Triphenylamine derivative polymer electrochromic porous film material as well as preparation method and application thereof
The preparation of triphenylamine derivative polymer electrochromic film is simplified by electrochemical deposition method, and the complex preparation of trianiline derivative polymer electrochromic films is solved in the prior art, and the low-cost and efficient preparation of porous films is achieved, with good optical and electrochemical properties and energy storage function.
Patent Information
- Application Number
- CN202411236034.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-04
- Publication Date
- 2024-12-27
AI Technical Summary
The preparation process of existing tripaniline derivative polymer electrochromic film materials is complicated, resulting in high manufacturing costs and affecting large-scale production and application.
The electrochemical deposition method is used to synthesize porous triphenylamine derivative polymer electrochromic films on the conductive matrix. The deposition process is carried out through a three-electrode system, using organic matter as solvent and organic salt as electrolytes. The triphenylamine derivative is within a specific potential range. Deposition, scan rate and turn count control to obtain a simplified preparation process.
The simple synthesis of triphenylamine derivative polymer electrochromic porous film is achieved, reducing costs, improving optical contrast and electrochemical response, possessing energy storage functions, and improving the cycling stability of a single component.
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Figure CN119191725A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of preparation of electrochromic energy storage materials, and specifically relates to a triphenylamine derivative polymer electrochromic porous film material and a preparation method and application thereof. Background Art
[0002] With the rapid development of human society and economy and the rapid growth of population, human demand for energy will continue to increase in the future. Fossil energy such as coal, oil, and natural gas are non-renewable resources. During use, they release a large amount of greenhouse and harmful gases to pollute the environment, which is not conducive to sustainable development. In modern society, energy consumption in commerce, residence, and transportation is rising day by day, and the research and development of environmentally friendly, energy-saving, and low-carbon materials is of great significance. Windows, which can be seen everywhere in life, are the main way for heat exchange between the inside and outside of buildings. Smart windows selectively absorb or reflect external light and solar radiation and prevent internal heat diffusion to achieve the purpose of regulating indoor temperature and light intensity. Therefore, smart windows are of great significance to energy saving and consumption reduction of buildings. Smart windows can be divided into: photochromic type, thermochromic type, and photoelectric conversion type. Electrochromic smart windows have the advantages of high optical contrast, good cycle stability, fast response time, and easy operation. According to weather changes, they can adjust the color and light transmittance of glass windows to achieve low energy consumption of buildings, conform to modernization development, meet the requirements of national energy conservation and emission reduction, and are the inevitable trend of future construction industry development.
[0003] The research on electrochromic materials has a long history. There were reports on electrochromic materials in the 1930s, but they did not attract much attention from researchers. 3 ) thin films, by applying an electric field to WO 3 The electrochromic phenomenon was observed in the thin film, and the concept of electrochromism was formally proposed. In 1973, Deb's paper discussed WO 3 The coloring mechanism of electrochromic technology was officially born. In the 1980s, Swedish scientist CG Granqvist and American scientist CM Lampert formally proposed the application of electrochromic technology in energy-saving windows and introduced the concept of smart windows. Since then, electrochromic technology has attracted the attention of domestic and foreign researchers due to its unique advantages and wide application scenarios, and has achieved many research results in the development of displays, electrochromic smart windows, glare-free reflectors and electrochromic information storage.
[0004] Electrochromism refers to the phenomenon that the optical properties (reflectivity, transmittance, absorptivity, etc.) of materials undergo stable and reversible changes by injecting or extracting charges (ions or electrons) under the action of an electric field, which is manifested in the reversible changes of color and transparency in appearance. Electrochromic materials can generally be divided into two types: inorganic electrochromic materials and organic electrochromic materials. Inorganic electrochromic materials have the advantages of good electrochemical cycle stability, a wide spectral adjustment range, strong radiation resistance and good bonding with the substrate. Organic electrochromic materials generally have low preparation costs, and have the advantages of a wide voltage window, a highly conductive doping state, easy molecular structure design and a short color change response time. As a new generation of electrochromic materials, conjugated polymers are popular because of their excellent processability, diverse colors, high optical contrast and fast switching characteristics, and have certain energy storage properties. Wu et al. used the oxidative coupling method to prepare the electrochromic and photoluminescent polymer CN-PTPA (Wu J., Liou G., High-Performance Electrofluorochromic Devices Based on Electrochromism and Photoluminescence-Active Novel Poly (4-Cyanotriphenylamine) [J]. Advanced Functional Materials, 2014, 24 (41): 6422-9) with excellent performance. However, the preparation process is cumbersome and requires complex preparation technology. In addition, the preparation cycle is long, which affects large-scale production and application. Therefore, simplifying the preparation method of polymer films has important practical significance for actual production and application. Summary of the invention
[0005] In order to overcome the problem that the preparation process of the current triphenylamine derivative polymer electrochromic thin film material is complicated and relies on complex preparation technology, resulting in high manufacturing costs, the present invention proposes the preparation of a triphenylamine derivative polymer and its copolymer electrochromic thin film material by electrochemical deposition and electropolymerization deposition in order to simplify the preparation process of the triphenylamine derivative polymer electrochromic thin film material. The purpose of the present invention is to provide a triphenylamine derivative polymer electrochromic porous thin film material and its preparation method and application. A porous triphenylamine derivative polymer electrochromic thin film is synthesized in one step on a conductive substrate using an electropolymerization method.
[0006] The purpose of the present invention is specifically achieved through the following technical solutions.
[0007] A method for preparing a triphenylamine derivative polymer electrochromic porous film material comprises one of the following methods: (1) Preparation of a triphenylamine derivative homopolymer electrochromic porous film: a deposition process is performed in a three-electrode system, and a cleaned conductive substrate is used as a working electrode. The electrolyte uses organic matter as a solvent, an organic salt as an electrolyte, and triphenylamine derivative monomers of different concentrations as precursors. A platinum column electrode is used as a counter electrode, and an Ag / AgCl electrode is used as a reference electrode. The triphenylamine derivative is deposited in a potential range of -1-2V, and the scanning rate is 20-200mV s -1 , continuously scan 5-100 circles, wash, and dry to obtain a triphenylamine derivative homopolymer electrochromic porous film.
[0008] (2) Preparation of triphenylamine derivative copolymer electrochromic porous film: The deposition process was carried out in a three-electrode system, using the cleaned conductive substrate as the working electrode. The electrolyte used organic matter as the solvent, organic salt as the electrolyte, and triphenylamine derivatives and copolymers of different molar ratios as precursors. The platinum column electrode was used as the counter electrode, and the Ag / AgCl electrode was used as the reference electrode. The copolymer film was deposited in the potential range of -1-2 V, with a scan rate of 20-200 mV s -1 , continuously scan 5-100 circles, wash, and dry to obtain the triphenylamine derivative copolymer electrochromic porous film.
[0009] Preferably, in methods (1) and (2), the triphenylamine derivative is a triphenylamine derivative, including 4-phenyltriphenylamine, TPAPy aniline, 4-(3,4-ethylenedioxythiophene)triphenylamine and other triphenylamine derivatives.
[0010] More preferably, in methods (1) and (2), the triphenylamine derivative is TPAPy.
[0011] Preferably, in method (1), the triphenylamine derivative solutions of different concentrations are 0.001-1 mol / L.
[0012] Further preferably, in method (1), the triphenylamine derivative solutions of different concentrations are 0.003 mol / L.
[0013] Preferably, in method (2), the comonomer is at least one of a thiophene derivative, an aniline derivative, a pyrrole derivative, an anthraquinone derivative, and an isoindigo derivative.
[0014] More preferably, in method (2), the comonomer is tri[4-(2-thienyl)phenyl]amine (TTPA).
[0015] Preferably, in method (2), the molar ratio of the triphenylamine derivative to the comonomer is 20:1-1:20.
[0016] Further preferably, in method (2), the molar ratio of the triphenylamine derivative to the comonomer is 3:1.
[0017] Preferably, in methods (1) and (2), the conductive substrate is at least one of glassy carbon, ITO conductive glass, carbon cloth, carbon paper, and tungsten trioxide.
[0018] Further preferably, in methods (1) and (2), the conductive substrate is ITO conductive glass.
[0019] Preferably, in methods (1) and (2), the organic matter is at least one of methanol, acetonitrile, dimethylformamide, dimethyl sulfoxide, propylene carbonate, tetrahydrofuran and dichloromethane.
[0020] More preferably, in methods (1) and (2), the organic matter is dichloromethane.
[0021] Preferably, in methods (1) and (2), the process of cleaning the conductive substrate is acetone ultrasonication for 15 minutes.
[0022] Preferably, in methods (1) and (2), the voltage range of the polymerization is -1-2V.
[0023] Further preferably, in methods (1) and (2), the polymerization voltage range is 0-1.6V.
[0024] Preferably, in methods (1) and (2), the number of polymerization cycles is 5-100 cycles.
[0025] More preferably, in methods (1) and (2), the number of polymerization cycles is 20 cycles.
[0026] Preferably, in methods (1) and (2), the electrolyte is at least one of lithium perchlorate, ammonium perchlorate, lithium hexafluorophosphate, and tetrabutylammonium hexafluorophosphate.
[0027] More preferably, in methods (1) and (2), the electrolyte is tetrabutylammonium hexafluorophosphate.
[0028] Preferably, in methods (1) and (2), the scanning rate is 20-200 mV s -1 .
[0029] Further preferably, in methods (1) and (2), the scanning rate is 100 mV s -1 .
[0030] Preferably, in methods (1) and (2), the drying environment is vacuum, the temperature is 20-100° C., and the drying time is 4-24 h.
[0031] Further preferably, in methods (1) and (2), the drying environment is vacuum, the temperature is 40° C., and the drying time is 8 h.
[0032] A triphenylamine derivative polymer electrochromic porous film material prepared by the above-mentioned preparation method and a preparation method thereof.
[0033] The above-mentioned triphenylamine derivative polymer electrochromic porous film material is used in electrochromic devices.
[0034] Compared with the prior art, the present invention has the following advantages and technical effects:
[0035] (1) The triphenylamine derivative polymer of the present invention is easy to synthesize and can be electrochemically deposited at room temperature in an atmospheric environment. In addition, the raw materials used are readily available and low in cost, and can be easily industrialized.
[0036] (2) The triphenylamine derivative polymer electrochromic porous film prepared by the present invention has good optical contrast and can change from orange to blue, as well as good electrochemical response and certain energy storage function.
[0037] (3) The present invention can achieve multiple color changes under different voltages by electrochemical copolymerization with comonomers, and can also improve the cycle stability of a single component. BRIEF DESCRIPTION OF THE DRAWINGS
[0038] Figure 1 Schematic diagram of the reaction flow of Examples 2 and 11 of the present invention.
[0039] Figure 2 The electrode material prepared in Example 11 of the present invention has a -1 Cyclic voltammetry polymerization curve.
[0040] Figure 3 This is a 50X optical microscope image of the electrode material prepared in Example 11 of the present invention. DETAILED DESCRIPTION
[0041] The specific implementation of the present invention is further described below in conjunction with examples and drawings, but the implementation of the present invention is not limited thereto.
[0042] Figure 1 The schematic diagram of the reaction process for preparing the triphenylamine derivative polymer electrochromic porous film material proposed in the present invention is shown in the following examples. Figure 1 The process operation is shown.
[0043] Example 1
[0044] Preparation of triphenylamine derivative homopolymer electrochromic porous film material: The deposition process was carried out in a three-electrode system. Cleaned ITO conductive glass was used as the working electrode. 1.55 g of tetrabutylammonium hexafluorophosphate and 19.2 mg of 4-phenyltriphenylamine were added to 40 ml of dichloromethane. A platinum column electrode was used as the counter electrode and an Ag / AgCl electrode was used as the reference electrode. CV deposition was carried out in the potential range of 0-1.5 V with a scan rate of 100 mV s -1 , scanned continuously for 20 circles, and the polymer film was repeatedly washed with dichloromethane and dried to obtain the poly(4-phenyltriphenylamine) electrochromic porous film.
[0045] Example 2
[0046] Preparation of triphenylamine derivative homopolymer electrochromic porous film material: The deposition process was carried out in a three-electrode system. Cleaned ITO conductive glass was used as the working electrode. 1.55 g of tetrabutylammonium hexafluorophosphate and 19.3 mg of TPAPy were added to 40 ml of dichloromethane. A platinum column electrode was used as the counter electrode and an Ag / AgCl electrode was used as the reference electrode. CV deposition was carried out in the potential range of 0-1.5 V with a scan rate of 100 mV s -1 , scanned continuously for 20 circles, and the polymer film was repeatedly washed with dichloromethane and dried to obtain the poly (4-pyridinetriphenylamine) (PTPAPy) electrochromic porous film.
[0047] Example 3
[0048] Preparation of triphenylamine derivative homopolymer electrochromic porous film material: The deposition process was carried out in a three-electrode system. Cleaned ITO conductive glass was used as the working electrode. 1.55 g of tetrabutylammonium hexafluorophosphate and 9.7 mg of TPAPy were added to 40 ml of dichloromethane. A platinum column electrode was used as the counter electrode and an Ag / AgCl electrode was used as the reference electrode. CV deposition was carried out in the potential range of 0-1.5 V with a scan rate of 100 mV s -1 , scanned continuously for 20 circles, and the polymer film was repeatedly washed with dichloromethane and dried to obtain the PTPAPy electrochromic porous film.
[0049] Example 4
[0050] Preparation of triphenylamine derivative homopolymer electrochromic porous film material: The deposition process was carried out in a three-electrode system. Cleaned ITO conductive glass was used as the working electrode. 1.55 g of tetrabutylammonium hexafluorophosphate and 19.3 mg of TPAPy were added to 40 ml of dichloromethane. A platinum column electrode was used as the counter electrode and an Ag / AgCl electrode was used as the reference electrode. CV deposition was carried out in the potential range of 0-1.8 V with a scan rate of 100 mV s -1, scanned continuously for 20 circles, and the polymer film was repeatedly washed with dichloromethane and dried to obtain the PTPAPy electrochromic porous film.
[0051] Example 5
[0052] Preparation of triphenylamine derivative homopolymer electrochromic porous film material: The deposition process was carried out in a three-electrode system. Cleaned ITO conductive glass was used as the working electrode. 1.55 g of tetrabutylammonium hexafluorophosphate and 19.3 mg of TPAPy were added to 40 ml of acetonitrile. A platinum column electrode was used as the working electrode and an Ag / AgCl electrode was used as the reference electrode. CV deposition was carried out in the potential range of 0-1.5 V with a scan rate of 100 mV s -1 , scanned continuously for 20 circles, and the polymer film was repeatedly washed with dichloromethane and dried to obtain the PTPAPy electrochromic porous film.
[0053] Example 6
[0054] Preparation of triphenylamine derivative homopolymer electrochromic porous film material: The deposition process was carried out in a three-electrode system. Cleaned ITO conductive glass was used as the working electrode. 1.55 g of tetrabutylammonium hexafluorophosphate and 19.3 mg of TPAPy were added to 40 ml of dichloromethane. A platinum column electrode was used as the counter electrode and an Ag / AgCl electrode was used as the reference electrode. CV deposition was carried out in the potential range of 0-1.5 V with a scan rate of 100 mV s -1 , scanned continuously for 40 circles, and the polymer film was repeatedly washed with dichloromethane and dried to obtain the PTPAPy electrochromic porous film.
[0055] Example 7
[0056] Preparation of triphenylamine derivative homopolymer electrochromic porous film material: The deposition process was carried out in a three-electrode system. Cleaned ITO conductive glass was used as the working electrode. 1.55 g of tetrabutylammonium hexafluorophosphate and 19.3 mg of TPAPy were added to 40 ml of dichloromethane. A platinum column electrode was used as the counter electrode and an Ag / AgCl electrode was used as the reference electrode. CV deposition was carried out in the potential range of 0-1.5 V with a scan rate of 50 mV s -1 , scanned continuously for 20 circles, and the polymer film was repeatedly washed with dichloromethane and dried to obtain the PTPAPy electrochromic porous film.
[0057] Example 8
[0058] Preparation of triphenylamine derivative homopolymer electrochromic porous film material: The deposition process was carried out in a three-electrode system. Cleaned ITO conductive glass was used as the working electrode. 1.55 g of tetrabutylammonium hexafluorophosphate and 19.6 mg of 4-thiophenetriphenylamine were added to 40 ml of dichloromethane. A platinum column electrode was used as the counter electrode and an Ag / AgCl electrode was used as the reference electrode. CV deposition was carried out in the potential range of 0-1.5 V with a scan rate of 100 mV s -1 , scanned continuously for 20 circles, and the polymer film was repeatedly washed with dichloromethane and dried to obtain the poly(4-thiophenetriphenylamine) electrochromic porous film.
[0059] Example 9
[0060] Preparation of triphenylamine derivative homopolymer electrochromic porous film material: The deposition process was carried out in a three-electrode system. Cleaned ITO conductive glass was used as the working electrode. 1.55 g of tetrabutylammonium hexafluorophosphate and 19.3 mg of TPAPy were added to 40 ml of dichloromethane. A platinum column electrode was used as the working electrode and an Ag / AgCl electrode was used as the reference electrode. CV deposition was carried out in the potential range of 0-1.5 V with a scan rate of 100 mV s -1 , scanned continuously for 20 circles, and the polymer film was repeatedly washed with dichloromethane and dried to obtain the PTPAPy electrochromic porous film.
[0061] Example 10
[0062] Preparation of triphenylamine derivative homopolymer electrochromic porous film material: The deposition process was carried out in a three-electrode system. Cleaned ITO conductive glass was used as the working electrode. 0.43 g of ammonium perchlorate and 19.3 mg of TPAPy were added to 40 ml of dichloromethane. A platinum column electrode was used as the counter electrode and an Ag / AgCl electrode was used as the reference electrode. CV deposition was carried out in the potential range of 0-1.5 V with a scan rate of 100 mV s -1 , scanned continuously for 40 circles, and the polymer film was repeatedly washed with dichloromethane and dried to obtain the PTPAPy electrochromic porous film.
[0063] Embodiment 11
[0064] Preparation of triphenylamine derivative copolymer electrochromic porous film material: The deposition process was carried out in a three-electrode system. Cleaned ITO conductive glass was used as the working electrode. 1.55 g of tetrabutylammonium hexafluorophosphate, 14.5 mg of TPAPy and 4.9 mg of TTPA were added to 40 ml of dichloromethane. A platinum column electrode was used as the counter electrode and an Ag / AgCl electrode was used as the reference electrode. The potential range was 0-1.5 V and the scan rate was 100 mV s -1, scanned 20 times continuously, and the polymer film was repeatedly washed with dichloromethane and dried to obtain the electrochromic porous film of TPAPy and TTPA copolymer (P(TPAPy-co-TTPA)). Figure 2 As shown in the figure, with the increase of the number of polymerization cycles, the curve continues to expand outward, indicating that the active monomers continue to polymerize on the surface of the conductive substrate, and the formed polymer film is deposited on the conductive layer, and finally a P(TPAPy-co-TTPA) film is obtained. The morphology of the P(TPAPy-co-TTPA) film material prepared above is shown in the figure. Figure 3 As shown in the figure, interconnected particles are formed, indicating that the porous film material is successfully prepared. The formation of this porous structure is conducive to the rapid embedding and extraction of electrolyte ions, greatly improving the color change response speed of the material. The interconnected porous material has a lower impedance and the structure is not easily destroyed during the application process, which is conducive to improving the cycle stability of the material.
[0065] Example 12
[0066] Preparation of triphenylamine derivative copolymer electrochromic porous film material: Deposition process was carried out in a three-electrode system, using cleaned ITO conductive glass as the working electrode, adding 1.55g tetrabutylammonium hexafluorophosphate, 19.3mg TPAPy and 31mg 3,4-ethylenedioxythiophene (EDOT) in 40ml dichloromethane, platinum column electrode as the working electrode, Ag / AgCl electrode as the reference electrode. Deposition was carried out in the potential range of 0-1.6V, and the scan rate was 100mV s -1 , scanned continuously for 20 circles, and the copolymer film was repeatedly washed with dichloromethane and dried to obtain the P(TPAPy-co-EDOT) electrochromic porous film.
[0067] Embodiment 13
[0068] Preparation of triphenylamine derivative copolymer electrochromic porous film material: Deposition process was carried out in a three-electrode system, using cleaned ITO conductive glass as the working electrode, adding 0.43g ammonium perchlorate, 14.5mg TPAPy and 4.9mg TTPA in 40ml dichloromethane, platinum column electrode as the counter electrode, and Ag / AgCl electrode as the reference electrode. P(TPAPy-co-TTPA) copolymer film was deposited in the potential range of 0-1.5V, with a scan rate of 100mV s -1 , scanned continuously for 20 circles, and the polymer film was repeatedly washed with dichloromethane and dried to obtain the P(TPAPy-co-TTPA) electrochromic porous film.
[0069] Embodiment 14
[0070] Preparation of triphenylamine derivative copolymer electrochromic porous film material: Deposition process was carried out in a three-electrode system, using cleaned ITO conductive glass as the working electrode, adding 1.55g tetrabutylammonium hexafluorophosphate, 9.7mg TPAPy and 9.8mg TTPA in 40ml dichloromethane, platinum column electrode as the counter electrode, and Ag / AgCl electrode as the reference electrode. P(TPAPy-co-TTPA) copolymer film was deposited in the potential range of 0-1.5V, with a scan rate of 100mV s -1 , scanned continuously for 20 circles, and the polymer film was repeatedly washed with dichloromethane and dried to obtain the P(TPAPy-co-TTPA) electrochromic porous film.
[0071] Embodiment 15
[0072] Preparation of triphenylamine derivative copolymer electrochromic porous film material: Deposition process was carried out in a three-electrode system, using cleaned ITO conductive glass as the working electrode, adding 1.55g tetrabutylammonium hexafluorophosphate, 14.5mg TPAPy and 4.9mg TTPA in 40ml dichloromethane, platinum column electrode as the counter electrode, and Ag / AgCl electrode as the reference electrode. P(TPAPy-co-TTPA) copolymer film was deposited in the potential range of 0-1.5V, with a scan rate of 100mV s -1 , scanned continuously for 40 circles, and the polymer film was repeatedly washed with dichloromethane and dried to obtain the P(TPAPy-co-TTPA) electrochromic porous film.
[0073] Example 16
[0074] Preparation of triphenylamine derivative copolymer electrochromic porous film material: Deposition process was carried out in a three-electrode system, using cleaned ITO conductive glass as the working electrode, adding 1.55g tetrabutylammonium hexafluorophosphate, 14.5mg TPAPy and 4.9mg TTPA in 40ml dichloromethane, platinum column electrode as the working electrode, and Ag / AgCl electrode as the reference electrode. P(TPAPy-co-TTPA) copolymer film was deposited in the potential range of 0-1.8V, with a scan rate of 20mV s -1 , scanned continuously for 40 circles, and the polymer film was repeatedly washed with dichloromethane and dried to obtain the P(TPAPy-co-TTPA) electrochromic porous film.
[0075] Embodiment 17
[0076] Preparation of triphenylamine derivative copolymer electrochromic porous film material: Deposition process was carried out in a three-electrode system, using cleaned ITO conductive glass as the working electrode, adding 1.55g tetrabutylammonium hexafluorophosphate, 14.5mg TPAPy and 4.9mg TTPA in 40ml acetonitrile, platinum column electrode as the counter electrode, and Ag / AgCl electrode as the reference electrode. P(TPAPy-co-TTPA) copolymer film was deposited in the potential range of 0-1.5V, with a scan rate of 100mV s -1 , scanned continuously for 20 circles, and the polymer film was repeatedly washed with dichloromethane and dried to obtain the P(TPAPy-co-TTPA) electrochromic porous film.
[0077] Embodiment 18
[0078] Preparation of triphenylamine derivative copolymer electrochromic porous film material: Deposition process was carried out in a three-electrode system, using cleaned ITO conductive glass as the working electrode, adding 1.55g tetrabutylammonium hexafluorophosphate, 14.5mg TPAPy and 4.9mg TTPA in 40ml dichloromethane, platinum column electrode as the counter electrode, and Ag / AgCl electrode as the reference electrode. P(TPAPy-co-TTPA) copolymer film was deposited in the potential range of 0-1.5V, with a scan rate of 20mV s -1 , scanned continuously for 40 circles, and the polymer film was repeatedly washed with dichloromethane and dried to obtain the P(TPAPy-co-TTPA) electrochromic porous film.
[0079] Embodiment 19
[0080] Preparation of triphenylamine derivative copolymer electrochromic porous film material: Deposition process was carried out in a three-electrode system, using cleaned ITO conductive glass as the working electrode, adding 1.55g tetrabutylammonium hexafluorophosphate, 14.5mg TPAPy and 4.9mg TTPA in 40ml dichloromethane, platinum column electrode as the counter electrode, and Ag / AgCl electrode as the reference electrode. P(TPAPy-co-TTPA) copolymer film was deposited in the potential range of 0-1.5V, with a scan rate of 200mV s -1 , scanned continuously for 40 circles, and the polymer film was repeatedly washed with dichloromethane and dried to obtain the P(TPAPy-co-TTPA) electrochromic porous film.
Claims
1. A method for preparing a triphenylamine derivative polymer electrochromic porous film material, characterized in that: This includes one of the following methods: (1) Preparation of triphenylamine derivative homopolymer electrochromic porous film: An electrolyte containing a triphenylamine derivative monomer is prepared, and an electrochromic porous film of a triphenylamine derivative homopolymer is prepared on a conductive substrate by an electrochemical deposition method; (2) Preparation of triphenylamine derivative copolymer electrochromic porous film: A mixed electrolyte containing triphenylamine derivative monomers and electroactive monomers is prepared, and an electrochemical deposition method is used to prepare a triphenylamine derivative copolymer electrochromic porous film on a conductive substrate.
2. The method for preparing the triphenylamine derivative polymer electrochromic porous film material according to claim 1, characterized in that: The process parameters of method (1) are as follows: the deposition process is carried out in a three-electrode system, the cleaned conductive substrate is used as the working electrode; the electrolyte uses organic matter as the solvent, organic salt as the electrolyte, and the triphenylamine derivative as the electroactive monomer; the platinum column electrode is used as the counter electrode, and the Ag / AgCl electrode is used as the reference electrode; the triphenylamine derivative is deposited in the potential range of -1-2V, and the scanning rate is 20-200mV s -1 , continuously scan 5-100 circles, wash, and dry to obtain a triphenylamine derivative homopolymer electrochromic porous film.
3. The method for preparing the triphenylamine derivative polymer electrochromic porous film material according to claim 1, characterized in that: The process parameters of method (2) are as follows: the deposition process is carried out in a three-electrode system, the cleaned conductive substrate is used as the working electrode, the electrolyte uses organic matter as the solvent, the organic salt as the electrolyte, the triphenylamine derivative and the copolymer monomer as the precursor; the platinum column electrode is used as the counter electrode, and the Ag / AgCl electrode is used as the reference electrode; the copolymer film is deposited in the potential range of -1-2V, and the scanning rate is 20-200mV s -1 , continuously scan 5-100 circles, wash, and dry to obtain the triphenylamine derivative copolymer electrochromic porous film.
4. The method for preparing the triphenylamine derivative polymer electrochromic porous film material according to claim 1, characterized in that: In methods (1) and (2), the triphenylamine derivative is at least one of 4-phenyltriphenylamine, 4-pyridinetriphenylamine (TPAPy), 4-thiophenetriphenylamine, and 4-(3,4-ethylenedioxythiophene)triphenylamine; The conductive substrate is at least one of glassy carbon, indium tin oxide (ITO) glass, carbon cloth, carbon paper, Prussian blue and tungsten trioxide.
5. The method for preparing the triphenylamine derivative polymer electrochromic porous thin film material according to claim 2 or 3, characterized in that: The organic matter is at least one of methanol, acetonitrile, dimethylformamide, dimethyl sulfoxide, propylene carbonate, tetrahydrofuran and dichloromethane.
6. The method for preparing the triphenylamine derivative polymer electrochromic porous film material according to claim 2, characterized in that: In method (1), the triphenylamine derivative solution is 0.001-1 mol / L.
7. The method for preparing the triphenylamine derivative polymer electrochromic porous film material according to claim 3, characterized in that: In method (2), the comonomer is at least one of a thiophene derivative, an aniline derivative, a pyrrole derivative, an anthraquinone derivative, and an isoindigo derivative; The molar ratio of the triphenylamine derivative to the comonomer is 20:1-1:
20.
8. A porous polytriphenylamine derivative electrochromic thin film material prepared by the preparation method according to any one of claims 1 to 7.
9. Use of the triphenylamine derivative polymer electrochromic porous film preparation material as claimed in claim 8 in an electrochromic device.
10. Use of the triphenylamine derivative polymer electrochromic porous film material according to claim 8 in energy storage devices.