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

Abstract

The invention belongs to the technical field of energy storage materials, and particularly relates to an aqueous ammonium ion battery electrode material based on perylene diimide, a preparation method and application. Firstly, a perylene diimide compound and a preparation method are provided, the material is stable, the material is rich in carbonyl structures, and enol type conversion can be carried out in the charging and discharging process to combine / release ammonium ions to complete charge storage; the invention also provides a water-based battery prepared from the perylene diimide compound and a preparation method, and the water-based battery has reversible specific capacity of 190.62 mAh / g in 1M (NH4) 2SO4 solution and current density of 1A / g, and shows excellent rate capability. After 1000 cycles of continuous charging and discharging in a 1M (NH4) 2SO4 solution and at the current density of 10A / g, the lithium ion battery still has the specific capacity of 101.67 mAh / g, and the lithium ion battery is simple in preparation process, low in cost and wide in market application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of energy storage materials, and in particular relates to an aqueous ammonium ion battery electrode material based on perylene diimide, a preparation method and an application thereof. Technical Background

[0002] In recent years, as the awareness of environmental protection and resource conservation continues to increase, the research and development of new energy storage materials has received more and more attention. Aqueous ammonium ion batteries are new non-metallic energy storage batteries with ammonium ions as carriers, which have many advantages and broad development prospects. Ammonium ion resources are abundant, the cost of its compounds is low, and the price of aqueous electrolytes is not high, which reduces the overall cost of the battery. In addition, aqueous electrolytes are non-flammable and non-explosive, and are safe to use, reducing the safety risks of batteries during use and storage. They have a smaller hydration radius With a small molar mass (18 g / mol), it can realize the rapid migration and transfer of ions, quickly embed and de-embed in the electrode material without causing the collapse of the electrode material, and minimize the corrosion to the equipment in a neutral or weakly acidic environment.

[0003] However, the research and development of electrode materials is limited. In terms of positive electrode materials, such as Prussian blue analogs and metal oxides, although they are used, intercalation positive electrode materials have limited capacity and slow kinetics, and it is difficult to meet the requirements of high-performance batteries; in terms of negative electrode materials, although there are some options such as organic materials and synthetic polymer materials, there are problems such as irreversible embedding, electrode expansion, and electrolyte consumption, resulting in low Coulomb efficiency. In response to the above technical problems, Hanmei Jiang et al. found that regulating asymmetric bimetallic sites can reduce NH4 + The desolvation barrier of (H2O)4 at the electrode-electrolyte interface improves diffusion kinetics and structural stability; Ling, Dandan et al. synthesized oxygen-vacancy-rich Bi2SeO5 nanosheets by hydrothermal method to accelerate ion transport and improve material conductivity. Bao Zhuoheng et al. predicted the working potential of V2CTxMXene, which, as a low working potential anode, exhibited good pseudocapacitive behavior and cycle stability.

[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. + After combining with small organic molecules, the solubility increases and the electrode dissolution occurs easily. The steric hindrance effect of organic compounds leads to NH4 + The inability to fully utilize its active sites, resulting in low actual capacity and other problems, affects the electrochemical performance of the battery.

[0005] References:

[0006] Hanmei Jiang,Hao Yuan,Qiang Chen,Jiang Guo 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,PanLong,Duan Lunbo,Tang Hongjian,Wu Yuping,Hu Linfeng,Sun ZhengMing.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 of the invention

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

[0011] To achieve the above object, the technical solution adopted by the present invention is:

[0012] The primary purpose of the present invention is to provide perylene diimide compounds, the general structural formula of the perylene diimide compounds is shown in formula (I):

[0013]

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

[0015] The second object of the present invention is to provide a method for preparing 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 an aniline derivative in NMP to obtain solution B;

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

[0018] (3) After the reaction is completed, the mixture is cooled to room temperature, washed by centrifugation with ethanol and deionized water, and dried to obtain a perylene diimide compound.

[0019] Preferably, the aniline derivative described in step (1) includes 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 to aniline or aniline derivative in step (1) is from 1:2 to 1:3.

[0021] Preferably, the mixture in step (2) is stirred for 2 hours, the reaction temperature is set at 200° C., and the reaction time is 12-36 hours.

[0022] The third object of the present invention is to provide the use of the perylene diimide compound or the perylene diimide compound prepared by the preparation method in the preparation of aqueous ammonium ion battery electrode materials.

[0023] The fourth object of the present invention is an aqueous ammonium ion battery electrode based on perylene diimide compounds, which is prepared by the following method: perylene diimide compounds, conductive agents, binders and solvents are mixed to form electrode slurry, which is coated on a carbon sheet and dried at 50 to 100° C. to obtain an aqueous 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, and acetylene black; the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethyl cellulose, styrene-butadiene rubber, and polyacrylic acid; and the solvent is one or more of N-methylpyrrolidone, DMF, ethanol, and water.

[0025] The fifth object of the present invention is to provide a method for testing aqueous ammonium ion battery electrodes based on perylene diimide compounds, which is carried out in a three-electrode system. The preparation and assembly process of the three-electrode system is as follows:

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

[0027] (2) mixing a perylene diimide compound, a conductive agent, a binder and a solvent to prepare an electrode slurry, coating the slurry on a carbon sheet, and drying the slurry at 50 to 100° C. to obtain an aqueous ammonium ion battery negative electrode sheet, and using the aqueous ammonium ion battery negative electrode sheet as a working electrode;

[0028] (3) Insert the reference electrode and use (NH4)2SO4 solution as the electrolyte solution;

[0029] (4) Conduct battery performance test.

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

[0031] The present invention has the following effects:

[0032] (1) The present invention first provides a perylene diimide compound and provides a detailed preparation method of the perylene diimide compound. The preparation method is simple, the material is stable, and it is rich in carbonyl structure. It can undergo enol conversion during the charge and discharge process to combine / release ammonium ions to complete charge storage; the structure is regular and has a π-π conjugated structure, which enhances the conductivity and facilitates the rapid insertion / stripping of ions. In addition, the reasonable electron delocalization regulation of the 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 present invention provides an aqueous battery prepared from perylene diimide compounds and a preparation method thereof. The prepared aqueous battery has a reversible specific capacity of 190.62 mAh / g in a 1M (NH4)2SO4 solution and a current density of 1A / g, and exhibits excellent rate performance. In a 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 charge and discharge.

[0034] (3) The preparation process used in the present invention is simple, low-cost, and has broad market application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] The protection scope of the present invention is described in detail below with reference to the specific drawings.

[0036] Figure 1 This is the SEM image of the perylene diimide PTCDAn prepared in Example 1

[0037] Figure 2 The constant current charge-discharge curve of the perylene diimide PTCDAn prepared in Example 1

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

[0039] The present invention is described in detail below in conjunction with embodiments.

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

[0041] In the following implementation, the NMP solution is N-methylpyrrolidone, which is an aprotic solvent and is characterized by high polarity, high boiling point, low viscosity, and high thermal and chemical stability.

[0042] It should be noted that the following embodiments are not all experimental results conducted by the inventors, but only a reflection of some experimental results.

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

[0044] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of aniline 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 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 the solution were cooled to room temperature, and then centrifuged and washed with ethanol and deionized water, and dried to obtain perylene diimide PTCDAn, whose structure is shown in the following formula:

[0045]

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

[0047] Example 2: Preparation method of aqueous ammonium ion battery electrode material based on perylene diimide

[0048] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 2-fluoroaniline 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 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 the solution were cooled to room temperature, and then centrifuged and 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 aqueous ammonium ion battery electrode material based on perylene diimide

[0051] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 3-fluoroaniline 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 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 the solution were cooled to room temperature, and then centrifuged and 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 aqueous ammonium ion battery electrode material based on perylene diimide

[0054] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 4-fluoroaniline 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 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 the solution were cooled to room temperature, and then centrifuged and 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 aqueous ammonium ion battery electrode material based on perylene diimide

[0057] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 2-chloroaniline 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 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 the solution were cooled to room temperature, and then centrifuged and 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 aqueous ammonium ion battery electrode material based on perylene diimide

[0060] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 3-chloroaniline 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 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 the solution were cooled to room temperature, and then centrifuged and 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 aqueous ammonium ion battery electrode material based on perylene diimide

[0063] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 4-chloroaniline 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 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 the solution were cooled to room temperature, and then centrifuged and 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: Preparation method of aqueous ammonium ion battery electrode material based on perylene diimide

[0066] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 2-bromoaniline 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 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 the solution were cooled to room temperature, and then centrifuged and 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: Preparation method of aqueous ammonium ion battery electrode material based on perylene diimide

[0069] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 3-bromoaniline 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 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 the solution were cooled to room temperature, and then centrifuged and 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: Preparation method of aqueous ammonium ion battery electrode material based on perylene diimide

[0072] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 4-bromoaniline 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 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 the solution were cooled to room temperature, and then centrifuged and 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: Preparation method of aqueous ammonium ion battery electrode material based on perylene diimide

[0075] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 2-nitroaniline 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 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 the solution were cooled to room temperature, and then centrifuged and 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: Preparation method of aqueous ammonium ion battery electrode material based on perylene diimide

[0078] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of m-nitroaniline 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 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 the solution were cooled to room temperature, and then centrifuged and 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: Preparation method of aqueous ammonium ion battery electrode material based on perylene diimide

[0081] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 4-nitroaniline hydrochloride 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 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 the solution were cooled to room temperature, and then centrifuged and 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: Preparation method of aqueous ammonium ion battery electrode material based on perylene diimide

[0084] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 2-methylaniline 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 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 the solution were cooled to room temperature, and then centrifuged and 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: Preparation method of aqueous ammonium ion battery electrode material based on perylene diimide

[0087] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 3-methylaniline 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 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 the solution were cooled to room temperature, and then centrifuged and 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: Preparation method of aqueous ammonium ion battery electrode material based on perylene diimide

[0090] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 4-methylaniline 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 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 the solution were cooled to room temperature, and then centrifuged and 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 aqueous ammonium ion battery electrode material based on perylene diimide

[0093] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 2-aminobenzonitrile 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 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 the solution were cooled to room temperature, and then centrifuged and 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 aqueous ammonium ion battery electrode material based on perylene diimide

[0096] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 3-aminobenzonitrile 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 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 the solution were cooled to room temperature, and then centrifuged and 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 aqueous ammonium ion battery electrode material based on perylene diimide

[0099] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of p-aminobenzonitrile 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 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 the solution were cooled to room temperature, and then centrifuged and 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: Preparation method of aqueous ammonium ion battery electrode material based on perylene diimide

[0102] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 2-aminobenzoic acid 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 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 the solution were cooled to room temperature, and then centrifuged and 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: Preparation method of aqueous ammonium ion battery electrode material based on perylene diimide

[0105] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 3-aminobenzoic acid 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 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 the solution were cooled to room temperature, and then centrifuged and 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: Preparation method of aqueous ammonium ion battery electrode material based on perylene diimide

[0108] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 4-aminobenzoic acid 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 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 the solution were cooled to room temperature, and then centrifuged and 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 aqueous ammonium ion battery electrode material based on perylene diimide

[0111] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 2-aminophenol 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 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 the solution were cooled to room temperature, and then centrifuged and 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 aqueous ammonium ion battery electrode material based on perylene diimide

[0114] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 3-aminophenol 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 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 the solution were cooled to room temperature, and then centrifuged and 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 aqueous ammonium ion battery electrode material based on perylene diimide

[0117] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 4-aminophenol 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 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 the solution were cooled to room temperature, and then centrifuged and 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: Preparation method of aqueous ammonium ion battery electrode material based on perylene diimide

[0120] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 2-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 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 the solution were cooled to room temperature, and then centrifuged and 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: Preparation method of aqueous ammonium ion battery electrode material based on perylene diimide

[0123] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride was dissolved in 5 mL of NMP to obtain solution A, and 1.25 mmol of 3-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 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 the solution were cooled to room temperature, and then centrifuged and 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: Preparation method of aqueous ammonium ion battery electrode material based on perylene diimide

[0126] 0.5 mmol of perylene-3,4,9,10-tetracarboxylic dianhydride 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 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 the solution were cooled to room temperature, and then centrifuged and 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:

[0127]

[0128] Example 29: Preparation of aqueous battery

[0129] It should be noted that in order to save space and reduce the repetitiveness of the experimental method, the preparation method of this embodiment only lists the method for preparing aqueous batteries using the perylene diimide PTCDAn prepared in Example 1. The perylene diimide organic materials prepared in other Examples 2-20 can all be used to prepare aqueous batteries by the following method, and there will be no significant difference in the performance of the prepared batteries.

[0130] The perylene diimide PTCDAn prepared in Example 1, the conductive agent superconducting carbon black Super P, and the binder polyvinylidene fluoride were mixed with N-methylpyrrolidone solvent in a mass ratio of 6:2:2 to prepare an electrode slurry, which was coated on a carbon sheet and vacuum dried at 60°C to obtain an aqueous ammonium ion battery negative electrode sheet. The aqueous 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 an aqueous battery with a three-electrode system, and the battery performance was tested.

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

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

[0133] In summary, the present invention provides perylene diimide compounds and provides a detailed preparation method of the perylene diimide compounds. The preparation method is simple, the material is stable, and it is rich in carbonyl structure. It can undergo enol conversion during the charge and discharge process to combine / release ammonium ions to complete charge storage; the structure is regular and has a π-π conjugated structure, which enhances the conductivity and facilitates rapid ion embedding / stripping. In addition, the reasonable electron delocalization regulation of perylene diimide organic materials weakens the steric hindrance effect, realizes reversible four-electron transfer, and enhances the cycle stability of electrode materials. The present invention also provides an aqueous battery prepared from perylene diimide compounds and a preparation method. The prepared aqueous battery has a reversible specific capacity of 190.62mAh / g at a current density of 1A / g in a 1M (NH4)2SO4 solution. It also exhibits excellent rate performance. In 1M (NH4)2SO4 solution and at a current density of 10A / g, the quinoneamine polymer perylene diimide PTCDAn still has a specific capacity of 101.67mAh / g after 1000 continuous charge and discharge cycles. The organic solvent used in the present invention 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 above specific implementation cases of the present invention are described in detail, but they are only examples, and the present invention is not limited to the specific implementation cases described above. For those skilled in the art, any equivalent modification and substitution of the present invention are also within the scope of the present invention. Therefore, the equalization and modification made without departing from the spirit and scope of the present invention should be included in the scope of the present invention.

Claims

1. A perylene diimide compound, characterized in that: The general structural formula of the perylene diimide compound is shown in formula (I): Among them, R is one of H, CH3, F, Cl, Br, I, NO2, CN, COOH, OH, OCH3, and is located at the ortho, meta or para position.

2. The method for preparing a perylene diimide compound according to claim 1, wherein: The steps include: (1) dissolving perylene-3,4,9,10-tetracarboxylic dianhydride in NMP to obtain solution A, and dissolving aniline or an aniline derivative in NMP to obtain solution B; (2) under magnetic stirring, slowly dripping solution B obtained in step (1) into solution A, stirring the mixture, transferring it into a PTFE autoclave mold, and reacting; (3) After the reaction is completed, the mixture is cooled to room temperature, washed by centrifugation with ethanol and deionized water, and dried to obtain a perylene diimide compound.

3. The preparation method according to claim 2, characterized in that: The aniline derivatives described in step (1) include 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.

4. The preparation method according to claim 2, characterized in that: The molar ratio of perylene-3,4,9,10-tetracarboxylic dianhydride to aniline or aniline derivative in step (1) is from 1:2 to 1:

3.

5. The preparation method according to claim 2, characterized in that: The mixture in step (2) is stirred for 2 hours, the reaction temperature is set at 200° C., and the reaction time is 12-36 hours.

6. Use of the perylene diimide compound according to claim 1 or the perylene diimide compound prepared by the preparation method according to any one of claims 2 to 5 in preparing an electrode material for an aqueous ammonium ion battery.

7. An aqueous ammonium ion battery electrode based on perylene diimide compounds, characterized in that: The preparation method is as follows: a perylene diimide compound, a conductive agent, a binder and a solvent are mixed to prepare 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.

8. The aqueous ammonium ion battery electrode according to claim 7, characterized in that 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, styrene-butadiene rubber, and polyacrylic acid; and the solvent is one or more of N-methylpyrrolidone, DMF, ethanol, and water.

9. A method for testing aqueous ammonium ion battery electrodes based on perylene diimide compounds, characterized in that: The three-electrode system is prepared and assembled as follows: (1) Using graphite sheet electrode as counter electrode; (2) mixing a perylene diimide compound, a conductive agent, a binder and a solvent to prepare an electrode slurry, coating the slurry on a carbon sheet, and drying the slurry at 50 to 100° C. to obtain an aqueous ammonium ion battery negative electrode sheet, and using the aqueous ammonium ion battery negative electrode sheet as a working electrode; (3) Insert the reference electrode and use (NH4)2SO4 solution as the electrolyte solution; (4) Conduct battery performance test.

10. The testing method according to claim 9, characterized in that: The mass ratio of the perylene diimide compound, the conductive agent and the binder is 6:2:2.

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