CN109037636A - A kind of preparation method of SiO/ carbon graphite composite negative pole material - Google Patents
A kind of preparation method of SiO/ carbon graphite composite negative pole material Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/362—Composites
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The present invention provides a kind of preparation method of SiO/ carbon graphite composite negative pole material, the following steps are included: 1) press (1~5): 10 mass ratio weighs SiO and sanding media is placed in and is sanded in machine jar body, and be sanded after grinding aid mixing is added by SiO nanosizing, obtain SiO suspension；2) a certain amount of inorganic carbon source is added in the SiO suspension and is continued to be sanded to being uniformly dispersed, it takes out in machine jar body from being sanded and is uniformly mixed with the aqueous solution of a certain amount of organic carbon source, solution A is formed, then carries out spray drying granulation, obtains the SiO powder of carbon source cladding；3) the SiO powder that the carbon source coats is placed in the high-temperature calcination under the atmosphere of inert gas in tube furnace, then cooled to room temperature, obtains SiO/ carbon composite；4) the SiO/ carbon composite and graphite are weighed by the mass ratio of 10:100, and ball-milling medium is added and carries out ball milling, SiO/ carbon composite is taken out after mixing with graphite, SiO/ carbon graphite composite negative pole material is made.
Description
[technical field]
The invention belongs to electrode material field more particularly to a kind of preparation methods of SiO/ carbon graphite composite negative pole material.
[background technique]
The negative electrode material of lithium battery be the performances such as efficiency for charge-discharge, cycle life for determining lithium battery key factor it
One.Currently, commercialized lithium battery is mainly using graphite as negative electrode material, the specific capacity of high-end graphite material is had reached in the market
360-365mAh/g, close to the theoretical specific capacity (372mAh/g) of graphite, therefore using graphite as the lithium battery of negative electrode material
The room for promotion of energy density is limited, is unable to satisfy the requirement of power battery high-energy density.And silicon based anode material because its compared with
High theoretical specific capacity (high temperature 4200mAh/g, room temperature 3580mAh/g), lower de- lithium current potential (< 0.5V), environmental-friendly, storage
The advantages such as amount is abundant, cost is relatively low and be considered as great potential next-generation lithium ion battery with high energy density negative electrode material.
In silicon based anode material, SiO material with the volume in high capacity (2600mAh/g), cyclic process due to becoming
The lithia and lithium metasilicate for changing irreversible formation during being less than Si material, first charge-discharge can play buffering in cyclic process
Effect, and cycle performance is better than Si material, becomes one of the substitute products of commercialization graphite cathode.But SiO material is embedding
Biggish volume expansion can be generated during lithium, destroys conductive network, and dusting easily occurs for material in cyclic process, makes battery capacity
Rapid decay；And the intrinsic conductivity of SiO is far below graphite, and serious electrode polarization can be generated in high current charge-discharge；?
In charge and discharge process, since the generation of solid electrolyte interface film (SEI) constantly consumes Li+, coulombic efficiency is caused to reduce.
In the prior art, SiO material modification method mainly has: nanosizing and Composite.Nanosizing can alleviate volume
Expansion, while the diffusion velocity of Li+ can be improved and increase the contact area of electrode active material and electrolyte, make Li+ it is de-/
Embedding reaction carries out more abundant；But the large specific surface area of nano material, it prepares and needs to add a large amount of bonding in electrode process
Agent is unfavorable for improving battery performance, and preparation cost is higher.The research direction of Composite is mainly the amorphous carbon graphite of SiO/
Three-component compound system is absorbed the volume expansion of SiO as buffering matrix using graphite, then coats one layer by composite material surface
Conductivity height and the good material of compatibility of electrolyte, contact of the barrier material with electrolyte, to improve the conductivity of material and follow
Ring performance；But surface coats too thick amorphous carbon and can reduce the coulombic efficiency of material, while being unfavorable for improving adding for material
Work performance.
[summary of the invention]
The present invention proposes a kind of preparation method of SiO/ carbon graphite composite negative pole material, is used to prepare that expansion rate is small, conductance
Rate is high, homogeneity is good and the high silicon based anode material of coulombic efficiency for the first time.
To achieve the goals above, the present invention provides a kind of preparation method of SiO/ carbon graphite composite negative pole material, including
Following steps:
1) press (1~5): 10 mass ratio weighs SiO and sanding media is placed in and is sanded in machine jar body, and it is mixed that grinding aid is added
It is sanded after conjunction by SiO nanosizing, obtains SiO suspension；Wherein, the revolving speed of sand milling is 300~800r/min, and the time is sanded
For 5~20h；
2) a certain amount of inorganic carbon source is added in the SiO suspension and continues to be sanded to being uniformly dispersed, from sand mill tank
It takes out in body and is uniformly mixed with the aqueous solution of a certain amount of organic carbon source, form solution A, then carry out spray drying granulation, obtain
The SiO powder coated to carbon source；Wherein, the mass ratio of SiO and inorganic carbon source is 100:(1~20), SiO, inorganic carbon source and have
Machine carbon source accounts for the 10~20% of the solution A gross mass；
3) the SiO powder that the carbon source coats is placed in the high-temperature calcination under the atmosphere of inert gas in tube furnace, then certainly
It is so cooled to room temperature, obtains SiO/ carbon composite；
4) the SiO/ carbon composite and graphite are weighed by the mass ratio of 10:100, and ball-milling medium is added and carries out ball
Mill, SiO/ carbon composite is taken out after mixing with graphite, and SiO/ carbon graphite composite negative pole material is made.
In a preferred embodiment, in step 1), the granularity of the SiO is 300 mesh；The sanding media is zirconium
Pearl, the diameter of the zirconium pearl are 0.2mm；The grinding aid is alcohol, and the mass ratio of the grinding aid and SiO are (1~10): 1.
In a preferred embodiment, the inorganic carbon source is carbon nanotube, graphene, by vapour deposition process preparation
One or more of carbon nano-fiber；The organic carbon source is glucose, citric acid, pitch, polyvinylpyrrolidone, poly- second
One or more of glycol, sucrose, polyvinyl alcohol, polyacrylic acid, polyvinyl chloride, phenolic resin.
In a preferred embodiment, in step 2), the inlet temperature of spray drying device is 120~180 DEG C, outlet
Temperature is 80~120 DEG C, and flow velocity is 500~2000ml/h.
In a preferred embodiment, in step 2), the time of sand milling is 2h, the SiO, inorganic carbon source and organic carbon
Source accounts for the 20% of the solution A gross mass.
In a preferred embodiment, in step 3), the process of the high-temperature calcination is, first with 5~10 DEG C/min's
Rate is warming up to 600~800 DEG C, is then warming up to 950~1100 DEG C with the rate of 1~5 DEG C/min, then keep the temperature 1~4h.
In a preferred embodiment, the inert gas includes one or more of helium, argon gas and nitrogen.
In a preferred embodiment, in step 4), the quality of the ball-milling medium and the SiO/ carbon composite
Ratio with the mixing quality of graphite is (2~10): 1.
In a preferred embodiment, the ball-milling medium include diameter be respectively 5mm, 8mm, 10mm agate bead and
Corresponding mass ratio is 1.2:0.6:0.2.
In a preferred embodiment, in step 4), the revolving speed of ball milling is 100~300r/min, Ball-milling Time is 1~
5h。
Compared with prior art, the invention has the beneficial effects that:
(1) nanometer sand milling technology is first passed through by SiO nanosizing, and nanometer size effect can alleviate material in charge and discharge process
The structural stress variation that middle volume expansion generates, improves the structural stability of material；The reduction of material particle size can be shortened simultaneously
The diffusion path of Li+ improves the diffusion velocity of Li+, improves the big multiplying power discharging property of material；And the reduction of partial size increases material
The specific surface area of material increases the contact area of active material and electrolyte, so that de-/embedding reaction of Li+ is carried out more abundant, reduces
Electrode polarization；
(2) pass through liquid-phase C coating technology after the carbon material of SiO nano grain surface one layer of high conductivity of cladding, cladding
The second particle of formation is made of multiple SiO nano particles, and SiO nano particle is dispersed in carbon material, is effectively avoided
The reunion of SiO nanoparticle；And carbon coating can inhibit the volume expansion of SiO, the conductivity for improving material, barrier material and electricity
The contact of solution liquid improves the cycle performance of material to reduce the generation of SEI film；The second particle formed after cladding maintains
SiO nanoparticle activity reduces the specific surface area of material entirety simultaneously, avoids consuming in electrode production process a large amount of viscous
Agent is tied, the processing performance for improving material is conducive to；
(3) make amorphous Si O that disproportionated reaction occur by high-temperature calcination (being higher than 850 DEG C), generate well-distributed nanometer
Si crystallite and unbodied SiO2, can to avoid material the embedding lithium in part and lead to material dusting, improve the stable structure of material
Property；
(4) SiO/ carbon composite and graphite progress is compound, graphite particle can be SiO material in charge and discharge process
Volume expansion provide buffering matrix, to improve the stability of electrode entirety.
In conclusion SiO/ carbon graphite composite negative pole material expansion rate prepared by the present invention is small, conductivity is high, homogeneity
It is good, and coulombic efficiency is high for the first time, has good cyclical stability.
[Detailed description of the invention]
Fig. 1 is the flow chart of the preparation method of SiO/ carbon graphite composite negative pole material provided by the invention.
Fig. 2 is that the SiO/ carbon graphite that the preparation method of SiO/ carbon graphite composite negative pole material provided by the invention obtains is multiple
Close the SEM figure of negative electrode material.
Fig. 3 is what the preparation method of SiO/ carbon graphite composite negative pole material provided by the invention was obtained according to embodiment 2
SiO/ carbon graphite composite negative pole material under 0.1C multiplying power before charging and discharging curve twice.
Fig. 4 is what the preparation method of SiO/ carbon graphite composite negative pole material provided by the invention was obtained according to embodiment 2
100 charging cycle curves of the SiO/ carbon graphite composite negative pole material under 0.1C multiplying power.
[specific embodiment]
Referring to Fig. 1, the present invention provides a kind of preparation method of SiO/ carbon graphite composite negative pole material, including following step
It is rapid:
1) nanosizing: press (1~5): 10 mass ratio weighs SiO and sanding media is placed in and is sanded in machine jar body, and is added
It is sanded after grinding aid mixing by SiO nanosizing, obtains SiO suspension；Wherein, the revolving speed of sand milling is 300~800r/min,
The sand milling time is 5~20h.In this step, the grinding aid is alcohol, and the mass ratio of the grinding aid and SiO are (1~10):
1。
2) carbon coating: a certain amount of inorganic carbon source is added in the SiO suspension and continues to be sanded to being uniformly dispersed, from sand
It takes out in grinding machine tank body and is uniformly mixed with the aqueous solution of a certain amount of organic carbon source, form solution A, then carry out spray drying and make
Grain obtains the SiO powder of carbon source cladding；Wherein, SiO and the mass ratio of inorganic carbon source are 100:(1~20), SiO, inorganic carbon source
And organic carbon source accounts for the 10~20% of the solution A gross mass.In this step, the inorganic carbon source be carbon nanotube, graphene,
By one or more of the carbon nano-fiber of vapour deposition process preparation；The organic carbon source be glucose, citric acid, pitch,
One of polyvinylpyrrolidone, polyethylene glycol, sucrose, polyvinyl alcohol, polyacrylic acid, polyvinyl chloride, phenolic resin are several
Kind；The inlet temperature of spray drying device is 120~180 DEG C, and outlet temperature is 80~120 DEG C, and flow velocity is 500~2000ml/
h。
3) it is disproportionated: the SiO powder that the carbon source coats is placed in the high-temperature calcination under the atmosphere of inert gas in tube furnace,
Cooled to room temperature again obtains SiO/ carbon composite.In this step, the inert gas includes helium, argon gas and nitrogen
One or more of.The process of the high-temperature calcination is first to be warming up to 600~800 DEG C with the rate of 5~10 DEG C/min, so
950~1100 DEG C are warming up to the rate of 1~5 DEG C/min afterwards, then keeps the temperature 1~4h.
4) graphite is compound: weighing the SiO/ carbon composite and graphite by the mass ratio of 10:100, and ball milling Jie is added
Matter carries out ball milling, and SiO/ carbon composite is taken out after mixing with graphite, and SiO/ carbon graphite composite negative pole material is made.
In this step, the ratio of the mixing quality of the quality of the ball-milling medium and the SiO/ carbon composite and graphite be (2~
10):1；The revolving speed of ball milling is 100~300r/min, and Ball-milling Time is 1~5h.Preferably, the ball-milling medium includes diameter point
Not Wei 5mm, 8mm, 10mm agate bead and corresponding mass ratio be 1.2:0.6:0.2.
SiO/ carbon graphite composite negative pole material pattern prepared by the present invention is spherical in shape, as shown in Figure 2.
Embodiment 1
By the mass ratio of 1:10 weigh 300 mesh SiO and as sanding media diameter be 0.2mm zirconium pearl be placed in sand milling
It in machine jar body, and is sanded after the mixing of grinding aid alcohol is added by SiO nanosizing, obtains SiO suspension.Wherein, SiO and wine
The mass ratio of essence is 1:2, and the revolving speed of sand milling is 500r/min, and the sand milling time is 10h.
Carbon nanotube is added in above-mentioned SiO suspension and continues to be sanded about 2h to being uniformly dispersed, is taken from being sanded in machine jar body
It is uniformly mixed out and with aqueous citric acid solution, forms solution A, then carry out spray drying granulation, obtain the SiO powder of carbon source cladding
Body.Wherein, SiO and the mass ratio of carbon nanotube are 100:10, and SiO, carbon nanotube and citric acid account for the solution A gross mass
20%；The inlet temperature of spray drying device is 160 DEG C, and outlet temperature is 120 DEG C, flow velocity 800ml/h.
The SiO powder that above-mentioned carbon source coats is placed in the high-temperature calcination under the atmosphere of nitrogen in tube furnace, with 5 DEG C/min's
Rate is warming up to 750 DEG C, is then warming up to 950 DEG C with the rate of 2 DEG C/min, after keeping the temperature 2h, then cooled to room temperature, it obtains
SiO/ carbon composite.
The SiO/ carbon composite and graphite are weighed by the mass ratio of 10:100, by the quality and SiO/ carbon of ball-milling medium
The ratio of the mixing quality of composite material and graphite is that ball-milling medium progress ball milling is added in 5:1, and ball-milling medium is agate bead (diameter
For 5mm, 8mm, 10mm and corresponding mass ratio is 1.2:0.6:0.2), the revolving speed of ball milling is 150r/min, Ball-milling Time 2h,
SiO/ carbon composite is taken out after mixing with graphite, SiO/ carbon graphite composite negative pole material is made.
Embodiment 2
By the mass ratio of 1:10 weigh 300 mesh SiO and as sanding media diameter be 0.2mm zirconium pearl be placed in sand milling
It in machine jar body, and is sanded after the mixing of grinding aid alcohol is added by SiO nanosizing, obtains SiO suspension.Wherein, SiO and wine
The mass ratio of essence is 1:2, and the revolving speed of sand milling is 500r/min, and the sand milling time is 10h.
Graphene is added in above-mentioned SiO suspension and continues to be sanded about 2h to being uniformly dispersed, is taken out from being sanded in machine jar body
And be uniformly mixed with glucose solution, solution A is formed, then carry out spray drying granulation, obtains the SiO powder of carbon source cladding.
Wherein, the mass ratio of SiO and graphene is 100:10, and SiO, graphene and glucose account for the 20% of the solution A gross mass；Spray
The inlet temperature of mist drying equipment is 150 DEG C, and outlet temperature is 90 DEG C, flow velocity 600ml/h.
The SiO powder that above-mentioned carbon source coats is placed in the high-temperature calcination under the atmosphere of nitrogen in tube furnace, with 5 DEG C/min's
Rate is warming up to 800 DEG C, is then warming up to 1000 DEG C with the rate of 1 DEG C/min, after keeping the temperature 1h, then cooled to room temperature, it obtains
To SiO/ carbon composite.
The SiO/ carbon composite and graphite are weighed by the mass ratio of 10:100, by the quality and SiO/ carbon of ball-milling medium
The ratio of the mixing quality of composite material and graphite is that ball-milling medium progress ball milling is added in 5:1, and ball-milling medium is agate bead (diameter
For 5mm, 8mm, 10mm and corresponding mass ratio is 1.2:0.6:0.2), the revolving speed of ball milling is 200r/min, Ball-milling Time 2h,
SiO/ carbon composite is taken out after mixing with graphite, SiO/ carbon graphite composite negative pole material is made.
Embodiment 3
By the mass ratio of 1:10 weigh 300 mesh SiO and as sanding media diameter be 0.2mm zirconium pearl be placed in sand milling
It in machine jar body, and is sanded after the mixing of grinding aid alcohol is added by SiO nanosizing, obtains SiO suspension.Wherein, SiO and wine
The mass ratio of essence is 1:2, and the revolving speed of sand milling is 500r/min, and the sand milling time is 10h.
The carbon nano-fiber prepared by vapour deposition process is added in above-mentioned SiO suspension and continues to be sanded about 2h extremely dispersion
It is even, it takes out in machine jar body from being sanded and is uniformly mixed with aqueous povidone solution, form solution A, then done by spraying
Dry granulation obtains the SiO powder of carbon source cladding.Wherein, the mass ratio of SiO and carbon nano-fiber is 100:10, SiO, nano-sized carbon
Fiber and polyvinylpyrrolidone account for the 20% of the solution A gross mass；The inlet temperature of spray drying device is 150 DEG C, out
Mouth temperature is 100 DEG C, flow velocity 1000ml/h.
The SiO powder that above-mentioned carbon source coats is placed in the high-temperature calcination under the atmosphere of nitrogen in tube furnace, with 10 DEG C/min
Rate be warming up to 850 DEG C, be then warming up to 1050 DEG C with the rate of 2 DEG C/min, after keeping the temperature 1h, then cooled to room temperature,
Obtain SiO/ carbon composite.
The SiO/ carbon composite and graphite are weighed by the mass ratio of 10:100, by the quality and SiO/ carbon of ball-milling medium
The ratio of the mixing quality of composite material and graphite is that ball-milling medium progress ball milling is added in 5:1, and ball-milling medium is agate bead (diameter
For 5mm, 8mm, 10mm and corresponding mass ratio is 1.2:0.6:0.2), the revolving speed of ball milling is 150r/min, Ball-milling Time 5h,
SiO/ carbon composite is taken out after mixing with graphite, SiO/ carbon graphite composite negative pole material is made.
Embodiment 4
By the mass ratio of 1:10 weigh 300 mesh SiO and as sanding media diameter be 0.2mm zirconium pearl be placed in sand milling
It in machine jar body, and is sanded after the mixing of grinding aid alcohol is added by SiO nanosizing, obtains SiO suspension.Wherein, SiO and wine
The mass ratio of essence is 1:2, and the revolving speed of sand milling is 500r/min, and the sand milling time is 10h.
Carbon nanotube is added in above-mentioned SiO suspension and continues to be sanded about 2h to being uniformly dispersed, is taken from being sanded in machine jar body
It is uniformly mixed out and with glucose solution, forms solution A, then carry out spray drying granulation, obtain the SiO powder of carbon source cladding
Body.Wherein, SiO and the mass ratio of carbon nanotube are 100:10, and SiO, carbon nanotube and glucose account for the solution A gross mass
20%；The inlet temperature of spray drying device is 150 DEG C, and outlet temperature is 90 DEG C, flow velocity 600ml/h.
The SiO powder that above-mentioned carbon source coats is placed in the high-temperature calcination under the atmosphere of nitrogen in tube furnace, with 5 DEG C/min's
Rate is warming up to 800 DEG C, is then warming up to 1000 DEG C with the rate of 1 DEG C/min, after keeping the temperature 1h, then cooled to room temperature, it obtains
To SiO/ carbon composite.
The SiO/ carbon composite and graphite are weighed by the mass ratio of 10:100, by the quality and SiO/ carbon of ball-milling medium
The ratio of the mixing quality of composite material and graphite is that ball-milling medium progress ball milling is added in 5:1, and ball-milling medium is agate bead (diameter
For 5mm, 8mm, 10mm and corresponding mass ratio is 1.2:0.6:0.2), the revolving speed of ball milling is 200r/min, Ball-milling Time 2h,
SiO/ carbon composite is taken out after mixing with graphite, SiO/ carbon graphite composite negative pole material is made.
Further, preparation, the button of pole piece are carried out to SiO/ carbon graphite composite negative pole material made from Examples 1 to 4
The assembling of battery and electrochemical property test.Specific steps are as follows: the SiO/ carbon graphite composite negative pole as made from Examples 1 to 4
Material is mixed with conductive carbon black, sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR) 91:5:1.6:2.4 in mass ratio, is added
Deionized water is stirred as solvent；After mixing evenly, it is spread evenly across in copper foil current collector using coating apparatus, at 90 DEG C
It is toasted in vacuum oven for 24 hours, is then suppressed uniformly by twin rollers, the round pole that diameter is 14mm finally is made with sheet-punching machine
Piece；It is again to electrode with metal lithium sheet, diaphragm is polypropylene screen (Celgard 2300), and electrolyte is 1mol/L lithium hexafluoro phosphate
With the mixed solution of the ethylene carbonate of isometric ratio, dimethyl carbonic ether, the group in the vacuum glove box full of high pure nitrogen
2025 button cells are dressed up, electrochemical property test is carried out, test result is as shown in table 1.With 0.1C multiplying power, (1C is pressed when test
450mAh/g meter) charge and discharge cycles are carried out, voltage range is 0~2V, and cycle-index is 100 times.
1 performance test table of table
The SiO/ carbon graphite composite negative pole material being prepared it can be seen from data in table 1 by Examples 1 to 4 has
There are higher coulombic efficiency for the first time and good cyclical stability.It should be noted that using embodiment 2 obtain SiO/ carbon/
The preceding charging and discharging curve twice and 100 charging cycle curves of the button cell of composite cathode material of silicon/carbon/graphite preparation are respectively such as Fig. 3
And shown in Fig. 4.The button of the SiO/ carbon graphite composite negative pole material preparation obtained it can be seen from Fig. 3 and Fig. 4 by embodiment 2
Battery has good cyclical stability, the coulombic efficiency still with higher after 100 circulations.
The present invention, by SiO appropriateness nanosizing, is added inorganic carbon source and is sanded, improve inorganic carbon source by sand-blast
Dispersibility；The carbon material of one layer of high conductivity is coated in SiO nano grain surface by liquid-phase C coating technology, is formed after cladding
Second particle be made of multiple SiO nano particles, SiO nano particle is dispersed in carbon material, avoids SiO nanometers
The reunion of particle reduces the specific surface area of material entirety while keeping SiO nanoparticle activity, electrode is avoided to prepare
A large amount of binders are consumed in journey, improve the processing performance of material；Make SiO that disproportionated reaction occur by high-temperature heat treatment, generates and divide
The good nano Si crystallite of cloth and amorphous Si O2, can avoid the embedding lithium in part of material and lead to material dusting, improve material
Structural stability.In conclusion the preparation method of SiO/ carbon graphite composite negative pole material provided by the present invention is obtained
SiO/ carbon graphite composite negative pole material expansion rate is small, conductivity is high, homogeneity is good, and coulombic efficiency is high for the first time, has good
Cyclical stability.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is to combine specific preferred embodiment to institute of the present invention
The further description of work is, and it cannot be said that specific implementation of the invention is confined to these explanations.It is all in spirit of the invention and
Made any modifications, equivalent replacements, and improvements etc., should be included within the scope of the present invention within principle.
Claims (10)
1. a kind of preparation method of SiO/ carbon graphite composite negative pole material, which comprises the following steps:
1) press (1~5): 10 mass ratio weighs SiO and sanding media is placed in and is sanded in machine jar body, and after grinding aid mixing is added
It is sanded SiO nanosizing, obtains SiO suspension；Wherein, the revolving speed of sand milling is 300~800r/min, and it is 5 that the time, which is sanded,
~20h；
2) a certain amount of inorganic carbon source is added in the SiO suspension and is continued to be sanded to being uniformly dispersed, from being sanded in machine jar body
It takes out and is uniformly mixed with the aqueous solution of a certain amount of organic carbon source, form solution A, then carry out spray drying granulation, obtain carbon
The SiO powder of source cladding；Wherein, SiO and the mass ratio of inorganic carbon source are 100:(1~20), SiO, inorganic carbon source and organic carbon
Source accounts for the 10~20% of the solution A gross mass；
3) the SiO powder that the carbon source coats is placed in the high-temperature calcination under the atmosphere of inert gas in tube furnace, then naturally cold
But to room temperature, SiO/ carbon composite is obtained；
4) the SiO/ carbon composite and graphite are weighed by the mass ratio of 10:100, and ball-milling medium is added and carries out ball milling, it will
SiO/ carbon composite takes out after mixing with graphite, and SiO/ carbon graphite composite negative pole material is made.
2. the preparation method of SiO/ carbon graphite composite negative pole material as described in claim 1, it is characterised in that: in step 1),
The granularity of the SiO is 300 mesh；The sanding media is zirconium pearl, and the diameter of the zirconium pearl is 0.2mm；The grinding aid is wine
The mass ratio of essence, the grinding aid and SiO are (1~10): 1.
3. the preparation method of SiO/ carbon graphite composite negative pole material as described in claim 1, it is characterised in that: described inorganic
Carbon source is carbon nanotube, graphene, by one or more of carbon nano-fiber of vapour deposition process preparation；The organic carbon source
For glucose, citric acid, pitch, polyvinylpyrrolidone, polyethylene glycol, sucrose, polyvinyl alcohol, polyacrylic acid, polyvinyl chloride,
One or more of phenolic resin.
4. the preparation method of SiO/ carbon graphite composite negative pole material as described in claim 1, it is characterised in that: in step 2),
The inlet temperature of spray drying device is 120~180 DEG C, and outlet temperature is 80~120 DEG C, and flow velocity is 500~2000ml/h.
5. the preparation method of SiO/ carbon graphite composite negative pole material as described in claim 1, it is characterised in that: in step 2),
The time of sand milling is 2h, and the SiO, inorganic carbon source and organic carbon source account for the 20% of the solution A gross mass.
6. the preparation method of SiO/ carbon graphite composite negative pole material as described in claim 1, it is characterised in that: in step 3),
The process of the high-temperature calcination is first 600~800 DEG C to be warming up to the rate of 5~10 DEG C/min, then with 1~5 DEG C/min's
Rate is warming up to 950~1100 DEG C, then keeps the temperature 1~4h.
7. the preparation method of SiO/ carbon graphite composite negative pole material as described in claim 1, it is characterised in that: the inertia
Gas includes one or more of helium, argon gas and nitrogen.
8. the preparation method of SiO/ carbon graphite composite negative pole material as described in claim 1, it is characterised in that: in step 4),
The ratio of the mixing quality of the quality of the ball-milling medium and the SiO/ carbon composite and graphite is (2~10): 1.
9. the preparation method of SiO/ carbon graphite composite negative pole material as claimed in claim 8, it is characterised in that: the ball milling
Medium include diameter be respectively 5mm, 8mm, 10mm agate bead and corresponding mass ratio be 1.2:0.6:0.2.
10. the preparation method of SiO/ carbon graphite composite negative pole material as described in claim 1, it is characterised in that: step 4)
In, the revolving speed of ball milling is 100~300r/min, and Ball-milling Time is 1~5h.
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