Sulfur-doped oxygen-nitrogen-enriched conjugated organic material and application thereof in Li < + > / Zn < 2 + > ion battery

Abstract

The invention belongs to the field of metal ion battery material synthesis, and particularly provides a sulfur-doped oxygen-nitrogen-enriched conjugated organic material and application thereof in Li < + > / Zn < 2 + > ion batteries. The preparation method comprises the following steps: firstly, preparing 2, 3, 8, 9, 14, 15-hexachlorodiquinoline [2, 3-a: 2 ', 3'-c] phenazine (HANT-Cl) by taking cyclohexanehexone and dichlorobenzene diamine as raw materials, and then synthesizing 6S6O and the derivative thereof by taking HATN-Cl, sodium sulfide nonahydrate and a naphthoquinone derivative as raw materials. The obtained electrode material contains a plurality of oxidation-reduction active sites, multi-electron storage can be carried out, the transfer rate of electrons is improved through the large pi conjugated structure of the conjugated quinoneazine material, and therefore the high theoretical specific capacity and the excellent rate performance are achieved. Due to the addition of the sulfur element, the oxidation-reduction potential of the material is improved, the energy density of a battery can be improved, and the material has a wide application prospect in a Li < + > / Zn < 2 + > ion battery system.

Description

Technical Field

[0001] This invention belongs to the field of metal-ion battery material synthesis, specifically providing a sulfur-doped oxygen-rich nitrogen-conjugated organic material and its application in Li + / Zn 2+ Applications in ion batteries. Background Technology

[0002] With the acceleration of global industrialization and excessive reliance on fossil fuels, energy crises and environmental pollution have become severe challenges facing human society. Developing efficient and clean renewable energy sources (such as solar and wind power) and their supporting large-scale energy storage systems is a key strategy for achieving sustainable development. Against this backdrop, electrochemical energy storage devices, especially metal-ion batteries represented by lithium-ion and zinc-ion batteries, are playing a crucial role due to their high energy density, rechargeability, and environmental friendliness.

[0003] Currently, commercial lithium-ion batteries generally use inorganic electrode materials (such as lithium cobalt oxide and lithium iron phosphate). Although these materials have advantages such as high energy density and long cycle life, their development also faces significant bottlenecks: the uneven distribution, limited reserves, and high prices of key metal resources such as cobalt and nickel lead to high costs and supply chain risks; the synthesis of inorganic materials usually involves high-temperature heat treatment, which consumes a lot of energy and is prone to environmental pollution; their crystal structure is relatively rigid, and the volume changes significantly during repeated ion insertion / extraction, limiting further improvements in rate performance and cycle stability.

[0004] To overcome the aforementioned disadvantages, organic electrode materials have emerged. They are primarily composed of abundant carbon, hydrogen, oxygen, and nitrogen elements, making them readily available, inexpensive, and environmentally friendly. Furthermore, the flexible design of organic molecular structures allows for the achievement of high theoretical capacity and rapid reaction kinetics through functional group modification. More importantly, their flexible molecular structure can effectively buffer volumetric strain during charge and discharge processes, potentially leading to superior cycle life.

[0005] Given the immense potential of organic electrode materials, developing novel battery systems to match them is imperative. Among these, lithium-ion batteries, with their mature technology, remain a crucial platform for pursuing high energy density systems. However, the scarcity of lithium resources has also raised widespread concerns. Therefore, aqueous zinc-ion batteries, with their abundant reserves, lower cost, and inherent safety, have attracted significant interest from the research community. Zinc metal anodes possess high theoretical capacity and low redox potential; combined with organic cathode materials, they can be used to construct next-generation energy storage systems that combine economic efficiency, safety, and environmental friendliness.

[0006] Therefore, developing novel organic electrode materials suitable for high-performance lithium-ion batteries, especially the more promising zinc-ion batteries, has significant scientific research value and broad commercial prospects. Summary of the Invention

[0007] The purpose of this invention is to provide a class of sulfur-doped oxygen-rich nitrogen-conjugated organic materials, their preparation methods and applications, in order to solve the problems of low capacity and poor cycle stability that have always existed in inorganic electrode materials.

[0008] The structural formula of the sulfur-doped oxygen-rich nitrogen-conjugated organic material of this invention is shown below:

[0009] R1 and R2 are derived from nitro, amino, methyl, ethyl, hydroxy or phenyl.

[0010] This material contains multiple redox active sites, enabling multi-electron storage, thus exhibiting a high theoretical specific capacity, greater than 300 mAh g⁻¹. -1 Secondly, the large π-conjugated structure of conjugated quinone azine materials increases the electron transfer rate, thus resulting in excellent rate performance. Furthermore, the addition of sulfur increases the redox potential of the material to some extent, which can improve the energy density of the battery.

[0011] The sulfur-doped oxygen-rich nitrogen-conjugated organic material of the present invention preferably consists of one of the following nine compounds:

[0012]

[0013] The preparation method of the sulfur-doped oxygen-rich nitrogen-conjugated organic material of the present invention includes the following steps: (1) Cyclohexanehexanone (octahydrate) and dichlorophenylenediamine were added to an organic solvent and refluxed in an oil bath at 100-160 °C for 32 h under nitrogen protection. After cooling to room temperature, the solvent was removed by filtration and the mixture was washed and dried under vacuum to obtain a light green solid, 2,3,8,9,14,15-hexachlorodiquinoline[2,3-a:2',3'-c]phenazine (HATN-Cl).

[0014] The molar ratio of cyclohexanehexanone hydrate to dichlorophenylenediamine is 1:2 to 1:4; the organic solvent is acetic acid or nitric acid.

[0015] (2) Dissolve the HATN-Cl and sodium sulfide nonahydrate prepared in step (1) in an organic solvent and mix thoroughly by ultrasonic vibration. Then add different naphthoquinone derivatives and reflux the mixture in an oil bath at 120-180 °C for 24-48 h under nitrogen protection. After cooling to room temperature, filter to remove the solvent and wash. After vacuum drying, a reddish-brown solid is obtained, which is tribenzothiazine dione [2,3-b] (1,4,5,8,9,12-hexaazatriphenyl) (6S6O) or its derivatives.

[0016] The naphthoquinone derivative is selected from one of the following: dichloronaphthoquinone, 2,3-dichloro-7-nitro-1,4-naphthoquinone, 2,3-dichloro-7-amino-1,4-naphthoquinone, 2,3-dichloro-6-methyl-1,4-naphthoquinone, 2,3-dichloro-6,7-dimethyl-1,4-naphthoquinone, 2,3-dichloro-6-ethyl-1,4-naphthoquinone, 2,3-dichloro-6-hydroxy-1,4-naphthoquinone, 2,3-dichloro-6-hydroxy-7-methyl-1,4-naphthoquinone, and 2,3-dichloro-6-phenyl-1,4-naphthoquinone.

[0017] The molar ratio of 2,3,8,9,14,15-hexachlorodiquinoline[2,3-a:2',3'-c]phenazine, naphthoquinone derivatives, and sodium sulfide nonahydrate is 1:2:2 to 1:4:4. The organic solvent is N-methyl-2-pyrrolidone (NMP) or N,N-2-methylformamide (DMF).

[0018] The sulfur-doped oxygen-rich nitrogen conjugated organic material of the present invention is used to prepare cathode materials for lithium-ion batteries or zinc-ion batteries.

[0019] The preparation method of the cathode material is as follows: sulfur-doped oxygen-rich nitrogen conjugated organic material, conductive additives and binders are dispersed evenly in a solvent and coated onto a current collector, and then vacuum dried to obtain the organic cathode material.

[0020] Furthermore, the conductive additive is carbon black, Super P, Ketjen black, activated carbon, graphene, or carbon nanotubes, and the binder is polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, or styrene-butadiene rubber. The current collector is 300-mesh stainless steel mesh, titanium mesh, carbon paper, aluminum foil, or copper foil.

[0021] The mass ratio of sulfur-doped oxygen-rich nitrogen-conjugated organic material, conductive additive, and binder was 8:1:1. Vacuum drying was carried out at 110 °C for 18 hours.

[0022] Beneficial effects: The conjugated organic material of the present invention contains multiple redox active sites, enabling multi-electron storage, and therefore has a high theoretical specific capacity, greater than 300 mAh g⁻¹. -1Secondly, the large π-conjugated structure of conjugated quinone azine materials increases the electron transfer rate, thus resulting in excellent rate performance. Furthermore, the addition of sulfur increases the redox potential of the material to some extent, which can improve the energy density of the battery. Attached Figure Description

[0023] Figure 1 This is the solid-state carbon NMR spectrum of conjugated quinone azine organic electrode material I from Example 1.

[0024] Figure 2 This is the infrared spectrum of conjugated quinone azine organic electrode material I from Example 1.

[0025] Figure 3 This is the CV curve of a lithium-ion battery prepared using organic electrode material I from Example 1.

[0026] Figure 4 This is a rate performance graph of a lithium-ion battery prepared using organic electrode material I in Example 1 at different current densities.

[0027] Figure 5 The above shows the charge-discharge curves of the lithium-ion battery prepared using organic electrode material I from Example 1.

[0028] Figure 6 This is a cycle stability diagram of a lithium-ion battery prepared using organic electrode material I from Example 1.

[0029] Figure 7 This is the CV curve of the zinc-ion battery prepared using organic electrode material I in Example 1.

[0030] Figure 8 This is a rate performance graph of a zinc-ion battery prepared with organic electrode material I in Example 1 at different current densities.

[0031] Figure 9 This is the charge-discharge curve of the zinc-ion battery prepared using organic electrode material I in Example 1.

[0032] Figure 10 This is a cycle stability diagram of a zinc-ion battery prepared using organic electrode material I from Example 1.

[0033] Figure 11 This is a rate performance graph of the lithium-ion battery using organic electrode material II from Example 3 at different current densities.

[0034] Figure 12 The above are the charge-discharge curves of the lithium-ion battery prepared using organic electrode material II in Example 3.

[0035] Figure 13 This is a cycle performance diagram of the lithium-ion battery using organic electrode material II from Example 3. Detailed Implementation

[0036] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Furthermore, the technical features described in the various embodiments of the invention below can be combined with each other as long as they do not conflict with each other.

[0037] Example 1: The synthesis route of organic electrode material I is as follows:

[0038]

[0039] First, 1 mmol of cyclohexanehexanone octahydrate, 2 mmol of dichlorophenylenediamine, and 150 ml of acetic acid (HOAc) were added to a three-necked round-bottom flask. The mixture was heated to 140 °C in an oil bath under N2 atmosphere and stirred under reflux for 24 h. The temperature was then increased to 160 °C and the reaction continued for 6 h. After the reaction was complete, the mixture was cooled to room temperature, and the suspension was filtered. The filter cake was washed five times with hot ethanol, then washed five times with water, and finally dried under vacuum at 60 °C for 8 h to obtain a light green solid, which was the intermediate 2,3,8,9,14,15-hexachlorodiquinoline[2,3-a:2',3'-c]phenazine (HATN-Cl), with a yield of 96%.

[0040] 1 mmol HATN-Cl and 2 mmol g Na₂S·9H₂O were dissolved in 40 mL of N-methylpyrrolidone solution. The mixture was then sonicated for 10 minutes to ensure thorough mixing before adding 2 mmol dichloronaphthoquinone. The reaction mixture was refluxed with continuous stirring at 140 °C for 24 h. After the reaction was complete, the mixture was cooled to room temperature, filtered, and washed five times with hot ethanol, followed by five washes with water. The product was dried under vacuum at 60 °C for 12 h. Finally, recrystallization was performed using DMF, followed by the same filtration and drying process. A dark red solid 6S₆O organic electrode material I was obtained with a yield of 90%.

[0041] Solid-state carbon NMR spectrum of organic electrode material I as follows Figure 1As shown, the 13C NMR spectrum of 6S6O has nine distinct peaks, appearing at approximately 133.7 ppm (peak a), 126.09 ppm (peak b), 133.5 ppm (peak c), 176.8 ppm (peak d), 133.4 ppm (peak e), 133.1 ppm (peak f), 126.27 ppm (peak g), 141 ppm (peak h), and 135.2 ppm (peak i). The positions of the tested peaks are consistent with the theoretically simulated peaks, indicating that the prepared product is the target product 6S6O.

[0042] The infrared spectrum of organic electrode material I is as follows: Figure 2 As shown in the figure, a relatively obvious carbonyl peak, carbon-nitrogen double bond peak, and carbon-nitrogen single bond peak appear at 700 cm⁻¹. -1 The appearance of a unique carbon-sulfur single bond peak confirms the synthesis of 6S6O.

[0043] Organic electrode material I is used not only as a positive electrode material for zinc and lithium-ion batteries, but also in aqueous or organic potassium, sodium, magnesium, aluminum, and calcium-ion batteries.

[0044] Organic electrode material I was used to prepare a positive electrode material for lithium-ion batteries. The organic positive electrode material, Ketjen black, and polyvinylidene fluoride (mass ratio 8:1:1) were uniformly dispersed in N-methyl-2-pyrrolidone (NMP), and uniformly coated onto aluminum foil using a coater. The mixture was then vacuum dried at 60 °C for 4 h, followed by vacuum drying at 110 °C overnight to obtain the organic positive electrode.

[0045] A lithium-ion battery was assembled using an organic positive electrode, a lithium sheet as the negative electrode, a porous polypropylene membrane as the separator, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) solution as the electrolyte, and a mixed solvent of 1,3-dioxolane (DOL) and dimethyl ethylene glycol (DME) as the solvent. The voltage testing window is 1.3V to 3.8V.

[0046] Figure 3 Cyclic voltammetry curves of a lithium-ion battery assembled with organic electrode material I at different scan rates are shown in the figure. The redox peaks remain well-formed, with two distinct pairs of redox peaks. The average potential of the first pair of redox peaks is approximately 1.61 V, and the average potential of the second pair is approximately 2.37 V. With increasing scan rate, the peak current increases slightly and exhibits a regular change, indicating good stability of the redox reaction.

[0047] Figure 4 The rate performance of lithium-ion batteries assembled with this material is plotted at different current densities. (0.1, 0.2, 0.3, 0.5, 1.0, and 2.0 A g) -1The reversible capacities corresponding to the current densities are 282, 238, 227, 214, 208, and 195 mAhg, respectively. -1 When the current density recovers to 0.1 A g -1 At that time, the battery's reversible capacity recovered to 236 mAh g. -1 This represents 83.7% of its initial capacity. From the corresponding charge / discharge curves ( Figure 5 The data also shows that the battery has a stable discharge-charge voltage platform, proving that 6S6O has a high specific capacity and excellent rate performance.

[0048] Figure 6 Lithium-ion batteries assembled using this material have a performance of 0.1 A g. -1 Cycling performance at current density. The first discharge capacity after battery activation is 282 mAh g. -1 After 2000 cycles, the capacity is 170 mA hg. -1 The capacity retention rate was 60.3%, and the coulombic efficiency was close to 100%. This indicates that the battery has good cycle stability.

[0049] Organic electrode material I was used to prepare a positive electrode material for zinc-ion batteries. The organic positive electrode material, Ketjen black, and polyvinylidene fluoride (mass ratio 8:1:1) were uniformly dispersed in N-methyl-2-pyrrolidone (NMP), uniformly coated onto carbon paper, and then vacuum dried at 60 °C for 4 h, followed by vacuum drying at 110 °C overnight to obtain the organic positive electrode.

[0050] A zinc-ion battery was assembled using an organic positive electrode, a zinc sheet as the negative electrode, a glass fiber membrane as the separator, and a 1M ZnSO4 solution as the electrolyte. The voltage testing window is 0.1V to 1.6V.

[0051] Figure 7 Cyclic voltammetry curves of a zinc-ion battery assembled with organic electrode material I at different scan rates are shown in the figure. The redox peaks remain well-formed, and two pairs of distinct redox peaks can be observed. For detailed analysis, please refer to the cyclic voltammetry curves of lithium-ion batteries.

[0052] Figure 8 The rate performance of zinc-ion batteries assembled with this material at different current densities is shown in the graph. Figure 9 The corresponding charge-discharge curves are shown. At the initial current density, the average battery capacity reaches 250 mAh g⁻¹. -1 As the current density increases, the battery capacity decreases slowly; as the current density decreases, the battery capacity increases steadily. When the current density returns to 0.1 A g... -1 At that time, the battery capacity recovered to 220mAh g -1It achieves 88% of the average capacity at the initial current density. Simultaneously, a very clear charge-discharge plateau is observed in the corresponding charge-discharge curves, proving that this material also possesses good rate performance for zinc-ion batteries.

[0053] Figure 10 Lithium-ion batteries assembled using this material have a performance of 0.1 A g. -1 Cycling performance at current density. The first discharge capacity after battery activation is 265 mAh g. -1 After 2000 cycles, the capacity is 189 mA hg. -1 The capacity retention was 71.3%, and the coulombic efficiency was close to 100%. The capacity decreased slowly with cycling, and after 3500 charge-discharge cycles, the capacity was 162 mA hg. -1 The capacity retention rate was 61.1%, and the coulombic efficiency remained close to 100%. This indicates that the material also exhibits good cycle stability when applied to zinc-ion batteries.

[0054] Example 2: The molar ratio of cyclohexanehexanone octahydrate and dichlorophenylenediamine was changed to 1:4, and the other conditions were the same as in Example 1. The final yield of intermediate HATN-Cl was 92%.

[0055] The molar ratio of HATN-Cl, sodium sulfide nonahydrate, and dichloronaphthoquinone was changed to 1:4:4, and the other conditions were the same as in Example 1. The final yield of product 6S6O was 87%.

[0056] The remaining steps are the same as in Example 1.

[0057] Lithium-ion batteries assembled with this product have performance values ​​of 0.1, 0.2, 0.3, 0.5, 1.0, and 2.0 A g. -1 The reversible capacities corresponding to the current densities are 312, 298, 286, 275, 262, and 245 mAh g, respectively. -1 .

[0058] Example 3: By replacing dichloronaphthoquinone with 2,3-dichloro-7-nitro-1,4-naphthoquinone, and with the other conditions remaining the same as in Example 1, organic electrode material II was obtained with a yield of 81%.

[0059] Organic electrode material II was used to prepare lithium-ion batteries. The electrode preparation method and battery assembly were the same as in Example 1.

[0060] Figure 11 The rate performance of lithium-ion batteries assembled with organic electrode material II is shown in the graphs at different current densities, with a voltage range of 1.3-3.8V. At a current density of 0.1A g... -1 The battery capacity reaches 280 mAh g-1 When the current density increases to 2Ag -1 At that time, the battery capacity was still 170mAh g. -1 about.

[0061] Figure 12 Lithium-ion batteries assembled using organic electrode material II at 0.1 A g -1 The charge-discharge curves show a clear charging and discharging plateau, indicating that the material also has good rate performance when applied to lithium-ion batteries.

[0062] Figure 13 Lithium-ion batteries assembled using organic electrode material II at 0.1 A g -1 Cycling performance at current density. The first discharge capacity after battery activation is 280 mAh g. -1 After 2500 cycles, the capacity is 231 mAh g. -1 The capacity retention rate is 82.2%, and the coulombic efficiency is close to 100%. This indicates that the battery has good cycle stability.

[0063] Example 4: The molar ratio of cyclohexanehexanone octahydrate and dichlorophenylenediamine was changed to 1:4, and the other conditions were the same as in Example 1, to obtain the intermediate HATN-Cl with a yield of 82%.

[0064] By replacing dichloronaphthoquinone with 2,3-dichloro-7-nitro-1,4-naphthoquinone, and changing the molar ratio of HATN-Cl, sodium sulfide nonahydrate, and 2,3-dichloro-7-nitro-1,4-naphthoquinone to 1:4:4, and keeping the other conditions the same as in Example 1, organic electrode material II was obtained with a yield of 75%.

[0065] The lithium-ion battery assembled with this organic electrode material II was tested at 0.1 A g. -1 Cycling performance at current density. The first discharge capacity after battery activation is 296 mAh g. -1 After 2000 cycles, the capacity is 245 mAh g. -1 The capacity retention rate is 82.8%, and the coulombic efficiency is close to 100%. This indicates that the battery has good cycle stability.

[0066] Example 5: First, 1 mmol of cyclohexanehexanone octahydrate, 4 mmol of dichlorophenylenediamine, and 150 ml of acetic acid (HOAc) were added to a three-necked round-bottom flask. The mixture was heated to 140 °C in an oil bath under N2 atmosphere and stirred under reflux for 24 h. The temperature was then increased to 160 °C and the reaction continued for another 6 h. After the reaction was completed, the mixture was cooled to room temperature, and the suspension was filtered. The filter cake was washed with hot ethanol and water and dried under vacuum at 60 °C for 8 h to obtain a light green solid, which was the intermediate product 2,3,8,9,14,15-hexachlorodiquinoline[2,3-a:2',3'-c]phenazine (HATN-Cl), with a yield of 97%.

[0067] 1 mmol HATN-Cl and 4 mmol g Na₂S·9H₂O were dissolved in 40 mL of N-methylpyrrolidone solution. The mixture was then sonicated for 10 minutes to ensure thorough mixing before adding 4 mmol 2,3-dichloro-6-hydroxy-1,4-naphthoquinone. The reaction mixture was refluxed with continuous stirring at 140 °C for 48 h. After the reaction was complete, the mixture was cooled to room temperature, filtered, and washed with hot ethanol and water. The product was dried under vacuum at 60 °C for 12 h. Finally, recrystallization was performed using DMF, followed by the same filtration and drying process. The yield was 89%.

[0068] Lithium-ion batteries assembled with this organic electrode material achieve a speed of 0.1 A g. -1 The initial discharge capacity at the current density is 328 mAh g. -1 After 2000 cycles, the capacity is 276 mAh g. -1 The capacity retention rate is 84.1%, and the coulombic efficiency is close to 100%. This indicates that the battery has good cycle stability.

[0069] Example 6: The preparation process of the intermediate product 2,3,8,9,14,15-hexachlorodiquinoline[2,3-a:2',3'-c]phenazine (HATN-Cl) is the same as in Example 5.

[0070] 1 mmol HATN-Cl and 4 mmol g Na₂S·9H₂O were dissolved in 40 mL of N-methylpyrrolidone solution. The mixture was then sonicated for 10 minutes to ensure thorough mixing before adding 4 mmol 2,3-dichloro-6-hydroxy-7-methyl-1,4-naphthoquinone. The reaction mixture was refluxed with continuous stirring at 140 °C for 48 h. After the reaction was complete, the mixture was cooled to room temperature, filtered, and washed with hot ethanol and water. It was then dried under vacuum at 60 °C for 12 h. Finally, recrystallization was performed using DMF, followed by the same filtration and drying process. The yield was 89%.

[0071] Lithium-ion batteries assembled with this organic electrode material achieve a speed of 0.1 A g. -1 The initial discharge capacity at the current density is 297 mAh g. -1 After 2000 cycles, the capacity is 254 mAh g. -1 The capacity retention rate is 85.5%, and the coulomb efficiency is close to 100%.

[0072] Example 7: The preparation process of the intermediate product 2,3,8,9,14,15-hexachlorodiquinoline[2,3-a:2',3'-c]phenazine (HATN-Cl) is the same as in Example 5.

[0073] 1 mmol HATN-Cl and 4 mmol g Na₂S·9H₂O were dissolved in 40 mL of N-methylpyrrolidone solution. The mixture was then sonicated for 10 minutes to ensure thorough mixing before adding 4 mmol 2,3-dichloro-6-phenyl-1,4-naphthoquinone. The reaction mixture was refluxed with continuous stirring at 140 °C for 48 h. After the reaction was complete, the mixture was cooled to room temperature, filtered, and washed with hot ethanol and water. It was then dried under vacuum at 60 °C for 12 h. Finally, recrystallization was performed using DMF, followed by the same filtration and drying process. The yield was 89%.

[0074] Lithium-ion batteries assembled with this organic electrode material achieve a speed of 0.1 A g. -1 The initial discharge capacity at the current density is 306 mAh g. -1 After 2000 cycles, the capacity is 242 mAh g. -1 The capacity retention rate was 79.1%, and the coulomb efficiency was close to 100%.

[0075] Compare with Example 1: First, 1 mmol of cyclohexanehexanone octahydrate, 2 mmol of dichlorophenylenediamine, and 150 ml of acetic acid (HOAc) were added to a three-necked round-bottom flask. The mixture was heated to 140 °C in an oil bath under N2 atmosphere and stirred under reflux for 24 h. The temperature was then increased to 160 °C and the reaction continued for another 6 h. After the reaction was complete, the mixture was cooled to room temperature, and the suspension was filtered. The filter cake was washed five times with hot ethanol, then washed five times with water, and finally dried under vacuum at 60 °C for 8 h to obtain a light green solid, which was the intermediate product 2,3,8,9,14,15-hexachlorodiquinoline[2,3-a:2',3'-c]phenazine (HATN-Cl), with a yield of 96%.

[0076] 1 mmol HATN-Cl and 2 mmol dichloronaphthoquinone were mixed and refluxed with continuous stirring at 140 °C for 24 h. No dark red product was observed after the reaction.

[0077] Electrochemical performance of 2,3,8,9,14,15-hexachlorodiquinoline[2,3-a:2',3'-c]phenazine (HATN-Cl)

[0078] This organic electrode material was used to prepare a positive electrode material for lithium-ion batteries. The organic positive electrode material, Ketjen black, and polyvinylidene fluoride (mass ratio 8:1:1) were uniformly dispersed in N-methyl-2-pyrrolidone (NMP), and uniformly coated onto aluminum foil using a coater. The mixture was then vacuum dried at 60 °C for 4 h, followed by vacuum drying at 110 °C overnight to obtain the organic positive electrode.

[0079] A lithium-ion battery was assembled using an organic positive electrode, a lithium sheet as the negative electrode, a porous polypropylene membrane as the separator, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) solution as the electrolyte, and a mixed solvent of 1,3-dioxolane (DOL) and dimethyl ethylene glycol (DME) as the solvent. The voltage testing window is 1.3V to 3.8V.

[0080] The lithium-ion battery assembled with this material has a first-cycle discharge capacity of 152 mAh g. -1 After 2000 cycles, the capacity is 81 mA hg. -1 The capacity retention rate was 53.3%.

Claims

1. A sulfur-doped, oxygen-rich, nitrogen-conjugated organic material, characterized in that, The structural formula of the conjugated organic material is as follows: ， wherein R1, R2 are selected from nitro, amino, methyl, ethyl, hydroxyl or phenyl.

2. The sulfur-doped, oxygen-rich nitrogen-conjugated organic material of claim 1, wherein, The conjugated organic material is selected from one of the following compounds: 、 、 、 、 、 、 、 or .

3. A method of producing the sulfur-doped oxygen-rich nitrogen-conjugated organic material according to claim 1, characterized by, The preparation method comprises the following steps: (1) adding cyclohexanone octahydrate and dichlorobenzene diamine into an organic solvent, heating and refluxing under oil bath for 32 hours under nitrogen protection; after cooling to room temperature, removing the solvent by suction filtration and washing, and vacuum drying to obtain 2,3,8,9,14,15-hexachloro diquinoxaline [2,3-a:2',3'-c] phenazine HATN-Cl as a light green solid; (2) mixing the light green solid 2,3,8,9,14,15-hexachloro diquinoxaline [2,3-a:2',3'-c] phenazine obtained in step (1) and sodium sulfide nonahydrate into an organic solvent and ultrasonically oscillating to mix thoroughly, then adding a naphthoquinone derivative, heating and refluxing under oil bath under nitrogen protection, cooling to room temperature, removing the solvent by suction filtration and washing, and vacuum drying to obtain triphenothioxanthene dione [2,3-b] (1,4,5,8,9,12-hexaazatriphenyl) 6S6O or a derivative thereof as a red-brown solid.

4. The method for preparing sulfur-doped oxygen-rich nitrogen-conjugated organic materials according to claim 3, characterized in that, In step (1), the molar ratio of cyclohexanone octahydrate and dichlorobenzene diamine is 1:2-1:4, the organic solvent is acetic acid or nitric acid, and the reflux reaction temperature is 100-160 ℃.

5. The method for preparing sulfur-doped oxygen-rich nitrogen-conjugated organic materials according to claim 3, characterized in that, In step (2), the naphthoquinone derivative is selected from one of the following: dichloronaphthoquinone, 2,3-dichloro-7-nitro-1,4-naphthoquinone, 2,3-dichloro-7-amino-1,4-naphthoquinone, 2,3-dichloro-6-methyl-1,4-naphthoquinone, 2,3-dichloro-6,7-dimethyl-1,4-naphthoquinone, 2,3-dichloro-6-ethyl-1,4-naphthoquinone, 2,3-dichloro-6-hydroxy-1,4-naphthoquinone, 2,3-dichloro-6-hydroxy-7-methyl-1,4-naphthoquinone, and 2,3-dichloro-6-phenyl-1,4-naphthoquinone.

6. The method for preparing sulfur-doped oxygen-rich nitrogen-conjugated organic materials according to claim 3, characterized in that, In step (2), the molar ratio of 2,3,8,9,14,15-hexachloro diquinoxaline [2,3-a:2',3'-c] phenazine, the naphthoquinone derivative and sodium sulfide nonahydrate is 1:2:2-1:4:4, the organic solvent is N-methyl-2-pyrrolidone or N,N-2-methyl formamide, the reflux reaction temperature is 120-180 ℃, and the reaction time is 24-48 hours.

7. Use of the sulfur-doped oxygen-enriched nitrogen-coordinated organic material according to claim 1, characterized in that The sulfur-doped oxygen-rich nitrogen conjugated organic material is applied to the preparation of a lithium ion battery or zinc ion battery positive electrode material.

8. Use of a sulfur-doped oxygen-rich nitrogen-coordinated organic material according to claim 7, characterized in that, The sulfur-doped oxygen-rich nitrogen conjugated organic material, a conductive additive and a binder are uniformly dispersed in a solvent and coated on a current collector, vacuum dried to obtain an organic positive electrode material, cut into slices, and assembled into a battery.

9. Use of a sulfur-doped oxygen-rich nitrogen-coordinated organic material according to claim 8, characterized in that, The conductive additive is carbon black, Super P, Ketjen black, activated carbon, graphene or carbon nanotube; the binder is polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol or styrene butadiene rubber; and the current collector is 300-mesh stainless steel mesh, titanium mesh, carbon paper, aluminum foil or copper foil.

10. Use of the sulfur-doped oxygen-enriched nitrogen-coordinated organic material according to claim 8, characterized in that The mass ratio of the sulfur-doped oxygen-rich nitrogen conjugated organic material, the conductive additive and the binder is 8:1:1, the vacuum drying temperature is 110 ℃, and the drying time is 18 hours.

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