CN102832376B - Preparation method for silicon carbon composite material for lithium ion battery negative electrode - Google Patents

Preparation method for silicon carbon composite material for lithium ion battery negative electrode Download PDF

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CN102832376B
CN102832376B CN201210287731.XA CN201210287731A CN102832376B CN 102832376 B CN102832376 B CN 102832376B CN 201210287731 A CN201210287731 A CN 201210287731A CN 102832376 B CN102832376 B CN 102832376B
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silicon
ball
composite material
lithium ion
ion battery
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CN102832376A (en
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朱敏
陈宇龙
胡仁宗
刘辉
曾美琴
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South China University of Technology SCUT
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Abstract

The invention discloses a preparation method for a silicon carbon composite material for a lithium ion battery negative electrode. The method comprises the following steps: primary ball milling: a step of adding a grinding aid into elementary silicon for ball milling; and secondary ball milling: a step of mixing silicon powder obtained after primary ball milling with carbon powder and adding a grinding aid for ball milling again. The mass content of the carbon powder is 20 to 80%. A discharge gas medium employed in the dielectric barrier discharge plasma assisted high-energy ball milling method is inert gas. According to the invention, silicon in the composite material prepared in the invention can be finely and uniformly distributed on a carbon matrix, effective refining of silicon can be carried out on the basis that the integrity of graphite sheets is ensured, reversible capacity of a battery is improved, the problems of volume expansion and poor conductivity of a silicon-based electrode are alleviated, and comprehensive performance of the lithium ion battery is improved.

Description

A kind of preparation method of silicon carbon composite material for lithium ion battery negative electrode
Technical field
The present invention relates to lithium ion battery technology, particularly a kind of preparation method of silicon carbon composite material for lithium ion battery negative electrode.
Background technology
Compared to other secondary cells, lithium ion battery have energy density large, have extended cycle life, operating voltage advantages of higher.This makes it be widely used in the life of people, becomes the ideal source of current various portable electric appts.The performance of lithium ion battery decides primarily of the electrode material of its inside.Material with carbon element is current business-like lithium ion battery negative material, this is because its have discharge platform steadily, discharge and recharge good reversibility and low cost and other advantages, but meanwhile, also there is theoretical specific capacity low (372mAh/g), poor safety performance and the shortcoming such as irreversible capacity is large first in the carbon negative pole material such as graphite.Wherein theoretical capacity this shortcoming low does not solve by improving preparation technology, becomes the essence obstacle of limiting lithium ion cell development, so need to research and develop Novel cathode material for lithium ion battery.
In the substitution material of numerous Carbon anode, silica-base material receives the concern of numerous researchers with the theoretical capacity of its superelevation (4200mAh/g).It is moderate that silica-base material also has embedding lithium/de-lithium voltage, not easily reacts with electrolyte and the advantage such as aboundresources.But there are two fatal defects in silicon based anode material: one is because silicon crystal is similar to adamantine crystal structure, it can produce huge change in volume (>300%) in the process of embedding lithium-Tuo lithium, thus cause electrode material efflorescence gradually in cyclic process, active material departs from collector, causes cycle performance to decline; Two is because silicon is semiconductor, and add that the phase in version in charge and discharge process makes its irreversible capacity large, efficiency for charge-discharge is lower.
In order to overcome the problems referred to above, research in recent years persons propose various improving one's methods, as the heterogeneous doping etc. of the preparation of nano-silicon/porous silicon particle, the surface treatment of silicon grain, silicon thin film, silicide.Wherein silicide comprises the oxide of silicon and silica-based compound.The irreversible capacity of nano simple substance silicon is high, and cycle performance is poor, and easily reunites; Irreversible capacity is higher first for the oxide of silicon, and needs to consume more electrolyte; Below the problem of the poorly conductive of silicon can not both fundamentally be changed.By contrast, adopt the route of silica-based compound can have on more composition and technologic change, and then effectively solve silicon-based anode Problems existing.Silicon-metal and silico-carbo etc. is comprised again in complex systems.The system bulking effect of silicon-metal system is alleviated not obvious, and capability retention is poor.Therefore the research of silico-carbo system has good prospect.
Carbon class negative pole has good conductivity, and in the process of embedding lithium-Tuo lithium, change in volume is very little, silicon-carbon is carried out compound, can realize their mutual supplement with each other's advantages, have practical significance for the lithium ion battery negative material preparing excellent performance.
Summary of the invention
The object of the invention is to overcome the above-mentioned shortcoming of prior art and deficiency, a kind of preparation method of silicon carbon composite material for lithium ion battery negative electrode is provided, prepares silicon grain less, the compound be more evenly distributed.
Object of the present invention is achieved through the following technical solutions:
A preparation method for silicon carbon composite material for lithium ion battery negative electrode, comprises the following steps:
First step ball milling: first adding grinding aid in elemental silicon carries out ball milling;
Second step ball milling: after the Si powder after first step ball milling and the mixing of carbon raw material powder end, add grinding aid and carry out ball milling again.
The mass percentage at described carbon raw material powder end is 20 ~ 80%.
Described grinding aid is absolute ethyl alcohol.
In described first step mechanical milling process, the quality of grinding aid is 1 ~ 7% of elemental silicon.
In described second step mechanical milling process, the quality of grinding aid is 1 ~ 5% of Si powder and carbon raw material powder end gross mass.
Described ball milling adopts dielectric barrier discharge plasma auxiliary high-energy ball-milling method.
The discharge gas medium that described dielectric barrier discharge plasma auxiliary high-energy ball-milling method adopts is inert gas.
In described first step mechanical milling process, the mass ratio of abrading-ball and elemental silicon is 30:1 ~ 60:1.
In described second step mechanical milling process, the ratio of quality and the Si powder of abrading-ball and the gross mass at carbon raw material powder end is 30:1 ~ 70:1.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the present invention passes through first by elemental silicon ball milling, again by two step ball grinding methods of ball milling after elemental silicon and the mixing of carbon raw material, obtain more tiny silicon grain, make its being more evenly distributed on carbon base body, more can utilize buffering effect and the high conductivity of carbon base body, can cycle performance of battery be improved.
(2) the present invention adds grinding aid absolute ethyl alcohol in the Si-C composite material of preparation, effectively can prevent the reuniting effect of nanoscalar silicon particles, what make silicon even dispersion is distributed on the matrix of carbon, the relieving effect of carbon base body can effectively be brought into play, for good battery performance provides powerful guarantee.
(3) using plasma of the present invention assists ball-milling method, and energy is high, can effective refinement silicon grain.In electrion environment, due to the generation of a large amount of high energy electron, the energy transferring of electric field gives neutral particle, makes the atomic zonule of particle be subject to very high electron bombardment, causes stress to be concentrated and easily fragmentation.This makes the silicon grain of fragility be more prone to refinement, can reach nanoscale.Nano level silicon grain can effectively reduce the Volumetric expansion of electrode in charge and discharge process, is conducive to the stability of holding electrode, improves its cycle performance.
(4) using plasma auxiliary ball of the present invention still obviously can detect (002) crystallographic plane diffraction peak of graphite after grinding standby product powder ball milling 5h; And under identical parameters, the graphite peaks of general milling is almost vanished from sight.This is because the high work input of on-mechanical power makes whole mechanical milling process be a process heated up, this is also a graphited process promoting carbon, so the present invention can make the layer structure of carbon in silicon-carbon compound keep good, reduce the capacitance loss caused because of structural deterioration, effectively can improve the efficiency of battery.
(5) in Process During High Energy Ball Milling of the present invention, the synergy of plasma particle flux, hot-fluid and mechanical ball-milling force serves the effect that part suppresses powder to be reunited, and makes the Si even particulate dispersion of micro nano structure on graphite matrix.
Accompanying drawing explanation
Fig. 1 is that the back scattering SEM of Si carbon-base composite material prepared by embodiment 1 schemes.
Fig. 2 is the cycle performance curve chart of Si carbon-base composite material prepared by embodiment 1.
Fig. 3 is Si 50c 50the XRD spectra of the different Ball-milling Time sample of composite material: (a) 5h; (b) 10h.
Fig. 4 is the charging and discharging curve figure under the different cycle-indexes of Si-C composite material prepared by embodiment 5.
Fig. 5 is Si-C composite material cycle performance curve chart prepared by embodiment 6.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
The preparation method of the silicon carbon composite material for lithium ion battery negative electrode of the present embodiment is as follows:
First step ball milling: add the absolute ethyl alcohol grinding aid that quality is elemental silicon quality 2% in elemental silicon, adopt dielectric barrier discharge plasma auxiliary high-energy ball grinding method ball milling, wherein the mass ratio of abrading-ball and elemental silicon is 30:1, and Ball-milling Time is 10h;
Second step ball milling: the Si powder that first step ball milling is obtained and the mixing of carbon raw material powder end, wherein the mass ratio of Si powder and carbon raw material is 1:4, add the absolute ethyl alcohol that quality is 2% of abrasive material gross mass, adopt dielectric barrier discharge plasma auxiliary high-energy ball grinding method ball milling, wherein abrading-ball is 30:1 with the ratio of Si powder and carbon raw material powder end gross mass, Ball-milling Time is 5 h, obtains silicon carbon composite material for lithium ion battery negative electrode.
Wherein the concrete steps of dielectric barrier discharge plasma auxiliary high-energy ball grinding method are as follows:
(1) front shroud and the electrode bar of ball grinder is installed, and front shroud is connected with the positive and negative two-stage of plasma electrical source respectively with the iron core in electrode bar, wherein, the iron core in electrode bar connects the positive pole of plasma electrical source, and front shroud connects the negative pole of plasma electrical source;
(2) in ball grinder, load abrading-ball and the good starting powder of proportioning;
(3) by vacuum valve, ball grinder is vacuumized, be then filled with argon gas, make the force value in ball grinder reach 0.12MPa;
(4) connect plasma electrical source, arranging plasma electrical source voltage is 15KV, and electric current is 1.5A, discharge frequency 60KHz, startup drive motors drive exciting block, makes frame and the ball grinder be fixed in frame vibrates simultaneously, carries out dielectric barrier discharge plasma auxiliary high-energy ball milling.Described exciting block adopts double-amplitude 5mm ~ 10mm, motor speed 930 ~ 1400r/min.
Si carbon-base composite powder Si prepared by the present embodiment 20c 80back scattering SEM figure see Fig. 1, as seen from the figure, after ball milling, silicon grain is not evenly distributed on carbon base body, not agglomeration, and this is conducive to the high power capacity giving full play to silicon materials.
The Si carbon-base composite powder prepared by the present embodiment, conductive agent super-p and binding agent PVDF in mass ratio 8:1:1 mix to be coated on Copper Foil and are made into electrode slice.In argon gas atmosphere glove box, using lithium metal as to electrode, ethylene carbonate (EC)+dimethyl carbonate (DMC)+1MLiPF 6for electrolyte, be assembled into button cell and test.Test condition is: charging and discharging currents density is 100uA/cm 2, discharge and recharge by voltage be 0.01V ~ 1.5V(vs.Li +/ Li).Test the cycle performance figure that obtains and see Fig. 2, as seen from the figure, the composite material prepared of the present embodiment first reversible capacity is 870.3mAh/g, and after 85 circulations, discharge capacity remains on 410.2mAh/g.
Embodiment 2
The preparation method of the silicon carbon composite material for lithium ion battery negative electrode of the present embodiment, the Ball-milling Time except second step ball milling is except 10h, and all the other are all same with embodiment 1.
Test result shows, composite material Si prepared by the present embodiment 20c 80reversible capacity be first 953.2mAh/g.After 85 circulations, discharge capacity remains on 582.9mAh/g.
Embodiment 3
The preparation method of the silicon carbon composite material for lithium ion battery negative electrode of the present embodiment, the grinding aid quality except first step ball milling is 1% of elemental silicon quality; The grinding aid quality of second step ball milling is 1% of mixed Si powder and carbon raw material powder end gross mass, and mill ball quality is outside 70:1 with the ratio of Si powder and carbon raw material powder end gross mass, and all the other are all same with embodiment 1.
Test result shows, composite material Si prepared by the present embodiment 20c 80reversible capacity be first 938.4mAh/g, 85 times circulation after discharge capacity remain on 432.8mAh/g.
Embodiment 4
The preparation method of the silicon carbon composite material for lithium ion battery negative electrode of the present embodiment, except in second step ball milling, the mass ratio of Si powder and carbon raw material is 3:7, and abrading-ball is outside 60:1 with the ratio of Si powder and carbon raw material powder end gross mass, and all the other are all same with embodiment 1.
Test result shows, composite material Si prepared by the present embodiment 30c 70reversible capacity be first 1230.4mAh/g, 85 times circulation after discharge capacity remain on 399mAh/g.
Embodiment 5
The preparation method of the silicon carbon composite material for lithium ion battery negative electrode of the present embodiment, except in second step ball milling, the mass ratio at Si powder and carbon raw material powder end is except 1:1, and all the other and embodiment 1 are together.
Si carbon-base composite material Si prepared by the present embodiment 50c 50xRD collection of illustrative plates see (a) curve in Fig. 3.
Test result shows, composite material Si prepared by the present embodiment 50c 50reversible capacity be first 1439.9mAh/g, 85 times circulation after discharge capacity remain on 381.4mAh/g,
Embodiment 6
The preparation method of the silicon carbon composite material for lithium ion battery negative electrode of the present embodiment, except second step Ball-milling Time is 1 0h, all the other and embodiment 5 are together.
Si carbon-base composite material Si prepared by the present embodiment 50c 50xRD collection of illustrative plates see (b) curve in Fig. 3.
Test the cycle performance figure obtained and see Fig. 5, as seen from the figure, composite material Si prepared by the present embodiment 50c 50reversible capacity be first 983.5mAh/g.After 85 circulations, discharge capacity remains on 558.3mAh/g.
Embodiment 7
The preparation method of the silicon carbon composite material for lithium ion battery negative electrode of the present embodiment, the grinding aid quality except first step ball milling is 7% of elemental silicon quality, and the quality of abrading-ball and the mass ratio of elemental silicon are 60:1; In second step ball milling, the mass ratio at silica flour and carbon raw material powder end is 7:3, and Ball-milling Time is outside 15h, and all the other and embodiment 1 are together.
Test result shows, composite material Si prepared by the present embodiment 70c 30reversible capacity be first 2030.6mAh/g, 50 times circulation after discharge capacity remain on 335.6mAh/g.
Embodiment 8
The preparation method of the silicon carbon composite material for lithium ion battery negative electrode of the present embodiment, the grinding aid quality except second step ball milling is 5% of mixed-powder quality, and abrading-ball is outside 50:1 with the ratio of Si powder and carbon raw material powder end gross mass, and all the other are all same with embodiment 7.
Test result shows, composite material Si prepared by the present embodiment 70c 30reversible capacity be first 1987.8mAh/g, 50 times circulation after discharge capacity remain on 359.7mAh/g.
Above-described embodiment is the present invention's preferably execution mode; but embodiments of the present invention are not limited by the examples; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (7)

1. a preparation method for silicon carbon composite material for lithium ion battery negative electrode, is characterized in that, comprises the following steps:
First step ball milling: first adding grinding aid absolute ethyl alcohol in elemental silicon carries out ball milling;
Second step ball milling: after the Si powder after first step ball milling and the mixing of carbon raw material powder end, add grinding aid absolute ethyl alcohol and carry out ball milling again; Described ball milling adopts dielectric barrier discharge plasma auxiliary high-energy ball-milling method, and concrete steps are as follows:
(1) front shroud and the electrode bar of ball grinder is installed, and front shroud is connected with the positive and negative two-stage of plasma electrical source respectively with the iron core in electrode bar, wherein, the iron core in electrode bar connects the positive pole of plasma electrical source, and front shroud connects the negative pole of plasma electrical source;
(2) in ball grinder, load abrading-ball and the good starting powder of proportioning;
(3) by vacuum valve, ball grinder is vacuumized, be then filled with argon gas, make the force value in ball grinder reach 0.12MPa;
(4) connect plasma electrical source, arranging plasma electrical source voltage is 15KV, and electric current is 1.5A, discharge frequency 60KHz, startup drive motors drive exciting block, makes frame and the ball grinder be fixed in frame vibrates simultaneously, carries out dielectric barrier discharge plasma auxiliary high-energy ball milling; Described exciting block adopts double-amplitude 5mm ~ 10mm, motor speed 930 ~ 1400r/min.
2. the preparation method of silicon carbon composite material for lithium ion battery negative electrode according to claim 1, is characterized in that, the mass percentage at described carbon raw material powder end is 20 ~ 80%.
3. the preparation method of silicon carbon composite material for lithium ion battery negative electrode according to claim 1, is characterized in that, in described first step mechanical milling process, the quality of grinding aid is 1 ~ 7% of elemental silicon.
4. the preparation method of silicon carbon composite material for lithium ion battery negative electrode according to claim 1, is characterized in that, in described second step mechanical milling process, the quality of grinding aid is 1 ~ 5% of Si powder and carbon raw material powder end gross mass.
5. the preparation method of silicon carbon composite material for lithium ion battery negative electrode according to claim 1, is characterized in that, the discharge gas medium that described dielectric barrier discharge plasma auxiliary high-energy ball-milling method adopts is inert gas.
6. the preparation method of silicon carbon composite material for lithium ion battery negative electrode according to claim 1, is characterized in that, in described first step mechanical milling process, the mass ratio of abrading-ball and elemental silicon is 30:1 ~ 60:1.
7. the preparation method of silicon carbon composite material for lithium ion battery negative electrode according to claim 1, is characterized in that, in described second step mechanical milling process, the ratio of quality and the Si powder of abrading-ball and the gross mass at carbon raw material powder end is 30:1 ~ 70:1.
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CN105692630A (en) * 2016-01-13 2016-06-22 中国科学院物理研究所 Doped and mixed nanophase material and preparation method and application thereof
CN107331842A (en) * 2017-06-30 2017-11-07 华南理工大学 It is a kind of with the antimony trisulfide base negative material of high reversible capacity and its preparation and application
CN109873132A (en) * 2017-12-05 2019-06-11 北京交通大学 A method of preparing the silicon-carbon nanocomposite of fine and close cladding
CN108448103A (en) * 2018-04-25 2018-08-24 华南理工大学 A kind of high performance silicon carbon composite with nucleocapsid and preparation method thereof and the application in lithium ion battery
CN108899522B (en) * 2018-07-06 2020-06-12 湖北工程学院 High-capacity silicon-carbon negative electrode material, preparation method and application
CN110336024A (en) * 2019-08-19 2019-10-15 银隆新能源股份有限公司 A kind of lithium ion battery silicon-carbon cathode material and preparation method thereof
CN112635730B (en) * 2020-12-17 2022-04-22 华南理工大学 Silica-based negative electrode material with high reversible capacity and preparation and application thereof

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