CN103346342B - Aluminium is for silicon doping apatite-type lanthanum silicate solid electrolyte and preparation method thereof - Google Patents
Aluminium is for silicon doping apatite-type lanthanum silicate solid electrolyte and preparation method thereof Download PDFInfo
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- CN103346342B CN103346342B CN201310243863.7A CN201310243863A CN103346342B CN 103346342 B CN103346342 B CN 103346342B CN 201310243863 A CN201310243863 A CN 201310243863A CN 103346342 B CN103346342 B CN 103346342B
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Abstract
The present invention relates to a kind of aluminium for silicon doping apatite-type lanthanum silicate solid electrolyte and preparation method thereof, its chemical formula is La9.33Si6-XAlXO26-X/2, wherein the span of x is 0.2-2.0, includes following steps: get La according to stoichiometric proportion2O3, aluminium source and ethyl orthosilicate, with La2O3, aluminium source is initiation material, joins in the mixed solution of nitric acid and absolute ethyl alcohol and dissolves completely, then add urea and ethyl orthosilicate to form precursor solution in mixed solution, regulates pH value, formation precursor gel after insulation; Take out aqueous precursor gel burning, grinding and compressing, last sintering. The invention has the beneficial effects as follows: its cost is low, burning time is 5-7min, and the reaction time is short, and preparation technology is simple, has realized synthesizing under middle cryogenic conditions; Products obtained therefrom purity is high; Improve the electrolytical electrical conductivity of lanthanum silicate.
Description
Technical field
The present invention relates to a kind of aluminium for silicon doping apatite-type lanthanum silicate solid electrolyte and preparation method thereof, belong to soild oxideFuel cell technology field.
Background technology
SOFC (SOFC) is a kind of energy conversion device that directly chemical energy is converted into electric energy, and it hasEfficiently, the series of advantages such as environmental friendliness, life-span be long, have before wide application in fields such as generating, traffic, Aero-SpaceScape. Solid electrolyte is the core component of SOFC, plays the important function of isolation reacting gas and delivery of oxygen ion, and its electricity is ledThe size of performance directly affects the performance of fuel cell. SOFC operating temperature higher (800-1000 DEG C), to electrolyte, electricityThe performance requirement harshness of the utmost point, zirconia (YSZ) electrolyte of traditional stabilized with yttrium oxide needs at high temperature just can maintainThe electrical conductivity advantage that it is higher, also can cause the shortcomings such as the slow degradable corrosion of material, bad interfacial reaction, high cost, oneDetermine to have restricted in degree the commercialized development of SOFC. Under the middle low temperature in succession occurring, there is the fluorite type CeO of high ionic conductivity2Base, Bi2O3, there is equally insoluble problem in base and perovskite electrolyte. Therefore, exploitation excellent performance is novelThe middle low temperature that electrolyte is realized SOFC has great importance.
As a kind of novel solid electrolyte, apatite-type La9.33(SiO4)6O2Under middle low temperature, there is high ionic conductanceRate and lower activation energy, stability of material is good, and hot expansibility and electrode material match, and have the soild oxide of being applied toThe potentiality of fuel cell. For it is applied in SOFC better, by doping vario-property, explore new preparation technology and carryThe electrical conductivity of high lanthanum silicate, becomes the emphasis of current research. With regard to doping position, be mainly to replace around the cation of lanthanum position,The doping research of system is also not comprehensive, particularly to seldom report of silicon position doping.
Research shows, the fault of construction that doping causes is the key that affects ionic conductivity, and cation vacancy and interstitial oxygen concentration canEffectively improve the electrolytical electrical conductivity of lanthanum silicate, and the contribution of interstitial oxygen concentration is larger. Now about the synthetic work of apatite-type lanthanum silicateSkill mainly contains high temperature solid-state method and sol-gel process, further develops but shortcoming separately has all limited it.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of aluminium for silicon doping apatite-type lanthanum silicate for above-mentioned prior artSolid electrolyte and preparation method thereof, has improved the electrolytical electrical conductivity of lanthanum silicate, at lambda sensor, film, soild oxideThe various fields such as fuel cell have good application prospect.
The present invention solves the problems of the technologies described above adopted technical scheme: aluminium is for silicon doping apatite-type lanthanum silicate solid electrolyte,Its chemical formula is La9.33Si6-XAlXO26-X/2, wherein the span of x is 0.2-2.0.
Aluminium, for the preparation method of silicon doping apatite-type lanthanum silicate solid electrolyte, by the following technical solutions, includes following stepRapid: according to La9.33Si6-XAlXO26-X/2Stoichiometric proportion get La2O3, aluminium source and ethyl orthosilicate, wherein the value model of xEnclose for 0.2-2.0, with La2O3, aluminium source is initiation material, join in the mixed solution of nitric acid and absolute ethyl alcohol and dissolve completely,In mixed solution, add urea and ethyl orthosilicate to form precursor solution again, regulate pH value, after insulation, form precursor solidifyingGlue; Take out aqueous precursor gel burning, grinding and compressing, last sintering can obtain aluminium for silicon doping apatite-type lanthanum silicateSolid electrolyte.
Press such scheme, described aluminium source is aluminium oxide or aluminum nitrate.
Press such scheme, described adjusting pH value is to adopt ammoniacal liquor to regulate pH value to 4-6.
Press such scheme, described insulation refers at 70-80 DEG C of insulation 2-4h.
Press such scheme, described burning, grinding, concrete technology compressing and sintering refers to that taking out aqueous precursor gel existsLight for 500-700 DEG C, burning 5-7min obtains spongy powder; After being ground, spongy powder calcines 8-12h at 800-900 DEG CObtain high-purity powder; Again grind after at 225-250MPa forming under the pressure, then sintering 3h-5h at 1400-1600 DEG C.
Urea-nitrate combustion method proposed by the invention, in aqueous precursor gel combustion process, nitric acid is the molten of metal oxideAgent, nitrate and urea generation combustion reaction that reaction generates; Excessive nitric acid occurs with the ammoniacal liquor that regulates precursor solution pH valueNeutralization reaction generates ammonium nitrate, and ammonium nitrate is also important fuel, can with urea generation combustion reaction; Aqueous precursor gel is lowerTemperature is lighted rear liberated heat, and the reaction that can maintain self continues to go on, and burning liberated heat contributes to productThe formation of crystalline phase, decomposes a large amount of gas of generation and makes product fine size.
HNO3+NH4OH→NH4NO3+H2O
CO(NH2)2+3NH4 ++3NO3 -→4N2↑+CO2↑+8H2O↑
Aluminium for the combustion synthesis reaction formula of silicon doping apatite-type lanthanum silicate solid electrolyte can schematic representation be:
The invention has the beneficial effects as follows: raw material that the present invention adopts contains urea, its cost is low, and burning time is 5-7min, anti-Short between seasonable, adopt urea-nitrate combustion method, its preparation technology is simple, has realized La9.33Si6-XAlXO26-X/2Middle low temperature barSynthesizing under part; The present invention is that wet method is synthetic, accurately controls each constituent content in the plastic stage, and different component mixes, instituteObtain product purity high; The aluminium ion substitute doping silicon ion that ionic radius is larger, has increased lanthanum silicate oxygen ion vacancy concentration, makesObtain oxonium ion and there is more transmission space, effectively improved the electrolytical electrical conductivity of lanthanum silicate, at lambda sensor, film, solidThe various fields such as oxide body fuel cell have good application prospect.
Brief description of the drawings
Fig. 1 is that embodiment 1 gained aluminium is for silicon doping apatite-type lanthanum silicate solid electrolyte (La9.33Si5.5Al0.5O25.75) XX ray diffraction collection of illustrative plates (XRD).
Detailed description of the invention
Further introduce the present invention below by embodiment, but embodiment can not be construed as limiting the invention.
Embodiment 1
According to mol ratio La:Si:Al=9.33:5.5:0.5, take successively La2O3, ethyl orthosilicate and Al (NO3)3, useAppropriate absolute ethyl alcohol and HNO3Fully dissolve, then add urea and ethyl orthosilicate, 40 DEG C of heating are uniformly mixed before formationDrive liquid solution, by ammoniacal liquor adjusting pH value to 4, and be placed in 80 DEG C of water bath devices, after insulation 3h, obtain water white transparency presomaGel. Aqueous precursor gel is put into the Muffle furnace that is preheated to 600 DEG C, gel is heated and evaporates and burn rapidly, is accompanied by yellowishThe combustion flame of look, whole combustion process continues about 5-7min, obtains the foam powder of platinum sponge shape. Primary product is carried outGrind, calcine 12h at 800 DEG C, obtain high-purity La of well-crystallized9.33Si5.5Al0.5O25.75Powder. Further grinding gainedCalcining powder, compressing under 250MPa pressure, after 1400 DEG C of sintering 3h, obtain aluminium for silicon doping apatite-type lanthanum silicateSolid electrolyte. Fig. 1 is that gained aluminium is for silicon doping apatite-type lanthanum silicate solid electrolyte (La9.33Si5.5Al0.5O25.75) XX ray diffraction collection of illustrative plates (XRD), as shown in the figure, can find out, product diffraction maximum is obvious, and intensity is high, and thing is mutually single, contrast markAccurate PDF card diffraction data, finds that the rear cell parameter of aluminium doping slightly increases, but p63/ m apatite-type crystal structure does not changeBecome. Adopt AC impedence method, after the polishing of gained electrolyte is cleaned, on two faces, respectively smear evenly silver slurry of one deck, and electricity consumptionFlatiron is welded on two faces of silver electrode filamentary silver as lead-in wire, connects respectively working electrode and the reference electrode of electrochemical workstation,Under test different temperatures, the ac impedance spectroscopy of (400-800 DEG C), calculates La9.33Si5.5Al0.5O25.75Electrical conductivity at 800 DEG CCan reach 4.56 × 10-3S·cm-1。
Embodiment 2
According to mol ratio La:Si:Al=9.33:5:1, take successively La2O3, ethyl orthosilicate and Al (NO3)3, with appropriateAbsolute ethyl alcohol and HNO3Fully dissolve, then add urea and ethyl orthosilicate, 40 DEG C of heating are uniformly mixed formation presomaSolution, by ammoniacal liquor adjusting pH value to 5, and is placed in 80 DEG C of water bath devices, after insulation 3h, obtains water white transparency aqueous precursor gel.Aqueous precursor gel is put into the Muffle furnace that is preheated to 550 DEG C, gel is heated and evaporates and burn rapidly, is accompanied by flaxen combustionThe flame that makes a fire, whole combustion process continues about 5-7min, obtains the foam powder of platinum sponge shape. Primary product is ground,At 850 DEG C, calcine 10h, obtain high-purity La of well-crystallized9.33Si5AlO25.75Powder. Further grind the calcining powder of gained,Compressing under 250MPa pressure, after 1500 DEG C of sintering 3h, obtain aluminium for silicon doping apatite-type lanthanum silicate solid electrolyte.Adopt AC impedence method, test La9.33Si5AlO25.75Electrolytical electrical conductivity, can reach 3.53 × 10 at 800 DEG C-3S·cm-1。
Embodiment 3
According to mol ratio La:Si:Al=9.33:4:2, take successively La2O3, ethyl orthosilicate and Al (NO3)3, use appropriate nothingWater-ethanol and HNO3Fully dissolve, then add urea and ethyl orthosilicate, 40 DEG C of heating are uniformly mixed that to form presoma moltenLiquid, by ammoniacal liquor adjusting pH value to 6, and is placed in 80 DEG C of water bath devices, after insulation 3h, obtains colorless transparent gel. By gelPut into the Muffle furnace that is preheated to 650 DEG C, gel is heated and evaporates and burn rapidly, is accompanied by flaxen combustion flame, wholeCombustion process continues about 5-7min, obtains the foam powder of platinum sponge shape. Primary product is ground to calcining at 900 DEG C8h, obtains high-purity La of well-crystallized9.33Si4Al2O25Powder. Further grind the calcining powder of gained, press at 250MPaCompressing under power, after 1600 DEG C of sintering 3h, obtain aluminium for silicon doping apatite-type lanthanum silicate solid electrolyte. Adopt and exchangeImpedance method, test La9.33Si4Al2O25Electrolytical electrical conductivity, can reach 1.21 × 10 at 800 DEG C-3S·cm-1。
Claims (2)
1. aluminium is for the preparation method of silicon doping apatite-type lanthanum silicate solid electrolyte, and its chemical formula is La9.33Si6-XAlXO26-X/2，Wherein the span of x is 0.2-2.0, includes following steps: according to La9.33Si6-XAlXO26-X/2Stoichiometric proportion getLa2O3, aluminium source and ethyl orthosilicate, with La2O3, aluminium source is initiation material, joins the mixed solution of nitric acid and absolute ethyl alcoholIn dissolve completely, then to adding in mixed solution urea and ethyl orthosilicate to form precursor solution, regulate pH value, after insulationForm precursor gel; Take out aqueous precursor gel burning, grinding and compressing, last sintering can obtain aluminium for silicon doping phosphorusLime stone type lanthanum silicate solid electrolyte; Described aluminium source is aluminium oxide or aluminum nitrate; Described adjusting pH value is to adopt ammoniacal liquor to adjustJoint pH value is to 4-6; Described burning, grinding, concrete technology compressing and sintering refers to and takes out aqueous precursor gel at 500-700DEG C light, burning 5-7min obtains spongy powder; After spongy powder is ground, at 800-900 DEG C, calcining 8-12h obtainsHigh-purity powder; Again grind after at 225-250MPa forming under the pressure, then sintering 3h-5h at 1400-1600 DEG C.
2. the preparation method for silicon doping apatite-type lanthanum silicate solid electrolyte by aluminium claimed in claim 1, is characterized in thatDescribed insulation refers at 70-80 DEG C of insulation 2-4h.
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| CN106816615A (en) * | 2016-11-28 | 2017-06-09 | 佛山市尚好门窗有限责任公司 | A kind of new middle low temperature SOFC electrolytes and preparation method thereof |
| CN109713346A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Adulterate apatite-type lanthanum silicate and its preparation method and application in silicon position |
| CN107819131A (en) * | 2017-10-27 | 2018-03-20 | 深圳大学 | A kind of low-resistivity solid oxide fuel cell electrode and preparation method thereof |
| CN108493470A (en) * | 2018-03-21 | 2018-09-04 | 辽宁工业大学 | A kind of solid electrolyte and preparation method thereof of the compound regulation and control of vacancy/interstitial oxygen concentration |
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| CN1635658A (en) * | 2004-11-09 | 2005-07-06 | 施秀英 | Middle and low temperature ceramic oxide fuel cell and preparation process |
| CN101508437A (en) * | 2009-02-20 | 2009-08-19 | 山东大学 | Process for producing medium-temperature solid-oxide fuel battery electrolyte material lanthanum silicate powder |
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| CN1635658A (en) * | 2004-11-09 | 2005-07-06 | 施秀英 | Middle and low temperature ceramic oxide fuel cell and preparation process |
| CN101508437A (en) * | 2009-02-20 | 2009-08-19 | 山东大学 | Process for producing medium-temperature solid-oxide fuel battery electrolyte material lanthanum silicate powder |
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