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CN103647056A - 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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Publication number
CN103647056A
CN103647056A CN201310628520.2A CN201310628520A CN103647056A CN 103647056 A CN103647056 A CN 103647056A CN 201310628520 A CN201310628520 A CN 201310628520A CN 103647056 A CN103647056 A CN 103647056A
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carbon
silicon oxide
sio
composite negative
particularly preferably
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CN103647056B (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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Priority to KR1020140088590A priority patent/KR20150062918A/en
Priority to JP2014157771A priority patent/JP6235430B2/en
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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
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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 SiO xbase composite negative pole material, preparation method and battery
Technical field
The present invention relates to lithium ion battery negative material field, particularly, the present invention relates to a kind of New Si Ox base composite negative pole material and preparation method thereof, and the lithium ion battery that uses this negative material.
Background technology
Lithium ion battery prepared by prior art mainly adopts graphite-like material with carbon element as negative electrode active material, as: Delanium, native graphite, MCMB etc.Yet this class carbon negative pole material carries out battery process optimization through material over more than 20 years self modification as heterogeneous coated, doping etc., its practice capacity has approached the theoretical specific capacity (372mAh/g) of material, and pole piece limit compacted density is less than 1.8g/cm 3, make its volume energy density reach certain limit, be difficult to have again breakthrough lifting.So traditional pure graphite-like material with carbon element is difficult to meet the requirement of electronics miniaturization, high-energy-density gradually.
Silicon is as lithium ion battery negative material, and its theoretical specific capacity value is 4200mAh/g, becomes a kind of material that has potentiality that substitutes native graphite and Delanium.Yet the volumetric expansion that ion cathode material lithium prepared by silicon materials exists in charge and discharge process (approximately 300%) can cause active particle efflorescence, and then lose and electrically contact and cause capacity to be decayed fast.Silica material, although its theoretical specific capacity is less than pure silicon material, its bulk effect in battery charge and discharge process relatively little (approximately 200%), therefore, silica material is more easily broken through restriction, realizes early commercialization.
CN103219504A discloses silicon monoxide composite negative pole material and preparation method thereof for a kind of lithium ion battery, this negative material is comprised of 10%～30% composite particulate material and 70～90% native graphites or Delanium by mass percentage, and composite particulate material is the silicon monoxide that is coated with carbon nano-tube and agraphitic carbon coating layer.In this invention, use traditional VC hybrid mode to make SiO/C particle and graphite material bad dispersibility, the two bond strength is low simultaneously, makes cycle performance poor; And CVD method carbon nano-tube can make material more excessive than table, and coulomb efficiency is low first, existing stage application is more difficult.
CN102593426A discloses a kind of preparation method of lithium battery silicon-carbon cathode material, comprises the synthetic silicon dioxide microsphere (SiO that contains nano silica fume xmicroballoon), by SiO xmicroballoon mixes coated rear carbonization with cold primer-oil.This invention also discloses the SiO that the method makes x/ C microballoon and Delanium fusion form the ion cathode material lithium obtaining.Though used simple fusion in this invention, the SiO of micro-sphere structure x/ C(D 50=12 ± 2 μ m) because contacting, can not form clad structure with graphite material, the two is that single dispersion, bond strength are low, material cycle performance is poor, used larger material of actual bodily harm (as pyridine, acetone, toluene, oxolane) etc. simultaneously, environmental pollution is large, and material first coulomb efficiency is larger compared with conventional graphite gap, limited by the positive electrode of existing stage coupling, be difficult to industrialization and use.
Therefore, develop a kind of high power capacity, cycle performance technical barrier excellent, that high, the eco-friendly negative material of coulomb efficiency is affiliated field first.
Summary of the invention
For the deficiencies in the prior art, one of object of the present invention is to provide a kind of SiO xbase composite negative pole material, the volume energy density of described negative material is high, cycle performance is excellent, high, the environmental friendliness of coulomb efficiency first.
SiO of the present invention xbase composite negative pole material comprises silica material, material with carbon element and amorphous c coating layer, and described silica material is wrapped in material with carbon element particle surface, and described amorphous c coating layer is outermost coating layer, and wherein, described silica material is silica (SiO x) or the silica (SiO after coated modified carbon x/ C).
Preferably, described SiO xsiO in base composite negative pole material xcontent is 0～60.0wt%, and reversible specific capacity is adjustable at 360.0～1200.0mAh/g; Described SiO xcontent can be 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 SiO xthe median particle diameter of base composite negative pole material is 10.0～45.0 μ m, and more preferably 10～35.0 μ m, are particularly preferably 13.0～25.0 μ m.
Preferably, described SiO xthe specific area of base composite negative pole material is 1.0～15.0m 2/ g, is particularly preferably 2.0～6.0m 2/ g.
Preferably, described SiO xthe powder body compacted density of base composite negative pole material is 1.0～2.0g/cm 3, be particularly preferably 1.2～1.8g/cm 3.
Preferably, described SiO xbase composite negative pole material magnetic foreign body (Fe, Cr, Ni, Zn) total amount is below 0.1ppm.
Preferably, described SiO ximpurity 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 in base composite negative pole material.
Preferably, described silica material is micron order; Preferably, the median particle diameter (D of described silica material 50) be 1.0～10.0 μ m, more preferably 1.0～8.0 μ m, are particularly preferably 1.0～6.0 μ m.
Preferably, described silica material particle is non-spherical, is particularly preferably irregularity pattern.
Preferably, in described silica material, silicon particle grain size is 1.0～100.0nm, and more preferably 1.0～50.0nm, is particularly preferably 1.0～30.0nm.
Preferably, in described silica material, carbon content is, below 30.0wt%, to be particularly preferably below 20.0wt%.
Preferably, described silica material specific area is 1.0～15.0m 2/ g, powder body compacted density is 0.5～1.8g/cm 3.
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 a kind or the combination of at least 2 kinds in soft carbon, hard carbon or graphite; Preferably, described graphite is a kind or at least combination of two or more arbitrary proportion in Delanium, native graphite or MCMB.
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 μ m, is particularly preferably 10.0～20.0 μ m.
Preferably, the mass ratio of described silica material and material with carbon element is 1:1～1:99, and more preferably 1:3～1:49, is particularly preferably 1:4～1:24.
Described amorphous c coating layer is organic carbon source cracking carbon; Described organic carbon source is any one in can the carbonaceous organic material of Pintsch process.
Preferably, described amorphous c coating layer accounts for SiO x0.1～50.0wt% of base composite negative pole material, such as 0.2wt%, 0.3wt%, 0.5wt%, 1wt%, 2wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 46wt%, 47wt%, 48wt%, 49wt% etc.
Two of object of the present invention is to provide a kind of lithium ion battery, and described lithium ion battery comprises SiO of the present invention xbase composite negative pole material.
Three of object of the present invention is to provide a kind of described SiO xthe preparation method of base composite negative pole material, comprises the following steps:
(1) silica material and material with carbon element are carried out to mechanical fusion treatment, obtain presoma I material;
(2) adopt organic carbon source that presoma I material is carried out to the coated processing of solid phase, obtain presoma II material;
(3) by presoma II material at high temperature sintering, obtain composite material.
Preferably, step is carried out after (3): the composite material that (4) obtain step (3) is pulverized, sieved and remove magnetic, obtains the SiO that median particle diameter is 10.0～45.0 μ m xbase composite negative pole material.
The described raw silicon oxide material of step (1), for nano-silicon particle is dispersed to the particle forming in amorphous silicon oxide, adopts state of the art to make.
Preferably, the preparation method of the described silica material of step (1) comprises: by raw silicon oxide material (that is, SiO x) carry out Physical Processing or coated modified carbon, obtain silica material; Preferably, described Physical Processing comprises: raw silicon oxide material is pulverized, sieved, except magnetic obtains the silicon oxide particle that median particle diameter is 1.0～10.0 μ m; Preferably, described pulverizing is a kind or the combination of at least 2 kinds of ball milling, air-flow crushing or mechanical crushing; Preferably, described coated modified carbon comprises: raw silicon oxide material is carried out to Physical Processing and obtain the silicon oxide particle that median particle diameter is 0.1～10.0 μ m, then carry out that carbon is coated, heat treatment, pulverizing, screening, except magnetic obtains median particle diameter, be 1.0～10.0 μ m silica materials; Preferably, described raw silicon oxide material is that nano-silicon particle is dispersed to the particle forming in amorphous silicon oxide; Preferably, described nano-silicon particle crystallite dimension is 1.0～100.0nm, and more preferably 1.0～50.0nm, is particularly preferably 1.0～30.0nm; Preferably, described carbon be coated as solid phase is coated, in coated a kind of liquid phase coating or gas phase; The coated carbon source used of described carbon is any in can the carbonaceous organic material of Pintsch process, be preferably a kind or the combination of at least 2 kinds in carbohydrate, ester class, hydro carbons, organic acid or high molecular polymer, more preferably a kind in polyvinyl chloride, polyvinyl butyral resin, polyacrylonitrile, polyacrylic acid, polyethylene glycol, polypyrrole, polyaniline, sucrose, glucose, maltose, citric acid, pitch, furfural resin, epoxy resin, phenolic resins, methane, ethene or acetylene or the combination of at least 2 kinds; Preferably, the heat treatment process of described coated modified carbon is carried out under protective gas environment; Preferably, described protective gas is a kind or the combination of at least 2 kinds in nitrogen, helium, neon, argon gas, Krypton, xenon or hydrogen, is particularly preferably a kind or the combination of at least 2 kinds in nitrogen, helium, argon gas or hydrogen; Preferably, described shield gas flow rate is 0.5～10.0L/min, and more preferably 0.5～5.0L/min, is particularly preferably 1.0～4.0L/min; Preferably, the heating rate of the heat treatment process of described coated modified carbon be 20.0 ℃/below min, more preferably 1.0～15.0 ℃/min, is 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 ℃, more preferably 600.0～1050.0 ℃, is particularly preferably 750.0～1000.0 ℃; Preferably, the temperature retention time of the heat treatment process of described coated modified carbon is 0.5h at least, and more preferably 0.5～20.0h, is particularly preferably 1.0～10.0h; Preferably, after the heat treatment process of described coated modified carbon completes, naturally cool to room temperature.
Preferably, the described mechanical fusion treatment of step (1) comprises: silica material and material with carbon element are added in fusion machine, and adjusting rotary speed is 500.0～3000.0r/min, and cutter gap width is 0.05～0.5cm, merges at least 0.5h, obtains presoma I material; Preferably, described rotating speed is 800.0～2000.0r/min; Preferably, described cutter gap width is 0.1～0.3r/min; Preferably, described time of fusion is 0.5～10.0h, is particularly preferably 1.0～3.0h.
In mechanical fusion process, silicon oxide particle and material with carbon element are placed in close gap, the effect of the power that is constantly squeezed and shearing force, under the effect of frictional force, silica and material with carbon element particle contact interface can reach a kind of mechanical molten condition, make silicon oxide particle in material with carbon element particle surface high degree of dispersion, keep the combination of height between the two.
Preferably, the coated processing of the described solid phase of step (2) comprises: presoma I material and organic carbon source are joined in VC high efficient mixer, and coated processing is 0.5h at least, obtains presoma II material.
Preferably, the described organic carbon source of step (2) is Powdered, median particle diameter (D 50) be 0.5～20.0 μ m, be particularly preferably 1.0～5.0 μ m.
The described organic carbon source of step (2) is any in can the carbonaceous organic material of Pintsch process; Preferably, the described organic carbon source of step (2) is a kind or the combination of at least 2 kinds in carbohydrate, ester class, hydro carbons, organic acid or high molecular polymer, more preferably a kind in polyvinyl chloride, polyvinyl butyral resin, sucrose, glucose, maltose, citric acid, pitch, furfural resin, epoxy resin or phenolic resins or the combination of at least 2 kinds.
Preferably, the mass ratio of step (2) described presoma I material and organic carbon source is 1:2～1:19, is particularly preferably 1:3～1:19.
In the coated process of VC solid phase, in paddle by High Rotation Speed and taper, the acting in conjunction in storehouse is brought to the top of hybrid chamber by organic carbon source powder and presoma I material composite material by bottom, when it reaches top, fall back to again mixing bunker center, so repetitive process can reach one fast, the mixed effect of efficient, good dispersion; Paddle is pressed close to storehouse in taper simultaneously, in the coated process of VC solid phase, carbon source powder and presoma I material are constantly placed in the close gap of the two, there is identical effect with fusion process in step (1), make carbon source powder can disperse well and be attached to presoma I material granule surface.
Preferably, the described sintering of step (3) carries out under protective gas environment; Preferably, described protective gas is a kind or the combination of at least 2 kinds in nitrogen, helium, neon, argon gas, Krypton, xenon or hydrogen, is particularly preferably a kind or the combination of at least 2 kinds in nitrogen, helium, argon gas or hydrogen; Preferably, described shield gas flow rate is 0.5～10.0L/min, and more preferably 0.5～5.0L/min, is particularly preferably 1.0～4.0L/min.
Preferably, programming rate during the described sintering of step (3) be 20.0 ℃/below min, more preferably 1.0～15.0 ℃/min, is particularly preferably 2.0～10.0 ℃/min.
Preferably, the described sintering temperature of step (3) is 500.0～1150.0 ℃, more preferably 600.0～1050.0 ℃, is particularly preferably 750.0～1000.0 ℃.
Preferably, the described sintering time of step (3) is 0.5h at least, and more preferably 0.5～20.0h, is particularly preferably 1.0～10.0h.
Preferably, after the described sintering of step (3) completes, naturally cool to room temperature.
Presoma II material is through high temperature sintering, and organic carbon source cracking carbon-coating can be fixed on silicon oxide particle material with carbon element particle surface effectively, has greatly promoted the bond strength of silicon oxide particle and material with carbon element particle contact interface; This carbon-coating is wrapped in its inside by silicon oxide particle and material with carbon element particle simultaneously, good conduction and buffering effect have been played, with this, formed good conductive network and buffering skeleton, in charge and discharge process, can have been kept well, thereby significantly promote the cycle performance of material.
SiO of the present invention xbase composite negative pole material adopts following methods to prepare lithium ion battery: by negative material, conductive agent and binding agent (91～94) by mass percentage: (1～3): (3～6) are dissolved in them in solvent and mix, are coated on Copper Foil collector, vacuum drying, makes cathode pole piece; Then the anode pole piece of being prepared by traditional maturation process, electrolyte, barrier film, shell adopt conventional production process assembling lithium ion battery; Described conductive agent is the carbon class material that optional conductivity is good; Described binding agent is a kind or the combination of at least 2 kinds of polyimide resin, acrylic resin, polyvinylidene fluoride, polyvinyl alcohol, sodium carboxymethylcellulose or butadiene-styrene rubber; The positive electrode active materials that described anode pole piece adopts is the ternary material of selling on the market, rich lithium material, cobalt acid lithium, lithium nickelate, spinel lithium manganate, layer dress LiMn2O4 or LiFePO4 etc.; Described lithium ion battery kind is conventional aluminum hull, box hat or Soft Roll lithium rechargeable battery.
Compared with prior art, SiO of the present invention xmachinery merges and solid phase coating technology combines the mode of adopting base composite negative pole material successfully realized micron order silicon oxide particle at material with carbon element particle surface dispersed and covered effect, silicon oxide particle is high in material with carbon element particle surface good dispersion, the two bond strength, has greatly promoted the cycle performance (1000 circulation volume conservation rates are more than 80%) of material; And high (>90% breaks through SiO to efficiency first xtheoretical efficiency), low thermal expansion (with graphite-phase when), the long-life, in the whole preparation process of this negative material, environmental friendliness is pollution-free simultaneously, cost is low; Can reality preferentially apply to high-end consumption electronic product, break single conventional graphite class negative material market on the market.
Accompanying drawing explanation
Fig. 1 is the Electronic Speculum picture of presoma I material in the embodiment of the present invention 1;
Fig. 2 is the Electronic Speculum 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.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
SiO raw material ball is milled to the silicon oxide particle that median particle diameter is 0.1～5.0 μ m, by itself and phenolic resins in mass ratio 90:10 be dispersed in ethanol, dry; Then be placed in tunnel cave, under argon shield gaseous environment, flow is 2.0L/min, with 1 ℃/min heating rate, be warming up to 1150.0 ℃, constant temperature 0.5h, naturally cool to room temperature, then with airslide disintegrating mill pulverize, 325 mesh sieves divide that to obtain median particle diameter be 1.0～5.0 μ m, carbon content is 0.5～5.0% silica material;
By the above-mentioned silica material making and carbon content be not less than 99.0%, median particle diameter be 8.0～20.0 μ m natural graphite powders in mass ratio 1:19 be added in fusion machine, merge 0.5h, obtain presoma I material;
By presoma I material and median particle diameter be 0.5～5.0 μ m asphalt powder in mass ratio 1:9 join in VC high efficient mixer, mix the coated 0.5h of processing, obtain presoma II material;
Presoma II material is placed in to tunnel cave; under argon gas and hydrogen gaseous mixture protection of the environment; flow is 1.0L/min; with 10.0 ℃/min heating rate, be warming up to 1050.0 ℃; constant temperature 0.5h; naturally cool to room temperature, then with mechanical crusher pulverizing, 200 mesh sieves, divide the composite negative pole material that obtains median particle diameter 10.0～35.0 μ m.
Embodiment 2
By SiO 1.5raw material ball is milled to the silicon oxide particle that median particle diameter is 0.1～2.0 μ m, by itself and citric acid in mass ratio 70:30 be dispersed in ethanol, dry; Then be placed in tunnel cave, under argon shield gaseous environment, flow is 10.0L/min, with 20.0 ℃/min heating rate, be warming up to 500.0 ℃, constant temperature 20.0h, naturally cool to room temperature, then with airslide disintegrating mill pulverize, 325 mesh sieves divide that to obtain median particle diameter be 1.0～10.0 μ m, carbon content is 5.0～20.0% silica materials;
By the above-mentioned silica material making and carbon content be not less than 99.0%, median particle diameter be 8.0～20.0 μ m graphous graphite powders in mass ratio 1:3 be added in fusion machine, merge 3.0h, obtain presoma I material;
By presoma I material and median particle diameter be 0.5～5.0 μ m glucose powder in mass ratio 1:1 join in VC high efficient mixer, the coated 1.0h that processes, obtains presoma II material;
Presoma II material is placed in to tunnel cave; under argon gas and hydrogen gaseous mixture protection of the environment; flow is 2.0L/min; with 10.0 ℃/min heating rate, be warming up to 1050.0 ℃; constant temperature 0.5h; naturally cool to room temperature, then with mechanical crusher pulverizing, 200 mesh sieves, divide the composite negative pole material that obtains median particle diameter 10.0～35.0 μ m.
Embodiment 3
By SiO 0.5raw material ball is milled to the silicon oxide particle that median particle diameter is 1.0～10.0 μ m, then the silicon oxide particle making and carbon content are not less than to 99.0%, median particle diameter be 15.0～25.0 μ m carbonaceous mesophase spherules in mass ratio 1:99 be added in fusion machine, merge 10.0h, obtain presoma I material;
By presoma I material and median particle diameter be 5.0～10.0 μ m phenolic resins powder in mass ratio 1:49 join in VC high efficient mixer, mix the coated 1.0h of processing, obtain presoma II material;
Presoma II material is placed in to tunnel cave; under nitrogen protection environment; flow is 0.5L/min; with 20.0 ℃/min heating rate, be warming up to 1150.0 ℃; constant temperature 0.5h; naturally cool to room temperature, then with mechanical crusher pulverizing, 200 mesh sieves, divide and obtain the composite negative pole material that median particle diameter is 10.0～40.0 μ m.
Embodiment 4
By SiO 1.1raw material ball is milled to the silicon oxide particle that median particle diameter is 1.0～10.0 μ m, be placed in rotary furnace and pass into methane gas, at 600.0 ℃, and then the coated 2.0h of gas phase, be then placed in tunnel cave, under nitrogen protection gaseous environment, flow is 0.5L/min, with 5.0 ℃/min heating rate, be warming up to 1000.0 ℃, constant temperature 2.0h, naturally cools to room temperature, then with airslide disintegrating mill pulverize, 325 mesh sieves divide that to obtain median particle diameter be 1.0～10.0 μ m, carbon content is 5.0～10.0% silica materials;
By the above-mentioned silica material making and carbon content be not less than 99.0%, median particle diameter be the soft material with carbon element of 15.0～25.0 μ m in mass ratio 1:1 be added in fusion machine, merge 0.5h, obtain presoma I material;
By presoma I material and median particle diameter be 5.0～10.0 μ m citric acid powder in mass ratio 1:15 join in VC high efficient mixer, the coated 2.0h that processes, obtains presoma II material;
Presoma II material is placed in to tunnel cave; under argon shield environment; flow is 1.5L/min; with 5.0 ℃/min heating rate, be warming up to 500.0 ℃; constant temperature 20.0h; naturally cool to room temperature, then with mechanical crusher pulverizing, 200 mesh sieves, divide and obtain the composite negative pole material that median particle diameter is 10.0～45.0 μ m.
Embodiment 5
By SiO 1.0raw material ball is milled to the silicon oxide particle that median particle diameter is 1.0～10.0 μ m, by itself and citric acid in mass ratio 90:10 be dispersed in ethanol, dry; Then be placed in tunnel cave, under argon shield gaseous environment, flow is 2.0L/min, with 1.0 ℃/min heating rate, be warming up to 750.0 ℃, constant temperature 0.5h, naturally cool to room temperature, then with airslide disintegrating mill pulverize, 325 mesh sieves divide that to obtain median particle diameter be 1.0～10.0 μ m, carbon content is 0.5～5.0% silica material;
By the above-mentioned silica material making and carbon content be not less than 99.0%, median particle diameter be 8.0～20.0 μ m natural graphite powders in mass ratio 1:3 be added in fusion machine, merge 0.5h, obtain presoma I material;
By presoma I material and median particle diameter be 0.5～5.0 μ m asphalt powder in mass ratio 1:9 join in VC high efficient mixer, the coated 2.0h that processes, obtains presoma II material;
Presoma II material is placed in to tunnel cave; under argon gas and hydrogen gaseous mixture protection of the environment; flow is 2.0L/min; with 10.0 ℃/min heating rate, be warming up to 1050.0 ℃; constant temperature 1.5h; naturally cool to room temperature, then with mechanical crusher pulverizing, 200 mesh sieves, divide the composite negative pole material that obtains median particle diameter 10.0～35.0 μ m.
Comparative example 1
Manufacture silica material with embodiment 2 same process, by the silica material making and carbon content be not less than 99.0%, median particle diameter be 8.0～20.0 μ m graphous graphite powders in mass ratio 1:3 be added in fusion machine, merge 0.5h, 200 mesh sieves divide and obtain the composite negative pole material that median particle diameter is 10.0～30.0 μ m.
Comparative example 2
Manufacture silica material with embodiment 4 same process, then silica material and carbon content are not less than to 99.0%, median particle diameter is the soft material with carbon element of 15～25.0 μ m 1:3 in mass ratio, adopt prior art to mix as VC mixer, 200 mesh sieves divide and obtain the composite negative pole material that median particle diameter is 10.0～30.0 μ m.
Adopt following methods to test the negative material of embodiment 1～5 and comparative example 1～2:
Powder body compacted density of the present invention adopts the test of CARVER powder-compacting machine, wherein, and the volume of quality/test sample of powder body compacted density=test sample; Pole piece compacted density=(negative plate quality-Copper Foil quality)/(thickness after the compacting of pole piece area * pole piece).
Adopt the full-automatic specific area of Tristar3000 of Micromeritics Instrument Corp. U.S.A and the specific area of lacunarity analysis instrument test material.
Adopt the average grain diameter of Ma Erwen laser particle analyzer MS2000 test material particle size range and feed particles.
Adopt X-ray diffractometer X ' Pert Pro, the structure of PANalytical test material.
The surface topography of the employing S4800 of Hitachi, Ltd sem observation sample, granular size etc.
Adopt following methods test electrochemistry cycle performance: by negative material, conductive agent and binding agent by mass percentage 94:1:5 they are dissolved in solvent and are mixed, control solid content 50%, be coated on Copper Foil collector, vacuum drying, make cathode pole piece; Then the tertiary cathode pole piece of being prepared by traditional maturation process, the LiPF of 1mol/L 6/ EC+DMC+EMC(v/v=1:1:1) electrolyte, Celgard2400 barrier film, shell adopt conventional production process to assemble 18650 cylinder cells.The charge-discharge test of cylindrical battery on the LAND of the Jin Nuo Electronics Co., Ltd. battery test system of Wuhan, at normal temperature condition, 0.2C constant current charge-discharge, charging/discharging voltage is limited in 2.75～4.2V.
The Electrochemical results of the negative material that embodiment 1-5 and comparative example 1-2 are prepared is as shown in table 1.
Table 1
Figure BDA0000426886180000121
Figure BDA0000426886180000131
From above experimental result, negative material prepared by the method for the invention has excellent chemical property, stable circulation.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to the selection of the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, concrete mode etc., within all dropping on protection scope of the present invention and open scope.

Claims (10)

1. a SiO xbase composite negative pole material, comprise silica material, material with carbon element and amorphous c coating layer, described silica material is wrapped in material with carbon element particle surface, and described amorphous c coating layer is outermost coating layer, wherein, described silica material is silica or the silica after coated modified carbon.
2. SiO as claimed in claim 1 xbase composite negative pole material, is characterized in that, described SiO xsiO in base composite negative pole material xcontent is 0～60.0wt%, and reversible specific capacity is adjustable at 360.0～1200.0mAh/g;
Preferably, 0.5≤x≤1.5;
Preferably, described SiO xthe median particle diameter of base composite negative pole material is 10.0～45.0 μ m, and more preferably 10.0～35.0 μ m, are particularly preferably 13.0～25.0 μ m;
Preferably, described SiO xthe specific area of base composite negative pole material is 1.0～15.0m 2/ g, is particularly preferably 2.0～6.0m 2/ g;
Preferably, described SiO xthe powder body compacted density of base composite negative pole material is 1.0～2.0g/cm 3, be particularly preferably 1.2～1.8g/cm 3;
Preferably, described SiO xbase composite negative pole material magnetic foreign body (Fe, Cr, Ni, Zn) total amount is below 0.1ppm;
Preferably, described SiO ximpurity 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 in base composite negative pole material.
3. SiO as claimed in claim 1 or 2 xbase composite negative pole material, is characterized in that, described silica material is micron order; Preferably, the median particle diameter of described silica material is 1.0～10.0 μ m, and more preferably 1.0～8.0 μ m, are particularly preferably 1.0～6.0 μ m;
Preferably, described silica material particle is non-spherical, is particularly preferably irregularity pattern;
Preferably, in described silica material, silicon particle grain size is 1.0～100.0nm, and more preferably 1.0～50.0nm, is particularly preferably 1.0～30.0nm;
Preferably, in described silica material, carbon content is below 30.0wt%, is particularly preferably below 20.0wt%;
Preferably, described silica material specific area is 1.0～15.0m 2/ g, powder body compacted density is 0.5～1.8g/cm 3;
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 a kind or the combination of at least 2 kinds in soft carbon, hard carbon or graphite; Preferably, described graphite is a kind or at least combination of two or more arbitrary proportion in Delanium, native graphite or MCMB;
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 μ m, is particularly preferably 10.0～20.0 μ m;
Preferably, the mass ratio of described silica material and material with carbon element is 1:1～1:99, and more preferably 1:3～1:49, is particularly preferably 1:4～1:24;
Preferably, described amorphous c coating layer accounts for SiO x0.1～50.0wt% of base composite negative pole material.
4. a lithium ion battery, is characterized in that, described lithium ion battery comprises SiO described in claim 1-3 any one xbase composite negative pole material.
5. a SiO as described in claim 1-3 any one xthe preparation method of base composite negative pole material, comprises the following steps:
(1) silica material and material with carbon element are carried out to mechanical fusion treatment, obtain presoma I material;
(2) adopt organic carbon source that presoma I material is carried out to the coated processing of solid phase, obtain presoma II material;
(3) by presoma II material at high temperature sintering, obtain composite material.
6. method as claimed in claim 5, is characterized in that, step is carried out after (3): the composite material that (4) obtain step (3) is pulverized, sieved and remove magnetic, obtains the SiO that median particle diameter is 10.0～45.0 μ m xbase composite negative pole material.
7. the method as described in claim 5 or 6, is characterized in that, the preparation method of the described silica material of step (1) comprises: by raw silicon oxide material (that is, SiO x) carry out Physical Processing or coated modified carbon, obtain silica material;
Preferably, described Physical Processing comprises: raw silicon oxide material is pulverized, sieved, except magnetic obtains the silicon oxide particle that median particle diameter is 1.0～10.0 μ m;
Preferably, described coated modified carbon comprises: raw silicon oxide material is carried out to Physical Processing and obtain the silicon oxide particle that median particle diameter is 0.1～10.0 μ m, then carry out that carbon is coated, heat treatment, pulverizing, screening, except magnetic obtains median particle diameter, be 1.0～10.0 μ m silica materials;
Preferably, described raw silicon oxide material is that nano-silicon particle is dispersed to the particle forming in amorphous silicon oxide; Preferably, described nano-silicon particle crystallite dimension is 1.0～100.0nm, and more preferably 1.0～50.0nm, is particularly preferably 1.0～30.0nm;
Preferably, the coated carbon source used of described carbon is a kind or the combination of at least 2 kinds in carbohydrate, ester class, hydro carbons, organic acid or high molecular polymer, more preferably a kind in polyvinyl chloride, polyvinyl butyral resin, polyacrylonitrile, polyacrylic acid, polyethylene glycol, polypyrrole, polyaniline, sucrose, glucose, maltose, citric acid, pitch, furfural resin, epoxy resin, phenolic resins, methane, ethene or acetylene or the combination of at least 2 kinds;
Preferably, the heat treatment process of described coated modified carbon is carried out under protective gas environment;
Preferably, the heating rate of the heat treatment process of described coated modified carbon be 20.0 ℃/below min, more preferably 1.0～15.0 ℃/min, is 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 ℃, more preferably 600.0～1050.0 ℃, is particularly preferably 750.0～1000.0 ℃;
Preferably, the temperature retention time of the heat treatment process of described coated modified carbon is 0.5h at least, and more preferably 0.5～20.0h, is particularly preferably 1.0～10.0h.
8. the method as described in claim 5-7 any one, it is characterized in that, the described mechanical fusion treatment of step (1) comprises: silica material and material with carbon element are added in fusion machine, adjusting rotary speed is 500.0～3000.0r/min, cutter gap width is 0.05～0.5cm, merge at least 0.5h, obtain presoma I material;
Preferably, described rotating speed is 800.0～2000.0r/min;
Preferably, described cutter gap width is 0.1～0.3r/min;
Preferably, described time of fusion is 0.5～10.0h, is particularly preferably 1.0～3.0h.
9. the method as described in claim 5-8 any one, is characterized in that, the coated processing of the described solid phase of step (2) comprises: presoma I material and organic carbon source are joined in VC high efficient mixer, and coated processing is 0.5h at least, obtains presoma II material;
Preferably, the described organic carbon source of step (2) is Powdered, and median particle diameter is 0.5～20.0 μ m, is particularly preferably 1.0～5.0 μ m;
Preferably, the described organic carbon source of step (2) is a kind or the combination of at least 2 kinds in carbohydrate, ester class, hydro carbons, organic acid or high molecular polymer, more preferably a kind in polyvinyl chloride, polyvinyl butyral resin, sucrose, glucose, maltose, citric acid, pitch, furfural resin, epoxy resin or phenolic resins or the combination of at least 2 kinds;
Preferably, the mass ratio of step (2) described presoma I material and organic carbon source is 1:2～1:19, is particularly preferably 1:3～1:19.
10. the method as described in claim 5-9 any one, is characterized in that, the described sintering of step (3) carries out under protective gas environment; Preferably, described protective gas is a kind or the combination of at least 2 kinds in nitrogen, helium, neon, argon gas, Krypton, xenon or hydrogen, is particularly preferably a kind or the combination of at least 2 kinds in nitrogen, helium, argon gas or hydrogen; Preferably, described shield gas flow rate is 0.5～10.0L/min, and more preferably 0.5～5.0L/min, is particularly preferably 1.0～4.0L/min;
Preferably, programming rate during the described sintering of step (3) be 20.0 ℃/below min, more preferably 1.0～15.0 ℃/min, is particularly preferably 2.0～10.0 ℃/min;
Preferably, the described sintering temperature of step (3) is 500.0～1150.0 ℃, more preferably 600.0～1050.0 ℃, is particularly preferably 750.0～1000.0 ℃;
Preferably, the described sintering time of step (3) is 0.5h at least, and more preferably 0.5～20.0h, is particularly preferably 1.0～10.0h;
Preferably, after the described sintering of step (3) completes, naturally cool to room temperature.
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