CN110085850A - A kind of preparation method of the carbon-coated Si-C composite material of multilayer - Google Patents

A kind of preparation method of the carbon-coated Si-C composite material of multilayer Download PDF

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CN110085850A
CN110085850A CN201910416407.5A CN201910416407A CN110085850A CN 110085850 A CN110085850 A CN 110085850A CN 201910416407 A CN201910416407 A CN 201910416407A CN 110085850 A CN110085850 A CN 110085850A
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carbon
mixture
coated
composite material
multilayer
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CN110085850B (en
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杨建锋
岳亮
卢源明
段传阳
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Inner Mongolia Snow New Material Technology Co ltd
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SHENZHEN SINUO INDUSTRIAL DEVELOPMENT CO LTD
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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
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

A kind of preparation method of the carbon-coated Si-C composite material of multilayer, comprising the following steps: weigh silicon powder and dispersing agent, add in solvent and carry out dispersion the first mixture of formation, the solid content of the first mixture is 10%~15%；First mixture is ground；Carbon source is dispersed in a solvent to form carbon source slurry, the solid content of carbon source slurry is 5%-8%, and carbon source slurry is added into the first mixture and is ground, and the carbon-coated nano-silicone wire/carbon composite mortar of first layer is made；Carbon source and graphite is added into the carbon-coated nano-silicone wire/carbon composite mortar of first layer, then forms the second mixture after adding stirring solvent dispersion, the solid content of the second mixture is 10%；Second mixture is contained in drying receptacle and is spray-dried to obtain sample, then sample is put into calcining vessel and is calcined under the protection of inert gas, is cooled down after the completion of calcining, the carbon-coated Si-C composite material of multilayer is made.

Description

A kind of preparation method of the carbon-coated Si-C composite material of multilayer
[technical field]
The present invention relates to lithium cell cathode material technical field more particularly to a kind of carbon-coated Si-C composite materials of multilayer Preparation method.
[background technique]
Graphite self-conductive is splendid, easily modified, therefore using graphite as the main material of lithium cell cathode material, still Graphite also has the not high disadvantage of capacity, limits the development of lithium battery.And the capacity of silicon materials is very high, although stone can be made up The disadvantages of not high disadvantage of black capacity, the but the phenomenon that volume of silicon materials is easily expanded or shunk, poorly conductive, these because Element is all unfavorable in the negative electrode material that silicon is applied to lithium battery, it is therefore desirable to by a series of modified measures, allow silicon materials It can be widely used in the negative electrode material of lithium battery, improve the performance of lithium battery, and then push the development of lithium electricity industry.For The above problem, current method of modifying be silica-base material is carried out cladding preparation can be used as lithium cell cathode material silicon-carbon it is compound Material can solve the not high defect of poorly conductive and capacity, but can not still inhibit the volume expansion of silica-base material well Problem.
In consideration of it, it is really necessary to provide a kind of preparation method of novel carbon-coated Si-C composite material of multilayer to overcome Drawbacks described above.
[summary of the invention]
The object of the present invention is to provide a kind of preparation method of the carbon-coated Si-C composite material of multilayer, the multilayer carbon of preparation The Si-C composite material of coated Si particle surface has multilayer carbon coating layer, based particles is avoided to expose carbon-coating, can be effective Ground inhibits the volume expansion of based particles, enhances the structural stability of the carbon-coated Si-C composite material of multilayer.
To achieve the goals above, the present invention provides a kind of preparation method of carbon-coated Si-C composite material of multilayer, packet Include following steps:
S1: weigh mass ratio be 1:0.01-0.1 silicon powder and dispersing agent, add in solvent with the speed of 250r/min into Row dispersion 1h forms the first mixture, and the solid content of the first mixture is 10%~15%；By the first mixture with 1200~ The revolving speed of 1450r/min grinds 4h；
S2: dispersing 1h for insoluble carbon source in a solvent and form carbon source slurry, and the solid content of carbon source slurry is 5%-8%, Then carbon source slurry is added and grinds 6h into the first mixture, the carbon-coated nano-silicone wire/carbon composite mortar of first layer is made；
S3: the soluble carbon source for accounting for silicon powder mass fraction 30%~50% is added and accounts for silicon powder mass fraction 30%~50% Graphite second layer carbon coating is carried out into the carbon-coated nano-silicone wire/carbon composite mortar of first layer, then add stirring solvent dispersion 1h After form the second mixture, the solid content of the second mixture is 10%；
S4: the second mixture is contained in drying receptacle and is spray-dried to obtain sample, then sample is put into and is forged In baking vessel and 300~500 DEG C, which are warming up to, with the heating rate of 3~5 DEG C/min under the protection of inert gas carries out calcining 3h, 700~1200 DEG C of 3~5h of calcining are warming up to the heating rate of 3~5 DEG C/min again, are cooled down after the completion of calcining, are made more The carbon-coated Si-C composite material of layer.
In a preferred embodiment, the solvent is ethyl alcohol.
In a preferred embodiment, the inlet temperature of drying receptacle is 90~150 DEG C, the outlet temperature of drying receptacle It is 70~90 DEG C.
In a preferred embodiment, the insoluble carbon source is pitch；The soluble carbon source includes grape One of sugar, citric acid, polyvinylpyrrolidone, carboxymethyl cellulose and polyethylene glycol or several mixtures.
In a preferred embodiment, the graphite be one of artificial graphite, natural graphite or expanded graphite or Several mixture of person.
In a preferred embodiment, the inert gas include one of helium, argon gas and nitrogen or Several mixtures.
Compared with prior art, beneficial effect is: the multilayer carbon coating silicon particle surface of preparation of the embodiment of the present invention Si-C composite material has multilayer carbon coating layer, avoids based particles from exposing carbon-coating, can effectively inhibit based particles Volume expansion enhances structural stability, for the first time coulombic efficiency and the electric conductivity of the carbon-coated Si-C composite material of multilayer.Separately Outside, using the Si-C composite material on the multilayer carbon coating silicon particle surface of preparation of the embodiment of the present invention, the battery further prepared Charge-discharge performance is stable, coulombic efficiency is high for the first time.
[Detailed description of the invention]
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the schematic diagram of the granule-morphology of the carbon-coated Si-C composite material of multilayer of preparation of the embodiment of the present invention；
Fig. 2 is the carbon-coated Si-C composite material of multilayer filling under 0.1C multiplying power for the first time prepared by the embodiment of the present invention 1 Discharge curve；
Fig. 3 is the carbon-coated Si-C composite material of multilayer 30 charge and discharges under 0.1C multiplying power prepared by the embodiment of the present invention 1 Electric cyclic curve figure；
Fig. 4 is the carbon-coated Si-C composite material of multilayer 30 charge and discharges under 0.1C multiplying power prepared by the embodiment of the present invention 1 Electrical efficiency curve graph.
[specific embodiment]
It is clear in order to be more clear the purpose of the present invention, technical solution and advantageous effects, below in conjunction with attached drawing and Specific embodiment, the present invention will be described in further detail.It should be understood that specific implementation described in this specification Mode is not intended to limit the present invention just for the sake of explaining the present invention.
The present invention provides a kind of preparation method of carbon-coated Si-C composite material of multilayer, comprising the following steps:
S1: weigh mass ratio be 1:0.01-0.1 silicon powder and dispersing agent, add in solvent with the speed of 250r/min into Row dispersion 1h forms the first mixture, and the solid content of the first mixture is 10%~15%；First mixture is contained in sand milling In machine, and opens sand mill and 4h is ground with the revolving speed of 1200~1450r/min；
S2: dispersing 1h for insoluble carbon source in a solvent and form carbon source slurry, and the solid content of carbon source slurry is 5%-8%, Then 6h will be ground in the first mixture that carbon source slurry is added into sand mill, it is multiple that the carbon-coated nano-silicone wire/carbon of first layer is made Close slurry；
S3: the soluble carbon source for accounting for silicon powder mass fraction 30%~50% is added and accounts for silicon powder mass fraction 30%~50% Graphite into the carbon-coated nano-silicone wire/carbon composite mortar of first layer, with compound to the carbon-coated nano-silicone wire/carbon of first layer obtained Slurry carries out second layer carbon coating, then forms the second mixture, the solid content of the second mixture after adding stirring solvent dispersion 1h It is 10%；
S4: the second mixture is contained in drying receptacle and is spray-dried to obtain sample, then sample is put into and is forged In baking vessel and 300~500 DEG C, which are warming up to, with the heating rate of 3~5 DEG C/min under the protection of inert gas carries out calcining 3h, 700~1200 DEG C of 3~5h of calcining are warming up to the heating rate of 3~5 DEG C/min again, are cooled down after the completion of calcining, are made more The carbon-coated Si-C composite material of layer.
Specifically, the inlet temperature of drying receptacle is 90~150 DEG C, the outlet temperature of drying receptacle is 70~90 DEG C.
Specifically, the solvent is ethyl alcohol.
Specifically, the insoluble carbon source is pitch；The soluble carbon source includes glucose, citric acid, poly- second Alkene is than one of pyrrolidone, carboxymethyl cellulose, polyethylene glycol or several mixtures.
Specifically, the graphite is one of artificial graphite, natural graphite or expanded graphite or several mixtures.
Specifically, the inert gas includes one of helium, argon gas, nitrogen or several mixtures.
Embodiment:
Embodiment 1:
It weighs 500g silicon powder and 25g polyvinylpyrrolidone adds in ethyl alcohol and disperses 1h the first mixture of formation, first is mixed The solid content for closing object is 10%, the first mixture is contained in sand mill, and grind 4h with the revolving speed of 1200r/min.
It weighs 150g pitch and adds to formation carbon source slurry in ethyl alcohol, the solid content of carbon source slurry is 8%, then starches carbon source Material, which is added, to be continued to grind 6h into the first mixture, obtains the carbon-coated nano-silicone wire/carbon composite mortar of first layer.
250g polyvinylpyrrolidone is added into the carbon-coated nano-silicone wire/carbon composite mortar of first layer, to obtained the One layer of carbon-coated nano-silicone wire/carbon composite mortar carries out second layer carbon coating, then adds again after 2250g ethyl alcohol is dispersed with stirring 2h The second mixture is formed, the solid content of the second mixture is 10%.
Second mixture is contained in drying receptacle and is spray-dried to obtain sample, and the inlet temperature of drying receptacle It is 110 DEG C, outlet temperature is 70 DEG C；Then sample is put into calcining vessel and under the protection of nitrogen with 3 DEG C/min rate It is warming up to 400 DEG C and carries out calcining 3h, then 850 DEG C of calcining 3h are warming up to 5 DEG C/min rate, cooled down, obtained after the completion of calcining To the carbon-coated Si-C composite material of multilayer.
The carbon-coated Si-C composite material of multilayer obtained is pressed with conductive carbon black, sodium carboxymethylcellulose, butadiene-styrene rubber The ratio of mass ratio 91:5:1.6:2.4 mixes, and deionized water is added and is stirred as solvent；After mixing evenly using coating Equipment is spread evenly across in copper foil current collector, is toasted for 24 hours in 90 DEG C of vacuum ovens, is then suppressed uniformly using twin rollers, The round pole piece that diameter is 14mm finally is made with sheet-punching machine.Using the circle pole piece, diaphragm, (diaphragm is poly- for Celgard 2300 Propylene film), electrolyte and battery case, be prepared into button cell, electrochemical property test carried out to the button cell.
By button cell to carry out charge and discharge cycles test under 0.1C multiplying power, voltage range is 0~2V, recycles 30 times, surveys The specific capacity of circulating and reversible for the first time of button cell is 456.2mAh/g out, and coulombic efficiency is 89.4% for the first time, is held after 30 circulations Measuring conservation rate is 92.54%.
Embodiment 2
It weighs 500g silicon powder and 25g polyvinylpyrrolidone adds in ethyl alcohol and disperses 1h the first mixture of formation, first is mixed The solid content for closing object is 10%, the first mixture is contained in sand mill, and grind 4h with the revolving speed of 1200r/min.
It weighs 150g pitch and adds to formation carbon source slurry in ethyl alcohol, the solid content of carbon source slurry is 8%, then starches carbon source Material, which is added, to be continued to grind 6h into the first mixture, obtains the carbon-coated nano-silicone wire/carbon composite mortar of first layer.
250g artificial graphite is added into the carbon-coated nano-silicone wire/carbon composite mortar of first layer, to first layer carbon obtained The nano-silicone wire/carbon composite mortar of cladding carries out second layer carbon coating, then adds 2250g ethyl alcohol again and be dispersed with stirring after 2h forming the Two mixtures, the solid content of the second mixture are 10%.
Second mixture is contained in drying receptacle and is spray-dried to obtain sample, and the inlet temperature of drying receptacle It is 110 DEG C, outlet temperature is 70 DEG C；Then sample is put into calcining vessel and under the protection of nitrogen with 3 DEG C/min rate It is warming up to 400 DEG C and carries out calcining 3h, then 850 DEG C of calcining 5h are warming up to 5 DEG C/min rate, cooled down, obtained after the completion of calcining To the carbon-coated Si-C composite material of multilayer.
The carbon-coated Si-C composite material of multilayer obtained is pressed with conductive carbon black, sodium carboxymethylcellulose, butadiene-styrene rubber The ratio of mass ratio 91:5:1.6:2.4 mixes, and deionized water is added and is stirred as solvent；After mixing evenly using coating Equipment is spread evenly across in copper foil current collector, is toasted for 24 hours in 90 DEG C of vacuum ovens, is then suppressed uniformly using twin rollers, The round pole piece that diameter is 14mm finally is made with sheet-punching machine.Using the circle pole piece, diaphragm, (diaphragm is poly- for Celgard 2300 Propylene film), electrolyte and battery case, be prepared into button cell, button type battery carries out electrochemical property test.
By button cell to carry out charge and discharge cycles test under 0.1C multiplying power, voltage range is 0~2V, recycles 30 times, surveys The specific capacity of circulating and reversible for the first time of button cell is 476.5mAh/g out, and coulombic efficiency is 84.3% for the first time, after 30 circulations Capacity retention ratio is 83.2%.
Embodiment 3
It weighs 500g silicon powder and the poly- diethanol of 25g adds in ethyl alcohol and disperses 1h the first mixture of formation, the first mixture Solid content is 10%, and the first mixture is contained in sand mill, and grinds 4h with the revolving speed of 1200r/min.
It weighs 150g pitch and adds to formation carbon source slurry in ethyl alcohol, the solid content of carbon source slurry is 8%, then starches carbon source Material, which is added, to be continued to grind 6h into the first mixture, obtains the carbon-coated nano-silicone wire/carbon composite mortar of first layer.
250g polyvinylpyrrolidone and 250g artificial graphite is added to the carbon-coated nano-silicone wire/carbon composite mortar of first layer In, to carry out second layer carbon coating to the carbon-coated nano-silicone wire/carbon composite mortar of first layer obtained, 4500g second is then added again Alcohol forms the second mixture after being dispersed with stirring 2h, and the solid content of the second mixture is 10%.
Second mixture is contained in drying receptacle and is spray-dried to obtain sample, and the inlet temperature of drying receptacle It is 110 DEG C, outlet temperature is 70 DEG C；Then sample is put into calcining vessel and under the protection of nitrogen with 3 DEG C/min rate It is warming up to 400 DEG C and carries out calcining 3h, then 850 DEG C of calcining 5h are warming up to 5 DEG C/min rate, cooled down, obtained after the completion of calcining To the carbon-coated Si-C composite material of multilayer.
The carbon-coated Si-C composite material of multilayer obtained is pressed with conductive carbon black, sodium carboxymethylcellulose, butadiene-styrene rubber The ratio of mass ratio 91:5:1.6:2.4 mixes, and deionized water is added and is stirred as solvent；After mixing evenly using coating Equipment is spread evenly across in copper foil current collector, is toasted for 24 hours in 90 DEG C of vacuum ovens, is then suppressed uniformly using twin rollers, The round pole piece that diameter is 14mm finally is made with sheet-punching machine.Using the circle pole piece, diaphragm, (diaphragm is poly- for Celgard 2300 Propylene film), electrolyte and battery case, be prepared into button cell, button type battery carries out electrochemical property test.
By button cell to carry out charge and discharge cycles test under 0.1C multiplying power, voltage range is 0~2V, recycles 30 times, surveys The specific capacity of circulating and reversible for the first time of button cell is 437.0mAh/g out, and coulombic efficiency is 87.49% for the first time, is recycled through 30 times Capacity retention ratio is 98.0% afterwards.
Embodiment 4
It weighs 500g silicon powder and the poly- diethanol of 25g adds in ethyl alcohol and disperses 1h the first mixture of formation, the first mixture Solid content is 10%, and the first mixture is contained in sand mill, and grinds 4h with the revolving speed of 1200r/min.
It weighs 150g pitch and adds to formation carbon source slurry in ethyl alcohol, the solid content of carbon source slurry is 8%, then starches carbon source Material, which is added, to be continued to grind 6h into the first mixture, obtains the carbon-coated nano-silicone wire/carbon composite mortar of first layer.
250g citric acid is added into the carbon-coated nano-silicone wire/carbon composite mortar of first layer, to first layer carbon packet obtained The nano-silicone wire/carbon composite mortar covered carries out second layer carbon coating, is then added after 2250g ethyl alcohol is dispersed with stirring 2h again and forms second Mixture, the solid content of the second mixture are 10%.
Second mixture is contained in drying receptacle and is spray-dried to obtain sample, and the inlet temperature of drying receptacle It is 110 DEG C, outlet temperature is 70 DEG C；Then sample is put into calcining vessel and under the protection of nitrogen with 3 DEG C/min rate It is warming up to 400 DEG C and carries out calcining 3h, then 950 DEG C of calcining 5h are warming up to 5 DEG C/min rate, cooled down, obtained after the completion of calcining To the carbon-coated Si-C composite material of multilayer.
The carbon-coated Si-C composite material of multilayer obtained is pressed with conductive carbon black, sodium carboxymethylcellulose, butadiene-styrene rubber The ratio of mass ratio 91:5:1.6:2.4 mixes, and deionized water is added and is stirred as solvent；After mixing evenly using coating Equipment is spread evenly across in copper foil current collector, is toasted for 24 hours in 90 DEG C of vacuum ovens, is then suppressed uniformly using twin rollers, The round pole piece that diameter is 14mm finally is made with sheet-punching machine.Using the circle pole piece, diaphragm, (diaphragm is poly- for Celgard 2300 Propylene film), electrolyte and battery case, be prepared into button cell, button type battery carries out electrochemical property test.
By button cell to carry out charge and discharge cycles test under 0.1C multiplying power, voltage range is 0~2V, recycles 30 times, surveys The specific capacity of circulating and reversible for the first time of the sample of button cell is 434.5mAh/g out, and coulombic efficiency is 88.2% for the first time, through 30 times Capacity retention ratio is 89.6% after circulation.
Fig. 1 is the schematic diagram of the granule-morphology of the carbon-coated Si-C composite material of multilayer of preparation of the embodiment of the present invention；Fig. 2 First charge-discharge curve graph of the carbon-coated Si-C composite material of multilayer under 0.1C multiplying power prepared for the embodiment of the present invention 1； Fig. 3 be the embodiment of the present invention 1 prepare the carbon-coated Si-C composite material of multilayer under 0.1C multiplying power 30 charge and discharge cycles songs Line chart；Fig. 4 be the embodiment of the present invention 1 prepare the carbon-coated Si-C composite material of multilayer under 0.1C multiplying power 30 charge and discharge imitate Rate curve graph.
By Fig. 1 to Fig. 4 it is found that the based particles surface of the carbon-coated Si-C composite material of multilayer is coated with multilayer carbon-coating, Firmly based particles are coated in multilayer carbon coating layer, based particles is avoided to expose carbon-coating, silicon can be effectively inhibited The volume expansion of base particle enhances the structural stability of the carbon-coated Si-C composite material of multilayer, and then is promoted and apply multilayer carbon The stability of the charge and discharge cycles of the battery of the preparation of silicon carbon composite materials of cladding.In addition, also improving multilayer carbon coating silicon substrate The coulombic efficiency for the first time and electric conductivity of the Si-C composite material of particle surface.
In summary: the Si-C composite material on the multilayer carbon coating silicon particle surface of preparation of the embodiment of the present invention has more Layer carbon coating layer, avoids based particles from exposing carbon-coating, can effectively inhibit the volume expansion of based particles, enhances multilayer carbon The structural stability of the Si-C composite material of cladding, for the first time coulombic efficiency and electric conductivity.In addition, using embodiment of the present invention system The Si-C composite material on standby multilayer carbon coating silicon particle surface, the battery charging and discharging stable cycle performance further prepared, head Secondary coulombic efficiency is high.
The present invention is not only in the description and the implementation described, therefore for the personnel of familiar field Other advantage and modification is easily implemented, therefore in the essence without departing substantially from universal defined by claim and equivalency range In the case where mind and range, the present invention is not limited to specific details, representative equipment and diagrams shown and described herein Example.

Claims (6)

1. a kind of preparation method of the carbon-coated Si-C composite material of multilayer, which comprises the following steps:
S1: the silicon powder and dispersing agent that mass ratio is 1:0.01-0.1 are weighed, adds in solvent and is divided with the speed of 250r/min It dissipates 1h and forms the first mixture, the solid content of the first mixture is 10%~15%；By the first mixture with 1200~1450r/ The revolving speed of min grinds 4h；
S2: insoluble carbon source is dispersed into 1h in a solvent and forms carbon source slurry, the solid content of carbon source slurry is 5%-8%, then Carbon source slurry is added and grinds 6h into the first mixture, the carbon-coated nano-silicone wire/carbon composite mortar of first layer is made；
S3: addition accounts for the soluble carbon source of silicon powder mass fraction 30%~50% and accounts for the stone of silicon powder mass fraction 30%~50% Ink carries out second layer carbon coating into the carbon-coated nano-silicone wire/carbon composite mortar of first layer, then adds shape after stirring solvent dispersion 1h At the second mixture, the solid content of the second mixture is 10%；
S4: the second mixture being contained in drying receptacle and is spray-dried to obtain sample, and sample is then put into calcining and is held 300~500 DEG C, which are warming up to, with the heating rate of 3~5 DEG C/min in device and under the protection of inert gas carries out calcining 3h, then with The heating rate of 3~5 DEG C/min is warming up to 700~1200 DEG C of 3~5h of calcining, is cooled down after the completion of calcining, and multilayer carbon is made The Si-C composite material of cladding.
2. the preparation method of the carbon-coated Si-C composite material of multilayer according to claim 1, which is characterized in that described molten Agent is ethyl alcohol.
3. the preparation method of the carbon-coated Si-C composite material of multilayer according to claim 1, which is characterized in that dry to hold The inlet temperature of device is 90~150 DEG C, and the outlet temperature of drying receptacle is 70~90 DEG C.
4. the preparation method of the carbon-coated Si-C composite material of multilayer according to claim 1, which is characterized in that described Insoluble carbon source is pitch；The soluble carbon source includes glucose, citric acid, polyvinylpyrrolidone, carboxymethyl cellulose One of element and polyethylene glycol or several mixtures.
5. the preparation method of the carbon-coated Si-C composite material of multilayer according to claim 1, which is characterized in that the stone Ink is one of artificial graphite, natural graphite or expanded graphite or several mixtures.
6. the preparation method of the carbon-coated Si-C composite material of multilayer according to claim 1, which is characterized in that described Inert gas includes one of helium, argon gas and nitrogen or several mixtures.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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