KR20240038580A - Electrolyte solution for lithium secondary battery and lithium secondary battery including the same - Google Patents
Electrolyte solution for lithium secondary battery and lithium secondary battery including the same Download PDFInfo
- Publication number
- KR20240038580A KR20240038580A KR1020230093842A KR20230093842A KR20240038580A KR 20240038580 A KR20240038580 A KR 20240038580A KR 1020230093842 A KR1020230093842 A KR 1020230093842A KR 20230093842 A KR20230093842 A KR 20230093842A KR 20240038580 A KR20240038580 A KR 20240038580A
- Authority
- KR
- South Korea
- Prior art keywords
- lithium secondary
- secondary battery
- electrolyte solution
- weight
- electrolyte
- Prior art date
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 58
- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 39
- 239000000654 additive Substances 0.000 claims abstract description 40
- 230000000996 additive effect Effects 0.000 claims abstract description 37
- 239000003960 organic solvent Substances 0.000 claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 22
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims description 40
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 150000008053 sultones Chemical class 0.000 claims description 5
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 abstract description 2
- 229940021013 electrolyte solution Drugs 0.000 description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 239000007774 positive electrode material Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000003660 carbonate based solvent Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- STGXUBIZGYMIRM-UHFFFAOYSA-N (5-ethyl-1,3-dioxan-5-yl)methyl prop-2-enoate Chemical compound C=CC(=O)OCC1(CC)COCOC1 STGXUBIZGYMIRM-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000004020 conductor Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 102100028667 C-type lectin domain family 4 member A Human genes 0.000 description 5
- 101000766908 Homo sapiens C-type lectin domain family 4 member A Proteins 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000011255 nonaqueous electrolyte Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- -1 fluorine-substituted carbonate Chemical class 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002931 mesocarbon microbead Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- IFDLFCDWOFLKEB-UHFFFAOYSA-N 2-methylbutylbenzene Chemical compound CCC(C)CC1=CC=CC=C1 IFDLFCDWOFLKEB-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000006257 cathode slurry Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- GHZRKQCHJFHJPX-UHFFFAOYSA-N oxacycloundecan-2-one Chemical compound O=C1CCCCCCCCCO1 GHZRKQCHJFHJPX-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000002360 preparation method Methods 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
- 238000003756 stirring Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- JYVXNLLUYHCIIH-UHFFFAOYSA-N (+/-)-mevalonolactone Natural products CC1(O)CCOC(=O)C1 JYVXNLLUYHCIIH-UHFFFAOYSA-N 0.000 description 1
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JGZFZZXWCPJDRH-UHFFFAOYSA-N 2-methyloxolane Chemical compound CC1CCCO1.CC1CCCO1 JGZFZZXWCPJDRH-UHFFFAOYSA-N 0.000 description 1
- OQXNUCOGMMHHNA-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2,2-dioxide Chemical compound CC1COS(=O)(=O)O1 OQXNUCOGMMHHNA-UHFFFAOYSA-N 0.000 description 1
- BGFBWRWYROQISE-UHFFFAOYSA-N 5-ethyl-1,3-dioxane-5-methanol Chemical compound CCC1(CO)COCOC1 BGFBWRWYROQISE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910018279 LaSrMnO Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910017246 Ni0.8Co0.1Mn0.1 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011884 anode binding agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 229940057061 mevalonolactone Drugs 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910021435 silicon-carbon complex Inorganic materials 0.000 description 1
- 239000011867 silicon-carbon complex material Substances 0.000 description 1
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
예시적인 실시예에 따른 1,3-디옥산계 첨가제; 유기 용매; 및 리튬 염을 포함하는 리튬 이차 전지용 전해액이 제공될 수 있다. 이에, 상기 리튬 이차 전지용 전해액을 포함한 리튬 이차 전지는 우수한 고온 특성을 갖는다.1,3-dioxane-based additive according to an exemplary embodiment; organic solvent; And an electrolyte solution for a lithium secondary battery containing a lithium salt may be provided. Accordingly, a lithium secondary battery containing the electrolyte for a lithium secondary battery has excellent high-temperature characteristics.
Description
본 발명은 리튬 이차 전지용 전해액 및 이를 포함하는 리튬 이차 전지에 관한 것이다. 보다 상세하게는, 용매 및 전해질 염을 포함하는 리튬 이차 전지용 전해액 및 이를 포함하는 리튬 이차 전지에 관한 것이다.The present invention relates to an electrolyte for lithium secondary batteries and a lithium secondary battery containing the same. More specifically, it relates to an electrolyte solution for a lithium secondary battery containing a solvent and an electrolyte salt, and a lithium secondary battery containing the same.
이차 전지는 충전 및 방전이 반복 가능한 전지로서, 정보 통신 및 디스플레이 산업의 발전에 따라, 캠코더, 휴대폰, 노트북PC 등과 같은 휴대용 전자통신 기기들의 동력원으로 널리 적용되고 있다. 또한, 최근에는 하이브리드 자동차와 같은 친환경 자동차의 동력원으로 이차 전지를 포함한 전지 팩이 개발 및 적용되고 있다.Secondary batteries are batteries that can be repeatedly charged and discharged, and with the development of the information and communication and display industries, they are widely used as a power source for portable electronic communication devices such as camcorders, mobile phones, and laptop PCs. Additionally, recently, battery packs including secondary batteries have been developed and applied as a power source for eco-friendly vehicles such as hybrid vehicles.
이차 전지로서 예를 들면, 리튬 이차 전지, 니켈-카드뮴 전지, 니켈-수소 전지 등을 들 수 있으며, 이들 중 리튬 이차 전지가 작동 전압 및 단위 중량당 에너지 밀도가 높으며, 충전 속도 및 경량화에 유리하다는 점에서 활발히 개발 및 적용되고 있다.Examples of secondary batteries include lithium secondary batteries, nickel-cadmium batteries, and nickel-hydrogen batteries. Among these, lithium secondary batteries have high operating voltage and energy density per unit weight, and are advantageous for charging speed and weight reduction. It is being actively developed and applied.
예를 들면, 리튬 이차 전지는 양극, 음극 및 분리막(세퍼레이터)을 포함하는 전극 조립체, 및 상기 전극 조립체를 함침시키는 전해액을 포함할 수 있다. 상기 리튬 이차 전지는 상기 전극 조립체 및 전해액을 수용하는 예를 들면, 파우치 형태의 외장재를 더 포함할 수 있다.For example, a lithium secondary battery may include an electrode assembly including a positive electrode, a negative electrode, and a separator, and an electrolyte solution for impregnating the electrode assembly. The lithium secondary battery may further include an exterior material, for example in the form of a pouch, that accommodates the electrode assembly and the electrolyte solution.
리튬 이차전지의 응용 범위가 확대되면서 보다 긴 수명, 고 용량 및 동작 안정성이 요구되고 있다. 이에 따라, 충방전 반복시에도 균일한 출력, 용량을 제공하는 리튬 이차 전지가 바람직하다.As the application range of lithium secondary batteries expands, longer lifespan, higher capacity, and operational stability are required. Accordingly, a lithium secondary battery that provides uniform output and capacity even during repeated charging and discharging is desirable.
그러나, 충방전 반복에 따라 예를 들면, 양극 활물질로 사용되는 상기 니켈계 리튬 금속 산화물의 표면 손상에 의해 출력, 용량이 감소할 수 있으며, 상기 니켈계 리튬 금속 산화물과 전해질과의 부반응이 야기될 수도 있다. 또한, 고온 또는 저온의 가혹한 환경에서 전지의 안정성이 열화될 수도 있다.However, depending on repeated charging and discharging, for example, the output and capacity may decrease due to surface damage of the nickel-based lithium metal oxide used as the positive electrode active material, and a side reaction between the nickel-based lithium metal oxide and the electrolyte may occur. It may be possible. Additionally, the stability of the battery may deteriorate in harsh environments of high or low temperatures.
예를 들면, 한국공개특허공보 제10-2021-0001837호에서와 같이 리튬 이차 전지용 비수 전해액에 첨가제를 부가하여 전지 특성을 개선하는 방법이 연구되고 있다.For example, as in Korea Patent Publication No. 10-2021-0001837, a method of improving battery characteristics by adding additives to the non-aqueous electrolyte solution for lithium secondary batteries is being studied.
본 발명의 일 과제는 향상된 열적, 화학적 안정성을 제공하는 리튬 이차 전지용 전해액을 제공하는 것이다.One object of the present invention is to provide an electrolyte solution for lithium secondary batteries that provides improved thermal and chemical stability.
본 발명의 일 과제는 상기 전해액을 포함하며 향상된 열적, 화학적 안정성을 갖는 리튬 이차 전지를 제공하는 것이다.One object of the present invention is to provide a lithium secondary battery containing the electrolyte solution and having improved thermal and chemical stability.
예시적인 실시예들에 따른 리튬 이차 전지용 전해액은 화학식 1로 표시되는 화합물을 포함하는 첨가제; 유기 용매; 및 리튬 염을 포함할 수 있다.Electrolyte solutions for lithium secondary batteries according to exemplary embodiments include an additive containing a compound represented by Formula 1; organic solvent; and lithium salts.
[화학식 1][Formula 1]
화학식 1에서, R1 내지 R10은 서로 동일하거나 상이하고 독립적으로 수소, 또는 치환 또는 비치환된 C1-C10 알킬기이며, L은 치환 또는 비치환된 C1-C10 알킬렌기일 수 있다. In Formula 1, R 1 to R 10 are the same or different from each other and independently represent hydrogen or a substituted or unsubstituted C 1 -C 10 alkyl group, and L may be a substituted or unsubstituted C 1 -C 10 alkylene group. .
일 실시예들에 있어서, 상기 R1 내지 R10은 서로 동일하거나 상이하고 독립적으로 수소, 치환 또는 비치환된 C1-C6 알킬기이며, L은 치환 또는 비치환된 C1 내지 C6 알킬렌기일 수 있다.In one embodiment, R 1 to R 10 are the same or different from each other and are independently hydrogen, a substituted or unsubstituted C 1 -C 6 alkyl group, and L is a substituted or unsubstituted C 1 to C 6 alkylene group. It could be a sign.
일 실시예들에 있어서, 상기 R1 내지 R10은 서로 동일하거나 상이하고 독립적으로 수소, 또는 비치환된 C1 내지 C6 알킬기이며, L은 비치환된 C1 내지 C6 알킬렌기일 수 있다. In one embodiment, R 1 to R 10 are the same or different from each other and independently represent hydrogen or an unsubstituted C 1 to C 6 alkyl group, and L may be an unsubstituted C 1 to C 6 alkylene group. .
일 실시예들에 있어서, 상기 첨가제는 상기 전해액 총 중량에 대해 0.1 내지 10중량% 포함될 수 있다.In one embodiment, the additive may be included in an amount of 0.1 to 10% by weight based on the total weight of the electrolyte solution.
일 실시예들에 있어서, 상기 첨가제는 상기 전해액 총 중량에 대해 0.3 내지 7중량% 포함될 수 있다.In one embodiment, the additive may be included in an amount of 0.3 to 7% by weight based on the total weight of the electrolyte solution.
일 실시예들에 있어서, 상기 전해액은 고리형 카보네이트계 화합물, 불소 치환된 고리형 카보네이트계 화합물, 설톤계 화합물, 고리형 설페이트계 화합물 및 플루오로포스페이트계 화합물로 구성된 그룹으로부터 선택된 적어도 하나의 보조 첨가제를 더 포함할 수 있다.In one embodiment, the electrolyte solution contains at least one auxiliary additive selected from the group consisting of cyclic carbonate-based compounds, fluorine-substituted cyclic carbonate-based compounds, sultone-based compounds, cyclic sulfate-based compounds, and fluorophosphate-based compounds. It may further include.
일 실시예들에 있어서, 상기 보조 첨가제는 상기 전해액 총 중량 중 0.01 내지 10중량%로 포함될 수 있다.In one embodiment, the auxiliary additive may be included in 0.01 to 10% by weight of the total weight of the electrolyte solution.
일 실시예들에 있어서, 상기 보조 첨가제는 상기 전해액 총 중량에 대해 0.05 내지 5중량%로 포함될 수 있다.In one embodiment, the auxiliary additive may be included in an amount of 0.05 to 5% by weight based on the total weight of the electrolyte solution.
일 실시예들에 있어서, 상기 유기 용매는 카보네이트계 유기용매, 에스테르계 유기용매, 에테르계 유기용매, 케톤계 유기용매 및 비양성자성 유기용매로 구성된 그룹으로부터 선택된 적어도 하나를 포함할 수 있다.In one embodiment, the organic solvent may include at least one selected from the group consisting of a carbonate-based organic solvent, an ester-based organic solvent, an ether-based organic solvent, a ketone-based organic solvent, and an aprotic organic solvent.
예시적인 실시예들에 따르는 리튬 이차 전지는 복수의 양극들 및 복수의 음극들이 반복 적층된 전극 조립체; 상기 전극 조립체를 수용하는 케이스; 및 상기 케이스 내에 상기 전극 조립체와 함께 수용되는 상술한 실시예들에 따른 리튬 이차 전지용 전해액을 포함한다.A lithium secondary battery according to exemplary embodiments includes an electrode assembly in which a plurality of positive electrodes and a plurality of negative electrodes are repeatedly stacked; a case accommodating the electrode assembly; and an electrolyte solution for a lithium secondary battery according to the above-described embodiments accommodated together with the electrode assembly in the case.
본 발명의 실시예들에 따르는 리튬 이차 전지용 전해액은 특정 함량의 1,3-디옥산(1,3-Dioxane)계열의 첨가제를 포함하여 고온 저장 특성이 향상된 리튬 이차 전지를 구현할 수 있다.The electrolyte solution for a lithium secondary battery according to embodiments of the present invention can implement a lithium secondary battery with improved high-temperature storage characteristics by including a specific content of a 1,3-Dioxane-based additive.
예를 들어, 고온에서 전지의 용량 유지율을 향상시키고, 저항 증가 및 두께 증가를 방지하여 셀 성능을 개선시킬 수 있다. For example, cell performance can be improved by improving the capacity maintenance rate of the battery at high temperatures and preventing increases in resistance and thickness.
도 1 및 도 2는 각각 예시적인 실시예들에 따른 리튬 이차 전지를 나타내는 개략적인 평면도 및 단면도이다.1 and 2 are schematic plan views and cross-sectional views, respectively, showing lithium secondary batteries according to example embodiments.
본 명세서에서 "~계 화합물"은 "~계 화합물"이 붙여지는 화합물, 및 그 화합물의 유도체를 의미할 수 있다.In this specification, “~-based compound” may mean a compound to which “~-based compound” is attached, and a derivative of the compound.
본 명세서에서 "Ca-Cb"는 "a 내지 b의 탄소(C) 원자 수"를 의미할 수 있다.In this specification, “C a -C b ” may mean “the number of carbon (C) atoms from a to b.”
<리튬 이차 전지용 전해액><Electrolyte for lithium secondary batteries>
예시적인 실시예들에 따른 리튬 이차 전지용 전해액은 리튬 염; 유기 용매; 및 화학식 1로 표시되는 화합물을 포함하는 첨가제를 포함할 수 있다. Electrolyte solutions for lithium secondary batteries according to exemplary embodiments include lithium salt; organic solvent; And it may include an additive containing a compound represented by Formula 1.
이하, 본 발명의 구성 요소들에 대해 보다 상세히 설명한다.Hereinafter, the components of the present invention will be described in more detail.
첨가제additive
예시적인 실시예들에 따른 리튬 이차 전지용 전해액은 화학식 1로 표시되는 화합물을 포함하는 첨가제를 포함할 수 있다.Electrolyte solutions for lithium secondary batteries according to exemplary embodiments may include an additive containing the compound represented by Chemical Formula 1.
[화학식 1][Formula 1]
화학식 1에서, R1 내지 R10은 각각 서로 독립적으로 서로 동일하거나 상이할 수 있다. In Formula 1, R 1 to R 10 may be independently the same or different from each other.
예를 들어, R1 내지 R10은 수소 또는 치환 또는 비치환된 C1 내지 C10 알킬기일 수 있다. 바람직하게는 수소, 치환 또는 비치환된 C1 내지 C6 알킬기일 수 있다. 더욱 바람직하게는 수소 또는 비치환된 C1 내지 C6 알킬기일 수 있다. For example, R 1 to R 10 may be hydrogen or a substituted or unsubstituted C 1 to C 10 alkyl group. Preferably, it may be hydrogen, a substituted or unsubstituted C 1 to C 6 alkyl group. More preferably, it may be hydrogen or an unsubstituted C 1 to C 6 alkyl group.
예를 들어, L은 치환 또는 비치환된 C1-C10 알킬렌기일 수 있다. 바람직하게는 치환 또는 비치환된 C1 내지 C6 알킬렌기일 수 있고, 더욱 바람직하게는 L은 비치환된 C1 내지 C6 알킬렌기일 수 있다. For example, L may be a substituted or unsubstituted C 1 -C 10 alkylene group. Preferably, it may be a substituted or unsubstituted C 1 to C 6 alkylene group, and more preferably, L may be an unsubstituted C 1 to C 6 alkylene group.
예를 들면, 상기 알킬기는 분자내에서 탄소와 수소로 이루어진 부분을를 의미할 수 있다. 상기 알킬기는 알케인(-CnH2n-)의 하나의 말단 탄소원자에서 하나의 수소 원자가 이탈된 형태를 의미할 수 있다. 예를 들면, CH3-CH2-CH2-은 프로필(propyl)기를 의미할 수 있다.For example, the alkyl group may refer to a portion consisting of carbon and hydrogen within a molecule. The alkyl group may refer to a form in which one hydrogen atom is removed from one terminal carbon atom of an alkane (-C n H 2n -). For example, CH 3 -CH 2 -CH 2 - may mean a propyl group.
예를 들면, 상기 알킬렌기는 알케인(-CnH2n-)의 양말단 탄소 원자에서 각각 하나의 수소 원자가 이탈된 형태를 의미할 수 있다. 예를 들면, -CH2-CH2-CH2-은 프로필렌(propylene)기를 의미할 수 있다.For example, the alkylene group may refer to a form in which one hydrogen atom is removed from each of the carbon atoms at both ends of an alkane (-C n H 2n -). For example, -CH 2 -CH 2 -CH 2 - may mean a propylene group.
예를 들면, "치환된"의 의미는 상기 알킬렌기의 수소 원자가 치환기로 치환됨으로써, 상기 알킬렌기의 탄소 원자에 치환기가 더 결합되어 있을 수 있다는 의미일 수 있다. 예를 들면, 상기 치환기는 할로겐기, C1-C6의 알킬기, C2-C6의 알케닐기, 아미노기, C1-C6의 알콕시기, C3-C7의 시클로알킬기 및 5-7각의 헤테로시클로알킬기 중 적어도 하나일 수 있다. For example, “substituted” may mean that the hydrogen atom of the alkylene group is replaced with a substituent, so that a substituent may be further bonded to the carbon atom of the alkylene group. For example, the substituents include halogen group, C 1 -C 6 alkyl group, C 2 -C 6 alkenyl group, amino group, C 1 -C 6 alkoxy group, C 3 -C 7 cycloalkyl group, and 5-7 It may be at least one of each heterocycloalkyl group.
일부 실시예들에서, 상기 치환기는 할로겐기 또는 C1-C6의 알킬기일 수 있다.In some embodiments, the substituent may be a halogen group or a C 1 -C 6 alkyl group.
상기 화학식 1로 표시되는 화합물을 포함하는 첨가제를 이차 전지용 전해액에 포함하는 경우, 고리형 에터의 분해 반응을 통해 전극 상에 견고한 고체 전해질 막(SEI) 형성을 유도하여 고온에서 안정한 전극 계면이 형성될 수 있다. 따라서, 유기 용매(예를 들어, EC, EMC 등)의 분해를 효과적으로 방지할 수 있고, 가스 발생 및 전지 두께 증가를 감소시킬 수 있다.When an additive containing the compound represented by Formula 1 is included in the electrolyte solution for a secondary battery, a stable electrode interface can be formed at high temperatures by inducing the formation of a solid solid electrolyte film (SEI) on the electrode through a decomposition reaction of cyclic ether. You can. Therefore, decomposition of organic solvents (eg, EC, EMC, etc.) can be effectively prevented, and gas generation and increase in battery thickness can be reduced.
일 실시예에 있어서, 상기 화학식 1로 표시되는 화합물은 (5-ethyl-1,3-dioxan-5-yl)methyl acrylate를 포함할 수 있다. 예를 들어, (5-ethyl-1,3-dioxan-5-yl)methyl acrylate는 화학식 1-1로 표기될 수 있다. In one embodiment, the compound represented by Formula 1 may include (5-ethyl-1,3-dioxan-5-yl)methyl acrylate. For example, (5-ethyl-1,3-dioxan-5-yl)methyl acrylate can be represented by formula 1-1.
[화학식 1-1][Formula 1-1]
예를 들어, (5-ethyl-1,3-dioxan-5-yl)methyl acrylate가 이차 전지의 전해액에 첨가제로 포함하는 경우, 아크릴레이트기에 의해 전극 상에 안정적인 SEI 막을 형성할 수 있어 고온 저장 특성을 향상시킬 수 있다. 또한, 전해액과 전극과의 반응에 의한 전해액의 분해를 억제하여 가스 발생을 줄일 수 있다. For example, when (5-ethyl-1,3-dioxan-5-yl)methyl acrylate is included as an additive in the electrolyte of a secondary battery, a stable SEI film can be formed on the electrode due to the acrylate group, resulting in high temperature storage properties. can be improved. In addition, gas generation can be reduced by suppressing decomposition of the electrolyte due to the reaction between the electrolyte and the electrode.
일 실시예에 있어서, 충분한 패시베이션 및 안정적인 SEI 막 형성을 구현을 고려하여 상기 첨가제 함량은 전해액 총 중량에 대해 0.1중량% 이상, 0.2중량% 이상, 0.3중량% 이상, 0.4중량% 이상, 0.5중량% 이상 또는 1중량% 이상으로 조절될 수 있다. 또한, 전해액에서의 리튬 이온 이동 및 활물질 활성을 고려하여, 첨가제의 함량은 전해액 총 중량에 대해 10중량% 이하, 9중량% 이하, 7중량% 이하, 6중량%이하, 5중량% 이하, 4.5중량% 이하, 4중량% 이하, 3.5중량% 이하, 3중량% 이하 또는 2중량% 이하로 조절될 수 있다.In one embodiment, considering the implementation of sufficient passivation and stable SEI film formation, the additive content is 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.4% by weight or more, and 0.5% by weight based on the total weight of the electrolyte. It can be adjusted to more than 1% by weight or more than 1% by weight. In addition, considering lithium ion movement and active material activity in the electrolyte, the additive content is 10% by weight or less, 9% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4.5% by weight or less, based on the total weight of the electrolyte. It can be adjusted to less than % by weight, less than 4% by weight, less than 3.5% by weight, less than 3% by weight, or less than 2% by weight.
보조 첨가제auxiliary additives
예시적인 실시예들에 따른 리튬 이차 전지용 전해액은, 상술한 첨가제와 함께, 보조 첨가제를 더 포함할 수 있다.The electrolyte solution for a lithium secondary battery according to exemplary embodiments may further include an auxiliary additive in addition to the additives described above.
일 실시예에 있어서, 상기 보조 첨가제는 예를 들어, 고리형 카보네이트계 화합물, 불소 치환된 카보네이트계 화합물, 설톤계 화합물, 고리형 설페이트계 화합물 및 포스페이트계 화합물을 포함할 수 있다. In one embodiment, the auxiliary additive may include, for example, a cyclic carbonate-based compound, a fluorine-substituted carbonate-based compound, a sultone-based compound, a cyclic sulfate-based compound, and a phosphate-based compound.
일 실시예에 있어서, 상기 보조 첨가제의 함량은 화학식 1로 표시되는 화합물을 포함하는 메인 첨가제와의 작용을 고려하여 예를 들면, 상기 비수 전해액 총 중량 중 10중량% 이하, 9중량% 이하, 8중량% 이하, 7중량% 이하, 6중량% 이하, 5중량% 이하, 4중량% 이하, 3중량% 이하, 2중량% 이하, 1중량% 이하로 조절될 수 있다. 또한, 상기 보조 첨가제의 함량은 SEI막 안정화를 고려하여 0.01중량% 이상, 0.02중량% 이상, 0.03중량% 이상, 0.05중량% 이상, 0.1중량% 이상, 0.2중량% 이상, 0.3중량% 이상, 0.4중량% 이상 또는 0.5중량% 이상으로 조절될 수 있다.In one embodiment, the content of the auxiliary additive is, for example, 10% by weight or less, 9% by weight or less, 8% by weight or less of the total weight of the non-aqueous electrolyte solution, considering the action with the main additive containing the compound represented by Formula 1. It can be adjusted to % by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, and 1% by weight or less. In addition, considering the stabilization of the SEI film, the content of the auxiliary additive is 0.01% by weight or more, 0.02% by weight or more, 0.03% by weight or more, 0.05% by weight or more, 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.4% by weight or more. It can be adjusted to more than 0.5% by weight or more than 0.5% by weight.
바람직하게 상기 보조 첨가제는 상기 비수 전해액 총 중량 중 약 0.01 내지 10중량, 바람직하게는 0.05 내지 7중량%, 보다 바람직하게는 0.05 내지 5중량%의 함량으로 포함될 수 있다. 상기 범위 내에서 메인 첨가제의 역할을 저해하지 않으면서, 보호 피막의 내구성을 증진시킬 수 있고, 고온 저장 특성을 향상시키는데 도움을 줄 수 있다. Preferably, the auxiliary additive may be included in an amount of about 0.01 to 10% by weight, preferably 0.05 to 7% by weight, and more preferably 0.05 to 5% by weight of the total weight of the non-aqueous electrolyte solution. Within the above range, the durability of the protective film can be improved without impairing the role of the main additive, and it can help improve high-temperature storage characteristics.
상기 고리형 카보네이트계 화합물은 비닐렌 카보네이트(vinylene carbonate, VC), 비닐 에틸렌 카보네이트(vinyl ethylene carbonate, VEC) 등을 포함할 수 있다. The cyclic carbonate-based compound may include vinylene carbonate (VC), vinyl ethylene carbonate (VEC), etc.
상기 불소 치환된 고리형 카보네이트계 화합물은 플루오로에틸렌 카보네이트(fluoroehtylene carbonate, FEC)를 포함할 수 있다.The fluorine-substituted cyclic carbonate-based compound may include fluoroethylene carbonate (FEC).
상기 설톤계 화합물은 1,3-프로판 설톤(1,3-propane sultone), 1,3-프로펜 설톤(1,3-propene sultone), 1,4-부탄 설톤(1,4-butane sultone) 등을 포함할 수 있다.The sultone-based compounds include 1,3-propane sultone, 1,3-propene sultone, and 1,4-butane sultone. It may include etc.
상기 고리형 설페이트계 화합물은 1,2-에틸렌 설페이트(1,2-ethylene sulfate), 1,2-프로필렌 설페이트(1,2-propylene sulfate) 등을 포함할 수 있다.The cyclic sulfate-based compound may include 1,2-ethylene sulfate, 1,2-propylene sulfate, etc.
상기 포스페이트계 화합물은 플루오로포스페이트계 화합물으로 리튬 디플루오로포스페이트를 포함할 수 있다. The phosphate-based compound is a fluorophosphate-based compound and may include lithium difluorophosphate.
바람직한 일 실시예에 있어서, 상기 보조 첨가제로서 불소 치환된 고리형 카보네이트계 화합물, 설톤계 화합물, 고리형 설페이트계 화합물 및 플루오로포스페이트계 화합물을 함께 사용할 수 있다. In a preferred embodiment, fluorine-substituted cyclic carbonate-based compounds, sultone-based compounds, cyclic sulfate-based compounds, and fluorophosphate-based compounds can be used together as the auxiliary additive.
상기 보조 첨가제를 추가함에 따라 전극의 내구성, 안정성을 보다 증진시킬 수 있다. 상기 보조 첨가제는 리튬 이온의 전해액 내 이동을 저해하지 않는 범위 내에서 적절한 함량으로 포함될 수 있다.By adding the auxiliary additive, the durability and stability of the electrode can be further improved. The auxiliary additive may be included in an appropriate amount within a range that does not inhibit the movement of lithium ions in the electrolyte solution.
유기 용매 및 리튬 염Organic solvents and lithium salts
상기 유기 용매는, 예를 들면, 상기 리튬 염, 상기 첨가제 및 상기 보조 첨가제에 대해 충분한 용해도를 가지며, 전지 내에서 반응성을 갖지 않는 유기 화합물을 포함할 수 있다.The organic solvent may include, for example, an organic compound that has sufficient solubility in the lithium salt, the additive, and the auxiliary additive and is not reactive in the battery.
일 실시예들에 있어서, 상기 유기 용매는 카보네이트계 유기용매, 에스테르계 유기용매, 에테르계 유기용매, 프로피오네이트계 유기용매 및 불소계 유기용매로 구성된 그룹으로부터 선택된 적어도 하나를 포함할 수 있다.In one embodiment, the organic solvent may include at least one selected from the group consisting of a carbonate-based organic solvent, an ester-based organic solvent, an ether-based organic solvent, a propionate-based organic solvent, and a fluorine-based organic solvent.
일 실시예에 있어서, 상기 유기 용매는 카보네이트계 용매를 포함할 수 있다. 예를 들어, 상기 카보네이트계 용매는 선형 카보네이트계 용매 및 환형 카보네이트계 용매를 포함할 수 있다. 일부 실시예들에서, 상기 유기 용매는 부피를 기준으로, 상기 선형 카보네이트계 용매를 상기 환형 카보네이트계 용매보다 더 많이 포함할 수 있다. 예를 들면, 상기 선형 카보네이트계 용매 및 환형 카보네이트계 용매의 혼합 부피비는 1:1 내지 9:1일 수 있으며, 바람직하게는 1.5:1 내지 4:1일 수 있다.In one embodiment, the organic solvent may include a carbonate-based solvent. For example, the carbonate-based solvent may include a linear carbonate-based solvent and a cyclic carbonate-based solvent. In some embodiments, the organic solvent may include more of the linear carbonate-based solvent than the cyclic carbonate-based solvent, based on volume. For example, the mixing volume ratio of the linear carbonate-based solvent and the cyclic carbonate-based solvent may be 1:1 to 9:1, and preferably 1.5:1 to 4:1.
예를 들면, 상기 선형 카보네이트계 용매는 디메틸카보네이트(DMC; dimethyl carbonate), 에틸메틸카보네이트(EMC; ethyl methyl carbonate), 디에틸카보네이트(DEC; diethyl carbonate), 메틸프로필카보네이트(methyl propyl carbonate), 에틸프로필카보네이트(ethyl propyl carbonate) 및 디프로필카보네이트(dipropyl carbonate) 중 적어도 하나를 포함할 수 있다.For example, the linear carbonate-based solvent includes dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), methyl propyl carbonate, and ethyl. It may include at least one of ethyl propyl carbonate and dipropyl carbonate.
예를 들면, 상기 환형 카보네이트계 용매는 에틸렌카보네이트(EC; ethylene carbonate), 프로필렌카보네이트(PC; propylene carbonate) 및 부틸렌 카보네이트(butylene carbonate) 중 적어도 하나를 포함할 수 있다.For example, the cyclic carbonate-based solvent may include at least one of ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate.
예를 들면, 상기 에스테르계 용매의 예로서 메틸 아세테이트 (methyl acetate, MA), 에틸 아세테이트 (ethyl acetate, EA), n-프로필 아세테이트 (n-propyl acetate, n-PA), 1,1-디메틸에틸 아세테이트 (1,1-dimethylethyl acetate, DMEA), 메틸프로피오네이트 (methyl propionate, MP), 에틸프로피오네이트 (ethyl propionate, EP), 감마-부티로락톤(γ-butyrolacton, GBL), 데카놀라이드(decanolide), 발레로락톤(valerolactone), 메발로노락톤(mevalonolactone), 카프로락톤(caprolactone) 등을 들 수 있다.For example, examples of the ester-based solvent include methyl acetate (MA), ethyl acetate (EA), n-propyl acetate (n-PA), and 1,1-dimethylethyl. Acetate (1,1-dimethylethyl acetate, DMEA), methyl propionate (MP), ethyl propionate (EP), gamma-butyrolacton (GBL), decanolide (decanolide), valerolactone, mevalonolactone, caprolactone, etc.
예를 들면, 상기 에테르계 용매는 디부틸에테르(dibutyl ether), 테트라에틸렌글리콜 디메틸에테르(TEGDME; tetraethylene glycol dimethyl ether), 디에틸렌글리콜 디메틸에테르(DEGDME; diethylene glycol dimethyl ether), 디메톡시에탄(dimethoxyethane), 테트라히드로퓨란(THF; tetrahydrofuran) 및 2-메틸테트라히드로퓨란(2-methyltetrahydrofuran) 중 적어도 하나를 포함할 수 있다.For example, the ether-based solvent is dibutyl ether, tetraethylene glycol dimethyl ether (TEGDME), diethylene glycol dimethyl ether (DEGDME), and dimethoxyethane. ), tetrahydrofuran (THF), and 2-methyltetrahydrofuran (2-methyltetrahydrofuran).
상기 케톤계 용매의 예로서 시클로헥사논(cyclohexanone)을 들 수 있다. 상기 알코올계 용매의 예로서 에틸알코올(ethyl alcohol), 이소프로필 알코올(isopropyl alcohol)등을 들 수 있다.An example of the ketone solvent may be cyclohexanone. Examples of the alcohol-based solvent include ethyl alcohol and isopropyl alcohol.
상기 비양성자성 용매는 니트릴계 용매, 디메틸포름아미드(dimethyl formamide, DMF) 등과 같은 등의 아미드계 용매, 1,3-디옥솔란 등의 디옥솔란계 용매, 설포란(sulfolane) 계 용매 등을 포함할 수 있다.The aprotic solvent includes nitrile-based solvents, amide-based solvents such as dimethyl formamide (DMF), dioxolane-based solvents such as 1,3-dioxolane, and sulfolane-based solvents. can do.
바람직한 일 실시예에 있어서, 상기 유기 용매로서 상기 카보네이트 계 용매가 사용될 수 있다. 예를 들면, 상기 유기 용매로서 에틸렌 카보네이트(EC), 에틸 메틸 카보네이트(EMC), 디에틸 카보네이트(DEC), 또는 이들의 조합을 포함할 수 있다. In a preferred embodiment, the carbonate-based solvent may be used as the organic solvent. For example, the organic solvent may include ethylene carbonate (EC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), or a combination thereof.
일 실시예에 있어서, 상기 전해질은 예를 들면, 리튬염을 포함할 수 있다. 상기 리튬염은 Li+X-로 표현될 수 있다.In one embodiment, the electrolyte may include, for example, lithium salt. The lithium salt can be expressed as Li +
예를 들면, 상기 리튬염의 음이온(X-)은 F-, Cl-, Br-, I-, NO3 -, N(CN)2 -, BF4 -, ClO4 -, PF6 -, (CF3)2PF4 -, (CF3)3PF3 -, (CF3)4PF2 -, (CF3)5PF-, (CF3)6P-, CF3SO3 -, CF3CF2SO3 -, (CF3SO2)2N-, (FSO2)2N- , CF3CF2(CF3)2CO-, (CF3SO2)2CH-, (SF5)3C-, (CF3SO2)3C-, CF3(CF2)7SO3 -, CF3CO2 -, CH3CO2 -, SCN- 및 (CF3CF2SO2)2N- 등일 수 있다. 이들은 단독으로 혹은 2 종 이상의 리튬염이 사용될 수 있다.For example, the anion (X - ) of the lithium salt is F - , Cl - , Br - , I - , NO 3 - , N(CN) 2 - , BF 4 - , ClO 4 - , PF 6 - , (CF 3 ) 2 PF 4 - , (CF 3 ) 3 PF 3 - , (CF 3 ) 4 PF 2 - , (CF 3 ) 5 PF - , (CF 3 ) 6 P - , CF 3 SO 3 - , CF 3 CF 2 SO 3 - , (CF 3 SO 2 ) 2 N - , (FSO 2 ) 2 N - , CF 3 CF 2 (CF 3 ) 2 CO - , (CF 3 SO 2 ) 2 CH - , (SF 5 ) 3 C - , (CF 3 SO 2 ) 3 C - , CF 3 (CF 2 ) 7 SO 3 - , CF 3 CO 2 - , CH 3 CO 2 - , SCN - and (CF 3 CF 2 SO 2 ) 2 N - may be the same. These may be used alone or two or more types of lithium salts may be used.
일부 실시예들에서, 상기 리튬 염은 LiBF4 및 LiPF6 중 적어도 하나를 포함할 수 있다.In some embodiments, the lithium salt may include at least one of LiBF 4 and LiPF 6 .
일 실시예에 있어서, 상기 리튬 염은 상기 유기 용매에 대해 0.01 내지 5M, 보다 좋게는 0.01 내지 2M의 농도로 포함될 수 있다. 상기 농도 범위 내에서 전지의 충방전시 리튬 이온 및/또는 전자의 원활히 이동될 수 있다.In one embodiment, the lithium salt may be included at a concentration of 0.01 to 5M, more preferably 0.01 to 2M, relative to the organic solvent. Within the above concentration range, lithium ions and/or electrons can be smoothly moved during charging and discharging of the battery.
<리튬 이차 전지><Lithium secondary battery>
본 발명의 실시예들은 상술한 전해액을 포함하는 리튬 이차 전지를 제공한다. Embodiments of the present invention provide a lithium secondary battery containing the above-described electrolyte solution.
예시적인 실시예들에 따르는 리튬 이차 전지는 복수의 양극들 및 복수의 음극들이 반복 적층된 전극 조립체; 상기 전극 조립체를 수용하는 케이스; 및 상기 케이스 내에 상기 전극 조립체와 함께 수용되는 상술한 실시예들에 따른 리튬 이차 전지용 전해액을 포함한다.A lithium secondary battery according to exemplary embodiments includes an electrode assembly in which a plurality of positive electrodes and a plurality of negative electrodes are repeatedly stacked; a case accommodating the electrode assembly; and an electrolyte solution for a lithium secondary battery according to the above-described embodiments accommodated together with the electrode assembly in the case.
도 1 및 도 2는 각각 예시적인 실시예들에 따른 리튬 이차 전지를 나타내는 개략적인 평면도 및 단면도이다. 예를 들면, 도 2는 도 1의 I-I' 라인을 따라 절단한 단면도이다.1 and 2 are schematic plan views and cross-sectional views, respectively, showing lithium secondary batteries according to example embodiments. For example, Figure 2 is a cross-sectional view taken along line II' of Figure 1.
도 1 및 도 2를 참조하면, 리튬 이차 전지는 양극(100), 음극(130) 및 상기 양극과 음극 사이에 개재된 분리막(140)을 포함하는, 전극 조립체를 포함할 수 있다.Referring to Figures 1 and 2, a lithium secondary battery may include an electrode assembly including a positive electrode 100, a negative electrode 130, and a separator 140 interposed between the positive electrode and the negative electrode.
상기 전극 조립체는 케이스(160) 내에 전해질과 함께 수용되어 전해질에 의해 함침될 수 있다.The electrode assembly may be accommodated with an electrolyte in the case 160 and impregnated with the electrolyte.
양극(100)은 양극 활물질을 양극 집전체(105)에 도포하여 형성한 양극 활물질 층(110)을 포함할 수 있다. 상기 양극 활물질은 리튬 이온을 가역적으로 인터칼레이션 및 디인터칼레이션 할 수 있는 화합물을 포함할 수 있다.The positive electrode 100 may include a positive electrode active material layer 110 formed by applying a positive electrode active material to the positive electrode current collector 105. The positive electrode active material may include a compound capable of reversibly intercalating and deintercalating lithium ions.
예시적인 실시예들에 있어서, 상기 양극 활물질은 리튬-전이금속 산화물을 포함할 수 있다. 예를 들면, 상기 리튬-전이금속 산화물은 니켈(Ni)을 포함하며, 코발트(Co) 또는 망간(Mn) 중 적어도 하나를 더 포함할 수 있다.In exemplary embodiments, the positive electrode active material may include lithium-transition metal oxide. For example, the lithium-transition metal oxide includes nickel (Ni) and may further include at least one of cobalt (Co) or manganese (Mn).
예를 들면, 상기 리튬-전이금속 산화물은 하기의 화학식 1로 표시될 수 있다.For example, the lithium-transition metal oxide may be represented by Formula 1 below.
[화학식 1][Formula 1]
Li1+aNi1-(x+y)CoxMyO2 Li 1+a Ni 1-(x+y) Co x M y O 2
상기 화학식 1 중, -0.05≤a≤0.2, 0.01≤x≤0.3, 0.01≤y≤0.3, 이고 M은 Mn, Mg, Sr, Ba, B, Al, Si, Ti, Zr 또는 W 중 선택되는 선택된 1종 이상의 원소일 수 있다.In Formula 1, -0.05≤a≤0.2, 0.01≤x≤0.3, 0.01≤y≤0.3, and M is selected from Mn, Mg, Sr, Ba, B, Al, Si, Ti, Zr or W. It may be one or more types of elements.
상기 화학식 1에 표시된 바와 같이, 상기 리튬-전이금속 화합물은 Ni, Co 및 M 중 Ni을 가장 많은 함량 또는 몰비로 포함할 수 있다. Ni은 실질적으로 리튬 이차 전지의 출력 및/또는 용량에 연관된 금속으로 기능할 수 있으며, Ni을 전이 금속들 중 가장 많은 양으로 포함함에 따라 고용량, 고출력 리튬 이차 전지를 구현할 수 있다.As shown in Formula 1, the lithium-transition metal compound may contain Ni in the highest content or molar ratio among Ni, Co, and M. Ni can substantially function as a metal related to the output and/or capacity of a lithium secondary battery, and by including Ni in the largest amount among transition metals, a high-capacity, high-output lithium secondary battery can be implemented.
일 실시예에 있어서, 화학식 1 중, 0.01≤x≤0.2, 0.01≤y≤0.2 일 수 있다. 일 실시예에 있어서, Ni의 몰비는 0.7 이상 또는 0.8 이상일 수 있다.In one embodiment, in Formula 1, 0.01≤x≤0.2 and 0.01≤y≤0.2. In one embodiment, the molar ratio of Ni may be 0.7 or more or 0.8 or more.
양극 활물질 또는 리튬-전이금속 산화물 중 Ni의 함량이 높아지는 경우, 상대적으로 화학적 안정성, 예를 들면 이차 전지의 고온 저장 안정성이 열화될 수 있다. 또한, 충/방전 반복에 따라 양극 활물질의 표면 손상 또는 전해액과의 부반응 등에 의해 고 Ni 함량에 따른 충분한 고출력/고용량 특성이 구현되지 않을 수 있다.If the Ni content in the positive electrode active material or lithium-transition metal oxide increases, the relative chemical stability, for example, high-temperature storage stability of the secondary battery, may be deteriorated. In addition, sufficient high output/high capacity characteristics due to high Ni content may not be realized due to surface damage of the positive electrode active material or side reactions with the electrolyte due to repeated charging/discharging.
그러나, 상술한 바와 같이 불소계 첨가제가, 양극 활물질 또는 리튬-전이금속 산화물 표면의 Ni과 배위 결합 또는 화학적 상호작용을 통해 결합하여 양극 활물질의 패시베이션을 제공할 수 있다. 따라서, 고 Ni 함량을 통한 고출력/고용량 특성을 고온 환경에서도 장시간 실질적으로 균일하게 유지할 수 있다.However, as described above, the fluorine-based additive may provide passivation of the positive electrode active material by combining with Ni on the surface of the positive electrode active material or lithium-transition metal oxide through coordination or chemical interaction. Therefore, high output/high capacity characteristics through high Ni content can be maintained substantially uniformly for a long time even in a high temperature environment.
상기 양극 활물질을 용매 내에서 바인더, 도전재 및/또는 분산재 등과 혼합 및 교반하여 슬러리를 제조할 수 있다. 상기 슬러리를 양극 집전체(105)에 코팅한 후, 압축 및 건조하여 양극(100)을 제조할 수 있다.A slurry can be prepared by mixing and stirring the positive electrode active material with a binder, a conductive material, and/or a dispersant in a solvent. After coating the slurry on the positive electrode current collector 105, the positive electrode 100 can be manufactured by compressing and drying.
양극 집전체(105)는 예를 들면, 스테인레스강, 니켈, 알루미늄, 티탄, 구리 또는 이들의 합금을 포함할 수 있으며, 바람직하게는 알루미늄 또는 알루미늄 합금을 포함할 수 있다.The positive electrode current collector 105 may include, for example, stainless steel, nickel, aluminum, titanium, copper, or an alloy thereof, and preferably includes aluminum or an aluminum alloy.
상기 바인더는, 예를 들면, 비닐리덴플루오라이드-헥사플루오로프로필렌 코폴리머(PVDF-co-HFP), 폴리비닐리덴플루오라이드(polyvinylidenefluoride, PVDF), 폴리아크릴로니트릴(polyacrylonitrile), 폴리메틸메타크릴레이트(polymethylmethacrylate) 등의 유기계 바인더, 또는 스티렌-부타디엔 러버(SBR) 등의 수계 바인더를 포함할 수 있으며, 카르복시메틸 셀룰로오스(CMC)와 같은 증점제와 함께 사용될 수 있다. The binder is, for example, vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidenefluoride (PVDF), polyacrylonitrile, polymethyl methacryl. It may include an organic binder such as polymethylmethacrylate or an aqueous binder such as styrene-butadiene rubber (SBR), and may be used with a thickener such as carboxymethyl cellulose (CMC).
예를 들면, 양극 바인더로서 PVDF 계열 바인더를 사용할 수 있다. 이 경우, 양극 활물질 층 형성을 위한 바인더의 양을 감소시키고 상대적으로 양극 활물질의 양을 증가시킬 수 있으며, 이에 따라 이차 전지의 출력, 용량을 향상시킬 수 있다.For example, a PVDF series binder can be used as the anode binder. In this case, the amount of binder for forming the positive electrode active material layer can be reduced and the amount of positive electrode active material can be relatively increased, thereby improving the output and capacity of the secondary battery.
상기 도전재는 활물질 입자들 사이의 전자 이동을 촉진하기 위해 포함될 수 있다. 예를 들면, 상기 도전재는 흑연, 카본 블랙, 그래핀, 탄소 나노 튜브 등과 같은 탄소계열 도전재 및/또는 주석, 산화주석, 산화티타늄, LaSrCoO3, LaSrMnO3와 같은 페로브스카이트(perovskite) 물질 등을 포함하는 금속 계열 도전재를 포함할 수 있다.The conductive material may be included to promote electron transfer between active material particles. For example, the conductive material may be a carbon-based conductive material such as graphite, carbon black, graphene, or carbon nanotubes, and/or a perovskite material such as tin, tin oxide, titanium oxide, LaSrCoO 3 , or LaSrMnO 3 It may include a metal-based conductive material including the like.
음극(130)은 음극 집전체(125), 및 음극 활물질을 음극 집전체(125)에 코팅하여 형성된 음극 활물질 층(120)을 포함할 수 있다.The negative electrode 130 may include a negative electrode current collector 125 and a negative electrode active material layer 120 formed by coating the negative electrode current collector 125 with a negative electrode active material.
상기 음극 활물질은 리튬 이온을 흡장 및 탈리할 수 있는, 당 분야에서 공지된 것이 특별한 제한 없이 사용될 수 있다. 예를 들면 결정질 탄소, 비정질 탄소, 탄소 복합체, 탄소 섬유 등의 탄소 계열 재료; 리튬 합금; 실리콘(Si) 계 화합물 또는 주석 등이 사용될 수 있다. 상기 비정질 탄소의 예로서 하드카본, 코크스, 메조카본 마이크로비드(mesocarbon microbead: MCMB), 메조페이스피치계 탄소섬유(mesophase pitch-based carbon fiber: MPCF) 등을 들 수 있다. As the anode active material, any material known in the art that can occlude and desorb lithium ions may be used without particular limitation. For example, carbon-based materials such as crystalline carbon, amorphous carbon, carbon composite, and carbon fiber; lithium alloy; Silicon (Si)-based compounds or tin may be used. Examples of the amorphous carbon include hard carbon, coke, mesocarbon microbeads (MCMB), and mesophase pitch-based carbon fiber (MPCF).
상기 결정질 탄소의 예로서 천연흑연, 인조흑연, 흑연화 코크스, 흑연화 MCMB, 흑연화 MPCF 등과 같은 흑연계 탄소를 들 수 있다. 상기 리튬 합금에 포함되는 원소로서 알루미늄, 아연, 비스무스, 카드뮴, 안티몬, 실리콘, 납, 주석, 갈륨 또는 인듐 등을 들 수 있다.Examples of the crystalline carbon include graphite-based carbon such as natural graphite, artificial graphite, graphitized coke, graphitized MCMB, and graphitized MPCF. Elements included in the lithium alloy include aluminum, zinc, bismuth, cadmium, antimony, silicon, lead, tin, gallium, and indium.
상기 실리콘계 화합물은 예를 들면, 실리콘, 실리콘 산화물 또는 실리콘 카바이드(SiC)와 같은 실리콘-탄소 복합 화합물을 포함할 수 있다.The silicon-based compound may include, for example, a silicon-carbon complex compound such as silicon, silicon oxide, or silicon carbide (SiC).
예를 들면, 상기 음극 활물질 및 용매 내에서 상술한 바인더, 도전재, 증점제 등과 함께 혼합 및 교반하여 슬러리 형태로 제조될 수 있다. 상기 슬러리를 음극 집전체(125)의 적어도 일면 상에 코팅한 후, 압축 및 건조하여 음극(130)을 제조할 수 있다. For example, it can be prepared in the form of a slurry by mixing and stirring the negative electrode active material and the above-described binder, conductive material, thickener, etc. in the solvent. The slurry may be coated on at least one side of the negative electrode current collector 125, and then compressed and dried to manufacture the negative electrode 130.
양극(100) 및 음극(130) 사이에는 분리막(140)이 개재될 수 있다. 분리막(140)은 에틸렌 단독중합체, 프로필렌 단독중합체, 에틸렌/부텐 공중합체, 에틸렌/헥센 공중합체, 에틸렌/메타크릴레이트 공중합체 등과 같은 폴리올레핀계 고분자로 제조한 다공성 고분자 필름을 포함할 수 있다. 분리막(140)은 고융점의 유리 섬유, 폴리에틸렌테레프탈레이트 섬유 등으로 형성된 부직포를 포함할 수도 있다.A separator 140 may be interposed between the anode 100 and the cathode 130. The separator 140 may include a porous polymer film made of polyolefin-based polymers such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer. The separator 140 may include a non-woven fabric made of high melting point glass fiber, polyethylene terephthalate fiber, etc.
일부 실시예들에 있어서, 음극(130)의 면적(예를 들면, 분리막(140)과 접촉 면적) 및/또는 부피는 양극(100)보다 클 수 있다. 이에 따라, 양극(100)으로부터 생성된 리튬 이온이 예를 들면, 중간에 석출되지 않고 음극(130)으로 원활히 이동될 수 있다.In some embodiments, the area (eg, contact area with the separator 140) and/or volume of the cathode 130 may be larger than that of the anode 100. Accordingly, for example, lithium ions generated from the anode 100 can be smoothly moved to the cathode 130 without precipitating in the middle.
예시적인 실시예들에 따르면, 양극(100), 음극(130) 및 분리막(140)에 의해 전극 셀이 정의되며, 복수의 전극 셀들이 적층되어 예를 들면, 젤리 롤(jelly roll) 형태의 전극 조립체(150)가 형성될 수 있다. 예를 들면, 분리막(140)의 권취(winding), 적층(lamination), 접음(folding) 등을 통해 전극 조립체(150)를 형성할 수 있다.According to exemplary embodiments, an electrode cell is defined by an anode 100, a cathode 130, and a separator 140, and a plurality of electrode cells are stacked, for example, an electrode in the form of a jelly roll. Assembly 150 may be formed. For example, the electrode assembly 150 can be formed through winding, lamination, folding, etc. of the separator 140.
전극 조립체(150)가 케이스(160) 내에 상술한 예시적인 실시예들에 따른 비수계 전해액과 함께 수용되어 리튬 이차 전지가 정의될 수 있다. 예시적인 실시예들에 따르면, 상기 전해질로서 비수 전해액을 사용할 수 있다.The electrode assembly 150 may be accommodated in the case 160 together with the non-aqueous electrolyte according to the above-described exemplary embodiments to define a lithium secondary battery. According to exemplary embodiments, a non-aqueous electrolyte solution may be used as the electrolyte.
도 1에 도시된 바와 같이, 각 전극 셀에 속한 양극 집전체(105) 및 음극 집전체로(125)부터 각각 전극 탭(양극 탭 및 음극 탭)이 돌출되어 케이스(160)의 일 측부까지 연장될 수 있다. 상기 전극 탭들은 케이스(160)의 상기 일측부와 함께 융착되어 케이스(160)의 외부로 연장 또는 노출된 전극 리드(양극 리드(107) 및 음극 리드(127))를 형성할 수 있다. As shown in FIG. 1, electrode tabs (positive electrode tab and negative electrode tab) protrude from the positive electrode current collector 105 and the negative electrode current collector 125 belonging to each electrode cell, respectively, and extend to one side of the case 160. It can be. The electrode tabs may be fused together with the one side of the case 160 to form electrode leads (positive lead 107 and negative lead 127) that extend or are exposed to the outside of the case 160.
상기 리튬 이차 전지는 예를 들면, 캔을 사용한 원통형, 각형, 파우치(pouch)형 또는 코인(coin)형 등으로 제조될 수 있다.The lithium secondary battery may be manufactured, for example, in a cylindrical shape using a can, a square shape, a pouch shape, or a coin shape.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 이들 실시예는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred embodiments are presented to aid understanding of the present invention, but these examples are only illustrative of the present invention and do not limit the scope of the appended claims, and are examples within the scope and technical idea of the present invention. It is obvious to those skilled in the art that various changes and modifications are possible, and it is natural that such changes and modifications fall within the scope of the appended patent claims.
합성예Synthesis example
(5-ethyl-1,3-dioxan-5-yl)methyl acrylate 합성Synthesis of (5-ethyl-1,3-dioxan-5-yl)methyl acrylate
둥근 바닥 플라스크에 교반기, 온도계, 냉각기를 장치하고 5-에틸-1,3-디옥산-5-메탄올 (50 g, 0.34 mol), 아크릴산 메틸 (73.6 g, 0.86 mol), 디옥틸 주석 옥사이드 (0.72 g), 4-메톡시페놀 (0.7 g) 과 노말 헥산 10 ml 투입 후 교반하였다. 반응액을 90℃로 승온하고 메탄올을 제거하며 24시간 교반하였다. 반응 완료 후 감압 증류하여 실시예 1의 화합물 a를 무색 액체 시료로서 61.6 g을 얻었다 (수득율 90%)A round-bottom flask was equipped with a stirrer, thermometer, and condenser, and 5-ethyl-1,3-dioxane-5-methanol (50 g, 0.34 mol), methyl acrylate (73.6 g, 0.86 mol), and dioctyl tin oxide (0.72 mol) were added to the flask. g), 4-methoxyphenol (0.7 g) and 10 ml of normal hexane were added and stirred. The reaction solution was heated to 90°C, methanol was removed, and stirred for 24 hours. After completion of the reaction, distillation under reduced pressure yielded 61.6 g of Compound a of Example 1 as a colorless liquid sample (yield 90%).
1H-NMR(500MHz, chloroform-d): 6.42(1H, d), 6.15(1H, dd), 5.86(1H, d), 4.97(1H, d), 4.69(1H, d), 4.36(2H, s), 3.88(2H, d), 3.53(2H, d), 1.36(2H, q), 0.86(3H, t)1H-NMR (500MHz, chloroform-d): 6.42(1H, d), 6.15(1H, dd), 5.86(1H, d), 4.97(1H, d), 4.69(1H, d), 4.36(2H, s), 3.88(2H, d), 3.53(2H, d), 1.36(2H, q), 0.86(3H, t)
실시예 및 비교예Examples and Comparative Examples
실시예 1Example 1
(1) 전해액의 제조(1) Preparation of electrolyte solution
1.0M의 LiPF6 용액(30:70 부피비의 EC/EMC 혼합 용매)을 준비하였다. 상기 LiPF6 용액에 전해액 총 중량을 기준으로, 플루오로에틸렌 카보네이트(FEC) 1중량%, 1,3-프로판 설톤(PS) 0.5중량% 및 1,3-프로펜 설톤(PRS) 0.5중량%를 투입하고, 상기 합성예에 따른 (5-ethyl-1,3-dioxan-5-yl)methyl acrylate 1중량%를 투입하여 전해액을 제조하였다.A 1.0M LiPF 6 solution (EC/EMC mixed solvent with a volume ratio of 30:70) was prepared. Based on the total weight of the electrolyte, 1% by weight of fluoroethylene carbonate ( FEC ), 0.5% by weight of 1,3-propane sultone (PS), and 0.5% by weight of 1,3-propene sultone (PRS) were added to the LiPF 6 solution. An electrolyte solution was prepared by adding 1% by weight of (5-ethyl-1,3-dioxan-5-yl)methyl acrylate according to the above synthesis example.
(2) 리튬 이차 전지 샘플의 제조(2) Preparation of lithium secondary battery samples
Li[Ni0.8Co0.1Mn0.1]O2 양극 활물질, carbon black 도전재, 폴리비닐리덴플루오라이드(PVdF) 바인더를 92:5:3의 중량비로 혼합하여 슬러리를 제조하였다. 상기 슬러리를 15㎛ 두께의 알루미늄박에 균일하게 도포하고, 130℃에서 진공 건조 및 압연하여 리튬 이차 전지용 양극을 제조하였다.A slurry was prepared by mixing Li[Ni 0.8 Co 0.1 Mn 0.1 ]O 2 positive electrode active material, carbon black conductive material, and polyvinylidene fluoride (PVdF) binder at a weight ratio of 92:5:3. The slurry was uniformly applied to a 15㎛ thick aluminum foil, vacuum dried and rolled at 130°C to produce a positive electrode for a lithium secondary battery.
인조흑연 및 천연흑연을 7:3의 중량비로 혼합한 음극 활물질 97중량%, 도전재로 Super-P 1중량%, 바인더로 스티렌-부타디엔 러버(SBR) 바인더 및 카르복시메틸 셀룰로오스(CMC) 중점제를 2중량% 혼합하여 음극 슬러리를 제조하였다. 상기 음극 슬러리를 15㎛ 두께의 구리박에 균일하게 코팅, 건조 및 프레스를 실시하여 음극을 제조하였다.97% by weight of anode active material mixed with artificial graphite and natural graphite in a weight ratio of 7:3, 1% by weight of Super-P as a conductive material, and styrene-butadiene rubber (SBR) binder and carboxymethyl cellulose (CMC) as a binder. A negative electrode slurry was prepared by mixing 2% by weight. The cathode slurry was uniformly coated, dried, and pressed on a 15㎛ thick copper foil to prepare a cathode.
상기 음극 슬러리를 일측에 돌출부(음극 탭)를 갖는 구리 박(15 ㎛ 두께)의 상기 돌출부를 제외한 영역 상에 균일하게 도포하고, 건조한 후, 압연하여 음극을 제조하였다.The cathode slurry was uniformly applied on an area of a copper foil (15 ㎛ thick) having a protrusion (cathode tab) on one side excluding the protrusion, dried, and rolled to prepare a cathode.
상술한 바와 같이 제조된, 양극 및 음극을 각각 소정의 사이즈로 절단하여 적층하고 상기 양극 및 음극 사이에 세퍼레이터(폴리에틸렌, 두께 20㎛)를 개재하여 전극 조립체를 형성한 후, 양극 및 음극의 탭부분을 각각 용접하였다. The anode and cathode manufactured as described above are cut to a predetermined size and stacked, and an electrode assembly is formed by interposing a separator (polyethylene, thickness 20㎛) between the anode and the cathode, and then tab portions of the anode and cathode. were welded respectively.
상기 전극 조립체를 파우치안에 넣고 전해질 주액부면을 제외한 3면을 실링 하였다. 이때 전극 탭이 있는 부분은 실링부에 포함시켰다. 실링부를 제외한 나머지 면을 통해 (1)에서 제조된 전해액을 주액하고 상기 나머지 면을 실링 후, 12시간 이상 함침 시켜 리튬 이차 전지 샘플을 제조하였다.The electrode assembly was placed in a pouch and all three sides except the electrolyte injection surface were sealed. At this time, the part with the electrode tab was included in the sealing part. A lithium secondary battery sample was prepared by injecting the electrolyte solution prepared in (1) through the remaining surface excluding the sealing portion, sealing the remaining surface, and impregnating the remaining surface for more than 12 hours.
실시예 2Example 2
전해액 제조 시, 첨가제 (5-ethyl-1,3-dioxan-5-yl)methyl acrylate의 함량을 0.5중량% 포함한 것을 제외하고는 실시예 1과 동일한 방법으로 이차 전지 샘플을 제조하였다.When preparing the electrolyte solution, a secondary battery sample was prepared in the same manner as in Example 1, except that 0.5% by weight of the additive (5-ethyl-1,3-dioxan-5-yl)methyl acrylate was included.
실시예 3Example 3
전해액 제조 시, 첨가제 (5-ethyl-1,3-dioxan-5-yl)methyl acrylate의 함량을 0.3중량% 포함한 것을 제외하고는 실시예 1과 동일한 방법으로 이차 전지 샘플을 제조하였다.When preparing the electrolyte solution, a secondary battery sample was prepared in the same manner as in Example 1, except that 0.3% by weight of the additive (5-ethyl-1,3-dioxan-5-yl)methyl acrylate was included.
비교예 1Comparative Example 1
전해액 제조 시, 첨가제로 (5-ethyl-1,3-dioxan-5-yl)methyl acrylate를 투입하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 이차 전지 샘플을 제조하였다.A secondary battery sample was prepared in the same manner as in Example 1, except that (5-ethyl-1,3-dioxan-5-yl)methyl acrylate was not added as an additive when preparing the electrolyte solution.
실험예Experiment example
(1) 초기 특성 평가 (1) Initial characteristic evaluation
1-1) 초기 용량 평가1-1) Initial capacity evaluation
실시예 및 비교예의 이차 전지에 각각에 대해 25℃에서 0.5C-rate CC/CV 충전(4.2V, 0.05C cut-off)한 후, 0.5C-rate CC방전(2.7V cut-off)을 수행한 후 방전 용량을 측정하였다. 3회 진행하였다.For each of the secondary batteries of the examples and comparative examples, 0.5C-rate CC/CV charging (4.2V, 0.05C cut-off) was performed at 25°C, followed by 0.5C-rate CC discharging (2.7V cut-off). After that, the discharge capacity was measured. It was conducted 3 times.
1-2) 내부 저항(DCIR) 평가1-2) Internal resistance (DCIR) evaluation
실시예 및 비교예의 이차 전지에 각각에 대해 SOC 60% 지점에서 C-rate를 0.2C, 0.5C, 1.0C, 1.5C, 2.0C, 2.5C, 3.0C로 증감시키고, 해당 C-rate의 충전 및 방전을 10초 진행할 때 전압의 종단 지점을 직선의 방정식으로 구성하여, 그 기울기를 DCIR로 채택하였다.For the secondary batteries of the examples and comparative examples, the C-rate was increased and decreased to 0.2C, 0.5C, 1.0C, 1.5C, 2.0C, 2.5C, and 3.0C at the SOC 60% point, and the corresponding C-rate was charged. And when the discharge was performed for 10 seconds, the terminal point of the voltage was constructed as a straight line equation, and the slope was adopted as DCIR.
(2) 60℃ 고온 저장 특성 평가(2) Evaluation of high temperature storage characteristics at 60℃
2-1) 내부 저항(DCIR) 평가2-1) Internal resistance (DCIR) evaluation
실시예 및 비교예의 이차 전지에 대해 상기 1-2)와 동일한 방법으로 내부 저항(D_DCIR)을 측정하였다. 평가 결과는 하기 표 1에 나타낸다. Internal resistance (D_DCIR) was measured for the secondary batteries of Examples and Comparative Examples in the same manner as 1-2) above. The evaluation results are shown in Table 1 below.
2-1) 용량 유지율(Ret) 평가2-1) Capacity retention rate (Ret) evaluation
실시예 및 비교예의 이차 전지를, 0.5C-rate CC 방전(2.7V cut-off)하여, 방전 용량을 측정하였다. 용량 유지율은 고온 저장 후의 방전 용량을 1-1) 측정한 초기 용량 대비 백분율로 계산하였다.The secondary batteries of Examples and Comparative Examples were subjected to 0.5C-rate CC discharge (2.7V cut-off) to measure the discharge capacity. The capacity retention rate was calculated as a percentage of the initial capacity measured by 1-1) the discharge capacity after high temperature storage.
용량 유지율(%)=(고온 저장 후의 방전용량/초기 용량)×100Capacity maintenance rate (%) = (discharge capacity after high temperature storage / initial capacity) × 100
평가 결과는 하기 표 1에 나타낸다.The evaluation results are shown in Table 1 below.
3-1) 두께 증가율(%) 평가3-1) Thickness increase rate (%) evaluation
실시예들 및 비교예들의 리튬 이차 전지를 25℃에서 0.5C CC/CV 충전(4.2V 0.05C CUT-OFF)한 후, 전지 두께 T1을 측정하였다.The lithium secondary batteries of Examples and Comparative Examples were charged at 0.5C CC/CV (4.2V 0.05C CUT-OFF) at 25°C, and then the battery thickness T1 was measured.
충전된 실시예들 및 비교예들의 리튬 이차 전지를 60℃ 대기 중 노출 조건에서 7주 동안 방치(항온 장치 이용)한 후, 전지 두께 T2를 측정하였다. 전지 두께는 평판 두께 측정 장치(Mitutoyo社, 543-490B)를 이용하여 측정하였다. 전지 두께 증가율은 하기와 같이 계산하였다.The charged lithium secondary batteries of Examples and Comparative Examples were left exposed to air at 60°C for 7 weeks (using a constant temperature device), and then the battery thickness T2 was measured. Battery thickness was measured using a flat plate thickness measuring device (Mitutoyo, 543-490B). The battery thickness increase rate was calculated as follows.
전지 두께 증가율(%) = T2/T1 × 100(%)Battery thickness increase rate (%) = T2/T1 × 100 (%)
평가 결과는 하기 표 1에 나타낸다.The evaluation results are shown in Table 1 below.
initial characteristics
(7주)high temperature storage
(7 weeks)
유지율(%)Volume
Retention rate (%)
표 1을 참조하면, 실시예 1 내지 3에 따른 리튬 이차 전지는 비교예 1에 따른 리튬 이차 전지에 비해, 고온 저장 특성 평가시의 용량 유지율이 높고 두께 증가율이 낮았다. 또한, 실시예 1 및 2에 따른 리튬 이차 전지는 비교예 1에 따른 리튬 이차 전지에 비해, 고온 저장 특성 평가시의 저항 증가율이 낮았다. Referring to Table 1, the lithium secondary batteries according to Examples 1 to 3 had a higher capacity retention rate and a lower thickness increase rate when evaluating high temperature storage characteristics compared to the lithium secondary batteries according to Comparative Example 1. In addition, the lithium secondary battery according to Examples 1 and 2 had a lower resistance increase rate when evaluating high temperature storage characteristics compared to the lithium secondary battery according to Comparative Example 1.
105: 양극 집전체
110: 양극 활물질 층
120: 음극 활물질 층
125: 음극 집전체
100: 양극
130: 음극
140: 분리막
150: 전극 조립체
160: 케이스
107: 양극 리드
127: 음극 리드105: positive electrode current collector 110: positive electrode active material layer
120: negative electrode active material layer 125: negative electrode current collector
100: anode 130: cathode
140: Separator 150: Electrode assembly
160: case
107: positive lead 127: negative lead
Claims (10)
유기 용매; 및
리튬 염을 포함하는, 리튬 이차 전지용 전해액:
[화학식 1]
(화학식 1에서, R1 내지 R10은 서로 동일하거나 상이하고 독립적으로 수소, 또는 치환 또는 비치환된 C1-C10 알킬기이며, L은 치환 또는 비치환된 C1-C10 알킬렌기임).
An additive containing a compound represented by Formula 1;
organic solvent; and
Electrolyte solution for lithium secondary battery containing lithium salt:
[Formula 1]
(In Formula 1, R 1 to R 10 are the same or different from each other and are independently hydrogen or a substituted or unsubstituted C 1 -C 10 alkyl group, and L is a substituted or unsubstituted C 1 -C 10 alkylene group) .
The method of claim 1, wherein R 1 to R 10 are the same or different from each other and are independently hydrogen, a substituted or unsubstituted C 1 -C 6 alkyl group, and L is a substituted or unsubstituted C 1 to C 6 alkylene group, Electrolyte for lithium secondary batteries.
The method according to claim 1, wherein R 1 to R 10 are the same or different from each other and independently hydrogen or an unsubstituted C 1 to C 6 alkyl group, and L is an unsubstituted C 1 to C 6 alkylene group, for a lithium secondary battery. Electrolyte.
The electrolyte solution for a lithium secondary battery according to claim 1, wherein the additive is contained in an amount of 0.1 to 10% by weight based on the total weight of the electrolyte solution.
The electrolyte solution for a lithium secondary battery according to claim 1, wherein the additive is contained in an amount of 0.3 to 7% by weight based on the total weight of the electrolyte solution.
The method according to claim 1, wherein the electrolyte further contains at least one auxiliary additive selected from the group consisting of cyclic carbonate-based compounds, fluorine-substituted cyclic carbonate-based compounds, sultone-based compounds, cyclic sulfate-based compounds, and fluorophosphate-based compounds. Containing an electrolyte for a lithium secondary battery.
The electrolyte solution for a lithium secondary battery according to claim 6, wherein the auxiliary additive is included in an amount of 0.01 to 10% by weight based on the total weight of the electrolyte solution.
The electrolyte solution for a lithium secondary battery according to claim 7, wherein the auxiliary additive is contained in an amount of 0.05 to 5% by weight based on the total weight of the electrolyte solution.
The electrolyte solution for a lithium secondary battery according to claim 1, wherein the organic solvent includes at least one selected from the group consisting of a carbonate-based organic solvent, an ester-based organic solvent, an ether-based organic solvent, a ketone-based organic solvent, and an aprotic organic solvent.
상기 전극 조립체를 수용하는 케이스; 및
상기 케이스 내에 상기 전극 조립체와 함께 수용되는 청구항 1의 리튬 이차 전지용 전해액을 포함하는, 리튬 이차 전지.An electrode assembly in which a plurality of anodes and a plurality of cathodes are repeatedly stacked;
a case accommodating the electrode assembly; and
A lithium secondary battery comprising the electrolyte solution for a lithium secondary battery of claim 1 accommodated together with the electrode assembly in the case.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US18/460,689 US20240120544A1 (en) | 2022-09-16 | 2023-09-05 | Electrolyte solution for lithium secondary battery and lithium secondary battery including the same |
| EP23197272.0A EP4340096A1 (en) | 2022-09-16 | 2023-09-13 | Electrolyte solution for lithium secondary battery and lithium secondary battery including the same |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20220117093 | 2022-09-16 | ||
| KR1020220117093 | 2022-09-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20240038580A true KR20240038580A (en) | 2024-03-25 |
Family
ID=90473757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020230093842A KR20240038580A (en) | 2022-09-16 | 2023-07-19 | Electrolyte solution for lithium secondary battery and lithium secondary battery including the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20240038580A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210001837A (en) | 2019-06-28 | 2021-01-06 | 솔브레인홀딩스 주식회사 | Electrolyte Solution Additive, Electrolyte Solution For Battery And Secondary Battery Comprising The Same |
-
2023
- 2023-07-19 KR KR1020230093842A patent/KR20240038580A/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210001837A (en) | 2019-06-28 | 2021-01-06 | 솔브레인홀딩스 주식회사 | Electrolyte Solution Additive, Electrolyte Solution For Battery And Secondary Battery Comprising The Same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11177507B2 (en) | Electrolyte for lithium secondary battery and lithium secondary battery including the same | |
| US20230198020A1 (en) | Non-aqueous electrolyte and lithium secondary battery including the same | |
| KR20210110018A (en) | Electrolyte for lithium secondary battery and lithium secondary battery including the same | |
| KR102488633B1 (en) | Electrolyte Additives for Secondary Batteries, Non-Aqueous Electrolytes for Lithium Secondary Batteries Containing the Same, and Lithium Secondary Batteries Including the Same | |
| KR20210123534A (en) | Non-aqueous electrolyte and lithium secondary battery including the same | |
| KR20210123606A (en) | Electrolyte for lithium secondary battery and lithium secondary battery including the same | |
| EP4340096A1 (en) | Electrolyte solution for lithium secondary battery and lithium secondary battery including the same | |
| KR20240038580A (en) | Electrolyte solution for lithium secondary battery and lithium secondary battery including the same | |
| EP4213263A2 (en) | Electrolyte solution for lithium secondary battery and lithium secondary battery including the same | |
| KR102503055B1 (en) | Electrolyte for lithium secondary battery and lithium secondary battery including the same | |
| US20220140393A1 (en) | Electrolyte Solution for Lithium Secondary Battery and Lithium Secondary Battery Including the Same | |
| KR102467447B1 (en) | Electrolyte for lithium secondary battery and lithium secondary battery comprising the same | |
| EP4287336A1 (en) | Electrolyte solution for lithium secondary battery and lithium secondary battery including the same | |
| US20230098975A1 (en) | Electrolyte for Lithium Secondary Battery and Lithium Secondary Battery Including the Same | |
| EP4303978A1 (en) | Electrolyte solution for lithium secondary battery and lithium secondary battery including the same | |
| US20220173436A1 (en) | Electrolyte Solution for Lithium Secondary Battery and Lithium Secondary Battery Including the Same | |
| EP4270584A1 (en) | Electrolyte solution for lithium secondary battery and lithium secondary battery including the same | |
| KR20240008505A (en) | Electrolyte solution for lithium secondary battery and lithium secondary battery including the same | |
| KR20240028923A (en) | Electrolyte solution for lithium secondary battery and lithium secondary battery including the same | |
| KR20230130552A (en) | Electrolyte solution for lithium secondary battery and lithium secondary battery including the same | |
| KR20240094799A (en) | Electrolyte solution for lithium secondary battery and lithium secondary battery including the same | |
| KR20240092897A (en) | Lithium secondary battery | |
| KR20230100270A (en) | Non-aqueous electrolyte and lithium secondary battery including the same | |
| KR20230161810A (en) | Electrolyte solution for lithium secondary battery and lithium secondary battery including the same | |
| KR20230161809A (en) | Electrolyte solution for lithium secondary battery and lithium secondary battery including the same |