CN117136453A - Lithium secondary battery with transition metal elution suppressed - Google Patents
Lithium secondary battery with transition metal elution suppressed Download PDFInfo
- Publication number
- CN117136453A CN117136453A CN202380011147.8A CN202380011147A CN117136453A CN 117136453 A CN117136453 A CN 117136453A CN 202380011147 A CN202380011147 A CN 202380011147A CN 117136453 A CN117136453 A CN 117136453A
- Authority
- CN
- China
- Prior art keywords
- secondary battery
- lithium secondary
- electrolyte
- additive
- positive electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 83
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000010828 elution Methods 0.000 title description 6
- 229910052723 transition metal Inorganic materials 0.000 title description 4
- 150000003624 transition metals Chemical class 0.000 title description 4
- 239000002000 Electrolyte additive Substances 0.000 claims abstract description 56
- 239000000654 additive Substances 0.000 claims abstract description 50
- 230000002427 irreversible effect Effects 0.000 claims abstract description 44
- 230000000996 additive effect Effects 0.000 claims abstract description 43
- 239000003792 electrolyte Substances 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- -1 cyclic carbonate compounds Chemical class 0.000 claims description 22
- 229910003002 lithium salt Inorganic materials 0.000 claims description 15
- 159000000002 lithium salts Chemical class 0.000 claims description 15
- 239000007774 positive electrode material Substances 0.000 claims description 15
- 239000006183 anode active material Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 8
- 230000002902 bimodal effect Effects 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 8
- 239000002210 silicon-based material Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- 229910010841 Li6Ni0.9Al0.1O4 Inorganic materials 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 5
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000003273 ketjen black Substances 0.000 claims description 4
- 229910021382 natural graphite Inorganic materials 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 229910010675 Li5Fe0.9Al0.1O4 Inorganic materials 0.000 claims description 3
- 229910010651 Li6Co0.5Fe0.5O4 Inorganic materials 0.000 claims description 3
- 229910010646 Li6Co0.9Al0.1O4 Inorganic materials 0.000 claims description 3
- 229910010832 Li6Mn0.9Al0.1O4 Inorganic materials 0.000 claims description 3
- 229910010822 Li6Ni0.5Fe0.5O4 Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 23
- 230000008901 benefit Effects 0.000 abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 239000011572 manganese Substances 0.000 description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000004020 conductor Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011255 nonaqueous electrolyte Substances 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 239000011356 non-aqueous organic solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910013716 LiNi Inorganic materials 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-BJUDXGSMSA-N (6Li)Lithium Chemical compound [6Li] WHXSMMKQMYFTQS-BJUDXGSMSA-N 0.000 description 1
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-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
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000010294 electrolyte impregnation Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- UQOULBWSWCWZJC-UHFFFAOYSA-N ethene;methyl hydrogen carbonate Chemical compound C=C.COC(O)=O UQOULBWSWCWZJC-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Abstract
The present application relates to a lithium secondary battery comprising Li containing excessive lithium in a positive electrode 6 CoO 4 Etc. as an irreversible additive while including the electrolyte additive of formula 1 having a specific molecular weight in the electrolyte, thereby achieving low battery resistance and effectively preventing metal ions from being eluted from the irreversible additive, and thus having the advantage of excellent battery performance and life.
Description
Technical Field
The present application relates to a lithium secondary battery that suppresses elution of metals, particularly transition metals, into an electrolyte.
The present application claims priority from korean patent application No.10-2022-0034571, filed on 21, 3, 2022, and korean patent application No.10-2023-0013790, filed on 1,2, 2023, the disclosures of which are incorporated herein by reference.
Background
In recent years, secondary batteries have been widely used in small-sized devices such as portable electronic devices, and in medium-sized devices such as battery packs or energy storage devices for hybrid vehicles or electric vehicles.
Graphite is mainly used as a negative electrode material of a lithium secondary battery, but it is difficult to achieve a high capacity of the lithium secondary battery since graphite has a low capacity of 372mAh/g per unit mass. Accordingly, in order to achieve high capacity of a lithium secondary battery, a negative electrode material such as silicon, tin, and oxides thereof, which forms a compound between lithium and metal, has been developed and used as a non-carbon negative electrode material having higher energy density than graphite. However, such a non-carbon anode material has a high capacity, but has the following drawbacks: due to its low initial efficiency, a large amount of lithium is consumed during the initial charge/discharge cycle, and irreversible capacity loss may be large.
In this regard, a method has been proposed that is capable of providing a source or reservoir of lithium ions to the positive electrode material and using a lithium ion battery having electrochemistry after the first cycleThe active material overcomes the irreversible capacity loss of the negative electrode so as to prevent the overall performance of the battery from being degraded. In particular, the use of oxides containing excess lithium, such as Li, is known 6 CoO 4 、Li 2 NiO 2 Or Li (lithium) 5 FeO 4 As a sacrificial positive electrode material or irreversible additive (or overdischarge suppressing agent).
However, this irreversible additive has about 10 due to its 2D percolation network -11 The very low powder conductivity of S/cm is close to that of the insulator. Such low powder conductivity is used to increase the resistance of the positive electrode, and such high resistance is used to reduce battery performance (e.g., capacity, etc.). Furthermore, the irreversible additive is structurally unstable, and thus can compensate for irreversible capacity loss of the negative electrode by preferentially providing lithium ions during an initial charge reaction of the battery. However, side reactions of the electrolyte may be caused due to lithium ion loss and elution of metal ions such as nickel (Ni) and cobalt (Co) from the residual product into the electrolyte. Thus, the irreversible additive has a limitation in that the performance (e.g., capacity retention, etc.) of the battery may be lowered.
Therefore, there is a need to develop a lithium secondary battery capable of containing an irreversible additive such as Li in a positive electrode that can compensate for the irreversible capacity loss of a negative electrode 6 CoO 4 Exhibits low resistance in the state of the like, and more effectively suppresses and/or prevents metal ions (M + ) From the irreversible additive into the electrolyte.
Prior art literature
[ patent literature ]
Patent document 1: japanese patent laid-open publication No. 2019-61750
Disclosure of Invention
[ technical problem ]
Accordingly, the present application is believed to solve at least some of the above problems. For example, one aspect of the present application provides a lithium secondary battery comprising a lithium containing excess lithium 6 CoO 4 Etc. as irreversible additives while exhibiting low cell resistance and inhibiting metal ion (M+) addition from irreversibleDissolving out the agent.
Technical scheme
In order to solve the above problems, according to an exemplary embodiment of the present application, there is provided a lithium secondary battery including: an electrode assembly including a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode; and an electrolyte composition comprising a lithium salt, an electrolyte additive having a unit represented by the following formula 1, and a nonaqueous solvent,
wherein the positive electrode comprises a positive electrode active layer containing an irreversible additive represented by the following formula 2, and
the electrolyte additive has a weight average molecular weight of less than 40,000g/mole:
[ 1]
[ 2]
Li a M b M’ 1-b O c
(wherein:
R 1 、R 2 and R is 3 Each hydrogen or an alkyl group having 1 to 6 carbon atoms,
R 4 and R is 5 Each an alkylene group having 1 to 6 carbon atoms,
p, q and r are each integers from 0 to 5,
m and n are each integers of 10 to 200,
m comprises one or more of Co, ni, mn and Fe,
m 'comprises one or more of Co, ni, mn, fe, al, mg, zn and Ti, provided that M and M' are different from each other, and
a. the ranges of b and c are respectively 1.50-6.5,0-1 and 1.5-4.5.
Specifically, in the unit represented by formula 1, R 1 、R 2 And R is 3 Each may be hydrogen or methyl, R 4 And R is 5 Each may be ethylene or propylene, and p, q and r may each beAn integer from 0 to 2.
Further, the m: n ratio of the unit represented by formula 1 may be 1:1.01 to 10.
In addition, the electrolyte additive may have a weight average molecular weight of 5,000 to 30,000g/mole.
Also, the electrolyte additive may have a bimodal molecular weight distribution, and may have a polydispersity index (PDI) of 1.2 to 5.0.
In addition, the content of the electrolyte additive may be less than 5 wt% based on the total weight of the electrolyte composition.
Also, the electrolyte composition may include an electrolyte auxiliary additive including one or more cyclic carbonate compounds selected from the group consisting of Vinylene Carbonate (VC), vinyl Ethylene Carbonate (VEC), and fluoroethylene carbonate (FEC); and one or more sultone compounds selected from the group consisting of 1, 3-Propane Sultone (PS), 1, 4-butane sultone, ethylene sultone, 1, 3-propylene sultone (PRS), 1, 4-butene sultone and 1-methyl-1, 3-propylene sultone.
In addition, the irreversible additive represented by formula 2 may include Li 6 CoO 4 、Li 6 NiO 4 、Li 2 NiO 2 、Li 6 MnO 4 、Li 2 MnO 3 、Li 5 FeO 4 、Li 6 Co 0.9 Al 0.1 O 4 、Li 6 Co 0.7 Zn 0.3 O 4 、Li 6 Ni 0.9 Al 0.1 O 4 、Li 6 Mn 0.9 Al 0.1 O 4 、Li 5 Fe 0.9 Al 0.1 O 4 、Li 6 Co 0.5 Fe 0.5 O 4 、Li 6 Ni 0.5 Fe 0.5 O 4 、Li 6 Ni 0.9 Al 0.1 O 4 One or more of the following.
Also, the irreversible additive may be contained in an amount of 0.01 to 5 wt% based on the total weight of the positive electrode active layer.
In addition, the positive electrode active layer may contain one or more of lithium metal oxides represented by formula 3 as a positive electrode active material:
[ 3]
Li x [Ni y Co z Mn w M 1 v ]O 2
Wherein:
M 1 comprises one or more elements selected from the group consisting of W, cu, fe, V, cr, ti, zr, zn, al, in, ta, Y, la, sr, ga, sc, gd, sm, ca, ce, nb, mg, B and Mo, and
x, y, z, w and v are each in the range of 1.0.ltoreq.x.ltoreq. 1.30,0.ltoreq.y <1, 0.ltoreq.z.ltoreq.1, 0.ltoreq.w.ltoreq.1, 0.ltoreq.v.ltoreq.0.1, provided that y+z+w+v=1.
Also, the anode may include an anode active layer that contains an anode active material, and the anode active material may contain one or more carbon materials selected from the group consisting of natural graphite, artificial graphite, expanded graphite, non-graphitized carbon, carbon black, acetylene black, and ketjen black.
In addition, the anode active material may further contain a material selected from silicon (Si), silicon carbide (SiC), and silicon oxide (SiO) q The method comprises the steps of carrying out a first treatment on the surface of the Provided that 0.8.ltoreq.q.ltoreq.2.5). In this case, the content of the silicon material may be 1 to 20 wt% based on the total weight of the anode active material.
According to another exemplary embodiment of the present application, there is provided a lithium secondary battery module including:
the lithium secondary battery of the present application; and
and a module case in which the lithium secondary battery is mounted.
[ advantageous effects ]
The lithium secondary battery of the present application includes Li containing excessive lithium in the positive electrode 6 CoO 4 Etc. as an irreversible additive while including the electrolyte additive of formula 1 having a specific molecular weight in the electrolyte, thereby achieving low battery resistance and effectively preventing metal ions from being eluted from the irreversible additive, and thus having the advantage of excellent battery performance and life.
Detailed Description
The present disclosure is capable of various modifications and various embodiments, and thus specific embodiments of the present disclosure are described in detail in the detailed description.
It should be understood, however, that the disclosure is not intended to be limited to the particular embodiments and includes all modifications, equivalents, or alternatives falling within the spirit and technical scope of the disclosure.
The terms "comprises," "comprising," and "having," as used herein, specify the presence of stated features, amounts, steps, actions, components, or members, or combinations thereof, and are understood not to foreclose the possibility of the presence or addition of one or more other features, amounts, steps, actions, components, members, or combinations thereof.
Moreover, when a layer, film, region, or panel is provided "on" another portion, this includes not only the case where one portion is provided "directly" on "another portion, but also the case where a third portion is interposed therebetween. In contrast, when a layer, film, region, or panel is disposed "under" another portion, this includes not only the case where one portion is disposed "directly" under "another portion, but also the case where a third portion is interposed therebetween. In addition, in the present application, "upper" may include not only the case of being provided at the upper part but also the case of being provided at the lower part.
In addition, unless specifically indicated otherwise, the symbol "×" refers to bonds formed between the ends of the same or different atoms or formulas.
In the present disclosure, the term "alkylene" also refers to a straight or branched chain divalent unsaturated hydrocarbon group. As an example, the alkylene group may be substituted or unsubstituted. Alkylene groups include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, t-butylene, pentylene, 3-pentylene, and the like, but the disclosure is not limited thereto.
In addition, in the present disclosure, the term "unit" or "repeat unit" refers to a constituent of an oligomer and/or polymer, and includes chemical structures derived from monomers used during polymerization.
Hereinafter, the present application will be described in detail.
Lithium secondary battery
According to an exemplary embodiment of the present application, there is provided a lithium secondary battery including:
an electrode assembly including a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode; and
an electrolyte composition comprising a lithium salt, an electrolyte additive having a unit represented by the following formula 1, and a nonaqueous solvent,
wherein the positive electrode comprises a positive electrode active layer containing an irreversible additive capable of providing excess lithium ions, and
the electrolyte additive has a weight average molecular weight of less than 40,000g/mole:
[ 1]
Wherein:
R 1 、R 2 and R is 3 Each hydrogen or an alkyl group having 1 to 6 carbon atoms,
R 4 and R is 5 Each an alkylene group having 1 to 6 carbon atoms,
p, q and r are each integers from 0 to 5,
m and n are each integers of 10 to 200.
The lithium secondary battery of the present application comprises: an electrode assembly including a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode; and an electrolyte composition impregnated into the electrode assembly.
In this case, the positive electrode may have a positive electrode active layer on the positive electrode current collector, the positive electrode active layer including a positive electrode active material and an irreversible additive capable of providing an excessive amount of lithium ions, and the electrolyte composition includes an electrolyte additive having a specific chemical structure and molecular weight to prevent and/or inhibit dissolution of metal from the irreversible additive after initial charge of the battery.
Specifically, the electrolyte additive used in the present application may have a unit represented by the following formula 1:
[ 1]
Wherein:
R 1 、R 2 and R is 3 Each hydrogen or an alkyl group having 1 to 6 carbon atoms,
R 4 and R is 5 Each an alkylene group having 1 to 6 carbon atoms,
p, q and r are each integers from 0 to 5,
m and n are each integers of 10 to 200.
More specifically, in the unit represented by formula 1, R 1 、R 2 And R is 3 Each may be hydrogen or methyl, R 4 And R is 5 Each may be ethylene or propylene, and p, q, and r may each be an integer from 0 to 2.
As an example, the unit represented by formula 1 may include one or more of the following structural formulas 1 to 4:
< Structure 1>
< Structure 2>
< Structure 3>
< Structure 4>
The unit represented by formula 1 may include a repeating unit derived from an alkyl acrylate having 1 to 6 carbon atoms, and thus may have excellent solubility in an organic solvent, particularly a nonaqueous solvent.
Furthermore, the unit represented by formula 1 includes a repeating unit containing a cyano group (-CN), and thus a coordination bond can be induced between the cyano group and a metal ion eluted from the irreversible additive, specifically, a transition metal ion such as nickel (Ni), cobalt (Co), manganese (Mn), and the like. Therefore, the unit represented by formula 1 can easily trap metal ions, thereby preventing an increase in the concentration of metal ions in the electrolyte.
Therefore, in the present application, in order to optimize the solubility of the unit represented by formula 1 in a nonaqueous solvent and the metal ion capturing efficiency, the ratio of the number (m) of repeating units derived from an alkyl acrylate having 1 to 6 carbon atoms to the number (n) of repeating units containing cyano groups may be adjusted to satisfy a certain ratio range. Specifically, the m: n ratio of the unit represented by formula 1 may be 1:1.01 to 10, more specifically the m: n ratio is 1:2 to 10, 1:2 to 8, 1:2 to 6, 1:3 to 7, 1:5 to 10, or 1:3 to 5. When the ratio of n in formula 1 is less than 1.01, the metal ion capturing efficiency may be significantly reduced, and also may cause an increase in battery resistance, thereby reducing the charge/discharge capacity. On the other hand, when the ratio of n is greater than 10, the ion conductivity may decrease, and the battery safety at high temperature may decrease.
Furthermore, the electrolyte additive may have a weight average molecular weight of less than 40,000g/mole. Specifically, the electrolyte additive may have a weight average molecular weight of 1,000 to 40,000g/mole;2,000 to 35,000g/mole;5,000 to 30,000g/mole;5,000 to 25,000g/mole;5,000 to 15,000g/mole;8,000 to 19,000g/mole; or 10,000 to 20,000g/mole. When the weight average molecular weight of the electrolyte additive is greater than or equal to 40,000g/mole, the electrolyte impregnation property and initial resistance and resistance increase rate of the battery may be significantly enhanced, resulting in a decrease in capacity. In this case, the efficiency of the extracted metal ion capture may also be significantly reduced due to the aggregation of the electrolyte additive itself being induced. Even without inducing aggregation, the electrolyte additive may form a precipitate with the trapped metal ions, blocking the pores of the separator, thereby causing a decrease in the electrical performance of the battery. Also, when the weight average molecular weight of the electrolyte additive is less than 1,000g/mole, the ability of the electrolyte additive to capture metal ions may not be sufficiently achieved, resulting in a significant increase in the concentration of metal ions dissolved in the electrolyte composition.
In addition, the electrolyte additive may have a bimodal molecular weight distribution pattern. The expression "having a bimodal molecular weight distribution pattern" may mean that the electrolyte composition includes the unit represented by formula 1, and also includes two electrolyte additives having different molecular weights. Here, the bimodal molecular weight distribution pattern can be measured by GPC and can be calculated using standard polystyrene conversion methods.
As one example, the electrolyte additive includes a unit represented by formula 1, wherein the electrolyte additive includes a first electrolyte additive having a weight average molecular weight of 12,000±500g/mole and a second electrolyte additive having a weight average molecular weight of 15,000±500 g/mole. In this case, when the electrolyte additive is measured by GPC, a bimodal spectrum having two peaks around 12,000 and 15,000 in molecular weight, respectively, can be obtained. In this case, the content of the second electrolyte additive may be 10 to 100 parts by weight based on 100 parts by weight of the first electrolyte additive having a smaller weight average molecular weight.
When the electrolyte additive having a bimodal molecular weight distribution is included in the present application, the dissolution rate of metal ions can be effectively reduced while minimizing the increase in resistance of the secondary battery.
Also, the polydispersity index (PDI) of the electrolyte additive may be 1.2 to 5.0. The polydispersity index (PDI) is a value (Mw/Mn) obtained by dividing the weight average molecular weight (Mw) of the electrolyte additive by the number average molecular weight (Mn). In this case, the polydispersity index of the electrolyte additive of the present application may be 1.2 to 4.5, 1.2 to 4.0, 1.2 to 3.5, 1.2 to 3.0, 1.2 to 2.5, 1.2 to 1.9, 1.5 to 2.5, 1.8 to 3.1, or 1.6 to 2.2.
As an example, the polydispersity index of the electrolyte additive may be 1.8 to 2.1.
As another example, the electrolyte additive includes a unit represented by formula 1, wherein when the electrolyte additive has a bimodal molecular weight distribution by including a first electrolyte additive having a weight average molecular weight of 12,000±500g/mole and a second electrolyte additive having a weight average molecular weight of 15,000±500g/mole, the polydispersity index of each of the first electrolyte additive and the second electrolyte additive may be 1.6 to 2.0.
In addition, the content of the electrolyte additive may be less than 5 wt% based on the total weight of the electrolyte composition. Specifically, the content of the electrolyte additive may be 0.05 to 5 wt% based on the total weight of the electrolyte composition; 0.05 to 4 wt%; 0.05 to 3 wt%; 0.1 to 2.5 wt.%; 0.1 to 2.2 wt.%; 0.2 to 1.6 wt.%; 0.9 to 1.9 wt.%; 1.6 to 2.3 wt.%; or 0.1 to 0.8 wt%.
In the present application, when the content of the electrolyte additive is adjusted within the content range, it is possible to prevent an increase in the internal resistance and a decrease in the ionic conductivity of the battery due to an excessive amount of the electrolyte additive. Also, it is possible to reduce side reactions between the electrolyte composition and the positive electrode active layer, and to prevent a decrease in the ability to trap metal ions due to trace amounts of electrolyte additives.
Meanwhile, the electrolyte composition includes a lithium salt and a nonaqueous solvent in addition to the above electrolyte additives.
In this case, the lithium salt may be applied without any particular limitation as long as it is used in the nonaqueous electrolyte in the art. In particular, the lithium salt may comprise a compound selected from the group consisting of LiCl, liBr, liI, liClO 4 、LiBF 4 、LiB 10 Cl10、LiPF 6 、LiCF 3 SO 3 、LiCF 3 CO 2 、LiAsF 6 、LiSbF 6 、LiAlCl 4 、CH 3 SO 3 Li、(CF 3 SO 2 ) 2 NLi and (FSO) 2 ) 2 One or more of the group consisting of NLi.
The concentration of the lithium salt is not particularly limited, but the lower limit of the suitable concentration range is 0.5mol/L or more, specifically 0.7mol/L or more, more specifically 0.9mol/L or more, and the upper limit of the suitable concentration range is 2.5mol/L or less, specifically 2.0mol/L or less, more specifically 1.5mol/L or less. When the concentration of the lithium salt is less than 0.5mol/L, the ionic conductivity may be lowered, resulting in degradation of the cycle characteristics and output characteristics of the nonaqueous electrolyte battery. Also, when the concentration of the lithium salt is more than 2.5mol/L, the viscosity of the electrolyte solution for the nonaqueous electrolyte battery may be increased, and thus the ionic conductivity may be lowered, and the cycle characteristics and output characteristics of the nonaqueous electrolyte battery may also be lowered.
Moreover, when a large amount of lithium salt is dissolved in a nonaqueous organic solvent at a time, the liquid temperature may rise due to the heat of dissolution of the lithium salt. In this way, when the temperature of the nonaqueous organic solvent is significantly increased due to the heat of solution of the lithium salt, decomposition of the fluorine-containing lithium salt can be promoted, thereby generating Hydrogen Fluoride (HF). Hydrogen Fluoride (HF) is undesirable because it can lead to reduced cell performance. Therefore, the temperature at which the lithium salt is dissolved in the nonaqueous organic solvent is not particularly limited, but may be adjusted in the range of-20 to 80 ℃, specifically in the range of 0 to 60 ℃.
In addition, the nonaqueous organic solvent used in the electrolyte composition may be applied without any particular limitation as long as it is used in the nonaqueous electrolyte in the art. Specifically, for example, aprotic organic solvents such as N-methyl-2-pyrrolidone, ethylene Carbonate (EC), propylene Carbonate (PC), propylene carbonate, butylene carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), γ -butyrolactone, 1, 2-Dimethoxyethane (DME), tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1, 3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfane, 1, 3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ether, methyl Propionate (MP), ethyl Propionate (EP), propyl Propionate (PP), and the like can be used as the nonaqueous organic solvents.
The nonaqueous organic solvent used in the present application may be used alone, or two or more of them may be used in any ratio and combination depending on the purpose. Among them, propylene carbonate, ethylene carbonate, fluoroethylene carbonate, diethyl carbonate, dimethyl carbonate and ethylene carbonate are particularly preferable in terms of electrochemical stability in oxidation/reduction reaction and chemical stability to heat or reaction with a solute.
In addition, the electrolyte composition may further include an electrolyte auxiliary additive, if necessary, in order to prevent collapse of the negative electrode due to decomposition of the nonaqueous electrolyte under high power conditions, or to further improve low-temperature high-rate discharge characteristics, high-temperature stability, overcharge protection, battery expansion inhibition effect at high temperatures, and the like.
Specifically, the electrolyte auxiliary additive may include one or more of a cyclic carbonate compound and a sultone compound, which may be preferably used in combination. In this case, during initial activation of the battery, a more uniform SEI film may be formed on the surface of the negative electrode, and high temperature stability may be improved, which may suppress gas generation due to electrolyte decomposition.
In this case, the cyclic carbonate compound may include one or more of Vinylene Carbonate (VC), vinyl Ethylene Carbonate (VEC), and fluoroethylene carbonate (FEC), and the sultone compound may include one or more of 1, 3-Propane Sultone (PS), 1, 4-butane sultone, ethylene sultone, 1, 3-propylene sultone (PRS), 1, 4-butene sultone, and 1-methyl-1, 3-propylene sultone.
Also, the electrolyte auxiliary additive may be contained in an amount of 0.01 to 10 wt%, specifically 0.05 to 5 wt%, or 1.5 to 3 wt%, based on the total weight of the electrolyte composition. In the present application, when the content of the electrolyte additive is adjusted within the content range, it is possible to prevent the additive from being present in a precipitated state at room temperature due to an excessive amount of the auxiliary additive, thereby causing deterioration in the resistance characteristics of the battery. Further, it is possible to prevent the effect of improving the high-temperature life characteristics from being insufficient due to the addition of trace amounts of auxiliary additives.
Meanwhile, the positive electrode may have a positive electrode active layer on the positive electrode current collector, the positive electrode active layer including a positive electrode active material and an irreversible additive capable of providing an excessive amount of lithium ions. Specifically, the positive electrode has a positive electrode active layer prepared by coating, drying, and pressing a slurry containing a positive electrode active material and an irreversible additive on a positive electrode current collector, and may optionally further include a conductive material, a binder, and other additives, if necessary.
In this case, the positive electrode active material is a material that can cause an electrochemical reaction on the positive electrode current collector, and may be a lithium composite transition metal oxide containing two or more elements selected from the group consisting of nickel (Ni), cobalt (Co), manganese (Mn), aluminum (Al), zinc (Zn), titanium (Ti), magnesium (Mg), chromium (Cr), and zirconium (Zr). For example, the positive electrode active material may include one or more of lithium metal oxides represented by formula 3 capable of reversibly intercalating and deintercalating lithium ions:
[ 3]
Li x [Ni y Co z Mn w M 1 v ]O 2
Wherein:
M 1 comprising one or more elements selected from the group consisting of W, cu, fe, V, cr, ti, zr, zn, al, in, ta, Y, la, sr, ga, sc, gd, sm, ca, ce, nb, mg, B and Mo,
x, y, z, w and v are each in the range of 1.0.ltoreq.x.ltoreq. 1.30,0.ltoreq.y <1, 0.ltoreq.z.ltoreq.1, 0.ltoreq.w.ltoreq.1, 0.ltoreq.v.ltoreq.0.1, provided that y+z+w+v=1.
When the lithium metal oxide represented by formula 3 is used as the positive electrode active material, the lithium metal oxide has an advantage of stably supplying high-capacity power and/or high-voltage power.
In this case, the lithium metal oxide represented by formula 3 may include lithium cobalt oxide (LiCoO) 2 ) Lithium nickel oxide (LiNiO) 2 ) Lithium manganese oxide (LiMnO) 2 And LiMn 2 O 4 Etc.) and lithium nickel cobalt manganese oxide (LiNi 0.8 Co 0.1 Mn 0.1 O 2 、LiNi 0.6 Co 0.2 Mn 0.2 O 2 、LiNi 0.9 Co 0.05 Mn 0.05 O 2 、LiNi 0.6 Co 0.2 Mn 0.1 Al 0.1 O 2 、LiNi 0.6 Co 0.2 Mn 0.15 Al 0.05 O 2 、LiNi 0.7 Co 0.1 Mn 0.1 Al 0.1 O 2 ) Etc.
Also, the content of the positive electrode active material may be 85 to 95 parts by weight, specifically 88 to 95 parts by weight, 90 to 95 parts by weight, 86 to 90 parts by weight, or 92 to 95 parts by weight, based on 100 parts by weight of the positive electrode active layer.
In addition, the positive electrode active layer contains a positive electrode active material exhibiting electrical activity, and an irreversible additive imparting irreversible capacity. In this case, the irreversible additive may be a compound represented by the following formula 2:
[ 2]
Li a M b M’ 1-b O c
Wherein:
m comprises one or more of Co, ni, mn and Fe,
m 'comprises one or more of Co, ni, mn, fe, al, mg, zn and Ti, provided that M and M' are different from each other,
a. the ranges of b and c are respectively 1.50-6.5,0-1 and 1.5-4.5.
When the irreversible additive contains an excess of lithium, lithium may be provided for lithium consumption by irreversible chemical/physical reactions at the anode during initial charging. Therefore, an increase in the charge capacity of the battery and a decrease in the irreversible capacity of the battery may be caused, thereby improving the life characteristics.
Such irreversible additives represented by formula 2 may include Li 6 CoO 4 、Li 6 NiO 4 、Li 2 NiO 2 、Li 6 MnO 4 、Li 2 MnO 3 、Li 5 FeO 4 、Li 6 Co 0.9 Al 0.1 O 4 、Li 6 Co 0.7 Zn 0.3 O 4 、Li 6 Ni 0.9 Al 0.1 O 4 、Li 6 Mn 0.9 Al 0.1 O 4 、Li 5 Fe 0.9 Al 0.1 O 4 、Li 6 Co 0.5 Fe 0.5 O 4 、Li 6 Ni 0.5 Fe 0.5 O 4 、Li 6 Ni 0.9 Al 0.1 O 4 One or more of the following.
Wherein the cobalt-based additive, such as Li, has a high lithium ion content as compared to nickel-containing oxides widely used in the art 6 CoO 4 Or Li (lithium) 6 Co 0.7 Zn 0.3 O 4 Can be used to replenish lithium ions lost in the irreversible reaction during initial activation of the battery, which can significantly improve the charge/discharge capacity of the battery. Also, the cobalt-based additive has no side reaction caused by elution of transition metal during charge/discharge cycles of the battery, compared to iron-and/or manganese-containing oxides widely used in the art, and thus the cobalt-based additive has an advantage of excellent battery stability.
In addition, the irreversible additive may have an average particle diameter of 0.1 to 10 μm, specifically an average particle diameter of 0.1 to 8 μm;0.1 to 5 μm;0.1 to 3 μm;0.5 to 2 μm;0.1 to 0.9 μm;0.1 to 0.5 μm;0.6 to 0.9 μm;1 to 4 μm;4 to 6 μm; or 6 to 9 μm. In the present application, when the average particle diameter of the irreversible additive is controlled within the above particle diameter range, it is possible to prevent the decrease in the powder conductivity of the irreversible additive while increasing the irreversible activity.
Also, the irreversible additive may be contained in an amount of 0.01 to 5 parts by weight based on the total weight of the positive electrode active layer. Specifically, the irreversible additive may be contained in an amount of 0.01 to 4 parts by weight based on the total weight of the positive electrode active layer; 0.01 to 3 parts by weight; 0.01 to 2 parts by weight; 0.1 to 1 part by weight; 0.5 to 2 parts by weight; 1 to 3 parts by weight; 2 to 4 parts by weight; 1.5 to 3.5 parts by weight; 0.5 to 1.5 parts by weight; 1 to 2 parts by weight; 0.1 to 0.9 parts by weight; or 0.3 to 1.2 parts by weight.
In addition, the positive electrode active layer may further include a binder, a conductive material, other additives, and the like in addition to the positive electrode active material and the irreversible additive.
In this case, the conductive material may be used to improve the performance (e.g., conductivity, etc.) of the positive electrode, and may include one or more selected from the group consisting of natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon nanotubes, graphene, and carbon fibers. For example, the conductive material may include acetylene black.
Also, the content of the conductive material may be 0.5 to 5 parts by weight based on 100 parts by weight of the positive electrode active layer. Specifically, the content of the conductive material may be 0.5 to 4 parts by weight based on 100 parts by weight of the positive electrode active layer; 0.5 to 3 parts by weight; 0.5 to 1 part by weight; 0.5 to 2 parts by weight; 1 to 3 parts by weight; 2 to 4 parts by weight; 1.5 to 3.5 parts by weight; 0.5 to 1.5 parts by weight; or 1 to 2 parts by weight.
In addition, the binder may include one or more resins selected from the group consisting of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, and copolymers thereof. As one example, the binder may include polyvinylidene fluoride.
Also, the positive electrode active layer may include 1 to 10 parts by weight, specifically 2 to 8 parts by weight, or 1 to 5 parts by weight of a binder based on 100 parts by weight of the positive electrode active layer.
In addition, the average thickness of the positive electrode active layer is not particularly limited, but may specifically be 50 μm to 300 μm, more specifically 100 μm to 200 μm;80 μm to 150 μm;120 μm to 170 μm;150 μm to 300 μm;200 μm to 300 μm; or 150 μm to 190 μm.
Also, as the positive electrode current collector in the positive electrode, a material having high conductivity without causing chemical changes in the corresponding battery may be used. For example, stainless steel, aluminum, nickel, titanium, calcined carbon, and the like can be used. In the case of aluminum or stainless steel, those surface-treated with carbon, nickel, titanium, silver, or the like can also be used. Also, the positive electrode current collector may have fine irregularities formed on the surface thereof to enhance the adhesive strength of the positive electrode active material, and may be in various forms thereof such as a film, a sheet, a foil, a net, a porous material, a foam, a non-woven fabric, and the like. In addition, the average thickness of the positive electrode current collector may be appropriately adjusted in the range of 3 to 500 μm in consideration of the conductivity and the total thickness of the manufactured positive electrode.
In addition, the anode may be manufactured by coating, drying, and pressing an anode active layer including an anode active material on an anode current collector. In this case, the anode active layer may optionally further include a conductive material, an organic binder polymer, and other additives as in the cathode, if necessary.
Here, the anode active material may include one or more selected from the group consisting of lithium metal, nickel metal, copper metal, SUS metal, carbon material capable of reversibly intercalating/deintercalating lithium ions, metal or an alloy of these metals with lithium, metal composite oxide, material capable of doping and dedoping lithium, and transition metal oxide.
As one example, the anode active material may include one or more carbon materials selected from the group consisting of natural graphite, artificial graphite, expanded graphite, non-graphitized carbon, carbon black, acetylene black, and ketjen black.
Also, the anode active material may further include a silicon material in addition to the carbon material in order to further enhance the charge/discharge capacity of the battery. The silicon material refers to a material including silicon atoms as a main component. In this case, as such a silicon material, silicon (Si), silicon carbide (SiC), silicon monoxide (SiO) or silicon dioxide (SiO) 2 ) May be used alone or in combination. When silicon monoxide (SiO) and silicon dioxide (SiO 2 ) When homogeneously mixed or compounded as a silicon (Si) -containing material and contained in the anode active layer, it can be formed of a silicon oxide (SiO q The method comprises the steps of carrying out a first treatment on the surface of the Provided that 0.8.ltoreq.q.ltoreq.2.5).
In addition, the content of the silicon material may be 1 to 20 wt%, specifically 3 to 10 wt%, based on the total weight of the anode active material; 8 to 15 wt.%; 13 to 18 wt.%; or 2 to 8 wt%. In the present application, when the content of the silicon material is adjusted within the content range as described above, the energy density of the battery can be maximized.
Also, the anode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the corresponding battery, and for example, copper, stainless steel, aluminum, nickel, titanium, calcined carbon, and the like may be used as the anode current collector, and in the case of copper or stainless steel, those surface-treated with carbon, nickel, titanium, silver, and the like may be used. In addition, the average thickness of the negative electrode current collector may be appropriately adjusted in the range of 1 to 500 μm in consideration of the conductivity and the total thickness of the manufactured negative electrode.
In addition, the form of the lithium secondary battery of the present application is not particularly limited, but may be, in particular, cylindrical, prismatic, pouch-shaped, or coin-shaped. According to an exemplary embodiment of the present application, the lithium secondary battery may be a cylindrical lithium secondary battery, a prismatic lithium secondary battery, a pouch-type lithium secondary battery, or a coin-type lithium secondary battery, particularly a pouch-type lithium secondary battery.
When the lithium secondary battery of the present application has the constitution as described above, lithium ions irreversibly lost during the initial charging process, i.e., the activation process, of the secondary battery can be retained, thereby improving the charge/discharge capacity. Also, metal ions originating from the positive electrode active layer can be effectively trapped to significantly reduce the concentration of metal ions dissolved in the electrolyte composition, thereby improving the increase in resistance and side reactions and the decrease in performance of the battery caused by the dissolved metal ions even under high temperature conditions.
Lithium secondary battery module
There is also provided, according to an exemplary embodiment of the present application, a lithium secondary battery module including:
the lithium secondary battery of the present application described above; and
and a module case in which the lithium secondary battery is mounted.
The lithium secondary battery module of the present application is a battery module including a plurality of unit cells, each of which includes the lithium secondary battery of the present application, and a module case configured to accommodate the plurality of unit cells.
When the lithium secondary battery module includes a plurality of the lithium secondary batteries of the present application as described above as unit cells, the lithium secondary battery module has the following advantages: has low initial resistance and low resistance increase rate and high voltage holding rate even under high temperature conditions, and has a characteristic of significantly reducing the concentration of metal ions eluted in the electrolyte composition.
Meanwhile, the present application provides a battery pack including the battery module and an apparatus including the battery pack as a power source.
In this case, specific examples of the apparatus include a power tool driven by a motor; electric vehicles, including Electric Vehicles (EVs), hybrid Electric Vehicles (HEVs), and plug-in hybrid electric vehicles (PHEVs); the electric two-wheel vehicle comprises an electric bicycle and an electric scooter; an electric golf cart; and an energy storage system, but the present application is not limited thereto.
Hereinafter, the present application will be described in further detail with reference to the following examples and experimental examples.
However, it should be understood that the following examples and experimental examples are only intended to illustrate the present application, and the contents of the present application are not limited to the following examples and experimental examples.
Examples and comparative examples
A) Preparation of electrolyte composition
LiPF to be lithium salt 6 And LiFSI were dissolved in solvents prepared by mixing Ethylene Carbonate (EC), ethylene Methyl Carbonate (EMC) and diethyl carbonate (DMC) in a volume ratio of 20:5:75 at concentrations of 0.8M and 0.7M, respectively, and the electrolyte additives were weighed and dissolved in the kinds and contents shown in table 1 below. Thereafter, vinylene Carbonate (VC) and 1, 3-Propane Sultone (PS) as electrolyte auxiliary additives were added at 2 wt% and 0.5 wt%, respectively, to prepare nonaqueous electrolyte compositions.
Here, in the case of example 5, two electrolyte additives having weight average molecular weights of 12,000g/mole and 15,000g/mole, respectively, and simultaneously containing the unit represented by formula 1 were mixed and used at a weight ratio of 1:1.
Further, the weight average molecular weight and PDI of the electrolyte additive were measured using Gel Permeation Chromatography (GPC), and the molecular weight distribution pattern was analyzed from the obtained spectrum. For Gel Permeation Chromatography (GPC), alliance 4 equipment was stabilized. When the apparatus was stabilized, a reference sample and a sampling sample were injected into the apparatus to obtain a chromatogram, and the molecular weight was calculated from the obtained results according to the analysis method (system: alliance 4, column: agilent PL mixed B, eluent: THF, flow rate: 0.1mL/min, temperature: 40 ℃, injection volume: 100 μl). The measurement results are shown in table 1.
TABLE 1
B) Manufacturing of lithium secondary battery
Preparation of LiNi 0.6 Co 0.2 Mn 0.1 Al 0.1 O 2 And LiNiO 2 (1:1, weight/weight) as a positive electrode active material, and the prepared active material, carbon black as a conductive material, and polyvinylidene fluoride as a binder were mixed in a weight ratio of 94:3:3 in N-methylpyrrolidone (NMP) to form a slurry. Thereafter, the slurry was cast on an aluminum sheet, dried at 120 ℃ in a vacuum oven, and then rolled to manufacture a positive electrode.
Separately, a material made of artificial graphite and silica (SiO 2 ) As a negative electrode active material, 97 parts by weight of the negative electrode active material and 3 parts by weight of Styrene Butadiene Rubber (SBR) were mixed in water to form a slurry. Then, the slurry was cast on a copper sheet, dried at 130 ℃ in a vacuum oven, and then rolled to manufacture a negative electrode.
An 18 μm thick separator composed of polypropylene was interposed between the obtained positive electrode and negative electrode, and inserted into the case. Thereafter, each of the electrolyte compositions prepared in examples 1 to 6 and comparative examples 1 to 3 was injected to manufacture a lithium secondary battery.
Experimental example
In order to evaluate the performance of the lithium secondary battery of the present application, the following experiment was performed.
A) Analysis of initial resistance
The lithium secondary batteries fabricated in examples and comparative examples were fully charged to 100% SOC under a voltage condition of 4.25V, respectively. Thereafter, the DC resistance of each of the fully charged lithium secondary batteries was measured, and the DC resistance deviation ratio of each of the lithium secondary batteries was calculated as an initial resistance based on the DC resistance value of the lithium secondary battery of comparative example 1 including HTCN as a single-molecule electrolyte additive. The results are shown in table 2 below.
B) Analysis of resistivity and Voltage Retention after high temperature storage
The lithium secondary batteries fabricated in examples and comparative examples were fully charged to 100% SOC under a voltage condition of 4.25V, respectively. Thereafter, the AC resistance and voltage of each fully charged lithium secondary battery were measured, and the battery was left at 72 ℃ for 55 days. After 55 days passed, the AC resistance and voltage of each charged lithium secondary battery at high temperature were measured again, and the resistance increase rate and the voltage holding rate were analyzed according to the measured resistance and voltage before and after high temperature storage. The results are shown in table 2 below.
C) Analysis of the elution amount of Metal ions after high temperature storage
Since the metal eluted into the electrolyte is reduced on the surface of the active material layer of the anode to induce side reactions, the content of metal ions remaining on the anode surface was measured for the lithium secondary battery subjected to the analysis of the resistivity increase rate and the voltage holding rate after the high temperature storage as described above.
Specifically, each of the lithium secondary batteries of examples and comparative examples, in which the resistivity increase rate and the voltage holding rate were analyzed, was disassembled to separate the negative electrode, and inductively coupled plasma analysis (ICP) was performed on the powder of the active material layer obtained by scraping the surface of the active material layer included in the negative electrode to measure the contents of nickel (Ni), cobalt (Co), and manganese (Mn) ions remaining on the surface of the negative electrode in ppm. The results are shown in table 2 below.
TABLE 2
As shown in table 2, it can be seen that the lithium secondary battery of the present application has low internal resistance of the battery and low resistance increase rate, high voltage holding rate and low metal dissolution rate even after storage at high temperature.
From these results, it can be seen that the lithium secondary battery of the present application includes Li containing excessive lithium in the positive electrode 6 CoO 4 Etc. as an irreversible additive while including the electrolyte additive of formula 1 having a specific molecular weight in the electrolyte, thereby achieving low battery resistance and effectively preventing metal ions from being eluted from the irreversible additive, and thus having excellent battery performance and life.
As described above, although the present application has been described with reference to the exemplary embodiments thereof, it will be understood by those skilled in the art or the ordinary skilled in the art that various modifications and changes may be made thereto without departing from the spirit and technical scope of the present application as described in the appended claims.
Therefore, the technical scope of the present application is not limited to what is described in the detailed description of the specification, but should be defined by the claims.
Claims (15)
1. A lithium secondary battery, the lithium secondary battery comprising:
an electrode assembly including a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode; and
an electrolyte composition comprising a lithium salt, an electrolyte additive having a unit represented by the following formula 1, and a nonaqueous solvent,
wherein the positive electrode comprises a positive electrode active layer containing an irreversible additive represented by the following formula 2, and
the electrolyte additive has a weight average molecular weight of less than 40,000g/mol:
[ 1]
[ 2]
Li a M b M’ 1-b O c
Wherein:
R 1 、R 2 and R is 3 Each hydrogen or an alkyl group having 1 to 6 carbon atoms,
R 4 and R is 5 Each an alkylene group having 1 to 6 carbon atoms,
p, q and r are each integers from 0 to 5,
m and n are each integers of 10 to 200,
m comprises one or more of Co, ni, mn and Fe,
m 'comprises one or more of Co, ni, mn, fe, al, mg, zn and Ti, provided that M and M' are different from each other, and
a. the ranges of b and c are respectively 1.50-6.5,0-1 and 1.5-4.5.
2. The lithium secondary battery according to claim 1, wherein, in the unit represented by formula 1,
R 1 、R 2 and R is 3 Each of which is hydrogen or methyl,
R 4 and R is 5 Each ethylene or propylene, and
p, q and r are each integers from 0 to 2.
3. The lithium secondary battery according to claim 1, wherein the m: n ratio of the unit represented by formula 1 is 1:1.01 to 10.
4. The lithium secondary battery according to claim 1, wherein the electrolyte additive has a weight average molecular weight of 5,000 to 30,000g/mol.
5. The lithium secondary battery according to claim 1, wherein the electrolyte additive has a bimodal molecular weight distribution.
6. The lithium secondary battery according to claim 1, wherein the electrolyte additive has a polydispersity index (PDI) of 1.2 to 5.0.
7. The lithium secondary battery according to claim 1, wherein the content of the electrolyte additive is less than 5 wt% based on the total weight of the electrolyte composition.
8. The lithium secondary battery according to claim 1, wherein the electrolyte composition comprises an electrolyte auxiliary additive comprising:
one or more cyclic carbonate compounds selected from the group consisting of Vinylene Carbonate (VC), vinyl Ethylene Carbonate (VEC) and fluoroethylene carbonate (FEC); and
one or more sultone compounds selected from the group consisting of 1, 3-Propane Sultone (PS), 1, 4-butane sultone, ethylene sultone, 1, 3-propylene sultone (PRS), 1, 4-butene sultone and 1-methyl-1, 3-propylene sultone.
9. The lithium secondary battery according to claim 1, wherein the irreversible additive represented by formula 2 comprises Li 6 CoO 4 、Li 6 NiO 4 、Li 2 NiO 2 、Li 6 MnO 4 、Li 2 MnO 3 、Li 5 FeO 4 、Li 6 Co 0.9 Al 0.1 O 4 、Li 6 Co 0.7 Zn 0.3 O 4 、Li 6 Ni 0.9 Al 0.1 O 4 、Li 6 Mn 0.9 Al 0.1 O 4 、Li 5 Fe 0.9 Al 0.1 O 4 、Li 6 Co 0.5 Fe 0.5 O 4 、Li 6 Ni 0.5 Fe 0.5 O 4 、Li 6 Ni 0.9 Al 0.1 O 4 One or more of the following.
10. The lithium secondary battery according to claim 1, wherein the irreversible additive is contained in an amount of 0.01 to 5 wt% based on the total weight of the positive electrode active layer.
11. The lithium secondary battery according to claim 1, wherein the positive electrode active layer contains one or more of lithium metal oxides represented by the following formula 3 as a positive electrode active material:
[ 3]
Li x [Ni y Co z Mn w M 1 v ]O 2
Wherein:
M 1 comprises one or more elements selected from the group consisting of W, cu, fe, V, cr, ti, zr, zn, al, in, ta, Y, la, sr, ga, sc, gd, sm, ca, ce, nb, mg, B and Mo, and
x, y, z, w and v are each in the range of 1.0.ltoreq.x.ltoreq. 1.30,0.ltoreq.y <1, 0.ltoreq.z.ltoreq.1, 0.ltoreq.w.ltoreq.1, 0.ltoreq.v.ltoreq.0.1, provided that y+z+w+v=1.
12. The lithium secondary battery according to claim 1, wherein the anode includes an anode active layer containing an anode active material, and
the negative electrode active material includes one or more carbon materials selected from the group consisting of natural graphite, artificial graphite, expanded graphite, non-graphitized carbon, carbon black, acetylene black, and ketjen black.
13. The lithium secondary battery according to claim 12, wherein the anode active material further comprises one or more silicon materials selected from the group consisting of: silicon (Si), silicon carbide (SiC) and silicon oxide SiO q Wherein q is more than or equal to 0.8 and less than or equal to 2.5.
14. The lithium secondary battery according to claim 13, wherein the silicon material is contained in an amount of 1 to 20 wt% based on the total weight of the anode active material.
15. A lithium secondary battery module, comprising:
the lithium secondary battery of claim 1; and
and a module case in which the lithium secondary battery is mounted.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2022-0034571 | 2022-03-21 | ||
| KR1020230013790A KR20230137231A (en) | 2022-03-21 | 2023-02-01 | Secondary battery inhibited with exsoltion of transition metal |
| KR10-2023-0013790 | 2023-02-01 | ||
| PCT/KR2023/001686 WO2023182648A1 (en) | 2022-03-21 | 2023-02-07 | Lithium secondary battery with inhibited metal dissolution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117136453A true CN117136453A (en) | 2023-11-28 |
Family
ID=88855006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202380011147.8A Pending CN117136453A (en) | 2022-03-21 | 2023-02-07 | Lithium secondary battery with transition metal elution suppressed |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117136453A (en) |
-
2023
- 2023-02-07 CN CN202380011147.8A patent/CN117136453A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2007273445A (en) | Polymer gel electrolyte and polymer secondary battery using the same | |
| CN110462909B (en) | Lithium ion secondary battery | |
| JP7378601B2 (en) | Non-aqueous electrolyte for lithium secondary batteries and lithium secondary batteries containing the same | |
| KR102318380B1 (en) | Electrolyte and lithium secondary battery comprising the same | |
| CN111384439A (en) | Non-aqueous electrolyte and lithium ion battery | |
| CN117136453A (en) | Lithium secondary battery with transition metal elution suppressed | |
| JP2022528246A (en) | Non-aqueous electrolyte solution additive for lithium secondary batteries, non-aqueous electrolyte solution for lithium secondary batteries and lithium secondary batteries containing this | |
| EP3879616A1 (en) | Electrolyte for lithium secondary battery and lithium secondary battery comprising same | |
| CN117136452A (en) | Lithium secondary battery with transition metal elution suppressed | |
| EP4307429A1 (en) | Lithium secondary battery with inhibited metal dissolution | |
| KR20230137231A (en) | Secondary battery inhibited with exsoltion of transition metal | |
| JP7460260B2 (en) | Non-aqueous electrolyte for lithium secondary batteries and lithium secondary batteries containing the same | |
| CN116964812B (en) | Nonaqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising same | |
| EP3940851B1 (en) | Electrolyte for lithium secondary battery and lithium secondary battery including the same | |
| CN110661028B (en) | Lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| EP4307430A1 (en) | Lithium secondary battery having suppressed metal elution | |
| CN116636042A (en) | Lithium secondary battery with improved safety | |
| CN117136444A (en) | Lithium secondary battery | |
| CN117157796A (en) | Nonaqueous electrolyte composition and lithium secondary battery comprising same | |
| KR20230137230A (en) | Secondary battery inhibited with exsoltion of transition metal | |
| CA3211234A1 (en) | Lithium secondary battery with enhanced safety | |
| US20230155177A1 (en) | Lithium Secondary Battery with Improved Safety | |
| CN117203817A (en) | Novel additive for nonaqueous electrolyte and lithium secondary battery including the same | |
| EP4290639A1 (en) | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising same | |
| US20240136579A1 (en) | Non-aqueous electrolyte solution composition and lithium secondary battery comprising same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |