KR20200020039A - Positive electrode active material for rechargable lithium battery and rechargable lithium battery including the same - Google Patents
Positive electrode active material for rechargable lithium battery and rechargable lithium battery including the same Download PDFInfo
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- KR20200020039A KR20200020039A KR1020180095245A KR20180095245A KR20200020039A KR 20200020039 A KR20200020039 A KR 20200020039A KR 1020180095245 A KR1020180095245 A KR 1020180095245A KR 20180095245 A KR20180095245 A KR 20180095245A KR 20200020039 A KR20200020039 A KR 20200020039A
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- Prior art keywords
- active material
- positive electrode
- lithium
- secondary battery
- electrode active
- Prior art date
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 49
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 24
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims abstract description 18
- 239000011247 coating layer Substances 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 11
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 239000006182 cathode active material Substances 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 9
- 239000010937 tungsten Substances 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 239000010953 base metal Substances 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 33
- -1 metalloid , alkaline earth metal Chemical class 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 2
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
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- 230000006872 improvement Effects 0.000 description 2
- 238000010406 interfacial reaction Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 229910052696 pnictogen Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- OIXUJRCCNNHWFI-UHFFFAOYSA-N 1,2-dioxane Chemical compound C1CCOOC1 OIXUJRCCNNHWFI-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910010093 LiAlO Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 239000011254 layer-forming composition Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical group CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 235000015041 whisky Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
본 발명은 리튬 이차 전지용 양극 활물질 및 이를 포함하는 리튬 이차 전지에 관한 것이다.The present invention relates to a cathode active material for a lithium secondary battery and a lithium secondary battery including the same.
최근, 휴대용 전자 기기뿐만 아니라 전기 자동차, 하이브리드 자동차 등의 중대형 장치 산업으로 확장됨에 따라 이들 장치의 전원으로 사용되는 리튬 이차 전지의 리튬 이차 전지의 고용량화를 위한 연구가 활발하다. Recently, as it expands to medium and large device industries such as electric vehicles and hybrid vehicles, as well as portable electronic devices, researches for increasing the capacity of lithium secondary batteries of lithium secondary batteries used as power sources for these devices have been actively conducted.
따라서, 리튬 이차 전지의 고용량화를 위하여 리튬 이차 전지의 핵심 소재인 양극 활물질의 성능 개선에 대한 연구가 활발하다.Therefore, researches for improving the performance of the positive electrode active material, which is a core material of the lithium secondary battery, have been actively conducted to increase the capacity of the lithium secondary battery.
현재 리튬 이차 전지의 양극 활물질로는 현재 LiCoO2 및 LiMn2O4 등이 주로 사용되고 있다. 그러나, LiCoO2의 경우 고용량의 전지를 구현하는 데 한계가 있고, LiMn2O4의 경우 에너지 밀도가 낮고, Mn이온 용출의 문제점으로 인해 수명특성이 떨어지는 단점이 있다.LiCoO 2 and LiMn 2 O 4 are currently used as positive electrode active materials for lithium secondary batteries. Etc. are mainly used. However, LiCoO 2 has a limitation in realizing a high capacity battery, LiMn 2 O 4 has a low energy density, and has a disadvantage in that its lifespan characteristics are poor due to the problem of Mn ion dissolution.
이에 따라 최근에는 고용량 전지의 구현이 가능한 니켈계 양극 활물질에 대한 관심이 높다. 그러나, 니켈계 양극 활물질의 경우 고용량 특성의 구현은 가능하나, 열안정성이 나쁘고, 고온에서의 수명 특성이 저하되는 문제점이 있다.Accordingly, in recent years, there is a high interest in the nickel-based cathode active material capable of implementing a high capacity battery. However, in the case of the nickel-based cathode active material, high capacity characteristics can be implemented, but thermal stability is poor, and there is a problem in that the life characteristics at high temperatures are deteriorated.
또한, 리튬 금속 산화물의 조성 외에, 양극 활물질의 표면에 존재하는 리튬 부산물에 따른 문제점이 대두되고 있다. 이러한 리튬 부산물로 인해, 배터리 싸이클이 증가할수록 전해액과 양극 활물질 표면 사이의 부반응으로 전해액이 분해되어 가스가 발생하게 되며, 이는 전지의 수명 특성을 저하시키게 된다. In addition, in addition to the composition of the lithium metal oxide, problems caused by lithium by-products present on the surface of the positive electrode active material are emerging. Due to the lithium by-products, as the battery cycle increases, the electrolyte is decomposed due to side reactions between the electrolyte and the surface of the positive electrode active material, and gas is generated, which degrades the battery life characteristics.
이에 따라 전해액과 양극 활물질 표면 사이의 부반응을 억제하기 위한 방안이 필요한 실정이다. Accordingly, there is a need for a method for suppressing side reactions between the electrolyte and the surface of the positive electrode active material.
본 실시예들은 리튬 이차 전지의 고용량 특성을 확보하면서도 수명 특성 및 열 안정성이 우수한 리튬 이차 전지용 양극 활물질 및 이를 포함하는 리튬 이자 전지를 제공하고자 한다. The embodiments provide a cathode active material for a lithium secondary battery and a lithium secondary battery including the same, while ensuring high capacity characteristics of the lithium secondary battery and having excellent life characteristics and thermal stability.
본 발명의 일 구현예에서는, 리튬 금속 산화물 입자; 및 상기 리튬 금속 산화물 입자 표면에 위치하는 코팅층;을 포함하고, 상기 코팅층은 텅스텐 산화물을 포함하는 것인 리튬 이차 전지용 양극 활물질을 제공한다. In one embodiment of the present invention, lithium metal oxide particles; And a coating layer positioned on the surface of the lithium metal oxide particles, wherein the coating layer includes tungsten oxide.
상기 텅스텐 산화물은, 추가적인 양이온으로 도핑될 수 있다. The tungsten oxide may be doped with additional cations.
상기 양이온은, B, Al, Si, Mg, Zn, Ti, Zr, V, Sr, Y, Ni, Co, Mn, 또는 이들의 조합일 수 있다. The cation may be B, Al, Si, Mg, Zn, Ti, Zr, V, Sr, Y, Ni, Co, Mn, or a combination thereof.
상기 텅스텐 산화물은 하기 화학식 1로 표시될 수 있다. The tungsten oxide may be represented by the following formula (1).
[화학식 1][Formula 1]
Li[LixWyM1-x-y]Oa Li [Li x W y M 1-xy ] O a
상기 화학식 1에서, W는 텅스텐을 의미하고, M은 비금속, 전이금속, 알칼리 토금속 또는 이들의 조합이고, 0≤x<1, 0≤y<1, 0<a<8이다. In Formula 1, W means tungsten, M is a base metal, transition metal, alkaline earth metal or a combination thereof, 0≤x <1, 0≤y <1, 0 <a <8.
상기 화학식 1에서, M은 B, Al, Si, Mg, Zn, Ti, Zr, V, Sr, Y, Ni, Co, Mn, 또는 이들의 조합일 수 있다. In Formula 1, M may be B, Al, Si, Mg, Zn, Ti, Zr, V, Sr, Y, Ni, Co, Mn, or a combination thereof.
상기 리튬 금속 산화물은, 하기 화학식 1로 표시되는 화합물을 포함할 수 있다. The lithium metal oxide may include a compound represented by Formula 1 below.
[화학식 1][Formula 1]
Li1 + k[M11-α M2α]O2 - βQβ Li 1 + k [M1 1-α M2 α ] O 2 - β Q β
상기 화학식 1에서, M1는 NixCoyMnz , 이고, M2는 Ti, Zr, Mg, M3, 또는 이들의 조합이고, 상기 M3는 알카리 토금속, 알칼리 금속, 3족 내지 12족 금속원소 및 13족 내지 15족 원소 중 적어도 하나를 포함하고, Q는 F, P 및 S 중 적어도 하나를 포함하며, -0.1 ≤ k ≤ 0.1, 0.0007≤ α ≤ 0.05, 0 ≤ β ≤ 0.1, 0.5 ≤ x ≤ 0.9, 0 ≤ y ≤ 0.2, 0 ≤ z ≤ 0.3 이다. In Formula 1, M1 is Ni x Co y Mn z , M2 is Ti, Zr, Mg, M3, or a combination thereof, M3 is an alkaline earth metal, an alkali metal, Group 3 to 12 metal elements and 13 At least one of a group to group 15 element, Q comprises at least one of F, P, and S, and -0.1 ≦ k ≦ 0.1, 0.0007 ≦ α ≦ 0.05, 0 ≦ β ≦ 0.1, 0.5 ≦ x ≦ 0.9 , 0 ≦ y ≦ 0.2, 0 ≦ z ≦ 0.3.
본 발명의 다른 일 구현예에서는, 양극; 음극; 그리고 전해액을 포함하고, 상기 양극은 전술한 본 발명의 일 구현예에 따른 리튬 이차 전지용 양극 활물질을 포함하는 리튬 이차 전지를 제공한다. In another embodiment of the present invention, a positive electrode; cathode; And it includes an electrolyte, the positive electrode provides a lithium secondary battery comprising a positive electrode active material for a lithium secondary battery according to an embodiment of the present invention described above.
본 발명의 일 구현예에 따른 양극 활물질은, 양극 활물질 표면에 생성되어 있는 리튬 부산물을 코팅층 형성을 통해 저감시킬 수 있다. In the cathode active material according to the embodiment of the present invention, lithium by-products generated on the surface of the cathode active material may be reduced by forming a coating layer.
상기 코팅층을 형성하여 양극활물질 표면과 전해액 사이의 계면 반응 반응을 억제시킬 수 있다. The coating layer may be formed to suppress an interfacial reaction reaction between the surface of the positive electrode active material and the electrolyte.
이러한 부산물 저감 및 계면 반응 억제 효과를 극대화시키기 위해 코팅층에 텅스텐을 적용시킬 수 있다. Tungsten may be applied to the coating layer in order to maximize the byproduct reduction and the interfacial reaction suppressing effect.
추가적으로, W이 적용된 코팅층에 양이온을 치환하여 복합적인 효과를 구현시킬 수 있다. 아울러, W이 적용된 코팅층에 양이온 치환하여 산화물의 구조적 안정성(결합력)을 향상시킬 수 있다. In addition, it is possible to implement a complex effect by replacing the cation in the coating layer W is applied. In addition, the structural stability (bonding force) of the oxide may be improved by cation substitution on the coating layer to which W is applied.
또한, 양이온 치환을 통한 텅스텐 용출을 억제시킬 수 있다. In addition, tungsten elution through cation substitution can be suppressed.
이러한 양극 활물질을 리튬 이차 전지에 적용하는 경우, 전지의 고용량화가 가능하면서도 우수한 열안정성을 가지며, 상온뿐 아니라 고온에서의 수명 특성도 우수한 리튬 이차 전지를 구현할 수 있다. When the positive electrode active material is applied to a lithium secondary battery, it is possible to increase the capacity of the battery and have excellent thermal stability, and can realize a lithium secondary battery having excellent life characteristics at high temperature as well as at room temperature.
이하, 첨부한 본 발명의 여러 실시예들에 대하여 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 상세히 설명한다. 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예들에 한정되지 않는다.Hereinafter, various embodiments of the present disclosure will be described in detail so that those skilled in the art may easily practice the present disclosure. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.
본 발명을 명확하게 설명하기 위해서 설명과 관계없는 부분은 생략하였으며, 명세서 전체를 통하여 동일 또는 유사한 구성요소에 대해서는 동일한 참조 부호를 붙이도록 한다.In order to clearly describe the present invention, parts irrelevant to the description are omitted, and like reference numerals designate like elements throughout the specification.
또한, 명세서 전체에서, 어떤 부분이 어떤 구성요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있는 것을 의미한다.In addition, throughout the specification, when a part is said to "include" a certain component, it means that it can further include other components, except to exclude other components unless specifically stated otherwise.
이하, 일 실시예에 따른 리튬 이차 전지용 양극 활물질, 및 이를 포함하는 리튬 이차 전지에 대하여 구체적으로 설명하기로 한다. Hereinafter, a cathode active material for a lithium secondary battery according to an embodiment, and a lithium secondary battery including the same will be described in detail.
리튬 이차 전지용 양극 활물질Cathode Active Material for Lithium Secondary Battery
본 발명의 일 구현예에서는, 리튬 금속 산화물 입자; 및 상기 리튬 금속 산화물 입자 표면에 위치하는 코팅층;을 포함하고, 상기 코팅층은 텅스텐 산화물을 포함하는 것인 리튬 이차 전지용 양극 활물질을 제공한다. In one embodiment of the present invention, lithium metal oxide particles; And a coating layer positioned on the surface of the lithium metal oxide particles, wherein the coating layer includes tungsten oxide.
보다 구체적으로, 상기 텅스텐 산화물은, 추가적인 양이온으로 도핑될 수 있다. 텅스텐이 적용된 코팅층에 양이온을 치환하여 복합적인 효과를 구현시킬 수 있다. 아울러, 텅스텐이 적용된 코팅층에 양이온 치환하여 산화물의 구조적 안정성(결합력)을 향상시킬 수 있다. 또한, 양이온 치환을 통한 텅스텐 용출을 억제시킬 수 있다. More specifically, the tungsten oxide may be doped with additional cations. Compounds can be implemented by substituting cations in the tungsten applied coating layer. In addition, the structural stability (bonding force) of the oxide may be improved by cation substitution on the tungsten applied coating layer. In addition, tungsten elution through cation substitution can be suppressed.
상기 양이온은, B, Al, Si, Mg, Zn, Ti, Zr, V, Sr, Y, Ni, Co, Mn, 또는 이들의 조합일 수 있다. The cation may be B, Al, Si, Mg, Zn, Ti, Zr, V, Sr, Y, Ni, Co, Mn, or a combination thereof.
각각의 양이온에 대한 기대되는 효과는 다음과 같다. The expected effects on each cation are as follows.
B의 경우, 활물질의 이온 전도도를 개선시킬 수 있다. In the case of B, the ionic conductivity of the active material can be improved.
Al의 경우, 표면 저항을 개선시킬 수 있다. 또한, 리튬 이온 반응성을 향상시킬 수 있다. In the case of Al, the surface resistance can be improved. In addition, the lithium ion reactivity can be improved.
Si의 경우, 활물질의 열안정성을 향상시킬 수 있다. In the case of Si, the thermal stability of the active material can be improved.
Mg 및 Zr의 경우, 활물질의 상변화를 억제시킬 수 있다. In the case of Mg and Zr, the phase change of the active material can be suppressed.
Zn 및 Ti의 경우, 전해액 분해에 의한 활물질 표면 보호 효과를 증대시킬 수 있다. In the case of Zn and Ti, the active material surface protection effect by electrolyte solution decomposition can be improved.
V의 경우, 표면 잔류 리튬 저감 효과가 증대될 수 있다. 또한, 이를 적용한 전지의 용량 개선 효과를 기대할 수 있다. In the case of V, the effect of reducing surface residual lithium can be increased. In addition, the capacity improvement effect of the battery to which it is applied can be expected.
Ni 및/또는 Co 및/또는 Mn의 경우, 표면 잔류 리튬 저감 효과가 증대될 수 있다. 또한 이를 적용한 전지의 용량 개선 효과를 기대할 수 있다. In the case of Ni and / or Co and / or Mn, the surface residual lithium reduction effect can be increased. In addition, the capacity improvement effect of the battery to which this is applied can be expected.
보다 구체적으로, 상기 텅스텐 산화물은 하기 화학식 1로 표시될 수 있다. More specifically, the tungsten oxide may be represented by the following formula (1).
[화학식 1][Formula 1]
Li[LixWyM1-x-y]Oa Li [Li x W y M 1-xy ] O a
상기 화학식 1에서, W는 텅스텐을 의미하고, M은 비금속, 전이금속, 준금속 , 알칼리 토금속 또는 이들의 조합이고, 0≤x<1, 0≤y<1, 0<a<8이다.In Formula 1, W means tungsten, M is a base metal, transition metal, metalloid , alkaline earth metal or a combination thereof, 0≤x <1, 0≤y <1, 0 <a <8.
상기 화학식 1에서, M은 B, Al, Si, Mg, Zn, Ti, Zr, V, Sr, Y, Ni, Co, Mn, 또는 이들의 조합일 수 있다.In Formula 1, M may be B, Al, Si, Mg, Zn, Ti, Zr, V, Sr, Y, Ni, Co, Mn, or a combination thereof.
상기 텅스텐은 다양한 산화수를 가질 수 있기 때문에, 다양한 결정 구조가 가능하다.Since the tungsten may have various oxidation numbers, various crystal structures are possible.
상기 리튬 금속 산화물은, 하기 화학식 1로 표시되는 화합물을 포함할 수 있다.The lithium metal oxide may include a compound represented by Formula 1 below.
[화학식 1][Formula 1]
Li1 + k[M11-α M2α]O2 - βQβ Li 1 + k [M1 1-α M2 α ] O 2 - β Q β
상기 화학식 1에서, M1는 NixCoyMnz , 이고, M2는 Ti, Zr, Mg, M3, 또는 이들의 조합이고, 상기 M3는 알카리 토금속, 알칼리 금속, 3족 내지 12족 금속원소 및 13족 내지 15족 원소 중 적어도 하나를 포함하고, Q는 F, P 및 S 중 적어도 하나를 포함하며, -0.1 ≤ k ≤ 0.1, 0.0007≤ α ≤ 0.05, 0 ≤ β ≤ 0.1, 0.5 ≤ x ≤ 0.9, 0 ≤ y ≤ 0.2, 0 ≤ z ≤ 0.3 이다. In Formula 1, M1 is Ni x Co y Mn z , M2 is Ti, Zr, Mg, M3, or a combination thereof, M3 is an alkaline earth metal, an alkali metal, Group 3 to 12 metal elements and 13 At least one of a group to group 15 element, Q comprises at least one of F, P, and S, and -0.1 ≦ k ≦ 0.1, 0.0007 ≦ α ≦ 0.05, 0 ≦ β ≦ 0.1, 0.5 ≦ x ≦ 0.9 , 0 ≦ y ≦ 0.2, 0 ≦ z ≦ 0.3.
상기 화학식 1에서, k는 -0.1 이상 및 0.1 이하일 수 있다. 따라서, Li의 몰 비율이 0.9 이상 및 1.1 이하일 수 있다. Li의 몰 비율이 0.9 보다 작은 경우에는 Ni가 Li상으로 혼입하기 쉽고 리튬 사이트의 메탈자리 점유율이 커져, 고용량 전지를 구현할 수 있는 Li-Ni복합 산화물을 얻기가 어렵다. 또한, Li의 몰 비율이 1.1보다 큰 경우에는 메탈 사이트로의 Li의 혼입이 많아져, 메탈 사이트에서 떨어져 나온 Ni가 Li상으로 혼입하고 리튬 사이트의 메탈 점유율이 커진다. 따라서, k는 상기 범위인 것이 바람직하고, 보다 구체적으로, 0= k =0.05 범위일 수 있다. In Chemical Formula 1, k may be greater than or equal to -0.1 and less than or equal to 0.1. Therefore, the molar ratio of Li may be 0.9 or more and 1.1 or less. When the molar ratio of Li is less than 0.9, Ni is easily incorporated into the Li phase, and the occupancy of metal sites in the lithium site increases, making it difficult to obtain a Li-Ni composite oxide capable of realizing a high capacity battery. In addition, when the molar ratio of Li is larger than 1.1, the incorporation of Li into the metal site increases, so that Ni separated from the metal site enters the Li phase and the metal occupancy ratio of the lithium site increases. Therefore, k is preferably in the above range, and more specifically, may be in the range of 0 = k = 0.05.
다음, 상기 화학식 1에서 M1는 층상 구조의 니켈계 리튬 금속 산화물, 즉, NixCoyMnz일 수 있다. Next, in Formula 1, M1 may be a nickel-based lithium metal oxide having a layered structure, that is, Ni x Co y Mn z .
또한, 상기 니켈계 리튬 금속 산화물은 Co 및 Mn을 포함하며, Co 및 Mn의 함유 비율인 y 및 z는 전술한 바와 같다. Co 및 Mn의 몰 비가 상기 범위를 만족하는 경우, 고용량을 구현할 수 있는 양극 활물질의 구조적 안정성이 향상될 수 있다.In addition, the nickel-based lithium metal oxide includes Co and Mn, y and z, the content ratio of Co and Mn are as described above. When the molar ratio of Co and Mn satisfies the above range, the structural stability of the positive electrode active material capable of realizing high capacity may be improved.
다음, M2 도펀트를 나타낸다. Next, the M2 dopant is shown.
먼저, M2는 적어도 3종의 도펀트를 포함할 수 있고, 필요에 따라 M3를 더 포함할 수 있다. 즉, M2는 TiaZrbMgcMd로 표시될 수 있다. M2의 총 몰비인 α, 즉, a+b+c+d는, 0.0007≤ α ≤ 0.05, 보다 구체적으로, 0.005≤ α ≤ 0.03 또는 0.008≤ α ≤ 0.04 범위일 수 있다. First, M2 may include at least three dopants, and may further include M3 as needed. That is, M2 may be represented as Ti a Zr b Mg c M d . Α, ie, a + b + c + d, which is the total molar ratio of M2, may range from 0.0007 ≦ α ≦ 0.05, more specifically 0.005 ≦ α ≦ 0.03 or 0.008 ≦ α ≦ 0.04.
본 실시예에 따른 양극 활물질에서 도펀트로 M2로 표시되는 3 종의 도펀트, 즉, Ti, Zr 및 Mg가 상기와 같은 비율로 포함되는 경우, 양극 활물질의 구조적 안정성 및 표면 안정화를 향상시킬 수 있다. In the positive electrode active material according to the present embodiment, when three kinds of dopants represented by M 2 as dopants, that is, Ti, Zr, and Mg are included in the above ratio, structural stability and surface stabilization of the positive electrode active material may be improved.
구체적으로, Ti는 0.0005 ≤ a ≤ 0.02, 또는 0.001 ≤ a ≤ 0.01의 비율로 포함될 수 있다. Ti가 상기와 같은 비율로 포함되는 경우 충방전 과정에서 리튬의 탈리 및 삽입이 이루어질 때 상기 니켈계 리튬 금속 산화물이 비가역 영역으로 상전이 되는 것을 제어할 수 있다. 아울러, 층상 결정 구조를 갖는 니켈게 금속 산화물 내의 c축의 팽창을 제어함으로써 양극 활물질의 구조적 안정성을 향상시킬 수 있다. Specifically, Ti may be included in a ratio of 0.0005 ≦ a ≦ 0.02, or 0.001 ≦ a ≦ 0.01. When Ti is included in the above ratio, the nickel-based lithium metal oxide may be controlled to be phase-changed into an irreversible region when lithium is detached and inserted in the charging and discharging process. In addition, it is possible to improve the structural stability of the positive electrode active material by controlling the expansion of the c-axis in the nickel crab metal oxide having a layered crystal structure.
또한, Zr은 0.0001 ≤ b ≤ 0.01, 또는 0.0005 ≤ b ≤ 0.005의 비율로 포함될 수 있다. Zr을 상기와 같은 비율로 포함하는 경우, Zr이 니켈계 리튬 금속 산화물 입자의 표면에 위치하는 전이 금속과 일부 치환되고, 니켈계 리튬 금속 산화물 입자의 표면에 Zr을 포함하는 산화물을 형성하여 양극 활물질 표면의 안정화를 향상시킬 수 있다. In addition, Zr may be included in a ratio of 0.0001 ≦ b ≦ 0.01, or 0.0005 ≦ b ≦ 0.005. When Zr is included in the above ratio, Zr is partially substituted with a transition metal located on the surface of the nickel-based lithium metal oxide particles, and an oxide containing Zr is formed on the surface of the nickel-based lithium metal oxide particles to form a cathode active material. It is possible to improve the stabilization of the surface.
한편, Mg는 0.0001 ≤ c ≤ 0.01, 또는 0.001 ≤ c ≤ 0.005 범위의 비율로 포함될 수 있다. Mg를 상기와 같은 비율로 포함하는 경우, 상기 층상 결정 구조를 갖는 니켈계 리튬 금속 산화물의 리튬층에서 리튬 사이트의 리튬과 니켈 간 양이온 혼합(cation mixing)이 발생하는 것을 억제할 수 있다. 이에 따라 양극 활물질의 구조적 안정성을 향상시킴으로써 고용량화와 동시에 수명 특성이 향상된 리튬 이차 전지를 구현할 수 있다.Meanwhile, Mg may be included in a ratio of 0.0001 ≦ c ≦ 0.01, or 0.001 ≦ c ≦ 0.005. When Mg is included in the above ratio, it is possible to suppress cation mixing between lithium and nickel in the lithium site in the lithium layer of the nickel-based lithium metal oxide having the layered crystal structure. Accordingly, by improving the structural stability of the positive electrode active material, it is possible to implement a lithium secondary battery having high capacity and improved life characteristics.
본 실시예의 상기 화학식 1에서, M3는 전술한 M1 및 M2를 제외한 도펀트로 알카리 토금속, 알칼리 금속, 3족 내지 12족 금속원소 및 13족 내지 15족 원소 중 적어도 하나를 포함할 수 있다. 예를 들면, 상기 M3는 Al, B, P, S, Mo, V, W, Ca, Na, Zn, Cr, Fe, Cu, Ru, Sr, Be, Si, Ge, Ba, K, Sr, Hf, Ta, Ga, Os, As 및 Sb 중 적어도 하나를 포함할 수 있으며, 보다 구체적으로, 상기 C는 Al 및 B 중 적어도 하나를 포함할 수 있다. 또는, 상기 M3는 Al 및 B를 모두 포함할 수 있다. In Formula 1 of the present embodiment, M3 may include at least one of an alkaline earth metal, an alkali metal, a Group 3 to 12 metal element, and a Group 13 to 15 element as a dopant except for M1 and M2. For example, M3 is Al, B, P, S, Mo, V, W, Ca, Na, Zn, Cr, Fe, Cu, Ru, Sr, Be, Si, Ge, Ba, K, Sr, Hf , Ta, Ga, Os, As, and Sb may include at least one, and more specifically, the C may include at least one of Al and B. Alternatively, the M3 may include both Al and B.
이때, 상기 화학식 1에서, 상기 Al의 몰 비율은, 0.001 ≤ Al ≤ 0.01, 보다 구체적으로, 0.002 ≤ Al ≤ 0.01 범위일 수 있다. 또한, 상기 B의 몰 비율은, 0.0001 ≤ B ≤ 0.001, 보다 구체적으로, 0.0005 ≤ B ≤ 0.001 범위일 수 있다. In this case, in Formula 1, the molar ratio of Al may be in the range of 0.001 ≦ Al ≦ 0.01, more specifically, 0.002 ≦ Al ≦ 0.01. In addition, the molar ratio of B may be 0.0001 ≦ B ≦ 0.001, more specifically, 0.0005 ≦ B ≦ 0.001.
Al을 상기와 같은 비율로 포함하는 경우, 본 실시예에 따른 양극 활물질의 열 안정성 및 구조 안정화가 가능하다. When Al is included in the above ratio, thermal stability and structure stabilization of the positive electrode active material according to the present embodiment are possible.
또한, B는 양극 활물질 입자의 치밀화에 관계하는 것으로 확인되는바, B를 상기와 같은 비율로 포함하는 경우, 전술한 니켈계 리튬 산화물의 1차 입자 간 결합을 견고하게 만들어 내부의 공극을 줄일 수 있고, 이온 전도도를 향상시킬 수 있다.In addition, it is confirmed that B is related to the densification of the positive electrode active material particles, and when B is included in the above ratio, it is possible to strengthen the bond between the primary particles of the nickel-based lithium oxide described above to reduce internal voids. And ionic conductivity can be improved.
리튬 이차 전지Lithium secondary battery
전술한 일 실시예에 따른 리튬 이차 전지용 양극 활물질은 리튬 이차 전지의 양극에 유용하게 사용될 수 있다. 즉, 본 발명의 일 실시예에 따른 리튬 이차 전지는 음극과 함께 전술한 양극 활물질을 포함하는 양극 및 전해질을 포함한다.The cathode active material for a lithium secondary battery according to the above-described embodiment may be usefully used for the cathode of a lithium secondary battery. That is, the lithium secondary battery according to an embodiment of the present invention includes a cathode and an electrolyte including the cathode active material described above together with the anode.
구체적으로, 본 발명의 일 실시예에 따른 리튬 이차 전지는 양극, 음극, 그리고 상기 양극과 상기 음극 사이에 배치된 세퍼레이터를 포함하는 전극 조립체를 포함할 수 있다. Specifically, the lithium secondary battery according to an embodiment of the present invention may include an electrode assembly including a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode.
상기 음극은, 음극 활물질, 바인더 및 선택적으로 도전재를 혼합하여 음극 활물질층 형성용 조성물을 제조한 후, 이를 구리 등의 음극 집전체에 도포하여 제조될 수 있다.The negative electrode may be prepared by mixing a negative electrode active material, a binder, and optionally a conductive material to prepare a composition for forming a negative electrode active material layer, and then applying the same to a negative electrode current collector such as copper.
상기 음극 활물질로는, 리튬을 인터칼레이션/디인터칼레이션할 수 있는 재료가 사용되고, 예를 들면, 리튬 금속이나 리튬 합금, 코크스, 인조 흑연, 천연 흑연, 유기 고분자 화합물 연소체, 탄소 섬유 등을 사용한다.As the negative electrode active material, a material capable of intercalating / deintercalating lithium is used, and for example, lithium metal, lithium alloy, coke, artificial graphite, natural graphite, organic polymer compound combustor, carbon fiber, or the like. Use
상기 바인더로는 폴리비닐알코올, 카르복시메틸셀룰로오스/스티렌-부타디엔러버, 히드록시프로필렌셀룰로오스, 디아세틸렌셀룰로오스, 폴리비닐클로라이드, 폴리비닐피롤리돈, 폴리테트라플루오로에틸렌, 폴리비닐리덴 플루오라이드, 폴리에틸렌 또는 폴리프로필렌 등을 사용할 수 있으나, 이에 한정되는 것은 아니다. 상기 바인더는 상기 음극 활물질층 형성용 조성물의 총량에 대하여 1 내지 30 중량%로 혼합될 수 있다.The binder may be polyvinyl alcohol, carboxymethyl cellulose / styrene-butadiene rubber, hydroxypropylene cellulose, diacetylene cellulose, polyvinyl chloride, polyvinylpyrrolidone, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene or Polypropylene may be used, but is not limited thereto. The binder may be mixed in an amount of 1 to 30 wt% based on the total amount of the composition for forming the negative electrode active material layer.
상기 도전재로는 전지에 화학적 변화를 유발하지 않으면서 도전성을 가진 것이라면 특별히 제한되는 것은 아니며, 구체적으로는 천연 흑연, 인조 흑연 등의 흑연; 아세틸렌 블랙, 케첸 블랙, 채널 블랙, 퍼네이스 블랙, 램프 블랙, 서머 블랙 등의 카본 블랙; 탄소 섬유, 금속 섬유 등의 도전성 섬유; 불화 카본, 알루미늄, 니켈 분말 등의 금속 분말; 산화아연, 티탄산 칼륨 등의 도전성 위스키; 산화 티탄 등의 도전성 금속 산화물; 폴리페닐렌 유도체 등의 도전성 소재 등이 사용될 수 있다. 상기 도전재는 상기 음극 활물질층 형성용 조성물의 총량에 대하여 0.1 내지 30 중량%로 혼합될 수 있다.The conductive material is not particularly limited as long as it has conductivity without causing chemical changes to the battery. Specifically, graphite such as natural graphite and artificial graphite; Carbon blacks such as acetylene black, Ketjen black, channel black, furnace black, lamp black and summer black; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used. The conductive material may be mixed in an amount of 0.1 to 30 wt% based on the total amount of the negative electrode active material layer forming composition.
상기 양극은, 일 실시예에 따른 리튬 이차 전지용 양극 활물질을 포함한다. 즉, 전술한 양극 활물질, 바인더 및 선택적으로 도전재를 혼합하여 양극 활물질층 형성용 조성물을 제조한 후, 이 조성물을 알루미늄 등의 양극 집전체에 도포하여 제조할 수 있다. 또한, 도전재, 결합제 및 용매는 전술한 양극의 경우와 동일하게 사용된다.The cathode includes a cathode active material for a rechargeable lithium battery according to one embodiment. That is, the above-mentioned positive electrode active material, a binder, and optionally a conductive material may be mixed to prepare a composition for forming a positive electrode active material layer, and then the composition may be applied to a positive electrode current collector such as aluminum. In addition, a conductive material, a binder, and a solvent are used similarly to the case of the positive electrode mentioned above.
상기 리튬 이차 전지에 충진되는 전해질로는 비수성 전해질 또는 공지된 고체 전해질 등을 사용할 수 있으며, 리튬염이 용해된 것을 사용할 수 있다.As the electrolyte filled in the lithium secondary battery, a non-aqueous electrolyte or a known solid electrolyte may be used, and a lithium salt may be used.
상기 리튬염은, 예를 들면, LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, Li(CF3SO2)2N, LiC4F9SO3, LiSbF6, LiAlO4, LiAlCl4, LiCl, 및 LiI로 이루어진 군에서 선택된 1종 이상을 사용할 수 있다. The lithium salt is, for example, LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiSbF 6 , LiAlO At least one selected from the group consisting of 4 , LiAlCl 4 , LiCl, and LiI can be used.
상기 비수성 전해질의 용매로는, 예를 들면, 에틸렌카보네이트, 프로필렌카보네이트, 부틸렌카보네이트, 비닐렌카보네이트 등의 환상 카보네이트; 디메틸카보네이트, 메틸에틸카보네이트, 디에틸카보네이트 등의 쇄상 카보네이트; 아세트산메틸, 아세트산에틸, 아세트산프로필, 프로피온산메틸, 프로피온산에틸, γ-부티로락톤 등의 에스테르류; 1,2-디메톡시에탄, 1,2-디에톡시에탄, 테트라히드로푸란, 1,2-디옥산, 2-메틸테트라히드로푸란 등의 에테르류; 아세토니트릴 등의 니트릴류; 디메틸포름아미드 등의 아미드류 등을 사용할 수 있으나, 이에 한정되는 것은 아니다. 이들을 단독 또는 복수 개를 조합하여 사용할 수 있다. 특히, 환상 카보네이트와 쇄상 카보네이트와의 혼합 용매를 바람직하게 사용할 수 있다.As a solvent of the said non-aqueous electrolyte, For example, Cyclic carbonate, such as ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate; Chain carbonates such as dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate; Esters such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate and γ-butyrolactone; Ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1,2-dioxane and 2-methyltetrahydrofuran; Nitriles such as acetonitrile; Amides, such as dimethylformamide, etc. can be used, but it is not limited to this. These can be used individually or in combination of multiple pieces. In particular, a mixed solvent of a cyclic carbonate and a linear carbonate can be preferably used.
또한 전해질로서, 폴리에틸렌옥시드, 폴리아크릴로니트릴 등의 중합체 전해질에 전해액을 함침한 겔상 중합체 전해질이나, LiI, Li3N 등의 무기 고체 전해질이 가능하다.As the electrolyte, a gel polymer electrolyte in which an electrolyte solution is impregnated with a polymer electrolyte such as polyethylene oxide or polyacrylonitrile, or an inorganic solid electrolyte such as LiI or Li 3 N can be used.
상기 세퍼레이터는 내화학성 및 소수성의 폴리프로필렌 등의 올레핀계 폴리머; 유리섬유, 폴리에틸렌 등으로 만들어진 시트나 부직포 등이 사용될 수 있다. 전해액으로 폴리머 등의 고체 전해액이 사용되는 경우 고체 전해액이 분리막을 겸할 수도 있다.The separator may be an olefin polymer such as polypropylene having chemical resistance and hydrophobicity; Sheets or nonwovens made of glass fibers, polyethylene, and the like can be used. When a solid electrolyte such as a polymer is used as the electrolyte, the solid electrolyte may also serve as a separator.
본 발명은 상기 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 제조될 수 있으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다.The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person of ordinary skill in the art to which the present invention pertains does not change the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.
Claims (7)
상기 리튬 금속 산화물 입자 표면에 위치하는 코팅층;
을 포함하고,
상기 코팅층은 텅스텐 산화물을 포함하는 것인 리튬 이차 전지용 양극 활물질.
Lithium metal oxide particles; And
A coating layer on the surface of the lithium metal oxide particles;
Including,
The coating layer comprises a tungsten oxide positive electrode active material for a lithium secondary battery.
상기 텅스텐 산화물은, 추가적인 양이온으로 도핑된 것인 리튬 이차 전지용 양극 활물질.
The method of claim 1,
The tungsten oxide is a positive electrode active material for a lithium secondary battery that is doped with an additional cation.
상기 양이온은, B, Al, Si, Mg, Zn, Ti, Zr, V, Sr, Y, Ni, Co, Mn, 또는 이들의 조합인 것인 리튬 이차 전지용 양극 활물질.
The method of claim 2,
The cation is B, Al, Si, Mg, Zn, Ti, Zr, V, Sr, Y, Ni, Co, Mn, or a combination thereof.
상기 텅스텐 산화물은 하기 화학식 1로 표시되는 것인 리튬 이차 전지용 양극 활물질:
[화학식 1]
Li[LixWyM1-x-y]Oa
상기 화학식 1에서,
W는 텅스텐을 의미하고,
M은 비금속, 전이금속, 알칼리 토금속 또는 이들의 조합이고,
0≤x<1, 0≤y<1, 0<a<8이다.
The method of claim 2,
The tungsten oxide is a cathode active material for a lithium secondary battery that is represented by the following formula (1):
[Formula 1]
Li [Li x W y M 1-xy ] O a
In Chemical Formula 1,
W means tungsten,
M is a base metal, transition metal, alkaline earth metal or a combination thereof,
0≤x <1, 0≤y <1, 0 <a <8.
상기 화학식 1에서, M은 B, Al, Si, Mg, Zn, Ti, Zr, V, Sr, Y, Ni, Co, Mn, 또는 이들의 조합인 것인 리튬 이차 전지용 양극 활물질.
The method of claim 4, wherein
In Chemical Formula 1, M is B, Al, Si, Mg, Zn, Ti, Zr, V, Sr, Y, Ni, Co, Mn, or a combination thereof.
상기 리튬 금속 산화물은,
하기 화학식 1로 표시되는 화합물을 포함하는 것인 리튬 이차 전지용 양극 활물질:
[화학식 1]
Li1 + k[M11-α M2α]O2 - βQβ
상기 화학식 1에서,
M1는 NixCoyMnz , 이고,
M2는 Ti, Zr, Mg, M3, 또는 이들의 조합이고,
상기 M3는 알카리 토금속, 알칼리 금속, 3족 내지 12족 금속원소 및 13족 내지 15족 원소 중 적어도 하나를 포함하고,
Q는 F, P 및 S 중 적어도 하나를 포함하며,
-0.1 ≤ k ≤ 0.1, 0.0007≤ α ≤ 0.05, 0 ≤ β ≤ 0.1, 0.5 ≤ x ≤0 0.9, 0 ≤ y ≤ 0.2, 0 ≤ z ≤ 0.3 이다.
The method of claim 1,
The lithium metal oxide,
A cathode active material for a lithium secondary battery comprising the compound represented by Formula 1 below:
[Formula 1]
Li 1 + k [M1 1-α M2 α ] O 2 - β Q β
In Chemical Formula 1,
M1 is a Ni x Co y Mn z,,
M2 is Ti, Zr, Mg, M3, or a combination thereof,
M3 includes at least one of an alkaline earth metal, an alkali metal, a Group 3 to 12 metal element, and a Group 13 to 15 element,
Q includes at least one of F, P, and S,
−0.1 ≦ k ≦ 0.1, 0.0007 ≦ α ≦ 0.05, 0 ≦ β ≦ 0.1, 0.5 ≦ x ≦ 0 0.9, 0 ≦ y ≦ 0.2, 0 ≦ z ≦ 0.3.
음극; 그리고
전해액을 포함하고,
상기 양극은 제1항 내지 제6항 중 어느 한 항에 따른 리튬 이차 전지용 양극 활물질을 포함하는 리튬 이차 전지.
anode;
cathode; And
Including an electrolyte solution,
The positive electrode is a lithium secondary battery comprising the positive electrode active material for a lithium secondary battery according to any one of claims 1 to 6.
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