CN108659812B - Efficient thermochromic nano composite powder with core-shell structure and preparation method thereof - Google Patents

Efficient thermochromic nano composite powder with core-shell structure and preparation method thereof Download PDF

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CN108659812B
CN108659812B CN201810450180.1A CN201810450180A CN108659812B CN 108659812 B CN108659812 B CN 108659812B CN 201810450180 A CN201810450180 A CN 201810450180A CN 108659812 B CN108659812 B CN 108659812B
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core
powder
thermochromic
tungsten bronze
shell structure
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CN108659812A (en
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肖秀娣
徐刚
程浩亮
郇昌梦
陆源
詹勇军
蒲泽伟
万溧
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Tibet New Energy Research And Demonstration Center
Guangzhou Institute of Energy Conversion of CAS
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Guangzhou Institute of Energy Conversion of CAS
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor

Abstract

The invention discloses a high-efficiency thermochromic nano composite powder with a core-shell structure, which is prepared from VO2The layer is a nuclear layer, and the tungsten bronze compound layer is a shell layer; the VO2The layer is vanadium dioxide nano powder, the minimum size in three-dimensional sizes of the vanadium dioxide nano powder is not more than 100nm, and the tungsten bronze compound layer is MxWO3Wherein M is selected from NH4+，Cs+，K+，Na+Or Li+Any one of (a); the value range of x is 0.01-0.8; the thickness of the tungsten bronze compound layer is less than 60nm, the shell layer absorbs heat by utilizing the infrared absorption characteristic of the tungsten bronze material, and the heat is rapidly transferred to the core layer VO through the tightly connected core-shell structure2Particles, causing phase change at elevated temperature, to reduce VO2The environmental temperature required for phase change is increased, and VO is increased2The thermal response speed of the material is reduced, the phase change reaction time is shortened, and the effect of high-efficiency thermochromism is achieved.

Description

Efficient thermochromic nano composite powder with core-shell structure and preparation method thereof
The technical field is as follows:
the invention relates to the field of energy-saving and environment-friendly new materials, in particular to high-efficiency thermochromic nano composite powder with a core-shell structure and a preparation method thereof.
Background art:
with the increasing exhaustion of global non-renewable energy and the increasing aggravation of the pollution problem of traditional petrochemical energy, the development and utilization of new energy have become a research hotspot and development trend of countries in the world. The solar energy is not only abundant in resource and inexhaustible in resource, but also free of any pollution to the environment, and is perfect clean energy. The most common utilization method of solar energy is lighting, but when sunlight (visible light band) is used for lighting, heat of the sunlight (near infrared band) is transmitted. When the temperature is higher in summer, the heat in the infrared region is hoped to be blocked to enter the room so as to reduce the load of an air conditioner, and when the temperature is lower in winter, the room needs to take more heat in the infrared region for heating. Therefore, the development of a material which can regulate and control sunlight according to seasonal changes, intelligently and efficiently utilize solar energy and has a thermochromic function is very important.
Vanadium dioxide (VO)2) The material is the most common thermochromic material, is a semiconductor at a low temperature, is transparent to an infrared region, is a metal phase at a high temperature and has a shielding effect on the infrared region. VO (vacuum vapor volume)2After the film is made, in the phase change process of high and low temperature, the visible light region can keep higher transmittance. VO is introduced into a reactor2The intelligent solar energy utilization device is applied to glass doors and windows, can intelligently regulate and control the transmission, reflection or absorption of incident light by sensing the change of the ambient temperature, fully utilizes sunlight all the year round, and achieves the purpose of intelligently and efficiently utilizing solar energy. Conveying applianceVO of the system2The thermochromic glass is prepared by a physical method (magnetron sputtering and the like), but the method has high cost and complex process and is difficult to realize large-area production. The other method is to synthesize VO first by a chemical method2The glass or plastic film with the thermochromic function is obtained by uniformly coating the glass or plastic film with the nano powder and the polymer which are compounded into slurry or mixed liquid, and finally the glass or plastic film with the thermochromic function is applied to glass doors and windows. Compared with the former method, the latter method has the advantages of low cost, simple process, easy large-scale production, wide application and the like. However, VO2The phase transition temperature is high, the thermal response is slow and the like, so that the practical application of the phase transition temperature is greatly hindered. Chinese patent CN102120615A discloses a preparation method and application of a thermochromic vanadium dioxide material, and fig. 12 shows that the phase change temperature is as high as 72 ℃ in the temperature rise process, thereby greatly limiting the practical application of the thermochromic vanadium dioxide material. The Chinese patents CN102295312B, CN104030356B and CN104030355B can reduce the phase transition temperature of vanadium dioxide by doping elements such as W, but simultaneously reduce the crystallinity and the phase transition latent heat of the vanadium dioxide, inhibit the sunlight regulation performance of the vanadium dioxide and greatly reduce the energy-saving efficiency of the vanadium dioxide. Aiming at improving VO2The thermal response characteristic of the material and the shortening of the phase change response time are newly researched so far.
The invention content is as follows:
the invention aims to aim at the prior VO2The problem of high phase transition temperature and poor thermal response of the thermochromic material is to provide high-efficiency thermochromic nano composite powder with a core-shell structure and a preparation method thereof, and the composite powder is VO2The tungsten bronze compound is taken as a shell layer, the infrared absorption characteristic of the tungsten bronze is utilized to ensure that the shell layer of the particles absorbs heat and rapidly transfers the heat to the core layer VO through a tightly connected core-shell structure2The temperature of the mixture is increased to generate phase change, thereby improving VO2The thermal response speed of the phase change material is reduced, the phase change response time is shortened, and the VO is reduced2The ambient temperature required for the phase change to occur.
The invention is realized by the following technical scheme:
high-efficiency thermochromic nano composite powder with core-shell structure, wherein VO is used as the composite powder2The layer is a nuclear layer, and the tungsten bronze compound layer is a shell layer; the VO2The layer is vanadium dioxide nano powder, the minimum size in three dimensions of the vanadium dioxide nano powder is not more than 100nm, preferably the size in three dimensions of the vanadium dioxide nano powder is not more than 100nm, and the vanadium dioxide nano powder is in the shape of a nearly spherical shape, an ellipsoidal shape, a cylindrical shape, a flake shape, a square block shape, a polygon shape and the like; the tungsten bronze compound layer is MxWO3Wherein M is selected from NH4+，Cs+，K+，Na+Or Li+Any one of (a); the value range of x is 0.01-0.8; the thickness of the tungsten bronze compound layer is less than 60nm, preferably not more than 50 nm.
The preparation method of the high-efficiency thermochromic nano composite powder with the core-shell structure comprises the following steps:
a) VO is introduced into a reactor2The powder is dispersed in a solvent, VO2Adding a surface modifier into the solvent with the mass percentage concentration of 1-50%, wherein the surface modifier is mixed with VO2Is 0.5-6: 1, and mixing and stirring to obtain the surface-modified VO2Mixing liquid A; the surface modifier is selected from at least one of polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, polyacetyl imine, acrylate copolymer, silane coupling agent and fluorine-containing surfactant;
b) adding a tungsten bronze precursor and a doping element compound into the mixed solution A, fully mixing and stirring to enable the tungsten bronze precursor to be attached to the surface of vanadium dioxide particles, adding a reducing agent, and reacting at a constant temperature of 25-180 ℃ to obtain mixed solution B; tungsten bronze precursor and VO2The mass ratio of (A) to (B) is 0.1-5: 1; the mass ratio of the doping element compound to the tungsten bronze precursor is 0.01-0.8: 1; the mass ratio of the reducing agent to the tungsten bronze precursor is 0.1-20: 1; the doping element compound is at least one selected from ammonia water, ammonium chloride, ammonium sulfate, ammonium bicarbonate, cesium hydroxide, cesium chloride, cesium sulfate, ammonium nitrate, cesium carbonate, potassium hydroxide, potassium chloride, potassium sulfate, potassium nitrate, cesium nitrate, potassium carbonate, sodium hydroxide, sodium chloride, sodium sulfate, sodium nitrate, sodium carbonate, lithium hydroxide, lithium chloride, lithium sulfate, lithium nitrate and lithium carbonate;
c) carrying out centrifugal precipitation on the solid phase components in the mixed solution B, and carrying out vacuum drying treatment at 100 ℃ to obtain vanadium dioxide powder C coated with the tungsten bronze precursor;
d) and (3) placing the powder C in a heating furnace for heat treatment at the temperature of 100 ℃ and 600 ℃ to obtain the thermochromic nano composite powder with the tungsten bronze-coated core-shell structure.
VO of step a)2Selected from phase A VO2B phase VO2M/R phase VO2P phase VO2At least one of (1).
The solvent in the step a) is at least one selected from water, methanol, ethanol, sorbitol, n-propanol, isopropanol, ethylene glycol, benzyl alcohol, hexane, toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl butanone, ethylene glycol monomethyl ether, propylene glycol methyl ether acetate, oleic acid and oleylamine.
In the step b), the tungsten bronze precursor is selected from at least one of tungstic acid, sodium tungstate, ammonium tungstate, tungsten hexachloride and tungsten trioxide; the reducing agent is at least one selected from citric acid, acetic acid, oleic acid, hydrochloric acid, oxalic acid, urea and sodium borohydride.
The constant temperature reaction time in the step b) is 0.5 to 4 hours.
The heat treatment time of the step d) is 0.5 to 8 hours.
The invention also protects the application of the high-efficiency thermochromic nano composite powder with the core-shell structure, and the high-efficiency thermochromic nano composite powder is used for preparing the high-efficiency thermochromic VO2The film is applied to window glass, building glass and automobile glass, efficiently utilizes and regulates sunlight, and can enable indoor or automobile interior to reach a comfortable temperature range all the year round.
The invention has the following beneficial effects:
1) construction with VO2The shell layer absorbs heat by utilizing the infrared absorption characteristic of the tungsten bronze material, and the heat is rapidly transferred to the core layer VO through the tightly connected core-shell structure2Particles, causing phase change at elevated temperature, to reduce VO2The environmental temperature required for phase change is increased, and VO is increased2The thermal response speed of the material is reduced, the phase change reaction time is shortened, and the effect of high-efficiency thermochromism is achieved.
2) The high-efficiency thermochromic nano composite powder with the core-shell structure can be used for preparing high-efficiency thermochromic VO2Film, which is applied to window glass and absorbs heat from tungsten bronze to make VO at high summer temperature2The particles are heated rapidly to generate phase change, and the heat of the infrared region of sunlight can be blocked; when the temperature is lower in winter, VO is caused by balance between heat absorbed by tungsten bronze and ambient temperature2The particles can not change phase at a low temperature, can permeate heat of a sunlight infrared region, and before and after the phase change, the tungsten bronze and the VO2The thermochromic film has higher visible light transmittance in a visible light area, and can not influence lighting, and can be applied to building glass, automobile glass and the like, so that sunlight can be efficiently utilized and regulated, and under the condition of not influencing lighting, a comfortable temperature range can be achieved indoors or in a vehicle all the year round, and the thermochromic film has a good application prospect.
Description of the drawings:
FIG. 1 is a schematic structural diagram of a high efficiency thermochromic nanocomposite powder of core-shell structure of the present invention;
wherein, 1, VO2Layer, 2, tungsten bronze compound layer.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1:
taking 5g of A-phase VO with the particle size of 90nm2Adding into a certain amount of water to prepare VO with the mass concentration of 30%2Adding 25g of polyvinyl alcohol into the suspension, and mixing and stirring for 30 min; adding 0.5g of ammonium tungstate and 0.015g of ammonium chloride, mixing and stirring for 30min to attach the precursor of the tungsten bronze to VO2Adding 10g of citric acid on the surface of the particles, reacting at the constant temperature of 80 ℃ for 1.5h to obtain suspension, centrifugally precipitating, and drying in vacuum at the temperature of 100 ℃ to obtain VO coated with the tungsten bronze precursor2Powder; putting the obtained powder into a heating furnace, and carrying out heat treatment at 400 ℃ for 2h to obtain VO2@(NH4)0.1WO3Core-shell structure nano composite powder, wherein core layer VO2Is M/R phase, shell (NH)4)0.1WO3Thickness ofIs 20 nm. VO prepared2@(NH4)0.1WO3The core-shell structure nano composite powder can make VO2The phase transition reaction time of (2) is shortened by 1 min.
Example 2
Taking 5g of B-phase VO with the particle diameter of 20nm2Adding into a certain amount of glycol to prepare VO with the mass concentration of 1%2Adding 2.5g of polyethylene glycol into the suspension, mixing and stirring for 30 min; adding 10g of sodium tungstate and 1.5g of sodium sulfate, mixing and stirring for 30min to attach the precursor of the tungsten bronze to the VO2Adding 10g of oxalic acid on the surface of the particles, reacting at 180 ℃ for 0.5h to obtain suspension, centrifugally precipitating, and vacuum drying at 100 ℃ to obtain VO coated with the tungsten bronze precursor2Powder; putting the obtained powder into a heating furnace, and performing heat treatment at 600 ℃ for 0.5h to obtain VO2@Na0.5WO3Core-shell structure nano composite powder, wherein core layer VO2Is M/R phase, shell Na0.5WO3Is 5 nm. VO prepared2@Na0.5WO3The core-shell structure nano composite powder can make VO2The phase transition reaction time of (2) is shortened by 3 min.
Example 3
Taking 5g of M/R phase VO with the particle size of 70nm2Adding into a certain amount of ethanol to prepare VO with the mass concentration of 10%2Adding 15g of polyacetyl imine into the suspension, and mixing and stirring for 30 min; adding 15g of tungstic acid and 0.75g of lithium carbonate, mixing and stirring for 30min to attach the precursor of the tungsten bronze to the VO2Adding 5g of urea on the surface of the particles, reacting at the constant temperature of 25 ℃ for 4h to obtain suspension, centrifugally precipitating, and drying in vacuum at 100 ℃ to obtain VO coated with the tungsten bronze precursor2Powder; putting the obtained powder into a heating furnace, and carrying out heat treatment at 100 ℃ for 8h to obtain VO2@Li0.3WO3Core-shell structure nano composite powder, wherein core layer VO2Is an M/R phase, shell Li0.3WO3Is 15 nm. VO prepared2@Li0.3WO3The core-shell structure nano composite powder can make VO2The phase transition reaction time of (2) is shortened by 2 min. .
Example 4
Taking 5g of P-phase VO with the particle size of 50nm2Adding into a certain amount of benzyl alcohol to prepare VO with the mass concentration of 5 percent2Adding 7.5g of fluorine-containing surfactant into the suspension, and mixing and stirring for 30 min; adding 20g of tungsten trioxide and 2g of cesium carbonate, mixing and stirring for 30min to attach the precursor of tungsten bronze to VO2Adding 20g of oleic acid on the surface of the particles, reacting for 1h at constant temperature of 120 ℃ to obtain suspension, centrifugally precipitating, and drying in vacuum at 100 ℃ to obtain VO coated with tungsten bronze precursor2Powder; putting the obtained powder into a heating furnace, and performing heat treatment at 300 ℃ for 3h to obtain VO2@Cs0.3WO3Core-shell structure nano composite powder, wherein core layer VO2Is M/R phase, shell Cs0.3WO3Is 10 nm. VO prepared2@Cs0.3WO3The core-shell structure nano composite powder can make VO2The phase transition reaction time of (2) is shortened by 4 min. .
Example 5
Taking 5g of M/R phase VO with the particle size of 80nm2Adding into a certain amount of isopropanol to prepare VO with the mass concentration of 20%2Adding 20g of polyvinylpyrrolidone into the suspension, and mixing and stirring for 30 min; adding 15g of sodium tungstate and 1.2g of sodium chloride, mixing and stirring for 30min to attach the precursor of the tungsten bronze to VO2Adding 1.5g of sodium borohydride on the surface of the particles, reacting for 3 hours at a constant temperature of 50 ℃ to obtain suspension, centrifugally precipitating, and drying in vacuum at 100 ℃ to obtain VO coated with the tungsten bronze precursor2Powder; putting the obtained powder into a heating furnace, and performing heat treatment at 150 ℃ for 6h to obtain VO2@Na0.4WO3Core-shell structure nano composite powder, wherein core layer VO2Is M/R phase, shell Na0.4WO3Is 15 nm. VO prepared2@Na0.4WO3The core-shell structure nano composite powder can make VO2The phase transition reaction time of (2) is shortened by 3 min. .
Example 6
Taking 5g of B-phase VO with the particle size of 60nm2Adding the mixture into a certain amount of butyl acetate to prepare VO with the mass concentration of 5 percent2Adding 10g of fluorine-containing surfactant into the suspension, and mixing and stirringStirring for 30 min; adding 15g of tungsten hexachloride and 0.9g of potassium nitrate, mixing and stirring for 30min to attach the precursor of tungsten bronze to VO2Adding 15g of citric acid on the surface of the particles, reacting at a constant temperature of 90 ℃ for 1.5h to obtain suspension, centrifugally precipitating, and drying in vacuum at 100 ℃ to obtain VO coated with the tungsten bronze precursor2Powder; putting the obtained powder into a heating furnace, and performing heat treatment at 500 ℃ for 1h to obtain VO2@K0.2WO3Core-shell structure nano composite powder, wherein core layer VO2Is M/R phase, shell K0.2WO3Is 10 nm. VO prepared2@K0.2WO3The core-shell structure nano composite powder can make VO2The phase transition reaction time of (2) is shortened by 2 min. .
Example 7
Taking 5g of M/R phase VO with the particle size of 50nm2Adding into a certain amount of toluene to prepare VO with the mass concentration of 2%2Adding 5g of silane coupling agent into the suspension, mixing and stirring for 30 min; adding 25g of tungsten hexachloride and 0.25g of cesium hydroxide, mixing and stirring for 30min to attach the precursor of tungsten bronze to VO2Adding 20g of acetic acid on the surface of the particles, reacting at the constant temperature of 60 ℃ for 2.5h to obtain suspension, centrifugally precipitating, and drying in vacuum at the temperature of 100 ℃ to obtain VO coated with the tungsten bronze precursor2Powder; putting the obtained powder into a heating furnace, and performing heat treatment at 200 ℃ for 5h to obtain VO2@Cs0.01WO3Core-shell structure nano composite powder, wherein core layer VO2Is M/R phase, shell Cs0.01WO3Is 5 nm. VO prepared2@Cs0.01WO3The core-shell structure nano composite powder can make VO2The phase transition reaction time of (2) is shortened by 1 min. .
Example 8
Taking 5g of M/R phase VO with the particle size of 100nm2Adding into a certain amount of oleic acid to prepare VO with the mass concentration of 50 percent2Adding 30g of acrylate copolymer into the suspension, and mixing and stirring for 30 min; adding 1g of ammonium tungstate and 0.8g of ammonium sulfate, mixing and stirring for 30min to attach the precursor of the tungsten bronze to the VO2Adding 2g hydrochloric acid on the surface of the particles, reacting at 70 deg.C for 2 hr to obtain suspension, and separatingAfter the core precipitation, vacuum drying is carried out at 100 ℃ to obtain the VO coated by the tungsten bronze precursor2Powder; putting the obtained powder into a heating furnace, and carrying out heat treatment at 250 ℃ for 4h to obtain VO2@(NH4)0.8WO3Core-shell structure nano composite powder, wherein core layer VO2Is M/R phase, shell (NH)4)0.8WO3Is 20 nm. VO prepared2@(NH4)0.8WO3The core-shell structure nano composite powder can make VO2The phase transition reaction time of (2) is shortened by 4 min.

Claims (10)

1. A preparation method of high-efficiency thermochromic nano composite powder with a core-shell structure is characterized by comprising the following steps:
a) VO is introduced into a reactor2The powder is dispersed in a solvent, VO2Adding a surface modifier into the solvent with the mass percentage concentration of 1-50%, wherein the surface modifier is mixed with VO2Is 0.5-6: 1, and mixing and stirring to obtain the surface-modified VO2Mixing liquid A; the surface modifier is selected from at least one of polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, polyacetyl imine, acrylate copolymer, silane coupling agent and fluorine-containing surfactant;
b) adding a tungsten bronze precursor and a doping element compound into the mixed solution A, fully mixing and stirring to enable the tungsten bronze precursor to be attached to the surface of vanadium dioxide particles, adding a reducing agent, and reacting at a constant temperature of 25-180 ℃ to obtain mixed solution B; tungsten bronze precursor and VO2The mass ratio of (A) to (B) is 0.1-5: 1; the mass ratio of the doping element compound to the tungsten bronze precursor is 0.01-0.8: 1; the mass ratio of the reducing agent to the tungsten bronze precursor is 0.1-20: 1; the doping element compound is at least one selected from ammonia water, ammonium chloride, ammonium sulfate, ammonium bicarbonate, cesium hydroxide, cesium chloride, cesium sulfate, ammonium nitrate, cesium carbonate, potassium hydroxide, potassium chloride, potassium sulfate, potassium nitrate, cesium nitrate, potassium carbonate, sodium hydroxide, sodium chloride, sodium sulfate, sodium nitrate, sodium carbonate, lithium hydroxide, lithium chloride, lithium sulfate, lithium nitrate and lithium carbonate;
c) carrying out centrifugal precipitation on the solid phase components in the mixed solution B, and carrying out vacuum drying treatment at 100 ℃ to obtain vanadium dioxide powder C coated with the tungsten bronze precursor;
d) and (3) placing the powder C in a heating furnace for heat treatment at the temperature of 100 ℃ and 600 ℃ to obtain the thermochromic nano composite powder with the tungsten bronze-coated core-shell structure.
2. The method for preparing the high-efficiency thermochromic nanocomposite powder with the core-shell structure according to claim 1, wherein the VO in the step a)2Selected from phase A VO2B phase VO2M/R phase VO2P phase VO2At least one of (1).
3. The method for preparing the high-efficiency thermochromic nanocomposite powder with the core-shell structure according to claim 1 or 2, wherein the solvent in the step a) is at least one selected from water, methanol, ethanol, sorbitol, n-propanol, isopropanol, ethylene glycol, benzyl alcohol, hexane, toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl butanone, ethylene glycol monomethyl ether, propylene glycol methyl ether acetate, oleic acid and oleylamine.
4. The preparation method of the high-efficiency thermochromic nanocomposite powder with the core-shell structure according to claim 1 or 2, wherein in the step b), the tungsten bronze precursor is at least one selected from tungstic acid, sodium tungstate, ammonium tungstate, tungsten hexachloride and tungsten trioxide.
5. The preparation method of the high-efficiency thermochromic nanocomposite powder with the core-shell structure according to claim 1 or 2, wherein in the step b), the reducing agent is at least one selected from citric acid, acetic acid, oleic acid, hydrochloric acid, oxalic acid, urea and sodium borohydride.
6. The preparation method of the high-efficiency thermochromic nanocomposite powder with the core-shell structure according to claim 1 or 2, wherein the constant-temperature reaction time in the step b) is 0.5 to 4 hours.
7. The preparation method of the high-efficiency thermochromic nanocomposite powder with a core-shell structure according to claim 1 or 2, wherein the heat treatment time in the step d) is 0.5 to 8 hours.
8. The preparation method of the core-shell structured high-efficiency thermochromic nano composite powder as claimed in claim 1, wherein the core-shell structured high-efficiency thermochromic nano composite powder is prepared from VO2The layer is a nuclear layer, and the tungsten bronze compound layer is a shell layer; the VO2The layer is vanadium dioxide nano powder, the minimum size in three-dimensional sizes of the vanadium dioxide nano powder is not more than 100nm, and the vanadium dioxide nano powder is in a shape of a nearly spherical shape, an ellipsoidal shape, a cylindrical shape, a flaky shape, a square block shape or a polygonal shape; the tungsten bronze compound layer is MxWO3Wherein M is selected from NH4+，Cs+，K+，Na+Or Li+Any one of (a); the value range of x is 0.01-0.8; the thickness of the tungsten bronze compound layer is less than 60 nm.
9. The high efficiency thermochromic nanocomposite powder of claim 8, wherein the vanadium dioxide nanopowder has a three dimensional size of no greater than 100nm and the tungsten bronze compound layer has a thickness of no greater than 50 nm.
10. The application of the high-efficiency thermochromic nano composite powder with the core-shell structure as claimed in claim 8, which is used for preparing high-efficiency thermochromic VO2The film is applied to window glass, building glass and automobile glass, efficiently utilizes and regulates sunlight, and can enable indoor or automobile interior to reach a comfortable temperature range all the year round.
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JP7379306B2 (en) * 2020-09-28 2023-11-14 東芝マテリアル株式会社 electrochromic element
CN113185863B (en) * 2021-04-13 2022-12-27 电子科技大学 Based on VO 2 Intelligent temperature control coating with core-shell structure and thermal variable emissivity
CN113667468B (en) * 2021-08-13 2022-07-01 广州中达新材料科技有限公司 Thermochromic material, light adjusting film and preparation method and application thereof
CN114395324B (en) * 2022-02-24 2023-08-01 北京国电富通科技发展有限责任公司 Thermochromic antifouling silicone rubber composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103803652A (en) * 2012-11-09 2014-05-21 深圳市润麒麟科技发展有限公司 High tungsten doping content nanometer VO2 powder material and preparation method thereof
CN105540667A (en) * 2015-12-30 2016-05-04 山东海容节能新材料有限公司 Preparation method of doping modified vanadium dioxide powder with lower phase transition temperature

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103803652A (en) * 2012-11-09 2014-05-21 深圳市润麒麟科技发展有限公司 High tungsten doping content nanometer VO2 powder material and preparation method thereof
CN105540667A (en) * 2015-12-30 2016-05-04 山东海容节能新材料有限公司 Preparation method of doping modified vanadium dioxide powder with lower phase transition temperature

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
VO2-WO3复合薄膜的制备及其热致变色-电致变色性能研究;窦维维等;《现代技术陶瓷》;20170630;第38卷(第3期);第226页 *

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