Conductive polymer based on quinacridone and preparation method and application thereof

Abstract

This invention relates to the field of energy storage materials technology, specifically to a conductive polymer based on quinacridone, its preparation method, and its application. The conductive polymer based on quinacridone is shown in formula (I): (I) In formula (I), n represents the average degree of polymerization, and n ranges from 10 to 2000. The conductive polymer based on quinacridone in this invention has good solubility and can be dissolved in a solvent to form a solution. It can then be sprayed to achieve large-area processing, which simplifies the preparation process of electrode materials. Using nickel foam as a conductive substrate, the prepared energy storage color-changing material still has a high areal capacitance at high current densities and good charge-discharge stability at different current densities. Furthermore, the amount of stored energy can be determined by observing the change in electrode color, which has great application prospects in the field of supercapacitors.

Description

Conductive polymers based on quinacridone, their preparation methods and applications Technical Field

[0001] This invention relates to the field of energy storage materials technology, specifically to conductive polymers based on quinacridone, their preparation methods, and applications. Background Technology

[0002] Renewable energy sources, due to their sustainability, are ideal alternatives to fossil fuels. Most renewable energy sources are intermittent, such as solar and wind power, leading to a significant demand for energy storage devices. Supercapacitors, as electrochemical energy storage devices, possess many desirable characteristics compared to traditional capacitors and batteries in energy storage systems, such as rapid charge / discharge rates, flexibility, and higher power density. They have the ability to bridge the gap between high-energy-density batteries and high-power-density capacitors. Therefore, supercapacitors hold promise for meeting the growing demand for energy storage and transmission and are attracting widespread attention among various energy storage devices.

[0003] Improving specific capacitance is a crucial research direction for supercapacitors, with the selection of electrode materials being particularly important. Compared to other materials, conductive polymers possess advantages such as excellent electrochemical properties, ease of structural modification, low cost, and environmental friendliness. Charge storage can be achieved through redox reactions on the electrode surface and in the bulk, making them potential electrode materials for supercapacitors. Quinacridone derivatives have attracted widespread interest in applications such as organic optoelectronic devices and ion detection. The Wang Yue research group at Jilin University synthesized an indenequinacridone derivative using 2-amino-substituted fluorene as a starting material, studied the effects of solvent polarity, concentration, and temperature on intermolecular hydrogen bonds, and investigated its film-forming properties. The Hua Jianli research group designed a thiocarbonyl-substituted quinacridone using the high-efficiency luminescence properties and carbonyl reactivity of quinacridone, and applied it to Hg... 2+ It has found applications in the field of probes.

[0004] Current research on quinacridones in energy storage and electrochromic materials faces challenges due to the poor solubility of quinacridone-based polymers. Therefore, they are typically applied directly to transparent conductive substrates, such as ITO, via electrochemical polymerization. However, ITO is essentially a glass substrate with a dense conductive layer of indium tin oxide (ITO), lacking microporous structures. Applying quinacridone-based polymer films directly to the ITO surface via electrochemical polymerization also results in a flat surface layer, as microporous structures are virtually nonexistent. For supercapacitors, a porous polymer film structure is crucial, providing more channels for ion insertion and extraction, thus enhancing capacitance. The inherent solubility of existing quinacridone-based polymers limits their application in energy storage electrode materials to electrochemical polymerization, restricting the choice of conductive substrates for polymerization. This electrochemical polymerization process severely hinders large-area processing and application, impeding industrial production. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a conductive polymer based on quinacridone and its preparation method, and apply it to energy storage color-changing electrode materials. This overcomes the problem that the conductive polymer based on quinacridone in the prior art has poor solubility, which means that when it is used as an energy storage electrode material, it can only be prepared by electrochemical polymerization film formation, which is not conducive to large-area processing.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] The first objective of this invention is to provide a conductive polymer based on quinacridone, as shown in formula (I):

[0008]

[0009] In equation (I), n represents the average degree of polymerization, and n takes values ​​from 10 to 2000.

[0010] Quinacridones are molecules containing imine groups and are commonly used as acceptor units. The nitrogen atoms in their molecular structure can also undergo redox reactions. Propylene dioxothiophene (proDOT), due to its stable oxidation state and good conductivity, is often used as an electrode material for p-type supercapacitors. Existing quinacridone-based conductive polymers suffer from poor solubility, therefore, their use as energy storage electrode materials can only be achieved through electrochemical polymerization film formation. However, in this invention, by introducing proDOT into the quinacridone system, it was found that not only was the polymer's solubility improved, but the resulting quinacridone-based conductive polymer can also be solution-processed, meaning it dissolves in solvents for large-area processing and use.

[0011] A second objective of this invention is to provide a method for preparing the above-described conductive polymer, comprising the following steps:

[0012] (1) The quinacridone derivative, N-bromosuccinimide and N,N-dimethylformamide were added to the reaction flask in sequence, and the reaction was carried out by heating in the dark. After separation and purification, the brominated product as shown in formula (III) was obtained, wherein the quinacridone derivative was as shown in formula (II).

[0013] (2) The brominated product, proDOT, K2CO3, catalyst and neopentanoic acid as shown in formula (III) are added to the reaction flask, and N,N-dimethylformamide is added under nitrogen protection. The mixture is heated and reacted. After the reaction is completed, the conductive polymer based on quinacridone is obtained by separation and purification, wherein the proDOT is as shown in formula (IV).

[0014] (II) (III) (Ⅳ)

[0015] Preferably, the molar ratio of the quinacridone derivative and N-bromosuccinimide in step (1) is 1:2 to 5.

[0016] Preferably, the volume of N,N-dimethylformamide added in step (1) is 8 to 16 mL / g based on the mass of the quinacridone derivative.

[0017] Preferably, the molar ratio of the brominated product, proDOT, and K2CO3 in step (2) is 1:1:2 to 3.

[0018] Preferably, the volume of N,N-dimethylformamide added in step (2) is 10-15 mL / g based on the mass of the brominated product.

[0019] Preferably, the heating reaction temperature in step (1) is 120-140°C, and the mixing and heating reaction temperature in step (2) is 90-140°C.

[0020] Further preferred, the separation and purification method in step (1) is as follows: after the reaction is completed, the mixture is extracted three times with water and dichloromethane. After the extract is concentrated, it is dehydrated with anhydrous sodium sulfate and purified by column chromatography. Silica gel is used as the stationary phase, and dichloromethane and petroleum ether are used as the mobile phase. The eluent containing the target compound is collected, the solvent is removed by rotary evaporation and dried.

[0021] Step (2) specifically involves adding the brominated product (C10QA-2Br) as shown in Formula (III), proDOT, K2CO3, and appropriate amounts of palladium acetate catalyst and neopentanoic acid to a three-necked round-bottom flask, and adding dry N,N-dimethylformamide under nitrogen protection. The mixture is then heated and stirred for 24 hours. The reaction mixture is cooled to room temperature and then precipitated in methanol. The solid is collected, dried, and placed in a Sogret extraction sleeve, and washed with methanol, acetone, hexane, and chloroform, respectively. The chloroform fraction is concentrated and precipitated in methanol. The solid is collected, dried, and a dark solid based conductive polymer of quinacridone is obtained.

[0022] A third objective of this invention is to provide the application of the quinacridone-based conductive polymer or the quinacridone-based conductive polymer prepared by the above-described method in energy storage color-changing electrode materials.

[0023] A fourth objective of the present invention is to provide an energy storage color-changing electrode comprising a nickel foam substrate and a quinacridone-based conductive polymer attached to the surface of the nickel foam substrate.

[0024] The fifth objective of this invention is to provide a method for preparing the aforementioned energy storage color-changing electrode, comprising the following steps:

[0025] (S.1) Dissolve the quinacridone-based conductive polymer in an organic solvent to prepare a quinacridone-based conductive polymer solution; (S.2) Spray the quinacridone-based conductive polymer solution onto the surface of a nickel foam substrate and dry it to obtain the energy storage color-changing electrode.

[0026] Preferably, the conductive polymer solution based on quinacridone comprises a conductive polymer based on quinacridone and chloroform, wherein the concentration of the conductive polymer based on quinacridone in the solution is 3–8 mg / mL.

[0027] Nickel foam possesses a loose and porous surface morphology, which can serve as a conductive substrate, increasing the specific surface area in contact with polymers. Simultaneously, the porous structure of nickel foam itself can contribute to double-layer capacitance properties. Using nickel foam as a conductive substrate and quinacridone-based polymers as electroactive materials holds promise for obtaining novel energy storage and color-changing electrode materials, improving their specific capacitance performance. Furthermore, direct spraying allows for large-area processing, while electrochemical polymerization is limited to small-area processing. Directly sprayed polymer particles can better adhere to nickel foam and penetrate deep into the polymer interior.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] (1) The conductive polymer based on quinacridone in this invention has good solubility. It can be dissolved in a solvent to form a solution and then sprayed to achieve large-area processing. It does not rely on electrochemical polymerization to prepare a film, thus simplifying the preparation process of electrode materials. It has great application prospects as an energy storage color-changing electrode material in industrial production.

[0030] (2) Using nickel foam as a framework and conductive substrate, the porous structure of nickel foam contributes to the double-layer capacitance, thus playing a synergistic role in energy storage. In addition, the porous structure of nickel foam can increase the specific surface area in contact with the polymer, thereby facilitating charge transport and ion insertion and extraction processes;

[0031] (3) Conductive polymers based on quinacridone are used as energy storage and color-changing materials, which can achieve high current densities (0.5 mA / cm²). 2 It still has a high areal capacitance (3.1 mF / cm²). 2 It exhibits good charge-discharge stability under different current densities, and the amount of stored energy can be determined by observing changes in electrode color, making it a promising candidate for application in the field of supercapacitors. Attached Figure Description

[0032] Figure 1 shows the synthetic route of the conductive polymer based on quinacridone in this invention.

[0033] Figure 2 shows the cyclic voltammetry curves of the nickel foam electrode in this invention at different scan rates.

[0034] Figure 3 shows the cyclic voltammetry curves of the energy storage color-changing electrode based on quinacridone conductive polymer with nickel foam substrate in this invention at different scan rates.

[0035] Figure 4 shows the charge-discharge curves of the nickel foam electrode in this invention at different current densities.

[0036] Figure 5 shows the charge-discharge curves of the energy storage color-changing electrode based on nickel foam and quinacridone conductive polymer in this invention at different current densities.

[0037] Figure 6 shows the area specific capacitance curves of the energy storage color-changing electrode based on nickel foam and quinacridone conductive polymer in this invention at different current densities.

[0038] Figure 7 shows the electrochromic properties of the energy storage color-changing electrode based on quinacridone conductive polymer with nickel foam as the substrate in this invention at different voltages. Detailed Implementation

[0039] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. Those skilled in the art will be able to implement the present invention based on these descriptions. Furthermore, the embodiments of the present invention described below are generally only some, not all, of the embodiments of the present invention. Therefore, all other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort should fall within the scope of protection of the present invention.

[0040] The synthetic route of the conductive polymer based on quinacridone in this invention is shown in Figure 1.

[0041] Example 1: Preparation of a color-changing energy storage electrode based on a quinacridone conductive polymer using nickel foam as a substrate (1) Synthesis of the quinacridone conductive polymer

[0042] Under nitrogen protection, quinacridone derivative (0.6 g, 1 mmol), N-bromosuccinimide (NBS) (0.62 g, 3.5 mmol), and 8 mL of N,N-dimethylformamide (DMF) were added sequentially to a reaction flask. The mixture was heated to reflux (120–140 °C) and reacted in the dark for 24 h. After the reaction was completed, the mixture was extracted three times with water and dichloromethane. The extract was concentrated and dehydrated with anhydrous sodium sulfate. The extract was then purified by column chromatography using silica gel as the stationary phase and dichloromethane and petroleum ether as the mobile phase. The eluent containing the target compound was collected, the solvent was removed by rotary evaporation, and the extract was dried to obtain C10QA-2Br as shown in formula (a).

[0043] ② The brominated product (C10QA-2Br) shown in formula (a) (374 mg, 0.50 mmol), proDOT (220 mg, 0.50 mmol), K2CO3 (172 mg, 1.25 mmol), and appropriate amounts of palladium acetate catalyst and neopentanoic acid were added to a three-necked round-bottom flask. Under nitrogen protection, 5 mL of dry N,N-dimethylformamide was added, and the mixture was heated at 120 °C and stirred for 24 h. The reaction mixture was cooled to room temperature and then precipitated in methanol. The solid was collected, dried, and placed in a Sogret extraction sleeve and washed with methanol, acetone, hexane, and chloroform, respectively. The chloroform fraction was concentrated and precipitated in methanol. The solid was collected, dried, and a dark solid was obtained as shown in formula (b) of the quinacridone-based conductive polymer (pQA-proDOT).

[0044] (a) (b)

[0045] (2) Cleaning the nickel foam

[0046] The nickel foam was cut into rectangles of approximately 0.9cm × 4cm, and then immersed in hydrochloric acid, deionized water and anhydrous ethanol in sequence and ultrasonically cleaned for 15 minutes. The nickel foam was then vacuum dried at 60°C for 2 hours to obtain a clean nickel foam conductive substrate.

[0047] (3) Preparation of a conductive polymer energy storage and color-changing electrode based on quinacridone with nickel foam as the substrate

[0048] The conductive polymer based on quinacridone shown in formula (b) was dissolved in chloroform to prepare a 4 mg / mL solution. Using nickel foam (0.9 cm × 4 cm) as a conductive substrate, the solution was uniformly sprayed onto the surface of the nickel foam using a spray gun. The nickel foam electrode material after spraying was dried in an oven for 1 h to remove chloroform, thus obtaining an energy storage color-changing electrode based on the conductive polymer of quinacridone with nickel foam as the substrate.

[0049] Example 2: Preparation of a color-changing energy storage electrode based on a quinacridone conductive polymer using nickel foam as a substrate (1) Synthesis of the quinacridone conductive polymer

[0050] Under nitrogen protection, quinacridone derivative (0.6 g, 1 mmol), N-bromosuccinimide (NBS) (0.36 g, 2 mmol), and N,N-dimethylformamide (DMF) 4.8 mL were added sequentially to a reaction flask, heated to reflux (120–140 °C), and reacted in the dark for 24 h. After the reaction was completed, the mixture was extracted three times with water and dichloromethane. The extract was concentrated and dehydrated with anhydrous sodium sulfate, and then purified by column chromatography using silica gel as the stationary phase and dichloromethane and petroleum ether as the mobile phase. The eluent containing the target compound was collected, the solvent was removed by rotary evaporation, and the eluent was dried to obtain C10QA-2Br as shown in formula (a).

[0051] ② The brominated product (C10QA-2Br) (374 mg, 0.50 mmol), proDOT (220 mg, 0.50 mmol), K2CO3 (172 mg, 1 mmol), and appropriate amounts of palladium acetate catalyst and neopentanoic acid were added to a three-necked round-bottom flask. Under nitrogen protection, 3.7 mL of dry N,N-dimethylformamide was added, and the mixture was stirred at 90 °C for 24 h. The reaction mixture was cooled to room temperature and then precipitated in methanol. The solid was collected, dried, and placed in a Sogret extraction sleeve and washed with methanol, acetone, hexane, and chloroform, respectively. The chloroform fraction was concentrated and precipitated in methanol. The solid was collected, dried, and a dark solid was obtained as shown in formula (b) of the quinacridone-based conductive polymer (pQA-proDOT).

[0052] (a) (b)

[0053] (2) Cleaning the nickel foam

[0054] The nickel foam was cut into rectangles of approximately 0.9cm × 4cm, and then immersed in hydrochloric acid, deionized water and anhydrous ethanol in sequence and ultrasonically cleaned for 15 minutes. The nickel foam was then vacuum dried at 60°C for 2 hours to obtain a clean nickel foam conductive substrate.

[0055] (3) Preparation of a conductive polymer energy storage and color-changing electrode based on quinacridone with nickel foam as the substrate

[0056] The conductive polymer based on quinacridone shown in formula (b) was dissolved in chloroform to prepare a 6 mg / mL solution. Using nickel foam (0.9 cm × 4 cm) as a conductive substrate, the solution was uniformly sprayed onto the surface of the nickel foam using a spray gun. The nickel foam electrode material after spraying was dried in an oven for 1 h to remove chloroform, thus obtaining an energy storage color-changing electrode based on the conductive polymer of quinacridone with nickel foam as the substrate.

[0057] Example 3: Preparation of a color-changing energy storage electrode based on a quinacridone conductive polymer using nickel foam as a substrate (1) Synthesis of the quinacridone conductive polymer

[0058] Under nitrogen protection, quinacridone derivative (0.6 g, 1 mmol), N-bromosuccinimide (NBS) (0.89 g, 5 mmol), and N,N-dimethylformamide (DMF) 9.6 mL were added sequentially to a reaction flask, heated to reflux (120–140 °C), and reacted in the dark for 24 h. After the reaction was completed, the mixture was extracted three times with water and dichloromethane. The extract was concentrated and dehydrated with anhydrous sodium sulfate, and then purified by column chromatography using silica gel as the stationary phase and dichloromethane and petroleum ether as the mobile phase. The eluent containing the target compound was collected, the solvent was removed by rotary evaporation, and the eluent was dried to obtain C10QA-2Br as shown in formula (a).

[0059] ② The brominated product (C10QA-2Br) shown in formula (a) (374 mg, 0.50 mmol), proDOT (220 mg, 0.50 mmol), K2CO3 (172 mg, 1.5 mmol), and appropriate amounts of palladium acetate catalyst and neopentanoic acid were added to a three-necked round-bottom flask, and 5.6 mL of dry N,N-dimethylformamide was added under nitrogen protection. The mixture was heated at 140 °C and stirred for 24 h. The reaction mixture was cooled to room temperature and then precipitated in methanol. The solid was collected, dried, and placed in a Sogret extraction sleeve and washed with methanol, acetone, hexane, and chloroform, respectively. The chloroform fraction was concentrated and precipitated in methanol. The solid was collected, dried, and a dark solid was obtained as shown in formula (b) of the quinacridone-based conductive polymer (pQA-proDOT).

[0060] (a) (b)

[0061] (2) Cleaning the nickel foam

[0062] The nickel foam was cut into rectangles of approximately 0.9cm × 4cm, and then immersed in hydrochloric acid, deionized water and anhydrous ethanol in sequence and ultrasonically cleaned for 15 minutes. The nickel foam was then vacuum dried at 60°C for 2 hours to obtain a clean nickel foam conductive substrate.

[0063] (3) Preparation of a conductive polymer energy storage and color-changing electrode based on quinacridone with nickel foam as the substrate

[0064] The conductive polymer based on quinacridone shown in formula (b) was dissolved in chloroform to prepare a solution of 8 mg / mL. Using nickel foam (0.9 cm × 4 cm) as a conductive substrate, the solution was uniformly sprayed onto the surface of the nickel foam using a spray gun. The nickel foam electrode material after spraying was dried in an oven for 1 h to remove chloroform, thus obtaining an energy storage color-changing electrode based on the conductive polymer of quinacridone with nickel foam as the substrate.

[0065] Example 4: Preparation of an energy storage color-changing electrode based on a quinacridone conductive polymer with nickel foam as the substrate. The difference between this example and Example 1 is that a 3 mg / mL solution was used when spraying the quinacridone conductive polymer.

[0066] Example 5: Preparation of an energy storage color-changing electrode based on a quinacridone conductive polymer with nickel foam as the substrate. The difference between this example and Example 1 is that a 5 mg / mL solution is used when spraying the quinacridone conductive polymer.

[0067] Comparative Example 1: Preparation of blank nickel foam electrode material

[0068] Specifically as follows:

[0069] Nickel foam was cut into rectangles of approximately 0.9 cm × 4 cm and then immersed in hydrochloric acid, deionized water, and anhydrous ethanol in sequence and ultrasonically cleaned for 15 min. The nickel foam was then vacuum dried at 60 °C for 2 h to obtain a clean conductive nickel foam substrate. The electrochemical and energy storage properties of the nickel foam were then studied.

[0070] [Performance Testing]

[0071] The electrochemical, electrochromic, and supercapacitor performance test results of Example 1 and Comparative Example 1 are as follows:

[0072] 1. Electrochemical and charge-discharge performance tests of blank nickel foam electrode materials:

[0073] (1) Electrochemical performance of blank nickel foam electrode material: The test method was as follows: 0.387 g of tetrabutylammonium hexafluorophosphate was added to a 10 mL volumetric flask and diluted to volume with chromatographic grade acetonitrile to obtain a 0.1 mol / L solution, which was used as the blank supporting electrolyte solution. Using the blank electrolyte solution as the test solution, a three-electrode system was constructed with the nickel foam electrode as the working electrode, a Pt sheet as the counter electrode, and Ag / AgCl as the reference electrode. The test voltage window was 0.6–1.1 V, and the scan rate was 50–500 mV / s. The test results are shown in Figure 2. As can be seen from Figure 2, the nickel foam electrode has a certain redox capability.

[0074] (2) Charge-discharge performance of the nickel foam electrode was tested as follows: 0.387 g of tetrabutylammonium hexafluorophosphate was added to a 10 mL volumetric flask and diluted to volume with chromatographic grade acetonitrile to obtain a 0.1 mol / L solution, which was used as the blank supporting electrolyte solution. Using the blank electrolyte solution as the test solution, a three-electrode system was constructed with the nickel foam electrode material as the working electrode, a Pt sheet as the counter electrode, and Ag / AgCl as the reference electrode. The test voltage window was 0.6–1.1 V, and the current density was 0.1 mA / cm². 2 0.2mA / cm 2 0.3mA / cm 2 0.5mA / cm 2 The charge-discharge performance of the electrode material was tested under constant current conditions, and the test results are shown in Figure 4. As can be seen from Figure 4, the nickel foam electrode has a certain charge storage capacity during the charge-discharge process.

[0075] 2. Electrochemical performance, charge-discharge performance, and electrochromic performance testing of an energy storage color-changing electrode based on a nickel foam substrate and a quinacridone-based conductive polymer:

[0076] (1) The electrochemical performance of the energy storage color-changing electrode based on nickel foam and a conductive polymer of quinacridone was tested. The test method was as follows: 0.387 g of tetrabutylammonium hexafluorophosphate was added to a 10 mL volumetric flask and diluted to volume with chromatographic grade acetonitrile to obtain a 0.1 mol / L solution, which was used as the blank supporting electrolyte solution. Using the blank electrolyte solution as the test solution, the energy storage color-changing electrode based on nickel foam and a conductive polymer of quinacridone was used as the working electrode, Pt sheet as the counter electrode, and Ag / AgCl as the reference electrode to form a three-electrode system. The test voltage window was 0.6–1.1 V, and the scan rate was 50–500 mV / s. The test results are shown in Figure 3. As can be seen from Figure 3, the energy storage color-changing electrode based on nickel foam and a conductive polymer of quinacridone has excellent redox behavior. Its cyclic voltammetry curve is close to rectangular in the voltage range of 0.6 V–1.1 V, indicating that it may have excellent charge storage capacity.

[0077] (2) The charge-discharge performance of the energy storage color-changing electrode based on nickel foam and a conductive polymer of quinacridone was tested as follows: 0.387 g of tetrabutylammonium hexafluorophosphate was added to a 10 mL volumetric flask and diluted to volume with chromatographic grade acetonitrile to obtain a 0.1 mol / L solution, which was used as the blank supporting electrolyte solution. Using the blank electrolyte solution as the test solution, the energy storage color-changing electrode material based on nickel foam and a conductive polymer of quinacridone was used as the working electrode, a Pt sheet as the counter electrode, and Ag / AgCl as the reference electrode to form a three-electrode system. The test voltage window was 0.6–1.1 V, and the current density was 0.1 mA / cm². 2 0.2mA / cm 2 0.3mA / cm 2 0.5mA / cm 2 The charge-discharge performance of the electrode material was tested under constant current conditions, and the test results are shown in Figure 5. As can be seen from Figure 5, the energy storage color-changing electrode based on quinacridone conductive polymer with nickel foam as the substrate exhibits excellent charge storage capability during charge and discharge. Furthermore, the areal capacitance of the polymer energy storage color-changing electrode under different current densities was calculated, as shown in Figure 6. The areal capacitance of the polymer does not change significantly under different current densities, indicating that the polymer energy storage color-changing electrode has good charge-discharge stability under different current densities.

[0078] (3) The electrochromic performance of the energy storage color-changing electrode based on nickel foam and a conductive polymer based on quinacridone was tested as follows: 0.387 g of tetrabutylammonium hexafluorophosphate was added to a 10 mL volumetric flask and diluted to volume with chromatographic grade acetonitrile to obtain a 0.1 mol / L solution, which was used as the blank supporting electrolyte solution. Using the blank electrolyte solution as the test solution, the energy storage color-changing electrode material based on nickel foam and a conductive polymer based on quinacridone was used as the working electrode, Pt sheet as the counter electrode, and Ag / AgCl as the reference electrode to form a three-electrode system. The electrochromic performance of the film in the wavelength range of 380–1100 nm was tested, and the test results are shown in Figure 7. As shown in Figure 7, when the applied voltage increases from 0V to 1.1V, the color of the energy storage color-changing electrode material based on nickel foam and quinacridone conductive polymer gradually changes from yellow to yellow-green. The color-changing process is shown in Table 1, indicating that the energy storage color-changing electrode material based on nickel foam and quinacridone conductive polymer has good electrochromic properties.

[0079] Table 1. Color change process of electrode materials

[0080] Voltage and color: 0V yellow, 0.6V light yellow, 1.1V yellow-green. surface.

Claims

1. A conductive polymer based on quinacridone, characterized in that, As shown in equation (Ⅰ): (Ⅰ) In equation (I), n represents the average degree of polymerization, and n takes values ​​from 10 to 2000.

2. A method for preparing the conductive polymer of claim 1, characterized in that, The process includes the following steps: (1) adding a quinacridone derivative, N-bromosuccinimide, and N,N-dimethylformamide sequentially to a reaction flask, heating and reacting in the dark, and then separating and purifying to obtain the brominated product as shown in formula (III), wherein the quinacridone derivative is shown in formula (II); (2) adding the brominated product as shown in formula (III), proDOT, K2CO3, catalyst, and neopentanoic acid to a reaction flask, and adding N,N-dimethylformamide under nitrogen protection, mixing and heating to react, and after the reaction is completed, separating and purifying to obtain the conductive polymer based on quinacridone, wherein the proDOT is shown in formula (IV); (II) (Ⅲ) (Ⅳ) 3. The method as described in claim 2, characterized in that, The molar ratio of the quinacridone derivative and N-bromosuccinimide in step (1) is 1:2 to 5.

4. The method as described in claim 2 or 3, characterized in that, The volume of N,N-dimethylformamide added in step (1) is 8 to 16 mL / g based on the mass of the quinacridone derivative.

5. The method as described in claim 2, characterized in that, The molar ratio of the brominated product, proDOT, and K2CO3 in step (2) is 1:1:2-3.

6. The method as described in claim 2 or 5, characterized in that, The volume of N,N-dimethylformamide added in step (2) is 10-15 mL / g based on the mass of the brominated product.

7. The method as described in claim 2, characterized in that, The heating reaction temperature in step (1) is 120-140°C, and the mixing heating reaction temperature in step (2) is 90-140°C.

8. The application of the conductive polymer based on quinacridone as described in claim 1 or the conductive polymer based on quinacridone prepared by the method described in any one of claims 2 to 7 in energy storage color-changing electrode materials.

9. An energy storage color-changing electrode, characterized in that, The invention includes a nickel foam substrate and a conductive polymer based on quinacridone as described in claim 1, which is attached to the surface of the nickel foam substrate.

10. A method for preparing the energy storage color-changing electrode according to claim 9, characterized in that, Includes the following steps: (S.1) Dissolve the quinacridone-based conductive polymer in an organic solvent to prepare a quinacridone-based conductive polymer solution; (S.2) Spray the quinacridone-based conductive polymer solution onto the surface of a nickel foam substrate and dry it to obtain the energy storage color-changing electrode.

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