CN108539186A - A kind of high-volume silicon-carbon negative electrode material and its preparation method and application - Google Patents
A kind of high-volume silicon-carbon negative electrode material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of high-volume silicon-carbon negative electrode materials and its preparation method and application, utilize ball milling, surfactant, the modes such as ultrasound and spray drying simultaneously optimize relevant technological parameter and carry out effective dispersion and compound to nano-silicon and carbon material, it is prepared with the Si-C composite material that height ratio capacity is 1000~1700mAh/g and long circulation life, present invention process is simple, it is of low cost, easily realize the technology path of industrialized production, utilize ball milling, surfactant, the modes such as ultrasound and spray drying simultaneously optimize relevant technological parameter and carry out effective dispersion and compound to nano-silicon and carbon material, the Si-C composite material with height ratio capacity and cycle performance is prepared.
Description
Technical field
The invention belongs to secondary battery technologies, and in particular to a kind of high-volume silicon-carbon negative electrode material and preparation method thereof
And application.
Background technology
In recent years, with the fast development and extensive use of various 3C electronic products and electric vehicle, people are to electricity
The increasingly raising that pond energy density requires, the material system of current battery cannot gradually meet high-energy density requirement.Just
For negative material, the theoretical capacity of widely commercialized graphite negative electrodes material is only 372mAh/g, can no longer meet lithium
Ion battery light weight, the demand for development of miniature, long continuation of the journey.Silicon materials are with the theoretical specific capacity that it is more than 10 times of graphite
(4200mAh/g, Li22Si5), wide and at low cost etc. the advantages in source become the emphasis and hot spot researched and developed at present.
But in Si to Li14Si5、Li22Si5During Deng transformation, along with big volume expansion (up to 300%),
Silicon particle rupture or dusting are easily caused, loses and contacts with electrode, the chemical property rapid deterioration of cathode, this seriously constrains silicon
The Industrialization of negative material.In order to inhibit and alleviate the volume expansion of silicium cathode, mainly have by the nanosizing of silicon, structure
There is the Si-C composite material of micro-nano structure to be improved.In Si-C composite material, carbon material can inhibit the reunion of nano-silicon
With the volume expansion of buffering silicon；The good electrical conductance of carbon material can effectively improve the electrical contact after silicon volume expansion simultaneously, from
And effectively improve the chemical property of material.High power capacity silicon carbon material (>In 700mAh/g), with increasing for silicone content,
The fine dispersion for how effectively realizing silicon nanoparticle reduces the absolute value of volume expansion, becomes raising high-specific-capacity silicon carbon
The most important thing of material circulation performance.
There are complex process, expensive and the problems such as be difficult to realize industrialized production for current most of technology paths.Such as
Patent CN20130307450.0 reports a kind of preparation method of nanometer silicon/graphene lithium ion battery cathode material, wherein relating to
And the preparation of graphene oxide glue sample solution, the process need to graphene oxide suspension be centrifuged repeatedly washing (until
Solution ph is neutrality), the process yield is low and expends great lot of water resources and time, is difficult to realize high power capacity silicon carbon material
Prepare with scale；Patent CN201510027926.4 then prepares nano silicon composite cathode material, mesh using chemical vapour deposition technique
Preceding chemical vapour deposition technique is also difficult to realize uniform deposition of the nano-silicon on graphite, and product homogeneity is poor and there are low outputs etc.
Problem.
Invention content
In view of the above-mentioned deficiencies in the prior art, the technical problem to be solved by the present invention is that providing a kind of high power capacity silicon
Carbon negative pole material and its preparation method and application, develops that a kind of nano-silicon is well dispersed, high power capacity of excellent electrochemical performance
The synthetic method of silicon-carbon cathode material (presoma).
The present invention uses following technical scheme：
A kind of preparation method of high-volume silicon-carbon negative electrode material, the quality percentage of element silicon in high-volume silicon-carbon negative electrode material
Number is 40~70%, and the mass percent of carbon is 30~60%, is as follows：
S1, the nano-silicon of required metering ratio and carbon material dispersion are subjected to wet ball grinding, rotational speed of ball-mill 300 in a solvent
~2000rpm, Ball-milling Time are 0.2~8.0h；
S2, it will be ultrasonically treated after the pulp dilution after step S1 ball millings, ultrasonic power is 500~2000W, when ultrasonic
Between be 0.5~2.0h；
S3,800~2000rpm of rotating speed, stirring will be controlled in the slurry after carbon source, surfactant addition step S2 ultrasounds
Mixture is made in 0.5~5h；
S4, control inlet and outlet temperatures, are spray-dried the mixture of step S3；
S5, it the mixture after step S4 drying is placed in tube furnace carries out heat treatment the Gao Rong with micro-nano structure is made
Silicon-carbon cathode material is measured, the grain size of silicon materials is 40~250nm in high-volume silicon-carbon negative electrode material, and the grain size of carbon material is 0.1
~20um.
Specifically, in step S1, the mass ratio of nano-silicon and carbon material is (4~2)：(1~3), Ball-milling Time be 0.5~
2.5h。
Further, carbon material is one kind or combinations thereof in graphite, nanofiber, graphene, porous carbon；Solvent is to go
One kind or combinations thereof in ionized water, ethyl alcohol, N-Methyl pyrrolidone, acetone, ethylene glycol.
Specifically, in step S2, it is 10~40% by the pulp dilution after step S1 ball millings to solid content, controls temperature 5
~10 DEG C.
Specifically, in step S3, nano-silicon, carbon source, surfactant mass ratio be 100：(10~40)：(3~20),
Carbon source is citric acid, sucrose, glucose, polyvinylpyrrolidone, starch, dextrin, polyaniline, pitch, phenolic resin, asphalt mixtures modified by epoxy resin
Any of or a combination of fat, polyimides；Surfactant is polyethylene glycol, calgon, triethyl group hexyl phosphoric acid
Any one of sodium, lauryl sodium sulfate, polyacrylamide, cetyl trimethylammonium bromide, silane coupling agent or its group
It closes.
Specifically, in step S4, the inlet temperature of spray drying is 150~250 DEG C, and outlet temperature is 90~160 DEG C, into
Liquid speed degree is 3~100mL/min.
Specifically, in step S5, the atmosphere of tube furnace is nitrogen, and temperature is 200~1000 DEG C, calcination time is 3~
12h。
A kind of high-volume silicon-carbon negative electrode material, silicon-carbon cathode material are with micro-nano structure, the mass percent of element silicon
40~70%, the mass percent of carbon is 30~60%, and the grain size of silicon materials is 40~250nm, and the grain size of carbon material is
0.1~20um.
Specifically, the grain size of silicon materials is 40~80nm；The grain size of carbon material is 2~8um.
A kind of negative electrode of lithium ion battery persursor material, is made using the high-volume silicon-carbon negative electrode material, the forerunner
Body material is used for and carbon source carries out secondary compound and cladding.
Compared with prior art, the present invention at least has the advantages that：
A kind of preparation method of high-volume silicon-carbon negative electrode material of the present invention, using ball milling, ultrasound, addition surfactant and
The Multiple techniques means such as spray drying improve raw material (nano-silicon, micron carbon) dispersibility, and method is easy to operate, it is easy to accomplish big rule
Mould produces.
Powerful impact force and fluid velocity are generated, it can be achieved that nanometer when further, using wet ball grinding (containing solvent)
Silicon and carbon material preferably disperse, are even compound, and effect is better than technologies such as stirrings.
Further, the use of ultrasound procedure, surfactant can further disperse nano-silicon, be reduced because of nanometer
Absolute volume expands caused by silicon is reunited.
Further, the present invention selects the higher carbon material of degree of graphitization, has charge/discharge capacity height and charge and discharge level
The advantages that platform is good, but the crystal structure difference between the edge and bottom surface of its crystallite is larger, and electrolyte is easily at the edge of crystallite
Side reaction occurs for part, and the irreversible capacity of material is high, and the carbon source that the present invention selects can be by amorphous random layer in carbonisation
Carbon changes to partial order graphite, reduces the irreversible capacity of material.
Further, the present invention becomes the forerunner of " nano-silicon-carbon material-carbon source " using spray dried form synthesis group
Slurry was dried rapidly with fine droplets within several seconds of short duration time, is avoided in conventional drying because of slurry by body, which
The problem of heated movement of drying time long nano-silicon, reunion, spray dried form is conducive to keep various raw materials in the slurry
The effect of the fine dispersion reached, this is great to the volume expansion question meaning for alleviating Si-C materials.
The present invention also provides a kind of high-volume silicon-carbon negative electrode material, have good dispersed structure, 1000~
The height ratio capacity of 1700mAh/g and excellent cycle performance are conducive to the energy density for improving lithium ion battery, adapt to current 3C
The demand for development of product and new-energy automobile light weight, miniature, long continuation of the journey.
Further, the high-volume silicon-carbon negative electrode material have micro-nano structure, wherein the grain size of silicon materials be 40~
80nm；The grain size of carbon material is 2~8um, and it is small small, secondary with micro materials specific surface area to combine the expansion of nano material absolute volume
Few advantage is reacted, material also has many advantages, such as to have extended cycle life in addition to specific capacity is high.
High-volume silicon-carbon negative electrode material of the present invention can be used as the presoma for preparing the more excellent silicon-carbon cathode material of chemical property
Or lithium ion battery negative material, the technology bottle of limitation high-volume silicon-carbon negative electrode material practical application can be solved to a certain extent
Neck.
In conclusion present invention process it is simple, of low cost, easy realize industrialized production technology path, using ball milling,
The modes such as surfactant, ultrasound and spray drying and optimize relevant technological parameter nano-silicon and carbon material are carried out it is effective
Disperse and compound, the Si-C composite material with height ratio capacity and cycle performance is prepared.
Below by drawings and examples, technical scheme of the present invention will be described in further detail.
Description of the drawings
Fig. 1 is the stereoscan photograph of silicon carbon material in embodiment 1；
Fig. 2 is the stereoscan photograph of silicon carbon material A in embodiment 4；
Fig. 3 is the stereoscan photograph of silicon carbon material B in embodiment 4.
Specific implementation mode
The present invention provides a kind of high-volume silicon-carbon negative electrode materials and preparation method thereof, using ball milling, surfactant, surpass
The modes such as sound and spray drying simultaneously optimize relevant technological parameter to nano-silicon and the effective dispersion of carbon material progress and compound, system
It is standby to obtain the Si-C composite material with height ratio capacity (1000~1700mAh/g) and cycle performance, it is simple for process, at low cost
Honest and clean, the easy technology path for realizing industrialized production.
A kind of high-volume silicon-carbon negative electrode material of the present invention, it is 40%~70% to have micro-nano structure, element silicon mass fraction,
Carbon mass fraction is 30%~60%；Utilize two kinds or more in ball milling, surfactant, ultrasound and spray drying of hand
Section carries out decentralized processing to raw material, and the grain size of silicon materials is 40~250nm, and the grain size of carbon material is 0.1~20um.
Preferably, the grain size of silicon materials is 40~80nm；The grain size of carbon material is 2~8um.
A kind of preparation method of high power capacity silicon carbon material of the present invention, includes the following steps：
S1, ball milling：The nano-silicon of required metering ratio and carbon material dispersion are subjected to wet ball grinding, rotational speed of ball-mill in a solvent
For 300~2000rpm, Ball-milling Time is 0.2~8.0h, it is preferable that Ball-milling Time is 0.5~2.5h；
Carbon material is any of or a combination of graphite, nanofiber, graphene, porous carbon；Solvent be deionized water,
Any of or a combination of ethyl alcohol, N-Methyl pyrrolidone, acetone, ethylene glycol.
S2, ultrasound：Pulp dilution after ball milling to solid content is ultrasonically treated for 10~40% in 5 DEG C, ultrasonic work(
Rate is 500~2000W, and ultrasonic time is 0.5~2.0h；
It is prepared by S3, slurry：Carbon source, surfactant are added in the slurry after ultrasound, are vigorously stirred 0.5~5h, rotating speed
800~2000rpm；
Carbon source can be citric acid, sucrose, glucose, polyvinylpyrrolidone, starch, dextrin, polyaniline, pitch, phenolic aldehyde
Any of or a combination of resin, epoxy resin, polyimides；Surfactant can be polyethylene glycol, calgon, three
In ethylhexyl phosphoric acid sodium, lauryl sodium sulfate, polyacrylamide, cetyl trimethylammonium bromide, silane coupling agent
It is any or combinations thereof.
S4, spray drying：Inlet temperature be 150~250 DEG C, outlet temperature be 90~160 DEG C, feed speed be 3~
100mL/min；
S5, heat treatment：Material is placed in the tube furnace of nitrogen atmosphere and is heat-treated, temperature is 200~1000 DEG C, is forged
The burning time is 3~12h；
Lithium ion battery negative material can be used as using high-volume silicon-carbon negative electrode material prepared by preparation method of the present invention,
Persursor material be can also be used as to carry out secondary compound and cladding with carbon source, to obtain performance more preferably silicon carbon material.
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.The present invention being described and shown in usually here in attached drawing is real
Applying the component of example can be arranged and be designed by a variety of different configurations.Therefore, the present invention to providing in the accompanying drawings below
The detailed description of embodiment be not intended to limit the range of claimed invention, but be merely representative of the selected of the present invention
Embodiment.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
The every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1
The synthesis of high-volume silicon-carbon negative electrode material
(1) ball milling：By the graphite of silicon, 8um that middle grain size is 230nm with 3.25:1 mass ratio, which is scattered in ethyl alcohol, to carry out
Ball milling, ratio of grinding media to material 8：1, rotating speed 1000rpm, Ball-milling Time 2h；
(2) ultrasonic：It is 20% by the slurry adjustment solid content after ball milling, in 5 DEG C of ultrasound 30min, ultrasonic power is
1300W；
(3) surfactant and carbon source are added：The ethyl alcohol of PVP8000, PEG20000 of 0.03mol/L are added into slurry
It is vigorously stirred 2.0h, rotating speed 800rpm；
(4) it is spray-dried：Entrance, outlet temperature are respectively 150,60 DEG C, feed speed 8mL/min；
(5) it is heat-treated：N2Atmosphere, 480 DEG C of 2h+850 DEG C of 3h.
The physico-chemical property of Si-C composite material characterizes：
The microscopic appearance of the silicon carbon material obtained under above-mentioned condition is shown in Fig. 1, it can be seen that nano particle and micron flakes material
Material is interspersed, and there are very thin clads for nano grain surface, it is achieved that nano-silicon and the good of micron graphite are divided
It dissipates and compound.Thermogravimetric method test result shows silicon in the material, the mass fraction of carbon is respectively 67%, 33%.
The Electrochemical Characterization of Si-C composite material：
By the silicon-carbon cathode material being prepared, Super-P, LA132 with mass ratio 8:1:1 mass ratio, it is molten in ethyl alcohol
The slurry being uniformly mixed is vigorously stirred in liquid, after slurry is equably coated onto in copper foil current collector, at 80 DEG C vacuum dry
2h is dried in case, is cut into the round pole piece of a diameter of 16mm.
Using metal lithium sheet as anode, PP/PE/PP microporous barriers (Celgard2400) are used as diaphragm, 1.15mol/L
(solvent is that volume ratio is 1 to LiPF6：1：1 ethylene carbonate, dimethyl carbonate and diethyl carbonate mixed liquor) as electrolysis
Liquid is assembled into button cell in the glove box of argon gas protection, carries out constant current charge-discharge test, and charge and discharge electric current is distinguished for the first time
For 300,150mA/g, from the 2nd cycle, charging and discharging currents are 1500,750mA/g, and charging/discharging voltage section is 0.01-
2.00V, cell testing results are listed in table 1.
Embodiment 2
(1) ball milling：By the graphite B of graphite A, 8um of silicon, 20um that grain size is 80nm with 45：25：5 mass ratio dispersion
Ball milling, ratio of grinding media to material 8 are carried out in ethyl alcohol：1, ball milling speed 400rpm, Ball-milling Time 2h；
(2) ultrasonic：Slurry solid content after ball milling is adjusted to 15%, in 5 DEG C of ultrasound 30min, ultrasonic power is
1000W；
(3) it is spray-dried：Entrance, outlet temperature are respectively 150,60 DEG C, feed speed 5mL/min, and presoma is made
C；
(4) carbon source is added：Coal tar pitch is added into slurry, adjustment solid content is 10%, is vigorously stirred 1.0h, rotating speed is
1500rpm；
(5) it is spray-dried：Entrance, outlet temperature are respectively 150,60 DEG C, feed speed 7.5mL/min；
(6) it is heat-treated：N2 atmosphere, 200 DEG C of 2h+850 DEG C of 3h.
Thermogravimetric method test result shows silicon in the material, the mass fraction of carbon is respectively 43%, 57%.Chemical property
For characterization with embodiment 1, electrochemical property test the results are shown in Table 1.
Embodiment 3
As different from Example 1, PVP8000 is changed to PVP55000, and other conditions are identical.
Embodiment 4
(1) ball milling：By the graphite of silicon, 8um that grain size is 80nm with 65:20 mass ratio, which is scattered in ethyl alcohol, carries out ball
Mill, ratio of grinding media to material 8：1, ball milling speed 400rpm, Ball-milling Time 2h；
(2) ultrasonic：Slurry adjustment after ball milling is fixed in 5 DEG C of ultrasounds 30min, ultrasonic power 800W；
(3) carbon source 1 is added：
The ethanol solution of 2.5mol/L citric acids is added into slurry, adjustment solid content is 5%, is vigorously stirred 1.5h, is turned
Speed is 1000rpm；
(2) it is spray-dried and is heat-treated：
Entrance, outlet temperature are respectively 150,95 DEG C, feed speed 20mL/min；Afterwards in N2 gas
Atmosphere, 400 DEG C of heat treatment 2h, obtains silicon carbon material (presoma) A；
(4) surfactant and carbon source 2 are added：To alcohol/water (volume ratio 5 of PVP8000, PEG20000：1) solution adds
Enter silicon carbon material (presoma) A, solid content is adjusted to 25%, is vigorously stirred 2h；
(5) it sprays：
Entrance, outlet temperature are respectively 180,100 DEG C；Feed speed is 60mL/min；
(6) it calcines：
N2Atmosphere, 400 DEG C of 2h+900 DEG C of 5h, obtains silicon carbon material B.
According to thermogravimetric method test result analysis it is found that silicon, graphite, citric acid pyrolytic carbon, PVP pyrolysis in silicon carbon material B
The mass fraction of carbon is respectively 64%, 21%, 3%, 12%.
Stereoscan photograph (see attached drawing 2) show silicon carbon material (presoma) A have spherical morphology, nano-silicon and graphite with
And citric acid pyrolytic carbon forms preferable composite construction.This embodiment gives through technologies such as ball milling, ultrasound and spray drying
Silicon carbon material A made from means as presoma, be re-introduced into PVP8000 be carbon source be made spherical morphology silicon carbon material B (see
Attached drawing 3), the tap density and cyclical stability of material can be effectively improved.
Embodiment 5
(1) ball milling：By the graphite of silicon, 8um that grain size is 80nm with 65：35 mass ratio, which is scattered in ethyl alcohol, carries out ball
Mill, ratio of grinding media to material 8：1, ball milling speed 1200rpm, Ball-milling Time 2h；
(2) ultrasonic：It is 10% by the slurry adjustment solid content after ball milling, in 5 DEG C of ultrasound 30min, ultrasonic power is
1300W；
(3) it is spray-dried：Entrance, outlet temperature are respectively 170,90 DEG C, feed speed 10mL/min；
(5) it is heat-treated：N2Atmosphere, 200 DEG C of 2h+850 DEG C of 3h.
Stereoscan photograph shows that nano-silicon reunion is distributed in graphite flake layer surface in the material.Electrochemical Characterization is same
Embodiment 1, electrochemical property test the results are shown in Table 1.
Comparative example 1
(1) ball milling：By the graphite of silicon, 8um that grain size is 80nm with 65：25 mass ratio, which is scattered in ethyl alcohol, carries out ball
Mill, ratio of grinding media to material 8：1, ball milling speed 400rpm, Ball-milling Time 2h；
(2) ultrasonic：By the slurry after ball milling in 5 DEG C of ultrasounds 30min, ultrasonic power 1500W；
(3) carbon source is added：Coal tar pitch is added into slurry, adjustment solid content is 5%, is vigorously stirred 2.0h, rotating speed is
900rpm；
(4) it is spray-dried：Entrance, outlet temperature are respectively 150,60 DEG C, feed speed 10mL/min；
(5) it is heat-treated：N2Atmosphere, 480 DEG C of 2h+850 DEG C of 3h.
Thermogravimetric method test result shows silicon in the material, the mass fraction of carbon is respectively 63%, 37%.
For Electrochemical Characterization with embodiment 1, electrochemical property test the results are shown in Table 1.
1 section Example of table and the chemical property of comparative example silicon carbon material summarize
The above content is merely illustrative of the invention's technical idea, and protection scope of the present invention cannot be limited with this, every to press
According to technological thought proposed by the present invention, any change done on the basis of technical solution each falls within claims of the present invention
Protection domain within.
Claims (10)
1. a kind of preparation method of high-volume silicon-carbon negative electrode material, which is characterized in that element silicon in high-volume silicon-carbon negative electrode material
Mass percent be 40~70%, the mass percent of carbon is 30~60%, is as follows：
S1, the nano-silicon of required metering ratio and carbon material dispersion being subjected to wet ball grinding in a solvent, rotational speed of ball-mill is 300~
2000rpm, Ball-milling Time are 0.2~8.0h；
S2, it will be ultrasonically treated after the pulp dilution after step S1 ball millings, ultrasonic power is 500~2000W, and ultrasonic time is
0.5~2.0h；
S3,800~2000rpm of rotating speed, stirring 0.5 will be controlled in the slurry after carbon source, surfactant addition step S2 ultrasounds
Mixture is made in~5h；
S4, control inlet and outlet temperatures, are spray-dried the mixture of step S3；
S5, it the mixture after step S4 drying is placed in tube furnace carries out heat treatment the high power capacity silicon with micro-nano structure is made
Carbon negative pole material, the grain size of silicon materials is 40~250nm in high-volume silicon-carbon negative electrode material, the grain size of carbon material is 0.1~
20um。
2. a kind of preparation method of high-volume silicon-carbon negative electrode material according to claim 1, which is characterized in that step S1
In, the mass ratio of nano-silicon and carbon material is (4~2)：(1~3), Ball-milling Time are 0.5~2.5h.
3. a kind of preparation method of high-volume silicon-carbon negative electrode material according to claim 2, which is characterized in that carbon material is
One kind or combinations thereof in graphite, nanofiber, graphene, porous carbon；Solvent is deionized water, ethyl alcohol, N- crassitudes
One kind or combinations thereof in ketone, acetone, ethylene glycol.
4. a kind of preparation method of high-volume silicon-carbon negative electrode material according to claim 1, which is characterized in that step S2
In, it is 10~40% by the pulp dilution after step S1 ball millings to solid content, controls 5~10 DEG C of temperature.
5. a kind of preparation method of high-volume silicon-carbon negative electrode material according to claim 1, which is characterized in that step S3
In, nano-silicon, carbon source, surfactant mass ratio be 100：(10~40)：(3~20), carbon source are citric acid, sucrose, Portugal
Any in grape sugar, polyvinylpyrrolidone, starch, dextrin, polyaniline, pitch, phenolic resin, epoxy resin, polyimides
Kind or combinations thereof；Surfactant is polyethylene glycol, calgon, triethyl group hexyl phosphoric acid sodium, lauryl sodium sulfate, gathers
Any of or a combination of acrylamide, cetyl trimethylammonium bromide, silane coupling agent.
6. a kind of preparation method of high-volume silicon-carbon negative electrode material according to claim 1, which is characterized in that step S4
In, the inlet temperature of spray drying is 150~250 DEG C, and outlet temperature is 90~160 DEG C, and feed speed is 3~100mL/min.
7. a kind of preparation method of high-volume silicon-carbon negative electrode material according to claim 1, which is characterized in that step S5
In, the atmosphere of tube furnace is nitrogen, and temperature is 200~1000 DEG C, and calcination time is 3~12h.
8. a kind of high-volume silicon-carbon negative electrode material, which is characterized in that silicon-carbon cathode material has micro-nano structure, the quality of element silicon
Percentage is 40~70%, and the mass percent of carbon is 30~60%, and the grain size of silicon materials is 40~250nm, carbon material
Grain size be 0.1~20um.
9. a kind of high-volume silicon-carbon negative electrode material according to claim 8, which is characterized in that the grain size of silicon materials be 40~
80nm；The grain size of carbon material is 2~8um.
10. a kind of lithium ion battery persursor material, which is characterized in that utilize the high power capacity silicon-carbon cathode of claim 8 or 9
Material is made, and the persursor material is used for and carbon source carries out secondary compound and cladding.
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