CN105576209B - A kind of high-capacity lithium ion cell silicon based anode material and preparation method thereof, lithium ion battery - Google Patents
A kind of high-capacity lithium ion cell silicon based anode material and preparation method thereof, lithium ion battery Download PDFInfo
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- CN105576209B CN105576209B CN201610080842.1A CN201610080842A CN105576209B CN 105576209 B CN105576209 B CN 105576209B CN 201610080842 A CN201610080842 A CN 201610080842A CN 105576209 B CN105576209 B CN 105576209B
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- 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
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- 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
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Abstract
The invention discloses a kind of high-capacity lithium ion cell silicon based anode material and preparation method thereof, lithium ion battery, the material includes nano-silicon, graphite, organic matter pyrolysis carbon and lithium fluoride, preparation process is by nano-silicon, graphite and pyrolytic carbon organic matter precursor are mixed, dry and vacuum bakeout, obtain composite material precursor, then composite material precursor is calcined to obtain the composite of pyrolysis carbon coating, lithium salt solution and fluoride aqueous solution are recycled in the surface in situ reaction generation lithium fluoride clad of composite, produce high-capacity lithium ion cell silicon based anode material.The present invention in silicon based composite material surface in situ by generating lithium fluoride, effectively improve the interfacial characteristics of material, improve the compactness and stability for the solid electrolyte film that material is formed in process of intercalation first, so as to improve the chemical property of material, battery first charge-discharge efficiency is more than 80%, and the capability retention 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, and in particular to a kind of high-capacity lithium ion cell silicon substrate
Negative material and preparation method thereof, lithium ion battery.
Background technology
Nowadays lithium rechargeable battery turns into the electrochmical power source of main flow, be widely used in most mobile terminals and set
Standby, compared to ni-mh, NI-G and lead-acid battery, lithium rechargeable battery has operating voltage height, and cycle life higher than energy
The advantages that long, developed rapidly in recent years, in the mobile devices such as notebook computer, digital camera, mobile phone, MP3 and MP4
Application it is more and more extensive.With mobile device to miniaturization and multifunction direction develop, to the energy of lithium rechargeable battery
Metric density and service life propose higher requirement, also due to the quick hair of various portable electric appts and electric automobile
Exhibition and extensive use, it is very urgent for the demand of energy height, the lithium ion battery having extended cycle life.Commercial Li-ion at present
The main negative material of battery is graphite, and because its theoretical capacity is low (372mAh/g), high-rate charge-discharge capability is poor, limits
The further raising of lithium ion battery energy.
Because silicon has highest theoretical specific capacity (4200mAh/g) and relatively low de- lithium current potential (being less than 0.5V), in recent years
To turn into one of lithium ion battery negative material of most potential substitution graphite.Li and Si can form LixSi(0<X≤4.4) close
Gold, it is considered that at normal temperatures, silicium cathode is mainly Li with rich lithium product caused by lithium alloyage3.7Si5Phase, capacity are up to
3572mAh/g, much larger than the theoretical capacity of graphite, but in charge and discharge process, huge Volume Changes can occur for silicon, cause
Material efflorescence, peel off, lose electrical contact, capacity attenuation is quickly.In the prior art by using reduce the particle diameter of silicon materials, by silicon
Porous material is made, reduces the dimension of silicon materials, prepare the modes such as Si-C composite material and improve silicon substrate to a certain extent and bear
The cyclical stability and first charge-discharge efficiency of pole, still, these Improving Measurements need higher cost, it is necessary to match phase mostly
The electrolyte answered could preferably play its performance, and the long-term cycle performance of material is still poor.Therefore, one is researched and developed
Kind, good cycle good with compatibility of electrolyte, and the silicon based anode material of advantage of lower cost is to improving lithium ion battery
Performance is significant.
The content of the invention
The technical problems to be solved by the invention are to overcome deficiency of the prior art, there is provided a kind of lithium ion battery silicon
Base negative material and preparation method thereof, lithium ion battery, the capacity of lithium ion battery as made from the negative material is high, cycle performance
It is good.
In order to solve the above technical problems, technical scheme proposed by the present invention is：
A kind of high-capacity lithium ion cell silicon based anode material, the high-capacity lithium ion cell silicon based anode material include
Nano-silicon, graphite, organic matter pyrolysis carbon and lithium fluoride, nano-silicon are attached to the surface of graphite, organic matter pyrolysis carbon-coated nano
Silicon/graphite, lithium fluoride cladding organic matter pyrolytic carbon, the lithium fluoride are that lithium salts and fluoride obtain through the in-situ preparation that chemically reacts
Arrive.
Above-mentioned high-capacity lithium ion cell silicon based anode material, it is preferred that the lithium salts be selected from lithium chloride, lithium sulfate,
One kind in lithium nitrate, lithium hydroxide, lithium acetate, the fluoride is water-soluble and the compound using fluorine as anion, choosing
One kind from hydrogen fluoride, sodium fluoride, potassium fluoride, ammonium acid fluoride, ammonium fluoride.
Above-mentioned high-capacity lithium ion cell silicon based anode material, it is preferred that the mass ratio of the nano-silicon and graphite is
1:3~20, organic matter pyrolysis carbon accounts for the 5%~20% of silicon based anode material gross mass, and lithium fluoride accounts for the total matter of silicon based anode material
The 1%~10% of amount.
Above-mentioned high-capacity lithium ion cell silicon based anode material, it is preferred that the nano-silicon is graininess, and particle diameter is
5nm~300nm；The graphite is one or two kinds of in Delanium, native graphite, and the graphite is graininess, grain
Footpath is 0.5 μm~20 μm.
Above-mentioned high-capacity lithium ion cell silicon based anode material, it is preferred that the organic matter pyrolysis carbon is that organic matter exists
Obtained under inert atmosphere through thermally decomposing to generate, the organic matter be selected from phenolic resin, citric acid, glucose, sucrose, chitosan,
One kind in polyvinylidene fluoride, pitch.
The inventive concept total as one, the present invention also provide the system of above-mentioned high-capacity lithium ion cell silicon based anode material
Preparation Method, comprise the following steps：
(1) nano-silicon is added in solvent and carries out ultrasonic disperse, then added graphite and mixed, add heat
Solution carbon organic matter precursor continues to mix, and obtained mixed solution is evaporated drying, then is obtained after carrying out vacuum bakeout
Si-C composite material presoma；
(2) the Si-C composite material presoma that step (1) obtains is subjected to calcination process under an inert atmosphere, then through grinding
Nano-silicon/graphite composite material of organic matter pyrolysis carbon coating is obtained after mill；
(3) composite that step (2) obtains is added in solvent be stirred it is scattered, then add lithium salt solution,
Fluoride aqueous solution is mixed, and obtained mixed solution produces described high-capacity lithium ion cell silicon substrate after being dried
Negative material.
Above-mentioned preparation method, it is preferred that in the step (1), the mass ratio of nano-silicon and graphite is 1:3~20, it is molten
Agent is deionized water, methanol, ethanol, ethylene glycol, propyl alcohol or 1-METHYLPYRROLIDONE, ultrasonic disperse when a length of 10~120 points
Clock, mixing is carried out 30~120 minutes after adding graphite, pyrolytic carbon organic matter precursor is selected from phenolic resin, citric acid, Portugal
One kind in grape sugar, sucrose, chitosan, polyvinylidene fluoride, pitch, the addition of pyrolytic carbon organic matter precursor is according to forerunner
The carbonation rate of body, the mass fraction (5%~20%) that combined organic pyrolytic carbon accounts for silicon based anode material gross mass are calculated；
Continue mixing 30~60 minutes after adding pyrolytic carbon organic matter precursor, the temperature of vacuum bakeout is 60 DEG C~120 DEG C, very
Sky baking when a length of 4~20 hours；In the step (2), inert atmosphere is argon gas, helium or nitrogen, particularly preferably argon
Gas, sintering temperature are 450 DEG C~1000 DEG C, a length of 3~12 hours during roasting.
Above-mentioned preparation method, it is preferred that in the step (3), composite be added in solvent be stirred it is scattered
30~60 minutes, solvent was deionized water；Lithium salt solution is the aqueous solution of lithium salts, and lithium salts is selected from lithium chloride, lithium sulfate, nitric acid
One kind in lithium, lithium hydroxide, lithium acetate, the mass fraction of lithium salt solution is 1%~10%, is mixed after adding lithium salt solution
Close stirring 30~60 minutes；Fluoride aqueous solution is the aqueous solution of fluoride, and fluoride is water-soluble and using fluorine as anion
Compound, one kind in hydrogen fluoride, sodium fluoride, potassium fluoride, ammonium acid fluoride, ammonium fluoride, the mass fraction of fluoride aqueous solution
For 1%~10%, persistently mixed 30~60 minutes after adding fluoride aqueous solution.The addition of lithium salt solution and fluoride aqueous solution
Measure the mass fraction (1% that silicon based anode material gross mass according to lithium salts and the mass fraction of fluoride aqueous solution, is accounted for reference to lithium fluoride
~10%) it is calculated with corresponding chemical equation.
Above-mentioned preparation method, it is preferred that in the step (3), dry be using spray drying, filter after wash again,
Vacuum drying or centrifugation after wash again, be dried in vacuo in a kind of mode carry out.Drying mode is directed to different synthesis materials
Being selected, the ammonium acetate such as obtained by lithium acetate and ammonium fluoride reaction in-situ can decompose at high temperature, therefore for such system
Preparation Method can obtain final product by the way of spray drying；The accessory substance for being difficult to be thermally decomposed for reaction in-situ generation,
Then need to separate by the way of vacuum filtration or centrifugation and remove, final product is obtained after then scrubbed and dry.
The present invention also provides a kind of high-capacity lithium ion cell, and the negative pole of the lithium ion battery is by above-mentioned high-capacity lithium ion battery
Ion battery silicon based anode material is prepared, or as the high-capacity lithium ion cell silicon substrate obtained by above-mentioned preparation method
Negative material is prepared.
The present invention prepares nano-silicon/stone by nano-silicon being scattered between graphite space or being attached to the surface of graphite
Black complex, then nano-silicon/graphite composite is dried, toasted and high temperature pyrolysis carbonization treatment, prepares pyrolytic carbon
Nano-silicon/graphite composite material of cladding, finally in the surface in situ reaction generation lithium fluoride clad of the composite, obtain
The high-capacity lithium ion cell silicon based anode material of the present invention.The preparation method can improve nano-silicon in silicon-carbon cathode material
Dispersiveness, improve structural stability of the material during removal lithium embedded, ensure that material has higher conductance, in pyrolytic carbon
The lithium fluoride clad of the surface in situ generation of clad is effectively wrapped in the surface of material granule, can be effectively improved material
Interfacial characteristics, improve the chemical property of silicon-carbon cathode material.
Compared with prior art, the present invention has advantages below：
(1) between nano-silicon is dispersed in graphite by the present invention, the reuniting effect of nano-silicon is effectively improved, is being filled for nano-silicon
Volumetric expansion in discharge process provides space, avoids nano-silicon from rupturing and cause performance degradation.
(2) present invention improves the conduction of composite using organic matter pyrolysis carbon coating in silicon and graphite particle surface
Property, while also make nano-silicon and graphite contact even closer, the contact resistance between nano-silicon and graphite is reduced, is advantageous to improve
The electric conductivity of material.
(3) present invention generates lithium fluoride clad in the silicon based composite material surface in situ of carbon coating, can be effectively improved
The interfacial characteristics of material, material is set to form more stable and fine and close solid electrolyte film (SEI films) in process of intercalation first,
Transport resistance of the lithium ion at interface is reduced, greatly improves the cycle performance of material, and directly adds lithium fluoride to material
In because it can not be wrapped in the surface of material granule, therefore the SEI film characters that material surface is formed will not be improved.
(4) present invention take part in the formation of SEI films in the lithium fluoride that the silicon based composite material surface in situ of carbon coating generates
Process, and reduce the reduction of organic solvent in electrolyte on negative material surface, so as to improve negative material first
Efficiency for charge-discharge, and reduction spy of the electrolyte in composite material surface can't be significantly improved into material by directly adding lithium fluoride
Property, i.e., it will not substantially reduce reduction of the electrolyte on negative material surface.
(5) button cell made of high-capacity lithium ion cell silicon based anode material of the invention, its first charge-discharge effect
Rate carries out 50 charge and discharge cycles, its capability retention is more than 85% more than 80% under 100mA/g current density.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph for the high-capacity lithium ion cell silicon based anode material that the embodiment of the present invention 1 obtains.
Fig. 2 is the head that button cell is made in the high-capacity lithium ion cell silicon based anode material that the embodiment of the present invention 1 obtains
Secondary charging and discharging curve figure.
Fig. 3 is that filling for button cell is made in the high-capacity lithium ion cell silicon based anode material that the embodiment of the present invention 1 obtains
Electric cyclic curve figure.
Fig. 4 is the charging cycle curve map that button cell is made in the Silicon Based Anode Materials for Lithium-Ion Batteries that comparative example 1 obtains.
Embodiment
For the ease of understanding the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
Embodiment 1
A kind of preparation method of high-capacity lithium ion cell silicon based anode material of the invention, comprises the following steps：
(1) silicon nanoparticle that 0.5g particle diameters are 80nm is added into progress ultrasonic disperse 60 in 100ml absolute ethyl alcohols to divide
Clock obtains nano-silicon dispersion liquid, and adding the Delanium that 5g particle diameters are 0.6 μm into dispersion liquid under lasting stirring condition is carried out
Mix, mixing time is 90 minutes, then adds 6.1g citric acids into dispersion liquid and persistently mix 60 minutes, is obtained
Mixed solution carries out water bath method and vacuum bakeout obtains Si-C composite material presoma at 60 DEG C after 8 hours；
(2) the Si-C composite material presoma that step (1) obtains is calcined 3 hours for 450 DEG C under argon gas protection, Ran Houjing
Grinding obtains being pyrolyzed nano-silicon/graphite composite material of carbon coating；
(3) composite for taking 3g steps (2) to obtain, which is added in deionized water to be stirred scattered 60 minutes, to be divided
Dispersion liquid, the lithium acetate aqueous solution that 40.2g mass fractions are 1% is then added into dispersion liquid and mix 45 minutes,
Continue under stirring condition, then be slowly added into dispersion liquid the ammonium fluoride aqueous solution that 2.3g mass fractions are 10% and persistently mix stir
Mix, mixing time is 30 minutes, and the high-capacity lithium ion cell silicon of the present invention is produced after obtained mixed solution is spray-dried
Base negative material.
High-capacity lithium ion cell silicon based anode material made from the present embodiment is by nano-silicon, Delanium, lemon acid heat
Carbon and lithium fluoride composition are solved, Fig. 1 is the scanning electron microscope (SEM) photograph for the high-capacity lithium ion cell silicon based anode material that the present embodiment obtains,
It can be seen that nano-silicon is attached to the surface of Delanium, citric acid pyrolysis carbon coating nano-silicon/Delanium, fluorine
Change the surface that lithium is coated on citric acid pyrolytic carbon.The matter of nano-silicon and Delanium in silicon based anode material made from the present embodiment
Amount is than being 1:10, the mass fraction of pyrolytic carbon is 10% in silicon based anode material, and the mass fraction of lithium fluoride is 5%.
The high-capacity lithium ion cell silicon based anode material that the present embodiment obtains is assembled into button cell, carries out electrochemistry
Performance test, Fig. 2 are that filling first for button cell is made in the high-capacity lithium ion cell silicon based anode material that the present embodiment obtains
Discharge curve, it can be seen that under 100mA/g current density, embedding lithium capacity is 563mAh/g first, is taken off first
Lithium capacity is 468mAh/g, first charge-discharge efficiency 83.1%；Fig. 3 is the high-capacity lithium-ion that the embodiment of the present invention 1 obtains
The charge and discharge cycles curve map of button cell is made in battery silicon based anode material, it can be seen that in 100mA/g electric current
Under density, it is 90.2% to circulate 50 weeks capability retentions.
Embodiment 2
A kind of preparation method of high-capacity lithium ion cell silicon based anode material of the invention, comprises the following steps：
(1) silicon nanoparticle that 0.5g particle diameters are 8nm is added into progress ultrasonic disperse in 200ml methanol to obtain for 120 minutes
To nano-silicon dispersion liquid, the native graphite that addition 2g particle diameters are 5 μm into dispersion liquid under lasting stirring condition carries out mixing and stirred
Mix, mixing time is 120 minutes, then adds 3.57g phenolic resin into dispersion liquid and persistently mix 30 minutes, and what is obtained is mixed
Close solution progress water bath method and 120 DEG C of vacuum bakeouts obtain Si-C composite material presoma after 4 hours；
(2) the Si-C composite material presoma that step (1) obtains is calcined 6 hours for 750 DEG C under argon gas protection, Ran Houjing
Grinding obtains being pyrolyzed nano-silicon/graphite composite material of carbon coating；
(3) composite for taking 1.5g steps (2) to obtain is added in deionized water to be stirred scattered 30 minutes and obtained
Dispersion liquid, the water lithium chloride solution that 2.7g mass fractions are 10% is then added into dispersion liquid and mix 30 minutes,
Under lasting stirring condition, then it is slowly added to the aqueous hydrogen fluoride solution that 12.7g mass fractions are 1% into dispersion liquid and persistently mixes
Stirring, mixing time are 60 minutes；Obtained mixed solution is first filtered by vacuum, then by obtained filter cake it is scrubbed and
It is dried in vacuo 12 hours at 80 DEG C, produces the high-capacity lithium ion cell silicon based anode material of the present invention.
High-capacity lithium ion cell silicon based anode material is by nano-silicon, native graphite, phenolic resin made from the present embodiment
Pyrolytic carbon and lithium fluoride composition, nano-silicon are attached to the surface of native graphite, phenolic resin pyrolysis carbon-coated nano silicon/natural stone
Ink, lithium fluoride are coated on the surface of phenolic resin pyrolysis carbon.In silicon based anode material made from the present embodiment nano-silicon with it is natural
The mass ratio of graphite is 1:4, the mass fraction of phenolic resin pyrolysis carbon is 20% in silicon based anode material, the quality point of lithium fluoride
Number is 10%.
The high-capacity lithium ion cell silicon based anode material that the present embodiment obtains is assembled into button cell, carries out electrochemistry
Performance test, the result of charge and discharge cycles test show that under 100mA/g current density, embedding lithium capacity is first
665.9mAh/g, it is 576mAh/g to take off lithium capacity first, and first charge-discharge efficiency 81.1%, circulating 50 weeks capability retentions is
86.5%.
Embodiment 3
A kind of preparation method of high-capacity lithium ion cell silicon based anode material of the invention, comprises the following steps：
(1) silicon nanoparticle that 0.5g particle diameters are 280nm is added in 100ml 1-METHYLPYRROLIDONEs and carries out ultrasound
Obtain nano-silicon dispersion liquid within scattered 40 minutes, it is 18 μm artificial that 10g particle diameters are added into dispersion liquid under lasting stirring condition
Graphite is mixed, and mixing time is 30 minutes, then is added 1.4g asphalt powders into dispersion liquid and persistently mixed 45 points
Clock, obtained mixed solution carries out water bath method and 80 DEG C of vacuum bakeouts obtain Si-C composite material presoma after 12 hours；
(2) by the Si-C composite material presoma that step (1) obtains argon gas protection under 950 DEG C be calcined 12 hours, then
Ground nano-silicon/the graphite composite material for obtaining being pyrolyzed carbon coating；
(3) composite for taking 6.5g steps (2) to obtain is added in deionized water to be stirred scattered 45 minutes and obtained
Dispersion liquid, the ammonium acid fluoride aqueous solution that 2.9g mass fractions are 5% is then slowly added in dispersion liquid and carries out mixing 60 points
Clock, persistently mixed under lasting stirring condition, then to the lithium hydroxide aqueous solution that 2.1g mass fractions are 5% is added into dispersion liquid
Stirring is closed, mixing time is 90 minutes；Obtained mixed solution is first centrifuged at a high speed, and then will centrifuge obtained product
It is scrubbed and be dried in vacuo 12 hours at 80 DEG C, produce the high-capacity lithium ion cell silicon based anode material of the present invention.
High-capacity lithium ion cell silicon based anode material is by nano-silicon, Delanium, asphalt pyrolysis made from the present embodiment
Carbon and lithium fluoride composition, nano-silicon are attached to the surface of Delanium, asphalt pyrolysis carbon-coated nano silicon/Delanium, fluorination
Lithium is coated on the surface of asphalt pyrolysis carbon.The mass ratio of nano-silicon and Delanium in silicon based anode material made from the present embodiment
For 1:20, the mass fraction of asphalt pyrolysis carbon is 5% in silicon based anode material, and the mass fraction of lithium fluoride is 1%.
The high-capacity lithium ion cell silicon based anode material that the present embodiment obtains is assembled into button cell, carries out electrochemistry
Performance test, the result of charge and discharge cycles test show that under 100mA/g current density, embedding lithium capacity is first
473.7mAh/g, it is 415mAh/g to take off lithium capacity first, and first charge-discharge efficiency 87.6%, circulating 50 weeks capability retentions is
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) silicon nanoparticle that 0.5g particle diameters are 80nm is added into progress ultrasonic disperse 60 in 100ml absolute ethyl alcohols to divide
Clock obtains nano-silicon dispersion liquid, and adding the Delanium that 5g particle diameters are 0.6 μm into dispersion liquid under lasting stirring condition is carried out
Mix, mixing time is 90 minutes, then adds 6.1g citric acids into dispersion liquid and persistently mix 60 minutes, is obtained
Mixed solution carries out water bath method and vacuum bakeout obtains Si-C composite material presoma at 60 DEG C after 8 hours；
(2) the Si-C composite material presoma that step (1) obtains is calcined 3 hours for 450 DEG C under argon gas protection, Ran Houjing
Grinding obtains being pyrolyzed nano-silicon/graphite composite material of carbon coating；
(3) composite for taking 3g steps (2) to obtain, which is added in deionized water to be stirred scattered 60 minutes, to be divided
Dispersion liquid, 0.16g lithium fluoride is then added into dispersion liquid and continues to mix 30 minutes, obtained mixed solution is dry through spraying
The Silicon Based Anode Materials for Lithium-Ion Batteries of this comparative example is produced after dry.
High-capacity lithium ion cell silicon based anode material made from this comparative example is by nano-silicon, Delanium, lemon acid heat
Solve carbon and lithium fluoride forms, the mass ratio of nano-silicon and Delanium is 1:10, the quality point of pyrolytic carbon in silicon based anode material
Number is 10%, and the mass fraction of lithium fluoride is 5%.
The high-capacity lithium ion cell silicon based anode material that this comparative example obtains is assembled into button cell, carries out electrochemistry
Performance test, Fig. 4 are the charging cycle curve map of Silicon Based Anode Materials for Lithium-Ion Batteries that this comparative example obtains, can be with from figure
Find out, under 100mA/g current density, 50 weeks capability retentions of circulation are only 59.5%, and cycle performance is much worse than the present invention
Obtained high-capacity lithium ion cell silicon based anode material.
Claims (10)
1. a kind of high-capacity lithium ion cell silicon based anode material, it is characterised in that the high-capacity lithium ion cell silicon substrate is born
Pole material includes nano-silicon, graphite, organic matter pyrolysis carbon and lithium fluoride, and nano-silicon is attached to the surface of graphite, organic matter pyrolysis
Carbon-coated nano silicon/graphite, lithium fluoride cladding organic matter pyrolytic carbon, the lithium fluoride are that lithium salts and fluoride are former through chemical reaction
Position generation obtains；The lithium fluoride cladding organic matter pyrolytic carbon is in the nano-silicon after organic matter pyrolysis carbon coating/graphite table
Face in-situ preparation lithium fluoride clad.
2. high-capacity lithium ion cell silicon based anode material as claimed in claim 1, it is characterised in that the lithium salts is selected from chlorine
Change one kind in lithium, lithium sulfate, lithium nitrate, lithium hydroxide, lithium acetate, the fluoride is water-soluble and using fluorine as anion
Compound, one kind 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 characterised in that the nano-silicon and stone
The mass ratio of ink is 1:3 ~ 20, organic matter pyrolysis carbon accounts for the 5% ~ 20% of silicon based anode material gross mass, and lithium fluoride accounts for silicon-based anode
The 1% ~ 10% of material gross mass.
4. the high-capacity lithium ion cell silicon based anode material as any one of claim 1 ~ 3, it is characterised in that described
Nano-silicon is graininess, and particle diameter is 5nm ~ 300nm；The graphite is one or two kinds of in Delanium, native graphite,
The graphite is graininess, and particle diameter is 0.5 μm ~ 20 μm.
5. the high-capacity lithium ion cell silicon based anode material as any one of claim 1 ~ 3, it is characterised in that described
Organic matter pyrolysis carbon be organic matter under an inert atmosphere through thermally decomposing to generate to obtain, the organic matter be selected from phenolic resin, lemon
One kind in acid, glucose, sucrose, chitosan, polyvinylidene fluoride, pitch.
6. a kind of preparation method of high-capacity lithium ion cell silicon based anode material as any one of claim 1 ~ 5,
It is characterised in that it includes following steps：
(1) nano-silicon is added in solvent and carries out ultrasonic disperse, then added graphite and mixed, add pyrolysis
Carbon organic matter precursor continues to mix, and obtained mixed solution is evaporated drying, then obtains silicon after carrying out vacuum bakeout
Carbon composite presoma；
(2) the Si-C composite material presoma that step (1) obtains is subjected to calcination process under an inert atmosphere, it is then ground
Nano-silicon/graphite composite material of organic matter pyrolysis carbon coating is obtained afterwards；
(3) composite that step (2) obtains is added in solvent and is stirred scattered, then addition lithium salt solution, fluorination
Thing solution is mixed, and obtained mixed solution produces described high-capacity lithium ion cell silicon-based anode after being dried
Material.
7. preparation method as claimed in claim 6, it is characterised in that in the step (1), the mass ratio of nano-silicon and graphite
For 1:3 ~ 20, the solvent is deionized water, methanol, ethanol, ethylene glycol, propyl alcohol or 1-METHYLPYRROLIDONE, ultrasonic disperse
Shi Changwei 10 ~ 120 minutes, add graphite after mixed when a length of 30 ~ 120 minutes, add pyrolytic carbon organic matter before
Drive continue after body to mix when a length of 30 ~ 60 minutes, the temperature of vacuum bakeout is 60 DEG C ~ 120 DEG C, the duration of vacuum bakeout
For 4 ~ 20 hours；In the step (2), sintering temperature is 450 DEG C ~ 1000 DEG C, a length of 3 ~ 12 hours during roasting；The step
(3) in, the solvent is deionized water, and the composite that step (2) obtains, which is added to, is stirred scattered duration in solvent
For 30 ~ 60 minutes, add lithium salt solution after mixed when a length of 30 ~ 60 minutes, add fluoride aqueous solution after carry out
Mixing when a length of 30 ~ 60 minutes；In the step (3), the drying is through true using washing after spray drying, suction filtration
Sky is dried or washs any of vacuum dried mode after centrifuging and carries out.
8. preparation method as claimed in claim 6, it is characterised in that in the step (1), the pyrolytic carbon organic matter forerunner
Body is one kind in phenolic resin, citric acid, glucose, sucrose, chitosan, polyvinylidene fluoride, pitch.
9. preparation method as claimed in claim 6, it is characterised in that in the step (3), the lithium salts be selected from lithium chloride,
One kind in lithium sulfate, lithium nitrate, lithium hydroxide, lithium acetate；The fluoride is water-soluble and the change using fluorine as anion
Compound, one kind in hydrogen fluoride, sodium fluoride, potassium fluoride, ammonium acid fluoride, ammonium fluoride；The mass fraction of the lithium salt solution
For 1% ~ 10%, the mass fraction of the fluoride aqueous solution is 1% ~ 10%.
10. a kind of high-capacity lithium ion cell, it is characterised in that the negative pole of the lithium ion battery is by such as claim 1 ~ 5
High-capacity lithium ion cell silicon based anode material described in any one is prepared, or by any one of claim 6 ~ 9 institute
High-capacity lithium ion cell silicon based anode material obtained by the preparation method stated is prepared.
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