A polyarylsulfone / polyarylketone electrochromic polymer film with electrochemical sites and its preparation method and application

Abstract

The present invention relates to a polyarylsulfone / polyarylketone electrochromic polymer film with electrochemical sites, and a preparation method and application thereof. The purpose of the present invention is to solve the problems of poor solubility and difficulty in film formation of polyarylsulfone / polyarylketone electrochromic polymers during the film preparation process. Method: The electrode is immersed in a monomer electrolyte solution containing an aniline structure and a carbazole structure, and the monomer is activated by electrochemical oxidation or reduction to undergo a polymerization reaction to form a polymer film on the surface of the electrode. Beneficial effects of the present invention: The polyarylsulfone and polyarylketone electrochromic films prepared by the method have good cycle stability, can be directly polymerized and grown on the electrode surface at room temperature and pressure to form a film, and the thickness of the film can be effectively controlled. The electrochromic film prepared by the method is simple to operate and has great development potential in practical applications, such as electrochromism, supercapacitors, electrically controlled fluorescence, aggregation-induced luminescence, and information storage.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a polyarylsulfone / polyarylketone electrochromic polymer film with electrochemical sites, a preparation method and an application thereof. Background Art

[0002] Electrochromism refers to the change in the optical properties of the material itself under the action of an external electric field, that is, the optical characteristics of electrically activated materials. This material can not only produce a significant change in appearance color after the voltage is applied, but also maintain this color change stably and permanently after the voltage disappears, making the electrochromic device more energy-efficient and maintaining its optical properties without consuming electricity. Therefore, electrochromic materials have been widely used and studied in energy-saving lighting systems such as buildings, automobiles, and airplanes. Due to the characteristics of its color change mechanism, this material has been widely used in key energy storage devices such as supercapacitors and lithium batteries.

[0003] Among the currently known electrochromic materials, polymer electrochromic materials themselves have rich color changes, high contrast and fast response speed. The conductive polymers that have received more attention include polyaniline, polyarylsulfone, polythiophene, polypyrrole and their derivatives. Studies have found that the materials have the advantages of good conductivity, high optical contrast and good reversibility of color change. However, in the process of film preparation, polyarylsulfone / polyarylketone polymers have poor solubility, which affects the later film formation effect and reduces the stability of the prepared electrochromic film. How to solve the problem of poor solubility and difficult film formation of polyarylsulfone / polyarylketone electrochromic polymers in the film preparation process is an important way to improve the periodic stability of films of this type of material. Summary of the invention

[0004] In order to solve the above problems, the present invention relates to a polyarylsulfone / polyarylketone electrochromic polymer film with electrochemical sites, and provides a method and application of preparing a high-performance polymer electrochromic film by an electrochemical polymerization method. The polyarylsulfone / polyarylketone electrochromic polymer has poor solubility and difficulty in film formation during the film preparation process. The method can make the polymerization process and the film formation process proceed simultaneously, and can improve the periodic stability of the electrochromic film without increasing the difficulty of the process.

[0005] The objective of the present invention is achieved through the following technical solutions:

[0006] A polyarylsulfone / polyarylketone electrochromic polymer film with electrochemical sites, wherein the raw material has a structure shown in formula (I)

[0007]

[0008] Wherein, X is one of the structures shown in X1 to X2:

[0009]

[0010] T is one of the structures shown in T1 to T4:

[0011]

[0012] A method for preparing a polyarylsulfone / polyarylketone electrochromic polymer film having electrochemical sites comprises the following steps:

[0013] Step 1: Select a standard three-electrode system: working electrode: tin-doped indium oxide (ITO) as a conductive material glass substrate; reference electrode: silver / silver ion electrode; counter electrode: platinum wire;

[0014] Step 2, dissolving the monomer containing aniline / carbazole structure in a solvent, and adding electrolyte to make the solution conductive;

[0015] Step 3: applying power and pressure to polymerize the monomers to form a linear structure polymer that grows on the surface of the ITO glass to form a film;

[0016] Step 4: Post-processing the film that has completed electrochemical polymerization to obtain a stable film.

[0017] Furthermore, the conductive base material in step 1 includes:

[0018] Glass substrate material coated with transparent conductive oxide, conductive oxide: antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), tin-doped indium oxide (ITO), molybdenum-doped indium oxide (IMO), aluminum-doped zinc oxide (AZO), calcium-doped zinc oxide (GZO);

[0019] Polymer conductive substrate materials: polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polycarbonate (PC), polyvinylidene fluoride (PVDF);

[0020] Other conductive substrate materials: silver nano transparent conductive substrate, carbon nanotube transparent substrate, graphene transparent conductive substrate.

[0021] Furthermore, the solvent in step 2 includes: one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, chloroform, ethylene carbonate, propylene carbonate, nitrobenzene, tetrahydrofuran, acetic acid, acetonitrile, and acetone solvents, which are configured into a solution with a concentration of 0.1 to 100 mg per milliliter.

[0022] Further, the electrolyte in step 2 includes: sodium salts, sodium chloride, sodium hydroxide, sodium nitrate, sodium perchlorate; potassium salts, potassium chloride, potassium nitrate, potassium hydroxide; ammonium salts, ammonium nitrate, ammonium sulfate, tetrabutylammonium hexafluorophosphate, triethylmethylammonium tetrafluoroborate; lithium salts, lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate; onium salts, N-dialkylpyrrolidinium salts, N-dialkylpiperidinium salts, N,N-dimethylpyrrolidinium tetrafluoroborate; acid electrolytes, hydrochloric acid, nitric acid, phosphoric acid. The experiment uses one or more of them and configures them into an electrolyte solution with a concentration of 0.1 to 1 mol per liter.

[0023] Furthermore, the pressure application mode in step 3 includes: cyclic voltammetry, constant voltage method and constant current method. The starting voltage range of cyclic voltammetry is -3.0 volts to 3.0 volts; the scan rate is 10 to 500 millivolts per second; the scan time is 0 to 10 minutes; the working voltage of the constant voltage method is -3.0 to 3.0 volts; the power-on time is 0 to 10 minutes; the working current of the constant current method is 0.05 mA to 10 mA; the power-on time is 0 to 120 minutes.

[0024] Furthermore, the post-treatment method in step 4 includes: rinsing, soaking and thermal annealing.

[0025] Furthermore, the elution solvent includes: volatile solvents: water, acetonitrile, ethanol, acetone; the immersion time: 5 to 30 minutes; the thermal annealing atmosphere: air, vacuum, nitrogen; the temperature range: 60 to 180°C; the thermal annealing time: 1 to 10 hours.

[0026] The invention discloses an application of a polyarylsulfone / polyarylketone electrochromic polymer film having electrochemical sites, which can be applied to the fields of electrochromism, electrically controlled fluorescence, aggregation-induced emission, information storage and supercapacitors.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] The present invention starts from the perspective of polymerization method, polymerizes the monomer with triphenylamine / carbazole structure by electrochemical polymerization method, and obtains a high-performance electrochromic polymer film. The film has good electroluminescent performance and thermal stability. The present invention polymerizes the monomer by electrochemical polymerization method, and directly grows on a conductive substrate to form a film, which is easy to mass produce and can meet the technical requirements of large-scale industrial production of traditional devices. Therefore, it has broad application prospects in electrochromism, supercapacitors, information storage and solar cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the embodiments of the present invention and the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. The drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without creative work.

[0030] Figure 1 is a flow chart of polymer P1 prepared in Example 1 of the present invention;

[0031] Figure 2 is the cyclic voltammogram of polymer P1 prepared in Example 1 of the present invention;

[0032] Figure 3 is the electrochemical spectrum of polymer P1 prepared in Example 1 of the present invention;

[0033] Figure 4 is the contrast ratio of polymer P1 prepared in Example 1 of the present invention;

[0034] Figure 5 is an It curve graph of polymer P1 prepared in Example 1 of the present invention;

[0035] Figure 6 is the coloring time of polymer P1 prepared in Example 1 of the present invention;

[0036] Figure 7 is an electrochemical spectrum of the device prepared in Example 6 of the present invention;

[0037] Figure 8 is the contrast ratio of the device prepared in Example 6 of the present invention;

[0038] Fig. 9 is an It curve diagram of the device prepared in Example 6 of the present invention;

[0039] Fig.10 is the coloring time of the device prepared in Example 6 of the present invention; DETAILED DESCRIPTION

[0040] The technical solutions of various embodiments of the present invention will be clearly described below, but these embodiments described are only part of the present invention, not all embodiments. The protection scope of the present invention includes other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative work.

[0041] For a clearer description, the following example will be used to describe in detail.

[0042] The preparation method of the polyarylsulfone / polyarylketone electrochromic polymer film having electrochemical sites of the present invention is achieved by the following steps:

[0043] The monomer raw material has the structure shown in formula (I)

[0044]

[0045] The monomer raw materials are synthesized by electrochemical polymerization methods: cyclic voltammetry, constant voltage method, and constant current method, and all have repeating units of the structure shown in formula (II):

[0046]

[0047] Where n is a positive integer, indicating the degree of polymerization;

[0048] X is one of the structures shown in X1~X2:

[0049]

[0050] T is one of the structures shown in T1 to T4:

[0051]

[0052] Furthermore, the raw material for electrochemical polymerization is M1 structure:

[0053]

[0054] It can form a P1 polymer having a structure shown in formula (III) by electrochemical polymerization:

[0055]

[0056] The present invention dissolves the monomer in one or more of the following solvents: N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, chloroform, ethylene carbonate, propylene carbonate, nitrobenzene, tetrahydrofuran, acetic acid, acetonitrile, and acetone, and prepares the solution with a concentration of 0.1 to 100 mg / ml.

[0057] The electrolytes include: sodium salts, such as sodium chloride, sodium hydroxide, sodium nitrate, and sodium perchlorate; potassium salts, such as potassium chloride, potassium nitrate, and potassium hydroxide; ammonium salts, such as ammonium nitrate, ammonium sulfate, tetrabutylammonium hexafluorophosphate, and triethylmethylammonium tetrafluoroborate; lithium salts, such as lithium perchlorate, lithium hexafluorophosphate, and lithium tetrafluoroborate; onium salts, such as N-dialkylpyrrolidinium salts, N-dialkylpiperidinium salts, and N,N-dimethylpyrrolidinium tetrafluoroborate; and acid electrolytes, such as one or more of hydrochloric acid, nitric acid, and phosphoric acid, configured into an electrolyte solution with a concentration of 0.1 to 1 mol per liter.

[0058] A standard three-electrode system was selected: working electrode: ITO conductive material glass as substrate; reference electrode: silver / silver ion electrode; counter electrode: platinum wire.

[0059] Conductive substrate materials include: glass substrate materials coated with transparent conductive oxides, conductive oxides: antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), tin-doped indium oxide (ITO), molybdenum-doped indium oxide (IMO), aluminum-doped zinc oxide (AZO), calcium-doped zinc oxide (GZO); polymer conductive substrate materials: polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polycarbonate (PC), polyvinylidene fluoride (PVDF); other conductive substrate materials: silver nano transparent conductive substrate, carbon nanotube transparent substrate, graphene transparent conductive substrate.

[0060] The system is pressurized by cyclic voltammetry, constant voltage method and constant current method. The starting voltage range of cyclic voltammetry is -3.0 volts to 3.0 volts; the scan rate is 10 to 500 millivolts per second; the scan time is 0 to 10 minutes; the working voltage of the constant voltage method is -3.0 to 3.0 volts; the power-on time is 0 to 10 minutes; the working current of the constant current method is 0.05 mA to 10 mA; and the power-on time is 0 to 120 minutes.

[0061] The prepared electrochromic polymer film is post-processed by elution, immersion and thermal annealing. The elution solvents are: volatile solvents, water, acetonitrile, ethanol, acetone; immersion time: 5 to 30 minutes; thermal annealing atmosphere: air, vacuum, nitrogen; temperature range: 60 to 180°C; thermal annealing time: 1 to 10 hours. After obtaining a stable film, subsequent related data measurements can be performed.

[0062] Example 1

[0063] The polymer film was prepared by cyclic voltammetry: a standard three-electrode system was used, with the working electrode being ITO glass, the reference electrode being silver / silver ion electrode, and the counter electrode being platinum wire; solution preparation: tetrabutylammonium perchlorate electrolyte was dissolved in a mixed solvent of acetonitrile and dichloromethane (1:3) to prepare a 0.1 mol / L solution; the voltage of the power supply was 0 to 1 volt, and the cycle was repeated 500 times; after the power supply was completed, the ITO glass electrode was rinsed with a dichloromethane solution, and then dried in a vacuum drying oven at 120°C for 5 hours to obtain a polymer electrochromic film prepared by cyclic voltammetry. The preparation process is as follows: Figure 1 shown.

[0064] Example 2

[0065] The polymer film was prepared by a constant voltage method: a standard three-electrode system was used, with ITO glass as the working electrode, silver / silver ion electrode as the reference electrode, and platinum wire as the counter electrode; solution preparation: tetrabutylammonium perchlorate electrolyte was dissolved in a mixed solvent of acetonitrile and dichloromethane (1:3) to prepare a 0.1 mol / L solution; the voltage was selected to be 1.5 volts, and the power-on time was 350 seconds; after the power-on ended, the ITO glass electrode was rinsed with a dichloromethane solution, and then dried in a vacuum drying oven at 120°C for 5 hours to obtain a polymer electrochromic film prepared by a constant voltage method.

[0066] Example 3

[0067] The polymer film was prepared by a constant current method: a standard three-electrode system was used, with ITO glass as the working electrode, silver / silver ion electrode as the reference electrode, and platinum wire as the counter electrode; solution preparation: tetrabutylammonium perchlorate electrolyte was dissolved in a mixed solvent of acetonitrile and dichloromethane (1:3) to prepare a 0.1 mol / L solution; the current was selected to be 0.25 mA, and the power was turned on for 30 minutes; after the power was turned on, the ITO glass electrode was rinsed with a dichloromethane solution, and then dried in a vacuum drying oven at 120°C for 5 hours to obtain a polymer electrochromic film prepared by a constant current method.

[0068] Example 4

[0069] The polymer electrochromic film prepared by the present invention was subjected to a cyclic voltammetry test. The electrolyte solution was a 0.1 mol / L electrolyte solution prepared by dissolving tetrabutylammonium perchlorate electrolyte in anhydrous acetonitrile solvent. The reference electrode was a silver / silver ion electrode, the platinum wire was a counter electrode, and the working electrode was an ITO glass with a polymer film. The scanning speed during the test was 100 millivolts per second, and the voltage window was 0 to 1.2 volts. The test was carried out in an argon atmosphere to eliminate the interference of oxygen in the air. Figure 2 As shown in the cyclic voltammetry curve, we can find the oxidation potential peak at 0.92 volts on the positive scanning curve of 0-1.2 volts, and the corresponding reduction potential peak on the negative scanning curve. This experimental result shows that the polymer does have relatively excellent electrochemical properties, and therefore has great application prospects in the field of electrochromism.

[0070] Example 5

[0071] The electrochromic performance of the polymer electrochromic film prepared by the present invention is tested using a standard three-electrode system, wherein the working electrode is ITO glass with a polymer film, the reference electrode is a silver / silver ion electrode, and the counter electrode is a platinum wire; the electrolyte is tetrabutylammonium perchlorate electrolyte dissolved in anhydrous acetonitrile solvent to prepare a 0.1 mol / L solution; the test method is to use an electrochemical workstation in conjunction with an ultraviolet-visible spectrum, and select a square wave potential method to test the electrochromic cycle stability of the polymer film at a specific wavelength, from Figure 3 It can be seen from the electrochemical spectrum that as the voltage increases, the peak at 365 nanometers decreases, while the peaks at 468 nanometers and 704 nanometers increase. The absorption peak of the polymer can change with the change of the applied voltage, indicating that the polymer prepared by the present invention has electrochromic properties. Figure 4 , 5 It can be seen that the contrast of the electrochromic film is large enough and there is no obvious attenuation after a certain number of cycles. Figure 6 It can be seen that the obtained polymer film has a short coloring time and good cycle stability. In summary, the polymer electrochromic film prepared by the present invention is beneficial for application in the optoelectronic field.

[0072] Example 6

[0073] Preparation of gel electrolyte-polymer film electrochromic / supercapacitor dual-function device: Select the prepared polymer film as the electrochromic layer, 1 mol / L lithium perchlorate polymethyl methacrylate gel as the electrolyte, and ethyl viologen as the ion storage layer, and encapsulate them into a "sandwich" structure with a curing glue to obtain a gel electrolyte-polymer film electrochromic device.

[0074] Example 7

[0075] The electrochromic performance of the gel electrolyte-polymer film electrochromic / supercapacitor dual-function device prepared by the present invention was tested. The reference electrode and the counter electrode were ITO glass, and the working electrode was ITO glass with a polymer film. The scanning speed during the test was 20 millivolts per second, and the voltage window was 0 to 2 volts. The test was carried out in a glove box. The test method was to use an electrochemical workstation in conjunction with a UV-visible spectrum, and select the square wave potential method to test the electrochromic cycle stability of the polymer film at a specific wavelength. Figure 7 It can be seen from the electrochemical spectrum that as the voltage increases, the absorption peak of the device changes with the applied voltage, indicating that the prepared device has electrochromic properties. Figure 8 , 9 It can be seen that the contrast of the device is large enough and there is no obvious attenuation after a certain number of cycles. Fig.10It can be seen that the obtained device has a short coloring time and good cycle stability. In summary, the device prepared by the present invention has good performance.

[0076] The present invention immerses the electrode in a monomer electrolyte solution containing an aniline structure / carbazole structure, utilizes electrochemical oxidation or reduction, activates the monomer to undergo polymerization reaction, and forms a polymer film on the electrode surface. The polyarylsulfone and polyarylketone electrochromic films prepared by the method have good cycle stability, can be directly polymerized on the electrode surface at room temperature and pressure, and can effectively control the thickness of the film. The electrochromic film prepared by the method is simple to operate and has great development potential in practical applications, such as electrochromism, supercapacitors, electrically controlled fluorescence, aggregation-induced luminescence, and information storage.

Claims

1. A method for preparing a polyarylsulfone electrochromic polymer film having electrochemical sites, characterized in that: The polymer has a structure shown in formula (I): Where n is a positive integer, indicating the degree of polymerization; The method for preparing the polyarylsulfone electrochromic polymer film comprises the following steps: Step 1: Select a standard three-electrode system: working electrode: tin-doped indium oxide (ITO) as the conductive material glass substrate; reference electrode: silver / silver ion electrode; counter electrode: platinum wire; Step 2, dissolving the monomer containing the aniline structure in a solvent, and adding an electrolyte to make the solution conductive; Among them, the structural formula of the monomer containing aniline structure is: Step 3: applying power and pressure to polymerize the monomers to form a linear structure polymer that grows on the surface of the ITO glass to form a film; Step 4: Post-processing the film that has completed electrochemical polymerization to obtain a stable film.

2. The method for preparing a polyarylsulfone electrochromic polymer film having electrochemical sites according to claim 1, characterized in that: The solvent in step 2 includes: one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, chloroform, ethylene carbonate, propylene carbonate, nitrobenzene, tetrahydrofuran, acetic acid, acetonitrile, and acetone solvents, which are configured into a solution with a concentration of 0.1 to 100 mg / ml.

3. The method for preparing a polyarylsulfone electrochromic polymer film having electrochemical sites according to claim 1, characterized in that: The electrolyte in step 2 includes: sodium salts: sodium chloride, sodium hydroxide, sodium nitrate, sodium perchlorate; potassium salts: potassium chloride, potassium nitrate, potassium hydroxide; ammonium salts: ammonium nitrate, ammonium sulfate, tetrabutylammonium hexafluorophosphate, triethylmethylammonium tetrafluoroborate; lithium salts: lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate; onium salts: N-dialkylpyrrolidinium salts, N-dialkylpiperidinium salts, N,N-dimethylpyrrolidinium tetrafluoroborate; acid electrolytes: hydrochloric acid, nitric acid, phosphoric acid; one or more of them are used to prepare an electrolyte solution with a concentration of 0.1 to 1 mol per liter.

4. The method for preparing a polyarylsulfone electrochromic polymer film having electrochemical sites according to claim 1, characterized in that: The pressurization mode in the step three includes: cyclic voltammetry, constant voltage method or constant current method; the starting voltage range of the cyclic voltammetry is -3.0 volts to 3.0 volts, the scanning rate is 10 to 500 millivolts per second, and the scanning time is 0 to 10 minutes. The working voltage of the constant voltage method is -3.0 to 3.0 volts, and the power-on time is 0 to 10 minutes. The working current of the constant current method is 0.05 mA to 10 mA, and the power-on time is 0 to 120 minutes.

5. The method for preparing a polyarylsulfone electrochromic polymer film having electrochemical sites according to claim 1, characterized in that: The post-treatment method in step 4 includes: rinsing, soaking and thermal annealing.

6. The method for preparing a polyarylsulfone electrochromic polymer film having electrochemical sites according to claim 5, characterized in that: The elution solvent includes: water, acetonitrile, ethanol or acetone; the immersion time is: 5 to 30 minutes; the thermal annealing atmosphere is air, vacuum or nitrogen, the thermal annealing temperature range is: 60 to 180°C, and the thermal annealing time is: 1 to 10 hours.

7. Use of the polyarylsulfone electrochromic polymer film with electrochemical sites prepared according to the preparation method of claim 1, wherein the application fields are electrochromism, electrically controlled fluorescence, aggregation-induced emission, information storage or supercapacitor.

Images