CN107785541A - A kind of Silicon-carbon composite material for lithium ion battery and preparation method thereof - Google Patents
A kind of Silicon-carbon composite material for lithium ion battery and preparation method thereof Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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Abstract
The present invention relates to a kind of Silicon-carbon composite material for lithium ion battery and preparation method thereof, Si-C composite material is dispersed and be embedded in the second particle structure formed between graphite material surface and graphite material by silicon materials；Described second particle surface and graphite material, the silicon materials of inside are coated with one layer of amorphous carbon, form the mutual random orientation of graphite material of second particle, second particle isotropic orientation.Acted on by the steric hindrance and cementability of high molecular polymer, effectively suppress the layering of floating, reunion and the silicon materials and graphite of silicon materials, it is dispersed in graphite flake to realize silicon materials, is formed with graphite effectively compound.Si-C composite material prepared by the present invention is used for lithium ion battery, shows that efficiency high, expansion be small, the advantages of having circulated, and the inventive method technical process is simple, easily realizes industrialized production.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of Silicon-carbon composite material for lithium ion battery and its
Preparation method.
Background technology
Lithium ion battery has a wide range of applications as energy-storage travelling wave tube, as negative pole material, the theoretical specific capacity of graphite
Only 372mAh/g.Nowadays, as the demand that lithium ion battery energy density is lifted, the actual specific capacity of graphite cathode have been sent out
Wave to the limit, it is developed potential and is extremely limited.
The theoretical specific capacity of silicon materials has reached 4200mAh/g, and reserves are huge in the earth's crust, is that high-energy of future generation is close
Spend the candidate material of lithium ion battery.But silicon, in embedded and abjection lithium, 300% expansion and contraction occurs for volume, in electricity
Efflorescence during the charge and discharge cycles of pond, come off, lose activity, so as to limit application of the silicon in lithium ion battery.Suppress silicon
Volumetric expansion in embedding lithium, the circulation of silicium cathode is improved into key difficulties.At present by entering by silicon nanosizing, with carbon material
Row is compound, can be effectively improved expansion and the cycle performance of silicium cathode.
Chinese patent CN103682287 A disclose a kind of preparation method of silicon based composite material, and this method is ground first
Silicon nanoparticle is embedded in village hollowing graphite layers, passes through fusion, VC mixing cladding organic carbon forerunners by graphite into village hollowing
Body, isotropism pressurized treatments and carbonization, obtain silicon based composite material.The preparation method process is complicated, and process conditions are harsh, work
Industry production is relatively difficult to achieve.Silica-base material is extruded closely knit, and the high rate performance of material is very limited.
Chinese patent CN102891297 A disclose a kind of Si-C composite material and preparation method thereof, and the composite is
Graphite, pitch and nanometer silicon composite structure, by the aqueous solution that graphite, pitch and micron silicon are added to sodium carboxymethylcellulose
Middle carry out ball milling, obtains the Si-C composite material presoma of Nano grade.The presoma is spray-dried, is carbonized, and obtains silicon
Carbon composite.This method uses sodium carboxymethylcellulose as bonding agent, the efflorescence for preventing silicon from triggering in charge and discharge process
Phenomenon, effectively improve the cycle performance of silicon.But this method carries out ball milling under sodium carboxymethylcellulose aqueous solution, spraying is done
Dry granulation, during high-energy ball milling, sodium carboxymethylcellulose long chain is easily interrupted so that and the viscosity of slurry system drastically declines,
So as to cause nano-silicon and graphite flake to be layered, therefore the dispersed of nano-silicon and graphite flake is not implemented in mechanical milling process.Secondly, drip
Green grass or young crops is oily material, is not infiltrated with water, is difficult to realize the uniform compound of silicon and carbon.3rd, the nano-silicon of surface non-oxidation layer is dredged
It is water-based relatively strong, it is spray-dried under pure aquatic system, steric hindrance and bonding effect due to no high molecular polymer, nano-silicon
Surface easily is floated to through graphite gap, causes nano-silicon to be reunited, after being fabricated to battery, is easily caused the excessive, powder of local expansion
Change, cycle performance is deteriorated.
Chinese patent CN104425802 A disclose a kind of preparation method of silicon based composite material.This method by base-material with
Conductive agent mixes, and is granulated by spray dried form.The base-material used is the mechanical mixture of emulsified asphalt, graphite and silica flour.Together
Sample, this method is spray-dried with aqueous slurry, and silicon nanoparticle easily floats, reunited, and causes the deterioration of cycle performance.
In existing system, nano-silicon disperses with the reunion in graphite recombination process along with nano-silicon, floating, nano-silicon
It is uneven, cause lithium ion battery head prepared by existing silicon materials to imitate low, Cycle Difference, expansion greatly.Therefore prepare with graphite and receive
Rice silicon is the Si-C composite material of matrix, and key is how to suppress the reunion of nano-silicon, floated, and control nano-silicon is in stone
It is dispersed in black system.
The content of the invention
It is an object of the invention to provide a kind of dispersed lithium ion battery of silicon materials in graphite flake to be answered with silicon-carbon
Condensation material, the composite are used for lithium ion battery and show efficiency high, expand performance that is small, having circulated.
To reach above-mentioned purpose, technical scheme provided by the invention is：
A kind of Silicon-carbon composite material for lithium ion battery, Si-C composite material are that silicon materials are dispersed and be embedded in graphite
The second particle structure formed between material surface and graphite material；Described second particle surface and the graphite material of inside
Material, silicon materials are coated with one layer of amorphous carbon, form the mutual random orientation of graphite material of second particle, second particle respectively to
Same sexual orientation.
The median particle diameter of described second particle is between 2~60 μm, it is preferable that between 4~30 μm, more preferably, 5
Between~15 μm.
Between monolithic graphite piece median particle diameter in graphite material is 1~15 μm, it is preferable that graphite leaf length is in 1~10 μ
Between m.
Silicon grain median particle diameter in silicon materials is between 0.01~5 μm, it is preferable that silicon grain median particle diameter 0.02~
Between 1 μm, more preferably, silicon grain median particle diameter is between 0.05~0.5 μm.
Between 0.001~2 μm of the thickness of amorphous carbon layer, it is preferable that the thickness of amorphous carbon is at 0.002~0.1 μm, more
Excellently, amorphous carbon thickness is between 0.005~0.05 μm.
In described Si-C composite material, content of graphite is 10~99wt%, it is preferable that content of graphite be 50~
80wt%.
Silicone content is 0.01~80wt%, it is preferable that silicone content is 0.1~40wt%, more preferably, silicone content be 5~
35wt%.
Agraphitic carbon content is 1~50wt%, it is preferable that agraphitic carbon content is 15~40wt%.
The present invention provides the preparation method of above-mentioned Silicon-carbon composite material for lithium ion battery, it is characterised in that：Including following
Step：
(1) graphite material and silicon materials are subjected to wet grinding with dispersant, solvent respectively, obtain graphite slurry and silicon slurry
Material, two kinds of slurries are mixed, obtain graphite/silicon mixed slurry；Or by graphite material and silicon materials simultaneously with dispersant, solvent
Wet grinding is carried out, obtains graphite/silicon mixed slurry；
(2) macromolecule polymer solution is prepared, the first carbon matrix precursor is dissolved with solvent, and and macromolecule polymer solution
Together add in the slurry obtained by step (1), carry out wet grinding, before obtaining the carbon of graphite/silicon/high molecular polymer/first
Drive body mixed slurry；Or dissolve the first carbon matrix precursor with solvent, and together it is added to step with high molecular polymer powder
(1) wet grinding is carried out in slurry obtained by, obtains the carbon matrix precursor mixed slurry of graphite/silicon/high molecular polymer/first；
(3) granulation is dried to the mixed slurry obtained by step (2), pyrocarbon is then carried out under non-oxidizing atmosphere
Change is handled；
(4) processing of the second carbon matrix precursor cladding is carried out to step (3) products therefrom, is then carried out under non-oxidizing atmosphere
High temperature cabonization；
(5) step (4) products therefrom crushed, sieve and except magnetic, the Si-C composite material is made.
Wherein, in step (1)：
Described graphite material is Delanium, native graphite, surface coated native graphite, expanded graphite, conductive stone
Ink, one kind in MCMB or at least two combination；
The silicon materials are crystalline silicon or non-crystalline silicon；The silicon materials be nano silicon particles, silicon nanowires, nano-tube,
Silicon nanorod, silicon nanorods, silicon micron particles, silicon micron bar, silicon micro wire；
The wet grinding uses appointing in high-speed stirred mill, ball mill, tube mill, type taper grinder, rod mill or sand mill
Meaning is a kind of；Preferably, the wet grinding uses sand mill.The sand mill is sanded, and is sanded using high energy mode, effectively
Linear velocity is 10~15m/s.
Solvent used in the wet grinding is organic solvent；Preferably, the organic solvent is methanol, ethanol, isopropyl
Alcohol, n-butanol, ethylene glycol, ether, acetone, 1-METHYLPYRROLIDONE, espeleton, tetrahydrofuran, benzene,toluene,xylene, N,
One kind or at least two combination in dinethylformamide, DMAC N,N' dimethyl acetamide or chloroform.
Dispersant used in the wet grinding is sodium tripolyphosphate, calgon, sodium pyrophosphate, cetyl front three
One kind or at least two combination in base ammonium bromide, polyacrylic acid, polyvinylpyrrolidone, Tween-80.
Wherein, in step (2)：
The high molecular polymer is polyacrylic acid, Sodium Polyacrylate, Lithium polyacrylate, polyvinylpyrrolidone, hydroxyl first
Base cellulose, sodium cellulose glycolate, hydroxyethyl cellulose, methyl hydroxyethylcellulose, ethylhydroxyethylcellulose, methyl hydroxyl
Propyl cellulose, carboxymethyl cellulose, sodium carboxymethylcellulose, gelatin, carragheen, pectin, propylene glycol alginate, alginic acid,
One kind or at least two combination in sodium alginate, lithium alginate, xanthans；
Further, in the high molecular polymer, polyacrylic acid, Sodium Polyacrylate, the molecular weight of Lithium polyacrylate
Preferably 400,000~80,000,000, carboxymethyl cellulose, the molecular weight of sodium carboxymethylcellulose be preferably 100,000~
1,000,000, the molecular weight of pectin is preferably 50,000~150,000, and the molecular weight of gelatin is preferably 10,000~300,
000, the molecular weight of xanthans is preferably 200,000~5,000,000, and alginic acid, sodium alginate, the molecular weight of lithium alginate are excellent
Elect 10,000~600,000 as.
The high molecular polymer accounts for 0.5~10wt% of solid in graphite/silicon mixed slurry, it is preferable that polyphosphazene polymer
Compound accounting is 1~5wt%.
First carbon matrix precursor is glucose, sucrose, chitosan, starch, citric acid, selected from coal tar pitch and petroleum asphalt, centre
Asphalt phase, phenolic resin, tar, naphtalene oil, carbolineum, polyvinyl chloride, polystyrene, polyvinylidene fluoride, polyethylene glycol oxide, poly- second
One kind or at least two combination in enol, epoxy resin, polyacrylonitrile, polymethyl methacrylate, or be step (2)
In the high molecular polymer；
Dissolve the solvent of the first carbon matrix precursor for water, methanol, ethanol, isopropanol, n-butanol, ethylene glycol, ether, acetone,
1-METHYLPYRROLIDONE, espeleton, tetrahydrofuran, benzene,toluene,xylene, N,N-dimethylformamide, N, N- dimethyl second
One kind or at least two combination in acid amides or chloroform；
The wet grinding uses appointing in high-speed stirred mill, ball mill, tube mill, type taper grinder, rod mill and sand mill
Meaning is a kind of；Preferably, the wet grinding uses sand mill；The sand mill is sanded, and is chained with not destroying high molecular molecule
Low speed sand milling is carried out premised on structure, the effective linear velocity of sand mill is 2~5m/s.
In process of lapping, the size of silicon grain reduces, and exposes the fresh surface of more non-oxidation layers, and its hydrophobicity compares
By force, little particle silicon is caused easily to float, so that and graphite laminated.Wet grinding is carried out in organic solvent system, can effectively be delayed
Solve this phenomenon.High molecular polymer is added in the form of solution or powder, the rotating speed of sand mill is reduced, does not destroy polyphosphazene polymer
Adduct molecule chain structure, high molecular polymer is dispersed in graphite/silicon/organic solvent system, on the surface of graphite and silicon
Huge network structure is formed, further suppresses floating and the reunion of silicon using the effect of its steric hindrance, realizes silicon and graphite
It is effective compound.
Wherein, in step (3)：
The drying mode uses spray dryer using spray drying, the spray drying device；
The temperature of the high temperature cabonization reaction is 500~1400 DEG C；
The heat time of the high temperature cabonization is 0.5~24 hour；
Non-oxidizing atmosphere is provided by following at least one gases during the high temperature cabonization：Nitrogen, argon gas, hydrogen,
Helium, neon or Krypton.
In spray-drying process, slurry atomization is droplet by the shower nozzle of spray dryer, the decentralized medium in drop
Tend to spread with decentralized medium in the interface rapid evaporation of drop and hot-air, the silicon grain of small size under the high temperature conditions
To droplet surface, decentralized medium is evaporated the surface that rear silicon grain is enriched in second particle.By high molecular polymer before spray drying
It is added to and huge polymer mesh structure is formed in slurry system, by the effect of its steric hindrance and adhesive effect, by silicon
Grain is firmly locked in graphite gap so that silicon grain is not easy with decentralized medium diffusive migration in spray-drying process, so as to shape
Into silicon grain inside second particle and structure that outer surface is dispersed.
Wherein, in step (4)：
The equipment of the second carbon matrix precursor cladding uses any in mechanical fusion machine, VC mixers or high speed dispersor
It is a kind of；
The second described carbon matrix precursor is selected from coal tar pitch and petroleum asphalt, mesophase pitch, polyvinyl alcohol, epoxy resin, poly- third
One or more combinations in alkene nitrile, polymethyl methacrylate；Coated according to VC mixers and high speed dispersor
During processing, it is optional can dissolve carbon matrix precursor solvent improve covered effect, selected solvent be water, methanol, ethanol, isopropanol,
N-butanol, ethylene glycol, ether, acetone, 1-METHYLPYRROLIDONE, tetrahydrofuran, benzene,toluene,xylene, N, N- dimethyl formyls
One kind at least two in amine, DMAC N,N' dimethyl acetamide or chloroform combines；
The reaction temperature of the high temperature cabonization is 500~1400 DEG C；Preferably, high temperature cabonization temperature is 700~1000 DEG C；
The heat time of high temperature cabonization is 0.5~24 hour；
The non-oxidizing atmosphere is provided by following at least one gases：Nitrogen, argon gas, hydrogen, helium, neon or krypton
Gas.
The present invention lithium ion battery negative material that also protection is prepared using above-mentioned Si-C composite material, with above-mentioned lithium
Ion battery cathode material prepares negative electrode of lithium ion battery, and the lithium-ion electric prepared with above-mentioned negative electrode of lithium ion battery
Pond.
Beneficial effect：
The present invention uses high molecular polymer, is added into when low speed is ground, with dispersed in graphite/silicon system,
The network structure formed by high molecular polymer, using its steric hindrance and bonding effect, makes silicon grain still dispersed
In graphite gap.Gained second particle is the finely dispersed structure of silicon nanoparticle, is avoided because nano-silicon is at secondary
The surface enrichment of grain causes the expansion of electrode slice subregion excessive, and SEI films are repeatedly destroyed and re-form, and electrolyte consumed
Hurry up, circulating battery be deteriorated the problem of.Si-C composite material and the inventive method processing step prepared by the present invention is simple, Yi Shi
Existing industrialized production.
Brief description of the drawings
Fig. 1 is the schematic diagram of the Si-C composite material.
Fig. 2 is SEM (SEM) photo under the Si-C composite material back scattering prepared by embodiment 1.
Fig. 3 is the SEM photograph under the Si-C composite material back scattering prepared by embodiment 2.
Fig. 4 is the X ray diffracting spectrum of the Si-C composite material prepared by embodiment 1.
Fig. 5 is cyclic curve of the full battery under 0.5C prepared by embodiment 1.
Fig. 6 is the SEM photograph of the Si-C composite material prepared by comparative example 1.
Fig. 7 is the SEM photograph of the Si-C composite material prepared by comparative example 1.
Embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1
It is 19 μm of Delanium to weigh 317g median particle diameters, and 422g median particle diameters are 200nm nano silica fume, 2400g
Ethanol, 22.17g sorbs ester -80, add sand mill in use 0.8mm zirconia ball ball milling 4h, sand mill linear velocity is 14m/
S, obtain graphite/silicon mixed slurry that median particle diameter is 5 μm.The PAA-Na solution that 739g molecular weight is 500,000 is weighed, by it
Solid content is diluted to 0.1wt% by 1wt%.222g starch is weighed, is dissolved in 2000g water.By 0.1wt% PAA-Na slurries
Added with starch solution in sand mill, above-mentioned slurry is further diluted to 5wt% with deionized water, reduces sand mill linear velocity
To 3m/s, continue ball milling 1h, obtain graphite/silicon/starch/PAA-Na mixed slurry.Above-mentioned slurry is carried out at spray drying
Reason, the EAT of spray dryer is 150 DEG C, and leaving air temp is 100 DEG C, rotary-atomizing rotating speed of shower nozzle 400Hz, charging rate
For 100g/min.Spray drying obtains the spherical or elliposoidal second particle that median particle diameter is 15 μm.By spherical or elliposoidal two
Secondary particle is put into the lower 900 DEG C of carbonizations 2h of argon atmosphere in electrothermal furnace, 5 DEG C/min of heating rate, makes starch carbonizing, obtains amorphous
Carbon is bonded and graphite/nanometer silicon composite material of cladding.Above-mentioned composite 740g, coal tar pitch 317g are weighed, adds VC mixing
10min is mixed in machine, fusion treatment 30min in fusion machine is added, by the material of above-mentioned pitch-coating in argon inert atmosphere
In, it is warming up to 900 DEG C and is carbonized 2 hours, crushes sieving after naturally cooling to room temperature, obtain silicon/stone of the secondary cladding of amorphous carbon
Black composite.
The Si-C composite material of above-mentioned preparation is characterized using following equipment, following examples use identical sign
Equipment.
Using the particle diameter distribution of the type laser particle analyzers of Dandong Bai Te BetterSize 2000 test Si-C composite material.
Using the surface topography of Hitachi SU8010 types SEM observation Si-C composite material.
Using the crystalline structure of Rigaku MiniFlex600 types x-ray diffractometer test Si-C composite material.
By native graphite, Si-C composite material and thickener, binding agent according to 87:10:1.5:1.5 ratio mixing is equal
It is even, coated on copper foil, electrode is made.It is blue using Wuhan by resulting negative plate and lithium piece assembling CR2016 type half-cells
Electronics limited company CT2001A types test equipment tests half-cell capacity and discharging efficiency.Half-cell capacity reaches
473.7mAh/g, first charge-discharge efficiency 93.0%, negative plate expansion rate is 49.0% after circulation in ten weeks.
Resulting cathode pole piece is wound by cutting, vacuum bakeout, together with the positive plate and barrier film of pairing
And after putting into correspondingly sized plastic-aluminum shell, inject a certain amount of electrolyte and seal, you can obtain one and completely contain silicium cathode
The full battery of lithium ion, full battery capacity and electric discharge are tested using the new Weir Electronics Co., Ltd. BTS79 types test equipment in Shenzhen
Efficiency.Full battery energy density reaches 718Wh/L, and 500 capability retentions of discharge and recharge are 85.1%, cell expansion 8.0%.
Half-cell and full battery is made using with the identical method of embodiment 1 in gained negative plate by following examples, and
The specific capacity and efficiency for charge-discharge of the half-cell and full battery are tested in identical equipment.
Embodiment 2
The native graphite that 633g median particle diameters are 19 μm is weighed, 90g median particle diameters are 200nm silicon nanowires, 2400g's
Ethanol, 25g cetyl trimethylammonium bromides, add in sand mill and use 0.8mm zirconia ball ball milling 4h, sand mill linear velocity
For 14m/s.Obtain graphite/silicon mixed slurry that median particle diameter is 5 μm.Weigh the PAA-Na that 833g molecular weight is 1,000,000
Solution, its solid content is diluted to 0.5% by 1%.250g sucrose is weighed, is dissolved in 2000g water.By PAA-Na solution and Portugal
Grape sugar juice is added in sand mill, and above-mentioned slurry further is diluted into 5wt% with deionized water, sand mill linear velocity is down to
3m/s, continue ball milling 1h, obtain graphite/silicon/sucrose/PAA-Na mixed slurry.Above-mentioned slurry is subjected to spray drying treatment,
The EAT of spray dryer is 150 DEG C, and outlet temperature is 100 DEG C, rotary-atomizing rotating speed of shower nozzle 400Hz, and charging rate is
100g/min.Spray drying obtains the spherical or elliposoidal second particle that median particle diameter is 15 μm.Spherical or elliposoidal is secondary
Particle is put into the lower 900 DEG C of carbonizations 2h of argon atmosphere in electrothermal furnace, 5 DEG C/min of heating rate, sucrose is carbonized, obtains amorphous carbon
Graphite/silicon composite of bonding and cladding.Above-mentioned composite particles 700g is taken, takes asphalt 174g, with VC mixers machinery
After mixing 10 minutes, add mechanical fusion machine and handle 30 minutes.By obtained above-mentioned composite in argon inert atmosphere, rise
Warm to 1000 DEG C are carbonized 2 hours, crush sieving after naturally cooling to room temperature, the graphite/silicon for obtaining the secondary cladding of amorphous carbon is multiple
Condensation material.
By native graphite, Delanium, Si-C composite material, thickener and binding agent according to 31:31:35:1.5:1.5
Ratio is well mixed, and coated on copper foil, pole piece is made.Half-cell and full battery are prepared in the way of embodiment 1, tests it
Chemical property.
It is 466.8mAh/g that half-cell, which tests its capacity, first charge-discharge efficiency 92.1%, negative plate after circulation in ten weeks
Expansion rate is 46.5%.Full battery testing, energy density 712Wh/L, capability retention is 85.0% after 500 discharge and recharges,
Cell expansion is 7.6%.
Embodiment 3
It is 21 μm of expanded graphite to weigh 475g median particle diameters, and 309g median particle diameters are 500nm silicon nanorods, 2400g
Ethylene glycol, 25g polyvinylpyrrolidones, add sand mill in, with 0.8mm zirconia ball ball milling 6h, the linear speed of sand mill
Spend for 15m/s, obtain graphite/silicon mixed slurry that median particle diameter is 4 μm.250g phenolic resin is weighed, is dissolved in 2000g second two
In alcohol.The pectin powder that 3.92g molecular weight is 10,000 is weighed, is together added with phenol resin solution in sand mill, further
Above-mentioned slurry is spent into ethylene glycol and is diluted to 5wt%, sand mill linear velocity is reduced to 3m/s, continues ball milling 1h, obtain graphite/
The mixed slurry of silicon/phenolic resin/pectin.Above-mentioned slurry is subjected to spray drying treatment, the EAT of spray dryer
For 150 DEG C, outlet temperature is 100 DEG C, rotary-atomizing rotating speed of shower nozzle 500Hz, charging rate 80g/min.Spray drying obtains
Median particle diameter is 10 μm of spherical or elliposoidal second particle.Spherical or elliposoidal second particle is put into argon atmospher in electrothermal furnace
Enclose it is lower 1000 DEG C carbonization 2h, 5 DEG C/min of heating rate, make phenolic resin carbonized, obtain amorphous carbon bonding and cladding graphite/
Nanometer silicon composite material.Above-mentioned composite particles 784g is taken, takes coal tar pitch 320g, adds 1280g DMAs
(DMAC), with after VC mixers mechanical mixture 10 minutes, vacuumize, after air in equipment is replaced into nitrogen, equipment is heated up
Continue stirring 30 minutes after to 200 DEG C, then reduce equipment rotating speed, open vacuum, until drying materials, are cooled to room temperature.Will
It is small to be warming up to 1100 DEG C of carbonizations 3 in argon inert atmosphere for silicon/graphite/amorphous carbon composite particles of obtained pitch-coating
When, sieving is crushed after naturally cooling to room temperature, obtains graphite/silicon composite of the secondary cladding of amorphous carbon.
By native graphite, Si-C composite material, thickener and binding agent according to 62:35:1.5:1.5 ratio mixing is equal
Even, coated on pole piece on copper foil, is made, method same as Example 1 prepares half-cell, full battery, tests its electrochemistry
Energy.
Prepared half-cell test, capacity 637.5mAh/g, first charge-discharge efficiency 89.1%, bears after circulation in ten weeks
Pole piece expansion rate is 70.7%.Full battery energy density is 783Wh/L, and capability retention is 81.6% after 500 discharge and recharges, electricity
Pond is expanded to 11.5%.
Embodiment 4
317g median particle diameters are weighed as 20 μm of surface coated native graphite, 500g 1-METHYLPYRROLIDONE (NMP),
12.5g PVP, add in sand mill, with 0.8mm zirconia ball ball milling 2h, obtain the graphite slurry that median particle diameter is 8 μm, sand
The linear velocity of grinding machine is 10m/s.The micron silica flour that 385g median particle diameters are 10 μm is weighed, 600g NMP, 12.5g PVP, is added
In sand mill, sand mill rotating speed 3000rpm, with 0.8mm zirconia ball ball milling 1h, the silicon slurry that median particle diameter is 1 μm is obtained,
Silicon slurry is added in above-mentioned graphite slurry and is well mixed, obtains graphite/silicon mixed slurry.7020g molecular weight is weighed as 500
Ten thousandth, solid content is 1% sodium carboxymethylcellulose (CMC-Na) slurry, adds in sand mill, further spends above-mentioned slurry
Ionized water is diluted to 5wt%, and it is 3m/s to reduce sand mill rotating speed, continues ball milling 1h, obtains silicon/graphite/CMC-Na mixing slurry
Material.Above-mentioned slurry is subjected to spray drying treatment, the EAT of spray dryer is 180 DEG C, and outlet temperature is 100 DEG C, rotation
Turn atomizer rotating speed 350Hz, charging rate 100g/min.Spray drying obtains the spherical or ellipsoid that median particle diameter is 20 μm
Shape second particle.Spherical or elliposoidal second particle is put into the lower 900 DEG C of carbonizations 2h of argon atmosphere in electrothermal furnace, heating rate 5
DEG C/min, CMC-Na is carbonized, obtain graphite/nanometer silicon composite material of amorphous carbon bonding and cladding.Weigh phenolic resin
43g adds 100g DMF, ultrasonic agitation, phenolic resin is dissolved in DMF.Add while stirring above-mentioned graphite flake/silicon grain/
Amorphous carbon composite powder 70g, 6m/s is risen to by dispersion impeller linear velocity, and stirring container temperature is risen into 150 DEG C.Reached in temperature
Continue scattered 10min after 150 DEG C.200 DEG C are then raised temperature to, holding is slowly stirred to DMF to be evaporated completely.By above-mentioned phenolic resin
The material of cladding is warming up to 900 DEG C and is carbonized 2 hours in argon inert atmosphere, crushes sieving after naturally cooling to room temperature, obtains
Silicon/graphite composite material of the secondary cladding of amorphous carbon.
By Delanium, Si-C composite material, thickener and binding agent according to 87:10:1.5:1.5 ratio mixing is equal
It is even, coated on copper foil, pole piece is made.Method according to embodiment 1 prepares half-cell, full battery, tests its chemical property.
Prepared half-cell test, capacity reach 457.4mAh/g, first charge-discharge efficiency 93.2%, after circulation in ten weeks
Negative plate expansion rate is 51.7%.Full battery energy density is 715Wh/L, and capability retention is 84.7% after 500 discharge and recharges,
Cell expansion is 8.4%.
Embodiment 5
The electrically conductive graphite that 633g median particle diameters are 4 μm is weighed, 341g median particle diameters are 200nm nanotube, 2400g's
DMF, 29g CTAB, add in sand mill and use 0.4mm zirconia ball ball milling 4h, the linear velocity of sand mill is 15m/s, in obtaining
It is worth silicon/graphite mixed slurry that particle diameter is 2 μm.Weigh 292g coal tar pitch to add in 2000g DMF, coal tar pitch suspension is made.
The PAA-Na powder that 9.74g molecular weight is 500,000 is weighed, is dissolved in ethanol, 1wt% solution is prepared, by PAA-Na solution
Mixed with coal tar pitch suspension, with DMF further by above-mentioned pulp dilution to 5wt%, it is 3m/s to reduce sand mill rotating speed, is continued
Ball milling 1h, obtain silicon/graphite/coal tar pitch/PAA-Na mixed slurry.Above-mentioned slurry is subjected to spray drying treatment, spraying
The EAT of drying machine is 150 DEG C, and outlet temperature is 100 DEG C, rotary-atomizing rotating speed of shower nozzle 500Hz, charging rate 50g/
min.Spray drying obtains the spherical or elliposoidal second particle that median particle diameter is 5 μm.Spherical or elliposoidal second particle is put
Enter the lower 1100 DEG C of carbonizations 2h of argon atmosphere in electrothermal furnace, 5 DEG C/min of heating rate, coal tar pitch is carbonized, obtain amorphous carbon and glue
Graphite/the nanometer silicon composite material for connecing and coating.Weigh asphalt 30g to add in 150g DMAC, ultrasonic agitation, stone is made
Oil asphalt suspension.Above-mentioned graphite flake/silicon grain/amorphous carbon composite powder 100g is added while stirring, by dispersion impeller linear speed
Degree rises to 6m/s, and stirring container temperature is risen into 160 DEG C.Continue scattered 10min after temperature reaches 160 DEG C.Then raise temperature to
200 DEG C, holding is slowly stirred to DMAC to be evaporated completely.By the material that above-mentioned asphalt coats in argon inert atmosphere,
2 hours are incubated at 400 DEG C, 1100 DEG C is then raised temperature to and is carbonized 2 hours, sieving is crushed after naturally cooling to room temperature, obtains without fixed
Silicon/graphite composite material of the secondary cladding of shape carbon.
By native graphite, MCMB, Si-C composite material, thickener and binding agent according to 41:41:15:1.5:1.5 ratio
It is well mixed, coated on copper foil, prepare electrode.Method according to embodiment 1 prepares half-cell and full battery testing material
Chemical property.
Half-cell test capacity is 481.7mAh/g, and efficiency is 92.5% first, the expansion rate of negative plate after circulation in ten weeks
For 35.8%.Full battery energy density is 719Wh/L, and capability retention is 84.2% after 500 discharge and recharges, is expanded to 5.8%.
Embodiment 6
It is 19 μm of carbonaceous mesophase spherules to weigh 633g median particle diameters, and 200g median particle diameters are 8 μm of micron silicon, 2400g
Ethanol, 25g polyvinylpyrrolidones, add sand mill in use 0.8mm zirconia ball ball milling 1.5h, the linear velocity of sand mill
For 14m/s, silicon/graphite slurry that median particle diameter is 10 μm is obtained.83.3g sodium alginate powders are weighed, are added in sand mill, will
Above-mentioned slurry is diluted to 5wt% with deionized water, and it be 3m/s to reduce sand mill linear velocity, continuation ball milling 1h, obtain graphite/silicon/
The mixed slurry of sodium alginate.Above-mentioned slurry is subjected to spray drying treatment, the EAT of spray dryer is 150 DEG C, is gone out
Mouth temperature is 100 DEG C, rotary-atomizing rotating speed of shower nozzle 350Hz, charging rate 100g/min.Spray drying obtains median particle diameter and is
25 μm of spherical or elliposoidal second particle.Spherical or elliposoidal second particle is put into lower 900 DEG C of argon atmosphere in electrothermal furnace
Be carbonized 2h, 5 DEG C/min of heating rate, sodium alginate is carbonized, and the graphite/nano-silicon for obtaining amorphous carbon bonding and cladding is compound
Material.Above-mentioned composite particles 600g is taken, takes asphalt 122g, after VC mixers mechanical mixture 10 minutes, machinery is added and melts
Conjunction machine is handled 30 minutes.By graphite flake/silicon grain/amorphous carbon composite particles of obtained pitch-coating in argon inert atmosphere
In, it is warming up to 900 DEG C and is carbonized 2 hours, crushes sieving after naturally cooling to room temperature, obtain silicon/stone of the secondary cladding of amorphous carbon
Black composite.
By native graphite, Si-C composite material, thickener and binding agent according to 77:20:1.5:1.5 ratio mixing is equal
It is even, coated on copper foil, prepare pole piece.Method according to embodiment 1 prepares half-cell and full battery testing its chemical property.
It is 478.6mAh/g that half-cell, which tests its capacity, first charge-discharge efficiency 92.6%, negative plate after circulation in ten weeks
Expansion rate be 62.3%.Full battery energy density is 710Wh/L, and 500 charge and discharge cycles capability retentions are 84.2%, electricity
Pond expansion 10.1%.
Embodiment 7
158g median particle diameters are weighed as 19 μm of Delanium, 200g 1-METHYLPYRROLIDONE (NMP), 4.74g PVP,
Add in sand mill, with 0.8mm zirconia ball ball milling 4h, the linear velocity of sand mill is 14m/s, obtains median particle diameter as 5 μm
Graphite slurry.The micron silicon rod that 791g median particle diameters are 5 μm is weighed, 1000g NMP, 23.73g PVP, adds sand mill
In, with 0.8mm zirconia ball ball milling 1h, the linear velocity of sand mill is 14m/s, obtains the silicon slurry that median particle diameter is 500nm,
Silicon slurry is added in above-mentioned graphite slurry and is well mixed.Citric acid 285g is weighed, is dissolved in deionized water.Weigh 9.49g
Hydroxyethyl cellulose powder, add in sand mill together with citric acid solution, further dilute above-mentioned slurry with deionized water
To 5wt%, it is 600rpm to reduce sand mill rotating speed, continues ball milling 1h, obtains the mixed of silicon/graphite/citric acid/hydroxyethyl cellulose
Close slurry.Above-mentioned slurry is subjected to spray drying treatment, the EAT of spray dryer is 180 DEG C, outlet temperature 100
DEG C, rotary-atomizing rotating speed of shower nozzle 400Hz, charging rate 100g/min.It is 15 μm spherical that spray drying, which obtains median particle diameter,
Or elliposoidal second particle.Spherical or elliposoidal second particle is put into the lower 900 DEG C of carbonizations 2h of argon atmosphere in electrothermal furnace, heating
5 DEG C/min of speed, makes citric acid be carbonized, and obtains graphite/nanometer silicon composite material of amorphous carbon bonding and cladding.Weigh poly- second
Enol 10g is added in 150g ethylene glycol, ultrasonic agitation, polyvinyl alcohol is dissolved in ethylene glycol.Above-mentioned stone is added while stirring
Ink sheet/silicon grain/amorphous carbon composite powder 95g, 6m/s is risen to by dispersion impeller linear velocity, and stirring container temperature is risen into 150
℃.Continue scattered 10min after temperature reaches 150 DEG C, holding is slowly stirred to ethylene glycol to be evaporated completely.By above-mentioned polyvinyl alcohol
The material of cladding is warming up to 900 DEG C and is carbonized 2 hours in argon inert atmosphere, crushes sieving after naturally cooling to room temperature, obtains
Silicon/graphite composite material of the secondary cladding of amorphous carbon.
By Delanium, Si-C composite material, thickener and binding agent according to 92:5:1.5:1.5 ratio is well mixed,
Coated on copper foil, pole piece is made.Method according to embodiment 1 prepares half-cell, full battery, tests its chemical property.
Prepared half-cell test, capacity reach 466.9mAh/g, first charge-discharge efficiency 93.1%, after circulation in ten weeks
The expansion rate of negative plate is 47.8%.Full battery energy density is 718Wh/L, and capability retention is after 500 discharge and recharges
84.4%, cell expansion 7.8%..
Embodiment 8
It is 19 μm of Delanium to weigh 633g median particle diameters, and 200g median particle diameters are 200nm nano silica fume, 2400g
Ethanol, 25g polyvinylpyrrolidones, add in sand mill and use 0.8mm zirconia ball ball milling 4h, the linear velocity of sand mill is
14m/s, obtain graphite/silicon slurry that median particle diameter is 5 μm.The gelatin solution that 833g relative molecular weights are 300,000 is weighed, will
Its solid content is diluted to 0.1wt% by 1%.250g glucose is weighed, is dissolved in 2000g water.0.1wt% PAA-Na is molten
Liquid is added in sand mill with glucose solution, and above-mentioned slurry further is spent into water is diluted to 5wt%, reduces sand mill linear velocity
To 4m/s, continue ball milling 1h, obtain graphite/silicon/glucose/PAA-Na mixed slurry.Above-mentioned slurry is spray-dried
Processing, the EAT of spray dryer is 150 DEG C, and leaving air temp is 100 DEG C, rotary-atomizing rotating speed of shower nozzle 400Hz, charging speed
Spend for 100g/min.Spray drying obtains the spherical or elliposoidal second particle that median particle diameter is 15 μm.By spherical or elliposoidal
Second particle is put into the lower 900 DEG C of carbonizations 2h of argon atmosphere in electrothermal furnace, 5 DEG C/min of heating rate, glucose is carbonized, obtains nothing
Graphite/the nanometer silicon composite material for carbon bonding and the cladding of shaping.Coal tar pitch 17g is taken to add in 70g N,N-dimethylformamides
(DMF), it is stirred by ultrasonic, coal tar pitch is formed partly soluble stable suspension in DMF.Above-mentioned graphite is added while stirring
Piece/silicon grain/amorphous carbon composite powder 84g, 6m/s is risen to by dispersion impeller linear velocity, and stirring container temperature is risen into 150 DEG C.
Continue scattered 10min after temperature reaches 150 DEG C.200 DEG C are then raised temperature to, holding is slowly stirred to DMF to be evaporated completely.Will be upper
The material of pitch-coating is stated in argon inert atmosphere, 900 DEG C is warming up to and is carbonized 2 hours, crushed after naturally cooling to room temperature
Sieve, obtains silicon/graphite composite material of the secondary cladding of amorphous carbon.
By Delanium, Si-C composite material, thickener and binding agent according to 77:20:1.5:1.5 ratio mixing is equal
It is even, coated on copper foil, pole piece is made.Method according to embodiment 1 prepares half-cell and its chemical property of full battery testing.
It is 480.4mAh/g that half-cell, which tests its capacity, first charge-discharge efficiency 92.2%, negative plate after circulation in ten weeks
Expansion rate be 49.0%.Full battery energy density is 713Wh/L, and capability retention is 84.6 after 500 discharge and recharges, and battery is swollen
Swollen is 8.0%.
Embodiment 9
The MCMB (MCMB) that 633g median particle diameters are 21 μm is weighed, 3g median particle diameters are 10 μm of micron silicon
Powder, 1200g ethanol, 19g polyvinylpyrrolidones, add in sand mill, the linear velocity of sand mill is 12m/s, with 1mm oxygen
Change zirconium ball ball milling 1h, obtain graphite/silicon mixed slurry that median particle diameter is 15 μm.190g glucose is weighed, 1000g is dissolved in and goes
In ionized water.It is that 40,000, solid content is 1%PAA-Na solution to weigh 633g molecular weight, and sand is together added with glucose solution
In grinding machine, above-mentioned slurry is further spent into ethylene glycol and is diluted to 5wt%, reduced sand mill linear velocity to 3m/s, continue ball milling
1h, obtain graphite/silicon/glucose/PAA-Na mixed slurry.Above-mentioned slurry is subjected to spray drying treatment, spray dryer
EAT be 150 DEG C, outlet temperature be 100 DEG C, rotary-atomizing rotating speed of shower nozzle 250Hz, charging rate 100g/min.Spray
Mist is dried to obtain the spherical or elliposoidal second particle that median particle diameter is 50 μm.Spherical or elliposoidal second particle is put into electric heating
The lower 900 DEG C of carbonizations 2h of argon atmosphere, 5 DEG C/min of heating rate, makes glucose be carbonized in stove, obtains amorphous carbon bonding and cladding
Graphite/silicon composite.Above-mentioned composite particles 633g is taken, takes coal tar pitch 30g, is added in 1000g DMF, with VC mixer machines
After tool mixes 10 minutes, vacuumize, after air in equipment is replaced into nitrogen, equipment is warming up to after 200 DEG C and continues stirring 30
Minute, equipment rotating speed is then reduced, opens vacuum, until drying materials, are cooled to room temperature.By the silicon of obtained pitch-coating/
Graphite/amorphous carbon composite particles are warming up to 1100 DEG C and are carbonized 3 hours, after naturally cooling to room temperature in argon inert atmosphere
Broken sieving, obtains graphite/silicon composite of the secondary cladding of amorphous carbon.
By above-mentioned gained Si-C composite material, thickener and binding agent according to 97:1.5:1.5 ratio is well mixed, and is applied
It is overlying on copper foil, pole piece is made, method same as Example 1 prepares half-cell, full battery, tests its chemical property.
Prepared half-cell test, capacity 378.2mAh/g, first charge-discharge efficiency 94.8%, bears after circulation in ten weeks
The expansion rate of pole piece is 37.1%.Full battery energy density is 681Wh/L, and capability retention is 86.0% after 500 discharge and recharges,
Cell expansion is 6.0%.
Comparative example 10
The native graphite that 106g median particle diameters are 20 μm is weighed, 500g ethanol, 3.18g PVP, is added in sand mill, sand
Grinding machine linear velocity is 14m/s, with 0.8mm zirconia ball ball milling 1.5h, obtains the graphite slurry that median particle diameter is 10 μm.Weigh
528g median particle diameters are 5 μm of micron silicon line, 800g ethanol, 15.84g PVP, are added in sand mill, sand mill linear velocity is
14m/s, with 0.8mm zirconia ball ball milling 1h, the silicon slurry that median particle diameter is 1 μm is obtained, silicon slurry is added into above-mentioned graphite
It is well mixed in slurry.The xanthan gum solution that 3170g molecular weight is 2,000,000, solid content is 1% is weighed, adds in sand mill, enters
Above-mentioned slurry is diluted to 5wt% by one step with deionized water, is reduced sand mill linear velocity and is down to 3m/s, continues ball milling 1h, obtain
The mixed slurry of graphite/silicon/xanthans.Above-mentioned slurry is subjected to spray drying treatment, the EAT of spray dryer is 180
DEG C, leaving air temp is 100 DEG C, rotary-atomizing rotating speed of shower nozzle 350Hz, charging rate 100g/min.Spray drying obtains intermediate value
Particle diameter is 25 μm of spherical or elliposoidal second particle.Spherical or elliposoidal second particle is put into electrothermal furnace under argon atmosphere
900 DEG C of carbonization 2h, 5 DEG C/min of heating rate, make xanthans be carbonized, and obtain graphite/nano-silicon of amorphous carbon bonding and cladding
Composite.Weigh coal tar pitch 42g and add 100g DMF, ultrasonic agitation, coal tar pitch is scattered in compared with good dissolving in DMF, shape
Into stable suspension.Above-mentioned graphite flake/silicon grain/amorphous carbon composite powder 63g is added while stirring, by dispersion impeller linear speed
Degree rises to 6m/s, and stirring container temperature is risen into 150 DEG C.Continue scattered 10min after temperature reaches 150 DEG C.Then raise temperature to
200 DEG C, holding is slowly stirred to DMF to be evaporated completely.By the material of above-mentioned pitch-coating in argon inert atmosphere, it is warming up to
900 DEG C are carbonized 2 hours, crush sieving after naturally cooling to room temperature, obtain silicon/graphite composite wood of the secondary cladding of amorphous carbon
Material.
By Delanium, above-mentioned Si-C composite material, binding agent according to 89:8:1.5:1.5 ratio is well mixed, coating
In on copper foil, pole piece is made.Method according to embodiment 1 prepares half-cell, full battery, tests its chemical property.
Prepared half-cell test, capacity reach 472.2mAh/g, first charge-discharge efficiency 92.9%, after circulation in ten weeks
The expansion rate of negative plate is 62.3%.Full battery energy density is 711Wh/L, and capability retention is after 500 discharge and recharges
84.3%, cell expansion 10.1%.
Comparative example 1
Si-C composite material is prepared according to mode substantially the same manner as Example 1, difference is：It is added without in sand grinding process
PAA-Na slurries.Mode same as Example 1 makes battery.
Half-cell is tested, capacity 475.6mAh/g, first charge-discharge efficiency 92.5%, negative plate after circulation in ten weeks
Expansion rate is 55.0%.Full battery energy density is 713Wh/L, and capability retention is 76.3% after 500 discharge and recharges, expansion rate
For 8.9%.Comparative example 2
Si-C composite material is prepared according to mode substantially the same manner as Example 2, difference is：Solvent changes in sand grinding process
Into deionized water, follow-up whole process is carried out under the system of deionized water.Mode same as Example 2 makes battery.
Half-cell is tested, capacity 469.0mAh/g, first charge-discharge efficiency 91.9%, negative plate after circulation in ten weeks
Expansion rate is 52.5%.Full battery energy density is 712Wh/L, and capability retention is 77.1% after 500 discharge and recharges, expansion rate
For 8.5%.Comparative example 3
Si-C composite material is prepared according to mode substantially the same manner as Example 5, difference is：Graphite and silicon grain are entered
PAA-Na slurries are added when row is sanded, whole process uses high-energy ball milling.Mode same as Example 5 makes battery.
Half-cell is tested, capacity 484.0mAh/g, first charge-discharge efficiency 92.1%, and negative plate is swollen after circulation in ten weeks
Swollen rate is 41.8%.Full battery energy density is 714Wh/L, and capability retention is 76.5% after 500 discharge and recharges, and expansion rate is
6.8%.
Comparative example 4
By native graphite, thickener and conductive agent according to 97:1.5:1.5 ratio is well mixed, and coated on copper foil, is made
Standby pole piece.Half-cell and full battery are prepared according to the identical method of embodiment 1, tests its chemical property.
Half-cell test capacity is 370.0mAh/g, first charge-discharge efficiency 94.2%, negative plate after circulation in ten weeks
Expansion rate is 29.0%.Full battery energy density is 678Wh/L, and 500 times circulation volume conservation rate is 87.0%, and cell expansion is
6.0%.Embodiment 1~10 and the data of comparative example 1~3 are as shown in table 1.
Table 1
It is described above, only it is presently preferred embodiments of the present invention, any formal limitation not is made to the present invention, it is any ripe
Professional and technical personnel is known, it is without departing from the scope of the present invention, real to more than according to the technical spirit of the present invention
Apply any simple modification, equivalent substitution that example made and improve etc., still fall within technical solution of the present invention protection domain it
It is interior.
Claims (10)
- A kind of 1. Silicon-carbon composite material for lithium ion battery, it is characterised in that：Si-C composite material is that silicon materials are dispersed simultaneously It is embedded in the second particle structure formed between graphite material surface and graphite material；Described second particle surface and inside Graphite material, silicon materials be coated with one layer of amorphous carbon, form the mutual random orientation of graphite material of second particle, it is secondary Grained isotropic is orientated.
- 2. Silicon-carbon composite material for lithium ion battery as claimed in claim 1, it is characterised in that：In described second particle It is worth particle diameter between 2~60 μm, between the monolithic graphite piece median particle diameter in graphite material is 1~15 μm, the silicon in silicon materials Particle median particle diameter is between 0.01~5 μm, between 0.001~2 μm of the thickness of amorphous carbon layer.
- 3. Silicon-carbon composite material for lithium ion battery as claimed in claim 1, it is characterised in that：Described Si-C composite material In, content of graphite is 10~99wt%, and silicone content is 0.01~80wt%, and agraphitic carbon content is 1~50wt%.
- 4. the preparation method of the Silicon-carbon composite material for lithium ion battery described in claim 1, it is characterised in that：Including following step Suddenly：(1) graphite material and silicon materials are subjected to wet grinding with dispersant, solvent respectively, obtain graphite slurry and silicon slurry, Two kinds of slurries are mixed, obtain graphite/silicon mixed slurry；Or graphite material and silicon materials are entered with dispersant, solvent simultaneously Row wet grinding, obtain graphite/silicon mixed slurry；(2) macromolecule polymer solution is prepared, the first carbon matrix precursor is dissolved with solvent, and with macromolecule polymer solution together Add in the slurry obtained by step (1), carry out wet grinding, obtain the carbon matrix precursor of graphite/silicon/high molecular polymer/first Mixed slurry；Or dissolve the first carbon matrix precursor with solvent, and together it is added to step (1) institute with high molecular polymer powder It is made in slurry and carries out wet grinding, obtains the carbon matrix precursor mixed slurry of graphite/silicon/high molecular polymer/first；(3) granulation is dried to the mixed slurry obtained by step (2), then carried out under non-oxidizing atmosphere at high temperature cabonization Reason；(4) processing of the second carbon matrix precursor cladding is carried out to step (3) products therefrom, high temperature is then carried out under non-oxidizing atmosphere Carbonization；(5) step (4) products therefrom crushed, sieve and except magnetic, the Si-C composite material is made.
- 5. the preparation method of Silicon-carbon composite material for lithium ion battery as claimed in claim 1, it is characterised in that：In step (1)：Described graphite material be Delanium, native graphite, surface coated native graphite, expanded graphite, electrically conductive graphite, in Between one kind in phase carbon microspheres or at least two combination；The silicon materials are crystalline silicon or non-crystalline silicon；The wet grinding uses any one in high-speed stirred mill, ball mill, tube mill, type taper grinder, rod mill or sand mill Kind；Solvent used in the wet grinding is organic solvent；Dispersant used in the wet grinding is cetyl trimethylammonium bromide, polyacrylic acid, polyvinylpyrrolidone, poly- One kind or at least two combination in sorb ester -80.
- 6. the preparation method of Silicon-carbon composite material for lithium ion battery as claimed in claim 1, it is characterised in that：In step (2)：The high molecular polymer is polyacrylic acid, Sodium Polyacrylate, Lithium polyacrylate, polyvinylpyrrolidone, methylol fibre Tie up element, sodium cellulose glycolate, hydroxyethyl cellulose, methyl hydroxyethylcellulose, ethylhydroxyethylcellulose, methylhydroxypropyl Cellulose, carboxymethyl cellulose, sodium carboxymethylcellulose, gelatin, carragheen, pectin, propylene glycol alginate, alginic acid, marine alga One kind or at least two combination in sour sodium, lithium alginate, xanthans；The high molecular polymer accounts for 0.5~10wt% of solid in graphite/silicon mixed slurry；First carbon matrix precursor is glucose, sucrose, chitosan, starch, citric acid, selected from coal tar pitch and petroleum asphalt, interphase drip Green grass or young crops, phenolic resin, tar, naphtalene oil, carbolineum, polyvinyl chloride, polystyrene, polyvinylidene fluoride, polyethylene glycol oxide, polyethylene One kind or at least two combination in alcohol, epoxy resin, polyacrylonitrile, polymethyl methacrylate, or in step (2) The high molecular polymer；The solvent for dissolving the first carbon matrix precursor is water, methanol, ethanol, isopropanol, n-butanol, ethylene glycol, ether, acetone, N- first Base pyrrolidones, espeleton, tetrahydrofuran, benzene,toluene,xylene, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide Or one kind in chloroform or at least two combination；The wet grinding uses any one in high-speed stirred mill, ball mill, tube mill, type taper grinder, rod mill and sand mill Kind.
- 7. the preparation method of Silicon-carbon composite material for lithium ion battery as claimed in claim 1, it is characterised in that：Step (3) In：The drying mode uses spray dryer using spray drying, the spray drying device；The temperature of the high temperature cabonization reaction is 500~1400 DEG C；The heat time of the high temperature cabonization is 0.5~24 hour；Non-oxidizing atmosphere is provided by following at least one gases during the high temperature cabonization：Nitrogen, argon gas, hydrogen, helium, Neon or Krypton.
- 8. the preparation method of Silicon-carbon composite material for lithium ion battery as claimed in claim 1, it is characterised in that：Step (4) In：The equipment of the second carbon matrix precursor cladding uses any one in mechanical fusion machine, VC mixers or high speed dispersor Kind；The second described carbon matrix precursor is selected from coal tar pitch and petroleum asphalt, mesophase pitch, polyvinyl alcohol, epoxy resin, polypropylene One or more combinations in nitrile, polymethyl methacrylate；The reaction temperature of the high temperature cabonization is 500~1400 DEG C；The heat time of high temperature cabonization is 0.5~24 hour；The non-oxidizing atmosphere is provided by following at least one gases：Nitrogen, argon gas, hydrogen, helium, neon or Krypton.
- A kind of 9. negative electrode of lithium ion battery, it is characterised in that：Prepared using the Si-C composite material described in claim 1.
- A kind of 10. lithium ion battery, it is characterised in that：Prepared using the negative electrode of lithium ion battery described in claim 9.
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