코늄 세륨계 페로브스카이트형 산화물로 이루어진 혼합이온 전도체로 한다.

Description

혼합이온 전도체 및 이것을 이용한 장치{Mixed ions containing conductor and device using the same}
본 발명은 혼합이온 전도체 및 이것을 이용한 연료전지, 가스센서 등 전기화학 장치에 관한 것이다.
본 출원인은 프로톤과 산소이온의 혼합이온 전도체에 대해서, 개발을 계속해 왔다(특개평 5-28820호 공보, 특개평 6-236114호 공보 등). 이 혼합이온 전도체는 기본적으로 바륨, 세륨을 기제로 한 페로브스카이트형 산화물로, 세륨의 일부를 치환원소(M)로 치환함으로써, 높은 이온전도체를 발생시킨 것이었다(일반식 : BaCe1-pMpO3-q). 특히 치환원소(M)의 치환량(p)을 0.16에서 0.23으로 하면 높은 도전성을 가지고, 종래 산소이온 전도체로서 이용되어져 왔던 지르코니아계 산화물(YSZ : 산화이트륨 안정화 지르코니아)보다도 고이온 전도성을 얻을 수 있었다. 치환원소(M)로는 희토류 원소가 적당하고, 특히 중희토류 원소는 원자반경 및 전하 밸런스의 관점에서 가장 적합하다.
이 재료를 고체 전해질로 이용한 새로운 연료전지, 센서 등, 전기화학장치도 개발되어져 왔다. 이 재료를 이용한 연료전지의 방전특성이나, 센서 특성은 종래에 없는 뛰어난 특성을 나타내고, 공업적으로도 뛰어난 것이 실제로 입증되고 있다. 이들의 관련특허출원으로는 특개평 5-234604호 공보, 특개평 5-290860호 공보, 특개평 6-223857호 공보, 특개평 6-290802호 공보, 특개평 7-65839호 공보, 특개평 7-136455호 공보, 특개평 8-29390호 공보, 특개평 8-162121호 공보, 특개평 8-220060호 공보 등이 있다.
그러나, 상기 재료는 화학적 안정성의 점에서 전혀 문제가 없는 것은 아닌데, 예를 들면 탄산가스 중에서는 바륨이 석출되는 경우가 있다. 이 문제에 대해 본 출원인은 특개평 8-107918호 공보에서 대책을 제시했다. 그러나, 상기 대책은 최선이 아니라 예를 들어, 저온 85℃, 습도 85%중에서의 방치시험 또는 수중열탕시험에서는 바륨의 석출이 관찰되었다. 또, 연료전지에서의 방전중과 같은 고수증기압하에서는 백금전극 근방에서 바륨의 편석이 보였다. 한편, 가스센서 등에서는 저온에서의 고이온 전도성의 장기유지나 산화물 자체의 내산성의 향상이 문제였다.
따라서, 본 발명은 본 출원인이 제안해 온 혼합이온 전도체의 화학적 안정성을 더욱 더 개선하는 것을 목적으로 한다.
상기 페로브스카이트형 산화물의 습도에 의한 부식의 주된 원인은 산화물 중의 편석 바륨이 일단 수산화바륨이 된 후에 탄산가스와 반응하여, 안정된 탄산바륨을 형성하기 때문이라고 추정된다. 따라서, 내습성을 증가시키기 위해, 본 발명에서는 이하의 페로브스카이트형 산화물로 이루어진 혼합이온 전도체를 이용한 것으로 했다.
즉, 본 발명의 제1 혼합이온 전도체는 식Baa(Ce1-bM1 b)LcO3-r(단, M1은 Ce를 제외한 3가 희토류 원소, L은 Zr, Ti, V, Nb, Cr, Mo, W, Fe, Co, Ni, Cu, Ag, Au, Pd, Pt, Bi, Sb, Sn, Pb 및 Ga 중에서 선택된 적어도 한 종류의 원소, a는 0. 9이상 1이하, b는 0.16이상 0.26이하, c는 0.01이상 0.1이하, r은 (2+b-2a)/2이상 1.5미만)으로 나타낸 페로브스카이트형 산화물로 이루어진 것을 특징으로 한다.
상기 혼합이온 전도체에서는 M1은 La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Y 및 Sc 중에서 선택된 적어도 한 종류의 원소인 것이 바람직하고, 특히 Gd 및 Y 중에서 선택된 적어도 한 종류의 원소가 적합하다.
또, L은 Zr, Ti, Fe, Co, Ni, Cu, Bi, Sn, Pb 및 Ga 중에서 선택된 적어도 한 종류의 원소가 바람직하고, Zr, Ti, Bi, Pb 및 Ga 중에서 선택된 적어도 한 종류의 원소가 더욱 바람직하다.
본 발명의 제2 혼합이온 전도체는 식BaeZr1-zM2 zO3-s(단, M2는 3가 희토류 원소, Bi, Ga, Sn, Sb 및 In 중에서 선택된 적어도 한 종류의 원소, e는 0.9이상 1이하, z는 0.01이상 0.3이하, s는 (2+z-2e)/2이상 1.5미만)으로 나타낸 페로브스카이트형 산화물로 이루어진 것을 특징으로 한다.
상기 혼합이온 전도체에서는 z는 0.16이상 0.3이하가 바람직하다. 또, M2은 3가 희토류 원소 및 In 중에서 선택된 적어도 한 종류의 원소가 바람직하고, Pr, Eu, Gd, Yb, Sc 및 In 중에서 선택된 적어도 한 종류의 원소가 더 바람직하다.
본 발명의 제3 혼합이온 전도체는 식BadZr1-x-yCexM3 yO3-t(M3는 3가 희토류 원소, Bi, Ga, Sn, Sb 및 In 중에서 선택된 적어도 한 종류의 원소, d는 0.98이상 1이하, x는 0.01이상 0.5이하, y는 0.01이상 0.3이하, t는 (2+y-2d)/2이상 1.5미만)으로 나타낸 페로브스카이트형 산화물로 이루어진 것을 특징으로 한다.
상기 제3 혼합이온 전도체에서는 M3이 Nd, Sm, Eu, Gd, Tb, Yb, Y, Sc 및 In중에서 선택된 적어도 한 종류의 원소인 것이 바람직하고, 특히 Gd, In, Y 및 Yb 중에서 선택된 적어도 한 종류의 원소가 적합하다.
본 발명의 혼합이온 전도체는 연료전지 등의 전기화학장치에 필요한 도전성을 가지면서 뛰어난 내습성도 겸비하고 있다.
또, 본 명세서에서 희토류 원소로는 Sc, Y 및 란탄족 원소(원자번호 57(La)∼71(Lu))를 지칭한다. 또, 상기 각 식에서 r, s 및 t는 부정비의 산소결손량에 의해 정해진다.
본 발명은 상기 혼합이온 전도체를 이용한 장치도 제공한다. 즉, 본 발명의 연료전지는 상기 혼합이온 전도체를 고체 전해질로 포함하는 것을 특징으로 한다. 또, 본 발명의 가스센서는 상기 혼합이온 전도체를 고체 전해질로서 포함하는 것을 특징으로 한다. 본 발명의 혼합이온 전도체를 이용함으로써, 내습성이 높고, 수명이 길며 고성능인 연료전지, 가스 센서 등의 전기장치가 된다.
도 1은 본 발명의 혼합이온 전도체를 이용한 연료전지의 일형태를 도시한 단면 절결도,
도 2는 본 발명의 혼합이온 전도체를 이용한 가스센서의 일형태를 도시한 단면도,
도 3은 본 발명의 혼합이온 전도체의 도전율의 예를 도시한 그래프이다.
<도면의 주요부분에 대한 부호의 설명>
1, 15 : 양극(공기극) 2, 14 : 고체 전해질
3, 16 : 음극(연료극) 4 : 분리기
5 : 연료가스(수소, 천연가스) 6 : 산화가스(공기)
7 : 적층유닛 13 : 확산률 조절구멍
17 : 기판 18 : 무기 접착제
19 : 히터
이하, 본 발명의 바람직한 실시형태에 대해서 설명한다.
본 발명의 혼합이온 전도체의 높은 전도성은 본 출원인에 의한 상기 공보에 기재된 바와 같이, 산소이온과 프로톤의 혼합이온 전도성에서 유래된다. 이 혼합이온 전도체의 내습성을 개선하기 위해, 상기 제1 혼합이온 전도체에서는 페로브스카이트형 산화물 중의 바륨량을 화학량론비 이하로 하여 적절한 치환원소를 도입하도록 했다. 이하, 혼합이온 전도체를 「첨가물계」전도체라고 한다.
또, 본 발명에 의하면, 내습성이 높은 혼합이온 전도체로서 상기 제2 혼합이온 전도체와 상기 제3 혼합이온 전도체가 제공된다. 이하, 이들의 혼합이온 전도체는 각각 「바륨 지르코늄계」전도체, 「바륨 지르코늄 세륨계」전도체라 한다. 이들 계에서는 프로톤 전도성을 나타내는 혼합이온 전도체이면서 높은 내습성을 얻을 수 있다.
상기 각 계의 혼합이온 전도체는 종래로부터 이용되어져 온 원료와 제조를 적용하면 얻을 수 있다. 제조의 일예는 실시예로서 후술한다.
이하, 본 발명의 혼합이온 전도체를 이용한 장치의 예에 대해서 설명한다.
도 1은 본 발명의 연료전지의 일형태의 사시도이다. 이 평판의 연료전지에는 고체 전해질(2)을 통해 양극(공기극)(1) 및 음극(연료극)(3)이 적층되어 있다. 그리고, 이 적층유닛(7) 사이에 분리기(4)가 사이에 끼워진 구조를 가지고 있다.
발전시에는 양극(1)에는 산화가스(6)(예를 들면 공기)가 공급되고, 음극(3)에는 연료가스(5)(예를 들면, 수소, 천연가스 등의 환원가스)가 공급된다. 각 전극에서의 산화환원반응에 따라 발생하는 전자는 외부로 꺼내진다.
도 2는 본 발명의 가스센서의 일형태의 단면도이다. 이 HC센서(탄화수소 센서)는 고체 전해질(14)을 통해 양극(15)과 음극(16)이 적층되어 있다. 이 적층채는 기판(세라믹 기판)(17)상의 사이에 공간이 유지되도록, 이 기판상에 무기접착제(18)로 고정되어 있다. 이 내부공간(20)은 확산률 조절구멍(13)을 통해 외부로 도통되어 있다.
이 센서에서는 양극(15, 16)간에 소정의 전압(예를 들면 1.2V)을 인가한 상태를 유지하면, 양극(15)에 접하는 공간에 존재하는 탄화수소의 농도에 따른 전류값이 출력으로서 얻어진다. 센서는 측정시에는 기판에 부착된 히터(19)에 의해 소정온도로 유지된다. 내부공간(20)으로 유입된 측정종류(탄화수소)의 유입량을 제한하기 위해 확산률 조절구멍(13)을 설치하는 것이 바람직하다.
또, 상기에서는 HC센서에 대해서 설명했지만 도시한 구조에서 양극과 음극을 바꿔넣으면, 산소센서로 할 수도 있다. 또, 본 발명의 혼합이온 전도체는 상기에 한하지 않고 각종의 전기화학장치에 적용할 수 있다.
(실시예)
이하, 본 발명을 실시예에 의해 더 상세히 설명하겠는데, 본 발명은 이하의 실시예에 의해 제한되는 것은 아니다.
본 실시예에서는 (표 1)∼(표 6)에 나타낸 페로브스카이트형 산화물을 합성했다. 각 산화물의 합성은 고상반응법을 이용했다. 바륨, 세륨, 지르코늄, 희토류 원소 등 각 원소의 산화분말을 각각 표 중의 조성비가 되도록 칭량하고, 마노 모르타르(agate mortar)중에서 에탄올 용매를 사용하여 분쇄 및 혼합했다. 충분히 혼합한 후, 용매를 비산시키고, 또 버너를 이용하여 탈지하고 다시 마노 모르타르 중에서 분쇄 및 혼합을 반복했다. 그 후, 원주형상으로 프레스성형하여 1300℃에서 10시간 소성했다. 소성 후, 대강 분쇄하여 다시 벤젠 용매 중에서 유성 볼 밀(ball mill) 분쇄에 의해 3㎛정도의 입자로 제조했다. 얻어진 분말을 150℃ 진공건조한 후, 2톤/㎠에서의 정수압 프레스에 의해 원주로 성형한 직후 1650℃에서 10시간 소성하여 소결체를 합성했다. 대부분의 샘플에 대해서는 충분히 치밀하게 단상 페로브스카이트형 산화물이 얻어졌다. 이렇게 얻은 각 샘플에 대해서 이하의 항목을 평가했다.
·열탕시험
내습시험의 가속시험으로서 100℃의 비등수 중에 샘플을 투입하여, Ba의 석출정도를 10시간후의 pH값으로 평가했다. 바륨의 석출과 함께 수용액 중의 pH값이 증가하는 것을 이용한 평가법이다. 내습성은 pH변화가 2이하인 경우를 아주 좋음(A), 2를 넘고 3.5이하인 경우를 좋음(B), 3.5를 넘고 4이하인 경우를 보통(C), 4를 넘는 경우를 나쁨(D)으로 판정했다.
·도전율
다음에, 상기 열탕시험 후의 샘플을 원주 소결체로부터 두께 0.5㎜로 직경 13㎜의 디스크상에 가공하고, 그 디스크의 양면에 각각 0.5㎠의 면적이 되도록 백금 페이스트를 도포해서 도금하여, 이온도전율 측정용 시료로 했다. 이 시료의 도전율은 공기중, 교류 임피던스법에 의한 저항값으로부터 산출했다. 측정온도는 500℃이다. 측정장치 중의 리드저항성분은 완전히 보정했다. 도전율(S/㎝)은 0.007이상을 A, 0.001이상 0.007미만을 B, 0.001미만을 C로 판정했다.
또, 도 3에 본 발명의 재료의 도전율의 일예를 아레니우스 플롯(Arrhenius plot)으로 나타낸다.
· 결정성
소결 후, 단상이 된 경우를 A, 다상이 된 경우를 B, 소결불가능한 경우를 C로 판정했다.
또, 각 표에 각각의 500℃에서의 도전율과 열탕시험의 pH평가결과와 함께 나타낸다.
(표 1)
(표 2)
(표 3)
(표 4)
(표 5)
(표 6)
평가 결과로부터 알 수 있는 바와 같이, 본 발명의 혼합이온 전도체는 내습성은 현저히 향상하고, 또 이온 전도성도 실용적인 레벨을 유지하고 있다.
본 실시예에서는 고상 소결법을 이용하여 합성했지만, 이것에 한정되지 않고 예를 들면 공침법, 질산염법, 스프레이 과립법 등의 수법을 이용하여 산화물을 합성해도 된다. 또, CVD법, 스퍼터링법 등의 성막법을 적용해도 된다. 또, 열 스프레이에 의해 제작해도 된다. 산화물의 형상도 한정되지 않고, 벌크나 막을 포함하는 어떤 형상이어도 된다.
이상과 같이, 본 발명의 혼합이온 전도체에 의하면 내습성이 현저히 향상하고, 또 이온전도성도 실용적인 레벨을 유지할 수 있다.

Claims (13)

  1. 삭제
  2. 삭제
  3. 삭제
  4. 삭제
  5. 삭제
  6. 삭제
  7. 삭제
  8. 삭제
  9. 식 BadZr1-x-yCexM3 yO3-t로 표시되고, 상기 식 중 M3는 3가 희토류 원소, Bi, Ga, Sn, Sb 및 In 중에서 선택된 적어도 한 종류의 원소, d는 0.98이상 1이하, x는 0.01이상 0.5이하, y는 0.01이상 0.3이하, t는(2+y-2d)/2이상 1.5미만인 페로브스카이트형 산화물로 이루어진 것을 특징으로 하는 혼합이온 전도체.
  10. 제 9항에 있어서, M3은 Nd, Sm, Eu, Gd, Tb, Yb, Y, Sc 및 In 중에서 선택된 적어도 한 종류의 원소인 것을 특징으로 하는 혼합이온 전도체.
  11. 제 10항에 있어서, M3은 Gd, In, Y 및 Yb 중에서 선택된 적어도 한 종류의 원소인 것을 특징으로 하는 혼합이온 전도체.
  12. 제 9항에 기재된 혼합이온 전도체를 고체 전해질로서 포함하는 것을 특징으로 하는 연료전지.
  13. 제 9항에 기재된 혼합이온 전도체를 고체 전해질로서 포함하는 것을 특징으로 하는 가스 센서.
KR1020000007509A 1999-02-17 2000-02-17 혼합이온 전도체 및 이것을 이용한 장치 KR100352099B1 (ko)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP99-038369 1999-02-17
JP3836999 1999-02-17

Related Child Applications (2)

Application Number Title Priority Date Filing Date
KR1020020022461A Division KR100352096B1 (ko) 1999-02-17 2002-04-24 혼합이온 전도체 및 이것을 이용한 장치
KR1020020022462A Division KR100352097B1 (ko) 1999-02-17 2002-04-24 혼합이온 전도체 및 이것을 이용한 장치

Publications (2)

Publication Number Publication Date
KR20010014488A KR20010014488A (ko) 2001-02-26
KR100352099B1 true KR100352099B1 (ko) 2002-09-12

Family

ID=12523378

Family Applications (3)

Application Number Title Priority Date Filing Date
KR1020000007509A KR100352099B1 (ko) 1999-02-17 2000-02-17 혼합이온 전도체 및 이것을 이용한 장치
KR1020020022462A KR100352097B1 (ko) 1999-02-17 2002-04-24 혼합이온 전도체 및 이것을 이용한 장치
KR1020020022461A KR100352096B1 (ko) 1999-02-17 2002-04-24 혼합이온 전도체 및 이것을 이용한 장치

Family Applications After (2)

Application Number Title Priority Date Filing Date
KR1020020022462A KR100352097B1 (ko) 1999-02-17 2002-04-24 혼합이온 전도체 및 이것을 이용한 장치
KR1020020022461A KR100352096B1 (ko) 1999-02-17 2002-04-24 혼합이온 전도체 및 이것을 이용한 장치

Country Status (5)

Country Link
US (3) US6528195B1 (ko)
EP (3) EP1029837B1 (ko)
KR (3) KR100352099B1 (ko)
CA (1) CA2298850A1 (ko)
DE (2) DE60002510T2 (ko)

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6517693B2 (en) * 2000-02-14 2003-02-11 Matsushita Electric Industrial Co., Ltd. Ion conductor
AUPQ653700A0 (en) * 2000-03-28 2000-04-20 Ceramic Fuel Cells Limited Surface treated electrically conductive metal element and method of forming same
WO2002013302A1 (en) * 2000-08-07 2002-02-14 Energieonderzoek Centrum Nederland Mixed oxide material, electrode and method of manufacturing the electrode and electrochemical cell comprising it
NL1015886C2 (nl) * 2000-08-07 2002-02-08 Stichting Energie Elektrode voor een elektrochemische cel.
US6770392B2 (en) * 2001-04-27 2004-08-03 Air Products And Chemicals, Inc. Ceria based solid electrolytes
ITMI20011519A1 (it) 2001-07-17 2003-01-17 Uni Degli Studi Di L Aquila Soluzioni solide a struttura perovskitica comprendenti metali nobili utili come catalizzatori
US7235171B2 (en) * 2001-07-24 2007-06-26 Matsushita Electric Industrial Co., Ltd. Hydrogen sensor, hydrogen sensor device and method of detecting hydrogen concentration
JP4162599B2 (ja) * 2002-03-08 2008-10-08 阿南化成株式会社 セリウム系複合酸化物、その焼結体及び製造法
EP1369949B1 (en) * 2002-06-06 2013-01-30 Panasonic Corporation Solid electrolyte fuel cell and manufacturing method thereof
WO2004074175A1 (ja) * 2003-02-24 2004-09-02 National University Corporation Nagoya University 水素ガス分離装置
JP4330151B2 (ja) 2003-02-24 2009-09-16 東京窯業株式会社 プロトン−電子混合伝導性セラミックス
EP1662512B1 (en) * 2003-09-03 2013-07-24 Panasonic Corporation Mixed ion conductor
US7625653B2 (en) * 2005-03-15 2009-12-01 Panasonic Corporation Ionic conductor
JP2007317627A (ja) * 2006-05-29 2007-12-06 Toyota Motor Corp 燃料電池
JP2008243627A (ja) * 2007-03-27 2008-10-09 Toyota Motor Corp プロトン伝導体、電気化学セル、およびプロトン伝導体の製造方法
WO2009025553A1 (en) * 2007-08-22 2009-02-26 Stichting Energieonderzoek Centrum Nederland Electrode for fixed oxide reactor and fixed oxide reactor
CN102123792B (zh) * 2009-04-28 2014-09-03 松下电器产业株式会社 光激发半导体和使用它的设备
US8906818B2 (en) 2009-10-13 2014-12-09 Recapping, Inc. High energy density ionic dielectric materials and devices
KR100985381B1 (ko) * 2009-12-22 2010-10-05 신일피엔에스 주식회사 합성수지 직포대의 접착방법 및 상기 방법으로 접착된 직포대
RU2495854C1 (ru) * 2012-04-03 2013-10-20 Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук Твердый электролит на основе оксида церия и церата бария
US9437343B2 (en) 2013-07-16 2016-09-06 Panasonic Intellectual Property Management Co., Ltd. Proton conductor
JP6132259B2 (ja) * 2013-07-18 2017-05-24 住友電気工業株式会社 燃料電池用複合材料、燃料電池用複合材料の製造方法及び燃料電池
JP6191090B2 (ja) 2013-08-27 2017-09-06 住友電気工業株式会社 燃料極用電極材料、固体電解質−電極積層体、固体電解質−電極積層体の製造方法及び燃料電池
WO2015114684A1 (ja) 2014-01-31 2015-08-06 パナソニックＩｐマネジメント株式会社 プロトン伝導体
US9458544B2 (en) 2014-02-07 2016-10-04 Panasonic Intellectual Property Management Co., Ltd. Organic hydride conversion device
US9896771B2 (en) 2014-02-07 2018-02-20 Panasonic Intellectual Property Management Co., Ltd. Dehydrogenation device
RU2550816C1 (ru) * 2014-05-16 2015-05-20 Открытое акционерное общество "ТВЭЛ" (ОАО "ТВЭЛ") Катодный материал для тотэ на основе медь-содержащих слоистых перовскитоподобных оксидов
CN104689817B (zh) * 2014-12-12 2017-02-22 湖北航特科技有限责任公司 一种机动车尾气净化用复合氧化物催化剂及其制备方法
US9527033B2 (en) * 2015-01-23 2016-12-27 Toyota Motor Engineering & Manufacturing North America, Inc. Mixed metal oxide catalyst
KR20170132140A (ko) * 2015-03-30 2017-12-01 스미토모덴키고교가부시키가이샤 프로톤 전도체, 연료 전지용 고체 전해질층, 셀 구조체 및 그것을 구비하는 연료 전지
CN111189901B (zh) * 2020-01-13 2021-06-29 吉林大学 Gd2Zr2O7固体电解质型甲醛传感器及其制备方法

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2882104B2 (ja) 1991-07-17 1999-04-12 松下電器産業株式会社 プロトン伝導体およびその製造方法
JP3160993B2 (ja) 1992-02-20 2001-04-25 松下電器産業株式会社 固体電解質型燃料電池
JPH05290860A (ja) 1992-04-09 1993-11-05 Matsushita Electric Ind Co Ltd 固体電解質型燃料電池の作製法
JPH06223857A (ja) 1993-01-25 1994-08-12 Matsushita Electric Ind Co Ltd 平板型固体電解質型燃料電池の連続放電装置
JP2864928B2 (ja) 1993-02-04 1999-03-08 松下電器産業株式会社 混合イオン導電体
JP3055350B2 (ja) 1993-04-01 2000-06-26 松下電器産業株式会社 バリウムセリウム型固体電解質燃料電池の運転方法
JP3340526B2 (ja) 1993-08-23 2002-11-05 松下電器産業株式会社 バリウムセリウム系酸化物固体電解質用の還元極およびその製造法
JP3253198B2 (ja) 1993-11-24 2002-02-04 松下電器産業株式会社 窒素酸化物還元装置
US6033632A (en) * 1993-12-08 2000-03-07 Eltron Research, Inc. Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them
EP0677741A3 (en) 1994-04-12 1996-05-01 Matsushita Electric Ind Co Ltd Oxygen sensor.
JP2948124B2 (ja) 1994-04-12 1999-09-13 松下電器産業株式会社 酸素センサー
JP3449642B2 (ja) 1994-07-12 2003-09-22 松下電器産業株式会社 一酸化炭素センサー
JPH08162121A (ja) 1994-12-07 1996-06-21 Matsushita Electric Ind Co Ltd バリウムセリウム系酸化物固体電解質燃料電池用燃料極およびその製造方法
JP3760475B2 (ja) 1995-01-19 2006-03-29 東ソー株式会社 ホタル石型ジルコニア系固体電解質
JP3498772B2 (ja) 1995-03-31 2004-02-16 株式会社豊田中央研究所 薄膜式ガスセンサ及びその製造方法
JPH0927330A (ja) 1995-07-11 1997-01-28 Tokyo Gas Co Ltd 固体電解質燃料電池の燃料極
JP2951887B2 (ja) 1996-04-26 1999-09-20 松下電器産業株式会社 混合イオン導電体
US6235417B1 (en) 1999-04-30 2001-05-22 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Natural Resources Two-phase hydrogen permeation membrane

Also Published As

Publication number Publication date
KR20010014488A (ko) 2001-02-26
KR100352096B1 (ko) 2002-09-13
KR20020053787A (ko) 2002-07-05
US7491461B2 (en) 2009-02-17
EP1281694B1 (en) 2008-08-27
EP1029837B1 (en) 2003-05-07
EP1029837A2 (en) 2000-08-23
CA2298850A1 (en) 2000-08-17
EP1284249A1 (en) 2003-02-19
EP1281694A1 (en) 2003-02-05
EP1029837A3 (en) 2000-09-20
US20050260477A1 (en) 2005-11-24
KR100352097B1 (ko) 2002-09-13
US6528195B1 (en) 2003-03-04
DE60002510D1 (de) 2003-06-12
DE60040097D1 (de) 2008-10-09
US20030124403A1 (en) 2003-07-03
KR20020053786A (ko) 2002-07-05
DE60002510T2 (de) 2004-04-08

Similar Documents

Publication Publication Date Title
KR100352099B1 (ko) 혼합이온 전도체 및 이것을 이용한 장치
JP4608047B2 (ja) 混合イオン伝導体およびこれを用いたデバイス
JP4608506B2 (ja) 混合イオン伝導体およびこれを用いたデバイス
JP3733030B2 (ja) イオン伝導体
US4562124A (en) Air electrode material for high temperature electrochemical cells
EP0896378B1 (en) Solid electrolyte type fuel battery
Alcock et al. Perovskite electrodes for sensors
US6517693B2 (en) Ion conductor
KR101165124B1 (ko) 이온 전도체
US20040214070A1 (en) Low sintering lanthanum ferrite materials for use as solid oxide fuel cell cathodes and oxygen reduction electrodes and other electrochemical devices
JP2000251533A (ja) 酸化物イオン混合伝導体とその用途
KR102399154B1 (ko) Co 및 Ti로 치환된 층상 페로브스카이트를 포함하는 고체산화물 연료전지용 공기극 소재, 및 이를 포함하는 고체산화물 연료전지용 공기극
JP4589683B2 (ja) 混合イオン伝導体
Tu et al. Gd1− x A x Mn1− y Co y O 3− δ (A= Sr, Ca) as a Cathode for Solid‐Oxide Fuel Cells
KR20060119701A (ko) 혼합 이온 전도체
JP2002097021A (ja) 高温導電性酸化物、燃料電池用電極及び該電極を用いた燃料電池
JP3446649B2 (ja) 酸化物イオン伝導体の製造方法
Doshi et al. Oxygen pumping characteristics of oxide ion electrolytes at low temperatures
JPH11228136A (ja) 酸化物イオン導電性材料
JP6819638B2 (ja) 酸化物イオン伝導体及び電気化学デバイス
Marina et al. Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
A107 Divisional application of patent
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20070823

Year of fee payment: 6

LAPS Lapse due to unpaid annual fee