CN100583516C - A cathode material for A and B adulterated SrTiO3 solid oxide fuel battery - Google Patents

A cathode material for A and B adulterated SrTiO3 solid oxide fuel battery Download PDF

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CN100583516C
CN100583516C CN200810056546A CN200810056546A CN100583516C CN 100583516 C CN100583516 C CN 100583516C CN 200810056546 A CN200810056546 A CN 200810056546A CN 200810056546 A CN200810056546 A CN 200810056546A CN 100583516 C CN100583516 C CN 100583516C
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anode
oxide fuel
solid oxide
anode material
doping
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CN101237046A (en
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赵海雷
李雪
高峰
周雄
张翠娟
陈宁
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University of Science and Technology Beijing USTB
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Abstract

The present invention relates to an anode material, in particular to a solid oxide fuel battery anode material. The anode material is characterized in that: the co-doping of an A-site La and a B-site Sc is carried out for the perovskite type SrTiO3; the molecular formula after doping is La0.30Sr0.70ScxTi1-xO3-delta, wherein, x is equal to 0.001-0.10. The A-site and the B-site co-doped anode material prepared by the present invention can be used for solid oxide fuel batteries, having stable performance and good chemical compatibility with electrolytes YSZ and LSGM. Along with the increase of Sc doping amount, the ionic conductivity of La0.30Sr0.70ScxTi1-xO3-delta is increased, and the ionic conductivity of La0.30Sr0.70ScxTi1-xO3-delta (x is equal to 0.10) at 800 DEG C is increased to 0.0095S.cm-1, so as to improve the work performance of SOFC and promote the practical process of SOFC.

Description

A kind of A, B position codope strontium titanates anode of solid oxide fuel cell material
Technical field
The present invention relates to a kind of anode material, be specifically related to a kind of anode of solid oxide fuel cell material.
Technical background
Solid Oxide Fuel Cell (SOFC) is a kind of novel device that directly chemical energy is converted into electric energy, has advantages such as energy conversion efficiency height, suitability of fuel are strong, cleaning, noiselessness, is one of the most potential green energy resource.Anode also claims fuel electrode, is the important component part of SOFC, and the performance of anode has directly influenced the overall performance of SOFC.In SOFC, fuel is in anode and oxonium ion reaction, therefore need anode that fuel oxidation is had stronger catalytic activity, under the reducing atmosphere of fuel, has higher structural stability, also need higher electronic conductance and ionic conductance, make electrolyte pass the oxonium ion of coming and arrive conversion zone smoothly, the electronics that reaction produces passes to external loop smoothly and produces electric current.
SOFC anode material commonly used at present is a Ni/YSZ cermet anode, and this anode has higher electronics and ionic conductance and catalytic activity.According to document E P Murray.T Tsai, S A Barnett.A direct-methane fuel cell with aceria-based anode.Nature, 1999,400:649-651 and Hideto Kurokawa, Liming Yang, Craig P.Jacobson, Lutgard C.De Jonghe, Steven J.Visco, Y-doped SrTiO 3Based sulfur tolerant anode forsolid oxide fuel cells.Journal ofPower Sources, 2007, the 164:510-518 report, when being fuel with the reformation natural gas, there are problems such as carbon laydown and sulfur poisoning in Ni/YSZ, simultaneously, finely divided Ni particle easily produces particle sintering and agglomeration traits when the SOFC hot operation, thereby reduces the catalytic activity of Ni.These problems all will cause the decay of battery operated performance.Therefore, it is urgent and necessary seeking the new SOFC anode material of can be to the catalysis of hydrocarbon fuel Direct Electrochemistry but not producing carbon laydown, it will make the hydrocarbon gas that are comparatively cheap, wide material sources that comprise gasoline, propane, natural gas etc. become possibility as SOFC fuel, and this will promote the commercialization process of SOFC.
The SrTiO that mixes 3It is a kind of rising SOFC anode material.According to document T.Kawada, T.Watanabe, A.Kaimai, K.Kawamura, Y. Nigara, J.Mizusaki, High temperature transportproperties in SrTiO 3Under an oxygen potential gradient.Solid State Ionics 108 (1998) 391-402 and F.Noll, W.M ü nch, I.Denk, J.Maier, SrTiO 3As a prototype of a mixed conductorConductivities, oxygen diffusion and boundary effects.Solid State Ionics 86-88 (1996) 711-717 report, SrTiO 3Has ABO 3The type perovskite structure can keep good thermal stability and structural stability in very wide partial pressure of oxygen and temperature range.The SrTiO of stoichiometric proportion 3Conductivity is very low, can not be directly used in anode material.But it has very strong doping ability in A, B position, and the doping by A, B bit element can improve the electronic conductance and the ionic conductance of material, and can improve the catalytic activity and the hot expansibility of material, thereby becomes one of preferred material of SOFC anode material.The SrTiO that mixes 3Show the character of mixed conductor, electrochemical reaction can take place on entire electrode, and this will reduce the concentration polarization of battery.Simultaneously, SrTiO 3Be full ceramic component, at high temperature have structural stability and the chemical stability higher than Ni/YSZ.The SrTiO that mixes 3Can with multiple electrolyte compatibility, physics and chemical reaction can not take place.In recent years, SrTiO 3The base anode material has caused people's very big interest.But the battery performance by this anode material assembling is desirable not enough, and power output is on the low side, and conductivity of electrolyte materials particularly ionic conductivity is on the low side.How to improve SrTiO by the selection of doped chemical kind and the control of doping 3Conductivity, become SrTiO 3Key point as SOFC anode material practicability.
According to document O.A.Marina, N.L. Canfield, J.W. Stevenson.Thermal, electrical, andelectrocatalytical properties of lanthanum-doped strontium titanate, Solid State Ionics, 2002 (149): 21-28 report: La doping SrTiO 3Conductivity be subjected to the influence of doping and partial pressure of oxygen bigger, the physics of this material and stable chemical performance in redox reaction.According to document [Solid Oxide Fuel Cell La xSr 1-xTiO 3The conductivity of anode material, investigation of materials journal, 21,2007,255-260] report: La is doped with the increase that is beneficial to conductivity, and is unfavorable for the densification of material, and the conductivity of the sample of reducing atmosphere preparation is higher.La mixes can improve conductivity of electrolyte materials, but electronic conductance and ionic conductance are collaborative processes when the SOFC anode material is worked, and the ionic conductance in the La strontium titanate doping perovskite anode material is far below the electronic conductance of material, this will cause causing bigger anode polarization phenomenon in the battery operation process, thereby the ionic conductance that how to improve anode material is one of key factor that improves SOFC anode material performance.In order further to improve the ionic conductance performance of anode material, need La doping SrTiO 3Anode performance carries out further structure and optimization in Properties.
Summary of the invention
The objective of the invention is to improve stoichiometric proportion SrTiO 3The material electronics electricity is led the defective on the low side with ionic conductivity, proposes a kind of stable performance, Solid Oxide Fuel Cell anode material La that conductivity is high 0.30Sr 0.70Sc xTi 1-xO 3-δ, promptly at Ca-Ti ore type SrTiO 3The A position carry out the doping of La, the doping control of Sc is carried out in the B position, improves the ionic conductivity of anode material, improves the operating characteristic of anode material, and then improves the SOFC service behaviour.This material and electrolyte YSZ, LSGM have good chemical compatibility.
Concrete technical scheme of the present invention is: Ca-Ti ore type SrTiO 3The A position be the doping of 30mol%La, B position Sc mixes, the molecular formula behind the codope is: La 0.30Sr 0.70Sc xTi 1-xO 3-δ, x=0.001-0.10 wherein.La 0.30Sr 0.70Sc xTi 1-xO 3-δIonic conductivity increase along with the increase of Sc doping, preferred molecular formula is La 0.30Sr 0.70Sc 0.10Ti 0.90O 3-δThe conductivity of this material in the time of 800 ℃ is 48.71S.cm -1, ionic conductivity is 0.0095S.cm -1Conductivity in the time of 1000 ℃ is 45.84S.cm -1, ionic conductivity is 0.010S.cm -1
Material of the present invention can be synthetic with solid reaction process, also can be synthetic with hydro thermal method and citric acid method.Be the synthetic method that example is introduced material of the present invention with the solid reaction process below, concrete steps are:
A, with raw material with La 2O 3Or La (NO 3) 3Or La 2(CO 3) 3, SrCO 3Or SrO or Sr (NO 3) 2, Sc 2O 3Or Sc (NO 3) 3, TiO 2According to La 0.30Sr 0.70Sc xTi 1-xO 3-δ(x=0.001-0.10) stoichiometric ratio preparation.
The SrTiO of b, above-mentioned A position, B position codope 3Material adopts solid phase method synthetic powder in 1200-1600 ℃, reducing atmosphere.
C, A position, the SrTiO of B position codope with synthetic 3After powder wet-milling or the dry grinding, sieve (100-200 order) prepares vacant doping SrTiO 3The anode fine powder.
D, in the A position, the SrTiO of B position codope 3Add the inflammable substance of 10-50 volume % in the anode fine powder, inflammable substance comprises carbon dust, starch, corn flour, resin, and dry-pressing or half-dried molded then in 1300-1650 ℃ of temperature lower calcination 2-16 hour, can prepare the porous anode block again; Or with the SrTiO of A position, B position codope 3The anode powder in add entry, soluble starch and ethyl cellulose and make slurry, adopt silk screen print method that it is coated in the fine and close YSZ or the LaGaO of doping equably 3The A of porous, the SrTiO of B position codope through 1100-1600 ℃ of temperature lower calcination 2-16 hour, are made in the electrolyte sheet surface 3Anode film.
The invention has the advantages that, to Ca-Ti ore type SrTiO 3Material carries out A, B position codope, thereby causes the increase of oxygen vacancy concentration, and with respect to the do not mix material of Sc of B position, its ionic conductivity is significantly improved, for La 0.30Sr 0.70Sc xTi 1-xO 3-δ(x=0.10) sample, the conductivity in the time of 800 ℃ are 48.71S.cm -1, ionic conductivity is 0.0095S.cm -1, form mixed conductor material a kind of perovskite structure, macroion conductivity.Control the incorporation of Sc ion, can obtain the perovskite structural material of single pure phase., occur without any impurity for doping Sc in B position is the x-ray diffraction pattern of 0.10 material as Fig. 1, material shows as pure perovskite structure.
Description of drawings
Fig. 1 is the synthetic La of solid reaction process of the present invention 0.30Sr 0.70Sc xTi 1-xO 3-δXRD figure during powder x=0.10, synthesis temperature are 1500 ℃.
The La that Fig. 2 synthesizes for the present invention 0.30Sr 0.70Sc xTi 1-xO 3-δThe temperature variant curve of total conductivity of (x=0.03,0.05,0.08,0.10) sample, sintering temperature is 1500 ℃.
The La that Fig. 3 synthesizes for the present invention 0.30Sr 0.70Sc xTi 1-xO 3-δThe temperature variant curve of ionic conductivity of (x=0.05,0.10) sample, sintering temperature is 1500 ℃.
Embodiment
Embodiment 1:La 0.30Sr 0.70Sc 0.10Ti 0.90O 3-δSolid reaction process synthetic
With La 2O 3, SrCO 3, Sc 2O 3, TiO 2Be raw material, according to La 0.30Sr 0.70Sc 0.10Ti 0.90O 3-δThe element ratio preparating mixture, be medium with alcohol, ball milling is 6 hours in the agate ball ball grinder, after mixing, dries in baking oven.The powder grinding of oven dry is sieved in (100 order), and the powder after sieving is contained in the alumina crucible, in 5%H 2In/Ar the atmosphere, 1300 ℃ of insulations were synthesized in 10 hours.Synthetic powder is sieved in (100 order), add the carbon dust of 40 volume %, 2 volume %PVA solution mix dry-pressing formedly, and the sample that makes is incubated 5 hours down at 1500 ℃, make the porous anode material.With 1300 ℃ of synthetic codope SrTiO 3Powder, dry-pressing formed under the 100MPa, 5%H 2In/Ar the atmosphere, 10 hours densification sinterings of 1500 ℃ of insulations, adopt four end leads method to measure the total conductivity of material, the measure and monitor the growth of standing timber ionic conductance of material of blocking electrode method, the conductivity during 1000 ℃ of this materials is 45.84S.cm -1, ionic conductivity is 0.010S.cm -1, as shown in Figure 3, the Sc doping is 0.10 o'clock, material all is higher than not vacant sample far away in ionic conductivity at each temperature.Under 1000 ℃ of conditions with YSZ, La 0.8Sr 0.2Ga 0.8Mg 0.2O 3Electrolyte does not have chemical reaction.
Embodiment 2:La 0.30Sr 0.70Sc 0.05Ti 0.95O 3-δHydro thermal method synthetic
With La (NO 3) 3, Sr (NO 3) 2, Sc (NO 3) 3, TiCl 4Be raw material, according to La 0.30Sr 0.70Sc 0.05Ti 0.95O 3-δThe element ratio preparating mixture, be solvent with the potassium hydroxide solution of 1mol/L, be reflected in the autoclave of sealing and carry out, autoclave is warming up to 150 ℃ of insulation 30min.Behind the autoclave natural cooling, with the washing of precipitate drying, the powder that obtains synthesizing.With synthetic powder sieve (160 order), get the 1g powder, add the soluble starch of 10% mass fraction and the ethyl cellulose of 2% mass fraction, add the 1ml deionized water at last, mix the back and be coated in the electrolyte YSZ surface of the densification that high temperature burns till with silk screen print method equably, be incubated 10 hours down at 1450 ℃, make the porous anode thin-film material.
Embodiment 3:La 0.30Sr 0.70Sc 0.08Ti 0.92O 3-δCitric acid method synthetic
Press La 0.30Sr 0.70Sc 0.08Ti 0.92O 3-δStoichiometric proportion take by weighing butyl titanate, La 2(CO 3) 3, Sc 2O 3And SrCO 3Earlier butyl titanate and ethylenediamine tetra-acetic acid (EDTA analyzes pure) are mixed, wherein the mol ratio of EDTA and titanium ion is 1: 1, and the back that is dissolved in water to clarification, adds La 80 ℃ of stirring in water bath again 2(CO 3) 3And SrCO 3In the mol ratio of citric acid and titanium ion is that 4: 1 ratio adds citric acid, regulates the pH value to 8-9 with ammoniacal liquor, obtains light yellow vitreosol through adding thermal agitation.Colloidal sol obtains clear gel after the drying in baking oven, gel obtains porous spongy coking product through the heating coking.With obtaining elementary powder after the grinding of coking product is presoma.In 500-600 ℃ of temperature range, elementary powder is heat-treated, obtain synthetic powder.Synthetic powder is sieved in (100 order), add the carbon dust of 40 volume %, 2 volume %PVA solution mix dry-pressing formedly, and the sample that makes is incubated 16 hours down at 1400 ℃, make the porous anode material.Under 1000 ℃ of conditions with YSZ, La 0.8Sr 0.2Ga 0.8Mg 0.2O 3Electrolyte does not have chemical reaction.
The present invention be before experiment according to Theoretical Calculation, draw to make and have La 0.30Sr 0.70Sc xTi 1-xO 3-δThe raw material proportioning of perovskite structural material is prepared burden according to proportioning.Show from the XRD figure (Fig. 1) of the powder that obtains, synthesized material with perovskite structure; According to the conductivity (Fig. 2) that experiment records, prove that La has been incorporated into the A position, Sc has been incorporated into the B position.

Claims (3)

1, a kind of A, B position codope strontium titanates anode of solid oxide fuel cell material is characterized in that, to Ca-Ti ore type SrTiO 3Carry out the codope of A position La, B position Sc, the molecular formula behind the codope is: La 0.30Sr 0.70Sc xTi 1-xO 3-δ, x=0.001-0.10 wherein.
2, A as claimed in claim 1, B position codope strontium titanates anode of solid oxide fuel cell material is characterized in that the preferred La of the molecular formula behind the codope 0.30Sr 0.70Sc 0.10Ti 0.90O 3-δ
3, the purposes of the described A of claim 1, B position codope strontium titanates anode of solid oxide fuel cell material, this material is used for Solid Oxide Fuel Cell.
CN200810056546A 2008-01-22 2008-01-22 A cathode material for A and B adulterated SrTiO3 solid oxide fuel battery Expired - Fee Related CN100583516C (en)

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Publication number Priority date Publication date Assignee Title
CN104779398A (en) * 2015-04-27 2015-07-15 上海邦民新能源科技有限公司 Solid oxide fuel cell anode material and anode provided with same
CN105976892B (en) * 2016-03-22 2017-11-03 红河学院 A kind of lanthanum indium codope strontium titanates conductor material and preparation method thereof
CN106098137B (en) * 2016-06-30 2018-05-11 红河学院 A kind of A vacant A, B position codope strontium titanates mixed conductor material
CN105989908B (en) * 2016-07-21 2018-03-09 红河学院 A kind of A, B position codope strontium titanates mixed conductor material
CN109592981B (en) * 2017-09-30 2021-06-15 中国科学院上海硅酸盐研究所 Porous rare earth titanate heat insulation material and preparation method and application thereof
CN109637694A (en) * 2018-12-21 2019-04-16 红河学院 A kind of A, B codope strontium titanates conductor material and preparation method thereof
CN113292340B (en) * 2021-06-02 2022-08-26 哈尔滨工业大学 High-piezoelectricity low-loss donor-acceptor co-doped piezoelectric ceramic, and preparation method and application thereof
CN117718059A (en) * 2024-02-07 2024-03-19 北京科技大学 Nickel sulfide loaded strontium aluminum titanate-doped photocatalytic composite material and preparation method thereof

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
Sc-substituted Oxygen Excess Titanates as FuelElectrodesfor SOFCs. Jesus Canales Vazquez et al.Journal of The Electrochemical Society,Vol.152 No.7. 2005
Sc-substituted Oxygen Excess Titanates as FuelElectrodesfor SOFCs. Jesus Canales Vazquez et al.Journal of The Electrochemical Society,Vol.152 No.7. 2005 *
The role of dopant concentration,A-site deficiencyand processing on the electrical properties of strontium- andtitanium-doped lanthanum scandate. Charles hatchwell et al.Solid State Ionics,Vol.167 . 2004
The role of dopant concentration,A-site deficiencyand processing on the electrical properties of strontium- andtitanium-doped lanthanum scandate. Charles hatchwell et al.Solid State Ionics,Vol.167 . 2004 *
固体氧化物燃料电池LaxSr1-xTiO3阳极材料的电导性能. 赵海雷等.材料研究学报，第21卷第3期. 2007
固体氧化物燃料电池LaxSr1-xTiO3阳极材料的电导性能. 赵海雷等.材料研究学报，第21卷第3期. 2007 *

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