CN115799643A - Nonaqueous electrolyte solution, lithium ion battery, battery module, battery pack, and electric device - Google Patents
Nonaqueous electrolyte solution, lithium ion battery, battery module, battery pack, and electric device Download PDFInfo
- Publication number
- CN115799643A CN115799643A CN202310062091.0A CN202310062091A CN115799643A CN 115799643 A CN115799643 A CN 115799643A CN 202310062091 A CN202310062091 A CN 202310062091A CN 115799643 A CN115799643 A CN 115799643A
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- CN
- China
- Prior art keywords
- lithium
- formula
- chf
- lithium ion
- carbonate
- Prior art date
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 78
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 59
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 36
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 36
- 239000013538 functional additive Substances 0.000 claims abstract description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 153
- -1 vinylene difluorocarbonate Chemical compound 0.000 claims description 51
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 41
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 36
- 239000000654 additive Substances 0.000 claims description 32
- 229910052731 fluorine Inorganic materials 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 30
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 25
- 239000008151 electrolyte solution Substances 0.000 claims description 24
- 229910052744 lithium Inorganic materials 0.000 claims description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 19
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 12
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 125000004428 fluoroalkoxy group Chemical group 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 7
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012453 solvate Substances 0.000 claims description 6
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 5
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 5
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 5
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 4
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000006729 (C2-C5) alkenyl group Chemical group 0.000 claims description 3
- 125000006730 (C2-C5) alkynyl group Chemical group 0.000 claims description 3
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 claims description 3
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004146 energy storage Methods 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 claims description 2
- 125000006650 (C2-C4) alkynyl group Chemical group 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 2
- 150000005678 chain carbonates Chemical class 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical compound C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 claims 1
- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 26
- 238000003860 storage Methods 0.000 abstract description 15
- 230000000052 comparative effect Effects 0.000 description 60
- 238000006243 chemical reaction Methods 0.000 description 51
- 239000003792 electrolyte Substances 0.000 description 48
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 28
- 239000011737 fluorine Substances 0.000 description 28
- 239000007788 liquid Substances 0.000 description 26
- 238000003756 stirring Methods 0.000 description 22
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 20
- ITVPBBDAZKBMRP-UHFFFAOYSA-N chloro-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound OP(O)(Cl)=O ITVPBBDAZKBMRP-UHFFFAOYSA-N 0.000 description 20
- 125000001424 substituent group Chemical group 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 17
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 14
- 239000012043 crude product Substances 0.000 description 14
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 13
- ODNBVEIAQAZNNM-UHFFFAOYSA-N 1-(6-chloroimidazo[1,2-b]pyridazin-3-yl)ethanone Chemical compound C1=CC(Cl)=NN2C(C(=O)C)=CN=C21 ODNBVEIAQAZNNM-UHFFFAOYSA-N 0.000 description 12
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 12
- 229910019142 PO4 Inorganic materials 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000010452 phosphate Substances 0.000 description 12
- XJAAVVLEUZQVNJ-UHFFFAOYSA-N trifluoromethylphosphonic acid Chemical compound OP(O)(=O)C(F)(F)F XJAAVVLEUZQVNJ-UHFFFAOYSA-N 0.000 description 12
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 11
- 229910001873 dinitrogen Inorganic materials 0.000 description 10
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 10
- 238000005292 vacuum distillation Methods 0.000 description 10
- 125000003342 alkenyl group Chemical group 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 125000000304 alkynyl group Chemical group 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 8
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 7
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 7
- 125000004093 cyano group Chemical group *C#N 0.000 description 7
- 229910052805 deuterium Inorganic materials 0.000 description 7
- 125000004043 oxo group Chemical group O=* 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 7
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 6
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
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- 150000003949 imides Chemical class 0.000 description 6
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
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- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
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- 125000006267 biphenyl group Chemical group 0.000 description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
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- 125000003107 substituted aryl group Chemical group 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- ACSIXWWBWUQEHA-UHFFFAOYSA-N clodronic acid Chemical compound OP(O)(=O)C(Cl)(Cl)P(O)(O)=O ACSIXWWBWUQEHA-UHFFFAOYSA-N 0.000 description 3
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- UUTWQLLIVDODPQ-OWOJBTEDSA-N (e)-4,4,4-trifluorobut-2-en-1-ol Chemical compound OC\C=C\C(F)(F)F UUTWQLLIVDODPQ-OWOJBTEDSA-N 0.000 description 1
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
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- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
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- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
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- IARLISDOOLYUNK-UHFFFAOYSA-N O[PH2]=N Chemical compound O[PH2]=N IARLISDOOLYUNK-UHFFFAOYSA-N 0.000 description 1
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- GTTGLTZAOFBCRM-UHFFFAOYSA-N P(O)(O)(O)=O.C[SiH](C)C Chemical compound P(O)(O)(O)=O.C[SiH](C)C GTTGLTZAOFBCRM-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
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- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical group [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
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- 125000000707 boryl group Chemical group B* 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
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- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
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- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 1
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- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
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- 239000011572 manganese Substances 0.000 description 1
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- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical compound C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 description 1
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
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Images
Classifications
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- 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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- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of batteries, in particular to a non-aqueous electrolyte, a lithium ion battery, a battery module, a battery pack and an electric device. Wherein the non-aqueous electrolyte comprises a lithium salt, a solvent and a functional additive, the functional additive comprises a compound with a structure shown in a formula I,
(I) is provided. The lithium ion battery applying the non-aqueous electrolyte has improved comprehensive properties such as rate capability, high-temperature cycle performance, high-temperature storage performance, high-temperature and low-temperature performance and safety performance.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a non-aqueous electrolyte, a lithium ion battery, a battery module, a battery pack and an electric device.
Background
In order to deal with the problems of increasingly severe environmental pollution and energy crisis, the demand of people for green energy is continuously rising. With the rapid development of clean energy in recent years, such as the large-area popularization and application of electric automobiles, mobile electronic devices, home-type intelligence and energy storage systems, the requirements for the comprehensive performance of lithium ion batteries are increasingly improved, and meanwhile, the requirements for the safety and the stability of battery devices are greatly improved, so that the abuse of the batteries is prevented, and the service lives of the batteries are prolonged. Generally, the introduction of functional additives into the electrolyte is considered to be one of the effective ways to improve the overall performance of lithium ion batteries. However, the electrolyte with single function or complex formulation combination can cause insufficient battery performance and can not achieve the purpose of use.
Therefore, there is a need to develop an electrolyte solution, which includes a specific additive or a combination of additives, so that when the electrolyte solution is used in a battery, the high-temperature storage performance, rate capability, low-temperature performance and cycle performance of a lithium ion battery can be effectively improved, and the safety performance of the lithium ion battery can be simultaneously considered.
Disclosure of Invention
In view of the above drawbacks of the prior art, an object of the present invention is to provide a nonaqueous electrolyte solution and a lithium ion battery using the same, wherein the nonaqueous electrolyte solution includes a compound having the structure shown in formula i, and generates a synergistic effect with other effective components in the electrolyte solution, so that a solid electrolyte interface with a compact, uniform and stable structure can be formed on the surfaces of a positive electrode and a negative electrode, the high-temperature storage performance, the rate capability, the low-temperature performance and the cycle performance of the lithium ion battery can be effectively improved, and free radicals can be effectively captured in time during high-temperature combustion to generate a flame retardant effect, thereby improving the safety performance of the lithium ion battery.
In order to achieve the above objects and other related objects, a first aspect of the present invention provides a nonaqueous electrolytic solution, including a lithium salt, a nonaqueous organic solvent, and a functional additive, the functional additive including a compound having a structure represented by formula i or a salt, polymorph, or solvate thereof;
Ⅰ
wherein: r F Selected from C1-C5 fluorine-containing alkyl, C1-C5 fluorine-containing alkoxy or-F; r 1 、R 2 Each independently selected from substituted or unsubstituted C2-C5 alkenyl, substituted or unsubstituted C2-C5 alkynyl, or substituted or unsubstituted C6-C10 aryl.
The second aspect of the present invention provides a method for preparing a nonaqueous electrolytic solution, comprising mixing a nonaqueous organic solvent, a lithium salt and a functional additive; the preparation method of the compound with the structure shown in the formula I comprises the following steps:
1) Mixing phosphorus oxychloride and anhydrous dichloromethane, and sequentially adding R in the inert gas atmosphere 1 OH solution and R 2 Reacting an OH solution to obtain a compound shown in a formula I;
ⅠⅠ
2) Reacting the compound of formula I in the step 1) with a fluoro reagent to obtain a compound of formula I; wherein R is 1 、R 2 As defined in the first aspect of the invention.
A third aspect of the present invention provides a lithium ion battery comprising a positive electrode, a negative electrode, a separator provided at an interval between the positive electrode and the negative electrode, and the nonaqueous electrolytic solution of the first aspect of the present invention.
A fourth aspect of the invention provides a battery module comprising the lithium ion battery of the third aspect of the invention.
A fifth aspect of the invention provides a battery pack including the battery module according to the fourth aspect of the invention.
A sixth aspect of the present invention provides an electric device including the lithium ion battery according to the third aspect of the present invention, the lithium ion battery being used as a power source of the electric device.
Compared with the prior art, the invention has the beneficial effects that: (1) The invention adopts the fluorine-containing phosphate compound with the structure shown in the formula I as the electrolyte additive, wherein the fluorine-containing phosphate compound can effectively improve the flame retardant property of the battery cell. The phosphate flame retardant additive is used independently, so that the viscosity of the electrolyte is increased, the conductivity of the electrolyte is reduced, and the performance of the lithium ion battery is influenced; the fluorine element is introduced into the phosphate flame-retardant additive, so that the viscosity of the phosphate is effectively reduced, the ionic conductivity of the electrolyte is improved, and the performance of the lithium ion battery is improved. The fluorine-containing phosphate ester compound also has good electrochemical reaction characteristics, and can form a compact and stable electrolyte interface (SEI film) on a negative electrode;
(2) Alkenyl, alkynyl or benzene rings connected with the fluorine-containing phosphate additive have unsaturation degrees, can be polymerized on the surface of a positive electrode to generate a stable electrolyte interface (CEI film), can effectively inhibit side reaction of an electrolyte and the positive electrode, inhibit dissolution of transition metal, improve the interface stability of the positive electrode, prevent continuous consumption and capacity reduction of lithium ions caused by continuous breakage and recombination of the CEI film in a circulation process, and are favorable for improving the circulation performance;
(3) Other additives in the electrolyte, namely fluoroethylene carbonate (FEC), vinylene Carbonate (VC), vinyl sulfate (DTD) and lithium bis (fluorosulfonyl) imide (LiFSI), can form a stable SEI film on a negative electrode, the DTD can modify SEI film components, the relative content of S, O atoms is increased, the impedance of Chi Jiemian of lithium ion is reduced, and the low-temperature performance can also be improved; the VC also has good thermal stability and the effect of effectively inhibiting cyclic gas production; the addition of LiFSI can reduce impedance, improve ionic conductivity, improve rate capability and improve high and low temperature performance. The combination of a plurality of additives can also generate synergistic effect, reduce the internal polarization effect of the battery, reduce the internal resistance of the battery, mutually promote the formation of an electrolyte interface and effectively protect the electrode;
(4) The fluorine-containing phosphate ester added into the electrolyte has higher reduction potential, can preferentially form a film on a negative electrode, can inhibit the reaction of other additives, reduces gas generation, and plays a role in protecting other additives; the additive can reduce the impedance of the lithium ion battery, improve the ionic conductivity, and improve the rate capability, high and low temperature performance, high temperature storage performance, high temperature cycle performance and safety performance under the synergistic effect.
The battery module, the battery pack and the electric device of the present invention include the lithium ion battery, and thus have at least the same advantages as the lithium ion battery.
Drawings
FIG. 1 is a H spectrum of a compound of formula 3 according to the present invention.
FIG. 2 is a F spectrum of a compound of formula 3 according to the present invention.
FIG. 3 is a spectrum of H of the compound of formula 4 according to the present invention.
FIG. 4 is a F spectrum of a compound of formula 4 according to the present invention.
FIG. 5 is a graph showing the comparative example 1 and the comparative examples 1 to 13 in the present invention. (for example, the abscissa is 0.33C, and comparative example 1, examples 1 to 13,0.5C, 1C and 2C are shown in the histogram from left to right).
FIG. 6 is a graph showing comparative example 1 to 13 rate charge. (for example, the abscissa is 0.33C, and comparative examples 1 to 13,0.5C, 1C and 2C are illustrated in the histogram from left to right).
FIG. 7 is a graph showing comparative example 1 to 13 rate discharges in accordance with the present invention. (for example, the abscissa is 0.33C, and comparative examples 1 to 13,1C, 3C and 5C are illustrated in the histogram from left to right).
FIG. 8 is a graph showing the comparative example 1 and examples 1 to 13 in which the discharge rate is compared. (for example, the abscissa is 0.33C, and comparative example 1, examples 1 to 13,1C, 3C and 5C are shown in the histogram from left to right in this order).
FIG. 9 is a graph comparing the retention rate and recovery rate of high-temperature storage capacity of comparative example 1 and examples 1 to 13 according to the present invention. (in the capacity retention rate, comparative example 1 and examples 1 to 13 are shown in the histogram from left to right, and the capacity recovery rate is as described above).
FIG. 10 is a graph comparing the retention rate and recovery rate of high-temperature storage capacity of comparative examples 1 to 13 according to the present invention. (in the capacity retention rate, comparative examples 1 to 13 are shown in the histogram from left to right, and the capacity recovery rate is described as before).
Detailed Description
The present inventors have conducted extensive research and study and have provided a nonaqueous electrolytic solution, a lithium ion battery, a battery module, a battery pack, and an electric device. In the non-aqueous electrolyte, through the synergy of functional additives such as lithium salt, a non-aqueous organic solvent and a compound with a structure shown in formula I, a compact and uniform solid electrolyte interface film with a stable structure can be formed on the surfaces of a positive electrode and a negative electrode, the high-temperature storage performance, the rate capability, the low-temperature performance and the cycle performance of the lithium ion battery can be effectively improved, and the safety performance of the lithium ion battery is improved. On this basis, the present application has been completed.
Definitions of terms the following words, phrases and symbols used in this specification have the meanings as generally described below, unless otherwise indicated.
Generally, the nomenclature used herein (e.g., IUPAC nomenclature) and the laboratory procedures described below (including those used in cell culture, organic chemistry, analytical chemistry, and pharmacology, etc.) are those well known and commonly employed in the art. Unless defined otherwise, all scientific and technical terms used herein in connection with the disclosure described herein have the same meaning as commonly understood by one of ordinary skill in the art. Furthermore, in the claims and/or the specification, the terms "a" or "an" when used in conjunction with the terms "comprising" or "a" may mean "one," but also consistent with the meaning of "one or more," at least one, "and" one or more than one. Similarly, the term "another" or "other" may mean at least a second or more.
It should be understood that whenever the terms "comprising" or "including" are used herein to describe various aspects, there are provided other similar aspects described as "consisting of …" and/or "consisting essentially of …".
Here, the bond is broken by wavy lines
Showing the point of attachment of the depicted group to the rest of the molecule. For example, R is illustrated below 1 Or R 2 Group of
Represents the attachment of said group to O of a compound of formula I.
Salts, solvates, polymorphs of the compounds of formula I described in this disclosure are also encompassed within the scope of this disclosure.
The term "salt", as used herein, refers to an inorganic or organic acid and/or base addition salt. Examples include: examples include: sulfate, hydrochloride, maleate, sulfonate, citrate, lactate, tartrate, fumarate, phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, oxalate, malonate, benzoate, mandelate, succinate, glycolate, p-toluenesulfonate and the like.
The term "polymorph" herein refers to a solid crystalline form of a compound disclosed herein or a complex thereof. Different polymorphs of the same compound exhibit different physical, chemical and/or spectral characteristics. Differences in physical properties include, but are not limited to, stability (e.g., thermal or light stability), compressibility and density (important for formulation and product production), and dissolution (which may affect bioavailability). The difference in stability causes a change in chemical reactivity (e.g., differential oxidation, as evidenced by a more rapid color change when composed of one polymorph than when composed of another polymorph) or mechanical properties (e.g., stored tablet fragments are converted to more thermodynamically stable polymorphs as dynamically preferred polymorphs) or both (tablets of one polymorph are more susceptible to degradation under high humidity). Other physical properties of polymorphs may affect their processing. For example, one polymorph may be more likely to form solvates than another, e.g., due to its shape or particle size distribution, or may be more difficult to filter or wash than another polymorph.
As used herein, the term "solvate" refers to a compound of the present disclosure or a salt thereof that comprises a stoichiometric or non-stoichiometric amount of solvent bound by force between non-covalent molecules. Preferred solvents are volatile and non-toxic and can be administered to humans in very small doses. Examples of solvents include, but are not limited to, water, isopropanol, ethanol, methanol, dimethyl sulfoxide (DMSO), ethyl acetate, acetic acid, and ethanolamine. The term "hydrate" refers to a complex in which the solvent molecule is water.
The term "substituted or unsubstituted", as used herein, alone or in combination, refers herein to substitution with one or more substituents selected from the group consisting of: deuterium, fluorine, cyano, nitro, hydroxyl, mercapto, carbonyl, ester, imide, amino, phosphine oxide, alkoxy, deuterated alkoxy, trifluoromethoxy, aryloxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, silyl, boryl, alkyl, deuterated alkyl, haloalkyl, amino-substituted alkylene, alkyl-NHC (O) -, alkyl-C (O) NH-, cycloalkyl, deuterated cycloalkyl, alkenyl, aryl, aralkyl, aralkenyl, alkylarylamino, aralkylamino, heteroaromatylamino, arylamino, arylphosphino, heteroaromato, acenaphthenyl, oxo, or unsubstituted; or substituted with a substituent linking two or more of the substituents exemplified above, or unsubstituted. For example, "a substituent linking two or more substituents" may include a biphenyl group, i.e., the biphenyl group may be an aromatic group, or a substituent linking two phenyl groups.
The term "fluoroalkyl" as used herein, alone or in combination, means an alkyl group in which one or more hydrogen atoms are each replaced by a fluorine atom. For example, the fluorine-containing alkyl group includes a C1-C5 fluorine-containing alkyl group, a C1-C4 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkyl group, or a C1-C2 fluorine-containing alkyl group. By way of illustration, "fluoroalkyl" includes but is not limited toNot restricted to-CF 3 、-CHF 2 、-CH 2 F、-CH 2 -CF 3 、-CH 2 -CHF 2 、-CH 2 -CH 2 F、-CH 2 -CH 2 - CF 3 、-CH 2 -CH 2 - CHF 2 、-CH 2 -CH 2 -CH 2 F、-CH 2 -CH 2 -CH 2 -CF 3 、-CH 2 -CH 2 -CH 2 -CHF 2 、-CH 2 -CH 2 - CH 2 -CH 2 F、-CH 2 -CH 2 -CH 2 -CH 2 -CF 3 、-CH 2 -CH 2 -CH 2 -CH 2 -CHF 2 、-CH 2 -CH 2 - CH 2 -CH 2 - CH 2 F. And the like.
The term "fluoroalkoxy" as used herein, alone or in combination, refers to an alkoxy group in which one or more hydrogen atoms are each replaced by a fluorine atom. Examples thereof include C1-C5 fluoroalkoxy group, C1-C4 fluoroalkoxy group, C1-C3 fluoroalkoxy group, and C1-C2 fluoroalkoxy group. By way of illustration, "fluoroalkoxy" includes but is not limited to-O-CF 3 、- O-CHF 2 、- O-CH 2 F、- O-CH 2 -CF 3 、- O-CH 2 -CHF 2 、- O-CH 2 -CH 2 F、-O-CH 2 -CH 2 - CF 3 、-O-CH 2 -CH 2 - CHF 2 、-O-CH 2 -CH 2 -CH 2 F、-O-CH 2 -CH 2 - CH 2 -CF 3 、-O-CH 2 -CH 2 -CH 2 -CHF 2 、-O-CH 2 -CH 2 -CH 2 -CH 2 F、-O-CH 2 -CH 2 - CH 2 -CH 2 -CF 3 、-O-CH 2 -CH 2 -CH 2 -CH 2 -CHF 2 、-O-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 F, and the like.
The term "alkenyl", as used herein, alone or in combination, includes straight or branched chain alkenyl groups, which may have a number of carbon atoms ranging, for example, from C2-C5, C2-C4, C2-C3, and the like. By way of example, alkenyl groups include, but are not limited to, ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, and the like. In the present disclosure, the "alkenyl" is an optionally substituted alkenyl. Substituted alkenyl refers to alkenyl substituted one or more times (e.g., 1-4, 1-3, or 1-2 times) with a substituent such as deuterium, hydroxyl, amino, mercapto, halogen, cyano, nitro, carbonyl, ester, oxo, imide, phosphine oxide, trifluoromethyl, trifluoromethoxy, C1-C3 alkyl, C1-C3 alkoxy, and any combination thereof. Preferred substituents may be, for example, -F, -CF 3 。
The term "alkynyl", as used herein, alone or in combination, includes alkynyl groups having straight or branched chains and which may have a number of carbon atoms, for example, from C2-C5, C2-C4, C2-C3, and the like. As examples, alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl and the like. In the present disclosure, the "alkynyl" is an optionally substituted alkenyl. Substituted alkynyl refers to alkynyl substituted one or more times (e.g., 1-4, 1-3, or 1-2 times) with a substituent such as deuterium, hydroxyl, amino, mercapto, halogen, cyano, nitro, carbonyl, ester, oxo, imide, phosphine oxide, trifluoromethyl, trifluoromethoxy, C1-C3 alkyl, C1-C3 alkoxy, and any combination thereof. Preferred substituents may be, for example, -F, -CF 3 And the like.
As used herein, the term "aryl", alone or in combination, refers to a monovalent carbocyclic aromatic group comprising one or more fused rings, such as C6-C10 aryl and the like. The aryl group can be a monocyclic arylene group or a polycyclic arylene group. In some embodiments, monocyclic aryl groups include, but are not limited to, phenyl, biphenyl, and the like. Polycyclic aryl groups include, but are not limited to, naphthyl and the like. In the present disclosure, the "aryl" is an optionally substituted aryl. Substituted aryl means aryl which is substituted one or more times (e.g. 1 to 4, 1 to 3 or 1 to 2 times) by a substituent, e.g. aryl is mono-, di-or tri-substituted by a substituent, wherein the substituent is optionally e.g. selected from deuterium, hydroxy, amino, mercapto, halogen, cyano, nitroA group, a carbonyl group, an ester group, an imide group, an oxo group, a phosphine oxide group, a trifluoromethyl group, a trifluoromethoxy group, a C1-C3 alkyl group, a C1-C3 alkoxy group, and any combination thereof. For example, the substituted aryl group may be benzyl or substituted benzyl, and the substituents of benzyl may be, for example, -F, -CF 3 And so on.
Herein, the term "vinyl sulfate" or the term "DTD" is used equivalently. The term "vinylene carbonate" or the term "VC" are used equally. The term "difluoroethylene carbonate" or the term "DFEC" are used equally. The term "fluoroethylene carbonate" or the term "FEC" are used equally. The term "tris (trimethylsilane) borate" or the term "TMSB" are used equally. The term "tris (trimethylsilane) phosphate" or the term "TMSP" is used equally. The term "lithium bis (fluorosulfonylimide") or the term "LiFSI" are used equally. The term "lithium difluorooxalato borate" or the term "LiODFB" are used equally. The term "lithium difluorophosphate" or the term "LiDFP" is used equally. The term "lithium hexafluorophosphate" or the term "LiPF 6 "is used equally. The term "lithium tetrafluoroborate" or the term "LiBF 4 "is used equally. The term "lithium perchlorate" or the term "LiClO 4 "is used equally. The term "lithium hexafluoroarsenate" or the term "LiAsF 6 "is used equally. The term "lithium hexafluorophosphate" or the term "LiPF 6 "is used equally. The term "lithium tetrafluoroborate" or the term "LiBF 4 "is used equally. The term "lithium perchlorate" or the term "LiClO 4 "is used equally. The term "lithium hexafluoroarsenate" or the term "LiAsF 6 "is used equally. The term "lithium hexafluorosilicate" or the term "LiSiF 6 "is used equally. The term "lithium aluminium tetrachloride" or the term "LiAlCl 4 "is used equally. The term "lithium bis (oxalato) borate" or the term "LiBOB" are used equivalently. The term "lithium chloride" or the term "LiCl" is used equivalently. The term "lithium bromide" or the term "LiBr" are used equally. The term "lithium iodide" or the term "LiI" are used equivalently. The term "lithium trifluoromethanesulfonate" or the term "LiOTF" is used equally. Operation of the artThe term "lithium bis (trifluoromethanesulfonate) imide" or the term "LiTFSI" are used equally. The term "diethyl carbonate" and the term "DEC" are used equally. The term "ethyl methyl carbonate" and the term "EMC" are used equally. The term "ethylene carbonate" and the term "EC" are used equivalently. The term "propylene carbonate" and the term "PC" are used equally.
Non-aqueous electrolyte
The present invention in a first aspect provides a nonaqueous electrolytic solution comprising: lithium salt, a non-aqueous organic solvent and a functional additive, wherein the functional additive comprises a compound with a structure shown in a formula I or a salt, a polymorphic substance or a solvate thereof.
The compound with the structure shown in the formula I is:
Ⅰ
wherein R is F Selected from C1-C5 fluorinated alkyl, C1-C5 fluorinated alkoxy, or-F. R 1 、R 2 Each independently selected from substituted or unsubstituted C2-C5 alkenyl, substituted or unsubstituted C2-C5 alkynyl, or substituted or unsubstituted C6-C10 aryl.
The invention relates to compounds of the formula I, the radical R F Is a fluorine-containing substituted group. Because the fluorine has larger electronegativity and strong electron-withdrawing effect, the LUMO energy level of the additive is reduced, and a stable SEI film can be preferentially formed on the negative electrode in a reduction way; r 1 、R 2 The group contains alkenyl, alkynyl, aryl and the like, has high degree of unsaturation, and can be polymerized into a stable CEI film on the surface of the anode. The compound with the structure shown in the formula I can form a stable film on the anode and also can form a stable SEI film on the cathode, the high-temperature storage performance is improved, the rate capability can be improved, and the compound can be synergistically acted with other additives in the formula, so that the low-temperature performance and the cycle performance can be improved.
In the compounds of the invention of the formula I, R F Selected from C1-C5 fluorine-containing alkyl. Optionally, R F Selected from C1-C5 fluorinated alkyl group, C1-C4 fluorinated alkyl groupAn alkyl group, a C1-C3 fluoroalkyl group, or a C1-C2 fluoroalkyl group. Further optionally, R F Is selected from-CF 3 、-CHF 2 、-CH 2 F、-CH 2 -CF 3 、-CH 2 -CHF 2 、-CH 2 -CH 2 F-CH 2 -CH 2 -CF 3 、-CH 2 -CH 2 - CHF 2 、-CH 2 -CH 2 -CH 2 F、-CH 2 -CH 2 -CH 2 -CF 3 、-CH 2 -CH 2 -CH 2 -CHF 2 、-CH 2 -CH 2 - CH 2 -CH 2 F、-CH 2 -CH 2 -CH 2 -CH 2 -CF 3 、-CH 2 -CH 2 -CH 2 -CH 2 -CHF 2 or-CH 2 -CH 2 - CH 2 -CH 2 - CH 2 F and the like.
In the compounds of the invention of the formula I, R F Selected from C1-C5 fluoroalkoxy groups. Optionally, R F Selected from C1-C5 fluorine-containing alkoxy, C1-C4 fluorine-containing alkoxy, C1-C3 fluorine-containing alkoxy or C1-C2 fluorine-containing alkoxy. Further optionally, R F Selected from-O-CF 3 、- O-CHF 2 、- O-CH 2 F、- O-CH 2 -CF 3 、- O-CH 2 -CHF 2 、- O-CH 2 -CH 2 F、-O-CH 2 -CH 2 - CF 3 、-O-CH 2 -CH 2 - CHF 2 、-O-CH 2 -CH 2 -CH 2 F、-O-CH 2 -CH 2 - CH 2 -CF 3 、-O-CH 2 -CH 2 -CH 2 -CHF 2 、-O-CH 2 -CH 2 -CH 2 -CH 2 F、-O-CH 2 -CH 2 - CH 2 -CH 2 -CF 3 、-O-CH 2 -CH 2 -CH 2 -CH 2 -CHF 2 or-O-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 F, and the like.
Of the compounds of the invention of the formula I, preferably, R F Is selected from-CF 3 、-CHF 2 、-CH 2 F、-CH 2 -CF 3 、-CH 2 -CHF 2 、-CH 2 -CH 2 F、-CH 2 -CH 2 - CF 3 、-CH 2 -CH 2 - CHF 2 、-CH 2 -CH 2 -CH 2 F、-CH 2 -CH 2 -CH 2 -CF 3 、-CH 2 -CH 2 -CH 2 -CHF 2 、-CH 2 -CH 2 - CH 2 -CH 2 F、-CH 2 -CH 2 -CH 2 -CH 2 -CF 3 、-CH 2 -CH 2 -CH 2 -CH 2 -CHF 2 、-CH 2 -CH 2 - CH 2 -CH 2 - CH 2 F、 -O-CF 3 、- O-CHF 2 、- O-CH 2 F、- O-CH 2 -CF 3 、- O-CH 2 -CHF 2 、- O-CH 2 -CH 2 F、-O-CH 2 -CH 2 - CF 3 、-O-CH 2 -CH 2 - CHF 2 、-O-CH 2 -CH 2 -CH 2 F、-O-CH 2 -CH 2 - CH 2 -CF 3 、-O-CH 2 -CH 2 -CH 2 -CHF 2 、-O-CH 2 -CH 2 -CH 2 -CH 2 F、-O-CH 2 -CH 2 - CH 2 -CH 2 -CF 3 、-O-CH 2 -CH 2 -CH 2 -CH 2 -CHF 2 、-O-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 F or-F; further preferably, R F Is selected from-CF 3 or-F.
In the compounds of the invention of the formula I, R 1 、R 2 Each independently selected from substituted or unsubstituted C2-C4 alkenyl, substituted or unsubstituted C2-C4 alkynyl, or substituted or unsubstituted C6-C8 aryl.
In the compounds of the invention of the formula I, R 1 、R 2 Each independently selected from ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, or the like. Wherein the aforementioned alkenyl group may beFurther substituted one or more times, the substituents can be, for example, deuterium, hydroxy, amino, mercapto, halogen, cyano, nitro, carbonyl, ester, oxo, imide, phosphine oxide, trifluoromethyl, trifluoromethoxy, C1-C3 alkyl, C1-C3 alkoxy, and any combination thereof. Preferably the substituent may be, for example, -F or-CF 3 。
In the compounds of the invention of the formula I, R 1 、R 2 Each independently selected from ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, and the like. Wherein the alkynyl group may be further substituted one or more times, and the substituent may be, for example, deuterium, hydroxyl, amino, mercapto, halogen, cyano, nitro, carbonyl, ester, oxo, imide, phosphine oxide, trifluoromethyl, trifluoromethoxy, C1-C3 alkyl, C1-C3 alkoxy, and any combination thereof. Preferred substituents may be, for example, -F or-CF 3 。
In the compounds of the invention of the formula I, R 1 、R 2 Each independently selected from phenyl, biphenyl, or naphthyl, and the like. The phenyl group, biphenyl group, naphthyl group, etc. may be further substituted one or more times, and examples of the substituent include deuterium, hydroxyl group, amino group, mercapto group, halogen, cyano group, nitro group, carbonyl group, ester group, oxo group, imide group, phosphine oxide group, trifluoromethyl group, trifluoromethoxy group, C1-C3 alkyl group, C1-C3 alkoxy group, and any combination thereof. Alternatively, the substituted aryl group may be benzyl or substituted benzyl, the substituents for benzyl being, for example, -F, -CF 3 And the like.
In a preferred embodiment, R 1 、R 2 Each independently selected from the group consisting of:
In the non-aqueous electrolyte provided by the invention, further, the compound with the structure shown in the formula I is selected from the following structures:
in the non-aqueous electrolyte provided by the invention, the functional additive in the electrolyte can comprise a compound shown as a formula I, and also can comprise any one or a combination of a plurality of compounds shown as formulas (1) to (40).
In the non-aqueous electrolyte provided by the invention, preferably, the compound with the structure shown in the formula I is selected from bis (propargyl-1-oxy) trifluoromethylphosphonate (shown in a structural formula 1), bis (allyl-1-oxy) trifluoromethylphosphonate (shown in a structural formula 2), bis (propargyl-1-oxy) fluorophosphonate (shown in a structural formula 3), bis (allyl-1-oxy) fluorophosphonate (shown in a structural formula 4), bis (2-methyl-2-propenyl-1-oxy) fluorophosphonate (shown in a structural formula 9), bis (2-trifluoromethyl-2-propenyl-1-oxy) fluorophosphonate (shown in a structural formula 11), diphenoxyfluorophosphonate (shown in a structural formula 13), allyl (2-propynyl-1-oxy) fluorophosphonate (shown in a structural formula 19), allyl (2-trifluoromethyl-2-propenyl-1-oxy) fluorophosphonate (shown in a structural formula 25), propargyl (2-trifluoromethyl-2-propenyl-1-oxy) fluorophosphonate (shown in a structural formula 27), and bis (8978-trifluoro-2-propenyl-1-oxy) fluorophosphonate (shown in a structural formula 29), one or more of allyl (2,3,3-trifluoro-2-propene-1-oxyl) fluorophosphate (the structural formula is shown as a formula 35) and propargyl (4,4,4-trifluoro-2-butene-1-oxyl) fluorophosphate (the structural formula is shown as a formula 39).
Specifically, the following structure is preferred:
in the non-aqueous electrolyte provided by the invention, the mass ratio of the compound with the structure shown in the formula I in the non-aqueous electrolyte is 0.1-3%. In some embodiments, the mass ratio of the compound having the structure represented by formula i in the nonaqueous electrolytic solution may be 0.1% to 0.5%, 0.5% to 1%, 1% to 1.5%, 1.5% to 2%, 2% to 2.5%, 2.5% to 3%, or the like. Within the range, the compound with the structure shown in the formula I can preferentially and stably form a film on a positive electrode and a negative electrode, effectively inhibit side reactions between electrolyte and a pole piece, improve interface stability, improve cycle performance, rate performance, high-temperature storage performance and the like of a lithium ion battery, and simultaneously effectively improve flame retardant property of the electrolyte and safety performance of the lithium ion battery; the excessively high proportion of the compound with the structure shown in the formula I can cause excessively thick film formation of the positive electrode and the negative electrode, so that the interfacial impedance of the positive electrode and the negative electrode is remarkably increased, and the performance of the battery is deteriorated. The compound with the structure shown in the formula I has poor film forming effect due to too low proportion, does not have obvious improvement effect on the performances such as circulation, high-temperature storage and the like, does not play a good flame retardant role, and does not have obvious improvement effect on the safety performance.
In the non-aqueous electrolyte provided by the invention, the functional additive further comprises other additives, and the other additives are selected from one or more of vinyl sulfate (DTD), fluoroethylene carbonate (FEC), vinylene Carbonate (VC), tris (trimethylsilane) borate (TMSB), tris (trimethylsilane) phosphate (TMSP), difluoroethylene carbonate (DFEC), lithium difluorosulfonimide (LiFSI), lithium difluorooxalato borate (LiODFB) and lithium difluorophosphate (LiDFP). Preferably, the other additive is one or more of vinyl sulfate (DTD), fluoroethylene carbonate (FEC), vinylene Carbonate (VC), lithium bis-fluorosulfonylimide (LiFSI), and the like. The compound with the structure shown in the formula I can preferentially form a film on a negative electrode, and can inhibit the reaction of other additives to play a role in protecting other additives; the compound with the structure shown in the formula I can be used together with other additives to effectively reduce the impedance of the battery cell, improve the ionic conductivity, and improve the rate capability, the low-temperature performance, the high-temperature storage performance, the high-temperature cycle performance and the safety performance.
In the non-aqueous electrolyte provided by the invention, the other additives account for 2-8% of the non-aqueous electrolyte by mass. In some embodiments, the proportion of the other additive in the nonaqueous electrolyte solution by mass may be, for example, 2% to 4%, 4% to 6%, or 6% to 8%. Within the range, other additives can form a stable SEI film on the negative electrode, modify the SEI film, reduce the impedance of the SEI film, and improve the high-low temperature performance and the rate performance of the battery cell; the high proportion of other additives may result in excessively thick film formation of the negative electrode, which increases impedance, or the FEC is easily decomposed to generate gas at high temperature, which causes severe expansion of the battery cell and deterioration of the battery cell performance. The low proportion of other additives can cause poor film forming effect of the negative electrode, the interface impedance can not be effectively reduced, and the performance of the battery cell is not obviously improved.
In the non-aqueous electrolyte provided by the invention, the lithium salt comprises lithium hexafluorophosphate (LiPF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium perchlorate (LiClO) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium hexafluorosilicate (LiSiF) 6 ) Lithium aluminum tetrachloride (LiAlCl) 4 ) One or more of lithium bis (oxalato) borate (LiBOB), lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI), lithium triflate (LiOTF), lithium bis (triflate) imide (LiTFSI).
In the non-aqueous electrolyte provided by the invention, the concentration of the lithium salt in the non-aqueous electrolyte is 1 mol/L-2 mol/L. In some embodiments, the concentration of the lithium salt in the nonaqueous electrolytic solution may also be 1mol/L to 1.5mol/L or 1.5mol/L to 2mol/L, and the like. Within the range, high lithium ion conductivity and stable lithium ion transmission can be ensured, incomplete lithium salt dissociation can be caused due to too high proportion of the lithium salt, the viscosity of the electrolyte is too high, the lithium ion transmission can be hindered, and the rate capability and the low-temperature performance can be reduced. The lithium salt is present in an excessively low proportion, resulting in poor electrochemical stability of the electrolyte.
In the nonaqueous electrolytic solution provided by the invention, the nonaqueous organic solvent comprises cyclic carbonate and/or chain carbonate. Further, the non-aqueous organic solvent is selected from one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
In the nonaqueous electrolyte provided by the invention, the mass ratio of the nonaqueous organic solvent in the nonaqueous electrolyte is 60-85%. In some embodiments, the weight ratio of the nonaqueous organic solvent in the nonaqueous electrolytic solution may be 60% to 70%, 70% to 80%, or 80% to 85%. Within the above range, the lithium salt and the additive can be well dissolved, and the proportion of the non-aqueous organic solvent is too high, which results in poor electrochemical stability of the electrolyte. The proportion of the non-aqueous organic solvent is too low, so that the lithium salt is not completely dissociated, and the viscosity of the electrolyte is too high.
The nonaqueous electrolytic solution provided by the first aspect of the present invention may be prepared by a method known in the art, for example, a nonaqueous organic solvent, a lithium salt, and an additive may be mixed uniformly.
The preparation method of the compound with the structure shown in the formula I comprises the following steps:
1) Mixing phosphorus oxychloride and anhydrous dichloromethane, and sequentially adding R in the inert gas atmosphere 1 OH solution and R 2 OH solution reacts to obtain a compound shown as a formula I;
ⅠⅠ
2) Reacting the compound of formula I in the step 1) with a fluoro reagent to obtain a compound of formula I; wherein R is 1 、R 2 As defined for the compounds of formula i in the first aspect of the invention.
In the preparation method provided by the invention, the step 1) is to mix phosphorus oxychloride and anhydrous dichloromethane, and sequentially add R in the inert gas atmosphere 1 OH solution and R 2 And (4) reacting the OH solution to obtain the compound shown in the formula I. Specifically, phosphorus oxychloride and anhydrous dichloromethane are mixed, nitrogen is introduced, and R is 1 OH is dissolved in anhydrous methylene dichlorideIn an alkane. At 0 ℃, adding R 1 And (3) slowly adding the OH solution into the mixed solution, keeping the reaction temperature at 0 ℃, and continuously stirring for reaction after the dripping is finished. R is to be 2 OH in anhydrous dichloromethane and R 2 And (3) slowly adding the OH solution into the mixed solution, keeping the reaction temperature at 0 ℃, continuing stirring for reaction after dripping, slowly raising the temperature to room temperature for reaction, distilling anhydrous dichloromethane at normal pressure to obtain a crude product, and then distilling under reduced pressure to obtain the compound shown in the formula I.
In the preparation method provided by the invention, the step 2) is to react the compound of the formula I with a fluoro reagent to obtain the compound of the formula I. Specifically, a fluoro reagent is mixed with anhydrous acetonitrile, nitrogen is replaced, the temperature of a system is reduced to-10 ℃, and a compound shown as a formula I is dripped at the temperature of-10 to 0 ℃; or mixing the fluoro reagent and anhydrous acetonitrile, and dropwise adding the compound shown in the formula II at room temperature. After the addition is finished, slowly raising the temperature to room temperature or high temperature, and reacting at room temperature or high temperature to obtain the compound shown in the formula I.
The fluorinating agent includes but is not limited to antimony trifluoride, C1-C5 fluorine-containing alkane, C1-C5 fluorine-containing alcohol, and the like. Wherein, the C1-C5 fluorine-containing alkane includes but is not limited to-CF 3 、-CHF 2 、-CH 2 F、-CH 2 -CF 3 、-CH 2 -CHF 2 、-CH 2 -CH 2 F, and the like. C1-C5 fluorine-containing alcohols such as-CH (OH) F, -C (OH) F 2 、-CH 2 - CH(OH)F、-CH 2 - C(OH)F 2 And the like.
Lithium ion battery
A third aspect of the present invention provides a lithium ion battery further comprising a positive electrode, a negative electrode, a separator, and a nonaqueous electrolytic solution selected from the nonaqueous electrolytic solutions of the first aspect of the present invention.
The positive electrode includes a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector. The positive current collector can adopt a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer. The positive electrode active material layer comprises a positive electrodeThe positive electrode active material layer may further include a conductive agent and a binder. The positive active material can be selected from one or more of lithium cobaltate, lithium manganate, lithium nickel manganese oxide, lithium nickel cobalt aluminate, lithium iron phosphate and lithium iron manganese phosphate, preferably, the positive active material used in the experiment is selected from lithium nickel cobalt manganese oxide, wherein the mole fraction of nickel is more than or equal to 0.5 and less than 1. Specifically, the nickel cobalt lithium manganate ternary material can be selected from LiNi 0.5 Co 0.2 Mn 0.3 O 2 、LiNi 0.6 Co 0.2 Mn 0.2 O 2 And LiNi 0.8 Co 0.1 Mn 0.1 O 2 And the like. Those skilled in the art can select conductive agents and binders suitable for use in lithium ion batteries in the art. The conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers, for example. The binder may include, for example, at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluoroacrylate resin.
In some embodiments, the positive electrode can be prepared by: dispersing the above-mentioned components for preparing the positive electrode, such as the positive electrode material, the conductive agent, the binder and any other components, in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; and coating the positive electrode slurry on a positive electrode current collector, and drying, cold pressing and the like to obtain the positive electrode.
The negative electrode includes a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector. The negative electrode current collector can adopt metal foil or a composite current collector. For example, as the metal foil, copper foil can be used. The composite current collector may include a polymer base layer and a metal layer formed on at least one surface of the polymer base material. The anode active material layer includes an anode active material, and the anode active material layer may further include a plasticizer, a conductive agent, and a binder. The negative active material may be selected from the group consisting of silicon carbon, natural graphite, artificial graphite, lithium titanate, amorphous carbon, and a combination of one or more of lithium metal. One skilled in the art can select plasticizers, conductive agents, and binders suitable for use in lithium ion batteries in the art. The conductive agent may be at least one selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers, for example. The binder may be selected from at least one of Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS), sodium carboxymethyl cellulose (CMC-Na), for example.
In some embodiments, the anode may be prepared by: dispersing the above components for preparing the negative electrode, such as the negative electrode material, the conductive agent, the binder and any other components, in a solvent (e.g., deionized water) to form a negative electrode slurry; and coating the negative electrode slurry on a negative electrode current collector, and drying, cold pressing and the like to obtain the negative electrode.
The lithium ion battery provided by the third aspect of the present invention can be prepared by a method known in the art. For example, the positive electrode, the isolating film and the negative electrode are sequentially stacked, so that the isolating film is positioned between the positive electrode and the negative electrode to play an isolating role, and then the bare cell is obtained by stacking; and placing the bare cell in an outer packaging shell, drying, injecting a non-aqueous electrolyte, and performing vacuum packaging, standing, formation, shaping and other processes to obtain the lithium ion battery.
Battery module
In a fourth aspect, the invention provides a battery module comprising any one or more of the lithium ion batteries of the third aspect of the invention. The number of lithium ion batteries in the battery module may be adjusted according to the application and capacity of the battery module.
Battery pack
The fifth aspect of the invention provides a battery pack, which comprises any one or more battery modules of the fourth aspect of the invention. That is, the battery pack includes any one or more of the lithium ion batteries according to the third aspect of the present invention.
The number of battery modules in the battery pack can be adjusted according to the application and capacity of the battery pack.
Electric device
In a sixth aspect, the invention provides an electric device comprising any one or more of the lithium ion batteries of the third aspect. The lithium ion battery may be used as a power source for the electric device. Preferably, the electric device may be, but is not limited to, a mobile device (e.g., a mobile phone, a notebook computer, etc.), an electric vehicle (e.g., a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc.), an electric train, a ship, a satellite, an energy storage system, etc.
The following examples are provided to further illustrate the advantageous effects of the present invention.
In order to make the objects, technical solutions and advantageous technical effects of the present invention more clear, the present invention is further described in detail below with reference to examples. However, it should be understood that the embodiments of the present invention are only for explaining the present invention and are not for limiting the present invention, and the embodiments of the present invention are not limited to the embodiments given in the specification. The examples were prepared under conventional conditions or conditions recommended by the material suppliers without specifying specific experimental conditions or operating conditions.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it should also be understood that references to a combination connection between one or more devices/appliances in the present disclosure are not intended to preclude the presence or addition of further devices/appliances either before or after the combination connection or between two of the devices/appliances specifically identified unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
In the following examples, reagents, materials and instruments used are commercially available unless otherwise specified.
The lithium ion battery anode material used in the comparative example and the embodiment of the invention is nickel cobalt lithium manganate, wherein the mole fraction of nickel is more than or equal to 0.5 and less than 1, the cathode is made of artificial graphite, the electrolyte injection amount of each battery is 4g, the following different electrolytes are selected as the embodiment, and the comparative example 1 is a conventional electrolyte.
Comparative example 1
Preparing an electrolyte:
electrolyte is prepared in a dry room (the dew point of the preparation environment is lower than minus 40 ℃), and Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC) and Ethylene Carbonate (EC) are mixed according to the volume ratio of 5:2:3 was mixed as an organic solvent to prepare a total of 100mL. To the solvent was added LiPF having a lithium salt molar concentration of 1.2mol/L 6 Respectively adding a solvent and fluoroethylene carbonate (FEC) accounting for 1 percent of the total mass of lithium salt, vinylene Carbonate (VC) accounting for 1 percent of the total mass of the solvent and the lithium salt, ethylene sulfate (DTD) accounting for 2 percent of the total mass of the solvent and the lithium bifluoride sulfimide (LiFSI) into the electrolyte, stirring the mixture until the mixture is completely dissolved to obtain the electrolyte of the lithium ion battery in a comparative example 1, injecting the prepared electrolyte into a soft package battery, and carrying out the working procedures of standing, formation, capacity grading and the like to obtain the lithium ion battery A.
Example 1
Preparation of di (propargyl-1-oxy) trifluoromethylphosphonate (structural formula shown in formula 1):
the method comprises the following steps: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask and mixed, purged with nitrogen gas for 30ml/min, propargyl alcohol (112 g) was dissolved in anhydrous dichloromethane (100 g). Slowly adding the propargyl alcohol solution into a three-neck flask at 0 ℃, keeping the reaction temperature at 0 ℃, continuously stirring to react for 0.5 h after dripping, slowly raising the temperature to room temperature to react for 8 h, distilling anhydrous dichloromethane at normal pressure to obtain a crude product, and then distilling under reduced pressure to obtain colorless transparent liquid di (propargyl-1-oxyl) chlorophosphate (163.6 g) with the yield of 87%.
Step two: cesium fluoride (142 g) was added to a three-necked flask, under nitrogen blanket, bis (propargyl-1-oxy) chlorophosphate (163.6 g) and anhydrous acetonitrile (500 g) were added to the three-necked flask, and (trifluoromethyl) trimethylsilane (133 g) was added dropwise at room temperature. After the addition, the temperature was slowly raised to 80 ℃ and the reaction was refluxed for 5 hours. The reaction was detected to be complete by GC. Filtering, and distilling under reduced pressure to obtain clear liquid di (propargyl-1-oxy) trifluoromethyl phosphonate (145.8 g), the purity is 99.0 percent, and the yield is 93 percent.
Preparing an electrolyte:
in contrast to comparative example 1, 1% of bis (propargyl-1-oxy) trifluoromethylphosphonate was added to give lithium ion battery B.
Example 2
Preparation of bis (allyl-1-oxy) trifluoromethylphosphonate (formula 2):
the method comprises the following steps: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask and mixed, purged with nitrogen gas for 30ml/min, and allyl alcohol (116 g) was dissolved in anhydrous dichloromethane (100 g). Slowly adding the allyl alcohol solution into a three-mouth bottle at 0 ℃, keeping the reaction temperature at 0 ℃, continuously stirring to react for 0.5 h after dripping, slowly raising the temperature to room temperature to react for 8 h, distilling anhydrous dichloromethane at normal pressure to obtain a crude product, and then distilling under reduced pressure to obtain colorless transparent liquid di (allyl-1-oxy) chlorophosphonate (165.2 g) with the yield of 86%.
Step two: cesium fluoride (140.4 g) was added to a three-necked flask, nitrogen blanketed, bis (allyl-1-oxy) chlorophosphate (165.2 g) and anhydrous acetonitrile (500 g) were added to the three-necked flask, and (trifluoromethyl) trimethylsilane (131.5 g) was added dropwise at room temperature. After the addition, the temperature was slowly raised to 80 ℃ and the reaction was refluxed for 5 hours. The reaction was detected to be complete by GC. Filtering, and distilling under reduced pressure to obtain clear liquid bis (allyl-1-oxy) trifluoromethyl phosphonate (139.2 g), with purity of 99.2% and yield of 92%.
Preparing an electrolyte:
in contrast to comparative example 1, 1% of bis (allylic-1-oxy) trifluoromethylphosphonate was added to give lithium ion battery C.
Example 3
Preparation of di (propargyl-1-oxy) fluorophosphonate (structural formula shown in formula 3):
the method comprises the following steps: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask and mixed, purged with nitrogen gas for 30ml/min, propargyl alcohol (112 g) was dissolved in anhydrous dichloromethane (100 g). Slowly adding the propargyl alcohol solution into a three-neck flask at 0 ℃, keeping the reaction temperature at 0 ℃, continuously stirring to react for 0.5 h after dripping, slowly raising the temperature to room temperature to react for 8 h, distilling anhydrous dichloromethane at normal pressure to obtain a crude product, and then distilling under reduced pressure to obtain colorless transparent liquid di (propargyl-1-oxyl) chlorophosphate (163.6 g) with the yield of 85 percent.
Step two: antimony trifluoride (76 g) was charged into a three-necked flask, 50 mL anhydrous acetonitrile was added, nitrogen was substituted, and the system was cooled to-10 ℃. Di (propargyl-1-oxy) chlorophosphate (163.6 g) was added dropwise at-10 to 0 ℃. After the addition was completed, the temperature was slowly raised to room temperature, and the reaction was carried out at room temperature for 3 hours. The reaction was detected to be complete by GC. Vacuum distillation is carried out to obtain clear liquid di (propargyl-1-oxy) fluorophosphate (134.6 g) with the purity of 99.2 percent and the yield of 90 percent.
Preparing an electrolyte:
different from the comparative example 1, a solvent and di (propargyl-1-oxy) fluorophosphonate accounting for 1% of the total mass of lithium salt are added into the electrolyte, the mixture is stirred until the mixture is completely dissolved to obtain the lithium ion battery electrolyte of the example 3, the prepared electrolyte is injected into a soft package battery, and the lithium ion battery D is obtained after the working procedures of standing, formation, capacity grading and the like.
Example 4
Preparation of di (allyl-1-oxy) fluorophosphonate (structural formula shown in formula 4):
the method comprises the following steps: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask and mixed, purged with nitrogen gas for 30ml/min, and allyl alcohol (116 g) was dissolved in anhydrous dichloromethane (100 g). Slowly adding the allyl alcohol solution into a three-mouth bottle at 0 ℃, keeping the reaction temperature at 0 ℃, continuously stirring to react for 0.5 h after dripping, slowly raising the temperature to room temperature to react for 8 h, distilling anhydrous dichloromethane at normal pressure to obtain a crude product, and distilling under reduced pressure to obtain a colorless transparent liquid, namely bis (allyl-1-oxy) chlorophosphonate (165.2 g), wherein the yield is 84%.
Step two: antimony trifluoride (75 g) was added to a three-necked flask, 50 mL anhydrous acetonitrile was added, nitrogen was substituted, and the system was cooled to-10 ℃. Di (allyl-1-oxy) chlorophosphate (165.2 g) was added dropwise at-10 to 0 ℃. After the addition was completed, the temperature was slowly raised to room temperature, and the reaction was carried out at room temperature for 3 hours. The reaction was complete by GC. The distillation under reduced pressure gave the clear liquid bis (allyl-1-oxy) fluorophosphate (131.5 g) in 99.1% purity and 93% yield.
Preparing an electrolyte:
in contrast to comparative example 1, 1% of di (allyl-1-oxy) fluorophosphonate was added to give lithium ion battery E.
Example 5
Preparation of bis (2-methyl-2-propen-1-yloxy) fluorophosphonate (formula 9):
the method comprises the following steps:
phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask and mixed, purged with nitrogen at 30ml/min, and 2-methyl-2-propen-1-ol (144.2 g) was dissolved in anhydrous dichloromethane (100 g). Slowly adding the 2-methyl-2-propylene-1-alcohol solution into a three-necked bottle at 0 ℃, keeping the reaction temperature at 0 ℃, continuously stirring to react for 0.5 h after finishing dropping, slowly raising the temperature to room temperature to react for 8 h, distilling anhydrous dichloromethane at normal pressure to obtain a crude product, and distilling under reduced pressure to obtain a colorless transparent liquid di (2-methyl-2-propylene-1-oxyl) chlorophosphonate (179.7 g), wherein the yield is 82%.
Step two: antimony trifluoride (71.5 g) was added to a three-necked flask, 50 mL anhydrous acetonitrile was added, nitrogen was replaced, and the temperature of the system was lowered to-10 ℃. Di (2-methyl-2-propylene-1-oxyl) clodronate (179.7 g) is added dropwise at-10 to 0 ℃. After the addition was completed, the temperature was slowly raised to room temperature, and the reaction was carried out at room temperature for 3 hours. The reaction was detected to be complete by GC. Vacuum distillation is carried out to obtain clear liquid di (2-methyl-2-propylene-1-oxyl) fluorophosphonate (143.1 g) with the purity of 99.0 percent and the yield of 90 percent.
Preparing an electrolyte:
in contrast to comparative example 1, 0.5% of bis (2-methyl-2-propen-1-yloxy) fluorophosphonate was added to give a lithium ion battery F.
Example 6
Preparation of bis (2-trifluoromethyl-2-propen-1-oxy) fluorophosphonate (structural formula shown in formula 11):
the method comprises the following steps: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask and mixed, purged with nitrogen at 30ml/min, and 2-trifluoromethyl-2-propen-1-ol (252.2 g) was dissolved in anhydrous dichloromethane (100 g). Slowly adding the 2-trifluoromethyl-2-propylene-1-alcohol solution into a three-necked bottle at 0 ℃, keeping the reaction temperature at 0 ℃, continuously stirring to react for 0.5 h after finishing dropping, slowly raising the temperature to room temperature to react for 8 h, distilling anhydrous dichloromethane at normal pressure to obtain a crude product, and distilling under reduced pressure to obtain a colorless transparent liquid bis (2-trifluoromethyl-2-propylene-1-oxyl) chlorophosphonate (252.7 g), wherein the yield is 82%.
Step two: antimony trifluoride (68 g) was charged into a three-necked flask, 50 mL anhydrous acetonitrile was added, nitrogen was substituted, and the temperature of the system was lowered to-10 ℃. Di (2-trifluoromethyl-2-propylene-1-oxyl) clodronate (252.7 g) is added dropwise at-10 to 0 ℃. After the addition was completed, the temperature was slowly raised to room temperature, and the reaction was carried out at room temperature for 3 hours. The reaction was detected to be complete by GC. Vacuum distillation is carried out to obtain clear liquid di (2-trifluoromethyl-2-propylene-1-oxyl) fluorophosphonate (201.8 g) with the purity of 99.1 percent and the yield of 90 percent.
Preparing an electrolyte:
in contrast to comparative example 1, the lithium ion battery G was obtained at a LiPF6 concentration of 1.1mol/L and further 1% of bis (2-trifluoromethyl-2-propen-1-yloxy) fluorophosphonate was added.
Example 7
Preparation of diphenoxyfluorophosphonate (structural formula shown in formula 13):
the method comprises the following steps: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask and mixed, purged with nitrogen at 30ml/min, and phenol (188.2 g) was dissolved in anhydrous dichloromethane (100 g). Slowly adding the phenol solution into a three-mouth bottle at 0 ℃, keeping the reaction temperature at 0 ℃, continuously stirring to react for 0.5 h after dripping, slowly raising the temperature to room temperature to react for 8 h, distilling anhydrous dichloromethane at normal pressure to obtain a crude product, and then distilling under reduced pressure to obtain colorless transparent liquid diphenoxy chlorophosphonate (228.3 g) with the yield of 85%.
Step two: antimony trifluoride (76 g) was charged into a three-necked flask, 50 mL anhydrous acetonitrile was added, nitrogen was substituted, and the system was cooled to-10 ℃. Diphenyl oxy-chlorophosphonate (228.3 g) was added dropwise at-10 to 0 ℃. After the addition was completed, the temperature was slowly raised to room temperature, and the reaction was carried out at room temperature for 3 hours. The reaction was detected to be complete by GC. Vacuum distillation is carried out to obtain clear liquid diphenoxyl fluorophosphonate (184.3 g), the purity is 99.5 percent, and the yield is 91 percent.
Preparing an electrolyte:
in contrast to comparative example 1, the lithium ion battery H was obtained with a LiPF6 concentration of 1.1mol/L and with the addition of 1% diphenoxyfluorophosphonate.
Example 8
Preparation of bis (2,3,3-trifluoro-2-propen-1-oxyl) fluorophosphonate (formula 29):
the method comprises the following steps: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask and mixed, purged with nitrogen gas for 30ml/min, and 2,3,3-trifluoro-2-propen-1-ol (224 g) was dissolved in anhydrous dichloromethane (100 g). Slowly adding 2,3,3-trifluoro-2-propylene-1-alcohol solution into a three-necked bottle at 0 ℃, keeping the reaction temperature at 0 ℃, continuously stirring to react for 0.5 h after dripping, slowly raising the temperature to room temperature to react for 8 h, distilling anhydrous dichloromethane at normal pressure to obtain a crude product, and distilling under reduced pressure to obtain colorless transparent liquid bis (2,3,3-trifluoro-2-propylene-1-oxyl) chlorophosphonate (243.6 g), wherein the yield is 84%.
Step two: antimony trifluoride (71.5 g) was added to a three-necked flask, 50 mL anhydrous acetonitrile was added, nitrogen was replaced, and the temperature of the system was lowered to-10 ℃. Di (2,3,3-trifluoro-2-propylene-1-oxyl) clodronate (243.6 g) is added dropwise at-10 to 0 ℃. After the addition was completed, the temperature was slowly raised to room temperature, and the reaction was carried out at room temperature for 3 hours. The reaction was detected to be complete by GC. Vacuum distillation is carried out to obtain clear liquid di (2,3,3-trifluoro-2-propylene-1-oxyl) fluorophosphonate (195.8 g), the purity is 99.5 percent, and the yield is 90 percent.
Preparing an electrolyte:
in contrast to comparative example 1, a 1.1mol/L concentration of LiPF6 was added with 0.5% of bis (2,3,3-trifluoro-2-propen-1-yloxy) fluorophosphonate to give a lithium ion battery I.
Example 9
Preparation of allyl (2-propyne-1-oxyl) fluorophosphate (structural formula is shown as formula 19):
the method comprises the following steps: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask and mixed, purged with nitrogen gas for 30ml/min, and allyl alcohol (58 g) was dissolved in anhydrous dichloromethane (50 g). Slowly adding an allyl alcohol solution into a three-mouth bottle at 0 ℃, keeping the reaction temperature at 0 ℃, continuously stirring to react 0.5 h after finishing dropping, dissolving propargyl alcohol (56 g) into anhydrous dichloromethane (50 g), slowly adding the propargyl alcohol solution into the three-mouth bottle, keeping the reaction temperature at 0 ℃, continuously stirring to react 0.5 h after finishing dropping, slowly raising the temperature to room temperature to react 8 h, distilling the anhydrous dichloromethane at normal pressure to obtain a crude product, and then distilling under reduced pressure to obtain colorless transparent liquid allyl (2-propyne-1-oxy) chlorophosphate (136.2 g), wherein the yield is 82%.
Step two: antimony trifluoride 62.5 g was added to a three-necked flask, 50 mL anhydrous acetonitrile was added, nitrogen was substituted, and the temperature of the system was lowered to-10 ℃. Allyl (2-propyn-1-oxyl) chlorophosphate (136.2 g) is added dropwise at-10 to 0 ℃. After the addition was complete, the temperature was slowly raised to room temperature and the reaction was carried out at room temperature for 3 hours. The reaction was complete by GC. Vacuum distillation was carried out to obtain clear liquid allyl (2-propyne-1-oxy) fluorophosphate (106 g) with a purity of 99.2% and a yield of 90%.
Preparing an electrolyte:
in contrast to comparative example 1, 1% of allyl (2-propyn-1-yloxy) fluorophosphate was further added to give a lithium ion battery J.
Example 10
Preparation of allyl (2-trifluoromethyl-2-propen-1-oxyl) fluorophosphate (structural formula is shown in formula 25):
the method comprises the following steps: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask and mixed, purged with nitrogen gas for 30ml/min, and allyl alcohol (58 g) was dissolved in anhydrous dichloromethane (50 g). Slowly adding an allyl alcohol solution into a three-mouth bottle at 0 ℃, keeping the reaction temperature at 0 ℃, continuously stirring to react 0.5 h after finishing dropping, slowly adding a 2-trifluoromethyl-2-propylene-1-ol (126 g) into anhydrous dichloromethane (50 g), slowly adding a 2-trifluoromethyl-2-propylene-1-alcohol solution into the three-mouth bottle, keeping the reaction temperature at 0 ℃, continuously stirring to react 0.5 h after dropping, slowly raising the temperature to room temperature to react 8 h, distilling the anhydrous dichloromethane at normal pressure to obtain a crude product, and then distilling under reduced pressure to obtain a colorless transparent liquid allyl (2-trifluoromethyl-2-propylene-1-oxy) chlorophosphate (190.5 g), wherein the yield is 82%.
Step two: antimony trifluoride 64.4 g was added to a three-necked flask, 50 mL anhydrous acetonitrile was added, nitrogen was substituted, and the temperature of the system was lowered to-10 ℃. Allyl (2-trifluoromethyl-2-propen-1-oxy) chlorophosphate (190.5 g) was added dropwise at-10 to 0 ℃. After the addition was completed, the temperature was slowly raised to room temperature, and the reaction was carried out at room temperature for 3 hours. The reaction was detected to be complete by GC. Vacuum distillation was carried out to obtain clear liquid allyl (2-trifluoromethyl-2-propen-1-yloxy) fluorophosphate (148.2 g) with a purity of 98.9% and a yield of 90%.
Preparing an electrolyte:
in contrast to comparative example 1, lithium ion battery K was obtained by adding 0.5% of FEC and 0.5% of VC, and further adding 1% of allyl (2-trifluoromethyl-2-propen-1-yloxy) fluorophosphate.
Example 11
Preparation of propargyl (2-trifluoromethyl-2-propen-1-oxyl) fluorophosphate (structural formula is shown as formula 27):
the method comprises the following steps: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask and mixed, purged with nitrogen gas for 30ml/min, propargyl alcohol (56 g) was dissolved in anhydrous dichloromethane (50 g). Slowly adding a propargyl alcohol solution into a three-mouth bottle at 0 ℃, keeping the reaction temperature at 0 ℃, continuously stirring to react 0.5 h after finishing dropping, slowly adding a 2-trifluoromethyl-2-propen-1-ol (126 g) into anhydrous dichloromethane (50 g), slowly adding a 2-trifluoromethyl-2-propen-1-ol solution into the three-mouth bottle, keeping the reaction temperature at 0 ℃, continuously stirring to react 0.5 h after finishing dropping, slowly raising the temperature to room temperature to react 8 h, distilling the anhydrous dichloromethane at normal pressure to obtain a crude product, and then distilling under reduced pressure to obtain colorless transparent liquid propargyl (2-trifluoromethyl-2-propen-1-oxyl) chlorophosphate (183.8 g), wherein the yield is 83%.
Step two: antimony trifluoride 62.5 g was added to a three-necked flask, 50 mL anhydrous acetonitrile was added, nitrogen was substituted, and the temperature of the system was lowered to-10 ℃. Propargyl (2-trifluoromethyl-2-propen-1-oxy) chlorophosphate (183.8 g) was added dropwise at-10 to 0 ℃. After the addition was completed, the temperature was slowly raised to room temperature, and the reaction was carried out at room temperature for 4 hours. The reaction was detected to be complete by GC. Vacuum distillation is carried out to obtain clear liquid propargyl (2-trifluoromethyl-2-propylene-1-oxy) fluorophosphate (141.2 g) with the purity of 99.1 percent and the yield of 92 percent.
Preparing an electrolyte:
in contrast to comparative example 1, 0.5% of FEC and 0.5% of VC were added, and 1% of allyl (2-trifluoromethyl-2-propen-1-yloxy) fluorophosphate was further added to obtain a lithium ion battery L.
Example 12
Preparation of allyl (2,3,3-trifluoro-2-propen-1-oxyl) chlorophosphate (formula 35):
the method comprises the following steps: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask and mixed, purged with nitrogen gas for 30ml/min, and allyl alcohol (58 g) was dissolved in anhydrous dichloromethane (50 g). Slowly adding an allyl alcohol solution into a three-mouth bottle at 0 ℃, keeping the reaction temperature at 0 ℃, continuously stirring to react 0.5 h after finishing dropping, dissolving 2,3,3-trifluoro-2-propen-1-ol (112 g) into anhydrous dichloromethane (50 g), slowly adding 2,3,3-trifluoro-2-propen-1-alcohol solution into the three-mouth bottle, keeping the reaction temperature at 0 ℃, continuously stirring to react 0.5 h after dropping, slowly increasing the temperature to room temperature to react 10 h, distilling the anhydrous dichloromethane at normal pressure to obtain a crude product, and then distilling under reduced pressure to obtain colorless transparent liquid allyl (2,3,3-trifluoro-2-propen-1-oxy) chloro phosphate (175.4 g) with the yield of 82%.
Step two: antimony trifluoride 62.5 g was added to a three-necked flask, 50 mL anhydrous acetonitrile was added, nitrogen was substituted, and the temperature of the system was lowered to-10 ℃. Allyl (2,3,3-trifluoro-2-propene-1-oxyl) chlorophosphate (175.4 g) is added dropwise at-10 to 0 ℃. After the addition was completed, the temperature was slowly raised to room temperature, and the reaction was carried out at room temperature for 4 hours. The reaction was detected to be complete by GC. Vacuum distillation was carried out to obtain clear liquid allyl (2,3,3-trifluoro-2-propene-1-oxyl) fluorophosphate (127.8 g) with purity of 99.3% and yield of 90%.
Preparing an electrolyte:
in contrast to comparative example 1, 0.5% of allyl (2-trifluoromethyl-2-propen-1-oxyl) fluorophosphate was added to give a lithium ion battery M.
Example 13
Preparation of propargyl (4,4,4-trifluoro-2-butene-1-oxyl) fluorophosphate (with the structural formula shown in the formula 39):
the method comprises the following steps: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask and mixed, purged with nitrogen gas for 30ml/min, propargyl alcohol (56 g) was dissolved in anhydrous dichloromethane (50 g). Slowly adding a propargyl alcohol solution into a three-mouth bottle at 0 ℃, keeping the reaction temperature at 0 ℃, continuously stirring to react 0.5 h after finishing dropping, slowly adding 4,4,4-trifluoro-2-butene-1-ol (126 g) into anhydrous dichloromethane (50 g), slowly adding 4,4,4-trifluoro-2-butene-1-alcohol solution into the three-mouth bottle, keeping the reaction temperature at 0 ℃, continuously stirring to react 0.5 h after dropping, slowly increasing the temperature to room temperature to react 8 h, distilling the anhydrous dichloromethane at normal pressure to obtain a crude product, and then distilling under reduced pressure to obtain colorless transparent liquid propargyl (4,4,4-trifluoro-2-butene-1-oxyl) chlorophosphate (g) with the yield of 82%.
Step two: antimony trifluoride 17.8 g was added to a three-necked flask, 80 mL anhydrous acetonitrile was added, nitrogen was substituted, and the temperature of the system was lowered to-10 ℃. Propargyl (4,4,4-trifluoro-2-butene-1-oxyl) chlorophosphate (189 g) is added dropwise at-10 to 0 ℃. After the addition was completed, the temperature was slowly raised to room temperature, and the reaction was carried out at room temperature for 5 hours. The reaction was detected to be complete by GC. Vacuum distillation gave a clear liquid propargyl (4,4,4-trifluoro-2-butene-1-oxyl) fluorophosphate (132.9 g) in 99.0% purity in 90% yield.
Preparing an electrolyte:
in contrast to comparative example 1, 0.5% of allyl (2-trifluoromethyl-2-propen-1-oxyl) fluorophosphate was added to obtain a lithium ion battery N.
Comparative example 2
Electrolyte is prepared in a dry room (the dry room dew point is lower than minus 40 ℃), and Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC) and Ethylene Carbonate (EC) are mixed according to the volume ratio of 5:2:3 was mixed as an organic solvent to prepare a total of 100mL. To the solvent was added LiPF having a lithium salt molar concentration of 1.2mol/L 6 Respectively adding a solvent and fluoroethylene carbonate (FEC) accounting for 1 percent of the total mass of lithium salt and di (propargyl-1-oxy) trifluoromethylphosphonate (the structural formula is shown as formula 1) accounting for 1 percent of the total mass of lithium salt into the electrolyte, stirring until the solvents are completely dissolved to obtain the electrolyte of the lithium ion battery of the comparative example 2, injecting the prepared electrolyte into a soft package battery, and obtaining the lithium ion battery O after the working procedures of standing, formation, capacity grading and the like.
Comparative example 3
Different from the comparative example 2, fluoroethylene carbonate (FEC) and bis (allyl-1-oxy) trifluoromethylphosphonate (structural formula is shown in formula 2) with the total mass of the solvent and the lithium salt being 1% respectively are added to obtain the lithium ion battery P.
Comparative example 4
Different from the comparative example 2, the lithium ion battery Q is obtained by adding fluoroethylene carbonate (FEC) and di (propargyl-1-oxy) fluorophosphonate (structural formula is shown in formula 3) which are 1 percent of the total mass of the solvent and the lithium salt respectively.
Comparative example 5
Different from the comparative example 2, the solvent and fluoroethylene carbonate (FEC) and di (allyl-1-oxy) fluorophosphonate (structural formula is shown in formula 4) with the total mass of lithium salt being 1 percent are respectively added to obtain the lithium ion battery R.
Comparative example 6
Different from the comparative example 2, 1% of fluoroethylene carbonate (FEC), 1% of Vinylene Carbonate (VC), 2% of vinyl sulfate (DTD) and 1% of bis (propargyl-1-oxy) trifluoromethylphosphonate (structural formula shown in formula 1) by the total mass of the solvent and the lithium salt are respectively added to obtain the lithium ion battery S.
Comparative example 7
Different from the comparative example 2, 1% of fluoroethylene carbonate (FEC), 1% of Vinylene Carbonate (VC), 2% of vinyl sulfate (DTD) and bis (allyl-1-oxy) trifluoromethylphosphonate (structural formula is shown in formula 2) in terms of the total mass of the solvent and the lithium salt are respectively added to obtain the lithium ion battery T.
Comparative example 8
Different from the comparative example 2, 1% of fluoroethylene carbonate (FEC), 1% of Vinylene Carbonate (VC), 2% of vinyl sulfate (DTD) and di (propargyl-1-oxy) fluorophosphonate (structural formula is shown in formula 3) in the total mass of the solvent and the lithium salt are respectively added to obtain the lithium ion battery U.
Comparative example 9
Different from the comparative example 2, 1% of fluoroethylene carbonate (FEC), 1% of Vinylene Carbonate (VC), 2% of vinyl sulfate (DTD) and di (allyl-1-oxy) fluorophosphonate (structural formula is shown in formula 4) in the total mass of the solvent and the lithium salt are respectively added to obtain the lithium ion battery V.
Comparative example 10
Different from the comparative example 2, 1% of fluoroethylene carbonate (FEC), 1% of lithium bis (fluorosulfonyl) imide (LiFSI) and 1% of bis (propargyl-1-oxy) trifluoromethylphosphonate (structural formula shown in formula 1) in terms of the total mass of the solvent and the lithium salt were added, respectively, to obtain the lithium ion battery W.
Comparative example 11
Different from the comparative example 2, 1% of fluoroethylene carbonate (FEC), 1% of lithium bis (fluorosulfonyl) imide (LiFSI) and bis (allyl-1-oxy) trifluoromethylphosphonate (structural formula shown in formula 2) in terms of the total mass of the solvent and the lithium salt were added, respectively, to obtain a lithium ion battery X.
Comparative example 12
Different from the comparative example 2, 1% of fluoroethylene carbonate (FEC), 1% of lithium bis (fluorosulfonyl) imide (LiFSI) and bis (propargyl-1-oxy) fluorophosphonate (structural formula shown in formula 3) in the total mass of the solvent and the lithium salt are respectively added to obtain the lithium ion battery Y.
Comparative example 13
Different from the comparative example 2, 1% of fluoroethylene carbonate (FEC), 1% of lithium bis (fluorosulfonyl) imide (LiFSI) and bis (allyl-1-oxy) fluorophosphonate (structural formula shown in formula 4) in the total mass of the solvent and the lithium salt are added respectively to obtain the lithium ion battery Z.
LiNi is selected as the anode material of the lithium ion battery used in the experiment 0.8 Co 0.1 Mn 0.1 O 2 (nickel cobalt lithium manganate is selected as the positive electrode material, wherein the mole fraction of nickel is more than or equal to 0.5 and less than 1), artificial graphite is selected as the negative electrode, the following experiments are carried out on the batteries obtained in comparative examples 1 to 13 and all the examples 1 to 13, and the test results are shown in tables 1 to 3.
(1) And (3) rate performance test: after formation and capacity grading, the batteries obtained in comparative examples 1 to 13 and examples 1 to 13 are respectively subjected to constant current charging of 0.33C, 0.5C, 1C and 2C to 4.25V and constant current discharging of 1C to 2.75V at 25 ℃, and then a double charge test is completed; and performing constant current discharge to 2.75V through 0.33C, 0.5C, 1C, 3C and 5C, respectively, performing constant current charging to 4.25V through 1C, completing a double discharge test, and calculating to obtain the charge-discharge capacity retention rate of the battery.
(2) And (3) testing high-temperature cycle performance: after formation and capacity grading, the batteries obtained in comparative examples 1 to 13 and examples 1 to 13 were charged at a constant current and a constant voltage of 1C to a voltage of 4.25V and a current of 0.05C at 45 ℃, and were left for 10min and discharged at a constant current of 1C to a voltage of 2.75V, which was a charge-discharge cycle. And (3) after the obtained battery is formed and subjected to capacity grading, 500 times of charge-discharge cycles are carried out at the temperature of 45 ℃, and the cycle capacity retention rate of the battery is calculated.
(3) And (3) testing the high-temperature storage performance: after formation and capacity grading, the batteries obtained in comparative examples 1 to 13 and examples 1 to 13 are charged to a voltage of 4.25V and a current of 0.05C at a constant current and a constant voltage of 1C at a temperature of 25 ℃, and the 1C capacity Q and the thickness H of the battery are recorded respectively; storing 7D of the battery in a full-charge state at 60 ℃, recording 1C discharge capacity Q1 and thickness H1 of the battery at 25 ℃, charging the battery to 4.25V of voltage and 0.05C of current at constant current and constant voltage of 1C, then discharging to 2.75V at constant current of 1C, recording 1C discharge capacity Q2, and calculating to obtain the capacity retention rate, recovery rate and expansion rate of the battery after storage.
(4) And (3) testing low-temperature discharge performance: after formation and capacity grading, the batteries obtained in comparative examples 1 to 13 and examples 1 to 13 are charged at a constant current and a constant voltage of 1C to a voltage of 4.25V and a current of 0.05C at a temperature of 25 ℃, and discharged at a constant current of 1C to a voltage of 2.75V, and then the discharge capacity Q3 is recorded; charging to 4.25V voltage and 0.05C current at constant current and constant voltage of 1C at 25 ℃, discharging to 2.75V at constant current of 1C at-20 ℃, recording discharge capacity Q4, and calculating to obtain the low-temperature discharge capacity retention rate of the battery.
The calculation formulas are respectively as follows:
capacity retention rate at 500 cycles = (cycle discharge capacity at 500 cycles/cycle discharge capacity at first cycles) × 100%; double charge capacity retention ratio = (any rate charge capacity/1C charge capacity) × 100%; a rate of retention of a rate of a double discharge capacity = (any rate discharge capacity/1C discharge capacity) × 100%; capacity retention ratio = Q1/Q × 100%; capacity recovery = Q2/Q × 100%; battery expansion rate = (H1-H)/hx 100%; discharge capacity retention ratio = Q4/Q3 × 100% at-20 ℃.
TABLE 1
TABLE 2
TABLE 3
As can be seen from comparison of performance data of examples and comparative examples in tables 1 to 3, after the fluorine-containing phosphate additive is added, because the fluorine-containing phosphate additive can stably form films on positive and negative electrodes, side reactions of the electrolyte are inhibited, and the interface stability is improved, the rate performance, the high-temperature storage performance and the cycle performance of the battery cell are improved; the added FEC can form a stable SEI film on the cathode, the DTD can modify SEI film components, the relative content of S, O atoms is improved, the impedance of Chi Jiemian of lithium ion is reduced, and the low-temperature performance can also be improved; the VC also has good thermal stability and the effect of effectively inhibiting cyclic gas production; the addition of LiFSI can reduce impedance, improve ionic conductivity, improve rate capability and improve high and low temperature performance; the combination of several additives can produce synergistic effect, reduce polarization effect inside the cell, lower internal resistance of the cell, promote the formation of electrolyte interface and protect electrode effectively. The multiplying power performance, the high-temperature storage performance, the high-low temperature performance and the cycle performance of the battery cell are further improved under the combined action of the fluorine-containing phosphate additive, the FEC, the DTD, the VC and the LiFSI.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (13)
1. A nonaqueous electrolyte is characterized by comprising a lithium salt, a nonaqueous organic solvent and a functional additive, wherein the functional additive comprises a compound with a structure shown in a formula I or a salt, a polymorphic substance or a solvate thereof;
Ⅰ
wherein:
R F selected from C1-C5 fluoroalkyl, C1-C5 fluoroalkoxy, or-F;
R 1 、R 2 each is independentIs selected from substituted or unsubstituted C2-C5 alkenyl, substituted or unsubstituted C2-C5 alkynyl, or substituted or unsubstituted C6-C10 aryl.
2. The nonaqueous electrolytic solution of claim 1, wherein in the compound having the structure represented by formula I, R is F Is selected from-CF 3 、-CHF 2 、-CH 2 F、-CH 2 -CF 3 、-CH 2 -CHF 2 、-CH 2 -CH 2 F、-CH 2 -CH 2 - CF 3 、-CH 2 -CH 2 - CHF 2 、-CH 2 -CH 2 -CH 2 F、-CH 2 -CH 2 -CH 2 -CF 3 、-CH 2 -CH 2 -CH 2 -CHF 2 、-CH 2 -CH 2 - CH 2 -CH 2 F、-CH 2 -CH 2 -CH 2 -CH 2 -CF 3 、-CH 2 -CH 2 -CH 2 -CH 2 -CHF 2 、-CH 2 -CH 2 - CH 2 -CH 2 - CH 2 F、 -O-CF 3 、- O-CHF 2 、- O-CH 2 F、- O-CH 2 -CF 3 、- O-CH 2 -CHF 2 、- O-CH 2 -CH 2 F、-O-CH 2 -CH 2 - CF 3 、-O-CH 2 -CH 2 - CHF 2 、-O-CH 2 -CH 2 -CH 2 F、-O-CH 2 -CH 2 - CH 2 -CF 3 、-O-CH 2 -CH 2 -CH 2 -CHF 2 、-O-CH 2 -CH 2 -CH 2 -CH 2 F、-O-CH 2 -CH 2 - CH 2 -CH 2 -CF 3 、-O-CH 2 -CH 2 -CH 2 -CH 2 -CHF 2 、-O-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 F or-F;
and/or, R 1 、R 2 Each independently selected from substituted or unsubstituted C2-C4 alkenyl, substituted or unsubstituted C2-C4 alkynyl, or substituted or unsubstituted C6-C8 aryl。
3. The nonaqueous electrolytic solution of claim 1, wherein R is 1 、R 2 Each independently selected from the group consisting of:
And/or, R F Is selected from-CF 3 or-F.
4. The nonaqueous electrolyte of claim 1~3, wherein the compound of formula I is selected from the following structures:
5. the nonaqueous electrolytic solution of claim 1, wherein the mass ratio of the compound having the structure represented by formula i in the nonaqueous electrolytic solution is 0.1% to 3%;
and/or the functional additive further comprises other additives selected from the group consisting of one or more combinations of vinyl sulfate, fluoroethylene carbonate, vinylene carbonate, tris (trimethylsilyl) borate, tris (trimethylsilyl) phosphate, vinylene difluorocarbonate, lithium difluorosulfonimide, lithium difluorooxalato borate, and lithium difluorophosphate;
and/or, the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium hexafluorosilicate, lithium aluminum tetrachloride, lithium bis (oxalato) borate, lithium chloride, lithium bromide, lithium iodide, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonate) imide;
and/or the non-aqueous organic solvent comprises cyclic carbonate and/or chain carbonate;
and/or the concentration of the lithium salt in the nonaqueous electrolytic solution is 1-2 mol/L;
and/or the mass ratio of the nonaqueous organic solvent in the nonaqueous electrolyte is 60-85%.
6. The nonaqueous electrolytic solution of claim 5, wherein the other additive is selected from one or more of the group consisting of vinyl sulfate, fluoroethylene carbonate, vinylene carbonate, and lithium bis-fluorosulfonylimide;
and/or the other additives account for 2 to 8 percent of the mass of the nonaqueous electrolyte;
and/or the non-aqueous organic solvent is selected from one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
7. The method of claim 1~6, wherein the method comprises mixing a nonaqueous organic solvent, a lithium salt, and a functional additive; the preparation method of the compound with the structure shown in the formula I comprises the following steps:
1) Mixing phosphorus oxychloride and anhydrous dichloromethane, and sequentially adding R in an inert gas atmosphere 1 OH solution and R 2 OH solution reacts to obtain a compound shown as a formula I;
ⅠⅠ
2) Subjecting the compound of formula II described in step 1)Reacting with a fluoro reagent to obtain a compound of formula I; wherein R is 1 、R 2 As defined in claim 1~4.
8. A lithium ion battery comprising a positive electrode, a negative electrode, a separator provided at an interval between the positive electrode and the negative electrode, and a nonaqueous electrolytic solution, wherein the nonaqueous electrolytic solution is the nonaqueous electrolytic solution according to any one of claims 1 to 6.
9. The lithium ion battery of claim 8, wherein the negative electrode comprises a negative active material selected from the group consisting of silicon carbon, natural graphite, artificial graphite, lithium titanate, amorphous carbon, and combinations of one or more of lithium metal;
and/or the positive electrode comprises a positive electrode active material, and the positive electrode active material is selected from one or more of lithium cobaltate, lithium manganate, lithium nickel cobalt aluminate, lithium iron phosphate and lithium iron manganese phosphate.
10. A battery module characterized by comprising the lithium ion battery according to claim 8 or 9.
11. A battery pack characterized by comprising the battery module according to claim 10.
12. An electric device, characterized by comprising the lithium ion battery according to claim 8 or 9 as a power source for the electric device.
13. The power consumer of claim 12, wherein the power consumer comprises a mobile device, an electric vehicle, an electric train, a satellite, a marine vessel, and an energy storage system.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116154293A (en) * | 2023-04-20 | 2023-05-23 | 河北省科学院能源研究所 | A kind of electrolytic solution and its preparation method and application |
| CN117936902A (en) * | 2024-01-26 | 2024-04-26 | 上海如鲲新材料股份有限公司 | High nickel silicon-based lithium ion battery electrolyte and high nickel silicon-based lithium ion battery |
| WO2024197645A1 (en) * | 2023-03-29 | 2024-10-03 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006286570A (en) * | 2005-04-05 | 2006-10-19 | Bridgestone Corp | Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery having it |
| US20080254361A1 (en) * | 2005-03-31 | 2008-10-16 | Bridgestone Corporation | Non-Aqueous Electrolyte for Battery and Non-Aqueous Electrolyte Secondary Battery Comprising the Same |
| CN104103852A (en) * | 2014-03-28 | 2014-10-15 | 珠海市赛纬电子材料有限公司 | Nonaqueous electrolyte of high-voltage lithium battery |
| CN105140566A (en) * | 2015-08-03 | 2015-12-09 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| CN105940544A (en) * | 2014-08-11 | 2016-09-14 | 关东电化工业株式会社 | Non-aqueous electrolyte containing monofluorophosphate ester and non-aqueous electrolyte battery using same |
| CN108110317A (en) * | 2016-11-25 | 2018-06-01 | 深圳新宙邦科技股份有限公司 | A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery |
| CN112448034A (en) * | 2019-09-05 | 2021-03-05 | 东莞市杉杉电池材料有限公司 | Non-aqueous electrolyte for high-voltage lithium ion battery and lithium ion battery |
| CN112448033A (en) * | 2019-09-05 | 2021-03-05 | 杉杉新材料（衢州）有限公司 | High-voltage lithium ion battery electrolyte and long-cycle-life high-voltage lithium ion battery |
| CN112625062A (en) * | 2020-12-17 | 2021-04-09 | 珠海冠宇电池股份有限公司 | Electrolyte additive, electrolyte containing additive and lithium ion battery |
| WO2022025241A1 (en) * | 2020-07-31 | 2022-02-03 | Ｍｕアイオニックソリューションズ株式会社 | Non-aqueous electrolyte solution and power storage device using same |
| CN114695943A (en) * | 2020-12-29 | 2022-07-01 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
-
2023
- 2023-01-18 CN CN202310062091.0A patent/CN115799643B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080254361A1 (en) * | 2005-03-31 | 2008-10-16 | Bridgestone Corporation | Non-Aqueous Electrolyte for Battery and Non-Aqueous Electrolyte Secondary Battery Comprising the Same |
| JP2006286570A (en) * | 2005-04-05 | 2006-10-19 | Bridgestone Corp | Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery having it |
| CN104103852A (en) * | 2014-03-28 | 2014-10-15 | 珠海市赛纬电子材料有限公司 | Nonaqueous electrolyte of high-voltage lithium battery |
| CN105940544A (en) * | 2014-08-11 | 2016-09-14 | 关东电化工业株式会社 | Non-aqueous electrolyte containing monofluorophosphate ester and non-aqueous electrolyte battery using same |
| CN105140566A (en) * | 2015-08-03 | 2015-12-09 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| CN108110317A (en) * | 2016-11-25 | 2018-06-01 | 深圳新宙邦科技股份有限公司 | A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery |
| CN112448034A (en) * | 2019-09-05 | 2021-03-05 | 东莞市杉杉电池材料有限公司 | Non-aqueous electrolyte for high-voltage lithium ion battery and lithium ion battery |
| CN112448033A (en) * | 2019-09-05 | 2021-03-05 | 杉杉新材料（衢州）有限公司 | High-voltage lithium ion battery electrolyte and long-cycle-life high-voltage lithium ion battery |
| WO2022025241A1 (en) * | 2020-07-31 | 2022-02-03 | Ｍｕアイオニックソリューションズ株式会社 | Non-aqueous electrolyte solution and power storage device using same |
| CN112625062A (en) * | 2020-12-17 | 2021-04-09 | 珠海冠宇电池股份有限公司 | Electrolyte additive, electrolyte containing additive and lithium ion battery |
| CN114695943A (en) * | 2020-12-29 | 2022-07-01 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024197645A1 (en) * | 2023-03-29 | 2024-10-03 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| CN116154293A (en) * | 2023-04-20 | 2023-05-23 | 河北省科学院能源研究所 | A kind of electrolytic solution and its preparation method and application |
| CN117936902A (en) * | 2024-01-26 | 2024-04-26 | 上海如鲲新材料股份有限公司 | High nickel silicon-based lithium ion battery electrolyte and high nickel silicon-based lithium ion battery |
| CN117936902B (en) * | 2024-01-26 | 2024-09-24 | 上海如鲲新材料股份有限公司 | High nickel silicon-based lithium ion battery electrolyte and high nickel silicon-based lithium ion battery |
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