CN111755747B - Non-aqueous electrolyte, battery containing non-aqueous electrolyte and vehicle containing battery - Google Patents
Non-aqueous electrolyte, battery containing non-aqueous electrolyte and vehicle containing battery Download PDFInfo
- Publication number
- CN111755747B CN111755747B CN201910246456.9A CN201910246456A CN111755747B CN 111755747 B CN111755747 B CN 111755747B CN 201910246456 A CN201910246456 A CN 201910246456A CN 111755747 B CN111755747 B CN 111755747B
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- China
- Prior art keywords
- additive
- electrolytic solution
- carbonate
- nonaqueous electrolytic
- group
- Prior art date
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 31
- 239000002687 nonaqueous vehicle Substances 0.000 title description 2
- 239000000654 additive Substances 0.000 claims abstract description 63
- 230000000996 additive effect Effects 0.000 claims abstract description 60
- -1 3, 5-dimethylpyridin-4-yl Chemical group 0.000 claims description 37
- 239000008151 electrolyte solution Substances 0.000 claims description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims description 13
- 159000000002 lithium salts Chemical class 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- 125000001188 haloalkyl group Chemical group 0.000 claims description 7
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 125000005059 halophenyl group Chemical group 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 4
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 4
- DVCMYAIUSOSIQP-UHFFFAOYSA-N phenyl 2,2,2-trifluoroacetate Chemical compound FC(F)(F)C(=O)OC1=CC=CC=C1 DVCMYAIUSOSIQP-UHFFFAOYSA-N 0.000 claims description 4
- XJYDIOOQMIRSSY-UHFFFAOYSA-N 1,3,2-dioxathiepane 2-oxide Chemical compound O=S1OCCCCO1 XJYDIOOQMIRSSY-UHFFFAOYSA-N 0.000 claims description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 3
- OQXNUCOGMMHHNA-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2,2-dioxide Chemical compound CC1COS(=O)(=O)O1 OQXNUCOGMMHHNA-UHFFFAOYSA-N 0.000 claims description 3
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 3
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910010088 LiAlO4 Inorganic materials 0.000 claims description 3
- 229910013188 LiBOB Inorganic materials 0.000 claims description 3
- 229910001559 LiC4F9SO3 Inorganic materials 0.000 claims description 3
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 3
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 3
- NVJBFARDFTXOTO-UHFFFAOYSA-N diethyl sulfite Chemical compound CCOS(=O)OCC NVJBFARDFTXOTO-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 claims description 3
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 3
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 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
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 3
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 150000008053 sultones Chemical class 0.000 claims description 3
- HDYQLGLEPPGPEV-UHFFFAOYSA-N benzyl 2,2,2-trifluoroacetate Chemical compound FC(F)(F)C(=O)OCC1=CC=CC=C1 HDYQLGLEPPGPEV-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- HYZVAVYBDNKXDG-UHFFFAOYSA-N 4-bromo-3,5-dimethylpyridine Chemical compound CC1=CN=CC(C)=C1Br HYZVAVYBDNKXDG-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 238000006864 oxidative decomposition reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical class OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003222 pyridines Chemical group 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 1
- FNRMMDCDHWCQTH-UHFFFAOYSA-N 2-chloropyridine;3-chloropyridine;4-chloropyridine Chemical compound ClC1=CC=NC=C1.ClC1=CC=CN=C1.ClC1=CC=CC=N1 FNRMMDCDHWCQTH-UHFFFAOYSA-N 0.000 description 1
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- MTAODLNXWYIKSO-UHFFFAOYSA-N 2-fluoropyridine Chemical compound FC1=CC=CC=N1 MTAODLNXWYIKSO-UHFFFAOYSA-N 0.000 description 1
- CCZWSTFVHJPCEM-UHFFFAOYSA-N 2-iodopyridine Chemical compound IC1=CC=CC=N1 CCZWSTFVHJPCEM-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 125000005921 isopentoxy group Chemical group 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
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([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
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VMVNZNXAVJHNDJ-UHFFFAOYSA-N methyl 2,2,2-trifluoroacetate Chemical group COC(=O)C(F)(F)F VMVNZNXAVJHNDJ-UHFFFAOYSA-N 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 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
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 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
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 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
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a non-aqueous electrolyte, a battery containing the non-aqueous electrolyte and a vehicle containing the battery. When the electrolyte is applied to a battery, the additive can form a film on the surfaces of a positive electrode and a negative electrode at the same time, and the battery still shows good cycle performance at a high voltage of 4.95V, so that the electrolyte shows better high-temperature stability and high-pressure stability than the electrolyte added with the film-forming additive in the prior art.
Description
Technical Field
The present invention relates to the field of nonaqueous electrolytic solutions, and particularly to a nonaqueous electrolytic solution, a battery containing the same, and a vehicle containing the battery.
Background
Since the 90 s of the 20 th century, lithium ion secondary batteries have reached a rapid development from birth. Generally, a lithium ion battery with a non-aqueous solute includes a lithium negative electrode, a lithium salt dissolved in an organic solvent, and an electrochemically active positive electrode material. During charging, lithium ions migrate from the positive electrode through the electrolyte to the negative electrode, while during discharging they flow in the opposite direction. In recent years, secondary lithium ion batteries with high energy density have been the subject of attention, and therefore, new active materials that can be used as secondary lithium batteries have been also noticed. Under the continuous reform and update of power batteries, more and more battery materials with higher energy density and higher application voltage are paid more and more attention, the electrolyte matched with a high-energy-density electrode material also becomes important, and the problem of the operation of the battery under high voltage is that the electrolyte can have parasitic reaction (generally oxidation decomposition reaction) with an anode interface, so that the service life of the battery is reduced. The key point of continuous research at present is to promote the oxidative decomposition potential of the electrolyte and to form a film on the surface of the anode to hinder the decomposition of the electrolyte under the influence of an anode interface, wherein the oxidative decomposition potential of the electrolyte is mainly promoted by seeking a novel solvent or an additive, so that the oxidative stability of the whole electrolyte system is reduced or reduced, the overall stability of the electrolyte is further promoted, the reduction of the oxidative reaction reduces the decomposition of the electrolyte, the sufficiency of the electrolyte in the circulating process is ensured, and the service life of the battery is prolonged; the latter is mostly electrolyte of additive type, choose one or several sacrificial additives, can take place oxidative decomposition reaction and form a membranous layer that can hinder electrolyte and anodal side reaction in advance before the electrolyte takes place to decompose, hinder the further decomposition of electrolyte, in order to promote the life-span of the battery.
The research of novel high voltage electrolyte is numerous, use the current system of novel solvent replacement more, have certain problem, if the conductivity is low, or have shortcomings such as viscosity big, and it is also a good compromise to use the additive to improve, present most additive all uses the oxidative decomposition electric potential that improves whole electrolyte system as the starting point, therefore can have in the electrolyte a small amount of solvent still can oxidative decomposition's possibility under the high potential to cause the electrolyte finally still to be consumed totally, cause the battery cycle in-process to take place the capacity and jump water. The positive electrode film forming additive also has the defects that the film layer is damaged due to the corrosion of the electrolyte when contacting with the electrolyte.
Disclosure of Invention
In order to solve the above problems, the present application provides a nonaqueous electrolytic solution including a lithium salt, a first organic solvent, and a first additive, the first additive having the following structural formula:
wherein, R1, R2, R3 and R4 are respectively and independently selected from one of hydrogen atom, alkyl, halogenated alkyl, alkoxy and halogen atom; r5 is selected from one of alkyl, haloalkoxy, phenyl and halophenyl; wherein the halogen is F, Cl, Br and I; n is 0 to 5 and is an integer.
Optionally, R1, R2, R3 and R4 are independently selected from alkyl with 1-5 carbon atoms, halogenated alkyl with 1-5 carbon atoms and alkoxy with 1-5 carbon atoms; r5 is one selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, a phenyl group and a halophenyl group.
Optionally, the first additive is one or more of 4- (3, 5-dimethylpyridin-4-yl) phenyl trifluoroacetate, 4- (3, 5-dimethylpyridin-4-yl) phenyl trifluoropropionate, 4- (3, 5-dimethylpyridin-4-yl) phenyl trimethyi-noate, 4- (3, 5-dimethylpyridin-4-yl) benzyl trifluoroacetate, and 4- (3, 5-dimethylpyridin-4-yl) benzyl trifluoropropionate.
Optionally, the content of the additive is 0.1-10% based on the total mass of the nonaqueous electrolyte.
Optionally, the nonaqueous electrolyte further contains a second additive, and the second additive includes one or more of 1, 3-propane sultone, 1, 4-butane sultone, propenyl-1, 3-sultone, ethylene sulfate, propylene sulfate, butylene sulfite, vinylene carbonate, fluoroethylene carbonate, lithium bis (fluorosulfonyl) imide in bis (oxalato) borate.
Optionally, the content of the second additive is 0.05% to 20% based on the total mass of the nonaqueous electrolyte.
Optionally, the first organic solvent is one or more selected from dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, dipropyl carbonate, ethylene carbonate, propylene carbonate, vinylene carbonate, gamma-butyrolactone, sultone, ethylene sulfite, propylene sulfite, methyl sulfide, diethyl sulfite, methyl formate, methyl acrylate, methyl butyrate and ethyl acetate.
Optionally, the lithium salt is selected from one or more of LiBOB, LiPF6, LiBF4, LiSbF6, LiClO4, LiCF3SO3, Li (CF3SO2)2N, LiC4F9SO3, LiAlO4, LiAsF6, LiAlCl4, LiCl, LiI and low fatty acid lithium carbonate, and the concentration of the lithium salt is 0.3 to 3 mol/L.
A second object of the present invention is to provide a battery including a battery case, and a cell and a nonaqueous electrolytic solution sealed in the battery case, the cell including a positive electrode, a negative electrode, and a separator, wherein the nonaqueous electrolytic solution is the above-mentioned nonaqueous electrolytic solution.
A third object of the invention is to provide a vehicle that contains the above battery.
Compared with the prior art, the invention has the beneficial effects that: the first additive is added into the non-aqueous electrolyte, the non-aqueous electrolyte is applied to a battery, the battery has good cycle performance under the high voltage of 4.95V, films can be formed on the surfaces of a positive electrode and a negative electrode at the same time, the structure of the first additive can prevent the electrolyte and other harmful substances from contacting with the films, the degradation of the electrolyte can be effectively reduced, the positive electrode and the negative electrode are protected from being influenced, the content of the electrolyte and the stability of an electrode material are ensured, and the service life of the battery is prolonged.
Detailed Description
The application provides a nonaqueous electrolyte, which contains a lithium salt, a first organic solvent and a first additive, wherein the first additive has the following structural formula:
wherein, R1, R2, R3 and R4 are respectively and independently selected from one of hydrogen atom, alkyl, halogenated alkyl, alkoxy and halogen atom; r5 is selected from one of alkyl, haloalkoxy, phenyl and halophenyl; wherein the halogen is F, Cl, Br and I; n is 0 to 5 and is an integer.
The molecular structure of the first additive used in the invention contains two functional groups of pyridine and ester group, and the two functional groups are distributed at two ends of the structure. Such additives are capable of undergoing redox on the electrode in preference to the solvent. When the ester group at one end is reduced to form a film on the negative electrode, the unreacted pyridine part at the other end can effectively prevent electrolyte solvent molecules from approaching the negative electrode, and can complex transition metal ions and acidic substances to prevent the transition metal ions and the acidic substances from depositing and damaging active materials on the negative electrode. When pyridine at one end is oxidized on the anode to form a film, unreacted ester group at the other end can also effectively prevent electrolyte solvent molecules from approaching the anode and consuming hydrofluoric acid (HF) generated in a system, so that the contact of the electrolyte and the anode and cathode film layers is blocked, the anode and cathode film layers are protected, the decomposition of the electrolyte is inhibited, and the cycle life of the battery is effectively prolonged.
According to the nonaqueous electrolytic solution provided by the present application, in the structural formula of the first additive, R1, R2, R3 and R4 may be the same or different, and the present application is not particularly limited.
When R1, R2, R3 and R4 are each independently selected from alkyl groups, they may be chain haloalkyl groups or cyclic alkyl groups, and the chain alkyl groups may be branched or straight-chain; preferably, an alkyl group having 1 to 5 carbon atoms is selected, and as examples of the alkyl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an n-pentyl group, an isopentyl group, and the like can be cited.
When R1, R2, R3 and R4 are each independently selected from haloalkyl groups, they may be a chain haloalkyl group or a cyclic haloalkyl group, and the chain haloalkyl group may be branched or straight; preferably, a halogenated alkyl group with the carbon number of 1-5 is selected, and further preferably, the halogenated alkyl group is a halogenated methyl group or a halogenated ethyl group, and after a plurality of experiments, the inventor of the application finds that the carbon chain length is related to the solubility, the longer the carbon chain is, the higher the non-polarity degree of the additive is, while the electrolyte is highly polar, and according to the principle of similar compatibility, the carbon chain length of the additive is too long, and the solubility of the additive is deteriorated; when the alkyl group is substituted with a halogen atom, all or part of the hydrogen atoms may be substituted.
As examples of the haloalkyl group, there may be mentioned trifluoromethyl, 2-fluoroethyl, 3-fluoro-n-propyl, 2-fluoroisopropyl, 4-fluoro-n-butyl, 3-fluoro-sec-butyl, 5-fluoro-n-pentyl, 4-fluoro-isopentyl and the like, and in the above specific examples, F may be substituted with Cl or Br or I.
When R1, R2, R3, and R4 are each independently selected from alkoxy groups, they may be chain alkoxy groups or cyclic alkoxy groups, and the chain alkoxy groups may be branched or straight; preferably, an alkoxy group having 1 to 5 carbon atoms is selected, and as examples of the alkoxy group, specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, n-pentoxy group, isopentoxy group, etc. can be mentioned, and it has been found through many experiments that the film forming property of the first additive is more preferable when the alkoxy group is more preferably one of methoxy group, ethoxy group and propoxy group.
When R5 is selected from alkyl, reference is made to the above description and no further description is given here.
When R5 is selected from haloalkoxy, it may be a chain haloalkoxy group, or a cyclic haloalkoxy group, and the chain haloalkoxy group may be branched or linear; preferably, the halogenated alkoxy group with the carbon number of 1-5 is selected, and further preferably, the halogenated alkoxy group is halogenated methoxy or halogenated ethoxy, and after a plurality of experiments, the inventor of the application finds that the carbon chain length is related to the solubility, the longer the carbon chain is, the higher the non-polarity degree of the additive is, while the electrolyte is highly polar, and according to the principle of similar compatibility, the carbon chain length of the additive is too long, and the solubility of the additive is deteriorated; when the halogen atom is substituted for the alkoxy group, all or part of the hydrogen atoms may be substituted.
As examples of the haloalkoxy group, there may be specifically mentioned trifluoromethoxy, 2-fluoroethoxy, 3-fluoro-n-propoxy, 2-fluoro-isopropoxy, 4-fluoro-n-butoxy, 3-fluoro-sec-butoxy, 5-fluoro-n-pentyloxy, 4-fluoro-isopentyloxy and the like, and in the above specific examples, F may be substituted by Cl or Br or I.
When R5 is selected from the group consisting of halophenyl, it may be ortho-substituted, meta-substituted or para-substituted, and the present application is not particularly limited.
Specifically, the first additive is one or more of 4- (3, 5-dimethylpyridin-4-yl) phenyl trifluoroacetate, - (3, 5-dimethylpyridin-4-yl) phenyl trifluoropropionate, 4- (3, 5-dimethylpyridin-4-yl) phenyl trimethyi-noate, 4- (3, 5-dimethylpyridin-4-yl) benzyl trifluoroacetate, and 4- (3, 5-dimethylpyridin-4-yl) benzyl trifluoropropionate.
According to the nonaqueous electrolytic solution of the present invention, one kind of the first additive may be added alone, or a plurality of kinds of the first additives may be added simultaneously. The content of the first additive is 0.1-10% based on the total mass of the non-aqueous electrolyte, and the first additive with the content is added into the electrolyte, so that a good film forming effect can be achieved, and the performance of the battery cannot be greatly influenced.
According to the nonaqueous electrolytic solution of the present invention, preferably, the nonaqueous electrolytic solution further contains a second additive, and the second additive includes at least one of 1,3 propane sultone, 1,4 butane sultone, propenyl-1, 3-sultone, vinyl sulfate, propylene sulfate, butylene sulfite, vinylene carbonate, fluoroethylene carbonate, lithium bis (fluorosulfonyl) imide. The additive and the film forming additive are jointly applied to the electrolyte, so that the stability of the battery is better.
The content of the second additive can be 0.05-20 wt% relative to 100 wt% of the nonaqueous solvent, the second additive can promote the first additive to form a stable SEI film on the surface of the negative electrode, and can protect the negative electrode, so that the cycle performance of the battery is further improved, but the second additive is excessively added to cause excessive consumption of active lithium.
According to the provided nonaqueous electrolytic solution of the present invention, the first organic solvent may use a nonaqueous solvent conventionally used by those skilled in the art, and may include, for example, one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, dipropyl carbonate, ethylene carbonate, propylene carbonate, vinylene carbonate, γ -butyrolactone, sultone, ethylene sulfite, propylene sulfite, methyl sulfide, diethyl sulfite, methyl formate, methyl acrylate, methyl butyrate, and ethyl acetate.
The nonaqueous electrolytic solution according to the present invention, wherein the selection of the lithium salt is not particularly required, may be a lithium salt conventionally used in a nonaqueous electrolytic solution, and may include, for example, one or more of LiBOB, LiPF6, LiBF4, LiSbF6, LiClO4, LiCF3SO3, Li (CF3SO2)2N, LiC4F9SO3, LiAlO4, LiAsF6, LiAlCl4, LiCl, LiI, and low-fatty-acid lithium carbonate. The concentration of the lithium salt is known to those skilled in the art and is generally 0.3 to 3mol/L, preferably 0.8 to 1.2 mol/L.
The first additive described herein can be prepared by the following steps.
Uniformly mixing halogenated pyridine, ester group substituted phenylboronic acid, an alkaline solution and a catalyst in a second solvent, heating and refluxing under the protection of inert gas, reacting for 12-24 h, cooling, extracting, drying and purifying to obtain the first additive.
The halogenated pyridine is one of bromopyridine, fluoropyridine, iodopyridine and chloropyridine, bromopyridine is preferred, the reaction activity is high, and the raw materials are easy to obtain.
The alkaline solution is one or more of sodium carbonate, sodium bicarbonate and cesium carbonate, and the purpose of the alkaline solution is to neutralize acidic byproducts in reaction products in time so as to promote the whole reaction system to proceed.
The catalyst is one or more of tetrakis (triphenylphosphine) palladium and palladium acetate.
The second solvent is one or more of toluene and tetrahydrofuran.
The inert gas is one or more of argon and nitrogen.
The preparation method of the non-aqueous electrolyte provided by the invention is a method conventionally used by those skilled in the art, namely, the components (including the lithium salt, the non-aqueous solvent, the first additive and/or the second additive) are uniformly mixed, and the mixing mode and the mixing sequence are not particularly limited in the invention. For example, the first organic solvent may be mixed uniformly, then the lithium salt may be added and mixed uniformly, and then the first additive may be added and mixed uniformly, or the second additive may be added together with the first additive.
The invention also provides a power battery which comprises a battery shell, and a battery core and a non-aqueous electrolyte which are sealed in the battery shell.
The nonaqueous electrolyte solution is the nonaqueous electrolyte solution, and the battery cell comprises a positive electrode, a negative electrode and a diaphragm. Since the present invention relates to only the improvement of the nonaqueous electrolyte of the battery in the prior art, other compositions and structures of the battery are not particularly limited, and are well known to those skilled in the art, and will not be described herein again.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
(1) Preparation of the first additive
Dissolving 3, 5-dimethyl-4-bromopyridine, 4- (trifluoroacetate) phenylboronic acid and tetrakis (triphenylphosphine) palladium in toluene, uniformly mixing, then adding a sodium carbonate aqueous solution (2.0mol/L), and refluxing for 24 hours under the protection of argon (inert gas), wherein the reaction temperature is 120 ℃. After the reaction is finished, cooling the mixture solution to room temperature, extracting with ethyl acetate, drying an organic phase with anhydrous magnesium sulfate, spin-drying a solvent to obtain a crude product, and separating by column chromatography to obtain a pure product of 4- (3, 5-dimethylpyridine-4-yl) phenyl trifluoroacetate, wherein the structural formula of the pure product is as follows:
(2) preparation of nonaqueous electrolyte:
the nonaqueous electrolyte solution for the lithium ion battery of this example was obtained by uniformly mixing Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a mass ratio of 1:1 in an argon glove box to obtain a nonaqueous solvent, dissolving 12% by weight of lithium hexafluorophosphate (LiPF6) in 100% by weight of the nonaqueous solvent, and adding 0.1% by weight of 4- (3, 5-dimethylpyridin-4-yl) phenyltrifluoroacetate thereto, and was designated as C1.
(3) Preparing a lithium ion battery:
mixing a positive electrode active substance (LiNi0.5Mn1.5O4), acetylene black and polyvinylidene fluoride according to a mixture ratio of 90: 5: 5, uniformly mixing, and pressing on an aluminum foil to obtain a positive plate; taking a metal lithium sheet as a negative plate; the button cell S1 is prepared by taking a PE/PP composite diaphragm as an ion exchange membrane, adopting the non-aqueous electrolyte C1 of the embodiment and adopting a conventional method in the field.
Example 2
Preparation of the first additive:
dissolving 3, 5-dimethyl-4-bromopyridine, 4- (trifluoropropionate) phenylboronic acid and tetrakis (triphenylphosphine) palladium in toluene, uniformly mixing, then adding a sodium carbonate aqueous solution (2.0mol/L), and refluxing for 24 hours under the protection of argon (inert gas), wherein the reaction temperature is 120 ℃. After the reaction is finished, cooling the mixture solution to room temperature, extracting with ethyl acetate, drying an organic phase with anhydrous magnesium sulfate, spin-drying a solvent to obtain a crude product, and separating by column chromatography to obtain a pure product of 4- (3, 5-dimethylpyridine-4-yl) phenyl trifluoropropionate, wherein the structural formula of the pure product is as follows:
nonaqueous electrolyte and button cells were prepared by the same procedure as in example 1, except that: in the step (2), 0.1% by weight of 4- (3, 5-dimethylpyridin-4-yl) phenyltrifluoroacetate was replaced with 0.5% by weight of 4- (3, 5-dimethylpyridin-4-yl) phenyltrifluoropropionate, and a lithium ion battery nonaqueous electrolytic solution C2 and a button cell S2 were prepared.
Example 3
Preparation of the first additive:
dissolving 3, 5-dimethyl-4-bromopyridine, 4- (trimethylacetate) phenylboronic acid and tetrakis (triphenylphosphine) palladium in toluene, uniformly mixing, then adding a sodium carbonate aqueous solution (2.0mol/L), and refluxing for 24 hours under the protection of argon (inert gas), wherein the reaction temperature is 120 ℃. After the reaction is finished, the mixture solution is cooled to room temperature, ethyl acetate is used for extraction, an organic phase is dried by anhydrous magnesium sulfate, a crude product is obtained after the solvent is dried by spinning, and the pure product of the 4- (3, 5-dimethylpyridine-4-yl) phenyl trimethyl acetate is obtained through column chromatography separation. The structural formula is as follows:
nonaqueous electrolyte and button cells were prepared by the same procedure as in example 1, except that: in the step (2), the lithium ion battery non-aqueous electrolyte C3 and the button cell S3 are prepared by replacing 0.1% by weight of 4- (3, 5-dimethylpyridin-4-yl) phenyl trifluoroacetate with 1% by weight of 4- (3, 5-dimethylpyridin-4-yl) phenyl trimethylacetate.
Example 4
Preparation of the first additive:
3, 5-dimethyl-4-bromopyridine, 4- (trifluoroacetic acid methyl ester group) phenylboronic acid and tetrakis (triphenylphosphine) palladium are dissolved in toluene, mixed uniformly, and then added with a sodium carbonate aqueous solution (2.0mol/L) and refluxed for 24 hours under the protection of argon (inert gas), wherein the reaction temperature is 120 ℃. After the reaction is finished, cooling the mixture solution to room temperature, extracting with ethyl acetate, drying an organic phase with anhydrous magnesium sulfate, spin-drying a solvent to obtain a crude product, and separating by column chromatography to obtain a pure product of 4- (3, 5-dimethylpyridine-4-yl) benzyl trifluoroacetate, wherein the structural formula of the product is as follows:
nonaqueous electrolyte and button cells were prepared by the same procedure as in example 1, except that: in the step (1), 5 weight percent of 4- (3, 5-dimethylpyridin-4-yl) benzyltrifluoroacetate is used for replacing 0.1 weight percent of 4- (3, 5-dimethylpyridin-4-yl) phenyltrifluoroacetate, and a lithium ion battery non-aqueous electrolyte C4 and a button cell S4 are prepared.
Example 5
Preparation of the first additive:
3, 5-dimethyl-4-bromopyridine, 4- (trifluoro-methyl propionate) phenylboronic acid and tetrakis (triphenyl phosphorus) palladium are dissolved in toluene, and after uniform mixing, an aqueous solution of sodium carbonate (2.0mol/L) is added and refluxed for 24 hours under the protection of argon (inert gas), and the reaction temperature is 120 ℃. After the reaction is finished, cooling the mixture solution to room temperature, extracting with ethyl acetate, drying an organic phase with anhydrous magnesium sulfate, spin-drying a solvent to obtain a crude product, and separating by column chromatography to obtain a pure product of 4- (3, 5-dimethylpyridine-4-yl) benzyl trifluoropropionate, wherein the structural formula of the pure product is as follows:
nonaqueous electrolyte and button cells were prepared by the same procedure as in example 1, except that: and (2) adding 7% of 4- (3, 5-dimethylpyridin-4-yl) benzyl trifluoropropionate instead of 0.1% of 4- (3, 5-dimethylpyridin-4-yl) phenyl trifluoroacetate by weight in the step (1) to prepare a lithium ion battery non-aqueous electrolyte C5 and a button cell S5.
Comparative example 1
Nonaqueous electrolyte and button cells were prepared by the same procedure as in example 1, except that: and (2) preparing a lithium ion battery non-aqueous electrolyte DC1 and a button cell DS1 without using an ester additive containing pyridine in the step (1).
Performance testing
(1) Testing of battery charging and discharging performance
Each of the experimental button cells S1 to S5 and DS1 was discharged to 0.005V at a constant current of 0.1mA at room temperature, then charged to 1.5V at a constant current of 0.1mA, the discharge capacity and the charge capacity of the cell were recorded, and the charge-discharge efficiency (%) -charge capacity/discharge capacity × 100% was calculated. The test results are shown in table 1.
TABLE 1
(2) Battery cycling test
Charging the battery to 4.95V at constant current and constant voltage with 1C multiplying power (about 0.5mA) at normal temperature, stopping the charging with 0.05mA, then discharging to 3.0V with 0.5mA constant current, recording the first charging capacity and discharging capacity, and calculating the discharging efficiency (%); after the charge and discharge cycles were repeated 100 times in this manner, the discharge capacity at the 100 th cycle was recorded, and the capacity retention (%) after the cycles was calculated as discharge capacity at 100 cycles/first discharge capacity × 100%; the cut-off voltage was 4.95V. The test results are shown in table 2.
As can be seen from tables 1 and 2, the effect of the first additive of the present invention is apparent, the battery prepared using the above electrolyte has good charge and discharge performance test and cycle test, and the battery can be applied at a high voltage of 4.95V.
TABLE 2
Claims (10)
1. A nonaqueous electrolyte solution, comprising a lithium salt, a first organic solvent, and a first additive, wherein the first additive has the following structural formula:
wherein, R1, R2, R3 and R4 are respectively and independently selected from one of hydrogen atom, alkyl, halogenated alkyl, alkoxy and halogen atom; r5 is selected from one of alkyl, haloalkoxy, phenyl and halophenyl; wherein the halogen is F, Cl, Br and I; n is 0 to 5 and is an integer.
2. The nonaqueous electrolytic solution of claim 1, wherein R1, R2, R3 and R4 are each independently selected from an alkyl group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms; r5 is one selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, a phenyl group and a halophenyl group.
3. The nonaqueous electrolytic solution of claim 1, wherein the first additive is one or more of 4- (3, 5-dimethylpyridin-4-yl) phenyltrifluoroacetate, 4- (3, 5-dimethylpyridin-4-yl) phenyltrifluoropropionate, 4- (3, 5-dimethylpyridin-4-yl) phenyltrimethyiacetate, 4- (3, 5-dimethylpyridin-4-yl) benzyltrifluoroacetate, and 4- (3, 5-dimethylpyridin-4-yl) benzyltrifluoropropionate.
4. The nonaqueous electrolytic solution of claim 1, wherein the additive is contained in an amount of 0.1% to 10% based on the total mass of the nonaqueous electrolytic solution.
5. The nonaqueous electrolytic solution of claim 1, further comprising a second additive, wherein the second additive comprises one or more of 1,3 propane sultone, 1,4 butane sultone, propenyl-1, 3-sultone, vinyl sulfate, propylene sulfate, butylene sulfite, vinylene carbonate, fluoroethylene carbonate, lithium bis (fluorosulfonyl) imide and lithium bis (fluorosulfonyl) imide.
6. The nonaqueous electrolytic solution of claim 5, wherein the content of the second additive is 0.05% to 20% based on the total mass of the nonaqueous electrolytic solution.
7. The nonaqueous electrolytic solution of claim 1, wherein the first organic solvent is one or more selected from dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, dipropyl carbonate, ethylene carbonate, propylene carbonate, vinylene carbonate, gamma-butyrolactone, sultone, ethylene sulfite, propylene sulfite, methyl sulfide, diethyl sulfite, methyl formate, methyl acrylate, methyl butyrate and ethyl acetate.
8. The nonaqueous electrolytic solution of claim 1, wherein the lithium salt is one or more selected from the group consisting of LiBOB, LiPF6, LiBF4, LiSbF6, LiClO4, LiCF3SO3, Li (CF3SO2)2N, LiC4F9SO3, LiAlO4, LiAsF6, LiAlCl4, LiCl, LiI, and lithium carbonate low in fatty acid, and the concentration of the lithium salt is 0.3 to 3 mol/L.
9. A battery comprising a battery case, and a cell and a nonaqueous electrolytic solution sealed in the battery case, the cell comprising a positive electrode, a negative electrode and a separator, wherein the nonaqueous electrolytic solution is the nonaqueous electrolytic solution according to any one of claims 1 to 8.
10. A vehicle incorporating the battery of claim 9.
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