Perylene diimide-based aqueous ammonium-ion battery electrode material, preparation method and application

Abstract

The application belongs to the technical field of energy storage materials, and particularly relates to a water-based ammonium ion battery electrode material based on perylene diimide, a preparation method and application. First, a perylene diimide compound and a preparation method are provided. The material is stable, rich in carbonyl structure, can undergo enol tautomerization to bind / release ammonium ions to complete charge storage during charging and discharging. A water-based battery prepared from the perylene diimide compound and a preparation method are provided. In a 1M (NH4)2SO4 solution and under a current density of 1A / g, the battery has a reversible specific capacity of 190.62 mAh / g and excellent rate performance. In a 1M (NH4)2SO4 solution and under a current density of 10A / g, the battery still has a specific capacity of 101.67 mAh / g after 1000 cycles of continuous charging and discharging. The preparation process is simple, the cost is low, and the market application prospect is wide.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of energy storage materials, and particularly relates to a water-based ammonium ion battery electrode material based on perylene diimide, a preparation method and application. TECHNICAL BACKGROUND

[0002] In recent years, with the increasing awareness of environmental protection and resource conservation of the whole human race, the research and development of new energy storage materials have attracted more and more attention. The water-based ammonium ion battery is a new non-metallic energy storage battery with ammonium ion as the carrier, which has many advantages and broad development prospects. Ammonium ion resources are abundant, and its compounds have low cost. The water-based electrolyte is not expensive, which reduces the overall cost of the battery. The water-based electrolyte is not flammable and explosive, and is safe to use, which reduces the safety risk of the battery in use and storage. Ammonium ion has a small hydration radius and a small molar mass (18 g / mol), which can realize fast migration and transmission of ions, fast intercalation and deintercalation in electrode materials without causing collapse of the electrode materials, and can minimize corrosion of equipment in a neutral or weakly acidic environment.

[0003] However, the research and development of electrode materials are limited. In terms of positive electrode materials, although Prussian blue analogues and metal oxides have been applied, the intercalation type positive electrode materials have limited capacity and slow kinetics, which are difficult to meet the requirements of high-performance batteries. In terms of negative electrode materials, although some options such as organic materials and synthetic polymer materials exist, there are problems such as irreversible intercalation, electrode swelling, electrolyte consumption, and low coulombic efficiency. In view of the above technical problems, Hanmei Jiang et al. found that regulating asymmetric bimetallic sites can reduce the desolvation energy barrier of NH4 + (H2O)4 at the electrode-electrolyte interface, improve diffusion kinetics and structural stability; Ling, Dandan et al. synthesized Bi2SeO5 nanosheets rich in oxygen vacancies by a hydrothermal method, which accelerated ion transmission and improved the electrical conductivity of the material. Bao Zhuoheng et al. predicted the working potential of V2CTxMXene, which exhibited good pseudocapacitive behavior and cycle stability as a low-working-potential anode.

[0004] Compared with many energy storage electrodes, organic electrode materials have broad development prospects due to their high designability, simple preparation, high theoretical capacity, environmental friendliness and abundant resources. However, the solubility of NH4 + combined with small organic molecules increases, which easily leads to electrode dissolution, and the steric hindrance effect of organic compounds causes NH4 + to be unable to fully utilize its active sites, which leads to low actual capacity and affects the electrochemical performance of the battery.

[0005] REFERENCES

[0006] Hanmei Jiang, Hao Yuan, Qiang Chen, Jianguo Sun, Yanyan Liu, Yifu Zhang, Yong-wei Zhang, Changgong Meng, John Wang, Zhenghui Pan. Regulation of Asymmetric Bimetallic NiFe Sites Boost Fast Desolvation Kinetics for Long-cycling Ammonium-Ion Storage. Energy Storage Mater., 2024, 103647

[0007] Ling, Dandan, et al. "Oxygen Vacancy-Enriched Bi2SeO5 Nanosheets with Dual Mechanism for Ammonium-Ion Batteries." ACS Nano 2023, 17, 24, 25222-25233. DOI: 10.1021 / acsnano.3c08460.

[0008] Bao Zhuoheng, Lu Chengjie, Liu Qiang, Ye Fei, Li Weihuan, Zhou Yang, Pan Long, Duan Lunbo, Tang Hongjian, Wu Yuping, Hu Linfeng, Sun Zheng Ming. An acetate electrolyte for enhanced pseudocapacitve capacity in aqueous ammonium ion batteries. Nature Communications, 2024, 15(1): 1934.

[0009] DOI: https: / / doi.org / 10.1038 / s41467-024-46317-5 SUMMARY

[0010] In view of the above deficiencies of the prior art, the present application aims to develop a preparation method and application of perylene diimide-based aqueous ammonium ion battery electrode material to solve the problems of low electrode capacity and poor cycle stability of ammonium ion batteries at the present stage.

[0011] To achieve the above object, the technical scheme adopted by the present application is:

[0012] The primary object of the present application is to provide a perylene diimide compound, the structural general formula of which is shown as formula (I).

[0013]

[0014] wherein R is one of H, CH3, F, Cl, Br, I, NO2, CN, COOH, OH, OCH3, located at ortho, meta or para position.

[0015] The second object of the present application is to provide a preparation method of the perylene diimide compound, comprising the following steps:

[0016] (1) dissolving perylene-3,4,9,10-tetracarboxylic dianhydride in NMP to obtain solution A, and dissolving aniline or aniline derivative in NMP to obtain solution B;

[0017] (2) under magnetic stirring, slowly dropping solution B obtained in step (1) into solution A, stirring the mixture, transferring into a PTFE autoclave mold, and reacting;

[0018] (3) after the reaction is completed, cooling to room temperature, centrifugal washing with ethanol and deionized water, and drying to obtain the perylene diimide compound.

[0019] Preferably, the aniline derivative in step (1) comprises 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, 2-nitroaniline, m-nitroaniline, 4-nitroaniline hydrochloride, 2-aminobenzonitrile, 3-aminobenzonitrile, p-aminobenzonitrile, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminomethoxyphenol, 3-aminomethoxyphenol, 4-aminomethoxyphenol.

[0020] Preferably, the molar ratio of perylene-3,4,9,10-tetracarboxylic dianhydride and aniline or aniline derivative in step (1) is from 1:2 to 1:3.

[0021] Preferably, the stirring time of the mixture in step (2) is 2 hours, the reaction temperature is set to 200℃, and the reaction time is 12-36 hours.

[0022] The third object of the present application is to provide the application of the perylene diimide compound or the perylene diimide compound prepared by the preparation method in the preparation of water-based ammonium ion battery electrode material.

[0023] The fourth object of the present application is a water-based ammonium ion battery electrode based on perylene diimide compounds, which is prepared by mixing perylene diimide compounds, a conductive agent, a binder and a solvent to prepare an electrode homogenate, coating the electrode homogenate on a carbon sheet, and drying at 50-100 DEG C to obtain a water-based ammonium ion battery negative electrode.

[0024] Preferably, the conductive agent is one or more of superconducting carbon black, graphite, carbon nanotubes, graphene, silver nanoparticles, copper nanoparticles, polyaniline, polypyrrole, ketjen black, acetylene black; the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethyl cellulose, butadiene rubber and polyacrylic acid; and the solvent is one or more of N-methyl pyrrolidone, DMF, ethanol and water.

[0025] The fifth object of the present application is to provide a test method for a water-based ammonium ion battery electrode based on perylene diimide compounds, which is carried out in a three-electrode system prepared and assembled as follows:

[0026] (1) using a graphite sheet electrode as a counter electrode;

[0027] (2) mixing perylene diimide compounds, a conductive agent, a binder and a solvent to prepare an electrode homogenate, coating the electrode homogenate on a carbon sheet, and drying at 50-100 DEG C to obtain a water-based ammonium ion battery negative electrode sheet, using the water-based ammonium ion battery negative electrode sheet as a working electrode;

[0028] (3) inserting a reference electrode, and using (NH4)2SO4 solution as an electrolyte solution;

[0029] (4) testing the battery performance.

[0030] Preferably, the mass ratio of perylene diimide compounds, a conductive agent and a binder is 6:2:2.

[0031] The present application has the following effects:

[0032] (1) the present application first provides perylene diimide compounds, and in detail provides a preparation method of the perylene diimide compounds, the preparation method is simple, the material is stable, rich in carbonyl structure, can undergo enol tautomerization to combine / release ammonium ions to complete charge storage during charging and discharging; the structure is regular and has a π-π conjugated structure, which enhances the electrical conductivity and is beneficial to the rapid embedding / exfoliation of ions. In addition, the reasonable electron delocalization regulation of perylene diimide organic material weakens the steric hindrance effect, realizes reversible four-electron transfer, and enhances the cycle stability of the electrode material.

[0033] (2) The application provides a water-based battery prepared from a perylene diimide compound and a preparation method.

[0034] (3) The preparation process used in the application is simple, low in cost and has wide market application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0035] The scope of protection of the application is described in detail below in combination with specific drawings.

[0036] Figure 1 SEM image of perylene diimide PTCDAn prepared for Example 1

[0037] Figure 2 Constant current charge-discharge curve of perylene diimide PTCDAn prepared for Example 1

[0038] Figure 3 Cycle stability curve of perylene diimide PTCDAn prepared for Example 1 DETAILED DESCRIPTION

[0039] The application is described in detail below in combination with examples.

[0040] It should be noted that, in the following examples, unless otherwise specified, the methods used are conventional methods, and in the following examples, unless otherwise specified, the reagents and consumables used can be purchased on the market.

[0041] In the following examples, the NMP solution is N-methyl pyrrolidone, which is an aprotic solvent. Its characteristics are large polarity, high boiling point, small viscosity, high thermal stability and chemical stability.

[0042] It should be noted that the following examples are not all experimental results of the inventors, but only reflect part of the experimental results.

[0043] Example 1: Preparation method of water-based ammonium ion battery electrode material based on perylene diimide

[0044] A solution A was prepared by dissolving 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride in 5 mL of NMP, and a solution B was prepared by dissolving 1.25 mmol of aniline in 5 mL of NMP. Then, solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold for reaction at 200°C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water and dried to obtain a perylene diimide PTCDAn, the structure of which is shown in the following formula:

[0045]

[0046] The SEM image of the prepared perylene diimide PTCDAn is shown in Figure 1 .

[0047] Example 2, preparation method of perylene diimide-based aqueous ammonium ion battery electrode material

[0048] A solution A was prepared by dissolving 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride in 5 mL of NMP, and a solution B was prepared by dissolving 1.25 mmol of 2-fluoroaniline in 5 mL of NMP. Then, solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold for reaction at 200°C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0049]

[0050] Example 3, preparation method of perylene diimide-based aqueous ammonium ion battery electrode material

[0051] A solution A was prepared by dissolving 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride in 5 mL of NMP, and a solution B was prepared by dissolving 1.25 mmol of 3-fluoroaniline in 5 mL of NMP. Then, solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold for reaction at 200°C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0052]

[0053] Example 4, preparation method of perylene diimide-based aqueous ammonium ion battery electrode material

[0054] Perylene-3,4,9,10-tetracarboxylic dianhydride 0.5 mmol was dissolved in 5 mL NMP to obtain solution A, and 1.25 mmol of 4-fluoroaniline was dissolved in 5 mL NMP to obtain solution B. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours and then transferred into a 25 mL PTFE autoclave mold, and reacted at 200°C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water, and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0055]

[0056] Example 5, preparation method of perylene diimide-based aqueous ammonium ion battery electrode material

[0057] Perylene-3,4,9,10-tetracarboxylic dianhydride 0.5 mmol was dissolved in 5 mL NMP to obtain solution A, and 1.25 mmol of 2-chloroaniline was dissolved in 5 mL NMP to obtain solution B. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours and then transferred into a 25 mL PTFE autoclave mold, and reacted at 200°C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water, and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0058]

[0059] Example 6, preparation method of perylene diimide-based aqueous ammonium ion battery electrode material

[0060] Perylene-3,4,9,10-tetracarboxylic dianhydride 0.5 mmol was dissolved in 5 mL NMP to obtain solution A, and 1.25 mmol of 3-chloroaniline was dissolved in 5 mL NMP to obtain solution B. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours and then transferred into a 25 mL PTFE autoclave mold, and reacted at 200°C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water, and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0061]

[0062] Example 7, preparation method of perylene diimide-based aqueous ammonium ion battery electrode material

[0063] A solution A was prepared by dissolving 0.5 mmol of perylene-3,4,9,10- tetracarboxylic dianhydride in 5 mL of NMP, and a solution B was prepared by dissolving 1.25 mmol of 4-chloroaniline in 5 mL of NMP. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold and reacted at 200 °C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0064]

[0065] Example 8, method for preparing perylene diimide-based aqueous ammonium ion battery electrode material

[0066] A solution A was prepared by dissolving 0.5 mmol of perylene-3,4,9,10- tetracarboxylic dianhydride in 5 mL of NMP, and a solution B was prepared by dissolving 1.25 mmol of 2-bromoaniline in 5 mL of NMP. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold and reacted at 200 °C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0067]

[0068] Example 9, method for preparing perylene diimide-based aqueous ammonium ion battery electrode material

[0069] A solution A was prepared by dissolving 0.5 mmol of perylene-3,4,9,10- tetracarboxylic dianhydride in 5 mL of NMP, and a solution B was prepared by dissolving 1.25 mmol of 3-bromoaniline in 5 mL of NMP. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold and reacted at 200 °C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0070]

[0071] Example 10, method for preparing perylene diimide-based aqueous ammonium ion battery electrode material

[0072] A solution A was prepared by dissolving 0.5 mmol of perylene-3,4,9,10- tetracarboxylic dianhydride in 5 mL of NMP, and a solution B was prepared by dissolving 1.25 mmol of 4-bromoaniline in 5 mL of NMP. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold and reacted at 200 °C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0073]

[0074] Example 11, a preparation method of a perylene diimide-based aqueous ammonium ion battery electrode material

[0075] A solution A was prepared by dissolving 0.5 mmol of perylene-3,4,9,10- tetracarboxylic dianhydride in 5 mL of NMP, and a solution B was prepared by dissolving 1.25 mmol of 2-nitroaniline in 5 mL of NMP. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold and reacted at 200 °C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0076]

[0077] Example 12, a preparation method of a perylene diimide-based aqueous ammonium ion battery electrode material

[0078] A solution A was prepared by dissolving 0.5 mmol of perylene-3,4,9,10- tetracarboxylic dianhydride in 5 mL of NMP, and a solution B was prepared by dissolving 1.25 mmol of 2-nitroaniline in 5 mL of NMP. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold and reacted at 200 °C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0079]

[0080] Example 13, a preparation method of a perylene diimide-based aqueous ammonium ion battery electrode material

[0081] Solution A was prepared by dissolving 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride in 5 mL of NMP, and solution B was prepared by dissolving 1.25 mmol of 4-nitroaniline hydrochloride in 5 mL of NMP. Solution B was then slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold and reacted at 200°C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0082]

[0083] Example 14, method for preparing perylene diimide-based aqueous ammonium ion battery electrode material

[0084] Solution A was prepared by dissolving 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride in 5 mL of NMP, and solution B was prepared by dissolving 1.25 mmol of 2-methylaniline in 5 mL of NMP. Solution B was then slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold and reacted at 200°C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0085]

[0086] Example 15, method for preparing perylene diimide-based aqueous ammonium ion battery electrode material

[0087] Solution A was prepared by dissolving 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride in 5 mL of NMP, and solution B was prepared by dissolving 1.25 mmol of 3-methylaniline in 5 mL of NMP. Solution B was then slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold and reacted at 200°C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0088]

[0089] Example 16, method for preparing perylene diimide-based aqueous ammonium ion battery electrode material

[0090] Perylene-3,4,9,10-tetracarboxylic dianhydride 0.5 mmol was dissolved in 5 mL NMP to obtain solution A, and 1.25 mmol of 4-methylaniline was dissolved in 5 mL NMP to obtain solution B. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours and then transferred into a 25 mL PTFE autoclave mold, and reacted at 200°C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water, and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0091]

[0092] Example 17, preparation method of perylene diimide-based aqueous ammonium ion battery electrode material

[0093] Perylene-3,4,9,10-tetracarboxylic dianhydride 0.5 mmol was dissolved in 5 mL NMP to obtain solution A, and 1.25 mmol of 2-aminobenzonitrile was dissolved in 5 mL NMP to obtain solution B. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours and then transferred into a 25 mL PTFE autoclave mold, and reacted at 200°C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water, and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0094]

[0095] Example 18, preparation method of perylene diimide-based aqueous ammonium ion battery electrode material

[0096] Perylene-3,4,9,10-tetracarboxylic dianhydride 0.5 mmol was dissolved in 5 mL NMP to obtain solution A, and 1.25 mmol of 3-aminobenzonitrile was dissolved in 5 mL NMP to obtain solution B. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours and then transferred into a 25 mL PTFE autoclave mold, and reacted at 200°C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water, and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0097]

[0098] Example 19, preparation method of perylene diimide-based aqueous ammonium ion battery electrode material

[0099] Solution A was prepared by dissolving 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride in 5 mL of NMP, and solution B was prepared by dissolving 1.25 mmol of 4-aminobenzoic acid in 5 mL of NMP. Solution B was then slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold and reacted at 200 °C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0100]

[0101] Example 20, method for preparing perylene diimide-based aqueous ammonium ion battery electrode material

[0102] Solution A was prepared by dissolving 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride in 5 mL of NMP, and solution B was prepared by dissolving 1.25 mmol of 2-aminobenzoic acid in 5 mL of NMP. Solution B was then slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold and reacted at 200 °C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0103]

[0104] Example 21, method for preparing perylene diimide-based aqueous ammonium ion battery electrode material

[0105] Solution A was prepared by dissolving 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride in 5 mL of NMP, and solution B was prepared by dissolving 1.25 mmol of 3-aminobenzoic acid in 5 mL of NMP. Solution B was then slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold and reacted at 200 °C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0106]

[0107] Example 22, method for preparing perylene diimide-based aqueous ammonium ion battery electrode material

[0108] Perylene-3,4,9,10-tetracarboxylic dianhydride 0.5 mmol was dissolved in 5 mL NMP to obtain solution A, and 1.25 mmol of 4-aminobenzoic acid was dissolved in 5 mL NMP to obtain solution B. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours and then transferred into a 25 mL PTFE autoclave mold, and reacted at 200°C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water, and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0109]

[0110] Example 23, preparation method of perylene diimide-based aqueous ammonium ion battery electrode material

[0111] Perylene-3,4,9,10-tetracarboxylic dianhydride 0.5 mmol was dissolved in 5 mL NMP to obtain solution A, and 1.25 mmol of 2-aminophenol was dissolved in 5 mL NMP to obtain solution B. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours and then transferred into a 25 mL PTFE autoclave mold, and reacted at 200°C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water, and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0112]

[0113] Example 24, preparation method of perylene diimide-based aqueous ammonium ion battery electrode material

[0114] Perylene-3,4,9,10-tetracarboxylic dianhydride 0.5 mmol was dissolved in 5 mL NMP to obtain solution A, and 1.25 mmol of 3-aminophenol was dissolved in 5 mL NMP to obtain solution B. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours and then transferred into a 25 mL PTFE autoclave mold, and reacted at 200°C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water, and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0115]

[0116] Example 25, preparation method of perylene diimide-based aqueous ammonium ion battery electrode material

[0117] A solution A was prepared by dissolving 0.5 mmol of perylene-3,4,9,10- tetracarboxylic dianhydride in 5 mL of NMP, and a solution B was prepared by dissolving 1.25 mmol of 4-aminophenol in 5 mL of NMP. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold and reacted at 200 °C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0118]

[0119] Example 26, a preparation method of a perylene diimide-based aqueous ammonium ion battery electrode material

[0120] A solution A was prepared by dissolving 0.5 mmol of perylene-3,4,9,10- tetracarboxylic dianhydride in 5 mL of NMP, and a solution B was prepared by dissolving 1.25 mmol of 2-methoxyaniline in 5 mL of NMP. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold and reacted at 200 °C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0121]

[0122] Example 27, a preparation method of a perylene diimide-based aqueous ammonium ion battery electrode material

[0123] A solution A was prepared by dissolving 0.5 mmol of perylene-3,4,9,10- tetracarboxylic dianhydride in 5 mL of NMP, and a solution B was prepared by dissolving 1.25 mmol of 3-methoxyaniline in 5 mL of NMP. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold and reacted at 200 °C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then centrifugally washed with ethanol and deionized water and dried to obtain a perylene diimide organic material, the structure of which is shown in the following formula:

[0124]

[0125] Example 28, a preparation method of a perylene diimide-based aqueous ammonium ion battery electrode material

[0126] Perylene-3,4,9,10-tetracarboxylic dianhydride 0.5 mmol was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 4-methoxyaniline was dissolved in 5 mL of NMP to obtain solution B. Then solution B was slowly dripped into solution A under magnetic stirring, and the mixture was stirred for 2 hours before being transferred into a 25 mL PTFE autoclave mold and reacted at 200°C for 24 hours. After waiting for the reaction to end, the product and solution were cooled to room temperature, and then washed and dried by centrifugation with ethanol and deionized water to obtain the perylene diimide organic material, the structure of which is shown in the following formula:

[0127]

[0128] Example 29, preparation of a water-based battery

[0129] It should be noted that, in order to save space and reduce the repeatability of the experimental method, the preparation method of this embodiment is only to list the method for preparing a water-based battery from the perylene diimide PTCDAn prepared in Example 1. The perylene diimide organic materials prepared in Examples 2-20 can also be used to prepare a water-based battery by the following method, and the performance of the battery prepared by the following method will not be significantly different.

[0130] The perylene diimide PTCDAn prepared in Example 1, the conductive agent Super P, and the binder polyvinylidene fluoride were mixed in a mass ratio of 6:2:2 with N-methyl pyrrolidone solvent to prepare an electrode homogenate, which was coated on a carbon sheet and vacuum dried at 60°C to obtain a water-based ammonium ion battery negative electrode sheet. A water-based ammonium ion battery negative electrode sheet was used as a working electrode, a graphite sheet electrode was used as a counter electrode, an Ag / AgCl electrode was used as a reference electrode, and a 1M (NH4)2SO4 solution was used as an electrolyte solution to assemble a three-electrode system water-based battery, which was subjected to battery performance testing.

[0131] The constant current charge-discharge curve of the prepared perylene diimide PTCDAn is shown in Figure 2 At a current density of 1A / g and in a 1M (NH4)2SO4 solution, the perylene diimide PTCDAn has a reversible specific capacity of 190.62 mAh / g and exhibits excellent rate performance.

[0132] The cycle stability curve of the prepared perylene diimide PTCDAn is shown in Figure 3 At a current density of 10A / g and in a 1M (NH4)2SO4 solution, the quinone amine polymer perylene diimide PTCDAn still has a specific capacity of 101.67 mAh / g after 1000 cycles of continuous charge-discharge.

[0133] In summary, the present application provides a perylene diimide compound, and in detail provides a preparation method of the perylene diimide compound, the preparation method is simple, the material is stable, rich in carbonyl structure, can occur enol conversion in the charging and discharging process to combine / release ammonium ion to complete the storage of charge; the structure is regular and has a π-π conjugated structure, which enhances the conductivity and is beneficial to the rapid embedding / exfoliation of ions. In addition, the reasonable electron delocalization regulation of perylene diimide organic material weakens the steric hindrance effect, realizes the reversible four-electron transfer, and enhances the cycle stability of the electrode material. The present application also provides a water-based battery prepared from the perylene diimide compound and a preparation method thereof. The prepared water-based battery has a reversible specific capacity of 190.62 mAh / g under 1M (NH4) 2SO4 solution and a current density of 1A / g, and shows excellent rate performance. Under 1M (NH4) 2SO4 solution and a current density of 10A / g, the quinone amine polymer perylene diimide PTCDAn still has a specific capacity of 101.67 mAh / g after 1000 cycles of continuous charging and discharging. The organic solvent used in the present application is easy to recycle, the preparation process is green and environmentally friendly, the cost is low, and the market application prospect is broad.

[0134] The specific implementation cases of the present application are described in detail above, but they are only examples, and the present application is not limited to the specific implementation cases described above. Any equivalent modification and replacement of the present application for those skilled in the art is also within the scope of the present application. Therefore, any equivalent transformation and modification without departing from the spirit and scope of the present application should be covered within the scope of the present application.

Claims

1. Use of a perylene diimide compound in the preparation of an electrode material for an aqueous ammonium ion battery, the perylene diimide compound having a general structure as shown in formula (I): wherein R is H. wherein The perylene diimide compound, a conductive agent, a binder and a solvent are mixed to form an electrode slurry, which is coated on a carbon sheet and dried at 50-100°C to obtain a negative electrode for an aqueous ammonium ion battery.

2. A water-based ammonium ion battery electrode based on perylene diimide compounds, characterized by, The perylene diimide compound has a general structure as shown in formula (I): wherein R is H. The conductive agent is one or more of superconducting carbon black, graphite, carbon nanotubes, graphene, silver nanoparticles, copper nanoparticles, polyaniline, polypyrrole, Ketjen black and acetylene black; the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethyl cellulose, butadiene-styrene rubber and polyacrylic acid; and the solvent is one or more of N-methylpyrrolidone, DMF, ethanol and water.

3. The aqueous ammonium-ion battery electrode of claim 2, wherein, The test is performed in a three-electrode system, which is prepared and assembled as follows:

4. A test method for a perylene diimide-based aqueous ammonium-ion battery electrode, characterized by, (1) a graphite sheet electrode is used as a counter electrode; (2) the perylene diimide compound, the conductive agent, the binder and the solvent are mixed to form an electrode slurry, which is coated on a carbon sheet and dried at 50-100°C to obtain a negative electrode sheet for an aqueous ammonium ion battery, and the negative electrode sheet is used as a working electrode; (3) a reference electrode is inserted, and an (NH4)2SO4 solution is used as an electrolyte solution; (4) battery performance is tested. The perylene diimide compound has a general structure as shown in formula (I): wherein R is H. The mass ratio of the perylene diimide compound, the conductive agent and the binder is 6:2:

2.

5. The test method of claim 4, wherein, ​

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