CN106784741A - A kind of carbon-silicon composite material, its preparation method and the lithium ion battery comprising the composite - Google Patents
A kind of carbon-silicon composite material, its preparation method and the lithium ion battery comprising the composite Download PDFInfo
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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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- 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
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- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- 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
- H01M4/621—Binders
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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
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- H—ELECTRICITY
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- 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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- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of lithium ion battery the invention discloses carbon-silicon composite material, its preparation method and comprising the composite, the carbon-silicon composite material includes the kernel of amorphous carbon, and is scattered in the shell formed in pyrolytic carbon layer by nano-silicon.The method of the present invention is simple, easy to operate, it is environment-friendly, it is adapted to large-scale production, the carbon-silicon composite material Stability Analysis of Structures for preparing, it is very high that the good dispersion and nano-silicon of nano-silicon are wrapped by degree, as the negative material of lithium ion battery, show de- lithium specific capacity very high, good cycle and fill excellent soon, take off lithium specific capacity in more than 391.7mAh/g, more than 95.3%, 10min charge rates are up to 90.2% for 50 capability retentions of 1.0C constant current charge-discharges.
Description
Technical field
The invention belongs to electrochemistry and technical field of lithium ion battery negative, it is related to a kind of composite, its preparation
Method and the lithium ion battery comprising the composite, more particularly to a kind of carbon-silicon composite material, its preparation method, and comprising
The carbon-silicon composite material as negative material lithium ion battery.
Background technology
The high rate performance of traditional graphite material, cryogenic property are poor, and theoretical capacity only has 372mAh/g, which has limited
Its application in electrokinetic cell field.Unsetting (soft carbon, hard carbon) has relatively more excellent multiplying power, circulation, cryogenic property, is system
One of ideal material of standby electrokinetic cell.Its shortcoming is that the specific capacity of amorphous carbon is relatively low, wherein, pure soft carbon capacity is difficult to reach
To more than 300mAh/g, ripe pure hard carbon product capacity typically also can only achieve 450mAh/g, and amorphous carbon jolt ramming
Density is all relatively low, in the long run, is still insufficient for the requirement of electric automobile endurance.
Improving the method for carbon material volumetric properties has doping, compound, oxidation etc..Wherein, silicon has quality specific volume higher
Amount (4200mAh/g), is combined using silicon and amorphous carbon, can keep the basis of the excellent multiplying power of amorphous carbon, cryogenic property
On further lift its volumetric properties, prepare and fill high power capacity carbon compound cathode materials soon suitable for electrokinetic cell.
The difficult point prepared containing silicon composite cathode material is to improve its cycle performance.At present, it is common for preparing silicon substrate
The method of material has：The nanosizing of silicon, porous, alloying；Silicon is embedded into buffer matrix；Clad is formed in silicon face
(clad can be conducting polymer, macromolecule pyrolytic carbon, metal etc.).These methods can to a certain extent suppress silicon and exist
Volumetric expansion during embedding de- lithium, so as to improve its cycle performance.
As patent CN 103337612A disclose a kind of nanoporous silicon-carbon composite cathode material and preparation method thereof.Should
Method obtains the nanoporous silicon-carbon composite cathode material of a kind of high-performance, high stability by etching silicon-carbon ternary-alloy material
Material, it is simple to operate.But, the structure of this material is difficult to ensure that first effect higher, relatively costly in practical application.
As patent CN103618074A discloses a kind of method of use polymer microsphere embedding nano silicon, improve silicon-carbon and answer
The dispersiveness of nano-silicon in negative material is closed, so as to alleviate the bulk effect of silicon in process of intercalation, its cycle performance is improved, but
The operation of the preparation method of the patent disclosure is more, process is cumbersome, and the value of practical application is not high.
Therefore, a kind of excellent multiplying power that can keep amorphous carbon negative material, circulation and low-temperature characteristics, raising are developed
Its capacity characteristic, but simple operations be easy to industrialized production method be urgent need to resolve technological difficulties.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to invent a kind of high power capacity carbon-silicon composite material, its system
Preparation Method and the lithium ion battery comprising the carbon-silicon composite material, carbon-silicon composite material Stability Analysis of Structures of the invention, nano-silicon
Good dispersion and nano-silicon are wrapped by that degree is very high, as the negative material of lithium ion battery, show de- lithium ratio very high
Capacity, good cycle and fills excellent soon, takes off lithium specific capacity in more than 391.7mAh/g, 50 appearances of 1.0C constant current charge-discharges
More than 95.3%, 10min charge rates are up to 90.2% for amount conservation rate.
It is that, up to above-mentioned purpose, the present invention is adopted the following technical scheme that：
In a first aspect, the present invention provides a kind of carbon-silicon composite material, the carbon-silicon composite material includes kernel and cladding
In the shell of core surface, wherein, the kernel is amorphous carbon, the shell be scattered in pyrolytic carbon layer by nano-silicon and
Formed.
Preferably, the median particle diameter of the carbon-silicon composite material is 5 μm~60 μm, for example, can be 5 μm, 7 μm, 8 μm, 10 μ
m、12μm、15μm、17μm、19μm、22μm、24μm、25μm、26μm、28μm、30μm、33μm、35μm、38μm、40μm、45μm、
48 μm, 52 μm, 56 μm or 60 μm etc., preferably 8 μm~30 μm, more preferably 10 μm~25 μm.
Preferably, the specific surface area of the carbon-silicon composite material is 0.8m2/ g~3.5m2/ g, for example, can be 0.8m2/g、
1m2/g、1.2m2/g、1.4m2/g、1.6m2/g、1.8m2/g、2m2/g、2.3m2/g、2.6m2/g、3m2/g、3.2m2/ g or 3.5m2/
G etc., preferably 1.1m2/ g~2.0m2/g。
Preferably, the compacted density of the carbon-silicon composite material is 0.9g/cm3~2.0g/cm3, for example, can be 0.9g/
cm3、1.1g/cm3、1.3g/cm3、1.5g/cm3、1.6g/cm3、1.7g/cm3、1.8g/cm3Or 2g/cm3Deng being for example preferably
1.0g/cm3~1.4g/cm3。
Preferably, the amorphous carbon includes soft carbon and/or hard carbon.
" soft carbon and/or hard carbon " of the present invention refers to：Can be soft carbon, or hard carbon, can also be soft carbon and hard
The mixture of carbon.
In the present invention, the kernel is amorphous carbon, the median particle diameter of the amorphous carbon be preferably 5 μm~30 μm, example
It such as can be 5 μm, 6 μm, 7 μm, 9 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 17 μm, 20 μm, 22 μm, 25 μm, 28 μm or 30 μm
Deng preferably 7~20 μm, more preferably 9 μm~15 μm；
Preferably, the median particle diameter of the nano-silicon be 25nm~300nm, for example can for 25nm, 35nm, 45nm, 50nm,
60nm、75nm、80nm、90nm、100nm、110nm、125nm、135nm、140nm、150nm、160nm、175nm、190nm、
210nm, 230nm, 245nm, 260nm, 280nm or 300nm etc., preferably 80nm~200nm.
Preferably, the thickness of the shell is 0~3.0 μm, and does not include 0.
Preferably, the pyrolytic carbon layer is that the binding agent is preferably wrapped as obtained from binding agent and carbon source by pyrolysis
Include in pitch, polyvinyl alcohol or phenolic resin any one or at least two mixture, but be not limited to above-mentioned enumerating
Adhesive, pyrolytic carbon can be converted into carbonisation for others and the adhesive with adhesive effect can also be used for the present invention.
Preferably, the carbon source preferably includes pitch and/or macromolecular compound.
" pitch and/or macromolecular compound " of the present invention refers to：Can be pitch, or macromolecular compound,
Can also be the mixture of pitch and macromolecular compound.
The macromolecular compound can be for example polymer and carbohydrate etc., but be not limited to polymer and carbohydrate, other
The macromolecular compound of species also can be used for the present invention as carbon source.
Preferably, the macromolecular compound includes that macromolecule is epoxy resin, phenolic resin, furfural resin, ureaformaldehyde tree
In fat, polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, PEO, Kynoar, acrylic resin or polyacrylonitrile
Any one or at least two mixture, but be not limited to the macromolecular compound enumerated, carbon bag commonly used in the art
Cover and can also be used for the present invention with carbon source.
Second aspect, the present invention provides the preparation method of carbon-silicon composite material as described in relation to the first aspect, methods described bag
Include following steps：
(1) surface modification is carried out to amorphous carbon using binding agent；
(2) amorphous carbon of the binding agent modification for obtaining step (1) is combined with nano-silicon, then compound to what is obtained
Product carries out the first carbonization, obtains the first carbon silicon composite precursor；
(3) the first carbon silicon composite precursor obtained to step (2) using carbon source carries out coating modification, obtains the second carbon silicon
Composite precursor, then the second carbon silicon composite precursor to obtaining carries out the second carbonization, obtains carbon-silicon composite material.
Used as the optimal technical scheme of the method for the invention, methods described is additionally included in the carbonization of step (2) first and completes
Afterwards, the step of being sieved to the first product for obtaining of carbonization, the mesh number of the screen cloth that the sieving is used is 200 mesh or 325 mesh, preferably
It is 325 mesh.
Used as the another optimal technical scheme of the method for the invention, methods described is additionally included in the carbonization of step (3) second
After the completion of, the second product for obtaining of carbonization is crushed, is sieved and the step of except magnetic.
Preferably, step (1) described amorphous carbon includes soft carbon and/or hard carbon, for example, can be soft carbon, hard carbon, or soft carbon
With the mixture of hard carbon.
Preferably, step (1) described binding agent include pitch, polyvinyl alcohol or phenolic resin in any one or at least
Two kinds of mixture, but be not limited to the above-mentioned binding agent enumerated, it is other through carbonization can be converted into pyrolytic carbon with viscous
The binding agent of knot effect can also be used for the present invention.
Binding agent in the present invention is converted into pyrolytic carbon in follow-up carbonisation, such that it is able to make nano-silicon not only receive
The cladding of the pyrolytic carbon being converted into the follow-up carbon source for adding, also receives the cladding of the pyrolytic carbon that binding agent is converted into, so as to carry
High nano-silicon is wrapped by degree.
Preferably, the median particle of step (1) described bonding agent be less than or equal to 5 μm, for example can for 5 μm, 4.5 μm, 4 μm,
3.5 μm, 3 μm, 2 μm, 1.5 μm, 1 μm, 0.8 μm or 0.5 μm etc., preferably less than equal to 2 μm.
Preferably, the method that step (1) described surface modification is used modifies any in method or liquid phase modification method for solid phase
It is a kind of.Wherein, the preparation process of the solid phase modification method is：Binding agent and amorphous carbon are placed in VC mixers, are mixed
Close, then, mixed material is added in fusion machine and is merged, obtain the amorphous carbon of binding agent modification.
The preparation process of liquid phase modification method is：Binding agent is dissolved in solvent, amorphous carbon is added, stirring is steamed
Dry solvent, obtains the amorphous carbon of binding agent modification.
Preferably, in the solid phase modification method, during mixing, the rotating speed of VC mixers is 500r/min~3000r/min, example
Such as can for 500r/min, 700r/min, 800r/min, 1000r/min, 1200r/min, 1500r/min, 1750r/min,
1850r/min、2000r/min、2200r/min、2300r/min、2400r/min、2500r/min、2600r/min、2800r/
Min or 3000r/min etc..
Preferably, in the solid phase modification method, the time of the mixing (or breaing up) is no less than 15min, for example, can be
15min、25min、30min、40min、50min、1h、1.2h、1.5h、1.8h、2h、2.4h、2.7h、3h、4h、6h、8h、10h、
12h or 15h etc., preferably 30min；
Preferably, in the solid phase modification method, during fusion, the rotating speed for merging machine is 500r/min~3000r/min, for example
Can be 500r/min, 600r/min, 900r/min, 1000r/min, 1200r/min, 1400r/min, 1600r/min, 1800r/
Min, 2000r/min, 2200r/min, 2300r/min, 2400r/min, 2500r/min, 2600r/min, 2750r/min or
3000r/min etc.；Cutter gap width in fusion machine is preferably 0.01cm~0.5cm, for example can for 0.01cm, 0.03cm,
0.05cm, 0.1cm, 0.15cm, 0.2cm, 0.3cm, 0.35cm, 0.4cm or 0.5cm etc.；
Preferably, in the solid phase modification method, time of the fusion is no less than 0.5h, for example can for 0.5h, 1h,
1.5h, 2h, 2.4h, 3.5h, 4h, 5h, 6.5h, 7h, 8h, 9h, 10h, 12h, 15h, 20h, 24h, 28h, 30h, 32h, 34h or
36h etc., preferably 45min.
Preferably, in the liquid phase modification method, the solvent is appointing in tetrahydrofuran, toluene, carbon disulfide, alcohol or water
Meaning it is a kind of or at least two mixtures.
Preferably, step (2) the compound method is：Step (1) is obtained binding agent modification amorphous carbon and
Nano-silicon is added in solvent, stirring, solvent evaporated, is obtained so as in the presence of binding agent, make nano-silicon be bonded to step (1)
The surface of the amorphous carbon of the binding agent modification arrived, obtains combination product.
Preferably, in step (2) the compound method, the solvent is any one in isopropanol, ethanol or water
Or at least two mixture.
Preferably, step (2) it is described first carbonization carry out in an inert atmosphere, the inert atmosphere include nitrogen atmosphere,
In argon gas atmosphere, neon atmosphere, helium atmosphere, xenon atmosphere or Krypton atmosphere any one or at least two combination.
Preferably, step (2) it is described first carbonization temperature be 400 DEG C~800 DEG C, for example can for 400 DEG C, 450 DEG C,
475 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, 620 DEG C, 650 DEG C, 700 DEG C, 750 DEG C or 800 DEG C etc..
Preferably, step (2) it is described first carbonization time be 2h~6h, for example can for 2h, 2.3h, 2.5h, 2.7h,
3h, 3.4h, 3.7h, 4h, 4.5h, 4.8h, 5h, 5.2h, 5.5h, 5.8h or 6h etc..
Preferably, during being warmed up to the temperature of step (2) first carbonization, heating rate is 1 DEG C/min~10
DEG C/min, for example can be 1 DEG C/min, 3 DEG C/min, 5 DEG C/min, 6 DEG C/min, 8 DEG C/min or 10 DEG C/min etc..
Preferably, step (3) described carbon source includes pitch and/or macromolecular compound, and the macromolecular compound is for example
Can be polymer and carbohydrate etc..
Preferably, the macromolecular compound includes epoxy resin, phenolic resin, furfural resin, Lauxite, polyethylene
In alcohol, polyvinyl chloride, polyethylene glycol, PEO, Kynoar, acrylic resin or polyacrylonitrile any one or
At least two mixture, but it is not limited to the macromolecular compound enumerated, carbon coating carbon source commonly used in the art
Can be used for the present invention.
Preferably, counted by 100wt% of the gross mass of carbon source and the first carbon silicon composite precursor, step (3) described carbon source
Mass percent be 5wt%~20wt%, for example can for 5wt%, 7wt%, 8wt%, 9wt%, 10wt%, 12wt%,
13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt% or 20wt% etc., preferably 8wt%~13wt%.
Preferably, the method that step (3) described coating modification is used is solid phase cladding process, liquid phase coating method, fusion cladding
Method or spray drying cladding process in any one.Wherein, the preparation process of the solid phase cladding process is：First carbon silicon is combined
Presoma is placed in VC mixers with carbon source, is mixed, and obtains the second carbon silicon composite precursor.
The preparation process of the liquid phase coating method is：First carbon silicon composite precursor and carbon source are added in solvent, are stirred
Mix, solvent evaporated, obtain the second carbon silicon composite precursor.
It is described fusion cladding process preparation process be：First carbon silicon composite precursor is added in the machine of fusion with carbon source
Row fusion, obtains the second carbon silicon composite precursor.
It is described spray drying cladding process preparation process be：First carbon silicon composite precursor and carbon source are added to solvent
In, stirring obtains mixed slurry, is spray-dried, and obtains the second carbon silicon composite precursor.
Preferably, in the solid phase cladding process, during mixing, the rotating speed of VC mixers is 500r/min~3000r/min, example
Such as can for 500r/min, 650r/min, 800r/min, 1000r/min, 1250r/min, 1450r/min, 1600r/min,
1900r/min, 2150r/min, 2300r/min, 2500r/min, 2700r/min or 3000r/min etc..
Preferably, in the solid phase cladding process, the time of the mixing (or breaing up) is no less than 15min, for example, can be
15min, 30min, 50min, 1h, 1.5h, 2h, 3h, 5h, 8h, 10h, 12h, 15h, 18h, 24h or 36h etc., preferably 30min；
Preferably, in the liquid phase coating method, the solvent is appointing in tetrahydrofuran, toluene, carbon disulfide, alcohol or water
Meaning it is a kind of or at least two mixtures.
Preferably, in the fusion cladding process, during fusion, the rotating speed for merging machine is 500r/min~3000r/min, for example
Can for 500r/min, 800r/min, 1000r/min, 1250r/min, 1700r/min, 2000r/min, 2300r/min,
2600r/min, 2800r/min or 3000r/min etc., the gap width of the cutter in fusion machine is 0.01cm~0.5cm, for example
Can be 0.01cm, 0.05cm, 0.1cm, 0.2cm, 0.3cm, 0.4cm or 0.5cm etc..
Preferably, in the fusion cladding process, time of the fusion is no less than 0.5h, for example can for 1h, 2h, 3h, 5h,
7h, 10h, 12h, 15h, 24h, 30h, 36h or 48h etc., preferably 45min.
Preferably, in the spray drying cladding process, the solvent is in tetrahydrofuran, toluene, carbon disulfide, alcohol or water
Any one or at least two mixture.
Preferably, in the spray drying cladding process, the condition of the spray drying is：Inlet temperature is 250 DEG C~400
DEG C, preferably 300 DEG C；Outlet temperature is 90 DEG C~115 DEG C, preferably 110 DEG C；The solid of mixed slurry for being spray-dried contains
It is 10wt%~30wt% to measure；The feed rate of mixed slurry is 10mL/min~40mL/min during spray drying.
In the spray drying cladding process, inlet temperature be 250 DEG C~400 DEG C, for example, 250 DEG C, 275 DEG C, 300 DEG C,
320 DEG C, 350 DEG C, 360 DEG C, 380 DEG C or 400 DEG C etc..
In the spray drying cladding process, outlet temperature be 90 DEG C~115 DEG C, for example, 90 DEG C, 92 DEG C, 95 DEG C, 100
DEG C, 103 DEG C, 106 DEG C, 110 DEG C or 115 DEG C etc..
In the spray drying cladding process, the solid content of the slurry for being spray-dried is 10wt%~30wt%, for example
Can be 10wt%, 12wt%, 15wt%, 17wt%, 20wt%, 22wt%, 24wt%, 26wt%, 28wt% or 30wt% etc..
In the spray drying cladding process, the feed rate of mixed slurry is 10mL/min~40mL/ during spray drying
Min, for example can for 10mL/min, 15mL/min, 18mL/min, 20mL/min, 25mL/min, 30mL/min, 33mL/min,
36mL/min or 40mL/min etc..
Preferably, step (3) it is described second carbonization carry out in an inert atmosphere, the inert atmosphere include nitrogen atmosphere,
In argon gas atmosphere, neon atmosphere, helium atmosphere, xenon atmosphere or Krypton atmosphere any one or at least two combination.
Preferably, step (3) it is described second carbonization temperature be 900 DEG C~1100 DEG C, for example can for 900 DEG C, 920 DEG C,
940 DEG C, 960 DEG C, 985 DEG C, 1000 DEG C, 1025 DEG C, 1050 DEG C, 1080 DEG C or 1100 DEG C etc..
Preferably, step (3) it is described second carbonization time be 2h~4h, for example can for 2h, 2.5h, 3h, 3.2h,
3.5h, 3.6h, 3.8h or 4h etc..
Preferably, during the temperature of step (2) second carbonization is warmed up to from the temperature of the first carbonization, heat up speed
Rate be 1 DEG C/min~10 DEG C/min, for example can for 1 DEG C/min, 3 DEG C/min, 5 DEG C/min, 6 DEG C/min, 7 DEG C/min, 8 DEG C/
Min, 9 DEG C/min or 10 DEG C/min etc..
The third aspect, the present invention provides a kind of negative material, and the negative material is that the carbon silicon described in first aspect is combined
Material.
Fourth aspect, the present invention provides a kind of lithium ion battery, and the lithium ion battery is included as described in relation to the first aspect
Carbon-silicon composite material is used as negative material.
Compared with prior art, the invention has the advantages that：
(1) present invention can be converted into the adhesive of pyrolytic carbon from through being carbonized, by first with adhesive to amorphous carbon
Surface modification is carried out, then the further composite Nano silicon under the adhesive effect of adhesive, is carbonized then at relatively low temperature control one
After carry out carbon source cladding, be finally carbonized in temperature control two higher, obtain carbon-silicon composite material.Method of the present invention operation letter
It is single, it is adapted to large-scale production.
(2) in carbon-silicon composite material of the invention, on the one hand adding for binding agent improve amorphous carbon and nano-silicon
Active force, it is suppressed that silicon nanoparticle from agglomeration so that nano-silicon can equably be compound to amorphous carbon material table
Face, the bulk effect of silicon and the influence to its structure during the de- lithium of reduction；On the other hand, binding agent is converted in carbonisation
It is pyrolytic carbon, the pyrolytic carbon converted with carbon source cooperatively coats nano-silicon so as to improve the degree that is wrapped by of nano-silicon, wraps
Cover that effect is good, can effectively suppress the expansion of silicon, improve the chemical properties such as cycle performance.And, it is dispersed with the heat of nano-silicon
Solution carbon forms conductive network, compensate for the inferior position of silicon poorly conductive, is conducive to playing and improving the capacity and first effect of silicon.
(3) Stability Analysis of Structures of carbon-silicon composite material that the present invention is prepared, nano-silicon is uniformly dispersed and is wrapped by degree
It is very high, the negative material of lithium ion battery is highly suitable as, battery is made using carbon-silicon composite material of the invention, show
De- lithium specific capacity very high, good cycle and fills excellent soon, takes off lithium specific capacity in more than 391.7mAh/g, and 1.0C is permanent
More than 95.3%, 10min charge rates are up to 90.2% for stream 50 capability retentions of discharge and recharge.
Brief description of the drawings
Fig. 1 is the mechanism explanation schematic diagram that the present invention prepares carbon-silicon composite material；
Fig. 2A and Fig. 2 B are respectively the SEM figures of the combination product of comparative example 1 and embodiment 1；
Fig. 3 A are the SEM figures of the amorphous carbon (i.e. soft carbon) before embodiment 1 is modified；
Fig. 3 B are the SEM figures of the amorphous carbon (i.e. the soft carbon of hard pitch modification) after embodiment 1 is modified；
Fig. 3 C and 3D are respectively SEM figure of the carbon-silicon composite material of embodiment 1 at 10000 times and 10000 times；
Fig. 4 A are the carbon-silicon composite material XRD curves of embodiment 1 and embodiment 2；
Fig. 4 B are that the carbon-silicon composite material for preparing of embodiment 1 and embodiment 2 is made battery and is buckleing as negative material
Electrochemical property test is carried out under the conditions of electrical testing, the first charge-discharge curve for obtaining；
Fig. 5 is made battery under the conditions of electricity is buckled with 1.0C for the composite of embodiment 1 and comparative example 1 as negative material
Multiplying power is circulated performance test, the cycle performance curve for obtaining；
Fig. 6 is made battery under cylindrical battery test condition for the carbon-silicon composite material of embodiment 1 as negative material
Tested, obtained rapid charging performance curve；Wherein, the carbon-silicon composite material of SSC-1 correspondences embodiment 1, SSC-2 correspondence embodiments
2 carbon-silicon composite material, the composite of Ref-1 correspondence comparative examples 1.
Specific embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by specific embodiment.
The mechanism that the present invention prepares carbon-silicon composite material illustrates schematic diagram referring to Fig. 1.
Prepared at identical conditions as negative material using the composite that embodiment 1-5 and comparative example 1 are prepared
Battery.
Specific button cell is prepared and is prepared using method well known in the art.
The preparation method of specific cylindrical battery is as follows：By negative material, conductive agent and binding agent by mass percentage
94:1:5 mix their dissolvings in a solvent, and control solid content is coated in copper foil current collector, vacuum drying, system 50%
Obtain cathode pole piece；Then tertiary cathode pole piece, the LiPF6/EC+DMC+EMC (v/v of 1mol/L for being prepared by traditional maturation process
=1:1:1) electrolyte, Celgard2400 barrier films, shell assemble 18650 cylinder cells using conventional production process.
The charge-discharge performance and first effect of battery are tested under the conditions of electrical testing is detained：Wherein, button electrical testing condition is：First with CC
The mode of+CV is discharged (constant pressure after i.e. first constant current), and then charged (constant current), and the perseverance during charging and discharging in the way of CC
Stream multiplying power is 0.1C, and the blanking voltage that constant current turns constant pressure is 5mV, and test result is shown in Table 2.
The high rate performance of battery is tested under cylindrical battery test condition, in Wuhan Jin Nuo Electronics Co., Ltd.s LAND electricity
Tested in normal temperature condition in the test system of pond, charging/discharging voltage is limited in 2.0V~4.2V, and test result is shown in Table 2.
The rapid charging performance of battery is tested under cylindrical battery test condition, CC+CV is carried out using 6C in test process and is filled
Electricity, test result is referring to Fig. 6.
Embodiment 1
(1) surface modification：Modify method by solid phase with binding agent carries out surface modification to amorphous carbon, specifically, accurately
47.6g hard pitches and 456.4g soft carbons are weighed, the two is placed in and is mixed 30min in VC mixers, the rotating speed of VC mixers
3000r/min.Then, the material of gained is put into fusion machine, merges 45min, merge the rotating speed 3000r/min of machine, obtained
The soft carbon of hard pitch modification, labeled as SC@LQ；
(2) it is combined：Nano silica fume, dispersant are added in isopropanol, high-energy ball milling, ball milling condition is, rotating speed 300r/
Min, ball milling 24h, obtain silicon slurry.It is accurate to weigh silicon slurry (conversion is 2.8g silicon, and solvent is isopropanol), ultrasonic disperse
30min, it is standby.Under conditions of being stirred at room temperature, the soft carbon (SC@LQ) that 36.0g hard pitches are modified is added to above-mentioned ultrasound
In silicon slurry afterwards, heating water bath after magnetic agitation 45min, solvent evaporated is transferred in 120 DEG C of baking ovens after gained material is broken up
Drying, obtains combination product；
(3) first carbonizations：Under the protection of inert gas, be carbonized the combination product that step (2) is obtained 3h at 600 DEG C,
Heating rate during from room temperature to 600 DEG C is 3 DEG C/min, after the completion of carbonization, is cooled to room temperature, 325 eye mesh screen mistakes
Sieve, obtains the first carbon silicon composite precursor；
(4) coating modification：(gross mass with pitch and the first carbon silicon composite precursor is as 100wt% to use 9.3wt%
Meter) pitch carry out solid phase cladding, specific encapsulation steps are：The first carbon silicon composite precursor and drip are weighed according to mass ratio
Green grass or young crops, the two is well mixed, and obtains the second carbon silicon composite precursor；
(5) second carbonizations：Then under the protection of inert gas by step (4) gained the second carbon silicon composite precursor with 3
DEG C/min speed from room temperature to 980 DEG C, be carbonized 3h at 980 DEG C, and room temperature, 325 eye mesh screen mistakes are cooled to after the completion of carbonization
Sieve, has just obtained carbon-silicon composite material, is named as SSC-1.
Using the carbon-silicon composite material of the present embodiment as negative material be used for lithium ion battery, gained battery have be filled with soon
And the good characteristic such as high power capacity.
The specific surface area and granularity data of the carbon-silicon composite material of the present embodiment are shown in Table 1.
The de- lithium capacity of the battery being made as negative pole using the carbon-silicon composite material of the present embodiment, first effect (de- lithium capacity/embedding
Lithium capacity) and 18650 cylindrical battery multiplying power charging capacitys the results are shown in Table 2.
Fig. 2A and Fig. 2 B are respectively the SEM figures of the combination product of comparative example 1 and embodiment 1.As seen from the figure, in comparative example 1
Binding agent modification is not carried out to amorphous carbon and directly the silicon with nanosizing is combined, the silicon of nanosizing occurs in that very serious
From agglomeration, and be non-uniformly dispersed in the surface and gap of amorphous carbon particles (Fig. 2A)；And in embodiment 1 first
Soft carbon is modified using hard pitch, the soft carbon and the silicon of nanosizing that hard pitch is modified again then are combined, nanosizing
Silicon is equably bonded in the surface (Fig. 2 B) of amorphous carbon soft carbon, it is indicated above that modification of the binding agent to amorphous carbon can rise
To the promotion finely dispersed effect of nano-silicon.
Fig. 3 A are the SEM figures of the amorphous carbon (i.e. soft carbon) before embodiment 1 is modified；Fig. 3 B are the nothing after embodiment 1 is modified
The SEM figures of setting carbon (i.e. the soft carbon of hard pitch modification)；The carbon-silicon composite material that Fig. 3 C and 3D are respectively embodiment 1 exists
10000 times and 10000 times of SEM figures.As seen from the figure, it is soft after solid phase modification compared with (Fig. 3 A) before the modification of soft carbon solid phase
The surface of carbon forms a layer binder clad, i.e. hard pitch clad (Fig. 3 B).Using the amorphous of binding agent modification
Carbon is combined with silicon, and silicon can evenly and densely be compound to the surface (Fig. 3 C and Fig. 3 D) of soft carbon
Fig. 4 A are the carbon-silicon composite material XRD curves of embodiment 1 and embodiment 2.As seen from the figure in SSC-1, SSC-2
The characteristic peak of soft carbon and silicon can be respectively found in XRD curves, is shown, the material for preparing of the present invention strictly soft carbon,
Silicon composite.
Fig. 4 B are that the carbon-silicon composite material for preparing of embodiment 1 and embodiment 2 is made battery and is buckleing as negative material
Electrochemical property test is carried out under the conditions of electrical testing, the first charge-discharge curve for obtaining.As seen from the figure, repaiied using solid phase, liquid phase
The charging and discharging curve of decorations gained Si-C composite material almost overlaps, and maintains the distinctive charging and discharging curve shape of soft carbon substantially
Shape, it is indicated above that it is that its volumetric properties is lifted on the basis of soft carbon silicon-carbon to be carried out to soft carbon composite modified.
Fig. 5 enters for the composite of embodiment 1 and comparative example 1 is made battery as negative material under the conditions of electrical testing is buckled
Row electrochemical property test, the cycle performance curve for obtaining.As seen from the figure, the cycle performance of the SSC-1 that embodiment 1 is obtained
The cycle performance of the Ref-1 that comparative example 1 is obtained is substantially better than, binding agent (being hard pitch in embodiment 1) is used to amorphous
Carbon (being soft carbon in embodiment 1) carries out surface modification, the active force between soft carbon and nano-silicon is improve, so as to inhibit nanometer
Silicon grain from agglomeration, nano-silicon is equably compound to the surface of amorphous carbon, and due to the binding agent in the present invention
And the follow-up carbon source for adding is converted into pyrolytic carbon after carbonisation so that the degree that is wrapped by of nano-silicon is greatly enhanced,
The dispersed and intact cladding of silicon in carbon-silicon composite material advantageously reduces the bulk effect of silicon during de- lithium to it
The influence of structure, so as to improve its cycle performance.
Fig. 6 is the rapid charging performance curve of the carbon-silicon composite material of embodiment 1.The battery that the SSC-1 of embodiment 1 is made is in 6C
Multiplying power under constant-voltage charge after first constant-current charge, constant-current charge to charge rate during 7.8min is 76.2%；Continue constant-voltage charge extremely
Charge rate is 90.2% during 10min, shows very excellent rapid charging performance.
Embodiment 2
(1) surface modification：Modify method by liquid phase with binding agent carries out surface modification to amorphous carbon, accurately weighs 3.4g
, be added to for hard pitch under conditions of room temperature magnetic agitation in 100mL tetrahydrofurans (THF) solution by hard pitch, stirring
1h, obtains the THF solution of pitch, to 32.6g soft carbons are added in the THF solution of pitch, heats solvent evaporated, obtains hard pitch and repaiies
The soft carbon of decorations.
(2) it is combined：Nano silica fume, dispersant are added in isopropanol, high-energy ball milling, ball milling condition is, rotating speed 300r/
Min, ball milling 24h, obtain silicon pulp solution.After the soft carbon and ultrasonic disperse 1h of the hard pitch modification obtained by step (1)
Silicon slurry (conversion is 2.8g silicon, and solvent is isopropanol) is added sequentially in the isopropanol solvent of 80mL, room temperature high-speed stirred
45min, heats solvent evaporated, and drying in 120 DEG C of baking ovens is transferred to after gained material is broken up, and obtains combination product.
(3) first carbonizations：Under the protection of inert gas, be carbonized the combination product that step (2) is obtained 3h at 600 DEG C,
3 DEG C/min of heating rate during from room temperature to 600 DEG C, after the completion of carbonization, is cooled to room temperature, and gained carbonized stock is entered
The eye mesh screen of row 325 sieves, and obtains the first carbon silicon composite precursor.
(4) coating modification：(gross mass with pitch and the first carbon silicon composite precursor is as 100wt% to use 9.3wt%
Meter) pitch carry out solid phase cladding, specific encapsulation steps are：The first carbon silicon composite precursor and drip are weighed according to mass ratio
Green grass or young crops, the two is well mixed, and obtains the second carbon silicon composite precursor.
(5) second carbonizations：Then it is under the protection of inert gas that gained the second carbon silicon composite precursor is fast with 3 DEG C/min
From room temperature to 980 DEG C, be carbonized rate 3h at 980 DEG C, and room temperature is cooled to after the completion of carbonization, and the sieving of 325 eye mesh screens is just obtained
Carbon-silicon composite material, is named as SSC-2.
Using the carbon-silicon composite material of the present embodiment as negative material be used for lithium ion battery, gained battery have be filled with soon
And the good characteristic such as high power capacity.
The specific surface area and granularity data of the carbon-silicon composite material of the present embodiment are shown in Table 1.
The de- lithium capacity of the battery being made as negative pole using the carbon-silicon composite material of the present embodiment, first effect (de- lithium capacity/embedding
Lithium capacity) and 18650 cylindrical battery multiplying power charging capacitys the results are shown in Table 2.
Embodiment 3
(1) surface modification：Modify method by liquid phase with binding agent carries out surface modification to amorphous carbon.Accurately weigh 3.4g
Phenolic resin, during hard pitch to be added to 100mL ethanol under conditions of room temperature magnetic agitation, stirs 1h, obtains phenolic resin
Ethanol solution, in the ethanol of phenolic resin add 32.6g soft carbons, heat solvent evaporated, obtain phenolic resin modification it is soft
Carbon.
(2) it is combined：Nano silica fume, dispersant are added in isopropanol, high-energy ball milling, ball milling condition is, rotating speed 300r/
Min, ball milling 24h, obtain silicon slurry.It is accurate to weigh silicon slurry (conversion is 2.8g silicon, and solvent is isopropanol), ultrasonic disperse
45min, obtains silicon slurry, standby.Under conditions of being stirred at room temperature, the soft carbon that 3.6g polyvinyl alcohol is modified is added to above-mentioned super
In silicon slurry after sound, heating water bath after stirring 60min, solvent evaporated is transferred to baking in 120 DEG C of baking ovens after gained material is broken up
It is dry, obtain combination product；
(3) first carbonizations：Under the protection of inert gas, be carbonized the combination product that step (2) is obtained 3h at 600 DEG C,
Heating rate during from room temperature to 400 DEG C is 3 DEG C/min, after the completion of carbonization, is cooled to room temperature, 325 eye mesh screen mistakes
Sieve, obtains the first carbon silicon composite precursor；
(4) coating modification：(gross mass with pitch, phenolic resin and the first carbon silicon composite precursor is to use 9.3wt%
100wt% is counted) pitch and the mixture of phenolic resin carry out solid phase cladding, specific encapsulation steps are：According to mass ratio
Weigh the mixture of the first carbon silicon composite precursor and pitch and phenolic resin, by the first carbon silicon composite precursor, pitch and
Phenolic resin merges 45min in being added to fusion machine, and the rotating speed for merging machine is 2750r/min, the gap of the cutter in fusion machine
Width is 0.2cm, and fusion obtains the second carbon silicon composite precursor；
(5) second carbonizations：Then step (4) the second carbon silicon composite precursor of gained is existed under the protection of inert gas
Be carbonized 3h at 1000 DEG C, from room temperature to 1000 DEG C during heating rate be 5 DEG C/min, room is cooled to after the completion of carbonization
Temperature, 325 eye mesh screens sieving, has just obtained carbon-silicon composite material, is named as SSC-3.
Using the carbon-silicon composite material of the present embodiment as negative material be used for lithium ion battery, gained battery have be filled with soon
And the good characteristic such as high power capacity.
The specific surface area and granularity data of the carbon-silicon composite material of the present embodiment are shown in Table 1.
The de- lithium capacity of the battery being made as negative pole using the carbon-silicon composite material of the present embodiment, first effect (de- lithium capacity/embedding
Lithium capacity) and 18650 cylindrical battery multiplying power charging capacitys the results are shown in Table 2.
Embodiment 4
(1) surface modification：Modify method by liquid phase with binding agent carries out surface modification to hard carbon.Accurately weigh 3.4g high temperature
, be added to for hard pitch under conditions of room temperature magnetic agitation in 100mL tetrahydrofurans (THF) solution by pitch, stirs 1h, obtains
The THF solution of pitch, to 32.6g hard carbons are added in the THF solution of pitch, heats solvent evaporated, obtains hard pitch modification
Hard carbon.
(2) it is combined：Nano silica fume, dispersant are added in isopropanol, high-energy ball milling, ball milling condition is, rotating speed 300r/
Min, ball milling 24h, obtain silicon pulp solution.It is accurate to weigh silicon slurry (conversion is 2.8g silicon, and solvent is isopropanol), ultrasonic disperse
2h, it is standby.Under conditions of being stirred at room temperature, the hard carbon that 36g hard pitches are modified is added in the silicon slurry after above-mentioned ultrasound,
Heating water bath after stirring 35min, solvent evaporated is transferred to drying in 110 DEG C of baking ovens after gained material is broken up, obtain compound product
Thing；
(3) first carbonizations：Step (2) is obtained into part combination product under the protection of inert gas, be carbonized 2h at 800 DEG C,
Heating rate during from room temperature to 800 DEG C is 3 DEG C/min, after the completion of carbonization, is cooled to room temperature, 325 eye mesh screen mistakes
Sieve, obtains the first carbon silicon composite precursor；
(4) coating modification：(gross mass with pitch and the first carbon silicon composite precursor is as 100wt% to use 9.3wt%
Meter) pitch carry out solid phase cladding, specific encapsulation steps are：The first carbon silicon composite precursor and drip are weighed according to mass ratio
Green grass or young crops, the two is well mixed, and obtains the second carbon silicon composite precursor.
(5) second carbonizations：Then under the protection of inert gas by step (4) gained the second carbon silicon composite precursor with 3
DEG C/min from room temperature to 980 DEG C, be carbonized 2h at 980 DEG C, is cooled to room temperature after the completion of carbonization, the sieving of 325 eye mesh screens, just
Carbon-silicon composite material has been obtained, SSC-4 has been named as.
Using the carbon-silicon composite material of the present embodiment as negative material be used for lithium ion battery, gained battery have be filled with soon
And the good characteristic such as high power capacity.
The specific surface area and granularity data of the carbon-silicon composite material of the present embodiment are shown in Table 1.
The de- lithium capacity of the battery being made as negative pole using the carbon-silicon composite material of the present embodiment, first effect (de- lithium capacity/embedding
Lithium capacity) and 18650 cylindrical battery multiplying power charging capacitys the results are shown in Table 2.
Embodiment 5
(1) surface modification：Modify method by liquid phase with binding agent carries out surface modification to amorphous carbon, accurately weighs 3.4g
Phenolic resin, during phenolic resin to be dissolved in 100mL ethanol solutions under conditions of room temperature magnetic agitation, obtains the second of phenolic resin
Alcoholic solution, to 32.6g hard carbons are added in the ethanol solution of phenolic resin, heats solvent evaporated, obtains the hard of phenolic resin modification
Carbon.
(2) it is combined：By the silicon slurry (folding after the hard carbon and ultrasonic disperse 1.3h of the phenolic resin modification obtained by step (1)
It is 2.8g silicon to calculate, and solvent is isopropanol) it is added in the isopropanol solvent of 80mL, room temperature high-speed stirred 40min, heating is evaporated molten
Agent, is transferred to drying in 95 DEG C of baking ovens after gained material is broken up, obtain combination product.
(3) first carbonizations：Under the protection of inert gas, be carbonized the combination product that step (3) is obtained 4h at 700 DEG C,
5 DEG C/min of heating rate during from room temperature to 700 DEG C, after the completion of carbonization, is cooled to room temperature, and gained carbonized stock is entered
The eye mesh screen of row 325 sieves, and obtains the first carbon silicon composite precursor.
(4) coating modification：(gross mass with pitch and the first carbon silicon composite precursor is as 100wt% to use 9.3wt%
Meter) pitch carry out spray drying cladding, specific encapsulation steps are：The first carbon silicon composite precursor is weighed according to mass ratio
And pitch, the two is mixed to join in isopropanol solvent, stirring obtains the mixed slurry that solid content is 20wt%, is sprayed
Dry that (condition of spray drying is：300 DEG C of inlet temperature, 110 DEG C of outlet temperature, feed rate is 30mL/min), obtain
Two carbon silicon composite precursors；
(5) second carbonizations：Then under the protection of inert gas by gained the second carbon silicon composite precursor at 980 DEG C carbon
Change 3h, from room temperature to 980 DEG C during heating rate be 3 DEG C/min, room temperature, 325 mesh sieves are cooled to after the completion of carbonization
Net sieving, has just obtained carbon-silicon composite material, is named as SSC-5.
Using the carbon-silicon composite material of the present embodiment as negative material be used for lithium ion battery, gained battery have be filled with soon
And the good characteristic such as high power capacity.
The specific surface area and granularity data of the carbon-silicon composite material of the present embodiment are shown in Table 1.
The de- lithium capacity of the battery being made as negative pole using the carbon-silicon composite material of the present embodiment, first effect (de- lithium capacity/embedding
Lithium capacity) and 18650 cylindrical battery multiplying power charging capacitys the results are shown in Table 2.
Comparative example 1
In addition to surface modification is not carried out to soft carbon, other preparation methods and condition are same as Example 1.
Specifically, comprise the following steps：
(1) soft carbon (SC) is prepared, it is standby；
(2) it is combined：Accurate to weigh silicon slurry (conversion is 2.8g silicon, and solvent is isopropanol), ultrasonic disperse 30min is obtained
Silicon slurry, it is standby.Under conditions of being stirred at room temperature, 36.0g soft carbons (SC) are added in the silicon slurry after above-mentioned ultrasound, stirring
Heating water bath after 45min, solvent evaporated is transferred to drying in 120 DEG C of baking ovens after gained material is broken up, obtain combination product；
(3) first carbonizations：Under the protection of inert gas, be carbonized the combination product that step (3) is obtained 3h at 600 DEG C,
Heating rate during from room temperature to 600 DEG C is 3 DEG C/min, after the completion of carbonization, is cooled to room temperature, 325 eye mesh screen mistakes
Sieve, obtains the first carbon silicon composite precursor；
(4) coating modification：(gross mass with pitch and the first carbon silicon composite precursor is as 100wt% to use 9.3wt%
Meter) pitch carry out solid phase cladding, specific encapsulation steps are：The first carbon silicon composite precursor and drip are weighed according to mass ratio
Green grass or young crops, the two is well mixed, and obtains the second carbon silicon composite precursor；
(5) second carbonizations：Then step (4) gained is obtained into the second carbon silicon composite precursor under the protection of inert gas
Be carbonized 3h at 980 DEG C, and the heating rate from during step (3) room temperature to 980 DEG C is 3 DEG C/min, has been carbonized
Room temperature is cooled to after, the sieving of 325 eye mesh screens has just obtained carbon-silicon composite material, has been named as Ref-1.
The specific surface area and granularity data of the carbon-silicon composite material of this comparative example are shown in Table 1.
(de- lithium capacity/embedding lithium holds for the de- lithium capacity of the battery being made as negative pole using the composite of this comparative example, first effect
Amount) and 18650 cylindrical battery multiplying power charging capacitys the results are shown in Table 2.
Table 1
Table 2
As shown in Table 2, the carbon-silicon composite material that prepared by the present invention has very excellent as the battery that negative material is made
High rate performance, 5C/1C charging capacity conservation rates are up to 85.7%.
Applicant states that the present invention illustrates method detailed of the invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of carbon-silicon composite material, it is characterised in that the carbon-silicon composite material includes kernel and is coated on the kernel
The shell on surface, wherein, the kernel is amorphous carbon, and the shell is to be scattered in pyrolytic carbon layer by nano-silicon and formed
's.
2. carbon-silicon composite material according to claim 1, it is characterised in that the median particle diameter of the carbon-silicon composite material is
5 μm~60 μm, preferably 8 μm~30 μm, more preferably 10 μm~25 μm；
Preferably, the specific surface area of the carbon-silicon composite material is 0.8m2/ g~3.5m2/ g, preferably 1.1m2/ g~2.0m2/g；
Preferably, the compacted density of the carbon-silicon composite material is 0.9g/cm3~2.0g/cm3, preferably 1.0g/cm3~
1.4g/cm3。
3. carbon-silicon composite material according to claim 1 and 2, it is characterised in that the amorphous carbon include soft carbon and/or
Hard carbon；
Preferably, the median particle diameter of amorphous carbon is 5 μm~30 μm, more preferably preferably 7 μm~20 μm, 9 μm~15 μ
m；
Preferably, the median particle diameter of the nano-silicon is 25nm~300nm, preferably 80nm~200nm；
Preferably, the thickness of the shell is 0~3.0 μm, and does not include 0；
Preferably, the pyrolytic carbon layer is as being as obtained from binding agent and carbon source by pyrolysis；
Preferably, mixing of the binding agent including any one in pitch, polyvinyl alcohol or phenolic resin or at least two
Thing；
Preferably, the carbon source includes pitch and/or macromolecular compound；
Preferably, the macromolecular compound include epoxy resin, phenolic resin, furfural resin, Lauxite, polyvinyl alcohol,
In polyvinyl chloride, polyethylene glycol, PEO, Kynoar, acrylic resin or polyacrylonitrile any one or extremely
Few two kinds mixture.
4. the preparation method of the carbon-silicon composite material as described in claim any one of 1-3, it is characterised in that methods described includes
Following steps：
(1) surface modification is carried out to amorphous carbon using binding agent；
(2) amorphous carbon of the binding agent modification for obtaining step (1) is combined with nano-silicon, then the combination product to obtaining
The first carbonization is carried out, the first carbon silicon composite precursor is obtained；
(3) the first carbon silicon composite precursor obtained to step (2) using carbon source carries out coating modification, obtains the second carbon silicon and is combined
Presoma, then the second carbonization is carried out, obtain carbon-silicon composite material.
5. method according to claim 4, it is characterised in that methods described is additionally included in the carbonization of step (2) first and completes
Afterwards, the step of being sieved to the first product for obtaining of carbonization, the mesh number of the screen cloth that the sieving is used is 200 mesh or 325 mesh, preferably
It is 325 mesh；
Preferably, methods described is additionally included in after the completion of the carbonization of step (3) second, and powder is carried out to the product that the second carbonization is obtained
Broken, sieving and the step of except magnetic.
6. the method according to claim 4 or 5, it is characterised in that step (1) described amorphous carbon include soft carbon and/or
Hard carbon；
Preferably, step (1) described binding agent includes any one in pitch, polyvinyl alcohol or phenolic resin or at least two
Mixture；
Preferably, the median particle of step (1) described bonding agent is less than or equal to 5 μm, preferably less than equal to 2 μm；
Preferably, the method that step (1) described surface modification is used is any one in solid phase modification method or liquid phase modification method；
Wherein, the preparation process of the solid phase modification method is：Binding agent and amorphous carbon are placed in VC mixers, are mixed, so
Afterwards, mixed material is added in fusion machine and is merged, obtain the amorphous carbon of binding agent modification；
The preparation process of liquid phase modification method is：Binding agent is dissolved in solvent, amorphous carbon is added, stirring is evaporated molten
Agent, obtains the amorphous carbon of binding agent modification；
Preferably, in the solid phase modification method, during mixing, the rotating speed of VC mixers is 500r/min~3000r/min；
Preferably, in the solid phase modification method, the time of the mixing is no less than 15min, preferably 30min；
Preferably, in the solid phase modification method, during fusion, the rotating speed for merging machine is 500r/min~3000r/min, in fusion machine
Cutter gap width be preferably 0.01cm~0.5cm；
Preferably, in the solid phase modification method, the time of the fusion is no less than 0.5h, preferably 45min；
Preferably, in the liquid phase modification method, the solvent is any one in tetrahydrofuran, toluene, carbon disulfide, alcohol or water
Kind or at least two mixture.
7. the method according to claim any one of 4-6, it is characterised in that step (2) the compound method is：Will step
The amorphous carbon and nano-silicon of the binding agent modification that (1) obtains suddenly are added in solvent, are stirred, solvent evaporated, so that nanometer
Silicon is bonded to the surface of the amorphous carbon of the binding agent modification that step (1) is obtained, and obtains combination product；
Preferably, in step (2) the compound method, the solvent is for any one in isopropanol, ethanol or water or extremely
Few two kinds mixture；
Preferably, step (2) first carbonization is carried out in an inert atmosphere, and the inert atmosphere includes nitrogen atmosphere, argon gas
In atmosphere, neon atmosphere, helium atmosphere, xenon atmosphere or Krypton atmosphere any one or at least two combination；
Preferably, the temperature of step (2) first carbonization is 400 DEG C~800 DEG C；
Preferably, the time of step (2) first carbonization is 2h~6h；
Preferably, be warmed up to step (2) it is described first carbonization temperature during, heating rate be 1 DEG C/min~10 DEG C/
min。
8. the method according to claim any one of 4-7, it is characterised in that step (3) described carbon source include pitch and/or
Macromolecular compound；
Preferably, the macromolecular compound include epoxy resin, phenolic resin, furfural resin, Lauxite, polyvinyl alcohol,
In polyvinyl chloride, polyethylene glycol, PEO, Kynoar, acrylic resin or polyacrylonitrile any one or extremely
Few two kinds mixture；
Preferably, counted by 100wt% of the gross mass of carbon source and the first carbon silicon composite precursor, the matter of step (3) described carbon source
Amount percentage is 5wt%~20wt%, preferably 8wt%~13wt%；
Preferably, the method that step (3) described coating modification is used for solid phase cladding process, liquid phase coating method, fusion cladding process or
Spray drying cladding process in any one；Wherein, the preparation process of the solid phase cladding process is：By the first carbon silicon compound precursor
Body is placed in VC mixers with carbon source, is mixed, and obtains the second carbon silicon composite precursor；
The preparation process of the liquid phase coating method is：First carbon silicon composite precursor and carbon source are added in solvent, are stirred, steamed
Dry solvent, obtains the second carbon silicon composite precursor；
It is described fusion cladding process preparation process be：First carbon silicon composite precursor is added in the machine of fusion with carbon source and is melted
Close, obtain the second carbon silicon composite precursor；
It is described spray drying cladding process preparation process be：First carbon silicon composite precursor and carbon source are added in solvent, are stirred
Mix and obtain mixed slurry, be spray-dried, obtain the second carbon silicon composite precursor；
Preferably, in the solid phase cladding process, during mixing, the rotating speed of VC mixers is 500r/min~3000r/min；
Preferably, in the solid phase cladding process, the time of the mixing is no less than 15min, preferably 30min；
Preferably, in the liquid phase coating method, the solvent is any one in tetrahydrofuran, toluene, carbon disulfide, alcohol or water
Kind or at least two mixture；
Preferably, in the fusion cladding process, during fusion, the rotating speed for merging machine is 500r/min~3000r/min, in fusion machine
Cutter gap width be 0.01cm~0.5cm；
Preferably, in the fusion cladding process, the time of the fusion is no less than 0.5h, preferably 45min；
Preferably, in the spray drying cladding process, the solvent is appointing in tetrahydrofuran, toluene, carbon disulfide, alcohol or water
Meaning it is a kind of or at least two mixtures；
Preferably, in the spray drying cladding process, the condition of the spray drying is：Inlet temperature is 250 DEG C~400 DEG C,
Preferably 300 DEG C；Outlet temperature is 90 DEG C~115 DEG C, preferably 110 DEG C；The solid content of the mixed slurry for being spray-dried
It is 10wt%~30wt%；The feed rate of mixed slurry is 10mL/min~40mL/min during spray drying；
Preferably, step (3) second carbonization is carried out in an inert atmosphere, and the inert atmosphere includes nitrogen atmosphere, argon gas
In atmosphere, neon atmosphere, helium atmosphere, xenon atmosphere or Krypton atmosphere any one or at least two combination；
Preferably, the temperature of step (3) second carbonization is 900 DEG C~1100 DEG C；
Preferably, the time of step (3) second carbonization is 2h~4h；
Preferably, during the temperature of step (2) second carbonization is warmed up to from the temperature of the first carbonization, heating rate is
1 DEG C/min~10 DEG C/min.
9. a kind of negative material, it is characterised in that the negative material is the carbon silicon composite wood described in claim any one of 1-3
Material.
10. a kind of lithium ion battery, it is characterised in that the lithium ion battery includes negative material as claimed in claim 9.
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