CN116936909A - High-voltage electrolyte for lithium battery - Google Patents
High-voltage electrolyte for lithium battery Download PDFInfo
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- CN116936909A CN116936909A CN202210370742.8A CN202210370742A CN116936909A CN 116936909 A CN116936909 A CN 116936909A CN 202210370742 A CN202210370742 A CN 202210370742A CN 116936909 A CN116936909 A CN 116936909A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 110
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 82
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 42
- -1 fluoro sulfonamide compound Chemical class 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 25
- 239000010439 graphite Substances 0.000 claims abstract description 25
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 13
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 125000002757 morpholinyl group Chemical group 0.000 claims description 6
- 125000005936 piperidyl group Chemical group 0.000 claims description 6
- 125000000719 pyrrolidinyl group Chemical group 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- 125000004992 haloalkylamino group Chemical group 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 229910015965 LiNi0.8Mn0.1Co0.1O2 Inorganic materials 0.000 claims description 2
- 229910001412 inorganic anion Inorganic materials 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
- SASNBVQSOZSTPD-UHFFFAOYSA-N n-methylphenethylamine Chemical group CNCCC1=CC=CC=C1 SASNBVQSOZSTPD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 41
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- USPTVMVRNZEXCP-UHFFFAOYSA-N sulfamoyl fluoride Chemical compound NS(F)(=O)=O USPTVMVRNZEXCP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 12
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 229910013716 LiNi Inorganic materials 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- GRGCWBWNLSTIEN-UHFFFAOYSA-N trifluoromethanesulfonyl chloride Chemical compound FC(F)(F)S(Cl)(=O)=O GRGCWBWNLSTIEN-UHFFFAOYSA-N 0.000 description 6
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 description 5
- 239000012267 brine Substances 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 229910012820 LiCoO Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- KGPPDNUWZNWPSI-UHFFFAOYSA-N flurotyl Chemical compound FC(F)(F)COCC(F)(F)F KGPPDNUWZNWPSI-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JFCHSQDLLFJHOA-UHFFFAOYSA-N n,n-dimethylsulfamoyl chloride Chemical compound CN(C)S(Cl)(=O)=O JFCHSQDLLFJHOA-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C307/00—Amides of sulfuric acids, i.e. compounds having singly-bound oxygen atoms of sulfate groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C307/04—Diamides of sulfuric acids
- C07C307/06—Diamides of sulfuric acids having nitrogen atoms of the sulfamide groups bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
- C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C311/09—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton the carbon skeleton being further substituted by at least two halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
- C07D295/26—Sulfur atoms
-
- 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
-
- 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a high-voltage electrolyte for a lithium battery, and belongs to the technical field of lithium battery electrolytes. The electrolyte comprises an organic solvent, wherein the organic solvent is a fluoro sulfonamide compound. The fluoro sulfonamide compound is used as a solvent of the lithium metal/ion battery electrolyte, and can effectively improve the voltage resistance performance and the lithium metal/graphite compatibility of the electrolyte. Meanwhile, the solvent can form a stable interface protection layer on the anode, and side reaction of electrolyte is reduced, so that excellent cycle performance is realized. According to the invention, the lithium salt and the fluoro-sulfonamide solvent in the high-voltage electrolyte for the lithium metal/ion battery are specifically combined, and the concentration and the proportion are further optimized, so that the lithium metal/graphite high-voltage electrolyte added with the lithium metal/graphite high-voltage electrolyte disclosed by the invention has excellent compatibility with positive and negative electrodes, and further the long cycle life and high coulombic efficiency of the lithium battery are realized.
Description
Technical Field
The invention belongs to the technical field of lithium battery electrolyte, and particularly relates to high-voltage electrolyte for a lithium battery.
Background
Since commercialization in 1991, lithium-based batteries have been widely used in the fields of portable electronic products, electric vehicles, large-sized energy storage power stations, and the like, because of their advantages such as high energy density, long cycle life, no memory effect, and rapid charge and discharge. As the requirements of people on the endurance mileage of lithium batteries are continuously increased, the negative electrode material is developed from graphite to a negative electrode with high specific capacity according to the formula of energy density=specific capacity. Lithium metal has attracted many scholars' research as a negative electrode material with extremely high specific capacity. Due to the lowest deposition potential of lithium metal itself, conventional commercial electrolytes composed of lithium hexafluorophosphate and carbonate solvents undergo severe reduction reactions on the negative electrode side, resulting in reduced coulombic efficiency. Therefore, it is imperative to design a new electrolyte matching lithium metal electrodes for lithium metal batteries. On the other hand, the positive electrode material has LiFePO with lower original working potential 4 LiNi to high pressure 0.8 Mn 0.1 Co 0.1 O 2 And the like, and simultaneously, higher requirements are also put on the oxidation resistance of the electrolyte.
To meet the requirement of stable cycling of both high voltage positive electrodes and lithium metal/graphite negative electrodes requires reasonable design of the composition of the electrolyte. At present, no electrolyte consisting of a single solvent and a single lithium salt that can satisfy the conditions can realize stable circulation of the high-voltage lithium metal/ion battery for a while.
Currently, many scholars are working to develop high-concentration or locally high-concentration electrolytes to match high-voltage lithium metal/ion batteries in order to meet both high-voltage positive electrodes and lithium metal/graphite negative electrodes. Document "Chen S, zheng J, mei D, et al high-Voltage Lithoum-Metal Batteries Enabled by LocalAdvanced Materials,2018:1706102 refers to the addition of bis trifluoroethyl ether in a 2-fold molar ratio to solvent to a high concentration electrolyte of dimethyl carbonate, li||LiNi at 4.3V 1/3 Co 1/3 Mn 1/3 O 2 The button cell was cycled only 700 cycles, with a capacity retention of 80%. Literature "Ren XD, zhang XH, shadife Z, et al design Advanced In Situ Electrode/Electrolyte Interphases for Wide Temperature Operation of 4.5.5V Li LiCoO ] 2 Advanced Materials,2020, 32 (49): 2004898 mentions that adding tetrafluoroethyl tetrafluoropropyl ether in 3 times mole ratio of solvent to high concentration electrolyte of dimethoxyethane, li I LiCoO at 4.5V 2 The button cell was cycled for 800 cycles with a capacity retention of 82%. Although some high-concentration or local high-concentration systems are currently capable of maintaining a high-voltage lithium metal system for a period of time, they are not practical from an economic cost standpoint, and the capacity is later severely attenuated as charge and discharge proceeds.
In addition, although some sulfonamide-based electrolytes in the prior art, for example, the invention application published as US2019/0386363 A1 discloses non-aqueous electrolytes of fluorosulfonamides for lithium-air secondary batteries, wherein the disclosed fluorosulfonamide-based electrolytes can only be used to improve the high-voltage stability of lithium-air secondary batteries, the long-term stability is worth mentioning. The alkyl fluorosulfonamide disclosed in the patent application publication CN 105470571A can only be used as an additive and not used alone as a solvent due to the limitation of its own structure, and the long-term stability is to be improved. The electrolyte disclosed in the patent application publication CN 113454805A contains trifluoromethylsulfonyl chloride, and is extremely easily subjected to a reduction reaction on the negative electrode side, and therefore, can be used only as an additive for the electrolyte. In addition, in the inventions of CN 112062715A and CN 114142088A, the sulfonamide is used as an electrolyte salt and an electrolyte additive, respectively, and cannot be used as a solvent for an electrolyte.
Disclosure of Invention
Aiming at the problems of poor high-voltage resistance, low coulombic efficiency and the like of the current commercial electrolyte to a lithium metal/ion battery, the invention aims to provide a high-voltage electrolyte solvent for the lithium metal/ion battery, which has a wide electrochemical window of more than 5V and good compatibility with a lithium metal/graphite negative electrode, and greatly improves the cycle life of the high-voltage lithium metal/ion battery.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides application of a fluoro sulfonamide compound, wherein the fluoro sulfonamide compound is used as an organic solvent of lithium battery electrolyte, and the general formula of the fluoro sulfonamide compound is shown in a structural formula I or a structural formula II:
wherein R is 1 The method comprises the following steps: aliphatic cyclic alkylamino, benzenoalkylamino, anilino or haloalkylamino; r is R 2 The method comprises the following steps: fluoroalkylamine groups.
Preferably, said R 1 Selected from pyrrolidinyl, morpholinyl, piperidyl, N-methylphenylamino or-N [ (CH) 2 ) n CX 3 ] 2 N is any positive integer from 1 to 4, and X=F, cl, br or I; r is R 2 is-N [ (CH) 2 ) n CF 3 ] 2 N is any positive integer from 1 to 4.
More preferably, said R 1 Selected from pyrrolidinyl, morpholinyl, piperidyl, N-methylphenylethylamino or-N (CH) 2 CF 3 ) 2 ，R 2 is-N (CH) 2 CF 3 ) 2 。
The invention provides a high-voltage electrolyte for a lithium battery, which comprises an organic solvent, wherein the organic solvent is a fluoro-sulfonamide compound, and the general formula of the fluoro-sulfonamide compound is shown as a structural formula I or a structural formula II:
wherein R is 1 The method comprises the following steps: aliphatic cyclic alkylamino, benzenoalkylamino, anilino or haloalkylamino; r is R 2 The method comprises the following steps: fluoroalkylamine groups.
Preferably, the fluoro sulfonamide compound accounts for 70% -95% of the total mass of the electrolyte.
Preferably, said R 1 Selected from pyrrolidinyl, morpholinyl, piperidyl, N-methylphenylamino or-N [ (CH) 2 ) n CX 3 ] 2 N is any positive integer from 1 to 4, and X=F, cl, br or I; r is R 2 is-N [ (CH) 2 ) n CF 3 ] 2 N is any positive integer from 1 to 4.
More preferably, said R 1 Selected from pyrrolidinyl, morpholinyl, piperidyl, N-methylphenylethylamino or-N (CH) 2 CF 3 ) 2 ，R 2 is-N (CH) 2 CF 3 ) 2 。
The high-voltage electrolyte for the lithium battery further comprises a lithium salt, wherein the lithium salt is at least one of inorganic anion lithium salt and organic anion lithium salt such as lithium hexafluorophosphate, lithium difluorosulfonimide, lithium bis (trifluoromethylsulfonyl) imide, lithium tetrafluoroborate, lithium bisoxalato borate, lithium difluorooxalato borate and lithium difluorophosphate.
Preferably, the concentration of the lithium salt is 0.5 to 3.0mol/L.
The solvent is used for preparing the high-voltage lithium metal/ion battery electrolyte, so that Li LiNi can be realized 0.8 Co 0.1 Mn 0.1 O 2 The button cell still has 80% capacity retention rate after 200 circles of circulation within the voltage range of 2.8-4.7V, and the average coulomb efficiency is as high as more than 99.7%; grLiCoO 2 The button cell has 82% capacity retention rate after 200 circles of circulation in the voltage range of 3.0-4.55V, and the average coulomb efficiency is as high as more than 99.8%, which is far higher than the performance of the current high-voltage electrolyte.
The invention provides a lithium battery, which comprises a positive electrode, a negative electrode and the high-voltage electrolyte.
The active material in the positive electrode is LiCoO 2 Or LiNi 0.8 Mn 0.1 Co 0.1 O 2 。
The active material of the negative electrode is lithium metal or graphite. The positive and negative electrode active materials may have a surface capacity of 0.5 to 5mAh cm -2 。
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides application of a fluoro-sulfonamide compound, which is used as a solvent of lithium metal/ion battery electrolyte, and can effectively improve the voltage resistance performance and the lithium metal/graphite compatibility of the electrolyte. Meanwhile, the solvent can form a stable interface protection layer on the anode, and side reaction of electrolyte is reduced, so that excellent cycle performance is realized.
(2) According to the invention, the lithium salt and the fluoro-sulfonamide solvent in the high-voltage electrolyte for the lithium metal/ion battery are specifically combined, and the concentration and the proportion are further optimized, so that the lithium metal/graphite high-voltage electrolyte added with the lithium metal/graphite high-voltage electrolyte disclosed by the invention has excellent compatibility with positive and negative electrodes, and further the long cycle life and high coulombic efficiency of the lithium battery are realized.
(3) The high-voltage electrolyte for the lithium metal/ion battery belongs to an electrolyte system with high ionic conductivity, wide electrochemical window, good film forming performance and excellent multiplying power performance, and has wide application prospect in the lithium metal/ion battery.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the solvent synthesized in example 1 dissolved in deuterated DMSO.
FIG. 2 is a diagram showing the Li LiNi content of the electrolyte prepared in example 1 0.8 Co 0.1 Mn 0.1 O 2 Cycle life curves in batteries.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the solvent synthesized in example 2 dissolved in deuterated DMSO.
FIG. 4 is a preparation in example 2In Gr LiCoO 2 Cycle life graph in a battery.
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the solvent synthesized in example 3 dissolved in deuterated DMSO.
FIG. 6 is a diagram showing the Li LiNi content of the electrolyte prepared in example 3 0.8 Co 0.1 Mn 0.1 O 2 Charge-discharge curve in a battery.
FIG. 7 is a Li LiCoO sample of the electrolyte prepared in example 4 2 Charge-discharge curve in a battery.
FIG. 8 is Li LiNi of the electrolyte prepared in example 5 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in a battery.
FIG. 9 is a diagram showing the Li LiNi content of the electrolyte prepared in example 6 0.8 Co 0.1 Mn 0.1 O 2 Charge-discharge curve in a battery.
FIG. 10 shows the LiLiNi in Li| of the commercial ester-based electrolyte prepared in comparative example 1 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in a battery.
FIG. 11 is a schematic diagram showing the LiLiCoO of the commercial ester-based electrolyte prepared in comparative example 2 2 Cycle life graph in a battery.
FIG. 12 is a graph showing Li LiNi of the commercial modified ester-based electrolyte prepared in comparative example 3 0.8 Co 0.1 Mn 0.1 O 2 Charge-discharge curve in a battery.
Detailed Description
Example 1
A high-voltage lithium metal/graphite electrolyte solvent for a lithium battery is prepared by the following steps:
4.26g (0.06 mol) of pyrrolidine (molecular weight M=71) and 8.08g (0.08 mol) of triethylamine (Et 3 N, molecular weight M=101) was dissolved in 120ml of tetrahydrofuran, 10.11g (0.06 mol) of a solution of trifluoromethylsulfonyl chloride (molecular weight M=168.5) dissolved in 40ml of tetrahydrofuran was added dropwise thereto, reacted at-60℃for at least 72 hours, then slowly raised to 0℃and taken out, a sufficient amount of concentrated hydrochloric acid was added first, and then a product was obtained, separated and filtered, and the filtrate was retained, washed with brineAdding anhydrous magnesium sulfate for dewatering (4 h), filtering to obtain filtrate, rotary evaporating at 40deg.C, removing residual liquid, distilling at 125deg.C under reduced pressure, adding the obtained liquid into molecular sieve overnight to obtain solvent with high purity, and the structural formula is shown in formula I.
And dissolving a certain amount of lithium bis (fluorosulfonyl) imide in the obtained solvent to ensure that the concentration of lithium bis (fluorosulfonyl) imide is 0.5mol/L, and stirring until the electrolyte is completely clarified, thus obtaining the high-voltage lithium metal/graphite electrolyte for the lithium battery.
FIG. 1 shows the results of characterization by H-NMR spectra, wherein characteristic peaks at a and b represent H at C atom attached to N atom and CH after one C is separated from N atom, respectively, on the ring 2 H above.
FIG. 2 shows the concentration of 0.5mol/L electrolyte prepared from the solvent and lithium difluorosulfimide salt of example 1 at Li LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in battery, wherein the face capacity of positive electrode is 2mAh cm -2 The capacity of the negative electrode surface is 4mAh cm -2 . As can be seen from FIG. 2, the electrolyte has a capacity retention rate of up to 80% and an average coulombic efficiency of up to 99.7% or more after 200 cycles of circulation. Compared with the traditional commercial ester-based electrolyte, the circulation capacity retention rate and the coulombic efficiency are greatly improved.
Example 2
A high-voltage lithium metal/graphite electrolyte solvent for a lithium battery is prepared by the following steps:
10.86g (0.06 mol) of bis (2, 2-trifluoroethyl) amine (molecular weight M=181) and 8.08g (0.08 mol) of triethylamine (Et) 3 N, molecular weight M=101) in 120ml tetrahydrofuran, dropwise adding 10.11g (0.06 mol) of trifluoromethyl sulfonyl chloride (molecular weight M=168.5) in 40ml tetrahydrofuran, reacting at-60 ℃ for at least 72h, slowly raising to 0 ℃ and taking out, adding enough concentrated hydrochloric acid, obtaining a product, separating liquid, filtering, retaining filtrate, washing with brine,adding anhydrous magnesium sulfate for dewatering (4 h), filtering to obtain filtrate, rotary evaporating at 40deg.C, removing residual liquid, distilling at 125deg.C under reduced pressure, adding the obtained liquid into molecular sieve overnight to obtain solvent with high purity, and the structural formula is shown in formula II.
And dissolving a certain amount of lithium bis (fluorosulfonyl) imide in the obtained solvent to ensure that the concentration of lithium bis (fluorosulfonyl) imide is 1.0mol/L, and stirring until the electrolyte is completely clarified, thus obtaining the high-voltage lithium metal/graphite electrolyte for the lithium battery.
FIG. 3 shows the results of characterization by H-NMR spectra, wherein characteristic peaks at positions a and b represent H at the C atom attached to the N atom and CH after one C is separated from the N atom, respectively, on the ring 2 H above.
FIG. 4 shows the electrolyte prepared from the solvent of example 2 and lithium difluorosulfimide at a concentration of 1.0mol/L at Gr LiCoO 2 Cycle life graph in battery, wherein the face capacity of positive electrode is 5mAh cm -2 The capacity of the negative electrode surface is 5mAh cm -2 . As can be seen from fig. 4, even at a charge cut-off voltage of up to 4.55V, the capacity retention rate of 82% was still obtained for 200 cycles, and the average coulomb efficiency was as high as 99.8% or more. And the commercial ester-based electrolyte has a capacity retention of less than 80% and an average coulombic efficiency of less than 99% after 100 cycles under such conditions.
Example 3
A high-voltage lithium metal/graphite electrolyte solvent for a lithium battery is prepared by the following steps:
5.22g (0.06 mol) of morpholine (molecular weight M=87) and 8.08g (0.08 mol) of triethylamine (Et 3 N, molecular weight M=101) was dissolved in 120ml of tetrahydrofuran, 10.11g (0.06 mol) of a solution of trifluoromethylsulfonyl chloride (molecular weight M=168.5) dissolved in 40ml of tetrahydrofuran was added dropwise thereto, reacted at-60℃for at least 72 hours, then slowly raised to 0℃and taken out, a sufficient amount of concentrated hydrochloric acid was added first, then a product was obtained, the filtrate was separated and filtered, washed with brine, and anhydrous magnesium sulfate was added to removeFiltering to obtain filtrate, rotary steaming at 40deg.C, removing residual liquid, distilling at 125deg.C under reduced pressure, adding the obtained liquid into molecular sieve overnight to obtain solvent with high purity, and the structural formula is shown in formula III.
And dissolving a certain amount of lithium bis (fluorosulfonyl) imide in the obtained solvent to ensure that the concentration of lithium bis (fluorosulfonyl) imide is 3.0mol/L, and stirring until the electrolyte is completely clarified, thus obtaining the high-voltage lithium metal/graphite electrolyte for the lithium battery.
FIG. 5 shows the results of characterization by H-NMR spectra, wherein characteristic peaks at positions a and b represent H at the C atom attached to the N atom and CH after one C is separated from the N atom, respectively, on the ring 2 H above.
FIG. 6 shows the concentration of 3.0mol/L electrolyte prepared from the solvent and lithium difluorosulfimide salt of example 3 at Li LiNi 0.8 Co 0.1 Mn 0.1 O 2 Charge-discharge curve in battery, wherein the surface capacity of positive electrode is 0.5mAh cm -2 The capacity of the negative electrode surface is 2mAh cm -2 . As can be seen from fig. 6, liNi 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material has obvious charge and discharge platform in the high-voltage electrolyte and is highly reversible. As the cycle number increases, the specific discharge capacity decays not sharply, which shows that the electrolyte is suitable for LiNi 0.8 Co 0.1 Mn 0.1 O 2 High compatibility of the positive electrode material and the Li metal negative electrode.
Example 4
A high-voltage lithium metal/graphite electrolyte solvent for a lithium battery is prepared by the following steps:
8.1g (0.06 mol) of bis-N-methyl-2-phenylethylamine (CAS: 589-08-2, molecular weight M=135) and 8.08g (0.08 mol) of triethylamine (Et 3 N, molecular weight M=101) in 120ml of tetrahydrofuran, 10.11g (0.06 mol) of trifluoromethylsulfonyl chloride (molecular weight M=168.5) in 40ml of tetrahydrofuran was added dropwise thereto and reacted at-60 ℃At least 72h, slowly heating to 0deg.C, taking out, adding enough concentrated hydrochloric acid, separating to obtain product, filtering, retaining filtrate, washing with brine, adding anhydrous magnesium sulfate for dewatering (4 h), filtering to obtain filtrate, rotary-steaming at 40deg.C, removing residual liquid, distilling at 125deg.C under reduced pressure, adding the obtained liquid into molecular sieve overnight, and obtaining solvent with high purity, wherein the structural formula is shown in formula IV.
And dissolving a certain amount of lithium bis (fluorosulfonyl) imide in the obtained solvent to ensure that the concentration of lithium bis (fluorosulfonyl) imide is 0.5mol/L, and stirring until the electrolyte is completely clarified, thus obtaining the high-voltage lithium metal/graphite electrolyte for the lithium battery.
FIG. 7 is a solution of 0.5mol/L electrolyte in LiLiCoO prepared from the solvent prepared in example 4 and lithium difluorosulfimide salt 2 Charge-discharge curve in battery, wherein the surface capacity of positive electrode is 2mAh cm -2 The capacity of the negative electrode surface is 4mAh cm -2 . As can be seen from fig. 7, liCoO 2 The positive electrode material can be charged and discharged in the high-voltage electrolyte in a high-efficiency and reversible manner. Along with the circulation, the specific discharge capacity only has small amplitude attenuation, which shows the excellent high-voltage resistance performance of the electrolyte and the good compatibility with Li metal cathodes.
Example 5
A high-voltage lithium metal/graphite electrolyte solvent for a lithium battery is prepared by the following steps:
5.1g (0.06 mol) of piperidine (molecular weight M=85) and 8.08g (0.08 mol) of triethylamine (Et 3 N, molecular weight M=101) was dissolved in 120ml of tetrahydrofuran, 10.11g (0.06 mol) of a solution of trifluoromethylsulfonyl chloride (molecular weight M=168.5) dissolved in 40ml of tetrahydrofuran was added dropwise thereto, reacted at-60℃for at least 72 hours, then slowly raised to 0℃and taken out, a sufficient amount of concentrated hydrochloric acid was added first, then a product was obtained, which was separated and filtered, the filtrate was retained, washed with brine, dehydrated (4 hours) by adding anhydrous magnesium sulfate, the filtrate was taken out by filtration, the residual liquid was taken out by rotary distillation at 40℃and distilled under reduced pressure at 125℃to obtain a liquid, which was added to a molecular sieveThe solvent with higher purity is obtained overnight, and the structural formula is shown as formula V.
And dissolving a certain amount of lithium bis (fluorosulfonyl) imide in the obtained solvent to ensure that the concentration of lithium bis (fluorosulfonyl) imide is 1.0mol/L, and stirring until the electrolyte is completely clarified, thus obtaining the high-voltage lithium metal/graphite electrolyte for the lithium battery.
FIG. 8 shows the concentration of 1.0mol/L electrolyte prepared from the solvent prepared in example 5 and lithium difluorosulfimide in LiLiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in battery, wherein the face capacity of positive electrode is 2mAh cm -2 The capacity of the negative electrode surface is 4mAh cm -2 . As can be seen from FIG. 8, the capacity retention rate of 80% can be maintained for 200 cycles, and the average coulombic efficiency is as high as 99.8%. While little capacity remains after 200 cycles of commercial electrolyte.
Example 6
A high-voltage lithium metal/graphite electrolyte solvent for a lithium battery is prepared by the following steps:
10.86g (0.06 mol) of bis (2, 2-trifluoroethyl) amine (molecular weight M=181) and 8.08g (0.08 mol) of triethylamine (Et) 3 N, molecular weight M=101) was dissolved in 120ml tetrahydrofuran, to which was added dropwise a solution of 8.61g (0.06 mol) of dimethylaminosulfonyl chloride (molecular weight M=143.5) dissolved in 40ml tetrahydrofuran, reacted at-60℃for at least 72 hours, then slowly raised to 0℃and taken out, a sufficient amount of concentrated hydrochloric acid was added first, then a product was obtained, which was separated and filtered, the filtrate was kept, washed with brine, anhydrous magnesium sulfate was added to remove water (4 hours), the filtrate was taken out by filtration, the residual liquid was taken out by rotary evaporation at 40℃and distilled under reduced pressure at 125℃to obtain a liquid, which was added to a molecular sieve overnight to obtain a solvent of higher purity, the structural formula being shown in formula VI.
And dissolving a certain amount of lithium bis (fluorosulfonyl) imide in the obtained solvent to ensure that the concentration of lithium bis (fluorosulfonyl) imide is 0.5mol/L, and stirring until the electrolyte is completely clarified, thus obtaining the high-voltage lithium metal/graphite electrolyte for the lithium battery.
FIG. 9 is a graph showing the concentration of 0.5mol/L electrolyte in Li LiNi prepared from the solvent prepared in example 6 and lithium difluorosulfonimide salt 0.8 Co 0.1 Mn 0.1 O 2 Charge-discharge curve in battery, wherein the surface capacity of positive electrode is 1mAh cm -2 The capacity of the negative electrode surface is 4mAh cm -2 . As can be seen from FIG. 8, the capacity retention rate of 77% can be maintained for 200 cycles, and the average coulombic efficiency is as high as 99.7% or more.
Comparative example 1
An amount of lithium hexafluorophosphate was slowly dissolved in a volume ratio of 3:7 of ethylene carbonate and dimethyl carbonate to give a lithium salt lithium hexafluorophosphate concentration of 1.0mol/L. Stirring until the electrolyte is completely clarified, and obtaining the commercial ester-based electrolyte of the lithium battery.
FIG. 10 shows the electrolyte prepared in comparative example 1 at Li LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cycle life graph in battery, wherein the face capacity of positive electrode is 2mAh cm -2 The capacity of the negative electrode surface is 4mAh cm -2 . As can be seen from fig. 10, the above electrolyte had almost no remaining specific discharge capacity after 50 cycles, no capacity remained after 100 cycles, and the coulombic efficiency became 0. Compared with the high-voltage electrolyte, the cycle performance of the invention is greatly reduced.
Comparative example 2
An amount of lithium hexafluorophosphate was slowly dissolved in the volume ratio of 1:1:1 of ethylene carbonate, diethyl carbonate and methylethyl carbonate to give a lithium salt lithium hexafluorophosphate concentration of 1.2mol/L. Stirring until the electrolyte is completely clarified, and obtaining the commercial ester-based electrolyte of the lithium battery.
FIG. 11 is a graph showing the Gr LiCoO of the electrolyte prepared in comparative example 2 2 Cycle life graph in battery, wherein the face capacity of positive electrode is 5mAh cm -2 The capacity of the negative electrode surface is 5mAh cm -2 . As can be seen from fig. 11At a charge cut-off voltage as high as 4.55V, the cyclic capacity decays rapidly, and the capacity retention rate after 200 cycles is 40.8%. In addition, the fluctuation of the coulombic efficiency is large, the average coulombic efficiency is 98.9%, and the commercial standard of the high-voltage electrolyte is far from being reached.
Comparative example 3
Slowly dissolving a certain amount of lithium hexafluorophosphate in ethylene carbonate and dimethyl carbonate with the volume ratio of 3:7, then slowly adding an additive of ethylene carbonate to ensure that the concentration of lithium hexafluorophosphate is 1mol/L, and stirring until the electrolyte is completely clarified, thereby obtaining the commercial modified ester-based electrolyte of the lithium battery.
FIG. 12 is a graph showing the Li LiNi content of the electrolyte prepared in comparative example 3 0.8 Co 0.1 Mn 0.1 O 2 Charge-discharge curve in battery, wherein the surface capacity of positive electrode is 2mAh cm -2 The capacity of the negative electrode surface is 4mAh cm -2 . As can be seen from fig. 12, liNi 0.8 Co 0.1 Mn 0.1 O 2 In the commercial modified ester-based electrolyte, the positive electrode material only has good charge and discharge platforms in the first circle and the tenth circle. After 100 cycles, normal charge and discharge are not possible, and the reversible capacity rapidly decays to 0.
Li LiNi in examples 1 to 6 and comparative examples 1 to 3 0.8 Co 0.1 Mn 0.1 O 2 And Li LiCoO 2 Button half cell and Gr LiCoO 2 Manufacturing and testing of button type full batteries:
(1) Positive pole piece: liNi is added to 0.8 Co 0.1 Mn 0.1 O 2 Or LiCoO 2 Adding the binder PVDF and the conductive carbon black into N-methyl pyrrolidone (NMP) according to the ratio of 9:0.5:0.5, and uniformly mixing to obtain slurry; then coating the aluminum foil current collector, drying at 100 ℃, rolling, and cutting a wafer with the diameter of 12mm by a sheet punching machine;
(2) Li negative electrode: adopting a metal lithium sheet with the diameter of 15mm and the thickness of 20 mu m;
(3) Gr (graphite) anode: adding MCMB, a binder PAALi and conductive carbon black into water according to the ratio of 9:0.5:0.5, and uniformly mixing to obtain slurry; then coating the copper foil current collector, drying at 80 ℃, rolling, and cutting a wafer with the diameter of 14mm by a sheet punching machine;
(4) Electrolyte solution: the electrolytes prepared in examples 1 to 6 and comparative examples 1 to 3;
(5) A diaphragm: cutting a polyethylene single-layer diaphragm wafer with the diameter of 19mm by a sheet punching machine;
(6) And (3) battery assembly: in glove box (O) 2 ＜0.1ppm，H 2 O < 0.1 ppm), assembling the button lithium battery according to the sequence of positive electrode shell-positive electrode wafer-diaphragm wafer-negative electrode wafer-stainless steel sheet-spring piece-negative electrode shell, adding the electrolyte prepared in the examples 1-6 and the comparative examples 1-3, and finally packaging to obtain a test battery;
(7) And (3) battery testing:
the electrolytes in examples 1 to 6 and comparative examples 1 to 3 correspond to batteries 1 to 9, li LiNi 0.8 Co 0.1 Mn 0.1 O 2 (2.8-4.7V) and Li LiCoO 2 (3-4.55V) button half cell and Gr LiCoO 2 After the button type full battery is activated for 3 circles at the room temperature (25 ℃), the multiplying power of 0.1C and the multiplying power of 0.5C are circulated for a long time; the test results are shown in FIGS. 2,4 and 6-12, and the results analysis and conclusion are described in examples and comparative examples, respectively.
Claims (10)
1. The application of the fluoro-sulfonamide compound is characterized in that the fluoro-sulfonamide compound is used as an organic solvent of lithium battery electrolyte, and the general formula of the fluoro-sulfonamide compound is shown as a structural formula I or a structural formula II:
wherein R is 1 The method comprises the following steps: aliphatic cyclic alkylamino, benzenoalkylamino, anilino or haloalkylamino; r is R 2 The method comprises the following steps: fluoroalkylamine groups.
2. The use of a fluorosulfonamide compound according to claim 1, wherein said R 1 Selected from the group consisting of pyrrolidinyl, morpholinyl, piperidyl, and N-methylPhenethylamine groups, N-methylanilino groups or-N [ (CH) 2 ) n CX 3 ] 2 N is any positive integer from 1 to 4, and X=F, cl, br or I; r is R 2 is-N [ (CH) 2 ) n CF 3 ] 2 N is any positive integer from 1 to 4.
3. The high-voltage electrolyte for the lithium battery is characterized by comprising an organic solvent, wherein the organic solvent is a fluoro-sulfonamide compound, and the general formula of the fluoro-sulfonamide compound is shown as a structural formula I or a structural formula II:
wherein R is 1 The method comprises the following steps: aliphatic cyclic alkylamino, benzenoalkylamino, anilino or haloalkylamino; r is R 2 The method comprises the following steps: fluoroalkylamine groups.
4. The high-voltage electrolyte according to claim 3, wherein the fluorosulfonamide compound accounts for 70% -95% of the total mass of the electrolyte.
5. The high voltage electrolyte of claim 3 wherein R 1 Selected from pyrrolidinyl, morpholinyl, piperidyl, N-methylphenylamino or-N [ (CH) 2 ) n CX 3 ] 2 N is any positive integer from 1 to 4, and X=F, cl, br or I; r is R 2 is-N [ (CH) 2 ) n CF 3 ] 2 N is any positive integer from 1 to 4.
6. The high voltage electrolyte of claim 3 further comprising an electrolyte lithium salt, wherein the lithium salt is at least one of an inorganic anion lithium salt and an organic anion lithium salt of lithium hexafluorophosphate, lithium bis (trifluoromethylsulfonyl) imide, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium difluorooxalato borate, and lithium difluorophosphate.
7. The high voltage electrolyte according to claim 6, wherein the concentration of the lithium salt is 0.5 to 3.0mol/L.
8. A lithium battery comprising a positive electrode, a negative electrode and the high voltage electrolyte of any one of claims 4-7.
9. The lithium battery according to claim 8, wherein the active material in the positive electrode is LiCoO 2 And LiNi 0.8 Mn 0.1 Co 0.1 O 2 The active material in the negative electrode is lithium metal or graphite.
10. The lithium battery according to claim 9, wherein the positive and negative electrode active materials have a surface capacity of 0.5 to 5mAh cm -2 。
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