CN106410177B - A kind of elliposoidal SiOx/ graphite cathode composite materials and its preparation method and application - Google Patents
A kind of elliposoidal SiOx/ graphite cathode composite materials and its preparation method and application Download PDFInfo
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- CN106410177B CN106410177B CN201610976258.4A CN201610976258A CN106410177B CN 106410177 B CN106410177 B CN 106410177B CN 201610976258 A CN201610976258 A CN 201610976258A CN 106410177 B CN106410177 B CN 106410177B
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- 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
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- 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
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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
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- 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
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- 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 provides a kind of elliposoidal SiOx/ graphite cathode composite materials for using graphite and the sub- silicon of oxidation to be prepared for raw material and its preparation method and application.The method uses graphite and the sub- silicon block of oxidation using slurry drying and elliposoidal technology, and finally to effectively reduce specific surface area for raw material using cladding, advantageously form stable SEI films；Since the good scattered and rational cavity of the sub- silicon of oxidation makes material circulation excellent performance.
Description
Technical field
The present invention relates to a kind of elliposoidal SiOx/ graphite cathode composite material, more particularly to elliposoidal SiOx/ graphite cathode
Application of the composite material as height ratio capacity lithium ion battery negative material.
Background technology：
Lithium ion battery have it is higher than energy, self discharge is small, service life is long, green non-pollution outstanding advantages of it is wide
General is applied in portable electronic products and electric automobile.With the development and progress of society, lithium ion battery further should
With there is an urgent need for improving energy density, the electrode material for developing height ratio capacity is one of effective way.
In negative material, mainly carbon material commercialized at present, its theoretical specific capacity is relatively low, about 372mAhg-1.And silicon is because having high theoretical specific capacity (about 3579mAhg-1) and receive more and more attention, it is considered as most to have
One of material of graphite cathode may be substituted.It is huge but silicon can produce about 300% volume change during Li insertion extraction
Volume change the dusting 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 smaller than pure silicon material, its bulk effect in battery charge and discharge process is opposite
Smaller (about 200%), therefore, aoxidizes sub- silicon materials and is easier to break through limitation, realize commercialization early.It is industrial most common
SiOx(0<x<2) material is exactly to aoxidize sub- silicon, SiOxIt is a kind of binary phase materials, SiOxBy particle diameter it is minimum (<Amorphous Si 1nm)
And SiO2Composition.SiOxStructure can be adjusted by the simple means such as heat treatment, ball milling and etching.By in protective atmosphere
Under to SiOxSiO can be promoted by carrying out heat treatmentxGeneration disproportionated reaction, forms Si and SiO2Two-phase.In general, SiOxAt 800 DEG C
Original impalpable structure is kept below；When temperature rises to 900~1000 DEG C, SiOxDisproportionated reaction takes place；With
Temperature continues to rise, SiOxDisproportionation it is obvious all the more, the crystal grain of Si simple substance is also gradually grown up.The generation of disproportionated 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 electro-chemical activity is lost.Therefore the control for sintering temperature is also a problem.
Therefore, inventor devises a kind of excellent scheme, and the program using the technique of slurry drying, realizes SiO firstx
Fine dispersion and fixation, further using air-flow vortex micro mist reshaping technology, using graphite spheroidization equipment, using suitable
Carburizing temperature prepares the elliposoidal SiO that cycle efficieny is higher first and cycle performance is excellentx/ graphite cathode composite material.
The content of the invention
Present invention aims at pass through rational structure design and preparation method, there is provided one kind is sub- using graphite and oxidation
Silicon prepares elliposoidal SiO for raw materialxThe method of/graphite cathode composite material, and its performance is studied.The present invention is first
The technique dried using slurry, realizes SiOxFine dispersion and fixation, further using air-flow vortex micro mist reshaping technology, warp
Cavity structure can be compressed later by crossing air-flow vortex shaping, so as to improve the tap density of material, and use graphite nodule
Shape equipment, the elliposoidal that cycle efficieny is higher first and cycle performance is excellent is prepared using suitable carburizing temperature
SiOx/ graphite cathode composite material.
Present invention firstly provides a kind of elliposoidal SiOx/ graphite cathode composite material, the wherein SiO of the composite materialxContent
For 30-80%, carbon content 20-70%, 0<x<2, wherein, carbon material mainly based on graphitized carbon, is present in sphere
Portion, particle surface are amorphous carbon, it is characterised in that the complex microsphere is equally distributed ellipsoidal particle, and average diameter is
3-25 μm, tap density is more than 0.8.
It is further preferred that the cavity volume accounts for the 20-80% of elliposoidal composite material, it is preferable that 40-50%.
It is further preferred that the grain diameter meets：1.5≤(D90-D10)/D50≤2, BET specific surface area for (8 ±
5) m2·g-1。
It is further preferred that the average diameter of particles is 7-23 μm, 1.5≤(D90-D10)/D50≤2, BET compare surface
Product is (5 ± 2) m2·g-1。
Further object of the present invention is to provide the elliposoidal SiOxThe application of/graphite cathode composite material.
Application provided by the present invention is elliposoidal SiOx/ graphite cathode composite material should 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 material, including it is as follows：
After step 1) will aoxidize sub- silica flour ball mill grinding, inorganic carbon source is added, weight average molecular weight is 50000-1000000's
Polymeric additive, hydroxyl dispersant continue ball milling, obtain uniformly mixed slurry；
Mixture obtained by step 1) is added suitable solvent, mechanical agitation by step 2), and suitable viscosity is arrived in adjusting；
The suitable sample of viscosity obtained by step 3), is dried processing, obtains solid state powder A；
It for the graphite of 50-325 mesh is raw material that step 4), which uses particle diameter, adds raw materials into air-flow vortex pulverizing mill and is refined
Processing；
Graphite after step 4) refinement is isolated the solid powder B of appropriate particle size by step 5) using cyclone separation system；
B obtained by the obtained powders A of step 3) and step 5) after mixing, is added spheroidization device, nodularization by step 6)
After a certain period of time, the oxidation Asia silicon and carbon elliposoidal composite material of appropriate particle size are obtained using cyclone separator；
Step 7) is coated elliposoidal composite material obtained by step 6), and cladding uses graphite；
The solid particle that step 7) obtains is obtained ellipsoid by step 8) in inert non-oxidizing property atmosphere high temperature carbonization treatment
Shape SiOx/ graphite cathode composite material；
Preferably, it is 20nm-10mm that sub- silicon is aoxidized described in step 1)；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, mesocarbon microspheres, graphene, carbon nanotubes；Institute
Polymeric additive is stated as at least one of following substances：Phenolic resin, pitch, polyvinylidene fluoride (PVDF), polyethylene
Pyrrolidones (PVP), polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO), polyvinyl chloride (PVC), polyacrylonitrile (PAN), poly- second
Alkynes, polyaniline, polythiophene, weight average molecular weight are preferably 100000-800000；
Preferably, hydroxyl dispersant described in step 1) is at least one of following substances：Glucose, sucrose, citric acid,
Sodium alginate, carboxymethyl cellulose, hydroxypropyl cellulose, gelatin, starch, chitosan, alginic acid.
Preferably, silica flour and the mass ratio of inorganic carbon source are (1-9) in step 1)：(9-1), is preferably (2-8)：(8-2),
Concretely 2：8、3：7、4：6、5：5、6：4、7：3、8：2；The sum of mass concentration of silica flour and inorganic carbon source can in the slurry
For 1~50%；The polymeric additive ratio is the 1~20% of silica flour and inorganic carbon source gross mass, the hydroxy compounds
Dispersive agent ratio is the 10~50% of silica flour and inorganic carbon source gross mass.
Preferably, solvent described in step 2) is following one or several kinds：Water, methanol, ethanol, acetone, benzene, chloroform
Deng；Viscosity is tested in the case where temperature is 293K, and viscosity can be 1-1000mPas, is preferably 100-500mPas.
Preferably, drying proposal described in step 3) uses one kind in following scheme：Forced air drying, is dried under reduced pressure, is cold
Lyophilized dry, spray drying；Drying temperature is no more than 200 DEG C, and the value, Δ x of x changes is less than 5%, and controls material oxidation degree,
Avoid introducing unnecessary oxygen.
Preferably, graphite described in step 4) is the one or several kinds in graphite：Scaly graphite, cryptocrystalline stone
Ink, expanded graphite, Delanium, native graphite.
Preferably, suitable particle diameter described in step 5) is 0.5-30 μm, is preferably 1.5-25 μm.
Preferably, the step 6) spheroidization device is air-flow vortex balling machine, and wherein classifying turbine rotating speed is 500-
6000rpm, internal lobe wheel speed are 3000-6600rpm.
Preferably, non-oxidizing atmosphere described in step 8) is provided by following at least one gases：Nitrogen, argon gas, helium,
The sintering temperature is 400-1200 DEG C, is preferably 450-1000 DEG C, and programming rate is 1-15 DEG C/min, preferably 1-5 DEG C/
Min, sintering time 1-15h, are preferably 2-6h.
Preferably, the polymeric additive is polyacrylonitrile (PAN)；The hydroxyl dispersant is carboxymethyl cellulose at the same time
Element.
Further object of the present invention is to provide the elliposoidal SiOx/ graphite cathode composite materials that preceding method is prepared.
In addition, also providing the application for the elliposoidal SiOx/ graphite cathode composite materials that preceding method is prepared, the application is ellipsoid
Application of the shape SiOx/ graphite cathodes composite material as battery electrode material, especially as lithium ion battery negative material
Using.
In addition, the present invention also provides a kind of energy storage elements, the energy storage elements contain preceding method and are prepared into
The elliposoidal SiOx/ graphite cathode composite materials arrived, the preferred lithium ion battery of the energy storage elements.
The present invention also provides a kind of portable electric appts, the electronic equipment is ellipse using being prepared containing preceding method
The above-mentioned energy storage elements of spherical SiO x/ graphite cathode composite materials, the preferred mobile phone of the portable electric appts, photograph
Camera, video camera, MP3, MP4, laptop.
Compared with prior art, the present invention uses graphite and the sub- silicon block of oxidation to be dried for raw material using slurry
Shaping 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.It can be compressed cavity structure after air-flow vortex shaping, from
And the tap density of material is improved, and specific surface area is finally effectively reduced using cladding, advantageously form stable SEI films；
Since the good scattered and rational cavity of the sub- silicon of oxidation makes material circulation excellent performance.
Brief description of the drawings
Fig. 1 is the electron scanning micrograph of 5 gained elliposoidal SiOx/ graphite cathode composite materials of embodiment.
Fig. 2 is survey of the obtained elliposoidal SiOx/ graphite cathodes composite material of embodiment 9 under 100mA/g current densities
Try data.
Fig. 3 is that the section of 5 gained elliposoidal SiOx/ graphite cathode composite materials of embodiment characterizes, using focused ion beam
Material is processed.
Embodiment
The present invention is further described with reference to specific embodiment, the present invention is not limited to following case study on implementation.
Test method described in following embodiments, is conventional method unless otherwise specified；The reagent and material, such as
Without specified otherwise, can obtain from commercial channels.
Embodiment 1
Prepare elliposoidal SiOx/ graphite cathode composite materials
Step 1)：After the oxidation Asia silica flour ball mill grinding of particle diameter 1mm, granularity is 300nm or so after crushing, sub- by oxidation
Silicon：Graphite=2：8 mass ratio mixing, using water as solvent, PAN is polymeric additive, weight average molecular weight 300000, sucrose
For hydroxyl dispersant, for the quality of PAN polymeric additives to aoxidize the 3% of sub- silicon and graphite gross mass, the quality of sucrose is oxygen
Change the 10% of sub- silicon and graphite gross mass, ball milling obtains uniformly mixed slurry；
Step 2)：Suitable quantity of water is added, more than 5h is stirred at room temperature, obtains the slurry that viscosity is 200m Pas；
Step 3)：Slurry is subjected to spray drying treatment, treatment temperature is 150 DEG C, obtains powders A；
Step 4)：Native graphite is crushed using air-flow vortex pulverizing mill and carries out micronization processes, the grain of the native graphite
Footpath is 100 mesh；
Step 5)：Graphite after step 4) is refined isolates the solid powder B of appropriate particle size using cyclone separation system；
Step 6)：By powders A：B=8：Added after 2 uniform mixing in balling machine, wherein classifying turbine rotating speed is
4000rpm, internal lobe wheel speed are 6500rpm, and elliposoidal compound is obtained by shaping in 20 minutes；
Step 7)：The elliposoidal compound is coated using graphite coat scheme, solid phase method for coating, add 8% drip
Blue or green powder, forms uniform compound.
Step 8)：The compound is sintered for 450 DEG C in nitrogen atmosphere, heating rate is 5 DEG C/min, sinters 6h, finally
Arrive elliposoidal SiOx/ graphite cathode composite materials.
The characterization of elliposoidal composite material：
The particle diameter of the Si-C composite material obtained under above-mentioned condition is detected with Japan Electronics scanning electron microscope (JEOL-6700F)
And size distribution, the results showed that for the size distribution of Si-C composite material than more uniform, particle diameter (is shown in Table 1) between 1~20 μm, institute
State and measure the material tap density with powder tap density instrument and be more than 0.80g/cm3It is shown in Table 1.
The Electrochemical Characterization of elliposoidal SiOx/ graphite cathode composite materials：
Elliposoidal SiOx/ graphite cathodes composite material, acetylene black and the sodium carboxymethylcellulose that will be prepared in embodiment 1
(binding agent) is with mass ratio 80：10：10 mixing are made into slurry, are homogeneously applied to obtain electrode diaphragm in copper foil current collector.With
Metal lithium sheet is used as to electrode, and microporous polypropylene membrane (Celgard 2400) is used as membrane, and (solvent is volume to 1mol/L LiPF6
Than for 1：1 ethylene carbonate and dimethyl carbonate mixed liquor, wherein the vinylidene carbonic ester of addition 5%, 2% carbonic acid is sub-
Vinyl acetate) electrolyte is used as, button cell is assembled into the glove box of argon gas protection, carries out charge-discharge test, test program
For 100mA/g, charging/discharging voltage section is 0.01~1.0V, and cell testing results are listed in table 1-2.
Embodiment 2
Embodiment 2 and embodiment 1 difference lies in：
The sub- silicon of oxidation in step 1)：Graphite=4：6 mass ratioes, the particle diameter for aoxidizing sub- silicon is 5mm, and material particle size is after crushing
1μm；
Slurry viscosity obtained by step 2) is 100mPas；
The particle diameter of the step 4) native graphite is 300 mesh.
Cathode, anode, electrolyte and the battery of battery assemble same as Example 1, the sub- silicon of gained oxidation and carbon electrode material
The composition of material and the test result of battery are listed in table 1-2.
Embodiment 3
Embodiment 3 and embodiment 1 difference lies in：
Graphite is replaced with carbon nanotubes in step 1), aoxidizes sub- silicon：Carbon nanotubes=6：4 mass ratioes, aoxidize the grain of sub- silicon
Footpath is 5mm, and material particle size is 1 μm after crushing；
Slurry viscosity obtained by step 2) is 100mPas；
Step 3) the drying means, which uses, to be dried under reduced pressure；Temperature is less than 180 DEG C；
The particle diameter of the step 4) native graphite is 300 mesh.
The characterization of the sub- silicon of oxidation and carbon composite is same as Example 1.
Cathode, anode, electrolyte and the battery of battery assemble same as Example 1, the sub- silicon of gained oxidation and carbon electrode material
The composition of material and the test result of battery are listed in table 1-2.
Embodiment 4
Embodiment 4 and embodiment 1 difference lies in：
Polyacrylonitrile (PAN) is replaced with phenolic resin in step 1), the weight average molecular weight of phenolic resin is 700000；
Slurry is freeze-dried by step 3), obtains powders A.
The characterization of the sub- silicon of oxidation and carbon composite is same as Example 1.
Cathode, anode, electrolyte and the battery of battery assemble same as Example 1, the sub- silicon of gained oxidation and carbon electrode material
The composition of material and the test result of battery are listed in table 1-2.
Embodiment 5
Embodiment 5 and embodiment 1 difference lies in：
Polyacrylonitrile (PAN) is replaced with polyvinyl alcohol in step 1)；
Step 6) is by powders A：B=6：Added after 4 uniform mixing in balling machine, wherein classifying turbine rotating speed is 1000rpm,
Internal lobe wheel speed is 3500rpm, and elliposoidal compound is obtained by shaping in 40 minutes.
The characterization of the sub- silicon of oxidation and carbon composite is same as Example 1.
Cathode, anode, electrolyte and the battery of battery assemble same as Example 1, the sub- silicon of gained oxidation and carbon electrode material
The composition of material and the test result of battery are listed in table 1-2.
Embodiment 6
Embodiment 6 and embodiment 1 difference lies in：
Polyacrylonitrile (PAN) is replaced with polyvinyl alcohol in step 1)；
Step 6) is by powders A：B=4：Added after 6 uniform mixing in balling machine, wherein classifying turbine rotating speed is 4000rpm,
Internal lobe wheel speed is 6500rpm, and elliposoidal compound is obtained by shaping in 40 minutes.
The characterization of the sub- silicon of oxidation and carbon composite is same as Example 1.
Cathode, anode, electrolyte and the battery of battery assemble same as Example 1, the sub- silicon of gained oxidation and carbon electrode material
The composition of material and the test result of battery are listed in table 1-2.
Embodiment 7
Embodiment 7 and embodiment 1 difference lies in：
Polyacrylonitrile (PAN) is replaced with polyaniline in step 1)；Hydroxyl dispersant is carboxymethyl cellulose；The sub- silicon of oxidation：Stone
Ink=8：2 mass ratioes
Step 6) is by powders A：B=2：Added after 8 uniform mixing in balling machine, wherein classifying turbine rotating speed is 4000rpm,
Internal lobe wheel speed is 6500rpm, and elliposoidal compound is obtained by shaping in 40 minutes.
The characterization of the sub- silicon of oxidation and carbon composite is same as Example 1.
Cathode, anode, electrolyte and the battery of battery assemble same as Example 1, the sub- silicon of gained oxidation and carbon electrode material
The composition of material and the test result of battery are listed in table 1-2.
Embodiment 8
Embodiment 8 and embodiment 1 difference lies in：
Polyacrylonitrile (PAN) is replaced with polyaniline in step 1)；Hydroxyl dispersant is carboxymethyl cellulose；The sub- silicon of oxidation：Stone
Ink=8：2 mass ratioes
Step 3) the drying means, which uses, to be dried under reduced pressure；Temperature is less than 180 DEG C；
Step 6) is by powders A：B=2：Added after 8 uniform mixing in balling machine, wherein classifying turbine rotating speed is 4000rpm,
Internal lobe wheel speed is 6500rpm, and elliposoidal compound is obtained by shaping in 40 minutes；
Step 8) 600 DEG C of sintering in nitrogen atmosphere by the compound, heating rate is 5 DEG C/min, sinters 6h, finally
To elliposoidal SiOx/ graphite cathode composite materials.
The characterization of the sub- silicon of oxidation and carbon composite is same as Example 1.
Cathode, anode, electrolyte and the battery of battery assemble same as Example 1, the sub- silicon of gained oxidation and carbon electrode material
The composition of material and the test result of battery are listed in table 1-2.
Embodiment 9
Embodiment 9 and embodiment 1 difference lies in：
Polyacrylonitrile (PAN) is replaced with polyaniline in step 1)；Hydroxyl dispersant is carboxymethyl cellulose；
Step 3) the drying means, which uses, to be dried under reduced pressure；Temperature is less than 180 DEG C；
Step 6) is by powders A：B=4：Added after 6 uniform mixing in balling machine, wherein classifying turbine rotating speed is 4000rpm,
Internal lobe wheel speed is 6500rpm, and elliposoidal compound is obtained by shaping in 40 minutes；
Step 8) 750 DEG C of sintering in nitrogen atmosphere by the compound, heating rate is 5 DEG C/min, sinters 6h, finally
To elliposoidal SiOx/ graphite cathode composite materials.
The characterization of the sub- silicon of oxidation and carbon composite is same as Example 1.
Cathode, anode, electrolyte and the battery of battery assemble same as Example 1, the sub- silicon of gained oxidation and carbon electrode material
The composition of material and the test result of battery are listed in table 1-2.
Embodiment 10
Embodiment 10 and embodiment 1 difference lies in：
Polyacrylonitrile (PAN) is replaced with polyaniline in step 1), 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) is by powders A：B=2：Added after 8 uniform mixing in balling machine, wherein classifying turbine rotating speed is 4000rpm,
Internal lobe wheel speed is 6500rpm, and elliposoidal compound is obtained by shaping in 40 minutes；
Step 8) 900 DEG C of sintering in nitrogen atmosphere by the compound, heating rate is 5 DEG C/min, sinters 6h, finally
To elliposoidal SiOx/ graphite cathode composite materials.
The characterization of the sub- silicon of oxidation and carbon composite is same as Example 1.
Cathode, anode, electrolyte and the battery of battery assemble same as Example 1, the sub- silicon of gained oxidation and carbon electrode material
The composition of material and the test result of battery are listed in table 1-2.
Embodiment 11
Embodiment 11 and embodiment 1 difference lies in：
Polyacrylonitrile (PAN) is replaced with polyaniline in step 1), 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) is by powders A：B=2：Added after 8 uniform mixing in balling machine, wherein classifying turbine rotating speed is 4000rpm,
Internal lobe wheel speed is 6500rpm, and elliposoidal compound is obtained by shaping in 40 minutes；
Step 8) 1000 DEG C of sintering in nitrogen atmosphere by the compound, heating rate is 5 DEG C/min, sinters 6h, finally
Arrive elliposoidal SiOx/ graphite cathode composite materials.
The characterization of the sub- silicon of oxidation and carbon composite is same as Example 1.
Cathode, anode, electrolyte and the battery of battery assemble same as Example 1, the sub- silicon of gained oxidation and carbon electrode material
The composition of material and the test result of battery are listed in table 1-2.
Embodiment 12
Embodiment 12 and embodiment 1 difference lies in：
Polyacrylonitrile (PAN) is replaced with polyaniline in step 1), 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) is by powders A：B=2：Added after 8 uniform mixing in balling machine, wherein classifying turbine rotating speed is 5000rpm,
Internal lobe wheel speed is 6500rpm, and elliposoidal compound is obtained by shaping in 40 minutes；
Step 8) 1200 DEG C of sintering in nitrogen atmosphere by the compound, heating rate is 5 DEG C/min, sinters 6h, finally
Arrive elliposoidal SiOx/ graphite cathode composite materials.
The characterization of the sub- silicon of oxidation and carbon composite is same as Example 1.
Cathode, anode, electrolyte and the battery of battery assemble same as Example 1, the sub- silicon of gained oxidation and carbon electrode material
The composition of material and the test result of battery are listed in table 1-2.
Comparative example 1
Sub- Si powder will be aoxidized, is directly used as electrode material.
The characterization of the electrode material is same as Example 1.
Cathode, anode, electrolyte and the battery of battery assemble same as Example 1, the composition and electricity of the electrode obtained material
The test result in pond is listed in table 1-2.
Comparative example 2
After sub- silica flour ball mill grinding will be aoxidized, by the sub- silicon of oxidation：Graphite=2：8 mass ratio mixing, using water as solvent,
PAN is polymeric additive, and weight average molecular weight 300000, sucrose is hydroxyl dispersant, and the quality of PAN polymeric additives is
The 3% of the sub- silicon of oxidation and graphite gross mass, to aoxidize the 10% of sub- silicon and graphite gross mass, ball milling is mixed the quality of sucrose
Uniform slurry；
Suitable quantity of water is added, more than 5h is stirred at room temperature, obtains the slurry that viscosity is 200mPas.
Slurry is spray-dried, inlet temperature is 180 DEG C, which is sintered for 450 DEG C in nitrogen atmosphere,
Heating rate is 5 DEG C/min, sinters 6h, and final arrives SiOx/ graphite cathode composite materials.
The characterization of the composite material is same as Example 1.
Cathode, anode, electrolyte and the battery of battery assemble same as Example 1, the composition and electricity of the electrode obtained material
The test result in pond is listed in table 1-2.
Comparative example 3
After sub- silica flour ball mill grinding will be aoxidized, by the sub- silicon of oxidation：Graphite=4：6 mass ratio mixing, using water as solvent,
PAN is polymeric additive, and weight average molecular weight 300000, sucrose is hydroxyl dispersant, and more than 5h is stirred at room temperature, obtains
Viscosity is the slurry of 200mPas.Slurry is spray-dried, inlet temperature is 180 DEG C, obtains powders A.Using air-flow
Vortex pulverizing mill crushes native graphite and cyclonic separation obtains powder B.By powders A：B=4：It is after 6 uniformly mix, this is compound
Thing 300 DEG C of sintering in nitrogen atmosphere, heating rate is 5 DEG C/min, sinters 6h, and final arrives SiOx/ graphite cathode composite woods
Material.
The characterization of the sub- silicon of oxidation and carbon composite is same as Example 1.
Cathode, anode, electrolyte and the battery of battery assemble same as Example 1, the sub- silicon of gained oxidation and carbon electrode material
The composition of material and the test result of battery are listed in table 1-2.
Comparative example 4
After sub- silica flour ball mill grinding will be aoxidized, by the sub- silicon of oxidation：Graphite=4：6 mass ratio mixing, PAN add for polymer
Add agent, add in balling machine, wherein classifying turbine rotating speed is 4000rpm, and internal lobe wheel speed is 6500rpm, whole by 20 minutes
Shape obtains elliposoidal compound.The compound is sintered for 1200 DEG C in nitrogen atmosphere, heating rate is 5 DEG C/min, sinters 6h,
Final arrives SiOx/ graphite cathode composite materials.
The characterization of the sub- silicon of oxidation and carbon composite is same as Example 1.
Cathode, anode, electrolyte and the battery of battery assemble same as Example 1, the sub- silicon of gained oxidation and carbon electrode material
The composition of material and the test result of battery are listed in table 1-2.
Comparative example 5
After sub- silica flour ball mill grinding will be aoxidized, by the sub- silicon of oxidation：Graphite=4：6 mass ratio mixing, PAN add for polymer
Add agent, add in balling machine, wherein classifying turbine rotating speed is 4000rpm, and internal lobe wheel speed is 6500rpm, whole by 20 minutes
Shape obtains elliposoidal compound.The elliposoidal compound is coated using graphite coat scheme, by the compound in nitrogen atmosphere
In 1200 DEG C sintering, heating rate be 5 DEG C/min, sinter 6h, finally arrives elliposoidal SiOx/ graphite cathode composite materials.
The characterization of the sub- silicon of oxidation and carbon composite is same as Example 1.
Cathode, anode, electrolyte and the battery of battery assemble same as Example 1, the sub- silicon of gained oxidation and carbon electrode material
The composition of material and the test result of battery are listed in table 1-2.
Comparative example 6
Comparative example 6 and embodiment 1 difference lies in：
Polyacrylonitrile (PAN) is replaced with polyaniline in step 1), the weight average molecular weight of phenolic resin is 700000；Hydroxyl disperses
Agent is alginic acid；
Step 6) is by powders A：B=4：Added after 6 uniform mixing in balling machine, wherein classifying turbine rotating speed is 4000rpm,
Internal lobe wheel speed is 6500rpm, and elliposoidal compound is obtained by shaping in 40 minutes；
Without the cladding process of step (7)
Step 8) 1200 DEG C of sintering in nitrogen atmosphere by the compound, heating rate is 5 DEG C/min, sinters 6h, finally
Arrive elliposoidal SiOx/ graphite cathode composite materials.
The composition of table 1 embodiment 1-12 and comparative example 1-6 and/structural parameters
The performance parameter of table 2 embodiment 1-12 and comparative example 1-5
Claims (9)
1. a kind of elliposoidal SiOx/ graphite cathode composite materials, the wherein SiO of the composite materialxContent is 30-80%, carbon content
For 20-70%, 0<x<2, wherein, carbon material mainly based on graphitized carbon, is present in ball interior, and particle surface is amorphous
Carbon, it is characterised in that the complex microsphere is equally distributed ellipsoidal particle, and average diameter is 3-25 μm, and particle has cavity
Structure, tap density are more than 0.80g/cm3, also, the composite material is prepared via a method which：
Step 1), after the sub- silica flour ball mill grinding of oxidation, adds inorganic carbon source, weight average molecular weight is the poly- of 50000-1000000
Compound additive, hydroxyl dispersant continue ball milling, obtain uniformly mixed slurry；
Step 2), adds suitable water, mechanical agitation, suitable viscosity is arrived in adjusting by the mixture obtained by step 1)；
Step 3), the suitable sample of gained viscosity, carries out spray drying treatment, obtains solid state powder A；
Step 4), it for the graphite of 50-325 mesh is raw material to use particle diameter, adds raw materials into air-flow vortex pulverizing mill and carries out at refinement
Reason；
Step 5), the graphite after step 4) is refined isolate the solid powder B of appropriate particle size using cyclone separation system；
Step 6), adds air-flow vortex apparatus for shaping by B obtained by the obtained powders A of step 3) and step 5) after mixing,
Shaping obtains the oxidation Asia silicon and carbon elliposoidal composite material of appropriate particle size after a certain period of time, using cyclone separator；
Step 7), elliposoidal composite material obtained by step 6) is coated；
Step 8), elliposoidal is obtained by the solid particle that step 7) obtains in inert non-oxidizing property atmosphere high temperature carbonization treatment
SiOx/ graphite cathode composite materials,
Wherein described polymeric additive is polyaniline, and the hydroxyl dispersant is carboxymethyl cellulose.
2. the graphite cathode composite material of elliposoidal SiOx/ described in claim 1, it is characterised in that the grain diameter meets：
The average diameter of particles is 7-23 μm, and 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 materials according to one of claim 1-2, specific steps
It is as follows：
Step 1), after the sub- silica flour ball mill grinding of oxidation, adds inorganic carbon source, weight average molecular weight is the poly- of 50000-1000000
Compound additive, hydroxyl dispersant continue ball milling, obtain uniformly mixed slurry；
Step 2), adds suitable water, mechanical agitation, suitable viscosity is arrived in adjusting by the mixture obtained by step 1)；
Step 3), the suitable sample of gained viscosity, carries out spray drying treatment, obtains solid state powder A；
Step 4), it for the graphite of 50-325 mesh is raw material to use particle diameter, adds raw materials into air-flow vortex pulverizing mill and carries out at refinement
Reason；
Step 5), the graphite after step 4) is refined isolate the solid powder B of appropriate particle size using cyclone separation system；
Step 6), adds air-flow vortex apparatus for shaping by B obtained by the obtained powders A of step 3) and step 5) after mixing,
Shaping obtains the oxidation Asia silicon and carbon elliposoidal composite material of appropriate particle size after a certain period of time, using cyclone separator；
Step 7), elliposoidal composite material obtained by step 6) is coated；
Step 8), elliposoidal is obtained by the solid particle that step 7) obtains in inert non-oxidizing property atmosphere high temperature carbonization treatment
SiOx/ graphite cathode composite materials,
Wherein described polymeric additive is polyaniline, and the hydroxyl dispersant is carboxymethyl cellulose..
4. preparation method according to claim 3, it is 8nm-10mm that sub- silicon is aoxidized wherein described in step 1)；After grinding
Material particle size is 10nm-3 μm, and the inorganic carbon source is selected from following at least one：Delanium, native graphite, intermediate-phase carbon are micro-
Ball, graphene, carbon nanotubes；Silica flour and the mass ratio of carbon source are (3-7) in step 1)：(3-7)；Sub- silicon is aoxidized in the solution
It is 1-50% with the sum of the mass concentration of inorganic carbon source；The polymeric additive ratio is the sub- silicon of oxidation and the total matter of inorganic carbon source
The 1-20% of amount, the hydroxyl dispersive agent ratio are the sub- silicon of oxidation and the 10-50% of inorganic carbon source gross mass.
5. preparation method according to claim 3, it is characterised in that viscosity described in step 2) is surveyed in the case where temperature is 293K
Examination, is 100-500mPas；Graphite described in step 4) is the one or several kinds in following graphite：Scaly graphite, cryptocrystalline
Graphite, expanded graphite, Delanium, native graphite；Suitable particle diameter described in step 5) is 1.5-25 μm.
6. any one of the claim 1-2 any one of them anode material or claim 3-5 preparation method obtains
Application of the anode material arrived as battery electrode material.
7. the application described in claim 6, wherein the battery electrode material is lithium ion battery negative material.
A kind of 8. energy storage elements, it is characterised in that：Containing claim 1-2 any one of them anode material or
The anode material that any one of the claim 3-5 preparation methods obtain.
A kind of 9. portable electric appts, it is characterised in that：Energy storage elements described in usage right requirement 8.
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