CN112968154B - Conductive composite material, preparation method thereof and application thereof in lithium ion battery electrode - Google Patents

Conductive composite material, preparation method thereof and application thereof in lithium ion battery electrode Download PDF

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CN112968154B
CN112968154B CN202110141955.9A CN202110141955A CN112968154B CN 112968154 B CN112968154 B CN 112968154B CN 202110141955 A CN202110141955 A CN 202110141955A CN 112968154 B CN112968154 B CN 112968154B
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composite material
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CN112968154A (en
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曹余良
姜倩荣
赵阿龙
艾新平
杨汉西
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Wuhan University WHU
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    • 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
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • 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
    • 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 conductive composite material, a preparation method thereof and application thereof in lithium ion battery electrodes. The composite material comprises a hollow conductive polymer pipe and a conductive material, wherein the conductive material is uniformly dispersed in the conductive polymer pipe in an incomplete filling mode, and the inner diameter of the conductive polymer pipe is 100-4000 nm. The preparation method comprises the following steps: and (2) performing electrostatic spinning on an electrostatic spinning solution containing a high molecular polymer and a conductive material to obtain nano-fiber yarns, dispersing the nano-fiber yarns into a hydrochloric acid solution containing a conductive polymer monomer, adding an initiator to perform polymerization reaction to obtain the nano-fiber yarns with the surfaces coated with the conductive polymer, and finally adding the nano-fiber yarns into an organic solvent to fully dissolve the high molecular polymer in the nano-fiber yarns to obtain the conductive composite material. The conductive composite material has good conductive and ion conductive properties, and when the conductive composite material is used in an electrode as a conductive agent, the polarization phenomenon under the conditions of large current charging and discharging can be effectively eliminated, the battery expansion is relieved, and the rate capability and the cycle performance are improved.

Description

Conductive composite material, preparation method thereof and application thereof in lithium ion battery electrode
Technical Field
The invention belongs to the technical field of conductive materials, and particularly relates to a conductive composite material, a preparation method thereof and application thereof in a lithium ion battery electrode.
Background
The lithium ion battery is a high-capacity long-life environment-friendly battery, has the advantages of high voltage, large specific energy, long cycle life, good safety performance, small self-discharge, no memory effect, rapid charge and discharge, wide working temperature range and the like, and is widely applied to the fields of energy storage, electric automobiles, portable electronic products and the like. With the development of society and the popularization of charging piles, especially compared with fuel vehicles, the charging speed of the charging pile is far less than the demand of consumers. Therefore, the rate capability of lithium ion batteries is also increasingly required.
Currently, a commercial lithium ion battery generally uses SP, CNT and graphene as a carbon tube, and particularly, with the requirement of higher rate performance, the application of CNT and graphene is more and more extensive. However, with the design of thick electrodes for increasing energy density, the transmission path of lithium ions is increasing continuously; along with the high compaction design of the electrode, the porosity of the pole piece is continuously reduced; leading to increasingly difficult electrolyte penetration. As the polarization of the electrode increases during high-rate charging of the battery, lithium deposition may occur in a local area, eventually leading to deterioration of the safety and cycle performance of the battery.
CN106941167A discloses a porous composite negative electrode material for a lithium ion battery, which is prepared by adding a pore-forming agent into an electrospinning solution, preparing composite fibers through electrospinning, and removing the pore-forming agent in the composite fibers through thermal decomposition, solvent in an organic solvent or chemical corrosion, so that pores are formed in the composite fibers, and the porosity of the negative electrode material is increased. However, the porous graphite used by the electrode plate is 3-15um micron-sized, and most of pores generated by cold pressing of the electrode plate after pore forming are still flattened by the pressing roller.
With the higher and higher energy density requirement of the market on the battery products, how to solve the problems of porosity and poor lithium ion conductivity caused by the continuous increase of the thickness and the continuous increase of the compaction density becomes a limitation for improving the rate capability. Therefore, it is urgently needed to solve the above problems by some new materials or processes.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a conductive composite material, a preparation method thereof and application thereof in lithium ion battery electrodes. The conductive composite material has good conductive and ion conductive properties, and when the conductive composite material is used as a conductive agent in a lithium ion battery electrode, the polarization phenomenon under the condition of large-current charge and discharge can be effectively eliminated, the battery expansion is relieved, and the rate capability and the cycle performance are improved.
In order to solve the technical problems, the invention provides the following technical scheme:
providing a lithium ion battery electrode conductive agent which is a conductive composite material and comprises a hollow conductive polymer tube and a conductive material, wherein the conductive material is uniformly dispersed in the conductive polymer tube in an incomplete filling manner, and the inner diameter of the conductive polymer tube is 100-4000 nm; the conductive material is any one or combination of at least two of nanoscale conductive carbon black, carbon nanotubes or graphene.
According to the scheme, the conductive polymer is one of polyaniline, polypyrrole or polythiophene.
According to the scheme, the mass ratio of the conductive material to the conductive polymer pipe is 0.1-0.3: 1.
According to the scheme, the wall thickness of the hollow conductive polymer tube is 100-500 nm.
The preparation method of the electrode conductive agent of the lithium ion battery comprises the following steps:
1) carrying out electrostatic spinning on an electrostatic spinning solution containing a high molecular polymer and a conductive material to obtain nano-fiber yarns;
2) uniformly dispersing the nano-fiber filaments obtained in the step 1) into a hydrochloric acid solution containing a conductive polymer monomer, and then adding a certain initiator to perform a polymerization reaction to obtain the nano-fiber filaments coated with the conductive polymer on the surface;
3) adding an organic solvent into the nanofiber filaments coated with the conductive polymer on the surfaces obtained in the step 2), and stirring to fully dissolve the high molecular polymer in the nanofiber filaments to obtain the conductive composite material.
According to the scheme, in the step 1), the high molecular polymer is any one or a combination of at least two of polymethyl methacrylate, polystyrene, polyethylene and polyvinyl acetate.
According to the scheme, in the step 1), the conductive material is any one or a combination of at least two of nanoscale conductive carbon black, carbon nanotubes or graphene.
According to the scheme, in the step 1), the mass ratio of the conductive material to the high molecular polymer is 0.1-1: 1.
According to the scheme, in the step 1), the concentration of the high molecular polymer and the conductive material in the electrostatic spinning solution containing the high molecular polymer and the conductive material is 5-20%.
According to the scheme, in the step 1), the preparation method of the electrostatic spinning solution containing the high molecular polymer and the conductive material comprises the following steps: adding the high molecular polymer and the conductive material into a solvent, and stirring for 1-6h at the temperature of 40-100 ℃ to obtain the electrostatic spinning solution containing the high molecular polymer and the conductive material, wherein the solvent is any one or the combination of at least two of N, N-dimethylformamide, dimethyl furan, dimethyl sulfoxide and N-methylpyrrolidone. The purpose of the heating and stirring is to sufficiently dissolve the high molecular weight polymer material in the solvent.
According to the scheme, in the step 1), the technological parameters of electrostatic spinning are as follows: the voltage is 10-30kV, the spinning speed is 20-100mL/min, and the electrode distance is 15-30 cm.
The nanofiber material with a specific size is obtained by regulating and controlling the voltage, the spinning speed and the electrode distance, and the diameter of the obtained nanofiber is smaller when the voltage is higher, the spinning speed is slower or the electrode distance is longer. In addition, the solvent is fully volatilized by adjusting the parameters: the slower the spinning speed or the larger the electrode distance, the more the solvent evaporation is favored. The solvent is only required to be fully volatilized.
According to the scheme, in the step 2), the mass ratio of the conductive polymer monomer to the nanofiber filaments is 0.8-1: 1. The higher the proportion of the conductive polymer monomer, the thicker the hollow tube wall, and the stronger the pressure resistance.
According to the scheme, in the step 2), the conductive polymer monomer is any one of aniline, pyrrole and thiophene.
According to the scheme, in the step 2), the concentration of the hydrochloric acid is 0.5-1.5 mol/L.
According to the scheme, in the step 2), the nano-fiber filaments are uniformly dispersed into a hydrochloric acid solution containing a conductive polymer monomer by stirring for 2-6 hours.
According to the scheme, in the step 2), the mass ratio of the initiator to the conductive polymer monomer is 1: 1-1.5.
According to the scheme, in the step 2), the initiator is any one of ferric trichloride, ammonium persulfate, potassium persulfate and hydrogen peroxide.
According to the scheme, in the step 2), the polymerization reaction temperature is-20-30 ℃, and the polymerization reaction time is 6-18 h.
According to the scheme, in the step 3), the organic solvent is any one or a combination of at least two of toluene, tetrahydrofuran, xylene and amyl acetate.
According to the scheme, in the step 3), the stirring time is 2-6 h.
According to the scheme, in the step 3), the mass ratio of the nanofiber filaments coated with the conductive polymer on the surface to the organic solvent is 1: 10-20.
Provides an application of the lithium ion battery electrode conductive agent in a lithium ion battery electrode.
According to the scheme, the electrode is at least one of a battery anode or a battery cathode.
According to the above scheme, the electrode comprises an electrode active material, a conductive composite material, a binder and a current collector.
Compared with the prior art, the invention has the following beneficial effects:
1. the conductive composite material provided by the invention takes a hollow conductive polymer pipe as a skeleton structure, and the inner diameter can be regulated and controlled at will, so that the circulation of electrolyte from a pipeline is facilitated; meanwhile, the conductive material is uniformly dispersed and filled in the pipeline, so that the smoothness of the pipeline is ensured, the material is endowed with good conductivity, and the conductive polymer pipe is good in conductivity, so that the conductive composite material not only has good conductivity, but also has good ion conductivity, which is not possessed by all carbon pipes at present.
2. When the conductive composite material is used as a conductive agent in a lithium ion battery electrode, on one hand, due to good conductivity and ion conductivity, the conductive composite material can effectively eliminate the polarization phenomenon caused by inconsistent electron and ion transmission capacities under the condition of large current charging and discharging, so that the battery rate discharge platform is higher and the rate performance is better; on the other hand, combined material's skeleton texture is conducting polymer, and polymer itself possesses certain flexibility, and when the battery circulated to the later stage, because the side reaction of electrolyte, battery thickness constantly expanded can cause the serious deformation of battery and the decay of electrical property, and combined material when using as the conducting agent in as the electrode, when as the lithium ion drain passageway, can constantly be compressed at this in-process, release hollow volume to play the effect of alleviating battery inflation and promotion cycle performance.
3. Firstly, preparing a high molecular polymer and a conductive material together through electrostatic spinning to obtain a nanofiber filament, then coating a layer of conductive polymer on the surface of the nanofiber filament, and finally fully dissolving the high molecular polymer in the nanofiber filament through an organic solvent to obtain a conductive composite material; after the high molecular polymer is dissolved, the conductive material is uniformly dispersed and distributed in the hollow pipeline formed by the conductive polymer, so that the pipeline smoothness of the hollow conductive polymer pipe is ensured, the ion conduction capability is enhanced, and the conductivity of the composite material is further enhanced; the method has the advantages of simple preparation process, low process cost and industrial production prospect.
Drawings
Fig. 1 is a surface SEM image of a lithium iron phosphate positive electrode made of the conductive composite material prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The preparation method of the conductive composite material comprises the following steps:
step 1, adding polymethyl methacrylate and conductive material conductive carbon black into an organic solvent N, N-dimethylformamide, heating and stirring for 6h at 40 ℃, and preparing an electrostatic spinning solution A with the concentration of the polymethyl methacrylate and the conductive material being 5%, wherein the mass ratio of the conductive material to the polymethyl methacrylate is 0.1: 1. And (3) carrying out electrostatic spinning on the solution A to obtain the nano-fiber yarn with the diameter of 302nm by electrostatic spinning equipment with the voltage of 10kV, the spinning speed of 100mL/min and the electrode distance of 30 cm.
Step 2, adding the nanofiber filaments obtained in the step 1 into a 1mol/L hydrochloric acid solution of aniline, wherein the mass ratio of aniline to nanofiber filaments is 0.8:1, stirring is carried out at 500 revolutions per minute for 6 hours, and the nanofiber filaments are uniformly dispersed to obtain a mixed liquid B;
and 3, adding ammonium sulfate into the mixed liquid B obtained in the step 2, wherein the mass ratio of aniline to ammonium persulfate is 1.5:1, and polymerizing for 18 hours at the temperature of-20 ℃ at the rotating speed of 600 revolutions per minute. After the reaction is finished, carrying out suction filtration to obtain the nano-fiber filaments coated with polyaniline on the surface;
step 4, adding toluene into the nano-fiber wire coated with polyaniline in the surface obtained in the step 3, wherein the mass ratio of the nano-fiber wire coated with polyaniline to the toluene is 1: 10; stirring at 200 r/min for 6h, and filtering and drying to obtain the conductive composite material.
Example 2
The preparation method of the conductive composite material comprises the following steps:
step 1, adding polystyrene and a conductive material carbon nano tube into an organic solvent dimethylfuran, heating and stirring for 3 hours at 60 ℃, and preparing an electrostatic spinning solution A with the concentration of the polystyrene and the conductive material of 10%, wherein the mass ratio of the conductive material to the polystyrene is 0.2: 1. And (3) carrying out electrostatic spinning on the solution A by electrostatic spinning equipment with the set voltage of 20kV, the spinning speed of 60mL/min and the electrode distance of 20cm to obtain the nano-fiber filament with the diameter of 734 nm.
Step 2, adding the nanofiber filaments obtained in the step 1 into a 1mol/L hydrochloric acid solution of pyrrole, wherein the mass ratio of the pyrrole to the nanofiber filaments is 0.9:1, and stirring at 1000 rpm for 4 hours to obtain a mixed liquid B;
and 3, adding hydrogen peroxide into the mixed liquid B obtained in the step 2, wherein the mass ratio of pyrrole to hydrogen peroxide is 1.2:1, and polymerizing for 12 hours at the temperature of 0 ℃ and at the rotating speed of 1000 revolutions per minute. After the reaction is finished, carrying out suction filtration to obtain the nano-fiber filaments coated with polypyrrole on the surface;
and 4, adding dimethylbenzene into the polypyrrole-coated nano-fiber obtained in the step 3, wherein the mass ratio of the polypyrrole-coated nano-fiber to the dimethylbenzene is 1:15, stirring at 400 rpm for 4 hours, and then carrying out suction filtration and drying to obtain the conductive composite material.
Example 3
The preparation method of the conductive composite material comprises the following steps:
step 1, adding polyvinyl acetate and conductive material graphene into an organic solvent N-methyl pyrrolidone, heating and stirring for 1h at 100 ℃, and preparing an electrostatic spinning solution A with the concentration of the polyvinyl acetate and the conductive material being 20%, wherein the mass ratio of the conductive material to the polyvinyl acetate is 0.3: 1. And (3) carrying out electrostatic spinning on the solution A by using electrostatic spinning equipment with the voltage of 30kV, the spinning speed of 20mL/min and the electrode distance of 15cm to obtain the nano-fiber yarn with the diameter of 1326 nm.
Step 2, adding the nanofiber filaments obtained in the step 1 into a 1mol/L hydrochloric acid solution of thiophene, wherein the mass ratio of thiophene to nanofiber filaments is 1:1, and stirring at 2000 rpm for 2 hours to obtain a mixed liquid B;
and 3, adding ferric trichloride into the mixed liquid B obtained in the step 2, wherein the mass ratio of thiophene to ferric trichloride is 1:1, and polymerizing for 6 hours at the temperature of 30 ℃ at the rotating speed of 1500 r/min. After the reaction is finished, carrying out suction filtration to obtain the nano-fiber filament coated with polythiophene on the surface;
step 4, adding amyl acetate into the nano-fiber filaments coated with polythiophene on the surface obtained in the step 3, wherein the mass ratio of the nano-fiber filaments coated with polythiophene on the surface to the amyl acetate is 1: 15; stirring at 600 rpm for 2h, and filtering and drying to obtain the conductive composite material.
Comparative example 1
This comparative example used a commercially available carbon nanotube with a diameter of 8 nm.
Comparative example 2
This comparative example used commercially available conductive carbon black.
The conductive composites prepared in examples 1-3 were used as conductive agents in conventional 2016 button cells with consistent positive and negative electrode formulations for all samples, along with commercially available conductive agents as provided in comparative examples 1-2. In the positive electrode, the proportion of the active material of the lithium iron phosphate positive electrode is 90.0 percent, the conductive composite material or the commercial conductive agent is 5.0 percent, and the binder PVDF is 5.0 percent. The negative electrode uses a metallic lithium plate.
The positive electrode sheets obtained in examples 1 to 3 and comparative example 2 had a thickness ofAbout 200 um; the thickness of the positive pole piece prepared in the comparative example 1 is about 200um and about 50um of the conventional positive pole piece, wherein the compaction density is 2.5g/cm 3 。
And respectively carrying out rate performance test on the prepared batteries. The results are shown in table 1 below:
TABLE 1
Figure GDA0003640773930000061
From the data results of examples 1-3, it can be seen that the smaller the inner diameter is, the more dense the ion and electron flow channels are, and the better the corresponding rate performance is, under the same thickness of the positive electrode and the same formulation ratio.
From the results of the two sets of data of different thicknesses in comparative example 1, it can be seen that the larger the thickness is, the longer the migration distance of ions is, under the same formulation ratio and the same compacted density. The battery rate performance and cycle performance are degraded due to increased battery polarization.
From the data results of examples 1-3 and comparative examples 1-2, it can be seen that the rate performance improvement of all examples is very significant under extreme conditions of ultra-high thickness of 200um and high compaction. The reason is mainly that under the conditions of ultrahigh thickness and high compaction, the migration capability of ions is poor, and the battery polarization is increased, so that the rate performance of the battery is reduced. Comparative example 1 is a carbon nanotube, which has almost no ion conduction capability, so the rate performance is the worst; comparative example 2 is conductive carbon black, which has a weak ion conductivity, so the performance is better than that of comparative example 1.
For commercial batteries, the greater the thickness of the positive electrode, the higher the energy density of the battery that can be designed. Compared with commercial conductive carbon black and carbon nanotubes, the conductive agent provided by the invention can greatly improve the rate capability of the button cell under the condition that the thickness of the positive electrode is several times of the conventional thickness. Provides a very excellent composite material which can conduct electricity and ions for the design of commercial batteries. Meanwhile, the design of active materials with different particle sizes in different commercial batteries can be matched by regulating and controlling the size of the inner diameter.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.

Claims (10)

1. The electrode conductive agent for the lithium ion battery is characterized by being a conductive composite material, wherein the conductive composite material comprises a hollow conductive polymer tube and a conductive material, the conductive material is uniformly dispersed in the conductive polymer tube in an incomplete filling manner, and the inner diameter of the conductive polymer tube is 100-4000 nm; the conductive material is any one or combination of at least two of nanoscale conductive carbon black, carbon nanotubes or graphene.
2. The lithium ion battery electrode conductive agent of claim 1, wherein the mass ratio of the conductive material to the conductive polymer tube is 0.1-0.3: 1.
3. The lithium ion battery electrode conductive agent of claim 1, wherein the wall thickness of the hollow conductive polymer tube is 100-500 nm.
4. The lithium ion battery electrode conductive agent of claim 1, wherein the conductive polymer is one of polyaniline, polypyrrole, or polythiophene.
5. The preparation method of the lithium ion battery electrode conductive agent of any one of claims 1 to 4, characterized by comprising the following steps:
1) carrying out electrostatic spinning on an electrostatic spinning solution containing a high molecular polymer and a conductive material to obtain nano-fiber yarns;
2) uniformly dispersing the nano-fiber filaments obtained in the step 1) into a hydrochloric acid solution containing a conductive polymer monomer, and then adding a certain initiator to perform a polymerization reaction to obtain the nano-fiber filaments coated with the conductive polymer on the surface;
3) adding an organic solvent into the nanofiber filaments coated with the conductive polymer on the surfaces obtained in the step 2), and stirring to fully dissolve the high molecular polymer in the nanofiber filaments to obtain the conductive composite material.
6. The production method according to claim 5,
in the step 1), the high molecular polymer is any one or a combination of at least two of polymethyl methacrylate, polystyrene, polyethylene and polyvinyl acetate; the conductive material is any one or the combination of at least two of nanoscale conductive carbon black, carbon nano tubes or graphene;
in the step 2), the conductive polymer monomer is any one of aniline, pyrrole and thiophene; the initiator is any one of ferric trichloride, ammonium persulfate, potassium persulfate and hydrogen peroxide;
in the step 3), the organic solvent is any one or a combination of at least two of toluene, tetrahydrofuran, xylene and amyl acetate.
7. The preparation method according to claim 5, wherein in the step 1), the mass ratio of the conductive material to the high molecular polymer is 0.1-1: 1; in the step 2), the mass ratio of the conductive polymer monomer to the nano-fiber filament is 0.8-1:1, and the mass ratio of the initiator to the conductive polymer monomer is 1: 1-1.5; and in the step 3), the mass ratio of the nanofiber filaments coated with the conductive polymer on the surface to the organic solvent is 1: 10-20.
8. The method according to claim 5, wherein the step 1) comprises a step of preparing an electrospinning solution containing the high molecular polymer and the conductive material by: adding a high molecular polymer and a conductive material into a solvent, and stirring for 1-6h at the temperature of 40-100 ℃ to obtain an electrostatic spinning solution containing the high molecular polymer and the conductive material, wherein: in the electrostatic spinning solution, the concentration of the high molecular polymer and the conductive material is 5-20%; the solvent is any one or the combination of at least two of N, N-dimethylformamide, dimethyl furan, dimethyl sulfoxide and N-methylpyrrolidone; the technological parameters of electrostatic spinning are as follows: the voltage is 10-30kV, the spinning speed is 20-100mL/min, and the electrode distance is 15-30 cm.
9. The preparation method according to claim 5, wherein in the step 2), the polymerization reaction temperature is-20 to 30 ℃, and the polymerization reaction time is 6 to 18 hours; in the step 3), the stirring time is 2-6 h.
10. Use of the lithium ion battery electrode conductive agent of any one of claims 1-4 in a lithium ion battery electrode.
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