CN107565115A - Preparation method, silicon-carbon cathode material and the lithium ion battery of silicon-carbon cathode material - Google Patents
Preparation method, silicon-carbon cathode material and the lithium ion battery of silicon-carbon cathode material Download PDFInfo
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- CN107565115A CN107565115A CN201710767145.8A CN201710767145A CN107565115A CN 107565115 A CN107565115 A CN 107565115A CN 201710767145 A CN201710767145 A CN 201710767145A CN 107565115 A CN107565115 A CN 107565115A
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Abstract
The invention belongs to technical field of lithium ion, is related to a kind of preparation method of silicon-carbon cathode material, silicon-carbon cathode material and lithium ion battery.The preparation method of silicon-carbon cathode material provided by the invention, comprises the following steps：(a) using silicon monoxide as matrix material, silicon monoxide is heated, makes silicon monoxide that disproportionated reaction generation c SiO occur；(b) c SiO are positioned in chemical vapor deposition stove, heated up under protective atmosphere, be passed through carbon source after being warming up to reaction temperature, carry out vapor deposition reaction, obtain c SiO/C, wherein carbon source is liquid or solid chemical compound；(c) by c SiO/C after corroding corrosion, silicon-carbon cathode material c SiO/Si/C are obtained.Present invention process is simple, easy to operate, and obtained silicon-carbon cathode material is provided simultaneously with the high storage lithium characteristic of silicon class material and the high circulation stability of carbons material, and specific capacity is high, good conductivity, good cycle.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of preparation method of silicon-carbon cathode material, silicon-carbon
Negative material and lithium ion battery.
Background technology
In existing secondary cell system, no matter from development space, or from the life-span, than energy, operating voltage and from
From the point of view of the technical indicators such as discharge rate, lithium ion battery is all current most competitive secondary cell.With electronics technology not
Disconnected development, higher requirement is it is also proposed to lithium ion battery, it is necessary to higher energy density, more preferable cycle life, more preferable
High/low temperature charge-discharge performance and security performance etc., this requires lithium ion battery to need to obtain into one with positive pole, negative material
Step ground development and perfection.
The more lithium ion battery negative material of current practice is carbon material, such as native graphite, graphitized intermediate-phase
Carbosphere etc..In non-carbon negative material, silicon has a high theoretical specific capacity, relatively low storage lithium response voltage platform, and
Distribution of the silicon in nature is very wide, and the content in the earth's crust is only second to oxygen, therefore silicon based anode material is a kind of great development
The novel high-energy material of prospect.However, the electronic conductivity and ionic conductivity of silicon are relatively low, cause the power of its electrochemical reaction
Learn poor-performing；The cyclical stability of common pure silicon is poor.And phase transformation and volumetric expansion of the silicon during lithiumation can produce
Larger stress, cause lead rupture efflorescence, resistance increase, cycle performance rapid drawdown.
Research currently for silicon based anode material is mainly to be pyrolyzed after silica flour is carried out into ball milling mixing with carbon source material, with
Silico-carbo composite is prepared, to alleviate the Study of Volume Expansion in battery charge and discharge process, improves the cyclicity of silica-base material
Energy.However, the preparation method of existing silico-carbo composite, also there is certain weak point, for example, the selection of carbon source
Scope is limited, and cost is high and ineffective, and cycle performance improves and unobvious etc.；In addition, method operating procedure is numerous and diverse, reacted
Journey is difficult to control, less stable, is unfavorable for industrialized development application.
In consideration of it, special propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of preparation method of silicon-carbon cathode material, and technique is simple, easy to operate, system
The silicon-carbon cathode material obtained is provided simultaneously with the high storage lithium characteristic of silicon class material and the high circulation stability of carbons material, specific capacity
Height, kinetics performance are good.
The second object of the present invention is to provide a kind of silicon-carbon cathode material, and the volume that can effectively suppress silicium cathode is swollen
It is swollen, there is excellent electric conductivity, and specific capacity is high, good cycle.
The third object of the present invention is to provide a kind of lithium ion battery, and the lithium ion battery specific capacity is high, cycle performance
It is good, electrochemical performance.
To achieve the above object, the technical solution adopted by the present invention is：
According to an aspect of the present invention, the present invention provides a kind of preparation method of silicon-carbon cathode material, including following step
Suddenly：
(a) using silicon monoxide as matrix material, silicon monoxide is heated, makes silicon monoxide that disproportionated reaction occur
Generate c-SiO；
(b) c-SiO is positioned in chemical vapor deposition stove, heated up under protective atmosphere, be warming up to reaction temperature
Carbon source is passed through after degree, vapor deposition reaction is carried out, obtains c-SiO/C；
(c) c-SiO/C is obtained into silicon-carbon cathode material c-SiO/Si/C after corroding corrosion.
As further preferred technical scheme, the granularity of the silicon monoxide matrix material is 400~600 mesh, is preferably
450~550 mesh, more preferably 500 mesh.
As further preferred technical scheme, in step (a), the detailed process that disproportionated reaction occurs for silicon monoxide is：
Silicon monoxide is placed in heater, is first warming up to 80~120 DEG C with 2~8 DEG C/min heating rate, insulation
700~1000 DEG C are warming up to 2~8 DEG C/min heating rate again after 0.5~2h, after being incubated 1~3h, room temperature is cooled to, obtains
To c-SiO；
Preferably, the heater is provided with quartz boat, zirconium oxide boat or aluminium oxide boat.
As further preferred technical scheme, in step (b), in the c-SiO/C C content be 3wt%~
10wt%；
Preferably, described carbon source is polystyrene, glucose, sucrose, phenolic resin, epoxy resin, ferrocene ethanol
Any one in solution, ferrocene acetone soln, cobalt nitrate ethanol solution, benzene, toluene or dimethylbenzene；
Preferably, described reaction temperature is 700~1200 DEG C；
Preferably, described chemical vapor deposition stove is tube furnace, rotary furnace or Muffle furnace；
Preferably, described protective atmosphere is any one in nitrogen, helium, argon gas or neon.
As further preferred technical scheme, described carbon source is polystyrene, and c- is obtained by vapor deposition reaction
SiO/C detailed process is：
The c-SiO and copper powder are subjected to ball milling, is well mixed, obtains mixture；The mixture is placed in chemical gas
The side of phase cvd furnace, the polystyrene is placed in the opposite side of chemical vapor deposition stove；First purified under protective atmosphere
0.3~1h, then mixture area is warming up to 700~900 DEG C with 3~7 DEG C/min heating rate, polystyrene area is warming up to
300~500 DEG C, after being incubated 2~4h, room temperature is cooled to, that is, obtains described c-SiO/C；
Preferably, in addition to the pre-treatment step for copper powder, micron-sized copper powder is first cleaned by ultrasonic through acetone soln
20~40min, then it is cleaned by ultrasonic 10~30min with the acid solution that concentration is 20%~40%, then copper powder is cleaned with water,
Dry, then ball milling is carried out with c-SiO；
Preferably, the step of in addition to removing copper powder, the obtained sample after cooling is placed in ferric chloride solution and removed
Copper powder, then washed respectively with the acid solution and water that concentration is 5%~15%, that is, obtain described c-SiO/C；
Preferably, described c-SiO/C is and the graphite being evenly distributed on c-SiO matrixes by c-SiO matrixes
Alkene forms.
As further preferred technical scheme, described carbon source is ferrocene ethanol solution, is obtained by vapor deposition reaction
Detailed process to c-SiO/C is：
The c-SiO is placed in chemical vapor deposition stove, 0.3~1h is first purified under protective atmosphere, then with 3~7
DEG C/min heating rate is warming up to 900~1100 DEG C, ferrocene ethanol solution is passed through, carries out 2~5h of vapor deposition reaction, so
Carbon elimination source cooling of dropping back obtains described c-SiO/C to room temperature；
Preferably, the concentration range of described ferrocene ethanol solution is 5~20mg/mL；
Preferably, in addition to by the ferrocene ethanol solution heated under conditions of 40~60 DEG C, then be passed through chemical gas
The step of vapor deposition reaction is carried out in phase cvd furnace；
Preferably, described c-SiO/C is by c-SiO matrixes, and the carbon being evenly distributed on c-SiO matrixes is received
Mitron forms.
As further preferred technical scheme, described carbon source is toluene, and c-SiO/C is obtained by vapor deposition reaction
Detailed process be：
The c-SiO is placed in chemical vapor deposition stove, 0.3~1h is first purified under protective atmosphere, then with 3~7
DEG C/min heating rate is warming up to 700~1000 DEG C, toluene is passed through, 1~4h of vapor deposition reaction is carried out, then removes carbon source
Room temperature is cooled to, that is, obtains described c-SiO/C；
Preferably, in addition to by the toluene heated under conditions of 40~60 DEG C, then be passed through chemical vapor deposition
The step of vapor deposition reaction is carried out in stove；
Preferably, described c-SiO/C is by c-SiO matrixes, and the nothing being evenly distributed on c-SiO matrixes is determined
Type carbon forms.
As further preferred technical scheme, in step (c), the corrosive liquid is 3wt%~20wt% hydrofluoric acid water
The hydrofluoric acid aqueous solution of solution, preferably 5wt%~10wt%；
Preferably, the mass ratio of the c-SiO/C and hydrofluoric acid are 1：1.2~1.5, time of corrosion treatment for 5~
30min；
Preferably, the step for being washed with water and drying also is included after corrosion treatment, dry temperature is preferably 90~120
℃。
According to another aspect of the present invention, the present invention also provides a kind of silicon-carbon cathode material, by above-described silicon-carbon
The preparation method of negative material is made.
According to another aspect of the present invention, the present invention also provides a kind of lithium ion battery, and its negative pole includes described above
Silicon-carbon cathode material.
Compared with prior art, the beneficial effects of the present invention are：
1st, the present invention is using silicon monoxide as raw material, pass sequentially through high temperature disproportionated reaction, with the vapor deposition reaction of carbon source with
And etching operation step, obtain the compound negative material of the silicon-carbon of porous type；What wherein carbon source was selected be carbon containing liquid or
Solid compounds, compared with gaseous carbon source commonly used in the prior art, raw material sources of the present invention are more extensive, and cost is low, raw material
It is environment-friendly, and preparation process is easily operated, and convenient control, process conditions are simple and easy, and energy consumption is low, obtained silicon-carbon cathode
Material is provided simultaneously with the high storage lithium characteristic of silicon class material and the high circulation stability of carbons material, and specific capacity is high, kinetics
Performance is good.
2nd, silicon-carbon cathode material of the invention, in one layer of carbon-coating of area load of silicon substrate material, carbon-coating not only increases
The electric conductivity of material, and can prevent silicon core is broken to be scattered, composite is effectively prevent in charge and discharge process due to body
Product changes and ruptures and crush, and improves silicon bulk effect, ensure that the structural stability of material, improve the electrochemical reaction of material
Dynamic performance；In addition, further improving the surface chemical structure of silica-base material, reduce it and contacted with the direct of electrolyte, promoted
Stable, thin and compact solid electrolyte film is formed in electrode surface, improves electrode/electrolyte interface compatibility, so as to carry
The cycle performance of high electrode.
3rd, present invention process is simple, reproducible, and whole production process is without the equipment of complexity, and production cost is low, efficiency
Height, obtained product stability is good, is easy to large-scale industrial production, has good application prospect on lithium ion battery.
4th, lithium ion battery and silicon-carbon cathode material provided by the invention, cost is low, stable performance, and specific capacity is high, leads
It is electrically good, have extended cycle life, electrochemical performance.
Brief description of the drawings
, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical scheme of the prior art
The required accompanying drawing used is briefly described in embodiment or description of the prior art, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before creative work is not paid
Put, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is the XRD (X-ray diffractogram) for the silicon-carbon cathode material that the embodiment of the present invention 3 provides, and abscissa is diffraction
Angle, ordinate are intensity；In figure, represent successively from bottom to top be matrix material SiO, disproportionation generation c-SiO, gas phase sinks
The XRD for the c-SiO/Si/C that the c-SiO/C and corrosion that product obtains are obtained；
Fig. 2 is that the SEM for the silicon-carbon cathode material that the embodiment of the present invention 3 provides schemes (Scanning Electron
Microscope scanning electron microscope (SEM) photographs)；That Fig. 2 (a) and Fig. 2 (b) is represented respectively is the c-SiO/C and corrosion that vapour deposition obtains
Obtained c-SiO/Si/C SEM figures；
Fig. 3 is the lithium ion battery made of silicon-carbon cathode material prepared by the embodiment of the present invention 3 at the 1st time, 10 times, 20 times
Charge and discharge cycles curve, abscissa are specific capacity (mAhg- 1), ordinate is voltage (V)；Fig. 3 (a), Fig. 3 (b) and Fig. 3
(c) what is represented respectively is following for the c-SiO/Si/C that matrix material SiO, the obtained c-SiO/C of vapour deposition and corrosion obtain
Ring curve；
Fig. 4 is the cycle-index-electric discharge for the lithium ion battery that silicon-carbon cathode material prepared by the embodiment of the present invention 3 is made
Specific volume spirogram, abscissa are cycle-index, and ordinate is specific discharge capacity (mAhg- 1)。
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment and embodiment, but this area skill
Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and be not construed as the model of the limitation present invention
Enclose.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.Actual conditions person is indicated, is suggested according to normal condition or manufacturer
Condition carry out.Agents useful for same or the unreceipted production firm person of instrument, it is the conventional products that can be obtained by commercially available purchase.
In a first aspect, present embodiment provides a kind of preparation method of silicon-carbon cathode material, comprise the following steps：
(a) using silicon monoxide as matrix material, silicon monoxide is heated, makes silicon monoxide that disproportionated reaction occur
Generate c-SiO；
(b) c-SiO is positioned in chemical vapor deposition stove, heated up under protective atmosphere, be warming up to reaction temperature
Carbon source is passed through after degree, vapor deposition reaction is carried out, obtains c-SiO/C；Wherein described carbon source is solid-state or liquefied compound；
(c) c-SiO/C is obtained into silicon-carbon cathode material c-SiO/Si/C after corroding corrosion.
By silicon-carbon cathode material made from the preparation method of silicon-carbon cathode material provided by the invention, can overcome existing
The defects of can not all meeting needs when the negative material of silicon materials and carbon material as lithium ion battery being used alone in technology, can
To give full play to the function of silicon and carbon, there is preferable structural stability.On the one hand, the superior electric conductivity of carbon-coating is make use of, more
The problem of having mended silicon grain poorly conductive, improve the electric conductivity of material；On the other hand, electrification is increased by silicon substrate material
Reaction interface is learned, improves the electrochemical reaction dynamic performance of material, improves the cycle performance of electrode；In addition, by silicon substrate
One layer of carbon-coating of body material surface uniform load, the surface texture of silicon can be improved, reduce it and contacted with the direct of electrolyte, promoted
Stable, thin and compact solid electrolyte film is formed in electrode surface, improves electrode/electrolyte interface compatibility, Jin Erti
The cycle performance of high electrode.
The present invention is matrix material with silicon monoxide (or sub- silicon of oxidation, SiO), and selects the carbon source of liquid or solid-state,
Compared with matrix material commonly used in the prior art and gaseous carbon source, raw material sources are extensive, and cost is low, and operating process is easier to control
System, simple and easy, energy consumption is low, it is easier to scale industrial production.
SiO is first carried out high temperature disproportionated reaction generation c-SiO by the present invention, and what wherein c-SiO was represented is silicon and titanium dioxide
Silicon, silicon grain are evenly distributed in the matrix of silica, can effectively avoid the generation of some side reaction things.
C-SiO and carbon source are placed in chemical vapor deposition stove again and carry out vapor deposition reaction, obtains c-SiO/C, its
What middle c-SiO/C was represented is that one layer of C (carbon-coating) is uniformly loaded on the surface of c-SiO materials.In the present invention, choosing can be passed through
Different types of carbon source is selected, under suitable reaction temperature and time, chemical vapor deposition is carried out, to deposit different shape
Carbon, and then prepare the silicon carbon material of different electric conductivity, cycle performance and specific capacity.
Then (or etching) is corroded to c-SiO/C using corrosive liquid again, to remove silica, prevented
The reunion of silicon grain, prepare the silicon carbon material c-SiO/Si/C of porous type；That wherein c-SiO/Si/C is represented is c-SiO/
The silicon carbon material that C is obtained after erosion removal silica.In the present invention, silicon carbon material can be adjusted by the control corrosion rate time
Pore size.
In a kind of optional embodiment, the granularity of the silicon monoxide matrix material is 400~600 mesh, is preferably
450~550 mesh, more preferably 500 mesh.
In a detailed embodiment, optionally, the granularity of silicon monoxide matrix material is 400 mesh, 450 mesh, 500
Mesh, 550 mesh or 600 mesh.
The mean particle size of silicon monoxide matrix material in present embodiment is in 500 mesh or so, and raw material is easy to get, favorably
In subsequent operation, and the structural stability that has had of obtained material and dynamic performance.
In a kind of optional embodiment, in step (a), the detailed process that disproportionated reaction occurs for silicon monoxide is：
Silicon monoxide is placed in heater, is first warming up to 80~120 DEG C with 2~8 DEG C/min heating rate, insulation
700~1000 DEG C are warming up to 2~8 DEG C/min heating rate again after 0.5~2h, after being incubated 1~3h, room temperature is cooled to, obtains
To c-SiO；
Preferably, silicon monoxide is placed in heater, first with 4~6 DEG C/min under air, nitrogen or argon atmosphere
Heating rate be warming up to 90~110 DEG C, be incubated after 1~1.5h and be warming up to 750~850 DEG C again with identical heating rate, protect
After 1.5~2.5h of temperature, room temperature is cooled to, obtains c-SiO；
Preferably, the heater is provided with quartz boat, zirconium oxide boat or aluminium oxide boat.
Using the atmosphere heating mode of segmented, the generation of some side reaction things can be effectively avoided, moreover it is possible to control thin
The content of grain, disproportionated reaction effect are more preferable.
Heater in the present embodiment mode can be the tubular type with quartz boat, zirconium oxide boat or aluminium oxide boat etc.
Stove, silicon monoxide is placed in these resistant to elevated temperatures quartz boats, zirconium oxide boat or aluminium oxide boat and carries out heating heating again.
In a detailed embodiment, optionally, silicon monoxide is placed in quartz boat, zirconium oxide boat or aluminium oxide boat
In, first with 2 DEG C/min, 3 DEG C/min, 4 DEG C/min, 5 DEG C/min, 6 DEG C/min, 7 DEG C/min or 8 DEG C/min under air atmosphere
Heating rate is warming up to 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C or 120 DEG C, is incubated after 0.5h, 1h, 1.5h or 2h again with same liter
Warm speed is warming up to 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C or 1000 DEG C, be incubated 1h, 1.5h, 2h, 2.5h or
After 3h, room temperature is cooled to, obtains c-SiO.
Explanation is needed exist for, " room temperature " of the present invention represents 20~30 DEG C of temperature.It is cooled to the side of room temperature
Formula is preferably to naturally cool to room temperature.
In a kind of optional embodiment, in step (b), in the c-SiO/C C content be 3wt%~
10wt%；
Preferably, described carbon source is polystyrene, glucose, sucrose, phenolic resin, epoxy resin, ferrocene ethanol
Any one in solution, ferrocene acetone soln, cobalt nitrate ethanol solution, benzene, toluene or dimethylbenzene；
Preferably, described reaction temperature is 700~1200 DEG C；
Preferably, described chemical vapor deposition stove is tube furnace, rotary furnace or Muffle furnace；
Preferably, described protective atmosphere is any one in nitrogen, helium, argon gas or neon.
The time of vapor deposition reaction is different, required c-SiO and the mass ratio of carbon source, or the ratio shared by carbon source
Example is also different.Under conditions of certain vapor deposition reaction time, it can be obtained by changing c-SiO and carbon source mass ratio
There must be the C of different weight percentage composition c-SiO/C.
In a detailed embodiment, optionally, the reaction temperature of vapour deposition be 700 DEG C, 750 DEG C, 800 DEG C, 850
DEG C, 900 DEG C, 950 DEG C, 1000 DEG C, 1050 DEG C, 1100 DEG C, 1150 DEG C or 1200 DEG C.
Carbon source in the present invention can be roughly divided into three classes, and one kind is polystyrene type solid carbon source, and two classes are ferrocene
Ethanol solution class, three classes are toluene classes.Wherein, polystyrene type includes polystyrene or polystyrene etc.；Ferrocene ethanol is molten
Liquid class includes ferrocene ethanol solution, ferrocene acetone soln, ferrocene methanol solution, ferric nitrate ethanol solution and cobalt nitrate second
Alcoholic solution etc., wherein, ferrocene, ferric nitrate, cobalt nitrate are catalyst, and methanol, ethanol, acetone are solvent, can also include class
As the catalysts and solvents such as ferric sulfate, propyl alcohol combination；Toluene class includes benzene, toluene and dimethylbenzene etc.；In addition, in the present invention
Carbon source also includes glucose, sucrose, the phenolic resin carbohydrate similar with epoxy resin etc. and resinae carbon source, what it was vapor-deposited
Operating condition is similar with the operating condition of the carbon source of toluene class.
The present invention mainly loads out the carbon-coating of three kinds of different shapes by above-mentioned three classes carbon source on silicon substrate material.Below
Illustrated respectively by taking polystyrene, ferrocene ethanol solution and toluene as an example；It is understood that described carbon source and unlimited
Can also be any one in above-mentioned carbon source in these three.
In a kind of optional embodiment, described carbon source is polystyrene, and c- is obtained by vapor deposition reaction
SiO/C detailed process is：
The c-SiO and copper powder are subjected to ball milling, is well mixed, obtains mixture；The mixture is placed in chemical gas
The side of phase cvd furnace, the polystyrene is placed in the opposite side of chemical vapor deposition stove；First purified under protective atmosphere
0.3~1h, then mixture area is warming up to 700~900 DEG C with 3~7 DEG C/min heating rate, polystyrene area is warming up to
300~500 DEG C, after being incubated 2~4h, room temperature is cooled to, that is, obtains described c-SiO/C；
Preferably, in addition to the pre-treatment step for copper powder, micron-sized copper powder is first cleaned by ultrasonic through acetone soln
20~40min, then it is cleaned by ultrasonic 10~30min with the hydrochloric acid solution that concentration is 20%~40%, then copper powder is cleaned with water,
Dry, then ball milling is carried out with c-SiO；
Preferably, the step of in addition to removing copper powder, the obtained sample after cooling is placed in ferric chloride solution and removed
Copper powder, then washed respectively with the hydrochloric acid solution and water that concentration is 5%~15%, that is, obtain described c-SiO/C；
Preferably, described c-SiO/C is and the graphite being evenly distributed on c-SiO matrixes by c-SiO matrixes
Alkene forms.
Copper powder in present embodiment, catalytic action can be played, prepare the carbon of graphene form.With polystyrene type
For carbon source, carry out that vapour deposition prepares by aforesaid operations mode is that several layer graphene thin slices are supported on c-SiO surfaces.
In a detailed embodiment, optionally, under protective atmosphere purify 0.3h, 0.4h, 0.5h, 0.6h,
0.7h, 0.8h, 0.9h or 1h, then make to mix with 3 DEG C/min, 4 DEG C/min, 5 DEG C/min, 6 DEG C/min or 7 DEG C/min heating rate
Compound area is warming up to 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C or 900 DEG C, polystyrene area be warming up to 300 DEG C, 350 DEG C, 400 DEG C,
450 DEG C or 500 DEG C, after being incubated 2h, 3h or 4h, it is cooled to room temperature.
In a detailed embodiment, optionally, by micron-sized copper powder first through acetone soln be cleaned by ultrasonic 20min,
25min, 30min, 35min or 40min, then with concentration be 20%, 30% or 40% hydrochloric acid solution be cleaned by ultrasonic 10min,
15min, 20min, 25min or 30min, then with water by copper powder cleaning, drying.Wherein, water is preferably deionized water, and drying is excellent
Elect vacuum drying as.
In a kind of optional embodiment, described carbon source is ferrocene ethanol solution, is obtained by vapor deposition reaction
Detailed process to c-SiO/C is：
The c-SiO is placed in chemical vapor deposition stove, 0.3~1h is first purified under protective atmosphere, then with 3~7
DEG C/min heating rate is warming up to 900~1100 DEG C, ferrocene ethanol solution is passed through, carries out 2~5h of vapor deposition reaction, so
Carbon elimination source cooling of dropping back obtains described c-SiO/C to room temperature；
Preferably, the concentration range of described ferrocene ethanol solution is 5~20mg/mL；
Preferably, in addition to by the ferrocene ethanol solution heated under conditions of 40~60 DEG C, then be passed through chemical gas
The step of vapor deposition reaction is carried out in phase cvd furnace；
Preferably, described c-SiO/C is by c-SiO matrixes, and the carbon being evenly distributed on c-SiO matrixes is received
Mitron forms.
Preferably, carry out vapor deposition reaction process before, by ferrocene ethanol solution under conditions of 45~55 DEG C water
Bath is heated, and heating water bath is persistently carried out during vapor deposition reaction, until after the completion of vapor deposition reaction, removes the same of carbon source
When remove heating water bath.Ferrocene in present embodiment, catalytic action can be played, using ferrocene ethanol solution class as carbon
Source, carry out that vapour deposition prepares by aforesaid operations mode is carbon nanotube loaded on c-SiO surfaces.
In a detailed embodiment, optionally, under protective atmosphere purify 0.3h, 0.4h, 0.5h, 0.6h,
0.7h, 0.8h, 0.9h or 1h, then heated up with 3 DEG C/min, 4 DEG C/min, 5 DEG C/min, 6 DEG C/min or 7 DEG C/min heating rate
To 900 DEG C, 950 DEG C, 1000 DEG C, 1050 DEG C or 1100 DEG C, be passed through ferrocene ethanol solution, carry out vapor deposition reaction 2h, 3h,
4h or 5h, then removes carbon source, naturally cools to room temperature.
In a detailed embodiment, optionally, the concentration of ferrocene ethanol solution be 5mg/mL, 10mg/mL,
15mg/mL or 20mg/mL.
In a kind of optional embodiment, described carbon source is toluene, and c-SiO/C is obtained by vapor deposition reaction
Detailed process be：
The c-SiO is placed in chemical vapor deposition stove, 0.3~1h is first purified under protective atmosphere, then with 3~7
DEG C/min heating rate is warming up to 700~1000 DEG C, toluene is passed through, 1~4h of vapor deposition reaction is carried out, then removes carbon source
Room temperature is cooled to, that is, obtains described c-SiO/C；
Preferably, in addition to by the toluene heated under conditions of 40~60 DEG C, then be passed through chemical vapor deposition
The step of vapor deposition reaction is carried out in stove；
Preferably, described c-SiO/C is by c-SiO matrixes, and the nothing being evenly distributed on c-SiO matrixes is determined
Type carbon forms.
Preferably, carry out vapor deposition reaction process before, by toluene under conditions of 45~55 DEG C heating water bath, gas phase
Heating water bath is persistently carried out during deposition reaction, until after the completion of vapor deposition reaction, water-bath is removed while removing carbon source
Heating.
Using toluene class as carbon source, carrying out vapour deposition by aforesaid operations mode, prepare is that unformed carbon is supported on
C-SiO surfaces.
In a detailed embodiment, optionally, under protective atmosphere purify 0.3h, 0.4h, 0.5h, 0.6h,
0.7h, 0.8h, 0.9h or 1h, then heated up with 3 DEG C/min, 4 DEG C/min, 5 DEG C/min, 6 DEG C/min or 7 DEG C/min heating rate
To 700 DEG C, 750 DEG C, 00 DEG C, 850 DEG C, 900 DEG C, 950 DEG C or 1000 DEG C, be passed through toluene, carry out vapor deposition reaction 1h, 2h,
3h or 4h, then removes carbon source, naturally cools to room temperature.
In a detailed embodiment, optionally, toluene is placed in 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C or 60 DEG C of water-bath
In heated.
In a kind of optional embodiment, in step (c), the corrosive liquid is 3wt%~20wt% hydrofluoric acid water
The hydrofluoric acid aqueous solution of solution, preferably 5wt%~10wt%；
Preferably, the mass ratio of the c-SiO/C and hydrofluoric acid are 1：1.2~1.5, time of corrosion treatment for 5~
30min；
Preferably, the step for being washed with water and drying also is included after corrosion treatment, dry temperature is preferably 90~120
℃。
By corrosion can remove silica, prepare the silicon carbon material of porous type, it is however generally that, hydrofluoric acid relative to
C-SiO/C can be slightly excessive；Under certain hydrofluoric acid concentration, the hole of silicon carbon material can be adjusted by the control corrosion rate time
Footpath size.
In a detailed embodiment, optionally, the concentration of hydrofluoric acid aqueous solution be 3wt%, 4wt%, 5wt%,
6wt%, 8wt%, 10wt%, 12wt%, 14wt%, 15wt%, 16wt%, 18wt% or 20wt%.
In a detailed embodiment, optionally, the time of corrosion treatment be 5min, 10min, 15min, 20min,
25min or 30min.
In a detailed embodiment, optionally, dry be preferably be dried in vacuo, dry temperature be 90 DEG C, 100
DEG C, 110 DEG C or 120 DEG C.
Second aspect, present embodiment provides a kind of silicon-carbon cathode material, by the system of above-described silicon-carbon cathode material
Preparation Method is made.
The third aspect, present embodiment provides a kind of lithium ion battery, including positive pole, negative pole, barrier film and electrolyte, described
Negative pole includes above-described silicon-carbon cathode material.
In present embodiment second aspect and the third aspect, lithium ion battery negative material, which removes, uses above-mentioned silicon-carbon cathode material
Material is used as beyond active material, and remaining composition and structure refer to prior art；Its system of positive pole, negative pole and lithium ion battery structure
Preparation Method refers to routine techniques, is added with differing only in lithium ion battery negative material for routine techniques by the
The silicon-carbon cathode material that the preparation method of silicon-carbon cathode material described in one side obtains.
The silicon-carbon cathode material that Pass through above-mentioned technical proposal is prepared, there is preferable chemical property, as lithium
Ion battery cathode material uses, and cost is low, stable performance, good conductivity, and specific capacity is high, has extended cycle life.
The present invention deposits different carbon microscopic appearances using different carbon sources, so prepare with different electric conductivity,
The silicon carbon material of specific capacity and cycle performance；And the different carbon silicium cathode of microcosmic particle diameter is prepared by the difference of etching time
Material, and then improve the performance of battery.Using above-mentioned technical proposal, the optimal pore size for the silicon-carbon cathode material prepared
For 3.2nm, average grain diameter is 8.85 μm, and first discharge specific capacity at room temperature is in more than 980mAh/g.
With reference to specific embodiment, comparative example and accompanying drawing, the invention will be further described.
Embodiment 1
A kind of preparation method of silicon-carbon cathode material, comprises the following steps：
(a) disproportionated reaction：Using silicon monoxide as matrix material, the granularity of silicon monoxide matrix material is 450 mesh, to an oxygen
SiClx is heated, and makes silicon monoxide that disproportionated reaction generation c-SiO occur；
(b) vapor deposition reaction：C-SiO is positioned in chemical vapor deposition stove, first purified under argon gas protection
0.5h, then 1000 DEG C are warming up to 5 DEG C/min heating rate, ferrocene ethanol solution is passed through, carries out vapor deposition reaction 3h,
Obtain c-SiO/C, C content is 5wt% in wherein c-SiO/C；
(c) corrode：C-SiO/C is placed in 5wt% hydrofluoric acid aqueous solution, after stirring immersion 10min, uses deionization
Water washing, dried at 100 DEG C, obtain silicon-carbon cathode material c-SiO/Si/C.
Embodiment 2
A kind of preparation method of silicon-carbon cathode material, comprises the following steps：
(a) disproportionated reaction：Using silicon monoxide as matrix material, the granularity of silicon monoxide matrix material is 500 mesh, to an oxygen
SiClx is heated, and makes silicon monoxide that disproportionated reaction generation c-SiO occur；
(b) vapor deposition reaction：C-SiO is positioned in chemical vapor deposition stove, first purified under argon gas protection
0.5h, then 800 DEG C are warming up to 5 DEG C/min heating rate, toluene is passed through, vapor deposition reaction 2h is carried out, obtains c-SiO/
C content is 6wt% in C, wherein c-SiO/C；
(c) corrode：C-SiO/C is placed in 5wt% hydrofluoric acid aqueous solution, after stirring immersion 15min, uses deionization
Water washing, dried at 100 DEG C, obtain silicon-carbon cathode material c-SiO/Si/C.
Embodiment 3
A kind of preparation method of silicon-carbon cathode material, comprises the following steps：
(a) disproportionated reaction：Using silicon monoxide as matrix material, the granularity of silicon monoxide matrix material is 500 mesh, by an oxygen
SiClx is placed in the heater with aluminium oxide boat, and first 100 are warming up to 5 DEG C/min heating rate under argon atmosphere
DEG C, it is incubated after 1h and is warming up to 800 DEG C again with identical heating rate, after being incubated 2h, is cooled to room temperature, silicon monoxide during this
Generation disproportionated reaction generates c-SiO；
(b) vapor deposition reaction：C-SiO and copper powder are subjected to ball milling, is well mixed, obtains mixture；Mixture is put
In the side of double temperature-area tubular furnaces, polystyrene is placed in the opposite side of double temperature-area tubular furnaces；First purified under argon gas protection
0.5h, then mixture area is warming up to 800 DEG C with 5 DEG C/min heating rate, polystyrene area is warming up to 400 DEG C, is incubated 3h
Afterwards, room temperature is naturally cooled to, obtains c-SiO/C；C content is 7wt% in wherein c-SiO/C；
Obtained c-SiO/C is by c-SiO matrixes, and the number layer graphene being evenly distributed on c-SiO matrixes is thin
Piece forms；
(c) corrode：C-SiO/C is placed in 5wt% hydrofluoric acid aqueous solution, the mass ratio of c-SiO/C and hydrofluoric acid
For 1：After 1.2, stirring immersion 10min, it is washed with deionized, is dried in vacuo at 100 DEG C, obtain silicon-carbon cathode material c-
SiO/Si/C。
Embodiment 4
A kind of preparation method of silicon-carbon cathode material, comprises the following steps：
(a) disproportionated reaction：Using silicon monoxide as matrix material, the granularity of silicon monoxide matrix material is 600 mesh, by an oxygen
SiClx is placed in the tube furnace with zirconium oxide boat, and first 120 DEG C are warming up to 6 DEG C/min heating rate under argon atmosphere,
900 DEG C are warming up to identical heating rate again after insulation 2h, after being incubated 3h, is cooled to room temperature, silicon monoxide is sent out during this
Raw disproportionated reaction generation c-SiO；
Step (b) and (c) are same as Example 3.
Embodiment 5
A kind of preparation method of silicon-carbon cathode material, comprises the following steps：
(b) vapor deposition reaction：Micron-sized copper powder is first cleaned by ultrasonic 30min through acetone soln, then is with concentration
30% hydrochloric acid solution is cleaned by ultrasonic 20min, is then cleaned copper powder with deionized water, is dried in vacuo；
Copper powder after c-SiO and drying is subjected to ball milling, is well mixed, obtains mixture；Mixture is placed in dual temperature area pipe
The side of formula stove, polystyrene is placed in the opposite side of double temperature-area tubular furnaces；First purify 1h under argon hydrogen mixing gas shielded, then with
3 DEG C/min heating rate makes mixture area be warming up to 750 DEG C, and polystyrene area is warming up to 300 DEG C, naturally cold after being incubated 2h
But to room temperature；
Obtained sample after cooling is placed in ferric chloride solution and removes copper powder, then respectively with the hydrochloric acid that concentration is 10%
Solution and water are washed, and obtain c-SiO/C；C content is 8wt% in wherein c-SiO/C；
Obtained c-SiO/C is by c-SiO matrixes, and the number layer graphene being evenly distributed on c-SiO matrixes is thin
Piece forms；
Step (a) and (c) are same as Example 3.
Embodiment 6
A kind of preparation method of silicon-carbon cathode material, comprises the following steps：
(b) vapor deposition reaction：Micron-sized copper powder is first cleaned by ultrasonic 40min through acetone soln, then is with concentration
40% hydrochloric acid solution is cleaned by ultrasonic 30min, is then cleaned copper powder with deionized water, is dried in vacuo；
Copper powder after c-SiO and drying is subjected to ball milling, is well mixed, obtains mixture；Mixture is placed in dual temperature area pipe
The side of formula stove, polystyrene is placed in the opposite side of double temperature-area tubular furnaces；0.3h is first purified under helium gas shielded, then with 7
DEG C/min heating rate makes mixture area be warming up to 900 DEG C, and polystyrene area is warming up to 500 DEG C, after being incubated 4h, natural cooling
To room temperature；
Obtained sample after cooling is placed in ferric chloride solution and removes copper powder, then respectively with the hydrochloric acid that concentration is 15%
Solution and water are washed, and obtain c-SiO/C；C content is 8wt% in wherein c-SiO/C；
Obtained c-SiO/C is by c-SiO matrixes, and the number layer graphene being evenly distributed on c-SiO matrixes is thin
Piece forms；
Step (a) and (c) are same as Example 3.
Embodiment 7
A kind of preparation method of silicon-carbon cathode material, comprises the following steps：
(c) corrode：C-SiO/C is placed in 10wt% hydrofluoric acid aqueous solution, the mass ratio of c-SiO/C and hydrofluoric acid
For 1：After 1.5, stirring immersion 5min, it is washed with deionized, is dried in vacuo at 90 DEG C, obtain silicon-carbon cathode material c-
SiO/Si/C。
Step (a) and (b) are same as Example 3.
Embodiment 8
A kind of preparation method of silicon-carbon cathode material, comprises the following steps：
(b) vapor deposition reaction：C-SiO is placed in rotary furnace, 1h is first purified under nitrogen protection atmosphere, then with 6
DEG C/min heating rate is warming up to 1100 DEG C, ferrocene ethanol solution is placed in 50 DEG C of water-bath and heated, then is passed through
Ferrocene ethanol solution, vapor deposition reaction 5h is carried out, carbon source is then removed and is cooled to room temperature, that is, obtain c-SiO/C；Wherein
The concentration of ferrocene ethanol solution is 10mg/mL；
Obtained c-SiO/C is and the CNT group being evenly distributed on c-SiO matrixes by c-SiO matrixes
Into；
Step (a) and (c) are same as Example 3.
Embodiment 9
A kind of preparation method of silicon-carbon cathode material, comprises the following steps：
(b) vapor deposition reaction：C-SiO is placed in rotary furnace, 0.6h is first purified under argon atmosphere, then with 4
DEG C/min heating rate is warming up to 1000 DEG C, toluene is placed in 50 DEG C of water-bath and heated, then toluene is passed through, enter promoting the circulation of qi
Phase deposition reaction 4h, then remove carbon source and be cooled to room temperature, that is, obtain c-SiO/C；C content is in wherein c-SiO/C
6wt%；
Obtained c-SiO/C is and the agraphitic carbon group being evenly distributed on c-SiO matrixes by c-SiO matrixes
Into；
Step (a) and (c) are same as Example 3.
Embodiment 10
A kind of preparation method of silicon-carbon cathode material, except ferrocene ethanol solution in step (b) is replaced with into cobalt nitrate
Ethanol solution, remaining step are same as Example 8.
Embodiment 11
A kind of preparation method of silicon-carbon cathode material, except toluene in step (b) is replaced with into dimethylbenzene, remaining step is equal
It is same as Example 9.
Comparative example 1
A kind of preparation method of silicon-carbon cathode material, step (a) as different from Example 3, remaining step with implementation
Example 3 is identical.
(a) disproportionated reaction：Using the silicon monoxide of 500 mesh as matrix material, silicon monoxide is placed in heater, in temperature
Spend for 1500 DEG C, time be 6h under conditions of carry out disproportionated reaction, obtain c-SiO.
Comparative example 2
A kind of preparation method of silicon-carbon cathode material, step (b) as different from Example 3, remaining step with implementation
Example 3 is identical.
(b) vapor deposition reaction：It is placed in after c-SiO and copper powder are mixed in chemical vapor deposition stove, under argon gas protection
1000 DEG C are warming up to 10 DEG C/min heating rate, is passed through polystyrene carbon source, it is cold after carrying out chemical vapour deposition reaction 6h
But to room temperature, c-SiO/C is obtained.
Comparative example 3
A kind of preparation method of silicon-carbon cathode material, step (b) as different from Example 9, remaining step with implementation
Example 9 is identical.
(b) vapor deposition reaction：C-SiO and toluene are placed in chemical vapor deposition stove, in argon atmosphere, temperature
Spend to carry out vapor deposition reaction 8h under conditions of 650 DEG C, be cooled to room temperature, that is, obtain c-SiO/C.
Comparative example 4
A kind of preparation method of silicon-carbon cathode material, step (c) as different from Example 3, remaining step with implementation
Example 3 is identical.
(c) corrode：C-SiO/C is placed in 30wt% hydrofluoric acid aqueous solution, the mass ratio of c-SiO/C and hydrofluoric acid
For 1：After 1.01, stirring immersion 60min, it is washed with deionized, is dried at 125 DEG C, obtain silicon-carbon cathode material c-SiO/
Si/C。
Comparative example 5
A kind of preparation method of silicon-carbon cathode material, using the preparation side of carbon-silicon composite material of the prior art
Method；High temperature disproportionated reaction including silicon monoxide, and corrosion remove the step of silica is to prepare carbon-silicon composite material.
The silicon-carbon cathode material that each embodiment and comparative example are prepared carries out XRD tests and SEM sweep tests.Its
In, only it is described in detail by taking embodiment 3 as an example.Represented successively from bottom to top in Fig. 1 be matrix material SiO in embodiment 3,
It is disproportionated the c-SiO of generation, the c-SiO/C that vapour deposition obtains and the c-SiO/Si/C that corrosion obtains XRD.From Fig. 1
Spectrogram on it can be seen that SiO have diffraction maximum one wider and that diffracted intensity is low at 20~30 °, illustrate SiO be it is amorphous
State；The c-SiO obtained after high temperature disproportionated reaction in 28 °, 47 ° 56 ° except in addition to 20~30 ° have diffraction maximum, spreading out
Peak is penetrated, there occurs disproportionated reaction, the Si oxide (dioxy of silicon and amorphous state comprising crystalline state by SiO at high temperature for this explanation
SiClx)；And the diffraction maximum form passed through after vapour deposition and corrosion is without too big change.
Fig. 2 (a) and Fig. 2 (b) respectively illustrates the SEM figures of the c-SiO/C and c-SiO/Si/C in embodiment 3.From Fig. 2
In it can be seen that after vapour deposition, after loading one layer of carbon on c-SiO surface, obtained c-SiO/C composites
The granule-morphology of raw material is maintained, but particle surface becomes somewhat coarse；And the silicon-carbon cathode material obtained after excessive erosion
Expect that c-SiO/Si/C surface topography is preferable.
Electrochemical property test
Silicon-carbon cathode material made from embodiment 1-11 and comparative example 1-5 is made into half-cell respectively, and tests its phase
Powered-down chemical property, test result are as shown in table 1.Wherein, prepared by half-cell：Using active material as positive pole, lithium piece is negative pole group
Button cell is dressed up, conductive agent uses conductive carbon Super " p ", and barrier film celgard2400, electrolyte is from 1mol/L's
LiPF6Conducting salt and DMC：DEC：EC (wt%)=1：1：1 solvent.Test condition is：Discharge and recharge blanking voltage be 0.01~
First charge-discharge specific capacity is tested under 1.5V, 0.1C state, test loop efficiency 50 times under 0.5C, test result is as shown in table 1.
The electrochemical property test result of table 1
As can be seen from Table 1, silicon-carbon cathode material initial charge/discharge specific capacity provided by the invention is high, has extended cycle life,
Stability is good；The chemical property of silicon-carbon cathode material made from 1-11 of the embodiment of the present invention is substantially due to comparative example 1-5.Tool
Body says, the preparation method of silicon-carbon cathode material provided by the invention, not only better than the preparation side of existing silicon-carbon cathode material
Method, and the model of disproportionated reaction mode of operation, vapor deposition reaction mode of operation and the etching operation parameter limited in the present invention
In enclosing, obtained silicon-carbon cathode material, there is more excellent chemical property, specific capacity is higher, and cyclical stability is more preferable.
In addition, Fig. 3 (a), Fig. 3 (b) and Fig. 3 (c) respectively illustrate matrix material SiO in embodiment 3, vapour deposition obtains
C-SiO/C and corrosion obtained c-SiO/Si/C the 1st time, 10 times, 20 charge and discharge cycles curves；Fig. 4 shows it
Cycle-index-specific discharge capacity figure.Can also further it find out from Fig. 3 and Fig. 4, under identical testing conditions,
The silicon-carbon cathode material c-SiO/Si/C finally given specific capacity is high, and stable circulation is more preferable.
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, either which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (10)
1. a kind of preparation method of silicon-carbon cathode material, it is characterised in that comprise the following steps：
(a) using silicon monoxide as matrix material, silicon monoxide is heated, makes silicon monoxide that disproportionated reaction generation occur
C-SiO；
(b) c-SiO is positioned in chemical vapor deposition stove, heated up under protective atmosphere, after being warming up to reaction temperature
Carbon source is passed through, vapor deposition reaction is carried out, obtains c-SiO/C；
(c) c-SiO/C is obtained into silicon-carbon cathode material c-SiO/Si/C after corroding corrosion.
2. the preparation method of silicon-carbon cathode material according to claim 1, it is characterised in that the silicon monoxide matrix material
The granularity of material is 400~600 mesh, preferably 450~550 mesh, more preferably 500 mesh.
3. the preparation method of silicon-carbon cathode material according to claim 1, it is characterised in that in step (a), silicon monoxide
Occur disproportionated reaction detailed process be：
Silicon monoxide is placed in heater, is first warming up to 80~120 DEG C with 2~8 DEG C/min heating rate, insulation 0.5
700~1000 DEG C are warming up to 2~8 DEG C/min heating rate again after~2h, after being incubated 1~3h, room temperature is cooled to, obtains
C-SiO；
Preferably, the heater is provided with quartz boat, zirconium oxide boat or aluminium oxide boat.
4. the preparation method of silicon-carbon cathode material according to claim 1, it is characterised in that in step (b), the c-
C content is 3wt%~10wt% in SiO/C；
Preferably, described carbon source be polystyrene, glucose, sucrose, phenolic resin, epoxy resin, ferrocene ethanol solution,
Any one in ferrocene acetone soln, cobalt nitrate ethanol solution, benzene, toluene or dimethylbenzene；
Preferably, described reaction temperature is 700~1200 DEG C；
Preferably, described chemical vapor deposition stove is tube furnace, rotary furnace or Muffle furnace；
Preferably, described protective atmosphere is any one in nitrogen, helium, argon gas or neon.
5. the preparation method of silicon-carbon cathode material according to claim 4, it is characterised in that described carbon source is polyphenyl second
Alkene, the detailed process that c-SiO/C is obtained by vapor deposition reaction are：
The c-SiO and copper powder are subjected to ball milling, is well mixed, obtains mixture；The mixture is placed in chemical vapor deposition
The side of product stove, the polystyrene is placed in the opposite side of chemical vapor deposition stove；The first purifying 0.3 under protective atmosphere~
1h, then make mixture area be warming up to 700~900 DEG C with 3~7 DEG C/min heating rate, polystyrene area is warming up to 300~
500 DEG C, after being incubated 2~4h, room temperature is cooled to, that is, obtains described c-SiO/C；
Preferably, in addition to the pre-treatment step for copper powder, micron-sized copper powder is first cleaned by ultrasonic 20 through acetone soln~
40min, then it is cleaned by ultrasonic 10~30min with the acid solution that concentration is 20%~40%, then copper powder is cleaned with water, done
It is dry, then carry out ball milling with c-SiO；
Preferably, the step of in addition to removing copper powder, the obtained sample after cooling is placed in ferric chloride solution and removes copper powder,
Washed respectively with the acid solution and water that concentration is 5%~15% again, that is, obtain described c-SiO/C；
Preferably, described c-SiO/C is and the graphene group being evenly distributed on c-SiO matrixes by c-SiO matrixes
Into.
6. the preparation method of silicon-carbon cathode material according to claim 4, it is characterised in that described carbon source is ferrocene
Ethanol solution, the detailed process that c-SiO/C is obtained by vapor deposition reaction are：
The c-SiO is placed in chemical vapor deposition stove, first under protective atmosphere purify 0.3~1h, then with 3~7 DEG C/
Min heating rate is warming up to 900~1100 DEG C, is passed through ferrocene ethanol solution, carries out 2~5h of vapor deposition reaction, then
Remove carbon source and be cooled to room temperature, that is, obtain described c-SiO/C；
Preferably, the concentration range of described ferrocene ethanol solution is 5~20mg/mL；
Preferably, in addition to by the ferrocene ethanol solution heated under conditions of 40~60 DEG C, then be passed through chemical vapor deposition
The step of vapor deposition reaction being carried out in product stove；
Preferably, described c-SiO/C is and the CNT being evenly distributed on c-SiO matrixes by c-SiO matrixes
Composition.
7. the preparation method of silicon-carbon cathode material according to claim 4, it is characterised in that described carbon source is toluene,
The detailed process that c-SiO/C is obtained by vapor deposition reaction is：
The c-SiO is placed in chemical vapor deposition stove, first under protective atmosphere purify 0.3~1h, then with 3~7 DEG C/
Min heating rate is warming up to 700~1000 DEG C, is passed through toluene, carries out 1~4h of vapor deposition reaction, it is cold then to remove carbon source
But to room temperature, that is, described c-SiO/C is obtained；
Preferably, in addition to by the toluene heated, then be passed through in chemical vapor deposition stove under conditions of 40~60 DEG C
The step of carrying out vapor deposition reaction；
Preferably, described c-SiO/C is and the agraphitic carbon being evenly distributed on c-SiO matrixes by c-SiO matrixes
Composition.
8. the preparation method of the silicon-carbon cathode material according to any one of claim 1~7, it is characterised in that step (c)
In, the corrosive liquid is 3wt%~20wt% hydrofluoric acid aqueous solution, preferably 5wt%~10wt% hydrofluoric acid aqueous solution；
Preferably, the mass ratio of the c-SiO/C and hydrofluoric acid are 1：1.2~1.5, the time of corrosion treatment is 5~30min；
Preferably, the step for being washed with water and drying also is included after corrosion treatment, dry temperature is preferably 90~120 DEG C.
9. a kind of silicon-carbon cathode material, it is characterised in that as the system of the silicon-carbon cathode material described in any one of claim 1~8
Preparation Method is made.
10. a kind of lithium ion battery, it is characterised in that its negative pole includes the silicon-carbon cathode material described in claim 9.
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| CN111403708A (en) * | 2020-03-25 | 2020-07-10 | 广东凯金新能源科技股份有限公司 | Lithium ion battery silicon monoxide composite negative electrode material and preparation method thereof, and lithium ion battery |
| CN112635731A (en) * | 2020-12-17 | 2021-04-09 | 浙江锂宸新材料科技有限公司 | Preparation method of composite nano-silicon negative electrode material based on conductive carbon aerogel and product thereof |
| CN112635731B (en) * | 2020-12-17 | 2021-11-02 | 浙江锂宸新材料科技有限公司 | Preparation method of composite nano-silicon negative electrode material based on conductive carbon aerogel and product thereof |
| CN113023738A (en) * | 2021-03-03 | 2021-06-25 | 昆山宝创新能源科技有限公司 | Silicon-based composite material, preparation method thereof and battery |
| CN114864869A (en) * | 2022-05-30 | 2022-08-05 | 上海瑞浦青创新能源有限公司 | Negative electrode and preparation method and application thereof |
| CN115050966A (en) * | 2022-08-11 | 2022-09-13 | 楚能新能源股份有限公司 | Silicon-carbon negative electrode material and preparation method thereof |
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