CN104030356A - Vanadium dioxide doped powder, and film and preparation method thereof - Google Patents
Vanadium dioxide doped powder, and film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a vanadium dioxide doped powder, and a film and a preparation method thereof. The chemical composition of the vanadium dioxide doped powder is V[1-x]M[x]O[2], x is greater than 0 and not greater than 0.5, M is a doped element, and the doped element is Mg or Al, and can be used for improving the optical performances of the vanadium dioxide doped powder and adjusting the phase transition temperature of the vanadium dioxide doped powder.
Description
Technical field
The present invention relates to the hypovanadic oxide powder preparation in chemical field and Material Field, particularly doped vanadium dioxide powder, and its preparation method and application.
Background technology
Under the situation that global energy supply is becoming tight and environment goes from bad to worse, energy-saving and emission-reduction have become the common target in countries in the world.The portion report that United Nations Environment Programme (UNEP) delivers on December 11st, 2009 claims: Global Emissions of Greenhouse Gas has 1/3 to consume energy relevant with buildings.China is energy consumption big country, and the energy of annual loss is equivalent to 1,500,000,000 tons of standard coals, and wherein 30% left and right is architectural energy consumption.And the most serious in architectural energy consumption be glass, its energy waste accounts for 50% of whole building energy consumption.Therefore by advancing building energy-saving, exploitation energy-saving glass, is expected to significantly reduce greenhouse gas emission and energy consumption.
Can there is reversible transformation in rutile phase hypovanadic oxide, changed into the Rutile Type (R phase) of high temperature state by the monoclinic phase (M phase) of low temperature in the time of 68 DEG C.In phase transformation, the optical property of vanadium dioxide, electric property, magnetic performance etc. all can be reversible change along with occurring.Just therefore, vanadium dioxide has outstanding advantage aspect intelligent control.Intellectuality response by vanadium dioxide to environment, in the time of low temperature (68 DEG C of <), vanadium dioxide has higher transmitance in infrared region; When high temperature (68 DEG C of >), vanadium dioxide embodies higher reflection and absorption in infrared region.In phase transition process, the transmitance of visible region is almost constant, as the preferred material of smart window, can reduce refrigeration and heating energy consumption, increases residence comfort, economizes on resources simultaneously, preserves the ecological environment.The Development patterns of building Sustainable development is had to important contribution.
At present, vanadium dioxide is applied to smart window and also has following subject matter: the adjusting function of (one) vanadium dioxide film is difficult to exceed 10%; (2) visible light transmissivity is not high, is still difficult to exceed 50% through the vanadium dioxide film visible ray integration transmitance of optimizing, and can not reach the requirement of indoor lighting; (3) infrared ability of regulation and control deficiency, when visible light transmissivity reaches 50%, before and after phase transformation, sunlight ability of regulation and control is less than 10%.(4) the more ugly yellow that vanadium dioxide embodies, can not meet esthetic requirement.
The film that the vanadium dioxide of the doping of report is prepared taking Physical and Liquid preparation methods film, as main, comprise that reactive sputtering, evaporation reaction method, chemical Vapor deposition process, pulse laser degrade method and hydrothermal method.For the preparation of doping vanadium oxide powder body, patent CN 10164900A has mentioned the doped vanadium dioxide powder that adds tungsten to prepare particle diameter≤50nm, but this patent documentation adopts the method for high temperature sintering to prepare R phase hypovanadic oxide powder from B phase hypovanadic oxide powder, its crystalline phase is difficult to control.And disclosed doped vanadium dioxide powder is devoted to regulate and control by doped metallic elements the transformation temperature of vanadium dioxide more in prior art, doped element used adopts tungsten, molybdenum more, adulterates.
Application hypovanadic oxide powder and hypovanadic oxide powder and the compound film of preparing of other materials, method is simple, is convenient to large-scale operation, not only can transform for the energy-saving of original glass port, and can be coated on different substrates, expands the applicability of vanadium dioxide.But prepare vanadium dioxide film and coating, the pattern to hypovanadic oxide powder and particle diameter all have special requirement, require hypovanadic oxide powder to have excellent dispersiveness.The disclosed prepared hypovanadic oxide powder of doped element that added in above-mentioned prior art, its size is large (being greater than 100nm) mostly, it is often column (length-to-diameter ratio is greater than 10:1 mostly), doped element can not regulate and control crystallization phases, the dispersiveness of the doped vanadium dioxide powder making is also bad, should not be for the preparation of vanadium dioxide film and coating.
Patent CN 102120615 A have mentioned and have comprised scandium, titanium, chromium, manganese, iron, cobalt, nickel, copper and zinc, and described tin and near element thereof comprise the doping of the elements such as indium, antimony, tin, gallium, germanium, lead and bismuth, and appearance and size problem has been discussed.Above method can not solve transformation temperature simultaneously, performance of control and transmitance problem.European patent WO2010038202-A1 and US Patent No. 2011260123-A1 have reported the preparation and application of magnesium doping vanadium oxide film, but this method complex process is difficult for industrialization, do not use the report of magnesium doping vanadium oxide powder body at present.Taking the organic pad pasting of flexibility prepared as base of hypovanadic oxide powder of doping, knifing or film etc. can be good at embodying the optical property before and after hypovanadic oxide powder phase transformation, and prepares easyly, and easily operation, has good application prospect.
Summary of the invention
The inventor finds that by research magnesium-doped in vanadium dioxide or aluminium can regulate and control pattern and the particle diameter of vanadium dioxide, thereby shows favorable optical performance and lower transformation temperature.
One aspect of the present invention provides a kind of doped vanadium dioxide powder, and the chemical constitution of described doped vanadium dioxide powder is V
1-xm
xo
2, 0<x≤0.5, wherein M is doped element, described doped element M is Mg or Al, and described doped element M is for improving the optical property of described doped vanadium dioxide powder and the transformation temperature of the described doped vanadium dioxide powder of adjusting.Wherein preferably 0.005≤x≤0.3, especially preferably 0.005≤x≤0.05.
Adopt the present invention, the doped element (magnesium or aluminium) specifying by doping, can control hypovanadic oxide powder size and pattern, can control the little and homogeneous of hypovanadic oxide powder size that makes preparation, this powder has high visible light transmissivity and the good infrared performance of control of high low temperature, can reduce Rutile Type vanadium oxide phase alternating temperature simultaneously, and this doped vanadium dioxide powder stable crystal form, it uses for example, in dispersion agent (polyvinylpyrrolidone) good dispersity at water, be easy to be coated on substrate, be suitable for preparing film and the coating of hypovanadic oxide powder, can be applicable to smart window, flexible lamina, optoelectronic switch, the fields such as thermistor and optical information storage and thermal insulating coating.
In the present invention, described doped vanadium dioxide powder is preferably bar-shaped or particulate state.The length-to-diameter ratio of powder is preferably 1:1～50:1.Described doped vanadium dioxide powder is of a size of between the μ m of 5nm～1 adjustable, preferably at least one dimension, is not more than 100nm, more preferably in three dimensions, is all not more than 100nm, most preferably in three dimensions, is all not more than 70nm.The described bar-shaped corynebacterium that is preferably, described particulate state can be such as subsphaeroidal, oval, snowflake shape, cube, sheet shape etc.
In the present invention, doped vanadium dioxide powder comprises rutile phase hypovanadic oxide or pure rutile phase hypovanadic oxide, and the shared ratio of rutile phase hypovanadic oxide can, up to 80%, even can reach 100%.In the present invention, doped vanadium dioxide powder not only has controlled size and pattern, also has semi-conductor-Metal Phase Transition character, and the transformation temperature of doped vanadium dioxide powder of the present invention is adjustable continuously between 10～68 DEG C.
The present invention also provides a kind of method of preparing above-mentioned doped vanadium dioxide powder, described method for example comprises, according to stoichiometric ratio (molar ratio of dopant ion and vanadium ion can at 1:1000 between 1:1) doping reagent is added in the precursor liquid containing tetravalence vanadium, stir, hydro-thermal reaction 0.01～96 hour at 160～400 DEG C.
Preferably, the temperature of described hydro-thermal reaction is 200～250 DEG C, and the described hydro-thermal reaction time is 16～48 hours.
Precursor liquid containing tetravalence vanadium can be by making water-soluble soluble vanadium raw material.Conventional soluble vanadium raw material can be trivalent, tetravalence or pentavalent vanadium and/or its hydrate.Should understand, in the time adopting trivalent or pentavalent vanadic salts and/or its hydrate as vanadium raw materials, can be first to form tetravalence vanadic salts through pre-treatment such as oxidation or reduction water-soluble again, or first trivalent or pentavalent vanadic salts and/or its hydrate are made to tetravalence vanadium solution through oxidation or reduction after water-soluble again.That is to say, precursor liquid processing can be trivalent vanadium and oxygenant with doping the mixing of reagent, also can be the solution of tetravalence vanadium and mixing or tetravalence vanadium and the suspension liquid of alkali reaction and mixing of doping reagent of doping reagent, can also be pentavalent vanadium and reductive agent (for example oxalic acid, methyl alcohol, glucose, formaldehyde, one or several reductive agents wherein such as formic acid) the mixing of mixed solution and doping reagent.The source (vanadium source) of the tetravalence vanadium in precursor liquid can be the compound of trivalent vanadium, can be the compound of tetravalence vanadium, can be also the compound of pentavalent vanadium.Wherein, the compound of trivalent vanadium comprises Vanadosulfuric acid (V
2(SO
4)
3) or the compound of other trivalent vanadiums.The compound of tetravalence vanadium comprises one or several the mixing in vanadylic sulfate, dichloro vanadyl, oxalic acid vanadyl, hydrogen-oxygen vanadyl.The compound of pentavalent vanadium can be the pentavalent compound of the vanadium such as Vanadium Pentoxide in FLAKES, ammonium meta-vanadate.
Described doping reagent comprises compound or the simple substance of magnesium, can be also compound or the simple substance of aluminium.The compound of magnesium comprises one or several in magnesium oxide, magnesium chloride, magnesium hydroxide, magnesium nitrate, magnesium sulfate, magnesium fluoride, magnesium nitride.The compound of aluminium comprises one or several in aluminum oxide, aluminum chloride, aluminium hydroxide, aluminum nitrate, Tai-Ace S 150.
Again, can before interpolation doping reagent or after doping reagent, add alkaline reagents to process precursor liquid, adopt alkaline reagents titration precursor liquid until generate suspension liquid, the pH of the terminal of titration be 2～12, is preferably 5～10.The method is operation and control easily, and without specific installation.
The alkaline reagents that the present invention adopts can be ammoniacal liquor, aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, sodium bicarbonate aqueous solution, wet chemical, potassium bicarbonate aqueous solution etc. or its arbitrary combination; Be preferably ammoniacal liquor, aqueous sodium hydroxide solution, potassium hydroxide aqueous solution.The concentration of alkaline reagents used can be 0.1～5mol/L, is preferably 0.1～2mol/L.
Before hydro-thermal reaction, with the presoma of alkali pretreated water thermal response, the temperature of reaction of hydro-thermal reaction is subsequently low, reaction can a step complete, and yield is high.And the size of the doped vanadium dioxide particle obtaining and pattern can be controlled in specialized range.
The present invention also provides a kind of vanadium dioxide dispersion liquid that comprises above-mentioned hypovanadic oxide powder.Wherein, the solid content of the powder of dispersion liquid is adjustable, and the amount of for example hypovanadic oxide powder can be 0.0001～500g/L, is preferably 0.1g/L.
The present invention also provides a kind of vanadium dioxide film, and it is coated on suitable matrix by above-mentioned vanadium dioxide dispersion liquid and makes.Described vanadium dioxide film transmitance is adjustable, and transformation temperature is adjustable, and ABSORPTION EDGE hypsochromic shift is moving.For example, the visible ray sun power integration transmitance of described vanadium dioxide film is 20%～85%.The Mott transformation temperature of described vanadium dioxide film is adjustable in the scope of 10 DEG C～68 DEG C.Moving 10nm～the 100nm of ABSORPTION EDGE hypsochromic shift of described vanadium dioxide film.
Vanadium dioxide film provided by the invention can be applicable in preparation energy-saving and emission-reduction equipment or energy information equipment, for example, for example, for thermochromism film, energy-saving coatings, energy saving paint, intelligent power saving glass curtain wall, temperature control unit (sun power temperature control unit) and energy-saving coating.For example, be applicable to directly manufacture energy-saving glass, also can be for existing simple glass be transformed, can also be applied to the reducing energy consumption on the surface such as existing building, car and boat.Hypovanadic oxide powder of the present invention also can be applicable to energy information equipment, comprises micro photo electric switch device, thermistor, battery material and optical information storage part etc.
The energy-conservation film that adopts doped vanadium dioxide powder of the present invention to prepare, technique is simple, cost is low, be widely used, and have can be comparable or more excellent with his method (as sputtering method and dectroless plating) spectral response curve.
Brief description of the drawings
Fig. 1 is the XRD figure spectrum of the magnesium doped vanadium dioxide powder that makes of the non-impurity-doped hypovanadic oxide powder that makes of embodiment 1 and embodiment 2;
Fig. 2 is the transmission electron microscope pattern of the magnesium doped vanadium dioxide powder that makes of embodiment 2;
Fig. 3 is the transmission electron microscope pattern of the magnesium doped vanadium dioxide powder that makes of embodiment 3;
Fig. 4 is the transmission electron microscope pattern of the magnesium doped vanadium dioxide powder that makes of embodiment 4;
Fig. 5 is the transmission electron microscope pattern of the magnesium doped vanadium dioxide powder that makes of embodiment 5;
Fig. 6 is the transmission electron microscope pattern of the aluminium doped vanadium dioxide powder that makes of embodiment 6;
Fig. 7 is the DSC curve of the magnesium doped vanadium dioxide powder that makes of the non-impurity-doped hypovanadic oxide powder that makes of embodiment 1 and embodiment 2;
Fig. 8 is the transmittance curve of the film of being prepared by magnesium doped vanadium dioxide powder that makes of embodiment 10.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that following embodiment and/or accompanying drawing are only for the present invention is described, and unrestricted the present invention.
The invention provides the hydro-thermal technology of preparing of magnesium or aluminium doped vanadium dioxide powder, specifically the present invention has provided the method for the vanadium dioxide nano powder of preparing magnesium or aluminium doping in solution, this powder has high visible light transmissivity and the good infrared performance of control of high low temperature, can reduce Rutile Type vanadium oxide transformation temperature simultaneously, and prepare the dispersion liquid of doped vanadium dioxide powder, can be applicable to smart window, flexible lamina, the fields such as optoelectronic switch, thermistor and optical information storage and thermal insulating coating.
First, provide a kind of doped vanadium dioxide powder, the chemical constitution of this doped vanadium dioxide powder is V
1-xm
xo
2in formula, 0<x≤0.5, preferably 0.005≤x≤0.3, more preferably, 0.03≤x≤0.1, in addition, 0.005≤x≤0.025 is also preferred, and M is doped element, and doped element can be controlled described doped vanadium dioxide powder size and pattern, and finally show good optical property and reduce transformation temperature.
The powder that this doping is used can be magnesium (Mg), and aluminium (Al) and near ion thereof adulterate, preferably magnesium doping.To 1 μ m not etc., stable crystal form, is rutile phase hypovanadic oxide powder to the granular size 5nm of prepared adulterated powder.The pattern of powder can be bar-shaped, particulate state etc.
The present invention can use the salt of tetravalent vanadium ion as vanadium source, for example vanadylic sulfate (VOSO
4), dichloro vanadyl (VOCl
2) and oxalic acid vanadyl pentahydrate (VOC
2o
45H
2the quaternary salts of vanadium such as O).
Vanadium used in the present invention source can also be pentavalent vanadium as vanadium pentoxide, ammonium meta-vanadate etc., its reductive agent can be oxalic acid, methyl alcohol, glucose, formaldehyde, one or several reductive agents wherein such as formic acid.
Vanadium used in the present invention source can also be trivalent vanadium, for example Vanadosulfuric acid (V
2(SO
4)
3).It can obtain tetravalence vanadium through oxidizer treatment.
Reaction taking pentavalent salt and reductive agent as precursor, can directly add doping reagent; Or be precursor taking quaternary salts as precursor through the suspension liquid of basic solution titration, add doping reagent; Or the suspension liquid or the throw out that use quaternary salts and doping reagent jointly to be obtained by alkalimetric titration are that precursor reacts.
The alkaline reagents of using as titration can adopt ammoniacal liquor, aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, sodium bicarbonate aqueous solution, wet chemical, potassium bicarbonate aqueous solution etc. or its arbitrary combination; Be preferably ammoniacal liquor, aqueous sodium hydroxide solution, potassium hydroxide aqueous solution.It is favourable preferably adopting the alkaline reagents of 0.1～2mol/L.When titration completes, the pH value of suspension liquid is generally 2～12, and the amount of alkaline reagents used is the amount that can form suspension liquid.Titration, is easily observed and controls as titration end point there is suspension liquid, without extras.
The element adulterating in vanadium dioxide can be magnesium, also can be aluminium etc. for regulating and controlling the metal of vanadium dioxide transformation temperature and optical property, can be also near element magnalium in the periodic table of elements but should understand.Particularly, can adopt compound or the simple substance of magnesium, also can adopt compound or the simple substance of aluminium.The compound of magnesium comprises one or several in magnesium oxide, magnesium chloride, magnesium hydroxide, magnesium nitrate, magnesium sulfate, magnesium fluoride, magnesium nitride.The compound of aluminium comprises one or several in aluminum oxide, aluminum chloride, aluminium hydroxide, aluminum nitrate, Tai-Ace S 150.Adopt these doped elements, can controlled doping hypovanadic oxide powder size and pattern, regulate and control the transformation temperature of vanadium dioxide simultaneously and change the optical property of vanadium dioxide.Doped element in doping reagent and the mol ratio of the tetravalent vanadium ion aqueous solution can be determined according to the doping of doped element, for example can select in the present invention 1:1000～1:1.
Hydrothermal temperature can be 160～400 DEG C, is preferably 200～350, more preferably 250～300 DEG C.In these temperature ranges, the more high generation that is more conducive to rutile phase hypovanadic oxide of temperature.The hydro-thermal reaction time can be 0.1～96 hour, can adjust along with temperature of reaction, is preferably 4～60 hours.It will be appreciated by those skilled in the art that and can select suitable reactor according to charging capacity, hydro-thermal reaction packing ratio can be 50～90% conventionally.
Hydro-thermal reaction product separation and dry can adopt centrifugal drying, also can adopt lyophilize etc. other can be dried the method for powder but should understand.
The doped vanadium dioxide powder that the present invention makes has single chemical constitution, determines that by X-ray diffraction (XRD) its crystal formation is single vanadium dioxide M phase structure.Prepare shape and the particle diameter of gained doped vanadium dioxide powder by transmission electron microscope (TEM) observation present embodiment, doped vanadium dioxide powder prepared by present embodiment is particulate state or corynebacterium (referring to Fig. 2～6), size mainly concentrates between the μ m of 5nm～1, especially between 10nm～200.
The present invention also provides the dispersion liquid that comprises a kind of above-mentioned doped vanadium dioxide powder, and its dispersion liquid can be water-based, can be also oiliness, and the solid content of its powder is 0.1% to 50%(0.0001～500g/L).Doped vanadium dioxide powder grinding distribution, in water, is added to dispersion agent in stirring, for example polyvinylpyrrolidone, stirring, ultrasonic 30min～2h, can make vanadium dioxide dispersion liquid.Doped vanadium dioxide powder of the present invention has all shown extraordinary dispersiveness in water He in dispersion agent.To make dispersion liquid and be coated on matrix, for example glass substrate, make vanadium dioxide film after dry.The visible light transmissivity of the doped vanadium dioxide film that the present invention makes is high, and its visible ray sun power integration transmitance is 20%～85%.For example, referring to Fig. 8, its illustrate one not doped vanadium dioxide film and magnesium-doped vanadium dioxide film example respectively at 25 DEG C with 90 DEG C at the transmitance measured, L wherein represents relation curve between film transmitance and the wavelength of 25 DEG C of tests of low temperature (curve a and d), H represents relation curve between optical transmittance and the wavelength of 90 DEG C of tests of high temperature (curve b and c), as can be seen from the figure no matter be under high temperature or low temperature, relatively unadulterated vanadium dioxide film, the visible light transmissivity of magnesium-doped vanadium dioxide film is improved.Should be understood that and dispersion liquid can also be coated on to other suitable matrixes to prepare film, suitable matrix comprises plastic base, silicon substrate and metal substrate.Can be applied to like this thermochromism film, energy-saving coatings, energy saving paint, intelligent power saving glass curtain wall, temperature control unit (for example sun power temperature control unit) and energy-saving coating.For example, be applicable to directly manufacture energy-saving glass, also can be for existing simple glass be transformed, can also be applied to the reducing energy consumption on the surface such as existing building, car and boat.Hypovanadic oxide powder of the present invention also can be applicable to energy information equipment, comprises micro photo electric switch device, thermistor, battery material and optical information storage part etc.
Compared with the hypovanadic oxide powder of the present invention and existing other element dopings, there is following advantage:
1. visible light transmissivity exceedes 50%, and sunlight ability of regulation and control is greater than 10% simultaneously;
2. ABSORPTION EDGE generation blue shift, blue shift 15～40nm, the color of film shoals;
Transformation temperature reduce with the increase of doping and transformation temperature reduce adjustable.
Should understand; the above-mentioned embodiment that the present invention describes in detail; and following examples are only not used in and limit the scope of the invention for the present invention is described, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjust and 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 temperature of reaction that following example is concrete, time, charging capacity etc. are only also examples in OK range,, and do not really want to be defined in the below concrete numerical value of example.The raw material, the reagent that adopt can be synthesized and be made by purchase marketable material or traditional chemical transform mode.The experimental technique of unreceipted actual conditions in the following example, conventionally according to normal condition, for example, is the condition in " the smooth organic chemistry handbook of Bel Si " (Chemical Industry Press, 1996), or the condition of advising according to manufacturer.Ratio and per-cent are based on molar mass, unless stated otherwise.Unless otherwise defined or described herein, the familiar same meaning of all specialties used herein and scientific words and those skilled in the art.In addition any method and material similar to described content or that be equal to all can be applicable in the inventive method.Other aspects of the present invention, due to disclosure herein, are that appearance is intelligible to those skilled in the art.
Embodiment 1
First preparation is containing the Vanadium Pentoxide in FLAKES solution 80ml of 0.001mol/L, adds 0.001g oxalic acid and stirs into the solution of homogeneous.Solution is put into reactor and add above-mentioned solution sealing.In the cooling rear taking-up of 240 DEG C of reaction 24h, centrifugal drying obtains hypovanadic oxide powder, and its chemical formula is VO
2.As shown in Fig. 1 XRD spectra, its crystalline phase is M phase.The hypovanadic oxide powder that this embodiment makes is of a size of 50nm, and transformation temperature is 68 DEG C.
Embodiment 2
First preparation is containing the Vanadium Pentoxide in FLAKES solution 80ml of 0.001mol/L, adds 0.005g oxalic acid and stirs into the solution of homogeneous.To the MgNO that adds 2.67mg in solution
36H
2o, stirs, and above-mentioned solution is put into reactor and add above-mentioned solution sealing.In the cooling rear taking-up of 240 DEG C of reaction 24h, centrifugal drying obtains hypovanadic oxide powder, and its chemical formula is V
1.94mg
0.06o
2.As shown in Fig. 1 XRD spectra, its crystalline phase is M phase, and as shown in Fig. 2 TEM photo, the hypovanadic oxide powder making is also corynebacterium, is of a size of 10-300nm.The transformation temperature of the hypovanadic oxide powder that this embodiment makes is 55 DEG C.
Embodiment 3:
First preparation, containing the vanadylic sulfate solution 80ml of 0.001mol/L, is used potassium hydroxide to be titrated to and occurs suspension liquid.To the MgNO that adds 5.33mg in solution
36H
2o, stirs, and above-mentioned solution is put into reactor and add above-mentioned solution sealing.In 240 DEG C of reaction 16h, cooling rear taking-up; Centrifugal drying obtains hypovanadic oxide powder, and its chemical formula is V
1.9mg
0.1o
2.As shown in Fig. 3 TEM photo, the hypovanadic oxide powder making is also corynebacterium, is of a size of 10-200nm.The crystalline phase of the hypovanadic oxide powder that this embodiment makes is M phase, and transformation temperature is 50 DEG C.
Embodiment, 4
First preparation, containing the vanadylic sulfate solution 80ml of 0.002mol/L, is used potassium hydroxide to be titrated to and occurs suspension liquid.To the MgNO that adds 20mg in solution
36H
2o, stirs, and above-mentioned solution is put into reactor and add above-mentioned solution sealing.In 240 DEG C of reaction 20h, cooling rear taking-up, centrifugal drying obtains hypovanadic oxide powder, and its chemical formula is V
1.87mg
0.13o
2.As shown in Fig. 4 TEM photo, the hypovanadic oxide powder making is particulate state, is of a size of 30-200nm.The crystalline phase of the hypovanadic oxide powder that this embodiment makes is M phase, and transformation temperature is 49 DEG C.
Embodiment 5
First preparation is containing the vanadylic sulfate solution 80ml of 0.002mol/L, to the MgNO that adds 20mg in solution
36H2O, the use potassium hydroxide that stirs is titrated to and occurs suspension liquid, above-mentioned solution is put into reactor and add above-mentioned solution sealing.In 240 DEG C of reaction 20h, cooling rear taking-up, centrifugal drying obtains doped vanadium dioxide powder.As shown in Fig. 5 TEM photo, the hypovanadic oxide powder making is particulate state, is of a size of 100nm.The crystalline phase of the hypovanadic oxide powder that this embodiment makes is M phase, and transformation temperature is 55 DEG C.
Embodiment 6
First preparation, containing the dichloro vanadyl solution 80ml of 0.002mol/L, is used potassium hydroxide to be titrated to and occurs suspension liquid.To the Al that adds 20mg in solution
2o
3, stir, above-mentioned solution is put into reactor and add above-mentioned solution sealing.In 240 DEG C of reaction 20h, cooling rear taking-up, centrifugal drying obtains doped vanadium dioxide powder V
1.87al
0.13o
2.As shown in Figure 6, be of a size of 80nm.The crystalline phase of the hypovanadic oxide powder that this embodiment makes is M phase, and transformation temperature is 60 DEG C.
Embodiment 7
First preparation, containing the dichloro vanadyl solution 80ml of 0.002mol/L, is used potassium hydroxide to be titrated to and occurs suspension liquid.To the Al that adds 2mg in solution
2o
3, stir, above-mentioned solution is put into reactor and add above-mentioned solution sealing.In 240 DEG C of reaction 24h, cooling rear taking-up, centrifugal drying obtains doped vanadium dioxide powder V
1.99al
0.01o
2, be of a size of 100nm.The crystalline phase of the hypovanadic oxide powder that this embodiment makes is M phase, and transformation temperature is 60 DEG C.
Embodiment 8
First preparation, containing the dichloro vanadyl solution 80ml of 0.002mol/L, is used potassium hydroxide to be titrated to and occurs suspension liquid.To the Al that adds 0.5mg in solution
2o
3, stir, above-mentioned solution is put into reactor and add above-mentioned solution sealing.In 250 DEG C of reaction 20h, cooling rear taking-up, centrifugal drying obtains doped vanadium dioxide powder V
1.97al
0.03o
2, be of a size of 90nm.The crystalline phase of the hypovanadic oxide powder that this embodiment makes is M phase, and transformation temperature is 64 DEG C.
Embodiment 9
After hypovanadic oxide powder prepared 0.1g embodiment 2 is ground, put into the small beaker containing 100ml water, and constantly stir, add 0.05g PVP K-30, ultrasonic 60min after stirring 30min, makes dispersion liquid.
Embodiment 10
Gained dispersion liquid is coated on substrate and (as PET flexible membrane, is not limited to flexible membrane, glass etc.), then after dry in room temperature or baking oven, can make vanadium dioxide film.
The above-mentioned film making is measured respectively to its transmitance in 25 DEG C with 90 DEG C, and scope is at 250nm within the scope of 2600nm, and its test result is shown in accompanying drawing 8.L wherein represents the relation curve between film transmitance and the wavelength of 25 DEG C of tests of low temperature, and H represents the relation curve between optical transmittance and the wavelength of 90 DEG C of tests of high temperature.
Industrial applicability: hypovanadic oxide powder of the present invention, dispersion liquid can be widely used in energy-saving and emission-reduction equipment, for example energy-conservation film, energy-saving coatings, sun power temperature control unit; Or energy information equipment, for example, micro photo electric switch device, thermistor, battery material and optical information storage part.The method of preparing hypovanadic oxide powder of the present invention, technique is simple, cost is low, yield is high, is applicable to scale production.
Claims (12)
1. a doped vanadium dioxide powder, is characterized in that, the chemical constitution of described doped vanadium dioxide powder is V
1-xm
xo
2, 0<x≤0.5, wherein M is doped element, described doped element M is Mg or Al, and described doped element M is for improving the optical property of described doped vanadium dioxide powder and the transformation temperature of the described doped vanadium dioxide powder of adjusting.
2. doped vanadium dioxide powder according to claim 1, is characterized in that, 0<x≤0.5.
3. doped vanadium dioxide powder according to claim 2, is characterized in that, 0.005≤x≤0.3.
4. according to the doped vanadium dioxide powder described in any one in claims 1 to 3, it is characterized in that, described doped vanadium dioxide powder is bar-shaped or particulate state.
5. according to the doped vanadium dioxide powder described in any one in claim 1 to 4, it is characterized in that, described doped vanadium dioxide powder is of a size of between the μ m of 5nm～1 adjustable.
6. according to the doped vanadium dioxide powder described in any one in claim 1 to 5, it is characterized in that, the crystalline phase of described doped vanadium dioxide powder is Rutile Type.
7. the preparation method of the doped vanadium dioxide powder described in any one in a claim 1 to 6, it is characterized in that, comprise: according to stoichiometric ratio, doping reagent is added in the precursor liquid containing tetravalence vanadium, stirs, hydro-thermal reaction 0.01～96 hour at 160～400 DEG C.
8. preparation method according to claim 7, is characterized in that, the temperature of described hydro-thermal reaction is 200～250 DEG C, and the described hydro-thermal reaction time is 16～48 hours.
9. a vanadium dioxide film, is characterized in that, described vanadium dioxide film is coated on matrix by the dispersion liquid that contains the hypovanadic oxide powder described in any one in claim 1～6 and makes.
10. vanadium dioxide film according to claim 9, is characterized in that, the visible ray sun power integration transmitance of described vanadium dioxide film is 20%～85%.
11. according to the vanadium dioxide film described in claim 9 or 10, it is characterized in that, the Mott transformation temperature of described vanadium dioxide film is adjustable in the scope of 10 DEG C～68 DEG C.
12. according to the vanadium dioxide film described in any one in claim 9～11, it is characterized in that the moving 10nm～100nm of ABSORPTION EDGE hypsochromic shift of described vanadium dioxide film.
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| CN105753050A (en) * | 2014-12-18 | 2016-07-13 | 刘闽苏 | A preparing method of rutile vanadium dioxide nanometer particles and the particles |
| CN108585849A (en) * | 2018-05-16 | 2018-09-28 | 中国科学院新疆理化技术研究所 | A kind of preparation method of critical NTC thermistor |
| CN110156340A (en) * | 2019-05-24 | 2019-08-23 | 武汉大学 | A kind of temperature sensitive type VO2The preparation method of photocuring flexible membrane |
| CN111613400A (en) * | 2020-05-11 | 2020-09-01 | 上海交通大学 | Normal-temperature NTC thermistor film and preparation method thereof |
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