CN110808395A - Neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte and preparation method thereof - Google Patents
Neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte and preparation method thereof Download PDFInfo
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- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 41
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 41
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000011701 zinc Substances 0.000 title claims abstract description 38
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 35
- 229910052779 Neodymium Inorganic materials 0.000 title claims abstract description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 31
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 title claims abstract description 30
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 title claims abstract description 25
- 229910052586 apatite Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004202 carbamide Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000011787 zinc oxide Substances 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003825 pressing Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 7
- -1 oxygen ions Chemical class 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- QHDUJTCUPWHNPK-UHFFFAOYSA-N methyl 7-methoxy-2h-indazole-3-carboxylate Chemical compound COC1=CC=CC2=C(C(=O)OC)NN=C21 QHDUJTCUPWHNPK-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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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
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte and a preparation method thereof. The chemical formula of the solid electrolyte is La9.33NdxSi6‑yZnyO26‑y+3x/2Wherein the value range of x is 0.6-0.8, and the value range of y is 0.9-1.1. The preparation method comprises the following steps: 1) reacting La with nitric acid2O3Dissolving the neodymium source mixture in absolute ethyl alcohol to form sol; 2) continuously adding a zinc source and tetraethyl orthosilicate, adjusting the pH of the sol to 4-5, and adding urea to obtain precursor sol; 3) aging to obtain precursor gel, drying, burning, grinding, pressing and molding, and sintering to obtain the neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte. Through neodymium and zinc co-doping, the conductivity of the apatite lanthanum silicate solid electrolyte is improved, the sintering temperature is reduced, the operation is simple, the raw materials are low, and the application prospect is wide.
Description
Technical Field
The invention relates to the technical field of solid oxide fuel cells, in particular to a neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte and a preparation method thereof.
Background
The Solid Oxide Fuel Cell (SOFC) is a device for generating electricity through the reaction of fuel gas and oxidizing gas at high temperature, directly converts the chemical energy of the reaction into electric energy, avoids the problem that the conventional electricity generation needs to be converted into electric energy through multiple energy conversions, which causes a large amount of energy loss, is used as a new energy source, has a simple electricity generation mode, is environment-friendly and pollution-free, and is a green energy source material. The solid electrolyte is an important medium for ion conduction, and plays an important role in SOFC, isolating reaction gas and transporting oxygen ions during the whole operation process of the fuel cell. Yttria-stabilized zirconia (YSZ) is one of the traditional solid electrolytes, but has many disadvantages such as too high working temperature, complex preparation process, interphase diffusion, too high cost and the like, and the application of the yttria-stabilized zirconia in various fields is limited to a great extent. Therefore, a new solid electrolyte material needs to be found to replace the traditional YSZ solid electrolyte material.
The prior solid electrolyte material with high ionic conductivity at medium and low temperature is fluorite CeO2Base, Bi2O3Electrolytes of the perovskite type, the ionic conductance of which is related to oxygen vacancies caused by non-stoichiometry, CeO2Radical and doped Bi2O3The working temperature range of the base electrolyte material is narrow, and the electronic conductance causing a short-circuit channel is easily generated under low oxygen partial pressure and reducing atmosphere; the perovskite electrolyte material mainly has the problems of poor sintering performance, poor compatibility between the electrolyte and an electrode material and the like.
Apatite lanthanum silicate electrolyte La9.33+x(SiO4)6O2+3x/2It is considered to be the most potential solid electrolyte material due to its low activation energy and high oxygen ion conductivity at medium and low temperatures. In order to improve the performance of the apatite lanthanum silicate electrolyte, it is usually modified by ion doping. However, most of the existing ion doping is single ion doping, and the performance improvement is limited. The preparation method mainly comprises a high-temperature solid-phase combustion method, a sol-gel method and the like, but the preparation methods have the defects of high synthesis temperature, easy occurrence of impurities and the like.
Therefore, a method for simply and effectively doping double ions into the lanthanum silicate solid electrolyte to further improve the performance of the lanthanum silicate solid electrolyte is needed to be found.
Disclosure of Invention
The invention aims to provide a neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte and a preparation method thereof, which effectively increase the interstitial oxygen concentration in lanthanum silicate crystals, improve the conductivity of the apatite lanthanum silicate solid electrolyte and reduce the sintering temperature through co-doping of neodymium and zinc, and have wide application prospects in the fields of novel solid batteries, chemical sensors, solid oxide fuel cells and the like.
In order to solve the technical problems, the invention provides the following technical scheme:
provides a neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte with the chemical formula of La9.33NdxSi6- yZnyO26-y+3x/2Wherein the value range of x is 0.6-0.8, and the value range of y is 0.9-1.1.
The preparation method of the neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte comprises the following specific steps:
1) reacting La with nitric acid2O3Dissolving the neodymium source mixture in absolute ethyl alcohol to form sol;
2) adding a zinc source and tetraethyl orthosilicate into the sol obtained in the step 1), adjusting the pH of the sol to 4-5, stirring until the sol is clear, adding urea, and continuously stirring and clarifying to obtain precursor sol;
3) aging the precursor sol obtained in the step 2) to obtain precursor gel, and then drying, burning, grinding, press-forming and sintering to obtain the precursor gel with the chemical formula of La9.33NdxSi6-yZnyO26-y+3x/2The neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte;
wherein, according to the chemical formula La9.33NdxSi6-yZnyO26-y+3x/2The lanthanum source, the neodymium source, the silicon source and the zinc source are weighed according to the stoichiometric ratio, the value range of x is 0.6-0.8, and the value of y is 0.9-1.1.
In the scheme, in the step 1), the neodymium source is neodymium oxide or neodymium nitrate.
In the scheme, in the step 2), the zinc source is zinc oxide or zinc nitrate.
In the scheme, in the step 2), ammonia water is adopted to adjust the pH value of the sol to 4-5.
In the scheme, in the step 3), the aging temperature of the precursor sol is 70-90 ℃, and the aging time is 2-6 h.
In the above scheme, in step 3), the drying conditions are as follows: drying in vacuum at 100-120 deg.c for 10-16 hr.
In the above scheme, in the step 3), the burning, grinding and press forming process specifically comprises the following steps: igniting the dried precursor gel at the temperature of 600-750 ℃, continuously burning for 6-9 minutes to obtain spongy lanthanum silicate powder, grinding the spongy powder to micron level, calcining at the temperature of 800-900 ℃ for 6-12 hours to obtain high-crystallinity powder, and molding the obtained powder under the pressure of 200-300 MPa.
In the above scheme, in step 3), the sintering conditions are as follows: the formed blank is sintered for 3-6h at the temperature of 1200-1400 ℃.
The combustion synthesis reaction of neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte can be briefly expressed as follows:
the invention has the beneficial effects that:
1. the invention adopts zinc ions to replace silicon sites, the zinc ions are divalent, tetravalent silicon ions are replaced, the number of interstitial oxygen can be increased, the ionic radius of the zinc ions is larger than that of the silicon, the migration channel of the interstitial oxygen ions can be increased after the zinc replaces the silicon, the negative positive ion vacancy can be reduced by replacing lanthanum sites with trivalent rare earth metal neodymium ions, so that the repulsive force of the positive ion vacancy to the negative interstitial oxygen ions is reduced, the mobility of the interstitial oxygen ions is increased, the conductivity of the lanthanum silicate solid electrolyte can be effectively improved by double doping of zinc and neodymium, and the temperature can reach 2.01 multiplied by 10 at 650 DEG C-3S/cm, reduces the use temperature, and has wide application prospect in the fields of novel solid batteries, chemical sensors, solid oxide fuel cells and the like.
2. The invention adopts a urea-nitrate combustion method, a precursor consisting of urea and nitrate is ignited at a lower temperature in a combustion stage, the released heat can ensure that the self reaction continues, the respective dosage of different components can be accurately controlled in a sol stage, and the different components are uniformly mixed at a molecular/atomic level, so that accurate double-ion doping is realized.
3. The zinc is also used as a good sintering aid, so that the sintering temperature of the lanthanum silicate solid electrolyte is reduced, and the energy consumption is reduced.
4. Simple operation, cheap and easily obtained raw materials, low cost and low energy consumption.
Drawings
FIG. 1 shows a neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte La prepared in example 1 of the present invention9.33Nd0.6Si5ZnO25.3X-ray diffraction pattern of (a).
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following embodiments are further described.
Example 1
A preparation method of neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte comprises the following steps of: nd: si: zn 9.33: 0.6: 5: 1, weighing La2O3、Nd2O3ZnO and tetraethyl orthosilicate for standby, and the specific steps are as follows:
1) will weigh the La2O3And Nd2O3Mixing the mixture with absolute ethyl alcohol and dissolving the mixture with nitric acid to form sol;
2) adding ZnO and tetraethyl orthosilicate into the sol obtained in the step 1), uniformly mixing, adjusting the pH to 5 with ammonia water, stirring until the mixture is clear, adding urea serving as a combustion improver, and continuously stirring until the mixture is clear to obtain precursor sol;
3) aging the precursor sol obtained in the step 2) at 80 ℃ for 2h to obtain precursor gel, drying the precursor gel in a vacuum drying oven at 100 ℃ for 12h, then putting the dried precursor gel in a muffle furnace preheated to 650 ℃ for ignition, wherein the whole combustion reaction process lasts for 6-9 min to obtain sponge lanthanum silicate powder, grinding the powder to micron level, calcining the powder at 900 ℃ for 8h, performing compression molding on the calcined powder under the pressure of 250MPa, and sintering the molded blank at 1300 ℃ for 3h to obtain the product with the chemical formula of La9.33Nd0.6Si5ZnO25.9The neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte.
FIG. 1 shows neodymium, zinc-doped apatite lanthanum silicate solid electrolyte (La)9.33Nd0.6Si5ZnO25.9) X-ray diffraction pattern (XRD). As can be seen from figure 1, compared with the data of a standard PDF card, the neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte prepared by the method has no impurity phase, and the apatite structure of lanthanum silicate is not damaged after doping.
The conductivity of the resulting solid electrolyte was measured by an alternating current impedance method. Cleaning and polishing the prepared electrolyte wafer, coating a layer of uniform conductive silver paste on the upper surface and the lower surface of the electrolyte wafer, calcining the conductive silver paste at 700 ℃ for 3 hours to remove organic impurities in the silver paste, welding two silver wires serving as leads on the upper surface and the lower surface of the electrolyte respectively, connecting a working electrode and a reference electrode of an electrochemical workstation, testing the alternating current impedance spectrum of the electrolyte at low temperature (400-9.33Nd0.6Si5ZnO25.9The conductivity of the conductive coating can reach 2.01 multiplied by 10 at 650 DEG C-3S/cm。
Example 2
A preparation method of neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte comprises the following steps of: nd: si: zn 9.33: 0.8: 5: 1, weighing La2O3、Nd2O3ZnO and tetraethyl orthosilicate for standby, and the specific steps are as follows:
1) will weigh the La2O3And Nd2O3Mixing with anhydrous ethanol and adding nitric acidDissolving to form sol;
2) adding ZnO and tetraethyl orthosilicate into the sol obtained in the step 1), uniformly mixing, adjusting the pH to 4 by using ammonia water, stirring until the mixture is clear, adding urea serving as a combustion improver, and continuously stirring until the mixture is clear to obtain precursor sol;
3) aging the precursor sol obtained in the step 2) at 80 ℃ for 3h to obtain precursor gel, drying the precursor gel in a vacuum drying oven at 100 ℃ for 10h, then putting the dried precursor gel in a muffle furnace preheated to 650 ℃ for ignition, continuing the whole combustion reaction process for 6-9 min to obtain spongy lanthanum silicate powder, grinding the spongy lanthanum silicate powder to micron level, calcining the spongy lanthanum silicate powder at 800 ℃ for 10h, performing compression molding on the calcined lanthanum silicate powder under the pressure of 250MPa, and sintering the molded blank at 1300 ℃ for 3h to obtain the lanthanum silicate with the chemical formula9.33Nd0.8Si5ZnO26.2The neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte.
La test by AC impedance method in the same manner as in example 19.33Nd0.8Si5ZnO26.2The conductivity of the electrolyte can reach 1.42 x 10 at 650 deg.C-3S/cm。
Claims (9)
1. The neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte is characterized in that the chemical formula of the solid electrolyte is La9.33NdxSi6-yZnyO26-y+3x/2Wherein the value range of x is 0.6-0.8, and the value range of y is 0.9-1.1.
2. The preparation method of the neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte according to claim 1 is characterized by comprising the following specific steps:
1) reacting La with nitric acid2O3Dissolving the neodymium source mixture in absolute ethyl alcohol to form sol;
2) adding a zinc source and tetraethyl orthosilicate into the sol obtained in the step 1), adjusting the pH of the sol to 4-5, stirring until the sol is clear, adding urea, and continuously stirring and clarifying to obtain precursor sol;
3) the precursor sol obtained in the step 2) is addedAging to obtain precursor gel, drying, burning, grinding, press forming, and sintering to obtain La9.33NdxSi6-yZnyO26-y+3x/2The neodymium and zinc co-doped apatite lanthanum silicate solid electrolyte;
wherein, according to the chemical formula La9.33NdxSi6-yZnyO26-y+3x/2The lanthanum source, the neodymium source, the silicon source and the zinc source are weighed according to the stoichiometric ratio, the value range of x is 0.6-0.8, and the value of y is 0.9-1.1.
3. The method according to claim 2, wherein in the step 1), the neodymium source is neodymium oxide or neodymium nitrate.
4. The method according to claim 2, wherein the zinc source in step 2) is zinc oxide or zinc nitrate.
5. The method according to claim 2, wherein in the step 2), the pH of the sol is adjusted to 4 to 5 using ammonia water.
6. The preparation method according to claim 2, wherein in the step 3), the aging temperature of the precursor sol is 70-90 ℃ and the aging time is 2-6 h.
7. The method according to claim 2, wherein in the step 3), the drying conditions are as follows: drying in vacuum at 100-120 deg.c for 10-16 hr.
8. The preparation method according to claim 2, wherein in the step 3), the burning, grinding and press forming processes are specifically as follows: igniting the dried precursor gel at the temperature of 600-750 ℃, continuously burning for 6-9 minutes to obtain spongy lanthanum silicate powder, grinding the spongy powder to micron level, calcining at the temperature of 800-900 ℃ for 6-12 hours to obtain high-crystallinity powder, and molding the obtained powder under the pressure of 200-300 MPa.
9. The method according to claim 2, wherein in the step 3), the sintering conditions are as follows: the formed blank is sintered for 3-6h at the temperature of 1200-1400 ℃.
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