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CN-121427065-B - Transparent conductive material, preparation method and application

CN121427065BCN 121427065 BCN121427065 BCN 121427065BCN-121427065-B

Abstract

The invention relates to the field of organic electrochromic materials, in particular to a transparent conductive material, a preparation method and application. The transparent conductive material simultaneously introduces two independent carbonyl groups into a molecular main chain, realizes accurate coordination of energy level, polarity and charge transmission performance through differential regulation and control of oxygen or nitrogen atoms, can be used as an ion storage layer, an electrode modification layer or an active functional layer in an electrochromic device, can realize rapid and reversible optical modulation under lower voltage (+ -1.0V), has high optical contrast (delta T 550 > 65%), shorter response time (delta T392 > s) and excellent cycle stability (cycle retention rate more than 3X 10 4 times is more than 95%), and has wide application prospect in the fields of intelligent display, energy-saving building and flexible electronics.

Inventors

  • WANG YILIN
  • MEI ZHENYUAN
  • HE YAOWU
  • MENG HONG

Assignees

  • 北京大学深圳研究生院

Dates

Publication Date
20260508
Application Date
20251229

Claims (8)

  1. 1. A transparent conductive material characterized by the following molecular formula: -represents the site where adjacent repeat units are linked by fusion; a is O or NR, R is selected from H, ether chain, fluorine-containing ether chain, phosphate chain or quaternary ammonium salt chain; n is an integer of 5 to 500.
  2. 2. The transparent conductive material according to claim 1, wherein R is selected from the group consisting of: Wherein R 1 、R 2 and R 3 are independent alkyl groups; X is selected from fluorine, chlorine, bromine, iodine or phosphate; y is an integer of 1 to 10.
  3. 3. The transparent conductive material according to claim 1, characterized by a structure selected from the group consisting of: 。
  4. 4. the method for preparing a transparent conductive material as claimed in claim 1, comprising the steps of: The method specifically comprises the following steps: s1, 2, 5-diamino-1, 4-benzene diboronic acid (A-1) and 2, 3-dibromo diethyl fumarate (A-2) are subjected to suzuki coupling reaction polymerization in the presence of a catalyst according to a molar ratio of 1:1 to obtain an intermediate A-3; S2, the intermediate A-3 is subjected to transesterification or ester amidation under the catalysis of strong acid to form a lactone or lactam compound A-4.
  5. 5. The method of manufacturing according to claim 4, further comprising the steps of: s3, reacting the lactam compound A-4 with a halogenated compound to obtain a target product A-5, wherein the reaction process is as follows: 。
  6. 6. use of the transparent conductive material according to any one of claims 1-3 in electrochromic devices.
  7. 7. The use according to claim 6, wherein the electrochromic device is a p-n type complementary electrochromic device, proDOT or a derivative thereof is a p-type electrochromic layer, and the transparent conductive material is an n-type ion storage layer.
  8. 8. The use of claim 6, wherein the electrochromic device further comprises a gel electrolyte as an ion conducting medium between the p-type electrochromic layer and the n-type ion storage layer.

Description

Transparent conductive material, preparation method and application Technical Field The invention relates to the field of organic electrochromic materials, in particular to a transparent conductive material, a preparation method and application. Background The organic electrochromic material has great application potential in the fields of intelligent dimming windows, flexible display, energy-saving buildings and the like because of being capable of realizing reversible color change under low voltage. In recent years, researchers have developed a variety of electrochromic polymer systems based on conjugated backbones through molecular design and energy level regulation. However, the existing materials generally have the problem that the performance is difficult to consider, namely, an oxygen-containing polymer with an ester bond or lactone structure is limited in electron transmission capability and poor in electrochemical stability although the oxygen-containing polymer has good solubility and flexibility, and is easy to degrade under long-term circulation or high-temperature and high-humidity conditions, and another nitrogen-containing polymer with an amide or imide structure is high in electron affinity and good in stability, but is poor in film forming property and interface compatibility, and high in processing temperature and complex post-treatment process are needed. Recent studies have shown that the number of carbonyl groups in the polymer backbone and their interactions with heteroatoms (O or N) have a decisive influence on the molecular energy level structure, the polarity distribution and the ion transport properties. For example, various work in JACS (2022), macromolecules (2024) and Advanced Functional Materials (2023-2024) have shown that the stability of n-type polymers depends on the electron coupling region formed by carbonyl groups and heteroatoms in the molecular backbone, and that related studies in ANGEWANDTE CHEMIE (2024-2025) and Nature Communications (2024) have further demonstrated that adjusting the electron density of the heteroatoms can significantly improve doping efficiency and carrier mobility. However, these studies mostly focused on a single type of structural system, i.e. either oxygen-containing ester polymers or nitrogen-containing amide or imide polymers, have not systematically explored the possibility of the two types of structures acting synergistically in the same molecular framework. Matching of the ion storage layer to the electrode interface is particularly critical in electrochromic devices. Although the traditional PEDOT-PSS or n-PBDF material has certain conductivity and stability, the polarity distribution is single, and the comprehensive performance requirements of low-voltage driving, high optical contrast, long cycle life and the like are difficult to be simultaneously considered. Disclosure of Invention Aiming at the problems, the transparent conductive material provided by the invention can simultaneously introduce two independent carbonyl groups into a molecular main chain, and realize accurate coordination of energy level, polarity and charge transmission performance through differential regulation and control of oxygen or nitrogen atoms, so as to construct the electrochromic polymer with high stability and high response performance. The invention provides a transparent conductive material, which has the following molecular formula: a is O or NR, R is selected from H, ether chain, fluorine-containing ether chain, phosphate chain or quaternary ammonium salt chain; n is an integer of 5 to 500. In a preferred embodiment of the invention, R is selected from the following: Wherein R 1、R2 and R 3 are independent alkyl groups; X is selected from fluorine, chlorine, bromine, iodine or phosphate; y is an integer of 1 to 10. In a preferred embodiment of the invention, the structure is selected from the following: 。 In another aspect of the present invention, there is also provided a method for preparing the aforementioned transparent conductive material, comprising the steps of: The method specifically comprises the following steps: s1, 2, 5-diamino-1, 4-benzene diboronic acid (A-1) and 2, 3-dibromo diethyl fumarate (A-2) are subjected to suzuki coupling reaction polymerization in the presence of a catalyst according to a molar ratio of 1:1 to obtain an intermediate A-3; S2, the intermediate A-3 is subjected to transesterification or ester amidation under the catalysis of strong acid to form a lactone or lactam compound A-4. In a preferred embodiment of the invention, the method further comprises the steps of: s3, reacting the lactam compound A-4 with a halogenated compound to obtain a target product A-5, wherein the reaction process is as follows: 。 In a third aspect of the invention, there is also provided the use of said transparent conductive material in an electrochromic device. In a preferred embodiment of the present invention, the electrochromic device i