CN107611415A - A kind of preparation method of the spherical porous silicium cathode material of lithium ion battery - Google Patents
A kind of preparation method of the spherical porous silicium cathode material of lithium ion battery Download PDFInfo
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Abstract
The present invention relates to technical field of lithium ion battery negative, and in particular to a kind of to utilize spherical porous silicium cathode material of lithium ion battery that silica is raw material preparation and preparation method thereof.The spherical porous silicium cathode material of lithium ion battery of the present invention, it uses nano silicon as raw material, regulate and control the preparing spherical SiO 2 ball cluster of water oil phase interface interaction formation different-grain diameter by surfactant using inverse emulsion polymerization technology, recycle the means such as metallothermic reduction to prepare spherical porous silicium cathode material.The material is spherical, and particle diameter can improve the chemical property of silicon materials between 1 micron to 100 microns, improve silicium cathode tap density, while reduces the Volume Changes of material and reduce silicon and contacted with the direct of electrolyte.
Description
Technical field
The present invention relates to technical field of lithium ion battery negative, and in particular to one kind is raw material system using silica
The preparation method of the spherical porous silicium cathode material of standby lithium ion battery.
Background technology
For commercial lithium ion battery mainly using transistion metal compound as positive pole, graphite-like carbon material is negative pole at present, its
Maximum power density also can only achieve 150Wh/kg, can not meet high energy compact power, electrokinetic cell and energy-accumulating power station etc.
Field is to high-energy-density and the demand of high power density.Therefore high-power, the high-capacity lithium ion cell of stable performance are developed
Electrode material, constructing novel electrode structure system has important Research Significance and application prospect.
In lithium ion battery negative material, silicon has highest theory lithium storage content (4200mAh/g), more than conventional graphite
10 times of electrode (372mAh/g), it is one of most promising high performance lithium ionic cell cathode material.But silicon is in discharge and recharge
Serious bulk effect in journey be present, the stress inside particle can cause breakage of particles and efflorescence, it is difficult to form stable solid
Dielectric film, so as to cause material and collector to lose electrical contact, ultimately result in material and lose activity, limit the reality of silicon materials
Apply on border.The problem of presently, there are for silicon-based anode, to improve the chemical property of silicon materials, it is necessary to reduce the volume of material
Change and reduction silicon contact with the direct of electrolyte, make material more practical by the optimization to material and modification.
When silicon grain size is nanoscale, bulk effect of the silicon during lithiumation will be suppressed significantly, reduce particle
Efflorescence, in recent years, people are prepared for controllable one-dimensional silicon nanowires by all means, nano-structure porous silicon, and other are special
Structural form.These structures can improve the chemical property of material in terms of several.It is presoma for example with silane,
One-dimensional silicon nanowires is prepared on stainless steel substrate；Using nano silicon as silicon source, nano-silicon is obtained using magnesiothermic reduction
Powder；But most patent and document are to prepare based on the nano silica fume of high-specific surface area.Although nano silica-base material has
High surface-active, higher chemical property can be played, but nano-silicon negative material still has specific surface area high, reunites tight
Weight, tap density is low, and individual particle internal resistance is big, the practical problems such as electrical conductivity is low.It is unfavorable for practical application.Therefore high vibration density is prepared
Degree, spheric granules respectively have practical significance for the commercial applications of silicon based anode material.The preparation for the micron silicon reported at present
Method is roughly divided into two classes, and one kind obtains multi-pore micron silicon using micron silicon alloy as raw material (silicon-aluminum alloy), by corrosion；Separately
One kind is to obtain micron silicon by the purifying of high-purity scrap silicon.The micron silicon that above two method obtains has that particle diameter is random,
The shortcomings that micron grain size can not regulate and control.Therefore jolt ramming of the exploitation spherical silicium cathode material of controlledly synthesis micron to raising negative material
Density, while ensure certain high-specific surface area to promote reactivity that there is double action.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of electrochemistry that can improve silicon materials
Can, improve silicium cathode tap density, while reduce material Volume Changes and reduction silicon and electrolyte direct contact lithium from
The sub- spherical porous silicium cathode material of battery.
A kind of preparation method of the spherical porous silicium cathode material of lithium ion battery of the present invention, it comprises the following steps：
A, monodisperse silica is synthesized：According to volume ratio 0.5~10:50~180, tetraethyl orthosilicate is dispersed in anhydrous
In ethanol, then ammoniacal liquor is added dropwise, stirs 1~48h, obtain monodisperse silica；
B, inverse emulsion polymerization：According to 0.1~1g of solid-to-liquid ratio:1~50mL, the monodisperse silica that a steps are obtained
It is scattered to be added drop-wise in deionized water in the oil phase containing emulsifying agent, 1~5min of stirring and emulsifying, evaporate, obtain preparing spherical SiO 2
Ball cluster；
C, metallothermic reduction：The silica spheres cluster that b is obtained is with sodium chloride according to mass ratio 1:1~20 mixing, adds
Ionized water, 0.5~5h is stirred, is evaporated moisture at 90~100 DEG C；According still further to silica and metallic reducing agent mass ratio 1:
0.1~10 mixing, under an inert atmosphere, 500~1000 DEG C are warming up to 1~10 DEG C/min speed, are incubated 1~12h, cooling
To room temperature, the product after cooling is soaked in acid, washed, dries, produces.
A kind of preparation method of the above-mentioned spherical porous silicium cathode material of lithium ion battery, ammoniacal liquor wherein described in a steps
Concentration is 10~38wt%.
Further, the preparation method of the spherical porous silicium cathode material of above-mentioned a kind of lithium ion battery, wherein in a steps also
Contain one kind in template CTAB, F127, polystyrene microsphere, carbon ball.
Further, the preparation method of the spherical porous silicium cathode material of above-mentioned a kind of lithium ion battery, institute wherein in b step
Emulsifying agent is stated as DTAB, DTAC, TTAB, 14
Alkyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, sorbitan monostearate, anhydrous sorbitol list oleic acid
Ester, sorbitan sesquioleate, anhydrous sorbitol list isomery stearate, methyl glycol fatty acid ester, propane diols list are stearic
Acid esters, glycerin monostearate, Hypermer 2296, Hypermer 2524, Hypermer 2234, Hypermer B-246
SF、Hypermer 1083 SF、Hypermer 1599A、Hypermer B-210、Hypermer 1031、Hypermer B-
206th, Triton X-100, APES, the synthol of polyoxyethylene -6, alkoxylate C12/C15 alcohol, poly-
Oxygen ethene -6C12/C15 alcohol, the one or more of APEO natural fatty alcohol.
Further, the preparation method of the spherical porous silicium cathode material of above-mentioned a kind of lithium ion battery, institute wherein in b step
State oil phase for ethane, propane, normal butane, heptane, nonane, decane, n-hexane, 1- octadecylenes, dodecane, hexadecane, iso-butane,
One or more in pentane, neopentane, isopentane, neohexane, isohexane, hexamethylene, normal octane, isooctane.
A kind of preparation method of the above-mentioned spherical porous silicium cathode material of lithium ion battery, metal is also wherein described in step c
Former agent is at least one of magnesium, aluminium, lithium, sodium, potassium metal dust；The particle diameter of the metal dust is 100~300 mesh.
A kind of preparation method of the above-mentioned spherical porous silicium cathode material of lithium ion battery, indifferent gas wherein described in step c
Atmosphere is one kind in nitrogen, argon gas, helium.
Further, the preparation method of the spherical porous silicium cathode material of above-mentioned a kind of lithium ion battery, institute wherein in step c
State to soak the product after cooling in acid and be specially：First the product after cooling is soaked in hydrochloric acid or sulfuric acid and goes to clean
Matter, then 1~30min of hydrofluoric acid dips with 1~10wt%.
Further, the preparation method of the spherical porous silicium cathode material of above-mentioned a kind of lithium ion battery, wherein the hydrochloric acid
Or the concentration of sulfuric acid is 1~36wt%.
The spherical porous silicium cathode material of lithium ion battery that above-mentioned preparation method is prepared, the spherical porous silicium cathode
The particle diameter of material is 1~100 μm.
The beneficial effects of the invention are as follows：The spherical porous silicium cathode material of lithium ion battery of the present invention, it uses nano-silica
SiClx is raw material, and regulating and controlling water oil phase interface interaction by surfactant using inverse emulsion polymerization technology forms different-grain diameter
Preparing spherical SiO 2 ball cluster, the means such as metallothermic reduction are recycled to prepare spherical porous silicium cathode material.The material is spherical, grain
Footpath can improve the chemical property of silicon materials between 1 micron to 100 microns, improve silicium cathode tap density, reduce simultaneously
The Volume Changes and reduction silicon of material contact with the direct of electrolyte；Its preparation method is easily controllable, and material composition is uniform, pattern
Controllable with particle, tap density is high, and obtained material can be directly used for lithium ion battery negative material.
Brief description of the drawings
The schematic diagram of the spherical porous silicium cathode material of lithium ion battery prepared by Fig. 1 present invention；
The scanning electron microscope diagram of silica spheres cluster prepared by Fig. 2 present invention；
The scanning electron microscope diagram of the spherical porous silicium cathode material of lithium ion battery prepared by Fig. 3 present invention；
The cycle performance curve for the spherical porous silicium cathode material of lithium ion battery that Fig. 4 present invention is prepared by embodiment 2；
The constant current for the spherical porous silicium cathode material different multiplying of lithium ion battery that Fig. 5 present invention is prepared by embodiment 2 is filled
Discharge curve.
Embodiment
Technical scheme is described in further detail with reference to specific embodiment, but protection scope of the present invention is not
It is confined to as described below.
Embodiment 1
4.5 milliliters of tetraethyl orthosilicates are first dissolved in 45.5 milliliters of absolute ethyl alcohols, added 9 milliliters of ammoniacal liquor, 25 milliliters go
The mixed liquor of ionized water, 30 milliliters of absolute ethyl alcohols, stir 6 hours, silica and 60 DEG C of dryings are collected by centrifugation.Take 0.4 gram two
Silica is dissolved in 10 milliliters of deionized water, and ultrasonic disperse, obtains aqueous phase；Take 40 milliliters hexadecane and 0.09 gram
Hypermer 2296 is mixed, and obtains oil phase；Aqueous phase is added drop-wise to oil phase, emulsified 3 minutes at 8000 revs/min, at 98 DEG C
Stand 4 hours.It is collected by centrifugation to obtain silica spheres, in atmosphere 350 DEG C of insulations, 30 minutes organics removals.To obtain two
Silicon oxide ball is with sodium chloride according to mass ratio 1：5 mixing, add 30 milliliters of deionized water and stir 2 hours, be evaporated at 94 DEG C.
According still further to silica and magnesium powder 1：1 mass ratio mixing, under argon gas protection, it is small to be placed in 700 DEG C of insulations 5 of closed system
When.Take out and first cleaned with 100 milliliters of 1M hydrochloric acid after cooling, then obtained with 50 milliliter 5% of hydrofluoric acid wash, collected by suction
The spherical silicon of um porous.
Embodiment 2
4 milliliters of tetraethyl orthosilicates are first dissolved in 90 milliliters of absolute ethyl alcohols, have added 9 milliliters of ammoniacal liquor, 30 milliliters of deionizations
The mixed liquor of water, 45 milliliters of absolute ethyl alcohols, stir 12 hours, silica and 60 DEG C of dryings are collected by centrifugation.Take 0.6 gram of titanium dioxide
Silicon is dissolved in 10 milliliters of deionized water, and ultrasonic disperse, obtains aqueous phase；Take 40 milliliters of 1- octadecylenes and 0.1 gram of Hypermer
2296 mix, and obtain oil phase；Aqueous phase is added drop-wise to oil phase, emulsified 2 minutes at 9000 revs/min, it is small to stand 5 at 98 DEG C
When.It is collected by centrifugation to obtain silica spheres, in atmosphere 450 DEG C of insulations, 60 minutes organics removals.The silica that will be obtained
Ball is with sodium chloride according to mass ratio 1：10 mixing, add 50 milliliters of deionized water and stir 3 hours, be evaporated at 92 DEG C.Press again
According to silica and magnesium powder 1：1 mass ratio mixing, under argon gas protection, it is placed in 650 DEG C of closed system and is incubated 5 hours.Treat
Take out after cooling and first cleaned with 110 milliliters of 1M hydrochloric acid, then micron is obtained with 50 milliliter 5% of hydrofluoric acid wash, collected by suction
Porous silicon ball.
The preparation flow schematic diagram of the spherical porous silicium cathode material of lithium ion battery of the present invention as shown in Figure 1, to above-mentioned system
Standby um porous silicon ball is scanned Electronic Speculum test, and the scanning electron microscope diagram of obtained silica spheres cluster is shown in Fig. 2 institutes
Show；The scanning electron microscope diagram of the spherical porous silicium cathode material of lithium ion battery prepared by the present invention is as shown in Figure 3；To preparing
Obtained lithium ion battery negative material, carries out electro-chemical test, and the constant current of obtained cycle performance curve and different multiplying is filled
Discharge curve is shown in attached Figure 4 and 5 respectively.
It can be drawn from figure：Monodisperse silica is self-assembled into regular silica spheres by inverse emulsion polymerization
Cluster, then after magnesiothermic reduction, remain to keep ball cluster pattern.The spherical porous silicium cathode material of lithium ion battery of the present invention discharges first
Specific capacity 2322mAh/g, charge specific capacity 1230mAh/g, coulombic efficiency is 53% first, but the coulombic efficiency in following cycle
Rise, the 4th circle rises to 96%, 98% is always held at after the 8th circle, its specific capacity is maintained at 1150mAh/g after 100 circle circulations
Left and right.This material also can stably carry out discharge and recharge under different multiplying powers, as multiplying power reduces, specific capacity increase.
Embodiment 3
5 milliliters of tetraethyl orthosilicates are first dissolved in 55 milliliters of absolute ethyl alcohols, then 5 milliliters of ammoniacal liquor, 30 milliliters of deionizations have been added dropwise
The mixed liquor of water, 45 milliliters of absolute ethyl alcohols, stir 12 hours, silica and 60 DEG C of dryings are collected by centrifugation.Take 0.6 gram of titanium dioxide
Silicon is dissolved in 10 milliliters of deionized water, and ultrasonic disperse, obtains aqueous phase；The dodecane and 0.12 gram of span-80 for taking 60 milliliters mix
Stirring is closed, obtains oil phase；Aqueous phase is added drop-wise to oil phase, emulsified 4 minutes at 9000 revs/min, 5 hours are stood at 98 DEG C.Centrifugation
Collection obtains silica spheres, in atmosphere 550 DEG C of insulations, 30 minutes organics removals.By obtained silica spheres and chlorination
Sodium is according to mass ratio 1：15 mixing, add 70 milliliters of deionized water and stir 4 hours, be evaporated at 90 DEG C.According still further to titanium dioxide
Silicon and magnesium powder 1：0.9 mass ratio mixing, under argon gas protection, it is placed in 650 DEG C of closed system and is incubated 3 hours.After cooling
Taking-up is first cleaned with 110 milliliters of 1M hydrochloric acid, then obtains micron porous silicon with 30 milliliter 5% of hydrofluoric acid wash, collected by suction
Ball.
Embodiment 4
3 milliliters of tetraethyl orthosilicates are first dissolved in 45.5 milliliters of absolute ethyl alcohols, then be added dropwise 9 milliliters of ammoniacal liquor and 45 milliliters go from
The mixed liquor of sub- water, stir 10 hours, silica and 60 DEG C of dryings are collected by centrifugation.0.5 gram of silica is taken to be dissolved in 20 milliliters
Deionized water, and ultrasonic disperse obtains aqueous phase；The 1- octadecylenes and 0.15 gram of mixing of Hypermer 2524 for taking 90 milliliters stir
Mix, obtain oil phase；Aqueous phase is added drop-wise to oil phase, emulsified 1 minute at 8000 revs/min, 4 hours are stood at 98 DEG C.It is collected by centrifugation
Silica spheres are obtained, in atmosphere 450 DEG C of insulations, 30 minutes organics removals.By obtained silica spheres and sodium chloride by
According to mass ratio 1：8 mixing, add 40 milliliters of deionized water and stir 1 hour, be evaporated at 95 DEG C.According still further to silica and magnesium
Powder 1：1.1 mass ratio mixing, under argon gas protection, it is placed in 700 DEG C of closed system and is incubated 5 hours.Take out after cooling first
Cleaned with 150 milliliters of 1M hydrochloric acid, then um porous silicon ball is obtained with 25 milliliter 5% of hydrofluoric acid wash, collected by suction.
Described above is only the preferred embodiment of the present invention, it should be understood that the present invention is not limited to described herein
Form, the exclusion to other embodiment is not to be taken as, and can be used for various other combinations, modification and environment, and can be at this
In the text contemplated scope, it is modified by the technology or knowledge of above-mentioned teaching or association area.And those skilled in the art are entered
Capable change and change does not depart from the spirit and scope of the present invention, then all should be in the protection domain of appended claims of the present invention
It is interior.
Claims (10)
1. a kind of preparation method of the spherical porous silicium cathode material of lithium ion battery, it is characterised in that comprise the following steps：
A, monodisperse silica is synthesized：According to volume ratio 0.5~10:50~180, tetraethyl orthosilicate is dispersed in absolute ethyl alcohol
In, then ammoniacal liquor is added dropwise, 1~48h is stirred, obtains monodisperse silica；
B, inverse emulsion polymerization：According to 0.1~1g of solid-to-liquid ratio:1~50mL, the monodisperse silica that a steps obtain is disperseed
In deionized water, it is added drop-wise in the oil phase containing emulsifying agent, 1~5min of stirring and emulsifying, evaporates, obtain preparing spherical SiO 2 ball
Cluster；
C, metallothermic reduction：The silica spheres cluster that b is obtained is with sodium chloride according to mass ratio 1:1~20 mixing, adds deionization
Water, 0.5~5h is stirred, is evaporated moisture at 90~100 DEG C；According still further to silica and metallic reducing agent mass ratio 1:0.1~
10 mixing, under an inert atmosphere, 500~1000 DEG C are warming up to 1~10 DEG C/min speed, 1~12h is incubated, is cooled to room
Temperature, the product after cooling is soaked in acid, washed, dried, produce.
2. a kind of preparation method of the spherical porous silicium cathode material of lithium ion battery according to claim 1, its feature exist
In the concentration of ammoniacal liquor described in a steps is 10~38wt%.
3. a kind of preparation method of the spherical porous silicium cathode material of lithium ion battery according to claim 1 or 2, its feature
It is, also containing one kind in template CTAB, F127, polystyrene microsphere, carbon ball in a steps.
4. a kind of preparation method of the spherical porous silicium cathode material of lithium ion battery according to claim 1, its feature exist
In emulsifying agent described in b step is DTAB, DTAC, CPC
Base ammonium bromide, tetradecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, sorbitan monostearate, dehydration
Sorbitol monooleate, sorbitan sesquioleate, anhydrous sorbitol list isomery stearate, methyl glycol fatty acid ester,
Propylene glycol monostearate, glycerin monostearate, Hypermer 2296, Hypermer 2524, Hypermer 2234,
Hypermer B-246 SF、Hypermer 1083 SF、Hypermer 1599A、Hypermer B-210、Hypermer
1031st, Hypermer B-206, Triton X-100, APES, the synthol of polyoxyethylene -6, alcoxyl
Base C12/C15 alcohol, the C12/C15 of polyoxyethylene -6 alcohol, the one or more of APEO natural fatty alcohol.
5. a kind of preparation method of the spherical porous silicium cathode material of lithium ion battery according to claim 1 or 4, its feature
Be, oil phase described in b step be ethane, propane, normal butane, heptane, nonane, decane, n-hexane, 1- octadecylenes, dodecane,
One kind in hexadecane, iso-butane, pentane, neopentane, isopentane, neohexane, isohexane, hexamethylene, normal octane, isooctane
It is or a variety of.
6. a kind of preparation method of the spherical porous silicium cathode material of lithium ion battery according to claim 1, its feature exist
In metallic reducing agent described in step c is at least one of magnesium, aluminium, lithium, sodium, potassium metal dust；The grain of the metal dust
Footpath is 100~300 mesh.
7. a kind of preparation method of the spherical porous silicium cathode material of lithium ion battery according to claim 1 or 6, its feature
It is, inert atmosphere described in step c is one kind in nitrogen, argon gas, helium.
8. a kind of preparation method of the spherical porous silicium cathode material of lithium ion battery according to claim 1, its feature exist
In the product after cooling soaked in acid described in step c being specially：First by the product after cooling in hydrochloric acid or sulfuric acid
The removal of impurity, then 1~30min of hydrofluoric acid dips with 1~10wt% are removed in immersion.
9. a kind of preparation method of the spherical porous silicium cathode material of lithium ion battery according to claim 8, its feature exist
In the concentration of the hydrochloric acid or sulfuric acid is 1~36wt%.
10. the spherical porous silicium cathode material of lithium ion battery that the preparation method described in any one of claim 1~9 is prepared
Material, it is characterised in that the particle diameter of the spherical porous silicium cathode material is 1~100 μm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108715451A (en) * | 2018-06-15 | 2018-10-30 | 辽宁科技大学 | It is a kind of avoid by-product generate magnesiothermic reduction prepare pure silicon material method |
| CN110562985A (en) * | 2019-09-23 | 2019-12-13 | 北京化工大学 | preparation method and application of porous silicon nanowire |
| CN111446432A (en) * | 2020-04-20 | 2020-07-24 | 上海交通大学 | Preparation method of nano silicon/carbon composite negative electrode material for lithium ion battery |
| CN114400327A (en) * | 2022-01-07 | 2022-04-26 | 上海交通大学 | Preparation method of nano silicon-carbon negative electrode material |
| CN116969464A (en) * | 2023-09-22 | 2023-10-31 | 中石油深圳新能源研究院有限公司 | Lithium ion battery negative electrode material and preparation method thereof |
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