CN106711461A - Spherical porous silicon/carbon composite material as well as preparation method and application thereof - Google Patents
Spherical porous silicon/carbon composite material as well as preparation method and application thereof Download PDFInfo
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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 spherical porous silicon/carbon composite material as well as a preparation method and application thereof. The spherical porous silicon/carbon composite material is structurally characterized in that a SiOx/C matrix, graphite with small particle size and a conductive agent are dispersed in porous amorphous carbon, wherein the average particle diameter is 12-25mu m; the method comprises the following steps of carrying out first coating on a SiOx raw material with powder pitch, and performing heat treatment so as to obtain a SiOx/C material; then performing ball milling by use of a wet method so as to reduce the particle diameter of powder, adding a carbon source adhesive, the graphite with the small particle diameter and the conductive agent, and performing high-speed dispersion, thereby obtaining pulp; and finally performing spray granulation and sintering on the pulp, thereby obtaining the final spherical porous silicon/carbon composite material. According to the invention, SiOx is dispersed in cracking carbon, the graphite and the conductive agent, so that SiOx volume expansion during a charge/discharge process is buffered, and the conductibility is enhanced; by virtue of the porous structure, the imbibition rate and cycle performance of the material can be effectively improved; by virtue of bitumencarb coating and high-heat treatment performed in advance, SiOx is prevented from being directly contacted with an electrolyte, and furthermore, the stability and first efficiency of the silicon/carbon material are improved.
Description
Technical field
The invention belongs to field of lithium ion battery material, and in particular to a kind of spherical porous Si-C composite material and its preparation
Method and purposes.
Background technology
In recent years, as the acceleration of new-energy automobile industry is advanced, electrokinetic cell rapidly becomes the focus of business circles investment,
High-performance of the exploitation with independent intellectual property right, high safety, inexpensive lithium-ion-power cell are extremely urgent, and lithium-ion electric
Negative material used by pond is one of the key factor for determining its performance.The lithium ion battery negative material researched and developed at present
Mainly there are carbon material and the major class of non-carbon material two, in non-carbons negative material, silicon materials have theoretical ratio higher due to it
Capacity（Li22Si5：4200mAh/g）With relatively low intercalation potential（vs Li+/Li）, while silicon rich reserves, cost on earth
Relatively low, environmental sound, thus be a kind of very rising lithium ion battery negative material.Silicon based anode material is main
The problems such as facing poorly conductive and cycle performance difference, typically solves these problems using being combined.Carbon is with its flexible, good electricity
It is preferable that the advantages of subconductivity, less density, less volumetric expansion, appropriate embedding lithium ability, turns into silicon based anode material
Active matrix.
Silica-base material and carbon material are combined and have been carried out numerous studies at present, and form a series of patents.CN
102263245A discloses a kind of preparation method of spherical porous composite cathode material for lithium ion cell, by Si oxide high energy ball
Mixing with graphite after mill carries out mist projection granulating, and the globular material that then will be obtained sinters obtain spherical porous lithium in an inert atmosphere
Ion battery composite negative pole material.The particle obtained after invention spray drying is only one layer of the surface porous material of amorphous carbon
Material, in lithium battery, the silicon in material is easy to exposure in the electrolytic solution, it is difficult to form the SEI films of stabilization, and then causes charge and discharge
Electrical efficiency is low, cycle performance of battery is poor.CN 103474667A disclose a kind of Si-C composite material and preparation method thereof, use
Nano-silicon adds graphite to be mixed, and then CVD coats one layer of carbon, then one layer of carbon of liquid phase coating, finally crushes and obtains final material
Material.Si-C composite material prepared by the method by including nano-silicon/graphite particle, the first carbon coating layer and organic outside interior successively
Cracking carbon-coating, with excellent cycle performance and rate charge-discharge performance.But the method complex operation, and CVD is employed,
It is relatively costly, be not suitable for industrialization.
The content of the invention
The purpose of the present invention is to solve the shortcomings of the prior art, there is provided it is a kind of with specific capacity higher, first efficiency,
Good cycle performance and preparation technology cost is relatively low, is adapted to spherical porous Si-C composite material of industrialization and preparation method thereof
With purposes.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of spherical porous Si-C composite material, its
Innovative point is：The Si-C composite material structure is SiOx/ C matrix, small particle graphite and conductive agent are dispersed in porous nothing to be determined
In shape carbon, the graphite average grain diameter is 12-25 μm；
The SiOx/ C matrix is the SiO of carbon coatingxMatrix, the span of the x is the SiO more than 0 and less than 2x/C
Matrix average grain diameter is 1-5 μm；
The small particle graphite is the one kind in Delanium, native graphite and carbonaceous mesophase spherules, the average grain of the graphite
Footpath is 1-10 μm；
The conductive agent is from the combination of one or more in acetylene black, Super P, carbon fiber and CNT.
Another object of the present invention is to disclose a kind of preparation method of spherical porous Si-C composite material, and its innovative point exists
In：Comprise the following steps that：
（1）By a certain proportion of SiOxPowder adds VCJ heating batch mixer stirring a period of times with asphalt powder, then in inertia
Heated up under atmosphere and coated；
（2）By the material after cladding, high-temperature heat treatment for a period of time and is sieved under an inert atmosphere, obtains SiOx/ C matrix；
（3）By SiOx/ C matrix is added in organic solvent, and it is 1-5 μm to use agitating ball mill wet grinding to particle diameter, is obtained
SiOx/ C slurries；
（4）Slurry, carbon source binding agent, small particle graphite and the conductive agent that will be obtained after grinding carry out high speed dispersion, then spray
Drying-granulating obtains spherical precursor；
（5）Finally spherical precursor is sintered under an inert atmosphere, sieve classification is crossed and is obtained final spherical porous silicon-carbon composite wood
Material.
Further, the step（1）In SiOxPowder average particle size is 5-20 μm；The asphalt powder is dripped for oil
Blue or green or coal tar pitch, average grain diameter is 2-10 μm；The SiOxThe mass percent 60-90 of powder and asphalt powder：1-40；It is described
Speed of agitator is 60-100rpm, mixing time 0.5-3h；The inert gas is a kind in nitrogen, argon gas, helium, neon；
1-5 DEG C of the heating rate/min, 200-500 DEG C of intensification terminal, soaking time is 1-5h.
Further, the step（2）In inert atmosphere for the inert gas be nitrogen, argon gas, helium, neon in
1 kind；Heat treatment 10-20 DEG C of the heating rate/min, 900-1100 DEG C of intensification terminal, soaking time is 3-10h.
Further, the step（3）In organic solvent be 1 in ethanol, ethylene glycol, isopropanol, acetone, n-butanol
Kind；The agitating ball mill speed of agitator is 150-300rpm, and milling time is 1-5h；The slurry solid content is 5%-15%.
Further, the step（4）In carbon source binding agent be glucose, sucrose, citric acid, polyethylene glycol, poly- second
One kind in enol butyral, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, mass fraction is 5%-
20%；The small particle graphite is a kind in Delanium, native graphite and carbonaceous mesophase spherules, and average grain diameter is 1-10 μm,
Mass fraction is 40%-70%；The conductive agent is one or more in acetylene black, Super P, carbon fiber and CNT
Combination, mass fraction is 1%-5%；The high speed dispersion mixing uses high speed dispersor, and the rotating speed is 500-1500rpm, institute
Jitter time is stated for 0.5-3h, the slurry solid content is 10-30%.
Further, the step（4）In spray drying granulation use centrifugal spraying granulator, inlet temperature is 180-
220 DEG C, outlet temperature is 90-120 DEG C；The sponging granulator feed pump frequency is 10-20Hz, and atomizing disk frequency is 250-
300Hz。
Further, the step（5）In inert atmosphere for the inert gas be nitrogen, argon gas, helium, neon in
1 kind；Sintering 5-10 DEG C of the heating rate/min, 400-700 DEG C of intensification terminal, soaking time is 3-10h.
Another object of the present invention is to disclose a kind of purposes of spherical porous Si-C composite material, and its innovative point is：
The spherical porous Si-C composite material can be used as negative material manufacture lithium ion battery.
Beneficial effects of the present invention are as follows：The present invention can form porous knot when carbon source binding agent sintering is cracked into carbon
Structure, can accommodate SiOxThe Volume Changes in charge and discharge process, while fully and electrolyte contacts, having final silicon carbon material
Standby specific capacity and good cycle performance higher.Using pitch as carbon source elder generation SiOxMaterial surface coats one layer of carbon, and leads to
Cross high-temperature process and be disproportionated into nano Si and be dispersed in SiO2In, it is to avoid SiO when ultimately forming loose structurexExposure in the electrolytic solution, is carried
The silicon carbon material stability and efficiency first for preparing are risen；SiOxSmall particle graphite and cracking carbon around/C can further delay
Volume Changes are rushed, and increases the electric conductivity of material, the Si-C composite material that further prepared by lifting together with the conductive agent for adding
With good cycle performance；Silicon carbon material preparation method cost of the invention is relatively low, easily amplifies, and is especially suitable for industrialization.
Brief description of the drawings
Fig. 1 is material surface scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 1；
Fig. 2 is material section scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 1；
Fig. 3 is the SiO before and after the high-temperature heat treatment of the embodiment of the present invention 1x/ C-material X ray diffracting spectrum；
Fig. 4 for the embodiment of the present invention 1 Si-C composite material as negative pole when button cell loop test figure.
Specific embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation
Content disclosed by book understands other advantages of the invention and effect easily.
A kind of spherical porous Si-C composite material, Si-C composite material structure is SiOx/ C matrix, small particle graphite and lead
Electric agent is dispersed in porous amorphous carbon, and graphite average grain diameter is 12-25 μm；
SiOx/ C matrix is the SiO of carbon coatingxMatrix, the span of x is more than 0 and less than 2, SiOx/ C matrix average grain diameter
It is 1-5 μm；
Small particle graphite is the one kind in Delanium, native graphite and carbonaceous mesophase spherules, and the average grain diameter of graphite is 1-10 μ
m；
Conductive agent is from the combination of one or more in acetylene black, Super P, carbon fiber and CNT.
A kind of preparation method of spherical porous Si-C composite material, comprises the following steps that：
（1）By a certain proportion of SiOxPowder adds VCJ heating batch mixer stirring a period of times with asphalt powder, then in inertia
Heated up under atmosphere and coated；SiOxPowder average particle size is 5-20 μm；Asphalt powder is asphalt or coal tar pitch, average grain
Footpath is 2-10 μm；SiOxThe mass percent 60-90 of powder and asphalt powder：1-40；Speed of agitator is 60-100rpm, stirring
Time 0.5-3h；Inert gas is a kind in nitrogen, argon gas, helium, neon；1-5 DEG C of heating rate/min, intensification terminal
200-500 DEG C, soaking time is 1-5h.
（2）By the material after cladding, high-temperature heat treatment for a period of time and is sieved under an inert atmosphere, obtains SiOx/ C matrix；
Inert atmosphere is that inert gas is a kind in nitrogen, argon gas, helium, neon；Heat treatment 10-20 DEG C of heating rate/min, heats up
900-1100 DEG C of terminal, soaking time is 3-10h.
（3）By SiOx/ C matrix is added in organic solvent, and it is 1-5 μm to use agitating ball mill wet grinding to particle diameter, is obtained
To SiOx/ C slurries；Organic solvent is a kind in ethanol, ethylene glycol, isopropanol, acetone, n-butanol；Agitating ball mill stirring turns
Speed is 150-300rpm, and milling time is 1-5h；Slurry solid content is 5%-15%.
（4）Slurry, carbon source binding agent, small particle graphite and the conductive agent that will be obtained after grinding carry out high speed dispersion, then
Spray drying granulation obtains spherical precursor；Carbon source binding agent is glucose, sucrose, citric acid, polyethylene glycol, polyvinyl alcohol contracting
One kind in butyraldehyde, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, mass fraction is 5%-20%；Granule
Footpath graphite is a kind in Delanium, native graphite and carbonaceous mesophase spherules, and average grain diameter is 1-10 μm, and mass fraction is
40%-70%；Conductive agent is the combination of one or more in acetylene black, Super P, carbon fiber and CNT, and mass fraction is
1%-5%；High speed dispersion mixing uses high speed dispersor, and rotating speed is 500-1500rpm, and jitter time is 0.5-3h, and slurry contains admittedly
It is 10-30% to measure, and spray drying granulation uses centrifugal spraying granulator, and inlet temperature is 180-220 DEG C, and outlet temperature is 90-
120℃；Sponging granulator feed pump frequency is 10-20Hz, and atomizing disk frequency is 250-300Hz.
（5）Finally spherical precursor is sintered under an inert atmosphere, mistake sieve classification obtains final spherical porous silicon-carbon and answers
Condensation material, inert atmosphere is that inert gas is a kind in nitrogen, argon gas, helium, neon；Sintering 5-10 DEG C of heating rate/min,
400-700 DEG C of intensification terminal, soaking time is 3-10h.
A kind of purposes of spherical porous Si-C composite material, spherical porous Si-C composite material can be used as negative material manufacture
Lithium ion battery.
Embodiment 1
It is prepared by Si-C composite material：It is 2.5 by SiOx powder that 2.4kg average grain diameters D50 is 6 μm and 0.6kg average grain diameters D50
μm asphalt powder add VCJ heating mixers, unlatching is stirred and is passed through high pure nitrogen and drains air, and rotating speed is
80rpm, the time is 1h, is kept stirring for, and is then warming up to 400 DEG C of insulation 2h with the heating rate of 3 DEG C/min, and collection obtains pitch
The SiOx materials of cladding.Using batch-type furnace in a nitrogen atmosphere, the SiOx to pitch-coating is heat-treated, with 10 DEG C/min's
Speed is warming up to 1000 DEG C of insulation 5h and sieves, the SiOx/C materials after being heat-treated.Take the SiOx/C after 500g heat treatments
Material uses agitating ball mill wet grinding, and used as solvent, solid content is 15% to ethanol, rotating speed 260rpm, milling time 3h, will
Slurry and 150g polyvinylpyrrolidones, the Delanium that 1000g average grain diameters are 6.5 μm, the 30g conductive agents Super- for obtaining
P and 3000g ethanol adds high speed dispersor dispersion 1h, and rotating speed is 1000rpm.Then the slurry that will be obtained uses centrifugal spray
Drying-granulating machine drying-granulating, inlet temperature is 190 DEG C, and outlet temperature is 95 DEG C, and atomizer rotating speed 18000rpm dries atmosphere
It is nitrogen atmosphere, obtains spherical precursor.Finally spherical precursor is sintered in a nitrogen atmosphere using pusher furnace, with 5 DEG C/
The speed of min is warming up to 700 DEG C of sintering 3h, obtains final silicon carbon material.
It is prepared by negative plate：Electrode slice slurry is prepared by stirring then be coated on Copper Foil using automatic spray dryer and
Into slurry solvent is deionized water, and conductive agent is Super-p, and binding agent adds SBR emulsion for carboxymethylcellulose calcium, activity
Material, conductive agent and binding agent ratio are 8:1:1.
It is prepared by battery：Button half-cell using lithium piece as to electrode, in glove box according to anode cover, electrode slice, every
The order assembling CR2025 button cells of film, lithium piece, stainless steel gasket, nickel foam and negative electrode casing, electrolyte is using 1mol/L's
Used as electrolyte, solvent is 1 to LiPF6:1:1 EC/EMC/DMC, adds 10%FEC.
Battery testing：Using the charging and discharging curve of blue electrical testing button cell, 0.1C rate charge-discharges, blanking voltage
0.005-1.5V。
The Si-C composite material scanning electron microscope (SEM) photograph of preparation is as shown in Figures 1 and 2, it can be seen that the material for obtaining is ball
Shape loose structure, spheroidization degree is very good, and there is the cotton-shaped carbon of cracking on surface.Accompanying drawing 3 is the SiOx/C materials X before and after heat treatment
X ray diffraction collection of illustrative plates, it can be seen that material is non crystalline structure before heat treatment, and the peak of Si is occurred in that after heat treatment, shows that SiOx occurs
Disproportionation.
The charging and discharging curve test knot of the button cell prepared as negative material using Si-C composite material of the invention
Really as shown in fig. 4, it can be seen that the specific capacity of material is 617.5mAh/g or so, efficiency 90.04% or so, circulate 20 times first
Capability retention is 97.0%.
Embodiment 2
" 0.6kg asphalt powder " in embodiment 1 is changed to " 0.3kg asphalt powder " by embodiment 2, and other are constant.
Embodiment 3
" average grain diameter is 6.5 μm of Delanium " in embodiment 1 be changed to embodiment 3 " average grain diameter is 6.7 μm natural
Graphite ", other are constant.
Comparative example
It is prepared by Si-C composite material：Remove high-temperature heat treatment pitch-coating SiOx/ C-material this step, i.e., " using batch-type furnace in nitrogen
Under gas atmosphere, to the SiO of pitch-coatingxIt is heat-treated, 1000 DEG C of insulation 5h is warming up to the speed of 10 DEG C/min and is sieved,
SiO after being heat-treatedx/ C-material." this step, other are consistent with embodiment 1.
Si-C composite material button electricity relevant parameter prepared by embodiment 1-3 and comparative example is as shown in the table：
From above table, embodiment 1, embodiment 2 and the reversible capacity first of embodiment 3, first efficiency and 20 circulations
Capability retention is above comparative example.
The present invention can form loose structure when carbon source binding agent sintering is cracked into carbon, can accommodate SiOxIn discharge and recharge
During Volume Changes, while fully and electrolyte contacts, final silicon carbon material is possessed specific capacity higher and good
Cycle performance.Using pitch as carbon source elder generation SiOxMaterial surface coats one layer of carbon, and is disproportionated into nano Si by high-temperature process
It is dispersed in SiO2In, it is to avoid SiO when ultimately forming loose structurexExposure in the electrolytic solution, improves the silicon carbon material stabilization of preparation
Property and first efficiency；SiOxSmall particle graphite and cracking carbon around/C further buffer volumes can change, and with addition
Conductive agent increases the electric conductivity of material together, and the Si-C composite material that further prepared by lifting has good cycle performance；This
The silicon carbon material preparation method cost of invention is relatively low, easily amplifies, and is especially suitable for industrialization.
Above-described embodiment is presently preferred embodiments of the present invention, is not the limitation to technical solution of the present invention, as long as
Without the technical scheme that creative work can be realized on the basis of above-described embodiment, it is regarded as falling into patent of the present invention
Rights protection scope in.
Claims (9)
1. a kind of spherical porous Si-C composite material, it is characterised in that：The Si-C composite material structure is SiOxIt is/C matrix, small
Particle diameter graphite and conductive agent are dispersed in porous amorphous carbon, and the graphite average grain diameter is 12-25 μm；
The SiOx/ C matrix is the SiO of carbon coatingxMatrix, the span of the x is the SiO more than 0 and less than 2x/C
Matrix average grain diameter is 1-5 μm；
The small particle graphite is the one kind in Delanium, native graphite and carbonaceous mesophase spherules, the average grain of the graphite
Footpath is 1-10 μm；
The conductive agent is from the combination of one or more in acetylene black, Super P, carbon fiber and CNT.
2. a kind of preparation method of spherical porous Si-C composite material as claimed in claim 1, it is characterised in that：Specific steps
It is as follows：
By a certain proportion of SiOxPowder adds VCJ heating batch mixer stirring a period of times with asphalt powder, then in inert atmosphere
Lower intensification is coated；
By the material after cladding, high-temperature heat treatment for a period of time and is sieved under an inert atmosphere, obtains SiOx/ C matrix；
By SiOx/ C matrix is added in organic solvent, and it is 1-5 μm to use agitating ball mill wet grinding to particle diameter, obtains SiOx/C
Slurry；
Slurry, carbon source binding agent, small particle graphite and the conductive agent that will be obtained after grinding carry out high speed dispersion, are then spray-dried
Granulation obtains spherical precursor；
Finally spherical precursor is sintered under an inert atmosphere, sieve classification is crossed and is obtained final spherical porous Si-C composite material.
3. the preparation method of spherical porous Si-C composite material according to claim 2, it is characterised in that：The step
（1）In SiOxPowder average particle size is 5-20 μm；The asphalt powder is asphalt or coal tar pitch, and average grain diameter is 2-10
μm；The SiOxThe mass percent 60-90 of powder and asphalt powder：1-40；The speed of agitator is 60-100rpm, stirring
Time 0.5-3h；The inert gas is a kind in nitrogen, argon gas, helium, neon；1-5 DEG C of the heating rate/min, rises
200-500 DEG C of warm terminal, soaking time is 1-5h.
4. the preparation method of spherical porous Si-C composite material according to claim 2, it is characterised in that：The step
（2）In inert atmosphere be the inert gas be a kind in nitrogen, argon gas, helium, neon；The heat treatment heating rate
10-20 DEG C/min, 900-1100 DEG C of intensification terminal, soaking time is 3-10h.
5. the preparation method of spherical porous Si-C composite material according to claim 2, it is characterised in that：The step
（3）In organic solvent be a kind in ethanol, ethylene glycol, isopropanol, acetone, n-butanol；The agitating ball mill speed of agitator
It is 150-300rpm, milling time is 1-5h；The slurry solid content is 5%-15%.
6. the preparation method of spherical porous Si-C composite material according to claim 2, it is characterised in that：The step
（4）In carbon source binding agent for glucose, sucrose, citric acid, polyethylene glycol, polyvinyl butyral resin, polyvinylpyrrolidone,
One kind in polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, mass fraction is 5%-20%；The small particle graphite be Delanium,
1 kind in native graphite and carbonaceous mesophase spherules, average grain diameter is 1-10 μm, and mass fraction is 40%-70%；The conductive agent is
The combination of one or more in acetylene black, Super P, carbon fiber and CNT, mass fraction is 1%-5%；The high speed point
Scattered mixing uses high speed dispersor, and the rotating speed is 500-1500rpm, and the jitter time is 0.5-3h, and the slurry contains admittedly
It is 10-30% to measure.
7. the preparation method of spherical porous Si-C composite material according to claim 2, it is characterised in that：The step
（4）In spray drying granulation use centrifugal spraying granulator, inlet temperature is 180-220 DEG C, and outlet temperature is 90-120 DEG C；
The sponging granulator feed pump frequency is 10-20Hz, and atomizing disk frequency is 250-300Hz.
8. the preparation method of spherical porous Si-C composite material according to claim 2, it is characterised in that：The step
（5）In inert atmosphere be the inert gas be a kind in nitrogen, argon gas, helium, neon；The sintering heating rate 5-
10 DEG C/min, 400-700 DEG C of intensification terminal, soaking time is 3-10h.
9. a kind of purposes of spherical porous Si-C composite material as claimed in claim 1, it is characterised in that：It is described spherical porous
Si-C composite material can be used as negative material manufacture lithium ion battery.
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