Industrial method for producing nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salts

Abstract

The present invention discloses an industrial manufacturing method of nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation coordination tungsten salt, and the application of nano-alkali metal tungsten bronze coating. The method of the present invention applies one-step low-temperature heating hydrolysis to synthesize nano-alkali metal tungsten bronze, without the need for special equipment in the manufacturing process, without the need for high temperature and high pressure, with mild process conditions, low energy consumption, short cycle, high production volume, high yield, and low cost. The synthesized product has good crystallinity, and its components are Cs x WO3, Rb x WO3, K x WO3, Na x WO3, where X = 0.2 - 0.33. The particle length of the synthesized short rod-shaped alkali metal tungsten bronze is 10 - 150 nm, the diameter is 10 - 50 nm, and the size in each direction of the synthesized equiaxed alkali metal tungsten bronze is less than 100 nm. All of the above powders have excellent near-infrared shielding performance, visible light transmission performance, good ultraviolet shielding performance, and certain mid- and far-infrared shielding performance. The nano-alkali metal tungsten bronze coating manufactured by the present invention has a simple and controllable manufacturing process, high near-infrared shielding performance, and excellent ultraviolet shielding performance.

Description

Technical Field

[0001] The present invention relates to an alkali metal tungsten bronze nanomaterial, and particularly to an industrial manufacturing method of nano-alkali metal tungsten bronze by hydrolysis of a low-temperature cation coordination tungsten salt, and the use of the manufactured nano-alkali metal tungsten bronze in a building decoration curtain wall to achieve heat insulation and temperature reduction performance.

Background Art

[0002] Alkali metal tungsten bronze is a typical non-stoichiometric compound, and its chemical formula is M x WO3(0≦X≦0.33). Because it has a one-dimensional tunnel structure labeled with a special six-membered ring and mixed-valence W ions, it is given many excellent physicochemical properties such as photothermal conversion, selective light absorption, and near-infrared shielding, and has broad application prospects in fields such as energy, military, architecture, and medical.

[0003] With the wide application of alkali metal tungsten bronze nanomaterials, its manufacturing technology has become increasingly important. Currently, the manufacture of alkali metal tungsten bronze powder mainly includes the following methods.

[0004] Solid-phase method: In the solid-phase method, generally, a simple metal, oxide or salt and tungsten and tungsten oxides are mixed, and various types of alkali metal tungsten bronzes are obtained by solid-phase reaction under conditions such as higher temperature, pressure or ball milling. However, the alkali metal tungsten bronze synthesized by this method is difficult to control in morphology, and the particle size of the product is relatively large.

[0005] Wet chemical method: The wet chemical method mainly includes the solvothermal method and the hydrothermal method. The wet chemical method features mild synthesis conditions, simple operation, and easy control of the size and morphology of the products. The alkali metal tungsten bronze nanopowders produced by the wet chemical method have a narrow particle size distribution, a low degree of powder aggregation, and do not require high-temperature annealing treatment in a reducing atmosphere. However, due to the low concentration of reactants and the high reaction temperature and pressure, special equipment (reaction kettle) is required in the synthesis process, there is a certain risk in the reaction, the reaction time is long, and the single production volume is extremely low, which is not suitable for industrial production.

[0006] High-temperature reduction method: In the high-temperature reduction method, hydrogen gas needs to be introduced during the heating process at a high temperature (800 °C). The manufacturing process is complex, the utilization rate of raw materials is low, and there is a certain risk (H. Takeda, K. Adachi, J. Am. Ceramic Soc., 2007, 90(12), 4059 - 4061). Solvothermal or hydrothermal reactions also require a high reaction temperature (generally above 200 °C), and the manufacturing time is as long as 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 wall materials with decorative effects commonly used in modern large-scale and high-rise buildings. Due to limitations in materials and processing processes, curtain walls do not meet the requirements of thermal physical elements (thermal radiation, condensation) and sound insulation, fire protection, etc., and have not achieved good development and popularity. Currently, with the combination of curtain wall processes and science and technology, in response to the global call for energy conservation, smart curtain walls such as glass curtain walls, solar power generation curtain walls, ventilation duct breathing curtain walls, and smart curtain walls sensitive to wind and rain are showing the unique charm of architecture.

[0008] In order to achieve energy conservation of coating materials in architectural decorative curtain walls, it is urgent to provide an industrial processing method for manufacturing alkali metal tungsten bronze materials on a large scale at low temperature.

Summary of the Invention

[0009] One objective of the present invention is to provide an industrial method for producing nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salts. Because this production method is carried out during the hydrolysis process, the reaction time is short, the reaction temperature is low (40°C to 95°C), and low-cost industrial production of alkali metal tungsten bronze nanomaterials is realized. The method of the present invention synthesizes nano-alkali metal tungsten bronze by applying a one-step low-temperature heating hydrolysis, and its component is Cs x WO3, Rb x WO3, K x WO3, Na x The composition is WO3, where X = 0.2-0.33. The nano-alkali metal tungsten bronze produced by the method of the present invention has a short rod-shaped structure and an equiaxed structure. The synthesized short rod-shaped alkali metal tungsten bronze nanoparticles have a length of 10-150 nm and a diameter of 10-50 nm, while the synthesized equiaxed alkali metal tungsten bronze nanoparticles have a size of less than 100 nm in each direction. The above products have good crystallinity and excellent visible light transmittance, near-infrared shielding performance, good ultraviolet shielding, and a certain degree of mid-to-far infrared shielding performance. The present invention obtains alkali metal tungsten bronze nanopowder under low temperature and no pressure conditions by precisely controlling the coordination between the product obtained by hydrolysis of the tungsten source in the reaction system and the alkali metal element, and by reacting in a liquid phase below the boiling point of the solvent. By precisely controlling the stirring speed, reaction time, and temperature of the reaction system, the crystallization rate can be controlled and the particle size of alkali metal tungsten bronze can be controlled. The tungsten source, alkali metal source, deionized water, and alcohol solution used in this invention are all environmentally friendly reagents and have low costs. The reaction system used in the method of this invention operates at low temperatures, without high pressure, produces a uniform product morphology, has a short production cycle, low energy consumption, requires no special equipment, has high yields, and produces large volumes of products.

[0010] A second objective of the present invention is to provide large-scale, low-cost production of glass curtain walls by industrially spray-coating an alkali metal tungsten bronze paint onto a glass surface. The coating manufacturing method proposed in the present invention does not require special equipment, has a simple process, and has a short manufacturing cycle. The coating manufactured in the present invention has excellent near-infrared shielding performance, high visible light transmittance, good ultraviolet shielding performance, and excellent heat insulation performance.

[0011] The present invention provides an industrial method for producing nano-alkali metal tungsten bronze by hydrolysis of a low-temperature cation-coordinated tungsten salt, comprising the following steps: Step 1: Preparation of alkali metal source solution; Step 11: Add deionized water to the first stirring vessel; Step 12: Add the alkali metal source to the first stirring vessel; Step 13: Set the mixture to atmospheric pressure, with a dissolution temperature of 10°C to 40°C and a stirring speed of 200 r / min to 600 r / min; after stirring for 1 min to 15 min, prepare the alkali metal source solution; Step 2: Preparation of tungsten source solution; Step 21: Add the tungsten source to the second stirring vessel; Step 22: Add the alcohol solution to the second stirring vessel; Step 23: Set the mixture to atmospheric pressure, with a dissolution temperature of 10°C to 40°C and a stirring speed of 200 r / min to 600 r / min; after stirring for 10 min to 60 min, produce the tungsten source solution; Step three: Heat in a water bath to produce a nano-alkali metal tungsten bronze dispersion by hydrolysis; Dosage: To produce 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; Production of alkali metal tungsten bronze dispersion by one-step low-temperature heating hydrolysis: Add alkali metal source solution, tungsten source solution, and deionized water to a water bath heating vessel (3); set the water bath temperature to 40-95°C and the stirring speed to 200 r / min-1000 r / min, and after stirring for 90 min-2880 min, obtain alkali metal tungsten bronze dispersion; Step 4, solid-liquid separation; Step 5: Production of nano-alkali metal tungsten bronze powder by drying; The alkali metal tungsten bronze liquid produced in step four is dried in a vacuum resistance furnace, and the vacuum level is set to 1 × 10⁻⁶. -2 Pa~1×10 -4 Alkali metal tungsten bronze powder is obtained by setting the temperature to Pa, drying at a temperature of 50°C to 100°C, and drying for 180 min to 720 min.

[0012] The advantages of this invention in industrially producing nano-alkali metal tungsten bronze by employing the hydrolysis of low-temperature cation-coordinated tungsten salts are as follows:

[0013] [1] Industrial production of nano-alkali metal tungsten bronze by employing hydrolysis of low-temperature cation-coordinated tungsten salts achieves the synthesis of pure-phase alkali metal tungsten bronze under low-temperature and low-pressure conditions, the process conditions are mild, the crystallinity of the product is good, subsequent calcination is unnecessary, and energy consumption is low.

[0014] [2] Industrial production of nano-alkali metal tungsten bronze using hydrolysis of low-temperature cation-coordinated tungsten salts is possible because it does not require strict conditions on the type of raw materials and there are many types of alkali metal sources and solvents that can be used.

[0015] [3] Industrially producing nano-alkali metal tungsten bronze by employing the hydrolysis of low-temperature cation-coordinated tungsten salts has a simple industrial flow, a short production cycle, and does not require special high-temperature, high-pressure equipment.

[0016] [4] Industrial production of nano-alkali metal tungsten bronze using hydrolysis of low-temperature cation-coordinated tungsten salts yields high yields and large production volumes.

[0017] [5] Industrially producing nano-alkali metal tungsten bronze by employing hydrolysis of low-temperature cation-coordinated tungsten salts allows for control of the synthesis period of the pure phase alkali metal tungsten bronze by stirring time and stirring speed, and does not affect the morphology of the pure phase cesium tungsten bronze.

[0018] [6] Industrial production of nano-alkali metal tungsten bronze by employing the hydrolysis of low-temperature cation-coordinated tungsten salts is not sensitive to the volume of the reaction vessel, the volume of the liquid phase, and the material, and the production volume can be easily controlled by increasing the volume of the reaction vessel or the volume of the liquid phase.

[0019] [7] Industrial production of nano-alkali metal tungsten bronze using hydrolysis of low-temperature cation-coordinated tungsten salts yields superior product performance.

[0020] [8] In the spray coating process, the present invention sets the distance between the ultrasonic atomizing nozzle array and the upper surface of the pre-coat substrate to 5 to 20 cm, enabling the ultrasonic atomizing nozzle array to achieve large-area spray coating in a short time in a spray coating area of ​​0.8 m × 0.8 m or more, and then hardens with hot air to improve the bonding strength between the coating and the glass surface. [Brief explanation of the drawing]

[0021] [Figure 1] This is a flowchart illustrating the industrial production method of nano-alkali metal tungsten bronze by hydrolysis of a low-temperature cation-coordinated tungsten salt according to the present invention. [Figure 2] This is a flowchart for manufacturing a glass curtain wall using nano-alkali metal tungsten bronze obtained by industrial production by hydrolysis of the low-temperature cation-coordinated tungsten salt of the present invention. In Figure 2, T represents a temperature sensor, F represents a pressure gauge, and P represents a flow meter and a valve installed in the passage. [Figure 3] This is a cross-sectional view of the structure of the first stirring vessel of the present invention. [Figure 4] This is a cross-sectional view of the structure of the second stirring vessel of the present invention. [Figure 5] This is a cross-sectional view of the structure of the water bath heating container of the present invention. [Figure 6] This is a cross-sectional view of the structure of the solid-liquid separator of the present invention. [Figure 7] This is a schematic diagram of the nozzle array arrangement of the spray coater of the present invention. [Figure 8] These are the XRD patterns of the target products obtained in Examples 1, 2, 3, and 4. [Figure 9] This is an SEM image of the target product obtained in Example 1. [Figure 10] This is an SEM image of the target product obtained in Example 2. [Figure 11] This is an SEM image of the target product obtained in Example 3. [Figure 12] This is an SEM image of the target product obtained in Example 4. [Figure 13] This is a diagram showing the near-infrared shielding performance of the powder obtained in Example 1. [Figure 14] This diagram shows the far-infrared shielding performance of the powder obtained in Example 1. [Figure 15] These are the UV-Vis-NIR transmission spectra of the composite films of the target product obtained in Examples 1, 2, 3, and 4 with PVA. [Figure 16] This is a time-dependent temperature curve inside a sealed box when a quartz glass coated with a PVA / M0.3WO3 thin film in Example 1 is irradiated with a 50W solar lamp. [Modes for carrying out the invention]

[0022] The present invention will be described in more detail below with reference to the drawings and embodiments.

[0023] As shown in Figure 1, the present invention provides an industrial method for producing nano-alkali metal tungsten bronze by hydrolysis of a low-temperature cation-coordinated tungsten salt, the method comprising the following manufacturing steps.

[0024] Step 1: Preparation of alkali metal source solution; Step 11: Add deionized water to the first stirring vessel; Step 12: Add the alkali metal source to the first stirring vessel; In this invention, the alkali metal source includes a salt of one or two of the hydroxides, chlorides, and nitrates, sulfates, and carbonates corresponding to the alkali metal ions.

[0025] The hydroxide is cesium hydroxide, potassium hydroxide, or sodium hydroxide.

[0026] The chloride salt is cesium chloride, rubidium chloride, potassium chloride, or sodium chloride.

[0027] The nitrate is cesium nitrate, potassium nitrate, or sodium nitrate.

[0028] The sulfate salt is cesium sulfate, potassium sulfate, or sodium sulfate.

[0029] The carbonate is cesium carbonate, potassium carbonate, or sodium carbonate.

[0030] Step 13: At atmospheric pressure, the dissolution temperature is set 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, the alkali metal source solution is produced.

[0031] The alkali metal source concentration in the manufactured alkali metal source solution ranges from 0.1 mol / L to 6 mol / L.

[0032] As shown in Figure 3, in the present invention, the first stirring container 1 is a double-layered stainless steel round tub. A stirrer 1E is installed inside the first stirring container 1, and the stirrer 1E provides the stirring speed during the production process of the first solution, with a stirring speed of 200 r / min to 600 r / min.

[0033] Above the cylinder 1A of the first stirring vessel 1, an alkali metal source supply port 1A1, a deionized water supply port 1A2, and an exhaust port 1A3 are installed; the exhaust port 1A3 discharges gases generated during the manufacturing process of the alkali metal source solution to ensure safety during the manufacturing process of the alkali metal source solution; below the cylinder 1A, an alkali metal source solution outlet 1A4 is installed. The outlet 1A4 can communicate with the water bath heating vessel 3 via connected piping, and as shown in Figure 2, a pressure gauge, flow meter, valve, etc. can be installed in this piping.

[0034] A base 1B is installed at the bottom of the first stirring vessel 1. The base 1B supports the stirring vessel and stabilizes the first stirring vessel 1 in its operating state.

[0035] In this invention, a temperature sensor is installed in the first stirring vessel 1 to monitor the temperature during the manufacturing process of the alkali metal source solution and to measure the dissolution temperature during the manufacturing process of the alkali metal source solution. If the current dissolution temperature is higher than the set dissolution temperature (10°C to 40°C), the stirring speed is reduced.

[0036] Step 2: Preparation of tungsten source solution; Step 21: Add the tungsten source to the second stirring vessel; In this invention, the tungsten source is tungsten hexachloride (WCl6) or tungsten tetrachloride (WCl4).

[0037] Step 22: Add the alcohol solution to the second stirring vessel; In this invention, the alcohol solution is one or more combinations of methanol (CH3OH), ethanol (CH3CH2OH), n-propanol (CH3(CH2)2OH), isopropanol (CH(CH3)2OH), and n-butanol (CH3(CH2)3OH).

[0038] Step 23: Set the mixture to atmospheric pressure, a dissolution temperature of 15°C to 40°C, and a stirring speed of 200 r / min to 600 r / min; after stirring for 10 min to 60 min, produce the tungsten source solution.

[0039] The tungsten source concentration of the manufactured tungsten source solution is between 0.04 mol / L and 1 mol / L.

[0040] As shown in Figure 4, in the present invention, the second stirring container 2 is a double-layered stainless steel round tub. A stirrer 2E is installed inside the second stirring container 2, and the stirrer 2E provides the stirring speed during the production process of the tungsten source solution, with a stirring speed of 200 r / min to 600 r / min.

[0041] Above cylinder 2A of the second stirring vessel 2, a tungsten source supply port 2A1, an alcohol source supply port 2A2, and an exhaust port 2A3 are installed. The exhaust port 2A3 discharges gases generated during the production of the tungsten source solution to ensure safety during the production process of the tungsten source solution. Below cylinder 2A, an outlet 2A4 for the tungsten source mixed solution is installed. The outlet 2A4 can communicate with the water bath heating vessel 3 via connected piping, and as shown in Figure 2, a pressure gauge, flow meter, valve, etc., can be installed in this piping.

[0042] A base 2B is installed at the bottom of the second stirring vessel 2. The base 2B supports the stirring vessel while stabilizing the stirring vessel 1 in its operating state. On the outer wall of the inner housing 2C of the second stirring container 2, a resistance wire 2D is wound, that is, the resistance wire 2D is installed between the outer wall of the inner housing 2C and the inner wall of the cylinder 2A, and a heat insulating material is filled. When manufacturing the tungsten source solution, if the measured temperature of the second stirring container 2 is lower than the set dissolution temperature as measured by a thermometer, it is necessary to provide a heat source by the resistance wire 2D and heat the tungsten source solution in the manufacturing process.

[0043] In the present invention, in order to monitor the temperature in the manufacturing process of the tungsten source solution, a temperature sensor is installed in the second stirring container 2 to measure the dissolution temperature in the manufacturing process of the second solution. If the current dissolution temperature is lower than the set dissolution temperature (10°C to 40°C), the resistance wire 2D is activated to heat the tungsten source solution in the manufacturing process.

[0044] In the present invention, the second stirring container 2 can also be adopted for manufacturing the alkali metal source mixed solution.

[0045] In the present invention, the first stirring container 1 can also be adopted for manufacturing the tungsten source mixed solution.

[0046] Step 3: Heating in a water bath and generating a nano-alkali metal tungsten bronze dispersion by hydrolysis; As shown in FIGS. 1, 2, and 5, in the present invention, an alkali metal cation (M + ) and a tungsten salt are coordinated, and then deionized water is added to complete the stepwise hydrolysis of the tungsten salt coordinated with the alkali metal cation. Finally, in order to obtain a nano-alkali metal tungsten bronze dispersion, the alkali metal source solution is mixed with the tungsten source solution using a water bath heating container. In the present invention, a means of performing hydrolysis after coordination is adopted to quickly limit the desired alkali metal element (M) into the product M x WO3, and M +This avoids the drawback of not being involved in the subsequent hydrolysis reaction and significantly improves the utilization rate of element M. The electronic structure change due to coordination reduces hexavalent tungsten in the mixed solution of alkali metal source solution and tungsten source solution, thereby rapidly forming the crystal-forming particles necessary for nano-alkali metal tungsten bronze in the mixed solution and industrially accelerating the hydrolysis reaction rate.

[0047] Dosage: To produce 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.

[0048] Production of alkali metal tungsten bronze dispersion by one-step low-temperature heating hydrolysis: Add alkali metal source solution, tungsten source solution, and deionized water to a water bath heating vessel; set the water bath temperature to 40°C to 90°C, set the stirring speed of the water bath heating vessel to 200 r / min to 1000 r / min, and stir for 90 min to 2880 min to obtain alkali metal tungsten bronze dispersion.

[0049] In this invention, the production of alkali metal tungsten bronze dispersions using a low-temperature environment of 40°C to 95°C provided by the water bath heating vessel 3 achieves the synthesis of alkali metal tungsten bronze under extremely mild process conditions, avoiding the extreme conditions (high temperature, high pressure) required for the two conventional methods, the solvothermal and hydrothermal methods. Using a water bath heating vessel instead of specialized high-temperature, high-pressure equipment allows for the use of equipment of medium to low complexity instead of highly complex equipment.

[0050] Using the water bath heating vessel 3 to produce nano-alkali metal tungsten bronze dispersions avoids the use of high-temperature, high-pressure specialized equipment in large-scale production processes. On the other hand, using a water bath heater instead of high-temperature, high-pressure specialized equipment significantly reduces equipment purchase costs; on the other hand, the water bath heater is easy to operate and does not increase significant time costs (e.g., experimenter training) when changing process equipment, nor does it introduce the factory / laboratory design costs (e.g., heating, electrical wiring, etc.) required for excessive equipment replacement.

[0051] The production of alkali metal tungsten bronze dispersions using a water bath heater in a low-temperature environment (40°C to 95°C) enables the use of medium-to-low complexity equipment instead of high-complexity equipment, and low-risk process flows instead of high-risk process flows. By enabling temperature control and introducing stirring operations, process selectivity is expanded, the controllability of reaction progress is improved, process safety is significantly enhanced, the time cost required for the same production volume is reduced, and production energy consumption is lowered.

[0052] Refer to the water bath heating container 3 designed according to the present invention shown in Figure 5. The water bath heating container 3 is divided into a heating cylinder 3C and a water bath cylinder 3A, and is made of stainless steel. A heating coil 3D is installed between the heating cylinder 3C and the water bath cylinder 3A, and tap water is injected into the water bath cylinder 3A. A stirrer 3E is installed inside the heating cylinder 3C, and the stirrer 3E provides the stirring speed during the dispersion production process, with a stirring speed of 200 r / min to 1000 r / min.

[0053] Above the water bath heating container 3, a CA supply port 3A1 (for injecting alkali metal source solution), a CB supply port 3A2 (for injecting tungsten source solution), a CC supply port 3A3 (for injecting deionized water), and an exhaust port 3A4 are installed, with the exhaust port 3A4 discharging gas generated during the dispersion manufacturing process; below the cylinder 3A, a dispersion outlet 3A5 is installed. The dispersion outlet 3A5 can communicate with a solid-liquid separator 4 via connected piping, and pressure gauges, flow meters, valves, etc., can be installed in this piping.

[0054] A base 3B is installed at the bottom of the water bath heating container 3. The base 3B supports the water bath heating container while stabilizing it in the stirring state.

[0055] In this invention, a heating coil 3D (such as a resistance wire) is wrapped around the outer wall of the heating cylinder 3C of the water bath heating container 3, and the container is immersed in tap water. That is, the heating coil 3D and the water necessary for heating the water bath are placed between the outer wall of the heating cylinder 3C and the inner wall of the water bath cylinder 3A, the heating coil 3D provides a heat source to the tap water, and an insulating material is wrapped around the outer wall of the water bath cylinder 3A. When manufacturing the dispersion, if the measured temperature of the water bath heating container 3 is lower than the set water bath temperature as measured by a thermometer, it is necessary to heat the tap water with the heating coil 3D to provide a heat source for manufacturing the dispersion.

[0056] In this invention, a temperature sensor is installed in the water bath heating container 3 to monitor the temperature during the manufacturing process of the dispersion, and the dissolution temperature during the manufacturing process of the dispersion is measured.

[0057] Step 4, solid-liquid separation; In the present invention, as shown in Figures 1, 2, and 6, during the solid-liquid separation process, a washing solution is added and the mixture is washed multiple times to remove organic and inorganic impurities that may be adsorbed onto the surface of the product remaining after the reaction. This purifies the product and prevents secondary aggregation of nano-alkali metal tungsten bronze particles in the dispersion.

[0058] In this invention, the washing solution is methanol (CH3OH), ethanol (CH3CH2OH), acetone (C3H6O); or a combination of methanol and deionized water; a combination of ethanol and deionized water; or a combination of acetone and deionized water.

[0059] Step 41: Add the alkali metal tungsten bronze dispersion to the solid-liquid separator 4, and after standing for 20 to 100 minutes, obtain the first precipitate and the first supernatant; and then drain the first supernatant. In this invention, the maximum amount of alkali metal tungsten bronze dispersion liquid that enters the solid-liquid separator 4 is two-thirds of the solid-liquid separator capacity.

[0060] Step 42: Add washing solution to solid-liquid separator 4 so that the washing solution is 2 to 5 times the amount 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 stand for 20 to 100 min to obtain the second precipitate and second supernatant; and then discharge the second supernatant; Step 43: Add washing solution to solid-liquid separator 4 so that the washing solution is 2 to 5 times the volume of the second 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 stand for 20 to 100 min to obtain the third precipitate and the third supernatant; and then discharge the third supernatant; Step 47: Washing solution is added to the solid-liquid separator 4 so that the solvent is 2 to 5 times the amount of the third precipitate; the stirring speed of the solid-liquid separator is set to 200 r / min to 600 r / min; and after stirring for 10 min to 60 min, an alkali metal tungsten bronze dispersion is obtained.

[0061] Figure 6 shows a solid-liquid separator 4 designed according to the present invention. The solid-liquid separator 4 is a double-layered stainless steel round container. An agitator 4E is installed inside the solid-liquid separator 4, and the agitator 4E provides the stirring speed during the separation process of the dispersion liquid, with a stirring speed of 200 r / min to 600 r / min.

[0062] Above cylinder 4A of solid-liquid separator 4, there are DA supply port 4A1 (for injecting alkali metal tungsten bronze dispersion), DB supply port 4A2 (for injecting washing solution), and DA discharge port 4A3 (for discharging supernatant); below cylinder 4A, there is a DB discharge port 4A4, which is for discharging alkali metal tungsten bronze solution. In Figure 2, the DB discharge port 4A4 can be connected to a third agitator via a connected pipe, and a pressure gauge, flow meter, valve, etc. can be installed in this pipe.

[0063] A base 4B is installed at the bottom of the solid-liquid separator 4. The base 4B supports the solid-liquid separator while stabilizing it in the agitation state.

[0064] Step 5: Production of nano-alkali metal tungsten bronze powder by drying; In this invention, in order to analyze the performance of the nano-alkali metal tungsten bronze liquid material produced in step four, it is necessary to dry the nano-alkali metal tungsten bronze liquid to obtain nano-alkali metal tungsten bronze powder. The cesium tungsten bronze liquid produced in step four is dried in a vacuum resistance furnace, and the vacuum level is set to 1 × 10⁻⁶. -2 Pa~1×10 -4 Nano-alkali metal tungsten bronze powder is obtained by setting the temperature to Pa, drying at a temperature of 50°C to 100°C, and drying for 180 min to 720 min.

[0065] Analysis of nanoalkali metal tungsten bronze powder produced by the present invention method using XRD patterns revealed that the chemical formula M x It satisfies the requirements of WO3 (0.2 ≤ X ≤ 0.33). A preferred component produced by the method of the present invention is Cs 0.30 WO3 powder, Rb 0.28 WO3 powder, K 0.32 WO3 powder and Na 0.33WO3 powder is available. According to calculations of the raw materials and product yields, the industrial yield of the manufactured nanocesium tungsten bronze powder is 70% to 85%, the industrial yield of nanorubidium tungsten bronze powder is 70% to 85%, the industrial yield of nanopotassium tungsten bronze powder is 60% to 80%, and the industrial yield of nanosodium tungsten bronze powder is 50% to 75%.

[0066] Analysis by SEM spectroscopy revealed that the nanoalkali metal tungsten bronze powder produced by the method of the present invention is short rod-shaped or equiaxed, with the short rod-shaped structure having a length of 10-150 nm and a diameter of 10-50 nm, and the equiaxed structure having a size of less than 100 nm in each direction.

[0067] In this invention, Figure 1 illustrates a powder process for the industrial production of nano-alkali metal tungsten bronze by hydrolysis of a low-temperature cation-coordinated tungsten salt. The difference in the process lies in the production of an alkali metal tungsten bronze dispersion by a single-step low-temperature heating hydrolysis. Synthesis of pure alkali metal tungsten bronze in a water bath under low temperature and no-pressure conditions is achieved, the process conditions are mild, the product (nano-alkali metal tungsten bronze powder) has good crystallinity, subsequent calcination is unnecessary, and energy consumption is low.

[0068] In the industrial production of the nano-alkali metal tungsten bronze liquid shown in Figure 1, as shown in Figure 2, the nano-alkali metal tungsten bronze liquid is applied to produce nano-alkali metal tungsten bronze paint, a nano-alkali metal tungsten bronze coating is produced on a glass plate using the nano-alkali metal tungsten bronze paint, and a glass curtain wall is produced using the glass supported by the nano-alkali metal tungsten bronze coating, which leads to indoor temperature reduction. The process for industrially producing the nano-alkali metal tungsten bronze coating according to the present invention is as follows.

[0069] Step 1: Preparation of alkali metal source solution; Step 11: Add deionized water to the first stirring vessel; Step 12: Add the alkali metal source to the first stirring vessel; In this invention, the alkali metal source includes a salt of one or two of the hydroxides, chlorides, and nitrates, sulfates, and carbonates corresponding to alkali metal ions.

[0070] The hydroxide is cesium hydroxide, potassium hydroxide, or sodium hydroxide.

[0071] The chloride salt is cesium chloride, rubidium chloride, potassium chloride, or sodium chloride.

[0072] The nitrate is cesium nitrate, potassium nitrate, or sodium nitrate.

[0073] The sulfate salt is cesium sulfate, potassium sulfate, or sodium sulfate.

[0074] The carbonate is cesium carbonate, potassium carbonate, or sodium carbonate.

[0075] Step 13: Set the mixture to atmospheric pressure, a dissolution temperature of 10°C to 40°C, and a stirring speed of 200 r / min to 600 r / min; after stirring for 10 min to 60 min, produce the alkali metal source solution.

[0076] The alkali metal source concentration in the manufactured alkali metal source solution is between 0.5 mol / L and 5 mol / L.

[0077] Step 2: Preparation of tungsten source solution; Step 21: Add the tungsten source to the second stirring vessel; In the present invention, the tungsten source is tungsten hexachloride (WCl6) or tungsten tetrachloride (WCl4).

[0078] Step 22: Add the alcohol solution to the second stirring vessel; In this invention, the alcohol solution is one or more combinations of methanol (CH3OH), ethanol (CH3CH2OH), n-propanol (CH3(CH2)2OH), isopropanol (CH(CH3)2OH), and n-butanol (CH3(CH2)3OH).

[0079] Step 23: Set the mixture to atmospheric pressure, with a dissolution temperature of 15°C to 40°C and a stirring speed of 200 r / min to 600 r / min; after stirring for 10 min to 60 min, produce the tungsten source solution.

[0080] The tungsten source concentration of the manufactured tungsten source solution is between 0.05 mol / L and 1 mol / L.

[0081] Step three: Heat in a water bath to produce a nano-alkali metal tungsten bronze dispersion by hydrolysis; Dosage: To produce 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.

[0082] Production of alkali metal tungsten bronze dispersion by one-step low-temperature heating hydrolysis: Add alkali metal source solution, tungsten source solution, and deionized water to a water bath heating vessel; set the water bath temperature to 40°C to 90°C, set the stirring speed of the water bath heating vessel to 200 r / min to 1000 r / min, and stir for 90 min to 2880 min to obtain the dispersion.

[0083] Step 4, solid-liquid separation; In this invention, the washing solution is methanol (CH3OH), ethanol (CH3CH2OH), acetone (C3H6O); or a combination of methanol and deionized water; a combination of ethanol and deionized water; or a combination of acetone and deionized water.

[0084] Step 41: Add the alkali metal tungsten bronze dispersion to the solid-liquid separator and let it stand for 20-100 minutes to obtain the first precipitate and the first supernatant; then drain the first supernatant; Step 42: Add washing solution to the solid-liquid separator so that the washing solution is 2 to 5 times the volume 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 stand for 20 to 100 min to obtain the second precipitate and second supernatant; and then discharge the second supernatant; Step 43: Add washing solution to the solid-liquid separator so that the washing solution is 2 to 5 times the volume of the second precipitate; set the stirring speed of the solid-liquid separator to 200 r / min to 600 r / min, stir for 10 to 60 minutes, then let stand for 20 to 100 minutes to obtain the third precipitate and the third supernatant; and then drain the third supernatant; Step 47: Add washing solution to the solid-liquid separator so that the solvent is 0.5 to 2 times the amount of the third precipitate; set the stirring speed of the solid-liquid separator to 200 r / min to 600 r / min; and after stirring for 10 min to 60 min, obtain an alkali metal tungsten bronze dispersion.

[0085] Step 5: Manufacturing of alkali metal tungsten bronze paint; Dosage (parts by weight): Alkali metal tungsten bronze dispersion: PVA: Deionized water = 1:2~15:80~130

[0086] Add alkali metal tungsten bronze dispersion, PVA (polyvinyl alcohol), and deionized water to the third stirring vessel; set the stirring speed of the third stirring vessel to 100 r / min to 400 r / min; and after stirring for 30 min to 120 min, obtain alkali metal tungsten bronze paint; In the present invention, the structure of the third stirring vessel may be the same as the structure of the first stirring vessel.

[0087] Step 6: Manufacturing of glass curtain walls by spray coating process; The alkali metal tungsten bronze paint is injected into the spray coater tank via piping, and the spray coat distance H from the nozzle to the upper surface of the glass plate is set to 0.5-2 cm; the flow rate of the alkali metal tungsten bronze paint is 1-7 ml / min.

[0088] The hot air supplied by the hot air blower is at a temperature of 22°C to 40°C, and the conveyor roller speed is 10 r / min to 60 r / min. After curing, a nano-alkali metal tungsten bronze coating is produced on the upper surface of the glass.

[0089] In this invention, a glass curtain wall is manufactured from glass supported with a nano-alkali metal tungsten bronze coating, and in order to realize a large-sized spray coat on the glass curtain wall, an array nozzle arrangement structure is adopted as shown in Figure 7. An array of ultrasonic atomizing nozzles 5C are arranged on plate 5A of the nozzle mechanism 5, the ultrasonic atomizing nozzles 5C are connected to the tank of the spray coater via a soft tube, and are connected to the outlet of a third stirring container via tank piping, a post 5B is installed in the center of plate 5A and the post 5B is fixed to the housing of the spray coater.

[0090] In this invention, the ultrasonic atomizing nozzle 5C has a nozzle diameter of 10 to 30 mm and an outlet diameter of 0.5 to 2 mm. The number of ultrasonic atomizing nozzles 5C installed on plate 5A is determined by the size of the manufactured glass curtain wall, the nozzle diameter, and the outlet diameter.

[0091] Example 1: Cesium Tungsten Bronze (Cs) 0.30 WO3 Manufacturing As shown in Figure 2, steps one to four of the present invention are an industrial method for producing nano-alkali metal tungsten bronze by hydrolysis of a low-temperature cation-coordinated tungsten salt, and steps five to six are a method for producing a nano-alkali metal tungsten bronze coating. The nano-alkali metal tungsten bronze produced by the method of the present invention was manufactured into a nano-alkali metal tungsten bronze paint, and then a spray-coating process was used to produce a nano-alkali metal tungsten bronze coating on a glass plate, and the glass supported with the nano-alkali metal tungsten bronze coating was applied to a glass curtain wall. This embodiment specifically refers to the production and application of nano-cesium tungsten bronze and its coating. The specific manufacturing process is as follows.

[0092] Step 1: Preparation of cesium source solution; Dosage: In the cesium source solution, the cesium source concentration was 1 mol / L.

[0093] Cesium chloride (CsCl) and deionized water were added to the first stirring vessel; the mixture was stirred at atmospheric pressure, with a dissolution temperature of 25°C and a stirring speed of 400 r / min, for 5 minutes to prepare the cesium source solution.

[0094] Step 2: Preparation of tungsten source solution; Dosage: The tungsten source concentration in the tungsten source solution was 0.1 mol / L.

[0095] WCl6 and CH3CH2OH were added to a second stirring vessel; the mixture was stirred at atmospheric pressure, with a dissolution temperature of 30°C and a stirring speed of 300 r / min, for 25 minutes to prepare the tungsten source solution.

[0096] Step three: Heat in a water bath to produce a nanocesium tungsten bronze dispersion by hydrolysis; Dosage: To produce 1 kg of cesium tungsten bronze powder, 0.61 kg of cesium source solution and 46.12 kg of tungsten source solution were required.

[0097] Preparation of dispersion by one-step low-temperature heating hydrolysis: Cesium source solution and tungsten source solution were added to a water bath heating vessel; the water bath temperature was set to 70°C, the stirring speed of the water bath heating vessel was set to 500 r / min, and after stirring for 240 min, a dispersion was obtained.

[0098] Step 4, solid-liquid separation; In Example 1, the washing solution was CH3CH2OH.

[0099] Step 41: Add the dispersion to the solid-liquid separator and let it stand for 60 minutes to obtain the first precipitate and the first supernatant; then drain the first supernatant; Step 42: Add washing solution to the solid-liquid separator so that the washing solution is three times the volume of the first precipitate; set the stirring speed of the solid-liquid separator to 300 r / min, stir for 30 minutes, then let stand for 90 minutes to obtain the second precipitate and second supernatant; and then drain the second supernatant; Step 43: Add washing solution to the solid-liquid separator so that the washing solution is three times the volume of the second precipitate; set the stirring speed of the solid-liquid separator to 300 r / min, stir for 60 minutes, then let stand for 60 minutes to obtain the third precipitate and the third supernatant; and then drain the third supernatant; Step 47: Deionized water was added to the solid-liquid separator so that the solvent was 1:1 the amount of the third precipitate; the stirring speed of the solid-liquid separator was set to 300 r / min; and after stirring for 30 minutes, a cesium tungsten bronze dispersion was obtained.

[0100] Characteristics and performance of cesium tungsten bronze powder produced by the method of Example 1 The cesium tungsten bronze dispersion produced in step four is dried in a vacuum resistance furnace at a drying temperature of 60°C and vacuum drying for 240 minutes, and Cs 0.30 WO3 cesium tungsten bronze powder, i.e., powder, was obtained. According to calculations of the raw materials and product yield, Cs 0.30 The industrial yield of WO3 powder was high at 80%.

[0101] In the XRD pattern shown in Figure 8, the cesium tungsten bronze powder produced by the method of Example 1 shows that all diffraction peaks are Cs. 0.30 It belonged to WO3 and demonstrated the synthesis of pure cesium tungsten bronze.

[0102] In the SEM spectrum shown in Figure 9, the Cs produced by the method of Example 1 0.30 The WO3 powder was in the form of short rods, with the length of the short rod-shaped structure being 10 to 140 nm and the diameter being 10 to 20 nm.

[0103] In the UV-Vis-NIR spectrum shown in Figure 13, Cs produced by the method of Example 1 0.30 WO3 powder exhibited excellent near-infrared shielding performance, high visible light transmittance, and good ultraviolet shielding performance.

[0104] In the FTIR spectrum shown in Figure 14, Cs produced by the method of Example 1 0.30 WO3 powder exhibited a certain degree of far-infrared shielding performance.

[0105] In the UV-Vis-NIR spectrum shown in Figure 15, Cs produced by the method of Example 1 0.30 The composite film of WO3 powder and PVA exhibited high near-infrared absorption performance, ultraviolet shielding performance, and high visible light transmission performance.

[0106] Step 5: Manufacturing of cesium tungsten bronze paint; Dosage (parts by weight): Cesium tungsten bronze dispersion: PVA: Deionized water = 1:5:94 A cesium tungsten bronze dispersion, PVA, and deionized water were added to a third stirring vessel; the stirring speed of the third stirring vessel was set to 300 r / min; and after stirring for 60 minutes, a cesium tungsten bronze coating was obtained.

[0107] Step 6: Manufacturing of glass curtain walls by spray coating process; The cesium tungsten bronze paint was injected into the spray coater's tank via piping, and the spray coat distance H from the nozzle to the upper surface of the glass plate was set to 1 cm; the flow rate of the cesium tungsten bronze paint was 4 ml / min.

[0108] The hot air supplied by the hot air blower was at a temperature of 35°C, and the conveying roller speed was 50 r / min. After curing, a cesium tungsten bronze coating was produced on the glass surface.

[0109] The cesium tungsten bronze coating on the upper surface of the glass shown in Figure 16 was irradiated with a 50W halogen lamp at a distance of 20 cm from the upper surface of the glass for photothermal conversion and thermal insulation performance measurements. Compared to quartz glass without thermal insulation coating or with only PVA coating, the glass with thermal insulation coating on the upper surface manufactured in Example 1 reduced the temperature inside the box by 13°C, a decrease of 18.6%. 0.3 The thermal insulation principle of the WO3 coating is that the cesium tungsten bronze in the coating absorbs near-infrared light, which is then converted into heat outside the box, thereby achieving thermal insulation. Therefore, the Cs produced by the method of Example 1 0.3 The WO3 coating possessed high light-to-heat conversion and heat-insulating properties.

[0110] Cs on the upper surface manufactured in Example 1 0.3 By reversing the glass with WO3 coating, the insulating coating on the glass surface is placed inside the box, Cs 0.3 By utilizing the WO3 coating, high photothermal conversion and thermal insulation performance are achieved, allowing heat to be stored within the box. By adjusting the relative positions of the thermal insulation coatings manufactured in Example 1, effective thermal management can be achieved.

[0111] The one-step low-temperature heating hydrolysis method employed in this invention utilizes forced hydrolysis of metal salts under acidic conditions to produce dispersed, uniform nanoparticles. Compared to hydrothermal and solvothermal methods, the method of this invention has a lower reaction temperature, higher yield, and is safer due to the absence of pressure during the reaction. Both hydrothermal and solvothermal methods are synthesis methods that utilize the chemical reaction of substances in solution under constant temperature (100°C to 1000°C) and pressure (1 MPa to 100 MPa) conditions.

[0112] Example 2: Rubidium Tungsten Bronze Rb 0.28 WO3 Manufacturing As shown in Figure 1, the method for industrially producing nanorubidium tungsten bronze by hydrolysis of a low-temperature cation-coordinated tungsten salt according to the present invention includes the following manufacturing steps.

[0113] Step 1: Preparation of rubidium source solution; Dosage: The rubidium source concentration in the rubidium source solution was 1 mol / L.

[0114] Rubidium chloride (RbCl) and deionized water were added to the first stirring vessel; the mixture was stirred for 20 minutes at atmospheric pressure, with a dissolution temperature of 25°C and a stirring speed of 400 r / min, to prepare the rubidium source solution.

[0115] Step 2: Preparation of tungsten source solution; Dosage: The tungsten source concentration in the tungsten source solution was 0.1 mol / L.

[0116] WCl6 and CH3CH2OH were added to a second stirring vessel; the mixture was stirred at atmospheric pressure, with a dissolution temperature of 40°C and a stirring speed of 300 r / min for 50 minutes to prepare the tungsten source solution.

[0117] Step three: Heat in a water bath to produce a nanorubidium tungsten bronze dispersion by hydrolysis; Dosage: To produce 1 kg of cesium tungsten bronze powder, 0.61 kg of rubidium source solution and 49.2 kg of tungsten source solution were required.

[0118] Preparation of dispersion by one-step low-temperature heating hydrolysis: Rubidium source solution and tungsten source solution were added to a water bath heating vessel; the water bath temperature was set to 70°C, the stirring speed of the water bath heating vessel was set to 500 r / min, and after stirring for 600 min, a dispersion was obtained.

[0119] Step 4, solid-liquid separation; In Example 2, the washing solution was CH3CH2OH.

[0120] Step 41: Add the dispersion to the solid-liquid separator and let it stand for 40 minutes to obtain the first precipitate and the first supernatant; then drain the first supernatant; Step 42: Add washing solution to the solid-liquid separator so that the washing solution is 3.5 times the volume of the first precipitate; set the stirring speed of the solid-liquid separator to 400 r / min, stir for 20 minutes, then let stand for 80 minutes to obtain the second precipitate and the second supernatant; and then drain the second supernatant; Step 43: Add washing solution to the solid-liquid separator so that the washing solution is three times the volume of the second precipitate; set the stirring speed of the solid-liquid separator to 400 r / min, stir for 20 minutes, then let stand for 80 minutes to obtain the third precipitate and the third supernatant; and then drain the third supernatant; Step 47: Washing solution was added to the solid-liquid separator so that the solvent was 1:1 the amount of the third precipitate; the stirring speed of the solid-liquid separator was set to 400 r / min; and after stirring for 30 minutes, a rubidium tungsten bronze dispersion was obtained.

[0121] Characteristics and performance of rubidium tungsten bronze manufactured by the method of Example 2 The rubidium tungsten bronze dispersion produced in step four is dried in a vacuum resistance furnace at a drying temperature of 60°C and a vacuum drying time of 480 min to obtain rubidium tungsten bronze powder, i.e., Rb 0.28WO3 powder was obtained. According to the calculation of the raw materials and product yield, Rb 0.28 The industrial yield of WO3 powder was high at 75%.

[0122] In the XRD pattern shown in Figure 8, the rubidium tungsten bronze powder produced by the method of Example 2 shows that all diffraction peaks are Rb. 0.28 It was shown that pure rubidium tungsten bronze, belonging to the WO3 phase, was synthesized.

[0123] In the SEM spectrum shown in Figure 9, Rb produced by the method of Example 2 0.28 The WO3 powder was in the form of short rods, with the length of the short rod-shaped structure being 10 to 100 nm and the diameter being 15 to 30 nm.

[0124] When measured by UV-Vis-NIR spectroscopy, the Rb produced by the method in Example 2 was found to be 0.28 WO3 powder exhibited excellent near-infrared shielding performance, high visible light transmittance, and good ultraviolet shielding performance.

[0125] FTIR spectroscopy revealed that the Rb produced by the method in Example 2 0.28 WO3 powder exhibited a certain degree of far-infrared shielding performance.

[0126] In the UV-Vis-NIR spectrum shown in Figure 15, Rb produced by the method of Example 2 0.28 The composite film of WO3 powder and PVA exhibited high near-infrared absorption performance, ultraviolet shielding performance, and high visible light transmission performance.

[0127] Step 5: Manufacturing of rubidium tungsten bronze paint; Dosage (parts by weight): Rubidium tungsten bronze dispersion: PVA: Deionized water = 1:6:94 Rubidium tungsten bronze dispersion, PVA, and deionized water were added to a third stirring vessel; the stirring speed of the third stirring vessel was set to 300 r / min; and after stirring for 50 minutes, rubidium tungsten bronze paint was obtained.

[0128] Step 6: Manufacturing of glass curtain walls by spray coating process; Rubidium tungsten bronze paint was injected into the spray coater's tank via piping, and the spray coat distance H from the nozzle to the upper surface of the glass plate was set to 2 cm; the flow rate of the rubidium tungsten bronze paint was 3.5 ml / min.

[0129] The hot air supplied by the hot air blower was at a temperature of 40°C, and the conveying roller speed was 40 r / min. After curing, a rubidium tungsten bronze coating was produced on the glass surface.

[0130] The rubidium tungsten bronze coating on the upper surface of the glass shown in Figure 16 was irradiated with a 50W halogen lamp at a distance of 20 cm from the upper surface of the glass for photothermal conversion and thermal insulation performance measurements. Compared to quartz glass without thermal insulation coating or with only PVA coating, the glass with thermal insulation coating on the upper surface manufactured in Example 2 reduced the temperature inside the box by 15.5°C, a decrease of 22.1%. 0.28 The thermal insulation principle of the WO3 coating is that the rubidium tungsten bronze in the coating absorbs near-infrared light, which is then converted into heat outside the box, thereby achieving thermal insulation. Therefore, the Rb produced by the method of Example 2 0.28 The WO3 coating possessed high light-to-heat conversion and heat-insulating properties.

[0131] Cs on the upper surface manufactured in Example 2 0.3 By reversing the glass with WO3 coating, the insulating coating on the glass surface is placed inside the box, Rb 0.28 By utilizing the WO3 coating, high photothermal conversion and thermal insulation performance are achieved, allowing heat to be stored within the box. By adjusting the relative positions of the thermal insulation coatings manufactured in Example 2, effective thermal management can be achieved.

[0132] Example 3: Potassium Tungsten Bronze K0.32 WO3 Manufacturing As shown in Figure 1, the industrial method for producing nanopotassium tungsten bronze by hydrolysis of a low-temperature cation-coordinated tungsten salt according to the present invention includes the following manufacturing steps.

[0133] Step 1: Preparation of potassium source solution; Dosage: The potassium source concentration in the potassium source solution was 2 mol / L.

[0134] Potassium chloride (KCl) and deionized water were added to the first stirring vessel; the mixture was stirred for 20 minutes at atmospheric pressure, with the dissolution temperature set to 25°C and the stirring speed to 400 r / min, after which the potassium source solution was prepared.

[0135] Step 2: Preparation of tungsten source solution; Dosage: The tungsten source concentration in the tungsten source solution was 0.1 mol / L.

[0136] WCl6 and CH3CH2OH were added to a second stirring vessel; the mixture was stirred at atmospheric pressure, with a dissolution temperature of 40°C and a stirring speed of 300 r / min for 50 minutes to prepare the tungsten source solution.

[0137] Step three: Heat in a water bath to produce a nano-potassium tungsten bronze dispersion by hydrolysis; Dosage: To produce 1 kg of potassium tungsten bronze powder, 0.85 kg of potassium source solution and 49.2 kg of tungsten source solution were required.

[0138] Preparation of dispersion by one-step low-temperature heating hydrolysis: Potassium source solution and tungsten source solution were added to a water bath heating vessel; the water bath temperature was set to 70°C, the stirring speed of the water bath heating vessel was set to 500 r / min, and after stirring for 720 minutes, a dispersion was obtained.

[0139] Step 4, solid-liquid separation; In Example 3, the cleaning solution was C3H6O.

[0140] Step 41: Add the dispersion to the solid-liquid separator and let it stand for 90 minutes to obtain the first precipitate and the first supernatant; then drain the first supernatant; Step 42: Add washing solution to the solid-liquid separator so that the washing solution is four times the amount of the first precipitate; set the stirring speed of the solid-liquid separator to 300 r / min, stir for 50 minutes, then let stand for 60 minutes to obtain the second precipitate and second supernatant; and then drain the second supernatant; Step 43: Add washing solution to the solid-liquid separator so that the washing solution is four times the amount of the second precipitate; set the stirring speed of the solid-liquid separator to 300 r / min, stir for 40 minutes, then let stand for 40 minutes to obtain the third precipitate and the third supernatant; and then drain the third supernatant; In step 47, washing solution was added to the solid-liquid separator so that the solvent was 1.5 times the amount of the third precipitate; the stirring speed of the solid-liquid separator was set to 300 r / min; and after stirring for 60 min, a potassium tungsten bronze dispersion was obtained.

[0141] Characteristics and performance of potassium tungsten bronze produced by the method of Example 3 The potassium tungsten bronze dispersion produced in step four is dried in a vacuum resistance furnace at a drying temperature of 60°C and under vacuum for 480 minutes to obtain potassium tungsten bronze powder, i.e., K 0.32 WO3 powder was obtained. According to the calculation of the raw materials and product yield, K 0.32 The industrial yield of WO3 powder was high at 75%.

[0142] In the XRD pattern shown in Figure 8, the potassium tungsten bronze powder produced by the method of Example 3 shows that all diffraction peaks are K 0.32 It belonged to WO3, indicating the synthesis of pure potassium tungsten bronze.

[0143] In the SEM spectrum shown in Figure 9, K produced by the method of Example 3 0.32 The WO3 powder had an equiaxed morphology, and the size distribution of the equiaxed structure was 15 to 100 nm.

[0144] When measured by UV-Vis-NIR spectroscopy, the K produced by the method in Example 3 was found to be 0.32 WO3 powder exhibited excellent near-infrared shielding performance, high visible light transmittance, and good ultraviolet shielding performance.

[0145] FTIR spectroscopy revealed that the K produced by the method in Example 3 0.32 WO3 powder exhibited a certain degree of far-infrared shielding performance.

[0146] In the UV-Vis-NIR spectrum shown in Figure 15, K produced by the method of Example 3 0.32 The composite film of WO3 powder and PVA exhibited high near-infrared absorption performance, ultraviolet shielding performance, and high visible light transmission performance.

[0147] Step 5: Manufacturing of potassium tungsten bronze paint; Dosage (parts by weight): Potassium tungsten bronze dispersion: PVA: Deionized water = 1:5:100 Potassium tungsten bronze dispersion, PVA, and deionized water were added to a third stirring vessel; the stirring speed of the third stirring vessel was set to 400 r / min; and after stirring for 40 minutes, potassium tungsten bronze paint was obtained.

[0148] Step 6: Manufacturing of glass curtain walls by spray coating process; Potassium tungsten bronze paint was injected into the spray coater's tank via piping, and the spray coat distance H = 1.5 cm from the nozzle to the upper surface of the glass plate was set; the flow rate of potassium tungsten bronze paint was 3 ml / min.

[0149] The hot air supplied by the hot air blower was at a temperature of 40°C, and the conveying roller speed was 60 r / min. After curing, a potassium tungsten bronze coating was produced on the glass surface.

[0150] The potassium tungsten bronze coating on the upper surface of the glass shown in Figure 16 was irradiated with a 50W halogen lamp at a distance of 20cm from the upper surface of the glass for photothermal conversion and thermal insulation performance measurements. Compared to quartz glass without thermal insulation coating or with only PVA coating, the glass with thermal insulation coating on the upper surface manufactured in Example 3 lowered the temperature inside the box by 7.5°C, a decrease of 10.7%. 0.32 The thermal insulation principle of the WO3 coating is that the potassium tungsten bronze in the coating absorbs near-infrared light, which is then converted into heat outside the box, thereby achieving thermal insulation. Therefore, the K manufactured by the method of Example 3 0.32 The WO3 coating exhibited high light-to-heat conversion and heat-insulating properties.

[0151] On the upper surface manufactured in Example 3, K 0.32 By reversing the glass with WO3 coating, the insulating coating on the glass surface is placed inside the box, K 0.32 By utilizing the WO3 coating, high photothermal conversion and thermal insulation performance are achieved, allowing heat to be stored within the box. By adjusting the relative positions of the thermal insulation coatings manufactured in Example 3, effective thermal management can be achieved.

[0152] Example 4: Sodium Tungsten Bronze Na 0.33 WO3 Manufacturing As shown in Figure 1, the method for industrially producing nanosodium tungsten bronze by hydrolysis of a low-temperature cation-coordinated tungsten salt according to the present invention includes the following manufacturing steps.

[0153] Step 1: Preparation of sodium source solution; Dosage: The sodium source concentration in the sodium source solution was 2 mol / L.

[0154] Sodium chloride (NaCl) and deionized water were added to the first stirring vessel; the mixture was stirred at atmospheric pressure, with a dissolution temperature of 25°C and a stirring speed of 400 r / min, for 10 minutes to prepare the sodium source solution.

[0155] Step 2: Preparation of tungsten source solution; Dosage: The tungsten source concentration in the tungsten source solution was 0.1 mol / L.

[0156] WCl6 and CH3CH2OH were added to a second stirring vessel; the mixture was stirred at atmospheric pressure, with a dissolution temperature of 40°C and a stirring speed of 300 r / min for 50 minutes to prepare the tungsten source solution.

[0157] Step three: Heat in a water bath to produce a nano-sodium tungsten bronze dispersion by hydrolysis; Dosage: To produce 1 kg of sodium tungsten bronze powder, 2.32 kg of sodium source solution and 61.5 kg of tungsten source solution were required.

[0158] Preparation of dispersion by one-step low-temperature heating hydrolysis: Sodium source solution and tungsten source solution were added to a water bath heating vessel; the water bath temperature was set to 70°C, the stirring speed of the water bath heating vessel was set to 500 r / min, and after stirring for 1440 min, a dispersion was obtained.

[0159] Step 4, solid-liquid separation; In Example 4, the washing solution was CH3OH.

[0160] Step 41: Add the dispersion to the solid-liquid separator and let it stand for 20 minutes to obtain the first precipitate and the first supernatant; then drain the first supernatant; Step 42: Add washing solution to the solid-liquid separator so that the washing solution is 4.5 times the volume of the first precipitate; set the stirring speed of the solid-liquid separator to 200 r / min, stir for 20 minutes, then let stand for 20 minutes to obtain the second precipitate and second supernatant; and then drain the second supernatant; Step 43: Add washing solution to the solid-liquid separator so that the washing solution is 4.5 times the volume of the second precipitate; set the stirring speed of the solid-liquid separator to 200 r / min, stir for 50 minutes, then let stand for 70 minutes to obtain the third precipitate and the third supernatant; and then drain the third supernatant; Step 47: Washing solution was added to the solid-liquid separator so that the solvent was five times the amount of the third precipitate; the stirring speed of the solid-liquid separator was set to 200 r / min; and after stirring for 20 minutes, a sodium tungsten bronze dispersion was obtained.

[0161] Characteristics and performance of sodium tungsten bronze produced by the method of Example 4 The sodium tungsten bronze dispersion produced in step four is dried in a vacuum resistance furnace at a drying temperature of 60°C for 480 minutes under vacuum to obtain sodium tungsten bronze powder, i.e., Na 0.33 WO3 powder was obtained. According to calculations of the raw materials and product yield, Na 0.33 The industrial yield of WO3 powder was high at 60%.

[0162] In the XRD pattern shown in Figure 8, the sodium tungsten bronze powder produced by the method of Example 4 shows that all diffraction peaks are Na 0.33 It was found to belong to WO3, indicating the synthesis of pure sodium tungsten bronze.

[0163] In the SEM spectrum shown in Figure 9, the Na produced by the method of Example 4 0.33 The WO3 powder was in the form of short rods, with the length of the short rod-shaped structure being 20-150 nm and the diameter being 20-50 nm.

[0164] When measured by UV-Vis-NIR spectroscopy, the Na produced by the method in Example 4 was found to be 0.33 WO3 powder exhibited excellent near-infrared shielding performance, high visible light transmittance, and good ultraviolet shielding performance.

[0165] FTIR spectroscopy revealed that the Na produced by the method in Example 4 0.33WO3 powder exhibited a certain degree of far-infrared shielding performance.

[0166] In the UV-Vis-NIR spectrum shown in Figure 15, the Na produced by the method of Example 4 0.33 The composite film of WO3 powder and PVA exhibited high near-infrared absorption performance, ultraviolet shielding performance, and high visible light transmission performance.

[0167] Step 5: Manufacturing of sodium tungsten bronze paint; Dosage (parts by weight): Sodium tungsten bronze dispersion: PVA: Deionized water = 1.5:7:120 Sodium tungsten bronze dispersion, PVA, and deionized water were added to the third stirring vessel; the stirring speed of the third stirring vessel was set to 300 r / min; and after stirring for 100 min, sodium tungsten bronze paint was obtained.

[0168] Step 6: Manufacturing of glass curtain walls by spray coating process; Sodium tungsten bronze paint was injected into the spray coater tank via piping, and the spray coat distance H from the nozzle to the upper surface of the glass plate was set to 1 cm; the flow rate of sodium tungsten bronze paint was 2 ml / min.

[0169] The hot air supplied by the hot air blower was at a temperature of 40°C, and the conveying roller speed was 50 r / min. After curing, an insulating coating was produced on the glass surface.

[0170] To achieve large-scale spray coating of glass curtain walls, the present invention employs an array nozzle arrangement structure as shown in Figure 7. Ultrasonic atomizing nozzles 5C are arranged in an array on plate 5A of nozzle mechanism 5, the ultrasonic atomizing nozzles 5C are connected to the spray coater's tank via soft tubes, a post 5B is installed in the center of plate 5A, and the post 5B is fixed to the housing of the spray coater.

[0171] In this invention, the ultrasonic atomizing nozzle 5C had a nozzle diameter of 20 mm and an outlet diameter of 1.5 mm. The number of ultrasonic atomizing nozzles 5C installed on plate 5A was determined according to the size of the glass curtain wall being manufactured, the nozzle diameter, and the outlet diameter.

[0172] The sodium tungsten bronze coating on the upper surface of the glass shown in Figure 16 was irradiated with a 50W halogen lamp at a distance of 20 cm from the upper surface of the glass for photothermal conversion and thermal insulation performance measurements. Compared to quartz glass without thermal insulation coating or with only PVA coating, the glass with thermal insulation coating on the upper surface manufactured in Example 4 reduced the temperature inside the box by 10°C, with a temperature drop of 14.3%. 0.33 The thermal insulation principle of the WO3 coating is that the sodium tungsten bronze in the coating absorbs near-infrared light, which is then converted into heat outside the box, thereby achieving thermal insulation. Therefore, the Na produced by the method of Example 4 0.33 The WO3 coating possessed high light-to-heat conversion and heat-insulating properties.

[0173] Na on the upper surface produced in Example 4 0.33 By reversing the glass with a WO3 coating, the insulating coating on the glass surface is placed inside the box, Na 0.33 By utilizing the WO3 coating, high photothermal conversion and thermal insulation performance are achieved, allowing heat to be stored within the box. By adjusting the relative positions of the thermal insulation coatings manufactured in Example 4, effective thermal management can be achieved.

[0174] Example 5: Cesium Tungsten Bronze (Cs) 0.23 WO3 Manufacturing As shown in Figure 2, the nanocesium tungsten bronze obtained by applying the industrial production method of hydrolysis of low-temperature cation-coordinated tungsten salts of the present invention, and the method for producing a nanocesium tungsten bronze coating by a spray-coating process, include the following manufacturing steps.

[0175] Step 1: Preparation of cesium source solution; Dosage: The cesium source concentration in the cesium source solution was 0.2 mol / L.

[0176] CsOH and deionized water were added to the first stirring vessel; the mixture was stirred at atmospheric pressure, with a dissolution temperature of 40°C and a stirring speed of 400 r / min, for 20 minutes to prepare the cesium source solution.

[0177] Step 2: Preparation of tungsten source solution; Dosage: The tungsten source concentration in the tungsten source solution was 0.15 mol / L.

[0178] WCl6 and CH3(CH2)2OH were added to a second stirring vessel; the mixture was stirred at atmospheric pressure, with a dissolution temperature of 30°C and a stirring speed of 500 r / min, for 20 minutes to prepare the tungsten source solution.

[0179] Step three: Heat in a water bath to produce a nanocesium tungsten bronze dispersion by hydrolysis; Dosage: To produce 1 kg of cesium tungsten bronze powder, 6.5 kg of cesium source solution and 36.32 kg of tungsten source solution were required.

[0180] Preparation of dispersion by one-step low-temperature heating hydrolysis: Cesium source solution and tungsten source solution were added to a water bath heating vessel; the water bath temperature was set to 80°C and the stirring speed of the water bath heating vessel to 500 r / min, and after stirring for 360 min, a dispersion was obtained.

[0181] Step 4, solid-liquid separation; In Example 5, the washing solution was CH3CH2OH.

[0182] Step 41: Add the dispersion to the solid-liquid separator and let it stand for 100 minutes to obtain the first precipitate and the first supernatant; then drain the first supernatant; Step 42: Add washing solution to the solid-liquid separator so that the washing solution is 3.5 times the volume of the first precipitate; set the stirring speed of the solid-liquid separator to 400 r / min, stir for 30 minutes, then let stand for 40 minutes to obtain the second precipitate and the second supernatant; and then drain the second supernatant; Step 43: Add washing solution to the solid-liquid separator so that the washing solution is 3.5 times the volume of the second precipitate; set the stirring speed of the solid-liquid separator to 400 r / min, stir for 80 min, then let stand for 70 min to obtain the third precipitate and the third supernatant; and then drain the third supernatant; Step 47: Deionized water was added to the solid-liquid separator so that the solvent was four times the amount of the third precipitate; the stirring speed of the solid-liquid separator was set to 500 r / min; and after stirring for 50 min, a cesium tungsten bronze dispersion was obtained.

[0183] Step 5: Manufacturing of cesium tungsten bronze paint; Dosage (parts by weight): Cesium tungsten bronze dispersion: PVA: Deionized water = 1:5:100 A cesium tungsten bronze dispersion, PVA, and deionized water were added to a third stirring vessel; the stirring speed of the third stirring vessel was set to 400 r / min; and after stirring for 90 minutes, a cesium tungsten bronze coating was obtained.

[0184] Step 6: Manufacturing of glass curtain walls by spray coating process; The cesium tungsten bronze paint was injected into the spray coater's tank via piping, and the spray coat distance H from the nozzle to the upper surface of the glass plate was set to 1 cm; the flow rate of the cesium tungsten bronze paint was 7 ml / min.

[0185] The hot air supplied by the hot air blower was at a temperature of 35°C, and the conveying roller speed was 20 r / min. After curing, an insulating coating was produced on the glass surface.

[0186] To achieve large-scale spray coating of glass curtain walls, the present invention employs an array nozzle arrangement structure as shown in Figure 7. Ultrasonic atomizing nozzles 5C are arranged in an array on plate 5A of nozzle mechanism 5, the ultrasonic atomizing nozzles 5C are connected to the spray coater's tank via soft tubes, a post 5B is installed in the center of plate 5A, and the post 5B is fixed to the housing of the spray coater.

[0187] In this invention, the ultrasonic atomizing nozzle 5C had a nozzle diameter of 10 mm and an outlet diameter of 1 mm. The number of ultrasonic atomizing nozzles 5C installed on plate 5A was determined according to the size of the glass curtain wall being manufactured, as well as the nozzle diameter and outlet diameter.

[0188] Characteristics and performance of cesium tungsten bronze produced by the method of Example 5 XRD pattern analysis revealed that the cesium tungsten bronze powder produced by the method of Example 5 showed that all diffraction peaks were Cs. 0.23 It belonged to WO3 and demonstrated the synthesis of pure cesium tungsten bronze.

[0189] SEM spectroscopy analysis revealed that the Cs produced by the method in Example 5 0.23 The WO3 powder was in the form of short rods, with the length of the short rod-shaped structure being 30-140 nm and the diameter being 15-40 nm.

[0190] Analysis by UV-Vis-NIR spectroscopy revealed that the Cs produced by the method in Example 5 0.23 WO3 powder possessed high near-infrared absorption, ultraviolet shielding, and visible light transmission properties.

[0191] When the thermal insulation coating on the glass surface was measured by its photothermal conversion and thermal insulation performance, the thermal insulation coating manufactured in Example 5 exhibited high photothermal conversion and thermal insulation performance.

[0192] Example 6: Sodium Tungsten Bronze Na0.30 WO3 Manufacturing This invention involves synthesizing a sodium tungsten bronze alkoxide precursor by employing a combination of hydrolysis and coprecipitation methods, and then synthesizing sodium tungsten bronze at low temperature in the original liquid phase, and includes the following manufacturing steps.

[0193] As shown in Figure 2, the method for producing a nanosodium tungsten bronze coating by a spray-coating process using industrially produced nanosodium tungsten bronze obtained by hydrolysis of a low-temperature cation-coordinated tungsten salt according to the present invention includes the following manufacturing steps.

[0194] Step 1: Preparation of sodium source solution; Dosage: The sodium source concentration in the sodium source solution was 2 mol / L.

[0195] NaCl and deionized water were added to the first stirring vessel; the mixture was stirred at atmospheric pressure, with a dissolution temperature of 40°C and a stirring speed of 300 r / min, for 15 minutes to prepare the sodium source solution.

[0196] Step 2: Preparation of tungsten source solution; Dosage: The tungsten source concentration in the tungsten source solution was 0.075 mol / L.

[0197] WCl6 and CH3CH2OH were added to a second stirring vessel; the mixture was stirred at atmospheric pressure, with a dissolution temperature of 35°C and a stirring speed of 400 r / min, for 25 minutes to prepare the tungsten source solution.

[0198] Step three: Heat in a water bath to produce a nano-sodium tungsten bronze dispersion by hydrolysis; Dosage: To produce 1 kg of cesium tungsten bronze powder, 2.2 kg of sodium source solution and 55.42 kg of tungsten source solution were required.

[0199] Preparation of dispersion by one-step low-temperature heating hydrolysis: Sodium source solution and tungsten source solution were added to a water bath heating vessel; the water bath temperature was set to 74°C, the stirring speed of the water bath heating vessel was set to 400 r / min, and after stirring for 1500 min, a dispersion was obtained.

[0200] Step 4, solid-liquid separation; In Example 6, the washing solution was CH3CH2OH.

[0201] Step 41: Add the dispersion to the solid-liquid separator and let it stand for 30 minutes to obtain the first precipitate and the first supernatant; then drain the first supernatant; Step 42: Add washing solution to the solid-liquid separator so that the washing solution is twice the volume of the first precipitate; set the stirring speed of the solid-liquid separator to 500 r / min, stir for 40 minutes, then let stand for 40 minutes to obtain the second precipitate and second supernatant; and then drain the second supernatant; Step 43: Add washing solution to the solid-liquid separator so that the washing solution is twice the volume of the second precipitate; set the stirring speed of the solid-liquid separator to 400 r / min, stir for 50 minutes, then let stand for 50 minutes to obtain the third precipitate and the third supernatant; and then drain the third supernatant; Step 47: Deionized water was added to the solid-liquid separator so that the solvent was three times the amount of the third precipitate; the stirring speed of the solid-liquid separator was set to 300 / min; and after stirring for 60 minutes, a sodium tungsten bronze dispersion was obtained.

[0202] Production of sodium tungsten bronze powder by drying The sodium tungsten bronze dispersion produced in step four is dried in a vacuum resistance furnace at a drying temperature of 70°C and under vacuum for 300 minutes to obtain sodium tungsten bronze powder, i.e., Na 0.30 WO3 powder was obtained. According to calculations of the raw materials and product yield, Na 0.30 The industrial yield of WO3 powder was 65%.

[0203] Step 5: Manufacturing of sodium tungsten bronze paint; Dosage (parts by weight): Sodium tungsten bronze dispersion: PVA: Deionized water = 1.5:7:120 Sodium tungsten bronze dispersion, PVA, and deionized water were added to the third stirring vessel; the stirring speed of the third stirring vessel was set to 300 r / min; and after stirring for 100 min, sodium tungsten bronze paint was obtained.

[0204] Step 6: Manufacturing of glass curtain walls by spray coating process; Sodium tungsten bronze paint was injected into the spray coater tank via piping, and the spray coat distance H = 1.5 cm from the nozzle to the upper surface of the glass plate was set; the flow rate of sodium tungsten bronze paint was 1 ml / min.

[0205] The hot air supplied by the hot air blower was at a temperature of 40°C, and the conveying roller speed was 50 r / min. After curing, an insulating coating was produced on the glass surface.

[0206] To achieve large-scale spray coating of glass curtain walls, the present invention employs an array nozzle arrangement structure as shown in Figure 7. Ultrasonic atomizing nozzles 5C are arranged in an array on plate 5A of nozzle mechanism 5, the ultrasonic atomizing nozzles 5C are connected to the spray coater's tank via soft tubes, a post 5B is installed in the center of plate 5A, and the post 5B is fixed to the housing of the spray coater.

[0207] In this invention, the ultrasonic atomizing nozzle 5C had a nozzle diameter of 20 mm and an outlet diameter of 1.5 mm. The number of ultrasonic atomizing nozzles 5C installed on plate 5A was determined according to the size of the glass curtain wall being manufactured, as well as the nozzle diameter and outlet diameter.

[0208] Characteristics and performance of sodium tungsten bronze produced by the method of Example 6 XRD pattern analysis revealed that the sodium tungsten bronze powder produced by the method in Example 6 showed that all diffraction peaks were Na0.30 It was found to belong to WO3, indicating the synthesis of pure sodium tungsten bronze.

[0209] SEM spectroscopy analysis revealed that the Na produced by the method in Example 6 0.30 The WO3 powder was in the form of short rods, with the length of the short rod-shaped structure being 30-140 nm and the diameter being 15-40 nm.

[0210] Analysis by UV-Vis-NIR spectroscopy revealed that the Na produced by the method in Example 6 0.30 WO3 powder possessed high near-infrared absorption, ultraviolet shielding, and visible light transmission properties.

[0211] When the thermal insulation coating on the glass surface was measured by its photothermal conversion and thermal insulation performance, the thermal insulation coating manufactured in Example 6 exhibited high photothermal conversion and thermal insulation performance.

[0212] The above description represents only preferred embodiments of the present invention, and those skilled in the art can make several modifications and alterations without departing from the principles of the present invention, and such modifications and alterations should be considered to fall within the scope of protection of the present invention.

Claims

1. An industrial method for producing nano-alkali metal tungsten bronze by hydrolysis of a low-temperature cation-coordinated tungsten salt, comprising the following steps: Step 1: Preparation of alkali metal source solution; Step 11: Add deionized water to the first stirring vessel; A stirrer is installed inside the first stirring vessel (1), and above the cylinder (1A) of the first stirring vessel (1), an alkali metal source supply port (1A1), a deionized water supply port (1A2), and an exhaust port (1A3) are installed; below the cylinder (1A), an alkali metal source solution outlet (1A4) is installed; Step 12: Add the alkali metal source to the first stirring vessel; The alkali metal source comprises a salt of one or two of the hydroxides, chlorides, and nitrates, sulfates, and carbonates corresponding to the alkali metal ions; The hydroxide is cesium hydroxide, potassium hydroxide, or sodium hydroxide; The chloride salt is cesium chloride, rubidium chloride, potassium chloride, or sodium chloride; The nitrate is cesium nitrate, potassium nitrate, or sodium nitrate; The sulfate salt is cesium sulfate, potassium sulfate, or sodium sulfate; The carbonate is cesium carbonate, potassium carbonate, or sodium carbonate; Step 13: Set the mixture to atmospheric pressure, with a dissolution temperature of 10°C to 40°C and a stirring speed of 200 r / min to 600 r / min; after stirring for 1 min to 15 min, prepare the alkali metal source solution; The alkali metal ion concentration of the manufactured alkali metal source solution is between 0.02 mol / L and 10 mol / L; Step two, preparation of the tungsten source solution; Step 21, add the tungsten source to the second stirring vessel; The tungsten source is tungsten hexachloride or tungsten tetrachloride; A stirrer (2E) is installed inside the second stirring vessel (2); a tungsten source supply port (2A1), an alcohol source supply port (2A2), and an exhaust port (2A3) are installed above the cylinder (2A) of the second stirring vessel (2); a tungsten source mixed solution outlet (2A4) is installed below the cylinder (2A); a resistance wire (2D) is installed between the outer wall of the inner casing (2C) of the second stirring vessel (2) and the inner wall of the cylinder (2A); Step 22: Add the alcohol solution to the second stirring vessel; The alcohol solution is one or more combinations of methanol, ethanol, n-propanol, isopropanol, and n-butanol; Step 23: Set the dissolution temperature to 10°C to 40°C and the stirring speed to 200 r / min to 600 r / min at atmospheric pressure; after stirring for 10 min to 60 min, produce the tungsten source solution; The tungsten source concentration of the manufactured tungsten source solution is between 0.02 mol / L and 1 mol / L; Step three: Heat in a water bath to produce a nano-alkali metal tungsten bronze dispersion by hydrolysis; Dosage: To produce 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; Production of alkali metal tungsten bronze dispersion by one-step low-temperature heating hydrolysis: The alkali metal source solution produced in step one, the tungsten source solution produced in step two, and deionized water are added to the water bath heating container (3); the water bath temperature is set to 40 to 95°C and 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; 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 installed between the heating cylinder (3C) and the water bath cylinder (3A), with tap water in the water bath cylinder (3A); an agitator (3E) is installed inside the heating cylinder (3C); and above the water bath heating container (3) are a CA supply port (3A1), a CB supply port (3A2), a CC supply port (3A3), and an exhaust port (3A4); Step 4, solid-liquid separation; The washing solution is methanol, ethanol, acetone; or a combination of methanol and deionized water; a combination of ethanol and deionized water; or a combination of acetone and deionized water; Step 41: The alkali metal tungsten bronze dispersion produced in Step 3 is added to the solid-liquid separator (4), and after standing for 20 to 100 minutes, the first precipitate and the first supernatant are obtained; the first supernatant is discharged; Step 42: Add washing solution to the solid-liquid separator (4) so ​​that the washing solution is 2 to 5 times the amount 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 stand for 20 to 100 min to obtain the second precipitate and the second supernatant; discharge the second supernatant; Step 43: Add washing solution to the solid-liquid separator (4) so ​​that the washing solution is 2 to 5 times the amount of the second 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 stand for 20 to 100 min to obtain the third precipitate and the third supernatant; discharge the third supernatant; Step 44: Add washing solution to the solid-liquid separator (4) so ​​that the solvent is 2 to 5 times the amount 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, obtain a nano-alkali metal tungsten bronze dispersion; A stirrer (4E) is installed inside the solid-liquid separator (4); above the cylinder (4A) of the solid-liquid separator (4), a DA supply port (4A1), a DB supply port (4A2), and a DA discharge port (4A3) are installed; below the cylinder (4A), a DB discharge port (4A4) is installed; Step 5: Production of nano-alkali metal tungsten bronze powder by drying; The alkali metal tungsten bronze liquid produced in step four is dried in a vacuum resistance furnace, and the vacuum level is set to 1 × 10⁻⁶. －２ Pa ~ 1 x 10 －４ By setting the temperature to Pa, the drying temperature to 50°C to 100°C, and the drying time to 180 min to 720 min, alkali metal tungsten bronze powder is obtained. Industrial method for producing nano-alkali metal tungsten bronze by hydrolysis of low-temperature cation-coordinated tungsten salts.

2. Synthesize nano-alkali metal tungsten bronze by applying low-temperature hydrothermal decomposition of a process, and the components of the nano-alkali metal tungsten bronze are Cs ｘ WO ３ , Rb ｘ WO ３ , K ｘ WO ３ , Na ｘ WO ３ , where 0.2 ≤ X ≤ 0.33 An industrial method for producing nano-alkali metal tungsten bronze by hydrolysis of a low-temperature cation-coordinated tungsten salt according to claim 1, characterized in that

3. As a component of the manufactured nano-alkali metal tungsten bronze powder, Cs ０．３０ WO ３ Powder, Rb ０．２８ WO ３ powder, K ０．３２ WO ３ Powder or Na ０．３３ WO ３ There is a powder, An industrial method for producing nano-alkali metal tungsten bronze by hydrolysis of a low-temperature cation-coordinated tungsten salt according to claim 1, characterized in that

4. The manufactured nanoalkali metal tungsten bronze powder is in the form of a short rod or equiaxed, the short rod-shaped structure has a length of 10 to 150 nm and a diameter of 10 to 50 nm, and the equiaxed structure has a size in each direction of less than 100 nm. An industrial method for producing nano-alkali metal tungsten bronze by hydrolysis of a low-temperature cation-coordinated tungsten salt according to claim 1, characterized in that

5. The industrial yield of the manufactured nanocesium tungsten bronze powder is 70% to 85%, the industrial yield of nanorubidium tungsten bronze powder is 70% to 85%, the industrial yield of nanopotassium tungsten bronze powder is 60% to 80%, and the industrial yield of nanosodium tungsten bronze powder is 50% to 75%. An industrial method for producing nano-alkali metal tungsten bronze by hydrolysis of a low-temperature cation-coordinated tungsten salt according to claim 1, characterized in that

6. An industrial method for producing a nanoalkali metal tungsten bronze coating using the nanoalkali metal tungsten bronze solution described in claim 1, comprising the following steps: Step 1: Preparation of alkali metal source solution; Step 11: Add deionized water to the first stirring vessel; Step 12: Add the alkali metal source to the first stirring vessel; The alkali metal source comprises a salt of one or two of the hydroxides, chlorides, and nitrates, sulfates, and carbonates corresponding to the alkali metal ions; The hydroxide is cesium hydroxide, potassium hydroxide, or sodium hydroxide; The chloride salt is cesium chloride, rubidium chloride, potassium chloride, or sodium chloride; The nitrate is cesium nitrate, potassium nitrate, or sodium nitrate; The sulfate salt is cesium sulfate, potassium sulfate, or sodium sulfate; The carbonate is cesium carbonate, potassium carbonate, or sodium carbonate; Step 13: Set the mixture to atmospheric pressure, with a dissolution temperature of 10°C to 40°C and a stirring speed of 200 r / min to 600 r / min; after stirring for 1 min to 15 min, prepare the alkali metal source solution; The alkali metal ion concentration of the manufactured alkali metal source solution is between 0.05 mol / L and 5 mol / L; Step two, preparation of the tungsten source solution; Step 21, add the tungsten source to the second stirring vessel; The tungsten source is tungsten hexachloride or tungsten tetrachloride; Step 22: Add the alcohol solution to the second stirring vessel; The alcohol solution is one or more combinations of methanol, ethanol, n-propanol, isopropanol, and n-butanol; Step 23: Set the dissolution temperature to 15°C to 40°C and the stirring speed to 200 r / min to 600 r / min at atmospheric pressure; after stirring for 10 min to 60 min, produce the tungsten source solution; The tungsten source concentration of the manufactured tungsten source solution is between 0.05 mol / L and 1 mol / L; Step three: Heat in a water bath to produce a nano-alkali metal tungsten bronze dispersion by hydrolysis; Dosage: To produce 1 kg of nano-alkali metal tungsten bronze powder, 0.23 kg to 36 kg of alkali metal source solution and 3.68 kg to 123 kg of tungsten source solution are required; Production of alkali metal tungsten bronze dispersion by one-step low-temperature heating hydrolysis: The alkali metal source solution produced in step one, the tungsten source solution produced in step two, and deionized water are added to a water bath heating vessel; the water bath temperature is set to 40°C to 90°C, and after stirring at a stirring speed of 200 r / min to 1000 r / min for 90 min to 2880 min, a dispersion is obtained; Step 4, solid-liquid separation; The washing solution is methanol, ethanol, acetone; or a combination of methanol and deionized water; a combination of ethanol and deionized water; or a combination of acetone and deionized water; Step 41: The alkali metal tungsten bronze dispersion prepared in Step 3 is added to the solid-liquid separator, and after standing for 20 to 100 minutes, the first precipitate and the first supernatant are obtained; the first supernatant is discharged; Step 42: Add washing solution to the solid-liquid separator so that the washing solution is 2 to 5 times the amount of the first precipitate; set the stirring speed of the solid-liquid separator to 200 r / min to 600 r / min, stir for 10 to 60 min, then let stand for 20 to 100 min to obtain the second precipitate and the second supernatant; discharge the second supernatant; Step 43: Add washing solution to the solid-liquid separator so that the washing solution is 2 to 5 times the amount of the second 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 stand for 20 to 100 min to obtain the third precipitate and the third supernatant; discharge the third supernatant; Step 44: Add washing solution to the solid-liquid separator so that the solvent is 0.5 to 2 times the amount 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, obtain alkali metal tungsten bronze dispersion; Step 5: Manufacturing of alkali metal tungsten bronze paint; Dosage: Alkali metal tungsten bronze dispersion: PVA: Deionized water = 1:2 to 15:80 to 130; The alkali metal tungsten bronze dispersion, PVA, and deionized water produced in step four are added to the third stirring vessel; the stirring speed of the third stirring vessel is set to 100 r / min to 400 r / min; and after stirring for 30 min to 120 min, alkali metal tungsten bronze paint is obtained; Step 6: Manufacturing of a glass curtain wall by spray coating process; The alkali metal tungsten bronze paint is injected into the spray coater tank via piping, and the spray coat distance H from the nozzle to the upper surface of the glass plate is set to 0.5 to 2 cm; the flow rate of the alkali metal tungsten bronze paint is 1 to 7 ml / min; The hot air supplied by the hot air blower is at a temperature of 22°C to 40°C, and the conveyor roller speed is 10 r / min to 60 r / min. After curing, a nano-alkali metal tungsten bronze coating is produced on the upper surface of the glass. An industrial method for manufacturing nano-alkali metal tungsten bronze coatings using nano-alkali metal tungsten bronze solution, characterized by the above.

7. The manufactured nano-alkali metal tungsten bronze coating will be applied to glass curtain walls. An industrial method for producing a nanoalkali metal tungsten bronze coating using the nanoalkali metal tungsten bronze solution according to claim 6, characterized in that

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