CN109216686A - A kind of lithium ion battery silicon-carbon composite material and preparation method - Google Patents
A kind of lithium ion battery silicon-carbon composite material and preparation method Download PDFInfo
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- CN109216686A CN109216686A CN201811182489.3A CN201811182489A CN109216686A CN 109216686 A CN109216686 A CN 109216686A CN 201811182489 A CN201811182489 A CN 201811182489A CN 109216686 A CN109216686 A CN 109216686A
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- Prior art keywords
- carbon
- silicon
- composite material
- lithium ion
- ion battery
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Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 31
- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 25
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 239000011246 composite particle Substances 0.000 claims abstract description 14
- 229910021332 silicide Inorganic materials 0.000 claims abstract description 10
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 238000005118 spray pyrolysis Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000000889 atomisation Methods 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 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 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 150000003377 silicon compounds Chemical class 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052710 silicon Inorganic materials 0.000 abstract description 23
- 239000010703 silicon Substances 0.000 abstract description 21
- 239000002210 silicon-based material Substances 0.000 abstract description 8
- 238000005245 sintering Methods 0.000 abstract description 4
- 239000007769 metal material Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 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 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229910021426 porous silicon Inorganic materials 0.000 description 4
- 229910021487 silica fume Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910017758 Cu-Si Inorganic materials 0.000 description 2
- 229910017931 Cu—Si Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 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 description 2
- PNUGDRJNKILROY-UHFFFAOYSA-N [C].[Si].[Li] Chemical compound [C].[Si].[Li] PNUGDRJNKILROY-UHFFFAOYSA-N 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000010410 dusting Methods 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000005720 sucrose Substances 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
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- -1 conductivity is low Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229920005546 furfural resin Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—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
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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)
- 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 lithium ion battery silicon-carbon composite material and preparation methods, belong to technical field of lithium ion.The composite material includes: the composite particles comprising nano-silicon, carbon material, nanometer inert metal or metal silicide, and it is coated on the carbon-coating on the composite particles surface, the composite material is the porous secondary structure with micron-scale, it is mixed by nano-silicon, carbon material, metal salt and organic carbon source solution, is made through spray pyrolysis and sintering carbonization.The composite material can give full play of the synergistic effect of silicon, carbon and metal material, and the electrochemistry capacitance of silicon materials is high, and carbon material increases electric conductivity, and inert metal or metal silicide can further increase electric conductivity and reduce volume change；Porous secondary structure effectively improves tap density and has adapted to the volume expansion of silicon to mitigate mechanical stress.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of lithium ion battery silicon-carbon composite material and its system
Preparation Method.
Background technique
Since with good charge and discharge cycles stability, graphite-like carbon negative pole material is still widely used in business lithium
In ion battery, but its theoretical capacity is very limited (372mAh/g).With the development of consumer electronics and electric car, people
Higher and higher to the energy density requirement of lithium ion battery, there is an urgent need to develop the negative electrode of lithium ion battery material of new high capacity for this
Material.In all kinds of novel storage lithium titanate cathode materials, silicon possesses highest theoretical capacity (4212mAh/g)；Silicon based anode material simultaneously
Also have many advantages, such as that from a wealth of sources, cheap, intercalation potential is low, there is no toxicity.Therefore silicon, which is considered next-generation, most business
Change the negative electrode material of application prospect.
However, there are serious volume expansion and contractions in charge and discharge process for silicon, this can make the continuous dusting of silicon, and then lead
It causes gradually to disengage and lose the electrical contact with collector between electrode active material and collector, so that electrode cycle performance is rapid
Decline.The destruction of simultaneous electrode structure, the silicon face newly exposed can be formed constantly during with electrolyte contacts
New solid electrolyte film (SEI), to be difficult to form stable SEI, this will lead to efficiency for charge-discharge reduction, and capacity attenuation adds
It is acute.In addition, silicon itself is semiconductor material, conductivity is low, and conductive agent need to be added to improve the electronic conductance of electrode.For effectively
Silicon materials are applied in lithium ion battery, need to improve its first charge-discharge coulombic efficiency and electrochemical cycle stability.
Currently, acquisition capacity is higher, and cyclicity is more stable in order to reduce volume expansion of silicon during lithium ion deintercalation
Silicon based anode material, research work both domestic and external is concentrated mainly on the nanosizing of silicon materials and prepared based on nano-silicon each
The silicon based composite material of kind pattern, structure.
Porous silicon/carbon composite and application are prepared by raw material of diatomite as CN102208636A discloses one kind, is had
Body discloses: preparing porous silicon by silicon source of diatomite first, then compound to be prepared for porous silicon/charcoal multiple porous silicon and carbon material
Condensation material is to reduce preparation cost and alleviate the bulk effect of silicon.
Nian Liu et al. reports a kind of Si@C of yolk-eggshell structure.Si is completely coated on it by very thin carbon-coating
In, intermediate void layer allows Si Particle free to expand without destroying carbon-coating.At 0.1C, Si@C discharge capacity is reachable
2800mAh/g；After 1000 circulations, capacity keeps 74% (Nian Liu et al.A yolk-shell designfor
stabilized and scalable Li-ion battery alloy anodes[J].Nano Lett,2012,12(6):
3315)。
Sujong Chae etc. is prepared for Fe-Cu-Si trielement composite material using spray pyrolysis, and reversible capacity reaches
1287mAh/g, coulombic efficiency is up to 91% (Sujong Chae al.Micron-sized Fe-Cu-Si ternary
composite anodes for high energy Li-ion batteries[J].Energy Environ.Sci.,
2016,9,1251-1257)。
CN102790204A discloses a kind of preparation method of silicon carbon lithium ion battery cathode, specific open: first
Polymer Solution and silicon powder, graphite are mixed to get mixed liquor；Then freeze-drying removes solvent, and final high temperature sintering obtains
Silicon carbon lithium ion battery cathode.
CN104332594A discloses a kind of silicon based anode material and its preparation method and application, the silicon based anode material packet
Graphene, silicon nanoparticle and nano-metal particle with layer structure are included, silicon nanoparticle and nano-metal particle are embedding
In the layer structure of the graphene.
Although these silicon based anode materials alleviate the volume occurred when the embedding de- lithium of silicon materials itself to a certain extent
Expansion and blockage effect, but since it is with biggish specific surface area, it can disappear in the contact in cyclic process and with electrolyte
A large amount of lithium ion is consumed, so as to cause the increase of side reaction and the reduction of coulombic efficiency, thereby reduces cycle performance and capacity
Conservation rate；On the other hand, the composite materials such as these single silico-carbo, silicon-metals, which can't be fully solved existing for silicon materials, asks
Topic or Volumetric expansion can not be solved thoroughly or conductivity is also wait improve or preparation cost is high, to influence it
Practical application.
Summary of the invention
The purpose of the present invention is to provide it is a kind of it is low in cost, specific capacity is high, Volumetric expansion is low, conductivity is high, with
The good Si-C composite material of battery electrolyte compatibility.
To achieve the above object, the present invention provides a kind of lithium ion battery silicon-carbon composite material, which includes:
Composite particles comprising nano-silicon, carbon material, nanometer inert metal or metal silicide, and it is coated on the composite particles table
The carbon-coating in face；The lithium ion battery silicon-carbon composite material is the porous secondary structure of micron-scale.
Composite material provided by the invention is the porous secondary structure with micron-scale, wherein being embedded in many nano-scales
Silicon, carbon, inert metal or metal silicide grain, while outer layer uniformly coats pyrolytic carbon can give full play of silicon, carbon and
The synergistic effect of metal material；And porous secondary structure effectively increases tap density and adapts to the volume expansion of silicon to mitigate
Mechanical stress.
Preferably, the partial size of the nano-silicon is 50-900nm, the partial size of carbon material is 10nm-100 μm, nanometer inertia
The partial size of metal or metal silicide is 10-100nm, carbon layers having thicknesses 10-50nm.
Preferably, by percentage to the quality, in the lithium ion battery silicon-carbon composite material nano-silicon be 10-60%,
Carbon material is 30-80%, nanometer inert metal or metal silicide are 5-20%, carbon-coating 5-20%.By adjusting silicon, carbon materials
Material and inactive metal sill, can control volume expansion, coulombic efficiency and the specific capacity of composite material, to regulate and control electrode
The capacity and cycle life of material.
Preferably, the pore size of the lithium ion battery silicon-carbon composite material is 30-l00nm, porosity 10-
100%.Hole is conducive to electrolyte and infiltrates and accelerate ionic conduction.
The present invention also provides a kind of method for preparing the lithium ion battery silicon-carbon composite material, the method includes
Following steps:
(1) nano-silicon, carbon material, metal salt and organic carbon source solution are mixed, obtains precursor solution；
(2) precursor solution is spray-dried, obtains Si-C-M composite material first product；
(3) it disperses Si-C-M composite material first product in organic carbon source solution, after removing solvent again in an inert atmosphere
Sintering carbonization, is made the lithium ion battery silicon-carbon composite material.
Preferably, after the nano-silicon is by silica material and metallic reducing agent mixing and ball milling, then be soaked in acid
Impurity is removed, separation is made.Silica material causes reduction reaction in Mechanical Milling Process, obtains silicon nanoparticle.More
To be preferred, the partial size of nano-silicon obtained is 50-200nm.
The present invention prepares nano-silicon using the method for mechanical ball mill from the silica material of low cost, greatly saves
Production cost is saved, preferably, silica material and metallic reducing agent 1:2 ball milling on ball mill in molar ratio.
Preferably, the silica material be diatomite, mesoporous silicon oxide, porous molecular screen, quartz or
Artificial synthesized silica；The metallic reducing agent is magnesium, calcium, lithium, sodium or potassium metal powder.The acid be hydrochloric acid or
Sulfuric acid.
Preferably, the carbon material is natural graphite, artificial graphite, expanded graphite, graphene, carbon black, active carbon
At least one of with carbon nanotube.The partial size of the carbon material is 10nm-100 μm.
Preferably, the metal salt is at least one of iron, copper, zinc, manganese, cobalt, nickel salt.More preferably, described
Metal salt is ferric nitrate, copper nitrate or manganese nitrate.
More preferably, nano-silicon: carbon material: the mass ratio of metal salt is 1:1:0.5 in step (1).
Preferably, in step (1) and (3), the organic carbon source be sucrose, glucose, fructose, citric acid, starch,
Cellulose, pitch, coal tar, butadiene-styrene rubber, polyvinyl alcohol, carboxymethyl cellulose, polyvinyl chloride, polystyrene, polyacrylonitrile,
At least one of furfural resin, phenolic resin, epoxy resin.
The solvent that the organic carbon source uses can for water, ethyl alcohol, butanol, methanol, acetone, ethyl acetate, tetrahydrofuran,
N-Methyl pyrrolidone, pyrrole instigate, chloroform or hexamethylene.
More preferably, the organic carbon source solution is glucose solution, aqueous citric acid solution or sugarcane in step (1)
Sugar aqueous solution；In step (3), the organic carbon source solution be pitch-tetrahydrofuran solution, polyacrylonitrile-ethanol solution or
Epoxy resin-ethanol solution.
In step (2), precursor solution is atomized using spray drying process, as solvent volatilization and presoma are decomposed
Form microcellular structure.The present invention is by atomization so that nano-silicon, carbon material, metallic are evenly distributed on the porous of carbon source cladding
In microballoon.Preferably, being brought by carrier gas spraying hot in situ in 200-900 DEG C of progress in reacting furnace after precursor solution atomization
Solution.
In step (3), further carbon source carbonization package facilitates the structural stability and electric conductivity that increase composite material.
The carbon-coating is agraphitic carbon.The temperature of the sintering carbonization is 600-1200 DEG C.In the step, it can be adjusted by carbon source cladding
Control the hole and structure of composite material.Preferably, the mass ratio of Si-C-M composite material first product and organic carbon source is 4:1.
In heating carbonisation, metal salt generates inert metal or metal silicide grain, further increases conductive
Property and reduce volume change, to reduce side effect, improve coulombic efficiency.
It is that the present invention has the utility model has the advantages that
(1) the porous second level knot with micron-scale that Si-C composite material provided by the invention is made of nanocrystal
Structure, the material can give full play of the synergistic effect of silicon, carbon and metal material, and the electrochemistry capacitance of silicon materials is high, carbon material
Increase electric conductivity, inert metal or metal silicide can further increase electric conductivity and reduce volume change；Porous second level knot
Structure effectively improves tap density and has adapted to the volume expansion of silicon to mitigate mechanical stress.
(2) from inexpensive silica material nano-silicon is first made using the method for mechanical ball mill, then in the present invention
Again by mixing with carbon material, metal salt and organic carbon source, spray pyrolysis, and the method for pyrolysis carbonization are prepared by nanocrystal
The micron Si-C composite material of composition, this method have many advantages, such as low in cost, and operating procedure is simple.
Detailed description of the invention
Fig. 1 is the battery first charge-discharge curve graph based on Si-C composite material made from embodiment 1；
Fig. 2 is the circulating battery curve graph based on Si-C composite material made from embodiment 1.
Specific embodiment
Below by specific embodiment, the present invention is further elaborated, it is noted that following instance is merely to illustrate
The present invention rather than limit the scope of the invention.In addition, it should also be understood that, those skilled in the art according to above-mentioned invention do by content
Nonessential improved adjustment out, should belong to protection scope of the present invention.
Embodiment 1
Firstly, being in molar ratio 1:2 ball milling on ball mill by silica material diatomite and magnesium powder, then by ball milling
Mixture afterwards is immersed in hydrochloric acid, then uses deionized water, the washing such as ethyl alcohol, and separation obtains nano-silicon after drying.
Then the nano silica fume particle for being 50nm by the partial size of 0.2g synthesis, the graphite of 0.2g, the ferric nitrate difference of 0.1g
It is added to alone in the aqueous solution for the glucose that concentration is 0.2M, ultrasonic disperse 30min forms the suspension or solution hooked；
Then three kinds of solution are put together and is continuesd to mix uniformly.
Secondly, above-mentioned resulting mixed liquor to be carried out using spray drying process at 200 DEG C to spraying cracking, it is multiple that Si-C-M is made
Condensation material first product；
Then, the above-mentioned Si-C composite material of 0.2g and 0.05g pitch are used to ultrasonic disperse 90min, shape in tetrahydrofuran
It at uniform suspension, is then dried in vacuo at 80 DEG C, obtains the mixture of Si-C-M composite particles and pitch.
Finally the mixture of Si-C-M composite particles and pitch after drying is put into tube furnace, under protection of argon gas,
Roasting charing is carried out at 900 DEG C to get final Si-C-M composite material.
Embodiment 2
Firstly, being in molar ratio 1:2 ball milling on ball mill by silica material porous molecular screen and lithium block, then will
Mixture after ball milling is immersed in sulfuric acid, then uses deionized water, the washing such as ethyl alcohol, and separation obtains nano-silicon after drying.
Then the nano silica fume particle for being 100nm by the partial size of 0.2g synthesis, the graphite of 0.2g, the copper nitrate difference of 0.1g
It is added to alone in the aqueous solution for the citric acid that concentration is 0.2M, ultrasonic disperse 30min forms the suspension or solution hooked；
Then three kinds of solution are put together and is continuesd to mix uniformly.
Secondly, above-mentioned resulting mixed liquor to be carried out using spray drying process at 500 DEG C to spraying cracking, it is multiple that Si-C-M is made
Condensation material first product；
Then, the above-mentioned Si-C-M composite material first product of 0.2g and 0.05g polyacrylonitrile are used into ultrasonic disperse in ethanol
90min forms uniform suspension, is then dried in vacuo at 80 DEG C, and Si-C-M composite particles and polyacrylonitrile are obtained
Mixture.
Finally the mixture of Si-C-M composite particles and polyacrylonitrile after drying is put into tube furnace, is protected in argon gas
Under, roasting charing is carried out at 1000 DEG C to get final Si-C-M composite material.
Embodiment 3
Firstly, being in molar ratio 1:2 ball milling on ball mill by silica material quartz and sodium block, then by ball milling
Mixture afterwards is immersed in hydrochloric acid, then uses deionized water, the washing such as ethyl alcohol, and separation obtains nano-silicon after drying.
Then the nano silica fume particle for being 200nm by the partial size of 0.2g synthesis, the graphite of 0.2g, the manganese nitrate difference of 0.1g
It is added to alone in the aqueous solution for the sucrose that concentration is 0.2M, ultrasonic disperse 30min forms the suspension or solution hooked；So
Three kinds of solution are put together afterwards and are continuesd to mix uniformly.
Secondly, above-mentioned resulting mixed liquor to be carried out using spray drying process at 700 DEG C to spraying cracking, it is multiple that Si-C-M is made
Condensation material first product；
Then, the above-mentioned Si-C composite material first product of 0.2g and 0.05g epoxy resin are used into ultrasonic disperse in ethanol
90min forms uniform suspension, is then dried in vacuo at 80 DEG C, and Si-C-M composite particles and epoxy resin are obtained
Mixture.
Finally the mixture of Si-C-M composite particles and epoxy resin after drying is put into tube furnace, is protected in argon gas
Under, roasting charing is carried out at 1200 DEG C to get final Si-C-M composite material.
Embodiment 4
Firstly, being in molar ratio 1:2 ball milling on ball mill by silica material diatomite and magnesium powder, then by ball milling
Mixture afterwards is immersed in hydrochloric acid, then uses deionized water, the washing such as ethyl alcohol, and separation obtains nano-silicon after drying.
Then the nano silica fume particle for being 50nm by the partial size of 0.2g synthesis, the graphite of 0.2g and the carbon nanotube of 0.05g,
The ferric nitrate of 0.1g is added to alone respectively in the aqueous solution for the glucose that concentration is 0.2M, and ultrasonic disperse 30min, formation hooks
Suspension or solution；Then four kinds of solution are put together and is continuesd to mix uniformly.
Secondly, above-mentioned resulting mixed liquor to be carried out using spray drying process at 200 DEG C to spraying cracking, it is multiple that Si-C-M is made
Condensation material first product；
Then, the above-mentioned Si-C composite material first product of 0.2g and 0.05g pitch are used into ultrasonic disperse in tetrahydrofuran
90min forms uniform suspension, is then dried in vacuo at 80 DEG C, and the mixing of Si-C-M composite particles and pitch is obtained
Object.
Finally the mixture of Si-C-M composite particles and pitch after drying is put into tube furnace, under protection of argon gas,
Roasting charing is carried out at 900 DEG C to get final Si-C-M composite material.
Application examples
Si-C composite material prepared by embodiment 1-4 is used as conductive agent, carboxylic first as negative electrode active material, carbon black (SP)
Base sodium cellulosate (CMC) and butadiene-styrene rubber (SBR) are used as bonding agent, according to quality than Si-C composite material: SP:CMC:SBR=
90:5:2:3 mixing, using deionized water as dispersing agent, is made solid content about 50%, viscosity 2000- after agitated
The slurry of 4000mPa.s is coated on copper foil, button cell or flexible packaged battery is prepared into after drying, cold pressing, cut-parts, slitting
The cathode pole piece in pond；The LiPF that electrolyte is l M with concentration6Lithium salts, with the ethylene carbonate of mass ratio EC:EMC:DEC=1:1:1
The mixture of ester, methyl ethyl carbonate and diethyl carbonate is as non-aqueous organic solvent.
The button cell prepared as negative electrode active material through the above method to Si-C composite material prepared by embodiment 1 exists
Current density is 200mA/g, and voltage range carries out initial capacity test and cycle performance test under the conditions of being 0.01-2.5V, point
Result shown in Fig. 1 and Fig. 2 is not obtained.
As seen from Figure 1, Figure 2, which has excellent discharge capacity.Under the current density of 200mA/g, Si-C-M electricity
Pole first circle specific discharge capacity is 1113mAh/g, and first circle coulombic efficiency is 87%.Its capacity remains at after 80 circle circulations
970mAh/g or so, and its coulombic efficiency in 80 circle circulations maintains 100% or so.This shows that porous second level micron is multiple
Condensation material shows preferable structural advantage, can provide enough spaces effectively to accommodate the expansion and dusting of Si.The silicon
Carbon composite excellent electrochemical performance can be used as the good negative electrode material of lithium ion battery.
Claims (10)
1. a kind of lithium ion battery silicon-carbon composite material characterized by comprising include nano-silicon, carbon material, nanometer inertia gold
The composite particles of category or metal silicide, and it is coated on the carbon-coating on the composite particles surface；The lithium ion battery silicon-carbon
Composite material is the porous secondary structure of micron-scale.
2. lithium ion battery silicon-carbon composite material as described in claim 1, which is characterized in that the partial size of the nano-silicon is
50-900nm, the partial size of carbon material are 10nm-100 μm, and the partial size of nanometer inert metal or metal silicide is 10-100nm, carbon
Layer is with a thickness of 10-50nm.
3. lithium ion battery silicon-carbon composite material as described in claim 1, which is characterized in that by percentage to the quality, described
In lithium ion battery silicon-carbon composite material nano-silicon be 10-60%, carbon material 30-80%, nanometer inert metal or metallic silicon
Compound is 5-20%, carbon-coating 5-20%.
4. lithium ion battery silicon-carbon composite material as described in claim 1, which is characterized in that the lithium ion battery silicon-carbon
The pore size of composite material is 30-100nm, porosity 10-100%.
5. the preparation method of lithium ion battery silicon-carbon composite material according to any one of claims 1-4, which is characterized in that packet
Include following steps:
(1) nano-silicon, carbon material, metal salt and organic carbon source solution are mixed, obtains precursor solution；
(2) precursor solution is spray-dried, obtains Si-C-M composite material first product；
(3) it disperses Si-C-M composite material first product in organic carbon source solution, is sintered in an inert atmosphere again after removing solvent
The lithium ion battery silicon-carbon composite material is made in carbonization.
6. preparation method as claimed in claim 5, which is characterized in that the nano-silicon is restored by silica material and metal
It after agent mixing and ball milling, then is soaked in acid and removes impurity, separation is made.
7. preparation method as claimed in claim 6, which is characterized in that the silica material is diatomite, mesoporous two
Silica, porous molecular screen, quartz or artificial synthesized silica；The metallic reducing agent be magnesium, calcium, lithium, sodium or
Potassium metal powder.
8. preparation method as claimed in claim 5, which is characterized in that the carbon material is natural graphite, artificial graphite, swollen
At least one of swollen graphite, graphene, carbon black, active carbon and carbon nanotube.
9. preparation method as claimed in claim 5, which is characterized in that the metal salt is iron, copper, zinc, manganese, cobalt, nickel salt
At least one of.
10. preparation method as claimed in claim 5, which is characterized in that in step (2), after precursor solution atomization, by carrier gas
It brings into reacting furnace in 200-900 DEG C of progress spray pyrolysis in situ.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102007627A (en) * | 2008-04-18 | 2011-04-06 | 株式会社丰田自动织机 | Negative electrode for lithium ion secondary battery, and method for production thereof |
| CN103346305A (en) * | 2013-07-01 | 2013-10-09 | 华南师范大学 | Preparation and application of lithium battery silicon-carbon composite material taking synthetic graphite as carrier |
| CN104332621A (en) * | 2014-09-27 | 2015-02-04 | 奇瑞汽车股份有限公司 | Method for preparing hollow nano silicon microsphere through metal thermal reduction and lithium ion battery |
| CN108511719A (en) * | 2018-03-29 | 2018-09-07 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of bivalve layer structural composite material, preparation method and the lithium ion battery comprising the composite material |
-
2018
- 2018-10-11 CN CN201811182489.3A patent/CN109216686B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102007627A (en) * | 2008-04-18 | 2011-04-06 | 株式会社丰田自动织机 | Negative electrode for lithium ion secondary battery, and method for production thereof |
| CN103346305A (en) * | 2013-07-01 | 2013-10-09 | 华南师范大学 | Preparation and application of lithium battery silicon-carbon composite material taking synthetic graphite as carrier |
| CN104332621A (en) * | 2014-09-27 | 2015-02-04 | 奇瑞汽车股份有限公司 | Method for preparing hollow nano silicon microsphere through metal thermal reduction and lithium ion battery |
| CN108511719A (en) * | 2018-03-29 | 2018-09-07 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of bivalve layer structural composite material, preparation method and the lithium ion battery comprising the composite material |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107195871A (en) * | 2017-04-06 | 2017-09-22 | 中国计量大学 | A kind of preparation method that SiOx/C negative materials are synthesized by carrier low temperature of carbon material |
| US12100833B2 (en) * | 2018-11-13 | 2024-09-24 | Guangdong Kaijin New Energy Technology Co., Ltd. | Hollow/porous silicon-based composite material and preparation method thereof |
| US20210273221A1 (en) * | 2018-11-13 | 2021-09-02 | Guangdong Kaijin New Energy Technology Co., Ltd. | Hollow/porous silicon-based composite material and preparation method thereof |
| CN109755555A (en) * | 2019-01-22 | 2019-05-14 | 山东玉皇新能源科技有限公司 | Silicon carbon material and preparation method thereof |
| CN111755669A (en) * | 2019-03-27 | 2020-10-09 | 贝特瑞新材料集团股份有限公司 | Composite material, preparation method and application thereof |
| CN112086624A (en) * | 2019-06-12 | 2020-12-15 | 识骅科技股份有限公司 | Manufacturing method of composite carbon-silicon cathode substrate and composite carbon-silicon cathode substrate manufactured by manufacturing method |
| CN112086624B (en) * | 2019-06-12 | 2022-11-29 | 芯量科技股份有限公司 | Manufacturing method of composite carbon-silicon negative electrode substrate and composite carbon-silicon negative electrode substrate made by the manufacturing method |
| CN110993910A (en) * | 2019-11-29 | 2020-04-10 | 国联汽车动力电池研究院有限责任公司 | A kind of silicon carbon composite material and preparation method thereof |
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| CN117199327B (en) * | 2023-11-07 | 2024-05-03 | 南通大学 | Quick-charging silicon-based negative electrode material for lithium battery and preparation method thereof |
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