Electrochemical preparation method and application of triphenylamine polymer film
By designing tripaniline polymers and preparing them through electrochemical polymerization, the problems of insufficient stability and processing performance of existing electrochromic materials are solved, and materials with high stability and excellent electrochromic properties are prepared, with wide applications prospect.
Patent Information
- Application Number
- CN202311047365.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-08-18
- Publication Date
- 2025-02-21
AI Technical Summary
There are shortcomings in the stability and processing performance of existing electrochromic materials, which are difficult to meet the needs of large-scale production and application.
By designing tripaniline polymers, D-A monomers were constructed by Suzuki coupling reaction using anthraquinone as an electron acceptor and tripaniline, and electrochromic materials were prepared by electrochemical polymerization.
It realizes high stability and easy-to-synthetic electrochromic materials, with excellent electrochromic properties and potential energy storage application value.
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Figure CN119490310A_ABST
Abstract
Description
A technical field
[0001] The invention belongs to the technical field of organic photoelectric materials, and specifically relates to an electrochemical preparation method of a triphenylamine polymer, and its application in the fields of electrochromism and electrochemical energy storage. 2. Background Technology
[0002] Applying current or voltage to a substance causes it to undergo a redox reaction. Different redox states have different optical absorption and reflection properties, which results in macroscopic color changes. This phenomenon is called electrochromism. Electrochromism is an emerging technology with broad application prospects and market potential.
[0003] Electrochromic materials are the most important components of electrochromic devices, and they play a vital role in device performance. Compared with inorganic materials, organic materials are easy to chemically modify and have good processing properties, and are currently the most promising materials for large-scale production. Triphenylamine (TPA) molecules exhibit ultrafast electron transfer rate constants and good hole transport properties in organic optoelectronic material applications due to their unique structure and properties. The lone pair of electrons on the central N atom can be easily electrochemically oxidized to single cation radicals, accompanied by color changes, so that triphenylamine and its derivatives are often used as electrochromic materials. Most aromatic amine materials are colorless unless they have intramolecular charge transfer (ICT) interactions with electron acceptors. When they appear in the form of free radical cations, aromatic amines show a noticeable color change in organic solutions. Due to the electron-rich ability of triphenylamine as an electron donor, it is expected to become a very promising electrochromic (EC) material. This type of compound can be formed into a film by electrochemical polymerization and exhibits excellent electrochromic properties, which has potential application value. 3. Summary of the invention
[0004] The present invention uses molecular design, anthraquinone as an electron acceptor, triphenylamine as an electron donor, constructs a type of DA-type monomer through Suzuki coupling reaction, and prepares an electrochromic material through electrochemical polymerization. This type of electrochromic material has high stability, is easy to synthesize, and has potential application value.
[0005] Another object of the present invention is to provide a method for preparing triphenylamine compounds, which has a simple preparation operation process, mild reaction conditions, high yield, simple purification process, and high application value.
[0006] The present invention provides a triphenylamine polymer electrochromic material, the monomer structure of which is represented by the general formula (I):
[0007]
[0008] The synthesis method of the triphenylamine polymer electrochromic material monomer is as follows: 2,6-dibromoanthraquinone and 4-triphenylamine borate undergo Suzuki coupling reaction to obtain the electrochromic material shown in formula (I). The details are as follows:
[0009] 2,6-Dibromoanthraquinone (500 mg, 1.366 mmol), 4-boric acid triphenylamine (1.184 g, 4.098 mmol), potassium carbonate (1.131 g, 8.196 mmol), tetrakis(triphenylphosphine)palladium (157 mg, 0.1366 mmol) were quickly added into a 100 mL reaction bottle in sequence, and then 50 mL of N,N-dimethylformamide was added, and the reaction was evacuated and filled with nitrogen. The reaction temperature was 90°C and refluxed for 24 hours. After the reaction was completed by spot plate monitoring, extraction was performed, and finally AQ-TPA was purified by column chromatography.
[0010] The synthesis process is:
[0011] During the reaction, the molar ratio of 2,6-dibromoanthraquinone, 4-triphenylamine borate, potassium carbonate and tetrakis(triphenylphosphine)palladium is 1:3:6:0.1, the reaction temperature is 90° C., and the reaction time is 20 to 24 hours.
[0012] The monomer represented by formula (I) is dissolved in a mixed solvent of toluene and acetonitrile in a volume ratio of 4:1, tetrabutylammonium hexafluorophosphate is used as an electrolyte, and cyclic voltammetry polymerization is performed at 0-1.5V, with a scan rate of 0.1V / s and a cycle number of 10-30, and a polymer film is obtained after electrochemical polymerization; the initial concentration of the tetrabutylammonium hexafluorophosphate is 0.1mol / L; the initial concentration of the monomer represented by formula (I) is 1mmol / L. Indium tin oxide (ITO) transparent conductive glass is used as a working electrode, a platinum wire is used as a counter electrode, and a silver wire is used as a reference electrode, and the monomer is polymerized into a film and deposited on the surface of ITO.
[0013] Using an electrochemical workstation, UV-visible-near infrared absorption spectroscopy characterized the electrochemical properties, electrochromic properties and energy storage properties of the prepared polymer film. The study found that the polymer film has good electrochemical redox properties, can achieve reversible color changes from reddish brown to blue at different voltages, and achieves a high degree of color regulation in the visible light region.
[0014] Compared with the prior art, the advantages of the present invention are: a triphenylamine polymer film is obtained by electrochemical polymerization, and it is applied to the fields of electrochromism and energy storage, and has potential application prospects in the fields of smart windows, displays, zinc ion batteries, etc. BRIEF DESCRIPTION OF THE DRAWINGS
[0015] Figure 1This is the cyclic voltammogram of the electrochemical polymerization of the monomer AQ-TPA synthesized in Example 1 of the present invention.
[0016] Figure 2 This is an absorption spectrum diagram of the polymer film based on monomer AQ-TPA synthesized in Example 1 of the present invention under different voltages.
[0017] Figure 3 Cyclic voltammograms of the polymer thin film gel device based on monomer AQ-TPA synthesized in Example 1 of the present invention at different scan rates.
[0018] Figure 4 This is a constant current charge and discharge diagram of the polymer thin film gel energy storage device based on monomer AQ-TPA synthesized in Example 1 of the present invention. DETAILED DESCRIPTION
[0019] Example 1: Preparation of Monomer AQ-TPA
[0020] Steps: 2,6-dibromoanthraquinone (500 mg, 1.366 mmol), 4-triphenylamine borate (1.184 g, 4.098 mmol), potassium carbonate (1.131 g, 8.196 mmol), tetrakis(triphenylphosphine)palladium (157 mg, 0.1366 mmol) were added to a 100 mL reaction bottle in sequence, and then 50 mL of N,N-dimethylformamide was added, and the reaction was evacuated and filled with nitrogen. The reaction temperature was 90°C and refluxed for 24 hours. After the reaction was completed by spot plate monitoring, extraction was performed, and finally AQ-TPA was purified by column chromatography. 1 HNMR (600MHz, CDCl3) δ8.53 (s, 2H), 8.37 (d, J=8.2Hz, 2H), 7.99 (d, J=10.2Hz, 2H), 7.6 3 (d, J=6.7Hz, 4H), 7.32-7.29 (m, 8H), 7.17 (dd, J=8.7, 4.4Hz, 12H), 7.10-7.07 (m, 4H).
[0021] Example 2: Electrochemical polymerization of monomer AQ-TPA and characterization of electrochromic properties
[0022] 0.387g TBAPF6 was dissolved in a mixed solution of 8mL toluene and 2mL acetonitrile to prepare an electrolyte. The monomer AQ-TPA was dissolved in 10mL electrolyte to prepare a monomer solution (1mmol / L). The monomer solution was subjected to 0-1.5V cyclic voltammetry polymerization with a polymerization scan rate of 0.1V / s. A polymer film was obtained by electrochemical polymerization, and then dedoped in the electrolyte at 0V for 60s. All subsequent electrochemical tests were performed in the electrolyte.
[0023] Attached Figures 1 to 4The graphs are based on the electrochemical polymerization CV curve of monomer AQ-TPA, the absorption spectrum of polymer film at different voltages, the cyclic voltammogram of polymer film device at different scan rates, and the constant current charge and discharge graph of polymer film gel energy storage device. The test results show that the polymer film prepared by the present invention has good electrochemical redox properties and excellent stability, and can achieve reversible color change from reddish brown to blue at different voltages. The polymer film device shows a small polarization phenomenon, and shows its hybrid energy storage mode based on pseudocapacitance, as well as its high capacitance at 0.1 mA / cm 2 It exhibits good energy storage behavior at low current density.
Claims
1. A triphenylamine organic polymer electrochromic material, characterized in that: The monomer has the chemical structure of formula (I):
2. The method for preparing a triphenylamine organic polymer electrochromic material monomer AQ-TPA according to claim 1, characterized in that: The method comprises the following steps: 2,6-dibromoanthraquinone and 4-triphenylamine borate undergo Suzuki coupling reaction to generate target monomer AQ-TPA. Preparation of AQ-TPA: 2,6-dibromoanthraquinone (500 mg, 1.366 mmol), 4-triphenylamine borate (1.184 g, 4.098 mmol), potassium carbonate (1.131 g, 8.196 mmol), and tetrakis(triphenylphosphine)palladium (157 mg, 0.1366 mmol) were quickly added to a 100 mL reaction bottle in sequence, and then 50 mL of N,N-dimethylformamide was added. The reaction was evacuated and filled with nitrogen. The reaction temperature was 90°C and refluxed for 24 hours. After the reaction was completed by spot plate monitoring, extraction was performed, and finally AQ-TPA was purified by column chromatography.
3. The method for preparing a triphenylamine organic polymer electrochromic material monomer according to claim 2, characterized in that: In the synthesis method, the molar ratio of 2,6-dibromoanthraquinone, 4-triphenylamine borate, potassium carbonate and tetrakis(triphenylphosphine)palladium is 1:3:6:0.1, the reaction temperature is 90° C., and the reaction time is 20 to 24 hours.
4. The triphenylamine organic polymer electrochromic material according to claim 1 is prepared by an electrochemical polymerization method.
5. The electrochemical polymerization preparation method of a triphenylamine organic polymer electrochromic material according to claim 4, characterized in that: The following steps are involved: The monomer represented by formula (I) is dissolved in a mixed solvent of toluene and acetonitrile in a volume ratio of 4:1, tetrabutylammonium hexafluorophosphate is used as an electrolyte, and polymerization is carried out by cyclic voltammetry at 0-1.5V, the polymerization scan rate is 0.1V / s, the number of cycles is 10-30, and a polymer film is obtained after electrochemical polymerization; the initial concentration of the tetrabutylammonium hexafluorophosphate is 0.1mol / L; the initial concentration of the monomer represented by formula (I) is 1mmol / L, indium tin oxide (ITO) transparent conductive glass is used as a working electrode, a platinum wire is used as a counter electrode, and a silver wire is used as a reference electrode, and the film is deposited on the surface of ITO by electrochemical polymerization.