CN114388887A - Electrolyte and lithium ion battery - Google Patents
Electrolyte and lithium ion battery Download PDFInfo
- Publication number
- CN114388887A CN114388887A CN202011139437.5A CN202011139437A CN114388887A CN 114388887 A CN114388887 A CN 114388887A CN 202011139437 A CN202011139437 A CN 202011139437A CN 114388887 A CN114388887 A CN 114388887A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- lithium
- additive
- carbonate
- equal
- 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
- 239000003792 electrolyte Substances 0.000 title claims abstract description 104
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 74
- 239000000654 additive Substances 0.000 claims abstract description 66
- 230000000996 additive effect Effects 0.000 claims abstract description 64
- -1 cyclic lactone compound Chemical class 0.000 claims abstract description 58
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 14
- 150000002367 halogens Chemical class 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 8
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical group FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 22
- 229910052744 lithium Inorganic materials 0.000 claims description 22
- 238000006467 substitution reaction Methods 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 150000005678 chain carbonates Chemical class 0.000 claims description 8
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 8
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 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
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 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 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 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 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 24
- 238000002161 passivation Methods 0.000 abstract description 11
- 238000007086 side reaction Methods 0.000 abstract description 7
- 239000007789 gas Substances 0.000 abstract description 6
- 150000002431 hydrogen Chemical class 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000005954 phosphonylation reaction Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 20
- 229940125904 compound 1 Drugs 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000010405 anode material Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000010523 cascade reaction Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 206010016766 flatulence Diseases 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- ONJSLAKTVIZUQS-UHFFFAOYSA-K manganese(3+);triacetate;dihydrate Chemical compound O.O.[Mn+3].CC([O-])=O.CC([O-])=O.CC([O-])=O ONJSLAKTVIZUQS-UHFFFAOYSA-K 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000005499 phosphonyl group Chemical group 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ISCHCBAXHSLKOZ-XBXARRHUSA-N (e)-5-phenylpent-4-enoic acid Chemical compound OC(=O)CC\C=C\C1=CC=CC=C1 ISCHCBAXHSLKOZ-XBXARRHUSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000006024 2-pentenyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004373 HOAc Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910012701 LiCo1-xMxO2 Inorganic materials 0.000 description 1
- 229910012938 LiCo1−xMxO2 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910011902 LiFe1-xMxPO4 Inorganic materials 0.000 description 1
- 229910010595 LiFe1−xMxPO4 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910014382 LiMn2-yMyO4 Inorganic materials 0.000 description 1
- 229910014556 LiMn2−yMyO4 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910016289 MxO2 Inorganic materials 0.000 description 1
- 229910000979 O alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052796 boron 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
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[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
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011887 silicon containing negative electrode material Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910021483 silicon-carbon alloy Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
-
- 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
- H01M10/05—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
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Abstract
The application discloses electrolyte and lithium ion battery, the electrolyte includes organic solvent, lithium salt and first additive, first additive is selected from at least one in the phosphonylation cyclic lactone compound that has the structure shown in formula I:
wherein n is more than or equal to 1 and less than or equal to 3, x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1; wherein R is1、R2、R3And R4Each independently selected from hydrogen, halogen, substituted or unsubstituted C1～C5Alkyl, substituted or unsubstituted C2～C5Unsaturated hydrocarbon group, substituted or unsubstituted C6～C10Aryl, and substituted or unsubstituted C7～C10An alkaryl group. At the present applicationThe disclosed electrolyte can form a passivation film with low impedance and high polymerization degree on the surface of a positive pole piece by introducing the phosphonylated cyclic lactone compound, can remarkably reduce side reactions of the electrolyte and a positive pole material interface under high voltage, and can inhibit gas generation of a battery while obviously improving the high-voltage cycle performance and storage performance of the lithium ion battery.
Description
Technical Field
The present application relates generally to the field of battery technology, and more particularly to an electrolyte and a lithium ion battery.
Background
The lithium ion battery has the advantages of high specific energy, long cycle life, no memory effect and the like, and is generally applied to consumer electronics, new energy automobiles and large-scale energy storage equipment. At present, electronic products such as smart phones and new energy automobiles have higher and higher requirements on energy density of lithium ion batteries, and the energy density of the batteries can be improved by improving the energy density of the existing materials, such as the cut-off voltage of the anode material.
The problem of increasing the cut-off voltage of the anode material is also faced: for example, the increase of voltage aggravates the interface side reaction of the electrolyte and the anode material, and the electrolyte is easily oxidized to cause the battery to swell; in addition, the transition metal ions are eluted from the positive electrode material and migrate to the negative electrode through the electrolyte, and the SEI on the surface of the negative electrode is broken, resulting in rapid degradation of the battery capacity.
Therefore, on the premise of improving the cut-off voltage of the anode material, how to reduce the side reaction of the electrolyte and the interface of the anode material and ensure the stability of the anode/electrolyte interface is of great significance for improving the high-voltage stability and the cycle performance of the battery and preventing the battery from flatulence.
Disclosure of Invention
In view of the above-mentioned defects or shortcomings in the prior art, it is desirable to provide an electrolyte and a lithium ion battery, so as to reduce side reactions at the interface between the electrolyte and the positive electrode material, achieve comprehensive improvement of high-voltage cycle performance and storage performance of the battery, and effectively alleviate the battery flatulence by forming a high-voltage stable and cycle stable passivation film on the positive electrode of the lithium ion battery.
As a first aspect of the present application, the present application provides an electrolyte.
Preferably, the electrolyte comprises an organic solvent, a lithium salt and a first additive, wherein the first additive is at least one selected from phosphonylated cyclic lactone compounds with the structure shown in formula I:
wherein n is more than or equal to 1 and less than or equal to 3, x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1;
wherein R is1、R2、R3And R4Each independentlySelected from hydrogen, halogen, substituted or unsubstituted C1～C5Alkyl, substituted or unsubstituted C2～C5Unsaturated hydrocarbon group, substituted or unsubstituted C6～C10Aryl, and substituted or unsubstituted C7～C10An alkaryl group.
Preferably, the substitution includes partial substitution and complete substitution, and the substituted substituent is selected from at least one of halogen, cyano, carboxyl and sulfonic acid.
Preferably, the first additive is selected from at least one of the following compounds:
preferably, the mass percentage of the first additive in the electrolyte is 0.1-10%, preferably 1-5%.
Preferably, the additive also comprises a second additive, wherein the second additive is fluoroethylene carbonate; or the like, or, alternatively,
the second additive is one or a combination of more of vinyl sulfate, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorobis-oxalato phosphate and lithium tetrafluorooxalato phosphate and fluoroethylene carbonate.
Preferably, the mass percentage of the second additive in the electrolyte is 1-30%, and preferably 2-15%.
Preferably, the organic solvent includes a cyclic carbonate and/or a chain carbonate;
the cyclic carbonate is selected from at least one of ethylene carbonate, propylene carbonate, butylene carbonate and gamma-butyrolactone;
the chain carbonate is at least one selected from dimethyl carbonate, diethyl carbonate, methylethyl carbonate, methylpropyl carbonate, methyl formate, ethyl acetate, methyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate and butyl propionate.
Preferably, the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium difluorooxalato borate, lithium bis (trifluoromethylsulfonyl) imide, lithium difluorosulfonylimide, lithium trifluoromethylsulfonate and lithium dioxaoxalato borate.
As a second aspect of the present application, there is provided a lithium ion battery.
Preferably, the lithium ion battery comprises a positive plate, a negative plate, a diaphragm arranged between the positive plate and the negative plate, and the electrolyte according to the first aspect of the present application.
Preferably, the negative electrode sheet includes a silicon-containing negative electrode sheet.
The beneficial effect of this application:
the electrolyte disclosed by the application can form a passivation film with low impedance and high polymerization degree on the surface of a positive pole piece by introducing the phosphonyl cyclic lactone compound, can remarkably reduce the side reaction of the interface of the electrolyte and a positive pole material under high voltage, and can inhibit the gas generation of a battery while obviously improving the high-voltage cycle performance and the storage performance of the lithium ion battery.
Detailed Description
The present application will be described in further detail with reference to examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail with reference to examples.
It is noted that the endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and that such ranges or values are understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the description of the present application, the terms "first", "second", and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated.
Unless otherwise specified, all raw materials referred to in the present application are commercially available raw materials.
According to a first aspect of the present application, there is provided an electrolyte comprising an organic solvent, a lithium salt and a first additive selected from at least one phosphonocyclic lactone compound having a structure represented by formula i:
wherein n is more than or equal to 1 and less than or equal to 3, x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1; that is, n is 1,2, 3; x is 0, 1; y is 0, 1;
wherein R is1、R2、R3And R4Each independently selected from hydrogen, halogen, substituted or unsubstituted C1～C5Alkyl, substituted or unsubstituted C2～C5Unsaturated hydrocarbon group, substituted or unsubstituted C6～C10Aryl, and substituted or unsubstituted C7～C10An alkaryl group.
The phosphonylated cyclic lactone compound shown in formula I can form films on a negative electrode and a positive electrode at the same time, and an exemplary film forming mechanism is as follows: the cyclic lactone has a cyclic lactone structure and a phosphono structure, wherein the cyclic lactone can undergo a ring-opening polymerization reaction in the first charging (formation); specifically, when the electrolyte is formed, the phosphonylated cyclic lactone compound is dissolved in an organic solvent comprising cyclic carbonate and/or chain carbonate, wherein the carbonyl group of the cyclic lactone can be attacked by the ethoxy group with negative charge, such as ethyl acetate, in the organic solvent, and the oxygen of the cyclic lactone can be attacked by the carbonyl group with positive charge, so that the phosphonylated cyclic lactone compound is subjected to ring-opening polymerization reaction to form a passivation film with high polymerization degree and orderly arrangement, which is covered on the surface of the negative electrode, active sites on the surface of the negative electrode are effectively reduced, and the electrolyte solvent is prevented from being dissolved in the organic solventCarrying out reduction decomposition on the surface of the negative electrode; the phosphorus-oxygen double bond in the phosphonyl structure has lone electron pairs, the phosphorus-oxygen double bond can react on the surface of the anode material to form a passivation film with high polymerization degree, the phosphonyl cyclic lactone compound has lower oxidation potential and can be oxidized and decomposed on the surface of the anode in preference to organic solvents such as carbonic ester and the like to form a complete, compact, good-uniformity and lower-impedance passivation film, and O released by the anode active material can be absorbed2-、O2 2-Plasma reduces the release of active oxygen of the positive active material, thereby reducing the gas production by reducing the irreversible oxidation of the active oxygen on the electrolyte under high voltage and improving the gas expansion phenomenon in the storage process of the battery; the increase of the interface impedance of the positive electrode in the circulating and storing processes can be effectively inhibited, and the circulating life and the storing performance of the battery are improved; through the cyclic lactone structure and the phosphonyl structure, the phosphonylated cyclic lactone compound shown in the formula I can be adapted to a lithium ion battery with a high-voltage positive electrode.
In addition, the phosphonyl cyclic lactone compound shown in the formula I has good thermal stability, and when the compound is used as a battery electrolyte additive, the high-temperature performance of the battery can be improved, and the high-temperature storage performance of the battery can be obviously improved.
Exemplary halogens include, but are not limited to, halogen atoms such as F, Cl, Br, and the like; substituted or unsubstituted C1～C5Alkanyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, and the like; substituted or unsubstituted C2～ C5The unsaturated hydrocarbon group may be an alkene or an alkyne, wherein the number and position of carbon-carbon double bonds or triple bonds are not particularly limited, and examples thereof include, but are not limited to, ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, ethynyl, 1-propynyl, 1-butynyl, 1-pentynyl, and the like; substituted or unsubstituted C6～C10Aryl groups include, but are not limited to, phenyl, tolyl, xylyl, ethylphenyl, n-propylphenyl, n-butylphenyl, and the like; substituted or unsubstituted C7～C10Alkaryl groups include, but are not limited to, benzyl, alpha-methylbenzyl, 1-methyl-1-phenylethyl, 2-phenylpropyl, 2-methyl-2-phenylpropyl, 3-phenylbutyl, 4-phenylbutyl, and the like.
Further, in some preferred embodiments, the substitution includes partial substitution and complete substitution, and the substituted substituent is selected from at least one of halogen, cyano, carboxyl, and sulfonic acid.
That is, the substitution may be mono-substituted or poly-substituted, including complete substitution; when fully substituted, all of the H in the above-described alkyl, unsaturated alkyl, aryl and alkaryl groups are substituted with substituents.
The halogen comprises halogen atoms such as F, Cl and Br, and has stronger electronegativity, so that a C-X bond (X represents the halogen) is stronger than the bond energy of a C-H bond, which is beneficial to improving the thermal stability of the first additive, and the reduction potential of the first additive is improved after the halogen is substituted, so that a better SEI film is at least formed on the cathode of the battery; the cyano (-CN) group can be complexed with metal ions, so that the activity of the metal ions is reduced, the deposition of the metal ions on the surfaces of the positive electrode and the negative electrode is reduced, and the side reaction in the battery is reduced; the sulfonic acid group can help the first additive to form a compact and high-lithium-ion-conductivity protective film on the surface of the anode material, effectively inhibit oxidative decomposition caused by direct contact of the electrolyte and the anode material under high voltage, and improve the high-voltage cycle performance of the battery.
Further, in some preferred embodiments, the first additive may be synthesized using a bifunctional reaction, i.e., an addition cyclization tandem reaction, of a phosphorus radical, which may be provided by a phosphine-hydrogen compound, such as H-phosphite, with a carboxyl-containing olefinic substrate, which employs an internal olefinic acid with a carbon-carbon double bond, according to the following reaction scheme
Shown in the figure:
the reaction process is as follows: the phosphine-hydrogen compound and the olefinic acid were charged into a vessel, and 3.0 equivalents of manganese triacetate dihydrate (Mn (OAc) 3.2H) were added2O) as an initiator of phosphorus free radicals and simultaneously as an oxidant, and reacting in a solvent acetic acid (HOAc) at a constant temperature of 60 ℃ for 8h to obtain the phosphonylated cyclic lactone compound.
Illustratively, n ═ 1,2,3, for the synthesis of five-membered ring frameworks, six-membered ring frameworks and seven-membered ring frameworks;
illustratively, R1Selected from hydrogen, halogen, substituted or unsubstituted Ox-C1～C5Alkyl, substituted or unsubstituted Ox-C2～C5Unsaturated hydrocarbon group, substituted or unsubstituted Ox-C6～C10Aryl, and substituted or unsubstituted Ox-C7～C10Alkaryl, wherein x is 0 or 1; r2Selected from hydrogen, halogen, substituted or unsubstituted Oy-C1～C5Alkyl, substituted or unsubstituted Oy-C2～C5Unsaturated hydrocarbon group, substituted or unsubstituted Oy-C6～C10Aryl, and substituted or unsubstituted Oy-C7～C10Alkaryl, wherein y is 0 or 1; r1And R4Each independently selected from hydrogen, halogen, substituted or unsubstituted C1～C5Alkyl, substituted or unsubstituted C2～C5Unsaturated hydrocarbon group, substituted or unsubstituted C6～C10Aryl, and substituted or unsubstituted C7～C10An alkaryl group; r5May be hydrogen. The substitution includes partial substitution and complete substitution, and the substituted substituent is selected from at least one of halogen, cyano, carboxyl and sulfonic acid group.
Further, in some preferred embodiments, the first additive is selected from at least one of the following compounds, which have a simple structure, a simple preparation process, and excellent yield:
Wherein, the preparation of the compounds 1 to 7 is carried out by referring to the addition cyclization tandem reaction. Illustratively, the synthesis of one preferred embodiment of compound 6 may be:
adding 20mL of 5-phenyl-4-pentenoic acid, 20mL of diisopropyl phosphite and 50mL of acetic acid into a 250mL four-neck flask in sequence, adding 3.0 equivalent of manganese triacetate dihydrate, reacting the mixture in a constant-temperature water bath at 60 ℃ for 8 hours, filtering after the reaction is finished, and concentrating under reduced pressure to obtain a target product with the yield of 82%.
Further, in some preferred embodiments, the mass percentage of the first additive in the electrolyte is 0.1-10%.
When the content of the first additive is too low, the first additive is not enough to react on the surfaces of the anode and cathode materials to form a passive film, and the protective effect on the electrode cannot be exerted; when the content of the first additive is too high, on one hand, the SEI film is excessively modified, so that the stability of the SEI film is deteriorated, and on the other hand, the viscosity of the electrolyte is increased, so that the cycle performance of the lithium ion battery is deteriorated. Preferably, the lower limit of the amount of the first additive may be 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, etc., and any number therebetween, and the upper limit of the amount of the first additive may be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc., and any number therebetween.
Further, in some more preferred embodiments, the mass percentage of the first additive in the electrolyte is 1-5%, and the mass percentage range of the first additive can significantly improve the high-voltage cycle storage performance of the lithium ion battery and can fully exert the protection effect of the electrode.
Further, in some preferred embodiments, the composition further comprises a second additive, wherein the second additive is fluoroethylene carbonate; or the like, or, alternatively,
the second additive is one or a combination of more of vinyl sulfate, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorobis-oxalato phosphate and lithium tetrafluorooxalato phosphate and fluoroethylene carbonate.
When a high-capacity silicon-containing material, such as a silicon-carbon material, is used as a negative electrode to improve the energy density of the lithium ion battery, the stability of an electrode/electrolyte interface is poor due to the extremely large volume expansion of silicon, and a stable passivation film with excellent mechanical properties can be formed on the surface of the negative electrode by adding FEC (forward error correction), so that the instability of the negative electrode/electrolyte interface caused by the volume expansion of the silicon-containing negative electrode material in the cycle period can be relieved to a certain extent, and the cycle life of the battery is prolonged; in order to ensure that a passivation film with enough mechanical strength is formed, the addition amount of FEC is often large, the thermal stability of FEC is poor, and a large amount of gas can be generated at high temperature to influence the storage electrochemical performance of the battery, so that the battery cannot meet the requirement of long-term use in a high-temperature environment;
in this embodiment, by adding the second additive containing FEC, the electrolyte of the present application can be applied to a battery equipped with a high-voltage positive electrode and a silicon-containing negative electrode at the same time, so as to ensure the stability of the positive and negative electrolyte interfaces at the same time; wherein, for example, the F group of the FEC would react with R of the first additive1、R2、R3And/or R4Reactions such as substitution and the like occur, so that a synergistic effect is generated between the FEC and the phosphonyl cyclic lactone compound, and the components and the structure of the SEI film are optimized to form a more stable SEI film; the components and the structure of the SEI film are related to organic solvents and additives in the electrolyte, the main components of the SEI film comprise lithium carbonate, alkyl lithium carbonate, organic polymers and the like, and the main components of the SEI film can be changed through the reaction between FEC and certain components of the SEI film or phosphonyl cyclic lactone compounds and certain components of the SEI film or the reaction between FEC and phosphonyl cyclic lactone compounds, for example, F substituent groups appear on R groups of alkyl lithium carbonate, and the like, so that the structure of the SEI film is changed, for example, the thickness or the density of the SEI film is changed; the SEI film formed has changed composition and structure, and can effectively prevent the swelling and stripping of the negative electrode material, thereby further improving the cycle life of the battery.
Further, in some preferred embodiments, the second additive is 1 to 30% by weight of the electrolyte, the content of the second additive, in particular, the fluoroethylene carbonate, in the electrolyte is too low to exert a synergistic effect with the first additive to optimize the components and the structure of the SEI film, and the content of the second additive, in particular, the fluoroethylene carbonate, in the electrolyte is too high, so that the thermal stability of the electrolyte is deteriorated, and the high-temperature cycle storage performance of the lithium ion battery is deteriorated.
In the method, the phosphonyl cyclic lactone compound and the fluoroethylene carbonate are used together, so that the addition amount of the fluoroethylene carbonate in the electrolyte is greatly reduced, the content of the fluoroethylene carbonate is far lower than that of the conventional electrolyte system, the gas generation of the battery at high temperature can be greatly reduced by reducing the content of the fluoroethylene carbonate, the thermal stability of the battery is improved, and the high-temperature storage performance of the battery is improved; compared with fluoroethylene carbonate, the phosphonyl cyclic lactone compound has better thermal stability, and the high-temperature storage performance of the battery can be obviously improved when the compound is used as the first additive. Preferably, the lower limit of the fluoroethylene carbonate content can be 1%, 1.5%, 2%, 3%, 1.0%, 1.5%, 2.0%, 3.0%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, etc., and any number therebetween, and the upper limit of the fluoroethylene carbonate content can be 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, etc., and any number therebetween.
Further, in some more preferred embodiments, the second additive is 2 to 15% by mass of the electrolyte.
Further, in some preferred embodiments, one skilled in the art may select one or more of vinyl sulfate, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorobis-oxalato phosphate and lithium tetrafluorooxalato phosphate as a second additive to be used in combination with FEC in an appropriate amount to assist in forming a protective film with more excellent performance on the positive and negative electrodes, and further improve the interfacial stability of the electrolyte.
Further, in some preferred embodiments, the organic solvent includes cyclic carbonates and/or chain carbonates;
the cyclic carbonate is selected from at least one of ethylene carbonate, propylene carbonate, butylene carbonate and gamma-butyrolactone;
the chain carbonate is at least one selected from dimethyl carbonate, diethyl carbonate, methylethyl carbonate, methylpropyl carbonate, methyl formate, ethyl acetate, methyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate and butyl propionate.
The cyclic carbonate and the chain carbonate have the advantages of good oxidation reduction resistance, high dielectric constant and low viscosity as solvents used for lithium ion batteries.
Further, in some preferred embodiments, the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium bis (fluorooxalato) borate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium triflate and lithium bis (oxalato) borate.
The lithium salt has the advantages of high conductivity, good thermal stability and good electrochemical stability, and can enhance the conductivity and electrochemical stability of the battery electrolyte when being applied to the preparation process of the battery electrolyte. Preferably, the concentration of the lithium salt in the electrolyte is 0.8-1.5 mol/L.
According to a second aspect of the present application, there is provided a lithium ion battery comprising a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, and further comprising an electrolyte as described in the second aspect of the present application.
In this embodiment, the positive electrode includes a positive electrode current collector and a positive electrode membrane containing a positive electrode active material provided on the positive electrode current collector. Illustratively, the positive electrode current collector may be, but is not limited to, a metal foil or the like (e.g., aluminum foil or the like), and the positive electrode active material is selected from transition metal oxides of lithium selected from LiCoO2、LiMn2O4、 LiMnO2、Li2MnO4、LiFePO4、LiNixCoyMnzO2、Li1+aMn1-xMxO2、LiCo1-xMxO2、LiFe1-xMxPO4、LiMn2-yMyO4、Li2Mn1-xO4Wherein M is at least one selected from Ni, Co, Mn, Al, Cr, Mg, Zr, Mo, V, Ti, B, F and Y, and a is more than or equal to 0<0.2, x is more than or equal to 0, y and z are less than or equal to 1. The metal oxide has the advantages of high energy density, good cycle performance and the like.
The negative electrode comprises a negative electrode current collector and a negative electrode diaphragm containing a negative electrode active material, which is arranged on the negative electrode current collector. Illustratively, the negative electrode current collector may include, but is not limited to, a metal foil or the like (e.g., a copper foil or the like), and the negative electrode active material is selected from at least one of natural graphite, artificial graphite, soft carbon, hard carbon, lithium titanate, silicon-carbon alloy, and silicon-oxygen alloy, which are easily subjected to a lithium ion intercalation and deintercalation reaction, and may be a preferred choice of the negative electrode active material; further preferably, the negative active material includes a material containing SiOxWherein x is 0.9-1.8, 0.9-1.0, 1.0-1.2, 1.2E1.4, 1.4-1.6, or 1.6-1.8.
The membrane may be selected from polyethylene, polypropylene, polyvinylidene fluoride, and multilayer composite membranes of polyethylene, polypropylene, polyvinylidene fluoride.
Wherein, the outer side of the lithium ion battery is also provided with a package, such as an aluminum plastic film, a stainless steel cylinder, a square aluminum shell and the like.
Further, in some preferred embodiments, the negative electrode sheet comprises a silicon-containing negative electrode sheet, for example, the negative electrode sheet comprises a silicon carbon material, so that the energy density of the lithium ion battery is higher.
Example 1
Preparation of positive plate of lithium ion battery
LiCoO as positive electrode active material2Mixing the conductive agent Super-P, CNT and the adhesive PVDF according to the mass ratio of 95.5:2:1:1.5, dispersing the mixture in N-methylpyrrolidone (NMP), and uniformly stirring and mixing to obtain positive electrode slurry; and uniformly coating the anode slurry on an aluminum foil, drying, and performing cold pressing and slitting processes to obtain the anode plate.
Preparation of (II) lithium ion battery negative plate
Mixing a negative active material SiO, a negative active material graphite, a conductive agent Super-P, a binder SBR and a thickening agent CMC according to a mass ratio of 15:80:2:1:2, dispersing in deionized water, and stirring and mixing uniformly to obtain a negative slurry; and uniformly coating the negative electrode slurry on a copper foil, drying, and then performing cold pressing and slitting processes to obtain the negative electrode sheet.
(III) preparation of electrolyte
Mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) according to the mass ratio of EC to DEC to EMC of 3 to 2 to 5 to obtain an organic solvent; adding lithium salt LiPF to the organic solvent6To LiPF6The molar concentration of (A) is 1.1 mol/L; then, compound 1 (first additive) was added to the organic solvent in an amount of 1% by mass based on the total mass of the electrolyte, and fluoroethylene carbonate (second additive) was added in an amount of 3% by mass based on the total mass of the electrolyte.
(IV) preparation of lithium ion batteries
The method comprises the steps of preparing a bare cell from a positive plate, a negative plate and an isolating film (PE film) by a lamination process, filling the cell into an aluminum-plastic film packaging shell, injecting electrolyte, sequentially sealing, standing, hot-cold pressing, forming, grading and the like to obtain the soft package lithium ion battery.
Example 2
A lithium ion battery was fabricated according to the method of example 1, except that in the electrolyte fabrication step, fluoroethylene carbonate was added in an amount of 5% based on the total mass of the electrolyte.
Example 3
A lithium ion battery was fabricated according to the method of example 1, except that in the electrolyte fabrication step, the compound 1 was added in an amount of 2% by mass and the fluoroethylene carbonate was added in an amount of 5% by mass.
Example 4
A lithium ion battery was fabricated according to the method of example 1, except that in the electrolyte fabrication step, the compound 1 was added in an amount of 3% by mass and the fluoroethylene carbonate was added in an amount of 5% by mass.
Example 5
A lithium ion battery was fabricated according to the method of example 1, except that in the electrolyte fabrication step, a mixture of fluoroethylene carbonate and lithium difluorophosphate was used as the second additive, wherein the compound 1 was added in an amount of 2% by mass, the fluoroethylene carbonate was added in an amount of 5% by mass, and the lithium difluorophosphate was added in an amount of 1% by mass.
Example 6
A lithium ion battery was fabricated according to the method of example 1, except that in the electrolyte fabrication step, the compound 1 was added in an amount of 2% by mass and fluoroethylene carbonate was added in an amount of 10% by mass.
Example 7
A lithium ion battery was fabricated according to the method of example 1, except that in the electrolyte fabrication step, compound 4 was used as the first additive, wherein the compound 4 was added in an amount of 2% by mass and fluoroethylene carbonate was added in an amount of 5% by mass.
Example 8
A lithium ion battery was fabricated according to the method of example 1, except that in the step of fabricating the electrolyte, compound 4 was used as the first additive in the step of fabricating the electrolyte, wherein the amount of compound 4 added was 3% and the amount of fluoroethylene carbonate added was 5% of the total mass of the electrolyte.
Example 9
A lithium ion battery was fabricated according to the method of example 1, except that in the electrolyte fabrication step, compound 7 was used as the first additive, wherein the amount of compound 7 added was 2% and the amount of fluoroethylene carbonate added was 5% of the total mass of the electrolyte.
Example 10
A lithium ion battery was fabricated according to the method of example 1, except that in the electrolyte fabrication step, compound 7 was used as the first additive, and a mixture of fluoroethylene carbonate and lithium difluorophosphate was used as the second additive, wherein the compound 7 was added in an amount of 2% by mass, the fluoroethylene carbonate was added in an amount of 5% by mass, and the lithium difluorophosphate was added in an amount of 1% by mass.
Example 11
A lithium ion battery was fabricated according to the method of example 1, except that in the electrolyte fabrication step, the compound 1 was added in an amount of 0.1% by mass and the fluoroethylene carbonate was added in an amount of 5% by mass.
Example 12
A lithium ion battery was fabricated according to the method of example 1, except that in the electrolyte fabrication step, the compound 1 was added in an amount of 0.1% by mass and the fluoroethylene carbonate was added in an amount of 30% by mass.
Example 13
A lithium ion battery was fabricated according to the method of example 1, except that in the electrolyte fabrication step, the compound 1 was added in an amount of 5% by mass and the fluoroethylene carbonate was added in an amount of 15% by mass.
Example 14
A lithium ion battery was fabricated according to the method of example 1, except that in the electrolyte fabrication step, the compound 1 was added in an amount of 10% by mass and the fluoroethylene carbonate was added in an amount of 2% by mass.
Comparative example 1
A lithium ion battery was manufactured according to the method of example 1, except that the second additive was not added in the step of manufacturing the electrolyte, wherein the amount of the compound 1 added was 2% of the total mass of the electrolyte.
Comparative example 2
A lithium ion battery was manufactured according to the method of comparative example 1, except that in the step of manufacturing the electrolyte, compound 7 was used as the first additive, and the amount of compound 7 added was 2% of the total mass of the electrolyte.
Comparative example 3
A lithium ion battery was fabricated according to the method of example 1, except that the first additive was not added in the step of fabricating the electrolyte, wherein the fluoroethylene carbonate was added in an amount of 5% by mass based on the total mass of the electrolyte.
Comparative example 4
A lithium ion battery was fabricated according to the method of example 1, except that, in the step of fabricating the electrolyte, no second additive was added, and triethyl phosphonoacetate was used as the first additive, wherein the amount of triethyl phosphonoacetate added was 2% of the total mass of the electrolyte.
Comparative example 5
A lithium ion battery was fabricated according to the method of example 1, except that triethyl phosphonoacetate was used as the first additive in the electrolyte fabrication step, wherein triethyl phosphonoacetate was added in an amount of 2% by mass and fluoroethylene carbonate was added in an amount of 5% by mass of the electrolyte.
Comparative example 6
A lithium ion battery was manufactured according to the method of example 1, except that the compound 1 was added in an amount of 0.05% of the total mass of the electrolyte in the step of manufacturing the electrolyte.
Comparative example 7
A lithium ion battery was manufactured according to the method of example 1, except that the compound 1 was added in an amount of 20% by mass of the total mass of the electrolyte in the step of manufacturing the electrolyte.
Comparative example 8
A lithium ion battery was fabricated according to the method of example 1, except that in the electrolyte fabrication step, fluoroethylene carbonate was added in an amount of 0.1% based on the total mass of the electrolyte.
Comparative example 9
A lithium ion battery was fabricated according to the method of example 1, except that in the electrolyte fabrication step, fluoroethylene carbonate was added in an amount of 40% based on the total mass of the electrolyte.
Specifically, the additives and their contents contained in the electrolytes of examples 1 to 14 and comparative examples 1 to 9 are shown in the following table:
then, the performance of the lithium ion batteries prepared in examples 1 to 14 and comparative examples 1 to 9 was tested by the following methods, respectively.
(I) Normal temperature cycle Performance test
At 25 ℃, the lithium ion battery is charged to 4.5V by using a constant current of 1C, the lithium ion battery is charged to a cut-off current of 0.05C by using a constant voltage of 4.5V, and after the lithium ion battery is placed for 30min, the lithium ion battery is discharged to 2.7V by using a constant current of 1C, the process is marked as a charge-discharge cycle process, and the discharge capacity of the time is the discharge capacity of the first cycle. And (4) carrying out a cyclic charge-discharge test on the lithium ion battery according to the mode, and taking the discharge capacity of the 500 th cycle.
The capacity retention (%) after 500 cycles of the lithium ion battery was [ discharge capacity at 500 cycles/discharge capacity at first cycle ] × 100%.
(II) high temperature cycle Performance test
At 45 ℃, the lithium ion battery is charged to 4.5V by using a constant current of 1C, then charged to a cut-off current of 0.05C by using a constant voltage of 4.5V, and after the lithium ion battery is placed for 30min, the lithium ion battery is discharged to 2.7V by using a constant current of 1C, and the process is marked as a charge-discharge cycle process, and the discharge capacity of the time is the discharge capacity of the first cycle. And (4) carrying out a cyclic charge-discharge test on the lithium ion battery according to the mode, and taking the discharge capacity of the 300 th cycle.
The capacity retention (%) of the lithium ion battery after 300 cycles was [ discharge capacity at 300 cycles/discharge capacity at first cycle ] × 100%.
(III) high-temperature storage Performance test
Charging the lithium ion battery to 4.5V at a constant current of 1C at 25 ℃, then charging at a constant voltage of 4.5V until the cut-off current is 0.05C, standing for 30min, discharging the lithium ion battery to 2.7V at a constant current of 1C, and taking the discharge capacity as an initial capacity C0Measuring the volume V of the battery before storage0. Then transferring the lithium ion battery to a high-temperature test cabinet for storage for 14 days at 55 ℃; taking out the test battery after storage, standing at room temperature for 12 hours, and measuring the volume V of the stored battery1Discharging the lithium ion battery to 2.7V at 1C constant current, and recording discharge capacity C1Standing for 30min, charging to 4.5V with 1C constant current, charging to 0.05C with 4.5V constant voltage, standing for 30min, discharging to 2.5V with 1C constant current, and recording discharge capacity C2；
Capacity remaining ratio (%) ═ C1/C0×100％；
Capacity recovery ratio (%) ═ C2/C0×100％；
Battery volume expansion ratio (%) [ (V)1-V0)/V0]×100％。
The performance test results of the lithium ion batteries prepared in examples 1 to 14 and comparative examples 1 to 9 are shown in the following table:
from the results given in the table above, compared with comparative examples 1 to 9, the lithium ion batteries of examples 1 to 14 are significantly improved in terms of normal temperature cycle, high temperature cycle, and high temperature storage performance. Therefore, the electrolyte can be better adapted to the high-energy silicon-carbon cathode material, can normally work for a long time under high voltage, and ensures the excellent high-temperature storage performance and cycle performance of the battery.
From the comparison between the example 1 and the comparison 1, it can be seen that the normal temperature cycle performance of the lithium ion battery formed by the electrolyte only containing the first additive is close to that of the example 1, and the high temperature cycle performance is slightly weaker than that of the example 1, which indicates that the electrolyte containing the first additive can significantly reduce the side reaction of the electrolyte and the interface of the positive electrode material under high voltage by forming a stable passivation film on the surface of the positive electrode plate, and obviously improve the high voltage cycle performance of the lithium ion battery;
as can be seen from the comparison between examples 1 to 6 and 11 to 14 and comparative examples 1 and between example 9 and comparative example 2, the first additive (phosphonylated cyclic lactone compound) and the second additive (FEC) have a synergistic effect, and the combination of the two can simultaneously improve the cycle performance and the high-temperature storage performance of the battery, at least can obviously improve the high-temperature storage performance of the battery;
through comparison between a comparative example 1 and a comparative example 4, the phosphonylated cyclic lactone compound has obvious advantages in application to the high-voltage positive electrode lithium ion battery electrolyte compared with linear ester compounds such as triethyl phosphonoacetate, which indicates that the linear ester compounds such as triethyl phosphonoacetate cannot form an effective protective film on the surface of a positive electrode, and also indicates that the phosphonylated cyclic lactone compound with a cyclic lactone structure has a more excellent positive electrode film-forming effect compared with the linear phosphono compound, can remarkably improve the high-voltage cycle performance of a battery, can inhibit the swelling of the battery, and can improve the high-temperature storage performance of the battery;
by comparing examples 3, 7 and 9 with comparative example 5, it can be seen that after triethyl phosphonoacetate is used in combination with FEC, in addition to the significant improvement of normal temperature cycle, high temperature cycle and high temperature storage even deteriorate, indicating that even though the passivation film formed by combining with FEC is poor in effect, close to the effect of FEC alone, it cannot effectively improve the high temperature performance of the silicon anode cell;
as can be seen from comparison of comparative examples 6 and 7 with example 1, when the content of compound 1 is too low (0.05%), the positive and negative electrodes cannot be protected, and when the content of compound 1 is too high (20%), the viscosity of the electrolyte may increase due to too high content, which deteriorates the cycle performance of the battery;
as can be seen from comparison of comparative examples 8 and 9 with example 1, when the fluoroethylene carbonate content is too low (0.1%), it is insufficient to exert a synergistic effect with compound 1, and both the cycle performance and the high-temperature storage performance are lowered; when the content of the fluoroethylene carbonate is too high (40%), although the cycle performance of the battery is improved, the high-temperature cycle storage performance of the lithium ion battery is obviously deteriorated due to the poor thermal stability of the fluoroethylene carbonate, and particularly, the volume expansion rate of the battery is obviously increased.
It should be noted that, although only additive compound 1, compound 4, compound 6 and compound 7 are exemplified in the examples of the present specification, according to other embodiments of the lithium ion battery of the present application, the lithium ion battery electrolyte additive may be one or more of the additive compounds mentioned in other claims.
In summary, the electrolyte provided by the application can effectively improve the high-temperature storage performance of the battery by adding the phosphonylated cyclic lactone compound while ensuring the excellent cycle performance of the battery. In addition, the component of a passivation film of a positive electrode interface and a negative electrode interface can be optimized through the synergistic effect of the phosphonylated cyclic lactone compound and the fluoroethylene carbonate, so that the high capacity retention rate of the lithium battery in the circulating process is ensured, and the high-temperature storage performance of the battery is further improved.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (10)
1. An electrolyte, comprising: the lithium salt is prepared from an organic solvent, a lithium salt and a first additive, wherein the first additive is at least one of phosphonylated cyclic lactone compounds with the structure shown in formula I:
wherein n is more than or equal to 1 and less than or equal to 3, x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1;
wherein R is1、R2、R3And R4Each independently selected from hydrogen, halogen, substituted or unsubstituted C1～C5Alkyl, substituted or unsubstituted C2～C5Unsaturated hydrocarbon group, substituted or unsubstituted C6～C10Aryl, and substituted or unsubstituted C7～C10An alkaryl group.
2. The electrolyte of claim 1, wherein the substitution includes partial substitution and complete substitution, and the substituted substituent is selected from at least one of a halogen group, a cyano group, a carboxyl group, and a sulfonic acid group.
3. The electrolyte of claim 1, wherein the first additive is selected from at least one of the following compounds:
4. the electrolyte of claim 1, wherein the first additive is present in the electrolyte in an amount of 0.1 to 10% by weight, preferably 1 to 5% by weight.
5. The electrolyte of claim 1, further comprising a second additive, wherein the second additive is fluoroethylene carbonate; or the like, or, alternatively,
the second additive is one or a combination of more of vinyl sulfate, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorobis-oxalato phosphate and lithium tetrafluorooxalato phosphate and fluoroethylene carbonate.
6. The electrolyte of claim 5, wherein the second additive is present in the electrolyte in an amount of 1 to 30% by weight, preferably 2 to 15% by weight.
7. The electrolyte of claim 1, wherein the organic solvent comprises a cyclic carbonate and/or a chain carbonate;
the cyclic carbonate is selected from at least one of ethylene carbonate, propylene carbonate, butylene carbonate and gamma-butyrolactone;
the chain carbonate is at least one selected from dimethyl carbonate, diethyl carbonate, methylethyl carbonate, methylpropyl carbonate, methyl formate, ethyl acetate, methyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate and butyl propionate.
8. The electrolyte of claim 1, wherein the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium bis (fluorooxalato) borate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium trifluoromethylsulfonate, and lithium bis (oxalato) borate.
9. A lithium ion battery comprising a positive electrode sheet, a negative electrode sheet, and a separator interposed between the positive electrode sheet and the negative electrode sheet, characterized by further comprising the electrolyte according to any one of claims 1 to 8.
10. The lithium ion battery of claim 9, wherein the negative electrode tab comprises a silicon-containing negative electrode tab.
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