A sulfur-aminophenol polymer composite material, its preparation method and application

Abstract

The present invention discloses a sulfur-aminophenol polymer composite material, a preparation method and an application thereof. The method includes: mixing an aminophenol monomer, an oxidant and elemental sulfur, and heating and reacting at 100-600 °C, and cooling to obtain a solid crude product; removing inorganic and organic impurities from the solid crude product by dissolution and washing to obtain a sulfur-aminophenol polymer composite material A1; mixing elemental sulfur and an aminophenol polymer, and heating and reacting at 100-600 °C, and cooling to obtain a sulfur-aminophenol polymer composite material A2; removing elemental sulfur from the sulfur-aminophenol polymer composite material A1 or A2 by heating evaporation / sublimation or dissolution and washing to obtain a sulfur-aminophenol polymer composite material B with a reduced or completely removed elemental sulfur content. Using the sulfur-aminophenol polymer composite material as a cathode material for secondary batteries in the present invention has the advantages of low cost, high specific capacity, high Coulomb efficiency, good cycle stability, etc.

Description

Technical Field

[0001] The invention relates to the fields of physical chemistry, organic chemistry, polymer science and material science technology, and in particular to a sulfur-aminophenol polymer composite material and a preparation method and application thereof. Background Art

[0002] Due to the limitations of theoretical specific capacity of positive and negative electrodes and metal (cobalt, nickel, lithium) resources, traditional lithium-ion battery technology is difficult to meet people's increasingly high requirements in terms of energy density, price and sustainability. Therefore, the development of high specific energy positive electrode materials and battery systems that are not limited by resources is an important topic in the field of electrochemical energy storage. Lithium-sulfur batteries with elemental sulfur as the positive electrode and metallic lithium as the negative electrode have a capacity of 2600Wh kg -1 The theoretical energy density is 5 to 7 times that of the current mainstream lithium-ion battery system. Moreover, sulfur is an important byproduct of the petroleum industry, with an annual output of 70 million tons, and a very cost-effective (ChemElectroChem, 2017, 4: 2975). In addition, the sulfur positive electrode can also be matched with the metallic sodium and potassium negative electrodes to form sodium-sulfur and potassium-sulfur batteries, further enhancing the advantages in sustainability and cost.

[0003] At present, alkali metal-sulfur battery technology still faces many scientific and technological problems in industrial application. Taking lithium-sulfur batteries as an example, elemental sulfur undergoes a complex solid-liquid-solid transformation process during discharge: first, the solid S 8 is reduced to Li 2 S x (x=8~4), then Li 2 S x is further reduced to a poorly soluble solid product Li 2 S 2 and Li 2 S. Li dissolved in the electrolyte 2 S x The intermediate products will be consumed continuously by chemical or electrochemical reactions on the surface of the lithium negative electrode, or will shuttle between the positive and negative electrodes during charging, leading to problems such as continuous attenuation of battery capacity and reduced coulombic efficiency. 8 Completely converted to Li 2 S will cause a volume change of ~80%, and the electronic and ionic conductivities of both are relatively low. These factors lead to problems such as continuous deterioration of the electrode structure, sluggish reaction kinetics, low capacity utilization, and poor cycle stability.

[0004] The main strategy to solve the above problems is to use various carbon materials (including nitrogen-doped carbon), inorganic metal compounds, metal-organic frameworks and organic polymers as coating layers, host materials or binders for sulfur in the positive electrode, and utilize their electronic conduction, physical confinement, chemical adsorption and chemical catalysis. Among them, commonly used organic polymers include polyaniline (PAni), polypyrrole (PPy), polythiophene (PTh), poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonic acid) (PEDOT:PSS) and other conductive polymers (J.Am.Chem.Soc.,2013,135:16736;Nano Lett.,2013,13:5534;Adv.Mater.,2017,29:1700587;CN105449179B;CN105390665B). However, these conductive polymers have low specific surface areas, poor mixing uniformity with elemental sulfur, and poor Li 2 S x The effect of improving the long-term cycle stability of sulfur cathodes is usually limited due to problems such as weak adsorption capacity. Although increasing the mass ratio of polymer / elemental sulfur or performing complex structural designs (such as coating, core-shell, and lamination) can enhance the sulfur fixation effect, it will also significantly reduce the overall energy density of the sulfur cathode or greatly increase the preparation cost, which is not conducive to practical application.

[0005] Therefore, it is necessary to develop a sulfur-polymer composite positive electrode material with low cost, high specific capacity, high coulombic efficiency and good cycle stability. Summary of the invention

[0006] The present invention aims to provide a sulfur-aminophenol polymer composite material and a preparation method thereof. The sulfur-aminophenol polymer composite material used as a secondary battery positive electrode material has the advantages of low cost, high specific capacity, high coulombic efficiency, good cycle stability, etc. The one-pot in-situ method is used to simultaneously complete the polymerization of aminophenol monomers and the composite of sulfur, which will significantly simplify the preparation process and reduce costs, and is conducive to promoting the practical application of the material.

[0007] In order to achieve the above object, the present invention adopts the following technical solution:

[0008] In a first aspect of the present invention, a method for preparing a sulfur-aminophenol polymer composite material is provided, wherein the sulfur-aminophenol polymer composite material comprises sulfur-aminophenol polymer composite material A1, sulfur-aminophenol polymer composite material A2, and sulfur-aminophenol polymer composite material B; the method comprises:

[0009] The aminophenol monomer, an oxidant and elemental sulfur are mixed and heated at 100-600° C. for reaction, and a solid crude product is obtained after cooling; wherein the aminophenol monomer is a mixture of one or more of o-aminophenol, m-aminophenol and p-aminophenol;

[0010] The solid crude product is dissolved and washed to remove inorganic and organic impurities to obtain a sulfur-aminophenol polymer composite material A1;

[0011] Elemental sulfur and aminophenol polymer are mixed and heated at 100-600° C. for reaction, and then cooled to obtain sulfur-aminophenol polymer composite material A2; wherein the aminophenol polymer is polymerized by chemical oxidation or electrochemical oxidation using one or more of o-aminophenol, m-aminophenol, and p-aminophenol as monomers.

[0012] The sulfur-aminophenol polymer composite material A1 or A2 is heated for evaporation / sublimation or dissolved and washed to remove the contained elemental sulfur, thereby obtaining a sulfur-aminophenol polymer composite material B with reduced or completely removed elemental sulfur content.

[0013] Furthermore, the molar ratio of the aminophenol monomer, the oxidant and elemental sulfur is 1:(1-15):(0-20); and the mass ratio of the elemental sulfur to the aminophenol polymer is 10:1-1:3.

[0014] Furthermore, the oxidant includes at least one of peroxymonosulfuric acid and its salts, peroxydisulfuric acid and its salts, sulfur dioxide, sulfur trioxide, concentrated sulfuric acid, and trivalent iron salts, perchlorates, hypochlorites, permanganates, dichromates, chromic acid, concentrated nitric acid, bromine, iodine, peroxide, chloranil and 2,3-dichloro-5,6-dicyanobenzoquinone.

[0015] Furthermore, the heating reaction is carried out at 100 to 600° C. for 1 to 4320 minutes; and the reaction atmosphere of the heating reaction is selected from vacuum, air, nitrogen or inert gas.

[0016] In the second aspect of the present invention, a sulfur-aminophenol polymer composite material prepared by the method is provided.

[0017] In the third aspect of the present invention, a derivative or multiple complex with sulfur-aminophenol polymer composite material as the main body is provided, wherein the derivative or multiple complex with sulfur-aminophenol polymer composite material as the main body includes a derivative or multiple complex with sulfur-aminophenol polymer composite material A1 as the main body, a derivative or multiple complex with sulfur-aminophenol polymer composite material A2 as the main body, and a derivative or multiple complex with sulfur-aminophenol polymer composite material B as the main body;

[0018] The preparation method of the derivative or multiple composite with sulfur-aminophenol polymer composite material as the main body is to add additives to the heating reaction or to compound the reaction raw materials with additives before conducting the heating reaction, wherein the additives include at least one of carbon materials, metal compounds and chalcogenide elements; the carbon material is selected from conductive carbon black, activated carbon, carbon nanotubes, carbon fibers, graphite, graphene, hard carbon, soft carbon, and porous carbon; the metal compound is selected from carbides, nitrides, oxides, sulfides, phosphides, selenides, tellurides, and MXenes; and the chalcogenide elements are selected from selenium and tellurium.

[0019] In the fourth aspect of the present invention, there is provided the use of the sulfur-aminophenol polymer composite material or the derivative or multiple composite with the sulfur-aminophenol polymer composite material as the main body in the preparation of a positive electrode of a battery.

[0020] In the fifth aspect of the present invention, a battery positive electrode is provided, which is prepared by mixing 30% to 99% active material, 1% to 70% conductive agent and 0% to 40% binder by mass and coating or pressing them on a current collector, wherein the active material is the sulfur-aminophenol polymer composite material or a derivative or multiple composite with the sulfur-aminophenol polymer composite material as the main body.

[0021] In a sixth aspect of the present invention, a battery is provided, wherein the battery is assembled by matching the battery positive electrode with the battery negative electrode directly or after pre-lithium / sodium / potassium treatment.

[0022] One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:

[0023] (1) The monomers such as o-aminophenol, m-aminophenol and p-aminophenol used in the present invention are easy to obtain and have low cost.

[0024] (2) The one-pot in-situ preparation method of the sulfur-aminophenol polymer composite material provided by the present invention is to synthesize the aminophenol monomer, oxidant and elemental sulfur in one step by heating reaction without adding additional reaction solvent. It has the advantages of simple process, low cost, environmental friendliness and easy large-scale production.

[0025] (3) The structure of the sulfur-aminophenol polymer composite material prepared according to the method of the present invention is very conducive to the solid-solid conversion reaction: the conjugated polymer skeleton is conducive to electron conduction, and the rich benzene ring units are conducive to the generation of CS x -C (x ≥ 2) covalent bond, the rich oxazine ring structure not only has adsorption and catalytic effects on sulfur species, but also can contribute additional capacity; the larger specific surface area is conducive to increasing the sulfur content and strengthening the confinement effect.

[0026] (4) The sulfur-aminophenol polymer composite material prepared according to the method of the present invention has the advantages of high specific capacity, high coulombic efficiency, good cycle stability, etc. as a secondary battery positive electrode material.

[0027] (5) The sulfur-aminophenol polymer composite material synthesized according to the method of the present invention can be applied to various alkali metal batteries such as lithium, sodium, potassium, etc., and can also be applied to corresponding ion batteries by pre-lithium / sodium / potassium treatment of the positive electrode or the negative electrode. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are result data of some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0029] Figure 1 (a) X-ray diffraction spectrum, (b) thermogravimetric curve, (c) infrared spectrum and (d) scanning electron microscope image of S-PoAP-300-130;

[0030] Figure 2 (a) Cycling performance and (b) corresponding charge-discharge curves of S-PoAP-300-130 in lithium secondary batteries using ether electrolytes;

[0031] Figure 3 (a) X-ray diffraction spectrum and (b) infrared spectrum of S-PoAP-300-32;

[0032] Figure 4 (a) Cycling performance and (b) corresponding charge-discharge curves of S-PoAP-300-32 in lithium secondary batteries using ether electrolytes;

[0033] Figure 5 (a) X-ray diffraction spectrum and (b) infrared spectrum of S-PoAP-350-1320A;

[0034] Figure 6 (a) Cycling performance and (b) corresponding charge-discharge curves of S-PoAP-350-1320A in lithium secondary batteries using ether electrolytes;

[0035] Figure 7 (a) X-ray diffraction spectrum and (b) infrared spectrum of S-PoAP-350-137;

[0036] Figure 8(a) Cycling performance and (b) corresponding charge-discharge curves of S-PoAP-350-137 in lithium secondary batteries using ester electrolytes;

[0037] Fig. 9 (a) Cycling performance and (b) corresponding charge-discharge curves of S-PoAP-350-137 in sodium secondary batteries using ester electrolytes;

[0038] Fig.10 (a) X-ray diffraction spectrum and (b) infrared spectrum of S-PmAP-350-137;

[0039] Fig.11 (a) Cycling performance and (b) corresponding charge-discharge curves of S-PmAP-350-137 in lithium secondary batteries using ester electrolytes;

[0040] Fig.12 (a) Cycling performance and (b) corresponding charge-discharge curves of S-PmAP-350-137 in sodium secondary batteries using ester electrolytes;

[0041] Fig.13 (a) Cycling performance and (b) corresponding charge-discharge curves of S-PmAP-350-137 in potassium secondary batteries using ester electrolytes;

[0042] Fig.14 (a) X-ray diffraction spectrum and (b) infrared spectrum of S-PpAP-350-137;

[0043] Fig.15 (a) Cycling performance and (b) corresponding charge-discharge curves of S-PpAP-350-137 in lithium secondary batteries using ester electrolytes;

[0044] Fig.16 (a) Cycling performance and (b) corresponding charge-discharge curves of S-PpAP-350-137 in sodium secondary batteries using ester electrolytes;

[0045] Fig.17 (a) Cycling performance and (b) corresponding charge-discharge curves of S-PpAP-350-137 in potassium secondary batteries using ester electrolytes. DETAILED DESCRIPTION

[0046] The present invention will be described in detail below in conjunction with specific implementations and examples, and the advantages and various effects of the present invention will be more clearly presented. It should be understood by those skilled in the art that these specific implementations and examples are used to illustrate the present invention, rather than to limit the present invention.

[0047] Throughout the specification, unless otherwise specifically stated, the terms used herein should be understood as meanings commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. In the event of a conflict, the present specification takes precedence.

[0048] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or obtained by existing methods.

[0049] According to a typical embodiment of the present invention, a method for preparing a sulfur-aminophenol polymer composite material is provided, wherein the sulfur-aminophenol polymer composite material includes sulfur-aminophenol polymer composite material A1, sulfur-aminophenol polymer composite material A2, and sulfur-aminophenol polymer composite material B; the method comprises:

[0050] Step S101, mixing aminophenol monomer, oxidant and elemental sulfur, heating at 100-600° C. for reaction, and obtaining a solid crude product after cooling; wherein the aminophenol monomer is a mixture of one or more of o-aminophenol, m-aminophenol and p-aminophenol.

[0051] The solid crude product is dissolved and washed to remove inorganic and organic impurities to obtain a sulfur-aminophenol polymer composite material A1;

[0052] In step S101,

[0053] The oxidant is at least one of permonosulfuric acid and its salts, peroxydisulfuric acid and its salts, sulfur dioxide, sulfur trioxide, concentrated sulfuric acid, and trivalent iron salts, perchlorates, hypochlorites, permanganates, dichromates, chromic acid, concentrated nitric acid, bromine, iodine, peroxide, chloranil and 2,3-dichloro-5,6-dicyanobenzoquinone.

[0054] The molar ratio of the aminophenol monomer, the oxidant and elemental sulfur is 1:(1-15):(0-20).

[0055] When the oxidant is a sulfur-containing oxidant and can provide sufficient sulfur to complex with the aminophenol polymer, there is no need to add additional elemental sulfur.

[0056] The molar ratio of aminophenol monomer to oxidant is preferably 1:(2-12). This molar ratio range is conducive to obtaining sulfur-aminophenol polymers with high polymerization degree and yield. If too little oxidant is added, it has the adverse effect of reducing the polymerization degree and yield. If too much oxidant is added, it has the adverse effect of wasting raw materials and increasing costs.

[0057] The mixing method is stacking, stirring, grinding, ball milling, sand milling, solid-gas (sulfur dioxide, sulfur trioxide) mixing or solid-liquid (liquid oxidant, elemental sulfur solution) mixing.

[0058] The reaction container used for the heating reaction is in a sealed or semi-sealed state, with or without vibration and rotation, and the reactants are with or without stirring.

[0059] The reaction atmosphere of the heating reaction is vacuum, air, nitrogen or inert gas.

[0060] The heating method is heating furnace heating, oil / sand bath heating or microwave heating.

[0061] The reaction temperature of the heating reaction is 100-600°C, and the reaction time is 1-4320 minutes. The heating program is a constant or multi-stage temperature and time within the range. The reaction temperature is preferably 200-550°C, and the reaction time is preferably 60-1440 minutes.

[0062] Regarding the method of removing inorganic impurities other than elemental sulfur and low molecular weight organic impurities by dissolving and washing the solid crude product, the washing liquid includes but is not limited to one or more of water, methanol, ethanol, propanol, isopropanol, n-butanol, acetone, n-hexane, cyclohexane, dichloromethane, chloroform, N-methylpyrrolidone, N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide, sulfolane, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, ammonia water, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, and potassium iodide aqueous solution.

[0063] Step S102, mixing elemental sulfur and aminophenol polymer, heating at 100-600° C. for reaction, and cooling to obtain sulfur-aminophenol polymer composite material A2; wherein the aminophenol polymer is polymerized by chemical oxidation or electrochemical oxidation using one or more of o-aminophenol, m-aminophenol, and p-aminophenol as monomers.

[0064] In step S102,

[0065] The mass ratio of elemental sulfur to aminophenol polymer is 10:1 to 1:3. This mass ratio range is conducive to taking into account both energy density and cycle stability. If too much elemental sulfur is added, the cycle stability will be adversely affected. If too much aminophenol polymer is added, the energy density will be reduced and the cost will be increased. The mass ratio is preferably 6:1 to 1:2.

[0066] The elemental sulfur and the aminophenol polymer are mixed in a manner of stacking, stirring, grinding, ball milling, sand milling or solid (polymer)-liquid (elemental sulfur solution) mixing.

[0067] The reaction container used for the heating reaction is in a sealed or semi-sealed state, with or without vibration and rotation, and the reactants are with or without stirring.

[0068] The reaction atmosphere of the heating reaction is vacuum, air, nitrogen or inert gas.

[0069] The heating method is heating furnace heating, oil / sand bath heating or microwave heating.

[0070] The reaction temperature of the heating reaction is 100-600°C, and the reaction time is 1-4320 minutes. The heating program is a constant or multi-stage temperature and time within the range. The reaction temperature is preferably 200-450°C, and the reaction time is preferably 60-1440 minutes.

[0071] Step S103, further removing elemental sulfur from the sulfur-aminophenol polymer composite material A1 or A2 by heating evaporation / sublimation or dissolution washing, so as to obtain a sulfur-aminophenol polymer composite material B with reduced or completely removed elemental sulfur content.

[0072] In step S103,

[0073] For the method of removing elemental sulfur contained in the composite material by heating evaporation / sublimation, the heating temperature is 100-500°C, the heating time is 1-2880 minutes, and the heating atmosphere is vacuum, air, nitrogen or inert gas. The heating temperature is preferably 200-400°C, the heating time is preferably 30-720 minutes, and the heating atmosphere is preferably vacuum or nitrogen.

[0074] Regarding the method of removing elemental sulfur contained in the composite material by dissolving and washing, the washing liquid includes but is not limited to non-polar solvents such as benzene, toluene, carbon tetrachloride, carbon disulfide, and hot alkaline solutions such as lithium hydroxide, sodium hydroxide, and potassium hydroxide.

[0075] The obtained product sulfur-aminophenol polymer composite material B has a significantly lower or even zero sulfur content than the sulfur-aminophenol polymer composite material A1 obtained in step S101 and the sulfur-aminophenol polymer composite material A2 obtained in step S102, which will reduce the specific capacity but is beneficial to improving the coulombic efficiency and cycle stability.

[0076] As an optional implementation, an additive is added to the heating reaction of step S101 or step S102, or the reaction raw materials are first compounded with the additive and then subjected to the heating reaction, and the other preparation processes are the same as steps S101 to S103, to prepare a derivative or a multiple complex with the sulfur-aminophenol polymer composite material as the main body.

[0077] The additives are added to change / improve the physical and chemical properties (such as electronic conductivity) of the composite material, and the additives include at least one of a carbon material, a metal compound and a chalcogenide element; the carbon material is selected from conductive carbon black, activated carbon, carbon nanotubes, carbon fibers, graphite, graphene, hard carbon, soft carbon, and porous carbon; the metal compound is selected from carbides, nitrides, oxides, sulfides, phosphides, selenides, tellurides, and MXenes; and the chalcogenide element is selected from selenium and tellurium.

[0078] The present invention also provides the use of the sulfur-aminophenol polymer composite material prepared above or its derivatives or multiple composites mainly in secondary alkali metal (lithium, sodium, potassium) batteries and alkali metal ion batteries, and the preparation methods of the corresponding positive electrodes and batteries.

[0079] According to another typical embodiment of the present invention, a positive electrode of a battery is provided, and a preparation method is as follows:

[0080] Step S201, dispersing and mixing the active material, the conductive agent and the binder in a solvent in a certain proportion, or adopting a dry mixing method without adding a solvent; the active material is the sulfur-aminophenol polymer composite material or a derivative or a multiple composite with the sulfur-aminophenol polymer composite material as the main body; the mass percentage of each component is: active material 30% to 99%, conductive agent 1% to 70%, binder 0% to 40%, and the sum of the three is 100%.

[0081] In step S201,

[0082] The conductive agent is any one or a mixture of graphite, conductive carbon black, acetylene black, Super P, Ketjen black, carbon nanotubes, carbon fibers, activated carbon, graphene (reduced graphene oxide) and fullerene. The conductive agent is preferably conductive carbon black, acetylene black, Super P, Ketjen black or carbon nanotubes.

[0083] The binder is any one or a mixture of polytetrafluoroethylene or its copolymer, polyvinylidene fluoride or its copolymer, polyethylene oxide or its copolymer, polyvinyl alcohol or its copolymer, sodium carboxymethyl cellulose combined with styrene-butadiene rubber or its copolymer, polyether or its copolymer, polyester or its copolymer and polyacrylic acid or polyacrylate. The binder is preferably polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, sodium polyacrylate or lithium polyacrylate.

[0084] The solvent is any one or a mixture of water, ethanol, methanol, propanol, isopropanol, n-butanol, N-methylpyrrolidone, N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide, sulfolane and caprolactam. The solvent is preferably water, ethanol, isopropanol or N-methylpyrrolidone.

[0085] Step S202, coating the mixture on the current collector or pressing it on the current collector after rolling, and forming an electrode after drying. If dry mixing is used, it is also possible not to dry.

[0086] In step S202,

[0087] The current collector is made of any one of aluminum, copper, nickel, titanium, molybdenum, stainless steel and carbon, and is in the form of any one of foil (sheet), mesh, fiber paper and foam metal. The current collector is preferably aluminum mesh or aluminum foil.

[0088] The drying temperature is a constant or variable temperature between 20 and 200° C., and the drying atmosphere is any one of vacuum, air, nitrogen, argon and helium.

[0089] According to another typical embodiment of the present invention, a battery is provided, wherein the battery is assembled by directly or after pre-lithium / sodium / potassium treatment of the battery positive electrode and matching with the battery negative electrode. The preparation method of the corresponding battery is:

[0090] Method 1: Match the battery positive electrode with a metal lithium / sodium / potassium negative electrode or a lithium / sodium / potassium alloy negative electrode, separate the two electrodes with a separator, add an electrolyte, and assemble the battery in an inert atmosphere.

[0091] The diaphragm is any one or a composite diaphragm composed of polyethylene, polypropylene, polytetrafluoroethylene or its copolymer, polyimide, cellulose and glass fiber diaphragms, as well as modified diaphragms based on these diaphragms. The diaphragm is preferably a polypropylene diaphragm or a glass fiber diaphragm.

[0092] The electrolyte is a solution prepared by dissolving a corresponding metal (lithium, sodium, potassium) salt in a solvent, and the salt concentration is 0.1 to 5.0 mol L –1 . The salt is any one of perchlorate, hexafluorophosphate, tetrafluoroborate, trifluoromethanesulfonate, bisoxalate borate, difluorooxalate borate, bisfluorosulfonyl imide salt and bis(trifluoromethanesulfonyl)imide salt, or a mixture of several of them. The solvent is any one of ethylene carbonate, vinylene carbonate, fluoroethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 1,3-dioxolane, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyvinyl alcohol oligomer, acetonitrile, cyclopentane sulfone, dimethyl sulfoxide and γ-butyrolactone, or a mixture of several of them.

[0093] The inert atmosphere is any one of nitrogen, argon and helium or a mixture of several of them. The atmosphere is preferably argon.

[0094] Method 2: Assemble the battery by matching the positive electrode of the battery with the negative electrode such as graphite, silicon, carbon / silicon, hard carbon, soft carbon, etc., but the positive electrode or the negative electrode needs to be chemically or electrochemically pre-lithiated / sodium / potassiumized, so that one of them changes from an oxidized state without lithium / sodium / potassium to a reduced state with lithium / sodium / potassium inserted. The pre-lithiated / sodium / potassiumization method includes a chemical method of contacting the electrode with lithium / sodium / potassium metal or metal organic reagent to cause a redox reaction, and an electrochemical method of pre-discharging the electrode in an electrochemical device. The other preparation processes are the same as those of method 1.

[0095] The metal organic reagent for chemical pre-lithiation / sodium / potassium is an aromatic hydrocarbon solution such as biphenyl and naphthalene in which lithium / sodium / potassium is dissolved.

[0096] The electrolyte and negative electrode used in the electrochemical pre-lithiation / sodium / potassium device are the same as those in method 1, and the atmosphere is any one of nitrogen, argon and helium or a mixed atmosphere of several of them.

[0097] The sulfur-aminophenol polymer composite material or the derivative or multiple composite material based on the sulfur-aminophenol polymer composite material can also be used in solid-state batteries using solid electrolytes. The solid electrolytes include inorganic solid electrolytes, solid polymer electrolytes and composite polymer electrolytes. The solid-state batteries include all-solid-state batteries that do not use liquid electrolytes at all, and semi-solid and quasi-solid-state batteries that partially use liquid electrolytes.

[0098] The sulfur-aminophenol polymer composite material of the present application and its preparation method and application are described in detail below in combination with embodiments, comparative examples and experimental data.

[0099] The monomers used in the present invention [o-aminophenol (oAP), m-aminophenol (mAP) and p-aminophenol (pAP)] are all commercially available and do not require further purification. The oxidants used are mostly commercially available or easily prepared (such as sulfur dioxide and sulfur trioxide, and metal sulfides such as zinc sulfide and nickel sulfide can be used to oxidize the gas generated during the roasting process). The aminophenol polymers used [poly-o-aminophenol (PoAP), poly-m-aminophenol (PmAP) and poly-p-aminophenol (PpAP)] can be synthesized from the above monomers by various chemical and electrochemical oxidation methods, which have been reported in a large number of literatures and have high yields.

[0100] Example 1

[0101] The preparation method of a sulfur-aminophenol polymer composite material and its application in a secondary battery provided in this embodiment include the following steps performed in sequence:

[0102] (1) Weigh o-aminophenol and ammonium persulfate in a molar ratio of 1:3, grind and mix, and place in a stainless steel reactor. The reactor is in a semi-sealed state (the threaded reactor cover is tightened, but the gas can still escape).

[0103] (2) The stainless steel reactor containing the reaction raw materials in step (1) is placed in a tubular furnace with nitrogen passing through one end, and a sodium hydroxide aqueous solution is passed through the other end of the tubular furnace for tail gas treatment.

[0104] (3) The tube furnace was heated to 300° C., the reaction was carried out at a constant temperature for 10 hours, and a solid crude product was obtained after cooling.

[0105] (4) washing the solid crude product in step (3) with water and ethanol to remove inorganic impurities other than elemental sulfur and low molecular weight organic impurities, and drying at 80°C.

[0106] (5) The product in step (4) was washed with toluene and ethanol to further remove the elemental sulfur contained therein and dried at 80°C to obtain a sulfur-poly-o-aminophenol composite material, named S-PoAP-300-130. Its X-ray diffraction spectrum is as follows: Figure 1 The thermogravimetric curve is shown in a. Figure 1 As shown in b, the infrared spectrum Figure 1 c, the microscopic morphology is as follows Figure 1 As shown in d.

[0107] (6) The S-PoAP-300-130 obtained in step (5) is mixed with a conductive agent Ketjen black and a binder polytetrafluoroethylene in a mass ratio of 6:3:1, using a water / isopropyl alcohol mixture as a solvent, into a clay-like state and rolled on a double-roller to form a film. After drying, the film is cut into small discs of appropriate diameter and pressed onto an aluminum mesh current collector to form an electrode sheet.

[0108] (7) Using the electrode sheet prepared in step (6) as the positive electrode, the metal lithium sheet as the negative electrode, and a polypropylene film (Celgard2325) as the separator, add an appropriate amount of electrolyte [1 mol L -1 A solution of lithium bis(trifluoromethanesulfonyl)imide dissolved in a mixture of 1,3-dioxolane / ethylene glycol dimethyl ether, i.e., 1 M LiTFSI / DOL-DME] was assembled into a CR2016-type button cell in an argon-filled glove box.

[0109] (8) The battery prepared in step (7) was charged at 100 mA g in a voltage range of 1.3 to 3.8 V. -1 The charge and discharge cycles were performed at a current density of 1000 Hz (based on the mass of the composite material). The electrochemical properties are shown in Table 1. Figure 2 As shown, S-PoAP-300-130 exhibits 230mAh g -1 The reversible specific capacity (based on the mass of the composite material) is 81% (relative to the reversible specific capacity) after 100 cycles.

[0110] Example 2

[0111] The preparation method of a sulfur-aminophenol polymer composite material and its application in a secondary battery provided in this embodiment include the following steps performed in sequence:

[0112] (1) Elemental sulfur and poly-o-aminophenol are weighed in a mass ratio of 3:2, ground and mixed, and placed in a glass tube with one end sealed.

[0113] (2) The glass tube containing the reaction raw materials in step (1) is evacuated to a pressure lower than 0.1 MPa, and the tube is melt-sealed under a butane flame.

[0114] (3) The sealed glass tube containing the reaction raw materials in step (2) was heated to 300°C, and the reaction was carried out at a constant temperature for 10 hours. After cooling, a sulfur-poly-o-aminophenol composite material was obtained, which was named S-PoAP-300-32. Its X-ray diffraction spectrum is as follows: Figure 3 As shown in a, the infrared spectrum is Figure 3 As shown in b.

[0115] (4) The S-PoAP-300-32 obtained in step (3) is mixed with a conductive agent Ketjen black and a binder polytetrafluoroethylene in a mass ratio of 6:3:1, using a water / isopropyl alcohol mixture as a solvent, into a clay-like state and rolled on a double-roller to form a film. After drying, the film is cut into small discs of appropriate diameter and pressed onto an aluminum mesh current collector to form an electrode sheet.

[0116] (5) Using the electrode sheet prepared in step (4) as the positive electrode, the metal lithium sheet as the negative electrode, and a polypropylene film (Celgard2325) as the separator, add an appropriate amount of electrolyte [1 mol L -1 A solution of lithium bis(trifluoromethanesulfonyl)imide dissolved in a mixture of 1,3-dioxolane / ethylene glycol dimethyl ether, i.e., 1 M LiTFSI / DOL-DME] was assembled into a CR2016-type button cell in an argon-filled glove box.

[0117] (6) The battery prepared in step (5) was charged at 300 mA g in a voltage range of 1.5 to 3.5 V. -1 The charge and discharge cycles were carried out at a current density of 1000 s (based on the mass of sulfur). The electrochemical performance is shown in Figure 2. Figure 4 As shown, S-PoAP-300-32 exhibits 1641 mAh g -1 The reversible specific capacity (based on the mass of sulfur) is 69% (relative to the reversible specific capacity) after 50 cycles.

[0118] Example 3

[0119] The preparation method of a sulfur-aminophenol polymer composite material and its application in a secondary battery provided in this embodiment include the following steps performed in sequence:

[0120] (1) Weigh o-aminophenol, ammonium persulfate and elemental sulfur in a molar ratio of 1:3:20, grind and mix, and place in a glass tube with one end sealed.

[0121] (2) The glass tube containing the reaction raw materials in step (1) is evacuated to a pressure lower than 0.1 MPa, and the tube is melt-sealed under a butane flame.

[0122] (3) The sealed glass tube containing the reaction raw materials in step (2) is heated to 350° C., and the reaction is carried out at a constant temperature for 10 hours. After cooling, a solid crude product is obtained.

[0123] (4) washing the solid crude product in step (3) with water and ethanol to remove inorganic impurities other than elemental sulfur and low molecular weight organic impurities and drying at 80° C. to obtain a sulfur-poly-o-aminophenol composite material named S-PoAP-350-1320A. Its X-ray diffraction spectrum is as follows: Figure 5 As shown in a, the infrared spectrum is Figure 5 As shown in b.

[0124] (5) The S-PoAP-350-1320A obtained in step (4) is mixed with a conductive agent Ketjen black and a binder polytetrafluoroethylene in a mass ratio of 6:3:1, using a water / isopropyl alcohol mixture as a solvent, into a clay-like state and rolled on a double-roller to form a film. After drying, the film is cut into small discs of appropriate diameter and pressed onto an aluminum mesh current collector to form an electrode sheet.

[0125] (6) Using the electrode sheet prepared in step (5) as the positive electrode, the metal lithium sheet as the negative electrode, and a polypropylene film (Celgard2325) as the separator, add an appropriate amount of electrolyte [1 mol L -1 A solution of lithium bis(trifluoromethanesulfonyl)imide dissolved in a mixture of 1,3-dioxolane / ethylene glycol dimethyl ether, i.e., 1 M LiTFSI / DOL-DME] was assembled into a CR2016-type button cell in an argon-filled glove box.

[0126] (7) The battery prepared in step (6) was charged at 1000 mA g in a voltage range of 1.5 to 3.5 V. -1 The charge and discharge cycles were carried out at a current density of 1000 s (based on the mass of sulfur). The electrochemical performance is shown in Figure 2. Figure 6 As shown, S-PoAP-350-1320A exhibits 1094mAhg -1 The reversible specific capacity (based on the mass of sulfur) is 71% after 50 cycles (relative to the reversible specific capacity).

[0127] Example 4

[0128] The preparation method of a sulfur-aminophenol polymer composite material and its application in a secondary battery provided in this embodiment include the following steps performed in sequence:

[0129] (1) Weigh o-aminophenol, ammonium persulfate and elemental sulfur in a molar ratio of 1:3:7, grind and mix, and place in a glass tube with one end sealed.

[0130] (2) The glass tube containing the reaction raw materials in step (1) is evacuated to a pressure lower than 0.1 MPa, and the tube is melt-sealed under a butane flame.

[0131] (3) The sealed glass tube containing the reaction raw materials in step (2) is heated to 350° C., and the reaction is carried out at a constant temperature for 10 hours. After cooling, a solid crude product is obtained.

[0132] (4) washing the solid crude product in step (3) with water and ethanol to remove inorganic impurities other than elemental sulfur and low molecular weight organic impurities, and drying at 80°C.

[0133] (5) The product in step (4) was washed with toluene and ethanol to further remove the elemental sulfur contained therein and dried at 80°C to obtain a sulfur-poly-o-aminophenol composite material named S-PoAP-350-137. Its X-ray diffraction spectrum is as follows: Figure 7 As shown in a, the infrared spectrum is Figure 7 As shown in b.

[0134] (6) The S-PoAP-350-137 obtained in step (5) is mixed with a conductive agent Ketjen black and a binder polytetrafluoroethylene in a mass ratio of 6:3:1, using a water / isopropyl alcohol mixture as a solvent, into a clay-like state, and rolled on a double-roller to form a film. After drying, the film is cut into small discs of appropriate diameter and pressed onto an aluminum mesh current collector to form an electrode sheet.

[0135] (7) Using the electrode sheet prepared in step (6) as the positive electrode, the metal lithium sheet as the negative electrode, and a polypropylene film (Celgard2325) as the separator, add an appropriate amount of electrolyte (1 mol L -1 A solution of lithium hexafluorophosphate dissolved in a mixture of ethylene carbonate / diethyl carbonate, i.e. 1M LiPF 6 / EC–DEC) and assembled into CR2016 button cells in an argon-filled glove box.

[0136] (8) The battery prepared in step (7) was charged at 100 mA g in a voltage range of 1.0 to 3.0 V. -1 The charge and discharge cycles were carried out at a current density of (based on the mass of the composite material, the same below). The electrochemical performance is as follows Figure 8 As shown, S-PoAP-350-137 exhibits 479 mAh g -1The reversible specific capacity of the composite material is 84% ​​(based on the mass of the composite material, the same below). After 100 cycles, the capacity retention rate is 84% ​​(relative to the reversible specific capacity, the same below). The charge and discharge curves show typical solid-solid conversion characteristics.

[0137] (9) Using the electrode sheet prepared in step (6) as the positive electrode, the metal sodium sheet as the negative electrode, and a polypropylene film (Celgard2325) and a glass fiber membrane as the separator, add an appropriate amount of electrolyte (1 mol L -1 A solution of sodium hexafluorophosphate dissolved in a mixture of ethylene carbonate / diethyl carbonate, i.e. 1M NaPF 6 / EC–DEC) and assembled into CR2025 button cells in an argon-filled glove box.

[0138] (10) The battery prepared in step (9) was charged at 200 mA g in a voltage range of 0.8 to 3.0 V. -1 The charge and discharge cycles were carried out at a current density of . Fig. 9 As shown, S-PoAP-350-137 exhibits 356 mAh g -1 The reversible specific capacity is 66% after 30 cycles.

[0139] Example 5

[0140] The preparation method of a sulfur-aminophenol polymer composite material and its application in a secondary battery provided in this embodiment include the following steps performed in sequence:

[0141] (1) m-Aminophenol, ammonium persulfate and elemental sulfur were weighed in a molar ratio of 1:3:7, ground and mixed, and placed in a glass tube with one end sealed.

[0142] (2) The glass tube containing the reaction raw materials in step (1) is evacuated to a pressure lower than 0.1 MPa, and the tube is melt-sealed under a butane flame.

[0143] (3) The sealed glass tube containing the reaction raw materials in step (2) is heated to 350° C., and the reaction is carried out at a constant temperature for 10 hours. After cooling, a solid crude product is obtained.

[0144] (4) washing the solid crude product in step (3) with water and ethanol to remove inorganic impurities other than elemental sulfur and low molecular weight organic impurities, and drying at 80°C.

[0145] (5) The product in step (4) was washed with toluene and ethanol to further remove the elemental sulfur contained therein and dried at 80° C. to obtain a sulfur-poly(m-aminophenol) composite material, named S-PmAP-350-137. Its X-ray diffraction spectrum is as follows: Fig.10 As shown in a, the infrared spectrum is Fig.10 As shown in b.

[0146] (6) The S-PmAP-350-137 obtained in step (5) is mixed with a conductive agent Ketjen black and a binder polytetrafluoroethylene in a mass ratio of 6:3:1, using a water / isopropanol mixture as a solvent, into a clay-like state and rolled into a film on a double-roller. After drying, the film is cut into small discs of appropriate diameter and pressed onto an aluminum mesh current collector to form an electrode sheet.

[0147] (7) Using the electrode sheet prepared in step (6) as the positive electrode, the metal lithium sheet as the negative electrode, and a polypropylene film (Celgard2325) as the separator, add an appropriate amount of electrolyte (1 mol L -1 A solution of lithium hexafluorophosphate dissolved in a mixture of ethylene carbonate / diethyl carbonate, i.e. 1M LiPF 6 / EC–DEC) and assembled into CR2016 button cells in an argon-filled glove box.

[0148] (8) The battery prepared in step (7) was charged at 100 mA g in a voltage range of 1.0 to 3.0 V. -1 The charge and discharge cycles were carried out at a current density of (based on the mass of the composite material, the same below). The electrochemical performance is as follows Fig.11 As shown, S-PmAP-350-137 exhibited 558 mAh g -1 The reversible specific capacity of the composite material is 73% (based on the mass of the composite material, the same below). After 40 cycles, the capacity retention rate is 73% (relative to the reversible specific capacity, the same below). The charge and discharge curves show typical solid-solid conversion characteristics.

[0149] (9) Using the electrode sheet prepared in step (6) as the positive electrode, the metal sodium sheet as the negative electrode, and a polypropylene film (Celgard2325) and a glass fiber membrane as the separator, add an appropriate amount of electrolyte (1 mol L -1 A solution of sodium hexafluorophosphate dissolved in a mixture of ethylene carbonate / diethyl carbonate, i.e. 1M NaPF 6 / EC–DEC) and assembled into CR2025 button cells in an argon-filled glove box.

[0150] (10) The battery prepared in step (9) was charged at 200 mA g in a voltage range of 0.8 to 3.0 V. -1 The charge and discharge cycles were carried out at a current density of . Fig.12 As shown, S-PmAP-350-137 exhibits 510 mAh g -1 The reversible specific capacity is 44% after 30 cycles.

[0151] (11) Using the electrode sheet prepared in step (6) as the positive electrode, the metal potassium sheet as the negative electrode, and a polypropylene film (Celgard2325) and a glass fiber membrane as the separator, add an appropriate amount of electrolyte (1 mol L -1 Potassium hexafluorophosphate dissolved in ethylene carbonate / diethyl carbonate mixture, i.e. 1M KPF 6 / EC–DEC) and assembled into CR2025 button cells in an argon-filled glove box.

[0152] (12) The battery prepared in step (11) was charged at 100 mA g in a voltage range of 1.0 to 3.0 V. -1 The charge and discharge cycles were carried out at a current density of . Fig.13 As shown, S-PmAP-350-137 exhibited 343 mAh g -1 The reversible specific capacity is 53% after 30 cycles.

[0153] Example 6

[0154] The preparation method of the monosulfide-aminophenol polymer composite material provided in this embodiment and its application in a secondary battery include the following steps performed in sequence:

[0155] (1) p-Aminophenol, ammonium persulfate and elemental sulfur were weighed in a molar ratio of 1:3:7, ground and mixed, and placed in a glass tube with one end sealed.

[0156] (2) The glass tube containing the reaction raw materials in step (1) is evacuated to a pressure lower than 0.1 MPa, and the tube is melt-sealed under a butane flame.

[0157] (3) The sealed glass tube containing the reaction raw materials in step (2) is heated to 350° C., and the reaction is carried out at a constant temperature for 10 hours. After cooling, a solid crude product is obtained.

[0158] (4) washing the solid crude product in step (3) with water and ethanol to remove inorganic impurities other than elemental sulfur and low molecular weight organic impurities, and drying at 80°C.

[0159] (5) The product in step (4) was washed with toluene and ethanol to further remove the elemental sulfur contained therein and dried at 80° C. to obtain a sulfur-poly(p-aminophenol) composite material named S-PpAP-350-137. Its X-ray diffraction spectrum is as follows: Fig.14 As shown in a, the infrared spectrum is Fig.14 As shown in b.

[0160] (6) The S-PpAP-350-137 obtained in step (5) is mixed with a conductive agent Ketjen black and a binder polytetrafluoroethylene in a mass ratio of 6:3:1, using a water / isopropyl alcohol mixture as a solvent, into a clay-like state, and rolled on a double-roller to form a film. After drying, the film is cut into small discs of appropriate diameter and pressed onto an aluminum mesh current collector to form an electrode sheet.

[0161] (7) Using the electrode sheet prepared in step (6) as the positive electrode, the metal lithium sheet as the negative electrode, and a polypropylene film (Celgard2325) as the separator, add an appropriate amount of electrolyte (1 mol L -1 A solution of lithium hexafluorophosphate dissolved in a mixture of ethylene carbonate / diethyl carbonate, i.e. 1M LiPF 6 / EC–DEC) and assembled into CR2016 button cells in an argon-filled glove box.

[0162] (8) The battery prepared in step (7) was charged at 100 mA g in a voltage range of 1.0 to 3.0 V. -1 The charge and discharge cycles were carried out at a current density of (based on the mass of the composite material, the same below). The electrochemical performance is as follows Fig.15 As shown, S-PpAP-350-137 exhibited 434 mAh g -1 The reversible specific capacity of the composite material is 81% (based on the mass of the composite material, the same below). After 50 cycles, the capacity retention rate is 81% (relative to the reversible specific capacity, the same below). The charge and discharge curves show typical solid-solid conversion characteristics.

[0163] (9) Using the electrode sheet prepared in step (6) as the positive electrode, the metal sodium sheet as the negative electrode, and a polypropylene film (Celgard2325) and a glass fiber membrane as the separator, add an appropriate amount of electrolyte (1 mol L -1 A solution of sodium hexafluorophosphate dissolved in a mixture of ethylene carbonate / diethyl carbonate, i.e. 1M NaPF 6 / EC–DEC) and assembled into CR2025 button cells in an argon-filled glove box.

[0164] (10) The battery prepared in step (9) was charged at 200 mA g in a voltage range of 0.8 to 3.0 V. -1 The charge and discharge cycles were carried out at a current density of . Fig.16 As shown, S-PpAP-350-137 exhibited 398 mAh g -1 The reversible specific capacity is 70% after 30 cycles.

[0165] (11) Using the electrode sheet prepared in step (6) as the positive electrode, the metal potassium sheet as the negative electrode, and a polypropylene film (Celgard2325) and a glass fiber membrane as the separator, add an appropriate amount of electrolyte (1 mol L -1 Potassium hexafluorophosphate dissolved in ethylene carbonate / diethyl carbonate mixture, i.e. 1M KPF 6 / EC–DEC) and assembled into CR2025 button cells in an argon-filled glove box.

[0166] (12) The battery prepared in step (11) was charged at 100 mA g in a voltage range of 1.0 to 3.0 V. -1 The charge and discharge cycles were carried out at a current density of . Fig.17 As shown, S-PpAP-350-137 exhibited 266 mAh g -1 The reversible specific capacity is 72% after 30 cycles.

[0167] Finally, it should be noted that the terms "comprises," "includes," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article, or apparatus.

[0168] Although the preferred embodiments of the present invention have been described, those skilled in the art may make additional changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention.

[0169] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

Claims

1. A preparation method of a sulfur-aminophenol polymer composite material, characterized in that, the sulfur-aminophenol polymer composite material includes at least one of sulfur-aminophenol polymer composite material A1, sulfur-aminophenol polymer composite material A2, and sulfur-aminophenol polymer composite material B; the method includes: Mixing an aminophenol monomer, an oxidant, and elemental sulfur, and then heating and reacting at 100-600 °C, and cooling to obtain a solid crude product; wherein, the aminophenol monomer is one or a mixture of o-aminophenol, m-aminophenol, and p-aminophenol; Removing inorganic and organic impurities from the solid crude product by dissolution and washing to obtain sulfur-aminophenol polymer composite material A1; Mixing elemental sulfur with an aminophenol polymer and then heating and reacting at 100-600 °C, and cooling to obtain sulfur-aminophenol polymer composite material A2; wherein, the aminophenol polymer is polymerized from one or more of o-aminophenol, m-aminophenol, and p-aminophenol as monomers by chemical oxidation or electrochemical oxidation; Removing the contained elemental sulfur from the sulfur-aminophenol polymer composite material A1 or A2 by heating evaporation / sublimation or dissolution and washing to obtain sulfur-aminophenol polymer composite material B with a reduced or completely removed elemental sulfur content; The molar ratio of the aminophenol monomer, the oxidant, and elemental sulfur is: 1:(1-15):(0-20), and elemental sulfur is not 0; the mass ratio of elemental sulfur to the aminophenol polymer is 10:1-1:3; The oxidant includes at least one of permonosulfuric acid and its salts, sulfur dioxide, sulfur trioxide, concentrated sulfuric acid, and perchlorates, hypochlorites, permanganates, dichromates, chromic acid, concentrated nitric acid, bromine, iodine, peroxides, chloranil, and 2,3-dichloro-5,6-dicyanobenzoquinone; The heating reactions are all carried out at 100-600 °C for 1-4320 minutes; the reaction atmosphere of the heating reactions is selected from vacuum, air, or inert gas.

2. A sulfur-aminophenol polymer composite material prepared by using the preparation method described in claim 1.

3. A derivative or multiple composite material with a sulfur-aminophenol polymer composite material as the main body, characterized in that, the preparation method of the derivative or multiple composite material adopts the preparation method described in claim 1, and an additive is added during the heating reaction or the reaction raw materials are first compounded with the additive and then the heating reaction is carried out. The additive includes at least one of carbon materials, metal compounds, and chalcogen element simple substances; the carbon materials are selected from conductive carbon black, activated carbon, carbon nanotubes, carbon fibers, graphite, graphene, hard carbon, and soft carbon, the metal compounds are selected from carbides, nitrides, oxides, sulfides, phosphides, selenides, tellurides, MXene, and the chalcogen element simple substances are selected from selenium and tellurium.

4. The application of the sulfur-aminophenol polymer composite material described in claim 2 or the derivative or multiple composite material with a sulfur-aminophenol polymer composite material as the main body described in claim 3 in the preparation of a battery positive electrode.

5. A battery positive electrode, characterized in that, The positive electrode is prepared by uniformly mixing and coating or pressing 30% - 99% active material, 1% - 70% conductive agent, and 0% - 40% binder by mass fraction on a current collector. The active material is the sulfur-aminophenol polymer composite material described in claim 2, or a derivative or multiple composite material with the sulfur-aminophenol polymer composite material as the main body described in claim 3.

6. The battery positive electrode according to claim 5, characterized in that the conductive agent includes any one or a mixture of several of graphite, conductive carbon black, carbon nanotubes, carbon fibers, activated carbon, graphene, and fullerenes; the binder includes any one or a mixture of several of polytetrafluoroethylene or its copolymer, polyvinylidene fluoride or its copolymer, polyethylene oxide or its copolymer, polyvinyl alcohol or its copolymer, sodium carboxymethyl cellulose combined with styrene-butadiene rubber, polyether or its copolymer, polyester or its copolymer, polyacrylic acid or polyacrylate.

7. A battery, characterized in that the battery is assembled by directly matching or after pre-lithiation or pre-sodiation or pre-potassiation treatment of the battery positive electrode described in claim 5 or 6 with a battery negative electrode.

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