CN1597535A - Preparation of potassium lithium niobate nanometer powder using citric acid gelification method - Google Patents
Preparation of potassium lithium niobate nanometer powder using citric acid gelification method Download PDFInfo
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- CN1597535A CN1597535A CN 200410043777 CN200410043777A CN1597535A CN 1597535 A CN1597535 A CN 1597535A CN 200410043777 CN200410043777 CN 200410043777 CN 200410043777 A CN200410043777 A CN 200410043777A CN 1597535 A CN1597535 A CN 1597535A
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Abstract
A process for preparing nano-potasium lithium niobate includes such steps as dissolving Nb2O3 in HF, adding ammonium oxalate, dropping ammonia water to form Nb(OH)5, ageing filtering, washing, dissolving it in citric acid to form Nb-citric acid solution, mixing it with lithium carbonate and potassium carbonate, regulating pH value, adding ethanediol to generate precursor solution, heating to become gel solid, and calcining.
Description
Technical field:
The present invention relates to a kind of preparation method of inorganic materials, be specifically related to a kind of preparation method of lithium potassium niobate nano-powder.
Background technology:
Lithium potassium niobate has good electro-optical properties and non-linear optical property, can be in wider wave range under the room temperature (790～920nm) realize non-critical phase matchings, are converted into blue light.Therefore KLN is good blue light double-frequency material.Simultaneously, KLN also is a kind of photorefractive material.At present, lithium potassium niobate (K
3Li
2-xNb
5+xO
15+2x, 0≤x＜0.5, KLN) powder adopts sol-gel (sol-gel) method and solid reaction process preparation more.Aforesaid method all has 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 potassium, butanols lithium etc., these raw materials do not have homemade commodity, 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 (＞1100 ℃), the powder sintering activity is low.
Summary of the invention:
The present invention adopts the citrate gel method to prepare the lithium potassium niobate nano-powder, and solve that metal alkoxide is difficult for obtaining in the sol-gel technology, cost an arm and a leg and the problem of hydrolysis very easily, and the problem that overcomes 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
+: K
+=(5+x): (2-x): 3 ratio is mixed Quilonum Retard, Nb-citric acid solution and salt of wormwood, after fully stirring, adds excessive citric acid, and the mol ratio that makes metal ion and citric acid is 1: 3, with ammoniacal liquor the pH value of solution is transferred to 6～7; C, add ethylene glycol in mixed solution, stirring forms the lithium potassium niobate precursor solution; D, with this solution at 60～100 ℃ of following heating 20～30h, obtain the heavy-gravity gelatinous solid; E, at last with this gel at 900 ℃ of following calcining 2h, obtain nanometer K
3Li
2-xNb
5+xO
15+2xPowder, wherein 0≤x＜0.5.The present invention is with Nb
2O
5Be initial feed, synthetic a kind of new niobium source can prepare the KLN powder in the aqueous solution.This for simplify preparation technology, reduce cost, to reduce environmental pollution significant.The present invention adopts citrate gel prepared KLN powder first, this method is to be sequestrant with the citric acid, forms the water-soluble metal carboxylate compound with metallic ion coordination, by the ethylene glycol polymerization, obtain aqueous precursor gel, 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 KLN powder as new niobium source with this; (2) can prepare the KLN powder from the aqueous solution, solve the problem of the metal alkoxide facile hydrolysis of 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, 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 K of gained behind calcining 2h under 900 ℃
3Li
2Nb
5O
15The TEM figure of powder, Fig. 2 are gained K behind 900 ℃ of following calcining 2h
3Li
2Nb
5O
15The XRD figure spectrum of powder.
Embodiment:
Embodiment one: present embodiment is carried 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
+: K
+=(5+x): (2-x): 3 ratio is mixed Quilonum Retard, Nb-citric acid solution and salt of wormwood, after fully stirring, adds excessive citric acid, makes metal ion (Nb
5+, Li
+, K
+) with the mol ratio of citric acid be 1: 3, with ammoniacal liquor the pH value of solution is transferred to 6～7; C, add ethylene glycol in mixed solution, stirring forms the lithium potassium niobate precursor solution; D, with this solution at 60～100 ℃ of following heating 20～30h, obtain the heavy-gravity gelatinous solid; E, at last with this gel at 900 ℃ of following calcining 2h, obtain nanometer K
3Li
2-xNb
5+xO
15+2xPowder, wherein 0≤x＜0.5.
Embodiment two: present embodiment is carried out according to following step: 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 (ICP) 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, and then the salt of wormwood with 0.15mol adds wherein, after fully stirring, adds excessive citric acid, makes metal ion (Nb
5+, Li
+, K
+) with the mol ratio of citric acid be 1: 3, with ammoniacal liquor the pH value of solution is transferred to 6～7; In c, the ethylene glycol adding solution with 1.5mol, stirring forms the lithium potassium niobate precursor solution; D, with this solution at 80 ℃ of following heating 24h, obtain the heavy-gravity gelatinous solid; E, at last with this gel at 900 ℃ of following calcining 2h, obtain nanometer K
3Li
2Nb
5O
15Powder.The powder that is obtained is single tungsten bronze(s) phase nanometer K
3Li
2Nb
5O
15Powder, 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 tungsten bronze(s) phase.
Claims (1)
1, the citrate gel method prepares the lithium potassium niobate nano-powder, it is characterized in that it 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
+: K
+=(5+x): (2-x): 3 ratio is mixed Quilonum Retard, Nb-citric acid solution and salt of wormwood, after fully stirring, adds excessive citric acid, and the mol ratio that makes metal ion and citric acid is 1: 3, with ammoniacal liquor the pH value of solution is transferred to 6～7; C, add ethylene glycol in mixed solution, stirring forms the lithium potassium niobate precursor solution; D, with this solution at 60～100 ℃ of following heating 20～30h, obtain the heavy-gravity gelatinous solid; E, at last with this gel at 900 ℃ of following calcining 2h, obtain nanometer K
3Li
2-xNb
5+xO
15+2xPowder, wherein 0≤x＜0.5.
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|---|---|---|---|
| CN 200410043777 CN1597535A (en) | 2004-08-06 | 2004-08-06 | Preparation of potassium lithium niobate nanometer powder using citric acid gelification method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410043777 CN1597535A (en) | 2004-08-06 | 2004-08-06 | Preparation of potassium lithium niobate nanometer powder using citric acid gelification method |
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ID=34665447
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101944602A (en) * | 2010-09-27 | 2011-01-12 | 彩虹集团公司 | Preparation method of nano-ternary complex lithium-ion battery cathode material |
| CN102030530A (en) * | 2010-11-24 | 2011-04-27 | 华中科技大学 | Preparation method of potassium-sodium niobate leadless piezo-electric ferroelectric ceramic |
| CN102153350A (en) * | 2011-05-07 | 2011-08-17 | 大连交通大学 | Method for preparing potassium niobate nano powder |
| CN104163627A (en) * | 2014-07-15 | 2014-11-26 | 华南理工大学 | Preparation method of KNbO3 nano solid solution with adjustable optical band gap |
| CN105195129A (en) * | 2014-05-30 | 2015-12-30 | 东北大学 | Columbate-loaded diatomite ball visible-light-driven photocatalyst and preparation method thereof |
-
2004
- 2004-08-06 CN CN 200410043777 patent/CN1597535A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101944602A (en) * | 2010-09-27 | 2011-01-12 | 彩虹集团公司 | Preparation method of nano-ternary complex lithium-ion battery cathode material |
| CN102030530A (en) * | 2010-11-24 | 2011-04-27 | 华中科技大学 | Preparation method of potassium-sodium niobate leadless piezo-electric ferroelectric ceramic |
| CN102153350A (en) * | 2011-05-07 | 2011-08-17 | 大连交通大学 | Method for preparing potassium niobate nano powder |
| CN102153350B (en) * | 2011-05-07 | 2012-11-21 | 大连交通大学 | Method for preparing potassium niobate nano powder |
| CN105195129A (en) * | 2014-05-30 | 2015-12-30 | 东北大学 | Columbate-loaded diatomite ball visible-light-driven photocatalyst and preparation method thereof |
| CN104163627A (en) * | 2014-07-15 | 2014-11-26 | 华南理工大学 | Preparation method of KNbO3 nano solid solution with adjustable optical band gap |
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