CN101599546A - A kind of cathode material for solid-oxide fuel cell and application - Google Patents
A kind of cathode material for solid-oxide fuel cell and application Download PDFInfo
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- CN101599546A CN101599546A CNA2008100117128A CN200810011712A CN101599546A CN 101599546 A CN101599546 A CN 101599546A CN A2008100117128 A CNA2008100117128 A CN A2008100117128A CN 200810011712 A CN200810011712 A CN 200810011712A CN 101599546 A CN101599546 A CN 101599546A
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- 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
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- 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 present invention relates to Solid Oxide Fuel Cell, is LSM (strontium lanthanum manganese oxide) cathode material and application thereof that a kind of transition elements titanium or scandium mix specifically.This cathode material consists of (La
1-xSr
x)
1-yMn
1-zM
zO
3 ± δ, (0＜x＜1,0＜y＜1,0＜z≤1 ,-1＜δ＜1), M is titanium elements or scandium element.By mass percentage, cathode of solid oxide fuel cell is made up of above-mentioned cathode material of 1-100% and 0-99% electrolyte; Described electrolyte is 5-20mol%Y
2O
3Stable ZrO
2, 5-20mol%Sc
2O
3Stable ZrO
2, Sm
xCe
1-xO
2, Gd
xCe
1-xO
2, Y
xCe
1-xO
2, La
xCe
1-xO
2, La
1-xSr
xGa
1-yMg
yO
3In (0＜x＜1,0＜y＜1) one or more.Utilize the present invention can improve strontium lanthanum manganese oxide cathode material catalytic oxidation-reduction reactive activity, quicken the course of reaction of oxygen on the cathode material surface, reduce cathodic polarization, thereby effectively improve the power output of Solid Oxide Fuel Cell, the output performance of 600 ℃ of batteries improves more than 2 times than standard strontium lanthanum manganese oxide battery.
Description
Technical field
The present invention relates to Solid Oxide Fuel Cell, high-performance modified strontium lanthanum manganese oxide (LSM) the perovskite cathode material for solid-oxide fuel cell and the application thereof of transition elements titanium or scandium doping specifically.
Background technology
Solid Oxide Fuel Cell (SOFC) be a kind of be electrolyte membrance with the solid oxygen ion conductor, can be converted into chemical energy the generation technology of electric energy.The Solid Oxide Fuel Cell fuel source is abundant, can directly make fuel with natural gas, synthesis gas, biogas, liquefied gas and other hydrocarbon; NO
xAnd SO
xDischarge low.The SOFC generating efficiency can reach 50%, combines with other technology (as gas turbine), and generating efficiency can reach 60-70%.
Monocell is the core component of Solid Oxide Fuel Cell, is made up of electrolyte, anode and negative electrode.Has ABO
3The strontium lanthanum manganese oxide of type perovskite structure (LSM, the A position is strontium and lanthanum element, the B position is a manganese element) be to study at present and the most widely used cathode material.LSM is at high temperature highly stable, is all mating aspect chemical compatibility and the thermal compatibility with the electrolyte of using always.The major defect of LSM cathode material is that intrinsic oxygen catalytic reduction activity is lower.Simultaneously, because LSM is pure electronic conductor, lack ionic conductivity, cause the effecting reaction zone of electrode little, cathodic polarization is more remarkable.
In recent years, the electrolytic thin-membrane Development of Preparation Technology makes the working temperature of SOFC can be reduced to below 800 ℃.Yet along with the reduction of operating temperature, the chemical property of LSM cathode material sharply descends, and negative electrode has become the principal element of restriction hull cell performance.At the characteristics of LSM negative electrode, the strategy that improves cathode performance has two kinds: a kind of is that electrolyte that LSM cathode material and macroion electricity are led is mixed, improves the chemical property of negative electrode by the expansion three phase boundary.Another kind of approach is under the prerequisite that guarantees perovskite structure to be mixed in the A position of LSM and B position or replace, and improves the hydrogen reduction activity of LSM cathode material.People broad research use Pr, the La element that Nd, Sm, Gd, Yb, rare earth elements such as Y replace LSM perovskite A position constitutes the chemical property of SOFC negative electrode.Multiple factors such as comprehensive thermal coefficient of expansion, conductivity, reactivity are found Pr
xSr
1-xMnO3 (0＜x＜1), Nd
xSr
1-xMnO3 (0＜x＜1) is more promising cathode material (referring to J.Electrochem.Soc., 142 (1995) 1519-1524).Research at present more to mixing or the element that replaces mainly concentrates on the later transition elements of period 4 Mn LSM perovskite B position.The new cathode material such as the La that form after mixing
xSr
1-xFeO3 (0＜x＜1, LSF), La
xSr
1-xCoO3 (0＜x＜1, LSC), La
xSr
1-xCoFeO3 ((0＜x＜1), LSCF), La
xSr
1-xCuO3 (0＜x＜1, LSCu), La
xSr
1-xCo
yCu
1-yO3 (LSCCu) wait except having certain electronic conductance, also has certain ionic conductivity by 0＜x＜1,0＜y＜1.When they were used as negative electrode, the cathodic oxygen reduction conversion zone was not only limited to the three-phase reaction interface place, but expands to whole cathode surface, greatly reduces cathodic polarization (referring to Solid state Ionics 138 (2000) 143-152; Solid State Ionics, 148 (2002) 545-549; Mater.Resear.Bull.38 (2003) 231-239; Journal of power sources, 113 (2003) 1-10; Solid State Ionics, 176 (2005) 1341-1350).The disadvantage of above-mentioned material is relatively poor with YSZ electrolyte chemical compatibility commonly used.When its battery long-time stability as with the supporting cathode material of novel electrolytes the time and to external world the tolerance of environment also remain further investigation.
Summary of the invention
In the present invention, the applicant is with the basis of traditional LSM cathode material as new cathode material exploitation, by to B position doping transition elements scandium or titanium, and improve the hydrogen reduction activity of LSM cathode material, thereby reduce cathodic polarization in conjunction with the modulation of A position strontium and lanthanum element.
Purpose of the present invention is intended to solve the lower problem of LSM in the Solid Oxide Fuel Cell (strontium lanthanum manganese oxide) cathode material catalytic activity, introduce transition elements titanium or scandium by B position at LSM (strontium lanthanum manganese oxide) perovskite material, adjust the ratio of A position strontium and lanthanum element simultaneously, thereby change the structure of cathode material active constituent, improve the electrocatalytic oxidation reducing activity of LSM (strontium lanthanum manganese oxide) cathode material, reduce the polarization overpotential of LSM (strontium lanthanum manganese oxide) negative electrode, improve the power output of battery.
For achieving the above object, the technical solution used in the present invention is:
Cathode material for solid-oxide fuel cell, this cathode material are LSM (strontium lanthanum manganese oxide) electric conducting material that transition elements titanium or scandium mix; It consists of (La
1-xSr
x)
1-yMn
1-zM
zO
3 ± δ, (0＜x＜1,0＜y＜1,0＜z≤1 ,-1＜δ＜1), M is titanium elements or scandium element.The synthetic of this cathode material can be adopted conventional citric acid method, hydrothermal synthesis method, glycine method, coprecipitation, firing method or high-temperature solid phase reaction method.
A kind of solid-oxide fuel battery three-in-one component (MEA) comprises anode, dielectric film and negative electrode.MEA anode manufacturing materials is the metal/oxide composite ceramics, and wherein metallic catalyst comprises Ni, Co, and Cu, Rh, Fe, Pt, Pd, one or more among Mo and the Ti, oxide comprises 5-20mol%Y
2O
3Stable ZrO
2, 5-20mol% Sc
2O
3Stable ZrO
2, Sm
xCe
1-xO
2(SDC) (0＜x＜1), Gd
xCe
1-xO
2(GDC) (0＜x＜1), Y
xCe
1-xO
2(YDC) (0＜x＜1), La
xCe
1-xO
2(LDC) (0＜x＜1), La
1-xSr
xGa
1-yMg
yO
3In (0＜x＜1,0＜y＜1) one or more; The mass percentage content of metallic catalyst is 1%-100%;
MEA dielectric film manufacturing materials is 5-20mol%Y
2O
3Stable ZrO
2, 5-20mol%Sc
2O
3Stable ZrO
2, Sm
xCe
1-xO
2(SDC) (0＜x＜1), Gd
xCe
1-xO
2(GDC) (0＜x＜1), Y
xCe
1-xO
2(YDC) (0＜x＜1), La
xCe
1-xO
2(LDC) (0＜x＜1), La
1-xSr
xGa
1-yMg
yO
3In (0＜x＜1,0＜y＜1) one or more; Dielectric film can adopt method preparations such as high temperature sintering, vapour deposition, sol-gel, plasma spray coating, and its thickness is 0.01 micron to 5000 microns, and annealing temperature is in 200 ℃ of-1500 ℃ of interval ranges;
The MEA negative electrode can be made of separately LSM (strontium lanthanum manganese oxide) cathode material that above-mentioned transition elements titanium or scandium mix, and also can be made of LSM (strontium lanthanum manganese oxide) cathode material of this transition elements titanium or scandium doping and the composite material that electrolyte is formed.The mass percentage content of LSM (strontium lanthanum manganese oxide) cathode material in the MEA negative electrode that above-mentioned transition elements titanium or scandium mix is 1-100%; Described electrolyte is 5-20mol%Y
2O
3Stable ZrO
2, 5-20mol%Sc
2O
3Stablize ZrO
2, Sm
xCe
1-xO
2(SDC) (0＜x＜1), Gd
xCe
1-xO
2(GDC) (0＜x＜1), Y
xCe
1-xO
2(YDC) (0＜x＜1), La
xCe
1-xO
2(LDC) (0＜x＜1), La
1-xSr
xGa
1-yMg
yO
3In (0＜x＜1,0＜y＜1) one or more.The MEA negative electrode adopts The tape casting, silk screen print method, coating process, vapour deposition process or plasma spraying process preparation on dielectric film, and 200-1300 ℃ of annealing, its THICKNESS CONTROL is between 0.01 micron to 2000 microns.
That the structure of described three-in-one component MEA can adopt is plate, cast, flat-tube type, honeycomb type and other various makes; Can adopt multiple structures such as dielectric film self-cradling type, cathode support type, anode support type.
The present invention has following advantage:
1. adopt the cathode material for solid-oxide fuel cell of the present invention's preparation, can be by changing titanium or scandium doping, the strontium of A position and the effective modulation cathode material of the composition catalytic oxidation-reduction reactive activity and the conductivity of lanthanum of B position.
2. adopt the compound cathode of solid oxide fuel battery of the present invention's preparation, can be by changing the content of this cathode material in the composite cathode, the formation of the sintering temperature of composite cathode and effective control cathode/electrolyte interface of the preparation method of composite cathode and negative electrode micro-structural.
2. it is simple to adopt the present invention to carry out the technology of Solid Oxide Fuel Cell MEA preparation, can adopt multiple routine techniques preparation.Be specially: at first, adopt The tape casting, dry pressing or extrusion moulding to prepare the anode assembly.With above-mentioned cathode material and electrolyte mixing, evenly be mixed and made into slurry with binding agent then, by The tape casting, silk screen print method, coating process its preparation on dielectric film, is formed at high temperature sintering at last.
3. the present invention can be used for the Solid Oxide Fuel Cell of multiple configurations such as plate, cast, flat-tube type, honeycomb type; Be applicable to multiple solid oxide fuel cell applications field, as compact power, decentralized power s etc.
Embodiment
Embodiment 1
La
0.8Sr
0.2Mn
0.98Sc
0.02O
3Synthetic: with 2.61g La
2O
3Generate La (NO with rare nitric acid (the 4ml red fuming nitric acid (RFNA) is dissolved in 10ml water) dissolving
3)
3The aqueous solution, and then with 0.85g Sr (NO
3)
2, 0.136g Sc (NO
3)
3.6H
2O and 7.015g Mn (NO
3)
2(quality percentage composition 50%) solution joins above-mentioned La (NO
3)
3In the aqueous solution, stirring is dissolved it fully, forms clear solution.Add the 7.82g Triammonium citrate according to metal ion and 1: 1 ratio of Triammonium citrate, and to transfer pH with nitric acid be 1-2.Add thermal agitation to form the transparent and uniform gel, be placed on burning formation raw powder on the electric furnace then.The powder of preparation grain shape rule.This fluffy raw powder at 900 ℃ of calcining 3h, is obtained the lanthanum strontium manganese perovskite cathode material that scandium mixes.
To be equipped with NiO-YSZ/YSZ two-in-one by burning legal system altogether, burnt altogether 4 hours at proper temperature, obtains the anode assembly.Adopt cladding process to prepare La
0.8Sr
0.2Mn
0.98Sc
0.02O
3-YSZ composite cathode was proper temperature roasting 2 hours.With hydrogen is fuel gas, and oxygen is oxidant, 650 ℃ of-800 ℃ of test battery performances.Maximum power density reaches 1.44Wcm in the time of 800 ℃
-2Maximum power density reaches 0.38Wcm in the time of 650 ℃
-2, than standard La
0.8Sr
0.2MnO
3-YSZ battery performance improves 2 times.
Embodiment 2
La
0.8Sr
0.2Mn
0.95Sc
0.05O
3Synthetic: with 2.61g La
2O
3Generate La (NO with rare nitric acid (the 4ml red fuming nitric acid (RFNA) is dissolved in 10ml water) dissolving
3)
3The aqueous solution, and then with 0.85g Sr (NO
3)
2, 0.339g Sc (NO
3)
3.6H
2O and 6.80g Mn (NO
3)
2(quality percentage composition 50%) solution joins above-mentioned La (NO
3)
3In the aqueous solution, stirring is dissolved it fully, forms clear solution.Add the 7.86g Triammonium citrate according to metal ion and 1: 1 ratio of Triammonium citrate, and to transfer pH with nitric acid be 1-2.Add thermal agitation to form the transparent and uniform gel, be placed on burning formation raw powder on the electric furnace then.The powder of preparation grain shape rule.This fluffy raw powder at 900 ℃ of calcining 3h, is obtained the lanthanum strontium manganese perovskite cathode material that scandium mixes.
To be equipped with NiO-YSZ/YSZ two-in-one by burning legal system altogether, burnt altogether 4 hours at proper temperature, obtains the anode assembly.Adopt silk screen print method to prepare La
0.8Sr
0.2Mn
0.95Sc
0.05O
3-YSZ composite cathode was proper temperature roasting 2 hours.With hydrogen is fuel gas, and oxygen is oxidant, 650 ℃ of-800 ℃ of test battery performances.Maximum power density reaches 1.31Wcm in the time of 800 ℃
-2Maximum power density reaches 0.40Wcm in the time of 650 ℃
-2, than standard La
0.8Sr
0.2MnO
3-YSZ battery performance improves 2.2 times.
Embodiment 3
La
0.8Sr
0.2Mn
0.9Ti
0.1O
3Synthetic: with 2.61g La
2O
3Generate La (NO with rare nitric acid (the 4ml red fuming nitric acid (RFNA) is dissolved in 10ml water) dissolving
3)
3The aqueous solution, and then with 0.85g Sr (NO
3)
2And 6.44gMn (NO
3)
2(quality percentage composition 50%) solution joins above-mentioned La (NO
3)
3In the aqueous solution, stirring is dissolved it fully, forms clear solution.Add the 7.46g Triammonium citrate according to metal ion and 1: 1 ratio of Triammonium citrate, and to transfer pH with nitric acid be 1-2.The 0.68g butyl titanate is joined 1.99g ethylene glycol, stir 30min.Be heated to 70 ℃, the 1.68g citric acid be dissolved in the above-mentioned solution butyl titanate: citric acid: ethylene glycol=1: 4: 16.Above-mentioned solution is added in the metal-nitrate solutions, adds thermal agitation and form transparent and uniform colloidal sol.Be placed on burning formation raw powder on the electric furnace then.This fluffy raw powder at 1100 ℃ of calcining 3h, is obtained titanium doped lanthanum strontium manganese perovskite cathode material.
To be equipped with NiO-YSZ/YSZ two-in-one by burning legal system altogether, burnt altogether 4 hours at proper temperature, obtains the anode assembly.Adopt cladding process to prepare La
0.8Sr
0.2Mn
0.9Ti
0.1O
3-YSZ composite cathode was 1100 ℃ of roastings 2 hours.With hydrogen is fuel gas, and oxygen is oxidant, 600 ℃ of-800 ℃ of test battery performances.Maximum power density reaches 1.21Wcm in the time of 800 ℃
-2Maximum power density reaches 0.19Wcm in the time of 600 ℃
-2, than standard La
0.8Sr
0.2MnO
3-YSZ battery performance improves 2.38 times.
Embodiment 4
La
0.8Sr
0.2Mn
0.6Ti
0.4O
3Synthetic: with 2.61g La
2O
3Generate La (NO with rare nitric acid (the 4ml red fuming nitric acid (RFNA) is dissolved in 10ml water) dissolving
3)
3The aqueous solution, and then with 0.85g Sr (NO
3)
2And 4.29gMn (NO
3)
2(quality percentage composition 50%) solution joins above-mentioned La (NO
3)
3In the aqueous solution, stirring is dissolved it fully, forms clear solution.Add the 6.48g Triammonium citrate according to metal ion and 1: 1 ratio of Triammonium citrate, and to transfer pH with nitric acid be 1-2.The 2.72g butyl titanate is joined the dissolving of 7.96g ethylene glycol, add the 6.72g citric acid then, be heated to 70 ℃ and stir 30min formation transparent and uniform solution.Above-mentioned solution is added in the metal-nitrate solutions, adds thermal agitation and form transparent and uniform colloidal sol.Be placed on burning formation raw powder on the electric furnace then.This fluffy raw powder at 1100 ℃ of calcining 3h, is obtained titanium doped lanthanum strontium manganese perovskite cathode material.
It is two-in-one to prepare NiO-GDC/GDC by dry pressing, burns altogether 4 hours at proper temperature, obtains the anode assembly.Adopt silk screen print method to prepare La
0.8Sr
0.2Mn
0.6Ti
0.4O
3-GDC composite cathode was proper temperature roasting 2 hours.With hydrogen is fuel gas, and oxygen is oxidant, 600 ℃ of-800 ℃ of test battery performances.Maximum power density reaches 0.63Wcm in the time of 800 ℃
-2
Embodiment 5
La
0.8Sr
0.2Mn
0.1Ti
0.9O
3Synthetic: with 2.61g La
2O
3Generate La (NO with rare nitric acid (the 4ml red fuming nitric acid (RFNA) is dissolved in 10ml water) dissolving
3)
3The aqueous solution, and then with 0.85g Sr (NO
3)
2And 0.715gMn (NO
3)
2(quality percentage composition 50%) solution joins above-mentioned La (NO
3)
3In the aqueous solution, stirring is dissolved it fully, forms clear solution.Add the 4.86g Triammonium citrate according to metal ion and 1: 1 ratio of Triammonium citrate, and to transfer pH with nitric acid be 1-2.The 6.12g butyl titanate is joined 17.9g ethylene glycol, stir 30min.Be heated to 70 ℃, the 15.1g citric acid be dissolved in the above-mentioned solution butyl titanate: citric acid: ethylene glycol=1: 4: 16.Above-mentioned solution is added in the metal-nitrate solutions, adds thermal agitation and form transparent and uniform colloidal sol.Be placed on burning formation raw powder on the electric furnace then.This fluffy raw powder at 1100 ℃ of calcining 3h, is obtained titanium doped lanthanum strontium manganese perovskite cathode material.
To be equipped with NiO-YSZ/YSZ two-in-one by burning legal system altogether, burnt altogether 4 hours at proper temperature, obtains the anode assembly.Adopt cladding process to prepare La
0.8Sr
0.2Mn
0.1Ti
0.9O
3-YSZ composite cathode was proper temperature roasting 2 hours.With hydrogen is fuel gas, and oxygen is oxidant, 600 ℃ of-800 ℃ of test battery performances.Maximum power density is 0.88Wcm in the time of 800 ℃
-2
Embodiment 6
(La
0.8Sr
0.2)
0.9Mn
0.9Ti
0.1O
3Synthetic: with 2.35g La
2O
3Generate La (NO with rare nitric acid (the 4ml red fuming nitric acid (RFNA) is dissolved in 10ml water) dissolving
3)
3The aqueous solution, and then with 0.765g Sr (NO
3)
2With 6.44g Mn (NO
3)
2(quality percentage composition 50%) solution joins above-mentioned La (NO
3)
3In the aqueous solution, stirring is dissolved it fully, forms clear solution.Add the 7.0g Triammonium citrate according to metal ion and 1: 1 ratio of Triammonium citrate, and to transfer pH with nitric acid be 1-2.The 0.68g butyl titanate is joined 1.99g ethylene glycol, stir 30min.Be heated to 70 ℃, the 1.68g citric acid be dissolved in the above-mentioned solution butyl titanate: citric acid: ethylene glycol=1: 4: 16.Above-mentioned solution is added in the metal-nitrate solutions, adds thermal agitation and form transparent and uniform colloidal sol.Be placed on burning formation raw powder on the electric furnace then.This fluffy raw powder at 1100 ℃ of calcining 3h, is obtained titanium doped lanthanum strontium manganese perovskite cathode material.
To be equipped with NiO-YSZ/YSZ two-in-one by burning legal system altogether, burnt altogether 4 hours at proper temperature, obtains the anode assembly.Adopt cladding process preparation (La
0.8Sr
0.2)
0.9Mn
0.9Ti
0.1O
3-YSZ composite cathode was proper temperature roasting 2 hours.With hydrogen is fuel gas, and oxygen is oxidant, 600 ℃ of-800 ℃ of test battery performances.Maximum power density reaches 1.86Wcm in the time of 800 ℃
-2, maximum power density reaches 0.50Wcm in the time of 600 ℃
-2, than standard (La
0.8Sr
0.2)
0.9MnO
3-YSZ battery performance improves 1.3 times.
Embodiment 7
(La
0.8Sr
0.2)
0.8Mn
0.1Ti
0.9O
3Synthetic: with 2.61g La
2O
3Generate La (NO with rare nitric acid (the 4ml red fuming nitric acid (RFNA) is dissolved in 10ml water) dissolving
3)
3The aqueous solution, and then with 0.85g Sr (NO
3)
2With 0.715g Mn (NO
3)
2(quality percentage composition 50%) solution joins above-mentioned La (NO
3)
3In the aqueous solution, stirring is dissolved it fully, forms clear solution.Add the 3.95g Triammonium citrate according to metal ion and 1: 1 ratio of Triammonium citrate, and to transfer pH with nitric acid be 1-2.The 6.12g butyl titanate is joined 17.9g ethylene glycol, stir 30min.Be heated to 70 ℃, the 15.1g citric acid be dissolved in the above-mentioned solution butyl titanate: citric acid: ethylene glycol=1: 4: 16.Above-mentioned solution is added in the metal-nitrate solutions, adds thermal agitation and form transparent and uniform colloidal sol.Be placed on burning formation raw powder on the electric furnace then.This fluffy raw powder at 1100 ℃ of calcining 3h, is obtained titanium doped lanthanum strontium manganese perovskite cathode material.
To be equipped with NiO-YSZ/YSZ two-in-one by burning legal system altogether, burnt altogether 4 hours at proper temperature, obtains the anode assembly.Adopt cladding process preparation (La
0.8Sr
0.2)
0.8Mn
0.1Ti
0.9O
3-YSZ composite cathode was proper temperature roasting 2 hours.With hydrogen is fuel gas, and oxygen is oxidant, 600 ℃ of-800 ℃ of test battery performances.Maximum power density reaches 1.04Wcm in the time of 800 ℃
-2
Utilize the present invention can improve strontium lanthanum manganese oxide cathode material catalytic oxidation-reduction reactive activity, quicken the course of reaction of oxygen on the cathode material surface, reduce cathodic polarization, thereby effectively improve the power output of Solid Oxide Fuel Cell, the output performance of 600 ℃ of batteries improves more than 2 times than standard strontium lanthanum manganese oxide battery.
Claims (7)
1. cathode material for solid-oxide fuel cell is characterized in that: this cathode material is the LSM electric conducting material that transition elements titanium or scandium mix; It consists of (La
1-xSr
x)
1-yMn
1-zM
zO
3 ± δ, 0＜x＜1,0＜y＜1,0＜z≤1 wherein ,-1＜δ＜1, M is titanium elements or scandium element.
2. the application of the described cathode material of claim 1 in solid-oxide fuel battery three-in-one component MEA, this MEA comprises anode, dielectric film and negative electrode, it is characterized in that: described negative electrode, by mass percentage, form by 1-100% claims 1 described cathode material and 0-99% electrolyte; Described electrolyte is 5-20mol%Y
2O
3Stable ZrO
2, 5-20mol%Sc
2O
3Stable ZrO
2, Sm
xCe
1-xO
2, Gd
xCe
1-xO
2, Y
xCe
1-xO
2, La
xCe
1-xO
2, La
1-xSr
xGa
1-yMg
yO
3In one or more, 0＜x＜1,0＜y＜1 wherein.
3. according to the described application of claim 2, it is characterized in that: its manufacturing materials of the anode of described MEA is the metal/oxide composite ceramics, and wherein metallic catalyst comprises Ni, Co, Cu, Rh, Fe, Pt, Pd, Mo, one or more among the Ti; Oxide comprises Sm
xCe
1-xO
2, Gd
xCe
1-xO
2, Y
xCe
1-xO
2, La
xCe
1-xO
2, Y
2O
3Stable ZrO
2, Sc
2O
3Stable ZrO
2, La
1-xSr
xGa
1-yMg
yO
3In one or more, 0＜x＜1,0＜y＜1 wherein; The mass percentage content of metallic catalyst in composite ceramics is 1%-100%.
4. according to the described application of claim 2, it is characterized in that: the dielectric film of described MEA is Sm
xCe
1-xO
2, Gd
xCe
1-xO
2, Y
xCe
1-xO
2, La
xCe
1-xO
2, Y
2O
3Stable ZrO
2, Sc
2O
3Stable ZrO
2, La
1-xSr
xGa
1-yMg
yO
3In one or more, 0＜x＜1,0＜y＜1 wherein.
5. according to the described application of claim 4, it is characterized in that: dielectric film adopts high temperature sintering, vapour deposition, sol-gel or plasma spray process preparation, its thickness is 0.01 micron to 5000 microns, and annealing temperature is in 200 ℃ of-1500 ℃ of interval ranges.
6. according to the described application of claim 2, it is characterized in that: the cell cathode of described MEA adopts The tape casting, silk screen print method, coating process, vapour deposition process or plasma spraying process preparation on dielectric film, 200-1300 ℃ of annealing, its THICKNESS CONTROL is between 0.01 micron to 2000 microns.
7. according to the described application of claim 2, it is characterized in that: the structure of described three-in-one component MEA can adopt plate, cast, flat-tube type or honeycomb type; Adopt dielectric film self-cradling type, cathode support type or anode support type structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN102005579A (en) * | 2010-10-14 | 2011-04-06 | 华北电力大学 | Method for preparing LSM (Lanthanum Strontium Manganate) cathode of solid oxide fuel cell |
| CN102683728A (en) * | 2012-05-14 | 2012-09-19 | 杨绍华 | Anode-supported solid oxide fuel cell and preparation method thereof |
| WO2012151798A1 (en) * | 2011-05-09 | 2012-11-15 | 东南大学 | Black conductive ceramic composite and preparation method thereof |
| DE102012221427A1 (en) | 2011-11-30 | 2013-06-06 | Robert Bosch Gmbh | Fuel cell system i.e. high temperature-fuel cell system, for use in e.g. vehicle, has fuel cells connected in series and/or parallel by interconnectors, where part of interconnectors is made from material with perovskite structure |
| CN104659378B (en) * | 2015-02-07 | 2016-11-23 | 大连理工大学 | A kind of intermediate temperature solid oxide fuel cell nanofiber composite cathode preparation method |
| CN106887631A (en) * | 2015-12-12 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of method for improving perovskite oxide cathodic stability |
| CN108470918A (en) * | 2018-03-12 | 2018-08-31 | 北京科技大学 | A kind of anion doped La of F0.8Sr0.2MnFxO3-x-δCathode material and preparation method thereof |
| CN109417183A (en) * | 2016-07-08 | 2019-03-01 | 圣安德鲁斯大学董事会 | For the method from perovskite metal oxides production electrode catalyst |
| CN109841841A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of high-temperature fuel cell cathode material and its preparation and application |
| CN109904470A (en) * | 2017-12-11 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of cathode material for solid-oxide fuel cell |
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| CN111235589A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | High-temperature electrolytic cell cathode material and preparation and application thereof |
| CN111477881A (en) * | 2020-03-19 | 2020-07-31 | 华南理工大学 | NiFe alloy nanoparticle coated Pr0.8Sr1.2(FeNi)O4-Material and method for producing the same |
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| CN102005579B (en) * | 2010-10-14 | 2013-04-03 | 华北电力大学 | Method for preparing LSM (Lanthanum Strontium Manganate) cathode of solid oxide fuel cell |
| CN102005579A (en) * | 2010-10-14 | 2011-04-06 | 华北电力大学 | Method for preparing LSM (Lanthanum Strontium Manganate) cathode of solid oxide fuel cell |
| WO2012151798A1 (en) * | 2011-05-09 | 2012-11-15 | 东南大学 | Black conductive ceramic composite and preparation method thereof |
| DE102012221427A1 (en) | 2011-11-30 | 2013-06-06 | Robert Bosch Gmbh | Fuel cell system i.e. high temperature-fuel cell system, for use in e.g. vehicle, has fuel cells connected in series and/or parallel by interconnectors, where part of interconnectors is made from material with perovskite structure |
| CN102683728A (en) * | 2012-05-14 | 2012-09-19 | 杨绍华 | Anode-supported solid oxide fuel cell and preparation method thereof |
| CN104659378B (en) * | 2015-02-07 | 2016-11-23 | 大连理工大学 | A kind of intermediate temperature solid oxide fuel cell nanofiber composite cathode preparation method |
| CN106887631A (en) * | 2015-12-12 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of method for improving perovskite oxide cathodic stability |
| CN109417183B (en) * | 2016-07-08 | 2022-05-24 | 圣安德鲁斯大学董事会 | Method for producing electrode catalyst from perovskite metal oxide |
| CN109417183A (en) * | 2016-07-08 | 2019-03-01 | 圣安德鲁斯大学董事会 | For the method from perovskite metal oxides production electrode catalyst |
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| CN109841841A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of high-temperature fuel cell cathode material and its preparation and application |
| CN109904470A (en) * | 2017-12-11 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of cathode material for solid-oxide fuel cell |
| CN109904470B (en) * | 2017-12-11 | 2021-05-11 | 中国科学院大连化学物理研究所 | Cathode material of solid oxide fuel cell |
| CN108470918A (en) * | 2018-03-12 | 2018-08-31 | 北京科技大学 | A kind of anion doped La of F0.8Sr0.2MnFxO3-x-δCathode material and preparation method thereof |
| CN111235589A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | High-temperature electrolytic cell cathode material and preparation and application thereof |
| CN111235589B (en) * | 2018-11-29 | 2021-06-01 | 中国科学院大连化学物理研究所 | High-temperature electrolytic cell cathode material and preparation and application thereof |
| CN110061248A (en) * | 2019-05-05 | 2019-07-26 | 常熟理工学院 | Anti-carbon sulfur resistive poisons anode of solid oxide fuel cell and preparation method thereof |
| CN111477881A (en) * | 2020-03-19 | 2020-07-31 | 华南理工大学 | NiFe alloy nanoparticle coated Pr0.8Sr1.2(FeNi)O4-Material and method for producing the same |
| CN112928314A (en) * | 2021-01-23 | 2021-06-08 | 西安石油大学 | Preparation method of solid oxide fuel cell |
| CN113809343A (en) * | 2021-09-17 | 2021-12-17 | 中国科学技术大学 | Carbon dioxide resistant solid oxide fuel cell cathode material and preparation method thereof |
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