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CN-119781220-B - High-stability electrochromic film and preparation method and application thereof

CN119781220BCN 119781220 BCN119781220 BCN 119781220BCN-119781220-B

Abstract

The invention discloses a high-stability electrochromic film, a preparation method and application thereof, wherein the electrochromic film comprises a conductive material and an electrochromic layer, the electrochromic layer is a quasi-plane heterogeneous interface metal oxide, and the thickness of the electrochromic layer is 10-1000 nm; the preparation method comprises the following steps of fixing a conductive material on a sample frame, placing the conductive material in an electron beam cavity, preprocessing the conductive material, then adopting high-energy ion to assist electron beam evaporation, and depositing metal oxide on the conductive material by evaporation to obtain the electrochromic film. The high-stability electrochromic film, the preparation method and the application thereof overcome the trade-off between high stability and ultra-fast switching performance under the assistance of high-energy ions, and show remarkable overall electrochromic performance, including high optical contrast, ultra-fast switching speed and excellent stability.

Inventors

  • LV YING
  • LI PAN
  • LIU XINGYUAN
  • GUO XIAOYANG
  • WANG TIENAN

Assignees

  • 中国科学院长春光学精密机械与物理研究所

Dates

Publication Date
20260505
Application Date
20241231

Claims (10)

  1. 1. The high-stability electrochromic film is characterized by comprising a conductive material and an electrochromic layer, wherein the electrochromic layer is a quasi-plane heterogeneous interface metal oxide, the thickness of the electrochromic layer is 10-1000 nm, the surface of the conductive material is pretreated by high-energy ion bombardment, and the metal oxide is formed on the pretreated conductive material by high-energy ion auxiliary electron beam evaporation.
  2. 2. The electrochromic film with high stability according to claim 1, wherein the metal oxide is one or more of WO 3 、MoO 3 、NiO、TiO 2 .
  3. 3. The method for preparing the high-stability electrochromic film according to any one of claims 1-2, which is characterized by comprising the following steps of fixing a conductive material on a sample frame, placing the sample frame in an electron beam cavity, preprocessing the conductive material, and then adopting high-energy ion auxiliary electron beam evaporation to deposit metal oxide on the conductive material by evaporation to obtain the electrochromic film.
  4. 4. The method of preparing a high stability electrochromic film according to claim 3, wherein the vacuum degree in the electron beam cavity is 1X 10 -4 Pa～5×10 -3 Pa, and the surface of the conductive material is pretreated by high energy ion bombardment.
  5. 5. The method for preparing a high-stability electrochromic film according to claim 3, wherein the metal oxide is deposited on the pretreated conductive material by vapor deposition at a rate of 0.1-1 nm.s -1 at 20-300 ℃.
  6. 6. The method of claim 3, wherein the high-energy ion is one or more of oxygen ion, argon ion and nitrogen ion.
  7. 7. The method of claim 6, wherein the acceleration voltage of the high-energy ions is 130-300V.
  8. 8. An electrochromic device is characterized by comprising an electrochromic film, an electrolyte layer, a conductive layer and a protective layer, wherein the electrochromic film is obtained by the preparation method according to any one of claims 3-6.
  9. 9. The electrochromic device of claim 8, wherein the electrolyte layer is a gel electrolyte, and the preparation method of the gel electrolyte comprises the steps of uniformly mixing PMMA and PC, heating and swelling in an oven at 60-80 ℃ for 15-20 hours to obtain transparent gel, adding LiClO 4 and acetonitrile, and then stirring on a magnetic stirrer at 60-80 ℃ for 10-15 hours to uniformly distribute electrolyte salt on the transparent gel, and finally forming the gel electrolyte.
  10. 10. The electrochromic device of claim 9, wherein the molecular weight of PMMA is 10-15 ten thousand, and the mass ratio of PMMA, PC, liClO 4 to acetonitrile is (3-5): 8-12): 1-2): 5-10.

Description

High-stability electrochromic film and preparation method and application thereof Technical Field The invention relates to the technical field of electrochromic films, in particular to a high-stability electrochromic film and a preparation method and application thereof. Background Electrochromic refers to the dynamic adjustment of the visual color and optical properties of Electrochromic (EC) materials and devices through electrochemical redox reactions under small external voltage or current stimuli. EC technology has great application potential in various fields, including smart windows for energy-saving buildings, energy-saving displays and adaptive camouflage systems. Currently, various advanced EC materials include organic polymers, inorganic metal oxides, and plasmonic nanomaterials. Among them, inorganic EC materials, such as transition metal oxides, e.g., tungsten oxide and nickel oxide, have gained considerable attention due to their good cost-to-performance ratio, abundant reserves, and special photo-thermal stability. However, most inorganic EC materials have an inherently brittle and dense microstructure, which presents a significant challenge for the development of EC materials and devices, which strongly limits their development and wide range of practical applications when combining ultra-fast switching speeds, practically required durability, and perfect mechanical flexibility. Currently, there have been studies attempting to improve the performance of WO 3 thin films by optimizing their deposition process and interface design. However, the prior art has not fully utilized the design of the quasi-planar heterogeneous interface to effectively enhance electrochromic properties, and in particular, there is a large room for improvement in terms of improving response speed and stability. To address the above challenges, various strategies are being explored, such as developing nanostructured and/or composite EC materials, optimizing electrolyte ions, and constructing new electrode materials, among others. The low-dimensional nano-structured EC film comprises nano points, nano wires, nano rods, nano sheets and a nano porous film, and compared with the traditional compact film, the contact area with electrolyte can be increased, the charge transmission distance is shortened, the internal stress is relieved, and the optical contrast, response time and flexibility are remarkably improved. Although great progress has been made with the aid of nanotechnology, these improvements in performance are generally achieved at the expense of stability, since high reactivity induces side reactions during repeated cycles, degradation of the microstructural fluid and a great decrease in stability. Research shows that precise adjustment of the heterogeneous interfaces in the nanostructured EC nanocomposite and the planar heterogeneous interfaces on the EC/electrolyte interlayer are also effective strategies to improve their overall performance. These efforts highlight the importance of heterogeneous interface engineering and offer a promising feature by creating a rich heterogeneous interface that produces rapid mass and charge transfer to address the inherent limitations of single-phase nanomaterials. Some artificial solid electrolyte layers at the EC layer/electrolyte heterogeneous interface can also act as buffers, enhancing the elasticity and stability of the film. In contrast, the heterogeneous interface modulation of the electrode/EC layer is often neglected, which is the site where non-uniform electron transfer occurs and ion diffusion driving forces are generated, which is expected to be closely related to the final EC performance. Recent reports have demonstrated that the above speculation can effectively improve EC performance by creating a nanostructured interface between the electrode and the EC layer. For example, self-assembled two-dimensional TiO 2/Mxene heterostructures have good balanced porosity and connectivity, can improve ion and electron transport efficiency in flexible EC devices, and have superior mechanical and electrochemical stability (> 1000 cycles). In addition, porous tin dioxide nanoplatelet scaffolds loaded with multiple active EC materials can significantly improve cycling durability (> 2000 cycles) and light modulation (WO 3@SnO2 is 86%). However, there remains a hurdle in the large-scale, straightforward and reliable control building and integration of nanostructured heterointerfaces with customizable features, which illustrates the necessity of further enhancing the heterointerface design to achieve widespread implementation. Disclosure of Invention The invention aims to provide a high-stability electrochromic film, a preparation method and application thereof, and aims to solve the problem that the improvement of the performance of an EC material usually comes at the expense of stability and the performance and the stability cannot be simultaneously improved. In order to achiev