CN101734720A - Method for preparing vanadium dioxide ultrafine powder - Google Patents
Method for preparing vanadium dioxide ultrafine powder Download PDFInfo
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- CN101734720A CN101734720A CN200910247863A CN200910247863A CN101734720A CN 101734720 A CN101734720 A CN 101734720A CN 200910247863 A CN200910247863 A CN 200910247863A CN 200910247863 A CN200910247863 A CN 200910247863A CN 101734720 A CN101734720 A CN 101734720A
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Abstract
The invention relates to a method for preparing vanadium dioxide ultrafine powder, which belongs to the technical field of chemical materials. The method comprises the steps of adopting an alkoxide of tetravalent or pentavalent vanadium as a reactant, and adopting non-oxidizing atmosphere for sintering under the condition of 250-800 DEG C, to obtain rutile type vanadium dioxide (VO2) ultrafine powder with phase change property. The method can obtain the powder with the primary particle size of about dozens of nanometers by short-term treatment, also obtain the sub-micron and micron vanadium dioxide (VO2) powder by prolonging the reaction time, and realize the preparation of the doped powder by adding the corresponding doping reactant. The preparation process is simple, and the safety is good, thereby being applicable to large-scale industrial preparation and popularization.
Description
Technical field
Having the present invention relates to the preparation method's of vanadium dioxide ultrafine powder preparation method, more precisely is a kind of vanadium dioxide (VO with phase-change characteristic that obtains by thermal treatment
2) preparation method of superfine powder, belong to the nano-powder field.
Background technology
Vanadium dioxide (VO
2) be a kind of transition metal oxide with phase-change characteristic.Body monocrystalline VO
2Material takes place mutually to change near 68 ℃, changes cubic metallic state under the high temperature into from low temperature monocline semi-conductor attitude down, with it correspondence comprise optics, electricity, and physicals such as magnetics is undergone mutation.And its phase transition temperature can be adjusted to needed codomain by methods such as doping.Based on vanadium dioxide (VO
2) the phase transformation performance of this uniqueness, it is at the energy-saving coating material, optical memory material, the non-refrigeration focal surface material, aspects such as laser protective material are widely used.
Vanadium dioxide (VO
2) technology of preparing of powder is a key link of these material promotion and application, along with VO2 material especially application prospect aspect energy-conservation, also just causing increasing concern about the new synthetic technology of preparing of material.Utilize the synthetic VO of precursor of vanadium at present
2Powder body material be that inorganic vanadium raw materials obtains by long heat treatment mostly.Adopt the vanadium raw materials V of pentavalent as number of patent application ZL200510020970.0
2O
5Prepare as reactant with oxalic acid and to undope and mix VO
2Nano-powder obtains powder granularity and is tens nanometers, is mainly used in the polymeric film that the polymer of solar heat intelligent control disperses.The quaternary inorganic precursor also has relevant report, adopts the inorganic vanadic salts VOSO of quaternary as number of patent application 200610024387.X
4Precursor has prepared, and yardstick is the following vanadium dioxide (VO of 100nm
2) nano-powder, by mixing and doping in solution, and, obtain the adjustable V of transformation temperature through operations such as filtration, washing, drying, crystallizations
(1-x)M
xO
2(0＜x＜0.06) powder can be used for fields such as smart window coating and measuring resistance.In general, vanadium dioxide (VO
2) powder preparing is based on inorganic salt precursor system, and the alkoxide of employing vanadium prepares the vanadium dioxide (VO of phase-change characteristic
2) powder body material do not have relevant report.And adopt inorganic salt system to prepare vanadium dioxide (VO at present
2) powder generally needs the precursor prepared in reaction process of more complicated, operation is more, and this will produce very big fringe cost for suitability for industrialized production.Based on this, the present invention has adopted the metal alkoxide of vanadium as reactant, does not need reducing atmosphere in the preparation process, by the raw material thermal treatment of certain hour, can obtain having the vanadium dioxide (VO of phase-change characteristic
2) superfine powder.This process safety is simple, is a kind of more pervasive method of the metal alkoxide at vanadium, is suitable for the vanadium dioxide (VO that mass preparation has phase-change characteristic
2) powder.Adopt the vanadium dioxide (VO of this prepared
2) powder can be applied to aspects such as smart window, intelligent paint coating.
Summary of the invention
In order to solve VO
2The complex process of nano powder preparation process, control should not realize, and the toxicity problem that reduces precursor, and the alkoxide that we have adopted vanadium is main pre-reaction material, adopt the brief heat treating prepared except having the adjustable VO of phase-change characteristic and temperature
2Superfine powder, it is less that the short period of time is handled gained powder yardstick, and the primary particle yardstick is about tens nanometers.Long time treatment also can obtain submicron, micron order vanadium dioxide (VO
2) powder.And by doping process, transformation temperature can be adjusted as required.
Prepare a kind of vanadium dioxide (VO provided by the present invention
2) preparation of superfine powder, its concrete processing step is as follows:
(1) selecting the alkoxide of tetravalence vanadium for use is reactant, and perhaps the alkoxide of pentavalent vanadium is sneaked into coordinative solvent, and adding oxalic acid obtains thick material;
The preferred compound that adds Mo, Ti or W in the above-mentioned steps, 1～10wt% of the alkoxide of add-on tetravalence vanadium or the alkoxide of pentavalent vanadium, the soluble salt of the compound of described Mo, Ti or W further preferred Mo, Ti or W, further preferred wolframic acid.
(2) step (1) products therefrom is carried out sintering in vacuum or protective atmosphere, temperature range is 250-800 ℃, is incubated 1～10 hour.
Preferred methyl ethyl diketone vanadyl of the alkoxide of described tetravalence vanadium and/or dichloro two luxuriant vanadium; The preferred Virahol vanadyl of the alkoxide of described pentavalent vanadium etc.
Described protective atmosphere preferred nitrogen or argon gas.
Vanadium dioxide (the VO that the present invention makes
2) superfine powder can be nano level, submicron order or micron order can be used for association areas such as intelligent temperature control coating.
The present invention has the following advantages:
1, the short period of time handles and can prepare the vanadium dioxide (VO with tens nanoscales
2) superfine powder, long time treatment can obtain submicron, and micron order has the vanadium dioxide (VO of phase-change characteristic
2) powder.
2, synthesis technique is simple, does not need complicated production unit, and save energy is suitable for the preparation of extensive powder.
3, reaction process does not need protection of reducing atmosphere, is beneficial to safety in production.
4, can realize the convenient of vanadium dioxide (VO2) superfine powder mixed, transformation temperature can be adjusted by mixing.
Description of drawings
Fig. 1 is vanadium dioxide (VO
2) the XRD figure spectrum of superfine powder.
Fig. 2 is vanadium dioxide (VO
2) the TEM collection of illustrative plates of superfine powder.
Can know that by the XRD figure spectrum under certain treatment condition, resulting powder is pure rutile-type vanadium dioxide (VO
2-M) crystallization phases, the median size size of utilizing the Scherrer formula to calculate is 7.1nm.TEM result can know that the vanadium dioxide particle of gained shows different-shape, and its size of particles is about below the 20nm.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1
Adopt the alkoxide of tetravalence vanadium to prepare the vanadium dioxide ultrafine powder that undopes
Get methyl ethyl diketone vanadyl 10g, through simply grinding, powder is put into diameter 35mm, in the quartz boat of length 200mm, and to place diameter be the tube furnace of 100mm.Feed nitrogen (2.5L/min), be warming up to 500 ℃, insulation 2h can obtain plain vanadium dioxide ultrafine powder.
Embodiment 2
Prepare adulterated vanadium dioxide ultrafine powder
Get methyl ethyl diketone vanadyl 100g, wolframic acid 2.4g places and carries out mechanically mixing and grinding in the ball mill, 100 rev/mins of mixing velocities, mixing time one hour.Remove mixed powder 20g, put into diameter 35mm, in the quartz boat of length 200mm, pave lamellar, and to place diameter be the tube furnace of 100mm.Feed nitrogen (2.5L/min), be warming up to 500 ℃, insulation 2h can obtain adulterated vanadium dioxide ultrafine powder.
Embodiment 3
Adopt the alkoxide of pentavalent vanadium to prepare plain vanadium dioxide ultrafine powder
Get Virahol vanadyl 20g adding 50ml acetone and obtain thick material, add dissolved oxalic acid in the entry (Virahol vanadyl and oxalic acid mass ratio are 1: 3) after waiting to stablize.Leave standstill and stir up to no longer including gas and emerge, and evaporate into dried powder at stink cupboard.Get this powder and place diameter 35mm, in the quartz boat of length 200mm, pave lamellar, and to place diameter be the tube furnace of 100mm.Feed nitrogen (2.5L/min), be warming up to 500 ℃, insulation 2h can obtain vanadium dioxide ultrafine powder.
Claims (6)
1. the preparation method of vanadium dioxide ultrafine powder is characterized in that comprising the steps:
(1) selecting the alkoxide of tetravalence vanadium for use is reactant, and perhaps the alkoxide of pentavalent vanadium is sneaked into coordinative solvent, and adding oxalic acid obtains thick material;
(2) step (1) products therefrom is carried out sintering in vacuum or protective atmosphere, temperature range is 250-800 ℃, is incubated 1～10 hour.
2. by the preparation method of the described vanadium dioxide ultrafine powder of claim 1, it is characterized in that adding in the step (1) compound of Mo, Ti or W, 1～10wt% of the alkoxide of add-on tetravalence vanadium or the alkoxide of pentavalent vanadium.
3. by the preparation method of the described vanadium dioxide ultrafine powder of claim 2, it is characterized in that the preferred methyl ethyl diketone vanadyl of alkoxide and/or the dichloro two luxuriant vanadium of described tetravalence vanadium; The preferred Virahol vanadyl of the alkoxide of described pentavalent vanadium etc.
4. by the preparation method of the described vanadium dioxide ultrafine powder of claim 2, the compound that it is characterized in that described Mo, Ti or W is the soluble salt of Mo, Ti or W.
5. by the preparation method of the described vanadium dioxide ultrafine powder of claim 3, the soluble salt that it is characterized in that described Mo, Ti or W is a wolframic acid.
6. by the preparation method of the described vanadium dioxide ultrafine powder of claim 1, it is characterized in that described protective atmosphere is nitrogen or argon gas.
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| CN 200910247863 CN101734720B (en) | 2009-12-31 | 2009-12-31 | Method for preparing vanadium dioxide ultrafine powder |
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| CN 200910247863 CN101734720B (en) | 2009-12-31 | 2009-12-31 | Method for preparing vanadium dioxide ultrafine powder |
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| CN101734720A true CN101734720A (en) | 2010-06-16 |
| CN101734720B CN101734720B (en) | 2013-05-29 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464354A (en) * | 2010-11-05 | 2012-05-23 | 中国科学院上海硅酸盐研究所 | Rutile-phase vanadium dioxide composition, coating containing same and performance of rutile-phase vanadium dioxide composition |
| CN105753050A (en) * | 2014-12-18 | 2016-07-13 | 刘闽苏 | A preparing method of rutile vanadium dioxide nanometer particles and the particles |
| CN111850684A (en) * | 2019-04-30 | 2020-10-30 | 中国科学技术大学 | Preparation method of vanadium dioxide-based single crystal and vanadium dioxide-based single crystal |
| CN112174206A (en) * | 2020-10-16 | 2021-01-05 | 成都先进金属材料产业技术研究院有限公司 | Method for directly preparing vanadium dioxide by taking vanadyl acetylacetonate as vanadium source |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304299C (en) * | 2005-04-25 | 2007-03-14 | 四川大学 | Process for preparing vanadium dioxide nano powder |
-
2009
- 2009-12-31 CN CN 200910247863 patent/CN101734720B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464354A (en) * | 2010-11-05 | 2012-05-23 | 中国科学院上海硅酸盐研究所 | Rutile-phase vanadium dioxide composition, coating containing same and performance of rutile-phase vanadium dioxide composition |
| CN102464354B (en) * | 2010-11-05 | 2015-01-21 | 中国科学院上海硅酸盐研究所 | Rutile-phase vanadium dioxide composition, coating containing same and performance of rutile-phase vanadium dioxide composition |
| CN105753050A (en) * | 2014-12-18 | 2016-07-13 | 刘闽苏 | A preparing method of rutile vanadium dioxide nanometer particles and the particles |
| CN111850684A (en) * | 2019-04-30 | 2020-10-30 | 中国科学技术大学 | Preparation method of vanadium dioxide-based single crystal and vanadium dioxide-based single crystal |
| CN112174206A (en) * | 2020-10-16 | 2021-01-05 | 成都先进金属材料产业技术研究院有限公司 | Method for directly preparing vanadium dioxide by taking vanadyl acetylacetonate as vanadium source |
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| CN101734720B (en) | 2013-05-29 |
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Effective date of registration: 20221101 Address after: 215400 No.6 Liangfu Road, Taicang City, Suzhou City, Jiangsu Province Patentee after: Jiangsu Institute of advanced inorganic materials Address before: 200050 No. 1295 Dingxi Road, Shanghai Patentee before: SHANGHAI INSTITUTE OF CERAMICS, CHINESE ACADEMY OF SCIENCES |
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