CN103647056B - SiOx based composite negative electrode material, preparation method and battery - Google Patents

SiOx based composite negative electrode material, preparation method and battery Download PDF

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CN103647056B
CN103647056B CN201310628520.2A CN201310628520A CN103647056B CN 103647056 B CN103647056 B CN 103647056B CN 201310628520 A CN201310628520 A CN 201310628520A CN 103647056 B CN103647056 B CN 103647056B
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sio
methods
negative pole
composite negative
base composite
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CN103647056A (en
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岳敏
余德馨
李胜
任建国
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BTR New Material Group Co Ltd
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Shenzhen BTR New Energy Materials 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/36—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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 relates to a high-capacity SiOx based composite negative electrode material, a preparation method and a battery, wherein the negative electrode material comprises a silicon oxide material, a carbon material and an amorphous carbon coating layer; the silicon oxide material is silicon oxide or silicon oxide material modified in a carbon coating manner; surfaces of carbon material particles are coated with the silicon oxide material. A preparation method of the high-capacity SiOx based composite negative electrode material comprises the steps of performing physical processing or carbon coating modification on a silicon oxide raw material, thus obtaining a micron-sized silicon oxide material; and then mechanically fusing, coating with a solid phase and sintering at a high temperature to obtain the high-capacity negative electrode material. Through the high-capacity SiOx based composite negative electrode material, the effect of uniform dispersing and coating of the micron-sized silicon oxide particles on the surfaces of the carbon material particles can be achieved by virtue of the combination of mechanical fusion and solid-phase coating processes. The silicon oxide particles are well dispersed on the surface of the carbon material particle; the strength of bonding between the silicon oxide particles and the carbon material particles is high; the recycling performance of the material can be greatly improved; and meanwhile, the high-capacity SiOx based composite negative electrode material is high in first efficiency (breaking through the theoretical efficiency of SiOx), low in expansion rate, long in service life, environmental-friendly, pollution-free and low in cost.

Description

A kind of SiOXBase composite negative pole material, preparation method and battery
Technical field
The present invention relates to lithium ion battery negative material field, in particular it relates to a kind of new SiOx base is combined Negative material and preparation method thereof, and the lithium ion battery using this negative material.
Background technology
The lithium ion battery of prior art preparation mainly adopts graphite-like material with carbon element as negative electrode active material, such as：Artificial Graphite, native graphite, MCMB etc..However, this class carbon negative pole material is through itself modification of material over more than 20 years such as Multiphase cladding, doping etc. carry out battery process optimization, and its practice capacity is close to the theoretical specific capacity (372mAh/ of material G), pole piece limit compacted density is less than 1.8g/cm3So that its volume energy density has reached certain limit, it is difficult to there is breakthrough again Property lifting.So, traditional pure graphite-like material with carbon element is gradually difficult to meet the requirement of electronics miniaturization, high-energy-density.
Silicon as lithium ion battery negative material, its theoretical specific capacity value be 4200mAh/g, become replacement native graphite with A kind of material of the great potential of Delanium.However, the ion cathode material lithium of silicon materials preparation is deposited in charge and discharge process Volumetric expansion (about 300%) active particle efflorescence can be caused, and then lose electrical contact and lead to capacity rapid decay.Oxidation Silicon materials are although its theoretical specific capacity is less than pure silicon material, but its bulk effect in battery charge and discharge process is relatively small (about 200%), therefore, silica material is easier to break through restriction, realizes commercialization early.
CN 103219504 A discloses a kind of lithium ion battery silicon monoxide composite cathode material and preparation method thereof, This negative material is by mass percentage by 10%～30% composite particulate material and 70～90% native graphites or Delanium group Become, composite particulate material is the silicon monoxide being coated with CNT and agraphitic carbon clad.Using traditional VC in this invention Hybrid mode makes SiO/C granule and graphite material bad dispersibility, simultaneously the two bond strength low so that cycle performance is poor；And CVD growth CNT can make that material is more excessive than table, and coulombic efficiency is low first, and existing stage application is more difficult.
CN 102593426 A discloses a kind of preparation method of lithium battery silicon carbon anode material, contains nanometer including synthesis Silicon dioxide microsphere (the SiO of silica flourxMicrosphere), by SiOxMicrosphere mixes carbonization after cladding with cold primer-oil.This invention also discloses The SiO that the method is obtainedx/ C microsphere and Delanium fusion form the ion cathode material lithium obtaining.Though employing in this invention Simple fusion, but the SiO of micro-sphere structurex/C(D50=12 ± 2 μm) with graphite material because contacting and can not form clad structure, two Be that single dispersing, bond strength are low between person, material circulation poor performance, be simultaneously used to actual bodily harm larger material (as pyridine, third Ketone, toluene, oxolane) etc., environmental pollution is big, and material coulombic efficiency is larger compared with conventional graphite gap first, by existing rank The positive electrode of section coupling limits it is difficult to industrialization is used.
Therefore, develop that a kind of high power capacity, cycle performance are excellent, coulombic efficiency is high first, eco-friendly negative material is The technical barrier of art.
Content of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of SiOxBase composite negative pole material, institute The volume energy density stating negative material is high, cycle performance is excellent, coulombic efficiency is high first, environmental friendliness.
SiO of the present inventionxBase composite negative pole material comprises silica material, material with carbon element and amorphous c coating layer, institute State silica material and be wrapped in carbon material particles surface, described amorphous c coating layer is outermost clad, wherein, described oxidation Silicon materials are silicon oxide (SiOx) or the silicon oxide (SiO after coated modified carbonx/C).
Preferably, described SiOxSiO in base composite negative pole materialxContent is 0～60.0wt%, and reversible specific capacity is 360.0 ～1200.0mAh/g is adjustable；Described SiOxContent can for such as 1wt%, 2wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 56wt%, 57wt%, 58wt% Or 59wt% etc..
Preferably, 0.5≤x≤1.5.
Preferably, described SiOxThe median particle diameter of base composite negative pole material is 10.0～45.0 μm, more preferably 10 ～35.0 μm, particularly preferably 13.0～25.0 μm.
Preferably, described SiOxThe specific surface area of base composite negative pole material is 1.0～15.0m2/ g, particularly preferably 2.0～ 6.0m2/g.
Preferably, described SiOxThe powder body compacted density of base composite negative pole material is 1.0～2.0g/cm3, particularly preferably 1.2～1.8g/cm3.
Preferably, described SiOxBase composite negative pole material magnetic foreign body (Fe, Cr, Ni, Zn) total amount is below 0.1ppm.
Preferably, described SiOxImpurity Fe in base composite negative pole material<30.0ppm、Co<5.0ppm、Cu<5.0ppm、 Ni<5.0ppm、Al<10.0ppm、Cr<5.0ppm、Zn<5.0ppm、Ca<5.0ppm、Mn<5.0ppm.
Preferably, described silica material is micron order；Preferably, the median particle diameter (D of described silica material50) be 1.0～10.0 μm, more preferably 1.0～8.0 μm, particularly preferably 1.0～6.0 μm.
Preferably, described silica material granule is non-spherical, particularly preferably irregular pattern.
Preferably, in described silica material, silicon particle grain size is 1.0～100.0nm, more preferably 1.0～ 50.0nm, particularly preferably 1.0～30.0nm.
Preferably, in described silica material, carbon content is below 30.0wt%, particularly preferably below 20.0wt%.
Preferably, described silica material specific surface area is 1.0～15.0m2/ g, powder body compacted density is 0.5～1.8g/ cm3.
Preferably, described silica material magnetic foreign body (Fe, Cr, Ni, Zn) total amount is less than 0.1ppm.
Preferably, described silica material impurity Fe<20.0ppm、Co<5.0ppm、Cu<5.0ppm、Ni<5.0ppm、 Al<10.0ppm、Cr<5.0ppm、Zn<5.0ppm、Ca<5.0ppm、Mn<5.0ppm.
Preferably, described material with carbon element is the combination of a kind or at least 2 kinds in soft carbon, hard carbon or graphite；Preferably, described Graphite is Delanium, the combination of a kind in native graphite or MCMB or at least two or more arbitrary proportion.
Preferably, described material with carbon element phosphorus content is not less than 99.0%.
Preferably, the median particle diameter of described material with carbon element is 8.0～25.0 μm, particularly preferably 10.0～20.0 μm.
Preferably, described silica material and the mass ratio of material with carbon element are 1:1～1:99, more preferably 1:3～1: 49, particularly preferably 1:4～1:24.
Described amorphous c coating layer cracks carbon for organic carbon source；Described organic carbon source be can Pintsch process carbon containing organic Any one in thing.
Preferably, described amorphous c coating layer accounts for SiOx0.1～50.0wt% of base composite negative pole material, for example 0.2wt%, 0.3wt%, 0.5wt%, 1wt%, 2wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 46wt%, 47wt%, 48wt%, 49wt% etc..
The second object of the present invention is to provide a kind of lithium ion battery, and described lithium ion battery comprises of the present invention SiOxBase composite negative pole material.
The third object of the present invention is to provide a kind of described SiOxThe preparation method of base composite negative pole material, including following Step：
(1) silica material and material with carbon element are carried out mechanical fusion process, obtain presoma I material；
(2) presoma I material is carried out by solid phase cladding process using organic carbon source, obtain presoma II material；
(3) presoma II material at high temperature is sintered, obtain composite.
Preferably, carry out after step (3)：(4) composite that step (3) obtains is pulverized, sieved and remove magnetic, in obtaining Value particle diameter is 10.0～45.0 μm of SiOxBase composite negative pole material.
The described raw silicon oxide material of step (1), is that nano-silicon particle is dispersed to the particle constituting in amorphous silicon oxide, adopts It is obtained with state of the art.
Preferably, the preparation method of the described silica material of step (1) includes：By raw silicon oxide material (that is, SiOx) carry out Physical Processing or coated modified carbon, obtain silica material；Preferably, described Physical Processing includes：Raw silicon oxide material is pulverized, Screening, except magnetic obtains the silicon oxide particle that median particle diameter is 1.0～10.0 μm；Preferably, described pulverize as ball milling, comminution by gas stream Or the combination of a kind or at least 2 kinds of mechanical activation comminution；Preferably, described coated modified carbon includes：Raw silicon oxide material is carried out physics Processing obtains the silicon oxide particle that median particle diameter is 0.1～10.0 μm, then carries out carbon coating, heat treatment, pulverizing, screening, removes It is 1.0～10.0 μm of silica materials that magnetic obtains median particle diameter；Preferably, described raw silicon oxide material is dispersed to for nano-silicon particle The particle constituting in amorphous silicon oxide；Preferably, described nano-silicon particle crystallite dimension is 1.0～100.0nm, further It is preferably 1.0～50.0nm, particularly preferably 1.0～30.0nm；Preferably, described carbon coating is solid phase cladding, liquid phase coating Or a kind in gas phase cladding；Carbon source used by described carbon coating be can any one in the carbonaceous organic material of Pintsch process, preferably 1 kind in saccharide, esters, hydro carbons, organic acid or high molecular polymer or at least 2 kinds of combination, more preferably polychlorostyrene second Alkene, polyvinyl butyral resin, polyacrylonitrile, polyacrylic acid, Polyethylene Glycol, polypyrrole, polyaniline, sucrose, glucose, Fructus Hordei Germinatus 1 kind in sugar, citric acid, Colophonium, furfural resin, epoxy resin, phenolic resin, methane, ethylene or acetylene or at least 2 kinds of group Close；Preferably, the heat treatment process of described coated modified carbon is carried out under protective gas；Preferably, described protective gas For the combination of a kind in nitrogen, helium, neon, argon, Krypton, xenon or hydrogen or at least 2 kinds, particularly preferably nitrogen, helium 1 kind in gas, argon or hydrogen or at least 2 kinds of combination；Preferably, described shield gas flow rate is 0.5～10.0L/min, More preferably 0.5～5.0L/min, particularly preferably 1.0～4.0L/min；Preferably, at the heat of described coated modified carbon The heating rate of reason process be 20.0 DEG C/below min, more preferably 1.0～15.0 DEG C/min, particularly preferably 2.0～ 10.0℃/min；Preferably, the temperature of the heat treatment process of described coated modified carbon is 500.0～1150.0 DEG C, excellent further Elect 600.0～1050.0 DEG C as, particularly preferably 750.0～1000.0 DEG C；Preferably, described coated modified carbon is heat treated The temperature retention time of journey is at least 0.5h, more preferably 0.5～20.0h, particularly preferably 1.0～10.0h；Preferably, institute After the completion of stating the heat treatment process of coated modified carbon, naturally cool to room temperature.
Preferably, the described mechanical fusion of step (1) processes and includes：Silica material and material with carbon element are added to fusion machine In, regulation rotating speed is 500.0～3000.0r/min, and cutter gap width is 0.05～0.5cm, merges at least 0.5h, before obtaining Drive body I material；Preferably, described rotating speed is 800.0～2000.0r/min；Preferably, described cutter gap width be 0.1～ 0.3cm；Preferably, described time of fusion is 0.5～10.0h, particularly preferably 1.0～3.0h.
In mechanofusion process, silicon oxide particle and material with carbon element are placed in close gap, and be constantly squeezed power With the effect of shearing force, in the presence of frictional force, silicon oxide and carbon material particles contact interface can reach a kind of mechanical fusion shape State, so that silicon oxide particle is while carbon material particles apparent height disperses, keeps the combination of height between the two.
Preferably, step (2) described solid phase cladding processes and includes：Presoma I material and organic carbon source are added to VC high In effect mixer, cladding processes at least 0.5h, obtains presoma II material.
Preferably, the described organic carbon source of step (2) is powder, median particle diameter (D50) it is 0.5～20.0 μm, particularly preferably For 1.0～5.0 μm.
The described organic carbon source of step (2) is can any one in the carbonaceous organic material of Pintsch process；Preferably, step (2) Described organic carbon source is the combination of a kind or at least 2 kinds in saccharide, esters, hydro carbons, organic acid or high molecular polymer, enters one Step is preferably polrvinyl chloride, polyvinyl butyral resin, sucrose, glucose, maltose, citric acid, Colophonium, furfural resin, epoxy 1 kind in resin or phenolic resin or at least 2 kinds of combination.
Preferably, the mass ratio of step (2) described presoma I material and organic carbon source is 1:2～1:19, particularly preferably 1:3～1:19.
During VC solid phase cladding, by the collective effect in storehouse in the stirring paddle of high-speed rotation and taper by organic carbon Source power and presoma I material mixing material, by the top of bottom belt to hybrid chamber, return when it reaches top again Fall mixing bunker center, such repetitive process can reach a quick, efficient, mixed effect for good dispersion；Stirring paddle simultaneously Press close to storehouse in taper, carbon source powder and presoma I material are constantly placed in the close gap of the two during VC solid phase cladding In, there is identical effect with fusion process in step (1) so that carbon source powder can disperse well and be attached to presoma I material Material particle surface.
Preferably, the described sintering of step (3) is carried out under protective gas；Preferably, described protective gas be nitrogen, 1 kind in helium, neon, argon, Krypton, xenon or hydrogen or at least 2 kinds of combination, particularly preferably nitrogen, helium, argon Or a kind in hydrogen or at least 2 kinds of combination；Preferably, described shield gas flow rate is 0.5～10.0L/min, excellent further Elect 0.5～5.0L/min, particularly preferably 1.0～4.0L/min as.
Preferably, programming rate during the described sintering of step (3) is 20.0 DEG C/below min, more preferably 1.0～ 15.0 DEG C/min, particularly preferably 2.0～10.0 DEG C/min.
Preferably, the described sintering temperature of step (3) is 500.0～1150.0 DEG C, more preferably 600.0～1050.0 DEG C, particularly preferably 750.0～1000.0 DEG C.
Preferably, the described sintering time of step (3) is at least 0.5h, more preferably 0.5～20.0h, particularly preferably For 1.0～10.0h.
Preferably, after the completion of the described sintering of step (3), naturally cool to room temperature.
Silicon oxide particle can be fixed on carbon through high temperature sintering, organic carbon source cracking carbon-coating by presoma II material effectively Material granule surface, greatly improves the bond strength of silicon oxide particle and carbon material particles contact interface；This carbon-coating will simultaneously Silicon oxide particle and carbon material particles are wrapped in inside it, serve good conduction and buffering effect, are defined well with this Conductive network and cushioning frame, can be kept well in charge and discharge process, thus significantly lifted material circulation Performance.
SiO of the present inventionxBase composite negative pole material prepares lithium ion battery using following methods：By negative material, conductive agent With binding agent by mass percentage (91～94):(1～3):Their dissolvings are mixed, are coated on Copper Foil collection by (3～6) in a solvent On fluid, vacuum drying, prepared cathode pole piece；Then by the anode pole piece of traditional maturation process preparation, electrolyte, barrier film, outer Shell adopts conventional production process to assemble lithium ion battery；Described conductive agent is the excellent carbons material of optional electrical conductivity；Described viscous Knot agent is polyimide resin, acrylic resin, polyvinylidene fluoride, polyvinyl alcohol, sodium carboxymethyl cellulose or butadiene-styrene rubber 1 kind or at least 2 kinds of combination；The positive electrode active materials that described anode pole piece adopts are the ternary material of commercial type, richness Lithium material, cobalt acid lithium, lithium nickelate, spinel lithium manganate, layer dress LiMn2O4 or LiFePO4 etc.；Described lithium ion battery species is Conventional aluminum hull, box hat or Soft Roll lithium rechargeable battery.
Compared with prior art, SiO of the present inventionxBase composite negative pole material is mutually tied with solid phase coating technology using mechanical fusion The mode closed is successfully realized micron order silicon oxide particle carbon material particles surface is dispersed and covered effect, silicon oxide Grain carbon material particles Dispersion on surface is good, the two bond strength is high, greatly improves cycle performance (1000 circulations of material Capability retention is more than 80%)；And first efficiency high (>90% breakthrough SiOxTheoretical efficiency), low thermal expansion is (with graphite-phase When), the long-life, simultaneously in the whole preparation process of this negative material, environmental friendliness is pollution-free, low cost；Can be actual preferential Apply to high-end consumption electronic product, break single conventional graphite class negative material market on the market.
Brief description
Fig. 1 is the electron microscopic picture of presoma I material in the embodiment of the present invention 1；
Fig. 2 is the electron microscopic picture of composite negative pole material in the embodiment of the present invention 1；
Fig. 3 is the section picture of composite negative pole material in the embodiment of the present invention 1；
Fig. 4 is the XRD figure of composite negative pole material in the embodiment of the present invention 1；
Fig. 5 is the composite negative pole material cycle performance curve of the embodiment of the present invention 1.
Specific embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that described reality Apply example to be only to aid in understanding the present invention, be not construed as the concrete restriction to the present invention.
Embodiment 1
SiO raw material is milled to the silicon oxide particle that median particle diameter is 0.1～5.0 μm, it is pressed quality with phenolic resin Ratio 90:10 dispersions in ethanol, are dried；It is subsequently placed in tunnel cave, under argon protective gas environment, flow is 2.0L/ Min, is warming up to 1150.0 DEG C with 1 DEG C/min heating rate, and constant temperature 0.5h naturally cools to room temperature, then uses jet mill Pulverize, 325 mesh sieves are got median particle diameter and are 1.0～5.0 μm, carbon content is 0.5～5.0% silica material；
Above-mentioned prepared silica material and carbon content are not less than 99.0%, median particle diameter natural for 8.0～20.0 μm Graphite powder in mass ratio 1：19 add to fusion machine, merge 0.5h, obtain presoma I material；
Presoma I material and median particle diameter are 0.5～5.0 μm of asphalt powder in mass ratio 1:9 are added to VC efficiently mixes In conjunction machine, mixing cladding processes 0.5h, obtains presoma II material；
Presoma II material is placed in tunnel cave, under argon and hydrogen gaseous mixture environmental protection, flow is 1.0L/min, It is warming up to 1050.0 DEG C with 10.0 DEG C/min heating rate, constant temperature 0.5h, naturally cool to room temperature, then use mechanical crusher powder Broken, 200 mesh sieves get the composite negative pole material of 10.0～35.0 μm of median particle diameter.
Embodiment 2
By SiO1.5Raw material is milled to the silicon oxide particle that median particle diameter is 0.1～2.0 μm, and it is pressed quality with citric acid Ratio 70:30 dispersions in ethanol, are dried；It is subsequently placed in tunnel cave, under argon protective gas environment, flow is 10.0L/ Min, is warming up to 500.0 DEG C with 20.0 DEG C/min heating rate, and constant temperature 20.0h naturally cools to room temperature, then uses comminution by gas stream Machine is pulverized, 325 mesh sieves are got median particle diameter and are 1.0～10.0 μm, and carbon content is 5.0～20.0% silica materials；
Above-mentioned prepared silica material and carbon content are not less than 99.0%, median particle diameter artificial for 8.0～20.0 μm Graphite powder in mass ratio 1：3 add to fusion machine, merge 3.0h, obtain presoma I material；
Presoma I material and median particle diameter are 0.5～5.0 μm of glucose powder in mass ratio 1:1 to be added to VC efficient In mixer, cladding processes 1.0h, obtains presoma II material；
Presoma II material is placed in tunnel cave, under argon and hydrogen gaseous mixture environmental protection, flow is 2.0L/min, It is warming up to 1050.0 DEG C with 10.0 DEG C/min heating rate, constant temperature 0.5h, naturally cool to room temperature, then use mechanical crusher powder Broken, 200 mesh sieves get the composite negative pole material of 10.0～35.0 μm of median particle diameter.
Embodiment 3
By SiO0.5Raw material is milled to the silicon oxide particle that median particle diameter is 1.0～10.0 μm, the silicon oxide being then obtained Granule and carbon content are not less than 99.0%, median particle diameter for 15.0～25.0 μm of carbonaceous mesophase spherules in mass ratio 1：99 add to In fusion machine, merge 10.0h, obtain presoma I material；
Presoma I material and median particle diameter are 5.0～10.0 μm of Phenolic resin powder in mass ratio 1:49 are added to VC In high efficient mixer, mixing cladding processes 1.0h, obtains presoma II material；
Presoma II material is placed in tunnel cave, under nitrogen environmental protection, flow be 0.5L/min, with 20.0 DEG C/ Min heating rate is warming up to 1150.0 DEG C, and constant temperature 0.5h naturally cools to room temperature, then with mechanical crusher pulverizing, 200 mesh Screening obtains the composite negative pole material that median particle diameter is 10.0～40.0 μm.
Embodiment 4
By SiO1.1Raw material is milled to the silicon oxide particle that median particle diameter is 1.0～10.0 μm, is placed in rotary furnace and is passed through first Alkane gas, at 600.0 DEG C, gas phase cladding 2.0h, is then followed by being placed in tunnel cave, under nitrogen protective gas environment, stream Measure as 0.5L/min, be warming up to 1000.0 DEG C with 5.0 DEG C/min heating rate, constant temperature 2.0h, naturally cool to room temperature, Ran Houyong Jet mill is pulverized, 325 mesh sieves are got median particle diameter and are 1.0～10.0 μm, and carbon content is 5.0～10.0% silicon oxide materials Material；
It is 15.0～25.0 μm of soft carbons that above-mentioned prepared silica material and carbon content are not less than 99.0%, median particle diameter Material in mass ratio 1：1 adds to fusion machine, merges 0.5h, obtains presoma I material；
Presoma I material and median particle diameter are 5.0～10.0 μm of citric acid powders in mass ratio 1:15 are added to VC height In effect mixer, cladding processes 2.0h, obtains presoma II material；
Presoma II material is placed in tunnel cave, under argon environmental protection, flow be 1.5L/min, with 5.0 DEG C/ Min heating rate is warming up to 500.0 DEG C, and constant temperature 20.0h naturally cools to room temperature, then with mechanical crusher pulverizing, 200 mesh Screening obtains the composite negative pole material that median particle diameter is 10.0～45.0 μm.
Embodiment 5
By SiO1.0Raw material is milled to the silicon oxide particle that median particle diameter is 1.0～10.0 μm, and it is pressed quality with citric acid Ratio 90:10 dispersions in ethanol, are dried；It is subsequently placed in tunnel cave, under argon protective gas environment, flow is 2.0L/ Min, is warming up to 750.0 DEG C with 1.0 DEG C/min heating rate, and constant temperature 0.5h naturally cools to room temperature, then uses jet mill Pulverize, 325 mesh sieves are got median particle diameter and are 1.0～10.0 μm, carbon content is 0.5～5.0% silica material；
Above-mentioned prepared silica material and carbon content are not less than 99.0%, median particle diameter natural for 8.0～20.0 μm Graphite powder in mass ratio 1：3 add to fusion machine, merge 0.5h, obtain presoma I material；
Presoma I material and median particle diameter are 0.5～5.0 μm of asphalt powder in mass ratio 1:9 are added to VC efficiently mixes In conjunction machine, cladding processes 2.0h, obtains presoma II material；
Presoma II material is placed in tunnel cave, under argon and hydrogen gaseous mixture environmental protection, flow is 2.0L/min, It is warming up to 1050.0 DEG C with 10.0 DEG C/min heating rate, constant temperature 1.5h, naturally cool to room temperature, then use mechanical crusher powder Broken, 200 mesh sieves get the composite negative pole material of 10.0～35.0 μm of median particle diameter.
Comparative example 1
Technique same as Example 2 manufactures silica material, and the silica material being obtained and carbon content are not less than 99.0%th, median particle diameter is 8.0～20.0 μm of graphous graphite powders in mass ratio 1：3 add to fusion machine, fusion 0.5h, and 200 Mesh sieve gets the composite negative pole material that median particle diameter is 10.0～30.0 μm.
Comparative example 2
Technique same as Example 4 manufactures silica material, then silica material and carbon content are not less than 99.0%, Median particle diameter is 15～25.0 μm of soft carbon materials in mass ratio 1：3, using prior art such as VC mixer mix homogeneously, 200 mesh Screening obtains the composite negative pole material that median particle diameter is 10.0～30.0 μm.
Using following methods, the negative material of embodiment 1～5 and comparative example 1～2 is tested：
Powder body compacted density of the present invention adopts CARVER powder-compacting machine to test, wherein, powder body compacted density= The volume of the quality/test sample of test sample；Pole piece compaction density=(negative pole tablet quality-Copper Foil quality)/(pole-piece area × Thickness after pole piece compacting).
Using the full-automatic specific surface area of the Tristar3000 of Micromeritics Instrument Corp. U.S.A and lacunarity analysis instrument test material Specific surface area.
Average grain using Malvern laser particle analyzer MS 2000 test material particle size range and feed particles Footpath.
Using X-ray diffractometer X ' Pert Pro, the structure of PANalytical test material.
Using the surface topography of Hitachi, Ltd S4800 sem observation sample, granular size etc..
Test electrochemistry cycle performance using following methods：By negative material, conductive agent and binding agent by mass percentage 94：1：Their dissolvings are mixed by 5 in a solvent, control solid content 50%, are coated in copper foil current collector, vacuum drying, system Obtain cathode pole piece；Then by the LiPF of the tertiary cathode pole piece of traditional maturation process preparation, 1mol/L6/EC+DMC+EMC(v/v =1:1:1) electrolyte, Celgard2400 barrier film, shell adopt conventional production process to assemble 18650 cylinder cells.Cylinder The charge-discharge test of battery on Wuhan Jin Nuo Electronics Co., Ltd. LAND battery test system, in normal temperature condition, 0.2C constant current Discharge and recharge, charging/discharging voltage is limited in 2.75～4.2V.
The Electrochemical results of the negative material prepared by embodiment 1-5 and comparative example 1-2 are as shown in table 1.
Table 1
From above experimental result, the negative material of the method for the invention preparation has excellent chemical property, Stable circulation.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment, But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention, The interpolation of the equivalence replacement to each raw material of product of the present invention and auxiliary element, selection of concrete mode etc., all fall within the present invention's Within the scope of protection domain and disclosure.

Claims (78)

1. a kind of SiOxBase composite negative pole material, comprises silica material, material with carbon element and amorphous c coating layer, described silicon oxide Material is wrapped in carbon material particles surface, and described amorphous c coating layer is outermost clad, and wherein, described silica material is Silicon oxide after coated modified carbon；Described silica material is 1 with the mass ratio of material with carbon element:1～1:99, described silicon oxide material The median particle diameter of material is 1.0～10.0 μm, and the median particle diameter of described material with carbon element is 8.0～25.0 μm；In described silica material Carbon content is below 30.0wt%, 0.5≤x≤1.5.
2. SiO as claimed in claim 1xBase composite negative pole material is it is characterised in that described SiOxIn base composite negative pole material SiOxContent is 1～60.0wt%, and reversible specific capacity is adjustable in 360.0～1200.0mAh/g.
3. SiO as claimed in claim 1xBase composite negative pole material is it is characterised in that described SiOxBase composite negative pole material Median particle diameter is 10.0～45.0 μm.
4. SiO as claimed in claim 3xBase composite negative pole material is it is characterised in that described SiOxBase composite negative pole material Median particle diameter is 10.0～35.0 μm.
5. SiO as claimed in claim 4xBase composite negative pole material is it is characterised in that described SiOxBase composite negative pole material Median particle diameter is 13.0～25.0 μm.
6. SiO as claimed in claim 1xBase composite negative pole material is it is characterised in that described SiOxBase composite negative pole material Specific surface area is 1.0～15.0m2/g.
7. SiO as claimed in claim 6xBase composite negative pole material is it is characterised in that described SiOxBase composite negative pole material Specific surface area is 2.0～6.0m2/g.
8. SiO as claimed in claim 1xBase composite negative pole material is it is characterised in that described SiOxBase composite negative pole material Powder body compacted density is 1.0～2.0g/cm3.
9. SiO as claimed in claim 8xBase composite negative pole material is it is characterised in that described SiOxBase composite negative pole material Powder body compacted density is 1.2～1.8g/cm3.
10. SiO as claimed in claim 1xBase composite negative pole material is it is characterised in that described SiOxBase composite negative pole material magnetic Property foreign body Fe, Cr, Ni, Zn total amount be below 0.1ppm.
11. SiO as claimed in claim 1xBase composite negative pole material is it is characterised in that described SiOxIn base composite negative pole material Impurity Fe<30.0ppm、Co<5.0ppm、Cu<5.0ppm、Ni<5.0ppm、Al<10.0ppm、Cr<5.0ppm、Zn< 5.0ppm、Ca<5.0ppm、Mn<5.0ppm.
12. SiO as claimed in claim 1xBase composite negative pole material is it is characterised in that the median particle diameter of described silica material For 1.0～8.0 μm.
13. SiO as claimed in claim 12xBase composite negative pole material is it is characterised in that the intermediate value grain of described silica material Footpath is 1.0～6.0 μm.
14. SiO as claimed in claim 1xBase composite negative pole material is it is characterised in that described silica material granule is aspheric Shape.
15. SiO as claimed in claim 14xBase composite negative pole material is it is characterised in that described silica material granule is not Regular pattern.
16. SiO as claimed in claim 1xBase composite negative pole material it is characterised in that in described silica material silicon particle brilliant Grain size is 1.0～100.0nm.
17. SiO as claimed in claim 16xBase composite negative pole material is it is characterised in that silicon particle in described silica material Grain size is 1.0～50.0nm.
18. SiO as claimed in claim 17xBase composite negative pole material is it is characterised in that silicon particle in described silica material Grain size is 1.0～30.0nm.
19. SiO as claimed in claim 1xBase composite negative pole material it is characterised in that in described silica material carbon content be Below 20.0wt%.
20. SiO as claimed in claim 1xBase composite negative pole material is it is characterised in that described silica material specific surface area is 1.0～15.0m2/ g, powder body compacted density is 0.5～1.8g/cm3.
21. SiO as claimed in claim 1xBase composite negative pole material is it is characterised in that described silica material magnetic foreign body Fe, Cr, Ni, Zn total amount is less than 0.1ppm.
22. SiO as claimed in claim 1xBase composite negative pole material is it is characterised in that described silica material impurity Fe< 20.0ppm、Co<5.0ppm、Cu<5.0ppm、Ni<5.0ppm、Al<10.0ppm、Cr<5.0ppm、Zn<5.0ppm、Ca< 5.0ppm、Mn<5.0ppm.
23. SiO as claimed in claim 1xBase composite negative pole material it is characterised in that described material with carbon element be soft carbon, hard carbon or 1 kind in graphite or at least 2 kinds of combination.
24. SiO as claimed in claim 23xBase composite negative pole material is it is characterised in that described graphite is Delanium, natural 1 kind in graphite or MCMB or the combination of at least two or more arbitrary proportion.
25. SiO as claimed in claim 1xBase composite negative pole material is it is characterised in that described material with carbon element phosphorus content is not less than 99.0%.
26. SiO as claimed in claim 1xBase composite negative pole material is it is characterised in that the median particle diameter of described material with carbon element is 10.0～20.0 μm.
27. SiO as claimed in claim 1xBase composite negative pole material is it is characterised in that described silica material and material with carbon element Mass ratio is 1:3～1:49.
28. SiO as claimed in claim 27xBase composite negative pole material is it is characterised in that described silica material and material with carbon element Mass ratio be 1:4～1:24.
29. SiO as claimed in claim 1xBase composite negative pole material is it is characterised in that described amorphous c coating layer accounts for SiOx 0.1～50.0wt% of base composite negative pole material.
A kind of 30. lithium ion batteries are it is characterised in that described lithium ion battery comprises SiO described in any one of claim 1-29x Base composite negative pole material.
31. one kind SiO as described in any one of claim 1-29xThe preparation method of base composite negative pole material, comprises the following steps：
(1) silica material and material with carbon element are carried out mechanical fusion process, obtain presoma I material；
(2) presoma I material is carried out by solid phase cladding process using organic carbon source, obtain presoma II material；
(3) presoma II material at high temperature is sintered, obtain composite.
32. methods as claimed in claim 31 are it is characterised in that carry out after step (3)：(4) by being combined that step (3) obtains Material disintegrating, sieve and remove magnetic, obtain the SiO that median particle diameter is 10.0～45.0 μmxBase composite negative pole material.
33. methods as claimed in claim 31 are it is characterised in that the preparation method of the described silica material of step (1) includes： By raw silicon oxide material SiOxCarry out coated modified carbon, obtain silica material.
34. methods as claimed in claim 33 are it is characterised in that described coated modified carbon includes：Raw silicon oxide material is carried out Physical Processing obtains the silicon oxide particle that median particle diameter is 0.1～10.0 μm, then carries out carbon coating, heat treatment, pulverizing, sieve Dividing, obtaining median particle diameter except magnetic is 1.0～10.0 μm of silica materials.
35. methods as claimed in claim 33 are it is characterised in that described raw silicon oxide material is dispersed to amorphous for nano-silicon particle The particle constituting in matter silicon oxide.
36. methods as claimed in claim 35 it is characterised in that described nano-silicon particle crystallite dimension be 1.0～ 100.0nm.
37. methods as claimed in claim 36 are it is characterised in that described nano-silicon particle crystallite dimension is 1.0～50.0nm.
38. methods as claimed in claim 37 are it is characterised in that described nano-silicon particle crystallite dimension is 1.0～30.0nm.
39. methods as claimed in claim 33 it is characterised in that carbon source used by described carbon coating be saccharide, esters, hydro carbons, 1 kind in organic acid or high molecular polymer or at least 2 kinds of combination.
40. methods as claimed in claim 39 are it is characterised in that carbon source used by described carbon coating is polrvinyl chloride, polyethylene Butyral, polyacrylonitrile, polyacrylic acid, Polyethylene Glycol, polypyrrole, polyaniline, sucrose, glucose, maltose, citric acid, 1 kind in Colophonium, furfural resin, epoxy resin, phenolic resin, methane, ethylene or acetylene or at least 2 kinds of combination.
41. methods as claimed in claim 34 are it is characterised in that the heat treatment process of described coated modified carbon is in protective gas Carry out under environment.
42. methods as claimed in claim 34 are it is characterised in that the heating rate of the heat treatment process of described coated modified carbon For 20.0 DEG C/below min.
43. methods as claimed in claim 42 are it is characterised in that the heating rate of the heat treatment process of described coated modified carbon For 1.0～15.0 DEG C/min.
44. methods as claimed in claim 43 are it is characterised in that the heating rate of the heat treatment process of described coated modified carbon For 2.0～10.0 DEG C/min.
45. methods as claimed in claim 34 are it is characterised in that the temperature of the heat treatment process of described coated modified carbon is 500.0～1150.0 DEG C.
46. methods as claimed in claim 45 are it is characterised in that the temperature of the heat treatment process of described coated modified carbon is 600.0～1050.0 DEG C.
47. methods as claimed in claim 46 are it is characterised in that the temperature of the heat treatment process of described coated modified carbon is 750.0～1000.0 DEG C.
48. methods as claimed in claim 34 are it is characterised in that the temperature retention time of the heat treatment process of described coated modified carbon It is at least 0.5h.
49. methods as claimed in claim 48 are it is characterised in that the temperature retention time of the heat treatment process of described coated modified carbon For 0.5～20.0h.
50. methods as claimed in claim 49 are it is characterised in that the temperature retention time of the heat treatment process of described coated modified carbon For 1.0～10.0h.
51. methods as claimed in claim 31 are it is characterised in that the described mechanical fusion of step (1) processes inclusion：By silicon oxide Material and material with carbon element add to fusion machine, regulation rotating speed be 500.0～3000.0r/min, cutter gap width be 0.05～ 0.5cm, merges at least 0.5h, obtains presoma I material.
52. methods as claimed in claim 51 are it is characterised in that described rotating speed is 800.0～2000.0r/min.
53. methods as claimed in claim 51 are it is characterised in that described cutter gap width is 0.1～0.3cm.
54. methods as claimed in claim 51 are it is characterised in that described time of fusion is 0.5～10.0h.
55. methods as claimed in claim 54 are it is characterised in that described time of fusion is 1.0～3.0h.
56. methods as claimed in claim 31 are it is characterised in that step (2) described solid phase cladding processes and includes：By presoma I material and organic carbon source are added in VC high efficient mixer, and cladding processes at least 0.5h, obtains presoma II material.
57. methods as claimed in claim 31 it is characterised in that the described organic carbon source of step (2) be powder, median particle diameter For 0.5～20.0 μm.
58. methods as claimed in claim 57 it is characterised in that the described organic carbon source of step (2) median particle diameter be 1.0～ 5.0μm.
59. methods as claimed in claim 31 it is characterised in that the described organic carbon source of step (2) be saccharide, esters, hydro carbons, 1 kind in organic acid or high molecular polymer or at least 2 kinds of combination.
60. methods as claimed in claim 59 are it is characterised in that the described organic carbon source of step (2) is polrvinyl chloride, polyethylene In butyral, sucrose, glucose, maltose, citric acid, Colophonium, furfural resin, epoxy resin or phenolic resin a kind or At least 2 kinds of combination.
61. methods as claimed in claim 31 are it is characterised in that the matter of step (2) described presoma I material and organic carbon source Amount ratio is 1:2～1:19.
62. methods as claimed in claim 61 are it is characterised in that the matter of step (2) described presoma I material and organic carbon source Amount ratio is 1:3～1:19.
63. methods as claimed in claim 31 are it is characterised in that the described sintering of step (3) is carried out under protective gas.
64. methods as described in claim 63 are it is characterised in that described protective gas is nitrogen, helium, neon, argon, krypton 1 kind in gas, xenon or hydrogen or at least 2 kinds of combination.
Method as described in 65. such as claim 64 is it is characterised in that described protective gas is in nitrogen, helium, argon or hydrogen 1 kind or at least 2 kinds of combination.
66. methods as described in claim 63 are it is characterised in that described shield gas flow rate is 0.5～10.0L/min.
67. methods as described in claim 66 are it is characterised in that described shield gas flow rate is 0.5～5.0L/min.
68. methods as described in claim 67 are it is characterised in that described shield gas flow rate is 1.0～4.0L/min.
69. methods as claimed in claim 31 it is characterised in that step (3) described sintering when programming rate be 20.0 DEG C/ Below min.
70. methods as described in claim 69 it is characterised in that programming rate during the described sintering of step (3) be 1.0～ 15.0℃/min.
71. methods as described in claim 70 it is characterised in that programming rate during the described sintering of step (3) be 2.0～ 10.0℃/min.
72. methods as claimed in claim 31 are it is characterised in that the described sintering temperature of step (3) is 500.0～1150.0 ℃.
73. methods as described in claim 72 are it is characterised in that the described sintering temperature of step (3) is 600.0～1050.0 ℃.
74. methods as described in claim 73 are it is characterised in that the described sintering temperature of step (3) is 750.0～1000.0 ℃.
75. methods as claimed in claim 31 are it is characterised in that the described sintering time of step (3) is at least 0.5h.
76. methods as described in claim 75 are it is characterised in that the described sintering time of step (3) is 0.5～20.0h.
77. methods as described in claim 76 are it is characterised in that the described sintering time of step (3) is 1.0～10.0h.
78. methods as claimed in claim 31 are it is characterised in that after the completion of the described sintering of step (3), naturally cool to room Temperature.
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