CN106025219A - Spherical silicon-oxygen-carbon negative electrode composite material and preparation method and application thereof - Google Patents
Spherical silicon-oxygen-carbon negative electrode composite material and preparation method and application thereof Download PDFInfo
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- CN106025219A CN106025219A CN201610464959.XA CN201610464959A CN106025219A CN 106025219 A CN106025219 A CN 106025219A CN 201610464959 A CN201610464959 A CN 201610464959A CN 106025219 A CN106025219 A CN 106025219A
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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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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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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
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- 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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a spherical silicon-oxygen-carbon negative electrode composite material, which is of a three-layer structure comprising an inner layer, an intermediate layer and an outer layer, wherein the inner layer is an SiOx/graphite substrate; the intermediate layer is an amorphous carbon coating layer; the outer layer is a carbon nanotube coating layer; the mass of the inner layer SiOx/graphite substrate accounts for 80%-90% of total mass of the spherical silicon-oxygen-carbon negative electrode composite material; the mass of the intermediate layer amorphous carbon accounts for 5%-10% of total mass of the spherical silicon-oxygen-carbon negative electrode composite material; and the outer layer carbon nanotube accounts for 5%-10% of total mass of the spherical silicon-oxygen-carbon negative electrode composite material. The grain diameter of the adopted SiOx substrate is smaller than 5 microns; the grain diameter is relatively small; intercalation and deintercalation of active substances are facilitated; higher specific capacity can be obtained; meanwhile, a dispersing agent is added when an SiOx sample is ground; and condition that the SiOx with a relatively small grain diameter is agglomerated in quantity to affect the performance is prevented.
Description
Technical field
The invention belongs to lithium ion battery negative material preparation and energy storage device field, be specifically related to
A kind of spherical silica anode composite and its production and use.
Background technology
Silicon materials can substitute current commercialization graphite material well as lithium ion battery negative material, and it has specific volume
The plurality of advantages such as amount height, good, the nontoxic pollution-free of safety, and in the earth's crust, abundance is only second to oxygen, wide material sources.Although silicon material
Material can solve the problems of current commercialization carbon negative pole material, but also faces two serious problems: first, and silicon is as half
Conductor material, electrical conductivity is relatively low, and during causing lithium ion deintercalation, irreversible degree is relatively big, and coulombic efficiency is relatively low first；Second,
Silicon during Lithium-ion embeding and deintercalation change in volume up to 400%(Li22Si5), thus cause electrode structure to be broken
Bad, it is difficult to form stable SEI(solid electrolyte interface) film, there is powder of detached, and then has a strong impact on the electricity of preparation in pole piece
Pond cycle performance.Compared with silica-base material, siloxy (SiOx) material can react in process of intercalation first generation Li2O and
Li4SiO4Substrate, can buffer silicon materials change in volume during removal lithium embedded, thus cycle performance is more compared with silicon materials
Good.By SiOxMaterial and carbon carry out being compounded to form silica carbon (SiOx-C) material, can improve the cycle performance of battery further.
This is because at SiOxMaterial surface one layer of carbon of cladding, is possible not only to the change in volume during padded coaming removal lithium embedded, and
The electric conductivity of material can be increased.
At present, the carbon cladding for the SiO electrode material prepared has been carried out numerous studies, and defines a series of
Patent.CN 102263245A discloses the preparation method of a kind of spherical porous composite cathode material for lithium ion cell, is aoxidized by silicon
Mix with graphite after thing high-energy ball milling and carry out mist projection granulating, then the globular material obtained is sintered in an inert atmosphere and obtain ball
Shape porous lithium ion cell composite negative pole material.The granule that this invention obtains after being spray-dried is surface only one layer of amorphous carbon
Porous material, in lithium battery, the silicon in material is easy to expose in the electrolytic solution, it is difficult to forms stable SEI film, and then leads
Efficiency for charge-discharge is low, cycle performance of battery is poor in cause.
CN 103199252A discloses a kind of lithium-ion battery silicon-carbon anode material and preparation method thereof, by SiO material
Carry out being thermally treated resulting in monocrystal silicon or Uniform polycrystalline silicon is dispersed in SiOxIn Si oxide, then by the Si oxide that obtains and
Graphite composite powder, organic carbon source mix and are distributed in solvent, are dried and sinter in inert atmosphere or reducing atmosphere, pulverize
To oxygen-containing Si-C composite material, uniformly it is mixed to get lithium-ion battery silicon-carbon anode material the most again with graphite composite powder.This
Bright needs carry out heat treatment specially to SiO material, and the most oxygen-containing Si-C composite material particle diameter is difficult to control to, and processing characteristics is bad,
It is not suitable for industrialization.
For the deficiencies in the prior art, it is an object of the invention to provide a kind of lithium ion battery negative material and preparation thereof
Method.Described lithium ion battery negative material has higher specific capacity, good processing characteristics and stable charge and discharge cycles
Performance.
Summary of the invention
The present invention is directed to existing silica carbon composite silicon easily expose in the electrolytic solution thus efficiency for charge-discharge is low, needs
Individually heat treatment SiOxCause preparation technology to be not suitable for the defect of industrialized production, now provide a kind of preparation method the simplest
List, cost are relatively low, it is adaptable to spherical silica anode composite of industrialized production and its production and use.
For solving above-mentioned technical problem, the technical solution used in the present invention is: a kind of spherical silica anode composite,
Its innovative point is: include internal layer, intermediate layer and outer layer three-decker, and described internal layer is SiOx/ graphite matrix, described intermediate layer
For amorphous carbon, described outer layer is CNT, described internal layer SiOx/ graphite matrix quality accounts for spherical silica Carbon anode composite wood
The percentage ratio of material gross mass is 80-90%, and described intermediate layer amorphous carbon quality accounts for spherical silica anode composite gross mass
Percentage ratio be 5-10%, described outer layer carbon nanotube mass accounts for the percentage ratio of spherical silica anode composite gross mass and is
5-10%；Described SiOxMatrix is to have on crystal structure characteristic and SiO or Si and SiOxThe consistent feature of complex,
The span of described X is more than 0 and less than 2；Described silica carbon composite is shaped as spherical or class is spherical, described silica carbon
The particle diameter of composite is 5-45 μm.
Another object of the present invention is to disclose a kind of spherical silica anode composite preparation method, and its innovative point exists
In: comprise the following steps:
(1) by SiOxMaterial, dispersant and organic solvent are mixed into slurry, use sand mill to be ground to SiOxParticle diameter is less than 5 μm；
(2) slurry, graphite and the organic carbon source that obtain after grinding carry out high speed dispersion, then drying-granulating；
(3) heat up under protective atmosphere sintering by the spherical or spherical particle obtained, and is then cooled to room temperature, obtains amorphous
The SiO of carbon claddingx/ graphite material；
(4) SiO that amorphous carbon is coated withx/ graphite material mixes with catalyst precursor, then passes through chemical vapour deposition technique
It is coated with one layer of CNT, obtains final spherical silica carbon negative pole material.
Further, the slurry solid content in described step (1) is 10-45%；Described SiOxMaterial is directly to buy or logical
Cross SiO2Prepare than pyroreaction with equimolar with Si；Described dispersant is organic carbon source dispersant commonly used in the art,
One or both mixing being preferably in sodium carboxymethyl cellulose, polyvinyl alcohol, described dispersant addition accounts for gross mass
0.5-2%。
Further, the organic solvent in described step (1) be methanol, ethanol, ethylene glycol, propanol, isopropanol, 1,2-third
Glycol, 1,3-propylene glycol, glycerol, n-butyl alcohol, 1,2-butanediol, 1,3 butylene glycol, 1,4-butanediol, n-amyl alcohol, acetone, first
In base ethyl ketone, methyl propyl ketone, ethyl propyl ketone, methyl butyl ketone, ethyl n-butyl ketone and methyl amyl ketone 1
Kind, preferably a kind in ethanol, ethylene glycol, isopropanol, acetone and n-butyl alcohol；SiO after described grindingxParticle diameter is 50-
5000nm, preferably 100-1000nm.
Further, the graphite in described step (2) is native graphite, Delanium, micro crystal graphite, carbonaceous mesophase spherules
With the one kind or two or more combination in soft carbon；Described graphite particle diameter D50For 2-8 μm；Described graphite and SiOxMass ratio be 1:
3-3:1；Described organic carbon source is glucose, sucrose, citric acid, Polyethylene Glycol, polyvinyl butyral resin, polyvinylpyrrolidine
In ketone, polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, epoxy resin, phenolic resin, Colophonium, starch, cellulose, polyaniline 1
Planting or combination of more than two kinds, the quality that described organic carbon source adds is by carbon content and SiOxThe mass ratio of/graphite is 1:18-1:
8。
Further, the high speed dispersion in described step (2) uses high speed dispersor, arranges speed of agitator 500-
2000rpm, mixing time 0.5-2h；Described drying-granulating uses sponging granulator, and inlet temperature is 220-280 DEG C, outlet temperature
Degree is for 90-120 DEG C；Described sponging granulator charging pump frequency is 10-20Hz, and atomizing disk frequency is 250-300Hz.
Further, the protective atmosphere in described step (3) is 1 in noble gas, reducing gas or vacuum atmosphere
Plant or the combination of at least 2 kinds；Described noble gas is a kind in nitrogen, argon, helium, neon, and described reducing gas is hydrogen
One or both combination in gas, carbon monoxide, described vacuum atmosphere pressure is less than less than 0.1MPa, preferably pressure
0.05MPa；Described heating rate is 1-20 DEG C/min, preferably 5-15 DEG C/min；Described sintering temperature is 200-800 DEG C, excellent
Elect 300-600 DEG C as；Described sintering time is 2-15 hour, preferably 4-10 hour.
Further, the concretely comprising the following steps of the mixing in described step (4): the SiO that amorphous carbon is coated withx/ graphite material
Material and catalyst precursor add to organic solvent, and solid content is 5-40%, and stirring is to being dried；Described catalyst precursor is
In ferric nitrate, nickel acetate or copper sulfate a kind；Described catalyst precursor mass fraction 1%-10%；Described organic solvent is first
Alcohol, ethanol, ethylene glycol, propanol, isopropanol, 1,2-propylene glycol, 1,3-propylene glycol, glycerol, n-butyl alcohol, 1,2-butanediol, 1,
3-butanediol, 1,4-butanediol, n-amyl alcohol, acetone, methyl ethyl ketone, methyl propyl ketone, ethyl propyl ketone, methyl butyl first
In in ketone, ethyl n-butyl ketone, methyl amyl ketone a kind, preferably ethanol, ethylene glycol, isopropanol, acetone, n-butyl alcohol
1 kind.
Further, the chemical vapour deposition technique bag carbon in described step (4) is particularly as follows: be passed through noble gas emptying sky
Gas, is warming up to uniform temperature, then passes to gas phase organic carbon source gas, deposits one layer of CNT；Described chemical gaseous phase deposits
Rotary furnace is carried out；Described noble gas is a kind in nitrogen, argon, helium, neon, and described inert gas flow is 2-
12L/min, preferably 3-6L/min；Described gas phase organic carbon source be methane, ethane, ethylene, acetylene, propane, propylene, butane,
In butylene, pentane, Ketohexamethylene, benzene,toluene,xylene, styrene, ethylbenzene, phenol, cresol a kind or the combination of at least 2 kinds,
Being preferably a kind or the combination of at least 2 kinds in methane, ethylene, acetylene, benzene, toluene, styrene, phenol, described gas phase is organic
Carbon source flow is 0.5-8L/min, preferably 1-5L/min；Described heating rate is 1-20 DEG C/min, preferably 5-15 DEG C/
min；Described warming temperature terminal is 500-1100 DEG C, preferably 600-900 DEG C；Described sedimentation time 0.5-8 hour, is preferably
1-5 hour.
Another object of the present invention is the purposes disclosing a kind of spherical silica anode composite, and its innovative point exists
In: lithium ion cell high-capacity negative pole, and the lithium battery that employing negative pole is prepared from can be used as.
Beneficial effects of the present invention is as follows:
(1) SiO that the present invention usesxMatrix particle diameter can be to below 1 μm, and particle diameter is less, contributes to active substance removal lithium embedded, permissible
Obtain higher specific capacity；SiO simultaneouslyxSample adds dispersant when grinding, and prevents the SiO that particle diameter is lessxA large amount of reunite thus
Affect performance.
(2) present invention uses the mode of mist projection granulating high temperature sintering to carry out carbon cladding first, by amorphous for one layer of porous
Carbon is coated on SiOx/ graphite matrix surface, can increase the change in volume during its electric conductivity, buffering removal lithium embedded, it is possible to
Obtain size tunable, the sphere material of regular shape.
(3) present invention is in order to avoid silicon exposure in the electrolytic solution, it is difficult to forms stable SEI film, have employed chemical gaseous phase
The method of deposition has carried out secondary carbon cladding, one layer of CNT at Surface coating, promotes electric conductivity further, reduces volume
Bulking effect, during chemical gaseous phase deposition bag carbon, pyroreaction can directly obtain monocrystal silicon or Uniform polycrystalline silicon is divided simultaneously
It is dispersed in SiOxIn Si oxide, it is to avoid single heat treatment process, technique is the simplest.
Accompanying drawing explanation
Fig. 1 is the structural representation of the present invention；
Fig. 2 is spherical silica anode composite SiO of embodiment 1xMatrix transmission electron microscope picture；
Fig. 3 is the spherical silica anode composite carbon coating layer transmission electron microscope picture of embodiment 1；
Fig. 4 is the spherical silica anode composite scanning electron microscope (SEM) photograph of embodiment 1；
Fig. 5 is that the spherical silica anode composite of embodiment 1 is as button cell loop test figure during negative pole.
Detailed description of the invention
By particular specific embodiment, embodiments of the present invention being described below, those skilled in the art can be by this explanation
Content disclosed by book understands other advantages and effect of the present invention easily.
A kind of spherical silica anode composite, including internal layer, intermediate layer and outer layer three-decker, internal layer is SiOx3/
Graphite matrix 2, intermediate layer is amorphous carbon 4, and outer layer is CNT 1, internal layer SiOx3/ graphite matrix 2 mass accounts for spherical silica
The percentage ratio of anode composite gross mass is 80-90%, and intermediate layer amorphous carbon 4 mass accounts for spherical silica Carbon anode and is combined
The percentage ratio of material gross mass is 5-10%, and outer layer CNT 1 mass accounts for the hundred of spherical silica anode composite gross mass
Proportion by subtraction is 5-10%；SiOxMatrix 3 is to have on crystal structure characteristic and SiO or Si and SiOxThe consistent spy of complex
Levying, the span of X is more than 0 and less than 2；Silica carbon composite is shaped as spherical or class is spherical, silica carbon composite
Particle diameter be 5-45 μm.
Embodiment 1
(1) liquid-phase C cladding: by the SiO of 200 mesh of the 250g of purchasexThe dispersant carboxymethyl of sample and mass fraction 1.5% is fine
Dimension element sodium uses sand mill to be ground to particle diameter less than 1 μm, and solvent is acetone, and solid content is 10%, is subsequently added into 250g average
The native graphite of particle diameter 4.7 μm and the dispersion of 46g polyvinyl alcohol high-speed stirred, speed of agitator 500rpm, time 0.5h, then spray
Drying-granulating；Sponging granulator inlet temperature 220 DEG C, outlet temperature 100 DEG C, charging pump frequency 10Hz, materialization dish frequency
250Hz；The carbon source cladding spherical SiO that will obtainx/ graphite granule puts into the sintering that heats up in atmosphere furnace, and atmosphere is that nitrogen adds 10% hydrogen
Gas, 1 DEG C/min of heating rate, sintering temperature 400 DEG C, the time is 4 hours, obtains the spherical SiO of amorphous carbon claddingx/ graphite
Sample.
(2) chemical vapor carbon deposition cladding: the spherical SiO that amorphous carbon is coated withx/ graphite sample 95g and 5g nickel acetate
Putting in acetone, controlling solid content is 35%, stirs to being dried with the speed of 500rpm；Desciccate is placed in rotary furnace,
Being passed through argon, flow is 4L/min, is warming up to 900 DEG C with 1 DEG C/min, then passes to ethylene, and flow is 2L/min, and deposition 2 is little
Time, it is down to room temperature, obtains the spherical silica carbon composite of particle diameter 5-45 μm.
(3) prepared by negative plate: electrode slice is prepared slurry by stirring and then used automatic spray dehydrator to be coated in Copper Foil
On form, slurry solvent is deionized water, and conductive agent is Super-p, and binding agent is that carboxymethyl cellulose adds SBR emulsion,
Active substance, conductive agent and binding agent ratio are 6:2:2.
(4) prepared by battery: button half-cell use lithium sheet as to electrode, in glove box according to anode cover, electrode slice,
The order of barrier film, lithium sheet, stainless steel gasket, nickel foam and negative electrode casing assembles CR2025 button cell, and electrolyte uses 1mol/L
LiPF6As electrolyte, solvent is the EC/EMC/DMC of 1:1:1, adds 10%FEC.
(5) battery testing: the cycle charge-discharge curve of employing blue electricity system test button cell, 0.1C rate charge-discharge,
Blanking voltage 0.005-1.5V.
Use transmission electron microscope that matrix and the carbon coating layer of final spherical silica carbon composite are characterized, result such as figure
2, shown in 3；Fig. 2 is internal layer SiOxThe transmission electron microscope picture of matrix, it can be seen that nano level crystal Si is embedded in amorphous SiOxInside,
Show that the present invention passes through during CVD bag carbon that pyroreaction can directly obtain single crystalline Si or polycrystalline Si is dispersed in SiOx
In Si oxide, eliminate special heat treatment process.Fig. 3 is the transmission electron microscope picture of carbon coating layer, it can be seen that middle carbon
Clad is amorphous carbon, and outer layer carbon coating layer is CNT.This two-layer carbon coating layer can promote the conductance of final material
Rate also weakens Volumetric expansion, prevents Si sill from directly contacting with electrolyte simultaneously, it is possible to obtain higher discharge and recharge effect
Rate and cycle performance.
Using scanning electron microscope to characterize final spherical silica carbon-carbon composite material surface pattern, result is as shown in Figure 4.Can
With see final material all for spherical or spherical particle, particle diameter is below 45 μm.
The charging and discharging curve of the button cell that the spherical silica carbon composite of the employing present invention is prepared as negative material
Test result is as shown in Figure 5, it can be seen that the first discharge specific capacity of material exists in about 850mAh/g, initial charge specific capacity
About 720mAh/g, efficiency is close to 85% first, circulates 20 charge specific capacity and be about 650mAh/g, capacity under 0.1C multiplying power
Conservation rate is more than 90%.
Embodiment 2
(1) liquid-phase C cladding: by the SiO of 200 mesh of the 300g of purchasexThe dispersant carboxymethyl of sample and mass fraction 1.5% is fine
Dimension element sodium uses sand mill to be ground to particle diameter less than 1 μm, and solvent is acetone, and solid content is 10%, is subsequently added into 200g average
The native graphite of particle diameter 4.7 μm and the dispersion of 46g polyvinyl alcohol high-speed stirred, speed of agitator 500rpm, time 0.5h, then spray
Drying-granulating；Sponging granulator inlet temperature 220 DEG C, outlet temperature 100 DEG C, charging pump frequency 10Hz, materialization dish frequency
250Hz；The carbon source cladding spherical SiO that will obtainx/ graphite granule puts into the sintering that heats up in atmosphere furnace, and atmosphere is that nitrogen adds 10% hydrogen
Gas, 1 DEG C/min of heating rate, sintering temperature 500 DEG C, the time is 4 hours, obtains the spherical SiO of amorphous carbon claddingx/ graphite
Sample.
(2) chemical vapor carbon deposition cladding: the spherical SiO that amorphous carbon is coated withx/ graphite sample 95g and 5g nickel acetate
Putting in acetone, controlling solid content is 35%, stirs to being dried with the speed of 500rpm；Desciccate is placed in rotary furnace,
Being passed through argon, flow is 4L/min, is warming up to 800 DEG C with 1 DEG C/min, then passes to ethylene, and flow is 2L/min, and deposition 2 is little
Time, it is down to room temperature, obtains the spherical silica carbon composite of particle diameter 5-45 μm.
Prepared by negative plate, battery is prepared consistent with embodiment 1 with battery testing.
Embodiment 3
(1) liquid-phase C cladding: by the SiO of 200 mesh of the 200g of purchasexThe dispersant carboxymethyl of sample and mass fraction 1.5% is fine
Dimension element sodium uses sand mill to be ground to particle diameter less than 1 μm, and solvent is ethanol, and solid content is 10%, is subsequently added into 300g average
The native graphite of particle diameter 4.7 μm and the dispersion of 46g polyvinyl alcohol high-speed stirred, speed of agitator 500rpm, time 0.5h, then spray
Drying-granulating；Sponging granulator inlet temperature 220 DEG C, outlet temperature 100 DEG C, charging pump frequency 10Hz, materialization dish frequency
250Hz；The carbon source cladding spherical SiO that will obtainx/ graphite granule puts into the sintering that heats up in atmosphere furnace, and atmosphere is that nitrogen adds 10% hydrogen
Gas, 1 DEG C/min of heating rate, sintering temperature 400 DEG C, the time is 6 hours, obtains the spherical SiO of amorphous carbon claddingx/ graphite
Sample.
(2) chemical vapor carbon deposition cladding: the spherical SiO that amorphous carbon is coated withx/ graphite sample 95g and 5g copper sulfate
Putting in acetone, controlling solid content is 35%, stirs to being dried with the speed of 500rpm；Desciccate is placed in rotary furnace,
Being passed through argon, flow is 4L/min, is warming up to 1000 DEG C with 1 DEG C/min, then passes to ethylene, and flow is 2L/min, and deposition 2 is little
Time, it is down to room temperature, obtains the spherical silica carbon composite of particle diameter 5-45 μm.
Prepared by negative plate, battery is prepared consistent with embodiment 1 with battery testing.
Silicon carbon material button electricity relevant parameter prepared by embodiment 1-3 is as shown in table 1:
Table 1
The one spherical silica anode composite of the present invention, can be used as lithium ion cell high-capacity negative pole, and adopt
The lithium battery being prepared from negative pole.
The silica carbon composite of the present invention has higher specific capacity, good processing characteristics and preferable cyclicity
Can, it is suitable as lithium ion battery negative material；The preparation method that the present invention provides is relatively easy, cost is relatively low, it is adaptable to work
Industry metaplasia is produced.
The SiO that the present invention usesxMatrix 3 particle diameter is below 5 μm, and particle diameter is less, contributes to active substance removal lithium embedded, permissible
Obtain higher specific capacity；SiO simultaneouslyxSample adds dispersant when grinding, and prevents the SiO that particle diameter is lessxA large amount of reunite thus
Affect performance；The mode using mist projection granulating high temperature sintering carries out carbon cladding first, is coated on by one layer of porous amorphous carbon 4
SiOx/ graphite matrix 2 surface, can increase the change in volume during its electric conductivity, buffering removal lithium embedded, it is possible to obtain particle diameter
Controlled, the sphere material of regular shape；In order to avoid silicon exposes in the electrolytic solution, it is difficult to form stable SEI film, have employed
The method learning vapour deposition has carried out secondary carbon cladding, one layer of CNT 1 at Surface coating, promotes electric conductivity further,
Reducing Volumetric expansion, during chemical gaseous phase deposition bag carbon, pyroreaction can directly obtain monocrystal silicon or polycrystalline simultaneously
Silicon is dispersed in SiOxIn Si oxide, it is to avoid single heat treatment process, technique is the simplest.
Above-described embodiment is presently preferred embodiments of the present invention, is not the restriction to technical solution of the present invention, as long as
The technical scheme that can realize on the basis of above-described embodiment without creative work, is regarded as falling into patent of the present invention
Rights protection in the range of.
Claims (10)
1. a spherical silica anode composite, it is characterised in that: include internal layer, intermediate layer and outer layer three-decker, institute
Stating internal layer is SiOx/ graphite matrix, described intermediate layer is amorphous carbon, and described outer layer is CNT, described internal layer SiOx/ stone
It is 80-90% that ink substrate quality accounts for the percentage ratio of spherical silica anode composite gross mass, described intermediate layer amorphous carbonaceous
It is 5-10% that amount accounts for the percentage ratio of spherical silica anode composite gross mass, and described outer layer carbon nanotube mass accounts for spherical silicon
The percentage ratio of oxygen anode composite gross mass is 5-10%；Described SiOxMatrix is to have on crystal structure characteristic and SiO
Or Si and SiOxThe consistent feature of complex, the span of described X is more than 0 and less than 2；Described silica carbon is combined
Material shape is spherical or class is spherical, and the particle diameter of described silica carbon composite is 5-45 μm.
2. a spherical silica anode composite preparation method as claimed in claim 1, it is characterised in that: include following
Step:
(1) by SiOxMaterial, dispersant and organic solvent are mixed into slurry, use sand mill to be ground to SiOxParticle diameter is less than 5 μm；
(2) slurry, graphite and the organic carbon source that obtain after grinding carry out high speed dispersion, then drying-granulating；
(3) heat up under protective atmosphere sintering by the spherical or spherical particle obtained, and is then cooled to room temperature, obtains amorphous
The SiO of carbon claddingx/ graphite material；
(4) SiO that amorphous carbon is coated withx/ graphite material mixes with catalyst precursor, then passes through chemical vapour deposition technique
It is coated with one layer of CNT, obtains final spherical silica carbon negative pole material.
One the most according to claim 2 spherical silica anode composite preparation method, it is characterised in that: described step
Suddenly the slurry solid content in (1) is 10-45%；Described SiOxMaterial is for directly buying or passing through SiO2High temperature is compared with equimolar with Si
Reaction preparation；Described dispersant is organic carbon source dispersant commonly used in the art, preferably sodium carboxymethyl cellulose, poly-second
One or both mixing in enol, described dispersant addition accounts for the 0.5-2% of gross mass.
One the most according to claim 2 spherical silica anode composite preparation method, it is characterised in that: described step
Suddenly the organic solvent in (1) be methanol, ethanol, ethylene glycol, propanol, isopropanol, 1,2-propylene glycol, 1,3-propylene glycol, glycerol,
N-butyl alcohol, 1,2-butanediol, 1,3 butylene glycol, 1,4-butanediol, n-amyl alcohol, acetone, methyl ethyl ketone, methyl propyl ketone, second
In base propyl group ketone, methyl butyl ketone, ethyl n-butyl ketone and methyl amyl ketone a kind, preferably ethanol, ethylene glycol,
In isopropanol, acetone and n-butyl alcohol a kind；SiO after described grindingxParticle diameter is 50-5000nm, preferably 100-1000nm.
One the most according to claim 2 spherical silica anode composite preparation method, it is characterised in that: described step
Suddenly one kind or two or more during the graphite in (2) is native graphite, Delanium, micro crystal graphite, carbonaceous mesophase spherules and soft carbon
Combination；Described graphite particle diameter D50For 2-8 μm；Described graphite and SiOxMass ratio be 1:3-3:1；Described organic carbon source is Portugal
Grape sugar, sucrose, citric acid, Polyethylene Glycol, polyvinyl butyral resin, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylonitrile, poly-
One kind or two or more combination in acrylic acid, epoxy resin, phenolic resin, Colophonium, starch, cellulose, polyaniline, described in have
The quality that machine carbon source adds is by carbon content and SiOxThe mass ratio of/graphite is 1:18-1:8.
One the most according to claim 2 spherical silica anode composite preparation method, it is characterised in that: described step
Suddenly the high speed dispersion in (2) uses high speed dispersor, arranges speed of agitator 500-2000rpm, mixing time 0.5-2h；Described dry
Dry pelletize uses sponging granulator, and inlet temperature is 220-280 DEG C, and outlet temperature is 90-120 DEG C；Described sponging granulator supplies
Material pump frequency is 10-20Hz, and atomizing disk frequency is 250-300Hz.
One the most according to claim 2 spherical silica anode composite preparation method, it is characterised in that: described step
Suddenly the protective atmosphere in (3) is a kind in noble gas, reducing gas or vacuum atmosphere or the combination of at least 2 kinds；Described lazy
Property gas is a kind in nitrogen, argon, helium, neon, and described reducing gas is one or both in hydrogen, carbon monoxide
Combination, described vacuum atmosphere pressure less than 0.1MPa, preferably pressure less than 0.05MPa；Described heating rate is 1-20 DEG C/
Min, preferably 5-15 DEG C/min；Described sintering temperature is 200-800 DEG C, preferably 300-600 DEG C；Described sintering time is 2-
15 hours, preferably 4-10 hour.
One the most according to claim 2 spherical silica anode composite preparation method, it is characterised in that: described step
Suddenly the concretely comprising the following steps of the mixing in (4): the SiO that amorphous carbon is coated withx/ graphite material and catalyst precursor add to having
In machine solvent, solid content is 5-40%, and stirring is to being dried；Described catalyst precursor is in ferric nitrate, nickel acetate or copper sulfate
1 kind；Described catalyst precursor mass fraction 1-10%；Described organic solvent be methanol, ethanol, ethylene glycol, propanol, isopropanol,
1,2-propylene glycol, 1,3-propylene glycol, glycerol, n-butyl alcohol, 1,2-butanediol, 1,3 butylene glycol, 1,4-butanediol, n-amyl alcohol,
Acetone, methyl ethyl ketone, methyl propyl ketone, ethyl propyl ketone, methyl butyl ketone, ethyl n-butyl ketone, methyl amyl first
In in ketone a kind, preferably ethanol, ethylene glycol, isopropanol, acetone, n-butyl alcohol a kind.
One the most according to claim 2 spherical silica anode composite preparation method, it is characterised in that: described step
Suddenly the chemical vapour deposition technique bag carbon in (4) is particularly as follows: be passed through noble gas evacuation of air, is warming up to uniform temperature, then leads to
Enter gas phase organic carbon source gas, deposit one layer of CNT；Described chemical gaseous phase is deposited in rotary furnace and carries out；Described indifferent gas
Body is a kind in nitrogen, argon, helium, neon, and described inert gas flow is 2-12L/min, preferably 3-6L/min；Institute
State gas phase organic carbon source be methane, ethane, ethylene, acetylene, propane, propylene, butane, butylene, pentane, Ketohexamethylene, benzene, toluene,
In dimethylbenzene, styrene, ethylbenzene, phenol, cresol a kind or the combination of at least 2 kinds, preferably methane, ethylene, acetylene, benzene, first
In benzene, styrene, phenol a kind or the combination of at least 2 kinds, described gas phase organic carbon source flow is 0.5-8L/min, preferably
For 1-5L/min；Described heating rate is 1-20 DEG C/min, preferably 5-15 DEG C/min；Described warming temperature terminal is 500-
1100 DEG C, preferably 600-900 DEG C；Described sedimentation time 0.5-8 hour, preferably 1-5 hour.
10. the purposes of a spherical silica anode composite as claimed in claim 1, it is characterised in that: can by with
Do lithium ion cell high-capacity negative pole, and the lithium battery that employing negative pole is prepared from.
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