CN110098402A - A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof - Google Patents
A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof Download PDFInfo
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- CN110098402A CN110098402A CN201910485648.5A CN201910485648A CN110098402A CN 110098402 A CN110098402 A CN 110098402A CN 201910485648 A CN201910485648 A CN 201910485648A CN 110098402 A CN110098402 A CN 110098402A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The Si-C composite material and preparation method thereof that the present invention relates to a kind of for lithium ion battery, the Si-C composite material is the Si-C composite material containing Copper-cladding Aluminum Bar, and the Si-C composite material is to be obtained and the second particle being compounded to form is by being crushed by silicon materials, copper compound and carbon material；And the Si-C composite material surface coats one layer of carbon or non-carbon coated.Compared to traditional silicon-carbon cathode, Si-C composite material prepared by the present invention shows higher coulombic efficiency and capacity for lithium ion battery, relatively low activation polarization effect, it has been obviously improved energy density, high rate performance and the cycle performance of lithium ion battery, present invention process process is simple, is easy to realize industrial production.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to a kind of Si-C composite material for lithium ion battery and its
Preparation method.
Background technique
It is close for energy due to the fast development and extensive use of various portable electronic devices and electric car in recent years
The demand for the lithium ion battery that degree is high, has extended cycle life is increasingly urgent to.The negative electrode material master of current commercialized lithium ion battery
To be graphite, but since theoretical capacity is low (372mAh/g), limit further increasing for lithium ion battery energy density.In crowd
In more novel cathode material for lithium ion batteries, silicium cathode material has the high capacity advantage that can not be equal to of other negative electrode materials
(Li22Si5, theoretical lithium storage content 4200mAh/g), it is 11 times or more of current commercialization carbon negative pole material theoretical capacity.But
Silicon causes it in cyclic process along with biggish volume expansion, causes the loss of capacity.Meanwhile silicon is as semiconductor,
Conductivity is lower, causes silicium cathode polarization larger, further results in that the internal resistance of cell is larger, and high rate performance is poor.And it is embedding
There are serious bulk effect during de- lithium, volume change is about 400%, will cause electrode material dusting and electrode material
Material is separated with collector.In addition, the silicium cathode material being exposed in electrolyte is continuous due to the bulk effect in charge and discharge process
Fresh surface is formed, therefore consumes electrolyte persistently to generate SEI film, reduces the cycle performance of electrode material.Silica-base material
Drawbacks described above seriously limit its commercialized application.
In order to solve the problems, such as that silicium cathode is above-mentioned various, the research of silicium cathode material is concentrated mainly on both at home and abroad at present following
Several aspects: (1) size of silicon particle is merely reduced, uses nano silicon particles, such as to slow down the bulk effect of silicon particle.But it receives
The silicon particle of riceization causes battery coulombic efficiency very low due to large specific surface area, and in cyclic process, silicon particle surface
SEI is generated repeatedly, is caused the SEI film on surface thicker, has been obstructed the conduction of electronics, causes the inactivation of particle, limit battery
Cycle performance.(2) preparation has the silicon materials of special nanostructure, such as nano-tube, silicon nanowires, porous silicon, but such
Method higher cost, and yield is lower, is only suitable for laboratory research at present.(3) by silicon and conductive additive, amorphous carbon, stone
The carbon materials such as ink are compound, prepare Si-C composite material.Such composite material is due to having both the high capacity of silicon and following for graphite material
Ring performance has attracted the attention of numerous researchers.But graphite and agraphitic carbon content in such material is excessively high and silicone content
The actual use capacity that will lead to material when lower is relatively low.(4) silicon materials or Si-C composite material are subjected to surface cladding, made
Material keeps stable SEI in the circulation of lithium ion battery, reduces the generation of side reaction to improve coulombic efficiency.
Chinese patent CN108832077A discloses a kind of preparation method of Copper-cladding Aluminum Bar core-shell structure Si-C composite material, should
Method is coated on the surface of nano-silicon using phenolic resin and polyethyleneimine, is complexed using polyethyleneimine and copper ion, shape
At chelate, it is evenly distributed on the surface of nano-silicon, by high-temperature process, obtains Si-C composite material.This method has synthesized copper
The Si-C composite material of doping, but in the synthesis process, copper ion quantity is more difficult to control, and the doping of silicon is more difficult quantitative, than
More difficult formation cupro silicon.This method must be less than the nano silica fume of 100nm using median particle diameter, and material specific surface area is larger,
More SEI is generated when embedding lithium for the first time, causes its head effect lower.It utilizes complex reaction, generates chelate, and reaction condition compares
Harshness, meanwhile, nano silica fume need to be surface-treated with hydrofluoric acid, and specific operation process is more complicated.Synthesized by this method
Si-C composite material blends system in graphite, shows lower first effect and capacity, while recycling poor.
Chinese patent CN102891297A discloses a kind of Si-C composite material and preparation method thereof, which is stone
Ink, pitch and nanometer silicon composite structure, by the way that graphite, pitch and micron silicon to be added in the aqueous solution of sodium carboxymethylcellulose
Ball milling is carried out, the Si-C composite material presoma of Nano grade is obtained.The presoma is spray-dried, is carbonized, and silicon-carbon is obtained
Composite material.This method graphite and amorphous carbon improve the conductivity between silicon particle and surface, but and do not solve silicon material
Expect the high problem of resistivity itself, the big problem of still performance polarization after battery is made.This method synthesis technology is complicated simultaneously,
Using high molecular polymer as the stabilizer of system, but it is easy to interrupt high molecular polymer in mechanical milling process, thus
Cause slurry system unstable, nano-silicon is easy to reunite, and after being fabricated to battery, part expands excessive, dusting, and cycle performance becomes
Difference.
Chinese patent CN107785095A discloses porous silicon electrocondution slurry and its preparation of a kind of copper doped and graphene
Method.Porous silicon, copper and graphene are mixed together ball milling by this method, and nanometer powder is made, and stabilizer, dispersing agent is added and has
Cathode of lithium battery slurry is made in airborne body.This method mixes copper with silicon, it is intended to improve the stability and conduction of slurry
Property, the introducing of copper are provided solely for the effect of conductive agent, and the electric conductivity of silicon does not effectively improve.
Application publication number is that the Chinese patent literature of CN108807861A discloses a kind of lithium ion battery irregular shape
Second particle of shape and preparation method thereof.The second particle carries out secondary granulation by 0.01~5 μm of Si-C composite material,
It is crushed again, obtains the second particle of irregular shape, there is that conductive agent is evenly dispersed inside second particle, second particle surface
Coat one layer of amorphous carbon.Synthesized irregular second particle is applied in lithium ion battery, cathode have compacted density it is high,
The advantage that second particle is non-breakable, pole piece interparticle contact point is more, polarization is lower.The second particle is using non-modified
Silicon materials synthesized by, original silicon material resistivity is higher, and synthesized second particle electric conductivity is poor, thereby reduces battery
First charge discharge efficiency, cause the energy density of battery lower, high rate performance is poor.
The Chinese patent literature that application publication number is CN105161695A discloses a kind of negative electrode of lithium ion battery with spherical
Active material particle and preparation method thereof, application.The spherical active material particle be by a kind of fibrous carbon with it is micro-nano
Spherical composite pellets made from the spray-dried method of silicon isoreactivity material grains of scale.The spherical active material particle is not
It is the great porous structure of specific surface area by secondary cladding.Therefore the coulombic efficiency for the first time of lithium ion battery made of the material
It is lower, the first run efficiency shown such as embodiment only 60%.In addition, porous structure means that the density of the material is lower,
It is lower to will lead to lithium ion battery energy density made of the material.In addition, contained by the spherical active material particle
Fibrous carbon be up to 16.7% or more, other than causing higher specific surface area and lower density, also result in material
Activity substance content is lower, to cause the capacity of composite material lower.
Therefore, lower for the intrinsic conductivity of silicon, lead to that battery polarization is big, resistance is high, energy density is low, high rate performance
The problem of difference, is not solved effectively, and be the technical problem in the field.
Summary of the invention
The Si-C composite material and preparation method thereof that the object of the present invention is to provide a kind of for lithium ion battery solves to make
Higher for the silicon resistivity of semiconductor, in lithium ion battery applications, polarizing, larger, energy density is lower, circulation is poor is asked
Topic.
To achieve the above object, present invention provide the technical scheme that
A kind of Si-C composite material for lithium ion battery, the Si-C composite material are that the silicon-carbon containing Copper-cladding Aluminum Bar is compound
Material, the Si-C composite material are to pass through the second particle being compounded to form by silicon materials, copper compound and carbon material to pass through again
Cross the Si-C composite material of broken formation.
Further, the Si-C composite material surface coats one layer of carbon.
The silicon materials median particle diameter is between 0.1~10 μm；The second particle median particle diameter 2~50 μm it
Between；The median particle diameter of the Si-C composite material is between 0.2~15 μm.
Preferably, the median particle diameter of the silicon materials Si-C composite material is between 1~10 μm；More preferably, the silicon-carbon
The median particle diameter of composite material is between 2~7 μm；More preferably, the median particle diameter of the Si-C composite material is between 3~8.
Preferably, the median particle diameter of the second particle is between 10~40 μm；More preferably, in the second particle
It is worth partial size between 15~30 μm.
Preferably, the median particle diameter of the Si-C composite material is between 1~10 μm；More preferably, the silicon-carbon is compound
The median particle diameter of material is between 2~7 μm；More preferably, the median particle diameter of the Si-C composite material is between 3~8 μm.
In the Si-C composite material, silicone content between 74~98%, copper coin cellulose content between 0.1~20%,
Carbon content is between 0.1~20%；The cladding carbon-coating on Si-C composite material surface is amorphous carbon or graphitized carbon.
The preparation method of the Si-C composite material for lithium ion battery is also disclosed in the present invention: including following step
It is rapid:
1) in a solvent by the first carbon matrix precursor and the dissolution of copper presoma, the two is mixed, mixed solution is made, silicon is added
Material, dispersing agent, and be uniformly mixed, obtain silicon/first carbon matrix precursor/copper presoma mixed slurry；
2) granulation is dried to the obtained mixed slurry of step 1), pyrocarbon is then carried out under non-oxidizing atmosphere
Change processing；
3) break process is carried out to step 2) products therefrom, obtains broken material；
4) step 3) products therefrom sieve and except magnetic, the Si-C composite material of the uncoated carbon in surface is made；
The Si-C composite material for preparing coated with carbon needs to follow the steps below processing again to step 3) products therefrom:
5) to product obtained by step 3) using the second carbon matrix precursor carry out carbon coating, then under non-oxidizing atmosphere into
The processing of row high temperature cabonization,
6) step 5) products therefrom sieve and except magnetic, obtain carbon-coated Si-C composite material.
In step 1), first carbon matrix precursor is glucose, sucrose, chitosan, starch, citric acid, gelatin, seaweed
Acid, carboxymethyl cellulose, sodium carboxymethylcellulose, selected from coal tar pitch and petroleum asphalt, phenolic resin, tar, naphtalene oil, carbolineum, polychlorostyrene second
Alkene, polystyrene, polyvinylidene fluoride, polyvinylpyrrolidone, polyethylene glycol oxide, polyvinyl alcohol, epoxy resin, polypropylene
One of nitrile, polymethyl methacrylate or a variety of combinations；
The copper presoma be one of copper acetate, copper sulphate, copper chloride, copper nitrate, copper carbonate, Kocide SD or
A variety of combinations；
The solvent is water, methanol, ethyl alcohol, isopropanol, n-butanol, ethylene glycol, ether, acetone, N- crassitude
Ketone, espeleton, tetrahydrofuran, benzene,toluene,xylene, n,N-Dimethylformamide, n,N-dimethylacetamide, three chloromethanes
One of alkane or a variety of combinations；
The silicon materials are crystalline silicon or amorphous silicon；
In step 2):
The drying-granulating is carried out by the way of spray drying；
The high temperature cabonization is using any one in rotary furnace, roller kilns, pushed bat kiln, atmosphere batch-type furnace or tube furnace；
The temperature of the high temperature cabonization reaction is 500-1000 DEG C, and soaking time is 0.5-72 hours；
The non-oxidizing atmosphere is provided by following at least one gases: nitrogen, argon gas, hydrogen, helium, neon, Krypton.
In step 3), the crumbling method is carried out by the way of air-flow crushing or mechanical crushing.
In step 5):
The cladding of second carbon matrix precursor, carbonizing apparatus can be completed at the same time using chemical vapour deposition reactor furnace；
The coating equipment of second carbon matrix precursor can also using mechanical fusion machine, VC mixing machine, high speed disperser,
Any one progress in reaction kettle；
Second carbon matrix precursor is selected from coal tar pitch and petroleum asphalt, mesophase pitch, acetylene, ethylene, ethane, methane, gathers
One of vinyl alcohol, epoxy resin, polyacrylonitrile, polymethyl methacrylate or a variety of combinations；
The high temperature cabonization device therefor is any in rotary furnace, roller kilns, pushed bat kiln, atmosphere batch-type furnace or tube furnace
It is a kind of；
The temperature of the high temperature cabonization reaction is 600-1100 DEG C, and soaking time is 0.5-72 hours；
The non-oxidizing atmosphere is provided by following at least one gases: nitrogen, argon gas, hydrogen, helium, neon, Krypton.
The present invention also protects the negative electrode of lithium ion battery containing above-mentioned Si-C composite material.
Further, in the negative electrode of lithium ion battery, mass ratio shared by silicon-carbon cathode material is 80~96%；The cathode
In also contain organic polymer binder, the organic macromolecular adhesives be carboxymethyl cellulose, carboxymethyl cellulose lithium,
Sodium carboxymethylcellulose, butadiene-styrene rubber, polyacrylic acid, Sodium Polyacrylate, Lithium polyacrylate, polystyrene acrylic acid copolymer,
Polyacrylate copolymer, polyimides, polyamidoimide, polyacrylonitrile, is gathered carboxymethyl cellulose-acrylic copolymer
Acrylonitrile acrylic copolymer, sodium alginate, lithium alginate, ethylene acrylic acid co polymer, hydrogel, xanthan gum, gathers alginic acid
At least one of ethylene oxide, polyvinyl alcohol, poly acrylic acid-poly vinyl alcohol cross-linked copolymer or a variety of combinations.
Preferably, organic polymer binder at least contains a kind of high tensile and a kind of high resiliency shape in the cathode
The binder of change.By the way that the organic polymer binder of high tensile and high resiliency deformation characteristic to be applied in combination, make silicon material
Material surface is wrapped up by these binders, and the expansion of particle on the one hand can be inhibited to reduce the destruction to SEI film to a certain extent,
On the other hand still particle can be closely connect after silicon materials repeatedly expansion-contraction with particle, particle and collector, is protected
The electrical activity of material is held, to promote the cycle performance of battery.
The present invention also protects the lithium ion battery prepared using above-mentioned negative electrode of lithium ion battery.
The present invention uniformly mixes copper presoma with silicon materials, carbon material, and by high-temperature calcination, carbon restores copper presoma
At elemental copper, at high temperature, copper atom is spread into silicon materials, in conjunction with silicon atom, forms Cu-Si alloy, and copper atom
Diffusional resistance it is smaller, therefore in silicon materials Cu-Si alloy generation it is relatively uniform.
As semiconductor, the resistivity of silicon is high, reaches 2.3*105Ω m, the resistivity of metallic copper only 1.75*10-8
Excellent electronics conduction, therefore the silicon after Copper-cladding Aluminum Bar, resistance are played in the presence of Cu atom in Ω m, Cu-Si alloy
Rate significantly reduces, and the self-conductance rate of silicon is greatly improved.
Compared with prior art, the beneficial effects of the present invention are:
1. forming Cu-Si alloy containing the Si-C composite material of Copper-cladding Aluminum Bar, copper atom and silicon atom prepared by the present invention, greatly
The resistivity of material is reduced greatly, is applied in lithium ion battery, is significantly reduced the internal resistance of battery, improve battery for the first time
Coulombic efficiency, and then improve the high rate performance and energy density of battery；
2. Si-C composite material prepared by the present invention is irregular pattern, when making electrode, irregular particle is mutually filled out
Intergranular gap is filled, the compacted density of electrode is greatly improved, also, contacting with each other property is more preferable between irregular particle, significantly
The contact internal resistance of electrode is reduced, and then improves the high rate performance of battery.
3. Si-C composite material prepared by the present invention is irregular pattern, after being prepared into electrode, assembled battery, particle is connect
Contacting surface is bigger, it is easier to realize the conducting of lithium ion, the significant increase high rate performance of battery.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) map of Si-C composite material prepared by embodiment 1.
Fig. 2 is the XRD spectrum of Si-C composite material prepared by comparative example 2.
Fig. 3 is scanning electron microscope (SEM) photo of Si-C composite material prepared by embodiment 1.
Fig. 4 is the SEM photograph of Si-C composite material prepared by embodiment 1.
Fig. 5 is the SEM photograph of Si-C composite material prepared by comparative example 2.
Fig. 6 is the full battery cyclic curve of Si-C composite material prepared by embodiment 1.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Embodiment 1
500g sucrose is weighed, 24.9g copper sulphate is dissolved in 2000g deionized water, forms homogeneous solution.It takes in 1000g
It is worth the crystal silicon powder that partial size is 1 μm, is sufficiently stirred with above-mentioned slurry, is uniformly mixed.Slurry is subjected to spray drying granulation, is obtained
The second particle that median particle diameter is 13 μm.By the dry powder after spray drying in argon inert atmosphere, it is small that 10 are heated at 600 DEG C
When, so that sucrose is carbonized, the second particle after being carbonized.Above-mentioned second particle is subjected to air-flow crushing, is taken above-mentioned smashed
Si-C composite material 800g, coal tar pitch 114g are added in mechanical fusion machine, and high speed fusion treatment 30 minutes, obtain at 1500 rpm
The spherical silicon composite particles coated to coal tar pitch.By above-mentioned material in argon inert atmosphere, 2 hours are kept the temperature at 300 DEG C, with
After be warming up to 850 DEG C be carbonized 3 hours, be sieved after cooled to room temperature, obtain median particle diameter be 1.3 μm have amorphous carbon
The Si-C composite material of cladding.
It is characterized using Si-C composite material of the following equipment to above-mentioned preparation, following embodiment is all made of identical characterization
Equipment.
Using the particle diameter distribution of 2000 type laser particle analyzer of Dandong Bai Te BetterSize test Si-C composite material.
Using the crystalline structure of Rigaku miniFlex600 type x-ray diffractometer test Si-C composite material.
Using the surface topography of Hitachi SU8010 type scanning electron microscope observation Si-C composite material.
Fig. 1 show the XRD spectrum of Si-C composite material prepared by embodiment 1, from map as it can be seen that being 44.5 ° in 2 θ
With 45.1 °, have apparent Cu-Si alloy peak, show the generation for having Cu-Si alloy inside prepared Si-C composite material.
Fig. 2 show the XRD spectrum of Si-C composite material prepared by comparative example 2, from map as it can be seen that being 44.5 ° in 2 θ
With 45.1 °, the appearance at no Cu-Si alloy peak, show the Si-C composite material prepared under the conditions of comparative example do not generate Cu-Si conjunction
Gold.
Fig. 3 show the SEM photograph that Si-C composite material prepared by embodiment 1 amplifies 500 times, and photo is as it can be seen that implement
Random pattern is presented in Si-C composite material prepared by example 1, and the equally distributed bright spot in surface is Cu enrichment of element region.
Fig. 4 show the SEM photograph that Si-C composite material prepared by embodiment 1 amplifies 20000 times, and photo is as it can be seen that reality
Applying Si-C composite material surface prepared by example 1 has apparent Cu-Si alloy to be distributed.
Fig. 5 show the SEM photograph that Si-C composite material prepared by comparative example 2 amplifies 20000 times, and photo is shown, right
One layer of carbon film of Si-C composite material coated with uniform prepared by ratio 2, distribution of the surface without Cu-Si alloy.
80 parts of above-mentioned Si-C composite material is taken, 10 parts of conductive additive, 10 parts of binder, is homogenized, applies under water-based system
Cloth is dried, is rolled, and obtains siliceous cathode pole piece.
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 25.4 Ω cm.
Full battery assessment: siliceous cathode pole piece obtained above by cutting, vacuum bakeout, with the positive plate matched and every
After film is wound together and puts into plastic-aluminum shell of corresponding size, injects a certain amount of electrolyte and seal, can be obtained after chemical conversion
To a complete siliceous negative electrode lithium ion full battery.It should with the cell tester test of new Weir Electronics Co., Ltd., Shenzhen
Capacity and average voltage of the full battery under 0.2C discharge current recycle 200 capacity under 0.5C charge-discharge velocity and keep
Rate data.Thus it is 94.1%, volume energy density 815.4Wh/L that the constant current for the first time for obtaining full battery, which is filled with ratio, 200 times
Capacity retention ratio after charge and discharge cycles is 84.3%.
Embodiment 2
25g glucose is weighed, 156g copper sulphate is dissolved in 2000g ethyl alcohol, forms homogeneous solution.Take 1000g intermediate value grain
The crystal silicon powder that diameter is 4.5 μm, is sufficiently stirred with above-mentioned slurry, is uniformly mixed.Slurry is subjected to spray drying granulation, is obtained
It is worth the second particle that partial size is 26 μm.By the dry powder after spray drying in argon inert atmosphere, heated 6 hours at 700 DEG C,
Glucose is set to be carbonized, the second particle after being carbonized.Second particle after carbonization is subjected to air-flow crushing, after taking above-mentioned crushing
Particle 800g took the asphalt 50g of 200 meshes, after ten minutes with VC mixing machine mechanical mixture, in the atmosphere of nitrogen protection
Under, equipment is warming up to 300 DEG C while stirring, continues stirring 30 minutes, is then cooled to room temperature.By above-mentioned material in argon
In gas inert atmosphere, 2 hours are kept the temperature at 300 DEG C, 900 DEG C is then raised temperature to and is carbonized 2 hours, mistake after cooled to room temperature
Sieve, obtaining median particle diameter is 5.3 μm with amorphous carbon-coated Si-C composite material.
87 parts of above-mentioned Si-C composite material is taken, 3 parts of conductive additive, 10 parts of binder, is homogenized, applies under water-based system
Cloth is dried, is rolled, and obtains siliceous cathode pole piece.
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 1.8 Ω cm.
The volume energy density for measuring full battery reaches 824.5Wh/L, and it is 94.7% that constant current, which is filled with ratio, 200 charge and discharges
Capacity retention ratio after electricity circulation is 81.9%.
Embodiment 3
667g sucrose is weighed, 156g copper acetate is dissolved in 2000g deionized water, forms homogeneous solution.It takes in 1000g
The amorphous silicon powders that value partial size is 8 μm, the single-walled carbon nanotube slurry that 25g solid content is 0.4%, 50g polyvinylpyrrolidone, with
Above-mentioned slurry is sufficiently stirred, and is uniformly mixed.Slurry is subjected to spray drying granulation, obtains secondary that median particle diameter is 46 μm
Grain.By the dry powder after spray drying in argon inert atmosphere, is heated 2 hours at 800 DEG C, so that sucrose is carbonized, be carbonized
Second particle material afterwards.Second particle material after taking above-mentioned carbonization carries out air-flow break process, and obtaining median particle diameter is 10 μ
The Si-C composite material of m.
Take 90 parts of above-mentioned Si-C composite material, 4 parts of conductive additive, 6 parts of binder, be homogenized, be coated under water-based system,
It dries, roll, obtain siliceous cathode pole piece.
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 6.4 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 840.8Wh/L, and constant current is filled
Entering ratio is 94.0%, and the capacity retention ratio after 200 charge and discharge cycles is 81.6%.
Embodiment 4
74.8g copper sulphate is weighed, is dissolved in 1500g deionization, homogeneous solution is formed, weighs 12.5g carboxymethyl cellulose
Plain sodium is added in above-mentioned solution, mixed solution is made.Taking 1000g median particle diameter is 5 μm of amorphous silicon powders, is filled with above-mentioned slurry
Divide stirring, is uniformly mixed.Slurry is subjected to spray drying granulation, obtains the second particle that median particle diameter is 30 μm.It will do by spraying
Dry powder after dry heats 6 hours at 500 DEG C in argon inert atmosphere, so that sodium carboxymethylcellulose is carbonized, after obtaining carbonization
Second particle.Above-mentioned second particle is subjected to mechanical crushing processing, takes above-mentioned smashed Si-C composite material 800g, mistake
The asphalt 100g of 200 meshes is added in mechanical fusion machine, at 1500 rpm high speed fusion treatment 30 minutes, obtains coal drip
The spherical silicon composite particles of blueness cladding.By above-mentioned material in argon inert atmosphere, 2 hours are kept the temperature at 300 DEG C, is then heated up
It is carbonized 2 hours to 1000 DEG C, is sieved after cooled to room temperature, obtaining median particle diameter is that 6 μm have is amorphous carbon-coated
Si-C composite material.
Take 85 parts of above-mentioned Si-C composite material, 7 parts of conductive additive, 8 parts of binder, be homogenized, be coated under water-based system,
It dries, roll, obtain siliceous cathode pole piece.
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 7.0 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 830.6Wh/L, and constant current is filled
Entering ratio is 94.3%, and the capacity retention ratio after 200 charge and discharge cycles is 82.3%.
Embodiment 5
167g sucrose is weighed, 63g copper chloride is dissolved in 2000g methanol, forms homogeneous solution.Take 1000g median particle diameter
It for 5.2 μm of amorphous silicon powders, is sufficiently stirred, is uniformly mixed with above-mentioned slurry.Slurry is subjected to spray drying granulation, obtains intermediate value
The second particle that partial size is 35 μm.By the dry powder after spray drying in argon inert atmosphere, heats 2 hours, make at 600 DEG C
Sucrose carbonization, the second particle after being carbonized.Second particle after carbonization is mechanically pulverized, broken material is obtained
Material takes above-mentioned broken rear material 1000g, is added in CVD kiln, N is arranged2Flow velocity 25L/h is heated up with 10 DEG C/min of rate
To 900 DEG C, it is passed through C at this time2H2Gas, by N2And C2H2Flow velocity is adjusted to 20L/h, 900 DEG C constant temperature 2 hours, cross screen out magnetic after
Obtain the carbon-coated Si-C composite material that median particle diameter is 6.5 μm.
80 parts of above-mentioned Si-C composite material is taken, 10 parts of conductive additive, 10 parts of binder, is homogenized, applies under water-based system
Cloth is dried, is rolled, and obtains siliceous cathode pole piece
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 2.4 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 838.9Wh/L, and constant current is filled
Entering ratio is 94.5%, and the capacity retention ratio after 200 charge and discharge cycles is 83.7%
Embodiment 6
100g asphalt is taken, the n,N-Dimethylformamide of 1000g is added, stirs, mixed slurry is made.It weighs
74.8g copper sulphate is dissolved in 500g methanol, and copper-bath is added in above-mentioned slurry, and weighing 1000g median particle diameter is 7 μ
The amorphous silicon powders of m are added in above-mentioned mixed slurry, and stirring is uniformly mixed.Slurry is subjected to spray drying granulation, obtains intermediate value
The second particle that partial size is 42 μm.By the dry powder after spray drying in argon inert atmosphere, heats 5 hours, make at 900 DEG C
Asphalt carbonization, obtains second particle material.Above-mentioned second particle material progress air-flow is crushed, by sieving, except after magnetic
Obtain the Si-C composite material that median particle diameter is 8.8 μm.
Take 96 parts of above-mentioned Si-C composite material, 1 part of conductive additive, 3 parts of binder, be homogenized, be coated under water-based system,
It dries, roll, obtain siliceous cathode pole piece.
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 27.7 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 845.6Wh/L, and constant current is filled
Entering ratio is 94.0%, and the capacity retention ratio after 200 charge and discharge cycles is 80.7%.
Embodiment 7
29g coal tar pitch is weighed, 1500g tetrahydrofuran is added, stirring forms uniformly mixed slurry.Weigh 2.5g sulfuric acid
Copper is dissolved in the methanol of 500g, and copper-bath is added in above-mentioned slurry, weighs the crystal that 1000g median particle diameter is 4 μm
Silicon powder is added in above-mentioned slurry and stirs, and is uniformly mixed.Slurry is subjected to spray drying granulation, obtaining median particle diameter is 25 μm
Second particle.By the dry powder after spray drying in argon inert atmosphere, is heated 4 hours at 800 DEG C, coal tar pitch is made to be carbonized,
Second particle after being carbonized.Above-mentioned second particle is subjected to air-flow crushing, obtains broken material.After taking 800g broken
Material, coal tar pitch 46g after ten minutes with VC mixing machine mechanical mixture under the atmosphere of nitrogen protection, incites somebody to action while stirring
Equipment is warming up to 300 DEG C, continues stirring 30 minutes, is then cooled to room temperature.By above-mentioned material in argon inert atmosphere,
2 hours are kept the temperature at 300 DEG C, 800 DEG C is then raised temperature to and is carbonized 4 hours, be sieved after cooled to room temperature, obtaining median particle diameter is
5 μm have amorphous carbon-coated Si-C composite material.
82 parts of above-mentioned Si-C composite material is taken, 8 parts of conductive additive, 10 parts of binder, is homogenized, applies under water-based system
Cloth is dried, is rolled, and obtains siliceous cathode pole piece.
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 37.1 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 829.5Wh/L, and constant current is filled
Entering ratio is 93.3%, and the capacity retention ratio after 200 charge and discharge cycles is 83.1%.
Embodiment 8
5g glucose is weighed, 467.9g copper acetate is dissolved in 1700g ethyl alcohol, forms mixed solution.Take 1000g intermediate value grain
The amorphous silicon powders that diameter is 10 μm stir, and are uniformly mixed.Slurry is subjected to spray drying granulation, obtaining median particle diameter is 50 μm
Second particle.By the dry powder after spray drying in argon inert atmosphere, is heated 3 hours at 1000 DEG C, glucose is made to be carbonized,
Second particle after being carbonized.Above-mentioned second particle is subjected to air-flow crushing, sieves, be 15 μm except median particle diameter is obtained after magnetic
Si-C composite material.
Take 91 parts of above-mentioned Si-C composite material, 0.5 part of conductive additive, 8.5 parts of binder, under water-based system homogenate,
It is coated with, dries, rolls, obtain siliceous cathode pole piece.
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 2.4 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 853.5Wh/L, and constant current is filled
Entering ratio is 94.2%, and the capacity retention ratio after 200 charge and discharge cycles is 79.4%.
Embodiment 9
156g copper acetate is weighed, is dissolved in 1800g deionized water, taking 1000g median particle diameter is 0.1 μm of crystalline silicon
Powder, is added the Sodium Polyacrylate glue of 286g solid content 10%, and stirring is uniformly mixed.Slurry is subjected to spray drying granulation, is obtained
The second particle for being 2 μm to median particle diameter.By the dry powder after spray drying in argon inert atmosphere, it is small that 2 are heated at 600 DEG C
When, so that Sodium Polyacrylate is carbonized, the second particle material after being carbonized.Above-mentioned second particle material is subjected to air-flow crushing,
Obtain broken material.Above-mentioned smashed Si-C composite material 800g is taken, is added in CVD kiln, N is set2Flow velocity 25L/
H is warming up to 900 DEG C with 10 DEG C/min of rate, is passed through C at this time2H2Gas, by N2And C2H2Flow velocity is adjusted to 20L/h, 900
DEG C constant temperature 2 hours.Obtaining median particle diameter is 0.2 μm with carbon-coated Si-C composite material.
Take 86 parts of above-mentioned Si-C composite material, 7 parts of conductive additive, 7 parts of binder, be homogenized, be coated under water-based system,
It dries, roll, obtain siliceous cathode pole piece.
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 1.8 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 812.4Wh/L, and constant current is filled
Entering ratio is 95.0%, and the capacity retention ratio after 200 charge and discharge cycles is 85.3%.
Embodiment 10
623.9g copper acetate is weighed, is dissolved in 2000g deionization, homogeneous solution is formed, weighs 12.5g carboxymethyl cellulose
Plain sodium is added in above-mentioned solution, mixed solution is made.Taking 1000g median particle diameter is 1 μm of crystal silicon powder, is filled with above-mentioned slurry
Divide stirring, is uniformly mixed.Slurry is subjected to spray drying granulation, obtains the second particle that median particle diameter is 10 μm.It will do by spraying
Dry powder after dry heats 2 hours at 600 DEG C in argon inert atmosphere, so that sodium carboxymethylcellulose is carbonized, after obtaining carbonization
Second particle.Above-mentioned second particle is subjected to air-flow crushing, obtains smashed material.Above-mentioned material 800g is taken, 200 mesh are crossed
The asphalt 34.3g of sieve is added in mechanical fusion machine, and high speed fusion treatment 30 minutes, obtain coal tar pitch packet at 1500 rpm
The material covered.By above-mentioned material in argon inert atmosphere, 2 hours are kept the temperature at 300 DEG C, it is small to then raise temperature to 900 DEG C of carbonizations 2
When, sieving after cooled to room temperature removes magnetic, obtains median particle diameter and be 1.3 μm having amorphous carbon-coated silicon-carbon compound
Material.
Take 93 parts of above-mentioned Si-C composite material, 2 parts of conductive additive, 5 parts of binder, be homogenized, be coated under water-based system,
It dries, roll, obtain siliceous cathode pole piece.
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 0.4 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 816.2Wh/L, and constant current is filled
Entering ratio is 95.1%, and the capacity retention ratio after 200 charge and discharge cycles is 83.5%.
Embodiment 11
13g asphalt is taken, the n,N-Dimethylformamide of 1000g is added, stirs, mixed slurry is made.Weigh 74.8g
Copper sulphate is dissolved in 500g methanol, and copper-bath is added in above-mentioned slurry, weighs the crystalline substance that 1000g median particle diameter is 2 μm
Body silicon powder, stirring are uniformly mixed.Slurry is subjected to spray drying granulation, obtains the second particle that median particle diameter is 13 μm.It will spray
Dry powder after mist is dry heats 4 hours at 850 DEG C in argon inert atmosphere, so that asphalt is carbonized, after being carbonized
Second particle material.Above-mentioned second particle is mechanically pulverized, smashed material is obtained.Take above-mentioned broken rear material
800g crosses the asphalt 45.7g of 200 meshes, after ten minutes with VC mixing machine mechanical mixture, under the atmosphere of nitrogen protection,
Equipment is warming up to 300 DEG C while stirring, continues stirring 30 minutes, is then cooled to room temperature.By above-mentioned material in argon gas
In inert atmosphere, 2 hours are kept the temperature at 300 DEG C, 800 DEG C is then raised temperature to and is carbonized 4 hours, be sieved after cooled to room temperature,
Except magnetic, obtaining median particle diameter is 2.5 μm with amorphous carbon-coated Si-C composite material.
Take 88 parts of above-mentioned Si-C composite material, 6 parts of conductive additive, 6 parts of binder, be homogenized, be coated under water-based system,
It dries, roll, obtain siliceous cathode pole piece.
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 6.8 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 816.7Wh/L, and constant current is filled
Entering ratio is 94.6%, and the capacity retention ratio after 200 charge and discharge cycles is 84.2%.
Embodiment 12
167g sucrose is taken, 312g copper acetate is added in the deionized water of 2000g, and mixed solution is made in stirring.It weighs
The crystal silicon powder that 1000g median particle diameter is 3 μm, stirring are uniformly mixed.Slurry is subjected to spray drying granulation, obtains intermediate value grain
The second particle that diameter is 15 μm.By the dry powder after spray drying in argon inert atmosphere, is heated 4 hours at 600 DEG C, make sugarcane
Sugar charcoal, the second particle material after being carbonized.Above-mentioned second particle material progress air-flow is crushed, broken material is obtained
Material.Above-mentioned material 800g is taken, the asphalt 34.3g of 200 meshes was taken, after ten minutes with VC mixing machine mechanical mixture, in nitrogen
Under the atmosphere of gas shielded, equipment is warming up to 300 DEG C while stirring, continues stirring 30 minutes, is then cooled to room temperature.It will
Above-mentioned material keeps the temperature 2 hours at 300 DEG C in argon inert atmosphere, then raises temperature to 900 DEG C and is carbonized 2 hours, natural cooling
It is sieved after to room temperature, removes magnetic, obtaining median particle diameter is 3.8 μm with amorphous carbon-coated Si-C composite material.
Take 92 parts of above-mentioned Si-C composite material, 6 parts of conductive additive, 2 parts of binder, be homogenized, be coated under water-based system,
It dries, roll, obtain siliceous cathode pole piece.
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 2.5 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 824.7Wh/L, and constant current is filled
Entering ratio is 94.8%, and the capacity retention ratio after 200 charge and discharge cycles is 81.6%.
Comparative example 1:
Take the amorphous nano silica fume and 1500g ethyl alcohol that 1000g median particle diameter is 0.1 μm, 10g cetyl trimethyl bromine
Change ammonium, dispersion is sanded with the zirconium oxide bead of 0.3mm in sand mill, until obtaining the nano silicon particles that median particle diameter is 0.1 μm
Slurry.20g Ketjen black powder is added into slurry, continues to be sanded 30 minutes.250g sucrose is dissolved in 2250g deionized water to match
At aqueous sucrose solution.Aqueous sucrose solution pours into sand mill, is sufficiently mixed 30 minutes with nano silicon particles slurry.By what is be uniformly mixed
It is 10% that silicon particle/Ketjen black/sucrose dehydrated alcohol/water slurry, which is further diluted to solid content with deionized water, with laggard
Row spray drying treatment.The median particle diameter of obtained spherical second particle is about 28 μm.By the dry powder after spray drying in argon gas
It in inert atmosphere, is heated 2 hours at 700 DEG C, sucrose is made to be carbonized, obtain silicon particle/section's qin of amorphous carbon bonding and cladding
Black composite particles.Above-mentioned spherical composite pellets are all subjected to air-flow crushing processing, obtaining median particle diameter is 11 μm irregular
The composite particles of shape.Above-mentioned composite particles 530g, the asphalt 424g of 2000 mesh is taken to be divided with VC mixing machine mixed at high speed 10
Mechanical fusion machine is added, at 1500 rpm high speed fusion treatment 30 minutes in Zhong Hou, obtains silicon particle/section of asphalt cladding
Qin is black/amorphous carbon composite particles.By above-mentioned material in argon inert atmosphere, 2 hours are kept the temperature at 300 DEG C, is then heated up
It is carbonized 2 hours to 900 DEG C, sieving is crushed after cooled to room temperature, obtains the silicon particle with amorphous carbon coating layer/section's qin
Black/amorphous carbon composite particles.
80 parts of above-mentioned Si-C composite material is taken, 10 parts of conductive additive, 10 parts of binder, is homogenized, applies under water-based system
Cloth is dried, is rolled, and obtains siliceous cathode pole piece.
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 231.2 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 771.0Wh/L, and battery is permanent
It is 82.5% that stream, which is filled with the capacity retention ratio than being 91.6%, after 200 charge and discharge cycles,.
Fig. 5 is the XRD spectrum of Si-C composite material prepared by comparative example 1, as it can be seen that the silicon carbon material of synthesis from map
In, the appearance at no Cu-Si alloy peak.
Comparative example 2:
Si-C composite material is prepared according to mode substantially the same manner as Example 1, difference is: being not added during slurry material
Enter copper sulphate.Mode same as Example 1 makes battery.
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 104.9 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 789.3Wh/L, and battery is permanent
It is 80.3% that stream, which is filled with the capacity retention ratio than being 90.3%, after 200 charge and discharge cycles,.
Comparative example 3:
Si-C composite material is prepared according to mode substantially the same manner as Example 2, difference is: being not added during slurry material
Enter copper acetate.Mode same as Example 2 makes battery.
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 209.7 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 798.1Wh/L, and battery is permanent
It is 78.1% that stream, which is filled with the capacity retention ratio than being 90.9%, after 200 charge and discharge cycles,.
Comparative example 4:
Si-C composite material is prepared according to mode substantially the same manner as Example 3, difference is: being not added during slurry material
Enter copper acetate.Mode same as Example 3 makes battery.
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 280.9 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 813.9Wh/L, and battery is permanent
It is 77.8% that stream, which is filled with the capacity retention ratio than being 90.2%, after 200 charge and discharge cycles,.
Comparative example 5:
Si-C composite material is prepared according to mode substantially the same manner as Example 5, difference is: being not added during slurry material
Enter copper acetate.Mode same as Example 5 makes battery.
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 349.5 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 812.1Wh/L, and battery is permanent
It is 79.8% that stream, which is filled with the capacity retention ratio than being 90.7%, after 200 charge and discharge cycles,.
Comparative example 6:
Si-C composite material is prepared according to mode substantially the same manner as Example 7, difference is: during slurry, increased
Material fragmentation to median particle diameter is 0.08 μm by husky honed journey.Mode same as Example 7 makes battery.
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 33.9 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 803.0Wh/L, and battery is permanent
It is 79.2% that stream, which is filled with the capacity retention ratio than being 89.6%, after 200 charge and discharge cycles,.
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, any ripe
Professional and technical personnel is known, without departing from the scope of the present invention, according to the technical essence of the invention, to the above reality
Any simple modifications, equivalent substitutions and improvements etc. made by example are applied, it is fallen within the scope of protection of the technical scheme of the present invention
It is interior.
Claims (10)
1. a kind of Si-C composite material for lithium ion battery, it is characterised in that: the Si-C composite material contains Copper-cladding Aluminum Bar, institute
The Si-C composite material stated is to pass through the second particle being compounded to form by silicon materials, copper compound and carbon material using crushing-type
At Si-C composite material.
2. the Si-C composite material according to claim 1 for lithium ion battery, it is characterised in that: the silicon-carbon is multiple
Condensation material surface coats one layer of carbon.
3. the Si-C composite material according to claim 1 for lithium ion battery, it is characterised in that: the silicon materials
Median particle diameter is between 0.1~10 μm；The second particle median particle diameter is between 2~50 μm；The silicon-carbon composite wood
Expect median particle diameter between 0.2~15 μm.
4. the Si-C composite material according to claim 2 for lithium ion battery, it is characterised in that: the silicon-carbon is multiple
In condensation material, silicone content between 74~98%, copper content between 0.1~20%, carbon content is between 0.1~20%；Silicon
The carbon coating layer of carbon-carbon composite material surface is amorphous carbon or graphitized carbon.
5. the preparation method of the Si-C composite material described in claim 1 for lithium ion battery, it is characterised in that: including with
Lower step:
1) in a solvent by the first carbon matrix precursor and the dissolution of copper presoma, the two is mixed, mixed solution is made, silicon material is added
Material, and be uniformly mixed, obtain silicon/first carbon matrix precursor/copper presoma mixed slurry；
2) granulation is dried to the obtained mixed slurry of step 1), is then carried out at high warm under non-oxidizing atmosphere
Reason；
3) break process is carried out to step 2) products therefrom, obtains Si-C composite material；
4) step 3) products therefrom sieve and except magnetic, the Si-C composite material of the uncoated carbon in surface is made.
6. the preparation method of the Si-C composite material as claimed in claim 2 for lithium ion battery, which is characterized in that right
It is required that step 3) products therefrom carries out the following processing again in 5:
5) carbon coating is carried out using the second carbon matrix precursor to product obtained by step 3), is then carried out under non-oxidizing atmosphere high
Warm carbonization treatment；
6) step 5) products therefrom sieve and except magnetic, obtain carbon-coated Si-C composite material.
7. the preparation method of the Si-C composite material according to claim 5 for lithium ion battery, which is characterized in that
In step 2), the drying-granulating is carried out by the way of spray drying；
The high-temperature heat treatment is using any one in rotary furnace, roller kilns, pushed bat kiln, atmosphere batch-type furnace or tube furnace；
The temperature of the high-temperature heat treatment is 500-1100 DEG C, and soaking time is 0.5-72 hours；
The non-oxidizing atmosphere is provided by following at least one gases: nitrogen, argon gas, hydrogen or helium.
In step 3), the crumbling method uses air-flow crushing or mechanical crushing.
8. the preparation method of the Si-C composite material according to claim 6 for lithium ion battery, which is characterized in that
In step 5),
Second carbon matrix precursor coats, the equipment of carbonization can be completed at the same time using chemical vapour deposition reactor furnace；
The equipment of the second carbon matrix precursor cladding can also use mechanical fusion machine, VC mixing machine, high speed disperser, reaction kettle
In any one；
Second carbon matrix precursor is selected from coal tar pitch and petroleum asphalt, mesophase pitch, acetylene, ethylene, ethane, methane, polyethylene
One of alcohol, epoxy resin, polyacrylonitrile, polymethyl methacrylate or a variety of combinations；
The reaction temperature of the high temperature cabonization is 500~1100 DEG C；
The heating time of high temperature cabonization is 0.5~72 hour；
The non-oxidizing atmosphere is provided by following at least one gases: nitrogen, argon gas, hydrogen, helium, neon or Krypton.
9. a kind of negative electrode of lithium ion battery, it is characterised in that: containing the described in any item Si-C composite materials of claim 1-3,
In negative electrode of lithium ion battery, mass ratio shared by silicon-carbon cathode material is 80~96%；Also contain organic polymer in the cathode
Binder.
10. a kind of lithium ion battery, it is characterised in that: prepared using the negative electrode of lithium ion battery of claim 9.
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