CN114497741B - High-voltage electrolyte and lithium ion battery - Google Patents
High-voltage electrolyte and lithium ion battery Download PDFInfo
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- CN114497741B CN114497741B CN202210143020.9A CN202210143020A CN114497741B CN 114497741 B CN114497741 B CN 114497741B CN 202210143020 A CN202210143020 A CN 202210143020A CN 114497741 B CN114497741 B CN 114497741B
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- electrolyte
- lithium
- ion battery
- lithium ion
- carbonate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 113
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 91
- 239000000654 additive Substances 0.000 claims abstract description 50
- 230000000996 additive effect Effects 0.000 claims abstract description 46
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 45
- -1 silicon sulfamoyl lithium salt Chemical compound 0.000 claims abstract description 31
- 239000007774 positive electrode material Substances 0.000 claims abstract description 22
- 239000003223 protective agent Substances 0.000 claims abstract description 21
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 20
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 18
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 23
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 21
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 19
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 125000005910 alkyl carbonate group Chemical group 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 238000006467 substitution reaction Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 5
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 5
- 239000010406 cathode material Substances 0.000 claims description 5
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 5
- 229910001437 manganese ion Inorganic materials 0.000 claims description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 5
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 4
- RAHGWTWOXAELNS-UHFFFAOYSA-N 2-fluorohexanedinitrile Chemical compound N#CC(F)CCCC#N RAHGWTWOXAELNS-UHFFFAOYSA-N 0.000 claims description 4
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 claims description 4
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- WUICPPBYLKNKNS-UHFFFAOYSA-N benzene-1,2,3-tricarbonitrile Chemical compound N#CC1=CC=CC(C#N)=C1C#N WUICPPBYLKNKNS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- DFJYZCUIKPGCSG-UHFFFAOYSA-N decanedinitrile Chemical compound N#CCCCCCCCCC#N DFJYZCUIKPGCSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- LNLFLMCWDHZINJ-UHFFFAOYSA-N hexane-1,3,6-tricarbonitrile Chemical compound N#CCCCC(C#N)CCC#N LNLFLMCWDHZINJ-UHFFFAOYSA-N 0.000 claims description 4
- BTNXBLUGMAMSSH-UHFFFAOYSA-N octanedinitrile Chemical compound N#CCCCCCCC#N BTNXBLUGMAMSSH-UHFFFAOYSA-N 0.000 claims description 4
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 4
- JEXYCADTAFPULN-UHFFFAOYSA-N 1-propylsulfonylpropane Chemical compound CCCS(=O)(=O)CCC JEXYCADTAFPULN-UHFFFAOYSA-N 0.000 claims description 3
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 2
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 17
- 210000001787 dendrite Anatomy 0.000 abstract description 16
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 6
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 6
- 239000007773 negative electrode material Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 125000002560 nitrile group Chemical group 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910013872 LiPF Inorganic materials 0.000 description 8
- 101150058243 Lipf gene Proteins 0.000 description 8
- 230000002401 inhibitory effect Effects 0.000 description 8
- 238000013508 migration Methods 0.000 description 8
- 230000005012 migration Effects 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 6
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 5
- 150000002825 nitriles Chemical group 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910013246 LiNiMnO Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- SOUBRVXEOBMUKO-UHFFFAOYSA-N pentane-1,3,3,5-tetracarbonitrile Chemical compound N#CCCC(C#N)(C#N)CCC#N SOUBRVXEOBMUKO-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- PRZFAGGNAKJNQW-UHFFFAOYSA-N 3-methyl-1,2-benzothiazol-5-amine Chemical compound C1=C(N)C=C2C(C)=NSC2=C1 PRZFAGGNAKJNQW-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910015866 LiNi0.8Co0.1Al0.1O2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides an electrolyte for a lithium ion battery, which comprises a nonaqueous organic solvent, electrolyte lithium salt and a multifunctional additive; the multifunctional additive comprises a lithium silasulfamoyl salt, an anode and cathode protective agent and an additive. The silicon sulfamoyl lithium salt in the electrolyte has proper LUMO energy level and HOMO energy level, can form a film on the surfaces of positive and negative electrode materials, has a stable film structure, improves the interface compatibility of the positive electrode and the negative electrode, and improves the high-voltage performance and the cycle performance of the battery; the anode and cathode protection additive is nitrile substance containing a plurality of cyano groups, which not only captures metal ions separated out from the ternary anode material under high voltage to form complex to prevent the complex from forming metal dendrite on the cathode after entering the electrolyte, but also can form strong bond with the cathode, thereby improving the components of SEI film, enhancing the toughness and conductivity of SEI film and further improving the interface stability of the cathode. Moreover, the preparation method of the electrolyte is simple, the process is controllable, and the electrolyte is more suitable for industrial popularization and application.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, relates to electrolyte for a lithium ion battery and the lithium ion battery, and particularly relates to high-voltage electrolyte and the lithium ion battery.
Background
A lithium ion battery is a secondary battery (rechargeable battery) that operates mainly by means of lithium ions moving between a positive electrode and a negative electrode. During charge and discharge, li + To-and-fro intercalation and deintercalation between two electrodes: during charging, li + De-intercalation from the positive electrode, and intercalation into the negative electrode through the electrolyte, wherein the negative electrode is in a lithium-rich state; the opposite is true when discharging. Batteries generally employ materials containing lithium as electrodes, which are representative of modern high performance batteries. Lithium ion batteries generally include a positive electrode, a negative electrode, and a separatorThe electrolyte and the shell have the advantages of high working voltage, high specific energy, long cycle life, light weight, less self discharge, no memory effect, high cost performance and the like, and become the main selection object of the chargeable power supply in the fields of high-power electric vehicles, artificial satellites, aerospace and the like.
However, the existing lithium ion battery system is difficult to meet the requirements of high energy density and high safety of electric automobiles, and as is well known, the energy density of the battery is determined by the capacity and the voltage, so that the means for improving the energy density of the lithium ion battery comprises a silicon-carbon negative electrode with high capacity and a positive electrode material with high cut-off voltage and high capacity. The prior method mainly uses a high-capacity negative electrode and a high-capacity high-voltage positive electrode material, and for the positive electrode material, the content of nickel in the ternary positive electrode material can be increased, the charge cut-off voltage can be increased, and the discharge capacity can be improved, wherein LiNiMnO 4 ，LiNi 0.5 Mn 1.5 O 4 Other nickel-rich ternary materials (LiNi 0.8 Co 0.1 Mn 0.1 O 2 、LiNi 0.8 Co 0.1 Al 0.1 O 2 ) The lithium ion deintercalation reaction can occur under higher voltage (more than 4.2V), and new hopes are brought for improving the energy density of the lithium ion battery. However, two important problems exist under high voltage conditions, which affect the application: (1) The carbonate electrolyte of the conventional lithium ion battery is easy to decompose under high voltage, so that the charge and discharge efficiency of the lithium ion battery is reduced, a film with larger impedance is formed, and the cycle performance is deteriorated; (2) The common positive electrode material is more easily dissolved out of metal ions under the high-voltage condition, and metal dendrites are formed by diffusing electrolyte to the negative electrode, so that active lithium is lost, and the cycling stability and safety of the battery are affected. The electrolyte plays a vital role as a blood vessel of the lithium ion battery, so that the development of a multifunctional electrolyte applied to the high-nickel lithium ion battery is imperative.
In order to solve the above problems, a great deal of research work is being conducted by many research institutions, universities and even battery factories. As disclosed in the prior art, a multifunctional electrolyte (application publication number CN110148784 a) is disclosed, which is made up of a nonaqueous organic solvent, a conductive lithium salt, a negative electrode film-forming additive, a positive electrode film-forming additive, an expanding gas suppressing additive, and a low-resistance additive. The negative electrode film forming additive is one or more of fluorinated cyclic carbonates, the positive electrode additive is a nitrile compound with more than two nitrile groups, the flatulence inhibitor is at least one of tetravinyl silane, maleic anhydride, succinic anhydride, 2-methyl maleic anhydride and phthalic anhydride, and the low-impedance additive is at least one of lithium difluorophosphate and vinyl sulfate. The multifunctional electrolyte prepared by adding the combination of the additives with different functions improves the performance of the lithium ion battery. However, there is still a problem that the effect is exerted only on one of the positive electrode film formation and the negative electrode film formation in most cases, and the overall effect is still unsatisfactory.
Therefore, how to find a suitable electrolyte for lithium ion batteries, especially for lithium ion batteries made of high-nickel ternary materials, can better solve the above problems, and has become one of the problems to be solved by many first-line researchers and scientific research enterprises in the field.
Disclosure of Invention
In view of the above, the invention provides a lithium ion battery and an electrolyte for the lithium ion battery, in particular a high-voltage electrolyte for the lithium ion battery, and the lithium ion battery provided by the invention can form a film on the surfaces of positive and negative electrode materials, has a stable film structure, and improves the high-temperature performance and the cycle performance of the battery; and can prevent negative dendrite, improve the stability of the negative interface, and greatly relieve the problem of metal ion dissolution in the ternary positive electrode charging and discharging process.
The invention provides an electrolyte for a lithium ion battery, which comprises a nonaqueous organic solvent, electrolyte lithium salt and a multifunctional additive;
the multifunctional additive comprises a lithium silasulfamoyl salt, an anode and cathode protective agent and an additive.
Preferably, the lithium silasulfamoyl salt has a structure as shown in formula (I):
wherein R is 1 ～R 8 Each independently selected from one or more of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted linear alkyl carbonate group;
the substitution is in particular a fluorine atom substitution and/or a chlorine atom substitution.
Preferably, the alkyl is a C1-C20 alkyl;
the alkoxy is C1-C20 alkoxy;
the phenyl is C6-C20 phenyl;
the straight-chain alkyl carbonate group is a C1-C20 straight-chain alkyl carbonate group.
Preferably, the lithium silasulfamate comprises one or more of the structures shown in formulas (Ia) - (Ic);
preferably, the positive and negative electrode protecting agent comprises a polycyanonitrile compound;
the mass ratio of the silicon sulfamoyl lithium salt to the electrolyte is 1-10%;
the dosage of the anode and cathode protective agent accounts for 1% -5% of the total mass of the electrolyte;
the dosage of the additive accounts for 0.5-5% of the total mass of the electrolyte.
Preferably, the positive and negative electrode protecting agent comprises one or more of adiponitrile, succinonitrile, glutaronitrile, sebaconitrile, suberonitrile, 1,3, 6-hexanetricarbonitrile, 1,3, 5-pentanetrimitrile, 2-difluorosuccinonitrile, 2-fluoroadiponitrile and tricyanobenzene;
the additive comprises one or more of ethylene carbonate, fluoroethylene carbonate, ethylene sulfate, propylene sulfite and lithium difluorophosphate;
the electrolyte lithium salt includes one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorosulfonimide, lithium bisoxalato borate, and lithium difluorooxalato borate.
Preferably, the nonaqueous organic solvent comprises at least two or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, fluoroethylene carbonate, N-methylacetamide, N-methylformamide, dimethylformamide, diethylformamide, dimethyl sulfoxide, sulfolane, diphenyl sulfoxide, thionyl chloride, dipropyl sulfone and N-sulfolane;
the non-aqueous organic solvent accounts for 80-85% of the electrolyte by mass;
the concentration of the electrolyte lithium salt in the electrolyte is 0.6-1.5 mol/L.
The invention provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and the electrolyte in any one of the technical schemes.
Preferably, the lithium ion battery comprises a ternary positive electrode material lithium ion battery and LiNiMnO 4 Cathode material lithium ion battery or LiNi 0.5 Mn 1.5 O 4 A positive electrode material lithium ion battery;
the lithium ion battery is a lithium ion battery with at least one charge and discharge cycle;
the electrolyte contains a complex formed by metal cations dissolved out by the positive electrode and a positive and negative electrode protective agent.
Preferably, the lithium ion battery comprises a high-nickel ternary cathode material lithium ion battery;
the metal cations include one or more of nickel ions, manganese ions, and aluminum ions;
the complex is also compounded on one or more of the positive electrode, the separator and the negative electrode.
The invention provides an electrolyte for a lithium ion battery, which comprises a nonaqueous organic solvent, electrolyte lithium salt and a multifunctional additive; the multifunctional additive comprises a lithium silasulfamoyl salt, an anode and cathode protective agent and an additive. Compared with the prior art, the invention aims at the defects of the prior lithium ion battery positive electrode material, particularly the problems of the cycle performance and the thermal stability of the high-nickel ternary positive electrode material, and particularly aims at the fact that a single additive applied in the prior art only plays an effect on one aspect of positive electrode film formation or negative electrode film formation. In addition, in the prior art, the positive electrode film forming additive forms a film in preference to the electrolyte solvent, and the formed oxide film can prevent the electrolyte from being oxidatively decomposed at the positive electrode, but the inhibition effect of metal ions is only dependent on the shielding effect of the oxide film, so that the effect of inhibiting ion dissolution is not ideal. The positive electrode or negative electrode protective agent suppresses decomposition of the electrolyte solvent by forming an SEI film or a CEI film as a shielding film, and has a problem in that the effect is not obvious.
The invention creatively obtains the lithium ion battery electrode liquid, and the electrolyte contains the silicon sulfamoyl lithium salt with a specific structure and the anode and cathode protective agent with a specific proportion, in particular to a high-nickel lithium ion battery under the conditions of high temperature and high voltage. The silicon sulfamoyl lithium salt has proper LUMO energy level and HOMO energy level, can form a film on the surfaces of positive and negative electrode materials, has a stable film structure, improves the interface compatibility of the positive electrode and the negative electrode, and improves the high-voltage performance and the cycle performance of the battery; the anode and cathode protection additive is nitrile substance containing multiple cyano groups, which not only captures metal ions separated out from ternary anode material under high voltage to form complex to prevent metal dendrite from forming on the cathode after entering electrolyte, but also can form strong bond with the cathode to improve components of SEI film, enhance toughness and conductivity, and further improve interface stability of the cathode
According to the lithium ion battery electrolyte provided by the invention, the silicon sulfamoyl lithium salt is used as a film forming additive, and has proper LUMO energy level and HOMO energy level due to the special structure and the special group, and can form a film stably on the surfaces of positive and negative electrode materials, so that the high-voltage performance and the cycle performance of the battery are improved. The anode and cathode protection additive has high stability and oxidation resistance at the anode, and the cyano group has stronger coordination capacity, so that metal ions dissolved out by the anode can be complexed, and the decomposition effect of the anode on electrolyte is reduced; the components of the SEI film are improved at the negative electrode, the toughness of the SEI film is enhanced, the growth of lithium dendrites is inhibited, and the safety is improved. The two additives and other additives are synergistic mutually, so that the interface compatibility of the anode and the cathode is improved, and the high-voltage cycle performance and the safety of the battery are improved. Moreover, the preparation method of the electrolyte is simple, the process is controllable, and the electrolyte is more suitable for industrial popularization and application.
Experimental results show that the lithium ion battery electrolyte added with the lithium silamide salt provided by the invention has obvious advantages in capacity retention rate under the condition of 4.6V cut-off voltage compared with a lithium ion soft package battery without the electrolyte, and the additive is proved to have obvious improvement in high-voltage cycle performance of a ternary lithium ion battery.
Detailed Description
For further understanding of the present invention, the technical aspects of the present invention will be clearly and fully described in connection with the following embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs analytically pure or conventional purity in the field of lithium ion batteries.
In the present invention, R is as follows 1 ～R 8 The definition of a specific group of (a) is not particularly limited, and may be defined as usual by substituents well known to those skilled in the art, and the meaning and exact definition thereof can be precisely known to those skilled in the art based on the common general knowledge in the art.
The invention provides an electrolyte for a lithium ion battery, which comprises a nonaqueous organic solvent, electrolyte lithium salt and a multifunctional additive;
the multifunctional additive comprises a lithium silasulfamoyl salt, an anode and cathode protective agent and an additive.
The invention is in principle not particularly limited to the specific structure of the lithium silasulfamoyl salt, and a person skilled in the art can select and adjust the lithium silasulfamoyl salt according to application conditions, product performance and quality requirements, and the lithium silasulfamoyl salt preferably has the structure shown in a formula (I):
wherein R is 1 ～R 8 Each independently is preferably one or more of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted linear alkyl carbonate group, more preferably independently is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted linear alkyl carbonate group. In the present invention, the substitution is particularly preferably a fluorine atom substitution and/or a chlorine atom substitution, and more preferably a fluorine atom substitution or a chlorine atom substitution.
More specifically, the alkyl group is preferably a C1 to C20 alkyl group, more preferably a C5 to C16 alkyl group, and still more preferably a C9 to C12 alkyl group. The alkoxy group is preferably a C1 to C20 alkoxy group, more preferably a C5 to C16 alkoxy group, and still more preferably a C9 to C12 alkoxy group. The phenyl group is preferably a C6 to C20 phenyl group, more preferably a C8 to C18 phenyl group, still more preferably a C10 to C16 phenyl group, and still more preferably a C12 to C14 phenyl group. The linear alkyl carbonate group is preferably a C1 to C20 linear alkyl carbonate group, more preferably a C5 to C16 linear alkyl carbonate group, and still more preferably a C9 to C12 linear alkyl carbonate group.
More specifically, the lithium silasulfamate preferably includes one or more of the structures represented by the formulas (Ia) to (Ic);
the invention is characterized in that the mass ratio of the silicon sulfamoyl lithium salt to the electrolyte is not particularly limited, and can be selected and adjusted according to application conditions, product performance and quality requirements by a person skilled in the art, and the invention is used for better forming a stable SEI protective film on the surface of the anode and the cathode, improving interface compatibility, inhibiting growth of lithium dendrite, better inhibiting migration of positive metal ions to the cathode, and improving high-pressure cycle performance and safety of a battery, wherein the mass ratio of the silicon sulfamoyl lithium salt to the electrolyte is preferably 1% -10%, more preferably 2% -9%, more preferably 3% -8%, and more preferably 4% -7%.
The invention is in principle not particularly limited in the specific selection of the positive and negative electrode protective agent, and a person skilled in the art can select and adjust the positive and negative electrode protective agent according to the application condition, the product performance and the quality requirement. More specifically, the positive and negative electrode protecting agents preferably include one or more of adiponitrile, succinonitrile, glutaronitrile, sebaconitrile, suberonitrile, 1,3, 6-hexanetricarbonitrile, 1,3, 5-pentanetetracarbonitrile, 2-difluorosuccinonitrile, 2-fluoroadiponitrile and tricyanobenzene, more preferably adiponitrile, succinonitrile, glutaronitrile, sebaconitrile, suberonitrile, 1,3, 6-hexanetricarbonitrile, 1,3, 5-pentanetetracarbonitrile, 2-difluorosuccinonitrile, 2-fluoroadiponitrile or tricyanobenzene.
The invention is characterized in that the usage amount of the positive and negative electrode protective agent is not particularly limited, and can be selected and adjusted according to the application condition, the product performance and the quality requirement by a person skilled in the art, and the invention is used for better forming a stable SEI protective film on the surface of the positive and negative electrodes at the same time, improving the interface compatibility, inhibiting the growth of lithium dendrites, better inhibiting the migration of positive electrode metal ions to the negative electrode, and improving the high-pressure cycle performance and the safety of the battery, wherein the usage amount of the positive and negative electrode protective agent is 1% -5% of the total mass of the solution, more preferably 1.5% -4.5%, more preferably 2% -4%, and more preferably 2.5% -3.5%.
The present invention is not particularly limited in principle, and the specific selection of the additive may be selected and adjusted by those skilled in the art according to the application situation, product performance and quality requirements, and the present invention is to better form a stable SEI protective film on the positive and negative electrode surfaces at the same time, improve interfacial compatibility, inhibit the growth of lithium dendrites, better inhibit the migration of positive metal ions to the negative electrode, and improve the high-voltage cycle performance and safety of the battery, and the additive preferably includes one or more of ethylene carbonate, fluoroethylene carbonate, ethylene sulfate, propylene sulfite and lithium difluorophosphate, more preferably ethylene carbonate, fluoroethylene carbonate, ethylene sulfate, propylene sulfite or lithium difluorophosphate.
The invention is characterized in that the additive is used in an amount which is not particularly limited in principle and can be selected and adjusted according to the application condition, the product performance and the quality requirement by a person skilled in the art, the stable SEI protective film is formed on the surface of the positive electrode and the negative electrode simultaneously, the interface compatibility is improved, the growth of lithium dendrites is inhibited, the migration of positive electrode metal ions to the negative electrode is inhibited better, the high-pressure cycle performance and the safety of the battery are improved, the additive is used in an amount which is 0.5% -5%, more preferably 1.5% -4.5%, more preferably 1.5% -4%, more preferably 2% -3.5% and more preferably 2.5% -3% of the total quality of the solution.
The electrolyte lithium salt is not particularly limited in principle, and can be selected and adjusted according to application conditions, product performance and quality requirements by a person skilled in the art, and the electrolyte lithium salt is better in forming a stable SEI protective film on the surfaces of the positive electrode and the negative electrode, improving interface compatibility, inhibiting growth of lithium dendrites, better inhibiting migration of positive electrode metal ions to the negative electrode and improving high-voltage cycle performance and safety of a battery.
The nonaqueous organic solvent is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, and the nonaqueous organic solvent is preferably selected from at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, fluoroethylene carbonate, N-methylacetamide, N-methylformamide, dimethylformamide, diethylformamide, dimethyl sulfoxide, sulfolane, diphenyl sulfoxide, thionyl chloride, dipropyl sulfone and N-sulfolane, more preferably ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, fluoroethylene carbonate, N-methylacetamide, diethyl sulfoxide, dimethyl sulfoxide, sulfolane, or a combination of at least two of sulfolane, dimethyl sulfone, diphenyl sulfoxide, dimethyl sulfone and N-sulfolane, and further preferably ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl carbonate, fluoroethylene carbonate, N-methylacetamide, N-methylformamide, dimethyl sulfoxide, dimethyl sulfone and N-sulfolane.
The nonaqueous organic solvent accounts for 80-85% of the electrolyte, preferably 81-84% of the nonaqueous organic solvent, and more preferably 82-83% of the electrolyte.
The above steps of the present invention provide a high voltage electrolyte for a lithium ion battery. In the electrolyte, the lithium silasulfamate is provided with silamino ions, has lone pair electrons, and after being combined with lithium ions, the energy level of HOMO is raised and is higher than that of solvent molecules of carbonates, and the lithium silasulfamate is oxidized in preference to the solvent molecules at the positive electrode to form a stable protective film; and the lithium silasulfamate has two double bonds of S=O, and the unsaturated bond of S=O leads to the enhancement of the oxidability, the LUMO energy level is lower than that of solvent molecules of carbonic esters, and the lithium silasulfamate is reduced in preference to the solvent molecules at the cathode to form a stable protective film. In the electrolyte, the nitrile compound contains two or more cyano groups, the bond energy of a carbon-nitrogen triple bond is higher, the oxidation resistance is strong, meanwhile, the carbon-nitrogen triple bond of the cyano groups is SP hybridization, the electronegativity of the N atom end is strong, a great amount of C atom end electron cloud is adsorbed, the formed CN dipole moment is high, the C atom end has strong positive charge, the CN triple bond leads to the formation of a lone pair electron at the C atom end, and the lone pair electron is easily captured by d-space orbitals of metal to form coordination. The electrolyte can be subjected to complexation with dissolved positive electrode ions (nickel/cobalt/manganese), so that the active ions on the surface of the positive electrode are masked, the decomposition effect of the electrode on the electrolyte is reduced, and meanwhile, metal ions are prevented from being separated out in a metal dendrite form on the negative electrode, and the battery performance is influenced; and the nitrile compound can act on the SEI film of the negative electrode, improve the components of the SEI film, improve the content of inorganic components such as LiF and the like, and increase the firmness and flexibility of the SEI film, thereby inhibiting the growth of lithium dendrites, reducing irreversible capacity and improving safety.
The invention provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and the electrolyte in any one of the technical schemes.
In the lithium ion battery of the present invention, the selection of the related raw materials, structures and parameters and the corresponding preferred principles thereof are in one-to-one correspondence with the selection of the related raw materials, structures and parameters and the corresponding preferred principles thereof in the electrolyte of the lithium ion battery, and are not described in detail herein.
The invention is in principle not particularly limited to the types of the lithium ion battery, and can be selected and adjusted according to the application condition, the product performance and the quality requirement by the skilled in the art, and the invention is better to form a stable SEI protective film on the surface of the positive electrode and the negative electrode simultaneously, improve the interface compatibility, inhibit the growth of lithium dendrite, better inhibit the migration of positive metal ions to the negative electrode and improve the high-voltage cycle performance and the safety of the battery, wherein the lithium ion battery preferably comprises a ternary positive electrode material lithium ion battery and LiNiMnO 4 Cathode material lithium ion battery or LiNi 0.5 Mn 1.5 O 4 Positive electrode material lithium ion battery, more preferably high nickel ternary positive electrode material lithium ion battery, liNiMnO 4 Cathode material lithium ion battery or LiNi 0.5 Mn 1.5 O 4 Positive electrode material lithium ion battery.
The invention is in principle not particularly limited to the state of the lithium ion battery, and the lithium ion battery is well known to those skilled in the art, and can be selected and adjusted according to application conditions, product performance and quality requirements.
The invention is in principle not particularly limited to other components in the electrolyte, the types of lithium ion batteries well known to those skilled in the art can be selected and adjusted according to application conditions, product performance and quality requirements, and the electrolyte preferably contains a complex formed by metal cations dissolved out by a positive electrode and positive and negative protective agents.
The specific components of the metal cations are not particularly limited in principle, and the specific components are selected and adjusted according to the application condition, the product performance and the quality requirement of a lithium ion battery well known to a person skilled in the art, and the metal cations preferably comprise one or more of nickel ions, manganese ions and aluminum ions, more preferably nickel ions, manganese ions or aluminum ions, so that a stable SEI protective film is formed on the surface of the positive electrode and the negative electrode simultaneously, the interface compatibility is improved, the growth of lithium dendrites is inhibited, the migration of positive electrode metal ions to the negative electrode is inhibited better, and the high-voltage cycle performance and the safety of the battery are improved.
The complex is preferably compounded on one or more of a positive electrode, a diaphragm and a negative electrode, and more preferably compounded in the positive electrode, the diaphragm or the negative electrode.
The above steps of the present invention provide a high voltage electrolyte for a lithium ion battery and a lithium ion battery.
The invention discloses a lithium ion battery high-voltage electrolyte and a lithium ion battery thereof. The electrolyte contains a film forming additive lithium silasulfamate which has proper LUMO energy level and HOMO energy level, can form a film stably on the surfaces of positive and negative electrode materials, improves the interface compatibility of the positive electrode and the negative electrode, and improves the high-voltage performance and the cycle performance of the battery; the anode and cathode protection additive is nitrile substance containing a plurality of cyano groups, which not only captures metal ions separated out from the ternary anode material under high voltage to form complex to prevent the complex from forming metal dendrite on the cathode after entering the electrolyte, but also can form strong bond with the cathode, thereby improving the components of SEI film, enhancing the toughness and conductivity of SEI film and further improving the interface stability of the cathode.
The electrolyte film-forming additive provided by the invention adopts the lithium silasulfamate, the compound is used in lithium ion battery electrolyte for the first time, and reasonable HOMO and LUMO can form a film on an anode and a cathode at the same time; the anode and cathode protection additive adopts nitrile compounds containing a plurality of cyano groups, which not only can complex metal ions dissolved out by the anode, but also can inhibit migration of the metal ions to the cathode, and can improve components of an SEI film on the cathode, inhibit growth of lithium dendrites and further improve safety, especially aiming at metal cations such as nickel ions and manganese ions dissolved out by the high-nickel anode under the conditions of high temperature and high voltage. The two additives have synergistic effect, so that the interface compatibility of the anode and the cathode is improved, and the high-voltage cycle performance and the safety of the battery are improved. Moreover, the preparation method of the electrolyte is simple, the process is controllable, and the electrolyte is more suitable for industrial popularization and application.
Experimental results show that the lithium ion battery electrolyte added with the lithium silamide salt provided by the invention has obvious advantages in capacity retention rate under the condition of 4.6V cut-off voltage compared with a lithium ion soft package battery without the electrolyte, and the additive is proved to have obvious improvement in high-voltage cycle performance of a ternary lithium ion battery.
For further explanation of the present invention, an electrolyte for a lithium ion battery and a lithium ion battery provided by the present invention are described in detail below with reference to examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given only for further explanation of features and advantages of the present invention, and not limitation of claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
The reagents used in the following examples of the present invention are all commercially available.
Preparation of film-forming additive:
the whole reaction system is added with dichloromethane, triethylamine and trityl silylamine into a three-neck flask with a constant pressure dropping funnel under the condition of nitrogen protection at-30 ℃ and continuously stirred for 1-3 h. The reaction was continued at low temperature for 12 hours after the methylene chloride solution of 2- (trifluoromethoxy) benzenesulfonyl chloride was slowly added with stirring. After the reaction is completed, naHCO is used 3 Saturated solution was extracted three times, the organic layers were combined and dried over anhydrous Na 2 SO 4 Drying, filtering, and performing reduced pressure rotary evaporation to obtain the prepared silasulfamoyl ligand. Then slowly adding the n-butyl lithium solution at the temperature of minus 80 ℃ and continuously reacting for 4 to 8 hours under the condition of low temperature, no water and no oxygen. And slowly heating to room temperature after the reaction is finished to obtain the silicon sulfamoyl lithium of the additive, and pumping to obtain the additive.
Example 1
EC (ethylene carbonate) was prepared in a glove box having both a water content and an oxygen content of less than 0.1 ppm: DMC (dimethyl carbonate): EMC (methyl ethyl carbonate) was mixed well in a ratio of 4:2:4. Adding LiPF with certain mass into the mixed solution under the condition of keeping the temperature outside the reaction vessel below 5 DEG C 6 After (lithium hexafluorophosphate), stirring until 1mol/L solution is prepared, adding 5% (based on the mass of the nonaqueous organic solvent and electrolyte lithium salt, 100%) of lithium silasulfamate (structure shown in the following formula) and 3% of 1,3, 5-pentane trimethyl nitrile and 2% of FEC (fluoroethylene carbonate), and stirring uniformly to obtain the electrolyte.
The electrolyte prepared in example 1 of the present invention was subjected to performance test, see example 7.
Example 2
At a water content and an oxygen content of less than 0.1ppmEC (ethylene carbonate) in glove box: DMC (dimethyl carbonate): EMC (methyl ethyl carbonate) was mixed well in a ratio of 4:2:4. Adding LiPF with certain mass into the mixed solution under the condition of keeping the temperature outside the reaction vessel below 5 DEG C 6 After (lithium hexafluorophosphate) stirring until 1mol/L solution was prepared, 5% (100% based on the mass of the nonaqueous organic solvent and the electrolyte lithium salt) of lithium silasulfamate (structure same as in example 1) and 3% of glutaronitrile and 2% of DTD (vinyl sulfate) were added, and the electrolyte was obtained after stirring uniformly.
The electrolyte prepared in example 2 of the present invention was subjected to performance test, see example 7.
Example 3
EC (ethylene carbonate) was prepared in a glove box having both a water content and an oxygen content of less than 0.1 ppm: DMC (dimethyl carbonate): EMC (methyl ethyl carbonate) was mixed well in a ratio of 4:2:4. Adding LiPF with certain mass into the mixed solution under the condition of keeping the temperature outside the reaction vessel below 5 DEG C 6 After (lithium hexafluorophosphate), stirring until 1mol/L solution is prepared, adding 5% (based on the mass of the nonaqueous organic solvent and electrolyte lithium salt, 100%) of lithium silasulfamate (structure shown in the following formula) and 3% of 1,3, 5-pentane trimethyl nitrile and 2% of FEC (fluoroethylene carbonate), and stirring uniformly to obtain the electrolyte.
The electrolyte prepared in example 3 of the present invention was subjected to performance test, see example 7.
Example 4
EC (ethylene carbonate) was prepared in a glove box having both a water content and an oxygen content of less than 0.1 ppm: DMC (dimethyl carbonate): EMC (methyl ethyl carbonate) was mixed well in a ratio of 4:2:4. Adding LiPF with certain mass into the mixed solution under the condition of keeping the temperature outside the reaction vessel below 5 DEG C 6 After stirring to prepare 1mol/L solution, 5% (based on the mass of the nonaqueous organic solvent and the electrolyte lithium salt, 100%) of the solution is addedLithium silamide (structure same as example 3) and 3% glutaronitrile with 2% DTD (vinyl sulfate), and the electrolyte was obtained after uniform stirring.
The electrolyte prepared in example 4 of the present invention was subjected to performance test, see example 7.
Example 5
EC (ethylene carbonate) was prepared in a glove box having both a water content and an oxygen content of less than 0.1 ppm: DMC (dimethyl carbonate): EMC (methyl ethyl carbonate) was mixed well in a ratio of 4:2:4. Adding LiPF with certain mass into the mixed solution under the condition of keeping the temperature outside the reaction vessel below 5 DEG C 6 After (lithium hexafluorophosphate), stirring until 1mol/L solution is prepared, adding 5% (based on the mass of the nonaqueous organic solvent and electrolyte lithium salt, 100%) of lithium silasulfamate (structure shown in the following formula) and 3% of 1,3, 5-pentane trimethyl nitrile and 2% of FEC (fluoroethylene carbonate), and stirring uniformly to obtain the electrolyte.
The electrolyte prepared in example 5 of the present invention was subjected to performance test, see example 7.
Example 6
EC (ethylene carbonate) was prepared in a glove box having both a water content and an oxygen content of less than 0.1 ppm: DMC (dimethyl carbonate): EMC (methyl ethyl carbonate) was mixed well in a ratio of 4:2:4. Adding LiPF with certain mass into the mixed solution under the condition of keeping the temperature outside the reaction vessel below 5 DEG C 6 After (lithium hexafluorophosphate) stirring until 1mol/L solution was prepared, 5% (100% based on the mass of the nonaqueous organic solvent and the electrolyte lithium salt) of lithium silasulfamate (structure same as in example 5) and 3% of glutaronitrile and 2% of DTD (vinyl sulfate) were added, and the electrolyte was obtained after stirring uniformly.
The electrolyte prepared in example 6 of the present invention was subjected to performance test, see example 7.
Comparative example 1
At a water content and an oxygen content of less than 0.1ppmEC (ethylene carbonate) in glove box: DMC (dimethyl carbonate): EMC (methyl ethyl carbonate) was mixed well in a ratio of 4:2:4. Adding LiPF with certain mass into the mixed solution under the condition of keeping the temperature outside the reaction vessel below 5 DEG C 6 After (lithium hexafluorophosphate) stirring until 1mol/L solution was prepared, 3% of 1,3, 5-pentanetrimonitrile and 2% of FEC (fluoroethylene carbonate) were added, and after stirring uniformly, comparative example electrolyte 1 was obtained.
Comparative example 2
EC (ethylene carbonate) was prepared in a glove box having both a water content and an oxygen content of less than 0.1 ppm: DMC (dimethyl carbonate): EMC (methyl ethyl carbonate) was mixed well in a ratio of 4:2:4. Adding LiPF with certain mass into the mixed solution under the condition of keeping the temperature outside the reaction vessel below 5 DEG C 6 After (lithium hexafluorophosphate), stirring continuously until 1mol/L solution is prepared, then adding 3% of glutaronitrile and 2% of DTD (vinyl sulfate), and stirring uniformly to obtain comparative example electrolyte 2.
Example 7
The electrolytes prepared in examples 1 to 6 and comparative examples were assembled into soft-pack lithium ion batteries according to the following method: the positive electrode active material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 The negative electrode active material is artificial graphite, the diaphragm is ceramic coated diaphragm, and the positive electrode, the negative electrode and the diaphragm are laminated and then injected into the electrolyte prepared in the examples and the comparative examples, and then encapsulated, and the lithium ion soft package battery is obtained through the steps of formation, capacity division and the like.
The batteries assembled in examples 1 to 6 and comparative example were subjected to a normal temperature cycle performance test: at room temperature (25 ℃), constant current charge to 4.2V at 1C, constant voltage charge to 0.05C,1C discharge to 3V were counted as one cycle. After 500 times of charge and discharge, the 500 th cycle discharge capacity is recorded, the 500 th cycle capacity retention rate is calculated, and the calculation formula is as follows:
500 th cycle capacity retention = (500 th cycle discharge capacity/first cycle discharge capacity) ×100%
High temperature cycle performance test was performed on the batteries assembled in examples 1 to 6 and comparative examples: in a constant temperature oven at 25 ℃, charging to 4.6V at a constant current of 1C, constant voltage charging is stopped to 0.05C, and 1C discharging to 3V is counted as one cycle. After 500 times of charge and discharge, the 500 th cycle discharge capacity is recorded, the 500 th cycle capacity retention rate is calculated, and the calculation formula is the same as the above formula.
Referring to table 1, table 1 is a comparison table of the cycle capacity retention rates of lithium ion batteries prepared from the electrolytes prepared in examples 1 to 6 and comparative example 1 according to the present invention.
TABLE 1
As can be seen from the electrical performance test results of the lithium ion battery in Table 1, the lithium ion battery electrolyte added with the lithium silicate sulfamide salt has obvious advantages in capacity retention rate under the condition of 4.6V cut-off voltage compared with the lithium ion soft package battery without the electrolyte, and the additive is proved to have obvious improvement in high-voltage cycle performance of the ternary lithium ion battery.
The foregoing has outlined rather broadly the principles and embodiments of the present invention in order that the detailed description of the invention that follows may be better understood, and in order that the present invention may be practiced by anyone skilled in the art, including in any regard to the manufacture and use of the device or system, and in order that the present invention may be better understood. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (10)
1. An electrolyte for a lithium ion battery, characterized in that the electrolyte comprises a nonaqueous organic solvent, an electrolyte lithium salt and a multifunctional additive;
the multifunctional additive comprises a lithium silasulfamoyl salt, an anode and cathode protective agent and an additive;
the lithium silasulfamoyl salt has a structure as shown in formula (I):
wherein R is 1 ～R 8 Each independently selected from one or more of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted linear alkyl carbonate group;
the substitution is in particular a fluorine atom substitution and/or a chlorine atom substitution.
2. The electrolyte of claim 1, wherein the alkyl is a C1-C20 alkyl;
the alkoxy is C1-C20 alkoxy.
3. The electrolyte of claim 1, wherein the phenyl group is a C6-C20 phenyl group;
the straight-chain alkyl carbonate group is a C1-C20 straight-chain alkyl carbonate group.
4. The electrolyte of claim 1, wherein the lithium silasulfamate comprises one or more of the structures of formulas (Ia) - (Ic);
5. the electrolyte of claim 1, wherein the positive and negative electrode protecting agent comprises a polycyano nitrile compound;
the mass ratio of the silicon sulfamoyl lithium salt to the electrolyte is 1-10%;
the dosage of the anode and cathode protective agent accounts for 1% -5% of the total mass of the electrolyte;
the dosage of the additive accounts for 0.5-5% of the total mass of the electrolyte.
6. The electrolyte of claim 1, wherein the positive and negative electrode protecting agent comprises one or more of adiponitrile, succinonitrile, glutaronitrile, sebaconitrile, suberonitrile, 1,3, 6-hexanetricarbonitrile, 1,3, 5-pentanetrimitrile, 2-difluorosuccinonitrile, 2-fluoroadiponitrile and tricyanobenzene;
the additive comprises one or more of ethylene carbonate, fluoroethylene carbonate, ethylene sulfate, propylene sulfite and lithium difluorophosphate;
the electrolyte lithium salt includes one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorosulfonimide, lithium bisoxalato borate, and lithium difluorooxalato borate.
7. The electrolyte of claim 1, wherein the nonaqueous organic solvent comprises a combination of at least two or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, fluoroethylene carbonate, N-methylacetamide, N-methylformamide, dimethylformamide, diethylformamide, dimethylsulfoxide, sulfolane, diphenylsulfoxide, thionyl chloride, dipropyl sulfone, and N-sulfolane;
the non-aqueous organic solvent accounts for 80-85% of the electrolyte by mass;
the concentration of the electrolyte lithium salt in the electrolyte is 0.6-1.5 mol/L.
8. A lithium ion battery comprising a positive electrode, a negative electrode, a separator and the electrolyte of any one of claims 1 to 7.
9. The lithium ion battery of claim 8, wherein the lithium ion battery comprises a ternary positive electrode material lithium ion battery, liNiMnO 4 Cathode material lithium ion battery or LiNi 0.5 Mn 1.5 O 4 A positive electrode material lithium ion battery;
the lithium ion battery is a lithium ion battery with at least one charge and discharge cycle;
the electrolyte contains a complex formed by metal cations dissolved out by the positive electrode and a positive and negative electrode protective agent.
10. The lithium ion battery of claim 9, wherein the lithium ion battery comprises a high nickel ternary positive electrode material lithium ion battery;
the metal cations include one or more of nickel ions, manganese ions, and aluminum ions;
the complex is also compounded on one or more of the positive electrode, the separator and the negative electrode.
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| KR20190053365A (en) * | 2017-11-10 | 2019-05-20 | 솔브레인 주식회사 | Electrolyte and lithium secondary battery comprising the same |
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