CN112707382A - Preparation method and application of nitrogen and sulfur doped porous hollow carbon spheres - Google Patents

Preparation method and application of nitrogen and sulfur doped porous hollow carbon spheres Download PDF

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CN112707382A
CN112707382A CN202011604310.6A CN202011604310A CN112707382A CN 112707382 A CN112707382 A CN 112707382A CN 202011604310 A CN202011604310 A CN 202011604310A CN 112707382 A CN112707382 A CN 112707382A
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nitrogen
hollow carbon
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sulfur doped
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高立雅
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Dongguan Xiaowa Technology Co ltd
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/05Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
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    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to the technical field of lithium ion battery cathode materials, and discloses a nitrogen and sulfur doped porous hollow carbon sphere which is used as a lithium ion battery cathode active material, has a unique porous and hollow structure, larger specific surface area and rich pore structure, shortens a diffusion path of lithium ions, promotes the extraction and the insertion of the lithium ions, thereby improving the actual specific capacity of the cathode material, improving the electrochemical properties of the porous hollow carbon spheres due to the existence of nitrogen in the porous hollow carbon spheres in the forms of pyrrole nitrogen, pyridine nitrogen and graphite nitrogen, having higher electronic conductivity and conductivity, improving the rate capability of the cathode material, and sulfur doping is beneficial to expanding the spacing between carbon layers, the pore structure and the specific surface area of the porous hollow carbon sphere are further improved, the exposure of a lithium ion de-intercalation site is more sufficient, and the lithium storage performance is more excellent.

Description

Preparation method and application of nitrogen and sulfur doped porous hollow carbon spheres
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a preparation method and application of nitrogen and sulfur doped porous hollow carbon spheres.
Background
In recent years, the problems of energy crisis and environmental pollution are not ignored, new energy storage and conversion devices, such as lithium ion batteries, capacity batteries, supercapacitors and the like, are vigorously developed in various countries of the world, wherein the lithium ion batteries have the advantages of large energy density, good cycle performance, no memory effect, wide working temperature limit and the like, and are widely applied to the aspects of electronic products, electric bicycles, new energy electric vehicles and the like.
The carbon-based negative electrode material of the lithium ion battery, which is currently in a research hotspot, mainly comprises graphite carbon, porous activated carbon, carbon aerogel, graphene, carbon nanotubes and the like, and the porous carbon-based material has a rich microporous structure, a large specific surface area, a good lithium ion diffusion coefficient and electronic conductivity, stable cycle performance and rich sources, and is a carbon-based negative electrode material of the lithium ion battery with great development potential.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method and application of a nitrogen and sulfur doped porous hollow carbon sphere, which has higher actual specific capacity and excellent cycling stability when used as a lithium ion battery cathode material.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of nitrogen and sulfur doped porous hollow carbon spheres comprises the following steps:
(1) adding distilled water solvent and nano SiO into a reaction bottle2Adding an ethanol solution of dopamine hydrochloride after uniform ultrasonic dispersion, dropwise adding concentrated ammonia water, controlling the concentration of the ammonia water in the total solution to be 0.4-0.6%, stirring at a constant speed for reaction for 24-48h, adding an acetone solvent, standing for sedimentation, performing low-speed centrifugal separation, washing and drying to obtain the polydopamine nano-particle-coated nano SiO with the shell-core structure2
(2) Coating polydopamine nano particles with nano SiO2Placing the mixture in sodium hydroxide solution, stirring at a constant speed for reaction, etching, and removing nano SiO2And (4) centrifuging the core to remove the solvent, and washing the core with distilled water until the core is neutral to obtain the polydopamine nano hollow microspheres.
(3) Adding ethanol solvent, polydopamine nano hollow microspheres and benzyl mercaptan into a reaction bottle, uniformly dispersing by ultrasonic wave, uniformly stirring at 30-50 ℃ for reaction for 15-25h, distilling under reduced pressure to remove the solvent, washing with distilled water and ethanol, and drying to obtain the benzyl mercaptan grafted polydopamine nano hollow microspheres.
(4) And (3) putting the benzyl mercaptan grafted polydopamine nano hollow microspheres into an atmosphere furnace for high-temperature carbonization to obtain nitrogen and sulfur doped hollow carbon spheres.
(5) Uniformly grinding the nitrogen-sulfur doped hollow carbon spheres and potassium hydroxide, placing the mixture in an atmosphere furnace for high-temperature etching, and washing the mixture to be neutral by using distilled water to obtain the nitrogen-sulfur doped porous hollow carbon spheres which are applied to the negative electrode material of the lithium ion battery.
Preferably, the nano SiO in the step (1)2The particle size of the compound is 100-500nm, and the mass ratio of the compound to the dopamine hydrochloride is 100: 120-180.
Preferably, the mass ratio of the polydopamine nano hollow microspheres to the benzylmercaptan in the step (3) is 100: 200-400.
Preferably, the high-temperature carbonization in the step (4) is carried out in a nitrogen atmosphere and is carbonized at 650-750 ℃ for 2-3 h.
Preferably, the mass ratio of the nitrogen-sulfur doped hollow carbon spheres to the potassium hydroxide in the step (5) is 100: 150-.
Preferably, the high-temperature etching in the step (5) is performed at 600-650 ℃ for 1-2h in a nitrogen atmosphere.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the nitrogen and sulfur doped porous hollow carbon sphere is prepared by nano SiO2As a core, by a solution oxidation method and an interface synthesis method, in nano SiO2Generating a layer of nano poly dopamine on the surface, and removing nano SiO by sodium hydroxide etching2The core is adopted to obtain the polydopamine nano hollow microsphere, and the nano SiO is regulated and controlled2The particle size of the poly-dopamine is controlled, and the shape of the hollow structure of the poly-dopamine is controlled if nano SiO is used2The particle size of (A) is too small, the hollow structure is easy to collapse, and the nano SiO2The particle size of (2) is too large, which results in that the particle size of the nano poly dopamine is increased and the specific surface area is reduced.
According to the nitrogen and sulfur doped porous hollow carbon sphere, the Michael addition reaction is carried out on the polydopamine and the sulfydryl of the benzylmercaptan, so that the benzylmercaptan grafted polydopamine nano hollow microsphere is realized, the polydopamine is used as a carbon source and a nitrogen source, the benzylmercaptan is used as a sulfur source, the nitrogen and sulfur doped porous hollow carbon sphere is obtained through high-temperature carbonization, and further through high-temperature etching of potassium hydroxide, the nitrogen and sulfur doped porous hollow carbon sphere is obtained and used as a lithium ion battery cathode active material, has a unique porous and hollow structure, is larger in specific surface area and rich in pore structure, shortens the diffusion path of lithium ions, promotes the extraction and the insertion of the lithium ions, so that the actual specific capacity of the cathode material is improved, and the nitrogen is doped in the porous hollow carbon sphere in the form of pyrrole nitrogen, pyridine nitrogen and graphite nitrogen, so that the electrochemical property of the porous hollow carbon sphere is improved, and the electronic conductivity and conductivity are higher, the multiplying power performance of the cathode material is improved, sulfur doping is beneficial to expanding the spacing of carbon layers, the pore structure and the specific surface area of the porous hollow carbon spheres are further improved, the exposure of lithium ion de-intercalation sites is more sufficient, and the lithium storage performance is more excellent.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a preparation method of a nitrogen and sulfur doped porous hollow carbon sphere comprises the following steps:
(1) adding distilled water solvent and nano SiO with the particle size of 100-500nm into a reaction bottle2Adding an ethanol solution of dopamine hydrochloride after ultrasonic dispersion is uniform, wherein the nano SiO is2The mass ratio of the nano-grade polydopamine nanoparticle to the dopamine hydrochloride is 100:120-180, strong ammonia water is dripped, the concentration of the ammonia water in the total solution is controlled to be 0.4-0.6%, the mixture is stirred at a constant speed for reaction for 24-48h, an acetone solvent is added for standing and sedimentation, and the mixture is centrifugally separated at a low speed, washed and dried to obtain the nano-grade SiO coated polydopamine nano-particle with a shell-core structure2
(2) Coating polydopamine nano particles with nano SiO2Placing the mixture in sodium hydroxide solution, stirring at a constant speed for reaction, etching, and removing nano SiO2And (4) centrifuging the core to remove the solvent, and washing the core with distilled water until the core is neutral to obtain the polydopamine nano hollow microspheres.
(3) Adding ethanol solvent, 100: 200-.
(4) Placing the benzyl mercaptan grafted polydopamine nano hollow microspheres in an atmosphere furnace, and carbonizing at 650-750 ℃ for 2-3h in a nitrogen atmosphere to obtain nitrogen-sulfur doped hollow carbon spheres.
(5) Uniformly grinding the nitrogen-sulfur doped hollow carbon spheres and potassium hydroxide in a mass ratio of 100:150-250, placing the mixture in an atmosphere furnace, etching the mixture at a high temperature of 600-650 ℃ in a nitrogen atmosphere for 1-2h, and washing the mixture to be neutral by using distilled water to obtain the nitrogen-sulfur doped porous hollow carbon spheres which are applied to the lithium ion battery cathode material.
Example 1
(1) Adding distilled water solvent and nano SiO with particle size of 100nm into a reaction bottle2Adding an ethanol solution of dopamine hydrochloride after ultrasonic dispersion is uniform, wherein the nano SiO is2The mass ratio of the nano-grade polydopamine nanoparticle to dopamine hydrochloride is 100:120, dropwise adding concentrated ammonia water, controlling the concentration of the ammonia water in the total solution to be 0.4%, stirring at a constant speed for reaction for 24 hours, adding an acetone solvent, standing for settling, performing low-speed centrifugal separation, washing and drying to obtain the nano-grade SiO coated polydopamine nano-particle with a shell-core structure2
(2) Coating polydopamine nano particles with nano SiO2Placing the mixture in sodium hydroxide solution, stirring at a constant speed for reaction, etching, and removing nano SiO2And (4) centrifuging the core to remove the solvent, and washing the core with distilled water until the core is neutral to obtain the polydopamine nano hollow microspheres.
(3) Adding ethanol solvent, polydopamine nano hollow microspheres and benzyl mercaptan in a mass ratio of 100:200 into a reaction bottle, uniformly dispersing by ultrasonic, uniformly stirring and reacting at 30 ℃ for 15 hours, carrying out reduced pressure distillation to remove the solvent, washing with distilled water and ethanol, and drying to obtain the benzyl mercaptan grafted polydopamine nano hollow microspheres.
(4) And (3) placing the benzyl mercaptan grafted polydopamine nano hollow microspheres in an atmosphere furnace, and carbonizing at 650 ℃ for 2h in a nitrogen atmosphere to obtain nitrogen and sulfur doped hollow carbon spheres.
(5) Uniformly grinding the nitrogen-sulfur doped hollow carbon spheres and potassium hydroxide in a mass ratio of 100:150, placing the mixture in an atmosphere furnace, etching the mixture at a high temperature for 1h at 600 ℃ in a nitrogen atmosphere, and washing the mixture to be neutral by using distilled water to obtain the nitrogen-sulfur doped porous hollow carbon spheres 1.
Example 2
(1) Adding distilled water solvent and nano SiO with particle size of 200nm into a reaction bottle2Adding an ethanol solution of dopamine hydrochloride after ultrasonic dispersion is uniform, wherein the nano SiO is2The mass ratio of the nano-grade polydopamine nanoparticle to dopamine hydrochloride is 100:140, dropwise adding concentrated ammonia water, controlling the concentration of the ammonia water in the total solution to be 0.5%, stirring at a constant speed for reaction for 48 hours, adding an acetone solvent, standing for settling, performing low-speed centrifugal separation, washing and drying to obtain the nano-grade SiO coated polydopamine nano-particle with a shell-core structure2
(2) Coating polydopamine nano particles with nano SiO2Placing the mixture in sodium hydroxide solution, stirring at a constant speed for reaction, etching, and removing nano SiO2And (4) centrifuging the core to remove the solvent, and washing the core with distilled water until the core is neutral to obtain the polydopamine nano hollow microspheres.
(3) Adding ethanol solvent, polydopamine nano hollow microspheres and benzyl mercaptan in a mass ratio of 100:250 into a reaction bottle, uniformly dispersing by ultrasonic, uniformly stirring and reacting at a constant speed at 40 ℃ for 20 hours, carrying out reduced pressure distillation to remove the solvent, washing with distilled water and ethanol, and drying to obtain the benzyl mercaptan grafted polydopamine nano hollow microspheres.
(4) And (3) placing the benzyl mercaptan grafted polydopamine nano hollow microspheres in an atmosphere furnace, and carbonizing at 750 ℃ for 2.5h in a nitrogen atmosphere to obtain nitrogen and sulfur doped hollow carbon spheres.
(5) Uniformly grinding the nitrogen-sulfur doped hollow carbon spheres and potassium hydroxide in a mass ratio of 100:180, placing the mixture in an atmosphere furnace, etching the mixture at a high temperature for 2 hours at 600 ℃ in a nitrogen atmosphere, and washing the mixture to be neutral by using distilled water to obtain the nitrogen-sulfur doped porous hollow carbon spheres 2.
Example 3
(1) Adding distilled water solvent and nano SiO with particle size of 200nm into a reaction bottle2Adding an ethanol solution of dopamine hydrochloride after ultrasonic dispersion is uniform, wherein the nano SiO is2The mass ratio of the nano-grade polydopamine nanoparticle to dopamine hydrochloride is 100:160, dropwise adding concentrated ammonia water, controlling the concentration of the ammonia water in the total solution to be 0.5%, stirring at a constant speed for reaction for 36 hours, adding an acetone solvent, standing for settling, performing low-speed centrifugal separation, washing and drying to obtain the nano-grade SiO coated polydopamine nano-particle with a shell-core structure2
(2) Coating polydopamine nano particles with nano SiO2Placing the mixture in sodium hydroxide solution, stirring at a constant speed for reaction, etching, and removing nano SiO2And (4) centrifuging the core to remove the solvent, and washing the core with distilled water until the core is neutral to obtain the polydopamine nano hollow microspheres.
(3) Adding ethanol solvent, polydopamine nano hollow microspheres and benzyl mercaptan in a mass ratio of 100:320 into a reaction bottle, uniformly dispersing by ultrasonic, uniformly stirring and reacting at 40 ℃ for 20 hours, carrying out reduced pressure distillation to remove the solvent, washing with distilled water and ethanol, and drying to obtain the benzyl mercaptan grafted polydopamine nano hollow microspheres.
(4) And (3) placing the benzyl mercaptan grafted polydopamine nano hollow microspheres in an atmosphere furnace, and carbonizing at 700 ℃ for 2.5h in a nitrogen atmosphere to obtain the nitrogen and sulfur doped hollow carbon spheres.
(5) Uniformly grinding the nitrogen-sulfur doped hollow carbon spheres and potassium hydroxide in a mass ratio of 100:220, placing the mixture in an atmosphere furnace, etching the mixture at a high temperature for 1.5h in a nitrogen atmosphere at 620 ℃, and washing the mixture to be neutral by using distilled water to obtain the nitrogen-sulfur doped porous hollow carbon spheres 3.
Example 4
(1) Adding distilled water solvent and nano SiO with particle size of 500nm into a reaction bottle2Adding an ethanol solution of dopamine hydrochloride after ultrasonic dispersion is uniform, wherein the nano SiO is2Adding ammonia water at a mass ratio of 100:180 with dopamine hydrochloride, controlling the concentration of ammonia water in the total solution to be 0.6%, stirring at constant speed for reaction for 48h, adding propaneThe ketone solvent is stood for sedimentation, centrifugally separated at low speed, washed and dried to obtain the polydopamine nano-particle coated nano SiO with the shell-core structure2
(2) Coating polydopamine nano particles with nano SiO2Placing the mixture in sodium hydroxide solution, stirring at a constant speed for reaction, etching, and removing nano SiO2And (4) centrifuging the core to remove the solvent, and washing the core with distilled water until the core is neutral to obtain the polydopamine nano hollow microspheres.
(3) Adding ethanol solvent, polydopamine nano hollow microspheres and benzyl mercaptan in a mass ratio of 100:400 into a reaction bottle, uniformly dispersing by ultrasonic, uniformly stirring and reacting for 25 hours at a constant speed at 50 ℃, removing the solvent by reduced pressure distillation, washing with distilled water and ethanol, and drying to obtain the benzyl mercaptan grafted polydopamine nano hollow microspheres.
(4) And (2) placing the benzyl mercaptan grafted polydopamine nano hollow microspheres in an atmosphere furnace, and carbonizing at 750 ℃ for 3h in a nitrogen atmosphere to obtain nitrogen and sulfur doped hollow carbon spheres.
(5) Uniformly grinding the nitrogen-sulfur doped hollow carbon spheres and potassium hydroxide in a mass ratio of 100:250, placing the mixture in an atmosphere furnace, etching the mixture at a high temperature for 2 hours at 650 ℃ in a nitrogen atmosphere, and washing the mixture to be neutral by using distilled water to obtain the nitrogen-sulfur doped porous hollow carbon spheres 4.
Comparative example 1
(1) Adding distilled water solvent and nano SiO with particle size of 50nm into a reaction bottle2Adding an ethanol solution of dopamine hydrochloride after ultrasonic dispersion is uniform, wherein the nano SiO is2Dropping concentrated ammonia water with the mass ratio of 1:1 to dopamine hydrochloride, controlling the concentration of the ammonia water in the total solution to be 0.6%, stirring at a constant speed for reaction for 48 hours, adding an acetone solvent, standing for settling, performing low-speed centrifugal separation, washing and drying to obtain the poly-dopamine nano particle coated nano SiO with the shell-core structure2
(2) Coating polydopamine nano particles with nano SiO2Placing the mixture in sodium hydroxide solution, stirring at a constant speed for reaction, etching, and removing nano SiO2And (4) centrifuging the core to remove the solvent, and washing the core with distilled water until the core is neutral to obtain the polydopamine nano hollow microspheres.
(3) Adding ethanol solvent, polydopamine nano hollow microspheres and benzyl mercaptan in a mass ratio of 100:150 into a reaction bottle, uniformly dispersing by ultrasonic, uniformly stirring and reacting for 25 hours at 30 ℃, removing the solvent by reduced pressure distillation, washing with distilled water and ethanol, and drying to obtain the benzyl mercaptan grafted polydopamine nano hollow microspheres.
(4) And (2) placing the benzyl mercaptan grafted polydopamine nano hollow microspheres in an atmosphere furnace, and carbonizing at 750 ℃ for 3h in a nitrogen atmosphere to obtain nitrogen and sulfur doped hollow carbon spheres.
(5) Uniformly grinding the nitrogen-sulfur doped hollow carbon spheres and potassium hydroxide in a mass ratio of 100:120, placing the mixture in an atmosphere furnace, etching the mixture at a high temperature for 2 hours at 620 ℃ in a nitrogen atmosphere, and washing the mixture to be neutral by using distilled water to obtain a nitrogen-sulfur doped porous hollow carbon sphere contrast 1.
Placing nitrogen-sulfur doped porous hollow carbon spheres, conductive agent carbon black and adhesive polyvinylidene fluoride in an N-methyl pyrrolidone solvent according to a mass ratio of 80:10:10, coating slurry on a copper foil current collector, drying and punching an electrode plate to obtain a working negative electrode of the lithium ion battery, taking a lithium sheet as a working positive electrode, taking a diaphragm as a polypropylene porous membrane and taking 1mol/L electrolyte of LiPF6And (3) assembling the solution and the battery shell into a CR2026 type button battery, and performing cyclic voltammetry test and battery performance test in a CHI760D electrochemical workstation, wherein the test standard is GB/T2433and 2019.
Figure BDA0002872562210000081

Claims (6)

1. A nitrogen and sulfur doped porous hollow carbon sphere is characterized in that: the preparation method of the nitrogen and sulfur doped porous hollow carbon sphere comprises the following steps:
(1) adding nano SiO into distilled water solvent2Adding an ethanol solution of dopamine hydrochloride after uniform ultrasonic dispersion, dropwise adding concentrated ammonia water, controlling the concentration of the ammonia water in the total solution to be 0.4-0.6%, and reacting for 24-48h to obtain the polydopamine nano-particle coated nano SiO with the shell-core structure2
(2) Coating polydopamine nano particles with nano SiO2Placing in sodium hydroxide solution, reacting, etching, and removing nanometer SiO2A core is adopted to obtain the polydopamine nano hollow microsphere;
(3) adding the polydopamine nano hollow microspheres and benzyl mercaptan into an ethanol solvent, uniformly dispersing by ultrasonic, and reacting for 15-25h at 30-50 ℃ to obtain the benzyl mercaptan grafted polydopamine nano hollow microspheres;
(4) placing the benzyl mercaptan grafted polydopamine nano hollow microspheres in an atmosphere furnace for high-temperature carbonization to obtain nitrogen and sulfur doped hollow carbon spheres;
(5) uniformly grinding the nitrogen-sulfur doped hollow carbon spheres and potassium hydroxide, placing the mixture in an atmosphere furnace for high-temperature etching, and washing the mixture to be neutral by using distilled water to obtain the nitrogen-sulfur doped porous hollow carbon spheres which are applied to the negative electrode material of the lithium ion battery.
2. The nitrogen and sulfur doped porous hollow carbon sphere of claim 1, wherein: the nano SiO in the step (1)2The particle size of the compound is 100-500nm, and the mass ratio of the compound to the dopamine hydrochloride is 100: 120-180.
3. The nitrogen and sulfur doped porous hollow carbon sphere of claim 1, wherein: the mass ratio of the polydopamine nano hollow microspheres to the benzylmercaptan in the step (3) is 100: 200-400.
4. The nitrogen and sulfur doped porous hollow carbon sphere of claim 1, wherein: the high-temperature carbonization in the step (4) is carried out in a nitrogen atmosphere and is carbonized at the temperature of 650-750 ℃ for 2-3 h.
5. The nitrogen and sulfur doped porous hollow carbon sphere of claim 1, wherein: the mass ratio of the nitrogen-sulfur doped hollow carbon spheres to the potassium hydroxide in the step (5) is 100: 150-250.
6. The nitrogen and sulfur doped porous hollow carbon sphere of claim 1, wherein: and (5) etching at 600-650 ℃ for 1-2h in a nitrogen atmosphere.
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