CN1257131C - Method of preparing lithium niobate nanometer powder at low-temp by citric acid gel method - Google Patents
Method of preparing lithium niobate nanometer powder at low-temp by citric acid gel method Download PDFInfo
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- CN1257131C CN1257131C CN 200410043776 CN200410043776A CN1257131C CN 1257131 C CN1257131 C CN 1257131C CN 200410043776 CN200410043776 CN 200410043776 CN 200410043776 A CN200410043776 A CN 200410043776A CN 1257131 C CN1257131 C CN 1257131C
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Abstract
The present invention relates to a method for preparing nanometer lithium niobate powder at a low temperature by a citric acid gelatin method, particularly to a method for preparing lithium niobate. The present invention comprises the following steps: a. Nb2O5 is dissolved in HF, and then excessive ammonium oxalate solution is added; after thorough mixing, ammonia water is dropped to the solution to form white Nb(OH)5 precipitates; after being aged, filtered and washed, the precipitates are dissolved in citric acid water solution to form yellowish Nb-citric acid solution; b. lithium carbonate is added to the Nb-citric acid solution, and is fully dissolved by stirring; c. excessive citric acid solution is added to the solution; d. then ethylene glycol is added to the solution, and lithium niobate precursor solution is formed after uniform stirring; e. the solution is heated to obtain viscous gelatinous solid; f. finally, the gelatin is calcined to obtain the nanometer LiNbO3 powder. The present invention has the advantages of low cost, low environment pollution and simple technology.
Description
Technical field
The present invention relates to a kind of preparation method of Lithium niobium trioxide nano-powder.
Background technology
Lithium niobium trioxide is a kind of important ferroelectric material, it has good piezoelectricity, electric light, acousto-optic, thermoelectricity, light is sold off and a series of special propertys such as nonlinear optical property, because these characteristics, Lithium niobium trioxide has been widely used in devices such as photoconduction, photomodulator, photoswitch, nonvolatile memory, surface acoustic wave and second harmonic generator at present.For LiNbO
3The polycrystalline ceramics powder, sol-gel technology and the solid reaction processes of adopting prepare more, but aforesaid method all has its limitation separately, there is following shortcoming as the sol-gel method: (1) raw materials used metal alkoxide that is generally, as ethanol niobium, butanols niobium, butanols lithium etc., these raw materials do not have homemade commodity, and import reagent costs an arm and a leg, and the price of the five ethanol niobiums of producing as the Inorgtech company of the famous production metal alkoxide of Britain is 1300 pounds/L.(2) feed metal alkoxide very easily hydrolysis in air, therefore the condition that requires in preparation process is very harsh, except requiring the preparation powder, also to need strict rare gas element, as protections such as nitrogen in non-aqueous system.(3) owing to use a large amount of organic solvents, easily cause environmental pollution.And the mixing of solid reaction process reactant is inhomogeneous; The products therefrom stoichiometric ratio is inaccurate; Calcining temperature higher (1000 ℃), the powder sintering activity is low.
Summary of the invention
The present invention utilizes citrate gel method low temperature to prepare the method for Lithium niobium trioxide nano-powder, solved in the sol-gel technology metal alkoxide and be difficult for obtaining, cost an arm and a leg and the problem of hydrolysis very easily, this method also can overcome the problem of solid reaction process calcining temperature height, powder sintering poor activity.The present invention carries out according to following step: a, with Nb
2O
5Be dissolved among the HF under 70～90 ℃, to wherein adding excessive ammonium oxalate solution, behind the thorough mixing, dropping ammonia forms the Nb (OH) of white in solution then
5Throw out, this throw out be 70～90 ℃ of following ageings 10～14 hours, after filtration, after the washing, be dissolved in the aqueous citric acid solution, forms flaxen Nb-citric acid solution; B, be Nb according to mol ratio
5+: Li
+=1: 1 ratio joins Quilonum Retard in the Nb-citric acid solution, stirs it is fully dissolved; C, add excessive citric acid solution in solution, the mol ratio that makes metal ion and citric acid is 1: (1.5～3); D, ethylene glycol is added in the above-mentioned solution then, the mol ratio of ethylene glycol and citric acid is (1～2): 1, and the back that stirs forms the Lithium niobium trioxide precursor solution; E, with this solution at 60～100 ℃ of following heating 20～30h, obtain the heavy-gravity gelatinous solid; F, at last with this gel at 600～800 ℃ of following calcining 2～3h, obtain nanometer LiNbO
3Powder.The present invention is with Nb
2O
5Be initial feed, synthetic a kind of new niobium source can prepare LiNbO in the aqueous solution
3Powder, and calcining temperature is low, easily obtains the active nano-powder of high sintering, and this is for simplifying preparation technology, reduce cost, reduce environmental pollution, preparing the high sintering activity LiNbO of nano level
3Powder is significant.Citrate gel method of the present invention is to be sequestrant with the citric acid, forms the water-soluble metal carboxylate compound with metallic ion coordination, by the ethylene glycol polymerization, obtains aqueous precursor gel, and gel calcining under high temperature can obtain ceramic powder.This method has following advantage: (1) adopts the Nb that easily obtains
2O
5Be initial feed, prepare the citric acid compound of niobium, and substitute niobium alkoxides in the sol-gel technology, synthetic LiNbO as new niobium source with this
3Powder; (2) can from the aqueous solution, prepare LiNbO
3Powder, the problem of the metal alkoxide facile hydrolysis of solution sol-gel method, environmental pollution is little; (3) can reach the uniform mixing of molecular level, and accurately control stoichiometric ratio; (4) low synthesis temperature (600 ℃), powder sintering activity are good, and the gained powder granularity is a nano level; (5) technology is simple, need not complex apparatus.
Description of drawings:
Fig. 1 is the LiNbO of gained behind calcining 2h under 600 ℃
3The TEM figure of powder, Fig. 2 are gained LiNbO behind 600 ℃ of following calcining 2h
3The XRD figure spectrum of powder.
Embodiment:
Embodiment one: present embodiment is achieved in that a, with Nb
2O
5Be dissolved among the HF under 70～90 ℃, to wherein adding excessive ammonium oxalate solution, behind the thorough mixing, dropping ammonia forms the Nb (OH) of white in solution then
5Throw out, this throw out be 70～90 ℃ of following ageings 10～14 hours, after filtration, after the washing, be dissolved in the aqueous citric acid solution, forms flaxen Nb-citric acid solution; B, be Nb according to mol ratio
5+: Li
+=1: 1 ratio joins Quilonum Retard in the Nb-citric acid solution, stirs it is fully dissolved; C, add excessive citric acid solution in solution, the mol ratio that makes metal ion and citric acid is 1: (1.5～3); D, ethylene glycol is added in the above-mentioned solution then, the mol ratio of ethylene glycol and citric acid is (1～2): 1, and the back that stirs forms the Lithium niobium trioxide precursor solution; E, with this solution at 60～100 ℃ of following heating 20～30h, obtain the heavy-gravity gelatinous solid; F, at last with this gel at 600～800 ℃ of following calcining 2～3h, obtain nanometer LiNbO
3Powder.
Embodiment two: present embodiment is achieved in that a, with Nb
2O
5Be dissolved among the HF under 80 ℃, to wherein adding excessive ammonium oxalate solution, behind the thorough mixing, dropping ammonia forms the Nb (OH) of white in solution then
5Throw out, this throw out be 80 ℃ of following ageings 12 hours, after filtration, after the washing, be dissolved in the aqueous citric acid solution, forms flaxen Nb-citric acid solution, adopts inductively coupled plasma emmission spectrum (IP) method to measure the concentration that GOLD FROM PLATING SOLUTION belongs to Nb; B, get the Nb-citric acid solution and (contain Nb
5+0.5mol), the Quilonum Retard of 0.1mol is added in the Nb-citric acid solution, stirring is fully dissolved it; C, add excessive citric acid solution in solution, the mol ratio that makes metal ion and citric acid is 1: 3; D, ethylene glycol is added in the above-mentioned solution then, the mol ratio of ethylene glycol and citric acid is 1.8: 1, and the back that stirs forms the Lithium niobium trioxide precursor solution; E, with this solution at 80 ℃ of following heating 24h, obtain the heavy-gravity gelatinous solid; F, at last with this gel at 600 ℃ of following calcining 2h, obtain nanometer LiNbO
3Powder.From Fig. 1 as seen, the median size of gained powder is 30～50nm, is shaped as sphere.From Fig. 2 as seen, diffraction peak is single LiNbO
3Phase.
Claims (1)
1, utilizes citrate gel method low temperature to prepare the method for Lithium niobium trioxide nano-powder, it is characterized in that it carries out according to following step: a, Nb
2O
5Be dissolved among the HF under 70～90 ℃, to wherein adding excessive ammonium oxalate solution, behind the thorough mixing, dropping ammonia forms the Nb (OH) of white in solution then
5Throw out, this throw out be 70～90 ℃ of following ageings 10～14 hours, after filtration, after the washing, be dissolved in the aqueous citric acid solution, forms flaxen Nb-citric acid solution; B, be Nb according to mol ratio
5+: Li
+=1: 1 ratio joins Quilonum Retard in the Nb-citric acid solution, stirs it is fully dissolved; C, add excessive citric acid solution in solution, the mol ratio that makes metal ion and citric acid is 1: 3; D, ethylene glycol is added in the above-mentioned solution then, the mol ratio of ethylene glycol and citric acid is 2: 1, and the back that stirs forms the Lithium niobium trioxide precursor solution; E, with this solution at 60～100 ℃ of following heating 20～30h, obtain the heavy-gravity gelatinous solid; F, at last with this gel at 600～800 ℃ of following calcining 2～3h, obtain nanometer LiNbO
3Powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410043776 CN1257131C (en) | 2004-08-06 | 2004-08-06 | Method of preparing lithium niobate nanometer powder at low-temp by citric acid gel method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410043776 CN1257131C (en) | 2004-08-06 | 2004-08-06 | Method of preparing lithium niobate nanometer powder at low-temp by citric acid gel method |
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| CN1597613A CN1597613A (en) | 2005-03-23 |
| CN1257131C true CN1257131C (en) | 2006-05-24 |
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| CN 200410043776 Expired - Fee Related CN1257131C (en) | 2004-08-06 | 2004-08-06 | Method of preparing lithium niobate nanometer powder at low-temp by citric acid gel method |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102760876B (en) * | 2011-04-29 | 2015-05-27 | 中国科学院物理研究所 | Niobate and niobate composite material and application of niobate composite material to secondary lithium battery |
| CN103107340B (en) * | 2013-01-24 | 2016-05-25 | 青岛克瑞化工有限公司 | A kind of preparation method of LiFePO 4 material conductive agent |
| CN103922405B (en) * | 2014-04-18 | 2015-08-12 | 山东大学 | A kind of mass synthetic method of even mg-doped lithium niobate polycrystal |
| CN107151142B (en) * | 2017-05-26 | 2020-06-16 | 中电科技德清华莹电子有限公司 | Method for synthesizing polycrystalline material with high-melting-point doping elements |
| CN109939701B (en) * | 2018-12-12 | 2020-05-26 | 常州大学 | Preparation method and application of rare earth fluoride/lithium niobate composite photocatalytic material |
| CN114540026A (en) * | 2022-02-21 | 2022-05-27 | 中国科学院深圳先进技术研究院 | Lithium niobate quantum material, preparation method thereof and photoelectric device |
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