CN105742599B - Si-C composite material and preparation method thereof and negative electrode material and battery - Google Patents
Si-C composite material and preparation method thereof and negative electrode material and battery Download PDFInfo
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims description 49
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000007773 negative electrode material Substances 0.000 title description 18
- 239000003575 carbonaceous material Substances 0.000 claims description 30
- 239000002210 silicon-based material Substances 0.000 claims description 27
- 239000002105 nanoparticle Substances 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 229910000765 intermetallic Inorganic materials 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 13
- 238000001694 spray drying Methods 0.000 claims description 10
- 229910021332 silicide Inorganic materials 0.000 claims description 7
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007767 bonding agent Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 239000011258 core-shell material Substances 0.000 description 15
- 239000002002 slurry Substances 0.000 description 13
- 239000010410 layer Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000005507 spraying Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- -1 silicon oxide compound Chemical class 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910015877 MSiy Inorganic materials 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
-
- 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
- H01M4/582—Halogenides
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Silicon Compounds (AREA)
Abstract
The present invention relates to a kind of Si-C composite materials comprising three-layer nuclear shell structure, innermost layer are silicon materials, and middle layer is metallic compound, and outermost layer is carbon material；Silicon materials are selected from one or more of silicon, Si oxide and metal silicide.Above-mentioned Si-C composite material is additionally provided with the middle layer of metallic compound between silicon materials and carbon material, effectively improves the interfacial contact between silicon materials and carbon material, keeps Si-C composite material more stable in use.The electric conductivity of the Si-C composite material is promoted, and energy density also has promotion.The Si-C composite material is easier to bond with collector in subsequent ingredient use process, it is not easy to reunite or drop off, improve Si-C composite material cycle performance.Preparation method, technology difficulty is low, and equipment is simple, is conducive to industrialized production.The invention also discloses preparation method, negative electrode material and the batteries of a kind of above-mentioned Si-C composite material.
Description
Technical field
The present invention relates to field of batteries, more particularly to a kind of Si-C composite material and preparation method thereof and negative electrode material and
Battery.
Background technique
Compared with traditionally graphite cathode material, silicon have superelevation theoretical specific capacity (4200mAh/g) and it is lower take off
Lithium current potential (< 0.5V), and the voltage platform of silicon is slightly above graphite, is less likely to occur surface analysis lithium behavior, safety in charging
More preferably, therefore the new research direction of negative electrode material of battery can be become.
But since silicon is semiconductor material, when as cell negative electrode material, self-conductance rate is lower, and lithium ion is filling
Insertion and abjection in discharge process can make silicon volume occur 300% or more expansion and contraction, can make powder body material structure by
It gradually collapses, eventually leads to electrode active material and collector is detached from, cycle performance of battery is caused to substantially reduce.
For the cycle performance for improving silica-base material, cyclical stability is improved, while keeping its original high-energy density special
Property.Usually by silica-base material Composite, Si-C composite material is formed.Because of carbon material electronic conductivity with higher and ion
Conductivity can significantly improve the high rate performance of silica-base material, inhibit bulk effect of the silicon in cyclic process.In addition, carbon material
Silicon can be obstructed and directly contacted with electrolyte, irreversible capacity is reduced.
But the interfacial contact of silicon materials and carbon material between the two is poor in traditional Si-C composite material, and tradition
Preparation of silicon carbon composite materials technology difficulty it is big, the device is complicated, is unfavorable for industrialized production.
Summary of the invention
Based on this, it is necessary to for the interfacial contact of silicon materials and carbon material between the two in existing Si-C composite material
It is good and prepare simple Si-C composite material to provide a kind of interfacial contact for problem poor and that preparation process difficulty is big.
A kind of Si-C composite material comprising the first core-shell structure, the kernel of first core-shell structure are nanoparticle,
The shell of first core-shell structure is carbon material；The nanoparticle is the second core-shell structure, second core-shell structure
Kernel is silicon materials；The shell of second core-shell structure is metallic compound；The silicon materials are selected from silicon, Si oxide and gold
Belong to one or more of silicide.
Above-mentioned Si-C composite material, including two core-shell structures, that is to say, that be additionally provided between silicon materials and carbon material
The middle layer of metallic compound effectively improves the interface between silicon materials and carbon material by the middle layer of metallic compound and connects
Touching property；Keep Si-C composite material more stable in use.Above-mentioned Si-C composite material, due to joined metal compound
Object, improves the electric conductivity of Si-C composite material, and energy density also has promotion.Above-mentioned Si-C composite material, by nucleocapsid knot
The secondary cladding of the nanoparticle of structure, be easier in subsequent ingredient use process and collector bond, it is not easy to reunite or
It drops off, improves Si-C composite material cycle performance.In addition, being directly coated on by setting middle layer to reduce carbon material
The difficulty on silicon materials surface, equipment is simple, is conducive to industrialized production.
The general formula of the silicon oxide compound is SiO in one of the embodiments,x, wherein 0.5≤x≤1.5；The gold
The general formula for belonging to silicide is MSiy, wherein M is selected from one or more of Fe, Ni, Cr, Mn, Ti and Co, 0.5≤y≤2.
In one of the embodiments, the metallic compound be selected from one of metal oxide and metal halide or
It is several.
The carbon material is in carbon nanotube, carbonaceous mesophase spherules, graphene and hard carbon in one of the embodiments,
One or more.
The median particle diameter of the nanoparticle is 10-600nm in one of the embodiments,.
The median particle diameter of the Si-C composite material is 1-100 μm in one of the embodiments,.
The present invention also provides a kind of preparation methods of above-mentioned Si-C composite material.
A kind of preparation method of Si-C composite material, includes the following steps:
Metallo-organic compound is dispersed in the first decentralized medium, silicon materials are added and are uniformly mixed, are then spray-dried
Obtain the first presoma；The silicon materials are one or more of silicon, Si oxide and metal silicide；
First presoma is calcined under atmosphere at 350-1000 DEG C, obtains nanoparticle；
The nanoparticle is uniformly mixed with bonding agent, is gradually added carbon material, ultrasonic disperse obtains the second presoma；
Second presoma is sintered at 300-900 DEG C, obtains Si-C composite material.
Above-mentioned preparation method, technique are easy to control, and do not need complicated production equipment, and required equipment is few, and production capacity is big, favorably
In the industrialization large-scale production of Si-C composite material.In addition, above-mentioned preparation method, improves the utilization rate of silicon.
The drying temperature of the spray drying is 100~400 DEG C in one of the embodiments,.
The present invention also provides a kind of negative electrode materials.
A kind of negative electrode material comprising Si-C composite material provided by the present invention.
Above-mentioned negative electrode material, due to using Si-C composite material provided by the present invention, to improve the conduction of negative electrode material
Property, energy density also has promotion, and cycle life increases.
The present invention also provides a kind of batteries.
A kind of battery comprising negative electrode material provided by the present invention.
Above-mentioned battery, due to using negative electrode material provided by the present invention, energy density is high, and has extended cycle life.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, right below in conjunction with specific embodiment
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are only used to explain the present invention,
It is not intended to limit the present invention.
A kind of Si-C composite material, including the first core-shell structure, the kernel of first core-shell structure are nanoparticle, this
The shell of one core-shell structure is carbon material；Nanoparticle is the second core-shell structure, and the kernel of second core-shell structure is silicon materials；
The shell of second core-shell structure is metallic compound.That is, Si-C composite material includes three-layer nuclear shell structure, it is most interior
Layer is silicon materials, and middle layer is metallic compound, and outermost layer is carbon material.
Wherein, silicon materials are located at innermost layer, are the inner cores of core-shell structure.Silicon materials of the invention are selected from silicon, silicon aoxidizes
One or more of object and metal silicide.Silicon can select crystalline silicon, can also select amorphous silicon.Silicon oxide compound refers to
The compound that silicon and oxygen are formed, general formula SiOx, wherein 0 x≤2 <；Preferably, 0.5≤x≤1.5.Metal silicide refers to
The solid solution of the compound and/or metal M and silicon of metal M and silicon.The general formula of metal silicide is MSiy, wherein M be selected from Fe,
One or more of Ni, Cr, Mn, Ti and Co, 0.2≤y≤4；Preferably, 0.5≤y≤2.Preferably, the intermediate value of silicon materials
Partial size is 10-300nm.It is highly preferred that the partial size of silicon materials is not more than 200nm.
Wherein, metallic compound refers to the inorganic compound containing metallic element.Preferably, metallic compound is metal
Nonmetallic compound.It is highly preferred that metallic compound is selected from one or more of metal oxide, metal halide.For example, oxygen
Change titanium, aluminium oxide, magnesium chloride, zinc chloride, zinc oxide etc..
Wherein, carbon material is located at the outermost layer of Si-C composite material.Carbon material can be direct with electrolyte to avoid silicon materials
It contacts and bring adverse effect, since the contact performance of carbon material and electrolyte is preferable, so as to improve entire silicon-carbon composite wood
The contact performance of material and electrolyte.
Carbon material can select various carbon materials, such as natural graphite, artificial graphite, carbon black etc..Preferably, carbon material selects
From one or more of carbon nanotube, carbonaceous mesophase spherules, graphene and hard carbon.
Preferably, the phosphorus content of carbon material is greater than 99wt%, can further improve the performance of Si-C composite material in this way.
Preferably, the median particle diameter of nanoparticle is 10-600nm.
Preferably, the median particle diameter of Si-C composite material is 1-100 μm.Si-C composite material is raw in subsequent battery in this way
During production, in ingredient slurry technique, it is possible to reduce agglomeration is easy to bond with collector after baking, improves silicon-carbon
The binding force of composite material and collector.
Above-mentioned Si-C composite material, including two core-shell structures, that is to say, that be additionally provided between silicon materials and carbon material
The middle layer of metallic compound effectively improves the interface between silicon materials and carbon material by the middle layer of metallic compound and connects
Touching property；Keep Si-C composite material more stable in use.Above-mentioned Si-C composite material, due to joined metal compound
Object, improves the electric conductivity of Si-C composite material, and energy density also has promotion.Above-mentioned Si-C composite material, by nucleocapsid knot
The secondary cladding of the nanoparticle of structure, be easier in subsequent ingredient use process and collector bond, it is not easy to reunite or
It drops off, improves Si-C composite material cycle performance.In addition, being directly coated on by setting middle layer to reduce carbon material
The difficulty on silicon materials surface, equipment is simple, is conducive to industrialized production.
The present invention also provides a kind of preparation methods of above-mentioned Si-C composite material.
A kind of preparation method of Si-C composite material, includes the following steps:
S1, metallo-organic compound is dispersed in the first decentralized medium, silicon materials is added and are uniformly mixed, then do by spraying
It is dry to obtain the first presoma；
S2, the first presoma is calcined under atmosphere at 350-1000 DEG C, obtains nanoparticle；
S3, nanoparticle is uniformly mixed with bonding agent, is gradually added carbon material, ultrasonic disperse obtains the second presoma；
S4, the second presoma is sintered at 300-900 DEG C, obtains Si-C composite material.
In S1, metallo-organic compound refers to carbon atom and the compound that metallic atom Direct Bonding is formed, and is bonded shape
Formula can be covalent bond, ionic bond, fit key etc..Metallo-organic compound is the metal of the metallic compound in nanoparticle
Source, metallic compound selects suitable substance in the nanoparticle that metallo-organic compound synthesizes as needed.Preferably, metal
Organic compound is selected from one or more of alkyl metal cpd and metal organic complex.Wherein, metal alkyl chemical combination
Object is preferably selected from trimethyl aluminium, zinc methide etc..Metal organic complex is preferably selected from two luxuriant magnesium, the luxuriant magnesium of diformazan two etc..
In S1, the effect of the first decentralized medium is to be uniformly dispersed silicon materials and metallo-organic compound, thus just
The outside of silicon materials is overlayed in metallo-organic compound.Preferably, the first decentralized medium be organic solvent, such as ether, hexane,
Acetone etc..
In S1, in spray drying process, the slurry that dispersion is formed is by spraying, dry.Preferably, it is spray-dried
Slurry obtained by wet ball grinding.It, can be suitably selected from spray drying according to the diameter for the nanoparticle that spray drying is formed
Slurry in the concentration of particle, the partial size of abrading-ball, the revolving speed of ball mill etc..
In spray drying, to the method that slurry is spray-dried, as long as can be by the spraying droplets of slurry to height
The method for evaporating the first decentralized medium in slurry in the gas of temperature, then be not particularly limited, can be used common spraying
Drying means.Such as desiccant gas is supplied, and into spray-drying installation the temperature in device is remained drying
The state of temperature, from spray nozzles such as rotating disk nozzle, fluid tips to the drop of device internal spraying slurry.
In spray drying, drying temperature is preferably 100~400 DEG C, and particularly preferably 110~300 DEG C, more preferably
120~200 DEG C.The aggregation that spray-dried product can be reduced in this way, keeps the particle of spray-dried product smaller, is more advantageous to nanoparticle
The formation of son.
The size of the drop of slurry when for being sprayed in spray drying process to slurry, selection can make to do by spraying
The diameter of dry object preferably becomes the diameter of the drop of the slurry of 10-600nm.
In S2, the calcination temperature of the first presoma is preferably 450~700 DEG C, and the calcination time of the first presoma is preferred
For 8~15h.
In S2, atmosphere according to the first presoma and can need synthesizing nano-particle to select；If such as nanometer
Containing metal oxide in particle, in the preferred oxygen atmosphere of atmosphere.If containing metal chloride in nanoparticle, in atmosphere
Preferably chlorine atmosphere.
In S3, the effect of binder is that carbon material is adhered to the outside of nanoparticle.Preferably, binder is selected from
Polyvinylpyrrolidone, polyurethane, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polychlorostyrene
One or more of ethylene, the polyvinyl chloride of carboxylation, polyvinyl fluoride polytetrafluoroethylene (PTFE), polyvinylidene fluoride.According to binder
Property it is different, can choose using the second dispersing agent.Likewise, the effect of the second decentralized medium is, by nanoparticle, bonding
Agent and carbon material are uniformly dispersed, consequently facilitating carbon material is coated on the outside of nanoparticle.Preferably, the second dispersion is situated between
Matter is also organic solvent.
In S4, the sintering temperature of the second presoma is preferably 400~600 DEG C, and sintering time is preferably 7~12h.
Above-mentioned preparation method, technique are easy to control, and do not need complicated production equipment, and required equipment is few, and production capacity is big, favorably
In the industrialization large-scale production of Si-C composite material.In addition, above-mentioned preparation method, improves the utilization rate of silicon.
The present invention also provides a kind of negative electrode materials.
A kind of negative electrode material comprising Si-C composite material provided by the present invention.
It is, of course, understood that can also contain other intercalation materials of li ions in negative electrode material, i.e., silicon-carbon of the invention is compound
Material is used in compounding with other intercalation materials of li ions.Other intercalation materials of li ions, such as natural graphite particles, cathode titanium base material etc..
Above-mentioned negative electrode material, due to using Si-C composite material provided by the present invention, to improve the conduction of negative electrode material
Property, energy density also has promotion, and cycle life increases.
The present invention also provides a kind of batteries.
A kind of battery comprising negative electrode material provided by the present invention.
Other components and its connection relationship in battery can use various parts known in those skilled in the art
And its various connection relationships, details are not described herein.
Above-mentioned battery, due to using negative electrode material provided by the present invention, so that its energy density is high, and cycle life
It is long.
Below in conjunction with specific embodiment, the present invention is further elaborated.
Embodiment one
It disperses metallo-organic compound (trimethyl aluminium, 8.5g) in hexane, silicon materials are then added, and (silicon powder, 10 receive
Rice, 200g), stirring 1h obtains slurry.Then slurry is input in spray dryer, before being dried to obtain first at 100 DEG C
Drive body.
First presoma is sent into continuous reactor and calcines 9.5h at 500 DEG C under oxygen atmosphere；Obtain nanoparticle
Son.
It disperses nanoparticle, binder Kynoar PVDF in N-Methyl pyrrolidone NMP, then by carbon material
(carbon nanotube, 10g) is scattered in hexane, stirs 1h.Then the dry 3h at 110 DEG C, obtains the second presoma.
Second presoma is sent into continuous reactor and is sintered 11.5h at 750 DEG C.
Obtained Si-C composite material, is denoted as A1.
Embodiment two
Embodiment two is basically the same as the first embodiment, with embodiment one except that: silicon materials (SiO2, 200 nanometers,
150g), metallo-organic compound (the luxuriant magnesium of dimethyl two, 5.6g), carbon material (graphene, 8g)；Other parts and embodiment one
It is identical.
Obtained Si-C composite material, is denoted as A2.
Embodiment three
Embodiment three is basically the same as the first embodiment, with embodiment one except that: silicon materials (SiO2, 300 nanometers,
250g), metallo-organic compound (ferrocene, 9.5g), carbon material (carbonaceous mesophase spherules, 12g)；Other parts and embodiment one
It is identical.
Obtained Si-C composite material, is denoted as A3.
Performance test
Partial size test:
Partial size test is carried out to Si-C composite material A1-A3 using 3000 particle instrument of Malvern Mastersizer.It surveys
Test result is shown in Table 1.
Electrochemical property test:
It is tested using capacity and cycle performance of the simulated battery to Si-C composite material A1-A3.
Simulated battery is assembled in the H full of high-purity argon gas2O and O2Content is respectively less than in the glove box of 0.1ppm and carries out.It adopts
It is simulated battery with CR2025 type button cell, using lithium piece (purity > 99.9%) as to electrode, polyethylene monolayer film
It (ENTEK) is diaphragm, electrolyte is 1mol/L LiPF6Ethylene carbonate (EC)/dimethyl carbonate (DMC) mixed solution.
Constant current charge-discharge survey is carried out to the simulated battery assembled using new prestige battery test system (specification 5V, 2mA)
Examination.Electrochemistry loop test current density is 100mAg-1, it is 100~4000mA/g, electricity that high rate capability, which tests current density,
Pressure range is 0.02~1.5V, and test temperature is 25 DEG C.Test result is shown in Table 1.
Table 1
As can be seen from the above table, Si-C composite material provided by the present invention has excellent cycle performance, and specific capacity
It is higher.
Claims (2)
1. a kind of preparation method of Si-C composite material, which comprises the steps of:
Metallo-organic compound is dispersed in the first decentralized medium, silicon materials are added and are uniformly mixed, then spray drying obtains
First presoma；The silicon materials are one or more of silicon, Si oxide and metal silicide；
First presoma is calcined under atmosphere at 350-1000 DEG C, so that metallo-organic compound reaction life
At metallic compound, nanoparticle is obtained；The metallic compound is selected from titanium oxide, aluminium oxide, zinc oxide；
The nanoparticle is uniformly mixed with bonding agent, is gradually added carbon material, ultrasonic disperse obtains the second presoma；
Second presoma is sintered at 300-900 DEG C, obtains Si-C composite material.
2. preparation method according to claim 1, which is characterized in that the drying temperature of the spray drying is 100~400
℃。
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| CN107623104A (en) * | 2017-09-25 | 2018-01-23 | 常州市宇科不绣钢有限公司 | A kind of structure silicon-based negative material of multi-buffer and preparation method thereof |
| CN109841803B (en) * | 2017-11-28 | 2021-12-07 | 宁德时代新能源科技股份有限公司 | Silicon-carbon composite material, preparation method thereof and secondary battery containing material |
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| US10608241B2 (en) * | 2018-04-17 | 2020-03-31 | GM Global Technology Operations LLC | Methods of preparing lithium metal anodes |
| CN108807927B (en) * | 2018-06-25 | 2021-10-15 | 南通百川新材料有限公司 | Silicon-carbon composite negative electrode material and preparation method thereof |
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| CN109841823A (en) * | 2019-03-19 | 2019-06-04 | 宁德新能源科技有限公司 | Negative electrode material and the electrochemical appliance and electronic device for using it |
| CN110416515B (en) * | 2019-07-24 | 2022-03-04 | 东莞东阳光科研发有限公司 | Lithium ion battery, negative electrode material for lithium ion battery and preparation method thereof |
| CN111146421B (en) * | 2019-12-26 | 2022-03-18 | 宁德新能源科技有限公司 | Negative electrode material, and electrochemical device and electronic device comprising same |
| CN113036137A (en) * | 2021-03-05 | 2021-06-25 | 昆山宝创新能源科技有限公司 | Lithium ion battery cathode material and preparation method and application thereof |
| CN115863572A (en) * | 2022-12-05 | 2023-03-28 | 浙江新安化工集团股份有限公司 | A kind of silicon carbon composite material, battery negative electrode and preparation method |
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