CN103794769B - The preparation method of lithium ion battery negative material - Google Patents

The preparation method of lithium ion battery negative material Download PDF

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CN103794769B
CN103794769B CN201410055120.1A CN201410055120A CN103794769B CN 103794769 B CN103794769 B CN 103794769B CN 201410055120 A CN201410055120 A CN 201410055120A CN 103794769 B CN103794769 B CN 103794769B
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composite
lithium ion
ion battery
preparation
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CN103794769A (en
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尚玉明
崔涛
王要武
何向明
李建军
王莉
张森
高剑
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Tsinghua University
Jiangsu Huadong Institute of Li-ion Battery Co Ltd
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Tsinghua University
Jiangsu Huadong Institute of Li-ion Battery Co Ltd
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Priority to PCT/CN2015/070977 priority patent/WO2015124049A1/en
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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
    • 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
    • H01M4/58—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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 a kind of preparation method of lithium ion battery negative material, CNT and softex kw are added in deionized water, sonic oscillation, then add ethanol and ammoniacal liquor further sonic oscillation, obtain the alkaline dispersion liquid of CNT; The ethanolic solution of ethyl orthosilicate is added drop-wise in the alkaline dispersion liquid of this CNT, 30 ~ 60 DEG C of reactions, produces precipitation; Separate and wash this precipitation by deionized water; Be placed in reacting furnace 550 ~ 600 DEG C of sintering under inert atmosphere; Mix with zinc powder, be placed in reacting furnace, under inert atmosphere, 650 ~ 700 DEG C of sintering, obtain sintered product; Put into acid solution, react 30 ~ 60 DEG C of stirrings, separate and dry solid product; And mix with carbon source and dispersion solvent, concentrate drying is placed in reacting furnace, and under inert atmosphere, 600 ~ 800 DEG C of sintering, obtain CNTs/Si/C composite.

Description

The preparation method of lithium ion battery negative material
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, relate in particular to a kind of preparation method of Silicon Based Anode Materials for Lithium-Ion Batteries.
Background technology
Commercially produce LiCoO from Sony in 19912/ C rocking chair battery, that rechargeable lithium ion batteries has become is portable, the important component part of amusement, calculating and telecommunication apparatus, indispensable in the rich informationalized mobile devices such as field camera, MP4 player, notebook computer and mobile phone. Meanwhile, be subject to the pressure of petroleum reserves and environmental protection, countries in the world are all at competitively Developing Hybrid Vehicle Industry and pure electric automobile in recent years, and will progressively replace traditional fuel-engined vehicle, to reduce the pollution of vehicle exhaust to environment. Lithium-ion electric pool technology advanced and in the application in electric automobile field, has excited the research boom in global range.
At present, business-like lithium ion battery adopts graphite as negative material, and its source is abundant, cheap, stable operating voltage, but theoretical embedding lithium capacity only has 372mAh/g. Up to now, in negative material, the theoretical capacity of silicon is the highest, as Li and Si alloying formation Li4.4When Si, theoretical capacity is 4212mAh/g, much larger than the theoretical capacity of graphite; Meanwhile, silicon is safer more reliable than graphite cathode, so worldwide studied widely. But also there is the shortcoming of self in silicium cathode material: (1) silicium cathode in charge and discharge process with larger Volume Changes (volumetric expansion is up to 300%), strong stress causes silicon grain generation efflorescence, and then separate with conductive agent, peel off from collector, thereby cause sizable irreversible capacity that discharges first, reduced cycle performance. (2) silicon materials electric conductivity is poor, and this has also affected its cycle performance under high current charge-discharge.
For solving the problem of silicium cathode material expansion efflorescence and poorly conductive, current taked method is mainly prepares One Dimension Silicon nano wire or two-dimentional silicon nano thin-film. But these two kinds of methods need large-scale, expensive equipment, and preparation technology is numerous and diverse, is difficult to realize commercial application.
Summary of the invention
In view of this, the necessary preparation method that a kind of silica-based lithium ion battery negative material with better cycle performance and applicable industrial applications is provided.
A kind of preparation method of lithium ion battery negative material, comprise the following steps: CNT and softex kw are added in deionized water, sonic oscillation, then add ethanol and ammoniacal liquor further sonic oscillation, obtain the alkaline dispersion liquid of CNT; The ethanolic solution of ethyl orthosilicate is added drop-wise in the alkaline dispersion liquid of this CNT, 30 ~ 60 DEG C of reactions, produces precipitation; Separate and wash this precipitation by deionized water, after being dried, obtaining CNTs/CTAB/SiO2Composite; By this CNTs/CTAB/SiO2Composite is placed in reacting furnace, and under inert atmosphere, 550 ~ 600 DEG C of sintering, obtain CNTs/SiO2Composite; By this CNTs/SiO2Composite mixes with zinc powder, is placed in reacting furnace, and under inert atmosphere, 650 ~ 700 DEG C of sintering, obtain sintered product; This sintered product is put into acid solution, react 30 ~ 60 DEG C of stirrings, separate and dry solid product, obtain CNTs/Si composite; And this CNTs/Si composite is mixed with carbon source and dispersion solvent, concentrate drying is placed in reacting furnace, and under inert atmosphere, 600 ~ 800 DEG C of sintering, obtain CNTs/Si/C composite.
The present invention is directed to silicium cathode poorly conductive and in charge and discharge process, can produce the problem of serious bulk effect, a kind of preparation method of negative material has been proposed, first generate nanometer grade silica clad in carbon nano tube surface, then surperficial silica is reduced to silicon, by carbon coating technology, obtain a kind of CNTs/Si/C multilayer coating structure composite afterwards. During using this composite as lithium ion battery negative material, silicon is sandwiched between two kinds of material with carbon elements, and the effect that CNT and carbon play cushion suppresses the expansion efflorescence of silicon in charge and discharge process. Meanwhile, utilize the satisfactory electrical conductivity of external coating carbon and the three-dimensional conductive network of internal layer CNT formation can increase the electric conductivity of silicon materials. Therefore, the cycle performance of silicium cathode material is improved. Production technology of the present invention is simple, does not use complex apparatus, easily realizes suitability for industrialized production.
Brief description of the drawings
Fig. 1 is the TEM figure of the lithium ion battery negative material of the embodiment of the present invention 1.
Fig. 2 is the XRD figure of the lithium ion battery negative material of the embodiment of the present invention 1.
Fig. 3 is lithium ion battery negative material and the cycle performance contrast of pure silicon powder in battery of the embodiment of the present invention 1.
Following detailed description of the invention further illustrates the present invention in connection with above-mentioned accompanying drawing.
Detailed description of the invention
Below in conjunction with the accompanying drawings and the specific embodiments the preparation method of lithium ion battery negative material provided by the invention is described in further detail.
Embodiment of the present invention provides a kind of preparation method of lithium ion battery negative material, comprises the following steps:
S1, adds CNT (CNTs) and softex kw (CTAB) in deionized water, sonic oscillation, then add ethanol and ammoniacal liquor further sonic oscillation, obtain the alkaline dispersion liquid of CNTs;
S2, is added drop-wise to the ethanolic solution of ethyl orthosilicate in the alkaline dispersion liquid of this CNTs, 30 ~ 60 DEG C of reactions, produces precipitation;
S3, separates and washs this precipitation by deionized water, after being dried, obtains CNTs/CTAB/SiO2Composite;
S4, by this CNTs/CTAB/SiO2Composite is placed in reacting furnace, and under inert atmosphere, 550 ~ 600 DEG C of sintering, obtain CNTs/SiO2Composite;
S5, by this CNTs/SiO2Composite mixes with zinc powder, is placed in reacting furnace, and under inert atmosphere, 650 ~ 700 DEG C of sintering, obtain sintered product;
S6, puts into acid solution by this sintered product, reacts 30 ~ 60 DEG C of stirrings, separates and dry solid product, obtains CNTs/Si composite;
S7, mixes this CNTs/Si composite with carbon source and dispersion solvent, concentrate drying is placed in reacting furnace, and under inert atmosphere, 600 ~ 800 DEG C of sintering, obtain CNTs/Si/C composite.
In this step S1, the time of this sonic oscillation can be 1 ~ 4 hour. This CNTs can be SWCN or the multi-walled carbon nano-tubes of diameter 10 ~ 40nm. The mass ratio of this CNTs and CTAB can be 1:10 ~ 1:30. In the dicyandiamide solution of this alkalescence dispersion liquid, the volume fraction of water can be 20 ~ 40%, and the volume fraction of ethanol can be 60% ~ 80%, and the volume fraction of ammoniacal liquor can be 1 ~ 2%. The amount of this CNTs adding is by the cubage of CNTs in end product CNTs/Si/C composite, and the mass fraction of CNTs in CNTs/Si/C composite can be 10% ~ 30%. In the alkaline dispersion liquid of CNTs, CTAB is coated on carbon nano tube surface.
In this step S2, particularly, when alkaline dispersion liquid that can this CNTs of mechanical agitation, drip, can be 12 ~ 18 hours the reaction time of 30 ~ 60 DEG C. The volume fraction of the ethanolic solution of this ethyl orthosilicate can be 4% ~ 10%. The addition of this ethyl orthosilicate is by the cubage of Si in end product CNTs/Si/C composite, and the mass fraction of Si in CNTs/Si/C composite can be 50%-80%. The rate of addition of the ethanolic solution of this ethyl orthosilicate can be 0.5ml/min ~ 1ml/min.
In this step S3, particularly, can pass through centrifuge centrifugation, take out lower sediment, and use deionized water cyclic washing, until filtrate is neutral, subsequently this precipitation is put into 80 ~ 120 DEG C of vacuum drying chambers and dried 12 ~ 24 hours, obtain this CNTs/CTAB/SiO2Composite. This centrifuge speed can be 4000r/min ~ 4500r/min, and centrifugation time can be 10 minutes ~ 15 minutes. At this CNTs/CTAB/SiO2In composite, CTAB is connected silica with CNT, and silica is coated on carbon nano tube surface by CTAB.
In this step S4, this sintering time can be 6 ~ 8 hours. At this CNTs/SiO2In composite, silica is directly coated on carbon nano tube surface.
In this step S5, this sintering time can be 1 ~ 2 hour. This CNTs/SiO2The mass ratio of composite and zinc powder can be 1:1 ~ 1:1.5.
In this step S6, the concentration of this acid solution can be 0.1 ~ 1mol/L, for example, can be 0.1 ~ 1mol/LHCl solution, and the stirring reaction time can be 1 ~ 2 hour. This separation dry solid product can be specifically to use deionized water cyclic washing, until filtrate is neutral, then puts into 80 ~ 120 DEG C of vacuum drying chambers and dry 12 ~ 24 hours. In this CNTs/Si composite, silicon is directly coated on carbon nano tube surface.
In this step S7, this sintering time can be 4 ~ 6 hours. This carbon source can be one or more in glucose, sucrose, petroleum coke, phenolic resins, polyvinyl alcohol, polymethyl methacrylate, polypropylene, PLA, starch, polyarylether, polyester, polyurethane, polyarylate, polyether-ketone, polyether sulfone and polyimides. The mass fraction of the RESEARCH OF PYROCARBON that selected carbon source generates in CNTs/Si/C composite can be 10% ~ 30%. This dispersion solvent can be one or more in methyl alcohol, ethanol, water, acetone, ethyl acetate, chloroform, toluene, ether, benzinum, dimethyl formamide, dimethylacetylamide, N-methyl pyrrole Lip river alkane ketone and dimethyl sulfoxide (DMSO), and addition is 50-100 times of this CNTs/Si composite quality. In this CNTs/Si/C composite, silicon face is coated carbon-coating further, is CNT thereby form inside, and centre is silicon layer, the composite that outside is carbon-coating. By adjusting CNT, silicon and the mass fraction of carbon in CNTs/Si/C composite, can control the thickness of silicon layer, make the CNT of both sides and carbon-coating can effectively suppress the Volume Changes of silicon in charge and discharge process.
At this step S4, in S5 and S7, this inert atmosphere can be nitrogen or argon gas.
The preparation method of the described negative material by the embodiment of the present invention, can first generate nanometer grade silica clad in carbon nano tube surface, then surperficial silica is reduced to silicon, by carbon coating technology, obtains a kind of CNTs/Si/C multilayer coating structure composite afterwards. During using this composite as lithium ion battery negative material, silicon is sandwiched between two kinds of material with carbon elements, and the effect that CNT and carbon play cushion suppresses the expansion efflorescence of silicon in charge and discharge process. Meanwhile, utilize the satisfactory electrical conductivity of external coating carbon and the three-dimensional conductive network of internal layer CNT formation can increase the electric conductivity of silicon materials. The present invention is without preparing silicon nanowires by complicated technique, but can obtain the effect similar or more excellent to silicon nanowires, and production technology is simple, easily realizes suitability for industrialized production.
Embodiment 1
S1, takes 200mgCNTs and 6gCTAB, joins in 60ml deionized water, and sonic oscillation 1 hour, adds 120ml absolute ethyl alcohol, continues after ultrasonic 1 hour, then adds 5ml ammoniacal liquor, obtains the alkaline dispersion liquid of CNTs.
S2, the ethanolic solution of the ethyl orthosilicate that dose volume mark is 6% is slowly added drop-wise to the ethanolic solution of this ethyl orthosilicate of 100ml in the alkaline dispersion liquid of this CNTs under mechanical agitation, rate of addition is 1ml/min, after dropwising, control 40 DEG C of reaction temperatures, continue reaction 18 hours.
S3, by centrifuge with the rotating speed of 4000r/min centrifugal 15 minutes for step S2 products therefrom, takes out lower sediment, by precipitate with deionized water cyclic washing, until filtrate is neutral, subsequently precipitation is put into 80 DEG C of vacuum drying chambers and dried 24 hours, obtain CNTs/CTAB/SiO2Composite.
S4, by this CNTs/CTAB/SiO2Composite moves into the tubular react furnace of nitrogen protection, and 550 DEG C of sintering 8 hours, obtain CNTs/SiO2Composite.
S5, by this CNTs/SiO2Composite and 2.5g zinc powder fully mix in the tubular react furnace of rear immigration nitrogen protection, 650 sintering 2 hours.
S6, processes step S5 gained solid 1 hour with 60 DEG C of 0.1mol/LHCl solution, uses deionized water cyclic washing, until filtrate is neutral, then puts into 80 DEG C of vacuum drying chambers and dries 24 hours, obtains CNTs/Si composite.
S7, is placed in container by this CNTs/Si composite, adds 0.55g glucose and 80g ethanol, stirs 2 hours to mixing; By dry gained mixture reduced pressure concentration, ethanol reclaims and reuses, and solid product moves in the tubular react furnace of nitrogen protection, and 700 DEG C of sintering 6 hours, obtain this CNTs/Si/C composite.
The CNTs/Si/C composite obtaining is by transmission electron microscope observing, and TEM photo as shown in Figure 1. Refer to Fig. 2, this CNTs/Si/C composite is carried out to XRD test, the characteristic peak of C, CNTs and Si all marks in Fig. 2. The CNTs/Si/C composite of embodiment 1 is assembled to lithium ion battery as negative active core-shell material, and just very lithium metal, carries out charge-discharge performance test. And assemble control cell, difference only adopts pure silicon powder at negative active core-shell material, carries out under the same conditions charge-discharge performance test. The test result of two kinds of batteries as shown in Figure 3, although can see that the battery of pure silicon powder has higher specific capacity in the time of initial charge, but along with the increase of cycle-index sharp-decay. Although and the initial charge capacity of CNTs/Si/C composite is lower, cyclical stability is improved largely than pure silicon powder, after circulation repeatedly, still have higher capability retention.
Embodiment 2
S1, takes 200mgCNTs and 4gCTAB, joins in 70ml deionized water, and sonic oscillation 2 hours, adds 100ml absolute ethyl alcohol, continues after ultrasonic 2 hours, then adds 4ml ammoniacal liquor, obtains the alkaline dispersion liquid of CNTs.
S2, the ethanolic solution of the ethyl orthosilicate that dose volume mark is 10% is slowly added drop-wise to the ethanolic solution of this ethyl orthosilicate of 40ml in the alkaline dispersion liquid of this CNTs under mechanical agitation, rate of addition is 0.5ml/min, after dropwising, control 60 DEG C of reaction temperatures, continue reaction 12 hours.
S3, by centrifuge with the rotating speed of 4500r/min centrifugal 10 minutes for step S2 products therefrom, takes out lower sediment, by precipitate with deionized water cyclic washing, until filtrate is neutral, subsequently precipitation is put into 120 DEG C of vacuum drying chambers and dried 12 hours, obtain CNTs/CTAB/SiO2Composite.
S4, by this CNTs/CTAB/SiO2Composite moves into the tubular react furnace of nitrogen protection, and 600 DEG C of sintering 6 hours, obtain CNTs/SiO2Composite.
S5, by this CNTs/SiO2Composite and 2g zinc powder fully mix in the tubular react furnace of rear immigration nitrogen protection, 685 sintering 2 hours.
S6, processes step S5 gained solid 2 hours with 30 DEG C of 0.5mol/LHCl solution, uses deionized water cyclic washing, until filtrate is neutral, then puts into 120 DEG C of vacuum drying chambers and dries 12 hours, obtains CNTs/Si composite.
S7, is placed in container by this CNTs/Si composite, adds 0.37g polyvinyl alcohol and 60g chloroform, stirs 3 hours to mixing; By dry gained mixture reduced pressure concentration, chloroform reclaims and reuses, and solid product moves in the tubular react furnace of nitrogen protection, and 800 DEG C of sintering 4 hours, obtain this CNTs/Si/C composite.
In addition, those skilled in the art also can do other and change in spirit of the present invention, and certainly, the variation that these do according to spirit of the present invention, within all should being included in the present invention's scope required for protection.

Claims (9)

1. a preparation method for lithium ion battery negative material, comprises the following steps:
CNT and softex kw are added in deionized water, sonic oscillation, then addEnter ethanol and ammoniacal liquor further sonic oscillation, obtain the alkaline dispersion liquid of CNT;
The ethanolic solution of ethyl orthosilicate is added drop-wise in the alkaline dispersion liquid of this CNT, 30～60DEG C reaction, produces precipitation;
Separate and wash this precipitation by deionized water, after being dried, obtaining CNTs/CTAB/SiO2Composite;
By this CNTs/CTAB/SiO2Composite is placed in reacting furnace, under inert atmosphere 550～600 DEG CSintering, obtains CNTs/SiO2Composite;
By this CNTs/SiO2Composite mixes with zinc powder, is placed in reacting furnace, under inert atmosphere650～700 DEG C of sintering, obtain sintered product;
This sintered product is put into acid solution, react 30～60 DEG C of stirrings, separate and be dried solidPhase product, obtains CNTs/Si composite; And
This CNTs/Si composite is mixed with carbon source and dispersion solvent, and concentrate drying is placed on insteadAnswer in stove, under inert atmosphere, 600～800 DEG C of sintering, obtain CNTs/Si/C composite, and this carbon source isGlucose, sucrose, petroleum coke, phenolic resins, polyvinyl alcohol, polymethyl methacrylate, polypropylene,In PLA, starch, polyarylether, polyurethane, polyarylate, polyether-ketone, polyether sulfone and polyimidesOne or more.
2. the preparation method of lithium ion battery negative material as claimed in claim 1, is characterized in that, this carbonThe mass fraction of nanotube in this CNTs/Si/C composite is 10%～30%.
3. the preparation method of lithium ion battery negative material as claimed in claim 1, is characterized in that, silicon existsMass fraction in this CNTs/Si/C composite is 50%-80%.
4. the preparation method of lithium ion battery negative material as claimed in claim 1, is characterized in that, carbon existsMass fraction in this CNTs/Si/C composite is 10%～30%.
5. the preparation method of lithium ion battery negative material as claimed in claim 1, is characterized in that, this carbonThe mass ratio of nanotube and softex kw is 1:10～1:30.
6. the preparation method of lithium ion battery negative material as claimed in claim 1, is characterized in that, this justThe volume fraction of the ethanolic solution of silester is 4%～10%.
7. the preparation method of lithium ion battery negative material as claimed in claim 1, is characterized in that, this justThe rate of addition of the ethanolic solution of silester is 0.5mL/min～1mL/min.
8. the preparation method of lithium ion battery negative material as claimed in claim 1, is characterized in that, should CNTs/SiO2The mass ratio of composite and zinc powder is 1:1～1:1.5.
9. the preparation method of lithium ion battery negative material as claimed in claim 1, is characterized in that, this acidSolution is 0.1～1mol/LHCl solution.
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