CN104716312B - Silicon-carbon composite material for lithium ion battery, preparation method and application of silicon-carbon composite material - Google Patents
Silicon-carbon composite material for lithium ion battery, preparation method and application of silicon-carbon composite material Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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Abstract
The invention provides a silicon-carbon composite material for a lithium ion battery, a preparation method and application of the silicon-carbon composite material. The silicon-carbon composite material for the lithium ion battery is 0.7-1.1 g/cm＜3＞ in tap density, and is prepared from a porous silicon-carbon composite material and carbon filled in pores, wherein the silicon content in the porous silicon-carbon composite material is 10-40%, and the carbon content is 60-90%. The composite material is low in cost, high in practicability, and capable of being prepared in large scale; the composite material is high in tap density, and meanwhile multiple buffer layers are arranged, so that the problem that the silicon-based material as a lithium ion battery cathode material is poor in circulation can be solved.
Description
Technical field
The present invention relates to a kind of preparation method of Si-C composite material and its application as lithium ion battery negative material.
Background technology
With petroleum resources worsening shortages and environmental pollution it is increasingly severe, develop reproducible clean energy resource and increasingly weigh
Will.The research and development of electric automobile have become one of global focus at present, and wherein lithium ion battery is used as its core technology
Extremely pay attention to.There are lithium ion battery the outstanding advantages such as specific energy height, long service life, green non-pollution to be widely used
In portable electronic products and electric automobile.At present business-like lithium ion battery negative material is mainly material with carbon element, but its
Theoretical specific capacity is only 372mAh/g, cannot increasingly meet requirement of the lithium ion battery applications field to high-power, high power capacity.
Therefore, the new type lithium ion battery for developing height ratio capacity is extremely urgent with negative material.
Silicon has high theoretical specific capacity (4200mAh/g) and removal lithium embedded, and being used as lithium ion battery negative most has prospect
One of material, and rich reserves, cost are relatively low in the earth.But silicon materials adjoint serious body during removal lithium embedded
Product change (～300%), causes the destruction and efflorescence of material structure, and then causes electrode cracking with active material from collector
Come off, after repeatedly circulating, capacity is decayed rapidly, limits application of the silicon materials in field of lithium ion battery.Therefore, how to improve
The cyclical stability of silicon materials, is the focus and emphasis of current research.
At present, mainly by the nanosizing of silicon and silicon based composite material improving the cyclical stability of silicon.But silicon nanometer
Line, nano-tube preparation process are complicated, yield poorly, it is difficult to which industrialization large-scale production, degree of being practical are low.Due to carbons material
With preferable flexible, good electron conduction, less volumetric expansion, and can be had by the cushion that carbon matrix is formed
The volumetric expansion of the alleviation silicon materials of effect, improves the cyclical stability of silicon class material.
The content of the invention
The technical problem to be solved is to overcome that existing Si-C composite material first circle coulombic efficiency is low, circulation is steady
Qualitative difference, high cost, preparation technology are not suitable for the defect of industrialized production.There is provided a kind of low cost, tap density it is high, can be big
Silicon-carbon composite material for lithium ion battery of large-scale production and preparation method thereof, and effectively solved by multi-buffering-layer
The defect of silicon class material, improves the cyclical stability of Si-C composite material.
The present invention improves a kind of Silicon-carbon composite material for lithium ion battery first, with higher tap density, vibration density
Spend for 0.7-1.1g/cm3, it is made up of with the carbon being filled in its hole porous Si-C composite material, porous carbon-silicon composite material
Middle silicone content is 10%-40%, and carbon content is 60%-90%.Preferably, the silicon face in porous Si-C composite material is coated
Amorphous carbon or alundum (Al2O3).
Silicon-carbon composite material for lithium ion battery provided by the present invention is to prepare in accordance with the following steps：
1) by sanded treatment after silica flour ball mill grinding, the silica flour after process is dispersed in into macromolecule polymer solution or containing aluminium
It is in the solution or the colloid containing silicon source in source and ultrasonically treated, make silica flour suspend in the solution, prevent to reunite.
2) by step 1) obtained by solution decompression rotary evaporation remove solvent after, be sintered under non-oxidizing atmosphere,
The thickness of amorphous carbon or alundum (Al2O3), amorphous carbon or alundum (Al2O3) is coated for 5-30nm, content in silicon face
For 0.5%-10%.
3) by step 2) obtained by the silica flour that coats with inorganic carbon source, hydroxy compounds dispersant, weight average molecular weight be
The polymeric additive of 50000-400000 carries out mechanical agitation, is uniformly mixed, the suitable weak solution of viscosity.
4) by step 3) obtained by weak solution carry out spray drying treatment, obtain Si-C composite material, and non-oxidizable
Be sintered under atmosphere, obtain the Si-C composite material of porous, in porous carbon-silicon composite material silicone content be 20%-60%, carbon
Content is 40%-80%, and tap density is 0.6-0.9g/cm3。
5) in step 4) obtained by Si-C composite material hole in, fill inorganic or organic carbon source, configuration viscosity it is higher
Concentrated solution, carry out spray drying treatment, obtain the spherical composite of densification, and be sintered under non-oxidizing atmosphere,
The Silicon-carbon composite material for lithium ion battery of high-tap density, stable circulation is finally given, silicone content is in composite
10%-40%, carbon content are 60%-90%, and tap density is 0.7-1.1g/cm3。
Wherein step 1) described in the particle diameter of silica flour be 50nm-20 μm, the particle diameter of the silica flour after milled processed is 30nm-
500nm；The high molecular polymer is at least one in following substances：Phenolic resin, pitch, polyvinylidene fluoride
(PVDF), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO), polyvinyl chloride (PVC), polypropylene
Nitrile (PAN), polyacetylene, glucose, sucrose, citric acid, sodium alginate, carboxymethylcellulose calcium, hydroxypropyl cellulose, poly- second two
Alcohol, gelatin, starch, shitosan, alginic acid；At least one of the source of aluminium for following substances:It is aluminium isopropoxide, three aluminium ethylates, secondary
Aluminium butoxide, aluminum acetate, preferably aluminium isopropoxide.
Wherein step 2) described in the condition of rotary evaporation be：Temperature is 30 DEG C -70 DEG C, and preferably 60 DEG C, rotary speed is
30-150 rev/min, preferably 120 revs/min；The thickness of amorphous carbon or alundum (Al2O3) is preferably 10-20nm, and content is excellent
Elect 1%-5% as.
Step 2), 4) and 5) described in non-oxidizing atmosphere provided by following at least one gases：Nitrogen, argon gas, helium,
The sintering temperature be 500-1100 DEG C, preferably 700-1000 DEG C, programming rate be 1-15 DEG C/min, preferably 1-5 DEG C/
Min, sintering time are 1-15h, preferably 2-6h.
Step 3) described in inorganic carbon source be selected from following at least one：Soft carbon, hard carbon, Scaly graphite, aphanitic graphite, people
Make graphite, electrically conductive graphite, MCMB, Graphene, CNT；The polymeric additive be following substances in extremely
Few one kind：It is phenolic resin, pitch, polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), poly-
Ethylene oxide (PEO), polyvinyl chloride (PVC), polyacrylonitrile (PAN), polyacetylene, polyaniline, polythiophene；The hydroxy compounds
At least one of the dispersant for following substances：Glucose, sucrose, citric acid, sodium alginate, carboxymethylcellulose calcium, hydroxypropyl are fine
Dimension element, gelatin, starch, shitosan, alginic acid；The viscosity is to test under 293K in temperature, and viscosity can be 1-104MPa s,
Preferably 100-500mPa s.
Step 3) in silica flour can be (1-8) with the mass ratio of inorganic carbon source：(2-9), preferably (2-7)：(3-8), specifically
Can be 2:8、3:7、4:6、5:5、6:4、7:3、8:2；In the solution, silica flour can be 1- with the mass concentration sum of inorganic carbon source
50%.The additives ratio is silica flour and the 0.1-30% of inorganic carbon source gross mass, preferably 1%-10%, the dispersion
Agent ratio is the 0.1-60%, preferably 20%-40% of silica flour and carbon source gross mass.
Step 4) and 5) described in be spray-dried air inlet temperature can be 120-220 DEG C, preferably 160-220 DEG C, discharging
Mouth temperature is 60 DEG C -120 DEG C, preferably 60-100 DEG C.The spray drying device feed pump frequency can be 10-50Hz.
Step 5) described in inorganic or organic carbon source be the high carbon source of phosphorus content or graphitized carbon, selected from it is following at least
It is a kind of:Delanium, electrically conductive graphite, MCMB, Graphene, carbon nanometer, coal tar, asphalt, phenolic resin, sea
Mosanom, carboxymethylcellulose calcium, hydroxypropyl cellulose, gelatin, polyvinylpyrrolidone (PVP)；The viscosity in temperature is
Test under 293K, viscosity can be 100-106MPa s, preferably 300-800mPa s.
The particle diameter of Si-C composite material provided by the present invention is 1-20 μm；The silica flour of uniform cladding is uniformly dispersed in material
The inside of material；By way of being repeatedly spray-dried, fine and close spherical Si-C composite material is formed；Solved by multi-buffering-layer
Defect of the silicon class material in lithium battery applications.
Another object of the present invention is to provide the application of the Si-C composite material.
Application provided by the present invention is application of the silicon carbide composite particles as battery electrode material, especially as lithium from
The application of sub- cell negative electrode material.
Compared with prior art, the present invention is provided preparation method low cost, degree of being practical is high, can prepare on a large scale,
Capacity controllable, excellent performance, and the Si-C composite material for obtaining is integrated with the advantage of Si-C composite material and porous material, passes through
Multi-buffering-layer, improve silica-base material as cyclicity that lithium ion battery negative material is present it is poor, coulombic efficiency is low asks
Topic, and we can also prepare reversible capacity in 400- by the ratio of silica flour and carbon source in regulation and control experimentation
Composite between 1200mAh/g.
Description of the drawings
Electron scanning micrographs of the Fig. 1 for 1 gained Sample Spray dry of embodiment.
Fig. 2 is the electron scanning micrograph that embodiment 1 obtains Sample Spray dry after carbon source filling.
Fig. 3 be the Si-C composite material obtained with embodiment 1 as negative material, under the conditions of 100mA/g constant current charge-discharges
First circle charging and discharging curve.
Fig. 4 be the Si-C composite material obtained with embodiment 2 as negative material, under the conditions of 100mA/g constant current charge-discharges
First circle charging and discharging curve.
Fig. 5 is the electron scanning micrograph of the fine and close Si-C composite material product obtained with embodiment 8.
Specific embodiment
With reference to specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Experimental technique described in following embodiments, if no special instructions, is conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
The preparation of embodiment 1, Si-C composite material and its electrochemical property test：
By business silica flour with after ball mill pretreatment, addition sand mill carries out sand milling, the silica flour of the size needed for obtaining.Press
Silica flour：Glucose=10:Silica flour, with water as solvent, is dispersed in the aqueous solution containing glucose by ultrasonically treated by 1 ratio
In, the solution for obtaining is reduced pressure at 60 DEG C rotary evaporation, after by sample at 600 DEG C of blanket of nitrogen sintering processes, obtain without fixed
The silica flour of shape carbon coating.
By silica flour：Graphite=7:3 mass ratio mixing, with water as solvent, PVP is additive, and sucrose is dispersant, in room
Lower stirring more than the 5h of temperature, obtains the slurry that viscosity is 100mPa s.Slurry is spray-dried, inlet temperature is 180
DEG C, discharging opening temperature be 100 DEG C, after by Sample Spray dry 600 DEG C sinter, obtain the Si-C composite material of porous, porous
In carbon-silicon composite material, silicone content is 65%, and carbon content is 35%, and tap density is 0.63g/cm3。
Sample after sintering is mixed with electrically conductive graphite, carboxymethylcellulose calcium, more than 10h is stirred, obtaining viscosity is
The slurry of 400mPa s, slurry is spray-dried, inlet temperature be 200 DEG C, discharging opening temperature be 90 DEG C, after will spray
Mist drying sample is sintered for 1000 DEG C in a nitrogen atmosphere, obtains the Si-C composite material of densification, and carbon content is 55%, and silicone content is
45%, tap density is 0.76g/cm3。
The sign of silicon carbide composite particles：
The particle diameter of the Si-C composite material obtained under above-mentioned condition is detected with NEC's ESEM (JEOL-6700F)
And size distribution, as a result show the size distribution of Si-C composite material than more uniform, particle diameter between 1-20 μm (see Fig. 2).
The Electrochemical Characterization of silicon carbide composite particles：
By the Si-C composite material prepared in embodiment 1, acetylene black and Kynoar (binding agent) with mass ratio
80：10：10 mixing are made into slurry, are homogeneously applied to obtain cathode membrane in copper foil current collector.Using metal lithium sheet as positive pole,
Microporous polypropylene membrane (Celgard 2400) is used as barrier film, 1mol/L LiPF6(it is 1 that solvent is volume ratio：1 ethylene carbonate
With dimethyl carbonate mixed liquor) as electrolyte, button cell is assembled in the glove box of argon gas protection, carries out charge and discharge electrical measurement
Examination, test program is 100mA/g, and it is 0.01～1.0V that charging/discharging voltage is interval, and first circle charging and discharging curve is shown in Fig. 3.Battery testing
As a result it is listed in table 1.
First charge-discharge cycle efficieny is more than 80%, and initial charge capacity is 880mAh/g, circulates 50 charging specific volumes afterwards
Measure as 723mAh/g.
Embodiment 2：
By business silica flour with after ball mill pretreatment, addition sand mill carries out sand milling, the silica flour of the size needed for obtaining.Press
Silica flour：Citric acid=10:1 ratio, with water as solvent, is dispersed in silica flour containing lemon aqueous acid by ultrasonically treated
In, the solution for obtaining is reduced pressure at 60 DEG C rotary evaporation, after by sample at 600 DEG C of argon atmospher sintering processes, obtain carbon bag
The silica flour for covering.
By silica flour：Graphite=6:4 mass ratio mixing, with water as solvent, PVP is additive, and sucrose is dispersant, in room
Lower stirring more than the 5h of temperature, obtains the slurry that viscosity is 100mPa s.Slurry is spray-dried, inlet temperature is 180
DEG C, discharging opening temperature is 100 DEG C, after by Sample Spray dry in 600 DEG C of argon atmospher sintering, obtain the silicon-carbon composite wood of porous
Material, in porous carbon-silicon composite material, silicone content is 54%, and carbon content is 46%, and tap density is 0.74g/cm3。
Sample after sintering is mixed with electrically conductive graphite, carboxymethylcellulose calcium, more than 10h is stirred, obtaining viscosity is
The slurry of 400mPa s, slurry is spray-dried, inlet temperature be 200 DEG C, discharging opening temperature be 90 DEG C, after will spray
Mist drying sample obtains the Si-C composite material of densification in 1000 DEG C of sintering of argon atmospher, and in carbon-silicon composite material, silicone content is
34%, carbon content is 66%, and tap density is 0.8g/cm3。
The positive pole of battery, negative pole, electrolyte and battery assemble same as Example 1, the composition of gained silicon carbide composite particles
And table 1 is listed in the test result of simulated battery, first circle charging and discharging curve is shown in Fig. 4.
Embodiment 3：
By business silica flour with after ball mill pretreatment, addition sand mill carries out sand milling, the silica flour of the size needed for obtaining.Press
Silica flour：Sucrose=10:1 ratio, with water as solvent, is dispersed in silica flour in the aqueous solution containing sucrose by ultrasonically treated,
The solution for obtaining is reduced pressure at 60 DEG C rotary evaporation, after by sample at 600 DEG C of blanket of nitrogen sintering processes, obtain carbon coating
Silica flour.
By silica flour：Graphite=5:5 mass ratio mixing, with water as solvent, starch is additive, and sucrose is dispersant,
More than 5h is stirred under room temperature, obtains the slurry that viscosity is 100mPa s.Slurry is spray-dried, inlet temperature is 180
DEG C, discharging opening temperature is 100 DEG C, after by Sample Spray dry in 600 DEG C of blanket of nitrogen sintering, obtain the silicon-carbon composite wood of porous
Material, in porous carbon-silicon composite material, silicone content is 44%, and carbon content is 56%, and tap density is 0.76g/cm3。
Sample after sintering is mixed with electrically conductive graphite, carboxymethylcellulose calcium, more than 10h is stirred, obtaining viscosity is
The slurry of 400mPa s, slurry is spray-dried, inlet temperature be 200 DEG C, discharging opening temperature be 90 DEG C, after will spray
Mist drying sample obtains the Si-C composite material of densification in 1000 DEG C of sintering of blanket of nitrogen, and in carbon-silicon composite material, silicone content is
24%, carbon content is 76%, and tap density is 0.83g/cm3。
The positive pole of battery, negative pole, electrolyte and battery assemble same as Example 1, the composition of gained silicon carbide composite particles
And table 1 is listed in the test result of simulated battery.
Embodiment 4：
By business silica flour with after ball mill pretreatment, addition sand mill carries out sand milling, the silica flour of the size needed for obtaining.Press
Silica flour：PVP=10:1 ratio, with water as solvent, is dispersed in silica flour in the aqueous solution containing PVP by ultrasonically treated, will
The solution for obtaining reduces pressure at 60 DEG C rotary evaporation, after by sample at 600 DEG C of argon atmospher sintering processes, obtain the silicon of carbon coating
Powder.
By silica flour：Graphite=4:6 mass ratio mixing, with water as solvent, gelatin is additive, 5h is stirred at room temperature with
On, obtain the slurry that viscosity is 100mPa s.Slurry is spray-dried, inlet temperature is 180 DEG C, discharging opening temperature
For 100 DEG C, after by Sample Spray dry in 600 DEG C of argon atmospher sintering, obtain the Si-C composite material of porous, porous carbon silicon is combined
In material, silicone content is 35%, and carbon content is 65%, and tap density is 0.74g/cm3。
Sample after sintering is mixed with electrically conductive graphite, carboxymethylcellulose calcium, more than 10h is stirred, obtaining viscosity is
The slurry of 400mPa s, slurry is spray-dried, inlet temperature be 200 DEG C, discharging opening temperature be 90 DEG C, after will spray
Mist drying sample obtains the Si-C composite material of densification in 1000 DEG C of sintering of argon atmospher, and in carbon-silicon composite material, silicone content is
18%, carbon content is 82%, and tap density is 0.85g/cm3。
The positive pole of battery, negative pole, electrolyte and battery assemble same as Example 1, the composition of gained silicon carbide composite particles
And table 1 is listed in the test result of simulated battery.
Embodiment 5：
By business silica flour with after ball mill pretreatment, addition sand mill carries out sand milling, the silica flour of the size needed for obtaining.Press
Silica flour：Aluminium isopropoxide=10:1 ratio, with isopropanol as solvent, is dispersed in silica flour containing aluminium isopropoxide by ultrasonically treated
Aqueous isopropanol in, the solution for obtaining is reduced pressure at 60 DEG C rotary evaporation, after by sample at 600 DEG C of helium-atmosphere at sintering
Reason, obtains the silica flour of alundum (Al2O3) cladding.
By silica flour：Graphite=6:4 mass ratio mixing, with water as solvent, polyacrylonitrile is additive, and sucrose is dispersion
Agent, is stirred at room temperature more than 5h, obtains the slurry that viscosity is 100mPa s.Slurry is spray-dried, inlet temperature
For 180 DEG C, discharging opening temperature is 100 DEG C, after by Sample Spray dry in 600 DEG C of sintering of helium-atmosphere, the silicon-carbon for obtaining porous is multiple
Condensation material, in porous carbon-silicon composite material, silicone content is 54%, and carbon content is 46%, and tap density is 0.71g/cm3。
Sample after sintering is mixed with electrically conductive graphite, carboxymethylcellulose calcium, more than 10h is stirred, obtaining viscosity is
The slurry of 400mPa s, slurry is spray-dried, inlet temperature be 200 DEG C, discharging opening temperature be 90 DEG C, after will spray
Mist drying sample obtains the Si-C composite material of densification in 1000 DEG C of sintering of helium-atmosphere, and in carbon-silicon composite material, silicone content is
34%, carbon content is 66%, and tap density is 0.81g/cm3。
The positive pole of battery, negative pole, electrolyte and battery assemble same as Example 1, the composition of gained silicon carbide composite particles
And table 1 is listed in the test result of simulated battery.
Embodiment 6：
By business silica flour with after ball mill pretreatment, addition sand mill carries out sand milling, the silica flour of the size needed for obtaining.Silicon
Powder：Three aluminium ethylate=10:Silica flour, with ethanol as solvent, is dispersed in the second containing three aluminium ethylates by ultrasonically treated by 1 ratio
In alcoholic solution, the solution for obtaining is reduced pressure at 60 DEG C rotary evaporation, after by sample at 600 DEG C of argon atmospher sintering processes, obtain
To the silica flour of alundum (Al2O3) cladding.
By silica flour：Graphite=6:4 mass ratio mixing, with water as solvent, PVP is additive, and the weight average molecular weight of PVP is
300000, sucrose is dispersant, and more than 5h is stirred at room temperature, and obtains the slurry that viscosity is 100mPa s.Slurry is sprayed
Mist is dried, and inlet temperature is 180 DEG C, and discharging opening temperature is 100 DEG C, after by Sample Spray dry in 600 DEG C of argon atmospher sintering,
The Si-C composite material of porous is obtained, silicone content is 45% in porous carbon-silicon composite material, and carbon content is 55%, and tap density is
0.74g/cm3。
Sample after sintering is mixed with electrically conductive graphite, carboxymethylcellulose calcium, more than 10h is stirred, obtaining viscosity is
The slurry of 400mPa s, slurry is spray-dried, inlet temperature be 200 DEG C, discharging opening temperature be 90 DEG C, after will spray
Mist drying sample obtains the Si-C composite material of densification in 1000 DEG C of sintering of argon atmospher, and in carbon-silicon composite material, silicone content is
33%, carbon content is 67%, and tap density is 0.86g/cm3。
The positive pole of battery, negative pole, electrolyte and battery assemble same as Example 1, the composition of gained silicon carbide composite particles
And table 1 is listed in the test result of simulated battery.
Embodiment 7：
Other conditions are same as Example 6, and difference is silica flour：Graphite=5:5.
The silicone content of the fine and close Si-C composite material of gained is 28%, and carbon content is 72%, and tap density is 0.85g/cm3。
The composition of gained silicon carbide composite particles and table 1 is listed in the test result of simulated battery.
Embodiment 8：
By business silica flour with after ball mill pretreatment, addition sand mill carries out sand milling, the silica flour of the size needed for obtaining.Silicon
Powder：Aluminium secondary butylate=10:Silica flour, with sec-butyl alcohol as solvent, is disperseed in aqueous by 1 ratio by ultrasonically treated, will
To solution reduce pressure at 60 DEG C rotary evaporation, after by sample at 600 DEG C of blanket of nitrogen sintering processes, obtain alundum (Al2O3) bag
The silica flour for covering.
By silica flour：Graphite=4:6 mass ratio mixing, with water as solvent, PVP is additive, and sucrose is dispersant, in room
Lower stirring more than the 5h of temperature, obtains the slurry that viscosity is 100mPa s.Slurry is spray-dried, inlet temperature is 180
DEG C, discharging opening temperature is 100 DEG C, after by Sample Spray dry in 600 DEG C of blanket of nitrogen sintering, obtain the silicon-carbon composite wood of porous
Material, in porous carbon-silicon composite material, silicone content is 34%, and carbon content is 66%, tap density 0.79g/cm3。
Sample after sintering is mixed with Graphene, gelatin, asphalt, more than 10h is stirred, obtaining viscosity is
The slurry of 400mPa s, slurry is spray-dried, inlet temperature be 200 DEG C, discharging opening temperature be 90 DEG C, after will spray
Mist drying sample obtains the Si-C composite material of densification in 1000 DEG C of sintering of blanket of nitrogen, and in composite, silicone content is 22%, carbon
Content is 78%, and tap density is 0.9g/cm3。
The positive pole of battery, negative pole, electrolyte and battery assemble same as Example 1, the composition of gained silicon carbide composite particles
And table 1 is listed in the test result of simulated battery, stereoscan photograph such as Fig. 5 of gained densification Si-C composite material.
Embodiment 9：
By business silica flour with after ball mill pretreatment, addition sand mill carries out sand milling, the silica flour of the size needed for obtaining.Silicon
Powder：Aluminum acetate=10:1 ratio, dissolves aluminum acetate by solvent of water, alumine hydroxide colloid is obtained, leads to after being sufficiently stirred for hydrolysis
Cross ultrasonically treated by silica flour dispersed gained alumine hydroxide colloid, the solution for obtaining reduced pressure at 60 DEG C rotary evaporation,
Afterwards by sample at 600 DEG C of argon atmospher sintering processes, obtain the silica flour of alundum (Al2O3) cladding.
By silica flour：Graphite=4:6 mass ratio mixing, with water as solvent, sodium alginate is additive, and citric acid is dispersion
Agent, is stirred at room temperature more than 5h, obtains the slurry that viscosity is 100mPa s.Slurry is spray-dried, inlet temperature
For 180 DEG C, discharging opening temperature is 100 DEG C, after by Sample Spray dry in 600 DEG C of sintering of argon atmospher, the silicon-carbon for obtaining porous is multiple
Condensation material, in porous carbon-silicon composite material, silicone content is 35%, and carbon content is 65%, and tap density is 0.77g/cm3。
Sample after sintering is mixed with asphalt, carboxymethylcellulose calcium, more than 10h is stirred, obtaining viscosity is
The slurry of 400mPa s, slurry is spray-dried, inlet temperature be 200 DEG C, discharging opening temperature be 90 DEG C, after will spray
Mist drying sample obtains the Si-C composite material of densification in 1000 DEG C of sintering of argon atmospher, and in composite, silicone content is 19%, carbon
Content is 81%, and tap density is 0.88g/cm3。
The positive pole of battery, negative pole, electrolyte and battery assemble same as Example 1, the composition of gained silicon carbide composite particles
And table 1 is listed in the test result of simulated battery.
Comparative example 1：
By silica flour：Graphite=4:6 mass ratio mixing, with water as solvent, PVP is additive, and sucrose is dispersant, in room
Lower stirring more than the 5h of temperature, obtains the slurry that viscosity is 100mPa s.Slurry is spray-dried, inlet temperature is 180
DEG C, discharging opening temperature be 100 DEG C, after by Sample Spray dry 1000 DEG C sinter, the Si-C composite material tap density for obtaining
For 0.5g/cm3.The positive pole of battery, negative pole, electrolyte and battery assemble same as Example 1, the group of gained silicon carbide composite particles
Into and be listed in table 1 in the test result of simulated battery.
Comparative example 2：
By silica flour：Glucose=10:1 ratio, with water as solvent, is dispersed in silica flour containing grape by ultrasonically treated
Sugar the aqueous solution in, by the solution for obtaining at 60 DEG C rotary evaporation, after by sample at 600 DEG C sintering processes, obtain carbon bag
The silica flour for covering.
By silica flour：Graphite=6:4 mass ratio mixing, with water as solvent, PVP is additive, and sucrose is dispersant, in room
Lower stirring more than the 5h of temperature, obtains the slurry that viscosity is 100mPa s.Slurry is spray-dried, inlet temperature is 180
DEG C, discharging opening temperature be 100 DEG C, after by Sample Spray dry 1000 DEG C sinter, the Si-C composite material tap density for obtaining
For 0.53g/cm3。
The positive pole of battery, negative pole, electrolyte and battery assemble same as Example 1, the composition of gained silicon carbide composite particles
And table 1 is listed in the test result of simulated battery.
Comparative example 3：
By silica flour：Graphite=4:6 mass ratio mixing, with water as solvent, PVP is additive, and sucrose is dispersant, in room
Lower stirring more than the 5h of temperature, obtains the slurry that viscosity is 100mPa s.Slurry is spray-dried, inlet temperature is 180
DEG C, discharging opening temperature be 100 DEG C, after by Sample Spray dry 600 DEG C sinter.
Sample after sintering is mixed with electrically conductive graphite, more than 10h is stirred, the slurry that viscosity is 400mPa s is obtained, will
Slurry is spray-dried, inlet temperature be 200 DEG C, discharging opening temperature be 90 DEG C, after by Sample Spray dry at 1000 DEG C
Sintering, obtains the Si-C composite material of densification, and tap density is 0.75g/cm3。
The positive pole of battery, negative pole, electrolyte and battery assemble same as Example 1, the composition of gained silicon carbide composite particles
And table 1 is listed in the test result of simulated battery.
The composition of table 1, Si-C composite material and under the conditions of 100mA/g constant current charge-discharge test result
Claims (10)
1. a kind of preparation method of Silicon-carbon composite material for lithium ion battery, comprises the following steps that：
1) by sanded treatment after silica flour ball mill grinding, the silica flour after process is dispersed in into the solution containing silicon source or containing silicon source
It is in colloid and ultrasonically treated, make silica flour suspend in the solution, prevent to reunite；
2) by step 1) obtained by solution decompression rotary evaporation remove solvent after, be sintered under non-oxidizing atmosphere, in silicon
Surface coating alundum (Al2O3), the thickness of alundum (Al2O3) is 5 30nm, and content is 0.5% 10%；
3) by step 2) obtained by the silica flour that coats be 50000 with inorganic carbon source, hydroxy compounds dispersant, weight average molecular weight
400000 polymeric additive carries out mechanical agitation, is uniformly mixed, the suitable weak solution of viscosity；
4) by step 3) obtained by weak solution carry out spray drying treatment, obtain Si-C composite material, and in non-oxidizing atmosphere
Under be sintered, obtain the Si-C composite material of porous, in porous carbon-silicon composite material, silicone content is 20% 60%, carbon content
For 40% 80%, tap density is 0.6 0.9g/cm3；
5) in step 4) obtained by Si-C composite material hole in, fill inorganic or organic carbon source, configure higher dense of viscosity
Solution, carries out spray drying treatment, obtains the spherical composite of densification, and is sintered under non-oxidizing atmosphere, finally
Silicon-carbon composite material for lithium ion battery is obtained, silicone content is 10% 40% in composite, carbon content is 60% 90%, is shaken
Real density is 0.7 1.1g/cm3。
2. method according to claim 1, it is characterised in that：Step 1) described in silica flour particle diameter be 20 μm of 50nm, grind
The particle diameter of the silica flour after mill process is 30nm 500nm；At least one of the source of aluminium selected from following substances:Aluminium isopropoxide, three second
Aluminium alcoholates, aluminium secondary butylate, aluminum acetate, Tributyl aluminate.
3. the method according to one of claim 12, it is characterised in that：Wherein step 2) described in rotary evaporation condition
For：Temperature is 30 DEG C 70 DEG C, and rotary speed is 30 150 revs/min；The thickness of alundum (Al2O3) is 10 20nm, and content is
1% 5%.
4. the method according to one of claim 12, it is characterised in that：Step 2), 4) and 5) described in non-oxidizing gas
Atmosphere is provided by following at least one gases：Nitrogen, argon gas, helium, the sintering temperature are 500 1100 DEG C, and programming rate is 1
15 DEG C/min, sintering time is 1 15h.
5. the method according to one of claim 12, it is characterised in that：Step 3) described in inorganic or organic carbon source be selected from
Following at least one：Soft carbon, hard carbon, Scaly graphite, aphanitic graphite, Delanium, electrically conductive graphite, MCMB, stone
Black alkene, CNT；The additive is at least one in following substances：It is phenolic resin, pitch, polyvinylidene fluoride, poly-
Vinylpyrrolidone, polyvinyl alcohol, polyethylene glycol oxide, polyvinyl chloride, polyacrylonitrile, polyacetylene, polyaniline, polythiophene；It is described
At least one of the dispersant for following substances：Glucose, sucrose, citric acid, sodium alginate, carboxymethylcellulose calcium, hydroxypropyl are fine
Dimension element, polyethylene glycol, gelatin, starch, shitosan, alginic acid；The viscosity is to test under 293K in temperature, and viscosity can be 1
104mPa·s。
6. the method according to one of claim 12, it is characterised in that：Step 4) and 5) described in be spray-dried air inlet
Temperature is 120 220 DEG C, and discharging opening temperature is 60 DEG C 120 DEG C, and the spray drying device feed pump frequency is 10 30Hz.
7. the method according to one of claim 12, it is characterised in that：Step 5) described in carbon source be selected from following
It is at least one:Delanium, electrically conductive graphite, MCMB, Graphene, carbon nanometer, coal tar, asphalt, phenolic aldehyde tree
Fat, sodium alginate, carboxymethylcellulose calcium, hydroxypropyl cellulose, gelatin, polyvinylpyrrolidone；The viscosity in temperature is
Test under 293K, viscosity can be 100 106mPa·s。
8. the method according to one of claim 12, it is characterised in that：Step 5) described in carbon source contain gelatin simultaneously
And Graphene.
9. the Si-C composite material that arbitrary methods described is prepared in claim 18.
10. application of the Si-C composite material described in claim 9 as lithium ion battery negative material.
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| EP3133690A1 (en) * | 2015-07-20 | 2017-02-22 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Silicon-carbon composite particulate material |
| CN105552357B (en) * | 2016-01-29 | 2018-10-02 | 银隆新能源股份有限公司 | Lithium titanate electrode material and preparation method thereof |
| CN105702924B (en) * | 2016-01-29 | 2018-10-02 | 银隆新能源股份有限公司 | Lithium titanate electrode material and preparation method thereof |
| DE102016203352A1 (en) * | 2016-03-01 | 2017-09-07 | Wacker Chemie Ag | Process for processing electrode materials for batteries |
| CN105742599B (en) * | 2016-03-18 | 2019-04-26 | 苏州协鑫集成科技工业应用研究院有限公司 | Si-C composite material and preparation method thereof and negative electrode material and battery |
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| CN114975980A (en) * | 2019-03-19 | 2022-08-30 | 宁德新能源科技有限公司 | Negative electrode material, and electrochemical device and electronic device using same |
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| CN101153358A (en) * | 2006-09-28 | 2008-04-02 | 深圳市比克电池有限公司 | Method of producing silicon carbon negative pole material of lithium ion battery |
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