CN108054351A - A kind of lithium ion battery, silicon-carbon cathode material used and preparation method thereof - Google Patents
A kind of lithium ion battery, silicon-carbon cathode material used and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of lithium ion batteries, silicon-carbon cathode material used and preparation method thereof, the silicon-carbon cathode material be the slurry containing nano silica fume or nano oxidized sub- silica flour is mixed with micron order graphite powder, coal tar soft asphalt kneading, coking, crushing, then obtained after carrying out surface chemistry vapor deposition processing.Nano-silicon/oxidation Asia silicon particle asphalt carbon first is disperseed to be fixed in graphite particle by the present invention; again barish silicon particle surface is protected with vapor deposition charcoal; the specific capacity of prepared silicon carbon cathode material significantly improves; capacity retention ratio is high during battery iterative cycles; to the adaptable of electrolyte; battery high comprehensive performance, is with a wide range of applications.
Description
Technical field
The invention belongs to lithium electric material field, be related to electrochemistry and carbon carbon composite field more particularly to a kind of lithium from
Sub- battery, silicon-carbon cathode material used and preparation method thereof.
Background technology
Lithium ion battery have energy density is big, operating voltage is high, small, light weight, pollution-free, fast charging and discharging,
The excellent properties of have extended cycle life etc., thus very big concern and extensive use have been obtained in recent years.Lithium ion battery is with carbon
Cellulosic material is cathode, makees anode with the compound containing lithium；For negative material, although graphite negative electrodes material is half at present
Reality in battery takes off lithium capacity and is up to 365mAh/g (theoretically the reversible lithium storage capacity of graphite can reach 372mAh/g), but still
Can not meet the needs of high energy density cells, by taking 18650 lithium batteries as an example, graphite cathode can not meet more than 3.0Ah
The energy density requirement of battery, to meet market demands must develop a kind of cathode of new high-energy density long circulation life
Material.
In order to improve the specific capacity of negative material and improve charge-discharge performance, researcher begins one's study non-carbon cathode material
Material, the study found that the theoretical capacity of silicon is far above the capacity of graphite, capacity can reach 4200mAh/g, and it is theoretical to aoxidize sub- silicon
Capacity 2043mAh/g takes off lithium potential plateau 0.45V or so；But silica-base material is there is also apparent electrical property defect, mainly
Volume contraction and the expansion that silica-base material can generate 100%~300% during removal lithium embedded, cause cycle performance of battery compared with
Difference, it is difficult to be used alone.Researcher transfers to be directed to the exploitation of silicon carbon cathode material, holds to lithium ion battery to be hoisted
Amount, solution silicon is caused in charge and discharge process due to volume expansion contraction and electrolyte contacts, constantly forms new interface, from
And influence the cycle life problem of battery.
In recent years, someone disperses nano silica-base material using slurry or common distribution is nano silicon-based and conductive nano agent
Material, then using pitch-coating or dipping after, then the silicon-carbon cathode material technology of preparing that carbonizes occurs, and improves to some extent
The cycle performance of silicon carbon cathode material, but since it uses the technique carbonized again after pitch (hydrocarbon) cladding or dipping,
It is substantially first coated with hydrocarbon or impregnates material, then carbonized at 700 DEG C or more, departed from protium, be left
Carbon form layer of charcoal on silicon materials surface, and such carbon-coating is not fine and close enough, uniformly, it is impossible to effectively limit silicon particle
Contact with electrolyte can not effectively limit the expansion of silicon particle, so its properties of product is also far from reaching people's
It is expected.
The content of the invention
The present invention provides a kind of lithium ion battery, silicon-carbon cathode material used and preparation method thereof, by using mixed
It pinches, coking, first disperses to be fixed in graphite particle by nano-silicon/oxidation Asia silicon particle asphalt carbon, then protected with vapor deposition charcoal
Barish silicon particle surface is protected, the specific capacity of prepared silicon carbon cathode material significantly improves, in battery iterative cycles mistake
Capacity retention ratio is high in journey, and to the adaptable of electrolyte, battery high comprehensive performance is with a wide range of applications.
In order to achieve the above object, the present invention is realized using following technical scheme：
A kind of preparation method of silicon-carbon cathode material, includes the following steps：
1) slurry containing nano silica fume or nano oxidized sub- silica flour is mixed with micron order graphite powder, coal tar soft asphalt
Pinch mixing；The weight percent of each component is as follows：
Slurry containing nano silica fume or nano oxidized sub- silica flour：5~30wt%；
Micron order graphite powder：30~45wt%；
Coal tar soft asphalt：40~55wt%；
2) mixture made from step 1) is subjected to coking, the graphite pitch for obtaining siliceous substrates material is burnt；
3) the graphite pitch coke powder of siliceous substrates material made from step 2) is broken, the graphite pitch for obtaining siliceous substrates material is burnt
Powder；
4) surface chemistry vapor deposition processing is carried out to the graphite pitch coke powder material of siliceous substrates material made from step 3), obtained
To silicon carbon cathode material.
It is described containing nano silica fume or the slurry of nano oxidized sub- silica flour is to use nano silica fume or nano oxidized sub- silica flour
Sand mill is evenly spread in solvent, and the percent weight solids level in slurry is 5~30wt%, and the solvent is carbolic oil, washes
The arbitrary mixing of one or two or more kinds in oil, carbolineum.
The grain size of the nano silica fume or nano oxidized sub- silica flour is 500~700nm.
The micron order graphite powder is that grain size is 500~12000 μm of graphite material, graphite material is Delanium,
The mixture that one or both of native graphite mixes in any proportion.
By slurry and micron order graphite powder, coal tar containing nano silica fume or nano oxidized sub- silica flour in the step 1)
Oily maltha kneading mixing carries out in kneading machine, and kneading temperature is 30~70 DEG C, when the kneading time 2~5 is small.
In the step 2) by mixture progress coking be under nitrogen protection, by mixed material heating to 550~700 DEG C into
Row coking is handled, and when coking processing time is 5~8 small, the graphite pitch for obtaining block siliceous substrates material is burnt.
The graphite pitch coke powder of siliceous substrates material is broken to D50=5~20 μm in the step 3).
Surface chemistry vapor deposition processing is 1000~1200 DEG C using CVD method, deposition charcoal temperature in the step 4), is sunk
When the carbon deposit time is 1~10 small, carbon-source gas are one or more gases in ethylene, propylene, acetylene and alkanes gas
Mixing.
A kind of silicon-carbon cathode material of the present invention, applied to lithium ion battery, the silicon-carbon cathode material has core
Dual cladding structure outside substance and core substance, wherein core substance are nano-silicon/nano oxidized sub- silicon particle and graphite
The homogeneous mixture of grain, the external sheath structure in dual cladding structure are vapor deposition layer of charcoal, and internal layer clad structure is pitch
Layer of charcoal.
A kind of lithium ion battery of the present invention, the lithium ion battery include preparation described in any one of the present invention
Silicon-carbon cathode material made from method.
Compared with prior art, the beneficial effects of the invention are as follows：
1) nano-silicon or nano oxidized sub- silicon are introduced in carbon material, gram volume has been more than the theoretical appearance of graphite material
Amount, so that the charge and discharge gram volume of battery substantially increases；
2) silica-base material is mixed using slurry form with carbon material, and nano-silicon/oxidation Asia silicon is made preferably to be dispersed in carbon materials
Material is internal, and quality is evenly；
3) surface chemistry vapor deposition processing is carried out to the graphite pitch coke powder material after coking, makes nano-silicon/oxidation Asia silicon
Particle is especially deposited charcoal package by external coke, has been fettered the expansion of silicon/oxidation Asia silicon, has been efficiently solved volume expansion and ask
Topic, and solve the problems, such as silica-base material and electrolyte contacts, thus circulation volume conservation rate is improved well；
2) preparation process flow is simple, easily controllable, and device therefor is industrialization conventional equipment, it is easy to accomplish industrialization
Production.
Specific embodiment
A kind of preparation method of silicon-carbon cathode material of the present invention, includes the following steps：
1) slurry containing nano silica fume or nano oxidized sub- silica flour is mixed with micron order graphite powder, coal tar soft asphalt
Pinch mixing；The weight percent of each component is as follows：
Slurry containing nano silica fume or nano oxidized sub- silica flour：5~30wt%；
Micron order graphite powder：30~45wt%；
Coal tar soft asphalt：40~55wt%；
2) mixture made from step 1) is subjected to coking, the graphite pitch for obtaining siliceous substrates material is burnt；
3) the graphite pitch coke powder of siliceous substrates material made from step 2) is broken, the graphite pitch for obtaining siliceous substrates material is burnt
Powder；
4) surface chemistry vapor deposition processing is carried out to the graphite pitch coke powder material of siliceous substrates material made from step 3), obtained
To silicon carbon cathode material.
It is described containing nano silica fume or the slurry of nano oxidized sub- silica flour is to use nano silica fume or nano oxidized sub- silica flour
Sand mill is evenly spread in solvent, and the percent weight solids level in slurry is 5~30wt%, and the solvent is carbolic oil, washes
The arbitrary mixing of one or two or more kinds in oil, carbolineum.
The grain size of the nano silica fume or nano oxidized sub- silica flour is 500~700nm.
The micron order graphite powder is that grain size is 500~12000 μm of graphite material, graphite material is Delanium,
The mixture that one or both of native graphite mixes in any proportion.
By slurry and micron order graphite powder, coal tar containing nano silica fume or nano oxidized sub- silica flour in the step 1)
Oily maltha kneading mixing carries out in kneading machine, and kneading temperature is 30~70 DEG C, when the kneading time 2~5 is small.
In the step 2) by mixture progress coking be under nitrogen protection, by mixed material heating to 550~700 DEG C into
Row coking is handled, and when coking processing time is 5~8 small, the graphite pitch for obtaining block siliceous substrates material is burnt.
The graphite pitch coke powder of siliceous substrates material is broken to D50=5~20 μm in the step 3).
Surface chemistry vapor deposition processing is 1000~1200 DEG C using CVD method, deposition charcoal temperature in the step 4), is sunk
When the carbon deposit time is 1~10 small, carbon-source gas are one or more gases in ethylene, propylene, acetylene and alkanes gas
Mixing.
A kind of silicon-carbon cathode material of the present invention, applied to lithium ion battery, the silicon-carbon cathode material has core
Dual cladding structure outside substance and core substance, wherein core substance are nano-silicon/nano oxidized sub- silicon particle and graphite
The homogeneous mixture of grain, the external sheath structure in dual cladding structure are vapor deposition layer of charcoal, and internal layer clad structure is pitch
Layer of charcoal.
A kind of lithium ion battery of the present invention, the lithium ion battery include preparation described in any one of the present invention
Silicon-carbon cathode material made from method.
The technical problem to be solved by the present invention is to by preparing uniformly and fine and close carbon-coating, prevent silica-base material as far as possible
Contact of the interface with electrolyte simultaneously effective limits the undue volume expansion of silica-base material and shrinks and cause what lattice caved in ask
Topic.A kind of preparation method of the silicon-carbon cathode material provided is by using kneading, coking, first nano-silicon/oxidation Asia silicon
Particle asphalt carbon disperses to be fixed in graphite particle, then protects barish silicon particle surface with vapor deposition charcoal.And gas
Mutually deposition charcoal, be carbon source gas at 700 degree or more, first and protium depart to form carbon atom, the carbon atom is at 1000~1200 DEG C
Under hot conditions, substrate material surface is deposited on.For this deposition charcoal for high temperature carbonization charcoal, finer and close and distribution is equal
It is even, it is reacted so as to which silicon particle is more effectively protected not formed with electrolyte, also can more effectively limit silicon particle and use
Overinflation and contraction in the process, so, the discharge capacity for the first time of silicon-carbon cathode material prepared by the present invention is high, cycle life
It is long, it is adaptable to electrolyte.
Lithium ion battery silicon-carbon cathode material obtained by the present invention is tested using following methods：
Grain size D50 is measured：A small amount of sample is taken to add in beaker, 1-2 drop surfactants is added, adds in a small amount of distilled water
It stirs evenly, ultrasonic oscillation 3 minutes, is tested, reached corresponding to 50% volume with Britain's Malvern MS2000 laser particle analyzers
Part grain size is D50 grain sizes.
Electric performance test：Using half-cell test method；CR2430 type button cells are made, using lithium piece as to electrode, electricity
Solution liquid is 1M LiPF6+EC:EMC:DMC=1:1:1 (volume ratio), membrane are answered for tri- layers of micropores of Celgard2300PP/PE/PP
Close film, cathode：SP：CMC：SBR presses 95：2：1.5：1.5 ratios match somebody with somebody synthetic slurry, are then applied on copper-foil conducting electricity, and 120 DEG C dry
Dry 2h, using roller press, the roll-forming under the pressure of 10MPa.After positive, negative electrode plate, membrane and electrolyte are assembled, punching press
Sealing.All assembling process carry out in the dry glove box full of argon gas.
Electrochemical property test：It is carried out on U.S. ArbinBT2000 type cell testers, charge and discharge system：1) constant current
It discharges (0.6mA, 0.01V)；2) (10min) is stood；3) constant-current charge (0.6mA, 2.000V).Measure lithium ion of the present invention
By repeating aforesaid operations, charge/discharge test 300 is carried out in the lithium ion battery for the initial capacity and coulombic efficiency of battery
Secondary cycling.
For the present invention in addition to special instruction, percentage used is all mass percent.Raw material used or reagent are except spy
Do not mentionlet alone it is bright outside, it is commercially available.
Following embodiment is being implemented down based on the technical solution of the present invention, gives detailed embodiment and tool
The operating process of body, but protection scope of the present invention is not limited to following embodiments.Method therefor is such as without spy in following embodiments
It is conventional method not mentionlet alone bright.
【Embodiment 1】
In the present embodiment, the weight percent of each component is in silicon-carbon cathode material：Contain nano silica fume or nano oxidized
The slurry of sub- silica flour：18wt%；Micron order graphite powder：38wt%；Coal tar soft asphalt：48wt%；
Will by the graphite pitch coke powder of step 1)-step 3) of the present invention siliceous substrates material 4wt% obtained afterwards, point
The coke powder particle of D50=12.0 μm of average grain diameter is formed after grade；
Coke powder particle is put into rotary furnace, carries out surface chemistry vapor deposition processing with CVD method, whole process is carried out using nitrogen
Protection, deposition charcoal temperature is 1000 DEG C, when the deposition charcoal time is 1 small, cools to room temperature with the furnace after heat preservation, finally obtains silicon
Carbon negative pole material.
After tested, discharge capacity is 463.8mAh/g to silicon-carbon cathode material prepared by the present embodiment for the first time, is discharged for the first time
Efficiency is 87.5%, and capacity retention ratio is 81.1% after 300 weeks Xun Huans.
【Embodiment 2】
In the present embodiment, the weight percent of each component is in silicon-carbon cathode material：Contain nano silica fume or nano oxidized
The slurry of sub- silica flour：18wt%；Micron order graphite powder：38wt%；Coal tar soft asphalt：48wt%；
Will by the graphite pitch coke powder of step 1)-step 3) of the present invention siliceous substrates material 4wt% obtained afterwards, point
The coke powder particle of D50=12.0 μm of average grain diameter is formed after grade；
Coke powder particle is put into rotary furnace, carries out surface chemistry vapor deposition processing with CVD method, whole process is carried out using nitrogen
Protection, deposition charcoal temperature is 1000 DEG C, when the deposition charcoal time is 3 small, cools to room temperature with the furnace after heat preservation, finally obtains silicon
Carbon negative pole material.
After tested, discharge capacity is 468.0mAh/g to silicon-carbon cathode material prepared by the present embodiment for the first time, is discharged for the first time
Efficiency is 88.3%, and capacity retention ratio is 82.3% after 300 weeks Xun Huans.
【Embodiment 3】
In the present embodiment, the weight percent of each component is in silicon-carbon cathode material：Contain nano silica fume or nano oxidized
The slurry of sub- silica flour：18wt%；Micron order graphite powder：38wt%；Coal tar soft asphalt：48wt%；
Will by the graphite pitch coke powder of step 1)-step 3) of the present invention siliceous substrates material 4wt% obtained afterwards, point
The coke powder particle of D50=12.0 μm of average grain diameter is formed after grade；
Coke powder particle is put into rotary furnace, carries out surface chemistry vapor deposition processing with CVD method, whole process is carried out using nitrogen
Protection, deposition charcoal temperature is 1000 DEG C, when the deposition charcoal time is 5 small, cools to room temperature with the furnace after heat preservation, finally obtains silicon
Carbon negative pole material.
After tested, discharge capacity is 473.3mAh/g to silicon-carbon cathode material prepared by the present embodiment for the first time, is discharged for the first time
Efficiency is 89.3%, and capacity retention ratio is 83.1% after 300 weeks Xun Huans.
【Embodiment 4】
In the present embodiment, the weight percent of each component is in silicon-carbon cathode material：Contain nano silica fume or nano oxidized
The slurry of sub- silica flour：18wt%；Micron order graphite powder：38wt%；Coal tar soft asphalt：48wt%；
Will by the graphite pitch coke powder of step 1)-step 3) of the present invention siliceous substrates material 4wt% obtained afterwards, point
The coke powder particle of D50=12.0 μm of average grain diameter is formed after grade；
Coke powder particle is put into rotary furnace, carries out surface chemistry vapor deposition processing with CVD method, whole process is carried out using nitrogen
Protection, deposition charcoal temperature is 1100 DEG C, when the deposition charcoal time is 1 small, cools to room temperature with the furnace after heat preservation, finally obtains silicon
Carbon negative pole material.
After tested, discharge capacity is 465.0mAh/g to silicon-carbon cathode material prepared by the present embodiment for the first time, is discharged for the first time
Efficiency is 87.9%, and capacity retention ratio is 81.8% after 300 weeks Xun Huans.
【Embodiment 5】
In the present embodiment, the weight percent of each component is in silicon-carbon cathode material：Contain nano silica fume or nano oxidized
The slurry of sub- silica flour：18wt%；Micron order graphite powder：38wt%；Coal tar soft asphalt：48wt%；
Will by the graphite pitch coke powder of step 1)-step 3) of the present invention siliceous substrates material 4wt% obtained afterwards, point
The coke powder particle of D50=12.0 μm of average grain diameter is formed after grade；
Coke powder particle is put into rotary furnace, carries out surface chemistry vapor deposition processing with CVD method, whole process is carried out using nitrogen
Protection, deposition charcoal temperature is 1100 DEG C, when the deposition charcoal time is 3 small, cools to room temperature with the furnace after heat preservation, finally obtains silicon
Carbon negative pole material.
After tested, discharge capacity is 471.2mAh/g to silicon-carbon cathode material prepared by the present embodiment for the first time, is discharged for the first time
Efficiency is 88.9%, and capacity retention ratio is 82.5% after 300 weeks Xun Huans.
【Embodiment 6】
In the present embodiment, the weight percent of each component is in silicon-carbon cathode material：Contain nano silica fume or nano oxidized
The slurry of sub- silica flour：18wt%；Micron order graphite powder：38wt%；Coal tar soft asphalt：48wt%；
Will by the graphite pitch coke powder of step 1)-step 3) of the present invention siliceous substrates material 4wt% obtained afterwards, point
The coke powder particle of D50=12.0 μm of average grain diameter is formed after grade；
Coke powder particle is put into rotary furnace, carries out surface chemistry vapor deposition processing with CVD method, whole process is carried out using nitrogen
Protection, deposition charcoal temperature is 1100 DEG C, when the deposition charcoal time is 5 small, cools to room temperature with the furnace after heat preservation, finally obtains silicon
Carbon negative pole material.
After tested, discharge capacity is 485.5mAh/g to silicon-carbon cathode material prepared by the present embodiment for the first time, is discharged for the first time
Efficiency is 91.5%, and capacity retention ratio is 85.5% after 300 weeks Xun Huans.
【Embodiment 7】
In the present embodiment, the weight percent of each component is in silicon-carbon cathode material：Contain nano silica fume or nano oxidized
The slurry of sub- silica flour：18wt%；Micron order graphite powder：38wt%；Coal tar soft asphalt：48wt%；
Will by the graphite pitch coke powder of step 1)-step 3) of the present invention siliceous substrates material 4wt% obtained afterwards, point
The coke powder particle of D50=12.0 μm of average grain diameter is formed after grade；
Coke powder particle is put into rotary furnace, carries out surface chemistry vapor deposition processing with CVD method, whole process is carried out using nitrogen
Protection, deposition charcoal temperature is 1200 DEG C, when the deposition charcoal time is 1 small, cools to room temperature with the furnace after heat preservation, finally obtains silicon
Carbon negative pole material.
After tested, discharge capacity is 466.9mAh/g to silicon-carbon cathode material prepared by the present embodiment for the first time, is discharged for the first time
Efficiency is 88.1%, and capacity retention ratio is 82.1% after 300 weeks Xun Huans.
【Embodiment 8】
In the present embodiment, the weight percent of each component is in silicon-carbon cathode material：Contain nano silica fume or nano oxidized
The slurry of sub- silica flour：18wt%；Micron order graphite powder：38wt%；Coal tar soft asphalt：48wt%；
Will by the graphite pitch coke powder of step 1)-step 3) of the present invention siliceous substrates material 4wt% obtained afterwards, point
The coke powder particle of D50=12.0 μm of average grain diameter is formed after grade；
Coke powder particle is put into rotary furnace, carries out surface chemistry vapor deposition processing with CVD method, whole process is carried out using nitrogen
Protection, deposition charcoal temperature is 1200 DEG C, when the deposition charcoal time is 3 small, cools to room temperature with the furnace after heat preservation, finally obtains silicon
Carbon negative pole material.
After tested, discharge capacity is 475.9mAh/g to silicon-carbon cathode material prepared by the present embodiment for the first time, is discharged for the first time
Efficiency is 89.8%, and capacity retention ratio is 83.6% after 300 weeks Xun Huans.
【Embodiment 9】
In the present embodiment, the weight percent of each component is in silicon-carbon cathode material：Contain nano silica fume or nano oxidized
The slurry of sub- silica flour：18wt%；Micron order graphite powder：38wt%；Coal tar soft asphalt：48wt%；
Will by the graphite pitch coke powder of step 1)-step 3) of the present invention siliceous substrates material 4wt% obtained afterwards, point
The coke powder particle of D50=12.0 μm of average grain diameter is formed after grade；
Coke powder particle is put into rotary furnace, carries out surface chemistry vapor deposition processing with CVD method, whole process is carried out using nitrogen
Protection, deposition charcoal temperature is 1500 DEG C, when the deposition charcoal time is 5 small, cools to room temperature with the furnace after heat preservation, finally obtains silicon
Carbon negative pole material.
After tested, discharge capacity is 483.4mAh/g to silicon-carbon cathode material prepared by the present embodiment for the first time, is discharged for the first time
Efficiency is 90.5%, and capacity retention ratio is 85.8% after 300 weeks Xun Huans.
【Comparative example 1】
In the present embodiment, the graphite pitch coke powder of siliceous substrates material 4wt% obtained in embodiment 9 forms after classification
The coke powder particle of D50=12.0 μm of average grain diameter, directly as silicon-carbon cathode material.
After tested, discharge capacity is 453.2mAh/g to silicon-carbon cathode material prepared by the present embodiment for the first time, is discharged for the first time
Efficiency is 85.5%, and capacity retention ratio is 69.0% after 300 weeks Xun Huans.
【Comparative example 2】
In the present embodiment, by coke powder particle obtained in comparative example, after being coated with coal tar asphalt in kettle is coated,
By 1200 degree, constant temperature 5 carbonizes when small, is cooled to room temperature, and obtained charing cladding material is as silicon-carbon cathode material.
After tested, discharge capacity is 452.0mAh/g to silicon-carbon cathode material prepared by the present embodiment for the first time, is discharged for the first time
Efficiency is 85.3%, and capacity retention ratio is 75.0% after 300 weeks Xun Huans.
Above-described embodiment see the table below after summarizing with silicon-carbon cathode material test result prepared by comparative example：
As can be seen from the above table, the discharge capacity for the first time of the silicon-carbon cathode material prepared using the method for the invention is more
Height, cycle life are longer.
Referred to fully test using the performance of silicon-carbon cathode material after CVD method progress surface chemistry vapor deposition processing
It marks, the raw material and processing procedure early period employed in above example are consistent, and use different chemical vapor depositions
Technological parameter, so that final test result has comparability.But the material composition composition and step 1)-step 3) of the present invention
Technological parameter be not limited to above-described embodiment.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of silicon-carbon cathode material, which is characterized in that include the following steps：
1) slurry containing nano silica fume or nano oxidized sub- silica flour is mixed with micron order graphite powder, coal tar soft asphalt kneading
It closes；The weight percent of each component is as follows：
Slurry containing nano silica fume or nano oxidized sub- silica flour：5~30wt%；
Micron order graphite powder：30~45wt%；
Coal tar soft asphalt：40~55wt%；
2) mixture made from step 1) is subjected to coking, the graphite pitch for obtaining siliceous substrates material is burnt；
3) it is the graphite pitch coke powder of siliceous substrates material made from step 2) is broken, obtain the graphite pitch coke powder of siliceous substrates material
Material；
4) surface chemistry vapor deposition processing is carried out to the graphite pitch coke powder material of siliceous substrates material made from step 3), obtains silicon
Carbon cathode material.
2. the preparation method of a kind of silicon-carbon cathode material according to claim 1, which is characterized in that described to contain nano-silicon
The slurry of powder or nano oxidized sub- silica flour is to evenly spread to nano silica fume or nano oxidized sub- silica flour in solvent with sand mill,
Percent weight solids level in slurry is 5~30wt%, the solvent is carbolic oil, washing oil, one kind in carbolineum or two kinds with
Upper arbitrary mixing.
A kind of 3. preparation method of silicon-carbon cathode material according to claim 1 or 2, which is characterized in that the nano-silicon
The grain size of powder or nano oxidized sub- silica flour is 500~700nm.
A kind of 4. preparation method of silicon-carbon cathode material according to claim 1, which is characterized in that the micron order graphite
Powder is the graphite material that grain size is 500~12000 μm, and graphite material is one or both of Delanium, native graphite
The mixture mixed in any proportion.
5. the preparation method of a kind of silicon-carbon cathode material according to claim 1, which is characterized in that will in the step 1)
It is mixed that slurry containing nano silica fume or nano oxidized sub- silica flour is mixed with micron order graphite powder, coal tar soft asphalt kneading
Pinch what is carried out in machine, kneading temperature is 30~70 DEG C, when the kneading time 2~5 is small.
6. the preparation method of a kind of silicon-carbon cathode material according to claim 1, which is characterized in that will in the step 2)
Mixture carry out coking be under nitrogen protection, by mixed material heating to 550~700 DEG C progress coking processing, coking handle when
Between for 5~8 it is small when, the graphite pitch for obtaining block siliceous substrates material is burnt.
7. the preparation method of a kind of silicon-carbon cathode material according to claim 1, which is characterized in that will in the step 3)
The graphite pitch coke powder of siliceous substrates material is broken to D50=5~20 μm.
A kind of 8. preparation method of silicon-carbon cathode material according to claim 1, which is characterized in that table in the step 4)
Face chemical vapor deposition process uses CVD method, and deposition charcoal temperature is 1000~1200 DEG C, when the deposition charcoal time is 1~10 small, carbon
Source gas body is one or more gas mixings in ethylene, propylene, acetylene and alkanes gas.
9. a kind of silicon-carbon cathode material, applied to lithium ion battery, which is characterized in that the silicon-carbon cathode material has core material
Dual cladding structure outside matter and core substance, wherein core substance are nano-silicon/nano oxidized sub- silicon particle and graphite particle
Homogeneous mixture, the external sheath structure in dual cladding structure is vapor deposition layer of charcoal, and internal layer clad structure is asphalt carbon
Layer.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes system described in claim 1-8 any one
Silicon-carbon cathode material made from Preparation Method.
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