CN114086321A - Method for preparing carbon/lithium sulfide composite material based on coaxial electrostatic spinning technology - Google Patents

Method for preparing carbon/lithium sulfide composite material based on coaxial electrostatic spinning technology Download PDF

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CN114086321A
CN114086321A CN202111410542.2A CN202111410542A CN114086321A CN 114086321 A CN114086321 A CN 114086321A CN 202111410542 A CN202111410542 A CN 202111410542A CN 114086321 A CN114086321 A CN 114086321A
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polyvinylpyrrolidone
carbon
molecular weight
composite material
lithium sulfide
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CN114086321B (en
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曹海亮
吴玉程
苗艳勤
吕琛山
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Lei Nengzhi Manufacturing (Zhangjiagang) Technology Co.,Ltd.
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Taiyuan University of Technology
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825—Composite fibres
    • D04H1/43828—Composite fibres sheath-core
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C7/00—Heating or cooling textile fabrics
    • D06C7/04—Carbonising or oxidising
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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

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  • Textile Engineering (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Fibers (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a method for preparing a carbon/lithium sulfide composite material based on a coaxial electrostatic spinning technology, and relates to the field of electrode materials of lithium-sulfur batteries. Mixing low molecular weight polyvinylpyrrolidone with high molecular weight polyvinylpyrrolidone, and adding lithium sulfate to form a core solution for coaxial electrostatic spinning; obtaining a non-woven fabric film by using a coaxial electrostatic spinning technology, carrying out pre-oxidation and carbonization treatment on the non-woven fabric film, and respectively forming holes and channels on a shell and a core by using low-molecular-weight polyvinylpyrrolidone in a carbonization process to obtain a self-supporting shell with multiple holes, wherein the inner core is a multi-channel carbon fiber structure and provides an electron and ion transmission channel; meanwhile, lithium sulfate reacts with carbonized polyvinylpyrrolidone in situ at high temperature to generate lithium sulfide. The method solves the problem of volume expansion of sulfur, does not need to add an adhesive and a conductive agent, does not need to carry sulfur, is nontoxic and harmless, has low cost and is environment-friendly.

Description

Method for preparing carbon/lithium sulfide composite material based on coaxial electrostatic spinning technology
Technical Field
The invention relates to the field of lithium-sulfur battery electrode materials, in particular to a method for preparing a carbon/lithium sulfide composite material based on a coaxial electrostatic spinning technology.
Background
Clean and efficient new energy sources, such as wind energy, water energy and solar energy, have a lot of problems, such as regional influence, low energy conversion rate and the like. The theoretical specific capacity of the lithium-sulfur battery is up to 1672 mAh/g, so that the volume of the lithium-sulfur battery is lighter compared with other lithium ion batteries, and sulfur has the advantages of abundant reserves, low cost, low environmental pollution and the like. However, the lithium sulfur battery has many problems to be solved, such as poor conductivity of elemental sulfur, volume expansion of sulfur during charge and discharge, and shuttling of polysulfide. The carbon nanofiber prepared by the electrostatic spinning technology is applied to the lithium-sulfur battery, has strong structural design, is easy to dope and modify, and can be self-supported without using an adhesive or a conductive agent.
The preparation of the carbon/lithium sulfide composite material is to prepare lithium sulfide first and then compound the lithium sulfide with the porous carbon material. The method has a complex operation process, carbon and lithium sulfide are difficult to be uniformly compounded, and the preparation of the lithium sulfide material has very high requirements on production equipment and environment. According to the patent report of the existing lithium sulfide material preparation, hydrogen sulfide gas is generated or used in the process of producing and preparing lithium sulfide, so that on one hand, the environment is polluted, and on the other hand, the personal safety is threatened. There is a need to improve the existing methods of preparing carbon/lithium sulfide composite materials.
Disclosure of Invention
The invention provides a method for preparing a carbon/lithium sulfide composite material based on a coaxial electrostatic spinning technology, aiming at solving the problems of cost increase, sulfur simple substance expansion and poor conductivity caused by adding a binder and a conductive agent to the conventional lithium-sulfur battery cathode material.
The invention is realized by the following technical scheme: a method for preparing a carbon/lithium sulfide composite material based on a coaxial electrostatic spinning technology comprises the following steps:
(1) adding water and ethanol serving as solvents into low-molecular-weight polyvinylpyrrolidone and high-molecular-weight polyvinylpyrrolidone K90 in a certain mass ratio, and stirring overnight to obtain a shell solution, wherein the low-molecular-weight polyvinylpyrrolidone adopts any one or more of K16-K18 or K30; the low molecular weight polyvinylpyrrolidone generally refers to the average molecular weight of 8000-58000, and the high molecular weight polyvinylpyrrolidone generally refers to the average molecular weight of 1300000;
(2) adding water and ethanol serving as solvents into low-molecular-weight polyvinylpyrrolidone and high-molecular-weight polyvinylpyrrolidone K90 in a certain mass ratio, uniformly stirring, adding lithium sulfate, and stirring overnight to obtain a core solution, wherein the low-molecular-weight polyvinylpyrrolidone adopts any one or more of K16-K18 or K30;
(3) carrying out coaxial electrospinning on the obtained shell solution and the core solution to obtain a non-woven fabric film;
(4) and carrying out pre-oxidation treatment and high-temperature carbonization treatment on the obtained non-woven fabric film to obtain the carbon fiber material with the multi-channel central core and the porous shell.
In summary, the process forms a core solution for coaxial electrospinning by mixing low molecular weight polyvinylpyrrolidone with high molecular weight polyvinylpyrrolidone and adding lithium sulfate. Obtaining a non-woven fabric film by using a coaxial electrostatic spinning technology, carrying out pre-oxidation and carbonization treatment on the non-woven fabric film, and respectively forming holes and channels on a shell and a core by using low-molecular-weight polyvinylpyrrolidone in a carbonization process to obtain a self-supporting shell with multiple holes, wherein the inner core is a multi-channel carbon fiber structure and provides an electron and ion transmission channel; meanwhile, lithium sulfate reacts with carbonized polyvinylpyrrolidone in situ at high temperature to generate lithium sulfide.
Preferably, the mass ratio of the polyvinylpyrrolidone with low molecular weight to the polyvinylpyrrolidone with high molecular weight K90 added in the step (1) is 1: 5 to 4.
Preferably, the mass ratio of the polyvinylpyrrolidone with low molecular weight to the polyvinylpyrrolidone with high molecular weight K90 added in the step (2) is 1: 4 to 2.
Preferably, the total mass concentration of the low molecular weight polyvinylpyrrolidone and the high molecular weight polyvinylpyrrolidone K90 added into the shell solution in the step (1) is 12-14%.
Preferably, the total mass concentration of the polyvinylpyrrolidone with low molecular weight and the polyvinylpyrrolidone with high molecular weight K90 added into the core solution in the step (2) is 10-20%.
Preferably, the mass ratio of water to ethanol in the step (1) and the step (2) is 1.5-1.2: 1.
preferably, the mass of the lithium sulfate added in the step (2) is 0.6 g-1 g.
Preferably, in the step (3), the coaxial electrospinning parameters are as follows: the voltage is 12-18 kV, and the rotating speed of the roller collector is 400-600 r/min.
Preferably, in the step (4), the pre-oxidation process is carried out in the air atmosphere of a muffle furnace, the temperature is 240-270 ℃, the heating rate is 1-3 ℃/min, and the heat preservation time is 2-3 h.
Preferably, in the step (4), the carbonization process is carried out in a tubular furnace under the argon atmosphere, the temperature is 700-900 ℃, the heating rate is 2-5 ℃/min, and the heat preservation time is 1-2 h.
Compared with the prior art, the invention has the following beneficial effects: according to the method for preparing the carbon/lithium sulfide composite material based on the coaxial electrostatic spinning technology, the lithium sulfate and the carbon material are subjected to in-situ reaction to prepare the product, the lithium sulfate is low in cost, the lithium sulfide is prepared by the in-situ reaction of the lithium sulfate, sulfur carrying is not needed, the problem of volume expansion of sulfur is solved, an adhesive and a conductive agent are not needed, and the method is simple, non-toxic, harmless, low in cost and environment-friendly.
Drawings
Fig. 1 is a high-power scan of the carbon/lithium sulfide composite prepared in example 1.
Fig. 2 is a low-power scan of the carbon/lithium sulfide composite prepared in example 2.
Detailed Description
The present invention will be further described with reference to the following specific examples and the accompanying drawings, which are not intended to limit the invention in any way. Unless otherwise indicated, reagents and materials used in the present invention are commercially available.
A method for preparing a carbon/lithium sulfide composite material based on a coaxial electrostatic spinning technology comprises the following steps:
(1) adding water and ethanol serving as solvents into low-molecular-weight polyvinylpyrrolidone and high-molecular-weight polyvinylpyrrolidone K90 in a certain mass ratio, and stirring overnight to obtain a shell solution, wherein the low-molecular-weight polyvinylpyrrolidone adopts any one or more of K16-K18 or K30;
(2) adding water and ethanol serving as solvents into low-molecular-weight polyvinylpyrrolidone and high-molecular-weight polyvinylpyrrolidone K90 in a certain mass ratio, uniformly stirring, adding lithium sulfate, and stirring overnight to obtain a core solution, wherein the low-molecular-weight polyvinylpyrrolidone adopts any one or more of K16-K18 or K30;
(3) carrying out coaxial electrospinning on the obtained shell solution and the core solution to obtain a non-woven fabric film;
(4) and carrying out pre-oxidation treatment and high-temperature carbonization treatment on the obtained non-woven fabric film to obtain the carbon fiber material with the multi-channel central core and the porous shell.
The following examples all employ preferred schemes: adding polyvinylpyrrolidone with low molecular weight and polyvinylpyrrolidone with high molecular weight K90 in the step (1) according to the mass ratio of 1: 5-4, adding polyvinylpyrrolidone with low molecular weight and polyvinylpyrrolidone K90 with high molecular weight into the shell solution, wherein the total mass concentration of the polyvinylpyrrolidone with low molecular weight and the polyvinylpyrrolidone K90 with high molecular weight is 12% -14%; adding the polyvinylpyrrolidone with low molecular weight and the polyvinylpyrrolidone with high molecular weight K90 in the step (2) according to the mass ratio of 1: 4-2, adding 10-20% of polyvinylpyrrolidone with low molecular weight and polyvinylpyrrolidone with high molecular weight K90 into the core solution, wherein the mass of the lithium sulfate added in the step (2) is 0.6-1 g; the mass ratio of water to ethanol in the step (1) and the step (2) is 1.5-1.2: 1; in the step (3), the coaxial electrostatic spinning parameters are as follows: the voltage is 12-18 kV, and the rotating speed of the roller collector is 400-600 r/min; in the step (4), the pre-oxidation process is carried out in the air atmosphere of a muffle furnace, the temperature is 240-270 ℃, the heating rate is 1-3 ℃/min, and the heat preservation time is 2-3 h; and the carbonization process is carried out in a tubular furnace under the argon atmosphere, the temperature is 700-900 ℃, the heating rate is 2-5 ℃/min, and the heat preservation time is 1-2 h. In the following examples: the low molecular weight polyvinylpyrrolidone used was K30.
Example 1:
step 1: 10g of a mixture of water and ethanol as a solvent (water to ethanol mass ratio: 1.5: 1) were added to 1.24g of polyvinylpyrrolidone K90 and 0.25 g of polyvinylpyrrolidone K30, and stirred overnight to obtain a shell solution.
Step 2: 10g of a mixture of water and ethanol as a solvent (water to ethanol mass ratio: 1.5: 1) were added 0.87g of polyvinylpyrrolidone K90 and 0.4 g of polyvinylpyrrolidone K30, and after homogenization, 0.98g of lithium sulfate was added and stirred overnight to obtain a core solution.
And step 3: setting parameters of electrostatic spinning: the voltage is 12kV, the rotating speed of the rotating shaft receiver is 450 r/min, the receiving distance is 15cm, the advancing speed of the injector for the shell solution is 0.6mL/h, the advancing speed of the injector for the core solution is 0.4mL/h, and the electrostatic spinning fiber film can be obtained after 10h of electrospinning.
And 4, step 4: and carrying out pre-oxidation treatment on the obtained non-woven fabric fiber film for 2h at 250 ℃ in an air atmosphere in a tubular furnace, wherein the heating rate is 1 ℃/min.
And 5: carbonizing the film obtained by pre-oxidation at 750 ℃ for 1h under the argon atmosphere, wherein the heating rate is 2 ℃/min; the carbon fiber material with a multi-channel central core and a porous shell is obtained.
Fig. 1 is a high-power scan of the carbon/lithium sulfide composite prepared in example 1. As can be seen from the figure, the polyvinylpyrrolidone with low molecular weight forms pores on the surface of the carbon fiber, and the pores can increase the specific surface area, improve the ion transmission rate and improve the electrical conductivity.
Example 2:
step 1: 10g of a mixture of water and ethanol as a solvent (water to ethanol mass ratio: 1.5: 1) were added to 1.2 g of polyvinylpyrrolidone K90 and 0.26 g of polyvinylpyrrolidone K30, and stirred overnight to obtain a shell solution.
Step 2: 10g of a mixture of water and ethanol as a solvent (water to ethanol mass ratio: 1.5: 1) were added to 1.3 g of polyvinylpyrrolidone K90 and 0.45 g of polyvinylpyrrolidone K30, and after homogenization, 0.7g of lithium sulfate was added and stirred overnight to obtain a core solution.
And step 3: setting parameters of electrostatic spinning: the voltage is 15kV, the rotating speed of the rotating shaft receiver is 500r/min, the receiving distance is 15cm, the advancing speed of the injector for the shell solution is 0.6mL/h, the advancing speed of the injector for the core solution is 0.4mL/h, and the electrostatic spinning fiber film can be obtained after 10h of electrospinning.
And 4, step 4: and carrying out preoxidation treatment on the obtained non-woven fabric fiber film for 2h at 270 ℃ in an air atmosphere in a tubular furnace, wherein the heating rate is 1 ℃/min.
And 5: and carbonizing the film obtained by pre-oxidation at 800 ℃ for 2h under the argon atmosphere, wherein the heating rate is 3 ℃/min. The carbon fiber material with a multi-channel central core and a porous shell is obtained.
Fig. 2 is a low-power scanning image of the carbon/lithium sulfide composite material prepared in example 2, and it can be seen that the carbon/lithium sulfide composite electrode material prepared by the method is entirely carbon fiber with uniform diameter, and the uniform structure can improve the stability of the battery.
Example 3:
step 1: 10g of a mixture of water and ethanol as a solvent (water to ethanol mass ratio: 1.5: 1) were added to 1.2 g of polyvinylpyrrolidone K90 and 0.3 g of polyvinylpyrrolidone K16, and stirred overnight to obtain a shell solution.
Step 2: 10g of a mixture of water and ethanol as a solvent (water to ethanol mass ratio: 1.5: 1) were added to 1.35g of polyvinylpyrrolidone K90 and 0.5 g of polyvinylpyrrolidone K16, and after homogenization, 0.8g of lithium sulfate was added and stirred overnight to obtain a core solution.
And step 3: setting parameters of electrostatic spinning: the voltage is 17kV, the rotating speed of the rotating shaft receiver is 500r/min, the receiving distance is 20cm, the advancing speed of the injector for the shell solution is 0.6mL/h, the advancing speed of the injector for the core solution is 0.4mL/h, and the electrostatic spinning fiber film can be obtained after 10h of electrospinning.
And 4, step 4: the obtained non-woven fabric fiber film is pre-oxidized for 1.5h at 260 ℃ in the air atmosphere in a tubular furnace, and the heating rate is 3 ℃/min.
And 5: and carbonizing the film obtained by pre-oxidation at 850 ℃ for 1.5h under the argon atmosphere, wherein the heating rate is 5 ℃/min. The carbon fiber material with a multi-channel central core and a porous shell is obtained.
Example 4:
step 1: 10g of a mixture of water and ethanol as a solvent (water to ethanol mass ratio: 1.5: 1) were added to 1.25g of polyvinylpyrrolidone K90 and 0.25 g of polyvinylpyrrolidone K18, and stirred overnight to obtain a shell solution.
Step 2: 10g of a mixture of water and ethanol as a solvent (water to ethanol mass ratio: 1.5: 1) were added with 2.0 g of polyvinylpyrrolidone K90 and 0.5 g of polyvinylpyrrolidone K18, and after homogenization, 1.0 g of lithium sulfate was added and stirred overnight to obtain a core solution.
And step 3: setting parameters of electrostatic spinning: the voltage is 18kV, the rotating speed of the rotating shaft receiver is 550r/min, the receiving distance is 18cm, the advancing speed of the injector of the shell solution is 0.6mL/h, the advancing speed of the injector of the core solution is 0.4mL/h, and the electrostatic spinning fiber film can be obtained after 10h of electrospinning.
And 4, step 4: and pre-oxidizing the obtained non-woven fabric fiber film for 1h at 270 ℃ in an air atmosphere in a tubular furnace at the heating rate of 2 ℃/min.
And 5: carbonizing the film obtained by pre-oxidation at 900 ℃ for 1h under the argon atmosphere, wherein the heating rate is 3 ℃/min. The carbon fiber material with a multi-channel central core and a porous shell is obtained.
The scope of the invention is not limited to the above embodiments, and various modifications and changes may be made by those skilled in the art, and any modifications, improvements and equivalents within the spirit and principle of the invention should be included in the scope of the invention.

Claims (10)

1. A method for preparing a carbon/lithium sulfide composite material based on a coaxial electrostatic spinning technology is characterized by comprising the following steps: the method comprises the following steps:
(1) adding water and ethanol serving as solvents into low-molecular-weight polyvinylpyrrolidone and high-molecular-weight polyvinylpyrrolidone K90 in a certain mass ratio, and stirring overnight to obtain a shell solution, wherein the low-molecular-weight polyvinylpyrrolidone adopts any one or more of K16-K18 or K30;
(2) adding water and ethanol serving as solvents into low-molecular-weight polyvinylpyrrolidone and high-molecular-weight polyvinylpyrrolidone K90 in a certain mass ratio, uniformly stirring, adding lithium sulfate, and stirring overnight to obtain a core solution, wherein the low-molecular-weight polyvinylpyrrolidone adopts any one or more of K16-K18 or K30;
(3) carrying out coaxial electrospinning on the obtained shell solution and the core solution to obtain a non-woven fabric film;
(4) and carrying out pre-oxidation treatment and high-temperature carbonization treatment on the obtained non-woven fabric film to obtain the carbon fiber material with the multi-channel central core and the porous shell.
2. The method for preparing the carbon/lithium sulfide composite material based on the coaxial electrospinning technology according to claim 1, wherein: adding polyvinylpyrrolidone with low molecular weight and polyvinylpyrrolidone with high molecular weight K90 in the step (1) according to the mass ratio of 1: 5 to 4.
3. The method for preparing the carbon/lithium sulfide composite material based on the coaxial electrospinning technology according to claim 1, wherein: adding the polyvinylpyrrolidone with low molecular weight and the polyvinylpyrrolidone with high molecular weight K90 in the step (2) according to the mass ratio of 1: 4 to 2.
4. The method for preparing the carbon/lithium sulfide composite material based on the coaxial electrospinning technology according to claim 1, wherein: the total mass concentration of the polyvinylpyrrolidone with low molecular weight and the polyvinylpyrrolidone with high molecular weight K90 added into the shell solution in the step (1) is 12-14%.
5. The method for preparing the carbon/lithium sulfide composite material based on the coaxial electrospinning technology according to claim 1, wherein: and (3) adding polyvinylpyrrolidone with low molecular weight and polyvinylpyrrolidone K90 with high molecular weight into the core solution in the step (2), wherein the total mass concentration of the polyvinylpyrrolidone with low molecular weight and the polyvinylpyrrolidone K90 with high molecular weight is 10-20%.
6. The method for preparing the carbon/lithium sulfide composite material based on the coaxial electrospinning technology according to claim 1, wherein: the mass ratio of water to ethanol in the step (1) and the step (2) is 1.5-1.2: 1.
7. the method for preparing the carbon/lithium sulfide composite material based on the coaxial electrospinning technology according to claim 1, wherein: the mass of the lithium sulfate added in the step (2) is 0.6 g-1 g.
8. The method for preparing the carbon/lithium sulfide composite material based on the coaxial electrospinning technology according to claim 1, wherein: in the step (3), the coaxial electrostatic spinning parameters are as follows: the voltage is 12-18 kV, and the rotating speed of the roller collector is 400-600 r/min.
9. The method for preparing the carbon/lithium sulfide composite material based on the coaxial electrospinning technology according to claim 1, wherein: in the step (4), the pre-oxidation process is carried out in the air atmosphere of a muffle furnace, the temperature is 240-270 ℃, the heating rate is 1-3 ℃/min, and the heat preservation time is 2-3 h.
10. The method for preparing the carbon/lithium sulfide composite material based on the coaxial electrospinning technology according to claim 1, wherein: in the step (4), the carbonization process is carried out in a tubular furnace under the argon atmosphere, the temperature is 700-900 ℃, the heating rate is 2-5 ℃/min, and the heat preservation time is 1-2 h.
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