CN103996834B - A kind of silicon based anode material with silane coupler and conducting polymer double-coating structure and preparation method and application - Google Patents
A kind of silicon based anode material with silane coupler and conducting polymer double-coating structure and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of silicon based anode material with silane coupler and conducting polymer double-coating structure and preparation method and application.Described silicon based anode material is with elemental silicon as substrate, it is coated with silane coupler decorative layer in substrate, silane coupler decorative layer is coated with protonic acid doping state electrically conductive polyaniline, preparation method is: silane coupler and silica flour are carried out ultrasonic being blended by (1), reflux at a certain temperature, silica flour is modified；(2) it is blended ultrasonic in acid solution system for the silica flour after aniline monomer and modification, then carries out in-situ polymerization, obtain being coated with the silicon based composite material of conducting polymer；(3) by described mixed solution washing, sucking filtration, vacuum drying, obtaining having silane coupler and the silicon based anode material of conducting polymer double-coating structure, it is entrained in graphite the negative material that can be used for preparing lithium ion battery.The present invention is simple, low cost of manufacture, favorable reproducibility, it is simple to large-scale industrial production.
Description
Technical field
The invention belongs to lithium ion battery negative material and technical field of electrochemistry, relate to one have silane coupler and
Silicon based anode material of conducting polymer double-coating structure and preparation method and application.
Background technology
In the last few years, lithium ion battery had relative to secondary cells such as traditional lead-acid battery, iron cell, Ni-MH batteries
High-energy-density, high output voltage, low self-discharge, memory effect be little and advantages of environment protection, and is widely used
With research.The performance of lithium ion battery critical material is the important deciding factor of battery performance, and the exploitation of negative material improves
It it is global scientific research focus.The negative materials such as silicon materials, material with carbon element, tin material, lithium titanate, metal-oxide have obtained extensively
Research.But the lithium-ion battery system that these negative materials assemble exists, and cycle performance is poor, specific energy density is low, cost is high,
The defect such as poor stability, consistency problem, it is difficult to meet the requirement of power energy-storage battery.
Silicon based anode material is owing to its theoretical specific capacity is low more than 4200 mAh/g, intercalation potential, actual specific capacity is more than
3000 mAh/g, in the rich content of nature, the advantage, always lithium ion battery negative material such as cost of material relative moderate
Study hotspot.But the shortcomings such as the coulombic efficiency first of silicon materials is low, high rate performance is poor, cycle performance is poor seriously inhibit silicon
Base negative material large-scale application in lithium ion battery.
For the silicon based anode material of development cycle excellent performance, researcher has been developed for multiple technologies means to silicon materials
It is modified improving.Graphite, hard carbon, Colophonium, CNT, carbon nano-fiber, metal nano-tube etc. have been used for being coated with silica-based
Negative material.Such as prepared Si with regular texture such as N. Kurita2C52H18, this material is relative to C54H18Can embed in a large number
Lithium ion, and its structure also can reduce the irreversible reaction of lithium ion abjection, has good cycle performance.N. Dimov etc.
Use steam sedimentation at elementary silicon Surface coating one layer of material with carbon element, obtain the granule that average-size is 18 μm, specific capacity exists
More than 600mAh/g, higher than the theoretical specific capacity (372 mAh/g) of material with carbon element, cycle performance is suitable with material with carbon element, same to elemental silicon
Compare and improve a lot.Z. S. Wen etc. are by carrying out pyrolytic to the resin inserting graphite and elemental silicon, obtain silicon-carbon multiple
Compound, its specific capacity reaches 800～900 mAh/g, and after circulating 20 times, its specific capacity is stable at 600 mAh/g.B.J.
The prepared SiSn such as Neudecker0.87O1.20N1.72, specific capacity, close to 800 mAh/g, remains to be maintained at after 10000 discharge and recharges
600 mAh/g, discharge voltage 4.1～2.7V, circulation irreversible capacity loss is within 0.002% every time, but too high cost resistance
Hinder its business-like process.
Silane coupler is that people study the earliest, apply coupling agent the earliest, has that consumption is few, the advantage of low cost.By
Having X and R two class chemical group in silane coupled agent molecule, wherein R is can be combined with high molecular polymer organic simultaneously
Functional group；X is can be with the hydrolyzable groups of the hydroxyl reaction in silicon surface oxidation layer.Therefore silane coupler is at high molecular polymerization
Effect of coupling is played in interaction between thing and inorganic system.
Therefore, need badly at present and find modification method and the preparation side of a kind of simple silicon based anode material
Method, makes silicon based anode material have both higher coulombic efficiency first and preferable cyclical stability, it is thus possible to meet power simultaneously
The requirement of battery.
Summary of the invention
It is an object of the invention to provide and a kind of there is the silica-based of silane coupler and conducting polymer double-coating structure
Negative material and preparation method and application, uses silane coupler to modify silica flour, and it is poly-that silane coupler is positioned at conduction
Serving function served as bridge between compound organic coating layer and the inorganic system substrate of silica flour, the method is simple, manufacturing cost
Low, favorable reproducibility, it is simple to large-scale industrial production.
It is an object of the invention to be achieved through the following technical solutions:
A kind of silicon based anode material with silane coupler and conducting polymer double-coating structure, with elemental silicon as base
The end, being coated with silane coupler decorative layer in substrate, it is poly-that silane coupler decorative layer is coated with protonic acid doping state conduction
Aniline.
A kind of above-mentioned silicon based anode material preparation method with silane coupler and conducting polymer double-coating structure,
Its step is as follows:
(1) silane coupler and silica flour are carried out ultrasonic being blended, reflux at a certain temperature, silica flour is modified；Its
In: the preparation method of silica flour is the one of vapor phase method, sol-gal process, the sedimentation method, microemulsion method, ball-milling method；The grain of silica flour
Footpath interval range is between 20 to 2000 nm；Silane coupler is γ aminopropyl triethoxysilane, γ-(2,3-epoxy
Third oxygen) propyl trimethoxy silicane, γ (methacryloxypropyl) propyl trimethoxy silicane, octyltri-ethoxysilane, two
Methyl dimethoxysilane, methyl tributanoximo silane, the one of isocyanatopropyl triethoxysilane；Silane coupler
Addition is the 0.01-10% of silica flour mass fraction；Reflux temperature is 40-120 DEG C, and return time is 1-24 h；
(2) silica flour after aniline monomer and modification is carried out ultrasonic being blended, then in the acid solution system of Bronsted acid
Add Ammonium persulfate., carry out in-situ polymerization, obtain being coated with the silicon based composite material of conducting polymer；Wherein: Bronsted acid is salt
Acid, DBSA, camphorsulfonic acid, p-methyl benzenesulfonic acid, pyrovinic acid, normal-butyl/ethyl phosphonic acid, n-decane base phosphoric acid,
The mixture of one or more in benzyl phosphoric acid, benzoic acid；Polymeric reaction temperature is 0-10 DEG C, Ammonium persulfate. and aniline
The ratio adding quality is 1:2-1:4, and the silica flour after modification is 4:1-1:1 with the mass ratio of aniline, and polymerization reaction time is 4-
10 h。
(3) by described mixed solution washing, sucking filtration, vacuum drying, obtain that there is silane coupler and conducting polymer is double
The silicon based anode material of layer clad structure；Wherein: vacuum drying temperature is 45-55 DEG C, and the vacuum drying time is 10-12 h.
Prepared by said method has silane coupler and the silicon based anode material of conducting polymer double-coating structure, can
Being entrained in graphite, the silicon based anode material with silane coupler and conducting polymer double-coating structure accounts for content of graphite
1~98%。
The silane coupler modified silica flour of the present invention, forms decorative layer at silicon substrate surface, then leads at its Surface Creation
Electric polymer clad, owing to the function served as bridge of silane coupler, silicon base and outermost conducting polymer are tightly combined, energy
Effectively stop the expansion efflorescence effect of silicon, make silicon based anode material have higher coulombic efficiency first and preferable stable circulation
Property, to meet the requirement of electrokinetic cell.
Advantages of the present invention is as follows:
(1) modifying elemental silicon with silane coupler and form the first clad, what surface in situ generation outside was combined closely leads
Electric polymer clad, improves coulombic efficiency first and the cyclical stability of silicon based anode material, can meet electrokinetic cell
Requirement.
(2) this modified technique is applicable to all silicon based anode materials, simple, low cost of manufacture, favorable reproducibility, it is simple to
Large-scale industrial production.
(3) silicon-based anode of the present invention has higher specific capacity relative to the silicon-based anode of prior art, the most right
The cycle performance of existing silicium cathode is greatly improved, and after being entrained in graphite, has the performance of graphite cathode material very
The lifting of big degree.
(4) silicon based anode material obtained by the present invention has infrared spectrum as shown in Figure 5, and its characteristic peak is
2972cm-1、2926cm-1And 1735cm-1。
Accompanying drawing explanation
Fig. 1 is the reaction principle figure of silane coupler and elemental silicon substrate；
Fig. 2 is the reaction unit schematic diagram of in-situ polymerization；
Fig. 3 is the SEM figure of silane coupler modified front silicon based anode material；
Fig. 4 is the SEM of the silicon based anode material (embodiment 1) of silane coupler and conducting polymer double-coating structure
Figure；
Fig. 5 is the infrared spectrum of the silicon based anode material with silane coupler clad；
Fig. 6 is the silicon based anode material (embodiment 4) with silane coupler and conducting polymer double-coating structure
Cycle performance curve；
Fig. 7 is the cycle performance diagram of the silicon based anode material with conducting polymer double-coating structure.
Detailed description of the invention
Further illustrating the present invention below by embodiment and comparative example, these embodiments are only intended to the present invention is described,
The invention is not restricted to following example.Every technical solution of the present invention is modified or equivalent, without deviating from this
The spirit and scope of bright technical scheme, all should contain in protection scope of the present invention.
Embodiment 1:
1,0.1g γ (methacryloxypropyl) propyl trimethoxy silicane is mixed in three mouthfuls of 45mL ethanol and 5mL water
Flask hydrolyzes, after adding 4.9g silica flour, ultrasonic mixing 0.5h；Air velocity be 200mL/min, temperature be 80 DEG C, magnetic force
Reflux under stirring condition 10 h, be vacuum dried 12h at 55 DEG C, finally give the γ (methacryloxypropyl) that mass concentration is 2%
The silicon based anode material of propyl trimethoxy silicane surface modification.The reaction principle figure of silane coupler and elemental silicon substrate such as figure
Shown in 1, from the beginning of elemental silicon substrate, the first clad is silane coupler decorative layer, and the second clad is protonic acid doping state
Electrically conductive polyaniline.There is the infrared spectrum of silane coupler clad as it is shown in figure 5, at 2972 and 2926 cm-1Absorbing occurs in place
Peak, this absworption peak correspond to the stretching vibration of c h bond.
2, by 0.045g aniline monomer and 0.2g modification silica flour in the hydrochloric acid system of 30mL 3.1% percentage by volume ultrasonic
0.5 h is blended, and ultrasonic power is 1.5w/cm, and supersonic frequency is 30kHz, and then at 0-5 DEG C, dropping contains 0.0216g over cure
Sulfuric acid solution 30 mL of 1.5% percentage by volume of acid ammonium, carries out in-situ polymerization, polyreaction in reaction unit shown in Fig. 2
Time is 10 h.
3, the mixed solution in step 2 is used distilled water and ethanol alternately washing 2-3 time, sucking filtration, vacuum drying, obtain
There is silane coupler and the silicon based anode material of conducting polymer double-coating structure, do with water circulating pump sucking filtration final vacuum
Dry, vacuum drying temperature is 60 DEG C, and the vacuum drying time is 12 h.
In comparative example, silica flour is reunited more serious (such as Fig. 3), and prepare there is silane coupler and conducting polymer is double
The silicon based anode material of layer clad structure is the spheroid (such as Fig. 4) that granule is complete, and reunion situation is alleviated, and granular size is about
For 20-8000 nm.
From the silicon based anode material cycle performance curve of Fig. 7 silane coupler clad structure, filling first of material
Capacitance 2271.2 mAh/g, first charge-discharge efficiency is 69.8%, and after 200 circulations, charging capacity is 1441.48
MAh/g, capacity is maintained at about 1400 mAh/g, has the performance of excellence.
Embodiment 2:
1,0.25g γ (methacryloxypropyl) propyl trimethoxy silicane is mixed in three mouthfuls of 45mL ethanol and 5mL water
Flask hydrolyzes, after adding 4.75g silica flour, ultrasonic mixing 0.5h；Air velocity be 200mL/min, temperature be 80 DEG C, magnetic force
Reflux under stirring condition 10 h, be vacuum dried 12h at 55 DEG C, finally give the γ (methacryloxypropyl) that mass concentration is 5%
The silicon based anode material of propyl trimethoxy silicane surface modification.
2,0.045 g aniline monomer is surpassed in the hydrochloric acid system of 30mL 3.1% percentage by volume with 0.2g modification silica flour
Sound is blended 0.5 h, and ultrasonic power is 1.5w/cm, and supersonic frequency is 30kHz, and then at 0-5 DEG C, dropping contains 0.0216g mistake
Hydrochloric acid solution 30 mL of 3.1% percentage by volume of ammonium sulfate, carries out in-situ polymerization, and polymerization reaction time is 10 h.
3, the mixed solution in step 2 is used distilled water and ethanol alternately washing 2-3 time, sucking filtration, vacuum drying, obtain
There is silane coupler and the silicon based anode material of conducting polymer double-coating structure, do with water circulating pump sucking filtration final vacuum
Dry, vacuum drying temperature is 60 DEG C, and the vacuum drying time is 12 h.
From the silicon based anode material cycle performance curve of Fig. 7 silane coupler clad structure, filling first of material
Capacitance 2156.14 mAh/g, first charge-discharge efficiency is 70.2%, and after 200 circulations, charging capacity is 1553.28
MAh/g, capacity is maintained at about 1550 mAh/g, has the performance of excellence.
Embodiment 3:
1,0.1g γ (methacryloxypropyl) propyl trimethoxy silicane is mixed in three mouthfuls of 45mL ethanol and 5mL water
Flask hydrolyzes, after adding 4.9g silica flour, ultrasonic mixing 0.5h；Air velocity be 200mL/min, temperature be 80 DEG C, magnetic force
Reflux under stirring condition 10 h, be vacuum dried 12h at 55 DEG C, finally give the γ (methacryloxypropyl) that mass concentration is 2%
The silicon based anode material of propyl trimethoxy silicane surface modification.
2, by 0.09g aniline monomer and 0.2g modification silica flour in the hydrochloric acid system of 30mL 3.1% percentage by volume ultrasonic
0.5 h is blended, and ultrasonic power is 1.5w/cm, and supersonic frequency is 30kHz, and then at 0-5 DEG C, dropping contains 0.0432g over cure
Hydrochloric acid solution 30 mL of 3.1% percentage by volume of acid ammonium, carries out in-situ polymerization, and polymerization reaction time is 10 h.
3, the mixed solution in step 2 is used distilled water and ethanol alternately washing 2-3 time, sucking filtration, vacuum drying, obtain
There is silane coupler and the silicon based anode material of conducting polymer double-coating structure, do with water circulating pump sucking filtration final vacuum
Dry, vacuum drying temperature is 60 DEG C, and the vacuum drying time is 12 h.
From the silicon based anode material cycle performance curve of Fig. 7 silane coupler clad structure, filling first of material
Capacitance 1893.61 mAh/g, first charge-discharge efficiency is 71.7%, and after 200 circulations, charging capacity is 1201.83
MAh/g, capacity is maintained at about 1200 mAh/g, has the performance of excellence.
Embodiment 4:
1,0.25g γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane is mixed in 45mL ethanol and the three of 5mL water
Mouth flask hydrolyzes, after adding 4.75g silica flour, ultrasonic mixing 0.5h；Air velocity be 200mL/min, temperature be 80 DEG C, magnetic
Reflux under power stirring condition 10 h, be vacuum dried 12h at 55 DEG C, finally give γ-(2,3-epoxy third that mass concentration is 5%
Oxygen) silicon based anode material of propyl trimethoxy silicane surface modification.
2, by 0.09g aniline monomer and 0.2g modification silica flour in the hydrochloric acid system of 30mL 3.1% percentage by volume ultrasonic
0.5 h is blended, and ultrasonic power is 1.5w/cm, and supersonic frequency is 30kHz, and then at 0-5 DEG C, dropping contains 0.0432g over cure
Hydrochloric acid solution 30 mL of 3.1% percentage by volume of acid ammonium, carries out in-situ polymerization, and polymerization reaction time is 10 h.
3, the mixed solution in step 2 is used distilled water and ethanol alternately washing 2-3 time, sucking filtration, vacuum drying, obtain
There is silane coupler and the silicon based anode material of conducting polymer double-coating structure, do with water circulating pump sucking filtration final vacuum
Dry, vacuum drying temperature is 60 DEG C, and the vacuum drying time is 12 h.
From the silicon based anode material cycle performance curve of Fig. 7 silane coupler clad structure, filling first of material
Capacitance 1797.67 mAh/g, first charge-discharge efficiency is 68.9%, and after 200 circulations, charging capacity is 1295.05
MAh/g, capacity is maintained at about 1300 mAh/g, has the performance of excellence.
Embodiment 5:
1,0.25g γ (methacryloxypropyl) propyl trimethoxy silicane is mixed in three mouthfuls of 45mL ethanol and 5mL water
Flask hydrolyzes, after adding 4.75g silica flour, ultrasonic mixing 0.5h；Air velocity be 200mL/min, temperature be 80 DEG C, magnetic force
Reflux under stirring condition 10 h, be vacuum dried 12h at 55 DEG C, finally give the γ (methacryloxypropyl) that mass concentration is 5%
The silicon based anode material of propyl trimethoxy silicane surface modification.
2,0.045 g aniline monomer is surpassed in the hydrochloric acid system of 30mL 3.1% percentage by volume with 0.2g modification silica flour
Sound is blended 0.5 h, and ultrasonic power is 1.5w/cm, and supersonic frequency is 30kHz, and then at 0-5 DEG C, dropping contains 0.0216g mistake
Hydrochloric acid solution 30 mL of 3.1% percentage by volume of ammonium sulfate, carries out in-situ polymerization, and polymerization reaction time is 10 h.
3, the mixed solution in step 2 is used distilled water and ethanol alternately washing 2-3 time, sucking filtration, vacuum drying, obtain
There is silane coupler and the silicon based anode material of conducting polymer double-coating structure, do with water circulating pump sucking filtration final vacuum
Dry, vacuum drying temperature is 60 DEG C, and the vacuum drying time is 12 h.
4, by what step (3) prepared, there is silane coupler and the silicon-based anode material of conducting polymer double-coating structure
Expect to add with the mass fraction ratio of 20% and mix with graphite, obtain having high power capacity, good circulation performance for lithium-ion electric
The negative material in pond.
Be there is the silicon based anode material cycle performance curve of silane coupler and conducting polymer double-coating structure by Fig. 7
Visible, the initial charge capacity 728.83mAh/g of material, first charge-discharge efficiency is 87.00%, charges after 200 circulations
Capacity is 648.43 mAh/g, and capacity is maintained at about 650mAh/g, has the performance of excellence.
Embodiment 6:
1,0.25g γ (methacryloxypropyl) propyl trimethoxy silicane is mixed in three mouthfuls of 45mL ethanol and 5mL water
Flask hydrolyzes, after adding 4.75g silica flour, ultrasonic mixing 0.5h；Air velocity be 200mL/min, temperature be 80 DEG C, magnetic force
Reflux under stirring condition 10 h, be vacuum dried 12h at 55 DEG C, finally give the γ (methacryloxypropyl) that mass concentration is 5%
The silicon based anode material of propyl trimethoxy silicane surface modification.
2,0.045 g aniline monomer is surpassed in the hydrochloric acid system of 30mL 3.1% percentage by volume with 0.2g modification silica flour
Sound is blended 0.5 h, and ultrasonic power is 1.5w/cm, and supersonic frequency is 30kHz, and then at 0-5 DEG C, dropping contains 0.0216g mistake
Hydrochloric acid solution 30 mL of 3.1% percentage by volume of ammonium sulfate, carries out in-situ polymerization, and polymerization reaction time is 10 h.
3, the mixed solution in step 2 is used distilled water and ethanol alternately washing 2-3 time, sucking filtration, vacuum drying, obtain
There is silane coupler and the silicon based anode material of conducting polymer double-coating structure, do with water circulating pump sucking filtration final vacuum
Dry, vacuum drying temperature is 60 DEG C, and the vacuum drying time is 12 h.Copper modification silica flour is 4:1 with the mass ratio of aniline.
4, by what step (3) prepared, there is silane coupler and the silicon-based anode material of conducting polymer double-coating structure
Expect that the additional proportion with 50% mixes with graphite.
Be there is the silicon based anode material cycle performance curve of silane coupler and conducting polymer double-coating structure by Fig. 7
Visible, initial charge capacity 1264.07 mAh/g of material, first charge-discharge efficiency is 77.2%, fills after 200 circulations
Capacitance is 1083.66 mAh/g, and capacity is maintained at about 1080 mAh/g, has the performance of excellence.
Comparative example is undressed elemental silicon material.
Each embodiment is as shown in table 1 with the test case contrast of comparative example.
Table 1
Claims (9)
1. a silicon based anode material with silane coupler and conducting polymer double-coating structure, it is characterised in that described
Silicon based anode material, with elemental silicon as substrate, is coated with silane coupler decorative layer in substrate, outside silane coupler decorative layer
It is coated with protonic acid doping state electrically conductive polyaniline;
The preparation method of the described silicon based anode material with silane coupler and conducting polymer double-coating structure, specifically walks
Rapid as follows:
(1) silane coupler and silica flour are carried out ultrasonic being blended, reflux at a temperature of 40-120 DEG C, silica flour is modified；Its
In: the addition of silane coupler is the 0.01-10% of silica flour mass fraction；
(2) silica flour after aniline monomer and modification is carried out ultrasonic being blended in the acid solution system of Bronsted acid, be subsequently adding
Ammonium persulfate., carries out in-situ polymerization, obtains being coated with the silicon based composite material of conducting polymer；Wherein: Ammonium persulfate. and aniline
The ratio of addition quality be 1:2-1:4, the silica flour after modification is 4:1-1:1 with the mass ratio of aniline；
(3) by described mixed solution washing, sucking filtration, vacuum drying, obtain that there is silane coupler and conducting polymer bilayer bag
Cover the silicon based anode material of structure；
Described Bronsted acid be DBSA, camphorsulfonic acid, p-methyl benzenesulfonic acid, pyrovinic acid, normal-butyl/ethyl phosphonic acid,
The mixture of one or more in n-decane base phosphoric acid, benzyl phosphoric acid, benzoic acid.
2. described in a claim 1, there is silane coupler and the silicon based anode material of conducting polymer double-coating structure
Preparation method, it is characterised in that described method step is as follows:
(1) silane coupler and silica flour are carried out ultrasonic being blended, reflux at a temperature of 40-120 DEG C, silica flour is modified；Its
In: the addition of silane coupler is the 0.01-10% of silica flour mass fraction；
(2) silica flour after aniline monomer and modification is carried out ultrasonic being blended in the acid solution system of Bronsted acid, be subsequently adding
Ammonium persulfate., carries out in-situ polymerization, obtains being coated with the silicon based composite material of conducting polymer；Wherein: Ammonium persulfate. and aniline
The ratio of addition quality be 1:2-1:4, the silica flour after modification is 4:1-1:1 with the mass ratio of aniline；
(3) by described mixed solution washing, sucking filtration, vacuum drying, obtain that there is silane coupler and conducting polymer bilayer bag
Cover the silicon based anode material of structure.
The silicon based anode material with silane coupler and conducting polymer double-coating structure the most according to claim 2
Preparation method, it is characterised in that the preparation method of described silica flour be vapor phase method, sol-gal process, the sedimentation method, microemulsion method,
The one of ball-milling method.
4. according to described in Claims 2 or 3, there is silane coupler and the silicon-based anode of conducting polymer double-coating structure
The preparation method of material, it is characterised in that the particle size interval scope of described silica flour is between 20 to 2000 nm.
The silicon based anode material with silane coupler and conducting polymer double-coating structure the most according to claim 2
Preparation method, it is characterised in that described silane coupler is γ aminopropyl triethoxysilane, γ-(2,3-epoxy third
Oxygen) propyl trimethoxy silicane, γ (methacryloxypropyl) propyl trimethoxy silicane, octyltri-ethoxysilane, diformazan
Base dimethoxysilane, methyl tributanoximo silane, the one of isocyanatopropyl triethoxysilane.
The silicon based anode material with silane coupler and conducting polymer double-coating structure the most according to claim 2
Preparation method, it is characterised in that described return time is 1-24 h.
The silicon based anode material with silane coupler and conducting polymer double-coating structure the most according to claim 2
Preparation method, it is characterised in that described polymeric reaction temperature is 0-10 DEG C, and polymerization reaction time is 4-10 h.
The silicon based anode material with silane coupler and conducting polymer double-coating structure the most according to claim 2
Preparation method, it is characterised in that described vacuum drying temperature is 45-55 DEG C, and the vacuum drying time is 10-12 h.
9. the silicon based anode material doping with silane coupler and conducting polymer double-coating structure described in claim 1
The application of the negative material of lithium ion battery is prepared in graphite.
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