CN105655605A - Cathode catalyst for solid oxide fuel cell, composite cathode material and preparation method thereof - Google Patents

Cathode catalyst for solid oxide fuel cell, composite cathode material and preparation method thereof Download PDF

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CN105655605A
CN105655605A CN201610027063.5A CN201610027063A CN105655605A CN 105655605 A CN105655605 A CN 105655605A CN 201610027063 A CN201610027063 A CN 201610027063A CN 105655605 A CN105655605 A CN 105655605A
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oxide
cathode material
cathod catalyst
composite cathode
doping
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CN105655605B (en
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沈雪松
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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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

Abstract

The invention discloses a cathode catalyst for a solid oxide fuel cell, a composite cathode material and a preparation method thereof. The cathode catalyst is strontium titanate doped with perovskite structure. The chemical formula of (Sr1-xCx)1-nTi1-yDyO3 is met, wherein C is one or more of Mg, Ca and Ba, D is one or more of Sc, V, Cr, Co, Mn, Ni, Fe, Cu, Zn, x and y are the mole percentage contents, x is larger than or equal to 0 or smaller than or equal to 0.95, y is larger than 0 and smaller than or equal to 0.95, and n is larger than or equal to 0 and smaller than or equal to 0.08. The preparation method comprises the step of ball milling mixing, the step of sintering and the step of ball milling again. The invention further discloses the composite cathode material comprising the cathode catalyst for the solid oxide fuel cell. After the cathode catalyst is added, the performance of the solid oxide fuel cell is obviously better than that of the solid oxide fuel cell with no cathode catalyst.

Description

SOFC cathod catalyst, composite cathode material and preparation method thereof
Technical field
The present invention relates to a kind of high-performance solid oxidate combined electrode of fuel cell material, particularly relate to a kind of SOFC cathod catalyst, composite cathode material and preparation method thereof.
Background technology
SOFC is a kind of all solid state energy conversion device that chemical energy in fuel can be converted into electric energy by the mode of electrochemical reaction. It is mainly by anode, negative electrode and electrolyte composition. Generally, oxygen reduction reaction is there is in the air (oxygen) passed in negative electrode at the three phase boundary place of cathode internal, the three phase boundary that the oxonium ion that reaction generates is transmitted to anode interior by solid electrolyte is in hydrogen generation hydroxide reaction, and the electronics that reaction generates flows into negative electrode by external current loop and forms Guan Bi circuit generating acting.
The cathode material of SOFC is mainly mixed by electronic conductive material and oxygen-ion conductive material, oxygen-ion conductive material in negative electrode is generally made up of electrolyte, and current three major types electrolyte is the zirconium oxide (Stabilized-ZrO after stablizing2), the cerium oxide (Doped-CeO of doping2) and Ishihara invention lanthanum gallate series (US6844098B1).
Electronic conductive material in negative electrode is generally made up of five big classes: lanthanum manganate perovskite structural material (JBGoodenough, TheoryoftheRoleofCovalenceinthePerovskite-TypeManganites [LaM (the II)] MnO of doping3, PhysicalReview, 1955,100 (2): 564), cobalt acid lanthanum perovskite structural material (ANPetrov, OFKononchuk, etc., Crystalstructure, the electricalandmagneticpropertiesofLa of doping1-xSrxCoO3SolidStateIonics, 199580 (95): 189), cadmium ferrite perovskite structural material (the YTeraoka of doping, etc., OxygenpermeationThroughPerovskite-TypeOxides, ChemistryLetters, 1985,14 (11): 1743;StructureandElectricalPropertiesofLa1-xSrxCo1-yFeyO3.Part1.ThesystemLa0.8Sr0.2Co1-yFeyO3, 1995,76 (3): 259; StructureandElectricalPropertiesofLa1-xSrxCo1-yFeyO3.Part2.ThesystemLa1-xSrxCo0.2Fe0.8O31995,76 (3): 273), nickel acid lanthanum perovskite structural material (RChiba, etc., the AninvestigationofLaNi of doping1-xFexO3Asacathodematerialforsolidoxidefuelcells, SolidStateIonics, 1999,124 (26): 281) and doping K2NiF4Type structure nickelate (SJSkinner, etc., OxygendiffusionandsurfaceexchangeinLa2-xSrxNiO4SolidStateIonics, 2000,135 (1): 709; A.Aguadero, etc., EvalutionoftheLa2Ni1-xCuxO4systemasSOFCcathodematerialswith8YSZandLSGMaselectrolyte,SolidStateIonics,2008,179(11):393)��
Compared to current applicable combination electrode material, higher cathode performance means higher generating efficiency, such that it is able to reduce the cost of battery pile, plays vital effect to the commercialization of SOFC is universal.
Summary of the invention
Defect for prior art, an object of the present invention is in that to provide a kind of SOFC cathod catalyst, this cathode catalyst material can add in the negative electrode of other all solids oxide fuel cell, reaches to improve the purpose of chemical property.
The two of the purpose of the present invention are in that the preparation method providing a kind of above-mentioned cathod catalyst.
The three of the purpose of the present invention are in that to provide a kind of SOFC composite cathode material comprising above-mentioned cathod catalyst.
The four of the purpose of the present invention are in that the preparation method providing above-mentioned composite cathode material, and the method is simple.
To achieve these goals, present invention employs techniques below scheme:
A kind of SOFC cathod catalyst, described cathod catalyst is the strontium titanates of the perovskite structure of doping, meets following chemical general formula: (Sr1-xCx)1-nTi1-yDyO3, wherein C is one or more in Mg, Ca, Ba, and D is one or more in Sc, V, Cr, Co, Mn, Ni, Fe, Cu, Zn; X, y are the molar content of respective element, and 0��x��0.95,0 < y��0.95; 0��n��0.08.
In above-mentioned cathod catalyst, as a kind of preferred implementation, the granularity of described cathod catalyst is for being not more than 5 ��m; It is highly preferred that the granularity of described cathod catalyst is 0.005��5 ��m; Further, 0��x��0.3,0 < y��0.9, n=0.
The preparation method of above-mentioned cathod catalyst, it is preferred to use solid-phase synthesis is prepared, it is more preferred to, the concrete preparation method of described cathod catalyst powder is as follows:
Ball milling blend step: according to the molar content of elements various in prepared cathod catalyst by the raw material SrCO of respective amount3��TiO2Wet ball grinding is carried out until raw material is sufficiently mixed uniformly with the oxide treating doped chemical;
Sintering step: the product after described wet ball grinding is sintered 5��20 hours after drying at 1100 DEG C��1500 DEG C;
Ball milling step again: the product after sintering is carried out wet ball grinding again until particle diameter meets the requirements.
Comprise the composite cathode material of the SOFC of above-mentioned cathod catalyst.
In above-mentioned composite cathode material, as a kind of preferred implementation, described composite cathode material also includes cathode material and high oxygen-ion conductive material; It is highly preferred that the 0.05-40% that the quality of described cathod catalyst is cathode material, high oxygen-ion conductive material and cathod catalyst quality sum; Further, the quality of described high oxygen-ion conductive material is cathode material and the 30-70% of high oxygen-ion conductive material quality sum.
In above-mentioned composite cathode material, as a kind of preferred implementation, described cathode material is nickelate and the A of the doping of the ferrite of the doping of the cobaltatess of the doping of the manganite of the doping of perovskite structure, perovskite structure, perovskite structure, perovskite structure2NiO4One or more in the nickelate of structure.
In above-mentioned composite cathode material, as a kind of preferred implementation, described high oxygen-ion conductive material is one or more in the zirconium oxide of metal oxide stability, the cerium oxide of doped metallic oxide and the lanthanum gallate of strontium magnesium cobalt codope.
In above-mentioned composite cathode material, as a kind of preferred implementation, in the zirconium oxide of described metal oxide stability, described metal-oxide is one or more in calcium oxide, magnesium oxide, Scia, yittrium oxide, lanthana, praseodymium oxide, Dineodymium trioxide, promethium oxide, Disamarium trioxide, europium oxide, Gadolinia., terbia. Diterbium trioxide, dysprosia, holmia, Erbia, Dithulium trioxide, ytterbium oxide and luteium oxide; It is highly preferred that in the zirconium oxide of described metal oxide stability, the content of described metal-oxide is 1-20mol%.
In above-mentioned composite cathode material, as a kind of preferred implementation, in the cerium oxide of described doped metallic oxide, described metal-oxide is one or more in calcium oxide, magnesium oxide, Scia, yittrium oxide, lanthana, praseodymium oxide, Dineodymium trioxide, promethium oxide, Disamarium trioxide, europium oxide, Gadolinia., terbia. Diterbium trioxide, dysprosia, holmia, Erbia, Dithulium trioxide, ytterbium oxide and luteium oxide; It is highly preferred that the cerium oxide of described doped metallic oxide meets following chemical general formula: Ce1-xMxO2, wherein, 0.05��x��0.3, M is one or more in calcium, magnesium, scandium, yttrium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutecium;
Further, the lanthanum gallate of described strontium magnesium cobalt codope meets following chemical general formula: La0.8Sr0.2Ga0.8Mg0.2-xCoxO3, wherein 0��x��0.15.
The preparation method of the composite cathode material of above-mentioned SOFC, comprises the steps:
Step one, mixes cathode material powder and high oxygen-ion conductive material powder and grinds, obtaining two system combination electrodes; The quality of wherein said high oxygen-ion conductive material powder is the 30%��70% of two system combination electrode gross masses;
Step 2, adds cathod catalyst powder in described two system combination electrodes, mixes and grind, obtaining composite cathode material described in three-system; The quality of wherein said cathod catalyst powder is the 0.05-40% of composite cathode material gross mass described in three-system.
Compared with prior art, there is advantages that
The cathode catalyst material of the present invention can add in the negative electrode of other all solids oxide fuel cell, thus improving chemical property. The performance adding the SOFC after cathod catalyst of the present invention is substantially better than the performance of the SOFC being not added with cathod catalyst.
Accompanying drawing explanation
Fig. 1 is the power generation performance figure of the monocell after adopting the composite cathode material of the embodiment of the present invention 1 preparation to assemble;
Fig. 2 is the power generation performance figure of the monocell after adopting the composite cathode material of the embodiment of the present invention 2 preparation to assemble;
Fig. 3 is the power generation performance figure of the monocell after adopting the composite cathode material of the embodiment of the present invention 3 preparation to assemble.
Detailed description of the invention
In order to make inventive feature, effect etc. clearly, present invention is described in greater detail below.
A kind of SOFC cathod catalyst provided by the invention, described cathod catalyst is the strontium titanates of the perovskite structure of doping, meets following chemical general formula: (Sr1-xCx)1-nTi1-yDyO3, wherein C is one or more in Mg, Ca, Ba, and D is one or more in Sc, V, Cr, Co, Mn, Ni, Fe, Cu, Zn; X and y is the molar content of respective element and 0��x��0.95,0 < y��0.95; 0��n��0.08.
Specifically, cathod catalyst is the strontium titanates (DopedSrTiO of the perovskite structure of a kind of doping3). Doping is divided into two kinds:
The first is only at the strontium titanates SrTiO of B location doping3, meet perovskite structure ABO3Or meet the perovskite structure A of location A defect1-nBO3(0��n��0.08). Namely, only when B location adulterates, the strontium titanates of the perovskite structure of doping has following chemical general formula: A1-nTi1-yDyO3(i.e. (Sr1-xCx)1-nTi1-yDyO3Middle x=0), wherein D is one or more in Sc, V, Cr, Co, Mn, Ni, Fe, Cu, Zn; 0 < y��0.95 (such as 0.01,0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85 or 0.9).
The second is to adulterate at B location again in location A doping. The strontium titanates of the perovskite structure now adulterated has following chemical general formula: (Sr1-xCx)1-nTi1-yDyO3, wherein C is Mg, Ca, one or more in Ba, D is Sc, V, Cr, Co, Mn, Ni, Fe, Cu, one or more in Zn, (such as x is 0.01 in 0 < x��0.95, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85 or 0.9), (such as y is 0.01 in 0 < y��0.95, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85 or 0.9), 0��n��0.08.
Comprehensive both the above doping situation, the cathod catalyst of the present invention has following chemical general formula: (Sr1-xCx)1-nTi1-yDyO3, wherein C is one or more in Mg, Ca, Ba, and D is one or more in Sc, V, Cr, Co, Mn, Ni, Fe, Cu, Zn, 0��x��0.95,0 < y��0.95; 0��n��0.08.
In order to realize good effect, the granularity of cathod catalyst of the present invention is preferably not greater than 5 ��m (such as: 1-5 ��m, 0.5-4 ��m, 0.01-0.1 ��m, 0.05-0.2 ��m, 0.001 ��m, 0.05 ��m, 0.3 ��m, 1.5 ��m, 2 ��m, 2.5 ��m, 3 ��m, 3.5 ��m, 4 ��m, 4.5 ��m, 5 ��m). It is highly preferred that the granularity of described cathod catalyst is 0.005��5 ��m.
In above-mentioned cathod catalyst, described x is preferably: 0��x��0.3, y are preferably: 0 < y��0.9, n are preferably 0.
Above-mentioned cathod catalyst can be prepared by conventional inorganic materials synthesis methods such as solid reaction process, solution combustion synthetic method, coprecipitation, hydrothermal synthesis method, collosol and gel synthetic method, polymer complex methods. Preferably, above-mentioned cathod catalyst adopts solid reaction process to be prepared, and concrete technology is as follows:
Ball milling blend step: according to the molar content of elements various in prepared cathod catalyst by the raw material SrCO of respective amount3��TiO2Wet ball grinding is carried out until raw material is sufficiently mixed uniformly with the oxide of the element treated representated by the oxide of doped chemical and C and/or D;
Sintering step: the product after described wet ball grinding is sintered after drying under 1100 DEG C��1500 DEG C (such as 1110 DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C, 1300 DEG C, 1350 DEG C, 1400 DEG C, 1450 DEG C, 1490 DEG C) 5��20 hours (such as 6h, 8h, 12h, 15h, 18h, 19h);
Ball milling step again: the product after sintering is carried out wet ball grinding again until particle diameter meets the requirements, finally gives cathod catalyst powder.
In the preparation method of above-mentioned cathod catalyst, as a kind of preferred implementation, it is ethanol at the medium of wet ball grinding described in described ball milling blend step, ball material mass ratio is 30/1��50/1 (such as 32:1,38:1,42:1,45:1,48:1), rotating speed is 200��400rpm (such as 210rpm, 250rpm, 300rpm, 320rpm, 340rpm, 360rpm, 380rpm), and Ball-milling Time is 15-30h (such as 16h, 18h, 20h, 24h, 26h, 28h, 29h).
In the preparation method of above-mentioned cathod catalyst, as a kind of preferred implementation, in described ball milling step again, the medium of described wet ball grinding is ethanol, ball material mass ratio is 20/1��40/1 (such as 20:1,25:1,30:1,35:1,40:1), rotating speed is 500��1000rpm (such as 510rpm, 560rpm, 600rpm, 700rpm, 800rpm, 850rpm, 950rpm), and Ball-milling Time is 0.5-10h (such as 0.5h, 1h, 2h, 4h, 6h, 8h, 10h).
The preparation method of cathod catalyst of the present invention is simple, and by first time ball milling by raw material mix homogeneously, sintering makes raw material generation high temperature solid state reaction generate perovskite structure oxide ABO in atmosphere afterwards3Or A1-nBO3, and then sintering afterproduct grinds to form the cathod catalyst powder of fine particle powder and the present invention by ball milling.
A kind of composite cathode material of the SOFC comprising above-mentioned cathod catalyst, described composite cathode material also includes cathode material and high oxygen-ion conductive material; Preferably, the quality of described cathod catalyst is the 0.15-40% (such as 0.16%, 0.2%, 0.3%, 0.4%, 0.8%, 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 39%) of cathode material, high oxygen-ion conductive material and cathod catalyst quality sum; The quality of described high oxygen-ion conductive material is the 30-70% (such as 31%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 69%) of cathode material and high oxygen-ion conductive material quality sum.
In above-mentioned composite cathode material, described cathode material is nickelate (DopedNickelate-BasedPerovskite) and the A of the doping of the ferrite (DopedFerrite-BasedPerovskite) of the doping of the cobaltatess (DopedCobaltite-BasedPerovskite) of the doping of the manganite (DopedManganite-BasedPerovskite) of the doping of perovskite structure, perovskite structure, perovskite structure, perovskite structure2NiO4Nickelate (the A of structure2NiO4TypeNickelate) one or more in. Below these several typical existing cathode materials are illustrated.
The manganite (DopedManganite-BasedPerovskite) of the doping of perovskite structure:
(1) the manganite perovskite AMnO of location A doping3Meet perovskite structure ABO3Or meet the perovskite structure A of location A defect1-nBO3(0��n��0.08). Wherein location A is the combination of lanthanide series and alkaline-earth metal, and namely only when location A adulterates, the manganite perovskite of location A doping meets following chemical general formula: (Ln1-xCx)1-nMnO3, wherein Ln is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and C is one or more in Mg, Ca, Sr, Ba;0 < x��0.95,0��n��0.08.
(2) the manganite perovskite AMn of B location doping1-yDyO3Meet perovskite structure ABO3Or the perovskite structure A of location A defect1-nBO3(0��n��0.08). Wherein B location is the combination of manganese element and variable valency metal, and namely only when B location adulterates, the manganite perovskite of B location doping meets following chemical general formula: A1-nMn1-yDyO3, wherein D is one or more in Sc, Ti, V, Cr, Fe, Co, Ni, Cu, Zn; A is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; 0 < y��0.95,0��n��0.08.
(3) when A and B location adulterate simultaneously, the manganite of the doping of perovskite structure meets following chemical general formula: (Ln1-xCx)1-nMn1-yDyO3, wherein Ln is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and C is one or more in Mg, Ca, Sr, Ba, and D is one or more in Sc, Ti, V, Cr, Fe, Co, Ni, Cu, Zn; 0 < x��0.95,0 < y��0.95,0��n��0.08.
Comprehensive three of the above doping situation, the manganite of the doping of the perovskite structure that the present invention uses preferably meets following chemical general formula: (Ln1-xCx)1-nMn1-yDyO3, wherein Ln is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and C is one or more in Mg, Ca, Sr, Ba, and D is one or more in Sc, Ti, V, Cr, Fe, Co, Ni, Cu, Zn; X, y are the molar content of respective element, and 0��x��0.95 (such as x is 0.01,0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85 or 0.9), 0 < y��0.95 (such as y is 0.01,0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85 or 0.9), 0��n��0.08, is zero during x and y difference.
The cobaltatess (DopedCobaltite-BasedPerovskite) of the doping of perovskite structure:
(1) the cobaltatess perovskite ACoO of location A doping3Meet perovskite structure ABO3Or meet the perovskite structure A of location A defect1-nBO3(0��n��0.08). Wherein location A is the combination of lanthanide series and alkaline-earth metal, and namely only when location A adulterates, the cobaltatess of the doping of perovskite structure meet following chemical general formula: (Ln1-xCx)1-nCoO3, wherein Ln is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; C is one or more in Mg, Ca, Sr, Ba; 0 < x��0.95.
(2) the cobaltatess perovskite ACo of B location doping1-yDyO3Meet perovskite structure ABO3Or meet the perovskite structure A of location A defect1-nBO3(0��n��0.08). Wherein B location is the combination of cobalt element and variable valency metal, and namely only when B location adulterates, the cobaltatess of the doping of perovskite structure meet following chemical general formula: A1-nCo1-yDyO3, wherein A is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and D is one or more in Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn; 0 < y��0.95,0��n��0.08.
(3) when A and B location adulterate simultaneously, the cobaltatess of the doping of perovskite structure meet following chemical general formula: (Ln1-xCx)1-nCo1-yDyO3, wherein Ln is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and C is one or more in Mg, Ca, Sr, Ba, and D is one or more in Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn;0 < x��0.95,0 < y��0.95,0��n��0.08.
Comprehensive three of the above doping situation, the cobaltatess of the doping of the perovskite structure that the present invention uses preferably meet following chemical general formula: (Ln1-xCx)1-nCo1-yDyO3, wherein Ln is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and C is one or more in Mg, Ca, Sr, Ba, and D is one or more in Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn; X, y are the molar content of respective element, and 0��x��0.95 (such as x is 0.01,0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85 or 0.9), 0 < y��0.95 (such as y is 0.01,0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85 or 0.9) 0��n��0.08, is zero during x and y difference.
The ferrite (DopedFerrite-BasedPerovskite) of the doping of perovskite structure:
(1) the ferrite perovskite AFeO of location A doping3Meet perovskite structure ABO3Or meet the perovskite structure A of location A defect1-nBO3(0��n��0.08). Wherein location A is the combination of lanthanide series and alkaline-earth metal, and namely only when location A adulterates, the ferrite of the doping of perovskite structure meets following chemical general formula: (Ln1-xCx)1-nFeO3, wherein Ln is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; C is one or more in Mg, Ca, Sr, Ba; 0 < x��0.95.
(2) the ferrite perovskite AFe of B location doping1-yDyO3Meet perovskite structure ABO3Or meet the perovskite structure A of location A defect1-nBO3(0��n��0.08). Wherein B location is the combination of ferrum element and variable valency metal, and namely only when B location adulterates, the ferrite of the doping of perovskite structure meets following chemical general formula: A1-nFe1-yDyO3, wherein A is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; D is one or more in Sc, Ti, V, Cr, Co, Mn, Ni, Cu, Zn; 0 < y��0.95;
(3) when A and B location adulterate simultaneously, the ferrite of the doping of perovskite structure meets following chemical general formula: (Ln1-xCx)1-nFe1-yDyO3, wherein Ln is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; C is one or more in Mg, Ca, Sr, Ba; D is one or more in Sc, Ti, V, Cr, Co, Mn, Ni, Cu, Zn; 0 < x��0.95; 0 < y��0.95; 0��n��0.08.
Comprehensive three of the above doping situation, the ferrite of the doping of the perovskite structure that the present invention uses preferably meets following chemical general formula: (Ln1-xCx)1-nFe1-yDyO3, wherein Ln is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and C is one or more in Mg, Ca, Sr, Ba, and D is one or more in Sc, Ti, V, Cr, Co, Mn, Ni, Cu, Zn; ; X, y are the molar content of respective element, and 0��x��0.95 (such as x is 0.01,0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85 or 0.9), 0 < y��0.95 (such as y is 0.01,0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85 or 0.9) 0��n��0.08, is zero during x and y difference.
The nickelate (DopedNickelate-BasedPerovskite) of the doping of perovskite structure:
(1) the nickelate perovskite ANiO of location A doping3Meet perovskite structure ABO3Or meet the perovskite structure A of location A defect1-nBO3(0��n��0.08). Wherein location A is the combination of lanthanide series and alkaline-earth metal, and namely only when location A adulterates, the nickelate of the doping of perovskite structure meets following chemical general formula: (Ln1-xCx)1-nNiO3, wherein Ln is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; C is one or more in Mg, Ca, Sr, Ba; 0 < x��0.95.
(2) the ferrite perovskite ANi of B location doping1-yDyO3Meet perovskite structure ABO3Or meet the perovskite structure A of location A defect1-nBO3(0��n��0.08). Wherein B location is the combination of nickel element and variable valency metal, and namely only when B location adulterates, the ferrite of the doping of perovskite structure meets following chemical general formula: A1-nNi1-yDyO3, wherein A is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; D is one or more in Sc, Ti, V, Cr, Co, Mn, Fe, Cu, Zn; 0 < y��0.95;
(3) when A and B location adulterate simultaneously, the nickelate of the doping of perovskite structure meets following chemical general formula: (Ln1-xCx)1-nNi1-yDyO3, wherein Ln is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; C is one or more in Mg, Ca, Sr, Ba; D is one or more in Sc, Ti, V, Cr, Co, Mn, Fe, Cu, Zn; 0 < x��0.95; 0 < y��0.95; 0��n��0.08.
Comprehensive three of the above doping situation, the nickelate of the doping of the perovskite structure that the present invention uses preferably meets following chemical general formula: (Ln1-xCx)1-nNi1-yDyO3, wherein Ln is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and C is one or more in Mg, Ca, Sr, Ba, and D is one or more in Sc, Ti, V, Cr, Co, Mn, Fe, Cu, Zn; ; X, y are the molar content of respective element, and 0��x��0.95 (such as x is 0.01,0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85 or 0.9), 0 < y��0.95 (such as y is 0.01,0.05,0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85 or 0.9), 0��n��0.08, is zero during x and y difference.
A2BO4Nickelate (the A of structure2NiO4TypeNickelate):
(1) the nickelate A of location A doping2NiO4Meet structure A2BO4Or meet the structure (A of location A defect2)1-nBO4(0��n��0.08). Wherein location A is the combination of lanthanide series and alkaline-earth metal, namely only when location A adulterates, and A2BO4The nickelate of structure meets following chemical general formula: (Ln2-xCx)1-nNiO4, wherein Ln is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; C is one or more in Mg, Ca, Sr, Ba; 0 < x��1.8.
(2) the nickelate A of B location doping2NiO4Meet structure A2BO4Or meet the structure (A of location A defect2)1-nBO4(0��n��0.08). Wherein B location is the combination of nickel element and variable valency metal, namely only when B location adulterates, and A2BO4The nickelate of structure meets following chemical general formula: A2Ni1-yDyO4, wherein A is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and D is one or more in Sc, Ti, V, Cr, Co, Mn, Fe, Cu, Zn;0 < y��0.95.
(3) when A and B location adulterate simultaneously, A2BO4The nickelate of structure meets following chemical general formula: (Ln2-xCx)1-nNi1-yDyO4, wherein Ln is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; C is one or more in Mg, Ca, Sr, Ba; D is one or more in Sc, Ti, V, Cr, Co, Mn, Fe, Cu, Zn; 0 < x��1.8; 0 < y��0.95; 0��n��0.08.
Comprehensive three of the above doping situation, the A that the present invention uses2BO4The nickelate of structure preferably meets following chemical general formula: (Ln2-xCx)1-nNi1-yDyO4, wherein Ln is one or more in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and C is one or more in Mg, Ca, Sr, Ba, and D is one or more in Sc, Ti, V, Cr, Co, Mn, Fe, Cu, Zn, x, y is the molar content of respective element, and (such as x is 0.01 in 0��x��1.8, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7), (such as y is 0.01 in 0 < y��0.95, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85 or 0.9), 0��n��0.08, it is zero during x and y difference.
At above-mentioned composite cathode material, described high oxygen-ion conductive material is preferably one or more in the zirconium oxide of metal oxide stability, the cerium oxide of doped metallic oxide and the lanthanum gallate of strontium magnesium cobalt codope. Below these three height oxygen-ion conductive material is discussed in detail.
Zirconium oxide (the StabilizedZrO of metal oxide stability2) in, conventional metal-oxide is calcium oxide (CaO), magnesium oxide (MgO), and one or more in some rare earth oxides, described rare earth oxide such as yittrium oxide (Y2O3), Scia (Sc2O3), lanthana (La2O3), praseodymium oxide (Pr2O3), Dineodymium trioxide (Nd2O3), promethium oxide (Pm2O3), Disamarium trioxide (Sm2O3), europium oxide (Eu2O3), Gadolinia. (Gd2O3), terbia. Diterbium trioxide (Tb2O3), dysprosia (Dy2O3), holmia (Ho2O3), Erbia (Er2O3), Dithulium trioxide (Tm2O3), ytterbium oxide (Yb2O3), luteium oxide (Lu2O3). Preferably, in the zirconium oxide of described metal oxide stability, the content of described metal-oxide is 1-20mol% (such as 2mol%, 4mol%, 5mol%, 6mol%, 7mol%, 8mol%, 9mol%, 10mol%, 11mol%, 12mol%, 13mol%, 14mol%, 15mol%, 17mol%, 19mol%). Specifically, general material has 8mol%Y2O3The ZrO of doping2[(Y2O3)0.08(ZrO2)0.92], 10mol%Sc2O3The ZrO of doping2[(Sc2O3)0.1(ZrO2)0.9], 10mol%Sc2O3And 1mol%CeO2The ZrO of doping2[(Sc2O3)0.1(CeO2)0.01(ZrO2)0.89], 10mol%Sc2O3And 1mol%Al2O3The ZrO of doping2[(Sc2O3)0.1(Al2O3)0.01(ZrO2)0.89], 6mol%Sc2O3And 1mol%Al2O3The ZrO of doping2[(Sc2O3)0.06(Al2O3)0.01(ZrO2)0.93]��
Cerium oxide (the DopedCeO of doped metallic oxide2) in, conventional metal-oxide is calcium oxide (CaO), magnesium oxide (MgO), and one or more in some rare earth oxides. Described rare earth oxide can be yittrium oxide (Y2O3), Scia (Sc2O3), lanthana (La2O3), praseodymium oxide (Pr2O3), Dineodymium trioxide (Nd2O3), promethium oxide (Pm2O3), Disamarium trioxide (Sm2O3), europium oxide (Eu2O3), Gadolinia. (Gd2O3), terbia. Diterbium trioxide (Tb2O3), dysprosia (Dy2O3), holmia (Ho2O3), Erbia (Er2O3), Dithulium trioxide (Tm2O3), ytterbium oxide (Yb2O3), luteium oxide (Lu2O3).These metal-oxides MO or M2O3CeO after doping2For: Ce1-xMxO2(0.05��x��0.3), M is one or more in above-mentioned metallic element and calcium, magnesium, yttrium, scandium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutecium.
Lanthanum gallate (Sr, Mg, the andCoco-dopedLaGaO of strontium magnesium cobalt codope3) in, the lanthanum gallate of described strontium magnesium cobalt codope meets following chemical general formula: La0.8Sr0.2Ga0.8Mg0.2-xCoxO3(0��x��0.15, such as x is 0,0.05,0.1,0.12,0.14).
Above-mentioned cathode material powder and high oxygen-ion conductive material powder can be prepared by conventional inorganic materials synthesis methods such as the anti-method of solid phase, solution combustion synthetic method, coprecipitation, hydrothermal synthesis method, collosol and gel synthetic method, polymer complex methods. Also can directly buy from companies such as FuelCellMaterials.
The preparation method of the composite cathode material of above-mentioned SOFC, comprises the steps:
Step one, mixes cathode material powder and high oxygen-ion conductive material powder and grinds, obtaining two system combination electrodes; The quality of wherein said high oxygen-ion conductive material powder is the 30%��70% of two system combination electrode gross masses;
Step 2, adds above-mentioned cathod catalyst powder in described two system combination electrodes, mixes and grind, obtaining composite cathode material described in three-system; The quality of wherein said cathod catalyst powder is the 0.05-40% of composite cathode material gross mass described in three-system.
In the preparation method of above-mentioned composite cathode material, as a kind of preferred implementation, in described step one, the powder particle particle diameter of described cathode material is 0.3��1.5 ��m (such as: 0.4 ��m, 0.5-1 ��m, 0.5 ��m, 0.6 ��m, 0.7 ��m, 0.8 ��m, 0.9 ��m, 1.2 ��m, 1.3 ��m, 1.4 ��m); The powder particle particle diameter of described high oxygen-ion conductive material is 0.3��1.5 ��m (such as: 0.3-0.5 ��m, 0.5-1 ��m, 0.4 ��m, 0.5 ��m, 0.6 ��m, 0.7 ��m, 0.8 ��m, 0.9 ��m, 1.0 ��m, 1.1 ��m, 1.4 ��m).
In the preparation method of above-mentioned composite cathode material, as a kind of preferred implementation, in described step 2, the particle diameter of described cathod catalyst powder is not more than 5 ��m (such as: 1-5 ��m, 0.5-4 ��m, 0.01-0.1 ��m, 0.05-0.2 ��m, 0.001 ��m, 0.05 ��m, 0.3 ��m, 1.5 ��m, 2 ��m, 2.5 ��m, 3 ��m, 3.5 ��m, 4 ��m, 4.5 ��m, 5 ��m). It is highly preferred that the granularity of described cathod catalyst is 0.005��5 ��m.
In the preparation method of above-mentioned composite cathode material, as a kind of preferred implementation, in described step one and described step 2, described grinding is wet ball grinding, concrete technology parameter is: the range of speeds 200��400rpm (such as 210rpm, 250rpm, 28rpm, 310rpm, 330rpm, 360rpm, 390rpm), ball material quality is than scope 20/1��40/1 (such as 20:1,25:1,30:1,35:1,40:1), medium is ethanol, Ball-milling Time 20-24h (such as 21h, 22h, 23h). Grinding in this two step is mainly used in uniform for various mixing of materials.
The using method of above-mentioned three-system composite cathode material, including: first, above-mentioned three-system composite cathode material and organic bond are mixed and made into electrode slurry; Then, utilizing the method for silk screen printing that described electrode slurry is printed in bath surface, thickness of electrode controls at 10��100 ��m;Difference according to type of electrodes, by described electrode sintering 1h��10h (such as: 2h, 3h, 5h, 6h, 7h, 8h, 9h) in 900 DEG C��1300 DEG C (such as: 910 DEG C, 950 DEG C, 1000 DEG C, 1100 DEG C, 1200 DEG C, 1250 DEG C, 1290 DEG C).
Below for the zirconium oxide of the manganite-metal oxide stability of the doping of perovskite structure-cathod catalyst series composite cathode material, prove to add the feature performance benefit of the composite cathode material of catalyst, the concrete generated output adopting full battery testing method test SOFC monocell. It is also provided with the normal cell of contrast in embodiments, (the Sc that the electrolyte of this contrast standard battery adopts thickness to be 200 ��m2O3)0.10(CeO2)0.01(ZrO2)0.89Electrolyte, electrode material powder all obtains from FuelCellMaterials company. It addition, adopt the method for silk screen printing to print the NiO-(Sc of top surface area 0.64cm in electrolyte sheet side2O3)0.10(CeO2)0.01(ZrO2)0.89Anode slurry, as anode, sinters 1��5 hour (the contrast standard battery used in following example has all sintered 4h) after drying in 1100 DEG C��1400 DEG C (the contrast standard battery used in following example all carries out at 1300 DEG C). Opposite side at electrolyte sheet adopts the (La of the method printing top surface area 0.64cm of silk screen printing0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Cathode slurry, as standard cathode, sinters 1��5 hour (the contrast standard battery used in following example has all sintered 4h) after drying in 1100 DEG C��1300 DEG C (the contrast standard battery used in following example all carries out at 1200 DEG C).
The monocell performance test methods of following example and normal cell is as follows: carrying out monocell performance test under 800 DEG C of furnace temperature, anode passes into the hydrogen being mixed with 3vol% steam, and negative electrode passes into air.
The manganite of the doping of the various perovskite structures used in following example and the zirconium oxide of metal oxide stability are all purchased from FuelCellMaterials.
Embodiment 1
(1) synthesize the strontium titanates of the perovskite structure of Fe2O3 doping with solid-phase synthesis, its chemical formula is as follows: SrTi1-yFeyO3; Y=0.35.
A. by the SrCO of purity >=99.9%3��TiO2��Fe2O3Three kinds of raw materials are according to chemical formula SrTi0.65Fe0.35O3Middle metallic element molar percentage mix, and in ethanol medium ball milling 24 hours, rotating speed 300rpm, ball material mass ratio 40/1.
B. the product after ball milling is dried, sinter 10 hours in 1400 DEG C afterwards.
C. after sintering, at ethanol medium, rotating speed is 800rpm, and when ball material mass ratio 35/1, ball milling 10 hours is 0.06 ��m to mean particle size.
(2) at standard two system composite cathode material
(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89(wherein (Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Quality account for whole standard composite cathode material quality 50%, particle mean size is 1.2 ��m) the above-mentioned cathod catalyst of middle addition, mix and grind, grinding condition is as follows: ball milling 24 hours in ethanol medium, rotating speed 300rpm, ball material mass ratio 40/1, finally gives the composite cathode material powder of three-system. Wherein, above-mentioned cathod catalyst accounts for the mass percent of the composite cathode material powder of three-system is 10% (i.e. SrTi0.65Fe0.35O3/(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89=1/9.
Adopt following methods that the performance of the composite cathode material powder of this three-system is tested:
First, adding organic bond in above-mentioned composite cathode powder and make composite cathode slurry, wherein above-mentioned composite cathode powder is 5:5 with the mass ratio of organic binder bond.
Then, adopt the method for silk screen printing at the (Sc of 200 ��m2O3)0.10(CeO2)0.01(ZrO2)0.89NiO-(the Sc of electrolyte sheet side printing top surface area 0.64cm2O3)0.10(CeO2)0.01(ZrO2)0.89Anode slurry, as anode, sinters 4 hours after drying in 1300 DEG C.Opposite side at electrolyte sheet adopts the above-mentioned composite cathode slurry of the method printing top surface area 0.64cm of silk screen printing as negative electrode, sinters 4 hours after drying in 1200 DEG C.
Fig. 1 shows interpolation 10%SrTi0.65Fe0.35O3(the La of powder0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89The monocell power generation performance of composite cathode, it can be seen that add 10%SrTi in standard two system composite cathode material0.65Fe0.35O3Rear battery performance is better than normal cell performance, and the maximum power density of battery is from 501mWcm-2Increase to 600mWcm-2��
Embodiment 2
In three-system composite cathode material prepared by the present embodiment, except the cathod catalyst SrTi added0.65Fe0.35O3Content be different from beyond embodiment 1, other are all identical with embodiment 1, in the present embodiment, cathod catalyst SrTi0.65Fe0.35O3The mass percent accounting for the composite cathode material powder of three-system is 20% (i.e. SrTi0.65Fe0.35O3/(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89=2/8.
The performance methodology of the composite cathode material powder of three-system prepared by the present embodiment is with embodiment 1. Result is referring to Fig. 2, as it can be seen, add 20%SrTi in standard two system composite cathode material0.65Fe0.35O3Rear battery performance is better than normal cell performance, and the maximum power density of battery is from 501mWcm-2Increase to 822mWcm-2��
Embodiment 3
In three-system composite cathode material prepared by the present embodiment, except the cathod catalyst SrTi added0.65Fe0.35O3Content be different from beyond embodiment 1, other are all identical with embodiment 1, in the present embodiment, cathod catalyst SrTi0.65Fe0.35O3The mass percent accounting for the composite cathode material powder of three-system is 40% (i.e. SrTi0.65Fe0.35O3/(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89=4/6.
The performance methodology of the composite cathode material powder of three-system prepared by the present embodiment is with embodiment 1. Result is referring to Fig. 3, as it can be seen, add 40%SrTi in standard two system composite cathode material0.65Fe0.35O3Rear battery performance is better than normal cell performance, and the maximum power density of battery is from 501mWcm-2Increase to 540mWcm-2��
Embodiment 4
In three-system composite cathode material prepared by the present embodiment, except the cathod catalyst SrTi added0.95Fe0.05O3Chemical composition and content be different from beyond embodiment 1, other are all identical with embodiment 1, in the present embodiment, cathod catalyst SrTi0.95Fe0.05O3The mass percent accounting for the composite cathode material powder of three-system is 20% (i.e. SrTi0.95Fe0.05O3/(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89=2/8.
The performance methodology of the composite cathode material powder of three-system prepared by the present embodiment is with embodiment 1. Result shows, adds 20%SrTi in standard two system composite cathode material0.95Fe0.05O3Rear battery performance is better than normal cell performance, and the maximum power density of battery is 720mWcm-2��
Embodiment 5
In three-system composite cathode material prepared by the present embodiment, except the cathod catalyst SrTi added0.1Fe0.9O3Chemical composition and content be different from beyond embodiment 1, other are all identical with embodiment 1, in the present embodiment, cathod catalyst SrTi0.1Fe0.9O3The mass percent accounting for the composite cathode material powder of three-system is 20% (i.e. SrTi0.1Fe0.9O3/(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89=2/8.
The performance methodology of the composite cathode material powder of three-system prepared by the present embodiment is with embodiment 1. Result shows, adds 20%SrTi in standard two system composite cathode material0.1Fe0.9O3Rear battery performance is better than normal cell performance, and the maximum power density of battery is 542mWcm-2��
Embodiment 6
In three-system composite cathode material prepared by the present embodiment, except the cathod catalyst Sr added0.8Ba0.2Ti0.65Fe0.35O3Chemical composition and content be different from beyond embodiment 1, other are all identical with embodiment 1, in the present embodiment, cathod catalyst Sr0.8Ba0.2Ti0.65Fe0.35O3The mass percent accounting for the composite cathode material powder of three-system is 20% (i.e. Sr0.8Ba0.2Ti0.65Fe0.35O3/(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89=2/8.
The performance methodology of the composite cathode material powder of three-system prepared by the present embodiment is with embodiment 1. Result shows, adds 20%Sr in standard two system composite cathode material0.8Ba0.2Ti0.65Fe0.35O3Rear battery performance is better than normal cell performance, and the maximum power density of battery is 540mWcm-2��
Embodiment 7
In three-system composite cathode material prepared by the present embodiment, except the cathod catalyst Sr added0.8Ca0.2Ti0.65Fe0.35O3Chemical composition and content be different from beyond embodiment 1, other are all identical with embodiment 1, in the present embodiment, cathod catalyst Sr0.8Ca0.2Ti0.65Fe0.35O3The mass percent accounting for the composite cathode material powder of three-system is 20% (i.e. Sr0.8Ca0.2Ti0.65Fe0.35O3/(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89=2/8.
The performance methodology of the composite cathode material powder of three-system prepared by the present embodiment is with embodiment 1. Result shows, adds 20%Sr in standard two system composite cathode material0.8Ca0.2Ti0.65Fe0.35O3Rear battery performance is better than normal cell performance, and the maximum power density of battery is 538mWcm-2��
Embodiment 8
In three-system composite cathode material prepared by the present embodiment, except the cathod catalyst Sr added0.8Mg0.2Ti0.65Fe0.35O3Chemical composition and content be different from beyond embodiment 1, other are all identical with embodiment 1, in the present embodiment, cathod catalyst Sr0.8Mg0.2Ti0.65Fe0.35O3The mass percent accounting for the composite cathode material powder of three-system is 20% (i.e. Sr0.8Mg0.2Ti0.65Fe0.35O3/(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89=2/8.
The performance methodology of the composite cathode material powder of three-system prepared by the present embodiment is with embodiment 1. Result shows, adds 20%Sr in standard two system composite cathode material0.8Mg0.2Ti0.65Fe0.35O3Rear battery performance is better than normal cell performance, and the maximum power density of battery is 571mWcm-2��
Comparative example 1
In the three-system composite cathode material of this contrast preparation, except the cathod catalyst SrTi added0.65Fe0.35O3Amount be different from beyond embodiment 1, other are all identical with embodiment 1, in the present embodiment, cathod catalyst SrTi0.65Fe0.35O3The mass percent accounting for the composite cathode material powder of three-system is 0.1% (i.e. SrTi0.65Fe0.35O3/(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89=0.01/9.99.
The performance methodology of the composite cathode material powder of three-system prepared by the present embodiment is with embodiment 1. Result shows, adds 0.1%SrTi in standard two system composite cathode material0.65Fe0.35O3Rear battery performance is basic and normal cell performance is fair, and the maximum power density of battery is 502mWcm-2��
Comparative example 2
By cathod catalyst SrTi0.65Fe0.35O3Join (Sc2O3)0.10(CeO2)0.01(ZrO2)0.89In (particle mean size is 1.2 ��m), wherein cathod catalyst and (Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Mass ratio be 2:8, the two is mixed and grinds, grinding condition is as follows: ball milling 24 hours in ethanol medium, rotating speed 300rpm, and ball material mass ratio 40/1 finally gives composite cathode material powder.
Employing is tested with the performance of the composite cathode material powder that this comparative example is prepared by the method that embodiment 1 is identical, and the maximum power density of battery is 350mWcm-2��

Claims (10)

1. a SOFC cathod catalyst, it is characterised in that described cathod catalyst is the strontium titanates of the perovskite structure of doping, meets following chemical general formula: (Sr1-xCx)1-nTi1-yDyO3, wherein C is one or more in Mg, Ca, Ba, and D is one or more in Sc, V, Cr, Co, Mn, Ni, Fe, Cu, Zn; X, y are the molar content of respective element, and 0��x��0.95,0 < y��0.95; 0��n��0.08.
2. cathod catalyst according to claim 1, it is characterised in that the granularity of described cathod catalyst is for being not more than 5 ��m; Preferably, the granularity of described cathod catalyst is 0.005��5 ��m;
Further, 0��x��0.3,0 < y��0.9, n=0.
3. the preparation method of cathod catalyst described in claim 1 or 2, it is characterised in that described cathod catalyst powder adopts solid-phase synthesis to be prepared, it is preferable that the concrete preparation method of described cathod catalyst powder is as follows:
Ball milling blend step: according to the molar content of elements various in prepared cathod catalyst by the raw material SrCO of respective amount3��TiO2Wet ball grinding is carried out until raw material is sufficiently mixed uniformly with the oxide treating doped chemical;
Sintering step: the product after described wet ball grinding is sintered 5��20 hours after drying at 1100 DEG C��1500 DEG C;
Ball milling step again: the product after sintering is carried out wet ball grinding again until particle diameter meets the requirements.
4. the composite cathode material of the SOFC comprising cathod catalyst described in claim 1 or 2.
5. composite cathode material according to claim 4, it is characterised in that described composite cathode material also includes cathode material and high oxygen-ion conductive material; Preferably, the quality of described cathod catalyst is the 0.05-40% of cathode material, high oxygen-ion conductive material and cathod catalyst quality sum; It is highly preferred that the quality of described high oxygen-ion conductive material is cathode material and the 30-70% of high oxygen-ion conductive material quality sum.
6. composite cathode material according to claim 5, it is characterized in that, described cathode material is nickelate and the A of the doping of the ferrite of the doping of the cobaltatess of the doping of the manganite of the doping of perovskite structure, perovskite structure, perovskite structure, perovskite structure2NiO4One or more in the nickelate of structure.
7. composite cathode material according to claim 5, it is characterised in that described high oxygen-ion conductive material is one or more in the zirconium oxide of metal oxide stability, the cerium oxide of doped metallic oxide and the lanthanum gallate of strontium magnesium cobalt codope.
8. composite cathode material according to claim 7, it is characterized in that, in the zirconium oxide of described metal oxide stability, described metal-oxide is one or more in calcium oxide, magnesium oxide, Scia, yittrium oxide, lanthana, praseodymium oxide, Dineodymium trioxide, promethium oxide, Disamarium trioxide, europium oxide, Gadolinia., terbia. Diterbium trioxide, dysprosia, holmia, Erbia, Dithulium trioxide, ytterbium oxide and luteium oxide; Preferably, in the zirconium oxide of described metal oxide stability, the content of described metal-oxide is 1-20mol%.
9. composite cathode material according to claim 7, it is characterized in that, in the cerium oxide of described doped metallic oxide, described metal-oxide is one or more in calcium oxide, magnesium oxide, Scia, yittrium oxide, lanthana, praseodymium oxide, Dineodymium trioxide, promethium oxide, Disamarium trioxide, europium oxide, Gadolinia., terbia. Diterbium trioxide, dysprosia, holmia, Erbia, Dithulium trioxide, ytterbium oxide and luteium oxide; Preferably, the cerium oxide of described doped metallic oxide meets following chemical general formula: Ce1-xMxO2, wherein, 0.05��x��0.3, M is one or more in calcium, magnesium, scandium, yttrium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutecium;
Further, the lanthanum gallate of described strontium magnesium cobalt codope meets following chemical general formula: La0.8Sr0.2Ga0.8Mg0.2-xCoxO3, wherein 0��x��0.15.
10. the preparation method of the composite cathode material of the arbitrary described SOFC of claim 4-9, it is characterised in that comprise the steps:
Step one, mixes cathode material powder and high oxygen-ion conductive material powder and grinds, obtaining two system combination electrodes;The quality of wherein said high oxygen-ion conductive material powder is the 30%��70% of two system combination electrode gross masses;
Step 2, adds cathod catalyst powder in described two system combination electrodes, mixes and grind, obtaining composite cathode material described in three-system; The quality of wherein said cathod catalyst powder is the 0.05-40% of composite cathode material gross mass described in three-system.
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CN108091884A (en) * 2016-11-21 2018-05-29 中国科学院大连化学物理研究所 A kind of cathode of solid oxide fuel cell and application
CN108091884B (en) * 2016-11-21 2020-04-28 中国科学院大连化学物理研究所 Solid oxide fuel cell cathode and application
CN107425205A (en) * 2017-07-18 2017-12-01 新奥科技发展有限公司 A kind of anode of solid oxide fuel cell material and its fuel cell
CN110391442A (en) * 2018-04-18 2019-10-29 阜阳师范学院 A kind of Eu2O3、Y2O3Codope ZrO2Low-melting glass flour complexes and preparation method thereof
CN111229219A (en) * 2018-11-29 2020-06-05 中国科学院大连化学物理研究所 Tail gas combustion catalyst and preparation and application thereof
CN111229250A (en) * 2018-11-29 2020-06-05 中国科学院大连化学物理研究所 Ethanol reforming catalyst and preparation and application thereof
CN113258086A (en) * 2021-04-30 2021-08-13 南京工业大学 Three-phase conductor proton conductor composite cathode material and preparation method thereof
CN113258086B (en) * 2021-04-30 2022-09-27 南京工业大学 Three-phase conductor proton conductor composite cathode material and preparation method thereof
CN114267847A (en) * 2021-12-15 2022-04-01 常州大学 Novel bimetallic oxygen reduction electrocatalyst
CN114267847B (en) * 2021-12-15 2024-01-23 常州大学 Bimetallic oxygen reduction electrocatalyst

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