A method for one-pot in-situ preparation of sulfur-phenylenediamine polymer composite and application thereof

Abstract

The application discloses a one-pot in-situ preparation method of a sulfur-phenylenediamine polymer composite material and application thereof, and the method comprises the following steps: mixing phenylenediamine monomers, an oxidizing agent and elemental sulfur, and then heating and reacting at 100-600 DEG C to obtain a solid crude product; removing inorganic and organic impurities by dissolving and washing the solid crude product to obtain a sulfur-phenylenediamine polymer composite material A; removing the contained elemental sulfur by heating evaporation / sublimation or dissolving and washing the sulfur-phenylenediamine polymer composite material A to obtain a sulfur-phenylenediamine polymer composite material B with reduced or completely removed elemental sulfur. The polymerization of the phenylenediamine monomers and the complexation of sulfur are simultaneously completed by the one-pot in-situ method, so that the preparation process is simplified, the cost is reduced, and the practical application of the material is promoted. The prepared sulfur-phenylenediamine polymer composite material has the advantages of high specific capacity, high coulombic efficiency and good cycle stability as a positive electrode material of a secondary battery.

Description

Technical Field

[0001] This invention relates to the fields of physical chemistry, organic chemistry, polymer science and materials science, and in particular to a method for one-pot in-situ preparation of sulfur-phenylenediamine polymer composite materials and its application. Background Technology

[0002] Lithium-sulfur batteries represent a new generation of electrochemical energy storage systems following lithium-ion batteries, boasting advantages such as abundant resources, low cost, and high energy density. However, the charge-discharge reaction of the sulfur cathode involves a complex solid-liquid-solid transformation process. The intermediate product, lithium polysulfides, is readily soluble in organic electrolytes, leading to active material dissolution and loss, self-discharge, and shuttle behavior, resulting in poor cycle stability and low coulombic efficiency. Furthermore, the low electronic and ionic conductivity of elemental sulfur and the final discharge product, Li₂S, along with their large volume changes during interconversion, also reduce sulfur capacity utilization and exacerbate capacity decay. On the other hand, sodium-sulfur and potassium-sulfur batteries can eliminate dependence on lithium resources, representing more sustainable and lower-cost new battery systems, but they also face similar scientific and technological challenges as lithium-sulfur batteries.

[0003] Using organic polymers as coating layers or host materials for physical or chemical composites with sulfur is one effective approach to solving the aforementioned problems. In terms of physical composites, the literature mainly reports on typical conductive polymers such as polyaniline (PAni), polypyrrole (PPy), and poly(3,4-ethylenedioxythiophene) (PEDOT). Utilizing their electronic conductivity, physical confinement, and chemical adsorption effects, the utilization rate and cycle stability of sulfur can be improved to some extent. However, since the dissolution problem of lithium polysulfides has not been fundamentally solved, the long-term cycle stability of these composites is still difficult to reach practical levels. In terms of chemical composites, a classic material is sulfurized polyacrylonitrile (Adv. Mater., 2002, 14:963). Through high-temperature heating and chemical reaction, sulfur is converted into sulfur as CS... x The -C (x≥2) covalent bonds are attached to the pyrolytic polyacrylonitrile backbone, and the main process during charge-discharge is a solid-solid conversion reaction, which fundamentally eliminates the generation and dissolution of polysulfides, thus achieving excellent long-cycle stability. Currently, there are still various controversies regarding the specific structure of sulfurized polyacrylonitrile, and its sulfur content is relatively low (<50wt%), which reduces the overall energy density of the battery. Due to the rich structure and strong designability of organic polymers, many reaction mechanisms are similar to sulfurized polyacrylonitrile, and sulfur-polymer composites with comparable or even better electrochemical performance are yet to be developed. Furthermore, these composites are generally obtained through a two-step method of first synthesizing the polymer and then reacting it with elemental sulfur in a melt reaction, which is relatively complex and costly.

[0004] Therefore, it is necessary to develop a one-pot in-situ preparation method that simultaneously completes the polymerization of monomers and the composite of sulfur to obtain sulfur-polymer composite cathode materials with low cost, high specific capacity, high coulombic efficiency, and good cycle stability. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing a sulfur-phenylenediamine polymer composite material. This method uses a one-pot in-situ method to simultaneously complete the polymerization of phenylenediamine monomers and the compounding of sulfur, which will significantly simplify the preparation process and reduce costs, thus promoting the practical application of this material. The sulfur-phenylenediamine polymer composite material prepared has advantages such as high specific capacity, high coulombic efficiency, and good cycle stability as a positive electrode material for secondary batteries.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] In a first aspect of the present invention, a method for one-pot in-situ preparation of a sulfur-phenylenediamine polymer composite material is provided, wherein the sulfur-phenylenediamine polymer composite material comprises sulfur-phenylenediamine polymer composite material A and sulfur-phenylenediamine polymer composite material B; the method includes:

[0008] The phenylenediamine monomer, oxidant, and elemental sulfur are homogenized and then heated to react at 100–600°C. After cooling, a solid crude product is obtained. The phenylenediamine monomer is one or a mixture of o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine.

[0009] The solid crude product was dissolved and washed to remove inorganic and organic impurities, yielding sulfur-phenylenediamine polymer composite material A.

[0010] The sulfur-phenylenediamine polymer composite material A is removed by heating and evaporation / sublimation or by dissolution and washing to obtain sulfur-phenylenediamine polymer composite material B with reduced or completely removed elemental sulfur content.

[0011] Furthermore, the molar ratio of the phenylenediamine monomer, oxidant, and elemental sulfur is 1:(1-15):(0-20).

[0012] Furthermore, the oxidant includes at least one of persulfate and its salts, persulfate and its salts, sulfur dioxide, sulfur trioxide, concentrated sulfuric acid, and ferric salts, perchlorates, hypochlorites, permanganates, dichromates, chromic acid, concentrated nitric acid, bromine, iodine, peroxides, chloroquinone, and 2,3-dichloro-5,6-dicyanobenzoquinone.

[0013] Furthermore, the heating reaction is carried out at a reaction temperature of 100–600°C for 1–4320 minutes; the reaction atmosphere of the heating reaction is selected from vacuum, air, nitrogen, or an inert gas.

[0014] In a second aspect of the invention, a sulfur-phenylenediamine polymer composite material prepared by the method is provided.

[0015] In a third aspect of the invention, a derivative or multiple complex based on a sulfur-phenylenediamine polymer composite material is provided, wherein the derivative or multiple complex based on the sulfur-phenylenediamine polymer composite material includes a derivative or multiple complex based on sulfur-phenylenediamine polymer composite material A and a derivative or multiple complex based on sulfur-phenylenediamine polymer composite material B.

[0016] The method for preparing the derivative or multiple complex based on the sulfur-phenylenediamine polymer composite material involves adding an additive during the heating reaction or first compounding the reaction raw materials with the additive before carrying out the heating reaction. The additive includes at least one of carbon materials, metal compounds, and chalcogen elements. The carbon materials are selected from conductive carbon black, activated carbon, carbon nanotubes, carbon fibers, graphite, graphene, hard carbon, soft carbon, and porous carbon. The metal compounds are selected from carbides, nitrides, oxides, sulfides, phosphides, selenides, tellurides, and MXene. The chalcogen elements are selected from selenium and tellurium.

[0017] In a fourth aspect of the invention, the application of the aforementioned sulfur-phenylenediamine polymer composite material or its derivatives or multiple composites based on the sulfur-phenylenediamine polymer composite material in the preparation of a battery cathode is provided.

[0018] In a fifth aspect of the invention, a battery positive electrode is provided, wherein the positive electrode is prepared by uniformly coating or pressing 30% to 99% active material, 1% to 70% conductive agent and 0% to 40% binder, by mass fraction, onto a current collector, wherein the active material is the sulfur-phenylenediamine polymer composite material or a derivative or multiple composite material based on the sulfur-phenylenediamine polymer composite material.

[0019] In a sixth aspect of the invention, a battery is provided, wherein the battery is assembled by directly or after pre-lithiation / sodium / potassium treatment with a battery negative electrode.

[0020] One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:

[0021] (1) The monomers such as o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine used in this invention are readily available and inexpensive.

[0022] (2) The one-pot in-situ preparation method of sulfur-phenylenediamine polymer composite material provided by the present invention is to synthesize phenylenediamine monomer, oxidant and elemental sulfur by heating reaction in one step without the need to add additional reaction solvent. It has the advantages of simple process, low cost, environmental friendliness and easy large-scale production.

[0023] (3) The one-pot in-situ preparation method of sulfur-phenylenediamine polymer composite material provided by the present invention can adjust the sulfur content and the content of elemental sulfur by controlling the feeding ratio of phenylenediamine monomer, oxidant, elemental sulfur and whether to further remove elemental sulfur (to obtain composite materials A and B respectively), so as to achieve a balance between energy density and cycle stability.

[0024] (4) The structure of the thio-phenylenediamine polymer composite material prepared according to the method of the present invention is very favorable for realizing the solid-solid conversion reaction: the conjugated polymer skeleton is conducive to electron conduction, and the abundant benzene ring units are conducive to the generation of CS. x -C (x≥2) covalent bonds, and abundant polar C=N bonds not only have adsorption and catalytic effects on sulfur species, but also contribute additional capacity.

[0025] (5) The sulfur-phenylenediamine polymer composite material prepared according to the method of the present invention has the advantages of high specific capacity, high coulombic efficiency and good cycle stability as a positive electrode material for secondary batteries.

[0026] (6) The sulfur-phenylenediamine polymer composite material prepared according to the method of the present invention can be applied to various alkali metal batteries such as lithium, sodium, and potassium, and can also be applied to corresponding ion batteries by pre-lithiation of positive or negative electrodes. Attached Figure Description

[0027] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are the result data of some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0028] Figure 1 (a) X-ray diffraction pattern and (b) infrared spectrum of S-PoPDA-400-130;

[0029] Figure 2 (a) Cyclic performance and (b) corresponding charge-discharge curves of S-PoPDA-400-130 in lithium secondary batteries using ester electrolyte;

[0030] Figure 3 (a) X-ray diffraction pattern, (b) thermogravimetric curve, (c) infrared spectrum and (d) scanning electron microscope image of S-PoPDA-350-137;

[0031] Figure 4 (a) Cycle performance and (b) corresponding charge-discharge curves for S-PoPDA-350-137 in lithium secondary batteries using ester electrolytes; (c) Rate performance and (d) corresponding charge-discharge curves.

[0032] Figure 5 (a) Cyclic performance and (b) corresponding charge-discharge curves of S-PoPDA-350-137 in a sodium secondary battery using an ester electrolyte;

[0033] Figure 6 (a) Cyclic performance and (b) corresponding charge-discharge curves of S-PoPDA-350-137 in a potassium secondary battery using an ester electrolyte;

[0034] Figure 7 (a) X-ray diffraction pattern and (b) infrared spectrum of S-PoPDA-350-1320B;

[0035] Figure 8 (a) Cyclic performance and (b) corresponding charge-discharge curves of S-PoPDA-350-1320B in a lithium secondary battery using an ester electrolyte;

[0036] Figure 9 (a) X-ray diffraction pattern and (b) infrared spectrum of S-PoPDA-350-1320A;

[0037] Figure 10 (a) Cyclic performance and (b) corresponding charge-discharge curves of S-PoPDA-350-1320A in a lithium secondary battery using an ether electrolyte;

[0038] Figure 11 (a) X-ray diffraction pattern and (b) infrared spectrum of S-PmPDA-350-137;

[0039] Figure 12 (a) Cyclic performance and (b) corresponding charge-discharge curves of S-PmPDA-350-137 in lithium secondary batteries using ester electrolyte;

[0040] Figure 13 (a) Cyclic performance and (b) corresponding charge-discharge curves of S-PmPDA-350-137 in a sodium secondary battery using an ester electrolyte;

[0041] Figure 14 (a) Cyclic performance and (b) corresponding charge-discharge curves of S-PmPDA-350-137 in a potassium secondary battery using an ester electrolyte;

[0042] Figure 15 (a) X-ray diffraction pattern and (b) infrared spectrum of S-PpPDA-350-137;

[0043] Figure 16 (a) Cyclic performance and (b) corresponding charge-discharge curves of S-PpPDA-350-137 in lithium secondary batteries using ester electrolyte;

[0044] Figure 17 (a) Cyclic performance and (b) corresponding charge-discharge curves of S-PpPDA-350-137 in a sodium secondary battery using an ester electrolyte;

[0045] Figure 18 (a) Cyclic performance and (b) corresponding charge-discharge curves of S-PpPDA-350-137 in a potassium secondary battery using an ester electrolyte. Detailed Implementation

[0046] The present invention will be described in detail below with reference to specific embodiments and examples, thereby making the advantages and various effects of the present invention more clearly apparent. Those skilled in the art should understand that these specific embodiments and examples are for illustrative purposes only and are not intended to limit the present invention.

[0047] Throughout this specification, unless otherwise specified, the terminology used herein should be understood as having the meaning commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In the event of any conflict, this specification shall prevail.

[0048] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be obtained by purchasing them from the market or by existing methods.

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

[0050] Step S101: The phenylenediamine monomer, oxidant and elemental sulfur are mixed and heated to react at 100-600°C. After cooling, a solid crude product is obtained. The phenylenediamine monomer is one or more of o-phenylenediamine, m-phenylenediamine and p-phenylenediamine.

[0051] In step S101,

[0052] The oxidant is at least one of persulfate and its salts, persulfate and its salts, sulfur dioxide, sulfur trioxide, concentrated sulfuric acid, and ferric salts, perchlorates, hypochlorites, permanganates, dichromates, chromic acid, concentrated nitric acid, bromine, iodine, peroxides, chloroquinone, and 2,3-dichloro-5,6-dicyanobenzoquinone.

[0053] The molar ratio of the phenylenediamine monomer, oxidant, and elemental sulfur is 1:(1-15):(0-20).

[0054] When the oxidant is a sulfur-containing oxidant and can provide enough sulfur to recombine with the phenylenediamine polymer, there is no need to add additional elemental sulfur.

[0055] The preferred molar ratio of phenylenediamine monomer to oxidant is 1:(2-12). This molar ratio range is beneficial for obtaining phenylenediamine polymers with high degree of polymerization and yield. If too little oxidant is added, it will have the adverse effect of reducing the degree of polymerization and yield. If too much oxidant is added, it will have the adverse effect of wasting raw materials and increasing costs.

[0056] The mixing methods include stacking, stirring, grinding, ball milling, sand milling, solid-gas (sulfur dioxide, sulfur trioxide) mixing, or solid-liquid (liquid oxidant, elemental sulfur solution) mixing.

[0057] The reaction vessel used for the heating reaction is in a sealed or semi-sealed state, with or without vibration or rotation, and the reactants are with or without stirring.

[0058] The reaction atmosphere for the heating reaction is a vacuum, air, nitrogen, or an inert gas.

[0059] The heating method is furnace heating, oil / sand bath heating, or microwave heating.

[0060] The heating reaction is carried out at a temperature of 100–600°C for a duration of 1–4320 minutes. The heating program consists of a constant or varying temperature and time within this range. The preferred reaction temperature is 200–550°C, and the preferred reaction time is 60–1440 minutes.

[0061] Step S102: Remove inorganic and organic impurities from the solid crude product by dissolution and washing to obtain sulfur-phenylenediamine polymer composite material A.

[0062] In step S102

[0063] For methods of removing inorganic impurities other than elemental sulfur and low molecular weight organic impurities by dissolving and washing solid crude products, the washing liquid includes, but is not limited to, one or more of the following: 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, aqueous solution of sodium hydroxide, aqueous solution of potassium hydroxide, and aqueous solution of potassium iodide.

[0064] Step S103: Remove the elemental sulfur contained in the sulfur-phenylenediamine polymer composite material A by heating and evaporating / sublimating or dissolving and washing, to obtain sulfur-phenylenediamine polymer composite material B with reduced or completely removed elemental sulfur content.

[0065] In step S103

[0066] For the method of removing elemental sulfur from composite materials 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 an inert gas. Preferably, the heating temperature is 200–400°C, the heating time is 30–720 minutes, and the heating atmosphere is preferably vacuum or nitrogen.

[0067] For methods of dissolving and washing to remove elemental sulfur contained in composite materials, the washing liquid includes, but is not limited to, non-polar solvents such as benzene, toluene, carbon tetrachloride, and carbon disulfide, as well as hot alkaline solutions such as lithium hydroxide, sodium hydroxide, and potassium hydroxide.

[0068] The sulfur-phenylenediamine polymer composite material B obtained in step S102 has a significantly lower elemental sulfur content, even to zero. This will reduce the specific capacity but will help improve coulombic efficiency and cycle stability.

[0069] As an optional implementation, an additive is added to the heating reaction in step S101, or the reactants are first compounded with the additive before the heating reaction is carried out. Other preparation processes are the same as in steps S101 to S103, and a derivative or multiple complex based on a sulfur-phenylenediamine polymer composite material is obtained.

[0070] Additives are added to modify / improve the physicochemical properties (such as electronic conductivity) of the composite material. The additives include at least one of carbon materials, metal compounds, and chalcogen elements. The carbon materials are selected from conductive carbon black, activated carbon, carbon nanotubes, carbon fibers, graphite, graphene, hard carbon, soft carbon, and porous carbon. The metal compounds are selected from carbides, nitrides, oxides, sulfides, phosphides, selenides, tellurides, and MXene. The chalcogen elements are selected from selenium and tellurium.

[0071] The present invention also provides the application of the sulfur-phenylenediamine polymer composite material or its derivatives or multiple composites based on the sulfur-phenylenediamine polymer composite material in secondary alkali metal (lithium, sodium, potassium) batteries and alkali metal ion batteries, as well as the preparation methods of the corresponding positive electrode and battery.

[0072] According to another typical embodiment of the present invention, a battery positive electrode is provided, and the preparation method is as follows:

[0073] Step S201: Disperse and mix the active material, conductive agent, and binder in a solvent in a certain proportion, or dry mixing without solvent can be used; the active material is the sulfur-phenylenediamine polymer composite material or a derivative or multiple composite material based on the sulfur-phenylenediamine polymer composite material; 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%.

[0074] In step S201

[0075] The conductive agent is any one or a mixture of several of the following: 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.

[0076] The binder is any one or a mixture of several of the following: polytetrafluoroethylene or its copolymers, polyvinylidene fluoride or its copolymers, polyethylene oxide or its copolymers, polyvinyl alcohol or its copolymers, sodium carboxymethyl cellulose combined with styrene-butadiene rubber or its copolymers, polyether or its copolymers, polyester or its copolymers, and polyacrylic acid or polyacrylate. The binder is preferably polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, sodium polyacrylate, or lithium polyacrylate.

[0077] The solvent is any one or a mixture of several of the following: 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.

[0078] Step S202: Coat the mixture onto the current collector or roll it onto the current collector, and dry it to form an electrode. If dry mixing is used, drying is not required.

[0079] In step S202

[0080] 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 foamed metal. The current collector is preferably aluminum mesh or aluminum foil.

[0081] The drying temperature is a constant or varying temperature between 20 and 200°C, and the drying atmosphere is any one of vacuum, air, nitrogen, argon, and helium.

[0082] According to another typical embodiment of the present invention, a battery is provided, wherein the battery is assembled by directly or after pre-lithiation / sodium / potassium treatment with a negative electrode. The corresponding battery preparation method is as follows:

[0083] Method 1: Match the positive electrode of the battery with a lithium / sodium / potassium metal negative electrode or an alloy negative electrode containing lithium / sodium / potassium, separate the two electrodes with a membrane, add electrolyte, and assemble the battery in an inert atmosphere.

[0084] The separator is a composite separator composed of any one or more of polyethylene, polypropylene, polytetrafluoroethylene or copolymers thereof, polyimide, cellulose and glass fiber separators, as well as modified separators based on these separators. The separator is preferably a polypropylene separator or a glass fiber separator.

[0085] The electrolyte is a solution prepared by dissolving the corresponding metal (lithium, sodium, potassium) salt in a solvent, with a salt concentration of 0.1–5.0 mol / L. –1 The salt is any one or a mixture of several of the following: perchlorate, hexafluorophosphate, tetrafluoroborate, trifluoromethanesulfonate, bis(oxalate)borate, difluorooxalateborate, bis(fluorosulfonyl)imide salt, and bis(trifluoromethanesulfonyl)imide salt. The solvent is any one or a mixture of several of the following: ethylene carbonate, vinylene carbonate, fluoroethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl 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, sulfolane, dimethyl sulfoxide, and γ-butyrolactone.

[0086] The inert atmosphere is any one or a mixture of nitrogen, argon, and helium. Argon is preferred.

[0087] Method 2: Assemble the battery by matching the positive electrode with negative electrodes such as graphite, silicon, carbon / silicon, hard carbon, and soft carbon. However, the positive or negative electrode needs to undergo chemical or electrochemical pre-lithiation / sodium / potassium treatment, changing one of them from an oxidized state without lithium / sodium / potassium to a reduced state with lithium / sodium / potassium intercalation. Pre-lithiation / sodium / potassium treatment methods include chemical methods involving contacting the electrode with lithium / sodium / potassium metals or organometallic reagents to induce a redox reaction, and electrochemical methods involving pre-discharging the electrode in an electrochemical device. Other preparation processes are the same as in Method 1.

[0088] The chemically pre-lithiated / sodium / potassium-modified organometallic reagent is a solution of aromatic hydrocarbons such as biphenyl, naphthalene, etc., in which lithium, sodium, and potassium have been dissolved.

[0089] The electrolyte and negative electrode used in the electrochemical pre-lithiation / sodium / potassium-ionization device are the same as those in Method 1, and the atmosphere is any one or a mixture of nitrogen, argon and helium.

[0090] The sulfur-phenylenediamine polymer composite material or its derivatives or multiple composites based on the sulfur-phenylenediamine polymer composite material can also be applied to 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, as well as semi-solid-state and quasi-solid-state batteries that partially use liquid electrolytes.

[0091] The following will describe in detail a method for one-pot in-situ preparation of sulfur-phenylenediamine polymer composite materials and its application, in conjunction with examples, comparative examples and experimental data.

[0092] The monomers used in this invention [o-phenylenediamine (oPDA), m-phenylenediamine (mPDA), and p-phenylenediamine (pPDA)] are all commercially available and require no further purification. The oxidants used are mostly commercially available or easily prepared (such as sulfur dioxide and sulfur trioxide, which can be gases generated during the oxidative roasting of metal sulfides such as zinc sulfide and nickel sulfide).

[0093] Example 1

[0094] This embodiment provides a method for one-pot in-situ preparation of sulfur-phenylenediamine polymer composite materials and their application in secondary batteries, comprising the following steps performed sequentially:

[0095] (1) Weigh o-phenylenediamine and ammonium persulfate in a molar ratio of 1:3, grind and mix them and place them in a glass tube with one end closed.

[0096] (2) Evacuate the glass tube containing the reaction raw materials in step (1) until the pressure is below 0.1 MPa, and melt and seal the tube under a butane flame.

[0097] (3) Heat the sealed glass tube containing the reaction raw materials in step (2) to 400°C, keep it at a constant temperature for 10 hours, and then cool it to obtain a solid crude product.

[0098] (4) Wash the solid crude product from step (3) with water and ethanol to remove inorganic impurities other than elemental sulfur and low molecular weight organic impurities, and dry it at 80°C.

[0099] (5) The product from step (4) was washed with toluene and ethanol to further remove the elemental sulfur and dried at 80°C to obtain a sulfur-poly(o-phenylenediamine) composite material, named S-PoPDA-400-130. Its X-ray diffraction pattern is as follows: Figure 1 As shown in a, the infrared spectrum is as follows: Figure 1 As shown in b.

[0100] (6) The S-PoPDA-400-130 obtained in step (5) is mixed with the conductive agent Ketjen black and the binder polytetrafluoroethylene in a mass ratio of 6:3:1, with water / isopropanol mixture as solvent, to form a clay-like substance. The mixture is then rolled into a film on a roller press, dried, cut into small round pieces of appropriate diameter, and pressed onto an aluminum mesh current collector to form an electrode sheet.

[0101] (7) Using the electrode sheet prepared in step (6) as the positive electrode, the lithium metal sheet as the negative electrode, and the polypropylene membrane (Celgard 2325) as the separator, add an appropriate amount of electrolyte (1 mol L). -1 Lithium hexafluorophosphate was dissolved in a solution of ethylene carbonate / diethyl carbonate (i.e., 1M LiPF6 / EC–DEC) and assembled into CR2016 coin cells in an argon-filled glove box.

[0102] (8) The battery obtained in step (7) is subjected to a voltage range of 1.0 to 3.0V at 100mA g. -1 Charge-discharge cycles were performed using a current density (based on the mass of the composite material). Electrochemical performance was as follows: Figure 2 As shown, S-PoPDA-400-130 exhibits a capacity of 444 mAh g. -1 The reversible specific capacity (based on the quality of the composite material) retains 70% of its capacity after 200 cycles (relative to the reversible specific capacity), and the charge-discharge curves exhibit typical solid-solid conversion characteristics.

[0103] Example 2

[0104] This embodiment provides a method for one-pot in-situ preparation of sulfur-phenylenediamine polymer composite materials and their application in secondary batteries, comprising the following steps performed sequentially:

[0105] (1) Weigh o-phenylenediamine, ammonium persulfate and elemental sulfur in a molar ratio of 1:3:7, grind and mix them and place them in a glass tube with one end closed.

[0106] (2) Evacuate the glass tube containing the reaction raw materials in step (1) until the pressure is below 0.1 MPa, and melt and seal the tube under a butane flame.

[0107] (3) Heat the sealed glass tube containing the reaction raw materials in step (2) to 350°C, keep it at a constant temperature for 10 hours, and then cool it to obtain a solid crude product.

[0108] (4) Wash the solid crude product from step (3) with water and ethanol to remove inorganic impurities other than elemental sulfur and low molecular weight organic impurities, and dry it at 80°C.

[0109] (5) The product from step (4) was washed with toluene and ethanol to further remove the elemental sulfur, and then dried at 80°C to obtain a sulfur-poly(o-phenylenediamine) composite material, named S-PoPDA-350-137. Its X-ray diffraction pattern is as follows: Figure 3 As shown in figure a, the thermogravimetric curve is as follows: Figure 3 As shown in b, the infrared spectrum is as follows: Figure 3 As shown in c, the microstructure is as follows Figure 3 As shown in d.

[0110] (6) The S-PoPDA-350-137 obtained in step (5) is mixed with the conductive agent Ketjen black and the binder polytetrafluoroethylene in a mass ratio of 6:3:1, with water / isopropanol mixture as solvent, to form a clay-like substance. The mixture is then rolled into a film on a roller press, dried, cut into small round pieces of appropriate diameter, and pressed onto an aluminum mesh current collector to form an electrode sheet.

[0111] (7) Using the electrode sheet prepared in step (6) as the positive electrode, the lithium metal sheet as the negative electrode, and the polypropylene membrane (Celgard 2325) as the separator, add an appropriate amount of electrolyte (1 mol L). -1 Lithium hexafluorophosphate was dissolved in a solution of ethylene carbonate / diethyl carbonate (i.e., 1M LiPF6 / EC–DEC) and assembled into CR2016 coin cells in an argon-filled glove box.

[0112] (8) The battery obtained in step (7) is subjected to a voltage range of 1.0 to 3.0V at 100mA g. -1 Charge-discharge cycles were performed at a current density (based on the mass of the composite material, the same below). Electrochemical performance is as follows: Figure 4 As shown, S-PoPDA-350-137 exhibits a capacity of 528 mAh g. -1 The reversible specific capacity (based on the mass of the composite material, the same below) was 79% after 100 cycles (relative to the reversible specific capacity, the same below), and at 2000 mA g -1 It still has 315mAh g at current density -1Its reversible specific capacity and charge-discharge curve exhibit typical solid-solid conversion characteristics.

[0113] (9) Using the electrode sheet prepared in step (6) as the positive electrode, the sodium metal sheet as the negative electrode, and a combination of polypropylene membrane (Celgard 2325) and glass fiber membrane as the diaphragm, add an appropriate amount of electrolyte (1 mol L) dropwise. -1 Sodium hexafluorophosphate was dissolved in a solution of ethylene carbonate / diethyl carbonate (i.e., 1M NaPF6 / EC–DEC) and assembled into CR2025 coin cells in an argon-filled glove box.

[0114] (10) The battery obtained in step (9) is subjected to a voltage range of 0.8 to 3.0V at 100mA g. -1 The current density was used for charge-discharge cycles. Electrochemical performance was as follows: Figure 5 As shown, S-PoPDA-350-137 exhibits a capacity of 432 mAh g in sodium batteries. -1 The reversible specific capacity has a capacity retention rate of 86% after 30 cycles.

[0115] (11) Using the electrode sheet prepared in step (6) as the positive electrode, the potassium metal sheet as the negative electrode, and a combination of polypropylene membrane (Celgard 2325) and glass fiber membrane as the diaphragm, add an appropriate amount of electrolyte (1 mol L) dropwise. -1 Potassium hexafluorophosphate was dissolved in a solution of ethylene carbonate / diethyl carbonate (i.e., 1M KPF6 / EC–DEC) and assembled into CR2025 button cells in an argon-filled glove box.

[0116] (12) The battery obtained in step (11) is subjected to a voltage range of 1.0 to 3.0V at 100mA g. -1 The current density was used for charge-discharge cycles. Electrochemical performance was as follows: Figure 6 As shown, S-PoPDA-350-137 exhibits a capacity of 302 mAh g in potassium batteries. -1 The reversible specific capacity has a capacity retention rate of 65% after 30 cycles.

[0117] Example 3

[0118] This embodiment provides a method for one-pot in-situ preparation of sulfur-phenylenediamine polymer composite materials and their application in secondary batteries, comprising the following steps performed sequentially:

[0119] (1) Weigh o-phenylenediamine, ammonium persulfate and elemental sulfur in a molar ratio of 1:3:20, grind and mix them and place them in a stainless steel reactor. The reactor is in a semi-sealed state (the threaded lid is tightened, but gas can still escape).

[0120] (2) Place the stainless steel reactor containing the reaction raw materials in step (1) into a tube furnace with nitrogen gas flowing through one end, and pass sodium hydroxide aqueous solution through the other end of the tube furnace for tail gas treatment.

[0121] (3) Heat the tube furnace to 350°C and react at a constant temperature for 10 hours. After cooling, a solid crude product is obtained.

[0122] (4) Wash the solid crude product from step (3) with water and ethanol to remove inorganic impurities other than elemental sulfur and low molecular weight organic impurities, and dry it at 80°C.

[0123] (5) The product from step (4) was washed with toluene and ethanol to further remove the elemental sulfur, and then dried at 80°C to obtain a sulfur-poly(o-phenylenediamine) composite material, named S-PoPDA-350-1320B. Its X-ray diffraction pattern is as follows: Figure 7 As shown in a, the infrared spectrum is as follows: Figure 7 As shown in b.

[0124] (6) The S-PoPDA-350-1320B obtained in step (5) is mixed with the conductive agent Ketjen black and the binder polytetrafluoroethylene in a mass ratio of 6:3:1, with water / isopropanol mixture as solvent, to form a clay-like substance. The mixture is then rolled into a film on a roller press, dried, cut into small round pieces of appropriate diameter, and pressed onto an aluminum mesh current collector to form an electrode sheet.

[0125] (7) Using the electrode sheet prepared in step (6) as the positive electrode, the lithium metal sheet as the negative electrode, and the polypropylene membrane (Celgard 2325) as the separator, add an appropriate amount of electrolyte (1 mol L). -1 Lithium hexafluorophosphate was dissolved in a solution of ethylene carbonate / diethyl carbonate (i.e., 1M LiPF6 / EC–DEC) and assembled into CR2016 coin cells in an argon-filled glove box.

[0126] (8) The battery obtained in step (7) is subjected to a voltage range of 1.0 to 3.0V at 100mA g. -1 Charge-discharge cycles were performed using a current density (based on the mass of the composite material). Electrochemical performance was as follows: Figure 8 As shown, S-PoPDA-350-1320B exhibits a capacity of 463 mAh g. -1 The reversible specific capacity (based on the quality of the composite material) retains 80% of its capacity after 100 cycles (relative to the reversible specific capacity), and the charge-discharge curves exhibit typical solid-solid conversion characteristics.

[0127] Example 4

[0128] This embodiment provides a method for one-pot in-situ preparation of sulfur-phenylenediamine polymer composite materials and their application in secondary batteries, comprising the following steps performed sequentially:

[0129] (1) Weigh o-phenylenediamine, ammonium persulfate and elemental sulfur in a molar ratio of 1:3:20, grind and mix them and place them in a glass tube with one end closed.

[0130] (2) Evacuate the glass tube containing the reaction raw materials in step (1) until the pressure is below 0.1 MPa, and melt and seal the tube under a butane flame.

[0131] (3) Heat the sealed glass tube containing the reaction raw materials in step (2) to 350°C, keep it at a constant temperature for 10 hours, and then cool it to obtain a solid crude product.

[0132] (4) The solid crude product from step (3) was washed with water and ethanol to remove inorganic impurities other than elemental sulfur and low molecular weight organic impurities, and then dried at 80°C to obtain a sulfur-poly(o-phenylenediamine) composite material, named S-PoPDA-350-1320A. Its X-ray diffraction pattern is as follows: Figure 9 As shown in a, the infrared spectrum is as follows: Figure 9 As shown in b.

[0133] (5) The S-PoPDA-350-1320A obtained in step (4) is mixed with conductive agent Ketjen black and binder polytetrafluoroethylene in a mass ratio of 6:3:1, with water / isopropanol mixture as solvent, to form a clay-like substance. The mixture is then rolled into a film on a roller press, dried, cut into small round pieces of appropriate diameter, and pressed onto an aluminum mesh current collector to form an electrode sheet.

[0134] (6) Using the electrode sheet obtained in step (5) as the positive electrode, the lithium metal sheet as the negative electrode, and the polypropylene membrane (Celgard 2325) as the separator, add an appropriate amount of electrolyte [1 mol L]. -1 Lithium bis(trifluoromethanesulfonyl)imide was dissolved in a solution of a mixture of 1,3-dioxolane / ethylene glycol dimethyl ether, i.e., 1M LiTFSI / DOL-DME], and assembled into a CR2016 coin cell in an argon-filled glove box.

[0135] (7) The battery obtained in step (6) is subjected to a voltage range of 1.5 to 3.5V at 1000mA g. -1 Charge-discharge cycles were performed using a current density (based on the mass of the composite material). Electrochemical performance was as follows: Figure 10 As shown, the S-PoPDA-350-1320A exhibits a capacity of 770 mAh g. -1 The reversible specific capacity (based on the quality of the composite material) retains 71% of its capacity after 50 cycles (relative to the reversible specific capacity), and its charge-discharge curve exhibits typical solid-liquid-solid transformation characteristics.

[0136] Example 5

[0137] This embodiment provides a method for one-pot in-situ preparation of sulfur-phenylenediamine polymer composite materials and their application in secondary batteries, comprising the following steps performed sequentially:

[0138] (1) Weigh out m-phenylenediamine, ammonium persulfate and elemental sulfur in a molar ratio of 1:3:7, grind and mix them and place them in a glass tube with one end closed.

[0139] (2) Evacuate the glass tube containing the reaction raw materials in step (1) until the pressure is below 0.1 MPa, and melt and seal the tube under a butane flame.

[0140] (3) Heat the sealed glass tube containing the reaction raw materials in step (2) to 350°C, keep it at a constant temperature for 10 hours, and then cool it to obtain a solid crude product.

[0141] (4) Wash the solid crude product from step (3) with water and ethanol to remove inorganic impurities other than elemental sulfur and low molecular weight organic impurities, and dry it at 80°C.

[0142] (5) The product from step (4) was washed with toluene and ethanol to further remove the elemental sulfur, and then dried at 80°C to obtain a sulfur-poly(m-phenylene diamine) composite material, named S-PmPDA-350-137. Its X-ray diffraction pattern is as follows: Figure 11 As shown in a, the infrared spectrum is as follows: Figure 11 As shown in b.

[0143] (6) The S-PmPDA-350-137 obtained in step (5) is mixed with the conductive agent Ketjen black and the binder polytetrafluoroethylene in a mass ratio of 6:3:1, with water / isopropanol mixture as solvent, to form a clay-like substance. The mixture is then rolled into a film on a roller press, dried, cut into small round pieces of appropriate diameter, and pressed onto an aluminum mesh current collector to form an electrode sheet.

[0144] (7) Using the electrode sheet prepared in step (6) as the positive electrode, the lithium metal sheet as the negative electrode, and the polypropylene membrane (Celgard 2325) as the separator, add an appropriate amount of electrolyte (1 mol L). -1 Lithium hexafluorophosphate was dissolved in a solution of ethylene carbonate / diethyl carbonate (i.e., 1M LiPF6 / EC–DEC) and assembled into CR2016 coin cells in an argon-filled glove box.

[0145] (8) The battery obtained in step (7) is subjected to a voltage range of 1.0 to 3.0V at 100mA g. -1 Charge-discharge cycles were performed at a current density (based on the mass of the composite material, the same below). Electrochemical performance is as follows: Figure 12As shown, S-PmPDA-350-137 exhibits a capacity of 584 mAh g. -1 The reversible specific capacity (based on the quality of the composite material, the same below) was 79% after 50 cycles (relative to the reversible specific capacity, the same below), and the charge-discharge curve showed typical solid-solid conversion characteristics.

[0146] (9) Using the electrode sheet prepared in step (6) as the positive electrode, the sodium metal sheet as the negative electrode, and a combination of polypropylene membrane (Celgard 2325) and glass fiber membrane as the diaphragm, add an appropriate amount of electrolyte (1 mol L) dropwise. -1 Sodium hexafluorophosphate was dissolved in a solution of ethylene carbonate / diethyl carbonate (i.e., 1M NaPF6 / EC–DEC) and assembled into CR2025 coin cells in an argon-filled glove box.

[0147] (10) The battery obtained in step (9) is subjected to a voltage range of 0.8 to 3.0V at 200mA g. -1 The current density was used for charge-discharge cycles. Electrochemical performance was as follows: Figure 13 As shown, S-PmPDA-350-137 exhibits a capacity of 545 mAh g in sodium batteries. -1 The reversible specific capacity has a capacity retention rate of 56% after 30 cycles.

[0148] (11) Using the electrode sheet prepared in step (6) as the positive electrode, the potassium metal sheet as the negative electrode, and a combination of polypropylene membrane (Celgard 2325) and glass fiber membrane as the diaphragm, add an appropriate amount of electrolyte (1 mol L) dropwise. -1 Potassium hexafluorophosphate was dissolved in a solution of ethylene carbonate / diethyl carbonate (i.e., 1M KPF6 / EC–DEC) and assembled into CR2025 button cells in an argon-filled glove box.

[0149] (12) The battery obtained in step (11) is subjected to a voltage range of 1.0 to 3.0V at 100mA g. -1 The current density was used for charge-discharge cycles. Electrochemical performance was as follows: Figure 14 As shown, S-PmPDA-350-137 exhibits a capacity of 288 mAh g in potassium batteries. -1 The reversible specific capacity has a capacity retention rate of 65% after 30 cycles.

[0150] Example 6

[0151] This embodiment provides a method for one-pot in-situ preparation of sulfur-phenylenediamine polymer composite materials and their application in secondary batteries, comprising the following steps performed sequentially:

[0152] (1) Weigh p-phenylenediamine, ammonium persulfate and elemental sulfur in a molar ratio of 1:3:7, grind and mix them and place them in a glass tube with one end closed.

[0153] (2) Evacuate the glass tube containing the reaction raw materials in step (1) until the pressure is below 0.1 MPa, and melt and seal the tube under a butane flame.

[0154] (3) Heat the sealed glass tube containing the reaction raw materials in step (2) to 350°C, keep it at a constant temperature for 10 hours, and then cool it to obtain a solid crude product.

[0155] (4) Wash the solid crude product from step (3) with water and ethanol to remove inorganic impurities other than elemental sulfur and low molecular weight organic impurities, and dry it at 80°C.

[0156] (5) The product from step (4) was washed with toluene and ethanol to further remove the elemental sulfur, and then dried at 80°C to obtain a sulfur-poly(p-phenylene diamine) composite material, named S-PpPDA-350-137. Its X-ray diffraction pattern is as follows: Figure 15 As shown in a, the infrared spectrum is as follows: Figure 15 As shown in b.

[0157] (6) The S-PpPDA-350-137 obtained in step (5) is mixed with the conductive agent Ketjen black and the binder polytetrafluoroethylene in a mass ratio of 6:3:1, with water / isopropanol mixture as solvent, to form a clay-like substance. The mixture is then rolled into a film on a roller press, dried, cut into small round pieces of appropriate diameter, and pressed onto an aluminum mesh current collector to form an electrode sheet.

[0158] (7) Using the electrode sheet prepared in step (6) as the positive electrode, the lithium metal sheet as the negative electrode, and the polypropylene membrane (Celgard 2325) as the separator, add an appropriate amount of electrolyte (1 mol L). -1 Lithium hexafluorophosphate was dissolved in a solution of ethylene carbonate / diethyl carbonate (i.e., 1M LiPF6 / EC–DEC) and assembled into CR2016 coin cells in an argon-filled glove box.

[0159] (8) The battery obtained in step (7) is subjected to a voltage range of 1.0 to 3.0V at 100mA g. -1 Charge-discharge cycles were performed at a current density (based on the mass of the composite material, the same below). Electrochemical performance is as follows: Figure 16 As shown, S-PpPDA-350-137 exhibits a capacity of 585 mAh g. -1 The reversible specific capacity (based on the quality of the composite material, the same below) was 87% after 50 cycles (relative to the reversible specific capacity, the same below), and the charge-discharge curve showed typical solid-solid conversion characteristics.

[0160] (9) Using the electrode sheet prepared in step (6) as the positive electrode, the sodium metal sheet as the negative electrode, and a combination of polypropylene membrane (Celgard 2325) and glass fiber membrane as the diaphragm, add an appropriate amount of electrolyte (1 mol L) dropwise. -1 Sodium hexafluorophosphate was dissolved in a solution of ethylene carbonate / diethyl carbonate (i.e., 1M NaPF6 / EC–DEC) and assembled into CR2025 coin cells in an argon-filled glove box.

[0161] (10) The battery obtained in step (9) is subjected to a voltage range of 0.8 to 3.0V at 100mA g. -1 The current density was used for charge-discharge cycles. Electrochemical performance was as follows: Figure 17 As shown, S-PpPDA-350-137 exhibits a capacity of 506 mAh g in sodium batteries. -1 The reversible specific capacity has a capacity retention rate of 82% after 30 cycles.

[0162] (11) Using the electrode sheet prepared in step (6) as the positive electrode, the potassium metal sheet as the negative electrode, and a combination of polypropylene membrane (Celgard 2325) and glass fiber membrane as the diaphragm, add an appropriate amount of electrolyte (1 mol L) dropwise. -1 Potassium hexafluorophosphate was dissolved in a solution of ethylene carbonate / diethyl carbonate (i.e., 1M KPF6 / EC–DEC) and assembled into CR2025 button cells in an argon-filled glove box.

[0163] (12) The battery obtained in step (11) is subjected to a voltage range of 1.0 to 3.0V at 100mA g. -1 The current density was used for charge-discharge cycles. Electrochemical performance was as follows: Figure 18 As shown, S-PpPDA-350-137 exhibits a capacity of 317 mAh g in potassium batteries. -1 The reversible specific capacity has a capacity retention rate of 84% after 30 cycles.

[0164] Finally, it should be noted that the terms “comprising,” “including,” or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0165] Although preferred embodiments of the invention have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments as well as all changes and modifications falling within the scope of the invention.

[0166] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A method of one-pot in-situ preparation of sulfur-phenylenediamine polymer composite material, characterized in that, The sulfur-phenylenediamine polymer composite includes sulfur-phenylenediamine polymer composite A or sulfur-phenylenediamine polymer composite B; the method includes: The phenylenediamine monomer, the oxidizing agent and the elemental sulfur are mixed and then heated and reacted at 100-600 ℃, and a solid crude product is obtained after cooling; wherein the phenylenediamine monomer is a mixture of one or more of o-phenylenediamine, m-phenylenediamine and p-phenylenediamine; The solid crude product is washed by dissolution to remove inorganic and organic impurities, and a sulfur-phenylenediamine polymer composite A is obtained. The sulfur-phenylenediamine polymer composite A is heated and evaporated / sublimated or washed by dissolution to remove the elemental sulfur contained therein, and a sulfur-phenylenediamine polymer composite B with reduced or completely removed elemental sulfur is obtained.

2. The production method according to claim 1, characterized by, The oxidizing agent includes at least one of permonosulfuric acid and its salts, perdisulfuric acid and its salts, sulfur dioxide, sulfur trioxide, concentrated sulfuric acid, and trivalent iron salts, perchlorate salts, hypochlorite salts, permanganate salts, dichromate salts, chromic acid, concentrated nitric acid, bromine, iodine, peroxides, chloranil and 2,3-dichloro-5,6-dicyano-benzoquinone.

3. The production method according to claim 1, characterized by, The heating reaction is carried out at a reaction temperature of 100-600 ℃ for 1-4320 minutes; and the reaction atmosphere of the heating reaction is selected from vacuum, air, nitrogen or inert gas.

4. A multiple composite with a sulfur-phenylenediamine polymer composite as the main body, characterized by The method includes: The sulfur-phenylenediamine polymer composite A or the sulfur-phenylenediamine polymer composite B prepared by the method of any one of claims 1-3 is used as a main body of a multiple composite; The method for preparing the multiple composite with the sulfur-phenylenediamine polymer composite as a main body is to add an additive in the heating reaction of the method of any one of claims 1-3 or to first compound the reaction raw materials of the method of any one of claims 1-3 with an additive and then perform the heating reaction; the additive includes at least one of a carbon material, a metal compound and an elemental sulfur family 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 MXene; and the elemental sulfur family element is selected from selenium and tellurium.

5. The use of the multiple composite with the sulfur-phenylenediamine polymer composite as a main body in claim 4 in the preparation of a battery positive electrode.

6. A battery positive electrode, characterized by, The positive electrode is prepared by uniformly mixing 30%-99% active material, 1%-70% conductive agent and 0%-40% binder in mass fraction and then coating or pressing on a current collector; and the active material is the sulfur-phenylenediamine polymer composite prepared by the method of any one of claims 1-3 or the multiple composite with the sulfur-phenylenediamine polymer composite as a main body in claim 4.

7. The battery cathode of claim 6, wherein, The conductive agent includes any one or mixture of several of graphite, conductive carbon black, acetylene black, carbon nanotube, carbon fiber, activated carbon, graphene and fullerene; the binder includes any one or 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 compounded with styrene-butadiene rubber or its copolymer, polyether or its copolymer, polyester or its copolymer, polyacrylic acid or polyacrylic acid salt.

8. A battery, characterized by The battery is matched and assembled by the battery positive electrode of claim 6 or 7 directly or after pre-lithiation, pre-sodiation or pre-potassiation treatment.

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