CN105576209A - High-capacity silicon-based anode material for lithium ion battery and preparation method thereof, and lithium ion battery - Google Patents
High-capacity silicon-based anode material for lithium ion battery and preparation method thereof, and lithium ion battery Download PDFInfo
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Abstract
The invention discloses a high-capacity silicon-based anode material for a lithium ion battery and a preparation method thereof, and the lithium ion battery. The material comprises nanometer silicon, graphite, organic matter pyrolytic carbon and lithium fluoride. A preparation method comprises the following steps of carrying out mixing, drying and vacuum baking on the nanometer silicon, the graphite and a pyrolytic carbon organic matter precursor to obtain a composite precursor, baking the composite precursor to obtain a pyrolytic carbon coated composite, and utilizing lithium salt solution and fluoride solution to carry out in-situ reaction on the surface of the composite to generate a lithium fluoride coating layer, namely the high-capacity silicon-based anode material for the lithium ion battery. Through in-situ generation of the lithium fluoride on the surface of the silicon-based composite, the interface characteristic of the material is effectively improved, the compactness and the stability of a solid electrolyte membrane formed by the material in the first lithium insertion process is improved, so that the electrochemical performance of the material is improved, the first charge and discharge efficiency of the battery is more than 80%, and the capacity retention ratio after 50 charge and discharge cycles is more than 85%.
Description
Technical field
The present invention relates to technical field of lithium ion battery negative, be specifically related to a kind of high-capacity lithium ion cell silicon based anode material and preparation method thereof, lithium ion battery.
Background technology
Nowadays lithium rechargeable battery has become the chemical power source of main flow, be widely used in most mobile terminal device, compared to ni-mh, NI-G and lead-acid battery, lithium rechargeable battery has the advantages such as operating voltage is high, specific energy is high and have extended cycle life, obtain in recent years and develop rapidly, the application in the mobile devices such as notebook computer, digital camera, mobile phone, MP3 and MP4 is more and more extensive.Along with mobile device is to miniaturized and multifunction future development, to the energy density of lithium rechargeable battery and have higher requirement useful life, equally due to fast development and the extensive use of various portable electric appts and electric automobile, the demand of lithium ion battery that is high for energy, that have extended cycle life is very urgent.The main negative material of current commercial Li-ion battery is graphite, and due to its theoretical capacity low (372mAh/g), high-rate charge-discharge capability is poor, limits the further raising of lithium ion battery energy.
Because silicon has the highest theoretical specific capacity (4200mAh/g) and lower de-lithium current potential (being less than 0.5V), become one of lithium ion battery negative material of the most potential replacement graphite in recent years.Li and Si can form Li
xsi (0<x≤4.4) alloy, it is generally acknowledged at normal temperatures, the rich lithium product mainly Li that silicium cathode and lithium alloyage produce
3.7si
5phase, capacity is up to 3572mAh/g, and much larger than the theoretical capacity of graphite, but in charge and discharge process, huge change in volume can occur silicon, causes material efflorescence, peels off, loses electrical contact, and capacity attenuation is very fast.By adopting the particle diameter of reduction silicon materials, silicon being made porous material, reduce the dimension of silicon materials, preparing cyclical stability and first charge-discharge efficiency that the modes such as Si-C composite material improve silicon-based anode to a certain extent in prior art, but, these Improving Measurements need higher cost mostly, need to mate corresponding electrolyte and could play its performance preferably, and the long-term cycle performance of material is still poor.Therefore, it is a kind of good with compatibility of electrolyte to research and develop, good cycle, and the silicon based anode material of advantage of lower cost is significant to the performance improving lithium ion battery.
Summary of the invention
Technical problem to be solved by this invention is, overcomes deficiency of the prior art, provides a kind of Silicon Based Anode Materials for Lithium-Ion Batteries and preparation method thereof, lithium ion battery, and the capacity of lithium ion battery obtained by this negative material is high, good cycle.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is:
A kind of high-capacity lithium ion cell silicon based anode material, described high-capacity lithium ion cell silicon based anode material comprises nano-silicon, graphite, organic matter pyrolysis carbon and lithium fluoride, nano-silicon is attached to the surface of graphite, organic matter pyrolysis carbon-coated nano silicon/graphite, the coated organic substance RESEARCH OF PYROCARBON of lithium fluoride, described lithium fluoride is that lithium salts and fluoride obtain through chemical reaction in-situ preparation.
Above-mentioned high-capacity lithium ion cell silicon based anode material, preferably, described lithium salts is selected from the one in lithium chloride, lithium sulfate, lithium nitrate, lithium hydroxide, lithium acetate, described fluoride is water soluble and take fluorine as the compound of anion, is selected from the one in hydrogen fluoride, sodium fluoride, potassium fluoride, ammonium acid fluoride, ammonium fluoride.
Above-mentioned high-capacity lithium ion cell silicon based anode material, preferably, the mass ratio of described nano-silicon and graphite is 1:3 ~ 20, and organic matter pyrolysis carbon accounts for 5% ~ 20% of silicon based anode material gross mass, and lithium fluoride accounts for 1% ~ 10% of silicon based anode material gross mass.
Above-mentioned high-capacity lithium ion cell silicon based anode material, preferably, described nano-silicon is graininess, and particle diameter is 5nm ~ 300nm; Described graphite is selected from one in Delanium, native graphite or two kinds, and described graphite is graininess, and particle diameter is 0.5 μm ~ 20 μm.
Above-mentioned high-capacity lithium ion cell silicon based anode material, preferably, described organic matter pyrolysis carbon is that organic substance obtains through thermal decomposition generation under an inert atmosphere, and described organic substance is selected from the one in phenolic resins, citric acid, glucose, sucrose, shitosan, polyvinylidene fluoride, pitch.
As a total inventive concept, the present invention also provides the preparation method of above-mentioned high-capacity lithium ion cell silicon based anode material, comprises the following steps:
(1) nano-silicon is joined in solvent carry out ultrasonic disperse, then add graphite and carry out mix and blend, add RESEARCH OF PYROCARBON organic matter precursor again and continue mix and blend, the mixed solution obtained carries out evaporation drying, then obtains Si-C composite material presoma after carrying out vacuum bakeout;
(2) the Si-C composite material presoma that step (1) obtains is carried out calcination process under an inert atmosphere, then after grinding, obtain the coated nano-silicon/graphite composite material of organic matter pyrolysis carbon;
(3) composite material that step (2) obtains is joined in solvent carry out dispersed with stirring, then add lithium salt solution, fluoride aqueous solution carries out mix and blend, after the mixed solution obtained carries out drying, namely obtain described high-capacity lithium ion cell silicon based anode material.
Above-mentioned preparation method, preferably, in described step (1), the mass ratio of nano-silicon and graphite is 1:3 ~ 20, solvent is deionized water, methyl alcohol, ethanol, ethylene glycol, propyl alcohol or 1-METHYLPYRROLIDONE, the duration of ultrasonic disperse is 10 ~ 120 minutes, mix and blend is carried out 30 ~ 120 minutes after adding graphite, RESEARCH OF PYROCARBON organic matter precursor is selected from phenolic resins, citric acid, glucose, sucrose, shitosan, polyvinylidene fluoride, one in pitch, the addition of RESEARCH OF PYROCARBON organic matter precursor is according to the carbonation rate of presoma, the mass fraction (5% ~ 20%) that combined organic RESEARCH OF PYROCARBON accounts for silicon based anode material gross mass calculates, continue mix and blend after adding RESEARCH OF PYROCARBON organic matter precursor 30 ~ 60 minutes, the temperature of vacuum bakeout is 60 DEG C ~ 120 DEG C, and the duration of vacuum bakeout is 4 ~ 20 hours, in described step (2), inert atmosphere is argon gas, helium or nitrogen, is particularly preferably argon gas, and sintering temperature is 450 DEG C ~ 1000 DEG C, and roasting duration is 3 ~ 12 hours.
Above-mentioned preparation method, preferably, in described step (3), composite material joins in solvent and carries out dispersed with stirring 30 ~ 60 minutes, and solvent is deionized water; Lithium salt solution is the aqueous solution of lithium salts, and lithium salts is selected from the one in lithium chloride, lithium sulfate, lithium nitrate, lithium hydroxide, lithium acetate, and the mass fraction of lithium salt solution is 1% ~ 10%, carries out mix and blend 30 ~ 60 minutes after adding lithium salt solution; Fluoride aqueous solution is the aqueous solution of fluoride, fluoride is water soluble and take fluorine as the compound of anion, be selected from the one in hydrogen fluoride, sodium fluoride, potassium fluoride, ammonium acid fluoride, ammonium fluoride, the mass fraction of fluoride aqueous solution is 1% ~ 10%, continues mix and blend 30 ~ 60 minutes after adding fluoride aqueous solution.The addition of lithium salt solution and fluoride aqueous solution, according to the mass fraction of lithium salts and fluoride aqueous solution, accounts for the mass fraction (1% ~ 10%) of silicon based anode material gross mass in conjunction with lithium fluoride and corresponding chemical equation calculates.
Above-mentioned preparation method, preferably, in described step (3), dry for washing again after adopting spraying dry, suction filtration, vacuumize or centrifugal after wash again, a kind of mode in vacuumize carries out.Drying mode is selected for different synthesis materials, and the ammonium acetate as obtained by lithium acetate and ammonium fluoride reaction in-situ can at high temperature be decomposed, therefore spray-dired mode can be adopted to obtain end product for this type of preparation method; Reaction in-situ is generated to the accessory substance being difficult to decomposes, then need to adopt vacuum filtration or centrifugal mode to be separated removal, then after washing and drying, obtain end product.
The present invention also provides a kind of high-capacity lithium ion cell, the negative pole of described lithium ion battery is prepared by above-mentioned high-capacity lithium ion cell silicon based anode material, or the high-capacity lithium ion cell silicon based anode material obtained by above-mentioned preparation method prepares.
The present invention prepares nano-silicon/graphite composite by the surface being scattered in by nano-silicon between graphite space or be attached to graphite, then drying, baking and high temperature pyrolysis carbonization treatment are carried out to nano-silicon/graphite composite, prepare nano-silicon/graphite composite material that RESEARCH OF PYROCARBON is coated, finally generate lithium fluoride coating layer in the surface in situ reaction of this composite material, obtain high-capacity lithium ion cell silicon based anode material of the present invention.This preparation method can improve the dispersiveness of nano-silicon in silicon-carbon cathode material, improve the structural stability of material in removal lithium embedded process, ensure that material has higher conductance, the lithium fluoride coating layer generated at the surface in situ of RESEARCH OF PYROCARBON coating layer is wrapped in the surface of material granule effectively, effectively can improve the interfacial characteristics of material, improve the chemical property of silicon-carbon cathode material.
Compared with prior art, the present invention has the following advantages:
(1) nano-silicon is dispersed between graphite by the present invention, effectively improves the reuniting effect of nano-silicon, for the volumetric expansion of nano-silicon in charge and discharge process provides space, avoids nano-silicon break and cause performance degradation.
(2) the present invention uses organic matter pyrolysis carbon to be coated on silicon and graphite granule surface, improve the conductivity of composite material, also make nano-silicon and graphite contact more tight simultaneously, reduce the contact resistance between nano-silicon and graphite, be conducive to the conductivity improving material.
(3) the present invention generates lithium fluoride coating layer at the silicon based composite material surface in situ that carbon is coated, effectively can improve the interfacial characteristics of material, material is made to form more stable and fine and close solid electrolyte film (SEI film) in embedding lithium process first, reduce the transport resistance of lithium ion at interface, greatly improve the cycle performance of material, and directly add because it can not be wrapped in the surface of material granule in lithium fluoride to material, therefore the SEI film character that material surface formed can not be improved.
(4) the present invention take part in the forming process of SEI film at the lithium fluoride that the silicon based composite material surface in situ that carbon is coated generates, and to decrease in electrolyte organic solvent in the reduction on negative material surface, thus improve the first charge-discharge efficiency of negative material, and directly add in lithium fluoride to material and significantly can't improve the reduction characteristic of electrolyte at composite material surface, namely significantly can not reduce the reduction of electrolyte on negative material surface.
(5) button cell made of high-capacity lithium ion cell silicon based anode material of the present invention, its first charge-discharge efficiency is more than 80%, and under the current density of 100mA/g, carry out 50 charge and discharge cycles, its capability retention is more than 85%.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the high-capacity lithium ion cell silicon based anode material that the embodiment of the present invention 1 obtains.
Fig. 2 is the first charge-discharge curve chart that high-capacity lithium ion cell silicon based anode material that the embodiment of the present invention 1 obtains makes button cell.
Fig. 3 is the charging cycle curve chart that high-capacity lithium ion cell silicon based anode material that the embodiment of the present invention 1 obtains makes button cell.
Fig. 4 is the charging cycle curve chart that Silicon Based Anode Materials for Lithium-Ion Batteries that comparative example 1 obtains makes button cell.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Embodiment 1
A preparation method for high-capacity lithium ion cell silicon based anode material of the present invention, comprises the following steps:
(1) be that the silicon nanoparticle of 80nm joins in 100ml absolute ethyl alcohol and carries out ultrasonic disperse and obtain nano-silicon dispersion liquid in 60 minutes by 0.5g particle diameter, under Keep agitation condition, add 5g particle diameter in dispersion liquid is that the Delanium of 0.6 μm carries out mix and blend, mixing time is 90 minutes, in dispersion liquid, add 6.1g citric acid again continue mix and blend 60 minutes, the mixed solution obtained carries out water bath method and vacuum bakeout obtained Si-C composite material presoma after 8 hours at 60 DEG C;
(2) Si-C composite material presoma step (1) obtained 450 DEG C of roastings 3 hours under argon shield, then obtain the coated nano-silicon/graphite composite material of RESEARCH OF PYROCARBON through grinding;
(3) get composite material that 3g step (2) obtains to join in deionized water and carry out dispersed with stirring and obtain dispersion liquid in 60 minutes, then add in dispersion liquid 40.2g mass fraction be 1% the lithium acetate aqueous solution carry out mix and blend 45 minutes, under Keep agitation condition, slowly add in dispersion liquid again 2.3g mass fraction be 10% ammonium fluoride aqueous solution continue mix and blend, mixing time is 30 minutes, namely obtains high-capacity lithium ion cell silicon based anode material of the present invention after the mixed solution obtained is spray-dried.
The high-capacity lithium ion cell silicon based anode material that the present embodiment obtains is made up of nano-silicon, Delanium, citric acid RESEARCH OF PYROCARBON and lithium fluoride, Fig. 1 is the scanning electron microscope (SEM) photograph of the high-capacity lithium ion cell silicon based anode material that the present embodiment obtains, as can be seen from the figure, nano-silicon is attached to the surface of Delanium, citric acid RESEARCH OF PYROCARBON clad nano silicon/Delanium, lithium fluoride is coated on the surface of citric acid RESEARCH OF PYROCARBON.In the silicon based anode material that the present embodiment obtains, the mass ratio of nano-silicon and Delanium is 1:10, and in silicon based anode material, the mass fraction of RESEARCH OF PYROCARBON is 10%, and the mass fraction of lithium fluoride is 5%.
The high-capacity lithium ion cell silicon based anode material obtained by the present embodiment is assembled into button cell, carry out electrochemical property test, Fig. 2 is the first charge-discharge curve chart that high-capacity lithium ion cell silicon based anode material that the present embodiment obtains makes button cell, as can be seen from the figure, under the current density of 100mA/g, embedding lithium capacity is 563mAh/g first, and de-lithium capacity is 468mAh/g first, and first charge-discharge efficiency is 83.1%; Fig. 3 is the charge and discharge cycles curve chart that high-capacity lithium ion cell silicon based anode material that the embodiment of the present invention 1 obtains makes button cell, and as can be seen from the figure, under the current density of 100mA/g, the 50 weeks capability retentions that circulate are 90.2%.
Embodiment 2
A preparation method for high-capacity lithium ion cell silicon based anode material of the present invention, comprises the following steps:
(1) be that the silicon nanoparticle of 8nm joins in 200ml methyl alcohol and carries out ultrasonic disperse and obtain nano-silicon dispersion liquid in 120 minutes by 0.5g particle diameter, under Keep agitation condition, add 2g particle diameter in dispersion liquid is that the native graphite of 5 μm carries out mix and blend, mixing time is 120 minutes, in dispersion liquid, add 3.57g phenolic resins again continue mix and blend 30 minutes, the mixed solution obtained carries out water bath method and 120 DEG C of vacuum bakeouts obtained Si-C composite material presoma after 4 hours;
(2) Si-C composite material presoma step (1) obtained 750 DEG C of roastings 6 hours under argon shield, then obtain the coated nano-silicon/graphite composite material of RESEARCH OF PYROCARBON through grinding;
(3) get composite material that 1.5g step (2) obtains to join in deionized water and carry out dispersed with stirring and obtain dispersion liquid in 30 minutes, then add in dispersion liquid 2.7g mass fraction be 10% water lithium chloride solution carry out mix and blend 30 minutes, under Keep agitation condition, slowly add in dispersion liquid again 12.7g mass fraction be 1% aqueous hydrogen fluoride solution continue mix and blend, mixing time is 60 minutes; The mixed solution obtained first carries out vacuum filtration, then by the vacuumize 12 hours through washing and at 80 DEG C of the filter cake that obtains, obtains high-capacity lithium ion cell silicon based anode material of the present invention.
The high-capacity lithium ion cell silicon based anode material that the present embodiment obtains is made up of nano-silicon, native graphite, phenolic resins pyrolysis carbon and lithium fluoride, nano-silicon is attached to the surface of native graphite, phenolic resins pyrolysis carbon-coated nano silicon/native graphite, lithium fluoride is coated on the surface of phenolic resins pyrolysis carbon.In the silicon based anode material that the present embodiment obtains, the mass ratio of nano-silicon and native graphite is 1:4, and in silicon based anode material, the mass fraction of phenolic resins pyrolysis carbon is 20%, and the mass fraction of lithium fluoride is 10%.
The high-capacity lithium ion cell silicon based anode material obtained by the present embodiment is assembled into button cell, carry out electrochemical property test, the result display of charge and discharge cycles test, under the current density of 100mA/g, embedding lithium capacity is 665.9mAh/g first, de-lithium capacity is 576mAh/g first, and first charge-discharge efficiency is 81.1%, and the 50 weeks capability retentions that circulate are 86.5%.
Embodiment 3
A preparation method for high-capacity lithium ion cell silicon based anode material of the present invention, comprises the following steps:
(1) be that the silicon nanoparticle of 280nm joins in 100mlN-methyl pyrrolidone and carries out ultrasonic disperse and obtain nano-silicon dispersion liquid in 40 minutes by 0.5g particle diameter, under Keep agitation condition, add 10g particle diameter in dispersion liquid is that the Delanium of 18 μm carries out mix and blend, mixing time is 30 minutes, in dispersion liquid, add 1.4g asphalt powder again continue mix and blend 45 minutes, the mixed solution obtained carries out water bath method and 80 DEG C of vacuum bakeouts obtained Si-C composite material presoma after 12 hours;
(2) Si-C composite material presoma step (1) obtained 950 DEG C of roastings 12 hours under argon shield, then obtain the coated nano-silicon/graphite composite material of RESEARCH OF PYROCARBON through grinding;
(3) get composite material that 6.5g step (2) obtains to join in deionized water and carry out dispersed with stirring and obtain dispersion liquid in 45 minutes, then slowly add in dispersion liquid 2.9g mass fraction be 5% the ammonium acid fluoride aqueous solution carry out mix and blend 60 minutes, under Keep agitation condition, again to add in dispersion liquid 2.1g mass fraction be 5% lithium hydroxide aqueous solution continue mix and blend, mixing time is 90 minutes; The mixed solution obtained first carries out high speed centrifugation separation, then by the centrifugal product obtained through washing and vacuumize 12 hours at 80 DEG C, obtain high-capacity lithium ion cell silicon based anode material of the present invention.
The high-capacity lithium ion cell silicon based anode material that the present embodiment obtains is made up of nano-silicon, Delanium, asphalt pyrolysis carbon and lithium fluoride, nano-silicon is attached to the surface of Delanium, asphalt pyrolysis carbon-coated nano silicon/Delanium, lithium fluoride is coated on the surface of asphalt pyrolysis carbon.In the silicon based anode material that the present embodiment obtains, the mass ratio of nano-silicon and Delanium is 1:20, and the mass fraction of silicon based anode material medium pitch RESEARCH OF PYROCARBON is 5%, and the mass fraction of lithium fluoride is 1%.
The high-capacity lithium ion cell silicon based anode material obtained by the present embodiment is assembled into button cell, carry out electrochemical property test, the result display of charge and discharge cycles test, under the current density of 100mA/g, embedding lithium capacity is 473.7mAh/g first, de-lithium capacity is 415mAh/g first, and first charge-discharge efficiency is 87.6%, and the 50 weeks capability retentions that circulate are 96.2%.
Comparative example 1
The preparation method of the Silicon Based Anode Materials for Lithium-Ion Batteries of this comparative example, comprises the following steps:
(1) be that the silicon nanoparticle of 80nm joins in 100ml absolute ethyl alcohol and carries out ultrasonic disperse and obtain nano-silicon dispersion liquid in 60 minutes by 0.5g particle diameter, under Keep agitation condition, add 5g particle diameter in dispersion liquid is that the Delanium of 0.6 μm carries out mix and blend, mixing time is 90 minutes, in dispersion liquid, add 6.1g citric acid again continue mix and blend 60 minutes, the mixed solution obtained carries out water bath method and vacuum bakeout obtained Si-C composite material presoma after 8 hours at 60 DEG C;
(2) Si-C composite material presoma step (1) obtained 450 DEG C of roastings 3 hours under argon shield, then obtain the coated nano-silicon/graphite composite material of RESEARCH OF PYROCARBON through grinding;
(3) get composite material that 3g step (2) obtains to join in deionized water and carry out dispersed with stirring and obtain dispersion liquid in 60 minutes, then in dispersion liquid, add 0.16g lithium fluoride and continue mix and blend 30 minutes, after the mixed solution obtained is spray-dried, namely obtaining the Silicon Based Anode Materials for Lithium-Ion Batteries of this comparative example.
The high-capacity lithium ion cell silicon based anode material that this comparative example obtains is made up of nano-silicon, Delanium, citric acid RESEARCH OF PYROCARBON and lithium fluoride, the mass ratio of nano-silicon and Delanium is 1:10, in silicon based anode material, the mass fraction of RESEARCH OF PYROCARBON is 10%, and the mass fraction of lithium fluoride is 5%.
The high-capacity lithium ion cell silicon based anode material this comparative example obtained is assembled into button cell, carry out electrochemical property test, Fig. 4 is the charging cycle curve chart of the Silicon Based Anode Materials for Lithium-Ion Batteries that this comparative example obtains, as can be seen from the figure, under the current density of 100mA/g, the 50 weeks capability retentions that circulate are only 59.5%, and cycle performance is far worse than the high-capacity lithium ion cell silicon based anode material that the present invention obtains.
Claims (10)
1. a high-capacity lithium ion cell silicon based anode material, it is characterized in that, described high-capacity lithium ion cell silicon based anode material comprises nano-silicon, graphite, organic matter pyrolysis carbon and lithium fluoride, nano-silicon is attached to the surface of graphite, organic matter pyrolysis carbon-coated nano silicon/graphite, the coated organic substance RESEARCH OF PYROCARBON of lithium fluoride, described lithium fluoride is that lithium salts and fluoride obtain through chemical reaction in-situ preparation.
2. high-capacity lithium ion cell silicon based anode material as claimed in claim 1, it is characterized in that, described lithium salts is selected from the one in lithium chloride, lithium sulfate, lithium nitrate, lithium hydroxide, lithium acetate, described fluoride is water soluble and take fluorine as the compound of anion, is selected from the one in hydrogen fluoride, sodium fluoride, potassium fluoride, ammonium acid fluoride, ammonium fluoride.
3. high-capacity lithium ion cell silicon based anode material as claimed in claim 1, it is characterized in that, the mass ratio of described nano-silicon and graphite is 1:3 ~ 20, and organic matter pyrolysis carbon accounts for 5% ~ 20% of silicon based anode material gross mass, and lithium fluoride accounts for 1% ~ 10% of silicon based anode material gross mass.
4. the high-capacity lithium ion cell silicon based anode material according to any one of claims 1 to 3, is characterized in that, described nano-silicon is graininess, and particle diameter is 5nm ~ 300nm; Described graphite is selected from one in Delanium, native graphite or two kinds, and described graphite is graininess, and particle diameter is 0.5 μm ~ 20 μm.
5. the high-capacity lithium ion cell silicon based anode material according to any one of claims 1 to 3, it is characterized in that, described organic matter pyrolysis carbon is that organic substance obtains through thermal decomposition generation under an inert atmosphere, and described organic substance is selected from the one in phenolic resins, citric acid, glucose, sucrose, shitosan, polyvinylidene fluoride, pitch.
6. a preparation method for the high-capacity lithium ion cell silicon based anode material according to any one of Claims 1 to 5, is characterized in that, comprise the following steps:
(1) nano-silicon is joined in solvent carry out ultrasonic disperse, then add graphite and carry out mix and blend, add RESEARCH OF PYROCARBON organic matter precursor again and continue mix and blend, the mixed solution obtained carries out evaporation drying, then obtains Si-C composite material presoma after carrying out vacuum bakeout;
(2) the Si-C composite material presoma that step (1) obtains is carried out calcination process under an inert atmosphere, then after grinding, obtain the coated nano-silicon/graphite composite material of organic matter pyrolysis carbon;
(3) composite material that step (2) obtains is joined in solvent carry out dispersed with stirring, then add lithium salt solution, fluoride aqueous solution carries out mix and blend, after the mixed solution obtained carries out drying, namely obtain described high-capacity lithium ion cell silicon based anode material.
7. preparation method as claimed in claim 6, it is characterized in that, in described step (1), the mass ratio of nano-silicon and graphite is 1:3 ~ 20, described solvent is deionized water, methyl alcohol, ethanol, ethylene glycol, propyl alcohol or 1-METHYLPYRROLIDONE, the duration of ultrasonic disperse is 10 ~ 120 minutes, the duration carrying out mix and blend after adding graphite is 30 ~ 120 minutes, the duration continuing mix and blend after adding RESEARCH OF PYROCARBON organic matter precursor is 30 ~ 60 minutes, the temperature of vacuum bakeout is 60 DEG C ~ 120 DEG C, and the duration of vacuum bakeout is 4 ~ 20 hours; In described step (2), sintering temperature is 450 DEG C ~ 1000 DEG C, and roasting duration is 3 ~ 12 hours; In described step (3), described solvent is deionized water, it is 30 ~ 60 minutes that the composite material that step (2) obtains joins the duration carrying out dispersed with stirring in solvent, the duration carrying out mix and blend after adding lithium salt solution is 30 ~ 60 minutes, and the duration carrying out mix and blend after adding fluoride aqueous solution is 30 ~ 60 minutes; In described step (3), described drying be adopt spraying dry, wash after suction filtration through vacuumize or centrifugal after any one mode of washing in vacuumize carry out.
8. preparation method as claimed in claim 6, it is characterized in that, in described step (1), described RESEARCH OF PYROCARBON organic matter precursor is the one in phenolic resins, citric acid, glucose, sucrose, shitosan, polyvinylidene fluoride, pitch.
9. preparation method as claimed in claim 6, it is characterized in that, in described step (3), described lithium salts is selected from the one in lithium chloride, lithium sulfate, lithium nitrate, lithium hydroxide, lithium acetate; Described fluoride is water soluble and take fluorine as the compound of anion, is selected from the one in hydrogen fluoride, sodium fluoride, potassium fluoride, ammonium acid fluoride, ammonium fluoride; The mass fraction of described lithium salt solution is 1% ~ 10%, and the mass fraction of described fluoride aqueous solution is 1% ~ 10%.
10. a high-capacity lithium ion cell, it is characterized in that, the negative pole of described lithium ion battery is prepared by the high-capacity lithium ion cell silicon based anode material such as according to any one of Claims 1 to 5, or the high-capacity lithium ion cell silicon based anode material obtained by preparation method according to any one of claim 6 ~ 9 prepares.
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