CN109192957A - The Si-C composite material and preparation method and lithium ion battery of porous spherical core-shell structure - Google Patents
The Si-C composite material and preparation method and lithium ion battery of porous spherical core-shell structure Download PDFInfo
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Abstract
The Si-C composite material and preparation method and lithium ion battery of porous spherical core-shell structure, method include: S1 preparation Si/SiO2Nano particle mixed solution 1；S2 prepares the mixed solution 2 of polymer 1 and polymer 2；S3 prepares spraying precursor spherical Si/SiO2/ polymer composites；S4 prepares Si-C composite material: first sintering obtains porous spherical Si/SiO2/C composite material, and then strong acid etching removes the SiO2 layers of Si/C composite material to get porous spherical core-shell structure.The present invention is in the polymer by two kinds of different thermal decomposition temperatures, and first the low polymer of thermal decomposition temperature is burnt up in heating in air, forms nano aperture, high temperature cabonization is then carried out in inert gas, is formed by hole different from being carbonized naturally using single carbon source.The Si-C composite material that the present invention obtains is multicore core-shell structure spherical agglomerates, and surface has that obvious nano aperture, specific surface area are small, tap density is high；It is had clear improvement using its charge/discharge capacity of the lithium ion battery of the Si-C composite material and cycle performance.
Description
Technical field
The present invention relates to a kind of Si-C composite material and its preparation method and applications, more particularly to one kind to have porous spherical nucleocapsid
The Si-C composite material and its preparation method and lithium ion battery of structure, belong to lithium ion battery negative material preparation technical field.
Technical background
With the continuous development of lithium ion battery technology, current commercialized positive electrode is many kinds of, but is commercialized
Negative electrode material still or use graphite-like carbon negative pole material.Although graphite type material volume change in charge and discharge process
Small, stable structure, but the intrinsic theoretical specific capacity of graphite only has 372mAh/g, it is easy analysis under fast charge and low temperature in addition
Lithium, there are serious safety problems, greatly limit the development of lithium ion battery.In other numerous negative electrode materials
In, silicon based anode material is up to the theoretical specific capacity of 4200mAh/g with it, is not easy to analyse a system such as lithium, rich reserves, cheap
Column unique advantage and potentiality attract the sight of more and more researchers.
However there is also two maximum problems for silicon based anode material in practical applications: 1, in charge and discharge process up to
On the one hand 300% volume change, so mechanicals efforts caused by huge bulk effect occur silicon materials itself
Dusting, it is difficult to form stable SEI film on surface, to constantly consume electrolyte, cause efficiency for charge-discharge low；Another party
Face makes silicon active material fall off and lose activity with collector, leads to capacity attenuation, poor circulation.2, silicon itself is
The intrinsic conductivity of semiconductor material, material is lower, and only 10-4The S/cm order of magnitude influences the high rate performance and capacity of material
It plays.
In order to overcome the disadvantages described above of silicon based anode material, researchers would generally be modified it, change in numerous
In property means, most common improvement means are substantially summarized as two kinds at this stage: one is the processing of the nanosizing of material, such as nano-silicon
Ball [Adv.Mater 19:4067-4070；CN105118973A], silicon nanowires and nanotube [Nano Lett 9:491-495；
CN105609749A；CN102139876A], silicon nano thin-film [Power Sources 161:617-622] etc..Nanosizing can be with
Reduce the absolute volume variation degree of silicon, reduces lithium ion diffusion length, improve the chemical property of material；Another kind is to prepare
Composite material [Power Sources 163:1003-1039；Nano Lett 9:3844-3847；CN106848273A；
CN106129371A], it coated, adulterated to obtain volume compensation by introducing the small material of good conductivity, volume change
With increase electric conductivity, the cycle performance of material is improved.
Comparison patent CN103107317A discloses a kind of preparation method of Si-C composite material.The patent mainly passes through nanometer
Silicon surface oxidation, hydro-thermal method carbon coating, finally etch away silicon surface oxidation layer, obtain the Si-C composite material of core-shell structure.It should
Method can overcome silicium cathode material capacity attenuation problem to a certain extent, and discharge capacity is up to 1269~2571mAh/g for the first time,
40% or so, capacity and circulation have greatly improved capacity retention ratio after 100 weeks circulations.However the patent uses hydro-thermal method
Carbon coating is carried out, obtained material morphology has randomness, it is difficult to obtain uniform, stable pattern, while this method is formed
Hole number it is few and aperture is small, subsequent to be difficult to perform etching and clean, last hydro-thermal method needs the environment of high temperature and pressure, to equipment
Requirement it is relatively high, it is difficult to continuous production, the consistency between batch are poor.
Summary of the invention
The technical problem to be solved in the present invention is to provide the Si-C composite materials and its system of a kind of porous spherical core-shell structure
The lithium ion battery of Preparation Method and the Si-C composite material using this porous spherical core-shell structure.
In order to solve the above-mentioned technical problem, the invention adopts the following technical scheme:
A kind of preparation method of the Si-C composite material of porous spherical core-shell structure is provided, comprising the following steps:
S1, it prepares mixed solution 1: first nano silica fume being subjected to surface oxidation treatment in air, obtain to surface layer and be oxidized
Si/SiO2Nano particle, oxidizing temperature are 350 DEG C~600 DEG C, and oxidization time is 1h~10h, and then its ultrasonic disperse exists
In organic solvent 1, organic dispersing agent is added, mixed solution 1 is obtained after ultrasonic disperse；
S2, prepare mixed solution 2: by polymer 1 dissolve by heating in organic solvent 2, dissolve by heating temperature be 60 DEG C~
100℃；Polymer 2 is added, it is lasting to stir, it is completely dissolved using waste heat, obtains mixed solution 2；
S3, prepare spraying presoma: mixed solution 2 be added in mixed solution 1, be sufficiently stirred be uniformly dispersed to obtain mix it is molten
Liquid 3 obtains spherical Si/SiO2/ polymer composites using spray dryer mist projection granulating, i.e. presoma by spraying；
S4, Si-C composite material is prepared: first in air by spraying precursor spherical Si/SiO2/ polymer composites
Then 200 DEG C~400 DEG C sintering 1h~5h are placed in lower 600 DEG C~1600 DEG C sintering 3h~20h of inert atmosphere again, then natural
It is cooled to room temperature to obtain porous spherical Si/SiO2/ C composite, the porous spherical Si/SiO that then will be obtained2/ C composite
Etching is impregnated in strong acid solution removes SiO2Then layer cleans, the dry Si/C composite wood to get porous spherical core-shell structure
Material；
In the above method, nano silica fume: organic dispersing agent: polymer 1: polymer 2: the mass ratio of organic solvent is 1:
(0.001~0.01): (1~20): (0.1~1): (10~50), the quality of organic solvent are organic solvent 1 and organic solvent 2
Quality summation, polymer 1 and polymer can be dissolved in organic solvent 1 and organic solvent 2, and the polymer 1 with polymerize
Object 2 has different thermal decomposition temperatures, and the thermal decomposition temperature for measuring few polymer 2 is in the air calcination temperature of step S4
Within the scope of 200 DEG C~400 DEG C, for first melting pore-forming.
Preferably,
The partial size of the nano silica fume is 20nm~800nm.
Further,
Organic dispersing agent in step S1 be neopelex, lauryl sodium sulfate, triethyl group hexyl phosphoric acid,
One or more of methyl anyl alcohol, cellulose derivative, polyacrylamide or other organic dispersing agents with same effect
Combination.
Further,
Polymer 1 in step S2 be polyacrylonitrile, Kynoar, polypropylene, polyethylene, polyvinyl chloride, polyamide,
The combination of one or more of polylactic acid etc..
Further,
Polymer 2 in step S2 is polymethyl methacrylate (PMMA), polyethylene glycol, ethene-vinyl acetate are copolymerized
The combination of one or more of object, polyethylene glycol adipate or other polymer with similar effect.
Further,
The organic solvent 1, organic solvent 2 respectively n,N-Dimethylformamide, n,N-dimethylacetamide, acetone,
Tetrahydrofuran, the combination of one or more of dimethyl sulfoxide etc..
Preferably, organic solvent 1 and organic solvent 2 use identical organic solvent.
Further,
The spray drying frequency of spray dryer is 20HZ~100HZ, the intake air temperature of spray dryer in step S3
It is 120 DEG C~300 DEG C, air outlet temperature is 70 DEG C~150 DEG C.
Further,
Inert atmosphere is N in step S42One of atmosphere, Ar atmosphere, He atmosphere are a variety of.
Further,
In step S4 strong acid solution be hydrofluoric acid (HF) solution, volumetric concentration be 5%~40%, etch period be 0.1h~
24h。
The present invention also provides Si-C composite material made from above-mentioned preparation method, the Si-C composite material has porous ball
Forming core shell structure.
The present invention also provides the lithium ion batteries comprising Si-C composite material made from above-mentioned preparation method, constitute lithium ion
The negative electrode material of battery cathode is the above method Si-C composite material obtained with porous spherical core-shell structure.
Beneficial effects of the present invention:
1, preparation method of the invention in pore-creating technique by using the polymer of two kinds of different thermal decomposition temperatures, first
The low polymer of heating burn-up thermal decomposition temperature in air, forms nano aperture, then the higher polymer of thermal decomposition temperature
High temperature cabonization is carried out in inert gas, is formed by hole different from common be carbonized naturally using single carbon source.
2, the Si-C composite material of porous spherical core-shell structure obtained has following innovative point by the method for the invention:
(1) product appearance structure is novel: the Si-C composite material that the present invention obtains is the spherical agglomerated of multicore core-shell structure
Body, and surface has apparent nano aperture, specific surface area is small, tap density is high, different from common monocore-shell Si/
C-material.
(2) electrochemistry can be further improved: after tested, 1C first discharge specific capacity is up to 2270mAh/g or more, stablizes
Specific discharge capacity is 1585mAh/g or more, and capacity retention ratio still has 95% or more after recycling within 200 weeks, charge/discharge capacity and circulation
Performance has clear improvement.
This is because: the nanosizing of silicon particle and the carbon coating in situ on surface can significantly improve silicon particle electric conductivity.This
The invention Si-C composite material obtained with porous spherical core-shell structure, firstly, its unique porous core-shell structure can be
Silicon particle during removal lithium embedded reserve volume expansion space, prevent silicon particle due to volume expansion and dusting effect and from
It falls off and loses activity on collector, improve the cycle performance of material.Secondly, spherical structure is conducive to improve pine dress and the vibration of material
Real density, and then improve the volume energy density of material；And porous structure is then conducive to the infiltration of electrolyte, provides for lithium ion
More transmission channels improve the high rate performance of material.In addition, this unique porous core-shell structure is avoided that silicon active particle
The rapid decay reunited and " electrochemistry sintering " is caused to cause capacity, while compared with single core-shell structure particle, the structure
Specific surface area can be reduced, electrolyte side reaction is reduced, improves coulombic efficiency.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the flow diagram for the Si-C composite material that present invention preparation has porous spherical core-shell structure；
Fig. 2 is the three-dimensional structure signal of the method for the present invention Si-C composite material obtained with porous spherical core-shell structure
Figure；
Fig. 3 is the cycle performance of the Si-C composite material obtained with porous spherical core-shell structure of the embodiment of the present invention 1
Figure.
Specific embodiment
In order to preferably illustrate the content of the invention, below by specific embodiment to further verifying of the invention.It is special
Illustrate herein, embodiment is only that more directly description is of the invention, they are a part of the invention, cannot be to structure of the present invention
At any restrictions.
Embodiment 1:
As shown in Figure 1, the preparation method of the present embodiment Si-C composite material, its step are as follows:
S1, prepare raw material, take the nano silica fume 50g of 100nm, 400 DEG C of heating 3h, obtain surface layer by oxygen in air atmosphere
The Si/SiO of change2Nano particle is added to 100gN, in dinethylformamide (DMF) solution and adds the dodecane of 0.05g
Base benzene sulfonic acid sodium salt ultrasonic disperse, obtains mixed solution 1.
S2,200g polyacrylonitrile (PAN) is added in 500gN, dinethylformamide (DMF) solution, 70 DEG C of heating are molten
Solution adds 50g polymethyl methacrylate (PMMA) to uniform liquid, lasting stirring using waste-heat to being completely dissolved,
Obtain mixed solution 2；
Nano silica fume: organic dispersing agent: polymer 1: polymer 2: the mass ratio of solvent is 1:0.001:4:1:12；
S3, the addition of the mixed solution 1 step S2 of step S1 is obtained being sufficiently stirred in mixed solution 2 and being uniformly dispersed to obtain
Mixed solution 3, setting spray dryer are sprayed frequency 40HZ, keep 240 DEG C of air intake air temperature of heating, air outlet temperature 85
DEG C, start for mixed solution 3 to be spray-dried, obtains spherical Si/SiO2/ polymer composites；
S4, by obtained spraying material (spherical Si/SiO2/ polymer composites) it is placed in sintering furnace first in air atmosphere
Lower 250 DEG C of sintering 2h, then 800 DEG C of sintering 8h, cooled to room temperature obtain porous spherical Si/SiO under nitrogen protection2/C
Composite material.The porous spherical Si/SiO that will be obtained2The hydrofluoric acid solution that/C composite concentration is 10% etches 12h and removes
SiO2Layer, it is dry after being cleaned up repeatedly with deionized water, the Si/C composite material of porous spherical core-shell structure is obtained, sample is denoted as
Product Y1.
Embodiment 2:
The preparation method of the present embodiment Si-C composite material, its step are as follows:
S1, the nano silica fume 40g for taking 800nm, 600 DEG C of heating 1h, obtain the Si/ being oxidized to surface layer in air atmosphere
SiO2Nano particle is added into 100g tetrahydrofuran solution and adds the triethyl group hexyl phosphoric acid ultrasonic disperse of 0.05g, obtains
Mixed solution 1.
S2,200g Kynoar is added in 500g tetrahydrofuran solution, 100 DEG C dissolve by heating to uniform liquid, then
30g polyethylene glycol is added, lasting stirring, to being completely dissolved, obtains mixed solution 2 using waste-heat；
Nano silica fume: organic dispersing agent: polymer 1: polymer 2: the mass percent of solvent is 1:0.00125:4:
0.75:15；
S3, the addition of the mixed solution 1 step S2 of step S1 is obtained being sufficiently stirred in mixed solution 2 and being uniformly dispersed to obtain
Mixed solution 3, setting spray dryer are sprayed frequency 100HZ, keep 300 DEG C of air intake air temperature of heating, air outlet temperature
150 DEG C, starts for mixed solution 3 to be spray-dried, obtain spherical Si/SiO2/ polymer composites.
S4, by obtained spraying material (spherical Si/SiO2/ polymer composites) it is placed in sintering furnace first in air atmosphere
Lower 200 DEG C of sintering 5h, then 1600 DEG C of sintering 4h, cooled to room temperature obtain porous spherical Si/ under Ar atmosphere protection
SiO2/ C composite.The porous spherical Si/SiO that will be obtained2The hydrofluoric acid solution that/C composite concentration is 40% etches
0.1h removes SiO2Layer, it is dry after being cleaned up repeatedly with deionized water, obtain the Si/C composite wood of porous spherical core-shell structure
Material, is denoted as sample Y2.
Embodiment 3:
The preparation method of the present embodiment Si-C composite material, its step are as follows:
S1, the nano silica fume 60g for taking 20nm, 350 DEG C of heating 10h, obtain the Si/ being oxidized to surface layer in air atmosphere
SiO2Nano particle is added into 100g dimethyl sulphoxide solution and adds the neopelex ultrasonic disperse of 0.09g,
Obtain mixed solution 1.
S2,300g polyamide is added in 500g dimethyl sulphoxide solution, 60 DEG C dissolve by heating to uniform liquid, add
60g ethylene-vinyl acetate copolymer, lasting stirring, to being completely dissolved, obtain mixed solution 2 using waste-heat；
Nano silica fume: organic dispersing agent: polymer 1: polymer 2: the mass percent of solvent is 1:0.0015:5:1:
10；
S3, the addition of the mixed solution 1 step S2 of step S1 is obtained being sufficiently stirred in mixed solution 2 and being uniformly dispersed to obtain
Mixed solution 3, setting spray dryer are sprayed frequency 200HZ, keep 120 DEG C of air intake air temperature of heating, air outlet temperature
70 DEG C, starts for mixed solution 3 to be spray-dried, obtain spherical Si/SiO2/ polymer composites.
S4, by obtained spraying material (spherical Si/SiO2/ polymer composites) it is placed in sintering furnace first in air atmosphere
Lower 400 DEG C of sintering 1h, then 600 DEG C of sintering 12h, cooled to room temperature obtain porous spherical Si/ under nitrogen atmosphere protection
SiO2/ C composite.The porous spherical Si/SiO that will be obtained2The hydrofluoric acid solution etching that/C composite concentration is 5% is for 24 hours
Remove SiO2Layer, it is dry after being cleaned up repeatedly with deionized water, the Si/C composite material of porous spherical core-shell structure is obtained, is remembered
For sample Y3.
Embodiment 4:
The preparation method of the present embodiment Si-C composite material, its step are as follows:
S1, the nano silica fume 80g for taking 500nm, 350 DEG C of heating 10h, obtain the Si/ being oxidized to surface layer in air atmosphere
SiO2Nano particle is added to 100gN, in dinethylformamide (DMF) solution and adds the dodecyl benzene sulfonic acid of 0.8g
Sodium ultrasonic disperse obtains mixed solution 1.
S2,1600g polylactic acid is added in 500gN, dinethylformamide (DMF) solution, 60 DEG C dissolve by heating to equal
One liquid adds 40g polyethylene glycol adipate, and lasting stirring, to being completely dissolved, obtains mixed solution using waste-heat
2；
Nano silica fume: organic dispersing agent: polymer 1: polymer 2: the mass percent of solvent is 1:0.01:20:0.5:
50；
S3, the addition of the mixed solution 1 step S2 of step S1 is obtained being sufficiently stirred in mixed solution 2 and being uniformly dispersed to obtain
Mixed solution 3, setting spray dryer are sprayed frequency 200HZ, keep 120 DEG C of air intake air temperature of heating, air outlet temperature
70 DEG C, starts for mixed solution 3 to be spray-dried, obtain spherical Si/SiO2/ polymer composites.
S4, by obtained spraying material (spherical Si/SiO2/ polymer composites) it is placed in sintering furnace first in air atmosphere
Lower 200 DEG C of sintering 5h, then 600 DEG C of sintering 12h, cooled to room temperature obtain porous spherical Si/ under He atmosphere protection
SiO2/ C composite.The porous spherical Si/SiO that will be obtained2The hydrofluoric acid solution etching that/C composite concentration is 5% is for 24 hours
Remove SiO2Layer, it is dry after being cleaned up repeatedly with deionized water, the Si/C composite material of porous spherical core-shell structure is obtained, is remembered
For sample Y4.
By the lithium ion battery biomass carbon negative electrode material sample of number Y1~Y4 prepared in the above embodiments and according to right
Si-C composite material made from method than file CN103107317A embodiment 1 and pure silicon nano particle as negative electrode material and
Conductive agent (conductive black), binder (Kynoar) are added N- methyl by the mass ratio of 8:1:1 and give a tongue-lashing in pyrrolidone, prepare
Lithium ion battery anode slurry is coated on 8 μm of copper foils, electrode slice is made as battery cathode, lithium metal is anode, 1mol/L
LiFP6 is electrolyte, is assembled into battery, is denoted as battery number DC1~DC6, current density be 0.1C, voltage window 0.01
Cycle life test is carried out under the conditions of~1.5V, test result is as follows table 1:
The electric property of each material sample of table 1 and battery obtained
Analysis of conclusion:
According to attached drawing 1: in preparation method provided by the invention, using spray drying centrifugal principle rapid draing simultaneously
Obtain the spherical Si/SiO with spherical morphology2/ polymer composites, by adjusting atomizer frequency in spray-drying process
With the spherical structure of available 5~30 microns of concentration of solution.Due to raw material Si/SiO2Partial size very little there was only 20~
800nm or so, script are dispersed in a polymer solution, so in spraying globulation, Si/SiO2Bead
It is easy to be formed together 5~30 microns of (Si/SiO with polymer solution2/ polymer) big ball, and polymer solution is
With mobility and viscosity, so can be naturally Si/SiO in globulation2Packet is in inside, such Si/SiO2Just become
Core inside big ball.Because the partial size of big ball is bigger, multiple Si/SiO can be naturally enveloped inside big ball2Core.
Meanwhile the present invention is by designing two different polymer (polymer 1 and polymer 2) and special sintering side
Formula can first burn up the lower polymer of one of thermal decomposition temperature (measuring few polymer 2) during the sintering process and be allowed to shape
At macropore, and the higher polymer of another thermal decomposition temperature that do not burn up then becomes carbon, to form porous Si/SiO2/C
Big ball.
Finally, passing through hydrofluoric acid and SiO2SiO can be etched away by reacting2, and the SiO removed2Part space then
Space can be provided for Si volume expansion.
As shown in Fig. 2, Si/C composite material produced by the present invention has porous spherical core-shell structure as shown in the figure.
Emphasis makes analysis to the chemical property of sample Y1, as shown in figure 3,200 weeks capacity retention ratios reach 95%,
Coulombic efficiency reaches 99%.
From the result of upper table 1 it can be seen that compound using the Si/C of porous spherical core-shell structure made from the method for the present invention
Material is substantially better than pure silicon nano particle and documents as the electric property of lithium ion battery made from negative electrode material
Carbon-silicon composite material made from method disclosed in CN103107317A.
The above is a specific embodiment of the invention, but any restrictions cannot be constituted to the present invention, therefore need special
It points out, it is all based on the present invention, it is made any modification and is all fallen within the scope of the present invention with improvement.
Claims (10)
1. the preparation method of the Si-C composite material of porous spherical core-shell structure, which comprises the following steps:
S1, it prepares mixed solution 1: nano silica fume being first subjected to surface oxidation treatment in air, obtain the Si/ being oxidized to surface layer
SiO2Nano particle, oxidizing temperature are 350 DEG C~600 DEG C, and oxidization time is 1h~10h, then by its ultrasonic disperse organic
In solvent 1, organic dispersing agent is added, mixed solution 1 is obtained after ultrasonic disperse；
S2, it prepares mixed solution 2: polymer 1 is dissolved by heating in organic solvent 2, dissolving by heating temperature is 60 DEG C~100
℃；Polymer 2 is added, it is lasting to stir, it is completely dissolved using waste heat, obtains mixed solution 2；
S3, it prepares spraying presoma: mixed solution 2 is added in mixed solution 1, is sufficiently stirred and is uniformly dispersed to obtain mixed solution 3,
Using spray dryer mist projection granulating, spherical Si/SiO2/ polymer composites are obtained, i.e. presoma by spraying；
S4, Si-C composite material is prepared: by first 200 DEG C in air of spraying precursor spherical Si/SiO2/ polymer composites
Then~400 DEG C of sintering 1h~5h are placed in lower 600 DEG C~1600 DEG C sintering 3h~20h of inert atmosphere again, then naturally cool to
Room temperature obtains porous spherical Si/SiO2/ C composite, the porous spherical Si/SiO that then will be obtained2/ C composite is in strong acid
Etching is impregnated in solution removes SiO2Then layer cleans, the dry Si/C composite material to get porous spherical core-shell structure；
In the above method, nano silica fume: organic dispersing agent: polymer 1: polymer 2: the mass ratio of organic solvent is 1:(0.001
~0.01): (1~20): (0.1~1): (10~50), the quality of organic solvent are the quality of organic solvent 1 and organic solvent 2
Summation, polymer 1 and polymer can be dissolved in organic solvent 1 and organic solvent 2, and the polymer 1 has with polymer 2
Different thermal decomposition temperatures, and the thermal decomposition temperature for measuring few polymer 2 be in 200 DEG C of the air calcination temperature of step S4~
Within the scope of 400 DEG C, for first melting pore-forming.
2. the preparation method of the Si-C composite material of porous spherical core-shell structure according to claim 1, which is characterized in that
The partial size of the nano silica fume is 20nm~800nm.
3. the preparation method of the Si-C composite material of porous spherical core-shell structure according to claim 1 or 2, feature exist
In the organic dispersing agent in step S1 is neopelex, lauryl sodium sulfate, triethyl group hexyl phosphoric acid, methyl
The combination of one or more of amylalcohol, cellulose derivative, polyacrylamide.
4. the preparation method of the Si-C composite material of porous spherical core-shell structure according to claim 1 or 2, feature exist
In the polymer 1 in step S2 is polyacrylonitrile, Kynoar, polypropylene, polyethylene, polyvinyl chloride, polyamide, poly- cream
The combination of one or more of acid.
5. the preparation method of the Si-C composite material of porous spherical core-shell structure according to claim 1 or 2, feature exist
In the polymer 2 in step S2 is polymethyl methacrylate, polyethylene glycol, ethylene-vinyl acetate copolymer, polyadipate
The combination of one or more of glycol ester.
6. the preparation method of the Si-C composite material of porous spherical core-shell structure according to claim 1 or 2, feature exist
In,
The organic solvent 1, organic solvent 2 are respectively n,N-Dimethylformamide, n,N-dimethylacetamide, acetone, tetrahydro
Furans, the combination of one or more of dimethyl sulfoxide.
7. the preparation method of the Si-C composite material of porous spherical core-shell structure according to claim 1 or 2, feature exist
In,
The spray drying frequency of spray dryer is 20HZ~100HZ in step S3, and the intake air temperature of spray dryer is 120
DEG C~300 DEG C, air outlet temperature is 70 DEG C~150 DEG C.
8. the preparation method of the Si-C composite material of porous spherical core-shell structure according to claim 1 or 2, feature exist
In,
Strong acid solution is hydrofluoric acid solution in step S4, and volumetric concentration is 5%~40%, and etch period is 0.1h~for 24 hours.
9. a kind of Si-C composite material, which is characterized in that Si-C composite material side as described in the claims 1 or 2
Method is made, and the Si-C composite material has porous spherical core-shell structure.
10. a kind of lithium ion battery, which is characterized in that constitute the negative electrode material of negative electrode of lithium ion battery as claims 1 or 2 institute
Si-C composite material made from the method stated, the Si-C composite material have porous spherical core-shell structure.
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