CN106410177A - Ellipsoidal SiOx/graphite cathode composite material and preparation method and application thereof - Google Patents

Ellipsoidal SiOx/graphite cathode composite material and preparation method and application thereof Download PDF

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CN106410177A
CN106410177A CN201610976258.4A CN201610976258A CN106410177A CN 106410177 A CN106410177 A CN 106410177A CN 201610976258 A CN201610976258 A CN 201610976258A CN 106410177 A CN106410177 A CN 106410177A
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graphite
silicon
sub
elliposoidal
composite
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CN106410177B (en
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郭玉国
李金熠
徐泉
殷雅侠
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Beijing One Gold Amperex Technology Ltd
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Institute of Chemistry CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 invention provides an ellipsoidal SiOx/graphite cathode composite material prepared from raw materials including graphite and silicon monoxide, and a preparation method of application of the ellipsoidal SiOx/graphite cathode composite material. According to the method, the graphite and the silicon monoxide blocks are used as the raw materials, a slurry drying and ellipsoid technology is used, finally, wrapping is implemented, specific surface area is reduced effectively, and a stable SEI film is formed; and owing to good dispersion and reasonable cavities of the silicon monoxide, the circulating performance of the material is excellent.

Description

A kind of elliposoidal SiOx/ graphite cathode composite and its preparation method and application
Technical field
The present invention relates to a kind of elliposoidal SiOx/ graphite cathode composite, particularly to elliposoidal SiOx/ graphite cathode Composite is as the application of height ratio capacity lithium ion battery negative material.
Background technology：
Lithium ion battery has that specific energy is high, self discharge is little, the outstanding advantages such as long service life, green non-pollution are wide General is applied in portable electronic products and electric automobile.With social development and progress, further should of lithium ion battery With needing raising energy density badly, the electrode material of exploitation height ratio capacity is one of effective way.
In negative material, business-like at present mainly material with carbon element, its theoretical specific capacity is relatively low, about 372mAh g-1.And silicon is because having high theoretical specific capacity (about 3579mAh g-1) and receive more and more attention, it is considered as to have most One of material of graphite cathode may be substituted.But silicon can produce about 300% change in volume during Li insertion extraction, huge Change in volume the efflorescence of silicon electrode can be caused to peel off, make to lose electrical contact between silicon grain and between silicon and collector.Oxygen Change sub- silicon materials although its theoretical specific capacity is less than pure silicon material, but its bulk effect in battery charge and discharge process is relatively Less (about 200%), therefore, the sub- silicon materials of oxidation are easier to break through restriction, realize commercialization early.Industrial modal SiOx(0<x<2) material is exactly the sub- silicon of oxidation, SiOxIt is a kind of binary phase materials, SiOxBy particle diameter minimum (<Amorphous Si 1nm) And SiO2Composition.SiOxStructure can be adjusted by simple means such as heat treatment, ball milling and etchings.By in protective atmosphere Under to SiOxCarry out heat treatment and can promote SiOxThere is dismutation reaction, form Si and SiO2Biphase.In general, SiOxAt 800 DEG C Hereinafter keep original impalpable structure；When temperature rises to 900～1000 DEG C, SiOxStart dismutation reaction；With The continuation of temperature rises, SiOxDisproportionation obvious all the more, the crystal grain of Si simple substance is also gradually grown up.The generation of dismutation reaction also promotes SiOxChemical property change：With the intensification of disproportionation degree, SiOxThe specific capacity of electrode is gradually reduced；When disproportionation reaches To a certain extent, SiOxSubstantially lose electro-chemical activity.It is also a difficult problem therefore for the control of sintering temperature.
Therefore, inventor devises a kind of excellent scheme, and the program, initially with the technique of slurry drying, realizes SiOx Fine dispersion and fixation, further adopt air-flow vortex micro mist reshaping technology, using graphite spheroidization equipment, using suitable Carburizing temperature is preparing elliposoidal SiO that cycle efficieny first is higher and cycle performance is excellentx/ graphite cathode composite.
Content of the invention
Present invention aim at by rational structure design and preparation method, providing a kind of sub- using graphite and oxidation Silicon prepares elliposoidal SiO for raw materialxThe method of/graphite cathode composite, and its performance is studied.The present invention is first Using the technique of slurry drying, realize SiOxFine dispersion and fixation, further adopt air-flow vortex micro mist reshaping technology, warp Cavity structure being made to be compressed after crossing air-flow vortex shaping, thus improving the tap density of material, and using graphite nodule Shape equipment, to prepare the elliposoidal that cycle efficieny is higher first and cycle performance is excellent using suitable carburizing temperature SiOx/ graphite cathode composite.
Present invention firstly provides a kind of elliposoidal SiOx/ graphite cathode composite, the wherein SiO of this compositexContent For 30-80%, carbon content is 20-70%, 0<x<2, wherein, material with carbon element, mainly based on graphitized carbon, is present in ball interior, For amorphous carbon it is characterised in that this complex microsphere is equally distributed ellipsoidal particle, average diameter is 3-25 to particle surface μm, tap density is more than 0.8.
It is further preferred that described cavity volume accounts for the 20-80% of elliposoidal composite it is preferable that 40-50%.
It is further preferred that described grain diameter meets：1.5≤(D90-D10)/D50≤2, BET specific surface area be (8 ± 5)m2·g-1.
It is further preferred that described average diameter of particles is 7-23 μm, 1.5≤(D90-D10)/D50≤2, BET specific surface Amass as (5 ± 2) m2·g-1.
Further object of the present invention is to provide described elliposoidal SiOxThe application of/graphite cathode composite.
Application provided by the present invention is elliposoidal SiOx/ graphite cathode composite answering as battery electrode material With especially as the application of lithium ion battery negative material.
The present invention further provides elliposoidal SiOxThe preparation method of/graphite cathode composite, including as follows：
Step 1) sub- silica flour ball mill pulverizing will be aoxidized after, add inorganic carbon source, weight average molecular weight to be 50000-1000000's Polymeric additive, hydroxyl dispersant proceed ball milling, the slurry being uniformly mixed；
Step 2) by step 1) mixture of gained adds appropriate solvent, mechanical agitation, is adjusted to suitable viscosity；
Step 3) the suitable sample of gained viscosity, it is dried process, obtain solid state powder A；
Step 4) adopt the graphite that particle diameter is 50-325 mesh to be raw material, add raw materials into air-flow vortex pulverizing mill and refined Process；
Step 5) by step 4) graphite after refinement isolates the pressed powder B of appropriate particle size using cyclone separation system；
Step 6) by step 3) the powders A obtaining and step 5) after gained B mixs homogeneously, add spheroidization device, nodularization Oxidation Asia silicon and the carbon elliposoidal composite of appropriate particle size after certain time, is obtained using cyclone separator；
Step 7) by step 6) gained elliposoidal composite coated, cladding adopts graphite；
Step 8) by step 7) solid particle that obtains obtains ellipsoid in inert non-oxidizing property atmosphere high temperature carbonization treatment Shape SiOx/ graphite cathode composite；
Preferably, step 1) described in the sub- silicon of oxidation be 20nm-10mm；Material particle size after grinding is 10nm-3 μm, institute State inorganic carbon source and be selected from following at least one：Delanium, native graphite, MCMB, Graphene, CNT；Institute State at least one that polymeric additive is in following substances：Phenolic resin, Colophonium, polyvinylidene fluoride (PVDF), polyethylene Ketopyrrolidine (PVP), polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO), polrvinyl chloride (PVC), polyacrylonitrile (PAN), poly- second Alkynes, polyaniline, polythiophene, weight average molecular weight is preferably 100000-800000；
Preferably, step 1) described in hydroxyl dispersant be following substances at least one：Glucose, sucrose, citric acid, Sodium alginate, carboxymethyl cellulose, hydroxypropyl cellulose, gelatin, starch, shitosan, alginic acid.
Preferably, step 1) in the mass ratio of silica flour and inorganic carbon source be (1-9)：(9-1), preferably (2-8)：(8-2), Concretely 2：8、3：7、4：6、5：5、6：4、7：3、8：2；In described slurry, silica flour can with the mass concentration sum of inorganic carbon source For 1～50%；Described polymeric additive ratio is the 1～20% of silica flour and inorganic carbon source gross mass, described hydroxy compounds Dispersive agent ratio is the 10～50% of silica flour and inorganic carbon source gross mass.
Preferably, step 2) described in solvent be following one or several：Water, methanol, ethanol, acetone, benzene, chloroform Deng；Viscosity is tested under temperature is for 293K, and viscosity can be 1-1000mPa s, preferably 100-500mPa s.
Preferably, step 3) described in drying proposal adopt one of following scheme：Forced air drying, drying under reduced pressure, cold Lyophilizing is dry, spray drying；Baking temperature is less than 200 DEG C, and the value, Δ x of x change is less than 5%, and controls material oxidation degree, Avoid introducing unnecessary oxygen.
Preferably, step 4) described in graphite be one of graphite or several：Scaly graphite, cryptocrystalline stone Ink, expanded graphite, Delanium, native graphite.
Preferably, step 5) described in suitable particle diameter be 0.5-30 μm, preferably 1.5-25 μm.
Preferably, step 6) described spheroidization device be air-flow vortex balling machine, wherein classifying turbine rotating speed be 500- 6000rpm, interior wheel speed is 3000-6600rpm.
Preferably, step 8) described in non-oxidizing atmosphere by following at least one gases provide：Nitrogen, argon, helium, Described sintering temperature is 400-1200 DEG C, preferably 450-1000 DEG C, and programming rate is 1-15 DEG C/min, preferably 1-5 DEG C/ Min, sintering time is 1-15h, preferably 2-6h.
Preferably, described polymeric additive is polyacrylonitrile (PAN)；Described hydroxyl dispersant is carboxymethyl cellulose simultaneously Element.
Further object of the present invention is the elliposoidal SiOx/ graphite cathode composite providing preceding method to prepare. Additionally, also providing the application of elliposoidal SiOx/ graphite cathode composite that preceding method prepares, described application is ellipsoid Shape SiOx/ graphite cathode composite as the application of battery electrode material, especially as lithium ion battery negative material Application.
In addition, the present invention also provides a kind of energy storage elements, described energy storage elements contain preceding method and are prepared into The elliposoidal SiOx/ graphite cathode composite arriving, the preferred lithium ion battery of this energy storage elements.
The present invention also provides a kind of portable electric appts, and this electronic equipment is ellipse using prepare containing preceding method The above-mentioned energy storage elements of spherical SiO x/ graphite cathode composite, the preferred mobile phone of this portable electric appts, photograph Machine, video camera, MP3, MP4, notebook computer.
Compared with prior art, the present invention adopts graphite and the sub- silicon block of oxidation is raw material, using slurry drying Molding and air-flow vortex shaping technique, realize SiOxFine dispersion and fixation.Compared with the process route of pure silicon material, the party Case cost is lower and technique is easier to prepare on a large scale.Cavity structure can be made after air-flow vortex shaping to be compressed, from And improve the tap density of material, and finally specific surface area is effectively reduced using cladding, advantageously form stable SEI film； Because the good dispersion of the sub- silicon of oxidation and rational cavity make material circulation excellent performance.
Brief description
Fig. 1 is the electron scanning micrograph of embodiment 5 gained elliposoidal SiOx/ graphite cathode composite.
Survey under 100mA/g electric current density for the elliposoidal SiOx/ graphite cathode composite that Fig. 2 obtains for embodiment 9 Examination data.
Fig. 3 is that the section of embodiment 5 gained elliposoidal SiOx/ graphite cathode composite characterizes, using focused ion bundle Material is processed.
Specific embodiment
With reference to specific embodiment, the present invention is further described, the present invention is not limited to following case study on implementation.
Test method described in following embodiments, if no special instructions, is conventional method；Described reagent and material, such as No specified otherwise, all can obtain from commercial channels.
Embodiment 1
Preparation elliposoidal SiOx/ graphite cathode composite
Step 1)：After the silica flour ball mill pulverizing of the oxidation of particle diameter 1mm Asia, after pulverizing, granularity is 300nm, sub- by oxidation Silicon：Graphite=2：8 mass ratio mixing, with water as solvent, PAN is polymeric additive, and weight average molecular weight is 300000, sucrose For hydroxyl dispersant, the quality of PAN polymeric additive is the 3% of the sub- silicon of oxidation and graphite gross mass, and the quality of sucrose is oxygen Change the 10% of sub- silicon and graphite gross mass, the slurry that ball milling is uniformly mixed；
Step 2)：Add suitable quantity of water, 5h more than is stirred at room temperature, obtain the slurry that viscosity is 200m Pa s；
Step 3)：Slurry is carried out spray drying treatment, treatment temperature is 150 DEG C, obtains powders A；
Step 4)：Using air-flow vortex pulverizing mill, native graphite is pulverized and carry out micronization processes, the grain of described native graphite Footpath is 100 mesh；
Step 5)：By step 4) graphite after refinement isolates the pressed powder B of appropriate particle size using cyclone separation system；
Step 6)：By powders A：B=8：Add in balling machine after 2 uniform mixing, wherein classifying turbine rotating speed is 4000rpm, interior wheel speed is 6500rpm, obtains elliposoidal complex through shaping in 20 minutes；
Step 7)：Using graphite coat scheme, this elliposoidal complex is coated, solid phase method for coating, add 8% drip Calomelas end, forms uniform complex.
Step 8)：This complex is sintered for 450 DEG C in nitrogen atmosphere, heating rate is 5 DEG C/min, sinters 6h, finally To elliposoidal SiOx/ graphite cathode composite.
The sign of elliposoidal composite：
Detect the particle diameter of the Si-C composite material obtaining under above-mentioned condition with NEC scanning electron microscope (JEOL-6700F) And particle size distribution, result shows that the particle size distribution ratio of Si-C composite material is more uniform, and particle diameter (is shown in Table 1) between 1～20 μm, institute State and measure this material tap density more than 0.80g/cm with powder tap density instrument3It is shown in Table 1.
The Electrochemical Characterization of elliposoidal SiOx/ graphite cathode composite：
By the elliposoidal SiOx/ graphite cathode composite of preparation, acetylene black and sodium carboxymethyl cellulose in embodiment 1 (binding agent) is with mass ratio 80：10：10 mixing are made into slurry, are homogeneously applied in copper foil current collector obtain electrode diaphragm.With As to electrode, as barrier film, (solvent is volume to 1mol/L LiPF6 to microporous polypropylene membrane (Celgard 2400) to metal lithium sheet Than for 1：1 ethylene carbonate and dimethyl carbonate mixed liquor, wherein add 5% vinylidene carbonic ester, 2% carbonic acid Asia second Alkene ester) as electrolyte, it is assembled into button cell in the glove box of argon protection, carries out charge-discharge test, test program is 100mA/g, charging/discharging voltage is interval to be 0.01～1.0V, and cell testing results are listed in table 1-2.
Embodiment 2
Embodiment 2 is with the difference of embodiment 1：
Step 1) middle oxidation Asia silicon：Graphite=4：6 mass ratioes, the particle diameter of the sub- silicon of oxidation is 5mm, and after pulverizing, material particle size is 1μm；
Step 2) gained slurry viscosity be 100mPa s；
Step 4) described native graphite particle diameter be 300 mesh.
The positive pole of battery, negative pole, electrolyte and battery assembling are same as Example 1, and gained aoxidizes sub- silicon and carbon electrode material The test result of the composition of material and battery is listed in table 1-2.
Embodiment 3
Embodiment 3 is with the difference of embodiment 1：
Step 1) in graphite, the sub- silicon of oxidation are replaced with CNT：CNT=6：4 mass ratioes, the grain of the sub- silicon of oxidation Footpath is 5mm, and after pulverizing, material particle size is 1 μm；
Step 2) gained slurry viscosity be 100mPa s；
Step 3) described Drying method adopts drying under reduced pressure；Temperature is less than 180 DEG C；
Step 4) described native graphite particle diameter be 300 mesh.
The sub- silicon of oxidation is same as Example 1 with the sign of carbon composite.
The positive pole of battery, negative pole, electrolyte and battery assembling are same as Example 1, and gained aoxidizes sub- silicon and carbon electrode material The test result of the composition of material and battery is listed in table 1-2.
Embodiment 4
Embodiment 4 is with the difference of embodiment 1：
Step 1) in polyacrylonitrile (PAN) is replaced with phenolic resin, the weight average molecular weight of phenolic resin is 700000；
Step 3) slurry is carried out lyophilization, obtain powders A.
The sub- silicon of oxidation is same as Example 1 with the sign of carbon composite.
The positive pole of battery, negative pole, electrolyte and battery assembling are same as Example 1, and gained aoxidizes sub- silicon and carbon electrode material The test result of the composition of material and battery is listed in table 1-2.
Embodiment 5
Embodiment 5 is with the difference of embodiment 1：
Step 1) in polyvinyl alcohol replace polyacrylonitrile (PAN)；
Step 6) by powders A：B=6：Add in balling machine after 4 uniform mixing, wherein classifying turbine rotating speed is 1000rpm, Interior wheel speed is 3500rpm, obtains elliposoidal complex through shaping in 40 minutes.
The sub- silicon of oxidation is same as Example 1 with the sign of carbon composite.
The positive pole of battery, negative pole, electrolyte and battery assembling are same as Example 1, and gained aoxidizes sub- silicon and carbon electrode material The test result of the composition of material and battery is listed in table 1-2.
Embodiment 6
Embodiment 6 is with the difference of embodiment 1：
Step 1) in polyvinyl alcohol replace polyacrylonitrile (PAN)；
Step 6) by powders A：B=4：Add in balling machine after 6 uniform mixing, wherein classifying turbine rotating speed is 4000rpm, Interior wheel speed is 6500rpm, obtains elliposoidal complex through shaping in 40 minutes.
The sub- silicon of oxidation is same as Example 1 with the sign of carbon composite.
The positive pole of battery, negative pole, electrolyte and battery assembling are same as Example 1, and gained aoxidizes sub- silicon and carbon electrode material The test result of the composition of material and battery is listed in table 1-2.
Embodiment 7
Embodiment 7 is with the difference of embodiment 1：
Step 1) in polyaniline replace polyacrylonitrile (PAN)；Hydroxyl dispersant is carboxymethyl cellulose；The sub- silicon of oxidation：Stone Ink=8：2 mass ratioes
Step 6) by powders A：B=2：Add in balling machine after 8 uniform mixing, wherein classifying turbine rotating speed is 4000rpm, Interior wheel speed is 6500rpm, obtains elliposoidal complex through shaping in 40 minutes.
The sub- silicon of oxidation is same as Example 1 with the sign of carbon composite.
The positive pole of battery, negative pole, electrolyte and battery assembling are same as Example 1, and gained aoxidizes sub- silicon and carbon electrode material The test result of the composition of material and battery is listed in table 1-2.
Embodiment 8
Embodiment 8 is with the difference of embodiment 1：
Step 1) in polyaniline replace polyacrylonitrile (PAN)；Hydroxyl dispersant is carboxymethyl cellulose；The sub- silicon of oxidation：Stone Ink=8：2 mass ratioes
Step 3) described Drying method adopts drying under reduced pressure；Temperature is less than 180 DEG C；
Step 6) by powders A：B=2：Add in balling machine after 8 uniform mixing, wherein classifying turbine rotating speed is 4000rpm, Interior wheel speed is 6500rpm, obtains elliposoidal complex through shaping in 40 minutes；
Step 8) this complex is sintered for 600 DEG C in nitrogen atmosphere, heating rate is 5 DEG C/min, sinters 6h, final To elliposoidal SiOx/ graphite cathode composite.
The sub- silicon of oxidation is same as Example 1 with the sign of carbon composite.
The positive pole of battery, negative pole, electrolyte and battery assembling are same as Example 1, and gained aoxidizes sub- silicon and carbon electrode material The test result of the composition of material and battery is listed in table 1-2.
Embodiment 9
Embodiment 9 is with the difference of embodiment 1：
Step 1) in polyaniline replace polyacrylonitrile (PAN)；Hydroxyl dispersant is carboxymethyl cellulose；
Step 3) described Drying method adopts drying under reduced pressure；Temperature is less than 180 DEG C；
Step 6) by powders A：B=4：Add in balling machine after 6 uniform mixing, wherein classifying turbine rotating speed is 4000rpm, Interior wheel speed is 6500rpm, obtains elliposoidal complex through shaping in 40 minutes；
Step 8) this complex is sintered for 750 DEG C in nitrogen atmosphere, heating rate is 5 DEG C/min, sinters 6h, final To elliposoidal SiOx/ graphite cathode composite.
The sub- silicon of oxidation is same as Example 1 with the sign of carbon composite.
The positive pole of battery, negative pole, electrolyte and battery assembling are same as Example 1, and gained aoxidizes sub- silicon and carbon electrode material The test result of the composition of material and battery is listed in table 1-2.
Embodiment 10
Embodiment 10 is with the difference of embodiment 1：
Step 1) in polyacrylonitrile (PAN) is replaced with polyaniline, the weight average molecular weight of phenolic resin is 700000；Hydroxyl disperses Agent is carboxymethyl cellulose；The sub- silicon of oxidation：Graphite=8：2 mass ratioes
Step 6) by powders A：B=2：Add in balling machine after 8 uniform mixing, wherein classifying turbine rotating speed is 4000rpm, Interior wheel speed is 6500rpm, obtains elliposoidal complex through shaping in 40 minutes；
Step 8) this complex is sintered for 900 DEG C in nitrogen atmosphere, heating rate is 5 DEG C/min, sinters 6h, final To elliposoidal SiOx/ graphite cathode composite.
The sub- silicon of oxidation is same as Example 1 with the sign of carbon composite.
The positive pole of battery, negative pole, electrolyte and battery assembling are same as Example 1, and gained aoxidizes sub- silicon and carbon electrode material The test result of the composition of material and battery is listed in table 1-2.
Embodiment 11
Embodiment 11 is with the difference of embodiment 1：
Step 1) in polyacrylonitrile (PAN) is replaced with polyaniline, the weight average molecular weight of phenolic resin is 700000；Hydroxyl disperses Agent is alginic acid；The sub- silicon of oxidation：Graphite=8：2 mass ratioes
Step 6) by powders A：B=2：Add in balling machine after 8 uniform mixing, wherein classifying turbine rotating speed is 4000rpm, Interior wheel speed is 6500rpm, obtains elliposoidal complex through shaping in 40 minutes；
Step 8) this complex is sintered for 1000 DEG C in nitrogen atmosphere, heating rate is 5 DEG C/min, sinters 6h, finally To elliposoidal SiOx/ graphite cathode composite.
The sub- silicon of oxidation is same as Example 1 with the sign of carbon composite.
The positive pole of battery, negative pole, electrolyte and battery assembling are same as Example 1, and gained aoxidizes sub- silicon and carbon electrode material The test result of the composition of material and battery is listed in table 1-2.
Embodiment 12
Embodiment 12 is with the difference of embodiment 1：
Step 1) in polyacrylonitrile (PAN) is replaced with polyaniline, the weight average molecular weight of phenolic resin is 700000；Hydroxyl disperses Agent is alginic acid；The sub- silicon of oxidation：Graphite=8：2 mass ratioes
Step 6) by powders A：B=2：Add in balling machine after 8 uniform mixing, wherein classifying turbine rotating speed is 5000rpm, Interior wheel speed is 6500rpm, obtains elliposoidal complex through shaping in 40 minutes；
Step 8) this complex is sintered for 1200 DEG C in nitrogen atmosphere, heating rate is 5 DEG C/min, sinters 6h, finally To elliposoidal SiOx/ graphite cathode composite.
The sub- silicon of oxidation is same as Example 1 with the sign of carbon composite.
The positive pole of battery, negative pole, electrolyte and battery assembling are same as Example 1, and gained aoxidizes sub- silicon and carbon electrode material The test result of the composition of material and battery is listed in table 1-2.
Comparative example 1
Sub- Si powder will be aoxidized, be directly used as electrode material.
The sign of this electrode material is same as Example 1.
The positive pole of battery, negative pole, electrolyte and battery assembling are same as Example 1, the composition of the electrode obtained material and electricity The test result in pond is listed in table 1-2.
Comparative example 2
After sub- silica flour ball mill pulverizing will be aoxidized, by the sub- silicon of oxidation：Graphite=2：8 mass ratio mixing, with water as solvent, PAN is polymeric additive, and weight average molecular weight is 300000, and sucrose is hydroxyl dispersant, and the quality of PAN polymeric additive is The sub- silicon of oxidation and the 3% of graphite gross mass, the quality of sucrose is the 10% of the sub- silicon of oxidation and graphite gross mass, and ball milling is mixed Uniform slurry；
Add suitable quantity of water, 5h more than is stirred at room temperature, obtain the slurry that viscosity is 200mPa s.
Slurry is spray-dried, inlet temperature is 180 DEG C, this complex is sintered for 450 DEG C in nitrogen atmosphere, Heating rate is 5 DEG C/min, sinters 6h, final to SiOx/ graphite cathode composite.
The sign of this composite is same as Example 1.
The positive pole of battery, negative pole, electrolyte and battery assembling are same as Example 1, the composition of the electrode obtained material and electricity The test result in pond is listed in table 1-2.
Comparative example 3
After sub- silica flour ball mill pulverizing will be aoxidized, by the sub- silicon of oxidation：Graphite=4：6 mass ratio mixing, with water as solvent, PAN is polymeric additive, and weight average molecular weight is 300000, and sucrose is hydroxyl dispersant, 5h more than is stirred at room temperature, obtains Viscosity is the slurry of 200mPa s.Slurry is spray-dried, inlet temperature is 180 DEG C, obtains powders A.Using air-flow Vortex pulverizing mill pulverizes native graphite and cyclonic separation obtains powder B.By powders A：B=4：After 6 uniform mixing, this is combined Thing 300 DEG C of sintering in nitrogen atmosphere, heating rate is 5 DEG C/min, sinters 6h, final to SiOx/ graphite cathode composite wood Material.
The sub- silicon of oxidation is same as Example 1 with the sign of carbon composite.
The positive pole of battery, negative pole, electrolyte and battery assembling are same as Example 1, and gained aoxidizes sub- silicon and carbon electrode material The test result of the composition of material and battery is listed in table 1-2.
Comparative example 4
After sub- silica flour ball mill pulverizing will be aoxidized, by the sub- silicon of oxidation：Graphite=4：6 mass ratio mixing, PAN adds for polymer Plus agent, add in balling machine, wherein classifying turbine rotating speed is 4000rpm, interior wheel speed is 6500rpm, whole through 20 minutes Shape obtains elliposoidal complex.This complex is sintered for 1200 DEG C in nitrogen atmosphere, heating rate is 5 DEG C/min, sinters 6h, Final to SiOx/ graphite cathode composite.
The sub- silicon of oxidation is same as Example 1 with the sign of carbon composite.
The positive pole of battery, negative pole, electrolyte and battery assembling are same as Example 1, and gained aoxidizes sub- silicon and carbon electrode material The test result of the composition of material and battery is listed in table 1-2.
Comparative example 5
After sub- silica flour ball mill pulverizing will be aoxidized, by the sub- silicon of oxidation：Graphite=4：6 mass ratio mixing, PAN adds for polymer Plus agent, add in balling machine, wherein classifying turbine rotating speed is 4000rpm, interior wheel speed is 6500rpm, whole through 20 minutes Shape obtains elliposoidal complex.Using graphite coat scheme, this elliposoidal complex is coated, by this complex in nitrogen atmosphere In 1200 DEG C of sintering, heating rate is 5 DEG C/min, sinters 6h, final to elliposoidal SiOx/ graphite cathode composite.
The sub- silicon of oxidation is same as Example 1 with the sign of carbon composite.
The positive pole of battery, negative pole, electrolyte and battery assembling are same as Example 1, and gained aoxidizes sub- silicon and carbon electrode material The test result of the composition of material and battery is listed in table 1-2.
Comparative example 6
Comparative example 6 is with the difference of embodiment 1：
Step 1) in polyacrylonitrile (PAN) is replaced with polyaniline, the weight average molecular weight of phenolic resin is 700000；Hydroxyl disperses Agent is alginic acid；
Step 6) by powders A：B=4：Add in balling machine after 6 uniform mixing, wherein classifying turbine rotating speed is 4000rpm, Interior wheel speed is 6500rpm, obtains elliposoidal complex through shaping in 40 minutes；
Do not carry out the cladding process of step (7)
Step 8) this complex is sintered for 1200 DEG C in nitrogen atmosphere, heating rate is 5 DEG C/min, sinters 6h, finally To elliposoidal SiOx/ graphite cathode composite.
The composition of table 1 embodiment 1-12 and comparative example 1-6 and/structural parameters
Table 2 embodiment 1-12 and the performance parameter of comparative example 1-5

Claims (8)

1. a kind of elliposoidal SiOx/ graphite cathode composite, anode material, the wherein SiO of this compositexContent is 30-80%, carbon content is 20-70%, 0<x<2, wherein, material with carbon element, mainly based on graphitized carbon, is present in ball interior, For amorphous carbon it is characterised in that this complex microsphere is equally distributed ellipsoidal particle, average diameter is 3-25 μ on grain surface M, granule has cavity structure, and tap density is more than 0.80g cm3.
2. the composite of elliposoidal SiOx/ graphite cathode described in claim 1 is it is characterised in that described grain diameter meets： 1.5≤(D90-D10)/D50≤2, BET specific surface area is (8 ± 5) m2·g-1；It is further preferred that described average diameter of particles For 7-23 μm, 1.5≤(D90-D10)/D50≤2, BET specific surface area is (5 ± 2) m2·g-1.
3. the preparation method of the elliposoidal SiOx/ graphite cathode composite according to one of claim 1-2, concrete steps As follows：
Step 1), after sub- silica flour ball mill pulverizing will be aoxidized, add inorganic carbon source, weight average molecular weight to be the poly- of 50000-1000000 Compound additive, hydroxyl dispersant proceed ball milling, the slurry being uniformly mixed；
Step 2), by step 1) mixture of gained adds appropriate water, mechanical agitation, is adjusted to suitable viscosity；
Step 3), the suitable sample of gained viscosity, carry out spray drying treatment, obtain solid state powder A；
Step 4), using particle diameter for 50-325 mesh graphite be raw material, add raw materials into air-flow vortex pulverizing mill and carry out at refinement Reason；
Step 5), by step 4) graphite after refinement goes out the pressed powder B of appropriate particle size using cyclone separation system sub-argument；
Step 6), by step 3) the powders A obtaining and step 5) after gained B mixs homogeneously, add air-flow vortex apparatus for shaping, Oxidation Asia silicon and the carbon elliposoidal composite of appropriate particle size after shaping certain time, is obtained using cyclone separator；
Step 7), by step 6) gained elliposoidal composite coated；
Step 8), by step 7) solid particle that obtains obtains elliposoidal in inert non-oxidizing property atmosphere high temperature carbonization treatment SiOx/ graphite cathode composite.
4. preparation method according to claim 3, wherein step 1) described in the sub- silicon of oxidation be 8nm-10mm；After grinding Material particle size is 10nm-3 μm, and described inorganic carbon source is selected from following at least one：Delanium, native graphite, intermediate-phase carbon are micro- Ball, Graphene, CNT；Described polymeric additive is at least one in following substances：Phenolic resin, Colophonium, poly- partially Difluoroethylene (PVDF), Polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO), polrvinyl chloride (PVC), polyacrylonitrile (PAN), polyacetylene, polyaniline, polythiophene, weight average molecular weight is 50000-1000000, preferably 100000-800000；Described hydroxyl dispersant is at least one of following substances：Glucose, sucrose, citric acid, sodium alginate, Carboxymethyl cellulose, hydroxypropyl cellulose, gelatin, starch, shitosan, alginic acid, further preferably carboxymethyl cellulose and alginic acid； Preferably, step 1) in the mass ratio of silica flour and carbon source be (1-8)：(2-9), preferably (3-7)：(3-7), specially 3：7、4： 6、5：5、6：4、7：3；The mass concentration sum aoxidizing sub- silicon in described solution with inorganic carbon source is 1-50%；Described polymer adds Plus agent ratio is to aoxidize the 1-20% of sub- silicon and inorganic carbon source gross mass, described hydroxyl dispersive agent ratio can be the sub- silicon of oxidation and nothing The 10-50% of machine carbon source gross mass；Most preferably, described polymeric additive is polyacrylonitrile (PAN)；Described hydroxyl dispersant simultaneously For carboxymethyl cellulose.
5. the preparation method according to one of claim 3-4 is it is characterised in that step 2) described in viscosity in temperature be Test under 293K, viscosity can be 1-1000mPa s, preferably 100-500mPa s；Step 4) described in graphite be stone One of ink or several：Scaly graphite, aphanitic graphite, expanded graphite, Delanium, native graphite；Step 5) in institute State suitable particle diameter and be 0.5-30 μm, preferably 1.5-25 μm；Step 6) described spheroidization device be air-flow vortex balling machine, wherein Classifying turbine rotating speed is 500-6000rpm, and interior wheel speed is 3000-6600rpm；Step 8) described in non-oxidizing atmosphere by Following at least one gases provide：Nitrogen, argon, helium, described sintering temperature is 400-1200 DEG C, preferably 450-1000 DEG C, programming rate is 1-15 DEG C/min, preferably 1-5 DEG C/min, and sintering time is 1-15h, preferably 2-6h.
6. the preparation-obtained negative pole of one of the anode material described in any one of claim 1-2 or claim 3-5 Composite as the application of battery electrode material, especially as the application of lithium ion battery negative material.
7. a kind of energy storage elements it is characterised in that：Containing the anode material described in any one of claim 1-2 or The preparation-obtained anode material of one of claim 3-5.
8. a kind of portable electric appts it is characterised in that：Usage right requires the energy storage elements described in 7.
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