CN-117555185-B - Electrochromic device based on carbon-rich carbon nitride conjugated polymer, and assembly method and application thereof

CN117555185BCN 117555185 BCN117555185 BCN 117555185BCN-117555185-B

Abstract

The invention relates to an electrochromic device based on carbon-rich carbon nitride conjugated polymer, and an assembly method and application thereof, belonging to the technical field of intelligent electrochromic devices. The electrochromic/photochromic device comprises the carbon-rich carbon nitride electrode and the FTO conductive glass which are oppositely arranged, double-sided insulating glue for sealing and attaching the carbon-rich carbon nitride electrode and the FTO conductive glass, and electrolyte solution injected into a gap between the carbon-rich carbon nitride electrode and the FTO conductive glass, and the electrochromic/photochromic device is simple in assembly method, easy to operate and good in application prospect in the aspect of intelligent dimming glass Windows (Smart Windows).

Inventors

TANG XIAO
LIU TINGTING
ZENG YUE
LI YANHONG
JING CHUAN
LING FALING
YANG HONGMEI
KANG TAO

Assignees

重庆邮电大学

Dates

Publication Date: 20260505
Application Date: 20231031

Claims (7)

1. An electrochromic device based on carbon-rich carbon nitride conjugated polymer is characterized by comprising a carbon-rich carbon nitride electrode, FTO conductive glass, double-sided insulating glue, and electrolyte solution, wherein the carbon-rich carbon nitride electrode and the FTO conductive glass are oppositely arranged, the double-sided insulating glue is used for sealing and bonding the carbon-rich carbon nitride electrode and the FTO conductive glass, and the electrolyte solution is injected into a gap between the carbon-rich carbon nitride electrode and the FTO conductive glass; The carbon-rich carbon nitride electrode is prepared by soaking an FTO conductive glass sheet sintered with a titanium dioxide nano film in an aqueous solution of carbon-rich carbon nitride conjugated polymer with the concentration of more than or equal to 0.001g/mL, standing at room temperature for more than 12 hours for chemical adsorption, taking out, and airing at room temperature to obtain the carbon-rich carbon nitride electrode; The carbon-rich carbon nitride conjugated polymer aqueous solution is prepared by the following steps: S1) mixing dicyandiamide, citric acid and deionized water according to a mass ratio of 1:1.9:60 to obtain a reactant, and introducing the reactant into a hydrothermal reaction kettle for hydrothermal reaction to obtain a precursor; s2) sealing and storing the precursor obtained in the step S1 in an ammonia atmosphere at room temperature to perform curing reaction to obtain a carbon-rich carbon nitride conjugated polymer aqueous solution; S3) freeze-drying the carbon-rich carbon nitride conjugated polymer aqueous solution obtained in the step S2 at the temperature of-80 ℃ and the vacuum degree of below 30Pa to obtain the carbon-rich carbon nitride conjugated polymer; S4) dissolving the carbon-rich carbon nitride conjugated polymer prepared in the step S3 in deionized water to prepare an aqueous solution of the carbon-rich carbon nitride conjugated polymer with the concentration of more than or equal to 0.001 g/mL; wherein, when the temperature of the hydrothermal reaction in S1 is 200 ℃ and the heat preservation time is 30min, the sealing preservation time in S2 is 8 months or 10 months; And when the temperature of the hydrothermal reaction in the S1 is 190 ℃ and the heat preservation time is 30min, the sealing preservation time in the S2 is 12 months or 14 months.
2. The electro/photochromic device of claim 1 wherein the method for preparing the FTO conductive glass sheet with the sintered titanium dioxide nano film comprises coating the titanium dioxide nano-crystal sol with particle size not more than 50nm on the FTO conductive glass to form a uniform colloid film, drying at 80 ℃ and calcining at 450 ℃ for 3min to obtain the FTO conductive glass sheet with the sintered titanium dioxide nano film; The thickness of the titanium dioxide nano film on the FTO conductive glass sheet sintered with the titanium dioxide nano film is 1-10 mu m.
3. The electro/photochromic device of claim 1 wherein the carbon-rich carbon nitride conjugated polymer has the structural formula Wherein n is an integer of 1 or more.
4. The electro/photochromic device of claim 1 wherein the electrolyte solution comprises ethylene carbonate or propylene carbonate, acetonitrile, lithium iodide, tetrabutylammonium hexafluorophosphate, wherein the mass ratio of ethylene carbonate or propylene carbonate, acetonitrile, lithium iodide to tetrabutylammonium hexafluorophosphate is 10:2-5:0.2-1.5:0.7-2.
5. The electro/photochromic device of claim 1 wherein the double-sided insulating adhesive is 3m 300lse tape.
6. The method for assembling an electro/photochromic device of any one of claims 1 to 5, wherein the method for assembling comprises the steps of: And (3) oppositely placing the carbon-rich carbon nitride electrode and the FTO conductive glass, wherein the carbon-rich carbon nitride conjugated polymer in the carbon-rich carbon nitride electrode faces the conductive surface of the FTO conductive glass, sealing and attaching the conductive surface by double-sided insulating glue, and then injecting electrolyte solution into a gap between the carbon-rich carbon nitride electrode and the FTO conductive glass, so that the electric/photochromic device based on the carbon-rich carbon nitride conjugated polymer can be assembled.
7. Use of an electro/photochromic device according to any one of claims 1 to 5 for the preparation of an electro/photochromic smart dimming glazing.

Description

Electrochromic device based on carbon-rich carbon nitride conjugated polymer, and assembly method and application thereof Technical Field The invention belongs to the technical field of color-changing devices, and relates to an electrochromic/photochromic device based on a carbon-rich carbon nitride conjugated polymer, and an assembly method and application thereof. Background The intelligent dimming glass window is a functional device with light transmission characteristics (such as transmissivity, transmitted light wavelength and the like) capable of being adjusted through external excitation, and is mainly applied to scenes needing to dynamically adjust sunlight or light transmission rate, such as building glass curtain walls, automobile windows, airplane portholes, optical darkrooms and the like. Materials with special effects such as electrochromic, photochromic, thermochromic, piezochromic and the like can be used for manufacturing intelligent dimming glass windows. Among various materials, the electrochromic material has highest controllability, can accurately adjust light transmittance through voltage, has wide application prospect in the technical field of intelligent glass windows, can achieve a light modulation effect by utilizing solar radiation, is suitable for field environment, has the advantages of environmental protection and energy saving, and has respective characteristics and advantages when thermochromic and piezochromic devices are stressed on different external actions. Thus, device versatility, and in particular multi-factor excitability, is an important direction of smart window development. Currently, the types of electrochromic materials mainly comprise inorganic electrochromic materials (such as tungsten trioxide and titanium dioxide), conjugated conductive polymer electrochromic materials (such as Polystyrene (PANI), polypyrrole (PPY), poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) and the like), organic micromolecular electrochromic materials (such as viologen and derivatives thereof), metal organic complexes (such as Prussian Blue (PB) and the like). The electrochromic device generally comprises a transparent conductive substrate, an ion storage layer, an ion transport layer, a color change layer and a conductive optical window. Organic small molecules and metal organic complexes are not suitable for manufacturing large-size devices, and are generally used for manufacturing small sensors or detectors, such as medical drug test papers or devices, electronic displays and the like. The organic electrochromic material and the conjugated conductive polymer are used for preparing large-size devices, so that the organic electrochromic material and the conjugated conductive polymer are widely applied to intelligent dimming glass windows. The electrochromic material has the remarkable advantages of strong optical modulation, easy obtainment of high contrast over 90 percent, complete opaque darkness effect of the window, wide transmissivity adjustment space and support of gradient dimming. In recent years, a visible and infrared dual-band light modulation effect is also discovered, and the dual-function effect of light modulation and temperature adjustment is expected to be realized in the future. The conjugated conductive polymer can realize 40-60% of optical modulation contrast, has the remarkable advantages of easy processing property and suitability for commercial mass production, and has the main defects that the color change stability of ① devices is not ideal, especially under the condition of deep color change, local electrode reaction is easy to be poor, and the dimming effect is remarkably attenuated. Although the electrolyte can be recovered by updating, the maintenance cost of the electrolyte in actual use is greatly increased, and ② has a remarkable large-area performance attenuation effect. As the intelligent window generally needs to adopt FTO or ITO conductive glass as a conductive base material, the resistance is a plane resistance (generally 10-20 ohm/cm < 2 >). As the area increases, the resistance increases significantly. Since both types of electrochromic materials generally operate based on a lithium ion intercalation and deintercalation mechanism, there is a significant overpotential effect, resulting in a voltage window for their operation that is close to the limit state that the electrolyte can withstand. The increase of the resistance of the conductive substrate aggravates the overpotential effect, so that the color-changing performance of the device is reduced, the larger optical modulation contrast is attenuated, the dimming effect is seriously affected, and the ③ needs to apply voltage to maintain the coloring state, so that the energy consumption of the device is increased. The application scenario of electrochromic devices requires that they be in a colored state most of the time to reduce the light transmittance. Although ma