CN107611394A - A kind of nuclear shell structure nano silicon/graphene composite negative pole of carbon coating and preparation method thereof - Google Patents
A kind of nuclear shell structure nano silicon/graphene composite negative pole of carbon coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses the nuclear shell structure nano of a kind of carbon coating silicon/graphene composite negative pole and preparation method thereof, the composite negative pole material is using nano silicon or silicate as silicon source, nano silicon or the silicate uniform adsorption in graphene oxide layer are realized by electrostatic self-assembled with graphene oxide colloidal sol, obtain silica/graphene oxide composite material or silicate/graphene oxide composite material, then by the material at low temperature in-situ reducing, obtain nano-silicon/graphene composite material, carbon compound coating is finally carried out, obtains object.The application has been made by simple technique while has had the advantages that the composite negative pole material that coulombic efficiency is high, cycle performance is excellent.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of nuclear shell structure nano silicon/graphite of carbon coating
Alkene composite negative pole material and preparation method thereof.
Background technology
The specific capacity of commercial li-ion cell positive material has reached its limiting value substantially at present, it is difficult to have again rapid
Lifting, thus the development of negative material will play vital effect to the security, energy density and service life of battery.
The theoretical gram volume of silica-base material can reach 4200mAh/g (Li in existing negative material22Si5), and security
Good (current potential of lithium insertion silicon is less than 0.5V, in the absence of the common imbedding problem of solvent molecule), raw material rich reserves, cost is low, is
One of lithium ion battery negative material most with prospects.But in charge and discharge process, silicon can occur huge volume and become
Change (100%~300%), cause material efflorescence, peel off, lose electrical contact, capacity attenuation quickly, therefore the research master of silicium cathode
The bulk effect for how reducing silicon materials is concentrated on, improves its cycle performance.
In order to suppress silicon volumetric expansion, ensure Stability Analysis of Structures of the material in charge and discharge process, keep silicon materials particle it
Between, electrical contact good between material and electrolyte and between material and collector.For this, people have attempted a variety of methods, bag
Include prepare amorphous si film, nano-silicon, porous silicon, Si oxide, siliceous nonmetallic compound, siliceous metal compound, silicon/
Carbon composite, silicon/metal (activity or inertia) composite etc..Lithium ion is quickly through crystal grain boundaries and and silicon during embedding lithium
Amorphous lithium silicon compound is combined to form, silicon grain will not recrystallize when taking off lithium, and in the absence of phase transformation, local volume is reversible swollen
It is swollen to be greatly reduced with contraction, so as to improve the cycle performance of material.Graphene has bi-dimensional cellular shape lattice structure, compares graphite
Reversible lithium storage capacity (theoretical specific capacity 372mAh/g) it is high；The number of plies is reduced to be advantageous to obtain higher reversible capacity.Research
It was found that：Adsorbable 1 Li in the both sides of graphene sheet layer+, therefore the theoretical specific capacity of graphene is twice of graphite, i.e.,
744mAh/g.Although with higher theoretical specific capacity, if graphene to be used alone as to the negative material of lithium ion battery, still need
Solves the problems such as big irreversible specific capacity and voltage delay.But graphene has high specific surface area (2600m2/ g), it is excellent
Electronic conductivity energy, good thermal property and engineering properties, by its with nano-silicon it is compound can not only alleviate de- lithium during
Material structure caused by silicon volumetric expansion changes, and the electron transfer rate of nanometer silicium cathode is also improved, so as to improve nano-silicon
Chemical property.But the biggest problem that this method faces is how active nano silicon particles to be effectively uniformly distributed in base
In body, regional area caused by silicon grain reunion is avoided particle expansion or contraction occur, so as to cause to lose electrical contact between particle,
Deterioration in material properties.
Patent CN103400970A discloses a kind of nanometer silicon/graphene lithium ion battery cathode material and its preparation side
Method.Its preparation process step：(1) lithium metal and cosolvent are dissolved in the first kind solvent of water under an argon atmosphere and prepared
Electronics solution；(2) under an argon atmosphere, silicon tetrachloride is added dropwise in the reactor into step (1), it is molten that acquisition is in electronics
The suspension for the nano-silicon particle that granularity in liquid is 10~100nm；(3) using water as dispersant, graphite oxide or stone are configured
Black alkene suspension, nitric acid is added, washing to neutrality, vacuum drying, obtained product surpasses with the second class solvent after supersound process
Plastic sample solution is matched somebody with somebody in sonication；(4) glue sample solution made from step (3) is added dropwise in the solution of step (2) dropwise, stirred,
Again by being ultrasonically treated, disperse nano-silicon and graphene；(5) mixed solution arrived of step (4) is separated by differential centrifugation,
Calcining obtains combination electrode material in vacuum filtration and the dry tube furnace protected after argon gas.Although gained composite is one
Determine solve the problems, such as that silicon nanoparticle is dispersed in degree, however its to still have efficiency first low, poor circulation
Shortcoming, still there is 40% or so capacity attenuation after 100 circulations, and its preparation process is complex.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of core of the good carbon coating of cyclical stability
Shell structural nano silicon/graphene composite negative pole and preparation method thereof, make obtained material while there is coulombic efficiency height, follow
The advantages of ring function admirable.
To solve above-mentioned technical problem, the technical solution adopted in the present invention is as follows：
A kind of preparation method of nuclear shell structure nano silicon/graphene composite negative pole of carbon coating, it includes following step
Suddenly：
(1) using nano silicon or silicate as silicon source, nano-silica is prepared by cationic surfactant modification
SiClx dispersion liquid or silicate solutions, are then mixed with graphene oxide colloidal sol, and nano-silica is realized by electrostatic self-assembled
SiClx or the silicate uniform adsorption in graphene oxide layer, obtain quasi- two-dimensional structure unit silica/graphite oxide
Alkene composite or silicate/graphene oxide composite material；Nano silicon dioxide dispersion or silicate solutions and oxygen
The mixing of graphite alkene colloidal sol is that convection current mixing is compound in T-shaped tubular reactor；
(2) by the quasi- two-dimensional structure unit silica/graphene oxide composite material or silicate/graphite oxide
Alkene composite is launched to nitrogen after drying in the fused salt under protecting, using in-situ reducing technology under low temperature, make silica or
Person's silicate and graphene oxide are reduced simultaneously, and are easy to the characteristic of stacking and spheroidization using graphene, by standard two
Nuclear shell structure nano silicon/the graphene composite material being layering is formed after tieing up nano-silicon/graphene spheroidization of construction unit,
Reaction carries out pickling after terminating；Pickling refers to clean the nano-silicon/graphene composite material using dilute hydrochloric acid solution；
(3) in spheroidization equipment, by nano-silicon/graphene composite material after reduction and a certain amount of graphite and carbon source
Material carries out compound coating, and then carbonization obtains nano-silicon/graphene of the core shell structure of carbon coating under inert gas shielding
Composite negative pole material.
In the step of preparation method of nuclear shell structure nano silicon/graphene composite negative pole of above-mentioned carbon coating (1), institute
State particle diameter≤10nm of nano silicon, the concentration that solution is made in the silicate is 10~80mg/ml, the nano-silica
SiClx or silicate and cationic surfactant are according to mass ratio 100：The ratio of (1~20) carries out ultrasonic mixing processing
0.5~1h obtains nano silicon dioxide dispersion or silicate solutions.
In the step of preparation method of nuclear shell structure nano silicon/graphene composite negative pole of above-mentioned carbon coating (1), institute
Cationic surfactant is stated as DTAB, 3- aminopropyls triethyl silicane, dodecyl dimethyl benzyl
Ammonium chloride or PDDA.
In the step of preparation method of nuclear shell structure nano silicon/graphene composite negative pole of above-mentioned carbon coating (1), institute
State the graphene oxide colloidal sol that graphene oxide colloidal sol refers to be prepared using Hummers methods, the graphene oxide colloidal sol
Concentration be 1~5mg/ml, the solid matter in the graphene oxide colloidal sol and the nanometer of cationic surfactant modification
The mass ratio of silica or silicate is 0.10~0.5:1.
In the step of preparation method of nuclear shell structure nano silicon/graphene composite negative pole of above-mentioned carbon coating (2), institute
It is aluminium chloride and aluminium powder to state fused salt, under low temperature in-situ reducing refer to the silica/graphene oxide composite material or
Silicate/graphene oxide composite material, aluminium chloride and aluminium powder according to silicon source used, aluminium chloride and aluminium powder mass ratio 1:8:
5~10h is incubated under the conditions of being 150~250 DEG C in temperature after 0.8 mixing.
In the step of preparation method of nuclear shell structure nano silicon/graphene composite negative pole of above-mentioned carbon coating (3), institute
It is pitch, sucrose, glucose, polyvinyl alcohol, polyethylene glycol, phenolic resin, polyacrylonitrile, polypyrrole and polyphenyl to state carbon source material
It is more than one or both of amine；The mass ratio of the carbon source material and graphite is 0.5~2:10, the nano-silicon/graphene
The mass ratio of composite and graphite is 0.5~2:10.
In the step of preparation method of nuclear shell structure nano silicon/graphene composite negative pole of above-mentioned carbon coating (3), institute
Stating the condition of carbonization is：600~900 DEG C are warming up to 2~5 DEG C/min heating rate, is incubated 2~10h.
The spheroidization equipment that above-mentioned steps (3) use is spray dryer.
In the preparation method of nuclear shell structure nano silicon/graphene composite negative pole of above-mentioned carbon coating, the carbon coating
Core shell structure nano-silicon/graphene composite negative pole in silicon mass content be 5%~20%.
Nano-silicon/graphene composite negative pole of the core shell structure of the carbon coating obtained using above-mentioned preparation method, it is
With the compound spherical three-dimensional structure for talking raw material of nano-silicon/graphene.
Nano-silicon/graphene composite negative pole of the core shell structure of above-mentioned carbon coating is used to make negative electrode of lithium ion battery
Piece.
Compared with prior art, the present invention at least has the advantages that：
The present invention is compound with graphene oxide colloidal sol using silica or silicate as silicon source, and by carbon coating or
The compound nuclear shell structure nano silicon/graphene composite negative pole for obtaining carbon coating, the specific surface area of graphene can be substantially reduced,
So as to be advantageous to improve the efficiency first of composite negative pole material.
The preparation method of above-mentioned nuclear shell structure nano silicon/graphene composite negative pole is by nano silicon or silicic acid
Salt realizes its uniform adsorption in graphene oxide layer by electrostatic self-assembled, using low-temperature in-site reduction technique, prepares
Composite realize nano-dispersed of the nano silicon particles in graphene-based lamella, avoid silicon grain reunite cause partial zones
There is particle expansion or shunk to cause to lose electrical contact and deterioration in material properties between particle in domain, simultaneously as selected nano-silicon
The granularity of particle is sufficiently small, even if efflorescence, also has the silicon materials for comparing large scale and graphene keeps good contact, can be effective
" isolated island " effect is avoided, it is higher so as to obtain capacity, and stability, high rate performance and cycle performance are all preferably nano combined negative
Pole material.
The preparation method of nuclear shell structure nano silicon/graphene composite negative pole of carbon coating of the present invention has technique
Simply, it is easily operated, safety and environmental protection, the advantages that large-scale production.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Embodiment 1
This example is less than 10nm nanometer titanium dioxide using surfactant PDDA and diameter
Silicon grain.0.16g surfactant PDDAs are weighed first to be scattered in distilled water, are sufficiently stirred one
After the section time, 0.9g nano silicons are added, ultrasonic disperse 0.5h, are centrifuged, are cleaned, drying, cation is obtained and repaiies
The nanometer silicon dioxide material of decorations.
2mg/ml graphene oxide colloidal sol is prepared using Hummers methods.By the cation modified of above-mentioned preparation
Nanometer silicon dioxide material is added in 100ml graphene oxide colloidal sols, is uniformly mixed, and nanometer two is prepared in freeze-drying
Silica/graphene oxide powder.
By nano silicon/graphene oxide powder of above-mentioned preparation, mixed with 7.2g aluminium chloride, 0.72g aluminium powders
It is even, after the lower 200 DEG C of constant temperature 5h of argon gas atmosphere, naturally cool to room temperature.Obtained material is cleaned with dilute hydrochloric acid solution, is prepared into
To nano-silicon/graphene composite material.
Weigh 0.5g pitches to be dissolved in distilled water, add 5g graphite materials and above-mentioned nano-silicon/graphene composite material,
1000r/min stirrings 3h obtains mixed slurry, is spray-dried to obtain by peristaltic pump by mixed slurry under stirring condition
Precursor：The inlet temperature of the spray drying is 220 DEG C, and outlet temperature is 100~120 DEG C.
The precursor of above-mentioned preparation is subjected to carbonization treatment in high-temperature atmosphere furnace, under high-purity Ar gas atmosphere protection, with 5
DEG C/min heating rate is gradually heating to 900 DEG C, constant temperature 3h from room temperature, grinding is taken out after being cooled to room temperature, obtains carbon coating
Core shell structure nano-silicon/graphene composite negative pole.
The preparation method of lithium ion battery：
Negative material obtained above and conductive agent (SP), binding agent (CMC/SBR) are stirred and prepare electrode slurry
Material, slurry is uniformly coated in the copper foil current collector that thickness is 9 μm, 12h is dried under 105 DEG C of vacuum conditions, cutting is born
Pole piece.2032 type button cells are formed in the glove box full of high-purity argon gas.With new prestige battery test system button type battery
Charge-discharge performance test is carried out, discharge and recharge blanking voltage scope is 5mV~1.5V, and test temperature is 25 DEG C, following embodiment
Use identical method of testing.
Embodiment 2
This example is less than 10nm nano-silica using surfactant sodium dodecyl base dimethyl benzyl ammonium chloride and diameter
Silicon carbide particle.Weigh 0.16g surfactant sodium dodecyl base dimethyl benzyl ammonium chlorides first to be scattered in distilled water, fully
After stirring a period of time, 0.8g nano silicons are added, ultrasonic disperse 0.5h, are centrifuged, are cleaned, drying, obtain sun
The nanometer silicon dioxide material of ion modification.
2mg/ml graphene oxide colloidal sol is prepared using Hummers methods.By the cation modified of above-mentioned preparation
Nanometer silicon dioxide material is added in 100ml graphene oxide colloidal sols, is uniformly mixed, and nanometer two is prepared in freeze-drying
Silica/graphene oxide powder.
By nano silicon/graphene oxide powder of above-mentioned preparation, mixed with 6.4g aluminium chloride and 0.64g aluminium powders
It is even, after the lower 250 DEG C of constant temperature 5h of argon gas atmosphere, naturally cool to room temperature.Obtained material is cleaned with dilute hydrochloric acid solution, is prepared into
To nano-silicon/graphene composite material.
Weigh 1g glucose to be dissolved in distilled water, add 6g graphite materials and above-mentioned nano-silicon/graphene composite material,
1000r/min stirrings 3h obtains mixed slurry, is spray-dried to obtain by peristaltic pump by mixed slurry under stirring condition
Precursor：The inlet temperature of the spray drying is 220 DEG C, and outlet temperature is 100~120 DEG C.
The precursor of above-mentioned preparation is subjected to carbonization treatment in high-temperature atmosphere furnace, under high-purity Ar atmosphere protection, with 2 DEG C/
Min heating rate is gradually heating to 600 DEG C, constant temperature 10h from room temperature, takes out grinding after being cooled to room temperature, obtains carbon coating
Nano-silicon/graphene composite negative pole of core shell structure.
Embodiment 3
This example is less than 10nm nano silicon using surfactant 3- aminopropyls triethyl silicane and diameter
Grain.0.16g surfactant 3- aminopropyl triethyl silicanes are weighed first to be scattered in distilled water, are sufficiently stirred a period of time
Afterwards, 0.8g nano silicons are added, ultrasonic disperse 1h, are centrifuged, are cleaned, drying, obtain cation modified nanometer
Earth silicon material.
5mg/ml graphene oxide colloidal sol is prepared using Hummers methods.By the cation modified of above-mentioned preparation
Nanometer silicon dioxide material is added in 20ml graphene oxide solutions, is uniformly mixed, and nanometer two is prepared in freeze-drying
Silica/graphene oxide powder.
By nano silicon/graphene oxide powder of above-mentioned preparation, mixed with 6.4g aluminium chloride and 0.64g aluminium powders
It is even, after the lower 200 DEG C of constant temperature 5h of argon gas atmosphere, naturally cool to room temperature.Obtained material is cleaned with dilute hydrochloric acid solution, is prepared into
To nano-silicon/graphene composite material.
Weigh 0.7g sucrose to be dissolved in distilled water, add 3.5g graphite materials and above-mentioned nano-silicon/graphene composite wood
Material, 1000r/min stirrings 3h obtain mixed slurry, by peristaltic pump be spray-dried by mixed slurry under stirring condition
To precursor：The inlet temperature of the spray drying is 220 DEG C, and outlet temperature is 100~120 DEG C.
The precursor of above-mentioned preparation is subjected to carbonization treatment in high-temperature atmosphere furnace, under high-purity Ar gas atmosphere protection, with 3
DEG C/min heating rate is gradually heating to 800 DEG C, constant temperature 3h from room temperature, grinding is taken out after being cooled to room temperature, obtains carbon coating
Core shell structure nano-silicon/graphene composite negative pole.
Embodiment 4
This example is less than 10nm nano-silica using surfactant sodium dodecyl base dimethyl benzyl ammonium chloride and diameter
Silicon carbide particle.0.16g surfactant sodium dodecyl base dimethyl benzyl ammonium chlorides are weighed first to be scattered in distilled water, are fully stirred
After mixing a period of time, 0.8g nano silicons are added, ultrasonic disperse 1h, are centrifuged, are cleaned, drying, obtain cation
The nanometer silicon dioxide material of modification.
2mg/ml graphene oxide colloidal sol is prepared using Hummers methods.By the cation modified of above-mentioned preparation
Nanometer silicon dioxide material is added in 100ml graphene oxide colloidal sols, is uniformly mixed, and nanometer two is prepared in freeze-drying
Silica/graphene oxide powder.
By nano silicon/graphene oxide powder of above-mentioned preparation, mixed with 6.4g aluminium chloride and 0.64g aluminium powders
It is even, after the lower 250 DEG C of constant temperature 5h of argon gas atmosphere, naturally cool to room temperature.Obtained material is cleaned with dilute hydrochloric acid solution, is prepared into
To nano-silicon/graphene composite material.
Weigh 1g phenolic resin to be dissolved in absolute ethyl alcohol, add 7g graphite materials and above-mentioned nano-silicon/grapheme material,
1000r/min stirrings 3h obtains mixed slurry, is spray-dried to obtain by peristaltic pump by mixed slurry under stirring condition
Precursor：The inlet temperature of the spray drying is 220 DEG C, and outlet temperature is 100~120 DEG C.
The precursor of above-mentioned preparation is subjected to carbonization treatment in high-temperature atmosphere furnace：Under high-purity Ar gas atmosphere protection, with 5
DEG C/min heating rate is gradually heating to 700 DEG C, constant temperature 3h from room temperature, grinding is taken out after being cooled to room temperature, obtains carbon coating
Core shell structure nano-silicon/graphene composite negative pole.
Embodiment 5
This example uses surfactant PDDA and glass fibre.0.16g tables are weighed first
Face activating agent PDDA is scattered in distilled water, after being sufficiently stirred a period of time, adds 0.8g glass
Glass fiber, ultrasonic disperse 1h, centrifuge, clean, drying, obtain cation modified nanometer glass fiber material.
2mg/ml graphene oxide colloidal sol is prepared using Hummers methods.By the cation modified of above-mentioned preparation
Glass fiber material is added in 100ml graphene oxide colloidal sols, is uniformly mixed, and nano-glass fibre is prepared in freeze-drying
Dimension/graphene oxide powder.
By glass fibre/graphene oxide powder of above-mentioned preparation, it is well mixed with 6.4g aluminium chloride, 0.64g aluminium powders, in
After the lower 250 DEG C of constant temperature 6h of argon gas atmosphere, room temperature is naturally cooled to.Obtained material is cleaned with dilute hydrochloric acid solution, is prepared and is received
Rice silicon/graphene composite material.
Weigh 1g phenolic resin to be dissolved in absolute ethyl alcohol, add 7g graphite materials and above-mentioned nano-silicon/grapheme material,
1000r/min stirrings 3h obtains mixed slurry, is spray-dried to obtain by peristaltic pump by mixed slurry under stirring condition
Precursor：The inlet temperature of the spray drying is 220 DEG C, and outlet temperature is 100~120 DEG C.
The precursor of above-mentioned preparation is subjected to carbonization treatment in high-temperature atmosphere furnace：Under high-purity Ar gas atmosphere protection, with 5
DEG C/min heating rate is gradually heating to 700 DEG C, constant temperature 3h from room temperature, grinding is taken out after being cooled to room temperature, obtains carbon coating
Core shell structure nano-silicon/graphene composite negative pole.
The composite negative pole material that the various embodiments described above are prepared is used for electrochemical property test knot during lithium ion battery
Fruit is as shown in table 1：
The electrochemical property test result of table 1
As it can be seen from table 1 the obtained composite negative pole material of preparation method of the present invention be used for it is reversible during lithium ion battery
Capacity is compared with high circulation excellent performance.Negative material prepared by the preparation method optimized using the present invention is used for lithium ion battery by table
Reveal good chemical property.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, however, it is to be understood that ability
Field technique personnel can be designed that a lot of other modifications and embodiment, and these modifications and embodiment will fall in the application public affairs
Within the spirit and spirit opened.More specifically, can be to the group of theme combination layout in the range of disclosure
A variety of variations and modifications are carried out into part and/or layout.In addition to the variations and modifications carried out to building block and/or layout,
To those skilled in the art, other purposes also will be apparent.
Claims (9)
1. the preparation method of nuclear shell structure nano silicon/graphene composite negative pole of a kind of carbon coating, it is characterised in that it is wrapped
Include following steps：
(1) using nano silicon or silicate as silicon source, nano silicon is prepared by cationic surfactant modification
Dispersion liquid or silicate solutions, are then mixed with graphene oxide colloidal sol, and nano silicon is realized by electrostatic self-assembled
Or silicate uniform adsorption in graphene oxide layer, obtain silica/graphene oxide composite material or silicic acid
Salt/graphene oxide composite material；
(2) thrown after drying the silica/graphene oxide composite material or silicate/graphene oxide composite material
It is put into the fused salt under nitrogen protection, in-situ reducing obtains nano-silicon/graphene composite material under low temperature, and reaction terminates laggard
Row pickling；
(3) in spheroidization equipment, by nano-silicon/graphene composite material after reduction and a certain amount of graphite and carbon source material
Compound coating is carried out, the nano-silicon/graphene for the core shell structure for obtaining carbon coating that is then carbonized under inert gas shielding is compound
Negative material.
2. the preparation method of nuclear shell structure nano silicon/graphene composite negative pole of carbon coating according to claim 1,
It is characterized in that particle diameter≤the 10nm of step (1) described nano silicon, the nano silicon or silicate and sun
Ionic surface active agent is according to mass ratio 100：The ratio of (1~20) carries out ultrasonic mixing and handles 0.5~1h acquisition nano-silicas
SiClx dispersion liquid or silicate solutions.
3. the preparation method of nuclear shell structure nano silicon/graphene composite negative pole of carbon coating according to claim 1,
It is characterized in that step (1) described cationic surfactant is DTAB, 3- aminopropyl triethyl group silicon
Alkane, dodecyl benzyl dimethyl ammonium chloride or PDDA.
4. the preparation method of nuclear shell structure nano silicon/graphene composite negative pole of carbon coating according to claim 1,
It is characterized in that the concentration of step (1) the graphene oxide colloidal sol is 1~5mg/ml, consolidating in the graphene oxide colloidal sol
Body material is 0.10~0.5 with the nano silicon of cationic surfactant modification or the mass ratio of silicate:1.
5. the preparation method of nuclear shell structure nano silicon/graphene composite negative pole of carbon coating according to claim 1,
It is characterized in that step (2) described fused salt is aluminium chloride and aluminium powder, in-situ reducing refers to the silica/oxidation under low temperature
Graphene composite material or silicate/graphene oxide composite material, aluminium chloride and aluminium powder according to silicon source used, aluminium chloride and
The mass ratio 1 of aluminium powder:8:5~10h is incubated under the conditions of being 150~250 DEG C in temperature after 0.8 mixing.
6. the preparation method of nuclear shell structure nano silicon/graphene composite negative pole of carbon coating according to claim 1,
It is characterized in that step (3) described carbon source material be pitch, it is sucrose, glucose, polyvinyl alcohol, polyethylene glycol, phenolic resin, poly-
It is more than one or both of acrylonitrile, polypyrrole and polyaniline；The mass ratio of the carbon source material and graphite is 0.5~2:
10, the mass ratio of the nano-silicon/graphene composite material and graphite is 0.5~2:10.
7. the preparation method of nuclear shell structure nano silicon/graphene composite negative pole of carbon coating according to claim 1,
It is characterized in that the condition of step (3) described carbonization is：600~900 DEG C are warming up to 2~5 DEG C/min heating rate, insulation
2~10h.
8. the preparation method of nuclear shell structure nano silicon/graphene composite negative pole of carbon coating according to claim 1,
It is characterized in that the mass content of silicon is 5% in nano-silicon/graphene composite negative pole of the core shell structure of the carbon coating
~20%.
A kind of 9. nanometer of the core shell structure for the carbon coating that preparation method using described in claim 1~8 any one obtains
Silicon/graphene composite negative pole.
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