CN106067547A - Carbon-coated nano 3 SiC 2/graphite alkene cracks carbon-coating composite, preparation method and the lithium ion battery comprising this composite - Google Patents
Carbon-coated nano 3 SiC 2/graphite alkene cracks carbon-coating composite, preparation method and the lithium ion battery comprising this composite Download PDFInfo
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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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- 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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Abstract
The present invention relates to a kind of carbon-coated nano 3 SiC 2/graphite alkene cracking carbon-coating composite, its preparation method and the lithium ion battery comprising this composite.The composite of the present invention includes being dispersed in, by carbon-coated nano silicon, the spheroidal particle formed in graphene film, and it is coated on the cracking carbon-coating on spheroidal particle surface, wherein, described carbon-coated nano silicon includes nano-silicon and is coated on the cladding carbon-coating on nano-silicon surface.In the present invention, method is simple, processing characteristics is excellent, and environmental friendliness, the carbon-coated nano 3 SiC 2/graphite alkene cracking carbon-coating composite structure prepared is stable, and compacted density is high, as the negative material of lithium ion battery, show good performance, its capacity of negative plates height, high rate performance and cycle performance are excellent, and reversible capacity is more than 1500mAh/g first, and coulombic efficiency is more than 90% first, 500 circulation volume conservation rates are more than 90%, and expand low.
Description
Technical field
The invention belongs to electrochemistry and lithium ion battery negative material field, relate to a kind of composite, its preparation method
And comprise the lithium ion battery of this composite, particularly relate to a kind of carbon-coated nano silicon-Graphene-cracking carbon-coating composite wood
Material, its preparation method, and comprise this composite lithium ion battery as negative material.
Background technology
Lithium ion battery is compared with the batteries such as plumbic acid, NI-G, ni-mh, due to its higher energy density, longer use
The features such as life-span, less volume, memory-less effect, become one of focus of energy field research now.The most commercial lithium
Ion battery cathode material is widely used graphite and modified graphite, its theoretical capacity only 372mAh/g, significantly constrains high-energy
The development of electrokinetic cell.In various Novel anode materials, silicon-based anode have uniqueness advantage and potentiality, theoretical capacity up to
4200mAh/g, simultaneously in charge and discharge process the voltage of its removal lithium embedded low low with electrolyte reactivity, security performance is good.But
That silicon can occur violent volumetric expansion (0～300%) in removal lithium embedded course of reaction, thus cause material structure destruction and
Efflorescence, causes structure collapses, ultimately results in electrode active material and departs from collector, causes capacity to be decayed rapidly, cycle performance
Deteriorate.This bulk effect also results in silicon and is difficult to be formed stable solid electrolyte interface film (SEI film) in the electrolytic solution, companion
Along with the destruction of electrode structure, constantly forming new SEI film at the silicon face exposed, the corrosion and the capacity that exacerbate silicon decline
Subtract.Additionally, silicium cathode to there is also electrical conductivity low, the defects such as high rate performance is not good enough, and coulombic efficiency is relatively low.Therefore, research and development are a kind of high
Electric conductivity, high power capacity, high first charge-discharge efficiency, low bulk are lithium ion battery necks with the silicium cathode material of good cycling stability
The technical barrier in territory.
CN 102306757B discloses the preparation method of a kind of silicon graphene composite negative pole material, described
Silicon graphene composite negative pole material by 10～the Graphene of the silica flour of 99%, 1～90% and 0～40% without fixed
Shape carbon forms, and the preparation method of described silicon graphene composite negative pole material is: first carry out the first step: by silica flour
Dispersed with graphene oxide be uniformly dispersed, be then spray-dried in a solvent, inlet temperature at 120～220 DEG C,
Outlet temperature at 80～140 DEG C, remove solvent, be then placed in high temperature furnace, be passed through protection its body, be warming up to 500～
1100 DEG C carry out high annealing, are incubated 1～24h, make graphene oxide reduce, be cooled to room temperature, then carry out second step:
Prepared material is placed in high temperature furnace, protective gas is warming up to 600～1100 DEG C, is then loaded into gaseous state by protective gas
Carbon source or liquid carbon source, be incubated 1～12h, obtain silicon graphene composite negative pole material；Second step it is also possible that
Operation: the material first step obtained makes it dispersed in a solvent by supersound process and stirring together with solid-state carbon source,
Solvent evaporated, transfers in high temperature furnace, is warming up to 600～1100 DEG C in protective gas, is incubated 1～12h, obtains lithium ion
Battery 3 SiC 2/graphite alkene composite negative pole material.The composite negative pole material that this invention prepares has outstanding cycle performance, with gold
Belonging to lithium sheet is to electrode, the silicon graphene composite negative pole material of this invention is assembled into battery and tests, table
Having revealed the reversible capacity first of 562～1525mAh/g, coulombic efficiency is 42～70% first.But, its coulombic efficiency first
The lowest all below 70%, have a strong impact on its actual application.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of carbon-coated nano silicon-Graphene-cracking carbon
Layer composite, its preparation method and comprise the lithium ion battery of this composite, the carbon-coated nano silicon-graphite of the present invention
The Stability Analysis of Structures of alkene-cracking carbon-coating composite, using it as the negative material as lithium ion battery, shows the highest
The high rate performance of electric conductivity, capacity of negative plates and excellence and cycle performance, reversible capacity is more than 1500mAh/g, first coulomb first
Efficiency is more than 90%, and 500 circulation volume conservation rates are more than 90%, and expand low.
For reaching above-mentioned purpose, the present invention by the following technical solutions:
An object of the present invention is to provide a kind of carbon-coated nano silicon-Graphene-cracking carbon-coating composite, described
Composite includes being dispersed in, by carbon-coated nano silicon, the spheroidal particle formed in graphene film, and is coated on described
The cracking carbon-coating on spheroidal particle surface；Wherein, described carbon-coated nano silicon includes nano-silicon and is coated on the bag on nano-silicon surface
Cover carbon-coating.
The internal structure of the carbon-coated nano silicon-Graphene-cracking carbon-coating composite of the present invention sees Fig. 1.
Preferably, the median particle diameter of described composite is 1 μm～30 μm, such as, can be 1 μm, 1.5 μm, 2 μm, 3 μm, 4 μ
m、5μm、7μm、8.5μm、10μm、12μm、13μm、15μm、16μm、17.5μm、18μm、20μm、22μm、23μm、24.5μm、27
μm or 30 μm etc., preferably 2 μm～25 μm, more preferably 4 μm～15 μm.
Preferably, described composite is a kind of porous silicon-base composite negative pole material, and its specific surface area is less, for 1m2/g
～30m2/ g, such as, can be 1m2/g、3m2/g、5m2/g、8m2/g、9.5m2/g、10m2/g、13m2/g、16m2/g、18m2/g、
19m2/g、20m2/g、22.5m2/g、25m2/g、26.5m2/g、28m2/ g or 30m2/ g etc., preferably 2m2/ g～10m2/g。
Preferably, the powder body compacted density of described composite is 0.5g/cm3～2.5g/cm3, such as, can be 0.5g/
cm3、0.6g/cm3、0.7g/cm3、0.75g/cm3、0.8g/cm3、0.88g/cm3、0.95g/cm3、1g/cm3、1.2g/cm3、
1.3g/cm3、1.5g/cm3、1.8g/cm3Or 2g/cm3Deng, preferably 0.8g/cm3～2g/cm3。
Preferably, be in terms of 100% by the gross mass of composite, the mass percent of nano-silicon be 10wt%～
60wt%, can be such as 10wt%, 13wt%, 16wt%, 20wt%, 23wt%, 25wt%, 27.5wt%, 30wt%,
34wt%, 37wt%, 40wt%, 42wt%, 45wt%, 50wt%, 53.5wt%, 56wt% or 60wt% etc..
Preferably, it is in terms of 100% by the gross mass of composite, is coated on the quality hundred of the cladding carbon-coating on nano-silicon surface
Proportion by subtraction is 5wt%～30wt%, can be such as 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 17.5wt%, 20wt%,
23wt%, 26wt%, 28wt% or 30wt% etc..
Preferably, be in terms of 100% by the gross mass of composite, the mass percent of graphene film be 5wt%～
50wt%, can be such as 5wt%, 10wt%, 13wt%, 15wt%, 18wt%, 20wt%, 22wt%, 25wt%, 30wt%,
33wt%, 35wt%, 37wt%, 40wt%, 43.5wt%, 47wt% or 50wt% etc..
Preferably, it is in terms of 100% by the gross mass of composite, is coated on the quality of the cracking carbon-coating on spheroidal particle surface
Percentage ratio is 10wt%～40wt%, can be such as 10wt%, 12.5wt%, 14wt%, 16wt%, 18wt%, 21wt%,
24wt%, 28wt%, 30wt%, 33wt%, 35wt%, 38wt% or 40wt% etc..
The median particle diameter of described nano-silicon is 5nm～300nm, can be such as 5nm, 10nm, 20nm, 25nm, 35nm,
50nm、60nm、70nm、80nm、90nm、100nm、120nm、135nm、145nm、160nm、180nm、200nm、220nm、
235nm, 250nm, 260nm, 270nm, 285nm or 300nm etc..
Preferably, the specific surface area of described nano-silicon is 10m2/ g～500m2/ g, such as, can be 10m2/g、20m2/g、
30m2/g、50m2/g、65m2/g、80m2/g、100m2/g、120m2/g、140m2/g、165m2/g、180m2/g、200m2/g、
215m2/g、230m2/g、245m2/g、270m2/g、300m2/g、320m2/g、340m2/g、355m2/g、380m2/g、400m2/g、
425m2/g、450m2/g、480m2/ g or 500m2/ g etc..
Preferably, the cladding carbon-coating being coated on nano-silicon surface described in is that gaseous carbon source vapour deposition obtains.
Preferably, described gaseous carbon source is methane, ethane, propane, ethylene, acetylene, the benzene of gaseous state, the toluene of gaseous state, gas
Any a kind or the combination of at least 2 kinds in the acetone of the dimethylbenzene of state, the ethanol of gaseous state or gaseous state.
Preferably, described in be coated on nano-silicon surface cladding carbon-coating thickness be 5nm～500nm, can be such as 5nm,
10nm、20nm、30nm、50nm、60nm、75nm、85nm、100nm、120nm、135nm、150nm、170nm、185nm、200nm、
220nm、240nm、260nm、270nm、285nm、300nm、320nm、340nm、360nm、380nm、400nm、410nm、
430nm, 450nm, 470nm or 500nm etc..
Preferably, described graphene film is formed by stacking by single-layer graphene, and the thickness of described graphene film is preferably 50nm
～300nm, can be such as 50nm, 70nm, 80nm, 100nm, 120nm, 135nm, 150nm, 170nm, 185nm, 200nm,
215nm, 225nm, 250nm, 260nm, 275nm or 300nm etc..
Preferably, the cracking carbon-coating being coated on spheroidal particle surface described in is obtained through cracking by organic carbon source.
Preferably, described organic carbon source include but not limited to alkanes, cycloalkane, alkene, alkynes, aromatic hydrocarbon, polymer,
Any a kind or the combination of at least 2 kinds in saccharide, organic acid, resinae macromolecular material, it is conventional that other this areas carry out cladding
Organic carbon source can also be used for the present invention, preferably methane, ethane, ethylene, phenol, Colophonium, epoxy resin, phenolic resin, bran
Urea formaldehyde, Lauxite, polyvinyl alcohol, polrvinyl chloride, Polyethylene Glycol, poly(ethylene oxide), Kynoar, acrylic resin and
Any a kind or the combination of at least 2 kinds in polyacrylonitrile.
Preferably, described in be coated on spheroidal particle surface cracking carbon-coating thickness be 0.5 μm～5 μm, can be such as 0.5
μm, 1 μm, 1.2 μm, 1.5 μm, 2 μm, 2.2 μm, 2.4 μm, 2.7 μm, 3 μm, 3.5 μm, 3.8 μm, 4 μm, 4.5 μm or 5 μm etc..
The two of the purpose of the present invention are to provide carbon-coated nano as above silicon-Graphene-cracking carbon-coating composite wood
The preparation method of material, said method comprising the steps of:
(1) use gaseous carbon source that nano-silicon is carried out vapour deposition, obtain carbon-coated nano silicon；
(2) use step (1) the carbon-coated nano silicon that obtains and graphene film, prepare homodisperse system, be then dried and make
Grain, obtains spheroidal particle；Wherein, in described spheroidal particle, carbon-coated nano silicon is dispersed between graphene film；
(3) spheroidal particle step (2) obtained and organic carbon source mixing, obtain homogeneous mixture；
(4) homogeneous mixture obtaining step (3) is sintered, and obtains carbon-coated nano silicon-Graphene-cracking carbon-coating
Composite.
As the optimal technical scheme of the method for the invention, described method is additionally included in after step (4) sintered, and enters
The step of magnetic is pulverized, sieves and removed to row cooling and the product obtaining sintering.
Preferably, after step (4) has sintered, carry out being cooled to room temperature.
Preferably, step (1) described gaseous carbon source is methane, ethane, propane, ethylene, acetylene, the benzene of gaseous state, gaseous state
Any a kind or the mixture of at least 2 kinds in the acetone of toluene, the dimethylbenzene of gaseous state, the ethanol of gaseous state or gaseous state, above-mentioned enumerates
Mixture be gaseous state.
Due to, methane, ethane, propane, ethylene and acetylene are gaseous state under normal temperature condition, and benzene,toluene,xylene,
It is liquid under ethanol and acetone room temperature, makes them become gaseous state to respective boiling point to make so that heat these several liquid carbon source
With, illustrate: the boiling point of benzene is 80 DEG C, thus the benzene boiling point more than 80 DEG C to it need to be heated when using so that it becomes gaseous state
Benzene is re-used as gaseous carbon source and uses.
The gaseous carbon source of the present invention is not limited to gaseous carbon source that the above-mentioned room temperature enumerated is gaseous state or room temperature is in a liquid state
Liquid carbon source be heated to the gaseous carbon source that more than boiling point becomes, appointing of gaseous carbon source under other room temperature or liquid carbon source
The product that the mixture of a kind or at least 2 kinds of anticipating obtains after pyrolytic also can be as gaseous carbon source for the present invention.
Preferably, the process of step (1) described vapour deposition is: is placed in atmosphere furnace by nano-silicon, is passed through carbon source, carries out
Heat treatment.
Preferably, during described vapour deposition, described atmosphere furnace is tube furnace, batch-type furnace, rotary furnace, tunnel kiln
Or any a kind in ejection plate kiln.
Preferably, during described vapour deposition, the temperature of described heat treatment is 500 DEG C～1000 DEG C, such as, can be
500 DEG C, 600 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C or 1000 DEG C etc..
Preferably, during described vapour deposition, the time of described heat treatment is 2h～5h, can be such as 2h, 2.5h,
3h, 3.2h, 3.5h, 4h, 4.3h, 4.5h or 5h etc..
Preferably, the mass ratio of the nano-silicon in step (2) described carbon-coated nano silicon and graphene film be (60～
140): 20, can be such as 60:20,70:20,80:20,85:20,90:20,100:20,120:20,130:20 or 140:20 etc..
Preferably, the technology that step (2) described drying-granulating uses is stirring-granulating method, boiling granulation method, spray drying
Any a kind or the combination of at least 2 kinds in comminution granulation, pressure forming comminution granulation, the heat fusing method of forming.
Preferably, the equipment that step (2) described drying-granulating uses is pelletize drum, cone drum comminutor, roller pelletizer, pinches
Conjunction machine, drum mixer, hammer powder blend machine, vertical shaft type powder blend machine, belt powder blend machine, lower the curtain granule machine, spray
Mist drying machine, desk-top squeezer, vacuum depression bar comminutor, single screw extruder pelletizer, twin-screw extruder comminutor, model punching press
Machine, to any a kind or the combination of at least 2 kinds in roller gear comminutor.
Preferably, the preparation process of step (2) described homodisperse system is: carbon-coated nano silicon step (1) obtained
Mix with graphene film, then the mixed-powder obtained is added in organic solvent, ultrasonic agitation, formed homodisperse mixed
Close slurry；Again slurry is placed in high speed dispersor, dispersion stirring, obtains homodisperse system.
Preferably, in the preparation process of homodisperse system, described organic solvent is oxolane, dimethyl acetylamide, C1-
Any a kind or the combination of at least 2 kinds in C6 alcohol and C3-C8 ketone, described C1-C6 alcohol be preferably methanol, ethanol, ethylene glycol, third
Alcohol, isopropanol, 1,2-propylene glycol, 1,3-propylene glycol, glycerol, n-butyl alcohol, 1,2-butanediol, 1,3 butylene glycol, 1,4-fourth two
In alcohol, n-amyl alcohol and 2-hexanol a kind or the combination of at least 2 kinds, described C3-C8 ketone is preferably acetone, methyl ethyl ketone, methyl
Propyl group ketone, N-Methyl pyrrolidone, ethyl propyl ketone, methyl butyl ketone, ethyl n-butyl ketone, methyl amyl ketone and
Any a kind or the combination of at least 2 kinds in methyl hexyl ketone..
Preferably, in the preparation process of homodisperse system, the time of described ultrasonic agitation is 0.1h～1h, such as, can be
0.1h, 0.2h, 0.3h, 0.4h, 0.45h, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1h etc..
Preferably, in the preparation process of homodisperse system, described high speed dispersor is homogenizer, planetary mixer, twin shaft
In dispersion machine, single guide pillar dispersion machine, double guide pillar dispersion machine, de-airing mixer, ball mill, sand mill any a kind or at least 2 kinds
Combination.
Preferably, in the preparation process of homodisperse system, described dispersion stirring time be 1h～5h, can be such as 1h,
2h, 2.5h, 3h, 3.5h, 4h, 4.3h, 4.7h or 5h etc..
Preferably, the mass ratio of step (3) described spheroidal particle and organic carbon source is (60～150): 30, such as, can be
60:30,63:30,65:30,70:30,85:30,100:30,115:30,130:30 or 150:30 etc..
Step (3) described organic carbon source include but not limited to alkanes, cycloalkane, alkene, alkynes, aromatic hydrocarbon, polymer,
Any a kind or the combination of at least 2 kinds in saccharide, organic acid, resinae macromolecular material, it is conventional that other this areas carry out cladding
Organic carbon source can also be used for the present invention, preferably methane, ethane, ethylene, phenol, Colophonium, epoxy resin, phenolic resin, bran
Urea formaldehyde, Lauxite, polyvinyl alcohol, polrvinyl chloride, Polyethylene Glycol, poly(ethylene oxide), Kynoar, acrylic resin and
Any a kind or the combination of at least 2 kinds in polyacrylonitrile.
The states of matter of the organic carbon source that the solid phase cladding process of step of the present invention (3) and liquid phase coating method use indefinite, can
To be solid-state, it is also possible to be liquid, it is also possible to be gaseous state, when the organic carbon source that step (3) described organic carbon source is solid-state, have
The particle diameter of machine carbon source is preferably 5 μm～20 μm, such as, can be 5 μm, 8 μm, 10 μm, 12.5 μm, 14 μm, 15 μm, 17 μm, 18.5 μm
Or 20 μm etc..
Preferably, any a kind during the preparation method of described homogeneous mixture is solid phase cladding process or liquid phase coating method；Its
In, the preparation process of described solid phase cladding process is: spheroidal particle step (2) obtained and organic carbon source mix homogeneously, is placed in
In VC mixer, mix, obtain homogeneous mixture.
The preparation process of described liquid phase coating method is: the spheroidal particle and the organic carbon source that step (2) are obtained are distributed to molten
In agent, mixing, it is dried, obtains homogeneous mixture.
Preferably, in solid phase cladding process, during mixing, the frequency of VC mixer is 5Hz～50Hz, can be such as 5Hz,
10Hz, 15Hz, 20Hz, 23Hz, 25Hz, 30Hz, 35Hz, 40Hz, 45Hz or 50Hz etc..
Preferably, in solid phase cladding process, the time of mixing at more than 30min, can be such as 30min, 40min, 50min,
60min, 80min, 100min, 110min, 120min, 150min, 180min or 200min etc., preferably 0.5h～5h, enter one
Step is preferably 0.5h～3h.
Preferably, in liquid phase coating method, solvent is water and/or organic solvent.
" water and/or organic solvent " of the present invention refers to: can be water, it is also possible to be organic solvent, it is also possible to be water and
The mixture of organic solvent.
Preferably, the temperature of step (4) described sintering is 400 DEG C～1200 DEG C, can be such as 400 DEG C, 500 DEG C, 600
DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 900 DEG C, 950 DEG C, 1000 DEG C, 1100 DEG C or 1200 DEG C etc..
Preferably, the time of step (4) described sintering is 0.5h～10h, can be such as 0.5h, 1h, 1.2h, 1.5h, 2h,
2.5h, 3h, 4h, 5h, 5.5h, 6h, 7h, 8h, 9h or 10h etc..
Preferably, carrying out under conditions of being sintered in protective gas protection described in step (4), described protective gas is preferred
For a kind in nitrogen, helium, neon, argon, Krypton and xenon or the combination of at least 2 kinds；
Preferably, being sintered in firing furnace carrying out described in step (4), described firing furnace is preferably vacuum drying oven, batch-type furnace, returns
Converter, roller kilns, pushed bat kiln or tube furnace.
The three of the purpose of the present invention are to provide a kind of negative material, and described negative material is above-mentioned carbon-coated nano
Silicon-Graphene-cracking carbon-coating composite.
The four of the purpose of the present invention are to provide a kind of lithium ion battery, and described lithium ion battery comprises above-mentioned carbon cladding
Nano-silicon-Graphene-cracking carbon-coating composite is as the negative material in lithium ion battery.
In the present invention as follows to prepare the method for lithium ion battery as negative material: by carbon-coated nano silicon-Graphene-
Cracking carbon-coating composite is as the negative material of lithium ion battery, then by this negative material, conductive agent, thickening agent and bonding
Agent (88～94) by mass percentage: (1～4): (1～4): (1～4) dissolving mixes in a solvent, is coated on copper foil current collector
On, vacuum drying, prepared cathode pole piece；Then the anode pole piece prepared by tradition maturation process, electrolyte, barrier film, shell are adopted
It is assembled into lithium ion battery by conventional production process.
Preferably, in above-mentioned preparation process, described conductive agent is graphite powder, acetylene black, carbon fiber, CNT, carbon black
(SP) a kind in or the combination of at least 2 kinds.
Preferably, in above-mentioned preparation process, described thickening agent is sodium carboxymethyl cellulose (CMC).
Preferably, in above-mentioned preparation process, described binding agent is polyimide resin, acrylic resin, poly-inclined difluoro second
1 kind or the combination of at least 2 kinds of alkene, polyvinyl alcohol, sodium carboxymethyl cellulose or butadiene-styrene rubber.
Preferably, in above-mentioned preparation process, positive electrode active materials is commercial type the three of described anode pole piece employing
Unit's material, rich lithium material, cobalt acid lithium, lithium nickelate, spinel lithium manganate, layer dress LiMn2O4 or LiFePO4 a kind or at least 2 kinds
Combination.
Preferably, lithium ion battery kind of the present invention is conventional aluminum hull, box hat or soft bag lithium ionic cell.
Compared with prior art, the method have the advantages that
(1) method of the present invention prepares carbon bag by gas phase deposition technology, high speed dispersion technology and drying-granulating technology
Cover nano-silicon and make itself and Graphene mixing granulation be combined into spheroidal particle, in conjunction with homogeneous modification technology outside spheroidal particle
Cladding cracking carbon-coating, it is achieved that the cladding of double carbon-coatings and the perfection with Graphene are combined, and wherein, carbon-coated nano silicon uniformly divides
Dissipating formation spheroidal particle between graphene sheet layer, spheroidal particle external sheath has cracking carbon-coating.The work of the method for the invention
Skill is simple, and processing characteristics is good and environmental friendliness is pollution-free.
(2) carbon-coated nano silicon-Graphene-cracking carbon-coating composite structure that the present invention prepares is stable, compares table
Low (the 2m of area2/ g～10m2/ g), the high (1.2g/cm of compacted density3～1.5g/cm3), it is highly suitable as lithium ion battery
Negative material, carbon-coated nano silicon is dispersed between graphene sheet layer formation spheroidal particle, is coated with outside spheroidal particle
Cracking carbon-coating, Graphene this structure in the composite has not only acted as the effect of conductive network, has also acted support rib
The effect of frame, the unique texture that Graphene is formed with double-deck carbon-coating, greatly reduce in charge and discharge process the volumetric expansion of silicon and
Blockage effect, moreover it is possible to avoid silicon nanoparticle reunion in cyclic process, intercepts silicon and directly contacts with electrolyte, be greatly improved
The chemical property of material, shows high rate performance and the cycle performance of the highest electric conductivity, capacity of negative plates and excellence, first
Reversible capacity is more than 1500mAh/g, and coulombic efficiency is more than 90% first, and 500 circulation volume conservation rates are more than 90%, and expand
Low.
Accompanying drawing explanation
Fig. 1 is the internal structure schematic diagram of the carbon-coated nano silicon-Graphene-cracking carbon-coating composite of the present invention, its
In, 1 is cladding carbon-coating, and 2 is nano-silicon, and 3 is graphene film, and 4 is cracking carbon-coating；
Fig. 2 is the scanning electricity of the carbon-coated nano silicon-Graphene-cracking carbon-coating composite of the embodiment of the present invention 1 preparation
Sub-microscope (SEM) picture；
Fig. 3 is the XRD figure of the carbon-coated nano silicon-Graphene-cracking carbon-coating composite of the embodiment of the present invention 1 preparation；
Fig. 4 is that the carbon-coated nano silicon-Graphene-cracking carbon-coating composite of the embodiment of the present invention 1 preparation is as negative pole
Material is made battery and is carried out electrochemical property test, the first charge-discharge curve obtained；
Fig. 5 is that the carbon-coated nano silicon-Graphene-cracking carbon-coating composite of the embodiment of the present invention 1 preparation is as negative pole
Material is made battery and is carried out electrochemical property test, the cycle performance curve obtained.
Detailed description of the invention
Further illustrate technical scheme below in conjunction with the accompanying drawings and by detailed description of the invention.
Make at identical conditions using the composite that embodiment 1-6 and comparative example 1-2 prepare as negative material
Standby battery also tests its chemical property, and the preparation method of concrete battery is as follows: negative material, conductive agent and binding agent are pressed
Mass percent 94:1:5 is dissolved and is mixed in a solvent, and control solid content, 50%, is coated in copper foil current collector, and vacuum is dried
Cathode pole piece dry, prepared；Then by tradition maturation process prepare tertiary cathode pole piece, the LiPF of 1mol/L6/EC+DMC+EMC
(v/v=1:1:1) electrolyte, Celgard2400 barrier film, shell use conventional production process to assemble 18650 cylinder cells.
The cylindrical battery obtained is carried out discharge and recharge survey on Wuhan Jin Nuo Electronics Co., Ltd. LAND battery test system
Examination, test condition is normal temperature condition, and 0.2C constant current charge-discharge, charging/discharging voltage is limited in 2.75V～4.2V.
Embodiment 1
(1) silica flour that median particle diameter is 40nm is placed in rotary furnace, is passed through methane and carries out carbon cladding, with 5 DEG C/min liter
Temperature ramp, to 800 DEG C, is incubated 3h, naturally cools to room temperature, obtain carbon-coated nano silicon.
(2) by carbon-coated nano silicon and graphene film (thickness is 50nm) by the nano-silicon in carbon-coated nano silicon: graphite
Mass ratio=the 80:20 of alkene uniformly mixes, and then adds in dehydrated alcohol by mixed-powder, ultrasonic agitation 30min, shape
The most scattered mixed slurry；Again slurry is placed in high speed dispersor, dispersion stirring 1h, obtains carbon-coated nano silicon and stone
The homodisperse system of ink alkene sheet.Then homodisperse system is processed through atomizing exsiccator, obtain spheroidal particle.
(3) the Colophonium 60:30 in mass ratio that the spheroidal particle obtained in step (2) and particle diameter are 7 μm is carried out proportioning, so
After add in dehydrated alcohol, process through high speed dispersor and form the composite mortar of mix homogeneously after 1h, then by composite mortar
Drying processes, and obtains the homogeneous mixture of spheroidal particle and organic carbon source.
(4) precursor three is placed in batch-type furnace, is passed through argon, be warming up to 1050 DEG C with 10 DEG C/min heating rate, protect
Temperature 10h, naturally cools to room temperature, pulverizes, sieve and remove magnetic, obtains particle diameter and is 1 μm～30 μm obtain silicon-graphene composite negative
Material.
Fig. 2 is the SEM figure of carbon-coated nano silicon-Graphene-cracking carbon-coating composite that the present embodiment 1 prepares,
As seen from the figure, composite individual particle spherical in shape dispersion.
Fig. 3 is the XRD figure of carbon-coated nano silicon-Graphene-cracking carbon-coating composite that the present embodiment 1 prepares,
As can be observed from Figure, the most weak silicon diffraction maximum, carbon-free peak, this is nothing mainly due to conductive additive and cracking carbon
Setting state.
Fig. 4 is that carbon-coated nano silicon-Graphene-cracking carbon-coating composite of obtaining of the present embodiment 1 is as negative material
Prepare battery and carry out electrochemical property test, the first charge-discharge curve obtained, as seen from the figure, the charge and discharge first of this material
Electricity coulombic efficiency is 91.3%, capacity 1695.1mAh/g.
Fig. 4 is that carbon-coated nano silicon-Graphene-cracking carbon-coating composite of obtaining of the present embodiment 1 is as negative material
Preparing battery and carry out electrochemical property test, the cycle performance curve obtained, as seen from the figure, this material has excellence
Cycle performance, circulating 500 weeks capability retentions is 91.9%.
Embodiment 2
(1) silica flour that median particle diameter is 5nm is placed in rotary furnace, is passed through methane and carries out carbon cladding, heat up with 5 DEG C/min
Ramp, to 800 DEG C, is incubated 3h, naturally cools to room temperature, obtain carbon-coated nano silicon.
(2) by carbon-coated nano silicon and graphene film (thickness is 100nm) by the nano-silicon in carbon-coated nano silicon: graphite
Mass ratio=the 80:20 of alkene uniformly mixes, and then adds in dehydrated alcohol by mixed-powder, ultrasonic agitation 30min, shape
The most scattered mixed slurry；Again slurry is placed in high speed dispersor, dispersion stirring 1h, obtains carbon-coated nano silicon and stone
The homodisperse system of ink alkene sheet.Then composite mortar drying pelletize is processed, obtain spheroidal particle.
(3) spheroidal particle obtained in step (2) is joined with the epoxy resin 60:30 in mass ratio that particle diameter is 3 μm
Ratio, mix homogeneously is placed in VC mixer, and regulating frequency is 30Hz, mixes 60min, obtains spheroidal particle and organic carbon source
Homogeneous mixture.
(4) precursor three is placed in batch-type furnace, is passed through argon, be warming up to 1050 DEG C with 10 DEG C/min heating rate, protect
Temperature 10h, naturally cools to room temperature, pulverizes, sieve and remove magnetic, obtains particle diameter and is 1 μm～30 μm obtain silicon-graphene composite negative
Material.
Embodiment 3
(1) silica flour that median particle diameter is 50nm is placed in rotary furnace, is passed through methane and carries out carbon cladding, with 5 DEG C/min liter
Temperature ramp, to 800 DEG C, is incubated 3h, naturally cools to room temperature, obtain carbon-coated nano silicon.
(2) carbon-coated nano silicon and thickness are about the graphene film of 60nm by the nano-silicon in carbon-coated nano silicon: stone
Mass ratio=the 80:20 of ink alkene uniformly mixes, and then adds in dehydrated alcohol by mixed-powder, ultrasonic agitation 30min,
Form homodisperse mixed slurry；Again slurry is placed in high speed dispersor, dispersion stirring 1h, obtain carbon-coated nano silicon and
The homodisperse system of graphene film.Then composite mortar drying pelletize is processed, obtain spheroidal particle.
(3) spheroidal particle obtained in step (2) is joined with the epoxy resin 60:30 in mass ratio that particle diameter is 3 μm
Ratio, mix homogeneously is placed in VC mixer, and regulating frequency is 30Hz, mixes 60min, obtains spheroidal particle and organic carbon source
Homogeneous mixture.
(4) precursor three is placed in batch-type furnace, is passed through argon, be warming up to 1050 DEG C with 10 DEG C/min heating rate, protect
Temperature 10h, naturally cools to room temperature, pulverizes, sieve and remove magnetic, obtains particle diameter and is 1 μm～30 μm obtain silicon-graphene composite negative
Material.
Embodiment 4
(1) silica flour that median particle diameter is 300nm is placed in rotary furnace, is passed through methane and carries out carbon cladding, with 5 DEG C/min liter
Temperature ramp, to 800 DEG C, is incubated 3h, naturally cools to room temperature, obtain carbon-coated nano silicon.
(2) carbon-coated nano silicon and thickness are about the graphene film of 60nm by the nano-silicon in carbon-coated nano silicon: stone
Mass ratio=the 80:20 of ink alkene uniformly mixes, and then adds in dehydrated alcohol by mixed-powder, ultrasonic agitation 30min,
Form homodisperse mixed slurry；Again slurry is placed in high speed dispersor, dispersion stirring 1h, obtain carbon-coated nano silicon and
The homodisperse system of graphene film.Then composite mortar is processed through atomizing exsiccator, obtain spheroidal particle.
(3) spheroidal particle obtained in step (2) is joined with the epoxy resin 60:30 in mass ratio that particle diameter is 3 μm
Ratio, mix homogeneously is placed in VC mixer, and regulating frequency is 30Hz, mixes 60min, obtains spheroidal particle and organic carbon source
Homogeneous mixture.
(4) precursor three is placed in batch-type furnace, is passed through argon, be warming up to 1050 DEG C with 10 DEG C/min heating rate, protect
Temperature 10h, naturally cools to room temperature, pulverizes, sieve and remove magnetic, obtains particle diameter and is 1 μm～30 μm obtain silicon-graphene composite negative
Material.
Embodiment 5
(1) silica flour that median particle is 100nm is placed in rotary furnace, is passed through ethane and carries out vapour deposition, heating rate
It is 5 DEG C/min, is warming up to 750 DEG C of insulation 4h, naturally cools to room temperature, obtain carbon-coated nano silicon.
(2) by carbon-coated nano silicon and graphene film (thickness is 80nm) by the nano-silicon in carbon-coated nano silicon: graphite
Mass ratio=the 60:20 of alkene uniformly mixes, and then adds in dehydrated alcohol by mixed-powder, ultrasonic agitation 40min, shape
The most scattered mixed slurry；Again slurry is placed in high speed dispersor, dispersion stirring 3h, obtains carbon-coated nano silicon and stone
The homodisperse system of ink alkene sheet.Then homodisperse system is processed through atomizing exsiccator, obtain spheroidal particle.
(3) the Colophonium 70:30 in mass ratio that the spheroidal particle obtained in step (2) and particle diameter are 8 μm is carried out proportioning, so
After add in dehydrated alcohol, process through high speed dispersor and form the composite mortar of mix homogeneously after 1h, then by composite mortar
Drying processes, and obtains the homogeneous mixture of spheroidal particle and organic carbon source.
(4) precursor three is placed in batch-type furnace, is passed through argon, be warming up to 900 DEG C with 10 DEG C/min heating rate, insulation
5h, naturally cools to room temperature, pulverizes, sieves and remove magnetic, obtains particle diameter and is 10 μm～15 μm obtain silicon-graphene composite negative material
Material.
Embodiment 6
(1) silica flour that median particle is 160nm is placed in rotary furnace, is passed through ethane and carries out vapour deposition, heating rate
It is 5.0 DEG C/min, is warming up to 850 DEG C of insulation 3.5h, naturally cools to room temperature, obtain carbon-coated nano silicon.
(2) by carbon-coated nano silicon and graphene film (thickness is 120nm) by the nano-silicon in carbon-coated nano silicon: graphite
Mass ratio=the 100:20 of alkene uniformly mixes, and then adds in dehydrated alcohol by mixed-powder, ultrasonic agitation 45min,
Form homodisperse mixed slurry；Again slurry is placed in high speed dispersor, dispersion stirring 3.5h, obtains carbon-coated nano silicon
Homodisperse system with graphene film.Then homodisperse system is processed through atomizing exsiccator, obtain spheroidal particle.
(3) the Colophonium 80:30 in mass ratio that the spheroidal particle obtained in step (2) and particle diameter are 10 μm is carried out proportioning,
It is then added in dehydrated alcohol, after high speed dispersor processes 1h, forms the composite mortar of mix homogeneously, then by composite pulp
Material drying processes, and obtains the homogeneous mixture of spheroidal particle and organic carbon source.
(4) precursor three is placed in batch-type furnace, is passed through argon, be warming up to 760 DEG C with 10 DEG C/min heating rate, insulation
6.5h, naturally cools to room temperature, pulverizes, sieves and remove magnetic, obtains particle diameter and is 12 μm～18 μm obtain silicon-graphene composite negative
Material.
Comparative example 1
In addition to step (2) is without graphene film, other preparation methoies and condition are same as in Example 1, obtain composite wood
Material.
Comparative example 2
In addition to not carrying out step (3), other preparation methoies and condition are same as in Example 1, obtain composite.
Comparative example 3
In addition to not carrying out step (1), other preparation methoies and condition are same as in Example 1, obtain composite.
Table 1
As seen from the above table, the composite that comparative example 1 and comparative example 2 obtain carries out detection knot as lithium ion battery negative
Fruit display, discharge capacity and first charge-discharge efficiency are low, and efficiency is only 80.5%～84.5% first, circulate 500 weeks capacity and protect
Holdup is only 60.4%～68.3%；
Porous silicon-base composite negative pole material prepared by the described method that the embodiment of the present invention 1～6 prepares, specific surface area
Low (2.0m2/ g～10.0m2/ g), the high (1.2g/cm of compacted density3～1.5g/cm3), make the electric discharge appearance that battery testing obtains
Amount is more than 90.0% more than 1500mAh/g, initial coulomb efficiency, circulates 500 weeks capability retentions all more than 90%.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and auxiliary element
Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (10)
1. carbon-coated nano silicon-Graphene-cracking carbon-coating composite, it is characterised in that described composite include by
Carbon-coated nano silicon is dispersed in the spheroidal particle formed in graphene film, and is coated on described spheroidal particle surface
Cracking carbon-coating；Wherein, described carbon-coated nano silicon includes nano-silicon and is coated on the cladding carbon-coating on nano-silicon surface.
Composite the most according to claim 1, it is characterised in that the median particle diameter of described composite is 1 μm～30 μ
M, preferably 2 μm～25 μm, more preferably 4 μm～15 μm；
Preferably, the specific surface area of described composite is 1m2/ g～30m2/ g, preferably 2m2/ g～10m2/g；
Preferably, the powder body compacted density of described composite is 0.5g/cm3～2.5g/cm3, preferably 0.8g/cm3～2g/
cm3；
Preferably, be in terms of 100% by the gross mass of composite, the mass percent of described nano-silicon be 10wt%～
60wt%；
Preferably, be in terms of 100% by the gross mass of composite, described in be coated on nano-silicon surface cladding carbon-coating quality hundred
Proportion by subtraction is 5wt%～30wt%；
Preferably, be in terms of 100% by the gross mass of composite, the mass percent of described graphene film be 5wt%～
50wt%；
Preferably, be in terms of 100% by the gross mass of composite, described in be coated on spheroidal particle surface cracking carbon-coating quality
Percentage ratio is 10wt%～40wt%.
Composite the most according to claim 1 and 2, it is characterised in that the median particle diameter of described nano-silicon is preferably 5nm
～300nm；
Preferably, the specific surface area of described nano-silicon is 10m2/ g～500m2/g；
Preferably, the cladding carbon-coating being coated on nano-silicon surface described in is that gaseous carbon source vapour deposition obtains；
Preferably, described gaseous carbon source is methane, ethane, propane, ethylene, acetylene, the benzene of gaseous state, the toluene of gaseous state, gaseous state
Any a kind or the combination of at least 2 kinds in the acetone of dimethylbenzene, the ethanol of gaseous state or gaseous state；
Preferably, the thickness of the cladding carbon-coating being coated on nano-silicon surface described in is 5nm～500nm；
Preferably, described graphene film is to be formed by stacking by single-layer graphene；
Preferably, the thickness of described graphene film is 50nm～300nm；
Preferably, the cracking carbon-coating being coated on spheroidal particle surface described in is obtained through cracking by organic carbon source；
Preferably, described organic carbon source include alkanes, cycloalkane, alkene, alkynes, aromatic hydrocarbon, polymer, saccharide, organic acid,
Any a kind or the combination of at least 2 kinds in resinae macromolecular material, preferably methane, ethane, ethylene, phenol, Colophonium, ring
Epoxy resins, phenolic resin, furfural resin, Lauxite, polyvinyl alcohol, polrvinyl chloride, Polyethylene Glycol, poly(ethylene oxide), poly-partially
Any a kind or the combination of at least 2 kinds in fluorothene, acrylic resin and polyacrylonitrile；
Preferably, the thickness of the cracking carbon-coating being coated on spheroidal particle surface described in is 0.5 μm～5 μm.
4. the preparation side of the carbon-coated nano silicon-Graphene-cracking carbon-coating composite as described in any one of claim 1-3
Method, it is characterised in that said method comprising the steps of:
(1) use gaseous carbon source that nano-silicon is carried out vapour deposition, obtain carbon-coated nano silicon；
(2) use step (1) the carbon-coated nano silicon that obtains and graphene film, prepare homodisperse system, then drying-granulating,
To spheroidal particle；Wherein, in described spheroidal particle, carbon-coated nano silicon is dispersed between graphene film；
(3) spheroidal particle step (2) obtained and organic carbon source mixing, obtain homogeneous mixture；
(4) homogeneous mixture obtaining step (3) is sintered, and obtains carbon-coated nano silicon-Graphene-cracking carbon-coating and is combined
Material.
Method the most according to claim 4, it is characterised in that described method is additionally included in after step (4) sintered, and enters
The step of magnetic is pulverized, sieves and removed to row cooling and the product obtaining sintering.
6. according to the method described in claim 4 or 5, it is characterised in that step (1) described gaseous carbon source be methane, ethane, third
Alkane, ethylene, acetylene, the benzene of gaseous state, the toluene of gaseous state, the dimethylbenzene of gaseous state, the ethanol of gaseous state, gaseous state acetone in any 1
Plant or the combination of at least 2 kinds；
Preferably, the process of step (1) described vapour deposition is: is placed in atmosphere furnace by nano-silicon, is passed through carbon source, carries out at heat
Reason；
Preferably, during described vapour deposition, described atmosphere furnace is tube furnace, batch-type furnace, rotary furnace, tunnel kiln or pushes away
In plate kiln any a kind；
Preferably, during described vapour deposition, the temperature of described heat treatment is 500 DEG C～1000 DEG C；
Preferably, during described vapour deposition, the time of described heat treatment is 2h～5h.
7. according to the method described in any one of claim 4-6, it is characterised in that in step (2) described carbon-coated nano silicon
Nano-silicon is (60～140) with the mass ratio of graphene film: 20；
Preferably, the technology that step (2) described drying-granulating uses is stirring-granulating method, boiling granulation method, spray drying granulation
Any a kind or the combination of at least 2 kinds in method, pressure forming comminution granulation, the heat fusing method of forming；
Preferably, the equipment that step (2) described drying-granulating uses is pelletize drum, cone drum comminutor, roller pelletizer, kneading
Machine, drum mixer, hammer powder blend machine, vertical shaft type powder blend machine, belt powder blend machine, lower the curtain granule machine, spraying
Drying machine, desk-top squeezer, vacuum depression bar comminutor, single screw extruder pelletizer, twin-screw extruder comminutor, model punching press
Machine, to any a kind or the combination of at least 2 kinds in roller gear comminutor；
Preferably, the preparation process of step (2) described homodisperse system is: carbon-coated nano silicon step (1) obtained and stone
Ink alkene sheet mixing, then adds in organic solvent by the mixed-powder obtained, ultrasonic agitation, forms homodisperse mixing slurry
Material；Again slurry is placed in high speed dispersor, dispersion stirring, obtains homodisperse system；
Preferably, in the preparation process of described homodisperse system, described organic solvent is oxolane, dimethyl acetylamide, C1-
Any a kind or the combination of at least 2 kinds in C6 alcohol and C3-C8 ketone, described C1-C6 alcohol be preferably methanol, ethanol, ethylene glycol, third
Alcohol, isopropanol, 1,2-propylene glycol, 1,3-propylene glycol, glycerol, n-butyl alcohol, 1,2-butanediol, 1,3 butylene glycol, 1,4-fourth two
Any a kind or the combination of at least 2 kinds in alcohol, n-amyl alcohol and 2-hexanol, described C3-C8 ketone be preferably acetone, methyl ethyl ketone,
Methyl propyl ketone, N-Methyl pyrrolidone, ethyl propyl ketone, methyl butyl ketone, ethyl n-butyl ketone, methyl amyl first
Any a kind or the combination of at least 2 kinds in ketone and methyl hexyl ketone.；
Preferably, in the preparation process of described homodisperse system, the time of described ultrasonic agitation is 0.1～1h；
Preferably, in the preparation process of described homodisperse system, described high speed dispersor is homogenizer, planetary mixer, twin shaft
In dispersion machine, single guide pillar dispersion machine, double guide pillar dispersion machine, de-airing mixer, ball mill, sand mill any a kind or at least 2 kinds
Combination；
Preferably, in the preparation process of described homodisperse system, the time of described dispersion stirring is 1h～5h.
8. according to the method described in any one of claim 4-7, it is characterised in that step (3) described spheroidal particle and organic carbon
The mass ratio in source is (60～150): 30；
Step (3) described organic carbon source include alkanes, cycloalkane, alkene, alkynes, aromatic hydrocarbon, polymer, saccharide, organic acid,
Any a kind or the combination of at least 2 kinds in resinae macromolecular material, preferably methane, ethane, ethylene, phenol, Colophonium, ring
Epoxy resins, phenolic resin, furfural resin, Lauxite, polyvinyl alcohol, polrvinyl chloride, Polyethylene Glycol, poly(ethylene oxide), poly-partially
Any a kind or the combination of at least 2 kinds in fluorothene, acrylic resin and polyacrylonitrile；
Preferably, when the organic carbon source that step (3) described organic carbon source is solid-state, the particle diameter of organic carbon source is 5 μm～20 μm；
Preferably, any a kind during the preparation method of described homogeneous mixture is solid phase cladding process or liquid phase coating method；Wherein,
The preparation process of described solid phase cladding process is: spheroidal particle step (2) obtained and organic carbon source mix homogeneously, is placed in VC and mixes
In conjunction machine, mix, obtain homogeneous mixture；
The preparation process of described liquid phase coating method is: the spheroidal particle and the organic carbon source that step (2) are obtained are distributed in solvent,
Mixing, is dried, obtains homogeneous mixture；
Preferably, in described solid phase cladding process, during mixing, the frequency of VC mixer is 5Hz～50Hz；
Preferably, in described solid phase cladding process, the time of mixing at more than 30min, preferably 0.5h～5h, more preferably
0.5h～3h；
Preferably, in described liquid phase coating method, solvent is water and/or organic solvent；
Preferably, the temperature of step (4) described sintering is 400 DEG C～1200 DEG C；
Preferably, the time of step (4) described sintering is 0.5h～10h；
Preferably, carrying out under conditions of being sintered in protective gas protection described in step (4), described protective gas is preferably nitrogen
Any a kind or the combination of at least 2 kinds in gas, helium, neon, argon, Krypton and xenon；
Preferably, being sintered in firing furnace carrying out described in step (4), described firing furnace is preferably vacuum drying oven, batch-type furnace, revolution
Stove, roller kilns, pushed bat kiln or tube furnace.
9. a negative material, it is characterised in that described negative material is the carbon-coated nano described in any one of claim 1-5
Silicon-Graphene-cracking carbon-coating composite.
10. a lithium ion battery, it is characterised in that described lithium ion battery comprises answering described in any one of claim 1-5
Condensation material is as negative material.
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