CN109473633A - A kind of lithium ion cell nano silicon substrate composite fibre negative electrode material and preparation method thereof - Google Patents

A kind of lithium ion cell nano silicon substrate composite fibre negative electrode material and preparation method thereof Download PDF

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CN109473633A
CN109473633A CN201710799031.1A CN201710799031A CN109473633A CN 109473633 A CN109473633 A CN 109473633A CN 201710799031 A CN201710799031 A CN 201710799031A CN 109473633 A CN109473633 A CN 109473633A
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nano silicon
lithium ion
spinning
negative electrode
electrode material
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CN109473633B (en
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刘仁虎
余德馨
胡博
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Shanghai Shanshan Technology Co Ltd
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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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • 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
    • 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 present invention relates to technical field of lithium ion, specifically a kind of lithium ion cell nano silicon substrate composite fibre negative electrode material and preparation method thereof, it is characterised in that: including nanofiber matrix and the nano silicon-based active particles and the conducting polymer that are dispersed in nanofiber matrix；The mass fraction of the nanofiber matrix is 5-97%, and the mass fraction of nano silicon-based active particles is 2-70%, and the mass fraction of the conducting polymer is 1-25%；The nanofiber matrix uses the spinning solution electrostatic spinning for forming polymer dissolution in organic solvent to obtain；The nano silicon-based being particle is siliceous at least one of compound or compound.The present invention is compared with the existing technology, easy to operate, process environmental protection；And prepared negative electrode material not only electronic conduction ability with higher, but also the volume expansion and structure dusting of nano silicon-based active particles can be effectively relieved, improve cycle performance.

Description

A kind of lithium ion cell nano silicon substrate composite fibre negative electrode material and preparation method thereof
Technical field
The present invention relates to technical field of lithium ion, specifically a kind of lithium ion cell nano silicon substrate composite fibre Negative electrode material and preparation method thereof.
Background technique
Lithium ion battery has the advantages such as chemical property is good, environment friendly and pollution-free, price is low and is widely used.Lithium from The negative electrode material of sub- battery is generally graphite carbon material, such current material is already close to its theoretical specific capacity (372mAh/ G), but with the fast development in portable electronic product and electric car field, graphite carbon material has been difficult to meet continuous The demand of the high-energy density of growth.In recent years, the silica-base materials such as Si, SiOx, SiOx/C are higher by graphite type material several times with it Theoretical specific capacity and be increasingly interested by researchers, and become research hotspot and the following lithium ion battery negative material Development trend.
Although silica-base material theoretical specific capacity with higher, under conditions of high level removal lithium embedded, volume becomes Change huge, causes silica-base material granule atomization, electric conductivity to reduce, cyclical stability is poor.Currently, solution includes by silicon substrate Expect particle coated modified carbon, porous and alloying.Although these methods achieve certain effect, preparation method is all It is complex, not only long preparation period, or even the high energy consumption process such as also need high temperature sintering.Therefore, lithium ion battery silicon substrate is negative Pole Material Field is badly in need of a kind of method easy to operate, process is environmentally friendly.
Electrostatic spinning is effective ways that are a kind of cheap and efficiently preparing nano-fiber material.Polymer precursor passes through Uniform nanofibrous structures can be formed after this method processing.Nanoscale fibrous material can be prepared.It is examined through patent Rope, having the Chinese invention patent that Authorization Notice No. is CN103305965B, to disclose a kind of silicon-carbon with nanometer micropore gap compound A kind of tool has been prepared using the method that electrostatic spinning combines oxidation, carbonization in material and preparation method thereof and purposes There is the Si-C composite material of nanometer micropore gap structure, thus under the premise of guaranteeing the electron transport ability of material entirety, to receive Cushion space is reserved in the expansion of rice silicon particle；Application publication number is that the Chinese invention patent of CN104037390A discloses one kind Silicon/carbon nanocoils carried titanium dioxide lithium cell cathode material preparation method, is obtained using electrostatic spinning and oxidation, carbonizatin method Titanium dioxide comprehensive silicon/carbon nanocoils negative electrode material, material specific capacity with higher and cycle performance；Application publication number is The Chinese invention patent of CN105118974A discloses a kind of silicon based anode material and preparation method thereof, using electrostatic spinning and more A kind of carbon coating silicon/carbon nano-fiber is made in the method for secondary carbonization, alleviates the volume expansion and structure fragmentation of silicon particle.
Above-mentioned three patents are aoxidized and were carbonized having carried out after electrostatic spinning process obtains nano-composite fiber Journey, it is therefore an objective to sinter fibrous matrix into carbon to improve the electronic conduction ability of material entirety.But oxidation and carbonisation are equal For high temperature, high energy consumption process, and repeatedly fibrous material is heat-treated under different temperatures different atmosphere but also process is multiple It is miscellaneous to be difficult to control.
Summary of the invention
The purpose of the present invention is overcome the deficiencies in the prior art, it is only necessary to by the composite nano fiber after electrostatic spinning low Vacuum drying is carried out under temperature and removes solvent, and final lithium ion battery negative material can be obtained；On the one hand in the composite material Nano silicon-based active particles there is the cladding of conducting polymer to can be improved electronic conduction ability, it is on the other hand nanofiber-based Body can be used as secondary cladding, the volume expansion and structure dusting of nano silicon-based active particles can be effectively relieved, to mention High cycle performance.
To achieve the above object, a kind of lithium ion cell nano silicon substrate composite fibre negative electrode material is designed, it is characterised in that:
Including nanofiber matrix and the nano silicon-based active particles and the conduction that are dispersed in nanofiber matrix Polymer；The mass fraction of the nanofiber matrix is 5-97%, and the mass fraction of nano silicon-based active particles is 2- 70%, the mass fraction of the conducting polymer is 1-25%；
The nanofiber matrix uses the spinning solution electrostatic spinning for forming polymer dissolution in organic solvent to obtain； The polymer is polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, polyacrylonitrile, polyimides, gathers inclined fluorine One of ethylene is a variety of；The concentration of polymer is 5wt%-20wt% in spinning solution；
The nano silicon-based being particle is siliceous at least one of compound or compound；
The conducting polymer be polyaniline, polyparaphenylene, polypyrrole or polythiophene or the polyaniline, polyparaphenylene, One of the derivative or a variety of of polypyrrole, polythiophene；The conducting polymer state is that solid phase nano particle or liquid phase are molten Liquid.
The siliceous compound or compound is Si, SiOx, Si-M alloy, in Si/C, SiOx/C, Si-M/C At least one, wherein M is metal or metal oxide, and 0≤x≤2, C are organic carbon, inorganic carbon, graphite, graphene, carbon nanometer Pipe or carbon fiber.
The nano silicon-based active particles diameter is in 10-500nm.
The diameter of the nanofiber matrix is in 100-1000nm.
1000≤conducting polymer number-average molecular weight≤300,000.
The organic solvent is at least one of ethyl alcohol, dimethylformamide, dimethyl acetamide or dimethyl sulfoxide.
The metal or metal oxide M is Li, Li2O、Co、CoO、Fe、Fe2O3、Mg、MgO、Sn、SnO、Ti、 TiO2, Ag, AgO or Cr.
A kind of preparation method of lithium ion cell nano silicon substrate composite fibre negative electrode material, it is characterised in that: including as follows Preparation step:
(1), raw material mixes: the nano silicon-based active particles are uniformly mixed to form mixture with conducting polymer H1；
(2), prepare spinning solution: by polymer stirring and dissolving in organic solvent and deaeration processing be configured to uniform spinning Liquid H2；
(3), it prepares blend spinning liquid: mixture H1 being dispersed with stirring in spinning solution H2, uniform blend spinning is obtained Liquid H3；
(4), electrostatic spinning: blend spinning liquid H3 is encased in syringe, carries out electrostatic spinning off field in high-pressure electrostatic, Spinning solution thread curing molding in air, then low-temperature vacuum drying is to get arriving lithium ion cell nano silicon substrate composite fibre Negative electrode material.
The voltage of electric field of the electrostatic spinning is 12-30kV；Spinning flow velocity amount is 0.5-1.5mL/h；Spinning distance is 8-30cm；The temperature of spinning environment is 25-30 DEG C；Air humidity is 25-45%.
Nano silicon-based active particles are mixed with conducting polymer using solid phase mixing or solid-liquid in the raw material mixing Any mode mix, when solid phase mixing, mixed using ball milling or mechanical stirring, when solid-liquid is mixed using centrifugation, Ultrasonic mixing.
The present invention is compared with the existing technology, it is only necessary to which the composite nano fiber after electrostatic spinning is carried out vacuum at low temperature Solvent is dried and removed, final lithium ion battery negative material can be obtained, is no longer needed to through high temperature, the oxidation of high energy consumption, carbonization Process, easy to operate, process environmental protection；And prepared lithium ion cell nano silicon substrate composite nano fiber negative electrode material is not only Electronic conduction ability with higher, and volume expansion and the structure powder of nano silicon-based active particles can be effectively relieved Change, improves cycle performance.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of lithium ion cell nano silicon substrate composite fibre negative electrode material in the embodiment of the present invention 1.
Fig. 2 be lithium ion cell nano silicon substrate composite fibre negative electrode material prepared in the embodiment of the present invention 2 for the first time Charging and discharging curve.
Fig. 3 is prepared in the embodiment of the present invention 2 follows for lithium ion cell nano silicon substrate composite fibre negative electrode material 50 weeks Ring capacity retention ratio schematic diagram.
Referring to Fig. 1, wherein 100 be nano silicon-based active particles；200 be conducting polymer；300 be nanofiber-based Body.
Specific embodiment
The present invention is further described through below with reference to embodiment.It should be noted that being previously mentioned in following embodiment Specific substance, be intended only as it is a kind of citing be illustrated, be not limited thereto, i.e., under the same terms, can also with the present invention Unlisted other substances with identical functions substitute in embodiment.
Embodiment 1
As shown in Figure 1, the lithium ion cell nano silicon substrate composite fibre negative electrode material in the present invention, including it is nanofiber-based Body, nano silicon-based active particles, conducting polymer, with hydrogen bond between the conducting polymer and nano silicon-based active particles Effect and physical contact be connected with each other, and between nano silicon-based active particles and particle by conducting polymer bridging one It rises.
Wherein, the mass fraction of nanofiber matrix is 5-97%, and the mass fraction of nano silicon-based active particles is 2- 70%, the mass fraction of the conducting polymer is 1-25%, and the diameter of nanofiber matrix is received between 100-1000nm Rice silicon-based active composition granule average diameter is preferably between 10-500nm.
The nanofiber matrix uses the spinning solution electrostatic spinning for forming polymer dissolution in organic solvent to obtain； The polymer is polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, polyacrylonitrile, polyimides, gathers inclined fluorine One of ethylene is a variety of；And the concentration of polymer is 5wt%-20wt% in spinning solution；The organic solvent is ethyl alcohol, two At least one of methylformamide, dimethyl acetamide or dimethyl sulfoxide；
The nano silicon-based being particle is siliceous at least one of compound or compound；Described is siliceous Compound or compound are at least one of Si, SiOx, Si-M alloy, Si/C, SiOx/C, Si-M/C, and wherein M is metal Or metal oxide, 0≤x≤2, C are organic carbon, inorganic carbon, graphite, graphene, carbon nanotube or carbon fiber；The metal Or metal oxide M is Li, Li2O、Co、CoO、Fe、Fe2O3、Mg、MgO、Sn、SnO、Ti、TiO2, Ag, AgO or Cr.
The conducting polymer be polyaniline, polyparaphenylene, polypyrrole or polythiophene or the polyaniline, polyparaphenylene, One of the derivative or a variety of of polypyrrole, polythiophene；The conducting polymer state is that solid phase nano particle or liquid phase are molten Liquid.
Further, the nano silicon-based active particles diameter is in 10-500nm.
Further, the diameter of the nanofiber matrix is in 100-1000nm.
Further, 1000≤conducting polymer number-average molecular weight≤300,000.
Embodiment 2
It is uniform that the nano Si of 30g partial size 30nm and 2g polyaniline powder are put into solid phase mixing in ball mill, obtain mixture H1；
The polyacrylonitrile powder for weighing 20g molecular weight Mw=15 ten thousand is added in the DMF of 200g, under room temperature, stirring and dissolving 8h obtains the Solution H 2 that mass fraction is 9%；
H1 is added in H2,5h is dispersed with stirring, obtains Si blend spinning liquid evenly dispersed in the DMF solution of PAN H3；
H3 is added in syringe, is squeezed out spinning solution with the flow of 0.9mL/h, the electrostatic under the high voltage electric field of 15kV Spinning receives distance 15cm, and environment temperature is 25 DEG C, and air humidity 40%, dynamic analysis of spinning is formed and collected through air curing Then aluminium foil surface carries out low-temperature vacuum drying 12h with 60 DEG C, vacuum degree 50mbar and obtains lithium ion battery to remove solvent Nano silicon-based composite fibre negative electrode material.
It is prepared into lithium ion battery using the material, after tested, the specific discharge capacity of the material has reached 2028mAh/g, Referring to fig. 2, first effect is 82%, and capacity retention ratio is 76% or more after recycling within 50 weeks, and referring to Fig. 3, pole piece expansion rate is down to 50% Below.
Embodiment 3
It is uniform that the nano Si of 20g partial size 40nm and 2g polypyrrole powder are put into solid phase mixing in machine mixer, obtained Mixture H1；
The polyacrylonitrile powder for weighing 20g molecular weight Mw=15 ten thousand is added in the DMF of 200g, under room temperature, stirring and dissolving 8h obtains the Solution H 2 that mass fraction is 9%；
H1 is added in H2,6h is dispersed with stirring, obtains Si blend spinning liquid evenly dispersed in the DMF solution of PAN H3；
H3 is added in syringe, is squeezed out spinning solution with the flow of 0.9mL/h, the electrostatic under the high voltage electric field of 15kV Spinning receives distance 15cm, and environment temperature is 25 DEG C, and air humidity 40%, dynamic analysis of spinning is formed and collected through air curing Then aluminium foil surface carries out low-temperature vacuum drying 12h with 60 DEG C, vacuum degree 50mbar and obtains lithium ion battery to remove solvent Nano silicon-based composite fibre negative electrode material.
It is prepared into lithium ion battery using the material, after tested, the specific discharge capacity of the material has reached 1831mAh/g, Head effect is 84%, and capacity retention ratio is 74% or more after recycling within 50 weeks, and pole piece expansion rate is down to 50% or less.
Embodiment 4
The nano Si of 25g partial size 80nm is carried out liquid phase using ultrasound with 100g PEDOT:PSS solution to mix, is obtained Even mixed liquor H1；Wherein, PEDOT content accounts for PSS 1wt% in PEDOT:PSS solution；
The polyacrylonitrile powder for weighing 20g molecular weight Mw=18 ten thousand is added in the DMF of 200g, under room temperature, stirring and dissolving 8h obtains the Solution H 2 that mass fraction is 9%；
H1 is added in H2,8h is dispersed with stirring, obtains Si blend spinning liquid evenly dispersed in the DMF solution of PAN H3；
Blend spinning liquid is added in syringe, is squeezed out spinning solution with the flow of 1.0mL/h, in the high-voltage electricity of 15kV Electrostatic spinning off field receives distance 16cm, and environment temperature is 30 DEG C, and air humidity 35%, dynamic analysis of spinning is formed through air curing And collect in aluminium foil surface, low-temperature vacuum drying 12h is then carried out with 60 DEG C, vacuum degree 50mbar and obtains lithium to remove solvent The nano silicon-based composite fibre negative electrode material of ion battery.
It is prepared into lithium ion battery using the material, after tested, the specific discharge capacity of the material has reached 1753mAh/g, Head effect is 87%, and capacity retention ratio is 77% or more after recycling within 50 weeks, and pole piece expansion rate is down to 50% or less.
The above description is only an embodiment of the present invention, and it cannot be said that specific implementation of the invention is only limited to these instructions. For those skilled in the art to which the present invention belongs, under the premise of not departing from benzene inventive concept, if can also make Dry equivalent substitute or obvious modification, all shall be regarded as belonging to protection scope of the present invention.

Claims (10)

1. a kind of lithium ion cell nano silicon substrate composite fibre negative electrode material, it is characterised in that:
Including nanofiber matrix and the nano silicon-based active particles and the conducting polymer that are dispersed in nanofiber matrix Object；The mass fraction of the nanofiber matrix is 5-97%, and the mass fraction of nano silicon-based active particles is 2-70%, institute The mass fraction for stating conducting polymer is 1-25%；
The nanofiber matrix uses the spinning solution electrostatic spinning for forming polymer dissolution in organic solvent to obtain；It is described Polymer be polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, polyacrylonitrile, polyimides, Kynoar One of or it is a variety of；And the concentration of polymer is 5wt%-20wt% in spinning solution；
The nano silicon-based being particle is siliceous at least one of compound or compound；
The conducting polymer is polyaniline, polyparaphenylene, polypyrrole or polythiophene or the polyaniline, polyparaphenylene, poly- pyrrole It coughs up, one of the derivative of polythiophene or a variety of；The conducting polymer state is solid phase nano particle or liquid solution.
2. a kind of lithium ion cell nano silicon substrate composite fibre negative electrode material as described in claim 1, it is characterised in that:
The siliceous compound or compound be Si, SiOx, Si-M alloy, in Si/C, SiOx/C, Si-M/C at least One kind, wherein M be metal or metal oxide, 0≤x≤2, C be organic carbon, inorganic carbon, graphite, graphene, carbon nanotube or Carbon fiber.
3. a kind of lithium ion cell nano silicon substrate composite fibre negative electrode material as described in claim 1, it is characterised in that: described Nano silicon-based active particles diameter is in 10-500nm.
4. a kind of lithium ion cell nano silicon substrate composite fibre negative electrode material as described in claim 1, it is characterised in that: described The diameter of nanofiber matrix is in 100-1000nm.
5. a kind of lithium ion cell nano silicon substrate composite fibre negative electrode material as described in claim 1, it is characterised in that: 1000 ≤ conducting polymer number-average molecular weight≤300,000.
6. a kind of lithium ion cell nano silicon substrate composite fibre negative electrode material as described in claim 1, it is characterised in that: described Organic solvent is at least one of ethyl alcohol, dimethylformamide, dimethyl acetamide or dimethyl sulfoxide.
7. a kind of lithium ion cell nano silicon substrate composite fibre negative electrode material as described in claim 1, it is characterised in that: described Metal or metal oxide M be Li, Li2O、Co、CoO、Fe、Fe2O3、Mg、MgO、Sn、SnO、Ti、TiO2, Ag, AgO or Cr.
8. a kind of preparation method of negative electrode material as described in any one of claims 1 to 7, it is characterised in that: including making as follows Standby step:
(1), raw material mixes: the nano silicon-based active particles are uniformly mixed to form mixture H1 with conducting polymer；
(2), prepare spinning solution: by polymer stirring and dissolving in organic solvent and deaeration processing be configured to uniform spinning solution H2；
(3), it prepares blend spinning liquid: mixture H1 being dispersed with stirring in spinning solution H2, uniform blend spinning liquid H3 is obtained；
(4), electrostatic spinning: blend spinning liquid H3 is encased in syringe, carries out electrostatic spinning, spinning off field in high-pressure electrostatic Liquid thread curing molding in air, then low-temperature vacuum drying is to get arriving lithium ion cell nano silicon substrate composite fibre cathode Material.
9. preparation method as claimed in claim 8, it is characterised in that: the voltage of electric field of the electrostatic spinning is 12-30kV；It spins Silk liquid stream rate is 0.5-1.5mL/h；Spinning distance is 8-30cm；The temperature of spinning environment is 25-30 DEG C；Air humidity is 25-45%.
10. preparation method as claimed in claim 8, it is characterised in that: nano silicon-based active particles in the raw material mixing Mixed with conducting polymer using any mode that solid phase mixing or solid-liquid mix, when solid phase mixing, using ball milling or Mechanical stirring mixing, when solid-liquid is mixed using centrifugation, ultrasonic mixing.
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