CN116365035A - Electrolyte and battery - Google Patents
Electrolyte and battery Download PDFInfo
- Publication number
- CN116365035A CN116365035A CN202310522200.2A CN202310522200A CN116365035A CN 116365035 A CN116365035 A CN 116365035A CN 202310522200 A CN202310522200 A CN 202310522200A CN 116365035 A CN116365035 A CN 116365035A
- Authority
- CN
- China
- Prior art keywords
- additive
- electrolyte
- lithium
- halogen
- substituted
- 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
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 81
- 239000000654 additive Substances 0.000 claims abstract description 98
- 230000000996 additive effect Effects 0.000 claims abstract description 98
- -1 lithium alkyl sulfonate Chemical class 0.000 claims abstract description 37
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 125000005843 halogen group Chemical class 0.000 claims description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 23
- 229910052736 halogen Inorganic materials 0.000 claims description 23
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 8
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 8
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 8
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 8
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- 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 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 6
- 229940090181 propyl acetate Drugs 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 4
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 4
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 4
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 4
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- 239000004305 biphenyl Chemical group 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 3
- 239000010410 layer Substances 0.000 abstract description 18
- 239000007774 positive electrode material Substances 0.000 abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 13
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 7
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000011149 active material Substances 0.000 abstract description 3
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000011241 protective layer Substances 0.000 abstract description 3
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- 125000001188 haloalkyl group Chemical group 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000011056 performance test Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 125000006165 cyclic alkyl group Chemical group 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 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 2
- 230000009471 action Effects 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 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
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 2
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910018040 Li 1+x Ni Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 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
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 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
- 230000003247 decreasing effect Effects 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
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 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
- 238000004146 energy storage Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000004969 haloethyl group Chemical group 0.000 description 1
- 125000004970 halomethyl group Chemical group 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 150000002430 hydrocarbons Chemical group 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
- 239000003273 ketjen black Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 125000003136 n-heptyl 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])* 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
- 229910021382 natural graphite Inorganic materials 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
- 239000011356 non-aqueous organic solvent Substances 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
- 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
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process 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
- 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
- 238000007493 shaping process Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 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
- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 238000009461 vacuum packaging Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses an electrolyte and a battery, wherein the electrolyte comprises the following components: at least one of the first additive and the second additive, a solvent and an electrolyte; the structural formula of the first additive is structural formula (1), and the second additive is at least one selected from structural formulas (2) and (3). The first additive contains sulfonate compounds, the chain sulfonate compounds can improve the oxidation resistance of the electrolyte, the electrolyte is not easy to oxidize under high temperature and high voltage, lithium alkyl sulfonate can be formed at the anode in the formation stage, the ion conductivity of the SEI film is increased, and the high-temperature cycle resistance of the battery is improved. The cyano group in the second additive can complex cobalt ions in the positive electrode active layer to form a protective layer, so that the cobalt ions in the positive electrode active layer are prevented from being dissolved out, the cycle performance of the lithium ion battery is improved, and the first additive and the second additive can prevent electrolyte from entering the active material layer to corrode the positive electrode active material, so that the battery has excellent high-temperature cycle performance and high-temperature storage performance.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to electrolyte and a battery.
Background
Lithium ion batteries are widely used in various electronic products due to their advantages of high specific energy density, long cycle life, and the like, and have been widely used in electric vehicles, various electric tools, and energy storage devices in recent years. With the expansion of the application range of lithium ion batteries, the sizes of the batteries are also increased, the safety performance of the batteries is particularly important, and meanwhile, higher requirements are put on the energy density of the batteries. In order to increase the energy density of the battery, it is a common path to further increase the voltage of the positive electrode material of the lithium ion battery, but as the limiting voltage of the positive electrode material is continuously increased, the gram capacity of the positive electrode material is gradually increased, and the high temperature performance of the battery is seriously deteriorated, resulting in the reduction of the cycle performance of the battery.
Disclosure of Invention
The embodiment of the invention aims to provide an electrolyte and a battery, which are used for solving the problem that the high-temperature performance of the battery is seriously deteriorated, so that the cycle performance of the battery is reduced.
In a first aspect, an embodiment of the present invention provides an electrolyte, including:
at least one of the first additive and the second additive, a solvent and an electrolyte;
the structural formula of the first additive is shown as a structural formula (1):
wherein n is a positive integer, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Independently selected from one of alkane with 1-20 carbon atoms, halogenated alkane or halogen atom;
the second additive is selected from at least one of the structural formula (2) and the structural formula (3),
wherein a, b, c, d, e, f is a positive integer.
Optionally, the first additive is selected from at least one of structural formulas 1-1 to 1-5,
optionally, the electrolyte comprises a first additive, wherein the mass of the first additive is 0.1% -10% of the mass of the electrolyte.
Optionally, the second additive is selected from at least one of structural formulas 2-1 to 2-4,
optionally, the electrolyte comprises a second additive, wherein the mass of the second additive is 0.5% -10% of the mass of the electrolyte.
Optionally, the electrolyte further comprises:
a third additive, the structural formula of the third additive is
R 7 、R 8 、R 9 、R 10 、R 11 、R 12 Independently selected from C substituted or unsubstituted with halogen 1 -C 20 C which is substituted or unsubstituted by halogen, is an alkanyl, unsaturated alkenyl, or C which is substituted or unsubstituted by halogen 3 -C 20 Cycloalkyl of (C), phenyl substituted or unsubstituted by halogen, biphenyl substituted or unsubstituted by halogen, C substituted or unsubstituted by halogen 6 -C 26 A phenylalkyl group of (C), a condensed ring aromatic hydrocarbon group substituted or unsubstituted by halogen, a hydrogen atom.
Optionally, the third additive is selected from at least one of structural formulas 3-1 to 3-40,
optionally, the mass of the third additive is 1% -10% of the mass of the electrolyte.
Optionally, the electrolyte is selected from at least one of lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorooxalato borate, lithium bistrifluoromethylsulfonyl imide, lithium difluorobisoxalato phosphate, lithium tetrafluoroborate, lithium bisoxalato borate, lithium hexafluoroantimonate, lithium hexafluoroarsonate, lithium bis (pentafluoroethylsulfonyl) imide, lithium tris (trifluoromethylsulfonyl) methyllithium and lithium bis (trifluoromethylsulfonyl) imide; and/or
The solvent comprises at least one of carbonate and carboxylate, wherein the carbonate comprises at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate; the carboxylic acid ester comprises at least one of propyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, propyl propionate, ethyl propionate, methyl butyrate and ethyl n-butyrate; and/or
The electrolyte further comprises: at least one of 1,3, 6-hexanetrinitrile and 1, 3-propane sultone.
In a second aspect, embodiments of the present invention provide a battery comprising the electrolyte described in the above embodiments.
The electrolyte of the embodiment of the invention comprises the following components: at least one of the first additive and the second additive, a solvent and an electrolyte; the structural formula of the first additive is structural formula (1), and the second additive is at least one selected from structural formulas (2) and (3). The first additive contains sulfonate compound, the chain sulfonate compound can improve the oxidation resistance of the electrolyte, the electrolyte is not easy to oxidize under high temperature and high voltage, lithium alkyl sulfonate can be formed on one side of an anode in a formation stage, the ion conductivity of the SEI film is increased, and the high temperature cycle resistance of the battery is improved. The cyano group in the second additive can fully complex cobalt ions in the positive electrode active layer to form a protective layer, so that the cobalt ions in the positive electrode active layer are prevented from being dissolved out, the cycle performance of the lithium ion battery is improved, and the first additive and the second additive can prevent electrolyte from entering the active material layer to corrode the positive electrode active material, so that the battery has excellent high-temperature cycle performance and high-temperature storage performance.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The terms first, second and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that embodiments of the invention may be practiced otherwise than as described herein. Furthermore, in the description and claims, "and/or" means at least one of the connected objects, and the character "/", generally means that the associated object is an "or" relationship.
The electrolyte and the battery provided by the embodiment of the invention are described in detail below through specific embodiments and application scenes thereof.
The electrolyte of the embodiment of the invention comprises the following components:
at least one of the first additive and the second additive, a solvent and an electrolyte;
the structural formula of the first additive is shown as a structural formula (1):
wherein n is a positive integer, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Independently selected from one of alkane with 1-20 carbon atoms, halogenated alkane or halogen atom; n may be an even number and n may be less than or equal to 30.R is R 1 、R 2 、R 3 、R 4 、R 5 、R 6 May be different from each other or the same as each other.
When R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 When each is independently a halogen alkyl group selected from the group consisting of a C1-20 halogen alkyl group, the specific type of the halogen alkyl group is not particularly limited, and may be selected according to practical requirements, for example, a chain (halogen-substituted) alkyl group and a (halogen-substituted) cyclic alkyl group, wherein the chain halogen alkyl group further includes a linear halogen alkyl group and a branched halogen alkyl group, and the cyclic halogen alkyl group may have a substituent or may not have a substituent. As examples of the halogen alkane group, specific examples may be given: halomethyl, haloethyl, halo-n-propyl, halo-isopropyl, halo-cyclopropyl, halo-n-butyl, halo-isobutyl, halo-sec-butyl, halo-tert-butyl, halo-cyclobutyl, halo-n-pentyl, halo-isopentyl, halo-tert-pentyl, halo-neopentyl, halo-cyclopentyl, halo-tert-pentyl halo-2, 2-dimethylpropyl, halo-1-ethylpropyl, halo-1-methylbutyl, halo-2-methylbutyl, halo-n-hexyl halogenated isohexyl, halogenated-2-hexyl, halogenated-3-hexyl, halogenated-cyclohexyl, halogenated-2-methylpentyl, halogenated-3-methylpentyl halo-1, 2-trimethylpropyl, halo-3, 3-dimethylbutyl, halo-n-heptyl, halo-2-heptyl, halo-3-heptyl, halo-2-methylhexyl, halo-3-methylhexyl, halo-4-methylhexyl, halo-isoheptyl, halo-cycloheptyl, halo-n-octyl, halo-cyclooctyl, halo-nonyl, halo-decyl, halo-undecyl, halo-dodecyl, halo-tridecyl, halo-tetradecyl, halo-pentadecyl, halo-hexadecyl, halo-heptadecyl, halo-octadecyl, halo-nonadecyl, halo-eicosylA hydrocarbon group. For example, the halogen substituted atom may be a fluorine atom substitution.
The second additive is selected from at least one of the structural formula (2) and the structural formula (3),
wherein a, b, c, d, e, f is a positive integer.
a. b, c, d, e, f can be odd and a, b, c, d, e, f can be less than or equal to 30.
The electrolyte may be at least one selected from the group consisting of lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorooxalato borate, lithium bistrifluoromethylsulfonyl imide, lithium difluorobisoxalato phosphate, lithium tetrafluoroborate, lithium bisoxalato borate, lithium hexafluoroantimonate, lithium hexafluoroarsenate, lithium bis (pentafluoroethylsulfonyl) imide, lithium tris (trifluoromethylsulfonyl) methyl lithium and lithium bis (trifluoromethylsulfonyl) imide. The solvent may be a nonaqueous organic solvent, and the solvent may include at least one of a carbonate and a carboxylate, the carbonate including at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methylethyl carbonate; the carboxylic acid ester comprises at least one of propyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, propyl propionate, ethyl propionate, methyl butyrate and ethyl n-butyrate. The specific types of electrolyte and solvent may be selected according to the practice.
The electrolyte of the embodiment of the invention comprises the following components: at least one of the first additive and the second additive, a solvent and an electrolyte; the structural formula of the first additive is structural formula (1), and the second additive is at least one selected from structural formulas (2) and (3). The first additive contains sulfonate compound, the chain sulfonate compound can improve the oxidation resistance of the electrolyte, the electrolyte is not easy to oxidize under high temperature and high voltage, lithium alkyl sulfonate can be formed on one side of an anode in a formation stage, the ion conductivity of the SEI film is increased, and the high temperature cycle resistance of the battery is improved. The cyano group in the second additive can fully complex cobalt ions in the positive electrode active layer to form a protective layer, so that the cobalt ions in the positive electrode active layer are prevented from being dissolved out, the cycle performance of the lithium ion battery is improved, and the first additive and the second additive can prevent electrolyte from entering the active material layer to corrode the positive electrode active material, so that the battery has excellent high-temperature cycle performance and high-temperature storage performance.
In some embodiments, the first additive may be selected from at least one of formulas 1-1 to 1-5,
the first additive may be selected from one of structural formulas 1-1 to 1-5, and the first additive may be simultaneously selected from a plurality of structural formulas 1-1 to 1-5, for example, the first additive may be simultaneously selected from structural formulas 1-1 and 1-3, and the first additive may be selected from structural formulas 1-1 to 1-5 according to the actual use.
In some embodiments, the electrolyte may include a first additive, which may be 0.1% -10% by mass of the electrolyte. For example, the mass of the first additive may be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.3%, 1.5%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.5%, 2.6%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8%, 5%, 6%, 7%, 8%, 9% or 10% of the mass of the electrolyte, and the specific content of the first additive may be selected according to the actual use.
In an embodiment of the present invention, the second additive may be selected from at least one of structural formulas 2-1 to 2-4,
the second additive may be selected from one of structural formulas 2-1 to 2-4, and the second additive may be simultaneously selected from a plurality of structural formulas 2-1 to 2-4, for example, the second additive may be simultaneously selected from structural formulas 2-1 and 2-2, the second additive may be simultaneously selected from structural formulas 2-1 and 2-4, and the second additive may be actually selected from structural formulas 2-1 to 2-4.
Alternatively, the electrolyte may include a second additive, and the mass of the second additive may be 0.5% to 10% of the mass of the electrolyte. For example, the mass of the second additive may be 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.3%, 1.5%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.5%, 2.6%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8%, 5%, 6%, 7%, 8%, 9% or 10% of the mass of the electrolyte, and the specific content of the second additive may be selected according to the actual use.
In some embodiments, the electrolyte may further include: a third additive, the structural formula of the third additive is
R 7 、R 8 、R 9 、R 10 、R 11 、R 12 May be independently selected from C substituted or unsubstituted with halogen 1 -C 20 C which is substituted or unsubstituted by halogen, is an alkanyl, unsaturated alkenyl, or C which is substituted or unsubstituted by halogen 3 -C 20 Cycloalkyl of (C), phenyl substituted or unsubstituted by halogen, biphenyl substituted or unsubstituted by halogen, C substituted or unsubstituted by halogen 6 -C 26 A phenylalkyl group of (C), a condensed ring aromatic hydrocarbon group substituted or unsubstituted by halogen, a hydrogen atom. The third additive has high thermal stability, and can improve the thermal stability of the electrolyte under the premise of meeting the requirement of interfacial film formation, thereby improving the thermal stability of the battery at high temperature, and the first additive and the third additive can improve the oxidation resistant window of the electrolyteThe second additive can be more fully combined with cobalt ions of the positive electrode active layer at the positive electrode, so that the cycle performance of the lithium battery is improved.
When R is 7 、R 8 、R 9 、R 10 、R 11 、R 12 When substituted with a halogen atom, the substituted halogen atom may be: F. cl, I, etc. When R is 7 、R 8 、R 9 、R 10 、R 11 、R 12 When each is independently an alkyl group having 1 to 20 carbon atoms, the specific type of the alkyl group is not particularly limited, and may be selected according to practical requirements, for example, a chain (halogen-substituted) alkyl group and a (halogen-substituted) cyclic alkyl group, wherein the chain alkyl group may include a straight chain alkyl group and a branched alkyl group, and the cyclic alkyl group may have a substituent or may not have a substituent. As examples of the alkane group, specific examples may be given: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, cyclopentyl, 2-dimethylpropyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, n-hexyl, isohexyl, 2-hexyl, 3-hexyl, cyclohexyl, 2-methylpentyl, 3-methylpentyl, 1, 2-trimethylpropyl, 3-dimethylbutyl, n-heptyl, 2-heptyl, 3-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, isoheptyl, cycloheptyl, n-octyl, cyclooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl.
In an embodiment of the present invention, the third additive may be selected from at least one of structural formulas 3-1 to 3-40,
the third additive may be selected from one of structural formulas 3-1 to 3-40, the third additive may be simultaneously selected from a plurality of structural formulas 3-1 to 3-40, for example, the third additive may be simultaneously selected from structural formulas 3-1 and 3-4, the third additive may be simultaneously selected from structural formulas 3-1 and 3-11, the third additive may be simultaneously selected from structural formulas 3-20 and 3-23, and the third additive may be actually selected from structural formulas 3-1 to 3-40. The third additive contains fluorine atoms, is a fluorinated solvent with higher thermal stability, and can improve the thermal stability of the whole electrolyte on the premise of meeting the requirement of interfacial film formation, thereby improving the thermal stability of the battery.
In some embodiments, the mass of the third additive may be 1% -10% of the mass of the electrolyte. For example, the mass of the third additive may be 1%, 1.2%, 1.3%, 1.5%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.5%, 2.6%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8%, 5% or 6% of the mass of the electrolyte, and the specific content of the third additive may be selected according to the actual use.
Alternatively, the electrolyte may be selected from at least one of lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorooxalato borate, lithium bistrifluoromethylsulfonyl imide, lithium difluorobisoxalato phosphate, lithium tetrafluoroborate, lithium bisoxalato borate, lithium hexafluoroantimonate, lithium hexafluoroarsonate, lithium bis (pentafluoroethylsulfonyl) imide, lithium tris (trifluoromethylsulfonyl) methyllithium, and lithium bis (trifluoromethylsulfonyl) imide. For example, the electrolyte may be selected from lithium hexafluorophosphate and lithium bistrifluoromethylsulfonylimide, and the specific kind of electrolyte may be selected according to the actual use.
Alternatively, the solvent may include at least one of a carbonate and a carboxylate, and the carbonate may include at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethylmethyl carbonate; the carboxylic acid ester may include at least one of propyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, propyl propionate, ethyl propionate, methyl butyrate, and ethyl n-butyrate. For example, the solvent may include ethylene carbonate, propyl acetate, and the specific kind of solvent may be selected according to the practice.
Optionally, the electrolyte may further include: at least one of 1,3, 6-hexanetrinitrile and 1, 3-propane sultone.
The battery of the embodiment of the invention comprises the electrolyte described in the embodiment. The battery having the electrolyte described in the above examples has excellent high-temperature cycle performance and high-temperature storage performance.
The electrolyte can be used for a lithium ion battery, and the battery can be a lithium ion battery. The lithium ion battery may further include a positive electrode sheet containing a positive electrode active material, a negative electrode sheet containing a negative electrode active material, and a separator. The positive electrode sheet may include a positive electrode current collector and a positive electrode active material layer coated on one or both side surfaces of the positive electrode current collector, and the positive electrode active material layer may include a positive electrode active material, a conductive agent, and a binder. The negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer coated on one or both side surfaces of the negative electrode current collector, the negative electrode active material layer including a negative electrode active material, a conductive agent, and a binder. The positive electrode active material layer may include the following components in percentage by mass: 80-99.8wt% of positive electrode active material, 0.1-10wt% of conductive agent, and 0.1-10wt% of binder. The positive electrode active material layer may include the following components in percentage by mass: 90-99.6wt% of positive electrode active material, 0.2-5wt% of conductive agent and 0.2-5wt% of binder. The mass percentage of each component in the anode active material layer can be as follows: 80-99.8wt% of negative electrode active material, 0.1-10wt% of conductive agent, and 0.1-10wt% of binder. The mass percentage of each component in the anode active material layer can be as follows: 90-99.6wt% of negative electrode active material, 0.2-5wt% of conductive agent and 0.2-5wt% of binder. The conductive agent is selected from conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fiber, carbon nanotube, and combinations thereof,At least one of metal powder and carbon fiber. The binder may be at least one selected from sodium carboxymethyl cellulose, styrene-butadiene latex, polytetrafluoroethylene, and polyethylene oxide. The negative electrode active material may be artificial graphite, silicon carbon/graphite, silicon oxygen/graphite. The carbon-based negative electrode material may include at least one of artificial graphite, natural graphite, mesophase carbon microspheres, hard carbon, and soft carbon. The positive electrode active material can be selected from one or more of transition metal lithium oxide, lithium iron phosphate and lithium manganate, and the chemical formula of the transition metal lithium oxide can be Li 1+x Ni y Co z M (1-y-z) O 2 Wherein, -0.1 is less than or equal to x is less than or equal to 1,0 is less than or equal to y is less than or equal to 1,0 is less than or equal to z is less than or equal to 1, and 0 is less than or equal to y+z is less than or equal to 1; wherein M may be one or more of Mg, zn, ga, ba, al, fe, cr, sn, V, mn, sc, ti, nb, mo, zr.
The invention will be further illustrated with reference to a few specific examples.
Example 1
Preparing a positive plate:
lithium cobalt oxide (LiCoO) as a positive electrode active material 2 ) Mixing polyvinylidene fluoride (PVDF), conductive carbon black (SP, super P) and Carbon Nano Tube (CNT) according to the mass ratio of 96:2:1.5:0.5, adding N-methyl pyrrolidone (NMP), and stirring under the action of a vacuum stirrer until the mixed system becomes anode active slurry with uniform fluidity; uniformly coating anode active slurry on two surfaces of an aluminum foil; and drying the coated aluminum foil, and then rolling and slitting to obtain the required positive plate.
Preparing a negative electrode sheet:
the negative electrode active material artificial graphite, sodium carboxymethylcellulose (CMC-Na), styrene-butadiene rubber, conductive carbon black (SP) and single-walled carbon nanotubes (SWCNTs) are mixed according to the mass ratio of 94.5:2.5:1.5:1:0.5, deionized water is added, and negative electrode active slurry is obtained under the action of a vacuum stirrer; uniformly coating the anode active slurry on two surfaces of a copper foil; and (3) airing the coated copper foil at room temperature, transferring to an 80 ℃ oven for drying for 10 hours, and then carrying out cold pressing and slitting to obtain the negative plate.
Preparation of electrolyte:
example 1
Electrolyte, solvent and additive are mixed to obtain electrolyte, and the components in the electrolyte (based on 100% of the total mass of the electrolyte) are as follows:
organic solvent: ethylene carbonate 5%, propylene carbonate 10%, propyl acetate 15%, propyl propionate 47%, total 77%;
electrolyte lithium salt: lithium hexafluorophosphate (LiPF) 6 )，13％；
A first additive: structural formulas 1-3,1%;
and a second additive: structural formula 2-3,4%;
third additive: structural formula 3-37,5%;
preparation of a lithium ion battery:
laminating the prepared positive plate, the prepared negative plate and the prepared isolating film according to the sequence of the positive plate, the prepared isolating film and the prepared negative plate, and then winding to obtain the battery cell; and placing the battery core in an outer packaging aluminum foil, injecting the electrolyte into the outer packaging, and performing the procedures of vacuum packaging, standing, formation, shaping, sorting and the like to obtain the lithium ion battery. The charge and discharge range of the battery can be 3.0-4.5V.
The main difference between examples 2-32 and comparative examples 1 and 1 is that the additive types and amounts are different, and when the additive amounts of the above examples and comparative examples are changed, the missing or increased mass ratio can be supplemented by increasing or decreasing the propyl propionate content in the organic solvent, so as to ensure that the mass ratio of other components is unchanged. The specific components and amounts of the other examples and comparative examples can be as shown in table 1.
TABLE 1 Components and contents in electrolytes in examples and comparative examples
Performance test of the batteries in the above examples and comparative examples
1) 45 ℃ cycle performance test
The batteries in the above examples and comparative examples were subjected to charge-discharge cycles at 45 ℃ in a charge-discharge cutoff voltage range at a rate of 1C for 1000 weeks, the discharge capacity at the 1 st week was measured as x1 mAh, and the discharge capacity at the nth week was measured as y1 mAh; the capacity at week N divided by the capacity at week 1 gives the cyclic capacity retention rate at week N r1=y1/x 1.
2) 85 ℃ high temperature storage test
Firstly, standing the battery with the chemical components for 10min, then standing for 10min at 0.2C and 3V, then fully charging at 0.5C, stopping at 0.05C, and standing for 10min. And testing the voltage, the internal resistance and the thickness of the full-charge state at the temperature of 25+/-5 ℃, placing the full-charge state in an oven at the temperature of 85 ℃ for 8 hours, taking out the voltage, the internal resistance and the thickness of the thermal state battery, and performing capacity retention and recovery tests.
The lithium ion batteries obtained in examples and comparative examples were subjected to 45 ℃ cycle performance test and 85 ℃ storage performance test, respectively, and the test results are shown in table 2 below.
Table 2 performance test of lithium ion batteries in examples and comparative examples
From the experimental data, the additive in the electrolyte can improve the high-temperature cycle and high-temperature storage performance of the battery.
While the present invention has been described with reference to the above-described embodiments, it is to be understood that the same is not limited to the above-described embodiments, but rather that the same is intended to be illustrative only, and that many modifications may be made by one of ordinary skill in the art without departing from the spirit of the invention and scope of the appended claims.
Claims (10)
1. An electrolyte, comprising:
at least one of the first additive and the second additive, a solvent and an electrolyte;
the structural formula of the first additive is shown as a structural formula (1):
wherein n is a positive integer, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Independently selected from one of alkane with 1-20 carbon atoms, halogenated alkane or halogen atom;
the second additive is selected from at least one of the structural formula (2) and the structural formula (3),
wherein a, b, c, d, e, f is a positive integer.
2. The electrolyte of claim 1, wherein the first additive is selected from at least one of structural formulas 1-1 to 1-5,
3. the electrolyte of claim 1, wherein the electrolyte comprises a first additive, the first additive being present in an amount of 0.1% to 10% by mass of the electrolyte.
4. The electrolyte according to any one of claims 1 to 3, wherein the second additive is selected from at least one of structural formulae 2 to 1 to 2 to 4,
5. the electrolyte of any one of claims 1-3, wherein the electrolyte comprises a second additive, the mass of the second additive being 0.5% -10% of the mass of the electrolyte.
6. The electrolyte of claim 1, further comprising:
a third additive, the structural formula of the third additive is
R 7 、R 8 、R 9 、R 10 、R 11 、R 12 Independently selected from C substituted or unsubstituted with halogen 1 -C 20 C which is substituted or unsubstituted by halogen, is an alkanyl, unsaturated alkenyl, or C which is substituted or unsubstituted by halogen 3 -C 20 Cycloalkyl of (C), phenyl substituted or unsubstituted by halogen, biphenyl substituted or unsubstituted by halogen, C substituted or unsubstituted by halogen 6 -C 26 A phenylalkyl group of (C), a condensed ring aromatic hydrocarbon group substituted or unsubstituted by halogen, a hydrogen atom.
7. The electrolyte of claim 6, wherein the third additive is selected from at least one of structural formulas 3-1 to 3-40,
8. the electrolyte of claim 6, wherein the mass of the third additive is 1% -10% of the mass of the electrolyte.
9. The electrolyte of claim 1, wherein the electrolyte is selected from at least one of lithium hexafluorophosphate, lithium difluorophosphate, lithium difluorooxalato borate, lithium bistrifluoromethylsulfonyl imide, lithium difluorobisoxalato phosphate, lithium tetrafluoroborate, lithium bisoxalato borate, lithium hexafluoroantimonate, lithium hexafluoroarsonate, lithium bis (pentafluoroethylsulfonyl) imide, lithium tris (trifluoromethylsulfonyl) methyl lithium, and lithium bis (trifluoromethylsulfonyl) imide; and/or
The solvent comprises at least one of carbonate and carboxylate, wherein the carbonate comprises at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate; the carboxylic acid ester comprises at least one of propyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, propyl propionate, ethyl propionate, methyl butyrate and ethyl n-butyrate; and/or
The electrolyte further comprises: at least one of 1,3, 6-hexanetrinitrile and 1, 3-propane sultone.
10. A battery comprising the electrolyte of any one of claims 1-9.
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| CN202310522200.2A CN116365035A (en) | 2023-05-10 | 2023-05-10 | Electrolyte and battery |
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