CN103794769A - Preparation method of negative electrode material of lithium ion battery - Google Patents
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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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Abstract
The invention relates to a preparation method of a negative electrode material of a lithium ion battery. The preparation method comprises the following steps: adding a carbon nanometer pipe and cetyl trimethylammonium bromide to de-ionized water, performing sonic oscillation, adding ethanol and ammonia, and further performing sonic oscillation to obtain an alkaline dispersion of a carbon nanometer pipe; dropwise adding an ethanol solution of ethyl orthosilicate into the alkaline dispersion of the carbon nanometer pipe, and reacting at 30-60 DEG C to generate sedimentation; separating and washing the sedimentation by de-ionized water; placing in a reacting furnace, and sintering under inert atmosphere at 550-600 DEG C; mixing the product and zinc powder, placing in the reacting furnace, and sintering under inert atmosphere at 650-700 DEG C to obtain a sintering product; placing the sintering product in an acid solution, stirring for reacting at 30-60 DEG C, and separating and drying a solid phase product; and uniformly mixing the solid phase product with a carbon source and a disperse solvent, drying the mixture for concentration, placing the concentrated mixture in the reacting furnace, and sintering under inert atmosphere at 600-800 DEG C to obtain the 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)
1. a preparation method for lithium ion battery negative material, comprises 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, and concentrate drying is placed in reacting furnace, and under inert atmosphere, 600 ~ 800 ℃ of sintering, obtain CNTs/Si/C composite material.
2. the preparation method of lithium ion battery negative material as claimed in claim 1, is characterized in that, the mass fraction of this carbon nano-tube in this CNTs/Si/C composite material is 10% ~ 30%.
3. the preparation method of lithium ion battery negative material as claimed in claim 1, is characterized in that, the mass fraction of silicon in this CNTs/Si/C composite material is 50%-80%.
4. the preparation method of lithium ion battery negative material as claimed in claim 1, is characterized in that, the mass fraction of carbon in this CNTs/Si/C composite material is 10% ~ 30%.
5. the preparation method of lithium ion battery negative material as claimed in claim 1, is characterized in that, the mass ratio of this carbon nano-tube and softex kw is 1:10 ~ 1:30.
6. the preparation method of lithium ion battery negative material as claimed in claim 1, is characterized in that, the volume fraction of the ethanolic solution of this tetraethoxysilane is 4% ~ 10%.
7. the preparation method of lithium ion battery negative material as claimed in claim 1, is characterized in that, the rate of addition of the ethanolic solution of this tetraethoxysilane is 0.5 ml/min ~ 1 ml/min.
8. the preparation method of lithium ion battery negative material as claimed in claim 1, is characterized in that, this CNTs/SiO
2the mass ratio of composite material and zinc powder is 1:1 ~ 1:1.5.
9. the preparation method of lithium ion battery negative material as claimed in claim 1, is characterized in that, this acid solution is 0.1 ~ 1 mol/L HCl solution.
10. the preparation method of lithium ion battery negative material as claimed in claim 1, it is characterized in that, this carbon source is 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.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102214817A (en) * | 2010-04-09 | 2011-10-12 | 清华大学 | Carbon/silicon/carbon nano composite structure cathode material and preparation method thereof |
| CN103242684A (en) * | 2013-05-09 | 2013-08-14 | 中国科学院深圳先进技术研究院 | Silicon dioxide coated carbon nano-tubes and preparation method thereof |
| CN103367726A (en) * | 2013-07-10 | 2013-10-23 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material and preparation method thereof as well as lithium ion battery |
| CN103474666A (en) * | 2013-07-23 | 2013-12-25 | 江苏华东锂电技术研究院有限公司 | Preparation method for negative electrode active material of lithium ion battery |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100576610C (en) * | 2006-12-22 | 2009-12-30 | 比亚迪股份有限公司 | A kind of silicon composite and preparation method thereof that contains |
| CN101439972B (en) * | 2007-11-21 | 2013-01-09 | 比亚迪股份有限公司 | Silicon-carbon composite material, preparation thereof, battery cathode and lithium ionic cell |
| CN102008968B (en) * | 2010-11-11 | 2012-11-07 | 太原理工大学 | Solid superacid mesoporous material and preparation method thereof |
| CN103794769B (en) * | 2014-02-18 | 2016-05-04 | 江苏华东锂电技术研究院有限公司 | The preparation method of lithium ion battery negative material |
-
2014
- 2014-02-18 CN CN201410055120.1A patent/CN103794769B/en active Active
-
2015
- 2015-01-19 WO PCT/CN2015/070977 patent/WO2015124049A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102214817A (en) * | 2010-04-09 | 2011-10-12 | 清华大学 | Carbon/silicon/carbon nano composite structure cathode material and preparation method thereof |
| CN103242684A (en) * | 2013-05-09 | 2013-08-14 | 中国科学院深圳先进技术研究院 | Silicon dioxide coated carbon nano-tubes and preparation method thereof |
| CN103367726A (en) * | 2013-07-10 | 2013-10-23 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material and preparation method thereof as well as lithium ion battery |
| CN103474666A (en) * | 2013-07-23 | 2013-12-25 | 江苏华东锂电技术研究院有限公司 | Preparation method for negative electrode active material of lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| KUNLUN DING,ETAL.: ""A simple route to coat mesoporous SiO2 layer on carbon nanotubes"", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
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