阅读说明：本技术 一种黑色显示的多层聚合物薄膜及其制备方法和应用 (Multilayer polymer film for black display and preparation method and application thereof ) 是由 张�诚 闫拴马 李维军 付海长 于 2019-08-12 设计创作，主要内容包括：一种黑色显示的多层聚合物薄膜,所述薄膜由如下方法制备：首先,在单体溶液(Ⅰ)中,利用原位电化学聚合方法,电沉积一层红色的聚合物薄膜；其次,在单体溶液(Ⅱ)中,利用循环伏安聚合法,继续电沉积一层绿色的聚合物薄膜；最后,在单体溶液(Ⅲ)中,利用循环伏安聚合法,再电沉积一层蓝色的聚合物薄膜,最终得到多层聚合物薄膜。以及提供所述黑色显示的多层聚合物薄膜的制备方法和应用。本发明更加简单和可控,所制备的黑色显示的聚合物电致变色材料与现有的材料相比,展现出更加优异的电致变色性能。(A black-displaying multilayer polymeric film, said film prepared by a process comprising: firstly, electrodepositing a layer of red polymer film in a monomer solution (I) by using an in-situ electrochemical polymerization method; secondly, in the monomer solution (II), a layer of green polymer film is continuously electrodeposited by using a cyclic voltammetry polymerization method; and finally, electrodepositing a layer of blue polymer film in the monomer solution (III) by using a cyclic voltammetry polymerization method to finally obtain the multilayer polymer film. And a method for preparing the multilayer polymer film for black display and application thereof. The invention is simpler and controllable, and compared with the existing material, the prepared polymer electrochromic material with black display shows more excellent electrochromic performance.)

1. a black-displaying multilayer polymeric film, wherein said film is prepared by a process comprising: in a three-electrode system which takes ITO glass as a working electrode, a platinum wire as a counter electrode and an Ag/AgCl electrode as a reference electrode, three monomer solutions are prepared by using polymeric precursors of three polymers respectively showing red, green and blue, combining a supporting electrolyte and an electrolytic solvent, and are sequentially named as a monomer solution (I), a monomer solution (II) and a monomer solution (III); firstly, electrodepositing a layer of red polymer film in a monomer solution (I) by using an in-situ electrochemical polymerization method; secondly, in the monomer solution (II), a layer of green polymer film is continuously electrodeposited by using a cyclic voltammetry polymerization method; and finally, electrodepositing a layer of blue polymer film in the monomer solution (III) by using a cyclic voltammetry polymerization method to finally obtain the multilayer polymer film.

2. a method for preparing a black displaying multilayer polymer film according to claim 1, comprising the steps of: firstly, electrodepositing a layer of red polymer film in a monomer solution (I) by using an in-situ electrochemical polymerization method; secondly, in the monomer solution (II), a layer of green polymer film is continuously electrodeposited by using a cyclic voltammetry polymerization method; and finally, electrodepositing a layer of blue polymer film in the monomer solution (III) by using a cyclic voltammetry polymerization method to finally obtain the multilayer polymer film.

3. The method according to claim 2, wherein the prepared monomer solution has a concentration of the polymeric precursor of 0.5 to 5mg/ml and a concentration of the supporting electrolyte of 0.05 to 0.3 mol/L.

4. The preparation method according to claim 2, wherein the electrolytic solvent is dichloromethane, acetonitrile or a mixed solvent of dichloromethane and acetonitrile in any proportion, and the supporting electrolyte is tetrabutylammonium hexafluorophosphate, tetrabutylammonium perchlorate, lithium perchlorate or ionic liquid.

5. The method of claim 2, wherein the in situ electrochemical polymerization is cyclic voltammetry, potentiostatic method, or galvanostatic method.

6. The method according to claim 5, wherein the in-situ electrochemical polymerization method is a cyclic voltammetric polymerization method, wherein the voltage range in the cyclic voltammetric polymerization method is-1.0V-1.5V, the scanning speed is 0.1mV/s to 0.5mV/s, and the number of polymerization cycles is 5 to 15.

7. The method according to claim 2, wherein the organic solvent of the washed polymer film is dichloromethane, acetonitrile, or a mixed solvent of dichloromethane and acetonitrile at any ratio.

8. the method according to claim 2, wherein the electrochemical polymerization sequence of the three monomers is (I) to (II) to (III), and the number of cycles of the cyclic voltammetric polymerization of the three monomers is the same as 8.

9. Use of a black-displaying multilayer polymer film according to claim 1 as an electrochromic material for black display.

10. The use according to claim 9, wherein the black-displaying multilayer polymer film is suitable for use in smart windows, automotive rearview mirrors, flat panel displays, and flexible wearable devices.

Technical Field

The invention relates to a black display multilayer polymer film and a preparation method thereof, and the film can be used as an electrochromic active material and can be applied to intelligent windows, automobile rearview mirrors, flat panel displays and wearable devices.

Background

"Electrochromism" (EC) refers to a phenomenon in which a material exhibits a reversible change in macroscopic color due to a redox reaction under the action of a voltage. Through decades of development, electrochromic materials are currently mainly classified into: inorganic electrochromic materials, organic electrochromic materials and inorganic-organic composite electrochromic materials. Compared with inorganic electrochromic materials, organic electrochromic materials, especially conductive polymer electrochromic materials have higher optical contrast, wider color modulation range, faster response time and more excellent processing performance, so that the organic electrochromic materials attract more and more researchers to pay attention, and electrochromic devices based on the organic electrochromic materials show great potential application values in the fields of intelligent windows, automobile rearview mirrors, flat panel displays and flexible wearable devices.

Among the existing polymer electrochromic materials, the electrochromic material with black display is the least one electrochromic material reported at present, because the black electrochromic material requires that the polymer must realize absorption (400nm-800nm) in the whole visible region, which puts very high requirements on the design and synthesis of the material. In 2008, j.r. reynolds et al synthesized the first black-appearing polymeric electrochromic material by constructing and adjusting donor-acceptor structures (natural materials,2008,7, 795-799). However, the disadvantage is that the synthesis process of the material is complicated and difficult to control. In 2016, professor xuchun leaf in China (New J. chem,2016,40,5231-5237) prepared a polymer electrochromic material with black display through a solution blending method. The material is relatively simple to prepare, but the prepared material has poor electrochromic performance, mainly represented by low optical contrast and slow response speed.

Therefore, based on the background of the prior art, it is necessary to develop a simple and controllable method for preparing a high-performance black display polymer electrochromic material.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention provides a polymer film for black display, which can realize reversible conversion of color from black to transparent as an electrochromic material, and has high optical contrast, fast response time and good cycling stability; simultaneously, a simple and controllable method for preparing the polymer film is provided; in addition, the prepared polymer film is used as an electrochromic active material to be applied to electrochromic devices such as intelligent windows, automobile rearview mirrors, flat panel displays and wearable equipment.

The technical scheme adopted by the invention for solving the technical problems is as follows:

A black-displaying multilayer polymeric film, said film prepared by a process comprising: in a three-electrode system which takes ITO glass as a working electrode, a platinum wire as a counter electrode and an Ag/AgCl electrode as a reference electrode, three monomer solutions are prepared by using polymeric precursors of three polymers respectively showing red, green and blue, combining a supporting electrolyte and an electrolytic solvent, and are sequentially named as a monomer solution (I), a monomer solution (II) and a monomer solution (III); firstly, electrodepositing a layer of red polymer film in a monomer solution (I) by using an in-situ electrochemical polymerization method; secondly, in the monomer solution (II), a layer of green polymer film is continuously electrodeposited by using a cyclic voltammetry polymerization method; and finally, electrodepositing a layer of blue polymer film in the monomer solution (III) by using a cyclic voltammetry polymerization method to finally obtain the multilayer polymer film.

A method of preparing a black-displaying multilayer polymer film, the method comprising the steps of: firstly, electrodepositing a layer of red polymer film in a monomer solution (I) by using an in-situ electrochemical polymerization method; secondly, in the monomer solution (II), a layer of green polymer film is continuously electrodeposited by using a cyclic voltammetry polymerization method; and finally, electrodepositing a layer of blue polymer film in the monomer solution (III) by using a cyclic voltammetry polymerization method to finally obtain the multilayer polymer film.

In the prepared monomer solution, the concentration of the polymerization precursor is 0.5-5 mg/ml (preferably 1-3 mg/ml), and the concentration of the supporting electrolyte is 0.05-0.3 mol/L (preferably 0.1-0.1 mol/L).

The electrolytic solvent is dichloromethane and acetonitrile, or a mixed solvent of dichloromethane and acetonitrile in any proportion, preferably a mixed solvent of dichloromethane and acetonitrile;

The supporting electrolyte is tetrabutylammonium hexafluorophosphate, tetrabutylammonium perchlorate, lithium perchlorate or ionic liquid, and tetrabutylammonium hexafluorophosphate is preferred.

The in-situ electrochemical polymerization method is a cyclic voltammetry method, a potentiostatic method or a galvanostatic method.

The in-situ electrochemical polymerization method is a cyclic voltammetry polymerization method, the voltage range in the cyclic voltammetry polymerization method is-1.0V-1.5V (preferably-0.6V-1.1V), the scanning speed is 0.1 mV/s-0.5 mV/s (preferably 0.2 mV/s-0.4 mV/s), and the number of polymerization cycles is 5-15 (preferably 6-10);

The organic solvent of the washed polymer film is dichloromethane, acetonitrile or a mixed solvent of dichloromethane and acetonitrile in any proportion, and preferably the mixed solvent of dichloromethane and acetonitrile.

The electrochemical polymerization sequence of the three monomers is (I) to (II) to (III), and the cyclic voltammetry polymerization cycles of the three monomers are the same and are also 8.

Use of the black-displaying multilayer polymer film according to claim 1 as an electrochromic material for black display.

The black-display multilayer polymer film is suitable for intelligent windows, automobile rearview mirrors, flat panel displays and flexible wearable equipment.

The multilayer polymer film of the invention is used as an electrochromic material to display black in a neutral state and transparent light blue in an oxidized state, stable and reversible color switching can be carried out between the two states, and the material has high optical contrast and fast response time at a specific wavelength.

The multilayer polymer electrochromic film has an optical contrast ratio of 50-80% at 1100 nm; the optical contrast at 550nm is 40-60%;

the coloring time of the multilayer polymer electrochromic film under 1100nm is 1.0 s-3.0 s; the fading time is 0.5 s-2.5 s; the coloring time at 550nm is 0.8 s-3.5 s; the fading time is 0.5 s-2.8 s;

Compared with the prior art, the invention has the beneficial effects that: provided is a method for preparing a polymer electrochromic material for black display, which is simpler and controllable than the prior art, and the prepared polymer electrochromic material for black display exhibits more excellent electrochromic properties than the prior materials, and is expected to be used in smart windows, automobile rearview mirrors, flat displays and flexible wearable devices.

drawings

FIG. 1 is the molecular structure of three polymerized monomers used in examples 1 and 2;

FIG. 2 is the optical absorption at different voltages of the multilayer polymer film prepared in example 1;

FIG. 3 is a graph of transmittance over time at specific wavelengths for multiple potential steps from-0.6 to 1.0V for a multilayer polymer film prepared in example 1;

FIG. 4 is the optical absorption at different voltages for the multilayer polymer film prepared in example 2;

FIG. 5 is a plot of transmission over time at specific wavelengths for multiple potential steps from-0.6 to 1.0V for the multilayer polymer film prepared in example 2.

Detailed Description

the invention is further described below with reference to the accompanying drawings.