Organic nitrogen-containing polyquinone materials, their preparation methods and applications in organic lithium-ion batteries

Abstract

The present invention belongs to the field of synthesis of lithium-ion battery materials, and specifically discloses a class of organic nitrogen-containing polyquinone materials, a preparation method thereof, and an application in organic lithium-ion batteries. 2,3,5,6-Tetraamino-1,4-benzoquinone and cyclohexanehexone hydrate are added to an organic solvent, refluxed under nitrogen protection, cooled, washed with water, vacuum dried, and then sintered in a tube furnace to obtain a product. Then, the prepared product is reacted with a diamine or dinitrile compound to obtain quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaneone derivatives with different substitutions. The derivative has carbon-nitrogen double bonds and carbon-oxygen double bonds with rich electrochemical reaction activities, and at the same time reduces the solubility of the compound by expanding the conjugated structure, solving the battery stability problem caused by solubility. The lithium-ion battery assembled therefrom has excellent specific capacity and good cycle stability.

Description

Technical Field

[0001] The present invention belongs to the field of synthesis of lithium-ion battery materials, and specifically discloses a class of organic nitrogen-containing polyquinone materials, a preparation method thereof, and an application thereof in organic lithium-ion batteries. Background Art

[0002] The rapidly increasing energy demand makes it extremely urgent to research new energy sources that are pollution-free and sustainable. The high-energy-density, long-cycle-life, and easy-scale-production lithium-ion batteries (LIBs) are widely used in various fields due to their advantages. However, their development is restricted by the relatively low capacity of the cathode materials. Currently, the commercial inorganic cathodes of LIBs mainly include transition metal oxides or phosphates, such as LiCoO 2 , LiFePO 4 or LiNi x Mn y Co z O 2 etc. Their energy density has approached the upper limit of the theoretical value, but it is still difficult to meet the growing demand for energy storage applications. At the same time, it is very difficult to further increase their capacity without affecting the cycle stability and safety. In addition, these inorganic cathodes are mainly produced from their respective corresponding ores, and the widespread use of inorganic cathodes will also increase the consumption of non-renewable ores. To solve the above problems, green organic electroactive compounds are gradually becoming very promising electrode materials for the next-generation batteries.

[0003] Compared with inorganic cathodes, organic electrode materials have a large theoretical capacity, are environmentally friendly, have low acquisition costs, have diverse structures and can be adjusted. So far, many organic electrode materials have been studied as the cathode materials of LIBs, including organic sulfur compounds, organic radicals, imine compounds, azo compounds, and carbonyl compounds, etc. 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 exposure of active sites, and low conductivity seriously hinder 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

[0004] The object of the present invention is to provide a high-performance cathode material, i.e., an organic nitrogen-containing polyquinone material quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone and its derivatives, for organic lithium-ion batteries. Using tetraaminobenzoquinone and commercially available cyclohexanehexanone hydrate as raw materials, a polycarbonyl organic electrode material quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone with more redox sites is constructed by a simple and easy method that is also suitable for large-scale production in the later stage. Then, it is further reacted with different diamine and dinitrile compounds to obtain quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivatives with different substitutions. When quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone and quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivatives with different substitutions are used as the cathode material of organic lithium-ion batteries, they have the advantages of high electrochemical capacity and long cycle life, and have broad application prospects.

[0005] 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. The quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivatives have the general formula structure shown in Formula 1 below:

[0006]

[0007] Among them, R is selected from one or two of 1,2-difluoroethane-1,2-diamine, 1,2-dichloroethane-1,2-diamine, 2,3-diaminobutanedinitrile, o-phenylenediamine, 2-amino-1,4-naphthoquinone, 2,3-diaminoquinoxaline or 2,3-diaminobenzquinoxaline-5,10-dione groups.

[0008] The structural formulas of quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone and its derivatives are as follows:

[0009]

[0010] The quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone and its derivatives of the above structure are specifically: quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative-decaone (A), 2,3,6,7,13,14,17,18-octafluorotetrapyridino benzotetraaza-pentapentadienone (B), 2,3,6,7,13,14,17,18-octachlorotetrapyridino benzotetraaza-pentapentadienone (C), 2,3,6,7,13,14,17,18-octanitrilotetrapyridino benzotetraaza-pentapentadienone (D), tetraphenyl, tetrapyridino benzotetraaza-pentapentadienone (E), tetra(1,4-dicarbonyl naphthyl)-tetrapyridino benzotetraaza-pentapentadienone (F), tetraquinoxaline tetrapyridino benzotetraaza-pentapentadienone (G) or tetra(benzoquinoxalin-5,10-dione)-tetrapyridino benzotetraaza-pentapentadienone (H).

[0011] The preparation method of the organic nitrogen-containing polyquinone material of the present invention comprises the following steps:

[0012] Step 1: Weigh 2,3,5,6-tetraamino-1,4-benzoquinone derivative and cyclohexanehexone hydrate and add them to an organic solvent. Under nitrogen protection, heat in an oil bath and reflux for 6 h; after the reactants are cooled to room temperature, filter off the solvent, collect the brown solid, wash it three times with hot water at 80 °C, and obtain the brown solid after vacuum drying;

[0013] Among them, the molar ratio of 2,3,5,6-tetraamino-1,4-benzoquinone derivative to cyclohexanehexone hydrate is 1:2 - 1:4.

[0014] The organic solvent is selected from ethanol aqueous solution, acetic acid, nitric acid, or a combination thereof.

[0015] Heat in an oil bath to 100 - 160 °C.

[0016] Step 2: Grind the above brown solid into powder, put it into a tube furnace, heat it to 300 °C for 6 h to obtain the product quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative-decaone.

[0017] Continue to carry out a reflux heating reaction (reaction conditions: reaction temperature is 100

[0018] -160 °C, duration is 12 - 24 h) on the above-prepared quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone with different diamine or dinitrile compounds to obtain quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivatives with different substitutions.

[0019] The diamine or dinitrile compound is selected from one of 1,2-difluoroethane-1,2-diamine, 1,2-dichloroethane-1,2-diamine, 2,3-diaminobutanedinitrile, o-phenylenediamine, 2-amino-1,4-naphthoquinone, 2,3-diaminoquinoxaline or 2,3-diaminobenzophenazine-5,10-dione.

[0020] The molar ratio of quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone to the diamine or dinitrile compound is 1:2 - 1:5.

[0021] The prepared quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative is used as the positive electrode material of an organic lithium-ion battery, and an organic lithium-ion battery is assembled with a lithium metal sheet.

[0022] The beneficial effects of the present invention are as follows:

[0023] The present invention prepares an organic nitrogen-containing polyquinone material, quinoxaline[2,3-b]phenazine

[0024] -1,2,3,4,6,8,9,10,11,13-decaone and its derivatives, and uses them as the positive electrode material of an organic lithium-ion battery to achieve the purpose of improving the electrochemical capacity and cycle life of the organic lithium-ion battery. The present invention not only provides an organic lithium-ion battery using a quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative as the positive electrode material, but also solves the problems of low actual electrochemical capacity and short cycle life caused by dissolution in the electrolyte solution commonly existing in existing organic lithium-ion batteries. Description of the Drawings

[0025] Figure 1 It is a reaction route diagram for preparing the quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative - decaone in Example 1.

[0026] Figure 2 It is a mass spectrum diagram of the quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative - decaone prepared in Example 1.

[0027] Figure 3 It is a nuclear magnetic carbon spectrum diagram of the quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative - decaone prepared in Example 1.

[0028] Figure 4The charge-discharge curve of the quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivative-decanone / / Li assembled for Example 1 at a current density of 0.1 A g -1 is shown below.

[0029] Figure 5 The cycling performance graph of the quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivative-decanone / / Li of Example 1 of the present invention at a current density of 1.0 A g -1 is shown below.

[0030] Figure 6 The rate performance graph of the quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone derivative-decanone / / Li of Example 1 of the present invention at different current densities is shown below.

[0031] Figure 7 The cycling performance graph of the 2,3,6,7,13,14,17,18-octafluorotetrapyridazino benzotetraaza -pentapentadienone / / Li of Example 2 of the present invention at a current density of 1.0 A g -1 is shown below.

[0032] Figure 8 The cycling performance graph of the 2,3,6,7,13,14,17,18-octachlorotetrapyridazino benzotetraaza -pentapentadienone / / Li of Example 3 of the present invention at a current density of 1.0 A g -1 is shown below.

[0033] Figure 9 The cycling performance graph of the organic lithium-ion battery 2’2-(1,4-phenyl)bis(1H-naphtho[2,3-d]imidazole-4,9-dione) / / Li at a current density of 1.0 A g -1 is shown below. Detailed implementation mode

[0034] The present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited to the following embodiments.

[0035] Example 1

[0036] Preparation and assembly of the organic lithium-ion battery quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone / / Li

[0037] (1) Preparation of quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone

[0038] Step 1: Weigh 1 mmol of 2,3,5,6-tetraamino-1,4-benzoquinone and 2.0 mmol of cyclohexanehexone octahydrate and add them to a three-necked flask containing 30 ml of acetic acid. Under nitrogen protection, heat the mixture in an oil bath to 120 °C and reflux for 6 h;

[0039] Step 2: Stop the reaction. After the reactants are cooled to room temperature, collect the brown solid by suction filtration, wash it 10 times by centrifugation with hot water at 80 °C, and dry it under vacuum to obtain a brown solid;

[0040] Step 3: Place the above brown solid in a tube furnace, heat it to 300 °C for 6 h to obtain the final product, which is quinoxalino[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone.

[0041] (2) Assembly of quinoxalino[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone / / Li for organic lithium-ion batteries

[0042] The assembly of quinoxalino[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone / / Li for organic lithium-ion batteries is carried out in a glove box filled with high-purity argon. Using the quinoxalino[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone prepared above as the positive electrode, metallic lithium as the negative electrode, and porous polypropylene membrane (Celgard 2400) as the separator, add the electrolyte to assemble a button battery (CR2032). The electrolyte is 1,3-dioxolane (DOL) and dimethoxyethane (DME) (volume ratio 1:1) dissolved with 1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 1 wt.% LiNO 3 ₃. The assembled button battery is kept stationary for 24 h before electrochemical testing.

[0043] Figure 1 This is the reaction route diagram for the preparation of quinoxalino[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone in this example. 2,3,5,6-Tetraamino-1,4-benzoquinone and cyclohexanehexone undergo an amide reaction during a simple and easy reflux operation to generate quinoxalino[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone, with a yield of 93%.

[0044] Figure 2The mass spectrum of quinoxalino[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaketone prepared in this example. The predicted molecular weight of quinoxalino[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaketone according to the molecular formula is 432, and the main mass-to-charge ratio in the mass spectrum is 432.53, which is the same as the predicted molecular weight.

[0045] Figure 3 The carbon-13 NMR spectrum of quinoxalino[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaketone prepared in Example 1. The peaks at 142.07, 141.30, 133.37, and 129.88 ppm correspond to the carbon peaks at positions a, b, c / d, and e in the molecular formula, respectively, further proving the synthesis of the product.

[0046] Figure 4 Charge-discharge curve of the quinoxalino[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaketone / / Li organic lithium-ion battery assembled in this example at a current density of 0.1 A g -1 The organic nitrogen-containing polyquinone material has a high initial discharge capacity of 334 mAh g -1 and exhibits a Coulombic efficiency close to 100%, showing excellent electrochemical reversibility and long-term cycle stability. This phenomenon may be attributed to the stable π-conjugated structure and high electronic conductivity of the material.

[0047] Figure 5 Cycling performance graph of the quinoxalino[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaketone / / Li lithium-ion battery in this example at a current density of 1.0 A g -1 As can be seen from the figure, at a current density of 1.0 A g -1 the assembled battery can still maintain 90.6% of its initial capacity after 1500 cycles.

[0048] Figure 6 Rate performance graph of the quinoxalino[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaketone derivative-decaketone / / Li lithium-ion battery in this example at different current densities. The battery obtained high discharge specific capacities of 334, 266, 242, 193, 167, and 144 mAh g -1 at current densities of 0.05, 0.1, 0.2, 0.5, 1.0, and 2.0 A g -1 respectively. When the current density returns to the initial 0.05 A g -1 the discharge specific capacity can return to 290 mAh g -1, demonstrating that the quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative - decaone prepared in Example 1 of the present invention not only has excellent rate performance but also has good reversibility.

[0049] Preparation and assembly of organic lithium-ion battery 2,3,6,7,13,14,17,18-octafluorotetrapyridazino[3,4-b]tetraazapentacenequinone / / Li

[0050] (1) The preparation process of quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative - decaone is the same as that in Example 1.

[0051] (2) Preparation of 2,3,6,7,13,14,17,18-octafluorotetrapyridazino[3,4-b]tetraazapentacenequinone

[0052] Weigh 1 mmol of quinoxaline[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, add them to a three-necked flask containing 30 ml of acetic acid, under nitrogen protection, heat in an oil bath to 120 °C, and reflux for 24 h. Stop the reaction, wait for the reactants to cool to room temperature, collect the solid by suction filtration, wash it 10 times with ethanol and deionized water respectively, and dry it in vacuo at 60 °C to obtain the final product 2,3,6,7,13,14,17,18-octafluorotetrapyridazino[3,4-b]tetraazapentacenequinone, with a yield of 91%.

[0053] (3) Assembly of organic lithium-ion battery 2,3,6,7,13,14,17,18-octafluorotetrapyridazino[3,4-b]tetraazapentacenequinone / / Li

[0054] The assembly of organic lithium-ion battery 2,3,6,7,13,14,17,18-octafluorotetrapyridazino[3,4-b]tetraazapentacenequinone / / Li is carried out in a glove box filled with high-purity argon. The assembly process is the same as that in Example 1.

[0055] Figure 7 This is the cyclic performance graph of 2,3,6,7,13,14,17,18-octafluorotetrapyridazino[3,4-b]tetraazapentacenequinone / / Li in Example 2 at a current density of 1.0 A g -1 As can be seen from the figure, at a current density of 1.0 A g -1 The assembled battery can still maintain 93.8% of its initial capacity after 1500 cycles.

[0056] Preparation and Assembly of Organic Lithium Ion Battery 2,3,6,7,13,14,17,18 - Octachlorotetrapyrazine Benzotetrazacyclopentapentadienone / / Li

[0057] (1) The preparation process of quinoxaline[2,3 - b]phenazine - 1,2,3,4,6,8,9,10,11,13 - decaketone derivative - decaketone is the same as that in Example 1.

[0058] (2) Preparation of 2,3,6,7,13,14,17,18 - Octachlorotetrapyrazine Benzotetrazacyclopentapentadienone

[0059] Weigh 1 mmol of quinoxaline[2,3 - b]phenazine - 1,2,3,4,6,8,9,10,11,13 - decaketone derivative - decaketone and 2.0 mmol of 1,2 - dichloroethane - 1,2 - diamine, add them to a three - necked flask containing 30 ml of acetic acid. Under nitrogen protection, heat it in an oil bath to 160 °C and reflux for 24 h. Stop the reaction. After the reactants cool to room temperature, collect the solid by suction filtration, wash it 10 times with ethanol and deionized water respectively, and dry it in vacuo at 60 °C to obtain the final product 2,3,6,7,13,14,17,18 - octachlorotetrapyrazine benzotetrazacyclopentapentadienone. The yield is 86%.

[0060] (3) Assembly of Organic Lithium Ion Battery 2,3,6,7,13,14,17,18 - Octachlorotetrapyrazine Benzotetrazacyclopentapentadienone / / Li

[0061] The assembly of organic lithium ion battery 2,3,6,7,13,14,17,18 - octachlorotetrapyrazine benzotetrazacyclopentapentadienone / / Li is carried out in a glove box filled with high - purity argon. The assembly process is the same as that in Example 1.

[0062] Figure 8 This is the cycle performance graph of 2,3,6,7,13,14,17,18 - octachlorotetrapyrazine benzotetrazacyclopentapentadienone / / Li in this example at a current density of 1.0 A g -1 As can be seen from the figure, at a current density of 1.0 A g -1 the assembled battery can still maintain 86.8% of its initial capacity after 1500 cycles.

[0063] Example 4 Preparation and Assembly of Organic Lithium Ion Battery 2,3,6,7,13,14,17,18 - Octanitrilotetrapyrazine Benzotetrazacyclopentapentadienone / / Li

[0064] (1) The preparation process of quinoxaline[2,3 - b]phenazine - 1,2,3,4,6,8,9,10,11,13 - decaketone derivative - decaketone is the same as that in Example 1.

[0065] (2) Preparation of 2,3,6,7,13,14,17,18-octacyanotetrapyridino-benzo-tetraazapentacenequinone

[0066] Weigh 1 mmol of quinoxalino[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative - decaone and 3.0 mmol of 2,3-diaminobutanedinitrile, add them to a three-necked flask containing 30 ml of ethanol aqueous solution. Under nitrogen protection, heat the oil bath to 100 °C and reflux for 12 h. Stop the reaction. After the reactants are cooled to room temperature, collect the solid by suction filtration, wash it 10 times with ethanol and deionized water respectively, and dry it in vacuum at 60 °C to obtain the final product 2,3,6,7,13,14,17,18-octacyanotetrapyridino-benzo-tetraazapentacenequinone, with a yield of 90%.

[0067] (3) Assembly of organic lithium-ion battery 2,3,6,7,13,14,17,18-octacyanotetrapyridino-benzo-tetraazapentacenequinone / / Li

[0068] The assembly of the organic lithium-ion battery 2,3,6,7,13,14,17,18-octacyanotetrapyridino-benzo-tetraazapentacenequinone / / Li is carried out in a glove box filled with high-purity argon. The assembly process is the same as that in Example 1.

[0069] The assembled battery still maintains 87.2% of its initial capacity after 1500 cycles at a current density of 1.0 A g -1

[0070] Example 5 Preparation and Assembly of Organic Lithium-Ion Battery Tetraquinoxalinotetrapyridino-benzo-tetraazapentacenequinone / / Li

[0071] (1) The preparation process of quinoxalino[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative - decaone is the same as that in Example 1.

[0072] (2) Preparation of tetraquinoxalinotetrapyridino-benzo-tetraazapentacenequinone

[0073] Weigh 1 mmol of quinoxalino[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, add them to a three-necked flask containing 30 ml of acetic acid. Under nitrogen protection, heat the oil bath to 120 °C and reflux for 24 h. Stop the reaction. After the reactants are cooled to room temperature, collect the solid by suction filtration, wash it 10 times with ethanol and deionized water respectively, and dry it in vacuum at 60 °C to obtain the final product tetraquinoxalinotetrapyridino-benzo-tetraazapentacenequinone, with a yield of 81%. ​

[0074] (3) Assembly of organic lithium-ion battery tetraquinoxaline tetrapyrazine benzotetraazacyclopenta-pentadienone / / Li

[0075] The assembly of the organic lithium-ion battery quinoxaline tetraquinoxaline tetrapyrazine benzotetraazacyclopenta-pentadienone / / Li was carried out in a glove box filled with high-purity argon. The assembly process was the same as that in Example 1.

[0076] The assembled battery still maintained 82.5% of its initial capacity after 1500 cycles at a current density of 1.0 A g -1 .

[0077] Example 6

[0078] Preparation and assembly of organic lithium-ion battery quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative-decaone / / Li

[0079] (1) Preparation of quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative-decaone

[0080] 1 mmol of 2,3,5,6-tetraamino-1,4-benzoquinone and 4.0 mmol of cyclohexanehexone octahydrate were weighed and added to a three-necked flask containing 30 ml of acetic acid. Under nitrogen protection, the mixture was heated to 120 °C in an oil bath and refluxed for 6 h; the preparation process was the same as that in Example 1. The product yield was 90%.

[0081] (2) Assembly of organic lithium-ion battery quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative-decaone / / Li

[0082] The assembly process was the same as that in Example 1.

[0083] At a current density of 1.0 A g -1 , the assembled battery still maintained 89.1% of its initial capacity after 1500 cycles.

[0084] Example 7 Preparation and assembly of organic lithium-ion battery tetraphenyl, tetrapyrazine benzotetraazacyclopenta-pentadienone / / Li

[0085] (1) The preparation process of quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative-decaone was the same as that in Example 6.

[0086] (2) Preparation of tetraphenyl, tetrapyrazine benzotetraazacyclopenta-pentadienone

[0087] Weigh 1 mmol of quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative - decaone and 5.0 mmol of o-phenylenediamine, add them to a three-necked flask containing 30 ml of acetic acid, under nitrogen protection, heat in an oil bath to 160 °C, and reflux for 12 h. Stop the reaction, wait for the reactants to cool to room temperature, collect the solid by suction filtration, wash it 10 times with ethanol and deionized water respectively, and dry it in vacuo at 60 °C to obtain the final product tetraphenyl, tetrapyrazine benzotetraazapentacenequinone, with a yield of 92%.

[0088] (3) Assembly of organic lithium-ion battery tetraphenyl, tetrapyrazine benzotetraazapentacenequinone / / Li

[0089] The assembly of the organic lithium-ion battery tetraphenyl, tetrapyrazine benzotetraazapentacenequinone / / Li is carried out in a glove box filled with high-purity argon. The assembly process is the same as in Example 1.

[0090] The assembled battery still maintains 94.8% of its initial capacity after 1500 cycles at a current density of 1.0 A g -1

[0091] Example 8 Preparation and assembly of organic lithium-ion battery tetra(1,4-dicarbonylnaphthyl)-tetrapyrazine benzotetraazapentacenequinone / / Li

[0092] (1) The preparation process of quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative - decaone is the same as in Example 6.

[0093] (2) Preparation of tetra(1,4-dicarbonylnaphthyl)-tetrapyrazine benzotetraazapentacenequinone

[0094] Weigh 1 mmol of quinoxaline[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, add them to a three-necked flask containing 30 ml of acetic acid, under nitrogen protection, heat in an oil bath to 120 °C, and reflux for 24 h. Stop the reaction, wait for the reactants to cool to room temperature, collect the solid by suction filtration, wash it 10 times with ethanol and deionized water respectively, and dry it in vacuo at 60 °C to obtain the final product tetra(1,4-dicarbonylnaphthyl)-tetrapyrazine benzotetraazapentacenequinone, with a yield of 85%.

[0095] (3) Assembly of organic lithium-ion battery tetra(1,4-dicarbonylnaphthyl)-tetrapyrazine benzotetraazapentacenequinone / / Li

[0096] ​Assembly of organic lithium-ion battery tetra(1,4-dicarbonyl naphthyl)-tetrazine benzotetraaza-pentapentadienone / / Li was carried out in a glove box filled with high-purity argon. The assembly process was the same as that in Example 1.

[0097] After 1500 cycles at a current density of 1.0 A g -1 the capacity of the assembled battery could still maintain 86.6% of the initial capacity.

[0098] Example 9 Preparation and assembly of organic lithium-ion battery tetra(benzoquinoxaline-5,10-dione)-tetrazine benzotetraaza-pentapentadienone / / Li

[0099] (1) The preparation process of quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decaone derivative-decaone was the same as that in Example 6.

[0100] (2) Preparation of tetra(benzoquinoxaline-5,10-dione)-tetrazine benzotetraaza-pentapentadienone

[0101] Weigh 1 mmol of quinoxaline[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, add them to a three-necked flask containing 30 ml of acetic acid, under nitrogen protection, heat in an oil bath to 120 °C, and reflux for 24 h. Stop the reaction, wait for the reactant to cool to room temperature, collect the solid by suction filtration, wash it 10 times with ethanol and deionized water respectively, and dry it in vacuum at 60 °C to obtain the final product tetra(benzoquinoxaline-5,10-dione)-tetrazine benzotetraaza-pentapentadienone, with a yield of 83%.

[0102] (3) Assembly of organic lithium-ion battery tetra(benzoquinoxaline-5,10-dione)-tetrazine benzotetraaza-pentapentadienone(H) / / Li

[0103] Assembly of organic lithium-ion battery tetra(benzoquinoxaline-5,10-dione)-tetrazine benzotetraaza-pentapentadienone / / Li was carried out in a glove box filled with high-purity argon. The assembly process was the same as that in Example 1.

[0104] After 1500 cycles at a current density of 1.0 A g -1 the capacity of the assembled battery could still maintain 93.2% of the initial capacity.

[0105] Control example Preparation and assembly of organic lithium-ion battery 2’2-(1,4-phenyl)bis(1H-naphtho[2,3-d]imidazole-4,9-dione) / / Li

[0106] (1) Preparation Process of 2’2-(1,4-phenyl) bis(1H-naphtho[2,3-d]imidazole-4,9-dione)

[0107] 0.376 g of 2,3-diamino-1,4-naphthoquinone (2 mmol) and 0.134 g of terephthalaldehyde (1 mmol) were added together into a flask, and then 8 mL of dimethyl sulfoxide solution (DMSO) was added. The mixture was stirred and reacted at 120 °C for 7 h. After cooling, the solvent was removed by suction filtration, and then ethanol and water were added successively for washing. Finally, recrystallization was carried out in DMF to obtain the yellowish-brown product 2’2-(1,4-phenyl) bis(1H-naphtho[2,3-d]imidazole-4,9-dione).

[0108] (2) Assembly of Organic Lithium-ion Battery 2’2-(1,4-phenyl) bis(1H-naphtho[2,3-d]imidazole-4,9-dione) / / Li

[0109] The assembly of the organic lithium-ion battery 2’2-(1,4-phenyl) bis(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 that in Example 1.

[0110] The assembled battery had a capacity retention of 57.8% of the initial capacity after 1500 cycles at a current density of 1.0 A g -1 .

Claims

1. A class of organic nitrogen-containing polyquinone compounds, characterized in that, the organic nitrogen-containing polyquinone compounds are: 2,3,6,7,13,14,17,18-octafluorotetrapyridazine benzotetraazacyclo-pentapentalenone, 2,3,6,7,13,14,17,18-octachlorotetrapyridazine benzotetraazacyclo-pentapentalenone, 2,3,6,7,13,14,17,18-octanitrilotetrapyridazine benzotetraazacyclo-pentapentalenone.

2. A preparation method of the organic nitrogen-containing polyquinone compound according to claim 1, characterized in that, the steps of the preparation method are as follows: Step 1: Weigh 2,3,5,6-tetraamino-1,4-benzoquinone and cyclohexanehexanone hydrate, add them to an organic solvent, under nitrogen protection, heat in an oil bath and reflux for 6 h; after the reactants are cooled to room temperature, filter off the solvent, collect the brown solid, and wash it three times with hot water at 80 °C, and obtain the brown solid quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone after vacuum drying; Step 2: React quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone with different diamine or dinitrile compounds to obtain differently substituted quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone compounds; The diamine or dinitrile compounds are selected from: 1,2-difluoroethane-1,2-diamine, 1,2-dichloroethane-1,2-diamine, 2,3-diaminobutanedinitrile.

3. The preparation method of the organic nitrogen-containing polyquinone compound according to claim 2, characterized in that, the molar ratio of 2,3,5,6-tetraamino-1,4-benzoquinone to cyclohexanehexanone hydrate in Step 1 is 1:2 - 1:

4.

4. The preparation method of the organic nitrogen-containing polyquinone compound according to claim 2, characterized in that, the organic solvent in Step 1 is selected from ethanol and acetic acid; the reflux reaction temperature is 100 - 160 °C.

5. The preparation method of the organic nitrogen-containing polyquinone compound according to claim 2, characterized in that, the molar ratio of quinoxaline[2,3-b]phenazine-1,2,3,4,6,8,9,10,11,13-decanone to the diamine or dinitrile compound in Step 2 is 1:2 - 1:

5.

6. The preparation method of the organic nitrogen-containing polyquinone compound according to claim 2, characterized in that, the reaction temperature in Step 2 is 100 - 160 °C, and the reaction time is 12 - 24 h.

7. The application 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 for organic lithium-ion batteries.

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