Method for industrially preparing nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salt

Abstract

The present invention discloses a method for industrially preparing nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salt, as well as the application of the nano-alkali metal tungsten bronze coating. The method of the present invention uses one-step low-temperature heating hydrolysis to synthesize nano-alkali metal tungsten bronze. The preparation process does not require special equipment, does not require high temperature and high pressure, has mild process conditions, low energy consumption, short cycle, high output, high yield and low cost. The synthesized product has good crystallinity, and is Cs X WO3, Rb X WO3, K X WO3, Na X WO3, where X = 0.2 to 0.33. The length of the synthesized short rod-shaped alkali metal tungsten bronze particles is 10 to 150 nm, and the diameter is 10 to 50 nm. The sizes of the synthesized equiaxial alkali metal tungsten bronze in all directions are less than 100 nm. The above powders all have excellent near-infrared shielding performance, visible light transmittance, good ultraviolet shielding performance and certain mid- and far-infrared shielding performance. The preparation process of the nano-alkali metal tungsten bronze coating prepared by the present invention is simple and controllable, and has high near-infrared shielding performance and excellent ultraviolet shielding performance.

Description

Technical Field

[0001] The present invention relates to alkali metal tungsten bronze nanomaterials, and more particularly to a method for industrially preparing nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salt, and the application of the prepared nano-alkali metal tungsten bronze on building decoration curtain walls to achieve heat insulation and cooling performance. Background Art

[0002] Alkali metal tungsten bronze is a typical non-stoichiometric compound with the chemical formula M X WO3 (0 ≤ X ≤ 0.33). Due to its special one-dimensional tunnel structure marked by six-membered rings and mixed-valence W ions, it endows many excellent physical and chemical properties, such as photothermal conversion, selective light absorption, near-infrared shielding, etc., making it have broad application prospects in the fields of energy, military, construction, medical treatment, etc.

[0003] With the wide application of alkali metal tungsten bronze nanomaterials, its preparation technology has become increasingly important. At present, the preparation of alkali metal tungsten bronze powder mainly includes:

[0004] Solid-phase method. The solid-phase method usually mixes elemental metals, oxides or salts with tungsten and tungsten oxides, and under conditions such as higher temperature, pressure or ball milling, through solid-phase reaction, different types of alkali metal tungsten bronze are obtained. However, the alkali metal tungsten bronze synthesized by this method is difficult to control the morphology, and the product particle size is relatively large.

[0005] Wet chemical method. The wet chemical method mainly includes: solvothermal method and hydrothermal method. The wet chemical method has mild synthesis conditions, simple operation, and relatively controllable product size and morphology. The particle size distribution of the alkali metal tungsten bronze nanopowders prepared by the wet chemical method is narrow, the powder agglomeration degree is light, and there is no need for high-temperature annealing treatment in a reducing atmosphere. However, the concentration of the reactants is low, and both the reaction temperature and pressure are relatively high. The synthesis process requires special equipment (reaction kettle), the reaction has certain risks, the reaction time is long, and the single output is extremely low, which is not easy for industrial production.

[0006] In addition, the high-temperature reduction method requires introducing hydrogen during the high-temperature heating (800 °C) process, the preparation process is cumbersome, the utilization rate of raw materials is low, and it has certain risks (H. Takeda, K. Adachi, J. Am. Ceramic Soc., 2007, 90(12), 4059-4061). Solvothermal or hydrothermal reactions also require relatively high reaction temperatures (usually above 200 °C), the preparation time is long, requiring more than ten hours or even several days (C. Guo, S. Yin, M. Yan, T. Sato, J. Mater. Chem., 2011, 21(13), 5099).

[0007] Architectural decorative curtain walls are lightweight walls with decorative effects commonly used in modern large-scale and high-rise buildings. Due to limitations in materials and processing technology, curtain walls have not been able to meet requirements such as thermal physical factors (thermal radiation, condensation), sound insulation, and fire prevention, and thus have not been well developed and promoted. Nowadays, due to the combination of curtain wall technology and science and technology, in response to the global call for energy conservation and emission reduction, intelligent curtain walls, such as glass curtain walls, solar photovoltaic curtain walls, ventilation duct breathing curtain walls, and intelligent wind and rain sensing curtain walls, will showcase the unique charm of buildings.

[0008] In order to achieve energy conservation and emission reduction of coating materials on architectural decorative curtain walls, there is an urgent need to provide an industrial processing method for preparing alkali metal tungsten bronze materials on a large scale at low temperatures. Summary of the Invention

[0009] One of the objectives of the present invention is to propose a method for industrially preparing nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salt. In this preparation method, due to short reaction time and low reaction temperature (40°C - 95°C) during the hydrolysis process, industrial production of alkali metal tungsten bronze nano-materials at low cost is achieved. The method of the present invention uses one-step low-temperature heating hydrolysis to synthesize nano-alkali metal tungsten bronze, and its composition is Cs X WO3, Rb X WO3, K X WO3, Na X WO3, where X = 0.2 - 0.33. The nano-alkali metal tungsten bronze obtained by the method of the present invention has a short rod-like and equiaxed structure. The length of the synthesized short rod-like alkali metal tungsten bronze nano-particles is 10 - 150 nm, and the diameter is 10 - 50 nm. The size of each direction of the synthesized equiaxed alkali metal tungsten bronze nano-particles is less than 100 nm. The above products have good crystallinity, excellent visible light transmittance, near-infrared shielding performance, as well as good ultraviolet shielding and certain mid- and far-infrared shielding performance. The present invention precisely regulates the coordination of the hydrolysis product of the tungsten source in the reaction system with alkali metal elements, and reacts in a liquid phase below the boiling point of the solvent, so as to obtain alkali metal tungsten bronze nano-powders under low-temperature and non-high-pressure conditions. And the crystallization rate can be controlled by precisely controlling the stirring speed, reaction time, and temperature of the reaction system, thereby controlling the particle size of alkali metal tungsten bronze. The tungsten source, alkali metal source, deionized water, and alcohol solution used in the present invention are all environmentally friendly reagents and have low costs. The reaction system temperature adopted by the method of the present invention is low, there is no high pressure, the product morphology is uniform, the preparation cycle is short, the energy consumption is low, special equipment is not required, the yield is high, and the output is large.

[0010] The second object of the present invention is to provide a large-scale and low-cost production method for obtaining a glass curtain wall by industrially spraying an alkali metal tungsten bronze coating on the glass surface. The coating preparation proposed by the present invention does not require special equipment, the process is simple, and the preparation period is short. The coating prepared by the present invention has excellent near-infrared shielding performance, high visible light transmittance, good ultraviolet shielding performance, and excellent heat insulation performance.

[0011] A method for industrially preparing nano-alkali metal tungsten bronze by hydrolysis of a low-temperature cationic coordination tungsten salt according to the present invention includes the following steps:

[0012] Step 1: Prepare an alkali metal source solution;

[0013] Step 11: Add deionized water to the first stirring container;

[0014] Step 12: Add the alkali metal source to the first stirring container;

[0015] Step 13: Under normal pressure, set the dissolution temperature to 10°C to 40°C and the stirring speed to 200 r / min to 600 r / min; after stirring for 1 min to 15 min, an alkali metal source solution is prepared;

[0016] Step 2: Prepare a tungsten source solution;

[0017] Step 21: Add the tungsten source to the second stirring container;

[0018] Step 22: Add the alcohol solution to the second stirring container;

[0019] Step 23: Under normal pressure, set the dissolution temperature to 10°C to 40°C and the stirring speed to 200 r / min to 600 r / min; after stirring for 10 min to 60 min, a tungsten source solution is prepared;

[0020] Step 3: Hydrolyze by water bath heating to generate a nano-alkali metal tungsten bronze dispersion;

[0021] Dosage: To prepare 1 kg of nano-alkali metal tungsten bronze powder, 0.18 kg to 90 kg of alkali metal source solution and 3.68 kg to 184 kg of tungsten source solution are required;

[0022] One-step low-temperature heating hydrolysis to prepare an alkali metal tungsten bronze dispersion: Add the alkali metal source solution, tungsten source solution and deionized water to the water bath heating container (3); set the water bath temperature to 40 - 95°C, the stirring speed to 200 r / min to 1000 r / min, and after stirring for 90 min to 2880 min, an alkali metal tungsten bronze dispersion is obtained;

[0023] Step 4: Solid-liquid separation;

[0024] Step 5: Dry to prepare nano-alkali metal tungsten bronze powder;

[0025] The alkali metal tungsten bronze solution prepared in Step 4 is dried in a vacuum resistance furnace, and the vacuum degree is pumped to 1×10 －2 Pa to 1×10 －4 Pa, the drying temperature is 50°C to 100°C, and the drying time is 180 min to 720 min to obtain alkali metal tungsten bronze powder.

[0026] The advantages of the present invention in industrially preparing nano-alkali metal tungsten bronze by hydrolyzing low-temperature cation-coordinated tungsten salt are as follows:

[0027] ① By industrially preparing nano-alkali metal tungsten bronze by hydrolyzing low-temperature cation-coordinated tungsten salt, the synthesis of pure-phase alkali metal tungsten bronze under low-temperature and low-pressure conditions is realized. The process conditions are mild, the product has good crystallinity, no subsequent calcination is required, and the energy consumption is low.

[0028] ② By industrially preparing nano-alkali metal tungsten bronze by hydrolyzing low-temperature cation-coordinated tungsten salt, the requirements for the types of raw materials are not high, and there are many types of alkali metal sources and solvents available.

[0029] ③ By industrially preparing nano-alkali metal tungsten bronze by hydrolyzing low-temperature cation-coordinated tungsten salt, the industrial process is simple, the preparation period is short, and no high-temperature and high-pressure special equipment is required.

[0030] ④ By industrially preparing nano-alkali metal tungsten bronze by hydrolyzing low-temperature cation-coordinated tungsten salt, the yield is high and the output is large.

[0031] ⑤ By industrially preparing nano-alkali metal tungsten bronze by hydrolyzing low-temperature cation-coordinated tungsten salt, the synthesis period of pure-phase alkali metal tungsten bronze can be controlled by the stirring time and stirring rate, and the morphology of pure-phase cesium tungsten bronze is not affected.

[0032] ⑥ By industrially preparing nano-alkali metal tungsten bronze by hydrolyzing low-temperature cation-coordinated tungsten salt, it is not sensitive to the volume of the reaction vessel, the liquid phase volume and the material. The output can be simply controlled by increasing the volume of the reaction vessel or the liquid phase volume.

[0033] ⑦ By industrially preparing nano-alkali metal tungsten bronze by hydrolyzing low-temperature cation-coordinated tungsten salt, the product has excellent performance.

[0034] ⑧ During the spraying process, the distance between the ultrasonic atomization nozzle array and the upper surface of the pre-coated substrate in the present invention is 5 to 20 cm, so that the ultrasonic atomization nozzle array can achieve short-time large-area spraying within not less than 0.8 m×0.8 m in the spraying area, and then cured by hot air, improving the bonding force between the coating and the glass surface. Description of the Drawings

[0035] Figure 1 It is a flow chart of the method for industrially preparing nano-alkali metal tungsten bronze by hydrolyzing low-temperature cation-coordinated tungsten salt of the present invention.

[0036] Figure 2 It is a flow chart of using the nano-alkali metal tungsten bronze prepared by the hydrolysis of the low-temperature cationic coordination tungsten salt of the present invention to make a glass curtain wall. In Figure 2 , T represents a temperature sensor, F represents a pressure gauge, P represents a flow meter, and valves are provided on the channel.

[0037] Figure 3 It is a structural sectional view of the first stirring container of the present invention.

[0038] Figure 4 It is a structural sectional view of the second stirring container of the present invention.

[0039] Figure 5 It is a structural sectional view of the water bath heating container of the present invention.

[0040] Figure 6 It is a structural sectional view of the solid-liquid separator of the present invention.

[0041] Figure 7 It is a schematic diagram of the nozzles arranged in an array in the spraying machine of the present invention.

[0042] Figure 8 It is the XRD pattern of the target products obtained in Examples 1, 2, 3, and 4.

[0043] Figure 9 It is the SEM photo of the target product obtained in Example 1.

[0044] Figure 10 It is the SEM photo of the target product obtained in Example 2.

[0045] Figure 11 It is the SEM photo of the target product obtained in Example 3.

[0046] Figure 12 It is the SEM photo of the target product obtained in Example 4.

[0047] Figure 13 It is the near-infrared shielding performance diagram of the powder obtained in Example 1.

[0048] Figure 14 It is the mid- and far-infrared shielding performance diagram of the powder obtained in Example 1.

[0049] Figure 15 It is the Uv-Vis-NIR transmission spectrum of the composite film of the target products obtained in Examples 1, 2, 3, and 4 and PVA.

[0050] Figure 16 It is in Example 1 with PVA / M coated 0.3The temperature change curve inside a sealed box over time when quartz glass of WO3 thin film is irradiated by a 50W solar lamp. Detailed implementation mode

[0051] The present invention will be further described in detail below with reference to the drawings and embodiments.

[0052] See Figure 1 As shown, the present invention provides a method for industrially preparing nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salt, which includes the following preparation steps:

[0053] Step 1, prepare an alkali metal source solution;

[0054] Step 11, add deionized water into the first stirring container;

[0055] Step 12, add the alkali metal source into the first stirring container;

[0056] In the present invention, the alkali metal source includes hydroxides, chlorides, and salts of one or two combinations of nitrates, sulfates, and carbonates corresponding to alkali metal ions.

[0057] The hydroxides include: cesium hydroxide, potassium hydroxide, or sodium hydroxide.

[0058] The chlorides include: cesium chloride, rubidium chloride, potassium chloride, or sodium chloride.

[0059] The nitrates include: cesium nitrate, potassium nitrate, or sodium nitrate.

[0060] The sulfates include: cesium sulfate, potassium sulfate, or sodium sulfate.

[0061] The carbonates include: cesium carbonate, potassium carbonate, or sodium carbonate.

[0062] Step 13, under normal pressure, set the dissolution temperature to 10°C to 40°C and the stirring speed to 200 r / min to 600 r / min; stir for 1 min to 15 min to obtain the alkali metal source solution.

[0063] The concentration of the alkali metal source in the obtained alkali metal source solution is 0.1 mol / L to 6 mol / L.

[0064] See Figure 3 As shown, in the present invention, the first stirring container 1 is a double-layer stainless steel round barrel. The inside of the first stirring container 1 is provided with a stirrer 1E, and the stirrer E is used to provide the stirring speed of the first solution during the preparation process, and the stirring speed is 200 r / min to 600 r / min.

[0065] Above the cylinder body 1A of the first stirring container 1, there are an alkali metal source feed port 1A1, a deionized water feed port 1A2, and an exhaust port 1A3; the exhaust port 1A3 is used to discharge the gas generated during the preparation of the alkali metal source solution to ensure the safety of the preparation process of the alkali metal source solution; below the cylinder body 1A, there is a discharge port 1A4 for the alkali metal source solution. The discharge port 1A4 can be connected to the water bath heating container 3 through a connected pipeline, and a pressure gauge, a flow meter, a valve, etc. can be set on this pipeline, such as Figure 2 .

[0066] The bottom of the first stirring container 1 is provided with a base 1B. On the one hand, the base 1B is used to support the stirring container, and on the other hand, it also keeps the first stirring container 1 stable during the working state.

[0067] In the present invention, in order to monitor the temperature of the alkali metal source solution during the preparation process, a temperature sensor is provided in the first stirring container 1 to measure the dissolution temperature of the alkali metal source solution during the preparation process. If the current dissolution temperature is higher than the set dissolution temperature (10°C to 40°C), the stirring speed is reduced.

[0068] Step two, prepare a tungsten source solution;

[0069] Step 21, add the tungsten source to the second stirring container;

[0070] In the present invention, the tungsten source is tungsten hexachloride (WCl6) or tungsten tetrachloride (WCl4).

[0071] Step 22, add the alcohol solution to the second stirring container;

[0072] In the present invention, the alcohol solution is one, two or a combination of more of methanol (CH3OH), ethanol (CH3CH2OH), n-propanol (CH3(CH2)2OH), isopropanol (CH(CH3)2OH), n-butanol (CH3(CH2)3OH).

[0073] Step 23, under normal pressure, set the dissolution temperature to 15°C to 40°C and the stirring speed to 200 r / min to 600 r / min; after stirring for 10 min to 60 min, a tungsten source solution is prepared.

[0074] The concentration of the tungsten source in the prepared tungsten source solution is 0.04 mol / L to 1 mol / L.

[0075] See Figure 4 As shown, in the present invention, the second stirring container 2 is a double-layer stainless steel round barrel. Inside the second stirring container 2, there is a stirrer 2E, and the stirrer 2E is used to provide the stirring speed of the tungsten source solution during the preparation process, and the stirring speed is 200 r / min to 600 r / min.

[0076] Above the cylinder body 2A of the second stirring container 2, there are a tungsten source inlet 2A1, an alcohol source inlet 2A2, and an exhaust port 2A3. The exhaust port 2A3 is used to discharge the gas generated during the preparation of the tungsten source solution to ensure the safety of the tungsten source solution preparation process; below the cylinder body 2A, there is an outlet 2A4 for the tungsten source mixed solution. The outlet 2A4 can be connected to the water bath heating container 3 through a connected pipeline, and a pressure gauge, a flow meter, a valve, etc. can be set on this pipeline, such as Figure 2 .

[0077] At the bottom of the second stirring container 2, there is a base 2B. On the one hand, the base 2B is used to support the stirring container, and on the other hand, it also keeps the stirring container stable during the working state.

[0078] On the outer wall of the inner shell 2C of the second stirring container 2, a resistance wire 2D is wound, that is, the resistance wire 2D is arranged between the outer wall of the inner shell 2C and the inner wall of the cylinder body 2A, and a heat insulating material is filled. When preparing the tungsten source solution, if the measured temperature in the second stirring container 2 is lower than the set dissolution temperature through the thermometer measurement, then the resistance wire 2D is needed to provide heat source to heat the tungsten source solution during the preparation process.

[0079] In the present invention, in order to monitor the temperature of the tungsten source solution during the preparation process, a temperature sensor is provided in the second stirring container 2 to measure the dissolution temperature of the second solution during the preparation process. If the current dissolution temperature is lower than the set dissolution temperature (10 °C to 40 °C), then the resistance wire 2D is turned on to heat the tungsten source solution during the preparation process.

[0080] In the present invention, the second stirring container 2 can also be used to prepare the alkali metal source mixed solution.

[0081] In the present invention, the first stirring container 1 can also be used to prepare the tungsten source mixed solution.

[0082] Step three, water bath heating to hydrolyze and generate a nano-alkali metal tungsten bronze dispersion;

[0083] See Figure 1 , Figure 2 , Figure 5 As shown, in the present invention, using the water bath heating container to mix the alkali metal source solution and the tungsten source solution is to make the alkali metal cations (M + ) coordinate with the tungsten salt, and then add deionized water, so as to complete the step-by-step hydrolysis of the tungsten salt coordinated by the alkali metal cations, and finally obtain a nano-alkali metal tungsten bronze dispersion. The present invention uses the means of coordination first and then hydrolysis to quickly limit the required alkali metal element (M) in the product M X WO3, avoiding M +The disadvantage of being unable to participate in the hydrolysis reaction in the later stage greatly improves the utilization rate of element M. Coordination-induced changes in the electronic structure reduce hexavalent tungsten in the mixed solution of the alkali metal source solution and the tungsten source solution, enabling the rapid formation of crystal-forming particles required for nano-alkali metal tungsten bronze in the mixed solution and accelerating the industrial hydrolysis reaction rate.

[0084] Dosage: To prepare 1 kg of alkali metal tungsten bronze powder, 0.31 kg to 18 kg of alkali metal source solution and 3.68 kg to 92 kg of tungsten source solution are required.

[0085] One-step low-temperature heating hydrolysis to prepare alkali metal tungsten bronze dispersion: Add the alkali metal source solution, tungsten source solution and deionized water into a water bath heating container; set the water bath temperature to 40°C to 90°C, set the stirring speed of the water bath heating container to 200 r / min to 1000 r / min, and after stirring for 90 min to 2880 min, obtain the alkali metal tungsten bronze dispersion.

[0086] In the present invention, a low-temperature environment of 40°C to 95°C provided by the water bath heating container 3 is used to prepare the alkali metal tungsten bronze dispersion, which realizes the synthesis of alkali metal tungsten bronze under extremely mild process conditions, avoiding the extreme conditions (high temperature, high pressure) required by the existing two traditional methods: solvothermal method and hydrothermal method. Using a water bath heating container instead of high-temperature and high-pressure special equipment realizes the replacement of high-complexity equipment with medium- and low-complexity equipment.

[0087] Using the water bath heating container 3 to prepare the nano-alkali metal tungsten bronze dispersion avoids the use of high-temperature and high-pressure special equipment in the large-scale production process. On the one hand, using a water bath heater instead of high-temperature and high-pressure special equipment can significantly reduce the equipment procurement cost; on the other hand, the water bath heater has strong operability and simple operation. In the process of realizing process equipment iteration, it will neither increase a large amount of time cost (such as the training of experimental personnel), nor introduce excessive factory / laboratory design costs (such as HVAC, power distribution, etc.) that may be required for equipment replacement.

[0088] Preparing the alkali metal tungsten bronze dispersion with a water bath heater under a low-temperature environment (40°C to 95°C) realizes the replacement of high-complexity equipment with medium- and low-complexity equipment, and low-risk process flows replace high-risk process flows: On the basis of temperature controllability, a stirring operation is introduced, expanding the process selectivity, improving the controllability of the reaction process, significantly enhancing the process safety, reducing the time cost required for the same output, and reducing the production energy consumption.

[0089] See Figure 5As shown in the water bath heating container 3 designed by the present invention, the water bath heating container 3 is divided into a heating cylinder 3C and a water bath cylinder 3A, and is processed from stainless steel. A heating coil 3D is provided between the heating cylinder 3C and the water bath cylinder 3A, and tap water is filled in the water bath cylinder 3A. A stirrer 3E is provided inside the heating cylinder 3C. The stirrer 3E is used to provide the stirring speed of the dispersion during preparation, and the stirring speed is 200 r / min to 1000 r / min.

[0090] Above the water bath heating container 3, there are a CA feed port 3A1 (for injecting the alkali metal source solution), a CB feed port 3A2 (for injecting the tungsten source solution), a CC feed port 3A3 (for injecting deionized water), and an exhaust port 3A4. The exhaust port 3A4 is used to discharge the gas generated during the preparation of the dispersion; a dispersion discharge port 3A5 is provided below the cylinder body 3A. The dispersion discharge port 3A5 can be connected to a solid-liquid separator 4 through a connected pipeline, and a pressure gauge, a flow meter, a valve, etc. can be provided on this pipeline.

[0091] The bottom of the water bath heating container 3 is provided with a base 3B. On the one hand, the base 3B is used to support the water bath heating container, and on the other hand, it also keeps the water bath heating container stable during the stirring working state.

[0092] In the present invention, a heating coil 3D (such as a resistance wire) is wound around the outer wall of the heating cylinder 3C of the water bath heating container 3 and immersed in tap water, that is, the heating coil 3D and the water required for water bath heating are arranged between the outer wall of the heating cylinder 3C and the inner wall of the water bath cylinder 3A. The heating coil 3D is used to provide heat for the tap water, and the outer wall of the water bath cylinder 3A is wrapped with heat insulation material. When preparing the dispersion, if the measured temperature in the water bath heating container 3 is lower than the set water bath temperature measured by the thermometer, then it is necessary to heat the tap water through the heating coil 3D to provide the heat source for preparing the dispersion.

[0093] In the present invention, in order to monitor the temperature of the dispersion during preparation, a temperature sensor is provided in the water bath heating container 3 to measure the dissolution temperature of the dispersion during preparation.

[0094] Step four, solid-liquid separation;

[0095] In the present invention, as shown in Figure 1 、 Figure 2 、 Figure 6 During the solid-liquid separation process, adding washing liquid for multiple washes can remove the organic and inorganic impurities that may be adsorbed on the surface of the product remaining from the reaction, purify the product, and avoid the secondary aggregation of the nano-alkali metal tungsten bronze particles in the dispersion.

[0096] In the present invention, the washing liquid is methanol (CH3OH), ethanol (CH3CH2OH), acetone (C3H6O); or a combination of methanol and deionized water; a combination of ethanol and deionized water; a combination of acetone and deionized water.

[0097] Step 41: Add the alkali metal tungsten bronze dispersion liquid to the solid-liquid separator 4, let it stand for 20 - 100 min to obtain the first precipitate and the first supernatant; and discharge the first supernatant.

[0098] In the present invention, the maximum dosage of the alkali metal tungsten bronze dispersion liquid added to the solid-liquid separator 4 is two-thirds of the capacity of the solid-liquid separator.

[0099] Step 42: Add the washing liquid to the solid-liquid separator 4, where the washing liquid is 2 - 5 times that of the first precipitate; set the stirring speed of the solid-liquid separator to 200 r / min - 600 r / min, stir for 10 min - 60 min and then let it stand for 20 - 100 min to obtain the second precipitate and the second supernatant; and discharge the second supernatant.

[0100] Step 43: Add the washing liquid to the solid-liquid separator 4, where the washing liquid is 2 - 5 times that of the second precipitate; set the stirring speed of the solid-liquid separator to 200 r / min - 600 r / min, stir for 10 min - 60 min and then let it stand for 20 - 100 min to obtain the third precipitate and the third supernatant; and discharge the third supernatant.

[0101] Step 47: Add the washing liquid to the solid-liquid separator 4, where the solvent is 2 - 5 times that of the third precipitate; set the stirring speed of the solid-liquid separator to 200 r / min - 600 r / min; stir for 10 min - 60 min to obtain the alkali metal tungsten bronze dispersion liquid.

[0102] See Figure 6 As shown in the solid-liquid separator 4 designed by the present invention, the solid-liquid separator 4 is a double-layer stainless steel cylinder. Inside the solid-liquid separator 4, there is a stirrer 4E, and the stirrer 4E is used to provide the stirring speed of the dispersion liquid during the separation process, and the stirring speed is 200 r / min - 600 r / min.

[0103] Above the cylinder body 4A of the solid-liquid separator 4, there are a DA feed port 4A1 (for injecting the alkali metal tungsten bronze dispersion liquid), a DB feed port 4A2 (for injecting the washing liquid), and a DA discharge port 4A3 (for discharging the supernatant); below the cylinder body 4A, there is a DB discharge port 4A4, and the DB discharge port 4A4 is used for discharging the alkali metal tungsten bronze liquid. In Figure 2 Among them. The DB discharge port 4A4 can be connected to a third stirrer through a pipeline, and a pressure gauge, a flow meter, a valve, etc. can be set on this pipeline.

[0104] The bottom of the solid-liquid separator 4 is provided with a base 4B. On the one hand, the base 4B is used to support the solid-liquid separator, and on the other hand, it also keeps the solid-liquid separator stable during the stirring operation state.

[0105] Step five, drying to prepare nano-alkali metal tungsten bronze powder;

[0106] In the present invention, in order to analyze the material properties of the nano-alkali metal tungsten bronze liquid obtained in step four, it is necessary to perform a drying treatment on the nano-alkali metal tungsten bronze liquid to obtain nano-alkali metal tungsten bronze powder. The cesium tungsten bronze liquid obtained in step four is dried in a vacuum resistance furnace, and the vacuum degree is pumped to 1×10 －2 Pa to 1×10 －4 Pa, the drying temperature is 50°C to 100°C, and the drying time is 180 min to 720 min, to obtain nano-alkali metal tungsten bronze powder.

[0107] Analyzing the nano-alkali metal tungsten bronze powder prepared by the method of the present invention through an XRD pattern, it meets the requirement of the chemical formula M X WO3 (0.2 ≤ X ≤ 0.33). The better components prepared by the method of the present invention include Cs 0.30 WO3 powder, Rb 0.28 WO3 powder, K 0.32 WO3 powder and Na 0.33 WO3 powder. Through the calculation of the input raw materials and the product yield, the industrial yield of the prepared nano-cesium tungsten bronze powder is 70% to 85%, the industrial yield of the nano-rubidium tungsten bronze powder is 70% to 85%, the industrial yield of the nano-potassium tungsten bronze powder is 60% to 80%, and the industrial yield of the nano-sodium tungsten bronze powder is 50% to 75%.

[0108] Analyzing the morphology of the nano-alkali metal tungsten bronze powder prepared by the method of the present invention through an SEM pattern, the morphology is short rod-shaped or equiaxial. The length of the short rod-shaped structure is 10 to 150 nm, the diameter is 10 to 50 nm, and the dimensions of each direction of the equiaxial structure are less than 100 nm.

[0109] In the present invention, Figure 1 It aims to introduce the process for the industrial preparation of nano-alkali metal tungsten bronze powder by the hydrolysis of low-temperature cation coordination tungsten salt. The difference in the process lies in the one-step low-temperature heating hydrolysis to prepare the alkali metal tungsten bronze dispersion liquid. It realizes the water bath synthesis of pure-phase alkali metal tungsten bronze under low-temperature and pressure-free conditions. The process conditions are mild, and the product (nano-alkali metal tungsten bronze powder) has good crystallinity, without subsequent calcination and with low energy consumption.

[0110] In combination with Figure 1 Under the industrialization of preparing nano-alkali metal tungsten bronze liquid, see Figure 2As shown, applying the nano-alkali metal tungsten bronze solution to make the nano-alkali metal tungsten bronze coating, making the nano-alkali metal tungsten bronze coating on the glass plate with the nano-alkali metal tungsten bronze coating, and using the glass loaded with the nano-alkali metal tungsten bronze coating to make the indoor cooling of the glass curtain wall. The steps for industrially making the nano-alkali metal tungsten bronze coating in the present invention are as follows:

[0111] Step 1, prepare the alkali metal source solution;

[0112] Step 11, add deionized water to the first stirring container;

[0113] Step 12, add the alkali metal source to the first stirring container;

[0114] In the present invention, the alkali metal source includes hydroxides corresponding to alkali metal ions, chlorides, and salts in the form of one or a combination of two of nitrates, sulfates, and carbonates.

[0115] The hydroxides mentioned above are: cesium hydroxide, potassium hydroxide, or sodium hydroxide.

[0116] The chlorides mentioned above are: cesium chloride, rubidium chloride, potassium chloride, or sodium chloride.

[0117] The nitrates mentioned above are: cesium nitrate, potassium nitrate, or sodium nitrate.

[0118] The sulfates mentioned above are: cesium sulfate, potassium sulfate, or sodium sulfate.

[0119] The carbonates mentioned above are: cesium carbonate, potassium carbonate, or sodium carbonate.

[0120] Step 13, under normal pressure, set the dissolution temperature to 10°C to 40°C and the stirring speed to 200 r / min to 600 r / min; stir for 10 min to 60 min to obtain the alkali metal source solution.

[0121] The concentration of the alkali metal source in the obtained alkali metal source solution is 0.5 mol / L to 5 mol / L.

[0122] Step 2, prepare the tungsten source solution;

[0123] Step 21, add the tungsten source to the second stirring container;

[0124] In the present invention, the tungsten source is tungsten hexachloride (WCl6) or tungsten tetrachloride (WCl4).

[0125] Step 22, add the alcohol solution to the second stirring container;

[0126] In the present invention, the alcohol solution is one, two or a combination of more than two of methanol (CH3OH), ethanol (CH3CH2OH), n-propanol (CH3(CH2)2OH), isopropanol (CH(CH3)2OH), and n-butanol (CH3(CH2)3OH).

[0127] Step 23: Under normal pressure, set the dissolution temperature to 15°C to 40°C and the stirring speed to 200 r / min to 600 r / min; after stirring for 10 min to 60 min, a tungsten source solution is prepared.

[0128] The concentration of the tungsten source in the prepared tungsten source solution is 0.05 mol / L to 1 mol / L.

[0129] Step 3: Hydrolyze by water bath heating to generate a nano alkali metal tungsten bronze dispersion.

[0130] Dosage: To prepare 1 kg of alkali metal tungsten bronze powder, 0.37 kg to 3.6 kg of alkali metal source solution and 3.68 kg to 73.6 kg of tungsten source solution are required.

[0131] One-step low-temperature heating hydrolysis to prepare alkali metal tungsten bronze dispersion: Add the alkali metal source solution, tungsten source solution and deionized water into a water bath heating container; set the water bath temperature to 40°C to 90°C, set the stirring speed of the water bath heating container to 200 r / min to 1000 r / min, and after stirring for 90 min to 2880 min, a dispersion is obtained.

[0132] Step 4: Solid-liquid separation.

[0133] In the present invention, the washing liquid is methanol (CH3OH), ethanol (CH3CH2OH), acetone (C3H6O); or a combination of methanol and deionized water; a combination of ethanol and deionized water; a combination of acetone and deionized water.

[0134] Step 41: Add the alkali metal tungsten bronze dispersion to a solid-liquid separator, let it stand for 20 to 100 min to obtain a first precipitate and a first supernatant; and discharge the first supernatant.

[0135] Step 42: Add the washing liquid to the solid-liquid separator, and the washing liquid is 2 to 5 times that of the first precipitate; set the stirring speed of the solid-liquid separator to 200 r / min to 600 r / min, stir for 10 min to 60 min, then let it stand for 20 to 100 min to obtain a second precipitate and a second supernatant; and discharge the second supernatant.

[0136] Step 43: Add washing liquid into the solid-liquid separator, where the amount of the washing liquid is 2 to 5 times that of the second precipitate; set the stirring speed of the solid-liquid separator at 200 r / min to 600 r / min, stir for 10 min to 60 min, then let it stand for 20 to 100 min to obtain the third precipitate and the third supernatant; and discharge the third supernatant.

[0137] Step 47: Add washing liquid into the solid-liquid separator, where the amount of the solvent is 0.5 to 2 times that of the third precipitate; set the stirring speed of the solid-liquid separator at 200 r / min to 600 r / min; stir for 10 min to 60 min to obtain an alkali metal tungsten bronze dispersion.

[0138] Step Five: Prepare an alkali metal tungsten bronze coating.

[0139] Dosage (parts by weight): alkali metal tungsten bronze dispersion: PVA: deionized water = 1: 2 to 15: 80 to 130.

[0140] Add the alkali metal tungsten bronze dispersion, PVA (polyvinyl alcohol), and deionized water into the third stirring container; set the stirring speed of the third stirring container at 100 r / min to 400 r / min; stir for 30 min to 120 min to obtain an alkali metal tungsten bronze coating.

[0141] In the present invention, the structure of the third stirring container can be the same as that of the first stirring container.

[0142] Step Six: Fabricate a glass curtain wall by a spraying process.

[0143] Inject the alkali metal tungsten bronze coating into the hopper of the spraying machine through a pipeline, and set the spraying distance H from the nozzle to the upper surface of the glass plate at 0.5 to 2 cm; the flow rate of the alkali metal tungsten bronze coating is 1 to 7 ml / min.

[0144] Under the hot air temperature of 22 °C to 40 °C provided by a hot air blower and at the transmission roller speed of 10 r / min to 60 r / min, after curing, a nano alkali metal tungsten bronze coating on the upper surface of the glass is fabricated.

[0145] In the present invention, the glass with a nano alkali metal tungsten bronze coating is used to fabricate a glass curtain wall. In order to achieve large-size spraying of the glass curtain wall, the present invention adopts a structure with an array of nozzles arranged. Refer to Figure 7 as shown. Ultrasonic atomizing nozzles 5C are arranged in an array on the flat plate 5A of the nozzle mechanism 5. The ultrasonic atomizing nozzles 5C are connected to the hopper of the spraying machine through a flexible conduit. The hopper is connected to the discharge port of the third stirring container through a pipeline. A column 5B is provided at the center of the flat plate 5A, and the column 5B is fixed to the housing of the spraying machine.

[0146] In the present invention, the nozzle diameter of the ultrasonic atomization nozzle 5C is 10 - 30 mm, and the nozzle orifice diameter is 0.5 - 2 mm. The number of ultrasonic atomization nozzles 5C arranged on the flat plate 5A is determined according to the size of the fabricated glass curtain wall, the nozzle diameter, and the nozzle orifice diameter.

[0147] Example 1 Preparation of cesium tungsten bronze Cs 0.30 WO3

[0148] See Figure 2 As shown, Steps 1 to 4 of the present invention are methods for the industrial preparation of nano-alkali metal tungsten bronze by the hydrolysis of low-temperature cation-coordinated tungsten salt, and Steps 5 to 6 are methods for the preparation of nano-alkali metal tungsten bronze coatings. The nano-alkali metal tungsten bronze obtained by the method of the present invention is made into a nano-alkali metal tungsten bronze coating material, and then a nano-alkali metal tungsten bronze coating is fabricated on a glass plate by a spraying process. The glass loaded with the nano-alkali metal tungsten bronze coating is applied to a glass curtain wall. In this example, the preparation and application of nano-cesium tungsten bronze and its coating are specifically referred to. The specific preparation steps are as follows:

[0149] Step 1, prepare a cesium source solution;

[0150] Dosage: The concentration of the cesium source in the cesium source solution is 1 mol / L.

[0151] Add cesium chloride (CsCl) and deionized water to the first stirring container; under normal pressure, set the dissolution temperature to 25 °C, the stirring speed to 400 r / min, and stir for 5 min to obtain the cesium source solution.

[0152] Step 2, prepare a tungsten source solution;

[0153] Dosage: The concentration of the tungsten source in the tungsten source solution is 0.1 mol / L.

[0154] Add WCl6 and CH3CH2OH to the second stirring container; under normal pressure, set the dissolution temperature to 30 °C, the stirring speed to 300 r / min, and stir for 25 min to obtain the tungsten source solution.

[0155] Step 3, perform water bath heating hydrolysis to generate a nano-cesium tungsten bronze dispersion;

[0156] Dosage: To prepare 1 kg of cesium tungsten bronze powder, 0.61 kg of cesium source solution and 46.12 kg of tungsten source solution are required.

[0157] One-step low-temperature heating hydrolysis to prepare a dispersion: Add the cesium source solution and the tungsten source solution to a water bath heating container; set the water bath temperature to 70 °C, set the stirring speed of the water bath heating container to 500 r / min, and stir for 240 min to obtain a dispersion.

[0158] Step 4, solid-liquid separation;

[0159] In Example 1, the washing liquid is CH3CH2OH.

[0160] Step 41: Add the dispersion liquid to the solid-liquid separator, let it stand for 60 min to obtain the first precipitate and the first supernatant; and discharge the first supernatant.

[0161] Step 42: Add the washing liquid to the solid-liquid separator, where the amount of the washing liquid is 3 times that of the first precipitate; set the stirring speed of the solid-liquid separator to 300 r / min, stir for 30 min, then let it stand for 90 min to obtain the second precipitate and the second supernatant; and discharge the second supernatant.

[0162] Step 43: Add the washing liquid to the solid-liquid separator, where the amount of the washing liquid is 3 times that of the second precipitate; set the stirring speed of the solid-liquid separator to 300 r / min, stir for 60 min, then let it stand for 60 min to obtain the third precipitate and the third supernatant; and discharge the third supernatant.

[0163] Step 47: Add deionized water to the solid-liquid separator, where the amount of the solvent is 1 time that of the third precipitate; set the stirring speed of the solid-liquid separator to 300 r / min; stir for 30 min to obtain the cesium tungsten bronze dispersion liquid.

[0164] Characteristics and properties of the cesium tungsten bronze powder prepared by the method of Example 1

[0165] Dry the cesium tungsten bronze dispersion liquid prepared in Step 4 in a vacuum resistance furnace at a drying temperature of 60 °C for 240 min under vacuum to obtain Cs 0.30 WO3 cesium tungsten bronze powder, that is, the powder. Through the calculation of the input raw materials and the product yield, Cs 0.30 The industrial yield of WO3 powder is as high as 80%.

[0166] In Figure 8 In the XRD pattern shown, all the diffraction peaks of the cesium tungsten bronze powder prepared by the method of Example 1 belong to Cs 0.30 WO3, indicating that pure-phase cesium tungsten bronze is synthesized.

[0167] In Figure 9 In the SEM pattern shown, the morphology of the Cs 0.30 WO3 powder prepared by the method of Example 1 is short rod-shaped, and the length of the short rod-shaped structure is 10 - 140 nm, and the diameter is 10 - 20 nm.

[0168] In Figure 13 In the Uv-Vis-NIR pattern shown, the Cs 0.30 WO3 powder prepared by the method of Example 1 has excellent near-infrared shielding performance, high visible light transmittance and good ultraviolet shielding performance.

[0169] In Figure 14 the FTIR spectrum shown, the Cs 0.30 WO3 powder prepared by the method of Example 1 has certain mid- and far-infrared shielding properties.

[0170] In Figure 15 the Uv-Vis-NIR spectrum shown, the Cs 0.30 WO3 powder and PVA composite film prepared by the method of Example 1 have high near-infrared absorption properties, ultraviolet shielding properties and high visible light transmittance properties.

[0171] Step five, prepare cesium tungsten bronze coating;

[0172] Dosage (parts by weight): cesium tungsten bronze dispersion: PVA: deionized water = 1:5:94.

[0173] Add cesium tungsten bronze dispersion, PVA and deionized water to the third stirring container; set the stirring speed of the third stirring container to 300 r / min; after stirring for 60 min, obtain cesium tungsten bronze coating;

[0174] Step six, fabricate a glass curtain wall by spraying process;

[0175] Inject the cesium tungsten bronze coating into the hopper of the spraying machine through a pipeline, and set the spraying distance H from the nozzle to the upper surface of the glass plate to 1 cm; the flow rate of the cesium tungsten bronze coating is 4 ml / min.

[0176] At a hot air temperature of 35 °C provided by a hot air blower and a transmission roller speed of 50 r / min, after curing, obtain a cesium tungsten bronze coating on the upper surface of the glass.

[0177] In Figure 16 the test of the photothermal conversion and heat insulation performance of the cesium tungsten bronze coating on the upper surface of the glass shown, irradiate the glass with a 50 W halogen lamp from a distance of 20 cm from the upper surface of the glass. Compared with the quartz glass without a heat insulation coating or only with a PVA coating, the glass with a heat insulation coating on the upper surface prepared in Example 1 reduces the temperature in the box by 13 °C, and the temperature drop reaches 18.6%. The Cs 0.3 WO3 coating prepared in Example 1 has a heat insulation principle that the cesium tungsten bronze in the coating absorbs near-infrared light and converts it into heat energy outside the box to achieve the heat insulation effect. Therefore, the Cs 0.3 WO3 coating prepared by the method of Example 1 has high photothermal conversion performance and heat insulation performance.

[0178] Flip the glass with a Cs 0.3 WO3 coating on the upper surface prepared in Example 1 so that the heat insulation coating on the upper surface of the glass is inside the box, and the Cs 0.3The WO3 coating has high photothermal conversion performance and heat insulation performance to store heat in the box. By adjusting the relative position of the heat insulation coating prepared in Example 1, effective heat management can be carried out.

[0179] The one-step low-temperature heating hydrolysis method adopted in the present invention utilizes the forced hydrolysis of metal salts under acidic conditions to produce uniformly dispersed nanoparticles. Compared with the hydrothermal method and the solvothermal method, the hydrolysis method in the present invention has a low reaction temperature, a high yield, no reaction pressure and is safer. Both the hydrothermal method and the solvothermal method refer to the synthesis carried out by the chemical reaction of substances in a solution under certain temperature (100°C to 1000°C) and pressure (1 MPa to 100 MPa) conditions.

[0180] Example 2 prepares rubidium tungsten bronze Rb 0.28 WO3

[0181] See Figure 1 As shown, the method for industrially preparing nano-rubidium tungsten bronze by low-temperature cation coordination tungsten salt hydrolysis of the present invention includes the following preparation steps:

[0182] Step 1, prepare a rubidium source solution;

[0183] Dosage: The concentration of the rubidium source in the rubidium source solution is 1 mol / L.

[0184] Add rubidium chloride (RbCl) and deionized water to the first stirring container; under normal pressure, set the dissolution temperature to 25°C, the stirring speed to 400 r / min, and stir for 20 min to obtain the rubidium source solution.

[0185] Step 2, prepare a tungsten source solution;

[0186] Dosage: The concentration of the tungsten source in the tungsten source solution is 0.1 mol / L.

[0187] Add WCl6 and CH3CH2OH to the second stirring container; under normal pressure, set the dissolution temperature to 40°C, the stirring speed to 300 r / min, and stir for 50 min to obtain the tungsten source solution.

[0188] Step 3, carry out water bath heating hydrolysis to generate a nano-rubidium tungsten bronze dispersion;

[0189] Dosage: To prepare 1 kg of cesium tungsten bronze powder, 0.61 kg of rubidium source solution and 49.2 kg of tungsten source solution are required.

[0190] One-step low-temperature heating hydrolysis to prepare a dispersion: Add the rubidium source solution and the tungsten source solution to the water bath heating container; set the water bath temperature to 70°C, set the stirring speed of the water bath heating container to 500 r / min, and stir for 600 min to obtain a dispersion.

[0191] Step 4, solid-liquid separation;

[0192] In Example 2, the washing solution is CH3CH2OH.

[0193] Step 41: Add the dispersion liquid to the solid-liquid separator. After standing for 40 min, the first precipitate and the first supernatant are obtained; and the first supernatant is discharged.

[0194] Step 42: Add the washing solution to the solid-liquid separator. The amount of the washing solution is 3.5 times that of the first precipitate; set the stirring speed of the solid-liquid separator to 400 r / min. After stirring for 20 min and then standing for 80 min, the second precipitate and the second supernatant are obtained; and the second supernatant is discharged.

[0195] Step 43: Add the washing solution to the solid-liquid separator. The amount of the washing solution is 3 times that of the second precipitate; set the stirring speed of the solid-liquid separator to 400 r / min. After stirring for 20 min and then standing for 80 min, the third precipitate and the third supernatant are obtained; and the third supernatant is discharged.

[0196] Step 47: Add the washing solution to the solid-liquid separator. The amount of the solvent is 1 times that of the third precipitate; set the stirring speed of the solid-liquid separator to 400 r / min; after stirring for 30 min, a rubidium tungsten bronze dispersion liquid is obtained.

[0197] The characteristics and properties of the rubidium tungsten bronze prepared by the method of Example 2

[0198] The rubidium tungsten bronze dispersion liquid prepared in Step 4 is dried in a vacuum resistance furnace at a drying temperature of 60 °C for 480 min to obtain rubidium tungsten bronze powder, i.e., Rb 0.28 WO3 powder. Through the calculation of the input raw materials and the product yield, the industrial yield of Rb 0.28 WO3 powder is as high as 75%.

[0199] In Figure 8 In the XRD pattern shown, all the diffraction peaks of the rubidium tungsten bronze powder prepared by the method of Example 2 belong to Rb 0.28 WO3, indicating that pure-phase rubidium tungsten bronze is synthesized.

[0200] In Figure 9 In the SEM pattern shown, the morphology of the Rb 0.28 WO3 powder prepared by the method of Example 2 is short rod-shaped, and the length of the short rod-shaped structure is 10 - 100 nm, and the diameter is 15 - 30 nm.

[0201] Tested by the Uv-Vis-NIR spectrum, the Rb 0.28 WO3 powder prepared by the method of Example 2 has excellent near-infrared shielding performance, high visible light transmittance and good ultraviolet shielding performance.

[0202] After testing by FTIR spectrum, the Rb 0.28 WO3 powder prepared by the method of Example 2 has certain mid- and far-infrared shielding properties.

[0203] In Figure 15 the shown Uv-Vis-NIR spectrum, the Rb 0.28 WO3 powder and PVA composite film prepared by the method of Example 2 have high near-infrared absorption properties, ultraviolet shielding properties and high visible light transmittance properties.

[0204] Step Five, prepare rubidium tungsten bronze coating;

[0205] Dosage (parts by weight): rubidium tungsten bronze dispersion: PVA: deionized water = 1: 6: 94.

[0206] Add rubidium tungsten bronze dispersion, PVA, and deionized water to the third stirring container; set the stirring speed of the third stirring container to 300 r / min; after stirring for 50 min, obtain rubidium tungsten bronze coating;

[0207] Step Six, fabricate a glass curtain wall by spraying process;

[0208] Inject the rubidium tungsten bronze coating into the hopper of the spraying machine through a pipeline, and set the spraying distance H from the nozzle to the upper surface of the glass plate to 2 cm; the flow rate of the rubidium tungsten bronze coating is 3.5 ml / min.

[0209] At a hot air temperature of 40 °C provided by a hot air blower and a transmission roller speed of 40 r / min, after curing, obtain a rubidium tungsten bronze coating on the upper surface of the glass.

[0210] In Figure 16 the test of the photothermal conversion and heat insulation performance of the rubidium tungsten bronze coating on the upper surface of the shown glass, irradiate the glass with a 50 W halogen lamp from a distance of 20 cm from the upper surface of the glass. Compared with the quartz glass without a heat insulation coating or only with a PVA coating, the glass with a heat insulation coating on the upper surface prepared in Example 2 reduces the temperature inside the box by 15.5 °C, and the temperature drop reaches 22.1%. The Rb 0.28 The heat insulation principle of the WO3 coating is that the rubidium tungsten bronze in the coating absorbs near-infrared light and converts it into heat energy outside the box to achieve the heat insulation effect. Therefore, the Rb 0.28 WO3 coating prepared by the method of Example 2 has high photothermal conversion performance and heat insulation performance.

[0211] Flip the glass with the Rb 0.28 WO3 coating on the upper surface prepared in Example 2 so that the heat insulation coating on the upper surface of the glass is inside the box, and the Rb 0.28The WO3 coating has high photothermal conversion performance and heat insulation performance, and stores heat in the box. By adjusting the relative position of the heat insulation coating prepared in Example 2, effective heat management can be carried out.

[0212] Example 3 prepares potassium tungsten bronze K 0.32 WO3

[0213] See Figure 1 As shown, the method for industrially preparing nano-potassium tungsten bronze by hydrolysis of low-temperature cationic coordination tungsten salt of the present invention includes the following preparation steps:

[0214] Step 1, prepare a potassium source solution;

[0215] Dosage: The concentration of the potassium source in the potassium source solution is 2 mol / L.

[0216] Add potassium chloride (KCl) and deionized water to the first stirring container; under normal pressure, set the dissolution temperature to 25 °C, the stirring speed to 400 r / min, and stir for 20 min to obtain the potassium source solution.

[0217] Step 2, prepare a tungsten source solution;

[0218] Dosage: The concentration of the tungsten source in the tungsten source solution is 0.1 mol / L.

[0219] Add WCl6 and CH3CH2OH to the second stirring container; under normal pressure, set the dissolution temperature to 40 °C, the stirring speed to 300 r / min, and stir for 50 min to obtain the tungsten source solution.

[0220] Step 3, heat by water bath to hydrolyze to generate a nano-potassium tungsten bronze dispersion;

[0221] Dosage: To prepare 1 kg of potassium tungsten bronze powder, 0.85 kg of potassium source solution and 49.2 kg of tungsten source solution are required.

[0222] One-step low-temperature heating hydrolysis to prepare a dispersion: Add the potassium source solution and the tungsten source solution to a water bath heating container; set the water bath temperature to 70 °C, set the stirring speed of the water bath heating container to 500 r / min, and stir for 720 min to obtain a dispersion.

[0223] Step 4, solid-liquid separation;

[0224] In Example 3, the washing solution is C3H6O.

[0225] Step 41, add the dispersion to a solid-liquid separator, let it stand for 90 min to obtain a first precipitate and a first supernatant; and drain the first supernatant;

[0226] Step 42: Add washing liquid to the solid-liquid separator. The amount of the washing liquid is 4 times that of the first precipitate. Set the stirring speed of the solid-liquid separator to 300 r / min. After stirring for 50 min, let it stand for 60 min to obtain the second precipitate and the second supernatant. Then discharge the second supernatant.

[0227] Step 43: Add washing liquid to the solid-liquid separator. The amount of the washing liquid is 4 times that of the second precipitate. Set the stirring speed of the solid-liquid separator to 300 r / min. After stirring for 40 min, let it stand for 40 min to obtain the third precipitate and the third supernatant. Then discharge the third supernatant.

[0228] Step 47: Add washing liquid to the solid-liquid separator. The amount of the solvent is 1.5 times that of the third precipitate. Set the stirring speed of the solid-liquid separator to 300 r / min. After stirring for 60 min, a potassium tungsten bronze dispersion is obtained.

[0229] Characteristics and properties of the potassium tungsten bronze prepared by the method of Example 3

[0230] Dry the potassium tungsten bronze dispersion obtained in Step 4 in a vacuum resistance furnace at a drying temperature of 60 °C for 480 min to obtain potassium tungsten bronze powder, i.e., K 0.32 WO3 powder. Through the calculation of the input raw materials and the output of the product, the industrial yield of K 0.32 WO3 powder is as high as 75%.

[0231] In Figure 8 In the XRD pattern shown, all the diffraction peaks of the potassium tungsten bronze powder prepared by the method of Example 3 belong to K 0.32 WO3, indicating that pure-phase potassium tungsten bronze is synthesized.

[0232] In Figure 9 In the SEM pattern shown, the morphology of the K 0.32 WO3 powder prepared by the method of Example 3 is equiaxed, and the size distribution of the equiaxed structure is 15 - 100 nm.

[0233] After testing by the Uv-Vis-NIR spectrum, the K 0.32 WO3 powder prepared by the method of Example 3 has excellent near-infrared shielding performance, high visible light transmittance, and good ultraviolet shielding performance.

[0234] After testing by the FTIR spectrum, the K 0.32 WO3 powder prepared by the method of Example 3 has certain mid- and far-infrared shielding performance.

[0235] In Figure 15 In the Uv-Vis-NIR spectrum shown, the K 0.32The WO3 powder and PVA composite film have high near-infrared absorption performance, ultraviolet shielding performance and high visible light transmittance performance.

[0236] Step Five, prepare the potassium tungsten bronze coating;

[0237] Dosage (parts by weight): potassium tungsten bronze dispersion: PVA: deionized water = 1:5:100.

[0238] Add the potassium tungsten bronze dispersion, PVA, and deionized water to the third stirring container; set the stirring speed of the third stirring container to 400 r / min; after stirring for 40 min, obtain the potassium tungsten bronze coating;

[0239] Step Six, fabricate the glass curtain wall by spraying process;

[0240] Inject the potassium tungsten bronze coating into the hopper of the spraying machine through a pipeline, and set the spraying distance H from the nozzle to the upper surface of the glass plate to 1.5 cm; the flow rate of the potassium tungsten bronze coating is 3 ml / min.

[0241] At a hot air temperature of 40 °C provided by the hot air blower and a transmission roller speed of 60 r / min, after curing, obtain the potassium tungsten bronze coating on the upper surface of the glass.

[0242] On Figure 16 In the test of the photothermal conversion and heat insulation performance of the potassium tungsten bronze coating on the upper surface of the glass shown, irradiate the glass with a 50 W halogen lamp from a distance of 20 cm from the upper surface of the glass. Compared with the quartz glass without a heat insulation coating or with only a PVA coating, the glass with a heat insulation coating on the upper surface prepared in Example 3 reduces the temperature in the box by 7.5 °C, and the temperature reduction rate reaches 10.7%. The K prepared in Example 3 0.32 The heat insulation principle of the WO3 coating is that the potassium tungsten bronze in the coating absorbs near-infrared light and converts it into heat energy outside the box to achieve the heat insulation effect. Therefore, the K prepared by the method of Example 3 0.32 The WO3 coating has high photothermal conversion performance and heat insulation performance.

[0243] Flip the glass with the K 0.32 WO3 coating on the upper surface so that the heat insulation coating on the upper surface of the glass is inside the box, and the K 0.32 WO3 coating can also store heat in the box with high photothermal conversion performance and heat insulation performance. By adjusting the relative position of the heat insulation coating prepared in Example 3, effective thermal management can be carried out.

[0244] Example 4 prepares sodium tungsten bronze Na 0.33 WO3

[0245] See Figure 1As shown in the figure, the method for the industrial preparation of nano-sodium tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salt of the present invention comprises the following preparation steps:

[0246] Step 1: Prepare a sodium source solution;

[0247] Dosage: The concentration of the sodium source in the sodium source solution is 2 mol / L.

[0248] Add sodium chloride (NaCl) and deionized water into the first stirring container; under normal pressure, set the dissolution temperature to 25 °C, the stirring speed to 400 r / min, and stir for 10 min to obtain the sodium source solution.

[0249] Step 2: Prepare a tungsten source solution;

[0250] Dosage: The concentration of the tungsten source in the tungsten source solution is 0.1 mol / L.

[0251] Add WCl6 and CH3CH2OH into the second stirring container; under normal pressure, set the dissolution temperature to 40 °C, the stirring speed to 300 r / min, and stir for 50 min to obtain the tungsten source solution.

[0252] Step 3: Hydrolyze by water bath heating to generate a nano-sodium tungsten bronze dispersion;

[0253] Dosage: To prepare 1 kg of sodium tungsten bronze powder, 2.32 kg of sodium source solution and 61.5 kg of tungsten source solution are required.

[0254] One-step low-temperature heating hydrolysis to prepare a dispersion: Add the sodium source solution and the tungsten source solution into a water bath heating container; set the water bath temperature to 70 °C, set the stirring speed of the water bath heating container to 500 r / min, and stir for 1440 min to obtain a dispersion.

[0255] [[ID=३०]]Step 4: Solid-liquid separation;

[0256] In Example 4, the washing solution is CH3OH.

[0257] Step 41: Add the dispersion into a solid-liquid separator, let it stand for 20 min to obtain the first precipitate and the first supernatant; and discharge the first supernatant;

[0258] Step 42: Add the washing solution into the solid-liquid separator, and the washing solution is 4.5 times that of the first precipitate; set the stirring speed of the solid-liquid separator to 200 r / min, stir for 20 min, then let it stand for 20 min to obtain the second precipitate and the second supernatant; and discharge the second supernatant;

[0259] Step 43: Add washing liquid into the solid-liquid separator. The amount of the washing liquid is 4.5 times that of the second precipitate. Set the stirring speed of the solid-liquid separator at 200 r / min. After stirring for 50 min, let it stand for 70 min to obtain the third precipitate and the third supernatant. Then discharge the third supernatant.

[0260] Step 47: Add washing liquid into the solid-liquid separator. The amount of the solvent is 5 times that of the third precipitate. Set the stirring speed of the solid-liquid separator at 200 r / min. After stirring for 20 min, obtain the sodium tungsten bronze dispersion.

[0261] Characteristics and properties of the sodium tungsten bronze prepared by the method of Example 4

[0262] Dry the sodium tungsten bronze dispersion prepared in Step Four in a vacuum resistance furnace at a drying temperature of 60 °C for 480 min to obtain sodium tungsten bronze powder, i.e., Na 0.33 WO3 powder. Through the calculation of the input raw materials and the output of the product, the industrial yield of the Na 0.33 WO3 powder is as high as 60%.

[0263] In the Figure 8 shown XRD pattern, all diffraction peaks of the sodium tungsten bronze powder prepared by the method of Example 4 belong to Na 0.33 WO3, indicating that pure-phase sodium tungsten bronze is synthesized.

[0264] In the Figure 9 shown SEM pattern, the morphology of the Na 0.33 WO3 powder prepared by the method of Example 4 is short rod-shaped, and the length of the short rod-shaped structure is 20 - 150 nm, and the diameter is 20 - 50 nm.

[0265] Tested by the Uv-Vis-NIR spectrum, the Na 0.33 WO3 powder prepared by the method of Example 4 has excellent near-infrared shielding performance, high visible light transmittance and good ultraviolet shielding performance.

[0266] Tested by the FTIR spectrum, the Na 0.33 WO3 powder prepared by the method of Example 4 has certain mid- and far-infrared shielding performance.

[0267] In the Figure 15 shown Uv-Vis-NIR spectrum, the Na 0.33 WO3 powder and the PVA composite film have high near-infrared absorption performance, ultraviolet shielding performance and high visible light transmittance performance.

[0268] Step Five: Prepare sodium tungsten bronze coating;

[0269] Dosage (parts by weight): Sodium tungsten bronze dispersion: PVA: Deionized water = 1.5:7:120.

[0270] Add sodium tungsten bronze dispersion, PVA, and deionized water into the third stirring container; set the stirring speed of the third stirring container to 300 r / min; after stirring for 100 min, obtain sodium tungsten bronze coating;

[0271] Step six, fabricate the glass curtain wall by spraying process;

[0272] Inject the sodium tungsten bronze coating into the hopper of the spraying machine through a pipeline, and set the spraying distance H from the nozzle to the upper surface of the glass plate to 1 cm; the flow rate of the sodium tungsten bronze coating is 2 ml / min.

[0273] At a hot air temperature of 40 °C provided by a hot air blower and a transmission roller speed of 50 r / min, after curing, obtain a heat insulation coating on the upper surface of the glass.

[0274] In order to achieve large-size spraying of the glass curtain wall, the present invention adopts a structure with an array of nozzles, as shown in Figure 7 As shown. Ultrasonic atomizing nozzles 5C are arranged in an array on the flat plate 5A of the nozzle mechanism 5. The ultrasonic atomizing nozzles 5C are connected to the hopper of the spraying machine through a flexible conduit. A column 5B is provided at the center of the flat plate 5A, and the column 5B is fixed to the housing of the spraying machine.

[0275] In the present invention, the nozzle diameter of the ultrasonic atomizing nozzle 5C is 20 mm, and the nozzle orifice diameter is 1.5 mm. The number of ultrasonic atomizing nozzles 5C arranged on the flat plate 5A is determined according to the size of the fabricated glass curtain wall, the nozzle diameter, and the nozzle orifice diameter.

[0276] In Figure 16 In the test of the photothermal conversion and heat insulation performance of the sodium tungsten bronze coating on the upper surface of the glass as shown, irradiate the glass with a 50 W halogen lamp from a distance of 20 cm from the upper surface of the glass. Compared with the quartz glass without a heat insulation coating or with only a PVA coating, the glass with a heat insulation coating on the upper surface prepared in Example 4 reduces the temperature inside the box by 10 °C, and the temperature drop reaches 14.3%. The heat insulation principle of the Na 0.33 WO3 coating prepared in Example 4 is that the sodium tungsten bronze in the coating absorbs near-infrared light and converts it into heat energy outside the box to achieve the heat insulation effect. Therefore, the Na 0.33 WO3 coating prepared by the method of Example 4 has high photothermal conversion performance and heat insulation performance.

[0277] Flip the glass with the Na 0.33 WO3 coating on the upper surface prepared in Example 4 so that the heat insulation coating on the upper surface of the glass is inside the box, and the Na 0.33The WO3 coating has high photothermal conversion performance and heat insulation performance to store heat in the box. By adjusting the relative position of the heat insulation coating prepared in Example 4, effective heat management can be carried out.

[0278] Example 5 prepares cesium tungsten bronze Cs 0.23 WO3

[0279] See Figure 2 As shown, for the method of preparing a nano-cesium tungsten bronze coating by spraying the nano-cesium tungsten bronze prepared by the industrial hydrolysis of low-temperature cation-coordinated tungsten salt of the present invention, it includes the following preparation steps:

[0280] Step 1, prepare a cesium source solution;

[0281] Dosage: The concentration of the cesium source in the cesium source solution is 0.2 mol / L.

[0282] Add CsOH and deionized water to the first stirring container; under normal pressure, set the dissolution temperature to 40 °C, the stirring speed to 400 r / min, and stir for 20 min to obtain the cesium source solution.

[0283] Step 2, prepare a tungsten source solution;

[0284] Dosage: The concentration of the tungsten source in the tungsten source solution is 0.15 mol / L.

[0285] Add WCl6 and CH3(CH2)2OH to the second stirring container; under normal pressure, set the dissolution temperature to 30 °C, the stirring speed to 500 r / min, and stir for 20 min to obtain the tungsten source solution.

[0286] Step 3, generate a nano-cesium tungsten bronze dispersion by water bath heating hydrolysis;

[0287] Dosage: To prepare 1 kg of cesium tungsten bronze powder, 6.5 kg of cesium source solution and 36.32 kg of tungsten source solution are required.

[0288] One-step low-temperature heating hydrolysis to prepare a dispersion: Add the cesium source solution and the tungsten source solution to the water bath heating container; set the water bath temperature to 80 °C, set the stirring speed of the water bath heating container to 500 r / min, and stir for 360 min to obtain a dispersion.

[0289] Step 4, solid-liquid separation;

[0290] In Example 5, the washing liquid is CH3CH2OH.

[0291] Step 41, add the dispersion to the solid-liquid separator, let it stand for 100 min to obtain the first precipitate and the first supernatant; and drain the first supernatant;

[0292] Step 42: Add washing liquid to the solid-liquid separator. The amount of the washing liquid is 3.5 times that of the first precipitate. Set the stirring speed of the solid-liquid separator at 400 r / min. After stirring for 30 min, let it stand for 40 min to obtain the second precipitate and the second supernatant. Then discharge the second supernatant.

[0293] Step 43: Add washing liquid to the solid-liquid separator. The amount of the washing liquid is 3.5 times that of the second precipitate. Set the stirring speed of the solid-liquid separator at 400 r / min. After stirring for 80 min, let it stand for 70 min to obtain the third precipitate and the third supernatant. Then discharge the third supernatant.

[0294] Step 47: Add deionized water to the solid-liquid separator. The amount of the solvent is 4 times that of the third precipitate. Set the stirring speed of the solid-liquid separator at 500 r / min. After stirring for 50 min, obtain the cesium tungsten bronze dispersion.

[0295] Step Five: Prepare the cesium tungsten bronze coating.

[0296] Dosage (parts by weight): cesium tungsten bronze dispersion: PVA: deionized water = 1:5:100.

[0297] Add the cesium tungsten bronze dispersion, PVA, and deionized water to the third stirring container. Set the stirring speed of the third stirring container at 400 r / min. After stirring for 90 min, obtain the cesium tungsten bronze coating.

[0298] Step Six: Spray the glass curtain wall.

[0299] Inject the cesium tungsten bronze coating into the hopper of the sprayer through a pipeline, and set the spraying distance H from the nozzle to the upper surface of the glass plate at 1 cm. The flow rate of the cesium tungsten bronze coating is 7 ml / min.

[0300] Under the hot air temperature of 35 °C provided by the hot air blower and the transmission roller speed of 20 r / min, after curing, obtain the heat insulation coating on the upper surface of the glass.

[0301] To achieve large-size spraying of the glass curtain wall, the present invention adopts a structure with an array of nozzles. See Figure 7 as shown. Ultrasonic atomizing nozzles 5C are arranged in an array on the flat plate 5A of the nozzle mechanism 5. The ultrasonic atomizing nozzles 5C are connected to the hopper of the sprayer through a flexible conduit. A column 5B is provided at the center of the flat plate 5A, and the column 5B is fixed to the housing of the sprayer.

[0302] In the present invention, the nozzle diameter of the ultrasonic atomizing nozzle 5C is 10 mm, and the jet diameter is 1 mm. The number of ultrasonic atomizing nozzles 5C arranged on the flat plate 5A is determined according to the size of the glass curtain wall to be fabricated, the nozzle diameter, and the jet diameter.

[0303] Characteristics and Properties of Cesium Tungsten Bronze Prepared by the Method of Example 5

[0304] According to the XRD pattern analysis, all diffraction peaks of the cesium tungsten bronze powder prepared by the method of Example 5 belong to Cs 0.23 WO3, indicating that pure-phase cesium tungsten bronze has been synthesized.

[0305] According to the SEM pattern analysis, the morphology of the Cs 0.23 WO3 powder prepared by the method of Example 5 is short rod-shaped, and the length of the short rod-shaped structure is 30 - 140 nm, and the diameter is 15 - 40 nm.

[0306] According to the Uv-Vis-NIR pattern analysis, the Cs 0.23 WO3 powder prepared by the method of Example 5 has high near-infrared absorption performance, ultraviolet shielding performance and high visible light transmittance performance.

[0307] According to the test of the photothermal conversion and heat insulation performance of the heat insulation coating on the upper surface of the glass, the heat insulation coating prepared in Example 5 has high photothermal conversion performance and heat insulation performance.

[0308] Preparation of Sodium Tungsten Bronze Na 0.30 WO3

[0309] The present invention synthesizes a sodium tungsten bronze alkoxide precursor by a hydrolysis method combined with a coprecipitation method and synthesizes sodium tungsten bronze at low temperature in the original liquid phase, which includes the following preparation steps:

[0310] See Figure 2 As shown, for the method of the nano sodium tungsten bronze coating prepared by the industrial preparation of low-temperature cation coordination tungsten salt hydrolysis of the present invention through a spraying process, it includes the following preparation steps:

[0311] Step 1, prepare a sodium source solution;

[0312] Dosage: The concentration of the sodium source in the sodium source solution is 2 mol / L.

[0313] Add NaCl and deionized water into the first stirring container; under normal pressure, set the dissolution temperature to 40 °C, the stirring speed to 300 r / min, and stir for 15 min to obtain the sodium source solution.

[0314] Step 2, prepare a tungsten source solution;

[0315] Dosage: The concentration of the tungsten source in the tungsten source solution is 0.075 mol / L.

[0316] Add WCl6 and CH3CH2OH into the second stirring container; under normal pressure, set the dissolution temperature to 35 °C, the stirring speed to 400 r / min, and stir for 25 min to obtain the tungsten source solution.

[0317] Step 3: Hydrolyze by water bath heating to generate a nano sodium tungsten bronze dispersion;

[0318] Dosage: To prepare 1 kg of cesium tungsten bronze powder, 2.2 kg of sodium source solution and 55.42 kg of tungsten source solution are required.

[0319] One-step low-temperature heating hydrolysis to prepare dispersion: Add the sodium source solution and tungsten source solution into a water bath heating container; Set the water bath temperature to 74 °C and the stirring speed of the water bath heating container to 400 r / min. After stirring for 1500 min, a dispersion is obtained.

[0320] Step 4: Solid-liquid separation;

[0321] In Example 6, the washing liquid is CH3CH2OH.

[0322] Step 41: Add the dispersion into a solid-liquid separator. After standing for 30 min, the first precipitate and the first supernatant are obtained; And discharge the first supernatant;

[0323] Step 42: Add the washing liquid into the solid-liquid separator. The washing liquid is 2 times that of the first precipitate; Set the stirring speed of the solid-liquid separator to 500 r / min. After stirring for 40 min and then standing for 40 min, the second precipitate and the second supernatant are obtained; And discharge the second supernatant;

[0324] Step 43: Add the washing liquid into the solid-liquid separator. The washing liquid is 2 times that of the second precipitate; Set the stirring speed of the solid-liquid separator to 400 r / min. After stirring for 50 min and then standing for 50 min, the third precipitate and the third supernatant are obtained; And discharge the third supernatant;

[0325] Step 47: Add deionized water into the solid-liquid separator. The solvent is 3 times that of the third precipitate; Set the stirring speed of the solid-liquid separator to 300 / min; After stirring for 60 min, a sodium tungsten bronze dispersion is obtained.

[0326] Dry to prepare sodium tungsten bronze powder

[0327] Dry the sodium tungsten bronze dispersion obtained in Step 4 in a vacuum resistance furnace at a drying temperature of 70 °C for 300 min to obtain sodium tungsten bronze powder, i.e., Na 0.30 WO3 powder. Through the calculation of the input raw materials and the product output, Na 0.30 The industrial yield of WO3 powder is 65%.

[0328] Step 5: Prepare sodium tungsten bronze coating;

[0329] Dosage (parts by weight): Sodium tungsten bronze dispersion: PVA: Deionized water = 1.5: 7: 120.

[0330] Add sodium tungsten bronze dispersion, PVA, and deionized water into the third stirring container; set the stirring speed of the third stirring container to 300 r / min; after stirring for 100 min, obtain sodium tungsten bronze coating;

[0331] Step six, fabricate the glass curtain wall by spraying process;

[0332] Inject the sodium tungsten bronze coating into the hopper of the spraying machine through a pipeline, and set the spraying distance H from the nozzle to the upper surface of the glass plate to 1.5 cm; the flow rate of the sodium tungsten bronze coating is 1 ml / min.

[0333] At a hot air temperature of 40 °C provided by a hot air blower and a transmission roller speed of 50 r / min, after curing, obtain a heat insulation coating on the upper surface of the glass.

[0334] To achieve large-size spraying of the glass curtain wall, the present invention adopts a structure with an array of nozzles. Refer to Figure 7 as shown. Ultrasonic atomizing nozzles 5C are arranged in an array on the flat plate 5A of the nozzle mechanism 5. The ultrasonic atomizing nozzles 5C are connected to the hopper of the spraying machine through a flexible conduit. A column 5B is provided at the center of the flat plate 5A, and the column 5B is fixed to the housing of the spraying machine.

[0335] In the present invention, the nozzle diameter of the ultrasonic atomizing nozzle 5C is 20 mm, and the nozzle orifice diameter is 1.5 mm. The number of ultrasonic atomizing nozzles 5C arranged on the flat plate 5A is determined according to the size of the fabricated glass curtain wall, the nozzle diameter, and the nozzle orifice diameter.

[0336] Characteristics and properties of sodium tungsten bronze prepared by the method of Example 6

[0337] According to the XRD pattern analysis, all diffraction peaks of the sodium tungsten bronze powder prepared by the method of Example 6 belong to Na 0.30 WO3, indicating that pure-phase sodium tungsten bronze is synthesized.

[0338] According to the SEM pattern analysis, the morphology of the Na 0.30 WO3 powder prepared by the method of Example 6 is short rod-shaped, and the length of the short rod-shaped structure is 30 - 140 nm, and the diameter is 15 - 40 nm.

[0339] According to the Uv-Vis-NIR pattern analysis, the Na 0.30 WO3 powder prepared by the method of Example 6 has high near-infrared absorption performance, ultraviolet shielding performance, and high visible light transmittance performance.

[0340] According to the test of the photothermal conversion and heat insulation performance of the heat insulation coating on the upper surface of the glass, the heat insulation coating prepared in Example 6 has high photothermal conversion performance and heat insulation performance.

[0341] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A method for industrially preparing nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salt, characterized in that It includes the following steps: Step 1, preparing an alkali metal source solution; Step 11, adding deionized water into the first stirring container; Inside the first stirring container (1), there is a stirrer. Above the cylinder body (1A) of the first stirring container (1), there are an alkali metal source feed port (1A1), a deionized water feed port (1A2), and an exhaust port (1A3); below the cylinder body (1A), there is a discharge port (1A4) for the alkali metal source solution; Step 12, adding the alkali metal source into the first stirring container; The alkali metal source includes hydroxides corresponding to alkali metal ions, chlorides, and salts of one or two combinations of nitrates, sulfates, and carbonates; The hydroxides are: cesium hydroxide, potassium hydroxide, or sodium hydroxide; The chlorides are: cesium chloride, rubidium chloride, potassium chloride, or sodium chloride; The nitrates are: cesium nitrate, potassium nitrate, or sodium nitrate; The sulfates are: cesium sulfate, potassium sulfate, or sodium sulfate; The carbonates are: cesium carbonate, potassium carbonate, or sodium carbonate; Step 13, under normal pressure, setting the dissolution temperature to 10°C - 40°C and the stirring speed to 200 r / min - 600 r / min; after stirring for 1 min - 15 min, an alkali metal source solution is prepared; The concentration of alkali metal ions in the prepared alkali metal source solution is 0.02 mol / L - 10 mol / L; Step 2, preparing a tungsten source solution; Step 21, adding the tungsten source into the second stirring container; The tungsten source is tungsten hexachloride or tungsten tetrachloride; Inside the second stirring container (2), there is a stirrer (2E); above the cylinder body (2A) of the second stirring container (2), there are a tungsten source feed port (2A1), an alcohol source feed port (2A2), and an exhaust port (2A3); below the cylinder body (2A), there is a discharge port (2A4) for the tungsten source mixed solution; between the outer wall of the inner shell (2C) of the second stirring container (2) and the inner wall of the cylinder body (2A), there is a heating wire (2D); Step 22, adding the alcohol solution into the second stirring container; The alcohol solution is a combination of one, two, or more of methanol, ethanol, n - propanol, isopropanol, and n - butanol; Step 23, under normal pressure, setting the dissolution temperature to 10°C - 40°C and the stirring speed to 200 r / min - 600 r / min; after stirring for 10 min - 60 min, a tungsten source solution is prepared; The concentration of the tungsten source in the prepared tungsten source solution is 0.02 mol / L - 1 mol / L; Step 3, generating a nano - alkali metal tungsten bronze dispersion by water - bath heating hydrolysis; Dosage: To prepare 1 kg of nano - alkali metal tungsten bronze powder, 0.18 kg - 90 kg of alkali metal source solution and 3.68 kg - 184 kg of tungsten source solution are required; One - step low - temperature heating hydrolysis to prepare an alkali metal tungsten bronze dispersion: adding the alkali metal source solution, the tungsten source solution, and deionized water into a water - bath heating container (3); setting the water - bath temperature to 40 - 95°C and the stirring speed to 200 r / min - 1000 r / min, after stirring for 90 min - 2880 min, an alkali metal tungsten bronze dispersion is obtained; The water-bath heating container (3) is divided into a heating cylinder (3C) and a water bath cylinder (3A), and a heating coil (3D) is provided between the heating cylinder (3C) and the water bath cylinder (3A). The water bath cylinder (3A) contains tap water. A stirrer (3E) is provided inside the heating cylinder (3C). Above the water-bath heating container (3), there are a CA feed inlet (3A1), a CB feed inlet (3A2), a CC feed inlet (3A3), and an exhaust port (3A4). Step four, solid-liquid separation; The washing liquid is methanol, ethanol, acetone; or a combination of methanol and deionized water; a combination of ethanol and deionized water; a combination of acetone and deionized water; Step 41, Add the alkali metal tungsten bronze dispersion to the solid-liquid separator (4), let it stand for 20 - 100 min to obtain the first precipitate and the first supernatant; and discharge the first supernatant; Step 42, Add the washing liquid to the solid-liquid separator (4), and the washing liquid is 2 - 5 times that of the first precipitate; Set the stirring speed of the solid-liquid separator to 200 r / min - 600 r / min, stir for 10 min - 60 min, then let it stand for 20 - 100 min to obtain the second precipitate and the second supernatant; and discharge the second supernatant; Step 43, Add the washing liquid to the solid-liquid separator (4), and the washing liquid is 2 - 5 times that of the second precipitate; Set the stirring speed of the solid-liquid separator to 200 r / min - 600 r / min, stir for 10 min - 60 min, then let it stand for 20 - 100 min to obtain the third precipitate and the third supernatant; and discharge the third supernatant; Step 47, Add the washing liquid to the solid-liquid separator (4), and the solvent is 2 - 5 times that of the third precipitate; Set the stirring speed of the solid-liquid separator to 200 r / min - 600 r / min; Stir for 10 min - 60 min to obtain the nano-alkali metal tungsten bronze dispersion; Inside the solid-liquid separator (4), there is a stirrer (4E); Above the cylinder body (4A) of the solid-liquid separator (4), there are a DA feed inlet (4A1), a DB feed inlet (4A2), and a DA discharge outlet (4A3); Below the cylinder body (4A), there is a DB discharge outlet (4A4); Step five, dry to prepare nano-alkali metal tungsten bronze powder; The alkali metal tungsten bronze liquid prepared in Step 4 is dried in a vacuum resistance furnace, with the vacuum degree pumped to 1×10 －2 Pa to 1×10 － 4 Pa, the drying temperature is 50°C to 100°C, and the drying time is 180 min to 720 min, to obtain alkali metal tungsten bronze powder.

2. The method for industrially preparing nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salt according to claim 1, characterized in that: Apply one-step low-temperature heating hydrolysis to synthesize nano-alkali metal tungsten bronze, whose composition is Cs X WO3, Rb X WO3, K X WO3, Na X WO3, where X = 0.2 - 0.

33.

3. The method for industrially preparing nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salt according to claim 1, characterized in that: The components for preparing the preferred nano-alkali metal tungsten bronze powder include Cs 0.30 WO3 powder, Rb 0.28 WO3 powder, K 0.32 WO3 powder or Na 0.33 WO3 powder.

4. The method for industrially preparing nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salt according to claim 1, characterized in that: The prepared nano-alkali metal tungsten bronze powder has a short rod shape or an equiaxial shape. The length of the short rod structure is 10 - 150 nm, the diameter is 10 - 50 nm, and the dimensions of each direction of the equiaxial structure are less than 100 nm.

5. The method for industrially preparing nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salt according to claim 1, characterized in that: The industrial yield of the prepared nano-cesium tungsten bronze powder is 70% - 85%, the industrial yield of the nano-rubidium tungsten bronze powder is 70% - 85%, the industrial yield of the nano-potassium tungsten bronze powder is 60% - 80%, and the industrial yield of the nano-sodium tungsten bronze powder is 50% - 75%.

6. A method for industrially manufacturing a nano-alkali metal tungsten bronze coating using the nano-alkali metal tungsten bronze solution prepared according to claim 1, characterized in that It includes the following steps: Step one, prepare the alkali metal source solution; Step 11, Add deionized water to the first stirring container; Step 12, Add the alkali metal source to the first stirring container; The alkali metal source includes hydroxides, chlorides corresponding to alkali metal ions, and salts of one or two combinations of nitrates, sulfates, and carbonates; The hydroxides described are: cesium hydroxide, potassium hydroxide or sodium hydroxide; The chlorides described are: cesium chloride, rubidium chloride, potassium chloride or sodium chloride; The nitrates described are: cesium nitrate, potassium nitrate or sodium nitrate; The sulfates described are: cesium sulfate, potassium sulfate or sodium sulfate; The carbonates described are: cesium carbonate, potassium carbonate or sodium carbonate; Step 13, under atmospheric pressure, set the dissolution temperature to 10°C - 40°C and the stirring speed to 200 r / min - 600 r / min; after stirring for 1 min - 15 min, an alkali metal source solution is prepared; The concentration of alkali metal ions in the prepared alkali metal source solution is 0.05 mol / L - 5 mol / L; Step two, prepare a tungsten source solution; Step 21, add the tungsten source to the second stirring container; The tungsten source is tungsten hexachloride or tungsten tetrachloride; Step 22, add the alcohol solution to the second stirring container; The alcohol solution is one, two or a combination of more of methanol, ethanol, n-propanol, isopropanol, n-butanol; Step 23, under atmospheric pressure, set the dissolution temperature to 15°C - 40°C and the stirring speed to 200 r / min - 600 r / min; after stirring for 10 min - 60 min, a tungsten source solution is prepared; The concentration of the tungsten source in the prepared tungsten source solution is 0.05 mol / L - 1 mol / L; Step three, hydrolyze by water bath heating to generate a nano alkali metal tungsten bronze dispersion; Dosage: To prepare 1 kg of nano alkali metal tungsten bronze powder, 0.23 kg - 36 kg of alkali metal source solution and 3.68 kg - 123 kg of tungsten source solution are required; One-step low-temperature heating hydrolysis to prepare an alkali metal tungsten bronze dispersion: Add the alkali metal source solution, tungsten source solution and deionized water to a water bath heating container; set the water bath temperature to 40°C - 90°C, the stirring speed to 200 r / min - 1000 r / min, and after stirring for 90 min - 2880 min, a dispersion is obtained; Step four, solid-liquid separation; The washing liquid is methanol, ethanol, acetone; or a combination of methanol and deionized water; a combination of ethanol and deionized water; a combination of acetone and deionized water; Step 41, add the alkali metal tungsten bronze dispersion to the solid-liquid separator, let it stand for 20 - 100 min to obtain the first precipitate and the first supernatant; and drain the first supernatant; Step 42, add the washing liquid to the solid-liquid separator, and the washing liquid is 2 - 5 times that of the first precipitate; set the stirring speed of the solid-liquid separator to 200 r / min - 600 r / min, stir for 10 min - 60 min and then let it stand for 20 - 100 min to obtain the second precipitate and the second supernatant; and drain the second supernatant; Step 43, add the washing liquid to the solid-liquid separator, and the washing liquid is 2 - 5 times that of the second precipitate; set the stirring speed of the solid-liquid separator to 200 r / min - 600 r / min, stir for 10 min - 60 min and then let it stand for 20 - 100 min to obtain the third precipitate and the third supernatant; and drain the third supernatant; Step 47: Add washing liquid into the solid-liquid separator, where the solvent is 0.5 to 2 times that of the third precipitate; set the stirring speed of the solid-liquid separator to 200 r / min to 600 r / min; after stirring for 10 min to 60 min, an alkali metal tungsten bronze dispersion is obtained; Step Five: Prepare an alkali metal tungsten bronze coating; Dosage: alkali metal tungsten bronze dispersion: PVA: deionized water = 1:2 to 15:80 to 130; Add the alkali metal tungsten bronze dispersion, PVA, and deionized water into the third stirring container; set the stirring speed of the third stirring container to 100 r / min to 400 r / min; after stirring for 30 min to 120 min, an alkali metal tungsten bronze coating is obtained; Step Six: Fabricate a glass curtain wall by spraying process; Inject the alkali metal tungsten bronze coating into the hopper of the sprayer through a pipeline, and set the spraying distance H from the nozzle to the upper surface of the glass plate to be 0.5 to 2 cm; the flow rate of the alkali metal tungsten bronze coating is 1 to 7 ml / min; At a hot air temperature of 22 °C to 40 °C provided by a hot air blower and a transmission roller speed of 10 r / min to 60 r / min, after curing, a nano alkali metal tungsten bronze coating on the upper surface of the glass is fabricated.

7. A method for industrializing a nano-alkali metal tungsten bronze coating using the nano-alkali metal tungsten bronze solution prepared according to claim 6, characterized in that: The fabricated nano alkali metal tungsten bronze coating is applied to the glass curtain wall.

8. A method for industrializing a nano-alkali metal tungsten bronze coating using the nano-alkali metal tungsten bronze solution prepared according to claim 6, characterized in that: The glass loaded with nano alkali metal tungsten bronze reduces the temperature inside the box by 10 °C to 15.5 °C, and the temperature drop reaches 10% to 25%.

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