CN110165187A - A kind of lithium ion battery silicon-carbon second particle material and preparation method thereof - Google Patents
A kind of lithium ion battery silicon-carbon second particle material and preparation method thereof Download PDFInfo
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- CN110165187A CN110165187A CN201910485939.4A CN201910485939A CN110165187A CN 110165187 A CN110165187 A CN 110165187A CN 201910485939 A CN201910485939 A CN 201910485939A CN 110165187 A CN110165187 A CN 110165187A
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- 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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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- 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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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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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- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of lithium ion battery silicon-carbon second particle materials and preparation method thereof, the Si-C composite material is the second particle adulterated containing copper, second particle is combined by silicon materials, conductive additive and carbon, inside second particle, carbonaceous conductive agent and the silicon primary particle for forming conductive network are evenly dispersed, and second particle can coat 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, and relatively low activation polarization effect has been obviously improved energy density, high rate performance and the cycle performance of lithium ion battery.Material preparation process of the present invention 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 lithium ion battery silicon-carbon second particle material 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 silicon materials
There are serious bulk effect during embedding de- lithium, volume change is about 400%, will cause electrode material dusting and electricity
Pole material is separated with collector.In addition, due to the bulk effect in charge and discharge process, the silicium cathode material that is exposed in electrolyte
Fresh surface is constantly formed, therefore consumes electrolyte persistently to generate SEI film, reduces the cycle performance of electrode material.Silicon substrate
The drawbacks described above of material seriously limits 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 the chemicals being related to is more dangerous and operating procedure is more multiple
It is miscellaneous.Si-C composite material synthesized by this method blends system in graphite, shows lower first effect and capacity, recycles simultaneously
It is 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 materials itself 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 by 0.01~5 μm primary particle carry out secondary granulation, then into
Row is broken, obtains the second particle of irregular shape, there is that conductive agent is evenly dispersed inside second particle, second particle surface cladding
One layer of amorphous carbon.Synthesized irregular second particle is applied in lithium ion battery, and cathode has compacted density high, secondary
The advantage that particle is non-breakable, pole piece interparticle contact point is more, polarization is lower.The second particle uses non-modified silicon
Synthesized by material, original silicon material resistivity is higher, and synthesized second particle electric conductivity is poor, thereby reduces the head of battery
Secondary efficiency causes the energy density of battery lower, and 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, for the low caused battery polarization of silicon intrinsic conductivity 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 object of the present invention is to provide a kind of lithium ion battery silicon-carbon second particle material and preparation method thereof, solve to make
It is higher for the silicon resistivity of semiconductor material, caused when applied to negative electrode of lithium ion battery battery polarization it is larger, circulation it is poor
Problem.
To solve the above problems, present invention provide the technical scheme that
A kind of lithium ion battery silicon-carbon second particle material, the Si-C composite material are secondary to adulterate containing copper
Particle, the second particle are combined by silicon materials, conductive additive and carbon, in the second particle, conduction addition
Agent is evenly dispersed with silicon materials.
Further, the second particle 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；Between 0.001~2 μm of thickness of the carbon coating layer.
Preferably, the median particle diameter of the silicon materials primary particle is between 1~8 μm；More preferably, the primary particle
Median particle diameter is between 2~7 μm；More preferably, the median particle diameter of the primary particle is between 3~8.
Preferably, the median particle diameter of the second particle is between 5~40 μm；More preferably, in the second particle
It is worth partial size between 10~30 μm.
In the second particle, silicone content between 74~98%, copper coin cellulose content between 0.1~20%, it is conductive
Additive level between 0.01~10%, carbon content is between 0.1~20%；Second particle coated with carbon bed is amorphous
Carbon or graphitized carbon.
The preparation method of the lithium ion battery silicon-carbon second particle material 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, conductive additive, dispersing agent, and be uniformly mixed, it is mixed to obtain silicon/first carbon matrix precursor/copper presoma/conductive additive
Close 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) step 2) products therefrom sieve and except magnetic, the compound second particle material of silicon-carbon of the uncoated carbon in surface is made
Material；The second particle that surface coats one layer of carbon is prepared, needs to follow the steps below processing again to step 2) products therefrom:
4) to product obtained by step 2) using the second carbon matrix precursor carry out carbon coating, then under non-oxidizing atmosphere into
The processing of row high temperature cabonization；
5) step 4) products therefrom sieve and except magnetic, obtain the compound second particle material of carbon-coated silicon-carbon.
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；
The conductive additive is Super P, Ketjen black, gas-phase growth of carbon fibre, acetylene black, electrically conductive graphite, carbon nanometer
One of pipe, graphene or a variety of combinations；
The dispersing agent is sodium tripolyphosphate, calgon, sodium pyrophosphate, cetyl trimethylammonium bromide, gathers
Acrylates, polyvinylpyrrolidone, polyoxyethylene sorbitan monooleate, alkylolamides, triethanolamine, phosphoric acid are pungent
One of rouge, lauryl sodium sulfate, neopelex, dodecylphosphoric acid methyl esters or a variety of combinations.
The dispersing agent can in the solvent effectively dispersed electro-conductive additive.The solvent can be formed with silicon
Uniform fluid, and dispersing agent and the first carbon matrix precursor can be completely dissolved, or formed with the first insoluble carbon matrix precursor
Even fluid.
By effectively stirring, dispersing, conductive additive uniform fold in each silicon primary particle surface and by its mutually
Connection, greatly improves the contact site between silicon particle, effectively reduces since the contact between silicon particle is bad and charge and discharge
Electricity caused by silicon particle dilation inactivates in electric process, and then has been obviously improved the cycle performance of battery.Simultaneously as leading
Electric additive it is evenly dispersed, further improve the conductivity inside second particle and between second particle, substantially reduce
The polarity effect of battery, improves the high rate performance of battery.
In step 2):
The drying-granulating technique 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 500-1100 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 or krypton
Gas.
In step 4):
The cladding of second carbon matrix precursor, carbonization technique can be completed at the same time using chemical vapour deposition reactor furnace；
The coating equipment of second carbon matrix precursor can also use mechanical fusion machine, VC mixing machine, reaction kettle, high speed
Any one progress in dispersion machine；
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 or krypton
Gas.
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 Si-C composite 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.
Si-C composite material provided by the invention is the second particle adulterated containing copper；Conduction inside second particle
Additive is evenly dispersed with silicon materials；The surface and inside of second particle can be coated with one layer of carbon or non-carbon coated.The present invention
Copper presoma is uniformly mixed with silicon materials, carbon matrix precursor, in high-temperature heat treatment, after carbon matrix precursor carbonization also by copper presoma
It originally is elemental copper, copper atom is spread into silicon materials, in conjunction with silicon atom, forms Cu-Si alloy, and the diffusion resistance of copper atom
Power is smaller, thus 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. the present invention uses the doping of metallic copper, Cu-Si alloy is formed with part silicon materials, greatly reduces composite material
Resistivity, be applied to lithium ion battery in, significantly reduce the internal resistance of battery, improve the coulombic efficiency for the first time of battery, into
And improve the high rate performance and energy density of battery；
2. silicon particle is fixed in the network or matrix of amorphous carbon, the network blocking of amorphous carbon electrolyte with
The contact on silicon particle surface reduces the formation of SEI to improve the coulombic efficiency of battery；Amorphous carbon network has simultaneously
Effect inhibits and the expansion of buffering silicon particle, and prevents silicon particle from gradually melting in charge and discharge process and at larger sized particle,
The failure for causing bigger expansion and part silicon materials, further improves the cycle performance of battery.
3. conductive additive uniform fold simultaneously connects silicon primary particle, the contact site between silicon particle is greatly improved, is had
Effect reduces since the contact between silicon particle is bad and silicon particle expands caused electricity inactivation, and then has been obviously improved electricity
The cycle performance in pond.Simultaneously as conductive additive is evenly dispersed, second particle inside and secondary are further improved
Conductivity between grain, greatly reduces the polarity effect of battery.
It is spherical or do not advise when making electrode 4. Si-C composite material prepared by the present invention is spherical or irregular shape
Then the second particle of shape is mutually inlayed, and the compacted density of electrode is greatly improved；Also, spherical or irregular second particle phase
Mutual contact enhancing, significantly reduces the contact internal resistance of electrode, and then improve the 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 Si-C composite material SEM photograph 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
The crystal silicon powder that value partial size is 3 μm, the single-walled carbon nanotube slurry that 50g 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 15 μm
Grain.By the dry powder after spray drying in argon inert atmosphere, is heated 10 hours at 600 DEG C, so that sucrose is carbonized, be carbonized
Second particle afterwards.Above-mentioned second particle 800g, coal tar pitch 114g are taken, is added in mechanical fusion machine, melts at a high speed at 1500 rpm
Processing 30 minutes is closed, the spherical silicon composite particles of coal tar pitch cladding are obtained.By above-mentioned material in argon inert atmosphere, 300
2 hours are kept the temperature at DEG C, 850 DEG C is then raised temperature to and is carbonized 3 hours, be sieved, obtained with amorphous carbon after cooled to room temperature
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 surface topography of Hitachi SU8010 type scanning electron microscope observation Si-C composite material.
Using the crystalline structure of Rigaku miniFlex600 type x-ray diffractometer test 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
Si-C composite material prepared by example 1 is second particle.
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
It applies Si-C composite material surface prepared by example 1 and apparent Cu-Si alloy occurs.
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, surface smoother, the distribution of no 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 30.2 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
Full battery is in capacity, average voltage and the capacity retention ratio data for recycling under 0.5C charge-discharge velocity 200 times under 0.2C.By
It is 93.9% that this constant current for the first time for obtaining full battery, which is filled with ratio, and volume energy density 817.2Wh/L, 200 charge and discharge follow
Capacity retention ratio after ring is 84.5%.
Embodiment 2
25g glucose is weighed, 156g copper sulphate is dissolved in 2000g ethyl alcohol, forms homogeneous solution.Take 1000g intermediate value grain
Diameter is 4.2 μm of crystal silicon powder, the single-walled carbon nanotube slurry that 25g solid content is 0.4%, 50g polyvinylpyrrolidone, and upper
It states slurry to be sufficiently stirred, be uniformly mixed.Slurry is subjected to spray drying granulation, obtains the second particle that median particle diameter is 26 μm.
By the dry powder after spray drying in argon inert atmosphere, is heated 6 hours at 700 DEG C, so that glucose is carbonized, after obtaining carbonization
Second particle.Above-mentioned second particle 800g is taken, the asphalt 50g of 200 meshes was taken, is divided with VC mixing machine mechanical mixture 10
Equipment is warming up to 300 DEG C while stirring under the atmosphere of nitrogen protection by Zhong Hou, continues stirring 30 minutes, then cooling
To room temperature.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, it is sieved after cooled to room temperature, obtains that there is 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 2.2 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 826.3Wh/L, and constant current is filled
Entering ratio is 94.2%, and the capacity retention ratio after 200 charge and discharge cycles is 82.1%.
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
Silicon carbide composite particles afterwards.
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 7.6 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 842.7Wh/L, and constant current is filled
Entering ratio is 94.3%, and the capacity retention ratio after 200 charge and discharge cycles is 81.8%.
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, and 400g solid content is
5% multi-walled carbon nanotube slurry, 50g polyvinylpyrrolidone are sufficiently stirred with above-mentioned slurry, are uniformly mixed.By slurry into
Row spray drying granulation obtains the second particle that median particle diameter is 30 μm.By the dry powder after spray drying in argon inert atmosphere
In, it is heated 6 hours at 500 DEG C, so that sodium carboxymethylcellulose is carbonized, the second particle after being carbonized.Take above-mentioned secondary
Grain 800g, crosses the asphalt 100g of 200 meshes, is added in mechanical fusion machine, high speed fusion treatment 30 is divided at 1500 rpm
Clock obtains the spherical silicon composite particles of coal tar pitch cladding.By above-mentioned material in argon inert atmosphere, it is small that 2 are kept the temperature at 300 DEG C
When, it then raises temperature to 1000 DEG C and is carbonized 2 hours, be sieved after cooled to room temperature, obtain that there is amorphous carbon-coated silicon-carbon
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 8.3 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 832.5Wh/L, and constant current is filled
Entering ratio is 94.1%, and the capacity retention ratio after 200 charge and discharge cycles is 82.5%.
Embodiment 5
167g sucrose is weighed, 74.8g copper sulphate is dissolved in 2000g methanol, forms homogeneous solution.Take 1000g intermediate value grain
Diameter is 5.2 μm of amorphous silicon powders, the single-walled carbon nanotube slurry that 50g solid content is 0.4%, 50g polyvinylpyrrolidone, and upper
It states slurry to be sufficiently stirred, be uniformly mixed.Slurry is subjected to spray drying granulation, obtains the second particle that median particle diameter is 35 μm.
By the dry powder after spray drying in argon inert atmosphere, is heated 2 hours at 600 DEG C, so that sucrose is carbonized, after being carbonized
Second particle.Above-mentioned composite material 1000g is taken, is added in CVD kiln, N is set2Flow velocity 25L/h, with 10 DEG C/min of rate
900 DEG C are warming up to, 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
Carbon-coated Si-C composite material is obtained after magnetic.
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 2.8 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 94.4%, and the capacity retention ratio after 200 charge and discharge cycles is 83.9%
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.Weigh the multi-wall carbon nano-tube that 500g solid content is 5%
Pipe slurry, 50g polyvinylpyrrolidone are sufficiently stirred with above-mentioned slurry, are uniformly mixed.Slurry is subjected to spray drying granulation,
Obtain the second particle that median particle diameter is 42 μm.By the dry powder after spray drying in argon inert atmosphere, heated at 900 DEG C
5 hours, asphalt is made to be carbonized, obtains Si-C composite material.
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 32.9 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 847.5Wh/L, and constant current is filled
Entering ratio is 93.8%, and the capacity retention ratio after 200 charge and discharge cycles is 80.9%.
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.50g gas-phase growth of carbon fibre is weighed, is sufficiently stirred with above-mentioned slurry, is mixed
It closes uniform.Slurry is subjected to spray drying granulation, obtains the second particle that median particle diameter is 25 μm.By the dry powder after spray drying
In argon inert atmosphere, is heated 4 hours at 800 DEG C, so that coal tar pitch is carbonized, the second particle after being carbonized.Take 800g
Second particle material, coal tar pitch 46g after ten minutes with VC mixing machine mechanical mixture under the atmosphere of nitrogen protection, are stirred on one side
Equipment is warming up to 300 DEG C on one side, continues stirring 30 minutes, is then cooled to room temperature.By above-mentioned material in argon inert atmosphere
In, 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, had after cooled to room temperature
Amorphous carbon-coated spherical 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 44.1 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 831.4Wh/L, and constant current is filled
Entering ratio is 93.2%, and the capacity retention ratio after 200 charge and discharge cycles is 84.0%.
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, stirring weigh the single-walled carbon nanotube that 250g solid content is 0.4%, 50g polyvinylpyrrolidine
Ketone is sufficiently stirred with above-mentioned slurry, is uniformly mixed.Slurry is subjected to spray drying granulation, obtains two that median particle diameter is 50 μm
Secondary particle.By the dry powder after spray drying in argon inert atmosphere, is heated 3 hours at 1000 DEG C, so that glucose is carbonized, obtain
To 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 2.8 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 855.4Wh/L, and constant current is filled
Entering ratio is 94.0%, and the capacity retention ratio after 200 charge and discharge cycles is 80.0%.
Embodiment 9
156g copper acetate is weighed, is dissolved in 1800g deionized water, taking 1000g median particle diameter is 7 μm of micro-crystal silicon
Powder, is added the Sodium Polyacrylate glue of 286g solid content 10%, and stirring, mixing weigh the multi wall carbon that 600g solid content is 5% and receive
Mitron is sufficiently stirred with above-mentioned slurry, is uniformly mixed.Slurry is subjected to spray drying granulation, obtaining median particle diameter is 18 μm
Second particle.By the dry powder after spray drying in argon inert atmosphere, is heated 2 hours at 600 DEG C, make Sodium Polyacrylate carbon
Change, obtains second particle material.Above-mentioned composite material 800g is taken, is added in CVD kiln, N is set2Flow velocity 25L/h, with 10 DEG C/
The rate of minute is warming up to 900 DEG C, is passed through C at this time2H2Gas, by N2And C2H2Flow velocity is adjusted to 20L/h, small in 900 DEG C of constant temperature 2
When.Obtain 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 2.1 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 814.2Wh/L, and constant current is filled
Entering ratio is 94.5%, and the capacity retention ratio after 200 charge and discharge cycles is 85.5%.
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, 30g vapor grown carbon
Fiber, 50g polyvinylpyrrolidone are sufficiently stirred with above-mentioned slurry, are uniformly mixed.Slurry is subjected to spray drying granulation, is obtained
The second particle for being 10 μm to median particle diameter.By the dry powder after spray drying in argon inert atmosphere, 2 are heated at 600 DEG C
Hour, so that sodium carboxymethylcellulose is carbonized, the second particle after being carbonized.Above-mentioned second particle 800g is taken, 200 meshes are crossed
Asphalt 34.3g is added in mechanical fusion machine, at 1500 rpm high speed fusion treatment 30 minutes, obtains coal tar pitch cladding
Spherical silicon composite particles.By above-mentioned material in argon inert atmosphere, 2 hours are kept the temperature at 300 DEG C, then raises temperature to 900 DEG C
Carbonization 2 hours, is sieved after cooled to room temperature, obtains having amorphous carbon-coated Si-C composite 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 0.5 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 818.1Wh/L, and constant current is filled
Entering ratio is 94.8%, and the capacity retention ratio after 200 charge and discharge cycles is 84.2%.
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.Weigh the single-walled carbon nanotube slurry that 125g solid content is 0.4%, 50g polyvinylpyrrolidine
Ketone is sufficiently stirred with above-mentioned slurry, is uniformly mixed.Slurry is subjected to spray drying granulation, obtains two that median particle diameter is 13 μm
Secondary particle.By the dry powder after spray drying in argon inert atmosphere, is heated 4 hours at 850 DEG C, asphalt is made to be carbonized,
Obtain Si-C composite material.Above-mentioned second particle 800g is taken, the asphalt 45.7g of 200 meshes was taken, it is mechanical with VC mixing machine
Equipment after ten minutes, under the atmosphere of nitrogen protection, is warming up to 300 DEG C while stirring by mixing, continues stirring 30 minutes,
It is then cooled to room temperature.By above-mentioned material in argon inert atmosphere, 2 hours are kept the temperature at 300 DEG C, then raises temperature to 800 DEG C
Carbonization 4 hours, is sieved after cooled to room temperature, obtains having 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 8.1 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 818.5Wh/L, and constant current is filled
Entering ratio is 94.1%, and the capacity retention ratio after 200 charge and discharge cycles is 84.9%.
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 amorphous silicon powders that 1000g median particle diameter is 6 μm, stirring are uniformly mixed.Weigh the single-walled carbon nanotube that 50g solid content is 0.4%
Slurry, 50g polyvinylpyrrolidone are sufficiently stirred with above-mentioned slurry, are uniformly mixed.Slurry is subjected to spray drying granulation, is obtained
The second particle for being 40 μm to median particle diameter.By the dry powder after spray drying in argon inert atmosphere, 4 are heated at 600 DEG C
Hour, so that sucrose is carbonized, obtains Si-C composite material.Above-mentioned second particle 800g is taken, the asphalt of 200 meshes was taken
Equipment after ten minutes with VC mixing machine mechanical mixture under the atmosphere of nitrogen protection, is warming up to by 34.3g while stirring
300 DEG C, continues stirring 30 minutes, be then cooled to room temperature.By above-mentioned material in argon inert atmosphere, 2 are kept the temperature at 300 DEG C
Hour, it then raises temperature to 900 DEG C and is carbonized 2 hours, be sieved after cooled to room temperature, obtain that there is amorphous carbon-coated silicon-carbon
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 3.0 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 826.6Wh/L, and constant current is filled
Entering ratio is 94.9%, and the capacity retention ratio after 200 charge and discharge cycles is 81.8%.
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 225.7 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 780.6Wh/L, and battery is permanent
It is 81.1% that stream, which is filled with the capacity retention ratio than being 91.6%, after 200 charge and discharge cycles,.
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 102.3 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 797.5Wh/L, and battery is permanent
It is 81.2% that stream, which is filled with the capacity retention ratio than being 90.2%, 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 204.7 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 806.4Wh/L, and battery is permanent
It is 78.9% that stream, which is filled with the capacity retention ratio than being 90.7%, 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 274.2 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 822.3Wh/L, and battery is permanent
It is 78.6% that stream, which is filled with the capacity retention ratio than being 90.0%, 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 341.1 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 820.5Wh/L, and battery is permanent
It is 80.6% that stream, which is filled with the capacity retention ratio than being 90.5%, 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
Husky honed journey, it is 0.08 μm that primary particle, which is crushed to median particle diameter, and second particle median particle diameter is 3.0 μm.With 7 phase of embodiment
Same mode makes battery.
Using four probe device test pole sheet resistivity of RTS-9 type, pole piece resistivity is 328.5 Ω cm.
Full battery appraisal procedure is with embodiment 1, and the volume energy density for measuring full battery reaches 811.3Wh/L, and battery is permanent
It is 80.0% that stream, which is filled with the capacity retention ratio than being 89.4%, 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 lithium ion battery silicon-carbon second particle material, it is characterised in that: the Si-C composite material is to contain copper
The second particle of doping, the second particle are combined by silicon materials, conductive additive and carbon, the second particle
In, conductive additive is evenly dispersed with silicon materials.
2. lithium ion battery according to claim 1 silicon-carbon second particle material, it is characterised in that: described secondary
Grain surface coats one layer of carbon.
3. lithium ion battery according to claim 2 silicon-carbon second particle material, 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 second particle table
Between 0.001~2 μm of thickness of face carbon coating layer.
4. lithium ion battery according to claim 2 silicon-carbon second particle material, it is characterised in that: described secondary
In grain, silicone content between 74~98%, copper coin cellulose content between 0.1~20%, conductive additive content 0.01~
Between 10%, carbon content is between 0.1~20%；Second particle material with carbon-coated surface layer is amorphous carbon or graphitized carbon.
5. the lithium ion battery described in claim 1 preparation method of silicon-carbon second particle material, 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, conductive additive, dispersing agent, and be uniformly mixed, obtain silicon/first carbon matrix precursor/copper presoma/conductive additive mixing
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) step 2) products therefrom sieve and except magnetic, the compound second particle material of silicon-carbon of the uncoated carbon in surface is made.
6. the lithium ion battery as claimed in claim 2 preparation method of silicon-carbon second particle material, it is characterised in that: to right
It is required that step 2) products therefrom carries out the following processing again in 5:
4) carbon coating is carried out using the second carbon matrix precursor to product obtained by step 2), is then carried out under non-oxidizing atmosphere high
Warm carbonization treatment；
5) step 4) products therefrom sieve and except magnetic, obtain the compound second particle material of carbon-coated silicon-carbon.
7. the lithium ion battery according to claim 5 preparation method of silicon-carbon second particle material, 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, helium, neon or Krypton.
8. the lithium ion battery according to claim 6 preparation method of silicon-carbon second particle material, which is characterized in that
In step 4),
Second carbon matrix precursor coats, the equipment of carbonization can use chemical vapour deposition reactor furnace；
The equipment of the second carbon matrix precursor cladding can also be using mechanical fusion machine, VC mixing machine, cladding kettle, high speed disperser
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 high-temperature heat treatment is using any one in rotary furnace, roller kilns, pushed bat kiln, atmosphere batch-type furnace or tube furnace；Institute
The reaction temperature for stating 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 1-4,
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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