CN108172812A - A kind of silicon-carbon cathode material available for power battery and preparation method thereof - Google Patents
A kind of silicon-carbon cathode material available for power battery and preparation method thereof Download PDFInfo
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- CN108172812A CN108172812A CN201810088301.2A CN201810088301A CN108172812A CN 108172812 A CN108172812 A CN 108172812A CN 201810088301 A CN201810088301 A CN 201810088301A CN 108172812 A CN108172812 A CN 108172812A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to electrochemical fields, are related to a kind of silicon-carbon cathode material available for power battery and preparation method thereof.It the described method comprises the following steps：（1）By the washing of micron order industrial silicon, purifying, crushed through sand mill, obtain nano-silicon；（2）Graphite sand is milled and broken obtains nano graphite powder；（3）By obtained nano-silicon, nano graphite powder, a certain amount of conductive agent is added, and after being sufficiently mixed with emulsified asphalt, be spray-dried, obtain near-spherical particle；（4）Obtained particle and organic carbon source will be spray-dried after mixing, and carry out secondary spray drying, obtain the silicon-carbon presoma of coated with carbon bed；（5）Under gas shield, silicon-carbon presoma is subjected to carbonization treatment, obtains silicon-carbon cathode material.The negative material has cycle and high rate performance well, and first circle is efficient, and preparation process is simple, and cost is relatively low, suitable for industrialized production.
Description
Technical field
The present invention relates to electrochemical fields, and in particular to a kind of silicon-carbon cathode material and its preparation available for power battery
Method.
Background technology
Lithium ion battery is the emphasis of electrochemical field research because of excellent properties such as energy density height, good cycles, and
It is increasingly becoming the major impetus source in new-energy automobile field.2 months 2017, the Ministry of Industry and Information Technology, State Development and Reform Commission, science and technology
Portion, Ministry of Finance's joint publication《Promote automobile power cell developing activity scheme（2017）》It is distinctly claimed the year two thousand twenty, novel lithium
The monomer of ion battery is more than 300 Wh/kg than energy.To realize this target, promote the fast development of power battery,
It is crucial to develop novel high-capacity high stable battery material.
Graphite is the main negative material of current power lithium battery, but its theoretical capacity only has 372 mAh/g, it is difficult to be met
At present for the requirement of power battery high-energy density.Silicon has theoretical capacity height（4200 mAh/g）, the advantages such as rich reserves,
It is expected to substitute graphite as next-generation power battery cathode material.The main reason for limiting silicon commercial applications is the volume effect of silicon
Should, huge volume expansion can generate a large amount of irreversible capacity loss, and first charge discharge efficiency is relatively low, as charge and discharge carry out, silicon table
Face SEI films（Solid electrolyte interface film）It can constantly crush and re-form, loop attenuation is serious.In addition the electric conductivity of silicon compared with
Difference, the volume expansion in charge and discharge process also result in active material and come off and inactivate from collector, and high rate performance is poor.
How effectively alleviating the volume expansion of silicon and improving materials conductive performance is particularly important.
The method of commercial applications most study is to prepare Si-C composite material by nano-silicon and carbon are compound at present, carbon tool
There are good cyclical stability and excellent electric conductivity, and silicon is compound can buffer the volume expansion of silicon, while improve composite wood
Expect electric conductivity.It is main including the traditional silicon carbon material compound with graphite, carbon black, soft carbon, hard carbon etc. and with carbon nanotube, graphene
Etc. the compound obtained novel silicon carbon material of new carbons, cladded type, embedded type can be also divided into according to the distribution mode difference of silicon
With molecule contacts type etc., graininess and network-type can be then divided into according to form, silicon-carbon can be also divided into according to the number of raw material type
Binary is compound with multiple elements design etc., and compared with pure silicon, cyclical stability is all significantly improved.Silicon carbon material is often selected at present
HIGH-PURITY SILICON is silicon source, and material cost is higher.Industrial silica fume is also known as metallic silicon, metal luster, in ingredient in addition to silicon, also few
The metal impurities such as iron, aluminium, the calcium of amount, cost is relatively low, by purifying, crushing to obtain nano-silicon applied to silicon-carbon cathode material, tool
There are very big cost advantage and application prospect.
Chinese patent CN103259005B provides one kind using superfine silica powder, conductive black and water-soluble resin as raw material system
It is spray-dried after standby slurry and calcines to obtain the method for 5 ~ 45 μm of silicon-carbon cathode material.The material is receives micro- tri compound knot
Structure, the amorphous carbon that resin is calcined provide buffering for the volume expansion of silicon, and the addition of conductive black compensates for silicon and without fixed
Shape carbon conductive can deficiency, but material is not avoided that being in direct contact for silicon and electrolyte, and conductive black is spherical
Grain, good conductive network can not be formed in material internal.Chinese patent CN105932245A discloses a kind of by silicon, graphite
Additive mixed calcining, then cladding calcining obtains the method for porous structure Si-C composite material again, improves the head of material
Efficiency is enclosed, and stability has certain promotion, but raw graphite grain size is larger, can not be mixed completely with nano-silicon in inside
Uniform, cushion performance variation after recycling for a long time is closed, and material internal electric conductivity is to be improved.
Invention content
The present invention proposes a kind of silicon-carbon cathode material available for power battery and preparation method thereof, the composite material with
Cheap micron silica flour is raw material, obtains the silicon of nanoscale by being sanded to crush, mixes, draw with obtained nano graphite powder is sanded
Enter a certain amount of conductive agent carbon nanotube, and the microballoon of nano-micro structure is dried to obtain with emulsified asphalt mixed atomizing；Again with it is organic
Carbon source mixing carries out secondary spray drying, calcining is made.The amorphous carbon layer energy that composite material surface organic carbon source is calcined
It is enough to promote to form stable SEI films in first circle charge and discharge process, avoid being in direct contact to the irreversible of lithium for silicon and electrolyte
Consumption improves first circle efficiency；Carbon nano-tube conductive is good, and with elasticity, stable lead can be formed in composite inner
Electric network promotes the quick transmission of ion and electronics；Nano silicone promotes its being uniformly distributed in material internal, graphite with graphite
The network structure formed with the soft carbon material that pitch is calcined provides good cushion space for the volume expansion of silicon.The material
Material can also improve its high rate performance while silicon-carbon cathode cyclical stability is improved, suitable for power battery cathode, and work
Skill is simple, and cost is relatively low, is suitble to industrialization amplification.
Realize the technical scheme is that：A kind of silicon-carbon cathode material available for power battery, negative material are table
Bread covers amorphous carbon, the spherical nano-micro structure that inside is made of nano silica fume, nano-graphite, soft carbon and carbon nanotube；Respectively
The weight percent of substance is：Nano silica fume 5 ~ 20%, nano-graphite 30 ~ 50%, carbon nanotube 5 ~ 20%, soft carbon 10-35%, remaining
For amorphous carbon.
The preparation method of the silicon-carbon cathode material available for power battery, step are as follows：
（1）The dispersion of micron industrial silica fume is configured to slurry in a solvent, is crushed in sand mill, nano-silicon is obtained after dry
Powder；
（2）Slurry is made in graphite powder dispersion in a solvent, is crushed in sand mill, is dried to obtain nano-graphite；
（3）Nano silica fume, nano-graphite, carbon nanotube and emulsified asphalt are mixed, add in deionized water or ethyl alcohol, is uniformly mixed
After obtain dispersion liquid A, dispersion liquid A is spray-dried, it is 180 ~ 250 DEG C that the condition of spray drying, which is inlet temperature, outlet
Temperature is 80 ~ 120 DEG C, obtains spherical particle；
（4）Organic carbon source is added in deionized water, obtains organic carbon source solution, by step（3）Obtained spherical particle
It is added in organic carbon source solution, obtains dispersion liquid B after mixing, dispersion liquid B is spray-dried, the item of spray drying
Part is：Inlet temperature is 180-250 DEG C, and outlet temperature is 80-120 DEG C, obtains silicon-carbon presoma；
（5）By step（4）Obtained silicon-carbon presoma is warming up to 800 ~ 1000 DEG C under gas shield, keeps the temperature, is cooled to room temperature,
Obtain silicon-carbon cathode material.
The step（1）And step（2）Middle solvent is deionized water, ethyl alcohol, ethylene glycol, glycerine, isopropanol, positive fourth
One kind in alcohol, acetone, chloroform, N-N dimethylformamides, N-Methyl pyrrolidone or methanol, the step（1）And step
（2）Solid content is 10 ~ 30% in slurry.
The step（1）Silicone content is more than 85% in middle micron silica flour, and the grain size of micron silica flour is 5 ~ 50 μm, in sand mill
The sand milling time is 5 ~ 10h, crushes the nano silica fume obtained after drying, the grain size of nano silica fume is 50 ~ 500nm.
The step（2）In graphite powder at least one of Delanium and spherical natural graphite, the grain of graphite powder
Diameter is 5 ~ 20 μm, and it is 5 ~ 10h that the time is sanded in sand mill, crushes the nano graphite powder obtained after drying, the grain of nano graphite powder
Diameter is 100 ~ 500nm.
The step（3）In carbon nanotube be at least one of single wall and multi-walled carbon nanotube.
The step（3）Solid content is 10 ~ 50% in dispersion liquid A, and the grain size of obtained spherical particle is 10 ~ 50 μm.
The step（4）Organic carbon source is sucrose, glucose, chitosan, citric acid, polyvinyl alcohol, polyaniline, fiber
Element, polyacrylonitrile or one kind in polyacrylic acid or arbitrary two kinds of mixing；In dispersion liquid B solid content be 15-50%, obtained silicon
The grain size of carbon matrix precursor is 10 ~ 50 μm.
The step（5）With 1 ~ 20 DEG C of min under gas shield-1Heating rate rise to 800 ~ 1000 DEG C, keep the temperature 2-
6h。
The step（5）Middle gas is the argon hydrogen gaseous mixture that high-purity argon gas, high pure nitrogen or hydrogen content are 5%.
The beneficial effects of the invention are as follows：It is unformed to prepare surface cladding using the method being spray-dried twice by the present invention
Carbon-coating receives micro- Si-C composite material.It is sanded to obtain the silicon and graphite powder of Nano grade using cheap micron silicon and graphite as raw material,
With carbon nanotube and emulsified asphalt be mixed with slurry spraying be dried to obtain spherical micro- compound of receiving, then again with organic carbon
Source is mixed with the secondary spray drying calcining of slurry and obtains micro- silicon-carbon cathode material of receiving of surface cladding amorphous carbon layer, surface packet
The amorphous carbon layer covered peomotes material and forms stable SEI films, improves the first circle efficiency and stability of material；Carbon nanometer
The introducing of pipe can form stable conductive network in composite inner, promote the quick transmission of lithium ion and electronics；Nanometer
Silicon promotes what its soft carbon material calcined in the homodisperse of material internal, graphite and pitch was formed with nano graphite powder
Network structure can provide good cushioning effect for the volume expansion of silicon.The present invention is easy to operate, is easy to industrialized production；The knot
The Si-C composite material of structure has good cyclical stability and high rate performance, has good application prospect.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention, for those of ordinary skill in the art, without creative efforts, can be with
Other attached drawings are obtained according to these attached drawings.
Fig. 1 is the scanning electron microscope (SEM) photograph of silicon-carbon composite cathode material that embodiment 1 obtains under 5.00k enlargement ratios.
Fig. 2 is the charge and discharge cycles curve graph of the silicon-carbon composite cathode material obtained in embodiment 1.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's all other embodiments obtained under the premise of not making the creative labor, belong to this hair
The range of bright protection.
In following embodiment, using the microcosmic shape of sample prepared by Hitachi S-3400N scanning electron microscope measure
Looks.Battery performance test is electric using the indigo plant of the model LANHE CT2001A of Wuhan Land Electronic Co., Ltd.'s production
Battery test system.
The experimental drug and method of actual conditions are not specified in the following example, according to customary commercial or condition or according to
Product manual uses, and in the following example, micron order industrial silica fume is repeatedly washed by deionized water and ethyl alcohol, uses 1M
HCl washing purifying 12h, use after 60 DEG C of dryings.
Carbon nanotube：Purchased from Suzhou Tan Feng graphenes Science and Technology Ltd.；
Emulsified asphalt：Purchased from Zhejiang Bo Feng urban engineering projects Co., Ltd, SBR modified cation emulsifiers, solid content 50%.
By silicon-carbon cathode material prepared by the present invention and acetylene black and Kynoar（PVDF）It is 8 according to mass ratio:1:1
In N-Methyl pyrrolidone（NMP）In slurry is made, be uniformly coated on copper foil drying and electrode be made.Electrolyte selects 1.0
mol L-1LiPF6Mixed organic solvents, solvent is that mass ratio is 1:1:1 EC:DEC:DMC, diaphragm are capillary polypropylene
Diaphragm, just extremely lithium piece, are processed into CR2025 button cells.Cycle performance test uses 100 mAg-1Current density carry out it is permanent
Charge-discharge test is flowed, charging/discharging voltage ranging from 0.005 ~ 2V is tested under normal temperature condition.
Embodiment 1
The preparation method of silicon-carbon cathode material in the present embodiment available for power battery is as follows：
The silica flour that grain size is 5 ~ 10 μm is disperseed in ethanol, to be configured to the slurry that solid content is 30%, is crushed in sand mill
5h, it is dry, the nano silica fume that grain size is 100 ~ 200nm is obtained, it is spare；It is 1 by mass ratio：1, grain size is 10 ~ 20 μm artificial
Graphite and native graphite dispersion in ethanol, are configured to the slurry that solid content is 30%, 5h are crushed in sand mill, dry, obtain
Grain size is the nano graphite powder of 100 ~ 200nm, spare；
10g nano silica fumes, 30g nano graphite powders, 90g emulsified asphalts, 5g single-walled carbon nanotubes are mixed, add in 540g deionizations
Water, stirring 6h obtain slurry, are spray-dried, and the inlet temperature for controlling spray dryer is 220 DEG C, outlet temperature 100
DEG C, supply disk frequency is 20Hz, and atomizing disk frequency is 300Hz, obtains spherical particle；
10g glucose is dissolved in 530g deionized waters, adds in the above-mentioned spherical particle being dried to obtain, stirring 6h is starched
Material, is spray-dried, and the inlet temperature for controlling spray dryer is 220 DEG C, and outlet temperature is 100 DEG C, and supply disk frequency is
20Hz, atomizing disk frequency are 300Hz, obtain silicon-carbon granular precursor；
In carbide furnace, the silicon-carbon granular precursor that above-mentioned spray drying is obtained is under protection of argon gas with 5 DEG C of min-1Liter
Warm rate rises to 800 DEG C, keeps the temperature 4h, and cooled to room temperature obtains the spherical powder that black grain size is 10 ~ 20 μm, as
Silicon-carbon cathode material.
Embodiment 2
The preparation method of silicon-carbon cathode material in the present embodiment available for power battery is as follows：
The silica flour that grain size is 10 ~ 20 μm or so is disperseed in methyl alcohol, to be configured to the slurry that solid content is 30%, in sand mill
8h is crushed, it is dry, the nano silica fume that grain size is 100 ~ 200nm is obtained, it is spare；Grain size is dispersed in for 10 ~ 20 μm of Delaniums
In methanol, the slurry that solid content is 30% is configured to, 5h is crushed in sand mill, dry, it is receiving for 100 ~ 200nm to obtain grain size
Rice graphite powder, it is spare；
By 10g nano silica fumes, 20g nano graphite powders, 110g emulsified asphalts, 5g single-walled carbon nanotubes mix, add in 580g go from
Sub- water, stirring 6h obtain slurry, are spray-dried, and the inlet temperature for controlling spray dryer is 200 DEG C, and outlet temperature is
100 DEG C, supply disk frequency is 20Hz, and atomizing disk frequency is 300Hz, obtains spherical particle；
10g sucrose is dissolved in 580g deionized waters, adds in the above-mentioned spherical particle being dried to obtain, stirring 6h obtains slurry,
It is spray-dried, the inlet temperature for controlling spray dryer is 200 DEG C, and outlet temperature is 100 DEG C, and supply disk frequency is
20Hz, atomizing disk frequency are 300Hz, obtain silicon-carbon granular precursor；
In carbide furnace, by the silicon-carbon granular precursor that above-mentioned spray drying obtains with 5 DEG C of min under high-purity argon gas protection-1
Heating rate rise to 800 DEG C, keep the temperature 3h, cooled to room temperature obtains the spherical powder that black grain size is 10 ~ 20 μm or so
End, as silicon-carbon cathode material.
Embodiment 3
The preparation method of silicon-carbon cathode material in the present embodiment available for power battery is as follows：
The silica flour that grain size is 1 ~ 5 μm is dispersed in isopropanol, the slurry that solid content is 30% is configured to, is crushed in sand mill
8h, it is dry, the nano silica fume that grain size is 100 ~ 150nm is obtained, it is spare；The spherical natural graphite that grain size is 5 ~ 10 μm is dispersed in
In isopropanol, the slurry that solid content is 30% is configured to, 8h is crushed in sand mill, dry, it is 100 ~ 150nm's to obtain grain size
Nano graphite powder, it is spare；
5g nano silica fumes, 20g nano graphite powders, 130g emulsified asphalts, 5g single-walled carbon nanotubes are mixed, add in 640g deionizations
Water, stirring 6h obtain slurry, are spray-dried, and the inlet temperature for controlling spray dryer is 180 DEG C, outlet temperature 80
DEG C, supply disk frequency is 20Hz, and atomizing disk frequency is 300Hz, obtains spherical particle；
10g chitosans are dissolved in 450g deionized waters, add in the above-mentioned spherical particle being dried to obtain, stirring 6h is starched
Material, is spray-dried, and the inlet temperature for controlling spray dryer is 180 DEG C, and outlet temperature is 80 DEG C, and supply disk frequency is
20Hz, atomizing disk frequency are 300Hz, obtain silicon-carbon granular precursor；
In carbide furnace, the silicon-carbon granular precursor that above-mentioned spray drying obtains is protected in the argon hydrogen gaseous mixture that hydrogen content is 5%
With 5 DEG C of min under shield-1Heating rate rise to 800 DEG C, keep the temperature 3h, cooled to room temperature obtains black grain size as 10 ~ 20 μ
The spherical powder of m, as silicon-carbon cathode material.
Embodiment 4
The preparation method of silicon-carbon cathode material in the present embodiment available for power battery is as follows：
The silica flour that grain size is 10 ~ 20 μm is disperseed in acetone, to be configured to the slurry that solid content is 10%, is crushed in sand mill
10h, it is dry, the nano silica fume that grain size is 150 ~ 250nm is obtained, it is spare；It is 1 by mass ratio：1,10 ~ 20 μm of grain size position it is artificial
Graphite and spherical natural graphite dispersion in acetone, are configured to the slurry that solid content is 10%, 10h are crushed in sand mill, do
It is dry, nano graphite powder of the grain size for 150 ~ 250nm or so is obtained, it is spare；
5g nano silica fumes, 20g nano graphite powders, 90g emulsified asphalts, 10g multi-walled carbon nanotubes are mixed, add in 290g deionizations
Water, stirring 6h obtain slurry, are spray-dried, and the inlet temperature for controlling spray dryer is 250 DEG C, outlet temperature 120
DEG C, supply disk frequency is 20Hz, and atomizing disk frequency is 300Hz, obtains spherical particle；
20g citric acids are dissolved in 270g deionized waters, add in the above-mentioned spherical particle being dried to obtain, stirring 6h is starched
Material, is spray-dried, and the inlet temperature for controlling spray dryer is 250 DEG C, and outlet temperature is 120 DEG C, and supply disk frequency is
20Hz, atomizing disk frequency are 300Hz, obtain silicon-carbon granular precursor；
In carbide furnace, by the silicon-carbon granular precursor that above-mentioned spray drying obtains with 10 DEG C of min under high pure nitrogen protection-1Heating rate rise to 900 DEG C, keep the temperature 6h, cooled to room temperature obtains the spherical powder that black grain size is 15 ~ 25 μm,
As silicon-carbon cathode material.
Embodiment 5
The preparation method of silicon-carbon cathode material in the present embodiment available for power battery is as follows：
The silica flour that grain size is 10 ~ 20 μm or so is dispersed in n-butanol, the slurry that solid content is 30% is configured to, in sand mill
Middle crushing 10h, it is dry, the nano silica fume that grain size is 100 ~ 150nm is obtained, it is spare；It is 1 by mass ratio：1, grain size is 5 ~ 10 μm
Delanium and spherical natural graphite be dispersed in n-butanol, be configured to solid content be 20% slurry, crushed in sand mill
8h, it is dry, the nano graphite powder that grain size is 100 ~ 150nm is obtained, it is spare；
It is 1 by 10g nano silica fumes, 30g nano graphite powders, 80g emulsified asphalts, 10g mass ratioes：1 single wall and multi-wall carbon nano-tube
Pipe mixes, and adds in 300g deionized waters, and stirring 6h obtains slurry, is spray-dried, controls the inlet temperature of spray dryer
It it is 250 DEG C, outlet temperature is 100 DEG C, and supply disk frequency is 20Hz, and atomizing disk frequency is 300Hz, obtains spherical particle；
10g polyvinyl alcohol is dissolved in 280g deionized waters, adds in the above-mentioned spherical particle being dried to obtain, stirring 6h is starched
Material, is spray-dried, and the inlet temperature for controlling spray dryer is 250 DEG C, and outlet temperature is 80 DEG C, and supply disk frequency is
20Hz, atomizing disk frequency are 300Hz, obtain silicon-carbon granular precursor；
In carbide furnace, the silicon-carbon granular precursor that above-mentioned spray drying is obtained is under protection of argon gas with 5 DEG C of min-1Liter
Warm rate rises to 800 DEG C, keeps the temperature 3h, and cooled to room temperature obtains the spherical powder that black grain size is 15 ~ 25 μm, as
Silicon-carbon cathode material.
Embodiment 6
The preparation method of silicon-carbon cathode material in the present embodiment available for power battery is as follows：
The silica flour that grain size is 10 ~ 20 μm is dispersed in N-N dimethylformamides, the slurry that solid content is 20% is configured to, in sand
5h is crushed in grinding machine, it is dry, nano silica fume of the grain size for 50 ~ 150nm or so is obtained, it is spare；It is 1 by mass ratio：1, grain size is
10-20 μm of Delanium and spherical natural graphite is dispersed in N-N dimethylformamides, is configured to the slurry that solid content is 10%
Material, crushes 5h in sand mill, dry, obtains the nano graphite powder that grain size is 300 ~ 500nm, spare；
15g nano silica fumes, 40g nano graphite powders, 60g emulsified asphalts, 5g multi-walled carbon nanotubes are mixed, add in 280g deionizations
Water, stirring 6h obtain slurry, are spray-dried, and the inlet temperature for controlling spray dryer is 250 DEG C, outlet temperature 100
DEG C, supply disk frequency is 20Hz, and atomizing disk frequency is 300Hz, obtains spherical particle；
10g polyethylene glycol is dissolved in 250g deionized waters, adds in the above-mentioned spherical particle being dried to obtain, stirring 6h is starched
Material, is spray-dried, and the inlet temperature for controlling spray dryer is 200 DEG C, and outlet temperature is 80 DEG C, and supply disk frequency is
20Hz, atomizing disk frequency are 300Hz, obtain silicon-carbon granular precursor；
In carbide furnace, the silicon-carbon granular precursor that above-mentioned spray drying is obtained is under protection of argon gas with 5 DEG C of min-1Liter
Warm rate rises to 900 DEG C, keeps the temperature 3h, and cooled to room temperature obtains the spherical powder that black grain size is 10 ~ 20 μm, as
Silicon-carbon cathode material.
Embodiment 7
The preparation method of silicon-carbon cathode material in the present embodiment available for power battery is as follows：
The silica flour that grain size is 40 ~ 50 μm is dispersed in N-Methyl pyrrolidone, the slurry that solid content is 10% is configured to, in sand
5h is crushed in grinding machine, it is dry, the nano silica fume that grain size is 300 ~ 500nm is obtained, it is spare；It is 1 by mass ratio：1, grain size is 5 ~ 10
μm Delanium and spherical natural graphite be dispersed in N-Methyl pyrrolidone, be configured to solid content be 30% slurry, in sand
5h is crushed in grinding machine, it is dry, the nano graphite powder that grain size is 100 ~ 200nm is obtained, it is spare；
By 15g nano silica fumes, 30g nano graphite powders, 50g emulsified asphalts, 10g single-walled carbon nanotubes mix, add in 150g go from
Sub- water, stirring 6h obtain slurry, are spray-dried, and the inlet temperature for controlling spray dryer is 200 DEG C, and outlet temperature is
120 DEG C, supply disk frequency is 20Hz, and atomizing disk frequency is 300Hz, obtains spherical particle；
15g polyacrylic acid is dissolved in 135g deionized waters, adds in the above-mentioned spherical particle being dried to obtain, stirring 6h is starched
Material, is spray-dried, and the inlet temperature for controlling spray dryer is 200 DEG C, and outlet temperature is 120 DEG C, and supply disk frequency is
20Hz, atomizing disk frequency are 300Hz, obtain silicon-carbon granular precursor；
In carbide furnace, the silicon-carbon granular precursor that above-mentioned spray drying is obtained is under protection of argon gas with 20 DEG C of min-1's
Heating rate rises to 1000 DEG C, keeps the temperature 2h, and cooled to room temperature obtains the spherical powder that black grain size is 20 ~ 30 μm, i.e.,
For silicon-carbon cathode material.
Embodiment 8
The preparation method of silicon-carbon cathode material in the present embodiment available for power battery is as follows：
The silica flour that grain size is 10 ~ 20 μm or so is disperseed in methyl alcohol, to be configured to the slurry that solid content is 30%, in sand mill
5h is crushed, it is dry, the nano silica fume that grain size is 150 ~ 200nm is obtained, it is spare；It is 1 by mass ratio：1, grain size is 10 ~ 20 μm
Delanium and native graphite dispersion in methyl alcohol, are configured to the slurry that solid content is 10%, 5h are crushed in sand mill, dry,
The nano graphite powder that grain size is 200 ~ 300nm is obtained, it is spare；
5g nano silica fumes, 40g nano graphite powders, 60g emulsified asphalts, 15g multi-walled carbon nanotubes are mixed, add in 120g deionizations
Water, stirring 6h obtain slurry, are spray-dried, and the inlet temperature for controlling spray dryer is 250 DEG C, outlet temperature 100
DEG C, supply disk frequency is 20Hz, and atomizing disk frequency is 300Hz, obtains spherical particle；
10g polyvinyl alcohol is dissolved in 110g deionized waters, adds in the above-mentioned spherical particle being dried to obtain, stirring 6h is starched
Material, is spray-dried, and the inlet temperature for controlling spray dryer is 250 DEG C, and outlet temperature is 100 DEG C, and supply disk frequency is
20Hz, atomizing disk frequency are 300Hz, obtain silicon-carbon granular precursor；
In carbide furnace, the silicon-carbon granular precursor that above-mentioned spray drying is obtained is under protection of argon gas with 10 DEG C of min-1's
Heating rate rises to 1000 DEG C, keeps the temperature 2h, and cooled to room temperature obtains the spherical powder that black grain size is 35 ~ 50 μm, i.e.,
For silicon-carbon cathode material.
Table 1 is the chemical property of power battery silicon-carbon cathode material obtained in case study on implementation 1 ~ 8.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (10)
1. a kind of silicon-carbon cathode material available for power battery, it is characterised in that：Negative material for surface coat amorphous carbon,
The spherical nano-micro structure that inside is made of nano silica fume, nano-graphite, soft carbon and carbon nanotube；The weight percent of each substance
For：Nano silica fume 5 ~ 20%, nano-graphite 30 ~ 50%, carbon nanotube 5 ~ 20%, soft carbon 10-35%, remaining is amorphous carbon.
2. a kind of preparation method of the silicon-carbon cathode material as described in claim 1 available for power battery, it is characterised in that
Step is as follows：
（1）The dispersion of micron industrial silica fume is configured to slurry in a solvent, is crushed in sand mill, nano-silicon is obtained after dry
Powder；
（2）Slurry is made in graphite powder dispersion in a solvent, is crushed in sand mill, is dried to obtain nano-graphite；
（3）Nano silica fume, nano-graphite, carbon nanotube and emulsified asphalt are mixed, add in deionized water or ethyl alcohol, is uniformly mixed
After obtain dispersion liquid A, dispersion liquid A is spray-dried, it is 180 ~ 250 DEG C that the condition of spray drying, which is inlet temperature, outlet
Temperature is 80 ~ 120 DEG C, obtains spherical particle；
（4）Organic carbon source is added in deionized water, obtains organic carbon source solution, by step（3）Obtained spherical particle
It is added in organic carbon source solution, obtains dispersion liquid B after mixing, dispersion liquid B is spray-dried, the item of spray drying
Part is：Inlet temperature is 180-250 DEG C, and outlet temperature is 80-120 DEG C, obtains silicon-carbon presoma；
（5）By step（4）Obtained silicon-carbon presoma is warming up to 800 ~ 1000 DEG C under gas shield, keeps the temperature, is cooled to room temperature,
Obtain silicon-carbon cathode material.
3. the preparation method of the silicon-carbon cathode material available for power battery according to claims 2, it is characterised in that：
The step（1）And step（2）Middle solvent is deionized water, ethyl alcohol, ethylene glycol, glycerine, isopropanol, n-butanol, acetone, chlorine
One kind in imitative, N-N dimethylformamides, N-Methyl pyrrolidone or methanol, the step（1）And step（2）It is solid in slurry
Content is 10 ~ 30%.
4. the preparation method of the silicon-carbon cathode material available for power battery according to claims 2, it is characterised in that：
The step（1）Silicone content is more than 85% in middle micron silica flour, and the grain size of micron silica flour is 5 ~ 50 μm, and the time is sanded in sand mill
For 5 ~ 10h, the nano silica fume obtained after drying is crushed, the grain size of nano silica fume is 50 ~ 500nm.
5. the preparation method of the silicon-carbon cathode material available for power battery according to claims 2, it is characterised in that：
The step（2）In graphite powder at least one of Delanium and spherical natural graphite, the grain size of graphite powder is 5 ~ 20 μ
M, it is 5 ~ 10h that the time is sanded in sand mill, crush it is dry after obtained nano graphite powder, the grain size of nano graphite powder for 100 ~
500nm。
6. the preparation method of the silicon-carbon cathode material available for power battery according to claims 2, it is characterised in that：
The step（3）In carbon nanotube be at least one of single wall and multi-walled carbon nanotube.
7. the preparation method of the silicon-carbon cathode material available for power battery according to claims 2, it is characterised in that：
The step（3）Solid content is 10 ~ 50% in dispersion liquid A, and the grain size of obtained spherical particle is 10 ~ 50 μm.
8. the preparation method of the silicon-carbon cathode material available for power battery according to claims 2, it is characterised in that：
The step（4）Organic carbon source is sucrose, glucose, chitosan, citric acid, polyvinyl alcohol, polyaniline, cellulose, polypropylene
One kind or arbitrary two kinds of mixing in nitrile or polyacrylic acid；Solid content is 15-50% in dispersion liquid B, obtained silicon-carbon presoma
Grain size is 10 ~ 50 μm.
9. the preparation method of the silicon-carbon cathode material available for power battery according to claims 2, it is characterised in that：
The step（5）With 1 ~ 20 DEG C of min under gas shield-1Heating rate rise to 800 ~ 1000 DEG C, keep the temperature 2-6h.
10. the preparation method of the silicon-carbon cathode material available for power battery according to claims 2, feature exist
In：The step（5）Middle gas is the argon hydrogen gaseous mixture that high-purity argon gas, high pure nitrogen or hydrogen content are 5%.
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