A sulfur-containing heterocyclic trihelix quinone organic battery cathode material and a preparation method thereof

Abstract

A kind of organic positive electrode molecule containing sulfur heterocycle triphenylene quinone and its preparation method.The molecular design is based on the propeller type structure formed by the expansion of the side wing benzene ring of triphenylene quinone through sulfide bond bridge.Further, the triphenylene quinone compound containing sulfur heterocycle is formed by connecting one of 2,3,6,7,14,15-hexachlorotriphenylene quinone, 2,3-difluorobenzoquinone, 2,3-dichloronaphthoquinone, 2,3-dichloroanthraquinone, 6,7-dichloroquinoxaline-5,8-dione and 2,3-dichloro-5,8-dihydroxynaphthalene-1,4-dione through sulfide bond to form propeller type triphenylene quinone molecule. The obtained organic positive electrode molecule containing sulfur heterocycle triphenylene quinone forms a two-dimensional supramolecular polymer through the π-π interaction of its side wings, which relieves the dissolution problem in ether electrolyte and shows excellent charge and discharge cycle stability. At the same time, the weak van der Waals force between the two-dimensional layers is beneficial to the rapid transmission of metal ions, realizing excellent rate performance. The provided electrochemically active positive electrode material can realize the performance of high capacity, high rate and long cycle life of organic battery.

Description

Technical Field

[0001] This invention relates to the field of secondary battery materials, specifically to a sulfur-containing heterocyclic triterpenoid quinone electrochemically active organic cathode material, its preparation method, and its application. Background Technology

[0002] To meet the growing demand for energy storage, developing new batteries with fast-charging capabilities has become a key technological challenge. The materials used in the electrodes significantly affect the charging and discharging speed of lithium-ion batteries. Traditional lithium-ion batteries are often based on transition metal oxides and graphite materials, resulting in low power density and long charging times, which is detrimental to the development of power batteries. Furthermore, the limited availability of transition metals and their environmental hazards lead to high production costs and fail to meet the needs of sustainable development.

[0003] Organic redox active materials, composed of abundant carbon, oxygen, hydrogen, and nitrogen, exhibit advantages such as high theoretical capacity, flexible structural design, and environmental friendliness, making organic secondary batteries a promising alternative for sustainable energy storage. Reported organic electrode materials mainly include conductive polymers, organosulfur compounds, organic free radicals, and quinones. Among them, quinones possess advantages such as high energy density and good reversibility. Patents such as CN111909008A and CN116454278A have invented a series of quinone-based small-molecule cathode materials; however, their battery capacity decays rapidly during cycle testing due to severe dissolution problems of small organic molecules in organic electrolytes. Articles such as Adv. Sci. 2015, 2, 1500124 and Angew. Chem. Int. Ed. 2024, e202412452 propose that forming small organic molecules into organic polymers or covalent organic frameworks (COFs) effectively alleviates the dissolution problem. However, polymers and COFs have low electronic conductivity, and COFs usually have long ion transport paths. Especially under fast charging conditions, it is difficult for ions to reach the active sites buried deep inside the one-dimensional channels, which will inevitably lead to insufficient utilization of redox active sites, thereby reducing the utilization rate of active sites and the rate performance of the battery. Summary of the Invention

[0004] The main objective of this invention is to provide a sulfur-containing heterocyclic triterpenoid quinone electrochemically active cathode material and its preparation method, and to apply it to organometallic batteries, thereby solving problems such as easy dissolution and poor ion diffusion kinetics of small organic molecule cathode materials.

[0005] The present invention adopts the following technical solution:

[0006] An electrochemically active molecule containing sulfur-containing heterocyclic tripterobenone, including propeller-shaped tripterobenone formed by 2,3,6,7,14,15-hexachlorotripterobenone compounds through thioether bond bridge-like extended flanks.

[0007] Specifically, the electrochemically active molecule of the sulfur-containing heterocyclic tripteronequinone includes propeller-shaped tripteronequinone formed by nucleophilic substitution reaction of 2,3,6,7,14,15-hexachlorotripteronequinone with any one of 2,3-difluorobenzoquinone, 2,3-dichloronaphthoquinone, 2,3-dichloroanthraquinone, 6,7-dichloroquinoxalin-5,8-dione and 2,3-dichloro-5,8-dihydroxynaphtho-1,4-dione.

[0008] This invention also provides a method for preparing a sulfur-containing heterocyclic tripteronequinone electrochemically active organic cathode material, comprising combining three reaction substrates by a solvothermal method to obtain a propeller-shaped tripteronequinone formed by the quinone compound through a thioether bond bridge-like extension wing. The three reaction substrates are 2,3,6,7,14,15-hexachlorotripteronequinone, sodium sulfide nonahydrate, and at least one quinone halogen compound that can react with the above two compounds to form a thioether bond.

[0009] Specifically, the propeller-shaped tripteroquinone structural material is obtained by reacting 2,3,6,7,14,15-hexachlorotripteroquinone with any one of 2,3-difluorobenzoquinone, 2,3-dichloronaphthoquinone, 2,3-dichloroanthraquinone, 6,7-dichloroquinoxalin-5,8-dione, and 2,3-dichloro-5,8-dihydroxynaphthyl-1,4-dione. Sodium sulfide nonahydrate is added to an organic solvent to link 2,3,6,7,14,15-hexachlorotripteroquinone with any one of the above monomers via a thioether bond, forming a propeller-shaped tripteroquinone molecule. The synthetic reaction formula is as follows:

[0010]

[0011] Furthermore, the preparation method of the sulfur-containing heterocyclic triterpenoid quinone electrochemically active molecule includes the following steps:

[0012] Step 1): Add 2,3,6,7,14,15-hexachlorotripteroquinone, sodium sulfide nonahydrate, and organic solvent to the reaction vessel, circulate the solution three times by freezing / vacuuming to remove oxygen, and react at 60-90°C for 1-3 hours to obtain a dark green reaction mixture.

[0013] Step 2): Add any one of the monomers 2,3-difluorobenzoquinone, 2,3-dichloronaphthoquinone, 2,3-dichloroanthraquinone, 6,7-dichloroquinoxaline-5,8-dione, and 2,3-dichloro-5,8-dihydroxynaphthyl-1,4-dione to the mixture, remove oxygen from the solution by freezing / vacuuming three times, and continue to react at 90-120°C for 36-64 hours to obtain a brown reaction mixture;

[0014] Step 3): Evaporate the organic solvent in the brown reaction mixture, wash the resulting solid sequentially with deionized water, ethanol, and tetrahydrofuran, and then dry it to obtain the target triterpenoid quinone compound.

[0015] Further, in step 1), the organic solvent is any one of dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide, and the quantitative molar ratio of 2,3,6,7,14,15-hexachlorotripteroenequinone to sodium sulfide nonahydrate is 1:6 to 1:6.5.

[0016] Further, in step 2), the molar ratio of the monomers of 2,3-difluorobenzoquinone, 2,3-dichloronaphthoquinone, 2,3-dichloroanthraquinone, 6,7-dichloroquinoxaline-5,8-dione and 2,3-dichloro-5,8-dihydroxynaphtho-1,4-dione to 2,3,6,7,14,15-hexachlorotripteroenequinone is 4:1 to 5:1.

[0017] A positive electrode comprises 45-70 wt% of triterpenoid quinone electrochemically active molecules containing sulfur heterocycles, 20-45 wt% of conductive additives, and 5-10 wt% of binder.

[0018] An organometallic battery includes a positive electrode, a negative electrode, a separator, and an electrolyte.

[0019] Furthermore, the negative electrode is a lithium metal negative electrode, a zinc metal negative electrode, or a sodium metal negative electrode.

[0020] Furthermore, the conductive additive is one of carbon nanotubes, conductive carbon black, or acetylene black, and the binder is one of polyvinylidene fluoride or polytetrafluoroethylene.

[0021] Furthermore, the electrolyte is lithium bis(trifluoromethanesulfonate)imide dissolved in a mixed solvent of 1,3-dioxolane and 1,2-dimethoxyethane.

[0022] The present invention has the following beneficial effects:

[0023] This invention provides a sulfur-containing heterocyclic tripterene-based organic cathode material and its preparation method, achieving long lifespan, high energy density, and high power density in organic secondary batteries. Using tripterenequinone as a precursor, the flanking molecule of tripterenequinone is extended, allowing supramolecular self-assembly between adjacent molecules under strong π-π interactions, forming a two-dimensional supramolecular polymer. The van der Waals forces between the layers of the two-dimensional supramolecular polymer are weak, and the interlayer spacing is easily increased during charge and discharge, enabling ions to rapidly transport to active sites. Its advantages include: 1. alleviating the dissolution problem of organic cathode materials and improving long-cycle stability; 2. achieving excellent rate performance while maintaining long-cycle stability; 3. possessing abundant active sites and a high voltage plateau, resulting in high theoretical capacity and energy density. This invention yields a sulfur-containing heterocyclic tripterenequinone organic cathode material, which significantly improves the cycle stability of organic cathode materials and possesses a rapid ion transport mechanism, exhibiting excellent rate performance. This has significant practical implications for promoting the development and application of organic cathode materials. Attached Figure Description

[0024] Figure 1 This is a molecular structure diagram of the sulfur-containing heterocyclic triterpenoid quinone in the embodiments of the present invention;

[0025] Figure 2 Liquid-phase NMR of the sulfur-containing heterocyclic triterpenoid organic molecule of Example 1 of this invention 1 H spectrum;

[0026] Figure 3 Solid-state NMR of the sulfur-containing heterocyclic triterpenoid organic molecule of Example 1 of this invention 13 C spectrum;

[0027] Figure 4 This is the mass spectrum of the triterpenoid organic molecule containing a sulfur heterocycle, as described in Example 1 of the present invention.

[0028] Figure 5 The infrared absorption spectrum of the sulfur-containing heterocyclic triterpenoid organic molecule of Example 1 of the present invention is shown.

[0029] Figure 6 This is a scanning electron microscope image of the sulfur-containing heterocyclic triterpenoid organic molecule of Example 1 of the present invention;

[0030] Figure 7 The charge-discharge curves of the sulfur-containing heterocyclic triptenequinone organic cathode / lithium metal battery are shown in the test examples of this invention.

[0031] Figure 8 The rate performance graph of the sulfur-containing heterocyclic triptenequinone organic cathode / lithium metal battery is shown in the test example of this invention.

[0032] Figure 9 This is a test graph showing the long-cycle stability of a sulfur-containing heterocyclic triptenequinone organic cathode / lithium metal battery, which is a test example of the present invention. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be described in detail below with reference to embodiments and accompanying drawings. It should be emphasized that the following description is merely exemplary and not intended to limit the scope or application of this invention.

[0034] This invention provides a sulfur-containing heterocyclic tripterobenone organic cathode material, wherein the active material is a propeller-shaped tripterobenone formed by extending the side wings of a quinone compound through thioether bonds. In some embodiments, the material is obtained by reacting 2,3,6,7,14,15-hexachlorotripterobenone with any one of 2,3-difluorobenzoquinone, 2,3-dichloronaphthoquinone, 2,3-dichloroanthraquinone, 6,7-dichloroquinoxaline-5,8-dione, and 2,3-dichloro-5,8-dihydroxynaphthoine-1,4-dione.

[0035] In some embodiments, the synthesis steps for preparing the sulfur-containing heterocyclic triterpenoid quinone organic cathode material specifically include the following steps:

[0036] 2,3,6,7,14,15-hexachlorotripteroquinone, sodium sulfide nonahydrate, and an organic solvent were added to a reaction vessel. The solution was circulated three times under freeze-drying and vacuum conditions to remove oxygen. The reaction was continued at 60–90°C for 1–3 hours to obtain a dark green reaction mixture. Then, any one of the monomers 2,3-difluorobenzoquinone, 2,3-dichloro-1,4-naphthoquinone, 2,3-dichloro-1,4-anthradinone, 6,7-dichloroquinoxaline-5,8-dione, and 2,3-dichloro-5,8-dihydroxynaphthyl-1,4-dione was added to the mixture. The solution was circulated three times under freeze-drying and vacuum conditions to remove oxygen. The reaction was continued at 60–90°C for 36–64 hours to obtain a brown reaction mixture. Finally, the organic solvent in the brown reaction mixture is evaporated, and the resulting solid is washed sequentially with deionized water, ethanol, and tetrahydrofuran and then dried (e.g., at 100°C for 24 hours) to obtain the target triterpenoid quinone compound.

[0037] In some embodiments, the organic solvent is any one of dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0038] In some embodiments, the quantitative molar ratio of 2,3,6,7,14,15-hexachlorotripteroquinone to sodium sulfide nonahydrate is 1:6 to 1:6.5.

[0039] In some embodiments, the amount of monomers added to 2,3-difluorobenzoquinone, 2,3-dichloro-1,4-naphthoquinone, 2,3-dichloro-1,4-anthradinone, 6,7-dichloroquinoxaline-5,8-dione, and 2,3-dichloro-5,8-dihydroxynaphtho-1,4-dione in a quantitative molar ratio to 2,3,6,7,14,15-hexachlorotripteroenequinone is 4:1 to 5:1.

[0040] This invention also provides a positive electrode sheet comprising 45-70 wt% of triptenequinone electrochemically active molecules containing sulfur heterocycles, 20-45 wt% of conductive additives, and 5-10 wt% of binder.

[0041] In some embodiments, the organic battery is one of an organolithium metal battery, an organosoil metal battery, and an organozinc metal battery.

[0042] This invention also provides a method for preparing the aforementioned sulfur-containing heterocyclic triterpenoid quinone cathode, comprising the following steps:

[0043] The triterenequinone electrochemically active positive electrode material containing sulfur heterocycles, the conductive agent and the binder are wet-milled and mixed evenly in N-methylpyrrolidone in a certain proportion, and then evenly coated on the current collector. After being dried in a forced-air oven, it is cut and further dried in a vacuum oven to obtain the positive electrode sheet.

[0044] In some embodiments, the method for preparing the sulfur-containing heterocyclic triterpenoid quinone cathode includes the following steps:

[0045] The sulfur-containing heterocyclic triterpenoid quinone electrochemically active molecule, conductive agent, and binder are mixed in N-methylpyrrolidone to form a uniform slurry, which is then coated onto the current collector and pre-dried in a forced-air oven at 80-100°C for 5 hours. The slurry is then cut to a diameter of 12 mm and dried in a vacuum oven at 100°C for 24-36 hours to obtain the positive electrode sheet.

[0046] In some embodiments, the conductive agent includes, but is not limited to, carbon nanotubes, conductive carbon black, acetylene black, etc., the binder includes, but is not limited to, polyvinylidene fluoride, polytetrafluoroethylene, etc., and the current collector includes, but is not limited to, aluminum foil, carbon-coated aluminum foil, carbon felt, etc.

[0047] This invention also provides an organometallic battery, comprising a positive electrode, a metal negative electrode, a separator, and an electrolyte, wherein the positive electrode is a triterpenoid positive electrode sheet containing sulfur heterocycles.

[0048] In some embodiments, the diaphragm is a glass fiber diaphragm, a polypropylene diaphragm, etc., and the electrolyte is lithium trifluoromethanesulfonate dissolved in a mixed solvent of 1,3-dioxolane and 1,2-dimethoxyethane in a volume ratio of 1:1.

[0049] The following describes specific embodiments of the present invention.

[0050] An embodiment of the present invention discloses a sulfur-containing heterocyclic tripteronequinone organic battery cathode material and its preparation method, comprising the following steps: adding a certain amount of 2,3,6,7,14,15-hexachlorotripteronequinone, sodium sulfide nonahydrate, and N,N-dimethylformamide solvent into a Shrek tube, wherein the quantitative molar ratio of 2,3,6,7,14,15-hexachlorotripteronequinone to sodium sulfide nonahydrate is 1:6 to 1:6.5; removing oxygen from the solution by freezing / vacuuming three times; and reacting at a temperature of 60 to 90°C for 1 to 3 hours to obtain a dark green reaction mixture solution. After cooling, any one of the monomers 2,3-difluorobenzoquinone, 2,3-dichloro-1,4-naphthoquinone, 2,3-dichloro-1,4-anthradinone, 6,7-dichloroquinoxalin-5,8-dione, and 2,3-dichloro-5,8-dihydroxynaphtho-1,4-dione is added to the mixture, with a quantitative molar ratio of 2,3,6,7,14,15-hexachlorotripteroquinone of 4:1 to 5:1. The oxygen in the solution is removed by three cycles of freezing / vacuuming. The mixture is then stirred and heated at 90–120°C for 36–64 hours to obtain a brown reaction mixture. Finally, the organic solvent in the brown reaction mixture is evaporated, and the resulting solid is washed sequentially with deionized water, ethanol, and tetrahydrofuran, and then dried at 100°C for 24 hours to obtain the target tripteroquinone compound.

[0051] An embodiment of the present invention discloses a method for preparing a positive electrode sheet for an organic battery, comprising mixing 45-70 wt% of a sulfur-containing heterocyclic triterpenoid quinone electrochemically active molecule, 20-45 wt% of a conductive additive, and 5-10 wt% of a binder in a solvent, coating the mixture onto a current collector, pre-drying it in an 80°C forced-air oven for 5 hours, cutting it into circular sheets, and then drying it in a 100°C vacuum oven for 24 hours to obtain the positive electrode sheet. The conductive additive includes, but is not limited to, carbon nanotubes, conductive carbon black, acetylene black, etc., the binder includes, but is not limited to, polyvinylidene fluoride, polytetrafluoroethylene, etc., the solvent is N-methylpyrrolidone, and the current collector includes aluminum foil, carbon-coated aluminum foil, carbon felt, etc.

[0052] An organic lithium metal battery according to an embodiment of the present invention is assembled from a sulfur-containing heterocyclic triptenequinone organic positive electrode, a lithium metal negative electrode, a suitable separator, and an electrolyte. In some embodiments, the separator is a glass fiber separator, a polypropylene separator, etc., and the electrolyte is a 1 mol / L lithium trifluoromethanesulfonate dissolved in a 1:1 volume ratio mixed solvent of 1,3-dioxolane and 1,2-dimethoxyethane.

[0053] Example 1:

[0054] The preparation of a sulfur-containing heterocyclic triterpenoid active material includes the following steps:

[0055] Weigh 60 mg of 2,3,6,7,14,15-hexachlorotripteroquinone and 160 mg of sodium sulfide nonahydrate, transfer to a Shrek tube, add 20 mL of N,N-dimethylformamide, and circulate the solution three times under freeze / vacuum conditions to remove oxygen. React at 75°C for 3 hours until the solution turns dark green. After cooling, add 100 mg of 2,3-dichloro-1,4-naphthoquinone, and circulate the solution three times under freeze / vacuum conditions to remove oxygen. Stir and heat at 100°C for 48 hours to obtain a brown reaction mixture. Evaporate the organic solvent in the brown reaction mixture, wash successively with 200 mL each of deionized water, ethanol, and tetrahydrofuran, and dry in a vacuum oven at 100°C to obtain the sulfur-containing heterocyclic tripteroquinone active material. Liquid chromatography-nuclear magnetic resonance (LC-NMR) analysis was performed. 1 H spectrum as shown Figure 2 As shown, solid-state NMR 13 C spectrum as shown Figure 3 As shown, the mass spectrometry is as follows Figure 4 As shown, the infrared absorption spectrum is as follows: Figure 5 As shown, the scanning electron microscope image is as follows: Figure 6 As shown.

[0056] Example 2:

[0057] The preparation of a sulfur-containing heterocyclic triterpenoid active material includes the following steps:

[0058] Weigh 60 mg of 2,3,6,7,14,15-hexachlorotripteroquinone and 160 mg of sodium sulfide nonahydrate, transfer them to a Shrek tube, add 20 mL of N,N-dimethylformamide, and circulate the solution three times under freeze / vacuum conditions to remove oxygen. React at 90 °C for 3 hours until the solution turns dark green. After cooling, add 120 mg of 2,3-dichloro-1,4-anthradinone, and circulate the solution three times under freeze / vacuum conditions to remove oxygen. Stir and heat at 120 °C for 48 hours to obtain a brown reaction mixture. Evaporate the organic solvent in the brown reaction mixture, wash successively with 200 mL each of water, ethanol, and tetrahydrofuran, and dry in a vacuum oven at 100 °C to obtain the sulfur-containing heterocyclic tripteroquinone active material.

[0059] Example 3:

[0060] The preparation of a sulfur-containing heterocyclic triterpenoid active material includes the following steps:

[0061] Weigh 60 mg of 2,3,6,7,14,15-hexachlorotripteroquinone and 160 mg of sodium sulfide nonahydrate, transfer them to a Shrek tube, add 20 mL of N,N-dimethylformamide, and circulate the solution three times under freeze / vacuum conditions to remove oxygen. React at 60°C for 3 hours until the solution turns dark green. After cooling, add 62 mg of 2,3-difluorobenzoquinone, and circulate the solution three times under freeze / vacuum conditions to remove oxygen. Stir and heat at 100°C for 48 hours to obtain a brown reaction mixture. Evaporate the organic solvent in the brown reaction mixture, wash successively with 200 mL each of water, ethanol, and tetrahydrofuran, and dry in a vacuum oven at 100°C to obtain the sulfur-containing heterocyclic tripteroquinone active material.

[0062] Example 4:

[0063] The preparation of a sulfur-containing heterocyclic triterpenoid active material includes the following steps:

[0064] Weigh 60 mg of 2,3,6,7,14,15-hexachlorotripteroquinone and 160 mg of sodium sulfide nonahydrate, transfer them to a Shrek tube, add 20 mL of N,N-dimethylacetamide, and circulate the solution three times under freeze / vacuum conditions to remove oxygen. React at 80°C for 3 hours until the solution turns dark green. After cooling, add 115 mg of 2,3-dichloro-5,8-dihydroxynaphthalene-1,4-dione, and circulate the solution three times under freeze / vacuum conditions to remove oxygen. Stir and heat at 90°C for 48 hours to obtain a brown reaction mixture. Evaporate the organic solvent in the brown reaction mixture, wash successively with 200 mL each of water, ethanol, and tetrahydrofuran, and dry in a vacuum oven at 100°C to obtain the sulfur-containing heterocyclic tripteroquinone active material.

[0065] Example 5:

[0066] The preparation of a sulfur-containing heterocyclic triterpenoid active material includes the following steps:

[0067] Weigh 60 mg of 2,3,6,7,14,15-hexachlorotripteroquinone and 160 mg of sodium sulfide nonahydrate, transfer them to a Shrek tube, add 20 mL of N,N-dimethylacetamide, and circulate the solution three times under freeze / vacuum conditions to remove oxygen. React at 80 °C for 3 hours until the solution turns dark green. After cooling, add 100 mg of 6,7-dichloroquinoxaline-5,8-dione, and circulate the solution three times under freeze / vacuum conditions to remove oxygen. Stir and heat at 120 °C for 48 hours to obtain a brown reaction mixture. Evaporate the organic solvent in the brown reaction mixture, wash successively with 200 mL each of water, ethanol, and tetrahydrofuran, and dry in a vacuum oven at 100 °C to obtain the sulfur-containing heterocyclic tripteroquinone active material.

[0068] Example 6:

[0069] The preparation of a sulfur-containing heterocyclic triterpenoid quinone cathode includes the following steps:

[0070] A sulfur-containing heterocyclic triterpenoid active molecule, conductive carbon black, and polyvinylidene fluoride were ground and mixed evenly at a mass ratio of 5:4:1. An appropriate amount of N-methylpyrrolidone was added dropwise, and the slurry was thoroughly stirred until fully mixed. This mixture was then coated onto an aluminum foil current collector and dried in an 80°C forced-air oven for 5 hours. The resulting slurry was cut into 12mm diameter discs and then dried in a 100°C vacuum drying oven for 24 hours. The active material loading ranged from 0.25 to 0.5 mg / cm³. 2 .

[0071] Test example:

[0072] Application and performance testing of a sulfur-containing heterocyclic triterpenoid quinone active cathode in fast-charging organic lithium metal batteries:

[0073] 1) Assembly of lithium metal battery: The positive electrode is the sulfur-containing heterocyclic triterpenoid quinone active material prepared in this invention, the negative electrode is lithium metal, the separator is a polypropylene separator, and the electrolyte is a 1 mol / L solution of lithium trifluoromethanesulfonate in 1,3-dioxolane and 1,2-dimethoxyethane, wherein the volume ratio of 1,3-dioxolane to 1,2-dimethoxyethane is 1:1. The battery is assembled using a CR2032 button cell, and the structure consists of a positive electrode cap, a gasket, a positive electrode sheet, an electrolyte, a separator, a lithium metal negative electrode, a gasket, a spring, and a negative electrode cap.

[0074] 2) Electrochemical testing: Under room temperature conditions, the lithium metal battery prepared in Example 1 was subjected to constant current charge-discharge testing on a Blue Electric CT2001A. The voltage range was 1.5–3.5V, and the current density was 90 mA / g. The charge-discharge curves are shown below. Figure 7 As shown, the maximum specific capacity reaches 288 mAh / g, the active sites are fully utilized, and the energy density is 738 Wh / kg; high-rate performance tests were conducted on the battery, such as... Figure 8 As shown, the voltage range is 1.5–3.5V. At an extremely high rate of 90C (27A / g), the battery charges to 65% of its total capacity in 25 seconds, demonstrating excellent rate performance. Long-cycle stability tests were also conducted on the battery. Figure 9 As shown, under a high current density of 15C (4.5A / g) and a long cycle stability test of 2000 cycles, the battery capacity retention rate was 90.88%, and the coulombic efficiency remained stable.

[0075] As can be seen from the above embodiments, the positive electrode sheet prepared by the above embodiments of the present invention has excellent rate performance and long cycle performance through ingenious molecular structure design, and solves the problems of dissolution of organic positive electrode materials and poor metal ion transport.

[0076] In summary, this invention provides a sulfur-containing heterocyclic tripterenequinone organic battery cathode material and its preparation method. Using tripterenequinone as a precursor, the sidewalls of the tripterenequinone molecule are extended, allowing for supramolecular self-assembly between adjacent molecules under strong π-π interactions, forming a two-dimensional supramolecular polymer. This polymer is poorly soluble in conventional electrolytes, effectively alleviating the dissolution problem of organic cathode materials and improving long-cycle stability. The van der Waals forces between the two-dimensional supramolecular polymer layers are weak, and the interlayer spacing is easily expanded during charge and discharge, allowing metal ions to rapidly transport to active sites and undergo redox reactions. Therefore, while maintaining long-cycle stability, it exhibits excellent rate performance. Furthermore, this structure has abundant active sites and a high voltage plateau, resulting in high theoretical capacity and energy density. Ultimately, this enables the application of high-energy-density, fast-charging, and long-cycle-stability organic cathode materials, which has significant practical implications for promoting the development and application of organic batteries.

[0077] The above description, in conjunction with specific / preferred embodiments, provides a further detailed explanation of the present invention. It should not be construed that the specific implementation of the present invention is limited to these descriptions. It should be understood that the above description is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A sulfur-heterocycle-containing trihelium quinone electrochemically active molecule, characterized in that, the trihelium quinone electrochemically active molecule comprises a propeller-type trihelium quinone formed by connecting 2,3,6,7,14,15-hexachlorotrihelium quinone to any one of 2,3-difluorobenzoquinone, 2,3-dichloronaphthoquinone, 2,3-dichloroanthraquinone, 6,7-dichloroquinoxaline-5,8-dione and 2,3-dichloro-5,8-dihydroxynaphthalene-1,4-dione by nucleophilic substitution reaction, and the corresponding structural formulae are as follows: 。 2. A process for the preparation of a sulfur-containing heterocyclic trihelical fullerene quinoid electrochemically active molecule as claimed in claim 1, characterized in that, The trihelium quinone electrochemically active molecule is obtained by combining three reaction substrates through a solvothermal method, the three reaction substrates being 2,3,6,7,14,15-hexachlorotrihelium quinone, sodium sulfide nine hydrates and at least one quinone halogen compound capable of forming a sulfide bond with the above two compounds; the quinone halogen compound is any one of 2,3-difluorobenzoquinone, 2,3-dichloronaphthoquinone, 2,3-dichloroanthraquinone, 6,7-dichloroquinoxaline-5,8-dione and 2,3-dichloro-5,8-dihydroxynaphthalene-1,4-dione.

3. The method for preparing the electrochemically active molecule of triterpenoid containing a sulfur heterocycle as described in claim 2, characterized in that, It comprises the following steps: Step 1): 2,3,6,7,14,15-hexachlorotrihelium quinone, sodium sulfide nine hydrates and an organic solvent are added to a reaction container, oxygen in the solution is removed by freezing / vacuum cycling three times, and the reaction is carried out at a temperature of 60-90℃ for 1-3 hours to obtain a dark green reaction mixture; Step 2): any one of 2,3-difluorobenzoquinone, 2,3-dichloronaphthoquinone, 2,3-dichloroanthraquinone, 6,7-dichloroquinoxaline-5,8-dione and 2,3-dichloro-5,8-dihydroxynaphthalene-1,4-dione monomer is added to the mixture, oxygen in the solution is removed by freezing / vacuum cycling three times, and the reaction is continued at a temperature of 90-120℃ for 36-64 hours to obtain a brown reaction mixture; Step 3): the organic solvent in the brown reaction mixture is evaporated, and the obtained solid is sequentially washed with deionized water, ethanol and tetrahydrofuran and dried to obtain the trihelium quinone electrochemically active molecule.

4. The method for preparing the electrochemically active molecule of triterpenoid quinone containing sulfur heterocycles as described in claim 3, characterized in that, In step 1), the organic solvent is any one of dimethyl sulfoxide, N,N-dimethylformamide and N,N-dimethylacetamide, and the quantitative molar ratio of 2,3,6,7,14,15-hexachlorotrihelium quinone to sodium sulfide nine hydrates is 1:6-1:6.

5.

5. The method for preparing the electrochemically active molecule of triterpenoid quinone containing sulfur heterocycles as described in claim 3, characterized in that, In step 2), the quantitative molar ratio of the monomer of 2,3-difluorobenzoquinone, 2,3-dichloronaphthoquinone, 2,3-dichloroanthraquinone, 6,7-dichloroquinoxaline-5,8-dione and 2,3-dichloro-5,8-dihydroxynaphthalene-1,4-dione to 2,3,6,7,14,15-hexachlorotrihelium quinone is 4:1-5:

1.

6. A positive electrode sheet characterized by comprising: It comprises 45-70wt% of the sulfur-heterocycle-containing trihelium quinone electrochemically active molecule as claimed in claim 1, 20-45wt% of a conductive additive and 5-10wt% of a binder.

7. An organic metal battery, characterized by, It comprises the positive electrode sheet as claimed in claim 6, a metal negative electrode, a separator and an electrolyte.

8. The organometallic battery of claim 7, wherein, The metal negative electrode is any one of lithium metal, zinc metal, and sodium metal; and the electrolyte is lithium bis(trifluoromethylsulfonyl)imide dissolved in a mixed solvent of 1,3-dioxolane and 1,2-dimethoxyethane.

Images