CN104638237A - Lithium ion battery SiO composite material as well as preparation method and application thereof - Google Patents
Lithium ion battery SiO composite material as well as preparation method and application thereof Download PDFInfo
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- CN104638237A CN104638237A CN201510026862.6A CN201510026862A CN104638237A CN 104638237 A CN104638237 A CN 104638237A CN 201510026862 A CN201510026862 A CN 201510026862A CN 104638237 A CN104638237 A CN 104638237A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- 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 lithium ion battery SiO composite material which comprises powder and a conductive carbon coating layer, wherein the chemical formula of the powder is SiOx; x is greater than 0.9 and less than 1.1; the volume of powder with particle diameters below 1.0mu m accounts for less than 15.0% of that of all the SiOx powder; D90/D10 is greater than 3.0 and less than 15.0; D90 is less than 25.0mu m; Dmax is less than 50.0mu m; and the median particle diameterD50 of the SiOx changes within 0.5-2.0mu m before and after carbon coating. When the composite material charges and discharges at 0-1.5V as a lithium ion battery cathode material, the reversible specific capacity is high (over 1,650mAh/g), the initial coulomb efficiency is up to a theoretical value (over 79.0%), and meanwhile the composite material has excellent cycle performance, excellent conductive performance and low volume expansion, is suitable for high-rate charge and discharge, and can be applied to the power market.
Description
Technical field
The invention belongs to lithium ion battery composite material field, particularly, the present invention relates to a kind of lithium ion battery and be oxidized sub-silicon composite, preparation method and its usage.
Background technology
All the time, because being oxidized the good bulk effect of sub-silicon (SiO), people attempt it can be used as lithium ion battery composite material, and it is generally acknowledged, SiO negative pole Mechanism of electrochemical behaviors of anhydrous is as follows:
SiO+Li→Li
2O+Si (1)
SiO+Li→Li
4SiO
4+Si (2)
Si+Li→Li
4.4Si (3)
When SiO is as composite material, its initial coulomb efficiency is low, mainly because first step reaction (formula 1) and (formula 2) is the Li of irreversible reaction, generation
2o, Li
4siO
4and the oxide of silicon contacts with organic electrolyte and to decompose and condensation etc. is reacted and consumed more lithium ion.
The Li generated
2o, Li
4siO
4separate out with back bone network, act as a kind of good original position buffer matrix, restrained effectively the bulk effect of active metal silicon grain in charge and discharge process; Also serve the effect of support and dispersed metal silicon accumulation regions particle simultaneously, avoid the agglomeration of small and dispersed metallic silicon accumulation regions particle in later stage charge and discharge cycles process, favourable to cyclical stability.This be also oxidized just sub-silicon (SiO) material always have an optimistic view of by people, realistic meaning becomes the soonest the topmost reason of composite material of future generation.
For oxidation sub-silicon materials, theoretical capacity and efficiency calculation as follows, assuming that:
(1) the above-mentioned reaction equation 1 and 3 of simple generation, net reaction is: SiO+6.4Li →+Li
4.4si+Li
2o; Calculating theoretical initial coulomb efficiency, first reversible specific capacity is: η
1=68.7%; Q
reversible 1=2679mAh/g;
(2) the above-mentioned reaction equation 2 and 3 of simple generation, net reaction is: 4SiO+17.2Li →+3Li
4.4si+Li
4siO
4, by theory calculate its theoretical initial coulomb efficiency, first reversible specific capacity be: η
2=76.7%; Q
reversible 2=2009mAh/g.
With regard to the SiO material of previous literature and patent report and use, capacity plays general less than 1500mAh/g, and efficiency, lower than 75.0%, also has the space of necessarily improving compared with its theoretical value; Pertinent literature report SiO material electric conductivity extreme difference simultaneously, the conductivity order of magnitude (<10 within the scope of insulator
-12s/cm).
CN 103236517A discloses a kind of lithium ion battery silicon based composite material and preparation method thereof, described lithium ion battery silicon based composite material is made up of silicon monoxide, macroscopic particles particle diameter is 10-25 μm, microstructure is the silicon nanoparticle of coated with silica, and inner silicon grain particle diameter is 20-30nm; This composite material is under 0.1C multiplying power, and discharge capacity 2010-2640mAh/g is first 420-790mAh/g after 50 circulations; In this patent, SiO material reversible capacity is less than 1500mAh/g, and efficiency is obvious less than 75% (0 ~ 2.0V) first, known under conventional 0 ~ 1.5V, efficiency can be lower, and conductivity improvement not being carried out to material, electrochemical polarization is serious, and high rate performance is poor.
CN 103441250 A discloses a kind of lithium rechargeable battery composite material, and this composite material take oxide containing silicon as raw material, fully mixes with graphite and pitch, adds conductive metal salt, prepares through high-energy ball milling and high-temperature heat treatment.Use the sub-silicon of oxidation (SiO) to obtain material for raw material in this patent of invention, though improved circulation and conductance property, reversible capacity is at 650mAh/g in left and right, and efficiency is but less than 70% first.
CN 103474631 A discloses the sub-silicon compound composite material of a kind of oxidation, and it comprises the sub-silicon substrate of oxidation, uniform deposition at the nano silicon material be oxidized on sub-silicon substrate and the nanometer conductive material coating layer being oxidized sub-silicon/nano-silicon surface.The preparation method of described oxidation sub-silicon compound composite material comprises nano-silicon chemical vapour deposition (CVD), nanometer conductive material coating modification, sieves and remove magnetic treatment.Though described oxidation sub-silicon compound composite material has improvement to a certain extent still to SiO composite material specific capacity (>1600mAh/g) and initial coulomb efficiency (>80%), the sub-silicon composite of this oxidation is on the basis of the original component structure of SiO material, artificially introduce the larger nano silicon material of volumetric expansion by the mode of physical bond at SiO particle surface, crystal grain comparatively disaster controls, and it is dispersed poor, the enormousness expansion issues that Si material itself brings can not get effective buffering and cannot avoid, and cycle performance is poor.
Therefore, for oxidation sub-silicon (SiO) material, at maintenance material system original component structure, the capacity significantly promoting it plays and initial coulomb efficiency, simultaneously improve its cycle performance and further its volumetric expansion of reduction be the technical barrier in affiliated field.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of oxidation sub-silicon composite.Described composite material is as lithium ion battery negative material discharge and recharge under 0 ~ 1.5V, reversible specific capacity high (>1650mAh/g), initial coulomb efficiency reaches theoretical value (>79.0%), and, possess excellent circulation, conductance property and low volumetric expansion simultaneously, be applicable to high rate charge-discharge, power market can be applied to.
To achieve these goals, present invention employs following technical scheme:
A kind of lithium ion battery is oxidized sub-silicon composite, and it is SiO by chemical formula
x(0.9<x<1.1) powder and conductive carbon coating layer composition; Wherein, SiO
xthe powder volume of middle particle diameter below 1.0 μm accounts for whole SiO
xless than 15.0%, 3.0<D of powder
90/ D
10<15.0, D
90<25.0 μm, D
max<50.0 μm; The coated front and back SiO of carbon
xmedian particle diameter D
50change is between 0.5 ~ 2.0 μm.
By SiO
xthe fine powder of particle diameter below 1.0 μm controls within 15.0%, can realize excellent initial coulomb efficiency and capacity plays characteristic, and result like this is owing to fine powder (<1.0 μm) SiO
xseed activity is large, and (interface Si valence state is from Si easily to introduce granular boundary oxidation in preparation section and rear end high-temperature process
2+→ Si
4+), it is unfavorable that the increase of the material monolithic oxygen content that this interface oxidation brings plays material initial coulomb efficiency and capacity.And, control 3.0<D
90/ D
10<15.0, D
90<25.0 μm, D
max<50.0 μm, narrower distribution state and bulky grain control, and can realize excellent cycle performance and more excellent bulk effect.
In addition, control SiO
xthe median particle diameter D of the coated front and back of conductive carbon
50change, at 0.5 ~ 2.0 μm, obviously can improve cyclical stability and the Volumetric expansion of material.When not destroying the coated result of top layer carbon, control to reduce SiO
xcarbon coated front and back median particle diameter D
50change, from the particle agglomeration being the reduction of in fact material, makes SiO as far as possible
xshow a monodisperse distribution state, reduce individual particle absolute volume to expand, the volumetric expansion that material is brought in charge and discharge process and mechanical stress well can be disperseed in material matrix, material electrode structure integrality in charge and discharge process have also been obtained good improvement simultaneously, thus easily can improve the cycle performance of material.
Preferably, described lithium ion battery is oxidized the BET specific surface area of sub-silicon composite is 1.0 ~ 3.0m
2/ g, such as 1.2m
2/ g, 1.4m
2/ g, 1.6m
2/ g, 1.8m
2/ g, 2.0m
2/ g, 2.2m
2/ g, 2.4m
2/ g, 2.6m
2/ g or 2.8m
2/ g.
Preferably, CuK αsource XRD determining lithium ion battery is utilized to be oxidized sub-silicon composite crystal structure, there is Si (111) characteristic peak within the scope of corresponding 2 θ=26.0 ~ 30.0 °, try to achieve Si (111) crystal face crystallite dimension between 2.0 ~ 15.0nm by Scherrer formula.
Preferably, utilize Raman spectrometer to measure lithium ion battery and be oxidized sub-silicon composite carbon coating layer architectural feature, corresponding 1345 ~ 1355cm
-1peak intensity I
dwith 1575 ~ 1595cm
-1peak intensity I
gratio I
d/ I
gbetween 0.5 ~ 2.0.
Preferably, the thickness utilizing profile scanning Electronic Speculum to record conductive carbon coating layer is 5.0 ~ 125.0nm, utilizes carbon and sulfur analytical instrument to record carbon content and accounts for the 0.5 ~ 20.0wt% being oxidized sub-silicon composite.
Preferably, 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 and Mn<5.0ppm in the sub-silicon composite of described oxidation.
Preferably, in the sub-silicon composite of described oxidation, the total amount of magnetic foreign body Fe, Cr, Ni and Zn is below 0.1ppm.
Preferably, SiO
xin powder, the mol ratio of O and Si is 0.9 ~ 1.1, such as 0.92,0.94,0.96,0.98,1,1.02,1.04,1.06 or 1.08.
Preferably, the sub-silicon composite D of described oxidation
10>1.0 μm, 3.0<D
50<15.0 μm, D
max<50 μm.
Preferably, the powder body compacted density of the sub-silicon composite of described oxidation is 1.0 ~ 1.5g/cm
3, such as 1.13g/cm
3, 1.16g/cm
3, 1.19g/cm
3, 1.24g/cm
3, 1.28g/cm
3, 1.32g/cm
3, 1.36g/cm
3, 1.4g/cm
3or 1.45g/cm
3.
In the present invention, ppm is the abbreviation of English parts per million, means the portion in every 1,000,000 parts, namely represents 1,000,000/(several), or claims PPM.
Two of object of the present invention is to provide a kind of lithium ion battery as above to be oxidized the preparation method of sub-silicon composite, said method comprising the steps of:
By SiO
x(0.9<x<1.1) the even coated one deck conductive carbon of powder surface, obtains lithium ion battery and is oxidized sub-silicon composite.
Preferably, the mode of coated with conductive carbon is that solid phase is coated, liquid phase coating or gas phase coated, be preferably gas phase coated.
Preferably, described gas phase is coated comprises the following steps:
(1) by SiO
xblock is placed in reactor and carries out 900 ~ 1150 DEG C of heat treatments, makes Si crystallite be dispersed in SiO
xin, obtain modification SiO
xparticle;
(2) by modification SiO
xparticle carries out fragmentation, pulverizing and classification, obtains SiO
xpowder;
(3) by SiO
xpowder is placed in rotary furnace and carries out the coated process of gas-phase carbon in 600 ~ 900 DEG C, obtains presoma;
(4) process is torn to adhesion particle in presoma, to control the coated front and back SiO of carbon
xmedian particle diameter D
50change is between 0.5 ~ 2.0 μm;
Optionally, step (5) is carried out:
(5) carry out mixing, sieving, except magnetic, drying and packing.
Traditional Si O in industry
xnegative material preparation technology: first by SiO
xblock is crushed to fine powder, and the carbon carrying out 600 ~ 900 DEG C is coated, and (namely disproportionation process makes tiny Si crystallite be dispersed in SiO then to carry out the high-temperature heat treatment of 900 ~ 1150 DEG C
xin).And present invention process changes this conventional fabrication process: first by SiO
xblock carries out the high-temperature heat treatment of 900 ~ 1150 DEG C, and tiny Si crystallite is dispersed in SiO
xin, then carry out the coated process of carbon of pulverizing process and 600 ~ 900 DEG C.Beneficial effect brought like this is: obviously can promote the initial coulomb efficiency and capacity performance that are oxidized sub-silicon materials.Owing to: by the high-temperature heat treatment operation of 900 ~ 1150 DEG C in advance, decrease oxidation (the block SiO of granular boundary
xparticulate oxidation contact-making surface comparatively SiO
xpowder is few, decreases the possibility of oxidation), the coated treatment process of carbon of material 600 ~ 900 DEG C is put finally simultaneously, avoid SiO so as much as possible
xhigh-temperature oxydation (relatively final operation be 900 ~ 1150 DEG C of Technologies for Heating Processing).
Preferably, step (1) described Si microcrystalline grain size is between 2.0 ~ 15.0nm.
Preferably, SiO
xmiddle O and Si mol ratio is 0.9 ~ 1.1, such as 0.92,0.94,0.96,0.98,1,1.02,1.04,1.06 or 1.08.
Preferably, described reactor is any one in rotary furnace, roller kilns, pushed bat kiln, box type furnace or tube furnace.
Preferably, described reactor furnace atmosphere is non-oxidizing atmosphere, is preferably the combination of any one or at least two kinds in nitrogen, helium, argon gas or hydrogen.
Preferably, step (2) described SiO
xin powder, the powder volume of particle diameter below 1.0 μm accounts for whole SiO
xless than 15.0%, 3.0<D of powder
90/ D
10<15.0, D
90<25.0 μm, D
max<50.0 μm.
Preferably, the equipment that step (2) is pulverized is any one in planetary ball mill, roll extrusion mill, Raymond mill, mechanical crusher, super-low temperature pulverizator, superheated steam pulverizer or airslide disintegrating mill.
Preferably, in the coated processing procedure of step (3) described gas-phase carbon, rotary furnace furnace atmosphere is non-oxidizing atmosphere, is preferably the combination of any one or at least two kinds in nitrogen, helium, argon gas or hydrogen.
Preferably, the organic carbon source gas that the coated processing procedure of step (3) described gas-phase carbon is selected is hydro carbons, is preferably the combination of any one or at least two kinds in methane, ethene, acetylene, propane, benzene,toluene,xylene, styrene or phenol.
Preferably, tearing the equipment that process adopts described in step (4) is any one in VC mixer, mechanical fusion machine or mechanical crusher.
Three of object of the present invention is to provide a kind of lithium ion battery, and described lithium ion battery comprises lithium ion battery as above and is oxidized sub-silicon composite.
Four of object of the present invention is to provide a kind of lithium ion battery as above to be oxidized the purposes of sub-silicon composite, and it is for the negative material of lithium ion battery.
Compared with the prior art, the present invention has following beneficial effect:
Compared with prior art, the present invention's control SiO
xparticle diameter is within the powder of 1.0 μm is to 15.0%, and control 3.0<D
90/ D
10<15.0, D
90<25.0 μm, D
max<50.0 μm, improves that the initial coulomb efficiency, the capacity that are oxidized sub-silicon composite play, cycle performance and bulk effect.Meanwhile, present invention employs traditional Si O in difference industry
xnegative material preparation technology, first by SiO
xblock carries out high-temperature heat treatment (900 ~ 1150 DEG C), and tiny Si crystallite is dispersed in SiO
xin, then carry out pulverizing process and the coated process of carbon (600 ~ 900 DEG C), this technique obviously can promote the initial coulomb efficiency and capacity performance that are oxidized sub-silicon materials.
Accompanying drawing explanation
Fig. 1 is oxidized sub-silicon composite electron microscopic picture in the embodiment of the present invention 1.
Fig. 2 is oxidized sub-silicon composite tangent plane picture in the embodiment of the present invention 1.
Fig. 3 is oxidized sub-silicon composite XRD to scheme in the embodiment of the present invention 1.
Fig. 4 is the Raman collection of illustrative plates being oxidized sub-silicon composite in the embodiment of the present invention 1.
Fig. 5 is oxidized sub-silicon composite first charge-discharge curve in the embodiment of the present invention 1.
Embodiment
Technical scheme of the present invention is further illustrated by embodiment below in conjunction with accompanying drawing.
Experimental technique in following embodiment, if no special instructions, is conventional method; Experiment material used, if no special instructions, is and is purchased available from routine biochemistry chemical reagent work.
Embodiment 1
(1) by SiO
x(0.9<x<1.1) block is placed in box type furnace, passes into argon atmosphere, is warming up to 1150 DEG C of high-temperature heat treatment 2h with 3 DEG C/min, makes Si crystallite be dispersed in SiO
xin, obtain modification SiO
xblock;
(2) by modification SiO
xblock carries out fragmentation, ultralow temperature is pulverized, control SiO
xpowder powder volume below 1.0 μm accounts for whole less than 15.0,3.0<D
90/ D
10<15.0, D
90<25.0 μm, D
max<50.0 μm;
(3) SiO of 100g is got
xpowder is placed in rotary furnace, is warming up to 600 DEG C, passes into acetylene gas with 3 DEG C/min, and flow is 0.2L/min, passes into N in whole course of reaction stove
2protective atmosphere, control flow is 0.1L/min, and reaction 10h, to presoma;
(4) put in mechanical fusion machine by above-mentioned presoma, control rotating speed is 1800r/min, merges 10min, control SiO
xcarbon coated front and back median particle diameter D
50be changed to 0.5 ~ 2.0 μm;
(5) mix, sieve, except magnetic, drying and packing, obtain being oxidized sub-silicon composite.
Fig. 1 is oxidized sub-silicon composite electron microscopic picture in the embodiment of the present invention 1, in visible composite material, fine particle is less, and is single dispersing primary particle.Fig. 2 is oxidized sub-silicon composite tangent plane picture in the embodiment of the present invention 1, as seen from Figure 2, be oxidized sub-silicon face conductive carbon layer thickness at 50 ~ 100nm, uniformity.Fig. 3 is the X ray diffracting spectrum being oxidized sub-silicon composite in the embodiment of the present invention 1, and as can be seen from the figure all samples exists an obvious broad peak within the scope of 2 θ=10 ~ 40 °, corresponding to SiO
xamorphous feature, Si (111) crystal face characteristic peak has been there is near 2 θ=28.4 °, this composite material of surface is separated out there being Si crystal after high-temperature process, and substitution Scherrer equation can be regarded as Si (111) crystal face crystallite dimension is 15.0nm.
Fig. 4 is the Raman collection of illustrative plates being oxidized sub-silicon composite in the embodiment of the present invention 1, at 1345 ~ 1355cm
-1place's peak intensity is I
dthe sub-silicon composite material mesexine disordering non crystalline structure carbon characteristic peak of corresponding oxidation, at 1575 ~ 1595cm
-1place peak intensity I
gthe crystalline structure carbon characteristic peak of corresponding ordering, the two ratio I
d/ I
gbe 2.0.Fig. 5 is oxidized sub-silicon composite first charge-discharge curve in the embodiment of the present invention 1, material discharges first (embedding lithium), and specific capacity is 2084.3mAh/g, charging (de-lithium) specific capacity 1632.0mAh/g, first charge-discharge efficiency reaches 78.3%.
Embodiment 2
(1) by SiO
xblock is placed in roller kilns, passes into argon atmosphere, is warming up to 900 DEG C of high-temperature heat treatment 10h with 3 DEG C/min, makes Si crystallite be dispersed in SiO
xin, obtain modification SiO
xblock;
(2) by modification SiO
xblock carries out mechanical crushing, classification grinding, control SiO
xpowder powder volume below 1.0 μm accounts for whole less than 15.0,3.0<D
90/ D
10<15.0, D
90<25.0 μm, D
max<50.0 μm;
(3) SiO of 100g is got
xpowder is placed in rotary furnace, is warming up to 900 DEG C, passes into methane gas with 5 DEG C/min, and flow is 0.2L/min, passes into N in whole course of reaction stove
2protective atmosphere, control flow is 0.1L/min, and reaction 2h, to presoma;
(4) put in VC mixer by above-mentioned presoma, control rotating speed is 400r/min, breaks up 10min, control SiO
xcarbon coated front and back median particle diameter D
50be changed to 0.5 ~ 2.0 μm;
(5) mix, sieve, except magnetic, drying and packing, obtain being oxidized sub-silicon composite.
Embodiment 3
(1) by SiO
x(0.9<x<1.1) block is placed in pushed bat kiln, passes into argon atmosphere, is warming up to 950 DEG C of high-temperature heat treatment 8h with 1 DEG C/min, makes Si crystallite be dispersed in SiO
xin, obtain modification SiO
xblock;
(2) by modification SiO
xblock carries out fragmentation, ultralow temperature is pulverized, control SiO
xpowder powder volume below 1.0 μm accounts for whole less than 15.0,3.0<D
90/ D
10<15.0, D
90<25.0 μm, D
max<50.0 μm;
(3) SiO of 100g is got
xpowder is placed in rotary furnace, is warming up to 850 DEG C, passes into propane gas with 5 DEG C/min, and flow is 5.0L/min, passes into N in whole course of reaction stove
2protective atmosphere, control flow is 1.5L/min.Reaction 10h, to presoma;
(4) put in mechanical fusion machine by above-mentioned presoma, control rotating speed is 1800r/min, merges 10min, control SiO
xcarbon coated front and back median particle diameter D
50be changed to 0.5 ~ 2.0 μm;
(5) mix, sieve, except magnetic, drying and packing, obtain being oxidized sub-silicon composite.
Comparative example 1
Compared with embodiment 1, wherein step (2) is: by the modification SiO obtained
xblock carries out planetary ball mill, wherein SiO
xpowder particle below 1.0 μm accounts for whole 15.0 ~ 20.0%, and all the other process in the same manner as in Example 1.This comparative example 1 main purpose is investigation less than 1.0 μm fine powder granule SiO
xon the impact of material property.Result of the test finds: increase SiO
xmiddle particle diameter is less than 1.0 μm of powder, and be oxidized sub-silicon composite capacity and efficiency meeting obviously deterioration, concrete data refer to table 1.
Comparative example 2
Compared with embodiment 1, do not carry out step (4), all the other process in the same manner as in Example 1.This comparative example 2 main purpose investigates SiO
xcarbon coated front and back granularity difference is on the impact of material property.Result of the test finds: do not carry out step (4) SiO
xcarbon coated front and back value particle diameter D
50be changed to 2.0 ~ 5.0 μm, be oxidized sub-silicon composite cycle performance and Volumetric expansion meeting obviously deterioration, concrete data refer to table 1.
Comparative example 3
Compared with embodiment 1, first by SiO
xblock carries out pulverization process, then carries out the coated and high-temperature heat treatment of carbon, this comparative example 3 main purpose be investigate pulverize, the coated and high-temperature heat treatment process sequencing of carbon on the impact of material property, specific as follows:
(1) by SiO
xblock carries out fragmentation, ultralow temperature is pulverized, control SiO
xpowder powder volume below 1.0 μm accounts for whole less than 15.0,3.0<D
90/ D
10<15.0, D
90<25.0 μm, D
max<50.0 μm;
(2) SiO of 100g is got
xfine powder is placed in rotary furnace, is warming up to 600 DEG C, passes into acetylene gas with 3 DEG C/min, and flow is 0.2L/min, passes into N in whole course of reaction stove
2protective atmosphere, control flow is 0.1L/min, and reaction 10h, to presoma;
(3) above-mentioned presoma is placed in box type furnace, passes into argon atmosphere, be warming up to 1150 DEG C of high-temperature heat treatment 2h with 3 DEG C/min, make Si crystallite be dispersed in SiO
xin, obtain presoma 2;
(4) put in mechanical fusion machine by above-mentioned presoma 2, control rotating speed is 1800r/min, merges 10min, control SiO
xcarbon coated front and back median particle diameter D
50be changed to 0.5 ~ 1.0 μm;
(5) mix, sieve, except magnetic, drying and packing, obtain being oxidized sub-silicon composite.
The negative material of following methods to embodiment 1 ~ 3 and comparative example 1 ~ 3 is adopted to test:
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 Malvern laser particle analyzer MS 2000 test material particle size range and distribution.
Adopt the surface topography, granular size etc. of Hitachi, Ltd S4800 sem observation sample.
Adopt X-ray diffractometer X ' Pert Pro, the structure of PANalytical test material, set within the scope of corresponding 2 θ=26.0 ~ 30.0 °, half-peak breadth is β, substitutes into Scherrer equation and calculates to obtain crystallite dimension, and this crystal grain evaluation method is for everybody is in common knowledge.
Adopt German Brooker G4ICARUS type infrared carbon sulfur analyzer to measure carbon content in material, setting records carbon content in the sub-silicon composite of oxidation.
Scanning electron microscopy GENESIS energy disperse spectroscopy (U.S., EDAX) subsidiary is at random adopted to come element kind and EDS maps situation in analysis of material, primary part observation carbon distribution situation.
Japanese HORIBA company XPLORA type confocal laser Raman spectrometer is adopted to measure material composition and structure in material.
Adopt U.S. PE company ICP emission spectrophotometer to measure Si content in material, German ELTRA company ONH-2000 type oxygen nitrogen hydrogen analyzer measures O content in material, tries to achieve O and Si mol ratio O/Si in material.
Adopt following methods test chemical property: material prepared by Example 1 ~ 3 and comparative example 1 ~ 3 is as negative material, mix according to the mass ratio of 60:20:20 with binding agent polyvinylidene fluoride (PVDF), conductive agent (Super-P), add appropriate 1-METHYLPYRROLIDONE (NMP) as dispersant furnishing slurry, be coated on Copper Foil, and through vacuumize, roll-in, be prepared into negative plate; Positive pole adopts metal lithium sheet, uses the LiPF of 1mol/L
6the electrolyte that three components mixed solvent mixes by EC:DMC:EMC=1:1:1 (v/v), employing microporous polypropylene membrane is barrier film, in the German Braun inert atmosphere glove box System Co., Ltd MB200B type glove box being full of argon gas, be assembled into CR2025 type button cell.The charge-discharge test of button cell is on the Jin Nuo Electronics Co., Ltd. LAND battery test system of Wuhan, and at normal temperature condition, 0.1C constant current charge-discharge, charging/discharging voltage is limited in 0.005 ~ 1.5V.
Adopt Measurement and Computation material volume bulking effect with the following method: (after circulation in 50 weeks the front pole piece thickness of pole piece thickness-circulation)/(before circulation pole piece thickness-copper thickness) * 100%
The test result of embodiment 1 ~ 3 and the negative material prepared by comparative example 1 ~ 3 as shown in Table 1 and Table 2.
Table 2
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. lithium ion battery is oxidized a sub-silicon composite, it is characterized in that, it is SiO by chemical formula
x(0.9<x<1.1) powder and conductive carbon coating layer composition; Wherein, SiO
xthe powder volume of middle particle diameter below 1.0 μm accounts for whole SiO
xless than 15.0%, 3.0<D of powder
90/ D
10<15.0, D
90<25.0 μm, D
max<50.0 μm; The coated front and back SiO of carbon
xmedian particle diameter D
50change is between 0.5 ~ 2.0 μm.
2. the sub-silicon composite of oxidation as claimed in claim 1, it is characterized in that, the BET specific surface area that described lithium ion battery is oxidized sub-silicon composite is 1.0 ~ 3.0m
2/ g;
Preferably, CuK αsource XRD determining lithium ion battery is utilized to be oxidized sub-silicon composite crystal structure, there is Si (111) characteristic peak within the scope of corresponding 2 θ=26.0 ~ 30.0 °, Si (111) crystal face crystallite dimension is between 2.0 ~ 15.0nm.
3. the sub-silicon composite of oxidation as claimed in claim 1 or 2, is characterized in that, utilizes Raman spectrometer to measure lithium ion battery and is oxidized sub-silicon composite carbon coating layer architectural feature, corresponding 1345 ~ 1355cm
-1peak intensity I
dwith 1575 ~ 1595cm
-1peak intensity I
gratio I
d/ I
gbetween 0.5 ~ 2.0;
Preferably, the thickness of conductive carbon coating layer is 5.0 ~ 125.0nm, and carbon content accounts for the 0.5 ~ 20.0wt% being oxidized sub-silicon composite.
4. the sub-silicon composite of the oxidation as described in one of claim 1-3, it is characterized in that, 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 and Mn<5.0ppm in the sub-silicon composite of described oxidation;
Preferably, in the sub-silicon composite of described oxidation, the total amount of magnetic foreign body Fe, Cr, Ni and Zn is below 0.1ppm;
Preferably, SiO
xin powder, the mol ratio of O and Si is 0.9 ~ 1.1;
Preferably, the sub-silicon composite D of described oxidation
10>1.0 μm, 3.0<D
50<15.0 μm, D
max<50 μm;
Preferably, the powder body compacted density of the sub-silicon composite of described oxidation is 1.0 ~ 1.5g/cm
3.
5. the lithium ion battery as described in one of claim 1-4 is oxidized a preparation method for sub-silicon composite, it is characterized in that, said method comprising the steps of:
By SiO
x(0.9<x<1.1) the even coated one deck conductive carbon of powder surface, obtains lithium ion battery and is oxidized sub-silicon composite.
6. method as claimed in claim 5, is characterized in that, the mode of coated with conductive carbon is that solid phase is coated, liquid phase coating or gas phase coated, be preferably gas phase coated.
7. method as claimed in claim 6, it is characterized in that, described gas phase is coated to be comprised the following steps:
(1) by SiO
xblock is placed in reactor and carries out 900 ~ 1150 DEG C of heat treatments, makes Si crystallite be dispersed in SiO
xin, obtain modification SiO
xparticle;
(2) by modification SiO
xparticle carries out fragmentation, pulverizing and classification, obtains SiO
xpowder;
(3) by SiO
xpowder is placed in rotary furnace and carries out the coated process of gas-phase carbon in 600 ~ 900 DEG C, obtains presoma;
(4) process is torn to adhesion particle in presoma, to control the coated front and back SiO of carbon
xmedian particle diameter D
50change is between 0.5 ~ 2.0 μm;
Optionally, step (5) is carried out:
(5) carry out mixing, sieving, except magnetic, drying and packing.
8. method as claimed in claim 7, it is characterized in that, step (1) described Si microcrystalline grain size is between 2.0 ~ 15.0nm;
Preferably, SiO
xmiddle O and Si mol ratio is 0.9 ~ 1.1;
Preferably, described reactor is any one in rotary furnace, roller kilns, pushed bat kiln, box type furnace or tube furnace;
Preferably, described reactor furnace atmosphere is non-oxidizing atmosphere, is preferably the combination of any one or at least two kinds in nitrogen, helium, argon gas or hydrogen;
Preferably, step (2) described SiO
xin powder, the powder volume of particle diameter below 1.0 μm accounts for whole SiO
xless than 15.0%, 3.0<D of powder
90/ D
10<15.0, D
90<25.0 μm, D
max<50.0 μm;
Preferably, the equipment that step (2) is pulverized is any one in planetary ball mill, roll extrusion mill, Raymond mill, mechanical crusher, super-low temperature pulverizator, superheated steam pulverizer or airslide disintegrating mill;
Preferably, in the coated processing procedure of step (3) described gas-phase carbon, rotary furnace furnace atmosphere is non-oxidizing atmosphere, is preferably the combination of any one or at least two kinds in nitrogen, helium, argon gas or hydrogen;
Preferably, the organic carbon source gas that the coated processing procedure of step (3) described gas-phase carbon is selected is hydro carbons, is preferably the combination of any one or at least two kinds in methane, ethene, acetylene, propane, benzene,toluene,xylene, styrene or phenol;
Preferably, tearing the equipment that process adopts described in step (4) is any one in VC mixer, mechanical fusion machine or mechanical crusher.
9. a lithium ion battery, is characterized in that, the described lithium ion battery lithium ion battery comprised as described in one of claim 1-4 is oxidized sub-silicon composite.
10. the lithium ion battery as described in one of claim 1-4 is oxidized a purposes for sub-silicon composite, it is characterized in that, it is for the negative material of lithium ion battery.
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Address after: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth, Patentee after: Beitrei New Materials Group Co., Ltd Address before: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth, Patentee before: Shenzhen BTR New Energy Materials Inc. |
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Inventor after: Yue Min Inventor after: Yu Dexin Inventor after: Ren Jianguo Inventor after: Li Sheng Inventor after: Huang Youyuan Inventor after: He Xueqin Inventor after: Pang Chunlei Inventor before: Yue Min Inventor before: Yu Dexin Inventor before: Ren Jianguo Inventor before: Li Sheng Inventor before: Huang Youyuan |