CN106207108B - Si-C composite material and the preparation method and application thereof based on macromolecule foaming microballoon - Google Patents
Si-C composite material and the preparation method and application thereof based on macromolecule foaming microballoon Download PDFInfo
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- CN106207108B CN106207108B CN201610535744.2A CN201610535744A CN106207108B CN 106207108 B CN106207108 B CN 106207108B CN 201610535744 A CN201610535744 A CN 201610535744A CN 106207108 B CN106207108 B CN 106207108B
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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
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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
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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
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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
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Abstract
The present invention is a kind of Si-C composite material and the preparation method and application thereof based on macromolecule foaming microballoon pore-creating mechanism.The Si-C composite material includes the hollow carbon shell being carbonized by foam microspheres, the nano-silicon for being carried on hollow carbon shell, and wherein hollow carbon shell content is 5 ~ 95wt%, and nanometer silicone content is 5 ~ 80wt%.There are conducting polymer clad or carbon coating layer, 1 ~ 20nm of coating thickness in nanometer silicon face.Si-C composite material disclosed by the invention is simple for process, equipment requirement is low, production efficiency is high, and material specific capacity is high（100mA·g‑1Up to 1000mAhg under current density‑1）, it can be used for field of lithium ion battery, it is widely used.
Description
Technical field
The invention belongs to materials and electrochemical field, and in particular to a kind of silicon based on macromolecule foaming microballoon pore-creating mechanism
Carbon composite and preparation method thereof, and the application as lithium ion battery negative material.
Background technology
In numerous lithium ion battery negative materials, graphitic conductive is good, electrode potential is low（<1.0vs. Li+/
Li）, cheap nontoxic, cyclical stability and chemical stability it is high, still occuping market mainstream at present（Such as natural graphite, artificial stone
Ink etc.）.But graphite specific capacity is already close to theoretical capacity（372mAh/g）, performance boost space is small.Thus, it is necessary to it opens
Send out Novel high-specific capacity flexible negative material.
The theoretical specific capacity of silicon is 10 times of graphite or more, and charge and discharge electrode potential is low, voltage platform is steady, is considered
It is the most possible next-generation negative material for substituting graphite material.But silicon materials are asked as negative material there is also following
Topic：1, in charge and discharge process, silicon materials can dusting due to reciprocal volume change, the silicon materials of dusting and external circuit electrical contact
Difference, reversible specific capacitance rapid decay；2, as semi-conducting material, silicon materials conductivity is low, and electrochemical reaction rates are limited.
To solve the problems, such as that silicon materials exist, those skilled in the art prepare silicon based composite material to improve electricity by design
Conductance, and enhancing structure stability simultaneously.Wherein, carbon material because chemical property is stable, conductive capability is strong, good toughness and become
The most commonly used compounding ingredients of silicon based composite material.And in Si-C composite material, and silicon materials are resisted with nano/micron hollow structure
Volumizing effect when charging is best.For example, Stanford University Yi Cui etc. by nano-silicon be coated on cavity volume be more than receive
In the carbon shell of rice silicon volume, in carbon shell internal reservation silicon volume expansion space, obtain with high cyclical stability
Yolk-shell structure Si-C composite materials（Nano Letters, 2012,12 (6)：3315-3321）.Pass through liquid surface
The agglomeration of power or mechanical pressure enhancing yolk-shell structure Si-C composite materials, the accumulation that can further enhance material are close
Degree（Nature Nanotechnology, 2014,9 (3):187-192, Energy ＆ Environmental Science,
2015,8 (8): 2371-2376）.However the technology uses SiO2Cladding-HF etching technics pore-creating, the toxicity and SiO of HF2Cladding
The extremely low production efficiency of process makes the mass production of the material become very difficult.The problem also exists in patent of invention
In technical solution disclosed in CN201510613252.6 and CN201410587251.4.
Patent of invention CN201210566788.3 discloses a kind of silicon nanoparticle filling carbon nano-pipe compound and its system
Preparation Method and application.The program is using the anodic alumina films with regular pore structure as template, first in anodic alumina films
Nano pore inner surface cracks organic lower carbon number hydrocarbons deposited carbon layer, then using silane as silicon source chemical vapor deposited silicon particle, finally
It removes anodic alumina films and obtains silicon nanoparticle filling carbon nano-pipe compound.In this method, complex process is existed simultaneously, it is raw
Production efficiency is low and alumina formwork chemical stability is high, the problem of being not easy to remove.
Patent of invention CN201510545414.7 discloses a kind of hollow porous carbon/silicon nanofiber of doped graphene
Lithium cell cathode material and preparation method thereof.The preparation process first obtains doping graphene oxide by coaxial electrostatic spinning technology
Polyacrylonitrile/polymethyl methacrylate/silicon dioxide nano fiber, then heat-treat to obtain through high temperature cabonization, magnesium powder and adulterate stone
Hollow porous carbon/silicon nanofiber lithium cell cathode material of black alkene.The very low electrostatic of production efficiency is used in the technique
Spining technology, and there are the magnesium powders of potential danger to heat-treat technology in large form production.
In summary, the preparation process of the Si-C composite material with hollow structure mostly uses template or Static Spinning at present
Silk technology, complex technical process, preparation condition are stringent, and the production efficiency and cost of material are severely limited.Therefore, how real
Now the efficient preparation of the Si-C composite material with hollow structure is lithium ion battery negative material field technology urgently to be resolved hurrily
Problem.
Invention content
In view of the deficiencies of the prior art, one of the objects of the present invention is to provide one kind being based on macromolecule foaming microballoon 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 microballoon, the Si-C composite material are received by the load of hollow carbon shell
Rice silicon is constituted.
Preferably, the nanometer silicon face has conducting polymer clad or carbon coating layer.
Preferably, the hollow carbon shell is made of the carbonization of macromolecule foaming microballoon, and content is 5 ~ 95wt%.
Preferably, the nano-silicon average particle size is 1 ~ 300nm.
Preferably, the nano-silicon is mono-dispersed nano silicon particle.
Preferably, in the Si-C composite material, nanometer silicone content is 5 ~ 80wt%.
Preferably, the conducting polymer clad can be polyacetylene, polythiophene, polypyrrole, polyaniline, polyhenylene,
One or several kinds of arbitrary combinations in polyphenylene ethylene and poly bis alkynes, 1 ~ 20nm of thickness.
Preferably, the carbon coating layer can be one or several kinds of in soft carbon, hard carbon, graphene, carbon nanotube
Arbitrary combination, 1 ~ 20nm of thickness.
The second object of the present invention is to provide a kind of preparation method of Si-C composite material, include the following steps：
（1）, will after macromolecule foaming microballoon foamable carbonization obtain hollow carbon shell；
（2）, nano-silicon is carried on hollow carbon shell.
Alternatively,
（1）, nano-silicon is carried on macromolecule foaming microballoon；
（2）, will after macromolecule foaming microballoon foamable carbonization obtain hollow carbon shell.
Preferably, foam microspheres carbonization parameter：400 ~ 1100 DEG C of temperature, time 20min ~ for 24 hours.
Preferably, cladding processing is carried out to nano-silicon using conducting polymer or carbon raw material；The carbon raw material will pass through carbon
Change is converted into carbon coating layer.It is gas phase cladding, liquid phase coating or solid phase cladding to coat processing mode；It is specific as follows：
Liquid phase coating：（1）, nano-silicon and cladding raw material handled under liquid-phase condition after, be dried to obtain conducting polymer packet
It covers or carbon-coated nano-silicon；（2）, by gained conducting polymer coat or carbon-coated nano-silicon to be carried on macromolecule foaming micro-
On ball；（3）, will load have conducting polymer coat or carbon-coated nano-silicon macromolecule foaming microballoon foamable after be carbonized
Obtain Si-C composite material.
Alternatively,（1）, nano-silicon is carried on macromolecule foaming microballoon；（2）, will load have nano-silicon macromolecule send out
Carbonization obtains Si-C composite material after bubble microballoon foamable；（3）, by Si-C composite material and cladding raw material under liquid-phase condition
After processing, it is dried to obtain conducting polymer cladding or carbon-coated Si-C composite material.
Alternatively,（1）, will after macromolecule foaming microballoon foamable carbonization obtain hollow carbon shell；（2）, nano-silicon loaded
In the Si-C composite material obtained on hollow carbon shell；（3）, by Si-C composite material and cladding raw material handled under liquid-phase condition
Afterwards, conducting polymer cladding or carbon-coated Si-C composite material are dried to obtain.
Gas phase coats：（1）, will after macromolecule foaming microballoon foamable carbonization obtain hollow carbon shell；（2）, by nano-silicon
It is carried on hollow carbon shell；（3）, by step（2）Product is placed in heating furnace, under 400 ~ 1000 DEG C of heating conditions, to heating
Carbon source gas is passed through in stove, in nano-silicon coated with carbon bed.
Alternatively,（1）, nano-silicon is carried on macromolecule foaming microballoon；（2）, by macromolecule foaming microballoon foamable
Carbonization obtains hollow carbon shell afterwards, carbon source gas is passed through in carbonisation, in nano-silicon coated with carbon bed.Wherein, the carbon
Property gas in source is one or more of methane, ethane, propane, butane, ethylene, acetylene, benzene,toluene,xylene.
Solid phase coats：（1）, cladding carbon raw material, nano-silicon be carried on macromolecule foaming microballoon；（2）, by macromolecule
Carbonization obtains hollow carbon shell after foam microspheres foamable.
Alternatively,（1）, will after macromolecule foaming microballoon foamable carbonization obtain hollow carbon shell；（2）, by coated polymer
Raw material, nano-silicon are carried on hollow carbon shell.
The third object of the present invention is that the above-mentioned Si-C composite material based on macromolecule foaming microballoon 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, the present invention has the advantages that：
It is said from the angle of preparation, the hollow carbon shell in Si-C composite material disclosed by the invention is existed by macromolecule foaming microballoon
Automatic foaming forms in heating carbonisation namely the formation of the hollow structure does not need any sacrificial template or special work
Skill designs；Relative to template or electrostatic spinning technique, in terms of production efficiency, cost and the feature of environmental protection, there is advantage outstanding.
It is said from the angle of performance, the hollow carbon shell not only has good electric conductivity, and silicon materials can be overcome conductive
The slow problem of electrochemical reaction rates caused by rate is low；And it can be swollen by being deformed into silicon materials volume in battery charging process
Swollen offer space, to promote the cyclical stability of material.
Si-C composite material disclosed by the invention is simple for process, equipment requirement is low, production efficiency is high, and material specific capacity
It is high（100mA·g-1Up to 1000mAhg under current density-1）, it can be used for field of lithium ion battery, it is widely used, have very
Good actual application value.
Description of the drawings
Fig. 1 indicates the scanning electron microscope (SEM) photograph for the Si-C composite material that embodiment 1 obtains.
Fig. 2 indicates the Si-C composite material of the acquisition of embodiment 1 in 300mA/g-1Constant current charge-discharge curve under electric density.
Fig. 3 indicates specific capacity curve of the Si-C composite material of the acquisition of embodiment 1 after different charge and discharge cycles.
Specific implementation mode
Specific embodiments of the present invention are described in detail below.
A kind of Si-C composite material based on macromolecule foaming microballoon pore-creating mechanism, the Si-C composite material are sent out by macromolecule
Hollow carbon shell load nano-silicon made of microballoon carbonization is steeped to constitute.
The nano-silicon average particle size is 1 ~ 300nm.The nanometer silicon face has conducting polymer clad or carbon coating
Layer, 1 ~ 20nm of coating thickness.
In Si-C composite material, nanometer silicone content is 5 ~ 80wt%, and hollow carbon shell content is 5 ~ 95wt%, nanometer silicon face
Clad content is 0 ~ 15wt%.
The preparation of above-mentioned Si-C composite material includes the combination of following procedure：（1）Macromolecule foaming microballoon is heated and is carbonized
Obtain hollow carbon shell；（2）Nano-silicon is carried on macromolecule foaming microballoon or hollow carbon shell.In process（1）、（2）Implement it
Before, in or after the process, cladding processing is carried out to nano-silicon using conducting polymer, carbon or carbon raw material；The carbon raw material will
It is converted into carbon coating layer by carbonization.
Specific preparation method following examples.
Embodiment 1
A kind of preparation of silicon carbon composite materials method based on macromolecule foaming microballoon is as follows：
1, nano-silicon is carried on macromolecule foaming microballoon：0.4g nano silica fumes are weighed, 6g foam microspheres are scattered in
In 15ml absolute ethyl alcohols, magnetic agitation 10min, ultrasonic 5min obtain powder then in 80 DEG C of dry 4h.
2, carbonization after macromolecule foaming microballoon foamable is obtained into hollow carbon shell：Powder obtained is kept the temperature at 100 DEG C
10min completes foaming process, and then the powder of foaming is placed in tube furnace and keeps 2h at 800 DEG C of nitrogen atmosphere, is cooled to room
Temperature obtains Si-C composite material product.
As shown in Figure 1, the scanning electron microscopic picture of the Si-C composite material.
According to the energy spectrum analysis figure of the Si-C composite material it is found that using power spectrum to silicon, the carbon in sample be distributed into
It has gone analysis, it is 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 for being then scattered in hollow carbon shell.
As shown in Fig. 2, the Si-C composite material is in 300mA/g-1Constant current charge-discharge curve under electric density.
As shown in figure 3, specific capacity curve of the Si-C composite material after different charge and discharge cycles.
Embodiment 2
A kind of preparation of silicon carbon composite materials method based on macromolecule foaming microballoon is as follows：
1, nano-silicon is carried on macromolecule foaming microballoon：0.4g nano silica fumes are weighed, 6g foam microspheres are scattered in
In 15ml deionized waters, magnetic agitation 10min, ultrasonic 5min obtain powder then in 80 DEG C of dry 10h.
2, carbonization after macromolecule foaming microballoon foamable is obtained into hollow carbon shell：Powder obtained is kept the temperature at 160 DEG C
10min completes foaming process, and then the powder of foaming is placed in tube furnace and keeps 20h at 400 DEG C of nitrogen atmosphere, is cooled to room
Temperature obtains Si-C composite material product.
Embodiment 3
A kind of preparation of silicon carbon composite materials method based on macromolecule foaming microballoon is as follows：
1, nano-silicon is carried on macromolecule foaming microballoon：5g nano silica fumes are weighed, 3g foam microspheres are scattered in 15ml
In absolute ethyl alcohol, magnetic agitation 10min, ultrasonic 15min obtain powder then in 80 DEG C of dry 2h.
2, carbonization after macromolecule foaming microballoon foamable is obtained into hollow carbon shell：Powder obtained is kept the temperature at 130 DEG C
10min completes foaming process, and then the powder of foaming is placed in tube furnace and keeps 20min at 1100 DEG C of argon atmospher, cooling
Si-C composite material product is obtained to room temperature.
Embodiment 4
A kind of preparation of silicon carbon composite materials method based on macromolecule foaming microballoon is as follows：
1, nano-silicon is carried on macromolecule foaming microballoon：1.9g nano silica fumes are weighed, 0.3g foam microspheres are scattered in
In 15ml absolute ethyl alcohols, magnetic agitation 10min, ultrasonic 5min obtain powder then in 80 DEG C of dry 4h.
2, carbonization after macromolecule foaming microballoon foamable is obtained into hollow carbon shell：Powder obtained is kept the temperature at 140 DEG C
20min completes foaming process, and then the powder of foaming is placed in tube furnace and keeps 5h at 700 DEG C of ammonia atmosphere, is cooled to room
Temperature obtains Si-C composite material product.
Embodiment 5
A kind of preparation of silicon carbon composite materials method based on macromolecule foaming microballoon, wherein using carbon material to nano-silicon
Cladding processing is carried out, cladding processing mode is liquid phase coating；It is specific as follows：
1, after nano-silicon and cladding raw material are handled under liquid-phase condition, it is dried to obtain the nano-silicon of carbon material cladding：It weighs
0.4g nano silica fumes, ultrasonic disperse is in 40ml absolute ethyl alcohols and the mixed solution of deionized water（Volume ratio is 1:1）, add
50 μ l ammonium hydroxide after ultrasonic 10min, are then added the formaldehyde magnetic agitation 30min of the resorcinol and 400 μ l of 0.4g, will mix
Solution move to water heating kettle, 80 DEG C, product centrifugal drying is obtained into the nano silica fume of phenolic resin cladding afterwards for 24 hours.
2, the nano-silicon that phenolic resin coats is carried on macromolecule foaming microballoon：It is received what gained phenolic resin coated
Rice silica flour is scattered in 3g foam microspheres in 15ml absolute ethyl alcohols, magnetic agitation 10min, ultrasonic 5min, then in 80 DEG C of dryings
4h obtains powder.
Carbonization obtains hollow carbon 3, load to be had to the macromolecule foaming microballoon foamable of phenolic resin cladding nano-silicon after
Shell：Powder obtained is kept the temperature into 10min at 150 DEG C and completes foaming process, then the powder of foaming is placed in tube furnace in nitrogen
Hydrogen mixed atmosphere（Hydrogen volume content 3%）5h is kept at 700 DEG C, room temperature is cooled to and obtains Si-C composite material product.
There is the carbon coating layer that phenolic resin carbonized is formed on nano silica fume surface in the composite material.
Embodiment 6
A kind of preparation of silicon carbon composite materials method based on macromolecule foaming microballoon, wherein using carbon material to nano-silicon
Cladding processing is carried out, cladding processing mode is liquid phase coating；It is specific as follows：
1, after nano-silicon and cladding raw material are handled under liquid-phase condition, it is dried to obtain the nano-silicon of carbon material cladding：It weighs
1.5g nano silica fumes, ultrasonic disperse is in 40ml deionized waters, then to 2g glucose is added, after ultrasonic 10min, by the molten of mixing
Liquid moves to water heating kettle, and 180 DEG C, product centrifugal drying is obtained carbon-coated nano silica fume afterwards for 24 hours.
2, carbon-coated nano-silicon is carried on macromolecule foaming microballoon：The carbon-coated nano silica fume of gained and 3g are sent out
Bubble microballoon is scattered in 15ml absolute ethyl alcohols, and magnetic agitation 10min, ultrasonic 5min obtain powder then in 80 DEG C of dry 4h.
Carbonization obtains hollow carbon shell 3, load to be had to the macromolecule foaming microballoon foamable of carbon-coated nano silicon after：It will system
The powder obtained keeps the temperature 20min at 140 DEG C and completes foaming process, and then the powder of foaming is placed in tube furnace in argon hydrogen gaseous mixture
Atmosphere（Hydrogen volume content 3%）2h is kept at 900 DEG C of atmosphere, room temperature is cooled to and obtains Si-C composite material product.
There is the carbon coating layer that glucose hydrothermal carbonization is formed on nano silica fume surface in the composite material.
Embodiment 7
A kind of preparation of silicon carbon composite materials method based on macromolecule foaming microballoon, wherein using carbon material to nano-silicon
Cladding processing is carried out, cladding processing mode coats for solid phase；It is specific as follows：
1, cladding carbon raw material, nano-silicon are carried on macromolecule foaming microballoon：1.2g nano silica fumes are weighed, 0.2g carbon is received
Mitron is scattered in 3g foam microspheres in 15ml acetone, and magnetic agitation 10min, ultrasonic 5min are obtained then in 80 DEG C of dry 4h
Powder.
2, carbonization after macromolecule foaming microballoon foamable is obtained into hollow carbon shell：Powder obtained is kept the temperature at 125 DEG C
10min completes foaming process, and then the powder of foaming is placed in tube furnace and keeps 15h at 800 DEG C of helium-atmosphere, is cooled to room
Temperature obtains Si-C composite material product.
Embodiment 8
A kind of preparation of silicon carbon composite materials method based on macromolecule foaming microballoon, wherein using carbon material to nano-silicon
Cladding processing is carried out, cladding processing mode coats for gas phase；It is specific as follows：
1, carbonization after macromolecule foaming microballoon foamable is obtained into hollow carbon shell：By 3g foam microspheres be scattered in 15ml without
In water-ethanol, magnetic agitation 10min, ultrasonic 5min, then in 80 DEG C of dry 4h, obtained powder is kept the temperature at 130-155 DEG C
10min completes foaming process, then keeps 10h at 600 DEG C, is cooled to room temperature and obtains the hollow carbon that foam microspheres are carbonized
Shell.
2, nano-silicon is carried on hollow carbon shell：It weighs 0.9g nano silica fumes and is scattered in 10ml with gained hollow carbon shell
In ionized water, magnetic agitation 10min, ultrasonic 5min obtain powder then in 80 DEG C of dry 4h.
3, the powder after drying is placed in the atmosphere tube type stove of diameter 80mm, 10cm is passed through into stove3/ min flow velocitys
Methane is warming up to 800 DEG C of holding 2h, is cooled to room temperature and obtains Si-C composite material product.
Nano silica fume surface in the composite material is coated with methane and deposits the carbon-coating to be formed.
Embodiment 9
A kind of preparation of silicon carbon composite materials method based on macromolecule foaming microballoon, wherein using carbon material to nano-silicon
Cladding processing is carried out, cladding processing mode coats for gas phase；It is specific as follows：
1, nano-silicon is carried on macromolecule foaming microballoon；1.5g nano silica fumes are weighed to be scattered in 3g foam microspheres
In 15ml absolute ethyl alcohols, magnetic agitation 10min, ultrasonic 5min obtain powder then in 80 DEG C of dry 4h.
2, carbonization after macromolecule foaming microballoon foamable is obtained into hollow carbon shell, carbon source gas is passed through in carbonisation
Body, in nano-silicon coated with carbon bed：Powder obtained is kept the temperature into 10min at 145 DEG C and completes foaming process, then by foaming
Powder is placed in the atmosphere tube type stove of diameter 80mm, and 50cm is passed through into stove3The acetylene of/min flow velocitys is warming up to 1000 DEG C of holdings
1h is cooled to room temperature and obtains Si-C composite material product.
Nano silica fume surface in the composite material is coated with acetylene and deposits the carbon-coating to be formed.
Embodiment 10
A kind of preparation of silicon carbon composite materials method based on macromolecule foaming microballoon, wherein utilize conducting polymer materials
Cladding processing is carried out to nano-silicon, cladding processing mode coats for solid phase；It is specific as follows：
1, carbonization after macromolecule foaming microballoon foamable is obtained into hollow carbon shell：By 3g foam microspheres be scattered in 15ml without
In water-ethanol, magnetic agitation 10min, ultrasonic 5min, then in 80 DEG C of dry 4h, obtained powder is kept the temperature at 130-155 DEG C
10min completes foaming process, then keeps 10h at 600 DEG C, is cooled to room temperature and obtains the hollow carbon that foam microspheres are carbonized
Shell.
2, coated polymer raw material, nano-silicon are carried on hollow carbon shell：By gained hollow carbon shell and 1.6g nanometers
Silica flour, 0.93g aniline and 1.98g phytic acid are added in 5ml deionized waters, and 1ml persulfuric acid is added dropwise into acquired solution
Aqueous ammonium（Contain ammonium persulfate 0.3g）, after being ultrasonically treated 5ml, in 80 DEG C of dry 1h, it is compound to be cooled to room temperature acquisition silicon-carbon
Material product.
Nano silica fume surface in the composite material is coated with polyaniline-coated layer.
It should be noted last that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although ginseng
According to embodiment, the present invention is described in detail, it will be understood by those of ordinary skill in the art that, to technical scheme of the present invention
It is modified or replaced equivalently, without departure from the spirit and scope of technical scheme of the present invention, should all cover the present invention's
In claims.
Claims (8)
1. a kind of Si-C composite material based on macromolecule foaming microballoon, it is characterised in that：Si-C composite material passes through hollow carbon
Shell loads nano-silicon and constitutes；The hollow carbon shell is made of the carbonization of macromolecule foaming microballoon.
2. the Si-C composite material according to claim 1 based on macromolecule foaming microballoon, it is characterised in that：The nanometer
Silicon face has conducting polymer clad or carbon coating layer.
3. the Si-C composite material according to claim 1 or 2 based on macromolecule foaming microballoon, it is characterised in that：It is described
Nano-silicon average particle size is 1 ~ 300nm.
4. the Si-C composite material according to claim 3 based on macromolecule foaming microballoon, it is characterised in that：Silicon-carbon is compound
In material, nanometer silicone content be 5 ~ 80wt%, hollow carbon shell content be 5 ~ 95wt%, nano-silicon surface coating layer content be 0 ~
15wt%。
5. the Si-C composite material according to claim 4 based on macromolecule foaming microballoon, it is characterised in that：Nano-silicon table
1 ~ the 20nm of coating thickness in face.
6. a kind of preparation of silicon carbon composite materials method based on macromolecule foaming microballoon, it is characterised in that：Include the following steps：
（1）, will after macromolecule foaming microballoon foamable carbonization obtain hollow carbon shell；
（2）, nano-silicon is carried on hollow carbon shell；
Alternatively,
（1）, nano-silicon is carried on macromolecule foaming microballoon；
（2）, will after macromolecule foaming microballoon foamable carbonization obtain hollow carbon shell.
7. the preparation of silicon carbon composite materials method based on macromolecule foaming microballoon described in claim 6, it is characterised in that：Foaming
Microballoon carbonization parameter：400 ~ 1100 DEG C of temperature, time 20min ~ for 24 hours.
8. the preparation of silicon carbon composite materials method according to claim 7 based on macromolecule foaming microballoon, it is characterised in that：
Cladding processing is carried out to nano-silicon using conducting polymer or carbon raw material；Coat processing mode be gas phase cladding, liquid phase coating or
Solid phase coats；It is specific as follows：
Liquid phase coating：（1）, nano-silicon and cladding raw material handle under liquid-phase condition after, be dried to obtain conducting polymer coat or
Carbon-coated nano-silicon；（2）, gained conducting polymer is coated or carbon-coated nano-silicon is carried on macromolecule foaming microballoon
On；（3）, will load have conducting polymer coat or carbon-coated nano-silicon macromolecule foaming microballoon foamable after be carbonized
To Si-C composite material；
Alternatively,（1）, nano-silicon is carried on macromolecule foaming microballoon；（2）, will load have the macromolecule foaming of nano-silicon micro-
Carbonization obtains Si-C composite material after ball foamable；（3）, by Si-C composite material and cladding raw material handled under liquid-phase condition
Afterwards, conducting polymer cladding or carbon-coated Si-C composite material are dried to obtain；
Alternatively,（1）, will after macromolecule foaming microballoon foamable carbonization obtain hollow carbon shell；（2）, nano-silicon is carried on
The Si-C composite material obtained on empty carbon shell；（3）, Si-C composite material and cladding raw material handles under liquid-phase condition after, it is dry
It is dry to obtain conducting polymer cladding or carbon-coated Si-C composite material；
Gas phase coats：（1）, will after macromolecule foaming microballoon foamable carbonization obtain hollow carbon shell；（2）, nano-silicon loaded
In on hollow carbon shell；（3）, by step（2）Product is placed in heating furnace, under 400 ~ 1000 DEG C of heating conditions, into heating furnace
It is passed through carbon source gas, in nano-silicon coated with carbon bed；
Alternatively,（1）, nano-silicon is carried on macromolecule foaming microballoon；（2）, by carbon after macromolecule foaming microballoon foamable
Change obtains hollow carbon shell, carbon source gas is passed through in carbonisation, in nano-silicon coated with carbon bed：Wherein, the carbon source
Gas is one or more of methane, ethane, propane, butane, ethylene, acetylene, benzene,toluene,xylene；
Solid phase coats：（1）, cladding carbon raw material, nano-silicon be carried on macromolecule foaming microballoon；（2）, by macromolecule foaming
Carbonization obtains hollow carbon shell after microballoon foamable；
Alternatively,（1）, will after macromolecule foaming microballoon foamable carbonization obtain hollow carbon shell；（2）, by coated polymer former material
Material, nano-silicon are carried on hollow carbon shell.
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| CN105190948B (en) | 2013-03-14 | 2019-04-26 | 14族科技公司 | The complex carbon material of electrochemical modification agent comprising lithium alloyage |
| US10195583B2 (en) | 2013-11-05 | 2019-02-05 | Group 14 Technologies, Inc. | Carbon-based compositions with highly efficient volumetric gas sorption |
| CN107074994B (en) | 2014-03-14 | 2021-12-14 | 14集团技术公司 | Novel method for solvent-free sol-gel polymerization and production of adjustable carbon structures therefrom |
| US20190097222A1 (en) | 2015-08-14 | 2019-03-28 | Energ2 Technologies, Inc. | Composites of porous nano-featured silicon materials and carbon materials |
| JP7115976B2 (en) | 2015-08-28 | 2022-08-09 | グループ１４・テクノロジーズ・インコーポレイテッド | Novel materials with very durable intercalation of lithium and methods for their production |
| JP7376360B2 (en) * | 2017-03-09 | 2023-11-08 | グループ１４・テクノロジーズ・インコーポレイテッド | Degradation of silicon-containing precursors on porous scaffold materials |
| CN107394163B (en) * | 2017-07-25 | 2020-03-17 | 陕西科技大学 | Copper-molybdenum-carbon dioxide composite material with hollow core-shell structure and preparation method and application thereof |
| CN109873136B (en) * | 2019-01-29 | 2021-10-22 | 鸿纳（东莞）新材料科技有限公司 | Preparation method of porosity-controllable graphene modified silicon-carbon composite material |
| US11335903B2 (en) | 2020-08-18 | 2022-05-17 | Group14 Technologies, Inc. | Highly efficient manufacturing of silicon-carbon composites materials comprising ultra low z |
| US11639292B2 (en) | 2020-08-18 | 2023-05-02 | Group14 Technologies, Inc. | Particulate composite materials |
| US11174167B1 (en) | 2020-08-18 | 2021-11-16 | Group14 Technologies, Inc. | Silicon carbon composites comprising ultra low Z |
| CN112467093A (en) * | 2020-10-23 | 2021-03-09 | 合肥国轩高科动力能源有限公司 | Carbon-silicon double-coated nitrogen-doped hollow carbon microsphere composite material and preparation method thereof |
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