CN109004203A - A kind of silicon-carbon composite cathode material and preparation method thereof - Google Patents

A kind of silicon-carbon composite cathode material and preparation method thereof Download PDF

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CN109004203A
CN109004203A CN201810873056.6A CN201810873056A CN109004203A CN 109004203 A CN109004203 A CN 109004203A CN 201810873056 A CN201810873056 A CN 201810873056A CN 109004203 A CN109004203 A CN 109004203A
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silicon
carbon
composite cathode
cathode material
preparation
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CN109004203B (en
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万水田
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INNER MONGOLIA SANXIN INDUSTRIAL 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/36—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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a kind of silicon-carbon composite cathode materials and preparation method thereof, belong to lithium ion battery material technical field.The preparation method of silicon-carbon composite cathode material of the invention includes the following steps: for silane coupling agent, porous carbon materials to be spray-dried after mixing in organic solvent, modified porous carbon material is made；By modified porous carbon material under silane gas existence condition, 1000-1200 DEG C of heat preservation 1-6h；Then it is cooled to 600-800 DEG C, in the presence of gas dopant, 1-6h is kept the temperature, silicon carbon material is made；The gas dopant is NH3、N2O、NO、N2O4One or more of combination；By silicon carbon material under carbon-source gas existence condition, 700-900 DEG C of heat preservation 1-12h to get.The silicon-carbon composite cathode material that the present invention prepares has the characteristics that specific capacity is high, electric conductivity is strong, good cycle, can be applied to the lithium ion battery of high-energy-density density.

Description

A kind of silicon-carbon composite cathode material and preparation method thereof
Technical field
The present invention relates to a kind of silicon-carbon composite cathode materials and preparation method thereof, belong to lithium ion battery material technology neck Domain.
Background technique
According to national new energy vehicle development plan, new energy vehicle industry proposes the energy density of lithium ion battery higher Requirement.For lithium ion battery, negative electrode material is its important component, and influences the important of battery energy density Factor.The negative electrode material of existing market is mainly based on graphite type material, but the relatively low limitation of the gram volume of graphite type material The raising of lithium ion battery energy density.And silicium cathode material it is high, resourceful with its gram volume the advantages that and studied The attention of person, and it is applied to the fields such as high-energy-density density lithium ion battery.But silicium cathode volume dilatation is high, electric conductivity Difference, which becomes, restricts its widely applied factor.
The expansion measure main method for reducing silicon materials at present has: 1) in nano silicon material coated with carbon material, improving Its electric conductivity and its volume dilatation of reduction；2) poroid template is prepared, and silicon materials are embedded in hole, reduces its expansion Rate；Or porous silica material is prepared, reduce its expansion；3) material that expansion rate is low, electric conductivity is strong, such as graphene, carbon are coated The materials such as nanotube, to reduce the expansion rate of silicon materials and improve its electric conductivity.But although above scheme is to silicon-carbon cathode material The expansion of material has some improvement, but effect is unobvious, for example cladding is uneven and coating thickness is thicker, nano-silicon is easy Itself reunite and cause its homogeneity is poor, clad electric conductivity of matter is poor etc., causes the specific capacity of Si-C composite material cannot be complete It brings into play entirely, while cycle performance and high rate performance are poor, it is made to be difficult to market-oriented popularization.
As Chinese invention patent that application publication number is CN107275590A disclose a kind of porous Si-C composite material and Preparation method, the material are first to obtain porous silicon by mechanical ball mill and acid etch by ferro-silicium, and mix with organic carbon source Conjunction is obtained by spraying pelletizing, high temperature cabonization.Although the material has certain change in capacity, first charge discharge efficiency and its cycle performance It is kind, but the expansion rate in material is still higher, electronic conduction sexual deviation, and charcoal coating thickness is thicker, influences its material Energy density plays.
Application publication number is that CN105355849A Chinese invention patent discloses a kind of cathode of lithium battery additive, the cathode Additive is in core-shell structure, and kernel is made of nano silica fume, lithium flour complexes, hollow carbon sphere, and shell is mainly by carbon nanotube, table Nano silica fume, lithium flour complexes, hollow carbon sphere are first uniformly mixed to obtain mixing in the preparation by face activating agent, dopant composition Carbon nanotube, surfactant are added in solvent and are uniformly mixed to obtain mixture B, then mix mixture A and mixture B by object A It is heat-treated 0.5-5h at 300-500 DEG C after closing uniformly, is mixed after adding dopant sodium chloride or sodium fluoride, in 600-1000 Carbonization treatment 1-10h at DEG C.It is doped with more other compositions in the material, causes the specific capacity of silicon materials to play and is limited System.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of silicon-carbon composite cathode material, to improve the ratio of silicon carbon material Capacity.
The object of the invention is also to provide silicon-carbon composite cathode materials made from a kind of above method.
To achieve the above object, the technical scheme is that
A kind of preparation method of silicon-carbon composite cathode material, includes the following steps:
1) silane coupling agent, porous carbon materials are spray-dried after mixing in organic solvent, are made modified porous Carbon material；
2) by modified porous carbon material under silane gas existence condition, 1000-1200 DEG C of heat preservation 1-6h；Then it is cooled to 600-800 DEG C, in the presence of gas dopant, 1-6h is kept the temperature, silicon carbon material is made；The gas dopant is NH3、N2O、NO、 N2O4One or more of combination；
3) by silicon carbon material under carbon-source gas existence condition, 700-900 DEG C of heat preservation 1-12h to get.
Porous carbon sill of sheet is soaked in silane coupling agent by the present invention first, after dry, is passed through silane gas and doping Agent gas carries out the primary depositing of silicon, is deposited on its surface by vapour deposition process generate carbon nanotube progress secondary deposition later And prepare Si-C composite material.Silane cracking, which is deposited in porous carbon sill of sheet hole, using vapour deposition process reduces charge and discharge The expansion of silicon in electric process, while outer layer carbon nanotube has many advantages, such as that mechanical strength is high, conductivity is strong, and utilizes vapor deposition Method has many advantages, such as that uniform doping, consistency are high, and the silicon-carbon composite cathode material finally prepared has specific capacity height, electric conductivity By force, the characteristics of good cycle, it can be applied to the lithium ion battery of high-energy-density density.
Silane coupling agent in step 1), porous carbon materials, organic solvent mass ratio be (0.1~1): (1~5): 100.
Silane coupling agent is gamma-aminopropyl-triethoxy-silane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy in step 1) Base silane, γ-(methacryloxypropyl) propyl trimethoxy silicane, octyltri-ethoxysilane, dimethyldimethoxysil,ne One of or several combinations.
In step 1) organic solvent be N-N- dimethylformamide, N-N- dimethyl acetamide, N-N- diethyl acetamide, N-methyl-2-pyrrolidone, gamma-butyrolacton, the combination of one or more of dimethyl sulfoxide.
Silane gas is monosilane (SiH in step 2)4), disilane (Si2H6) one or both of combination.
Carbon-source gas in step 3) is the combination of one or more of methane, acetylene, ethane, ethylene.
It is to mix silane coupling agent and organic solvent that silane coupling agent, porous carbon materials are uniformly mixed in organic solvent After closing uniformly, porous carbon materials are then added, are uniformly mixed.
Silane gas existence condition is first emptied with inert gas in confined space in step 2), then passes to silane Gas.
In step 2) in the presence of gas dopant, after keeping the temperature 1-6h, stopping is passed through gas dopant, is passed through indifferent gas Body.Then it is cooled to room temperature, crushes, obtains silicon carbon material.
Carbon-source gas existence condition is first emptied with inert gas in confined space in step 3), then passes to carbon source Gas.
In step 3) after 700-900 DEG C of heat preservation 1-12h, stopping is passed through carbon-source gas, is passed through inert gas.Then it is cooled to Room temperature.
Above-mentioned porous carbon materials are made using the method included the following steps: by oxidized asphalt, carbon disulfide, aluminium chloride, Carbon tetrachloride is separated by solid-liquid separation in 80-100 DEG C of progress cross-linking reaction, obtains presoma；Under an inert atmosphere by presoma, 1000- 1200 DEG C of sintering 1-3h, obtain porous carbon materials.
The time of the cross-linking reaction is 1.5-2h.
The corresponding oxidized asphalt for using 50-150g of the carbon disulfide of every 1L.
The corresponding aluminium chloride for using 1-5g of the oxidized asphalt of every 50-150g.
The corresponding carbon tetrachloride for using 10-15g of the oxidized asphalt of every 50-150g.
By oxidized asphalt, carbon disulfide, aluminium chloride, carbon tetrachloride 80-100 DEG C of progress cross-linking reaction be first will oxidation drip Blueness is uniformly mixed with carbon disulfide, aluminium chloride is added after being warming up to 80-100 DEG C, carbon tetrachloride carries out cross-linking reaction.
Oxidized asphalt is uniformly mixed with carbon disulfide to be stirred with the revolving speed of 50-200rpm.Stir 30min.
Cool down after 1000-1200 DEG C of sintering 1-3h, crush, sub-sieve, obtains porous carbon materials.Room is down to when the cooling Temperature.
Silicon-carbon composite cathode material made from the above method is core-shell structure, and core is nano-silicon/porous carbon composite, Shell is carbon nanotube.In silicon-carbon composite cathode material, the mass percentage of silicon is 1-30%.
Beneficial effects of the present invention:
The problems such as present invention is high for silicon-carbon cathode material expansion rate in the prior art, tap density is small and poorly conductive, Silicon materials are deposited on inside porous carbon materials by vapour deposition process, and in its outer layer deposition of carbon nanotubes, by sinking twice Product prepares the silicon-carbon composite cathode material that expansion rate is low, consistency is high, conductivity is good and tap density is high.The present invention by Porous carbon materials surface doping silane compound, and silane gas, which is carried out cracking, by chemical gas-phase method makes siliceous deposits in material Surface and porous carbon materials inside, improve the deposition uniformity of silicon, avoid the reunion of silicon itself, while silane compound With with porous carbon and the preferable combination of silicon deposits, the binding force between silicon/porous carbon composite can be improved, and The final tap density for improving material, reduces the expansion of material.It is passed through nitrogen source dopant gas, can be improved the conduction of its kernel Property, and improve the compatibility of silicon/porous carbon and electrolyte.Carbon nanotube is coated on inner nuclear material surface, avoids silicon materials direct With electrolyte contacts, the Probability of side reaction is reduced.
Detailed description of the invention
Fig. 1 schemes for the SEM of silicon-carbon composite cathode material obtained in embodiment 1.
Specific embodiment
Technical solution of the present invention is described further combined with specific embodiments below.
Embodiment 1
The preparation method of the silicon-carbon composite cathode material of the present embodiment, includes the following steps:
1) 100g oxidized asphalt and 1000mL carbon disulfide in a kettle, is added, is that 100rpm is quickly stirred with revolving speed 30min mixes oxidized asphalt uniformly with carbon disulfide.Then 90 DEG C are warming up to, the AlCl of 3g is added3With the CCl of 12g4, into Row cross-linking reaction 1h, is then filtered, and under an argon atmosphere by obtained solid composite material, is warming up to 1100 DEG C, is kept the temperature 2h；So After cool to room temperature, crushed, be classified to obtain porous carbon materials.
2) 0.5g gamma-aminopropyl-triethoxy-silane is added in the n,N-Dimethylformamide of 100mL, is uniformly dispersed The above-mentioned porous carbon materials of 3g are added afterwards, are spray-dried after mixing, and inlet temperature when spray drying is 150 DEG C, is obtained To modified porous carbon material.
3) modified porous carbon material is transferred in tube furnace, is first passed through nitrogen discharge inner air tube, then passes to first silicon Alkane gas continues to be passed through and be heated to 1100 DEG C, keeps the temperature 3h, stops being passed through monosilane gas later, cool to after emptying nitrogen 700 DEG C, ammonia is passed through as gas dopant, keeps the temperature 3h, stops logical ammonia gas dopant later, and change logical argon gas, Then Temperature fall obtains silicon carbon material to room temperature, crushing.
4) silicon carbon material is transferred in tube furnace, the air being passed through in argon gas discharge pipe then passes to methane gas Body, and 800 DEG C are heated to, 6h is kept the temperature, stops being passed through methane gas later, changes logical argon gas, Temperature fall to room temperature obtains Silicon-carbon composite cathode material.
The silicon-carbon composite cathode material of the present embodiment is core-shell structure, and core is nano-silicon/porous carbon composite, and shell is Carbon nanotube, the mass percentage of silicon oxide compound is 33% in silicon-carbon composite cathode material.
Embodiment 2
The preparation method of the silicon-carbon composite cathode material of the present embodiment, includes the following steps:
1) 50g oxidized asphalt and 1000mL carbon disulfide in a kettle, is added, is that 50rpm is quickly stirred with revolving speed 30min mixes oxidized asphalt uniformly with carbon disulfide.Then 80 DEG C are warming up to, the AlCl of 5g is added3With the CCl of 15g4, into Row cross-linking reaction 2h, is then filtered, and under an argon atmosphere by obtained solid composite material, is warming up to 1200 DEG C, is kept the temperature 1h；So After cool to room temperature, crushed, be classified to obtain porous carbon materials.
2) 0.1g γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane is added to the N-N- dimethylacetamide of 100mL In amine, the above-mentioned porous carbon materials of 5g are added after being uniformly dispersed, are spray-dried after mixing, import temperature when spray drying Degree is 100 DEG C, obtains modified porous carbon material.
3) modified porous carbon material is transferred in tube furnace, is first passed through nitrogen discharge inner air tube, then passes to second silicon Alkane gas continues to be passed through and be heated to 1000 DEG C, keeps the temperature 6h, stops being passed through b silane gas later, cool to after emptying nitrogen 800 DEG C, nitrous oxide is passed through as gas dopant, keeps the temperature 6h, stops logical gas dopant later, and change logical nitrogen gas Body, then Temperature fall to room temperature, crushing obtain silicon carbon material.
4) silicon carbon material is transferred in tube furnace, the air being passed through in nitrogen gas discharge pipe then passes to acetylene gas Body, and 700 DEG C are heated to, 1h is kept the temperature, stops being passed through acetylene gas later, changes logical nitrogen gas, Temperature fall to room temperature obtains Silicon-carbon composite cathode material.
The silicon-carbon composite cathode material of the present embodiment is core-shell structure, and core is nano-silicon/porous carbon composite, and shell is Carbon nanotube, the mass percentage of silicon oxide compound is 35% in silicon-carbon composite cathode material.
Embodiment 3
The preparation method of the silicon-carbon composite cathode material of the present embodiment, includes the following steps:
1) 150g oxidized asphalt and 1000mL carbon disulfide in a kettle, is added, is that 200rpm is quickly stirred with revolving speed 30min mixes oxidized asphalt uniformly with carbon disulfide.Then 100 DEG C are warming up to, the AlCl of 1g is added3With the CCl of 10g4, into Row cross-linking reaction 0.5h, is then filtered, and under an argon atmosphere by obtained solid composite material, is warming up to 1000 DEG C, is kept the temperature 3h； Then room temperature is cooled to, crushed, be classified to obtain porous carbon materials.
2) 1g dimethyldimethoxysil,ne is added in the gamma-butyrolacton of 100mL, it is above-mentioned that 1g is added after being uniformly dispersed Porous carbon materials are spray-dried after mixing, and inlet temperature when spray drying is 120 DEG C, obtain modified porous carbon Material.
3) modified porous carbon material is transferred in tube furnace, is first passed through argon gas discharge inner air tube, then passes to first silicon Alkane gas continues to be passed through and be heated to 1200 DEG C, keeps the temperature 1h, stops being passed through monosilane gas later, cool to after emptying nitrogen 600 DEG C, dinitrogen tetroxide is passed through as gas dopant, keeps the temperature 1h, stops logical gas dopant later, and change logical argon gas gas Body, then Temperature fall to room temperature, crushing obtain silicon carbon material.
4) silicon carbon material is transferred in tube furnace, the air being passed through in argon gas discharge pipe then passes to ethylene gas Body, and 900 DEG C are heated to, 1h is kept the temperature, stops being passed through ethylene gas later, changes logical argon gas, Temperature fall to room temperature obtains Silicon-carbon composite cathode material.
The silicon-carbon composite cathode material of the present embodiment is core-shell structure, and core is nano-silicon/porous carbon composite, and shell is Carbon nanotube, the mass percentage of silicon is 32% in silicon-carbon composite cathode material.
Comparative example
Silicon-carbon cathode in this comparative example is adopted as purchasing from Shenzhen City Beiterui New Energy Materials Co., Ltd The silicon-carbon cathode material of model S-500A.Wherein silicon oxide compound content 30%.
Test example
(1) SEM is tested
Silicon-carbon composite cathode material obtained in embodiment 1 is subjected to SEM test, test results are shown in figure 1.
As can be seen from Figure, grain structure is presented in the silicon-carbon composite cathode material in embodiment 1, and partial size is 5-15 μm, size distribution is uniformly, rationally.
(2) physical property and button electric performance test
Method in GBT24533-2009 " silicon/carbon/graphite in lithium ion batteries class negative electrode material " according to national standards, test implementation Specific surface area, tap density, specific capacity (being tested by button cell) and its conduction of example 1-3 and the silicon carbon material in comparative example Rate (is tested) by four probe method, while testing the high rate performance and cycle performance of its button cell.
High rate performance test condition: it is respectively 10C charging with multiplying power, is discharged with 1C；Voltage range 0.05-2V；Temperature 25 ± 3 DEG C of degree.
Cycle performance test condition: 1C charging, 1C electric discharge, voltage range 0.05-2V, 25 ± 3 DEG C of temperature；Cycle-index is 100 times.
Detain electrical testing condition:
Respectively by the silicon carbon material negative electrode active material preparation negative electrode tab (formula: silicon-carbon in Examples 1 to 3 and comparative example Material: CMC:SBR:SP:H2O=95:2.5:1.5:1:150), lithium piece uses LiPF as positive plate, electrolyte6/ EC+DEC, Electrolyte solvent volume ratio EC: DEC=1: 1, diaphragm is using polythene PE, the composite membrane of polypropylene PP and poly- second propylene PEP, button Being assemblied in the glove box for be flushed with hydrogen gas for formula battery carries out.Finally it is assembled into button cell A1, A2, A3 and B.Chemical property exists It is carried out on the indigo plant electricity CT2001A type cell tester of Wuhan, charging/discharging voltage scope control is 0.005~2.0V, charge-discharge magnification It is 0.1C.
Button cell A1, A2, A3 with comparative example 1 buckle electricity B test result compared with see the table below 1.
1 embodiment of table is compared with the performance of the silicon carbon material in comparative example
Embodiment 1 Embodiment 2 Embodiment 3 Comparative example
Tap density (g/cm3) 1.11 1.18 1.09 0.71
Specific capacity (mAh/g) 838.6 829.4 838.5 645.6
First charge discharge efficiency (%) 87.5 86.5 86.1 82.4
Resistivity (Ω m) 3×10-4 8×10-4 9×10-4 5×10-3
Specific surface area (g/m2) 65.4 67.8 68.3 8.3
Multiplying power (10C/1C, %) 90.1 88.6 86.2 80.1
It recycles (100 times, %) 83.6 81.8 80.3 72.1
As can be seen from Table 1, the specific capacity and its first charge discharge efficiency for the material that the present invention prepares are substantially better than comparative example, Reason is nanometer silicon compound uniform deposition on porous carbon materials, and is uniformly dispersed, and reduces the expansion of material, improves material The gram volume of material plays, simultaneously because material surface is coated with carbon nanotube, improves the electric conductivity of material.Due to porous carbon Material can increase the specific surface of composite material, be also beneficial to improve the imbibition liquid-keeping property of material, further improve its electrification Learn performance.
(3) soft-package battery is tested
Silicon carbon material in Example 1~3 and comparative example as negative electrode active material, using CMC/SBR as binder, with Super carbon black SP is conductive agent, carry out by solvent of secondary distilled water conjunction slurry, cathode pole piece is prepared in coating, is made with LiFePO4 Positive plate is prepared for positive active material.In electrolyte, solvent is EC/DEC/PC (EC:DEC:PC=1:1:1) as electrolysis Liquid, solute LiPF6.Using 2400 film of Celgard as diaphragm.5Ah soft-package battery C1, C2, C3 and D1 are prepared respectively.
Test the cycle performance (1.0C/1.0C) of the imbibition of negative electrode tab obtained, liquid-keeping property and lithium battery.Test side Method is carried out referring to standard GB/T/T 24533-2009 " silicon/carbon/graphite in lithium ion batteries class negative electrode material "；Simultaneously according to lithium-ion electric Tank discharge capacity and quality calculate the mass energy density of flexible packing lithium ion battery.
Test result see the table below 2~3.
The imbibition of 2 negative electrode tab of table, liquid-keeping property
Rate of liquid aspiration (mL/min) It protects liquid rate (electrolyte content/0h electrolyte content for 24 hours)
Embodiment 1 3.8 95.1%
Embodiment 2 3.6 94.3%
Embodiment 3 3.5 94.2%
Comparative example 1.2 83.1%
As shown in Table 2, the imbibition liquid-keeping property of negative electricity pole piece is significantly better than that comparative example, reason can in Examples 1 to 3 It can be: make silicon carbon material that there is high specific surface area using vapour deposition process and using porous carbon materials, improve its pole piece Imbibition liquid-keeping property, while shell cladding specific surface area of carbon nanotube it is big, can be further improved pole piece imbibition protect liquid Ability.
The cycle performance of 3 soft-package battery of table
As can be seen from Table 3, the cycle performance of soft-package battery is significantly better than that comparative example in Examples 1 to 3, analyzes reason It may is that nano-silicon uniform deposition using vapour deposition process in porous carbon hole, reduce nano-silicon charge and discharge process In expansion, while silane coupling agent have with porous carbon and the preferable binding force of nano-silicon, improve material between binding force, Improve its cycle performance.

Claims (9)

1. a kind of preparation method of silicon-carbon composite cathode material, which comprises the steps of:
1) silane coupling agent, porous carbon materials are spray-dried after mixing in organic solvent, modified porous carbon materials is made Material；
2) by modified porous carbon material under silane gas existence condition, 1000-1200 DEG C of heat preservation 1-6h；Then it is cooled to 600- 800 DEG C, in the presence of gas dopant, 1-6h is kept the temperature, silicon carbon material is made；The gas dopant is NH3、N2O、NO、N2O4 One or more of combination；
3) by silicon carbon material under carbon-source gas existence condition, 700-900 DEG C of heat preservation 1-12h to get.
2. the preparation method of silicon-carbon composite cathode material according to claim 1, it is characterised in that: silane is even in step 1) Join agent, porous carbon materials, organic solvent mass ratio be (0.1-1): (1-5): 100.
3. the preparation method of silicon-carbon composite cathode material according to claim 1, it is characterised in that: silane is even in step 1) Connection agent is gamma-aminopropyl-triethoxy-silane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, γ-(methacryl Oxygen) propyl trimethoxy silicane, octyltri-ethoxysilane, one or more of dimethyldimethoxysil,ne combination.
4. the preparation method of silicon-carbon composite cathode material according to claim 1, it is characterised in that: organic molten in step 1) Agent is N-N- dimethylformamide, N-N- dimethyl acetamide, N-N- diethyl acetamide, n-methyl-2-pyrrolidone, γ- The combination of one or more of butyrolactone, dimethyl sulfoxide.
5. the preparation method of silicon-carbon composite cathode material according to claim 1, it is characterised in that: silane gas in step 2) Body is the combination of one or both of monosilane, disilane.
6. the preparation method of silicon-carbon composite cathode material according to claim 1, it is characterised in that: the carbon source in step 3) Gas is the combination of one or more of methane, acetylene, ethane, ethylene.
7. the preparation method of silicon-carbon composite cathode material described in -6 any one according to claim 1, it is characterised in that: step 1) porous carbon materials in are made using the method included the following steps: by oxidized asphalt, carbon disulfide, aluminium chloride, four chlorinations Carbon is separated by solid-liquid separation in 80-100 DEG C of progress cross-linking reaction, obtains presoma；Under an inert atmosphere by presoma, 1000-1200 DEG C It is sintered 1-3h, obtains porous carbon materials.
8. the preparation method of silicon-carbon composite cathode material according to claim 7, it is characterised in that: the cross-linking reaction Time is 1.5-2h.
9. a kind of silicon-carbon composite cathode material as made from the method as described in claim 1.
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