CN115710230A

CN115710230A - Naphtho [2,3-d ] imidazole-4, 9-dione derivative used as positive electrode of organic lithium ion battery and preparation method thereof

Info

Publication number: CN115710230A
Application number: CN202211438143.1A
Authority: CN
Inventors: 许娟; 朱一方; 曹剑瑜
Original assignee: Changzhou University
Current assignee: Changzhou University
Priority date: 2022-11-16
Filing date: 2022-11-16
Publication date: 2023-02-24

Abstract

The invention belongs to the field of synthesis of lithium ion battery materials, and particularly provides a naphtho [2,3-d ] imidazole-4, 9-diketone derivative used as a positive electrode of an organic lithium ion battery and a preparation method thereof. Firstly, 2, 3-dichloro-1, 4-naphthoquinone and phthalimide potassium are taken as raw materials to prepare 2, 3-diamino-1, 4-naphthoquinone; then grafting 2, 3-diamino-1, 4-naphthoquinone on glacial acetic acid, terephthalaldehyde or 1,3, 5-mesitylene aldehyde respectively to obtain different substituted naphtho [2,3-d ] imidazole-4, 9-diketone derivatives. The organic lithium ion battery using the derivative as the positive electrode can obtain higher capacity and has better cycle stability. The preparation method is simple and easy to implement, and the obtained electrode material has good battery capacity and cycle life and has wide application prospect in a lithium ion battery system.

Description

Naphtho [2,3-d ] imidazole-4, 9-dione derivative used as positive electrode of organic lithium ion battery and preparation method thereof

Technical Field

The invention belongs to the field of synthesis of lithium ion battery materials, and particularly provides a naphtho [2,3-d ] imidazole-4, 9-diketone derivative used as a positive electrode of an organic lithium ion battery and a preparation method thereof.

Background

The ever-increasing energy demand has prompted the world to develop a variety of cleaner, more environmentally friendly energy storage technologies. Lithium Ion Batteries (LIBs) are widely used in the field of various electric vehicles and electric tools due to their advantages of high energy density, long cycle life, and easy mass production. The search for electrode materials with superior electrochemical performance has been the development direction of LIBs. The prior positive electrode materials of LIBs are mainly inorganic lithium salts, such as LiCoO ₂ 、LiMnO ₄ And LiFePO ₄ And the like. Although these inorganic lithium salts have been applied to commercial LIBs, the toxicity, high cost and poor recyclability of the transition metals therein inhibit further widespread use in new energy vehicles.

Over the past decade, redox-active organic molecules have attracted considerable interest as electrode materials for lithium ion batteries. Compared with transition metal-based inorganic electrode materials, the organic electrode material has the advantages of low cost, environmental friendliness, various structures, convenience in synthesis, adjustable electrochemical performance and the like. To date, many organic molecules with different redox species have been investigated as positive electrode materials for lithium ion batteries. Among them, conjugated carbonyl compounds are considered as the most promising materials because of their higher theoretical specific capacity, good electrochemical activity and ease of synthesis. However, their practical use is severely hampered by their dissolution problems in organic electrolytes, resulting in poor cycle stability, low coulombic efficiency and low specific capacity of conventional organic lithium ion batteries.

The existing method for solving the problem of low specific capacity of the organic lithium ion battery mainly focuses on increasing electrochemical active sites, such as grafting new active groups in an organic electrode material, but the existing electrode material also has the problems of low discharge capacity and low cycle life caused by dissolution or decomposition.

Disclosure of Invention

The invention aims to provide a high-performance positive electrode material naphtho [2,3-d ] imidazole-4, 9-diketone derivative for an organic lithium ion battery. The material has the advantages of easily obtained synthetic raw materials, simple and convenient synthetic method, easy large-scale production and high yield. The material is applied to the anode of the lithium ion battery, has the advantages of high electrochemical capacity and long cycle life, and has wide application prospect.

The technical scheme adopted by the invention is as follows: firstly, 2, 3-dichloro-1, 4-naphthoquinone and potassium phthalimide are used as raw materials, and the 2, 3-diamino-1, 4-naphthoquinone is prepared by adopting a reflux heating method under the protection of nitrogen. Then, the prepared 2, 3-diamino-1, 4-naphthoquinone is respectively reacted with glacial acetic acid, terephthalaldehyde or 1,3, 5-trimesic aldehyde to prepare 2-methyl-1H-naphtho [2,3-d ] imidazole-4, 9-ketone (IMNQ-1), 2 '-2- (1, 4-phenyl) p- (1H-naphtho [2,3-d ] imidazole-4, 9-dione (IMNQ-2) or 2,2' - (benzene-1, 3, 5-triyl) tri (1H-naphthyl [2,3-d ] imidazole-4, 9-dione (IMNQ-3), and finally, the three naphtho [2,3-d ] imidazole-4, 9-dione derivatives are taken as positive electrode materials and assembled into the organic lithium ion battery together with a metal lithium sheet.

The organic lithium ion battery using the naphtho [2,3-d ] imidazole-4, 9-diketone derivative as the anode material provided by the invention has the following specific operation:

(1) Dissolving 2, 3-dichloro-1, 4-naphthoquinone and potassium phthalimide in 200mL of acetonitrile solution, refluxing for 6-12h under the protection of nitrogen, cooling to room temperature, and filtering to obtain a yellow solid intermediate product. Putting the intermediate product into a round-bottom flask, adding 10mL of hydrazine hydrate, and reacting at 60 ℃ for 12 hours to prepare dark blue 2, 3-diamino-1, 4-naphthoquinone;

wherein the mass ratio of the 2, 3-dichloro-1, 4-naphthoquinone to the phthalimide potassium is 1.

(2) Adding 2, 3-diamino-1, 4-naphthoquinone into glacial acetic acid, and heating under reflux for 3-7 h under the protection of nitrogen. Cooling the product, washing with acetic acid, ethanol, diethyl ether and water, and drying to obtain gray product 2-methyl-1H-naphtho [2,3-d ] imidazole-4, 9-ketone (IMNQ-1);

wherein the mass ratio of the 2, 3-diamino-1, 4-naphthoquinone to the glacial acetic acid is 1.

Or adding 2, 3-diamino-1, 4-naphthoquinone and terephthalaldehyde into a flask together, adding 8mL of DMSO, and stirring at 80-120 ℃ for reaction for 3-7 h. After cooling, the solvent was removed by suction filtration, then ethanol and water were added in order to wash, and finally recrystallization in DMF gave a tan product of 2'2- (1, 4-phenyl) p- (1H-naphtho [2,3-d ] imidazole-4, 9-dione (IMNQ-2);

wherein the mass ratio of the 2, 3-diamino-1, 4-naphthoquinone to the terephthalaldehyde is 1.

Or dissolving 2, 3-diamino-1, 4-naphthoquinone and 1,3, 5-mesitylene in 15mL of dimethyl sulfoxide solution, placing the solution in an oil bath at the temperature of 80-120 ℃ for reaction for 6-24 h, cooling to room temperature after the reaction is finished, and filtering to separate out a brown yellow solid. Placing the brown yellow solid in a flask, adding 200mL of N, N-Dimethylformamide (DMF), heating and refluxing for 20 minutes, filtering, washing and drying the product to remove residual DMF to obtain bright yellow 2,2' - (benzene-1, 3, 5-triyl) tris (1H-naphthyl [2,3-d ] imidazole-4, 9-dione (IMNQ-3);

wherein the mass ratio of the 2, 3-diamino-1, 4-naphthoquinone to the 1,3, 5-mesitylene is 1.

(3) And (3) assembling the organic lithium ion battery by taking the naphtho [2,3-d ] imidazole-4, 9-diketone derivative prepared in the step (2) as a positive electrode and a lithium sheet as a negative electrode.

The diaphragm of the assembled battery is a porous polypropylene film (Celgard 2400) with the diameter of 19mm, and the electrolyte is dissolved with 1M LiTFSI and 1wt.% LiNO ₃ 1, 4-Dioxane (DOL) and ethylene glycol dimethyl ether (DME) (volume ratio 1.

The invention has the beneficial effects that: the invention prepares three naphtho [2,3-d ] imidazole-4, 9-dione derivatives which are 2, 3-diamino-1, 4-naphthoquinone (IMNQ-1), 2'2- (1, 4-phenyl) p- (1H-naphtho [2,3-d ] imidazole-4, 9-dione (IMNQ-2) and 2,2' - (benzene-1, 3, 5-triyl) tri (1H-naphthyl [2,3-d ] imidazole-4, 9-dione (IMNQ-3) respectively, and the naphtho [2,3-d ] imidazole-4, 9-dione is used as a positive electrode material of an organic lithium ion battery to achieve the aim of improving the electrochemical capacity and the cycle life of the organic lithium ion battery.

The invention not only provides an organic lithium ion battery using naphtho [2,3-d ] imidazole-4, 9-diketone derivatives as anode materials, but also solves the problems of low actual electrochemical capacity and short cycle life caused by dissolution in electrolyte of the existing organic lithium ion battery.

Description of the drawings:

FIG. 1 is a BET specific surface area graph of IMNQ-1 prepared in example 1.

FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of 2, 3-diamino-1, 4-naphthoquinone prepared in example 1.

FIG. 3 shows the current density of 0.1 Ag for the organic lithium ion battery IMNQ-1// Li assembled in example 1 ^-1 The following charge-discharge curve diagram.

FIG. 4 shows IMNQ-1// Li at a current density of 10 Ag for the assembled organic lithium ion battery of example 1 ^-1 Cycle life diagram of the following.

FIG. 5 shows the current density of 0.1 Ag for the organic lithium ion battery IMNQ-2// Li assembled in example 2 ^-1 The following charge-discharge curve.

FIG. 6 shows the current density of IMNQ-2// Li at 10 ag for the assembled organic lithium ion battery of example 2 ^-1 Cycle life diagram of the following.

FIG. 7 is a nuclear magnetic hydrogen spectrum of IMNQ-3 prepared in example 3.

FIG. 8 shows the current density of IMNQ-3// Li at 0.1 ag for the organic lithium ion battery assembled in example 3 ^-1 The following charge-discharge curve diagram.

FIG. 9 shows the current density of IMNQ-3// Li at 10 Ag for the organic lithium ion battery assembled in example 3 ^-1 Lower cycle life and coulombic efficiency plots.

FIG. 10 is a graph showing the charge and discharge curves of the assembled organolithium-ion battery e-PAQPy// Li of comparative example 1.

FIG. 11 is a graph showing the cycle life of the assembled organolithium-ion battery e-PAQPy// Li of comparative example 1.

Detailed Description

The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.

Example 1

(1) 10g of 2, 3-dichloro-1, 4-naphthoquinone and 16.5g of potassium phthalimide are jointly dissolved in 200mL of acetonitrile solution, reflux is carried out for 12 hours under the protection of nitrogen, the mixture is cooled to room temperature, and a yellow solid intermediate product is obtained after filtration. Putting the intermediate product into a round-bottom flask, adding 10mL of hydrazine hydrate, and reacting at 60 ℃ for 12 hours to prepare dark blue 2, 3-diamino-1, 4-naphthoquinone; the NMR spectrum of the prepared 2, 3-diamino-1, 4-naphthoquinone is shown in FIG. 2. Three hydrogen peaks are evident in the figure.

(2) 0.188g 2, 3-diamino-1, 4-naphthoquinone (1 mmol) was added to 30mL glacial acetic acid and heated under reflux under nitrogen for 7h. Cooling the product, washing with acetic acid, ethanol, diethyl ether and water, and oven drying to obtain gray product 2-methyl-1H-naphtho [2,3-d ]]Imidazol-4, 9-one (IMNQ-1) was prepared in an IMNQ-1 yield of 92% and a BET specific surface area of 48.9m2 g ^-1 (FIG. 1). The mass ratio of the 2, 3-diamino-1, 4-naphthoquinone to the glacial acetic acid is 1;

(3) To prepare 2-methyl-1H-naphtho [2,3-d ]]And (3) assembling the organic lithium ion battery IMNQ-1// Li by taking imidazole-4, 9-ketone (IMNQ-1) as a positive electrode and a lithium sheet as a negative electrode. The separator is a 19mm porous polypropylene film (Celgard 2400), and the electrolyte is a solution of 1M LiTFSI and 1wt.% LiNO ₃ 1, 4-Dioxane (DOL) and ethylene glycol dimethyl ether (DME) (volume ratio 1.

FIG. 3 shows the current density of 0.1 Ag for the organic lithium ion battery IMNQ-1// Li assembled in example 1 ^-1 The following charge-discharge curve. The electrochemical capacity of the battery is 268mAh g ^-1 。

FIG. 4 shows the current density of IMNQ-1// Li at 10 Ag for the organic lithium ion battery assembled in example 1 ^-1 Cycle life graph below. After 3000 cycles, the capacity of the IMNQ-1// Li of the organic lithium ion battery can still be kept at 191mAh g ^-1 The capacity retention rate was 71.3%.

Example 2

(1) 10g of 2, 3-dichloro-1, 4-naphthoquinone and 10g of phthalimide potassium are jointly dissolved in 200mL of acetonitrile solution, reflux is carried out for 6 hours under the protection of nitrogen, the mixture is cooled to room temperature, and a yellow solid intermediate product is obtained after filtration. Putting the intermediate product into a round-bottom flask, adding 10mL of hydrazine hydrate, and reacting at 60 ℃ for 12h to prepare dark blue 2, 3-diamino-1, 4-naphthoquinone;

(2) 0.402g of 2, 3-diamino-1, 4-naphthoquinone and 0.134g of terephthalaldehyde were added together to the flask, and 8mL of DMSO was further added thereto, followed by reaction with stirring at 120 ℃ for 7 hours. After cooling, removing the solvent by suction filtration, then sequentially adding ethanol and water for washing, and finally recrystallizing in DMF to obtain a brown yellow product of 2- (1, 4-phenyl) p- (1H-naphtho [2,3-d ] imidazole-4, 9-dione (IMNQ-2). The yield of IMNQ-2 is 94%. The mass ratio of 2, 3-diamino-1, 4-naphthoquinone to terephthalaldehyde is 3;

(3) An organic lithium ion battery IMNQ-2// Li was assembled by using 2'2- (1, 4-phenyl) p- (1H-naphtho [2,3-d ] imidazole-4, 9-dione (IMNQ-2) as a positive electrode and a lithium sheet as a negative electrode in the same manner as in example 1.

FIG. 5 shows the current density of 0.1 Ag for the organic lithium ion battery IMNQ-2// Li assembled in example 2 ^-1 The following charge-discharge curve diagram. The electrochemical capacity of the battery is 398mAh g ^-1 。

FIG. 6 shows the current density of IMNQ-2// Li at 10 Ag for the organic lithium ion battery assembled in example 2 ^-1 Cycle life diagram of the following. At a current density of 10 ag ^-1 The first-circle discharge capacity of the organic lithium ion battery IMNQ-1// Li is 292mAh g ^-1 After 1200 cycles, the capacity of the battery can still be kept at 218mAh g ^-1 The capacity retention rate was 74.7%.

Example 3

(1) 10g of 2, 3-dichloro-1, 4-naphthoquinone and 30g of phthalimide potassium are jointly dissolved in 200mL of acetonitrile solution, reflux is carried out for 12 hours under the protection of nitrogen, the mixture is cooled to room temperature, and a yellow solid intermediate product is obtained after filtration. Putting the intermediate product into a round-bottom flask, adding 10mL of hydrazine hydrate, and reacting at 60 ℃ for 12 hours to prepare dark blue 2, 3-diamino-1, 4-naphthoquinone;

(2) Dissolving 0.648g of 2, 3-diamino-1, 4-naphthoquinone and 0.162g of 1,3, 5-mesitylene-trimethyl aldehyde in 15mL of dimethyl sulfoxide solution, placing the solution in an oil bath at 120 ℃ for reaction for 24 hours, cooling the solution to room temperature after the reaction is finished, and filtering the solution to separate a brown yellow solid. Placing the brown yellow solid in a flask, adding 200mL of N, N-Dimethylformamide (DMF), heating and refluxing for 20 minutes, filtering, washing and drying the product to remove residual DMF, and obtaining bright yellow 2,2' - (benzene-1, 3, 5-triyl) tris (1H-naphthyl [2,3-d ] imidazole-4, 9-dione (IMNQ-3). The yield of IMNQ-3 is 97%. The mass ratio of 2, 3-diamino-1, 4-naphthoquinone to 1,3, 5-trimesic aldehyde is 4;

(3) The procedure for assembling an organic lithium ion battery IMNQ-3// Li using the prepared 2,2' - (benzene-1, 3, 5-triyl) tris (1H-naphthyl [2,3-d ] imidazole-4, 9-dione (IMNQ-3) as a positive electrode and a lithium plate as a negative electrode was the same as in example 1.

FIG. 7 shows the prepared IMNQ-3 nuclear magnetic hydrogen spectrum. As can be seen from the figure, the amino group peak at 5.45ppm disappeared while H was observed in comparison with the hydrogen nuclear magnetic resonance spectrum of 2, 3-diamino-1, 4-naphthoquinone in FIG. 2 _c And H _b The peaks shift to 8.00-7.99ppm and 8.36-8.38ppm, respectively. At the same time, a new peak appears at 9.32ppm, corresponding to H on the benzene ring _a Peak(s).

FIG. 8 shows the current density of IMNQ-3// Li at 0.1 ag for the organic lithium ion battery assembled in example 3 ^-1 The following charge-discharge curve diagram. The electrochemical capacity of the battery is 648mAh g ^-1 。

FIG. 9 shows the current density of IMNQ-2// Li at 10 Ag for the organic lithium ion battery assembled in example 3 ^-1 Cycle life diagram of the following. The capacity of the first turn is 410mAh g ^-1 After 3000 cycles, the capacity of the IMNQ-1// Li of the organic lithium ion battery is 308mAh g ^-1 The capacity retention rate was 75.1%.

Example 4

(1) 10g of 2, 3-dichloro-1, 4-naphthoquinone and 16.5g of potassium phthalimide are jointly dissolved in 200mL of acetonitrile solution, reflux is carried out for 12 hours under the protection of nitrogen, the mixture is cooled to room temperature, and a yellow solid intermediate product is obtained after filtration. Putting the intermediate product into a round-bottom flask, adding 10mL of hydrazine hydrate, and reacting at 60 ℃ for 12 hours to prepare dark blue 2, 3-diamino-1, 4-naphthoquinone;

(2) 0.189g of 2, 3-diamino-1, 4-naphthoquinone (1 mmol) was added to 54mL of glacial acetic acid and heated under reflux for 7h under nitrogen. After cooling the product, washing it with acetic acid, ethanol, ether and water respectively, and drying to obtain a gray product 2-methyl-1H-naphtho [2,3-d ] imidazole-4, 9-ketone (IMNQ-1). The yield of IMNQ-1 was 88%. The mass ratio of the 2, 3-diamino-1, 4-naphthoquinone to the glacial acetic acid is 1;

(3) To prepare 2-methyl-1H-naphtho [2,3-d]Imidazole-4, 9-ketone (IMNQ-1) is used as a positive electrode, and a lithium sheet is used as a negative electrodeAnd (3) assembling the organic lithium ion battery IMNQ-1// Li. The separator is a 19mm porous polypropylene film (Celgard 2400), and the electrolyte is a solution of 1M LiTFSI and 1wt.% LiNO ₃ 1, 4-Dioxane (DOL) and ethylene glycol dimethyl ether (DME) (volume ratio 1.

Organic lithium ion battery IMNQ-1// Li assembled with the organic material prepared in example 4 at a current density of 0.1 Ag ^-1 Electrochemical capacity at 259mAh g ^-1 At a current density of 10 Ag ^-1 The capacity retention rate after 3000 cycles of lower circulation is 66.7%.

Example 5

(2) 0.134g of 2, 3-diamino-1, 4-naphthoquinone and 0.402g of terephthalaldehyde were added together to a flask, and 8mL of DMSO was added thereto, followed by stirring at 120 ℃ for reaction for 7 hours. After cooling, the solvent was removed by suction filtration, then ethanol and water were sequentially added to wash, and finally recrystallization was carried out in DMF to obtain a tan product 2' (1, 4-phenyl) p- (1H-naphtho [2,3-d ] imidazole-4, 9-dione (IMNQ-2). Yield of IMNQ-2 was 91%. The mass ratio of 2, 3-diamino-1, 4-naphthoquinone to terephthalaldehyde was 1;

Organic lithium ion battery IMNQ-2// Li assembled with the organic electrode material prepared in example 5 at a current density of 0.1 Ag ^-1 Electrochemical capacity at the lower point is 486mAh g ^-1 At a current density of 10 ag ^-1 The capacity retention rate after 1200 cycles of the lower cycle was 88.9%.

Example 6

(1) 10g of 2, 3-dichloro-1, 4-naphthoquinone and 30g of phthalimide potassium are jointly dissolved in 200mL of acetonitrile solution, reflux is carried out for 12 hours under the protection of nitrogen, the mixture is cooled to room temperature, and a yellow solid intermediate product is obtained after filtration. Putting the intermediate product into a round-bottom flask, adding 10mL of hydrazine hydrate, and reacting at 60 ℃ for 12h to prepare dark blue 2, 3-diamino-1, 4-naphthoquinone;

(2) Dissolving 0.162g of 2, 3-diamino-1, 4-naphthoquinone and 0.648g of 1,3, 5-mesitylene in 15mL of dimethyl sulfoxide solution, placing the solution in an oil bath at 120 ℃ for reaction for 24 hours, cooling the solution to room temperature after the reaction is finished, and filtering to separate a brown yellow solid. Placing the brown yellow solid in a flask, adding 200mL of N, N-Dimethylformamide (DMF), heating and refluxing for 20 minutes, filtering, washing and drying the product to remove residual DMF, and obtaining bright yellow 2,2' - (benzene-1, 3, 5-triyl) tri (1H-naphthyl [2,3-d ] imidazole-4, 9-diketone (IMNQ-3). The yield of IMNQ-3 is 94%, the mass ratio of 2, 3-diamino-1, 4-naphthoquinone to 1,3, 5-trimesic aldehyde is 1;

Example 6 assembled organic lithium ion Battery IMNQ-3// Li at Current Density 0.1 Ag ^-1 The charge and discharge capacity is 633mAh g ^-1 And the capacity retention rate after 3000 cycles is 78.8%.

Comparative example 1 Synthesis of polypyrrole anthraquinone (e-PAQPy) and electrochemical Performance of assembled lithium ion Battery e-PAQPy// Li

A250 mL three-necked flask was charged with 2-aminoanthraquinone (0.9g, 4.032mmol), 2, 5-dimethoxytetrahydrofuran (1.05mL, 8.064mmol), N-dimethylformamide (90 mL), iodine (0.102g, 0.402mmol), and water (3.6 mL), and heated to 120 ℃ in an oil bath under nitrogen and refluxed for 3h. And (3) cooling the reactant to room temperature, adding 300mL of water, stirring to separate out a precipitate, standing for 2h, performing suction filtration to obtain a yellow solid filter cake, washing for 3-5 times by using warm water, and performing vacuum drying on the product at 60 ℃ for 12h to obtain the yield of about 87%.

100mg of pyrrole anthraquinone monomer is dissolved in 30mL of DMSO, 4mmol of LiClO4 is added, and the mixture is placed in an electrolytic cell. Under the protection of nitrogen, a carbon felt electrode is used as a working electrode and a counter electrode, an Ag electrode is used as a reference electrode, and electrolysis is carried out for 80 hours at a constant potential of 1.7V. After the reaction is finished, 300mL of water is added to precipitate, then a dark brown initial product is obtained by suction filtration, washed by deionized water for 3-5 times and dried in vacuum at 60 ℃ for 12h to obtain the polypyrrole anthraquinone (the yield is about 40%).

FIG. 10 is a charge/discharge diagram of an e-PAQPy// Li battery using the e-PAQPy prepared in comparative example 1 as a positive electrode. The battery capacity is 197mAh g ^-1 。

FIG. 11 is a graph of cycle life for an e-PAQPy// Li cell. After 600 cycles, the discharge capacity retention rate of the battery was 70%.

Claims

1. A process for the preparation of a naphtho [2,3-d ] imidazole-4, 9-dione derivative, characterized in that it comprises the following steps:

(1) Dissolving 2, 3-dichloro-1, 4-naphthoquinone and phthalimide potassium in acetonitrile solution, carrying out reflux reaction for 6-12h under the protection of nitrogen, cooling to room temperature, and filtering to obtain a yellow solid intermediate product; putting the yellow intermediate product into a round-bottom flask, adding hydrazine hydrate, and reacting at 60 ℃ for 12 hours to prepare dark blue 2, 3-diamino-1, 4-naphthoquinone;

(2) Adding 2, 3-diamino-1, 4-naphthoquinone into glacial acetic acid for reaction, cooling the product, washing with acetic acid, ethanol, diethyl ether and water respectively, and drying to obtain gray product 2-methyl-1H-naphtho [2,3-d ] imidazole-4, 9-ketone (IMNQ-1);

or

Adding 2, 3-diamino-1, 4-naphthoquinone and terephthalaldehyde into a flask together, adding a dimethyl sulfoxide solution, stirring for reaction, cooling, performing suction filtration to remove a solvent, sequentially adding ethanol and water for washing, and finally recrystallizing in DMF to obtain a brown yellow product of 2;

or

Dissolving 2, 3-diamino-1, 4-naphthoquinone and 1,3, 5-mesitylene in DMSO solution, placing in an oil bath for reaction, cooling to room temperature after the reaction is finished, filtering to separate out a tan solid, placing the tan solid in a flask, adding N, N-dimethylformamide, heating and refluxing for 20 minutes, filtering, washing and drying the product, and removing residual DMF to obtain bright yellow 2,2' - (benzene-1, 3, 5-triyl) tri (1H-naphthyl [2,3-d ] imidazole-4, 9-dione (IMNQ-3).

2. The process for producing a naphtho [2,3-d ] imidazole-4, 9-dione derivative according to claim 1, wherein the mass ratio of 2, 3-dichloro-1, 4-naphthoquinone to potassium phthalimide in step (1) is 1.

3. The method for preparing the naphtho [2,3-d ] imidazole-4, 9-dione derivative according to claim 1, wherein the mass ratio of the 2, 3-diamino-1, 4-naphthoquinone to the glacial acetic acid in the step (2) is 1.

4. The process for producing a naphtho [2,3-d ] imidazole-4, 9-dione derivative according to claim 1, wherein the mass ratio of 2, 3-diamino-1, 4-naphthoquinone to terephthalaldehyde in the step (2) is 1.

5. The process for producing a naphtho [2,3-d ] imidazole-4, 9-dione derivative according to claim 1, wherein the mass ratio of 2, 3-diamino-1, 4-naphthoquinone to 1,3, 5-trimesic aldehyde in step (2) is 1.

6. The naphtho [2,3-d ] imidazole-4, 9-dione derivative prepared according to any one of claims 1 to 5, wherein the naphtho [2,3-d ] imidazole-4, 9-dione derivative is 2-methyl-1H-naphtho [2,3-d ] imidazole-4, 9-one (IMNQ-1), 2 'l 2- (1, 4-phenyl) p- (1H-naphtho [2,3-d ] imidazole-4, 9-dione (IMNQ-2), or 2,2' - (benzene-1, 3, 5-triyl) tris (1H-naphtyl [2,3-d ] imidazole-4, 9-dione (IMNQ-3), having a molecular structural formula as follows:

R ₁ -R ₁₈ each of which is independently selected from H, alkyl, alkoxy, alkylthio, halogen, hydroxy, amino, nitro, mercapto, carboxy or cyano.

7. Use of the naphtho [2,3-d ] imidazole-4, 9-dione derivative prepared according to any one of claims 1 to 5 as a positive electrode material for an organic lithium ion battery.

8. The naphtho [2,3-d ] of claim 7]Use of imidazole-4, 9-dione derivatives, characterised in that they are naphtho [2,3-d ]]The imidazole-4, 9-diketone derivative is used as a positive electrode, a lithium sheet is used as a negative electrode, the organic lithium ion battery is assembled, a porous polypropylene membrane is selected as a diaphragm, and 1M LiTFSI and 1wt.% LiNO are dissolved in electrolyte ₃ 1, 4-Dioxane (DOL) and ethylene glycol dimethyl ether (DME).