CN111584843A - Polyaniline copolymer-porous carbon-g-C3N4Positive electrode material of lithium-sulfur battery and preparation method thereof - Google Patents
Polyaniline copolymer-porous carbon-g-C3N4Positive electrode material of lithium-sulfur battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of lithium-sulfur battery positive electrode materials, and discloses polyaniline copolymer-porous carbon-g-C3N4The positive electrode material of the lithium-sulfur battery comprises the following formula raw materials and components: porous carbon-g-C3N4Composite material, sublimed sulfur, aniline, m-aminobenzene sulfonic acid, initiator, surfactant and end capping agent. The polyaniline copolymer-porous carbon-g-C3N4Lithium-sulfur battery positive electrode material graphene carbon nitride g-C3N4By nitrogen with lithiumLithium in polysulfide forms chemical bond to carry out chemical adsorption, so that the loss of active sulfur substances is reduced, and the g-C is reduced by doping B3N4Internal resistance of, increase g-C3N4Of electrically conductive, porous carbon-g-C3N4The composite material has rich nano mesopores and pore structures, provides rich loading sites for active sulfur, has the specific capillary adsorption effect of the nano mesopores, physically adsorbs lithium polysulfide, coats the sulfur-loaded porous carbon-g-C with sulfonated polyaniline copolymer with excellent conductivity3N4The sulfonic acid groups can form chemisorptions to the lithium polysulfide.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur battery positive electrode materials, in particular to polyaniline copolymer-porous carbon-g-C3N4Lithium-sulfur battery positive electrodeA pole material and a method for producing the same.
Background
The lithium-sulfur battery is a lithium battery with metal lithium as a negative electrode and sulfur as a battery positive electrode, has the characteristics of high theoretical specific capacity and battery theoretical specific energy, rich elemental sulfur storage, low price, environmental friendliness and the like, and is a lithium battery with great development potential.
However, the ion conductivity and the electron conductivity of the current lithium-sulfur battery cathode material are poor, diffusion and transmission of electrons and ions are inhibited, the rate performance of the battery is influenced, and a lithium polysulfide compound produced by reaction is easily dissolved in electrolyte to generate a shuttle effect, so that active sulfur substances are lost, and the capacity of the battery is attenuated.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides polyaniline copolymer-porous carbon-g-C3N4The lithium-sulfur battery positive electrode material and the preparation method thereof solve the problem of poor conductivity of the lithium-sulfur battery positive electrode material and solve the problem that lithium polysulfide is easy to dissolve in electrolyte.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: polyaniline copolymer-porous carbon-g-C3N4The positive electrode material of the lithium-sulfur battery comprises the following formula raw materials in parts by weight: 8-30 parts of porous carbon-g-C3N4Composite material, 30-36 parts of sublimed sulfur, 10-15 parts of aniline and 4-8 parts of m-aminobenzene sulfonic acid22-26 parts of initiator, 0.5-1 part of surfactant and 3.5-6 parts of end capping agent.
Preferably, the initiator is ammonium persulfate.
Preferably, the surfactant is sodium dodecyl sulfate.
Preferably, the end-capping agent is p-diphenylamine.
Preferably, the porous carbon-g-C3N4The preparation method of the composite material comprises the following steps:
(1) adding distilled water, boric acid and melamine into a reaction bottle, placing the reaction bottle in an ultrasonic processor for ultrasonic dispersion treatment for 20-40min, placing the reaction bottle in a constant-temperature water bath kettle for heating to 70-80 ℃, stirring at constant speed until a solvent is evaporated, grinding a solid product into fine powder, placing the fine powder in a muffle furnace, heating to 520-560 ℃ at a heating rate of 3-8 ℃/min, carrying out heat preservation and calcination for 2-4h, washing a calcined product with distilled water, and fully drying to prepare the B-doped g-C3N4。
(2) Adding N, N-dimethylformamide solvent and B doped g-C into a reaction bottle3N4Placing a reaction bottle in a low-temperature cooling instrument, uniformly stirring for 20-25h at 10-30 ℃, pouring the solution into a film forming mold, fully drying to remove the solvent, washing the film by using distilled water and ethanol, placing the film in a mixed solvent of distilled water and ethanol, wherein the volume ratio of the solution to the solvent is 1:1-2, adding sodium hydroxide to adjust the pH value of the solution to 13-14, uniformly stirring for 1-3h at 50-70 ℃ to perform a defluorination and hydrogenation process, filtering to remove the solvent, washing the film by using distilled water and fully drying.
(3) Placing the film in an atmosphere resistance furnace, introducing nitrogen, heating to 820-3N4A composite material.
Preferably, the mass ratio of the boric acid to the melamine is 1: 30-60.
Preferably, said B is doped with g-C3N4The mass ratio of the polyvinylidene fluoride to the pore-foaming agent polymethyl methacrylate is 1:1.2-1.8: 0.2-0.6.
Preferably, the polyaniline copolymer-porous carbon-g-C3N4The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
(1) 8-30 parts of porous carbon-g-C3N4Mixing the composite material and 30-36 parts of sublimed sulfur, grinding the mixture into fine powder, placing the fine powder in a high-pressure reaction kettle, introducing nitrogen, heating the mixture to the temperature of 150 ℃ and 160 ℃, and carrying out melt diffusion reaction for 6-10 hours to prepare the sulfur-loaded porous carbon-g-C3N4A composite material.
(2) Introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of distilled water and ethanol, wherein the volume ratio of the distilled water to the mixed solvent is 5-8:1, and sulfur-loaded porous carbon-g-C3N4Performing ultrasonic dispersion treatment on the composite material and 0.5-1 part of surfactant sodium dodecyl sulfate for 30-60min, adding hydrochloric acid to adjust the pH value of the solution to 1-2, placing a reaction bottle in a low-temperature cooling instrument, adding 10-15 parts of aniline, 4-8 parts of m-aminobenzenesulfonic acid and 22-26 parts of initiator ammonium persulfate into the solution at 0-5 ℃, uniformly stirring and reacting for 3-5h, adding 3.5-6 parts of end capping agent p-diphenylamine, uniformly stirring and reacting for 2-5h, performing vacuum drying on the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the polyaniline copolymer-porous carbon-g-C3N4A positive electrode material for a lithium-sulfur battery.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the polyaniline copolymer-porous carbon-g-C3N4Lithium-sulfur battery positive electrode material graphene carbon nitride g-C3N4Contains high pyridine nitrogen content, and nitrogen atom can form chemical bond with lithium in lithium polysulfide to perform chemical adsorption on lithium polysulfide, thereby inhibiting lithiumThe shuttle effect of polysulfide reduces the loss of active sulfur substances, effectively reduces the capacity attenuation of the lithium-sulfur battery, and simultaneously, boric acid is used as a boron source, and the doping of B reduces g-C3N4Internal resistance of, increase g-C3N4And boric acid generates steam during high-temperature thermal cracking, and can be used as a pore-forming agent to enable the g-C to be in contact with the water3N4A large number of pore structures are formed inside, and transmission channels are provided for electrons and ions, so that the rate performance of the battery is improved.
The polyaniline copolymer-porous carbon-g-C3N4The positive electrode material of the lithium-sulfur battery takes polyvinylidene fluoride as a carbon source and polymethyl methacrylate as a pore-foaming agent, and porous carbon-g-C is obtained by high-temperature thermal cracking3N4The composite material has rich nano mesopores and pore structures, provides rich loading sites for active sulfur, has the specific capillary adsorption effect of the nano mesopores, and can reduce the battery capacity attenuation caused by the shuttle effect by physically adsorbing lithium polysulfide.
The polyaniline copolymer-porous carbon-g-C3N4The positive electrode material of the lithium-sulfur battery is prepared by forming sulfonated polyaniline copolymer by aniline and m-aminobenzenesulfonic acid through in-situ polymerization, so that sulfur-loaded porous carbon-g-C is completely coated3N4Compared with the traditional polyaniline, the sulfonated polyaniline copolymer has more excellent conductivity, the conductivity of the positive electrode material is improved, sulfonic acid groups can form chemical adsorption on lithium polysulfide, and simultaneously, the loss and shuttle effect caused by the dissolution of active sulfur in electrolyte are reduced under the synergistic action of the physical confinement effect of the polyaniline copolymer.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: polyaniline copolymer-porous carbon-g-C3N4The positive electrode material of the lithium-sulfur battery comprises the following formula raw materials in parts by weight: 8-30 parts of porous carbon-g-C3N4Composite material, 30-36 parts of sublimed sulfur, 10-15 parts of aniline, 4-8 parts of m-aminobenzene sulfonic acid and 22-26 parts of initiator0.5-1 part of surfactant and 3.5-6 parts of end capping agent, wherein the initiator is ammonium persulfate, the surfactant is sodium dodecyl sulfate, and the end capping agent is p-diphenylamine.
Porous carbon-g-C3N4The preparation method of the composite material comprises the following steps:
(1) adding distilled water, boric acid and melamine into a reaction bottle in a mass ratio of 1:30-60, placing the reaction bottle in an ultrasonic treatment instrument for ultrasonic dispersion treatment for 20-40min, placing the reaction bottle in a constant-temperature water bath kettle for heating to 70-80 ℃, uniformly stirring until a solvent is evaporated, grinding a solid product into fine powder, placing the fine powder in a muffle furnace, heating to 520-560 ℃, keeping the temperature and calcining for 2-4h, washing the calcined product with distilled water, and fully drying to obtain the B-doped g-C3N4。
(2) Adding N, N-dimethylformamide solvent into a reaction bottle, and doping B with g-C3N4The mass ratio of polyvinylidene fluoride to a pore-forming agent polymethyl methacrylate is 1:1.2-1.8:0.2-0.6, a reaction bottle is placed in a low-temperature cooling instrument, the mixture is stirred at a constant speed for 20-25h at 10-30 ℃, the solution is poured into a film forming mold, the solvent is fully dried and removed, distilled water and ethanol are used for washing a film, the film is placed in a mixed solvent of distilled water and ethanol, the volume ratio of the two is 1:1-2, sodium hydroxide is added to adjust the pH value of the solution to 13-14, the solution is stirred at a constant speed for 1-3h at 50-70 ℃, the defluorination and hydrogenation process is carried out, the solvent is removed by filtration, and the film is washed by distilled water and fully dried.
(3) Placing the film in an atmosphere resistance furnace, introducing nitrogen, heating to 820-3N4A composite material.
Polyaniline copolymer-porous carbon-g-C3N4Lithium-sulfur battery positive electrodeThe preparation method of the pole material comprises the following steps:
(1) 8-30 parts of porous carbon-g-C3N4Mixing the composite material and 30-36 parts of sublimed sulfur, grinding the mixture into fine powder, placing the fine powder in a high-pressure reaction kettle, introducing nitrogen, heating the mixture to the temperature of 150 ℃ and 160 ℃, and carrying out melt diffusion reaction for 6-10 hours to prepare the sulfur-loaded porous carbon-g-C3N4A composite material.
(2) Introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of distilled water and ethanol, wherein the volume ratio of the distilled water to the mixed solvent is 5-8:1, and sulfur-loaded porous carbon-g-C3N4Performing ultrasonic dispersion treatment on the composite material and 0.5-1 part of surfactant sodium dodecyl sulfate for 30-60min, adding hydrochloric acid to adjust the pH value of the solution to 1-2, placing a reaction bottle in a low-temperature cooling instrument, adding 10-15 parts of aniline, 4-8 parts of m-aminobenzenesulfonic acid and 22-26 parts of initiator ammonium persulfate into the solution at 0-5 ℃, uniformly stirring and reacting for 3-5h, adding 3.5-6 parts of end capping agent p-diphenylamine, uniformly stirring and reacting for 2-5h, performing vacuum drying on the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the polyaniline copolymer-porous carbon-g-C3N4A positive electrode material for a lithium-sulfur battery.
Example 1
(1) Preparation of B doped g-C3N4Component 1: adding distilled water, boric acid and melamine into a reaction bottle in a mass ratio of 1:30, placing the reaction bottle in an ultrasonic treatment instrument for ultrasonic dispersion treatment for 20 min, placing the reaction bottle in a constant-temperature water bath kettle for heating to 70 ℃, stirring at a constant speed until a solvent is evaporated, grinding a solid product into fine powder, placing the fine powder in a muffle furnace at a heating rate of 3 ℃/min, heating to 520 ℃, keeping the temperature and calcining for 2h, washing the calcined product with distilled water and fully drying to prepare the B-doped g-C3N4And (3) component 1.
(2) Preparation of activated porous carbon-g-C3N4Composite material 1: adding N, N-dimethylformamide solvent into a reaction bottle, and doping B with g-C3N4The component 1, polyvinylidene fluoride and pore-foaming agent polymethyl methacrylate with the mass ratio of 1:1.2:0.2 are placed in a reaction bottle of a low-temperature cooling instrumentStirring at constant speed for 20 h at 10 ℃, pouring the solution into a film forming mould, fully drying to remove the solvent, washing a film by using distilled water and ethanol, placing the film into a mixed solvent of distilled water and ethanol, wherein the volume ratio of the distilled water to the ethanol is 1:1, adding sodium hydroxide to adjust the pH value of the solution to 13, stirring at constant speed for 1h at 50 ℃, performing defluorination and hydrogenation processes, filtering to remove the solvent, washing the film by using distilled water and fully drying, placing the film into an atmosphere resistance furnace, introducing nitrogen, heating to 820 ℃, performing heat preservation and calcination for 3h, mixing and grinding a calcined product and potassium hydroxide to fine powder, wherein the mass ratio of the calcined product to the potassium hydroxide is 1:2, placing the film into the atmosphere resistance furnace, introducing nitrogen, heating to 3 ℃/min, performing heat preservation and activation treatment for 1h at 140 ℃, heating to 800 ℃, performing heat preservation and calcination for 2h, washing the calcined product with distilled water until neutral to prepare activated porous carbon-g-C3N4A composite material 1.
(3) Preparation of sulfur-loaded porous carbon-g-C3N4Composite material 1:30 parts of porous carbon-g-C3N4Mixing the composite material 1 and 30 parts of sublimed sulfur, grinding the mixture into fine powder, placing the fine powder in a high-pressure reaction kettle, introducing nitrogen, heating the mixture to 150 ℃, and carrying out melt diffusion reaction for 6 hours to prepare the sulfur-loaded porous carbon-g-C3N4A composite material 1.
(4) Preparation of polyaniline copolymer-porous carbon-g-C3N4Positive electrode material for lithium-sulfur battery 1: introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of distilled water and ethanol, wherein the volume ratio of the distilled water to the mixed solvent is 5:1, and sulfur-loaded porous carbon-g-C3N4Carrying out ultrasonic dispersion treatment on 1 part of composite material and 0.5 part of surfactant sodium dodecyl sulfate for 30 min, adding hydrochloric acid to adjust the pH value of the solution to 2, placing a reaction bottle in a low-temperature cooling instrument, adding 10 parts of aniline, 4 parts of m-aminobenzene sulfonic acid and 22 parts of initiator ammonium persulfate into the solution at 5 ℃, stirring at a constant speed for reaction for 3 hours, adding 3.5 parts of end capping agent p-diphenylamine, stirring at a constant speed for reaction for 2 hours, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the polyaniline copolymer-porous carbon-g-C3N4A positive electrode material 1 for lithium-sulfur batteries.
Example 2
(1) Preparation of B doped g-C3N4And (2) component: adding distilled water, boric acid and melamine into a reaction bottle in a mass ratio of 1:30, placing the reaction bottle in an ultrasonic treatment instrument for ultrasonic dispersion treatment for 40min, placing the reaction bottle in a constant-temperature water bath kettle for heating to 80 ℃, stirring at a constant speed until a solvent is evaporated, grinding a solid product into fine powder, placing the fine powder in a muffle furnace at a heating rate of 3 ℃/min, heating to 520 ℃, keeping the temperature and calcining for 2h, washing the calcined product with distilled water and fully drying to prepare the B-doped g-C3N4And (3) component 2.
(2) Preparation of activated porous carbon-g-C3N4Composite material 2: adding N, N-dimethylformamide solvent into a reaction bottle, and doping B with g-C3N4The preparation method comprises the following steps of putting a reaction bottle into a low-temperature cooling instrument, stirring at a constant speed of 30 ℃ for 25 hours, pouring the solution into a film forming mold, fully drying to remove the solvent, washing a film with distilled water and ethanol, putting the film into a mixed solvent of distilled water and ethanol, adjusting the volume ratio of the two to be 1:1, adding sodium hydroxide to adjust the pH value of the solution to 14, stirring at a constant speed of 50 ℃ for 1 hour to carry out a defluorination and hydrogenation process, filtering to remove the solvent, washing the film with distilled water, fully drying, putting the film into an atmosphere resistance furnace, introducing nitrogen, heating at a rate of 8 ℃/min, heating to 820 ℃, carrying out heat preservation and calcination for 5 hours, mixing and grinding a calcined product and potassium hydroxide to fine powder, wherein the mass ratio of the two is 1:2, putting the film into the atmosphere resistance furnace, introducing nitrogen, heating up at a rate of 8 ℃/min, keeping the temperature at 140 ℃ for activation treatment for 2h, heating up to 800 ℃, keeping the temperature for calcination for 2h, washing the calcined product with distilled water until the calcined product is neutral, and preparing the activated porous carbon-g-C3N4A composite material 2.
(3) Preparation of sulfur-loaded porous carbon-g-C3N4Composite material 2: 25 parts of porous carbon-g-C3N4Mixing the composite material 2 and 31 parts of sublimed sulfur, grinding the mixture into fine powder, placing the fine powder in a high-pressure reaction kettle, introducing nitrogen, heating the mixture to 150 ℃, and carrying out a melt diffusion reaction for 10 hours to prepare the sulfurSupported porous carbon-g-C3N4A composite material 2.
(4) Preparation of polyaniline copolymer-porous carbon-g-C3N4Lithium-sulfur battery positive electrode material 2: introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of distilled water and ethanol, wherein the volume ratio of the distilled water to the mixed solvent is 5:1, and sulfur-loaded porous carbon-g-C3N4Carrying out ultrasonic dispersion treatment on a composite material 2 and 0.6 part of surfactant sodium dodecyl sulfate for 30 min, adding hydrochloric acid to adjust the pH value of the solution to 2, placing a reaction bottle in a low-temperature cooling instrument, adding 11 parts of aniline, 5 parts of m-aminobenzenesulfonic acid and 23 parts of initiator ammonium persulfate into the solution at 5 ℃, stirring at a constant speed for reaction for 3h, adding 4.4 parts of end capping agent p-diphenylamine, stirring at a constant speed for reaction for 5h, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the polyaniline copolymer-porous carbon-g-C3N4A lithium sulfur battery positive electrode material 2.
Example 3
(1) Preparation of B doped g-C3N4And (3) component: adding distilled water, boric acid and melamine into a reaction bottle in a mass ratio of 1:45, placing the reaction bottle in an ultrasonic treatment instrument for ultrasonic dispersion treatment for 30 min, placing the reaction bottle in a constant-temperature water bath kettle for heating to 75 ℃, stirring at a constant speed until a solvent is evaporated, grinding a solid product into fine powder, placing the fine powder in a muffle furnace at a heating rate of 6 ℃/min, heating to 540 ℃, keeping the temperature and calcining for 3h, washing the calcined product with distilled water and fully drying to prepare the B-doped g-C3N4And (3) component.
(2) Preparation of activated porous carbon-g-C3N4Composite material 3: adding N, N-dimethylformamide solvent into a reaction bottle, and doping B with g-C3N4The component 3, polyvinylidene fluoride and a pore-foaming agent polymethyl methacrylate with the mass ratio of 1:1.5:0.4, placing a reaction bottle in a low-temperature cooling instrument, stirring at a constant speed for 22 hours at 20 ℃, pouring the solution into a film forming mold, fully drying to remove the solvent, washing the film by using distilled water and ethanol, placing the film in a mixed solvent of distilled water and ethanol with the volume ratio of 1:1.5, adding sodium hydroxide for regulationThe pH value of the solution is 14, the solution is stirred at a constant speed for 2h at 60 ℃ to carry out defluorination hydrogenation process, the solvent is removed by filtration, the film is washed by distilled water and fully dried, the film is placed in an atmosphere resistance furnace to be introduced with nitrogen, the heating rate is 5 ℃/min, the film is heated to 840 ℃ to be subjected to heat preservation and calcination for 4h, the calcination product and potassium hydroxide are mixed and ground into fine powder, the mass ratio of the two is 1:3, the film is placed in the atmosphere resistance furnace to be introduced with nitrogen, the heating rate is 5 ℃/min, the heat preservation and activation treatment is carried out for 1.5h at 160 ℃, the temperature is raised to 850 ℃, the heat preservation and calcination is carried out for 2.5 h, the calcination product is3N4A composite material 3.
(3) Preparation of sulfur-loaded porous carbon-g-C3N4Composite material 3: 20 parts of porous carbon-g-C3N4Mixing the composite material 3 and 32 sublimed sulfur, grinding the mixture into fine powder, placing the fine powder in a high-pressure reaction kettle, introducing nitrogen, heating the mixture to 155 ℃, and carrying out melt diffusion reaction for 8 hours to prepare the sulfur-loaded porous carbon-g-C3N4A composite material 3.
(4) Preparation of polyaniline copolymer-porous carbon-g-C3N4Lithium-sulfur battery positive electrode material 3: introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of distilled water and ethanol, wherein the volume ratio of the distilled water to the mixed solvent is 5:1, and sulfur-loaded porous carbon-g-C3N4Carrying out ultrasonic dispersion treatment on 3 parts of composite material and 0.7 part of surfactant sodium dodecyl sulfate for 60min, adding hydrochloric acid to adjust the pH value of the solution to 2, placing a reaction bottle in a low-temperature cooling instrument, adding 12.5 parts of aniline, 6 parts of m-aminobenzenesulfonic acid and 24 parts of initiator ammonium persulfate into the solution at 2 ℃, stirring at a constant speed for reaction for 3h, adding 4.8 parts of end capping agent p-diphenylamine, stirring at a constant speed for reaction for 3.5 h, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the polyaniline copolymer-porous carbon-g-C3N4A lithium sulfur battery positive electrode material 3.
Example 4
(1) Preparation of B doped g-C3N4And (4) component: adding distilled water, boric acid and melamine into a reaction bottle in a mass ratio of 1:45, and placing the reaction bottle in ultrasonic treatmentPerforming ultrasonic dispersion treatment in an instrument for 20 min, placing a reaction bottle in a constant-temperature water bath kettle, heating to 80 ℃, stirring at a constant speed until a solvent is evaporated, grinding a solid product to fine powder, placing the fine powder in a muffle furnace, heating to 560 ℃ at a heating rate of 3 ℃/min, keeping the temperature, calcining for 4h, washing the calcined product with distilled water, and fully drying to obtain the B-doped g-C3N4And (4) component.
(2) Preparation of activated porous carbon-g-C3N4The composite material 4: adding N, N-dimethylformamide solvent into a reaction bottle, and doping B with g-C3N4The component 4, polyvinylidene fluoride and a pore-forming agent polymethyl methacrylate, the mass ratio of the three components is 1:1.2:0.2, a reaction bottle is placed in a low-temperature cooling instrument, the solution is stirred at a constant speed for 20 hours at a temperature of 30 ℃, the solution is poured into a film forming mold, the solvent is sufficiently dried and removed, a film is washed by distilled water and ethanol, the film is placed in a mixed solvent of distilled water and ethanol, the volume ratio of the two is 1:1.5, sodium hydroxide is added to adjust the pH value of the solution to 14, the solution is stirred at a constant speed for 1 hour at a temperature of 70 ℃ to carry out the defluorination and hydrogenation process, the solvent is removed by filtration, the film is washed by distilled water and sufficiently dried, the film is placed in an atmosphere resistance furnace to be introduced with nitrogen, the heating rate is 3 ℃/min, the temperature is increased to 860 ℃, the temperature is preserved and calcined for 3 hours, the, heating up at a rate of 8 ℃/min, keeping the temperature at 180 ℃ for activation for 1h, heating up to 840 ℃, keeping the temperature for calcination for 2h, washing the calcination product with distilled water until the product is neutral, and preparing the activated porous carbon-g-C3N4A composite material 4.
(3) Preparation of sulfur-loaded porous carbon-g-C3N4The composite material 4: 14 parts of porous carbon-g-C3N4Mixing the composite material 4 and 34 parts of sublimed sulfur, grinding the mixture into fine powder, placing the fine powder in a high-pressure reaction kettle, introducing nitrogen, heating the mixture to 150 ℃, and carrying out melt diffusion reaction for 10 hours to prepare the sulfur-loaded porous carbon-g-C3N4A composite material 4.
(4) Preparation of polyaniline copolymer-porous carbon-g-C3N4Lithium-sulfur battery positive electrode material 4: introducing nitrogen into the reaction bottle to discharge airAdding a mixed solvent of distilled water and ethanol into the gas, wherein the volume ratio of the distilled water to the ethanol is 8:1, and sulfur-loaded porous carbon-g-C3N4Carrying out ultrasonic dispersion treatment on a composite material 4 and 0.8 part of surfactant sodium dodecyl sulfate for 60min, adding hydrochloric acid to adjust the pH value of the solution to 2, placing a reaction bottle in a low-temperature cooling instrument, adding 14 parts of aniline, 7 parts of m-aminobenzenesulfonic acid and 25 parts of initiator ammonium persulfate into the solution at 0 ℃, stirring at a constant speed for reaction for 4h, adding 5.2 parts of end capping agent p-diphenylamine, stirring at a constant speed for reaction for 5h, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the polyaniline copolymer-porous carbon-g-C3N4A lithium sulfur battery positive electrode material 4.
Example 5
(1) Preparation of B doped g-C3N4And (5) component: adding distilled water, boric acid and melamine into a reaction bottle in a mass ratio of 1:60, placing the reaction bottle in an ultrasonic treatment instrument for ultrasonic dispersion treatment for 40min, placing the reaction bottle in a constant-temperature water bath kettle for heating to 80 ℃, uniformly stirring until a solvent is evaporated, grinding a solid product into fine powder, placing the fine powder in a muffle furnace at a heating rate of 8 ℃/min, heating to 560 ℃, keeping the temperature and calcining for 4h, washing the calcined product with distilled water, and fully drying to obtain the B-doped g-C3N4And (5) component.
(2) Preparation of activated porous carbon-g-C3N4And (3) composite material 5: adding N, N-dimethylformamide solvent into a reaction bottle, and doping B with g-C3N4The preparation method comprises the following steps of putting a reaction bottle into a low-temperature cooling instrument, stirring at 30 ℃ for 25 hours at a constant speed, pouring the solution into a film forming mold, fully drying to remove a solvent, washing a film by using distilled water and ethanol, putting the film into a mixed solvent of distilled water and ethanol, adjusting the pH of the solution to 14 by adding sodium hydroxide, stirring at 70 ℃ for 3 hours at a constant speed to perform a defluorination and hydrogenation process, filtering to remove the solvent, washing the film by using distilled water, fully drying, putting the film into an atmosphere resistance furnace, introducing nitrogen, heating to 8 ℃/min, heating to 860 ℃ for preservation, wherein the mass ratio of the components 5, the polyvinylidene fluoride and the polymethyl methacrylate is 1:1.8:0.6, putting the reaction bottle into the low-temperature cooling instrument, pouring theCarrying out warm calcination for 5h, mixing and grinding the calcined product and potassium hydroxide into fine powder with the mass ratio of 1:4, putting the mixture into an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 8 ℃/min, carrying out heat preservation activation treatment at 180 ℃ for 2h, heating to 840 ℃, carrying out heat preservation calcination for 3h, washing the calcined product with distilled water until the calcined product is neutral, and preparing the activated porous carbon-g-C3N4A composite material 5.
(3) Preparation of sulfur-loaded porous carbon-g-C3N4And (3) composite material 5: 8 parts of porous carbon-g-C3N4Mixing the composite materials 5 and 36 with sublimed sulfur, grinding the mixture into fine powder, placing the fine powder in a high-pressure reaction kettle, introducing nitrogen, heating the mixture to 160 ℃, and carrying out melt diffusion reaction for 10 hours to prepare the sulfur-loaded porous carbon-g-C3N4A composite material 5.
(4) Preparation of polyaniline copolymer-porous carbon-g-C3N4Lithium-sulfur battery positive electrode material 5: introducing nitrogen into a reaction bottle to discharge air, adding a mixed solvent of distilled water and ethanol, wherein the volume ratio of the distilled water to the mixed solvent is 8:1, and sulfur-loaded porous carbon-g-C3N4Carrying out ultrasonic dispersion treatment on 5 parts of composite material and 1 part of surfactant sodium dodecyl sulfate for 60min, adding hydrochloric acid to adjust the pH value of the solution to 1, placing a reaction bottle in a low-temperature cooling instrument, adding 15 parts of aniline, 8 parts of m-aminobenzenesulfonic acid and 26 parts of initiator ammonium persulfate into the solution at 0 ℃, stirring at a constant speed for 5 hours, adding 6 parts of end capping agent p-diphenylamine, stirring at a constant speed for 5 hours, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the polyaniline copolymer-porous carbon-g-C3N4A lithium sulfur battery positive electrode material 5.
The polyaniline copolymer-porous carbon-g-C in examples 1-53N4Respectively adding the positive electrode material of the lithium-sulfur battery into an N-methylpyrrolidone solvent, adding polyvinylidene fluoride and acetylene black, uniformly stirring, coating the mixture on the surface of an aluminum foil, drying and cutting to obtain the positive electrode sheet of the lithium-sulfur battery, taking the lithium sheet as a negative electrode, taking Celgard2300 as a diaphragm, taking an electrolyte as a bis (trifluoromethane) sulfimide lithium +1, 3-dioxolane + ethylene glycol dimethyl ether solution, and assembling into a 2025 type electric battery in an argon atmosphereAnd the cell is subjected to electrochemical performance test in a CHI660D electrochemical workstation and a CT-3008W-5V 10 mA-S4 cell test system, and the test standard is GB/T36276-.
The polyaniline copolymer-porous carbon-g-C3N4Lithium-sulfur battery positive electrode material graphene carbon nitride g-C3N4The lithium polysulfide compound has high pyridine nitrogen content, nitrogen atoms of the compound can form chemical bonds with lithium in the lithium polysulfide to carry out chemical adsorption on the lithium polysulfide compound, so that the shuttle effect of the lithium polysulfide compound is inhibited, the loss of active sulfur substances is reduced, the capacity attenuation of the lithium sulfur battery is effectively reduced, and meanwhile, boric acid is used as a boron source, and the g-C is reduced by doping B3N4Internal resistance of, increase g-C3N4And boric acid generates steam during high-temperature thermal cracking, and can be used as a pore-forming agent to enable the g-C to be in contact with the water3N4A large number of pore structures are formed inside, and transmission channels are provided for electrons and ions, so that the rate performance of the battery is improved.
Polyvinylidene fluoride is used as a carbon source, polymethyl methacrylate is used as a pore-foaming agent, and porous carbon-g-C is obtained through high-temperature thermal cracking3N4The composite material has rich nano mesopores and pore structures, provides rich loading sites for active sulfur, has the specific capillary adsorption effect of the nano mesopores, and can reduce the battery capacity attenuation caused by the shuttle effect by physically adsorbing lithium polysulfide.
By in-situ polymerization, aniline and m-aminobenzenesulfonic acid form sulfonated polyaniline copolymer, so that sulfur-loaded porous carbon-g-C is completely coated3N4Compared with the traditional polyaniline, the sulfonated polyaniline copolymer has more excellent conductivity, the conductivity of the positive electrode material is improved, sulfonic acid groups can form chemical adsorption on lithium polysulfide, and simultaneously, the loss and shuttle effect caused by the dissolution of active sulfur in electrolyte are reduced under the synergistic action of the physical confinement effect of the polyaniline copolymer.
Claims (8)
1. Polyaniline copolymer-porous carbon-g-C3N4The positive electrode material of the lithium-sulfur battery comprises the following formula raw materials and components in parts by weight, and is characterized in that: 8-30 parts of porous carbon-g-C3N430-36 parts of sublimed sulfur, 10-15 parts of aniline, 4-8 parts of m-aminobenzene sulfonic acid, 22-26 parts of initiator, 0.5-1 part of surfactant and 3.5-6 parts of end capping agent.
2. The polyaniline copolymer-porous carbon-g-C as claimed in claim 13N4The lithium-sulfur battery positive electrode material is characterized in that: the initiator is ammonium persulfate.
3. The polyaniline copolymer-porous carbon-g-C as claimed in claim 13N4The lithium-sulfur battery positive electrode material is characterized in that: the surfactant is sodium dodecyl sulfate.
4. The polyaniline copolymer-porous carbon-g-C as claimed in claim 13N4The lithium-sulfur battery positive electrode material is characterized in that: the end-capping agent is p-diphenylamine.
5. The polyaniline copolymer-porous carbon-g-C as claimed in claim 13N4The lithium-sulfur battery positive electrode material is characterized in that: said porous carbon-g-C3N4The preparation method of the composite material comprises the following steps:
(1) adding boric acid and melamine into a distilled water solvent, carrying out ultrasonic dispersion treatment on the solution for 20-40min, heating the solution to 70-80 ℃, uniformly stirring until the solvent is evaporated, grinding a solid product to fine powder, placing the fine powder in a muffle furnace at the heating rate of 3-8 ℃/min, heating to 520-560 ℃, carrying out heat preservation and calcination for 2-4h, washing and drying the calcined product, and preparing the B-doped g-C3N4；
(2) Addition of B-doped g-C to N, N-dimethylformamide solvent3N4Stirring the solution at 10-30 ℃ for 20-25h, pouring the solution into a film forming mold, drying to remove the solvent and wash the film, putting the film into a mixed solvent of distilled water and ethanol with the volume ratio of 1:1-2, adding sodium hydroxide to adjust the pH value of the solution to 13-14, stirring at 50-70 ℃ for 1-3h at constant speed, filtering to remove the solvent, washing the film and drying;
(3) placing the film in an atmosphere resistance furnace, introducing nitrogen, heating to 820-3N4A composite material.
6. The polyaniline copolymer-porous carbon-g-C as claimed in claim 53N4The lithium-sulfur battery positive electrode material is characterized in that: the mass ratio of the boric acid to the melamine is 1: 30-60.
7. The polyaniline copolymer-porous carbon-g-C as claimed in claim 53N4The lithium-sulfur battery positive electrode material is characterized in that: the B is doped with g-C3N4The mass ratio of the polyvinylidene fluoride to the pore-foaming agent polymethyl methacrylate is 1:1.2-1.8: 0.2-0.6.
8. The polyaniline copolymer-porous carbon-g-C as claimed in claim 13N4The lithium-sulfur battery positive electrode material is characterized in that: the polyaniline copolymer-porous carbon-g-C3N4The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
(1) 8-30 parts of porous carbon-g-C3N4Mixing the composite material with 30-36 parts of sublimed sulfur, grinding the mixture into fine powder, placing the fine powder in a reaction kettle, introducing nitrogen, heating the mixture to the temperature of 150 ℃ and 160 ℃, and carrying outPerforming melt diffusion reaction for 6-10h to prepare the sulfur-loaded porous carbon-g-C3N4A composite material;
(2) adding sulfur-loaded porous carbon-g-C into a mixed solvent of distilled water and ethanol with a volume ratio of 5-8:1 in a nitrogen atmosphere3N4The preparation method comprises the following steps of performing bulk treatment on a composite material and 0.5-1 part of surfactant sodium dodecyl sulfate for 30-60min, adding hydrochloric acid to adjust the pH value of a solution to 1-2, adding 10-15 parts of aniline, 4-8 parts of m-aminobenzene sulfonic acid and 22-26 parts of initiator ammonium persulfate into the solution at 0-5 ℃, reacting for 3-5h, adding 3.5-6 parts of end capping agent p-diphenylamine, reacting for 2-5h, removing the solvent from the solution, washing a solid product, and drying to prepare the polyaniline copolymer-porous carbon-g-C3N4A positive electrode material for a lithium-sulfur battery.
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