CN106784695A - Prepare method, the composite and the lithium ion battery of CNT/SiC/ nano Si composites - Google Patents

Prepare method, the composite and the lithium ion battery of CNT/SiC/ nano Si composites Download PDF

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CN106784695A
CN106784695A CN201611217641.8A CN201611217641A CN106784695A CN 106784695 A CN106784695 A CN 106784695A CN 201611217641 A CN201611217641 A CN 201611217641A CN 106784695 A CN106784695 A CN 106784695A
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sio
nano
sic
composites
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齐小鹏
杨娟玉
卢世刚
王宁
史碧梦
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China Automotive Battery Research Institute Co Ltd
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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
    • 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
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Silicon Compounds (AREA)

Abstract

The invention discloses method, the composite and lithium ion battery that one kind prepares CNT/SiC/ nano Si composites.The method, by CNT and SiO2It is uniformly dispersed in aqueous, CNT/SiO is made after drying moisture, crushing, compressing, cutting2Porous pole piece；Using the above-mentioned porous pole pieces of CNT/SiO2 as negative electrode, constant-current electrolysis is passed through in molten-salt electrolysis liquid by SiO2Electroreduction is nano Si；A part of Si generates SiC with CNT reaction in the process, so as to CNT/SiC/ nano Si composites are obtained.The composite is prepared by the method.The negative material of the battery is the composite.The CNT/SiC/ nano Sis composite may simultaneously play the excellent electric conductivity of the height ratio capacity of nano Si, CNT, the advantage of the stability of SiC, can be used as lithium ion battery negative material；Disclosed method has nano Si raw material environment-friendly, cheap, preparation process low power consumption and other advantages.

Description

Prepare method, the composite and the lithium of CNT/SiC/ nano Si composites Ion battery
Technical field
CNT/SiC/ nano Si composite woods are prepared the invention belongs to field of composite material preparation, more particularly to one kind The method of material, the composite and lithium ion battery.
Background technology
Graphite negative electrodes material highest theoretical specific capacity is 372mAh/g, has seriously constrained lithium ion battery energy close The further raising of degree.Silicon (Si) have high theoretical specific capacity (3579mAh/g) and relatively low de- lithium current potential (~ 370mVvs.Li/Li+), it is considered to be the first-selected negative material of lithium ion battery of future generation.However, Si is in charge and discharge process Volume Changes are huge, easily lost with collector and electrically connected, and cause very poor (the Electrochemical and of cycle performance Solid-State Letters,2004,7(10):A306-A309)。
The content of the invention
For in the prior art without low cost, the phase for preparing CNT/SiC/ nano Si composites of low energy consumption The blank of pass method, it is an object of the present invention to provide one kind prepare CNT/SiC/ nano Si composites method, this be combined Material and lithium ion battery.
To realize first purpose of the invention, what the present invention was provided prepares CNT/SiC/ nano Si composites Method use following technical scheme：
The method for preparing CNT/SiC/ nano Si composites of present invention offer is comprised the following steps：
CNT and SiO2 are mixed, CNT/SiO is made2Porous pole piece；
Electroreduction CNT/SiO in fused salt2SiO in porous pole piece2Prepare CNT/SiC/ nano Sis Composite.
The method for preparing CNT/SiC/ nano Si composites of present invention offer can also further using following Technical scheme is realized.
Preferably, by CNT and SiO2Mixed, be made CNT/SiO2Porous pole piece includes following step Suddenly：
A certain amount of water is added in mixer batch can, by carbon nanotube dust or aqueous liquid dispersion containing CNT Pour into mixer batch can, stirring makes CNT be uniformly dispersed in aqueous；
SiO is added in batch can2Powder body material, stirring makes CNT and SiO2Be uniformly dispersed, obtain CNT/ SiO2The pureed mixture of/water；
CNT/the SiO that will be obtained2Compressing after pureed mixture drying moisture, the crushing of/water is carbon nanometer Pipe/SiO2Porous blocks material；
By the CNT/SiO2Porous blocks material is further cut into the CNT/SiO being sized2It is porous Pole piece.
Preferably, the CNT of the electroreduction in the fused salt/SiO2SiO in porous pole piece2Prepare carbon nanometer Pipe/SiC/ nano Si composites are comprised the following steps：
With the CNT/SiO2Porous pole piece as negative electrode, using graphite cake as anode, with CaCl2Fused salt is used as electricity Solution liquid, applies constant current, by CNT/SiO by between the negative electrode and anode2SiO in porous cathode2Electrolysis Nano Si is reduced to, a step part Si reacts to form SiC with CNT in the process；
By the negative electrode from CaCl2Taken out in fused salt, dispersed with stirring uses water filtering and washing in the aqueous solution, dried in vacuum CNT/SiC/ nano Si composites are obtained after case drying moisture.
Preferably, the CNT is single wall or multi-walled carbon nano-tubes, the span of caliber is 5~30nm.
Preferably, the SiO2Powder is nanoparticle powder, and the span of particle diameter is 5~100nm.
Preferably, the CNT and SiO2Mass ratio span be 1:199~1:4.
Preferably, the span of the thickness of the porous pole piece is 2~10mm.
Preferably, the CaCl2The span of the temperature of fused salt is 850~900 DEG C.
Preferably, the span of the current density for applying constant current described in step (2) is 100~1000A/ m2。
Present invention also offers a kind of CNT/SiC/ nano Si composites, the CNT/SiC/ nano Sis Composite is prepared by the method that the present invention is provided.
Present invention also offers a kind of lithium ion battery, the negative material of the lithium ion battery is provided by the present invention CNT/SiC/ nano Si composites for preparing of method.
CNT of the invention/SiC/ nano Si composites, it is advantageous in that, while playing the Fabrication of High Specific Capacitance of Si Amount, CNT excellent electric conductivity, the stability triple role of SiC, have as compound lithium ion battery negative material There is specific capacity and cyclical stability higher；The method for preparing CNT/SiC/ nano Si composites of the invention, uses SiO2It is the raw material of Si, environment-friendly and cheap, reaction temperature is prepared at 850~900 DEG C far below industrial during electrolysis The methods such as carbon thermal reduction, the Siemens Method of Si, energy consumption is relatively low.
Brief description of the drawings
By reading the detailed description of hereafter preferred embodiment, various other advantages and benefit is common for this area Technical staff will be clear understanding.Accompanying drawing is only used for showing the purpose of preferred embodiment, and is not considered as to the present invention Limitation.And in whole accompanying drawing, identical part is denoted by the same reference numerals.In the accompanying drawings：
Fig. 1 is CNT/SiO prepared by the embodiment of the present invention 22The scanning electron microscope diagram piece of porous cathode piece；
Fig. 2 is the scanning electron microscope diagram of CNT/SiC/ nano Si composites prepared by the embodiment of the present invention 2 Piece；
Fig. 3 is the X-ray diffraction spectrogram of CNT/SiC/ nano Si composites prepared by the embodiment of the present invention 2.
Specific embodiment
Further to illustrate the present invention to reach technological means and effect that predetermined goal of the invention is taken, below in conjunction with Accompanying drawing and preferred embodiment, to according to the method for preparing CNT/SiC/ nano Si composites proposed by the present invention, in detail Illustrate as after.
Inventor is by long-term experiment and extremely hard and bitter effort, it is found that nano Si is smaller due to size itself, charge and discharge During electric Volume Changes, the stress of material internal accumulation is easier release, so as to have preferable cycle performance.The preparation of nano Si The method method such as including chemical vapor deposition, thermal evaporation, chemical etching；However, these methods generally require reaction temperature higher Degree, expensive raw material or poisonous, dangerous chemical substance, are unfavorable for the production and preparation of extensive nano Si.Additionally, The good combination of materials of nano Si and other electric conductivity is formed into composite, is also effective way of the cycle performance for lifting Si Footpath.
Inventor long-term experiment and extremely hard and bitter effort, by composite Materials Design, by Si and other functions material Material is effectively combined, and can effectively lift the cyclical stability of Si base negative materials.For example, Si is good with other electric conductivities Good material compound can reduce it and lose electrical connection and deactivated probability；By " activity-nonactive " composite Design, Si is combined with other inert matters, can limit the overall cyclical stability of its Volume Changes lifting material.Carbon nanometer Pipe (CNT) has excellent electric conductivity and mechanical strength, and its special filamentary structure is also helped sets up what is consolidated Three-dimensional conductive network.Research confirms that the composite that CNT is constituted as conductive materials and Si shows specific volume higher Amount and cycle performance.SiC electric conductivity is poor, hardness is very high, can be combined with nano Si as inert matter, is received with limiting The Volume Changes of rice Si, the whole structural stability of lifting material.Although it is compound that CNT, SiC and nano Si are separately constituted Material has shown that excellent performance, but low cost, the preparation of low energy consumption of the composite of CNT/SiC/ nano Sis Method yet there are no relevant report.The composite of CNT/SiC/ nano Sis composition can simultaneously play the ratio high of nano Si The excellent electric conductivity of capacity, CNT, the stability of SiC, with good property during as lithium ion battery negative material Energy.
The terms "and/or", only a kind of incidence relation for describing affiliated partner, represents there may be three kinds of passes System, for example, A and/or B, is specifically interpreted as：A and B can simultaneously be included, can be with individualism A, it is also possible to individualism B, can possess above-mentioned three kinds of any one situations.
Embodiment 1：
1990g water is added in mixer batch can, 2.5g carbon nanotube dusts (5~30nm of caliber) are poured into planetary stirring Mix in machine batch can, high-speed stirred makes CNT be uniformly dispersed in aqueous in 30 minutes；Added in mixer batch can 497.5gSiO2Powder body material (SiO2Nano particle, 5~100nm of particle diameter), high-speed stirred makes CNT and SiO in 2 hours2Point Dissipate uniform, obtain CNT/SiO2The pureed mixture of/water；CNT/the SiO that will be obtained2The pureed mixture of/water is put In convection oven, in 150 DEG C of drying, 24 hours drying moisture, and the CNT obtained above-mentioned drying with mechanical crusher/ SiO2Solid mixt is crushed；By the CNT/SiO after crushing2Powder cold isostatic press room temperature, pressure be 185Mpa, Dwell time be 1 hour under the conditions of it is compressing be CNT/SiO2Porous blocks material；By above-mentioned CNT/SiO2It is many Hole block materials are cut into the CNT/SiO of 50 × 50 × 2mm2Porous pole piece.With above-mentioned CNT/SiO2Porous pole piece As negative electrode, using graphite cake as anode, with 850 DEG C of CaCl2Fused salt applies as electrolyte between the negative electrode and anode 0.5A (is 100A/m relative to cathode area current density2) electric current, by SiO2Electroreduction is nano Si；Electrolysis electricity reaches SiO in being 100% complete electroreduction pole piece to current efficiency in theory2When 1.3 times (10.4Ah) of institute's subfam. Spiraeoideae, terminate electricity Solution preocess, by the cathode sheets after electrolysis from CaCl2The dilute hydrochloric acid solution for being placed in 1000ml mass fractions about 2% is taken out in fused salt In, high-speed stirred makes CaCl in pole piece in 1 hour2Dissolving, while disperseing pole piece, obtains containing CNT/SiC/ nano Sis Composite CaCl2With the dispersion liquid of hydrochloric acid；With pure water filtering and washing CNT/SiC/ nano Si composites, to filtrate It is middle without chlorion；Filter cake is placed in vacuum drying oven, obtaining CNT/SiC/ after drying moisture within 24 hours in 120 DEG C of drying receives Rice Si composites.
Embodiment 2：
4750g water is added in mixer batch can, is by 1000g carbon nanotube dusts (5~30nm of caliber) mass fraction 5% carbon nano tube dispersion liquid is poured into planetary stirring machine batch can, and high-speed stirred makes CNT in aqueous in 30 minutes It is uniformly dispersed；To adding 450gSiO in mixer batch can2Powder body material (SiO2Nano particle, 5~100nm of particle diameter), high-speed stirring Mixing 2 hours makes CNT and SiO2It is uniformly dispersed, obtains CNT/SiO2The pureed mixture of/water；The carbon that will be obtained is received Mitron/SiO2The pureed mixture of/water is placed in convection oven, in 150 DEG C of drying, 24 hours drying moisture, and uses mechanical crusher CNT/SiO that above-mentioned drying is obtained2Solid mixt is crushed；By the CNT/SiO after crushing2Powder hot pressing Machine temperature be 1080 DEG C, pressure be 20Mpa, the dwell time be 2 hours under the conditions of it is compressing be CNT/SiO2It is porous Block materials；By above-mentioned CNT/SiO2Porous blocks material is cut into the CNT/SiO of 50 × 50 × 5mm2Multiaperture electrode Piece, the CNT/SiO2The scanning electron microscope diagram piece of porous pole piece is as shown in Figure 1.With above-mentioned CNT/SiO2 Porous pole piece as negative electrode, using graphite cake as anode, with 850 DEG C of CaCl2Fused salt as electrolyte, in the negative electrode and anode Between apply 1.5A (relative to cathode area current density be 300A/m2) electric current, by SiO2Electroreduction is nano Si；Electricity It is SiO in 100% complete electroreduction pole piece that solution electricity reaches current efficiency in theory21.5 times (27.74Ah) of institute's subfam. Spiraeoideae When, terminate electrolytic process, by the cathode sheets after electrolysis from CaCl2Taken out in fused salt and be placed in 1000ml mass fractions about 2% In dilute hydrochloric acid solution, high-speed stirred makes CaCl in pole piece in 1 hour2Dissolving, while disperse pole piece, obtain containing CNT/ SiC/ nano Si composites CaCl2With the dispersion liquid of hydrochloric acid；With pure water filtering and washing CNT/SiC/ nano Si composite woods Material, into filtrate without chlorion；Filter cake is placed in vacuum drying oven, carbon nanometer is obtained after drying moisture within 24 hours in 120 DEG C of drying Pipe/SiC/ nano Si composites.The scanning electron microscope diagram piece of the CNT of preparation/SiC/ nano Si composites is such as Shown in Fig. 2, X-ray diffraction spectrogram is as shown in Figure 3.
Wherein, Fig. 1 is CNT/SiO prepared by the embodiment of the present invention 22The SEM of porous cathode piece Picture；As seen from Figure 1, CNT and SiO2Powder is scattered than more uniform, and CNT does not have obvious agglomeration.Figure 2 is the scanning electron microscope diagram piece of CNT/SiC/ nano Si composites prepared by the embodiment of the present invention 2；Can by Fig. 2 See, CNT maintains its tubular morphology in product, the pattern of Si is mainly nano particle, size between 30~200nm, Nano Si is combined closely with CNT.
Embodiment 3：
3000g water is added in mixer batch can, is by 1000g carbon nanotube dusts (5~30nm of caliber) mass fraction 5% carbon nano tube dispersion liquid is poured into planetary stirring machine batch can, and high-speed stirred makes CNT in aqueous in 30 minutes It is uniformly dispersed；To adding 200gSiO in mixer batch can2Powder body material (SiO2Nano particle, 5~100nm of particle diameter), high-speed stirring Mixing 2 hours makes CNT and SiO2It is uniformly dispersed, obtains CNT/SiO2The pureed mixture of/water；The carbon that will be obtained is received Mitron/SiO2The pureed mixture of/water is placed in convection oven, in 150 DEG C of drying, 24 hours drying moisture, and uses mechanical crusher CNT/SiO that above-mentioned drying is obtained2Solid mixt is crushed；By the CNT/SiO after crushing2Powder hot pressing Machine temperature be 1080 DEG C, pressure be 20Mpa, the dwell time be 2 hours under the conditions of it is compressing be CNT/SiO2It is porous Block materials；By above-mentioned CNT/SiO2Porous blocks material is cut into the CNT/SiO of 50 × 50 × 10mm2It is porous Pole piece.With above-mentioned CNT/SiO2Porous pole piece as negative electrode, using graphite cake as anode, with 850 DEG C of CaCl2Fused salt conduct Electrolyte, it (is 300A/m relative to cathode area current density that 1.5A is applied between the negative electrode and anode2) electric current, will SiO2Electroreduction is nano Si；It is SiO in 100% complete electroreduction pole piece that electrolysis electricity reaches current efficiency in theory2Institute When 2 times (45.74Ah) of subfam. Spiraeoideae, terminate electrolytic process, by the cathode sheets after electrolysis from CaCl2Taken out in fused salt and be placed in In the dilute hydrochloric acid solution of 1000ml mass fractions about 2%, high-speed stirred makes CaCl in pole piece in 1 hour2Dissolving, while making pole piece point Dissipate, obtain containing CNT/SiC/ nano Si composites CaCl2With the dispersion liquid of hydrochloric acid；Received with pure water filtering and washing carbon Mitron/SiC/ nano Si composites, into filtrate without chlorion；Filter cake is placed in vacuum drying oven, is dried 24 hours at 120 DEG C CNT/SiC/ nano Si composites are obtained after drying moisture.
Contrast material：Micron Si powder body materials, D50=10 μm.
Li-ion batteries piles used by the present invention are filled with and the charge-discharge performance method of testing of material is：With embodiment 1~3 The CNT of preparation/SiC/ nano Sis or contrast material are active material, and Super-P carbon blacks are conductive agent, and PVDF is bonding Agent, is that solvent is sized mixing with 1-METHYLPYRROLIDONE after in mass ratio 8: 1: 1 is well mixed, and slurry is coated in the Copper Foil of 8 μ m-thicks On be made the pole piece of 1.0cm × 1.5cm, dry thickness needed for back roller is depressed into pole piece at 70 DEG C, dry 12h under 120 DEG C of vacuum, It is standby.It is that to electrode, the films of Celgard 2300 are barrier film with metal lithium sheet, 1mol/L LiPF6/EC+DEC+DMC (volume ratio 1: 1: 1) be electrolyte assembled battery.The charge-discharge performance of gained battery is tested with indigo plant electricity battery test system CT2001A testers. Charging/discharging voltage scope is 0.005~2.0V, charging and discharging currents density 80mA/g, tests the circulating battery capability retention of 10 weeks C10/C1。
Embodiment 1~3 prepare CNT/SiC/ nano Sis composite, contrast material (micron Si powder body materials, D50=10 μm) chemical property it is as shown in table 2.
Table 1：The experiment parameter of embodiment 1~3
Continued
Table 2：CNT/SiC/ nano Si composites prepared by embodiment 1~3, and comparative example material is used for lithium The chemical property of ion battery.
From table, compared with contrast material micron Si powders, CNT/SiC/ nano Sis prepared by embodiment 1~3 Not only efficiency is higher first for composite, and capability retention is higher, embodies more preferable cycle performance.Additionally, carbon nanometer The specific capacity of pipe/SiC/ nano Si composites also has obvious compared with commercialization graphite type material (300~360mAh/g) Advantage.
, but those skilled in the art once know basic creation although preferred embodiments of the present invention have been described Property concept, then can make other change and modification to these embodiments.So, appended claims are intended to be construed to include excellent Select embodiment and fall into having altered and changing for the scope of the invention.
Obviously, those skilled in the art can carry out various changes and modification without deviating from essence of the invention to the present invention God and scope.So, if these modifications of the invention and modification belong to the scope of the claims in the present invention and its equivalent technologies Within, then the present invention is also intended to comprising these changes and modification.

Claims (10)

1. the method that one kind prepares CNT/SiC/ nano Si composites, it is characterised in that comprise the following steps：
By CNT and SiO2Mixed, be made CNT/SiO2Porous pole piece；
Electroreduction CNT/SiO in fused salt2SiO in porous pole piece2CNT/SiC/ nano Sis are prepared to be combined Material.
2. method according to claim 1, it is characterised in that by CNT and SiO2Mixed, be made carbon nanometer Pipe/SiO2Porous pole piece is comprised the following steps：
A certain amount of water is added in mixer batch can, carbon nanotube dust or aqueous liquid dispersion containing CNT are poured into In mixer batch can, stirring makes CNT be uniformly dispersed in aqueous；
SiO is added in batch can2Powder body material, stirring makes CNT and SiO2It is uniformly dispersed, obtains CNT/SiO2/ water Pureed mixture；
CNT/the SiO that will be obtained2Compressing after pureed mixture drying moisture, the crushing of/water is CNT/SiO2 Porous blocks material；
By the CNT/SiO2Porous blocks material is further cut into the CNT/SiO being sized2Multiaperture electrode Piece.
3. method according to claim 1, it is characterised in that the CNT of the electroreduction in the fused salt/SiO2It is porous SiO in pole piece2CNT/SiC/ nano Si composites are prepared to comprise the following steps：
With the CNT/SiO2Porous pole piece as negative electrode, using graphite cake as anode, with CaCl2Fused salt is used as electrolysis Liquid, constant current is applied by between the negative electrode and anode, by CNT/SiO2SiO in porous cathode2Electrolysis is also Originally it was nano Si, a step part nano Si reacts to form SiC with CNT in the process；
By the negative electrode from CaCl2Taken out in fused salt, dispersed with stirring uses water filtering and washing in the aqueous solution, in vacuum drying oven drying CNT/SiC/ nano Si composites are obtained after moisture.
4. method according to claim 1, it is characterised in that the CNT is single wall or multi-walled carbon nano-tubes, pipe The span in footpath is 5~30nm.
5. method according to claim 1, it is characterised in that the SiO2Powder is nanoparticle powder, the value of particle diameter Scope is 5~100nm.
6. method according to claim 1, it is characterised in that the CNT and SiO2Mass ratio span It is 1: 199~1: 4.
7. method according to claim 1, it is characterised in that the span of the thickness of the porous pole piece is 2~ 10mm。
8. method according to claim 3, it is characterised in that the CaCl2The span of the temperature of fused salt be 850~ 900℃；
Preferably, the span of the current density of described applying constant current is 100~1000A/m2。
9. a kind of CNT/SiC/ nano Si composites, it is characterised in that by any described in claim 1~9 Method is prepared.
10. a kind of lithium ion battery, it is characterised in that the negative material of the lithium ion battery is by claim 1~8 CNT/SiC/ nano Si composites that any described method is prepared.
CN201611217641.8A 2016-12-26 2016-12-26 Prepare method, the composite and the lithium ion battery of CNT/SiC/ nano Si composites Pending CN106784695A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108717975A (en) * 2018-08-14 2018-10-30 银隆新能源股份有限公司 A kind of preparation method of negative material, battery and its negative material
CN115538155A (en) * 2022-10-17 2022-12-30 中南大学 Silicon carbide fiber composite electromagnetic wave-absorbing material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103107315A (en) * 2011-11-10 2013-05-15 北京有色金属研究总院 Nano silicon-carbon composite material and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103107315A (en) * 2011-11-10 2013-05-15 北京有色金属研究总院 Nano silicon-carbon composite material and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108717975A (en) * 2018-08-14 2018-10-30 银隆新能源股份有限公司 A kind of preparation method of negative material, battery and its negative material
CN115538155A (en) * 2022-10-17 2022-12-30 中南大学 Silicon carbide fiber composite electromagnetic wave-absorbing material and preparation method thereof
CN115538155B (en) * 2022-10-17 2023-08-22 中南大学 Silicon carbide fiber composite electromagnetic wave-absorbing material and preparation method thereof

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