WO2014048098A1 - Composite negative electrode material for lithium ion battery, preparation method thereof and lithium ion battery - Google Patents
Composite negative electrode material for lithium ion battery, preparation method thereof and lithium ion battery Download PDFInfo
- Publication number
- WO2014048098A1 WO2014048098A1 PCT/CN2013/073413 CN2013073413W WO2014048098A1 WO 2014048098 A1 WO2014048098 A1 WO 2014048098A1 CN 2013073413 W CN2013073413 W CN 2013073413W WO 2014048098 A1 WO2014048098 A1 WO 2014048098A1
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- WO
- WIPO (PCT)
- Prior art keywords
- lithium
- ion battery
- lithium ion
- negative electrode
- electrode material
- Prior art date
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 171
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 239000002131 composite material Substances 0.000 title claims abstract description 108
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 95
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 64
- -1 transition metal sulfide Chemical class 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 60
- 239000011247 coating layer Substances 0.000 claims abstract description 35
- 239000010936 titanium Substances 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 36
- 239000002002 slurry Substances 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 26
- 239000002482 conductive additive Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000002612 dispersion medium Substances 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- 150000003624 transition metals Chemical class 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000006230 acetylene black Substances 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000002134 carbon nanofiber Substances 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- 229910021382 natural graphite Inorganic materials 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- 239000004005 microsphere Substances 0.000 claims 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 abstract 1
- 229910003092 TiS2 Inorganic materials 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229910052960 marcasite Inorganic materials 0.000 abstract 1
- 229910052683 pyrite Inorganic materials 0.000 abstract 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 abstract 1
- 239000010405 anode material Substances 0.000 description 69
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 20
- 239000004575 stone Substances 0.000 description 18
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 13
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 9
- 230000003247 decreasing effect Effects 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 8
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229910000339 iron disulfide Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000003780 insertion Methods 0.000 description 6
- 230000037431 insertion Effects 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 102000004310 Ion Channels Human genes 0.000 description 4
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 4
- 239000002931 mesocarbon microbead Substances 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- KVIXPDSTVUISDR-UHFFFAOYSA-N SC(C(=O)N)S.NN Chemical compound SC(C(=O)N)S.NN KVIXPDSTVUISDR-UHFFFAOYSA-N 0.000 description 3
- TUDIUWZXQPVWJK-UHFFFAOYSA-N SNS.NN Chemical compound SNS.NN TUDIUWZXQPVWJK-UHFFFAOYSA-N 0.000 description 3
- 229930182558 Sterol Natural products 0.000 description 3
- FOHLLNJOGVSMMC-UHFFFAOYSA-N [Fe](=S)=S.[Li].[Li] Chemical compound [Fe](=S)=S.[Li].[Li] FOHLLNJOGVSMMC-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003432 sterols Chemical class 0.000 description 3
- 235000003702 sterols Nutrition 0.000 description 3
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- OPBRFYAINZSDAU-UHFFFAOYSA-N [Co]=S.[Li] Chemical compound [Co]=S.[Li] OPBRFYAINZSDAU-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- IQMAMZYAQFTIAU-UHFFFAOYSA-N lithium;sulfanylidenemolybdenum Chemical compound [Li].[Mo]=S IQMAMZYAQFTIAU-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- XIKYYQJBTPYKSG-UHFFFAOYSA-N nickel Chemical compound [Ni].[Ni] XIKYYQJBTPYKSG-UHFFFAOYSA-N 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- ZDNZHITXTQBUPT-UHFFFAOYSA-N nickel samarium Chemical compound [Ni].[Sm] ZDNZHITXTQBUPT-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052851 sillimanite Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
-
- 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
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
Definitions
- Lithium-ion battery composite anode material, preparation method thereof and lithium ion battery The application No. 201210362677.0 submitted to the Chinese Patent Office on September 26, 2012, the invention name is "a lithium ion battery composite anode The material and its preparation method and the priority of the Chinese patent application of the lithium ion battery are hereby incorporated by reference in its entirety.
- Technical field is "a lithium ion battery composite anode The material and its preparation method and the priority of the Chinese patent application of the lithium ion battery are hereby incorporated by reference in its entirety.
- the present invention relates to the field of lithium ion batteries, and in particular to a lithium ion battery composite anode material, a preparation method thereof and a lithium ion battery. Background technique
- lithium-ion batteries Since the 1990s, among many energy substitutes, lithium-ion batteries have attracted close attention due to their high energy density, good cycle performance, and no memory effect. With the development of low-carbon economy, lithium-ion batteries are actively developing in the direction of power vehicles and grid energy storage. Therefore, the development of lithium-ion batteries with high energy density and long cycle life has become the focus of research in the industry.
- lithium-ion batteries use carbon-based materials as negative electrodes, but carbon-based anode materials have many defects.
- the first charge and discharge forms a solid electrolyte interface film (SEI), causing irreversible capacity loss, insufficient cycle performance, and high temperature failure risk. And security risks, etc., these problems make carbon-based materials have been unable to meet the needs of energy storage batteries.
- SEI solid electrolyte interface film
- Some lithium-ion batteries use alloy materials as the anode material. Although the alloy materials have a high specific capacity, the alloy materials have large volume expansion and poor cycle performance, which cannot meet the needs of market applications.
- sulfur or sulfide such as NiS, FeS 2 , FeS, TiS 2
- Lithium batteries with electrode materials these materials have high lithium insertion capacity.
- the lithium insertion capacity of NiS and FeS 2 is about 600 mAh/g, but these materials have poor cycle performance because the sulfide active substances are prone to occur during charge and discharge.
- the agglomeration reduces the cycle performance, and the sulfide active material easily reacts with the electrolyte to decompose, resulting in a decrease in reversible capacity, and thus cannot meet the high cycle performance requirements of the energy storage battery. Summary of the invention
- the first aspect of the embodiments of the present invention provides a lithium ion battery composite anode material, which solves the problem that the sulfide anode material is easily agglomerated and easily decomposed with the electrolyte, thereby causing the battery to have low durability and circulation. Performance issues.
- a second aspect of the embodiments of the present invention provides a method for preparing a composite material of a lithium ion battery composite type.
- a third aspect of the embodiments of the present invention provides a lithium ion battery.
- an embodiment of the present invention provides a lithium ion battery composite anode material, including a transition metal sulfide, and a coating layer disposed on a surface of the transition metal sulfide, wherein the transition metal sulfide is NiS, One or more of FeS 2 , FeS, TiS 2 , MoS and Co 9 S 8 , and the material of the coating layer includes lithium titanate Li 4 Ti 5 0 12 .
- the lithium ion battery composite anode material provided by the present invention is composed of a transition metal sulfide and a coating layer disposed on the surface of the transition metal sulfide, wherein the transition metal sulfide is selected from NiS (Petrified Nickel) One or more of FeS 2 (di-cobalt iron), FeS (ferrous sulfide), TiS 2 (di-titanium), MoS (molybdenum sulfide), and Co 9 S 8 (cobalt sulfide). These transition metal sulfides have a high lithium intercalation capacity, and the lithium intercalation capacity of NiS and FeS 2 is about 600 mAh/g, so that the lithium ion battery composite anode material can have a high capacity.
- NiS Petrified Nickel
- the material of the cladding layer includes lithium titanate Li 4 Ti 5 0 12 , which has the following advantages: (1) lithium titanate is "zero strain, electrode material, according to the research results of S. Schamer et al. (J.of Electrochemical society, 146(3), 1999, 857, 861), cubic spinel lithium titanate during lithium ion intercalation-deintercalation, crystal The maximum lattice parameter is reduced from 8.3595 A to 8.3538 A. The lattice constant changes little, the volume change is small, and the structural stability is maintained, so it has excellent cycle performance. (2) Lithium titanate has a three-dimensional lithium ion channel.
- the lithium ion diffusion coefficient is one order of magnitude larger than that of the carbon-based anode material, which can improve the rate performance of the lithium battery; (3)
- the equilibrium potential of lithium titanate is about 1.55V, which can effectively prevent metal lithium deposition and improve the safety performance of the lithium ion battery.
- the SEI film formation potential is not reached, and the electrolyte does not undergo reductive decomposition on the surface of the lithium titanate, which is advantageous for maintaining the stability of the electrolyte and improving the cycle performance.
- lithium titanate has a low specific capacity, and the battery produced by the battery has a low energy density, and the lithium titanate material is expensive, which seriously affects the commercial use of lithium titanate as a negative electrode battery.
- the present invention coats lithium titanate Li 4 Ti 5 0 12 on the surface of the transition metal sulfide, and can coat the active site on the surface of the sulfide, thereby effectively protecting the transition metal sulfide and preventing the transition metal sulfide. It reacts with the electrolyte to prevent decomposition of the sulfide, and the lithium ion battery composite anode material has high capacity and good cycle stability and durability. In addition, due to lithium titanate
- 1 ⁇ 4 13 ⁇ 40 12 has a three-dimensional lithium ion channel with a large lithium ion diffusion coefficient, which can improve the rate performance of the lithium ion battery.
- the lithium insertion potential of these transition metal sulfide materials is close to that of lithium titanate Li 4 Ti 5 0 12 , so that the lithium ion battery composite anode material can have a stable and uniform charge and discharge platform.
- the coating layer has a thickness of 50 to 8000 nm. More preferably, the coating layer has a thickness of from 1000 to 4000 nm.
- the transition metal sulfide accounts for 10% to 95% of the total mass of the lithium ion battery composite anode material.
- the transition metal sulfide accounts for 60% to 80% of the total mass of the lithium-ion battery composite negative electrode material.
- the material of the coating layer may further include Conductive additive.
- the conductive additive is one or more of artificial graphite, natural graphite, acetylene black, carbon black, mesocarbon microbeads, carbon nanotubes, carbon nanofibers, phenolic resin, and sucrose.
- the conductive additive accounts for 1% to 5% of the total mass of the lithium ion battery composite negative electrode material.
- the lithium ion battery composite anode material provided by the first aspect of the present invention has high capacity, stable structure, does not react with the electrolyte, does not agglomerate, and finally can make the lithium ion battery have high durability. Properties and cycle stability; In addition, since the lithium titanate Li 4 Ti 5 0 12 has a large lithium ion diffusion coefficient, the rate performance of the lithium ion battery can be improved.
- an embodiment of the present invention provides a method for preparing a lithium ion battery composite anode material, comprising the following steps:
- the coating raw material lithium source is selected from one or more selected from the group consisting of lithium hydroxide, lithium hydroxide hydrate, lithium carbonate, lithium nitrate, lithium sulfate, lithium fluoride, lithium oxalate, lithium chloride and lithium acetate;
- the coated raw material titanium source is selected from one or more of titanium dioxide, titanium tetrachloride, titanium trichloride, titanium isopropoxide, tetrabutyl titanate, butyl titanate and n-propyl titanate;
- the transition metal sulphate is selected from one or more of NiS, FeS 2 , FeS, TiS 2 , MoS, and Co 9 S 8 ;
- the dispersion medium is selected from the group consisting of water, hydrazine, hydrazine-dimercaptoamide (DMF), hydrazine, hydrazine-dimercaptoacetamide (DMAc), N-2-mercaptopyrrolidone (NMP), tetrahydrofuran (THF), One or more of ethanol and sterol;
- the obtained slurry is coated by a sol-gel method, a hydrothermal reaction method, a microwave chemical method or a high-temperature solid phase method to obtain a lithium ion battery composite anode material;
- the pole material includes the transition metal sulfide, and a coating layer coated on the surface of the transition metal sulfide, and the material of the coating layer includes lithium titanate Li 4 Ti 5 0 12 .
- the coating layer has a thickness of 50 to 8000 nm. More preferably, the coating layer has a thickness of from 1000 to 4000 nm.
- the transition metal sulfide accounts for 10% to 95% of the total mass of the lithium ion battery composite anode material.
- the transition metal sulfide accounts for 60% to 80% of the total mass of the lithium-ion battery composite negative electrode material.
- the specific operation of the sol-gel method is as follows: drying the slurry at 60-80 ° C to obtain a precursor material, and placing the precursor material in a fluorocarbon furnace at 500-700 ° C for sintering 1 ⁇ 5 hours, after cooling to room temperature with the furnace, a lithium ion battery composite anode material is obtained.
- the specific operation of the hydrothermal reaction method is: transferring the slurry into a hydrothermal reaction kettle, and performing a hydrothermal ion exchange reaction at 150 to 160 ° C for 8 to 12 hours to obtain a black precipitate, and then placing the black precipitate at 500.
- the specific operation of the microwave chemical method is as follows: drying the slurry at 100-120 ° C to obtain a precursor material, placing the precursor material in an industrial microwave oven, and heating to 600 at 10 ° C / min. ⁇ 800 ° C, heat preservation for 1 to 4 hours, with the furnace cooling, the lithium ion battery composite anode material is obtained.
- the specific operation of the high-temperature solid phase method is: drying the slurry at 100-120 ° C to obtain a precursor material, and the precursor material is placed in a muffle furnace and sintered at 400-900 ° C. 0.5 to 10 hours, the furnace is cooled, and the lithium ion battery composite anode material is obtained.
- the coating material may further include a conductive additive, that is, a conductive additive is added in the step (1), and a lithium source, a titanium source, and a transition metal to be coated.
- a conductive additive is added in the step (1), and a lithium source, a titanium source, and a transition metal to be coated.
- the sulfide is uniformly dispersed in a dispersion medium to form a slurry.
- the conductive additive is one or more of artificial graphite, natural graphite, acetylene black, carbon black, mesocarbon microbeads, carbon nanotubes, carbon nanofibers, phenolic resin, and sucrose.
- the conductive additive accounts for 1% to 5% of the total mass of the lithium ion battery composite negative electrode material.
- a method for preparing a composite material of a lithium ion battery composite anode provided by the second aspect of the present invention provides a high capacity and a stable structure of the lithium ion battery composite anode material, which does not react with the electrolyte.
- the reaction, no agglomeration, and a large lithium ion diffusion coefficient, can make the lithium ion battery have high durability and cycle stability, and can improve the rate performance of the lithium ion battery.
- an embodiment of the present invention provides a lithium ion battery comprising the lithium ion battery composite anode material provided by the first aspect of the embodiments of the present invention.
- the lithium ion battery provided by the third aspect of the embodiment of the present invention has a long cycle life and has excellent discharge capacity and rate performance.
- FIG. 1 is a comparison of cycle performance of a lithium ion battery obtained in Example 1 of the present invention and Comparative Example 1.
- FIG. 2 is a comparison diagram of cycle performance of a lithium ion battery obtained in Example 2 and Comparative Example 2 of the present invention
- FIG. 3 is an embodiment of the present invention.
- Figure 3 is a comparison chart of the cycle performance of the lithium ion battery obtained in Example 3 and Comparative Example 3
- Figure 4 is a comparison chart of the cycle performance of the lithium ion battery obtained in Example 4 and Comparative Example 4 of the present invention
- Figure 5 is a graph showing the cycle performance of a lithium ion battery obtained in Example 5 and Comparative Example 5 of the present invention.
- a first aspect of the embodiments of the present invention provides a lithium ion battery composite anode material, which solves the problem that the stone telluride anode material is easily agglomerated and easily reacted with the electrolyte to decompose, thereby causing the battery to have low durability and cycle performance. problem.
- a second aspect of the embodiments of the present invention provides a method for preparing a lithium ion battery composite anode material.
- a third aspect of the embodiments of the present invention provides a lithium ion battery.
- an embodiment of the present invention provides a lithium ion battery composite anode material, including a transition metal sulfide, and a coating layer disposed on a surface of the transition metal sulfide, wherein the transition metal sulfide is NiS, One or more of FeS 2 , FeS, TiS 2 , MoS and Co 9 S 8 , and the material of the coating layer includes lithium titanate Li 4 Ti 5 0 12 .
- the lithium ion battery composite anode material provided by the present invention is composed of a transition metal sulfide and a coating layer disposed on the surface of the transition metal sulfide, wherein the transition metal sulfide is selected from NiS (Petrified Nickel) One or more of FeS 2 (di-cobalt iron), FeS (ferrous sulfide), TiS 2 (di-titanium), MoS (molybdenum sulfide), and Co 9 S 8 (cobalt sulfide). These transition metal sulfides have a high lithium intercalation capacity, and the lithium intercalation capacity of NiS and FeS 2 is about 600 mAh/g, so that the lithium ion battery composite anode material can have a high capacity.
- NiS Petrified Nickel
- the material of the cladding layer includes lithium titanate Li 4 Ti 5 0 12 , which has the following advantages: (1) lithium titanate is "zero strain, electrode material, according to the research results of S. Schamer et al. (J.of Electrochemical society, 146(3), 1999, 857, 861), cubic spinel lithium titanate during lithium ion intercalation-deintercalation, crystal The maximum lattice parameter is reduced from 8.3595 A to 8.3538 A. The lattice constant changes little, the volume change is small, and the structural stability is maintained, so it has excellent cycle performance. (2) Lithium titanate has a three-dimensional lithium ion channel.
- the lithium ion diffusion coefficient is one order of magnitude larger than that of the carbon-based anode material, which can improve the rate performance of the lithium battery; (3)
- the equilibrium potential of lithium titanate is about 1.55V, which can effectively prevent metal lithium deposition and improve the safety performance of the lithium ion battery.
- the SEI film formation potential is not reached, and the electrolyte does not undergo reductive decomposition on the surface of the lithium titanate, which is advantageous for maintaining the stability of the electrolyte and improving the cycle performance.
- lithium titanate has a low specific capacity, and the battery produced by the battery has a low energy density, and the lithium titanate material is expensive, which seriously affects the commercial use of lithium titanate as a negative electrode battery.
- the present invention coats lithium titanate Li 4 Ti 5 0 12 on the surface of the transition metal sulfide, and can coat the active site on the surface of the sulfide, thereby effectively protecting the transition metal sulfide and preventing the transition metal sulfide. It reacts with the electrolyte to prevent decomposition of the sulfide, and the lithium ion battery composite anode material has high capacity and good cycle stability and durability. In addition, due to lithium titanate
- 1 ⁇ 4 13 ⁇ 40 12 has a three-dimensional lithium ion channel with a large lithium ion diffusion coefficient, which can improve the rate performance of the lithium ion battery.
- the lithium insertion potential of these transition metal sulfide materials is close to that of lithium titanate Li 4 Ti 5 0 12 , so that the lithium ion battery composite anode material can have a stable and uniform charge and discharge platform.
- the embodiment of the present invention has no limitation on the position of the transition metal sulfide in the lithium ion battery composite anode material, and is coated in the coating layer; the embodiment of the present invention is applicable to the transition metal sulfide.
- the particle size is not particularly limited and can be coated in the coating layer.
- the coating layer has a thickness of 50 to 8000 nm. In the embodiment, the thickness of the coating layer is 1000 to 4000 nm.
- the transition metal sulfide accounts for 10% to 95% of the total mass of the lithium ion battery composite anode material.
- the transition metal sulfide accounts for the total mass of the lithium ion battery composite anode material. 60% ⁇ 80% of the amount.
- the transition metallite filler is selected from the group consisting of NiS (stone-filled nickel), FeS 2 (two-stone iron), FeS (stone-filled ferrous), TlS 2 (di-titanized titanium), MoS (diazepine molybdenum) And one or more of C0 9 S 8 (Petrified Cobalt).
- the transition metal stone telluride is two or more kinds, the ratio between the different transition metal petrochemicals is not particularly limited.
- the material of the cladding layer may further include a conductive additive in order to improve the conductivity of the lithium ion battery composite anode material.
- the conductive additive is one or more of artificial graphite, natural graphite, acetylene black, carbon black, mesocarbon microbeads, carbon nanotubes, carbon nanofibers, phenolic resin, and sucrose.
- the conductive additive accounts for 1% to 5% of the total mass of the lithium ion battery composite negative electrode material.
- the conductive additive is evenly distributed in the coating layer, located in the vicinity of the lithium titanate Li 4 Ti 5 0 12 material, that is, the conductive additive is uniformly incorporated into the lithium titanate Li 4 Ti 5 0 12 material, in the transition metal
- the surface of the stone A compound forms a mixed coating layer.
- the lithium ion battery composite anode material provided by the first aspect of the present invention has high capacity, stable structure, does not react with the electrolyte, does not agglomerate, and finally can make the lithium ion battery have high durability. Properties and cycle stability; In addition, since the lithium titanate Li 4 Ti 5 0 12 has a large lithium ion diffusion coefficient, the rate performance of the lithium ion battery can be improved.
- an embodiment of the present invention provides a method for preparing a lithium ion battery composite anode material, comprising the following steps:
- the lithium source of the coating raw material is selected from the group consisting of lithium hydroxide, lithium hydroxide hydrate, lithium carbonate, lithium nitrate, lithium sulfate, One or more of lithium fluoride, lithium oxalate, lithium chloride and lithium acetate;
- the coated raw material titanium source is selected from one or more of titanium dioxide, titanium tetrachloride, titanium trichloride, titanium isopropoxide, tetrabutyl titanate, butyl titanate and n-propyl titanate;
- the transition metal sulphate is selected from one or more of NiS, FeS 2 , FeS, TiS 2 , MoS, and Co 9 S 8 ;
- the dispersion medium is selected from the group consisting of water, hydrazine, hydrazine-dimercaptoamide (DMF), hydrazine, hydrazine-dimercaptoacetamide (DMAc), N-2-mercaptopyrrolidone (NMP), tetrahydrofuran (THF), One or more of ethanol and sterol;
- the negative electrode material includes the transition metal sulfide, and a coating layer coated on the surface of the transition metal sulfide, and the material of the coating layer includes lithium titanate Li 4 Ti 5 0 12 .
- the embodiment of the present invention has no limitation on the position of the transition metal sulfide in the lithium ion battery composite anode material, and is coated in the coating layer; the embodiment of the present invention is applicable to the transition metal sulfide.
- the particle size is not particularly limited and can be coated in the coating layer.
- the coating layer has a thickness of 50 to 8000 nm. In the embodiment, the thickness of the coating layer is 1000 to 4000 nm.
- the transition metal sulfide accounts for 10% to 95% of the total mass of the lithium ion battery composite anode material.
- the transition metal sulfide accounts for 60% to 80% of the total mass of the lithium ion battery composite negative electrode material.
- the transition metallite filler is selected from the group consisting of NiS (stone-filled nickel), FeS 2 (two-stone iron), FeS (stone-filled ferrous), TlS 2 (di-titanized titanium), MoS (diazepine molybdenum) And one or more of C0 9 S 8 (Petrified Cobalt).
- the transition metal stone telluride is two or more kinds, the ratio between the different transition metal petrochemicals is not particularly limited.
- the coated raw material lithium source and the titanium source are added in a stoichiometric ratio of lithium titanate Li 4 Ti 5 0 12 .
- the dispersion medium is selected from the group consisting of water, hydrazine, hydrazine-dimercaptoamide (DMF), hydrazine, hydrazine-dimercaptoacetamide (DMAc), N-2-mercaptopyrrolidone (NMP), tetrahydrofuran (THF), One or more of ethanol and sterol.
- DMF hydrazine
- DMAc hydrazine-dimercaptoacetamide
- NMP N-2-mercaptopyrrolidone
- THF tetrahydrofuran
- One or more of ethanol and sterol One or more of ethanol and sterol.
- the specific operation of the sol-gel method is as follows: drying the slurry at 60-80 ° C to obtain a precursor material, and placing the precursor material in a fluorocarbon furnace at 500-700 ° C for sintering 1 ⁇ 5 hours, after cooling to room temperature with the furnace, a lithium ion battery composite anode material is obtained.
- the specific operation of the hydrothermal reaction method is: transferring the slurry into a hydrothermal reaction kettle, and performing a hydrothermal ion exchange reaction at 150 to 160 ° C for 8 to 12 hours to obtain a black precipitate, and then placing the black precipitate at 500.
- the specific operation of the microwave chemical method is as follows: drying the slurry at 100-120 ° C to obtain a precursor material, placing the precursor material in an industrial microwave oven, and heating to 600 at 10 ° C / min. ⁇ 800 ° C, heat preservation for 1 to 4 hours, with the furnace cooling, the lithium ion battery composite anode material is obtained.
- the specific operation of the high-temperature solid phase method is: drying the slurry at 100-120 ° C to obtain a precursor material, and the precursor material is placed in a muffle furnace and sintered at 400-900 ° C. 0.5 to 10 hours, the furnace is cooled, and the lithium ion battery composite anode material is obtained.
- transition metal sulfide and lithium titanate Li 4 Ti 5 0 12 are described above, and will not be described herein.
- the coating material may be further The step includes a conductive additive, that is, a conductive additive is added in the step (1), and a lithium source, a titanium source, and a transition metal sulfide to be coated are uniformly dispersed in the dispersion medium to prepare a slurry.
- the conductive additive is one or more of artificial graphite, natural graphite, acetylene black, carbon black, mesocarbon microbeads, carbon nanotubes, carbon nanofibers, phenolic resin, and sucrose.
- the conductive additive accounts for 1% to 5% of the total mass of the lithium ion battery composite negative electrode material.
- the conductive additive is evenly distributed in the coating layer, located in the vicinity of the lithium titanate Li 4 Ti 5 0 12 material, that is, the conductive additive is uniformly incorporated into the lithium titanate Li 4 Ti 5 0 12 material, in the transition metal
- the surface of the stone A compound forms a mixed coating layer.
- a method for preparing a composite material of a lithium ion battery composite anode provided by the second aspect of the present invention provides a high capacity and a stable structure of the lithium ion battery composite anode material, which does not react with the electrolyte.
- the reaction, no agglomeration, and a large lithium ion diffusion coefficient, can make the lithium ion battery have high durability and cycle stability, and can improve the rate performance of the lithium ion battery.
- an embodiment of the present invention provides a lithium ion battery comprising the lithium ion battery composite anode material provided by the first aspect of the embodiments of the present invention.
- the lithium ion battery provided by the third aspect of the embodiment of the present invention has a long cycle life and has excellent discharge capacity and rate performance.
- the lithium ion battery composite anode material obtained in the present embodiment, the conductive carbon black, and the binder polyvinylidene fluoride PVDF are mixed in a mass ratio of 92:4:4 in N-2-mercaptopyrrolidone (NMP). Evenly, a mixed slurry was obtained, and the mixed slurry was applied to a 16 um aluminum foil, dried, and then cut into a pole piece, and a lithium piece was used as a counter electrode to assemble a CR2032 type button battery.
- the packaged battery was carried out in a glove box under an argon atmosphere using an EC:DMC (1:1 ratio by volume) mixture of 1 mol/L LiPF 6 and a Celgard 2400 separator.
- Embodiment 2 Embodiment 2
- Embodiment 3 Same as the first embodiment. Embodiment 3
- the slurry is dried in a drying oven at 110 ° C to obtain a precursor material, and the precursor material is placed in an industrial microwave oven, heated to 650 ° C at a rate of 10 ° C / min, kept for 2 hours, and cooled with the furnace.
- a lithium ion battery composite negative electrode material in which lithium titanate Li 4 Ti 5 0 12 was coated with nickel sulfide (NiS ) and sillimanite iron (FeS 2 ) was obtained.
- Embodiment 4 Same as the first embodiment. Embodiment 4
- Embodiment 5 Same as the first embodiment. Embodiment 5
- Embodiment 6 Same as the first embodiment. Embodiment 6
- the slurry is dried in a drying oven at 110 ° C to obtain a precursor material, and the precursor material is placed in an industrial microwave oven, heated to 650 ° C at a rate of 10 ° C / min, kept for 2 hours, and cooled with the furnace.
- a lithium ion battery composite negative electrode material of lithium titanate 1 ⁇ 4 13 ⁇ 40 12 coated with iron disulfide (FeS 2 ) was obtained.
- Nickel sulfide (NiS) not coated with lithium titanate Li 4 Ti 5 0 12 was assembled into a lithium ion battery in the same manner as in Example 1.
- a two-stone iron (FeS 2 ) which is not coated with lithium titanate Li 4 Ti 5 0 12 is assembled into a lithium ion battery in the same manner as in the first embodiment.
- a nickel-ion battery (NiS) and a two-stone iron (FeS 2 ) mixed anode material which are not coated with lithium titanate Li 4 Ti 5 0 12 are assembled into a lithium ion battery in the same manner as in the first embodiment.
- Co 9 S 8 (cobalt sulfide) not coated with lithium titanate Li 4 Ti 5 0 12 was assembled into a lithium ion battery, and the lithium ion battery prepared in the same manner as in the above first embodiment and the comparative example was used as a test battery. Used in the performance test of the following effect examples.
- the lithium ion batteries prepared in the above examples and comparative examples were subjected to a charge and discharge cycle test using a battery performance tester.
- the test conditions are: charging cut-off voltage to 2.5V, discharge cut-off voltage to 1.3V, current density of 0.07mA/cm 2 .
- Fig. 1 is a graph showing the comparison of cycle performance of a lithium ion battery obtained in Example 1 of the present invention and Comparative Example 1.
- the first specific specific capacity of the nickel-nickel (NiS) lithium ion battery composite anode material coated with lithium titanate Li 4 Ti 5 0 12 on the surface of the first embodiment is 423 mAh/g, and the ratio is not
- the first specific capacity of the coated stone-filled nickel (NiS) material was 500 mAh/g, but after 50 cycles, its specific capacity decreased to 197 mAh/g, only 39.4% of the first specific capacity;
- the lithium niobate (NiS) lithium ion battery composite anode material coated with lithium titanate Li 4 Ti 5 0 12 has a specific capacity decrease of 399 mAh/g after 50 cycles, which is 93% of the first specific capacity.
- the nickel sulfide material coated with lithium titanate Li 4 Ti 5 0 12 has a significant improvement in cycle
- Example 2 is a comparison diagram of cycle performance of a lithium ion battery obtained in Example 2 and Comparative Example 2 of the present invention. It can be seen from FIG. 2 that the first specific specific capacity of the lithium iron disulfide lithium ion battery composite anode material coated with lithium titanate Li 4 Ti 5 0 12 on the surface of the second embodiment is 556 mAh/g, and the comparative example is not coated.
- the first of the two stone-filled iron materials The secondary specific capacity is 600 mAh/g, but after 50 cycles, its specific capacity decreases to 125 mAh/g, which is only 21% of the first specific capacity; and the surface is coated with lithium titanate Li 4 Ti 5 0 12 After 50 cycles, the specific capacity of the lithium iron ion battery composite anode material decreased to 512 mAh/g, which is 92% of the first specific capacity.
- the results show that: the surface coated with lithium titanate Li 4 Ti 5 0 12
- the iron sulfide material has a significant improvement in cycle performance.
- Example 3 is a graph showing the cycle performance of a lithium ion battery obtained in Example 3 of the present invention and Comparative Example 3. It can be seen from FIG. 3 that the first specific capacity of the composite negative electrode material of the nickel sulfide and the lithium iron disulfide lithium ion battery coated with lithium titanate Li 4 Ti 5 0 12 on the surface of the third embodiment is 394 mAh/g, and the third comparative example The uncoated nickel sulfide and iron disulfide mixture had a first specific capacity of 500 mAh/g, but after 50 cycles, its specific capacity decreased to 165 mAh/g, only 30% of the first specific capacity; After 50 cycles of the nickel sulfide and lithium iron disulfide lithium ion battery composite anode materials coated with lithium titanate Li 4 Ti 5 0 12 , the specific capacity decreased to 370 mAh/g, which is 94% of the first specific capacity. : The surface is coated with lithium titanate Li 4 Ti 5 0 12 nickel sulfide and iron disulfide material,
- Example 4 is a graph showing the cycle performance of a lithium ion battery obtained in Example 4 and Comparative Example 4 of the present invention.
- the first specific specific capacity of the lithium sulfide molybdenum lithium ion battery composite anode material coated with lithium titanate Li 4 Ti 5 0 12 on the surface of the fourth embodiment is 324.2 mAh/g, and the comparative example is uncoated.
- the first specific capacity of the stone-filled molybdenum was 400 mAh/g, but after 50 cycles, its specific capacity decreased to 145.6 mAh/g, only 36.4% of the first specific capacity; and the surface coated with lithium titanate Li 4 Ti After 50 cycles of the 5 0 12 molybdenum sulfide lithium ion battery composite anode material, its specific capacity decreased to 298.5 mAh/g, which is 92.1% of the first specific capacity. Results: Surface coated with lithium titanate Li 4 Ti 5 The 0 12 molybdenum sulfide material has a significant improvement in cycle performance.
- Figure 5 is a graph showing the cycle performance of a lithium ion battery obtained in Example 5 and Comparative Example 5 of the present invention.
- the fourth embodiment of the surface coated with lithium titanate Li 4 Ti 5 0 12 cobalt sulfide lithium ion battery composite
- the first specific capacity of the negative electrode material was 298 mAh/g
- the first specific capacity of the four uncoated molybdenum sulfide was 350 mAh/g, but after 50 cycles, the specific capacity decreased to 73 mAh/g, only the first time ratio.
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Abstract
The embodiments of present invention provide a composite negative electrode material for a lithium ion battery, comprising a transition metal sulfide and a coating layer disposed on the surface of the transition metal sulfide, where said transition metal sulfide is one or more selected from the group consisting of NiS, FeS2, FeS, TiS2, MoS and Co9S8; and the material for said coating layer comprises lithium titanate (Li4Ti5O12). The composite negative electrode material for the lithium ion battery has high capacity, excellent cycling stability and durability. The embodiments of present invention also provide a preparation method for manufacturing said composite negative electrode material, and a lithium ion battery containing said composite negative electrode material.
Description
一种锂离子电池复合型负极材料及其制备方法和锂离子电池 本申请要求于 2012 年 9 月 26 日提交中国专利局的申请号为 201210362677.0, 其发明名称为 "一种锂离子电池复合型负极材料及其制备方法 和锂离子电池" 的中国专利申请的优先权， 其全部内容通过引用结合在本申请 中。 技术领域 Lithium-ion battery composite anode material, preparation method thereof and lithium ion battery The application No. 201210362677.0 submitted to the Chinese Patent Office on September 26, 2012, the invention name is "a lithium ion battery composite anode The material and its preparation method and the priority of the Chinese patent application of the lithium ion battery are hereby incorporated by reference in its entirety. Technical field
本发明涉及锂离子电池领域， 特别是涉及一种锂离子电池复合型负极材料 及其制备方法和锂离子电池。 背景技术 The present invention relates to the field of lithium ion batteries, and in particular to a lithium ion battery composite anode material, a preparation method thereof and a lithium ion battery. Background technique
自上世纪九十年代起， 在众多的能源替代产品中， 锂离子电池以较高的能 量密度、 良好的循环性能、 无记忆效应等特点受到人们的密切关注。 随着低碳 经济的方兴未艾， 锂离子电池正朝着动力汽车和电网储能等方向积极发展， 因 此， 开发能量密度高、 循环寿命长的锂离子电池已成为业界研究的重点。 Since the 1990s, among many energy substitutes, lithium-ion batteries have attracted close attention due to their high energy density, good cycle performance, and no memory effect. With the development of low-carbon economy, lithium-ion batteries are actively developing in the direction of power vehicles and grid energy storage. Therefore, the development of lithium-ion batteries with high energy density and long cycle life has become the focus of research in the industry.
目前商业化的锂离子电池大多采用碳系材料作为负极， 但碳系负极材料存 在很多缺陷， 例如， 首次充放电形成固体电解质界面膜（SEI )造成不可逆容量 损失， 循环性能不足， 存在高温失效风险和安全风险等， 这些问题使得碳系材 料已经无法满足储能电池的需求。 还有部分锂离子电池采用合金材料作为负极 材料， 合金材料虽然具有很高的比容量， 但是合金材料体积膨胀大， 循环性能 差， 无法满足市场化应用的需求。 At present, most commercial lithium-ion batteries use carbon-based materials as negative electrodes, but carbon-based anode materials have many defects. For example, the first charge and discharge forms a solid electrolyte interface film (SEI), causing irreversible capacity loss, insufficient cycle performance, and high temperature failure risk. And security risks, etc., these problems make carbon-based materials have been unable to meet the needs of energy storage batteries. Some lithium-ion batteries use alloy materials as the anode material. Although the alloy materials have a high specific capacity, the alloy materials have large volume expansion and poor cycle performance, which cannot meet the needs of market applications.
另外， 也有采用硫或硫化物（如 NiS, FeS2, FeS, TiS2 )材料作为负极储锂
电极材料的锂电池， 这些材料嵌锂容量高， 如 NiS和 FeS2的嵌锂容量为 600mAh/g 左右， 但这些材料循环性能较差， 原因是在充放电过程中， 硫化物活性物质易 发生团聚使得其循环性能降低， 且硫化物活性物质易与电解液反应而分解， 导 致可逆容量减少， 因此无法满足储能电池的高循环性能要求。 发明内容 In addition, sulfur or sulfide (such as NiS, FeS 2 , FeS, TiS 2 ) materials are also used as lithium storage for the negative electrode. Lithium batteries with electrode materials, these materials have high lithium insertion capacity. For example, the lithium insertion capacity of NiS and FeS 2 is about 600 mAh/g, but these materials have poor cycle performance because the sulfide active substances are prone to occur during charge and discharge. The agglomeration reduces the cycle performance, and the sulfide active material easily reacts with the electrolyte to decompose, resulting in a decrease in reversible capacity, and thus cannot meet the high cycle performance requirements of the energy storage battery. Summary of the invention
鉴于此，本发明实施例第一方面提供了一种锂离子电池复合型负极材料， 以 解决硫化物负极材料易团聚、 易与电解液反应而分解， 从而导致电池具有较低 的耐久性和循环性能的问题。 本发明实施例第二方面提供了一种锂离子电池复 合型负极材料的制备方法。 本发明实施例第三方面提供了一种锂离子电池。 In view of this, the first aspect of the embodiments of the present invention provides a lithium ion battery composite anode material, which solves the problem that the sulfide anode material is easily agglomerated and easily decomposed with the electrolyte, thereby causing the battery to have low durability and circulation. Performance issues. A second aspect of the embodiments of the present invention provides a method for preparing a composite material of a lithium ion battery composite type. A third aspect of the embodiments of the present invention provides a lithium ion battery.
第一方面，本发明实施例提供了一种锂离子电池复合型负极材料， 包括过渡 金属硫化物， 以及设置在所述过渡金属硫化物表面的包覆层， 所述过渡金属硫 化物为 NiS、 FeS2、 FeS、 TiS2、 MoS和 Co9S8中的一种或多种， 所述包覆层的 材料包括钛酸锂 Li4Ti5012。 In a first aspect, an embodiment of the present invention provides a lithium ion battery composite anode material, including a transition metal sulfide, and a coating layer disposed on a surface of the transition metal sulfide, wherein the transition metal sulfide is NiS, One or more of FeS 2 , FeS, TiS 2 , MoS and Co 9 S 8 , and the material of the coating layer includes lithium titanate Li 4 Ti 5 0 12 .
与现有技术相比，本发明提供的锂离子电池复合型负极材料由过渡金属硫化 物， 以及设置在过渡金属硫化物表面的包覆层组成， 其中， 过渡金属硫化物选 自 NiS (石 化镍）、 FeS2 (二石化铁）、 FeS (硫化亚铁）、 TiS2 (二石化钛）、 MoS (硫化钼）和 Co9S8 (硫化钴） 中的一种或多种。 这些过渡金属硫化物的嵌锂容 量高， 如 NiS和 FeS2的嵌锂容量为 600mAh/g左右， 因而能使锂离子电池复合 型负极材料具有较高的容量。 Compared with the prior art, the lithium ion battery composite anode material provided by the present invention is composed of a transition metal sulfide and a coating layer disposed on the surface of the transition metal sulfide, wherein the transition metal sulfide is selected from NiS (Petrified Nickel) One or more of FeS 2 (di-cobalt iron), FeS (ferrous sulfide), TiS 2 (di-titanium), MoS (molybdenum sulfide), and Co 9 S 8 (cobalt sulfide). These transition metal sulfides have a high lithium intercalation capacity, and the lithium intercalation capacity of NiS and FeS 2 is about 600 mAh/g, so that the lithium ion battery composite anode material can have a high capacity.
包覆层的材料包括钛酸锂 Li4Ti5012, 具有以下几大优势： （ 1 )钛酸锂为"零 应变，，电极材料， 根据 S.Schamer等人的研究结果 (J.of electrochemical society, 146(3),1999,857,861), 立方尖晶石结构的钛酸锂在锂离子嵌入-脱嵌过程中， 晶
格参数最大从 8.3595 A缩小到 8.3538 A, 晶格常数变化很小， 体积变化很小， 保 持了高度的结构稳定性， 因此具有优异的循环性能； （2 )钛酸锂具有三维锂离 子通道， 其锂离子扩散系数比碳系负极材料大一个数量级， 可提高锂电池的倍 率性能； （3 )钛酸锂的平衡电位约 1.55V, 可有效避免金属锂沉积， 提高了锂 离子电池的安全性能， 同时由于嵌锂电位高， 没有达到 SEI膜形成电位， 电解液 在钛酸锂表面基本不发生还原分解， 有利于维持电解液的稳定， 提高循环性能。 但是钛酸锂比容量低， 利用其制作的电池， 能量密度较低， 同时钛酸锂材料价 格较贵， 严重影响了钛酸锂为负极的电池的商业化使用。 The material of the cladding layer includes lithium titanate Li 4 Ti 5 0 12 , which has the following advantages: (1) lithium titanate is "zero strain, electrode material, according to the research results of S. Schamer et al. (J.of Electrochemical society, 146(3), 1999, 857, 861), cubic spinel lithium titanate during lithium ion intercalation-deintercalation, crystal The maximum lattice parameter is reduced from 8.3595 A to 8.3538 A. The lattice constant changes little, the volume change is small, and the structural stability is maintained, so it has excellent cycle performance. (2) Lithium titanate has a three-dimensional lithium ion channel. The lithium ion diffusion coefficient is one order of magnitude larger than that of the carbon-based anode material, which can improve the rate performance of the lithium battery; (3) The equilibrium potential of lithium titanate is about 1.55V, which can effectively prevent metal lithium deposition and improve the safety performance of the lithium ion battery. At the same time, due to the high lithium insertion potential, the SEI film formation potential is not reached, and the electrolyte does not undergo reductive decomposition on the surface of the lithium titanate, which is advantageous for maintaining the stability of the electrolyte and improving the cycle performance. However, lithium titanate has a low specific capacity, and the battery produced by the battery has a low energy density, and the lithium titanate material is expensive, which seriously affects the commercial use of lithium titanate as a negative electrode battery.
因此， 本发明将钛酸锂 Li4Ti5012包覆在所述过渡金属硫化物表面， 能将硫 化物表面的活性位点包覆， 从而有效保护过渡金属硫化物， 防止过渡金属硫化 物与电解液发生反应分解， 阻止硫化物发生团聚， 使锂离子电池复合型负极材 料具有高容量的同时， 具备良好的循环稳定性和耐久性。 此外， 由于钛酸锂Therefore, the present invention coats lithium titanate Li 4 Ti 5 0 12 on the surface of the transition metal sulfide, and can coat the active site on the surface of the sulfide, thereby effectively protecting the transition metal sulfide and preventing the transition metal sulfide. It reacts with the electrolyte to prevent decomposition of the sulfide, and the lithium ion battery composite anode material has high capacity and good cycle stability and durability. In addition, due to lithium titanate
1^41¾012具有三维锂离子通道，其锂离子扩散系数大， 因而可提高锂离子电池的 倍率性能。 且这些过渡金属硫化物材料的嵌锂电位与钛酸锂 Li4Ti5012接近， 因 而能使锂离子电池复合型负极材料具有平稳一致的充放电平台。 1^ 4 13⁄40 12 has a three-dimensional lithium ion channel with a large lithium ion diffusion coefficient, which can improve the rate performance of the lithium ion battery. Moreover, the lithium insertion potential of these transition metal sulfide materials is close to that of lithium titanate Li 4 Ti 5 0 12 , so that the lithium ion battery composite anode material can have a stable and uniform charge and discharge platform.
优选地， 所述包覆层的厚度为 50~8000nm。 更优选地， 所述包覆层的厚度 为 1000 ~ 4000nm。 Preferably, the coating layer has a thickness of 50 to 8000 nm. More preferably, the coating layer has a thickness of from 1000 to 4000 nm.
优选地， 所述过渡金属硫化物占所述锂离子电池复合型负极材料总质量的 10%~95%。 Preferably, the transition metal sulfide accounts for 10% to 95% of the total mass of the lithium ion battery composite anode material.
更优选地，所述过渡金属硫化物占所述锂萬子电池复合型负极材料总质量的 60% ~ 80%。 More preferably, the transition metal sulfide accounts for 60% to 80% of the total mass of the lithium-ion battery composite negative electrode material.
由于钛酸锂 Li4Ti5012具有较低的电子电导和离子电导能力， 因此为了提高 所述锂离子电池复合型负极材料的导电性能， 所述包覆层的材料可进一步包括
导电添加剂。 Since lithium titanate Li 4 Ti 5 0 12 has low electronic conductance and ionic conductivity, in order to improve the electrical conductivity of the lithium ion battery composite negative electrode material, the material of the coating layer may further include Conductive additive.
所述导电添加剂为人造石墨、 天然石墨、 乙炔黑、 炭黑、 中间相碳微球、 碳 纳米管、 碳纳米纤维、 酚醛树脂、 蔗糖中的一种或多种。 所述导电添加剂占所 述锂离子电池复合型负极材料总质量的 1%~5%。 The conductive additive is one or more of artificial graphite, natural graphite, acetylene black, carbon black, mesocarbon microbeads, carbon nanotubes, carbon nanofibers, phenolic resin, and sucrose. The conductive additive accounts for 1% to 5% of the total mass of the lithium ion battery composite negative electrode material.
本发明实施例第一方面提供的一种锂离子电池复合型负极材料， 具有高容 量， 且结构稳定， 不与电解液发生反应， 不发生团聚， 从而最终能使锂离子电 池具有较高的耐久性和循环稳定性； 另外， 由于钛酸锂 Li4Ti5012锂离子扩散系 数大， 因而可提高锂离子电池的倍率性能。 The lithium ion battery composite anode material provided by the first aspect of the present invention has high capacity, stable structure, does not react with the electrolyte, does not agglomerate, and finally can make the lithium ion battery have high durability. Properties and cycle stability; In addition, since the lithium titanate Li 4 Ti 5 0 12 has a large lithium ion diffusion coefficient, the rate performance of the lithium ion battery can be improved.
第二方面，本发明实施例提供了一种上述锂离子电池复合型负极材料的制备 方法， 包括以下步骤： In a second aspect, an embodiment of the present invention provides a method for preparing a lithium ion battery composite anode material, comprising the following steps:
( 1 )将包覆原料锂源、 钛源和待包覆的过渡金属硫化物在分散介质中搅拌 分散均匀， 制成浆料； (1) stirring and uniformly dispersing the coated raw material lithium source, the titanium source and the transition metal sulfide to be coated in a dispersion medium to form a slurry;
所述包覆原料锂源选自氢氧化锂、水合氢氧化锂、碳酸锂、硝酸锂、硫酸锂、 氟化锂、 草酸锂、 氯化锂和醋酸锂中的一种或几种； The coating raw material lithium source is selected from one or more selected from the group consisting of lithium hydroxide, lithium hydroxide hydrate, lithium carbonate, lithium nitrate, lithium sulfate, lithium fluoride, lithium oxalate, lithium chloride and lithium acetate;
所述包覆原料钛源选自二氧化钛、 四氯化钛、 三氯化钛、 异丙醇钛、 钛酸四 丁酯、 钛酸丁酯和钛酸正丙酯中的一种或多种； The coated raw material titanium source is selected from one or more of titanium dioxide, titanium tetrachloride, titanium trichloride, titanium isopropoxide, tetrabutyl titanate, butyl titanate and n-propyl titanate;
所述过渡金属石 υ化物选自 NiS、 FeS2、 FeS、 TiS2、 MoS和 Co9S8中的一种或 多种； The transition metal sulphate is selected from one or more of NiS, FeS 2 , FeS, TiS 2 , MoS, and Co 9 S 8 ;
所述分散介质选自水、 Ν,Ν-二曱基曱酰胺 (DMF)、 Ν,Ν-二曱基乙酰胺 (DMAc)、 N-2-曱基吡咯烷酮 (NMP)、 四氢呋喃 (THF)、 乙醇和曱醇中的一种或多 种； The dispersion medium is selected from the group consisting of water, hydrazine, hydrazine-dimercaptoamide (DMF), hydrazine, hydrazine-dimercaptoacetamide (DMAc), N-2-mercaptopyrrolidone (NMP), tetrahydrofuran (THF), One or more of ethanol and sterol;
( 2 )将得到的所述浆料通过溶胶 -凝胶法、 水热反应法、 微波化学法或高 温固相法进行包覆制得锂离子电池复合型负极材料； 所述锂离子电池复合型负
极材料包括所述过渡金属硫化物， 以及包覆在所述过渡金属硫化物表面的包覆 层， 所述包覆层的材料包括钛酸锂 Li4Ti5012。 (2) the obtained slurry is coated by a sol-gel method, a hydrothermal reaction method, a microwave chemical method or a high-temperature solid phase method to obtain a lithium ion battery composite anode material; the lithium ion battery composite type Negative The pole material includes the transition metal sulfide, and a coating layer coated on the surface of the transition metal sulfide, and the material of the coating layer includes lithium titanate Li 4 Ti 5 0 12 .
优选地， 所述包覆层的厚度为 50~8000nm。 更优选地， 所述包覆层的厚度 为 1000 ~ 4000nm。 Preferably, the coating layer has a thickness of 50 to 8000 nm. More preferably, the coating layer has a thickness of from 1000 to 4000 nm.
优选地， 所述过渡金属硫化物占所述锂离子电池复合型负极材料总质量的 10%~95%。 Preferably, the transition metal sulfide accounts for 10% to 95% of the total mass of the lithium ion battery composite anode material.
更优选地，所述过渡金属硫化物占所述锂萬子电池复合型负极材料总质量的 60% ~ 80%。 More preferably, the transition metal sulfide accounts for 60% to 80% of the total mass of the lithium-ion battery composite negative electrode material.
所述溶胶-凝胶法的具体操作为： 将所述浆料在 60~80°C下干燥， 得到前驱 体材料，将所述前驱体材料置于马氟炉中 500~700°C烧结 1~5小时， 随炉冷却至 室温， 即得到锂离子电池复合型负极材料。 The specific operation of the sol-gel method is as follows: drying the slurry at 60-80 ° C to obtain a precursor material, and placing the precursor material in a fluorocarbon furnace at 500-700 ° C for sintering 1 ~5 hours, after cooling to room temperature with the furnace, a lithium ion battery composite anode material is obtained.
所述水热反应法的具体操作为： 将所述浆料转入水热反应釜中， 在 150~160 °C下水热离子交换反应 8~12h , 得到黑色沉淀， 再将黑色沉淀置于 500~600°C的马弗炉中热处理 l~3h, 随炉冷却至室温， 即得到所述锂离子电池复 合型负极材料。 The specific operation of the hydrothermal reaction method is: transferring the slurry into a hydrothermal reaction kettle, and performing a hydrothermal ion exchange reaction at 150 to 160 ° C for 8 to 12 hours to obtain a black precipitate, and then placing the black precipitate at 500. The heat treatment in the muffle furnace of ~600 ° C for 1~3 h, and the furnace is cooled to room temperature to obtain the lithium ion battery composite anode material.
所述微波化学法的具体操作为： 将所述浆料在 100~120°C下干燥， 得到前驱 体材料， 将所述前驱体材料置于工业微波炉中， 以 10°C/min升温到 600~800°C , 保温 1~4小时， 随炉冷却， 即得到所述锂离子电池复合型负极材料。 所述高温固相法的具体操作为： 将所述浆料在 100~120°C下干燥， 得到前驱 体材料， 将所述前驱体材料置于马弗炉中在 400~900°C下烧结 0.5~10小时， 随 炉冷却， 即得到所述锂离子电池复合型负极材料。 The specific operation of the microwave chemical method is as follows: drying the slurry at 100-120 ° C to obtain a precursor material, placing the precursor material in an industrial microwave oven, and heating to 600 at 10 ° C / min. ~800 ° C, heat preservation for 1 to 4 hours, with the furnace cooling, the lithium ion battery composite anode material is obtained. The specific operation of the high-temperature solid phase method is: drying the slurry at 100-120 ° C to obtain a precursor material, and the precursor material is placed in a muffle furnace and sintered at 400-900 ° C. 0.5 to 10 hours, the furnace is cooled, and the lithium ion battery composite anode material is obtained.
其中， 关于过渡金属硫化物和钛酸锂 Li4Ti5012的具体叙述如前文所述， 此
处不再赘述。 Here, the specific description of the transition metal sulfide and lithium titanate Li 4 Ti 5 0 12 is as described above, I won't go into details here.
为了提高所述锂离子电池复合型负极材料的导电性能，所述包覆原料可进一 步包括导电添加剂， 即在步骤（1 ) 中加入导电添加剂， 与锂源、 钛源和待包覆 的过渡金属硫化物均匀分散在分散介质中， 制成浆料。 In order to improve the electrical conductivity of the lithium ion battery composite anode material, the coating material may further include a conductive additive, that is, a conductive additive is added in the step (1), and a lithium source, a titanium source, and a transition metal to be coated. The sulfide is uniformly dispersed in a dispersion medium to form a slurry.
所述导电添加剂为人造石墨、 天然石墨、 乙炔黑、 炭黑、 中间相碳微球、 碳 纳米管、 碳纳米纤维、 酚醛树脂、 蔗糖中的一种或多种。 所述导电添加剂占所 述锂离子电池复合型负极材料总质量的 1%~5%。 The conductive additive is one or more of artificial graphite, natural graphite, acetylene black, carbon black, mesocarbon microbeads, carbon nanotubes, carbon nanofibers, phenolic resin, and sucrose. The conductive additive accounts for 1% to 5% of the total mass of the lithium ion battery composite negative electrode material.
本发明实施例第二方面提供的一种锂离子电池复合型负极材料的制备方 法， 筒单易行， 制得的锂离子电池复合型负极材料具有高容量， 且结构稳定， 不与电解液发生反应， 不发生团聚， 锂离子扩散系数大， 从而能使锂离子电池 具有较高的耐久性和循环稳定性， 可提高锂离子电池的倍率性能。 A method for preparing a composite material of a lithium ion battery composite anode provided by the second aspect of the present invention provides a high capacity and a stable structure of the lithium ion battery composite anode material, which does not react with the electrolyte. The reaction, no agglomeration, and a large lithium ion diffusion coefficient, can make the lithium ion battery have high durability and cycle stability, and can improve the rate performance of the lithium ion battery.
第三方面，本发明实施例提供了一种锂离子电池，该锂离子电池包含本发明 实施例第一方面提供的锂离子电池复合型负极材料。 In a third aspect, an embodiment of the present invention provides a lithium ion battery comprising the lithium ion battery composite anode material provided by the first aspect of the embodiments of the present invention.
本发明实施例第三方面提供的锂离子电池循环寿命长，并且具有优良的放电 容量和倍率性能。 The lithium ion battery provided by the third aspect of the embodiment of the present invention has a long cycle life and has excellent discharge capacity and rate performance.
本发明实施例的优点将会在下面的说明书中部分阐明，一部分根据说明书是 显而易见的， 或者可以通过本发明实施例的实施而获知。 The advantages of the embodiments of the present invention will be set forth in part in the description which follows.
附图说明 DRAWINGS
图 1是本发明实施例一与对比例一所得锂离子电池的循环性能对比图； 图 2是本发明实施例二与对比例二所得锂离子电池的循环性能对比图； 图 3是本发明实施例三与对比例三所得锂离子电池的循环性能对比图； 图 4是本发明实施例四与对比例四所得锂离子电池的循环性能对比图；
图 5是本发明实施例五与对比例五所得锂离子电池的循环性能对比图。 具体实施方式 1 is a comparison of cycle performance of a lithium ion battery obtained in Example 1 of the present invention and Comparative Example 1. FIG. 2 is a comparison diagram of cycle performance of a lithium ion battery obtained in Example 2 and Comparative Example 2 of the present invention; FIG. 3 is an embodiment of the present invention. Figure 3 is a comparison chart of the cycle performance of the lithium ion battery obtained in Example 3 and Comparative Example 3; Figure 4 is a comparison chart of the cycle performance of the lithium ion battery obtained in Example 4 and Comparative Example 4 of the present invention; Figure 5 is a graph showing the cycle performance of a lithium ion battery obtained in Example 5 and Comparative Example 5 of the present invention. detailed description
以下所述是本发明实施例的优选实施方式，应当指出，对于本技术领域的普 通技术人员来说， 在不脱离本发明实施例原理的前提下， 还可以做出若干改进 和润饰， 这些改进和润饰也视为本发明实施例的保护范围。 The following are the preferred embodiments of the embodiments of the present invention, and it should be noted that those skilled in the art can make some improvements and refinements without departing from the principles of the embodiments of the present invention. And retouching is also considered to be the scope of protection of the embodiments of the present invention.
本发明实施例第一方面提供了一种锂离子电池复合型负极材料，以解决石 υ化 物负极材料易团聚、 易与电解液反应而分解， 从而导致电池具有较低的耐久性 和循环性能的问题。 本发明实施例第二方面提供了一种锂离子电池复合型负极 材料的制备方法。 本发明实施例第三方面提供了一种锂离子电池。 A first aspect of the embodiments of the present invention provides a lithium ion battery composite anode material, which solves the problem that the stone telluride anode material is easily agglomerated and easily reacted with the electrolyte to decompose, thereby causing the battery to have low durability and cycle performance. problem. A second aspect of the embodiments of the present invention provides a method for preparing a lithium ion battery composite anode material. A third aspect of the embodiments of the present invention provides a lithium ion battery.
第一方面，本发明实施例提供了一种锂离子电池复合型负极材料， 包括过渡 金属硫化物， 以及设置在所述过渡金属硫化物表面的包覆层， 所述过渡金属硫 化物为 NiS、 FeS2、 FeS、 TiS2、 MoS和 Co9S8中的一种或多种， 所述包覆层的 材料包括钛酸锂 Li4Ti5012。 In a first aspect, an embodiment of the present invention provides a lithium ion battery composite anode material, including a transition metal sulfide, and a coating layer disposed on a surface of the transition metal sulfide, wherein the transition metal sulfide is NiS, One or more of FeS 2 , FeS, TiS 2 , MoS and Co 9 S 8 , and the material of the coating layer includes lithium titanate Li 4 Ti 5 0 12 .
与现有技术相比，本发明提供的锂离子电池复合型负极材料由过渡金属硫化 物， 以及设置在过渡金属硫化物表面的包覆层组成， 其中， 过渡金属硫化物选 自 NiS (石 化镍）、 FeS2 (二石化铁）、 FeS (硫化亚铁）、 TiS2 (二石化钛）、 MoS (硫化钼）和 Co9S8 (硫化钴） 中的一种或多种。 这些过渡金属硫化物的嵌锂容 量高， 如 NiS和 FeS2的嵌锂容量为 600mAh/g左右， 因而能使锂离子电池复合 型负极材料具有较高的容量。 Compared with the prior art, the lithium ion battery composite anode material provided by the present invention is composed of a transition metal sulfide and a coating layer disposed on the surface of the transition metal sulfide, wherein the transition metal sulfide is selected from NiS (Petrified Nickel) One or more of FeS 2 (di-cobalt iron), FeS (ferrous sulfide), TiS 2 (di-titanium), MoS (molybdenum sulfide), and Co 9 S 8 (cobalt sulfide). These transition metal sulfides have a high lithium intercalation capacity, and the lithium intercalation capacity of NiS and FeS 2 is about 600 mAh/g, so that the lithium ion battery composite anode material can have a high capacity.
包覆层的材料包括钛酸锂 Li4Ti5012, 具有以下几大优势： （ 1 )钛酸锂为"零 应变，，电极材料， 根据 S.Schamer等人的研究结果 (J.of electrochemical society, 146(3),1999,857,861), 立方尖晶石结构的钛酸锂在锂离子嵌入-脱嵌过程中， 晶
格参数最大从 8.3595 A缩小到 8.3538 A, 晶格常数变化很小， 体积变化很小， 保 持了高度的结构稳定性， 因此具有优异的循环性能； （2 )钛酸锂具有三维锂离 子通道， 其锂离子扩散系数比碳系负极材料大一个数量级， 可提高锂电池的倍 率性能； （3 )钛酸锂的平衡电位约 1.55V, 可有效避免金属锂沉积， 提高了锂 离子电池的安全性能， 同时由于嵌锂电位高， 没有达到 SEI膜形成电位， 电解液 在钛酸锂表面基本不发生还原分解， 有利于维持电解液的稳定， 提高循环性能。 但是钛酸锂比容量低， 利用其制作的电池， 能量密度较低， 同时钛酸锂材料价 格较贵， 严重影响了钛酸锂为负极的电池的商业化使用。 The material of the cladding layer includes lithium titanate Li 4 Ti 5 0 12 , which has the following advantages: (1) lithium titanate is "zero strain, electrode material, according to the research results of S. Schamer et al. (J.of Electrochemical society, 146(3), 1999, 857, 861), cubic spinel lithium titanate during lithium ion intercalation-deintercalation, crystal The maximum lattice parameter is reduced from 8.3595 A to 8.3538 A. The lattice constant changes little, the volume change is small, and the structural stability is maintained, so it has excellent cycle performance. (2) Lithium titanate has a three-dimensional lithium ion channel. The lithium ion diffusion coefficient is one order of magnitude larger than that of the carbon-based anode material, which can improve the rate performance of the lithium battery; (3) The equilibrium potential of lithium titanate is about 1.55V, which can effectively prevent metal lithium deposition and improve the safety performance of the lithium ion battery. At the same time, due to the high lithium insertion potential, the SEI film formation potential is not reached, and the electrolyte does not undergo reductive decomposition on the surface of the lithium titanate, which is advantageous for maintaining the stability of the electrolyte and improving the cycle performance. However, lithium titanate has a low specific capacity, and the battery produced by the battery has a low energy density, and the lithium titanate material is expensive, which seriously affects the commercial use of lithium titanate as a negative electrode battery.
因此， 本发明将钛酸锂 Li4Ti5012包覆在所述过渡金属硫化物表面， 能将硫 化物表面的活性位点包覆， 从而有效保护过渡金属硫化物， 防止过渡金属硫化 物与电解液发生反应分解， 阻止硫化物发生团聚， 使锂离子电池复合型负极材 料具有高容量的同时， 具备良好的循环稳定性和耐久性。 此外， 由于钛酸锂Therefore, the present invention coats lithium titanate Li 4 Ti 5 0 12 on the surface of the transition metal sulfide, and can coat the active site on the surface of the sulfide, thereby effectively protecting the transition metal sulfide and preventing the transition metal sulfide. It reacts with the electrolyte to prevent decomposition of the sulfide, and the lithium ion battery composite anode material has high capacity and good cycle stability and durability. In addition, due to lithium titanate
1^41¾012具有三维锂离子通道，其锂离子扩散系数大， 因而可提高锂离子电池的 倍率性能。 且这些过渡金属硫化物材料的嵌锂电位与钛酸锂 Li4Ti5012接近， 因 而能使锂离子电池复合型负极材料具有平稳一致的充放电平台。 1^ 4 13⁄40 12 has a three-dimensional lithium ion channel with a large lithium ion diffusion coefficient, which can improve the rate performance of the lithium ion battery. Moreover, the lithium insertion potential of these transition metal sulfide materials is close to that of lithium titanate Li 4 Ti 5 0 12 , so that the lithium ion battery composite anode material can have a stable and uniform charge and discharge platform.
本发明实施例对所述过渡金属硫化物在锂离子电池复合型负极材料中的位 置没有限制， 被包覆于所述包覆层内即可； 本发明实施例对所述过渡金属硫化 物的颗粒大小没有特殊限制， 能被包覆于所述包覆层内即可。 The embodiment of the present invention has no limitation on the position of the transition metal sulfide in the lithium ion battery composite anode material, and is coated in the coating layer; the embodiment of the present invention is applicable to the transition metal sulfide. The particle size is not particularly limited and can be coated in the coating layer.
所述包覆层的厚度为 50~8000nm。 本实施方式中， 所述包覆层的厚度为 1000 ~ 4000nm。 The coating layer has a thickness of 50 to 8000 nm. In the embodiment, the thickness of the coating layer is 1000 to 4000 nm.
所述过渡金属硫化物占所述锂离子电池复合型负极材料总质量的 10%~95%。 The transition metal sulfide accounts for 10% to 95% of the total mass of the lithium ion battery composite anode material.
本实施方式中，所述过渡金属硫化物占所述锂离子电池复合型负极材料总质
量的 60 % ~ 80 %。 所述过渡金属石充化物选自 NiS (石充化镍）、 FeS2 (二石充化铁）、 FeS (石充化亚 铁）、 TlS2 (二石化钛）、 MoS (石 υ化钼）和 C09S8 (石 化钴） 中的一种或多种。 当过渡金属石 υ化物为两种或两种以上时， 不同过渡金属石 化物之间的比例没有 特殊限制。 In this embodiment, the transition metal sulfide accounts for the total mass of the lithium ion battery composite anode material. 60% ~ 80% of the amount. The transition metallite filler is selected from the group consisting of NiS (stone-filled nickel), FeS 2 (two-stone iron), FeS (stone-filled ferrous), TlS 2 (di-titanized titanium), MoS (diazepine molybdenum) And one or more of C0 9 S 8 (Petrified Cobalt). When the transition metal stone telluride is two or more kinds, the ratio between the different transition metal petrochemicals is not particularly limited.
由于钛酸锂 Li4Ti5012具有较低的电子电导和离子电导能力， 因此为了提高 所述锂离子电池复合型负极材料的导电性能， 所述包覆层的材料可进一步包括 导电添加剂。 Since the lithium titanate Li 4 Ti 5 0 12 has low electron conductance and ion conductivity, the material of the cladding layer may further include a conductive additive in order to improve the conductivity of the lithium ion battery composite anode material.
所述导电添加剂为人造石墨、 天然石墨、 乙炔黑、 炭黑、 中间相碳微球、 碳 纳米管、 碳纳米纤维、 酚醛树脂、 蔗糖中的一种或多种。 所述导电添加剂占所 述锂离子电池复合型负极材料总质量的 1%~5%。 The conductive additive is one or more of artificial graphite, natural graphite, acetylene black, carbon black, mesocarbon microbeads, carbon nanotubes, carbon nanofibers, phenolic resin, and sucrose. The conductive additive accounts for 1% to 5% of the total mass of the lithium ion battery composite negative electrode material.
所述导电添加剂均匀分布于所述包覆层中， 位于钛酸锂 Li4Ti5012材料附近， 即导电添加剂均匀掺入钛酸锂 Li4Ti5012材料中， 在所述过渡金属石 A化物表面形 成混合包覆层。 The conductive additive is evenly distributed in the coating layer, located in the vicinity of the lithium titanate Li 4 Ti 5 0 12 material, that is, the conductive additive is uniformly incorporated into the lithium titanate Li 4 Ti 5 0 12 material, in the transition metal The surface of the stone A compound forms a mixed coating layer.
本发明实施例第一方面提供的一种锂离子电池复合型负极材料， 具有高容 量， 且结构稳定， 不与电解液发生反应， 不发生团聚， 从而最终能使锂离子电 池具有较高的耐久性和循环稳定性； 另外， 由于钛酸锂 Li4Ti5012锂离子扩散系 数大， 因而可提高锂离子电池的倍率性能。 The lithium ion battery composite anode material provided by the first aspect of the present invention has high capacity, stable structure, does not react with the electrolyte, does not agglomerate, and finally can make the lithium ion battery have high durability. Properties and cycle stability; In addition, since the lithium titanate Li 4 Ti 5 0 12 has a large lithium ion diffusion coefficient, the rate performance of the lithium ion battery can be improved.
第二方面，本发明实施例提供了一种上述锂离子电池复合型负极材料的制备 方法， 包括以下步骤： In a second aspect, an embodiment of the present invention provides a method for preparing a lithium ion battery composite anode material, comprising the following steps:
( 1 )将包覆原料锂源、 钛源和待包覆的过渡金属硫化物在分散介质中搅拌 分散均匀， 制成浆料； (1) stirring and uniformly dispersing the coated raw material lithium source, the titanium source and the transition metal sulfide to be coated in a dispersion medium to form a slurry;
所述包覆原料锂源选自氢氧化锂、水合氢氧化锂、碳酸锂、硝酸锂、硫酸锂、
氟化锂、 草酸锂、 氯化锂和醋酸锂中的一种或几种； The lithium source of the coating raw material is selected from the group consisting of lithium hydroxide, lithium hydroxide hydrate, lithium carbonate, lithium nitrate, lithium sulfate, One or more of lithium fluoride, lithium oxalate, lithium chloride and lithium acetate;
所述包覆原料钛源选自二氧化钛、 四氯化钛、 三氯化钛、 异丙醇钛、 钛酸四 丁酯、 钛酸丁酯和钛酸正丙酯中的一种或多种； The coated raw material titanium source is selected from one or more of titanium dioxide, titanium tetrachloride, titanium trichloride, titanium isopropoxide, tetrabutyl titanate, butyl titanate and n-propyl titanate;
所述过渡金属石 υ化物选自 NiS、 FeS2、 FeS、 TiS2、 MoS和 Co9S8中的一种或 多种； The transition metal sulphate is selected from one or more of NiS, FeS 2 , FeS, TiS 2 , MoS, and Co 9 S 8 ;
所述分散介质选自水、 Ν,Ν-二曱基曱酰胺 (DMF)、 Ν,Ν-二曱基乙酰胺 (DMAc)、 N-2-曱基吡咯烷酮 (NMP)、 四氢呋喃 (THF)、 乙醇和曱醇中的一种或多 种； The dispersion medium is selected from the group consisting of water, hydrazine, hydrazine-dimercaptoamide (DMF), hydrazine, hydrazine-dimercaptoacetamide (DMAc), N-2-mercaptopyrrolidone (NMP), tetrahydrofuran (THF), One or more of ethanol and sterol;
( 2 )将得到的所述浆料通过溶胶 -凝胶法、 水热反应法、 微波化学法或高 温固相法进行包覆制得锂离子电池复合型负极材料； 所述锂离子电池复合型负 极材料包括所述过渡金属硫化物， 以及包覆在所述过渡金属硫化物表面的包覆 层， 所述包覆层的材料包括钛酸锂 Li4Ti5012。 (2) the obtained slurry is coated by a sol-gel method, a hydrothermal reaction method, a microwave chemical method or a high-temperature solid phase method to obtain a lithium ion battery composite anode material; the lithium ion battery composite type The negative electrode material includes the transition metal sulfide, and a coating layer coated on the surface of the transition metal sulfide, and the material of the coating layer includes lithium titanate Li 4 Ti 5 0 12 .
本发明实施例对所述过渡金属硫化物在锂离子电池复合型负极材料中的位 置没有限制， 被包覆于所述包覆层内即可； 本发明实施例对所述过渡金属硫化 物的颗粒大小没有特殊限制， 能被包覆于所述包覆层内即可。 The embodiment of the present invention has no limitation on the position of the transition metal sulfide in the lithium ion battery composite anode material, and is coated in the coating layer; the embodiment of the present invention is applicable to the transition metal sulfide. The particle size is not particularly limited and can be coated in the coating layer.
所述包覆层的厚度为 50~8000nm。 本实施方式中， 所述包覆层的厚度为 1000 ~ 4000nm。 The coating layer has a thickness of 50 to 8000 nm. In the embodiment, the thickness of the coating layer is 1000 to 4000 nm.
所述过渡金属硫化物占所述锂离子电池复合型负极材料总质量的 10%~95%。 The transition metal sulfide accounts for 10% to 95% of the total mass of the lithium ion battery composite anode material.
本实施方式中，所述过渡金属硫化物占所述锂离子电池复合型负极材料总质 量的 60 % ~ 80 %。 In this embodiment, the transition metal sulfide accounts for 60% to 80% of the total mass of the lithium ion battery composite negative electrode material.
所述过渡金属石充化物选自 NiS (石充化镍）、 FeS2 (二石充化铁）、 FeS (石充化亚 铁）、 TlS2 (二石化钛）、 MoS (石 υ化钼）和 C09S8 (石 化钴） 中的一种或多种。
当过渡金属石 υ化物为两种或两种以上时， 不同过渡金属石 化物之间的比例没有 特殊限制。 The transition metallite filler is selected from the group consisting of NiS (stone-filled nickel), FeS 2 (two-stone iron), FeS (stone-filled ferrous), TlS 2 (di-titanized titanium), MoS (diazepine molybdenum) And one or more of C0 9 S 8 (Petrified Cobalt). When the transition metal stone telluride is two or more kinds, the ratio between the different transition metal petrochemicals is not particularly limited.
所述包覆原料锂源和钛源按钛酸锂 Li4Ti5012的化学计量比加入。 The coated raw material lithium source and the titanium source are added in a stoichiometric ratio of lithium titanate Li 4 Ti 5 0 12 .
所述分散介质选自水、 Ν,Ν-二曱基曱酰胺 (DMF)、 Ν,Ν-二曱基乙酰胺 (DMAc)、 N-2-曱基吡咯烷酮 (NMP)、 四氢呋喃 (THF)、 乙醇和曱醇中的一种或多 种。 当分散介质为两种或两种以上混合使用时， 不同分散介质之间的比例没有 特殊限制。 The dispersion medium is selected from the group consisting of water, hydrazine, hydrazine-dimercaptoamide (DMF), hydrazine, hydrazine-dimercaptoacetamide (DMAc), N-2-mercaptopyrrolidone (NMP), tetrahydrofuran (THF), One or more of ethanol and sterol. When the dispersion medium is used in combination of two or more kinds, the ratio between the different dispersion mediums is not particularly limited.
所述溶胶-凝胶法的具体操作为： 将所述浆料在 60~80°C下干燥， 得到前驱 体材料，将所述前驱体材料置于马氟炉中 500~700°C烧结 1~5小时， 随炉冷却至 室温， 即得到锂离子电池复合型负极材料。 The specific operation of the sol-gel method is as follows: drying the slurry at 60-80 ° C to obtain a precursor material, and placing the precursor material in a fluorocarbon furnace at 500-700 ° C for sintering 1 ~5 hours, after cooling to room temperature with the furnace, a lithium ion battery composite anode material is obtained.
所述水热反应法的具体操作为： 将所述浆料转入水热反应釜中， 在 150~160 °C下水热离子交换反应 8~12h , 得到黑色沉淀， 再将黑色沉淀置于 500~600°C的马弗炉中热处理 l~3h, 随炉冷却至室温， 即得到所述锂离子电池复 合型负极材料。 The specific operation of the hydrothermal reaction method is: transferring the slurry into a hydrothermal reaction kettle, and performing a hydrothermal ion exchange reaction at 150 to 160 ° C for 8 to 12 hours to obtain a black precipitate, and then placing the black precipitate at 500. The heat treatment in the muffle furnace of ~600 ° C for 1~3 h, and the furnace is cooled to room temperature to obtain the lithium ion battery composite anode material.
所述微波化学法的具体操作为： 将所述浆料在 100~120°C下干燥， 得到前驱 体材料， 将所述前驱体材料置于工业微波炉中， 以 10°C/min升温到 600~800°C , 保温 1~4小时， 随炉冷却， 即得到所述锂离子电池复合型负极材料。 The specific operation of the microwave chemical method is as follows: drying the slurry at 100-120 ° C to obtain a precursor material, placing the precursor material in an industrial microwave oven, and heating to 600 at 10 ° C / min. ~800 ° C, heat preservation for 1 to 4 hours, with the furnace cooling, the lithium ion battery composite anode material is obtained.
所述高温固相法的具体操作为： 将所述浆料在 100~120°C下干燥， 得到前驱 体材料， 将所述前驱体材料置于马弗炉中在 400~900°C下烧结 0.5~10小时， 随 炉冷却， 即得到所述锂离子电池复合型负极材料。 The specific operation of the high-temperature solid phase method is: drying the slurry at 100-120 ° C to obtain a precursor material, and the precursor material is placed in a muffle furnace and sintered at 400-900 ° C. 0.5 to 10 hours, the furnace is cooled, and the lithium ion battery composite anode material is obtained.
其中， 关于过渡金属硫化物和钛酸锂 Li4Ti5012的具体叙述如前文所述， 此 处不再赘述。 Here, the specific description of the transition metal sulfide and lithium titanate Li 4 Ti 5 0 12 is as described above, and will not be described herein.
为了提高所述锂离子电池复合型负极材料的导电性能，所述包覆原料可进一
步包括导电添加剂， 即在步骤（1 ) 中加入导电添加剂， 与锂源、 钛源和待包覆 的过渡金属硫化物均匀分散在分散介质中， 制成浆料。 In order to improve the electrical conductivity of the lithium ion battery composite anode material, the coating material may be further The step includes a conductive additive, that is, a conductive additive is added in the step (1), and a lithium source, a titanium source, and a transition metal sulfide to be coated are uniformly dispersed in the dispersion medium to prepare a slurry.
所述导电添加剂为人造石墨、 天然石墨、 乙炔黑、 炭黑、 中间相碳微球、 碳 纳米管、 碳纳米纤维、 酚醛树脂、 蔗糖中的一种或多种。 所述导电添加剂占所 述锂离子电池复合型负极材料总质量的 1%~5%。 The conductive additive is one or more of artificial graphite, natural graphite, acetylene black, carbon black, mesocarbon microbeads, carbon nanotubes, carbon nanofibers, phenolic resin, and sucrose. The conductive additive accounts for 1% to 5% of the total mass of the lithium ion battery composite negative electrode material.
所述导电添加剂均匀分布于所述包覆层中， 位于钛酸锂 Li4Ti5012材料附近， 即导电添加剂均匀掺入钛酸锂 Li4Ti5012材料中， 在所述过渡金属石 A化物表面形 成混合包覆层。 The conductive additive is evenly distributed in the coating layer, located in the vicinity of the lithium titanate Li 4 Ti 5 0 12 material, that is, the conductive additive is uniformly incorporated into the lithium titanate Li 4 Ti 5 0 12 material, in the transition metal The surface of the stone A compound forms a mixed coating layer.
本发明实施例第二方面提供的一种锂离子电池复合型负极材料的制备方 法， 筒单易行， 制得的锂离子电池复合型负极材料具有高容量， 且结构稳定， 不与电解液发生反应， 不发生团聚， 锂离子扩散系数大， 从而能使锂离子电池 具有较高的耐久性和循环稳定性， 可提高锂离子电池的倍率性能。 A method for preparing a composite material of a lithium ion battery composite anode provided by the second aspect of the present invention provides a high capacity and a stable structure of the lithium ion battery composite anode material, which does not react with the electrolyte. The reaction, no agglomeration, and a large lithium ion diffusion coefficient, can make the lithium ion battery have high durability and cycle stability, and can improve the rate performance of the lithium ion battery.
第三方面，本发明实施例提供了一种锂离子电池，该锂离子电池包含本发明 实施例第一方面提供的锂离子电池复合型负极材料。 In a third aspect, an embodiment of the present invention provides a lithium ion battery comprising the lithium ion battery composite anode material provided by the first aspect of the embodiments of the present invention.
本发明实施例第三方面提供的锂离子电池循环寿命长，并且具有优良的放电 容量和倍率性能。 The lithium ion battery provided by the third aspect of the embodiment of the present invention has a long cycle life and has excellent discharge capacity and rate performance.
下面分多个实施例对本发明实施例进行进一步的说明。 其中， 本发明实施 例不限定于以下的具体实施例。 在不变主权利的范围内， 可以适当的进行变更 实施。 The embodiments of the present invention are further described below in various embodiments. However, the embodiments of the present invention are not limited to the specific embodiments below. Changes may be implemented as appropriate within the scope of the unchanging primary rights.
实施例一 Embodiment 1
一种锂离子电池复合型负极材料的制备方法 Method for preparing lithium ion battery composite anode material
( 1 )称取水合氢氧化锂（LiOH . H20 ) 8.4g、 二氧化钛 20g分散于 150mL 的去离子水中， 加入 2.3g 乙炔黑分散均勾； 再加入 89.7g石 υ化镍充分搅拌分散
均匀， 得到稠状浆料； (1) Weigh 8.4g of hydrated lithium hydroxide (LiOH. H 2 0 ), 20g of titanium dioxide dispersed in 150mL of deionized water, add 2.3g of acetylene black to disperse and hook; then add 89.7g of nickel samarium carbide to stir and disperse Evenly, a thick slurry is obtained;
( 2 )将浆料在 110°C干燥炉中干燥得到前驱体材料， 将前驱体材料置于工业 微波炉内， 以 10°C/min的速率升温到 700°C , 保温 1小时， 随炉冷却至室温， 得到钛酸锂 Li4Ti5012包覆硫化镍（NiS ) 的锂离子电池复合型负极材料。 (2) drying the slurry in a drying oven at 110 ° C to obtain a precursor material, placing the precursor material in an industrial microwave oven, heating to 700 ° C at a rate of 10 ° C / min, holding for 1 hour, cooling with the furnace To the room temperature, a lithium ion battery composite negative electrode material in which lithium titanate Li 4 Ti 5 0 12 was coated with nickel sulfide (NiS) was obtained.
锂离子电池的制备方法 Method for preparing lithium ion battery
将本实施例所得锂离子电池复合型负极材料、 导电炭黑、 粘结剂聚偏氟乙 婦 PVDF, 按质量比 92: 4: 4在 N-2-曱基吡咯綻酮（NMP ) 中混合均匀， 得到 混合浆料， 将混合浆料涂于 16um的铝箔上， 干燥后裁剪成极片， 以锂片为对电 极， 组装成 CR2032型扣式电池。 封装电池在氩气气氛的手套箱中进行， 电解液 采用 lmol/L LiPF6的 EC:DMC (体积比为 1: 1 )混合液， 隔膜采用 Celgard2400。 实施例二 The lithium ion battery composite anode material obtained in the present embodiment, the conductive carbon black, and the binder polyvinylidene fluoride PVDF are mixed in a mass ratio of 92:4:4 in N-2-mercaptopyrrolidone (NMP). Evenly, a mixed slurry was obtained, and the mixed slurry was applied to a 16 um aluminum foil, dried, and then cut into a pole piece, and a lithium piece was used as a counter electrode to assemble a CR2032 type button battery. The packaged battery was carried out in a glove box under an argon atmosphere using an EC:DMC (1:1 ratio by volume) mixture of 1 mol/L LiPF 6 and a Celgard 2400 separator. Embodiment 2
一种锂离子电池复合型负极材料的制备方法 Method for preparing lithium ion battery composite anode material
( 1 )将 13g碳酸锂均匀分散至 500mL水和无水乙醇溶液中（其中水和乙醇的 体积比为 4: 1), 按照 Ti: Li为 5: 4的摩尔比量取钛酸丁酯 75mL, 用 80mL 无水乙醇稀释后， 加到分散有碳酸锂的乙醇水溶液中， 搅拌均匀后再加入 176g 二硫化铁充分搅拌分散均匀， 得到混合浆料； (1) uniformly disperse 13 g of lithium carbonate in 500 mL of water and absolute ethanol (wherein the volume ratio of water to ethanol is 4:1), and take butyl titanate 75 mL in a molar ratio of Ti: Li of 5:4. After diluting with 80 mL of absolute ethanol, adding it to an aqueous solution of lithium carbonate dispersed in ethanol, stirring uniformly, and then adding 176 g of iron disulfide, stirring and dispersing uniformly to obtain a mixed slurry;
( 2 )将浆料在 110°C干燥炉中干燥得到前驱体材料， 置于马氟炉中 600°C烧 4小时,随炉冷却至室温， 得到钛酸锂 Li4Ti5012包覆二硫化铁（FeS2 ) 的锂离子 电池复合型负极材料。 (2) The slurry is dried in a drying oven at 110 ° C to obtain a precursor material, which is placed in a muffle furnace at 600 ° C for 4 hours, and cooled to room temperature with a furnace to obtain a lithium titanate Li 4 Ti 5 0 12 coating. Lithium ion battery composite anode material of iron disulfide (FeS 2 ).
锂离子电池的制备方法 Method for preparing lithium ion battery
同实施例一。
实施例三 Same as the first embodiment. Embodiment 3
一种锂离子电池复合型负极材料的制备方法 Method for preparing lithium ion battery composite anode material
( 1 )称取硝酸锂 15.5g、 二氧化钛 20g分散于 200mL的去离子水中，加入碳 黑 1.2g分散均匀， 再加入硫化镍 18.2g、 二硫化铁 18.2g充分搅拌分散均匀得到 稠状浆料； (1) Weigh 15.5g of lithium nitrate, 20g of titanium dioxide dispersed in 200mL of deionized water, add 1.2g of carbon black to disperse evenly, and then add 18.2g of nickel sulfide and 18.2g of iron disulfide, stir well to obtain a thick slurry;
( 2 )将浆料在 110°C干燥炉中干燥得到前驱体材料， 将前驱体材料置于工业 微波炉内， 以 10°C/min的速率升温到 650°C , 保温 2小时， 随炉冷却至室温， 得到钛酸锂 Li4Ti5012包覆硫化镍（NiS ) 和二石 A化铁 ( FeS2 )的锂离子电池复合 型负极材料。 (2) The slurry is dried in a drying oven at 110 ° C to obtain a precursor material, and the precursor material is placed in an industrial microwave oven, heated to 650 ° C at a rate of 10 ° C / min, kept for 2 hours, and cooled with the furnace. To the room temperature, a lithium ion battery composite negative electrode material in which lithium titanate Li 4 Ti 5 0 12 was coated with nickel sulfide (NiS ) and sillimanite iron (FeS 2 ) was obtained.
锂离子电池的制备方法 Method for preparing lithium ion battery
同实施例一。 实施例四 Same as the first embodiment. Embodiment 4
一种锂离子电池复合型负极材料的制备方法 Method for preparing lithium ion battery composite anode material
( 1 )将 20g醋酸锂均匀分散至无水乙醇溶液中， 按照 Ti: Li为 5: 4的摩尔 比量取异丙醇钛 107g, 用 200mL无水乙醇稀释后， 加到分散有醋酸锂的乙醇水 溶液中， 搅拌均勾后再加入 6.8g碳纳米管， 再加入 120g MoS (石 A化钼）充分搅 拌分散均匀， 得到凝胶 -溶胶浆料； (1) 20 g of lithium acetate was uniformly dispersed in an absolute ethanol solution, and 107 g of titanium isopropoxide was taken in a molar ratio of Ti: Li of 5:4, diluted with 200 mL of absolute ethanol, and added to the lithium acetate dispersed therein. In the aqueous ethanol solution, 6.8 g of carbon nanotubes were added after stirring, and then 120 g of MoS (stone molybdenum) was added and stirred well to obtain a gel-sol slurry;
( 2 )将凝胶 -溶胶浆料在 60°C干燥炉中干燥得到前驱体材料， 置于马氟炉中 650°C烧 2小时， 随炉冷却至室温， 得到钛酸锂 Li4Ti5012包覆 MoS (硫化钼）的 锂离子电池复合型负极材料。 (2) The gel-sol slurry is dried in a drying oven at 60 ° C to obtain a precursor material, which is placed in a muffle furnace at 650 ° C for 2 hours, and cooled to room temperature with a furnace to obtain lithium titanate Li 4 Ti 5 . 0 12 Lithium-ion battery composite anode material coated with MoS (molybdenum sulfide).
锂离子电池的制备方法 Method for preparing lithium ion battery
同实施例一。
实施例五 Same as the first embodiment. Embodiment 5
一种锂离子电池复合型负极材料的制备方法 Method for preparing lithium ion battery composite anode material
( 1 )称取水合氢氧化锂（LiOH . H20 ) 8.4g、 二氧化钛 20g分散于 250mL 的去离子水中， 分散均匀； 再加入 85.6g Co9S8 (石 υ化钴） 充分搅拌分散均匀， 得到混合液体； (1) Weigh 8.4g of hydrated lithium hydroxide (LiOH. H 2 0 ), 20g of titanium dioxide dispersed in 250mL of deionized water, and disperse evenly; add 85.6g of Co 9 S 8 (cobalt sulphate) and mix well. , obtaining a mixed liquid;
( 2 ) 随后将溶液转入水热反应釜中， 加入 4.5g导电乙炔黑在 160°C下水热 离子交换反应 10h, 得到黑色沉淀， 再将黑色沉淀置于 500°C的马弗炉中热处理 2h, 随炉冷却至室温， 得到钛酸锂 Li4Ti5012包覆 Co9S8 (石 A化钴）的锂离子电池 复合型负极材料。 (2) Subsequently, the solution was transferred to a hydrothermal reaction vessel, and 4.5 g of conductive acetylene black was added for hydrothermal ion exchange reaction at 160 ° C for 10 h to obtain a black precipitate, and the black precipitate was placed in a muffle furnace at 500 ° C for heat treatment. 2h, the furnace was cooled to room temperature to obtain a lithium ion battery composite anode material coated with lithium titanate Li 4 Ti 5 0 12 coated with Co 9 S 8 (stone cobalt).
锂离子电池的制备方法 Method for preparing lithium ion battery
同实施例一。 实施例六 Same as the first embodiment. Embodiment 6
一种锂离子电池复合型负极材料的制备方法 Method for preparing lithium ion battery composite anode material
( 1 )称取水合氢氧化锂（ LiOH · H20 ) 16.8g、 二氧化钛 40g分散于 150mL 的去离子水中； 加入 2.5g人造石墨,再加入 5.5g硫化镍充分搅拌分散均匀，得到 混合浆料； (1) Weigh hydrated lithium hydroxide (LiOH · H 2 0 ) 16.8g, titanium dioxide 40g dispersed in 150mL of deionized water; add 2.5g of artificial graphite, then add 5.5g of nickel sulfide, stir well and disperse evenly to obtain mixed slurry ;
( 2 )将浆料在 110°C干燥炉中干燥得到前驱体材料， 将前驱体材料置于工业 微波炉内， 以 10°C/min的速率升温到 700°C , 保温 1小时， 随炉冷却至室温， 得到钛酸锂 Li4Ti5012包覆硫化镍（NiS ) 的锂离子电池复合型负极材料。 (2) drying the slurry in a drying oven at 110 ° C to obtain a precursor material, placing the precursor material in an industrial microwave oven, heating to 700 ° C at a rate of 10 ° C / min, holding for 1 hour, cooling with the furnace To the room temperature, a lithium ion battery composite negative electrode material in which lithium titanate Li 4 Ti 5 0 12 was coated with nickel sulfide (NiS) was obtained.
锂离子电池的制备方法 Method for preparing lithium ion battery
同实施例一。
实施例七 Same as the first embodiment. Example 7
一种锂离子电池复合型负极材料的制备方法 Method for preparing lithium ion battery composite anode material
( 1 )称取硝酸锂 15.5g、 二氧化钛 20g分散于 500mL的去离子水中， 再加入 二硫化铁 410.5g充分搅拌分散均勾得到稠状浆料； (1) Weigh 15.5g of lithium nitrate, 20g of titanium dioxide dispersed in 500mL of deionized water, and then add 410.5g of iron disulfide to fully agitate and disperse to obtain a thick slurry;
( 2 )将浆料在 110°C干燥炉中干燥得到前驱体材料， 将前驱体材料置于工业 微波炉内， 以 10°C/min的速率升温到 650°C , 保温 2小时， 随炉冷却至室温， 得到钛酸锂 1^41¾012包覆二硫化铁（FeS2 ) 的锂离子电池复合型负极材料。 (2) The slurry is dried in a drying oven at 110 ° C to obtain a precursor material, and the precursor material is placed in an industrial microwave oven, heated to 650 ° C at a rate of 10 ° C / min, kept for 2 hours, and cooled with the furnace. To room temperature, a lithium ion battery composite negative electrode material of lithium titanate 1^ 4 13⁄40 12 coated with iron disulfide (FeS 2 ) was obtained.
锂离子电池的制备方法 Method for preparing lithium ion battery
同实施例一。 对比例一 Same as the first embodiment. Comparative example one
将未包覆钛酸锂 Li4Ti5012的硫化镍（NiS )组装成锂离子电池， 方法同实施 例一。 Nickel sulfide (NiS) not coated with lithium titanate Li 4 Ti 5 0 12 was assembled into a lithium ion battery in the same manner as in Example 1.
对比例二 Comparative example two
将未包覆钛酸锂 Li4Ti5012的二石 A化铁（ FeS2 )组装成锂离子电池， 方法同实 施例一。 A two-stone iron (FeS 2 ) which is not coated with lithium titanate Li 4 Ti 5 0 12 is assembled into a lithium ion battery in the same manner as in the first embodiment.
对比例三 Comparative example three
将未包覆钛酸锂 Li4Ti5012的硫化镍（NiS )和二石 A化铁（ FeS2 ) 混合负极材 料组装成锂离子电池， 方法同实施例一。 A nickel-ion battery (NiS) and a two-stone iron (FeS 2 ) mixed anode material which are not coated with lithium titanate Li 4 Ti 5 0 12 are assembled into a lithium ion battery in the same manner as in the first embodiment.
对比例四 Comparative example four
将未包覆钛酸锂 1^41¾012的 MoS (石 υ化钼）组装成锂离子电池， 方法同实 施例一
对比例五 The MoS (diamond molybdenum) which is not coated with lithium titanate 1^ 4 13⁄40 12 is assembled into a lithium ion battery, and the method is the same as that in the first embodiment. Comparative example five
将未包覆钛酸锂 Li4Ti5012的 Co9S8 (硫化钴）组装成锂离子电池， 方法同实 施例一 以上实施例和对比例中制得的锂离子电池为实验电池， 用于下述效果实施 例性能测试。 Co 9 S 8 (cobalt sulfide) not coated with lithium titanate Li 4 Ti 5 0 12 was assembled into a lithium ion battery, and the lithium ion battery prepared in the same manner as in the above first embodiment and the comparative example was used as a test battery. Used in the performance test of the following effect examples.
效果实施例 Effect embodiment
为对本发明实施例技术方案带来的有益效果进行有力支持， 特提供以下性 能测试： In order to strongly support the beneficial effects brought by the technical solutions of the embodiments of the present invention, the following performance tests are provided:
将上述实施例和对比例中制得的锂离子电池， 采用电池性能测试仪进行充 放电循环的测试。 测试条件为： 充电截至电压至 2.5V, 放电截至电压至 1.3V, 电流密度为 0.07mA/cm2。 The lithium ion batteries prepared in the above examples and comparative examples were subjected to a charge and discharge cycle test using a battery performance tester. The test conditions are: charging cut-off voltage to 2.5V, discharge cut-off voltage to 1.3V, current density of 0.07mA/cm 2 .
图 1 是本发明实施例一与对比例一所得锂离子电池的循环性能对比图。 从 图 1中可以看出， 实施例一表面包覆钛酸锂 Li4Ti5012的硫化镍（NiS )锂离子电 池复合型负极材料的首次比容量为 423 mAh/g,对比例一未包覆的石充化镍（ NiS ) 材料的首次比容量为 500 mAh/g, 但是其经过 50次循环以后， 其比容量下降为 197 mAh/g, 只有首次比容量的 39.4 % ; 而表面包覆钛酸锂 Li4Ti5012的硫化镍 ( NiS )锂离子电池复合型负极材料， 经过 50 次循环以后， 其比容量下降为 399mAh/g, 是首次比容量的 93 % ; 结果说明： 表面包覆钛酸锂 Li4Ti5012的硫化 镍材料， 其循环性能得到了显著改善。 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the comparison of cycle performance of a lithium ion battery obtained in Example 1 of the present invention and Comparative Example 1. As can be seen from FIG. 1, the first specific specific capacity of the nickel-nickel (NiS) lithium ion battery composite anode material coated with lithium titanate Li 4 Ti 5 0 12 on the surface of the first embodiment is 423 mAh/g, and the ratio is not The first specific capacity of the coated stone-filled nickel (NiS) material was 500 mAh/g, but after 50 cycles, its specific capacity decreased to 197 mAh/g, only 39.4% of the first specific capacity; The lithium niobate (NiS) lithium ion battery composite anode material coated with lithium titanate Li 4 Ti 5 0 12 has a specific capacity decrease of 399 mAh/g after 50 cycles, which is 93% of the first specific capacity. The nickel sulfide material coated with lithium titanate Li 4 Ti 5 0 12 has a significant improvement in cycle performance.
图 2是本发明实施例二与对比例二所得锂离子电池的循环性能对比图。 从 图 2中可以看出， 实施例二表面包覆钛酸锂 Li4Ti5012的二硫化铁锂离子电池复 合型负极材料的首次比容量为 556 mAh/g,对比例二未包覆的二石充化铁材料的首
次比容量为 600 mAh/g,但是其经过 50次循环以后，其比容量下降为 125 mAh/g, 只有首次比容量的 21 %； 而表面包覆钛酸锂 Li4Ti5012的二硫化铁锂离子电池复 合型负极材料， 经过 50次循环以后， 其比容量下降为 512mAh/g, 是首次比容 量的 92 % ; 结果说明： 表面包覆钛酸锂 Li4Ti5012的二硫化铁材料， 其循环性能 得到了显著改善。 2 is a comparison diagram of cycle performance of a lithium ion battery obtained in Example 2 and Comparative Example 2 of the present invention. It can be seen from FIG. 2 that the first specific specific capacity of the lithium iron disulfide lithium ion battery composite anode material coated with lithium titanate Li 4 Ti 5 0 12 on the surface of the second embodiment is 556 mAh/g, and the comparative example is not coated. The first of the two stone-filled iron materials The secondary specific capacity is 600 mAh/g, but after 50 cycles, its specific capacity decreases to 125 mAh/g, which is only 21% of the first specific capacity; and the surface is coated with lithium titanate Li 4 Ti 5 0 12 After 50 cycles, the specific capacity of the lithium iron ion battery composite anode material decreased to 512 mAh/g, which is 92% of the first specific capacity. The results show that: the surface coated with lithium titanate Li 4 Ti 5 0 12 The iron sulfide material has a significant improvement in cycle performance.
图 3是本发明实施例三与对比例三所得锂离子电池的循环性能对比图。 从 图 3中可以看出， 实施例三表面包覆钛酸锂 Li4Ti5012的硫化镍与二硫化铁锂离 子电池复合型负极材料的首次比容量为 394 mAh/g,对比例三未包覆的硫化镍及 二硫化铁混合材料的首次比容量为 500 mAh/g, 但是其经过 50次循环以后， 其 比容量下降为 165 mAh/g,只有首次比容量的 30 % ; 而表面包覆钛酸锂 Li4Ti5012 的硫化镍与二硫化铁锂离子电池复合型负极材料经过 50次循环以后， 其比容量 下降为 370mAh/g, 是首次比容量的 94 % ; 结果说明： 表面包覆钛酸锂 Li4Ti5012 的硫化镍及二硫化铁材料， 其循环性能得到了显著改善。 3 is a graph showing the cycle performance of a lithium ion battery obtained in Example 3 of the present invention and Comparative Example 3. It can be seen from FIG. 3 that the first specific capacity of the composite negative electrode material of the nickel sulfide and the lithium iron disulfide lithium ion battery coated with lithium titanate Li 4 Ti 5 0 12 on the surface of the third embodiment is 394 mAh/g, and the third comparative example The uncoated nickel sulfide and iron disulfide mixture had a first specific capacity of 500 mAh/g, but after 50 cycles, its specific capacity decreased to 165 mAh/g, only 30% of the first specific capacity; After 50 cycles of the nickel sulfide and lithium iron disulfide lithium ion battery composite anode materials coated with lithium titanate Li 4 Ti 5 0 12 , the specific capacity decreased to 370 mAh/g, which is 94% of the first specific capacity. : The surface is coated with lithium titanate Li 4 Ti 5 0 12 nickel sulfide and iron disulfide material, and its cycle performance is significantly improved.
图 4是本发明实施例四与对比例四所得锂离子电池的循环性能对比图。 从 图 4中可以看出， 实施例四表面包覆钛酸锂 Li4Ti5012的硫化钼锂离子电池复合 型负极材料的首次比容量为 324.2mAh/g, 对比例四未包覆的石充化钼的首次比容 量为 400 mAh/g, 但是其经过 50次循环以后， 其比容量下降为 145.6mAh/g, 只 有首次比容量的 36.4 %； 而表面包覆钛酸锂 Li4Ti5012的硫化钼锂离子电池复合 型负极材料经过 50次循环以后， 其比容量下降为 298.5mAh/g,是首次比容量的 92.1 % ; 结果说明： 表面包覆钛酸锂 Li4Ti5012的硫化钼材料， 其循环性能得到了 显著改善。 4 is a graph showing the cycle performance of a lithium ion battery obtained in Example 4 and Comparative Example 4 of the present invention. As can be seen from FIG. 4, the first specific specific capacity of the lithium sulfide molybdenum lithium ion battery composite anode material coated with lithium titanate Li 4 Ti 5 0 12 on the surface of the fourth embodiment is 324.2 mAh/g, and the comparative example is uncoated. The first specific capacity of the stone-filled molybdenum was 400 mAh/g, but after 50 cycles, its specific capacity decreased to 145.6 mAh/g, only 36.4% of the first specific capacity; and the surface coated with lithium titanate Li 4 Ti After 50 cycles of the 5 0 12 molybdenum sulfide lithium ion battery composite anode material, its specific capacity decreased to 298.5 mAh/g, which is 92.1% of the first specific capacity. Results: Surface coated with lithium titanate Li 4 Ti 5 The 0 12 molybdenum sulfide material has a significant improvement in cycle performance.
图 5是本发明实施例五与对比例五所得锂离子电池的循环性能对比图。 从 图 4中可以看出， 实施例四表面包覆钛酸锂 Li4Ti5012的硫化钴锂离子电池复合
型负极材料的首次比容量为 298mAh/g, 对比例四未包覆的硫化钼的首次比容量 为 350mAh/g, 但是其经过 50次循环以后， 其比容量下降为 73mAh/g, 只有首 次比容量的 20.8 %； 而表面包覆钛酸锂 Li4Ti5012的硫化钴锂离子电池复合型负 极材料经过 50次循环以后，其比容量下降为 273mAh/g,是首次比容量的 91.6 %； 结果说明： 表面包覆钛酸锂 Li4Ti5012的硫化钴材料， 其循环性能得到了显著改 善。
Figure 5 is a graph showing the cycle performance of a lithium ion battery obtained in Example 5 and Comparative Example 5 of the present invention. As can be seen from FIG. 4, the fourth embodiment of the surface coated with lithium titanate Li 4 Ti 5 0 12 cobalt sulfide lithium ion battery composite The first specific capacity of the negative electrode material was 298 mAh/g, and the first specific capacity of the four uncoated molybdenum sulfide was 350 mAh/g, but after 50 cycles, the specific capacity decreased to 73 mAh/g, only the first time ratio. 20.8% of the capacity; and the surface-coated lithium titanate Li 4 Ti 5 0 12 cobalt sulfide lithium ion battery composite anode material after 50 cycles, its specific capacity decreased to 273 mAh / g, is the first specific capacity of 91.6 % The results show that the cobalt sulfide material coated with lithium titanate Li 4 Ti 5 0 12 has a significant improvement in cycle performance.
Claims
1、 一种锂离子电池复合型负极材料， 其特征在于， 包括过渡金属石υ化物， 以及设置在所述过渡金属硫化物表面的包覆层， 所述过渡金属硫化物为 NiS、 FeS2、 FeS、 TiS2、 MoS和 Co9S8中的一种或多种， 所述包覆层的材料包括钛酸 锂 Li4Ti5012。 1. A composite negative electrode material for a lithium-ion battery, characterized by comprising a transition metal sulfide, and a coating layer provided on the surface of the transition metal sulfide, where the transition metal sulfide is NiS, FeS 2 , One or more of FeS, TiS 2 , MoS and Co 9 S 8 , and the material of the coating layer includes lithium titanate Li 4 Ti 5 0 12 .
2、 如权利要求 1所述的一种锂离子电池复合型负极材料， 其特征在于， 所 述包覆层的厚度为 50~8000nm。 2. A composite negative electrode material for lithium ion batteries according to claim 1, characterized in that the thickness of the coating layer is 50~8000nm.
3、 如权利要求 1所述的一种锂离子电池复合型负极材料， 其特征在于， 所 述过渡金属硫化物占所述锂离子电池复合型负极材料总质量的 10%~95%。 3. The composite negative electrode material for lithium ion batteries according to claim 1, wherein the transition metal sulfide accounts for 10% to 95% of the total mass of the composite negative electrode material for lithium ion batteries.
4、 如权利要求 1所述的一种锂离子电池复合型负极材料， 其特征在于， 所 述包覆层的材料进一步包括导电添加剂， 所述导电添加剂为人造石墨、 天然石 墨、 乙炔黑、 炭黑、 中间相碳微球、 碳纳米管、 碳纳米纤维、 酚醛树脂、 蔗糖 中的一种或多种， 所述导电添加剂占所述锂离子电池复合型负极材料总质量的 1%~5%。 4. A lithium-ion battery composite negative electrode material according to claim 1, characterized in that the material of the coating layer further includes a conductive additive, and the conductive additive is artificial graphite, natural graphite, acetylene black, carbon One or more of black, mesophase carbon microspheres, carbon nanotubes, carbon nanofibers, phenolic resin, and sucrose. The conductive additive accounts for 1% to 5% of the total mass of the lithium-ion battery composite negative electrode material. .
5、 一种锂离子电池复合型负极材料的制备方法， 其特征在于， 包括以下步 骤： 5. A method for preparing composite negative electrode materials for lithium-ion batteries, which is characterized by including the following steps:
( 1 )将包覆原料锂源、 钛源和待包覆的过渡金属硫化物在分散介质中搅拌 分散均匀， 制成浆料；
所述包覆原料锂源选自氢氧化锂、水合氢氧化锂、碳酸锂、硝酸锂、硫酸锂、 氟化锂、 草酸锂、 氯化锂和醋酸锂中的一种或几种； (1) Stir and disperse the coating raw materials lithium source, titanium source and transition metal sulfide to be coated in the dispersion medium to form a slurry; The coating raw material lithium source is selected from one or more of lithium hydroxide, hydrated lithium hydroxide, lithium carbonate, lithium nitrate, lithium sulfate, lithium fluoride, lithium oxalate, lithium chloride and lithium acetate;
所述包覆原料钛源选自二氧化钛、 四氯化钛、 三氯化钛、 异丙醇钛、 钛酸四 丁酯、 钛酸丁酯和钛酸正丙酯中的一种或多种； The coating raw material titanium source is selected from one or more of titanium dioxide, titanium tetrachloride, titanium trichloride, titanium isopropoxide, tetrabutyl titanate, butyl titanate and n-propyl titanate;
所述过渡金属石 υ化物选自 NiS、 FeS2、 FeS、 TiS2、 MoS和 Co9S8中的一种或 多种； The transition metal lithide is selected from one or more of NiS, FeS 2 , FeS, TiS 2 , MoS and Co 9 S 8 ;
所述分散介质选自水、 Ν,Ν-二曱基曱酰胺、 Ν,Ν-二曱基乙酰胺、 Ν-2-曱基吡 咯綻酮、 四氢呋喃、 乙醇和曱醇中的一种或多种； The dispersion medium is selected from one or more of water, N, N-dimethylformamide, N, N-dimethylacetamide, N-2-methylpyrrolidone, tetrahydrofuran, ethanol and methanol. kind;
( 2 )将得到的所述浆料通过溶胶 -凝胶法、 水热反应法、 微波化学法或高 温固相法进行包覆制得锂离子电池复合型负极材料； 所述锂离子电池复合型负 极材料包括所述过渡金属硫化物， 以及包覆在所述过渡金属硫化物表面的包覆 层， 所述包覆层的材料包括钛酸锂 Li4Ti5012。 (2) The obtained slurry is coated through a sol-gel method, a hydrothermal reaction method, a microwave chemical method or a high-temperature solid phase method to prepare a lithium-ion battery composite negative electrode material; the lithium-ion battery composite type The negative electrode material includes the transition metal sulfide, and a coating layer coating the surface of the transition metal sulfide. The material of the coating layer includes lithium titanate Li 4 Ti 5 0 12 .
6、 如权利要求 5所述的锂离子电池复合型负极材料的制备方法， 其特征在 于，所述过渡金属硫化物占所述锂离子电池复合型负极材料总质量的 10%~95%。 6. The method for preparing a composite negative electrode material for a lithium ion battery according to claim 5, wherein the transition metal sulfide accounts for 10% to 95% of the total mass of the composite negative electrode material for a lithium ion battery.
7、 如权利要求 5所述的锂离子电池复合型负极材料的制备方法， 其特征在 于， 所述包覆原料进一步包括导电添加剂， 所述导电添加剂为人造石墨、 天然 石墨、 乙炔黑、 炭黑、 中间相碳微球、 碳纳米管、 碳纳米纤维、 酚醛树脂、 蔗 糖中的一种或多种， 所述导电添加剂占所述锂离子电池复合型负极材料总质量 的 1%~5%。 7. The method for preparing composite negative electrode materials for lithium ion batteries according to claim 5, wherein the coating raw material further includes a conductive additive, and the conductive additive is artificial graphite, natural graphite, acetylene black, and carbon black. , one or more of mesophase carbon microspheres, carbon nanotubes, carbon nanofibers, phenolic resin, and sucrose, and the conductive additive accounts for 1% to 5% of the total mass of the lithium-ion battery composite negative electrode material.
8、 如权利要求 5所述的锂离子电池复合型负极材料的制备方法， 其特征在
于， 所述微波化学法的具体操作为： 将所述浆料在 100~120°C下干燥， 得到前驱 体材料， 将所述前驱体材料置于工业微波炉中， 以 10°C/min升温到 600~800°C , 保温 1~4小时， 随炉冷却， 即得到所述锂离子电池复合型负极材料。 8. The preparation method of composite negative electrode material for lithium ion batteries according to claim 5, characterized in that The specific operation of the microwave chemical method is: dry the slurry at 100~120°C to obtain a precursor material, place the precursor material in an industrial microwave oven, and raise the temperature at 10°C/min to 600~800°C, keep the temperature for 1~4 hours, and then cool in the furnace to obtain the composite negative electrode material for lithium ion batteries.
9、 如权利要求 5所述的锂离子电池复合型负极材料的制备方法， 其特征在 于， 所述高温固相法的具体操作为： 将所述浆料在 100~120°C下干燥， 得到前驱 体材料， 将所述前驱体材料置于马弗炉中在 400~900°C下烧结 0.5~10小时， 随 炉冷却， 即得到所述锂离子电池复合型负极材料。 9. The preparation method of composite negative electrode material for lithium ion batteries according to claim 5, characterized in that the specific operation of the high temperature solid phase method is: drying the slurry at 100~120°C to obtain Precursor material: The precursor material is placed in a muffle furnace and sintered at 400 to 900°C for 0.5 to 10 hours, and then cooled in the furnace to obtain the composite negative electrode material for the lithium ion battery.
10、 一种锂离子电池， 其特征在于， 所述锂离子电池包含权利要求 1~4任一 项所述的锂离子电池复合型负极材料。
10. A lithium-ion battery, characterized in that the lithium-ion battery includes the lithium-ion battery composite negative electrode material according to any one of claims 1 to 4.
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