CN105006549A - Carbon-silicon composite lithium ion battery cathode material and preparation method thereof - Google Patents
Carbon-silicon composite lithium ion battery cathode material and preparation method thereof Download PDFInfo
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Abstract
A carbon-silicon composite lithium ion battery cathode material and its preparation method are disclosed. Si which is used as an inner core is tightly coated with a SiO2 layer, and a hollow layer is arranged between the SiO2 layer and the outermost C coating layer. The inner core Si accounts for 30-70 wt% of mass of the composite material. The hollow layer is obtained by etching the SiO2 part of the middle layer on the synthesized Si/SiO2/C composite material. When used as a lithium ion battery cathode material in the field of electrochemical application, the material provided by the invention has advantages of high cyclic stability and high coulombic efficiency. There is less environmental pollution during the experimental process. The technology is easy to control and is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to high coulomb efficiency, long circulation life field of lithium ion battery, specifically refer to a kind of Si/SiO
2/ C part hollow composite cathode material of lithium ion battery and preparation method thereof.
Background technology
Since entering into 21 century, low-carbon (LC) becomes the synonym of environmental protection, social development and environmental protection contradiction day by day fierce.Along with the exhaustion of the conventional petroleum energy, people are more and more stronger to the demand of new forms of energy, and in view of the conventional petroleum energy is to the pollution of environment, the environmental requirement of people to new forms of energy is more and more higher.Lithium is all metallic element Plays electrode potentials the most negative (-3.04V) and the metallic element of quality the lightest (M=6.941), and therefore, lithium battery has the features such as the high and energy density of open circuit voltage is large.Lithium rechargeable battery becomes the study hotspot of novel energy with advantages such as its environmental protection low stain, cost is low, energy density is large, long service life, and is expected to the core technology becoming following electric automobile.
For lithium ion battery, the performance of positive and negative pole material directly can determine the performance of battery.In negative material.Elemental silicon as negative material because having very high theoretical specific capacity (Trill J H., Tao C.Q., Winter M., et al.J.Solid State Electrochem., 2011,15:349-356.) receive increasing concern, it is considered to most possibly one of material substituting graphite cathode, but silicon-based anode is not but slowly put in commercialization use.This is because silicon can produce the volumetric expansion/contraction of about 300% in embedding/de-lithium process, huge change in volume can cause the efflorescence of silicon electrode to peel off, make to lose electrical contact between silicon grain and between silicon and collector, the specific capacity of electrode sharply declines even complete failure (Szczech J R, Jin S.Energ.Environ.Sci., 201l, 4:56-72.).Usually, the reversible specific capacity of common pure silicon negative pole just can drop to almost nil (Li H, Huang X J, Chen L Q.Electrochemical and Solid-State Letters from 3000mAh/g in 5 circulations, 1999,2 (11): 547-549.).
At present, what study often is with the composite material of material with carbon element as silicium cathode, and on the one hand, the conductivity of material with carbon element is better, can make up the shortcoming of silicon materials poorly conductive, improves the conductivity of silicon based anode material; On the other hand, the change in volume of material with carbon element in doff lithium process very little (<10%), and material with carbon element has good lubrification usually, the carbon cushioning frame be made up of it can effectively suppress/alleviate the stereomutation of silicon in embedding/de-lithium process, electrode structure and conductivity are well maintained, and then the cyclical stability of silica-base material is improved.In addition, material with carbon element itself also has the activity of reversible embedding/de-lithium, and the specific capacity that can increase composite material like this can accelerate again lithium ion transmission rate in the composite.As Hu Yong Sheng group uses glucose as carbon source, use hydro thermal method at nano silicon particles outer cladding SiO
x/ C layer, defines Si/SiO
xthe nucleocapsid structure of/C, at 150mAg
-160 its capacity of circle that circulate under current density can maintain 1100mAhg
-1, and pure silicon negative material of comparing, cyclical stability and large current charge performance increase (Hu, Y.S., Rezan, D.C., Titirici, M.M., etal.Angew.Chem.Int.Ed.2008,47,1645 – 1649.).Nano silicon particles is added polyvinylidene fluoride 1-METHYLPYRROLIDONE and stirs final vacuum drying in 24 hours by Xu Yu Hong group, then the coated carbonized film of silicon face is made by pyrolysis, define the nucleocapsid structure of agraphitic carbon coated Si, after its 30 circle, capacity is 1290mAhg
-1capability retention is 97% (Xu, Y.H., Yin, G.P., Ma, Y.L., Zuo, P.J., Cheng, X.Q.J.Mater.Chem., 2010,20,3216 – 3220.).Si/C compound yolk/eggshell type structure has been prepared by Cui Yi group, and 1000 circle capability retentions reach 74%, and coulombic efficiency can reach 99.84% (Liu N., Wu H., McDowell M.T., Yao Y., Wang, C.M.Cui, Y., Nano Lett.2012,12,3315-3321).Si/SiO has prepared in Park Soojin group
xits cycle performance of core-shell structure nano wire and high rate performance all improve a lot (Lim, K.W., Lee, J.I., Yang, J., et al.ACS Appl.Mater.Interfaces2014,6,6340-6345).
From the above mentioned, although can find out that existing silicon/carbon complex method is a lot, Si/SiO is had
x/ C compound, Si/C compound, Si/SiO
xcompound, Si/C compound yolk/eggshell type structure, this several composite construction, the SiO outside Si
xor C layer is for which providing the effect of certain constraint change in volume, Si/C compound yolk/eggshell type structure then for which providing certain expansion space, can improve the cycle performance of silicium cathode material.
Summary of the invention
The object of this invention is to provide a kind of Si/SiO
2/ C part hollow composite cathode material of lithium ion battery, makes it have high cyclical stability, high coulombic efficiency; To promote that Si-C composite material is as negative material good industrialized application in lithium ion battery.
Another object of the present invention is to prepare the simple preparation method that effectively can realize above-mentioned material performance.
Technical scheme of the present invention is as follows
Si/SiO
2/ C part hollow composite cathode material of lithium ion battery is that its intimate is coated with one deck SiO using Si as kernel
2layer, SiO
2be voided layer between layer and outermost layer C coating layer; The mass percent scope that kernel Si accounts for described composite material is 30% ~ 70%.
Described voided layer is at synthesized Si/SiO
2in/C composite, by intermediate layer SiO
2partial etching obtains; Described Si/SiO
2/ C composite is that kernel Si is coated with SiO outward successively
2layer and C layer.
Si/SiO of the present invention
2the preparation method of/C part hollow composite cathode material of lithium ion battery, comprise the following steps: Si joins ultrasonic disperse in ammoniacal liquor, deionized water and absolute ethyl alcohol mixed solution, add tetraethoxysilane again, after stirring hydrolysis, with deionized water and absolute ethyl alcohol centrifuge washing, drying, obtains Si/SiO
2composite construction product; By Si/SiO
2in lower 650 DEG C ~ 850 DEG C carbonizations of Ar atmosphere after composite construction product and Kynoar, 1-METHYLPYRROLIDONE stir; By products therefrom Si/SiO after carbonization
2it is 0.5 ~ 4Mol/L HF that/C composite puts into concentration, to SiO
2centrifugal drying after partial etching, products therefrom is Si/SiO
2/ C part hollow composite cathode material of lithium ion battery; Si accounts for Si/SiO
2/ C part hollow composite construction mass percent scope is 30% ~ 70%; Described Si/SiO
2composite construction product and Kynoar mass ratio range are 10:1 ~ 4:1.
Described ammoniacal liquor and deionized water volume ratio scope are 1:5 ~ 1:2.Described ammoniacal liquor mass percent is 25% ~ 30%.
Described deionized water and absolute ethyl alcohol volume ratio scope are 1:5 ~ 1:10.
Deionized water and tetraethoxysilane volume ratio scope are 5:1 ~ 1:1.
Described Kynoar and 1-METHYLPYRROLIDONE mass ratio range are 1:20 ~ 1:10.
Polyethylene of dispersing agent pyrrolidones is added and Si mass ratio range is 1:10 ~ 1:1. in ultrasonic disperse process.
The preferred preparation method of the present invention is: described ammoniacal liquor and deionized water and absolute ethyl alcohol volume ratio scope are 1: 3 ~ 4: 20 ~ 25; Si and polyvinylpyrrolidone mass ratio are 3.5 ~ 4.5:1; Deionized water and tetraethoxysilane volume ratio are 1.5 ~ 2.5:1; Si/SiO
2composite construction and Kynoar mass ratio are 5.5 ~ 6.5:1; Kynoar and 1-METHYLPYRROLIDONE mass ratio are 1:16 ~ 17; Carburizing temperature is 650 DEG C ~ 700 DEG C; HF acid concentration is 0.5 ~ 1Mol/L.
Preferred version of the present invention also comprises kernel Si and accounts for Si/SiO
2/ C part hollow composite construction mass percent scope is 60% ~ 70%.
Inventor successfully synthesizes Si/SiO first through repeatedly testing and exploring
2/ C part hollow structural composite material.Material of the present invention is at Si outer cladding SiO
2coated C layer, then etch away sections SiO again after layer
2form Si/SiO
2/ C part hollow composite construction, namely reaches the SiO outside Si
2layer is for which providing the effect of certain constraint change in volume, Si/SiO
2and the voided layer between C provides certain expansion space for Si again, thus provide duplicate protection for Si.Gained Si/SiO of the present invention
2it is 707mgh/g that/C part hollow composite structure anode material cell 430 encloses rear specific capacity, and capability retention is 64.3%, and coulombic efficiency is 100% substantially entirely, with Si/SiO prepared by described Hu Yong Sheng group before
xthe nucleocapsid structure of/C, and the nucleocapsid structure lithium ion battery of agraphitic carbon coated Si prepared by Xu Yu Hong group, the cycle performances of 60 and 30 circles compare and improve a lot.Compared with the Si/C compound yolk/eggshell type structural behaviour prepared with Cui Yi group, although specific capacity is lower, gained Si/SiO of the present invention
2/ C part hollow composite structure anode material cell is at the coulombic efficiency of front 100 circles all higher than 100%, and Cui Yi group gained battery coulombic efficiency is a little less than 100%.Gao Lian group, prepared silicon core is coated by silica shell, there is certain space between the two, test specific capacity in experiment and can remain on 520-750mAh/g (high Lian Song's Sun Zhuan snowy peak Zhang Peng after 20 repeated charge-discharge cycles, silica-based lithium ion battery cathode material and its preparation method, number of patent application: 201310430247.2), and whether the cycle performance after 20 repeated charge can keep stable, unknown.And Si/SiO prepared by the present invention
2/ C part hollow composite construction in contrast specific capacity still can remain on 900-1000mAh/g after 20 repeated charge-discharge cycles, and the experiment of accompanying drawing part of the present invention also fully shows that cyclical stability of the present invention increases.
The above-mentioned Si/SiO shown prepared by the present invention
2/ C part hollow composite construction is used as lithium ion battery negative material and has higher electric discharge specific energy, good cycle, long service life, and this preparation method needs the equipment of employing simple, reaction condition is simple, environmental friendliness, production cost is low, is suitable for large-scale industrial production.Therefore, material of the present invention, as the electrochemical applications of lithium ion battery negative material, has the advantage of high cyclical stability and high coulomb efficiency.
Accompanying drawing explanation
Fig. 1 (a), (b) is respectively Si/SiO prepared by the present invention
2and Si/SiO
2the X ray diffracting spectrum (XRD) of/C after etching; The diffraction maximum of silicon is obvious as seen from the figure, SiO
2amorphous bag obvious, quantitatively calculated by XRD and etching rear amorphous SiO
2content decline to some extent, but still there is SiO
2amorphous bag, shows to there is SiO in products therefrom
2amorphous phase.
Fig. 2 (a), the transmission electron microscope photo that (b) is commodity Si and high power transmission electron microscope photo.Fig. 2 (c), the Si/SiO that (d) is prepared for the embodiment of the present invention 1
2sample transmission electron micrograph and high power transmission electron microscope photo; Can find out that the size of commodity Si is between 20-100nm and Si particle outer rim is smooth by Fig. 2 (a), can find out that the crystallinity of commodity Si is good by Fig. 2 (b), the outer of Si particle does not almost have amorphous layer.Through SiO
2coatedly can find out that Si nano particle forms the thick coating layer of 5-10nm outward by Fig. 2 (c).Fig. 2 (d) can find out the SiO found out clearly outside Si nano particle
2coating layer is amorphous, shows successfully to obtain Si/SiO
2nucleocapsid structure sample, consistent with XRD data.
Fig. 3 (a), (b) is respectively Si/SiO prepared by the embodiment of the present invention 2
2by Fig. 3 (a), the transmission electron microscope photo of/C part hollow composite construction sample and structural representation thereof, can find out that products therefrom is the nucleocapsid structure with hollow space, namely products therefrom is the Si/SiO shown in Fig. 3 (b)
2the hollow@C-structure of@;
Fig. 4,5 is the Si/SiO prepared in the embodiment of the present invention 2
2the chemical property figure of/C part hollow composite construction electrode material.Fig. 4 is the cyclic voltammogram that its 3-7 encloses, because its coincidence better shows the good cyclical stability of battery.Fig. 5 is the Si/SiO of preparation in the embodiment of the present invention 2
2the simple charging and discharging curve of/C part hollow composite construction electrode material, battery operation 430 encloses rear specific capacity is as seen from the figure 707mgh/g, and capability retention is 64.3%, and coulombic efficiency is 100% substantially entirely.Show Si/SiO prepared by the present invention
2/ C part hollow composite construction is used as lithium ion battery negative material and has higher electric discharge specific energy, good cycle, long service life, and this preparation method needs the equipment of employing simple, reaction condition is simple, environmental friendliness, production cost is low, is suitable for large-scale industrial production.
Embodiment
Be intended to further illustrate the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1
Si/SiO of the present invention
2the preparation of/C semi-hollow composite construction
Commodity Si to be added ammoniacal liquor, deionized water and absolute ethyl alcohol volume ratio be in the mixed solution of 1:5:50 and add ultrasonic 10 minutes of the PVP (polyvinylpyrrolidone) of Si quality 1/10, then add and the TEOS of deionized water volume ratio 5:1 (tetraethoxysilane).Stir 1h, with deionized water and absolute ethyl alcohol centrifuge washing three times, be placed on 60 DEG C of dryings in drying box, obtain Si/SiO
2composite construction product, Fig. 2 (c), (d) is the Si/SiO originally executing example preparation
2sample transmission electron micrograph and high power transmission electron microscope photo.By Si/SiO
2sample and mass ratio are after the PVDF (Kynoar) of 10:1 mixes, add PVDF (1-METHYLPYRROLIDONE) quality 20 times NMP stir after in the lower 850 DEG C of carbonization 2h of Ar atmosphere.After HF products therefrom being put into 0.5Mol/L etches 1h, with deionized water and absolute ethyl alcohol centrifuge washing five times, be placed in 60 DEG C of dryings, products therefrom is Si/SiO
2/ C semi-hollow composite construction.Si accounts for Si/SiO
2/ C part hollow composite construction mass percent scope is 30%.
Embodiment 2
Commodity Si to be added ammoniacal liquor, deionized water and absolute ethyl alcohol volume ratio be in the mixed solution of 1:3.18:23.56 and add ultrasonic 10 minutes of the PVP of Si quality 1/5, then add the TEOS with deionized water volume ratio 2:1.Stir 1h, with deionized water and absolute ethyl alcohol centrifuge washing three times, be placed on 60 DEG C of dryings in drying box, obtain Si/SiO
2composite construction product, by Si/SiO
2sample and mass ratio are after the PVDF of 6:1 mixes, add PVDF quality 20 times NMP stir after in the lower 650 DEG C of carbonization 2h of Ar atmosphere.After HF products therefrom being put into 0.5Mol/L etches 1h, with deionized water and absolute ethyl alcohol centrifuge washing five times, be placed in 60 DEG C of dryings, products therefrom is Si/SiO
2/ C semi-hollow composite construction.Si accounts for Si/SiO
2/ C part hollow composite construction mass percent scope is 63%.Fig. 3 (a) is for originally executing the Si/SiO of example preparation
2/ C part hollow composite construction sample transmission electron micrograph and high power transmission electron microscope photo.By Fig. 4,5 can to find out that battery operation 430 encloses rear specific capacity be 707mgh/g, and capability retention is 64.3%, and coulombic efficiency is 100% substantially entirely,
Embodiment 3
Commodity Si is added ammoniacal liquor, enters deionized water and absolute ethyl alcohol volume ratio and be in the mixed solution of 3:10:50 and add ultrasonic 10 minutes of the PVP of Si quality 1/5, then add the TEOS with deionized water volume ratio 1:1.Stir 1h, with deionized water and absolute ethyl alcohol centrifuge washing three times, be placed on 60 DEG C of dryings in drying box, obtain Si/SiO
2composite construction product, by Si/SiO
2sample and mass ratio are after the PVDF of 4:1 mixes, add PVDF quality 10 times NMP stir after in the lower 700 DEG C of carbonization 2h of Ar atmosphere.After HF products therefrom being put into 0.5Mol/L etches 1h, with deionized water and absolute ethyl alcohol centrifuge washing five times, be placed in 60 DEG C of dryings, products therefrom is Si/SiO
2/ C semi-hollow composite construction.Si accounts for Si/SiO
2/ C part hollow composite construction mass percent scope is 70%.
Embodiment 4
Commodity Si to be added ammoniacal liquor, deionized water and absolute ethyl alcohol volume ratio be in the mixed solution of 1:2:16 and add ultrasonic 10 minutes of the PVP of Si quality 1/1, then add the TEOS with deionized water volume ratio 1:1.Stir 1h, with deionized water and absolute ethyl alcohol centrifuge washing three times, be placed on 60 DEG C of dryings in drying box, obtain Si/SiO
2composite construction product, by Si/SiO
2sample and mass ratio are after the PVDF of 4:1 mixes, add PVDF quality 10 times NMP stir after in the lower 750 DEG C of carbonization 2h of Ar atmosphere.After HF products therefrom being put into 4Mol/L etches 10min, with deionized water and absolute ethyl alcohol centrifuge washing five times, be placed in 60 DEG C of dryings, products therefrom is Si/SiO
2/ C semi-hollow composite construction.Si accounts for Si/SiO
2/ C part hollow composite construction mass percent scope is 50%.
Claims (10)
1. a carbon silicon composite lithium ion battery cathode material, is characterized in that, Si is coated with one deck SiO as its intimate of kernel
2layer, SiO
2be voided layer between layer and outermost layer C coating layer; The mass percent scope that kernel Si accounts for described composite material is 30% ~ 70%.
2. a kind of carbon silicon composite lithium ion battery cathode material according to claim 1, it is characterized in that, described voided layer is at synthesized Si/SiO
2in/C composite, by intermediate layer SiO
2partial etching obtains; Described Si/SiO
2/ C composite is that kernel Si is coated with SiO outward successively
2layer and C layer.
3. a kind of carbon silicon composite lithium ion battery cathode material according to claim 1 and 2, it is characterized in that, kernel Si accounts for Si/SiO
2/ C part hollow composite construction mass percent scope is 60% ~ 70%.
4. the preparation method of a carbon silicon composite lithium ion battery cathode material, it is characterized in that, comprise the following steps: Si joins ultrasonic disperse in ammoniacal liquor, deionized water and absolute ethyl alcohol mixed solution, add tetraethoxysilane again, after stirring hydrolysis, with deionized water and absolute ethyl alcohol centrifuge washing, dry, obtain Si/SiO
2composite construction product; By Si/SiO
2in lower 650 DEG C ~ 850 DEG C carbonizations of Ar atmosphere after composite construction product and Kynoar, 1-METHYLPYRROLIDONE stir; By products therefrom Si/SiO after carbonization
2it is 0.5-4Mol/L HF acid that/C composite puts into concentration, to SiO
2centrifugal drying after partial etching, products therefrom is Si/SiO
2/ C part hollow composite cathode material of lithium ion battery; Si accounts for Si/SiO
2/ C part hollow composite construction mass percent scope is 30% ~ 70%; Described Si/SiO
2composite construction product and Kynoar mass ratio range are 10: 1 ~ 4: 1.
5. preparation method according to claim 4, is characterized in that, ammoniacal liquor and deionized water volume ratio scope are 1: 5 ~ 1: 2; Described deionized water and absolute ethyl alcohol volume ratio scope are 1: 5 ~ 1: 10.
6. preparation method according to claim 4, is characterized in that, deionized water and tetraethoxysilane volume ratio scope are 5: 1 ~ 1: 1.
7. preparation method according to claim 4, is characterized in that, described Kynoar and 1-METHYLPYRROLIDONE mass ratio range are 1: 20-1: 10.
8. preparation method according to claim 4, is characterized in that, adds polyethylene of dispersing agent pyrrolidones and Si mass ratio range is 1: 10 ~ 1 in ultrasonic disperse process: 1..
9. preparation method according to claim 4, is characterized in that, described ammoniacal liquor and deionized water and absolute ethyl alcohol volume ratio scope are 1: 3 ~ 4: 20 ~ 25; Si and polyvinylpyrrolidone mass ratio are 3.5 ~ 4.5: 1; Deionized water and tetraethoxysilane volume ratio are 1.5 ~ 2.5: 1; Si/SiO
2composite construction and Kynoar mass ratio are 5.5 ~ 6.5: 1; Kynoar and 1-METHYLPYRROLIDONE mass ratio are 1: 16 ~ 17; Carburizing temperature is 650 DEG C ~ 700 DEG C; HF acid concentration is 0.5 ~ 1Mol/L.
10. the preparation method according to any one of claim 4-9, is characterized in that, kernel Si accounts for Si/SiO
2/ C part hollow composite construction mass percent scope is 60% ~ 70%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208635A (en) * | 2011-05-06 | 2011-10-05 | 奇瑞汽车股份有限公司 | Lithium ion battery cathode material and manufacturing method thereof and lithium ion battery |
| CN103094533A (en) * | 2012-11-26 | 2013-05-08 | 中南大学 | Multi-core core-shell-structure silicon carbon composite negative pole material and preparation method thereof |
| CN103531760A (en) * | 2013-10-28 | 2014-01-22 | 北京化工大学 | Porous silicon carbon composite microsphere with yolk-eggshell structure and preparation method therefor |
-
2014
- 2014-07-20 CN CN201410344969.0A patent/CN105006549A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208635A (en) * | 2011-05-06 | 2011-10-05 | 奇瑞汽车股份有限公司 | Lithium ion battery cathode material and manufacturing method thereof and lithium ion battery |
| CN103094533A (en) * | 2012-11-26 | 2013-05-08 | 中南大学 | Multi-core core-shell-structure silicon carbon composite negative pole material and preparation method thereof |
| CN103531760A (en) * | 2013-10-28 | 2014-01-22 | 北京化工大学 | Porous silicon carbon composite microsphere with yolk-eggshell structure and preparation method therefor |
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| CN108352516A (en) * | 2015-11-09 | 2018-07-31 | 株式会社丰田自动织机 | Negative electrode active material |
| CN105514381A (en) * | 2015-12-25 | 2016-04-20 | 苏州格瑞动力电源科技有限公司 | Method for treating silicon negative materials of lithium ion battery |
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| CN108598413A (en) * | 2018-04-23 | 2018-09-28 | 桑德集团有限公司 | Preparation method and silicon-based anode active material, the lithium ion battery negative material and lithium ion battery of silicon-based anode active material |
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