CN103311526A - Monox/carbon composite material as well as preparation method and use thereof - Google Patents
Monox/carbon composite material as well as preparation method and use thereof Download PDFInfo
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Abstract
The invention relates to a monox/carbon composite material, comprising monox/graphene particles, organic matter pyrolysis carbon and graphite powder, wherein monox particles are adhered to the surface of a grapheme sheet; the organic matter pyrolysis carbon coats the monox/ graphene particles, and then is compounded with graphite. The preparation method of the monox/carbon composite material comprises the steps of: mixing monox particles with graphene to obtain the monox/graphene particles; coating organic carbon by obtained monox/graphene particles, thereby obtaining the monox/graphene material coated by the organic matter pyrolysis carbon; and mixing the obtained monox/graphene material coated by the organic matter pyrolysis carbon with the graphite powder, so as to obtain the monox/carbon composite material. The monox/carbon composite material is used as a lithium ion battery cathode material. Thus, the monox/carbon composite material has the characteristics of high first charge and discharge efficiency, excellent cycle performance and power charge and discharge properties, and low volume expansion effect.
Description
Technical field
The present invention relates to the lithium ion battery negative material field, particularly, the present invention relates to a kind of silica/carbon composite and preparation method thereof and purposes.
Background technology
The commercialization lithium ion battery mainly adopts the graphite-like material with carbon element as negative electrode active material.Yet, carbon class negative material makes it can not satisfy electronics miniaturization because of its specific capacity lower (372mAh/g) and automobile-used lithium ion battery is high-power, the high power capacity requirement, thereby needs high-energy-density, the high safety performance of the alternative material with carbon element of research and development, the new type lithium ion battery negative material of long circulation life.
Conventional metals silicon is as lithium ion battery negative material, and its theoretical specific capacity can reach 4200mAh/g.But its volumetric expansion that exists in charge and discharge process (about 300%) can cause the active particle efflorescence, and then loses and electrically contact and cause capacity to be decayed fast.Silica material, though its theoretical specific capacity is littler than pure silicon material, its bulk effect in battery charge and discharge process less relatively (about 200%), therefore, the easier breakthrough restriction of silica material realizes commercialization early.
CN 102694155A discloses a kind of Si-C composite material and preparation method thereof and has reached the lithium ion battery that uses this material preparation.The preparation method of this Si-C composite material may further comprise the steps: (1) mixes composite material, porousness carbon matrix material, the excessive hydrofluoric acid solution of the silicon dioxide coated nano silicon that silicon monoxide makes, and obtains being compounded with between porousness carbon matrix material hole the composite material of nano-silicon particle; (2) with the composite material that is compounded with the nano-silicon particle between the coated porous property of high molecular polymer carbon matrix material hole, under inert atmosphere, heating obtains the Si-C composite material that the porous carbon bag covers.Though this Si-C composite material is alleviated the powder of detached phenomenon of active particle in charge and discharge process to a certain extent, the volumetric expansion effect makes moderate progress, but this material cycle performance is still not good enough, and first charge-discharge efficiency has only about 70%, can't satisfy the commercialization requirement.
Inferior silicon composite cathode material of the disclosed a kind of lithium ion battery oxidation of CN 102306759A and preparation method thereof, this material preparation may further comprise the steps: (1) generates silicon nanoparticle and amorphous silica with the inferior silicon of oxidation high temperature sintering under inert atmosphere; (2) accurately take by weighing the inferior silicon of a certain amount of oxidation behind sintering and conductive agent, add in the planetary ball mill, mixing and ball milling namely obtains the inferior silicon composite cathode material of oxidation.The inferior silicon composite cathode material of this oxidation has high power capacity (800mAh/g), but cycle performance is very poor, and the 100 all capability retentions that circulate are only for original about 50%, and first charge-discharge efficiency is low, and are also far from the commercialization distance.
Therefore, developing a kind of cycle performance and the rate charge-discharge performance is good, first charge-discharge efficiency is high, the volumetric expansion effect is low lithium ion battery cathode material and its preparation method is the technical barrier in affiliated field.
Summary of the invention
At the deficiencies in the prior art, one of purpose of the present invention is to provide a kind of silica/carbon composite.With problem such as improve cycle performance and rate charge-discharge poor performance that silica material exists as lithium ion battery negative material, enclosed pasture efficient is low first, the volumetric expansion effect is big.
Described silica/carbon has first charge-discharge efficiency height, cycle performance and rate charge-discharge excellent performance and the lower characteristics of volumetric expansion effect as lithium ion battery negative material.
Described silica/carbon composite contains silica/Graphene particle, organic substance cracking carbon (organic carbon), graphite powder, wherein, silicon oxide particle adheres to the graphene film surface, and organic substance cracking carbon coats described silica/Graphene particle, and then compound with graphite.
Described silica/Graphene particle is the class spherical composite pellets that Graphene and silicon oxide particle obtain by granulation.Wherein, silicon oxide particle adheres to the graphene film surface, and is wrapped in well in the three-dimensional conductive network with internal cavity structures of Graphene formation.
Preferably, the mass ratio of described silicon oxide particle and Graphene is 1:9～9:1, for example: 1:8,1:7,1:6,1:5,1:4,1:3,1:2,1:1,2:1,3:1,4:1,5:1,6:1,7:1,8:1 etc., more preferably 4:6～9:1 is preferably 7:3～8:2 especially; The Graphene amount is very few, and the material monolithic conductivity is low, and rate charge-discharge performance and cycle performance can not get promoting; The Graphene amount is too much, and the material monolithic specific area is big, and material compaction is low, and first charge-discharge efficiency can reduce.
Preferably, the mass ratio of described silica/Graphene particle and organic substance cracking carbon is 98:2～90:10, for example: 98:3,98:4,98:5,98:6,98:7,98:8,98:9,98:10,90:9 etc., more preferably 96:4～90:10 is preferably 95:5～90:10 especially.
Preferably, the particle diameter of described silica/carbon composite is 1～60 μ m, and more preferably 3～55 μ m are preferably 5～45 μ m especially.
The carbon that described organic substance cracking carbon namely obtains by the organic substance cracking.
One of purpose of the present invention also is to provide a kind of preparation method of described silica/carbon composite, and this method is simple, environmental friendliness.
Described silica/carbon composite is to be raw material with silicon oxide particle, Graphene, organic carbon source and graphite powder, obtains through step such as mixing, coating, mixing successively.
Preferably, the preparation method of described silica/carbon composite may further comprise the steps:
(1) silicon oxide particle and Graphene mixing are obtained silica/Graphene particle;
(2) silica that step (1) is obtained/Graphene particle coats organic carbon, obtains silica/grapheme material that organic substance cracking carbon coats;
(3) silica/grapheme material that the organic substance cracking carbon that step (2) is obtained coats mixes with graphite powder, obtains silica/carbon composite.
Preferably, step (3) is carried out afterwards:
(4) pulverize, obtain silica/carbon composite that particle diameter is 1～60 μ m.
Preferably, the described silicon oxide particle of step (1) is dispersed to the particle that constitutes in the amorphous silicon oxide for the nano-silicon particle.
Described silicon oxide particle, more than one that adopt following two kinds of methods make: the mixture heating of silicon dioxide and metallic silicon is generated silicon monoxide gas, cooled off and separate out and obtain.By transmission electron microscope, can confirm that (1～10nm) is the state that is dispersed in the amorphous silicon oxide for the nano particle of silicon.Or the silicon oxide particle (representing with the SiO general formula) that said method is made heat-treats to carry out disproportionated reaction at 800～1100 ℃ and makes in the argon gas inert environments, the nano-silicon particle can be made 1～100nm by this kind disproportionated reaction.
Preferably, the described silicon oxide particle of step (1) is powder type; Described silicon oxide particle can for example, be obtained by ball mill grinding by the prior art/new technology preparation of any appropriate.
Preferably, the granularity of the described silicon oxide particle of step (1) is below the 10000nm, for example 1nm, 2nm, 5nm, 10nm, 20nm, 40nm, 60nm, 100nm, 200nm, 500nm, 1000nm, 1500nm, 1900nm, 2100nm, 2500nm, 2900nm, 3100nm, 3500nm, 4000nm, 5000nm, 6000nm, 7000nm, 8000nm, 9000nm, 9500nm, 9800nm, 9900nm, 9950nm, 9990nm etc., more preferably 30～3000nm is preferably 50～2000nm especially.
The described Graphene of step (1) can adopt prior art to obtain, and comprises oxidation-reduction method, mechanical stripping method, epitaxial growth method, chemical vapour deposition technique, electrochemical process or arc process etc.
Preferably, the described Graphene of step (1) is the single or multiple lift Graphene.
Preferably, the lamellar spacing of the described Graphene of step (1) is 0.4～8nm, and the lamella width is 1～20 μ m, and specific area is 100～600m
2/ g; Preferred especially, the lamellar spacing of described Graphene is 0.4～5nm, and the lamella width is 1～15 μ m, and specific area is 200～400m
2/ g.
Preferably, step (1) is described comprises silicon oxide particle and Graphene mixing: silicon oxide particle and Graphene are dispersed in the organic solvent, and ultrasonic, spray drying obtains silica/Graphene particle then; Preferably, described organic solvent is ether, alcohol and/or ketone, more preferably C1-C6 alcohol and/or C3-C8 ketone, methyl alcohol for example, ethanol, ethylene glycol, propyl alcohol, the 12-propylene glycol, the 13-propylene glycol, glycerol, n-butanol, 1, the 2-butanediol, 1, the 3-butanediol, 1, the 4-butanediol, n-amyl alcohol, the 2-hexanol, acetone, methyl ethyl ketone, methyl propyl ketone, the ethyl propyl ketone, methyl butyl ketone, ethyl normal-butyl ketone, 1 kind or at least 2 kinds combination in the methyl amyl ketone are preferably ethanol especially, ethylene glycol, isopropyl alcohol, 1 kind or at least 2 kinds combination in acetone or the n-butanol; Preferably, described dispersion liquid solid content is 5～40%, for example: 6%, 8%, 11%, 12%, 13%, 15%, 20%, 22%, 25%, 28%, 29%, 31%, 34%, 36%, 38% or 39% etc., more preferably 8～35%, be preferably 10～30% especially; Preferably, described ultrasonic time is 20min at least, for example 21min, 22min, 24min, 26min, 29min, 31min, 35min, 40min, 45min, 50min, 55min, 59min, 61min, 65min, 70min, 5min, 78min, 79min, 85min, 90min or 100min etc., more preferably 25～80min is preferably 30～60min especially.
Preferably, the described coating of step (2) adopts liquid phase to coat method or chemical vapour deposition technique (CVD).
Preferably, the described coating of step (2) adopts liquid phase to coat method; Preferably, described liquid phase coating method comprises: silica/Graphene particle and organic carbon source are dispersed in the organic solvent drying, under the protective gas environment, be warming up to 500～1150 ℃ of roastings then, be incubated at least 0.5 hour, cooling obtains silica/grapheme material that organic carbon coats; Preferably, described dispersion liquid solid content is 5～40%, for example: 6%, 8%, 11%, 12%, 13%, 15%, 20%, 22%, 25%, 28%, 29%, 31%, 34%, 36%, 38% or 39% etc., more preferably 8～35%, be preferably 10～30% especially; Preferably, described heating rate be 20 ℃/below the min, for example 0.1 ℃/min, 0.2 ℃/min, 0.5 ℃/min, 0.9 ℃/min, 2 ℃/min, 3 ℃/min, 5 ℃/min, 8 ℃/min, 9 ℃/min, 11 ℃/min, 13 ℃/min, 14 ℃/min, 16 ℃/min, 17 ℃/min, 18 ℃/min or 19 ℃/min etc., more preferably 1～15 ℃/min is preferably 1～10 ℃/min especially; Described sintering temperature can be for example 510 ℃, 520 ℃, 530 ℃, 550 ℃, 580 ℃, 590 ℃, 610 ℃, 650 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1050 ℃, 1090 ℃, 1110 ℃, 1130 ℃ or 1140 ℃ etc.; Preferably, described sintering temperature is 600～1100 ℃; Described temperature retention time can be for example 0.6 hour, 0.8 hour, 1 hour, 1.5 hours, 2 hours, 3 hours, 5 hours, 8 hours, 10 hours, 15 hours, 20 hours, 30 hours, 40 hours, 50 hours, 80 hours; 100 hours etc.; Preferably, the described nature that is cooled to cools off; Preferably, described protective gas is a kind or at least 2 kinds combination in nitrogen, helium, neon, argon gas, krypton gas or the xenon; Preferably, described organic solvent is ether, alcohol and/or ketone, more preferably C1-C6 alcohol and/or C3-C8 ketone, methyl alcohol for example, ethanol, ethylene glycol, propyl alcohol, 1, the 2-propylene glycol, 1, ammediol, glycerol, n-butanol, 1, the 2-butanediol, 1, the 3-butanediol, 1, the 4-butanediol, n-amyl alcohol, the 2-hexanol, acetone, methyl ethyl ketone, methyl propyl ketone, the ethyl propyl ketone, ethyl normal-butyl ketone, 1 kind or at least 2 kinds combination in the methyl amyl ketone are preferably ethanol especially, ethylene glycol, isopropyl alcohol, 1 kind or at least 2 kinds combination in acetone or the n-butanol; Preferably, described organic carbon source is a kind or at least 2 kinds combination in phenolic resins, furfural resin, epoxy resin, Lauxite, pitch, citric acid, glucose, sucrose, polyvinyl chloride, the polyvinyl butyral resin.
Preferably, chemical vapour deposition technique (CVD) is adopted in the described coating of step (2); Preferably, described chemical vapour deposition technique comprises: silica/Graphene particle is placed reactor, feed organic gas, be warming up to 500～1100 ℃, deposit at least 1 hour, obtain silica/grapheme material that organic carbon coats; Preferably, described reactor is rotary furnace; Preferably, described organic gas is the arene of hydro carbons and/or 1～3 ring, more preferably a kind or at least 2 kinds combination in the aromatic hydrocarbon of 1～3 ring such as methane, ethane, ethene, acetylene, propane, butane, butylene, pentane, iso-butane, hexane and cyclohexanone, benzene,toluene,xylene, styrene, ethylbenzene, diphenyl-methane, naphthalene, phenol, cresols, nitrobenzene, chlorobenzene is preferably a kind or at least 2 kinds combination in methane, ethene, acetylene, benzene,toluene,xylene, styrene or the phenol especially; Preferably, the flow of described organic gas is 0.5～10L/min, and more preferably 0.8～8L/min is preferably 1～5L/min especially; Preferably, described heating rate be 20 ℃/below the min, for example 0.1 ℃/min, 0.2 ℃/min, 0.5 ℃/min, 0.9 ℃/min, 2 ℃/min, 3 ℃/min, 5 ℃/min, 8 ℃/min, 9 ℃/min, 11 ℃/min, 13 ℃/min, 14 ℃/min, 16 ℃/min, 17 ℃/min, 18 ℃/min or 19 ℃/min etc., more preferably 1～15 ℃/min is preferably 1～10 ℃/min especially; Preferably, described chemical vapor deposition process temperature is preferably 600～1100 ℃, more preferably 700～1000 ℃; Be lower than 600 ℃, need the more long process time, be unfavorable for cost control, be higher than 1100 ℃, may have the generation of SiC inertia phase, unfavorable to the chemical property of material; Described temperature retention time can be for example 1.1 hours, 1.2 hours, 1.3 hours, 1.5 hours, 2 hours, 3 hours, 5 hours, 8 hours, 9 hours, 15 hours, 20 hours, 30 hours, 40 hours, 50 hours, 80 hours; 100 hours etc.; Preferably, described temperature retention time is 1～10 hour.
In the method for the invention, the carbon covering amount that adopts liquid phase to coat method is controlled by the organic substance addition, adopts the carbon covering amount of CVD method to control by control organic gas flow, sedimentation time and treatment temperature combination.
Preferably, described silica/the grapheme material that organic carbon is coated of step (3) mixes with graphite powder and comprises: silica/grapheme material and graphite powder that organic carbon is coated mix, and the capacity that obtains is at silica/carbon composite of 370～550mAh/g; Carry out in the described mixer that is blended in prior art such as the general VC mixer; Preferably, described graphite powder is a kind or at least 2 kinds combination in natural flake graphite, micro crystal graphite, crystallization veiny graphite, spherical natural graphite, Delanium or the carbonaceous mesophase spherules, is preferably a kind or at least 2 kinds combination in spherical natural graphite, Delanium or the carbonaceous mesophase spherules especially; (silica/grapheme material capacity of the organic carbon coating that supposition makes is C1 to silica/grapheme material that described capacity can coat by the control organic carbon at silica/carbon composite of 370～550mAh/g with mass ratio (X:Y) control of graphite powder, the graphite powder capacity is C2, can get the two mass ratio: C1*X+C2Y=370～550 by following method, wherein X+Y=1, C1 and C2 can record by assembled battery).
Preferably, airslide disintegrating mill or mechanical crusher are adopted in the described pulverizing of step (4).
Preferably, the preparation method of described silica/carbon composite may further comprise the steps:
(1) silicon oxide particle and Graphene are dispersed in the organic solvent, control solid content 10～30%, ultrasonic 30～60min, spray drying obtains silica/Graphene particle then;
(2) silica that step (1) is obtained/Graphene particle and organic carbon source are dispersed in the organic solvent, the control solid content is 10～30%, dry, under the protective gas environment, be warming up to 600～1100 ℃ of roastings with 1～10 ℃/min then, be incubated 0.5h at least, naturally cooling obtains silica/grapheme material that organic carbon coats; Perhaps the silica that step (1) is obtained/Graphene particle places rotary furnace, feeds organic gas, and flow is 1～5L/min, is warming up to 500～1100 ℃ with 1～10 ℃/min, and deposition 1～10h obtains silica/grapheme material that organic carbon coats;
(3) adopt the VC mixer, silica/grapheme material and graphite powder that the organic carbon of certain mass is coated mix, and the capacity that obtains is at silica/carbon composite of 370～550mAh/g;
(4) pulverize, obtain silica/carbon composite that particle diameter is 1～60 μ m.
One of purpose of the present invention also is to provide a kind of purposes of described silica/carbon composite, the specific capacity of described silica/carbon composite is adjustable at 370～550mAh/g, than present commercialization material with carbon element high a lot (ca.370mAh/g), can well be used as battery electrode material, particularly as the application of lithium ion battery negative material, also provide more broad selection space for different terminal equipment with lithium ion battery manufacturers.
Described lithium ion battery first charge-discharge efficiency height, cycle performance and rate charge-discharge performance are good, can apply to portable type electronic product or fields such as electric bicycle, electric automobile such as camera, video camera, MP3, MP4, mobile phone, notebook computer.
Beneficial effect
The present invention adopts the mist projection granulating mode well silicon oxide particle to be adhered to the graphene film surface, it is wrapped in the three-dimensional conductive network structure of Graphene formation, can keep the excellent electric contact between silicon oxide particle and the Graphene, shortened the evolving path of lithium ion, ionic conductivity and the electronic conductivity of material have been improved, thereby improved first charge-discharge efficiency and the cycle performance of material, adapted to high rate charge-discharge; Simultaneously, the good graphene film of toughness and the cavity structure that constitutes can cushion and hold the volumetric expansion in the active material particle charge and discharge process effectively; And even organic carbon-coating also played and kept the stable effect of material structure, avoided active material particle to lose in charge and discharge process and electrically contacted, thereby prolonged useful life of lithium ion battery.
In the present invention, if no special instructions, "/" mean " with ".
The present invention compared with prior art, this silica/material with carbon element first charge-discharge efficiency height, good cycle; High rate charge-discharge performance and security performance makes its range of application widen electric automobile field, extensive market from consumption electronic product simultaneously; And synthetic method is simple, easy to control, be easy to accomplish scale production.
Description of drawings
Fig. 1 (a) is the silica/Graphene particle Electronic Speculum picture of the embodiment of the invention 1.
Fig. 1 (b) is the part sectioned view of the silica/Graphene particle of the embodiment of the invention 1.
Fig. 2 is silica/grapheme material Electronic Speculum picture that the organic carbon of the embodiment of the invention 1 coats.
Fig. 3 is the silica/carbon composite Electronic Speculum picture of the embodiment of the invention 1.
Fig. 4 is silica/grapheme material XRD figure that the organic carbon of the embodiment of the invention 1 coats.
Fig. 5 is the silica/carbon composite cycle performance curve of the embodiment of the 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 that described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
With metallic silicon and silicon dioxide in molar ratio 1:1 mix, and make it under 100Pa, react and produce silica gas with 1350 ℃, make this gas under the decompression of 50Pa, separate out with 900 ℃ of coolings, obtain block product, pulverize this product with planetary ball mill then, obtaining granularity is the powder of 100～500nm.
Through chemical analysis as can be known, this powder consist of SiO, utilize the transmission electron microscope mirror can observe silicon and be scattered in the structure of amorphous silicon oxide with atom level/microcrystal state, the silicon crystal size in the silicon oxide particle is 4nm.
Prepare the Graphene powder according to disclosed oxide-reduction method embodiment one in the Chinese patent application numbers 201110157325.7, the graphene film layer thickness is 0.4～5nm, lamella width 1～15 μ m; Specific area 300m
2/ g.
The above-mentioned silicon oxide particle that makes and Graphene powder are dispersed in the ethanol by mass ratio 7:3, control solid content 15%, frequency 28KHz, power 1800W/cm
2, ultrasonic processing 30min, spray drying obtains silica/Graphene particle then.
Silica/Graphene particle and phenolic resins are dispersed in the ethanol by mass ratio 90:10, the control solid content is 25%, dry, under the argon gas atmosphere environment, be warming up to 800 ℃ of roastings with 5 ℃/min then, be incubated 3 hours, naturally cooling obtains silica/grapheme material that organic carbon coats, and wherein the mass ratio of silica/Graphene particle and organic substance cracking carbon is 95:5.
Silica/grapheme material that organic carbon is coated and Delanium 1:9 by mass percentage join in the VC mixer and mix 1h, obtain silica/carbon composite.
Silica/carbon composite is pulverized with mechanical crusher, obtained silica/carbon composite that particle diameter is 5～45 μ m.
Embodiment 2
Employing is compared with embodiment 1, and is different except the silicon oxide particle raw material, makes silica/carbon composite under the same process condition.
Wherein, the block product (representing with the SiO general formula) that makes in above-described embodiment 1 in the argon gas inert environments, is heat-treated at 1000 ℃, carry out disproportionated reaction, pulverize this product with planetary ball mill then, obtaining granularity is the powder of 200～1000nm.Utilize transmission electron microscope can observe silicon and be scattered in the structure of amorphous silicon oxide with the microcrystal state, the silicon crystal size in the silicon oxide particle is 5～30nm.
Embodiment 3
Compare with embodiment 1, except silicon oxide particle and Graphene powder adding proportion are 8:2, under the same process condition, make silica/carbon composite.
Embodiment 4
Under process conditions substantially the same manner as Example 2, make silica/carbon composite, difference is: in silica/grapheme material preparation process that organic carbon coats, use citric acid to be organic carbon source, and the mass ratio of silicon oxide particle and Graphene powder is 9:1, the sintering temperature of the mixture of silica/Graphene particle and citric acid is 500 ℃, roasting time is 15 hours, and the mass ratio of silica/Graphene particle and organic substance cracking carbon is 98:2.
Under process conditions substantially the same manner as Example 2, make silica/carbon composite, difference is: in silica/grapheme material preparation process that organic carbon coats, use chemical vapour deposition technique to coat organic carbon, and the mass ratio of silicon oxide particle and Graphene powder is 1:9.
Wherein said chemical vapour deposition technique comprises: silica/Graphene particle is placed rotary furnace, feed methane gas, flow is 3L/min, be warming up to 600 ℃ with 2 ℃/min, deposition 4h, obtain silica/grapheme material that organic carbon coats, wherein the mass ratio of silica/Graphene particle and organic substance cracking carbon is 95:5.
Embodiment 6
Make silica/carbon composite under process conditions substantially the same manner as Example 4, difference is: silica/grapheme material and Delanium mixed proportion that organic carbon coats are 2:8, and the chemical deposition temperature is 1100 ℃, and sedimentation time is 1h.
Embodiment 7
Compare with embodiment 6, in the silica/grapheme material preparation process except the organic carbon coating, use acetylene as carbon source, being warming up to 500 ℃ of sedimentation times is 20h, makes silica/carbon composite under the same process condition.Obtain silica/grapheme material that organic carbon coats, wherein the mass ratio of silica/Graphene particle and organic substance cracking carbon is 90:10.
Embodiment 8
Compare with embodiment 6, except the silica/grapheme material of organic carbon coating and the mixed process of graphite, using Delanium instead is spherical natural graphite, makes silica/carbon composite under the same process condition.
Comparative Examples 1
Adopt prior art for preparing Si oxide/carbon negative pole material as a comparison case 1.
Adopt the raw silicon oxide material among the embodiment 1, with silicon oxide particle and polyvinyl butyral resin by mass percentage 83:17 be dispersed in the ethanol, the control solid content is 25%, dry, under the nitrogen atmosphere environment, be warming up to 900 ℃ of roastings with 5 ℃/min then, be incubated 3 hours, naturally cooling, obtain the silica material that organic carbon coats, wherein the mass ratio of silicon oxide particle and organic substance cracking carbon is 95:5.
The silica material that organic carbon is coated and Delanium 1:9 by mass percentage join in the VC mixer and mix 1h, obtain silica/carbon composite.
Silica/carbon composite is pulverized with mechanical crusher, obtained silica/carbon composite that particle diameter is 5～45 μ m.
Comparative Examples 2
Adopt the raw silicon oxide material among the embodiment 2, silicon oxide particle is placed rotary furnace, feed ethylene gas, flow is 4L/min, be warming up to 1000 ℃ with 1 ℃/min, deposition 6h obtains the silica material that organic carbon coats, and wherein the silica material of organic carbon coating and the mass ratio of organic substance cracking carbon are 90:10.The silica material that organic carbon is coated and MCMB 2:8 by mass percentage join in the VC mixer and mix 1h, obtain silica/carbon composite.
Silica/carbon composite is pulverized with mechanical crusher, obtained silica/carbon composite that particle diameter is 5～45 μ m.
Adopt following method that the negative material of embodiment 1～8 and Comparative Examples 1～2 is tested:
Adopt the average grain diameter of Ma Erwen laser particle analyzer MS 2000 test material particle size range and feed particles.
With X-ray diffractometer X ' Pert Pro, the structure of PANalytical test material.
Adopt Japanese JSM-6700F electronic scanner microscope of science to observe surface topography, the granular size of sample.
Adopt following method test electrochemistry cycle performance: get the material of embodiment 1～8 and Comparative Examples 1～2 preparation as negative material, mix according to the mass ratio of 90:6:4 with conductive agent (Super-P), binding agent sodium carboxymethylcellulose (CMC), add an amount of pure water as dispersant furnishing slurry, be coated on the Copper Foil, and through vacuumize, roll-in, be prepared into negative plate; The anodal metal lithium sheet that adopts, the LiPF of use 1mol/L
6Three component mixed solvents are pressed EC:DMC:EMC=1:1:1(v/v) electrolyte that mixes, the employing microporous polypropylene membrane is barrier film, is assembled into CR2025 type button cell in being full of the German Braun inert atmosphere glove box MB200B of the System Co., Ltd type glove box of argon gas.The charge-discharge test of button cell on the Wuhan Jin Nuo LAND of Electronics Co., Ltd. battery test system, at normal temperature condition, the 0.1C constant current charge-discharge, charging/discharging voltage is limited in 0.005～1.5V.
The Electrochemical results of the negative material that embodiment 1～8 and Comparative Examples 1～2 are prepared is as shown in table 1.
Table 1
By above experimental result as can be known, the negative material of the method for the invention preparation has excellent chemical property and stable circulation performance.
Applicant's statement, the present invention illustrates detailed process equipment of the present invention and technological process by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and technological process, does not mean that namely the present invention must rely on above-mentioned detailed process equipment and technological process could be implemented.The person of ordinary skill in the field should understand, any improvement in the present invention to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. silica/carbon composite, it contains silica/Graphene particle, organic substance cracking carbon, graphite powder, and wherein, silicon oxide particle adheres to the graphene film surface, organic substance cracking carbon coats described silica/Graphene particle, and then compound with graphite.
2. silica/carbon composite as claimed in claim 1 is characterized in that, the mass ratio of described silicon oxide particle and Graphene is 1:9～9:1, and more preferably 4:6～9:1 is preferably 7:3～8:2 especially;
Preferably, the mass ratio of described silica/Graphene particle and organic substance cracking carbon is 98:2～90:10, and more preferably 96:4～90:10 is preferably 95:5～90:10 especially;
Preferably, the particle diameter of described silica/carbon composite is 1～60 μ m, and more preferably 3～55 μ m are preferably 5～45 μ m especially.
3. the preparation method of a silica/carbon composite as claimed in claim 1 or 2 may further comprise the steps:
(1) silicon oxide particle and Graphene mixing are obtained silica/Graphene particle;
(2) silica that step (1) is obtained/Graphene particle coats organic carbon, obtains silica/grapheme material that organic substance cracking carbon coats;
(3) silica/grapheme material that the organic substance cracking carbon that step (2) is obtained coats mixes with graphite powder, obtains silica/carbon composite.
4. method as claimed in claim 3 is characterized in that, step (3) is carried out afterwards: pulverize (4), obtains silica/carbon composite that particle diameter is 1～60 μ m;
Preferably, the described silicon oxide particle of step (1) is dispersed to the particle that constitutes in the amorphous silicon oxide for the nano-silicon particle;
Preferably, the described silicon oxide particle of step (1) is powder type;
Preferably, the granularity of the described silicon oxide particle of step (1) is below the 10000nm, and more preferably 30～3000nm is preferably 50～2000nm especially;
Preferably, the described Graphene of step (1) is the single or multiple lift Graphene;
Preferably, the lamellar spacing of the described Graphene of step (1) is 0.4～8nm, and the lamella width is 1～20 μ m, and specific area is 100～600m
2/ g, preferred especially, the lamellar spacing of described Graphene is 0.4～5nm, and the lamella width is 1～15 μ m, and specific area is 200～400m
2/ g.
5. as claim 3 or 4 described methods, it is characterized in that step (1) is described to comprise silicon oxide particle and Graphene mixing: silicon oxide particle and Graphene are dispersed in the organic solvent, and ultrasonic, spray drying obtains silica/Graphene particle then;
Preferably, described organic solvent is ether, alcohol and/or ketone, and more preferably C1-C6 alcohol and/or C3-C8 ketone are preferably a kind or at least 2 kinds combination in ethanol, ethylene glycol, isopropyl alcohol, acetone or the n-butanol especially;
Preferably, described dispersion liquid solid content is 5～40%, more preferably 8～35%, be preferably 10～30% especially;
Preferably, described ultrasonic time is 20min at least, and more preferably 25～80min is preferably 30～60min especially.
6. as each described method of claim 3-5, it is characterized in that the described coating of step (2) adopts liquid phase to coat method;
Preferably, described liquid phase coating method comprises: silica/Graphene particle and organic carbon source are dispersed in the organic solvent drying, under the protective gas environment, be warming up to 500～1150 ℃ of roastings then, be incubated at least 0.5 hour, cooling obtains silica/grapheme material that organic carbon coats;
Preferably, described dispersion liquid solid content is 5～40%, more preferably 8～35%, be preferably 10～30% especially;
Preferably, described heating rate be 20 ℃/below the min, more preferably 1～15 ℃/min is preferably 1～10 ℃/min especially;
Preferably, described sintering temperature is 600～1100 ℃;
Preferably, the described nature that is cooled to cools off;
Preferably, described protective gas is a kind or at least 2 kinds combination in nitrogen, helium, neon, argon gas, krypton gas or the xenon;
Preferably, described organic solvent is ether, alcohol and/or ketone, and more preferably C1-C6 alcohol and/or C3-C8 ketone are preferably a kind or at least 2 kinds combination in ethanol, ethylene glycol, isopropyl alcohol, acetone or the n-butanol especially;
Preferably, described organic carbon source is a kind or at least 2 kinds combination in phenolic resins, furfural resin, epoxy resin, Lauxite, pitch, citric acid, glucose, sucrose, polyvinyl chloride or the polyvinyl butyral resin.
7. as each described method of claim 3-5, it is characterized in that chemical vapour deposition technique (CVD) is adopted in the described coating of step (2);
Preferably, described chemical vapour deposition technique comprises: silica/Graphene particle is placed reactor, feed organic gas, be warming up to 500～1100 ℃, deposit at least 1 hour, obtain silica/grapheme material that organic carbon coats;
Preferably, described reactor is rotary furnace;
Preferably, described organic gas is the arene of hydro carbons and/or 1～3 ring, more preferably a kind in methane, ethane, ethene, acetylene, propane, butane, butylene, pentane, iso-butane, hexane, cyclohexanone, benzene,toluene,xylene, styrene, ethylbenzene, diphenyl-methane, naphthalene, phenol, cresols, nitrobenzene or the chlorobenzene or at least 2 kinds combination is preferably a kind or at least 2 kinds combination in methane, ethene, acetylene, benzene,toluene,xylene, styrene or the phenol especially;
Preferably, the flow of described organic gas is 0.5～10L/min, and more preferably 0.8～8L/min is preferably 1～5L/min especially;
Preferably, described heating rate be 20 ℃/below the min, more preferably 1～15 ℃/min is preferably 1～10 ℃/min especially;
Preferably, described chemical vapor deposition process temperature is preferably 600～1100 ℃, more preferably 700～1000 ℃;
Preferably, described temperature retention time is 1～10 hour.
8. as each described method of claim 3-7, it is characterized in that, described silica/the grapheme material that organic carbon is coated of step (3) mixes with graphite powder and comprises: silica/grapheme material and graphite powder that organic carbon is coated mix, and obtain silica/carbon composite;
Preferably, described graphite powder is a kind or at least 2 kinds combination in natural flake graphite, micro crystal graphite, crystallization veiny graphite, spherical natural graphite, Delanium or the carbonaceous mesophase spherules, is preferably a kind or at least 2 kinds combination in spherical natural graphite, Delanium or the carbonaceous mesophase spherules especially;
Preferably, airslide disintegrating mill or mechanical crusher are adopted in the described pulverizing of step (4).
9. as each described method of claim 3-8, it is characterized in that, said method comprising the steps of:
(1) silicon oxide particle and Graphene are dispersed in the organic solvent, control solid content 10～30%, ultrasonic 30～60min, spray drying obtains silica/Graphene particle then;
(2) silica that step (1) is obtained/Graphene particle and organic carbon source are dispersed in the organic solvent, the control solid content is 10～30%, dry, under the protective gas environment, be warming up to 600～1100 ℃ of roastings with 1～10 ℃/min then, be incubated 0.5h at least, naturally cooling obtains silica/grapheme material that organic carbon coats; Perhaps the silica that step (1) is obtained/Graphene particle places rotary furnace, feed organic compound gas, flow is 1～5L/min, is warming up to 500～1100 ℃ with 1～10 ℃/min, deposition 1～10h obtains silica/grapheme material that organic carbon coats;
(3) silica/grapheme material and the graphite powder that organic carbon is coated mixes, and obtains silica/carbon composite;
(4) pulverize, obtain silica/carbon composite that particle diameter is 1～60 μ m.
10. a lithium ion battery is characterized in that, described lithium ion battery contains claim 1 or 2 described silica/carbon composites.
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