CN110010860A - Composite negative pole material and lithium ion battery for lithium ion battery - Google Patents
Composite negative pole material and lithium ion battery for lithium ion battery Download PDFInfo
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- CN110010860A CN110010860A CN201910155881.7A CN201910155881A CN110010860A CN 110010860 A CN110010860 A CN 110010860A CN 201910155881 A CN201910155881 A CN 201910155881A CN 110010860 A CN110010860 A CN 110010860A
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- silicon
- carbon
- negative pole
- carbon nanotube
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- 239000002131 composite material Substances 0.000 title claims abstract description 106
- 239000000463 material Substances 0.000 title claims abstract description 98
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 44
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 157
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 136
- 239000004744 fabric Substances 0.000 claims abstract description 94
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 88
- 239000011248 coating agent Substances 0.000 claims abstract description 52
- 238000000576 coating method Methods 0.000 claims abstract description 52
- 239000002620 silicon nanotube Substances 0.000 claims abstract description 49
- 229910021430 silicon nanotube Inorganic materials 0.000 claims abstract description 49
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 239000000835 fiber Substances 0.000 claims abstract description 37
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 199
- 229910052710 silicon Inorganic materials 0.000 claims description 152
- 239000010703 silicon Substances 0.000 claims description 152
- 239000002070 nanowire Substances 0.000 claims description 88
- 229910052799 carbon Inorganic materials 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 47
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 38
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- 239000002121 nanofiber Substances 0.000 claims description 17
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 16
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- 238000001354 calcination Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
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- 238000002360 preparation method Methods 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 238000007323 disproportionation reaction Methods 0.000 claims description 11
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
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- 239000011261 inert gas Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002322 conducting polymer Substances 0.000 claims description 8
- 229920001940 conductive polymer Polymers 0.000 claims description 8
- 239000001294 propane Substances 0.000 claims description 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 238000005253 cladding Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000003345 natural gas Substances 0.000 claims description 6
- -1 γ-aminopropyl Chemical group 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000002048 multi walled nanotube Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000002109 single walled nanotube Substances 0.000 claims description 4
- 229910021384 soft carbon Inorganic materials 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 2
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 claims 1
- 238000007796 conventional method Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 238000007086 side reaction Methods 0.000 description 7
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- 239000007773 negative electrode material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 229920001197 polyacetylene Polymers 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000005662 electromechanics Effects 0.000 description 3
- MTKPOFJUULWZNU-UHFFFAOYSA-N ethoxysilicon Chemical compound CCO[Si] MTKPOFJUULWZNU-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 235000012149 noodles Nutrition 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 2
- 229910000570 Cupronickel Inorganic materials 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
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- 230000008859 change Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
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- 238000009830 intercalation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
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- 238000003199 nucleic acid amplification method Methods 0.000 description 1
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- 230000010287 polarization Effects 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M4/362—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses the composite negative pole materials and lithium ion battery for lithium ion battery.Wherein, composite negative pole material includes: silicon/carbon nano tube composite fibre cloth and carbon-coating, and the silicon/carbon nano tube composite fibre cloth includes the compound tow of silicon/carbon nanotube；The carbon-coating is formed in the silicon/carbon nano tube composite fibre cloth at least part surface.The composite negative pole material for being used for lithium ion battery, which is woven by the compound tow of silicon/carbon nanotube and coated carbon-coating, to be made, and can be directly used as negative electrode of lithium ion battery, have excellent energy density and cyclical stability.
Description
Technical field
The present invention relates to field of batteries, specifically, the present invention relates to the composite negative pole material of lithium ion battery and
Lithium ion battery.
Background technique
Requirement with electronic equipment, electric car to lithium ion battery energy density and cycle period is higher and higher, high
The research and development of the lithium ion battery of performance become more and more important, and wherein the raising of negative electrode material specific capacity can be such that battery energy density has larger
The promotion of amplitude.
Silicon has the embedding lithium specific capacity of up to 4200mAh/g, and intercalation potential is low, has good intercalation/deintercalation can
Inverse property becomes the new and effective lithium ion battery negative material of one kind for most having application prospect.But during removal lithium embedded, silicon
The volume change of sill is more than 300%, and can not only destroy battery structure also easily causes negative electrode material to fall off from collector,
Cause the cyclical stability of battery poor.And the intrinsic conductivity of silicon materials is very low, and the addition of silicon will increase the polarization of battery
Internal resistance.For problems, industry mainly uses nanosizing, Composite and designs the modes such as multistage porous structure to come pair at present
It is modified, but the effect is unsatisfactory, and generally existing preparation process is complicated, and composite material binding force is loose, cladding is uneven,
Not exclusively, it is difficult to realize amplification and commercialization.In order to alleviate the bulk effect of silicon materials, these techniques are added to a large amount of nonactive
Substance largely counteracts the high capacity advantage of silicon materials.As it can be seen that existing silicon materials cathode of lithium battery still needs into one
Step research.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is the composite negative pole material and lithium ion battery for proposing to be used for lithium ion battery.This is answered for lithium ion battery
Conjunction negative electrode material, which is woven by the compound tow of silicon/carbon nanotube and coated carbon-coating, to be made, and can be directly used as negative electrode of lithium ion battery, have
There are excellent energy density and cyclical stability.
In one aspect of the invention, the invention proposes a kind of composite negative pole materials for lithium ion battery.According to
The embodiment of the present invention, the composite negative pole material include: silicon/carbon nano tube composite fibre cloth and carbon-coating, the silicon/carbon nanotube
Complex fabric cloth includes the compound tow of silicon/carbon nanotube；The carbon-coating is formed in the silicon/carbon nano tube composite fibre cloth extremely
Few a part of surface.
Composite negative pole material according to an embodiment of the present invention, silicon/carbon nano tube composite fibre cloth are multiple by silicon/carbon nanotube
Plying beam weaves, and so as to which effectively Si therein is fixed, avoids the problem that cathode drops off, and improves Compound Negative
The cyclical stability of battery made by the material of pole.Silicon/surface coated carbon-coating of carbon nano tube composite fibre cloth can guarantee material
Expect surface without Si dew point, avoid applying in Si initiation side reaction is directly contacted with electrolyte.Silicon/carbon nanotube of the invention is compound
Fiber cloth is in fiber cloth-like, and negative electrode of lithium ion battery can be directly made after being cut to suitable shape, eliminates collector, glues
The use of the knot materials such as agent and corresponding close such as starchs, are coated and dried at the normal process steps, can promoted active material utilize space,
While improving battery energy density, save battery material cost, production process cost is significantly reduced.In addition, fiber cloth-like
Composite negative pole material, which can according to need, is cut into arbitrary shape, and have good flexibility, suitable for Special-shaped battery exploitation and
Using.
In addition, composite negative pole material according to the above embodiment of the present invention can also have the following additional technical features:
In some embodiments of the invention, the compound tow of silicon/carbon nanotube is by silicon nanowires and carbon nanotube
(CNTs) it is prepared by spinning processing, the silicon/carbon nano tube composite fibre cloth is by the compound tow of silicon/carbon nanotube
Braiding obtains.
In some embodiments of the invention, the diameter of the silicon nanowires is 1~200nm, and length is 0.5~300 μm；
The diameter of the carbon nanotube is 1~100nm, and length is 1~300 μm.
In some embodiments of the invention, the silicon nanowires is in pencil.
In some embodiments of the invention, the carbon nanotube is single-walled carbon nanotube and/or multi-walled carbon nanotube.
It in some embodiments of the invention, include precursor 1024~10240 in the compound tow of silicon/carbon nanotube
Root.
In some embodiments of the invention, the silicon nanowires accounts for the 0.1wt% of the composite negative pole material gross mass
~70wt%.
In some embodiments of the invention, the silicon nanowires account for the 1wt% of the composite negative pole material gross mass~
30wt%.
In some embodiments of the invention, the silicon/carbon nano tube composite fibre cloth and the mass ratio of the carbon-coating are
100:(0.01~10).
In some embodiments of the invention, the surface of the silicon nanowires have clad, the clad by soft carbon,
The formation of at least one of hard carbon and conducting polymer.
In some embodiments of the invention, the clad relative to the silicon nanowires accounting be 0.02wt%~
13wt%.
In some embodiments of the invention, the clad relative to the silicon nanowires accounting be 1wt%~
3wt%.
In some embodiments of the invention, the silicon/carbon nano tube composite fibre cloth is with a thickness of 30~300 μm.
In another aspect of this invention, the invention proposes a kind of sides of composite negative pole material for preparing above-described embodiment
Method.According to an embodiment of the invention, this method comprises: silicon nanowires and carbon nanotube are carried out spinning processing by (1), obtain silicon/
The compound tow of carbon nanotube；(2) the compound tow of silicon/carbon nanotube is subjected to braiding processing, it is compound obtains silicon/carbon nanotube
Fiber cloth；(3) carbon-coating is formed on the silicon/carbon nano tube composite fibre cloth at least part surface, obtains composite negative pole material
Material.
The production procedure of this method technique is simply controllable as a result, can be straight by the composite negative pole material that this method is prepared
It connects and is used as negative electrode of lithium ion battery, eliminate and prepare the conjunction of traditional pole piece containing collector and the normal process steps such as starch, be coated and dried, it can
Significantly reduce production process cost.
In addition, the method according to the above embodiment of the present invention for preparing composite negative pole material can also have it is following additional
Technical characteristic:
In some embodiments of the invention, the preparation method of the silicon nanowires includes: to mix silicon source and spin finish aid
Merge supply to electrostatic spinning machine, silicon-based nano fiber is prepared by method of electrostatic spinning；To the silicon-based nano fiber into
Row calcination processing obtains silicon nanofiber；The silicon nanofiber is subjected to reduction treatment or disproportionation processing, the silicon is obtained and receives
Rice noodles.
In some embodiments of the invention, the silicon source is selected from ethyl orthosilicate, three ethoxy silane of γ-aminopropyl, γ-
In (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane and γ-methacryloxypropyl trimethoxy silane at least it
One.
In some embodiments of the invention, the concentration of the silicon source is 4wt%~15wt%, the silicon source and the spinning
The mass ratio of silk auxiliary agent is 1:(0.4~3).
In some embodiments of the invention, the voltage of the electrostatic spinning machine is set as 8~20kV.
In some embodiments of the invention, the calcination processing air atmosphere and 500~1000 DEG C at a temperature of into
Row.
In some embodiments of the invention, the reduction treatment is in atmosphere of inert gases and 400~1000 DEG C of temperature
Lower progress is used as reducing agent using at least one of hydrogen, magnesium powder and carbon dust in the reduction treatment.
In some embodiments of the invention, the disproportionation processing is in atmosphere of inert gases and 400~1000 DEG C of temperature
Lower progress.
In some embodiments of the invention, the preparation method of the silicon nanowires further comprises: in the silicon nanometer
At least part surface of line forms clad.
In some embodiments of the invention, the preparation method of the carbon nanotube includes: in silicon substrate or iron-based plane
Catalyst and carbon source are introduced, growth obtains carbon nanotube under atmosphere of inert gases and growth temperature.
In some embodiments of the invention, the catalyst contain in Ni, Fe, Co, Pt, Ag and Cu at least it
One.
In some embodiments of the invention, the carbon source is in methane, ethane, propane, natural gas, ethyl alcohol and ethylene
At least one of.
In some embodiments of the invention, the growth temperature is 380~1000 DEG C.
In some embodiments of the invention, in step (3), using in methane, ethane, propane, natural gas and ethylene
At least one be used as carbon source, 400~1000 DEG C at a temperature of form the carbon-coating.
In another aspect of the invention, the invention proposes a kind of lithium ion batteries.According to an embodiment of the invention, the lithium
Ion battery includes: anode, cathode, diaphragm and electrolyte, and the cathode is formed by the composite negative pole material of above-described embodiment.By
This, which, as cathode, has and is retouched described previously for composite negative pole material by using above-mentioned composite negative pole material
The whole feature and advantage stated, this is no longer going to repeat them；In general, the lithium ion battery have excellent energy density and
The chemical properties such as cyclical stability.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures
Obviously and it is readily appreciated that, in which:
Fig. 1 is the method flow schematic diagram according to an embodiment of the invention for preparing composite negative pole material.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art
It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer,
For can be with conventional products that are commercially available.
In one aspect of the invention, the invention proposes a kind of composite negative pole materials for lithium ion battery.According to
The embodiment of the present invention, the composite negative pole material include: silicon/carbon nano tube composite fibre cloth and carbon-coating, the silicon/carbon nanotube
Complex fabric cloth includes the compound tow of silicon/carbon nanotube；The carbon-coating is formed in the silicon/carbon nano tube composite fibre cloth extremely
Few a part of surface.
Composite negative pole material according to an embodiment of the present invention, silicon/carbon nano tube composite fibre cloth are multiple by silicon/carbon nanotube
Plying beam weaves, and so as to which effectively Si therein is fixed, avoids the problem that cathode drops off, and improves Compound Negative
The cyclical stability of battery made by the material of pole.Silicon/surface coated carbon-coating of carbon nano tube composite fibre cloth can guarantee material
Expect surface without Si dew point, avoid applying in Si initiation side reaction is directly contacted with electrolyte.Silicon/carbon nanotube of the invention is compound
Fiber cloth is in fiber cloth-like, can eliminate collector directly as negative electrode of lithium ion battery after being cut to suitable shape, glue
The use of the knot materials such as agent and corresponding close such as starchs, are coated and dried at the normal process steps, can promoted active material utilize space,
While improving battery energy density, save battery material cost, production process cost is significantly reduced.In addition, fiber cloth-like
Composite negative pole material, which can according to need, is cut into arbitrary shape, and have good flexibility, suitable for Special-shaped battery exploitation and
Using.
Composite negative pole material according to an embodiment of the present invention is further described in detail below.
According to an embodiment of the invention, the above-mentioned compound tow of silicon/carbon nanotube (the compound tow of Si/CNTs) is by silicon nanowires
It is prepared with carbon nanotube (CNTs) by spinning processing.Inventors have found that handled by spinning, it can be by silicon nanowires
(or being silicon nanofiber) is spun into the precursor mutually wound with CNTs, is supported protection to silicon nanowires using CNTs, and
Contribute a part of embedding lithium capacity；There is the compound tow of Si/CNTs of macroscopical volume, Jin Erli by a number of precursor composition
It is woven to obtain silicon/carbon nano tube composite fibre cloth (Si/CNTs complex fabric cloth) with the compound tow of Si/CNTs.According to the present invention
Some embodiments, above-mentioned silicon nanowires be in tow shape, can be prepared by electrostatic spinning process, or derive from simple substance
One or more of silicon, Si oxide and silicon alloy；Above-mentioned carbon nanotube can use the single-walled carbon nanotube of oriented growth
(SWCNTs) and/or multi-walled carbon nanotube (MWCNTs).
According to an embodiment of the invention, the diameter of above-mentioned silicon nanowires can be 1~200nm, length can for 0.5~
300μm；The diameter of above-mentioned carbon nanotube can be 1~100nm, and length can be 1~300 μm.By control silicon nanowires with
On the one hand on the other hand the length and diameter of CNTs can also guarantee to spin in above range in order to the progress of spinning process
Si, CNTs content in the compound tow of Si/CNTs that silk obtains are easily controllable, and then are easy to join specific capacity of negative electrode material etc.
Number is adjusted.
It according to some embodiments of the present invention, include precursor 1024~10240 in the above-mentioned compound tow of silicon/carbon nanotube
Root.Thus, it is possible to be more convenient for the compound tow braiding of Si/CNTs Si/CNTs complex fabric cloth is made.If Si/CNTs is compound
Precursor quantity is very few in tow, then will lead to Si/CNTs complex fabric cloth thickness or consistency decline that braiding obtains, be unfavorable for
The performance of composite negative pole material performance made of Si/CNTs complex fabric cloth is subsequent.And if the compound tow Central Plains silk of Si/CNTs
Quantity is excessive, then is unfavorable for the control of Si content in the progress and composite negative pole material of knitting process.
According to some embodiments of the present invention, silicon nanowires accounts for 0.1wt%~70wt% of composite negative pole material gross mass.
The mass ratio of silicon nanowires can pass through the relative usage of silicon nanowires and CNTs in adjusting spinning process in the compound tow of Si/CNTs
To adjust.The dosage of silicon nanowires can be adjusted according to battery capacity design, realize that cathode specific capacity is adjustable, precisely to match
Positive electrode capacity achievees the purpose that capacitance balance.Inventors have found that accounting for composite negative pole material gross mass by controlling silicon nanowires
0.1wt%~70wt%, it is easy to cathode specific capacity is adjusted in conjunction with the thickness of Si/CNTs complex fabric cloth, it is positive and negative to realize
Pole capacity matching.Preferably, silicon nanowires accounts for 1wt%~30wt% of composite negative pole material gross mass, is more convenient for as a result, positive and negative
Pole capacity matching.
According to some embodiments of the present invention, the mass ratio of above-mentioned Si/CNTs pipe complex fabric cloth and above-mentioned carbon-coating can be with
For 100:(0.01~10), such as 100:0.1,100:0.5,100:1,100:3,100:5,100:8 or 100:10.Pass through control
Both systems mass ratio may further ensure that Si/CNTs pipe complex fabric cloth without Si dew point in above range, avoid applying in Si
It is directly contacted with electrolyte and causes side reaction.
According to some embodiments of the present invention, the surface of silicon nanowires has a clad, which can be by soft carbon, hard
The formation of at least one of carbon and conducting polymer.This is used for the clad of silicon nanowires in combination with multiple for Si/CNTs as a result,
The carbon-coating of condensating fiber cloth entirety realizes the secondary cladding to silicon nanowires, to guarantee that Si will not directly be contacted with battery electrolyte
And cause side reaction.The type of above-mentioned conducting polymer is not particularly restricted, and those skilled in the art can be according to practical need
Selected, specific example according to the present invention, above-mentioned conducting polymer can for selected from polyacetylene, it is poly- to styrene, it is poly-
One of pyrroles, polythiophene, polyaniline and polyphenylene sulfide are a variety of.It should be noted that the forming method of the clad is simultaneously
It is not particularly limited, can use the method for coating of this field routine by above-mentioned clad layer-forming on the surface of silicon nanowires.
According to some embodiments of the present invention, above-mentioned clad relative to silicon nanowires accounting can for 0.02wt%~
13wt%.Clad reflects the thickness of silicon nanowires clad relative to the accounting of silicon nanowires to a certain extent, if
Clad accounting is too low, then possibly can not effectively coat to silicon nanowires, cause Si exposed.And if clad accounting
It is excessively high, can not only cost of material be made to increase, it is also possible to cause the volume of Si/CNTs complex fabric cloth excessive, influence cathode performance.
It is highly preferred that above-mentioned clad is 1wt%~3wt%, the as a result, covered effect of silicon nanowires relative to the accounting of silicon nanowires
More preferably, comprehensive cost of material is lower.
According to some embodiments of the present invention.The thickness of above-mentioned Si/CNTs complex fabric cloth can be 30~300 μm.Such as
Preceding described, which is woven by the compound tow of Si/CNTs, is in fiber cloth-like.It can be held according to battery
Amount designs to adjust the thickness of Si/CNTs complex fabric cloth, realizes that cathode specific capacity is adjustable, is reached with precisely matching positive electrode capacity
The purpose of capacitance balance.Inventors have found that by control Si/CNTs complex fabric cloth with a thickness of 30~300 μm, it is easy to tie
Accounting of the silicon nanowires in composite negative pole material is closed to adjust cathode specific capacity, to realize positive and negative anodes capacity matching.According to this
The preferred embodiment of invention, Si/CNTs complex fabric cloth with a thickness of 80~150 μm, Si/CNTs complex fabric cloth as a result,
Performance, operability are more preferably.
As described above, composite negative pole material according to an embodiment of the present invention can have selected from following advantage at least it
One:
(1) similar woven fabric mode is used together with CNTs close weave, can to have silicon nanowires to silicon nanowires
Effect is fixed, and the problem of cathode drops off is avoided, and promotes circulating battery stability；
(2) silicon nanowires and Si/CNTs complex fabric cloth 2 times are coated, guarantees that material surface does not have Si dew point, keeps away
Exempt from silicon nanowires and directly contact electrolyte in the battery, causes side reaction；
(3) parameters such as the Si content to Si/CNTs complex fabric cloth, thickness can be designed according to battery capacity to adjust
Section realizes that cathode specific capacity is adjustable, and positive electrode capacity can precisely be matched by reaching, to achieve the purpose that capacitance balance；
(4) composite negative pole material can arbitrarily be cut according to cell shapes, provides convenience for the exploitation of Special-shaped battery；
(5) use for saving no-bonder sum aggregate fluid (foil) promotes active material and utilizes space, it is close to improve the energy content of battery
Degree saves battery material cost；
(6) it eliminates the need for closing involved in binder sum aggregate fluid preparation pole piece and the processes such as starches, is coated and dried, reduce
Production cost.
In another aspect of this invention, the invention proposes a kind of sides of composite negative pole material for preparing above-described embodiment
Method.According to an embodiment of the invention, this method comprises: silicon nanowires and carbon nanotube are carried out spinning processing by (1), obtain silicon/
The compound tow of carbon nanotube；(2) the compound tow of silicon/carbon nanotube is subjected to braiding processing, it is compound obtains silicon/carbon nanotube
Fiber cloth；(3) carbon-coating is formed on the silicon/carbon nano tube composite fibre cloth at least part surface, obtains composite negative pole material
Material.
The production procedure of this method technique is simply controllable as a result, can be straight by the composite negative pole material that this method is prepared
It connects and is used as negative electrode of lithium ion battery, eliminate and prepare the conjunction of traditional pole piece containing collector and the normal process steps such as starch, be coated and dried, it can
Significantly reduce production process cost.
The method according to an embodiment of the present invention for preparing composite negative pole material is described in detail below with reference to Fig. 1.Root
According to the embodiment of the present invention, this method comprises:
S100: spinning processing
In the step, silicon nanowires and carbon nanotube are subjected to spinning processing, obtain the compound tow of Si/CNTs.According to this
The specific example of invention, can be using conventional spinning process, by silicon nanowires and carbon nanotube weaving city Si/CNTs composite filament
Beam.
According to some embodiments of the present invention, the preparation method of above-mentioned silicon nanowires includes: to mix silicon source and spin finish aid
Merge supply to electrostatic spinning machine, silicon-based nano fiber is prepared by method of electrostatic spinning；Silicon-based nano fiber is forged
Burning processing, obtains silicon nanofiber；Silicon nanofiber is subjected to reduction treatment or disproportionation processing, obtains silicon nanowires.According to upper
The method of stating prepares silicon nanowires, and preparation method is simple, is suitable for large-scale production.The specific type of above-mentioned spin finish aid is not by spy
It does not limit, the spin finish aid that this field can be used common.Specific example according to the present invention, above-mentioned spin finish aid can use
At least one of polyvinyl alcohol (PVA) and polyacrylonitrile (PAN).
According to some embodiments of the present invention, above-mentioned silicon source can be for selected from ethyl orthosilicate, three ethoxy silicon of γ-aminopropyl
In alkane, γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane and γ-methacryloxypropyl trimethoxy silane extremely
It is one of few.The above silicon source is cheap and easy to get, from a wealth of sources, and silicon can be made by electrostatic spinning process with spin finish aid well
Nano wire.
According to some embodiments of the present invention, the concentration of above-mentioned silicon source can be 4wt%~15wt%, such as 4wt%,
5wt%, 6wt%, 8wt%, 10wt%, 12wt% or 15wt%；The mass ratio of above-mentioned silicon source and spin finish aid can be 1:
(0.4~3), such as 1:0.4,1:0.6,1:0.8,1:1,1:1.5,1:2,1:2.5 or 1:3.The silicon nanometer being prepared as a result,
Linear diameter, length parameter are easy to control, and intensity is high, can satisfy subsequent technique requirement.
According to some embodiments of the present invention, the voltage of above-mentioned electrostatic spinning machine is set as 8~20kV, such as 8kV,
10kV, 12kV, 15kV or 20kV.Thus, it is possible to be more convenient for controlling the parameters such as diameter, the length of silicon-based nano fiber product, more
Conducive to the progress of subsequent handling.
According to some embodiments of the present invention, above-mentioned calcination processing can air atmosphere and 500~1000 DEG C at a temperature of
It carries out, calcination temperature can be 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C or 1000 DEG C.Above-mentioned reduction treatment is in indifferent gas
Carried out at a temperature of body atmosphere and 400~1000 DEG C, reduction temperature can for 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C,
900 DEG C or 1000 DEG C；Reducing agent can be used as using at least one of hydrogen, magnesium powder and carbon dust in reduction treatment.Above-mentioned discrimination
Change processing can atmosphere of inert gases and 400~1000 DEG C at a temperature of carry out, disproportionation temperature can be 400 DEG C, 500 DEG C, 600
DEG C, 700 DEG C, 800 DEG C, 900 DEG C or 1000 DEG C.It restores or is disproportionated by first calcining silicon-based nano fiber product, Ke Yiyou
Effect removes the impurity in product, improves product silicon purity, to obtain the chemical properties such as more preferably embedding lithium capacity.
According to some embodiments of the present invention, the preparation method of above-mentioned silicon nanowires may further include: in silicon nanometer
At least part surface of line forms clad, which is formed by least one of soft carbon, hard carbon and conducting polymer.
The clad for being used for silicon nanowires is realized in combination with the carbon-coating for Si/CNTs complex fabric cloth entirety to silicon nanometer as a result,
The secondary cladding of line, to guarantee that Si will not directly be contacted with battery electrolyte and be caused side reaction.Above-mentioned conducting polymer
Type is not particularly restricted, and those skilled in the art can select according to actual needs, according to the present invention specifically to show
Example, above-mentioned conducting polymer can be selected from polyacetylene, gather in styrene, polypyrrole, polythiophene, polyaniline and polyphenylene sulfide
It is one or more.It should be noted that the forming method of the clad is not particularly restricted, it can be conventional using this field
Method for coating by above-mentioned clad layer-forming on the surface of silicon nanowires.
According to some embodiments of the present invention, the preparation method of above-mentioned carbon nanotube includes: to silicon substrate or iron-based plane (base
Bottom) on introduce catalyst and carbon source, growth obtains carbon nanotube under atmosphere of inert gases and growth temperature.Specifically, catalysis
Agent can introduce substrate by the sedimentation, switching method or electrochemistry galvanoplastic of this field maturation, and then be passed through carbon source, grow
To CNTs.
According to some embodiments of the present invention, above-mentioned catalyst contains in Ni, Fe, Co, Pt, Ag and Cu at least
One of.CNTs growth efficiency is high as a result, and the parameters such as obtained CNTs diameter, length are easily controllable.
According to some embodiments of the present invention, above-mentioned carbon source can for selected from methane, ethane, propane, natural gas, ethyl alcohol and
At least one of ethylene.CNTs growth efficiency is high as a result, and the parameters such as obtained CNTs diameter, length are easily controllable.Separately
Outside, above-mentioned carbon source is easy to separate from CNTs product, will not adversely affect to the purity of product.
According to some embodiments of the present invention, above-mentioned growth temperature can be 380~1000 DEG C of CNTs growth efficiencies as a result,
Height, and the parameters such as obtained CNTs diameter, length are easily controllable.
S200: braiding processing
In the step, the compound tow of Si/CNTs is subjected to braiding processing, obtains Si/CNTs complex fabric cloth.According to this hair
Bright specific example can weave the compound tow of Si/CNTs to obtain Si/CNTs composite fibre using conventional weaving process
Cloth.
S300: carbon coating
In the step, carbon-coating is formed at least part surface of Si/CNTs complex fabric cloth, obtains composite negative pole material
Material.By further coating carbon-coating to Si/CNTs complex fabric cloth, it may further ensure that material surface without Si dew point, avoids
Si is directly contacted with electrolyte in causes side reaction.It should be noted that at least one of Si/CNTs complex fabric cloth
The method that point surface forms carbon-coating is not particularly restricted, and can use the carbon coating technique of this field routine.
According to some embodiments of the present invention, can use in methane, ethane, propane, natural gas and ethylene at least it
One is used as carbon source, 400~1000 DEG C at a temperature of form above-mentioned carbon-coating, formed cladding carbon-coating temperature can for 400 DEG C,
500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C or 1000 DEG C.The formation efficiency of carbon-coating is high as a result, and the parameters such as thickness are easy to
Control.
In another aspect of the invention, the invention proposes a kind of lithium ion batteries.According to an embodiment of the invention, the lithium
Ion battery includes: anode, cathode, diaphragm and electrolyte, and the cathode is formed by the composite negative pole material of above-described embodiment.By
This, which, as cathode, has and is retouched described previously for composite negative pole material by using above-mentioned composite negative pole material
The whole feature and advantage stated, this is no longer going to repeat them；In general, the lithium ion battery have excellent energy density and
The chemical properties such as cyclical stability.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Conventional method
Composite negative pole material is prepared according to the following steps:
(1-1) prepares silicon nanowires: silicon source being mixed with polyvinyl alcohol (PVA) and is supplied to electrostatic spinning machine, by quiet
Silicon-based nano fiber is prepared in electrical spinning method；Calcination processing is carried out to silicon-based nano fiber, is obtained silica nano fibrous；
Silica nano fibrous progress reduction treatment or disproportionation are handled, silicon nanowires is obtained.
(1-2) prepares carbon nanotube: catalyst and carbon source is introduced on silicon-base plane, in atmosphere of inert gases and growth temperature
The lower growth of degree obtains carbon nanotube.
(1-3) carries out spinning using silicon nanowires and carbon nanotube, obtains Si/CNTs composite harness.
Si/CNTs complex fabric cloth is made in the braiding of Si/CNTs composite harness by (1-4).
(1-5) forms carbon-coating on the surface of Si/CNTs complex fabric cloth, obtains composite negative pole material.
Further, lithium ion battery is prepared according to the following steps:
(2-1) prepares anode pole piece: by the NCM811 positive electrode active materials of 94.5 parts by weight, the conductive black of 3 parts by weight
SP and the mixing of the Kynoar (PVDF) of 2.5 parts by weight, and add N-Methyl pyrrolidone and stir to form slurries, slurries are equal
It is even to be coated on plus plate current-collecting body aluminium foil, it is rolled after dry with roller, anode pole piece is made.
(2-2) prepares cathode pole piece: making cathode pole piece with the negative electrode material that step (1-5) is prepared.
(2-3) prepares diaphragm: the two-sided PE base coating diaphragm that diaphragm uses with a thickness of 30 μm.
(2-4) prepares electrolyte: methyl ethyl carbonate and ethylene carbonate being mixed according to volume ratio 70:30, and thereto
The lithium hexafluoro phosphate of 1.15mol/L is added as electrolyte.
(2-5) prepares shell: shell uses aluminum hull.
(2-6) prepares external terminal: positive terminal uses aluminium material, and negative terminal uses copper nickel plating material.
(2-7) prepares battery: by anode pole piece, diaphragm, the alternate formation battery core of cathode pole piece, connection terminal；Then it carries out
Primary sealing, injects electrolyte, secondary sealing；It successively carries out shelving-preliminary filling-evacuation-chemical conversion-partial volume, lithium ion battery is made.
Embodiment 1
Composite negative pole material is prepared according to conventional method, wherein
In step (1-1), silicon source uses ethyl orthosilicate, and concentration 4wt%, silicon source and PVA mass ratio are 1:0.4, quiet
Electrospun electromechanics pressure is set as 8kV；Calcination processing carries out at air atmosphere, 500 DEG C；Silicon is prepared by reduction treatment to receive
Rice noodles, reduction treatment carry out at nitrogen atmosphere, 400 DEG C, using hydrogen as reducing agent in reduction treatment.Gained silicon nanowires
Diameter is 50nm, and length is 50 μm.It is subsequent, carbon coating is carried out to gained silicon nanowires, carbon source uses coke, gained clad matter
Amount accounting is 1wt%.
In step (1-2), catalyst uses Ni simple substance, and carbon source uses methane, grows and obtain at nitrogen atmosphere, 380 DEG C
Carbon nanotube.Gained carbon nanotube diameter is 20nm, and length is 50 μm.
It include precursor 1024 in gained Si/CNTs composite harness in step (1-3).
In step (1-4), gained Si/CNTs complex fabric cloth with a thickness of 30 μm.
In step (1-5), using methane as carbon source, carbon-coating is formed at 400 DEG C, obtains composite negative pole material.The Compound Negative
The silicon nanowires content of pole material is 0.1wt%.
Subsequent the step of preparing lithium ion battery same conventional method.
Embodiment 2
Composite negative pole material is prepared according to conventional method, wherein
In step (1-1), silicon source uses ethyl orthosilicate, and concentration 10wt%, silicon source and PVA mass ratio are 1:1.2, quiet
Electrospun electromechanics pressure is set as 15kV；Calcination processing carries out at air atmosphere, 800 DEG C；Silicon is prepared by reduction treatment
Nano wire, reduction treatment carry out at nitrogen atmosphere, 600 DEG C, using carbon dust as reducing agent in reduction treatment.Gained silicon nanometer
Linear diameter is 150nm, and length is 200 μm.It is subsequent, carbon coating is carried out to gained silicon nanowires, carbon source uses carbon black, gained cladding
Layer quality accounting is 5wt%.
In step (1-2), catalyst uses Fe simple substance, and carbon source uses propane, grows and obtain at nitrogen atmosphere, 600 DEG C
Carbon nanotube.Gained carbon nanotube diameter is 50nm, and length is 200 μm.
It include precursor 2048 in gained Si/CNTs composite harness in step (1-3).
In step (1-4), gained Si/CNTs complex fabric cloth with a thickness of 100 μm.
In step (1-5), using methane as carbon source, carbon-coating is formed at 600 DEG C, obtains composite negative pole material.The Compound Negative
The silicon nanowires content of pole material is 5wt%.
Subsequent the step of preparing lithium ion battery same conventional method.
Embodiment 3
Composite negative pole material is prepared according to conventional method, wherein
In step (1-1), silicon source uses three ethoxy silane of γ-aminopropyl, concentration 10wt%, silicon source and PVA mass ratio
For 1:0.8, electrostatic spinning machine voltage is set as 12kV；Calcination processing carries out at air atmosphere, 700 DEG C；Pass through reduction treatment
Silicon nanowires is prepared, reduction treatment carries out at nitrogen atmosphere, 600 DEG C, using carbon dust as reducing agent in reduction treatment.
Gained silicon nanowires diameter is 100nm, and length is 150 μm.It is subsequent, carbon coating is carried out to gained silicon nanowires, carbon source is using burnt
Charcoal, gained clad quality accounting are 3wt%.
In step (1-2), catalyst uses Cu simple substance, and carbon source uses ethane, grows and obtain at nitrogen atmosphere, 420 DEG C
Carbon nanotube.Gained carbon nanotube diameter is 30nm, and length is 150 μm.
It include precursor 2048 in gained Si/CNTs composite harness in step (1-3).
In step (1-4), gained Si/CNTs complex fabric cloth with a thickness of 80 μm.
In step (1-5), using methane as carbon source, carbon-coating is formed at 600 DEG C, obtains composite negative pole material.The Compound Negative
The silicon nanowires content of pole material is 2wt%.
Subsequent the step of preparing lithium ion battery same conventional method.
Embodiment 4
Composite negative pole material is prepared according to conventional method, wherein
In step (1-1), silicon source uses γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, concentration 15wt%, silicon
Source and PVA mass ratio are 1:2, and electrostatic spinning machine voltage is set as 15kV；Calcination processing carries out at air atmosphere, 800 DEG C；It is logical
It crosses reduction treatment and silicon nanowires is prepared, reduction treatment carries out at nitrogen atmosphere, 800 DEG C, and hydrogen is used in reduction treatment
As reducing agent.Gained silicon nanowires diameter is 150nm, and length is 200 μm.It is subsequent, carbon coating is carried out to gained silicon nanowires,
Carbon source uses coke, and gained clad quality accounting is 8wt%.
In step (1-2), catalyst uses Co simple substance, and carbon source uses propane, grows and obtain at nitrogen atmosphere, 600 DEG C
Carbon nanotube.Gained carbon nanotube diameter is 100nm, and length is 200 μm.
It include precursor 10240 in gained Si/CNTs composite harness in step (1-3).
In step (1-4), gained Si/CNTs complex fabric cloth with a thickness of 150 μm.
In step (1-5), using methane as carbon source, carbon-coating is formed at 600 DEG C, obtains composite negative pole material.The Compound Negative
The silicon nanowires content of pole material is 30wt%.
Subsequent the step of preparing lithium ion battery same conventional method.
Embodiment 5
Composite negative pole material is prepared according to conventional method, wherein
In step (1-1), silicon source uses γ-methacryloxypropyl trimethoxy silane, concentration 15wt%, silicon
Source and PVA mass ratio are 1:3, and electrostatic spinning machine voltage is set as 20kV；Calcination processing carries out at air atmosphere, 1000 DEG C；
It is handled by disproportionation and silicon nanowires is prepared, disproportionation processing carries out at nitrogen atmosphere, 1000 DEG C.Gained silicon nanowires diameter
For 150nm, length is 200 μm.It is subsequent, carbon coating is carried out to gained silicon nanowires, carbon source uses polyacetylene, gained clad matter
Amount accounting is 13wt%.
In step (1-2), catalyst uses Pt simple substance, and carbon source uses ethylene, grows and obtain at nitrogen atmosphere, 800 DEG C
Carbon nanotube.Gained carbon nanotube diameter is 100nm, and length is 200 μm.
It include precursor 2048 in gained Si/CNTs composite harness in step (1-3).
In step (1-4), gained Si/CNTs complex fabric cloth with a thickness of 150 μm.
In step (1-5), using methane as carbon source, carbon-coating is formed at 800 DEG C, obtains composite negative pole material.The Compound Negative
The silicon nanowires content of pole material is 30wt%.
Subsequent the step of preparing lithium ion battery same conventional method.
Embodiment 6
Composite negative pole material is prepared according to conventional method, wherein
In step (1-1), silicon source uses ethyl orthosilicate, and concentration 15wt%, silicon source and PVA mass ratio are 1:2.5, quiet
Electrospun electromechanics pressure is set as 18kV；Calcination processing carries out at air atmosphere, 800 DEG C；It is handled by disproportionation and silicon is prepared
Nano wire, disproportionation processing carry out at nitrogen atmosphere, 800 DEG C.Gained silicon nanowires diameter is 200nm, and length is 300 μm.Afterwards
It is continuous, carbon coating is carried out to gained silicon nanowires, carbon source uses polyacetylene, and gained clad quality accounting is 13wt%.
In step (1-2), catalyst uses Ag simple substance, and carbon source uses ethyl alcohol, grows and obtain at nitrogen atmosphere, 800 DEG C
Carbon nanotube.Gained carbon nanotube diameter is 100nm, and length is 300 μm.
It include precursor 10240 in gained Si/CNTs composite harness in step (1-3).
In step (1-4), gained Si/CNTs complex fabric cloth with a thickness of 300 μm.
In step (1-5), using methane as carbon source, carbon-coating is formed at 800 DEG C, obtains composite negative pole material.The Compound Negative
The silicon nanowires content of pole material is 60wt%.
Subsequent the step of preparing lithium ion battery same conventional method.
Comparative example 1
Lithium ion battery is prepared according to the following steps:
(a) anode pole piece is prepared: by the NCM811 positive electrode active materials of 94.5 parts by weight, the conductive black SP of 3 parts by weight
It is mixed with the Kynoar (PVDF) of 2.5 parts by weight, and adds N-Methyl pyrrolidone and stir to form slurries, slurries are uniform
Coated on plus plate current-collecting body aluminium foil, is rolled after dry with roller, anode pole piece is made.
(b) cathode pole piece is prepared: by the artificial graphite (capacity >=355mAh/g) of 95.7 parts by weight, 0.5 parts by weight
The butadiene-styrene rubber (SBR) of conductive black SP, the sodium carboxymethylcellulose (CMC) of 1.5 parts by weight and 2.3 parts by weight mix, and
Addition deionized water stirs to form slurries, and slurries are coated uniformly on negative current collector copper foil, is carried out after dry with roller
It rolls, cathode pole piece is made.
(c) prepare diaphragm: the two-sided PE base coating diaphragm that diaphragm uses with a thickness of 30 μm.
(d) it prepares electrolyte: methyl ethyl carbonate and ethylene carbonate being mixed according to volume ratio 70:30, and added thereto
Enter the lithium hexafluoro phosphate of 1.15mol/L as electrolyte.
(e) prepare shell: shell uses aluminum hull.
(f) prepare external terminal: positive terminal uses aluminium material, and negative terminal uses copper nickel plating material.
(g) battery is prepared: by anode pole piece, diaphragm, the alternate formation battery core of cathode pole piece, connection terminal；Then one is carried out
Electrolyte, secondary sealing are injected in secondary sealing；It successively carries out shelving-preliminary filling-evacuation-chemical conversion-partial volume, lithium ion battery is made.
Comparative example 2
Composite negative pole material is prepared according to method substantially the same manner as Example 1, difference is, in step (1-1), silicon is received
Rice noodles directly carry out spinning with CNTs without carbon coating.
Subsequent the step of preparing lithium ion battery same conventional method.
Test case
(1) energy density is tested:
Battery made from above-described embodiment and comparative example is respectively taken into 5 measurements, 23 DEG C of energy densities.Measuring method are as follows: 23
At DEG C then electric current is turned into constant-voltage charge, cut-off current 0.05C with 0.5C constant current charging to upper limit voltage；It shelves
10min is discharged to 2.7V with 0.5C constant current, and measurement obtains the discharge capacity of battery；After shelving 10min, above-mentioned step is repeated
Rapid 3 times, calculate 3 discharge capacity average values.Use the weight of electronic balance weighing different type battery.23 are calculated according to the following formula
DEG C battery energy density:
Battery energy density=electric discharge average size × mean voltage/battery weight.
Test result is shown in Table 1.
(2) cycle performance is tested:
Battery, with 0.5C constant current charging to upper limit voltage, then turns constant-voltage charge, cut-off current at 23 DEG C
0.05C；10min is shelved, 2.7V is discharged to 0.5C constant current, measurement obtains the initial discharge capacity C of battery0；It shelves
After 10min, repeats the above steps 1500 times, make continuous charge-discharge test, the capacity C after obtaining battery 1500 times circulations1.It presses
The capacity surplus ratio of battery after 1500 circulations is calculated according to following formula:
Capacity surplus ratio=C1/C0× 100%.
Test result is shown in Table 1.
1 battery performance test result of table
Test result shows the lithium ion battery being prepared with composite negative pole material production battery cathode of the invention,
Relative to traditional lithium ion battery (comparative example 1), battery energy density is obviously improved, and cyclical stability is more preferably.From reality
Example 1 and comparative example 2 are applied as can be seen that influence difference of the carbon coating to battery energy density of silicon nanowires is unobvious, but if
Cancel the carbon coating layer of silicon nanowires and carbon-coating only is covered to Si/CNTs complex fabric cloth, does not ensure that electrode surface does not go out
Existing Si dew point, the cycle performance of battery are affected.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of composite negative pole material for lithium ion battery characterized by comprising
Silicon/carbon nano tube composite fibre cloth, the silicon/carbon nano tube composite fibre cloth include the compound tow of silicon/carbon nanotube；
Carbon-coating, the carbon-coating are formed in the silicon/carbon nano tube composite fibre cloth at least part surface.
2. composite negative pole material according to claim 1, which is characterized in that the compound tow of silicon/carbon nanotube is by silicon
Nano wire and carbon nanotube are prepared by spinning processing, and the silicon/carbon nano tube composite fibre cloth is by the silicon/carbon nanometer
Compound tow is managed to weave to obtain；
Optionally, the diameter of the silicon nanowires is 1~200nm, and length is 0.5~300 μm；The diameter of the carbon nanotube is
1~100nm, length are 1~300 μm；
Optionally, the silicon nanowires is in pencil；
Optionally, the carbon nanotube is single-walled carbon nanotube and/or multi-walled carbon nanotube；
It optionally, include precursor 1024~10240 in the compound tow of silicon/carbon nanotube.
3. composite negative pole material according to claim 2, which is characterized in that the silicon nanowires accounts for the composite negative pole material
Expect 0.1wt%~70wt% of gross mass；Preferably, the silicon nanowires accounts for the 1wt% of the composite negative pole material gross mass
~30wt%；
Optionally, the mass ratio of the silicon/carbon nano tube composite fibre cloth and the carbon-coating is 100:(0.01~10).
4. composite negative pole material according to claim 2, which is characterized in that the surface of the silicon nanowires has cladding
Layer, the clad are formed by least one of soft carbon, hard carbon and conducting polymer；
Optionally, the clad is 0.02wt%~13wt% relative to the accounting of the silicon nanowires；Preferably, the packet
Coating is 1wt%~3wt% relative to the accounting of the silicon nanowires.
5. composite negative pole material according to any one of claims 1 to 4, which is characterized in that the silicon/carbon nanotube is compound
Fiber cloth with a thickness of 30~300 μm, it is preferable that the silicon/carbon nano tube composite fibre cloth is with a thickness of 80~150 μm.
6. a kind of method for preparing the described in any item composite negative pole materials of Claims 1 to 5 characterized by comprising
(1) silicon nanowires and carbon nanotube are subjected to spinning processing, obtain the compound tow of silicon/carbon nanotube；
(2) the compound tow of silicon/carbon nanotube is subjected to braiding processing, obtains silicon/carbon nano tube composite fibre cloth；
(3) carbon-coating is formed on the silicon/carbon nano tube composite fibre cloth at least part surface, obtains composite negative pole material.
7. according to the method described in claim 6, it is characterized in that, the preparation method of the silicon nanowires include: by silicon source with
Spin finish aid is mixed and is supplied to electrostatic spinning machine, and silicon-based nano fiber is prepared by method of electrostatic spinning；To the silicon substrate
Nanofiber carries out calcination processing, obtains silicon nanofiber；The silicon nanofiber is subjected to reduction treatment or disproportionation processing, is obtained
To the silicon nanowires；
Optionally, the silicon source is selected from ethyl orthosilicate, three ethoxy silane of γ-aminopropyl, γ-(2,3- the third oxygen of epoxy) propyl three
At least one of methoxy silane and γ-methacryloxypropyl trimethoxy silane；
Optionally, the concentration of the silicon source is 4wt%~15wt%, and the silicon source and the mass ratio of the spin finish aid are 1:
(0.4~3)；
Optionally, the spin finish aid is selected from least one of polyvinyl alcohol and polyacrylonitrile；
Optionally, the voltage of the electrostatic spinning machine is set as 8~20kV；
Optionally, the calcination processing air atmosphere and 500~1000 DEG C at a temperature of carry out；
Optionally, the reduction treatment atmosphere of inert gases and 400~1000 DEG C at a temperature of carry out, in the reduction treatment
Reducing agent is used as using at least one of hydrogen, magnesium powder and carbon dust；
Optionally, the disproportionation processing atmosphere of inert gases and 400~1000 DEG C at a temperature of carry out；
Optionally, the preparation method of the silicon nanowires further comprises: at least part surface shape of the silicon nanowires
At clad.
8. according to the method described in claim 6, it is characterized in that, the preparation method of the carbon nanotube include: to silicon substrate or
Catalyst and carbon source are introduced in iron-based plane, growth obtains carbon nanotube under atmosphere of inert gases and growth temperature；
Optionally, the catalyst contains selected from least one of Ni, Fe, Co, Pt, Ag and Cu；
Optionally, the carbon source is selected from least one of methane, ethane, propane, natural gas, ethyl alcohol and ethylene；
Optionally, the growth temperature is 380~1000 DEG C.
9. according to the method described in claim 6, it is characterized in that, utilizing methane, ethane, propane, natural gas in step (3)
Be used as carbon source at least one of ethylene, 400~1000 DEG C at a temperature of form the carbon-coating.
10. a kind of lithium ion battery characterized by comprising anode, cathode, diaphragm and electrolyte, the cathode are wanted by right
1~5 described in any item composite negative pole materials are asked to be formed.
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| CN114284479A (en) * | 2021-12-22 | 2022-04-05 | 博路天成新能源科技有限公司 | Preparation method of novel carbon-silicon negative electrode material |
| CN114420940A (en) * | 2022-02-07 | 2022-04-29 | 大连中比动力电池有限公司 | Current collector for lithium ion secondary battery and preparation method and system thereof |
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