CN106025218A - Preparation method of high surface density silicon carbon negative material and application thereof - Google Patents
Preparation method of high surface density silicon carbon negative material and application thereof Download PDFInfo
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- H—ELECTRICITY
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Abstract
The invention provides a preparation method of a high surface density silicon carbon negative material and application thereof. The silicon carbon negative material is prepared through simple and efficient production technology in large scale, wherein the silicon carbon negative material is of a compact spherical structure, and is low in specific surface area and high in tap density and surface density; and the production technology mainly comprises grinding, atomizing and sintering, and is easy for commercial large-scale production. The high surface density silicon carbon negative material is used for a lithium ion battery, the capacity of a silicon carbon negative pole can be effectively improved, the quality and volume of the silicon carbon negative pole piece occupied in the whole battery are reduced, and the energy density of the battery is improved.
Description
Technical field
The present invention relates to the preparation method of a kind of high areal density silicon-carbon cathode material and as lithium ion battery negative material
The application of material.
Background technology:
Lithium ion battery has been widely used in electric automobile and portable electric appts, along with the development of society,
People are more and more higher to the energy density demand of battery, and current business-like lithium ion battery carbons negative material can not be expired
The demand of foot lithium ion battery with high energy density, therefore developing new negative material is that the urgent of lithium ion battery industry development is essential
Ask.Silicon class negative material has high specific capacity and suitable removal lithium embedded current potential it is considered to be there is most prospect to substitute carbons material
The negative material of application in lithium ion battery.But there is asking of serious volumetric expansion and poorly conductive in silicon class negative material
Topic, needs by reserved volumetric expansion space and reduces surface density raising chemical property.Under high areal density, silicon class negative pole material
Material is easy to produce the efflorescence of material and come off, and causes battery capacity fast decay.
Material with carbon element has the electric conductivity of excellence, and is possible to prevent the reunion of nano-silicon, the volumetric expansion of simultaneous buffering silicon,
Therefore silicon-carbon cathode material has broad application prospects in field of lithium ion battery.But most of silicon-carbon of report is born at present
Pole material is loose porous class material, and the space that loose structure needs by providing silicon to expand maintains the shape of electrode material
Looks.But in order to improve the energy density of battery, i.e. needing to improve the capacity of negative material, the face improving electrode slice again is close
Degree, but porous silicon material with carbon element tap density is relatively low, and under same surface density, electrode slice is the thickest, causes battery performance poor.
Summary of the invention
The invention provides a kind of high areal density silicon-carbon cathode material, solve silicon-carbon cathode material and use at high areal density
Under the conditions of, the defect that electrode slice is thicker, chemical property is poor.Provide a kind of technique simple, commercially viable large-scale production
The preparation method and applications of high areal density silicon-carbon cathode material.
The invention provides a kind of high areal density silicon-carbon cathode material, wherein silicone content is 3%-40%, preferably 5%-
20%；Carbon content is 60%-97%, preferably 80%-95%；Tap density is 0.46-1.2g/cm3, preferably 0.8-1.1g/
cm3, most preferably 0.85-1.0g/cm3, surface density is 5-30mg/cm2, preferably 10-25mg/cm2, specific surface area is 5-50m2/ g,
Preferably 5-15m2/ g, wherein carbon is presented in pyrolytic carbon, graphite and conductive carbon, and the content of pyrolytic carbon is 3%-20%, stone
The content of ink is 50%-90%, and conductive carbon content is 3%-15%.
High areal density silicon-carbon cathode material provided by the present invention prepares in accordance with the following steps:
1) being dispersed in the aqueous solution containing additive by micron order silica flour, the mean diameter of micron order silica flour is 0.5-10
μm, preferably 1 μm-5 μm, described additive is selected from high molecular polymer, or selected from containing aldehyde radical or the Organic substance of carboxyl and/or gold
Belong to organic compound, carry out wet ball grinding, obtain homodisperse slurry, in ball mill, then add conductive carbon additive,
Continue ball milling, make silica flour, conductive carbon additive dispersed in the solution；
2) ball mill control device frequency is turned down, preferably to below 50Hz, or preferably 10-40Hz, more preferably 20-
30Hz, add graphite with following group in the combination of additive, described in be combined as: high molecular polymer, containing aldehyde radical or carboxyl
The combination of the two or more compositions in organic compound, metallo-organic compound, ball milling at the low rotational speed, it is uniformly mixed
Slurry, the solid content of gained slurry is 10%-40%；Preferably, described silica flour and graphite ratio are 1:3-15 scale and the most excellent
Choosing, described silica flour is 1:2-6 with the weight ratio of described additive combination.
3) by step 2) after the spray-dried machine of slurry of gained shapes, it is sintered under non-oxidizing atmosphere, obtains
Fine and close spherical Si-C composite material.
Step 1) described high molecular polymer additive is selected from comprising but is not limited only to one or more in following substances:
Sodium carboxymethyl cellulose, hydroxypropyl cellulose, phenolic resin, sodium alginate, gelatin, starch, polyaniline, polythiophene, polyethylene
Ketopyrrolidine, polyacrylonitrile；Organic compound containing aldehyde radical or carboxyl is selected from the one comprised but be not limited only in following substances
Or multiple: glucose, sucrose, citric acid, Colophonium, chitosan；Metallo-organic compound is selected from including but not limited to following substances
In a kind of movable multiple: aluminum isopropylate., trialkylaluminium, dialkylaluminum chloride；Preferably high molecular polymer and containing aldehyde radical or carboxylic
The organic compound of base uses simultaneously, more preferably glucose and the combination of polyvinylpyrrolidone；Solvent used by wet ball grinding
One or more in following solvents: water, ethanol, acetone, ethyl acetate, sodium alginate soln, preferably sodium alginate are molten
Liquid；Conductive carbon additive is selected from comprising but is not limited only to one or more in following substances: Graphene, CNT,
Super-P, Ketjen black, white carbon black, acetylene black, the preferably combination of Graphene, CNT and Super-P.
Step 2) in the mean diameter of graphite be the one or many between 1 μm-20 μm, preferably mean diameter 1 μm-10 μm
Plant crystalline flake graphite；Described high molecular polymer is not limited only to one or more in following substances selected from comprising: phenolic aldehyde tree
Fat, epoxy resin, sodium carboxymethyl cellulose, hydroxypropyl cellulose, polyvinylpyrrolidone, polyacrylonitrile, starch, polyaniline,
Polythiophene, polyacrylamide；The described organic compound containing aldehyde radical or carboxyl is not limited only to following substances selected from comprising
In one or more: glucose, sucrose, chitosan, citric acid, Colophonium, citric acid, sodium alginate, gelatin；Organometallic
Compound is selected from multiple including but not limited to a kind of activity in following substances: aluminum isopropylate., trialkylaluminium, dialkylaluminum chloride；
Preferably high molecular polymer and the organic compound containing aldehyde radical or carboxyl uses simultaneously, more preferably glucose and polyvinylpyrrolidine
The combination of ketone.Preferably, step 1) identical with the additive in step 2；It is further preferred that step 1) and step 2) in additive be all
Glucose and the combination of polyvinylpyrrolidone.
Step 3) in spray dryer be enclosed spray dryer or open type spray dryer, spray dryer air inlet
Temperature is 160-350 DEG C, and discharging opening temperature is 80 DEG C-130 DEG C；Nebulizer is centrifugal type atomizer or the atomization of two fluid-types
Device, charging rate is 20-60r/min；Described sintering temperature is 600-1100 DEG C, and programming rate is 1-20 DEG C/min, is preferably
5-10℃/min；Sintering time is 1-10h, preferably 3-6h；Described non-oxidizing atmosphere one in following: nitrogen
Gas, argon；The tap density of fine and close spherical Si-C composite material is 0.6-1.2g/cm3, specific surface area is 5-50m2/g。
Wherein step 3) in the rotating speed of centrifugal type atomizer be 25000-35000r/min, two fluid-type nebulizer air inlets speed
Gas needed for spending for 4-10L/min, spray dryer is following middle one: air, nitrogen, argon.
Another object of the present invention provides the application of described high areal density silicon-carbon cathode material.
Application provided by the present invention is the application as lithium ion battery negative material of the high areal density silicon-carbon cathode material.
Compared with prior art, the silicon-carbon cathode material that the present invention provides has low specific surface area, high tap density,
Solve silicon-carbon cathode material defect of cyclical stability difference under high areal density.And preparation method simple and practicalization degree
Height, the reversible capacity of the silicon-carbon cathode material of extensive preparation is 400-700mAh/g, is better than current commercialization graphite type material
Theoretical specific capacity.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of the high areal density silicon carbon material obtained by embodiment 1.
Fig. 2 is the high areal density silicon carbon material electrode slice (10mg/cm obtained by embodiment 12), close at 100mA/g electric current
Under degree, the volume change of 100 circulations of discharging.
Detailed description of the invention
Being further described the present invention below in conjunction with specific embodiment, the present invention is not limited to following case study on implementation.
Test method described in following embodiment, if no special instructions, is conventional method；Described reagent and material, as
Without specified otherwise, all can obtain from commercial channels.
Embodiment 1
By silica flour that mean diameter is 1 μm with glucose, polyvinylpyrrolidone (weight ratio is 1:1:1) in aqueous
Carrying out wet ball grinding, the frequency of ball mill is 50Hz, after grinding 5h, is added thereto to conductive carbon additive Graphene, carbon nanometer
Pipe, Super P (weight ratio is 3:3:4), continue wet ball grinding 1h, obtain homodisperse slurry；After by ball mill frequency drop
Low for 20Hz, and it is added thereto to crystalline flake graphite, glucose, polyvinylpyrrolidone (weight ratio is 8:1:1), after ball milling 1h
Slurry to mix homogeneously.Being shaped through open type spray dryer by the slurry obtained, the nebulizer of spray dryer is two fluids
Nebulizer, gas used is air, and air inlet temperature is 220 DEG C, and air outlet temperature is 110 DEG C, and air velocity is 8L/min,
Charging rate is 35r/min.By the material that obtains at 800 DEG C, sintering 4h in argon gas atmosphere, programming rate is 5 DEG C/min.
Scanning electron microscope (JEOL-6700F) test above-mentioned under the conditions of the high areal density silicon-carbon cathode material that obtains
Pattern, by the specific surface area of BET method test material, the tap density of material, the thickness of electrode slice, surface density test result are shown in
Table 1, with thermogravimetric method test material in carbon and the content of silicon, the carbon in described high areal density silicon-carbon cathode material with cracking carbon,
Graphite, conductive carbon form exist, and it is 91% that carbon content accounts for the percentage by weight of final silicon-carbon cathode material, and wherein pyrolytic carbon accounts for
11%, graphite accounts for 71%, and conductive carbon accounts for 9%；Silica flour is uniformly dispersed in the inside of material, and silicone content accounts for final silicon-carbon cathode material
The 9% of material.
The Electrochemical Characterization of high areal density silicon-carbon cathode material:
By the silicon-carbon cathode material prepared in embodiment 1, Super-P, CMC and SBR with mass ratio 90:2:4:4's
Mass ratio, pulls an oar in aqueous, the slurry being uniformly mixed, after slurry is coated onto in copper foil current collector equably, 60
Vacuum drying oven dries at DEG C 8h, obtains the electrode slice of high areal density.Using metal lithium sheet as positive pole, microporous polypropylene membrane
(Celgard2500) as barrier film, 1mol/L LiPF6 (solvent be volume ratio be the ethylene carbonate of 1:1:1, dimethyl carbonate
With diethyl carbonate mixed liquor) as electrolyte, the glove box of argon shield is assembled into button cell, carry out constant current charge and discharge
Electrical testing, electric current density is 100mA/g, and charging/discharging voltage interval is 0.005-1.0V, and cell testing results is listed in table 1.
Embodiment 2
The silica flour that mean diameter is 2 μm is carried out wet with glucose, polyacrylonitrile (weight ratio is 1:2:2) in aqueous
Method ball milling, the frequency of ball mill is 70Hz, after grinding 5h, is added thereto to CNT, Graphene (weight ratio is 1:1), continues
Continuous wet ball grinding 1h, obtains homodisperse slurry；After ball mill frequency is reduced to 25Hz, and spherical graphite, Portugal wherein
Grape sugar, polyacrylonitrile (weight ratio is 5:1:2), the slurry being uniformly mixed after ball milling 1h；The slurry obtained is sprayed through open type
Mist drying machine shapes, and the nebulizer of spray dryer is twin fluid atomization device, and gas used is air, and air inlet temperature is
220 DEG C, air outlet temperature is 110 DEG C, and air velocity is 8L/min, and charging rate is 35r/min.By the material that obtains 800
At DEG C, sintering 4h in argon gas atmosphere, programming rate is 5 DEG C/min.
Method of testing is same as in Example 1, and the carbon in described high areal density silicon-carbon cathode material is to crack carbon, graphite, to lead
Electrical carbon form exists, and it is 89% that carbon content accounts for the percentage by weight of final silicon-carbon cathode material, and wherein pyrolytic carbon accounts for 13%, graphite
Accounting for 68%, conductive carbon accounts for 8%；Silica flour is uniformly dispersed in the inside of material, and silicone content accounts for the 11% of final silicon-carbon cathode material；
Other test result is listed in table 1.
Embodiment 3
The silica flour that mean diameter is 3 μm is carried out wet method in aqueous with sucrose, phenolic resin (weight ratio is 2:3:3)
Ball milling, the frequency of ball mill is 70Hz, after grinding 6h, is added thereto to Graphene, Super P (weight ratio is 2:3), continues wet
Method ball milling 1h, obtains homodisperse slurry；After ball mill frequency is reduced to 30Hz, and crystalline flake graphite, isopropanol wherein
Aluminum, glucose (weight ratio is 10:1:1), the slurry being uniformly mixed after ball milling 1h；By the slurry that obtains through open type spray dried
Dry machine shapes, and the nebulizer of spray dryer is twin fluid atomization device, and gas used is air, and air inlet temperature is 220 DEG C,
Air outlet temperature is 110 DEG C, and air velocity is 7L/min, and charging rate is 30r/min.By the material that obtains at 800 DEG C, argon
Sintering 4h in gas atmosphere, programming rate is 5 DEG C/min.
Method of testing is same as in Example 1, and the carbon in described high areal density silicon-carbon cathode material is to crack carbon, graphite, to lead
Electrical carbon form exists, and it is 87% that carbon content accounts for the percentage by weight of final silicon-carbon cathode material, and wherein pyrolytic carbon accounts for 15%, graphite
Accounting for 67%, conductive carbon accounts for 5%；Silica flour is uniformly dispersed in the inside of material, and silicone content accounts for the 13% of final silicon-carbon cathode material；
Other test result is listed in table 1.
Embodiment 4
The silica flour that mean diameter is 4 μm is carried out wet with glucose, polyacrylonitrile (weight ratio is 1:3:3) in aqueous
Method ball milling, the frequency of ball mill is 70Hz, after grinding 6h, is added thereto to Super P, continues wet ball grinding 1h, obtains uniformly
Scattered slurry；After ball mill frequency is reduced to 25Hz, and wherein spherical graphite, phenolic resin, sucrose (weight ratio is 9:
1:1), the slurry being uniformly mixed after ball milling 1h；The slurry obtained is shaped through open type spray dryer, spray dryer
Nebulizer is twin fluid atomization device, and gas used is air, and air inlet temperature is 220 DEG C, and air outlet temperature is 110 DEG C, gas
Flow Velocity is 8L/min, and charging rate is 35r/min.By the material that obtains at 800 DEG C, argon gas atmosphere sinters 4h, heats up
Speed is 5 DEG C/min.
Method of testing is same as in Example 1, and the carbon in described high areal density silicon-carbon cathode material is to crack carbon, graphite, to lead
Electrical carbon form exists, and it is 85% that carbon content accounts for the percentage by weight of final silicon-carbon cathode material, and wherein pyrolytic carbon accounts for 18%, graphite
Accounting for 55%, conductive carbon accounts for 12%；Silica flour is uniformly dispersed in the inside of material, and silicone content accounts for final silicon-carbon cathode material
15%；Other test result is listed in table 1.
Embodiment 5
The silica flour that mean diameter is 1 μm is carried out wet with polyacrylonitrile, citric acid (weight ratio is 1:1:1) in aqueous
Method ball milling, the frequency of ball mill is 70Hz, after grinding 6h, is added thereto to CNT, Super P (weight ratio is 1:2), continues
Continuous wet ball grinding 1h, obtains homodisperse slurry；After ball mill frequency is reduced to 20Hz, and crystalline flake graphite, drip wherein
Blue or green, citric acid (weight ratio is 9:1:1), the slurry being uniformly mixed after ball milling 1h；By the slurry that obtains through open type spray dried
Dry machine shapes, and the nebulizer of spray dryer is twin fluid atomization device, and gas used is air, and air inlet temperature is 220 DEG C,
Air outlet temperature is 110 DEG C, and air velocity is 8L/min, and charging rate is 35r/min.By the material that obtains at 800 DEG C, argon
Sintering 4h in gas atmosphere, programming rate is 5 DEG C/min.
Method of testing is same as in Example 1, and the carbon in described high areal density silicon-carbon cathode material is to crack carbon, graphite, to lead
Electrical carbon form exists, and it is 93% that carbon content accounts for the percentage by weight of final silicon-carbon cathode material, and wherein pyrolytic carbon accounts for 9%, graphite
Accounting for 79%, conductive carbon accounts for 7%；Silica flour is uniformly dispersed in the inside of material, and silicone content accounts for the 7% of final silicon-carbon cathode material；
Other test result is listed in table 1.
Embodiment 6
The silica flour that mean diameter is 3 μm is entered in aqueous with polyvinylpyrrolidone, sucrose (weight ratio is 1:1:1)
Row wet ball grinding, the frequency of ball mill is 65Hz, grinds after 6h, be added thereto to CNT, Super P (weight ratio is 1:
1), continue wet ball grinding 1h, obtain homodisperse slurry；After ball mill frequency is reduced to 20Hz, and scale stone wherein
Ink, Colophonium, phenolic resin (weight ratio is 10:1:1), the slurry being uniformly mixed after ball milling 1h；By the slurry obtained through opening
Formula spray dryer shapes, and the nebulizer of spray dryer is twin fluid atomization device, and gas used is air, air inlet temperature
Being 220 DEG C, air outlet temperature is 110 DEG C, and air velocity is 6L/min, and charging rate is 30r/min.The material obtained is existed
At 800 DEG C, sintering 4h in argon gas atmosphere, programming rate is 5 DEG C/min.
Method of testing is same as in Example 1, and the carbon in described high areal density silicon-carbon cathode material is to crack carbon, graphite, to lead
Electrical carbon form exists, and it is 95% that carbon content accounts for the percentage by weight of final silicon-carbon cathode material, and wherein pyrolytic carbon accounts for 7%, graphite
Accounting for 83%, conductive carbon accounts for 5%；Silica flour is uniformly dispersed in the inside of material, and silicone content accounts for the 5% of final silicon-carbon cathode material；
Other test result is listed in table 1.
Embodiment 7
Other conditions are same as in Example 1, and the additive that difference adds after being wet ball grinding is not " glucose
And polyvinylpyrrolidone ", but " phenolic resin and polyacrylonitrile ".
Embodiment 8
Other conditions are same as in Example 1, and the additive that difference adds after being wet ball grinding is not " glucose
And polyvinylpyrrolidone ", but " phenolic resin and glucose ".
Embodiment 9
Other conditions are same as in Example 2, and the additive that difference adds after being wet ball grinding is not " glucose
And polyacrylonitrile ", but " phenolic resin and sucrose ".
Embodiment 10
Other conditions are same as in Example 2, and the additive that difference adds after being wet ball grinding is not " glucose
And polyacrylonitrile ", but " phenolic resin and Colophonium ".
Comparative example 1
The silica flour that mean diameter is 1 μm is carried out wet ball grinding in aqueous, and the frequency of ball mill is 65Hz, grinds 6h
After, it is added thereto to CNT, Graphene, Super P (weight ratio is 3:3:4), continues wet ball grinding 1h, uniformly divided
The slurry dissipated；After ball mill frequency is reduced to 20Hz, and crystalline flake graphite wherein, the slurry being uniformly mixed after ball milling 1h
Material；Being shaped through open type spray dryer by the slurry obtained, the nebulizer of spray dryer is twin fluid atomization device, gas used
Body is air, and air inlet temperature is 220 DEG C, and air outlet temperature is 110 DEG C, and air velocity is 6L/min, and charging rate is 30r/
min.By the material that obtains at 800 DEG C, sintering 4h in argon gas atmosphere, programming rate is 5 DEG C/min.
Method of testing is same as in Example 1, and the carbon in described high areal density silicon-carbon cathode material is with graphite, conductive carbon form
Existing, it is 91% that carbon content accounts for the percentage by weight of final silicon-carbon cathode material, and graphite accounts for 81%, and conductive carbon accounts for 10%；Silica flour
Being uniformly dispersed in the inside of material, silicone content accounts for the 9% of final silicon-carbon cathode material；Other test result is listed in table 1.
Comparative example 2
The silica flour that mean diameter is 2 μm is carried out wet with glucose, polyacrylonitrile (weight ratio is 1:2:2) in aqueous
Method ball milling, the frequency of ball mill is 70Hz, after grinding 5h, obtains homodisperse slurry；After ball mill frequency is reduced to
25Hz, and it is added thereto to spherical graphite), the slurry being uniformly mixed after ball milling 1h；The slurry obtained is sprayed through open type
Drying machine shapes, and the nebulizer of spray dryer is twin fluid atomization device, and gas used is air, and air inlet temperature is 220
DEG C, air outlet temperature is 110 DEG C, and air velocity is 8L/min, and charging rate is 35r/min.By the material that obtains at 800 DEG C
Under, argon gas atmosphere sinters 4h, programming rate is 5 DEG C/min.
Method of testing is same as in Example 1, and the carbon in described high areal density silicon-carbon cathode material is to crack carbon, graphite, to lead
Electrical carbon form exists, and it is 89% that carbon content accounts for the percentage by weight of final silicon-carbon cathode material, and wherein cracking carbon accounts for 16%, graphite
Account for 73%；Silica flour is uniformly dispersed in the inside of material, and silicone content accounts for the 11% of final silicon-carbon cathode material；Other test result
It is listed in table 1.
Claims (8)
1. a high areal density silicon-carbon cathode material, wherein silicone content is 3%-40%, preferably 5%-20%；Carbon content is
60%-97%, preferably 80%-95%；Tap density is 0.6-1.2g/cm3, preferably 0.8-1.1g/cm3, most preferably 0.85-
1.0g/cm3, surface density is 5-40mg/cm2, preferably 10-30mg/cm2, more preferably 10-25mg/cm2, specific surface area is 5-
50m2/ g, preferably 5-15m2/ g, wherein carbon is presented in pyrolytic carbon, graphite and conductive carbon, and the content of pyrolytic carbon is 3%-
20%, the content of graphite is 50%-90%, and conductive carbon content is 3%-15%.
The preparation method of silicon-carbon cathode material the most according to claim 1, it is characterised in that specifically comprise the following steps that
1) being dispersed in the aqueous solution containing additive by micron order silica flour, the mean diameter of micron order silica flour is 0.5-10 μm,
Being preferably 1 μm-5 μm, described additive is selected from high molecular polymer, or selected from containing aldehyde radical or the Organic substance of carboxyl and/or metal
Organic compound, carries out wet ball grinding, obtains homodisperse slurry, then adds conductive carbon additive in ball mill, continue
Continuous ball milling, makes silica flour, conductive carbon additive dispersed in the solution；
2) ball mill control device frequency is turned down, preferably to below 50Hz, or preferably 10-40Hz, more preferably 20-30Hz, add
Enter graphite with following group in the combination of additive, described in be combined as: high molecular polymer, organic compound containing aldehyde radical or carboxyl
The combination of the two or more compositions in thing, metallo-organic compound, ball milling at the low rotational speed, the slurry being uniformly mixed, institute
The solid content obtaining slurry is 10%-40%；
3) by step 2) after the spray-dried machine of slurry of gained shapes, it is sintered under non-oxidizing atmosphere, obtains densification
Spherical Si-C composite material.
Preparation method the most according to claim 2, it is characterised in that step 1) described high molecular polymer additive is selected from
Comprise but be not limited only to one or more in following substances: sodium carboxymethyl cellulose, hydroxypropyl cellulose, phenolic resin, sea
Sodium alginate, gelatin, starch, polyaniline, polythiophene, polyvinylpyrrolidone, polyacrylonitrile；Containing aldehyde radical or the organic compound of carboxyl
Thing is not limited only to one or more in following substances selected from comprising: glucose, sucrose, citric acid, Colophonium, chitosan；Gold
Belong to organic compound selected from multiple including but not limited to a kind of activity in following substances: aluminum isopropylate., trialkylaluminium, dialkyl group
Aluminum chloride；Preferably high molecular polymer and the organic compound containing aldehyde radical or carboxyl uses simultaneously, more preferably glucose and poly-second
The combination of alkene pyrrolidone；One or more in following solvents of solvent used by wet ball grinding: water, ethanol, acetone, vinegar
Acetoacetic ester, sodium alginate soln, preferably sodium alginate soln；Conductive carbon additive is not limited only to following substances selected from comprising
In one or more: Graphene, CNT, Super-P, Ketjen black, white carbon black, acetylene black, preferably Graphene, CNT
Combination with Super-P.
4. according to the method described in any one of claim 2-3, it is characterised in that step 2) in the mean diameter of graphite be 1 μm-
One or more crystalline flake graphites between 20 μm, preferably mean diameter 1 μm-10 μm；Described high molecular polymer is selected from comprising
But it is not limited only to one or more in following substances: phenolic resin, epoxy resin, sodium carboxymethyl cellulose, hydroxypropyl are fine
Dimension element, polyvinylpyrrolidone, polyacrylonitrile, starch, polyaniline, polythiophene, polyacrylamide；Described containing aldehyde radical or carboxyl
Organic compound selected from comprising but be not limited only to one or more in following substances: glucose, sucrose, chitosan, lemon
Lemon acid, Colophonium, citric acid, sodium alginate, gelatin；Metallo-organic compound is selected from including but not limited to the one in following substances
Movable multiple: aluminum isopropylate., trialkylaluminium, dialkylaluminum chloride；Preferably high molecular polymer and organic containing aldehyde radical or carboxyl
Compound uses simultaneously, more preferably glucose and the combination of polyvinylpyrrolidone；Preferably, step 1) and step 2 in interpolation
Agent is identical；It is further preferred that step 1) and step 2) in additive be all the combination of glucose and polyvinylpyrrolidone.
5. according to the preparation method described in any one of claim 2-4, it is characterised in that step 3) in spray dryer for closing
Formula spray dryer or open type spray dryer, spray dryer air inlet temperature is 160-350 DEG C, and discharging opening temperature is 80
℃-130℃；Nebulizer is centrifugal type atomizer or two fluid-type nebulizers, and charging rate is 20-60r/min；Described sintering
Temperature is 600-1100 DEG C, and programming rate is 1-20 DEG C/min, preferably 5-10 DEG C/min；Sintering time is 1-10h, is preferably
3-6h；Described non-oxidizing atmosphere one in following: nitrogen, argon；Shaking of fine and close spherical Si-C composite material
Real density is 0.6-1.2g/cm3, specific surface area is 5-50m2/g。
Method the most according to claim 5, the rotating speed of centrifugal type atomizer is 25000-35000r/min, two fluid-type mists
Changing the gas needed for device intake velocity is 4-10L/min, spray dryer is following middle one: air, nitrogen, argon.
7. the high areal density silicon-carbon cathode material prepared according to described method arbitrary in claim 2-6, described negative pole material
Material, silicone content is 3%-40%, and carbon content is 60%-97%, and tap density is 0.4-1.2g/cm3, surface density is 5-30mg/
cm2, specific surface area is 5-50m2/g。
8. require that described in 7, high areal density silicon-carbon cathode material is as the application of lithium ion battery negative material according to profit.
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