CN117594877A - Electrolyte and lithium ion battery containing same - Google Patents
Electrolyte and lithium ion battery containing same Download PDFInfo
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- CN117594877A CN117594877A CN202311571647.5A CN202311571647A CN117594877A CN 117594877 A CN117594877 A CN 117594877A CN 202311571647 A CN202311571647 A CN 202311571647A CN 117594877 A CN117594877 A CN 117594877A
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- China
- Prior art keywords
- lithium
- electrolyte
- ion battery
- additive
- lithium ion
- Prior art date
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 44
- 239000003792 electrolyte Substances 0.000 title claims abstract description 39
- 239000000654 additive Substances 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- -1 fluorosulfonyl fragments Chemical group 0.000 claims abstract description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 6
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical group [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 229910013716 LiNi Inorganic materials 0.000 claims description 4
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- CHHOPPGAFVFXFS-UHFFFAOYSA-M [Li+].[O-]S(F)(=O)=O Chemical compound [Li+].[O-]S(F)(=O)=O CHHOPPGAFVFXFS-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- OWNSEPXOQWKTKG-UHFFFAOYSA-M lithium;methanesulfonate Chemical compound [Li+].CS([O-])(=O)=O OWNSEPXOQWKTKG-UHFFFAOYSA-M 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- MVGWWCXDTHXKTR-UHFFFAOYSA-J tetralithium;phosphonato phosphate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-]P([O-])(=O)OP([O-])([O-])=O MVGWWCXDTHXKTR-UHFFFAOYSA-J 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims 2
- 238000003860 storage Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 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
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 150000005678 chain carbonates Chemical class 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- PPMCFKAXXHZLMX-UHFFFAOYSA-N 1,3-dioxocan-2-one Chemical compound O=C1OCCCCCO1 PPMCFKAXXHZLMX-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- HQSLKNLISLWZQH-UHFFFAOYSA-N 1-(2-propoxyethoxy)propane Chemical compound CCCOCCOCCC HQSLKNLISLWZQH-UHFFFAOYSA-N 0.000 description 1
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-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
- OSSBKXMASZTOSG-UHFFFAOYSA-N 2-(trifluoromethyl)oxolane Chemical compound FC(F)(F)C1CCCO1 OSSBKXMASZTOSG-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013872 LiPF 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
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- VIEVWNYBKMKQIH-UHFFFAOYSA-N [Co]=O.[Mn].[Li] Chemical compound [Co]=O.[Mn].[Li] VIEVWNYBKMKQIH-UHFFFAOYSA-N 0.000 description 1
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 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
- 239000011889 copper foil Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CHCLGECDSSWNCP-UHFFFAOYSA-N methoxymethoxyethane Chemical compound CCOCOC CHCLGECDSSWNCP-UHFFFAOYSA-N 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses an electrolyte and a lithium ion battery containing the same, wherein the electrolyte comprises lithium salt, an organic solvent and an additive, and the structural formula of the additive is shown as a structural formula I:
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an electrolyte and a lithium ion battery containing the same.
Background
The lithium ion battery has the advantages of high working voltage, high energy density, environmental friendliness and the like, is widely applied to the fields of 3C consumer batteries, power batteries and energy storage batteries, and has wide application prospects in the fields of aerospace, national defense and military industry and the like.
Lithium ion batteries operate primarily by virtue of lithium ions moving between a positive electrode and a negative electrode. The high nickel ternary material is used as the positive electrode material of the lithium ion battery, has the advantages of high working voltage, low cost, environmental protection, low toxicity and the like, and has energy density which is higher than that of the traditional positive electrode material (such as LiCoO) 2 、Li 2 Mn 2 O 4 、LiFePO 4 Etc.) high. As the nickel content increases and the cobalt content decreases, the energy density of the ternary material gradually increases and the unit cost decreases, but the thermal stability and cycle performance are inferior to those of the low nickel ternary material. Conventional carbonate electrolyte can be oxidized and decomposed on the surface of the positive electrode of the battery under the high voltage of 4.4V, particularly under the high temperature condition, the oxidation and decomposition of the electrolyte can be accelerated, and the deterioration reaction of the positive electrode material is promoted.
Therefore, development of an electrolyte capable of reducing oxidative decomposition of the surface of the positive electrode to protect the positive electrode material, prolonging the service life of the positive electrode material, and further achieving excellent performance of the lithium ion battery is needed.
Disclosure of Invention
In order to solve the defects encountered at present, the invention aims to provide the electrolyte, and the additive in the electrolyte can reduce the surface activity of the positive electrode to inhibit the oxidative decomposition of the electrolyte, reduce the internal resistance of the battery and effectively improve the high-temperature storage performance and the high-temperature cycle performance of the lithium ion battery.
In order to achieve the above purpose, the invention provides an electrolyte, which comprises lithium salt, an organic solvent and an additive, wherein the structural formula of the additive is shown as a structural formula I:
wherein, in the structural formula I, R is a hydrocarbon group.
The electrolyte comprises lithium salt, an organic solvent and an additive, wherein the additive is shown in a structural formula I, contains 2 fluorosulfonyl fragments and contains a lithium ion source, so that the structural stability of an interface film can be further improved, the mobility of lithium ions is improved, and the performance of a lithium ion battery is improved.
It should be noted that the hydrocarbon group of the present invention may be either a chain hydrocarbon group such as a straight chain or a cyclic hydrocarbon group. Further, R is a C1-C12 hydrocarbon group, a heteroatom-containing C1-C12 hydrocarbon group, a C2-C6 cyclic hydrocarbon group or a heteroatom-containing C2-C6 cyclic hydrocarbon group. The hetero atom may be, but is not limited to, oxygen, nitrogen, sulfur, etc., and the hetero atom-containing cyclic hydrocarbon group means that the cyclic hydrocarbon group contains other types of atoms such as oxygen, nitrogen, sulfur, etc., in addition to carbon and hydrogen, and these hetero atoms may be directly bonded to carbon atoms or indirectly bonded to carbon atoms. Wherein C1-C12 represents a carbon number of 1-12, and C2-C6 represents a carbon number of 2-6.
In a preferred embodiment, the additive is selected from at least one of compounds 1 to 3,
in a preferred embodiment, the additive is used in an amount of about 0.05% -10.0% by weight of the total electrolyte, about 0.05% -5.0%, about 0.1% -8%, about 0.1% -5% by weight, and by way of example, the additive of the present invention is used in an amount of about 0.05%, about 0.1%, about 0.2%, about 0.3%, about 0.5%, about 0.8%, about 1%, about 1.5%, about 2.2%, about 2.5%, about 3.2%, about 3.5%, about 4.2%, about 3.5%, about 3.8%, about 4.4.5%, about 4.8%, about 5%, about 6% by weight of the total electrolyte, but is not limited to the recited values, and other non-recited values in this range of values are equally applicable.
In a preferred embodiment, the lithium salts of the present invention include lithium carbonate, lithium fluoride, lithium hydroxide, lithium iron phosphate. As an example, the lithium salt of the present invention includes, but is not limited to, lithium tetrafluoroborate (LiBF 4 ) Lithium fluorosulfonate (LiSO) 2 F) Lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium difluorophosphate (LiPO) 2 F 2 ) Lithium dioxalate borate (C) 4 BLiO 8 ) Lithium difluorooxalato borate (C) 2 BF 2 LiO 4 ) Lithium hexafluorophosphate (LiPF) 6 ) Lithium methylsulfonate (LiCH) 3 SO 3 ) Lithium perchlorate (LiClO) 4 ) Lithium difluorobis (oxalato) phosphate (LiDFBP), lithium diphosphate (LiPO) 2 F 2 ) Lithium triflate (LiCF) 3 SO 3 ) Lithium bis (fluorosulfonyl) imide (LiFSI), and the like.
In a preferred embodiment, the concentration of the lithium salt is 0.5M-1.5M, specifically but not limited to 0.5M, 0.8M, 1.0M, 1.1M, 1.2M, 1.3M, 1.4M, 1.5M. The mass of the lithium salt accounts for 5-20% of the total mass of the electrolyte, and is about 8-18% of the total mass of the electrolyte. For example, the mass of lithium salt is 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18% of the total mass of the electrolyte, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
In a preferred embodiment, the organic solvent is at least one of carbonate, carboxylate and ether compounds. Preferably a carbonate electrolyte, wherein the carbonate may be a cyclic carbonate or a chain carbonate, and examples of cyclic carbonates include, but are not limited to, ethylene Carbonate (EC), propylene carbonate, butylene Carbonate (BC), pentylene carbonate, vinylene Carbonate (VC), or derivatives thereof; chain carbonates include, but are not limited to, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), propylene Carbonate (PC).
In a preferred embodiment, the carboxylic acid ester is selected from cyclic carboxylic acid esters or chain carboxylic acid esters, as an example, the cyclic carboxylic acid esters are selected from at least one of gamma-butyrolactone, gamma-valerolactone, delta-valerolactone; the chain carboxylic acid ester is at least one selected from Methyl Acetate (MA), ethyl Acetate (EA), propyl acetate (EP), butyl acetate, propyl Propionate (PP) and butyl propionate.
In a preferred embodiment, the ether compound may be a cyclic ether or a chain ether, and the cyclic ether is exemplified by 1, 3-Dioxolane (DOL), 2-methyltetrahydrofuran (2-CH) 3 THF), 1, 4-Dioxane (DX), crown ether, tetrahydrofuran (THF), 2-trifluoromethyl tetrahydrofuran (2-CF) 3 -THF) at least one of; the chain ether is at least one selected from dimethoxymethane, ethylene glycol di-n-propyl ether, ethoxymethoxymethane, ethylene glycol di-n-butyl ether, diethoxymethane and diethylene glycol dimethyl ether.
In a preferred embodiment, the electrolyte of the present invention may further include an auxiliary agent, wherein the auxiliary agent is 0.01% -10% by mass of the total electrolyte, about 0.01% -8%, 0.01% -5%, 0.1% -10% by mass, and the auxiliary agent may be at least one selected from fluoroethylene carbonate (FEC), 1, 3-propenesulfonic acid lactone, ethylene sulfate (DTD), vinylene Carbonate (VC), ethylene Sulfite (ES), vinylene Carbonate (VC), and the cycle performance may be further improved by adding the auxiliary agent, preferably, the auxiliary agent is a mixture of fluoroethylene carbonate (FEC) and Vinylene Carbonate (VC), and the performance of the lithium ion battery may be more effectively improved.
Correspondingly, the invention also provides a lithium ion battery which comprises a positive electrode, a negative electrode and the electrolyte, and by using the electrolyte, the high-temperature storage performance and the high-temperature cycle performance of the lithium ion battery are effectively improved, and good low-temperature discharge performance can be obtained.
In a preferred embodiment, the positive electrode material is selected from the group consisting of lithium nickel cobalt manganese oxide, lithium manganese cobalt oxide, lithium cobalt oxide(e.g. LiCoO) 2 ) Lithium nickel cobalt oxide, lithium nickel oxide (e.g. LiNiO 2 ) Lithium manganese oxide (e.g. LiMnO 2 、LiMn 2 O 4 ) Lithium nickel manganese oxide. Preferably, the present invention adopts a high nickel ternary material as the positive electrode material of the lithium ion battery, and the positive electrode material is selected from nickel cobalt manganese oxide materials, specifically, the nickel cobalt manganese oxide material is high nickel cobalt manganese oxide LiNi x Co y Mn (1-x-y) M z O 2 Wherein, x is more than or equal to 0.6<0.9，x+y≤1，0≤z<0.08, M is any one of Al, mg, zr, ti.
In a preferred embodiment, the nickel cobalt manganese oxide material is LiNi x Co y Mn (1-x-y) M z O 2 X=0.6, y=0.2, m is Zr, and z=0.03.
In a preferred embodiment, the negative electrode material comprises a carbon-based negative electrode, a silicon-based negative electrode, or a silicon-carbon negative electrode material, preferably a silicon-carbon negative electrode material (10% silicon).
Detailed Description
In order to further illustrate the objects, technical solutions and advantageous effects of the present invention, the present invention will be further described with reference to specific examples. The specific conditions not specified in examples and comparative examples may be carried out under the conventional conditions or the conditions recommended by the manufacturer, and the reagents or instruments used are conventional products available commercially without specifying the manufacturer.
Example 1
1.1 preparation of electrolyte:
in a glove box (O) 2 ＜1ppm，H 2 O < 1 ppm), uniformly mixing Ethyl Propionate (EP), dimethyl carbonate (DMC) and diethyl carbonate (DEC) according to a mass ratio of 1:1:1, taking the obtained mixed solvent as an organic solvent, and adding an additive and an auxiliary agent to obtain a mixed solution. Sealing and packaging the mixed solution, freezing for 2 hr in a quick freezing chamber (-4deg.C), taking out, and placing in a glove box (O) filled with nitrogen 2 ＜1ppm，H 2 O < 1 ppm), slowly adding lithium salt into the mixed solution, mixingAnd (5) preparing the electrolyte after uniform.
1.2 preparation of positive plate:
ternary material LiNi 0.6 Co 0.2 Mn 0.2 Zr 0.03 O 2 Uniformly mixing a conductive agent SuperP, an adhesive PVDF and a Carbon Nano Tube (CNT) according to a mass ratio of 96.5:1.5:1:1 to prepare lithium ion battery anode slurry with certain viscosity, and coating the lithium ion battery anode slurry on an aluminum foil for a current collector, wherein the coating amount is 324g/m 2 Drying at 85 ℃ and then cold pressing; then trimming, cutting pieces, splitting, drying at 85 ℃ for 4 hours under vacuum condition after splitting, and welding the tab to prepare the lithium ion battery positive plate meeting the requirements.
1.3 preparation of a negative plate:
mixing artificial graphite and silicon according to a mass ratio of 90:10, preparing slurry with a conductive agent SuperP, a thickener CMC and an adhesive SBR (styrene butadiene rubber emulsion) according to a mass ratio of 95:1.5:1.0:2.5, uniformly mixing, coating the mixed slurry on two sides of a copper foil, drying, and rolling to obtain a negative plate, thus preparing the lithium ion battery negative plate meeting the requirements.
1.4 preparation of lithium ion batteries:
the positive plate, the negative plate and the diaphragm prepared according to the process are manufactured into a lithium ion battery with the thickness of 4.7mm, the width of 55mm and the length of 60mm through a lamination process, and the lithium ion battery is baked for 10 hours at the temperature of 75 ℃ in vacuum and injected with the electrolyte. After 24h of standing, charging to 4.45V with a constant current of 0.lC (180 mA), and then charging to a current falling to 0.05C (90 mA) with a constant voltage of 4.45V; then discharging to 3.0V at 0.2C (180 mA), repeating the charge and discharge for 2 times, and finally charging the battery to 3.8V at 0.2C (180 mA) to finish the manufacturing of the lithium ion battery.
Each of the examples and comparative examples was carried out in the manner described above, and the composition and content of the specific electrolytic solution are shown in Table 1.
Table 1 composition and content of electrolytes of examples and comparative examples
The lithium ion batteries prepared in each of the examples and comparative examples were subjected to a high-temperature storage performance test, a high-temperature cycle performance test, a normal-temperature cycle performance test, and a low-temperature performance test with reference to the following conditions, and the results are shown in table 2.
Normal temperature cycle performance test：
The lithium ion battery is charged and discharged at the normal temperature (25 ℃) at 1.0C/1.0C (the discharge capacity of the battery is C) 0 ) The upper limit voltage was 4.4V, and then charging and discharging at 1.0C/1.0C was performed for 500 weeks under normal temperature conditions (the discharge capacity of the battery was C) 1 ) The capacity retention rate was calculated.
Capacity retention= (C 1 /C 0 )*100％
High temperature cycle test：
The lithium ion battery is charged and discharged at 1.0C/1.0C once under the condition of overhigh temperature (45 ℃) (the discharge capacity of the battery is C) 0 ) The upper limit voltage was 4.4V, and then charging and discharging at 1.0C/1.0C was performed for 500 weeks under normal temperature conditions (the discharge capacity of the battery was C) 1 ) The capacity retention rate was calculated.
Capacity retention= (C 1 /C 0 )*100％
High temperature storage performance test：
Lithium ion batteries were charged and discharged at 0.3C/0.3C once (the discharge capacity of the battery was recorded as C) at normal temperature (25 ℃ C.) 0 ) Placing the battery in a 60 ℃ oven for 15d, and taking out the battery, wherein the upper limit voltage is 4.4V; the cell was placed in a 25 ℃ environment and subjected to 0.3C discharge (discharge capacity recorded as C 1 ) The method comprises the steps of carrying out a first treatment on the surface of the The lithium ion battery was then charged and discharged once at 0.3C/0.3C (the discharge capacity of the battery was recorded as C) 2 ) The capacity retention rate and the capacity recovery rate are calculated.
Capacity retention= (C 1 /C 0 )*100％
Capacity recovery rate= (C 2 /C 0 )*100％
Low temperature discharge performance test：
The lithium ion battery is charged and discharged once at 0.3C/0.3 under the condition of normal temperature (25 ℃) (the discharge capacity is C) 0 ) The upper limit voltage was 4.4V, then the battery was charged to 4.4V under a constant current and constant voltage of 0.5C, the battery was placed in an oven at-20 ℃ for 4 hours, 0.3C discharge (discharge capacity recorded as C) was performed on the battery at-20 ℃ with a cutoff voltage of 3.0V, and then the low-temperature discharge rate was calculated.
Low temperature discharge rate= (C1/C0) ×100%
Table 2 lithium ion battery performance test results
As can be seen from table 2, compared with each comparative example, the electrolyte of each example significantly improves the low-temperature discharge performance, the normal-temperature cycle performance, the high-temperature cycle performance, and the high-temperature storage performance of the lithium ion battery due to the addition of the compound shown in the structural formula i, which is likely to be that more fluorosulfonyl fragments easily participate in the formation of the CEI and the SEI, and the lithium ion source can improve the structural stability of the interface film, and improve the lithium ion mobility, so that the performance of the lithium ion battery is improved.
It can also be seen from Table 2 that the addition of the additives of the present invention, based on the additives of the present invention, provides better cycle performance and high temperature storage performance; when the auxiliary agents except VC are added, the low-temperature discharge performance of the composite material is obviously enhanced; when the VC/FEC mixed auxiliary agent is used in the electrolyte, the cycle performance and the high-temperature storage performance of the lithium ion battery are better.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the present invention can be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The electrolyte comprises lithium salt, an organic solvent and an additive, and is characterized in that the structural formula of the additive is shown as a structural formula I:
wherein, in the structural formula I, R is a hydrocarbon group.
2. The electrolyte of claim 1 wherein R is a C1-C12 hydrocarbyl group, a heteroatom-containing C1-C12 hydrocarbyl group, a C2-C6 cycloalkyl group, or a heteroatom-containing C2-C6 cycloalkyl group.
3. The electrolyte of claim 1, wherein the additive is at least one selected from the group consisting of compounds 1 to 3,
4. the electrolyte of claim 1 wherein the additive is present in an amount of from 0.05% to 10.0% of the total mass of the electrolyte.
5. The electrolyte of claim 1 wherein the lithium salt is selected from at least one of lithium tetrafluoroborate, lithium fluorosulfonate, lithium bistrifluoromethylsulfonyl imide, lithium difluorophosphate, lithium dioxaborate, lithium difluorooxalato borate, lithium hexafluorophosphate, lithium methylsulfonate, lithium perchlorate, lithium difluorobisoxalato phosphate, lithium diphosphate, lithium trifluoromethylsulfonate, lithium bisfluorosulfonyl imide.
6. The electrolyte of claim 1, wherein the organic solvent is selected from at least one of carbonate, carboxylate, and ether compounds.
7. The electrolyte of claim 1, further comprising an auxiliary agent selected from at least one of fluoroethylene carbonate, 1, 3-propenesulfonic acid lactone, ethylene sulfate, vinylene carbonate, ethylene sulfite, vinylene carbonate.
8. A lithium ion battery, characterized in that the electrolyte according to any one of claims 1-7 is used.
9. The lithium-ion battery of claim 8, comprising a positive electrode and a negative electrode, wherein the positive electrode is selected from nickel cobalt manganese oxide materials.
10. The lithium-ion battery of claim 9, wherein the nickel cobalt manganese oxide material is LiNi x Co y Mn (1-x-y) M z O 2 Wherein, x is more than or equal to 0.6<0.9，x+y≤1，0≤z<0.08, M is any one of Al, mg, zr, ti.
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