CN104030355B - doped vanadium dioxide powder and film and preparation method thereof - Google Patents
doped vanadium dioxide powder and film and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of doped vanadium dioxide powder and film and preparation method thereof, the chemical constitution of described doped vanadium dioxide powder is VO
1-xm
x, 0 & lt; X≤0.5, wherein M is doped element, and described doped element is fluorine, sulphur, chlorine, bromine or iodine, and described doped element M is for improving the pattern of described doped vanadium dioxide powder, transformation temperature, electric property and optical property.
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 film, and its preparation method and application.
Background technology
Current world energy sources demand increases with annual 2%, and in these energy about 30% consume architectural.For China, building energy consumption has accounted for 27.6% of social total energy consumption, and the energy consumption brought thus and environmental pollution constantly aggravate.Glass carries out heat energy, the permutable principal passage of light as building with the external world, accounts for 48% and 71% of total energy exchange respectively, therefore develop energy-saving glass, be expected to significantly reduce building energy consumption by the heat exchange of glass port in winter and summer.
So far, the energy-saving glass such as Low-E, gas-discoloration and electrochromism are mainly contained.But these energy-saving glass exist many disadvantages, use as Low-E glass is only suitable for summer, gas-discoloration glass structure relative complex, electrochomeric glass needs to consume extra energy.Intelligent power saving glass based on vanadium dioxide has that structure is simple, temperature response and scope can be in harmonious proportion light and reconcile efficiency advantages of higher, has become Intelligent energy-saving window study hotspot of future generation.
There is reversible phase in version in vanadium dioxide, temperature-rise period is the metallographic phase of tetragonal from monocline semiconductor phase-change near 68 DEG C.Along with structural changes, the character generation acute variation such as its optics, electricity and magnetics.For optical property, during low temperature, vanadium dioxide has high transmitance in infrared region; During high temperature, vanadium dioxide has high absorption and reflection in infrared region, and its transmitance is declined greatly.Meanwhile, in phase transition process, visible light transmissivity changes hardly, makes vanadium dioxide become the critical material of intelligent power saving glass.
Vanadium dioxide film adopts the method preparations such as sputtering method, chemical Vapor deposition process, ion implantation, sol-gel method usually, but these methods exist, and cost is high, control process is complicated, be not suitable for the deficiencies such as scale operation.In addition, coated glass cannot carry out reducing energy consumption to existing building glass.Intelligent power saving effect hypovanadic oxide powder will be had and be prepared into film, and both may be used for, on existing building glass, also may be used on new production glass.
Existing M/R phase hypovanadic oxide powder adopts the methods such as spray-wall interaction (US Patent No. 5427763), pyrolysis method (China is CN1321067C specially), sol-gel method (US Patent No. 6682596) and hydrothermal method (Chinese patent CN101391814A).
All there is the problems such as transformation temperature is high, visible light transmissivity is low, color is ugly in pure vanadium dioxide film, improves these deficiencies significant to vanadium dioxide intelligent window.Above-mentioned characteristic is regulated and controled by doping means usually.On vanadium dioxide doping film, Chinese patent CN102249552A discloses a kind of wet chemical for doped vanadium dioxide film, chooses the elements such as tungsten, molybdenum, titanium, aluminium, magnesium and adulterates.On hypovanadic oxide doped powder, Chinese patent CN101792182A discloses a kind of preparation method of tungsten-doped vanadium dioxide powder.Chinese patent CN102120615A before the applicant discloses a kind of doped vanadium dioxide powder preparation method, and choosing 21 ~ 30 transition element is doped element.On hypovanadic oxide doped powder, major part work all concentrates on research doping and reduces phase transition temperature of vanadium dioxide, not paying close attention to doping to affect its electric property, seldom paying close attention to optical property and the color of improving powder institute made membrane by adulterating to powder simultaneously.At present, hypovanadic oxide powder doping mainly concentrates in positive ion doping research, and negative ion doping research does not have substantially.
Summary of the invention
For the problems referred to above, the present inventor is by research finds in vanadium dioxide doped with fluorine, sulphur, chlorine, bromine, iodine negative ion can improve hypovanadic oxide powder pattern, transformation temperature, electric property and optical property.Therefore, the object of this invention is to provide a kind of doped vanadium dioxide powder, and then utilize adulterated powder to prepare vanadium dioxide film, not only reduce the transformation temperature of vanadium dioxide, also improve vanadium dioxide film color, improve its sunshade ability (high temperature sunlight integration transmitance), maintain film visible light transmissivity and sun power performance of control.
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 VO
2-xm
x, 0<x≤0.5, wherein M is doped element, and described doped element is fluorine, sulphur, chlorine, bromine or iodine, and described doped element M is for improving the pattern of described doped vanadium dioxide powder, transformation temperature, electric property and optical property.Wherein preferred 0.001<x≤0.5, more preferably 0.001<x≤0.1, most preferably 0.001<x≤0.05.
Adopt the present invention, by the doped element (fluorine of doping regulation, sulphur, chlorine, bromine or iodine), hypovanadic oxide powder size and pattern can be controlled, the hypovanadic oxide powder size that can control to make to prepare is little and homogeneous, and the transformation temperature of hypovanadic oxide powder can be improved, electric property and optical property, described doped vanadium dioxide powder has high visible light transmissivity and the infrared performance of control of good high/low temperature, and this doped vanadium dioxide powder stable crystal form, it is at water, good dispersity in dispersion agent (such as polyvinylpyrrolidone), be easy to be coated on metal or the substrate such as nonmetal, be suitable for preparing vanadium dioxide film and coating, energy-saving coatings can be applied to, energy saving paint, the fields such as temperature control unit (such as sun power temperature control unit) and energy-saving coating.
In the present invention, described doped vanadium dioxide powder is preferably particulate state, bar-shaped or flower-shaped.The length-to-diameter ratio of powder is preferably 1:1 ~ 100:1.Described doped vanadium dioxide powder is of a size of 10nm ~ 800nm, 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.Describedly bar-shapedly be preferably corynebacterium, described particulate state can be such as subsphaeroidal, oval, snowflake shape, cube, sheet shape etc.
Described doped vanadium dioxide powder is pressed into disk through 30Mpa pressure in 10mm cylindrical die, and the carrier concentration of powder disk is 10
15~ 10
21cm
-3between continuously adjustabe.
In the present invention, doped vanadium dioxide powder is rutile phase hypovanadic oxide.Again, described doped vanadium dioxide powder not only has controlled size and pattern, also has SEMICONDUCTOR-METAL phase in version character, transformation temperature continuously adjustabe between-30 ~ 90 DEG C of doped vanadium dioxide powder of the present invention.
The present invention also provides a kind of method preparing above-mentioned doped vanadium dioxide powder, described method comprises in the precursor liquid be added to the reagent that adulterates containing tetravalence vanadium according to the stoichiometric ratio molar ratio of the such as dopant ion and vanadium ion (can between 1:1000 to 1:1), stir, adopt precursor liquid described in alkaline reagents titration until generate suspension liquid, hydro-thermal reaction 1 ~ 240 hour at 150 ~ 400 DEG C.
In the present invention, the mol ratio of described dopant ion and vanadium ion is preferably 3:97 ~ 3:7, is more preferably 3:97 ~ 1:9.
Again, described hydrothermal temperature, is preferably 200 ~ 350 DEG C, is more preferably 250 ~ 300 DEG C.The described hydro-thermal reaction time is preferably 2 ~ 120 hours, is more preferably 4 ~ 40 hours.
The concentration of the described precursor liquid containing tetravalence vanadium can be 0.005 ~ 5mol/L, is preferably 0.01 ~ 0.5mol/L.Again, first can prepare the dopant ion aqueous solution by water-soluble for described doping reagent, its concentration can be 0.005 ~ 2mol/L, is preferably 0.01 ~ 0.5mol/L.
Precursor liquid containing tetravalence vanadium can by obtaining water-soluble for soluble vanadium raw material.Conventional soluble vanadium raw material can be trivalent, tetravalence or pentavalent vanadium and/or its hydrate.Should understand, when adopting trivalent or pentavalent vanadic salts and/or its hydrate as vanadium raw materials, first can form tetravalence vanadic salts through oxidation or the pre-treatment such as reduction water-soluble again, or first by trivalent or pentavalent vanadic salts and/or its hydrate water-soluble after again through oxidation or the obtained tetravalence vanadium solution of reduction.That is, precursor liquid process can be trivalent vanadium and oxygenant with the mixing of doping reagent, also it can be mixing or the suspension liquid of tetravalence vanadium and alkali reaction and mixing of the reagent that adulterates of solution and the doping reagent of tetravalence vanadium, can also be pentavalent vanadium and reductive agent (such as 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, also can be 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, vanadyl oxalate, 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 is one or more in hydrofluoric acid, Potassium monofluoride, Sodium Fluoride, Neutral ammonium fluoride, sodium bifluoride, potassium hydrogen fluoride, ammonium bifluoride, sodium-chlor, Repone K, ammonium chloride, hydrogenchloride, bariumchloride, calcium chloride, ammonium sulfide, sodium sulphite, potassium sulphide, Potassium Bromide, Sodium Bromide, brometo de amonio, sodium iodide, potassiumiodide, calcium iodide, ammonium iodide.In addition, the described dopant ion aqueous solution also can utilize iodine, sulphur, bromine and fluorochemical, sulfide, muriate, bromide, iodide to be prepared.
In the present invention, adopt alkaline reagents titration precursor liquid until generate suspension liquid.The pH of the terminal of titration is 2 ~ 12, is preferably 5 ~ 10, is more preferably 6 ~ 8.The method easily operates and controls, and without the need to specific installation.
Alkaline reagents of the present invention 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 0.5 ~ 5mol/L, is preferably 0.5 ~ 2mol/L.
The mol ratio of wherein said tetravalent vanadium ion and described dopant ion and alkaline reagents is 50:1 ~ 1:10, is preferably 10:1 ~ 1:5, is more preferably 5:1 ~ 1:2.
Before hydro-thermal reaction, with the presoma of oxygenation pretreatment hydro-thermal reaction, 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 obtained and pattern can control in specialized range.
In the present invention, the packing ratio of described hydro-thermal reaction can be 20 ~ 90%, preferably 30 ~ 80%, more preferably 50 ~ 80%.
The present invention also provides a kind of vanadium dioxide film, and it is obtained by the dispersion drying on substrate comprising described doped vanadium dioxide powder and properties-correcting agent.
Described vanadium dioxide film thickness can be 5nm ~ 1mm.Visible ray integration transmitance is 20 ~ 80%, and sun power regulation and control rate is 0% ~ 20%.High temperature sunlight integration transmitance (sunshade ability) is 10% ~ 60%, and film colourimetric number is less, and such as a* is between-20 ~ 20, and b* is between-20 ~ 40.
The present invention utilizes Liquid preparation methods doped vanadium dioxide powder, and use common vanadic salts and doping agent as raw material, cost is low, simple to operate.
Doped vanadium dioxide powder of the present invention can be applied to energy-saving coatings, energy saving paint, temperature control unit (such as sun power temperature control unit) and energy-saving coating.The reducing energy consumption on the surface such as existing building, car and boat can also be applied to.Doped vanadium dioxide 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.
Doped vanadium dioxide powder is prepared doped vanadium dioxide film by the present invention, not only reduces the transformation temperature of vanadium dioxide, also improves vanadium dioxide film color, improves its sunshade ability, maintains film visible light transmissivity and sun power performance of control.
Accompanying drawing explanation
The X-ray diffractogram of the hypovanadic oxide powder of Fig. 1 obtained by embodiment 1;
The transmission electron microscope figure of the hypovanadic oxide powder of Fig. 2 obtained by embodiment 1;
The intensification differential calorimetry curve of the hypovanadic oxide powder of Fig. 3 obtained by embodiment 1;
The X-ray diffractogram of the hypovanadic oxide powder of Fig. 4 obtained by embodiment 2;
The intensification differential calorimetry curve of the hypovanadic oxide powder of Fig. 5 obtained by embodiment 4
The curve of spectrum before and after the made thin film phase change of hypovanadic oxide powder of Fig. 6 obtained by embodiment 10;
The hypovanadic oxide powder institute made membrane chromaticity diagram of Fig. 7 obtained by embodiment 10, its mid point 1 represents pure vanadium dioxide film colourimetric number, and point 2 represents Fluorin doped vanadium dioxide film colourimetric number.
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 illustration of the present invention, and unrestricted the present invention.
The invention provides negative ion (such as fluorine, sulphur, chlorine, bromine or iodine) doped vanadium dioxide powder and hydro-thermal technology of preparing thereof, specifically The present invention gives fluorine, sulphur, chlorine, the vanadium dioxide nano powder of bromine or iodine doping and prepare the method for described powder in the solution, this powder has high visible light transmissivity and the infrared performance of control of good high/low temperature, Rutile Type vanadium oxide transformation temperature can be reduced simultaneously, and prepare doped vanadium dioxide powder film, can be applicable to energy-saving coatings, energy saving paint, the fields such as temperature control unit (such as sun power temperature control unit) and energy-saving coating.
First, provide a kind of doped vanadium dioxide powder, the chemical constitution of described doped vanadium dioxide powder is VO
2-xm
x0<x≤0.5, in formula, 0<x≤0.5, preferred 0.001<x≤0.5, more preferably 0.001<x≤0.1, most preferably 0.001<x≤0.05, wherein M is doped element, and doped element M is for improving the pattern of described doped vanadium dioxide powder, transformation temperature, electric property and optical property.
This doping can be fluorine, sulphur, chlorine, bromine or iodine doping.Prepared adulterated powder is of a size of 10nm ~ 800nm, is rutile phase hypovanadic oxide powder.The pattern of powder can be particulate state, bar-shaped or flower-shaped etc.
The present invention can use the salt of tetravalent vanadium ion as vanadium source, such as vanadylic sulfate (VOSO
4), dichloro vanadyl (VOCl
2) and vanadyl oxalate pentahydrate (VOC
2o
45H
2the quaternary salts of vanadium such as O).
Vanadium source used in the present invention can also be pentavalent vanadium as vanadium pentoxide, ammonium meta-vanadates etc., its reductive agent can be oxalic acid, methyl alcohol, glucose, formaldehyde, one or several reductive agents wherein such as formic acid.
Vanadium source used in the present invention can also be trivalent vanadium, such as Vanadosulfuric acid (V
2(SO
4)
3).It can obtain tetravalence vanadium through oxidizer treatment.
The present invention adopts alkaline reagents process tetravalent vanadium ion and the dopant ion aqueous solution to obtain the presoma treatment process of suspension liquid.Presoma treatment process can adopt alkaline reagents titration tetravalent vanadium ion and the dopant ion aqueous solution until generate suspension liquid.The above-mentioned suspension liquid obtained through alkaline purification subsequently, can obtain required doped vanadium dioxide powder through hydro-thermal reaction.
Alkaline reagents 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, more preferably aqueous sodium hydroxide solution.The alkaline reagents of preferred employing 0.5 ~ 5mol/L is favourable.When titration completes, the pH value of suspension liquid is generally 2 ~ 12, is preferably 5 ~ 10, is more preferably 6 ~ 8.The amount of alkaline reagents used is the amount that can form suspension liquid.Titration, to occur that suspension liquid is as titration end point, is easily observed and controls, without the need to extras.
The element adulterated in vanadium dioxide can be fluorine, sulphur, chlorine, bromine or iodine.Particularly, the dopant ion aqueous solution of the present invention can by respective compound dissolve be prepared, selected examination be hydrofluoric acid, Potassium monofluoride, Sodium Fluoride, Neutral ammonium fluoride, sodium bifluoride, potassium hydrogen fluoride, ammonium bifluoride, sodium-chlor, Repone K, ammonium chloride, hydrogenchloride, bariumchloride, calcium chloride, ammonium sulfide, sodium sulphite, potassium sulphide, Potassium Bromide, Sodium Bromide, brometo de amonio, sodium iodide, potassiumiodide, calcium iodide, ammonium iodide one or more.In addition, the described dopant ion aqueous solution also can utilize iodine, sulphur, bromine and fluorochemical, sulfide, muriate, bromide, iodide to be prepared.Adopt these doped elements, hypovanadic oxide powder size and pattern can be controlled, can control to make the hypovanadic oxide powder size prepared little and homogeneous, and the transformation temperature of hypovanadic oxide powder, electric property and optical property can be improved.The concentration of dopant ion and vanadium ion and mol ratio can be determined according to the doping of doped element, and the mol ratio of tetravalent vanadium ion and dopant ion and alkaline reagents can be 50:1 ~ 1:10 in the present invention, are preferably 10:1 ~ 1:5, are more preferably 5:1 ~ 1:2.The concentration of the tetravalent vanadium ion aqueous solution can be 0.005 ~ 5mol/L, is preferably 0.01 ~ 0.5mol/L.The concentration of the dopant ion aqueous solution can be 0.005 ~ 2mol/L, is preferably 0.01 ~ 0.5mol/L.Dopant ion and vanadium ion mol ratio can select 1:1000 ~ 1:1, are preferably 3:97 ~ 3:7, are more preferably 3:97 ~ 1:9.
Hydrothermal temperature can be 150 ~ 400 DEG C, is preferably 200 ~ 350 DEG C, is more preferably 250 ~ 300 DEG C.In these temperature ranges, the more high generation being more conducive to rutile phase hypovanadic oxide of temperature.The hydro-thermal reaction time is 1 ~ 240 hour, is preferably 2 ~ 120 hours, is more preferably 4 ~ 40 hours.The packing ratio of hydro-thermal reaction can be 20 ~ 90%, preferably 30 ~ 80%, more preferably 50 ~ 80%
Hydro-thermal reaction product separation and drying can adopt centrifugal drying, but should understand and also can adopt lyophilize etc. other can the method for dry powder.
The doped vanadium dioxide powder that the present invention obtains has single chemical constitution, determines that its crystal formation is single vanadium dioxide M phase structure by X-ray diffraction (XRD).Present embodiment is observed to prepare shape and the particle diameter of gained doped vanadium dioxide powder by transmission electron microscope (TEM), doped vanadium dioxide powder prepared by present embodiment is particulate state, bar-shaped or flower-shaped, size mainly concentrates between 10nm ~ 800nm, especially between 10nm ~ 100nm.
The present invention also provides the doped vanadium dioxide obtained by above-mentioned doped vanadium dioxide powder film.Particularly, can adopt and prepare with the following method: the container containing deionized water will be put into after the grinding of described doped vanadium dioxide powder, and constantly stir, and add a certain amount of properties-correcting agent, stir ultrasonic 1 ~ 60min after 1 ~ 120min, obtained dispersion liquid; By gained dispersion in metal substrate or nonmetallic substrate, then in room temperature or baking oven after drying, doped vanadium dioxide film can be obtained.
In an example embodiment, doped vanadium dioxide powder is 0.05 ~ 1g, is preferably 0.1 ~ 0.5g, is more preferably 0.2 ~ 0.3g.Deionized water 1 ~ 50mL, is preferably 1 ~ 10mL, is more preferably 5 ~ 10mL.PVP K-30 is 0.05 ~ 5g, is preferably 0.5 ~ 5g, is more preferably 0.5 ~ 2g.
Described properties-correcting agent comprises high molecular polymer properties-correcting agent, modified with organic acids agent and saccharide-modified dose etc.Described high molecular polymer properties-correcting agent includes but not limited to dispersion agent LBD-1, PEG-4000, PEG-4000, Povidone; Modified with organic acids agent includes but not limited to succsinic acid, cholic acid, Deoxycholic Acid; Saccharide-modified dose includes but not limited to semi-lactosi, sucrose, tetramethylolmethane; In addition properties-correcting agent also comprises urea.
Doped vanadium dioxide film thickness of the present invention is 5nm ~ 1mm, visible ray integration transmitance is 20 ~ 80%, sun power regulation and control rate is 0% ~ 20%, high temperature sunlight integration transmitance (sunshade ability) is 10% ~ 60%, film colourimetric number (, between-20 ~ 20, b* is between-20 ~ 40 for a*) is less.
Feature of the present invention and significantly innovation are:
(1) utilize Liquid preparation methods doped vanadium dioxide powder, use common vanadic salts and doping agent as raw material, cost is low, simple to operate.
(2) adulterated powder is prepared vanadium dioxide film, not only reduce the transformation temperature of vanadium dioxide, also improve vanadium dioxide film color, improve its sunshade ability, maintain film visible light transmissivity and sun power performance of control.
Above-mentioned doped vanadium dioxide powder can be applied to energy-saving coatings, energy saving paint, temperature control unit (such as sun power temperature control unit) and energy-saving coating.The reducing energy consumption on the surface such as existing building, car and boat can also be applied to.Doped vanadium dioxide 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 present invention, compared with the hypovanadic oxide powder of other element dopings existing, has following advantage:
1. visible light transmissivity is more than 50%, and sunlight ability of regulation and control is greater than 10% simultaneously;
2. ABSORPTION EDGE generation blue shift, blue shift 15 ~ 40nm, the lighter of film;
3. 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 for illustration of the present invention and limit 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 of reaction that following example is concrete, time, charging capacity 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.The raw material adopted, reagent can be obtained by purchase marketable material or the synthesis of traditional chemical transform mode.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition are such as the conditions in " the smooth organic chemistry handbook of Bel Si " (Chemical Industry Press, 1996), or according to the condition that manufacturer advises.Ratio and per-cent based on molar mass, unless stated otherwise.Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the same meaning be familiar with.In addition any or method of being equal to similar with described content and material all can be applicable in the inventive method.Other aspects of the present invention, due to disclosure herein, are easy understand to those skilled in the art.
Embodiment 1
The Fluorin doped hypovanadic oxide powder of doping molar percentage 20%
By 10gVOSO
4powder and 3gNH
4f is dissolved in 50ml deionized water, with the NaOH solution titration of 1mol/L, and constantly stir, to be titrated completely after suspension liquid loaded fill in the 50ml water heating kettle of 45ml deionized water, 230 DEG C of hydro-thermal reactions 96 hours, centrifugal drying obtains Fluorin doped hypovanadic oxide powder, is 20% through ultimate analysis fluorine atom mol ratio.As shown in Fig. 1 XRD spectra, its crystalline phase is pure M phase.From Fig. 2 TEM, can find that Fluorin doped vanadium dioxide is particulate state, size is at about 30nm.As Fig. 3 DSC curve shows that Fluorin doped hypovanadic oxide powder has phase transition property, transformation temperature is down to 35 DEG C, shows that Fluorin doped effectively can reduce transformation temperature, and during powder compressing tablet 25 DEG C, carrier concentration is 1.25 × 10
19cm
-3.
Embodiment 2
The chlorine doped vanadium dioxide powder of doping molar percentage 10%
By 10gVOC
2o
45H
2o powder and 2gKCl are dissolved in 50ml deionized water, with the NaOH solution titration of 1mol/L, and constantly stir, to be titrated completely after suspension liquid loaded fill in the 50ml water heating kettle of 45ml deionized water, 300 DEG C of hydro-thermal reactions 12 hours, centrifugal drying obtains chlorine doped vanadium dioxide powder, is 10% through ultimate analysis chlorine atomic molar ratio.The doped vanadium dioxide powder of chlorine shown in Fig. 4 thing is M phase mutually, and powder transformation temperature is 45 DEG C, and particle size is 40nm, and during powder compressing tablet 25 DEG C, carrier concentration is 3.2 × 10
18cm
-3.
Embodiment 3
The bromine doped vanadium dioxide powder of doping molar percentage 12%
By 10gVOCl
2powder and 3gNaBr are dissolved in 50ml deionized water, with the NaOH solution titration of 1mol/L, and constantly stir, to be titrated completely after suspension liquid loaded fill in the 50ml water heating kettle of 45ml deionized water, 300 DEG C of hydro-thermal reactions 12 hours, centrifugal drying obtains bromine doped vanadium dioxide powder, is 12% through ultimate analysis bromine atoms mol ratio.Bromine doped vanadium dioxide powder thing is M phase mutually, and transformation temperature is 50 DEG C, and particle size is 50nm, and during powder compressing tablet 25 DEG C, carrier concentration is 6.1 × 10
17cm
-3.
Embodiment 4
Doping molar percentage is the sulfur doping hypovanadic oxide powder of 8%
By 10gVOC
2o
45H
2o powder and 1.5g (NH
4)
2s is dissolved in 50ml deionized water, with the Na of 0.5mol/L
2cO
3solution titration, and constantly stirring, to be titrated completely after suspension liquid loaded fill in the 50ml water heating kettle of 45ml deionized water, 280 DEG C of hydro-thermal reactions 48 hours, centrifugal drying obtains sulfur doping hypovanadic oxide powder, is 8% through ultimate analysis sulphur atom mol ratio.Fig. 5 DSC curve shows that transformation temperature is 56 DEG C, and sulfur doping powder thing is M phase mutually, and particle size is 80nm, and during powder compressing tablet 25 DEG C, carrier concentration is 2.3 × 10
16cm
-3.
Embodiment 5
Doping molar percentage is the I2 doping hypovanadic oxide powder of 5%
Use 5gVOSO
4and 1.2gCaI
2be dissolved in 50ml deionized water, with the NH of 0.5mol/L
3h
2o solution titration, and constantly stirring, to be titrated completely after suspension liquid loaded fill in the 50ml water heating kettle of 45ml deionized water, 320 DEG C of hydro-thermal reactions 18 hours, centrifugal drying obtains I2 doping hypovanadic oxide powder, is 5% through ultimate analysis atomic iodine mol ratio.I2 doping powder thing is M phase mutually, and transformation temperature is 60 DEG C, and particle size is 70nm, and during powder compressing tablet 25 DEG C, carrier concentration is 8.7 × 10
16cm
-3.
Embodiment 6
Doping molar percentage is the Fluorin doped hypovanadic oxide powder of 1%
By 5gVOCl
2powder and 0.2gNaF are dissolved in 50ml deionized water, with the KOH solution titration of 2mol/L, and constantly stir, to be titrated completely after suspension liquid loaded fill in the 50ml water heating kettle of 45ml deionized water, 400 DEG C of hydro-thermal reactions 12 hours, centrifugal drying obtains Fluorin doped hypovanadic oxide powder, is 1% through ultimate analysis fluorine atom mol ratio.Fluorin doped powder thing is M phase mutually, and transformation temperature is 65 DEG C, and particle size is 100nm, and during powder compressing tablet 25 DEG C, carrier concentration is 5.9 × 10
16cm
-3.
Embodiment 7
The Fluorin doped hypovanadic oxide powder of doping molar percentage 10%
By 10gVOC
2o
45H
2o powder and 2gKF are dissolved in 50ml deionized water, with the NaOH solution titration of 1mol/L, and constantly stir, to be titrated completely after suspension liquid loaded fill in the 50ml water heating kettle of 45ml deionized water, 300 DEG C of hydro-thermal reactions 12 hours, centrifugal drying obtains Fluorin doped hypovanadic oxide powder, is 10% through ultimate analysis fluorine atom mol ratio.Adulterated powder thing is M phase mutually, and transformation temperature is 45 DEG C, and particle size is 40nm.
Embodiment 8
Doping molar percentage is the Fluorin doped hypovanadic oxide powder of 8%
By 10gVOC
2o
45H
2o powder and 1.2gKF are dissolved in 50ml deionized water, with the Na of 0.5mol/L
2cO
3solution titration, and constantly stirring, to be titrated completely after suspension liquid loaded fill in the 50ml water heating kettle of 45ml deionized water, 280 DEG C of hydro-thermal reactions 48 hours, centrifugal drying obtains Fluorin doped hypovanadic oxide powder, is 8% through ultimate analysis fluorine atom mol ratio.Adulterated powder thing is M phase mutually, and transformation temperature is 56 DEG C, and particle size is 50nm.
Embodiment 9
Doping molar percentage is the Fluorin doped hypovanadic oxide powder of 5%
Use 5gVOSO
4be dissolved in 50ml deionized water with 0.8gNaF, with the NH of 0.5mol/L
3h
2o solution titration, and constantly stirring, to be titrated completely after suspension liquid loaded fill in the 50ml water heating kettle of 45ml deionized water, 320 DEG C of hydro-thermal reactions 18 hours, centrifugal drying obtains Fluorin doped hypovanadic oxide powder, and its crystalline phase is also M phase, is 5% through ultimate analysis fluorine atom mol ratio.Adulterated powder thing is M phase mutually, and transformation temperature is 60 DEG C, and particle size is 70nm.
Embodiment 10
The small beaker containing 20ml water will be put into after the grinding of Fluorin doped hypovanadic oxide powder prepared by 1g embodiment 6, and constantly stir, add 0.5g PVP K-30, ultrasonic 60min after stirring 30min, obtained dispersion liquid.Adopt spin coating method by gained dispersion on glass substrate, then in room temperature or baking oven after drying, can vanadium dioxide film be obtained.Fig. 6 shows the Fluorin doped vanadium dioxide film curve of spectrum, light wave transmitance generation noticeable change before and after phase transformation.Utilize spectroscopic data to calculate, find that before and after thin film phase change, visible ray integration transmitance is 51.4% and 50.3%, high temperature sunlight integration transmitance is 38.6%, and the regulation and control rate of sun power is 13.9%, shows that film has excellent optical property.Fig. 7 provides film chromaticity diagram, can find out that a* and b* of Fluorin doped vanadium dioxide film is respectively 1.62 and 21.12, and the colourity a* of pure vanadium dioxide film and b* is respectively 3.62 and 23.67, show that Fluorin doped can effectively reduce film colourity, weaken film intrinsic yellow.
Embodiment 11
By I2 doping hypovanadic oxide powder prepared by 1g embodiment 5, prepare I2 doping vanadium dioxide film according to method for manufacturing thin film in embodiment 10.Before and after thin film phase change, visible ray integration transmitance is 46.7% and 45.9%, and high temperature sunlight integration transmitance is 37.3%, and the regulation and control rate of sun power is 11.2%, and the colourity a* of film and b* is respectively 1.9 and 23.12.
Embodiment 12
By Fluorin doped hypovanadic oxide powder prepared by 1g embodiment 9, prepare Fluorin doped vanadium dioxide film according to method for manufacturing thin film in embodiment 10.Before and after thin film phase change, visible ray integration transmitance is 48.7% and 47.2%, and high temperature sunlight integration transmitance is 34.3%, and the regulation and control rate of sun power is 12.3%, and the colourity a* of film and b* is respectively 1.4 and 20.33.
Embodiment 13
By sulfur doping hypovanadic oxide powder prepared by 1g embodiment 4, prepare sulfur doping vanadium dioxide film according to method for manufacturing thin film in embodiment 10.Before and after thin film phase change, visible ray integration transmitance is 41.5% and 42.7%, and high temperature sunlight integration transmitance is 34.1%, and the regulation and control rate of sun power is 9.7%, and the colourity a* of film and b* is respectively 0.61 and 20.84.
Embodiment 14
By Fluorin doped hypovanadic oxide powder prepared by 1g embodiment 8, prepare Fluorin doped vanadium dioxide film according to method for manufacturing thin film in embodiment 10.Before and after thin film phase change, visible ray integration transmitance is 45.2% and 44.7%, and high temperature sunlight integration transmitance is 30.1%, and the regulation and control rate of sun power is 10.4%, and the colourity a* of film and b* is respectively 0.21 and 18.57.
Industrial applicability: the method preparing hypovanadic oxide powder of the present invention, technique is simple, cost is low, yield is high, is applicable to scale production.Hypovanadic oxide powder of the present invention and film thereof can be applied to energy-saving coatings, energy saving paint, temperature control unit (such as sun power temperature control unit) and energy-saving coating; The reducing energy consumption on the surface such as existing building, car and boat can also be applied to; Can be applicable to again energy information equipment, comprise micro photo electric switch device, thermistor, battery material and optical information storage part etc.
Claims (14)
1. a doped vanadium dioxide powder, is characterized in that, the chemical constitution of described doped vanadium dioxide powder is VO
2-xm
x0<x≤0.5, wherein M is doped element, described doped element is fluorine, sulphur, chlorine, bromine or iodine, and described doped element M is for improving the pattern of described doped vanadium dioxide powder, transformation temperature, electric property and optical property, transformation temperature continuously adjustabe between-30 ~ 90 DEG C of described doped vanadium dioxide powder.
2. doped vanadium dioxide powder according to claim 1, is characterized in that, 0.001<x≤0.5.
3. doped vanadium dioxide powder according to claim 2, is characterized in that, 0.001<x≤0.1.
4. doped vanadium dioxide powder according to claim 3, is characterized in that, 0.001<x≤0.05.
5. doped vanadium dioxide powder according to any one of claim 1 to 4, is characterized in that, described doped vanadium dioxide powder is particulate state, bar-shaped or flower-shaped.
6. doped vanadium dioxide powder according to any one of claim 1 to 4, is characterized in that, described doped vanadium dioxide powder is of a size of 10nm ~ 800nm.
7. doped vanadium dioxide powder according to any one of claim 1 to 4, is characterized in that, the crystalline phase of described doped vanadium dioxide powder is Rutile Type.
8. doped vanadium dioxide powder according to any one of claim 1 to 4, is characterized in that, the carrier concentration of described doped vanadium dioxide powder is 10
15~ 10
21cm
-3between continuously adjustabe.
9. the preparation method of the doped vanadium dioxide powder according to any one of a claim 1 to 8, it is characterized in that, comprise: according to stoichiometric ratio, doping reagent is added in the precursor liquid containing tetravalence vanadium, stir, alkaline reagents titration is adopted to the addition of the precursor liquid of doping reagent until generate suspension liquid, hydro-thermal reaction 1 ~ 240 hour at 150 ~ 400 DEG C.
10. preparation method according to claim 9, is characterized in that, the temperature of described hydro-thermal reaction is 250 ~ 300 DEG C, and the described hydro-thermal reaction time is 4 ~ 40 hours.
11. 1 kinds of doped vanadium dioxide films, is characterized in that, described doped vanadium dioxide film is obtained on substrate by the dispersion of the doped vanadium dioxide powder according to any one of claim 1 to 8.
12. doped vanadium dioxide films according to claim 11, is characterized in that, the visible ray integration transmitance of described doped vanadium dioxide film is 20 ~ 80%, and sun power regulation and control rate is 0 ~ 20%.
13. doped vanadium dioxide films according to claim 11 or 12, it is characterized in that, the high temperature sunlight integration transmitance of described doped vanadium dioxide film is 10% ~ 60%.
14. doped vanadium dioxide films according to claim 11 or 12, it is characterized in that, the colourimetric number a* of described doped vanadium dioxide film is between-40 ~ 40, and b* is between-20 ~ 60.
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| CN102515563A (en) * | 2011-11-03 | 2012-06-27 | 中国科学院上海硅酸盐研究所 | Organic vanadium source for preparation of vanadium dioxide intelligent temperature control film and preparation method of film |
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| CN102515563A (en) * | 2011-11-03 | 2012-06-27 | 中国科学院上海硅酸盐研究所 | Organic vanadium source for preparation of vanadium dioxide intelligent temperature control film and preparation method of film |
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