CN115799643B - Nonaqueous electrolyte, lithium ion battery, battery module, battery pack, and power utilization device - Google Patents
Nonaqueous electrolyte, lithium ion battery, battery module, battery pack, and power utilization device Download PDFInfo
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- CN115799643B CN115799643B CN202310062091.0A CN202310062091A CN115799643B CN 115799643 B CN115799643 B CN 115799643B CN 202310062091 A CN202310062091 A CN 202310062091A CN 115799643 B CN115799643 B CN 115799643B
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- lithium
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- ion battery
- lithium ion
- battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 87
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 33
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 33
- 239000013538 functional additive Substances 0.000 claims abstract description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 155
- -1 lithium bis-fluorosulfonyl imide Chemical class 0.000 claims description 59
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 42
- 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 34
- 238000002360 preparation method Methods 0.000 claims description 33
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 24
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 16
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 239000007774 positive electrode material Substances 0.000 claims description 11
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- 238000002156 mixing Methods 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000012453 solvate Substances 0.000 claims description 6
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 4
- 238000004146 energy storage Methods 0.000 claims description 4
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- 229910052759 nickel Inorganic materials 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
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 3
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 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
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
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- 238000000926 separation method Methods 0.000 claims 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 46
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- 239000000243 solution Substances 0.000 description 29
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- ITVPBBDAZKBMRP-UHFFFAOYSA-N chloro-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound OP(O)(Cl)=O ITVPBBDAZKBMRP-UHFFFAOYSA-N 0.000 description 23
- 238000003756 stirring Methods 0.000 description 22
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 20
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- 238000004821 distillation Methods 0.000 description 19
- 238000007792 addition Methods 0.000 description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 17
- 239000011737 fluorine Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 239000012043 crude product Substances 0.000 description 14
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- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 12
- 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
- 239000010452 phosphate Substances 0.000 description 12
- 238000006467 substitution reaction Methods 0.000 description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 10
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 10
- 125000003342 alkenyl group Chemical group 0.000 description 9
- 230000000630 rising effect Effects 0.000 description 9
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 8
- 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
- 239000000463 material Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910052805 deuterium Inorganic materials 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 7
- 150000003949 imides Chemical class 0.000 description 7
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 7
- 125000004043 oxo group Chemical group O=* 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 125000004093 cyano group Chemical group *C#N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
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- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 5
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-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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- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 4
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- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 4
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
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- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 125000001691 aryl alkyl amino group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005241 heteroarylamino group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 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 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-M mandelate Chemical compound [O-]C(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-M 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 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
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000004426 substituted alkynyl group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 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 description 1
- 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
- 150000003624 transition metals Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of batteries, in particular to a nonaqueous electrolyte, a lithium ion battery, a battery module, a battery pack and an electric device. Wherein the nonaqueous electrolyte comprises a lithium salt, a solvent and a functional additive, the functional additive comprises a compound with a structure shown as a formula I,(I). The lithium ion battery using the non-aqueous electrolyte of the invention has improved comprehensive properties such as rate capability, high-temperature cycle capability, high-temperature storage capability, high-low temperature capability and safety performance.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a nonaqueous electrolyte, a lithium ion battery, a battery module, a battery pack and an electric device.
Background
In order to cope with the problems of increasingly serious environmental pollution and energy crisis, the demand of green energy is continuously rising. With the great development of clean energy in recent years, such as large-area popularization and application of electric automobiles, mobile electronic equipment, household intelligent energy storage systems and energy storage systems, the comprehensive performance requirements of lithium ion batteries are increasingly improved, and meanwhile, the safety and stability requirements of battery devices are greatly improved, so that the abuse of the batteries are prevented, and the batteries are endowed with longer service lives. In general, the incorporation 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 formula combination can cause insufficient battery performance and cannot achieve the purpose of use.
Therefore, it is needed to develop an electrolyte, which includes a specific additive or an additive combination, so that the electrolyte can effectively improve the high-temperature storage performance, the rate capability, the low-temperature performance and the cycle performance of the lithium ion battery when being used for the battery, and simultaneously, the safety performance of the lithium ion battery is considered.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a nonaqueous electrolyte and a lithium ion battery using the same, wherein the nonaqueous electrolyte comprises a compound with a structure as shown in formula i, and has a synergistic effect with other active ingredients in the electrolyte, so that a solid electrolyte interface with compact and uniform structure and stable structure can be formed on the surface of the positive electrode and the negative electrode, the high-temperature storage performance, the rate performance, the low-temperature performance and the cycle performance of the lithium ion battery can be effectively improved, and the flame retardant effect of free radicals can be effectively captured in time during high-temperature combustion, thereby improving the safety performance of the lithium ion battery.
To achieve the above and other related objects, a first aspect of the present invention provides a nonaqueous electrolyte comprising a lithium salt, a nonaqueous organic solvent, and a functional additive comprising a compound having a structure represented by formula i or a salt, polymorph or solvate thereof;
;
Ⅰ
Wherein: r is R F Selected from C1-C5 fluoroalkyl, C1-C5 fluoroalkoxy, or-F; r is R 1 、R 2 Each independently selected from a substituted or unsubstituted C2-C5 alkenyl group, a substituted or unsubstituted C2-C5 alkynyl group, or a substituted or unsubstituted C6-C10 aryl group.
The second aspect of the present invention provides a method for producing a nonaqueous electrolytic solution, which comprises mixing a nonaqueous organic solvent, a lithium salt and a functional additive to obtain; the preparation method of the compound with the structure shown in the formula I comprises the following steps:
1) Mixing phosphorus oxychloride with anhydrous dichloromethane, and sequentially adding R under inert gas atmosphere 1 OH solution and R 2 Reacting the OH solution to obtain a compound shown in the formula I;
;
ⅠⅠ
2) Reacting the compound shown in the formula II in the step 1) with a fluoro reagent to obtain a compound shown in the formula II; 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 disposed 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 a lithium ion battery according to the third aspect of the invention.
A fifth aspect of the invention provides a battery pack comprising the battery module of the fourth aspect of the invention.
A sixth aspect of the present invention provides an electric device comprising 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. When the phosphate flame retardant additive is used alone, the viscosity of the electrolyte is increased, so that the conductivity of the electrolyte is reduced, and the performance of the lithium ion battery is affected; fluorine is introduced into the phosphate flame retardant additive, so that the viscosity of phosphate is effectively reduced, the ionic conductivity of electrolyte is improved, the performance of the lithium ion battery is improved, and meanwhile, the fluorine-containing additive can generate fluorine free radicals at a certain temperature, and can adsorb hydroxyl free radicals, thereby blocking chain reaction and improving the safety of the lithium ion battery. The fluorine-containing phosphate compound also has good electrochemical reaction characteristics, and can form a compact and stable electrolyte interface (SEI film) on the negative electrode;
(2) Alkenyl, alkynyl or benzene rings connected with the fluorine-containing phosphate additive have unsaturation degree, can be polymerized on the surface of the positive electrode to generate a stable electrolyte interface (CEI film), can effectively inhibit side reaction of electrolyte and the positive electrode, inhibit dissolution of transition metal, improve the stability of the positive electrode interface, prevent continuous consumption and capacity reduction of lithium ions caused by continuous rupture and recombination of the CEI film in the circulation process, and is beneficial to improving the circulation performance;
(3) Other additives in the electrolyte, namely fluoroethylene carbonate (FEC), vinylene Carbonate (VC), ethylene sulfate (DTD) and lithium bis (fluorosulfonyl) imide (LiLSI), can form a stable SEI film on the negative electrode, the DTD can modify SEI film components, the relative content of S, O atoms is improved, the interface impedance of the lithium ion battery is reduced, and the low-temperature performance is also improved; VC also has good thermal stability and the effect of effectively inhibiting the 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 the additives can also produce a synergistic effect, reduce the internal polarization effect of the battery, reduce the internal resistance of the battery, mutually promote the formation of electrolyte interfaces and effectively protect electrodes;
(4) The fluorine-containing phosphate added in the electrolyte has higher reduction potential, can form a film on the negative electrode preferentially, can inhibit the reaction of other additives, reduces gas production, and plays a role in protecting other additives; the synergistic effect of the additives can reduce the impedance of the lithium ion battery, improve the ionic conductivity, and improve the rate capability, the high-low temperature capability, the high-temperature storage capability, the high-temperature circulation capability and the safety capability.
The battery module, the battery pack and the power utilization device comprise the lithium ion battery, and therefore have at least the same advantages as the lithium ion battery.
Drawings
FIG. 1 is an H-spectrum of a compound of formula 3 of the present invention.
FIG. 2 is a F-chart of the compound of formula 3 of the present invention.
FIG. 3 is an H-spectrum of a compound of formula 4 of the present invention.
FIG. 4 is a F-chart of the compound of formula 4 of the present invention.
Fig. 5 is a comparative charge graph of comparative example 1 and examples 1 to 13 of the present invention. (for example, the bar graph is shown with an abscissa of 0.33C, and comparative example 1, example 1 to example 13,0.5C, 1C, and 2C are described as follows in order from left to right).
Fig. 6 is a comparative charge graph of comparative examples 1 to 13 of the present invention. (illustrated by the abscissa of 0.33C, comparative examples 1 to 13,0.5C, 1C, and 2C are described earlier in the histogram from left to right).
Fig. 7 is a graph showing discharge comparisons at 1 to 13 magnifications of comparative examples of the present invention. (illustrated by the abscissa of 0.33C, comparative examples 1 to 13,1C, 3C, and 5C are described earlier in the histogram from left to right).
Fig. 8 is a graph showing the discharge ratio of comparative example 1 and examples 1 to 13 according to the present invention. (for example, the bar graph is shown with an abscissa of 0.33C, and comparative example 1, example 1 to examples 13,1C, 3C, and 5C are described in the foregoing order from left to right).
Fig. 9 is a graph showing the high temperature storage capacity retention rate versus recovery rate of comparative example 1 and examples 1 to 13 of the present application. (in the capacity retention ratio, comparative example 1, example 1 to example 13 are shown in the bar graph from left to right, and the capacity recovery ratio is the same as above).
FIG. 10 is a graph showing the comparison of the retention rate and recovery rate of the high-temperature storage capacity of comparative examples 1 to 13 of the present application. (in the capacity retention ratio, comparative examples 1 to 13 are shown in the column diagram from left to right, and the capacity recovery ratio is the same as described above).
Detailed Description
The present inventors have made extensive studies and studies to provide a nonaqueous electrolytic solution, a lithium ion battery, a battery module, a battery pack, and an electric device. In the nonaqueous electrolyte, through cooperation with the lithium salt, the nonaqueous organic solvent, the compound with the structure shown in the formula I and other functional additives, the solid electrolyte interface film with compact and uniform structure and stable structure can be formed on the surfaces of the positive electrode and the negative electrode, so that the high-temperature storage performance, the multiplying power performance, 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 set forth below in general, 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, pharmacology, and the like) 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. In addition, in the claims and/or the specification, the terms "a" or "an" when used in conjunction with the term "comprising" or noun may have the meaning of "one" but are also consistent with the meaning of "one or more", "at least one", and "one or more". Similarly, the term "another" or "other" may mean at least a second or more.
It will be understood that whenever aspects are described herein by the terms "comprising" or "including," other similar aspects are provided as described by "consisting of …" and/or "consisting essentially of ….
In this context, bonds broken by wavy lines
;
The points of attachment of the depicted groups to other parts of the molecule are shown. For example, R is depicted below 1 Or R is 2 Represented radicals
;
Representing the O-linkage of said group to the compound of formula I.
Salts, solvates, polymorphs of a compound of formula I described herein are also encompassed within the scope of the present disclosure.
In this context, the term "salt" refers in the present application to inorganic or organic acid and/or base addition salts. 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.
In this context, the term "polymorph" refers to a solid crystalline form of a disclosed compound of the application 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 faster color change when composed of one polymorph than another polymorph) or mechanical properties (e.g., as a dynamically preferred polymorph, stored tablet fragments are converted to more thermodynamically stable polymorphs) or both (tablets of one polymorph are more susceptible to degradation at high humidity). Other physical properties of polymorphs may affect their processing. For example, one polymorph may be more likely to form solvates than another polymorph, e.g., due to its shape or particle size distribution, or may be more difficult to filter or wash than another polymorph.
Herein, the term "solvate" refers to a compound of the present disclosure or a salt thereof, comprising a stoichiometric or non-stoichiometric solvent that is 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", used herein, alone or in combination, refers to substitution with one or more substituents selected from the group consisting of: deuterium, fluoro, cyano, nitro, hydroxy, mercapto, carbonyl, ester, imide, amino, phosphine oxide, alkoxy, deuteroalkoxy, trifluoromethoxy, aryloxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, silyl, boron, alkyl, deuteroalkyl, haloalkyl, amino-substituted alkylene, alkyl-NHC (O) -, alkyl-C (O) NH-, cycloalkyl, deuteroalkyl, alkenyl, aryl, aralkyl, aralkenyl, alkylaromatic, alkylamino, aralkylamino, heteroarylamino, arylamino, arylphosphino, heteroaryl, acenaphthylene, 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 with a fluorine atom. For example, it includes a C1-C5 fluoroalkyl group, a C1-C4 fluoroalkyl group, a C1-C3 fluoroalkyl group, or a C1-C2 fluoroalkyl group. As an illustration, "fluoroalkyl" 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、-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. Etc.
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 with a fluorine atom. Examples include C1-C5 fluoroalkoxy, C1-C4 fluoroalkoxy, C1-C3 fluoroalkoxy, or C1-C2 fluoroalkoxy. As an 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, etc.
The term "alkenyl" as used herein, alone or in combination, includes straight or branched alkenyl groups, the number of carbon atoms of which may be, for example, C2-C5, C2-C4, C2-C3, and the like. By way of example, alkenyl groups include, but are not limited to, vinyl, 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) with substituents such as 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. 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, the number of carbon atoms of which may be, for example, C2-C5, C2-C4, C2-C3, and the like. By way of example, alkynyl includes 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 groups substituted one or more times (e.g., 1-4, 1-3, or 1-2) with substituents such as 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. Preferred substituents may be, for example, -F, -CF 3 Etc.
The term "aryl" as used herein, alone or in combination, refers to a monovalent carbocyclic aromatic radical comprising one or more fused rings, such as a C6 to C10 aryl group and the like. Aryl groups may be monocyclic arylene groups or polycyclic arylene groups. 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 refers to aryl substituted one or more times (e.g., 1-4, 1-3, or 1-2) with a substituent, such as aryl mono-, di-, or tri-substituted with a substituent, wherein the substituent is optionally selected from, for example, deuterium, hydroxy, amino, mercapto, halogen, cyano, nitro, carbonyl, ester, imide, oxo, phosphine oxide, trifluoromethyl, trifluoromethoxy, C1-C3 alkyl, C1-C3 alkoxy, and any combination thereof. For example, the substituted aryl group may be benzyl or substituted benzyl, and the substituent of benzyl may be-F, -CF, for example 3 Etc.
The term "vinyl sulfate" or the term "DTD" is used equivalently herein. The term "vinylene carbonate" or the term "VC" is equally used. The term "bis-fluoroethylene carbonate" or the term "DFEC" is used equivalently. The term "fluoroethylene carbonate" or the term "FEC" is equally used. The term "tris (trimethylsilane)The borate ester "or the term" TMSB "is used equivalently. The term "tris (trimethylsilane) phosphate" or the term "TMSP" is used equivalently. The term "lithium bisfluorosulfonimide" or the term "LiFSI" is used equivalently. The term "lithium difluorooxalato borate" or the term "LiODFB" is equally used. The term "lithium difluorophosphate" or the term "LiDFP" is used equivalently. The term "lithium hexafluorophosphate" or the term "LiPF 6 "equivalently used. The term "lithium tetrafluoroborate" or the term "LiBF 4 "equivalently used. The term "lithium perchlorate" or the term "LiClO 4 "equivalently used. The term "lithium hexafluoroarsenate" or the term "LiAsF 6 "equivalently used. The term "lithium hexafluorophosphate" or the term "LiPF 6 "equivalently used. The term "lithium tetrafluoroborate" or the term "LiBF 4 "equivalently used. The term "lithium perchlorate" or the term "LiClO 4 "equivalently used. The term "lithium hexafluoroarsenate" or the term "LiAsF 6 "equivalently used. The term "lithium hexafluorosilicate" or the term "LiSiF 6 "equivalently used. The term "lithium aluminum tetrachloride" or the term "LiAlCl 4 "equivalently used. The term "lithium bisoxalato borate" or the term "LiBOB" is used equivalently. The term "lithium chloride" or the term "LiCl" is equally used. The term "lithium bromide" or the term "LiBr" is used equivalently. The term "lithium iodide" or the term "LiI" is used equivalently. The term "lithium triflate" or the term "LiOTF" is used equivalently. The term "lithium bis (trifluoromethylsulfonate)" or the term "LiTFSI" is used equivalently. The term "diethyl carbonate" and the term "DEC" are equally used. The term "methylethyl carbonate" and the term "EMC" are equally used. The term "ethylene carbonate" and the term "EC" are used equally. The term "propylene carbonate" and the term "PC" are used equally.
Nonaqueous electrolyte
The first aspect of the present invention provides a nonaqueous electrolytic solution comprising: lithium salt, nonaqueous organic solvent and functional additive, wherein the functional additive comprises a compound with a structure shown in a formula I or a salt, a polymorph or a solvate thereof.
The compound with the structure shown in the formula I is:
;
Ⅰ
wherein R is F Selected from C1-C5 fluoroalkyl, C1-C5 fluoroalkoxy, or-F. R is R 1 、R 2 Each independently selected from a substituted or unsubstituted C2-C5 alkenyl group, a substituted or unsubstituted C2-C5 alkynyl group, or a substituted or unsubstituted C6-C10 aryl group.
The compound of the application with the structure shown in the formula I, the group R F Is a fluorine-containing substituted group. Because fluorine has larger electronegativity, has strong electron-withdrawing effect, reduces the LUMO energy level of the additive, and can be reduced on the negative electrode preferentially to form a stable SEI film; r is R 1 、R 2 The group contains alkenyl, alkynyl, aryl and the like, has high unsaturation degree, and can be polymerized into a stable CEI film on the surface of the positive electrode. The compound with the structure shown in the formula I can form a stable SEI film on the anode and also can form a stable SEI film on the cathode, can improve the rate performance besides improving the high-temperature storage performance, and can improve the low-temperature performance and the cycle performance by synergistic effect with other additives in the formula.
In the compounds of the formula I, R F Selected from C1-C5 fluoroalkyl groups. Alternatively, R F Selected from C1-C5 fluoroalkyl, C1-C4 fluoroalkyl, C1-C3 fluoroalkyl, or C1-C2 fluoroalkyl. Further alternatively, R F 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, etc.
In the compounds of the formula I, R F Selected from C1-C5 fluoroalkoxy. Alternatively, R F Selected from the group consisting of C1-C5 fluoroalkoxy, C1-C4 fluoroalkoxy, C1-C3 fluoroalkoxy, and C1-C2 fluoroalkoxy. Further alternatively, R F Selected from the group consisting of-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, etc.
In the compounds of the formula I, R is preferably F 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 Selected from-CF 3 or-F.
In the compounds 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 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, and the like. Wherein the alkenyl groups may be further substituted one or more times, and the substituents may 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. Preferred substituents may be-F or-CF, for example 3 。
In the compounds 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 aforementioned alkynyl groups may be further substituted once orThe multiple substituents may 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. Preferred substituents may be-F or-CF, for example 3 。
In the compounds of the formula I, R 1 、R 2 Each independently selected from phenyl, biphenyl, naphthyl, and the like. Wherein the phenyl, biphenyl, or naphthyl groups, etc. may be further substituted one or more times, and the substituents may be 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, for example. Alternatively, the substituted aryl may be benzyl or substituted benzyl, and the substituents of the benzyl group may be, for example, -F, -CF 3 Etc.
In a preferred embodiment, R 1 、R 2 Each independently selected from the following groups:
、/>、/>、/>、/>、/>、/>、/>、/>、/>、、/>、/>、/>or->Etc.
In the nonaqueous electrolyte provided by the invention, the compound with the structure shown in the formula I is further selected from the following structures:
;
;
。
in the nonaqueous electrolyte provided by the invention, the functional additive in the electrolyte can comprise a compound shown in a formula I or any one or more of compounds shown in formulas (1) to (40).
In the nonaqueous electrolyte provided by the invention, preferably, the compound with the structure shown in the formula I is selected from bis (propargyl-1-oxo) trifluoromethylphosphonate (shown in the formula 1), bis (allyl-1-oxo) trifluoromethylphosphonate (shown in the formula 2), bis (propargyl-1-oxo) fluorophosphonate (shown in the formula 3), bis (allyl-1-oxo) fluorophosphonate (shown in the formula 4), bis (2-methyl-2-propen-1-oxo) fluorophosphonate (shown in the formula 9), bis (2-trifluoromethyl-2-propen-1-oxo) fluorophosphonate (shown in the formula 11), diphenoxyfluorophosphonate (shown in the formula 13), allyl (2-propyne-1-oxo) fluorophosphonate (shown in the formula 19), allyl (2-trifluoromethyl-2-propen-1-oxo) fluorophosphonate (shown in the formula 25), bis (2-methyl-2-propen-1-oxo) fluorophosphonate (shown in the formula 25), and bis (2-trifluoromethyl-2-propen-1-oxo) fluorophosphonate (shown in the formula 29, 2-fluoro-2-oxo) fluorophosphonate (shown in the formula 3 One or more of allyl (2, 3-trifluoro-2-propylene-1-oxy) fluorophosphate (structure formula shown in formula 35) and propargyl (4, 4-trifluoro-2-butene-1-oxy) fluorophosphate (structure formula shown in formula 39).
Specifically, the following structure is preferable:
;
;
。
in the nonaqueous electrolyte provided by the invention, the mass ratio of the compound with the structure shown in the formula I in the nonaqueous electrolyte is 0.1% -3%. In some embodiments, the mass ratio of the compound with the structure shown in the formula I in the non-aqueous electrolyte may be 0.1% -0.5%, 0.5% -1%, 1% -1.5%, 1.5% -2%, 2% -2.5% or 2.5% -3% or the like. In the range, the compound with the structure shown in the formula I can be formed into a film preferentially and stably at the positive and negative electrodes, so that side reactions of electrolyte and pole pieces are effectively inhibited, interface stability is improved, cycle performance, multiplying power performance, high-temperature storage performance and the like of the lithium ion battery are improved, flame retardant performance of the electrolyte is also effectively improved, and safety performance of the lithium ion battery is improved; the excessively high proportion of the compound with the structure shown in the formula I can cause the film formation of the positive electrode and the negative electrode to be excessively thick, so that the interface impedance of the positive electrode and the negative electrode is obviously 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 the excessively low proportion, has no obvious improvement effect on performances such as circulation, high-temperature storage and the like, has no good flame retardant effect, and has no obvious improvement on safety performance.
In the nonaqueous electrolyte provided by the invention, the functional additive further comprises other additives, wherein 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), bis (fluoroethylene carbonate) (DFEC), bis (fluorosulfonyl) imide Lithium (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-fluorosulfonyl imide (LiFSI), and the like. The other additives of the invention are matched with the compound with the structure shown in the formula I, so that obvious synergistic effect can be realized, the compound with the structure shown in the formula I can form a film on the negative electrode preferentially, and meanwhile, the reaction of the other additives can be inhibited, so that the effect of protecting the other additives is realized; the compound with the structure shown in the formula I can be used together with other additives to effectively reduce the impedance of a battery core, improve the ion conductivity and improve the rate capability, the low-temperature capability, the high-temperature storage capability, the high-temperature cycle capability and the safety performance.
In the nonaqueous electrolyte provided by the invention, the mass ratio of the other additives in the nonaqueous electrolyte is 2% -8%. In some embodiments, the mass ratio of the other additives in the non-aqueous electrolyte may be 2% -4%, 4% -6%, 6% -8%, etc. In the above 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 capability of the battery cell; the too high ratio of the other additives may cause the film formation of the negative electrode to be too thick, resulting in increased impedance, or the FEC is easy to decompose and produce gas at high temperature, resulting in severe expansion of the battery cell and resulting in deterioration of the battery cell performance. The too low ratio of the other additives can cause poor film forming effect of the negative electrode, interface impedance cannot be effectively reduced, and improvement on the performance of the battery core is not obvious.
In the nonaqueous electrolytic solution provided by the present invention, the lithium salt includes 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 ) Lithium bis (oxalato) borate (LiBOB), lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI), lithium triflate (LiOTF), lithium bis (trifluoromethane sulfonate) imide (LiTFSI).
In the nonaqueous electrolyte provided by the invention, the concentration of the lithium salt in the nonaqueous electrolyte is 1 mol/L-2 mol/L. In some embodiments, the concentration of the lithium salt in the nonaqueous electrolyte may also be 1 mol/L to 1.5mol/L or 1.5mol/L to 2mol/L, etc. In the above range, high lithium ion conductivity and stable lithium ion transmission can be ensured, and the lithium salt is incompletely dissociated due to the excessively high ratio of the lithium salt, so that the transmission of lithium ions can be blocked due to the excessively high viscosity of the electrolyte, and the rate performance and the low-temperature performance are reduced. Too low a ratio of the lithium salt may result in poor electrochemical stability of the electrolyte.
In the nonaqueous electrolyte provided by the invention, the nonaqueous organic solvent comprises cyclic carbonate and/or chain carbonate. Further, the nonaqueous organic solvent is selected from one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethylmethyl 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 mass ratio of the nonaqueous organic solvent in the nonaqueous electrolyte may be 60% -70%, 70% -80%, 80% -85%, or the like. In the above range, the lithium salt and the additive can be dissolved well, and too high a ratio of the nonaqueous organic solvent can result in poor electrochemical stability of the electrolyte. Too low a ratio of the nonaqueous organic solvent may result in incomplete dissociation of the lithium salt and excessive viscosity of the electrolyte.
The nonaqueous electrolyte solution according to the first aspect of the present invention may be prepared by a method known in the art, for example, by uniformly mixing a nonaqueous organic solvent, a lithium salt and an additive.
Wherein, the preparation method of the compound with the structure shown in the formula I comprises the following steps:
1) Mixing phosphorus oxychloride with anhydrous dichloromethane, and sequentially adding R under inert gas atmosphere 1 OH solution and R 2 Reacting the OH solution to obtain a compound shown in the formula I;
;
ⅠⅠ
2) Reacting the compound shown in the formula II in the step 1) with a fluoro reagent to obtain a compound shown in the formula II; 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, step 1) is to mix phosphorus oxychloride with anhydrous dichloromethane, and sequentially add R under inert gas atmosphere 1 OH solution and R 2 OH solution reaction to obtain the compound of formula II. Specifically, phosphorus oxychloride and anhydrous dichloromethane are mixed, nitrogen is introduced, and R is introduced 1 OH was dissolved in anhydrous dichloromethane. At 0 ℃, R is added 1 The OH solution was slowly added to the above mixed solution, the reaction temperature was kept at 0℃and after the completion of the dropping, the reaction was continued with stirring. R is R 2 OH was dissolved in anhydrous dichloromethane and R was taken up 2 And (3) slowly adding the OH solution into the mixed solution, keeping the reaction temperature at 0 ℃, continuously stirring for reaction after the reaction is completed, slowly heating to room temperature for reaction, distilling anhydrous dichloromethane at normal pressure to obtain a crude product, and performing reduced pressure distillation 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 shown in the formula II with a fluoro reagent to obtain the compound shown in the formula II. Specifically, a fluoro reagent is mixed with anhydrous acetonitrile, nitrogen is used for replacement, the temperature of the system is reduced to-10 ℃, and a compound of the formula I is dropwise added at-10-0 ℃; or the fluoro reagent is mixed with anhydrous acetonitrile, and the compound of the formula II is dropwise added at room temperature. After the addition, slowly heating to room temperature and/or high temperature, and reacting at room temperature and/or high temperature to obtain the compound shown in the formula I.
The fluoro reagent includes but is not limited to antimony trifluoride, C1-C5 fluorine-containing alkane, C1-C5 fluorine-containing alcohol, etc. Wherein the C1-C5 fluorine-containing alkane comprises, 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, etc. 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 Etc.
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 be 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 polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The positive electrode active material layer includes a positive electrode active material, and the positive electrode active material layer may further include a conductive agent and a binder. The positive electrode active material can be selected from one or a combination of a plurality of lithium cobalt oxide, lithium manganate, lithium nickel cobalt aluminate, lithium iron phosphate and lithium iron manganese phosphate, and preferably, the positive electrode active material used in the experiment is selected from the lithium nickel cobalt manganate, wherein the mole fraction of nickel is more than or equal to 0.5 and less than 1. Specifically, the ternary material of nickel cobalt lithium manganate can be specifically 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 One or more of the following. The person skilled in the art may select the conductive agent and binder suitable for use in lithium ion batteries. 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), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluoroacrylate resin.
In some embodiments, the positive electrode may be prepared by: dispersing the above components for preparing a positive electrode, such as a positive electrode material, a conductive agent, a binder and any other components, in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; and (3) coating the positive electrode slurry on a positive electrode current collector, and obtaining the positive electrode after the procedures of drying, cold pressing and the like.
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 a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The anode active material layer includes an anode active material, and may further include a plasticizer, a conductive agent, and a binder. The negative active material may be selected from one or more of silicon carbon, natural graphite, artificial graphite, lithium titanate, amorphous carbon, and lithium metal. The person skilled in the art may select plasticizers, conductive agents and binders suitable for use in lithium ion batteries. 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 at least one selected from styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), carboxymethyl chitosan (CMCS), and sodium carboxymethyl cellulose (CMC-Na), for example.
In some embodiments, the negative electrode may be prepared by: dispersing the above components for preparing a negative electrode, such as a negative electrode material, a conductive agent, a 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 obtaining the negative electrode after the procedures of drying, cold pressing and the like.
The lithium ion battery provided in the third aspect of the invention may be prepared by methods well known in the art. For example, stacking the positive electrode, the isolating film and the negative electrode in sequence, enabling the isolating film to be positioned between the positive electrode and the negative electrode to play a role of isolation, and then stacking to obtain a bare cell; and placing the bare cell in an outer packaging shell, drying, injecting nonaqueous electrolyte, and performing vacuum packaging, standing, formation, shaping and other procedures to obtain the lithium ion battery.
Battery module
A fourth aspect of 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
A fifth aspect of the present invention provides a battery pack comprising any one or more of the battery modules according to the fourth aspect of the present 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 may be adjusted according to the application and capacity of the battery pack.
Power utilization device
The sixth aspect of the invention provides an electric device, which comprises any one or more lithium ion batteries according to the third aspect of the invention. The lithium ion battery may be used as a power source for the power device. Preferably, the power utilization device may be, but is not limited to, a mobile device (e.g., a cell 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 watercraft, a satellite, an energy storage system, etc.
The advantageous effects of the present invention are further illustrated below with reference to examples.
In order to make the objects, technical solutions and advantageous technical effects of the present invention more clear, the present invention is described in further detail below with reference to examples. However, it should be understood that the examples of the present invention are merely for the purpose of explaining the present invention and are not intended to limit the present invention, and the examples of the present invention are not limited to the examples given in the specification. The specific experimental or operating conditions were not noted in the examples and were made under conventional conditions or under conditions recommended by the material suppliers.
Furthermore, it is to be understood that the reference to one or more method steps in this disclosure does not exclude the presence of other method steps before or after the combination step or the insertion of other method steps between these explicitly mentioned steps, unless otherwise indicated; it should also be understood that the combined connection between one or more devices/appliances referred to in the present invention does not exclude that other devices/appliances may be present before or after the combined device/appliance or that other devices/appliances may be interposed between the two explicitly mentioned devices/appliances unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention in which the invention may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the invention without substantial modification to the technical matter.
In the examples described below, reagents, materials and apparatus used are commercially available unless otherwise specified.
The lithium ion battery anode material used in the comparative example and the embodiment of the invention adopts nickel cobalt lithium manganate, wherein the mole fraction of nickel is less than or equal to 0.5 and less than 1, the cathode adopts 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
Preparation of electrolyte:
an electrolyte is arranged in a dry room (the dew point of the arrangement environment is lower than-40 ℃), and methyl ethyl carbonate (EMC), diethyl carbonate (DEC) and Ethylene Carbonate (EC) are mixed according to the volume ratio of 5:2:3 mixing as an organic solvent, and preparing 100mL in total. LiPF having a molar concentration of lithium salt of 1.2mol/L was added to the solvent 6 And respectively adding fluoroethylene carbonate (FEC), vinylene Carbonate (VC), ethylene sulfate (DTD) and lithium bis (fluorosulfonyl) imide (LiFSI) accounting for 1% of the total mass of the solvent and the lithium salt into the electrolyte, stirring until the solution is completely dissolved to obtain the lithium ion battery electrolyte of comparative example 1, injecting the prepared electrolyte into a soft-packed battery, and carrying out the procedures of standing, formation, capacity division and the like to obtain the lithium ion battery A.
Example 1
Preparation of bis (propargyl-1-oxy) trifluoromethylphosphonate (structural formula shown in formula 1):
step one: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask, mixed, purged with nitrogen at 30ml/min, and propargyl alcohol (112 g) was dissolved in anhydrous dichloromethane (100 g). At 0 ℃, the propargyl alcohol solution is slowly added into a three-mouth bottle, the reaction temperature is kept at 0 ℃, after the dripping is finished, the stirring reaction is continued for 0.5 h, then the reaction is slowly warmed to room temperature for 8 h, anhydrous dichloromethane is distilled under normal pressure, the crude product is obtained, and the colorless transparent liquid bis (propargyl-1-oxy) chlorophosphate (163.6 g) is obtained through reduced pressure distillation, and the yield is 87%.
Step two: cesium fluoride (142, g) was added to a three-necked flask, bis (propargyl-1-oxy) chlorophosphate (163.6, g) and anhydrous acetonitrile (500, g) were added to the flask under nitrogen, and (trifluoromethyl) trimethylsilane (133, g) was added dropwise at room temperature. After the addition was completed, the temperature was slowly raised to 80℃and the reaction was refluxed for 5 hours. The GC detects that the reaction was complete. Filtration and distillation under reduced pressure gave clear liquid bis (propargyl-1-oxo) trifluoromethylphosphonate (145.8. 145.8 g) having a purity of 99.0% and a yield of 93%.
Preparation of electrolyte:
unlike comparative example 1, 1% bis (propargyl-1-oxo) trifluoromethylphosphonate was also added to give lithium ion battery B.
Example 2
Preparation of bis (allyl-1-oxy) trifluoromethylphosphonate (structural formula shown in formula 2):
step one: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask, mixed, purged with nitrogen at 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 the temperature of 0 ℃, keeping the reaction temperature at the temperature of 0 ℃, continuously stirring for reacting for 0.5 h after the completion of dripping, slowly rising to the room temperature for reacting 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 bis (allyl-1-oxy) chlorophosphonate (165.2 g) with the yield of 86 percent.
Step two: cesium fluoride (140.4 g) was added to a three-necked flask, bis (allyl-1-oxy) chlorophosphate (165.2 g) and anhydrous acetonitrile (500 g) were added to the flask under nitrogen, and (trifluoromethyl) trimethylsilane (131.5 g) was added dropwise at room temperature. After the addition was completed, the temperature was slowly raised to 80℃and the reaction was refluxed for 5 hours. The GC detects that the reaction was complete. Filtration and distillation under reduced pressure gave clear liquid bis (allyl-1-oxy) trifluoromethylphosphonate (139.2. 139.2 g) having a purity of 99.2% and a yield of 92%.
Preparation of electrolyte:
unlike comparative example 1, 1% of bis (allyl-1-oxy) trifluoromethylphosphonate was also added to give lithium ion battery C.
Example 3
Preparation of bis (propargyl-1-oxy) fluorophosphonate (structural formula shown in formula 3):
step one: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask, mixed, purged with nitrogen at 30ml/min, and propargyl alcohol (112 g) was dissolved in anhydrous dichloromethane (100 g). At 0 ℃, the propargyl alcohol solution is slowly added into a three-mouth bottle, the reaction temperature is kept at 0 ℃, after the dripping is finished, the stirring reaction is continued for 0.5 h, then the reaction is slowly warmed to room temperature for 8 h, anhydrous dichloromethane is distilled under normal pressure, the crude product is obtained, and the colorless transparent liquid bis (propargyl-1-oxy) chlorophosphate (163.6 g) is obtained through reduced pressure distillation, and the yield is 85%.
Step two: antimony trifluoride (76 g) was added to a three-necked flask, and 50 mL of anhydrous acetonitrile was added thereto, and the system was cooled to-10 ℃ by nitrogen substitution. And dropwise adding di (propargyl-1-oxygen group) chlorophosphate (163.6 g) at the temperature of-10-0 ℃. After the addition was completed, the reaction was slowly warmed to room temperature and allowed to react at room temperature for 3 hours. The GC detects that the reaction was complete. Distillation under reduced pressure gave a clear liquid bis (propargyl-1-oxy) fluorophosphate (134.6. 134.6 g) with a purity of 99.2% in 90% yield.
Preparation of electrolyte:
unlike comparative example 1, di (propargyl-1-oxo) fluorophosphonate, which is 1% of the total mass of the solvent and lithium salt, was added to the above electrolyte, and stirred until completely dissolved, to obtain the electrolyte for lithium ion battery of example 3, and the prepared electrolyte was injected into a soft-packed battery, and subjected to the processes of standing, formation, capacity division, and the like, to obtain lithium ion battery D.
Example 4
Preparation of bis (allyl-1-oxy) fluorophosphonate (structural formula shown in formula 4):
step one: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask, mixed, purged with nitrogen at 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 the temperature of 0 ℃, keeping the reaction temperature at the temperature of 0 ℃, continuously stirring for reacting for 0.5 h after the completion of dripping, slowly rising to the room temperature for reacting 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 bis (allyl-1-oxy) chlorophosphonate (165.2 g) with the yield of 84 percent.
Step two: antimony trifluoride (75 g) was added to a three-necked flask, 50 mL of anhydrous acetonitrile was added thereto, and the system was cooled to-10 ℃ by nitrogen substitution. And dropwise adding di (allyl-1-oxy) chlorophosphate (165.2 g) at the temperature of minus 10-0 ℃. After the addition was completed, the reaction was slowly warmed to room temperature and allowed to react at room temperature for 3 hours. The GC detects that the reaction was complete. Distillation under reduced pressure gave a clear liquid bis (allyl-1-oxy) fluorophosphate (131.5. 131.5 g) with a purity of 99.1% and a yield of 93%.
Preparation of electrolyte:
unlike comparative example 1, 1% of bis (allyl-1-oxy) fluorophosphonate was also added to give lithium ion battery E.
Example 5
Preparation of bis (2-methyl-2-propen-1-yloxy) fluorophosphonate (structural formula shown in formula 9):
step one:
phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask, 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-ol solution into a three-mouth bottle at the temperature of 0 ℃, keeping the reaction temperature at the temperature of 0 ℃, continuously stirring for reacting for 0.5 h after dripping, slowly rising to the room temperature for reacting for 8 h, distilling anhydrous methylene dichloride under normal pressure to obtain a crude product, and distilling under reduced pressure to obtain colorless transparent liquid bis (2-methyl-2-propylene-1-oxy) chlorophosphonate (179.7 g) with the yield of 82 percent.
Step two: antimony trifluoride (71.5 g) was added to a three-necked flask, and 50 mL of anhydrous acetonitrile was added thereto, and the system was cooled to-10℃by nitrogen substitution. And dropwise adding di (2-methyl-2-propylene-1-oxy) chlorophosphonate (179.7-g) at the temperature of-10-0 ℃. After the addition was completed, the reaction was slowly warmed to room temperature and allowed to react at room temperature for 3 hours. The GC detects that the reaction was complete. Distillation under reduced pressure gave a clear liquid bis (2-methyl-2-propen-1-yloxy) fluorophosphonate (143.1. 143.1 g) having a purity of 99.0% and a yield of 90%.
Preparation of electrolyte:
unlike comparative example 1, 0.5% of bis (2-methyl-2-propen-1-yloxy) fluorophosphonate was also added to obtain lithium ion battery F.
Example 6
Preparation of bis (2-trifluoromethyl-2-propen-1-yloxy) fluorophosphonate (structural formula shown in formula 11):
step one: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask, 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-propen-1-ol solution into a three-mouth bottle at the temperature of 0 ℃, keeping the reaction temperature at the temperature of 0 ℃, continuously stirring to react for 0.5 h after dripping, slowly rising to room temperature to react for 8 h, distilling anhydrous dichloromethane under normal pressure to obtain a crude product, and distilling under reduced pressure to obtain colorless transparent liquid bis (2-trifluoromethyl-2-propen-1-oxyl) chlorophosphonate (252.7 g) with the yield of 82%.
Step two: antimony trifluoride (68 g) was added to a three-necked flask, and 50 mL of anhydrous acetonitrile was added thereto, and the system was cooled to-10℃by nitrogen substitution. And dropwise adding di (2-trifluoromethyl-2-propylene-1-oxy) chlorophosphonate (252.7 g) at the temperature of-10-0 ℃. After the addition was completed, the reaction was slowly warmed to room temperature and allowed to react at room temperature for 3 hours. The GC detects that the reaction was complete. Distillation under reduced pressure gave a clear liquid bis (2-trifluoromethyl-2-propen-1-yloxy) fluorophosphonate (201.8, g) having a purity of 99.1% and a yield of 90%.
Preparation of electrolyte:
unlike comparative example 1, liPF6 was at a concentration of 1.1mol/L and 1% bis (2-trifluoromethyl-2-propen-1-yloxy) fluorophosphonate was added to obtain lithium ion battery G.
Example 7
Preparation of diphenoxyfluorophosphonate (structural formula shown in formula 13):
step one: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask, mixed, purged with nitrogen at 30ml/min, and phenol (188.2 g) was dissolved in anhydrous dichloromethane (100 g). At 0 ℃, slowly adding a phenol solution into a three-mouth bottle, keeping the reaction temperature at 0 ℃, continuously stirring for reaction for 0.5 h after the reaction is completed, slowly heating to room temperature for reaction 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 diphenoxychlorophosphonate (228.3 g) with the yield of 85%.
Step two: antimony trifluoride (76 g) was added to a three-necked flask, and 50 mL of anhydrous acetonitrile was added thereto, and the system was cooled to-10 ℃ by nitrogen substitution. And dropwise adding diphenoxychlorophosphonate (228.3-g) at the temperature of-10-0 ℃. After the addition was completed, the reaction was slowly warmed to room temperature and allowed to react at room temperature for 3 hours. The GC detects that the reaction was complete. Distillation under reduced pressure gave a clear liquid diphenoxyfluorophosphonate (184.3 g) having a purity of 99.5% and a yield of 91%.
Preparation of electrolyte:
unlike comparative example 1, liPF6 was 1.1mol/L and 1% diphenoxyfluorophosphonate was added to obtain lithium ion battery H.
Example 8
Preparation of bis (2, 3-trifluoro-2-propen-1-yloxy) fluorophosphonate (structural formula shown in formula 29):
step one: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask, mixed, purged with nitrogen at 30ml/min, and 2, 3-trifluoro-2-propen-1-ol (224 g) was dissolved in anhydrous dichloromethane (100 g). Slowly adding the 2, 3-trifluoro-2-propylene-1-ol solution into a three-mouth bottle at the temperature of 0 ℃, keeping the reaction temperature at the temperature of 0 ℃, continuously stirring to react for 0.5 h after dripping, slowly rising to room temperature to react for 8 h, distilling anhydrous dichloromethane under normal pressure to obtain a crude product, and distilling under reduced pressure to obtain colorless transparent liquid bis (2, 3-trifluoro-2-propylene-1-oxy) chlorophosphonate (243.6 g) with the yield of 84 percent.
Step two: antimony trifluoride (71.5 g) was added to a three-necked flask, and 50 mL of anhydrous acetonitrile was added thereto, and the system was cooled to-10℃by nitrogen substitution. And dropwise adding bis (2, 3-trifluoro-2-propylene-1-oxy) chlorophosphonate (243.6 g) at the temperature of-10-0 ℃. After the addition was completed, the reaction was slowly warmed to room temperature and allowed to react at room temperature for 3 hours. The GC detects that the reaction was complete. Distillation under reduced pressure gave a clear liquid bis (2, 3-trifluoro-2-propen-1-yloxy) fluorophosphonate (195.8 g) having a purity of 99.5% and a yield of 90%.
Preparation of electrolyte:
unlike comparative example 1, liPF6 was at a concentration of 1.1mol/L and 0.5% of bis (2, 3-trifluoro-2-propen-1-yloxy) fluorophosphonate was added to obtain lithium ion battery I.
Example 9
Preparation of allyl (2-propyne-1-oxy) fluorophosphate (structural formula shown in formula 19):
step one: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask, mixed, purged with nitrogen at 30ml/min, and allyl alcohol (58 g) was dissolved in anhydrous dichloromethane (50 g). Slowly adding the allyl alcohol solution into a three-port bottle at the temperature of 0 ℃, keeping the reaction temperature at 0 ℃, continuously stirring to react for 0.5 h after dripping, dissolving propargyl alcohol (56 g) into anhydrous dichloromethane (50 g), slowly adding the propargyl alcohol solution into the three-port bottle, keeping the reaction temperature at 0 ℃, continuously stirring to react for 0.5 h after dripping, slowly rising to room temperature to react for 8 h, distilling the anhydrous dichloromethane at normal pressure to obtain a crude product, and performing reduced pressure distillation to obtain colorless transparent liquid allyl (2-propyne-1-oxyl) chlorophosphate (136.2 g), wherein the yield is 82%.
Step two: antimony trifluoride 62.5. 62.5 g was added to a three-necked flask, 50 mL of anhydrous acetonitrile was added thereto, and the system was cooled to-10℃by nitrogen substitution. Allyl (2-propyne-1-oxy) chlorophosphate (136.2 g) is added dropwise at the temperature of minus 10-0 ℃. After the addition was completed, the reaction was slowly warmed to room temperature and allowed to react at room temperature for 3 hours. The GC detects that the reaction was complete. Distillation under reduced pressure gave a clear liquid allyl (2-propyne-1-yloxy) fluorophosphate (106 g) having a purity of 99.2% and a yield of 90%.
Preparation of electrolyte:
unlike comparative example 1, 1% allyl (2-propyne-1-oxy) fluorophosphate was further added to obtain lithium ion battery J.
Example 10
Preparation of allyl (2-trifluoromethyl-2-propen-1-yloxy) fluorophosphate (structural formula shown in formula 25):
step one: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask, mixed, purged with nitrogen at 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 the temperature of 0 ℃, keeping the reaction temperature at 0 ℃, continuously stirring for reacting 0.5 h after dripping, dissolving 2-trifluoromethyl-2-propylene-1-ol (126 g) into anhydrous dichloromethane (50 g), slowly adding the 2-trifluoromethyl-2-propylene-1-ol solution into the three-mouth bottle, keeping the reaction temperature at 0 ℃, continuously stirring for reacting 0.5 h after dripping, slowly heating to room temperature for reacting 8 h, distilling the anhydrous dichloromethane at normal pressure to obtain a crude product, and then performing reduced pressure distillation to obtain colorless transparent liquid allyl (2-trifluoromethyl-2-propylene-1-oxy) chlorophosphate (190.5 g) with the yield of 82 percent.
Step two: antimony trifluoride 64.4. 64.4 g was added to a three-necked flask, and the system was cooled to-10 ℃ by adding 50 mL anhydrous acetonitrile and nitrogen substitution. Allyl (2-trifluoromethyl-2-propylene-1-oxy) chlorophosphate (190.5-g) is added dropwise at the temperature of minus 10-0 ℃. After the addition was completed, the reaction was slowly warmed to room temperature and allowed to react at room temperature for 3 hours. The GC detects that the reaction was complete. Distillation under reduced pressure gave clear liquid allyl (2-trifluoromethyl-2-propen-1-yloxy) fluorophosphate (148.2. 148.2 g), purity 98.9%, yield 90%.
Preparation of electrolyte:
unlike comparative example 1, 0.5% FEC and 0.5% VC were added, and 1% allyl (2-trifluoromethyl-2-propen-1-yloxy) fluorophosphate was also added to obtain lithium ion battery K.
Example 11
Preparation of propargyl (2-trifluoromethyl-2-propen-1-yloxy) fluorophosphate (structural formula shown in formula 27):
step one: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask, mixed, purged with nitrogen at 30ml/min, and 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 for reacting 0.5 h after dripping, dissolving 2-trifluoromethyl-2-propylene-1-ol (126 g) into anhydrous dichloromethane (50 g), slowly adding the 2-trifluoromethyl-2-propylene-1-ol solution into the three-mouth bottle, keeping the reaction temperature at 0 ℃, continuously stirring for reacting 0.5 h after dripping, slowly heating to room temperature for reacting 8 h, distilling the anhydrous dichloromethane at normal pressure to obtain a crude product, and then performing reduced pressure distillation to obtain colorless transparent liquid propargyl (2-trifluoromethyl-2-propylene-1-oxy) chlorophosphate (183.8 g) with the yield of 83%.
Step two: antimony trifluoride 62.5. 62.5 g was added to a three-necked flask, 50 mL of anhydrous acetonitrile was added thereto, and the system was cooled to-10℃by nitrogen substitution. Propargyl (2-trifluoromethyl-2-propen-1-oxy) chlorophosphate (183.8 g) is added dropwise at-10-0 ℃. After the addition was completed, the reaction was slowly warmed to room temperature and allowed to react at room temperature for 4 hours. The GC detects that the reaction was complete. Distillation under reduced pressure gave a clear liquid propargyl (2-trifluoromethyl-2-propen-1-yloxy) fluorophosphate (141.2. 141.2 g) with a purity of 99.1% in 92% yield.
Preparation of electrolyte:
unlike comparative example 1, 0.5% FEC and 0.5% VC were added, and 1% allyl (2-trifluoromethyl-2-propen-1-yloxy) fluorophosphate was also added to obtain lithium ion battery L.
Example 12
Preparation of allyl (2, 3-trifluoro-2-propen-1-oxy) chlorophosphate (structural formula shown in formula 35):
step one: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask, mixed, purged with nitrogen at 30ml/min, and allyl alcohol (58 g) was dissolved in anhydrous dichloromethane (50 g). Slowly adding 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, dissolving 2, 3-trifluoro-2-propylene-1-ol (112 g) into anhydrous dichloromethane (50 g), slowly adding 2, 3-trifluoro-2-propylene-1-ol solution into the three-mouth bottle, keeping the reaction temperature at 0 ℃, continuously stirring to react for 0.5 h after dripping, slowly rising to room temperature to react for 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-trifluoro-2-propylene-1-oxy) chlorophosphate (175.4 g) with the yield of 82 percent.
Step two: antimony trifluoride 62.5. 62.5 g was added to a three-necked flask, 50 mL of anhydrous acetonitrile was added thereto, and the system was cooled to-10℃by nitrogen substitution. Allyl (2, 3-trifluoro-2-propen-1-oxy) chlorophosphate (175.4. 175.4 g) is added dropwise at the temperature of minus 10-0 ℃. After the addition was completed, the reaction was slowly warmed to room temperature and allowed to react at room temperature for 4 hours. The GC detects that the reaction was complete. Distillation under reduced pressure gave clear liquid allyl (2, 3-trifluoro-2-propen-1-yloxy) fluorophosphate (127.8, g) with a purity of 99.3% and a yield of 90%.
Preparation of electrolyte:
unlike comparative example 1, 0.5% allyl (2-trifluoromethyl-2-propen-1-yloxy) fluorophosphate was also added to obtain lithium ion battery M.
Example 13
Preparation of propargyl (4, 4-trifluoro-2-butene-1-oxy) fluorophosphate (structural formula shown in formula 39):
step one: phosphorus oxychloride (153 g) and anhydrous dichloromethane (150 g) were added to a three-necked flask, mixed, purged with nitrogen at 30ml/min, and 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 for 0.5 h after the completion of dripping, dissolving 4, 4-trifluoro-2-butene-1-ol (126 g) into anhydrous dichloromethane (50 g), slowly adding the 4, 4-trifluoro-2-butene-1-ol solution into the three-mouth bottle, keeping the reaction temperature at 0 ℃, continuously stirring to react for 0.5 h after the completion of dripping, slowly rising to room temperature to react for 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-trifluoro-2-butene-1-oxy) chlorophosphate (189 g) with the yield of 82 percent.
Step two: antimony trifluoride 17.8. 17.8 g was added to a three-necked flask, and the system was cooled to-10℃by displacement with 80. 80 mL anhydrous acetonitrile and nitrogen. Propargyl (4, 4-trifluoro-2-butene-1-oxy) chlorophosphate (189 g) is added dropwise at the temperature of minus 10-0 ℃. After the addition was completed, the reaction mixture was slowly warmed to room temperature and reacted at room temperature for 5 hours. The GC detects that the reaction was complete. Distillation under reduced pressure gave a clear liquid propargyl (4, 4-trifluoro-2-buten-1-yloxy) fluorophosphate (132.9. 132.9 g) with a purity of 99.0% in a yield of 90%.
Preparation of electrolyte:
unlike comparative example 1, 0.5% allyl (2-trifluoromethyl-2-propen-1-yloxy) fluorophosphate was also added to obtain lithium ion battery N.
Comparative example 2
Preparing electrolyte in a dry room (the dew point of the dry room is lower than-40 ℃), and mixing methyl ethyl carbonate (EMC), diethyl carbonate (DEC) and Ethylene Carbonate (EC) according to a volume ratio of 5:2:3 mixing as an organic solvent, and preparing 100mL in total. LiPF having a molar concentration of lithium salt of 1.2mol/L was added to the solvent 6 And respectively adding fluoroethylene carbonate (FEC) accounting for 1% of the total mass of the solvent and lithium salt and 1% of bis (propargyl-1-oxo) trifluoromethyl phosphonate (shown in a structural formula 1) into the electrolyte, stirring until the fluoroethylene carbonate and the bis (propargyl-1-oxo) trifluoromethyl phosphonate are completely dissolved to obtain the lithium ion battery electrolyte of comparative example 2, injecting the prepared electrolyte into a soft-packed battery, and standing, forming, capacity-dividing and other procedures to obtain the lithium ion battery O.
Comparative example 3
Unlike comparative example 2, fluoroethylene carbonate (FEC) and bis (allyl-1-oxy) trifluoromethylphosphonate (structural formula shown in formula 2) were added in an amount of 1% by mass of the total of the solvent and lithium salt, respectively, to obtain lithium ion battery P.
Comparative example 4
Unlike comparative example 2, fluoroethylene carbonate (FEC) and bis (propargyl-1-oxy) fluorophosphonate (structural formula shown in formula 3) were added in an amount of 1% of the total mass of the solvent and lithium salt, respectively, to obtain lithium ion battery Q.
Comparative example 5
Unlike comparative example 2, fluoroethylene carbonate (FEC) and bis (allyl-1-oxy) fluorophosphonate (structural formula shown in formula 4) were added in an amount of 1% by mass of the total of the solvent and lithium salt, respectively, to obtain lithium ion battery R.
Comparative example 6
Unlike comparative example 2, fluoroethylene carbonate (FEC), vinylene Carbonate (VC), ethylene sulfate (DTD) and bis (propargyl-1-oxy) trifluoromethylphosphonate (structural formula shown in formula 1) were added in an amount of 1% by weight based on the total mass of the solvent and lithium salt, respectively, to obtain lithium ion battery S.
Comparative example 7
Unlike comparative example 2, fluoroethylene carbonate (FEC), vinylene Carbonate (VC), 2% ethylene sulfate (DTD) and bis (allyl-1-oxy) trifluoromethylphosphonate (structural formula shown in formula 2) were added in an amount of 1% by weight of the total of the solvent and lithium salt, respectively, to obtain a lithium ion battery T.
Comparative example 8
Unlike comparative example 2, fluoroethylene carbonate (FEC), vinylene Carbonate (VC), ethylene sulfate (DTD) and bis (propargyl-1-oxy) fluorophosphonate (structural formula shown in formula 3) were added in an amount of 1% by weight of the total of the solvent and lithium salt, respectively, to obtain a lithium ion battery U.
Comparative example 9
Unlike comparative example 2, fluoroethylene carbonate (FEC), vinylene Carbonate (VC), ethylene sulfate (DTD) and bis (allyl-1-oxy) fluorophosphonate (structural formula shown in formula 4) were added in an amount of 1% by weight based on the total mass of the solvent and lithium salt, respectively, to obtain a lithium ion battery V.
Comparative example 10
Unlike comparative example 2, fluoroethylene carbonate (FEC), 1% lithium bis (fluorosulfonyl) imide (LiFSI), and 1% bis (propargyl-1-oxy) trifluoromethylphosphonate (structural formula shown in formula 1) were added, respectively, to the total mass of the solvent and lithium salt, to obtain a lithium ion battery W.
Comparative example 11
Unlike comparative example 2, fluoroethylene carbonate (FEC), 1% lithium bis (fluorosulfonyl) imide (LiFSI), and bis (allyl-1-oxy) trifluoromethylphosphonate (structural formula shown in formula 2) were added, respectively, in an amount of 1% by mass based on the total mass of the solvent and lithium salt, to obtain lithium ion battery X.
Comparative example 12
Unlike comparative example 2, fluoroethylene carbonate (FEC), 1% lithium bis (fluorosulfonyl) imide (LiFSI), and bis (propargyl-1-oxy) fluorophosphonate (structural formula shown in formula 3) were added, respectively, in an amount of 1% by mass of the total of the solvent and lithium salt, to obtain a lithium ion battery Y.
Comparative example 13
Unlike comparative example 2, fluoroethylene carbonate (FEC), 1% lithium bis (fluorosulfonyl) imide (LiFSI) and bis (allyl-1-oxy) fluorophosphonate (structural formula shown in formula 4) were added, respectively, in an amount of 1% by mass based on the total mass of the solvent and lithium salt, to obtain a lithium ion battery Z.
LiNi is selected as the positive electrode material of the lithium ion battery used in the experiment 0.8 Co 0.1 Mn 0.1 O 2 (the positive electrode material is nickel cobalt lithium manganate, wherein the mole fraction of nickel is less than or equal to 0.5 and less than 1), the negative electrode material is artificial graphite, and the following experiments are carried out on the batteries obtained in comparative examples 1-13 and all the examples 1-13, and the test results are shown in tables 1-3.
(1) And (3) multiplying power performance test: after the batteries obtained in comparative examples 1-13 and examples 1-13 are formed and divided, the batteries are respectively charged to 4.25V by constant current of 0.33C, 0.5C, 1C and 2C and discharged to 2.75V by constant current of 1C at 25 ℃ to finish double charging test; and respectively performing constant current discharge to 2.75V at 0.33C, 0.5C, 1C, 3C and 5C and constant current charge to 4.25V at 1C to finish the double discharge test, and calculating to obtain the charge-discharge capacity retention rate of the battery.
(2) High temperature cycle performance test: after the batteries obtained in comparative examples 1-13 and examples 1-13 are formed and divided, the batteries are charged to 4.25V at a constant current and a constant voltage of 1C and a constant current of 0.05C at 45 ℃ and are placed for 10min, and are discharged to 2.75V at a constant current of 1C, wherein the charging and discharging cycles are the same. And (3) after the obtained battery is formed and subjected to capacity division, carrying out charge and discharge circulation for 500 times at 45 ℃, and calculating to obtain the circulation capacity retention rate of the battery.
(3) High temperature storage performance test: after the batteries obtained in comparative examples 1-13 and examples 1-13 are formed and divided, the batteries are charged to 4.25V at a constant current and a constant voltage of 1C and 0.05C at 25 ℃, and the capacity Q of 1C and the thickness H of the batteries are recorded respectively; storing the battery in a full-charge state at 60 ℃ for 7D, recording the discharge capacity Q1 and the battery thickness H1 of the battery 1C at 25 ℃, charging the battery to 4.25V at a constant current and constant voltage of 1C, discharging to 2.75V at a constant current of 1C after the battery is charged to the voltage of 0.05C at a constant current of 1C, recording the discharge capacity Q2 of 1C, and calculating to obtain the capacity retention rate, the recovery rate and the battery expansion rate of the battery after storage.
(4) Low temperature discharge performance test: after the batteries obtained in comparative examples 1 to 13 and examples 1 to 13 were formed and subjected to capacity division, the batteries were charged at a constant current and constant voltage of 1C to a voltage of 4.25V and a current of 0.05C at 25 ℃, and were discharged at a constant current of 1C to a voltage of 2.75V, and the discharge capacity Q3 was recorded; the battery is charged to 4.25V at a constant current and a constant voltage of 1C at 25 ℃ and 0.05C at-20 ℃, discharged to 2.75V at a constant current of 1C, the discharge capacity Q4 is recorded, and the low-temperature discharge capacity retention rate of the battery is calculated.
The calculation formulas are respectively as follows:
cycle 500 th cycle capacity retention= (500 th cycle discharge capacity/first cycle discharge capacity) ×100%; double charge capacity retention= (any one of the double charge capacities/1C charge capacity) ×100%; the discharge capacity retention= (any discharge capacity at a discharge capacity of 1C discharge capacity) ×100%; capacity retention = Q1/Q x 100%; capacity recovery = Q2/Q x 100%; cell expansion ratio= (H1-H)/h×100%; -20 ℃ discharge capacity retention = Q4/Q3 x 100%.
TABLE 1
;
TABLE 2
;
TABLE 3 Table 3
;
As can be seen from the comparison of the performance data of the examples and the comparative examples in tables 1-3, after the fluorine-containing phosphate additive is added, the fluorine-containing phosphate additive can form a film stably at the positive electrode and the negative electrode, inhibit the side reaction of electrolyte and improve the interface stability, thereby improving the multiplying power performance, the high-temperature storage performance and the cycle performance of the battery cell; the added FEC can form a stable SEI film on the negative electrode, the DTD can modify SEI film components, the relative content of S, O atoms is improved, the interface impedance of the lithium ion battery is reduced, and the low-temperature performance can be improved; VC also has good thermal stability and the effect of effectively inhibiting the cyclic gas production; the addition of LiFSI can reduce impedance, improve ionic conductivity, improve rate capability and improve high-low temperature performance; the combination of the additives can also produce a synergistic effect, reduce the internal polarization effect of the battery, reduce the internal resistance of the battery, mutually promote the formation of electrolyte interfaces and effectively protect the electrodes. The combination of the fluorine-containing phosphate additive and FEC, DTD, VC, liFSI further improves the multiplying power performance, the high-temperature storage performance, the high-temperature and low-temperature performance and the cycle performance of the battery cell.
While the invention has been described with respect to preferred embodiments thereof, it will be understood by those skilled in the art that various modifications and additions may be made without departing from the scope of the invention. Equivalent embodiments of the present invention will be apparent to those skilled in the art having the benefit of the teachings disclosed herein, when considered in the light of the foregoing disclosure, and without departing from the spirit and scope of the invention; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the technical solution of the present invention.
Claims (12)
1. The lithium ion battery comprises a positive electrode, a negative electrode, a separation film and a non-aqueous electrolyte, wherein the separation film is arranged between the positive electrode and the negative electrode at intervals, and the non-aqueous electrolyte comprises lithium salt, a non-aqueous organic solvent and a functional additive, and the functional additive comprises a compound with a structure shown in a formula I or a salt, a polymorph or a solvate of the compound;
Wherein:
R F selected from C1-C5 fluoroalkyl, 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 mass ratio of the compound with the structure shown in the formula I in the non-aqueous electrolyte is 0.1% -3%;
the functional additive also comprises other additives selected from the group consisting of vinyl sulfate, fluoroethylene carbonate, vinylene carbonate and lithium bis-fluorosulfonyl imide, wherein the mass ratio of the other additives is 2:1:1:1, a step of; the mass ratio of the other additives in the nonaqueous electrolyte is 2% -8%;
the positive electrode comprises a positive electrode active material, wherein the positive electrode active material is selected from nickel cobalt lithium manganate, and the mole fraction of nickel is more than or equal to 0.5 and less than 1.
2. The lithium ion battery of claim 1, wherein R in the compound of formula i F 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. 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 lithium ion battery of claim 1, wherein R 1 、R 2 Each independently selected from the following groups:
R F selected from-CF 3 or-F, and when R F When selected from-F, R 1 、R 2 Neither is equal to
4. A lithium-ion battery according to any one of claims 1 to 3, wherein the compound of formula i is selected from the group consisting of:
5. the lithium-ion battery of claim 1, wherein the battery comprises a plurality of lithium-ion batteries,
the nonaqueous organic solvent includes a cyclic carbonate and/or a chain carbonate;
and/or the concentration of the lithium salt in the nonaqueous electrolyte is 1mol/L to 2mol/L;
and/or the mass ratio of the nonaqueous organic solvent in the nonaqueous electrolyte is 60-85%.
6. The lithium ion battery of claim 5, wherein the nonaqueous organic solvent is selected from one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethylmethyl carbonate.
7. The lithium ion battery according to claim 1, wherein the nonaqueous electrolyte preparation 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 with anhydrous dichloromethane, and sequentially adding R under inert gas atmosphere 1 OH solution and R 2 Reacting the OH solution to obtain a compound shown in the formula I;
2) Reacting the compound shown in the formula II in the step 1) with a fluoro reagent to obtain a compound shown in the formula II; wherein R is 1 、R 2 As defined in claim 1.
8. The lithium ion battery of claim 1, wherein the negative electrode comprises a negative electrode active material selected from the group consisting of one or more of silicon carbon, natural graphite, artificial graphite, lithium titanate, amorphous carbon, and lithium metal.
9. A battery module characterized by comprising the lithium ion battery according to any one of claims 1 to 8.
10. A battery pack comprising the battery module according to claim 9.
11. An electric device comprising a lithium ion battery according to any one of claims 1 to 8, said lithium ion battery being used as a power source for said electric device.
12. The electrical device of claim 11, wherein the electrical device comprises a mobile device, an electric vehicle, an electric train, a satellite, a vessel, and an energy storage system.
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