Ternary co-doped vo2 powder, method of preparation, temperature response adjusting function radiation cooling coating prepared therefrom and method of preparation thereof

Abstract

The present application relates to ternary co-doped VO2 powder, preparation method, radiation cooling coating with temperature response adjustment function prepared by the same and preparation method thereof. The ternary co-doped VO2 powder contains 1.46-4.95 at% tungsten, 0.98-4.93 at% fluorine and 0.48-0.54 at% sulfur. The radiation cooling coating with temperature response adjustment function is prepared from the following components: 22-38 parts of water-based polymer resin, 20-35 parts of radiation cooling filler, 15-28 parts of titanium white powder, 3-10 parts of ternary co-doped VO2 powder, 4-10 parts of functional additives and 10-20 parts of diluent. The ternary co-doped VO2 powder has a phase transition temperature reduced to room temperature and has the advantages of long-term service and oxidation resistance. The radiation cooling coating prepared from the same can maintain high reflectivity and high emissivity for a long time under high temperature conditions, realizes efficient cooling of buildings, and improves infrared transmittance when the temperature is reduced, allows part of heat to enter the indoor, and keeps the living environment comfortable for a long time at different temperatures.

Description

Technical Field

[0001] This invention relates to the field of building energy-saving coatings, and in particular to ternary co-doped VO2 powder, its preparation method, a radiation cooling coating with temperature response regulation function prepared therefrom, and its preparation method. Background Technology

[0002] Since the first energy crisis in the 1970s, building energy conservation has gradually become a global issue. In southern my country, traditional air conditioning and refrigeration systems consume large amounts of electricity during hot seasons, leading to significant energy waste and environmental burden. To address this challenge, the construction industry has proposed various energy-saving and cooling technologies, including traditional insulation materials, solar reflective coatings, and radiative cooling coatings. However, these energy-saving technologies have some limitations. For example, traditional insulation materials such as rock wool and integrated panels are prone to water absorption, condensation, and peeling; while heat-reflective coatings typically only mitigate the thermal effect of sunlight and cannot actively cool the building.

[0003] Radiative cooling coatings achieve cooling through radiative heat exchange. Based on the natural phenomenon of thermal radiation, they lower building temperatures by altering the thermal radiation characteristics of the building surface. Specifically, the coating reflects most of the visible and infrared thermal radiation from the sun, while radiating excess heat outwards through atmospheric windows as electromagnetic waves with wavelengths of 8–13.5 μm. This allows for direct heat exchange with the vast cold field of space, achieving highly efficient cooling of the building surface to below ambient temperature. Thanks to the spontaneous nature of thermal radiation, the coating passively lowers the building temperature without any energy consumption, reducing reliance on traditional mechanical air conditioning systems, improving building energy efficiency, and enhancing indoor comfort.

[0004] However, current market products typically maintain cooling effects under both high and low temperature conditions. This can lead to excessively low interior building temperatures in winter or on cold nights, resulting in additional energy waste. Therefore, it is necessary to develop a new type of temperature-controlled radiative cooling coating that can intelligently adjust its cooling effect according to the ambient temperature, maximizing energy efficiency and comfort. Vanadium dioxide is a metal oxide with phase transition properties, its phase transition temperature being 68℃. The structural change before and after the phase transition causes a reversible transition of the substance from transmission to reflection of infrared light. Based on this property, it has been widely and successfully applied in the preparation of intelligent temperature-controlled films and temperature-controlled glass. However, there are no mature precedents for its application in the field of energy-saving coatings. Summary of the Invention

[0005] The purpose of this invention is to provide a ternary co-doped VO2 powder, its preparation method, a radiation-cooling coating with temperature-responsive adjustment function prepared therefrom, and the preparation method thereof. The ternary co-doped VO2 powder of this invention has a phase transition temperature that can be lowered to room temperature and possesses the advantage of long-term service life with oxidation resistance (it still retains temperature-responsive function after 90 days of outdoor placement). The radiation-cooling coating with temperature-responsive adjustment function prepared using it can maintain high reflectivity and high emissivity for a long time under high-temperature conditions, achieving efficient building cooling. Furthermore, it increases infrared transmittance when the temperature decreases, allowing some heat to enter the room and maintaining a comfortable living environment at different temperatures for a long time.

[0006] This invention is achieved through the following techniques:

[0007] The ternary co-doped VO2 powder contains 1.46–4.95 at% tungsten, 0.98–4.93 at% fluorine, and 0.48–0.54 at% sulfur.

[0008] The preparation method of ternary co-doped VO2 powder includes the following steps: mixing tungsten-fluorine-doped vanadium dioxide with sublimed sulfur powder, then immersing the mixed powder in ethanol, then adding alkylbenzene sulfonate or dodecyl sulfate, followed by sonication at 50-60℃ for 30-60 min under a nitrogen atmosphere; then drying the mixture into a paste under a nitrogen atmosphere; then mechanically grinding the obtained paste at a rate of 800-1200 r / min for more than 15 min, and then drying it under a nitrogen atmosphere to obtain tungsten-fluorine-sulfur ternary co-doped vanadium dioxide powder;

[0009] In tungsten-fluorine doped vanadium dioxide, the atomic ratio of tungsten, fluorine, and sublimed sulfur is 1.5–5:1–5:0.5.

[0010] Tungsten-fluorine-doped vanadium dioxide contains 1.5–5 at% tungsten and 1–5 at% fluorine;

[0011] The mass ratio of alkylbenzene sulfonate or dodecyl sulfate to tungsten-fluorine-doped vanadium dioxide and sublimed sulfur powder is 3-5:1000.

[0012] A radiation-cooling coating with temperature response regulation function is prepared from the following components in the following mass ratio:

[0013] The mixture contains 22-38 parts of water-based polymer resin, 20-35 parts of radiation cooling filler, 15-28 parts of titanium dioxide, 3-10 parts of vanadium dioxide powder co-doped with tungsten, fluorine and sulfur, 4-10 parts of functional additives and 10-20 parts of diluent.

[0014] Specifically, the waterborne polymer resin is one or any combination of two or more of the following: silicone-acrylic emulsion, styrene-acrylic emulsion, polyurethane emulsion, or acrylic emulsion.

[0015] Specifically, the radiation cooling filler includes one or any combination of two or more of the following: alumina, silicon dioxide, zinc oxide, and magnesium hydrogen phosphate, ranging from 1 to 100 μm.

[0016] Specifically, the titanium dioxide is rutile titanium dioxide with a particle size range of 0.5 to 1 μm.

[0017] Specifically, the functional additives include one or any combination of two or more of the following: thickeners, dispersants, wetting agents, defoamers, coupling agents, and pH adjusters.

[0018] Preferably, the diluent is deionized water.

[0019] A method for preparing a radiation-cooling coating with temperature response regulation function as described in the above technical solution includes the following steps:

[0020] The diluent was added to a vertical mixer equipped with a dispersion disc, followed by the addition of functional additives, and then mixed thoroughly.

[0021] Then add radiation cooling filler, titanium dioxide, and tungsten-fluorine-sulfur ternary doped vanadium dioxide powder and stir evenly.

[0022] Next, add water-based polymer resin and stir until homogeneous.

[0023] Finally, the above materials are transferred to a planetary grinder and ground for more than 30 minutes, and then filtered to obtain the radiation cooling coating with temperature response regulation function.

[0024] VO2 exists in various crystal structures. The M1 phase of VO2 (monoclinic, space group: P21 / c) has high transmittance in the infrared band at room temperature. When the temperature rises above its phase transition temperature (68°C), it transforms into the R phase (tetragonal, space group: P42 / mnm). The tungsten-fluorine-sulfur ternary doped vanadium dioxide powder used in this invention, like VO2, also exhibits various crystal structures. The M1 phase (monoclinic, space group: P21 / c) of the tungsten-fluorine-sulfur ternary doped vanadium dioxide has high transmittance in the infrared band at room temperature. When the temperature rises above its phase transition temperature (close to room temperature), it transforms into the R phase (tetragonal, space group: P42 / mnm).

[0025] The infrared transmittance decreases while the emissivity and reflectivity increase, and this phase transition process is reversible. However, undoped VO2 has a high phase transition temperature. Therefore, tungsten fluorine was used to dope VO2 to lower its phase transition temperature. The phase transition temperature generally decreases with increasing doping concentration, and after doping, the phase transition temperature can be as low as room temperature. Simultaneously, the addition of sulfur significantly extends and enhances the stability of the doped vanadium dioxide, ensuring the long-lasting effectiveness of the prepared coating. Therefore, it is suitable for application in radiation cooling coatings.

[0026] Compared with the disclosed prior art, the present invention has the following beneficial effects:

[0027] This invention prepares ternary co-doped VO2 powder, which has a phase transition temperature reduced to room temperature and has the advantage of long service life with anti-oxidation (it still has temperature response function after being placed outdoors for 90 days). Therefore, its properties are more stable and its service life is longer.

[0028] The radiation cooling coating with temperature response regulation function prepared by this invention overcomes the shortcomings of existing radiation cooling coatings that have fixed performance and cannot change the cooling efficiency according to actual needs. It achieves the purpose of automatically enhancing the cooling effect for a long time at high temperatures, reducing the cooling power and allowing some infrared heat flow to pass through at low temperatures. Moreover, this transformation is completely reversible, thereby avoiding additional energy consumption in winter or cold nights and achieving a more ideal year-round energy saving effect. Detailed Implementation

[0029] To better explain the present invention, the technical solutions of the present invention will be described in detail below. The described embodiments are some embodiments of the present invention, but not all embodiments.

[0030] Example 1

[0031] The preparation method of the ternary co-doped VO2 powder in this embodiment includes the following steps: mixing tungsten-fluorine-doped vanadium dioxide with sublimed sulfur powder, then immersing the mixed powder in ethanol, then adding alkylbenzene sulfonate, followed by sonication at 50°C for 60 min under a nitrogen atmosphere; then drying the mixture into a paste under a nitrogen atmosphere; then mechanically grinding the obtained paste at a rate of 800 r / min for more than 15 min, and then drying it under a nitrogen atmosphere to obtain tungsten-fluorine-sulfur ternary co-doped vanadium dioxide powder;

[0032] In the tungsten-fluorine-doped vanadium dioxide, the atomic ratio of tungsten, fluorine, and sublimed sulfur is 1.5:1:0.5; the tungsten-fluorine-doped vanadium dioxide contains 1.5 at% tungsten and 1 at% fluorine.

[0033] The mass ratio of alkylbenzene sulfonate to tungsten-fluorine-doped vanadium dioxide and sublimed sulfur powder is 3:1000.

[0034] The particle size D90 of the ternary co-doped VO2 powder prepared in this embodiment is 20 μm.

[0035] The ternary co-doped VO2 powder prepared in this embodiment was analyzed by EDS using a FEIApreo 2C & Bruker QUANTAX200 XFlash6|60 field emission scanning electron microscope-energy dispersive spectrometer. It can be seen that the distribution of V, O, W, F and S elements is close to the doping ratio. The percentages of W, F and S in the ternary co-doped VO2 powder prepared in this embodiment are 1.46%, 0.98% and 0.52% respectively.

[0036] In this embodiment, a radiation-cooling coating with temperature response regulation function is prepared from the following components in the following mass ratio: 28 parts of water-based polymer resin, 28 parts of radiation-cooling filler, 15 parts of titanium dioxide, 5 parts of ternary co-doped VO2 powder, 6 parts of functional additives, and 18 parts of diluent.

[0037] The preparation method of the radiation-cooling coating in this embodiment includes the following steps:

[0038] S1: Add 18 parts of diluent deionized water to a vertical mixer equipped with a dispersion disc, then add the functional additives (0.3 parts hydroxyethyl cellulose, 1.5 parts dodecyl alcohol ester, 1.1 parts dispersant, 0.6 parts wetting agent, 1.3 parts defoamer, and 0.9 parts silane coupling agent), and stir at 800 rpm for 15 minutes until completely dispersed.

[0039] S2: Add 5 parts of ternary co-doped VO2 powder, 28 parts of radiation cooling filler and 15 parts of titanium dioxide into the mixing tank in sequence, increase the speed to 1200 r / min and stir for 30 min until the powder is evenly dispersed.

[0040] S3: Reduce the rotation speed to 600r / min, add 28 parts of silicone-acrylic emulsion to the mixing tank, and continue stirring for 15min;

[0041] S4: Transfer the mixture in S3 to a planetary mill and grind it at 600 r / min for 30 min. Filter the mixture to obtain the radiation cooling coating with temperature response regulation function.

[0042] This embodiment also includes 0.2 parts of functional additives: a bactericide and a mildew inhibitor.

[0043] The radiation cooling filler is a mixture of zirconium oxide and alumina (1:1) with a particle size D90 of 80 μm.

[0044] The radiation-cooling coating obtained in this embodiment has a solar reflectance of 0.92 and an average emissivity of 0.97 at an atmospheric window of 814 μm when the temperature is above the phase transition temperature; a solar reflectance of 0.68 and an average emissivity of 0.76 at an atmospheric window of 814 μm when the temperature is below the phase transition temperature; after 30 minutes of infrared lamp irradiation, the glass plate coated with the coating of this invention has a temperature 41.2°C lower than the blank glass plate, and the heating rate is significantly slower when the temperature reaches 36.9°C; the contrast ratio is 0.94, the stain resistance is 10%; it does not bubble, peel, or crack after 600 hours of artificial weathering; and it still has temperature response function after 90 days of outdoor placement.

[0045] Example 2

[0046] The preparation method of the ternary co-doped VO2 powder in this embodiment includes the following steps: mixing tungsten-fluorine-doped vanadium dioxide with sublimed sulfur powder, then immersing the mixed powder in ethanol, then adding dodecyl sulfate, followed by sonication at 60°C for 30 min under a nitrogen atmosphere; then drying the mixture into a paste under a nitrogen atmosphere; then mechanically grinding the obtained paste at a rate of 1200 r / min for more than 15 min, and then drying it under a nitrogen atmosphere to obtain tungsten-fluorine-sulfur ternary co-doped vanadium dioxide powder;

[0047] In the tungsten-fluorine-doped vanadium dioxide, the atomic ratio of tungsten, fluorine, and sublimed sulfur is 2:2:0.5; the particle size D90 of the sublimed sulfur is 20 μm.

[0048] Tungsten-fluorine-doped vanadium dioxide contains 2 at% tungsten and 2 at% fluorine;

[0049] The mass ratio of dodecyl sulfate to tungsten-fluorine-doped vanadium dioxide and sublimed sulfur powder is 3.5:1000.

[0050] The samples in this embodiment were subjected to EDS energy dispersive spectroscopy analysis using a FEIApreo 2C & Bruker QUANTAX200 XFlash6|60 field emission scanning electron microscope-energy dispersive spectroscopy system. The distribution of V, O, W, F and S elements was analyzed. The percentages of W, F and S in the ternary co-doped VO2 powder prepared in this embodiment were 2.05%, 1.97% and 0.51%, respectively, which are close to the doping ratio.

[0051] The particle size D90 of the ternary co-doped VO2 powder prepared in this embodiment is 20 μm.

[0052] In this embodiment, a radiation-cooling coating with temperature response regulation function is prepared from the following components in the following mass ratio: 38 parts of water-based polymer resin, 21 parts of radiation-cooling filler, 20 parts of titanium dioxide, 3 parts of ternary co-doped VO2 powder, 8 parts of functional additives, and 10 parts of diluent.

[0053] The preparation method of the radiation-cooling coating in this embodiment includes the following steps:

[0054] S1: Add 10 parts of diluent deionized water to a vertical mixer with a dispersion disc, then add functional additives (0.4 parts of hydroxyethyl cellulose, stir at 800 r / min for 15 min until it is completely dispersed, then add 1.8 parts of alcohol ester dodecyl, 1.5 parts of dispersant, 0.9 parts of wetting agent, 1.7 parts of defoamer, and 1.3 parts of silane coupling agent) and continue stirring and dispersing for more than 10 min until uniform;

[0055] S2: Add 3 parts of ternary co-doped VO2 powder, 21 parts of radiation cooling filler and 20 parts of titanium dioxide to the mixing tank in sequence, increase the speed to 1200r / min and stir for 30min until the powder is evenly dispersed.

[0056] S3: Reduce the rotation speed to 600 r / min, add 38 parts of styrene-acrylic emulsion, and stir continuously for 15 min;

[0057] S4: Transfer the mixture in S3 to a planetary mill and grind it at 600 r / min for 30 min. Filter the mixture to obtain the radiation cooling coating with temperature response regulation function.

[0058] This embodiment also includes 0.3 parts of functional additives: bactericide and 0.1 parts of antifungal agent.

[0059] The radiation cooling filler is zinc oxide with a particle size D90 of 90 μm.

[0060] The radiation-cooling coating obtained in this embodiment has a solar reflectance of 0.95 and an average emissivity of 0.94 at an atmospheric window of 814 μm when the temperature is above the phase transition temperature; a solar reflectance of 0.69 and an average emissivity of 0.65 at an atmospheric window of 814 μm when the temperature is below the phase transition temperature; after 30 minutes of infrared lamp irradiation, the glass plate coated with the coating of this invention has a temperature 47.1°C lower than the blank glass plate, and the heating rate is significantly slower when the temperature reaches 35.3°C; the contrast ratio is 0.95, the stain resistance is 9%; it does not bubble, peel, or crack after 600 hours of artificial weathering; and it still has temperature response function after 90 days of outdoor placement.

[0061] Example 3

[0062] The preparation method of the ternary co-doped VO2 powder in this embodiment includes the following steps: mixing tungsten-fluorine-doped vanadium dioxide with sublimed sulfur powder, then immersing the mixed powder in ethanol, then adding alkylbenzene sulfonate, followed by sonication at 55°C for 45 min under a nitrogen atmosphere; then drying the mixture into a paste under a nitrogen atmosphere; then mechanically grinding the obtained paste at a rate of 1000 r / min for more than 15 min, and then drying it under a nitrogen atmosphere to obtain tungsten-fluorine-sulfur ternary co-doped vanadium dioxide powder;

[0063] In the tungsten-fluorine-doped vanadium dioxide, the atomic ratio of tungsten, fluorine, and sublimed sulfur is 3:3.5:0.5; the particle size D90 of the sublimed sulfur is 20 μm.

[0064] Tungsten-fluorine-doped vanadium dioxide contains 3 at% tungsten and 3.5 at% fluorine;

[0065] The mass ratio of alkylbenzene sulfonate salt to tungsten-fluorine-doped vanadium dioxide and sublimed sulfur powder is 4:1000.

[0066] The sample of this embodiment was subjected to EDS energy dispersive spectroscopy analysis using a FEIApreo 2C & Bruker QUANTAX200 XFlash6|60 field emission scanning electron microscope-energy dispersive spectroscopy system. The distribution of V, O, W, F and S elements can be seen. The percentages of W, F and S in the ternary co-doped VO2 powder prepared in this embodiment are 2.98%, 3.51% and 0.49% respectively, which are close to the doping ratio.

[0067] The particle size D90 of the ternary co-doped VO2 powder prepared in this embodiment is 20 μm.

[0068] In this embodiment, a radiation-cooling coating with temperature response regulation function is prepared from the following components in the following mass ratio: 22 parts of water-based polymer resin, 20 parts of radiation-cooling filler, 28 parts of titanium dioxide, 8 parts of ternary co-doped VO2 powder, 4 parts of functional additives, and 18 parts of diluent.

[0069] The preparation method of the radiation-cooling coating in this embodiment includes the following steps:

[0070] S1: Add 18 parts of diluent deionized water to a vertical mixer with a dispersion disc, then add functional additives (0.3 parts of hydroxyethyl cellulose, stir at 800 r / min for 15 min until it is completely dispersed, then add 0.9 parts of alcohol ester twelve, 0.7 parts of dispersant, 0.5 parts of wetting agent, 0.7 parts of defoamer, and 0.7 parts of silane coupling agent) and continue stirring and dispersing for more than 10 min.

[0071] S2: Add 8 parts of ternary co-doped VO2 powder, 20 parts of radiation cooling filler and 28 parts of titanium dioxide to the mixing tank in sequence, increase the speed to 1200r / min and stir for 30min until the powder is evenly dispersed.

[0072] S3: Reduce the speed to 600 r / min, add 22 parts of polyurethane emulsion to the mixing tank, and continue stirring for 15 min;

[0073] S4: Transfer the mixture in S3 to a planetary mill and grind it at 600 r / min for 30 min. Filter the mixture to obtain the radiation cooling coating with temperature response regulation function.

[0074] This embodiment also includes 0.1 parts of functional additives: bactericide and mildew inhibitor.

[0075] The radiation cooling filler is silicon dioxide with a particle size D90 of 100 μm.

[0076] The radiation-cooling coating obtained in this embodiment has a solar reflectance of 0.92 and an average emissivity of 0.94 at an atmospheric window of 814 μm when the temperature is above the phase transition temperature; and a solar reflectance of 0.52 and an average emissivity of 0.59 at an atmospheric window of 814 μm when the temperature is below the phase transition temperature. After irradiation with an infrared lamp for 30 minutes, the glass plate coated with the coating of this invention has a temperature 38.6°C lower than the blank glass plate, and the heating rate is significantly slower when the temperature reaches 30.6°C. The contrast ratio is 0.93, the stain resistance is 12%, and the artificial weathering resistance is 600 hours without blistering, peeling, or cracking. It still has temperature response function after being placed outdoors for 90 days.

[0077] Example 4

[0078] The preparation method of the ternary co-doped VO2 powder in this embodiment includes the following steps: mixing tungsten-fluorine-doped vanadium dioxide with sublimed sulfur powder, then immersing the mixed powder in ethanol, then adding alkylbenzene sulfonate, followed by sonication at 55°C for 45 min under a nitrogen atmosphere; then drying the mixture into a paste under a nitrogen atmosphere; then mechanically grinding the obtained paste at a rate of 1000 r / min for more than 15 min, and then drying it under a nitrogen atmosphere to obtain tungsten-fluorine-sulfur ternary co-doped vanadium dioxide powder;

[0079] In the tungsten-fluorine-doped vanadium dioxide, the atomic ratio of tungsten, fluorine, and sublimed sulfur is 1.5:1.5:0.5; the particle size D90 of the sublimed sulfur is 20 μm.

[0080] Tungsten-fluorine-doped vanadium dioxide contains 1.5 at% tungsten and 1.5 at% fluorine;

[0081] The mass ratio of alkylbenzene sulfonate to tungsten-fluorine-doped vanadium dioxide and sublimed sulfur powder is 4.5:1000.

[0082] The sample of this embodiment was subjected to EDS energy dispersive spectroscopy analysis using a FEIApreo 2C & Bruker QUANTAX200 XFlash6|60 field emission scanning electron microscope-energy dispersive spectroscopy system. The distribution of V, O, W, F and S elements can be seen. The percentages of W, F and S in the ternary co-doped VO2 powder prepared in this embodiment are 1.52%, 1.49% and 0.51% respectively, which are close to the doping ratio.

[0083] The particle size D90 of the ternary co-doped VO2 powder prepared in this embodiment is 20 μm.

[0084] In this embodiment, a radiation-cooling coating with temperature response regulation function is prepared from the following components in the following mass ratio: 27 parts of water-based polymer resin, 25 parts of radiation-cooling filler, 15 parts of titanium dioxide, 3 parts of ternary co-doped VO2 powder, 10 parts of functional additives, and 20 parts of diluent.

[0085] The preparation method of the radiation-cooling coating in this embodiment includes the following steps:

[0086] S1: Add 20 parts of diluent deionized water to a vertical mixer with a dispersion disc, add functional additives (0.4 parts of hydroxyethyl cellulose, stir at 800 r / min for 15 min until it is completely dispersed, then add 1.8 parts of alcohol ester dodecyl, 1.8 parts of dispersant, 1.1 parts of wetting agent, 2.1 parts of defoamer, and 1.8 parts of silane coupling agent in sequence), and continue to stir and disperse for more than 10 min;

[0087] S2: Add 3 parts of ternary co-doped VO2 powder, 25 parts of radiation cooling filler and 15 parts of titanium dioxide into the mixing tank in sequence, increase the speed to 1200 r / min and stir for 30 min until the powder is evenly dispersed.

[0088] S3: Reduce the speed to 600r / min, add 28 parts of acrylic emulsion to the mixing tank, and continue stirring for 15min;

[0089] S4: Transfer the mixture in S3 to a planetary mill and grind it at 600 r / min for 30 min. Filter the mixture to obtain the radiation cooling coating with temperature response regulation function.

[0090] This embodiment also includes 0.5 parts of functional additives: bactericide and mildew inhibitor.

[0091] The radiation cooling filler is zirconium oxide with a particle size D90 of 120 μm.

[0092] The radiation cooling coating obtained in this embodiment has a solar reflectance of 0.93 and an average emissivity of 0.96 at an atmospheric window of 814 μm when the temperature is above the phase transition temperature; and a solar reflectance of 0.72 and an average emissivity of 0.68 at an atmospheric window of 814 μm when the temperature is below the phase transition temperature. After irradiation with an infrared lamp for 30 minutes, the glass plate coated with the coating of this invention has a temperature 45.2°C lower than the blank glass plate, and the heating rate is significantly slower when the temperature reaches 35.3°C. The contrast ratio is 0.93, the stain resistance is 12%, and the artificial weathering resistance is 600 hours without blistering, peeling, or cracking. It still has temperature response function after being placed outdoors for 90 days.

[0093] Example 5

[0094] The preparation method of the ternary co-doped VO2 powder in this embodiment includes the following steps: mixing tungsten-fluorine-doped vanadium dioxide with sublimed sulfur powder, then immersing the mixed powder in ethanol, then adding alkylbenzene sulfonate, followed by sonication at 55°C for 45 min under a nitrogen atmosphere; then drying the mixture into a paste under a nitrogen atmosphere; then mechanically grinding the obtained paste at a rate of 1000 r / min for more than 15 min, and then drying it under a nitrogen atmosphere to obtain tungsten-fluorine-sulfur ternary co-doped vanadium dioxide powder;

[0095] In the tungsten-fluorine-doped vanadium dioxide, the atomic ratio of tungsten, fluorine, and sublimed sulfur is 1.5:1.5:0.5; the particle size D90 of the sublimed sulfur is 20 μm.

[0096] Tungsten-fluorine-doped vanadium dioxide contains 1.5 at% tungsten and 1.5 at% fluorine;

[0097] The mass ratio of alkylbenzene sulfonic acid to tungsten-fluorine-doped vanadium dioxide and sublimed sulfur powder is 5:1000.

[0098] The sample of this embodiment was subjected to EDS energy dispersive spectroscopy analysis using a FEIApreo 2C & Bruker QUANTAX200 XFlash6|60 field emission scanning electron microscope-energy dispersive spectroscopy system. The distribution of V, O, W, F and S elements can be seen. The percentages of W, F and S in the ternary co-doped VO2 powder prepared in this embodiment are 1.47%, 1.51% and 0.49% respectively, which are close to the doping ratio.

[0099] The particle size D90 of the ternary co-doped VO2 powder prepared in this embodiment is 20 μm.

[0100] In this embodiment, a radiation-cooling coating with temperature response regulation function is prepared from the following components in the following mass ratio: 25 parts of water-based polymer resin, 35 parts of radiation-cooling filler, 15 parts of titanium dioxide, 5 parts of ternary co-doped VO2 powder, 5 parts of functional additives, and 15 parts of diluent.

[0101] The preparation method of the radiation-cooling coating in this embodiment includes the following steps:

[0102] S1: Add 15 parts of diluent deionized water to a vertical mixer with a dispersion disc, add functional additives (0.3 parts of hydroxyethyl cellulose, stir at 800 r / min for 15 min until it is completely dispersed, then add 1.2 parts of alcohol ester dodecyl, 0.9 parts of dispersant, 0.5 parts of wetting agent, 1.1 parts of defoamer, and 0.7 parts of silane coupling agent in sequence), and continue to stir and disperse for more than 10 min;

[0103] S2: Add 5 parts of ternary co-doped VO2 powder, 35 parts of radiation cooling filler and 15 parts of titanium dioxide to the mixing tank in sequence, increase the speed to 1200 r / min and stir for 30 min until the powder is evenly dispersed.

[0104] S3: Reduce the speed to 600 r / min, add 25 parts of the mixed emulsion (styrene-acrylic emulsion: silicone-acrylic emulsion = 1:1) to the mixing tank, and continue to stir for 15 min;

[0105] S4: Transfer the mixture in S3 to a planetary mill and grind it at 600 r / min for 30 min. Filter the mixture to obtain the radiation cooling coating with temperature response regulation function.

[0106] This embodiment also includes 0.2 parts of functional additives: bactericide and 0.1 parts of antifungal agent.

[0107] The radiation cooling filler is a mixture of zirconium oxide and alumina, with a particle size D90 of 120 μm.

[0108] The radiation cooling coating obtained in this embodiment has a solar reflectance of 0.93 and an average emissivity of 0.98 at an atmospheric window of 8 14 μm when the temperature is above the phase transition temperature; a solar reflectance of 0.64 and an average emissivity of 0.77 at an atmospheric window of 8 14 μm when the temperature is below the phase transition temperature; after 30 minutes of infrared lamp irradiation, the glass plate coated with the coating of this invention has a temperature 46.5°C lower than the blank glass plate, and the heating rate is significantly slower when the temperature reaches 35.8°C; the contrast ratio is 0.94, the stain resistance is 8%; the artificial weathering resistance is 600 hours without blistering, peeling, or cracking; and it still has temperature response function after 90 days of outdoor placement.

[0109] Example 6

[0110] The preparation method of the ternary co-doped VO2 powder in this embodiment includes the following steps: mixing tungsten-fluorine-doped vanadium dioxide with sublimed sulfur powder, then immersing the mixed powder in ethanol, adding alkylbenzene sulfonate, and then sonicating at 55°C for 45 min under a nitrogen atmosphere; then drying the mixture into a paste under a nitrogen atmosphere; then mechanically grinding the obtained paste at a rate of 1000 r / min for more than 15 min, and then drying it under a nitrogen atmosphere to obtain tungsten-fluorine-sulfur ternary co-doped vanadium dioxide powder; wherein, the atomic ratio of tungsten, fluorine and sublimed sulfur in the tungsten-fluorine-doped vanadium dioxide is 5:5:0.5; the particle size D90 of the sublimed sulfur is 20 μm;

[0111] Tungsten-fluorine-doped vanadium dioxide contains 5 at% tungsten and 5 at% fluorine;

[0112] The mass ratio of alkylbenzene sulfonate to tungsten-fluorine-doped vanadium dioxide and sublimed sulfur powder is 5:1000.

[0113] The sample of this embodiment was subjected to EDS energy dispersive spectroscopy analysis using a FEIApreo 2C & Bruker QUANTAX200 XFlash6|60 field emission scanning electron microscope-energy dispersive spectroscopy system. The distribution of V, O, W, F and S elements can be seen. The percentages of W, F and S in the ternary co-doped VO2 powder prepared in this embodiment are 4.95%, 4.93% and 0.48% respectively, which are close to the doping ratio.

[0114] The particle size D90 of the ternary co-doped VO2 powder prepared in this embodiment is 20 μm.

[0115] In this embodiment, a radiation-cooling coating with temperature response regulation function is prepared from the following components in the following mass ratio: 27 parts of water-based polymer resin, 22 parts of radiation-cooling filler, 18 parts of titanium dioxide, 10 parts of ternary co-doped VO2 powder, 8 parts of functional additives, and 15 parts of diluent.

[0116] The preparation method of the radiation-cooling coating in this embodiment includes the following steps:

[0117] S1: Add 15 parts of diluent deionized water to a vertical mixer with a dispersion disc, add functional additives (0.4 parts of hydroxyethyl cellulose, stir at 800 r / min for 15 min until it is completely dispersed, then add 1.9 parts of alcohol ester dodecyl, 1.5 parts of dispersant, 0.9 parts of wetting agent, 1.8 parts of defoamer, and 1.2 parts of silane coupling agent) to the water, and continue stirring and dispersing for more than 10 min;

[0118] S2: Add 10 parts of ternary co-doped VO2 powder, 22 parts of radiation cooling filler and 18 parts of titanium dioxide to the mixing tank in sequence, increase the speed to 1200 r / min and stir for 30 min until the powder is evenly dispersed.

[0119] S3: Reduce the speed to 600r / min, add 27 parts of acrylic emulsion to the mixing tank, and continue stirring for 15min;

[0120] S4: Transfer the mixture in S3 to a planetary mill and grind it at 600 r / min for 30 min. Filter the mixture to obtain the radiation cooling coating with temperature response regulation function.

[0121] This embodiment also includes 0.2 parts of functional additives: bactericide and 0.1 parts of antifungal agent.

[0122] The radiation cooling filler is a mixture of zirconium oxide and alumina, with a particle size D90 of 100 μm.

[0123] The radiation-cooling coating obtained in this embodiment has a solar reflectance of 0.92 and an average emissivity of 0.95 at an atmospheric window of 814 μm when the temperature is above the phase transition temperature; and a solar reflectance of 0.46 and an average emissivity of 0.51 at an atmospheric window of 814 μm when the temperature is below the phase transition temperature. After 30 minutes of infrared lamp irradiation, the glass plate coated with the coating of this invention has a temperature 42.6°C lower than the blank glass plate, and the heating rate is significantly slower when the temperature reaches 26.6°C. The contrast ratio is 0.95, the stain resistance is 11%, and the artificial weathering resistance is 600 hours without blistering, peeling, or cracking. It still has temperature response function after being placed outdoors for 90 days.

[0124] Example 7

[0125] The preparation method of the ternary co-doped VO2 powder in this embodiment includes the following steps: mixing tungsten-fluorine-doped vanadium dioxide with sublimed sulfur powder, then immersing the mixed powder in ethanol, then adding alkylbenzene sulfonate, followed by sonication at 55°C for 45 min under a nitrogen atmosphere; then drying the mixture into a paste under a nitrogen atmosphere; then mechanically grinding the obtained paste at a rate of 1000 r / min for more than 15 min, and then drying it under a nitrogen atmosphere to obtain tungsten-fluorine-sulfur ternary co-doped vanadium dioxide powder;

[0126] In the tungsten-fluorine-doped vanadium dioxide, the atomic ratio of tungsten, fluorine, and sublimed sulfur is 2.5:2.0:0.5; the particle size D90 of the sublimed sulfur is 20 μm.

[0127] Tungsten-fluorine-doped vanadium dioxide contains 2.5 at% tungsten and 2.0 at% fluorine;

[0128] The mass ratio of alkylbenzene sulfonate to tungsten-fluorine-doped vanadium dioxide and sublimed sulfur powder is 5:1000.

[0129] The sample of this embodiment was subjected to EDS energy dispersive spectroscopy analysis using a FEIApreo 2C & Bruker QUANTAX200 XFlash6|60 field emission scanning electron microscope-energy dispersive spectroscopy system. The distribution of V, O, W, F and S elements can be seen. The percentages of W, F and S in the ternary co-doped VO2 powder prepared in this embodiment are 2.53%, 2.05% and 0.54%, respectively, which are close to the doping ratio.

[0130] The particle size D90 of the ternary co-doped VO2 powder prepared in this embodiment is 20 μm.

[0131] In this embodiment, a radiation-cooling coating with temperature response regulation function is prepared from the following components in the following mass ratio: 30 parts of water-based polymer resin, 25 parts of radiation-cooling filler, 20 parts of titanium dioxide, 5 parts of ternary co-doped VO2 powder, 6 parts of functional additives, and 14 parts of diluent.

[0132] The preparation method of the radiation-cooling coating in this embodiment includes the following steps:

[0133] S1: Add 14 parts of diluent deionized water to a vertical mixer with a dispersion disc, then add functional additives (0.3 parts of hydroxyethyl cellulose, stir at 800 r / min for 15 min until it is completely dispersed, then add 1.5 parts of alcohol ester dodecyl, 1.1 parts of dispersant, 0.6 parts of wetting agent, 1.3 parts of defoamer, and 0.9 parts of silane coupling agent) to the water, and continue stirring and dispersing for more than 10 min;

[0134] S2: Add 5 parts of ternary co-doped VO2 powder, 25 parts of radiation cooling filler and 20 parts of titanium dioxide to the mixing tank in sequence, increase the speed to 1200 r / min and stir for 30 min until the powder is evenly dispersed.

[0135] S3: Reduce the rotation speed to 600r / min, add 30 parts of styrene-acrylic emulsion to the mixing tank, and continue stirring for 15min;

[0136] S4: Transfer the mixture in S3 to a planetary mill and grind it at 600 r / min for 30 min. Filter the mixture to obtain the radiation cooling coating with temperature response regulation function.

[0137] This embodiment also includes 0.2 parts of functional additives: bactericide and 0.1 parts of antifungal agent.

[0138] The radiation cooling filler is a mixture of silicon dioxide and alumina (1:1) with a particle size D90 of 100 μm.

[0139] The radiation cooling coating obtained in this embodiment has a solar reflectance of 0.96 and an average emissivity of 0.98 at an atmospheric window of 814 μm when the temperature is above the phase transition temperature; a solar reflectance of 0.56 and an average emissivity of 0.61 at an atmospheric window of 814 μm when the temperature is below the phase transition temperature; after irradiation with an infrared lamp for 30 minutes, the glass plate coated with the coating of this invention is 50.3°C lower than the blank glass plate and the heating rate is significantly slower when the temperature reaches 31.2°C; the contrast ratio is 0.96, the stain resistance is 8%; the artificial weathering resistance is 600 hours without blistering, peeling, or cracking; and it still has temperature response function after being placed outdoors for 90 days.

[0140] Comparative Example 1

[0141] In this comparative example, a radiation-cooling coating is prepared from the following components in the following mass ratio: 30 parts of water-based polymer resin, 30 parts of radiation-cooling filler, 20 parts of titanium dioxide, 6 parts of functional additives, and 14 parts of diluent.

[0142] The preparation method of the radiation-cooling coating in this comparative example includes the following steps:

[0143] S1: Add 14 parts of deionized water to a vertical mixer with a dispersion disc, add 0.3 parts of hydroxyethyl cellulose to the water, stir at 800 r / min for 15 min until it is completely dispersed, then add 1.5 parts of alcohol ester dodecyl, 1.1 parts of dispersant, 0.6 parts of wetting agent, 1.3 parts of defoamer, and 0.9 parts of silane coupling agent in sequence, and continue to stir and disperse for more than 10 min;

[0144] S2: Add 30 parts of radiation cooling filler and 20 parts of titanium dioxide to the mixing tank in sequence, increase the speed to 1200 r / min, and stir for 30 min until the powder is evenly dispersed.

[0145] S3: Reduce the rotation speed to 600 r / min, add 30 parts of styrene-acrylic emulsion, 0.2 parts of bactericide, and 0.1 parts of mildew inhibitor to the mixing tank, and continue stirring for 15 min;

[0146] S4: Transfer the mixture in S3 to a planetary mill and grind it at 600 r / min for 30 min. Filter the mixture to obtain the radiation cooling coating with temperature response regulation function.

[0147] The radiation cooling filler is a mixture of silicon dioxide and alumina (1:1) with a particle size D90 of 100 μm.

[0148] The radiation-cooling coating obtained in this comparative example has a solar reflectance of 0.95 and an average emissivity of 0.97 at an atmospheric window of 814 μm; it has no temperature response function; after 30 minutes of infrared lamp irradiation, the glass plate coated with the coating of this invention is 49.6°C lower than the blank glass plate, and no abrupt change in the heating rate with increasing temperature was observed; the contrast ratio is 0.96, the stain resistance is 8%; and the artificial weathering resistance is 600 hours without blistering, peeling, or cracking.

[0149] Comparative Example 2

[0150] In this comparative example, a radiation-cooling coating with temperature response regulation function is prepared from the following components in the following mass ratio: 38 parts of water-based polymer resin, 21 parts of radiation-cooling filler, 20 parts of titanium dioxide, 3 parts of undoped vanadium dioxide powder, 8 parts of functional additives, and 10 parts of diluent.

[0151] The preparation method of the radiation-cooling coating in this comparative example includes the following steps:

[0152] S1: Add 10 parts of deionized water to a vertical mixer with a dispersion plate, add 0.4 parts of hydroxyethyl cellulose to the water, stir at 800 r / min for 15 min until it is completely dispersed, then add 1.8 parts of alcohol ester dodecyl, 1.5 parts of dispersant, 0.9 parts of wetting agent, 1.7 parts of defoamer, and 1.3 parts of silane coupling agent in sequence, and continue to stir and disperse for more than 10 min;

[0153] S2: Add 3 parts of undoped vanadium dioxide powder, 21 parts of radiation cooling filler, and 20 parts of titanium dioxide to the mixing tank in sequence, increase the speed to 1200 r / min, and stir for 30 min until the powder is evenly dispersed.

[0154] S3: Reduce the rotation speed to 600 r / min, add 38 parts of styrene-acrylic emulsion, 0.3 parts of bactericide, and 0.1 parts of mildew inhibitor to the mixing tank, and continue stirring for 15 min;

[0155] S4: Transfer the mixture in S3 to a planetary mill and grind it at 600 r / min for 30 min. Filter the mixture to obtain the radiation cooling coating with temperature response regulation function.

[0156] The radiation cooling filler is zinc oxide with a particle size D90 of 90 μm.

[0157] The radiation-cooling coating obtained in this comparative example has a solar reflectance of 0.93 and an average emissivity of 0.92 at an atmospheric window of 814 μm when the temperature is above the phase transition temperature; and a solar reflectance of 0.62 and an average emissivity of 0.63 at an atmospheric window of 814 μm when the temperature is below the phase transition temperature. After 30 minutes of infrared lamp irradiation, the glass plate coated with the coating of this invention is 49.2°C lower than the blank glass plate, and the heating rate is significantly slower when the temperature reaches 67.3°C. The contrast ratio is 0.93, the stain resistance is 8%, and the artificial weathering resistance is 600 hours without blistering, peeling, or cracking. After 90 days of outdoor placement, it no longer has temperature response function.

[0158] Comparative Example 3

[0159] In this comparative example, a radiation-cooling coating with temperature response regulation function is prepared from the following components in the following mass ratio: 27 parts of water-based polymer resin, 22 parts of radiation-cooling filler, 18 parts of titanium dioxide, 10 parts of tungsten-fluorine binary doped vanadium dioxide powder, 8 parts of functional additives, and 15 parts of diluent.

[0160] The preparation method of the radiation-cooling coating in this comparative example includes the following steps:

[0161] S1: Add 15 parts of deionized water to a vertical mixer with a dispersion plate, add 0.4 parts of hydroxyethyl cellulose to the water, stir at 800 r / min for 15 min until it is completely dispersed, then add 1.9 parts of alcohol ester dodecyl, 1.5 parts of dispersant, 0.9 parts of wetting agent, 1.8 parts of defoamer, and 1.2 parts of silane coupling agent in sequence, and continue to stir and disperse for more than 10 min;

[0162] S2: Add 10 parts of tungsten-fluorine binary doped vanadium dioxide powder, 22 parts of radiation cooling filler, and 18 parts of titanium dioxide to the mixing tank in sequence, increase the speed to 1200 r / min, and stir for 30 min until the powder is evenly dispersed.

[0163] S3: Reduce the speed to 600 r / min, add 27 parts of acrylic emulsion, 0.2 parts of bactericide, and 0.1 parts of mildew inhibitor to the mixing tank, and continue stirring for 15 min;

[0164] S4: Transfer the mixture in S3 to a planetary mill and grind it at 600 r / min for 30 min. Filter the mixture to obtain the radiation cooling coating with temperature response regulation function.

[0165] The tungsten-fluorine binary doped vanadium dioxide powder has a tungsten doping amount of 5.0 at, a fluorine doping amount of 5.0 at, and a particle size D90 of 20 μm.

[0166] The radiation cooling filler is a mixture of zirconium oxide and alumina, with a particle size D90 of 100 μm.

[0167] The sample in this embodiment was analyzed by EDS using a FEIApreo 2C & Bruker QUANTAX200 XFlash6|60 field emission scanning electron microscope-energy dispersive spectrometer. The distribution of V, O, W and F elements can be seen, indicating that W and F have been successfully incorporated into VO2, and their percentages are 5.02% and 4.89% respectively, which are close to the doping ratio.

[0168] The radiation-cooling coating obtained in this comparative example has a solar reflectance of 0.93 and an average emissivity of 0.93 at an atmospheric window of 814 μm when the temperature is above the phase transition temperature; and a solar reflectance of 0.44 and an average emissivity of 0.49 at an atmospheric window of 814 μm when the temperature is below the phase transition temperature. After 30 minutes of infrared lamp irradiation, the glass plate coated with the coating of this invention is 40.8°C lower than the blank glass plate, and the heating rate is significantly slower when the temperature reaches 27.1°C. The contrast ratio is 0.94, the stain resistance is 10%, and the artificial weathering resistance is 600 hours without blistering, peeling, or cracking. After 90 days of outdoor placement, it no longer has temperature response function.

[0169] The comparative examples 1-3 above further verified the temperature response function and long-term service advantage of tungsten, fluorine, and sulfur co-doped vanadium dioxide in this invention. Specifically, in Comparative Example 1, no vanadium dioxide powder was added, and the resulting coating showed no temperature response characteristics. In Comparative Example 2, undoped vanadium dioxide powder was used, and the resulting coating exhibited a sudden change in reflectivity and emissivity at 67.3℃, making it unsuitable for ordinary building exteriors. In Comparative Example 3, vanadium dioxide was doped with only tungsten and fluorine; although it possessed a transition temperature within the room temperature range, it lost its temperature response function within 90 days, indicating that sulfur doping is effective in extending service life.

[0170] The above description is only a partial embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A ternary co-doped V02 powder, characterized in that: The ternary co-doped vanadium dioxide powder contains 1.46-4.95 at% tungsten, 0.98-4.93 at% fluorine, and 0.48-0.54 at% sulfur.

2. A method for preparing a ternary co-doped V02 powder, characterized in that: The method comprises the following steps: mixing tungsten-fluorine-doped vanadium dioxide with sublimed sulfur powder, then immersing the mixed powder in ethanol, then adding alkyl benzene sulfonate or dodecyl sulfate, and then ultrasonicating for 30-60 min under a nitrogen atmosphere and at 50-60 ℃; then drying the mixture into a paste under the nitrogen atmosphere; then mechanically grinding the obtained paste at a speed of 800-1200 r / min for 15 min or more, and then drying under the nitrogen atmosphere to obtain the ternary co-doped vanadium dioxide powder; The atomic ratio of tungsten, fluorine and sublimed sulfur in the tungsten-fluorine-doped vanadium dioxide is 1.5-5:1-5:0.

5. The tungsten-fluorine-doped vanadium dioxide contains 1.5-5 at% tungsten and 1-5 at% fluorine. The mass ratio of alkyl benzene sulfonate or dodecyl sulfate to the sum of tungsten-fluorine-doped vanadium dioxide and sublimed sulfur powder is 3-5:1000.

3. A radiative cooling paint having a temperature response adjustment function, characterized by: The radiation cooling coating with temperature response adjustment function is prepared from the following components in the following mass ratio: The aqueous polymer resin is one or any combination of two or more of a silicone-acrylate emulsion, a styrene-acrylate emulsion, a polyurethane emulsion or an acrylic emulsion.

4. The radiative cooling coating with temperature-responsive regulation function according to claim 3, characterized in that: The radiation cooling filler comprises one or any combination of two or more of alumina, silica, zinc oxide or hydrogen magnesium phosphate with a particle size ranging from 1 to 100 μm.

5. The radiative cooling coating with temperature-responsive regulation function according to claim 3, characterized in that: The titanium white powder is rutile titanium dioxide with a particle size ranging from 0.5 to 1 μm.

6. The radiative cooling coating with temperature-responsive regulation function according to claim 3, characterized in that: The functional additive comprises one or any combination of two or more of a thickening agent, a dispersing agent, a wetting agent, an antifoaming agent, a coupling agent and a pH regulator.

7. The radiative cooling coating with temperature-responsive regulation function according to claim 3, characterized in that: The diluent is deionized water.

8. The radiative cooling coating with temperature-responsive regulation function according to claim 3, characterized in that: The method comprises the following steps:

9. The preparation method of the radiation-cooling coating with temperature response adjustment function according to any one of claims 3-8, characterized in that: (1) adding the diluent into a stirrer, and then adding the functional additive and stirring uniformly, (2) then adding the radiation cooling filler, the titanium white powder and the tungsten-fluorine-sulfur ternary doped vanadium dioxide powder and stirring uniformly; (3) then adding the aqueous polymer resin and stirring uniformly, (4) finally transferring the above materials to a grinder and grinding for 30 min or more, and then filtering to obtain the radiation cooling coating with temperature response adjustment function. The stirrer is a vertical stirrer with a dispersing disc, and the grinder is a planetary grinder.

10. The preparation method of the radiant cooling coating with temperature response adjustment function according to claim 9, characterized in that: ​