CN108448101B - Lithium-sulfur battery positive electrode material and preparation method and application thereof - Google Patents

Lithium-sulfur battery positive electrode material and preparation method and application thereof Download PDF

Info

Publication number
CN108448101B
CN108448101B CN201810335320.0A CN201810335320A CN108448101B CN 108448101 B CN108448101 B CN 108448101B CN 201810335320 A CN201810335320 A CN 201810335320A CN 108448101 B CN108448101 B CN 108448101B
Authority
CN
China
Prior art keywords
lithium
positive electrode
sulfur
sulfur battery
hollow carbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810335320.0A
Other languages
Chinese (zh)
Other versions
CN108448101A (en
Inventor
邹继兆
余良
曾燮榕
曾绍忠
黎晓华
姚跃超
刘世钰
涂文烜
陈双双
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen University
Original Assignee
Shenzhen University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen University filed Critical Shenzhen University
Priority to CN201810335320.0A priority Critical patent/CN108448101B/en
Publication of CN108448101A publication Critical patent/CN108448101A/en
Application granted granted Critical
Publication of CN108448101B publication Critical patent/CN108448101B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a lithium-sulfur battery positive electrode material, a preparation method thereof, a lithium-sulfur battery positive electrode and a lithium-sulfur battery. The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps: preparing a hollow carbon nano microsphere precursor; carbonizing and activating the hollow carbon nano microsphere precursor; depositing sulfur simple substance in the nitrogen-doped hollow carbon nano-microsphere for carbonization and activation treatment. The lithium-sulfur battery anode material prepared by the preparation method has large specific surface area, good wettability and high elemental sulfur content, remarkably improves the sulfur fixation performance, and effectively inhibits the electrochemical performance such as shuttle effect of polysulfide. The lithium-sulfur battery positive electrode and the lithium-sulfur battery contain the lithium-sulfur battery positive electrode material prepared by the method.

Description

Lithium-sulfur battery positive electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrode materials, in particular to a lithium-sulfur battery positive electrode material and a preparation method and application thereof.
Background
In order to cope with the increasing energy consumption demand of society, countries have vigorously developed renewable energy sources to gradually replace existing fossil energy sources. And energy storage and conversion devices play a key role in energy management. Secondary batteries are currently the most widely used energy storage devices, with lithium ion batteries occupying the major market due to their higher energy density (150-. However, as the actual energy density of the current lithium ion battery is very close to the theoretical energy density, huge breakthrough is difficult to generate.
Lithium sulfur batteries, in recent years, have been considered to be energy storage devices with great potential for development. The elemental sulfur has wide source, low price and environmental protection, the theoretical specific capacity of the elemental sulfur reaches 1675mAh/g, and the material is far higher than the most advanced lithium ion battery anode material at present. Despite its many advantages, lithium sulfur batteries have very poor cycling performance compared to lithium ion batteries.
Various materials are used to improve the performance of the sulfur positive electrode, and among them, carbon materials having good conductivity and large specific surface area and pore volume are considered as very promising positive electrode materials for lithium sulfur batteries. Carbon-based materials such as activated carbon, carbon nanotubes, graphene and the like have excellent conductivity, and the conductivity of the lithium-sulfur battery cathode material can be greatly improved by compounding the carbon material with sulfur, and the dissolution of polysulfide can be reduced due to the adsorption of carbon. The hollow carbon nano-microsphere not only has the advantages of low density, good surface permeability, large total pore volume and the like of hollow particles, but also has the characteristics of large specific surface area, high stability, porosity and the like of a carbon nano-material, so the hollow carbon nano-microsphere is considered to have a huge application prospect in the aspect of energy storage.
The traditional method for preparing the hollow carbon nano-microsphere comprises the following steps: firstly preparing SiO2And (3) waiting for the spherical template, then wrapping a precursor of the carbon material on the template, carbonizing the precursor, and corroding the template by using strong corrosive chemicals such as HF acid and the like to obtain a small amount of hollow carbon nano microspheres. The traditional hard template method for preparing the hollow carbon nano microspheres has the disadvantages of tedious process, long time consumption, low yield and high risk of chemicals. And the hollow carbon nano-microsphere prepared by the existing method has poor wettability, and the surface area utilization rate and the electrochemical performance are not ideal, so that the lithium-sulfur positive electrode material formed by the hollow carbon nano-microsphere prepared by the existing hard template method has non-ideal electrochemical performance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a lithium-sulfur battery positive electrode material and a preparation method thereof, so as to solve the technical problem that the electrochemical performance of the lithium-sulfur positive electrode material formed by the existing hollow carbon nano microspheres is not ideal.
The invention also aims to provide a lithium-sulfur battery positive electrode and a lithium-sulfur battery, so as to solve the technical problems of low initial charge-discharge capacity and rate capability and unsatisfactory cycle stability of the lithium-sulfur battery due to the lithium-sulfur positive electrode material of the conventional lithium-sulfur battery positive electrode and lithium-sulfur battery.
In order to achieve the above object, according to one aspect of the present invention, a method for preparing a positive electrode material for a lithium-sulfur battery is provided. The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
carrying out polymerization reaction on pyrrole and aniline in an aqueous solution containing a soft template to obtain a hollow carbon nano microsphere precursor;
washing and pulverizing the hollow carbon nano microsphere precursor, and then carrying out carbonization treatment and ammonia water activation treatment to obtain the nitrogen-doped hollow carbon nano microsphere;
and (2) mixing the aza hollow carbon nano-microspheres with elemental sulfur, and then carrying out heat treatment in a closed environment to volatilize the elemental sulfur and deposit the elemental sulfur in the nitrogen-doped hollow carbon nano-microspheres.
In another aspect of the present invention, a positive electrode material for a lithium-sulfur battery is provided. The lithium-sulfur battery positive electrode material is prepared by the preparation method of the lithium-sulfur battery positive electrode material.
In yet another aspect of the present invention, a lithium sulfur battery positive electrode is provided. The positive electrode of the lithium-sulfur battery comprises a current collector and a positive active layer combined on the current collector, wherein the positive active layer comprises a sulfur positive electrode material, a conductive agent and a binder, and the sulfur positive electrode material is the lithium-sulfur positive electrode material.
In yet another aspect of the present invention, a lithium sulfur battery is provided. The lithium-sulfur battery comprises a positive electrode and a negative electrode, and the positive electrode is the positive electrode of the lithium-sulfur battery.
Compared with the prior art, the preparation method of the lithium-sulfur battery cathode material directly disperses pyrrole and aniline in the aqueous solution containing the soft template for polymerization reaction to directly obtain the hollow carbon nano microsphere precursor, and then sintering and depositing elemental sulfur are carried out, so that the preparation method is relatively simple in process, easy to control conditions and high in efficiency, the prepared hollow carbon nano microsphere precursor is uniform in size and controllable in spherical shell thickness, and the precursor contains abundant nitrogen elements. After the carbonization treatment, the ammonia water activation treatment and the deposition of elemental sulfur are carried out, the prepared lithium-sulfur battery anode material has larger specific surface area, good wettability and high elemental sulfur content, the sulfur fixation performance is obviously improved, and the electrochemical performance such as shuttle effect of polysulfide and the like is effectively inhibited.
The lithium-sulfur battery anode material has a porous structure, and the surface of the anode material contains nitrogen functional groups and oxygen functional groups, and the elemental sulfur can be uniformly deposited inside and outside the porous structure of the nitrogen-oxygen doped hollow carbon nano-microsphere. Therefore, the lithium-sulfur battery positive electrode material has large specific surface area, good wettability and high elemental sulfur content, remarkably improves the sulfur fixation performance, and effectively inhibits the electrochemical performance such as shuttle effect of polysulfide.
The lithium-sulfur battery positive electrode and the lithium-sulfur battery contain the lithium-sulfur battery positive electrode material, so the lithium-sulfur battery positive electrode and the lithium-sulfur battery have high specific capacitance, and also have good rate performance and cycling stability.
Drawings
FIG. 1 is a schematic diagram of a precursor of a hollow carbon nanosphere prepared according to an embodiment of the present invention;
fig. 2 is a Scanning Electron Microscope (SEM) image of the hollow carbon nanosphere precursor prepared in example 1 of the present invention.
Fig. 3 is a Scanning Electron Microscope (SEM) picture of the sulfur-loaded nitrogen-doped carbon hollow carbon nanosphere material prepared in example 1 of the present invention, that is, the positive electrode material of the lithium-sulfur battery prepared in example 1;
FIG. 4 is a physical adsorption curve (BET) of nitrogen-doped hollow carbon nanospheres prepared in example 1 of the present invention;
FIG. 5 is a pore size distribution curve of nitrogen-doped hollow carbon nanospheres prepared in example 1 of the present invention;
fig. 6 is an X-ray photoelectron spectroscopy (XPS) image of the nitrogen-doped hollow carbon nanosphere prepared in example 1 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the invention belong. If a definition set forth in this section is contrary to or otherwise inconsistent with a definition set forth in the patents, patent applications, published patent applications, and other publications that are herein incorporated by reference, the definition set forth in this section prevails over the definition that is incorporated herein by reference.
In addition, the weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, it is within the scope of the disclosure of the description of the embodiments of the present invention to scale up or down the content of the related components according to the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiments of the present invention may be a unit of weight known in the chemical industry, such as μ g, mg, g, and kg.
In one aspect, embodiments of the present invention provide a method for preparing a positive electrode material of a lithium-sulfur battery. The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
step S01, preparing a hollow carbon nano microsphere precursor:
carrying out polymerization reaction on pyrrole and aniline in an aqueous solution containing a soft template to obtain a hollow carbon nano microsphere precursor;
s02, carbonizing and activating the hollow carbon nano microsphere precursor:
washing and pulverizing the hollow carbon nano microsphere precursor, and then carrying out carbonization treatment and ammonia water activation treatment to obtain the nitrogen-doped hollow carbon nano microsphere;
s03, depositing a sulfur simple substance in the nitrogen-doped hollow carbon nano-microspheres for carbonization and activation treatment:
and (2) mixing the aza hollow carbon nano-microspheres with elemental sulfur, and then carrying out heat treatment in a closed environment to volatilize the elemental sulfur and deposit the elemental sulfur in the nitrogen-doped hollow carbon nano-microspheres.
The method for polymerizing pyrrole and aniline in the aqueous solution containing the soft template in step S01 may be performed according to the following steps:
and adding the pyrrole and the aniline into the aqueous solution containing the soft template, then adding an initiator and carrying out polymerization reaction at 0-5 ℃.
In the first step, the concentration of pyrrole is controlled to be 0.3-0.6% by mass in the aqueous solution containing the soft template, and the concentration of aniline is 0.4-0.8% by mass in the aqueous solution containing the soft template. By controlling the concentration of the reactant, the polymerization reaction efficiency is effectively improved, and the particle size of the precursor of the hollow carbon nano microsphere can be effectively controlled and adjusted by controlling and adjusting the concentration of the reactant.
In a further embodiment, the initiator in the polymerization reaction is at least one of ammonium persulfate, potassium persulfate. In addition, the mass concentration of the initiator in the aqueous solution containing the soft template is 8-16%. The efficiency of the polymerization reaction between reactants and the yield of the polymer are improved by controlling the type and the content of the initiator.
In the polymerization reaction system in each of the above embodiments, due to the characteristics of the soft template, the soft template is added into the aqueous solution to form spherical droplets in the solution, such as the droplets shown in a in fig. 1, and after the aniline and pyrrole monomers are added, the aniline and pyrrole monomers enter the droplets of the soft template due to the hydrophobic characteristics thereof, such as shown in B in fig. 1, and after the initiator is further added, the aniline and the pyrrole monomers diffuse to the surface of the droplets of the soft template to react with the initiator in the water, specifically, the pyrrole undergoes a polymerization reaction under the action of the initiator to form polypyrrole, and the aniline undergoes a polymerization reaction under the action of the initiator to form polyaniline, so that after the polymerization reaction, the formed polymer is a mixture polymer of polyaniline and polypyrrole, specifically, a polymer coating layer is formed on the surface of the droplets of the soft template, that is hollow microspheres with polyaniline-polypyrrole as a protective layer (black part in the figure), as shown at C in fig. 1.
In step S01, in one embodiment, the mass ratio of the soft template to water in the reaction solution is (0.5-2): (70-99.5), and specifically, the soft template is triton X-100.
In addition, the reaction of the polymerization reactant such as aniline and the initiator in each of the above embodiments is very fast, so that the temperature of the polymerization reaction is controlled to be 0-5 ℃, and the polymerization rate of the polymer monomer is controlled by controlling the reaction temperature, so that the generated polymer can effectively coat the soft template, thereby generating the target hollow carbon nano microsphere precursor.
In the step S02, the hollow carbon nanosphere precursor is washed to remove the unreacted reactant and solvent residue, so that any washing method capable of removing the reactant and solvent residue is within the scope disclosed herein as long as the hollow carbon nanosphere precursor is not affected.
The pulverization treatment of the washed hollow carbon nano microsphere precursor can be carried out by a conventional method, for example, the hollow carbon nano microsphere precursor is pulverized according to the requirement of particle size.
In step S02, the carbonization treatment may be a conventional carbonization treatment, that is, the hollow carbon nanoparticle precursor after the pulverization treatment is thermally cracked, so as to crack the polymer to generate carbon. In one embodiment, the temperature of the carbonization treatment may be 700-1000 ℃. In addition, the carbonization treatment should be sufficient, for example, in an embodiment, the heat treatment time at 700-. In addition, the heat treatment temperature is controlled to be raised to 700-1000 ℃ at a temperature raising rate of 2-10 ℃/min. Therefore, the hollow carbon nano microsphere particles generated by carbonization are ensured to be complete and have a porous structure by controlling the temperature rise rate.
In one embodiment, the ammonia activation treatment is to perform heat treatment on the hollow carbon nano microsphere particles generated by carbonization in a protective atmosphere at the temperature of 700-1000 ℃; and the protective atmosphere contains a mixed gas of ammonia and water vapor generated by thermal decomposition of ammonia water. The hollow carbon nano microsphere particles are activated by ammonia gas, so that abundant nitrogen-containing functional groups and oxygen-containing functional groups are generated on the surfaces of the hollow carbon nano microsphere particles generated by carbonization, extra Faraday pseudo capacitance can be increased due to the existence of the nitrogen-containing functional groups and the oxygen-containing functional groups, the wettability of the surfaces of the hollow carbon nano microsphere particles is improved, the specific surface utilization rate of the hollow carbon nano microsphere particles is improved, the diffusion resistance of ions in electrolyte in material pores is reduced, lone-pair electrons can be provided, the transmission rate of the electrons in the material is increased, the ions in the electrolyte are attracted, the concentration of double electric layers is increased, and the electrochemical performance of the material is improved.
In a preferred embodiment, the carbonization treatment and the ammonia activation treatment are carried out by the following methods:
in protective atmosphere, carrying out heat treatment on the hollow carbon nano microsphere precursor subjected to pulverization treatment at the temperature of 700-1000 ℃; and the protective atmosphere contains a mixed gas of ammonia and water vapor generated by thermal decomposition of ammonia water. Thus, the carbonization treatment and the activation treatment are arranged in the same atmosphere for treatment, so that not only can abundant nitrogen-containing and oxygen-containing functional groups be generated on the surfaces of the hollow carbon nano microsphere particles generated by the carbonization treatment, the wettability of the hollow carbon nano microsphere particles is improved, but also the sulfur fixing performance can be achieved, and the shuttle effect of polysulfide in the charging and discharging process of the lithium sulfur battery is obviously improved; on the other hand, the porous structure on the surface of the lithium sulfur battery can be effectively improved, so that the pores of the porous structure have gradient pore diameters, such as a multi-level pore structure containing micropores, mesopores and macropores, of course, the porous structures with different pore diameters are randomly distributed, the porous structure with the porous pore diameter distribution can improve the content of the loaded elemental sulfur and the rate capability of the lithium sulfur battery in a synergistic effect, and can also improve the electrochemical properties such as cycling stability and the like.
In addition, the protective atmosphere for the carbonization or activation treatment may be provided by argon, and ammonia gas and water vapor volatilized by heating by introducing ammonia gas into the protective atmosphere may be introduced with the argon gas. As in one embodiment, the flow rate of argon may be set to 20-100ml/min, and the ammonia gas and water vapor should be sufficient for volatilization.
In the step S03, the elemental sulfur may volatilize after being heated, and then may be deposited on the surface of the nitrogen-doped hollow carbon nanospheres and in the porous structure thereof, so that the elemental sulfur may uniformly perform a rechecking with the nitrogen-doped hollow carbon nanospheres, thereby achieving the electrochemical performance of the positive electrode material of the lithium-sulfur battery. In one embodiment, the weight ratio of the nitrogen-doped hollow carbon nano-microsphere to elemental sulfur is controlled to be (3-8): (4-8); in another embodiment, the temperature of the heat treatment, i.e. the temperature for controlling the volatilization of the elemental sulfur is 150-.
In one embodiment, the nitrogen-doped hollow carbon nano-microspheres and elemental sulfur are fully ground and mixed uniformly in a CS2 solution, and then the mixture is placed in a closed container, and the sulfur is volatilized at a high temperature such as 150-250 ℃ and fully enters the pores of the hollow carbon nano-microspheres.
Therefore, the preparation method of the lithium-sulfur battery anode material has the advantages that the preparation process of the lithium-sulfur battery anode material is relatively simple, the conditions are easy to control, the efficiency is high, the defects of the existing hard template method are effectively avoided, the particle size of the prepared lithium-sulfur battery anode material can be controlled, the surface of the lithium-sulfur battery anode material contains a porous structure and is bonded with abundant nitrogen-containing functional groups and oxygen-containing functional groups, the lithium-sulfur battery anode material is endowed with a large specific surface area, good wettability and high elemental sulfur content, the sulfur fixing performance is remarkably improved, and the electrochemical performance such as shuttle effect of polysulfide is effectively inhibited.
Based on the preparation method of the lithium-sulfur battery cathode material, the embodiment of the invention also provides a lithium-sulfur battery cathode material, and specifically, the lithium-sulfur battery cathode material is prepared by the preparation method of the lithium-sulfur battery cathode material. Therefore, the lithium-sulfur battery cathode material has a porous structure, and the porous structure can be a multi-level pore structure with randomly distributed unequal pore diameters, such as a multi-level pore structure containing micropores, mesopores and macropores, and elemental sulfur is deposited in the porous structure or further outside the porous structure; on the other hand, the lithium-sulfur battery positive electrode material is doped with nitrogen and oxygen elements, has good wettability and high elemental sulfur content, remarkably improves the sulfur fixation performance, and effectively inhibits the electrochemical performance such as shuttle effect of polysulfide and the like. The lithium-sulfur battery positive electrode material has the structural characteristics, so that the lithium-sulfur battery positive electrode material has electrochemical properties such as high rate performance, cycling stability and the like. Through determination, the particle size of the lithium-sulfur battery positive electrode material is 50-150 nanometers.
On the other hand, based on the lithium-sulfur battery positive electrode material and the preparation method thereof, the embodiment of the invention also provides a lithium-sulfur battery positive electrode. The lithium sulfur battery positive electrode may include necessary components of the lithium sulfur battery positive electrode, such as a current collector and a positive active layer bonded on the current collector.
The current collector may be a commonly used positive current collector material, such as aluminum foil.
The positive electrode active layer may include a sulfur positive electrode material, a conductive agent, and a binder. Wherein, the weight ratio of the sulfur anode material, the conductive agent and the binder can be (60-90): (5-20): (5-20). The binder may be, but is not limited to PVDF, and the conductive agent may be, but is not limited to acetylene black. The electrode material is the above-described positive electrode material for a lithium-sulfur battery. Therefore, based on the characteristics of the above-described positive electrode material for lithium sulfur batteries. The lithium-sulfur battery positive electrode has high rate performance and initial charge-discharge capacity, and also has good cycle stability.
On the basis of the lithium-sulfur battery positive electrode, the embodiment of the invention also provides a lithium-sulfur battery. The lithium sulfur battery comprises necessary components, such as a positive electrode and a negative electrode, wherein the positive electrode is the positive electrode of the lithium sulfur battery of the embodiment of the invention. Thus, the lithium-sulfur battery has high rate performance and initial charge-discharge capacity, and also has good cycle stability.
The present invention will now be described in further detail with reference to specific lithium-sulfur battery positive electrode materials, methods of making the same, and applications thereof.
1. Lithium-sulfur battery positive electrode material and preparation method embodiment thereof
Example 1
The embodiment provides a lithium-sulfur battery cathode material and a preparation method thereof. The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
s11: adding 0.45g of 2 ℃ Triton X-100 solution into 450g of 2 ℃ deionized water, stirring for 60 minutes by using a magnetic stirrer, and uniformly mixing to form diluted Triton X-100 solution;
s12: 2.2g of pyrrole at the temperature of 2 ℃ and 2.8g of aniline at the temperature of 2 ℃ are added into the diluted triton X-100 solution prepared in the step, and the mixture is continuously stirred for 30min, so that the pyrrole and the aniline are uniformly distributed in the triton X-100 solution;
s13: adding newly prepared 60mL of 1M ammonium persulfate solution into the solution obtained in the step S12, slightly stirring for 30S, and then standing and reacting for 12h at the ambient temperature of 0 ℃;
s14: washing the product obtained in the step S13 for multiple times, performing suction filtration until the filtrate is nearly colorless, drying, grinding into powder to obtain the required hollow carbon nano microsphere precursor, and then sealing and storing the carbon nano microsphere precursor for later use;
s15: putting 1.5g of hollow carbon nano microsphere precursor into a corundum crucible, putting the crucible into a tubular furnace, introducing ammonia gas decomposed by heated ammonia water (50 ℃) and steam into the tubular furnace by using argon gas with the flow of 50ml/min, wherein the tubular furnace is filled with mixed gas of the argon gas, the steam and the ammonia gas;
s16: heating the tube furnace from room temperature at a heating rate of 5 ℃/min to 950 ℃, preserving the heat for 40min, and then cooling to room temperature to obtain the lithium-sulfur battery cathode material;
s17: 160mg of nitrogen-doped hollow carbon nano-microspheres and 240mg of elemental sulfur are fully ground in a mortar, and 4mL of CS is added2The solution is continued to grind until CS2And (3) putting the mixture into a closed container after complete volatilization, and preserving heat at 155 ℃ for 12 hours to ensure that sulfur is volatilized fully and enters pores of the hollow carbon nano microspheres to obtain the sulfur-loaded nitrogen-doped hollow carbon nano microspheres, namely the lithium-sulfur battery cathode material.
Example 2
The embodiment provides a lithium-sulfur battery cathode material and a preparation method thereof. The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
s11: adding 0.5g of Triton X-100 solution at the temperature of 0 ℃ into 450g of deionized water at the temperature of 0 ℃, and stirring for 30 minutes by using a magnetic stirrer to uniformly mix to form diluted Triton X-100 solution;
s12: 2.4g of pyrrole at the temperature of 0 ℃ and 3.0g of aniline at the temperature of 0 ℃ are added into the diluted triton X-100 solution prepared in the step, and the mixture is continuously stirred for 30min, so that the pyrrole and the aniline are uniformly distributed in the triton X-100 solution;
s13: adding 50mL of newly prepared 1M ammonium persulfate solution into the solution obtained in the step S12, slightly stirring for 30S, and then standing and reacting for 15h at the ambient temperature of 0 ℃;
s14: washing the product obtained in the step S13 for multiple times, performing suction filtration until the filtrate is nearly colorless, drying, grinding into powder to obtain the required hollow carbon nano microsphere precursor, and then sealing and storing the carbon nano microsphere precursor for later use;
s15: putting 1.5g of hollow carbon nano microsphere precursor into a corundum crucible, putting the crucible into a tubular furnace, introducing ammonia gas decomposed by heated ammonia water (40 ℃) and steam into the tubular furnace by using argon gas with the flow rate of 60ml/min, wherein the tubular furnace is filled with mixed gas of the argon gas, the steam and the ammonia gas;
s16: heating the tube furnace from room temperature at a heating rate of 4 ℃/min to 900 ℃, preserving the heat for 50min, and then cooling to room temperature to obtain the nitrogen-doped hollow carbon nano-microspheres;
s17: taking 150mg of nitrogen-doped hollow carbon nano-microspheres and 250mg of elemental sulfur, fully grinding in a mortar, and adding 4mL of CS2The solution is continued to grind until CS2And (3) after complete volatilization, putting the mixture into a closed container, and keeping the temperature at 200 ℃ for 12h to ensure that sulfur volatilizes and fully enters pores of the hollow carbon nano microspheres to obtain the sulfur-loaded nitrogen-doped hollow carbon nano microspheres, namely the lithium-sulfur battery cathode material.
Example 3
The embodiment provides a lithium-sulfur battery cathode material and a preparation method thereof. The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
s11: adding 0.40g of triton X-100 solution with the temperature of 1 ℃ into 450g of deionized water with the temperature of 1 ℃, and stirring for 60 minutes by using a magnetic stirrer to uniformly mix to form diluted triton X-100 solution;
s12: adding 1.5g of pyrrole at the temperature of 1 ℃ and 1.8 g of aniline at the temperature of 1 ℃ into the diluted triton X-100 solution prepared in the step, and continuing stirring for 20min to uniformly distribute the pyrrole and the aniline in the triton X-100 solution;
s13: adding newly prepared 45mL of 1M ammonium persulfate solution into the solution obtained in the step S12, slightly stirring for 50S, and then standing and reacting for 10h at the ambient temperature of 1 ℃;
s14: washing the product obtained in the step S13 for multiple times, performing suction filtration until the filtrate is nearly colorless, drying, grinding into powder to obtain the required hollow carbon nano microsphere precursor, and then sealing and storing the carbon nano microsphere precursor for later use;
s15: putting 2.0g of hollow carbon nano microsphere precursor into a corundum crucible, putting the crucible into a tubular furnace, introducing ammonia gas decomposed by heated ammonia water (65 ℃) and steam into the tubular furnace by using argon gas with the flow rate of 35ml/min, wherein the tubular furnace is filled with mixed gas of the argon gas, the steam and the ammonia gas;
s16: heating the tube furnace from room temperature at the heating rate of 6 ℃/min to 850 ℃, preserving the heat for 65min, and then cooling to room temperature to obtain the nitrogen-doped hollow carbon nano-microspheres;
s17: and heating the mixture in a tubular furnace from room temperature at the heating rate of 6 ℃/min to 850 ℃, preserving the heat for 65min, and then cooling the mixture to room temperature to obtain the nitrogen-doped hollow carbon nano-microspheres.
Example 4
The embodiment provides a lithium-sulfur battery cathode material and a preparation method thereof. The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
s11: adding 0.55g of 2 ℃ Triton X-100 solution into 450g of 2 ℃ deionized water, and stirring for 30min by using a magnetic stirrer to uniformly mix to form diluted Triton X-100 solution;
s12: 2.0g of pyrrole at the temperature of 2 ℃ and 2.0g of aniline at the temperature of 2 ℃ are added into the diluted triton X-100 solution prepared in the step, and the mixture is continuously stirred for 35min, so that the pyrrole and the aniline are uniformly distributed in the triton X-100 solution;
s13: adding 63mL of newly prepared 1M ammonium persulfate solution into the solution obtained in the step S12, slightly stirring for 25S, and then standing and reacting for 12h at the ambient temperature of 0 ℃;
s14: washing the product obtained in the step S13 for multiple times, performing suction filtration until the filtrate is nearly colorless, drying, grinding into powder to obtain the required hollow carbon nano microsphere precursor, and then sealing and storing the carbon nano microsphere precursor for later use;
s15: putting 1.6g of hollow carbon nano microsphere precursor into a corundum crucible, putting the crucible into a tubular furnace, introducing ammonia gas decomposed by heated ammonia water (25 ℃) and steam into the tubular furnace by using argon gas with the flow rate of 80ml/min, wherein the tubular furnace is filled with mixed gas of the argon gas, the steam and the ammonia gas;
s16: heating the tubular furnace from room temperature at a heating rate of 2 ℃/min to 925 ℃ and preserving heat for 55min, and then cooling to room temperature to obtain the nitrogen-doped hollow carbon nano-microspheres;
s17: taking 120mg of nitrogen-doped hollow carbon nano-microspheres, fully grinding 280mg of elemental sulfur in a mortar, and adding 6mL of CS2The solution is continued to grind until CS2Putting the mixture into a closed container after complete volatilizationAnd keeping the temperature at 170 ℃ for 10h to ensure that the sulfur is volatilized and fully enters pores of the hollow carbon nano-microspheres, thus obtaining the sulfur-loaded nitrogen-doped hollow carbon nano-microspheres.
Example 5
The embodiment provides a lithium-sulfur battery cathode material and a preparation method thereof. The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
s11: adding 0.48g of 2 ℃ Triton X-100 solution into 450g of 2 ℃ deionized water, and stirring for 45min by using a magnetic stirrer to uniformly mix to form diluted Triton X-100 solution;
s12: 2.0g of pyrrole at the temperature of 2 ℃ and 2.6g of aniline at the temperature of 2 ℃ are added into the diluted triton X-100 solution prepared in the step, and the mixture is continuously stirred for 60min, so that the pyrrole and the aniline are uniformly distributed in the triton X-100 solution;
s13: adding the newly prepared 1M ammonium persulfate solution of 42mL into the solution of the step S12, slightly stirring for 45S, and then standing and reacting for 18h at the ambient temperature of 0 ℃;
s14: washing the product obtained in the step S13 for multiple times, performing suction filtration until the filtrate is nearly colorless, drying, grinding into powder to obtain the required hollow carbon nano microsphere precursor, and then sealing and storing the carbon nano microsphere precursor for later use;
s15: putting 1.0g of hollow carbon nano microsphere precursor into a corundum crucible, putting the crucible into a tubular furnace, introducing ammonia gas decomposed by heated ammonia water (35 ℃) and steam into the tubular furnace by using argon gas with the flow rate of 75ml/min, wherein the tubular furnace is filled with mixed gas of the argon gas, the steam and the ammonia gas;
s16: heating the tubular furnace from room temperature at a heating rate of 8 ℃/min to 875 ℃ and preserving the heat for 120min, and then cooling to room temperature to obtain the nitrogen-doped hollow carbon nano-microspheres;
s17: taking 140mg of nitrogen-doped hollow carbon nano-microspheres, fully grinding 260mg of elemental sulfur in a mortar, and adding 4.5ml of CS2The solution is continued to grind until CS2Putting the mixture into a closed container after complete volatilization, and preserving heat at 158 ℃ for 14h to ensure that the sulfur is fully volatilized and enters the hollow carbon nano microspheresThen the nitrogen-doped hollow carbon nano-microsphere loaded with sulfur is obtained.
Further, the hollow carbon nanosphere precursor, the nitrogen-doped carbon hollow carbon nanosphere, and the sulfur-loaded nitrogen-doped carbon hollow carbon nanosphere prepared in embodiments 1 to 5 were subjected to scanning electron microscopy, respectively, wherein a scanning electron microscopy picture of the hollow carbon nanosphere precursor provided in embodiment 1 is shown in fig. 2, and a scanning electron microscopy of the nitrogen-doped carbon hollow carbon nanosphere is shown in fig. 3. As can be seen from fig. 2 and 3, the hollow carbon nanosphere precursor and the nitrogen-doped carbon hollow carbon nanosphere are both in a particle structure, and the particle size has a nanoscale and is uniform in size distribution. Scanning electron microscope scanning is performed on the sulfur-loaded nitrogen-doped carbon hollow carbon nanosphere lithium sulfur battery cathode material prepared in example 1, and it is known that the form and size of the sulfur-loaded nitrogen-doped carbon hollow carbon nanosphere lithium sulfur battery cathode material are substantially the same as those of the nitrogen-doped carbon hollow carbon nanosphere prepared in example 1. Examples 2 to 5 the scanning electron microscope images of the hollow carbon nanosphere precursor, the nitrogen-doped carbon hollow carbon nanosphere, and the sulfur-loaded nitrogen-doped carbon hollow carbon nanosphere were similar to those of example 1.
The nitrogen-doped carbon hollow carbon nanospheres prepared in examples 1 to 5 were further subjected to physical adsorption property and pore size distribution and X-ray photoelectron spectroscopy, wherein the physical adsorption curve (BET) of the nitrogen-doped carbon hollow carbon nanosphere of example 1 is shown in fig. 4, the pore size distribution curve is shown in fig. 5, and the X-ray photoelectron spectroscopy image is shown in fig. 6. As can be seen from FIG. 4, the nitrogen adsorption and desorption curves of the nitrogen-doped carbon hollow carbon nanospheres are typical I/IV type adsorption curves, and are all at low relative pressure (P/P)0<0.05)N2The adsorption quantity is increased sharply and then reaches the equilibrium rapidly, which shows that all the carbon nanobelt microsphere materials have a large number of micropores (< 2nm) structures at P/P0In the area with the range of 0.9-1, the desorption curve of all the carbon nanobelts is obviously lagged behind the adsorption curve, so that a lagged loop is formed, which indicates that a plurality of mesopores (2-50nm) and macropores (larger than 50nm) exist in the hollow carbon nano microsphere. As can be seen from fig. 5, the nitrogen-doped carbon hollow carbon nanospheres have a hierarchical pore structure with micropores, mesopores and macropores distributed therein; from FIG. 6It is known that the nitrogen-doped carbon hollow carbon nanosphere contains C, N, O elements, and therefore, the nitrogen-doped carbon hollow carbon nanosphere contains hydrophilic groups, namely nitrogen groups and oxygen groups.
Examples 2 to 5 the physical adsorption performance and pore size distribution of the sulfur-loaded nitrogen-doped carbon hollow carbon nanospheres and the results of X-ray photoelectron spectroscopy analysis were similar to those of example 1.
2. Lithium sulfur battery positive electrode and lithium sulfur battery examples
Example 6
The present embodiment provides a lithium sulfur battery positive electrode and a lithium sulfur battery.
The lithium sulfur battery of this example includes a positive electrode and other necessary components, wherein the positive electrode is prepared as follows:
160mg of nitrogen-doped hollow carbon nano-microspheres loaded with sulfur, 20mg of PVDF powder and 20mg of acetylene black are uniformly ground in a mortar with 2ml of N-methylpyrrolidone (NMP), then a coating with the thickness of 200 mu m is coated on an aluminum foil, the aluminum foil is placed in a vacuum drying oven and subjected to hollow drying at 60 ℃ for 12 hours, and then a sheet punching machine is used for punching the aluminum foil containing the electrode material into a positive electrode sheet.
Example 7
The present embodiment provides a lithium sulfur battery positive electrode and a lithium sulfur battery.
The lithium sulfur battery of this example includes a positive electrode and other necessary components, wherein the positive electrode is prepared as follows:
170mg of nitrogen-doped hollow carbon nano-microspheres loaded with sulfur, 15mg of PVDF powder and 15mg of acetylene black are uniformly ground in a mortar with 2ml of N-methylpyrrolidone (NMP), then a coating with the thickness of 100 microns is coated on an aluminum foil, the aluminum foil is placed in a vacuum drying oven and subjected to hollow drying at 65 ℃ for 12 hours, and then a sheet punching machine is used for punching the aluminum foil containing the electrode material into a positive electrode sheet.
Example 8
The present embodiment provides a lithium sulfur battery positive electrode and a lithium sulfur battery.
The lithium sulfur battery of this example includes a positive electrode and other necessary components, wherein the positive electrode is prepared as follows:
170mg of nitrogen-doped hollow carbon nano-microspheres loaded with sulfur, 13mg of PVDF powder and 17mg of acetylene black are uniformly ground in a mortar with 2.5ml of N-methylpyrrolidone (NMP), then a coating with the thickness of 50 mu m is coated on an aluminum foil, then the aluminum foil is placed in a vacuum drying oven and is subjected to hollow drying at 80 ℃ for 10 hours, and then a sheet punching machine is used for punching the aluminum foil containing the electrode material into a positive electrode plate.
Example 9
The present embodiment provides a lithium sulfur battery positive electrode and a lithium sulfur battery.
The lithium sulfur battery of this example includes a positive electrode and other necessary components, wherein the positive electrode is prepared as follows:
taking 150 nitrogen-doped hollow carbon nano-microspheres loaded with sulfur, 20mg PVDF powder and 30mg acetylene black, uniformly grinding the materials in a mortar with 3ml of N-methylpyrrolidone (NMP), coating the materials on an aluminum foil to form a 150-micron-thick coating, placing the coating on a vacuum drying oven, drying the coating in the air for 15 hours at 55 ℃, and punching the aluminum foil containing the electrode material into a positive electrode plate by using a punching machine.
Example 10
The present embodiment provides a lithium sulfur battery positive electrode and a lithium sulfur battery.
The lithium sulfur battery of this example includes a positive electrode and other necessary components, wherein the positive electrode is prepared as follows:
the preparation method comprises the steps of uniformly grinding 165mg of sulfur-loaded nitrogen-doped hollow carbon nano-microspheres, 15mg of PVDF powder and 20mg of acetylene black in a mortar with 3.5ml of N-methylpyrrolidone (NMP), coating a 200-micron-thick coating on an aluminum foil, placing the aluminum foil in a vacuum drying oven, drying the aluminum foil in the air at 75 ℃ for 10 hours, and punching the aluminum foil containing the electrode material into a positive electrode plate by using a punching machine.
The lithium sulfur batteries provided in examples 6 to 10 and the lithium sulfur batteries provided in comparative examples were subjected to the relevant electrochemical performance tests, respectively, according to the following measurement methods and results:
the determination method comprises the following steps: the voltage capacity curve of the cathode material at 0.1C rate and the cycle performance of the lithium-sulfur battery containing the cathode material at 0.2C rate were measured.
And (3) measuring results: example 6 provides a lithium sulfur battery at 0.The initial discharge capacity of the electrode under the 1C multiplying power can reach 1238 mA.h.g－1The initial discharge capacity of the electrode can reach 1026mA · h · g at 0.2C multiplying power－1And 452mA · h · g can be still maintained after 400 charge-discharge cycles under the multiplying power of 0.2C－1The capacity of (c).
Examples 7-10 also provide lithium sulfur cells having high electrochemical performance comparable to that of the lithium sulfur cell of example 6.
The prepared cathode material has large pore volume, high nitrogen content and spherical shape, so the prepared cathode material has higher capacity, can effectively inhibit shuttle effect in the charge and discharge process, and has higher capacity and better cycle stability compared with the cathode materials of lithium-sulfur batteries with publication numbers of CN107732202A and CN 107565116A.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (9)

1. A preparation method of a lithium-sulfur battery positive electrode material is characterized by comprising the following steps:
carrying out polymerization reaction on pyrrole and aniline in an aqueous solution containing a soft template to obtain a hollow carbon nano microsphere precursor;
washing and pulverizing the hollow carbon nano microsphere precursor, and then carrying out carbonization treatment and ammonia water activation treatment to obtain the nitrogen-doped hollow carbon nano microsphere;
mixing the nitrogen-doped hollow carbon nano-microspheres with elemental sulfur, and then carrying out heat treatment in a closed environment to volatilize the elemental sulfur and deposit the elemental sulfur in the nitrogen-doped hollow carbon nano-microspheres;
the carbonization treatment and ammonia water activation treatment method comprises the following steps:
in protective atmosphere, carrying out heat treatment on the hollow carbon nano microsphere precursor at the temperature of 700-1000 ℃; and the protective atmosphere contains a mixed gas of ammonia and water vapor generated by thermal decomposition of ammonia water.
2. The method according to claim 1, wherein the pyrrole and aniline are polymerized in an aqueous solution containing a soft template by the following method:
adding the pyrrole and the aniline into an aqueous solution containing the soft template, then adding an initiator and carrying out polymerization reaction at 0-5 ℃; and/or
The mass concentration of the pyrrole in the aqueous solution containing the soft template is 0.3-0.6%, and the mass concentration of the aniline in the aqueous solution containing the soft template is 0.4-0.8%.
3. The method of claim 2, wherein: the initiator is at least one of ammonium persulfate and potassium persulfate; and/or
The mass concentration of the initiator in the aqueous solution containing the soft template is 8-16%.
4. The method of claim 1, wherein: the time of the heat treatment is 20-120 min; and/or
The heat treatment temperature is raised to 700-1000 ℃ at a temperature raising rate of 2-10 ℃/min.
5. The production method according to any one of claims 1 to 4, wherein the mass ratio of the soft template to water in the aqueous solution of the soft template is (0.5 to 2): (70-99.5); and/or
The soft template is Triton X-100.
6. The production method according to any one of claims 1 to 4, characterized in that: the weight ratio of the nitrogen-doped hollow carbon nano microspheres to elemental sulfur is (3-8): (4-8); and/or
The temperature for volatilizing the elemental sulfur is 150-250 ℃.
7. A positive electrode material for a lithium-sulfur battery, which is prepared by the preparation method according to any one of claims 1 to 6.
8. A lithium sulfur battery positive electrode comprising a current collector and a positive active layer bonded on the current collector, characterized in that the positive active layer comprises a sulfur positive electrode material, a conductive agent and a binder, wherein the sulfur positive electrode material is the lithium sulfur positive electrode material according to claim 7.
9. A lithium sulfur battery comprising a positive electrode and a negative electrode, wherein the positive electrode is the lithium sulfur battery positive electrode of claim 8.
CN201810335320.0A 2018-04-12 2018-04-12 Lithium-sulfur battery positive electrode material and preparation method and application thereof Active CN108448101B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810335320.0A CN108448101B (en) 2018-04-12 2018-04-12 Lithium-sulfur battery positive electrode material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810335320.0A CN108448101B (en) 2018-04-12 2018-04-12 Lithium-sulfur battery positive electrode material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN108448101A CN108448101A (en) 2018-08-24
CN108448101B true CN108448101B (en) 2020-06-19

Family

ID=63200020

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810335320.0A Active CN108448101B (en) 2018-04-12 2018-04-12 Lithium-sulfur battery positive electrode material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN108448101B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109244393B (en) * 2018-08-27 2020-12-22 上海电力学院 Long-cycle high-rate-performance lithium-sulfur battery positive electrode material and preparation method thereof
CN109346689A (en) * 2018-09-27 2019-02-15 北京长城华冠汽车科技股份有限公司 A kind of preparation method of the hollow Nano carbon balls combination electrode material of N doping multi-pore channel
CN109980217A (en) * 2019-03-26 2019-07-05 华南理工大学 A kind of flexible self-supporting lithium-sulphur cell positive electrode and preparation method thereof based on natural fiber
CN110085846B (en) * 2019-05-16 2021-04-27 华北水利水电大学 Graphene-silicon dioxide composite aerogel sulfur-carrying material and preparation method and application thereof
CN110970606B (en) * 2019-11-21 2021-11-23 暨南大学 Nitrogen-doped hollow spherical carbon-coated sulfur positive electrode material and preparation method and application thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103949209A (en) * 2013-11-29 2014-07-30 中北大学 Plant based carbon material and preparation method thereof
CN105932230B (en) * 2016-04-27 2018-10-26 长沙矿冶研究院有限责任公司 A kind of nanometer rods porous carbon-sulphur composite positive pole and preparation method thereof, lithium-sulfur cell
CN107325787B (en) * 2017-07-05 2021-01-29 中国石油天然气股份有限公司 Hollow carbon nano-particles and wave-absorbing material prepared from same

Also Published As

Publication number Publication date
CN108448101A (en) 2018-08-24

Similar Documents

Publication Publication Date Title
CN108448101B (en) Lithium-sulfur battery positive electrode material and preparation method and application thereof
Xiao et al. A sulfur host based on cobalt–graphitic carbon nanocages for high performance lithium–sulfur batteries
CN108439369B (en) Nitrogen-oxygen co-doped hollow carbon nano-microsphere as well as preparation method and application thereof
US10978695B2 (en) Anode active material and anode for lithium-ion battery, method for preparing the anode active material, and lithium-ion battery
CN107256956B (en) Nitrogen-doped carbon-coated vanadium nitride electrode material and preparation method and application thereof
CN102916167B (en) Mesoporous silicon compound as lithium ion battery negative material and preparation method thereof
CN108666570B (en) Porous carbon nanobelt lithium-sulfur battery positive electrode material and preparation method and application thereof
CN106784690B (en) A kind of composite positive pole and preparation method thereof and all solid state lithium-sulfur cell
An et al. Dual carbon layer hybridized mesoporous tin hollow spheres for fast-rechargeable and highly-stable lithium-ion battery anodes
CN111362254A (en) Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material
Yin et al. Silicon nanoparticle self-incorporated in hollow nitrogen-doped carbon microspheres for lithium-ion battery anodes
Jiao et al. A controllable strategy for the self-assembly of WM nanocrystals/nitrogen-doped porous carbon superstructures (M= O, C, P, S, and Se) for sodium and potassium storage
CN111276684A (en) Preparation method and application of carbon-coated composite material
CN111785946B (en) Negative active material, preparation and application thereof
CN114122352A (en) Silicon-carbon negative electrode material for inducing silicon deposition by doping porous carbon and preparation method thereof
CN111564610B (en) Carbon-coated cuprous phosphide-copper composite particle modified by carbon nanotube and preparation method and application thereof
CN106848282B (en) Negative electrode material for non-aqueous electrolyte secondary battery and preparation method and application thereof
CN113161533A (en) MOF-derived ZnO @ C composite material and application thereof
Hu et al. Strategy for practically constructing high-capacity sulfur cathode by combining sulfur-hierarchical porous graphitic carbon composite with surface modification of polydopamine
CN112382759B (en) Preparation method of nitrogen-doped porous carbon-coated silicon composite nanofiber
CN117497723A (en) Preparation method of MOF-derived carbon-coated silicon nanoparticle-limited MXene composite anode material of lithium ion battery
Lin et al. A graphene oxide scaffold-encapsulated microcapsule for polysulfide-immobilized long life lithium–sulfur batteries
CN111146423A (en) Pre-lithiated binary topological structure phosphorus/carbon composite material and preparation method and application thereof
CN114920242B (en) Preparation method of high-capacity graphite composite material
CN107611417B (en) Capacity-controllable silicon-based lithium ion battery cathode material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant