CN107069017A - A kind of preparation method of nano silicon-based second particle - Google Patents
A kind of preparation method of nano silicon-based second particle Download PDFInfo
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- CN107069017A CN107069017A CN201710270686.XA CN201710270686A CN107069017A CN 107069017 A CN107069017 A CN 107069017A CN 201710270686 A CN201710270686 A CN 201710270686A CN 107069017 A CN107069017 A CN 107069017A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 invention belongs to energy storage research field, more particularly to a kind of preparation method of nano silicon-based second particle is specifically included：Step 1, mediate, mediated after nano silica-base material, silane coupler, solvent one are mixed, obtain mixture one, mediated after conductive agent, surfactant, solvent two are mixed, obtain mixture two；Step 2, scattered, mixture one that step 1 is obtained, the blending of mixture two is blended, it is scattered to obtain the mixed slurry that nano silica-base material is dispersed in conductive agent；Step 3, second particle is prepared, the mixed slurry pelletizing that step 2 is obtained obtains the second particle that particle diameter distribution is 1 μm~200 μm.When preparing nano silicon-based second particle using this method, maximizing silane coupler, the performance of surfactant reduce its consumption；It can also greatly reduce the usage amount of solvent one and solvent two, the excellent nano silicon-based second particle of processability simultaneously.
Description
Technical field
The invention belongs to energy storage research field, more particularly to a kind of preparation method of nano silicon-based second particle.
Background technology
Lithium ion battery is so that its specific energy is big, operating voltage is high, self-discharge rate is small, small volume, the advantage such as lightweight, from it
Since birth, revolutionary change just has been brought to energy storage field, is widely used in various portable electric appts and electronic
In automobile.However as the improvement of people's living standards, higher Consumer's Experience proposes higher requirement to lithium ion battery：
Quality is lighter, use time is longer etc..The more excellent electrode material of new performance is had to look for solve the above problems.
Current commercialized lithium ion battery negative material is mainly graphite, but because its theoretical capacity is only 372mAhg-
1, the active demand of user can not be met.Therefore, the negative material exploitation of more height ratio capacity is extremely urgent.It is used as lithium-ion electric
Pond negative material, silicon materials receive much concern always.Its theoretical capacity is 4200mAhg-1, is the graphite capacity having been commercialized
More than 10 times.And it to have low intercalation potential, low atomic wts, high-energy-density, price relatively inexpensive, environment-friendly etc. excellent
One of gesture, optimal selection as high-capacity cathode material of new generation.But silicon materials electric conductivity itself is poor, in charge and discharge process
Volumetric expansion is big and easily causes material structure destruction and mechanical crushing, therefore the decay of its cycle performance is fast, widely application by
To limitation.
Above-mentioned to inscribe in order to solve, prior art mainly has silicon grain nanosizing, adds conductive into silica-base material particle
Conductive material of function admirable etc., the electric conductivity for improving silica-base material integral particle, while solving material discharge and recharge
In journey the problems such as silica-base material mechanical crushing.But the based particles of nanostructured are easily reunited, disperse difficulty big；And conventional
Conductive agent material, general size is smaller (nanoscale), and specific surface area is larger, and scattered difficulty is bigger.But maximize conduction
The more excellent silicon substrate second particle of the conductive effect and processability of agent, it is necessary to ensure that nano silicon-based particle and conductive agent are equal
It is even scattered.
In view of this, can be by two kinds of scattered difficulty larger material (nanometer it is necessory to propose a kind of technical scheme
Silica-base material particle, conductive agent) it is dispersed, so as to prepare the silicon-carbon cathode material of function admirable.
The content of the invention
It is an object of the invention to：In view of the shortcomings of the prior art, a kind of system of the nano silicon-based second particle provided
Preparation Method.When preparing nano silicon-based second particle using this method, maximizing silane coupler, the performance of surfactant,
Reduce its consumption；The usage amount of solvent can also be greatly reduced simultaneously, the nano silicon-based second particle of function admirable is prepared.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of preparation method of nano silicon-based second particle, mainly comprises the following steps：Step 1, mediate, will be nano silicon-based
Material, silane coupler, solvent one are mediated after mixing, and obtain mixture one, conductive agent, surfactant, solvent two are mixed
After mediate, obtain mixture two；Step 2, scattered, mixture one that step 1 is obtained, the blending of mixture two is blended, disperses
The mixed slurry in conductive agent is dispersed in nano silica-base material；Step 3, second particle is prepared, by mixing that step 2 is obtained
Slurry pelletizing is closed, the nano silicon-based second particle that particle diameter distribution is 1 μm~200 μm is obtained.
Improved as one kind of preparation method of the present invention, the nano silica-base material is that nanometer elementary silicon and nano-silicon are aoxidized
At least one of thing.
Improved as one kind of preparation method of the present invention, the conductive agent includes conductive black, super conductive carbon, section's qin
At least one of black, CNT, graphene, acetylene black.
Improved as one kind of preparation method of the present invention, the kneading process described in step 1 is：By nano silica-base material and silicon
Alkane coupling agent is dry-mixed, and the kneading of solvent one is added afterwards, mixture one is obtained；Conductive agent is dry-mixed with surfactant, afterwards
The kneading of solvent two is added, mixture two is obtained.
Further, the dry mixing process and kneading process use planetary stirring machine, revolution rotating speed be 1~60 turn/
Min, rotation rotating speed is 0~500 turn/min.
Improved as one kind of preparation method of the present invention, in mixture one, also containing non-nano silica-base material negative pole
Grain.
Preferably, the non-nano silica-base material negative pole particle include native graphite, Delanium, carbonaceous mesophase spherules,
Soft carbon, hard carbon, petroleum coke, carbon fiber, thermal decomposed resins carbon, lithium carbonate, tin base cathode material, transition metal nitride, tinbase are closed
At least one of gold, germanium-base alloy, acieral, antimony-containing alloy, magnesium base alloy.
Improved as one kind of preparation method of the present invention, in mixture one, the silane coupler accounts for the mixture one
In the 0.01-10%wt of middle solid constituent, slurry solid content >=1%, mixture two, the surfactant accounts for conductive agent
0.01-10%wt, slurry solid content >=0.5%.
Preferably, in mixture one, the silane coupler accounts for the 0.05-2%wt of solid constituent in the mixture one,
Slurry solid content >=5%；The surfactant accounts for the 0.05-2%wt of conductive agent, slurry solid content >=2%.
Improved as one kind of preparation method of the present invention, the silane coupler is alkyl silane coupling agent, amino silane
In coupling agent, alkenyl silane coupling agent, epoxyalkylsilane coupling agent and alkyl acyloxy silane coupling agent at least
It is a kind of；The solvent one and solvent two are water, alcohols, ketone, alkanes, esters, aromatics, 1-METHYLPYRROLIDONE, dimethyl
At least one of acid amides, diethylformamide, dimethyl sulfoxide (DMSO) and tetrahydrofuran；The surfactant is wetting agent, divided
At least one of powder, bleeding agent, solubilizer, cosolvent, cosolvent.
Further, the silane coupler is VTES, MTMS, tetraethoxy
Silane, vinyltrimethoxy silane, methylvinyldimethoxysilane, γ-methacryloxypropyl trimethoxy
Silane, methacryloyloxypropyl methyl dimethoxysilane, γ aminopropyltriethoxy silane, γ-mercaptopropyi three
Methoxy silane, γ-cyanopropyl trimethoxy silane, γ-glycidoxypropyltrimethoxy base silane, β-(3,4- rings
Oxygen cyclohexyl) at least one of ethyl trimethoxy silane and γ-ureido-propyl trimethoxy silane；The wetting agent is
At least one of anionic and non-ionic wetting agent；The dispersant be fatty acid, aliphatic amide type, esters,
An at least class in paraffin class, metal soap, low molecule wax class, HPMA；The bleeding agent oozes for non-ionic and anionic
At least one of saturating agent.
Preferably, the anionic wetting agents include alkyl sulfate, sulfonate, aliphatic acid or fatty acid ester sulfuric acid
At least one of salt, carboxylic acid soaps and phosphate, the non-ionic wetting agent include polyoxyethylated alkyl phenol, polyoxy second
At least one of alkene fatty alcohol ether and polyoxyethylene polyoxypropylene block copolymer, it is double stearic that the dispersant includes vinyl
Acid amides, oleic acid acyl, glyceryl monostearate, glyceryl tristearate, atoleine, microcrystalline wax, barium stearate, stearic acid
At least one of zinc, calcium stearate, Tissuemat E and polyethylene glycol, the nonionic penetrant comprising JFC, JFC-1,
At least one of JFC-2 and JFC-E, the anionic bleeding agent comprising fast penetrant T, alkali-resistant penetrant OEP-70,
At least one of alkali-resistant penetrant AEP and seeping at high temperature agent JFC-M, the cosolvent include benzoic acid, sodium benzoate, bigcatkin willow
At least one of acid, sodium salicylate, p-aminobenzoic acid, urethane, urea, acid amides, acetamide, borax and KI, institute
Stating cosolvent includes at least one of ethanol, glycerine, propane diols and polyethylene glycol.
Improved as one kind of preparation method of the present invention, the dispersing mode in step 2 is kneading, ball milling, sand are ground, high pressure is equal
At least one of matter, high speed shear；Pelletizing mode in step 3 is spray drying.
The advantage of the invention is that：
It 1. is uniformly dispersed.In kneading process, silane coupler can be uniformly wrapped on to nano silica-base material particle surface, more
Be conducive to scattered between nano silica-base material particle.Similarly, surfactant can be also uniformly wrapped on to conductive agent surface, more
Be conducive to scattered between conductive agent particle.Simultaneously as individually scattering in advance, silane coupler and surface can be maximized
The performance of activating agent, both consumptions of reduction.
2. kneading process is used, in the case where guarantee is dispersed, moreover it is possible to the consumption of minimumization solvent one and solvent two,
So that the solid content of obtained slurry is improved as far as possible.Can now reduce energy consumption during spray drying, improve production efficiency,
Reduce production cost.Simultaneously as solid content is high, during spray drying, the quantity of solvent evaporated from mist particles will be reduced
(solvent volatilization process often by along with the relatively low conductive agent component of density from inside hair from particle to particle surface transport phenomena
Raw, the phenomenon for ultimately resulting in conductive agent skewness in second particle occurs), therefore its influence being distributed to conductive agent is more
Low, conductive agent distribution is more uniform in obtained second particle, and second particle has higher capacity, lower internal resistance.
Embodiment
The present invention and its advantage are described in detail with reference to embodiment, but the embodiment party of the present invention
Formula not limited to this.
Comparative example
Prepare the silicon-carbon second particle material that particle diameter is 10 μm：
Step 1, mix, by elemental silicon, conductive black, tetraethoxysilane, the polyvinylpyrrolidone that particle diameter is 100nm
(mass ratio is elemental silicon:Conductive black:Tetraethoxysilane:Polyvinylpyrrolidone=90:8.9:1:0.1) and NMP (Gu
Content is 0.5%) to mix 10h, obtains slurry.
Step 2, prepared by second particle, adjustable spraying drying condition, prepares the silicon-carbon that particle diameter is 10 μm secondary
Particle；Coated afterwards, being carbonized obtains finished product silicon-carbon cathode material.
Embodiment 1
Step 1, mediate：By elemental silicon that particle diameter is 100nm, (mass ratio is elemental silicon to tetraethoxysilane:Tetraethoxy
Silane=90:1), NMP (solid content is 1%) mixing after mediate, revolution rotating speed be 60 turns/min, rotation rotating speed for 500 turns/
Min, mediates 2h and obtains mixture one；By conductive black, polyvinylpyrrolidone, (mass ratio is conductive black:Polyvinyl pyrrole
Alkanone=8.9:0.1) and after NMP (solid content is 0.5%) mixing mediate, revolution rotating speed is 60 turns/min, rotation rotating speed is 500
Turn/min；Mediate 2h and obtain mixture two.
Step 2, it is blended scattered：(mass ratio is elemental silicon to mixture one, the mixture two that step 1 is obtained:Conductive black
=90:8.9) mix, continue to mediate, revolution rotating speed is 20 turns/min, rotation rotating speed is 300 turns/min；Mediate after 2h
Obtain the mixed slurry that elemental silicon is dispersed in conductive black.
Step 3, second particle is prepared：Adjustable spraying drying condition, prepares the silicon-carbon that particle diameter is 10 μm secondary
Particle；Coated afterwards, being carbonized obtains finished product silicon-carbon cathode material.
Embodiment 2
Difference from Example 1 is that the present embodiment comprises the following steps：
In step 1 by elemental silicon that particle diameter is 100nm, (mass ratio is elemental silicon to tetraethoxysilane:Tetraethoxysilane
=90:1), mediated after NMP (solid content is 5%) mixing, revolution rotating speed is 20 turns/min, rotation rotating speed is 300 turns/min,
Mediate 2h and obtain mixture one；By conductive black, polyvinylpyrrolidone, (mass ratio is conductive black:Polyvinylpyrrolidone
=8.9:0.1) and after NMP (solid content is 2%) mixing mediate, revolve round the sun as 20 turns/min, 300 turns/min is switched to certainly；Mediate 2h
Obtain mixture two.
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 3
Difference from Example 1 is that the present embodiment comprises the following steps：
In step 1 by elemental silicon that particle diameter is 100nm, (mass ratio is elemental silicon to tetraethoxysilane:Tetraethoxysilane
=90:1), mediated after NMP (solid content is 10%) mixing, revolution rotating speed is 10 turns/min, rotation rotating speed is 100 turns/min,
Mediate 4h and obtain mixture one；By conductive black, polyvinylpyrrolidone, (mass ratio is conductive black:Polyvinylpyrrolidone
=8.9:0.1) and NMP (solid content is 5%) mixing after mediate, revolution rotating speed be 10 turns/min, rotation rotating speed for 100 turns/
Min, mediates 4h and obtains mixture two；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 4
Difference from Example 1 is that the present embodiment comprises the following steps：
In step 1 by elemental silicon that particle diameter is 100nm, (mass ratio is elemental silicon to tetraethoxysilane:Tetraethoxysilane
=90:1), mediated after NMP (solid content is 20%) mixing, revolution rotating speed is 5 turns/min, rotation rotating speed is 10 turns/min, is pinched
Close 8h and obtain mixture one；By conductive black, polyvinylpyrrolidone, (mass ratio is conductive black:Polyvinylpyrrolidone=
8.9:0.1) and after NMP (solid content is 10%) mixing mediate, revolution rotating speed is 5 turns/min, rotation rotating speed is 10 turns/min, is pinched
Close 8h and obtain mixture two.
Step 2, (mass ratio is elemental silicon to mixture one, the mixture two step 1 obtained:Conductive black=90:8.9)
Mix, continue to mediate, revolution rotating speed is 8 turns/min, rotation rotating speed is that to obtain elemental silicon equal after 50 turns/min, kneading 6h
The even mixed slurry being scattered in conductive black.
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 5
Difference from Example 1 is that the present embodiment comprises the following steps：
Step 1, by elemental silicon that particle diameter is 100nm, (mass ratio is elemental silicon to tetraethoxysilane:Tetraethoxysilane
=90:1), mediated after NMP (solid content is 40%) mixing, revolution rotating speed is 1 turn/min, rotation rotating speed is 0 turn/min, is pinched
Close 20h and obtain mixture one；By conductive black, polyvinylpyrrolidone, (mass ratio is conductive black:Polyvinylpyrrolidone=
8.9:0.1) and after NMP (solid content is 15%) mixing mediate, revolution rotating speed is 1 turn/min, rotation rotating speed is 0 turn/min, is pinched
Close 20h and obtain mixture two.
Step 2, (mass ratio is elemental silicon to mixture one, the mixture two step 1 obtained:Conductive black=90:8.9)
Mix, continue to mediate, revolution rotating speed is 2 turns/min, rotation rotating speed is 10 turns/min；Elemental silicon is obtained after mediating 20h
It is dispersed in the mixed slurry in conductive black.
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 6
Difference from Example 1 is that the present embodiment comprises the following steps：
Step 1, be the 100nm sub- silicon of oxidation by particle diameter, Delanium, methylvinyldimethoxysilane, NMP (Gu
Content is that (mass ratio for wherein, aoxidizing sub- silicon and Delanium is 1 for kneading after 20%) mixing：9, aoxidize sub- silicon and artificial stone
The blending ingredients of ink and the mass ratio of methylvinyldimethoxysilane are 9:1), revolution rotating speed is 5 turns/min, rotation rotating speed
For 10 turns/min；Mediate 8h and obtain mixture one, graphene, polyoxyethylated alkyl phenol and NMP (solid content is 5%) are mixed
(graphene is 9 with polyoxyethylated alkyl phenol mass ratio for kneading afterwards:1), revolution rotating speed be 5 turns/min, rotation rotating speed be 10 turns/
min；Mediate 8h and obtain mixture two.
Step 2, the mixture one, (blending ingredients and stone of the sub- silicon of oxidation and Delanium of mixture two step 1 obtained
The mass ratio of black alkene is 9:1) mix, continue to mediate, revolution rotating speed is 8 turns/min, rotation rotating speed is 50 turns/min, is pinched
Obtain aoxidizing the mixed slurry that sub- silicon is dispersed in graphene after closing 6h.
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 7
Difference from Example 1 is that the present embodiment comprises the following steps：
Step 1, be the 100nm sub- silicon of oxidation by particle diameter, Delanium, methylvinyldimethoxysilane, NMP (Gu
Content is that (mass ratio for wherein, aoxidizing sub- silicon and Delanium is 1 for kneading after 10%) mixing：9, aoxidize sub- silicon and artificial stone
The blending ingredients of ink and the mass ratio of methylvinyldimethoxysilane are 9.99:0.01), revolution rotating speed is 20 turns/min,
Rotation rotating speed is 200 turns/min, mediates 8h and obtains mixture one；By graphene, polyoxyethylated alkyl phenol and NMP (solid contents
To mediate (graphene after 1%) mixing:Polyoxyethylated alkyl phenol mass ratio is 9.99:0.01), revolution rotating speed be 20 turns/
Min, rotation rotating speed is 200 turns/min, mediates 8h and obtains mixture two.
Step 2, mixture one, the mixture two step 1 obtained mix (the sub- silicon of oxidation and Delanium it is mixed
The mass ratio of charge-coupled point and graphene is 9:1), continue to mediate, revolution rotating speed is 20 turns/min, rotation rotating speed is 200 turns/min,
Obtain aoxidizing the mixed slurry that sub- silicon is dispersed in graphene after mediating 6h.
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 8
Difference from Example 1 is that the present embodiment comprises the following steps：
Step 1, by the sub- silicon of oxidation that particle diameter is 100nm, native graphite, (mass ratio of the sub- silicon of oxidation and native graphite is 1：
9), mediated after methylvinyldimethoxysilane, water (solid content is 10%) mixing and (wherein, aoxidize sub- silicon and natural stone
The mass ratio of ink is 1：9, aoxidize the blending ingredients and the mass ratio of methylvinyldimethoxysilane of sub- silicon and native graphite
For 9.95:0.05), revolution rotating speed is 20 turns/min, and rotation rotating speed is 200 turns/min, mediates 8h and obtains mixture one；By graphite
(the quality of graphene and polyoxyethylated alkyl phenol is mediated after alkene, polyoxyethylated alkyl phenol and water (solid content is 1%) mixing
Than for 9.95:0.05), revolution rotating speed is 20 turns/min, and rotation rotating speed is 200 turns/min, mediates 8h and obtains mixture two.
Step 2, mixture one, the mixture two step 1 obtained mix (the sub- silicon of oxidation and native graphite it is mixed
The mass ratio of charge-coupled point and graphene is 9:1), continue to mediate, revolution rotating speed is 20 turns/min, rotation rotating speed is 200 turns/min,
Obtain aoxidizing the mixed slurry that sub- silicon is dispersed in graphene after mediating 6h.
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 9
Difference from Example 4 is that the present embodiment comprises the following steps：
Step 1, by elemental silicon, the tetraethoxysilane (mass ratio of elemental silicon and tetraethoxysilane of the particle diameter for 100nm
For 90:1) dry-mixed (revolution rotating speed is 5 turns/min, rotation rotating speed is 10 turns/min, duration 2h) and, NMP is added afterwards, and (solid content is
20%) mediate, revolution rotating speed is 5 turns/min, rotation rotating speed is 10 turns/min, mediates 8h and obtains mixture one；By conductive black,
(mass ratio of conductive black and polyvinylpyrrolidone is 8.9 to polyvinylpyrrolidone:0.1) it is dry-mixed (revolution rotating speed be 5 turns/
Min, rotation rotating speed be 10 turns/min, duration 2h), afterwards add NMP (solid content is 10%) mediate, revolution rotating speed be 5 turns/
Min, rotation rotating speed is 10 turns/min, mediates 8h and obtains mixture two.
Step 2, (mass ratio of elemental silicon and conductive black is 90 to mixture one, the mixture two step 1 obtained:
8.9) mix, continue to mediate, revolution rotating speed is 8 turns/min, rotation rotating speed is 50 turns/min, and nanometer is obtained after mediating 6h
Silica-base material is dispersed in the mixed slurry in conductive agent.
It is other identical with embodiment 4, it is not repeated herein.
Embodiment 10
Difference from Example 4 is that the present embodiment comprises the following steps：
Step 2, (mass ratio of elemental silicon and conductive black is 90 to mixture one, the mixture two step 1 obtained:
8.9) mix, carry out high-pressure homogeneous (mixture is subjected to high-speed impact) processing, obtain nano silica-base material uniform
It is scattered in the mixed slurry in conductive agent.
It is other identical with embodiment 4, it is not repeated herein.
Battery is assembled：By comparative example, embodiment the 1-10 silicon-carbon cathode material prepared and conductive agent, bonding agent, molten
Agent stirring obtains electrode slurry, applies form negative electrode on a current collector afterwards；By negative electrode and anode electrode (cobalt acid lithium
For active material), barrier film assembling obtain naked battery core, enter afterwards bag carry out top side seal, drying, fluid injection, standing, chemical conversion, shaping,
Degasification obtains resultant battery.
Material properties test：
Gram volume is tested：Each embodiment and comparative example silicon carbon material are prepared by following flow in 25 DEG C of environment
Battery core carries out gram volume test：3min is stood, 0.2C constant-current charges to 4.2V, 4.2V constant-voltage charges to 0.05C stand 3min,
0.2C constant-current discharges obtain discharge capacity D1 to 3.0V, stand 3min, 0.2C constant-current discharges to 3.85V, stand complete after 3min
Into volume test, the weight of silicon carbon material, that is, obtain negative pole gram volume, acquired results are shown in Table 1 in D1 divided by negative electricity pole piece.
High rate performance is tested：Each embodiment and comparative example silicon carbon material are prepared by following flow in 25 DEG C of environment
Battery core carry out high rate performance test：3min is stood, 0.2C constant-current charges to 4.2V, 4.2V constant-voltage charges to 0.05C are stood
3min, 0.2C constant-current discharge obtain discharge capacity D1 to 3.0V, stand 3min, and 0.2C constant-current charges to 4.2V, 4.2V constant pressures are filled
Electricity stands 3min to 0.05C, and 2C constant-current discharges obtain discharge capacity D2 to 3.0V, stand 3min, high rate performance is completed afterwards
Test, battery high rate performance=D2/D1*100%, acquired results are shown in Table 1.
Loop test:The electricity prepared in 25 DEG C of environment by following flow to each embodiment and comparative example silicon carbon material
Core carries out loop test：3min is stood, 0.2C constant-current charges to 4.2V, 4.2V constant-voltage charges to 0.05C stand 3min, 0.2C
Constant-current discharge obtains discharge capacity D1 to 3.0V, stands 3min, then repeats that " 0.2C constant-current charges to 4.2V, 4.2V constant pressures are filled
Electricity stands 3min to 0.05C, 0.2C constant-current discharges obtain discharge capacity Di to 3.0V, stand 3min ", repeatedly 299 times altogether
To D300, loop test is completed afterwards, and calculating capability retention is D300/D1*100%, and acquired results are shown in Table 1.
The chemical property of the battery core of silicon-carbon cathode material system assembling prepared by table 1, different comparative examples and embodiment
It can be obtained by table 1, the present invention can prepare the nano silicon-based second particle of function admirable, be obtained with the particle preparation
The silicon-carbon cathode material arrived is as negative pole, and assembling obtained battery core has excellent chemical property.Specifically, comparative examples
It can be obtained with embodiment 1-5, with the increase of solid content, matching is suitable to mediate stirring technique, can prepare premium properties
Nano silicon-based second particle (obtained battery core has excellent chemical property).But solid content is too high by the scattered effect of influence
Really, so that material property declines.It can be obtained by embodiment 6-8, using the preparation method of the present invention, even if using less silicon
Alkane coupling agent and dispersant, can also reach excellent dispersion effect, and the battery of function admirable is made.It can be obtained by embodiment 1-10,
The present invention has universality.
According to the announcement and teaching of description above, those skilled in the art in the invention can also be to above-mentioned embodiment
Changed and changed.Therefore, the invention is not limited in above-mentioned embodiment, every those skilled in the art are at this
Made any conspicuously improved, replacement or modification belong to protection scope of the present invention on the basis of invention.In addition,
Although having used some specific terms in this specification, these terms merely for convenience of description, not to structure of the present invention
Into any limitation.
Claims (10)
1. a kind of preparation method of nano silicon-based second particle, mainly comprises the following steps：
Step 1, mediate, mediated after nano silica-base material, silane coupler, solvent one are mixed, mixture one is obtained, by conduction
Agent, surfactant, solvent two are mediated after mixing, and obtain mixture two；
Step 2, scattered, mixture one that step 1 is obtained, the blending of mixture two are blended, scattered to obtain nano silica-base material equal
The even mixed slurry being scattered in conductive agent；
Step 3, second particle is prepared, the mixed slurry pelletizing that step 2 is obtained obtains particle diameter distribution for 1 μm~200 μm
Nano silicon-based second particle.
2. the preparation method of nano silicon-based second particle according to claim 1, it is characterised in that：The nano-silicon base material
Expect at least one of nanometer elementary silicon and nanometer Si oxide.
3. the preparation method of nano silicon-based second particle according to claim 1, it is characterised in that：The conductive agent includes
At least one of conductive black, super conductive carbon, Ketjen black, CNT, graphene, acetylene black.
4. the preparation method of nano silicon-based second particle according to claim 1, it is characterised in that pinching described in step 1
Conjunction process is：Nano silica-base material is dry-mixed with silane coupler, the kneading of solvent one is added afterwards, obtains mixture one；Will
Conductive agent is dry-mixed with surfactant, and the kneading of solvent two is added afterwards, mixture two is obtained.
5. the preparation method of nano silicon-based second particle according to claim 4, it is characterised in that：The dry mixing process and
Kneading process uses planetary stirring machine, and revolution rotating speed is 1~60 turn/min, and rotation rotating speed is 0~500 turn/min.
6. the preparation method of nano silicon-based second particle according to claim 1, it is characterised in that：In mixture one,
Also contain non-nano silica-base material negative pole particle；Preferably, the non-nano silica-base material negative pole particle includes native graphite, people
Make graphite, carbonaceous mesophase spherules, soft carbon, hard carbon, petroleum coke, carbon fiber, thermal decomposed resins carbon, lithium carbonate, tin base cathode material, mistake
Cross at least one of metal nitride, kamash alloy, germanium-base alloy, acieral, antimony-containing alloy, magnesium base alloy.
7. the preparation method of nano silicon-based second particle according to claim 1, it is characterised in that：In mixture one, institute
State in the 0.01-10%wt that silane coupler accounts for solid constituent in the mixture one, slurry solid content >=1%, mixture two,
The surfactant accounts for the 0.01-10%wt of conductive agent, slurry solid content >=0.5%；Preferably, it is described in mixture one
Silane coupler accounts for the 0.05-2%wt of solid constituent in the mixture one, slurry solid content >=5%；The surfactant
Account for the 0.05-2%wt of conductive agent, slurry solid content >=2%.
8. the preparation method of nano silicon-based second particle according to claim 1, it is characterised in that：The silane coupler
For alkyl silane coupling agent, amino silicane coupling agent, alkenyl silane coupling agent, epoxyalkylsilane coupling agent and alkyl
At least one of acyloxy silane coupling agent；The solvent one and solvent two are water, alcohols, ketone, alkanes, esters, fragrance
At least one of class, 1-METHYLPYRROLIDONE, dimethylformamide, diethylformamide, dimethyl sulfoxide (DMSO) and tetrahydrofuran；Institute
It is at least one of wetting agent, dispersant, bleeding agent, solubilizer, cosolvent, cosolvent to state surfactant.
9. the preparation method of nano silicon-based second particle according to claim 8, it is characterised in that：The silane coupler
For VTES, MTMS, tetraethoxysilane, vinyltrimethoxy silane, methyl second
Alkenyl dimethoxysilane, γ-methacryloxypropyl trimethoxy silane, methacryloyloxypropyl methyl diformazan
TMOS, γ aminopropyltriethoxy silane, γ mercaptopropyitrimethoxy silane, γ-cyanopropyl trimethoxy
Silane, γ-glycidoxypropyltrimethoxy base silane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane and
At least one of γ-ureido-propyl trimethoxy silane；The wetting agent is in anionic and non-ionic wetting agent
It is at least one；The dispersant be fatty acid, aliphatic amide type, esters, paraffin class, metal soap, low molecule wax class,
An at least class in HPMA；The bleeding agent is at least one of non-ionic and anionic bleeding agent.
10. the preparation method of nano silicon-based second particle according to claim 1, it is characterised in that：It is scattered in step 2
Mode is at least one of kneading, ball milling, husky mill, high-pressure homogeneous, high speed shear；Pelletizing mode in step 3 is dry for spraying
It is dry.
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