CN102447112A - 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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- CN102447112A CN102447112A CN2011103998340A CN201110399834A CN102447112A CN 102447112 A CN102447112 A CN 102447112A CN 2011103998340 A CN2011103998340 A CN 2011103998340A CN 201110399834 A CN201110399834 A CN 201110399834A CN 102447112 A CN102447112 A CN 102447112A
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 81
- 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 29
- 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 67
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 55
- 239000002245 particle Substances 0.000 claims abstract description 14
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 80
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 62
- 239000005543 nano-size silicon particle Substances 0.000 claims description 58
- 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 34
- 238000000034 method Methods 0.000 claims description 31
- 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 27
- 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 21
- 235000012239 silicon dioxide Nutrition 0.000 claims description 19
- 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
- 238000005303 weighing Methods 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
- 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
- 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
- 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
- 230000007797 corrosion Effects 0.000 claims description 5
- 238000005260 corrosion Methods 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
- 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
- 238000000498 ball milling Methods 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 24
- 239000010703 silicon Substances 0.000 abstract description 23
- 229910052710 silicon Inorganic materials 0.000 abstract description 22
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000011856 silicon-based particle Substances 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
- 230000004087 circulation Effects 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 13
- 230000004888 barrier function 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
- 206010013786 Dry skin Diseases 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000001132 ultrasonic dispersion Methods 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000002253 acid Substances 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
- 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
- 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
- 230000006872 improvement 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
- 239000000126 substance Substances 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
- 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
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution 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
- 230000004927 fusion Effects 0.000 description 1
- 238000005087 graphitization Methods 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
- 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
- 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
- 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
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention 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 manufacturing technology field, be specifically related to a kind of Si-C composite material and preparation method thereof and contain the lithium ion battery negative material and the lithium ion battery of this Si-C composite material.
Background technology
Exhaustion day by day along with fossil fuel; And the fast development of portable electric appts and electric vehicle; The research of new forms of energy such as power-supply battery has become the focus that the whole world is paid close attention to, and wherein lithium ion battery is because of its energy density is high, power density is high, good cycle, environmental friendliness, structure variation and excellent specific property such as cheap are used widely.With regard to the structure of lithium ion battery, it mainly is 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 lithium ion battery performance.
To the demand for development of lithium-ion-power cell, require objectively that negative material has that high power capacity, rapid rate discharge and recharge, characteristics such as high thermal stability and low cost.The more negative material of practical application is a material with carbon element at present; Like native graphite, graphitization carbonaceous mesophase spherules etc.; Wherein the theoretical capacity of graphite cathode material is 372mAh/g; Actual capacity is at 320-350mAh/g, and 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) is when forming Li
4.4Theoretical capacity during the 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, and its volumetric expansion is up to 300%, the efflorescence render electrical electrode structure unstability of silicon and losing efficacy.Particularly common pure silicon, stable circulation is very poor, and the capacity that circulates after 5 times is just almost nil from reducing to more than the 3000mAh/g.
At present; More effectively prepare carbon-silicon composite material in the method for modifying to the proposition of lithium ion battery negative material the problems referred to above and alleviate the volumetric expansion in the 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 the method for utilizing " buffering skeleton " to come compensative material to expand.In theory, as long as the electrode potential of two kinds of materials is incomplete same, the phase of electro-chemical activity just can be embedded in the active skeleton of relative non-electrochemical, and non-active material plays the effect that disperses and cushion medium.Utilize the coordinating effect between each component of composite material, can reach the purpose of mutual supplement with each other's advantages.
Carbonaceous negative material change in volume in charge and discharge process is less relatively, and is the good conductor of electronics, therefore is selected as the dispersible carrier of dispersed silicon particle.The chemical property of silicon and carbon is close in addition, can combine closely.Silicon grain is if can be nano-dispersed in material with carbon element, the space between structure that material with carbon element itself is had and the silicon grain that is nano-dispersed all can be lithium ion provides a large amount of passages, increases the embedded location of lithium ion.Compound can the reaching of carbon silicon improved the silicon bulk effect, improves the purpose of its electrochemical stability.Therefore multiple material with carbon element is used to the negative material with compound preparation high power capacity of silicon and excellent cycle performance.One Chinese patent application numbers 200910037666.3 discloses the patent that name is called " a kind of preparation method of lithium ion battery silicon-carbon cathode material ", and this method is dispersed in preparation organogel in back in the cold primer-oil with nano silica fume, make product through dry, carbonization again.This method directly adopts nano silica fume as raw material, and cost height and poor effect because nano silica fume is easy to reunite, are difficult to be dispersed in the pitch matrix, cause prepared negative material cycle performance not good.
Summary of the invention
Technical problem to be solved by this invention is to the above-mentioned deficiency that exists in the prior art; A kind of Si-C composite material and preparation method thereof is provided; Technology is simple; Prepared Si-C composite material can effectively suppress the expansion of silicon volume, and the ion cathode material lithium of preparation has excellent electric conductivity thus, big, the good cycle of corresponding lithium ion battery specific capacity.
Solving the technical scheme that technical problem of the present invention adopted is that this Si-C composite material comprises that hollow porous carbon bag covers silicon nanoparticle, and the particle diameter of silicon nanoparticle is 5-80nm in the Si-C composite material, and wherein nano-silicon content is 10-90wt%.Adopt " nucleocapsid " structure of this uniqueness between porous carbon and silicon nanoparticle, to leave certain gap; Make electrode material in charge and discharge process, keep structural intergrity; Effectively suppress the expansion of silicon volume, thereby make the increase of enclosed pasture efficient and the irreversible capacity of electrode reduce.
The present invention also provides the preparation method of this Si-C composite material, may further comprise the steps:
(1) prepared polymer solution: high molecular polymer is dissolved in the solvent, gets the polymer solution of 1-20wt%;
(2) silicon monoxide is even with mixed with polymers: the polymer solution of silicon monoxide with step (1) gained mixed in proportion, fully disperse, remove and desolvate, get the composite material of polymer overmold silicon monoxide;
(3) high temperature carries out carbonization and disproportionated reaction: the composite material to the polymer overmold silicon monoxide of step (2) gained under protective atmosphere heats; Make high molecular polymer generation carburizing reagent; Silicon monoxide generation disproportionated reaction obtains the composite material that the porous carbon bag covers silicon dioxide/nano-silicon;
(4) corrosion removes silicon dioxide: the composite material that the porous carbon bag of step (3) gained is covered silicon dioxide/nano-silicon and corrosive liquid are by mass ratio 1: 5-1: 100 mix, stir separate after 0.5-24 hour Si-C composite material.
Preferably, the middle high molecular polymer of said step (1) comprises one or more in polyvinyl chloride, polymethyl methacrylate, polyacrylonitrile, phenolic resins, pitch, glucose, sucrose, the starch.
Correspondingly, according to selected high molecular polymer, solvent comprises water, ethanol, acetone, oxolane, chloroform, N-methyl pyrrolidone or N, one or more in the dinethylformamide in the said step (1).
Preferably, silicon monoxide mixes in proportion with polymer solution and refers to that silicon monoxide and polymer solution mass ratio are 1: 1-1: 200 in the said step (2); Fully disperse to refer to adopt ultrasonic dispersing 10-100 minute, ultrasonic frequency is 40,000 Hz.
Outside silicon monoxide, in heat treatment process, disproportionated reaction at high temperature takes place and generates silicon and silicon dioxide in silicon monoxide with polymer overmold, and the two evenly is mingled in together.Polymer cracking carbonization at high temperature simultaneously generates amorphous carbon; Polymer covering layer becomes the porous carbon shell after heat treatment like this; Silicon and coated with silica in inside, are handled product with corrosive liquid subsequently, and the silicon dioxide in the porous carbon shell is corroded; Stay 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 coat silicon grain through methods such as high-temperature decomposition, chemical vapour deposition technique and ball-milling methods, forms nucleocapsid structure, plays the volume cushioning effect, is the first-selection of preparation carbon-silicon composite material.
Above-mentioned Si-C composite material also can prepare through following method, specifically may further comprise the steps:
(1) silicon monoxide and mixed with polymers are even: silicon monoxide and high molecular polymer are taken by weighing in proportion, and with ball mill ball milling 0.5-24 hour, mixture of powders;
(2) high temperature carries out carbonization and disproportionated reaction: the mixture of powders to step (1) gained under protective atmosphere heats; Make high molecular polymer generation carburizing reagent; Silicon monoxide generation disproportionated reaction obtains the composite material that the porous carbon bag covers silicon dioxide/nano-silicon;
(3) corrosion removes silicon dioxide: the composite material that the porous carbon bag of step (2) gained is covered silicon dioxide/nano-silicon and corrosive liquid are by mass ratio 1: 5-1: 100 mix, stir separate after 0.5-24 hour Si-C composite material.
Preferably, silicon monoxide and high molecular polymer mass ratio are 1 in the above-mentioned steps (1): 9-9: 1.
Preferably, the temperature that said high temperature carries out carbonization and disproportionated reaction is 700-1500 ℃, and be 0.5-12 hour heating time.
Further preferably, the temperature that said high temperature carries out carbonization and disproportionated reaction is preferably 900-1200 ℃, is preferably 1-5h heating time.
Preferably, said protective atmosphere is the gaseous mixture of nitrogen, argon gas or argon gas and hydrogen.
Preferably, said corrosive liquid is the hydrofluoric acid aqueous solution of 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 after covering the composite material of silicon dioxide/nano-silicon with hydrofluoric acid aqueous solution corrosion porous carbon bag; Silicon dioxide is by reaction consumes in the porous carbon ball, and remaining equally distributed nano-silicon is stayed in the porous carbon shell.
Further preferably, said corrosive liquid is the hydrofluoric acid aqueous solution of 5-20wt%.
Preferably, said 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, said corrosive liquid is the NaOH of 1-30wt%.
Preferably, said high molecular polymer comprises one or more in polyvinyl chloride, polymethyl methacrylate, polyacrylonitrile, phenolic resins, pitch, glucose, sucrose, the starch.
The present invention also provides the lithium ion battery negative material of above-mentioned Si-C composite material preparation, and promptly this lithium ion battery negative material comprises the Si-C composite material of method for preparing.
Prepare the negative pole of lithium ion battery with above-mentioned lithium ion battery negative material, be assembled into lithium ion battery again, promptly this lithium ion battery comprises the negative pole for 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; Space between spherical structure that material with carbon element itself is had and the silicon grain that is nano-dispersed all can be lithium ion provides a large amount of passages; Increase the embedded location of lithium ion, improve the silicon bulk effect, improve its electrochemical stability.Have marked improvement aspect the specific capacity of improving lithium ion battery and the cycle performance, by the battery of made of the present invention, first discharge specific capacity has reached 537-2134mAh/g, still remains on 177-850mAh/g after 100 circulations.
Description of 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 cycle performance resolution chart in specific embodiment of the present invention.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, the present invention is described in further detail below in conjunction with accompanying drawing.
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.Used ultrasonic dispersing appearance frequency is 40,000 Hz.
Embodiment one
Take by weighing 0.4g phenolic resins and be dissolved in and obtain the polymer phenol resin solution in the 30mL ethanol, add the 0.80g silicon monoxide again, and ultrasonic dispersion 10min, make silicon monoxide be well-dispersed in the polymer phenol resin solution.Get the mixture of thickness after the stirring ethanol evaporation, promptly polymer phenolic resins coats the composite material of silicon monoxide, and it is changed in the porcelain boat; Under gaseous mixture (hydrogen content 5%) protection of argon gas and hydrogen, be warmed up to 1000 ℃; Be incubated 4 hours, phenolic resins generation carburizing reagent in this process, silicon monoxide generation disproportionated reaction; Take out the cooling back, gets the composite material of 1.0g porous carbon coated silica/silicon nanoparticle.
The gained composite material is joined in the 50mL 3wt% hydrofluoric acid solution; And behind the continuous stirring 10h gained suspended matter is leached; In whipping process; Silicon dioxide in the composite material and hydrofluoric acid reaction generate products such as water-soluble fluosilicic acid, and remaining equally distributed nano-silicon is stayed in the porous carbon shell.Fully wash products such as removing hydrofluoric acid, fluosilicic acid with distilled water subsequently; 100 ℃ promptly got the 0.5g Si-C composite material down in dry 12 hours; This Si-C composite material is mainly hollow porous carbon bag and covers silicon nanoparticle, and the silicon grain and other impurity that are not coated are on a small quantity also arranged.The preparation flow figure of this Si-C composite material is as shown in Figure 1.
The particle diameter that records silicon nanoparticle in this Si-C composite material through transmission electron microscope is 20nm, records through thermogravimetric analyzer that nano-silicon content is 51% in this Si-C composite material.
The gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10; Si-C composite material 0.24g wherein, acetylene black 0.03g, PVDF 0.03g; With NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry; Evenly be coated on the Copper Foil, 100 ℃ of vacuumize 24 hours makes Experimental cell and uses pole piece.With the lithium sheet is to electrode, and electrolyte is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
As shown in Figure 2; Press the battery of present embodiment made; First discharge specific capacity has reached 1573mAh/g; For the second time specific discharge capacity just drops to about 950mAh/g, and this mainly is to generate solid electrolyte membrane (SEI film) and part irreversible reaction (silicon grain that does not coat like part splits and comes off, composite material in have small amount of oxygen to combine the generation lithia with lithium) first in the discharge process to cause.But first charge-discharge is afterwards along with cycle-index increases; The decay of battery specific capacity is also not obvious; Still remain on 850mAh/g after 100 circulations, explain 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 two
Take by weighing the 1g polyvinyl chloride and be dissolved in the 30mL chloroform, add the 0.80g silicon monoxide again, and ultrasonic dispersion 60min.Stir behind the evaporation chloroform the mixture of thickness, it is changed in the porcelain boat, under argon shield, be warmed up to 900 ℃, be incubated 12 hours, take out the cooling back, gets the composite material of 1.1g porous carbon coated silica/silicon nanoparticle.
The gained composite material is joined in the 25mL 8wt% hydrofluoric acid solution, and behind the continuous stirring 6h gained suspended matter is leached, and fully wash with distilled water, 100 ℃ of dryings promptly got the 0.6g Si-C composite material in 12 hours.
Employing is 21nm with the particle diameter that embodiment one identical method records silicon nanoparticle in this Si-C composite material, and nano-silicon content is 43%.
The gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10; Si-C composite material 0.24g wherein, acetylene black 0.03g, PVDF 0.03g; With NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry; Evenly be coated on the Copper Foil, 100 ℃ of vacuumize 24 hours makes Experimental cell and uses pole piece.With the lithium sheet is to electrode, and electrolyte is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Press the battery of present embodiment made, first discharge specific capacity has reached 1352mAh/g, still remains on 593mAh/g after 100 circulations.
Embodiment three
Take by weighing the 3.2g polymethyl methacrylate and be dissolved in the 30mL acetone, add the 0.80g silicon monoxide again, and ultrasonic dispersion 100min.Stir behind the evaporation acetone the mixture of thickness, it is changed in the porcelain boat, under argon shield, be warmed up to 1050 ℃, be incubated 4 hours, take out the cooling back, gets the composite material of 1.5g porous carbon coated silica and silicon nanoparticle.
The gained composite material is joined in the 20mL 20wt% hydrofluoric acid solution, and behind the continuous stirring 1h gained suspended matter is leached, and fully wash with distilled water, 100 ℃ of dryings promptly got the 0.9g Si-C composite material in 12 hours.
Employing is 34nm with the particle diameter that embodiment one identical method records silicon nanoparticle in this Si-C composite material, and nano-silicon content is 31%.
The gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10; Si-C composite material 0.24g wherein, acetylene black 0.03g, PVDF 0.03g; With NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry; Evenly be coated on the Copper Foil, 100 ℃ of vacuumize 24 hours makes Experimental cell and uses pole piece.With the lithium sheet is to electrode, and electrolyte is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Press the battery of present embodiment made, first discharge specific capacity has reached 1231mAh/g, still remains on 633mAh/g after 100 circulations.
Embodiment four
Take by weighing 0.3g glucose and be dissolved in the mixed solvent of 30mL distilled water, add the 0.80g silicon monoxide again, and ultrasonic dispersion 50min.Stir behind the evaporation mixed solvent the mixture of thickness, it is changed in the porcelain boat, under argon shield, be warmed up to 1100 ℃, be incubated 1 hour, take out the cooling back, gets the composite material of 0.9g porous carbon coated silica and silicon nanoparticle.
The gained composite material is joined in the 5mL 40wt% hydrofluoric acid solution, and behind the continuous stirring 8h gained suspended matter is leached, and fully wash with distilled water, 100 ℃ of dryings promptly got the 0.4g Si-C composite material in 12 hours.
Employing is 46nm with the particle diameter that embodiment one identical method records silicon nanoparticle in this Si-C composite material, and nano-silicon content is 63%.
The gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10; Si-C composite material 0.24g wherein, acetylene black 0.03g, PVDF 0.03g; With NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry; Evenly be coated on the Copper Foil, 100 ℃ of vacuumize 24 hours makes Experimental cell and uses pole piece.With the lithium sheet is to electrode, and electrolyte is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Press the battery of present embodiment made, first discharge specific capacity has reached 1438mAh/g, still remains on 813mAh/g after 100 circulations.
Embodiment five
Take by weighing 2g glucose and 2g sucrose and be dissolved in the mixed solvent of 30mL ethanol and 30mL distilled water, add the 0.80g silicon monoxide again, and ultrasonic dispersion 50min.Stir behind the evaporation mixed solvent the mixture of thickness, it is changed in the porcelain boat, under nitrogen protection, be warmed up to 700 ℃, be incubated 12 hours, take out the cooling back, gets the composite material of 1.3g porous carbon coated silica and silicon nanoparticle.
The gained composite material is joined in the 40mL 5wt% hydrofluoric acid solution, and behind the continuous stirring 12h gained suspended matter is leached, and fully wash with distilled water, 100 ℃ of dryings promptly got the 0.7g Si-C composite material in 12 hours.
Employing is 5nm with the particle diameter that embodiment one identical method records silicon nanoparticle in this Si-C composite material, and nano-silicon content is 23%.
The gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10; Si-C composite material 0.24g wherein, acetylene black 0.03g, PVDF 0.03g; With NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry; Evenly be coated on the Copper Foil, 100 ℃ of vacuumize 24 hours makes Experimental cell and uses pole piece.With the lithium sheet is to electrode, and electrolyte is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Press the battery of present embodiment made, first discharge specific capacity has reached 537mAh/g, still remains on 223mAh/g after 100 circulations.
Embodiment six
Take by weighing 0.8g pitch and be dissolved in the 50mL oxolane, add the 0.80g silicon monoxide again, and ultrasonic dispersion 30min.Stir behind the evaporation oxolane the mixture of thickness, it is changed in the porcelain boat, under argon shield, be warmed up to 1500 ℃, be incubated 0.5 hour, take out the cooling back, gets the composite material of 1.2g porous carbon coated silica and silicon nanoparticle.
The gained composite material is joined in the 5mL 30wt% hydrofluoric acid solution, and behind the continuous stirring 6h gained suspended matter is leached, and fully wash with distilled water, 100 ℃ of dryings promptly got the 0.8g Si-C composite material in 12 hours.
Employing is 13nm with the particle diameter that embodiment one identical method records silicon nanoparticle in this Si-C composite material, and nano-silicon content is 37%.
The gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10; Si-C composite material 0.24g wherein, acetylene black 0.03g, PVDF 0.03g; With NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry; Evenly be coated on the Copper Foil, 100 ℃ of vacuumize 24 hours makes Experimental cell and uses pole piece.With the lithium sheet is to electrode, and electrolyte is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Press the battery of present embodiment made, first discharge specific capacity has reached 613mAh/g, still remains on 177mAh/g after 100 circulations.
Embodiment seven
Take by weighing the 3g polyacrylonitrile and be dissolved in 10mLN, in dinethylformamide and the 10mLN-methyl pyrrolidone, add the 0.80g silicon monoxide again, and ultrasonic dispersion 100min.Stir and evaporate N, get the mixture of thickness behind the dinethylformamide, it is changed in the porcelain boat, under argon shield, be warmed up to 1300 ℃, be incubated 0.5 hour, take out the cooling back, gets the composite material of 2.3g porous carbon coated silica and silicon nanoparticle.
The gained composite material is joined in the 20mL 10wt% sodium hydroxide solution, and behind the continuous stirring 3h gained suspended matter is leached, and fully wash with distilled water, 100 ℃ of dryings promptly got the 1.9g Si-C composite material in 12 hours.
Employing is 17nm with the particle diameter that embodiment one identical method records silicon nanoparticle in this Si-C composite material, and nano-silicon content is 11%.
The gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10; Si-C composite material 0.24g wherein, acetylene black 0.03g, PVDF 0.03g; With NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry; Evenly be coated on the Copper Foil, 100 ℃ of vacuumize 24 hours makes Experimental cell and uses pole piece.With the lithium sheet is to electrode, and electrolyte is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Press the battery of present embodiment made, first discharge specific capacity has reached 778mAh/g, still remains on 281mAh/g after 100 circulations.
Embodiment eight
Take by weighing 10.0g polyacrylonitrile and 8.8g silicon monoxide, ball mill mixing 30min in ball mill.It is changed in the porcelain boat, under argon shield, be warmed up to 1150 ℃, be incubated 3 hours, take out the cooling back.In the temperature-rise period last stage; When temperature reaches high molecular polymer polyacrylonitrile melt temperature; The fusion of polyacrylonitrile elder generation coats silicon monoxide, when temperature continuation rising reaches more than 700 ℃, and polyacrylonitrile generation carburizing reagent; Silicon monoxide generation disproportionated reaction, the composite material of 13g porous carbon coated silica and silicon nanoparticle.
The gained composite material is joined in the 100mL 5wt% sodium hydroxide solution; And behind the continuous stirring 30h gained suspended matter is leached; Silicon dioxide in the whipping process in the composite material and NaOH reaction generate water-soluble sodium metasilicate; Fully wash with distilled water subsequently and remove NaOH and sodium metasilicate; 100 ℃ of dryings promptly got the 5.2g Si-C composite material in 12 hours, and this composite material is mainly hollow porous carbon bag and covers silicon nanoparticle, and the silicon grain and other impurity that are not coated are on a small quantity also arranged.
Employing is 80nm with the particle diameter that embodiment one identical method records silicon nanoparticle in this Si-C composite material, and nano-silicon content is 57%.
The gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10; Si-C composite material 0.24g wherein, acetylene black 0.03g, PVDF 0.03g; With NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry; Evenly be coated on the Copper Foil, 100 ℃ of vacuumize 24 hours makes Experimental cell and uses pole piece.With the lithium sheet is to electrode, and electrolyte is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Press the battery of present embodiment made, first discharge specific capacity has reached 1556mAh/g, still remains on 825mAh/g after 100 circulations.
Embodiment nine
Take by weighing 15g starch and 8.80g silicon monoxide, ball mill mixing 30min in ball mill.It is changed in the porcelain boat, under argon shield, be warmed up to 950 ℃, be incubated 10 hours, take out the cooling back, gets the composite material of 15.0g porous carbon coated silica and silicon nanoparticle.
The gained composite material is joined in the 50mL 15wt% sodium hydroxide solution, and behind the continuous stirring 11h gained suspended matter is leached, and fully wash with distilled water, 100 ℃ of dryings promptly got the 9.3g Si-C composite material in 12 hours.
Employing is 13nm with the particle diameter that embodiment one identical method records silicon nanoparticle in this Si-C composite material, and nano-silicon content is 27%.
The gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10; Si-C composite material 0.24g wherein, acetylene black 0.03g, PVDF 0.03g; With NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry; Evenly be coated on the Copper Foil, 100 ℃ of vacuumize 24 hours makes Experimental cell and uses pole piece.With the lithium sheet is to electrode, and electrolyte is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Press the battery of present embodiment made, first discharge specific capacity has reached 1268mAh/g, still remains on 667mAh/g after 100 circulations.
Embodiment ten
Take by weighing 8g phenolic resins and 8.8g silicon monoxide, ball mill mixing 50min in ball mill.It is changed in the porcelain boat, under argon shield, be warmed up to 1150 ℃, be incubated 2 hours, take out the cooling back, gets the composite material of 13.1g porous carbon coated silica and silicon nanoparticle.
The gained composite material is joined in the 30mL 30wt% sodium hydroxide solution, and behind the continuous stirring 2h gained suspended matter is leached, and fully wash with distilled water, 100 ℃ of dryings got the 8.6g Si-C composite material in 12 hours.
Employing is 77nm with the particle diameter that embodiment one identical method records silicon nanoparticle in this Si-C composite material, and nano-silicon content is 32%.
The gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10; Si-C composite material 0.24g wherein, acetylene black 0.03g, PVDF 0.03g; With NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry; Evenly be coated on the Copper Foil, 100 ℃ of vacuumize 24 hours makes Experimental cell and uses pole piece.With the lithium sheet is to electrode, and electrolyte is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Press the battery of present embodiment made, first discharge specific capacity has reached 1107mAh/g, still remains on 631mAh/g after 100 circulations.
Embodiment 11
Take by weighing 0.98g phenolic resins and 8.8g silicon monoxide, ball mill mixing 50min in ball mill.It is changed in the porcelain boat, under argon shield, be warmed up to 1150 ℃, be incubated 2 hours, take out the cooling back, gets the composite material of 9.3g porous carbon coated silica and silicon nanoparticle.
The gained composite material is joined in the 1000mL 1wt% sodium hydroxide solution, and behind the continuous stirring 2h gained suspended matter is leached, and fully wash with distilled water, 100 ℃ of dryings got the 8.0g Si-C composite material in 12 hours.
Employing is 71nm with the particle diameter that embodiment one identical method records silicon nanoparticle in this Si-C composite material, and nano-silicon content is 90%.
The gained Si-C composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10; Si-C composite material 0.24g wherein, acetylene black 0.03g, PVDF 0.03g; With NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry; Evenly be coated on the Copper Foil, 100 ℃ of vacuumize 24 hours makes Experimental cell and uses pole piece.With the lithium sheet is to electrode, and electrolyte is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Press the battery of present embodiment made, first discharge specific capacity has reached 2134mAh/g, still remains on 417mAh/g after 100 circulations.
By above detailed description to the embodiment of the invention; Can understand and the invention solves conventional Si-C composite material clad nano silicon fully; 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 siliceous negative material capacity is little in the lithium ion battery, cycle performance is poor, expansive problem.
It is understandable that above execution mode only is the illustrative embodiments that adopts for principle of the present invention is described, yet the present invention is not limited thereto.For the one of ordinary skilled in the art, under the situation that does not break away from spirit of the present invention and essence, can make various modification and improvement, these modification also are regarded as protection scope of the present invention with improving.
Claims (17)
1. Si-C composite material, it is characterized in that: comprise that hollow porous carbon bag covers silicon nanoparticle, and the particle diameter of silicon nanoparticle is 5-80nm in the Si-C composite material, wherein nano-silicon content is 10-90wt%.
2. the preparation method of the described Si-C composite material of claim 1 is characterized in that may further comprise the steps:
(1) prepared polymer solution: high molecular polymer is dissolved in the solvent, gets the polymer solution of 1-20wt%;
(2) silicon monoxide is even with mixed with polymers: the polymer solution of silicon monoxide with step (1) gained mixed in proportion, fully disperse, remove and desolvate, get the composite material of polymer overmold silicon monoxide;
(3) high temperature carries out carbonization and disproportionated reaction: the composite material to the polymer overmold silicon monoxide of step (2) gained under protective atmosphere heats; Make high molecular polymer generation carburizing reagent; Silicon monoxide generation disproportionated reaction obtains the composite material that the porous carbon bag covers silicon dioxide/nano-silicon;
(4) corrosion removes silicon dioxide: the composite material that the porous carbon bag of step (3) gained is covered silicon dioxide/nano-silicon and corrosive liquid are by mass ratio 1: 5-1: 100 mix, stir separate after 0.5-24 hour Si-C composite material.
3. preparation method according to claim 2 is characterized in that the middle high molecular polymer of said step (1) comprises one or more in polyvinyl chloride, polymethyl methacrylate, polyacrylonitrile, phenolic resins, pitch, glucose, sucrose, the starch.
4. preparation method according to claim 3 is characterized in that solvent comprises water, ethanol, acetone, oxolane, chloroform, N-methyl pyrrolidone or N, one or more in the dinethylformamide in the said step (1).
5. preparation method according to claim 2 is characterized in that silicon monoxide mixes with polymer solution in proportion in the said step (2) and refers to that silicon monoxide and polymer solution mass ratio are 1: 1-1: 200; Fully disperse to refer to adopt ultrasonic dispersing 10-100 minute, ultrasonic frequency is 40,000 Hz.
6. the preparation method of the described Si-C composite material of claim 1 is characterized in that may further comprise the steps:
(1) silicon monoxide and mixed with polymers are even: silicon monoxide and high molecular polymer are taken by weighing in proportion, and with ball mill ball milling 0.5-24 hour, mixture of powders;
(2) high temperature carries out carbonization and disproportionated reaction: the mixture of powders to step (1) gained under protective atmosphere heats; Make high molecular polymer generation carburizing reagent; Silicon monoxide generation disproportionated reaction obtains the composite material that the porous carbon bag covers silicon dioxide/nano-silicon;
(3) corrosion removes silicon dioxide: the composite material that the porous carbon bag of step (2) gained is covered silicon dioxide/nano-silicon and corrosive liquid are by mass ratio 1: 5-1: 100 mix, stir separate after 0.5-24 hour Si-C composite material.
7. preparation method according to claim 6 is characterized in that middle silicon monoxide of said step (1) and high molecular polymer mass ratio are 1: 9-9: 1.
8. according to claim 2 or 6 described preparation methods, it is characterized in that the temperature that said high temperature carries out carbonization and disproportionated reaction is 700-1500 ℃, be 0.5-12 hour heating time.
9. preparation method according to claim 8 is characterized in that the temperature that said high temperature carries out carbonization and disproportionated reaction is 900-1200 ℃, and be 1-5h heating time.
10. according to claim 2 or 6 described preparation methods, it is characterized in that said protective atmosphere is the gaseous mixture of nitrogen, argon gas or argon gas and hydrogen.
11., it is characterized in that said corrosive liquid is the hydrofluoric acid aqueous solution of 3-40wt% according to claim 2 or 6 described preparation methods.
12. preparation method according to claim 11 is characterized in that said corrosive liquid is the hydrofluoric acid aqueous solution of 5-20wt%.
13., it is characterized in that said corrosive liquid is lithium hydroxide or potassium hydroxide or the NaOH of 0.4-30wt% according to claim 2 or 6 described preparation methods.
14. preparation method according to claim 13 is characterized in that said corrosive liquid is the NaOH of 1-30wt%.
15. preparation method according to claim 6 is characterized in that said high molecular polymer comprises one or more in polyvinyl chloride, polymethyl methacrylate, polyacrylonitrile, phenolic resins, pitch, glucose, sucrose, the starch.
16. a lithium ion battery negative material is characterized in that comprising the Si-C composite material with the arbitrary said method preparation of claim 2-15.
17. a lithium ion battery is characterized in that comprising the negative pole for preparing battery with the said lithium ion battery negative material of claim 16.
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