CN103794769A - Preparation method of negative electrode material of lithium ion battery - Google Patents
Preparation method of negative electrode material of lithium ion battery Download PDFInfo
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- CN103794769A CN103794769A CN201410055120.1A CN201410055120A CN103794769A CN 103794769 A CN103794769 A CN 103794769A CN 201410055120 A CN201410055120 A CN 201410055120A CN 103794769 A CN103794769 A CN 103794769A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000007773 negative electrode material Substances 0.000 title claims abstract 12
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 103
- 239000002131 composite material Substances 0.000 claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000007790 solid phase Substances 0.000 claims abstract 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 6
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 29
- 239000000463 material Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
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- 230000010355 oscillation Effects 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
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- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
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- 239000002210 silicon-based material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
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- 230000002427 irreversible effect Effects 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H01M4/62—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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- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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Abstract
本发明涉及一种锂离子电池负极材料的制备方法，将碳纳米管与十六烷基三甲基溴化铵加入去离子水中，超声振荡，再加入乙醇和氨水并进一步超声振荡，得到碳纳米管的碱性分散液；将正硅酸乙酯的乙醇溶液滴加到该碳纳米管的碱性分散液中，在30~60℃反应，产生沉淀；分离并用去离子水洗涤该沉淀；置于反应炉内，在惰性气氛下550~600℃烧结；与锌粉混合，置于反应炉内，在惰性气氛下650~700℃烧结，得到烧结产物；放入酸溶液中，在30~60℃搅拌进行反应，分离并干燥固相产物；以及与碳源和分散溶剂混合均匀，浓缩干燥后置于反应炉内，在惰性气氛下600~800℃烧结，得到CNTs/Si/C复合材料。
The invention relates to a preparation method of a negative electrode material of a lithium ion battery. Carbon nanotubes and cetyltrimethylammonium bromide are added to deionized water, ultrasonically oscillated, and then ethanol and ammonia water are added and further ultrasonically oscillated to obtain carbon nanotubes. Alkaline dispersion of carbon nanotubes; Add the ethanol solution of tetraethyl orthosilicate dropwise to the alkaline dispersion of carbon nanotubes, react at 30-60°C to produce a precipitate; separate and wash the precipitate with deionized water; place Sinter in a reaction furnace at 550~600°C under an inert atmosphere; mix with zinc powder, place in a reaction furnace, and sinter at 650~700°C under an inert atmosphere to obtain a sintered product; put it into an acid solution, heat it at 30~60 Stir at ℃ to react, separate and dry the solid phase product; and mix with carbon source and dispersion solvent evenly, concentrate and dry, place in a reaction furnace, and sinter at 600~800℃ under an inert atmosphere to obtain a CNTs/Si/C composite material.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, relate in particular to a kind of preparation method of Silicon Based Anode Materials for Lithium-Ion Batteries.
Background technology
Commercially produce LiCoO from Sony in 1991
2/ C rocking chair battery, that rechargeable lithium ion batteries has become is portable, the important component part of amusement, calculating and telecommunication apparatus, indispensable in the rich informationalized mobile devices such as field camera, MP4 player, notebook computer and mobile phone.Meanwhile, be subject to the pressure of petroleum reserves and environmental protection, countries in the world are all at competitively Developing Hybrid Vehicle Industry and pure electric automobile in recent years, and will progressively replace traditional fuel-engined vehicle, to reduce the pollution of vehicle exhaust to environment.Lithium-ion electric pool technology advanced and in the application in electric automobile field, has excited the research boom in global range.
At present, business-like lithium ion battery adopts graphite as negative material, and its source is abundant, cheap, stable operating voltage, but theoretical embedding lithium capacity only has 372 mAh/g.Up to now, in negative material, the theoretical capacity of silicon is the highest, as Li and Si alloying formation Li
4.4when Si, theoretical capacity is 4212 mAh/g, much larger than the theoretical capacity of graphite; Meanwhile, silicon is safer more reliable than graphite cathode, so worldwide studied widely.But also there is the shortcoming of self in silicium cathode material: (1) silicium cathode in charge and discharge process with larger change in volume (volumetric expansion is up to 300%), strong stress causes silicon grain generation efflorescence, and then separate with conductive agent, peel off from collector, thereby cause sizable irreversible capacity that discharges first, reduced cycle performance.(2) silicon materials conductivity is poor, and this has also affected its cycle performance under high current charge-discharge.
For solving the problem of silicium cathode material expansion efflorescence and poorly conductive, current taked method is mainly prepares One Dimension Silicon nano wire or two-dimentional silicon nano thin-film.But these two kinds of methods need large-scale, expensive equipment, and preparation technology is numerous and diverse, is difficult to realize commercial application.
Summary of the invention
In view of this, the necessary preparation method that a kind of silica-based lithium ion battery negative material with better cycle performance and applicable industrial applications is provided.
A kind of preparation method of lithium ion battery negative material, comprise the following steps: carbon nano-tube and softex kw are added in deionized water, sonic oscillation, then add ethanol and ammoniacal liquor further sonic oscillation, obtain the alkaline dispersion liquid of carbon nano-tube; The ethanolic solution of tetraethoxysilane is added drop-wise in the alkaline dispersion liquid of this carbon nano-tube, 30 ~ 60 ℃ of reactions, produces precipitation; Separate and wash this precipitation with deionized water, obtaining CNTs/CTAB/SiO after dry
2composite material; By this CNTs/CTAB/SiO
2composite material is placed in reacting furnace, and under inert atmosphere, 550 ~ 600 ℃ of sintering, obtain CNTs/SiO
2composite material; By this CNTs/SiO
2composite material mixes with zinc powder, is placed in reacting furnace, and under inert atmosphere, 650 ~ 700 ℃ of sintering, obtain sintered product; This sintered product is put into acid solution, react 30 ~ 60 ℃ of stirrings, separate and dry solid product, obtain CNTs/Si composite material; And this CNTs/Si composite material is mixed with carbon source and dispersion solvent, concentrate drying is placed in reacting furnace, and under inert atmosphere, 600 ~ 800 ℃ of sintering, obtain CNTs/Si/C composite material.
The present invention is directed to silicium cathode poorly conductive and in charge and discharge process, can produce the problem of serious bulk effect, a kind of preparation method of negative material has been proposed, first generate nanometer grade silica coating layer in carbon nano tube surface, then surperficial silicon dioxide is reduced to silicon, by carbon coating technology, obtain a kind of CNTs/Si/C multilayer coating structure composite material afterwards.During using this composite material as lithium ion battery negative material, silicon is sandwiched between two kinds of material with carbon elements, and the effect that carbon nano-tube and carbon play resilient coating suppresses the expansion efflorescence of silicon in charge and discharge process.Meanwhile, utilize the satisfactory electrical conductivity of external coating carbon and the three-dimensional conductive network of internal layer carbon nano-tube formation can increase the conductivity of silicon materials.Therefore, the cycle performance of silicium cathode material is improved.Production technology of the present invention is simple, does not use complex device, easily realizes suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the TEM figure of the lithium ion battery negative material of the embodiment of the present invention 1.
Fig. 2 is the XRD figure of the lithium ion battery negative material of the embodiment of the present invention 1.
Fig. 3 is lithium ion battery negative material and the cycle performance contrast of pure silicon powder in battery of the embodiment of the present invention 1.
Following embodiment further illustrates the present invention in connection with above-mentioned accompanying drawing.
Embodiment
Below in conjunction with the accompanying drawings and the specific embodiments the preparation method of lithium ion battery negative material provided by the invention is described in further detail.
Embodiment of the present invention provides a kind of preparation method of lithium ion battery negative material, comprises the following steps:
S1, adds carbon nano-tube (CNTs) and softex kw (CTAB) in deionized water, sonic oscillation, then add ethanol and ammoniacal liquor further sonic oscillation, obtain the alkaline dispersion liquid of CNTs;
S2, is added drop-wise to the ethanolic solution of tetraethoxysilane in the alkaline dispersion liquid of this CNTs, 30 ~ 60 ℃ of reactions, produces precipitation;
S3, separates and washs this precipitation with deionized water, obtains CNTs/CTAB/SiO after dry
2composite material;
S4, by this CNTs/CTAB/SiO
2composite material is placed in reacting furnace, and under inert atmosphere, 550 ~ 600 ℃ of sintering, obtain CNTs/SiO
2composite material;
S5, by this CNTs/SiO
2composite material mixes with zinc powder, is placed in reacting furnace, and under inert atmosphere, 650 ~ 700 ℃ of sintering, obtain sintered product;
S6, puts into acid solution by this sintered product, reacts 30 ~ 60 ℃ of stirrings, separates and dry solid product, obtains CNTs/Si composite material;
S7, mixes this CNTs/Si composite material with carbon source and dispersion solvent, concentrate drying is placed in reacting furnace, and under inert atmosphere, 600 ~ 800 ℃ of sintering, obtain CNTs/Si/C composite material.
In this step S1, the time of this sonic oscillation can be 1 ~ 4 hour.This CNTs can be Single Walled Carbon Nanotube or the multi-walled carbon nano-tubes of diameter 10 ~ 40 nm.The mass ratio of this CNTs and CTAB can be 1:10 ~ 1:30.In the dicyandiamide solution of this alkalescence dispersion liquid, the volume fraction of water can be 20 ~ 40%, and the volume fraction of ethanol can be 60% ~ 80%, and the volume fraction of ammoniacal liquor can be 1 ~ 2%.The amount of this CNTs adding is by the cubage of CNTs in end product CNTs/Si/C composite material, and the mass fraction of CNTs in CNTs/Si/C composite material can be 10% ~ 30%.In the alkaline dispersion liquid of CNTs, CTAB is coated on carbon nano tube surface.
In this step S2, particularly, when alkaline dispersion liquid that can this CNTs of mechanical agitation, drip, can be 12 ~ 18 hours the reaction time of 30 ~ 60 ℃.The volume fraction of the ethanolic solution of this tetraethoxysilane can be 4% ~ 10%.The addition of this tetraethoxysilane is by the cubage of Si in end product CNTs/Si/C composite material, and the mass fraction of Si in CNTs/Si/C composite material can be 50%-80%.The rate of addition of the ethanolic solution of this tetraethoxysilane can be 0.5 ml/min ~ 1 ml/min.
In this step S3, particularly, can pass through centrifuge centrifugation, take out lower sediment, and use deionized water cyclic washing, until filtrate is neutral, subsequently this precipitation is put into 80 ~ 120 ℃ of vacuum drying chambers and dried 12 ~ 24 hours, obtain this CNTs/CTAB/SiO
2composite material.This centrifuge speed can be 4000 r/min ~ 4500 r/min, and centrifugation time can be 10 minutes ~ 15 minutes.At this CNTs/CTAB/SiO
2in composite material, CTAB is connected silicon dioxide with carbon nano-tube, and silicon dioxide is coated on carbon nano tube surface by CTAB.
In this step S4, this sintering time can be 6 ~ 8 hours.At this CNTs/SiO
2in composite material, silicon dioxide is directly coated on carbon nano tube surface.
In this step S5, this sintering time can be 1 ~ 2 hour.This CNTs/SiO
2the mass ratio of composite material and zinc powder can be 1:1 ~ 1:1.5.
In this step S6, the concentration of this acid solution can be 0.1 ~ 1 mol/L, for example, can be 0.1 ~ 1 mol/L HCl solution, and the stirring reaction time can be 1 ~ 2 hour.This separation dry solid product can be specifically to use deionized water cyclic washing, until filtrate is neutral, then puts into 80 ~ 120 ℃ of vacuum drying chambers and dry 12 ~ 24 hours.In this CNTs/Si composite material, silicon is directly coated on carbon nano tube surface.
In this step S7, this sintering time can be 4 ~ 6 hours.This carbon source can be one or more in glucose, sucrose, petroleum coke, phenolic resins, polyvinyl alcohol, polymethyl methacrylate, polypropylene, PLA, starch, polyarylether, polyester, polyurethane, polyarylate, polyether-ketone, polyether sulfone and polyimides.The mass fraction of the RESEARCH OF PYROCARBON that selected carbon source generates in CNTs/Si/C composite material can be 10% ~ 30%.This dispersion solvent can be one or more in methyl alcohol, ethanol, water, acetone, ethyl acetate, chloroform, toluene, ether, benzinum, dimethyl formamide, dimethylacetylamide, N-methyl pyrrole Lip river alkane ketone and dimethyl sulfoxide (DMSO), and addition is 50-100 times of this CNTs/Si composite material quality.In this CNTs/Si/C composite material, silicon face is coated carbon-coating further, is carbon nano-tube thereby form inside, and centre is silicon layer, the composite material that outside is carbon-coating.By adjusting carbon nano-tube, silicon and the mass fraction of carbon in CNTs/Si/C composite material, can control the thickness of silicon layer, make the carbon nano-tube of both sides and carbon-coating can effectively suppress the change in volume of silicon in charge and discharge process.
At this step S4, in S5 and S7, this inert atmosphere can be nitrogen or argon gas.
The preparation method of the described negative material by the embodiment of the present invention, can first generate nanometer grade silica coating layer in carbon nano tube surface, then surperficial silicon dioxide is reduced to silicon, by carbon coating technology, obtains a kind of CNTs/Si/C multilayer coating structure composite material afterwards.During using this composite material as lithium ion battery negative material, silicon is sandwiched between two kinds of material with carbon elements, and the effect that carbon nano-tube and carbon play resilient coating suppresses the expansion efflorescence of silicon in charge and discharge process.Meanwhile, utilize the satisfactory electrical conductivity of external coating carbon and the three-dimensional conductive network of internal layer carbon nano-tube formation can increase the conductivity of silicon materials.The present invention is without preparing silicon nanowires by complicated technique, but can obtain the effect similar or more excellent to silicon nanowires, and production technology is simple, easily realizes suitability for industrialized production.
Embodiment 1
S1, takes 200 mg CNTs and 6 g CTAB, joins in 60 ml deionized waters, and sonic oscillation 1 hour, adds 120 ml absolute ethyl alcohols, continues after ultrasonic 1 hour, then adds 5 ml ammoniacal liquor, obtains the alkaline dispersion liquid of CNTs.
S2, dose volume mark is the ethanolic solution of 6% tetraethoxysilane, the ethanolic solution of 100 these tetraethoxysilanes of ml is slowly added drop-wise under mechanical agitation in the alkaline dispersion liquid of this CNTs, rate of addition is 1 ml/min, after dropwising, control 40 ℃ of reaction temperatures, continue reaction 18 hours.
S3, by centrifuge with the rotating speed of 4000 r/min centrifugal 15 minutes for step S2 products therefrom, takes out lower sediment, by precipitate with deionized water cyclic washing, until filtrate is neutral, subsequently precipitation is put into 80 ℃ of vacuum drying chambers and dried 24 hours, obtain CNTs/CTAB/SiO
2composite material.
S4, by this CNTs/CTAB/SiO
2composite material moves into the tubular react furnace of nitrogen protection, and 550 ℃ of sintering 8 hours, obtain CNTs/SiO
2composite material.
S5, by this CNTs/SiO
2composite material and 2.5 g zinc powders fully mix in the tubular react furnace of rear immigration nitrogen protection, 650 sintering 2 hours.
S6, processes step S5 gained solid 1 hour with 60 ℃ of 0.1mol/L HCl solution, uses deionized water cyclic washing, until filtrate is neutral, then puts into 80 ℃ of vacuum drying chambers and dries 24 hours, obtains CNTs/Si composite material.
S7, is placed in container by this CNTs/Si composite material, adds 0.55g glucose and 80g ethanol, stirs 2 hours to mixing; By dry gained mixture reduced pressure concentration, ethanol reclaims and reuses, and solid product moves in the tubular react furnace of nitrogen protection, and 700 ℃ of sintering 6 hours, obtain this CNTs/Si/C composite material.
The CNTs/Si/C composite material obtaining is by transmission electron microscope observing, and TEM photo as shown in Figure 1.Refer to Fig. 2, this CNTs/Si/C composite material is carried out to XRD test, the characteristic peak of C, CNTs and Si all marks in Fig. 2.The CNTs/Si/C composite material of embodiment 1 is assembled to lithium ion battery as negative active core-shell material, and just very lithium metal, carries out charge-discharge performance test.And assemble control cell, difference only adopts pure silicon powder at negative active core-shell material, carries out under the same conditions charge-discharge performance test.The test result of two kinds of batteries as shown in Figure 3, although can see that the battery of pure silicon powder has higher specific capacity in the time of initial charge, but along with the increase of cycle-index sharp-decay.Although and the initial charge capacity of CNTs/Si/C composite material is lower, cyclical stability is improved largely than pure silicon powder, after circulation repeatedly, still have higher capability retention.
Embodiment 2
S1, takes 200 mg CNTs and 4 g CTAB, joins in 70 ml deionized waters, and sonic oscillation 2 hours, adds 100 ml absolute ethyl alcohols, continues after ultrasonic 2 hours, then adds 4 ml ammoniacal liquor, obtains the alkaline dispersion liquid of CNTs.
S2, dose volume mark is the ethanolic solution of 10% tetraethoxysilane, the ethanolic solution of 40 these tetraethoxysilanes of ml is slowly added drop-wise under mechanical agitation in the alkaline dispersion liquid of this CNTs, rate of addition is 0.5 ml/min, after dropwising, control 60 ℃ of reaction temperatures, continue reaction 12 hours.
S3, by centrifuge with the rotating speed of 4500 r/min centrifugal 10 minutes for step S2 products therefrom, takes out lower sediment, by precipitate with deionized water cyclic washing, until filtrate is neutral, subsequently precipitation is put into 120 ℃ of vacuum drying chambers and dried 12 hours, obtain CNTs/CTAB/SiO
2composite material.
S4, by this CNTs/CTAB/SiO
2composite material moves into the tubular react furnace of nitrogen protection, and 600 ℃ of sintering 6 hours, obtain CNTs/SiO
2composite material.
S5, by this CNTs/SiO
2composite material and 2g zinc powder fully mix in the tubular react furnace of rear immigration nitrogen protection, 685 sintering 2 hours.
S6, processes step S5 gained solid 2 hours with 30 ℃ of 0.5mol/L HCl solution, uses deionized water cyclic washing, until filtrate is neutral, then puts into 120 ℃ of vacuum drying chambers and dries 12 hours, obtains CNTs/Si composite material.
S7, is placed in container by this CNTs/Si composite material, adds 0.37g polyvinyl alcohol and 60g chloroform, stirs 3 hours to mixing; By dry gained mixture reduced pressure concentration, chloroform reclaims and reuses, and solid product moves in the tubular react furnace of nitrogen protection, and 800 ℃ of sintering 4 hours, obtain this CNTs/Si/C composite material.
In addition, those skilled in the art also can do other and change in spirit of the present invention, and certainly, the variation that these do according to spirit of the present invention, within all should being included in the present invention's scope required for protection.
Claims (10)
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