CN104716312A - 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 PDF

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CN104716312A
CN104716312A CN201510106478.7A CN201510106478A CN104716312A CN 104716312 A CN104716312 A CN 104716312A CN 201510106478 A CN201510106478 A CN 201510106478A CN 104716312 A CN104716312 A CN 104716312A
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carbon
composite material
silicon
silica flour
viscosity
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CN104716312B (en
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郭玉国
孔一鸣
徐泉
殷雅侠
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Beijing One Gold Amperex Technology Ltd
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Institute of Chemistry CAS
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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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/13—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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

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

A kind of Silicon-carbon composite material for lithium ion battery and its preparation method and application
Technical field
The present invention relates to a kind of preparation method of Si-C composite material and the application as lithium ion battery negative material thereof.
Background technology
Along with the worsening shortages of petroleum resources and environmental pollution are more and more serious, develop reproducible clean energy resource and become more and more important.The research and development of current electric automobile have become one of global focus, and wherein lithium ion battery is extremely paid attention to as its core technology.Lithium ion battery has the outstanding advantages such as specific energy is high, long service life, green non-pollution and has been widely used in portable electronic products and electric automobile.Current business-like lithium ion battery negative material mainly material with carbon element, but its theoretical specific capacity is only 372mAh/g, more and more cannot meet lithium ion battery applications field to requirement that is high-power, high power capacity.Therefore, the new type lithium ion battery negative material developing height ratio capacity is very urgent.
Silicon has high theoretical specific capacity (4200mAh/g) and removal lithium embedded, is to be used as one of the most promising material of lithium ion battery negative, and rich reserves, cost are lower in the earth.But the change in volume (~ 300%) that silicon materials are adjoint serious in removal lithium embedded process, cause destruction and the efflorescence of material structure, and then cause electrode cracking and active material to come off from collector, repeatedly after circulation, capacity is decayed rapidly, limits the application of silicon materials in field of lithium ion battery.Therefore, how improving the cyclical stability of silicon materials, is the focus and emphasis of research at present.
At present, the cyclical stability of silicon is improved mainly through the nanometer of silicon and silicon based composite material.But silicon nanowires, nano-tube preparation process are complicated, yield poorly, be difficult to industrialization large-scale production, degree of being practical is low.Because carbon class material has good flexibility, good electron conduction, less volumetric expansion, and the resilient coating formed by carbon matrix effectively can alleviate the volumetric expansion of silicon materials, improves the cyclical stability of silicon class material.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defect that existing Si-C composite material first circle coulombic efficiency is low, cyclical stability is poor, cost is high, preparation technology is not suitable for suitability for industrialized production.Provide Silicon-carbon composite material for lithium ion battery that a kind of cost is low, tap density is high, can be mass-produced and preparation method thereof, and effectively solve the defect of silicon class material by multi-buffering-layer, improve the cyclical stability of Si-C composite material.
First the present invention improves a kind of Silicon-carbon composite material for lithium ion battery, has higher tap density, and tap density is 0.7-1.1g/cm 3, be made up of porous silicon carbon composite and the carbon be filled in its hole, in porous carbon silicon composite, silicone content is 10%-40%, and carbon content is 60%-90%.Preferably, the silicon face in porous silicon carbon composite is coated amorphous carbon or alundum (Al2O3).
Silicon-carbon composite material for lithium ion battery provided by the present invention prepares in accordance with the following steps:
1) by sanded after silica flour ball mill grinding, by process after silica flour be dispersed in macromolecule polymer solution or containing aluminium source solution or containing aluminium source colloid in and ultrasonic process, make silica flour suspend in the solution, prevent reunite.
2) by step 1) the solution decompression rotary evaporation of gained is except after desolventizing, sinter under non-oxidizing atmosphere, at the coated amorphous carbon of silicon face or alundum (Al2O3), the thickness of amorphous carbon or alundum (Al2O3) is 5-30nm, and content is 0.5%-10%.
3) by step 2) the coated good silica flour of gained and inorganic carbon source, hydroxy compounds dispersant, weight average molecular weight be that the polymeric additive of 50000-400000 carries out mechanical agitation, mixed, the weak solution that viscosity is suitable.
4) by step 3) weak solution of gained carries out spray drying treatment, obtain Si-C composite material, and sinter under non-oxidizing atmosphere, obtain the Si-C composite material of porous, in porous carbon silicon composite, silicone content is 20%-60%, carbon content is 40%-80%, and tap density is 0.6-0.9g/cm 3.
5) in step 4) in the hole of the Si-C composite material of gained, fill inorganic or organic carbon source, the concentrated solution that configuration viscosity is higher, carry out spray drying treatment, obtain fine and close spherical composite material, and sinter under non-oxidizing atmosphere, finally obtain the Silicon-carbon composite material for lithium ion battery of high-tap density, stable circulation, in composite material, silicone content is 10%-40%, and carbon content is 60%-90%, and tap density is 0.7-1.1g/cm 3.
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; Described high molecular polymer is at least one in following substances: phenolic resins, pitch, polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO), polyvinyl chloride (PVC), polyacrylonitrile (PAN), polyacetylene, glucose, sucrose, citric acid, sodium alginate, carboxymethyl cellulose, hydroxypropyl cellulose, polyethylene glycol, gelatin, starch, shitosan, alginic acid; Described aluminium source is at least one of following substances: aluminium isopropoxide, three aluminium ethylates, aluminium secondary butylate, aluminum acetate, is preferably aluminium isopropoxide.
Wherein step 2) described in the condition of rotary evaporation be: temperature is 30 DEG C-70 DEG C, preferably 60 DEG C, and 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 preferably 1%-5%.
Step 2), 4) and 5) described in non-oxidizing atmosphere provided by following at least one gas: nitrogen, argon gas, helium, described sintering temperature is 500-1100 DEG C, be preferably 700-1000 DEG C, programming rate is 1-15 DEG C/min, be preferably 1-5 DEG C/min, sintering time is 1-15h, is 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, Delanium, electrically conductive graphite, MCMB, Graphene, carbon nano-tube; Described polymeric additive is at least one in following substances: phenolic resins, pitch, polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO), polyvinyl chloride (PVC), polyacrylonitrile (PAN), polyacetylene, polyaniline, polythiophene; Described hydroxy compounds dispersant is at least one of following substances: glucose, sucrose, citric acid, sodium alginate, carboxymethyl cellulose, hydroxypropyl cellulose, gelatin, starch, shitosan, alginic acid; Described viscosity is tested under temperature is 293K, and viscosity can be 1-10 4mPas, is preferably 100-500mPas.
Step 3) in the mass ratio of silica flour and inorganic carbon source can be (1-8): (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 described solution, the mass concentration sum of silica flour and inorganic carbon source can be 1-50%.Described additives ratio is the 0.1-30% of silica flour and inorganic carbon source gross mass, and be preferably 1%-10%, described dispersive agent ratio is the 0.1-60% of silica flour and carbon source gross mass, is preferably 20%-40%.
Step 4) and 5) described in spraying dry air inlet temperature can be 120-220 DEG C, be preferably 160-220 DEG C, discharging opening temperature is 60 DEG C-120 DEG C, be preferably 60-100 DEG C.Described spray drying device charging pump frequency can be 10-50Hz.
Step 5) described in inorganic or organic carbon source be the carbon source or graphitized carbon that phosphorus content is high, be selected from following at least one: Delanium, electrically conductive graphite, MCMB, Graphene, carbon nanometer, coal tar, petroleum asphalt, phenolic resins, sodium alginate, carboxymethyl cellulose, hydroxypropyl cellulose, gelatin, polyvinylpyrrolidone (PVP); Described viscosity is tested under temperature is 293K, and viscosity can be 100-10 6mPas, is preferably 300-800mPas.
The particle diameter of Si-C composite material provided by the present invention is 1-20 μm; Evenly coated silica flour is dispersed in the inside of material uniformly; By repeatedly spray-dired mode, form fine and close spherical Si-C composite material; The defect of silicon class material in lithium battery applications is solved by multi-buffering-layer.
Another object of the present invention is to provide the application of described Si-C composite material.
Application provided by the present invention is the application of silicon carbide composite particles as battery electrode material, particularly as the application of lithium ion battery negative material.
Compared with prior art, preparation method's cost provided by the invention is low, degree of being practical is high, can prepare on a large scale, capacity controllable, excellent performance, and the Si-C composite material obtained is integrated with the advantage of Si-C composite material and porous material, pass through multi-buffering-layer, improve the problem that cyclicity is poor, coulombic efficiency is low that silica-base material exists as lithium ion battery negative material, and we by the ratio of silica flour and carbon source in regulation and control experimentation, can also prepare the composite material of reversible capacity between 400-1200mAh/g.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of embodiment 1 gained Sample Spray dry.
Fig. 2 is the electron scanning micrograph that embodiment 1 obtains that carbon source fills rear Sample Spray dry.
Fig. 3 be the Si-C composite material that obtains with embodiment 1 for negative material, the first circle charging and discharging curve under 100mA/g constant current charge-discharge condition.
Fig. 4 be the Si-C composite material that obtains with embodiment 2 for negative material, the first circle charging and discharging curve under 100mA/g constant current charge-discharge condition.
Fig. 5 is the electron scanning micrograph of the fine and close Si-C composite material product obtained with embodiment 8.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Experimental technique described in following embodiment, if no special instructions, is conventional method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
The preparation of embodiment 1, Si-C composite material and electrochemical property test thereof:
By business silica flour with after ball mill preliminary treatment, add sand mill and carry out sand milling, obtain the silica flour of required size.In silica flour: the ratio of glucose=10:1, take water as solvent, to be dispersed in by silica flour in the aqueous solution containing glucose by ultrasonic process, reduce pressure the solution obtained at 60 DEG C rotary evaporation, after by sample sintering processes at blanket of nitrogen 600 DEG C, obtain the silica flour that amorphous carbon is coated
By silica flour: the mass ratio mixing of graphite=7:3, take water as solvent, PVP is additive, and sucrose is dispersant, at room temperature stirs more than 5h, obtains the slurry that viscosity is 100mPas.Slurry is carried out spraying dry, and inlet temperature is 180 DEG C, and discharging opening temperature is 100 DEG C, after by Sample Spray dry at 600 DEG C of sintering, obtain the Si-C composite material of porous, in porous carbon silicon composite, silicone content is 65%, carbon content is 35%, and tap density is 0.63g/cm 3.
Sample after sintering is mixed with electrically conductive graphite, carboxymethyl cellulose, stir more than 10h, obtain the slurry that viscosity is 400mPas, slurry is carried out spraying dry, inlet temperature is 200 DEG C, discharging opening temperature is 90 DEG C, after by Sample Spray dry 1000 DEG C of sintering in a nitrogen atmosphere, obtain fine and close Si-C composite material, carbon content is 55%, silicone content is 45%, and tap density is 0.76g/cm 3.
The sign of silicon carbide composite particles:
The particle diameter of the Si-C composite material obtained under detecting above-mentioned condition with NEC ESEM (JEOL-6700F) and particle size distribution, result shows that the particle size distribution of Si-C composite material is relatively more even, and particle diameter is (see Fig. 2) between 1-20 μm.
The Electrochemical Characterization of silicon carbide composite particles:
The Si-C composite material prepared in embodiment 1, acetylene black and Kynoar (binding agent) are made into slurry with mass ratio 80:10:10 mixing, are coated to equably in copper foil current collector and obtain cathode membrane.Using metal lithium sheet as positive pole, microporous polypropylene membrane (Celgard 2400) as barrier film, 1mol/L LiPF 6ethylene carbonate and the dimethyl carbonate mixed liquor of 1:1 (solvent to be volume ratio be) is as electrolyte; button cell is assembled in the glove box of argon shield; carry out charge-discharge test; test program is 100mA/g; charging/discharging voltage interval is 0.01 ~ 1.0V, and first circle charging and discharging curve is shown in Fig. 3.Cell testing results lists in table 1.
First charge-discharge cycle efficieny is greater than 80%, and initial charge capacity is 880mAh/g, and the charge specific capacity after 50 times that circulates is 723mAh/g.
Embodiment 2:
By business silica flour with after ball mill preliminary treatment, add sand mill and carry out sand milling, obtain the silica flour of required size.In silica flour: the ratio of citric acid=10:1, take water as solvent, be dispersed in containing in lemon aqueous acid by ultrasonic process by silica flour, reduce pressure the solution obtained at 60 DEG C rotary evaporation, after by sample sintering processes at argon atmospher 600 DEG C, obtain the silica flour that carbon is coated
By silica flour: the mass ratio mixing of graphite=6:4, take water as solvent, PVP is additive, and sucrose is dispersant, at room temperature stirs more than 5h, obtains the slurry that viscosity is 100mPas.Slurry is carried out spraying dry, and inlet temperature is 180 DEG C, and discharging opening temperature is 100 DEG C, after by Sample Spray dry at argon atmospher 600 DEG C sintering, obtain the Si-C composite material of porous, in porous carbon silicon composite, silicone content is 54%, carbon content is 46%, and tap density is 0.74g/cm 3.
Sample after sintering is mixed with electrically conductive graphite, carboxymethyl cellulose, stir more than 10h, obtain the slurry that viscosity is 400mPas, slurry is carried out spraying dry, inlet temperature is 200 DEG C, discharging opening temperature is 90 DEG C, after by Sample Spray dry at argon atmospher 1000 DEG C sintering, obtain fine and close Si-C composite material, in carbon-silicon composite material, silicone content is 34%, carbon content is 66%, and tap density is 0.8g/cm 3.
The assembling of the positive pole of battery, negative pole, electrolyte and battery is identical with embodiment 1, the composition of gained silicon carbide composite particles and list in table 1 in the test result of simulated battery, and first circle charging and discharging curve is shown in Fig. 4.
Embodiment 3:
By business silica flour with after ball mill preliminary treatment, add sand mill and carry out sand milling, obtain the silica flour of required size.In silica flour: the ratio of sucrose=10:1, take water as solvent, to be dispersed in by silica flour in the aqueous solution containing sucrose by ultrasonic process, reduce pressure the solution obtained at 60 DEG C rotary evaporation, after by sample sintering processes at blanket of nitrogen 600 DEG C, obtain the silica flour that carbon is coated.
By silica flour: the mass ratio mixing of graphite=5:5, take water as solvent, starch is additive, and sucrose is dispersant, at room temperature stirs more than 5h, obtains the slurry that viscosity is 100mPas.Slurry is carried out spraying dry, and inlet temperature is 180 DEG C, and discharging opening temperature is 100 DEG C, after by Sample Spray dry at blanket of nitrogen 600 DEG C sintering, obtain the Si-C composite material of porous, in porous carbon silicon composite, silicone content is 44%, carbon content is 56%, and tap density is 0.76g/cm 3.
Sample after sintering is mixed with electrically conductive graphite, carboxymethyl cellulose, stir more than 10h, obtain the slurry that viscosity is 400mPas, slurry is carried out spraying dry, inlet temperature is 200 DEG C, discharging opening temperature is 90 DEG C, after by Sample Spray dry at blanket of nitrogen 1000 DEG C sintering, obtain fine and close Si-C composite material, in carbon-silicon composite material, silicone content is 24%, carbon content is 76%, and tap density is 0.83g/cm 3.
The assembling of the positive pole of battery, negative pole, electrolyte and battery is identical with embodiment 1, the composition of gained silicon carbide composite particles and list in table 1 in the test result of simulated battery.
Embodiment 4:
By business silica flour with after ball mill preliminary treatment, add sand mill and carry out sand milling, obtain the silica flour of required size.In silica flour: the ratio of PVP=10:1, take water as solvent, to be dispersed in by silica flour in the aqueous solution containing PVP by ultrasonic process, reduce pressure the solution obtained at 60 DEG C rotary evaporation, after by sample sintering processes at argon atmospher 600 DEG C, obtain the silica flour that carbon is coated.
By silica flour: the mass ratio mixing of graphite=4:6, take water as solvent, gelatin is additive, at room temperature stirs more than 5h, obtains the slurry that viscosity is 100mPas.Slurry is carried out spraying dry, and inlet temperature is 180 DEG C, and discharging opening temperature is 100 DEG C, after by Sample Spray dry at argon atmospher 600 DEG C sintering, obtain the Si-C composite material of porous, in porous carbon silicon composite, silicone content is 35%, carbon content is 65%, and tap density is 0.74g/cm 3.
Sample after sintering is mixed with electrically conductive graphite, carboxymethyl cellulose, stir more than 10h, obtain the slurry that viscosity is 400mPas, slurry is carried out spraying dry, inlet temperature is 200 DEG C, discharging opening temperature is 90 DEG C, after by Sample Spray dry at argon atmospher 1000 DEG C sintering, obtain fine and close Si-C composite material, in carbon-silicon composite material, silicone content is 18%, carbon content is 82%, and tap density is 0.85g/cm 3.
The assembling of the positive pole of battery, negative pole, electrolyte and battery is identical with embodiment 1, the composition of gained silicon carbide composite particles and list in table 1 in the test result of simulated battery.
Embodiment 5:
By business silica flour with after ball mill preliminary treatment, add sand mill and carry out sand milling, obtain the silica flour of required size.In silica flour: the ratio of aluminium isopropoxide=10:1, take isopropyl alcohol as solvent, silica flour is dispersed in the aqueous isopropanol containing aluminium isopropoxide by ultrasonic process, reduce pressure the solution obtained at 60 DEG C rotary evaporation, after by sample sintering processes at helium-atmosphere 600 DEG C, obtain the silica flour that alundum (Al2O3) is coated.
By silica flour: the mass ratio mixing of graphite=6:4, take water as solvent, polyacrylonitrile is additive, and sucrose is dispersant, at room temperature stirs more than 5h, obtains the slurry that viscosity is 100mPas.Slurry is carried out spraying dry, and inlet temperature is 180 DEG C, and discharging opening temperature is 100 DEG C, after by Sample Spray dry at helium-atmosphere 600 DEG C sintering, obtain the Si-C composite material of porous, in porous carbon silicon composite, silicone content is 54%, carbon content is 46%, and tap density is 0.71g/cm 3.
Sample after sintering is mixed with electrically conductive graphite, carboxymethyl cellulose, stir more than 10h, obtain the slurry that viscosity is 400mPas, slurry is carried out spraying dry, inlet temperature is 200 DEG C, discharging opening temperature is 90 DEG C, after by Sample Spray dry at helium-atmosphere 1000 DEG C sintering, obtain fine and close Si-C composite material, in carbon-silicon composite material, silicone content is 34%, carbon content is 66%, and tap density is 0.81g/cm 3.
The assembling of the positive pole of battery, negative pole, electrolyte and battery is identical with embodiment 1, the composition of gained silicon carbide composite particles and list in table 1 in the test result of simulated battery.
Embodiment 6:
By business silica flour with after ball mill preliminary treatment, add sand mill and carry out sand milling, obtain the silica flour of required size.Silica flour: the ratio of three aluminium ethylates=10:1, take ethanol as solvent, silica flour is dispersed in the ethanolic solution containing three aluminium ethylates by ultrasonic process, reduce pressure the solution obtained at 60 DEG C rotary evaporation, after by sample sintering processes at argon atmospher 600 DEG C, obtain the silica flour that alundum (Al2O3) is coated.
By silica flour: the mass ratio mixing of graphite=6:4, take water as solvent, PVP is additive, and the weight average molecular weight of PVP is 300000, and sucrose is dispersant, at room temperature stirs more than 5h, obtains the slurry that viscosity is 100mPas.Slurry is carried out spraying dry, and inlet temperature is 180 DEG C, and discharging opening temperature is 100 DEG C, after by Sample Spray dry at argon atmospher 600 DEG C sintering, obtain the Si-C composite material of porous, in porous carbon silicon composite, silicone content is 45%, carbon content is 55%, and tap density is 0.74g/cm 3.
Sample after sintering is mixed with electrically conductive graphite, carboxymethyl cellulose, stir more than 10h, obtain the slurry that viscosity is 400mPas, slurry is carried out spraying dry, inlet temperature is 200 DEG C, discharging opening temperature is 90 DEG C, after by Sample Spray dry at argon atmospher 1000 DEG C sintering, obtain fine and close Si-C composite material, in carbon-silicon composite material, silicone content is 33%, carbon content is 67%, and tap density is 0.86g/cm 3.
The assembling of the positive pole of battery, negative pole, electrolyte and battery is identical with embodiment 1, the composition of gained silicon carbide composite particles and list in table 1 in the test result of simulated battery.
Embodiment 7:
Other conditions are identical with embodiment 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/cm 3.The composition of gained silicon carbide composite particles and list in table 1 in the test result of simulated battery.
Embodiment 8:
By business silica flour with after ball mill preliminary treatment, add sand mill and carry out sand milling, obtain the silica flour of required size.Silica flour: the ratio of aluminium secondary butylate=10:1, take sec-butyl alcohol as solvent, by ultrasonic process by silica flour dispersion in aqueous, reduce pressure the solution obtained at 60 DEG C rotary evaporation, after by sample sintering processes at blanket of nitrogen 600 DEG C, obtain the silica flour that alundum (Al2O3) is coated.
By silica flour: the mass ratio mixing of graphite=4:6, take water as solvent, PVP is additive, and sucrose is dispersant, at room temperature stirs more than 5h, obtains the slurry that viscosity is 100mPas.Slurry is carried out spraying dry, and inlet temperature is 180 DEG C, and discharging opening temperature is 100 DEG C, after by Sample Spray dry at blanket of nitrogen 600 DEG C sintering, obtain the Si-C composite material of porous, in porous carbon silicon composite, silicone content is 34%, carbon content is 66%, tap density 0.79g/cm 3.
Sample after sintering is mixed with Graphene, gelatin, petroleum asphalt, stir more than 10h, obtain the slurry that viscosity is 400mPas, slurry is carried out spraying dry, inlet temperature is 200 DEG C, discharging opening temperature is 90 DEG C, after by Sample Spray dry at blanket of nitrogen 1000 DEG C sintering, obtain fine and close Si-C composite material, in composite material, silicone content is 22%, carbon content is 78%, and tap density is 0.9g/cm 3.
The assembling of the positive pole of battery, negative pole, electrolyte and battery is identical with embodiment 1, the composition of gained silicon carbide composite particles and list in table 1 in the test result of simulated battery, and the stereoscan photograph of gained densification Si-C composite material is as Fig. 5.
Embodiment 9:
By business silica flour with after ball mill preliminary treatment, add sand mill and carry out sand milling, obtain the silica flour of required size.Silica flour: the ratio of aluminum acetate=10:1, take water as dissolution with solvents aluminum acetate, obtained alumine hydroxide colloid after abundant stirring hydrolysis, by ultrasonic process by dispersed for silica flour gained alumine hydroxide colloid, reduce pressure the solution obtained at 60 DEG C rotary evaporation, after by sample sintering processes at argon atmospher 600 DEG C, obtain the silica flour that alundum (Al2O3) is coated.
By silica flour: the mass ratio mixing of graphite=4:6, take water as solvent, sodium alginate is additive, and citric acid is dispersant, at room temperature stirs more than 5h, obtains the slurry that viscosity is 100mPas.Slurry is carried out spraying dry, and inlet temperature is 180 DEG C, and discharging opening temperature is 100 DEG C, after by Sample Spray dry at argon atmospher 600 DEG C sintering, obtain the Si-C composite material of porous, in porous carbon silicon composite, silicone content is 35%, carbon content is 65%, and tap density is 0.77g/cm 3.
Sample after sintering is mixed with petroleum asphalt, carboxymethyl cellulose, stir more than 10h, obtain the slurry that viscosity is 400mPas, slurry is carried out spraying dry, inlet temperature is 200 DEG C, discharging opening temperature is 90 DEG C, after by Sample Spray dry at argon atmospher 1000 DEG C sintering, obtain fine and close Si-C composite material, in composite material, silicone content is 19%, carbon content is 81%, and tap density is 0.88g/cm 3.
The assembling of the positive pole of battery, negative pole, electrolyte and battery is identical with embodiment 1, the composition of gained silicon carbide composite particles and list in table 1 in the test result of simulated battery.
Comparative example 1:
By silica flour: the mass ratio mixing of graphite=4:6, take water as solvent, PVP is additive, and sucrose is dispersant, at room temperature stirs more than 5h, obtains the slurry that viscosity is 100mPas.Slurry is carried out spraying dry, and inlet temperature is 180 DEG C, and discharging opening temperature is 100 DEG C, after by Sample Spray dry at 1000 DEG C of sintering, the Si-C composite material tap density obtained is 0.5g/cm 3.The assembling of the positive pole of battery, negative pole, electrolyte and battery is identical with embodiment 1, the composition of gained silicon carbide composite particles and list in table 1 in the test result of simulated battery.
Comparative example 2:
In silica flour: the ratio of glucose=10:1, take water as solvent, silica flour be dispersed in the aqueous solution containing glucose by ultrasonic process, by the solution rotary evaporation at 60 DEG C obtained, after by sample sintering processes at 600 DEG C, obtain the silica flour that carbon is coated.
By silica flour: the mass ratio mixing of graphite=6:4, take water as solvent, PVP is additive, and sucrose is dispersant, at room temperature stirs more than 5h, obtains the slurry that viscosity is 100mPas.Slurry is carried out spraying dry, and inlet temperature is 180 DEG C, and discharging opening temperature is 100 DEG C, after by Sample Spray dry at 1000 DEG C of sintering, the Si-C composite material tap density obtained is 0.53g/cm 3.
The assembling of the positive pole of battery, negative pole, electrolyte and battery is identical with embodiment 1, the composition of gained silicon carbide composite particles and list in table 1 in the test result of simulated battery.
Comparative example 3:
By silica flour: the mass ratio mixing of graphite=4:6, take water as solvent, PVP is additive, and sucrose is dispersant, at room temperature stirs more than 5h, obtains the slurry that viscosity is 100mPas.Slurry is carried out spraying dry, and inlet temperature is 180 DEG C, and discharging opening temperature is 100 DEG C, after by Sample Spray dry at 600 DEG C of sintering.
Sample after sintering is mixed with electrically conductive graphite, stir more than 10h, obtain the slurry that viscosity is 400mPas, slurry is carried out spraying dry, inlet temperature is 200 DEG C, and discharging opening temperature is 90 DEG C, after by Sample Spray dry at 1000 DEG C of sintering, obtain fine and close Si-C composite material, tap density is 0.75g/cm 3.
The assembling of the positive pole of battery, negative pole, electrolyte and battery is identical with embodiment 1, the composition of gained silicon carbide composite particles and list in table 1 in the test result of simulated battery.
The composition of table 1, Si-C composite material and under 100mA/g condition the test result of constant current charge-discharge

Claims (10)

1. a Silicon-carbon composite material for lithium ion battery, its tap density is 0.7-1.1g/cm 3, be made up of porous silicon carbon composite and the carbon be filled in its hole, in porous carbon silicon composite, silicone content is 10%-40%, and carbon content is 60%-90%.
2. a preparation method for Silicon-carbon composite material for lithium ion battery, concrete steps are as follows:
1) by sanded after silica flour ball mill grinding, by process after silica flour be dispersed in high molecular polymer or containing aluminium source solution or containing aluminium source colloid in and ultrasonic process, make silica flour suspend in the solution, prevent reunite;
2) by step 1) the solution decompression rotary evaporation of gained is except after desolventizing, sinter under non-oxidizing atmosphere, at the coated amorphous carbon of silicon face or alundum (Al2O3), the thickness of amorphous carbon or alundum (Al2O3) is 5-30nm, and content is 0.5%-10%;
3) by step 2) the coated good silica flour of gained and inorganic carbon source, hydroxy compounds dispersant, weight average molecular weight be that the polymeric additive of 50000-400000 carries out mechanical agitation, mixed, the weak solution that viscosity is suitable;
4) by step 3) weak solution of gained carries out spray drying treatment, obtain Si-C composite material, and sinter under non-oxidizing atmosphere, obtain the Si-C composite material of porous, in porous carbon silicon composite, silicone content is 20%-60%, carbon content is 40%-80%, and tap density is 0.6-0.9g/cm 3;
5) in step 4) in the hole of the Si-C composite material of gained, fill inorganic or organic carbon source, the concentrated solution that configuration viscosity is higher, carry out spray drying treatment, obtain fine and close spherical composite material, and sinter under non-oxidizing atmosphere, finally obtain Silicon-carbon composite material for lithium ion battery, in composite material, silicone content is 10%-40%, and carbon content is 60%-90%, and tap density is 0.7-1.1g/cm 3.
3. method according to claim 2, is characterized in that: 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, described high molecular polymer comprises but is not limited only at least one in following substances: phenolic resins, pitch, polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO), polyvinyl chloride (PVC), polyacrylonitrile (PAN), polyacetylene, glucose, sucrose, citric acid, sodium alginate, carboxymethyl cellulose, hydroxypropyl cellulose, polyethylene glycol, gelatin, starch, shitosan, alginic acid, described aluminium source comprises but is not limited only at least one of following substances: aluminium isopropoxide, three aluminium ethylates, aluminium secondary butylate, aluminum acetate, Tributyl aluminate.
4. according to the method one of claim 2-3 Suo Shu, it is characterized in that: wherein step 2) described in the condition of rotary evaporation be: temperature is 30 DEG C-70 DEG C, and rotary speed is 30-150 rev/min; The thickness of amorphous carbon or alundum (Al2O3) is preferably 10-20nm, and content is preferably 1%-5%.
5. according to the method one of claim 2-4 Suo Shu, it is characterized in that: step 2), 4) and 5) described in non-oxidizing atmosphere provided by following at least one gas: nitrogen, argon gas, helium, described sintering temperature is 500-1100 DEG C, programming rate is 1-15 DEG C/min, and sintering time is 1-15h.
6., according to the method one of claim 2-5 Suo Shu, it is characterized 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, Graphene, carbon nano-tube; Described additive is at least one in following substances: phenolic resins, pitch, polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO), polyvinyl chloride (PVC), polyacrylonitrile (PAN), polyacetylene, polyaniline, polythiophene; Described dispersant is at least one of following substances: glucose, sucrose, citric acid, sodium alginate, carboxymethyl cellulose, hydroxypropyl cellulose, polyethylene glycol, gelatin, starch, shitosan, alginic acid; Described viscosity is tested under temperature is 293K, and viscosity can be 1-10 4mPas, is preferably 100-500mPas.
7. according to the method one of claim 2-6 Suo Shu, it is characterized in that: step 4) and 5) described in spraying dry air inlet temperature can be 120-220 DEG C, discharging opening temperature is 60 DEG C-120 DEG C, and described spray drying device charging pump frequency can be 10-30Hz.
8. according to the method one of claim 2-7 Suo Shu, it is characterized in that: step 5) described in carbon source be selected from following at least one: Delanium, electrically conductive graphite, MCMB, Graphene, carbon nanometer, coal tar, petroleum asphalt, phenolic resins, sodium alginate, carboxymethyl cellulose, hydroxypropyl cellulose, gelatin, polyvinylpyrrolidone (PVP), preferably simultaneously containing gelatin and graphitized carbon, more preferably simultaneously containing gelatin and electrically conductive graphite, or simultaneously containing gelatin and Graphene; Described viscosity is tested under temperature is 293K, and viscosity can be 100-10 6mPas.
9. the Si-C composite material that in claim 2-8, arbitrary described method prepares.
10. Si-C composite material according to claim 9 is as the application of lithium ion battery negative material.
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