Aza-aromatic fused ring polymer, preparation method and application thereof in preparation of aqueous zinc ion battery

Abstract

The application provides an azaheteroaromatic fused ring polymer, and belongs to the technical field of rechargeable batteries.The azaheteroaromatic fused ring polymer is obtained from 2,6-diaminoanthraquinone through a bromination reaction, a debromination reaction and a dehydration condensation reaction in sequence.The azaheteroaromatic fused ring polymer can be used as a positive electrode of a water-based zinc ion battery, can effectively improve the cycle stability and electrochemical performance of the water-based zinc ion battery, and can also improve the weather resistance of the water-based zinc ion battery.The application further provides a preparation method of the azaheteroaromatic fused ring polymer and application of the azaheteroaromatic fused ring polymer in preparation of a water-based zinc ion battery.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of rechargeable batteries, and particularly relates to a nitrogen heteroaromatic fused ring polymer, a preparation method thereof and application of the nitrogen heteroaromatic fused ring polymer in preparation of an aqueous zinc ion battery. BACKGROUND

[0002] Non-aqueous lithium ion batteries have the advantages of large specific capacity and long cycle life, and have become the mainstream energy storage system in mobile electronic devices and emerging hybrid electric vehicles. However, the scarcity of lithium resources, high price and serious safety hazards restrict the large-scale application of lithium batteries in power stations and other high-security sites. Moreover, the organic electrolyte is highly toxic and flammable, which increases the safety risk of the battery in practical application. Therefore, replacing the battery containing organic electrolyte with a water-based battery can not only improve the stability and safety of the energy storage system, but also obtain a more cost-effective battery device. The aqueous zinc ion battery (AZIBs) has the advantages of abundant resources, environmental friendliness, high theoretical capacity and fast kinetics of good redox potential 、 .

[0003] However, there is currently a lack of suitable positive electrode materials to meet the needs of aqueous zinc ion batteries under high and low temperature conditions. Inorganic positive electrode materials usually have a rigid structure, which often causes difficult ion intercalation behavior during charging and discharging, resulting in slow kinetics and low capacity of the electrochemical process. Compared with inorganic electrode materials, research on organic electrode materials has made continuous breakthroughs. Organic materials have inherent flexibility, adjustable performance through molecular engineering, abundant natural resources and recyclability, which provide an alternative and more diverse material space for electrode design. Traditional organic electrode materials have limited electronic delocalization and high solubility, which leads to poor conductivity, low redox activity, unstable electrochemical performance and other problems, limiting their application under harsh conditions. Therefore, it is of great significance to develop an electrode design strategy to adjust the electronic delocalization, improve the structural stability of the organic positive electrode material, realize structural stability and fast diffusion kinetics to enhance the comprehensive electrochemical performance of the organic positive electrode material. SUMMARY

[0004] In order to solve the problems of insufficient conductivity, unstable structure and low redox activity of existing organic positive electrode materials, the application provides a nitrogen heteroaromatic fused ring polymer. The nitrogen heteroaromatic fused ring polymer can be used as a positive electrode of an aqueous zinc ion battery, which can effectively improve the cycle stability and electrochemical performance of the aqueous zinc ion battery, and can also improve the weather resistance of the aqueous zinc ion battery.

[0005] The application also provides a preparation method of the nitrogen heteroaromatic fused ring polymer and application of the nitrogen heteroaromatic fused ring polymer in preparation of an aqueous zinc ion battery.

[0006] The present application is realized by the following technical solutions.

[0007] The present application provides a kind of azaheteroaromatic fused ring polymer, the structural formula of the azaheteroaromatic fused ring polymer is as follows: ;

[0008] Wherein, n is 3-100.

[0009] Based on the same inventive concept, the present application provides a kind of azaheteroaromatic fused ring polymer preparation method, the preparation method includes: 2,6-diaminoanthraquinone is sequentially subjected to bromination reaction, debromination reaction and dehydration condensation reaction, obtains azaheteroaromatic fused ring polymer.

[0010] Further, the preparation method specifically includes:

[0011] S1.2,6-diaminoanthraquinone (DAAQ) and N-bromosuccinimide are dissolved in organic solvent respectively, to obtain 2,6-diaminoanthraquinone solution and N-bromosuccinimide solution, the N-bromosuccinimide solution is added dropwise to the 2,6-diaminoanthraquinone solution at 0±5℃, after warming, bromination reaction is carried out under inert atmosphere, after reaction is completed, solvent is removed, the obtained crude product is washed, vacuum dried, to obtain 2,6-diamino-1,5-bromo-anthraquinone (DAAQ-Br);

[0012] S2.2,6-diamino-1,5-bromo-anthraquinone and hexanoic anhydride solution are subjected to microwave reaction under inert atmosphere at 170-190 ℃ for 0.5-1h, the obtained crude product is filtered, washed and vacuum dried, to obtain DAAQ-Br-C6;

[0013] S3.DAAQ-Br-C6, copper powder and iodine are added to organic solvent together, heated to 120-140 ℃ under inert atmosphere and reacted for 18-28h, after reaction is completed, filtration is carried out, the filtrate is poured into water to precipitate solid, then solid-liquid separation is carried out, the obtained solid is recrystallized with a mixed solution of tetrahydrofuran and ether, the crystal is washed, vacuum dried, to obtain Pre-PPP;

[0014] S4.Pre-PPP, dilute hydrochloric acid and 1,4-dioxane are mixed, heated at 150±10 ℃ for 40-54h, after cooling, solid-liquid separation is carried out, the obtained solid is washed and dried, to obtain azaheteroaromatic fused ring polymer (PPP);

[0015] Wherein, the structure formula of DAAQ-Br-C6 and Pre-PPP is as follows:

[0016] 、 .

[0017] Preferably, in step S1, the molar ratio of 2,6-diaminoanthraquinone and N-bromosuccinimide is 1:(2-3);

[0018] The inert atmosphere is argon or nitrogen;

[0019] The reaction temperature of the bromination reaction is 25±5 ℃, and the reaction time is 20-28 h;

[0020] The obtained crude product is washed and vacuum dried, specifically including:

[0021] The obtained crude product is washed with water and ethanol several times in turn, and then vacuum dried at 60-100 ℃ for 8-16 h.

[0022] Preferably, in step S2, the molar ratio of DAAQ-Br and hexanoic anhydride is 1:(5-15), the reaction temperature is 170-190 o C, and the reaction time is 0.5-1 h;

[0023] The obtained crude product is filtered, washed, and vacuum dried, specifically including:

[0024] The obtained crude product is filtered, and then washed with water and ethanol several times in turn, and the washed product is vacuum dried at 60-100 ℃ for 8-16 h.

[0025] Preferably, in step S3, the molar ratio of DAAQ-Br-C6, copper powder, and iodine is 1:(1.5-3.5):(0.01-0.5);

[0026] The obtained solid is recrystallized with a mixed solution of tetrahydrofuran and ether, and the crystals are washed and vacuum dried, specifically including:

[0027] The obtained solid is recrystallized with a mixed solution of tetrahydrofuran and ether, the volume ratio of tetrahydrofuran to ether is 1:(0.5-1.5), the crystals are washed with water and ethanol several times in turn, and then vacuum dried at 60-100 ℃ for 8-16 h.

[0028] Preferably, in step S4, the concentration of the dilute hydrochloric acid is 1.5-2.5 mol / L;

[0029] The volume ratio of 1,4-dioxane to the dilute hydrochloric acid is 1:(3-5);

[0030] The obtained solid is washed and dried to obtain a nitrogen-containing aromatic fused ring polymer, specifically including:

[0031] The obtained solid is washed with tetrahydrofuran, water and ethanol in sequence, and the washed product is dried at 60-100 DEG C under vacuum for 8-16 hours to obtain the nitrogen-containing aromatic fused ring polymer.

[0032] Based on the same inventive concept, the application provides an application of the nitrogen-containing aromatic fused ring polymer in an organic positive electrode material or preparation of the organic positive electrode material.

[0033] Based on the same inventive concept, the application provides an application of the nitrogen-containing aromatic fused ring polymer in preparation of a water-based zinc ion battery.

[0034] Based on the same inventive concept, the application further provides a wide-temperature-range water-based zinc ion battery containing the nitrogen-containing aromatic fused ring polymer.

[0035] The one or more technical solutions in the embodiments of the application have at least the following technical effects or advantages:

[0036] 1. The nitrogen-containing aromatic fused ring polymer can promote intermolecular charge hopping and carrier migration, promote the formation of open two-dimensional channels of aromatic rings, enhance pi electron delocalization and ion migration, thereby improving electron / ion conductivity and ensuring fast electrochemical kinetics at high / low temperatures.

[0037] 2. The nitrogen-containing aromatic fused ring polymer can be used for preparation of a battery positive electrode, and exhibits a higher reversible capacity under high / low temperature working conditions: at normal temperature 25 DEG C, the specific capacity is 205 mAh g -1 , the current density is 0.1 A -1 ; at high temperature 50 DEG C, the specific capacity is 214 mAh g -1 , the current density is 0.1 A -1 ; at low temperature-70 DEG C, the specific capacity is 85 mAh g -1 , the current density is 0.1 A -1 ; and has excellent cycle performance, with a long cycle life of more than 10000 times, and excellent rate performance.

[0038] 3.The nitrogen-containing aromatic fused ring polymer has high reversible capacity and fast charge transfer capability, and has great potential when applied to the positive electrode material of the aqueous zinc ion battery, solves the problems of poor conductivity, unstable structure and low redox activity of the existing organic positive electrode material, and the preparation raw material of the nitrogen-containing aromatic fused ring polymer is green and environmentally friendly, low in price, and has good application prospect.

[0039] 4.The application of the nitrogen-containing aromatic fused ring polymer in the preparation of the aqueous zinc ion battery, when the nitrogen-containing aromatic fused ring polymer is used to make the positive electrode of the aqueous zinc ion battery, has excellent specific capacity, fast electrochemical reaction kinetics, good rate performance, long cycle life and excellent weather resistance, thereby improving the cycle stability, electrochemical performance and weather resistance of the aqueous zinc ion battery, and the aqueous zinc ion battery has excellent comprehensive electrochemical performance. BRIEF DESCRIPTION OF DRAWINGS

[0040] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0041] Figure 1 TEM photo of the nitrogen-containing aromatic fused ring polymer synthesized in Example 1;

[0042] Figure 2 Infrared spectrum of the nitrogen-containing aromatic fused ring polymer synthesized in Example 1 and infrared spectrum of each step precursor;

[0043] Figure 3 Gel permeation chromatogram (GPC) of the polymer precursor Pre-PPP;

[0044] Figure 4 Thermogravimetric analysis chart of the nitrogen-containing aromatic fused ring polymer synthesized in Example 1;

[0045] Figure 5 Resistance and conductivity change curve chart of the nitrogen-containing aromatic fused ring polymer synthesized in Example 1 with temperature;

[0046] Figure 6 Constant current charge-discharge curve chart of the aqueous zinc ion battery with the nitrogen-containing aromatic fused ring polymer synthesized in Example 1 as the positive electrode material at different temperatures;

[0047] Figure 7 Rate performance chart of the aqueous zinc ion battery with the nitrogen-containing aromatic fused ring polymer synthesized in Example 1 as the positive electrode material at different temperatures;

[0048] Figure 8 The water-based zinc ion battery with the nitrogen-containing aromatic fused ring polymer synthesized in Example 1 as the positive electrode material has a cycle performance at different temperatures and current densities of 0.05 A g-1, 0.1 A g-1, 0.2 A g-1, 0.5 A g-1, and 1 A g-1. and different temperatures.

[0049] Figure 9 The water-based zinc ion battery with the nitrogen-containing aromatic fused ring polymer synthesized in Example 1 as the positive electrode material has a cycle performance at different temperatures and current densities of 0.05 A g-1, 0.1 A g-1, 0.2 A g-1, 0.5 A g-1, and 1 A g-1. -1 and different temperatures. DETAILED DESCRIPTION

[0050] The advantages and various effects of the present application will be more clearly presented by the following specific embodiments and examples. Those skilled in the art should understand that these specific embodiments and examples are used to illustrate the present application, not to limit the present application.

[0051] Throughout the specification, unless otherwise specifically indicated, the terms used herein are understood to have the meanings commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meaning as generally understood by those skilled in the art to which the present application belongs. If there is a contradiction, the present specification takes precedence.

[0052] Unless otherwise specifically indicated, the various raw materials, reagents, instruments and equipment used in the present application can be purchased from the market or can be prepared by existing methods.

[0053] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0054] The following will be combined with examples and experimental data to explain the nitrogen-containing aromatic fused ring polymer, the preparation method and its application in the preparation of water-based zinc ion battery in detail.

[0055] Example 1

[0056] The present embodiment provides a preparation method of a nitrogen-containing aromatic fused ring polymer, and the specific synthesis route and steps are as follows:

[0057] Synthesis route:

[0058] .

[0059] Synthesis steps:

[0060] (1) Bromination: 2,6-diaminoanthraquinone (DAAQ, 2.38 g, 10 mmol) was dissolved in 140 ml DMF and transferred into a three-necked flask; N-bromosuccinimide (3.75 g, 21 mmol) was dissolved in 20 ml DMF and slowly added into the flask at 0 °C for 30 min, and then the reaction was carried out at room temperature (25 °C) for 24 h under argon atmosphere. The solvent was removed by rotary evaporation under reduced pressure. The crude product was washed with water and ethanol (AR) in turn for several times, and dried in a vacuum oven at 80 °C for 12 h to obtain DAAQ-Br.

[0061] (2) Under argon atmosphere, a solution of DAAQ-Br (1.0 g, 2.5 mmol) and hexanoic anhydride (5 ml, 22 mmol) was heated to 180 °C by microwave for 0.5 h. After filtration, the product was washed with water and ethanol in turn for several times, and dried in a vacuum oven at 80 °C for 12 h to obtain DAAQ-Br-C6.

[0062] (3) De-bromination: DAAQ-Br-C6 (2.95 g, 5 mM), copper powder (0.65 g, 10 mM) and iodine (25 mg, 0.1 mM) were added into 75 ml DMF, and the reaction was carried out at 130 °C for 24 h under N2 atmosphere. The hot reaction mixture was filtered to collect the solution, and the mixture solution was poured into water to precipitate the solid product which was separated by suction filtration. The product was recrystallized from tetrahydrofuran and ether (1:1 by volume), and then washed with water and ethanol in turn for several times. Finally, the solid was dried in a vacuum oven at 80 °C for 12 h to obtain Pre-PPP.

[0063] (4) Dehydration and condensation: 0.434 g of Pre-PPP, 18 ml of HCl (2M) and 5 ml of 1,4-dioxane were added into a 50 ml reaction kettle, and the reaction was carried out at 150 °C for 48 h. The black product was recovered by filtration, washed with tetrahydrofuran, water and ethanol in turn, and then dried in a vacuum oven at 80 °C for 12 h to obtain the final product, azarene polymer (PPP).

[0064] The precursor Pre-PPP was tested by gel permeation chromatography (GPC). According to the relationship between the polymer and the precursor (n (PPP) =n (Pre-PPP) , it can be concluded that the range of n in the structural formula of the PPP prepared in this embodiment is 3-100.

[0065] Battery preparation: The prepared polymer, conductive carbon (ketjen black) and binder (PVDF) were mixed in a mass ratio of 6:3:1, NMP solution was added, the mixture was ground into a paste, then coated on a titanium foil, dried in a vacuum oven at 80-120°C for 8-12h, to prepare an electrode sheet. The positive electrode sheet was used as the positive electrode, the metal zinc foil as the negative electrode, the glass fiber separator was used to separate the two electrodes, the aqueous zinc perchlorate electrolyte was added, and the CR2032 button cell was assembled.

[0066] Related tests:

[0067] The polymerization degree of the polymer was obtained by testing gel permeation chromatography (GPC). High-resolution transmission electron microscopy (HRTEM) was tested using Themis Z instrument, Fourier transform infrared spectroscopy (FT-IR, Thermo Scientific Nicolet iS5) was used for spectral analysis of the polymer, thermogravimetric analysis (TGA, sta449f5) tested the thermal stability of PPP in air at 30-900°C, the polymer conductivity was tested using PPMS-9 temperature and field control platform + KEITHLEY 2400 source meter + KEITHLEY 2182A nanovolt meter to test the resistance and conductivity of the material at -50-50°C, and the electrochemical performance of the polymer was tested on NEWARE at 0.2-1.6 V voltage range and GITT test.

[0068] The test results are as follows:

[0069] Figure 1 The TEM photo of the nitrogen-containing aromatic fused ring polymer synthesized in Example 1, the material presents a disordered stacking state like graphite, showing its micro-morphology characteristics.

[0070] Figure 2 The infrared spectrum of the nitrogen-containing aromatic fused ring polymer synthesized in Example 1 and the infrared spectrum of the precursor at each step; the spectrum shows the chemical structure of the reaction product at each stage and the appearance / disappearance of the corresponding functional groups CH2, CH3, C-Br, C=N, C=O and -NH2, proving the rationality of the synthesis route and proving the preparation of the final product.

[0071] Figure 3 The gel permeation chromatogram (GPC) of the polymer precursor Pre-PPP, after calculation, the structure of the nitrogen-containing aromatic fused ring polymer is n=3-100.

[0072] Figure 4 The thermogravimetric analysis chart of the nitrogen-containing aromatic fused ring polymer synthesized in Example 1, from the chart it can be seen that the polymer has good structural thermal stability.

[0073] Figure 5 The resistance and conductivity of the nitrogen-containing aromatic fused ring polymer synthesized in Example 1 as a function of temperature (-50-50℃) are shown in the graph. It can be observed that as the temperature increases, the resistance of the nitrogen-containing aromatic fused ring polymer decreases and the electronic conductivity increases, and at room temperature it exhibits a high conductivity of 5.75 x 10 -4 S cm –1 .

[0074] Figure 6 The constant current charge-discharge curves of the aqueous zinc ion battery with the nitrogen-containing aromatic fused ring polymer synthesized in Example 1 as the positive electrode material at a current density of 0.1 A g -1 -1 and different temperatures are shown in the graph. At different temperatures, similar redox processes are exhibited, indicating that the temperature has no significant effect on the redox reaction of the nitrogen-containing aromatic fused ring polymer positive electrode. In addition, there is no obvious polarization phenomenon at high and low temperatures, indicating that the reaction kinetics of the nitrogen-containing aromatic fused ring polymer is stable at different temperatures.

[0075] Figure 7 The rate performance of the aqueous zinc ion battery with the nitrogen-containing aromatic fused ring polymer synthesized in Example 1 as the positive electrode material at different temperatures is shown in the graph. Within a current range of 0.1-20 A g -1 -1, the nitrogen-containing aromatic fused ring polymer positive electrode exhibits excellent rate performance at low / high temperatures, The capacity retention values at 0.1, 0.5, 1, 2, 5, 10, 20 and 30 A g -1 -1 are 79.0, 85.8, 86.1, 86.8, 86.5, 83.1, 80.0 and 76.3% compared with those at 25℃, respectively, showing a higher low-temperature capacity retention rate. When the current is restored to 0.1 A g -1 -1 from 20 A g -1, the capacity is restored to 210, 205, 161, 143 and at 50, 25, , and respectively, demonstrating the excellent stability and reversibility of the nitrogen-containing aromatic fused ring polymer positive electrode at different temperatures.

[0076] Figure 8 The cycle performance of the aqueous zinc ion battery with the nitrogen-containing aromatic fused ring polymer synthesized in Example 1 as the positive electrode material at a current density of and different temperatures is shown in the graph. The nitrogen-containing aromatic fused ring polymer positive electrode exhibits satisfactory 164, 166, 136, 114 and at 50, 25, , and The high discharge specific capacity and impressive stability after 10,000 cycles demonstrate that this polymer possesses superior electrochemical stability and energy storage capabilities.

[0077] Figure 9 This is a comparison of the ion diffusion coefficients of an aqueous zinc-ion battery using the nitrogen-containing aromatic fused-ring polymer synthesized in Example 1 as the positive electrode material at different temperatures. The results show that at 50, 25, ... and At temperatures of [temperature value missing], the nitrogen-aromatic fused-ring polymer cathode exhibits a high and stable diffusion coefficient, ranging from [temperature value missing] to [temperature value missing]. to This demonstrates the rapid reaction kinetics and superior ion transport capabilities of PPP.

[0078] It should be noted that by changing the ratio of raw materials in different steps, this invention can obtain the nitrogen-aromatic fused-ring polymer and exhibit excellent electrochemical performance.

[0079] In summary, this invention designs an organic electrode material—a nitrogen-containing aromatic fused-ring polymer—which has high reversible capacity and rapid charge transfer capability. These characteristics make this organic electrode material show great potential when applied as a cathode material for aqueous zinc-ion batteries.

[0080] Finally, it should be noted that the terms “comprising,” “including,” or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0081] Although preferred embodiments of the invention have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including both the preferred embodiments and all changes and modifications falling within the scope of the invention.

[0082] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A nitrogen heteroaromatic fused ring polymer, characterized by, The structural formula of the nitrogen heteroaromatic fused ring polymer is as follows: ; Wherein, n is 3-100.

2. The method for preparing a nitrogen-containing aromatic fused-ring polymer as described in claim 1, characterized in that, The preparation method comprises: sequentially performing bromination reaction, debromination reaction and dehydration condensation reaction on 2,6-diaminoanthraquinone to obtain the nitrogen-containing aromatic fused ring polymer.

3. The method for preparing a nitrogen-containing aromatic fused-ring polymer according to claim 2, characterized in that, The preparation method specifically comprises: S1. 2,6-diaminoanthraquinone and N-bromosuccinimide are dissolved in an organic solvent respectively to obtain 2,6-diaminoanthraquinone solution and N-bromosuccinimide solution, the N-bromosuccinimide solution is added dropwise into the 2,6-diaminoanthraquinone solution at 0±5℃, bromination reaction is carried out under inert atmosphere after warming, the solvent is removed after the reaction is completed, the obtained crude product is washed and vacuum dried to obtain 2,6-diamino-1,5-bromo-anthraquinone; S2. The 2,6-diamino-1,5-bromo-anthraquinone and hexanoic anhydride solution are subjected to microwave reaction under inert atmosphere at 170-190℃ for 0.5-1h, the obtained crude product is filtered, washed and vacuum dried to obtain DAAQ-Br-C6; S3. The DAAQ-Br-C6, copper powder and iodine are added into an organic solvent together, heated to 120-140℃ under inert atmosphere and reacted for 18-28h, the reaction is completed, the filtrate is poured into water to precipitate solid, then solid-liquid separation is carried out, the obtained solid is recrystallized with a mixed solution of tetrahydrofuran and ether, the crystal is washed and vacuum dried to obtain Pre-PPP; S4. The Pre-PPP, dilute hydrochloric acid and 1,4-dioxane are mixed, heated at 150±10℃ for 40-54h, then solid-liquid separation is carried out after cooling, the obtained solid is washed and dried to obtain the nitrogen-containing aromatic fused ring polymer; Wherein, the structures of the DAAQ-Br-C6 and the Pre-PPP are as follows: 、 。 4. The method for preparing a nitrogen-containing aromatic fused-ring polymer according to claim 3, characterized in that, In step S1, the molar ratio of 2,6-diaminoanthraquinone to N-bromosuccinimide is 1:(2-3); The inert atmosphere is argon or nitrogen; The reaction temperature of the bromination reaction is 25±5℃, and the reaction time is 20-28h; Wherein, the obtained crude product is washed and vacuum dried, specifically comprising: The obtained crude product is washed with water and ethanol several times in sequence, and then vacuum dried at 60-100℃ for 8-16h.

5. The method for preparing a nitrogen-containing aromatic fused-ring polymer according to claim 3, characterized in that, In step S2, the molar ratio of DAAQ-Br to hexanoic anhydride is 1:(5-15), the reaction temperature is 170-190 o C, and the reaction time is 0.5-1 h. Wherein, the obtained crude product is filtered, washed and vacuum dried, specifically comprising: The obtained crude product is filtered, and then washed with water and ethanol several times in sequence, and the washed product is vacuum dried at 60-100℃ for 8-16h.

6. The method for preparing a nitrogen-containing aromatic fused-ring polymer according to claim 3, characterized in that, In step S3, the molar ratio of the DAAQ-Br-C6, copper powder and iodine is 1:(1.5-3.5):(0.01-0.5); Wherein, the obtained solid is recrystallized with a mixed solution of tetrahydrofuran and ether, and the crystal is washed and vacuum dried, specifically comprising: The obtained solid is recrystallized with a mixed solution of tetrahydrofuran and ether, the volume ratio of tetrahydrofuran to ether is 1:(0.5-1.5), the crystal is washed with water and ethanol several times in sequence, and then vacuum dried at 60-100℃ for 8-16h.

7. The method for preparing a nitrogen-containing aromatic fused-ring polymer according to claim 3, characterized in that, In step S4, the concentration of the dilute hydrochloric acid is 1.5-2.5 mol / L; 1,4-dioxane and the volume ratio of the dilute hydrochloric acid is 1: (3-5) ; The obtained solid is washed with tetrahydrofuran, water and ethanol in sequence, and the washed product is vacuum dried at 60-100°C for 8-16 hours to obtain the nitrogen-containing aromatic fused ring polymer.

8. Use of the nitrogen-containing aromatic fused ring polymer of claim 1 as or for preparing an organic positive electrode material.

9. Use of the nitrogen-containing aromatic fused ring polymer of claim 1 for preparing a water-based zinc ion battery. The water-based zinc ion battery contains the nitrogen-containing aromatic fused ring polymer of claim 1.

10. A wide temperature range aqueous zinc-ion battery, characterized in that, ​

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