CN106848268A - A kind of carbon-silicon composite material, Preparation Method And The Use - Google Patents
A kind of carbon-silicon composite material, Preparation Method And The Use 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
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- 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
The present invention relates to a kind of carbon-silicon composite material, its preparation method and the purposes in lithium ion battery.Carbon-silicon composite material of the invention includes carbon substrate, catalyst and uniform nano level silicon grain and/or the silicon thin film being attached in carbon substrate.The method of the present invention includes：1) dispersion liquid of organic additive and catalyst is prepared；2) dried after carbon substrate is mixed with above-mentioned dispersion liquid, catalyst is modified the surface and interface in carbon substrate；3) carbon substrate of catalyst will be modified with to be transferred in CVD stoves; under protective atmosphere heat up, to reaction temperature after be passed through silicon source, react; the nano level silicon grain and/or silicon thin film that generation is catalytically decomposed are uniformly adhered to the surface and interface of carbon-based bottom material, obtain carbon-silicon composite material.The method of the present invention is easy to extensive preparation, and the silicon-carbon Compound Degree of product is high, is a kind of excellent cathode material of lithium ion battery.
Description
Technical field
The invention belongs to new negative electrode materials for lithium secondary batteries field, it is related to a kind of carbon-silicon composite, its preparation method
And purposes, more particularly to a kind of carbon-silicon composite, the preparation method using metal catalytic chemical vapor deposition and in lithium ion
The purposes of battery.
Background technology
Lithium ion battery has huge application prospect in mobile electronic equipment, electric automobile and extensive energy storage field
And extensive demand.The negative material of conventional lithium ion battery system selection is mainly graphite type material.Graphite type material is theoretical
Specific capacity is relatively low, only 372mAhg-1, it is difficult to meet requirement of the new type lithium ion battery to high-energy-density.Therefore develop new
Cathode material for high capacity lithium ion battery it is most important.
Silicon is used as lithium of new generation because possessing high theoretical specific capacity (4200mAh/g), suitable removal lithium embedded current potential
Ion battery cathode material is attracted wide attention and research interest.Silicon in charge and discharge process great volume change (>
300%) the shortcomings of initial coulomb efficiency is low caused by, cycle performance is poor turns into restriction silicon substrate lithium ion battery negative material commercially
The major obstacle of utilization.
In traditional method that nano-silicon is prepared by chemical vapour deposition technique, silicon source is after disassembly easily in carbon-based ground
The graininess or threadlike outgrowths of micron level are agglomerated on material, the unique advantage of nano-silicon is lost, and direct use is received
Nano-silicon is difficult to be uniformly dispersed in whole system during rice silicon silicon-carbon cathode material, and pole piece expands in causing charge and discharge process
Rate is excessive and then deteriorates material property.
CN 104103821B disclose a kind of preparation method of silicon-carbon cathode, and the method uses metal as catalyst, first
Si-SiO processed is decomposed by being catalyzed silicon sourcex, then obtained Si-SiO will be reacted by carrier gasxWith the carbon-based of carbonyl functional group's modification
Bottom material is combined.This method can be obtained the nano-silicon of height ratio capacity, but silicon cannot sufficiently be evenly distributed on carbon substrate
All surface and interfaces, cause cycle performance deterioration, the excessively high hidden danger of material volume expansion rate.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of carbon-silicon composite, its
Preparation method and use.Nano level silicon grain and/or silicon thin film are uniform and closely attached in carbon-silicon composite of the invention
The surface and interface in carbon-based bottom material, silicon-carbon Compound Degree is high, carbon-silicon composite of the invention, cladded type carbon silicon are combined
Material and accumulation type carbon-silicon composite material carry out half-cell test, as a result show, the specific volume reversible first of these three composites
In 430mAh/g~1350mAh/g, initial coulomb efficiency reaches more than 90% to amount, and, for cladded type carbon-silicon composite material
With accumulation type carbon-silicon composite material, capability retention is more than 95% within 50 weeks.
It is that, up to above-mentioned purpose, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of carbon-silicon composite, the carbon-silicon composite includes carbon substrate, catalysis
Agent and uniform nano level silicon grain and/or the silicon thin film being attached in carbon substrate.
" nano level silicon grain and/or silicon thin film " of the present invention refers to：Can be nano level silicon grain, or
Nano level silicon thin film, can also be the mixture of nano level silicon grain and nano level silicon thin film.
Preferably, the carbon substrate is inorganic carbon material, preferably natural spherical plumbago, natural flake graphite, artificial stone
In ink, soft carbon, hard carbon, carbonaceous mesophase spherules, Graphene, electrically conductive graphite or CNT any one or at least two group
Close.
Preferably, the catalyst is transition metal simple substance and/or transistion metal compound.
" transition metal simple substance and/or transistion metal compound " of the present invention refers to：Can be transition metal simple substance, also may be used
To be transistion metal compound, the mixture of transition metal simple substance and transistion metal compound is can also be.
Preferably, the catalyst is iron chloride, frerrous chloride, copper chloride, nickel chloride, ferric nitrate, nickel nitrate, nitric acid
In copper, ferric acetate, copper acetate, nickel acetate, iron simple substance, copper simple substance or nickel simple substance any one or at least two combination.
Preferably, a diameter of 1nm~200nm of the silicon grain, for example, 1nm, 3nm, 5nm, 10nm, 15nm, 20nm,
30nm、35nm、45nm、50nm、60nm、70nm、75nm、80nm、90nm、95nm、105nm、110nm、120nm、125nm、
135nm, 150nm, 170nm, 180nm or 200nm etc., preferably 1nm~50nm.
Preferably, the thickness of the silicon thin film be 1nm~200nm, for example, 2nm, 5nm, 8nm, 13nm, 18nm, 25nm,
30nm、40nm、50nm、60nm、70nm、80nm、90nm、100nm、110nm、120nm、130nm、145nm、150nm、165nm、
185nm or 200nm etc..
Preferably, the gross mass with the carbon-silicon composite is counted as 100%, the nano level silicon grain and/or silicon
The weight/mass percentage composition (being designated as silicone content) of film be 1%~80%, for example, 1%, 5%, 10%, 15%, 20%, 30%,
40%th, 45%, 50%, 60%, 65%, 70%, 75% or 80% etc..
Second aspect, the present invention provides the preparation method of carbon-silicon composite as described in relation to the first aspect, methods described bag
Include following steps：
(1) dispersion liquid of organic additive and catalyst is prepared；
(2) dried after the dispersion liquid of carbon substrate and step (1) is mixed, catalyst is modified the surface and interface in carbon substrate；
(3) product of step (2) is put into chemical vapor deposition (Chemical Vapor Deposition, CVD) instead
Answer in stove, heated up under the protection of protective gas, silicon source is passed through after being warming up to reaction temperature, stop after carrying out reaction a period of time
Silicon source is only passed through, the nano level silicon grain and/or silicon thin film that generation is catalytically decomposed are uniformly adhered to the table of carbon-based bottom material
Interface, obtains carbon-silicon composite.
Preferably, the reacting furnace is swinging CVD reacting furnaces.
In the present invention, the organic additive and the dissolved state of the dispersion liquid of catalyst prepared to step (1) are not construed as limiting,
Can be solution, or colloid, can also be suspension.
Preferably, step (1) described organic additive is polyethylene glycol, polyvinylpyrrolidone, polyvinyl chloride, polypropylene
Nitrile, polyacetylene, glucose, sucrose, alginic acid, sodium alginate, citric acid, sodium citrate, carboxymethylcellulose calcium, carbonyl propyl group fiber
In element, shitosan, starch or gelatin any one or at least two mixture.
Preferably, in the dispersion liquid of step (1) organic additive and catalyst, the matter of organic additive and catalyst
Amount is than being 1:10~2:1, for example, 1:10、1:9、1:8、1:7、1:6、1:5、1:4、1:3、1:2、1:1、1.5:1 or 2:1 etc..
In the present invention, using organic additive and catalyst preparation dispersion liquid, organic additive can be as carbon substrate mixed
The dispersant in liquid is closed, base material is not settled in drying process.
Preferably, the mass ratio of the catalyst in the dispersion liquid of step (2) carbon substrate and step (1) is 3:1~10:
1, for example, 3:1、3.5:1、4:1、5:1、5.5:1、6:1、7:1、7.5:1、8:1、9:1 or 10:1 etc..
Preferably, step (3) is crushed to the product that drying is obtained before after methods described is additionally included in step (2)
The step of obtaining powder.
Preferably, step (3) the CVD reacting furnaces are any one in double gas circuits or single gas circuit.
Preferably, step (3) described protective gas is non-oxidizing gas, preferably nitrogen, argon gas, hydrogen, hydrogen argon
Any one in gaseous mixture.
" hydrogen-argon-mixed " of the present invention refers to：The mixed gas being made up of hydrogen and argon gas.
Preferably, step (3) described protective gas is passed through speed for 5sccm~100sccm, for example, 5sccm,
10sccm、20sccm、30sccm、35sccm、40sccm、45sccm、50sccm、60sccm、65sccm、70sccm、80sccm、
85sccm, 90sccm or 100sccm etc..
Preferably, step (3) described silicon source is silicon base compound, preferably silane, a chlorosilane, dichlorosilane, trichlorine
In silane, silicochloroform, silicon ethane or a chlorine silicon ethane any one or at least two mixture.
Preferably, step (3) described silicon source is passed through speed for 0.2L/min~30L/min, for example, 0.2L/min,
0.5L/min、1L/min、2L/min、3L/min、5L/min、6L/min、8L/min、10L/min、12L/min、15L/min、
17L/min, 20L/min, 23L/min, 25L/min, 26L/min, 28L/min or 30L/min etc..
Preferably, the concentration of step (3) described silicon source be 1v%~80v%, for example, 1v%, 3v%, 5v%, 10v%,
15v%, 20v%, 25v%, 30v%, 35v%, 40v%, 45v%, 50v%, 60v%, 65v%, 70v%, 75v% or
80v% etc..
In the method for the present invention, the silicon source being passed through is gaseous state, if the silicon source selected is in itself gaseous state, is passed directly into i.e.
Can；If silicon source first is on-gaseous, needing first to gasify is converted into gaseous state and is passed through again.
Preferably, step (3) described reaction temperature be 250 DEG C~800 DEG C, for example, 250 DEG C, 280 DEG C, 300 DEG C, 325
℃、350℃、370℃、400℃、430℃、460℃、500℃、530℃、570℃、600℃、625℃、650℃、700℃、
720 DEG C, 740 DEG C, 760 DEG C, 780 DEG C or 800 DEG C etc..
Preferably, during step (3) described reaction, the working speed of swinging CVD reacting furnaces for 1r/min~
10r/min, for example, 1r/min, 2r/min, 3r/min, 3.5r/min, 4r/min, 6r/min, 7r/min, 8r/min, 9r/
Min or 10r/min etc..
Preferably, the time of step (3) described reaction be 0.5h~6h, for example, 0.5h, 1h, 1.5h, 2h, 2.5h, 3h,
3.5h, 4h, 5h, 5.5h or 6h etc., preferably 3h.
During the present invention prepares carbon-silicon composite, specific pattern (silicon grain or silicon thin film) and the silicon source of silicon
Species is selected and silicon source is passed through the relating to parameters such as speed, the size of nano level silicon grain, the thickness of silicon thin film and silicon
Content (weight/mass percentage composition of i.e. nano level silicon grain and/or silicon thin film) can be passed through speed, reaction temperature according to silicon source
Degree and reaction time isoparametric cooperation are adjusted, a diameter of 1nm~200nm of preferred silicon grain, preferred silicon thin film
Thickness be 1nm~200nm, preferred silicone content be 1%~80%, in above-mentioned this several preferred scopes, the carbon-silicon for obtaining
Composite property is more excellent, is conducive to lifting using the chemical property of its battery for preparing.
The third aspect, the present invention provides a kind of cladded type carbon-silicon composite material, and the cladded type carbon-silicon composite material is right
Carbon-silicon composite described in first aspect carries out carbon coating and sinters what is obtained.
Preferably, in the cladded type carbon-silicon composite material, the weight/mass percentage composition of silicon is 1%~80%, for example,
1%th, 3%, 6%, 10%, 14%, 18%, 23%, 25%, 30%, 35%, 40%, 43%, 47%, 50%, 55%, 60%,
65%th, 70%, 72.5%, 75% or 80% etc., the weight/mass percentage composition of carbon is 20%~99%, for example, 20%, 23%,
25%th, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 78%, 80%, 85%, 90%,
93%th, 95% or 99% etc..
When the present invention prepares cladded type carbon-silicon composite material, the carbon coating and sintering technology for using are prior art, ability
The method that field technique personnel are referred to prior art is prepared, it is highly preferred that the method that carbon coating is used includes but do not limit
In chemical vapor deposition, carbon source solid phase mixing or carbon source liquid phase mixing in any one.
Fourth aspect, the present invention provides a kind of accumulation type carbon-silicon composite material, and the accumulation type carbon-silicon composite material is to adopt
Secondary granulation is carried out with the carbon-silicon composite described in claim any one of 1-3 and sinters what is obtained.
Preferably, in the accumulation type carbon-silicon composite material, the weight/mass percentage composition of silicon is 1%~80%, for example,
1%th, 5%, 10%, 20%, 25%, 30%, 40%, 45%, 50%, 60%, 65%, 70% or 80% etc., the quality hundred of carbon
Point content is 20%~99%, for example, 20%, 30%, 35%, 40%, 50%, 55%, 60%, 70%, 75%, 80%,
85%th, 90%, 92.5%, 96%, 98% or 99% etc..
When the present invention prepares accumulation type carbon-silicon composite material, the secondary granulation and sintering technology for using are prior art, this
The method that art personnel are referred to prior art is prepared, it is highly preferred that secondary granulation use method include but
Be not limited to VC heating, fusion nodularization, spray drying or hydraulic press compressing tablet in any one.
5th aspect, the present invention provides a kind of negative pole, the negative pole comprising the carbon-silicon composite described in first aspect,
It is any one in the accumulation type carbon-silicon composite material described in cladded type carbon-silicon composite material or fourth aspect described in the third aspect
Kind or at least two combination.
6th aspect, the present invention provides a kind of lithium ion battery, and the lithium ion battery is comprising negative described in the 5th aspect
Pole.
Compared with the prior art, the present invention has the advantages that：
(1) carbon-silicon composite wood is prepared the invention provides a kind of metal catalytic chemical vapor deposition of utilization growth in situ
The method of material, using metal simple-substance and/or metallic compound as catalyst, first modifies in the table of carbon-based bottom material catalyst
Face, allows silicon source that nano level silicon grain and/or silicon thin film are stably generated when decomposing, and be uniformly adhered to carbon-based ground
Material surface and interface, is distributed on metal catalytic site, and nano level silicon grain and/or silicon thin film are tightly combined with carbon-based bottom material,
Silicon-carbon Compound Degree is high, and nano-silicon is difficult hardly possible during dispersed and conventional art chemical vapor deposition in solving conventional art
To stably generate the problem of nano-silicon, possesses advantage in practice.
Half is carried out to carbon-silicon composite of the invention, cladded type carbon-silicon composite material and accumulation type carbon-silicon composite material
Battery testing, as a result shows, the reversible specific capacity first of above-mentioned these three composites is first in 430mAh/g~1350mAh/g
Secondary coulombic efficiency reaches more than 90%, and, for cladded type carbon-silicon composite material and accumulation type carbon-silicon composite material, hold within 50 weeks
Amount conservation rate is more than 95%.
(2) method of the present invention is simple to operate, and is easy to heavy industrialization preparation.
Brief description of the drawings
Fig. 1 is the SEM figures of carbon-silicon composite prepared by embodiment 1；
Fig. 2 is the SEM figures of carbon-silicon composite prepared by embodiment 2；
Fig. 3 is the SEM figures of carbon-silicon composite prepared by embodiment 3；
The head weeks of the battery that Fig. 4 is prepared using cladded type carbon-silicon composite material (silicone content 20wt%) prepared by embodiment 1
Charging and discharging curve；
Fig. 5 is the SEM figures of carbon-silicon composite prepared by comparative example 1；
Fig. 6 is the head of battery prepared by cladded type carbon-silicon composite material (silicone content 3.8wt%) prepared using embodiment 2
All charging and discharging curves；
Fig. 7 is the head of battery prepared by accumulation type carbon-silicon composite material (silicone content 3.4wt%) prepared using embodiment 3
All charging and discharging curves；
Fig. 8 is the head of battery prepared by cladded type carbon-silicon composite material (silicone content 3.1wt%) prepared using embodiment 4
All charging and discharging curves.
Specific embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by specific embodiment.
Embodiment 1
(1) take during 120g ferric chloride hexahydrates, 75mL concentrated hydrochloric acids add 1725mL deionized waters and be stirred well to clarification and match somebody with somebody
Ferric chloride solution processed, is subsequently adding 60g polyethylene glycol and is stirred well to dissolving, obtains the dispersion liquid of polyethylene glycol and iron chloride.
(2) 900g natural flake graphites are taken and is added in the dispersion liquid obtained by step (1) and fully infiltrated, dried after stirring
It is dry, obtain the base material of catalytic metal surface and interface modification.
(3) base material that the catalytic metal surface and interface of step (2) is modified is added in swinging CVD stoves, in nitrogen
750 DEG C are heated under protection, then using the nitrogen of 3.5L/min flows as carrier gas, heating and gasifying are passed through with the speed of 5L/min
Trichlorosilane, reaction 3h after obtain carbon-silicon composite.
(4) carbon-silicon composite obtained by step (3) is carried out into bitumencarb bag by way of being calcined after solid phase mixing
Cover, the carbon coating for obtaining obtains cladded type carbon-silicon composite material, the gross mass with the cladded type carbon-silicon composite material is 100%
Meter, the mass percent shared by carbon coating layer be transformed as pitch is 2%~5%.
Material characterization：
Carbon-silicon composite the pattern of the present embodiment is observed using SEM (SEM), SEM is schemed such as Fig. 1 institutes
Show, it is seen that graphite base surface uniform deposition silicon nanoparticle, particle size is 10nm~20nm or so.
The silicon tested in cladded type carbon-silicon composite material obtained in the present embodiment using x ray fluorescence spectrometry (XRF) is contained
Amount, as a result shows, silicone content is 20.0wt%.
Electrochemical property test：
Electricity is prepared as electrode material using the carbon-silicon composite and cladded type carbon-silicon composite material of the present embodiment respectively
Pond.By electrode material and electrically conductive graphite (KS-6, conductive additive), carbon black (Super P, conductive additive), carboxymethyl cellulose
Plain (CMC, thickener), butadiene-styrene rubber (SBR, binding agent) are with 92:2:2:2:2 ratio mixing mashing, even application is in Copper Foil
Drying is made cathode pole piece on collector, and button cell is assembled in argon atmospher glove box, and barrier film used is microporous polypropylene membrane,
To electrode be metal lithium sheet, electrolyte for 1mol/L lithium hexafluoro phosphate (solvent be ethylene carbonate, methyl ethyl carbonate, carbonic acid
Dimethyl ester mixed liquor).
Button cell to preparing carry out charge-discharge test and cycle performance test, voltage range be 0.005V~
1.5V, current density is 50mA/g.
Fig. 4 is the test data of the button cell prepared as electrode material using cladded type carbon-silicon composite material, it is seen that bag
The reversible specific capacity first for covering type carbon-silicon composite material has reached 840mAh/g, and initial coulomb efficiency is 90%, and circulation in 50 weeks is surveyed
Examination capability retention 95%.
Embodiment 2
(1) take during 201g Copper dichloride dihydrates, 75mL concentrated hydrochloric acids add 1725mL deionized waters and be stirred well to clarification and match somebody with somebody
Copper chloride solution processed, is subsequently adding 20g glucose and is stirred well to dissolving, obtains the dispersion liquid of glucose and copper chloride.
(2) 900g natural spherical plumbagos are taken and is added in the dispersion liquid obtained by step (1) and fully infiltrated, dried after stirring
It is dry, obtain the base material of catalytic metal surface and interface modification.
(3) base material that the catalytic metal surface and interface of step (2) is modified is added in swinging CVD stoves, in argon gas
550 DEG C are heated under protection, then using the nitrogen of 3.5L/min flows as carrier gas, are passed through with the speed of 5L/min a certain amount of
Monosilane, carbon-silicon composite is obtained after reaction 1.5h.
(4) carbon-silicon composite obtained by step (3) is carried out into carbon coating using chemical vapour deposition technique, is re-sintered, obtained
To cladded type carbon-silicon composite material, counted with the gross mass of the cladded type carbon-silicon composite material as 100%, the carbon that vapour deposition is obtained
Mass percent shared by clad is 2%~5%.
Material characterization：
Observe the pattern of the carbon-silicon composite of the present embodiment using SEM, SEM figures as shown in Fig. 2 by
Figure as can be seen that graphite base material surface forms intensive nano silicon particles, the size of nano particle be about 20nm~
30nm。
The silicone content tested in cladded type carbon-silicon composite material obtained in the present embodiment using XRF, is as a result shown, silicone content
It is 3.8%.
Electrochemical property test：
Electricity is prepared as electrode material using the carbon-silicon composite and cladded type carbon-silicon composite material of the present embodiment respectively
Pond, and carry out charge-discharge test and cycle performance test.Prepare the method and condition of battery, and the method and condition tested
It is same as Example 1.
Fig. 6 is the test data of the battery for obtaining, the ratio reversible first of the cladded type carbon-silicon composite material of the present embodiment
Capacity 431mAh/g, initial coulomb efficiency 90%, 50 weeks loop test capability retentions 96%.
Embodiment 3
(1) take during 202g copper acetate monohydrates, 25mL concentrated hydrochloric acids add 1350mL deionized waters and be stirred well to clarification and match somebody with somebody
Acetic acid copper solution processed, is subsequently adding 20g polyvinylpyrrolidones and is stirred well to dissolving, obtains polyvinylpyrrolidone and acetic acid
The dispersion liquid of copper.
(2) 900g electrically conductive graphites are taken and are added in the dispersion liquid obtained by step (1) and fully infiltrated, dried after stirring,
Obtain the base material of catalytic metal surface and interface modification.
(3) base material that the catalytic metal surface and interface of step (2) is modified is added in swinging CVD stoves, in argon gas
550 DEG C are heated under protection, are then passed through with the speed of 6L/min a certain amount of as carrier gas with the nitrogen of 3.5L/min flows
Monosilane, carbon-silicon composite is obtained after reaction 3h.
(4) secondary granulation is carried out to the carbon-silicon composite obtained by step (3) as binding agent using pitch, it is secondary to make
The equipment that grain is used is VC heaters, is then sintered, and obtains accumulation type carbon-silicon composite material, compound with the accumulation type carbon silicon
The gross mass of material is 100% meter, and the content of the clad being converted into by pitch is 2%~5%.
Material characterization：
The pattern of the carbon-silicon composite of the present embodiment is observed using SEM, SEM is schemed as shown in figure 3, carbon
Substrate material surface forms uniform intensive silicon nanoparticle, and particle size is about 30nm~50nm.
The silicone content tested in cladded type carbon-silicon composite material obtained in the present embodiment using XRF, is as a result shown, silicone content
It is 3.4wt%.
Electrochemical property test：
Electricity is prepared as electrode material using the carbon-silicon composite and accumulation type carbon-silicon composite material of the present embodiment respectively
Pond, and carry out charge-discharge test and cycle performance test.Prepare the method and condition of battery, and the method and condition tested
It is same as Example 1.
Fig. 7 is the test data of the button cell for obtaining, and the accumulation type carbon-silicon composite material of the present embodiment first may be used
Inverse specific capacity 480mAh/g, initial coulomb efficiency 92%, 50 weeks loop test capability retentions 96%.
Embodiment 4
(1) take during 170g nickel acetates, 35mL concentrated hydrochloric acids add 1350mL deionized waters and be stirred well to clarification preparation acetic acid
Nickel solution, is subsequently adding 30g citric acids and is stirred well to dissolving, obtains the dispersion liquid of citric acid and nickel acetate.
(2) 900g natural spherical plumbagos are taken and is added in the dispersion liquid obtained by step (1) and fully infiltrated, dried after stirring
It is dry, obtain the base material of catalytic metal surface and interface modification.
(3) base material that the catalytic metal surface and interface of step (2) is modified is added in swinging CVD stoves, in argon gas
550 DEG C are heated under protection, are then passed through with the speed of 5L/min a certain amount of as carrier gas with the nitrogen of 3.5L/min flows
Monosilane, carbon-silicon composite is obtained after reaction 2h.
(4) carbon-silicon composite obtained by step (3) is carried out into bitumencarb bag by way of being calcined after solid phase mixing
Cover, the carbon coating for obtaining obtains cladded type carbon-silicon composite material, the gross mass with the cladded type carbon-silicon composite material is 100%
Meter, the mass percent shared by carbon coating layer be transformed as pitch is 2%~5%.
The silicone content tested in cladded type carbon-silicon composite material obtained in the present embodiment using XRF, is as a result shown, silicone content
It is 3.1wt%.
Electrochemical property test：
Electricity is prepared as electrode material using the carbon-silicon composite and cladded type carbon-silicon composite material of the present embodiment respectively
Pond, and carry out charge-discharge test and cycle performance test.Prepare the method and condition of battery, and the method and condition tested
It is same as Example 1.
Fig. 8 is the test data of the battery for obtaining, the ratio reversible first of the cladded type carbon-silicon composite material of the present embodiment
Capacity 440mAh/g, first efficiency 91.4%, 50 weeks loop test capability retentions 95%.
Comparative example 1
In addition to the dispersion liquid that step (1) replaces polyethylene glycol and iron chloride with the dispersion liquid of polyethylene glycol, other preparation sides
Method and condition are same as Example 1, prepare carbon-silicon composite, and further the composite after solid phase mixing by forging
The mode of burning carries out pitch carbon coating, obtains cladded type carbon-silicon composite material, and the carbon coating layer of pitch conversion content and reality
Apply example 1 identical.
Fig. 5 is the SEM figures of carbon-silicon composite prepared by comparative example 1, as seen from the figure, if not using metal catalytic
Agent, silicon is difficult uniform and stable formation nano-silicon and can form micron particles or micron thread during silicon processed, from
And the performance advantage of nano-silicon is lost, and the chemical property of the battery being prepared into can be reduced, the product shown in comparative example is first
Reversible specific capacity 480mAh/g, head effect are 83%, 50 weeks circulation conservation rates 83%.
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, it is characterised in that the carbon-silicon composite includes carbon substrate, catalyst and attachment
Nano level silicon grain and/or silicon thin film in carbon substrate.
2. carbon-silicon composite according to claim 1, it is characterised in that the carbon substrate is inorganic carbon material, preferably
For natural spherical plumbago, natural flake graphite, Delanium, soft carbon, hard carbon, carbonaceous mesophase spherules, Graphene, electrically conductive graphite or
In CNT any one or at least two combination；
Preferably, the catalyst is transition metal simple substance and/or transistion metal compound；
Preferably, the catalyst is iron chloride, frerrous chloride, copper chloride, nickel chloride, ferric nitrate, nickel nitrate, copper nitrate, vinegar
In sour iron, copper acetate, nickel acetate, iron simple substance, copper simple substance or nickel simple substance any one or at least two combination；
Preferably, a diameter of 1nm~200nm of the silicon grain, preferably 1nm~50nm；
Preferably, the thickness of the silicon thin film is 1nm~200nm.
3. carbon-silicon composite according to claim 1 and 2, it is characterised in that with the total of the carbon-silicon composite
Quality is counted for 100%, and the weight/mass percentage composition of the nano level silicon grain and/or silicon thin film is 1%~80%.
4. the preparation method of the carbon-silicon composite as described in claim any one of 1-3, it is characterised in that methods described bag
Include following steps：
(1) dispersion liquid of organic additive and catalyst is prepared；
(2) dried after the dispersion liquid of carbon substrate and step (1) is mixed；
(3) in the product of step (2) being put into chemical vapor deposition CVD reacting furnaces, heated up under the protection of protective gas,
Silicon source is passed through after being warming up to reaction temperature, is reacted, obtain carbon-silicon composite；
Preferably, the reacting furnace is swinging CVD reacting furnaces.
5. method according to claim 4, it is characterised in that step (1) described organic additive is polyethylene glycol, poly- second
Alkene pyrrolidone, polyvinyl chloride, polyacrylonitrile, polyacetylene, glucose, sucrose, alginic acid, sodium alginate, citric acid, citric acid
In sodium, carboxymethylcellulose calcium, carbonyl propyl cellulose, shitosan, starch or gelatin any one or at least two mixture；
Preferably, in the dispersion liquid of step (1) organic additive and catalyst, the mass ratio of organic additive and catalyst
It is 1:10~2:1；
Preferably, the mass ratio of the catalyst in the dispersion liquid of step (2) carbon substrate and step (1) is 3:1~10:1；
Preferably, step (3) is crushed to the product that drying is obtained before after methods described is additionally included in step (2)
The step of powder.
6. the method according to claim 4 or 5, it is characterised in that step (3) the CVD reacting furnaces are double gas circuits or list
Any one in gas circuit；
Preferably, step (3) described protective gas is non-oxidizing gas, preferably nitrogen, argon gas, hydrogen, the mixing of hydrogen argon
Any one in gas；
Preferably, the speed that is passed through of step (3) described protective gas is 5sccm~100sccm；
Preferably, step (3) described silicon source be silicon base compound, preferably silane, a chlorosilane, dichlorosilane, trichlorosilane,
In silicochloroform, silicon ethane or a chlorine silicon ethane any one or at least two mixture；
Preferably, the speed that is passed through of step (3) described silicon source is 0.2L/min~10L/min；
Preferably, the concentration of step (3) described silicon source is 1v%~80v%；
Preferably, step (3) described reaction temperature is 250 DEG C~800 DEG C；
Preferably, during step (3) described reaction, the working speed of swinging CVD reacting furnaces is 1r/min~10r/
min；
Preferably, the time of step (3) described reaction is 0.5h~6h, preferably 3h.
7. a kind of cladded type carbon-silicon composite material, it is characterised in that the cladded type carbon-silicon composite material is to claim 1-3
Carbon-silicon composite described in any one carries out carbon coating and sinters what is obtained；
Preferably, in the cladded type carbon-silicon composite material, the weight/mass percentage composition of silicon is 1%~80%, the quality percentage of carbon
Content is 20%~99%；
Preferably, the method that the carbon coating is used is included in the mixing of chemical vapor deposition, carbon source solid phase mixing or carbon source liquid phase
Any one.
8. a kind of accumulation type carbon-silicon composite material, it is characterised in that the accumulation type carbon-silicon composite material is to use claim
Carbon-silicon composite described in any one of 1-3 carries out secondary granulation and sinters what is obtained；
Preferably, in the accumulation type carbon-silicon composite material, the weight/mass percentage composition of silicon is 1%~80%, the quality percentage of carbon
Content is 20%~99%；
Preferably, the method that the secondary granulation is used is included in VC heating, fusion nodularization, spray drying or hydraulic press compressing tablet
Any one.
9. a kind of negative pole, it is characterised in that the negative pole includes carbon-silicon composite, the power described in claim any one of 1-3
Profit requires any one in the accumulation type carbon-silicon composite material described in cladded type carbon-silicon composite material or claim 8 described in 7
Kind or at least two combination.
10. a kind of lithium ion battery, it is characterised in that the lithium ion battery includes the negative pole described in claim 8.
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| CN107394176A (en) * | 2017-07-31 | 2017-11-24 | 中国地质大学（北京） | Si-C composite material, preparation method and application and lithium ion battery negative material |
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| CN110311125A (en) * | 2019-08-15 | 2019-10-08 | 马鞍山科达普锐能源科技有限公司 | A kind of lithium-ion battery silicon-carbon anode material and preparation method thereof |
| CN110518224A (en) * | 2019-09-09 | 2019-11-29 | 厦门大学 | A kind of preparation method of lithium ion battery carbon silicon anode material |
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Application publication date: 20170613 |