CN105098242B - Electrolyte and lithium ion battery comprising same - Google Patents
Electrolyte and lithium ion battery comprising same Download PDFInfo
- Publication number
- CN105098242B CN105098242B CN201510464212.XA CN201510464212A CN105098242B CN 105098242 B CN105098242 B CN 105098242B CN 201510464212 A CN201510464212 A CN 201510464212A CN 105098242 B CN105098242 B CN 105098242B
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- CN
- China
- Prior art keywords
- lithium
- ion battery
- lithium ion
- active material
- electrolyte
- Prior art date
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 103
- 239000003792 electrolyte Substances 0.000 title claims abstract description 62
- 239000011248 coating agent Substances 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 37
- -1 cyclic sulfate compound Chemical class 0.000 claims abstract description 36
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 17
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 125000005843 halogen group Chemical group 0.000 claims description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 23
- 229910052744 lithium Inorganic materials 0.000 claims description 23
- 239000007773 negative electrode material Substances 0.000 claims description 20
- 239000007774 positive electrode material Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 15
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#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
- 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 2
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 2
- 229910020923 Sn-O Inorganic materials 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910010248 TiO2—Li4Ti5O12 Inorganic materials 0.000 claims description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 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
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011149 active material Substances 0.000 abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 description 38
- 125000000217 alkyl group Chemical group 0.000 description 23
- 150000002430 hydrocarbons Chemical group 0.000 description 16
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 16
- 239000011888 foil Substances 0.000 description 12
- 125000001424 substituent group Chemical group 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 150000001923 cyclic compounds Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000011267 electrode slurry Substances 0.000 description 6
- 229940021013 electrolyte solution Drugs 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011356 non-aqueous organic solvent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 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
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910017704 MH-Ni Inorganic materials 0.000 description 1
- 229910017739 MH—Ni Inorganic materials 0.000 description 1
- 229910003307 Ni-Cd Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 125000002820 allylidene group Chemical group [H]C(=[*])C([H])=C([H])[H] 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 150000002500 ions Chemical class 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
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 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
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 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 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004804 winding 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application relates to an electrolyte and a lithium ion battery comprising the electrolyte, wherein the electrolyte comprises a lithium salt, an organic solvent and an additive, and the additive comprises lithium difluorophosphate and a cyclic sulfate compound. The electrolyte provided by the application is applied to the lithium ion battery, and particularly, after the electrolyte is applied to the lithium ion battery with high coating weight of the active material layer on the single surface of the pole piece, the high-temperature cycle performance of the lithium ion battery is improved, and the rate performance and the low-temperature discharge performance of the lithium ion battery are improved.
Description
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to electrolyte and a lithium ion battery comprising the electrolyte, and particularly the electrolyte is suitable for the lithium ion battery with high coating weight of active materials on a pole piece.
Background
In the rapidly developing information age, the demand of electronic products such as mobile phones, notebooks, cameras, etc. has increased year by year, and lithium ion batteries have been widely used in these fields. Meanwhile, lithium ion batteries have been actively developed in the fields of electric vehicles, hybrid vehicles, energy storage devices, and the like.
The lithium ion battery is used as a working power supply of electronic products, has the outstanding characteristics of high energy density, no memory effect, high working voltage and the like, and gradually replaces the traditional Ni-Cd battery and MH-Ni battery. However, as the market demand of electronic products expands and power and energy storage devices develop, the energy density of lithium ion batteries is also increasing, and therefore, it is urgent to develop lithium ion batteries with high energy density.
At present, the following methods are mainly used for improving the energy density of the lithium ion battery:
firstly, a high-voltage cathode material is developed, but the current cathode material applied to more than 4.4V is still imperfect, and part of electrolyte is unstable under high voltage;
secondly, a new material with high capacity is adopted, such as a silicon material, but the silicon material has serious expansion, low first-cycle coulomb efficiency and low cycle stability;
and thirdly, the energy density of the lithium ion battery is improved by improving the coating weight of the active material layer on the current collector. Although the method has high application feasibility, the dynamic deterioration of the lithium ion battery is serious due to the increase of the coating weight of the active substance on the unit current collector, for example, the mobility of lithium ions is seriously influenced, so that the lithium ion battery has the phenomena of poor rate capability, poor low-temperature performance and the like.
Therefore, it is now desired to provide an electrolyte solution that can improve high-temperature cycle performance, rate capability, and low-temperature discharge performance of a lithium ion battery when applied under conditions of high coating weight of an active material layer on a current collector in the lithium ion battery.
Disclosure of Invention
In order to solve the above problems, the present applicant has conducted intensive studies and, as a result, found that: the electrolyte containing lithium difluorophosphate and the cyclic sulfate compound is applied to a lithium ion battery, particularly a lithium ion battery with a high coating weight of an active material layer on a single surface of a current collector, and can improve the high-temperature cycle performance, the rate capability and the low-temperature discharge performance of the lithium ion battery, so that the application is completed.
The application aims to provide an electrolyte, which comprises a lithium salt, an organic solvent and an additive, wherein the additive comprises lithium difluorophosphate and a cyclic sulfate compound.
Specifically, the cyclic sulfate compound is one or more selected from the group consisting of compounds represented by the following formulas I and II:
in the formula I, n is an integer of 1-3,
in the formula II, m is an integer of 0 to 3,
in the formulae I and II, R1、R2、R3、R4、R5、R6、R7、R8Each independently is one selected from the group consisting of a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a sulfonic group, an alkyl group having 1 to 20 carbon atoms, an unsaturated alkyl group having 2 to 20 carbon atoms, and a group in which the alkyl group having 1 to 20 carbon atoms and the unsaturated alkyl group having 2 to 20 carbon atoms are substituted with a halogen atom, wherein the halogen atom is F, Cl, Br or I.
Another object of the present application is to provide a lithium ion battery, which includes a positive plate, a negative plate, a lithium battery diaphragm and the electrolyte provided by the present application, wherein the positive plate includes a positive current collector and a positive active material layer disposed on the positive current collector, wherein the positive active material layer includes a positive active material; the negative electrode sheet comprises a negative electrode current collector and a negative electrode active material layer arranged on the negative electrode current collector, wherein the negative electrode active material layer comprises a negative electrode active material; the lithium battery diaphragm is positioned between the positive plate and the negative plate.
In particular, in the lithium ion battery, the coating weight of the positive electrode active material layer on one surface of the positive electrode current collector is 0.026g/cm2The coating weight of the negative electrode active material layer on one surface of the negative electrode current collector was 0.013g/cm2The following.
The electrolyte provided by the application is applied to the lithium ion battery, and particularly after the electrolyte is applied to the lithium ion battery with high coating weight of the active material layer on the single surface of the pole piece, the high-temperature cycle performance of the lithium ion battery can be improved, and the rate performance and the low-temperature discharge performance of the lithium ion battery can be improved.
Detailed Description
The features and advantages of the present application will become more apparent and appreciated from the following detailed description of the application.
It is an object of the present application to provide a method of generating electricityAn electrolyte solution comprising a lithium salt, an organic solvent and an additive, wherein the additive comprises lithium difluorophosphate (L iPO)2F2) And cyclic sulfate ester compounds.
In the above electrolyte, the cyclic sulfate ester compound is one containing-O-SO2-cyclic compounds of the O-group. In particular, -O-SO2the-O-group is located on the ring of the cyclic compound.
In a preferred embodiment, the cyclic compound may be a five-membered cyclic compound, a six-membered cyclic compound, a seven-membered cyclic compound, an eight-membered cyclic compound. Further, a five-membered ring compound, a six-membered ring compound, an eight-membered ring compound are preferable, and further, a five-membered ring compound and/or a six-membered ring compound are preferable. Where there are several atoms in the ring, the ring is referred to as a "several-membered ring".
In the electrolyte, the specific type of the cyclic sulfate compound is not particularly limited, and may be selected according to actual needs.
In a preferred embodiment, the cyclic sulfate ester compound is one or more selected from the group consisting of compounds represented by the following formula I and formula II:
in the formula I, n is an integer of 1 to 3, and n is preferably 1 to 2.
When n is an integer of 2 or more, excluding the substituent R1、R2The substituents on the carbon atoms at different positions other than the carbon atom(s) in (b) may be the same or completely different, or the substituents on the carbon atoms at two or more different positions may be the same, and are not limited by specific reference numerals. For example, when n is 2, except that the substituent R is attached1、R2Of four carbon atoms other than the carbon atoms of (A)The substituents may be the same or different, or two or more of the four substituents may be the same.
In the formula II, m is an integer of 0 to 3, and preferably, m is 0 to 1.
When m is an integer of 2 or more, excluding the substituent R5、R6The substituents on the carbon atoms at different positions other than the carbon atom(s) in (b) may be the same or completely different, or the substituents on the carbon atoms at two or more different positions may be the same, and are not limited by specific reference numerals. For example, when m is 2, except that a substituent R is attached5、R6The four substituents on the remaining two carbon atoms other than the carbon atom(s) in (b) may be completely the same or different, or two or more of the four substituents may be the same.
In the above formula I and formula II, R1、R2、R3、R4、R5、R6、R7、R8Each independently is one selected from the group consisting of a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a sulfonic group, an alkyl group having 1 to 20 carbon atoms, an unsaturated alkyl group having 2 to 20 carbon atoms, and a group in which the alkyl group having 1 to 20 carbon atoms and the unsaturated alkyl group having 2 to 20 carbon atoms are substituted with a halogen atom, wherein the halogen atom is F, Cl, Br or I.
In particular, in the unsaturated hydrocarbon group having 2 to 20 carbon atoms, the unsaturated hydrocarbon group is a chain unsaturated hydrocarbon group.
In the above formula I, R1、R2、R3、R4May be different from each other or completely the same, or R1、R2、R3、R4Are the same or are R1、R2、R3、R4Any three of them are the same.
In the above formula II, R5、R6、R7、R8May be different from each other or completely the same, or R5、R6、R7、R8Are the same or are R5、R6、R7、R8Any three of them are the same.
When the alkyl group having 1 to 20 carbon atoms is selected, the specific type of the alkyl group is not particularly limited, and examples thereof include a chain alkyl group and a cyclic alkyl group. Among them, the chain alkyl group includes a straight chain alkyl group and a branched chain alkyl group. In particular, a straight chain alkyl group is selected.
Preferably, the selected carbon atoms of alkyl, more preferably, the selected carbon atoms of 1 ~ 10 alkyl, more preferably, the selected carbon atoms of 1 ~ 5 alkyl, more preferably, the selected carbon atoms of 1 ~ 3 alkyl.
Specific examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, heptyl, cycloheptyl, octyl, cyclooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl.
When the unsaturated hydrocarbon group having 2 to 20 carbon atoms is selected, the specific type of the unsaturated hydrocarbon group is not particularly limited, and may be selected according to actual needs. In particular, alkenyl and alkynyl groups are selected. The number of unsaturated bonds and the position of the unsaturated bond are not particularly limited, and an unsaturated hydrocarbon group having a desired structure may be selected according to the actual circumstances. For example, the number of unsaturated bonds may be 1, 2, 3, or 4. Specifically, the unsaturated bond is located at the terminal of the unsaturated hydrocarbon group, wherein the terminal is a position away from the attachment of the unsaturated hydrocarbon group to the ring.
When the number of the unsaturated bond is 1, in particular, the unsaturated bond is located at the terminal of the selected unsaturated hydrocarbon group, for example, when the number of the carbon atoms is 3 or more, the carbon atom on the unsaturated bond is not bonded to the ring.
In a preferred embodiment, an unsaturated hydrocarbon group having 2 to 10 carbon atoms is selected, more preferably an unsaturated hydrocarbon group having 2 to 5 carbon atoms is selected, and still more preferably an unsaturated hydrocarbon group having 2 to 3 carbon atoms is selected.
Specific examples of the unsaturated hydrocarbon group include: -CH ═ CH2、-CH2-CH＝CH2、-CH2CH2-CH＝CH2、-CH2CH2CH2-CH＝CH2、-C≡CH、-CH2-C≡CH、-CH2CH2-C≡CH、-CH2CH2CH2-C≡CH、-CH＝CH-CH＝CH2。
When the C1-20 alkyl group is substituted with a halogen atom, the number of halogen atoms and the substitution position are not particularly limited, and some or all of the hydrogen atoms in the alkyl group may be substituted as required. For example, the number of halogen atoms may be 1, 2, 3 or 4. In particular, the halogen atom is F, Cl.
When the number of substitution by halogen atoms is 2 or more, the halogen atoms may be the same or different, or the selected halogen atoms may be partially the same.
Examples of the group formed by substituting an alkyl group with a halogen atom include:
When the unsaturated hydrocarbon group having 2 to 20 carbon atoms is substituted with a halogen atom, the number of halogen atoms and the substitution position thereof are not particularly limited, and a part or all of the hydrogen atoms in the unsaturated hydrocarbon group may be substituted according to actual requirements. For example, the number of halogen atoms may be 1, 2, 3 or 4. In particular, the halogen atom is F, Cl.
When the number of substitution by halogen atoms is 2 or more, the halogen atoms may be the same or different, or the selected halogen atoms may be partially the same.
Examples of the group formed when the unsaturated hydrocarbon group is substituted with a halogen atom include:
In a preferred embodiment, R1、R2、R3、R4、R5、R6、R7、R8Each independently is one selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 2 to 10 carbon atoms, and a group in which the alkyl group having 1 to 10 carbon atoms and the unsaturated alkyl group having 2 to 10 carbon atoms are substituted with a fluorine atom or a chlorine atom.
In a further preferred embodiment, R1、R2、R3、R4、R5、R6、R7、R8Each independently is one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an unsaturated alkyl group having 2 to 5 carbon atoms, and a group in which the alkyl group having 1 to 5 carbon atoms and the unsaturated alkyl group having 2 to 5 carbon atoms are substituted with a fluorine atom or a chlorine atom.
In a still further preferred embodiment, R1、R2、R3、R4、R5、R6、R7、R8Each independently is one selected from hydrogen atom, C1-3 alkane group and C2-3 unsaturated alkyl group, especially, R1、R2、R3、R4、R5、R6、R7、R8Each independently is one of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, and an alkynyl group having 2 to 3 carbon atoms.
Specific examples of the cyclic sulfate ester compound include:
in the present application, the sources of the cyclic sulfate compound and lithium difluorophosphate are not particularly limited, and may be obtained commercially or synthesized according to a conventional method.
The research of the applicant finds that the electrolyte simultaneously contains lithium difluorophosphate (L iPO)2F2) And when the electrolyte is applied to a lithium ion battery with high coating weight of active substances on a pole piece, the high-temperature cycle performance of the lithium ion battery can be improved, particularly, the cycle performance of the lithium ion battery at 55-60 ℃ can be improved, the rate performance of the lithium ion battery and the low-temperature discharge performance of the lithium ion battery can be improved, wherein the mentioned low temperature is-10-0 ℃.
In particular, the electrolyte provided by the application is also suitable for a lithium ion battery with high coating weight of an active material layer on one surface of a current collector. Wherein the upper limit of the coating weight of the active material layer on the cathode can be up to 0.026g/cm2The lower limit of the coating weight of the active material layer on the cathode is not particularly limited as long as it is coated as required, and the upper limit of the coating weight of the active material layer on the anode may be up to 0.013g/cm2The lower limit of the coating weight of the active material on the anode is not particularly limited as long as the coating is performed as required. The coating weights mentioned above being all on one side of the current collectorCoating weight of active material layer.
Specifically, in the present application, the coating weight test method of the positive and negative electrode sheets is as follows: taking 20 current collector foils, wherein the area of each current collector foil is S, respectively weighing the weight of each current collector foil, and taking the average value of the weight of each current collector foil as M1; the same weight of slurry was applied to one side of each current collector foil, and after uniform application, dried at 120 ℃ for 1 hour, and tested to be substantially free of solvent. Then weighing the dried current collector foil with one side coated with the slurry, and taking the average value as M2; the coating weight M3 of the active material layer on one side of the current collector is calculated from the following formula.
M3＝(M2-M1)/S
In the present application, the active material layer is located on a positive electrode sheet or a negative electrode sheet in a lithium ion battery, wherein the active material layer includes an active material, a binder, and a conductive agent, wherein the active material in turn includes a positive electrode active material or a negative electrode active material.
In the electrolyte, the content of the cyclic sulfate compound is not particularly limited, and may be selected according to actual needs.
In a preferred embodiment, the content of the cyclic sulfate compound is 0.01 to 3% by weight of the total weight of the electrolyte, further the content of the cyclic sulfate compound is 0.15 to 2.5% by weight of the total weight of the electrolyte, and further the content of the cyclic sulfate compound is 0.3 to 1.5% by weight of the total weight of the electrolyte.
Research shows that when the content of the cyclic sulfate compound is too low, the low-temperature performance of the lithium ion battery is not substantially improved after the electrolyte is applied to the lithium ion battery, and when the content of the cyclic sulfate compound is too high, the electrolyte forms a thick Solid Electrolyte Interface (SEI) film on the surface of the pole piece, and the low-temperature performance of the lithium ion battery is further deteriorated.
In the electrolyte, the content of the cyclic sulfate compound is not particularly limited, and may be selected according to actual needs.
In a preferred embodiment, the content of lithium difluorophosphate is 0.05 to 0.8% by weight of the total weight of the electrolyte, further, the content of lithium difluorophosphate is 0.15 to 0.55% by weight of the total weight of the electrolyte, and further, the content of lithium difluorophosphate is 0.2 to 0.4% by weight of the total weight of the electrolyte.
The research shows that if L iPO2F2When the content of (A) is too low, the electrolyte basically has no improvement effect on the anode of the lithium ion battery, and if the content of (A) is too low, L iPO is used2F2When the content of (b) is too high, the electrolyte may passivate the positive electrode and the negative electrode, so that the dynamic performance of the lithium ion battery may be deteriorated, for example, the mobility of lithium ions may be reduced, and the high-temperature cycle performance, rate capability, and low-temperature discharge performance of the lithium ion battery may be reduced.
In the above electrolyte, the specific type of the lithium salt is not particularly limited, and may be selected according to actual needs.
In a preferred embodiment, the lithium salt is one or more selected from the group consisting of lithium hexafluorophosphate (L iPF)6) Lithium bistrifluoromethanesulfonylimide (L iN (CF)3SO2)2Abbreviated L iTFSI), lithium perchlorate (L iClO)4) Lithium hexafluoroarsenate (L iAsF)6) Lithium bis (oxalato) borate (L iB (C)2O4)2Abbreviated as L iBOB), lithium trifluoromethanesulfonate (L iCF)3SO3)。
In the electrolyte, the content of the lithium salt is not particularly limited, and may be selected according to actual requirements, for example, a conventional addition amount may be selected.
Particularly, the lithium salt is contained in an amount such that the molar concentration of the lithium salt in the electrolyte is 0.5 to 2 mol/L, and more particularly, the lithium salt is contained in an amount such that the molar concentration of the lithium salt in the electrolyte is 0.9 to 1.3 mol/L.
In the present application, the specific type of the organic solvent is not particularly limited, and may be selected according to actual requirements. In particular, one or more of the non-aqueous organic solvents are selected.
Specific examples of the nonaqueous organic solvent include: ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, gamma-butyrolactone, methyl formate, ethyl propionate, propyl propionate, tetrahydrofuran.
In the present application, the preparation method of the electrolyte is not particularly limited, and the electrolyte may be prepared according to a conventional method as long as the materials in the electrolyte are uniformly mixed. For example, a lithium salt, lithium difluorophosphate, and a cyclic sulfate compound are added to a solvent and mixed to obtain an electrolytic solution. The order of addition of the materials is not particularly limited. Specifically, the lithium salt is added into the organic solvent, then the lithium difluorophosphate and the cyclic sulfate compound are added into the organic solvent together for mixing, and particularly, the electrolyte is obtained after uniform mixing.
Another object of the present application is to provide a lithium ion battery, which includes a positive plate, a negative plate, a lithium battery diaphragm and an electrolyte, wherein the electrolyte is the electrolyte provided by the present application.
In the lithium ion battery, the positive plate comprises a positive current collector and a positive active material layer arranged on the positive current collector, wherein the positive active material layer comprises a positive active material, a binder and a conductive agent; the negative plate comprises a negative current collector and a negative active material layer arranged on the negative current collector, wherein the negative active material layer comprises a negative active material, a binder and a conductive agent; the lithium battery diaphragm is positioned between the positive plate and the negative plate. The specific types of the positive current collector, the positive active material, the negative current collector, the negative active material, the binder, the conductive agent and the lithium battery diaphragm are not particularly limited, are all conventional raw materials, and can be selected according to requirements.
In the lithium ion battery, the upper limit of the coating weight of the positive active material layer on the positive current collector can reach 0.026g/cm2In particular, the coating weight is 0.02g/cm2The lower limit of the coating weight of the positive active material on the positive electrode current collector is not particularly limited as long as the coating is performed as required; negative activity on negative current collectorThe upper limit of the coating weight of the material layer can be up to 0.013g/cm2In particular, the coating weight is 0.01g/cm2The lower limit of the coating weight of the negative electrode active material layer on the negative electrode current collector is not particularly limited as long as it is coated as required. The coating weight of the active material layer mentioned here is the coating weight of the active material layer on one side of the current collector.
In particular, in the lithium ion battery, the positive electrode current collector can be an aluminum foil; copper foil can be selected as the negative current collector; the binder can be one or more of polyvinylidene fluoride (PVDF), Styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC); the conductive agent can be one or more of superconducting carbon, carbon nano tubes, graphene and carbon nano fibers; the lithium battery diaphragm can be selected from polyethylene, polypropylene, polyvinylidene fluoride and multilayer composite films of the polyethylene, the polypropylene and the polyvinylidene fluoride; specific types of the materials are mentioned above, but the materials are not limited to the positive electrode current collector, the negative electrode current collector, the binder, the conductive agent and the lithium battery separator material mentioned above.
In a preferred embodiment, the positive active material is one or more of lithium cobaltate, lithium iron phosphate, lithium manganate and lithium nickel manganese cobalt ternary materials.
In a preferred embodiment, the negative active material is selected from the group consisting of metallic lithium, natural graphite, artificial graphite, mesophase micro carbon spheres (abbreviated as MCMB), hard carbon, soft carbon, silicon-carbon composite, L i-Sn alloy, L i-Sn-O alloy, Sn, SnO2Spinel-structured lithiated TiO2-Li4Ti5O12L i-Al alloy.
The lithium ion battery comprises the electrolyte provided by the application, so that the lithium ion battery provided by the application has excellent high-temperature cycle performance, particularly excellent high-temperature cycle performance at 55-60 ℃, and in addition, the lithium ion battery provided by the application has good rate performance and excellent low-temperature discharge performance, wherein the lithium ion battery has excellent low-temperature discharge performance at-10-0 ℃.
The preparation method of the lithium ion battery provided by the application is well known in the art, and the lithium ion battery provided by the application can be prepared according to the existing preparation method of the lithium ion battery.
Examples
The present application is further described below by specific examples. However, these examples are merely exemplary and do not set any limit to the scope of the present application.
In the following examples, comparative examples and test examples, reagents, materials and instruments used therefor were commercially available unless otherwise specified.
In the following experimental examples, comparative examples and test examples, the materials used were as follows:
organic solvent: ethylene Carbonate (EC), Propylene Carbonate (PC), diethyl carbonate (DEC).
L iPF lithium salt6、LiAsF6、LiClO4、LiB(C2O4)2、LiN(CF3SO2)2、LiCF3SO3。
Lithium difluorophosphate (L iPO)2F2)。
Cyclic sulfate compounds:
lithium battery diaphragm: polypropylene separator film with a thickness of 12 μm.
Examples 1 to 20 electrolyte solution 1#～20#Preparation of
In each of examples 1 to 20, the following preparation methods were used to prepare an electrolyte solution 1 in this order#～20#：
In a drying room, lithium salt is added into the mixture of EC, PC and DEC, and L iPO is added2F2And cyclic sulfate compound, mixingAfter homogenization, an electrolyte was prepared in which the EC and PP were mentioned in a ratio of EC: PC: DEC of 20: 60 and the molar concentration of lithium salt in the electrolyte was 1 mol/L.
In the above examples 1 to 20, the specific types of the lithium salt and the cyclic sulfate compound, and the sum of the contents of the respective materials, L iPO2F2Wherein, in the following table 1, the content of the cyclic sulfate ester compound is a weight percentage calculated based on the total weight of the electrolyte, L iPO2F2The content of (b) is a weight percentage calculated based on the total weight of the electrolyte.
TABLE 1
Comparative examples 1 to 6
In comparative examples 1 to 6, electrolytes 1 to 6 were prepared in sequence according to the preparation methods given in the examples, wherein the addition amounts of the respective materials used are as shown in table 2 below, and in table 1 below, the content of the cyclic sulfate ester compound is a weight percentage calculated based on the total weight of the electrolyte, L iPO2F2The content of (b) is a weight percentage calculated based on the total weight of the electrolyte.
TABLE 2
Note: "-" indicates that no material was added.
Test examples
Preparation of lithium ion battery
The electrolyte solutions 1 obtained in examples and comparative examples were mixed#～20#Respectively preparing 1-6 electrolyte solutions to obtain the lithium ion battery 1 in sequence according to the following steps#～20#1-6 of lithium ion battery:
(1) preparation of positive plate
Positive plate 1:
mixing lithium cobaltate (L iCoO)2) Mixing a binder (polyvinylidene fluoride) and a conductive agent (acetylene black) according to the mass ratio of lithium cobaltate to polyvinylidene fluoride to acetylene black of 98: 1, adding N-methyl pyrrolidone (NMP), and stirring under the action of a vacuum stirrer until the system becomes uniform and transparent to obtain anode slurry; uniformly coating the positive electrode slurry on an aluminum foil with the thickness of 12 mu m; drying the aluminum foil at room temperature, transferring the aluminum foil to a 120 ℃ oven for drying for 1h, forming an anode active material layer by anode slurry, and then performing cold pressing and slitting to obtain an anode plate, wherein the coating weight of the anode active material layer on one surface of the aluminum foil is 0.0200g/cm2。
Positive electrode plate 2:
the positive electrode sheet 2 was prepared according to the method of the positive electrode sheet 1, in which the positive electrode active material layer formed after drying the positive electrode slurry was different, and the coating weight of the positive electrode active material layer on one side of the aluminum foil was 0.026g/cm2The other conditions were unchanged.
(2) Preparation of negative plate
Negative electrode plate 1:
mixing artificial graphite, a thickener sodium carboxymethylcellulose (CMC) solution and a binder styrene-butadiene rubber emulsion according to the mass ratio of the artificial graphite to the sodium carboxymethylcellulose to the styrene-butadiene rubber emulsion of 98: 1, adding the mixture into a deionized water solvent, and stirring the mixture in a vacuum stirrer to obtain negative electrode slurry; uniformly coating the negative electrode slurry on a copper foil with the thickness of 8 mu m; the copper foil is dried at room temperature and then transferred to a 120 ℃ oven for drying for 1h, the negative electrode slurry forms a negative electrode active material layer, then a negative electrode sheet is obtained through cold pressing and slitting, wherein the coating weight of the negative electrode active material layer on one side of the copper foil is 0.010g/cm2。
And 2, negative plate 2:
the preparation of the negative electrode sheet 2 was carried out according to the method of the negative electrode sheet 1, in which the negative electrode active material layer formed after drying the negative electrode slurry was different, and the negative electrode active material layer was located on one side of the aluminum foilThe coating weight of the material layer was 0.0130g/cm2The other conditions were unchanged.
(3) Preparation of lithium ion battery
And separating the positive plate and the negative plate by using a lithium battery, winding the positive plate and the negative plate into a square bare cell, then filling an aluminum-plastic film, baking at 80 ℃ to remove water, injecting corresponding electrolyte, sealing, and performing the working procedures of standing, hot cold pressing, formation, clamping, capacity grading and the like to obtain the finished product of the lithium ion battery.
Lithium ion battery performance testing
(1) High temperature cycle performance testing of lithium ion batteries
The prepared lithium ion batteries are respectively tested according to the following methods:
after the lithium ion battery is charged to 0.05C under the constant voltage of 4.4V at the temperature of 55 ℃, the lithium ion battery is kept stand for 5 minutes, then the lithium ion battery is discharged to 3.0V under the constant current of 0.5C, the discharge capacity is the first discharge capacity of the lithium ion battery, and then the lithium ion battery, the electrolyte in the battery, the positive electrode sheet and the negative electrode sheet are respectively subjected to 40, 80, 120, 200 and 500 charge and discharge cycles according to the cycle conditions, so that the corresponding lithium ion battery, the electrolyte in the battery, the positive electrode sheet and the negative electrode sheet and the test result are shown in the table 3. The cycle retention was calculated as follows.
Capacity retention (%) after the N-th cycle of the lithium ion battery was × 100% (discharge capacity at the N-th cycle/first discharge capacity) in terms of percentage
TABLE 3
(2) Rate capability test for lithium ion battery
The prepared lithium ion batteries are respectively tested according to the following methods:
the lithium ion battery is placed still for 30 minutes at 25 ℃, then is charged to 4.4V at a constant current of 0.5C multiplying power, then is charged to 0.05C at a constant voltage of 4.4V, is placed still for 5 minutes, then is discharged to 3.0V at different multiplying powers of 0.2C, 0.5C, 1.0C and 2.0C, and is placed still for 5 minutes after the discharge is finished each time, and the discharge capacity of the lithium ion battery is recorded. The discharge capacity of the lithium ion battery at different discharge rates is calculated by the following formula based on the discharge capacity at 0.2C rate, and the corresponding lithium ion battery, the electrolyte selected in the battery, the positive electrode sheet, the negative electrode sheet and the results obtained by the test are shown in table 4.
Rate discharge capacity ratio (%) of the lithium ion battery (discharge capacity at the corresponding rate/discharge capacity at 0.2C rate) × 100%
(3) Low-temperature discharge performance test of lithium ion battery
The prepared lithium ion batteries are respectively tested according to the following methods:
standing the lithium ion battery for 30 minutes at 25 ℃, then charging the lithium ion battery to 4.4V at a constant current of 0.5C, then charging the lithium ion battery to 0.05C at a constant voltage of 4.4V, standing the lithium ion battery for 5 minutes, then standing the lithium ion battery for 4 hours at different temperatures of 25 ℃, 0 ℃ and-10 ℃, discharging the lithium ion battery to 3.0V at 0.5C, and standing the lithium ion battery for 5 minutes after each discharge is finished, and recording the discharge capacity of the lithium ion battery. The discharge capacity ratio of the lithium ion battery at different temperatures was calculated based on the 25 ℃ discharge capacity, and the corresponding lithium ion battery, the electrolyte in the battery, the positive and negative electrode sheets, and the results obtained by the test are shown in table 4.
The discharge capacity ratio (%) of the lithium ion battery at different temperatures was × 100% (discharge capacity at the corresponding temperature/discharge capacity at 25 ℃).
TABLE 4
As can be seen from tables 3 and 4, the ratio of lithium to lithiumThe capacity retention rate after circulation, the discharge capacity ratio under different multiplying power and the discharge capacity ratio under low temperature obtained by testing the ion batteries 1-6, and the lithium ion battery 1#～20#The comprehensive performance of the lithium ion battery is improved, for example, the capacity retention rate after circulation, the discharge capacity ratio under different multiplying factors and the discharge capacity ratio under low temperature are all improved to a large extent.
Therefore, when the electrolyte provided by the application is applied to a lithium ion battery, particularly the lithium ion battery with a high coating weight of an active material layer on one side of a pole piece, the comprehensive performance of the lithium ion battery, such as cycle performance, rate performance and low-temperature discharge performance, can still be improved.
Those skilled in the art to which the present application pertains can also make appropriate changes and modifications to the above-described embodiments, based on the disclosure of the above description. Therefore, the present application is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present application should fall within the scope of the claims of the present application.
Claims (7)
1. The lithium ion battery is characterized by comprising a positive plate, a negative plate, a lithium battery diaphragm and electrolyte, wherein the positive plate comprises a positive current collector and a positive active material layer arranged on the positive current collector, and the positive active material layer comprises a positive active material; the negative electrode sheet comprises a negative electrode current collector and a negative electrode active material layer arranged on the negative electrode current collector, wherein the negative electrode active material layer comprises a negative electrode active material; the lithium battery diaphragm is positioned between the positive plate and the negative plate; wherein the coating weight of the positive active material layer on one surface of the positive current collector is 0.026g/cm2The following; the electrolyte comprises a lithium salt, an organic solvent and an additive, wherein the additive comprises lithium difluorophosphate and a cyclic sulfate compound;
the cyclic sulfate compound is one or more of compounds shown in a formula II:
in the formula II, m is an integer of 0 to 3, and R5、R6、R7、R8Each independently selected from one of hydrogen atom, halogen atom, cyano group, carboxyl group, C1-20 alkyl group, C2-20 unsaturated alkyl group, and the C1-20 alkyl group and C2-20 unsaturated alkyl group are substituted by halogen atom, wherein the halogen atom is F, Cl, Br, I.
2. The lithium ion battery according to claim 1, wherein the content of the cyclic sulfate compound is 0.01 to 3% of the total weight of the electrolyte.
3. The lithium ion battery according to claim 1, wherein the content of the lithium difluorophosphate is 0.05 to 0.8% of the total weight of the electrolyte.
4. The lithium ion battery according to claim 1, wherein the lithium salt is one or more selected from the group consisting of lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimide, lithium perchlorate, lithium hexafluoroarsenate, lithium bisoxalato borate and lithium trifluoromethanesulfonate.
5. The lithium ion battery according to claim 1, wherein the organic solvent is one or more selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, γ -butyrolactone, methyl formate, ethyl propionate, propyl propionate, and tetrahydrofuran.
6. The lithium ion battery according to claim 1, wherein a coating weight of the negative electrode active material layer on one surface of the negative electrode current collector is 0.013g/cm2The following.
7. The lithium ion battery according to any one of claims 1 to 6, wherein the positive active material is one or more of lithium cobaltate, lithium iron phosphate, lithium manganate and lithium nickel manganese cobalt ternary material, and the negative active material is selected from metallic lithium, natural graphite, artificial graphite, mesophase micro carbon spheres, hard carbon, soft carbon, silicon-carbon composite, L i-Sn alloy, L i-Sn-O alloy, Sn, SnO2Spinel-structured lithiated TiO2-Li4Ti5O12L i-Al alloy.
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| CN202010668302.1A CN111769329B (en) | 2015-07-31 | 2015-07-31 | Lithium ion battery |
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| WO2017154908A1 (en) * | 2016-03-07 | 2017-09-14 | 株式会社 東芝 | Non-aqueous electrolyte cell and cell pack |
| CN107293782B (en) * | 2016-04-11 | 2020-09-04 | 宁德新能源科技有限公司 | Non-aqueous electrolyte and lithium ion battery |
| CN107293776A (en) * | 2016-04-12 | 2017-10-24 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery |
| CN107403958A (en) * | 2016-05-19 | 2017-11-28 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery |
| CN107403950A (en) * | 2016-05-19 | 2017-11-28 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery |
| CN105958120B (en) * | 2016-06-28 | 2019-05-21 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery using same |
| CN107221705A (en) * | 2017-04-25 | 2017-09-29 | 江苏楚汉新能源科技有限公司 | A kind of high-voltage lithium-ion battery electrolyte and high-voltage lithium ion batteries |
| CN109309256A (en) * | 2017-07-28 | 2019-02-05 | 宁德时代新能源科技股份有限公司 | Electrolyte and battery |
| CN109980277A (en) * | 2017-12-27 | 2019-07-05 | 张家港市国泰华荣化工新材料有限公司 | A kind of nonaqueous electrolytic solution and secondary cell |
| CN109994768A (en) * | 2017-12-29 | 2019-07-09 | 宁德时代新能源科技股份有限公司 | Electrolyte solution and secondary battery |
| CN110208716B (en) * | 2018-02-28 | 2020-07-03 | 宁德时代新能源科技股份有限公司 | Battery and method for testing residual active lithium capacity in negative pole piece after battery discharge |
| CN113130997B (en) | 2018-05-17 | 2022-07-05 | 宁德时代新能源科技股份有限公司 | Lithium ion battery, preparation method thereof and electric vehicle comprising lithium ion battery |
| CN110661027B (en) * | 2018-06-29 | 2021-05-04 | 宁德时代新能源科技股份有限公司 | Secondary battery |
| CN113067037A (en) * | 2021-05-17 | 2021-07-02 | 湖北亿纬动力有限公司 | Electrolyte and lithium ion battery comprising same |
| CN115347241B (en) * | 2022-10-14 | 2023-06-06 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
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| CN111769329B (en) | 2022-07-12 |
| CN105098242A (en) | 2015-11-25 |
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