CN106784717A - A kind of preparation method of nano silicon coated graphite negative material - Google Patents
A kind of preparation method of nano silicon coated graphite negative material Download PDFInfo
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- CN106784717A CN106784717A CN201611250975.5A CN201611250975A CN106784717A CN 106784717 A CN106784717 A CN 106784717A CN 201611250975 A CN201611250975 A CN 201611250975A CN 106784717 A CN106784717 A CN 106784717A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 239000000463 material Substances 0.000 title claims abstract description 115
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 112
- 239000010439 graphite Substances 0.000 title claims abstract description 112
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 18
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 71
- 239000000377 silicon dioxide Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000004115 Sodium Silicate Substances 0.000 claims description 13
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004111 Potassium silicate Substances 0.000 claims description 4
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 claims description 4
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000008239 natural water Substances 0.000 claims description 3
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 150000003377 silicon compounds Chemical class 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 abstract description 17
- -1 graphite silicon compound Chemical class 0.000 abstract description 2
- 238000013019 agitation Methods 0.000 abstract 1
- 229910001416 lithium ion Inorganic materials 0.000 description 61
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 58
- 239000002245 particle Substances 0.000 description 34
- 239000000499 gel Substances 0.000 description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 20
- 238000005516 engineering process Methods 0.000 description 17
- 239000013078 crystal Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- 230000014759 maintenance of location Effects 0.000 description 12
- 239000007773 negative electrode material Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 235000013339 cereals Nutrition 0.000 description 10
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000007770 graphite material Substances 0.000 description 8
- 230000001788 irregular Effects 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910016622 LixFe2O3 Inorganic materials 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910009866 Ti5O12 Inorganic materials 0.000 description 1
- ICVBNINMOKOHSQ-UHFFFAOYSA-N [C].O[Si](O)(O)O Chemical compound [C].O[Si](O)(O)O ICVBNINMOKOHSQ-UHFFFAOYSA-N 0.000 description 1
- IYHRTBGVUHKQKG-UHFFFAOYSA-M [Li+].[O-2].[O-2].[OH-].[Fe+2].[Fe+2] Chemical compound [Li+].[O-2].[O-2].[OH-].[Fe+2].[Fe+2] IYHRTBGVUHKQKG-UHFFFAOYSA-M 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of preparation method of nano silicon coated graphite negative material, first under agitation to certain Si:The graphite silicon compound mixed solution and dripping acid solution of C mol ratios, control pH, reaction temperature, the time of reaction system, the silica sol for obtaining, dry, obtain graphite silicic acid gel, graphite silicic acid gel is mixed with water again, is washed, filtered, dry graphite silicic acid gel, graphite silicic acid gel is thermally decomposed under vacuum, obtain nano silicon coated graphite negative material.The grain diameter of gained nano silicon coated graphite negative material is 1~35 μm, and it has specific discharge capacity and preferable cycle performance and high-rate characteristics higher higher.
Description
Technical field
The present invention relates to field of lithium ion battery material, a kind of nano silicon coated graphite negative pole material is more particularly to
The preparation method of material.A kind of nano silicon coated graphite negative material prepared by the present invention can serve as lithium ion battery
Negative electrode active material, manufactures lithium ion battery.
Background technology
At present, the negative material typically graphite material that lithium ion battery is used.The phase of lithium ion battery negative material
Research is closed also to be concentrated mainly on to the modified of native graphite, new CNT, Graphene, amorphous carbon and numerous metals
Oxide etc..Wherein, graphite is the carbon negative pole material for being used for lithium ion battery earliest, and its good conductivity, crystallinity is high, with complete
Whole layered crystal structure, insertion and the abjection of suitable lithium ion.But, graphite as lithium ion battery negative electrode active material
Material, because the features such as its is nonpolar, density is low, mechanical strength is poor, except graphite capacity is relatively low, charge-discharge performance compared with
Difference etc. is outside defect, during lithium ion battery negative electrode is manufactured graphite cathode also exist it is poor with the compatibility of water, point
Divergence is low, poor processability, the deficiency such as production process graphite dust pollution production environment and equipment.
The material of " having similar to graphite laminate structure " that CNT is made up of the coaxial carbon plate layer of single or multiple lift.
The sp of CNT2Hybrid structure and draw ratio high bring a series of excellent properties for it.This special microcosmic knot
Structure causes that the insert depth of lithium ion is small, stroke is short and embedded location is more (pipe interior and interlayer gap, hole etc.), while because of carbon
Nanotube conductive performance very well, with the conduction of preferable electronics and ion transport capacity, is suitable as lithium ion battery negative material.
Therefore, CNT is used as lithium ion battery negative material, it is clear that than traditional graphite electrode advantageously.But using carbon nanometer
Pipe there is also weak point directly as lithium ion battery negative material：1) irreversible capacity is larger first, first charge-discharge effect
Rate is than relatively low；2) carbon nanometer tube negative pole lacks the voltage platform of stabilization；3) there is current potential hysteresis in CNT.Additionally, carbon
The synthesis cost of nanotube is high.These all limit practical application of the CNT as lithium ion battery negative material.Stone
Black alkene (Graphene) be one kind only by carbon atom with sp2Hybridized orbit constitutes the flat film of hexangle type lattice, that is, only
One two-dimensional material of carbon atom thickness.Compared to other Carbon Materials such as CNT, Graphene has unique microstructure, this
So that Graphene has larger specific surface area and cellular void structure, with storage lithium ability higher.Additionally, material is in itself
With good chemical stability, high electron mobility and excellent mechanical property, it is had as electrode material and protrude
Advantage.Similar with CNT, coulombic efficiency is low, charge and discharge platform is higher and circulates due to circulating first for pure grapheme material
Less stable, synthesis cost are very high, commercial value shortcoming etc. defect, and the Carbon Materials of current commercialization can not be replaced directly to use
Make lithium ion battery negative material.Metal oxide-carbon is (such as：SnO、VO2、TiO2、LixFe2O3、Li4Mn2O12、Li4Ti5O12Cover
Carbon material etc.) material as lithium ion battery negative pole, due in organic electrolyte solution carbon surface formed can allow electronics and
The freely through passivation layer of lithium ion, while this passivation layer ensure that electrode good cycle performance, can cause electrode tight
The loss of the first charge-discharge irreversible capacity of weight, can even cause the structure change and poor electric contact of electrode interior sometimes.
In addition, being likely to cause battery failure because of the decomposition of protective layer under high temperature or producing safety problem.
In order to improve the above-mentioned not enough or defect of lithium ion battery negative material, function admirable, high security are produced
Lithium ion battery, those skilled in the relevant art mainly research and develop novel cathode material for lithium ion battery.Document " silicon monoxide/
Carbon/expanded graphite is used as lithium ion battery negative material [J] " (battery, 2016,46 (3)：121-124.) report：With poly- second
Enol butyral is carbon source, in silicon monoxide (SiO) coated with carbon bed then compound with expanded graphite, prepares lithium ion battery
The negative pole method of SiO/C/ exfoliated-graphite composites, it is said that：The 200mA/g multiplying powers of the SiO/C/ exfoliated-graphite composites
The 100th reversible specific capacity of circulation of discharge and recharge is 545mAh/g.Document " self-supporting WS2The Static Spinning of/carbon fibre composite
Silk is prepared and its as the application [J] of lithium ion battery negative material " (Science Bulletin, 2016,61 (8)：912) utilization is described
Electrostatic spinning technique is prepared for one kind " two-dimentional WS2Nanometer sheet is uniformly embedded in carbon nano-fiber composite material ", document claims, the skill
Composite membrane section bar material prepared by art does not need conductive agent, bonding agent, can be directly used as lithium ion battery negative, can be directly from
Make flexible battery device.Document " preparation of jute base carbon fibre/MnO/C lithium ion battery negative materials and its chemical property
[J] " (Chinese Journal of Inorganic Chemistry, 2016,32 (5)：811-817) describe and be with tossa, potassium permanganate and polymer pyrroles
Raw material, the technology of " carbon fiber/MnO/C " lithium ion battery negative material is prepared through more numerous and diverse step.Carbon fiber/MnO/C
Material has effective electron channel and the polynary cooperative effect on composition in structure, is showed as lithium cell cathode material
Go out specific capacity higher, good cycle performance and high rate performance.The document does not provide secure lithium ion battery
Practicable technological parameter and process conditions etc.." metatitanic acid high temperature solid-state method prepares lithium ion battery negative material point to document
Spar Li4Ti5O12[J] " (electronic original part and material, 2016,35 (3)：19-21) report and synthesize " point crystalline substance with solid reaction process
Stone-type Li4Ti5O12Negative material "." the spinel-type Li of document report4Ti5O12The first charge-discharge capacity of negative material " is
158.63mAh/g, (electric current) efficiency is 98.7%.Document " ZnFe2O4The preparation of lithium ion battery negative material and electrochemistry
[J] can be studied " (Journal of Inorganic Materials, 2016,31 (1)：34-38) have studied with hydro-thermal-solid phase that ZnFe chlorides are raw material
Reaction method prepares " ZnFe2O4The contents such as the technology and chemical property of negative material ".The ZnFe of document synthesis2O4Negative pole material
Expect to be nanometer porous spherical particle, with reversible specific capacity and relatively stable cycle performance higher.
Additionally, document " preparation of uniform load nickel oxide nanoparticle porous hard carbon ball and its high performance lithium ion battery
Negative material application [J] " (Acta PhySico-Chimica Sinica, 2015,31 (2)：268-276) describe it is a kind of using hydro-thermal method prepare lithium from
The technology of sub- cell negative electrode material.It is said that under the composite 100mA/g current density charge conditions of document report synthesis,
Initial charge specific capacity is 764mAh/g, and charge specific capacity is maintained at 777mAh/g after circulation in 100 weeks；800mA/g current densities
Under charge condition, charging capacity 380mAh/g." zinc replaces to spinelle Li document2MnTi3O8Lithium ion battery negative material is micro-
See the influence [J] of structure and chemical property " (non-ferrous metal engineering, 2015,5 (6)：1-6) synthesized with sol-gel process
Li2MnTi3O8Aqueous precursor gel material, adds ZnAc2, zinc substitution is prepared to spinelle Li through high-temperature calcination2MnTi3O8Lithium from
Sub- cell negative electrode material.Document claims：The zinc of synthesis replaces to spinelle Li2MnTi3O8Lithium ion battery negative material fills at 36 times
Specific capacity after discharge cycles is respectively 199.4mAh/g and 260.2mAh/g.Document " lithium ion battery negative material
Li4Ti5O12Synthesis and performance study [J] " (electrochemistry, 2015,21 (2)：181-186) describe with TiO2, lithium acetate for original
Material, synthesis in solid state lithium ion battery negative Li4Ti5O12The method of material.Report synthesis Li4Ti5O1210C high magnifications put first
Electric specific capacity reaches 143.0mAh/g." three-dimensional multistage hole class Graphene carries di-iron trioxide lithium ion battery negative material to document
[J] " (electrochemistry, 2015,21 (1)：66-71), with synthetic technologys such as numerous and diverse ion exchange, liquid phase reactor, solid phase roastings, close
Into and have studied three-dimensional porous Graphene and carry performance of the di-iron trioxide as lithium ion battery negative material.Document claims：Synthesis
Fe2O3The first discharge specific capacity of -3D HPG materials is up to 1745mAh/g, and 50 times circulation specific capacity is maintained at 1095mAh/g.
Document " multilevel hierarchy SnO2 nano flowers are used as high performance lithium ionic cell cathode material [J] " (Science Bulletin, 2015,60 (9)：
892-895) describe " flower-shape nano SnO2" negative material solvent-thermal method technology of preparing.Flower-shape nanometer prepared by the document
SnO2The reversible capacity of negative material is 350.7mAh/g." lamellar titanosilicate compound is used as lithium ion battery negative for document
Energy storage material [J] " (Chinese Journal of Inorganic Chemistry, 2015,31 (12)：2425-2431) have studied and use lamellar titanosilicate
Na4Ti2Si8O22·4H2O (Na-JDF-L1) prepares lithium ion battery negative material through ion-exchange.It is main by by TiO2
It is incorporated into Li (Na)-JDF-L1, effectively improves the coulombic efficiency first and multiplying power discharging property of material.
There are substantial amounts of synthesis about silica, modified and application patent to disclose.Chinese patent
(ZL200510064682.5, ZL 03105299.1) discloses " a kind of preparation method of nano silicon ", Chinese patent
(ZL 02155203.7) is disclosed " composite nano silica/ferroferric oxide grain material and preparation method thereof ", and China is specially
Sharp (application number 200610009601.4) discloses " method that nano silicon is prepared with rice hull ash ", Chinese patent (ZL
200410010304.2) " a kind of nano silicon dioxide particles preparation method ", Chinese patent (application number are disclosed
20081004251.0) " a kind of nano-silicon dioxide hollow sphere material and preparation method thereof ", Chinese patent (application number are disclosed
2006101300304.5) disclose " a kind of preparation method of hydrophobic nano-silica " etc..United States Patent (USP) " Light-
emitting device having a thin insulating film made of nitrogen and silicon
And an electrode made of conductive transparent oxide and silicon dioxide " are (specially
Sharp application number：7,902,747,2011.8) disclose a kind of " with the thin dielectric membrane as manufactured by nitrogen and silicon and by conductive, transparent
The light-emitting device of the electrode that oxide and silica are made ".Have no relevant nano silicon coated graphite negative material system
Standby technology is disclosed or used.
The content of the invention
The purpose of the present invention is to there are provided a kind of preparation method of nano silicon coated graphite negative material, side
The raw materials used abundance of method, technical equipment are relatively simple, easy, technological process is simple, production technology low cost, and preparation is received
Rice coated with silica graphite cathode material, with the particle size distribution range (particle diameter distribution of modified graphite used by depending on wider
With the preparation technology parameter of the covering amount of nano silicon and collosol and gel etc.), coated with silica amount is easily controlled, manufacture
The features such as lithium ion battery negative electrode has good processing characteristics and fillibility higher, compacted density higher.
The present invention is realized by following technical solution：A kind of described nano silicon coated graphite negative material
Preparation method, comprises the following steps：
A kind of preparation method of nano silicon coated graphite negative material, its step is：
The first step, silicon, carbon mol ratio Si will be contained:C is 1:5~1:20 graphite is (according to C12Graphite quality is calculated, below
It is identical) and the mixing of the silicon compound aqueous solution that concentration is 0.1~6mol/L, stir 10~120 minutes, obtain graphite-silication and close
Thing mixed solution；
Second step, stirred in room temperature (25~28 DEG C, same as below), with magnetic stirrer (magneton) or electric blender
Under conditions of, to the acid solution that graphite-silicon compound mixed solution and dripping concentration is 0.2~10mol/L, control reaction system
PH value be 2.5~5.5, continue stir 10~120 minutes, stand 2~24 hours, obtain grey or grey black or black stone
Ink-silica sol；
3rd step, by graphite-silica sol under the conditions of 65~120 DEG C dry 4~24 hours, obtain grey or grey black
Or black graphite-silicic acid gel；Graphite-silicic acid gel is mixed with the water that volume is graphite -2~5 times of Silica hydrogel volume, is stirred
10~120 minutes, wash with water graphite-silica sol to eluate be neutral (pH=6.8 or 7.0 or 7.2, as follows, slightly),
Filtering, that is, obtain grey or grey black or black graphite-silicic acid gel powder；
4th step, graphite-silicic acid gel powder is placed in temperature programmed control vacuum Muffle furnace, with 1~10 DEG C per minute
Heating rate is warming up to and is thermally decomposed under 350~750 DEG C, 0.1~0.01MPa vacuum conditions, is incubated 4~24h, naturally cools to
Room temperature, that is, obtain grey or grey black or black nano coated with silica powdered graphite；
In order to be better achieved the present invention, described silicon compound is sodium metasilicate, potassium silicate, ammonium silicate are therein any
Kind；
Described acid be hydrochloric acid, nitric acid, sulfuric acid or acetic acid it is therein any one；
Described water be natural water, running water, distilled water, redistilled water or deionized water it is therein any one.
The present invention compared with prior art, has the following advantages that and beneficial effect：
1st, the particle diameter distribution using a kind of nano silicon coated graphite negative material of present invention synthesis is wider, and main
To depend on the preparation technology parameter of the particle diameter, coated with silica amount and collosol and gel of graphite material to be modified, silica
Covering amount and cladding thickness it is easily controllable, and the nano silicon coated graphite negative material of easily controllable synthesis particle diameter
(refer to：Embodiment and accompanying drawing)；
2nd, a kind of nano silicon coated graphite negative material prepared using the present invention, manufactured lithium ion battery
With charging and discharging capacity higher and high-multiplying power discharge effect, highest specific discharge capacity reaches 523mAh/g (embodiment 5), does not wrap
The highest specific discharge capacity for covering the graphite (hereinafter referred to as " comparative sample ") of nano silicon is only 304mAh/g；5C multiplying powers
300 times charge and discharge cycles amount conservation rate is up to 98.2%, and comparative sample is 70.1%；500 times charge and discharge cycles capacity is protected
Holdup is up to 96.6% (embodiment 5), and comparative example is only 45.3% (accompanying drawing 12, accompanying drawing 13, accompanying drawing 14)；
3rd, a kind of nano silicon coated graphite negative material prepared using the present invention, because clad silica
Density it is larger, and machinery is higher, physical and chemical stability preferably, relatively low with the density and easy characteristic phase for forming more fine powder
Than, dispersion is easier in aqueous, with more preferable electrode slice processing characteristics, it is beneficial to improve cathode pole piece with electrolyte
Compatibility, and then the pole piece quality that improves and performance of lithium ion battery, and significantly improve lithium ion battery production efficiency；
4th, a kind of nano silicon coated graphite negative material prepared using the present invention, is used in the appropriate bonding agent that reduces
In the case of amount, pole piece dry linting, shedding phenomenon weaken significantly, and in lithium ion battery negative manufacturing process, it is right to effectively reduce
Workshop environment causes dust pollution, the social benefit with good economic benefits and significant environmental benefit sum；
5th, the particle of the silica of a kind of nano silicon coated graphite negative material prepared using the present invention
Footpath, thickness, the content of coated with silica layer etc. are easily controllable, can be according to different type lithium ion battery (rate lithiums
Ion battery, capacity type lithium ion battery etc.) the need for, prepare that coated with silica amount is different, grain diameter is different, electrical property
There is the nano silicon coated graphite negative material of different；
6th, using the present invention prepare a kind of nano silicon coated graphite material preparation process is flexible, equipment simple,
Raw material are cheap, the comprehensive low production cost of material, it is easy to accomplish large-scale industrial production.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of nano silicon coated graphite negative material prepared by embodiment 1；
Fig. 2 is the XRD of nano silicon coated graphite negative material prepared by embodiment 1；
Fig. 3 is the stereoscan photograph of nano silicon coated graphite negative material prepared by embodiment 2；
Fig. 4 is the stereoscan photograph of nano silicon coated graphite negative material prepared by embodiment 3；
Fig. 5 is the XRD of nano silicon coated graphite negative material prepared by embodiment 3；
Fig. 6 is the stereoscan photograph of nano silicon coated graphite negative material prepared by embodiment 4；
Fig. 7 is the stereoscan photograph of nano silicon coated graphite negative material prepared by embodiment 5；
Fig. 8 is the XRD of nano silicon coated graphite negative material prepared by embodiment 5；
Fig. 9 is the stereoscan photograph of nano silicon coated graphite negative material prepared by embodiment 6；
Figure 10 is the stereoscan photograph of nano silicon coated graphite negative material prepared by embodiment 7；
Figure 11 is the XRD of nano silicon coated graphite negative material prepared by embodiment 7；
Figure 12 is the highest specific capacity of each embodiment, 300 and 500 cyclic discharge capacity conservation rate comparison diagrams；
Figure 13 is exemplary embodiments and the charge and discharge cycles discharge capacity figure of comparative example 300；
Figure 14 is the charge and discharge cycles discharge capacity figure of exemplary embodiments (embodiment 5) 500；
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is done and is further described in detail.
Embodiment 1:
A kind of preparation method of nano silicon coated graphite negative material, its step is：
The first step, silicon, carbon mol ratio Si will be contained:C is 1:20 graphite and concentration is the ammonium silicate solution of 0.1mol/L
Mixing, stirs 120 minutes, obtains graphite-sodium metasilicate mixed solution；
Second step, in room temperature (25 or 26 or 27 or 28 DEG C, same as below), with magnetic stirrer (magneton) or electric mixing
Mix under conditions of machine stirring, to the acetum of graphite-ammonium silicate mixed solution and dripping 10mol/L concentration, control reactant
The pH value of system is 5.5, continues to stir 120 minutes, stands 4 hours, obtains grey or black graphite-silica sol；
3rd step, by graphite-silica sol under the conditions of 65 DEG C dry 24 hours, obtain black graphite-silicic acid gel, will
Graphite-silicic acid gel and volume mix for the water of graphite -5 times of silica sol volume, stir 30 minutes, with natural water washing stone
Ink-silica sol to eluate is neutral, filtering, that is, obtain black carbon-silicic acid gel powder；
4th step, graphite-silica sol powder is placed in temperature programmed control vacuum Muffle furnace, with 1 DEG C per minute of intensification
Speed be warming up under 350 DEG C, 0.01MPa vacuum conditions thermally decompose, be incubated 4h, naturally cool to room temperature (25 or 26 or 27 or
It is 28 DEG C, same as below), that is, obtain black nano coated with silica powdered graphite；
Pattern, particle diameter and the crystal for preparing nano silicon coated graphite negative material are determined with SEM, XRD technology
Structure, using the nano silicon coated graphite negative material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held
The lithium ion battery for 1000mAh is measured, the charge and discharge circulation that lithium ion battery is determined under the conditions of 0.2C, 5C charge-discharge magnification is electrical
Specific discharge capacity that, can prepare nano silicon coated graphite negative material etc., as a result shows：Prepare gained nanometer titanium dioxide
The pattern of silicon coated graphite material is the polymorphs such as irregular spheroid, barred body, and its particle size range is between 1~25 μm
(Fig. 1), average grain diameter is about 15 μm, and coated with silica layer crystal body is amorphous nano silicon, silica it is original
Crystalline particle particle diameter is in 1~25nm (Fig. 2, SiO2Diffraction maximum half-peak breadth is calculated, same as below)；Nano silicon coated graphite
The highest specific discharge capacity of negative material is 412mAh/g (0.2C multiplying powers), 5C multiplying powers, 300 charge and discharge cycles capability retentions
97.3%, 500 charge and discharge cycles capability retentions 92.2% (Figure 12).
Embodiment 2:
A kind of preparation method of nano silicon coated graphite negative material, its step is：
The first step, silicon, carbon mol ratio Si will be contained:C is 1:18 graphite and concentration is the potassium silicate solution of 0.2mol/L
Mixing, stirs 100 minutes, obtains graphite-sodium metasilicate mixed solution；
Second step, in room temperature, stirred with magnetic stirrer (magneton) or electric blender under conditions of, to graphite-silicon
The sulfuric acid solution of sour potassium mixed solution and dripping 8mol/L concentration, it is 4.5 to control the pH value of reaction system, continues to stir 100 points
Clock, stands 8 hours, obtains black graphite-silica sol；
3rd step, by graphite-silica sol under the conditions of 85 DEG C dry 20 hours, obtain black graphite-silicic acid gel；Will
Graphite-silicic acid gel and volume mix for the running water of graphite -4 times of silica sol volume, stir 30 minutes, with originally water washing
Graphite-silica sol to eluate is neutral, filtering, that is, obtain black graphite-silica sol powder；
4th step, grey or black graphite-silica sol powder are placed in temperature programmed control vacuum Muffle furnace, with per minute
5 DEG C of heating rate is warming up to and is thermally decomposed under 450 DEG C, 0.02MPa vacuum conditions, is incubated 8h, naturally cools to room temperature, obtains final product
To black nano coated with silica powdered graphite；
Pattern, particle diameter and the crystal for preparing nano silicon coated graphite negative material are determined with SEM, XRD technology
Structure, using the nano silicon coated graphite negative material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held
The lithium ion battery for 1000mAh is measured, the charge and discharge circulation that lithium ion battery is determined under the conditions of 0.2C, 5C charge-discharge magnification is electrical
Specific discharge capacity that, can prepare nano silicon coated graphite negative material etc., as a result shows：Prepare gained nanometer titanium dioxide
The pattern of silicon coated graphite material is the polymorphs such as irregular spheroid, barred body, and its particle size range is between 1~25 μm
(Fig. 3), average grain diameter is about 20 μm, and coated with silica layer crystal body is amorphous nano silicon, silica it is original
Crystalline particle particle diameter is in 1~25nm；The highest specific discharge capacity of nano silicon coated graphite negative material is 438mAh/g
(0.2C multiplying powers), 5C multiplying powers, 300 charge and discharge cycles capability retentions 98.1%, 500 charge and discharge cycles capability retentions
94.4% (Figure 12).
Embodiment 3:
A kind of preparation method of nano silicon coated graphite negative material, its step is：
The first step, silicon, carbon mol ratio Si will be contained:C is 1:15 graphite and concentration is the sodium silicate solution of 0.5mol/L
Mixing, stirs 80 minutes, obtains graphite-sodium metasilicate mixed solution；
Second step, in room temperature, stirred with magnetic stirrer (magneton) or electric blender under conditions of, to graphite-silicon
Sour sodium mixed solution and dripping concentration is the sulfuric acid solution of 6mol/L, controls the pH value of reaction system to be about 3.5, continues to stir
80 minutes, 12 hours are stood, obtain grey black graphite-silica sol；
3rd step, by graphite-silica sol under the conditions of 100 DEG C dry 16 hours, obtain grey or black graphite-silicic acid
Gel；Graphite-silicic acid gel is mixed with the distilled water water that volume is graphite -3 times of silica sol volume, 80 minutes is stirred, is used
Distilled water graphite water-silica sol to eluate is neutral, filtering, that is, obtain grey or black graphite-silica sol powder；
4th step, grey or black graphite-silica sol powder are placed in temperature programmed control vacuum Muffle furnace, with per minute
10 DEG C of heating rate is warming up to and is thermally decomposed under 550 DEG C, 0.04MPa vacuum conditions, is incubated 12h, naturally cools to room temperature, i.e.,
Obtain grey black nano silicon coated graphite powder；
Pattern, particle diameter and the crystal for preparing nano silicon coated graphite negative material are determined with SEM, XRD technology
Structure, using the nano silicon coated graphite negative material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held
The lithium ion battery for 1000mAh is measured, the charge and discharge circulation that lithium ion battery is determined under the conditions of 0.2C, 5C charge-discharge magnification is electrical
Specific discharge capacity that, can prepare nano silicon coated graphite negative material etc., as a result shows：Prepare gained nanometer titanium dioxide
The pattern of silicon coated graphite material is the polymorphs such as irregular spheroid, barred body, and its particle size range is between 1~25 μm
(Fig. 4), average grain diameter is about 15 μm, and coated with silica layer crystal body is amorphous nano silicon, silica it is original
Crystalline particle particle diameter is at 1~5nm (Fig. 5)；The highest specific discharge capacity of nano silicon coated graphite negative material is
464mAh/g (0.2C multiplying powers), 5C multiplying powers, 300 charge and discharge cycles capability retentions 95.3%, 500 charge and discharge cycles capacity
Conservation rate 92.7% (Figure 12).
Embodiment 4:
A kind of preparation method of nano silicon coated graphite negative material, its step is：
The first step, silicon, carbon mol ratio Si will be contained:C is 1:12.5 graphite and concentration is the sodium silicate solution of 1mol/L
Mixing, stirs 60 minutes, obtains graphite-sodium metasilicate mixed solution；
Second step, stirred in room temperature and with magnetic stirrer (magneton) or electric blender under conditions of, to graphite-silicon
Sour sodium mixed solution and dripping concentration is the hydrochloric acid solution of 4mol/L, and it is 2.5 to control the pH value of reaction system, continues to stir 60
Minute, 16 hours are stood, obtain grey or black graphite-silica sol；
3rd step, by graphite-silica sol under the conditions of 120 DEG C dry 12 hours, obtain grey black graphite-silicic acid coagulate
Glue；Graphite-silicic acid gel and volume are mixed for the redistilled water water of graphite -5 times of silicic acid gel volume, stir 60 minutes,
It is neutral, filtering with redistilled water water washing graphite-silica sol to eluate, that is, obtains grey black graphite-silica sol
Powder；
4th step, grey or black graphite-silica sol powder are placed in temperature programmed control vacuum Muffle furnace, with per minute
1~10 DEG C of heating rate is warming up to and is thermally decomposed under 550 DEG C, 0.06MPa vacuum conditions, is incubated 16h, naturally cools to room
Temperature, that is, obtain grey black nano silicon coated graphite powder.
Pattern, particle diameter and the crystal for preparing nano silicon coated graphite negative material are determined with SEM, XRD technology
Structure, using the nano silicon coated graphite negative material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held
The lithium ion battery for 1000mAh is measured, the charge and discharge circulation that lithium ion battery is determined under the conditions of 0.2C, 5C charge-discharge magnification is electrical
Specific discharge capacity that, can prepare nano silicon coated graphite negative material etc., as a result shows：Prepare gained nanometer titanium dioxide
The pattern of silicon coated graphite material is the polymorphs such as irregular spheroid, barred body, and its particle size range is between 1~25 μm
(Fig. 6), average grain diameter is about 10 μm, and coated with silica layer crystal body is amorphous nano silicon, silica it is original
Crystalline particle particle diameter is in 1~5nm；The highest specific discharge capacity of nano silicon coated graphite negative material is 504mAh/g
(0.2C multiplying powers), 5C multiplying powers, 300 charge and discharge cycles capability retentions 96.6%, 500 charge and discharge cycles capability retentions
991.5% (Figure 12).
Embodiment 5:
A kind of preparation method of nano silicon coated graphite negative material, its step is：
The first step, silicon, carbon mol ratio Si will be contained:C is 1:10 graphite and concentration is mixed for the sodium silicate solution of 2mol/L
Close, stir 40 minutes, obtain graphite-sodium metasilicate mixed solution；
Second step, in room temperature, stirred with magnetic stirrer (magneton) or electric blender under conditions of, to graphite-silicon
Sour sodium mixed solution and dripping concentration is the hydrochloric acid solution of 2mol/L, and it is 3.5 to control the pH value of reaction system, continues to stir 40 points
Clock, stands 12 hours, obtains grey black graphite-silica sol；
3rd step, by graphite-silica sol under the conditions of 120 DEG C dry 8 hours, obtain grey or black graphite-silicic acid
Gel (hereinafter referred to as Silica hydrogel)；By graphite-silicic acid gel with volume for the distilled water water of graphite -2 times of silica sol volume is mixed
Close, stirring 30 minutes, be neutral, filtering with distilled water graphite water-silica sol to eluate, that is, obtain grey black graphite-
Silica sol powder；
4th step, grey or black graphite-silica sol powder are placed in temperature programmed control vacuum Muffle furnace, with per minute
2 DEG C of heating rate is warming up to and is thermally decomposed under 650 DEG C, 0.08MPa vacuum conditions, is incubated 20h, naturally cools to room temperature, i.e.,
Obtain grey black nano silicon coated graphite powder；
Pattern, particle diameter and the crystal for preparing nano silicon coated graphite negative material are determined with SEM, XRD technology
Structure, using the nano silicon coated graphite negative material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held
The lithium ion battery for 1000mAh is measured, the charge and discharge circulation that lithium ion battery is determined under the conditions of 0.2C, 5C charge-discharge magnification is electrical
Specific discharge capacity that, can prepare nano silicon coated graphite negative material etc., as a result shows：Prepare gained nanometer titanium dioxide
The pattern of silicon coated graphite material is the polymorphs such as irregular particle, barred body, piece shape, and its particle size range is at 1~30 μm
Between (Fig. 7), average grain diameter is about 15 μm, and coated with silica layer crystal body is amorphous nano silicon, silica
Initial crystalline grain diameter is at 1~3nm (Fig. 8)；The highest specific discharge capacity of nano silicon coated graphite negative material is
523mAh/g (0.2C multiplying powers), 5C multiplying powers, 300 charge and discharge cycles capability retentions 95.2%, 500 charge and discharge cycles capacity
Conservation rate 92.7% (Figure 12, Figure 13, Figure 14).
Embodiment 6:
A kind of preparation method of nano silicon coated graphite negative material, its step is：
The first step, silicon, carbon mol ratio Si will be contained:C is 1:7.5 graphite and concentration is mixed for the sodium silicate solution of 4mol/L
Close, stir 20 minutes, obtain graphite-sodium metasilicate mixed solution；
Second step, room temperature, magnetic stirrer (magneton) or electric blender stirring under conditions of, to graphite-silicic acid
The hydrochloric acid solution of sodium mixed solution and dripping 2mol/L concentration, it is 3.5 to control the pH value of reaction system, continues to stir 20 points
Clock, stands 24 hours, obtains grey graphite-silica sol；
3rd step, by graphite-silica sol under the conditions of 120 DEG C dry 2 hours, obtain grey graphite-silicic acid gel；Will
Graphite-silicic acid gel mixes with the deionized water that volume is graphite -2 times of silica sol volume, stirs 120 minutes, uses deionization
Water washing graphite-silica sol to eluate is neutral, filtering, that is, obtain grey graphite-silica sol powder；
4th step, grey or black graphite-silica sol powder are placed in temperature programmed control vacuum Muffle furnace, with per minute
10 DEG C of heating rate is warming up to and is thermally decomposed under 350 DEG C, 0.1MPa vacuum conditions, is incubated 8h, naturally cools to room temperature, obtains final product
To grey or black nano coated with silica powdered graphite；
Pattern, particle diameter and the crystal for preparing nano silicon coated graphite negative material are determined with SEM, XRD technology
Structure, using the nano silicon coated graphite negative material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held
The lithium ion battery for 1000mAh is measured, the charge and discharge circulation that lithium ion battery is determined under the conditions of 0.2C, 5C charge-discharge magnification is electrical
Specific discharge capacity that, can prepare nano silicon coated graphite negative material etc., as a result shows：Prepare gained nanometer titanium dioxide
The pattern of silicon coated graphite negative material is the polymorph such as irregular spheroid, barred body, its particle size range 1~20 μm it
Between (Fig. 9), average grain diameter is about 15 μm, and coated with silica layer crystal body is amorphous nano silicon, the original of silica
Beginning, crystalline particle particle diameter was in 1~5nm；The highest specific discharge capacity of nano silicon coated graphite negative material is 481mAh/g
(0.2C multiplying powers), 5C multiplying powers, 300 charge and discharge cycles capability retentions 97.8%, 500 charge and discharge cycles capability retentions
95.6% (Figure 12).
Embodiment 7:
A kind of preparation method of nano silicon coated graphite negative material, its step is：
The first step, silicon, carbon mol ratio Si will be contained:C is 1:5 graphite and concentration is mixed for the sodium silicate solution of 6mol/L
Close, stir 10 minutes, obtain graphite-potassium silicate mixed solution；
Second step, room temperature, magnetic stirrer (magneton) or electric blender stirring under conditions of, to graphite-silicic acid
The hydrochloric acid solution of sodium mixed solution and dripping 10mol/L concentration, it is 3.5 to control the pH value of reaction system, continues to stir 10 minutes,
24 hours are stood, grey graphite-silica sol is obtained；
3rd step, by graphite-silica sol under the conditions of 120 DEG C dry 4 hours, obtain grey graphite-silicic acid gel；Will
Graphite-silicic acid gel mixes with the distilled water water that volume is graphite -5 times of silica sol volume, stirs 10 minutes, is washed with distillation
It is neutral, filtering to wash graphite-silica sol to eluate, that is, obtain grey graphite-silica sol powder；
4th step, grey graphite-silica sol powder is placed in temperature programmed control vacuum Muffle furnace, with 10 DEG C per minute
Heating rate is warming up to and is thermally decomposed under 750 DEG C, 0.1MPa vacuum conditions, is incubated 24h, naturally cools to room temperature, that is, obtain ash
Color nano silicon coated graphite powder；
Pattern, particle diameter and the crystal for preparing nano silicon coated graphite negative material are determined with SEM, XRD technology
Structure, using the nano silicon coated graphite negative material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held
The lithium ion battery for 1000mAh is measured, the charge and discharge circulation that lithium ion battery is determined under the conditions of 0.2C, 5C charge-discharge magnification is electrical
Specific discharge capacity that, can prepare nano silicon coated graphite negative material etc., as a result shows：Prepare gained nanometer titanium dioxide
The pattern of silicon coated graphite negative material is the polymorph such as irregular spheroid, barred body, its particle size range 1~35 μm it
Between (Figure 10), average grain diameter is about 15 μm, and coated with silica layer crystal body is amorphous nano silicon, the original of silica
Beginning crystalline particle particle diameter is at 1~3nm (Figure 11)；The highest specific discharge capacity of nano silicon coated graphite negative material is
433mAh/g (0.2C multiplying powers), 5C multiplying powers, 300 charge and discharge cycles capability retentions 96.7%, 500 charge and discharge cycles capacity
Conservation rate 94.1% (Figure 12).
Comparative example 8:
Using the graphite cathode material of uncoated nano silicon as negative electrode active material, manufacture cathode pole piece assembling is held
The lithium ion battery for 1000mAh is measured, the charge and discharge circulation that lithium ion battery is determined under the conditions of 0.2C, 5C charge-discharge magnification is electrical
Specific discharge capacity that, can prepare nano silicon coated graphite negative material etc., as a result shows：Uncoated nano silicon
Graphite cathode material highest specific discharge capacity be 304mAh/g (0.2C multiplying powers), 5C multiplying powers, 300 charge and discharge cycles capacity
Conservation rate 70.1%, 500 charge and discharge cycles capability retentions 45.3% (accompanying drawing 12).
As described above, you can preferably realize the present invention.
Claims (1)
1. a kind of preparation method of nano silicon coated graphite negative material, its step is：
The first step, silicon, carbon mol ratio Si will be contained:C is 1:5~1:20 graphite and concentration is that the silication of 0.1~6mol/L is closed
The thing aqueous solution mixes, and stirs 10~120 minutes, obtains graphite-silicon compound mixed aqueous solution；
Second step, in room temperature, stirred with magnetic stirrer or electric blender under conditions of, mix to graphite-silicon compound
The acid solution that concentration is 0.1~10mol/L is added dropwise in solution, it is 2.5~5.5 to control the pH value of reaction system, continues to stir 10
~120 minutes, 4~24 hours are stood, obtain grey or grey black or black graphite-silica sol；
3rd step, by graphite-silica sol under the conditions of 65~120 DEG C dry 2~24 hours, obtain grey or grey black or black
Colored stone ink-silicic acid gel；Graphite-silicic acid gel and volume are mixed for the water of carbon -2~5 times of silicic acid gel volume, stir 10~
120 minutes, to wash graphite-silica sol to eluate with water be neutral, filtering, obtain grey or grey black or black graphite-
Silica sol powder；
4th step, grey or grey black or black graphite-silica sol powder are placed in temperature programmed control vacuum Muffle furnace, with every
Minute 1~10 DEG C of heating rate is warming up in 350~750 DEG C, 4~24h of insulation, naturally cools to room temperature, 0.1~
Thermally decomposed under 0.01MPa vacuum conditions, obtain grey or grey black or black nano coated with silica powdered graphite；
Described silicon compound be sodium metasilicate, potassium silicate, ammonium silicate it is therein any one；
Described acid be hydrochloric acid, nitric acid, sulfuric acid or acetic acid it is therein any one；
Described water be natural water, running water, distilled water, redistilled water or deionized water it is therein any one.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109524630A (en) * | 2017-09-20 | 2019-03-26 | 上海杉杉科技有限公司 | A kind of preparation method of cladded type composite negative pole material |
| CN111320868A (en) * | 2018-12-17 | 2020-06-23 | 杜邦聚合物有限公司 | Polymer composition with high dielectric constant and low dielectric loss |
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| CN101210118A (en) * | 2006-12-29 | 2008-07-02 | 比亚迪股份有限公司 | Method for preparing carbon coating graphite/silicon oxide composite material |
| CN103515582A (en) * | 2013-10-10 | 2014-01-15 | 中国海洋石油总公司 | Preparation method of lithium ion battery silicon-carbon composite cathode material |
| CN104091952A (en) * | 2014-07-24 | 2014-10-08 | 常州大学 | A kind of novel lithium-ion battery negative electrode material and preparation method thereof |
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| CN101210118A (en) * | 2006-12-29 | 2008-07-02 | 比亚迪股份有限公司 | Method for preparing carbon coating graphite/silicon oxide composite material |
| CN103515582A (en) * | 2013-10-10 | 2014-01-15 | 中国海洋石油总公司 | Preparation method of lithium ion battery silicon-carbon composite cathode material |
| CN104091952A (en) * | 2014-07-24 | 2014-10-08 | 常州大学 | A kind of novel lithium-ion battery negative electrode material and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109524630A (en) * | 2017-09-20 | 2019-03-26 | 上海杉杉科技有限公司 | A kind of preparation method of cladded type composite negative pole material |
| CN111320868A (en) * | 2018-12-17 | 2020-06-23 | 杜邦聚合物有限公司 | Polymer composition with high dielectric constant and low dielectric loss |
| WO2020131212A1 (en) * | 2018-12-17 | 2020-06-25 | Dupont Polymers, Incorporated | Polymeric compositions with high dielectric constant and low dielectric loss |
| CN113614163A (en) * | 2018-12-17 | 2021-11-05 | 杜邦聚合物公司 | Polymer composition with high dielectric constant and low dielectric loss |
| CN111320868B (en) * | 2018-12-17 | 2023-02-28 | 杜邦聚合物有限公司 | Polymer composition with high dielectric constant and low dielectric loss |
| CN113614163B (en) * | 2018-12-17 | 2023-06-16 | 杜邦聚合物公司 | Polymer composition with high dielectric constant and low dielectric loss |
| US12247123B2 (en) | 2018-12-17 | 2025-03-11 | Celanese Polymers Holding, Inc. | Polymeric compositions with high dielectric constant and low dielectric loss |
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