Organic nitrogen-containing polyquinone material, preparation method thereof and application of organic nitrogen-containing polyquinone material in organic lithium ion battery

Abstract

The invention belongs to the field of lithium ion battery material synthesis, and particularly discloses an organic nitrogen-containing polyquinone material, a preparation method thereof and application of the organic nitrogen-containing polyquinone material in an organic lithium ion battery. The preparation method comprises the following steps: adding 2, 3, 5, 6-tetraamino-1, 4-benzoquinone and a cyclohexanehexone hydrate into an organic solvent, refluxing under the protection of nitrogen, cooling, washing with water, drying in vacuum, and sintering in a tubular furnace to obtain a product. And then reacting the prepared product with a diamine or dinitrile compound to obtain different substituted quinoxaline [2, 3-b] phenazine-1, 2, 3, 4, 6, 8, 9, 10, 11, 13-decaketone derivatives. The derivative has carbon-nitrogen double bonds and carbon-oxygen double bonds with abundant electrochemical reaction activity, the solubility of the compound is reduced by expanding a conjugated structure, the problem of battery stability caused by the solubility is solved, and a lithium ion battery assembled by the derivative has excellent specific capacity and good cycle stability.

Description

[0001] This application is a divisional application based on the invention patent application date: 2023.05.09, application number: 202310527619.7, invention name: Organic nitrogen-containing polyquinone material and preparation method thereof and application in organic lithium-ion battery Technical Field

[0002] The invention belongs to the field of lithium ion battery material synthesis, and specifically discloses a class of organic nitrogen-containing polyquinone materials, a preparation method thereof, and application in organic lithium ion batteries. Background Art

[0003] The rapid increase in energy demand has made it urgent to research pollution-free and sustainable new energy sources. Lithium-ion batteries (LIBs), efficient and green energy storage devices, have been widely used in various fields due to their high energy density, long cycle life and easy large-scale production. However, their development is limited by the low capacity of positive electrode materials. Currently, commercial LIBs inorganic positive electrodes mainly include transition metal oxides or phosphates, such as LiCoO2, LiFePO4 or LiNi x Mn y Co z O2, etc. Their energy density has reached its theoretical upper limit, but it still struggles to meet the growing demand for energy storage applications. Furthermore, it is difficult to further increase their capacity without compromising cycling stability and safety. Furthermore, these inorganic cathodes are primarily produced from their respective minerals, and their widespread use increases the consumption of non-renewable minerals. To address these issues, green organic electroactive compounds are emerging as promising electrode materials for next-generation batteries.

[0004] Compared with inorganic cathodes, organic electrode materials have high theoretical capacity, are environmentally friendly, have low acquisition costs, and have diverse and tunable structures. To date, many organic electrode materials have been studied as cathode materials for LIBs, including organosulfur compounds, organic free radicals, imine compounds, azo compounds, and carbonyl compounds. Among them, conjugated carbonyl compounds are more attractive in rechargeable batteries due to their relatively high theoretical capacity and fast redox kinetics. However, high solubility, low active site exposure, and low conductivity have seriously hindered their further development. To overcome these problems, it is necessary to design an extended conjugated carbonyl system with good structural stability, multiple redox-exposed active sites, and improved conductivity. Summary of the Invention

[0005] The present invention aims to provide a high-performance organic nitrogen-containing polyquinone material, quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone, and its derivatives for organic lithium-ion batteries. Using tetraaminobenzoquinone and commercial cyclohexanone hydrate as raw materials, a simple and easy-to-scale production method was used to construct a polycarbonyl organic electrode material, quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone, which has a large number of redox sites. This material was then reacted with various diamines and dinitrile compounds to obtain quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivatives with different substitutions. The application of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone and different substituted quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivatives as positive electrode materials for organic lithium-ion batteries has the advantages of high electrochemical capacity and long cycle life, and has broad application prospects.

[0006] The organic nitrogen-containing polyquinone material of the present invention is quinoxaline [2,3-b] phenazine-1,2,3,4,6,8,9,10,11,13-decaone and its derivatives, specifically: quinoxaline [2,3-b] phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivatives - decaone (A), 2,3,6,7,13,14,17,18-octafluorotetrapyrazine benzotetraaza heterocycle - pentapentadienone (B), 2,3,6,7,13,14,17,18-octachlorotetrapyrazine benzotetraaza heterocycle - pentapentadienone (C), 2,3,6,7,13,14,17,18-octachlorotetrapyrazine benzotetraaza heterocycle - pentapentadienone (D), 2,3,6,7,13,14,17,18-octachlorotetrapyrazine benzotetraaza heterocycle - pentapentadienone (E), 2,3,6,7,13,14,17,18-octachlorotetrapyrazine benzotetraaza heterocycle - pentapentadienone (F ...E), 2,3,6,7,13,14,17,18-octachlorotetrapy Pyrazinebenzotetraazacyclo-pentapentadienone (C), 2,3,6,7,13,14,17,18-octanitrile tetrapyrazinebenzotetraazacyclo-pentapentadienone (D), tetraphenyl, tetrapyrazinebenzotetraazacyclo-pentapentadienone (E), tetrakis(1,4-dicarbonylnaphthyl)-tetrapyrazinebenzotetraazacyclo-pentapentadienone (F), tetrakis(quinoxalinetetrapyrazinebenzotetraazacyclo-pentapentadienone (G) or tetrakis(benzoquinoxaline-5,10-dione)-tetrapyrazinebenzotetraazacyclo-pentapentadienone (H). The specific structural formula is as follows:

[0007]

[0008] The preparation method of the organic nitrogen-containing polyquinone material of the present invention comprises the following steps:

[0009] Step 1: Weigh 2,3,5,6-tetraamino-1,4-benzoquinone derivative and cyclohexanone hydrate and add them to an organic solvent. Under nitrogen protection, heat in an oil bath and reflux for 6 hours. After the reactants are cooled to room temperature, the solvent is removed by filtration, and a brown solid is collected. The solid is then washed three times with 80°C hot water and vacuum dried to obtain a brown solid.

[0010] The molar ratio of the 2,3,5,6-tetraamino-1,4-benzoquinone derivative to the cyclohexanone hydrate is 1:2-1:4.

[0011] The organic solvent is selected from aqueous ethanol, acetic acid, nitric acid, or a combination thereof.

[0012] Heat the oil bath to 100-160°C.

[0013] Step 2: Grind the brown solid into powder, place it in a tube furnace, heat it to 300 ° C for 6 h, and obtain the product quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative - decaone.

[0014] The quinoxaline [2,3-b] phenazine-1,2,3,4,6,8,9,10,11,13-decanone prepared above was further subjected to reflux heating reaction with different diamines or dinitrile compounds (reaction conditions: reaction temperature 100

[0015] -160 ° C, time for 12-24h) to obtain different substituted quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivatives.

[0016] The diamine or dinitrile compound is selected from one of 1,2-difluoroethane-1,2-diamine, 1,2-dichloroethane-1,2-diamine, 2,3-diaminosuccinonitrile, o-phenylenediamine, 2-amino-1,4-naphthoquinone, 2,3-diaminoquinoxaline and 2,3-diaminobenzoquinoxaline-5,10-dione.

[0017] The molar ratio of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone to the diamine or dinitrile compound is 1:2-1:5.

[0018] The prepared quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivative is used as the positive electrode material of the organic lithium-ion battery and assembled with metal lithium sheets to form an organic lithium-ion battery.

[0019] The beneficial effects of the present invention are:

[0020] The present invention prepares the organic nitrogen-containing polyquinone material quinoxaline [2,3-b] phenazine

[0021] -1,2,3,4,6,8,9,10,11,13-decanone and its derivatives, and using them as positive electrode materials for organic lithium-ion batteries, thereby achieving the purpose of improving the electrochemical capacity and cycle life of organic lithium-ion batteries. The present invention not only provides an organic lithium-ion battery using quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivatives as positive electrode materials, but also solves the common problems of low actual electrochemical capacity and short cycle life caused by dissolution in electrolytes in existing organic lithium-ion batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is the reaction scheme for preparing quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivatives - decanones in Example 1.

[0023] Figure 2 This is the mass spectrum of the quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivative - decanone prepared in Example 1.

[0024] Figure 3 This is the NMR carbon spectrum of the quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivative - decanone prepared in Example 1.

[0025] Figure 4 The organic lithium ion battery assembled for Example 1 is quinoxaline [2,3-b] phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivative-decanone / / Li at a current density of 0.1Ag -1 The charge and discharge curve diagram below.

[0026] Figure 5 Example 1 of the present invention is quinoxaline [2,3-b] phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivative-decanone / / Li at a current density of 1.0Ag -1 Lithium-ion battery cycle performance diagram.

[0027] Figure 6 This is a graph of the rate performance of a lithium-ion battery at different current densities of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivative-decanone / / Li according to Example 1 of the present invention.

[0028] Figure 7 Example 2 of the present invention 2,3,6,7,13,14,17,18-octafluorotetrapyrazine benzotetraazaheterocycle-pentadienone / / Li at a current density of 1.0Ag -1Lithium-ion battery cycle performance diagram.

[0029] Figure 8 Example 3 of the present invention 2,3,6,7,13,14,17,18-octachlorotetrapyrazine benzotetraazaheterocycle-pentadienone / / Li at a current density of 1.0Ag -1 Lithium-ion battery cycle performance diagram.

[0030] Figure 9 For organic lithium-ion batteries 2'2-(1,4-phenyl)-p-(1H-naphtho[2,3-d]imidazole-4,9-dione / / Li at a current density of 1.0Ag -1 Lithium-ion battery cycle performance diagram. DETAILED DESCRIPTION

[0031] The present invention will be further described below with reference to specific examples, but the present invention is not limited to the following examples.

[0032] Example 1

[0033] Preparation and Assembly of Quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone / / Li for Organic Lithium-ion Batteries

[0034] (1) Preparation of Quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone

[0035] Step 1: Weigh 1 mmol of 2,3,5,6-tetraamino-1,4-benzoquinone and 2.0 mmol of cyclohexanone octahydrate into a three-necked flask containing 30 ml of acetic acid. Under nitrogen protection, heat in an oil bath to 120°C and reflux for 6 h.

[0036] Step 2: Stop the reaction, wait for the reactant to cool to room temperature, collect the brown solid by suction filtration, wash it 10 times by centrifugation with 80°C hot water, and vacuum dry it to obtain a brown solid;

[0037] Step 3: Place the above brown solid in a tube furnace, heat to 300°C and heat for 6 hours to obtain the final product, which is quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone.

[0038] (2) Assembly of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone / / Li for organic lithium-ion batteries

[0039] The assembly of the organic lithium-ion battery (quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone / / Li) was performed in a glove box filled with high-purity argon. Coin cells (CR2032) were assembled using the aforementioned quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone as the positive electrode, metallic lithium as the negative electrode, and a porous polypropylene membrane (Celgard 2400) as the separator. The electrolyte consisted of 1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 1 wt.% LiNO₃ dissolved in 1,3-dioxolane (DOL) and ethylene glycol dimethyl ether (DME) (1:1 volume ratio). The assembled coin cells were left undisturbed for 24 hours before electrochemical testing.

[0040] Figure 1 This is the reaction scheme for preparing quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone in this example. 2,3,5,6-Tetraamino-1,4-benzoquinone and cyclohexanone undergo an amide reaction in a simple, refluxing procedure to produce quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone in 93% yield.

[0041] Figure 2 This is the mass spectrum of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone prepared in this example. Based on the molecular formula, the predicted molecular weight of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone is 432. The primary mass-to-nuclear ratio in the mass spectrum is 432.53, consistent with the predicted molecular weight.

[0042] Figure 3 This is the C NMR spectrum of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone prepared in Example 1. The peaks at 142.07, 141.30, 133.37, and 129.88 ppm correspond to the peaks of carbon atoms a, b, c / d, and e in the molecular formula, respectively, further confirming the synthesis of the product.

[0043] Figure 4 The organic lithium-ion battery assembled for this example is quinoxaline [2,3-b] phenazine-1,2,3,4,6,8,9,10,11,13-decanone / / Li at a current density of 0.1A -1 The organic nitrogen-containing polyquinone material has a high initial discharge capacity of 334 mAh g -1, and exhibited a coulombic efficiency close to 100%, showing excellent electrochemical reversibility and long-term cycling stability, which may be attributed to the stable π-conjugated structure and high electronic conductivity of the material.

[0044] Figure 5 For this example, quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone / / Li at a current density of 1.0A -1 The lithium-ion battery cycle performance diagram under 1.0Ag is shown in the figure. -1 At the same current density, the assembled battery can still maintain 90.6% of its initial capacity after 1500 cycles.

[0045] Figure 6 This is the rate performance diagram of the lithium ion battery at different current densities of quinoxaline [2,3-b] phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivatives-decanone / / Li in this example. -1 At current densities of 334, 266, 242, 193, 167, and 144 mAh g -1 When the current density returns to the initial 0.05A -1 When the discharge capacity is reduced to 290 mAh g -1 , proving that the quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivative - decanone prepared in Example 1 of the present invention not only has excellent rate performance, but also has good reversibility.

[0046] Example 2 Preparation and Assembly of Organic Lithium-ion Battery 2,3,6,7,13,14,17,18-Octafluorotetrapyrazinebenzotetraazacyclopentadienone / / Li

[0047] (1) The preparation process of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivative - decanone is the same as that in Example 1.

[0048] (2) Preparation of 2,3,6,7,13,14,17,18-octafluorotetrapyrazinebenzotetraazacyclopentadienone

[0049] Weigh 1 mmol of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative (decaone) and 5.0 mmol of 1,2-difluoroethane-1,2-diamine into a three-necked flask containing 30 ml of acetic acid. Heat to 120°C in an oil bath under nitrogen and reflux for 24 hours. Stop the reaction, cool the mixture to room temperature, and collect the solid by filtration. Wash it 10 times with ethanol and then deionized water, respectively. Dry it in a vacuum at 60°C to obtain the final product, 2,3,6,7,13,14,17,18-octafluorotetrapyrazinebenzotetraazacyclopentadienone, in a 91% yield.

[0050] (3) Assembly of 2,3,6,7,13,14,17,18-octafluorotetrapyrazinebenzotetraazacyclopentadienone / / Li organic lithium-ion battery

[0051] The assembly of the organic lithium-ion battery 2,3,6,7,13,14,17,18-octafluorotetrapyrazinebenzotetraazacyclopentadienone / / Li was carried out in a glove box filled with high-purity argon. The assembly process was the same as in Example 1.

[0052] Figure 7 For this example, 2,3,6,7,13,14,17,18-octafluorotetrapyrazinebenzotetraazacyclopentadienone / / Li at a current density of 1.0A -1 The lithium-ion battery cycle performance diagram. As can be seen from the figure, at 1.0Ag -1 At the same current density, the assembled battery can still maintain 93.8% of its initial capacity after 1500 cycles.

[0053] Example 3 Preparation and Assembly of Organic Lithium Ion Battery 2,3,6,7,13,14,17,18-Octacholo-tetrapyrazinebenzotetraazacyclopentadienone / / Li

[0054] (1) The preparation process of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivative - decanone is the same as that in Example 1.

[0055] (2) Preparation of 2,3,6,7,13,14,17,18-octachlorotetrapyrazinebenzotetraazacyclopentadienone

[0056] 1 mmol of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative (decaone) and 2.0 mmol of 1,2-dichloroethane-1,2-diamine were added to a three-necked flask containing 30 ml of acetic acid. Under nitrogen, the mixture was heated to 160°C in an oil bath and refluxed for 24 hours. The reaction was terminated, and the mixture was allowed to cool to room temperature. The solid was collected by filtration, washed 10 times with ethanol and 10 times with deionized water, and dried under vacuum at 60°C to obtain the final product, 2,3,6,7,13,14,17,18-octachlorotetrapyrazinebenzotetraazacyclopentadienone. The yield was 86%.

[0057] (3) Assembly of 2,3,6,7,13,14,17,18-octachlorotetrapyrazinebenzotetraazacyclopentadienone / / Li organic lithium-ion battery

[0058] The assembly of the organic lithium-ion battery 2,3,6,7,13,14,17,18-octachlorotetrapyrazinebenzotetraazacyclopentadienone / / Li was carried out in a glove box filled with high-purity argon. The assembly process was the same as in Example 1.

[0059] Figure 8 For this example, 2,3,6,7,13,14,17,18-octachlorotetrapyrazinebenzotetraazacyclopentadienone / / Li at a current density of 1.0Ag -1 The lithium-ion battery cycle performance diagram. As can be seen from the figure, at 1.0Ag -1 At the same current density, the assembled battery can still maintain 86.8% of its initial capacity after 1500 cycles.

[0060] Example 4 Preparation and Assembly of Organic Lithium Ion Battery 2,3,6,7,13,14,17,18-Octanitrile Tetrapyrazine Benzotetraazaheterocycle-Pentapentadienone / / Li

[0061] (1) The preparation process of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivative - decanone is the same as that in Example 1.

[0062] (2) Preparation of 2,3,6,7,13,14,17,18-octanonitrile tetrapyrazine benzotetraazaheterocyclic pentapentadienone

[0063] Weigh 1 mmol of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative (decaone) and 3.0 mmol of 2,3-diaminosuccinonitrile into a three-necked flask containing 30 ml of ethanol-water solution. Heat to 100°C in an oil bath under nitrogen and reflux for 12 hours. Stop the reaction, cool the mixture to room temperature, and collect the solid by filtration. Wash it 10 times with ethanol and then deionized water, respectively, and dry it in a vacuum at 60°C to obtain the final product, 2,3,6,7,13,14,17,18-octanitrile tetrapyrazinebenzotetraazacyclopentadienone, in a 90% yield.

[0064] (3) Assembly of 2,3,6,7,13,14,17,18-octanonitrile tetrapyrazine benzotetraazaheterocycle-pentadienone / / Li organic lithium-ion battery

[0065] The assembly of the organic lithium-ion battery 2,3,6,7,13,14,17,18-octanitrile tetrapyrazine benzotetraazacyclopentadienone / / Li was carried out in a glove box filled with high-purity argon. The assembly process was the same as in Example 1.

[0066] The assembled battery is at 1.0Ag -1 After 1500 cycles at the same current density, the capacity can still maintain 87.2% of the initial capacity.

[0067] Example 5 Preparation and Assembly of Organic Lithium Ion Battery Tetraquinoxaline Tetrapyrazine Benzotetraazaheterocycle-Pentapentadienone / / Li

[0068] (1) The preparation process of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivative - decanone is the same as that in Example 1.

[0069] (2) Preparation of Tetraquinoxaline Tetrapyrazine Benzotetraaza Heterocycle-Pentapentadienone

[0070] Weigh 1 mmol of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative (decaone) and 4.0 mmol of 2,3-diaminoquinoxaline into a three-necked flask containing 30 ml of acetic acid. Heat to 120°C in an oil bath under nitrogen and reflux for 24 hours. Stop the reaction, cool to room temperature, and collect the solid by filtration. Wash it 10 times with ethanol and then deionized water, then dry it in a vacuum at 60°C to obtain the final product, tetraquinoxaline tetrapyrazine benzotetraazacyclopentadienone, in 81% yield.

[0071] (3) Assembly of tetraquinoxaline tetrapyrazine benzotetraazaheterocycle-pentapentadienone / / Li for organic lithium-ion batteries

[0072] The assembly of the organic lithium-ion battery quinoxaline tetraquinoxaline tetrapyrazine benzotetraazaheterocycle-pentapentadienone / / Li was carried out in a glove box filled with high-purity argon. The assembly process was the same as in Example 1.

[0073] The assembled battery is at 1.0Ag -1 After 1500 cycles at the same current density, the capacity can still maintain 82.5% of the initial capacity.

[0074] Example 6

[0075] Preparation and Assembly of Quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone Derivatives-Decanone / / Li for Organic Lithium-ion Batteries

[0076] (1) Preparation of Quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivatives - decaone

[0077] 1 mmol of 2,3,5,6-tetraamino-1,4-benzoquinone and 4.0 mmol of cyclohexanone octahydrate were weighed and added to a three-necked flask containing 30 ml of acetic acid. Under nitrogen, the mixture was heated to 120°C in an oil bath and refluxed for 6 hours. The preparation process was the same as in Example 1. The product yield was 90%.

[0078] (2) Assembly of Quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivatives-Decanone / / Li for organic lithium-ion batteries

[0079] The assembly process is the same as that of Example 1.

[0080] At 1.0Ag -1 At the same current density, the assembled battery can still maintain 89.1% of its initial capacity after 1500 cycles.

[0081] Example 7 Preparation and Assembly of Organic Lithium Ion Battery Tetraphenyl, Tetrapyrazine Benzotetraazaheterocycle-Pentapentadienone / / Li

[0082] (1) The preparation process of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative - decaone is the same as that in Example 6.

[0083] (2) Preparation of tetraphenyl, tetrapyrazine benzotetraazaheterocycle-pentadienone

[0084] Weigh 1 mmol of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative (decaone) and 5.0 mmol of o-phenylenediamine into a three-necked flask containing 30 ml of acetic acid. Heat in an oil bath to 160°C under nitrogen and reflux for 12 hours. Stop the reaction, cool the mixture to room temperature, and collect the solid by filtration. Wash it 10 times with ethanol and 10 times with deionized water, respectively. Dry it in a vacuum at 60°C to obtain the final product, tetraphenyl-tetrapyrazinebenzotetraazacyclopentadienone, in a 92% yield.

[0085] (3) Assembly of tetraphenyl, tetrapyrazine benzotetraazaheterocycle-pentadienone / / Li for organic lithium-ion batteries

[0086] The assembly of the organic lithium-ion battery tetraphenyl, tetrapyrazine benzotetraazacyclopentadienone / / Li was carried out in a glove box filled with high-purity argon. The assembly process was the same as in Example 1.

[0087] The assembled battery is at 1.0Ag -1 After 1500 cycles at the same current density, the capacity can still maintain 94.8% of the initial capacity.

[0088] Example 8 Preparation and Assembly of Organic Lithium Ion Battery Tetrakis(1,4-dicarbonylnaphthyl)-tetrapyrazinebenzotetraazacyclopentadienone / / Li

[0089] (1) The preparation process of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative - decaone is the same as that in Example 6.

[0090] (2) Preparation of tetrakis(1,4-dicarbonylnaphthyl)-tetrapyrazinebenzotetraazacyclopentadienone

[0091] Weigh 1 mmol of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative (decaone) and 4.0 mmol of 2-amino-1,4-naphthoquinone into a three-necked flask containing 30 ml of acetic acid. Heat to 120°C in an oil bath under nitrogen and reflux for 24 hours. Stop the reaction, cool to room temperature, and collect the solid by filtration. Wash it 10 times with ethanol and then deionized water, then dry it in a vacuum at 60°C to obtain the final product, tetrakis(1,4-dicarbonylnaphthyl)-tetrapyrazinebenzotetraazacyclopentadienone, in an 85% yield.

[0092] (3) Assembly of tetrakis(1,4-dicarbonylnaphthyl)-tetrapyrazinebenzotetraazacyclopentadienone / / Li for organic lithium-ion batteries

[0093] The assembly of the organic lithium-ion battery tetrakis(1,4-dicarbonylnaphthyl)-tetrapyrazinebenzotetraazacyclopentadienone / / Li was carried out in a glove box filled with high-purity argon. The assembly process was the same as in Example 1.

[0094] The assembled battery is at 1.0Ag -1 After 1500 cycles at the same current density, the capacity can still maintain 86.6% of the initial capacity.

[0095] Example 9 Preparation and Assembly of Organic Lithium Ion Battery Tetrakis(benzoquinoxaline-5,10-dione)-Tetrapyrazinebenzotetraazacyclopentadienone / / Li

[0096] (1) The preparation process of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative - decaone is the same as that in Example 6.

[0097] (2) Preparation of Tetrakis(benzoquinoxaline-5,10-dione)-tetrapyrazinebenzotetraazacyclopentadienone

[0098] Weigh 1 mmol of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative (decaone) and 4.0 mmol of 2,3-diaminobenzoquinoxaline-5,10-dione) into a three-necked flask containing 30 ml of acetic acid. Heat to 120°C in an oil bath under nitrogen and reflux for 24 hours. Stop the reaction, cool to room temperature, and collect the solid by filtration. Wash it 10 times with ethanol and then deionized water, then dry it in a vacuum at 60°C to obtain the final product, tetrakis(benzoquinoxaline-5,10-dione)-tetrapyrazinebenzotetraazacyclopentadienone, in 83% yield.

[0099] (3) Assembly of organic lithium-ion batteries tetrakis(benzoquinoxaline-5,10-dione)-tetrapyrazinebenzotetraazacyclopentadienone(H) / / Li

[0100] The assembly of the organic lithium-ion battery tetrakis(benzoquinoxaline-5,10-dione)-tetrapyrazinebenzotetraazacyclopentadienone / / Li was carried out in a glove box filled with high-purity argon. The assembly process was the same as in Example 1.

[0101] The assembled battery is at 1.0Ag -1 After 1500 cycles at the same current density, the capacity can still maintain 93.2% of the initial capacity.

[0102] Preparation and assembly of comparative organic lithium-ion battery 2'2-(1,4-phenyl)-p-(1H-naphtho[2,3-d]imidazole-4,9-dione / / Li

[0103] (1) Preparation of 2'2-(1,4-phenyl)-p-(1H-naphtho[2,3-d]imidazole-4,9-dione

[0104] 0.376 g of 2,3-diamino-1,4-naphthoquinone (2 mmol) and 0.134 g of terephthalaldehyde (1 mmol) were added to a flask, followed by 8 mL of dimethyl sulfoxide (DMSO) solution. The mixture was stirred at 120°C for 7 hours. After cooling, the solvent was removed by filtration, and the product was washed with ethanol and then water. Finally, it was recrystallized from DMF to obtain the brownish-yellow product 2'2-(1,4-phenyl)-p-(1H-naphtho[2,3-d]imidazole-4,9-dione.

[0105] (2) Assembly of organic lithium-ion batteries 2'2-(1,4-phenyl)-p-(1H-naphtho[2,3-d]imidazole-4,9-dione / / Li

[0106] The assembly of the organic lithium-ion battery 2'2-(1,4-phenyl)-p-(1H-naphtho[2,3-d]imidazole-4,9-dione / / Li was carried out in a glove box filled with high-purity argon. The assembly process was the same as in Example 1.

[0107] The assembled battery is at 1.0Ag -1 After 1500 cycles at the same current density, the capacity can maintain 57.8% of the initial capacity.

Claims

1. A class of organic nitrogen-containing polyquinone materials, characterized in that: The structural formula of the organic nitrogen-containing polyquinone material is as follows:

2. A method for preparing an organic nitrogen-containing polyquinone material according to claim 1, characterized in that: The preparation method comprises the following steps: Step 1: Weigh a 2,3,5,6-tetraamino-1,4-benzoquinone derivative and cyclohexanone hydrate, add them to an organic solvent, and heat under reflux in an oil bath for 6 hours under nitrogen protection; after the reactants are cooled to room temperature, the solvent is removed by filtration, and a tan solid is collected, which is then washed three times with 80°C hot water and vacuum-dried to obtain a tan solid; the tan solid is ground into a powder, placed in a tube furnace, heated to 300°C for 6 hours, and obtains quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone; Step 2: reacting quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone with different diamines to obtain the compound of claim 1; The diamine is selected from o-phenylenediamine, 2-amino-1,4-naphthoquinone, 2,3-diaminoquinoxaline or 2,3-diaminobenzoquinoxaline-5,10-dione.

3. The method for preparing the organic nitrogen-containing polyquinone material according to claim 2, wherein: In step 1, the molar ratio of 2,3,5,6-tetraamino-1,4-benzoquinone to cyclohexanone hydrate is 1:2-1:

4.

4. The method for preparing the organic nitrogen-containing polyquinone material according to claim 2, wherein: In step 1, the organic solvent is ethanol, acetic acid or nitric acid; and the reflux reaction temperature is 100-160°C.

5. The method for preparing the organic nitrogen-containing polyquinone material according to claim 2, wherein: The molar ratio of quinoxalo[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone to the diamine compound is 1:2-1:

5.

6. The method for preparing the organic nitrogen-containing polyquinone material according to claim 2, wherein: In step 1, the reaction temperature is 100-160° C., and the reaction time is 12-24 h.

7. The use of the organic nitrogen-containing polyquinone compound according to claim 1, characterized in that: The organic nitrogen-containing polyquinone compound is used as a positive electrode material of an organic lithium-ion battery.

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