KR20170103507A - Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same - Google Patents
Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same Download PDFInfo
- Publication number
- KR20170103507A KR20170103507A KR1020160026500A KR20160026500A KR20170103507A KR 20170103507 A KR20170103507 A KR 20170103507A KR 1020160026500 A KR1020160026500 A KR 1020160026500A KR 20160026500 A KR20160026500 A KR 20160026500A KR 20170103507 A KR20170103507 A KR 20170103507A
- Authority
- KR
- South Korea
- Prior art keywords
- active material
- formula
- coating layer
- secondary battery
- lithium secondary
- Prior art date
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 239000011247 coating layer Substances 0.000 claims abstract description 28
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 24
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- 229910052796 boron Inorganic materials 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000006182 cathode active material Substances 0.000 claims description 29
- -1 Al (OH ) 3 Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 9
- 238000010304 firing Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910017119 AlPO Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 239000010955 niobium Substances 0.000 description 20
- 239000000843 powder Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000010936 titanium Substances 0.000 description 13
- 239000002131 composite material Substances 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000004020 conductor Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000011356 non-aqueous organic solvent Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 239000011812 mixed powder Substances 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 229910052800 carbon group element Inorganic materials 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000003660 carbonate based solvent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical compound FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 229910052795 boron group element Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- MYWGVEGHKGKUMM-UHFFFAOYSA-N carbonic acid;ethene Chemical compound C=C.C=C.OC(O)=O MYWGVEGHKGKUMM-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 150000005678 chain carbonates Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JYVXNLLUYHCIIH-UHFFFAOYSA-N (+/-)-mevalonolactone Natural products CC1(O)CCOC(=O)C1 JYVXNLLUYHCIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- RIWAPWDHHMWTRA-UHFFFAOYSA-N 1,2,3-triiodobenzene Chemical compound IC1=CC=CC(I)=C1I RIWAPWDHHMWTRA-UHFFFAOYSA-N 0.000 description 1
- PEBWOGPSYUIOBP-UHFFFAOYSA-N 1,2,4-trifluorobenzene Chemical compound FC1=CC=C(F)C(F)=C1 PEBWOGPSYUIOBP-UHFFFAOYSA-N 0.000 description 1
- KSXFNGRHPAHIQJ-UHFFFAOYSA-N 1,2,4-triiodobenzene Chemical compound IC1=CC=C(I)C(I)=C1 KSXFNGRHPAHIQJ-UHFFFAOYSA-N 0.000 description 1
- BBOLNFYSRZVALD-UHFFFAOYSA-N 1,2-diiodobenzene Chemical compound IC1=CC=CC=C1I BBOLNFYSRZVALD-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- UEMGWPRHOOEKTA-UHFFFAOYSA-N 1,3-difluorobenzene Chemical compound FC1=CC=CC(F)=C1 UEMGWPRHOOEKTA-UHFFFAOYSA-N 0.000 description 1
- SFPQFQUXAJOWNF-UHFFFAOYSA-N 1,3-diiodobenzene Chemical compound IC1=CC=CC(I)=C1 SFPQFQUXAJOWNF-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
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- QUGUFLJIAFISSW-UHFFFAOYSA-N 1,4-difluorobenzene Chemical compound FC1=CC=C(F)C=C1 QUGUFLJIAFISSW-UHFFFAOYSA-N 0.000 description 1
- LFMWZTSOMGDDJU-UHFFFAOYSA-N 1,4-diiodobenzene Chemical compound IC1=CC=C(I)C=C1 LFMWZTSOMGDDJU-UHFFFAOYSA-N 0.000 description 1
- WGPNJZYOHABTAS-UHFFFAOYSA-N 1,5,6-trichloro-5-methylcyclohexa-1,3-diene Chemical compound CC1(Cl)C=CC=C(Cl)C1Cl WGPNJZYOHABTAS-UHFFFAOYSA-N 0.000 description 1
- HLXVPOUBXXSTNB-UHFFFAOYSA-N 1,5,6-trifluoro-5-methylcyclohexa-1,3-diene Chemical compound CC1(F)C=CC=C(F)C1F HLXVPOUBXXSTNB-UHFFFAOYSA-N 0.000 description 1
- CXKUBSWJMNSYFO-UHFFFAOYSA-N 1,5-dichloro-5-methylcyclohexa-1,3-diene Chemical compound CC1(Cl)CC(Cl)=CC=C1 CXKUBSWJMNSYFO-UHFFFAOYSA-N 0.000 description 1
- PXMUFZLVYDRMJG-UHFFFAOYSA-N 1,5-difluoro-5-methylcyclohexa-1,3-diene Chemical compound CC1(F)CC(F)=CC=C1 PXMUFZLVYDRMJG-UHFFFAOYSA-N 0.000 description 1
- OLXMSYKIKJDKRQ-UHFFFAOYSA-N 1,5-diiodo-5-methylcyclohexa-1,3-diene Chemical compound CC1(I)CC(I)=CC=C1 OLXMSYKIKJDKRQ-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- MMZYCBHLNZVROM-UHFFFAOYSA-N 1-fluoro-2-methylbenzene Chemical compound CC1=CC=CC=C1F MMZYCBHLNZVROM-UHFFFAOYSA-N 0.000 description 1
- RINOYHWVBUKAQE-UHFFFAOYSA-N 1-iodo-2-methylbenzene Chemical compound CC1=CC=CC=C1I RINOYHWVBUKAQE-UHFFFAOYSA-N 0.000 description 1
- UDHAWRUAECEBHC-UHFFFAOYSA-N 1-iodo-4-methylbenzene Chemical compound CC1=CC=C(I)C=C1 UDHAWRUAECEBHC-UHFFFAOYSA-N 0.000 description 1
- YWWOHROKOFWJSP-UHFFFAOYSA-N 2,5,6-trichloro-5-methylcyclohexa-1,3-diene Chemical compound CC1(Cl)C=CC(Cl)=CC1Cl YWWOHROKOFWJSP-UHFFFAOYSA-N 0.000 description 1
- ZMTGTJVJFGMZKJ-UHFFFAOYSA-N 2,5,6-trifluoro-5-methylcyclohexa-1,3-diene Chemical compound CC1(F)C=CC(F)=CC1F ZMTGTJVJFGMZKJ-UHFFFAOYSA-N 0.000 description 1
- OPNQJIWBFJUXNO-UHFFFAOYSA-N 2,5-dichloro-5-methylcyclohexa-1,3-diene Chemical compound CC1(Cl)CC=C(Cl)C=C1 OPNQJIWBFJUXNO-UHFFFAOYSA-N 0.000 description 1
- UTWYQAQAMJSNCX-UHFFFAOYSA-N 2,5-difluoro-5-methylcyclohexa-1,3-diene Chemical compound CC1(F)CC=C(F)C=C1 UTWYQAQAMJSNCX-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- DNMSBVYZDQGYLU-UHFFFAOYSA-N 2-oxo-1,3-dioxolane-4-carbonitrile Chemical compound O=C1OCC(C#N)O1 DNMSBVYZDQGYLU-UHFFFAOYSA-N 0.000 description 1
- HIGQQEOWQNDHJD-UHFFFAOYSA-N 4,4-dichloro-1,3-dioxolan-2-one Chemical compound ClC1(Cl)COC(=O)O1 HIGQQEOWQNDHJD-UHFFFAOYSA-N 0.000 description 1
- RKDNQLPSWHNCFU-UHFFFAOYSA-N 4,5-dibromo-1,3-dioxolan-2-one Chemical compound BrC1OC(=O)OC1Br RKDNQLPSWHNCFU-UHFFFAOYSA-N 0.000 description 1
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 description 1
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- GPSZQZDENOVTHL-UHFFFAOYSA-N 4-nitro-1,3-dioxolan-2-one Chemical compound [O-][N+](=O)C1COC(=O)O1 GPSZQZDENOVTHL-UHFFFAOYSA-N 0.000 description 1
- PCEVCXPUGOBVFG-UHFFFAOYSA-N 5,6-dichloro-5-methylcyclohexa-1,3-diene Chemical compound CC1(Cl)C=CC=CC1Cl PCEVCXPUGOBVFG-UHFFFAOYSA-N 0.000 description 1
- CMTFMQAGUXZMHD-UHFFFAOYSA-N 5,6-difluoro-5-methylcyclohexa-1,3-diene Chemical compound CC1(F)C=CC=CC1F CMTFMQAGUXZMHD-UHFFFAOYSA-N 0.000 description 1
- DTWXIVZRKZIBPP-UHFFFAOYSA-N 5,6-diiodo-5-methylcyclohexa-1,3-diene Chemical compound CC1(I)C=CC=CC1I DTWXIVZRKZIBPP-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-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
- 229910013188 LiBOB 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
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- JYVXNLLUYHCIIH-ZCFIWIBFSA-N R-mevalonolactone, (-)- Chemical compound C[C@@]1(O)CCOC(=O)C1 JYVXNLLUYHCIIH-ZCFIWIBFSA-N 0.000 description 1
- 229910008326 Si-Y Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006773 Si—Y Inorganic materials 0.000 description 1
- 229910020997 Sn-Y Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910008859 Sn—Y Inorganic materials 0.000 description 1
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-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
- 229920005993 acrylate styrene-butadiene rubber polymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011326 fired coke Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 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
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229910021473 hassium Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 1
- 239000006051 mesophase pitch carbide Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 229940057061 mevalonolactone Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- GHZRKQCHJFHJPX-UHFFFAOYSA-N oxacycloundecan-2-one Chemical compound O=C1CCCCCCCCCO1 GHZRKQCHJFHJPX-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910021481 rutherfordium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910021477 seaborgium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RBYFNZOIUUXJQD-UHFFFAOYSA-J tetralithium oxalate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O RBYFNZOIUUXJQD-UHFFFAOYSA-J 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
-
- Y02E60/122—
Abstract
Description
리튬 이차 전지용 양극 활물질, 리튬 이차 전지용 양극 활물질의 제조 방법 및 리튬 이차전지용 양극 활물질에 관한 것이다. A cathode active material for a lithium secondary battery, a method for producing a cathode active material for a lithium secondary battery, and a cathode active material for a lithium secondary battery.
최근 휴대용 전자기기의 소형화 및 경량화 추세와 관련하여 이들 기기의 전원으로 사용되는 전지의 고성능화 및 대용량화에 대한 필요성이 높아지고 있다.Recently, with regard to the tendency to miniaturize and lighten portable electronic devices, there is an increasing need for high performance and large capacity of batteries used as power sources for these devices.
전지는 양극과 음극에 전기 화학 반응이 가능한 물질을 사용함으로써 전력을 발생시키는 것이다. 이러한 전지 중 대표적인 예로는 양극 및 음극에서 리튬 이온이 인터칼레이션/디인터칼레이션될 때의 화학전위(chemical potential)의 변화에 의하여 전기 에너지를 생성하는 리튬 이차 전지가 있다.Cells generate electricity by using materials that can electrochemically react to the positive and negative electrodes. A representative example of such a battery is a lithium secondary battery that generates electrical energy by a change in chemical potential when the lithium ions are intercalated / deintercalated in the positive electrode and the negative electrode.
상기 리튬 이차 전지는 리튬 이온의 가역적인 인터칼레이션/디인터칼레이션이 가능한 물질을 양극과 음극 활물질로 사용하고, 상기 양극과 음극 사이에 유기 전해액 또는 폴리머 전해액을 충전시켜 제조한다.The lithium secondary battery is manufactured by using a material capable of reversible intercalation / deintercalation of lithium ions as a positive electrode and a negative electrode active material, and filling an organic electrolyte or a polymer electrolyte between the positive electrode and the negative electrode.
리튬 이차 전지의 양극 활물질로는 리튬 복합금속 화합물이 사용되고 있으며, 그 예로 LiCoO2, LiMn2O4, LiNiO2, LiMnO2 등의 복합금속 산화물들이 연구되고 있다. As a cathode active material of a lithium secondary battery, a lithium composite metal compound is used. For example, composite metal oxides such as LiCoO 2 , LiMn 2 O 4 , LiNiO 2 and LiMnO 2 have been studied.
상기 양극 활물질 중 LiMn2O4, LiMnO2 등의 Mn계 양극 활물질은 합성하기도 쉽고, 값이 비교적 싸며, 과충전시 다른 활물질에 비하여 열적 안정성이 가장 우수하고, 환경에 대한 오염이 낮아 매력이 있는 물질이기는 하나, 용량이 적다는 단점을 가지고 있다.Of the above cathode active materials, Mn-based cathode active materials such as LiMn 2 O 4 and LiMnO 2 are easy to synthesize and are relatively inexpensive and have excellent thermal stability compared to other active materials in overcharging, However, it has a disadvantage of low capacity.
LiCoO2는 양호한 전기 전도도와 약 3.7V 정도의 높은 전지 전압을 가지며, 사이클 수명 특성, 안정성 또한 방전 용량 역시 우수하므로, 현재 상업화되어 시판되고 있는 대표적인 양극 활물질이다. 그러나 LiCoO2는 가격이 비싸기 때문에 전지 가격의 30% 이상을 차지하므로 가격 경쟁력이 떨어지는 문제점이 있다.LiCoO 2 is a typical cathode active material commercially available and commercially available since it has good electric conductivity, high battery voltage of about 3.7 V, excellent cycle life characteristics, stability and discharge capacity. However, since LiCoO 2 is expensive, it accounts for more than 30% of the battery price, which causes the price competitiveness to deteriorate.
또한 LiNiO2는 위에서 언급한 양극 활물질 중 가장 높은 방전 용량의 전지 특성을 나타내고 있으나, 합성하기 어려운 단점이 있다. 또한 니켈의 높은 산화상태는 전지 및 전극 수명 저하의 원인이 되며, 자기 방전이 심하고 가역성이 떨어지는 문제가 있다. 아울러, 안정성 확보가 완전하지 않아서 상용화에 어려움을 겪고 있다.LiNiO 2 also exhibits the highest discharge capacity of the battery among the above-mentioned cathode active materials, but it is difficult to synthesize LiNiO 2 . Also, the high oxidation state of nickel causes degradation of battery life and electrode life, and there is a problem that self discharge is severe and reversibility is low. In addition, it is difficult to commercialize it because the stability is not completely secured.
본 발명의 일 구현예는 수명 특성이 우수한 리튬 이차 전지용 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지를 제공하는 것이다.One embodiment of the present invention provides a cathode active material for a lithium secondary battery having excellent life characteristics, a method for producing the same, and a lithium secondary battery including the same.
본 발명의 일 구현예에서는, 하기 화학식 1로 표시되는 화합물을 포함하는 코어; 및 코어의 표면에 위치한 코팅층을 포함하는 리튬 이차 전지용 양극 활물질을 제공한다.In one embodiment of the present invention, a core comprising a compound represented by the following general formula (1); And a coating layer disposed on a surface of the core. The present invention also provides a cathode active material for a lithium secondary battery.
[화학식 1][Chemical Formula 1]
Li[LizA(1-z-a)Da]EbO2 -b Li [Li z A (1-za) D a ] E b O 2 -b
(상기 화학식 1에서 A는 NiαCoβMnγ이고, D는 Mg, Al, B, Zr, Mo, Nb 및 Ti로 이루어진 군에서 선택된 1종 이상의 원소이고, E는 P, F 및 S로 이루어진 군에서 선택된 1종 이상의 원소이고, -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05≤ β≤0.4 및 0.05≤ γ≤0.4 이다.)Wherein A is Ni ? Co ? Mn ? And D is at least one element selected from the group consisting of Mg, Al, B, Zr, Mo, Nb and Ti; E is P, F and S; , 0.05? Z? 0.1, 0? A? 0.05, 0? B? 0.05, 0.3??? 0.9, 0.05?? 0.4 and 0.05?? 0.4.
화학식 1에서, -0.05 ≤ z ≤ 0.05, 0.6 ≤ α ≤ 0.9, 0.05≤ β≤0.2 및 0.05≤ γ≤0.2일 수 있다.In the formula (1), -0.05? Z? 0.05, 0.6??? 0.9, 0.05?? 0.2 and 0.05???
화학식 1에서 D는 Mo, Nb, Zr, Ti 또는 이들의 조합일 수 있다.In formula (1), D may be Mo, Nb, Zr, Ti or a combination thereof.
화학식 1에서 D는 Mo, Nb 또는 이들의 조합일 수 있다.In formula (1), D may be Mo, Nb or a combination thereof.
화학식 1에서 D의 몰 도핑비율은 0.001 내지 0.01일 수 있다.The molar doping ratio of D in formula (1) may be 0.001 to 0.01.
코팅층은 Al, B 또는 이들의 조합을 포함할 수 있다.The coating layer may comprise Al, B or a combination thereof.
양극 활물질의 총 중량에 대하여 코팅층의 함량은 0.05 내지 1.0 중량%가 될 수 있다.The content of the coating layer may be 0.05 to 1.0% by weight based on the total weight of the cathode active material.
코팅층은 코어의 표면에 부분적으로 위치되는 아일랜드(Island) 형태일 수 있다.The coating layer may be in the form of an island that is partially located on the surface of the core.
코팅층은 F를 더 포함할 수 있다.The coating layer may further comprise F.
본 발명의 다른 일 구현예에서는, 하기 화학식 1로 표시되는 화합물을 포함하는 코어를 준비하는 단계; 코어와 코팅층을 형성하는 원료 화합물을 혼합하여 혼합물을 제조하는 단계; 및 혼합물을 소성하는 단계를 포함하는 리튬 이차 전지용 양극 활물질의 제조 방법을 제공한다.In another embodiment of the present invention, there is provided a method of preparing a core comprising the steps of: preparing a core comprising a compound represented by the following Formula 1; Preparing a mixture by mixing a core and a raw material compound forming a coating layer; And firing the mixture. The present invention also provides a method for producing a cathode active material for a lithium secondary battery.
[화학식 1][Chemical Formula 1]
Li[LizA(1-z-a)Da]EbO2 -b Li [Li z A (1-za) D a ] E b O 2 -b
(상기 화학식 1에서 A는 NiαCoβMnγ이고, D는 Mg, Al, B, Zr, Mo, Nb 및 Ti로 이루어진 군에서 선택된 1종 이상의 원소이고, E는 P, F 및 S로 이루어진 군에서 선택된 1종 이상의 원소이고, -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05≤ β≤0.4 및 0.05≤ γ≤0.4 이다.)Wherein A is Ni ? Co ? Mn ? And D is at least one element selected from the group consisting of Mg, Al, B, Zr, Mo, Nb and Ti; E is P, F and S; , 0.05? Z? 0.1, 0? A? 0.05, 0? B? 0.05, 0.3??? 0.9, 0.05?? 0.4 and 0.05?? 0.4.
화학식 1에서 -0.05 ≤ z ≤ 0.05, 0.6 ≤ α ≤ 0.9, 0.05≤ β≤0.2 및 0.05≤ γ≤0.2일 수 있다.In the formula (1), -0.05? Z? 0.05, 0.6??? 0.9, 0.05?? 0.2 and 0.05???
화학식 1에서 D는 Mo, Nb, Zr, Ti 또는 이들의 조합일 수 있다.In formula (1), D may be Mo, Nb, Zr, Ti or a combination thereof.
화학식 1에서 D는 Mo, Nb 또는 이들의 조합일 수 있다.In formula (1), D may be Mo, Nb or a combination thereof.
화학식 1에서 D의 몰 도핑비율은 0.001 내지 0.01일 수 있다.The molar doping ratio of D in formula (1) may be 0.001 to 0.01.
혼합물을 제조하는 단계에서, 원료 화합물은 알루미늄 공급원, 붕소 공급원 또는 이들의 조합일 수 있다.In the step of preparing the mixture, the starting compound may be an aluminum source, a boron source or a combination thereof.
혼합물을 제조하는 단계에서, 원료 화합물은 Al2O3, Al(OH)3, AlPO4, Al(NO3)3, B2O3, H3BO4, B(OH)3, Li2B4O7 또는 이들의 조합일 수 있다.In preparing the mixture, the raw material compound is Al 2 O 3, Al (OH ) 3, AlPO 4, Al (NO 3) 3, B 2
혼합물을 소성하는 단계에서, 소성 온도는 300 내지 450℃가 될 수 있다.In the step of firing the mixture, the firing temperature may be 300 to 450 캜.
본 발명의 또 다른 일 구현예에서는, 전술한 본 발명의 일 구현예에 따른 리튬 이차 전지용 양극 활물질을 포함하는 양극; 음극 활물질을 포함하는 음극; 및 전해질;을 포함하는 리튬 이차 전지를 제공한다. According to another embodiment of the present invention, there is provided a positive electrode comprising a positive electrode active material for a lithium secondary battery according to an embodiment of the present invention; A negative electrode comprising a negative electrode active material; And an electrolyte.
우수한 전지 특성을 갖는 양극 활물질 및 이를 포함하는 리튬 이차 전지를 제공할 수 있다.A positive electrode active material having excellent battery characteristics and a lithium secondary battery including the same can be provided.
도 1은 리튬 이차 전지의 개략도이다. 1 is a schematic view of a lithium secondary battery.
이하, 본 발명의 구현예를 상세히 설명하기로 한다. 다만, 이는 예시로서 제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구범위의 범주에 의해 정의될 뿐이다.Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.
본 발명의 일 구현예에서는, 하기 화학식 1로 표시되는 화합물을 포함하는 코어; 및 코어의 표면에 위치한 코팅층을 포함하는 리튬 이차 전지용 양극 활물질을 제공한다.In one embodiment of the present invention, a core comprising a compound represented by the following general formula (1); And a coating layer disposed on a surface of the core. The present invention also provides a cathode active material for a lithium secondary battery.
[화학식 1][Chemical Formula 1]
Li[LizA(1-z-a)Da]EbO2 -b Li [Li z A (1-za) D a ] E b O 2 -b
(상기 화학식 1에서 A는 NiαCoβMnγ이고, D는 Mg, Al, B, Zr, Mo, Nb 및 Ti로 이루어진 군에서 선택된 1종 이상의 원소이고, E는 P, F 및 S로 이루어진 군에서 선택된 1종 이상의 원소이고, -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05≤ β≤0.4 및 0.05≤ γ≤0.4 이다.)Wherein A is Ni ? Co ? Mn ? And D is at least one element selected from the group consisting of Mg, Al, B, Zr, Mo, Nb and Ti; E is P, F and S; , 0.05? Z? 0.1, 0? A? 0.05, 0? B? 0.05, 0.3??? 0.9, 0.05?? 0.4 and 0.05?? 0.4.
화학식 1에서, -0.05 ≤ z ≤ 0.05, 0.6 ≤ α ≤ 0.9, 0.05≤ β≤0.2 및 0.05≤ γ≤0.2일 수 있다.In the formula (1), -0.05? Z? 0.05, 0.6??? 0.9, 0.05?? 0.2 and 0.05???
본 발명의 일 구현예에 따른 양극 활물질은 리튬 이차 전지의 전지적 특성을 향상시킬 수 있다. 보다 구체적으로, 본 발명의 일 구현예에 따르면, 향상된 수명 특성을 가지는 양극 활물질을 제공할 수 있다.The cathode active material according to one embodiment of the present invention can improve the battery characteristics of the lithium secondary battery. More specifically, according to one embodiment of the present invention, a cathode active material having improved lifetime characteristics can be provided.
화학식 1에서 D는 Mo, Nb, Zr, Ti 또는 이들의 조합일 수 있다. 구체적으로 화학식 1에서 D는 Mo, Nb 또는 이들의 조합일 수 있다. 더욱 구체적으로 D는 Mo 및 Nb로 구성되고, Zr 또는 Ti가 도핑된 것일 수 있다.In formula (1), D may be Mo, Nb, Zr, Ti or a combination thereof. Specifically, in Formula 1, D may be Mo, Nb or a combination thereof. More specifically, D is composed of Mo and Nb, and may be doped with Zr or Ti.
화학식 1에서 D의 몰 도핑비율은 0.001 내지 0.01일 수 있다.The molar doping ratio of D in formula (1) may be 0.001 to 0.01.
몰리브덴은 전지특성에서 안전성, 열안정성을 향상시킨다. 몰리브덴의 함유량이, 너무 적으면 그 효과가 충분히 발휘되지 않고, 함유량이 너무 많으면 극도로 수명 특성이 악화된다.Molybdenum improves safety and thermal stability in battery characteristics. If the content of molybdenum is too small, the effect can not be sufficiently exhibited, and if the content is too large, the life characteristics are extremely deteriorated.
니오브는 몰리브덴의 수명 특성이 악화 되는 것을 억제하며, 니오브의 함유량은 너무 적으면 그 효과가 충분히 발휘되지 않는다.Niobium inhibits deterioration of the lifetime characteristics of molybdenum, and if the content of niobium is too small, the effect is not sufficiently exhibited.
또한, 몰리브덴 및 니오브 뿐 아니라 지르코늄 또는 티타늄을 더 포함 할 경우 다른 원소에 의한 특성 개선을 방해하는 일 없이 수명 특성을 더 개선시킬 수 있다.In addition, when zirconium or titanium is further contained in addition to molybdenum and niobium, lifetime characteristics can be further improved without hindering improvement of properties by other elements.
본 발명의 일 구현예에 따른 양극 활물질은 코어 표면에 코팅층을 포함하며, 코어 표면 개질을 통하여 전해액과의 부반응을 억제하여 전지특성을 더욱 향상시킨다.The positive electrode active material according to an embodiment of the present invention includes a coating layer on the core surface and further improves the battery characteristics by suppressing side reactions with the electrolyte through the modification of the core surface.
코팅층은 Al, B 또는 이들의 조합을 포함할 수 있다. 코팅층은 F를 더 포함할 수 있다. 코팅층에 F를 더 포함하여 전해액과의 젖음성을 떨어뜨려 부반응을 억제하는 역할을 수행하여 표면 안정화를 더 시킬 수 있다. F는 코어 내에 포함되는 F에서 유래될 수 있다.The coating layer may comprise Al, B or a combination thereof. The coating layer may further comprise F. The coating layer may further contain F to lower the wettability with the electrolyte, thereby suppressing the side reaction, thereby further stabilizing the surface. F may originate from F contained within the core.
양극 활물질의 총 중량에 대하여 코팅층의 함량은 0.05 내지 1.0 중량%가 될 수 있다. 코팅층의 중량비가 너무 적은 경우 코팅층의 역할이 감소할 수 있으며, 코팅층의 중량비가 너무 많은 경우 초기용량 감소 및 충방전 효율의 감소가 나타날 수 있다. 다만, 이에 제한되는 것은 아니다.The content of the coating layer may be 0.05 to 1.0% by weight based on the total weight of the cathode active material. If the weight ratio of the coating layer is too small, the role of the coating layer may be decreased. If the weight ratio of the coating layer is too large, initial capacity decrease and charge / discharge efficiency may be decreased. However, the present invention is not limited thereto.
본 발명의 다른 일 구현예에서는, 하기 화학식 1로 표시되는 화합물을 포함하는 코어를 준비하는 단계; 코어와 코팅층을 형성하는 원료 화합물을 혼합하여 혼합물을 제조하는 단계; 및 혼합물을 소성하는 단계를 포함하는 리튬 이차 전지용 양극 활물질의 제조 방법을 제공한다.In another embodiment of the present invention, there is provided a method of preparing a core comprising the steps of: preparing a core comprising a compound represented by the following Formula 1; Preparing a mixture by mixing a core and a raw material compound forming a coating layer; And firing the mixture. The present invention also provides a method for producing a cathode active material for a lithium secondary battery.
[화학식 1][Chemical Formula 1]
Li[LizA(1-z-a)Da]EbO2 -b Li [Li z A (1-za) D a ] E b O 2 -b
(상기 화학식 1에서 A는 NiαCoβMnγ이고, D는 Mg, Al, B, Zr, Mo, Nb 및 Ti로 이루어진 군에서 선택된 1종 이상의 원소이고, E는 P, F 및 S로 이루어진 군에서 선택된 1종 이상의 원소이고, -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05≤ β≤0.4 및 0.05≤ γ≤0.4 이다.)Wherein A is Ni ? Co ? Mn ? And D is at least one element selected from the group consisting of Mg, Al, B, Zr, Mo, Nb and Ti; E is P, F and S; , 0.05? Z? 0.1, 0? A? 0.05, 0? B? 0.05, 0.3??? 0.9, 0.05?? 0.4 and 0.05?? 0.4.
이하에서는 리튬 이차전지용 양극 활물질의 제조 방법을 각 단계별로 구체적으로 설명한다.Hereinafter, a method for producing a cathode active material for a lithium secondary battery will be described in detail.
먼저, 화학식 1로 표시되는 화합물을 포함하는 코어를 준비한다. 화학식 1로 표시되는 화합물에 대해서는 전술하였으므로, 반복되는 설명은 생략한다.First, a core containing the compound represented by the formula (1) is prepared. Since the compound represented by the formula (1) has been described above, repeated description is omitted.
다음으로, 코어와 코팅층을 형성하는 원료 화합물을 혼합하여 혼합물을 제조한다.Next, a mixture is prepared by mixing the raw material compound forming the core and the coating layer.
원료 화합물은 알루미늄 공급원, 붕소 공급원 또는 이들의 조합일 수 있다. 구체적으로 알루미늄 공급원은 Al2O3, Al(OH)3, AlPO4, Al(NO3)3 또는 이들의 조합일 수 있다. 또한 붕소 공급원은 B2O3, H3BO4, B(OH)3, Li2B4O7 또는 이들의 조합일 수 있다.The source compound may be an aluminum source, a boron source, or a combination thereof. More specifically, an aluminum source may be an Al 2 O 3, Al (OH ) 3, AlPO 4, Al (NO 3) 3 , or a combination thereof. The boron source may also be B 2 O 3 , H 3 BO 4 , B (OH) 3 , Li 2 B 4 O 7, or a combination thereof.
다음으로, 혼합물을 소성한다. 이 때, 소성 온도는 300 내지 450℃가 될 수 있다. 소성 온도가 너무 낮은 경우에는 코팅층과 코어 간의 반응성이 떨어져 코팅층의 유리(遊離) 등 코팅의 효과를 기대하기 어렵다. 또한, 소성 온도가 너무 높은 경우에는 Al 및 B 공급 물질이 코어에 과도하게 부착됨으로써 전지의 초기 용량의 감소와 함께 상온, 고온 및 저온에서의 수명 특성 저하가 일어날 수 있다.Next, the mixture is baked. At this time, the firing temperature may be 300 to 450 占 폚. When the firing temperature is too low, the reactivity between the coating layer and the core is low, and it is difficult to expect a coating effect such as free coating of the coating layer. In addition, when the firing temperature is too high, the Al and B supply materials are excessively attached to the core, so that the initial capacity of the battery may be decreased and the lifetime characteristics at room temperature, high temperature and low temperature may be deteriorated.
제조된 양극 활물질에 대한 설명은 앞서 설명된 본 발명의 일 구현예와 동일하므로 구체적인 설명은 생략하도록 한다.The description of the manufactured positive electrode active material is the same as that of the embodiment of the present invention described above, so a detailed description thereof will be omitted.
본 발명의 또 다른 일 구현예에서는, 양극, 음극 및 전해질을 포함하는 리튬 이차 전지며, 양극은 전류 집전체 및 전류 집전체 상에 형성된 양극 활물질층을 포함하며, 양극 활물질층은, 전술한 양극 활물질을 포함하는 것인 리튬 이차 전지를 제공한다. In another embodiment of the present invention, there is provided a lithium secondary battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode includes a current collector and a positive electrode active material layer formed on the current collector, A lithium secondary battery comprising an active material.
양극 활물질과 관련된 설명은 전술한 본 발명의 일 구현예와 동일하기 때문에 중복되는 설명을 생략하도록 한다. Since the description related to the cathode active material is the same as that of the embodiment of the present invention described above, redundant description will be omitted.
상기 양극 활물질층은 바인더 및 도전재를 포함할 수 있다. The cathode active material layer may include a binder and a conductive material.
상기 바인더는 양극 활물질 입자들을 서로 잘 부착시키고, 또한 양극 활물질을 전류 집전체에 잘 부착시키는 역할을 하며, 그 대표적인 예로는 폴리비닐알콜, 카르복시메틸셀룰로즈, 히드록시프로필셀룰로즈, 디아세틸셀룰로즈, 폴리비닐클로라이드, 카르복실화된 폴리비닐클로라이드, 폴리비닐플루오라이드, 에틸렌 옥사이드를 포함하는 폴리머, 폴리비닐피롤리돈, 폴리우레탄, 폴리테트라플루오로에틸렌, 폴리비닐리덴 플루오라이드, 폴리에틸렌, 폴리프로필렌, 스티렌-부타디엔 러버, 아크릴레이티드 스티렌-부타디엔 러버, 에폭시 수지, 나일론 등을 사용할 수 있으나, 이에 한정되는 것은 아니다.The binder serves to adhere the positive electrode active material particles to each other and to adhere the positive electrode active material to the current collector. Typical examples thereof include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl Polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-acrylonitrile, styrene-butadiene rubber, Butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, and the like, but not limited thereto.
상기 도전재는 전극에 도전성을 부여하기 위해 사용되는 것으로서, 구성되는 전지에 있어서, 화학변화를 야기하지 않고 전자 전도성 재료이면 어떠한 것도 사용가능하며, 그 예로 천연 흑연, 인조 흑연, 카본 블랙, 아세틸렌 블랙, 케첸블랙, 탄소섬유 등의 탄소계 물질; 구리, 니켈, 알루미늄, 은 등의 금속 분말 또는 금속 섬유 등의 금속계 물질; 폴리페닐렌 유도체 등의 도전성 폴리머; 또는 이들의 혼합물을 포함하는 도전성 재료를 사용할 수 있다.The conductive material is used for imparting conductivity to the electrode. Any conductive material can be used without causing any chemical change in the battery. Examples of the conductive material include natural graphite, artificial graphite, carbon black, acetylene black, Carbon-based materials such as black and carbon fiber; Metal powders such as copper, nickel, aluminum, and silver, or metal-based materials such as metal fibers; Conductive polymers such as polyphenylene derivatives; Or a mixture thereof may be used.
상기 음극은 집전체 및 상기 집전체 위에 형성된 음극 활물질층을 포함하며, 상기 음극 활물질층은 음극 활물질을 포함한다.The negative electrode includes a current collector and a negative active material layer formed on the current collector, and the negative active material layer includes a negative active material.
상기 음극 활물질로는 리튬 이온을 가역적으로 인터칼레이션/디인터칼레이션할 수 있는 물질, 리튬 금속, 리튬 금속의 합금, 리튬을 도프 및 탈도프할 수 있는 물질, 또는 전이 금속 산화물을 포함한다. The negative electrode active material includes a material capable of reversibly intercalating / deintercalating lithium ions, a lithium metal, an alloy of lithium metal, a material capable of doping and dedoping lithium, or a transition metal oxide.
상기 리튬 이온을 가역적으로 인터칼레이션/디인터칼레이션할 수 있는 물질로는 탄소 물질로서, 리튬 이온 이차 전지에서 일반적으로 사용되는 탄소계 음극 활물질은 어떠한 것도 사용할 수 있으며, 그 대표적인 예로는 결정질 탄소, 비정질 탄소 또는 이들을 함께 사용할 수 있다. 상기 결정질 탄소의 예로는 무정형, 판상, 린편상(flake), 구형 또는 섬유형의 천연 흑연 또는 인조 흑연과 같은 흑연을 들 수 있고, 상기 비정질 탄소의 예로는 소프트 카본(soft carbon: 저온 소성 탄소) 또는 하드 카본(hard carbon), 메조페이스 피치 탄화물, 소성된 코크스 등을 들 수 있다.As a material capable of reversibly intercalating / deintercalating lithium ions, any carbonaceous anode active material commonly used in lithium ion secondary batteries can be used as the carbonaceous material. Typical examples thereof include crystalline carbon , Amorphous carbon, or a combination thereof. Examples of the crystalline carbon include graphite such as natural graphite or artificial graphite in the form of amorphous, plate-like, flake, spherical or fibrous type. Examples of the amorphous carbon include soft carbon (soft carbon) Or hard carbon, mesophase pitch carbide, fired coke, and the like.
상기 리튬 금속의 합금으로는 리튬과 Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al 및 Sn으로 이루어진 군에서 선택되는 금속의 합금이 사용될 수 있다.As the lithium metal alloy, a lithium-metal alloy may be selected from the group consisting of lithium, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, An alloy of a selected metal may be used.
상기 리튬을 도프 및 탈도프할 수 있는 물질로는 Si, SiOx(0 < x < 2), Si-Y 합금(상기 Y는 알칼리 금속, 알칼리 토금속, 13족 원소, 14족 원소, 전이금속, 희토류 원소 및 이들의 조합으로 이루어진 군에서 선택되는 원소이며, Si은 아님), Sn, SnO2, Sn-Y(상기 Y는 알칼리 금속, 알칼리 토금속, 13족 원소, 14족 원소, 전이금속, 희토류 원소 및 이들의 조합으로 이루어진 군에서 선택되는 원소이며, Sn은 아님) 등을 들 수 있고, 또한 이들 중 적어도 하나와 SiO2를 혼합하여 사용할 수도 있다. 상기 원소 Y로는 Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, 및 이들의 조합으로 이루어진 군에서 선택될 수 있다.As the material capable of doping and dedoping lithium, Si, SiO x (0 <x <2), Si-Y alloy (Y is an alkali metal, an alkali earth metal, a Group 13 element, a Group 14 element, Rare earth elements and combinations thereof, but not Si), Sn, SnO 2 , Sn-Y (wherein Y is at least one element selected from the group consisting of alkali metals, alkaline earth metals, Group 13 elements, Group 14 elements, Element and an element selected from the group consisting of combinations thereof, and not Sn), and at least one of them may be mixed with SiO 2 . The element Y may be at least one element selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Se, Te, Po, and combinations thereof.
상기 전이 금속 산화물로는 바나듐 산화물, 리튬 바나듐 산화물 등을 들 수 있다.Examples of the transition metal oxide include vanadium oxide, lithium vanadium oxide, and the like.
상기 음극 활물질 층은 또한 바인더를 포함하며, 선택적으로 도전재를 더욱 포함할 수도 있다.The negative electrode active material layer also includes a binder, and may optionally further include a conductive material.
상기 바인더는 음극 활물질 입자들을 서로 잘 부착시키고, 또한 음극 활물질을 전류 집전체에 잘 부착시키는 역할을 하며, 그 대표적인 예로 폴리비닐알콜, 카르복시메틸셀룰로즈, 히드록시프로필셀룰로즈, 폴리비닐클로라이드, 카르복실화된 폴리비닐클로라이드, 폴리비닐플루오라이드, 에틸렌 옥사이드를 포함하는 폴리머, 폴리비닐피롤리돈, 폴리우레탄, 폴리테트라플루오로에틸렌, 폴리비닐리덴 플루오라이드, 폴리에틸렌, 폴리프로필렌, 스티렌-부타디엔 러버, 아크릴레이티드 스티렌-부타디엔 러버, 에폭시 수지, 나일론 등을 사용할 수 있으나, 이에 한정되는 것은 아니다.The binder serves to adhere the anode active material particles to each other and to adhere the anode active material to the current collector. Typical examples thereof include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, Such as polyvinyl chloride, polyvinyl fluoride, polymers comprising ethylene oxide, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, Styrene-butadiene rubber, epoxy resin, nylon, and the like may be used, but the present invention is not limited thereto.
상기 도전재는 전극에 도전성을 부여하기 위해 사용되는 것으로서, 구성되는 전지에 있어서, 화학변화를 야기하지 않고 전자 전도성 재료이면 어떠한 것도 사용가능하며, 그 예로 천연 흑연, 인조 흑연, 카본 블랙, 아세틸렌 블랙, 케첸블랙, 탄소섬유 등의 탄소계 물질; 구리, 니켈, 알루미늄, 은 등의 금속 분말 또는 금속 섬유 등의 금속계 물질; 폴리페닐렌 유도체 등의 도전성 폴리머; 또는 이들의 혼합물을 포함하는 도전성 재료를 사용할 수 있다.The conductive material is used for imparting conductivity to the electrode. Any conductive material can be used without causing any chemical change in the battery. Examples of the conductive material include natural graphite, artificial graphite, carbon black, acetylene black, Carbon-based materials such as black and carbon fiber; Metal powders such as copper, nickel, aluminum, and silver, or metal-based materials such as metal fibers; Conductive polymers such as polyphenylene derivatives; Or a mixture thereof may be used.
상기 집전체로는 구리 박, 니켈 박, 스테인레스강 박, 티타늄 박, 니켈 발포체(foam), 구리 발포체, 전도성 금속이 코팅된 폴리머 기재, 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다.The collector may be selected from the group consisting of a copper foil, a nickel foil, a stainless steel foil, a titanium foil, a nickel foam, a copper foil, a polymer substrate coated with a conductive metal, and a combination thereof.
상기 전류 집전체로는 Al을 사용할 수 있으나 이에 한정되는 것은 아니다.As the current collector, Al may be used, but the present invention is not limited thereto.
상기 음극과 양극은 활물질, 도전재 및 결착제를 용매 중에서 혼합하여 활물질 조성물을 제조하고, 이 조성물을 전류 집전체에 도포하여 제조한다. 이와 같은 전극 제조 방법은 당해 분야에 널리 알려진 내용이므로 본 명세서에서 상세한 설명은 생략하기로 한다. 상기 용매로는 N-메틸피롤리돈 등을 사용할 수 있으나 이에 한정되는 것은 아니다.The negative electrode and the positive electrode are prepared by mixing an active material, a conductive material and a binder in a solvent to prepare an active material composition, and applying the composition to a current collector. The method of manufacturing the electrode is well known in the art, and therefore, a detailed description thereof will be omitted herein. As the solvent, N-methylpyrrolidone or the like can be used, but it is not limited thereto.
상기 전해질은 비수성 유기 용매와 리튬염을 포함한다. The electrolyte includes a non-aqueous organic solvent and a lithium salt.
상기 비수성 유기 용매는 전지의 전기화학적 반응에 관여하는 이온들이 이동할 수 있는 매질 역할을 한다. The non-aqueous organic solvent serves as a medium through which ions involved in the electrochemical reaction of the battery can move.
상기 비수성 유기용매로는 카보네이트계, 에스테르계, 에테르계, 케톤계, 알코올계, 또는 비양성자성 용매를 사용할 수 있다. 상기 카보네이트계 용매로는 디메틸 카보네이트(DMC), 디에틸 카보네이트(DEC), 디프로필 카보네이트(DPC), 메틸프로필 카보네이트(MPC), 에틸프로필 카보네이트(EPC), 메틸에틸 카보네이트(MEC), 에틸렌 카보네이트(EC), 프로필렌 카보네이트(PC), 부틸렌 카보네이트(BC) 등이 사용될 수 있으며, 상기 에스테르계 용매로는 메틸 아세테이트, 에틸 아세테이트, n-프로필 아세테이트, 디메틸아세테이트, 메틸프로피오네이트, 에틸프로피오네이트, γ-부티로락톤, 데카놀라이드(decanolide), 발레로락톤, 메발로노락톤(mevalonolactone), 카프로락톤(caprolactone), 등이 사용될 수 있다. 상기 에테르계 용매로는 디부틸 에테르, 테트라글라임, 디글라임, 디메톡시에탄, 2-메틸테트라히드로퓨란, 테트라히드로퓨란 등이 사용될 수 있으며, 상기 케톤계 용매로는 시클로헥사논 등이 사용될 수 있다. 또한 상기 알코올계 용매로는 에틸알코올, 이소프로필 알코올 등이 사용될 수 있으며, 상기 비양성자성 용매로는 R-CN(R은 탄소수 2 내지 20의 직쇄상, 분지상, 또는 환 구조의 탄화수소기이며, 이중결합 방향 환 또는 에테르 결합을 포함할 수 있다) 등의 니트릴류 디메틸포름아미드 등의 아미드류, 1,3-디옥솔란 등의 디옥솔란류 설포란(sulfolane)류 등이 사용될 수 있다. The non-aqueous organic solvent may be a carbonate, ester, ether, ketone, alcohol, or aprotic solvent. Examples of the carbonate solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), methyl ethyl carbonate (MEC) EC), propylene carbonate (PC), and butylene carbonate (BC) may be used. As the ester solvent, methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate , gamma -butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone, and the like can be used. Examples of the ether solvent include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, and tetrahydrofuran. As the ketone solvent, cyclohexanone may be used have. As the alcoholic solvent, ethyl alcohol, isopropyl alcohol and the like can be used. As the aprotic solvent, R-CN (R is a linear, branched or cyclic hydrocarbon group having 2 to 20 carbon atoms, , A double bond aromatic ring or an ether bond), and dioxolanes such as 1,3-dioxolane, sulfolanes, and the like can be used.
상기 비수성 유기 용매는 단독으로 또는 하나 이상 혼합하여 사용할 수 있으며, 하나 이상 혼합하여 사용하는 경우의 혼합 비율은 목적하는 전지 성능에 따라 적절하게 조절할 수 있고, 이는 당해 분야에 종사하는 사람들에게는 널리 이해될 수 있다.The non-aqueous organic solvent may be used alone or in admixture of one or more. If the non-aqueous organic solvent is used in combination, the mixing ratio may be appropriately adjusted according to the desired cell performance. .
또한, 상기 카보네이트계 용매의 경우 환형(cyclic) 카보네이트와 사슬형(chain) 카보네이트를 혼합하여 사용하는 것이 좋다. 이 경우 환형 카보네이트와 사슬형 카보네이트는 1:1 내지 1:9의 부피비로 혼합하여 사용하는 것이 전해액의 성능이 우수하게 나타날 수 있다. In the case of the carbonate-based solvent, it is preferable to use a mixture of a cyclic carbonate and a chain carbonate. In this case, when the cyclic carbonate and the chain carbonate are mixed in a volume ratio of 1: 1 to 1: 9, the performance of the electrolytic solution may be excellent.
본 발명의 일 구현예에 따른 비수성 유기용매는 상기 카보네이트계 용매에 방향족 탄화수소계 유기용매를 더 포함할 수도 있다. 이때 상기 카보네이트계 용매와 방향족 탄화수소계 유기용매는 1:1 내지 30:1의 부피비로 혼합될 수 있다.The non-aqueous organic solvent according to an embodiment of the present invention may further include an aromatic hydrocarbon-based organic solvent in the carbonate-based solvent. In this case, the carbonate-based solvent and the aromatic hydrocarbon-based organic solvent may be mixed in a volume ratio of 1: 1 to 30: 1.
상기 방향족 탄화수소계 유기용매로는 하기 화학식 2의 방향족 탄화수소계 화합물이 사용될 수 있다.The aromatic hydrocarbon-based organic solvent may be an aromatic hydrocarbon-based compound represented by the following formula (2).
[화학식 2](2)
(상기 화학식 2에서, R1 내지 R6는 각각 독립적으로 수소, 할로겐, C1 내지 C10 알킬기, 할로알킬기 또는 이들의 조합이다.)(Wherein R 1 to R 6 are each independently hydrogen, halogen, a C1 to C10 alkyl group, a haloalkyl group, or a combination thereof)
상기 방향족 탄화수소계 유기용매는 벤젠, 플루오로벤젠, 1,2-디플루오로벤젠, 1,3-디플루오로벤젠, 1,4-디플루오로벤젠, 1,2,3-트리플루오로벤젠, 1,2,4-트리플루오로벤젠, 클로로벤젠, 1,2-디클로로벤젠, 1,3-디클로로벤젠, 1,4-디클로로벤젠, 1,2,3-트리클로로벤젠, 1,2,4-트리클로로벤젠, 아이오도벤젠, 1,2-디아이오도벤젠, 1,3-디아이오도벤젠, 1,4-디아이오도벤젠, 1,2,3-트리아이오도벤젠, 1,2,4-트리아이오도벤젠, 톨루엔, 플루오로톨루엔, 1,2-디플루오로톨루엔, 1,3-디플루오로톨루엔, 1,4-디플루오로톨루엔, 1,2,3-트리플루오로톨루엔, 1,2,4-트리플루오로톨루엔, 클로로톨루엔, 1,2-디클로로톨루엔, 1,3-디클로로톨루엔, 1,4-디클로로톨루엔, 1,2,3-트리클로로톨루엔, 1,2,4-트리클로로톨루엔, 아이오도톨루엔, 1,2-디아이오도톨루엔, 1,3-디아이오도톨루엔, 1,4-디아이오도톨루엔, 1,2,3-트리아이오도톨루엔, 1,2,4-트리아이오도톨루엔, 자일렌, 및 이들의 조합으로 이루어진 군에서 선택되는 것이다.The aromatic hydrocarbon-based organic solvent is selected from the group consisting of benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3- , 1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 4-trichlorobenzene, iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene, 1,2,3-triiodobenzene, 1,2,4 - triiodobenzene, toluene, fluorotoluene, 1,2-difluorotoluene, 1,3-difluorotoluene, 1,4-difluorotoluene, 1,2,3-trifluorotoluene, 1,2,4-trifluorotoluene, chlorotoluene, 1,2-dichlorotoluene, 1,3-dichlorotoluene, 1,4-dichlorotoluene, 1,2,3-trichlorotoluene, 1,2,4 - trichlorotoluene, iodotoluene, 1,2-diiodotoluene, 1,3-diiodotoluene, 1,4-diiodotol Yen, it is 1,2,3-tree-iodo toluene, 1,2,4-iodo toluene, xylene, and selected from the group consisting of.
상기 비수성 전해질은 전지 수명을 향상시키기 위하여 비닐렌 카보네이트 또는 하기 화학식 3의 에틸렌 카보네이트계 화합물을 더욱 포함할 수도 있다.The non-aqueous electrolyte may further include vinylene carbonate or an ethylene carbonate-based compound represented by the following formula (3) to improve battery life.
[화학식 3](3)
(상기 화학식 3에서, R7 및 R8는 각각 독립적으로 수소, 할로겐기, 시아노기(CN), 니트로기(NO2) 또는 C1 내지 C5 플루오로알킬기이고, 상기 R7과 R8중 적어도 하나는 할로겐기, 시아노기(CN), 니트로기(NO2) 또는 C1 내지 C5의 플루오로알킬기이다.)(In
상기 에틸렌 카보네이트계 화합물의 대표적인 예로는 디플루오로 에틸렌카보네이트, 클로로에틸렌 카보네이트, 디클로로에틸렌 카보네이트, 브로모에틸렌 카보네이트, 디브로모에틸렌 카보네이트, 니트로에틸렌 카보네이트, 시아노에틸렌 카보네이트 또는 플루오로에틸렌 카보네이트 등을 들 수 있다. 이러한 수명 향상 첨가제를 더욱 사용하는 경우 그 사용량은 적절하게 조절할 수 있다.Representative examples of the ethylene carbonate-based compound include diethylene carbonate, diethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate, fluoroethylene carbonate, and the like, such as difluoroethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, . When such a life improving additive is further used, its amount can be appropriately adjusted.
상기 리튬염은 유기 용매에 용해되어, 전지 내에서 리튬 이온의 공급원으로 작용하여 기본적인 리튬 이차 전지의 작동을 가능하게 하고, 양극과 음극 사이의 리튬 이온의 이동을 촉진하는 역할을 하는 물질이다. 이러한 리튬염의 대표적인 예로는 LiPF6, LiBF4, LiSbF6, LiAsF6, LiC4F9SO3, LiClO4, LiAlO2, LiAlCl4, LiN(CxF2x+1SO2)(CyF2y+1SO2)(여기서, x 및 y는 자연수임), LiCl, LiI 및 LiB(C2O4)2(리튬 비스옥살레이토 보레이트(lithium bis(oxalato) borate; LiBOB)로 이루어진 군에서 선택되는 하나 또는 둘 이상을 지지(supporting) 전해염으로 포함한다. 리튬염의 농도는 0.1 내지 2.0M 범위 내에서 사용하는 것이 좋다. 리튬염의 농도가 상기 범위에 포함되면, 전해질이 적절한 전도도 및 점도를 가지므로 우수한 전해질 성능을 나타낼 수 있고, 리튬 이온이 효과적으로 이동할 수 있다.The lithium salt is dissolved in an organic solvent to act as a source of lithium ions in the cell to enable operation of a basic lithium secondary battery and to promote the movement of lithium ions between the anode and the cathode. The lithium salt Representative examples are LiPF 6, LiBF 4, LiSbF 6 ,
리튬 이차 전지의 종류에 따라 양극과 음극 사이에 세퍼레이터가 존재할 수 도 있다. 이러한 세퍼레이터로는 폴리에틸렌, 폴리프로필렌, 폴리비닐리덴 플루오라이드 또는 이들의 2층 이상의 다층막이 사용될 수 있으며, 폴리에틸렌/폴리프로필렌 2층 세퍼레이터, 폴리에틸렌/폴리프로필렌/폴리에틸렌 3층 세퍼레이터, 폴리프로필렌/폴리에틸렌/폴리프로필렌 3층 세퍼레이터 등과 같은 혼합 다층막이 사용될 수 있음은 물론이다.Depending on the type of the lithium secondary battery, a separator may exist between the positive electrode and the negative electrode. The separator may be a polyethylene / polypropylene double layer separator, a polyethylene / polypropylene / polyethylene triple layer separator, a polypropylene / polyethylene / poly It is needless to say that a mixed multilayer film such as a propylene three-layer separator and the like can be used.
리튬 이차 전지는 사용하는 세퍼레이터와 전해질의 종류에 따라 리튬 이온 전지, 리튬 이온 폴리머 전지 및 리튬 폴리머 전지로 분류될 수 있고, 형태에 따라 원통형, 각형, 코인형, 파우치형 등으로 분류될 수 있으며, 사이즈에 따라 벌크 타입과 박막 타입으로 나눌 수 있다. 이들 전지의 구조와 제조방법은 이 분야에 널리 알려져 있으므로 상세한 설명은 생략한다.The lithium secondary battery can be classified into a lithium ion battery, a lithium ion polymer battery, and a lithium polymer battery depending on the type of the separator and electrolyte used. The lithium secondary battery can be classified into a cylindrical shape, a square shape, a coin shape, Depending on the size, it can be divided into bulk type and thin type. The structure and the manufacturing method of these cells are well known in the art, and detailed description thereof will be omitted.
도 1에 본 발명의 리튬 이차 전지의 대표적인 구조를 개략적으로 나타내었다. 도 1에 나타낸 것과 같이 상기 리튬 이차 전지(1)는 양극(3), 음극(2) 및 상기 양극(3)과 음극(2) 사이에 존재하는 세퍼레이터(4)에 함침된 전해액을 포함하는 전지 용기(5)와, 상기 전지 용기(5)를 봉입하는 봉입 부재(6)를 포함한다.FIG. 1 schematically shows a representative structure of the lithium secondary battery of the present invention. 1, the lithium secondary battery 1 includes a
이하 본 발명의 실시예 및 비교예를 기재한다. 그러나 하기의 실시예는 본 발명의 일 실시예 일 뿐 본 발명이 하기한 실시예에 한정되는 것은 아니다.Hereinafter, examples and comparative examples of the present invention will be described. However, the following examples are only illustrative of the present invention and are not intended to limit the scope of the present invention.
실시예Example
실시예Example 1 One
믹서에 NCM 복합 전이 금속수산화물(몰비는 Ni:Co:Mn = 60:20:20)과 분산된 MoO2 분말과 Nb2O5 분말, Li2CO3 분말을 건식 혼합하였다. 그리고, 건식 혼합된 분말을 890℃에서 8시간 동안 열처리하여 Li1 .01Ni0 .60Co0 .20Mn0 .20Mo0 .01Nb0 .005O2 로 표시되는 리튬 복합 화합물을 제조하였다.The mixed NCM complex transition metal hydroxide (Ni: Co: Mn = 60:20:20), the dispersed MoO 2 powder, the Nb 2 O 5 powder and the Li 2 CO 3 powder were dry mixed in the mixer. Then, the dry mixed powder was heat-treated at 890 ° C. for 8 hours to produce a lithium composite compound represented by Li 1 .01 Ni 0 .60 Co 0 .20 Mn 0 .20 Mo 0 .01 Nb 0 .005 O 2 .
또한, 제조된 리튬 복합 화합물을 리튬 복합 화합물 : Al(OH)3 분말 : B2O3 분말 = 100:0.4:0.2의 중량비율로 건식 혼합한 후 소성하여, 분산된 Al(OH)3 분말과 B2O3 분말이 상기 리튬 복합 화합물 표면에 균일하게 부착되도록 하였다. 그리고, 건식 혼합된 분말을 400 ℃에서 6시간 동안 열처리하여 양극 활물질을 제조하였다.Further, the produced lithium composite compound of lithium composite compound: Al (OH) 3 powder: B 2 O 3 powder = 100: 0.4 and then fired after dry-mixed in a weight ratio of 0.2, and the dispersed Al (OH) 3 powder, and B 2 O 3 powder was uniformly adhered to the surface of the lithium composite compound. Then, the dry mixed powder was heat-treated at 400 ° C for 6 hours to prepare a cathode active material.
실시예Example 2 2
실시예 1에서 Li1 .01Ni0 .60Co0 .20Mn0 .20Mo0 .01Nb0 .005Zr0 .005O2로 표시되는 리튬 복합 화합물을 제조한 것을 제외하고 동일하게 양극 활물질을 제조하였다.Example 1 In the Li 1 .01 Ni 0 .60 Co 0 .20 Mn 0 .20 Mo 0 .01 Nb 0 .005 Zr 0 .005 O and the same positive electrode active material, except that the prepared lithium composite compounds represented by the 2 .
실시예Example 3 3
실시예 1에서 Li1 .01Ni0 .60Co0 .20Mn0 .20Mo0 .01Nb0 .005Ti0 .005O2로 표시되는 리튬 복합 화합물을 제조한 것을 제외하고 동일하게 양극 활물질을 제조하였다.Example 1 In the Li 1 .01 Ni 0 .60 Co 0 .20 Mn 0 .20 Mo 0 .01 Nb 0 .005 Ti 0 .005 O and the same positive electrode active material, except that the prepared lithium composite compounds represented by the 2 .
비교예Comparative Example 1 One
믹서에 NCM 복합 전이 금속수산화물(몰비는 Ni:Co:Mn = 60:20:20) 1몰에 대해 Li2CO3이 1.01몰이 되는 비율(Li/Metal=1.01)로 Li2CO3을 넣고 건식 혼합하였다. 그리고, 건식 혼합된 분말을 890℃에서 8시간 동안 열처리하여 양극 활물질을 제조하였다.NCM composite transition metal hydroxide in the mixer (a molar ratio of Ni: Co: Mn = 60:20:20) of about 1 mol Li 2 CO 3 1.01 Li 2 CO 3 to be put into the mole ratio (Li / Metal = 1.01) dry . Then, the dry mixed powder was heat-treated at 890 캜 for 8 hours to prepare a cathode active material.
비교예Comparative Example 2 2
믹서에 NCM 복합 전이 금속수산화물(몰비는 Ni:Co:Mn = 60:20:20)과 분산된 MoO2 분말과 Nb2O5 분말, Li2CO3 분말을 건식 혼합하였다. 그리고, 건식 혼합된 분말을 890℃에서 8시간 동안 열처리하여 Li1 .01Ni0 .60Co0 .20Mn0 .20Mo0 .01Nb0 .005O2 로 표시되는 리튬 복합 화합물을 제조하였다.The mixed NCM complex transition metal hydroxide (Ni: Co: Mn = 60:20:20), the dispersed MoO 2 powder, the Nb 2 O 5 powder and the Li 2 CO 3 powder were dry mixed in the mixer. Then, the dry mixed powder was heat-treated at 890 ° C. for 8 hours to obtain Li 1 .01 Ni 0 .60 Co 0 .20 Mn 0 .20 Mo 0 .01 Nb 0 .005 O 2 ≪ / RTI >
비교예Comparative Example 3 3
비교예 1에서 제조된 리튬 복합 화합물을 상기 리튬 복합 화합물 : Al(OH)3 분말 : B2O3 분말 = 100:0.4:0.2의 중량비율로 건식 혼합한 후 소성하여, 분산된 Al(OH)3 분말과 B2O3 분말이 상기 리튬 복합 화합물 표면에 균일하게 부착되도록 하였다. 그리고, 건식 혼합된 분말을 400 ℃에서 6시간 동안 열처리하여 양극 활물질을 제조하였다.The lithium composite compound prepared in Comparative Example 1 was dry mixed at a weight ratio of the lithium composite compound: Al (OH) 3 powder: B 2 O 3 powder = 100: 0.4: 0.2, 3 powder and B 2 O 3 powder were uniformly adhered to the surface of the lithium composite compound. Then, the dry mixed powder was heat-treated at 400 ° C for 6 hours to prepare a cathode active material.
코인셀의Coin cell 제조 Produce
전술한 실시예 및 비교예에서 제조된 양극 활물질 95 중량%, 도전제로 카본 블랙(carbon black) 2.5 중량%, 결합제로 PVDF 2.5중량% 를 용제(솔벤트)인 N-메틸-2 피롤리돈(NMP) 5.0 중량%에 첨가하여 양극 슬러리를 제조하였다. 상기 양극 슬러리를 두께 20 내지 40㎛의 양극 집전체인 알루미늄(Al) 박막에 도포 및 진공 건조하고 롤 프레스(roll press)를 실시하여 양극을 제조하였다.95% by weight of the cathode active material prepared in the above-mentioned Examples and Comparative Examples, 2.5% by weight of carbon black as a conductive agent and 2.5% by weight of PVDF as a binder were dissolved in N-methyl-2-pyrrolidone (NMP ) To 5.0 wt% to prepare a positive electrode slurry. The positive electrode slurry was coated on an aluminum (Al) thin film as a positive electrode current collector having a thickness of 20 to 40 mu m, followed by vacuum drying and roll pressing to produce a positive electrode.
음극으로는 Li-금속을 이용하였다.Li-metal was used as the cathode.
이와 같이 제조된 양극과 Li-금속을 대극으로, 전해액으로는 1.15M LiPF6EC:DMC(1:1vol%)을 사용하여 코인 셀 타입의 반쪽 전지를 제조하였다.A coin-cell type half-cell was fabricated by using the thus prepared positive electrode and Li-metal as a counter electrode and using 1.15M LiPF6EC: DMC (1: 1 vol%) as an electrolyte solution.
충방전은 4.5-3.0V 범위에서 실시하였다. 수명의 경우 1.0C 율로 평가하였다.Charging and discharging were performed in the range of 4.5-3.0V. The life span was evaluated at 1.0C.
실험예Experimental Example 1: 전지 특성 평가 1: Evaluation of battery characteristics
하기 표 1은 상기의 실시예 및 비교예의 4.5V 초기 Formation, 율특성, 1cyle, 20cycle, 30cycle 용량 및 수명특성 데이터이다.Table 1 below shows the 4.5 V initial formations, rate characteristics, 1 cycle, 20 cycle, 30 cycle capacity and life characteristic data of the examples and comparative examples.
방전용량1CY
Discharge capacity
방전용량20CY
Discharge capacity
방전용량30CY
Discharge capacity
(20CY/
1CY, %)Life characteristics
(20CY /
1CY,%)
(30CY/
1CY, %)Life characteristics
(30CY /
1CY,%)
표 1에서 나타나듯이, 실시예 1 내지 3은 비교예 1 내지 3 보다 수명특성에서 우수한 전지특성을 나타낸다.As shown in Table 1, Examples 1 to 3 exhibited excellent battery characteristics in terms of life characteristics than Comparative Examples 1 to 3.
보다 구체적으로, 몰리브덴과 니오브를 포함하는 실시예 1은 포함하지 않는 비교예 3에 비하여 고온 고전압에서 우수한 수명 특성이 확인된다. 또한, 실시예 2 내지 3에서 지르코늄 또는 티타늄을 더 포함 할 경우 더 뛰어난 전지특성을 확인 할 수 있다. 비교예 1 및 비교예 2의 경우, 코팅층이 존재하지 아니하여 전지 특성이 열악함을 확인할 수 있다.More specifically, excellent lifetime characteristics at high temperature and high voltage are confirmed as compared with Comparative Example 3 which does not include Example 1 including molybdenum and niobium. Further, when zirconium or titanium is further contained in Examples 2 to 3, superior battery characteristics can be confirmed. In the case of Comparative Example 1 and Comparative Example 2, the coating layer was not present and the battery characteristics were poor.
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.It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.
1: 리튬 이차 전지 2: 음극
3: 양극 4: 세퍼레이터
5: 전지 용기 6: 봉입 부재1: lithium secondary battery 2: negative electrode
3: anode 4: separator
5: Battery container 6: Sealing member
Claims (18)
상기 코어의 표면에 위치한 코팅층을 포함하는 리튬 이차 전지용 양극 활물질:
[화학식 1]
Li[LizA(1-z-a)Da]EbO2 -b
(상기 화학식 1에서 A는 NiαCoβMnγ이고, D는 Mg, Al, B, Zr, Mo, Nb 및 Ti로 이루어진 군에서 선택된 1종 이상의 원소이고, E는 P, F 및 S로 이루어진 군에서 선택된 1종 이상의 원소이고, -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05≤ β≤0.4 및 0.05≤ γ≤0.4 이다.)A core comprising a compound represented by the following formula (1); And
And a coating layer disposed on the surface of the core.
[Chemical Formula 1]
Li [Li z A (1-za) D a ] E b O 2 -b
Wherein A is Ni ? Co ? Mn ? And D is at least one element selected from the group consisting of Mg, Al, B, Zr, Mo, Nb and Ti; E is P, F and S; , 0.05? Z? 0.1, 0? A? 0.05, 0? B? 0.05, 0.3??? 0.9, 0.05?? 0.4 and 0.05?? 0.4.
상기 화학식 1에서 -0.05 ≤ z ≤ 0.05, 0.6 ≤ α ≤ 0.9, 0.05≤ β≤0.2 및 0.05≤ γ≤0.2인 리튬 이차 전지용 양극 활물질.The method according to claim 1,
Wherein 0.05? Z? 0.05, 0.6?? 0.9, 0.05?? 0.2 and 0.05??? 0.2 in the above formula (1).
상기 화학식 1에서 D는 Mo, Nb, Zr, Ti 또는 이들의 조합인 리튬 이차 전지용 양극 활물질.The method according to claim 1,
In the above formula (1), D is Mo, Nb, Zr, Ti, or a combination thereof, as a cathode active material for a lithium secondary battery.
상기 화학식 1에서 D는 Mo, Nb 또는 이들의 조합인 리튬 이차 전지용 양극 활물질.The method according to claim 1,
In Formula 1, D is Mo, Nb, or a combination thereof, as a cathode active material for a lithium secondary battery.
상기 화학식 1에서 D의 몰 도핑비율은 0.001 내지 0.01 인 리튬 이차 전지용 양극 활물질.The method according to claim 1,
Wherein the molar doping ratio of D in Formula 1 is 0.001 to 0.01.
상기 코팅층은 Al, B 또는 이들의 조합을 포함하는 리튬 이차 전지용 양극 활물질.The method according to claim 1,
Wherein the coating layer comprises Al, B, or a combination thereof.
전체 양극 활물질의 총 중량에 대하여 상기 코팅층의 함량은 0.05 내지 1.0 중량%인 리튬 이차 전지용 양극 활물질.The method according to claim 1,
Wherein the content of the coating layer is 0.05 to 1.0 wt% based on the total weight of the entire cathode active material.
상기 코팅층은 상기 코어의 표면에 부분적으로 위치되는 아일랜드(Island) 형태인 리튬 이차 전지용 양극 활물질.The method according to claim 1,
Wherein the coating layer is in the form of an island partly located on the surface of the core.
상기 코팅층은 F를 더 포함하는 코팅층인 것인 리튬 이차 전지용 양극 활물질.The method according to claim 6,
Wherein the coating layer is a coating layer further comprising F. The positive electrode active material for a lithium secondary battery according to claim 1,
상기 코어와 코팅층을 형성하는 원료 화합물을 혼합하여 혼합물을 제조하는 단계; 및
상기 혼합물을 소성하는 단계를 포함하는 리튬 이차 전지용 양극 활물질의 제조 방법:
[화학식 1]
Li[LizA(1-z-a)Da]EbO2 -b
(상기 화학식 1에서 A는 NiαCoβMnγ이고, D는 Mg, Al, B, Zr, Mo, Nb 및 Ti로 이루어진 군에서 선택된 1종 이상의 원소이고, E는 P, F 및 S로 이루어진 군에서 선택된 1종 이상의 원소이고, -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05≤ β≤0.4 및 0.05≤ γ≤0.4 이다.)Preparing a core comprising a compound represented by Formula 1 below;
Preparing a mixture by mixing the core and a raw material compound forming a coating layer; And
And firing the mixture. The method for producing a cathode active material for a lithium secondary battery according to claim 1,
[Chemical Formula 1]
Li [Li z A (1-za) D a ] E b O 2 -b
Wherein A is Ni ? Co ? Mn ? And D is at least one element selected from the group consisting of Mg, Al, B, Zr, Mo, Nb and Ti; E is P, F and S; , 0.05? Z? 0.1, 0? A? 0.05, 0? B? 0.05, 0.3??? 0.9, 0.05?? 0.4 and 0.05?? 0.4.
상기 화학식 1에서 -0.05 ≤ z ≤ 0.05, 0.6 ≤ α ≤ 0.9, 0.05≤ β≤0.2 및 0.05≤ γ≤0.2인 리튬 이차 전지용 양극 활물질의 제조 방법.11. The method of claim 10,
Wherein 0.05? Z? 0.05, 0.6?? 0.9, 0.05?? 0.2 and 0.05??? 0.2 in the above formula (1).
상기 화학식 1에서 D는 Mo, Nb, Zr, Ti 또는 이들의 조합인 리튬 이차 전지용 양극 활물질의 제조 방법.11. The method of claim 10,
Wherein D in Formula 1 is Mo, Nb, Zr, Ti, or a combination thereof.
상기 화학식 1에서 D는 Mo, Nb 또는 이들의 조합인 리튬 이차 전지용 양극 활물질의 제조 방법.11. The method of claim 10,
Wherein D in Formula 1 is Mo, Nb or a combination thereof.
상기 화학식 1에서 D의 몰 도핑비율은 0.001 내지 0.01 인 리튬 이차 전지용 양극 활물질의 제조 방법.11. The method of claim 10,
Wherein the molar doping ratio of D in Formula 1 is 0.001 to 0.01.
상기 혼합물을 제조하는 단계에서, 상기 원료 화합물은 알루미늄 공급원, 붕소 공급원 또는 이들의 조합인 리튬 이차 전지용 양극 활물질의 제조 방법.11. The method of claim 10,
Wherein the raw material compound is an aluminum source, a boron source, or a combination thereof in the step of preparing the mixture.
상기 혼합물을 제조하는 단계에서, 상기 원료 화합물은 Al2O3, Al(OH)3, AlPO4, Al(NO3)3, B2O3, H3BO4, B(OH)3, Li2B4O7 또는 이들의 조합인 리튬 이차 전지용 양극 활물질의 제조 방법.11. The method of claim 10,
In the step of producing the above mixture, the raw material compound is Al 2 O 3, Al (OH ) 3, AlPO 4, Al (NO 3) 3, B 2 O 3, H 3 BO 4, B (OH) 3, Li 2 B 4 O 7, or a combination thereof, for producing a cathode active material for a lithium secondary battery.
상기 혼합물을 소성하는 단계에서, 소성 온도는 300 내지 450℃ 인 리튬 이차 전지용 양극 활물질의 제조 방법.11. The method of claim 10,
And calcining the mixture at a calcining temperature of 300 to 450 ° C.
음극 활물질을 포함하는 음극; 및
전해질;
을 포함하는 리튬 이차 전지.A positive electrode comprising the positive electrode active material for a lithium secondary battery according to any one of claims 1 to 9;
A negative electrode comprising a negative electrode active material; And
Electrolyte;
≪ / RTI >
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160026500A KR102114229B1 (en) | 2016-03-04 | 2016-03-04 | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
| PCT/KR2017/002270 WO2017150914A1 (en) | 2016-03-04 | 2017-03-02 | Positive electrode active material for lithium secondary battery, method for producing same and lithium secondary battery comprising same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160026500A KR102114229B1 (en) | 2016-03-04 | 2016-03-04 | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20170103507A true KR20170103507A (en) | 2017-09-13 |
| KR102114229B1 KR102114229B1 (en) | 2020-05-22 |
Family
ID=59744195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020160026500A KR102114229B1 (en) | 2016-03-04 | 2016-03-04 | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR102114229B1 (en) |
| WO (1) | WO2017150914A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11870070B2 (en) | 2018-01-24 | 2024-01-09 | Lg Energy Solution, Ltd. | Positive electrode active material for secondary battery, method of preparing the same, and lithium secondary battery including the positive electrode active material |
| US11876157B2 (en) | 2018-09-28 | 2024-01-16 | Lg Chem, Ltd. | Positive electrolyte active material for secondary battery, preparation method thereof, and lithium secondary battery including same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102328991B1 (en) * | 2017-09-19 | 2021-11-22 | 주식회사 엘지에너지솔루션 | Positive electrode active material for secondary battery and lithium secondary battery comprising the same |
| KR102268079B1 (en) * | 2017-11-21 | 2021-06-23 | 주식회사 엘지화학 | Positive electrode active material for secondary battery, method for preparing the same and lithium secondary battery comprising the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120028622A (en) * | 2010-09-15 | 2012-03-23 | 한양대학교 산학협력단 | Cathode active material for lithium secondary battery, method for manufacturing the same and lithium secondary battery using the same |
| KR20120099375A (en) * | 2009-08-27 | 2012-09-10 | 엔비아 시스템즈 인코포레이티드 | Metal oxide coated positive electrode materials for lithium-based batteries |
| KR20140117311A (en) * | 2013-03-26 | 2014-10-07 | 주식회사 엘앤에프신소재 | Cathode active material for lithium secondary battery and lithium secondary battery using the same |
| WO2016032290A1 (en) * | 2014-08-29 | 2016-03-03 | 주식회사 엘앤에프신소재 | Cathode active material for lithium secondary battery, method for preparing same and lithium secondary battery comprising same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015083901A1 (en) * | 2013-12-02 | 2015-06-11 | 주식회사 엘앤에프신소재 | Cathode active material for lithium secondary battery, method for producing same, and lithium secondary battery containing same |
-
2016
- 2016-03-04 KR KR1020160026500A patent/KR102114229B1/en active IP Right Grant
-
2017
- 2017-03-02 WO PCT/KR2017/002270 patent/WO2017150914A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120099375A (en) * | 2009-08-27 | 2012-09-10 | 엔비아 시스템즈 인코포레이티드 | Metal oxide coated positive electrode materials for lithium-based batteries |
| KR20120028622A (en) * | 2010-09-15 | 2012-03-23 | 한양대학교 산학협력단 | Cathode active material for lithium secondary battery, method for manufacturing the same and lithium secondary battery using the same |
| KR20140117311A (en) * | 2013-03-26 | 2014-10-07 | 주식회사 엘앤에프신소재 | Cathode active material for lithium secondary battery and lithium secondary battery using the same |
| WO2016032290A1 (en) * | 2014-08-29 | 2016-03-03 | 주식회사 엘앤에프신소재 | Cathode active material for lithium secondary battery, method for preparing same and lithium secondary battery comprising same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11870070B2 (en) | 2018-01-24 | 2024-01-09 | Lg Energy Solution, Ltd. | Positive electrode active material for secondary battery, method of preparing the same, and lithium secondary battery including the positive electrode active material |
| US11876157B2 (en) | 2018-09-28 | 2024-01-16 | Lg Chem, Ltd. | Positive electrolyte active material for secondary battery, preparation method thereof, and lithium secondary battery including same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102114229B1 (en) | 2020-05-22 |
| WO2017150914A1 (en) | 2017-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101757628B1 (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR101646911B1 (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR101682502B1 (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR101625838B1 (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR101609544B1 (en) | Cathode active material for lithium secondary battery and lithium secondary battery using the same | |
| KR20150063956A (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR101788561B1 (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR101309149B1 (en) | Method for manufacturing positive active material for rechargeable lithium battery and rechargeable lithium battery using the same | |
| KR101586806B1 (en) | Method for manufacturing positive active material for lithium secondary battery, positive active material for lithium secondary battery and lithium secondary battery | |
| KR102217753B1 (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR20160026307A (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR20170103505A (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR102114229B1 (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR101878920B1 (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR20160093854A (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR101904773B1 (en) | Positive active material for rechargeable lithium battery | |
| KR102085247B1 (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR101673178B1 (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR101668799B1 (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR20170106810A (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR101586804B1 (en) | Method for manufacturing positive active material for lithium secondary battery and positive active material for lithium secondary battery | |
| KR101646702B1 (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR20160083818A (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR101493747B1 (en) | Method for manufacturing positive active material for lithium secondary battery, positive active material for lithium secondary battery and lithium secondary battery | |
| KR20160093817A (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |