CN102447112B - Silicon-carbon composite material, preparation method thereof and cathode material containing same as well as lithium ion battery - Google Patents
Silicon-carbon composite material, preparation method thereof and cathode material containing same as well as lithium ion battery Download PDFInfo
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- CN102447112B CN102447112B CN201110399834.0A CN201110399834A CN102447112B CN 102447112 B CN102447112 B CN 102447112B CN 201110399834 A CN201110399834 A CN 201110399834A CN 102447112 B CN102447112 B CN 102447112B
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 83
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000010406 cathode material Substances 0.000 title abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 54
- 239000002245 particle Substances 0.000 claims abstract description 15
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 80
- 239000005543 nano-size silicon particle Substances 0.000 claims description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 62
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 50
- 239000002131 composite material Substances 0.000 claims description 43
- 229920000642 polymer Polymers 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 32
- 239000000377 silicon dioxide Substances 0.000 claims description 31
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- 229910052786 argon Inorganic materials 0.000 claims description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- 239000005011 phenolic resin Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229920001568 phenolic resin Polymers 0.000 claims description 9
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 238000005255 carburizing Methods 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000011295 pitch Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000008246 gaseous mixture Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 23
- 239000010703 silicon Substances 0.000 abstract description 22
- 229910052710 silicon Inorganic materials 0.000 abstract description 21
- 239000011856 silicon-based particle Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000002033 PVDF binder Substances 0.000 description 22
- 239000006230 acetylene black Substances 0.000 description 22
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 22
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 17
- 229910052744 lithium Inorganic materials 0.000 description 17
- 239000012153 distilled water Substances 0.000 description 13
- 230000004888 barrier function Effects 0.000 description 12
- 230000004087 circulation Effects 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229910013870 LiPF 6 Inorganic materials 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 11
- 239000006258 conductive agent Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 239000011889 copper foil Substances 0.000 description 11
- -1 ethyl carbonate ester Chemical class 0.000 description 11
- 229910052573 porcelain Inorganic materials 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000003825 pressing Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 230000008020 evaporation Effects 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 238000001132 ultrasonic dispersion Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910021487 silica fume Inorganic materials 0.000 description 3
- 235000019795 sodium metasilicate Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000001447 compensatory effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical group F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a silicon-carbon composite material, a preparation method thereof and a battery cathode made of the silicon-carbon composite material as well as a lithium ion battery. The silicon-carbon composite material comprises hollow porous carbon ball-enwrapped nanometer silicon particles; each nanometer silicon particle in the silicon-carbon composite material has a particle size of 5-80 nm, wherein the content of nanometer silicon is 10-90 wt percent. The silicon-carbon composite material has simple manufacturing process and can effectively restrain the expansion of silicon volume, so that the prepared lithium ion cathode material has excellent conductivity, and the corresponding lithium ion battery has large specific capacity and good cycling performance.
Description
Technical field
The invention belongs to battery manufacture technical field, the lithium ion battery negative material and the lithium ion battery that are specifically related to a kind of Si-C composite material and preparation method thereof and contain this Si-C composite material.
Background technology
Along with the exhaustion day by day of fossil fuel, and the fast development of portable electric appts and electric vehicle, the research of the new forms of energy such as power-supply battery has become the focus of global concern, wherein lithium ion battery because its energy density is high, power density is high, good cycle, environmental friendliness, structure diversification and the excellent specific property such as cheap be used widely.With regard to the structure of lithium ion battery, it is mainly made up of positive pole, negative pole, barrier film and electrolyte, and can the electrode performance of negative material further improve the decisive factor that becomes restriction performance of lithium ion battery.
For the demand for development of lithium-ion-power cell, objectively require that negative material has that high power capacity, rapid rate discharge and recharge, the feature such as high thermal stability and low cost.The more negative material of practical application is material with carbon element at present, as native graphite, graphitized intermediate-phase carbosphere etc., wherein the theoretical capacity of graphite cathode material is 372mAh/g, actual capacity is at 320-350mAh/g, high-rate charge-discharge capability is poor, has limited the development of lithium ion battery aspect high power capacity and high power.In non-carbon negative pole material, the theoretical capacity of silicon the highest (lithium storage content of monocrystalline silicon is 3800mAh/g), lithium and silicon form alloy Li
xsi (0 < x≤4.4), when forming Li
4.4theoretical capacity when Si compound is up to 4200mAh/g, much larger than the theoretical capacity of graphite; But the alloying of Si-Li alloy and removal alloying are accompanied by huge change in volume, its volumetric expansion is up to 300%, and the efflorescence of silicon causes electrode structure unstability and lost efficacy.Particularly common pure silicon, stable circulation is very poor, and the capacity after 5 times that circulates is just reduced to almost nil from 3000mAh/g above.
At present, in the method for modifying proposing for lithium ion battery negative material the problems referred to above, more effectively prepare carbon-silicon composite material and alleviate the volumetric expansion in battery charge and discharge process, the method has been widely used in the study on the modification of lithium ion battery negative material.
Preparing carbon-silicon composite material is to utilize " buffering skeleton " to carry out the method that compensative material expands.In theory, as long as the electrode potential of bi-material is incomplete same, the phase of electro-chemical activity just can be embedded in the skeleton of relative non-electrochemical activity, and non-active material plays the effect of dispersion and buffer medium.Utilize the coordinating effect between the each component of composite material, can reach the object of mutual supplement with each other's advantages.
Carbonaceous negative material change in volume in charge and discharge process is relatively little, and is the good conductor of electronics, is therefore selected as the dispersible carrier of dispersed silicon particle.The chemical property of silicon and carbon is close in addition, can combine closely.If silicon grain can be nano-dispersed in material with carbon element, the structure that material with carbon element itself has and be space between the silicon grain of nano-dispersed and all can be lithium ion a large amount of passages is provided, increases the embedded location of lithium ion.Compound can the reaching of carbon silicon improved silicon bulk effect, improves the object of its electrochemical stability.Therefore various carbon materials is used to and the compound negative material of preparing high power capacity and excellent cycle performance of silicon.Chinese Patent Application No. 200910037666.3 discloses the patent that name is called " a kind of preparation method of lithium ion battery silicon-carbon cathode material ", and the method prepares organogel after nano silica fume is dispersed in cold primer-oil, then drying, carbonization make product.The method directly adopts nano silica fume as raw material, and the high and poor effect of cost, because nano silica fume is easy to reunite, is difficult to be dispersed in pitch matrix, causes prepared negative material cycle performance not good.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, a kind of Si-C composite material and preparation method thereof is provided, technique is simple, prepared Si-C composite material can effectively suppress the expansion of silicon volume, the ion cathode material lithium of preparation has excellent electric conductivity thus, and corresponding lithium ion battery specific capacity is large, good cycle.
The technical scheme that solution the technology of the present invention problem adopts is that this Si-C composite material comprises that hollow porous carbon bag covers silicon nanoparticle, and in Si-C composite material, the particle diameter of silicon nanoparticle is 5-80nm, and wherein nano-silicon content is 10-90wt%.Adopt " nucleocapsid " structure of this uniqueness between porous carbon and silicon nanoparticle, to leave certain space, make electrode material holding structure integrality in charge and discharge process, effectively suppress the expansion of silicon volume, thereby the increase of coulomb efficiency and the irreversible capacity of electrode are reduced.
The present invention also provides the preparation method of this Si-C composite material, comprises the following steps:
(1) prepared polymer solution: high molecular polymer is dissolved in solvent, obtains the polymer solution of 1-20wt%;
(2) silicon monoxide is even with polymer mixed: silicon monoxide is mixed in proportion with the polymer solution of step (1) gained, fully disperse, then except desolventizing, obtain the composite material of polymer overmold silicon monoxide;
(3) high temperature carries out carbonization and disproportionated reaction: the composite material of the polymer overmold silicon monoxide to step (2) gained under protective atmosphere heats, make high molecular polymer generation carburizing reagent, silicon monoxide generation disproportionated reaction, obtains the composite material of porous carbon ball coated silica/nano-silicon;
(4) corrosion is except silicon dioxide: by the composite material of the porous carbon ball coated silica/nano-silicon of step (3) gained and corrosive liquid in mass ratio 1: 5-1: 100 mix, stir and separate to obtain Si-C composite material after 0.5-24 hour.
Preferably, the middle high molecular polymer of described step (1) comprises one or more in polyvinyl chloride, polymethyl methacrylate, polyacrylonitrile, phenolic resins, pitch, glucose, sucrose, starch.
Correspondingly, according to selected high molecular polymer, in described step (1), solvent comprises one or more in water, ethanol, acetone, oxolane, chloroform, 1-METHYLPYRROLIDONE or DMF.
Preferably, in described step (2), silicon monoxide mixes in proportion and refers to that silicon monoxide and polymer solution mass ratio are 1: 1-1: 200 with polymer solution; Fully disperse to refer to adopt ultrasonic wave to disperse 10-100 minute, ultrasonic frequency is 40,000 Hz.
By polymer overmold, outside silicon monoxide, in heat treatment process, at high temperature there is disproportionated reaction and generate silicon and silicon dioxide in silicon monoxide, and the two is evenly mixed in together.At high temperature cracking carbonization of polymer simultaneously generates amorphous carbon, after heat treatment, polymer covering layer becomes porous carbon shell like this, by silicon and coated with silica in inside, with corrosive liquid, product is processed subsequently, silicon dioxide in porous carbon shell is corroded, leave silicon nanoparticle, obtain the porous carbon clad nano silicon composite of " nucleocapsid " structure.
Amorphous carbon class material mostly has very high embedding lithium capacity, and is easy to by method coated Si particles such as high-temperature decomposition, chemical vapour deposition technique and ball-milling methods, forms nucleocapsid structure, plays volume cushioning effect, is the first-selection of preparing carbon-silicon composite material.
Above-mentioned Si-C composite material also can be prepared by the following method, specifically comprises the following steps:
(1) silicon monoxide and polymer mixed are even: silicon monoxide and high molecular polymer are taken in proportion, and with ball mill ball milling 0.5-24 hour, obtain mixture of powders;
(2) high temperature carries out carbonization and disproportionated reaction: under protective atmosphere, the mixture of powders of step (1) gained is heated, make high molecular polymer generation carburizing reagent, silicon monoxide generation disproportionated reaction, obtains the composite material of porous carbon ball coated silica/nano-silicon;
(3) corrosion is except silicon dioxide: by the composite material of the porous carbon ball coated silica/nano-silicon of step (2) gained and corrosive liquid in mass ratio 1: 5-1: 100 mix, stir and separate to obtain Si-C composite material after 0.5-24 hour.
Preferably, in above-mentioned steps (1), silicon monoxide and high molecular polymer mass ratio are 1: 9-9: 1.
Preferably, the temperature that described high temperature carries out carbonization and disproportionated reaction is 700-1500 DEG C, and be 0.5-12 hour heating time.
Further preferably, the temperature that described high temperature carries out carbonization and disproportionated reaction is preferably 900-1200 DEG C, is preferably 1-5h heating time.
Preferably, described protective atmosphere is the gaseous mixture of nitrogen, argon gas or argon gas and hydrogen.
Preferably, the hydrofluoric acid aqueous solution that described corrosive liquid is 3-40wt%.Hydrofluoric acid can react with silicon dioxide.Reaction equation is: SiO
2+ 4HF=SiF
4(gas)+2H
2o, when HF is excessive, SiO
2+ 6HF=H
2siF
6(fluosilicic acid)+2H
2o.Product is silicon tetrafluoride or water-soluble fluosilicic acid of gaseous state, thereby corrode with hydrofluoric acid aqueous solution after the composite material of porous carbon ball coated silica/nano-silicon, in porous carbon ball, silicon dioxide is reacted consumption, and remaining equally distributed nano-silicon is stayed in porous carbon shell.
Further preferably, the hydrofluoric acid aqueous solution that described corrosive liquid is 5-20wt%.
Preferably, described corrosive liquid also can be lithium hydroxide or potassium hydroxide or the NaOH of 0.4-30wt%.Lithium hydroxide or potassium hydroxide or NaOH can generate water-soluble lithium metasilicate or potassium silicate or sodium metasilicate with silicon dioxde reaction.
Further preferably, the NaOH that described corrosive liquid is 1-30wt%.
Preferably, described high molecular polymer comprises one or more in polyvinyl chloride, polymethyl methacrylate, polyacrylonitrile, phenolic resins, pitch, glucose, sucrose, starch.
The lithium ion battery negative material that the present invention also provides above-mentioned Si-C composite material to prepare, this lithium ion battery negative material comprises Si-C composite material prepared by said method.
Prepare the negative pole of lithium ion battery with above-mentioned lithium ion battery negative material, then be assembled into lithium ion battery, this lithium ion battery comprises the negative pole of preparing battery with above-mentioned lithium ion battery negative material.
The invention has the beneficial effects as follows: use simple and easy method to prepare Si-C composite material, this material comprises that hollow porous carbon bag covers silicon nanoparticle, the spherical structure that material with carbon element itself has and be space between the silicon grain of nano-dispersed and all can be lithium ion a large amount of passages is provided, increase the embedded location of lithium ion, improve silicon bulk effect, improve its electrochemical stability.Have marked improvement improving aspect the specific capacity of lithium ion battery and cycle performance, by the battery of made of the present invention, first discharge specific capacity has reached 537-2134mAh/g, after circulating for 100 times, still remains on 177-850mAh/g.
Brief description of the drawings
Fig. 1 is porous carbon clad nano silicon composite preparation flow figure in specific embodiment of the present invention;
Fig. 2 is ion cathode material lithium capacity circulating performance test figure in specific embodiment of the present invention.
Embodiment
For making those skilled in the art understand better technical scheme of the present invention, below in conjunction with accompanying drawing, the present invention is described in further detail.
Balls grinding machine of the present invention is to speed along the PM-0.4L type ball mill of development in science and technology Co., Ltd production in Nanjing.Ultrasonic wave separating apparatus frequency used is 40,000 Hz.
Embodiment mono-
Take 0.4g phenolic resins and be dissolved in and in 30mL ethanol, obtain polymer phenol resin solution, then add 0.80g silicon monoxide, and ultrasonic dispersion 10min, make silicon monoxide be well-dispersed in polymer phenol resin solution.After stirring ethanol evaporation, obtain the mixture of thickness; it is the composite material of the coated silicon monoxide of polymer phenolic resins; proceeded in porcelain boat; under gaseous mixture (hydrogen content 5%) protection of argon gas and hydrogen, be warmed up to 1000 DEG C; be incubated 4 hours, phenolic resins generation carburizing reagent in this process, silicon monoxide generation disproportionated reaction; cooling rear taking-up, obtains the composite material of 1.0g porous carbon coated silica/silicon nanoparticle.
Gained composite material is joined in 50mL 3wt% hydrofluoric acid solution, and after continuous stirring 10h, gained suspended matter is leached, in whipping process, silicon dioxide in composite material reacts products such as generating water-soluble fluosilicic acid with hydrofluoric acid, remaining equally distributed nano-silicon is stayed in porous carbon shell.Fully wash and remove the product such as hydrofluoric acid, fluosilicic acid with distilled water subsequently, the dry 0.5g Si-C composite material that obtains for 12 hours at 100 DEG C, this Si-C composite material is mainly hollow porous carbon bag and covers silicon nanoparticle, also has the silicon grain and other impurity that are not wrapped by a small quantity.The preparation flow figure of this Si-C composite material as shown in Figure 1.
The particle diameter that records silicon nanoparticle in this Si-C composite material by transmission electron microscope is 20nm, and recording nano-silicon content in this Si-C composite material by thermogravimetric analyzer is 51%.
Gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10, wherein Si-C composite material 0.24g, acetylene black 0.03g, PVDF 0.03g, this mixture is modulated into slurry with NMP (1-Methyl-2-Pyrrolidone), evenly be coated on Copper Foil, 100 DEG C of vacuumize 24 hours, makes experimental cell pole piece.Taking lithium sheet as to electrode, electrolyte is 1mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box that is full of argon gas atmosphere.
As shown in Figure 2, press the battery of the present embodiment made, first discharge specific capacity has reached 1573mAh/g, specific discharge capacity just drops to about 950mAh/g for the second time, and this is mainly to generate first solid electrolyte membrane (SEI film) and part irreversible reaction (come off as the not coated silicon grain of part splits, have in composite material a small amount of oxygen can with lithium in conjunction with generating lithia) in discharge process to cause.But first charge-discharge is afterwards along with cycle-index increases, battery special capacity fade is also not obvious, after 100 circulations, still remain on 850mAh/g, illustrate that the carbon shell of Si-C composite material has effectively suppressed the bulk effect of silicon, has improved the cycle performance of lithium ion battery.
Embodiment bis-
Take 1g polyvinyl chloride and be dissolved in 30mL chloroform, then add 0.80g silicon monoxide, and ultrasonic dispersion 60min.Stir evaporation after chloroform the mixture of thickness, proceeded in porcelain boat, under argon shield, be warmed up to 900 DEG C, be incubated 12 hours, cooling rear taking-up, obtains the composite material of 1.1g porous carbon coated silica/silicon nanoparticle.
Gained composite material is joined in 25mL 8wt% hydrofluoric acid solution, and after continuous stirring 6h, gained suspended matter is leached, and fully wash with distilled water, 100 DEG C of dry 0.6g Si-C composite materials that obtain for 12 hours.
The particle diameter that adopts the method identical with embodiment mono-to record silicon nanoparticle in this Si-C composite material is 21nm, and nano-silicon content is 43%.
Gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10, wherein Si-C composite material 0.24g, acetylene black 0.03g, PVDF 0.03g, this mixture is modulated into slurry with NMP (1-Methyl-2-Pyrrolidone), evenly be coated on Copper Foil, 100 DEG C of vacuumize 24 hours, makes experimental cell pole piece.Taking lithium sheet as to electrode, electrolyte is 1mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box that is full of argon gas atmosphere.
The battery of pressing the present embodiment made, first discharge specific capacity has reached 1352mAh/g, after 100 circulations, still remains on 593mAh/g.
Embodiment tri-
Take 3.2g polymethyl methacrylate and be dissolved in 30mL acetone, then add 0.80g silicon monoxide, and ultrasonic dispersion 100min.Stir evaporation after acetone the mixture of thickness, proceeded in porcelain boat, under argon shield, be warmed up to 1050 DEG C, be incubated 4 hours, cooling rear taking-up, obtains the composite material of 1.5g porous carbon coated silica and silicon nanoparticle.
Gained composite material is joined in 20mL 20wt% hydrofluoric acid solution, and after continuous stirring 1h, gained suspended matter is leached, and fully wash with distilled water, 100 DEG C of dry 0.9g Si-C composite materials that obtain for 12 hours.
The particle diameter that adopts the method identical with embodiment mono-to record silicon nanoparticle in this Si-C composite material is 34nm, and nano-silicon content is 31%.
Gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10, wherein Si-C composite material 0.24g, acetylene black 0.03g, PVDF 0.03g, this mixture is modulated into slurry with NMP (1-Methyl-2-Pyrrolidone), evenly be coated on Copper Foil, 100 DEG C of vacuumize 24 hours, makes experimental cell pole piece.Taking lithium sheet as to electrode, electrolyte is 1mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box that is full of argon gas atmosphere.
The battery of pressing the present embodiment made, first discharge specific capacity has reached 1231mAh/g, after 100 circulations, still remains on 633mAh/g.
Embodiment tetra-
Take in the mixed solvent that 0.3g glucose is dissolved in 30mL distilled water, then add 0.80g silicon monoxide, and ultrasonic dispersion 50min.Stir evaporation after mixed solvent the mixture of thickness, proceeded in porcelain boat, under argon shield, be warmed up to 1100 DEG C, be incubated 1 hour, cooling rear taking-up, obtains the composite material of 0.9g porous carbon coated silica and silicon nanoparticle.
Gained composite material is joined in 5mL 40wt% hydrofluoric acid solution, and after continuous stirring 8h, gained suspended matter is leached, and fully wash with distilled water, 100 DEG C of dry 0.4g Si-C composite materials that obtain for 12 hours.
The particle diameter that adopts the method identical with embodiment mono-to record silicon nanoparticle in this Si-C composite material is 46nm, and nano-silicon content is 63%.
Gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10, wherein Si-C composite material 0.24g, acetylene black 0.03g, PVDF 0.03g, this mixture is modulated into slurry with NMP (1-Methyl-2-Pyrrolidone), evenly be coated on Copper Foil, 100 DEG C of vacuumize 24 hours, makes experimental cell pole piece.Taking lithium sheet as to electrode, electrolyte is 1mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box that is full of argon gas atmosphere.
The battery of pressing the present embodiment made, first discharge specific capacity has reached 1438mAh/g, after 100 circulations, still remains on 813mAh/g.
Embodiment five
Take in the mixed solvent that 2g glucose and 2g sucrose is dissolved in 30mL ethanol and 30mL distilled water, then add 0.80g silicon monoxide, and ultrasonic dispersion 50min.Stir evaporation after mixed solvent the mixture of thickness, proceeded in porcelain boat, under nitrogen protection, be warmed up to 700 DEG C, be incubated 12 hours, cooling rear taking-up, obtains the composite material of 1.3g porous carbon coated silica and silicon nanoparticle.
Gained composite material is joined in 40mL 5wt% hydrofluoric acid solution, and after continuous stirring 12h, gained suspended matter is leached, and fully wash with distilled water, 100 DEG C of dry 0.7g Si-C composite materials that obtain for 12 hours.
The particle diameter that adopts the method identical with embodiment mono-to record silicon nanoparticle in this Si-C composite material is 5nm, and nano-silicon content is 23%.
Gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10, wherein Si-C composite material 0.24g, acetylene black 0.03g, PVDF 0.03g, this mixture is modulated into slurry with NMP (1-Methyl-2-Pyrrolidone), evenly be coated on Copper Foil, 100 DEG C of vacuumize 24 hours, makes experimental cell pole piece.Taking lithium sheet as to electrode, electrolyte is 1mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box that is full of argon gas atmosphere.
The battery of pressing the present embodiment made, first discharge specific capacity has reached 537mAh/g, after 100 circulations, still remains on 223mAh/g.
Embodiment six
Take 0.8g pitch and be dissolved in 50mL oxolane, then add 0.80g silicon monoxide, and ultrasonic dispersion 30min.Stir evaporation after oxolane the mixture of thickness, proceeded in porcelain boat, under argon shield, be warmed up to 1500 DEG C, be incubated 0.5 hour, cooling rear taking-up, obtains the composite material of 1.2g porous carbon coated silica and silicon nanoparticle.
Gained composite material is joined in 5mL 30wt% hydrofluoric acid solution, and after continuous stirring 6h, gained suspended matter is leached, and fully wash with distilled water, 100 DEG C of dry 0.8g Si-C composite materials that obtain for 12 hours.
The particle diameter that adopts the method identical with embodiment mono-to record silicon nanoparticle in this Si-C composite material is 13nm, and nano-silicon content is 37%.
Gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10, wherein Si-C composite material 0.24g, acetylene black 0.03g, PVDF 0.03g, this mixture is modulated into slurry with NMP (1-Methyl-2-Pyrrolidone), evenly be coated on Copper Foil, 100 DEG C of vacuumize 24 hours, makes experimental cell pole piece.Taking lithium sheet as to electrode, electrolyte is 1mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box that is full of argon gas atmosphere.
The battery of pressing the present embodiment made, first discharge specific capacity has reached 613mAh/g, after 100 circulations, still remains on 177mAh/g.
Embodiment seven
Take 3g polyacrylonitrile and be dissolved in 10mLN, in dinethylformamide and 10mLN-methyl pyrrolidone, then add 0.80g silicon monoxide, and ultrasonic dispersion 100min.Stir evaporation after DMF the mixture of thickness, proceeded in porcelain boat, under argon shield, be warmed up to 1300 DEG C, be incubated 0.5 hour, cooling rear taking-up, obtains the composite material of 2.3g porous carbon coated silica and silicon nanoparticle.
Gained composite material is joined in 20mL 10wt% sodium hydroxide solution, and after continuous stirring 3h, gained suspended matter is leached, and fully wash with distilled water, 100 DEG C of dry 1.9g Si-C composite materials that obtain for 12 hours.
The particle diameter that adopts the method identical with embodiment mono-to record silicon nanoparticle in this Si-C composite material is 17nm, and nano-silicon content is 11%.
Gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10, wherein Si-C composite material 0.24g, acetylene black 0.03g, PVDF 0.03g, this mixture is modulated into slurry with NMP (1-Methyl-2-Pyrrolidone), evenly be coated on Copper Foil, 100 DEG C of vacuumize 24 hours, makes experimental cell pole piece.Taking lithium sheet as to electrode, electrolyte is 1mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box that is full of argon gas atmosphere.
The battery of pressing the present embodiment made, first discharge specific capacity has reached 778mAh/g, after 100 circulations, still remains on 281mAh/g.
Embodiment eight
Take 10.0g polyacrylonitrile and 8.8g silicon monoxide, ball milling mixing 30min in ball mill.Proceeded in porcelain boat, under argon shield, be warmed up to 1150 DEG C, be incubated 3 hours, cooling rear taking-up.In the temperature-rise period last stage, when temperature reaches high molecular polymer polyacrylonitrile melt temperature, the coated silicon monoxide of the first melting of polyacrylonitrile, in the time that temperature continuation rising reaches more than 700 DEG C, polyacrylonitrile generation carburizing reagent, silicon monoxide generation disproportionated reaction, obtains the composite material of 13g porous carbon coated silica and silicon nanoparticle.
Gained composite material is joined in 100mL 5wt% sodium hydroxide solution, and after continuous stirring 30h, gained suspended matter is leached, silicon dioxide in whipping process in composite material reacts with NaOH and generates water-soluble sodium metasilicate, fully wash and remove NaOH and sodium metasilicate with distilled water subsequently, 100 DEG C of dry 5.2g Si-C composite materials that obtain for 12 hours, this composite material is mainly hollow porous carbon bag and covers silicon nanoparticle, also has the silicon grain and other impurity that are not wrapped by a small quantity.
The particle diameter that adopts the method identical with embodiment mono-to record silicon nanoparticle in this Si-C composite material is 80nm, and nano-silicon content is 57%.
Gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10, wherein Si-C composite material 0.24g, acetylene black 0.03g, PVDF 0.03g, this mixture is modulated into slurry with NMP (1-Methyl-2-Pyrrolidone), evenly be coated on Copper Foil, 100 DEG C of vacuumize 24 hours, makes experimental cell pole piece.Taking lithium sheet as to electrode, electrolyte is 1mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box that is full of argon gas atmosphere.
The battery of pressing the present embodiment made, first discharge specific capacity has reached 1556mAh/g, after 100 circulations, still remains on 825mAh/g.
Embodiment nine
Take 15g starch and 8.80g silicon monoxide, ball milling mixing 30min in ball mill.Proceeded in porcelain boat, be warmed up to 950 DEG C under argon shield, be incubated 10 hours, cooling rear taking-up, obtains the composite material of 15.0g porous carbon coated silica and silicon nanoparticle.
Gained composite material is joined in 50mL 15wt% sodium hydroxide solution, and after continuous stirring 11h, gained suspended matter is leached, and fully wash with distilled water, 100 DEG C of dry 9.3g Si-C composite materials that obtain for 12 hours.
The particle diameter that adopts the method identical with embodiment mono-to record silicon nanoparticle in this Si-C composite material is 13nm, and nano-silicon content is 27%.
Gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10, wherein Si-C composite material 0.24g, acetylene black 0.03g, PVDF 0.03g, this mixture is modulated into slurry with NMP (1-Methyl-2-Pyrrolidone), evenly be coated on Copper Foil, 100 DEG C of vacuumize 24 hours, makes experimental cell pole piece.Taking lithium sheet as to electrode, electrolyte is 1mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box that is full of argon gas atmosphere.
The battery of pressing the present embodiment made, first discharge specific capacity has reached 1268mAh/g, after 100 circulations, still remains on 667mAh/g.
Embodiment ten
Take 8g phenolic resins and 8.8g silicon monoxide, ball milling mixing 50min in ball mill.Proceeded in porcelain boat, be warmed up to 1150 DEG C under argon shield, be incubated 2 hours, cooling rear taking-up, obtains the composite material of 13.1g porous carbon coated silica and silicon nanoparticle.
Gained composite material is joined in 30mL 30wt% sodium hydroxide solution, and after continuous stirring 2h, gained suspended matter is leached, and fully wash with distilled water, 100 DEG C dry 12 hours 8.6g Si-C composite material.
The particle diameter that adopts the method identical with embodiment mono-to record silicon nanoparticle in this Si-C composite material is 77nm, and nano-silicon content is 32%.
Gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10, wherein Si-C composite material 0.24g, acetylene black 0.03g, PVDF 0.03g, this mixture is modulated into slurry with NMP (1-Methyl-2-Pyrrolidone), evenly be coated on Copper Foil, 100 DEG C of vacuumize 24 hours, makes experimental cell pole piece.Taking lithium sheet as to electrode, electrolyte is 1mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box that is full of argon gas atmosphere.
The battery of pressing the present embodiment made, first discharge specific capacity has reached 1107mAh/g, after 100 circulations, still remains on 631mAh/g.
Embodiment 11
Take 0.98g phenolic resins and 8.8g silicon monoxide, ball milling mixing 50min in ball mill.Proceeded in porcelain boat, be warmed up to 1150 DEG C under argon shield, be incubated 2 hours, cooling rear taking-up, obtains the composite material of 9.3g porous carbon coated silica and silicon nanoparticle.
Gained composite material is joined in 1000mL 1wt% sodium hydroxide solution, and after continuous stirring 2h, gained suspended matter is leached, and fully wash with distilled water, 100 DEG C dry 12 hours 8.0g Si-C composite material.
The particle diameter that adopts the method identical with embodiment mono-to record silicon nanoparticle in this Si-C composite material is 71nm, and nano-silicon content is 90%.
Gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10, wherein Si-C composite material 0.24g, acetylene black 0.03g, PVDF 0.03g, this mixture is modulated into slurry with NMP (1-Methyl-2-Pyrrolidone), evenly be coated on Copper Foil, 100 DEG C of vacuumize 24 hours, makes experimental cell pole piece.Taking lithium sheet as to electrode, electrolyte is 1mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box that is full of argon gas atmosphere.
The battery of pressing the present embodiment made, first discharge specific capacity has reached 2134mAh/g, after 100 circulations, still remains on 417mAh/g.
By the above detailed description to the embodiment of the present invention, can understand and the invention solves conventional Si-C composite material clad nano silicon completely, the problem that causes the bulk effect of silicon not to be effectively suppressed, adopt simple process to prepare the Si-C composite material of distribution homogeneous, solved that in lithium ion battery, siliceous negative material capacity is little, cycle performance is poor, expansive problem.
Be understandable that, above execution mode is only used to principle of the present invention is described and the illustrative embodiments that adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (16)
1. a preparation method for Si-C composite material, is characterized in that comprising the following steps:
(1) prepared polymer solution: high molecular polymer is dissolved in solvent, obtains the polymer solution of 1-20wt%;
(2) silicon monoxide is even with polymer mixed: silicon monoxide is mixed in proportion with the polymer solution of step (1) gained, fully disperse, then except desolventizing, obtain the composite material of polymer overmold silicon monoxide;
(3) high temperature carries out carbonization and disproportionated reaction: the composite material of the polymer overmold silicon monoxide to step (2) gained under protective atmosphere heats, make high molecular polymer generation carburizing reagent, silicon monoxide generation disproportionated reaction, obtains the composite material of porous carbon ball coated silica/nano-silicon;
(4) corrosion is except silicon dioxide: by the composite material of the porous carbon ball coated silica/nano-silicon of step (3) gained and corrosive liquid in mass ratio 1: 5-1: 100 mix, stir and separate to obtain Si-C composite material after 0.5-24 hour, this Si-C composite material comprises that the porous carbon bag of nucleocapsid structure covers silicon nanoparticle, between described porous carbon ball and described nano-silicon, leave space, and the particle diameter of silicon nanoparticle is 5-80nm in Si-C composite material, wherein nano-silicon content is 10-90wt%.
2. preparation method according to claim 1, is characterized in that the middle high molecular polymer of described step (1) comprises one or more in polyvinyl chloride, polymethyl methacrylate, polyacrylonitrile, phenolic resins, pitch, glucose, sucrose, starch.
3. preparation method according to claim 2, is characterized in that the middle solvent of described step (1) comprises one or more in water, ethanol, acetone, oxolane, chloroform, 1-METHYLPYRROLIDONE or DMF.
4. preparation method according to claim 1, is characterized in that in described step (2), silicon monoxide mixes in proportion and refers to that silicon monoxide and polymer solution mass ratio are 1: 1-1: 200 with polymer solution; Fully disperse to refer to adopt ultrasonic wave to disperse 10-100 minute, ultrasonic frequency is 40,000 Hz.
5. a preparation method for Si-C composite material, is characterized in that comprising the following steps:
(1) silicon monoxide and polymer mixed are even: silicon monoxide and high molecular polymer are taken in proportion, and with ball mill ball milling 0.5-24 hour, obtain mixture of powders;
(2) high temperature carries out carbonization and disproportionated reaction: under protective atmosphere, the mixture of powders of step (1) gained is heated, make high molecular polymer generation carburizing reagent, silicon monoxide generation disproportionated reaction, obtains the composite material of porous carbon ball coated silica/nano-silicon;
(3) corrosion is except silicon dioxide: by the composite material of the porous carbon ball coated silica/nano-silicon of step (2) gained and corrosive liquid in mass ratio 1: 5-1: 100 mix, stir and separate to obtain Si-C composite material after 0.5-24 hour, this Si-C composite material comprises that the porous carbon bag of nucleocapsid structure covers silicon nanoparticle, between described porous carbon ball and described nano-silicon, leave space, and the particle diameter of silicon nanoparticle is 5-80nm in Si-C composite material, wherein nano-silicon content is 10-90wt%.
6. preparation method according to claim 5, is characterized in that the middle silicon monoxide of described step (1) and high molecular polymer mass ratio are 1: 9-9: 1.
7. preparation method according to claim 1 or 5, is characterized in that the temperature that described high temperature carries out carbonization and disproportionated reaction is 700-1500 DEG C, and be 0.5-12 hour heating time.
8. preparation method according to claim 7, is characterized in that the temperature that described high temperature carries out carbonization and disproportionated reaction is 900-1200 DEG C, and be 1-5h heating time.
9. preparation method according to claim 1 or 5, is characterized in that described protective atmosphere is the gaseous mixture of nitrogen, argon gas or argon gas and hydrogen.
10. preparation method according to claim 1 or 5, is characterized in that described corrosive liquid is the hydrofluoric acid aqueous solution of 3-40wt%.
11. preparation methods according to claim 10, is characterized in that described corrosive liquid is the hydrofluoric acid aqueous solution of 5-20wt%.
12. preparation methods according to claim 1 or 5, is characterized in that described corrosive liquid is lithium hydroxide or potassium hydroxide or the NaOH of 0.4-30wt%.
13. preparation methods according to claim 12, is characterized in that described corrosive liquid is the NaOH of 1-30wt%.
14. preparation methods according to claim 5, is characterized in that described high molecular polymer comprises one or more in polyvinyl chloride, polymethyl methacrylate, polyacrylonitrile, phenolic resins, pitch, glucose, sucrose, starch.
15. 1 kinds of lithium ion battery negative materials, is characterized in that comprising the Si-C composite material of preparing with the arbitrary described method of claim 1-14.
16. 1 kinds of lithium ion batteries, is characterized in that comprising the negative pole of preparing battery with lithium ion battery negative material described in claim 15.
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| Electrospray Synthesis of Silicon/Carbon Nanoporous Microspheres as Improved Anode Materials for Lithium-Ion Batteries;Ya-Xia Yin等;《The Journal of Physical Chemistry》;20110623;第115卷(第29期);14148-14154 * |
| Jae-Hun Kim等.Enhanced cycle performance of SiO-C composite anode for lithium-ion batteries.《Journal of Power Sources》.2007,第170卷(第2期), * |
| Ya-Xia Yin等.Electrospray Synthesis of Silicon/Carbon Nanoporous Microspheres as Improved Anode Materials for Lithium-Ion Batteries.《The Journal of Physical Chemistry》.2011,第115卷(第29期), |
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