CN107425205A - A kind of anode of solid oxide fuel cell material and its fuel cell - Google Patents
A kind of anode of solid oxide fuel cell material and its fuel cell Download PDFInfo
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- CN107425205A CN107425205A CN201710583531.1A CN201710583531A CN107425205A CN 107425205 A CN107425205 A CN 107425205A CN 201710583531 A CN201710583531 A CN 201710583531A CN 107425205 A CN107425205 A CN 107425205A
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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
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
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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
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
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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
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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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
- 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
A kind of anode of solid oxide fuel cell material provided by the invention, including the oxide material with electron conduction, the oxide material with oxygen conduction, the oxide material chemical molecular formula with oxygen conduction is [(LnO1.5)x(Zr1‑yCeyO2)1‑x]1‑z[MO]z, wherein 0≤x≤0.2,0≤y≤1,0≤z≤0.2, Ln include metal oxide, rare earth oxide, and M is metallic element, additionally provides the battery for including above-mentioned anode material；It is an advantage of the current invention that making anode be not easy to be oxidized, enable battery performance stable for extended periods of time, the endurance issues for solving fuel cell anode materials, the economy of battery can be greatly increased.
Description
Technical field
The invention belongs to SOFC technical field, specially a kind of anode of solid oxide fuel cell
Material and its fuel cell.
Background technology
The anode material of SOFC mainly by electronic conductive material and oxygen-ion conductive material mixing and
Into the oxygen-ion conductive material in anode is generally made up of electrolyte, and three major types electrolyte is stable oxygen at present
Change zirconium (Stabilized-ZrO2Flourite), the cerium oxide (Doped-CeO of doping2Flourite) invented with Ishihara
Lanthanum gallate series (Doped-Lanthanum Gallates Perovskite；US 6844098 B1).Electronics in anode
The nickel that conductive material is formed by nickel oxide reduction is formed, while metallic nickel is the excellent of anode of solid oxide fuel cell reaction
Catalyst.So the anode material of SOFC is represented by NiO-Zirconia, NiO-Ceria, NiO-
Doped Lanthanum Gallates (nickel oxide is reduced to metallic nickel after anode is passed through fuel).Nickel oxide (NiO) and
In the mixture of oxygen-ion conductive material (Oxygen Ion Conductor), nickel oxide quality accounts for nickel oxide and oxonium ion is led
The 30wt%-wt80% of electric material quality sum.
Because the anode of SOFC is nickel and oxide ion conduction oxide mixture, the hydroxide of anode
Reaction just occurs on the contact surface of metallic nickel and oxide ion conduction oxide, and this interface is referred to as the three phase boundary of anode.In pole
Under the conditions of end, when leaking into air in anode so that reducing atmosphere is destroyed in anode, metallic nickel is oxidized to nickel oxide and causes sun
Pole three phase boundary is destroyed, and causes cell performance decay to reduce battery.Compared to traditional compound sun of nickel-oxide
Pole, total oxygen compound anode material have more preferable thermal expansion stability, more outstanding anti-oxidant durability.High-durability means
The longtime running cost of fuel cell can be reduced, the commercialization popularization to SOFC is played vital
Effect, therefore in field of solid oxide fuel, it is always that this area is ground to develop the anode material with premium properties
Study carefully personnel's urgent problem to be solved.
The content of the invention
To solve above mentioned problem in the prior art, the invention provides a kind of anode of solid oxide fuel cell material and
Its fuel cell, the purpose of realization are oxidized caused in the process of running to solve anode of solid oxide fuel cell material
Structure deterioration, the problems such as performance degradation.
To achieve these goals, technical scheme disclosed by the invention is：A kind of soild oxide combustion provided by the invention
Expect battery anode material, including the oxide material with electron conduction, the oxide material with oxygen conduction, institute
It is [(LnO to state the oxide material chemical molecular formula with oxygen conduction1.5)x(Zr1-yCeyO2)1-x]1-z[MO]z, wherein 0
≤ x≤0.2,0≤y≤1,0≤z≤0.2, Ln include metal oxide, rare earth oxide, and M is metallic element.
Traditional anode material is nickel-oxide composite anode, and nickel metal is oxidized into oxygen in high temperature oxidative atmosphere
Change nickel, the catalytic action and electric action that nickel oxide loses；Meanwhile its volume is significantly during nickel oxide is oxidized to for nickel
Increase, destroys the micro-tubular structure of electrode, exists so as to result in the performance degradation of anode material, Related Mechanism M.Ettler etc.
Journal of Power Source, it is described in detail in 195 (2010) 5452-5467.
Oxide multilayer anode material exists in the form of an oxide in cell operation, and its electric conductivity is imitated with electro-catalysis
Fruit is not influenceed by atmosphere in galvanic anode, and its material microstructure is not influenceed by atmosphere change, therefore battery performance can be grown
Phase keeps stable.
Further, the oxide material with electron conduction is the titanate perovskites (doped- of doping
AETiO3)AE1-xLmxTi1-yMixO3, wherein 0≤x≤0.5,0≤y≤0.7, Lm are rare earth element, Mi is metallic element, and AE is
Alkali metal.Alkali metal perovskite is a kind of material of stabilization, and its electrical conductivity and electro-catalysis can be greatly improved by doping
Performance, such as rare earth doped alkali metal perovskite have excellent electron conduction under reducing atmosphere；Metallic element adulterates
Alkali metal perovskite have more preferable electric catalyticing characteristic.
Preferably, the metal oxide Ln is any one or more than one in calcium oxide CaO, magnesia MgO.Oxidation
Calcium and the alkali metal perovskite of oxidation mg-doped have lower elements diffusion characteristic during the hot operation of battery, so as to protect
The steady in a long-term of electrode material is demonstrate,proved.
Preferably, rare earth oxide Ln is scandium oxide Sc2O3, yittrium oxide Y2O3, lanthana La2O3, praseodymium oxide
Pr2O3, neodymia Nd2O3, promethium oxide Pm2O3, samarium oxide Sm2O3, europium oxide Eu2O3, gadolinium oxide Gd2O3, terbium oxide Tb2O3、
Dysprosia Dy2O3, holimium oxide Ho2O3, erbium oxide Er2O3, thulium oxide Tm2O3, ytterbium oxide Yb2O3, luteium oxide Lu2O3In any one
Or more than one.Alkali metal perovskite is a kind of material of stabilization, and by rare earth doped element, alkali metal perovskite is in also Primordial Qi
There is excellent electron conduction under atmosphere.
Preferably, the metallic element M includes Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt.Metallic element doping
Alkali metal perovskite has more preferable electric catalyticing characteristic.
Preferably, the rare earth element Lm is yttrium Y, lanthanum La, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium
Any one in Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lu or more than one.Alkali metal perovskite is a kind of material of stabilization,
By rare earth doped element, alkali metal perovskite has excellent electron conduction under reducing atmosphere.
Preferably, the metallic element Mi include Sc, Cr, V, Mn, Fe, Co, Ni, Cu, Ga, Al, Mg, Nb, Zn, Ru, Rh,
Any one in Pd, Os, Ir, Pt or more than one.The alkali metal perovskite of metallic element doping has more preferable electric catalyticing characteristic.
Preferably, the alkali metal AE be barium Ba, strontium Sr, any one in calcium Ca or more than one.Alkali metal calcium
Titanium ore is a kind of material of stabilization, and by rare earth doped element, alkali metal perovskite has excellent electronics to lead under reducing atmosphere
Electrically.
Further, the oxide material with electron conduction is the Lanthanum Chromite (doped-LaCrO of doping3)
La1-xAMxCr1-yMexO3, wherein 0≤x≤0.5,0≤y≤0.7, AM are alkali metal, Me includes metallic element, transition gold
Belong to element.Lanthanum Chromite is a kind of material of stabilization, and its electrical conductivity and electrocatalysis characteristic can be greatly improved by doping, such as alkali gold
The Lanthanum Chromite of category doping has excellent electron conduction under oxidizing atmosphere；Metallic element, transition metal element doped chromic acid
Lanthanum has more preferable electric catalyticing characteristic and good electron conduction.
Preferably, alkali metal AM be barium Ba, strontium Sr, any one in calcium Ca or more than one.Alkali-metal-doped
Lanthanum Chromite has excellent electron conduction under oxidizing atmosphere.
Preferably, the metallic element Me is any one or more than one in magnesium Mg, aluminium Al.Metallic element, transition gold
The Lanthanum Chromite of category element doping has more preferable electric catalyticing characteristic and good electron conduction.
Preferably, the transition metal Me include Sc, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Os,
Any one in Ir, Pt or more than one.Metallic element, transition metal element doped Lanthanum Chromite have more preferable electro-catalysis special
Property, good electron conduction and sintering characteristic.
Further, the mass percent that is accounted in anode material of oxide material with oxygen conduction be more than
0% is less than 100%.
Further, the titanate perovskites (doped-AETiO of doping3)AE1-xLmxTi1-yMixO3In anode material
The mass percent accounted for is to be less than 100% more than 0%.
Further, the Lanthanum Chromite (doped-LaCrO of doping3)La1-xAMxCr1-yMexO3The matter accounted in anode material
It is to be less than 100% more than 0% to measure percentage
Further, the anode material also includes additional metal elements, what additional metal elements accounted in anode material
Mass percent is 0%~50%, and it is one or more kinds of that additional metal elements include Fe, Co, Ni, Cu, Ti, Cr.Compound
Metallic element is mixed into anode material can improve the electron conduction of anode, while transition metal also has preferable electro-catalysis
Effect.But excessive metallic element can cause the deficiency of oxygen-ion conductive material, while the oxidized risk of metal is also exacerbated,
So the amount of metallic element should control within the specific limits.
The invention also discloses a kind of SOFC, including above-mentioned anode material, above-mentioned anode material can
Battery is formed with electrolyte of the prior art, negative electrode, connector or bipolar plates.
To sum up, the beneficial effects of the invention are as follows：Using anode new material of the present invention, make anode be not easy to be oxidized, make battery
Performance can stable for extended periods of time, solve the endurance issues of fuel cell anode materials, the economy of battery can be greatly increased
Property.
Brief description of the drawings
Fig. 1 is 56wt%NiO-44wt% (Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Initial discharge during as anode is bent
Line with operation 5000 hours after discharge curve；
Fig. 2 is Fig. 2 40wt%La0.2Sr0.8Ti0.9Ni0.1O3- 60wt%Gd0.1Ce0.8Ni0.1O2It is initial during as anode
Discharge curve with operation 5000 hours after discharge curve.
Embodiment
The present invention is described in further detail below by specific embodiment.
Embodiment one：A kind of anode of solid oxide fuel cell material provided by the invention, including with electronic conduction
Property oxide material, have oxygen conduction oxide material, the oxide material with oxygen conduction
Chemical molecular formula is [(LnO1.5)x(Zr1-yCeyO2)1-x]1-z[MO]z, wherein x, y, z is that 0, Ln is the oxidation of any one metal
Thing, M are any one metallic element, and any one oxide material with electron conduction is led with described with oxonium ion
Electrical oxidation material mixing, obtains anode material, the anode material also can be with electrolyte of the prior art, negative electrode, connection
Body or bipolar plates composition battery.
Embodiment two：A kind of anode of solid oxide fuel cell material provided by the invention, including with electronic conduction
Property oxide material, have oxygen conduction oxide material, the oxide material with oxygen conduction
Chemical molecular formula is [(LnO1.5)x(Zr1-yCeyO2)1-x]1-z[MO]z, wherein x, z 0.2, y 1, Ln are any one rare earth
Element oxide, M Mn；
The oxide material with electron conduction is the titanate perovskites (doped-AETiO of doping3)AE1- xLmxTi1-yMixO3, wherein x, y 0, Lm are any one rare earth element, and Mi is any one metallic element, and AE is any one
Kind alkali metal.
The mass percent that the oxide material with oxygen conduction accounts in anode material be more than
0.1%, remaining is then the titanate perovskites (doped-AETiO of doping3)AE1-xLmxTi1-yMixO3。
Embodiment three：A kind of anode of solid oxide fuel cell material provided by the invention, including with electronic conduction
Property oxide material, have oxygen conduction oxide material, the oxide material with oxygen conduction
Chemical molecular formula is [(LnO1.5)x(Zr1-yCeyO2)1-x]1-z[MO]z, wherein x, z 0.1, y 0.5, Ln are calcium oxide CaO, M
For Fe；
The oxide material with electron conduction is the titanate perovskites (doped-AETiO of doping3)AE1- xLmxTi1-yMixO3, wherein x is 0.5, y 0.7, and Lm is that yttrium Y, Mi Sc, AE are barium Ba.
The mass percent that the oxide material with oxygen conduction accounts in anode material is 30%, institute
Stating anode material also includes additional metal elements, and the mass percent that additional metal elements account in anode material is 30%, attached
Metallic element is added to include Fe, Co, Ni, Cu, Ti, Cr mixture, remaining is then the titanate perovskites (doped- of doping
AETiO3)AE1-xLmxTi1-yMixO3。
The anode material also can form battery with electrolyte of the prior art, negative electrode, connector or bipolar plates.
Example IV：A kind of anode of solid oxide fuel cell material provided by the invention, including with electronic conduction
Property oxide material, have oxygen conduction oxide material, the oxide material with oxygen conduction
Chemical molecular formula is [(LnO1.5)x(Zr1-yCeyO2)1-x]1-z[MO]z, wherein x, z 0.05, y 0.8, Ln are magnesia MgO,
M is Co；
The oxide material with electron conduction is the titanate perovskites (doped-AETiO of doping3)AE1- xLmxTi1-yMixO3, wherein x is 0.3, y 0.3, and Lm is lanthanum La, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium
Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lu mixture, Mi V, Mn, Fe, Co, Ni, Cu, Ga, Al, Mg, Nb, Zn, Ru,
Rh, Pd, Os, Ir, Pt mixture, AE are strontium Sr, calcium Ca mixture.
The mass percent that the oxide material with oxygen conduction accounts in anode material is 50%, institute
Stating anode material also includes additional metal elements, and the mass percent that additional metal elements account in anode material is 1%, is added
Metallic element includes Fe, Co, Ni, Cu, Ti, Cr mixture, and remaining is then the titanate perovskites (doped- of doping
AETiO3)AE1-xLmxTi1-yMixO3。
The anode material also can form battery with electrolyte of the prior art, negative electrode, connector or bipolar plates.
Embodiment five：A kind of anode of solid oxide fuel cell material provided by the invention, including with electronic conduction
Property oxide material, have oxygen conduction oxide material, the oxide material with oxygen conduction
Chemical molecular formula is [(LnO1.5)x(Zr1-yCeyO2)1-x]1-z[MO]z, wherein x, z 0.05, y 0.8, Ln aoxidize for magnesia
Scandium Sc2O3, M Ni；
The oxide material with electron conduction is that the oxide material with electron conduction is doping
Lanthanum Chromite (doped-LaCrO3)La1-xAMxCr1-yMexO3, wherein x, y 0, AM are barium Ba, and Me is magnesium Mg, transition metal member
Element is Sc.
The mass percent that the oxide material with oxygen conduction accounts in anode material is 70%, institute
Stating anode material also includes additional metal elements, and the mass percent that additional metal elements account in anode material is 10%, attached
Metallic element is added to include Fe, Co, Ni, Cu, Ti, Cr mixture, remaining is then the Lanthanum Chromite (doped-LaCrO of doping3)
La1-xAMxCr1-yMexO3。
The anode material also can form battery with electrolyte of the prior art, negative electrode, connector or bipolar plates.
Embodiment six：A kind of anode of solid oxide fuel cell material provided by the invention, including with electronic conduction
Property oxide material, have oxygen conduction oxide material, the oxide material with oxygen conduction
Chemical molecular formula is [(LnO1.5)x(Zr1-yCeyO2)1-x]1-z[MO]z, wherein x, z 0.05, y 0.8, Ln are yittrium oxide Y2O3、
Lanthana La2O3, praseodymium oxide Pr2O3, neodymia Nd2O3, promethium oxide Pm2O3, samarium oxide Sm2O3, europium oxide Eu2O3, gadolinium oxide
Gd2O3 mixture, M Ru, Rh, Pd, Os mixture；
The oxide material with electron conduction is that the oxide material with electron conduction is doping
Lanthanum Chromite (doped-LaCrO3)La1-xAMxCr1-yMexO3, wherein x is 0.5, y 0.7, AM are strontium Sr, and Me is aluminium Al, mistake
Cross the mixture that metallic element is Ti, V, Mn, Fe, Co, Ni.
The mass percent that the oxide material with oxygen conduction accounts in anode material is 40%, institute
Stating anode material also includes additional metal elements, and the mass percent that additional metal elements account in anode material is 20%, attached
Metallic element is added to include Fe, Co, Ni, Cu, Ti, Cr mixture, remaining is then the Lanthanum Chromite (doped-LaCrO of doping3)
La1-xAMxCr1-yMexO3。
The anode material also can form battery with electrolyte of the prior art, negative electrode, connector or bipolar plates.
Embodiment seven：A kind of anode of solid oxide fuel cell material provided by the invention, including with electronic conduction
Property oxide material, have oxygen conduction oxide material, the oxide material with oxygen conduction
Chemical molecular formula is [(LnO1.5)x(Zr1-yCeyO2)1-x]1-z[MO]z, wherein x, z 0.05, y 0.8, terbium oxide Tb2O3, oxygen
Change dysprosium Dy2O3, holimium oxide Ho2O3, erbium oxide Er2O3, thulium oxide Tm2O3, ytterbium oxide Yb2O3, luteium oxide Lu2O3Mixture, M is
Ir, Pt mixture；
The oxide material with electron conduction is that the oxide material with electron conduction is doping
Lanthanum Chromite (doped-LaCrO3)La1-xAMxCr1-yMexO3, wherein x is 0.3, y 0.3, AM are calcium Ca, and Me is aluminium Al, mistake
Cross the mixture that metallic element is Cu, Zn, Ru, Rh, Pd, Os, Ir, Pt.
The mass percent that the oxide material with oxygen conduction accounts in anode material is 60%, institute
Stating anode material also includes additional metal elements, and the mass percent that additional metal elements account in anode material is 10%, attached
Metallic element is added to include Fe, Co, Ni, Cu, Ti, Cr mixture, remaining is then the Lanthanum Chromite (doped-LaCrO of doping3)
La1-xAMxCr1-yMexO3。
The anode material also can form battery with electrolyte of the prior art, negative electrode, connector or bipolar plates.
Embodiment seven：Using electron conducting oxide La0.2Sr0.8Ti0.9Ni0.1O3With oxide ion conduction oxide
Gd0.1Ce0.8Ni0.1O2Mixture as anode material, La0.2Sr0.8Ti0.9Ni0.1O3Account for the 40wt% of mixture gross mass
La0.2Sr0.8Ti0.9Ni0.1O3- 60wt%Gd0.1Ce0.8Ni0.1O2It can be obtained by any material synthetic method.
First, organic bond is added into above-mentioned composite anode powder and composite anode pole slurry is made, wherein above-mentioned multiple
The mass ratio for closing anode powder and organic binder bond is 5：5.
Then, using (Sc of the method for silk-screen printing at 200 μm2O3)0.10(CeO2)0.01(ZrO2)0.89Electrolyte sheet one
Side printing top surface area 0.64cm240wt%La0.2Sr0.8Ti0.9Ni0.1O3- 60wt%Gd0.1Ce0.8Ni0.1O2Anode slurry is made
For anode, after dryingMiddle sintering 4 hours.Printed in the opposite side of electrolyte sheet using the method for silk-screen printing
Surface area 0.64cm2(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Cathode slurry is done as negative electrode
After dryMiddle sintering 4 hours.
Mass ratio is 56 to 44 NiO- (Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Standard composite anode materials are also carried out
Performance test.To the NiO- (Sc that mass ratio is 56 to 442O3)0.10(CeO2)0.01(ZrO2)0.89Middle addition organic bond is made
Anode slurry, wherein the mass ratio of above-mentioned anode powder and organic binder bond is 5：5.
Then, using (Sc of the method for silk-screen printing at 200 μm2O3)0.10(CeO2)0.01(ZrO2)0.89Electrolyte sheet one
Side printing top surface area 0.64cm256wt%NiO-44wt% (Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Anode slurry conduct
Anode, dry afterMiddle sintering 4 hours.Upper table is printed using the method for silk-screen printing in the opposite side of electrolyte sheet
Area 0.64cm2(La0.8Sr0.2)0.98MnO3-(Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Cathode slurry is dried as negative electrode
Exist afterwardsMiddle sintering 4 hours.
Monocell performance test is carried out under furnace temperature, anode is passed through the hydrogen for being mixed with 3vol% vapor, cloudy
Pole is passed through air.The initial discharge curve of battery measures in the hydrogen of 3vol% vapor, is changed to anode atmosphere after test
The hydrogen of 90vol% vapor is included, battery is maintained at 400mAcm-2Lower operation 5000 hours, finally will be by anode atmosphere again
The hydrogen for including 3vol% vapor is changed to, now carries out discharge curve test.
Fig. 1 is 56wt%NiO-44wt% (Sc2O3)0.10(CeO2)0.01(ZrO2)0.89Initial discharge during as anode is bent
Line with operation 5000 hours after discharge curve, can show that discharge curve has deep fades after operation by figure.
Fig. 2 is 40wt%La0.2Sr0.8Ti0.9Ni0.1O3- 60wt%Gd0.1Ce0.8Ni0.1O2Initial discharge during as anode
Discharge curve after curve and operation 5000 hours, as seen from the figure, discharge curve are only slightly decayed operation is front and rear, explanation
40wt%La0.2Sr0.8Ti0.9Ni0.1O3- 60wt%Gd0.1Ce0.8Ni0.1O2Anode material has preferable durability.This new material solution
Determine the endurance issues of fuel cell anode materials, the economy of battery can be greatly increased.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (17)
1. a kind of anode of solid oxide fuel cell material, it is characterised in that the material includes the oxygen with electron conduction
Compound material, the oxide material with oxygen conduction, the oxide material chemistry point with oxygen conduction
Minor is [(LnO1.5)x(Zr1-yCeyO2)1-x]1-z[MO]z, wherein 0≤x≤0.2,0≤y≤1,0≤z≤0.2, Ln include gold
Belong to oxide, rare earth oxide, M is metallic element.
2. anode of solid oxide fuel cell material according to claim 1, it is characterised in that described to be led with electronics
Electrical oxide material is the titanate perovskites (doped-AETiO of doping3)AE1-xLmxTi1-yMixO3, wherein 0≤x≤
0.5,0≤y≤0.7, Lm are rare earth element, and Mi is metallic element, and AE is alkali metal.
3. anode of solid oxide fuel cell material according to claim 1, it is characterised in that the metal oxide
For any one in calcium oxide CaO, magnesia MgO or more than one.
4. anode of solid oxide fuel cell material according to claim 1, it is characterised in that rare earth oxide
For scandium oxide Sc2O3, yittrium oxide Y2O3, lanthana La2O3, praseodymium oxide Pr2O3, neodymia Nd2O3, promethium oxide Pm2O3, samarium oxide
Sm2O3, europium oxide Eu2O3, gadolinium oxide Gd2O3, terbium oxide Tb2O3, dysprosia Dy2O3, holimium oxide Ho2O3, erbium oxide Er2O3, oxygen
Change thulium Tm2O3, ytterbium oxide Yb2O3, luteium oxide Lu2O3In any one or more than one.
5. anode of solid oxide fuel cell material according to claim 1, it is characterised in that the metallic element bag
Include Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt.
6. anode of solid oxide fuel cell material according to claim 2, it is characterised in that the rare earth element is
Appoint in yttrium Y, lanthanum La, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lu
Meaning is one or more kinds of.
7. anode of solid oxide fuel cell material according to claim 2, it is characterised in that the metallic element bag
Include any one in Sc, Cr, V, Mn, Fe, Co, Ni, Cu, Ga, Al, Mg, Nb, Zn, Ru, Rh, Pd, Os, Ir, Pt or it is a kind of with
On.
8. anode of solid oxide fuel cell material according to claim 2, it is characterised in that the alkali metal
For any one in barium Ba, strontium Sr, calcium Ca or more than one.
9. anode of solid oxide fuel cell material according to claim 1, it is characterised in that described to be led with electronics
Electrical oxide material is the Lanthanum Chromite (doped-LaCrO of doping3)La1-xAMxCr1-yMexO3, wherein 0≤x≤0.5,0≤
Y≤0.7, AM are alkali metal, and Me includes metallic element, transition metal.
10. anode of solid oxide fuel cell material according to claim 9, it is characterised in that the alkali metal member
Element is barium Ba, strontium Sr, any one in calcium Ca or more than one.
11. anode of solid oxide fuel cell material according to claim 9, it is characterised in that the metallic element
For any one in magnesium Mg, aluminium Al or more than one.
12. anode of solid oxide fuel cell material according to claim 9, it is characterised in that the transition metal
Element includes any one or more than one in Sc, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Os, Ir, Pt.
13. anode of solid oxide fuel cell material according to claim 1, it is characterised in that led with oxonium ion
The mass percent that electrical oxide material accounts in anode material is to be less than 100% more than 0%.
14. anode of solid oxide fuel cell material according to claim 2, it is characterised in that the titanate of doping
Perovskite (doped-AETiO3)AE1-xLmxTi1-yMixO3The mass percent accounted in anode material is to be less than more than 0%
100%.
15. anode of solid oxide fuel cell material according to claim 9, it is characterised in that the Lanthanum Chromite of doping
(doped-LaCrO3)La1-xAMxCr1-yMexO3The mass percent accounted in anode material is to be less than 100% more than 0%.
16. the anode of solid oxide fuel cell material according to claim 2 or 9, it is characterised in that the anode material
Material also includes additional metal elements, and the mass percent that additional metal elements account in anode material is 0%~50%, adds gold
Belonging to element includes Fe, Co, Ni, Cu, Ti, Cr one or more.
17. a kind of SOFC, it is characterised in that including the anode material described in claim any one of 1-16
Material.
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| CN109244438A (en) * | 2018-11-22 | 2019-01-18 | 北京科技大学 | A method of perovskite structural material is coated on positive electrode particle surface |
| CN111180772A (en) * | 2020-01-06 | 2020-05-19 | 神华新能源有限责任公司 | Preparation method for preparing solid oxide fuel cell material |
| CN112701298A (en) * | 2019-10-07 | 2021-04-23 | 太阳诱电株式会社 | Solid oxide fuel cell and method for manufacturing same |
| CN113233518A (en) * | 2020-12-25 | 2021-08-10 | 南京工业大学 | Solid oxide fuel cell anode catalytic material with multi-carbon fuel catalytic hydrogen production function and preparation method thereof |
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