CN114932728A - A kind of electrically driven Joule thermochromic laminated glass with adjustable color and preparation method thereof - Google Patents

Abstract

An electrically-driven Joule thermochromic laminated glass with adjustable color and a preparation method thereof belong to the technical field of smart glass, in particular to an active thermochromic laminated glass with adjustable color and a preparation method thereof. The purpose of the present invention is to solve the problems of complicated preparation process and poor discoloration ability of the existing VO ₂ film. A color-tunable electrically driven Joule thermochromic laminated glass consists of a glass top layer, a thermochromic polymer layer, a transparent conductive oxide layer and a glass bottom layer. Preparation method: 1. Preparation of thermochromic polymer sandwich; 2. Assembly: Method 1: Coating by means of blade coating; Method 2: Coating by pouring method. Advantages: brighter color, not yellow; good physical and chemical stability, can slow down the deterioration of particles under strong light after encapsulation; can achieve active color change, Joule heat generated after power-on will force the phase change of thermochromic materials Change optical properties.

Description

A kind of electrically driven Joule thermochromic laminated glass with adjustable color and preparation method thereof

technical field

The invention belongs to the technical field of intelligent glass, and particularly relates to an active thermochromic laminated glass with adjustable color and a preparation method thereof.

Background technique

With the proposal of the dual carbon goal, energy conservation and emission reduction have become the top priority in various fields. Among them, windows widely existing in buildings, automobiles and other fields are a huge energy consumption gap. Due to the weak effect of windows on near-infrared heat regulation, their heat loss accounts for 60% of building energy consumption. The need for energy saving presents challenges, so it is necessary to develop advanced smart dimming glass. With the development of artificial intelligence, Internet of Things, smart home and other technologies, it is the general trend to realize the regulation of near-infrared heat transmittance by electronic control. However, the current electrochromic devices involve a multi-layer film system such as a color-changing layer, an electrode layer, and a solid-state electrolyte layer, which are complicated in structure and high in cost, which limit their large-scale applications. Thermochromic technology, as a passive dimming technology, has the characteristics of maintenance-free, simple structure, low cost, zero emission, and self-adjustment with temperature changes, and has received extensive attention. If passive thermochromic technology can be applied to the active driving force, it is possible to realize the design of low-cost electrochromic devices.

Thermochromic vanadium dioxide (VO ₂ ) is a typical thermochromic material. Pure VO ₂ will undergo a metal-insulator transition at around 68°C, and the optical properties will change dramatically before and after the transition. It has a wide range of application prospects. Its most significant feature is the thermal hysteresis effect, that is, there is a difference in the phase transition temperature between heating and cooling. Generally, because the phase transition requires the drive of superheat or subcooling, the phase transition temperature of heating is higher than the phase transition temperature of cooling. In fact, this thermal hysteresis effect can be used as a thermal switch, that is, the substrate can be heated by electricity to make it pass the phase transition temperature and undergo a phase transition, and the discoloration state can still be maintained after the power is turned off.

Vanadium dioxide also has some inherent problems. In addition to optical properties and phase transition temperature, the biggest problems faced in practical applications are poor physical and chemical stability, and the yellowish color is uncomfortable. At present, some people adjust the color temperature of the VO ₂ film by mixing the temperature-sensitive color-changing powder in the powder (China has published a patent "A Smart Window Film with Adjustable Cool and Warm Color Tones and Its Preparation Method", Publication No.: CN114262457A), and others Utilize _SiO2 to protect the film, and use cesium tungsten bronze to adjust the color at the same time (China's published patent "An intelligent thermal insulation composite coating with high visible light transmittance and its production method", publication number: CN113105765A), but additional The additional SiO ₂ or tungsten bronze film layer makes the process complicated, and the temperature-sensitive color-changing powder will weaken the modulation ability of VO ₂ itself, and there are still some problems in distance application.

SUMMARY OF THE INVENTION

The purpose of the present invention is to solve the problems of complicated preparation process and poor discoloration ability of the existing VO ₂ film, and to provide an electrically-driven Joule thermochromic laminated glass with adjustable color and a preparation method thereof.

An electrically driven Joule thermochromic laminated glass with adjustable color, which is composed of a top glass layer, a thermochromic polymer layer, a transparent conductive oxide layer and a glass bottom layer in order from top to bottom; the thermochromic polymer layer The layer is made of a polymer substrate, thermochromic powder, and a near-infrared light absorber.

A preparation method of electrically driven Joule thermochromic laminated glass with adjustable color, which is specifically completed according to the following steps:

1. Preparation of thermochromic polymer interlayer: first add thermochromic powder and near-infrared light absorber to ethanol, then add dispersant and defoamer, ultrasonically treat for 1h to 2h, then add polymer substrate, Aging for 0.5h-1.5h under stirring conditions to obtain a thermochromic polymer interlayer; the volume ratio of the ethanol to the dispersant is 20:(0.1-2), and the volume ratio of the ethanol to the defoamer is 20 : (0.1 to 2); the mass ratio of the polymer substrate to ethanol is 1: (5 to 10); the volume ratio of the polymer substrate to the thermochromic powder is 90: (5 to 10); The volume ratio of the polymer substrate to the near-infrared light absorber is 90:(0.5～5);

2. Assembly: Method 1: First adhere the transparent conductive oxide layer to one side of the glass bottom layer, then glue the mold on the surface of the transparent conductive oxide layer with glass glue or hot melt adhesive, and then place it on the coating machine, The thermochromic polymer interlayer obtained in step 1 is scraped and coated according to the mold by the method of blade coating, and then the top layer of the glass is covered by the parallel push method, and the film is naturally dried or heated to obtain a color-adjustable electric drive. Joule thermochromic laminated glass;

Method 2: First adhere the transparent conductive oxide layer to one side of the glass bottom layer, then use glass glue or hot melt adhesive to glue the mold on the surface of the transparent conductive oxide layer, and then use glass glue or hot melt adhesive to glue the glass The top layer is adhered to the mold in the form of alignment, and an empty groove is formed by the transparent conductive oxide layer, the mold and the glass top layer, and then the thermochromic polymer interlayer obtained in step 1 is poured into the hollow groove by the pouring method, and it is naturally dried to form a hollow groove. film or heating to obtain electrically driven Joule thermochromic laminated glass with adjustable color.

Advantages of the present invention: 1. The electrically-driven Joule thermochromic laminated glass with adjustable color prepared by the present invention belongs to a simple laminated structure, and the low-cost electrically-driven Joule thermochromic function is realized by using the Joule thermal heating function of the substrate. At the same time, the sandwich structure improves the physical and chemical stability of the film, and the light-absorbing additive in the glue can also improve its color. 2. The color-adjustable electric-driven Joule thermochromic laminated glass prepared by the present invention has brighter colors, rather than yellow; good physical and chemical stability, can slow down the deterioration of particles under strong light after encapsulation, and simultaneously The structure can prevent the oxidation of particles and matrix materials; it can realize active discoloration, and the inside of the laminated glass has a conductive film, and the Joule heat generated after power-on will force the phase change of the thermochromic material to change the optical properties. 3. The color-adjustable electric-driven Joule thermochromic laminated glass prepared by the invention is safe, and even if the laminated glass is broken, it is not easy to produce a large number of fragments flying out instantaneously.

Description of drawings

1 is a schematic structural diagram of the color-modulated electrically driven Joule thermochromic laminated glass described in Example 1, in which 1 represents a thermochromic polymer layer, 10 represents a polymer substrate, 11 represents a near-infrared light absorber, 12 represents the thermochromic powder, 2 represents the glass top layer, 3 represents the transparent conductive oxide layer, and 4 represents the glass bottom layer;

Fig. 2 is the DSC curve of the electrically driven Joule thermochromic laminated glass with adjustable color obtained in Example 2;

Fig. 3 is the transmission spectrum of the electrically driven Joule thermochromic laminated glass with adjustable color obtained in Example 2, in the figure, A represents the phase transmission spectrum at room temperature (20°C), and B represents the phase transmission spectrum at high temperature (80°C);

Figure 4 is the transmission spectrum of the color-modulated electrically driven Joule thermochromic laminated glass obtained in Comparative Example 1. In the figure, A represents the transmission spectrum of the room temperature (20°C) phase, and B represents the transmission spectrum of the high temperature (80°C) phase.

Detailed ways

Embodiment 1: This embodiment is an electrically driven Joule thermochromic laminated glass with adjustable color, which consists of a glass top layer 2, a thermochromic polymer layer 1, and a transparent conductive oxide layer 3 in order from top to bottom. and glass bottom layer 4;

The thermochromic polymer layer 1 is made of a polymer substrate 10 , a thermochromic powder 12 and a near-infrared light absorber 11 .

Embodiment 2: The difference between this embodiment and Embodiment 1 is that the thermochromic powder 12 is doped vanadium dioxide powder or doped vanadium dioxide-coated nanoparticles with an inert shell layer ; the doping element in the doped vanadium dioxide powder is one or more of tungsten, molybdenum, magnesium, zinc, zirconium and tin; the doped vanadium dioxide constitutes nanoparticles of core-shell structure The middle doping element is one or more of tungsten, molybdenum, magnesium, zinc, zirconium and tin, and the inert shell is a silica shell, a titania shell or a zirconia shell. Others are the same as the first embodiment.

Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that the thermochromic powder 12 is a SiO ₂ @M-phase VO ₂ ultrafine powder. Others are the same as in the first or second embodiment.

The SiO ₂ @M-phase VO ₂ ultrafine powder described in this embodiment is completed according to the following steps:

1. Initial mixing: add 4.0g of cetyltrimethylammonium bromide and 10mL of n-hexanol to 200mL of n-heptane, then add the water phase, and stir and mix at a temperature of 60°C for 30min to obtain a blue transparent emulsion;

The aqueous phase consists of 5mL VO ²⁺ precursor solution and 0.02g ammonium metatungstate;

The preparation process of the VO ²⁺ precursor solution is as follows: 100 mL of a hydrochloric acid solution with a concentration of 1 mol/L is mixed with 10.0 g of V ₂ O ₅ , 2.0 mL of ammonia monohydrate is added dropwise, and then the temperature is 60 ° C and the rotation speed is 500 rpm. Under magnetic stirring for 2h, the VO ²⁺ precursor solution was obtained;

2. Ultrasonic stirring: Add ammonia water with a concentration of 1 mol/L to the blue transparent emulsion obtained in step 1 under the combined action of ultrasound and stirring, adjust the pH to 10, and then continue the ultrasonic chemical reaction under the combined action of ultrasound and stirring for 2h , to obtain an alkaline mixture; the frequency of the ultrasonic wave is 30kHz, and the power is 100W; the rotating speed of the stirring is 500rpm;

3. Coating: first cool the alkaline mixture obtained in step 2 to room temperature, add 0.5 mL of ethyl orthosilicate, stir at a stirring speed of 700 rpm for 4 h, add 40 mL of diethylene glycol to promote phase separation, and then perform centrifugal separation and washing, drying at 80°C for 12h to obtain crude powder;

④: Annealing: The crude powder was annealed at a temperature of 900 °C for 1 h in a nitrogen atmosphere with a gas flow of 250 sccm to obtain a SiO ₂ @M-phase VO ₂ ultrafine powder.

Embodiment 4: The difference between this embodiment and Embodiments 1 to 3 is that the polymer substrate 10 is a high polymer transparent material, specifically polyvinylpyrrolidone, polymethyl methacrylate, polycarbonate, Polyurethane, polyvinyl butyral ester, polyvinylidene fluoride or polydimethylsiloxane. Others are the same as those in Embodiments 1 to 3.

Embodiment 5: This embodiment differs from Embodiments 1 to 4 in that: the near-infrared light absorber 11 is one or more of a tungsten bronze compound and a defect tungsten oxide; the tungsten bronze compound is Li _x WO _3-x , Na _x WO _3-x , K _x WO _3-x , Rb _x WO _3-x or Cs _x WO _3-x ; the defective tungsten oxide is WO _2.72 , WO _2.92 or WO _2.9 . Others are the same as the specific embodiments 1 to 4.

Embodiment 6: One of the differences between this embodiment and Embodiments 1 to 5 is that the volume ratio of the polymer substrate 10 to the thermochromic powder 12 in the thermochromic polymer layer 1 is 90:(5~ 10), the volume ratio of the polymer substrate 10 to the near-infrared light absorber 11 is 90:(0.5-5). Others are the same as the specific embodiments 1 to 5.

Embodiment 7: The difference between this embodiment and Embodiments 1 to 6 is that the transparent conductive oxide layer 3 is an indium tin oxide film, a fluorine-doped tin oxide film or a silver film film. Others are the same as the specific embodiments 1 to 6.

Embodiment 8: The difference between this embodiment and Embodiments 1 to 7 is that the thickness of the glass top layer 2 and the glass bottom layer 4 is 1 mm to 3 mm, and the thickness of the thermochromic polymer layer 1 is 0.2 μm ˜2 μm, and the thickness of the transparent conductive oxide layer 3 is 0.1 μm˜0.3 μm. Others are the same as the specific embodiments 1 to 7.

Specific embodiment 9: This embodiment is a preparation method of electrically driven Joule thermochromic laminated glass with adjustable color, which is characterized in that it is completed according to the following steps:

1. Preparation of thermochromic polymer interlayer: first add thermochromic powder 12 and near-infrared light absorber 11 to ethanol, then add dispersant and defoamer, ultrasonically treat for 1h to 2h, and then add polymer substrate 10. Aging under stirring conditions for 0.5h-1.5h to obtain a thermochromic polymer interlayer; the volume ratio of the ethanol to the dispersant is 20:(0.1-2), and the volume of the ethanol to the defoamer is 20: (0.1-2). The ratio is 20:(0.1-2); the mass ratio of the polymer substrate 10 to ethanol is 1:(5-10); the volume ratio of the polymer substrate 10 to the thermochromic powder 12 is 90:( 5-10); the volume ratio of the polymer substrate 10 to the near-infrared light absorber 11 is 90: (0.5-5);

2. Assembly: Method 1: First adhere the transparent conductive oxide layer 3 to one side of the glass bottom layer 4, and then glue the mold on the surface of the transparent conductive oxide layer 3 with glass glue or hot melt adhesive, and then place it on the surface of the transparent conductive oxide layer 3. On the cloth machine, the thermochromic polymer interlayer obtained in step 1 is scraped and coated according to the mold by the method of scraping coating, and then the top layer 2 of the cover glass is aligned with the method of parallel pushing, and it is naturally dried to form a film or heated to form a film, and the color can be obtained. Modulated electrically driven Joule thermochromic laminated glass;

Method 2: First, the transparent conductive oxide layer 3 is adhered to one side of the glass bottom layer 4, and then the mold is adhered to the surface of the transparent conductive oxide layer 3 by glass glue or hot melt adhesive, and then glass glue or hot melt adhesive is used. Adhere the glass top layer 2 on the mold in the form of alignment, and form an empty groove by the transparent conductive oxide layer 3, the mold and the glass top layer 2, and then use the pouring method to pour the thermochromic polymer sandwich obtained in step 1 into the hollow. In the tank, the film is naturally dried or heated to form a film to obtain an electrically driven Joule thermochromic laminated glass with adjustable color.

Embodiment 10: The difference between this embodiment and Embodiment 9 is that the dispersing agent in step 1 is a silane coupling agent KH-570, specifically γ-(methacryloyloxy)propyltrimethoxy Silane; the defoamer in step 1 is polyether-modified silicone oil or tributyl phosphate. Others are the same as in the ninth embodiment.

The content of the present invention is not limited to the content of the above-mentioned embodiments, and a combination of one or more specific embodiments can also achieve the purpose of the invention.

Adopt the following test to verify the effect of the present invention:

Example 1: An electrically driven Joule thermochromic laminated glass with adjustable color, which consists of a top glass layer 2, a thermochromic polymer layer 1, a transparent conductive oxide layer 3 and a glass bottom layer 4 in order from top to bottom ; The thickness of the glass top layer 2 and the glass bottom layer 4 is 1 mm, the thickness of the thermochromic polymer layer 1 is 0.5 μm, and the thickness of the transparent conductive oxide layer 3 is 0.1 μm;

The thermochromic polymer layer 1 is made of a polymer substrate 10 , a thermochromic powder 12 and a near-infrared light absorber 11 .

The thermochromic powder 12 is a SiO ₂ @M-phase VO ₂ ultrafine powder, which is carried out according to the following steps:

1. Initial mixing: add 4.0g of cetyltrimethylammonium bromide and 10mL of n-hexanol to 200mL of n-heptane, then add the water phase, stir and mix at a temperature of 60°C for 30min to obtain a blue transparent emulsion; The aqueous phase is composed of 5mL VO ²⁺ precursor solution and 0.02g ammonium metatungstate; the preparation process of the VO ²⁺ precursor solution is as follows: 100mL of hydrochloric acid solution with a concentration of 1mol/L and 10.0g V ₂ O ₅ are mixed, and then 2.0 mL of ammonia monohydrate was added dropwise, and then the reaction was performed by magnetic stirring at a temperature of 60 °C and a rotational speed of 500 rpm for 2 h to obtain a VO ²⁺ precursor;

2. Ultrasonic stirring: Add ammonia water with a concentration of 1 mol/L to the blue transparent emulsion obtained in step 1 under the combined action of ultrasound and stirring, adjust the pH to 10, and then continue the ultrasonic chemical reaction under the combined action of ultrasound and stirring for 2h , to obtain an alkaline mixture; the frequency of the ultrasonic wave is 30kHz, and the power is 100W; the rotating speed of the stirring is 500rpm;

3. Coating: first cool the alkaline mixture obtained in step 2 to room temperature, add 0.5 mL of ethyl orthosilicate, stir at a stirring speed of 700 rpm for 4 h, add 40 mL of diethylene glycol to promote phase separation, and then perform centrifugal separation and washing, drying at 80°C for 12h to obtain crude powder;

④: Annealing: The crude powder was annealed for 1 h at a temperature of 900 ℃ in a nitrogen atmosphere with a gas flow of 250 sccm to obtain a SiO ₂ @M-phase VO ₂ ultrafine powder.

The polymer substrate 10 described in Example 1 is polymethyl methacrylate.

The near-infrared light absorber 11 described in Example 1 is a tungsten bronze compound, specifically Cs _x WO _3-x .

The volume ratio of the polymer substrate 10 to the thermochromic powder 12 in the thermochromic polymer layer 1 described in Example 1 is 89:10, and the volume ratio of the polymer substrate 10 to the near-infrared light absorber 11 is 89: 1.

The transparent conductive oxide layer 3 described in Embodiment 1 is an indium tin oxide film.

The glass top layer 2 and the glass bottom layer 4 described in Example 1 are ordinary float glass.

1 is a schematic structural diagram of the color-modulated electrically driven Joule thermochromic laminated glass described in Example 1, in which 1 represents a thermochromic polymer layer, 10 represents a polymer substrate, 11 represents a near-infrared light absorber, 12 represents the thermochromic powder, 2 represents the glass top layer, 3 represents the transparent conductive oxide layer, and 4 represents the glass bottom layer.

Embodiment 2: as shown in Embodiment 1, a method for preparing an electrically driven Joule thermochromic laminated glass with adjustable color, which is specifically completed according to the following steps:

1. Preparation of thermochromic polymer interlayer: first add thermochromic powder 12 and near-infrared light absorber 11 to ethanol, then add dispersant and defoamer, ultrasonically treat for 1h to 2h, and then add polymer substrate 10, ageing under stirring conditions for 0.5h～1.5h to obtain a thermochromic polymer interlayer; the volume ratio of the ethanol to the dispersant is 20:0.5, and the volume ratio of the ethanol to the defoamer is 20: 0.5; the mass ratio of the polymer substrate 10 to ethanol is 1:8; the volume ratio of the polymer substrate 10 to the thermochromic powder 12 is 89:10; the polymer substrate 10 absorbs near-infrared light The volume ratio of agent 11 is 89:1;

2. Assembly: First, the transparent conductive oxide layer 3 is adhered to one side of the glass bottom layer 4, and then the mold is adhered to the surface of the transparent conductive oxide layer 3 with glass glue or hot melt adhesive, and then placed on the coating machine. The thermochromic polymer interlayer obtained in step 1 is scraped and coated according to the mold by the method of scraping coating, and then the top layer 2 of the cover glass is aligned with the method of parallel pushing, and it is naturally dried to form a film or heated to form a film to obtain a color-adjustable electric film. Driving Joule thermochromic laminated glass.

The color-modulated electrically driven Joule thermochromic laminated glass described in Example 2 is composed of a glass top layer 2, a thermochromic polymer layer 1, a transparent conductive oxide layer 3 and a glass bottom layer 4 in order from top to bottom; The thickness of the glass top layer 2 and the glass bottom layer 4 is 1 mm, the thickness of the thermochromic polymer layer 1 is 0.5 μm, and the thickness of the transparent conductive oxide layer 3 is 0.1 μm; the thickness of the thermochromic polymer layer 1 The thermochromic polymer interlayer obtained in step 1 of Example 2 is cured to form a film.

The thermochromic powder 12 described in Example 2 is SiO ₂ @M-phase VO ₂ ultrafine powder, which is carried out according to the following steps:

1. Initial mixing: add 4.0g of cetyltrimethylammonium bromide and 10mL of n-hexanol to 200mL of n-heptane, then add the water phase, stir and mix at a temperature of 60°C for 30min to obtain a blue transparent emulsion; The aqueous phase is composed of 5mL VO ²⁺ precursor solution and 0.02g ammonium metatungstate; the preparation process of the VO ²⁺ precursor solution is as follows: 100mL of hydrochloric acid solution with a concentration of 1mol/L and 10.0g V ₂ O ₅ are mixed, and then 2.0 mL of ammonia monohydrate was added dropwise, and then the reaction was performed by magnetic stirring at a temperature of 60 °C and a rotational speed of 500 rpm for 2 h to obtain a VO ²⁺ precursor;

2. Ultrasonic stirring: Add ammonia water with a concentration of 1 mol/L to the blue transparent emulsion obtained in step 1 under the combined action of ultrasound and stirring, adjust the pH to 10, and then continue the ultrasonic chemical reaction under the combined action of ultrasound and stirring for 2h , to obtain an alkaline mixture; the frequency of the ultrasonic wave is 30kHz, and the power is 100W; the rotating speed of the stirring is 500rpm;

3. Coating: first cool the alkaline mixture obtained in step 2 to room temperature, add 0.5 mL of ethyl orthosilicate, stir at a stirring speed of 700 rpm for 4 h, add 40 mL of diethylene glycol to promote phase separation, and then perform centrifugal separation and washing, drying at 80°C for 12h to obtain crude powder;

④: Annealing: The crude powder was annealed at a temperature of 900 °C for 1 h in a nitrogen atmosphere with a gas flow of 250 sccm to obtain a SiO ₂ @M-phase VO ₂ ultrafine powder.

The polymer substrate 10 described in Example 2 is polymethyl methacrylate.

The near-infrared light absorber 11 described in Example 2 is a tungsten bronze compound, specifically Cs _x WO _3-x .

In Embodiment 2, the transparent conductive oxide layer 3 is an indium tin oxide film.

The glass top layer 2 and the glass bottom layer 4 described in Example 2 are ordinary float glass.

Fig. 2 is the DSC curve of the electrically driven Joule thermochromic laminated glass with adjustable color obtained in Example 2. It can be seen from Fig. 2 that the phase of the electrically driven Joule thermochromic laminated glass with adjustable color obtained in Example 2 The transformation temperature is about 53.4 °C, and it can be transformed into the low-temperature M phase again when it is lower than 28.7 °C, which has a good thermal switching effect.

Comparative Example 1: Thermochromic polymer layer 1 without adding near-infrared light absorber 11 Comparison:

1. Preparation of thermochromic polymer interlayer: first add thermochromic powder 12 to ethanol, then add dispersant and defoamer, ultrasonically treat for 1h to 2h, then add polymer substrate 10, and age under stirring conditions for 0.5 h to 1.5 h to obtain a thermochromic polymer interlayer; the volume ratio of the ethanol to the dispersant is 20:0.5, and the volume ratio of the ethanol to the defoamer is 20:0.5; the polymer substrate The mass ratio of 10 to ethanol is 1:8; the volume ratio of the polymer substrate 10 to the thermochromic powder 12 is 89:10;

2. Assembly: First, the transparent conductive oxide layer 3 is adhered to one side of the glass bottom layer 4, and then the mold is adhered to the surface of the transparent conductive oxide layer 3 with glass glue or hot melt adhesive, and then placed on the coating machine. The thermochromic polymer interlayer obtained in step 1 is scraped and coated according to the mold by the method of scraping coating, and then the top layer 2 of the cover glass is aligned with the method of parallel pushing, and it is naturally dried to form a film or heated to form a film to obtain a color-adjustable electric film. Driving Joule thermochromic laminated glass.

The color-modulated electrically driven Joule thermochromic laminated glass of Comparative Example 1 is composed of a glass top layer 2, a thermochromic polymer layer 1, a transparent conductive oxide layer 3 and a glass bottom layer 4 in order from top to bottom; The thickness of the glass top layer 2 and the glass bottom layer 4 is 1 mm, the thickness of the thermochromic polymer layer 1 is 0.5 μm, and the thickness of the transparent conductive oxide layer 3 is 0.1 μm; the thickness of the thermochromic polymer layer 1 The thermochromic polymer interlayer obtained in step 1 of Example 2 is cured to form a film.

The thermochromic powder 12 described in Comparative Example 1 is SiO ₂ @M-phase VO ₂ ultrafine powder, which is carried out according to the following steps:

1. Initial mixing: add 4.0g of cetyltrimethylammonium bromide and 10mL of n-hexanol to 200mL of n-heptane, then add the water phase, stir and mix at a temperature of 60°C for 30min to obtain a blue transparent emulsion; The aqueous phase is composed of 5mL VO ²⁺ precursor solution and 0.02g ammonium metatungstate; the preparation process of the VO ²⁺ precursor solution is as follows: 100mL of hydrochloric acid solution with a concentration of 1mol/L and 10.0g V ₂ O ₅ are mixed, and then 2.0 mL of ammonia monohydrate was added dropwise, and then the reaction was performed by magnetic stirring at a temperature of 60 °C and a rotational speed of 500 rpm for 2 h to obtain a VO ²⁺ precursor;

2. Ultrasonic stirring: Add ammonia water with a concentration of 1 mol/L to the blue transparent emulsion obtained in step 1 under the combined action of ultrasound and stirring, adjust the pH to 10, and then continue the ultrasonic chemical reaction under the combined action of ultrasound and stirring for 2h , to obtain an alkaline mixture; the frequency of the ultrasonic wave is 30kHz, and the power is 100W; the rotating speed of the stirring is 500rpm;

3. Coating: first cool the alkaline mixture obtained in step 2 to room temperature, add 0.5 mL of ethyl orthosilicate, stir at a stirring speed of 700 rpm for 4 h, add 40 mL of diethylene glycol to promote phase separation, and then perform centrifugal separation and washing, drying at 80°C for 12h to obtain crude powder;

④: Annealing: The crude powder was annealed for 1 h at a temperature of 900 ℃ in a nitrogen atmosphere with a gas flow of 250 sccm to obtain a SiO ₂ @M-phase VO ₂ ultrafine powder.

In Comparative Example 1, the polymer substrate 10 is polymethyl methacrylate.

In Comparative Example 1, the transparent conductive oxide layer 3 is an indium tin oxide film.

In Comparative Example 1, the glass top layer 2 and the glass bottom layer 4 are ordinary float glass.

Fig. 3 is the transmission spectrum of the electrically driven Joule thermochromic laminated glass with adjustable color obtained in Example 2. In the figure, A represents the phase transmission spectrum at room temperature (20°C), and B represents the phase transmission spectrum at high temperature (80°C). 4 is the transmission spectrum of the electrically driven Joule thermochromic laminated glass with adjustable color obtained in Comparative Example 1. In the figure, A represents the transmission spectrum of the room temperature (20°C) phase, and B represents the transmission spectrum of the high temperature (80°C) phase. 3 and FIG. 4 are compared, it can be seen that the color-modulated electrically driven Joule thermochromic laminated glass obtained in Example 2 does not show the original yellow color, which shows that the present invention can absorb a part of the blue light after adding the near-infrared light absorber 11, thereby The compensation of color is realized, and finally the thermochromic polymer layer 1 does not show the original yellow color. potential.

Claims (10)

1. A color-adjustable electric-driven Joule thermochromic laminated glass is characterized in that the color-adjustable electric-driven Joule thermochromic laminated glass is composed of glass top layer (2), thermochromic polymerization from top to bottom in turn. The material layer (1), the transparent conductive oxide layer (3) and the glass bottom layer (4) are composed; The thermochromic polymer layer (1) is made of a polymer substrate (10), a thermochromic powder (12) and a near-infrared light absorber (11). 2. The electrically driven Joule thermochromic laminated glass with adjustable color according to claim 1, characterized in that the thermochromic powder (12) is doped vanadium dioxide powder or doped The vanadium dioxide coated inert shell layer nanoparticles; the doping element in the doped vanadium dioxide powder is one or more of tungsten, molybdenum, magnesium, zinc, zirconium and tin; the doped vanadium dioxide powder The doping elements in the nanoparticles that form the core-shell structure of the heterovanadium dioxide are one or more of tungsten, molybdenum, magnesium, zinc, zirconium and tin, and the inert shell is a silica shell, a titanium dioxide shell or a Zirconium dioxide shell. 3. The electrically driven Joule thermochromic laminated glass with adjustable color according to claim 2, wherein the thermochromic powder (12) is SiO ₂ @M phase VO ₂ ultrafine powder . 4. The electrically driven Joule thermochromic laminated glass with adjustable color according to claim 3, characterized in that the polymer substrate (10) is a high polymer transparent material, specifically polyvinylpyrrolidone, polyvinylpyrrolidone, polyvinylpyrrolidone Methyl methacrylate, polycarbonate, polyurethane, polyvinyl butyral, polyvinylidene fluoride or polydimethylsiloxane. 5. The electrically driven Joule thermochromic laminated glass with adjustable color according to claim 4, wherein the near-infrared light absorber (11) is a kind of tungsten bronze compound and defect tungsten oxide or several; the tungsten bronze compound is Li _x WO _3-x , Na _x WO _3-x , K _x WO _3-x , Rb _x WO _3-x or Cs _x WO _3-x ; the defective tungsten oxide is WO _2.72 , WO _2.92 or WO _2.9 . 6. The electrically driven Joule thermochromic laminated glass with adjustable color according to claim 5, characterized in that in the thermochromic polymer layer (1), the polymer substrate (10) and the thermochromic The volume ratio of the powder (12) is 90:(5-10), and the volume ratio of the polymer substrate (10) to the near-infrared light absorber (11) is 90:(0.5-5). 7. The electrically driven Joule thermochromic laminated glass with adjustable color according to claim 1, characterized in that the transparent conductive oxide layer (3) is an indium tin oxide film, a fluorine-doped tin oxide film or silver film. 8 . The electrically driven Joule thermochromic laminated glass with adjustable color according to claim 1 , wherein the thickness of the glass top layer ( 2 ) and the glass bottom layer ( 4 ) is 1 mm to 3 mm, and the thickness of the glass top layer ( 2 ) and the glass bottom layer ( 4 ) The thickness of the thermochromic polymer layer (1) is from 0.2 μm to 2 μm, and the thickness of the transparent conductive oxide layer (3) is from 0.1 μm to 0.3 μm. 9. the preparation method of the electrically driven Joule thermochromic laminated glass that a kind of color can be modulated as described in claim 1 to 8, it is characterized in that it is completed according to the following steps: 1. Preparation of thermochromic polymer interlayer: first add thermochromic powder (12) and near-infrared light absorber (11) into ethanol, then add dispersant and defoamer, ultrasonically treat for 1h to 2h, and then add A polymer substrate (10) is added and aged for 0.5h-1.5h under stirring conditions to obtain a thermochromic polymer interlayer; the volume ratio of the ethanol to the dispersant is 20:(0.1-2), and the ethanol The volume ratio to the defoamer is 20:(0.1-2); the mass ratio of the polymer substrate (10) to the ethanol is 1:(5-10); the polymer substrate (10) and the thermochromic The volume ratio of the powder (12) is 90:(5-10); the volume ratio of the polymer substrate (10) to the near-infrared light absorber (11) is 90:(0.5-5); 2. Assembly: Method 1: First adhere the transparent conductive oxide layer (3) to one side of the glass bottom layer (4), and then glue the mold on the surface of the transparent conductive oxide layer (3) with glass glue or hot melt adhesive Then put it on the coating machine, use the method of scraping coating to scrape the thermochromic polymer interlayer obtained in step 1 according to the mold, and then use the parallel push method to align the cover glass top layer (2), and naturally dry to form a film Or heating to form a film to obtain electrically driven Joule thermochromic laminated glass with adjustable color; Method 2: First, the transparent conductive oxide layer (3) is adhered to one side of the glass bottom layer (4), and then the mold is adhered to the surface of the transparent conductive oxide layer (3) by glass glue or hot melt adhesive, and then The glass top layer (2) is adhered to the mold in an aligned form by glass glue or hot melt adhesive, and an empty groove is formed by the transparent conductive oxide layer (3), the mold and the glass top layer (2). The obtained thermochromic polymer interlayer is poured into an empty tank, naturally dried to form a film or heated to form a film, to obtain an electrically driven Joule thermochromic laminated glass with adjustable color. 10. The method for preparing a color-adjustable electrically driven Joule thermochromic laminated glass according to claim 9, wherein the dispersing agent in step 1 is a silane coupling agent KH-570, specifically γ -(methacryloyloxy)propyltrimethoxysilane; the defoamer in step 1 is polyether-modified silicone oil or tributyl phosphate.

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