CN105655555B - A kind of Si-C composite material, preparation method and applications - Google Patents
A kind of Si-C composite material, preparation method and applications Download PDFInfo
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- CN105655555B CN105655555B CN201610022473.0A CN201610022473A CN105655555B CN 105655555 B CN105655555 B CN 105655555B CN 201610022473 A CN201610022473 A CN 201610022473A CN 105655555 B CN105655555 B CN 105655555B
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 30
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 26
- 239000010439 graphite Substances 0.000 claims abstract description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229910021426 porous silicon Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 23
- 229910021471 metal-silicon alloy Inorganic materials 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 20
- 238000005554 pickling Methods 0.000 abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 25
- 229910052710 silicon Inorganic materials 0.000 description 25
- 239000010703 silicon Substances 0.000 description 25
- 238000002156 mixing Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 DOPA amine salt Chemical class 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229960004502 levodopa Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 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
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of silicon-carbon preparation method, including step (1)：Carbon is compound：Silicon metal alloy compositions with graphite are mixed, using two pickling, porous Si-C composite material is made；Step (2)：Carbon coating：Porous Si-C composite material made from step (1) is mixed with organic carbon source, thermally treated obtained Si-C composite material.The invention also includes using Si-C composite material and its application in lithium battery is prepared made from above-mentioned preparation method.Present invention process is simple, abundant raw materials, cheap, is easy to scale preparation, is a kind of ideal preparation method.More excellent chemical property is shown as lithium ion battery negative material.
Description
Technical field
The present invention relates to technical field of lithium ion battery negative, and in particular to a kind of Si-C composite material, preparation side
Method and its application.
Background technology
Power battery is the heart of New-energy electric vehicle, is the key that New-energy electric vehicle industry development, however mesh
The energy density of the preceding lithium ion battery being widely used on mobile electronic product, security performance, high rate performance etc. are still
Requirement of the people on electric vehicle cannot be met, become the bottleneck that electric vehicle is hindered to be widely applied.Lithium-ion electric
Pond is made of positive and negative pole material, diaphragm and electrolyte, and wherein electrode material is the core of battery, decides battery electrochemical
Lithium performance is stored up, therefore the performance of negative electrode material directly affects the performance of lithium ion battery.It is main commercialized at present
Lithium ion battery negative material based on graphite cathode material, actual specific capacity already close to 372mAh/g theoretical value,
Relatively low theoretical capacity constrains the raising of the energy density of lithium ion battery, thus further research and development with height ratio capacity, excellent
Different cyclical stability and the negative material of safety are extremely urgent.
Silicon has the theoretical specific capacity of 4200mAh/g as lithium ion battery negative material, far above the capacity of graphite, makees
The energy density of raising battery that can be by a relatively large margin for negative material, and the discharge platform of silicon is slightly above graphite cathode material
Material is not likely to produce analysis lithium, and security performance is better than graphite, and in addition silicon capacity enriches, cheap, therefore is most promising at present
Lithium ion battery negative material.But silicon also has the shortcomings that apparent as lithium ion battery negative material, if silicon is as semiconductor
Material, its own conductivity are relatively low；In charge and discharge process, with the insertion and abjection of lithium ion, silicon materials volume change is larger,
Lead to material dusting, come off, eventually lead to and be detached from collector, cyclical stability is poor.
The chemical property of silica-base material is improved the methods of generally use doping, nanosizing to solve the above-mentioned problems.It is public
The number of opening discloses a kind of method that hollow Nano silicon ball is prepared using metallothermic reduction for CN104332621A Chinese patent literatures,
Silica nanosphere is restored using active metal, controlling the content of active metal makes it only restore silica nanosphere table
Face, and kernel is still silica, then using hydrochloric acid and hydrofluoric acid removal metal oxide and silica, is obtained hollow
Nano silicon spheres.Publication No. CN101179126B Chinese patent literatures disclose it is a kind of for lithium secondary battery include silicon based on
The electrode material of ingredient is wanted, which includes atomic ratio of at least one of boron, aluminium, gallium, the antimony and phosphorus element relative to silicon
1 × 10- 5To 1 × 10- 1In the range of dopant dose silicon is doped.These methods improve silicon substrate to a certain extent
The chemical property of material, however these preparation methods are more complicated, cost is higher, is not easy scale preparation, and chemical property
Need to be further improved.
Invention content
In order to obtain the Si-C composite material having compared with excellent electrochemical performance, the present invention provides a kind of silicon-carbon composite wood
Material, preparation method and applications.
A kind of preparation method of Si-C composite material, includes the following steps：
Step (1)：Carbon is compound：Silicon metal alloy compositions with graphite are mixed, using two pickling, porous silicon-carbon is made
Composite material；
Step (2)：Carbon coating：Porous Si-C composite material made from step (1) is mixed with organic carbon source, it is thermally treated
Si-C composite material is made.
Porous silicon (porous silicon-carbon composite wood is made by carrying out two acid corrosions to silicon metal alloy compositions in the present invention
Material), and by compound and carbon coating prepares Si-C composite material with carbon.In Si-C composite material, carbon and micropore there are effective
Ground has buffered the volume expansion of silicon, enhances the conduction and chemical property of silicon.The method of the present invention is simple for process, and raw material are rich
It is rich, cheap, be conducive to industry's enlarging production.
In step (1), silicon metal alloy compositions are clayed into power first with ball-milling method, are then mixed to prepare stone with graphite
Ink/silicon metal alloy composite material, wherein, the rotating speed of ball milling is 300~1000 revs/min, Ball-milling Time 2~48 hours；Silicon gold
The mixing quality ratio for belonging to alloy material and graphite is 0.2-5:1.
The present invention prepares graphite/silicon metal alloy composite material (powder) using high-energy ball milling method.Improve the mixing of raw material
Effect, while be conducive to the acid corrosion of subsequent step.
Preferably, in silicon metal alloy compositions, the content of silicon is 20~95wt%, other compositions be selected from iron, aluminium,
It is one or more in copper, chromium, nickel, tin, manganese, calcium, magnesium, cobalt, titanium and germanium.
Above-mentioned metallic element can be compounded to form stable alloy or partially-alloyed compound with silicon, have good metal
Ductility improves the processing performance of silicon metal alloy compositions.
The content of the silicon is silicon relative to the weight percent of silicon metal alloy compositions.It is further preferred that silicon is golden
Belong in alloy material, in addition to silicon, other are iron and/or aluminium.Acid is good to the corrosive effect of the eka-silicon metal alloy compositions, favorably
In the good porous Si-C composite material of processability.
Preferably, it is taken out by 100 mesh standard sieves of powder of graphite made from ball-milling method/silicon metal alloy composite material
Inspection, 100% passes through.
Silicon metal alloy and graphite are mixed in the ratio, by ball-milling method that Si metal alloys, C progress is compound, by carbon
Material is introduced into silicon metal alloy compositions.Graphite obtained/silicon metal alloy composite material removes stone using two acid elutions
Metallic element and Si oxide in ink/silicon metal alloy composite material.
Preferably, acid is one or more, the molar concentration in sulfuric acid, nitric acid, hydrochloric acid used by first of pickling
For 0.1~10mol/L.Further preferably, in first of pickling, using the aqueous solution of above-mentioned acid.
Graphite/silicon metal alloy composite material is immersed in above-mentioned acid solution, and is passed through stirring and improved sour and metal connect
It has a sudden inspiration meeting, preferably, mixing time is 10-20h, then filters and be washed with deionized repeatedly, be dried, remove stone
Metallic element in ink/silicon metal alloy composite material.
After first of pickling, then second pickling is carried out, preferably, acid is hydrofluoric acid used by second pickling,
Mass percent is 1%~20%.
Further preferably, the hydrofluoric acid that second pickling uses is aqueous solution.
Second pickling mode refers to first of pickling.
After second pickling, the multiple washing of filtered, deionized water and alcohol is dried to obtain porous silicon-carbon composite wood
Material.Porous Si-C composite material carries out the carbon coating of step (2) again.
Preferably, in step (2), the organic carbon source is selected from glucose, sucrose, citric acid, DOPA amine salt, first
It is one or more in aldehyde, phenolic resin, xylenol, polyacrylonitrile, polypyrrole, polyaniline and polythiophene.
In order to improve covered effect of the organic carbon source to porous Si-C composite material, can by above-mentioned organic carbon source using water or
Other solvents are dissolved；The effect and efficiency of porous Si-C composite material are filled to further improve organic carbon source, as excellent
It selects, in step (2), porous Si-C composite material is mixed with the solution of organic carbon source under positive pressure or negative pressure atmosphere.After mixing
Through heating up, solvent evaporated obtains silicon/graphite/organic carbon source mixing material.
Preferably, 0.05-0.5 times adding weight and being silicon weight in silicon metal alloy compositions of carbon in organic carbon source.
Further preferably, 0.1 times adding weight and being silicon weight in silicon metal alloy compositions of carbon in organic carbon source.
Silicon/graphite/organic carbon source mixing material is placed in tube furnace, hot place is carried out under the atmosphere of inert gas
It manages, oxygen, preferably nitrogen, argon gas or helium is not contained in the inert gas.
Preferably, the heat treatment temperature is 400~1200 DEG C, heat treatment time is 1~8 hour.
After the completion of heat treatment, washed using deionized water or absolute ethyl alcohol；Separation of solid and liquid (is such as filtered or is centrifuged)；It collects
Solid is vacuum dried, and the Si-C composite material is made.Preferably, vacuum drying temperature is 60~120 DEG C, drying time
It is 2~12 hours.
Preferably, the content of silicon is 5%~50wt% in the Si-C composite material finally prepared.
The invention also includes using Si-C composite material made from above-mentioned preparation method.
The invention also includes using application of the above-mentioned Si-C composite material as lithium ion battery negative material.
Negative electrode of lithium ion battery electrode, the electrode material are prepared using existing negative electrode of lithium ion battery electrode fabrication
Material is made of Si-C composite material (active material), conductive agent and binding agent.The conductive agent that uses, binding agent for it is existing often
Advise material.Such as, conductive carbon black (super-p), Kynoar (PVDF).
Such as, the Si-C composite material (active material) the method for the present invention being prepared：Conductive agent (conductive carbon black,
super-p)：Binding agent (Kynoar, PVDF), than mixing, adds a certain amount of N-Methyl pyrrolidone by certain mass
(NMP) solvent is uniformly mixed obtained slurry.Slurry is coated uniformly on copper foil using coating machine, is pressed after vacuum drying
Piece, slice, drying obtain the negative electrode of lithium ion battery electrode containing Si-C composite material of the present invention.
The invention also includes a kind of lithium ion battery, the Si-C composite material being prepared containing the above method.By described in
Si-C composite material by prior art preparation into electrode activity thing material (negative electrode of lithium ion battery electrode), then by existing
Technology is assembled into lithium ion.
The method of the present invention is simple for process, of low cost, can be mass-produced.The carbon silicon accounting of Si-C composite material obtained
Rationally, aperture is reasonable, has and preferably bears that volume adaptability to changes, large specific surface area, the depth of lithium ion deintercalation be small, ion expands
Dissipate that path is short, reversible capacity is high, coulombic efficiency is high, the advantages that having extended cycle life.
Description of the drawings
The XRD of Si-C composite material prepared by embodiment 1 in Fig. 1 present invention；
The XRD of Si-C composite material prepared by embodiment 2 in Fig. 2 present invention；
The silicon-carbon cathode material first charge-discharge curve that in Fig. 3 present invention prepared by embodiment 1；
The silicon-carbon cathode material first charge-discharge curve that in Fig. 4 present invention prepared by embodiment 2.
Specific embodiment
Following embodiment is implemented by aforesaid operations method：
Embodiment 1：
1st, the preparation of Si-C composite material
It is little particle to be crushed the Antaciron that silicone content is 65% using planetary ball mill, wherein, ball material mass ratio
About 5：1, rotating speed is 400 revs/min, and Ball-milling Time obtains Antaciron powder after 4 hours.Graphite 13g is weighed, silicone content is
65% Antaciron 10g and 20ml alcohol obtains graphite/silicon in 8 hours using ball mill with 450 revs/min of rotating speed ball milling
Ferroalloy composite material.Obtained graphite/Antaciron composite material is placed in beaker, adding in excessive molar concentration is
The sulfuric acid of 1mol/L, at normal temperatures using the removal ferrous metal element of magnetic stirrer 24 hours, reaction product using go from
Sub- water cleans 3 times；Then by product addition excess containing Si oxide is removed in the hydrofluoric acid solution that mass fraction is 5%, often
The lower magnetic agitation of temperature 12 hours, reaction product are respectively washed that obtain porous silicon/graphite 3 times compound using deionized water and hydrofluoric acid
Material.The aqueous solution (sucrose 5g) of the sucrose containing 5g is added to obtained porous silicon/graphite composite material, in negative pressure ring under room temperature
Magnetic agitation 3 hours is immersed in porous silicon gap in favor of sucrose solution in border, then at 90 DEG C magnetic agitation to aqueous solution
All it is evaporated (mixture, silicon/graphite/organic carbon source mixing material).Mixture is placed in tube furnace, in nitrogen environment with
The heating rate of 5 DEG C/min is heated to 700 DEG C, keeps the temperature 4 hours, naturally cools to room temperature；Distinguished again with deionized water and alcohol
Washing 3 times obtains Si-C composite material in dry 5 hours at 100 DEG C in vacuum drying oven.
2nd, the preparation of Si-C composite material cathode
Sample will be prepared by Si-C composite material (active material)：Conductive agent (conductive carbon black, super-p)：
Binding agent (Kynoar, PVDF)=8:1:1 mass ratio mixing, it is molten to add a certain amount of N-Methyl pyrrolidone (NMP)
Agent is uniformly mixed using magnetic agitation.Slurry is coated uniformly on copper foil using coating machine, in vacuum drying oven 100 DEG C it is true
Dry 10 hours of sky, after by tabletting, be sliced, it is dry, weigh etc. and to obtain pole piece, battery to be assembled.
3rd, the preparation and test of lithium ion battery
Dry pole piece is put into assembled battery in the glove box containing high-purity argon gas, in the button cell of assembling, just extremely
Si-C composite material, cathode are lithium piece, and diaphragm is polypropylene screen, electrolyte for be 1mol/L containing lithium salts lithium hexafluoro phosphate
(LiPF6), solvent is that volume ratio is 1：1：1 ethylene carbonate (EC)：Dimethyl carbonate (DMC)：Methyl ethyl carbonate (EMC).
Charge-discharge test, voltage tester ranging from 0.01~1.5V are carried out to lithium ion battery using blue electrical measurement test system constant current.
Embodiment 2
It is prepared according to preparation method same as Example 1, the difference is that raw material utilize the ferrosilicon that silicone content is 75%
It is prepared by alloy.
Material object prepared by embodiment is mutually characterized using polycrystal X ray diffractometer.
Fig. 1 and Fig. 2 is respectively a kind of XRD of Si-C composite material that embodiment 1 is prepared with embodiment 2 in the present invention,
In Fig. 1 and Fig. 2 in addition to crystalline silicon (2 θ=28.5,47.4,56.2,69.3,76.5) and carbon (2 θ=26.5,42.4,44.5,
54.5) other apparent impurity peaks are had no outside diffraction maximum, illustrate that the higher silicon-carbon composite wood of purity has been prepared in this method
Material.
Fig. 3 and Fig. 4 is embodiment 1 in the present invention and a kind of silicon-carbon cathode material of the preparation of embodiment 2 with the electricity of 50mA/g
The first charge-discharge curve that current density is tested in 0.01~1.5V voltage ranges.As can be seen from the figure its specific volume that discharges for the first time
Amount can reach 970mAh/g, and specific discharge capacity and coulombic efficiency are higher, and charge and discharge platform and typical silicon-carbon composite wood
Expect that charging and discharging curve is consistent.
The present invention provides a kind of method for preparing Si-C composite material simple for process, and it is abundant raw materials, cheap,
It is easy to scale preparation, is a kind of ideal preparation method.More excellent electrochemistry is shown as lithium ion battery negative material
Performance.
The explanation of book according to the above description, those skilled in the art in the invention can also carry out the above embodiment
Appropriate modifications and changes, therefore, all any modification, supplement or similar fashions made in the spirit of the present invention are replaced
It in generation etc., should all be included in the protection scope of the present invention.
Claims (3)
1. a kind of preparation method of Si-C composite material, which is characterized in that include the following steps：
It is little particle to be crushed the Antaciron that silicone content is 65% using planetary ball mill, wherein, ball material mass ratio is about
5：1, rotating speed is 400 revs/min, and Ball-milling Time obtains Antaciron powder after 4 hours；Graphite 13g is weighed, silicone content is 65%
Antaciron powder 10g and 20ml alcohol obtains graphite/ferrosilicon in 8 hours using ball mill with 450 revs/min of rotating speed ball milling
Alloy composite materials；
Obtained graphite/Antaciron composite material is placed in beaker, adds in the sulfuric acid that excessive molar concentration is 1mol/L,
At normal temperatures using 24 hours removal ferrous metal elements of magnetic stirrer, reaction product is cleaned 3 times using deionized water；So
Product is added in excessive containing removing Si oxide in the hydrofluoric acid solution that mass fraction is 5%, magnetic agitation 12 under room temperature afterwards
Hour, reaction product is respectively washed 3 times using deionized water and hydrofluoric acid and obtains porous silicon/graphite composite material；
Be added to the aqueous solution of the sucrose containing 5g to obtained porous silicon/graphite composite material, under room temperature in subnormal ambient magnetic force
3 hours are stirred so that sucrose solution is immersed in porous silicon gap, then magnetic agitation is all evaporated to aqueous solution at 90 DEG C；
Mixture is placed in tube furnace, is heated to 700 DEG C in nitrogen environment with the heating rate of 5 DEG C/min, heat preservation 4 is small
When, naturally cool to room temperature；It is washed respectively 3 times with deionized water and alcohol again, it is 5 hours dry at 100 DEG C in vacuum drying oven
Obtain Si-C composite material.
2. using Si-C composite material made from preparation method described in claim 1.
3. application of the Si-C composite material as claimed in claim 2 as lithium ion battery negative material.
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| CN106450192A (en) * | 2016-10-14 | 2017-02-22 | 浙江天能能源科技股份有限公司 | Silicon/carbon composite material for lithium ion battery and preparation method and application thereof |
| TWI615191B (en) * | 2016-10-17 | 2018-02-21 | Method for manufacturing porous substrate | |
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| CN106356520A (en) * | 2016-11-22 | 2017-01-25 | 天津赫维科技有限公司 | Preparation method of polymer composite silicon carbon negative electrode material |
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| CN110416515B (en) * | 2019-07-24 | 2022-03-04 | 东莞东阳光科研发有限公司 | Lithium ion battery, lithium ion battery cathode material and preparation method |
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| CN111490242B (en) * | 2020-04-27 | 2022-03-04 | 吉林唯圣能源科技开发有限公司 | Production method of silicon-carbon material |
| CN112599778B (en) * | 2020-12-15 | 2022-04-01 | 广东凯金新能源科技股份有限公司 | Silicon-carbon-based negative electrode material and preparation method thereof |
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