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CN113249091A - ATO (antimony tin oxide) coated cesium tungsten bronze composite nano powder and preparation method thereof - Google Patents

ATO (antimony tin oxide) coated cesium tungsten bronze composite nano powder and preparation method thereof Download PDF

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CN113249091A
CN113249091A CN202110545978.6A CN202110545978A CN113249091A CN 113249091 A CN113249091 A CN 113249091A CN 202110545978 A CN202110545978 A CN 202110545978A CN 113249091 A CN113249091 A CN 113249091A
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tungsten bronze
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CN113249091B (en
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吕鑫雨
谢亚东
薛宁
李明亚
王晓强
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Northeastern University Qinhuangdao
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Abstract

本发明的一种ATO包覆铯钨青铜复合纳米粉体及其制备方法，其中包覆层为掺锑二氧化锡ATO，复合纳米粉体的颗粒包括铯钨青铜内核和包覆所述铯钨青铜的掺锑二氧化锡ATO外壳，所述铯钨青铜内核的通式为CsxWO3，其中0.1≤x≤0.33。制备过程中通过在铯钨青铜表面包覆化学性质稳定的ATO，隔绝铯钨青铜内核与外界的水或氧气接触，提高了铯钨青铜的化学稳定性，并保持较好分散性，同时将ATO和铯钨青铜纳米粉CsxWO3的近红外吸收性能进行综合，在不影响铯钨青铜内核可见光高透过率及红外光高阻隔率性能基础上实现进一步提升，大幅优于现有红外阻隔涂料。An ATO-coated cesium tungsten bronze composite nano-powder and a preparation method thereof of the present invention, wherein the coating layer is antimony-doped tin dioxide ATO, and the particles of the composite nano-powder include a cesium tungsten bronze core and a coating of the cesium tungsten A bronze antimony-doped tin dioxide ATO shell, the general formula of the cesium tungsten bronze core is Cs x WO 3 , where 0.1≤x≤0.33. In the preparation process, the surface of cesium tungsten bronze is coated with chemically stable ATO, which isolates the core of cesium tungsten bronze from contact with water or oxygen outside, which improves the chemical stability of cesium tungsten bronze and maintains good dispersibility. Combined with the near-infrared absorption performance of cesium tungsten bronze nanopowder Cs x WO 3 , it can be further improved without affecting the high transmittance of visible light and high blocking rate of infrared light of the cesium tungsten bronze core, which is significantly better than the existing infrared blocking rate. coating.

Description

ATO (antimony tin oxide) coated cesium tungsten bronze composite nano powder and preparation method thereof
The technical field is as follows:
the invention belongs to the technical field of transparent heat-insulating powder, and particularly relates to ATO (antimony tin oxide) coated cesium tungsten bronze composite nano powder and a preparation method thereof.
Background art:
infrared is an electromagnetic wave having a wavelength between microwave and visible light, and the wavelength is 760nm to 2.5 mm. Infrared rays, particularly near infrared rays, have significant thermal effects, accounting for about half of the heat of solar radiation, and therefore need to be regulated in many fields. In the field of buildings, the infrared blocking glass/paint/sticking film can be used for reducing the heat radiated by near infrared rays, reducing the indoor temperature rise in summer and reducing the use amount of refrigeration equipment such as an air conditioner and the like, thereby achieving the purpose of saving energy. In the field of automobiles, the temperature in the automobile can be reduced by applying the infrared barrier glass/paint/film, so that the energy-saving purpose is achieved while the driving experience is better.
The inorganic materials with strong near infrared absorption or reflection properties reported at present mainly comprise noble metals (gold, silver, etc.), black compounds (ruthenium, rhodium and iridium-containing oxides), semiconductor oxides (FTO, AZO, ITO), rare earth hexaboride (PrB)6、NdB6、LaB6Etc.) and tungsten bronze-based functional materials. Such conductive oxide powders generally have a strong absorption capability for near infrared light having a wavelength of more than 1500 nm. In the tungsten bronze functional materials, cesium tungsten bronze has strong absorption capacity on near infrared light with the wavelength of 950nm to 1500nm, shows better stability and infrared absorption and photothermal conversion performance than other types of tungsten bronze, and becomes the mainstream of preparation and application.
Various documents show that cesium tungsten bronze (Cs) with excellent performance can be prepared by a traditional solid-phase reaction method, a gas-phase method or a solvothermal/hydrothermal methodxWO3) And (3) powder. The traditional solid phase reaction method has the advantages of simple operation, low capital investment and high yield, but the method can not control the morphology of the obtained product, has high agglomeration property and can be applied after ball milling secondary refinement. WO for Takeda H et al3·NH3As tungsten source, using M salt containing required metal elements as auxiliary raw materialMixing the two solutions, drying at 130 deg.C, and reacting in H2/N2Heating under mixed atmosphere of (1) and finally under N2Heating at 800 ℃ under the atmosphere to obtain a final product, and successfully preparing M0.33WO3(M ═ Na, Ti, Rb, Cs) and Na0.75WO3. The gas phase method can prepare nano materials with various shapes, but the method needs complicated experimental equipment, has higher requirements on experimental conditions and has large capital investment. In 1985, commercially available WO was used by M.Green and A.Travlos3Powder and metallic sodium are used as raw materials, the two raw materials are respectively heated, and sodium tungsten bronze (Na) is prepared by a co-evaporation methodxWO3) A film. The process for preparing the tungsten bronze by the solvent hot water thermal method is mature, the operation is simple, the equipment is simple, and various products with special shapes can be obtained. Guo C S and the like take ammonium paratungstate as a tungsten source, the ammonium paratungstate is dissolved in an ethylene glycol solution at 190 ℃, acetic acid is added after the solution is cooled to indoor temperature, and ammonium tungsten bronze is obtained by cleaning and drying after the solution reacts in a hydrothermal kettle at 200 ℃ for 72 h.
However, pure cesium tungsten bronze has insufficient absorption of infrared rays larger than 1500nm, has strong reducibility, and is easily oxidized at a high temperature. While cesium tungsten bronze is soluble in strongly alkaline solutions placed in an air atmosphere, as shown in the following equation.
2CsxWO3+x/2O2＝xCs2WO4+(2-x)WO3
2CsxWO3+(8-4x)NaOH+xO2＝4NaWO4+(4-2x)H2O
The invention content is as follows:
the invention aims to overcome the defect of insufficient stability of cesium tungsten bronze in the prior art, and provides antimony-doped tin dioxide ATO-coated cesium tungsten bronze composite nano powder which has excellent absorption performance and stability for infrared light with infrared wavelength of more than 1500nm and a preparation method thereof. Antimony-doped tin dioxide ATO coating is carried out on the surface of the cesium tungsten bronze, so that the chemical stability of the cesium tungsten bronze is improved. In addition, the nano powder keeps better dispersibility through the coating of the oxide layer. Moreover, the antimony-doped tin dioxide ATO coating can further improve the absorption capacity of the cesium tungsten bronze in an infrared light region with the wavelength of more than 1500nm under the condition of basically not influencing the high transmittance of visible light. The visible light transmission performance of the infrared barrier coating and the film prepared by the composite powder is well maintained by controlling the thickness and the uniformity of the oxide coating layer; when the composite powder is used for photo-thermal conversion, the photo-thermal conversion performance is enhanced due to the excellent sunlight absorption capacity of the oxide coating.
The preparation process comprises the following steps: mixing powder provided with a cesium source and a tungsten source, organic alcohol and organic acid, and then carrying out hydrothermal reaction to obtain a cesium tungsten bronze precursor solution, washing the cesium tungsten bronze precursor solution with deionized water and organic alcohol for three times, carrying out multiple centrifugal operations, drying in an oven to obtain cesium tungsten bronze powder, dissolving the cesium tungsten bronze powder in an alkaline alcohol solution or an aqueous solution, and then depositing an oxide shell on the surface of an inner core of the cesium tungsten bronze layer by a hydrolysis method to obtain the oxide-coated cesium tungsten bronze composite nano powder.
In order to achieve the purpose, the invention adopts the following technical scheme:
the particles of the composite nano powder comprise a cesium tungsten bronze core and an ATO shell coating the cesium tungsten bronze core, wherein the general formula of the cesium tungsten bronze core is CsxWO3Wherein x is more than or equal to 0.1 and less than or equal to 0.33, the cesium tungsten bronze kernel is a nanosphere, and the particle size of the nanosphere is 20-80 nm; the thickness of the ATO shell is less than or equal to 30nm, so that negative effects on the visible light transmittance of the composite nano powder caused by further thickening are avoided.
The core phase of the ATO-coated cesium tungsten bronze composite nano powder is hexagonal CsxWO3Cesium tungsten bronze phase, no impurity phase.
And (3) detecting chemical resistance stability: and respectively weighing 2g of the prepared ATO-coated cesium tungsten bronze composite nano powder, putting the powder into a sodium hydroxide solution with the pH value of 8 and a dilute hydrochloric acid solution with the pH value of 6, stirring for 24 hours, and washing and drying the powder. No phase change is detected by XRD. The powder is shown to have excellent chemical stability.
The preparation method of the ATO-coated cesium tungsten bronze composite nano powder comprises the following steps:
step 1, preparing a cesium tungsten bronze precursor:
(1) taking tungsten source powder and cesium source powder, and mixing the tungsten source powder and the cesium source powder according to a molar ratio: weighing the cesium source powder (0.3-1) by using an electronic balance, respectively dissolving the cesium source powder and the cesium source powder into a tungsten solution and a cesium solution, and uniformly mixing the tungsten solution and the cesium solution with an inducer to obtain a solution A, wherein the addition volume of the inducer is 15-25% of the sum of the volumes of the tungsten solution and the cesium solution;
(2) transferring the solution A into a hydrothermal kettle with the volume of 100ml, sealing the hydrothermal kettle for hydrothermal reaction at the temperature of 200-240 ℃ for 10-16 h;
(3) after the reaction is finished, taking out the precursor solution after the reaction kettle is cooled to room temperature;
step 2, preparing cesium tungsten bronze powder:
(1) washing the precursor solution with deionized water and absolute ethyl alcohol for three times, and performing multiple centrifugal operations;
(2) drying in an oven at 60 ℃ for 12h to obtain the dark blue cesium tungsten bronze nano powder CsxWO3。
Step 3, preparing ATO coated cesium tungsten bronze composite nano powder:
(1) dissolving cesium tungsten bronze nano powder in absolute ethyl alcohol, adding a dispersing agent accounting for 4-8% of the mass of the cesium tungsten bronze powder, and performing ultrasonic dispersion to form a stable suspension, wherein the ultrasonic power is 10 kHz-30 KHz, the temperature is 25-60 ℃, and the time is 20-120 min;
(2) by mol ratio, SnCl4Solution: SbCl31, uniformly mixing the solution (8-11) and the solution to obtain a clear mixed salt solution, and adjusting the pH value of the clear mixed salt solution to 8-10;
(3) under the condition that the oil bath temperature is 50-80 ℃, slowly dripping an ammonia water solution and a mixed salt solution into the stable suspension, and according to the mass ratio, mixing solutes in the mixed salt solution: and (3) adjusting the pH value of the system to be 2, stirring by using magnetic force in the reaction process to ensure that the system is uniform, curing for 2-4 h at 40-60 ℃ after precipitation is finished, and depositing the generated ATO on the surface of the inner core of the cesium tungsten bronze powder to form a coating layer to obtain the ATO-coated cesium tungsten bronze composite nano powder.
In the step 1(1), the tungsten source powder and the cesium source powder are both dissolved by using organic alcohol.
In the step 1 (1):
the cesium source is at least one selected from cesium sulfate, cesium chloride, cesium hydroxide and cesium carbonate, preferably cesium hydroxide;
the tungsten source is at least one selected from sodium tungstate, tungsten hexachloride, ammonium tungstate and ammonium metatungstate, and is preferably tungsten hexachloride;
the organic alcohol is at least one of ethanol, ethylene glycol, glycerol and benzyl alcohol;
the inducer is selected from at least one of glacial acetic acid, oleic acid, citric acid and ascorbic acid, preferably glacial acetic acid.
In the step 1(2), the cesium tungsten bronze core is formed through hydrothermal reaction based on the following chemical reaction formula:
CH3CH2OH+CH3COOH＝CH3CH2OOCCH3+H2O
2CH3CH2OH＝CH3CH2OCH2CH3+H2O
WCl6+3H2O＝WO3+6HCl
WO3+xCsOH+x/4C2H5OH＝CsxWO3+x/4CH3COOH+3x/4H2O
in the step 2 and 2, the cesium tungsten bronze nano-powder CsxWO3The particle size is 110 to 130 nm.
In the step 3(1), the dispersant is at least one selected from polyvinyl alcohol PVA, polyethylene glycol PEG, sodium dodecyl benzene sulfonate SDBS and cetyl trimethyl ammonium bromide CTAB, and preferably polyethylene glycol PEG.
In the step 3(3), ATO has the general formula SbxSnyO2Wherein x + y is 1, and y is 0.9-0.99.
In the step 3(3), the concentration of the ammonia water solution is 1-3 mol/L.
In the step 3(2), the SnCl4The solution concentration is 0.125mol/L, SbCl3The concentration of the solution was 0.167 mol/L.
In the step 3(2), the ATO-coated cesium tungsten bronze composite nano powder is used as an infrared barrier heat-insulation coating to prepare an infrared barrier heat-insulation film, the visible light transmittance of the infrared barrier heat-insulation film is 32.85% -79.80%, the absorption waveband of a near infrared region is 780-2500 nm, and the transmittance of the near infrared region is less than or equal to 32%, so that the infrared barrier heat-insulation film shows good combination of high visible light transmittance and high near infrared light absorption rate, specifically, the infrared barrier heat-insulation film has the transmittance of 75.20% -79.80% when the wavelength is 390nm, the transmittance of 32.85% -42.67% when the wavelength is 780nm, the transmittance of 23.04% -31.87% when the wavelength is 950nm, the transmittance of 11.03% -18.99% when the wavelength is 1500nm, and the transmittance of 8.00% -21.6% when the wavelength is 2500 nm.
The invention has the beneficial effects that:
according to the invention, the antimony-doped tin dioxide ATO-coated cesium tungsten bronze composite nano powder is prepared by a hydrothermal method and a chemical hydrolysis method in two steps, the process has the advantages of simplicity and convenience in control and simple process, and the prepared composite nano powder has excellent dispersibility and chemical stability and can be widely applied to infrared barrier energy-saving coatings and films.
The preparation method provided by the invention is convenient for controlling the phase of the formed product, simple and convenient in process, high in product yield and suitable for large-scale and low-cost production. The prepared composite powder has the outstanding advantages of excellent dispersion and high chemical stability. The composite powder can be widely used for preparing infrared barrier heat insulation coating or film.
Description of the drawings:
FIG. 1 is an X-ray diffraction (XRD) pattern of a cesium tungsten bronze core powder produced in example 1 of the present invention;
fig. 2 is a comparison graph of transmission spectra of the ATO-coated cesium tungsten bronze composite nano-powder prepared in example 1 of the present invention and the cesium tungsten bronze nano-material infrared blocking diaphragm.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples.
The oxide-coated cesium tungsten bronze composite nano powder (referred to as "composite nano powder", "nano powder" or "powder" for short) in one embodiment of the invention comprises a cesium tungsten bronze core and an antimony-doped tin dioxide ATO shell coating the cesium tungsten bronze core.
Cs is simultaneously taken as cesium tungsten bronze kernelxWO3Wherein x is more than or equal to 0.1 and less than or equal to 0.33. In this range, the higher the value of x, the stronger the absorption of infrared rays and the photothermal conversion of the powder. When the material is used in the infrared barrier energy-saving field (such as energy-saving paint and film), the maximum value of x is recommended.
The cesium tungsten bronze kernel is a nanosphere, and the particle size of the nanosphere is 20-80 nm.
In a preferable experimental mode, the thickness of the antimony-doped tin dioxide ATO shell is less than or equal to 30 nm. When the thickness is equal to the thickness, the antimony-doped tin dioxide ATO shell is transparent, so that the visible light transmission performance of the paint or film prepared by the composite powder is well maintained.
Specifically, the cesium tungsten bronze is prepared by a hydrothermal process based on a chemical reaction mechanism listed in the following formula, so that the process is simplified, the yield is high, and the cesium tungsten bronze is stably prepared.
CH3CH2OH+CH3COOH＝CH3CH2OOCCH3+H2O
2CH3CH2OH＝CH3CH2OCH2CH3+H2O
WCl6+3H2O＝WO3+6HCl
WO3+xCsOH+x/4C2H5OH＝CsxWO3+x/4CH3COOH+3x/4H2O
In the reaction of the present design, WCl6As an oxidant with other raw materials at high temperaturesUnder the hydrothermal action, a final cesium tungsten bronze phase is formed together. The WCl6Meanwhile, the cesium tungsten bronze reaction is a tungsten source, has a clear forming mechanism, can simplify the process, avoid the generation of byproducts, improve the yield, facilitate the control of the reaction and improve the reaction stability.
Compared with the existing preparation method using cesium oxide as a reducing agent, the cesium source (cesium hydroxide) in the formula as a reducing agent avoids the problem that the cesium oxide is relatively active and is easy to react with water, carbon dioxide and the like in the air to influence the metering and operation.
In some embodiments, the cesium source can be selected from at least one of cesium sulfate, cesium chloride, cesium hydroxide, cesium carbonate. Under the condition of keeping equivalent substance equivalent, the raw materials can be randomly combined based on the principle shown by the chemical reaction formula, and the synthesis of the cesium tungsten bronze powder is not influenced.
The concentration of each raw material in the reaction system may be selected according to the desired concentration of the finally formed product. The concentration of the final product formed has an effect on the dispersibility and particle size of the powder. Preferably, the concentration of the formed product is 30% or less, so that the dispersibility of the powder is better and the particle size distribution is more uniform. More preferably, the concentration of the formed product is 10-20%.
The hydrothermal synthesis temperature of the synthesized cesium tungsten bronze is 220 ℃, and the synthesis time is 12 h. When the hydrothermal synthesis temperature is increased, the time for its formation is shortened.
Based on the mechanism disclosed by the invention and shown by the chemical reaction equation, under the selected synthesis conditions, the materials are preferably prepared according to the stoichiometric ratio, and the yield of the obtained product is close to the theoretical value. Therefore, the concentration of the product in the reaction system and the yield of the cesium tungsten bronze powder can be controlled.
The test result shows that the conversion rate of the tungsten bronze after the hydrothermal reaction is more than or equal to 99 percent.
In one embodiment of the invention, the preparation of the oxide-coated cesium tungsten bronze composite nano powder by a hydrothermal method and a chemical hydrolysis method mainly comprises the following steps.
Preparing a cesium tungsten bronze precursor:
(1) weighing tungsten hexachloride and cesium hydroxide powder according to a molar ratio of 3:1 by using an electronic balance, and uniformly mixing to obtain a solution A;
(2) transferring the solution A into a hydrothermal kettle with the volume of 100ml, sealing, heating at 220 ℃, and reacting for 12 hours;
(3) and after the reaction is finished, taking out the precursor solution after the reaction kettle is cooled to room temperature.
Preparation of cesium tungsten bronze powder:
(1) washing the obtained precursor solution with deionized water and absolute ethyl alcohol for three times, and performing multiple centrifugal operations;
(2) drying in an oven at 60 deg.C for 12h to obtain dark blue nanometer Cs0.33WO3Powder samples.
Preparing an antimony-doped tin dioxide ATO-coated cesium tungsten bronze composite nano material:
(1) the obtained cesium tungsten bronze powder and one of the dispersants were dissolved in anhydrous ethanol and subjected to ultrasonic dispersion to form a stable suspension. And (3) simultaneously dropwise adding a coating oxide salt and ammonia water into the suspension, and adjusting the pH value of the suspension to deposit the oxide on the surface of the cesium tungsten bronze core to form a coating.
The composite nano material can be applied to infrared barrier heat insulation coatings. The infrared barrier thermal insulation coating can be used for forming an infrared barrier thermal insulation film.
The present invention will be described in detail below with reference to examples. It will also be understood that the following examples are included to further illustrate the present invention and are not to be construed as limiting the scope of the invention, which is intended to include the insubstantial modifications and adaptations of those skilled in the art in view of the foregoing description of the invention. In the following, the example specific process parameters are also only an example of suitable ranges, i.e. a person skilled in the art can select from the suitable ranges by the description herein, and are not limited to the specific values exemplified below.
Example 1:
1.5mmol of WCl6Dissolving in 40ml of absolute ethanol at room temperatureMagnetic stirring was performed for 10min to give a yellow solution. In a separate beaker, 0.5mmol CsOH. H2O is dispersed in 20ml of absolute ethanol. The obtained cesium hydroxide alcohol solution and 12ml of glacial acetic acid were added to a tungsten hexachloride alcohol solution to obtain a yellow solution. Pouring the solution into a hydrothermal reaction kettle, heating to 220 ℃, and reacting for 12 h. And after the reaction is finished, taking out the precursor solution after the reaction kettle is cooled to room temperature. Washing the obtained precursor solution with deionized water and absolute ethyl alcohol for three times, and performing multiple centrifugal operations; drying in an oven at 60 deg.C for 12h to obtain dark blue nanometer Cs0.33WO3The particle size of the powder sample is 110-130 nm.
Dispersing 2g of the cesium tungsten bronze powder in absolute ethyl alcohol, adding a dispersant polyethylene glycol (PEG) with the mass fraction of 5%, fully stirring, performing ultrasonic dispersion for 1h at the temperature of 40 ℃ at 25kHZ to obtain uniform and stable suspension, and taking SnCl with the concentration of 0.125mol/L and the concentration of 0.167mol/L respectively in the ratio of 10:14And SbCl3And (2) mixing the solutions to obtain a uniform and clear mixed salt solution, keeping the pH value of the mixed salt solution at 9, simultaneously and slowly dripping 2mol/L of ammonia water solution and the mixed salt solution into the suspension at the oil bath temperature of 60 ℃, keeping the pH value of the system at 2, and mixing solute in the mixed salt solution: cesium tungsten bronze powder is equal to 0.5, magnetic stirring is used in the reaction process to ensure the system to be uniform, the antimony-doped tin dioxide ATO-coated cesium tungsten bronze composite nano powder is collected, and the ATO component is Sb0.09Sn0..91O2。
FIG. 1 is a powder X-ray diffraction (XRD) pattern of the powder thus prepared. As can be seen from FIG. 1, the resulting phase is hexagonal Cs0.33WO3Cesium tungsten bronze phase, no other miscellaneous phases were detected. The result of inductively coupled plasma mass spectrometry on the supernatant is WO3The content is 0.066 wt%, which shows that the conversion rate of tungsten bronze is more than or equal to 99% after the hydrothermal reaction.
Fig. 2 is a graph comparing the transmittance spectra of the ATO-coated cesium tungsten bronze composite nanopowder and the cesium tungsten bronze core prepared in this example, wherein the transmittance of the composite nanopowder is 79.80% at a wavelength of 390nm, 38.53% at a wavelength of 780nm, 23.04% at a wavelength of 950nm, 12.00% at a wavelength of 1500nm, and 8.00% at a wavelength of 2500 nm.
The particle size of the composite nano powder obtained in the embodiment is 20-45 nm. 2g of the prepared zinc oxide coated cesium tungsten bronze composite nano material is respectively weighed and put into a sodium hydroxide solution with the pH value of 8 and a dilute hydrochloric acid solution with the pH value of 6, and after stirring for 24 hours, the powder is washed and dried. The phase is unchanged by XRD detection. The powder is shown to have excellent chemical stability.
Example 2:
1.5mmol WCl6Dissolved in 40ml of absolute ethanol and magnetically stirred at room temperature for 10min to give a yellow solution. In a separate beaker, 0.25mmoCsOH & H2O is dispersed in 20ml of absolute ethanol. The obtained cesium hydroxide alcohol solution and 12ml of glacial acetic acid were added to a tungsten hexachloride alcohol solution to obtain a yellow solution. Pouring the solution into a hydrothermal reaction kettle, heating to 240 ℃, and reacting for 10 h. And after the reaction is finished, taking out the precursor solution after the reaction kettle is cooled to room temperature. Washing the obtained precursor solution with deionized water and absolute ethyl alcohol for three times, and performing multiple centrifugal operations; drying in an oven at 60 deg.C for 12h to obtain dark blue nanometer Cs0.17WO3The particle size of the powder sample is 110-130 nm.
Dispersing 2g of the cesium tungsten bronze powder in absolute ethyl alcohol, adding 5% by mass of dispersant polyethylene glycol (PEG), fully stirring at the temperature of 40 ℃ at 25kHZ, performing ultrasonic dispersion for 1h to obtain uniform and stable suspension, and taking SnCl with the concentration of 0.125mol/L and 0.167mol/L respectively in the proportion of 10.5:14And SbCl3And (2) mixing the solutions to obtain a uniform and clear mixed salt solution, keeping the pH value of the mixed salt solution at 8, simultaneously and slowly dropwise adding 2mol/L of ammonia water solution and the mixed salt solution into the suspension at the oil bath temperature of 60 ℃, keeping the pH value of the system at 2, and keeping solute in the mixed salt solution: cesium tungsten bronze powder is equal to 0.5, magnetic stirring is used in the reaction process to ensure the system to be uniform, the antimony-doped tin dioxide ATO-coated cesium tungsten bronze composite nano powder is collected, and the ATO component is Sb0.05Sn0..95O2。
The particle size of the composite nano powder obtained in the embodiment is 25-50 nm. Inductively coupled plasma is performed on the supernatantThe result of mass spectrometry was WO3The content is 0.066 wt%, which shows that the conversion rate of tungsten bronze is more than or equal to 99% after the hydrothermal reaction. The chemical resistance was similar to that of example 1, but the near infrared ray absorption performance of the composite nanomaterial of this example was reduced due to the reduced content of Cs and Sb.
Wherein the composite powder has a transmittance of 75.20% at a wavelength of 390nm, a transmittance of 32.85% at a wavelength of 780nm, a transmittance of 31.87% at a wavelength of 950nm, a transmittance of 18.99% at a wavelength of 1500nm, and a transmittance of 21.6% at a wavelength of 2500 nm.
Example 3
1.5mmol of WCl6Dissolved in 40ml of absolute ethanol and magnetically stirred at room temperature for 10min to give a yellow solution. In a separate beaker, 0.375mmol CsOH. H2O is dispersed in 20ml of absolute ethanol. The obtained cesium hydroxide alcohol solution and 12ml of glacial acetic acid were added to a tungsten hexachloride alcohol solution to obtain a yellow solution. Pouring the solution into a hydrothermal reaction kettle, heating to 240 ℃, and reacting for 10 h. And after the reaction is finished, taking out the precursor solution after the reaction kettle is cooled to room temperature. Washing the obtained precursor solution with deionized water and absolute ethyl alcohol for three times, and performing multiple centrifugal operations; drying in an oven at 60 deg.C for 12h to obtain dark blue nanometer Cs0.25WO3The particle size of the powder sample is 110-130 nm.
Dispersing 2g of the cesium tungsten bronze powder in absolute ethyl alcohol, adding a dispersant polyethylene glycol (PEG) with the mass fraction of 5%, fully stirring, performing ultrasonic dispersion for 1h at the temperature of 40 ℃ at 25kHZ to obtain uniform and stable suspension, and taking SnCl with the concentration of 0.125mol/L and the concentration of 0.167mol/L respectively in the ratio of 10:14And SbCl3And (2) mixing the solutions to obtain a uniform and clear mixed salt solution, keeping the pH value of the mixed salt solution at 9, simultaneously and slowly dropwise adding 2mol/L of ammonia water solution and the mixed salt solution into the suspension at the oil bath temperature of 60 ℃, keeping the pH value of the system at 2, and keeping solute in the mixed salt solution: cesium tungsten bronze powder is equal to 0.5, magnetic stirring is used in the reaction process to ensure the system to be uniform, the antimony-doped tin dioxide ATO-coated cesium tungsten bronze composite nano powder is collected, and the ATO component is Sb0.09Sn0..91O2。
This implementationIn the examples, the particle size of the obtained composite nanopowder is 25 to 50 nm. The result of inductively coupled plasma mass spectrometry on the supernatant is WO3The content is 0.066 wt%, which shows that the conversion rate of tungsten bronze is more than or equal to 99% after the hydrothermal reaction. The chemical resistance is similar to that of example 1, but the composite nanomaterial of this example has a reduced visible light transmittance due to the reduced Cs content compared to example 1.
Wherein the composite powder has a transmittance of 77.32% at a wavelength of 390nm, a transmittance of 35.94% at a wavelength of 780nm, a transmittance of 26.88% at a wavelength of 950nm, a transmittance of 16.07% at a wavelength of 1500nm, and a transmittance of 9.66% at a wavelength of 2500 nm.
Example 4
1.5mmol of WCl6Dissolved in 40ml of absolute ethanol and magnetically stirred at room temperature for 10min to give a yellow solution. In a separate beaker, 0.5mmol CsOH. H2O is dispersed in 25ml of absolute ethanol. The obtained cesium hydroxide alcohol solution and 13ml of glacial acetic acid were added to a tungsten hexachloride alcohol solution to obtain a yellow solution. Pouring the solution into a hydrothermal reaction kettle, heating to 220 ℃, and reacting for 12 h. And after the reaction is finished, taking out the precursor solution after the reaction kettle is cooled to room temperature. Washing the obtained precursor solution with deionized water and absolute ethyl alcohol for three times, and performing multiple centrifugal operations; drying in an oven at 60 deg.C for 12h to obtain dark blue nanometer Cs0.33WO3The particle size of the powder sample is 110-130 nm.
Dispersing 2g of the cesium tungsten bronze powder in absolute ethyl alcohol, adding a dispersant polyethylene glycol (PEG) with the mass fraction of 5%, fully stirring, performing ultrasonic dispersion for 40min at the temperature of 40 ℃ at 25kHZ to obtain a suspension, and taking SnCl with the concentration of 0.125mol/L and 0.167mol/L respectively in the proportion of 10:14And SbCl3And (2) mixing the solutions to obtain a uniform and clear mixed salt solution, keeping the pH value of the mixed salt solution at 9, simultaneously and slowly dropwise adding 2mol/L of ammonia water solution and the mixed salt solution into the suspension at the oil bath temperature of 60 ℃, keeping the pH value of the system at 2, and keeping solute in the mixed salt solution: cesium tungsten bronze powder is equal to 0.55, magnetic stirring is used in the reaction process to ensure the system to be uniform, the antimony-doped tin dioxide ATO-coated cesium tungsten bronze composite nano-powder is collected, and the ATO component is Sb0.09Sn0..91O2。
The particle size of the composite nano powder obtained in the embodiment is 25-55 nm. The result of inductively coupled plasma mass spectrometry on the supernatant is WO3The content is 0.066 wt%, which shows that the conversion rate of tungsten bronze is more than or equal to 99% after the hydrothermal reaction. The chemical resistance is similar to that of example 1, but the agglomeration phenomenon of the cesium tungsten bronze core is not well improved due to the short ultrasonic dispersion time, and the visible light transmission performance of the composite nano material of the example is reduced.
Wherein the composite powder has a transmittance of 76.22% at a wavelength of 390nm, a transmittance of 34.99% at a wavelength of 780nm, a transmittance of 26.95% at a wavelength of 950nm, a transmittance of 14.08% at a wavelength of 1500nm, and a transmittance of 9.30% at a wavelength of 2500 nm.
Example 5
1.5mmol of WCl6Dissolved in 40ml of absolute ethanol and magnetically stirred at room temperature for 10min to give a yellow solution. In a separate beaker, 0.5mmol CsOH. H2O is dispersed in 20ml of absolute ethanol. The obtained cesium hydroxide alcohol solution and 12ml of glacial acetic acid were added to a tungsten hexachloride alcohol solution to obtain a yellow solution. Pouring the solution into a hydrothermal reaction kettle, heating to 220 ℃, and reacting for 12 h. And after the reaction is finished, taking out the precursor solution after the reaction kettle is cooled to room temperature. Washing the obtained precursor solution with deionized water and absolute ethyl alcohol for three times, and performing multiple centrifugal operations; drying in an oven at 60 deg.C for 12h to obtain dark blue nanometer Cs0.33WO3The particle size of the powder sample is 110-130 nm.
Dispersing 2g of the cesium tungsten bronze powder in absolute ethyl alcohol, adding a dispersant polyvinyl alcohol PVA with the mass fraction of 5%, fully stirring, performing ultrasonic dispersion for 1h at the temperature of 40 ℃ at 25kHZ to obtain a uniform and stable suspension, and taking SnCl with the concentration of 0.125mol/L and 0.167mol/L respectively in the proportion of 10:14And SbCl3And (2) mixing the solutions to obtain a uniform and clear mixed salt solution, keeping the pH value of the mixed salt solution at 9, simultaneously and slowly dropwise adding 2mol/L of ammonia water solution and the mixed salt solution into the suspension at the oil bath temperature of 60 ℃, keeping the pH value of the system at 2, and keeping solute in the mixed salt solution: cesium tungsten bronze powder 0.5Magnetic stirring is used in the reaction process to ensure the system to be uniform, and the antimony-doped stannic oxide ATO-coated cesium tungsten bronze composite nano-powder is collected, wherein the ATO component is Sb0.09Sn0..91O2。
The particle size of the composite nano powder obtained in the embodiment is 30-50 nm. The result of inductively coupled plasma mass spectrometry on the supernatant is WO3The content is 0.066 wt%, which shows that the conversion rate of tungsten bronze is more than or equal to 99% after the hydrothermal reaction. Chemical resistance was similar to example 1.
Wherein the composite powder has a transmittance of 78.63% at a wavelength of 390nm, a transmittance of 42.67% at a wavelength of 780nm, a transmittance of 24.01% at a wavelength of 950nm, a transmittance of 11.03% at a wavelength of 1500nm, and a transmittance of 8.16% at a wavelength of 2500 nm.
Comparative example 1:
1.5mmol WCl6Dissolved in 40ml of absolute ethanol and magnetically stirred at room temperature for 10min to give a yellow solution. In a separate beaker, 0.15mmoCsOH & H2O is dispersed in 20ml of absolute ethanol. The obtained cesium hydroxide alcohol solution and 12ml of glacial acetic acid were added to a tungsten hexachloride alcohol solution to obtain a yellow solution. Pouring the solution into a hydrothermal reaction kettle, heating to 220 ℃, and reacting for 10 hours. And after the reaction is finished, taking out the precursor solution after the reaction kettle is cooled to room temperature. Washing the obtained precursor solution with deionized water and absolute ethyl alcohol for three times, and performing multiple centrifugal operations; drying in an oven at 60 deg.C for 12h to obtain dark blue nanometer Cs0.1WO3Powder samples.
Dispersing 2g of the cesium tungsten bronze powder in absolute ethyl alcohol, adding 5% polyvinyl alcohol PVA by mass, fully stirring at 25kHZ and 40 ℃, ultrasonically dispersing for 1h to obtain uniform and stable suspension, and taking SnCl with the concentration of 0.125mol/L and 0.167mol/L respectively in a ratio of 10:14And SbCl3And (2) mixing the solutions to obtain a uniform and clear mixed salt solution, keeping the pH value of the mixed salt solution at 9, simultaneously and slowly dropwise adding 2mol/L of ammonia water solution and the mixed salt solution into the suspension at the oil bath temperature of 60 ℃, keeping the pH value of the system at 2, and keeping solute in the mixed salt solution: cesium tungsten bronze powder (0.5) is magnetically stirred during the reactionThe system is uniform, and the antimony-doped tin dioxide ATO-coated cesium tungsten bronze composite nano-powder is collected, wherein the ATO component is Sb0.09Sn0..91O2。
The particle size of the composite nano powder obtained in the embodiment is 25-50 nm. The result of inductively coupled plasma mass spectrometry on the supernatant is WO3The content is 0.066 wt%, which shows that the conversion rate of tungsten bronze is more than or equal to 99% after the hydrothermal reaction. The chemical resistance is similar to that of example 1, but the near infrared ray absorption performance of the composite nanomaterial of this example is poor due to the decreased contents of Cs and Sb.
Wherein the composite powder has a transmittance of 68.50% at a wavelength of 390nm, a transmittance of 25.62% at a wavelength of 780nm, a transmittance of 39.91% at a wavelength of 950nm, a transmittance of 26.09% at a wavelength of 1500nm, and a transmittance of 33.96% at a wavelength of 2500 nm.
Comparative example 2
1.5mmol of WCl6Dissolved in 40ml of absolute ethanol and magnetically stirred at room temperature for 10min to give a yellow solution. In a separate beaker, 0.5mmol CsOH. H2O is dispersed in 25ml of absolute ethanol. The obtained cesium hydroxide alcohol solution and 13ml of glacial acetic acid were added to a tungsten hexachloride alcohol solution to obtain a yellow solution. Pouring the solution into a hydrothermal reaction kettle, heating to 220 ℃, and reacting for 12 h. And after the reaction is finished, taking out the precursor solution after the reaction kettle is cooled to room temperature. Washing the obtained precursor solution with deionized water and absolute ethyl alcohol for three times, and performing multiple centrifugal operations; drying in an oven at 60 deg.C for 12h to obtain dark blue nanometer Cs0.33WO3Powder samples.
Dispersing 2g of the cesium tungsten bronze powder in absolute ethyl alcohol, adding 5% by mass of dispersant polyethylene glycol (PEG), fully stirring at the temperature of 40 ℃ at 25kHZ, performing ultrasonic dispersion for 1h to obtain uniform and stable suspension, and taking SnCl with the concentration of 0.125mol/L and 0.167mol/L respectively in the ratio of 15:14And SbCl3Mixing the solutions to obtain a uniform and clear mixed salt solution, keeping the pH value of the solution to be 9, simultaneously and slowly dripping 2mol/L of ammonia water solution and the mixed salt solution into the suspension at the oil bath temperature of 60 ℃, keeping the pH value of the system to be 2, and dissolving the mixed salt solution into the suspensionQuality: cesium tungsten bronze powder is equal to 0.5, magnetic stirring is used in the reaction process to ensure the system to be uniform, the antimony-doped tin dioxide ATO-coated cesium tungsten bronze composite nano powder is collected, and the ATO component is Sb0.06Sn0..94O2。
The particle size of the composite nano powder obtained in the embodiment is 30-50 nm. Wherein the composite powder has a transmittance of 67.56% at a wavelength of 390nm, a transmittance of 30.78% at a wavelength of 780nm, a transmittance of 29.68% at a wavelength of 950nm, a transmittance of 25.63% at a wavelength of 1500nm, and a transmittance of 31.96% at a wavelength of 2500 nm.
Comparative example 3
1.5mmol of WCl6Dissolved in 40ml of absolute ethanol and magnetically stirred at room temperature for 10min to give a yellow solution. In a separate beaker, 0.5mmol CsOH. H2O is dispersed in 20ml of absolute ethanol. The obtained cesium hydroxide alcohol solution and 12ml of glacial acetic acid were added to a tungsten hexachloride alcohol solution to obtain a yellow solution. Pouring the solution into a hydrothermal reaction kettle, heating to 220 ℃, and reacting for 12 h. And after the reaction is finished, taking out the precursor solution after the reaction kettle is cooled to room temperature. Washing the obtained precursor solution with deionized water and absolute ethyl alcohol for three times, and performing multiple centrifugal operations; drying in an oven at 60 deg.C for 12h to obtain dark blue nanometer Cs0.33WO3Powder samples.
Dispersing 2g of the cesium tungsten bronze powder in absolute ethyl alcohol, adding a dispersant polyethylene glycol (PEG) with the mass fraction of 5%, fully stirring, performing ultrasonic dispersion for 1h at the temperature of 40 ℃ at 8kHZ to obtain uniform and stable suspension, and taking SnCl with the concentration of 0.125mol/L and the concentration of 0.167mol/L respectively in the ratio of 10:14And SbCl3And (2) mixing the solutions to obtain a uniform and clear mixed salt solution, keeping the pH value of the mixed salt solution at 9, simultaneously and slowly dropwise adding 2mol/L of ammonia water solution and the mixed salt solution into the suspension at the oil bath temperature of 60 ℃, keeping the pH value of the system at 2, and keeping solute in the mixed salt solution: cesium tungsten bronze powder is equal to 0.55, magnetic stirring is used in the reaction process to ensure the system to be uniform, the antimony-doped tin dioxide ATO-coated cesium tungsten bronze composite nano-powder is collected, and the ATO component is Sb0.09Sn0..91O2。
The particle size of the composite nano powder obtained in the embodiment is 35-60 nm. Due to the fact that the frequency is low in ultrasonic dispersion, the cesium tungsten bronze nanoparticles still have an agglomeration phenomenon, good monodispersity of only one cesium tungsten bronze core in a cladding layer cannot be guaranteed, the transmittance of the composite powder is 58.64% when the wavelength is 390nm, 33.52% when the wavelength is 780nm, 29.01% when the wavelength is 950nm, 20.33% when the wavelength is 1500nm, and 22.81% when the wavelength is 2500 nm.

Claims (8)

1. The ATO-coated cesium tungsten bronze composite nano powder is characterized by comprising a cesium tungsten bronze core and an ATO shell coating the cesium tungsten bronze core, wherein the general formula of the cesium tungsten bronze core is CsxWO3Wherein x is more than or equal to 0.1 and less than or equal to 0.33, the cesium tungsten bronze kernel is a nanosphere, and the particle size of the nanosphere is 20-80 nm; the thickness of the ATO shell is less than or equal to 30 nm.
2. The ATO-coated cesium tungsten bronze composite nanopowder of claim 1, wherein said ATO-coated cesium tungsten bronze composite nanopowder has a core phase of hexagonal CsxWO3Cesium tungsten bronze phase, no impurity phase.
3. The preparation method of ATO coated cesium tungsten bronze composite nanopowder as recited in claim 1, characterized by comprising the steps of:
step 1, preparing a cesium tungsten bronze precursor:
(1) taking tungsten source powder and cesium source powder, and mixing the tungsten source powder and the cesium source powder according to a molar ratio: weighing the cesium source powder (0.3-1) by using an electronic balance, respectively dissolving the cesium source powder and the cesium source powder into a tungsten solution and a cesium solution, and uniformly mixing the tungsten solution and the cesium solution with an inducer to obtain a solution A, wherein the addition volume of the inducer is 15-25% of the sum of the volumes of the tungsten solution and the cesium solution;
(2) transferring the solution A into a hydrothermal kettle with the volume of 100ml, sealing the hydrothermal kettle for hydrothermal reaction at the temperature of 200-240 ℃ for 10-16 h;
(3) after the reaction is finished, taking out the precursor solution after the reaction kettle is cooled to room temperature;
step 2, preparing cesium tungsten bronze powder:
(1) washing the precursor solution with deionized water and absolute ethyl alcohol for three times, and performing multiple centrifugal operations;
(2) drying in an oven at 60 ℃ for 12h to obtain the dark blue cesium tungsten bronze nano powder CsxWO3；
Step 3, preparing ATO coated cesium tungsten bronze composite nano powder:
(1) dissolving cesium tungsten bronze nano powder in absolute ethyl alcohol, adding a dispersing agent accounting for 4-8% of the mass of the cesium tungsten bronze powder, and performing ultrasonic dispersion to form a stable suspension, wherein the ultrasonic power is 10 kHz-30 KHz, the temperature is 25-60 ℃, and the time is 20-120 min;
(2) by mol ratio, SnCl4Solution: SbCl31, uniformly mixing the solution (8-11) and the solution to obtain a clear mixed salt solution, and adjusting the pH value of the clear mixed salt solution to 8-10;
(3) under the condition that the oil bath temperature is 50-80 ℃, slowly dripping an ammonia water solution and a mixed salt solution into the stable suspension, and according to the mass ratio, mixing solutes in the mixed salt solution: and (3) adjusting the pH value of the system to be 2, stirring by using magnetic force in the reaction process to ensure that the system is uniform, curing for 2-4 h at 40-60 ℃ after precipitation is finished, and depositing the generated ATO on the surface of the inner core of the cesium tungsten bronze powder to form a coating layer to obtain the ATO-coated cesium tungsten bronze composite nano powder.
4. The method for preparing ATO-coated cesium tungsten bronze composite nanopowder according to claim 3, wherein in said step 1 (1):
the cesium source is at least one of cesium sulfate, cesium chloride, cesium hydroxide and cesium carbonate;
the tungsten source is at least one of sodium tungstate, tungsten hexachloride, ammonium tungstate and ammonium metatungstate;
the inducer is at least one selected from glacial acetic acid, oleic acid, citric acid and ascorbic acid.
5. According to claim 3The preparation method of the ATO-coated cesium tungsten bronze composite nano powder is characterized in that in the step 2(2), the cesium tungsten bronze nano powder CsxWO3The particle size is 110 to 130 nm.
6. The method for preparing ATO-coated cesium tungsten bronze composite nanopowder according to claim 3, wherein in said step 3(1), the dispersant is selected from at least one of polyvinyl alcohol (PVA), polyethylene glycol (PEG), Sodium Dodecyl Benzene Sulfonate (SDBS), Cetyl Trimethyl Ammonium Bromide (CTAB).
7. The method for preparing ATO-coated cesium tungsten bronze composite nanopowder according to claim 3, wherein in step 3(3), ATO has a general formula of SbxSnyO2Wherein x + y is 1, and y is 0.9-0.99.
8. The method for preparing ATO-coated cesium tungsten bronze composite nanopowder according to claim 3, wherein in the step 3(2), ATO-coated cesium tungsten bronze composite nanopowder is used as an infrared barrier thermal insulation coating to prepare an infrared barrier thermal insulation film, the infrared barrier thermal insulation film has a visible light transmittance of 32.85% -79.80%, a near infrared absorption band of 780-2500 nm, and a near infrared transmittance of less than or equal to 32%, and specifically, the infrared barrier thermal insulation film has a transmittance of 75.20% -79.80% at a wavelength of 390nm, a transmittance of 32.85% -42.67% at a wavelength of 780nm, a transmittance of 23.04% -31.87% at a wavelength of 950nm, a transmittance of 11.03% -18.99% at a wavelength of 1500nm, and a transmittance of 8.00% -21.6% at a wavelength of 2500 nm.
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