Electrode materials, electrode plates, preparation methods, and applications of all-organic batteries

Abstract

The present invention relates to an electrode material, electrode plate, preparation method, and application for an all-organic battery. The positive electrode material is a graphene composite nanomaterial rGO-g-PTMA, and the negative electrode material is a viologen cationic polymer PVBVEt(PF6)2. The electrode plates are synthesized from the electrode materials, a polyvinylidene fluoride solution, and a conductive agent, and then assembled into an all-organic battery. Compared with the existing technology, the present invention utilizes the graphene composite nanomaterial rGO-g-PTMA and the viologen cationic polymer PVBVEt(PF6)2 to produce a green and pollution-free all-organic battery with higher voltage, a stable charge and discharge voltage platform, and a large specific capacity.

Description

Technical Field

[0001] The present invention relates to the fields of new energy materials and electrochemistry, and in particular to an electrode material, an electrode plate, a preparation method and an application of an all-organic battery. Background Art

[0002] Over the past few decades, lithium-ion batteries have been widely developed and applied in various fields as an alternative energy source to fossil fuels. The cathode materials of traditional commercial lithium-ion batteries are typically transition metal oxides (such as LiFePO4 and LiCoO2), and the anode materials are typically graphite. However, the explosive growth in demand and the ever-expanding range of applications have increasingly highlighted the shortcomings of traditional lithium batteries, such as transition metal resource shortages, rising costs, poor safety, difficult waste recycling, and environmental pollution. Unlike inorganic electrode materials, organic electrode materials typically contain only elements such as C, H, O, N, and S, thus avoiding resource shortages and waste pollution. Furthermore, organic materials can be synthesized using various methods to achieve a variety of structures to meet diverse application requirements. Furthermore, during operation, inorganic materials are prone to significant deformation as ions are inserted and removed, which can disrupt the material structure and cause irreversible capacity fading and safety issues. Organic materials, on the other hand, are generally more flexible, thus avoiding these issues. Therefore, replacing traditional inorganic electrode materials with organic electrode materials can help address the bottlenecks currently facing commercial lithium batteries. However, existing all-organic batteries also have problems such as low voltage, unstable voltage platform and poor specific capacity. Therefore, solving the above problems will help to better develop the application of all-organic batteries. Summary of the Invention

[0003] The purpose of the present invention is to provide an electrode material, electrode plate, preparation method and application of an all-organic battery in order to overcome the defects of the above-mentioned prior art such as low voltage, unstable voltage platform and poor specific capacity of the all-organic battery.

[0004] The purpose of the present invention can be achieved by the following technical solutions:

[0005] One of the technical solutions of the present invention is to provide an electrode material for an all-organic battery, including an organic positive electrode material and an organic negative electrode material. The organic positive electrode material is named rGO-g-PTMA, which includes reduced graphene oxide (rGO) and poly (4-methacryloyloxy)-2,2,6,6-tetramethylpiperidinyl nitroxide (PTMA) grafted on the reduced graphene oxide; the organic negative electrode material is a viologen cationic polymer.

[0006] Furthermore, the mass of the poly (4-methacryloyloxy)-2,2,6,6-tetramethylpiperidinyl)nitroxide radical accounts for 45-55% of the total mass of rGO-g-PTMA, and the structural formula of the PVBVEt(PF6)2 is as follows: n=2~100.

[0007] The second technical solution of the present invention is to provide a method for preparing electrode materials for an all-organic battery, which is divided into the preparation of organic positive electrode materials and the preparation of organic negative electrode materials, and specifically includes the following steps:

[0008] (1) Preparation method of organic cathode material:

[0009] (1-1) Reduced graphene oxide is mixed with N-methylpyrrolidone solvent, and the monomer 2,2,6,6-tetramethyl-4-piperidinyl methacrylate and the initiator azobisisobutyronitrile are added under a nitrogen environment. The oxygen is removed by lyophilization, and the filtrate is filtered. The filtrate is washed with acetone multiple times to obtain the intermediate product rGO-g-PTMPM;

[0010] (1-2) mixing the rGO-g-PTMPM obtained in step (1-1) with methanol, adding deionized water, disodium ethylenediaminetetraacetic acid, sodium tungstate dihydrate, and hydrogen peroxide to react, washing with deionized water multiple times after the reaction, and freeze-drying to obtain an organic cathode material rGO-g-PTMA;

[0011] (2) Preparation method of organic negative electrode material:

[0012] (2-1) 4,4'-Bipyridine was dissolved in acetonitrile and bromoethane was added for reaction. After the reaction, the mixture was cooled to room temperature and the solvent was removed by distillation under reduced pressure. The resulting precipitate was dissolved in N,N-dimethylformamide and filtered. The filtrate was then precipitated with glacial ether to obtain VEtBr as a white solid product.

[0013] (2-2) Dissolving the VEtBr obtained in step (2-1) in acetonitrile, adding vinylbenzyl chloride for reaction, and filtering to remove the solvent after the reaction. The resulting precipitate is washed with diethyl ether several times and dried in vacuo to obtain a solid product, VBVEtBrCl;

[0014] (2-3) Dissolving the VBVEtBrCl obtained in step (2-2) in deionized water, adding potassium persulfate as an initiator, mixing, freezing, evacuating, then introducing nitrogen to deoxygenate, and freeze-drying to obtain a yellow product, PVBVEtBrCl;

[0015] (2-4) Dissolving the PVBVEtBrCl obtained in step (2-3) with deionized water, adding an NH4PF6 aqueous solution and stirring to precipitate an off-white solid, washing the off-white solid with deionized water several times, and vacuum drying to obtain an organic negative electrode material PVBVEt(PF6)2.

[0016] Furthermore, in step (1-1), the ratio of the reduced graphene oxide: N-methylpyrrolidone: 2,2,6,6-tetramethyl-4-piperidinyl methacrylate: initiator azobisisobutyronitrile is: 400 mg: 100 mL: 8 g: 87 mg; the reaction temperature for deoxygenation is 70° C., and the reaction time is 20 h;

[0017] In step (1-2), the mass ratio of the rGO-g-PTMPM to methanol is 1:182; deionized water, disodium ethylenediaminetetraacetic acid, sodium tungstate dihydrate and 30% hydrogen peroxide are added twice, respectively. The ratio of deionized water: disodium ethylenediaminetetraacetic acid: sodium tungstate dihydrate: 30% hydrogen peroxide solution added for the first time is 15 mL: 180 mg: 125 mg: 15 mL, the reaction temperature is room temperature, and the reaction time is 24 h; the ratio of deionized water: disodium ethylenediaminetetraacetic acid: sodium tungstate dihydrate: 30% hydrogen peroxide solution added for the second time is 5 mL: 65 mg: 62 mg: 5 mL, the reaction temperature is room temperature, and the reaction time is 24 h.

[0018] Furthermore, in step (2-1), the ratio of 4,4'-bipyridine to bromoethane is 5 g:600 μL; the reaction temperature after adding bromoethane is 90°C, and the reaction time is 24 h; the temperature of the added N,N-dimethylformamide is 100°C;

[0019] In step (2-2), the ratio of VEtBr: vinylbenzyl chloride is 0.96 g: 2 mL; the reaction temperature after adding vinylbenzyl chloride is 80° C., and the reaction time is 24 h; the vacuum drying temperature is 40° C., and the time is 4 h;

[0020] In step (2-3), the ratio of VBVEtBrCl to initiator potassium persulfate is 0.52 g:22.6 mg; before freeze-drying, the deoxygenated reaction system is reacted at 85° C. for 4 h.

[0021] In step (2-4), the vacuum drying temperature is 40° C. and the time is 8 h.

[0022] The third technical solution of the present invention is to provide an electrode plate for an all-organic battery, wherein the electrode plate contains the electrode material of the all-organic battery provided by the first technical solution.

[0023] A fourth technical solution of the present invention is to provide a method for preparing an electrode sheet of an all-organic battery, comprising the following steps:

[0024] (1) dissolving polyvinylidene fluoride in NMP solvent to prepare a polyvinylidene fluoride solution with a concentration of 0.02 g / mL;

[0025] (2) mixing the organic positive electrode material rGO-g-PTMA, polyvinylidene fluoride solution, and a first conductive agent, and adding NMP solvent and stirring to obtain a black and shiny first slurry; mixing the organic negative electrode material PVBVEt(PF6)2, polyvinylidene fluoride solution, and a second conductive agent, and adding NMP solvent and stirring to obtain a black and shiny second slurry;

[0026] (3) The first slurry and the second slurry obtained in step (2) are applied to aluminum foil respectively, and then vacuum dried and pressed into sheets to finally obtain a battery positive electrode sheet and a battery negative electrode sheet respectively.

[0027] Furthermore, in step (2), the mass ratio of the organic positive electrode material rGO-g-PTMA, polyvinylidene fluoride solution, and the first conductive agent is 8:1:1; the mass ratio of the organic negative electrode material PVBVEt(PF6)2, polyvinylidene fluoride solution, and the second conductive agent is 5:4:1; the first conductive agent is Super P, and the second conductive agent is Ketjen black.

[0028] Furthermore, in step (3), the vacuum drying temperature is 70° C. and the time is 12 h.

[0029] The fifth technical solution of the present invention is to provide an application of an electrode plate of an all-organic battery as provided in the third technical solution, wherein the electrode plate is used to be assembled into an all-organic battery.

[0030] The assembly method of the all-organic battery is as follows: a drop of electrolyte is dripped into the positive electrode shell of a 2025 button battery, the positive electrode plate of the battery is placed, three drops of electrolyte are dripped on the positive electrode plate of the battery, a Celgard 2400 separator is placed, three drops of electrolyte are dripped on the separator, the negative electrode plate of the battery is placed, a piece of nickel foam is placed, and finally the negative electrode shell is covered and compacted to obtain a button battery.

[0031] Furthermore, the electrolyte is a 2M lithium perchlorate (LiClO4) tetraethylene glycol dimethyl ether (TEGDME) solution.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] (1) The present invention adopts all-organic active electrode materials, with graphene composite nanomaterial rGO-g-PTMA as the positive electrode material and viologen cationic polymer PVBVEt(PF6)2 as the negative electrode material. The all-organic battery of the present invention has redox peaks at both 1.6V and 1.1V, showing a higher voltage, and a stable charge and discharge voltage platform at 1.6V and 1.1V. In addition, the all-organic battery of the present invention has a high capacity of up to 145.4mAh g -1The high discharge specific capacity, excellent coulombic efficiency and low resistance of 150Ω reflect the excellent performance of the all-organic battery of the present invention and are suitable for practical applications.

[0034] (2) The all-organic battery electrode material of the present invention does not contain rare transition metal elements and other polluting elements that are difficult to recycle and treat, has low production cost, and is green, environmentally friendly and sustainable. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is the cyclic voltammetry curve of rGO-g-PTMA / PVBVEt(PF6)2 all-organic battery.

[0036] Figure 2 This is the charge and discharge curve of rGO-g-PTMA / PVBVEt(PF6)2 all-organic battery.

[0037] Figure 3 This is the 200 cycle performance curve of rGO-g-PTMA / PVBVEt(PF6)2 all-organic battery.

[0038] Figure 4 This is the impedance curve of rGO-g-PTMA / PVBVEt(PF6)2 all-organic battery.

[0039] Figure 5 This is the charge and discharge curve of the rGO / PTMA / / PVBVEt(PF6)2 all-organic battery described in Example 1.

[0040] Figure 6 This is the charge and discharge curve of the rGO-g-PTMA / PVAEt(PF6)2 all-organic battery described in Example 2. DETAILED DESCRIPTION

[0041] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0042] In the following examples, unless otherwise specified, raw materials or processing techniques are conventional commercially available raw materials or conventional processing techniques in the art.

[0043] Example 1:

[0044] A method for preparing an organic cathode material for an all-organic battery comprises the following steps:

[0045] (1) Free radical polymerization: Add 400 mg of reduced graphene oxide and 100 mL of N-methylpyrrolidone to a Schlenk tube equipped with a stirrer and ultrasonically disperse for 1 h. Add 8 g (36 mmol) of 2,2,6,6-tetramethyl-4-piperidinyl methacrylate (TMPM) and 87 mg (0.53 mmol) of azobisisobutyronitrile (AIBN) under nitrogen atmosphere. The molar amount of initiator AIBN added is 1.5% of the molar amount of monomer TMPM. After deoxygenation three times, react in an oil bath at 70°C for 12 h and quench the reaction with air. Filter the reaction solution with a 0.22 μm pore size organic phase filter membrane, and then wash the solid portion with acetone three times to remove free polymer. Disperse 645 mg of the product rGO-g-PTMPM in 150 mL of methanol.

[0046] (2) Oxidation: The rGO-g-PTMPM methanol dispersion obtained in step (1) was ultrasonicated for 1 hour, 180 mg of disodium ethylenediaminetetraacetic acid, 125 mg of sodium tungstate dihydrate, and 15 mL of deionized water were added and mixed, and then 15 mL of a 30% hydrogen peroxide solution was slowly added dropwise. After reacting at room temperature for 24 hours, 65 mg of disodium ethylenediaminetetraacetic acid, 62 mg of sodium tungstate dihydrate, and 5 mL of deionized water were added and mixed, and then 5 mL of a 30% hydrogen peroxide solution was slowly added dropwise. After reacting at room temperature for another 24 hours, the reaction solution was filtered with a 0.22 μm organic phase filter membrane, the product was washed with deionized water three times, and freeze-dried to obtain 593 mg of the final product, an organic cathode material rGO-g-PTMA.

[0047] A method for preparing an organic negative electrode material for an all-organic battery comprises the following steps:

[0048] (1) Synthesis of VEtBr: 5 g of 4,4'-bipyridine (30 mmol) was added to an egg-shaped flask and dissolved in 35 mL of acetonitrile. 600 μL of bromoethane (8 mmol) was added to the reaction system and heated under reflux at 90°C for 24 h. After the reaction was completed, the system was cooled to room temperature and the solvent was removed by vacuum distillation. The resulting product was dissolved in N,N-dimethylformamide at 100°C and filtered while hot. The filtrate was precipitated with glacial ether to obtain 2 g of white solid product VEtBr (reaction yield 94%).

[0049] (2) Synthesis of VBVEtBrCl: 0.96 g of VEtBr (5 mmol) was placed in an egg-shaped flask and dissolved in 25 mL of acetonitrile. 2 mL of vinylbenzyl chloride (14 mmol) was added to the reaction system and heated under reflux at 80°C for 24 h. After the reaction, a yellow precipitate was formed. The solvent was removed by filtration, and the product was washed several times with diethyl ether. After vacuum drying at 40°C for 4 h, 1.36 g of solid product VBVEtBrCl was obtained (reaction yield: 65%).

[0050] (3) Synthesis of PVBVEtBrCl: 0.52 g of VBVEtBrCl (1.2 mmol) was added to a Schlenk flask and dissolved in 0.7 mL of deionized water. 22.6 mg of potassium persulfate (0.084 mmol) was added as an initiator. The system was frozen, evacuated, and then nitrogen was introduced three times to remove oxygen. The reaction was then continued at 85°C for 4 h. The system was freeze-dried to obtain 0.43 g of the yellow product, PVBVEtBrCl.

[0051] (4) Preparation of PVBVEt(PF6)2: 200 mg of PVBVEtBrCl was added to an egg-shaped flask and dissolved in 0.5 mL of deionized water. An excess of aqueous NH4PF6 solution was added and stirred to produce an off-white solid. The product was washed several times with deionized water and dried under vacuum at 40°C for 8 h to obtain 150 mg of PVBVEt(PF6)2 (reaction yield 85%).

[0052] The preparation of the positive electrode plate of the all-organic battery includes the following steps:

[0053] (1) Dissolve 0.32 g of polyvinylidene fluoride (PVDF) in 16 mL of N-methylpyrrolidone to obtain a PVDF solution with a concentration of 0.02 g / mL, and set aside.

[0054] (2) 80 mg of rGO-g-PTMA, 500 μL of PVDF solution, 10 mg of conductive agent Super P, and 2 mL of NMP solvent were added to a small reaction bottle and stirred thoroughly for 4 h to obtain a black, shiny, and uniform slurry;

[0055] (3) Cut the current collector aluminum foil into a 6 cm × 15 cm rectangular sheet, fix it on a glass substrate, evenly apply the slurry in step (2) with an applicator, place it in a vacuum drying oven at 70°C for 12 hours, and then use a tablet press to punch the aluminum foil coated with the positive electrode material into a circular electrode sheet with a diameter of 1.2 cm.

[0056] The method for preparing the negative electrode plate of an all-organic battery comprises the following steps:

[0057] (1) Dissolve 0.32 g of polyvinylidene fluoride (PVDF) in 16 mL of N-methylpyrrolidone to obtain a PVDF solution with a concentration of 0.02 g / mL, and set aside.

[0058] (2) Add 50 mg of PVBVEt(PF6)2, 500 μL of PVDF solution, 40 mg of the conductive agent Ketjen Black, and 2 mL of NMP solvent into a small reaction bottle and stir thoroughly for 4 h to obtain a black, shiny, uniform slurry;

[0059] (3) Cut the current collector aluminum foil into a 6 cm × 15 cm rectangular sheet, fix it on a glass substrate, evenly apply the slurry in step (2) with an applicator, place it in a vacuum drying oven at 70°C for 12 hours, and then use a tablet press to punch the aluminum foil coated with the negative electrode material into a circular electrode sheet with a diameter of 1.2 cm.

[0060] The all-organic battery is assembled in a glove box filled with a helium atmosphere and containing less than 0.5 ppm of water and oxygen. A drop of the full-cell electrolyte, a 2M solution of lithium perchlorate (LiClO4) in tetraethylene glycol dimethyl ether (TEGDME), is placed in the center of the positive electrode shell of a 2025 button cell. The positive electrode sheet is placed face-up, and three drops of electrolyte are added. A Celgard 2400 separator is then placed, followed by three drops of electrolyte. The negative electrode sheet is then placed, followed by a round nickel foam (1.2 cm in diameter). Finally, the negative electrode shell of the button cell is covered, compacted with a battery press, the surface cleaned, and the battery is bagged for later use.

[0061] Battery test cycle and rate results were completed on a Neware CT4008 battery test system with a cutoff voltage of 0-2 V. Cyclic voltammetry (CV) results were completed on a CHI 660E electrochemical workstation with a CV scan rate of 0.5 mV / s and a cutoff voltage of 0-2 V.

[0062] The cyclic voltammetry curve results are as follows Figure 1 As shown, two pairs of redox peaks can be seen at 1.1 V and 1.6 V, with potential differences of 0.28 V and 0.22 V, respectively, demonstrating the excellent redox reversibility of the all-organic battery.

[0063] The charge and discharge curve results are as follows Figure 2 As shown in the figure, two symmetrical redox platforms are visible at around 1.1 V and 1.6 V, and the discharge capacity is as high as 145.4 mAh g -1 .

[0064] 200 cycle performance curves are as follows Figure 3 As shown in the figure, the capacity decays by about 50% after 200 cycles, and the charge and discharge coulombic efficiency is close to 100% after the battery is activated and stabilized.

[0065] The impedance curve is as follows Figure 4 As shown, the battery has a relatively low resistance of 150Ω.

[0066] Comparative Example 1:

[0067] Compared with Example 1, most of the above are the same, except that the organic cathode material rGO-g-PTMA is replaced by rGO / PTMA. The rGO / PTMA material is prepared by physically mixing reduced graphene oxide rGO and polymer PTMA (Mn = 1000-10000). Figure 5The charge-discharge curves of the rGO / PTMA / PVBVEt(PF6)2 all-organic battery only show an inconspicuous redox platform, and the battery capacity is only 90 mAh g -1 , the charge-discharge coulombic efficiency is only 64%. Because physically blended composite materials lack covalent bonds, they are unstable and the active materials easily aggregate, resulting in low active site utilization and poor electrochemical performance of batteries assembled with this material. In Example 1, the all-organic battery prepared using covalently grafted rGO-g-PTMA as the positive electrode material exhibits excellent performance.

[0068] Comparative Example 2:

[0069] Compared with Example 1, most of the above are the same, except that PVBVEt(PF6)2 is replaced with a structurally similar organic negative electrode material PVAEt(PF6)2, the structure of which is as follows: n=2~100. Figure 6 The charge-discharge curve of the rGO-g-PTMA / PVAEt(PF6)2 all-organic battery has almost no redox platform, and the discharge capacity is only 100 mAh g -1 , with a Coulombic efficiency of 86%. In the PVAEt(PF6)2 material, the benzyl group attached to the viologen group is replaced with a methylene group, which reduces the stability of the molecular structure and thus affects the electrochemical performance of the material. In Example 1, the all-organic battery prepared using the viologen cationic polymer PVBVEt(PF6)2 with benzyl groups as the negative electrode material exhibited excellent performance.

[0070] The above description of the embodiments is intended to facilitate understanding and use of the invention by those skilled in the art. It will be apparent that those skilled in the art can readily make various modifications to these embodiments and apply the general principles described herein to other embodiments without requiring inventive effort. Therefore, the present invention is not limited to the above-described embodiments. Improvements and modifications made by those skilled in the art based on the disclosure of the present invention, without departing from the scope of the present invention, should be within the scope of protection of the present invention.

Claims

1. Application of an electrode material for an all-organic battery, characterized in that: The electrode material is used to assemble into an all-organic battery, which includes a positive electrode sheet composed of an organic positive electrode material and a negative electrode sheet composed of an organic negative electrode material. The organic positive electrode material is named rGO-g-PTMA, which includes reduced graphene oxide and poly (4-methacryloyloxy)-2,2,6,6-tetramethylpiperidinyl nitroxide) grafted on the reduced graphene oxide; the organic negative electrode material is a viologen cationic polymer PVBVEt(PF6)2; The mass of the poly (4-methacryloyloxy)-2,2,6,6-tetramethylpiperidinyl)nitroxide radical accounts for 45-55% of the total mass of the rGO-g-PTMA. The structural formula of the PVBVEt(PF6)2 is as follows: n=2~100.

2. A use according to claim 1, characterized in that The preparation of organic positive electrode materials and organic negative electrode materials specifically includes the following steps: (1) Preparation of organic cathode materials: (1-1) Reduced graphene oxide and N-methylpyrrolidone solvent were mixed uniformly, and 2,2,6,6-tetramethyl-4-piperidinyl methacrylate monomer and azobisisobutyronitrile initiator were added under nitrogen atmosphere. The oxygen was removed by lyophilization, and the filtrate was filtered. The filtrate was washed with acetone several times to obtain the intermediate product rGO-g-PTMPM; (1-2) mixing the rGO-g-PTMPM obtained in step (1-1) with methanol, adding deionized water, disodium ethylenediaminetetraacetic acid, sodium tungstate dihydrate, and hydrogen peroxide solution to react, washing with deionized water multiple times and freeze-drying after the reaction to obtain an organic cathode material rGO-g-PTMA; (2) Preparation of organic negative electrode materials: (2-1) 4,4'-Bipyridine was dissolved in acetonitrile and bromoethane was added for reaction. After the reaction, the mixture was cooled to room temperature and the solvent was removed by distillation under reduced pressure. The resulting precipitate was dissolved in N,N-dimethylformamide and filtered. The filtrate was then precipitated with glacial ether to obtain VEtBr as a white solid product. (2-2) Dissolving the VEtBr obtained in step (2-1) in acetonitrile, adding vinylbenzyl chloride for reaction, and filtering to remove the solvent after the reaction. The resulting precipitate is washed with diethyl ether several times and dried in vacuo to obtain a solid product, VBVEtBrCl; (2-3) Dissolving the VBVEtBrCl obtained in step (2-2) in deionized water, adding potassium persulfate as an initiator, mixing, freezing, evacuating, then introducing nitrogen to deoxygenate, and freeze-drying to obtain a yellow product, PVBVEtBrCl; (2-4) Dissolving the PVBVEtBrCl obtained in step (2-3) with deionized water, adding an excess of NH4PF6 aqueous solution and stirring to precipitate an off-white solid, washing the off-white solid with deionized water multiple times, and vacuum drying to obtain the organic negative electrode material PVBVEt(PF6)2.

3. The use according to claim 2, characterized in that In step (1-1), the ratio of reduced graphene oxide: N-methylpyrrolidone: 2,2,6,6-tetramethyl-4-piperidinyl methacrylate: initiator azobisisobutyronitrile is: 400 mg: 100 mL: 8 g: 87 mg; the reaction temperature for lyophilization and oxygen removal is 70° C., and the reaction time is 20 h; In step (1-2), the mass ratio of the rGO-g-PTMPM to methanol is 1:182; deionized water, disodium ethylenediaminetetraacetic acid, sodium tungstate dihydrate and 30% hydrogen peroxide are added twice, respectively. The ratio of deionized water: disodium ethylenediaminetetraacetic acid: sodium tungstate dihydrate: 30% hydrogen peroxide solution added for the first time is 15 mL: 180 mg: 125 mg: 15 mL, the reaction temperature is room temperature, and the reaction time is 24 h; the ratio of deionized water: disodium ethylenediaminetetraacetic acid: sodium tungstate dihydrate: 30% hydrogen peroxide solution added for the second time is 5 mL: 65 mg: 62 mg: 5 mL, the reaction temperature is room temperature, and the reaction time is 24 h.

4. The use according to claim 2, characterized in that In step (2-1), the ratio of 4,4'-bipyridine to bromoethane was 5 g:600 μL; the reaction temperature after adding bromoethane was 90°C, and the reaction time was 24 h; the temperature of the added N,N-dimethylformamide was 100°C; In step (2-2), the ratio of VEtBr: vinylbenzyl chloride is 0.96 g: 2 mL; the reaction temperature after adding vinylbenzyl chloride is 80° C., and the reaction time is 24 h; the vacuum drying temperature is 40° C., and the time is 4 h; In step (2-3), the ratio of VBVEtBrCl to initiator potassium persulfate is 0.52 g:22.6 mg; before freeze-drying, the deoxygenated reaction system is reacted at 85°C for 4 hours; In step (2-4), the vacuum drying temperature is 40° C. and the time is 8 h.

5. The use according to claim 1, characterized in that The method for preparing the electrode plate of the all-organic battery comprises the following steps: (1) dissolving polyvinylidene fluoride in NMP solvent to prepare a polyvinylidene fluoride solution with a concentration of 0.02 g / mL; (2) mixing the organic positive electrode material rGO-g-PTMA, polyvinylidene fluoride solution, and a first conductive agent, and adding NMP solvent and stirring to obtain a black and shiny first slurry; mixing the organic negative electrode material PVBVEt(PF6)2, polyvinylidene fluoride solution, and a second conductive agent, and adding NMP solvent and stirring to obtain a black and shiny second slurry; (3) The first slurry and the second slurry obtained in step (2) are applied to aluminum foil respectively, and then vacuum-dried and pressed into sheets to finally obtain a positive electrode sheet and a negative electrode sheet of a battery respectively.

6. The use according to claim 5, characterized in that In step (2), the mass ratio of the organic positive electrode material rGO-g-PTMA, polyvinylidene fluoride solution, and the first conductive agent is 8:1:1; the mass ratio of the organic negative electrode material PVBVEt(PF6)2, polyvinylidene fluoride solution, and the second conductive agent is 5:4:1; the first conductive agent is Super P, and the second conductive agent is Ketjen black.

7. The use according to claim 5, characterized in that In step (3), the vacuum drying temperature is 70° C. and the time is 12 h.

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