CN103693691A - Method of preparing vanadium dioxide by double-temperature area reduction process - Google Patents
Method of preparing vanadium dioxide by double-temperature area reduction process Download PDFInfo
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- CN103693691A CN103693691A CN201310713533.XA CN201310713533A CN103693691A CN 103693691 A CN103693691 A CN 103693691A CN 201310713533 A CN201310713533 A CN 201310713533A CN 103693691 A CN103693691 A CN 103693691A
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Abstract
The invention relates to a method of preparing vanadium dioxide by a double-temperature area reduction process. The method comprises the following steps: placing vanadium pentoxide and high-activity metal into a sealed system with negative pressure by spacing a certain distance; respectively heating vanadium pentoxide and the high-activity metal to different temperatures for thermally treating for determined time, so that oxygen partial pressure in the sealed system is lower than balanced oxygen partial pressure of vanadium pentoxide and vanadium pentoxide is reduced to obtain vanadium dioxide, wherein the high-activity metal is heated to a first temperature and vanadium pentoxide is heated to a second temperature lower than the first temperature; the heated high-activity metal reacts with oxygen gas in the sealed system to lower the oxygen partial pressure in the sealed system, so that the oxygen partial pressure of the sealed system is lower than the balanced oxygen partial pressure of vanadium pentoxide. The vanadium dioxide obtained by the method disclosed by the invention is controllable in crystalline phase and grain size, and has a morphology which is kept consistent or similar to that of a vanadium pentoxide precursor.
Description
Technical field
The present invention relates to the preparation method of hypovanadic oxide powder and film, be specifically related to a kind ofly by two warm area high activity metal assisted Reduction vanadium dioxide, prepare crystalline phase and the controlled hypovanadic oxide powder of particle diameter and the method for film.
Background technology
In the face of global energy dilemma, energy-saving building receives publicity just day by day, but current building has adopted the form of glass curtain wall in large quantities, and heat exchange therefore how to control glass port becomes most important to whole energy.High performance dimming film material, as low emissivity glass plated film and discoloration coating etc., will yield unusually brilliant results in this field, because they can, to the seeing through and reflection of the making one's options property of sunlight in particular range of wavelengths, maintain room temp and energy-conservation object thereby play.Wherein, vanadium dioxide (VO
2) be a class at the very promising thermochromic material in light modulation field because it has a metal/semiconductor phase transformation near 68 ℃, from Rutile Type, change monoclinic phase into.Before and after phase transformation can there is the variation of 4～5 orders of magnitude in the resistivity of vanadium dioxide, it also can be undergone mutation to the reflectivity of near infrared light simultaneously, because this characteristic vanadium dioxide film is widely used on smart window, can the heat exchange of active adjustment glass port by nernst cell internal and external temperature.Vanadium dioxide film adopts chemical method if chemical bath method, crystal pulling method and Physical are as method preparations such as magnetron sputtering methods conventionally.These methods all relate to precursor hypovanadic oxide powder, especially the preparation of target materials raw material of Physical.Hypovanadic oxide powder preparation method now or employing V
2o
5chemical reduction method (CN201110024215.3, CN200810202066.3, CN200610125435.4) in atmosphere reduction or solution.These method preparation process are relatively loaded down with trivial details, and some preparation method also needs to add organic solvent, the hypovanadic oxide powder stoichiometric ratio of final gained be difficult to control and preparation amount limited.
Summary of the invention
In the face of the problem that prior art exists, the object of the present invention is to provide and a kind ofly can prepare simply, fast the method for hypovanadic oxide powder and film.To this, we have used a kind of new method, under negative pressure, utilize heating high activity metal, make the oxygen reaction in metal and system, thereby reduce the oxygen partial pressure of whole system, when oxygen partial pressure is during lower than the equilibrium oxygen partial pres-sure of Vanadium Pentoxide in FLAKES, Vanadium Pentoxide in FLAKES is just reduced, thereby makes vanadium dioxide.
At this, the invention provides a kind of pair of warm area reduction method and prepare the method for vanadium dioxide, by Vanadium Pentoxide in FLAKES and high activity metal spaced apart be placed in the closed system with negative pressure, respectively described Vanadium Pentoxide in FLAKES and high activity metal are heated to different heat-treated specific times, thereby so that described closed system in oxygen partial pressure lower than the described Vanadium Pentoxide in FLAKES of equilibrium oxygen partial pres-sure of Vanadium Pentoxide in FLAKES, be reduced and obtain vanadium dioxide; Wherein, described high activity metal is heated to the first temperature, described Vanadium Pentoxide in FLAKES is heated to the second temperature lower than described the first temperature, thereby the middle oxygen reaction of the high activity metal being heated and described closed system reduces the oxygen partial pressure of described closed system and then make the oxygen partial pressure of described closed system lower than the equilibrium oxygen partial pres-sure of Vanadium Pentoxide in FLAKES.
In the present invention, under negative pressure, utilize heating high activity metal, make the oxygen reaction in metal and system, thereby reduce the oxygen partial pressure of whole system, when oxygen partial pressure is during lower than the equilibrium oxygen partial pres-sure of Vanadium Pentoxide in FLAKES, Vanadium Pentoxide in FLAKES is just reduced, thereby has made vanadium dioxide.The present invention uses two heating intervals, the material that plays reductive action is separated with the Vanadium Pentoxide in FLAKES being reduced, thereby can realize, the independent of both temperature controlled, and realized both interactions by the consistence of the whole air pressure of closed system, reach the object of reduction Vanadium Pentoxide in FLAKES.Present method can directly be processed Vanadium Pentoxide in FLAKES powder and film on a large scale, obtains hypovanadic oxide powder and film.With existing V
2o
5in atmosphere reduction or solution, chemical reduction method is compared, step of the present invention is simple, product-collecting is convenient, low for equipment requirements, preparation cycle is short, reduction effect is more remarkable, can obtain crystalline phase at low temperatures and particle diameter is controlled, and pattern can maintain consistent or approaching hypovanadic oxide powder and film with precursor Vanadium Pentoxide in FLAKES.
Preferably, described the first temperature is 600～1500 ℃, is preferably 700～1100 ℃.
Preferably, described the second temperature is 50～600 ℃, is preferably 200～500 ℃.
Preferably, described specific time is 0.5～12 hour.
Preferably, the pressure of described negative pressure is less than 100Pa, is preferably and is less than 1Pa.
Preferably, described high activity metal comprises a kind of in lithium, magnesium, aluminium, calcium, gallium, strontium, indium, barium or two or more combination arbitrarily.
In the present invention, described Vanadium Pentoxide in FLAKES comprises Vanadium Pentoxide in FLAKES powder and Vanadium Pentoxide in FLAKES film, the microscopic pattern of wherein said Vanadium Pentoxide in FLAKES powder comprises one or more the combination in ball, rod, band, pipe and irregular polygon, and described Vanadium Pentoxide in FLAKES film comprises the Vanadium Pentoxide in FLAKES film of preparing by one or more the combination in sol-gel method, silk screen print method, laser chemical vapor deposition method, hydrothermal crystallization method, electrophoretic method, magnetron sputtering method.
Beneficial effect of the present invention:
In the present invention, only need common vacuum system can realize the extensive preparation of vanadium dioxide powder and film.Beneficial effect of the present invention is, utilizes the auxiliary oxygen partial pressure that reduces whole system of high activity metal, makes the requirement of vacuum system greatly reduce; And Vanadium Pentoxide in FLAKES and high activity metal are separated, not only facilitate and collect sample, and can realize the independent of both temperature controlled, thereby cold zone can be controlled diameter of particle increase effectively.Vanadium dioxide crystalline phase and particle diameter that the present invention obtains are controlled, and pattern can remain consistent or approach with precursor Vanadium Pentoxide in FLAKES precursor.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the closed unit for the preparation of vanadium dioxide of an example of the present invention;
Fig. 2 is the TEM figure of the Vanadium Pentoxide in FLAKES powder as raw material of an example of the present invention;
The TEM that Fig. 3 is the hypovanadic oxide powder that made by method of the present invention by the Vanadium Pentoxide in FLAKES powder of Fig. 2 schemes;
Fig. 4 is the SEM figure of the Vanadium Pentoxide in FLAKES film as raw material of an example of the present invention;
The SEM that Fig. 5 is the vanadium dioxide film that made by method of the present invention by the Vanadium Pentoxide in FLAKES film of Fig. 4 schemes.
Embodiment
Below in conjunction with accompanying drawing and following embodiment, further illustrate the present invention, should be understood that accompanying drawing and following embodiment are only for the present invention is described, and unrestricted the present invention.
The object of the invention is to provide a kind of method of preparing simply, fast vanadium dioxide.The present invention utilizes high activity metal auxiliary, makes itself and intrasystem oxygen reaction, thereby has reduced the oxygen partial pressure of whole system, makes the requirement of rough vacuum system greatly reduce.In addition, our two independently heating intervals that artificially high reactivity reducing metal and Vanadium Pentoxide in FLAKES are placed in, are conducive to the collection of sample on the one hand; Can control independently both temperature on the other hand, so just, when high activity metal being heated to high temperature and reducing its equilibrium oxygen partial pres-sure, make Vanadium Pentoxide in FLAKES in low-temperature condition, more favourable to the control of vanadium dioxide particle diameter and crystalline phase.In addition, the method can be used for Vanadium Pentoxide in FLAKES prepared by any means, is with a wide range of applications.
In the present invention, raw material Vanadium Pentoxide in FLAKES used can comprise Vanadium Pentoxide in FLAKES powder and Vanadium Pentoxide in FLAKES film, wherein the microscopic pattern of Vanadium Pentoxide in FLAKES powder comprises one or more the combination in ball, rod, band, pipe and irregular polygon, and Vanadium Pentoxide in FLAKES film comprises the Vanadium Pentoxide in FLAKES film of preparing by one or more the combination in sol-gel method, silk screen print method, laser chemical vapor deposition method, hydrothermal crystallization method, electrophoretic method, magnetron sputtering method.
High activity metal used comprises a kind of in lithium, magnesium, aluminium, calcium, gallium, strontium, indium, barium or two or more combination arbitrarily.
Method of the present invention is carried out in the encloses container under negative pressure, and the pressure range of negative pressure is lower than 100Pa, preferably lower than 1Pa.In described method, the temperature in high activity metal interval can be 600～1500 ℃, preferably 700～1100 ℃.In method of the present invention, the temperature of Vanadium Pentoxide in FLAKES can be 50～600 ℃, preferably 200～500 ℃.The treatment time of method of the present invention can be 0.5～12h.
Preparation flow:
1) get the different heating interval that high activity metal and vanadium pentoxide powder or film are placed in respectively encloses container, be evacuated to the negative pressure of regulation, the schematic diagram of the closed system that the present invention is used can be shown in Figure 1, it can be the heatable pipe furnace of closed, by Vanadium Pentoxide in FLAKES and high activity metal, for example aluminium is placed on respectively the different positions that is spaced from each other a determining deviation in closed system, to apply different heating environments, the negative pressure of regulation can be less than 100Pa, preferably be less than 1Pa, in one example, be less than 0.1Pa;
2) high activity metal is interval and Vanadium Pentoxide in FLAKES interval is heated to different temperature, particularly, high activity metal is placed in to higher temperature (the first temperature, for example 600～1500 ℃, preferably 700～1100 ℃) region, and Vanadium Pentoxide in FLAKES is placed in to relatively low (the second temperature, for example 500～600 ℃, preferably 200～500 ℃) region, can simply install like this and realize two warm area restoring systems; Under negative pressure, utilize heating high activity metal, make the oxygen reaction in metal and system, thus the oxygen partial pressure of reduction whole system, when oxygen partial pressure is during lower than the equilibrium oxygen partial pres-sure of Vanadium Pentoxide in FLAKES, Vanadium Pentoxide in FLAKES is just reduced, thereby has made vanadium dioxide;
3) process after 0.5～12h, close heating power supply, after sample is cooling, obtain vanadium dioxide powder or film.
Referring to Fig. 2 and Fig. 3, its illustrate respectively as the Vanadium Pentoxide in FLAKES powder of raw material and after method of the present invention reduction the TEM figure of the hypovanadic oxide powder of gained, as seen from the figure, the pattern of hypovanadic oxide powder can remain consistent or approach with precursor Vanadium Pentoxide in FLAKES powder, and its particle diameter is 10～20nm.
Referring to Fig. 4 and Fig. 5, its illustrate respectively as the Vanadium Pentoxide in FLAKES film of raw material and after method of the present invention reduction the SEM figure of the vanadium dioxide film of gained, as seen from the figure, the pattern of vanadium dioxide film can remain consistent or approach with precursor Vanadium Pentoxide in FLAKES film, and its particle diameter is 100～300nm.
Further exemplify embodiment below to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention., those skilled in the art can do in suitable scope and be selected by explanation herein the temperature that following example is concrete, time etc. are only also examples in OK range,, and do not really want to be defined in the below concrete numerical value of example.
Embodiment 1
Take commercial Vanadium Pentoxide in FLAKES as raw material, aluminium is high reactivity reducing metal, puts into respectively the different heating interval of airtight tube type stove, and whole system is evacuated to after 0.1Pa, aluminium and Vanadium Pentoxide in FLAKES are heated to respectively to 800 ℃ and 400 ℃, after reaction 3h, close heating power supply.After sample is cooling, obtain vanadium dioxide.
Embodiment 2
Take homemade Vanadium Pentoxide in FLAKES nano-powder as raw material (Ding SJ, Liu ZQ, Li DZ, Zhao W, Huang FQ, ACS Applied Materials & Interfaces.2013,5,1630 – 1635), aluminium is high reactivity reducing metal, puts into respectively the different heating interval of airtight tube type stove, and whole system is evacuated to after 0.1Pa, aluminium and Vanadium Pentoxide in FLAKES are heated to respectively to 8500 ℃ and 200 ℃, after reaction 6h, close heating power supply.After sample is cooling, obtain vanadium dioxide nano powder.Fig. 2 and Fig. 3 illustrate respectively as the Vanadium Pentoxide in FLAKES powder of raw material and the TEM figure of the hypovanadic oxide powder making, and as seen from the figure, the pattern of hypovanadic oxide powder can remain consistent or approach with precursor Vanadium Pentoxide in FLAKES powder, and its particle diameter is 10～20nm.
Embodiment 3
Take commercial Vanadium Pentoxide in FLAKES as raw material, magnesium is high reactivity reducing metal, puts into respectively the different heating interval of airtight tube type stove, and whole system is evacuated to after 0.1Pa, aluminium and Vanadium Pentoxide in FLAKES are heated to respectively to 750 ℃ and 450 ℃, after reaction 5h, close heating power supply.After sample is cooling, obtain vanadium dioxide.
Embodiment 4
Get and take quartz as substrate, the Vanadium Pentoxide in FLAKES film of magnetron sputtering plating, aluminium is high reactivity reducing metal, puts into respectively the different heating interval of airtight tube type stove, whole system is evacuated to after 0.1Pa, aluminium and Vanadium Pentoxide in FLAKES are heated to respectively to 850 ℃ and 500 ℃.After reaction 1h, close heating power supply, after sample is cooling, obtain vanadium dioxide film.Fig. 4 and Fig. 5 illustrate respectively as the Vanadium Pentoxide in FLAKES film of raw material and the SEM figure of the vanadium dioxide film making, and as seen from the figure, the pattern of hypovanadic oxide powder can remain consistent or approach with precursor Vanadium Pentoxide in FLAKES powder, and its particle diameter is 100～300nm.
Embodiment 5
Get and take sheet glass as substrate, the Vanadium Pentoxide in FLAKES film of dip-coating method plated film, calcium is high reactivity reducing metal, puts into respectively the different heating interval of airtight tube type stove, whole system is evacuated to after 0.1Pa, aluminium and Vanadium Pentoxide in FLAKES are heated to respectively to 1100 ℃ and 350 ℃.After reaction 8h, close heating power supply, after sample is cooling, obtain vanadium dioxide film.
Embodiment 6
Get and take quartz as substrate, take homemade Vanadium Pentoxide in FLAKES microporous membrane as raw material (Ding SJ, Liu ZQ, Li DZ, Zhao W, Huang FQ, ACS Applied Materials & Interfaces.2013,5,1630 – 1635), aluminium is high reactivity reducing metal, puts into respectively the different heating interval of airtight tube type stove, whole system is evacuated to after 0.1Pa, aluminium and Vanadium Pentoxide in FLAKES are heated to respectively to 800 ℃ and 250 ℃.After reaction 8h, close heating power supply, after sample is cooling, obtain vanadium dioxide microporous membrane.
Industrial applicability: method of the present invention can directly be processed Vanadium Pentoxide in FLAKES powder and Vanadium Pentoxide in FLAKES film on a large scale, obtains high performance hypovanadic oxide powder and vanadium dioxide film.The present invention has bright prospects in the application aspect of vanadium dioxide.
Claims (10)
1. two warm area reduction methods are prepared the method for vanadium dioxide, it is characterized in that, described method comprises: by Vanadium Pentoxide in FLAKES and high activity metal spaced apart be placed in the closed system with negative pressure, respectively described Vanadium Pentoxide in FLAKES and high activity metal are heated to different heat-treated specific times, thereby so that described closed system in oxygen partial pressure lower than the described Vanadium Pentoxide in FLAKES of equilibrium oxygen partial pres-sure of Vanadium Pentoxide in FLAKES, be reduced and obtain vanadium dioxide; Wherein, described high activity metal is heated to the first temperature, described Vanadium Pentoxide in FLAKES is heated to the second temperature lower than described the first temperature, thereby the middle oxygen reaction of the high activity metal being heated and described closed system reduces the oxygen partial pressure of described closed system and then make the oxygen partial pressure of described closed system lower than the equilibrium oxygen partial pres-sure of Vanadium Pentoxide in FLAKES.
2. method according to claim 1, is characterized in that, described the first temperature is 600～1500 ℃.
3. method according to claim 2, is characterized in that, described the first temperature is 700～1100 ℃.
4. according to the method described in any one in claim 1～3, it is characterized in that, described the second temperature is 50～600 ℃.
5. method according to claim 4, is characterized in that, described the second temperature is 200～500 ℃.
6. according to the method described in any one in claim 1～5, it is characterized in that, described specific time is 0.5～12 hour.
7. according to the method described in any one in claim 1～6, it is characterized in that, the pressure of described negative pressure is less than 100Pa.
8. method according to claim 7, is characterized in that, the pressure of described negative pressure is less than 1Pa.
9. according to the method described in any one in claim 1～8, it is characterized in that, described high activity metal comprises a kind of in lithium, magnesium, aluminium, calcium, gallium, strontium, indium, barium or two or more combination arbitrarily.
10. according to the method described in any one in claim 1～9, it is characterized in that, described Vanadium Pentoxide in FLAKES comprises Vanadium Pentoxide in FLAKES powder and Vanadium Pentoxide in FLAKES film, the microscopic pattern of wherein said Vanadium Pentoxide in FLAKES powder comprises one or more the combination in ball, rod, band, pipe and irregular polygon, and described Vanadium Pentoxide in FLAKES film comprises the Vanadium Pentoxide in FLAKES film of preparing by one or more the combination in sol-gel method, silk screen print method, laser chemical vapor deposition method, hydrothermal crystallization method, electrophoretic method, magnetron sputtering method.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107010668A (en) * | 2017-05-18 | 2017-08-04 | 北京科技大学 | Hightemperature gas-phase reduction deposition prepares ultra-fine Magn é li phases VnO2n‑1The device and method of powder |
| CN110699670A (en) * | 2019-11-13 | 2020-01-17 | 西安近代化学研究所 | Preparation method of vanadium dioxide film |
| TWI800666B (en) * | 2018-07-31 | 2023-05-01 | 日商日本化學工業股份有限公司 | Method of producing vanadium dioxide |
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| CN1899970A (en) * | 2005-12-16 | 2007-01-24 | 大连理工大学 | Method for preparing high purity vanadium dioxide particles |
| KR20110057692A (en) * | 2009-11-24 | 2011-06-01 | 최승훈 | A manufacturing method of vanadium dioxide |
| CN102649583A (en) * | 2011-11-23 | 2012-08-29 | 中国科学技术大学 | Method for synthesizing monoclinic phase nano vanadium dioxide powder |
| CN102826604A (en) * | 2012-09-26 | 2012-12-19 | 中国科学院上海硅酸盐研究所 | Preparation method of vanadium dioxide powder |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1899970A (en) * | 2005-12-16 | 2007-01-24 | 大连理工大学 | Method for preparing high purity vanadium dioxide particles |
| KR20110057692A (en) * | 2009-11-24 | 2011-06-01 | 최승훈 | A manufacturing method of vanadium dioxide |
| CN102649583A (en) * | 2011-11-23 | 2012-08-29 | 中国科学技术大学 | Method for synthesizing monoclinic phase nano vanadium dioxide powder |
| CN102826604A (en) * | 2012-09-26 | 2012-12-19 | 中国科学院上海硅酸盐研究所 | Preparation method of vanadium dioxide powder |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107010668A (en) * | 2017-05-18 | 2017-08-04 | 北京科技大学 | Hightemperature gas-phase reduction deposition prepares ultra-fine Magn é li phases VnO2n‑1The device and method of powder |
| CN107010668B (en) * | 2017-05-18 | 2018-07-27 | 北京科技大学 | Hightemperature gas-phase reduction deposition prepares ultra-fine Magn é li phases VnO2n-1The device and method of powder |
| TWI800666B (en) * | 2018-07-31 | 2023-05-01 | 日商日本化學工業股份有限公司 | Method of producing vanadium dioxide |
| CN110699670A (en) * | 2019-11-13 | 2020-01-17 | 西安近代化学研究所 | Preparation method of vanadium dioxide film |
| CN110699670B (en) * | 2019-11-13 | 2021-11-23 | 西安近代化学研究所 | Preparation method of vanadium dioxide film |
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