CN103693691B - A kind of pair of warm area reduction method prepares the method for vanadium dioxide - Google Patents
A kind of pair of warm area reduction method prepares the method for vanadium dioxide Download PDFInfo
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Abstract
The present invention relates to the method that a kind of pair of warm area reduction method prepares vanadium dioxide, described method comprises: Vanadium Pentoxide in FLAKES and high activity metal are placed in the closed system with negative pressure spaced at a distance, respectively described Vanadium Pentoxide in FLAKES and high activity metal are heated to different heat-treated specific times, to make the oxygen partial pressure in described closed system lower than the equilibrium oxygen partial pres-sure of Vanadium Pentoxide in FLAKES thus described Vanadium Pentoxide in FLAKES is reduced and obtains 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 first temperature, the middle oxygen reaction of the high activity metal be heated and described closed system thus reduce the oxygen partial pressure of described closed system and then make the equilibrium oxygen partial pres-sure of oxygen partial pressure lower than Vanadium Pentoxide in FLAKES of described closed system.The vanadium dioxide crystalline phase that the present invention obtains and size tunable, pattern can remain consistent or close with precursor Vanadium Pentoxide in FLAKES 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 prepare the hypovanadic oxide powder of crystalline phase and size tunable and the method for film by two warm area high activity metal assisted Reduction vanadium dioxide.
Background technology
In the face of the energy dilemma in the whole world, energy-saving building receives publicity just day by day, but current building have employed the form of glass curtain wall in large quantities, and the heat exchange therefore how controlling 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 sunlight makes selective in particular range of wavelengths through and reflection, thus play and maintain room temp and energy-conservation object.Wherein, vanadium dioxide (VO
2) be the class thermochromic material very promising in light modulation field, because it has a metal/semiconductor phase transformation near 68 DEG C, namely change monoclinic phase into from Rutile Type.Before and after phase transformation can there is the change of 4 ~ 5 orders of magnitude in the resistivity of vanadium dioxide, it also can be undergone mutation near infrared light reflectance simultaneously, because this characteristic vanadium dioxide film is widely used on smart window, i.e. the heat exchange of active adjustment glass port by nernst cell internal and external temperature.Vanadium dioxide film adopts chemical method if chemical baths, crystal pulling method and Physical are as method preparations such as magnetron sputtering methods usually.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
5atmosphere is reduced or chemical reduction method (CN201110024215.3, CN200810202066.3, CN200610125435.4) in 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 prior art Problems existing, the object of the present invention is to provide a kind of method can preparing hypovanadic oxide powder and film simply, fast.To this, we used a kind of new method, under negative pressure, utilize heating high activity metal, make the oxygen reaction in metal and system, thus reduce the oxygen partial pressure of whole system, when the equilibrium oxygen partial pres-sure of oxygen partial pressure lower than Vanadium Pentoxide in FLAKES, Vanadium Pentoxide in FLAKES is just reduced, thus obtained vanadium dioxide.
At this, the invention provides the method that a kind of pair of warm area reduction method prepares vanadium dioxide, Vanadium Pentoxide in FLAKES and high activity metal are placed in the closed system with negative pressure spaced at a distance, respectively described Vanadium Pentoxide in FLAKES and high activity metal are heated to different heat-treated specific times, to make the oxygen partial pressure in described closed system lower than the equilibrium oxygen partial pres-sure of Vanadium Pentoxide in FLAKES thus described Vanadium Pentoxide in FLAKES is reduced and obtains 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 first temperature, the middle oxygen reaction of the high activity metal be heated and described closed system thus reduce the oxygen partial pressure of described closed system and then make the equilibrium oxygen partial pres-sure of oxygen partial pressure lower than Vanadium Pentoxide in FLAKES of described closed system.
In the present invention, under negative pressure, heating high activity metal is utilized, make the oxygen reaction in metal and system, thus reduce the oxygen partial pressure of whole system, when the equilibrium oxygen partial pres-sure of oxygen partial pressure lower than Vanadium Pentoxide in FLAKES, Vanadium Pentoxide in FLAKES is just reduced, thus has obtained vanadium dioxide.The present invention uses two heating intervals, the material playing reductive action is separated with the Vanadium Pentoxide in FLAKES be reduced, thus can realize controlling the independence of both temperature, and the interaction both being realized by the consistence of the overall air pressure of closed system, reach the object of reduction Vanadium Pentoxide in FLAKES.Present method can directly process Vanadium Pentoxide in FLAKES powder and film on a large scale, obtains hypovanadic oxide powder and film.With existing V
2o
5atmosphere is reduced or in 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 and size tunable at low temperatures, and pattern can maintain consistent or close hypovanadic oxide powder and film with precursor Vanadium Pentoxide in FLAKES.
Preferably, described first temperature is 600 ~ 1500 DEG C, is preferably 700 ~ 1100 DEG C.
Preferably, described second temperature is 50 ~ 600 DEG C, is preferably 200 ~ 500 DEG C.
Preferably, described specific time is 0.5 ~ 12 hour.
Preferably, the pressure of described negative pressure is less than 100Pa, is preferably less than 1Pa.
Preferably, described high activity metal comprises combinations a kind of or two or more arbitrarily in lithium, magnesium, aluminium, calcium, gallium, strontium, indium, barium.
In the present invention, described Vanadium Pentoxide in FLAKES comprises Vanadium Pentoxide in FLAKES powder and vanadium pentoxide films, the microscopic pattern of wherein said Vanadium Pentoxide in FLAKES powder comprises the combination of one or more in ball, rod, band, pipe and irregular polygon, and described vanadium pentoxide films comprises the vanadium pentoxide films prepared by the combination of one or more in sol-gel method, silk screen print method, laser induced chemical vapor depostion method, hydrothermal crystallisation methods, electrophoretic method, magnetron sputtering method.
Beneficial effect of the present invention:
In the present invention, common vacuum system is only needed can to realize the extensive preparation of vanadium dioxide powder and film.Beneficial effect of the present invention is, utilizes the auxiliary oxygen partial pressure reducing whole system of high activity metal, makes greatly to reduce the requirement of vacuum system; And Vanadium Pentoxide in FLAKES and high activity metal are separated, not only conveniently collect sample, and can realize controlling the independence of both temperature, cold zone thus effectively can control diameter of particle increase.The vanadium dioxide crystalline phase that the present invention obtains and size tunable, pattern can remain consistent or close 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 the present invention's example;
Fig. 2 is the TEM figure of the Vanadium Pentoxide in FLAKES powder as raw material of the present invention's example;
Fig. 3 is the TEM figure of the hypovanadic oxide powder obtained by method of the present invention by the Vanadium Pentoxide in FLAKES powder of Fig. 2;
Fig. 4 is the SEM figure of the vanadium pentoxide films as raw material of the present invention's example;
Fig. 5 is the SEM figure of the vanadium dioxide film obtained by method of the present invention by the vanadium pentoxide films of Fig. 4.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.
The object of the invention is to provide a kind of method preparing vanadium dioxide simply, fast.The present invention utilizes high activity metal to assist, and makes itself and intrasystem oxygen reaction, thus reduces the oxygen partial pressure of whole system, make greatly to reduce the requirement of low vacuum system.In addition, high reactivity reducing metal and Vanadium Pentoxide in FLAKES are placed in two independently heating intervals by artificially, are conducive to the collection of sample on the one hand; Both temperature can be controlled on the other hand independently, so just high activity metal is being heated to while high temperature reduces its equilibrium oxygen partial pres-sure, make Vanadium Pentoxide in FLAKES be in low-temperature condition, to the control of vanadium dioxide particle diameter and crystalline phase advantageously.In addition, the method can be used for Vanadium Pentoxide in FLAKES prepared by any means, is with a wide range of applications.
Raw material Vanadium Pentoxide in FLAKES used in the present invention can comprise Vanadium Pentoxide in FLAKES powder and vanadium pentoxide films, wherein the microscopic pattern of Vanadium Pentoxide in FLAKES powder comprises the combination of one or more in ball, rod, band, pipe and irregular polygon, and vanadium pentoxide films comprises the vanadium pentoxide films prepared by the combination of one or more in sol-gel method, silk screen print method, laser induced chemical vapor depostion method, hydrothermal crystallisation methods, electrophoretic method, magnetron sputtering method.
High activity metal used comprises combinations a kind of or two or more arbitrarily in lithium, magnesium, aluminium, calcium, gallium, strontium, indium, barium.
Carry out in method of the present invention encloses container under negative pressure, the pressure range of negative pressure lower than 100Pa, preferably lower than 1Pa.In described method, the temperature in high activity metal interval can be 600 ~ 1500 DEG C, preferably 700 ~ 1100 DEG C.In method of the present invention, the temperature of Vanadium Pentoxide in FLAKES can be 50 ~ 600 DEG C, preferably 200 ~ 500 DEG C.The treatment time of method of the present invention can be 0.5 ~ 12h.
Preparation flow:
1) the different heating interval that high activity metal and vanadium pentoxide powder or film are placed in encloses container is respectively got, 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, such as aluminium is placed in closed system the different positions being spaced from each other a determining deviation respectively, to apply different heating environments, the negative pressure of regulation can be less than 100Pa, preferably be less than 1Pa, in one example, 0.1Pa is less than;
2) high activity metal is interval and Vanadium Pentoxide in FLAKES interval is heated to different temperature, particularly, high activity metal is placed in higher temperature (the first temperature, such as 600 ~ 1500 DEG C, preferably 700 ~ 1100 DEG C) region, and Vanadium Pentoxide in FLAKES is placed in relatively low (the second temperature, such as 500 ~ 600 DEG C, preferably 200 ~ 500 DEG C) region, simply can realize two warm area restoring system by device like this; 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 the equilibrium oxygen partial pres-sure of oxygen partial pressure lower than Vanadium Pentoxide in FLAKES, Vanadium Pentoxide in FLAKES is just reduced, thus has obtained vanadium dioxide;
3) after processing 0.5 ~ 12h, close heating power supply, after sample cooling, namely obtain vanadium dioxide powder or film.
See 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 close with precursor Vanadium Pentoxide in FLAKES powder, and its particle diameter is 10 ~ 20nm.
See Fig. 4 and Fig. 5, its illustrate respectively as the vanadium pentoxide films 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 close with precursor vanadium pentoxide films, and its particle diameter is 100 ~ 300nm.
Exemplify embodiment below further 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.The temperature that following example is concrete, time etc. are also only examples in OK range, and namely, those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Embodiment 1
With commercial Vanadium Pentoxide in FLAKES for raw material, aluminium is high reactivity reducing metal, puts into the heating interval that airtight tube type stove is different respectively, after whole system is evacuated to 0.1Pa, aluminium and Vanadium Pentoxide in FLAKES are heated to 800 DEG C and 400 DEG C respectively, after reaction 3h, close heating power supply.After sample cooling, obtain vanadium dioxide.
Embodiment 2
With homemade Vanadium Pentoxide in FLAKES nano-powder for raw material (Ding SJ, Liu ZQ, Li DZ, Zhao W, Huang FQ, ACS AppliedMaterials & Interfaces.2013,5,1630 – 1635), aluminium is high reactivity reducing metal, puts into the heating interval that airtight tube type stove is different respectively, after whole system is evacuated to 0.1Pa, aluminium and Vanadium Pentoxide in FLAKES are heated to 850 DEG C and 200 DEG C respectively, after reaction 6h, close heating power supply.After sample cooling, obtain vanadium dioxide nano powder.Fig. 2 and Fig. 3 illustrates the TEM figure of Vanadium Pentoxide in FLAKES powder as raw material and obtained hypovanadic oxide powder respectively, and as seen from the figure, the pattern of hypovanadic oxide powder can remain consistent or close with precursor Vanadium Pentoxide in FLAKES powder, and its particle diameter is 10 ~ 20nm.
Embodiment 3
With commercial Vanadium Pentoxide in FLAKES for raw material, magnesium is high reactivity reducing metal, puts into the heating interval that airtight tube type stove is different respectively, after whole system is evacuated to 0.1Pa, aluminium and Vanadium Pentoxide in FLAKES are heated to 750 DEG C and 450 DEG C respectively, after reaction 5h, close heating power supply.After sample cooling, obtain vanadium dioxide.
Embodiment 4
Get with quartz is substrate, the vanadium pentoxide films of magnetron sputtering plating, aluminium is high reactivity reducing metal, puts into the heating interval that airtight tube type stove is different respectively, after whole system is evacuated to 0.1Pa, aluminium and Vanadium Pentoxide in FLAKES are heated to 850 DEG C and 500 DEG C respectively.Close heating power supply after reaction 1h, after sample cooling, obtain vanadium dioxide film.Fig. 4 and Fig. 5 illustrates the SEM figure of vanadium pentoxide films as raw material and obtained vanadium dioxide film respectively, and as seen from the figure, the pattern of hypovanadic oxide powder can remain consistent or close with precursor Vanadium Pentoxide in FLAKES powder, and its particle diameter is 100 ~ 300nm.
Embodiment 5
Get with sheet glass is substrate, the vanadium pentoxide films of dip-coating method plated film, calcium is high reactivity reducing metal, puts into the heating interval that airtight tube type stove is different respectively, after whole system is evacuated to 0.1Pa, aluminium and Vanadium Pentoxide in FLAKES are heated to 1100 DEG C and 350 DEG C respectively.Close heating power supply after reaction 8h, after sample cooling, obtain vanadium dioxide film.
Embodiment 6
Getting with quartz is substrate, with homemade Vanadium Pentoxide in FLAKES microporous membrane for 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 the heating interval that airtight tube type stove is different respectively, after whole system is evacuated to 0.1Pa, aluminium and Vanadium Pentoxide in FLAKES are heated to 800 DEG C and 250 DEG C respectively.Close heating power supply after reaction 8h, after sample cooling, obtain vanadium dioxide microporous membrane.
Industrial applicability: method of the present invention can directly process Vanadium Pentoxide in FLAKES powder and vanadium pentoxide films 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 (9)
1. a two warm area reduction method prepares the method for vanadium dioxide, it is characterized in that, described method comprises: Vanadium Pentoxide in FLAKES and high activity metal are placed in the closed system with negative pressure spaced at a distance, respectively described Vanadium Pentoxide in FLAKES and high activity metal are heated to different heat-treated specific times, to make the oxygen partial pressure in described closed system lower than the equilibrium oxygen partial pres-sure of Vanadium Pentoxide in FLAKES thus described Vanadium Pentoxide in FLAKES is reduced and obtains 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 first temperature, oxygen reaction in the high activity metal be heated and described closed system thus reduce the oxygen partial pressure of described closed system and then make the equilibrium oxygen partial pres-sure of oxygen partial pressure lower than Vanadium Pentoxide in FLAKES of described closed system, described high activity metal comprises combinations a kind of or two or more arbitrarily in lithium, magnesium, aluminium, calcium, gallium, strontium, indium, barium.
2. method according to claim 1, is characterized in that, described first temperature is 600 ~ 1500 DEG C.
3. method according to claim 2, is characterized in that, described first temperature is 700 ~ 1100 DEG C.
4. the method according to any one of claims 1 to 3, is characterized in that, described second temperature is 50 ~ 600 DEG C.
5. method according to claim 4, is characterized in that, described second temperature is 200 ~ 500 DEG C.
6. the method according to any one of claims 1 to 3, is characterized in that, described specific time is 0.5 ~ 12 hour.
7. the method according to any one of claims 1 to 3, 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. the method according to any one of claims 1 to 3, it is characterized in that, described Vanadium Pentoxide in FLAKES comprises Vanadium Pentoxide in FLAKES powder and vanadium pentoxide films, the microscopic pattern of wherein said Vanadium Pentoxide in FLAKES powder comprises the combination of one or more in ball, rod, band, pipe and irregular polygon, and described vanadium pentoxide films comprises the vanadium pentoxide films prepared by the combination of one or more in sol-gel method, silk screen print method, laser induced chemical vapor depostion method, hydrothermal crystallisation methods, electrophoretic method, magnetron sputtering method.
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