阅读说明：本技术 一种铯钨青铜/氧化钨复合材料的制备方法 (Preparation method of cesium tungsten bronze/tungsten oxide composite material ) 是由 杨明庆 赵林元 吕勇 牛春晖 李晓英 耿蕊 于 2019-10-31 设计创作，主要内容包括：本发明公开一种铯钨青铜/氧化钨复合材料的制备方法,包括如下步骤：在常压、室温下,将钨酸、铯盐加入去离子水中,搅拌均匀后加入乙二醇,搅拌得反应液；160-240℃下反应,离心、洗涤、干燥,得铯钨青铜/氧化钨复合材料；其中,反应液中钨酸与铯盐的质量之比为1:(0.22-1.86),反应液中铯盐的浓度为0.008-0.043g/mL。该方法中,铯钨青铜和氧化钨是同时生成的,复合材料中两者混合分布均匀,复合材料的各个部位的性能完全一致。此外,该制备工艺简单,重复性好,且可以实现规模化生产,具有良好的应用价值。同时,所得复合材料具有良好的红外光线吸收性能,在波长为1200-2500nm的范围内,近红外光的最低透光率为10％。(The invention discloses a preparation method of a cesium tungsten bronze/tungsten oxide composite material, which comprises the following steps: adding tungstic acid and cesium salt into deionized water at normal pressure and room temperature, uniformly stirring, adding ethylene glycol, and stirring to obtain a reaction solution; reacting at 160 ℃ and 240 ℃, centrifuging, washing and drying to obtain the cesium tungsten bronze/tungsten oxide composite material; wherein the mass ratio of the tungstic acid to the cesium salt in the reaction solution is 1 (0.22-1.86), and the concentration of the cesium salt in the reaction solution is 0.008-0.043 g/mL. In the method, the cesium tungsten bronze and the tungsten oxide are simultaneously generated, the cesium tungsten bronze and the tungsten oxide are uniformly mixed and distributed in the composite material, and the performances of all parts of the composite material are completely consistent. In addition, the preparation process is simple, has good repeatability, can realize large-scale production, and has good application value. Meanwhile, the obtained composite material has good infrared ray absorption performance, and the minimum light transmittance of near infrared light is 10% within the wavelength range of 1200-2500 nm.)

1. The preparation method of the cesium tungsten bronze/tungsten oxide composite material is characterized by comprising the following steps of:

adding tungstic acid and cesium salt into deionized water at normal pressure and room temperature, uniformly stirring, adding ethylene glycol, and stirring to obtain a reaction solution; reacting at 160 ℃ and 240 ℃, centrifuging, washing and drying to obtain the cesium tungsten bronze/tungsten oxide composite material;

wherein the mass ratio of the tungstic acid to the cesium salt in the reaction solution is 1 (0.22-1.86), and the concentration of the cesium salt in the reaction solution is 0.008-0.043 g/mL.

2. The method according to claim 1, wherein the mass ratio of ethylene glycol to cesium salt in the reaction solution is 1 (0.054-0.27).

3. The production method according to claim 1, wherein the purity of the tungstic acid is analytical grade, the purity of the ethylene glycol is 99.5%, and the resistivity of the deionized water is 18.2M Ω -cm.

4. The method of claim 1, wherein the reaction time is 0.5 to 16 hours.

5. The method of claim 1, wherein the drying is performed at 30-50 ℃ for 24-48 h.

6. The method of claim 1, wherein the washing is water washing.

7. A cesium tungsten bronze/tungsten oxide composite material produced by the production method as recited in any one of claims 1 to 6.

8. The cesium tungsten bronze/tungsten oxide composite material according to claim 7, wherein the mass ratio of cesium tungsten bronze to tungsten oxide in said composite material is 1 (0.25-2.13).

9. The cesium tungsten bronze/tungsten oxide composite material according to claim 7, wherein the composite material is an aggregate of nanoparticles and nanorods; wherein the particle size of the nano-particles is 10-20nm, and the length of the nano-rods is 60-150 nm.

10. The cesium tungsten bronze/tungsten oxide composite material according to claim 7, wherein the composite material has a light transmittance of near infrared light of 10% in the wavelength range of 1200-2500 nm.

Technical Field

The invention relates to the technical field of near-infrared absorption materials. More particularly, relates to a preparation method of a cesium tungsten bronze/tungsten oxide composite material.

Background

In the total energy consumption of society, the building consumption occupies about 30%, and the building energy consumption is more concentrated relative to other energy consumption time. Studies have shown that 73% of the heat in a building room enters through windows, and the heat transfer is primarily from sunlight. The solar radiation wave band mainly comprises an ultraviolet light wave band (240-400 nanometers), a visible light wave band (400-780 nanometers) and a near infrared wave band (780-2500 nanometers). The near infrared band, which is generally considered the major source of heat, accounts for approximately 52% of the total solar energy. Ordinary glass can not the selectivity to the sunlight and see through, therefore when the visible light sees through, the heat that is located near infrared light district also sees through in a large number, causes the indoor temperature to rise, makes the burden of cooling equipment such as air conditioner aggravate, the waste energy. Therefore, a material capable of shielding near infrared rays has received much attention (Wu X, Wang J, Zhan G, et al. applied Catalysis B: Environmental,2017,201: 128-136.).

The composite material can combine the unique and excellent performances of two different materials, not only maintains the advantages of the performances of the materials of each component, but also can obtain the comprehensive performances which can not be achieved by a single component material through the complementation and the correlation of the performances of each component. The tungsten bronze type material is a non-stoichiometric semiconductor material and has good piezoelectric, ferroelectric and nonlinear optical properties. Having a chemical formula of M_xWO₃And x is between 0 and 1, and the specific value depends on the doping amount of the cation. The M ion may be a monovalent alkali metal ion, a divalent metal ion, a rare earth element, or the like. (Liu J, Luo J, Shi F, et al. journal of Solid State Chemistry,2015,221: 255-.). Among a plurality of tungsten bronze materials, cesium tungsten bronze has unique conductivity, superconductivity, photochromism, electrochromism, optical performance and the like, and particularly has unique optical performance and a strong near infrared shielding function on a near infrared region. WO₃The material is a semiconductor material with a narrow forbidden band width, and is widely applied to the fields of solar cells, fuel cells, photocatalysis, intelligent windows and the like. At present, there are many raw materials and methods for separately preparing cesium tungsten bronze and tungsten oxide. And the method of mixing the two materials together is mainly a ball milling method. The method has low cost and simple operation, but the prepared material has the defects of low purity and uneven component distribution. In the material, the property of the material is greatly influenced by the uneven distribution of the components.

Therefore, it is required to develop a preparation method for uniformly compounding the cesium tungsten bronze and the tungsten oxide.

Disclosure of Invention

The invention aims to provide a preparation method of a cesium tungsten bronze/tungsten oxide composite material.

Another object of the present invention is to provide a cesium tungsten bronze/tungsten oxide composite material prepared by the above method.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a preparation method of a cesium tungsten bronze/tungsten oxide composite material, which comprises the following steps:

adding tungstic acid and cesium salt into deionized water at normal pressure and room temperature, uniformly stirring, adding ethylene glycol, and stirring to obtain a reaction solution; reacting at 160 ℃ and 240 ℃, centrifuging, washing and drying to obtain the cesium tungsten bronze/tungsten oxide composite material;

wherein the mass ratio of the tungstic acid to the cesium salt in the reaction solution is 1 (0.22-1.86), and the concentration of the cesium salt is 0.008-0.043 g/mL.

In a specific implementation process, the preparation process of the reaction solution comprises the following steps:

dispersing tungstic acid in deionized water at room temperature, and stirring for 0.2-6h to form yellow suspension;

at room temperature, cesium salt is dissolved in deionized water and stirred to form colorless transparent liquid;

adding cesium salt aqueous solution into the tungstic acid suspension, stirring for 0.2-6h, and uniformly mixing to form suspension;

adding ethylene glycol into the suspension, and stirring to obtain a reaction solution;

then the reaction liquid is moved into a reaction kettle and reacts at the temperature of 160-240 ℃;

and after the reaction is finished, centrifuging, washing and drying to obtain the cesium tungsten bronze/tungsten oxide composite material which is blue powder.

In the preparation method provided by the invention, tungstic acid and cesium salt are used as raw materials, ethylene glycol is used as a reducing agent, and the cesium tungsten bronze/tungsten oxide composite material is prepared by a simple solvothermal method. During the preparation process, the cesium tungsten bronze and the tungsten oxide are formed simultaneously, the mixing distribution of the cesium tungsten bronze and the tungsten oxide is uniform, and the performance of each part of the formed composite material is consistent during the use process. Overcomes the defect of uneven mixing of cesium tungsten bronze and tungsten oxide in the traditional ball milling mixing method.

The cesium tungsten bronze is a non-stoichiometric narrow-bandgap semiconductor material, has unique conductivity, superconductivity, photochromism, electrochromism and optical performance, can generate strong absorption for light with the wavelength of more than 1100nm, and is an excellent near infrared absorption material. Tungsten oxide is a semiconductor material with a narrow forbidden band width, and is widely applied to the fields of solar cells, fuel cells, photocatalysis, smart windows and the like. The two are combined, and the solar energy filter has good application in the aspects of intelligent windows, photocatalysis and sunlight filters.

According to the invention, the proportion of cesium tungsten bronze to tungsten oxide in the obtained composite material is regulated and controlled by controlling the concentration of added tungstic acid and cesium salt, so that the obtained composite material has more excellent near-infrared absorption performance; and in the concentration range, the uniform distribution of the obtained composite material is also ensured.

Preferably, the mass ratio of the ethylene glycol to the cesium salt in the reaction solution is 1 (0.054-0.27).

In the present invention, ethylene glycol is used as both a solvent and a reducing agent, and is added in an amount to ensure complete reaction.

Preferably, the purity of the tungstic acid is analytically pure, the purity of the ethylene glycol is 99.5%, and the resistivity of the deionized water is 18.2M omega cm.

Preferably, the reaction time of the reaction solution is 0.5 to 16 hours.

Preferably, the reaction time of the reaction solution is 0.5 to 16 hours.

Preferably, the drying is at 30-50 ℃ for 24-48 h.

Preferably, the washing is water washing.

The preparation method is a simple hydrothermal process, has simple process and good repeatability, can realize large-scale production, and has good application value.

In order to realize the second purpose of the invention, the following technical scheme is adopted:

the cesium tungsten bronze/tungsten oxide composite material prepared by the preparation method.

Preferably, the mass ratio of the cesium tungsten bronze to the tungsten oxide in the composite material is 1 (1.54-0.19). Under the mass ratio, the cesium atoms of the composite material are uniformly doped in the tungsten oxide, and the plasma resonance effect of elements is more favorably realized.

Preferably, the composite material is an aggregate of nanoparticles and nanorods; wherein the particle size of the nano-particles is 10-20nm, and the length of the nano-rods is 60-150 nm. The two compounds are uniformly combined, with both ingredients in the granules and in the rods.

Preferably, the composite material has the light transmittance of near infrared light of 10% in the wavelength range of 1200-2500 nm. The light transmittance of near infrared light of the composite material is rapidly reduced to 10 percent from about 20 percent at 780nm in the wavelength range of 780-1200 nm.

The invention has the following beneficial effects:

the invention provides a preparation method of a cesium tungsten bronze/tungsten oxide composite material, which takes tungstic acid and cesium salt as raw materials and prepares the composite material by completely and uniformly mixing the cesium tungsten bronze and tungsten oxide through a simple solvothermal process. The preparation process is simple, the repeatability is good, large-scale production can be realized, and the application value is good.

In addition, the cesium tungsten bronze/tungsten oxide composite material prepared by the preparation method provided by the invention has good infrared ray absorption performance, and the light transmittance of near infrared light is 10% within the range of wavelength of 1200-2500 nm.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

FIG. 1 shows an X-ray diffraction pattern of a sample of the composite material prepared in example 6 of the present invention.

FIG. 2 shows an X-ray diffraction pattern of a sample of the composite material prepared in example 8 of the present invention.

FIG. 3 shows a scanning electron micrograph of a composite sample prepared according to example 11 of the present invention.

FIG. 4 shows a transmission electron micrograph of a composite sample prepared according to example 11 of the present invention.

FIG. 5 shows the energy spectrum of a composite material prepared in example 11 of the present invention.

FIG. 6 shows the elemental distribution of a composite prepared in example 11 of the present invention.

FIG. 7 shows a UV-Vis-NIR transmission spectrum of a composite material prepared in example 3 of the present invention.

FIG. 8 is a graph showing an ultraviolet-visible-near infrared transmission spectrum of a composite material prepared in example 11 of the present invention.

Fig. 9 shows a graph of the ultraviolet-visible-near infrared transmission spectrum of the composite material prepared in comparative example 1 of the present invention.

FIG. 10 is a graph showing an ultraviolet-visible-near infrared transmission spectrum of a composite material prepared in comparative example 2 of the present invention.

Detailed Description

In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.

In the present invention, the preparation methods are all conventional methods unless otherwise specified. The starting materials used are available from published commercial sources unless otherwise specified, and the percentages are by mass unless otherwise specified.

Example 1

0.5g of tungstic acid is taken to be dispersed in 20mL of pure water at room temperature, and stirred into uniform dispersion liquid; 0.3g of cesium salt is dissolved in 10mL of pure water, added into the obtained dispersion, and stirred uniformly to form a suspension; adding 5mL of ethylene glycol into the obtained suspension, and uniformly stirring; adding the mixture into a reaction kettle, and reacting for 0.5h at 220 ℃; and centrifuging the obtained product, washing with water, and drying at the temperature of 30-50 ℃ for 24-48h to obtain the blue powder composite material. In the composite material, the mass ratio of the cesium tungsten bronze to the tungsten oxide is 1: 0.77.

Taking a proper amount of sample to carry out XRD detection. And comparing the obtained spectrogram with a standard spectrogram, finding that the composite material is formed by combining the spectrograms of cesium tungsten bronze (JCPDS 81-1244) and tungsten oxide (JCPDS 83-0951), and indicating that the prepared material is a cesium tungsten bronze/tungsten oxide composite material. And re-dispersing a small amount of dried sample in pure water (with the resistivity of 18.2M omega cm), respectively spotting on a silicon chip for observation by a scanning electron microscope and an ultrathin carbon film for observation by a transmission electron microscope, and observing by the scanning electron microscope and the transmission electron microscope to obtain a sample, wherein the sample is formed by aggregating nano particles with the particle size of 10-20nm and nano short rods with the length of 60-150 nm. The energy spectrum (EDS) proves that the material contains cesium, tungsten and oxygen components. The element distribution diagram shows that oxygen, tungsten and cesium in the material are in a uniform distribution state, and the cesium tungsten bronze and the tungsten oxide are proved to be uniformly compounded. And (3) taking a proper amount of powder sample to carry out ultraviolet visible near infrared spectrum test, wherein in an integrating sphere mode, the light transmittance of the tested sample at the wavelength of 780-1200nm is below 21%, and the light transmittance of the near infrared light at the wavelength of 1200-2500nm is basically maintained at 10%.

Example 2.

0.5g of tungstic acid is taken to be dispersed in 20mL of pure water at room temperature, and stirred into uniform dispersion liquid; 0.61g of cesium salt is dissolved in 10mL of pure water, added into the obtained dispersion, and stirred uniformly to form a suspension; adding 5mL of ethylene glycol into the obtained suspension, and uniformly stirring; adding the mixture into a reaction kettle, and reacting for 3 hours at 230 ℃; the obtained product is centrifuged, washed with water and dried at 30-50 ℃ for 24-48h to obtain blue powder. In the composite material, the mass ratio of the cesium tungsten bronze to the tungsten oxide is 1: 0.38.

Taking a proper amount of sample to carry out XRD detection. And comparing the obtained spectrogram with a standard spectrogram, finding that the composite material is formed by combining the spectrograms of cesium tungsten bronze (JCPDS 81-1244) and tungsten oxide (JCPDS 83-0951), and indicating that the prepared material is a cesium tungsten bronze/tungsten oxide composite material. And re-dispersing a small amount of dried sample in pure water (with the resistivity of 18.2M omega cm), respectively spotting on a silicon wafer for scanning electron microscope observation and an ultrathin carbon film for transmission electron microscope observation, and observing by using a scanning electron microscope and a transmission electron microscope to obtain a sample, wherein the sample is formed by aggregating nano particles with the particle size of 10-20nm and short rods with the length of 60-150 nm. The energy spectrum (EDS) proves that the material contains cesium, tungsten and oxygen components. The element distribution diagram shows that oxygen, tungsten and cesium in the material are in a uniform distribution state, and the cesium tungsten bronze and the tungsten oxide are proved to be uniformly compounded. And (3) taking a proper amount of powder sample to carry out ultraviolet visible near infrared spectrum test, wherein in an integrating sphere mode, the light transmittance of the tested sample at the wavelength of 780-1200nm is below 21%, and the light transmittance of the near infrared light at the wavelength of 1200-2500nm is basically maintained at 10%.

Example 3.

0.5g of tungstic acid is taken to be dispersed in 20mL of pure water at room temperature, and stirred into uniform dispersion liquid; 0.93g of cesium salt is dissolved in 10mL of pure water, added into the obtained dispersion, and stirred uniformly to form a suspension; adding 5mL of ethylene glycol into the obtained suspension, and uniformly stirring; adding the mixture into a reaction kettle, and reacting for 16 hours at 230 ℃; the obtained product is centrifuged, washed with water and dried at 30-50 ℃ for 24-48h to obtain blue powder. In the composite material, the mass ratio of the cesium tungsten bronze to the tungsten oxide is 1: 0.25.

Taking a proper amount of sample to carry out XRD detection. And comparing the obtained spectrogram with a standard spectrogram, finding that the composite material is formed by combining the spectrograms of cesium tungsten bronze (JCPDS 81-1244) and tungsten oxide (JCPDS 83-0951), and indicating that the prepared material is a cesium tungsten bronze/tungsten oxide composite material. And re-dispersing a small amount of dried sample in pure water (with the resistivity of 18.2M omega cm), respectively spotting on a silicon chip for observation by a scanning electron microscope and an ultrathin carbon film for observation by a transmission electron microscope, and observing by the scanning electron microscope and the transmission electron microscope to obtain a sample, wherein the sample is formed by aggregating nano particles with the particle size of 10-20nm and nano short rods with the length of 60-150 nm. The energy spectrum (EDS) proves that the material contains cesium, tungsten and oxygen components. The element distribution diagram shows that oxygen, tungsten and cesium in the material are in a uniform distribution state, and the cesium tungsten bronze and the tungsten oxide are proved to be uniformly compounded. An appropriate amount of powder samples are taken to perform ultraviolet visible near infrared spectrum test, as shown in fig. 7, in the integrating sphere mode, the light transmittance of the tested samples is below 21% at the wavelength of 780-1200nm, and the light transmittance of the tested samples is basically maintained at 10% at the wavelength of 1200-2500 nm.

Example 4.

1.0g of tungstic acid is taken to be dispersed in 20mL of pure water at room temperature, and stirred into uniform dispersion liquid; 0.61g of cesium salt is dissolved in 10mL of pure water, added into the obtained dispersion, and stirred uniformly to form a suspension; adding 5mL of ethylene glycol into the obtained suspension, and uniformly stirring; adding the mixture into a reaction kettle, and reacting for 3 hours at 160 ℃; the obtained product is centrifuged, washed with water and dried at 30-50 ℃ for 24-48h to obtain blue powder. In the composite material, the mass ratio of the cesium tungsten bronze to the tungsten oxide is 1: 0.76.

Taking a proper amount of sample to carry out XRD detection. And comparing the obtained spectrogram with a standard spectrogram, finding that the composite material is formed by combining the spectrograms of cesium tungsten bronze (JCPDS 81-1244) and tungsten oxide (JCPDS 83-0951), and indicating that the prepared material is a cesium tungsten bronze/tungsten oxide composite material. And re-dispersing a small amount of dried sample in pure water (with the resistivity of 18.2M omega cm), respectively spotting on a silicon wafer for scanning electron microscope observation and an ultrathin carbon film for transmission electron microscope observation, and observing by using a scanning electron microscope and a transmission electron microscope to obtain a sample, wherein the sample is formed by aggregating nano particles with the particle size of 10-20nm and short rods with the length of 60-150 nm. The energy spectrum (EDS) proves that the material contains cesium, tungsten and oxygen components. The element distribution diagram shows that oxygen, tungsten and cesium in the material are in a uniform distribution state, and the cesium tungsten bronze and the tungsten oxide are proved to be uniformly compounded. And (3) taking a proper amount of powder sample to carry out ultraviolet visible near infrared spectrum test, wherein in an integrating sphere mode, the light transmittance of the tested sample at the wavelength of 780-1200nm is below 21%, and the light transmittance of the near infrared light at the wavelength of 1200-2500nm is basically maintained at 10%.

Example 5.

1.2g of tungstic acid is taken to be dispersed in 20mL of pure water at room temperature, and stirred into uniform dispersion liquid; dissolving 1.2g of cesium salt in 10mL of pure water, adding the cesium salt into the obtained dispersion, and uniformly stirring to form a suspension; adding 5mL of ethylene glycol into the obtained suspension, and uniformly stirring; adding the mixture into a reaction kettle, and reacting for 6 hours at 240 ℃; the obtained product is centrifuged, washed with water and dried at 30-50 ℃ for 24-48h to obtain blue powder. In the composite material, the mass ratio of the cesium tungsten bronze to the tungsten oxide is 1: 0.46.

Taking a proper amount of sample to carry out XRD detection. And comparing the obtained spectrogram with a standard spectrogram, finding that the composite material is formed by combining the spectrograms of cesium tungsten bronze (JCPDS 81-1244) and tungsten oxide (JCPDS 83-0951), and indicating that the prepared material is a cesium tungsten bronze/tungsten oxide composite material. And re-dispersing a small amount of dried sample in pure water (with the resistivity of 18.2M omega cm), respectively spotting on a silicon wafer for scanning electron microscope observation and an ultrathin carbon film for transmission electron microscope observation, and observing by using a scanning electron microscope and a transmission electron microscope to obtain a sample, wherein the sample is formed by aggregating nano particles with the particle size of 10-20nm and short rods with the length of 60-150 nm. The energy spectrum (EDS) proves that the material contains cesium, tungsten and oxygen components. The element distribution diagram shows that oxygen, tungsten and cesium in the material are in a uniform distribution state, and the cesium tungsten bronze and the tungsten oxide are proved to be uniformly compounded. And (3) taking a proper amount of powder sample to carry out ultraviolet visible near infrared spectrum test, wherein in an integrating sphere mode, the light transmittance of the tested sample at the wavelength of 780-1200nm is below 21%, and the light transmittance of the near infrared light at the wavelength of 1200-2500nm is basically maintained at 10%.

Example 6.

1.8g of tungstic acid is taken to be dispersed in 20mL of pure water at room temperature, and stirred into uniform dispersion liquid; dissolving 1.5g of cesium salt in 10mL of pure water, adding the cesium salt into the obtained dispersion, and uniformly stirring to form a suspension; adding 5mL of ethylene glycol into the obtained suspension, and uniformly stirring; adding the mixture into a reaction kettle, and reacting for 16 hours at 240 ℃; the obtained product is centrifuged, washed with water and dried at 30-50 ℃ for 24-48h to obtain blue powder. In the composite material, the mass ratio of the cesium tungsten bronze to the tungsten oxide is 1: 0.56.

An appropriate amount of sample was taken for XRD detection, and the obtained result is shown in FIG. 1. And comparing the obtained spectrogram with a standard spectrogram, finding that the composite material is formed by combining the spectrograms of cesium tungsten bronze (JCPDS 81-1244) and tungsten oxide (JCPDS 83-0951), and indicating that the prepared material is a cesium tungsten bronze/tungsten oxide composite material. And re-dispersing a small amount of dried sample in pure water (with the resistivity of 18.2M omega cm), respectively spotting on a silicon chip for observation by a scanning electron microscope and an ultrathin carbon film for observation by a transmission electron microscope, and observing by the scanning electron microscope and the transmission electron microscope to obtain a sample, wherein the sample is formed by aggregating nano particles with the particle size of 10-20nm and nano short rods with the length of 60-150 nm. The energy spectrum (EDS) proves that the material contains cesium, tungsten and oxygen components. The element distribution diagram shows that oxygen, tungsten and cesium in the material are in a uniform distribution state, and the cesium tungsten bronze and the tungsten oxide are proved to be uniformly compounded. And (3) taking a proper amount of powder sample to carry out ultraviolet visible near infrared spectrum test, wherein in an integrating sphere mode, the light transmittance of the tested sample at the wavelength of 780-1200nm is below 21%, and the light transmittance of the near infrared light at the wavelength of 1200-2500nm is basically maintained at 10%.

Example 7.

1.8g of tungstic acid is taken to be dispersed in 20mL of pure water at room temperature, and stirred into uniform dispersion liquid; 0.61g of cesium salt is dissolved in 10mL of pure water, added into the obtained dispersion, and stirred uniformly to form a suspension; adding 7.5mL of glycol into the obtained suspension, and uniformly stirring; adding the mixture into a reaction kettle, and reacting for 3 hours at 160 ℃; the obtained product is centrifuged, washed with water and dried at 30-50 ℃ for 24-48h to obtain blue powder. In the composite material, the mass ratio of the cesium tungsten bronze to the tungsten oxide is 1: 1.37.

Taking a proper amount of sample to carry out XRD detection. And comparing the obtained spectrogram with a standard spectrogram, finding that the composite material is formed by combining the spectrograms of cesium tungsten bronze (JCPDS 81-1244) and tungsten oxide (JCPDS 83-0951), and indicating that the prepared material is a cesium tungsten bronze/tungsten oxide composite material. And re-dispersing a small amount of dried sample in pure water (with the resistivity of 18.2M omega cm), respectively spotting on a silicon wafer for scanning electron microscope observation and an ultrathin carbon film for transmission electron microscope observation, and observing by using a scanning electron microscope and a transmission electron microscope to obtain a sample, wherein the sample is formed by aggregating nano particles with the particle size of 10-20nm and short rods with the length of 60-150 nm. The energy spectrum (EDS) proves that the material contains cesium, tungsten and oxygen components. The element distribution diagram shows that oxygen, tungsten and cesium in the material are in a uniform distribution state, and the cesium tungsten bronze and the tungsten oxide are proved to be uniformly compounded. And (3) taking a proper amount of powder sample to perform ultraviolet visible near infrared spectrum test, and measuring that the light transmittance of the near infrared light of the sample is below 21% at the wavelength of 780-1200nm and is basically maintained at 10% at the wavelength of 1200-2500nm in an integrating sphere mode.

Example 8.

1.8g of tungstic acid is taken to be dispersed in 20mL of pure water at room temperature, and stirred into uniform dispersion liquid; dissolving 1.2g of cesium salt in 20mL of pure water, adding the cesium salt into the obtained dispersion, and uniformly stirring to form a suspension; adding 7.5mL of glycol into the obtained suspension, and uniformly stirring; adding the mixture into a reaction kettle, and reacting for 6 hours at 230 ℃; centrifuging the obtained product, washing with water, and drying at 30-50 deg.C for 24-48h to obtain blue powder. In the composite material, the mass ratio of the cesium tungsten bronze to the tungsten oxide is 1: 0.7.

An appropriate amount of sample was taken for XRD examination, and the obtained results are shown in FIG. 2. And comparing the obtained spectrogram with a standard spectrogram, finding that the composite material is formed by combining the spectrograms of cesium tungsten bronze (JCPDS 81-1244) and tungsten oxide (JCPDS 83-0951), and indicating that the prepared material is a cesium tungsten bronze/tungsten oxide composite material. And re-dispersing a small amount of dried sample in pure water (with the resistivity of 18.2M omega cm), respectively spotting on a silicon wafer for scanning electron microscope observation and an ultrathin carbon film for transmission electron microscope observation, and observing by using a scanning electron microscope and a transmission electron microscope to obtain a sample, wherein the sample is formed by aggregating nano particles with the particle size of 10-20nm and short rods with the length of 60-150 nm. The energy spectrum (EDS) proves that the material contains cesium, tungsten and oxygen components. The element distribution diagram shows that oxygen, tungsten and cesium in the material are in a uniform distribution state, and the cesium tungsten bronze and the tungsten oxide are proved to be uniformly compounded. And (3) taking a proper amount of powder sample to carry out ultraviolet visible near infrared spectrum test, wherein in an integrating sphere mode, the light transmittance of the tested sample at the wavelength of 780-1200nm is below 21%, and the light transmittance of the near infrared light at the wavelength of 1200-2500nm is basically maintained at 10%.

Example 9.

Dispersing 2.5g of tungstic acid in 40mL of pure water at room temperature, and stirring to form a uniform dispersion liquid; dissolving 1.2g of cesium salt in 20mL of pure water, adding the cesium salt into the obtained dispersion, and uniformly stirring to form a suspension; adding 7.5mL of glycol into the obtained suspension, and uniformly stirring; adding the mixture into a reaction kettle, and reacting for 16 hours at 160 ℃; the obtained product is centrifuged, washed with water and dried at 30-50 ℃ for 24-48h to obtain blue powder. In the composite material, the mass ratio of the cesium tungsten bronze to the tungsten oxide is 1: 0.97.

Taking a proper amount of sample to carry out XRD detection. And comparing the obtained spectrogram with a standard spectrogram, finding that the composite material is formed by combining the spectrograms of cesium tungsten bronze (JCPDS 81-1244) and tungsten oxide (JCPDS 83-0951), and indicating that the prepared material is a cesium tungsten bronze/tungsten oxide composite material. And re-dispersing a small amount of dried sample in pure water (with the resistivity of 18.2M omega cm), respectively spotting on a silicon wafer for scanning electron microscope observation and an ultrathin carbon film for transmission electron microscope observation, and observing by using a scanning electron microscope and a transmission electron microscope to obtain a sample, wherein the sample is formed by aggregating nano particles with the particle size of 10-20nm and short rods with the length of 60-150 nm. The energy spectrum (EDS) proves that the material contains cesium, tungsten and oxygen components. The element distribution diagram shows that oxygen, tungsten and cesium in the material are in a uniform distribution state, and the cesium tungsten bronze and the tungsten oxide are proved to be uniformly compounded. And (3) taking a proper amount of powder sample to carry out ultraviolet visible near infrared spectrum test, wherein in an integrating sphere mode, the light transmittance of the tested sample at the wavelength of 780-1200nm is below 21%, and the light transmittance of the near infrared light at the wavelength of 1200-2500nm is basically maintained at 10%.

Example 10.

Dispersing 2.5g of tungstic acid in 40mL of pure water at room temperature, and stirring to form a uniform dispersion liquid; dissolving 1.5g of cesium salt in 20mL of pure water, adding the cesium salt into the obtained dispersion, and uniformly stirring to form a suspension; adding 7.5mL of glycol into the obtained suspension, and uniformly stirring; adding the mixture into a reaction kettle, and reacting for 0.5h at 220 ℃; the obtained product is centrifuged, washed with water and dried at 30-50 ℃ for 24-48h to obtain blue powder. In the composite material, the mass ratio of the cesium tungsten bronze to the tungsten oxide is 1: 0.77.

Taking a proper amount of sample to carry out XRD detection. And comparing the obtained spectrogram with a standard spectrogram, finding that the composite material is formed by combining the spectrograms of cesium tungsten bronze (JCPDS 81-1244) and tungsten oxide (JCPDS 83-0951), and indicating that the prepared material is a cesium tungsten bronze/tungsten oxide composite material. And re-dispersing a small amount of dried sample in pure water (with the resistivity of 18.2M omega cm), respectively spotting on a silicon wafer for scanning electron microscope observation and an ultrathin carbon film for transmission electron microscope observation, and observing by using a scanning electron microscope and a transmission electron microscope to obtain a sample, wherein the sample is formed by aggregating nano particles with the particle size of 10-20nm and short rods with the length of 60-150 nm. The energy spectrum (EDS) proves that the material contains cesium, tungsten and oxygen components. The element distribution diagram shows that oxygen, tungsten and cesium in the material are in a uniform distribution state, and the cesium tungsten bronze and the tungsten oxide are proved to be uniformly compounded. And (3) taking a proper amount of powder sample to carry out ultraviolet visible near infrared spectrum test, wherein in an integrating sphere mode, the light transmittance of the tested sample at the wavelength of 780-1200nm is below 21%, and the light transmittance of the near infrared light at the wavelength of 1200-2500nm is basically maintained at 10%.

Example 11.

Dispersing 2.8g of tungstic acid in 40mL of pure water at room temperature, and stirring to form a uniform dispersion liquid; 0.61g of cesium salt is dissolved in 10mL of pure water, added into the obtained dispersion, and stirred uniformly to form a suspension; adding 10mL of glycol into the obtained suspension, and uniformly stirring; adding the mixture into a reaction kettle, and reacting for 3 hours at 230 ℃; the obtained product is centrifuged, washed with water and dried at 30-50 ℃ for 24-48h to obtain blue powder. In the composite material, the mass ratio of the cesium tungsten bronze to the tungsten oxide is 1: 2.13.

Taking a proper amount of sample to carry out XRD detection. And comparing the obtained spectrogram with a standard spectrogram, finding that the composite material is formed by combining the spectrograms of cesium tungsten bronze (JCPDS 81-1244) and tungsten oxide (JCPDS 83-0951), and indicating that the prepared material is a cesium tungsten bronze/tungsten oxide composite material. And re-dispersing a small amount of dried sample in pure water (with the resistivity of 18.2M omega cm), respectively spotting on a silicon wafer for observation by a scanning electron microscope and an ultrathin carbon film for observation by a transmission electron microscope, and observing by the scanning electron microscope (figure 3) and the transmission electron microscope (figure 4) to obtain a sample formed by aggregating nano particles with the particle size of 10-20nm and short rods with the length of 60-150 nm. As shown in fig. 5, the material was confirmed to contain cesium, tungsten, and oxygen components by energy spectroscopy (EDS). The elemental distribution diagram shows (fig. 6) that the oxygen, tungsten and cesium components in the material are in a uniformly distributed state, demonstrating that the cesium tungsten bronze and tungsten oxide are uniformly compounded. An appropriate amount of powder samples are taken to carry out ultraviolet visible near infrared spectrum test, and the result is shown in fig. 8, in the integrating sphere mode, the light transmittance of the tested samples is below 20% at the wavelength of 780-1200nm, and the light transmittance of the near infrared light is basically maintained at 10% at the wavelength of 1200-2500 nm.

Example 12.

Dispersing 3.0g of tungstic acid in 60mL of pure water at room temperature, and stirring to form a uniform dispersion liquid; dissolving 1.27g of cesium salt in 20mL of pure water, adding the cesium salt into the obtained dispersion, and uniformly stirring to form a suspension; adding 10mL of glycol into the obtained suspension, and uniformly stirring; adding the mixture into a reaction kettle, and reacting for 6 hours at 220 ℃; the obtained product is centrifuged, washed with water and dried at 30-50 ℃ for 24-48h to obtain blue powder. In the composite material, the mass ratio of the cesium tungsten bronze to the tungsten oxide is 1: 1.1.

Taking a proper amount of sample to carry out XRD detection. And comparing the obtained spectrogram with a standard spectrogram, finding that the composite material is formed by combining the spectrograms of cesium tungsten bronze (JCPDS 81-1244) and tungsten oxide (JCPDS 83-0951), and indicating that the prepared material is a cesium tungsten bronze/tungsten oxide composite material. And re-dispersing a small amount of dried sample in pure water (with the resistivity of 18.2M omega cm), respectively spotting on a silicon wafer for scanning electron microscope observation and an ultrathin carbon film for transmission electron microscope observation, and observing by using a scanning electron microscope and a transmission electron microscope to obtain a sample, wherein the sample is formed by aggregating nano particles with the particle size of 10-20nm and short rods with the length of 60-150 nm. The energy spectrum (EDS) proves that the material contains cesium, tungsten and oxygen components. The element distribution diagram shows that oxygen, tungsten and cesium in the material are in a uniform distribution state, and the cesium tungsten bronze and the tungsten oxide are proved to be uniformly compounded. And (3) taking a proper amount of powder sample to carry out ultraviolet visible near infrared spectrum test, wherein in an integrating sphere mode, the light transmittance of the tested sample at the wavelength of 780-1200nm is below 20%, and the light transmittance of the near infrared light at the wavelength of 1200-2500nm is basically maintained at 10%.

Example 13.

Dispersing 3.0g of tungstic acid in 60mL of pure water at room temperature, and stirring to form a uniform dispersion liquid; dissolving 1.5g of cesium salt in 20mL of pure water, adding the cesium salt into the obtained dispersion, and uniformly stirring to form a suspension; adding 10mL of glycol into the obtained suspension, and uniformly stirring; adding the mixture into a reaction kettle, and reacting for 16 hours at 240 ℃; the obtained product is centrifuged, washed with water and dried at 30-50 ℃ for 24-48h to obtain blue powder. In the composite material, the mass ratio of the cesium tungsten bronze to the tungsten oxide is 1: 0.93.

Taking a proper amount of sample to carry out XRD detection. And comparing the obtained spectrogram with a standard spectrogram, finding that the composite material is formed by combining the spectrograms of cesium tungsten bronze (JCPDS 81-1244) and tungsten oxide (JCPDS 83-0951), and indicating that the prepared material is a cesium tungsten bronze/tungsten oxide composite material. And re-dispersing a small amount of dried sample in pure water (with the resistivity of 18.2M omega cm), respectively spotting on a silicon wafer for scanning electron microscope observation and an ultrathin carbon film for transmission electron microscope observation, and observing by using a scanning electron microscope and a transmission electron microscope to obtain a sample, wherein the sample is formed by aggregating nano particles with the particle size of 10-20nm and short rods with the length of 60-150 nm. The energy spectrum (EDS) proves that the material contains cesium, tungsten and oxygen components. The element distribution diagram shows that oxygen, tungsten and cesium in the material are in a uniform distribution state, and the cesium tungsten bronze and the tungsten oxide are proved to be uniformly compounded. And (3) taking a proper amount of powder sample to carry out ultraviolet visible near infrared spectrum test, wherein in an integrating sphere mode, the light transmittance of the tested sample at the wavelength of 780-1200nm is below 20%, and the light transmittance of the near infrared light at the wavelength of 1200-2500nm is basically maintained at 10%.

Comparative example 1.

Dispersing 2.8g of tungstic acid in 40mL of pure water at room temperature, and stirring to form a uniform dispersion liquid; 0.5g of cesium salt is dissolved in 10mL of pure water, added into the obtained dispersion, and stirred uniformly to form a suspension; adding 10mL of glycol into the obtained suspension, and uniformly stirring; adding the mixture into a reaction kettle, and reacting for 3 hours at 230 ℃; the obtained product is centrifuged, washed with water and dried at 30-50 ℃ for 24-48h to obtain blue powder. In the composite material, the mass ratio of the cesium tungsten bronze to the tungsten oxide is 1: 2.6.

Taking a proper amount of sample to carry out XRD detection. And comparing the obtained spectrogram with a standard spectrogram, finding that the composite material is formed by combining the spectrograms of cesium tungsten bronze (JCPDS 81-1244) and tungsten oxide (JCPDS 83-0951), and indicating that the prepared material is a cesium tungsten bronze/tungsten oxide composite material. And re-dispersing a small amount of dried sample in pure water (with the resistivity of 18.2M omega cm), respectively spotting on a silicon wafer for scanning electron microscope observation and an ultrathin carbon film for transmission electron microscope observation, and observing by using a scanning electron microscope and a transmission electron microscope to obtain a sample, wherein the sample is formed by aggregating nano particles with the particle size of 10-20nm and short rods with the length of 60-150 nm. The energy spectrum (EDS) proves that the material contains cesium, tungsten and oxygen components. The element distribution diagram shows that oxygen, tungsten and cesium in the material are in a uniform distribution state, and the cesium tungsten bronze and the tungsten oxide are proved to be uniformly compounded. An appropriate amount of powder sample is taken to carry out ultraviolet visible near infrared spectrum test, as shown in fig. 9, under the mode of integrating sphere, the measured light transmittance of the sample at 780nm wavelength is 25%, the light transmittance at 1200nm wavelength is 14%, the near infrared shielding performance is reduced, and the light transmittance of the near infrared light can be basically maintained at about 14% at the wavelength of 1200nm and 2500 nm. The cesium tungsten bronze and tungsten oxide compositions in the material are controlled within a certain range.

Comparative example 2.

Dispersing 3.0g of tungstic acid in 60mL of pure water at room temperature, and stirring to form a uniform dispersion liquid; 0.3g of cesium salt is dissolved in 10mL of pure water, added into the obtained dispersion, and stirred uniformly to form a suspension; adding 7.5mL of glycol into the obtained suspension, and uniformly stirring; adding the mixture into a reaction kettle, and reacting for 3 hours at 230 ℃; the obtained product is centrifuged, washed with water and dried at 30-50 ℃ for 24-48h to obtain blue powder. In the composite material, the mass ratio of the cesium tungsten bronze to the tungsten oxide is 1: 4.64.

Taking a proper amount of sample to carry out XRD detection. And comparing the obtained spectrogram with a standard spectrogram, finding that the composite material is formed by combining the spectrograms of cesium tungsten bronze (JCPDS 81-1244) and tungsten oxide (JCPDS 83-0951), and indicating that the prepared material is a cesium tungsten bronze/tungsten oxide composite material. And re-dispersing a small amount of dried sample in pure water (with the resistivity of 18.2M omega cm), respectively spotting on a silicon wafer for scanning electron microscope observation and an ultrathin carbon film for transmission electron microscope observation, and observing by using a scanning electron microscope and a transmission electron microscope to obtain a sample, wherein the sample is formed by aggregating nano particles with the particle size of 10-20nm and short rods with the length of 60-150 nm. An appropriate amount of powder sample is taken to carry out ultraviolet visible near infrared spectrum test, as shown in fig. 10, under an integrating sphere mode, the measured light transmittance of the sample at the wavelength of 780nm is 41%, the light transmittance at the wavelength of 1200nm is 26%, the near infrared shielding performance is poor, and the cesium tungsten bronze and tungsten oxide components in the material are controlled within a certain range.

It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.