CN107634199A - A kind of nano-silicon, preparation method and its application in silicon-carbon composite cathode material and lithium ion battery - Google Patents

A kind of nano-silicon, preparation method and its application in silicon-carbon composite cathode material and lithium ion battery Download PDF

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CN107634199A
CN107634199A CN201710792080.2A CN201710792080A CN107634199A CN 107634199 A CN107634199 A CN 107634199A CN 201710792080 A CN201710792080 A CN 201710792080A CN 107634199 A CN107634199 A CN 107634199A
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silicon
nano
carbon composite
cathode material
composite cathode
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王成云
侯桃丽
陈校军
蒋新欣
邓昊昆
刘金成
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Eve Energy Co Ltd
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Eve Energy Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention provides a kind of nano-silicon, preparation method and its purposes in silicon-carbon composite cathode material and lithium ion battery.The invention provides a kind of method that low temperature molten salt method prepares pure silicon component nano-silicon, obtained nano-silicon is to assemble second particle of the particle diameter formed in 80 120nm by a silicon grain, it is highly suitable for preparing silicon-carbon composite cathode material, silicon carbon material is prepared by the method for mechanical fusion high temperature pyrolysis as silicon source using it, while the technical problem of solution is to improve the electronic conductivity of silicon materials, silicium cathode caused bulk effect during alloy and removal alloying can be effectively buffered, improves the structural stability in the cyclic process of material.Silicon-carbon cathode material prepared by the present invention has the advantages that initial coulomb efficiency height, good cycle, compacted density are high, electrode structure is stable, and the preparation process of nano-silicon and silicon-carbon composite cathode pole material is environment-friendly pollution-free.

Description

A kind of nano-silicon, preparation method and its in silicon-carbon composite cathode material and lithium-ion electric The application in pond
Technical field
The invention belongs to lithium ion battery negative material field, is related to a kind of nano-silicon, preparation method and applications, especially It is related to a kind of nano-silicon, preparation method and its application in silicon-carbon composite cathode material and lithium ion battery, and it is negative using this The lithium ion battery of pole material.
Background technology
Lithium ion battery is so that it is bigger than energy, operating voltage is high, service life cycle is long, small volume, in light weight, green ring The advantages such as guarantor are widely used in various portable electric appts and electric automobile.Current commercialized negative electrode of lithium ion battery material Material negative material is mainly graphite, including native graphite, Delanium etc., but its theoretical specific capacity is only 372mAh/g, difficult To meet the needs of lithium ion battery applications field is to high-energy-density power supply.Therefore, the lithium ion of Novel high-specific capacity flexible is developed Cell negative electrode material turns into urgent problem.
In non-carbon negative material, silica-base material is due to the theoretical embedding lithium capacity 4200mAh/g of highest, far above it The theoretical embedding lithium capacity of its all negative material, and the rich reserves (ranked second position in crustal elements content) of silicon, right and wrong often with The potential negative material as lithium ion battery of future generation, therefore as the focus of research.However, silica-base material is in high level Under conditions of removal lithium embedded, there is up to more than 300% bulk effect, resulting mechanicals efforts can cause silicon grain Broken, efflorescence, lose the electrical contact of silicon grain and collector, cause the sharp-decay of silicium cathode material capacity, show as The cyclical stability of extreme difference.In addition, silicon is a kind of semi-conducting material, its intrinsic conductivity is only 6.7 × 10-4S/cm.For upper Problem is stated, relatively effective in the method for modifying proposed at present is to prepare Si-C composite material to alleviate in battery charge and discharge process Volumetric expansion, the method had been widely used in the study on the modification of lithium ion battery negative material.
Yolk-eggshell structural porous silicon-carbon complex microsphere preparation method disclosed in CN103531760, its preparation section is excessively Complexity, inner hollow diameter control is excessively difficult, although certain expansion space of silicon can be supplied, tap density is not high, and electric conductivity is poor, And hf etching need to be used, environmental pollution is serious.The disclosed nothings prepared using PVC cladding silica flours of CN103000901 are determined The preparation method of shape carbon coating silicon grain, although bulk effect can stopped to a certain degree, electric conductivity is poor, and PVC bags Coating is more crisp, easily destroyed, is unfavorable for circulating for a long time.
When preparing silicon-carbon composite cathode material, silicon source species mainly includes the oxide of silicon, the halide of silicon, man-made glass Diatomite of fiber and natural minerals etc..Traditionally, silicon materials are mainly prepared using solid phase reduction silica, such as higher than 2000 DEG C carbon thermal reduction silica (Nagamori, M., Malinsky, I.＆Claveau, A.Metall.Trans.B17, 503-514(1986))；At 650 DEG C magnesiothermic reduction (Bao Z, Weatherspoon M R, Shian S, et al., Nature,446:172-175, (2007)) and more than under the conditions of 850 DEG C electrochemical reduction (Cho S K, Fan F R F, Bard AJ.,Angewandte Chemie,124:12912-12916(2012)).Silicon nano material prepared by these technologies is past It is longer and expensive toward the time, it is often more important that the impurity such as Si-Mg alloy come due to height temperate zone is difficult to divide from nano-silicon From.
Therefore, a kind of new environment-friendly low-temperature synthesis of nanometer silicon materials are developed with prepare high conductivity, high power capacity, Initial coulomb efficiency is high, the silicon-carbon composite cathode material of good cycling stability is significant, to the system of high-performance nano silicon It is standby and its be still the problem in current silica-base material field in application study prepared by silicon-carbon composite cathode material.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of nano-silicon, preparation method and its in silicon-carbon The purposes of composite negative pole material and lithium ion battery.The nano-silicon of the present invention is the two of the pure silicon component being made up of a silicon grain Secondary particle, it is highly suitable for preparing silicon-carbon composite cathode material, and silicon-carbon composite cathode is further made using it as silicon source Material, it can effectively lift the electronic conductivity of silicon materials, reduce the bulk effect of silicon, and silicon-carbon composite cathode material has head The advantages that secondary coulombic efficiency height, good cycle, compacted density are high, electrode structure is stable.
To realize above-mentioned technical purpose, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of nano-silicon, the nano-silicon is that a silicon grain assembles to be formed secondary Grain, the particle diameter of the second particle is in 80-120nm.
The nano-silicon of the present invention is a kind of pure silicon product, and it is that a silicon grain assembles the secondary pure silicon granules to be formed, grain Footpath is in 80-120nm, such as 80nm, 85nm, 88nm, 90nm, 95nm, 97nm, 100nm, 102nm, 105nm, 110nm, 115nm Or 120nm etc., preferably 100nm.
Preferably, the particle diameter of a silicon grain is in 20-30nm, for example, 20nm, 22nm, 23nm, 25nm, 26nm, 28nm or 30nm etc..
Second aspect, the present invention provide the preparation method of nano-silicon as described in relation to the first aspect, and methods described includes following Step：
(1) by AlCl3, reducing agent and silicon source be put into the reactor filled with protective atmosphere, seal, be warming up to 200- 500 DEG C of reactions, reducing agent reduce to silicon source, obtain including the sediment of nano-silicon；
(2) with acid cleaning sediment, be then placed in using ethanol as the HF solution of solvent in soak, vacuum drying obtain nanometer Silicon；
Wherein, the mol ratio of step (1) reducing agent and silicon source is more than reducing agent and silicon source in redox reaction Stoichiometric proportion, that is to say, that reducing agent is excessive in reaction.
In the method for the present invention, the temperature of step (1) described reaction is 200-500 DEG C, for example, 200 DEG C, 210 DEG C, 220 DEG C, 240 DEG C, 260 DEG C, 285 DEG C, 300 DEG C, 320 DEG C, 350 DEG C, 375 DEG C, 400 DEG C, 425 DEG C, 450 DEG C, 465 DEG C, 480 DEG C or 500 DEG C etc..If temperature is less than 200 DEG C, AlCl3It can not melt and watery fusion reaction environment is provided；If temperature is higher than 500 DEG C, Alusil alloy can be formed.
It is highly preferred that the temperature of step (1) described reaction is 250-350 DEG C, can not only provide on this condition good Environment is melted, reduces energy consumption, the generation of side reaction can also be reduced, lifts product purity.
In the present invention, step (1) described reactor is that can provide the reactor of hyperbaric environment, such as pressure cooker and reactor Deng.
As the optimal technical scheme of the preparation method of the nano-silicon, it is clear with acid that methods described is additionally included in step (2) Wash after sediment, be put into using ethanol as the HF solution of solvent in soak before, carry out the step of deionized water and ethanol clean.
Preferably, step (1) AlCl3Mass ratio with silicon source is (4-8):1, such as 4:1、5:1、5.5:1、6:1、 6.5:1、7:1 or 8:1 etc., be preferably (4-5):1.
Preferably, step (1) AlCl3, reducing agent and silicon source mass ratio be (4-8):(2-3):(1-3), such as 4:3:1、5:3:1、8:3:1、4:3:1.5、5:3:1.5、7:3:1.5、4:2.5:1 or 4.5:3:1 etc., be preferably (4-5):2:1.
Preferably, group of step (1) the described reducing agent including any one in magnesium powder, sodium powder or aluminium powder or at least two Close.
Preferably, step (1) described silicon source includes SiCl4、SiO2, in man-made vitreous fibres or natural mineral diatomite Any one or at least two combination.
Preferably, step (1) described protective atmosphere is any one in nitrogen, helium or argon gas or at least two Mixed atmosphere；
Preferably, the heating rate of step (1) described heating is 2-5 DEG C/min, for example, 2 DEG C/min, 3 DEG C/min, 3.5 DEG C/min, 4 DEG C/min, 4.5 DEG C/min or 5 DEG C/min etc..
Preferably, the time of step (1) described reaction is 6-10h, for example, 6h, 7h, 7.2h, 7.5h, 8h, 8.5h, 9h or 10h etc..
Preferably, step (2) it is described acid be 0.1-0.2M hydrochloric acid, concentration such as 0.1M, 0.12M, 0.15M, 0.18M or 0.2M etc..
Preferably, step (2) is described using ethanol as in the HF solution of solvent, HF mass fraction is 5%~20%, such as 5%th, 7%, 10%, 12.5%, 15%, 17%, 18%, 19% or 20% etc., preferably 10%.
Preferably, the time of step (2) described immersion is 15-45min, for example, 15min, 18min, 20min, 25min, 30min, 35min, 40min or 45min etc., preferably 20min.
Preferably, step (2) the vacuum drying temperature be 40-100 DEG C, such as 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C etc., preferably 80 DEG C.
As the further preferred technical scheme of the preparation method of the nano-silicon, the described method comprises the following steps：
(1) by 4-8 parts by weight AlCl3It is well mixed and is put into the pressure cooker full of nitrogen with 2-4 parts by weight magnesium powder, then Take 1-3 parts by weight SiCl4It is put into pressure cooker, seals, 200-500 DEG C of reaction 6-10h is warming up to 2-5 DEG C/min speed, Magnesium powder is to SiCl4Reduced, obtain including the sediment of nano-silicon；
Wherein, magnesium powder and SiCl4Mol ratio be more than 2:1；
(2) sediment is cleaned with 0.1-0.2M hydrochloric acid, is then cleaned with deionized water and ethanol, is finally putting into ethanol To soak 30min in the HF solution of solvent, nano-silicon is obtained in 50 DEG C of vacuum drying.
In the present invention, the action of step (2) sealing is fast, is preferably added to SiCl4Seal at once afterwards.
The third aspect, the present invention provide a kind of nano-silicon using described in first aspect and prepare silicon-carbon composite cathode as silicon source The method of material, specifically includes following steps：
Nano-silicon, graphite microparticles are placed in ball mill, ball milling disperses in the environment of organic solvent, vacuum drying It is placed in pitch in cone-type mixer and is slightly mixed afterwards, then the mixed-powder after thick mix is placed in mechanical fusion machine and carries out machinery Fusion, is finally heat-treated under the protection of inert gas, silicon-carbon composite cathode material is obtained after cooling.
As the optimal technical scheme of the preparation method of the silicon-carbon composite cathode material, silicon-carbon composite cathode material is prepared The mass fraction of raw material be：Nano-silicon 10-40%, graphite microparticles 30-80%, pitch 10-30%, such as nano-silicon 10%, Graphite microparticles 80%, pitch 10%；Nano-silicon 20%, graphite microparticles 60%, pitch 20%；Nano-silicon 30%, graphite microparticles 50%th, pitch 20%；Nano-silicon 40%, graphite microparticles 50%, pitch 10% etc..
Preferably, the graphite microparticles be flaky graphite, spherical graphite or Delanium in any one or at least Two kinds of combination.
Preferably, the median particle diameter of the graphite microparticles is 5-15 μm, such as 5 μm, 8 μm, 10 μm, 12.5 μm or 15 μm Deng.
Preferably, the organic solvent is ethanol, acetone, acetonitrile, tetrahydrofuran, chloroform, 1-METHYLPYRROLIDONE In DMF any one or at least two combination.
Preferably, the pitch be low temperature coal tar pitch, medium temperature coal pitch, coal tar pitch, slag oil asphalt, tar asphalt, In bitumen, graphite pitch or shale tar pitch any one or at least two combination.
Preferably, the median particle diameter of the pitch is 1-20 μm, such as 1 μm, 5 μm, 10 μm, 15 μm or 20 μm etc..
Preferably, the Ball-milling Time is 3-10h, such as 3h, 4h, 5h, 8h or 10h etc..
Preferably, the mechanical fusion machine is any one in horizontal fusion machine or vertical fusion machine.
Preferably, the rotating speed of the mechanical fusion machine is 500-1000r/min, and the mechanical fusion time is 15-60min.
Preferably, described be heat-treated is：500 DEG C first are risen to 0.5-5 DEG C/min heating rate, is incubated 1-200min, 900-1200 DEG C is risen to 0.5-10 DEG C/min heating rate again, is incubated 10-240min, last nature or program are cooled to room Temperature.
Preferably, the inert gas include nitrogen, argon gas, neon, helium or xenon in any one at least two Combination.
Fourth aspect, the present invention provide a kind of silicon-carbon composite cathode material, and the silicon-carbon composite cathode material is by third party Method described in face is prepared.
5th aspect, the present invention provide a kind of lithium ion battery, and the negative material in the negative electrode of lithium ion battery is the Silicon-carbon composite cathode material described in four aspects.
Preferably, the negative pole is prepared via a method which to obtain：By the silicon-carbon composite cathode material described in claim 9 Material, conductive agent and binding agent 80-94 by mass percentage：3-10：5-10 dissolvings mix in a solvent, coated on copper foil current collector On, it is dried in vacuo and negative pole is made.
Preferably, the conductive agent is Super P-Li, acetylene black, CNT, graphene, carbon nano-fiber or fowler Alkene any one or at least two combination.
Preferably, the binding agent is polyimide resin, acrylic resin, polyvinylidene fluoride, polyvinyl alcohol, carboxylic first In base sodium cellulosate, butadiene-styrene rubber or sodium alginate any one or at least two combination.
Preferably, the solvent is deionized water, 1-METHYLPYRROLIDONE, dimethylformamide, acetone or Methylethyl In ketone any one or at least two combination.
Compared with the prior art, the present invention has the advantages that：
(1) the invention provides a kind of new nano-silicon, it is the secondary of the pure silicon component that is made up of a silicon grain Particle, second particle particle diameter are highly suitable for preparing silicon-carbon composite cathode in 80-120nm, the nano-silicon of this pure silicon component Material, it is employed as silicon source and silicon-carbon composite cathode material is made, can effectively lifts the electronic conductivity of silicon materials, reduce the body of silicon Product effect, and improve the structural stability of electrode material in cyclic process.
(2) present invention prepares the nano-silicon of high-performance pure silicon component using low temperature molten salt method, using specific AlCl3It is molten Melt salt and reducing agent and silicon source closed and filled with the container of protective atmosphere, in 200-500 DEG C of reaction, be not only avoided that silicon The formation of aluminium alloy and Si-Mg alloy, the generation of side reaction can also be reduced, last pickling, immersion, obtains receiving for pure silicon component Rice silicon.
(3) nano-silicon for the high-performance pure silicon component that the present invention is prepared using low temperature molten salt method is as silicon source, knot The method for closing mechanical fusion-high temperature pyrolysis prepares silicon-carbon composite cathode material, obtained silicon-carbon composite cathode material Stability Analysis of Structures, While the electronic conductivity of silicon materials is improved, silicium cathode caused volume during alloy and removal alloying is effectively buffered Effect, improve structural stability of the electrode material in cyclic process.
(4) silicon-carbon cathode material for preparing of the present invention have initial coulomb efficiency height, good cycle, compacted density height, The advantages that electrode structure is stable.
(5) present invention prepare nano-silicon and silicon-carbon composite cathode material preparation process is environment-friendly pollution-free and synthesis temperature Spend low, it is easy to accomplish industrialization large-scale production.
Brief description of the drawings
Fig. 1 is the SEM figures of pure nano-silicon prepared by the embodiment of the present invention 1；
Fig. 2 is the XRD of pure nano-silicon prepared by the embodiment of the present invention 1；
Fig. 3 is the XRD of silicon-carbon cathode material prepared by the embodiment of the present invention 1；
Fig. 4 is the cycle performance curve of silicon-carbon cathode material prepared by the embodiment of the present invention 8.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
Embodiment 1：
Present embodiments provide a kind of nano-silicon and lithium ion battery silicon-carbon Compound Negative is prepared using the nano-silicon as silicon source The preparation method of pole material：
Prepare nano-silicon：
(1) by 5 parts by weight AlCl3It is well mixed and is put into stainless steel pressure cooker with 2 parts by weight magnesium powders, then takes 1 weight Part SiCl4It is put into pressure cooker, process above is carried out in the environment full of nitrogen.Then pressure cooker horse back heated sealed, 400 DEG C of reaction 6h are warming up to 2 DEG C/min speed, magnesium powder is to SiCl4Reduced, obtain including the sediment of nano-silicon；
(2) sediment for being cooled to room temperature is cleaned with 0.1M hydrochloric acid, is then cleaned with deionized water and ethanol, last sample Product soak 30min in the ethanol of dilution is the HF solution of solvent, and pure silicon sample, i.e. nano-silicon are obtained in 50 DEG C of vacuum drying.
Fig. 1 is the SEM figures of pure nano-silicon prepared by the present embodiment 1, and as seen from the figure, silica flour prepared by the condition is nanoscale Little particle forms.
Fig. 2 is the XRD of pure nano-silicon prepared by the present embodiment 1, and as seen from the figure, 2 θ are at 10-80 ° in x-ray diffraction spectra In the range of have clearly 5 diffraction maximums, all peaks meet the Si (JPCDS77-2111) of Emission in Cubic, and without other impurity Peak.
Prepare silicon-carbon composite cathode material of lithium ion battery：
A：By 120g spherical graphites ultrasonic disperse in 100ml absolute ethyl alcohols, above-mentioned nano-silicon 40g is then added into stone In black dispersion liquid, using planetary ball mill ball milling 7h, drum's speed of rotation 250r/min, then place 80 in vacuum drying chamber DEG C vacuum drying 3h；
B：60g medium temperature coal pitch is mixed with the silicon/graphite composite prepared in above-mentioned A in cone-type mixer, Incorporation time is 30min；Then said mixture is placed in horizontal mechanical fusion machine and carries out mechanical fusion, mechanical fusion machine Rotating speed is 800r/min, time of fusion 25min；Finally the mixture after fusion is transferred at tube furnace high temperature charing Reason, temperature program(me) are：500 DEG C are warming up to 2 DEG C/min speed at room temperature, 30min is incubated, then with 5 DEG C/min speed 1000 DEG C are warming up to, 180min is incubated, finally naturally cools to room temperature, pulverize and sieve and can obtain Si-C composite material.
Fig. 3 is the XRD of silicon-carbon cathode material prepared by embodiment 1.
In order to examine the performance of silicon-carbon composite cathode material of lithium ion battery of the present invention, half-cell is assembled into its progressive Can test.By the silicon-carbon composite cathode material of lithium ion battery of gained respectively with conductive agent super P-Li, binding agent CMC and SBR is according to mass ratio 80:10:10 ball milling mixings, the viscosity that mixture is adjusted with deionized water are made slurry, are coated uniformly on copper On paper tinsel, 80 DEG C of vacuum drying 8h, obtained experimental cell pole piece.Again using lithium piece as being assembled into electrode in glove box CR2032 type button cells, first circulation uses to be activated under 0.05C multiplying powers, afterwards using 0.2C rate charge-discharge voltage models Enclose and carry out cycle performance test for 0.01-1.5V, test result is as illustrated in chart 1.
Embodiment 2：
Present embodiments provide a kind of nano-silicon and lithium ion battery silicon-carbon Compound Negative is prepared using the nano-silicon as silicon source The preparation method of pole material：
Prepare nano-silicon：
(1) by 5 parts by weight AlCl3It is well mixed and is put into stainless steel pressure cooker with 3 parts by weight sodium powders, then takes 1 weight Part SiO2It is put into pressure cooker, process above is carried out in the environment full of nitrogen.Then pressure cooker horse back heated sealed, with 5 DEG C/min speed is warming up to 200 DEG C of reaction 10h, and magnesium powder is to SiO2Reduced, obtain including the sediment of nano-silicon；
(2) sediment for being cooled to room temperature is cleaned with 0.2M hydrochloric acid, is then cleaned with deionized water and ethanol, last sample Product soak 40min in the ethanol of dilution is the HF solution of solvent, and pure silicon sample, i.e. nano-silicon are obtained in 40 DEG C of vacuum drying.
Prepare silicon-carbon composite cathode material of lithium ion battery：
A：By 120g spherical graphites ultrasonic disperse in 100ml absolute ethyl alcohols, above-mentioned nano-silicon 15g is then added into stone In black dispersion liquid, using planetary ball mill ball milling 7h, drum's speed of rotation 250r/min, then place 80 in vacuum drying chamber DEG C vacuum drying 3h；
B：20g medium temperature coal pitch is mixed with the silicon/graphite composite prepared in above-mentioned A in cone-type mixer, Incorporation time is 30min；Then said mixture is placed in horizontal mechanical fusion machine and carries out mechanical fusion, mechanical fusion machine Rotating speed is 800r/min, time of fusion 25min；Finally the mixture after fusion is transferred at tube furnace high temperature charing Reason, temperature program(me) are：500 DEG C are warming up to 2 DEG C/min speed at room temperature, 30min is incubated, then with 5 DEG C/min speed 1000 DEG C are warming up to, 180min is incubated, finally naturally cools to room temperature, pulverize and sieve and can obtain Si-C composite material.
The making of electrode slice is carried out as described in example 1 above, is assembled into button cell, and circulation first uses 0.05C multiplying powers Activated, use 0.2C rate charge-discharges voltage range to carry out charge and discharge cycles test, test result for 0.01-1.5V afterwards As shown in table 1.
Embodiment 3：
Present embodiments provide a kind of nano-silicon and lithium ion battery silicon-carbon Compound Negative is prepared using the nano-silicon as silicon source The preparation method of pole material：
Prepare nano-silicon：
(1) by 6 parts by weight AlCl3It is well mixed and is put into stainless steel pressure cooker with 3 parts by weight magnesium powders, then takes 1.5 weights Amount part man-made vitreous fibres are put into pressure cooker, and process above is carried out in the environment full of nitrogen.Then pressure cooker horse back Heated sealed, 300 DEG C of reaction 8h being warming up to 3 DEG C/min speed, magnesium powder reduces to man-made vitreous fibres, comprising The sediment of nano-silicon；
(2) sediment for being cooled to room temperature is cleaned with 0.15M hydrochloric acid, is then cleaned with deionized water and ethanol, finally Sample soaks 20min in the ethanol of dilution is the HF solution of solvent, and pure silicon sample, i.e. nanometer are obtained in 60 DEG C of vacuum drying Silicon.
Prepare silicon-carbon composite cathode material of lithium ion battery：
A：By 120g spherical graphites ultrasonic disperse in 100ml absolute ethyl alcohols, above-mentioned nano-silicon 24g is then added into stone In black dispersion liquid, using planetary ball mill ball milling 7h, drum's speed of rotation 250r/min, then place 80 in vacuum drying chamber DEG C vacuum drying 3h；
B：25g medium temperature coal pitch is mixed with the silicon/graphite composite prepared in above-mentioned A in cone-type mixer, Incorporation time is 30min；Then said mixture is placed in horizontal mechanical fusion machine and carries out mechanical fusion, mechanical fusion machine Rotating speed is 800r/min, time of fusion 25min；Finally the mixture after fusion is transferred at tube furnace high temperature charing Reason, temperature program(me) are：500 DEG C are warming up to 2 DEG C/min speed at room temperature, 30min is incubated, then with 5 DEG C/min speed 1000 DEG C are warming up to, 180min is incubated, finally naturally cools to room temperature, pulverize and sieve and can obtain Si-C composite material.
The making of electrode slice is carried out as described in example 1 above, is assembled into button cell, and circulation first uses 0.05C multiplying powers Activated, use 0.2C rate charge-discharges voltage range to carry out charge and discharge cycles test, test result for 0.01-1.5V afterwards As shown in table 1.
Embodiment 4：
Present embodiments provide a kind of nano-silicon and lithium ion battery silicon-carbon Compound Negative is prepared using the nano-silicon as silicon source The preparation method of pole material：
Prepare nano-silicon：
(1) by 8 parts by weight AlCl3It is well mixed and is put into stainless steel pressure cooker with 3 parts by weight magnesium powders, then takes 1 weight Part SiCl4It is put into pressure cooker, process above is carried out in the environment full of nitrogen.Then pressure cooker horse back heated sealed, 350 DEG C of reaction 7h are warming up to 4 DEG C/min speed, magnesium powder is to SiCl4Reduced, obtain including the sediment of nano-silicon；
(2) sediment for being cooled to room temperature is cleaned with 0.12M hydrochloric acid, is then cleaned with deionized water and ethanol, finally Sample soaks 45min in the ethanol of dilution is the HF solution of solvent, and pure silicon sample, i.e. nanometer are obtained in 65 DEG C of vacuum drying Silicon.
Prepare silicon-carbon composite cathode material of lithium ion battery：
A：By 120g crystalline flake graphites ultrasonic disperse in 100ml absolute ethyl alcohols, above-mentioned nano-silicon 40g is then added into stone In black dispersion liquid, using planetary ball mill ball milling 7h, drum's speed of rotation 250r/min, then place 80 in vacuum drying chamber DEG C vacuum drying 3h；
B：60g medium temperature coal pitch is mixed with the silicon/graphite composite prepared in above-mentioned A in cone-type mixer, Incorporation time is 30min；Then said mixture is placed in horizontal mechanical fusion machine and carries out mechanical fusion, mechanical fusion machine Rotating speed is 800r/min, time of fusion 25min；Finally the mixture after fusion is transferred at tube furnace high temperature charing Reason, temperature program(me) are：500 DEG C are warming up to 2 DEG C/min speed at room temperature, 30min is incubated, then with 5 DEG C/min speed 1000 DEG C are warming up to, 180min is incubated, finally naturally cools to room temperature, pulverize and sieve and can obtain Si-C composite material.
The making of electrode slice is carried out as described in example 1 above, is assembled into button cell, and circulation first uses 0.05C multiplying powers Activated, use 0.2C rate charge-discharges voltage range to carry out charge and discharge cycles test, test result for 0.01-1.5V afterwards As shown in table 1.
Fig. 2 is the voltage capacity figure first of silicon-carbon cathode material prepared by embodiment 4.
Embodiment 5
Present embodiments provide a kind of nano-silicon and lithium ion battery silicon-carbon Compound Negative is prepared using the nano-silicon as silicon source The preparation method of pole material：
Prepare nano-silicon：
(1) by 8 parts by weight AlCl3It is well mixed and is put into stainless steel pressure cooker with 3 parts by weight magnesium powders, then takes 1.5 weights Measure part SiO2It is put into pressure cooker, process above is carried out in the environment full of nitrogen.Then pressure cooker horse back heated sealed, 250 DEG C of reaction 9h are warming up to 3.5 DEG C/min speed, magnesium powder is to SiO2Reduced, obtain including the sediment of nano-silicon；
(2) sediment for being cooled to room temperature is cleaned with 0.18M hydrochloric acid, is then cleaned with deionized water and ethanol, finally Sample soaks 35min in the ethanol of dilution is the HF solution of solvent, and pure silicon sample, i.e. nanometer are obtained in 55 DEG C of vacuum drying Silicon.
Prepare silicon-carbon composite cathode material of lithium ion battery：
A：By 120g spherical graphites ultrasonic disperse in 100ml absolute ethyl alcohols, above-mentioned nano-silicon 40g is then added into stone In black dispersion liquid, using planetary ball mill ball milling 7h, drum's speed of rotation 250r/min, then place 80 in vacuum drying chamber DEG C vacuum drying 3h；
B：55g coal tar pitchs are mixed with the silicon/graphite composite prepared in above-mentioned A in cone-type mixer, Incorporation time is 30min；Then said mixture is placed in horizontal mechanical fusion machine and carries out mechanical fusion, mechanical fusion machine Rotating speed is 800r/min, time of fusion 25min；Finally the mixture after fusion is transferred at tube furnace high temperature charing Reason, temperature program(me) are：500 DEG C are warming up to 2 DEG C/min speed at room temperature, 30min is incubated, then with 5 DEG C/min speed 1000 DEG C are warming up to, 180min is incubated, finally naturally cools to room temperature, pulverize and sieve and can obtain Si-C composite material.
The making of electrode slice is carried out as described in example 1 above, is assembled into button cell, and circulation first uses 0.05C multiplying powers Activated, use 0.2C rate charge-discharges voltage range to carry out charge and discharge cycles test, test result for 0.01-1.5V afterwards As shown in table 1.
Embodiment 6
Present embodiments provide a kind of nano-silicon and lithium ion battery silicon-carbon Compound Negative is prepared using the nano-silicon as silicon source The preparation method of pole material：
Prepare nano-silicon：
(1) by 7 parts by weight AlCl3It is well mixed and is put into stainless steel pressure cooker with 2.5 parts by weight magnesium powders, then takes 1 weight Amount part diatomite is put into pressure cooker, and process above is carried out in the environment full of nitrogen.Then sealing adds pressure cooker at once Heat, 350 DEG C of reaction 8.5h are warming up to 4 DEG C/min speed, magnesium powder reduces to diatomite, and it is heavy comprising nano-silicon to obtain Starch；
(2) sediment for being cooled to room temperature is cleaned with 0.15M hydrochloric acid, is then cleaned with deionized water and ethanol, finally Sample soaks 40min in the ethanol of dilution is the HF solution of solvent, and pure silicon sample, i.e. nanometer are obtained in 50 DEG C of vacuum drying Silicon.
Prepare silicon-carbon composite cathode material of lithium ion battery：
A：By 120g spherical graphites ultrasonic disperse in 100ml absolute ethyl alcohols, above-mentioned nano-silicon 40g is then added into stone In black dispersion liquid, using planetary ball mill ball milling 7h, drum's speed of rotation 250r/min, then place 80 in vacuum drying chamber DEG C vacuum drying 3h；
B：58g tar asphalts are mixed with the silicon/graphite composite prepared in above-mentioned A in cone-type mixer, mixed The conjunction time is 30min；Then said mixture is placed in horizontal mechanical fusion machine and carries out mechanical fusion, mechanical fusion machine turns Speed is 800r/min, time of fusion 25min；The mixture after fusion is finally transferred to tube furnace high temperature charing process, Temperature program(me) is：500 DEG C are warming up to 2 DEG C/min speed at room temperature, is incubated 30min, is then heated up with 5 DEG C/min speed To 1000 DEG C, 180min is incubated, room temperature is finally naturally cooled to, pulverizes and sieves and can obtain Si-C composite material.
The making of electrode slice is carried out as described in example 1 above, is assembled into button cell, and circulation first uses 0.05C multiplying powers Activated, use 0.2C rate charge-discharges voltage range to carry out charge and discharge cycles test, test result for 0.01-1.5V afterwards As shown in table 1.
Embodiment 7
Other conditions are same as Example 1, and difference is that conductive agent Super-Li, which is changed to carbon, during assembled battery receives Mitron, test result are as shown in table 1.
Embodiment 8
Other conditions are same as Example 1, and difference is binding agent CMC+SBR is changed to alginic acid during assembled battery Sodium, test result are as shown in table 1.
Fig. 4 is the cycle performance curve of silicon-carbon cathode material prepared by embodiment 8.
Embodiment 9
Other conditions are same as Example 1, and difference is binding agent CMC is changed to PVDF during assembled battery, and molten Agent is changed to 1-METHYLPYRROLIDONE by deionized water, and test result is as shown in table 1.
Comparative example 1
Other conditions are same as Example 1, and difference is to replace nano-silicon with ball milling silica flour of the prior art, surveys Test result is as shown in table 1.
Embodiment 1-9 and the correlated performance data of comparative example 1 are listed in the table below in 1.
Table 1
From table 1 it follows that silicon-carbon composite cathode material prepared by the method for the invention has excellent electrochemistry Performance, initial coulomb efficiency is high, compacted density is high, stable cycle performance.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.

Claims (10)

  1. A kind of 1. nano-silicon, it is characterised in that the nano-silicon is to assemble the second particle formed by once silicon grain, described two The particle diameter of secondary particle is in 80-120nm.
  2. 2. nano-silicon according to claim 1, it is characterised in that the particle diameter of the second particle is 100nm；
    Preferably, the particle diameter of a silicon grain is in 20-30nm.
  3. 3. the preparation method of nano-silicon as claimed in claim 1 or 2, it is characterised in that the described method comprises the following steps：
    (1) by AlCl3, reducing agent and silicon source be put into the reactor filled with protective atmosphere, seal, be warming up to 200-500 DEG C it is anti- Should, reducing agent reduces to silicon source, obtains including the sediment of nano-silicon；
    (2) with acid cleaning sediment, be then placed in using ethanol as the HF solution of solvent in soak, vacuum drying obtain nano-silicon；
    Wherein, the mol ratio of step (1) reducing agent and silicon source is more than reducing agent and the chemistry of silicon source in redox reaction Metering ratio.
  4. 4. the preparation method of nano-silicon according to claim 3, it is characterised in that methods described is additionally included in step (2) With acid clean sediment after, be put into using ethanol as the HF solution of solvent in soak before, carry out deionized water and ethanol cleaning The step of.
  5. 5. the method according to claim 3 or 4, it is characterised in that step (1) described AlCl3Mass ratio with silicon source is (4-8):1, be preferably (4-5):1；
    Preferably, step (1) AlCl3, reducing agent and silicon source mass ratio be (4-8):(2-3):(1-3), it is preferably (4- 5):2:1；
    Preferably, combination of step (1) the described reducing agent including any one in magnesium powder, sodium powder or aluminium powder or at least two；
    Preferably, step (1) described silicon source includes SiCl4、SiO2, man-made vitreous fibres or natural minerals diatomite in appoint Anticipate a kind of or at least two combinations；
    Preferably, step (1) described protective atmosphere is any one in nitrogen, helium or argon gas or at least two mixing Atmosphere；
    Preferably, step (1) described reactor is any one in pressure cooker or reactor；
    Preferably, the heating rate of step (1) described heating is 2-5 DEG C/min；
    Preferably, the time of step (1) described reaction is 6-10h；
    Preferably, the hydrochloric acid that step (2) acid is 0.1-0.2M；
    Preferably, step (2) is described using ethanol as in the HF solution of solvent, HF mass fraction is 5%~20%, is preferably 10%；
    Preferably, the time of step (2) described immersion is 15-45min, preferably 20min；
    Preferably, step (2) the vacuum drying temperature is 40-100 DEG C, preferably 80 DEG C.
  6. 6. according to the method described in claim any one of 3-5, it is characterised in that the described method comprises the following steps：
    (1) by 4-8 parts by weight AlCl3It is well mixed and is put into the pressure cooker full of nitrogen with 2-4 parts by weight magnesium powder, then takes 1-2 Parts by weight SiCl4It is put into pressure cooker, seals, 200-500 DEG C of reaction 6-10h, magnesium powder pair is warming up to 2-5 DEG C/min speed SiCl4Reduced, obtain including the sediment of nano-silicon；
    Wherein, magnesium powder and SiCl4Mol ratio be more than 2:1；
    (2) sediment is cleaned with 0.1-0.2M hydrochloric acid, is then cleaned with deionized water and ethanol, is finally putting into using ethanol to be molten 30min is soaked in the HF solution of agent, nano-silicon is obtained in 50 DEG C of vacuum drying.
  7. 7. a kind of method that nano-silicon using described in claim any one of 1-3 prepares silicon-carbon composite cathode material as silicon source, Specifically include following steps：
    Nano-silicon, graphite microparticles are placed in ball mill, ball milling disperses in the environment of organic solvent, after vacuum drying with Pitch is placed in cone-type mixer and slightly mixed, then the mixed-powder after thick mix is placed in into progress machinery in mechanical fusion machine and melted Close, be finally heat-treated under the protection of inert gas, silicon-carbon composite cathode material is obtained after cooling.
  8. 8. according to the method for claim 7, it is characterised in that prepare the mass fraction of the raw material of silicon-carbon composite cathode material For：Nano-silicon 10-40%, graphite microparticles 30-80%, pitch 10-30%；
    Preferably, the graphite microparticles are any one in flaky graphite, spherical graphite or Delanium or at least two Combination；
    Preferably, the median particle diameter of the graphite microparticles is 5-15 μm；
    Preferably, the organic solvent is ethanol, acetone, acetonitrile, tetrahydrofuran, chloroform, 1-METHYLPYRROLIDONE or N, In dinethylformamide any one or at least two combination；
    Preferably, the pitch be low temperature coal tar pitch, it is medium temperature coal pitch, coal tar pitch, slag oil asphalt, tar asphalt, natural In pitch, graphite pitch or shale tar pitch any one or at least two combination；
    Preferably, the median particle diameter of the pitch is 1-20 μm；
    Preferably, the Ball-milling Time is 3-10h；
    Preferably, the mechanical fusion machine is any one in horizontal fusion machine or vertical fusion machine；
    Preferably, the rotating speed of the mechanical fusion machine is 500-1000r/min, and the mechanical fusion time is 15-60min；
    Preferably, described be heat-treated is：500 DEG C first are risen to 0.5-5 DEG C/min heating rate, is incubated 1-200min, then with 0.5-10 DEG C/min heating rate rises to 900-1200 DEG C, is incubated 10-240min, last nature or program are cooled to room temperature；
    Preferably, the inert gas includes any one at least two group in nitrogen, argon gas, neon, helium or xenon Close.
  9. 9. a kind of silicon-carbon composite cathode material, it is characterised in that the silicon-carbon composite cathode material is as described in claim 7 or 8 Method be prepared.
  10. 10. a kind of lithium ion battery, it is characterised in that the negative material in the negative electrode of lithium ion battery is claim 9 institute The silicon-carbon composite cathode material stated；
    Preferably, the negative pole is prepared via a method which to obtain：By the silicon-carbon composite cathode material described in claim 9, lead Electric agent and binding agent 80-94 by mass percentage：3-10：5-10 dissolvings mix in a solvent, coated in copper foil current collector, very Sky dries obtained negative pole；
    Preferably, the conductive agent is Super P-Li, acetylene black, CNT, graphene, carbon nano-fiber or fullerene Any one or at least two combination；
    Preferably, the binding agent is polyimide resin, acrylic resin, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl fibre Tie up in plain sodium, butadiene-styrene rubber or sodium alginate any one or at least two combination；
    Preferably, the solvent is in deionized water, 1-METHYLPYRROLIDONE, dimethylformamide, acetone or methyl ethyl ketone Any one or at least two combination.
CN201710792080.2A 2017-09-05 2017-09-05 A kind of nano-silicon, preparation method and its application in silicon-carbon composite cathode material and lithium ion battery Pending CN107634199A (en)

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CN108306006A (en) * 2018-01-31 2018-07-20 北京国能电池科技股份有限公司 Negative material, negative plate and preparation method thereof, lithium ion battery and preparation method thereof
CN109081350A (en) * 2018-09-11 2018-12-25 浙江工业大学 A kind of method that watery fusion salt medium prepares nano-silicon
CN109873150A (en) * 2019-03-14 2019-06-11 西北师范大学 The method for preparing nanometer silicon composite material as raw material using palygorskite
CN110386604A (en) * 2019-08-09 2019-10-29 北方奥钛纳米技术有限公司 The preparation method of nano-silicon, silicon based anode material and preparation method thereof
CN110713187A (en) * 2019-09-23 2020-01-21 北京化工大学 Preparation method of silicon material and application of silicon material in lithium ion battery cathode
CN111193013A (en) * 2020-01-08 2020-05-22 青岛泰达华润新能源科技有限公司 Preparation method of silicon-carbon negative electrode material for lithium ion battery
CN111653735A (en) * 2020-02-24 2020-09-11 深圳市翔丰华科技股份有限公司 Low-temperature carbon-coated porous silicon composite negative electrode material and preparation method thereof
CN112421049A (en) * 2020-11-30 2021-02-26 成都新柯力化工科技有限公司 Method for preparing lithium battery silicon-carbon negative electrode material through ball milling and silicon-carbon negative electrode material
CN112467125A (en) * 2020-12-29 2021-03-09 山东硅纳新材料科技有限公司 Method for preparing novel silicon-carbon negative electrode material by using rice hull ash
CN113241434A (en) * 2021-05-13 2021-08-10 中南大学 Nano-aluminum cathode material of lithium ion battery and preparation method of nano-aluminum cathode material
CN114497509A (en) * 2022-02-08 2022-05-13 格龙新材料科技(常州)有限公司 Preparation method of silicon-carbon composite negative electrode material
CN115611282A (en) * 2022-11-07 2023-01-17 济南大学 Nano silicon, method for preparing nano silicon by liquid phase method and application

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CN108306006A (en) * 2018-01-31 2018-07-20 北京国能电池科技股份有限公司 Negative material, negative plate and preparation method thereof, lithium ion battery and preparation method thereof
CN109081350A (en) * 2018-09-11 2018-12-25 浙江工业大学 A kind of method that watery fusion salt medium prepares nano-silicon
CN109873150A (en) * 2019-03-14 2019-06-11 西北师范大学 The method for preparing nanometer silicon composite material as raw material using palygorskite
CN110386604A (en) * 2019-08-09 2019-10-29 北方奥钛纳米技术有限公司 The preparation method of nano-silicon, silicon based anode material and preparation method thereof
CN110713187A (en) * 2019-09-23 2020-01-21 北京化工大学 Preparation method of silicon material and application of silicon material in lithium ion battery cathode
CN111193013A (en) * 2020-01-08 2020-05-22 青岛泰达华润新能源科技有限公司 Preparation method of silicon-carbon negative electrode material for lithium ion battery
CN111653735A (en) * 2020-02-24 2020-09-11 深圳市翔丰华科技股份有限公司 Low-temperature carbon-coated porous silicon composite negative electrode material and preparation method thereof
CN112421049A (en) * 2020-11-30 2021-02-26 成都新柯力化工科技有限公司 Method for preparing lithium battery silicon-carbon negative electrode material through ball milling and silicon-carbon negative electrode material
CN112467125A (en) * 2020-12-29 2021-03-09 山东硅纳新材料科技有限公司 Method for preparing novel silicon-carbon negative electrode material by using rice hull ash
CN113241434A (en) * 2021-05-13 2021-08-10 中南大学 Nano-aluminum cathode material of lithium ion battery and preparation method of nano-aluminum cathode material
CN113241434B (en) * 2021-05-13 2023-02-28 中南大学 Nano-aluminum cathode material of lithium ion battery and preparation method of nano-aluminum cathode material
CN114497509A (en) * 2022-02-08 2022-05-13 格龙新材料科技(常州)有限公司 Preparation method of silicon-carbon composite negative electrode material
CN115611282A (en) * 2022-11-07 2023-01-17 济南大学 Nano silicon, method for preparing nano silicon by liquid phase method and application

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