Preparation method of visible-near infrared dual-band regulation electrochromic film

Abstract

The application discloses a preparation method of a visible-near-infrared dual-band regulation electrochromic film, and belongs to the technical field of electrochromic films. The preparation method comprises the following steps: spraying polyaniline dispersion liquid on a conductive glass substrate, annealing, obtaining a polyaniline film, continuously spraying silver dispersion liquid on the surface of the polyaniline film, repeating the process of spraying polyaniline dispersion liquid, annealing, spraying silver dispersion liquid and annealing, and obtaining the visible-near-infrared dual-band regulation electrochromic film. The voltage window of the visible-near-infrared dual-band regulation electrochromic film is -0.4V-1.5V, the electrochromic film has colorful color changes from yellow to green and then to blue, the dual-band regulation electrochromic film is yellow when a voltage of -0.4V is applied, has high visible and near-infrared light transmittance, the dual-band regulation electrochromic film is green when a voltage of 0.3V is applied, shields near-infrared light while maintaining high visible light transmittance, and the dual-band regulation electrochromic film is blue when a voltage of 1.5V is applied, and can shield most visible and near-infrared light.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of electrochromic thin films, and particularly relates to a preparation method of a visible-near-infrared dual-band modulation electrochromic thin film. BACKGROUND

[0002] The dual-band electrochromic thin film is a new technology, which improves the energy efficiency of buildings by dynamically and independently controlling the transmittance of near-infrared and visible light. At present, the research on the dual-band electrochromic thin film mainly focuses on inorganic electrochromic materials. However, due to the relatively fixed energy band structure of inorganic materials, the color change of the reported dual-band electrochromic thin film is relatively monotonous, which limits its large-scale application.

[0003] Organic polymer electrochromic materials such as polyaniline generally have rich color conversion capability. The polyaniline electrochromic thin film is expected to realize independent regulation of near-infrared and visible light, and at the same time make up for the disadvantage of single color change of inorganic electrochromic materials, thereby enriching the color of the thin film.

[0004] The color change of polyaniline in the visible light band is rich, but the transmittance change range in the near-infrared band is small. For example, Xu Kun et al., Electrochemistry, 2019, 25(06), studied the electrochromic properties of polyaniline thin film by combining potential step and cyclic voltammetry with ultraviolet-visible light spectrophotometry, found that the color of polyaniline thin film was variable, and the color changed between light yellow, green and blue, studied the electrochemical cyclic stability of polyaniline thin film in different color change intervals, and the research results showed that the thin film changed in the yellow to blue (0.4V-1.2V) and green to blue (0.8V-1.2V) intervals, but the electrochromic cyclic performance was poor, and the change of near-infrared transmittance was not particularly concerned. In order to improve the transmittance change of polyaniline material in the near-infrared band and realize the regulation of different optical modes, polyaniline needs to be modified; Chinese patent CN 115196885 A discloses a CeO2 / PANI electrochromic thin film with multi-color high cyclic stability and a preparation method thereof, which improves the cyclic stability to a certain extent, but the color contrast of the prepared composite thin film is not high and the thin film does not have dual-band modulation capability; Chinese patent CN 105130210 A discloses a preparation method of a three-dimensional ordered macroporous polyaniline / carbon composite electrochromic thin film. Due to the introduction of carbon, the conductivity of polyaniline is improved, and the electrochromic performance of polyaniline thin film is improved, but the thin film does not have dual-band modulation capability. Therefore, it is necessary to develop an electrochromic thin film which has multi-color variable color capability and visible-near-infrared dual-band modulation. SUMMARY

[0005] To solve the above technical problems, the application provides a preparation method of a visible-near-infrared dual-band regulation electrochromic film, which introduces silver nanoparticles and polyaniline film for layer-by-layer stacking and compounding, improves the modulation capacity of polyaniline material in the near-infrared band and enhances the electrochromic performance through the local surface plasmon resonance effect and good conductivity of the silver nanoparticles.

[0006] To achieve the above object, the application provides a preparation method of a visible-near-infrared dual-band regulation electrochromic film, which comprises the following steps:

[0007] Spray polyaniline dispersion liquid on the conductive glass substrate, anneal to obtain a polyaniline film, continue to spray silver dispersion liquid on the surface of the polyaniline film, anneal, and repeat the process of spraying polyaniline dispersion liquid, annealing and spraying silver dispersion liquid, annealing to obtain the visible-near-infrared dual-band regulation electrochromic film.

[0008] Further, the conductive glass is ITO conductive glass.

[0009] Further, the mass concentration of the polyaniline dispersion liquid is 0.8-10%, preferably 1%. Under the condition that the spraying amount of polyaniline is constant, the gradient experiment results of polyaniline dispersion liquids with different concentrations show that when the mass concentration of the polyaniline dispersion liquid is 1%, the optical modulation capacity and response time are optimal.

[0010] Further, the total spraying amount of the polyaniline dispersion liquid is 100-800 muL, preferably 200 muL. Under the condition that the concentration of the polyaniline dispersion liquid is limited, the gradient experiment results of different spraying amounts show that when the spraying amount is 200 muL, the optical modulation capacity and response time are optimal.

[0011] Further, the mass concentration of the silver dispersion liquid is 0.05-0.8 mg / mL, preferably 0.1 mg / mL. When the concentration is 0.1 mg / mL, the electrochromic performance is optimal.

[0012] Further, the silver dispersion liquid comprises silver nanoparticle dispersion liquid, silver nanowire dispersion liquid or silver nanoplate dispersion liquid.

[0013] Further, the total spraying amount of the silver dispersion liquid is 100-800 muL, preferably 100 muL, 200 muL, 300 muL, 400 muL or 500 muL. When the spraying amount is too high, the optical modulation capacity and response time decrease obviously.

[0014] Further, the number of layers of the visible-near-infrared dual-band regulation electrochromic film is 1-10, preferably 2, 3, 4, 5 or 6. When the number of layers increases, the amount of silver dispersion liquid sprayed increases, and the optical modulation capacity and response time decrease obviously.

[0015] Further, the annealing temperature is 80-120 DEG C, and the annealing time is 5-30 min. Annealing makes polyaniline and the ITO substrate tightly combined, and too high or too low annealing temperature will make the electrochromic performance decline.

[0016] The visible-near infrared dual-band regulation electrochromic film is prepared according to the preparation method, and the visible-near infrared dual-band regulation electrochromic film has a voltage window of -0.4 V-1.5 V, a coloring time of 6.7-18.1 s, and a bleaching time of 18.0-23.1 s.

[0017] Compared with the prior art, the present application has the following advantages and technical effects:

[0018] 1. The present application uses a simpler spraying method to prepare the composite film, which is simple to operate and has a lower cost. The visible-near infrared dual-band regulation electrochromic film can be prepared by directly spraying polyaniline and silver nano-dispersion liquid on the ITO glass substrate repeatedly, without a complex composite reaction, strong acid, strong alkali, strong corrosive chemical solvent, and complex chemical reaction container, so that the preparation process is simple and the cost is low.

[0019] 2. The composite film prepared by the present application has the ability of dual-band independent regulation and rich color change with high contrast. The electrochromic performance of the prepared composite film, such as response time and coloring efficiency, is greatly improved. The electrochromic film prepared by the method of the present application has the ability of visible-near infrared dual-band independent regulation, and has a voltage window of -0.4 V-1.5 V, and a multi-color change from yellow to green to blue. The dual-band regulation electrochromic film is yellow when a voltage of -0.4 V is applied, has a high visible and near infrared light transmittance; is green when a voltage of 0.3 V is applied, shields near infrared while maintaining a high visible light transmittance; and is blue when a voltage of 1.5 V is applied, can shield most visible and near infrared light. Compared with the pure polyaniline single-layer dual-band electrochromic film, the electrochromic response speed of the polyaniline / silver layer stacked composite electrochromic film is greatly improved. BRIEF DESCRIPTION OF DRAWINGS

[0020] The accompanying drawings, which form a part of the present application, are used to provide further understanding of the present application, and the schematic embodiments of the present application and their descriptions are used to explain the present application, and do not constitute improper limitations on the present application. In the drawings:

[0021] Figure 1 The transmittance spectrum diagram of the 1-layer polyaniline electrochromic film prepared for Example 1 under different voltages;

[0022] Figure 2 The response time diagram of the 1-layer polyaniline electrochromic film prepared for Example 1;

[0023] Figure 3 Transmission spectra of the 2-layer composite dual-band electrochromic film prepared for Example 2 at different voltages;

[0024] Figure 4 Response time plot of the 2-layer composite dual-band electrochromic film prepared for Example 2;

[0025] Figure 5 Transmission spectra of the 3-layer composite dual-band electrochromic film prepared for Example 3 at different voltages;

[0026] Figure 6 Response time plot of the 3-layer composite dual-band electrochromic film prepared for Example 3;

[0027] Figure 7 Transmission spectra of the 4-layer composite dual-band electrochromic film prepared for Example 4 at different voltages;

[0028] Figure 8 Response time plot of the 4-layer composite dual-band electrochromic film prepared for Example 4;

[0029] Figure 9 Transmission spectra of the 5-layer composite dual-band electrochromic film prepared for Example 5 at different voltages;

[0030] Figure 10 Response time plot of the 5-layer composite dual-band electrochromic film prepared for Example 5;

[0031] Figure 11 Transmission spectra of the 6-layer composite dual-band electrochromic film prepared for Example 6 at different voltages;

[0032] Figure 12 Response time plot of the 6-layer composite dual-band electrochromic film prepared for Example 6. DETAILED DESCRIPTION

[0033] Various example embodiments of the present application will now be described in detail with reference to the drawings. Such description, however, is to be considered in

[0034] It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application. Additionally, for a range of values of or intervals between the values stated in this detailed description are to be understood as not only including the explicitly stated values or interval endpoints, but each individual value or interval, to the exact midpoint, between each individual value or interval stated. Any smaller range between any two larger ranges, as context can permit, is also intended to be included in the present application. The upper and lower limits of these smaller ranges can independently be included or excluded in the ranges.

[0035] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as those commonly understood by one of ordinary skill in the art to which this application pertains. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application, the preferred methods and materials are described. All publications mentioned in the specification are incorporated by reference to disclose and describe the methods and / or materials in connection with which the publications are cited. In case of conflict between the content of the specification and that of any incorporated literature, the content of the specification controls.

[0036] Many modifications and variations of this application can be made in the light of the above teachings without departing from the spirit and scope thereof. Additional implementations of the application will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. The examples in the specification are exemplary only.

[0037] It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0038] The raw materials in the embodiments of the present application can be purchased.

[0039] The area of ITO conductive glass substrate in the following examples is 2x2cm 2 .

[0040] Example 1

[0041] Take 200μL polyaniline dispersion (mass concentration is 1%) and put it in a spray gun. Fix the ITO conductive glass substrate on the heating table at 100℃. Place the spray gun vertically above the ITO conductive glass substrate at a distance of 10cm and spray the polyaniline dispersion on the ITO substrate at a constant flow. After the spraying is completed, anneal and solidify at 100℃ for 15min to obtain an electrochromic film with only one layer of polyaniline.

[0042] The transmittance spectrum of the one-layer polyaniline electrochromic film prepared in this example under different voltages is shown in Figure 1 , and Figure 1It can be seen that the voltage window of the pure polyaniline electrochromic film is -0.4V-1.5V, when a voltage of -0.4V is applied, the film is yellow, at this time the film has a higher transmittance in the near-infrared and visible wave bands, when a voltage of 0.3V is applied, the film is green, at this time the film shields the near-infrared while maintaining a higher visible light transmittance, when a voltage of 1.5V is applied, the film is blue, at this time the film shields most of the near-infrared and visible light, has a dual wave band regulation performance, and the total solar light modulation amplitude of the film from the bleached state (-0.4V) to the colored state (1.5V) is 32.6%, the visible light wave band modulation amplitude is 27.9%, and the near-infrared wave band modulation amplitude is 42.1%. From the test results, it can be seen that the polyaniline film has good dual wave band regulation capability, rich color change and obvious color contrast. The response time diagram of the 1-layer polyaniline electrochromic film of Example 1 is shown in Figure 2 From Figure 2 It can be seen that the coloring time and bleaching time of the 1-layer polyaniline electrochromic film are 18.1s and 23.1s respectively.

[0043] Example 2

[0044] Take 200μL of polyaniline dispersion solution (mass concentration of 1%) and place it in a spray gun. Fix the ITO conductive glass substrate on the 100℃ heating table, place the spray gun vertically above the ITO conductive glass substrate at a distance of 10 centimeters and uniformly spray the polyaniline dispersion solution on the ITO substrate at a constant flow. After 100℃ annealing and curing for 5 minutes, then spray 100μL of silver nanowire dispersion solution (mass concentration of 0.1mg / mL) using the same spraying conditions. After spraying, anneal and cure at 100℃ for 15 minutes to obtain a 2-layer composite electrochromic film with 1-layer polyaniline film and 1-layer silver nanowire.

[0045] The transmittance spectrum diagram of the 2-layer composite electrochromic film prepared in this example under different voltages is shown in Figure 3 From Figure 3 It can be seen that the total solar light modulation amplitude of the 2-layer composite electrochromic film from the bleached state (-0.4V) to the colored state (1.5V) is 32.7%, the visible light wave band modulation amplitude is 26.4%, and the near-infrared wave band modulation amplitude is 42.4%. The response time diagram of the 2-layer composite electrochromic film is shown in Figure 4 From Figure 4 It can be seen that the coloring time and bleaching time of the 2-layer composite dual wave band electrochromic film are 7.6s and 18.0s respectively, which is a greater improvement compared to the response speed of the pure polyaniline film in Example 1.

[0046] Example 3

[0047] A 3-layer composite electrochromic film was prepared according to the method of Example 2 (100 μL of polyaniline film as the first layer, 200 μL of silver nanowires as the second layer, and 100 μL of polyaniline film as the third layer).

[0048] The transmittance spectrum of the 3-layer composite electrochromic film prepared in this example under different voltages is shown in Figure 5 From Figure 5 It can be seen that the total solar light modulation amplitude of the 3-layer composite electrochromic film is 29.3% from the bleached state (-0.4 V) to the colored state (1.5 V), the modulation amplitude in the visible light band is 26.6%, and the modulation amplitude in the near-infrared band is 36.5%. The response time graph of the 3-layer composite electrochromic film prepared in this example is shown in Figure 6 From Figure 6 It can be seen that the coloring time and bleaching time of the 3-layer composite electrochromic film are 10.5 s and 19.8 s, respectively.

[0049] Example 4

[0050] A 4-layer composite electrochromic film was prepared according to the method of Example 2 (100 μL of polyaniline film as the first layer, 150 μL of silver nanowires as the second layer, 100 μL of polyaniline film as the third layer, and 150 μL of silver nanowires as the fourth layer).

[0051] The transmittance spectrum of the 4-layer composite electrochromic film prepared in this example under different voltages is shown in Figure 7 From Figure 7 It can be seen that the total solar light modulation amplitude of the 4-layer composite electrochromic film is 29.3% from the bleached state (-0.4 V) to the colored state (1.5 V), the modulation amplitude in the visible light band is 21.8%, and the modulation amplitude in the near-infrared band is 41.9%. The transmittance spectrum of the 4-layer composite electrochromic film prepared in this example under different voltages is shown in Figure 8 From Figure 8 It can be seen that the coloring time and bleaching time of the 4-layer composite electrochromic film are 6.7 s and 18.0 s, respectively.

[0052] Example 5

[0053] A 5-layer composite electrochromic film was prepared according to the method of Example 2 (66.7 μL of polyaniline film as the first layer, 200 μL of silver nanowires as the second layer, 66.7 μL of polyaniline film as the third layer, 200 μL of silver nanowires as the fourth layer, and 66.7 μL of polyaniline film as the fifth layer).

[0054] The transmittance spectrum of the 5-layer composite electrochromic film prepared in this example under different voltages is shown in Figure 9 From Figure 9It can be seen that the total sunlight modulation amplitude of the 5-layer composite electrochromic film is 24.5% from bleached state (-0.4V) to colored state (1.5V), the visible light band modulation amplitude is 21.6%, and the near-infrared band modulation amplitude is 31.7%. The transmittance spectrum diagram of the 5-layer composite electrochromic film prepared in this embodiment under different voltages is shown in Figure 10 From Figure 10 It can be seen that the coloring time and bleaching time of the 5-layer composite electrochromic film are 9.0s and 19.8s respectively.

[0055] Example 6

[0056] A 6-layer composite electrochromic film is prepared according to the method of Example 2 (the first layer is 66.7μL of polyaniline film, the second layer is 166.7μL of silver nanowire, the third layer is 66.7μL of polyaniline film, the fourth layer is 166.7μL of silver nanowire, the fifth layer is 66.7μL of polyaniline film, and the sixth layer is 166.7μL of silver nanowire).

[0057] The transmittance spectrum diagram of the 6-layer composite electrochromic film prepared in this embodiment under different voltages is shown in Figure 11 From Figure 11 It can be seen that the total sunlight modulation amplitude of the 6-layer composite electrochromic film is 13.3% from bleached state (-0.4V) to colored state (1.5V), the visible light band modulation amplitude is 15.1%, and the near-infrared band modulation amplitude is 11.8%. The transmittance spectrum diagram of the 6-layer composite electrochromic film prepared in this embodiment under different voltages is shown in Figure 12 From Figure 12 It can be seen that the coloring time and bleaching time of the 6-layer composite electrochromic film are 9.7s and 21.4s respectively.

[0058] Example 7

[0059] The same as Example 2, except that the mass concentration of the polyaniline dispersion is 5%.

[0060] Example 8

[0061] The same as Example 2, except that the mass concentration of the silver nanowire dispersion is 0.5mg / mL.

[0062] Example 9

[0063] The same as Example 2, except that 100μL of silver nanoparticle dispersion is sprayed.

[0064] Example 10

[0065] The same as Example 2, except that the annealing temperature is 80℃.

[0066] Example 11

[0067] A 10-layer composite electrochromic thin film was prepared according to the method of Example 2 (40 μL of polyaniline thin film for the first layer, 180 μL of silver nanowire for the second layer, 40 μL of polyaniline thin film for the third layer, 180 μL of silver nanowire for the fourth layer, 40 μL of polyaniline thin film for the fifth layer, 180 μL of silver nanowire for the sixth layer, 40 μL of polyaniline thin film for the seventh layer, 180 μL of silver nanowire for the eighth layer, 40 μL of polyaniline thin film for the ninth layer, and 180 μL of silver nanowire for the tenth layer).

[0068] The total solar light modulation amplitude of the 10-layer composite electrochromic thin film prepared in this example was 9.3% from bleached state (-0.4 V) to colored state (1.5 V), the modulation amplitude in visible light band was 10.8%, and the modulation amplitude in near-infrared band was 7.4%. The coloring time and bleaching time of the 10-layer composite electrochromic thin film prepared in this example under different voltages were 15.2 s and 22.8 s, respectively.

[0069] Example 12

[0070] 50 μL of polyaniline dispersion (10% by mass) was taken into a spray gun, an ITO conductive glass substrate was fixed on a 100 °C heating table, the spray gun was vertically placed above the ITO conductive glass substrate at a distance of 10 cm and the polyaniline dispersion was uniformly sprayed on the ITO substrate at a constant flow rate, after 100 °C annealing and solidification for 30 min, 100 μL of silver nanosheet dispersion (0.8 mg / mL by mass) was sprayed using the same spraying conditions, after the spraying was completed, 100 °C annealing and solidification were carried out for 15 min, and the process was repeated until a 6-layer composite electrochromic thin film was obtained (50 μL of polyaniline thin film for the first layer, 100 μL of silver nanosheet for the second layer, 50 μL of polyaniline thin film for the third layer, 100 μL of silver nanosheet for the fourth layer, 50 μL of polyaniline thin film for the fifth layer, and 100 μL of silver nanosheet for the sixth layer).

[0071] The total solar light modulation amplitude of the 6-layer composite electrochromic thin film prepared in this example was 12.8% from bleached state (-0.4 V) to colored state (1.5 V), the modulation amplitude in visible light band was 13.9%, and the modulation amplitude in near-infrared band was 10.4%; the coloring time and bleaching time of the 6-layer composite electrochromic thin film prepared in this example under different voltages were 10.7 s and 20.4 s, respectively.

[0072] Example 13

[0073] Take 200 μL polyaniline dispersion (mass concentration of 0.8%) in the spray gun, fixed ITO conductive glass substrate on the heating stage at 100 ℃, the spray gun is vertically placed on the ITO conductive glass substrate above 10 cm and makes the polyaniline dispersion uniform spray on the ITO substrate with constant flow, 100 ℃ annealing solidification 10 min, then using the same spraying conditions spray 200 μL silver nanometer sheet dispersion (its mass concentration is 0.05 mg / mL), spray solidification 15 min, repeat the process until the 4 layers of composite electrochromic film (the first layer is 200 μL polyaniline film, the second layer is 200 μL silver nanometer sheet, the third layer is 200 μL polyaniline film, the fourth layer is 200 μL silver nanometer sheet).

[0074] The total solar light modulation amplitude of the 4 layers of composite electrochromic film prepared in the example from bleaching state (-0.4 V) to coloring state (1.5 V) is 8.1%, the visible light band modulation amplitude is 7.9%, and the near infrared band modulation amplitude is 8.2%; The coloring time and bleaching time of the 4 layers of composite double-band electrochromic film prepared in the example under different voltages are 15.0 s and 18.7 s respectively.

[0075] Example 14

[0076] Take 200 μL polyaniline dispersion (mass concentration of 3%) in the spray gun, fixed ITO conductive glass substrate on the heating stage at 100 ℃, the spray gun is vertically placed on the ITO conductive glass substrate above 10 cm and makes the polyaniline dispersion uniform spray on the ITO substrate with constant flow, 100 ℃ annealing solidification 10 min, then using the same spraying conditions spray 200 μL silver nanometer sheet dispersion (its mass concentration is 0.05 mg / mL), spray solidification 15 min, repeat the process until the 4 layers of composite double-band electrochromic film (the first layer is 200 μL polyaniline film, the second layer is 200 μL silver nanometer sheet, the third layer is 200 μL polyaniline film, the fourth layer is 200 μL silver nanometer sheet) are obtained.

[0077] The total solar light modulation amplitude of the 4 layers of composite electrochromic film prepared in the example from bleaching state (-0.4 V) to coloring state (1.5 V) is 8.1%, the visible light band modulation amplitude is 7.9%, and the near infrared band modulation amplitude is 8.2%; The coloring time and bleaching time of the 4 layers of composite double-band electrochromic film prepared in the example under different voltages are 15.0 s and 18.7 s respectively.

[0078] The electrochromic film prepared in each example is tested for its solar light modulation amplitude, visible light band modulation amplitude, near infrared band modulation amplitude and response time (t c is the coloring time, tb For the fading time), the test wavelength is 400nm-2500nm, the scanning speed is 600nm / min, and the results are shown in Table 1.

[0079] Table 1

[0080]

[0081]

[0082] The above merely is the preferred specific embodiment of the present application, but the protection scope of the present application is not limited to this, any person skilled in the art can easily think of the change or replacement within the technical range disclosed by the present application, which should be covered in the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A method for preparing a visible-near infrared dual-band modulated electrochromic thin film, characterized in that, The method comprises the following steps: Spraying a polyaniline dispersion liquid on a conductive glass substrate, annealing to obtain a polyaniline film, continuing to spray a silver dispersion liquid on the surface of the polyaniline film, annealing, and repeating the process of spraying a polyaniline dispersion liquid, annealing and spraying a silver dispersion liquid, annealing to prepare a visible-near infrared dual-band regulation electrochromic film; The mass concentration of the polyaniline dispersion liquid is 0.8-10%; The total spraying amount of the polyaniline dispersion liquid is 100-800 μL; The mass concentration of the silver dispersion liquid is 0.05-0.8 mg / mL; The total spraying amount of the silver dispersion liquid is 100-800 μL; The number of layers of the visible-near infrared dual-band regulation electrochromic film is 1-10; The silver nanoparticles and the polyaniline film are stacked and combined in the visible-near infrared dual-band regulation electrochromic film, the voltage window of the visible-near infrared dual-band regulation electrochromic film is-0.4 V to 1.5 V, the coloring time is 6.7-18.1 s, and the bleaching time is 18.0-23.1 s.

2. The method for preparing a visible-near infrared dual-band modulated electrochromic thin film according to claim 1, characterized in that, The silver dispersion liquid comprises a silver nanoparticle dispersion liquid, a silver nanowire dispersion liquid or a silver nanoplate dispersion liquid.

3. The method for preparing a visible-near-infrared dual-band modulated electrochromic thin film according to claim 1, characterized in that, The annealing temperature is 80-120 ℃, and the annealing time is 5-30 min.

4. A visible-near infrared dual band modulated electrochromic thin film, characterized in that, The visible-near infrared dual-band regulation electrochromic film prepared by the preparation method according to any one of claims 1-3 has a voltage window of-0.4 V to 1.5 V, a coloring time of 6.7-18.1 s, and a bleaching time of 18.0-23.1 s.

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