CN109713285A - A kind of silicon-carbon composite cathode material and preparation method thereof - Google Patents
A kind of silicon-carbon composite cathode material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of silicon-carbon composite cathode material, the nano-silicon prepared using CVD method, then nano-silicon is added in the DMF solution of polyacrylonitrile, electrostatic spinning is carried out in the electric field, obtain silicon-carbon composite fibre, silicon-carbon composite fibre, natural spherical plumbago and pitch are dissolved in solvent and are dispersed with stirring, spray pyrolysis is then carried out, high capacity Si-C composite material is made.The method of the present invention equipment is simple, easy to operate, has preferable prospects for commercial application.Silicon-carbon composite cathode material prepared by the present invention has very outstanding chemical property.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of silicon-carbon composite cathode material of lithium ion battery,
Preparation method.
Background technique
Performance of lithium ion battery is superior, widely used, has a extensive future, opposite with traditional lead-acid battery, nickel-cadmium cell and
The secondary cells such as nickel-metal hydride battery, lithium ion battery have energy density is high, open-circuit voltage is high, have extended cycle life, self-discharge rate is small,
The clear superiorities such as memory-less effect and green non-pollution.Lithium ion battery is with the continuous progress of technology in people's lives
In be widely used, such as portable electronic product, new energy vehicles field.However, the matter of lithium ion battery
It measures specific capacity (Whkg-1) and energy density per unit volume (WhL-1) needs further raising, to meet portable electronic product
Miniaturization and its requirement applied in terms of space flight, military affairs, peak load regulation network and electric car.Therefore, height ratio capacity and height are researched and developed
The lithium ion battery material of specific energy oneself become the very important research topic of current research work.
Silicon can form alloy with lithium, be up to 3675mAh/g as specific capacity of negative electrode material of lithium ion battery, be equivalent to
It is commercialized more than ten times of graphitic carbon capacity (372 mAhg-1).However silicon volume change during lithium ion deintercalation it is big (>
300%) electrical contact of the dusting and silicon and collector that cause electrode is reduced, and cause electric conductivity to be deteriorated reduces with the utilization rate of silicon.This
The features such as a little factors lead to the higher irreversible capacity of silica-base material and poor cyclical stability.In recent years, silica-base material is being improved
Chemical property in terms of obtain apparent progress, alleviated by preparing nano structural material, composite material and porous material
Volume change in cyclic process simultaneously improves its electric conductivity.
Polyacrylonitrile (PAN) solution of Li et al. incorporation nano-silicon particle is subjected to electrostatic spinning after oxidation carbonization and obtains silicon
Particle is embedded in the carbon nano-fiber in carbon base body, and using this as the negative electrode material for lithium ion battery, first capacity is reachable
1000mAh/g, after 50 times recycle, capacity attenuation to 700mAh/g is hereinafter, be primarily due in carbon base body not to the expansion of silicon
Cushion space is reserved, the raising of material circulation performance is limited；And apparent reunion, a large amount of silicon grain has occurred in silicon particle
Son is exposed on the surface of carbon nano-fiber.
Summary of the invention
The purpose of the invention is to overcome the deficiencies of the prior art and provide a kind of new porous silicon-carbon composite cathode material
And preparation method thereof.
The present invention is achieved by the following technical programs:
A kind of preparation method of silicon-carbon composite cathode material, which comprises the following steps:
A1, CVD method prepare nano-silicon: under nitrogen protection, silane gas being passed into reacting furnace, heating sends out silane gas
Heat is decomposed, and is then passed to carbon-source gas and is carried out carbon coating, finally cooled to room temperature under nitrogen protection, collects reacting furnace
Powder in burner hearth；
A2, electrostatic spinning prepare complex fiber material: the obtained powder of step A1 be added in the DMF solution of polyacrylonitrile,
Electrostatic spinning is carried out in the electric field, obtains the polyacrylonitrile fibre membrane of nano silicon particles, then polyacrylonitrile fibre membrane drying is gone
Except solvent, then polyacrylonitrile fibre membrane is placed in tube furnace and carries out pre-oxidation treatment, carries out carbon again after pre-oxidation treatment
Change processing, obtains silicon-carbon complex fiber material；
A3, granulation: natural spherical plumbago is dissolved in solvent, and silicon-carbon complex fiber material and the drip of step A2 preparation is then added
Blueness is dispersed with stirring, and then carries out spray pyrolysis, collects pyrolysis product, then carry out carbonization treatment under nitrogen protection, obtains silicon-carbon
Composite precursor；
A4, CVD cladding: silicon-carbon composite precursor prepared by step A3 is placed in the tube furnace with nitrogen and is heated, so
After be passed through carbon-source gas and coated, carried out after cladding it is cooling, be sieved, obtain silicon-carbon composite cathode material.
Further, a kind of preparation method of silicon-carbon composite cathode material, which comprises the following steps:
A1, silane gas thermal cvd prepare nano-silicon: under nitrogen protection, silane gas being passed into reacting furnace, reacting furnace
Temperature is controlled at 750-950 DEG C, thermally decomposes silane gas, is then passed to carbon-source gas and is carried out carbon coating, finally in nitrogen
Cooled to room temperature under gas shielded collects the powder in reacting furnace burner hearth；
A2, electrostatic spinning prepare complex fiber material: the obtained powder of step A1 be added in the DMF solution of polyacrylonitrile,
Electrostatic spinning is carried out in the electric field that electric field strength is 55-75KV/m, obtains the polyacrylonitrile fibre membrane of nano silicon particles, then will
Polyacrylonitrile fibre membrane, is then placed in tube furnace and carries out pre-oxidation treatment by polyacrylonitrile fibre membrane drying removal solvent,
Carbonization treatment is carried out after pre-oxidation treatment again, obtains silicon-carbon complex fiber material；
A3, granulation: natural spherical plumbago is dissolved in solvent, the silicon-carbon complex fiber material of step A2 preparation is then added, most
After pitch is added, be dispersed with stirring, then carry out spray pyrolysis, collect pyrolysis product, then carry out carbonization treatment under nitrogen protection,
Obtain silicon-carbon composite precursor.
A4, CVD cladding: silicon-carbon composite precursor prepared by step A3 is placed in the tube furnace with inert protective atmosphere,
It is heated to 900-1000 DEG C, carbon-source gas is then passed through with 1.0-2.0 L/min flow velocity, continues 8-15min, is taken out after cooling down
Sieving, obtains silicon-carbon composite cathode material.
Further, a kind of preparation method of silicon-carbon composite cathode material, which comprises the following steps:
A1, silane gas thermal cvd prepare nano-silicon: under nitrogen protection, by purity be 99.99% silane gas with 1.0-
The low flow velocity of 2.0 L/min is passed into reacting furnace, and reacting furnace temperature is controlled at 750-950 DEG C, makes silane gas that heat point occur
Solution is passed through carbon-source gas with 1.0-2.0 L/min low flow velocity and carries out carbon coating, the time of carbon coating is 6- after twenty minutes
10min, finally system cooled to room temperature under nitrogen protection, collects the powder in reacting furnace burner hearth；
A2, electrostatic spinning prepare complex fiber material: the step A1 powder collected be added in the DMF solution of polyacrylonitrile,
Then electrostatic spinning is carried out in the electric field that electric field strength is 55-75KV/m, obtains the polyacrylonitrile fibre membrane of nano silicon particles,
Polyacrylonitrile fibre membrane is dried to removal solvent under 60-80 DEG C of vacuum condition again, polyacrylonitrile fibre membrane is then placed in pipe
Pre-oxidation treatment is carried out in formula furnace, the pre-oxidation treatment is warming up to 230-300 DEG C with 3-5 DEG C/min rate, keeps 2-3h, moves back
Fire is cooling, then carries out carbonization treatment, obtains silicon-carbon complex fiber material；
A3, granulation: the granular size D50 natural spherical plumbago for being 10-15 μm being dissolved in solvent, 10-30min is dispersed with stirring,
Then the silicon-carbon complex fiber material of step A2 preparation is added, disperses 30-40min, is eventually adding pitch, disperses 20-40min,
Then spray pyrolysis is carried out, collects pyrolysis product, then carry out carbonization treatment under nitrogen protection, the temperature of carbonization treatment is 800-
950 DEG C, room temperature is cooled to after carbonization treatment, re-sieving obtains silicon-carbon composite precursor.
A4, CVD cladding: silicon-carbon composite precursor prepared by step A3 being placed in tube furnace, high pure nitrogen deoxygenation is passed through,
After oxygen content is lower than 200ppm, it is heated to 900-1000 DEG C with the rate of heat addition of 3-5 DEG C/min, then with 1.0-2.0 L/min
Flow velocity be passed through carbon-source gas, continue 8-15min, then cool to room temperature, take out sieving, obtain silicon-carbon composite cathode material.
Preferably, the carbon-source gas is one of methane, acetylene, ethylene, ethane or a variety of.
Preferably, in step A2, the powder and polyacrylonitrile/DMF solution mass ratio are 1:5-11, the polypropylene
Contain polyacrylonitrile 3.40-4.50 wt% in nitrile/DMF solution.
Preferably, in step A2, the temperature of the carbonization treatment is 850-950 DEG C, and heating rate is 3-5 DEG C/min, is reached
2-3h is kept the temperature when to 850-950 DEG C, the carbonization treatment is carried out under inert protective atmosphere.
Preferably, the inert protective atmosphere is helium or argon gas.
Preferably, in step A3, the solvent is one of ethylene glycol, methanol, ethyl alcohol, isopropanol or a variety of.
The invention has the following advantages that
CVD method of the present invention prepares nano-silicon, simple process, and outsourcing carbon-coating alleviates the bulk effect of silicon, enhances its electric conductivity, resistance
The only reunion of small nano silicon particles improves the stability of material.
Nano silicon particles are embedded into carbon fiber by the present invention using method of electrostatic spinning, and the silicon being prepared/carbon nanometer is multiple
Condensating fiber not only have preferable chemical property and also can directly as lithium ion battery cathode and not have to addition additional
Conductive agent and adhesive, simplify the preparation process of battery.
The silicon that the present invention is prepared using method of electrostatic spinning/carbon nano-composite fiber usually has the size of very little and straight
Diameter, and specific surface area is higher, fiber is evenly distributed, good gap structure energy buffer volumes expansion can also be formed between fiber, therefore
And the electrode material prepared by this method has very outstanding chemical property.
Negative electrode material outermost clad prepared by the present invention, which can be effectively prevented silicon particle and fall off from electrode body, to be made
At electrical contact loss, improve the mechanical stability of electrode material, additionally it is possible to significantly improve the electric conductivity of material.
The advantages of spray pyrolysis of the present invention is with respect to other granulating techniques are as follows: process is simply rapid, is easy to control, and obtains
Product be generally spheric granules.Using graphite as core, organic carbon source is binder, and Si-CNFs is as conductive agent, with mist projection granulating
Mode be prepared for high capacity Si-C composite material.One layer of agraphitic carbon is coated with CVD again, greatly improves silicon-carbon composite wood
The first effect of material.
The experimental results showed that the half-cell that high capacity Si-C composite material provided by the invention is assembled into has excellent electricity
Chemical property, first discharge specific capacity is 1400mAh/g or more, after first charge-discharge coulombic efficiency is 80% or more, 300 weeks
Capacity retention ratio is greater than 85%.The present invention solves silicon can generate about 300% volume expansion contraction during embedding de- lithium, huge
Volume change will cause the dusting of silicon electrode and peel off, make to lose electrical contact between silicon particle and between silicon and collector, it is electric
The specific capacity of pole sharply declines even entirely ineffective problem.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of porous silicon-carbon composite cathode material prepared by the present invention.
Fig. 2 is that porous silicon-carbon composite cathode material prepared by the present invention recycles 200 circle appearances after being prepared into lithium ion battery
Measure conservation rate schematic diagram.
Fig. 3 is the structural schematic diagram of porous silicon-carbon composite cathode material prepared by the present invention.
In attached drawing, 1-carbon coating layer, 2-nanocrystal silicon dioxide layers, 3-etching after remaining silicon, 4-etching after
The hole of generation.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Embodiment 1
It purges reacting furnace repeatedly with high pure nitrogen and vacuumizes, it is ensured that the safety of system, by high purity silane gas
(99.99%) it is flowed, and remained unchanged with the low flow velocity of 2.0 L/min, thermally decomposed silane at 950 DEG C, adopt after twenty minutes
With high purity acetylene (C2H2) gas is passed through in same furnace, carbon is carried out with the flow of 2.0 L/min at 950 DEG C and coats 6min, finally
System cooled to room temperature under nitrogen protection collects burner hearth powder S1.
S1 is taken to be added in the DMF solution of the polyacrylonitrile of mass fraction 3.40% (mass ratio of S1 and solution is 1:5),
With electrostatic spinning technique, (electrostatic spinning is the molding process of effect of polymer solution or solution by electrostatic field, works as band
The electric field force of the polymer solution of charge overcomes surface tension, when being squeezed out from spinning head, solvent flash evapn, and polymer solidification,
Form nanofiber) mixed solution is subjected to electrospinning in electric field strength 55KV/m electric field.The polypropylene of gained nano silicon particles
Nitrile tunica fibrosa is dried under 60 DEG C of vacuum conditions except solvent.It is subsequently placed in tube furnace and is pre-oxidized that (room temperature, rises by 3 DEG C/min
Temperature is to 230 DEG C of holding 2h)；And carbonization treatment after annealing cooling, (room temperature, 3 DEG C/min are warming up to 850 DEG C of heat preservation 2h, N2 gas
Atmosphere) the cooling taking-up of annealing, obtain silicon-carbon composite fibre Si-CNFs.
By granular size D50 be 10 μm natural spherical plumbago, sucrose, silicon-carbon composite fibre Si-CNFs is according to mass ratio
4:3:2 is added sequentially to be mixed in solvent, and solvent uses ethylene glycol.Natural graphite is first added to be dissolved in ethylene glycol, uses
It is high-power to be dispersed with stirring 10min, stirring frequency 1500Hz, silicon-carbon composite fibre Si-CNFs is added, disperses 30min, finally
Pitch is added, disperses 20min.Then spray pyrolysis is carried out, pyrolysis product is collected, using 800 DEG C of carbonization (N2Atmosphere protection
Under), it is cooled to room temperature re-sieving and obtains SGP-1(D50:12 μm of product silicon-carbon composite precursor).
Silicon-carbon composite precursor SGP-1 product is placed in tube furnace and (prepares nano-silicon equipment), high pure nitrogen row is passed through
Oxygen carries out in next step, being heated to 900 DEG C with the rate of heat addition of 4 DEG C/min after oxygen content is lower than 200ppm, at 900 DEG C, with
1.0 L/min flow velocitys are passed through high purity acetylene (C2H2) gas, continue 10min, sieving is taken out after cooling down, obtains finished product silicon-carbon
SGP-2(D50:20 μm of composite material).
Embodiment 2
It purges reacting furnace repeatedly with high pure nitrogen and vacuumizes, it is ensured that the safety of system, by high purity silane gas
(99.99%) it is flowed, and remained unchanged with the low flow velocity of 1.0 L/min, thermally decomposed at 750 DEG C using silane, after twenty minutes
Using high purity acetylene (C2H2) gas in same furnace, carries out carbon at 750 DEG C with the flow of 2.0 L/min and coat 10min,
Last system cooled to room temperature under nitrogen protection, collects burner hearth powder S1.
S1 is taken to be added in the DMF solution of 4.50% polyacrylonitrile (mass ratio of S1 and solution is 1:11), with electrostatic
Mixed solution is carried out electrospinning in electric field strength 75KV/m electric field by spining technology.The polyacrylonitrile fibre of gained nano silicon particles
Film is dried under 80 DEG C of vacuum conditions except solvent.It is subsequently placed in tube furnace and is pre-oxidized that (room temperature, is warming up to by 5 DEG C/min
300 DEG C of holding 3h)；And carbonization treatment (room temperature, 5 DEG C/min are warming up to 950 DEG C of heat preservation 3h, N2 atmosphere) after annealing cooling, it moves back
Fire is cooling to be taken out, and Si-CNFs is obtained.
Natural spherical plumbago (D50:15 μm), glucose, Si-CNFs are got out according to mass ratio 5:4:2.First by natural stone
Ink is dissolved in ethylene glycol, is dispersed with stirring using high-power, stirring frequency 1000Hz, is dispersed with stirring 30min, and Si-CNFs is added,
Disperse 40min, be eventually adding pitch, disperses 40min.Then spray pyrolysis is carried out, pyrolysis product is collected, using 950 DEG C of carbon
Change (N2Atmosphere), be cooled to room temperature re-sieving and obtain SGP-1(D50:30 μm of product).
SGP-1 product is placed in tube furnace, high pure nitrogen deoxygenation is passed through, is carried out after oxygen content is lower than 200ppm next
Step, is heated to 1000 DEG C with the rate of heat addition of 3 DEG C/min, at 1000 DEG C, is passed through high purity acetylene with 2.0 L/min flow velocitys
(C2H2) gas, continue 8min, sieving taken out after cooling down, obtains SGP-2(D50:50 μm of finished product Si-C composite material).
Embodiment 3
It purges experimental system repeatedly with high pure nitrogen and vacuumizes, it is ensured that the safety of system, by high purity silane gas
(99.99%) it is flowed, and remained unchanged with the low flow velocity of 1.5 L/min, thermally decomposed at 800 DEG C using silane, after twenty minutes
Using high purity acetylene (C2H2) gas is in same furnace, with the flow progress carbon coating 7min of 2.0 L/min at 800 DEG C, finally
System cooled to room temperature under nitrogen protection collects burner hearth powder S1.
Taking S1 to be added in the dimethylformamide (DMF) solution of 3.40% polyacrylonitrile, (mass ratio of S1 and solution is
1:9), mixed solution is subjected to electrospinning in electric field strength 55KV/m electric field with electrostatic spinning technique.Gained nano silicon particles
Polyacrylonitrile fibre membrane dried under 60 DEG C of vacuum conditions except solvent.Be subsequently placed in tube furnace and pre-oxidized (room temperature, 3
DEG C/min, it is warming up to 260 DEG C of holding 2h)；And carbonization treatment after annealing cooling, (room temperature, 3 DEG C/min are warming up to 850 DEG C of heat preservations
2h, N2Atmosphere) the cooling taking-up of annealing, obtain Si-CNFs.
Natural spherical plumbago (D50: 13 μm), Si-CNFs=2:2:1.Material is dispersed with stirring using high-power, and stirring frequency is
2000Hz, solvent use ethylene glycol.Natural graphite is first added to be dissolved in ethylene glycol, is dispersed with stirring 20min, Si-CNFs is added, point
35min is dissipated, pitch is eventually adding, disperses 30min.Then spray pyrolysis is carried out, pyrolysis product is collected, is carbonized using 900 DEG C
(N2Atmosphere), it is cooled to room temperature re-sieving and obtains product SGP-1(D50: 25 μm).
SGP-1 product is placed in tube furnace and (prepares nano-silicon equipment), high pure nitrogen deoxygenation is passed through, is lower than to oxygen content
It carries out in next step, being heated to 950 DEG C with the rate of heat addition of 5 DEG C/min after 200ppm, it is logical with 1.0 L/min flow velocitys at 950 DEG C
Enter high purity acetylene (C2H2) gas, continue 15min, sieving is taken out after cooling down, obtains finished product Si-C composite material SGP-2(D50:
40 μm).
Embodiment 4
It purges experimental system repeatedly with high pure nitrogen and vacuumizes, it is ensured that the safety of system, by high purity silane gas
(99.99%) it is flowed, and remained unchanged with the low flow velocity of 1.8 L/min, thermally decomposed at 900 DEG C using silane, after twenty minutes
Using high purity acetylene (C2H2) gas is in same furnace, with the flow progress carbon coating 6min of 2.0 L/min at 900 DEG C, finally
System cooled to room temperature under nitrogen protection is collected burner hearth powder (S1).
S1 is taken to be added in the DMF solution of 3.40% polyacrylonitrile (mass ratio of S1 and solution is 1:9), with electrostatic
Mixed solution is carried out electrospinning in electric field strength 55KV/m electric field by spining technology.The polyacrylonitrile fibre of gained nano silicon particles
Film is dried under 60 DEG C of vacuum conditions except solvent.It is subsequently placed in tube furnace and is pre-oxidized that (room temperature, is warming up to by 3 DEG C/min
230 DEG C of holding 2h)；And carbonization treatment after annealing cooling, (room temperature, 3 DEG C/min are warming up to 850 DEG C of heat preservations 2h, N2Atmosphere) it moves back
Fire is cooling to be taken out, and Si-CNFs is obtained.
Natural spherical plumbago (D50: 12 μm), Si-CNFs=5:3:2.Material is dispersed with stirring using high-power, and stirring frequency is
1300Hz, solvent use ethylene glycol.Natural graphite is first added to be dissolved in ethylene glycol, is dispersed with stirring 10min, Si-CNFs is added, point
30min is dissipated, pitch is eventually adding, disperses 25min.Then spray pyrolysis is carried out, pyrolysis product is collected, is carbonized using 800 DEG C
(N2Atmosphere), it is cooled to room temperature re-sieving and obtains product SGP-1(D50: 17 μm).
SGP-1 product is placed in tube furnace and (prepares nano-silicon equipment), high pure nitrogen deoxygenation is passed through, is lower than to oxygen content
It carries out in next step, being heated to 1000 DEG C with the rate of heat addition of 4 DEG C/min after 200ppm, at 1000 DEG C, with 1.0 L/min stream
Speed is passed through high purity acetylene (C2H2) gas, continue 10min, sieving is taken out after cooling down, obtains finished product Si-C composite material SGP-2
(D50: 23 μm).
Performance test
The silicon-carbon composite cathode material prepared to above-described embodiment 1~4 is tested for the property, and result is as shown in the table:
As can be seen from the above table, silicon-carbon composite cathode material provided by the invention is assembled into 2032 button cells with excellent electricity
Chemical property, the half-cell that high capacity Si-C composite material provided by the invention is assembled into have excellent chemical property,
First discharge specific capacity is 1400mAh/g or more, and first charge-discharge coulombic efficiency is 80% or more.
Claims (7)
1. a kind of preparation method of silicon-carbon composite cathode material, which comprises the following steps:
A1, CVD method prepare nano-silicon: under nitrogen protection, silane gas being passed into reacting furnace, heating sends out silane gas
Heat is decomposed, and is then passed to carbon-source gas and is carried out carbon coating, finally cooled to room temperature under nitrogen protection, collects reacting furnace
Powder in burner hearth；
A2, electrostatic spinning prepare complex fiber material: the obtained powder of step A1 be added in the DMF solution of polyacrylonitrile,
Electrostatic spinning is carried out in the electric field and obtains the polyacrylonitrile fibre membrane of nano silicon particles, then polyacrylonitrile fibre membrane is dried and is removed
Then polyacrylonitrile fibre membrane is placed in tube furnace and carries out pre-oxidation treatment, is carbonized again after pre-oxidation treatment by solvent
Processing, obtains silicon-carbon complex fiber material；
A3, granulation: natural spherical plumbago is dissolved in solvent, and silicon-carbon complex fiber material and the drip of step A2 preparation is then added
Blueness is dispersed with stirring, and then carries out spray pyrolysis, collects pyrolysis product, then carry out carbonization treatment under nitrogen protection, obtains silicon-carbon
Composite precursor；
A4, CVD cladding: silicon-carbon composite precursor prepared by step A3 is placed in the tube furnace with nitrogen and is heated, so
After be passed through carbon-source gas and coated, carried out after cladding it is cooling, be sieved, obtain silicon-carbon composite cathode material.
2. a kind of preparation method of silicon-carbon composite cathode material according to claim 1, which is characterized in that including following step
It is rapid:
A1, CVD method prepare nano-silicon: under nitrogen protection, silane gas being passed into reacting furnace, reacting furnace temperature control exists
750-950 DEG C, silane gas is thermally decomposed, then passes to carbon-source gas and carry out carbon coating, finally under nitrogen protection certainly
It is so cooled to room temperature, collects the powder in reacting furnace burner hearth；
A2, electrostatic spinning prepare complex fiber material: the obtained powder of step A1 be added in the DMF solution of polyacrylonitrile,
Electrostatic spinning is carried out in the electric field that electric field strength is 55-75KV/m, obtains the polyacrylonitrile fibre membrane of nano silicon particles, then will
Polyacrylonitrile fibre membrane, is then placed in tube furnace and carries out pre-oxidation treatment by polyacrylonitrile fibre membrane drying removal solvent,
Carbonization treatment is carried out after pre-oxidation treatment again, obtains silicon-carbon complex fiber material；
A3, granulation: natural spherical plumbago is dissolved in solvent, the silicon-carbon complex fiber material of step A2 preparation is then added, most
After pitch is added, be dispersed with stirring, then carry out spray pyrolysis, collect pyrolysis product, then carry out carbonization treatment under nitrogen protection,
Obtain silicon-carbon composite precursor；
A4, CVD cladding: silicon-carbon composite precursor prepared by step A3 is placed in tube furnace, high pure nitrogen deoxygenation is passed through, to oxygen
After content is lower than 200ppm, it is heated to 900-1000 DEG C, carbon-source gas is then passed through with 1.0-2.0 L/min flow velocity, continues 8-
15min takes out sieving after cooling down, obtains silicon-carbon composite cathode material.
3. a kind of preparation method of silicon-carbon composite cathode material according to claim 1, which is characterized in that including following step
It is rapid:
A1, silane gas thermal cvd prepare nano-silicon: under nitrogen protection, by purity be 99.99% silane gas with 1.0-
The low flow velocity of 2.0 L/min is passed into reacting furnace, and reacting furnace temperature is controlled at 750-950 DEG C, makes silane gas that heat point occur
Solution is passed through carbon-source gas with 1.0-2.0 L/min low flow velocity and carries out carbon coating, the time of carbon coating is 6- after twenty minutes
10min, finally system cooled to room temperature under nitrogen protection, collects the powder in reacting furnace burner hearth；
A2, electrostatic spinning prepare complex fiber material: the step A1 powder collected be added in the DMF solution of polyacrylonitrile,
Then electrostatic spinning is carried out in the electric field that electric field strength is 55-75KV/m, obtains the polyacrylonitrile fibre membrane of nano silicon particles,
Polyacrylonitrile fibre membrane is dried to removal solvent under 60-80 DEG C of vacuum condition again, polyacrylonitrile fibre membrane is then placed in pipe
Pre-oxidation treatment is carried out in formula furnace, the pre-oxidation treatment is warming up to 230-300 DEG C with 3-5 DEG C/min rate, keeps 2-3h, moves back
Fire is cooling, then carries out carbonization treatment, obtains silicon-carbon complex fiber material；
A3, granulation: the granular size D50 natural spherical plumbago for being 10-15 μm being dissolved in solvent, 10-30min is dispersed with stirring,
Then the silicon-carbon complex fiber material of step A2 preparation is added, disperses 30-40min, is eventually adding pitch, disperses 20-40min,
Then spray pyrolysis is carried out, collects pyrolysis product, then carry out carbonization treatment under nitrogen protection, the temperature of carbonization treatment is 800-
950 DEG C, room temperature is cooled to after carbonization treatment, re-sieving obtains silicon-carbon composite precursor；
A4, CVD cladding: silicon-carbon composite precursor prepared by step A3 is placed in tube furnace, high pure nitrogen deoxygenation is passed through, to oxygen
After content is lower than 200ppm, it is heated to 900-1000 DEG C with the rate of heat addition of 3-5 DEG C/min, then with the stream of 1.0-2.0 L/min
Speed is passed through carbon-source gas, continues 8-15min, then cools to room temperature, takes out sieving, obtains silicon-carbon composite cathode material.
4. a kind of preparation method of silicon-carbon composite cathode material according to claim 1-3, it is characterised in that: institute
Stating carbon-source gas is one of methane, acetylene, ethylene, ethane or a variety of.
5. a kind of preparation method of silicon-carbon composite cathode material according to claim 1-3, it is characterised in that: step
In rapid A2, the mass ratio of the DMF solution of the powder and polyacrylonitrile is 1:5-11, is contained in the DMF solution of the polyacrylonitrile
There is polyacrylonitrile 3.40-4.50 wt%.
6. a kind of preparation method of silicon-carbon composite cathode material according to claim 1-3, it is characterised in that: step
In rapid A2, the temperature of the carbonization treatment is 850-950 DEG C, and heating rate is 3-5 DEG C/min, heat preservation when reaching 850-950 DEG C
2-3h, the carbonization treatment are carried out under inert protective atmosphere.
7. a kind of preparation method of silicon-carbon composite cathode material according to claim 1-3, it is characterised in that: step
In rapid A3, the solvent is one of ethylene glycol, methanol, ethyl alcohol, isopropanol or a variety of.
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| CN201811647550.7A CN109713285A (en) | 2018-12-29 | 2018-12-29 | A kind of silicon-carbon composite cathode material and preparation method thereof |
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| CN110729471A (en) * | 2019-10-24 | 2020-01-24 | 长沙晟天新材料有限公司 | Silicon @ graphene/CVD carbon composite anode material for lithium ion battery and preparation method and application thereof |
| CN111193013A (en) * | 2020-01-08 | 2020-05-22 | 青岛泰达华润新能源科技有限公司 | Preparation method of silicon-carbon negative electrode material for lithium ion battery |
| CN111785945A (en) * | 2020-07-21 | 2020-10-16 | 湖南中科星城石墨有限公司 | Graphene-coated nano silicon and preparation method thereof, silicon-carbon negative electrode material and preparation method thereof |
| CN112226841A (en) * | 2020-10-23 | 2021-01-15 | 中国恩菲工程技术有限公司 | Preparation method and device of water-soluble polymer/inorganic nano powder composite fiber, lithium ion battery negative electrode material and preparation method |
| EP3835261A1 (en) * | 2019-12-12 | 2021-06-16 | CALB Technology Co., Ltd. | Silicon-graphite composite, preparation method thereof, and lithium battery anode and lithium battery containing silicon-graphite composite |
| CN113417069A (en) * | 2021-06-03 | 2021-09-21 | 南昌大学 | Method for preparing silicon cathode material based on electrostatic spinning technology and application thereof |
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| CN112226841A (en) * | 2020-10-23 | 2021-01-15 | 中国恩菲工程技术有限公司 | Preparation method and device of water-soluble polymer/inorganic nano powder composite fiber, lithium ion battery negative electrode material and preparation method |
| CN113417069A (en) * | 2021-06-03 | 2021-09-21 | 南昌大学 | Method for preparing silicon cathode material based on electrostatic spinning technology and application thereof |
| CN113636539A (en) * | 2021-07-13 | 2021-11-12 | 哈尔滨金纳科技有限公司 | Preparation method of high-dispersion carbon nanotube material |
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| CN114447284A (en) * | 2022-01-13 | 2022-05-06 | 东莞市无中有新能源科技有限公司 | Preparation method of graphene negative plate and lithium battery |
| CN114447284B (en) * | 2022-01-13 | 2024-04-05 | 东莞市无中有新能源科技有限公司 | Preparation method of graphene negative plate and lithium battery |
| CN116216874A (en) * | 2023-03-23 | 2023-06-06 | 重庆大学 | Water body restoration agent for controlling cyanobacteria bloom, preparation method and application |
| CN116216874B (en) * | 2023-03-23 | 2024-04-30 | 重庆大学 | Water body restoration agent for controlling cyanobacteria bloom, preparation method and application |
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