WO2022213668A1 - Electrolyte additive and non-aqueous electrolyte and lithium ion battery containing additive - Google Patents
Electrolyte additive and non-aqueous electrolyte and lithium ion battery containing additive Download PDFInfo
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- WO2022213668A1 WO2022213668A1 PCT/CN2021/140298 CN2021140298W WO2022213668A1 WO 2022213668 A1 WO2022213668 A1 WO 2022213668A1 CN 2021140298 W CN2021140298 W CN 2021140298W WO 2022213668 A1 WO2022213668 A1 WO 2022213668A1
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- WIPO (PCT)
- Prior art keywords
- lithium
- electrolyte
- structural formula
- additive
- alkyl
- Prior art date
Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 16
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 14
- 239000000654 additive Substances 0.000 title claims abstract description 7
- 230000000996 additive effect Effects 0.000 title claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000000262 haloalkenyl group Chemical group 0.000 claims abstract description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 3
- 125000003106 haloaryl group Chemical group 0.000 claims abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 6
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 5
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 5
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical group N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Chemical group OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 4
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 claims description 4
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 3
- 229940126062 Compound A Drugs 0.000 claims description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910013716 LiNi Inorganic materials 0.000 claims description 2
- AUBNQVSSTJZVMY-UHFFFAOYSA-M P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] AUBNQVSSTJZVMY-UHFFFAOYSA-M 0.000 claims description 2
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims description 2
- 125000005741 alkyl alkenyl group Chemical group 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 150000005678 chain carbonates Chemical class 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- RBBXSUBZFUWCAV-UHFFFAOYSA-N ethenyl hydrogen sulfite Chemical compound OS(=O)OC=C RBBXSUBZFUWCAV-UHFFFAOYSA-N 0.000 claims description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 2
- 125000005059 halophenyl group Chemical group 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 10
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical group O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 abstract description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006864 oxidative decomposition reaction Methods 0.000 abstract description 5
- 150000008064 anhydrides Chemical group 0.000 abstract 2
- 125000003342 alkenyl group Chemical group 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000004018 acid anhydride group Chemical group 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical group N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006866 deterioration Effects 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
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present application relates to the field of secondary batteries, in particular to an electrolyte additive, a non-aqueous electrolyte containing the additive, and a lithium ion battery.
- the cathode materials of commercial lithium-ion batteries mainly include lithium manganate, lithium cobaltate, ternary materials, and lithium iron phosphate.
- the charge cut-off voltage generally does not exceed 4.2V. It is increasingly important and urgent to improve the energy density of lithium-ion batteries.
- high-voltage (4.35V-5V) cathode materials are one of the more popular research directions, which achieves high energy density of batteries by increasing the charging depth of cathode active materials.
- the high-voltage materials found so far are mainly: 1) 4.35-4.5V LCO, the working voltage of LCO can be improved by doping modified elements Mg, Al, Ti, Zr or by coating means, but the resources of cobalt are limited, and the price Relatively high, so it is mainly used in small mobile terminals in the 3C field; 2) 5V nickel-manganese spinel (LNMS), after this material is modified by doping, it has good cycle performance even with conventional electrolytes.
- LNMS 5V nickel-manganese spinel
- the ternary material faces the problems of poor high temperature storage and serious gas production in the cycle.
- the newly developed coating or doping technology may not be perfect. Under high temperature conditions, the oxidative decomposition of the electrolyte will be accelerated, and the deterioration reaction of the positive electrode material will be promoted at the same time. Therefore, it is necessary to develop an electrolyte that can withstand a high voltage of 4.4V, so as to achieve excellent performance of lithium-ion batteries.
- the purpose of this application is to provide an electrolyte additive, a non-aqueous electrolyte containing the additive, and a lithium ion battery, the electrolyte can improve the high temperature storage and cycle performance of the battery, and is especially suitable for lithium ion batteries under high voltage systems.
- a first aspect of the present application provides an electrolyte additive, comprising a compound having structural formula 1 or structural formula 2,
- R 1 and R 2 are each independently selected from C 1 to C 12 alkyl, C 1 to C 12 haloalkyl, isocyanic acid substituted C 1 to C 12 alkyl, C 2 to C 12 alkyl Alkenyl, C 2 to C 12 haloalkenyl, C 6 to C 26 aryl or C 6 to C 26 haloaryl, R 3 is C 1 to C 12 alkyl.
- the electrolyte additive of the present application has connected barbituric acid groups and acid anhydride groups, which, relative to the combination of barbituric acid and acid anhydride, can form nitrogen-containing compounds at the electrode/electrolyte interface.
- Carbonate interface film this interface film has good thermal stability, can inhibit the oxidative decomposition of the electrolyte, and has a high performance of conducting lithium ions, which can significantly improve the conduction rate of lithium ions.
- the high temperature storage and cycling performance of the battery can be effectively improved.
- R 1 and R 2 are each independently selected from C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, isocyanic acid substituted C 2 to C 7 alkyl, phenyl or halo phenyl.
- the compound with structural formula 1 or structural formula 2 is selected from at least one of compound A to compound H,
- a second aspect of the present application provides a non-aqueous electrolyte, comprising a lithium salt, a non-aqueous organic solvent and the aforementioned electrolyte additive, and the weight percentage of the compound having the structural formula 1 or the structural formula 2 in the non-aqueous electrolyte is 0.1 ⁇ 5%.
- the lithium salt is selected from lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium difluorophosphate (LiPO 2 F 2 ), lithium bis-oxalate borate (C 4 BLiO 8 ), difluorooxalate borate Lithium (C 2 BF 2 LiO 4 ), Lithium Difluorobisoxalate Phosphate (LiDFBP), Lithium Tetrafluoroborate (LiBF 4 ), Lithium Tetrafluorooxalate Phosphate (LiOTFP), Lithium Bistrifluoromethanesulfonimide (LiN) (CF 3 SO 2 ) 2 ), lithium bisfluorosulfonimide (LiFSI), and lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), and the concentration is 0.5-1.5M.
- the non-aqueous organic solvent is selected from at least one of chain carbonate, cyclic carbonate and carboxylate.
- the non-aqueous organic solvent can be ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), propylene carbonate (PC), butyl acetate At least one of ester (n-Ba), ⁇ -butyrolactone ( ⁇ -Bt), propyl propionate (n-Pp), ethyl propionate (EP) and ethyl butyrate (Eb).
- ester n-Ba
- ⁇ -butyrolactone ⁇ -Bt
- propyl propionate n-Pp
- EP ethyl propionate
- Eb ethyl butyrate
- auxiliary agent in the non-aqueous electrolyte, and the auxiliary agent is selected from vinylene carbonate (VC), vinyl ethylene carbonate (VEC), fluoroethylene carbonate At least one of ester (FEC), vinyl sulfite (ES), 1,3 propane sultone (PS) and vinyl sulfate (DTD).
- VC vinylene carbonate
- VEC vinyl ethylene carbonate
- FEC fluoroethylene carbonate
- FEC vinyl sulfite
- PS 1,3 propane sultone
- DTD vinyl sulfate
- a third aspect of the present application further provides a lithium ion battery, comprising a positive electrode material, a negative electrode material and an electrolyte, the electrolyte is the aforementioned non-aqueous electrolyte, and the positive electrode material includes nickel cobalt manganese oxide.
- the chemical formula of the nickel cobalt manganese oxide is LiNi x Co y Mn (1-xy) M z O 2 , wherein 0.6 ⁇ x ⁇ 0.9, x+y ⁇ 1, 0 ⁇ z ⁇ 0.08, and M is At least one of Al, Mg, Zr and Ti.
- ethylene carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate ( EMC) mixture 87g as an organic solvent, add 0.5g compound A to obtain a mixed solution, then slowly add 12.5g of 1M LiPF 6 to the mixed solution, and mix uniformly to prepare an electrolyte.
- EC ethylene carbonate
- DEC diethyl carbonate
- EMC methyl ethyl carbonate
- Examples 1-15 and Comparative Examples 1-9 were prepared with reference to the following lithium batteries Methods A lithium-ion battery was prepared, and the first Coulomb efficiency test, normal temperature cycle performance, high temperature cycle performance, and high temperature storage tests were carried out respectively.
- the test conditions were as follows, and the test results are shown in Table 2.
- the nickel cobalt lithium manganate ternary material LiNi 0.8 Co 0.1 Mn 0.1 O 2 , the conductive agent SuperP, the binder PVDF and carbon nanotubes (CNT) were mixed uniformly in a mass ratio of 96:2:1:1 to make a certain viscosity.
- the natural graphite, conductive agent SuperP, thickener CMC, and adhesive SBR styrene-butadiene rubber latex
- the natural graphite, conductive agent SuperP, thickener CMC, and adhesive SBR styrene-butadiene rubber latex
- the positive electrode sheet, the negative electrode sheet and the separator prepared according to the above process were made into a lithium ion battery with a thickness of 4.7 mm, a width of 55 mm and a length of 60 mm through a lamination process, and were vacuum baked at 75 ° C for 10 h.
- High temperature storage performance test Under the condition of normal temperature (25°C), charge and discharge the lithium-ion battery once at 0.5C/0.5C (discharge capacity is recorded as C0), the upper limit voltage is 4.4V, and then at 0.5C constant current and constant voltage condition to charge the battery to 4.4V.
- the lithium-ion battery was stored in a 60°C high temperature box for 30 days. After taking it out, it was discharged at 0.5C at normal temperature (discharge capacity was recorded as C1); then it was charged and discharged at 0.5C/0.5C at normal temperature (discharged The capacity is recorded as C2), and the capacity retention rate and capacity recovery rate of the lithium-ion battery are calculated using the following formulas:
- Capacity recovery rate C2/C0*100%.
- Capacity retention rate (C1/C0)*100%.
- High temperature cycle test Under the condition of excessive high temperature (45°C), the lithium-ion battery is charged and discharged once at 1.0C/1.0C (battery discharge capacity is C0), and the upper limit voltage is 4.4V. Then charge and discharge at 1.0C/1.0C for 500 cycles at normal temperature (battery discharge capacity is C1),
- Capacity retention rate (C1/C0)*100%.
- Example 10 Compared Example 10 and Examples 12-15, it can be seen that adding some additives on the basis of the compound additive with structural formula 1 or structural formula 2, its cycle performance and high temperature performance are better. And when used in combination with VC and FEC, the performance is better, which may be due to the synergistic effect of the organic interface film formed by the compound at the electrode/electrolyte interface and the organic interface film formed by VC and FEC, which has higher thermal stability. It also has excellent selective permeability to lithium ions.
- the electrolyte additive of the application has connected barbituric acid groups and acid anhydride groups, which, compared with the combination of barbituric acid and acid anhydride, can be used in electrodes/electrolyzers.
- a nitrogen-containing carbonate interface film is formed at the liquid interface. This interface film has good thermal stability, can inhibit the oxidative decomposition of the electrolyte, and has a high performance of conducting lithium ions, which can significantly improve the conduction rate of lithium ions. Therefore, Better cycle performance and storage performance.
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Abstract
An electrolyte additive and a non-aqueous electrolyte and lithium ion battery containing the additive. The electrolyte additive comprises a compound having a structural formula (1) or a structural formula (2), wherein R1 and R2 are each independently selected from alkyl groups of C1 to C12, haloalkyl groups of C1 to C12, alkyl groups of isocyanate-substituted C1 to C12, alkenyl groups of C2 to C12, haloalkenyl groups of C2 to C12, aryl groups of C6 to C26, or haloaryl groups of C6 to C26; and R3 is an alkyl group from C1 to C12. The electrolyte additive of the present application has an attached barbituric acid group and anhydride group, and can form a nitrogen-containing carbonate interface film at an electrode/electrolyte interface. The interface film has good thermal stability, can inhibit the oxidative decomposition of an electrolyte, has a good lithium ion conduction performance, and can significantly increase the conduction rate of lithium ions. Therefore, the high-temperature storage and circulation performance of the battery can be effectively improved on the basis of the anhydride group, the barbituric acid group, and the nitrogen-containing carbonate interface film.
Description
本申请涉及二次电池领域，具体涉及一种电解液添加剂和含有该添加剂的非水电解液及锂离子电池。The present application relates to the field of secondary batteries, in particular to an electrolyte additive, a non-aqueous electrolyte containing the additive, and a lithium ion battery.
目前，商业用锂离子电池的正极材料主要有锰酸锂、钴酸锂、三元材料、磷酸亚铁锂几种，其充电截止电压一般不超过4.2V，随着科技的进步及市场的不断发展，提升锂离子电池的能量密度日益显得重要而迫切。除了现有材料和电池的制作工艺改进之外，高电压(4.35V-5V)正极材料是比较热门的研究方向之一，它是通过提升正极活性材料的充电深度来实现电池的高能量密度。At present, the cathode materials of commercial lithium-ion batteries mainly include lithium manganate, lithium cobaltate, ternary materials, and lithium iron phosphate. The charge cut-off voltage generally does not exceed 4.2V. It is increasingly important and urgent to improve the energy density of lithium-ion batteries. In addition to the improvement of existing materials and battery manufacturing process, high-voltage (4.35V-5V) cathode materials are one of the more popular research directions, which achieves high energy density of batteries by increasing the charging depth of cathode active materials.
目前发现的高电压材料主要有：1)4.35-4.5V LCO，通过掺杂改性元素Mg、Al、Ti、Zr或采用包覆手段来提高LCO的工作电压，但钴的资源有限，且价格相对较高，因而主要用于3C领域的小型移动终端中；2)5V镍锰尖晶石(LNMS)，这种材料通过掺杂改性之后，即使使用常规电解液，也有不错的循环性能和倍率性能，但安全性较差，且容量(130mAh/g)低，压实(3.1g/cm
3)低，相对其他高电压材料无明显优势；3)4.7V富锂高锰层状固溶体(OLO)，OLO容量(300mAh/g)、电压高，通过改性之后，首效能达到90％，但振实密度低(2.0g/cm
3)、没有电压平台、循环性能较差、严重的电压滞后、安全性能差，导致其应用受到限制；4)4.35-4.6V三元材料，对称型(442，333)高电压三元材料容量高，循环性能良好，通过改性后，其上限电压可以提升到4.6V，且三元材料资源丰富，在价格上较高电压LCO有明显优势。
The high-voltage materials found so far are mainly: 1) 4.35-4.5V LCO, the working voltage of LCO can be improved by doping modified elements Mg, Al, Ti, Zr or by coating means, but the resources of cobalt are limited, and the price Relatively high, so it is mainly used in small mobile terminals in the 3C field; 2) 5V nickel-manganese spinel (LNMS), after this material is modified by doping, it has good cycle performance even with conventional electrolytes. Rate performance, but poor safety, and low capacity (130mAh/g), low compaction (3.1g/cm 3 ), no obvious advantage over other high-voltage materials; 3) 4.7V lithium-rich high manganese layered solid solution ( OLO), OLO capacity (300mAh/g), high voltage, after modification, the initial efficiency reaches 90%, but low tap density (2.0g/cm 3 ), no voltage plateau, poor cycle performance, severe voltage Hysteresis and poor safety performance limit its application; 4) 4.35-4.6V ternary material, symmetrical (442, 333) high-voltage ternary material has high capacity and good cycle performance. After modification, its upper limit voltage can be It is raised to 4.6V, and the ternary material resources are abundant, and the higher voltage LCO has obvious advantages in price.
但是，随着上限电压的提升后，三元材料面临高温存储差、循环产气严重的问题。一方面可能是新开发的包覆或掺杂技术不太完善，另一方面即是电解液的匹配问题，常规的电解液在4.4V高电压下是会在电池正极表面氧化分解的， 特别在高温条件下，会加速电解液的氧化分解，同时促使正极材料的恶化反应。因此，必须开发一种能耐4.4V高电压的电解液，进而实现锂离子电池电性能的优良发挥。However, with the increase of the upper limit voltage, the ternary material faces the problems of poor high temperature storage and serious gas production in the cycle. On the one hand, the newly developed coating or doping technology may not be perfect. Under high temperature conditions, the oxidative decomposition of the electrolyte will be accelerated, and the deterioration reaction of the positive electrode material will be promoted at the same time. Therefore, it is necessary to develop an electrolyte that can withstand a high voltage of 4.4V, so as to achieve excellent performance of lithium-ion batteries.
申请内容Application content
本申请的目的在于提供一种电解液添加剂和含有该添加剂的非水电解液及锂离子电池，此电解液可提高电池的高温存储和循环性能，尤其适用于高电压体系下的锂离子电池。The purpose of this application is to provide an electrolyte additive, a non-aqueous electrolyte containing the additive, and a lithium ion battery, the electrolyte can improve the high temperature storage and cycle performance of the battery, and is especially suitable for lithium ion batteries under high voltage systems.
为实现上述目的，本申请第一方面提供了一种电解液添加剂，包含具有结构式1或结构式2的化合物，In order to achieve the above object, a first aspect of the present application provides an electrolyte additive, comprising a compound having structural formula 1 or structural formula 2,
其中，R
1、R
2各自独立地选自C
1至C
12的烷基、C
1至C
12的卤代烷基、异氰酸取代的C
1至C
12的烷基、C
2至C
12的烯基、C
2至C
12的卤代烯基、C
6至C
26的芳基或C
6至C
26的卤代芳基，R
3为C
1至C
12的烷基。
Wherein, R 1 and R 2 are each independently selected from C 1 to C 12 alkyl, C 1 to C 12 haloalkyl, isocyanic acid substituted C 1 to C 12 alkyl, C 2 to C 12 alkyl Alkenyl, C 2 to C 12 haloalkenyl, C 6 to C 26 aryl or C 6 to C 26 haloaryl, R 3 is C 1 to C 12 alkyl.
相对于现有技术，本申请的电解液添加剂具有相连的巴比妥酸基团和酸酐基团，其相对于巴比妥酸和酸酐的组合，能在电极/电解液界面处形成含氮的碳酸盐界面膜，此界面膜热稳定性好，可抑制电解液的氧化分解，且具有较高的 传导锂离子的性能，可显著提升锂离子的传导速率，因而在酸酐基团、巴比妥酸基团和含氮的碳酸盐界面膜的基础上，可有效提高电池的高温储存和循环性能。Compared with the prior art, the electrolyte additive of the present application has connected barbituric acid groups and acid anhydride groups, which, relative to the combination of barbituric acid and acid anhydride, can form nitrogen-containing compounds at the electrode/electrolyte interface. Carbonate interface film, this interface film has good thermal stability, can inhibit the oxidative decomposition of the electrolyte, and has a high performance of conducting lithium ions, which can significantly improve the conduction rate of lithium ions. On the basis of uric acid group and nitrogen-containing carbonate interfacial film, the high temperature storage and cycling performance of the battery can be effectively improved.
进一步的，R
1、R
2各自独立地选自C
1至C
6的烷基、C
1至C
6的卤代烷基、异氰酸取代的C
2至C
7的烷基、苯基或卤代苯基。
Further, R 1 and R 2 are each independently selected from C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, isocyanic acid substituted C 2 to C 7 alkyl, phenyl or halo phenyl.
更进一步的，具有结构式1或结构式2的化合物选自化合物A至化合物H中的至少一种，Further, the compound with structural formula 1 or structural formula 2 is selected from at least one of compound A to compound H,
本申请的第二方面提供了一种非水电解液，包括锂盐、非水有机溶剂和前述的电解液添加剂，所述具有结构式1或结构式2的化合物于非水电解液中的重量百分比为0.1～5％。A second aspect of the present application provides a non-aqueous electrolyte, comprising a lithium salt, a non-aqueous organic solvent and the aforementioned electrolyte additive, and the weight percentage of the compound having the structural formula 1 or the structural formula 2 in the non-aqueous electrolyte is 0.1～5%.
进一步的，所述锂盐选自六氟磷酸锂(LiPF
6)、高氯酸锂(LiClO
4)、二氟磷酸锂(LiPO
2F
2)、双草酸硼酸锂(C
4BLiO
8)、二氟草酸硼酸锂(C
2BF
2LiO
4)、二氟二草酸磷酸锂(LiDFBP)、四氟硼酸锂(LiBF
4)、四氟草酸磷酸锂(LiOTFP)、双三氟甲基磺酰亚胺锂(LiN(CF
3SO
2)
2)、双氟磺酰亚胺锂(LiFSI)、和三氟甲基磺酸锂(LiCF
3SO
3)中的至少一种，且浓度为0.5～1.5M。
Further, the lithium salt is selected from lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium difluorophosphate (LiPO 2 F 2 ), lithium bis-oxalate borate (C 4 BLiO 8 ), difluorooxalate borate Lithium (C 2 BF 2 LiO 4 ), Lithium Difluorobisoxalate Phosphate (LiDFBP), Lithium Tetrafluoroborate (LiBF 4 ), Lithium Tetrafluorooxalate Phosphate (LiOTFP), Lithium Bistrifluoromethanesulfonimide (LiN) (CF 3 SO 2 ) 2 ), lithium bisfluorosulfonimide (LiFSI), and lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), and the concentration is 0.5-1.5M.
进一步的，所述非水有机溶剂选自链状碳酸酯、环状碳酸酯和羧酸酯中的至少一种。更进一步的，非水有机溶剂可为碳酸乙烯酯(EC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸丙烯酯(PC)、乙酸丁酯(n-Ba)、γ-丁内酯(γ-Bt)、丙酸丙酯(n-Pp)、丙酸乙酯(EP)和丁酸乙酯(Eb)中的至少一种。Further, the non-aqueous organic solvent is selected from at least one of chain carbonate, cyclic carbonate and carboxylate. Further, the non-aqueous organic solvent can be ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), propylene carbonate (PC), butyl acetate At least one of ester (n-Ba), γ-butyrolactone (γ-Bt), propyl propionate (n-Pp), ethyl propionate (EP) and ethyl butyrate (Eb).
进一步的，还包括占非水电解液中的重量百分比为0.1～5％的助剂，所述助剂选自碳酸亚乙烯酯(VC)、乙烯基碳酸乙烯酯(VEC)、氟代碳酸乙烯酯(FEC)、亚硫酸乙烯酯(ES)、1,3丙磺酸内酯(PS)和硫酸乙烯酯(DTD)中的至少一种。Further, it also includes 0.1-5% by weight of an auxiliary agent in the non-aqueous electrolyte, and the auxiliary agent is selected from vinylene carbonate (VC), vinyl ethylene carbonate (VEC), fluoroethylene carbonate At least one of ester (FEC), vinyl sulfite (ES), 1,3 propane sultone (PS) and vinyl sulfate (DTD).
本申请第三方面还提供了一种锂离子电池，包括正极材料、负极材料和电解液，所述电解液为前述的非水电解液，且所述正极材料包括镍钴锰氧化物。进一步的，所述镍钴锰氧化物的化学式为LiNi
xCo
yMn
(1-x-y)M
zO
2，其中，0.6≤x<0.9，x+y＜1，0≤z<0.08，M为Al、Mg、Zr和Ti中的至少一种。
A third aspect of the present application further provides a lithium ion battery, comprising a positive electrode material, a negative electrode material and an electrolyte, the electrolyte is the aforementioned non-aqueous electrolyte, and the positive electrode material includes nickel cobalt manganese oxide. Further, the chemical formula of the nickel cobalt manganese oxide is LiNi x Co y Mn (1-xy) M z O 2 , wherein 0.6≤x<0.9, x+y<1, 0≤z<0.08, and M is At least one of Al, Mg, Zr and Ti.
为更好地说明本申请的目的、技术方案和有益效果，下面将结合具体实施例对本申请作进一步说明。需说明的是，下述实施所述方法是对本申请做的进 一步解释说明，不应当作为对本申请的限制。In order to better illustrate the purpose, technical solutions and beneficial effects of the present application, the present application will be further described below with reference to specific embodiments. It should be noted that the following implementation of the method is a further explanation for the application, and should not be used as a limitation to the application.
实施例1Example 1
在充满氮气的手套箱(O
2＜2ppm，H
2O＜3ppm)中，将重量比为1:1:1的碳酸乙烯酯(EC)、碳酸二乙酯(DEC)和碳酸甲乙酯(EMC)的混和物87g作为有机溶剂，加入0.5g化合物A得混合溶液，再向混合溶液中缓慢加入1M LiPF
612.5g，混合均匀后即制成电解液。
In a nitrogen-filled glove box (O 2 <2 ppm, H 2 O < 3 ppm), ethylene carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate ( EMC) mixture 87g as an organic solvent, add 0.5g compound A to obtain a mixed solution, then slowly add 12.5g of 1M LiPF 6 to the mixed solution, and mix uniformly to prepare an electrolyte.
实施例2～15和对比例1～9的电解液配方如表1所示，配制电解液的步骤同实施例1。The electrolyte formulations of Examples 2 to 15 and Comparative Examples 1 to 9 are shown in Table 1, and the steps for preparing electrolytes are the same as those of Example 1.
表1各实施例的电解液组分Electrolyte composition of each embodiment of table 1
以最高充电电压为4.4V的NCM811(LiNi
0.8Co
0.1Mn
0.1O
2)为正极材料，天然石墨为负极材料，以实施例1～15和对比例1～9的电解液参照下述锂电池制备方法制成锂离子电池，并分别进行首次库伦效率测试、常温循环性能、高温循环性能、高温存储测试，其测试条件如下，测试结果如表2所示。
Using NCM811 (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) with the highest charging voltage of 4.4V as the positive electrode material and natural graphite as the negative electrode material, the electrolytes of Examples 1-15 and Comparative Examples 1-9 were prepared with reference to the following lithium batteries Methods A lithium-ion battery was prepared, and the first Coulomb efficiency test, normal temperature cycle performance, high temperature cycle performance, and high temperature storage tests were carried out respectively. The test conditions were as follows, and the test results are shown in Table 2.
锂电池制备方法：Preparation method of lithium battery:
1.正极片的制备1. Preparation of positive electrode sheet
将镍钴锰酸锂三元材料LiNi
0.8Co
0.1Mn
0.1O
2、导电剂SuperP、粘接剂PVDF和碳纳米管(CNT)按质量比96:2:1:1混合均匀制成一定粘度的锂离子电池正极浆料，涂布在集流体用铝箔上，其涂布量为324g/m
2，在85℃下烘干后进行冷压；然后进行切边、裁片、分条，分条后在真空条件下85℃烘干4h，焊接极耳，制成满足要求的锂离子电池正极片。
The nickel cobalt lithium manganate ternary material LiNi 0.8 Co 0.1 Mn 0.1 O 2 , the conductive agent SuperP, the binder PVDF and carbon nanotubes (CNT) were mixed uniformly in a mass ratio of 96:2:1:1 to make a certain viscosity. Lithium-ion battery cathode slurry, coated on aluminum foil for current collector, the coating amount is 324g/m 2 , dried at 85°C, and then cold-pressed; then trimmed, cut, slit, and slit After drying at 85°C for 4 hours under vacuum conditions, the tabs were welded to produce a positive electrode sheet for lithium ion batteries that met the requirements.
2.负极片的制备2. Preparation of Anode Sheets
将天然石墨与导电剂SuperP、增稠剂CMC、粘接剂SBR(丁苯橡胶乳液)按质量比95:1.5:1.5:2的比例制成浆料，涂布在集流体铜箔上并在85℃下烘干，涂布量为168g/m
2；进行切边、裁片、分条，分条后在真空条件下110℃烘干4h， 焊接极耳，制成满足要求的锂离子电池负极片。
The natural graphite, conductive agent SuperP, thickener CMC, and adhesive SBR (styrene-butadiene rubber latex) were made into a slurry in a mass ratio of 95:1.5:1.5:2, which was coated on the current collector copper foil and placed on the current collector copper foil. Drying at 85°C with a coating weight of 168g/m 2 ; trimming, cutting and slitting, drying at 110°C for 4h under vacuum conditions after slitting, welding the tabs, and producing a lithium-ion battery that meets the requirements Negative sheet.
3.锂离子电池的制备3. Preparation of Li-ion Batteries
将根据上述工艺制备的正极片、负极片和隔膜经叠片工艺制作成厚度为4.7mm，宽度为55mm，长度为60mm的锂离子电池，在75℃下真空烘烤10h，注入实施例16和对比例1～5的非水电解液。静置24h后，用0.lC(180mA)的恒流充电至4.45V，然后以4.45V恒压充电至电流下降到0.05C(90mA)；然后以0.2C(180mA)放电至3.0V，重复2次充放电，最后再以0.2C(180mA)将电池充电至3.8V，完成电池制作。The positive electrode sheet, the negative electrode sheet and the separator prepared according to the above process were made into a lithium ion battery with a thickness of 4.7 mm, a width of 55 mm and a length of 60 mm through a lamination process, and were vacuum baked at 75 ° C for 10 h. Non-aqueous electrolytes of Comparative Examples 1 to 5. After standing for 24h, charge to 4.45V with a constant current of 0.1C (180mA), then charge with a constant voltage of 4.45V until the current drops to 0.05C (90mA); then discharge to 3.0V at 0.2C (180mA), repeat Charge and discharge twice, and finally charge the battery to 3.8V at 0.2C (180mA) to complete the battery production.
高温存储性能测试：在常温(25℃)条件下，对锂离子电池进行一次0.5C/0.5C充电和放电(放电容量记为C0)，上限电压为4.4V，然后在0.5C恒流恒压条件下将电池充电至4.4V。将锂离子电池置于60℃高温箱中保存30天，取出后，在常温条件下进行0.5C放电(放电容量记为C1)；然后在常温条件下进行0.5C/0.5C充电和放电(放电容量记为C2)，利用下面公式计算锂离子电池的容量保持率和容量恢复率：High temperature storage performance test: Under the condition of normal temperature (25℃), charge and discharge the lithium-ion battery once at 0.5C/0.5C (discharge capacity is recorded as C0), the upper limit voltage is 4.4V, and then at 0.5C constant current and constant voltage condition to charge the battery to 4.4V. The lithium-ion battery was stored in a 60°C high temperature box for 30 days. After taking it out, it was discharged at 0.5C at normal temperature (discharge capacity was recorded as C1); then it was charged and discharged at 0.5C/0.5C at normal temperature (discharged The capacity is recorded as C2), and the capacity retention rate and capacity recovery rate of the lithium-ion battery are calculated using the following formulas:
容量保持率＝C1/C0*100％Capacity retention rate=C1/C0*100%
容量恢复率＝C2/C0*100％。Capacity recovery rate=C2/C0*100%.
常温循环测试：在常温(25℃)条件下，对锂离子电池进行一次1.0C/1.0C充电和放电(电池放电容量为C0)，上限电压为4.4V，然后在常温条件下进行1.0C/1.0C充电和放电500周(电池放电容量为C1)，Normal temperature cycle test: Under the condition of normal temperature (25℃), charge and discharge the lithium-ion battery once at 1.0C/1.0C (the battery discharge capacity is C0), the upper limit voltage is 4.4V, and then conduct 1.0C/1.0C/ 1.0C charge and discharge for 500 cycles (battery discharge capacity is C1),
容量保持率＝(C1/C0)*100％。Capacity retention rate=(C1/C0)*100%.
高温循环测试：在过高温(45℃)条件下，对锂离子电池进行一次1.0C/1.0C充电和放电(电池放电容量为C0)，上限电压为4.4V。然后在常温条件下进行1.0C/1.0C充电和放电500周(电池放电容量为C1)，High temperature cycle test: Under the condition of excessive high temperature (45°C), the lithium-ion battery is charged and discharged once at 1.0C/1.0C (battery discharge capacity is C0), and the upper limit voltage is 4.4V. Then charge and discharge at 1.0C/1.0C for 500 cycles at normal temperature (battery discharge capacity is C1),
容量保持率＝(C1/C0)*100％。Capacity retention rate=(C1/C0)*100%.
表2循环和高温存储性能测试结果Table 2 Cycle and high temperature storage performance test results
从表2的结果可知，相对于对比例1～9，实施例1～15的高温和常温循环性能、高温存储性能皆能处于较佳的水平。这是由于本申请的电解液添加剂具有相连的巴比妥酸基团和酸酐基团，能在电极/电解液界面处形成含氮的碳酸盐界面膜，此界面膜热稳定性好，可抑制电解液的氧化分解，且具有较高的传导锂离子的性能，可显著提升锂离子的传导速率，因而在酸酐基团、巴比妥酸基团和含氮的碳酸盐界面膜的基础上，可有效提高电池的高温储存和循环性能。It can be seen from the results in Table 2 that, compared with Comparative Examples 1 to 9, the high temperature and normal temperature cycle performance and high temperature storage performance of Examples 1 to 15 can be at a better level. This is because the electrolyte additive of the present application has connected barbituric acid groups and acid anhydride groups, and can form a nitrogen-containing carbonate interface film at the electrode/electrolyte interface. The interface film has good thermal stability and can be It inhibits the oxidative decomposition of the electrolyte, and has a high performance of conducting lithium ions, which can significantly improve the conduction rate of lithium ions. It can effectively improve the high temperature storage and cycle performance of the battery.
而且，对比实施例10和实施例12-15可知，于具有结构式1或结构式2的 化合物添加剂的基础上再增加一些助剂，其循环性能和高温性能更佳。且和VC、FEC搭配使用时，性能更佳，可能是由于该化合物在电极/电解液界面处形成的有机界面膜与VC和FEC形成的有机界面膜产生了协同作用，具有较高的热稳定性，同时对锂离子具有较优的选择透过性。Moreover, comparing Example 10 and Examples 12-15, it can be seen that adding some additives on the basis of the compound additive with structural formula 1 or structural formula 2, its cycle performance and high temperature performance are better. And when used in combination with VC and FEC, the performance is better, which may be due to the synergistic effect of the organic interface film formed by the compound at the electrode/electrolyte interface and the organic interface film formed by VC and FEC, which has higher thermal stability. It also has excellent selective permeability to lithium ions.
对比实施例10和对比例5、7～8可知，申请的电解液添加剂具有相连的巴比妥酸基团和酸酐基团，其相对于巴比妥酸和酸酐的组合，能在电极/电解液界面处形成含氮的碳酸盐界面膜，此界面膜热稳定性好，可抑制电解液的氧化分解，且具有较高的传导锂离子的性能，可显著提升锂离子的传导速率，故循环性能和存储性能较佳。Comparing Example 10 and Comparative Examples 5 and 7 to 8, it can be seen that the electrolyte additive of the application has connected barbituric acid groups and acid anhydride groups, which, compared with the combination of barbituric acid and acid anhydride, can be used in electrodes/electrolyzers. A nitrogen-containing carbonate interface film is formed at the liquid interface. This interface film has good thermal stability, can inhibit the oxidative decomposition of the electrolyte, and has a high performance of conducting lithium ions, which can significantly improve the conduction rate of lithium ions. Therefore, Better cycle performance and storage performance.
最后应当说明的是，以上实施例仅用以说明本申请的技术方案而非对本申请保护范围的限制，尽管参照较佳实施例对本申请作了详细说明，本领域的普通技术人员应当理解，可以对本申请的技术方案进行修改或者等同替换，而不脱离本申请技术方案的实质和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application and not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should The technical solutions of the present application may be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present application.
Claims (10)
- 一种电解液添加剂，其特征在于，包含具有结构式1或结构式2的化合物，A kind of electrolyte additive, it is characterized in that, comprise the compound with structural formula 1 or structural formula 2,
其中，R 1、R 2各自独立地选自C 1至C 12的烷基、C 1至C 12的卤代烷基、异氰酸取代的C 1至C 12的烷基、C 2至C 12的烯基、C 2至C 12的卤代烯基、C 6至C 26的芳基或C 6至C 26的卤代芳基，R 3为C 1至C 12的烷基。 Wherein, R 1 and R 2 are each independently selected from C 1 to C 12 alkyl, C 1 to C 12 haloalkyl, isocyanic acid substituted C 1 to C 12 alkyl, C 2 to C 12 alkyl Alkenyl, C 2 to C 12 haloalkenyl, C 6 to C 26 aryl or C 6 to C 26 haloaryl, R 3 is C 1 to C 12 alkyl. - 如权利要求1所述的电解液添加剂，其特征在于，R 1、R 2各自独立地选自C 1至C 6的烷基、C 1至C 6的卤代烷基、异氰酸取代的C 2至C 7的烷基、苯基或卤代苯基。 The electrolyte additive according to claim 1, wherein R 1 and R 2 are each independently selected from C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, and isocyanic acid substituted C 2 to C7 alkyl, phenyl or halophenyl.
- 如权利要求1所述的电解液添加剂，其特征在于，所述具有结构式1或结构式2的化合物选自化合物A至化合物H中的至少一种，The electrolyte additive according to claim 1, wherein the compound having structural formula 1 or structural formula 2 is selected from at least one of compound A to compound H,
- 一种非水电解液，包括锂盐、非水有机溶剂和如权利要求1～3任一所述的电解液添加剂。A non-aqueous electrolyte solution, comprising a lithium salt, a non-aqueous organic solvent and the electrolyte solution additive according to any one of claims 1 to 3.
- 如权利要求4所述的非水电解液，其特征在于，所述具有结构式1或结构式2的化合物于非水电解液中的重量百分比为0.1～5％。The non-aqueous electrolyte solution according to claim 4, wherein the weight percentage of the compound having the structural formula 1 or the structural formula 2 in the non-aqueous electrolyte solution is 0.1-5%.
- 如权利要求4所述的非水电解液，其特征在于，所述锂盐选自六氟磷酸锂、高氯酸锂、二氟磷酸锂、双草酸硼酸锂、二氟草酸硼酸锂、二氟二草酸磷酸锂、四氟硼酸锂、四氟草酸磷酸锂、双三氟甲基磺酰亚胺锂、双氟磺酰亚胺 锂、三氟甲基磺酸锂中的至少一种。The non-aqueous electrolyte according to claim 4, wherein the lithium salt is selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium difluorophosphate, lithium bis-oxalate borate, lithium difluorooxalate borate, and difluorobisoxalate phosphoric acid At least one of lithium, lithium tetrafluoroborate, lithium tetrafluorooxalate phosphate, lithium bistrifluoromethanesulfonimide, lithium bisfluorosulfonimide, and lithium trifluoromethanesulfonate.
- 如权利要求4所述的非水电解液，其特征在于，所述非水有机溶剂选自链状碳酸酯、环状碳酸酯和羧酸酯中的至少一种。The non-aqueous electrolyte solution according to claim 4, wherein the non-aqueous organic solvent is selected from at least one of chain carbonate, cyclic carbonate and carboxylate.
- 如权利要求4所述的非水电解液，其特征在于，还包括助剂，所述助剂选自碳酸亚乙烯酯、乙烯基碳酸乙烯酯、氟代碳酸乙烯酯、亚硫酸乙烯酯、1,3丙磺酸内酯和硫酸乙烯酯中的至少一种。The non-aqueous electrolyte solution according to claim 4, further comprising an auxiliary agent selected from the group consisting of vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, vinyl sulfite, , at least one of 3 propane sultone and vinyl sulfate.
- 一种锂离子电池，包括正极材料、负极材料和电解液，其特征在于，所述电解液为权利要求4～8任一所述的非水电解液，且所述正极材料包括镍钴锰氧化物。A lithium ion battery, comprising a positive electrode material, a negative electrode material and an electrolyte, wherein the electrolyte is the non-aqueous electrolyte according to any one of claims 4 to 8, and the positive electrode material comprises nickel-cobalt-manganese oxide thing.
- 如权利要求9所述的锂离子电池，其特征在于，所述镍钴锰氧化物的化学式为LiNi xCo yMn (1-x-y)M zO 2，其中，0.6≤x<0.9，x+y＜1，0≤z<0.08，M为Al、Mg、Zr和Ti中的至少一种。 The lithium ion battery according to claim 9, wherein the chemical formula of the nickel cobalt manganese oxide is LiNi x Co y Mn (1-xy) M z O 2 , wherein 0.6≤x<0.9, x+ y<1, 0≤z<0.08, and M is at least one of Al, Mg, Zr, and Ti.
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| US4544743A (en) * | 1982-06-29 | 1985-10-01 | Societe Carbochimique | Salts of 1,3,5-oxadiazines-2,4,6-triones, 1,3,5-oxadiazines-2,4,6-triones and the preparation thereof |
| JP2002008719A (en) * | 2000-06-27 | 2002-01-11 | Mitsui Chemicals Inc | Nonaqueous electrolyte and secondary battery using the same |
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