CN107799728A - A kind of hollow Si-C composite material for lithium ion battery and preparation method thereof - Google Patents

A kind of hollow Si-C composite material for lithium ion battery and preparation method thereof Download PDF

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Publication number
CN107799728A
CN107799728A CN201610750364.0A CN201610750364A CN107799728A CN 107799728 A CN107799728 A CN 107799728A CN 201610750364 A CN201610750364 A CN 201610750364A CN 107799728 A CN107799728 A CN 107799728A
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graphite
silicon
composite material
hollow
graphite flake
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李喆
王岑
张和宝
叶兰
丁烨
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Ann Price (Nanjing) Co., Ltd.
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Nanjing Peace Jim Press 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
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Abstract

The present invention relates to a kind of hollow Si-C composite material and preparation method thereof, Si-C composite material is spherical or elliposoidal second particle；Described second particle is hollow-core construction, and shell is combined by graphite flake, silicon materials and amorphous carbon, and silicon materials are evenly affixed between graphite flake surface and graphite flake, and all graphite flake and silicon materials surfaces are all covered with amorphous carbon protective layer；Form the mutual random orientation of graphite flake of second particle.The Si-C composite material of the present invention has high capacity, coulombic efficiency height, expansion small, good cycle electrochemical properties when being used as negative electrode of lithium ion battery.The lithium ion battery of the preparation of the Si-C composite material has volume energy density height, small, good cycle the characteristic of expansion.The preparation technology of the present invention is simple, and raw material sources are wide, cost is low, and industrial applications of the Si-C composite material in field of lithium can be achieved.

Description

A kind of hollow Si-C composite material for lithium ion battery and preparation method thereof
Technical field
The present invention relates to field of lithium ion battery, and in particular to a kind of hollow Si-C composite material and preparation method thereof.
Background technology
Due to the fast development and extensive use of various portable electric appts and electric automobile, for energy density it is high, The demand for the lithium ion battery having extended cycle life is increasingly urgent.The negative material of current commercialized lithium ion battery is mainly stone Ink, but because theoretical capacity is low (372mAh/g), limit the further raising of lithium ion battery energy density.Numerous new In lithium ion battery negative material, silicium cathode material has the high power capacity advantage (Li that other negative materials can not be equal to22Si5, reason By lithium storage content 4200mAh/g), it is more than 11 times of current business carbon negative pole material theoretical capacity.But silicon materials electric conductivity Difference, while serious bulk effect during embedding de- lithium be present in it, volume change is about 400%, can cause electrode material Efflorescence and electrode material separate with collector.Further, since the bulk effect in charge and discharge process, in electrolyte Silicium cathode material constantly forms fresh surface, therefore persistently consumes electrolyte to generate SEI films, reduces the circulation of electrode material Performance.The drawbacks described above of silica-base material seriously limits its commercialized application.
In order to solve the above-mentioned various problems of silicium cathode, the research both at home and abroad to silicium cathode material at present is concentrated mainly on following Several aspects：(1) particle diameter of silicon grain is reduced, such as nano silica fume is used, to slow down the bulk effect of silicon grain.But nanosizing Silicon grain causes circulating battery efficiency very low because specific surface area is big；And nano silica fume can be again in subsequent cyclic process Bulky grain is agglomerated into, produces new bulk effect.(2) silicon materials with special nanostructured, such as nano-tube are prepared, silicon is received Rice noodles, porous silicon etc., but such a method cost is higher, and yield is relatively low, is only suitable for laboratory research at present.(3) by silicon and nothing The carbon materials such as carbon, graphite that shape are compound, prepare Si-C composite material.Such a composite had both had the high power capacity of silicon materials, again Good cyclical stability and electronic conductivity with carbon material, turns into study hotspot in recent years.
Authorization Notice No. is that CN100422112C Chinese patent literature discloses a kind of carbon with spherical nucleocapsid Silicon composite and its preparation method and purposes.Described carbon-silicon composite material has spherical design, core shell structure, and its kernel part is The mixture of graphitized intermediate-phase carbon bead, hard carbon ball and one kind in spherical graphite, two kinds or three kinds materials；Its shell by Carbon and silicon crystal grain composition.Authorization Notice No. is that CN102651476B Chinese patent literature discloses a kind of lithium ion battery silicon-carbon Composite negative pole material and preparation method thereof.Described silicon-carbon composite cathode material of lithium ion battery is dispersed in stone by silicon nanoparticle Core shell structure is formed on black carrier.To disclose a kind of silicon substrate compound for the Chinese patent literature that application publication number is CN104425802A Material, its preparation method, using and its obtained lithium ion battery.The material structure kernel is solid graphite particle, outside it It is coated with the composite layer of silicon grain, conductive agent and amorphous carbon composition.The kernel of three kinds of materials described above is solid Graphite-structure, it can not accommodate and alleviate expansion and contraction of the silicon grain during insertion/deintercalate lithium ions in shell, cause The expansion rate of cathode pole piece and battery is high；And silicon materials are coated on the shell of graphite particle, insertion/removal lithium embedded repeatedly from Easily depart from subprocess with graphite kernel and lose activity, cause cycle performance to decline.
Authorization Notice No. is that CN103367727B Chinese patent literature discloses a kind of lithium ion battery silicon-carbon cathode material Material and preparation method thereof.Described silicon-carbon cathode material includes nano-silicon, graphite polymeric body and organic cracking carbon.The graphite Condensate is made up of granular graphite, the embedding table for being clipped between granular graphite space or being attached to granular graphite of nano-silicon Face, organic cracking carbon-coated nano silicon/graphite polymeric body.The granular graphite of the material selection only plays attachment nano-silicon Effect, graphite particle is not coated for nano-silicon in itself and protective effect, is unfavorable for coulombic efficiency and circulates conservation rate Improve；Granular graphite specific surface area is smaller, and the silicon nanoparticle useful load of attachment is limited, is unfavorable for carrying for energy density It is high；The composite is comparatively dense, accommodates expansion during silicon grain insertion lithium ion without enough inner spaces, easily causes The problems such as expansion rate is high.
Application publication number is that CN103682287A Chinese patent literature discloses a kind of lithium ion battery silicon substrate Compound Negative Pole material, preparation method and battery.Described silicon based anode material kernel is that nano silicon particles are embedded in the interior of hollow graphite The structure that layer space is formed, shell is non-graphitic carbon material；Kernel is organic by nano-silicon with the graphite after village hollowing processing Obtained in solvent after combination drying.But nano silicon particles are easily reunited in drying process process, it is difficult to by nano silicon particles In scattering for hollow graphite inner homogeneous, and the nano-silicon reunited can gradually melt in charge and discharge process and into more large scale Silicon grain, its circulate and expansion character obvious deterioration occurs.The Chinese patent text that application publication number is CN104577084A Offer and disclose a kind of nano silicon composite cathode material for lithium ion battery, preparation method and lithium ion battery.Described silicon substrate is born Nano silicon particles are deposited in the internal layer space of hollow graphite by pole material by chemical vapour deposition technique, outside graphite matrix Shell is amorphous carbon coating layer and nanometer conductive material clad.Chemical vapor deposition prepares nano silicon particles in hollow plumbago space The vacuum equipment of complexity is needed, equipment manufacturing cost is higher, low production efficiency, it is difficult to industrialized production.Above-described two kinds of materials Amorphous carbon protective layer exist only in graphite matrix shell, the silicon grain inside graphite matrix does not have carbon protective layer.The material It is prepared into after cathode pole piece when carrying out rolling processing, outermost amorphous carbon protective layer is easy to be crushed, and causes it internal exposed Silicon grain be directly exposed in electrolyte, cause the decline of material circulation performance.
Therefore, existing silicium cathode material electrochemical performance is poor, preparation technology is complicated, is difficult in lithium ion battery Practical application, be art technical barrier.
The content of the invention
The purpose of the present invention is in view of the shortcomings of the prior art, there is provided a kind of capacity for lithium ion battery is high, circulation Long lifespan Si-C composite material low with expanding and preparation method thereof.
To reach above-mentioned purpose, technical scheme provided by the invention is：
A kind of hollow Si-C composite material, Si-C composite material are spherical or elliposoidal second particle；Described is secondary Particle is hollow-core construction, and shell is combined by graphite flake, silicon materials and amorphous carbon, and silicon materials are evenly affixed to graphite flake table Between face and graphite flake, all graphite flake and silicon materials surfaces are all covered with amorphous carbon protective layer；Form second particle The mutual random orientation of graphite flake.
For described second particle size between 2-60 μm, second particle inner space equivalent diameter is equivalent with second particle External diameter ratio is 1:20–19:Between 20；Graphite leaf length is between 0.05-20 μm, and thickness is between 0.001-2 μm；Silicon materials Median particle diameter is between 0.01-5 μm；Between 0.001-2 μm of amorphous carbon protective layer thickness；In the Si-C composite material, stone Black content is 10-99wt%, and silicon materials content is 0.01-80wt%, agraphitic carbon content 1-50wt%.
The present invention provides the preparation method of above-mentioned hollow Si-C composite material, comprises the following steps：
(1) graphite material and silicon materials are subjected to wet grinding with dispersant, solvent respectively, obtain graphite slurry and silicon slurry Material, two kinds of slurries are mixed, obtain graphite/silicon mixed slurry；Or by graphite material and silicon materials simultaneously with dispersant, solvent Wet grinding is carried out, obtains graphite/silicon mixed slurry；
(2) graphite/silicon mixed slurry and the first carbon precursor solution are sufficiently mixed, obtain finely dispersed graphite/silicon/ First carbon precursor mixed slurry；
(3) processing is dried in above-mentioned mixed slurry, it is secondary becomes the spherical or elliposoidal with hollow-core construction Particle, high temperature carbonization is then carried out in non-oxidizing atmosphere；
(4) cladding processing is carried out with the second carbon precursor to the product of step (3), then carried out in non-oxidizing atmosphere High temperature carbonization；
(5) crushing and screening is carried out and except magnetic to the product of step (4), obtains Si-C composite material.
Wherein, in step (1)：
The graphite material is one in Delanium, native graphite, expanded graphite, electrically conductive graphite and MCMB Kind or a variety of combinations；
The silicon materials are crystalline silicon or non-crystalline silicon, can be nano silicon particles, silicon nanowires, nano-tube, silicon nanometer One or more combinations in rod, silicon nanorods, silicon micron particles, silicon micron bar, silicon micro wire；
The wet grinding uses appointing in high-speed stirred mill, ball mill, tube mill, type taper grinder, rod mill or sand mill Meaning is a kind of；
The wet grinding solvent for use is water and/or organic solvent；The organic solvent be methanol, ethanol, isopropanol, N-butanol, ethylene glycol, ether, acetone, 1-METHYLPYRROLIDONE, espeleton, tetrahydrofuran, benzene,toluene,xylene, N, N- One or more combinations in dimethylformamide, DMAC N,N' dimethyl acetamide or chloroform.
Dispersant used in the wet grinding is sodium tripolyphosphate, calgon, sodium pyrophosphate, cetyl front three One or more groups in base ammonium bromide, polyacrylic acid, polyvinylpyrrolidone, polyoxyethylene sorbitan monooleate Close.
Wherein, in step (2)：
The mixed method is using any one in high speed dispersor, high-speed stirred mill, ball mill or sand mill；
The first carbon precursor is glucose, sucrose, chitosan, starch, citric acid, gelatin, alginic acid, carboxymethyl fibre Tie up element, sodium carboxymethylcellulose, selected from coal tar pitch and petroleum asphalt, phenolic resin, tar, naphtalene oil, carbolineum, polyvinyl chloride, polyphenyl second Alkene, polyvinylidene fluoride, polyvinylpyrrolidone, polyethylene glycol oxide, polyvinyl alcohol, epoxy resin, polyacrylonitrile, poly- methyl-prop One or more combinations in e pioic acid methyl ester；
Dissolve the solvent of the first carbon precursor for water, methanol, ethanol, isopropanol, n-butanol, ethylene glycol, ether, acetone, 1-METHYLPYRROLIDONE, espeleton, tetrahydrofuran, benzene,toluene,xylene, N,N-dimethylformamide, N, N- dimethyl second One or more combinations in acid amides, chloroform.
Wherein, in step (3)：
The drying process mode uses spray dryer；
The temperature of the high temperature cabonization reaction is 500-1400 DEG C, and soaking time is 0.5-24 hours；
The non-oxidizing atmosphere is provided by following at least one gases：Nitrogen, argon gas, hydrogen or helium.
Wherein, in step (4)：
The method for coating of the second carbon precursor uses any in mechanical fusion machine, VC mixers or high speed dispersor It is a kind of.
The second carbon precursor is selected from coal tar pitch and petroleum asphalt, polyvinyl alcohol, epoxy resin, polyacrylonitrile, poly- methyl-prop One or more combinations in e pioic acid methyl ester；When carrying out cladding processing according to VC mixers and high speed dispersor, it can be selected The solvent that the second carbon precursor can be dissolved improves covered effect, and selected solvent is water, methanol, ethanol, isopropanol, n-butanol, second Glycol, ether, acetone, 1-METHYLPYRROLIDONE, tetrahydrofuran, benzene,toluene,xylene, N,N-dimethylformamide, N, N- bis- One or more combinations in methylacetamide or chloroform.
The temperature of described high temperature cabonization reaction is 500-1400 DEG C, and soaking time is 0.5-24 hours；
The non-oxidizing atmosphere is provided by following at least one gases：Nitrogen, argon gas, hydrogen or helium.
The present invention lithium ion battery negative material that also protection is prepared using above-mentioned Si-C composite material, with above-mentioned lithium Ion battery cathode material prepares negative electrode of lithium ion battery, and the lithium-ion electric prepared with above-mentioned negative electrode of lithium ion battery Pond.
Beneficial effect：
The Si-C composite material of the present invention has capacity height, coulombic efficiency high, swollen when being used as negative electrode of lithium ion battery Swollen small, good cycle electrochemical properties.The lithium ion battery prepared with the Si-C composite material has volume energy close Degree is high, small, good cycle the characteristic of expansion.The preparation method of the Si-C composite material is simple, cost is low, reproducible, Required equipment is simple, can large-scale industrial production.The raw material sources of the Si-C composite material are wide, cheap.The invention The large-scale production containing silicium cathode in field of lithium ion battery can really be realized.The present invention compared with prior art, has such as Lower advantage：
The Si-C composite material is spherical or elliposoidal secondary composite particles, and the second particle is hollow-core construction, Shell is combined by graphite flake, silicon grain and amorphous carbon.Lithium ion battery negative electrode is made in the Si-C composite material When, the hollow-core construction of the second particle can alleviate silicon grain caused volumetric expansion in embedding lithium, so as to ensure pole piece and Battery has relatively low expansion rate in thickness direction, indeformable in pole piece and cell thickness direction.Silicon grain is evenly affixed to stone Between ink sheet all surface and graphite flake, every graphite flake and every silicon grain surface are all covered with amorphous carbon protective layer. Described amorphous carbon protective layer connects as one the higher graphite flake of specific surface area and silicon grain cladding, effectively reduces compound The specific surface area of material, SEI formation is reduced, be advantageous to improve coulombic efficiency.Silicon grain is fixed on graphite flake by amorphous carbon Between or graphite flake surface at, effectively suppress and buffering silicon grain expansion；And prevent silicon grain in charge and discharge process by Gradually melt and into larger sized particle, prevent from melting and after large scale silicon grain cause bigger expansion and the mistake of part silicon materials Effect.Every graphite flake and every silicon grain are covered or connected by amorphous carbon protective layer, and amorphous carbon provides excellent Electronics and lithium ion transport passage, improve the high rate performance of composite.The row of the graphite flake of described secondary composite particles Cloth isotropism, when cathode pole piece and lithium ion battery is prepared into, pole piece and battery are effectively reduced in thickness direction On expansion.
Brief description of the drawings
Fig. 1 is the structural representation of the Si-C composite material of the present invention.
Fig. 2 is 500 times of stereoscan photographs of Si-C composite material prepared by embodiment 1.
Fig. 3 is 3000 times of stereoscan photographs of Si-C composite material prepared by embodiment 1.
Fig. 4 is the cycle performance figure of the full battery containing silicium cathode prepared by embodiment 1.
Fig. 5 is the cycle performance figure of the full battery containing silicium cathode prepared by comparative example 1.
Embodiment
With reference to specific embodiment, the invention will be further described.
As shown in figure 1, a kind of Si-C composite material provided by the invention is spherical or elliposoidal second particle, described two Secondary particle is hollow-core construction 1, and shell is combined by graphite flake 2, silicon materials 3 and amorphous carbon 4, and silicon materials 3 are evenly affixed to Between all surface of graphite flake 2 and graphite flake 2, all graphite flake 2 and silicon materials 3 surfaces are all covered with amorphous carbon 4 and protected Layer.The mutual random orientation of graphite flake of described second particle.
Embodiment 1
The native graphite and 4500g dimethyl acetamides that 500g median particle diameters are 22 μm are taken, with 0.4mm's in sand mill Zirconium oxide bead is sanded 3 hours, obtains the graphite flake slurry that median particle diameter is 6 μm, takes out stand-by.With electron microscope observation graphite Piece, graphite leaf length is between 0.1-15 μm, and thickness is between 0.01-0.5 μm.It is 2 μm to take 500g second particles median particle diameter, The nano silica fume and 4500g dimethyl acetamides that primary particle median particle diameter is 0.2 μm, use 0.4mm oxidation in sand mill Zirconium pearl is sanded 2 hours, obtains the nano silicon particles slurry that median particle diameter is 0.3 μm.By 150g asphalt with 1350g dimethyl Acetamide is mixed into suspension.Above-mentioned graphite flake slurry and asphalt suspension are poured into sand mill, with nano silicon particles Slurry is sufficiently mixed 30 minutes.The dimethyl acetamide slurry of well mixed graphite flake/silicon grain/asphalt is further It is 5% to be diluted to solid content with dimethyl acetamide, then carries out spray drying treatment, 160 DEG C of EAT, outlet temperature 100 DEG C, rotary-atomizing rotating speed of shower nozzle 400Hz, charging rate 100g/min.Spray drying is obtained in hollow sphere second particle Value particle diameter is about 15 μm, and the ratio between cavity diameter and particle external diameter are about 15:20.By the dry powder after spray drying in argon inert gas In atmosphere, heated 2 hours at 800 DEG C, asphalt is carbonized, obtain graphite flake/silicon grain of amorphous carbon bonding and cladding Composite particles.Take coal tar pitch 425g to add in 3000g dimethyl acetamides, add above-mentioned graphite flake/silicon grain/nothing while stirring Shaped carbon composite powder 530g, and dispersion impeller speed is risen into 1000rpm, stirring container temperature is risen into 150 under nitrogen atmosphere ℃.Continue after temperature reaches 150 DEG C scattered 30 minutes.200 DEG C are then raised temperature to, holding is slowly stirred to dimethyl acetamide It is evaporated completely.By the material of above-mentioned pitch-coating in argon inert atmosphere, 2 hours are incubated at 300 DEG C, is then raised temperature to 1050 DEG C carbonize 1 hour, crush sieving after naturally cooling to room temperature, obtain graphite flake/silicon grain of the secondary cladding of amorphous carbon Composite particles.
Fig. 2 show the electron scanning micrograph of final products, 500 times of multiplication factor.It can be seen that the product is spherical Or the second particle of elliposoidal.The electron scanning micrograph that multiplication factor is 3000 times is illustrated in figure 3, it is therein secondary Particle shell is damaged, it can clearly be seen that internal have larger hollow space, shell is answered by graphite flake, silicon grain and amorphous carbon Conjunction forms.
Take above-mentioned 30 parts of Si-C composite material, 67 parts of native graphite, 1.5 parts of thickener, 1.5 parts of bonding agent, in water-based body It is homogenized, is coated with, dries, rolls under system, obtains siliceous cathode pole piece.
Half-cell is assessed：Siliceous cathode pole piece obtained above is stacked and dripped successively with barrier film, lithium piece, stainless steel gasket 2016 formula lithium ion half-cells are made in sealing after adding 200 μ L electrolyte.It is small with Lan electricity electronics limited company of Wuhan City (micro-) current range equipment test capacity and discharging efficiency.Measure the charging and discharging capacity reversible first of the half-cell containing silicium cathode For 614mAh/g, first charge-discharge efficiency 88.1%, negative plate expansion rate is 46.3% after circulation in ten weeks.
Full Cell Evaluation：Siliceous cathode pole piece obtained above by cutting, vacuum bakeout, with the positive plate that matches and every After film is wound and put into correspondingly sized plastic-aluminum shell together, inject a certain amount of electrolyte and seal, can be obtained after chemical conversion To a complete siliceous full battery of negative electrode lithium ion.Should with the cell tester test of new Weir Electronics Co., Ltd. of Shenzhen Full capacity, average voltage and the capability retention data that under 0.5C charge-discharge velocity circulate 500 time of the battery under 0.2C.By This volume energy density for obtaining full battery is 745Wh/L, and the capability retention after 500 charge and discharge cycles is 84.9%, swollen Swollen rate 7.9%.Fig. 4 is the cycle performance figure of the full battery containing silicium cathode prepared by embodiment 1.
Embodiment 2
Take the native graphite and 5400g absolute ethyl alcohols that 600g median particle diameters are 22 μm, 18g polyvinylpyrrolidones, in sand It is sanded 4 hours with 0.4mm zirconium oxide bead in grinding machine, obtains the graphite flake slurry that median particle diameter is 5 μm, take out stand-by.Electricity consumption The micro- sem observation graphite flake of son, graphite leaf length is between 0.1-13 μm, and thickness is between 0.01-0.5 μm.Take 300g bis- times Grain median particle diameter is 2 μm, the nano silica fume and 2700g absolute ethyl alcohols that primary particle median particle diameter is 0.2 μm, 9g polyvinyl pyrroles Alkanone, it is sanded 2 hours with 0.4mm zirconium oxide bead in sand mill, obtains the nano silicon particles that median particle diameter is 0.2 μm and starch Material.250g glucose is dissolved in 2250g deionized waters and is made into D/W.By graphite flake slurry and D/W Sand mill is poured into, is sufficiently mixed 30 minutes with nano silicon particles slurry.By well mixed graphite flake/silicon grain/glucose It is 5% that absolute ethyl alcohol/water slurry is further diluted to solid content with deionized water, then carries out spray drying treatment, enters wind-warm syndrome 190 DEG C of degree, 125 DEG C of outlet temperature, rotary-atomizing rotating speed of shower nozzle 400Hz, charging rate 80g/min.Spray drying obtains hollow The median particle diameter of spherical second particle is about 18 μm, and the ratio between cavity diameter and particle external diameter are about 15:20.After spray drying Dry powder heats 2 hours at 600 DEG C in argon inert atmosphere, glucose is carbonized, and obtains what amorphous carbon was bonded and coated Graphite flake/silicon grain composite particles.Above-mentioned composite particles 465g is taken, took the asphalt 370g of 325 mesh sieves, with VC mixers After mechanical mixture 10 minutes, 740g dimethylformamides are added, leads to nitrogen and continues to stir while equipment is warming up to after 300 DEG C Mix 30 minutes, be then cooled to room temperature.By the material of above-mentioned pitch-coating in argon inert atmosphere, it is small that 2 are incubated at 400 DEG C When, then raise temperature to 900 DEG C and carbonize 2 hours, crush sieving after naturally cooling to room temperature, obtain the stone of the secondary cladding of amorphous carbon Ink sheet/silicon grain composite particles.
Take above-mentioned 20 parts of Si-C composite material, 77 parts of native graphite, 1.5 parts of thickener, 1.5 parts of bonding agent, in water-based body It is homogenized, is coated with, dries, rolls under system, obtains siliceous cathode pole piece.
Half-cell and full Cell Evaluation method measure the discharge and recharge reversible first of the half-cell containing silicium cathode with embodiment 1 Specific capacity is 467mAh/g, and first charge-discharge efficiency 92.9%, negative plate expansion rate is 31.6% after circulation in ten weeks.Measure full electricity The volume energy density in pond reaches 752Wh/L, and the capability retention after 500 charge and discharge cycles is 85.5%, and expansion rate is 6.3%.
Embodiment 3
Take the Delanium and 1360g isopropanols that 240g median particle diameters are 19 μm, 5g polyvinylpyrrolidones, in sand mill The middle zirconium oxide bead with 0.4mm is sanded 2 hours, obtains the graphite flake slurry that median particle diameter is 6 μm, takes out stand-by.Use electronic display Micro mirror observes graphite flake, and graphite leaf length is between 0.1-15 μm, and thickness is between 0.01-0.5 μm.The 900g median particle diameters are taken to be 5 μm of polycrystalline silica flour and 5100g isopropanols, 18g polyvinylpyrrolidones, 3 are sanded with 0.4mm zirconium oxide bead in sand mill Hour, obtain the nano silicon particles slurry that median particle diameter is 0.4 μm.150g glucose is dissolved in into 2850g deionized waters to be made into D/W.Graphite flake slurry and D/W are poured into sand mill, 30 are sufficiently mixed with nano silicon particles slurry Minute.The isopropanol/water slurry of well mixed graphite flake/silicon grain/glucose is further diluted to deionized water solid Content is 8%, then carries out spray drying treatment, 180 DEG C of EAT, 120 DEG C of outlet temperature, rotary-atomizing rotating speed of shower nozzle 350Hz, charging rate 100g/min.The median particle diameter that spray drying obtains hollow sphere second particle is about 25 μm, and cavity is straight The ratio between footpath and particle external diameter are about 10:20.By the dry powder after spray drying in argon inert atmosphere, it is small that 4 are heated at 550 DEG C When, glucose is carbonized, obtain graphite flake/silicon grain composite particles of amorphous carbon bonding and cladding.Coal tar pitch 1050g is taken to add Enter in 4200g dimethylformamides, add above-mentioned graphite flake/silicon grain/amorphous carbon composite powder 580g while stirring, will divide Dissipate disk speed and rise to 1000rpm, stirring container temperature is risen to 150 DEG C under nitrogen atmosphere.Continue after temperature reaches 150 DEG C It is scattered 30 minutes.200 DEG C are then raised temperature to, holding is slowly stirred to dimethylformamide to be evaporated completely.By above-mentioned pitch-coating Material in argon inert atmosphere, be incubated 2 hours at 300 DEG C, then raise temperature to 1000 DEG C carbonize 2 hours, natural cooling Sieving is crushed after to room temperature, obtains graphite flake/silicon grain composite particles of the secondary cladding of amorphous carbon.
Take above-mentioned 50 parts of Si-C composite material, 47 parts of Delanium, 1.5 parts of thickener, 1.5 parts of bonding agent, in water-based body It is homogenized, is coated with, dries, rolls under system, obtains siliceous cathode pole piece.
Half-cell and full Cell Evaluation method measure the discharge and recharge reversible first of the half-cell containing silicium cathode with embodiment 1 Specific capacity is 898mAh/g, and first charge-discharge efficiency 86.5%, negative plate expansion rate is 61.9% after circulation in ten weeks.Measure siliceous The volume energy density of the full battery of negative pole is 787Wh/L, and the capability retention after 500 charge and discharge cycles is 80.8%, swollen Swollen rate 9.9%.
Embodiment 4
Take the Delanium that 500g median particle diameters are 19 μm, the silica flour and 3000g deionizations that 30g median particle diameters are 10 μm Water, 26g Sodium Polyacrylates, it is sanded 1 hour with 1mm zirconium oxide bead in sand mill, obtains graphite flake and silicon grain mixing slurry Material, now graphite flake median particle diameter is about 15 μm, and silicon grain median particle diameter is about 3 μm.By 75g glucose be dissolved in 500g go from Sub- water is made into D/W, pours into sand mill, is sufficiently mixed 30 minutes with graphite flake and silicon grain mixed slurry.Will mixing It is 10% that the water slurry of uniform graphite flake/silicon grain/glucose is further diluted to solid content with deionized water, is then carried out Spray drying treatment, 180 DEG C of EAT, 110 DEG C of outlet temperature, rotary-atomizing rotating speed of shower nozzle 250Hz, charging rate 100g/ min.The median particle diameter that spray drying obtains hollow sphere second particle is about that the ratio between 50 μm of cavity diameters and particle external diameter are about 8:20.By the dry powder after spray drying in argon inert atmosphere, heated 2 hours at 700 DEG C, glucose is carbonized, obtain Amorphous carbon is bonded and graphite flake/silicon grain composite particles of cladding.Above-mentioned composite particles 260g is taken, takes polyvinyl alcohol 40g, is used VC mixers mechanical mixture adds 150g water, leads to nitrogen and continue to stir while equipment is warming up to after 150 DEG C after 10 minutes 30 minutes, continue thereafter with stirring and insulation is evaporated to moisture, powder is cooled to room temperature.The material that above-mentioned polyvinyl alcohol coats is existed In argon inert atmosphere, 2 hours are incubated at 250 DEG C, 700 DEG C is then raised temperature to and carbonizes 3 hours, is broken after naturally cooling to room temperature Broken sieving, obtain graphite flake/silicon grain composite particles of the secondary cladding of amorphous carbon.
Take above-mentioned 50 parts of Si-C composite material, 47 parts of native graphite, 1.5 parts of thickener, 1.5 parts of bonding agent, in water-based body It is homogenized, is coated with, dries, rolls under system, obtains siliceous cathode pole piece.
Half-cell and full Cell Evaluation method measure the discharge and recharge reversible first of the half-cell containing silicium cathode with embodiment 1 Specific capacity is 410mAh/g, and first charge-discharge efficiency 93.6%, negative plate expansion rate is 55.0% after circulation in ten weeks.Measure siliceous The volume energy density of the full battery of negative pole is 713Wh/L, and the capability retention after 500 charge and discharge cycles is 84.2%, swollen Swollen rate 8.8%.
Embodiment 5
Take MCMB graphite and the 5400g deionized waters that 600g median particle diameters are 22 μm, 6g calgons, It is sanded 1.5 hours with 0.8mm zirconium oxide bead in sand mill, obtains the graphite flake slurry that median particle diameter is 10 μm, take out stand-by. 100g silicon micro wire and 900g deionized waters are taken, 2g calgons, 0.5 is sanded with 0.8mm zirconium oxide bead in sand mill Hour, obtain the silicon grain slurry that median particle diameter is 2 μm.250g sucrose is dissolved in into 1000g deionized waters, and to be made into sucrose water-soluble Liquid.Graphite flake slurry and aqueous sucrose solution are poured into sand mill, are sufficiently mixed 30 minutes with graphite flake and silicon grain mixed slurry. It is 5% that the water slurry of well mixed graphite flake/silicon grain/sucrose further is diluted into solid content with deionized water, then Carry out spray drying treatment, 150 DEG C of EAT, 105 DEG C of outlet temperature, rotary-atomizing rotating speed of shower nozzle 350Hz, charging rate 100g/min.It is about 30 μm that spray drying, which obtains the median particle diameter of hollow sphere second particle, cavity diameter and particle external diameter it Than being about 17:20.By the dry powder after spray drying in argon inert atmosphere, heated 2 hours at 800 DEG C, sucrose is carbonized, Obtain graphite flake/silicon grain composite particles of amorphous carbon bonding and cladding.Above-mentioned composite particles 375g is taken, took 100 mesh sieves Coal tar pitch powder 300g, after VC mixers mechanical mixture 10 minutes, after leading to nitrogen while equipment is warming up into 200 DEG C Continue stirring 30 minutes, be then cooled to room temperature.By the material of above-mentioned pitch-coating in argon inert atmosphere, at 300 DEG C Insulation 2 hours, then raise temperature to 900 DEG C and carbonize 2 hours, crush sieving after naturally cooling to room temperature, it is secondary to obtain amorphous carbon The graphite flake of cladding/silicon grain composite particles.
Take above-mentioned 40 parts of Si-C composite material, 27 parts of native graphite, 30 parts of Delanium, 1.5 parts of thickener, bonding agent 1.5 parts, it is homogenized, is coated with, dries, rolls under water-based system, obtains siliceous cathode pole piece.
Half-cell and full Cell Evaluation method measure the discharge and recharge reversible first of the half-cell containing silicium cathode with embodiment 1 Specific capacity is 441mAh/g, and first charge-discharge efficiency 92.3%, negative plate expansion rate is 45.4% after circulation in ten weeks.Measure siliceous The volume energy density of the full battery of negative pole is 737Wh/L, and the capability retention after 500 charge and discharge cycles is 83.2%, swollen Swollen rate 8.3%.
Embodiment 6
The Delanium that 650g median particle diameters are 15 μm is taken, 50g second particles median particle diameter is 2 μm, primary particle intermediate value The nano silica fume and 6300g absolute ethyl alcohols that particle diameter is 0.2 μm, 7g cetyl trimethylammonium bromides, use 0.4mm in sand mill Zirconium oxide bead be sanded 2 hours, obtain graphite flake and silicon grain mixed slurry, now graphite flake median particle diameter is about 5 μm, silicon Grain median particle diameter is about 0.2 μm.250g phenolic resin is dissolved in 2250g absolute ethyl alcohols and is made into phenol resin solution.By graphite Piece slurry and phenol resin solution pour into sand mill, are sufficiently mixed 30 minutes with silicon grain slurry.By well mixed graphite flake/ It is 5% that silicon grain/phenolic resin slurry, which is further diluted to solid content with absolute ethyl alcohol, then carries out spray drying treatment, enters 130 DEG C of air temperature, 95 DEG C of outlet temperature, rotary-atomizing rotating speed of shower nozzle 500Hz, charging rate 70g/min.During spray drying obtains The median particle diameter of empty spherical second particle is about 12 μm, and the ratio between cavity diameter and particle external diameter are about 18:20.After being spray-dried Dry powder in argon inert atmosphere, heated 2 hours at 900 DEG C, make phenolic resin carbonized, obtain amorphous carbon bonding and bag The graphite flake covered/silicon grain composite particles.Above-mentioned composite particles 390g is taken, the asphalt 300g of 200 mesh sieves was taken, and was mixed with VC Conjunction machine mechanical mixture is after 10 minutes, adds 300g dimethylformamides, lead to nitrogen while by equipment be warming up to 300 DEG C it is follow-up Continuous stirring 30 minutes, is then cooled to room temperature.By the material of above-mentioned pitch-coating in argon inert atmosphere, protected at 400 DEG C Temperature 2 hours, then raise temperature to 1000 DEG C and carbonize 2 hours, crush sieving after naturally cooling to room temperature, obtain the secondary bag of amorphous carbon The graphite flake covered/silicon grain composite particles.
Take above-mentioned 50 parts of Si-C composite material, 27 parts of MCMB, 20 parts of Delanium, 1.5 parts of thickener, bonding 1.5 parts of agent, is homogenized under water-based system, is coated with, dries, rolls, and obtains siliceous cathode pole piece.
Half-cell and full Cell Evaluation method measure the discharge and recharge reversible first of the half-cell containing silicium cathode with embodiment 1 Specific capacity is 400mAh/g, and first charge-discharge efficiency 94.3%, negative plate expansion rate is 32.2% after circulation in ten weeks.Measure siliceous The volume energy density of the full battery of negative pole is 724Wh/L, and the capability retention after 500 charge and discharge cycles is 86.3%, swollen Swollen rate 6.1%
Embodiment 7
The Delanium and 5400g dimethylformamides that 600g median particle diameters are 19 μm are taken, with 0.4mm's in sand mill Zirconium oxide bead is sanded 3 hours, obtains the graphite flake slurry that median particle diameter is 6 μm, takes out stand-by.Take 200g silicon micron bar with 1800g dimethylformamides, it is sanded 2 hours with 0.8mm zirconium oxide bead in sand mill, it is 0.5 μm to obtain median particle diameter Silicon grain slurry.100g coal tar pitch is scattered in 900g dimethylformamides and is made into pitch suspension.By graphite flake slurry and drip Blue or green suspension pours into sand mill, is sufficiently mixed 30 minutes with silicon grain slurry.By well mixed graphite flake/silicon grain/pitch Slurry carries out spray drying treatment, 180 DEG C of EAT, 110 DEG C of outlet temperature, rotary-atomizing rotating speed of shower nozzle 400Hz, charging speed Spend 80g/min.It is about 16 μm that spray drying, which obtains the median particle diameter of hollow sphere second particle, cavity diameter and particle external diameter it Than being about 17:20.By the dry powder after spray drying in argon inert atmosphere, heated 2 hours at 900 DEG C, make asphalt carbonization, Obtain graphite flake/silicon grain composite particles of amorphous carbon bonding and cladding.Coal tar pitch 200g is taken to add 1800g dimethyl formyls In amine, above-mentioned graphite flake/silicon grain/amorphous carbon composite powder 400g is added while stirring, dispersion impeller speed is risen to 1000rpm, stirring container temperature is risen to 150 DEG C under nitrogen atmosphere.Continue after temperature reaches 150 DEG C scattered 30 minutes. 200 DEG C are then raised temperature to, holding is slowly stirred to dimethylformamide to be evaporated completely.By the material of above-mentioned pitch-coating in argon gas In inert atmosphere, 2 hours are incubated at 300 DEG C, 900 DEG C is then raised temperature to and carbonizes 2 hours, crushed after naturally cooling to room temperature Sieve, obtains graphite flake/silicon grain composite particles of the secondary cladding of amorphous carbon.
Take above-mentioned 20 parts of Si-C composite material, 47 parts of MCMB, 30 parts of native graphite, 1.5 parts of thickener, bonding 1.5 parts of agent, is homogenized under water-based system, is coated with, dries, rolls, and obtains siliceous cathode pole piece.
Half-cell and full Cell Evaluation method measure the discharge and recharge reversible first of the half-cell containing silicium cathode with embodiment 1 Specific capacity is 470mAh/g, and first charge-discharge efficiency 91.7%, negative plate expansion rate is 38.3% after circulation in ten weeks.Measure siliceous The volume energy density of the full battery of negative pole is 742Wh/L, and the capability retention after 500 charge and discharge cycles is 86.0%, swollen Swollen rate 6.4%
Embodiment 8
The Delanium that 50g median particle diameters are 18 μm is taken, 500g second particles median particle diameter is 2 μm, primary particle intermediate value The nano silica fume and 5850g absolute ethyl alcohols that particle diameter is 0.2 μm, 16g polyvinylpyrrolidones, with 0.4mm oxygen in sand mill Change zirconium pearl to be sanded 2 hours, obtain graphite flake and silicon grain mixed slurry, now graphite flake median particle diameter is about 8 μm, in silicon grain Value particle diameter is about 0.3 μm.150g glucose is dissolved in 1350g deionized waters and is made into D/W.Glucose is water-soluble Liquid pours into sand mill, is sufficiently mixed 30 minutes with graphite flake/silicon grain slurry.By well mixed graphite flake/silicon grain/grape It is 4% that syrup material, which is further diluted to solid content with deionized water, then carries out spray drying treatment, 200 DEG C of EAT, goes out 140 DEG C of temperature of mouth, rotary-atomizing rotating speed of shower nozzle 350Hz, charging rate 100g/min.Spray drying obtains secondary of hollow sphere The median particle diameter of grain is about 20 μm, and the ratio between cavity diameter and particle external diameter are about 19:20.By the dry powder after spray drying in argon gas In inert atmosphere, heated 3 hours at 600 DEG C, glucose is carbonized, obtain graphite flake/silicon of amorphous carbon bonding and cladding Particles dispersed particle.Take coal tar pitch 90g to add in 800g tetrahydrofurans, it is fixed to add above-mentioned graphite flake/silicon grain/nothing while stirring Shape carbon composite powder 280g, rises to 1000rpm by dispersion impeller speed, stirring container temperature is risen into 150 DEG C under nitrogen atmosphere. Continue after temperature reaches 150 DEG C scattered 30 minutes.200 DEG C are then raised temperature to, holding is slowly stirred to tetrahydrofuran steams completely It is dry.By the material of above-mentioned pitch-coating in argon inert atmosphere, 2 hours are incubated at 300 DEG C, then raises temperature to 900 DEG C of charcoals Change 2 hours, crush sieving after naturally cooling to room temperature, obtain graphite flake/silicon grain composite particles of the secondary cladding of amorphous carbon.
Take above-mentioned 5 parts of Si-C composite material, 50 parts of Delanium, 42 parts of Delanium, 1.5 parts of thickener, bonding agent 1.5 Part, it is homogenized, is coated with, dries, rolls under water-based system, obtains siliceous cathode pole piece.
Half-cell and full Cell Evaluation method measure the discharge and recharge reversible first of the half-cell containing silicium cathode with embodiment 1 Specific capacity is 452mAh/g, and first charge-discharge efficiency 92.3%, negative plate expansion rate is 37.3% after circulation in ten weeks.Measure siliceous The volume energy density of the full battery of negative pole is 744Wh/L, and the capability retention after 500 charge and discharge cycles is 86.4%, swollen Swollen rate 6.5%
Embodiment 9
600g median particle diameters are taken as 4 μm of electrically conductive graphite and 5400g absolute ethyl alcohols, 6g cetyl trimethylammonium bromides, It is sanded 4 hours with 0.4mm zirconium oxide bead in sand mill, obtains the graphite flake slurry that median particle diameter is 2 μm, take out stand-by. It is 2 μm to take 100g second particles median particle diameter, the nano silica fume and 900g absolute ethyl alcohols that primary particle median particle diameter is 0.2 μm, 2g cetyl trimethylammonium bromides, it is sanded 3 hours with 0.4mm zirconium oxide bead in sand mill, obtains median particle diameter as 0.1 μm nano silicon particles slurry.250g sucrose is dissolved in 4500g deionized waters.Graphite flake slurry and aqueous sucrose solution are poured into Sand mill, it is sufficiently mixed 30 minutes with nano silicon particles slurry.By the anhydrous second of well mixed graphite flake/silicon grain/sucrose It is 4% that alcohol/water slurry is further diluted to solid content with deionized water, then carries out spray drying treatment, EAT 120 DEG C, 90 DEG C of outlet temperature, rotary-atomizing rotating speed of shower nozzle 500Hz, charging rate 50g/min.Spray drying obtains hollow sphere two The median particle diameter of secondary particle is about 5 μm, and the ratio between cavity diameter and particle external diameter are about 5:20.By the dry powder after spray drying in argon In gas inert atmosphere, heated 3 hours at 600 DEG C, sucrose is carbonized, obtain graphite flake/silicon of amorphous carbon bonding and cladding Particles dispersed particle.Above-mentioned composite 375g, the asphalt 300g of 2000 mesh are taken, with VC mixers mixed at high speed 10 minutes Afterwards, mechanical fusion machine is added, at 1500 rpm high speed fusion treatment 30 minutes, obtains graphite flake/silicon of asphalt cladding Grain composite particles.By above-mentioned material in argon inert atmosphere, 2 hours are incubated at 300 DEG C, then raises temperature to 900 DEG C of charings 2 Hour, sieving is crushed after naturally cooling to room temperature, obtains graphite flake/silicon grain composite particles of the secondary cladding of amorphous carbon.
Take above-mentioned 40 parts of Si-C composite material, 57 parts of Delanium, 1.5 parts of thickener, 1.5 parts of bonding agent, in water-based body It is homogenized, is coated with, dries, rolls under system, obtains siliceous cathode pole piece.
Half-cell and full Cell Evaluation method measure the discharge and recharge reversible first of the half-cell containing silicium cathode with embodiment 1 Specific capacity is 438mAh/g, and first charge-discharge efficiency 89.8%, negative plate expansion rate is 31.3% after circulation in ten weeks.Measure siliceous The volume energy density of the full battery of negative pole is 719Wh/L, and the capability retention after 500 charge and discharge cycles is 82.6%, swollen Swollen rate 6.0%
Comparative example 1
Technical process similar embodiment 1, when difference is to be coated with the second carbon matrix precursor, by merging machine pair Si-C composite material and the second carbon matrix precursor asphalt are handled 60 minutes.The effect of the processing is to carry out asphalt cladding Meanwhile material has been subjected to densification processing, obtained material is the full particle that median particle diameter is 11 μm.
Half-cell and full Cell Evaluation method measure the discharge and recharge reversible first of the half-cell containing silicium cathode with embodiment 1 Specific capacity is 606mAh/g, and first charge-discharge efficiency 90.3%, negative plate expansion rate is 53.2% after circulation in ten weeks.Measure siliceous The volume energy density of the full battery of negative pole is 738Wh/L, and the capability retention after 500 charge and discharge cycles is 79.3%, swollen Swollen rate 9.3%.Fig. 5 is the cycle performance figure of the full battery containing silicium cathode prepared by comparative example 1.
Comparative example 2
Technical process similar embodiment 2, the difference with embodiment 2 are that comparative example 2 is not added with graphite.
Half-cell and full Cell Evaluation method measure the discharge and recharge reversible first of the half-cell containing silicium cathode with embodiment 1 Specific capacity is 480mAh/g, and first charge-discharge efficiency 90.1%, negative plate expansion rate is 46.5% after circulation in ten weeks.Measure siliceous The volume energy density of the full battery of negative pole is 715Wh/L, and the capability retention after 500 charge and discharge cycles is 78.8%, swollen Swollen rate 8.8%
Comparative example 3
Any Si-C composite material is not added, only takes 97 parts of Delanium, 1.5 parts of thickener, 1.5 parts of bonding agent, in water Property system under be homogenized, be coated with, dry, rolling, obtain the pole piece without silicium cathode.
Half-cell and full Cell Evaluation method measure the charge and discharge reversible first of the half-cell without silicium cathode with embodiment 1 Electric specific capacity is 363mAh/g, and first charge-discharge efficiency 94.5%, negative plate expansion rate is 26.1% after circulation in ten weeks.Measure not The volume energy density of full battery containing silicium cathode is 684Wh/L, and the capability retention after 500 charge and discharge cycles is 87.1%, expansion rate 5.2%.
Embodiment electrochemical data collects：
It is described above, only it is presently preferred embodiments of the present invention, any formal limitation not is made to the present invention, it is any ripe Professional and technical personnel is known, it is without departing from the scope of the present invention, real to more than according to the technical spirit of the present invention Apply any simple modification, equivalent substitution that example made and improve etc., still fall within technical solution of the present invention protection domain it It is interior.

Claims (10)

  1. A kind of 1. hollow Si-C composite material, it is characterised in that：Si-C composite material is spherical or elliposoidal second particle；Institute The second particle stated is hollow-core construction, and shell is combined by graphite flake, silicon materials and amorphous carbon, and silicon materials are evenly affixed to Between graphite flake surface and graphite flake, all graphite flake and silicon materials surfaces are all covered with amorphous carbon protective layer；Form two The mutual random orientation of graphite flake of secondary particle.
  2. 2. hollow Si-C composite material as claimed in claim 1, it is characterised in that：Described second particle size is at 2-60 μm Between, second particle inner space equivalent diameter is with the equivalent external diameter ratio of second particle 1:20–19:Between 20；Graphite leaf length Between 0.05-20 μm, thickness is between 0.001-2 μm；The median particle diameter of silicon materials is between 0.01-5 μm；Amorphous carbon is protected Between 0.001-2 μm of covering thickness；In the Si-C composite material, content of graphite 10-99wt%, silicon materials content is 0.01-80wt%, agraphitic carbon content 1-50wt%.
  3. 3. the preparation method of the hollow Si-C composite material described in claim 1, it is characterised in that：Comprise the following steps：
    (1) graphite material and silicon materials are subjected to wet grinding with dispersant, solvent respectively, obtain graphite slurry and silicon slurry, Two kinds of slurries are mixed, obtain graphite/silicon mixed slurry；Or graphite material and silicon materials are entered with dispersant, solvent simultaneously Row wet grinding, obtain graphite/silicon mixed slurry；
    (2) graphite/silicon mixed slurry and the first carbon precursor solution are sufficiently mixed, obtain finely dispersed graphite/silicon/the first Carbon precursor mixed slurry；
    (3) processing is dried in above-mentioned mixed slurry, becomes the spherical or elliposoidal second particle with hollow-core construction, High temperature carbonization is then carried out in non-oxidizing atmosphere；
    (4) cladding processing is carried out with the second carbon precursor to the product of step (3), high temperature is then carried out in non-oxidizing atmosphere Charing；
    (5) crushing and screening is carried out and except magnetic to the product of step (4), obtains Si-C composite material.
  4. 4. the preparation method of hollow Si-C composite material as claimed in claim 3, it is characterised in that：In step (1)：
    The graphite material be Delanium, native graphite, expanded graphite, electrically conductive graphite and MCMB in one kind or A variety of combinations；
    The silicon materials are crystalline silicon or amorphous silicon；
    The wet grinding uses any one in high-speed stirred mill, ball mill, tube mill, type taper grinder, rod mill or sand mill Kind；
    The wet grinding solvent for use is water and/or organic solvent；
    Dispersant used in the wet grinding is sodium tripolyphosphate, calgon, sodium pyrophosphate, cetyl trimethyl bromine Change one or more combinations in ammonium, polyacrylic acid, polyvinylpyrrolidone, polyoxyethylene sorbitan monooleate.
  5. 5. the preparation method of hollow Si-C composite material as claimed in claim 3, it is characterised in that：In step (2)：
    The mixed method is using any one in high speed dispersor, high-speed stirred mill, ball mill or sand mill；
    The first carbon precursor is glucose, sucrose, chitosan, starch, citric acid, gelatin, alginic acid, carboxymethyl cellulose Element, sodium carboxymethylcellulose, selected from coal tar pitch and petroleum asphalt, phenolic resin, tar, naphtalene oil, carbolineum, polyvinyl chloride, polystyrene, Polyvinylidene fluoride, polyvinylpyrrolidone, polyethylene glycol oxide, polyvinyl alcohol, epoxy resin, polyacrylonitrile, polymethyl One or more combinations in sour methyl esters；
    The solvent for dissolving the first carbon precursor is water, methanol, ethanol, isopropanol, n-butanol, ethylene glycol, ether, acetone, N- first Base pyrrolidones, espeleton, tetrahydrofuran, benzene,toluene,xylene, N,N-dimethylformamide, N, N- dimethylacetamides One or more combinations in amine, chloroform.
  6. 6. the preparation method of hollow Si-C composite material as claimed in claim 3, it is characterised in that：In step (3)：
    The drying process mode uses spray dryer；
    The temperature of the high temperature cabonization reaction is 500-1400 DEG C, and soaking time is 0.5-24 hours；
    The non-oxidizing atmosphere is provided by following at least one gases：Nitrogen, argon gas, hydrogen or helium.
  7. 7. the preparation method of hollow Si-C composite material as claimed in claim 3, it is characterised in that：In step (4)：
    The method for coating of the second carbon precursor uses any one in mechanical fusion machine, VC mixers or high speed dispersor Kind；
    The second carbon precursor is selected from coal tar pitch and petroleum asphalt, polyvinyl alcohol, epoxy resin, polyacrylonitrile, polymethylacrylic acid One or more combinations in methyl esters；
    The temperature of described high temperature cabonization reaction is 500-1400 DEG C, and soaking time is 0.5-24 hours；
    The non-oxidizing atmosphere is provided by following at least one gases：Nitrogen, argon gas, hydrogen or helium.
  8. A kind of 8. lithium ion battery negative material, it is characterised in that：Prepared using the Si-C composite material described in claim 1 Lithium ion battery negative material.
  9. A kind of 9. negative electrode of lithium ion battery, it is characterised in that：Prepared using lithium ion battery negative material described in claim 8 Negative electrode of lithium ion battery.
  10. A kind of 10. lithium ion battery, it is characterised in that：Using described in claim 9 negative electrode of lithium ion battery prepare lithium from Sub- battery.
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CN115763822A (en) * 2023-01-06 2023-03-07 碳佳(北京)科技有限公司 Silicon-carbon negative electrode composite material, application and lithium battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN102709566A (en) * 2012-06-12 2012-10-03 力芯（青岛）新能源材料有限公司 Spherical silicon carbon composite anode material of lithium ion battery and preparation method for spherical silicon carbon composite anode material
CN103682287A (en) * 2013-12-19 2014-03-26 深圳市贝特瑞新能源材料股份有限公司 Lithium ion battery silicon-based composite anode material, preparation method thereof and battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN102709566A (en) * 2012-06-12 2012-10-03 力芯（青岛）新能源材料有限公司 Spherical silicon carbon composite anode material of lithium ion battery and preparation method for spherical silicon carbon composite anode material
CN103682287A (en) * 2013-12-19 2014-03-26 深圳市贝特瑞新能源材料股份有限公司 Lithium ion battery silicon-based composite anode material, preparation method thereof and battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JIN LI ET AL.: "Scalable synthesis of a novel structured graphite/silicon/pyrolyzed-carbon composite as anode material for high-performance lithium-ion batteries", 《JOURNAL OF ALLOYS AND COMPOUNDS》 *
JONG-HYUK LEE ET AL.: "Spherical silicon/graphite/carbon composites as anode material for lithium-ion batteries", 《JOURNAL OF POWER SOURCES》 *

Cited By (26)

* Cited by examiner, † Cited by third party
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CN110429257B (en) * 2019-08-02 2022-04-29 河南电池研究院有限公司 Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof
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CN112652742B (en) * 2019-10-10 2022-07-12 中国石油化工股份有限公司 Silicon-carbon composite material and preparation method and application thereof
CN112652742A (en) * 2019-10-10 2021-04-13 中国石油化工股份有限公司 Silicon-carbon composite material and preparation method and application thereof
CN110707314A (en) * 2019-11-21 2020-01-17 陕西煤业化工技术研究院有限责任公司 Silicon-carbon composite lithium ion battery cathode material and preparation method thereof
CN110970611A (en) * 2019-12-23 2020-04-07 北京理工大学重庆创新中心 Hierarchical silicon-carbon composite material and preparation method and application thereof
CN113302765A (en) * 2020-03-25 2021-08-24 宁德新能源科技有限公司 Negative electrode material, electrochemical device, and electronic device
CN113851635A (en) * 2020-06-28 2021-12-28 宝山钢铁股份有限公司 Silicon-carbon composite negative electrode material for lithium ion battery, preparation method of silicon-carbon composite negative electrode material and battery
CN114195116A (en) * 2020-09-02 2022-03-18 北京清创硅谷科技有限公司 Carbon-silicon composite material and preparation method thereof
CN112038618A (en) * 2020-09-04 2020-12-04 中国有色桂林矿产地质研究院有限公司 Nano silicon powder polymeric sphere composite negative electrode material with hollow structure and preparation method and application thereof
CN112582589A (en) * 2020-11-20 2021-03-30 万华化学(四川)有限公司 Silicon-graphite composite negative electrode material, preparation method and lithium ion battery prepared from silicon-graphite composite negative electrode material
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