CN106207108A - Si-C composite material based on macromolecule foaming microsphere and preparation method and application - Google Patents

Si-C composite material based on macromolecule foaming microsphere and preparation method and application Download PDF

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CN106207108A
CN106207108A CN201610535744.2A CN201610535744A CN106207108A CN 106207108 A CN106207108 A CN 106207108A CN 201610535744 A CN201610535744 A CN 201610535744A CN 106207108 A CN106207108 A CN 106207108A
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silicon
nano
composite material
macromolecule foaming
cladding
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CN106207108B (en
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康利涛
李亚娥
畅波
梁伟
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Taiyuan University of Technology
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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
    • H01M4/364—Composites as mixtures
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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

The present invention is a kind of Si-C composite material based on macromolecule foaming microsphere pore-creating mechanism and preparation method and application.Described Si-C composite material includes the hollow carbon shell obtained by foam microspheres carbonization, the nano-silicon being carried on hollow carbon shell, and wherein hollow carbon shell content is 5 ~ 95wt%, and nano-silicon content is 5 ~ 80wt%.Conducting polymer clad or carbon coating layer, coating thickness 1 ~ 20nm is had on nano-silicon surface.Si-C composite material technique disclosed by the invention is simple, equipment requirements is low, production efficiency is high, and high (the 100mA g of material specific capacity‑1Up to 1000mAh g under electric current density‑1), can be used for field of lithium ion battery, of many uses.

Description

Si-C composite material based on macromolecule foaming microsphere and preparation method and application
Technical field
The invention belongs to material and electrochemical field, be specifically related to a kind of silicon based on macromolecule foaming microsphere pore-creating mechanism Carbon composite and preparation method thereof, and the application as lithium ion battery negative material.
Background technology
In the middle of numerous lithium ion battery negative materials, graphitic conductive is good, electrode potential is low by (< 1.0vs. Li+/ Li), cheap nontoxic, cyclical stability high with chemical stability, the most still occuping market main flow is (such as native graphite, artificial stone Ink etc.).But, graphite specific capacity is already close to theoretical capacity (372mAh/g), and performance boost space is little.Thus, it is necessary to open Send out Novel high-specific capacity flexible negative material.
The theoretical specific capacity of silicon is more than 10 times of graphite, and discharge and recharge electrode potential is low, voltage platform steady, is considered It it is the negative material of future generation most possibly substituting graphite material.But, silicon materials, as negative material, there is also following asking Topic: 1, in charge and discharge process, silicon materials can the efflorescence because of reciprocal change in volume, the silicon materials of efflorescence and external circuit electrical contact Difference, reversible ratio electric capacity rapid decay；2, as semi-conducting material, silicon materials electrical conductivity is low, and electrochemical reaction rates is limited.
For solving the problem that silicon materials exist, those skilled in the art prepare silicon based composite material by design and improve electricity Conductance, and strengthen structural stability simultaneously.Wherein, material with carbon element because stable chemical nature, conductive capability are strong, good toughness and become The compounding ingredients that silicon based composite material is most commonly used.And in Si-C composite material, resist silicon materials with nano/micron hollow structure again Volumizing effect during charging is optimal.Such as, nano-silicon is coated on cavity volume more than receiving by Stanford University Yi Cui etc. In the carbon shell of rice silicon volume, in carbon shell internal reservation silicon volumetric expansion space, it is thus achieved that have high cyclical stability Yolk-shell structure Si-C composite material (Nano Letters, 2012,12 (6): 3315-3321).Opened by liquid surface Power or mechanical pressure strengthen the agglomeration of yolk-shell structure Si-C composite material, and the accumulation that can further enhance material is close Degree (Nature Nanotechnology, 2014,9 (3): 187-192, Energy & Environmental Science, 2015,8 (8): 2371-2376).But this technology uses SiO2Cladding-HF etching technics pore-creating, the toxicity of HF and SiO2Cladding The extremely low production efficiency of process makes the production in enormous quantities of this material become the most difficult.This problem also exists in patent of invention In the middle of technical scheme disclosed in CN201510613252.6 Yu CN201410587251.4.
Patent of invention CN201210566788.3 discloses a kind of silicon nanoparticle filling carbon nano-pipe complex and system thereof Preparation Method and application.The program is to have the anodic alumina films of regular pore structure as template, first at anodic alumina films Nano pore inner surface cracks organic lower carbon number hydrocarbons deposited carbon layer, then with silane for silicon source chemical vapor deposition silicon grain, finally Remove anodic alumina films and obtain silicon nanoparticle filling carbon nano-pipe complex.In the method, there is complex process simultaneously, raw Product efficiency is low, and alumina formwork chemical stability is high, is difficult to the problem removed.
Patent of invention CN201510545414.7 discloses the carbon/silicon nanofiber of the hollow porous of a kind of doped graphene Lithium cell cathode material and preparation method thereof.This preparation technology is first obtained doped with oxygen functionalized graphene by coaxial electrostatic spinning technology Polyacrylonitrile/polymethyl methacrylate/silicon dioxide nano fiber, then obtain, through high temperature cabonization, magnesium powder thermal reduction, the stone that adulterates Carbon/silicon nanofiber the lithium cell cathode material of the hollow porous of ink alkene.This technique have employed the electrostatic that production efficiency is the lowest Spining technology, and in large form produces, there is the magnesium powder thermal reduction technology of potential danger.
In summary, there is preparation technology many employings template or the Static Spinning of the Si-C composite material of hollow structure at present Silk technology, complex technical process, preparation condition are strict, and the production efficiency of material is severely limited with cost.Therefore, the most real The efficiently preparation of the Si-C composite material now with hollow structure is the technology that lithium ion battery negative material field is urgently to be resolved hurrily A difficult problem.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of based on macromolecule foaming microsphere pore-creating The Si-C composite material of mechanism.
The present invention adopts the following technical scheme that realization:
A kind of Si-C composite material based on macromolecule foaming microsphere, this Si-C composite material loads nano-silicon by hollow carbon shell Constitute.
Preferably, there are conducting polymer clad or carbon coating layer in described nano-silicon surface.
Preferably, described hollow carbon shell is made up of macromolecule foaming microsphere carbonization, and content is 5 ~ 95wt%.
Preferably, described nano-silicon particle mean size is 1 ~ 300nm.
Preferably, described nano-silicon is mono-dispersed nano silicon particle.
Preferably, in described Si-C composite material, nano-silicon content is 5 ~ 80wt%.
Preferably, described conducting polymer clad can be polyacetylene, polythiophene, polypyrrole, polyaniline, polyhenylene, One or several combination in any in polyphenylene ethylene and poly bis alkynes, thickness 1 ~ 20nm.
Preferably, described carbon coating layer can be one or several in soft carbon, hard carbon, Graphene, CNT Combination in any, thickness 1 ~ 20nm.
The two of the purpose of the present invention are to provide the preparation method of a kind of Si-C composite material, comprise the steps:
(1), carbonization after macromolecule foaming microsphere foamable is obtained hollow carbon shell；
(2), nano-silicon is carried on hollow carbon shell.
Or,
(1), nano-silicon is carried on macromolecule foaming microsphere；
(2), carbonization after macromolecule foaming microsphere foamable is obtained hollow carbon shell.
Preferably, foam microspheres carbonization parameter: temperature 400 ~ 1100 DEG C, time 20min ~ 24h.
Preferably, utilize conducting polymer or carbon raw material that nano-silicon is carried out cladding process；Described carbon raw material will pass through carbon Change and be converted into carbon coating layer.Cladding processing mode is gas phase cladding, liquid phase coating or solid phase cladding；Specific as follows:
Liquid phase coating: after (1), nano-silicon and cladding raw material process under liquid-phase condition, be dried to obtain conducting polymer cladding or The nano-silicon of carbon cladding；(2), the nano-silicon of gained conducting polymer cladding or carbon cladding is carried on macromolecule foaming microsphere On；(3), by be loaded with conducting polymer cladding or carbon cladding nano-silicon macromolecule foaming microsphere foamable after carbonization obtain To Si-C composite material.
Or, (1), nano-silicon is carried on macromolecule foaming microsphere；(2), the macromolecule being loaded with nano-silicon is sent out After bubble microsphere foamable, carbonization obtains Si-C composite material；(3), by Si-C composite material and cladding raw material under liquid-phase condition After process, it is dried to obtain conducting polymer cladding or the Si-C composite material of carbon cladding.
Or, (1), carbonization after macromolecule foaming microsphere foamable is obtained hollow carbon shell；(2), nano-silicon is loaded The Si-C composite material obtained on hollow carbon shell；(3), Si-C composite material and cladding raw material are processed under liquid-phase condition After, it is dried to obtain conducting polymer cladding or the Si-C composite material of carbon cladding.
Gas phase is coated with: (1), carbonization after macromolecule foaming microsphere foamable is obtained hollow carbon shell；(2), by nano-silicon It is carried on hollow carbon shell；(3), step (2) product is placed in heating furnace, under 400 ~ 1000 DEG C of heating conditions, to heating Stove is passed through carbon source gas, at nano-silicon coated with carbon bed.
Or, (1), nano-silicon is carried on macromolecule foaming microsphere；(2), by macromolecule foaming microsphere foamable Rear carbonization obtains hollow carbon shell, is passed through carbon source gas in carbonisation, at nano-silicon coated with carbon bed.Wherein, described carbon Property gas in source is one or more in methane, ethane, propane, butane, ethylene, acetylene, benzene,toluene,xylene.
Solid phase is coated with: (1), carbon coated raw material, nano-silicon are carried on macromolecule foaming microsphere；(2), by macromolecule After foam microspheres foamable, carbonization obtains hollow carbon shell.
Or, (1), carbonization after macromolecule foaming microsphere foamable is obtained hollow carbon shell；(2), by coated polymer Raw material, nano-silicon are carried on hollow carbon shell.
The three of the purpose of the present invention are, above-mentioned Si-C composite material based on macromolecule foaming microsphere is as cathode of lithium battery The application of material, i.e. lithium ion battery negative material are made by Si-C composite material.
Compared with prior art, there is advantages that
Saying from the angle of preparation, the hollow carbon shell in Si-C composite material disclosed by the invention is being heated by macromolecule foaming microsphere In carbonisation, automatic foaming forms, namely the formation of this hollow structure need not any sacrificial template or particularly technique sets Meter；Relative to template or electrostatic spinning technique, in terms of production efficiency, cost and the feature of environmental protection, there is prominent advantage.
Saying from the angle of performance, described hollow carbon shell not only has good electric conductivity, and silicon materials can be overcome to conduct electricity The rate slow problem of the low electrochemical reaction rates caused；And can be swollen by being deformed into silicon materials volume in battery charging process Swollen offer space, thus promote the cyclical stability of material.
Si-C composite material technique disclosed by the invention is simple, equipment requirements is low, production efficiency is high, and material specific capacity High (100mA g-1Up to 1000mAh g under electric current density-1), can be used for field of lithium ion battery, of many uses, have very Good actual application value.
Accompanying drawing explanation
Fig. 1 represents the scanning electron microscope (SEM) photograph of the Si-C composite material that embodiment 1 obtains.
Fig. 2 represents that Si-C composite material that embodiment 1 obtains is at 300mA/g-1Constant current charge-discharge curve under electricity density.
Fig. 3 represents Si-C composite material that embodiment 1 the obtains specific capacity curve after different charge and discharge cycles.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.
A kind of Si-C composite material based on macromolecule foaming microsphere pore-creating mechanism, this Si-C composite material is sent out by macromolecule The hollow carbon shell load nano-silicon that bubble microsphere carbonization is made is constituted.
Described nano-silicon particle mean size is 1 ~ 300nm.There are conducting polymer clad or carbon cladding in described nano-silicon surface Layer, coating thickness 1 ~ 20nm.
In Si-C composite material, nano-silicon content is 5 ~ 80wt%, and hollow carbon shell content is 5 ~ 95wt%, nano-silicon surface Clad content is 0 ~ 15wt%.
The preparation of above-mentioned Si-C composite material includes the combination of procedure below: macromolecule foaming microsphere is heated carbonization by (1) Obtain hollow carbon shell；(2) nano-silicon is carried on macromolecule foaming microsphere or hollow carbon shell.It is implemented in process (1), (2) Before, during or after, available conducting polymer, carbon or carbon raw material carry out cladding process to nano-silicon；Described carbon raw material will It is converted into carbon coating layer by carbonization.
Concrete preparation method below embodiment.
Embodiment 1
A kind of Si-C composite material preparation method based on macromolecule foaming microsphere is as follows:
1, nano-silicon is carried on macromolecule foaming microsphere: weigh 0.4g nano silica fume, 6g foam microspheres be scattered in 15ml without In water-ethanol, magnetic agitation 10min, ultrasonic 5min, then at 80 DEG C of dry 4h, obtain powder.
2, carbonization after macromolecule foaming microsphere foamable is obtained hollow carbon shell: by prepared powder 100 DEG C of insulations 10min completes foaming process, then the powder of foaming is placed in tube furnace at nitrogen atmosphere 800 DEG C holding 2h, is cooled to room Temperature obtains Si-C composite material product.
As it is shown in figure 1, the scanning electron microscopic picture of this Si-C composite material.
Energy spectrum analysis figure according to this Si-C composite material, utilize power spectrum the silicon in sample, carbon are distributed into Go analysis, found that two kinds of elements are evenly distributed in the sample, and a part of silicon is attached to the outer surface of hollow carbon shell, another portion Divide the inside being then scattered in hollow carbon shell.
As in figure 2 it is shown, this Si-C composite material is at 300mA/g-1Constant current charge-discharge curve under electricity density.
As it is shown on figure 3, the specific capacity curve that this Si-C composite material is after different charge and discharge cycles.
Embodiment 2
A kind of Si-C composite material preparation method based on macromolecule foaming microsphere is as follows:
1, being carried on macromolecule foaming microsphere by nano-silicon: weigh 0.4g nano silica fume, 6g foam microspheres is scattered in 15ml and goes In ionized water, magnetic agitation 10min, ultrasonic 5min, then at 80 DEG C of dry 10h, obtain powder.
2, carbonization after macromolecule foaming microsphere foamable is obtained hollow carbon shell: by prepared powder 160 DEG C of insulations 10min completes foaming process, then the powder of foaming is placed in tube furnace at blanket of nitrogen 400 DEG C holding 20h, is cooled to room Temperature obtains Si-C composite material product.
Embodiment 3
A kind of Si-C composite material preparation method based on macromolecule foaming microsphere is as follows:
1, nano-silicon is carried on macromolecule foaming microsphere: weighing 5g nano silica fume, it is anhydrous that 3g foam microspheres is scattered in 15ml In ethanol, magnetic agitation 10min, ultrasonic 15min, then at 80 DEG C of dry 2h, obtain powder.
2, carbonization after macromolecule foaming microsphere foamable is obtained hollow carbon shell: by prepared powder 130 DEG C of insulations 10min completes foaming process, and then the powder of foaming is placed in tube furnace at argon atmospher 1100 DEG C holding 20min, cooling Si-C composite material product is obtained to room temperature.
Embodiment 4
A kind of Si-C composite material preparation method based on macromolecule foaming microsphere is as follows:
1, being carried on macromolecule foaming microsphere by nano-silicon: weigh 1.9g nano silica fume, 0.3g foam microspheres is scattered in 15ml In dehydrated alcohol, magnetic agitation 10min, ultrasonic 5min, then at 80 DEG C of dry 4h, obtain powder.
2, carbonization after macromolecule foaming microsphere foamable is obtained hollow carbon shell: by prepared powder 140 DEG C of insulations 20min completes foaming process, then the powder of foaming is placed in tube furnace at ammonia atmosphere 700 DEG C holding 5h, is cooled to room Temperature obtains Si-C composite material product.
Embodiment 5
A kind of Si-C composite material preparation method based on macromolecule foaming microsphere, wherein, utilizes material with carbon element to carry out nano-silicon Cladding processes, and cladding processing mode is liquid phase coating；Specific as follows:
1, after nano-silicon and cladding raw material process under liquid-phase condition, it is dried to obtain the nano-silicon of material with carbon element cladding: weigh 0.4g Nano silica fume, ultrasonic disperse, in the mixed solution of 40ml dehydrated alcohol and deionized water (volume ratio is 1:1), adds 50 μ l Ammonia, after ultrasonic 10min, is subsequently adding resorcinol and formaldehyde magnetic agitation 30min of 400 μ l of 0.4g, molten by mix Liquid moves to water heating kettle, 80 DEG C, and product centrifugal drying obtains after 24h the nano silica fume of phenolic resin cladding.
2, the nano-silicon that phenolic resin is coated with is carried on macromolecule foaming microsphere: by receiving that gained phenolic resin is coated with Rice silica flour is scattered in 15ml dehydrated alcohol with 3g foam microspheres, magnetic agitation 10min, and then ultrasonic 5min is dried at 80 DEG C 4h, obtains powder.
3, by be loaded with phenolic resin cladding nano-silicon macromolecule foaming microsphere foamable after carbonization obtain hollow carbon Shell: prepared powder is completed foaming process at 150 DEG C of insulation 10min, then the powder of foaming is placed in tube furnace at nitrogen Keep 5h at hydrogen mixed atmosphere (hydrogen volume content 3%) 700 DEG C, be cooled to room temperature and obtain Si-C composite material product.
There is the carbon coating layer that phenolic resin carbonized is formed on nano silica fume surface in this composite.
Embodiment 6
A kind of Si-C composite material preparation method based on macromolecule foaming microsphere, wherein, utilizes material with carbon element to carry out nano-silicon Cladding processes, and cladding processing mode is liquid phase coating；Specific as follows:
1, after nano-silicon and cladding raw material process under liquid-phase condition, it is dried to obtain the nano-silicon of material with carbon element cladding: weigh 1.5g Nano silica fume, ultrasonic disperse is in 40ml deionized water, then to adding 2g glucose, after ultrasonic 10min, is moved by the solution of mixing To water heating kettle, 180 DEG C, after 24h, product centrifugal drying is obtained the nano silica fume of carbon cladding.
2, the nano-silicon that carbon is coated with is carried on macromolecule foaming microsphere: the nano silica fume that gained carbon is coated with is sent out with 3g Bubble microsphere is scattered in 15ml dehydrated alcohol, magnetic agitation 10min, and ultrasonic 5min, then at 80 DEG C of dry 4h, obtains powder.
3, after being loaded with the macromolecule foaming microsphere foamable of carbon-coated nano silicon, carbonization obtains hollow carbon shell: will system The powder obtained completes foaming process at 140 DEG C of insulation 20min, is then placed in tube furnace the powder of foaming at argon hydrogen gaseous mixture Keep 2h at atmosphere (hydrogen volume content 3%) atmosphere 900 DEG C, be cooled to room temperature and obtain Si-C composite material product.
There is the carbon coating layer that glucose hydrothermal carbonization is formed on nano silica fume surface in this composite.
Embodiment 7
A kind of Si-C composite material preparation method based on macromolecule foaming microsphere, wherein, utilizes material with carbon element to carry out nano-silicon Cladding processes, and cladding processing mode is solid phase cladding；Specific as follows:
1, carbon coated raw material, nano-silicon are carried on macromolecule foaming microsphere: weigh 1.2g nano silica fume, 0.2g CNT It is scattered in 15ml acetone with 3g foam microspheres, magnetic agitation 10min, ultrasonic 5min, then at 80 DEG C of dry 4h, obtains powder End.
2, carbonization after macromolecule foaming microsphere foamable is obtained hollow carbon shell: by prepared powder 125 DEG C of insulations 10min completes foaming process, then the powder of foaming is placed in tube furnace at helium-atmosphere 800 DEG C holding 15h, is cooled to room Temperature obtains Si-C composite material product.
Embodiment 8
A kind of Si-C composite material preparation method based on macromolecule foaming microsphere, wherein, utilizes material with carbon element to carry out nano-silicon Cladding processes, and cladding processing mode is gas phase cladding；Specific as follows:
1, carbonization after macromolecule foaming microsphere foamable is obtained hollow carbon shell: 3g foam microspheres is scattered in the anhydrous second of 15ml In alcohol, magnetic agitation 10min, ultrasonic 5min, then at 80 DEG C of dry 4h, the powder obtained is complete at 130-155 DEG C of insulation 10min Become foaming process, at 600 DEG C, then keep 10h, be cooled to room temperature and obtain the hollow carbon shell that foam microspheres carbonization obtains.
2, nano-silicon is carried on hollow carbon shell: weigh 0.9g nano silica fume and be scattered in 10ml with gained hollow carbon shell In ionized water, magnetic agitation 10min, ultrasonic 5min, then at 80 DEG C of dry 4h, obtain powder.
3, dried powder is placed in the atmosphere tube type stove of diameter 80mm, in stove, is passed through 10cm3/ min flow velocity Methane, is warmed up to 800 DEG C and keeps 2h, is cooled to room temperature and obtains Si-C composite material product.
Nano silica fume Surface coating in this composite has the carbon-coating of methane formation of deposits.
Embodiment 9
A kind of Si-C composite material preparation method based on macromolecule foaming microsphere, wherein, utilizes material with carbon element to carry out nano-silicon Cladding processes, and cladding processing mode is gas phase cladding；Specific as follows:
1, nano-silicon is carried on macromolecule foaming microsphere；Weigh 1.5g nano silica fume and 3g foam microspheres be scattered in 15ml without In water-ethanol, magnetic agitation 10min, ultrasonic 5min, then at 80 DEG C of dry 4h, obtain powder.
2, carbonization after macromolecule foaming microsphere foamable is obtained hollow carbon shell, carbonisation is passed through carbon source gas Body, at nano-silicon coated with carbon bed: prepared powder is completed foaming process, then by foaming at 145 DEG C of insulation 10min Powder is placed in the atmosphere tube type stove of diameter 80mm, is passed through 50cm in stove3The acetylene of/min flow velocity, is warmed up to 1000 DEG C of holdings 1h, is cooled to room temperature and obtains Si-C composite material product.
Nano silica fume Surface coating in this composite has the carbon-coating of acetylene formation of deposits.
Embodiment 10
A kind of Si-C composite material preparation method based on macromolecule foaming microsphere, wherein, utilizes conducting polymer materials to receiving Rice silicon carries out cladding process, and cladding processing mode is solid phase cladding；Specific as follows:
1, carbonization after macromolecule foaming microsphere foamable is obtained hollow carbon shell: 3g foam microspheres is scattered in the anhydrous second of 15ml In alcohol, magnetic agitation 10min, ultrasonic 5min, then at 80 DEG C of dry 4h, the powder obtained is complete at 130-155 DEG C of insulation 10min Become foaming process, at 600 DEG C, then keep 10h, be cooled to room temperature and obtain the hollow carbon shell that foam microspheres carbonization obtains.
2, coated polymer raw material, nano-silicon are carried on hollow carbon shell: by gained hollow carbon shell and 1.6g nanometer Silica flour, 0.93g aniline and 1.98g phytic acid join in the middle of 5ml deionized water, are added dropwise over 1ml persulfuric acid in gained solution Aqueous ammonium (containing Ammonium persulfate. 0.3g), after supersound process 5ml, at 80 DEG C of dry 1h, is cooled to room temperature acquisition silicon-carbon and is combined Material product.
Nano silica fume Surface coating in this composite has polyaniline-coated layer.
It should be noted last that, above example is only in order to illustrate technical scheme and unrestricted, although ginseng According to embodiment, the present invention has been described in detail, and it will be understood by those within the art that, to technical scheme Modifying or equivalent, without departure from the spirit and scope of technical scheme, it all should contain the present invention's In claims.

Claims (10)

1. a Si-C composite material based on macromolecule foaming microsphere, it is characterised in that: Si-C composite material passes through hollow carbon Shell load nano-silicon is constituted.
Si-C composite material based on macromolecule foaming microsphere the most according to claim 1, it is characterised in that: described hollow Carbon shell is made up of macromolecule foaming microsphere carbonization.
Si-C composite material based on macromolecule foaming microsphere the most according to claim 2, it is characterised in that: described nanometer Silicon face has conducting polymer clad or carbon coating layer.
4. according to the Si-C composite material based on macromolecule foaming microsphere described in claim 1 or 2 or 3, it is characterised in that: institute Stating nano-silicon particle mean size is 1 ~ 300nm.
Si-C composite material based on macromolecule foaming microsphere the most according to claim 4, it is characterised in that: silicon-carbon is combined In material, nano-silicon content is 5 ~ 80wt%, and hollow carbon shell content is 5 ~ 95wt%, nano-silicon surface coating layer content is 0 ~ 15wt%。
Si-C composite material based on macromolecule foaming microsphere the most according to claim 5, it is characterised in that: nano-silicon table Coating thickness 1 ~ the 20nm in face.
7. a Si-C composite material preparation method based on macromolecule foaming microsphere, it is characterised in that: comprise the steps:
(1), carbonization after macromolecule foaming microsphere foamable is obtained hollow carbon shell；
(2), nano-silicon is carried on hollow carbon shell；
Or,
(1), nano-silicon is carried on macromolecule foaming microsphere；
(2), carbonization after macromolecule foaming microsphere foamable is obtained hollow carbon shell.
8. the Si-C composite material preparation method based on macromolecule foaming microsphere described in claim 7, it is characterised in that: foaming Microsphere carbonization parameter: temperature 400 ~ 1100 DEG C, time 20min ~ 24h.
Si-C composite material preparation method based on macromolecule foaming microsphere the most according to claim 8, it is characterised in that: Utilize conducting polymer or carbon raw material that nano-silicon is carried out cladding process；Cladding processing mode be gas phase cladding, liquid phase coating or Solid phase is coated with；Specific as follows:
Liquid phase coating: after (1), nano-silicon and cladding raw material process under liquid-phase condition, be dried to obtain conducting polymer cladding or The nano-silicon of carbon cladding；(2), the nano-silicon of gained conducting polymer cladding or carbon cladding is carried on macromolecule foaming microsphere On；(3), by be loaded with conducting polymer cladding or carbon cladding nano-silicon macromolecule foaming microsphere foamable after carbonization obtain To Si-C composite material；
Or, (1), nano-silicon is carried on macromolecule foaming microsphere；(2), by micro-for the macromolecule foaming that is loaded with nano-silicon After ball foamable, carbonization obtains Si-C composite material；(3), Si-C composite material and cladding raw material are processed under liquid-phase condition After, it is dried to obtain conducting polymer cladding or the Si-C composite material of carbon cladding；
Or, (1), carbonization after macromolecule foaming microsphere foamable is obtained hollow carbon shell；(2) in, nano-silicon being carried on The Si-C composite material obtained on empty carbon shell；(3), Si-C composite material and cladding after raw material processes under liquid-phase condition, are done The dry Si-C composite material obtaining conducting polymer cladding or carbon cladding；
Gas phase is coated with: (1), carbonization after macromolecule foaming microsphere foamable is obtained hollow carbon shell；(2), nano-silicon is loaded On hollow carbon shell；(3), step (2) product is placed in heating furnace, under 400 ~ 1000 DEG C of heating conditions, in heating furnace It is passed through carbon source gas, at nano-silicon coated with carbon bed；
Or, (1), nano-silicon is carried on macromolecule foaming microsphere；(2), by carbon after macromolecule foaming microsphere foamable Change and obtain hollow carbon shell, carbonisation is passed through carbon source gas, at nano-silicon coated with carbon bed: wherein, described carbon source Gas is one or more in methane, ethane, propane, butane, ethylene, acetylene, benzene,toluene,xylene；
Solid phase is coated with: (1), carbon coated raw material, nano-silicon are carried on macromolecule foaming microsphere；(2), by macromolecule foaming After microsphere foamable, carbonization obtains hollow carbon shell；
Or, (1), carbonization after macromolecule foaming microsphere foamable is obtained hollow carbon shell；(2), by former for coated polymer material Material, nano-silicon are carried on hollow carbon shell.
10. Si-C composite material based on macromolecule foaming microsphere is as the application of lithium cell cathode material.
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