CN113140793A - High-voltage lithium ion electrolyte and application thereof - Google Patents
High-voltage lithium ion electrolyte and application thereof Download PDFInfo
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- CN113140793A CN113140793A CN202110339748.4A CN202110339748A CN113140793A CN 113140793 A CN113140793 A CN 113140793A CN 202110339748 A CN202110339748 A CN 202110339748A CN 113140793 A CN113140793 A CN 113140793A
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- Prior art keywords
- lithium
- carbonate
- lithium ion
- additive
- electrolyte
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 55
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- 239000000654 additive Substances 0.000 claims abstract description 67
- 230000000996 additive effect Effects 0.000 claims abstract description 48
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 18
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 150000003568 thioethers Chemical class 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 8
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 30
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 30
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 24
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 24
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 20
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- FLDNDAMSCINJDX-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 2-trimethylsilylethyl carbonate Chemical compound C[Si](C)(C)CCOC(=O)ON1C(=O)CCC1=O FLDNDAMSCINJDX-UHFFFAOYSA-N 0.000 claims description 9
- QGNRLAFFKKBSIM-UHFFFAOYSA-N prop-2-enylsulfanylbenzene Chemical compound C=CCSC1=CC=CC=C1 QGNRLAFFKKBSIM-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 4
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims 1
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- YQQKTCBMKQQOSM-UHFFFAOYSA-N trifluoromethylsulfanylbenzene Chemical compound FC(F)(F)SC1=CC=CC=C1 YQQKTCBMKQQOSM-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- 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
- H01M10/42—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
Landscapes
- 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 a high-voltage lithium ion electrolyte and application thereof, wherein the electrolyte comprises the following components in percentage by weight: 5-20 wt% of electrolyte lithium salt, 70-80 wt% of solvent, 0.1-10 wt% of thioether additive, 0.1-5 wt% of silicon additive and 0.1-5 wt% of other film-forming additive, wherein the thioether additive comprises any one of the following additives or a mixture of several of the following additives,
the silicon additive comprises any one or a mixture of several of the following components,
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-voltage lithium ion electrolyte and application thereof.
Background
The lithium ion battery as a novel green environment-friendly battery has the characteristics of large specific capacity, good safety, long cycle life and the like, so that the lithium ion battery is widely applied to the aspects of aerospace, wearable and medical electronic equipment, transportation, national safety and the like. The electrolyte is an important component of the lithium ion battery and is a bridge for connecting the anode and the cathode of the battery, so that the performance of the electrolyte can influence the performance of the lithium ion battery to a great extent, and the development of the novel electrolyte has important significance.
The addition of a small amount of additive can obviously improve the conductivity, the cycle performance, the safety and the like of the battery, and the novel silicon additive becomes the key point of the development at home and abroad in the development of the lithium secondary electrolyte. Chinese patent document CN104752766B discloses an electrolyte additive, which contains three silicon groups in the structural formula, and has a large molecular weight, poor compatibility with electrolyte, and poor high-temperature storage performance. Although the common thioether additive, namely the trifluoromethylphenylsulfide (PTS), improves the cycling stability of the battery under high voltage to a certain extent, the high-temperature and high-pressure cycling performance and the safety performance of the electrolyte still need to be improved.
Therefore, it is important to develop a high-voltage lithium ion electrolyte to improve the high-temperature and high-voltage cycle performance and safety of the battery.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art or the related art.
Therefore, an object of the present invention is to provide a high-voltage lithium ion electrolyte and an application thereof, which significantly improve high-temperature and high-voltage cycle performance and storage performance of a lithium ion battery, and improve safety.
In order to achieve the above object, a technical solution of a first aspect of the present invention provides a high-voltage lithium ion electrolyte, including the following components by weight:
5 to 20 weight percent of electrolyte lithium salt, 70 to 80 weight percent of solvent, 0.1 to 10 weight percent of thioether additive, 0.1 to 5 weight percent of silicon additive and 0.1 to 5 weight percent of other additives,
the thioether additive comprises any one or a mixture of several of the following components,
the silicon additive comprises any one or a mixture of several of the following components,
in the technical scheme, the thioether additive, the silicon additive and other additives jointly promote film formation, wherein the thioether additive can form a compact and uniform CEI film on the surface of a positive electrode material, improve the uniformity and stability of an electrode and an electrolyte phase interface film, inhibit further oxidation of an electrolyte, effectively prevent dissolution of metal ions and further inhibit side reactions on the surface of the electrode, improve the cycling stability of the battery under high voltage, and simultaneously can also consider a high-capacity silicon-carbon negative electrode, thereby avoiding the problems of large-amount electrolyte consumption and the like caused by repeated 'cracking-regeneration' of a solid electrolyte film (SEI film) due to volume expansion of a negative electrode material. The silicon additive can greatly improve the voltage resistance of the electrolyte, is not easy to decompose under high voltage, can eliminate HF generated by lithium salt hydrolysis by the silicon-based compound, inhibits gas generation and LiF enrichment in a graphite cathode in the battery charging and discharging processes, and simultaneously forms a Si-O-Si network structure on the surface of the graphite cathode under the catalysis of trace water, so that the damage of a solvent to the graphite cathode is inhibited. The synergistic effect of the thioether additive and the silicon additive obviously improves the high-temperature and high-pressure cycle performance, the storage performance and the safety of the lithium ion battery.
In the above technical solution, preferably, the electrolyte lithium salt is any one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium dioxalate borate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonate imide) imide, and lithium difluorinated oxalate borate, or a mixture of several of them.
In any of the above technical solutions, preferably, the solvent is one or a combination of dimethyl carbonate (DMC), Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC), Propylene Carbonate (PC), Methyl Propyl Carbonate (MPC), γ -butyrolactone (GBL), Ethyl Acetate (EA), Tetrahydrofuran (THF), Fluorobenzene (FB) and Acetonitrile (AN).
In any of the above technical solutions, preferably, the other additive is selected from one or more of Vinylene Carbonate (VC), Biphenyl (BP), triphenyl phosphite (TPP), 1, 3-Propane Sultone (PS), 1, 4-Butane Sultone (BS), Succinic Anhydride (SA) and fluoroethylene carbonate (FEC).
In any of the above technical solutions, preferably, a mixed solution prepared by dimethyl carbonate (DMC), Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) in a volume ratio of 1:2:1 is used as the solvent; the lithium salt is lithium hexafluorophosphate, and the concentration is 1.3 mol/L; other additives were 2.0 wt% Vinylene Carbonate (VC) and 1.0 wt% fluoroethylene carbonate (FEC).
In the technical scheme, 2.0 wt% Vinylene Carbonate (VC) and 1.0 wt% fluoroethylene carbonate (FEC) can be cooperated with thioether additives and silicon additives to jointly promote film formation, and the electrolyte compatibility of the formula components is good, the control of moisture and acidity is qualified, and the capacity, cycle life and safety of the battery are favorably improved.
In any of the above embodiments, preferably, the thioether additive is 2.0 wt% allyl phenyl sulfide; the silicon additive was 2.0 wt% 1- [2- (trimethylsilyl) ethoxycarbonyloxy ] pyrrolidine-2, 5-dione.
In the technical scheme, the capacity and the high-temperature and high-pressure cycle performance of the battery are high, the discharge capacity retention rate can reach 99.22% after 300 cycles under the test conditions of 3.0-4.45V and 45 ℃, and the 1C discharge capacity is 1585.31 mAh.
The technical scheme of the second aspect of the invention provides an application of a high-voltage lithium ion electrolyte, wherein the high-voltage lithium ion electrolyte is applied to a ternary/silicon-carbon system, a ternary/graphite system, a lithium iron phosphate/graphite system, a lithium manganate/graphite system and a lithium cobaltate/graphite system; the high-voltage lithium ion electrolyte is applied to lithium ion batteries, quasi-solid lithium batteries, solid lithium batteries and lithium air batteries.
The high-voltage lithium ion electrolyte and the application thereof provided by the invention have the following beneficial technical effects:
(1) the thioether additive is added into the electrolyte of the high-voltage lithium ion battery, so that a good electrode-interface film can be formed, and the thioether additive can be applied to the high-voltage lithium ion battery, so that the capacity retention rate of the battery can be improved, and the cycling stability of the battery can be obviously improved under the high-voltage condition.
(2) The silicon additive is added into the electrolyte of the high-voltage lithium ion battery, so that the voltage resistance of the electrolyte can be greatly improved, the electrolyte is difficult to decompose under high voltage, and HF generated by lithium salt hydrolysis can be removed by the silicon additive.
(3) The thioether additive, the silicon additive, other film forming additives, Vinylene Carbonate (VC) and fluoroethylene carbonate (FEC) jointly act to promote film formation, so that the voltage resistance of the electrolyte can be greatly improved, the electrolyte is not easy to decompose under high voltage, the compatibility of the electrolyte is high, the moisture and acidity of the electrolyte are controlled to be qualified, the safety is high, the capacity and the high-temperature and high-pressure cycle performance of the battery are high, the discharge capacity can reach 99.22% after the battery is cycled for 300 weeks under the test conditions of 3.0-4.45V and 45 ℃, and the discharge capacity at 1C is 1585.31 mAh.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The invention discloses a high-voltage lithium ion electrolyte and application thereof, and a person skilled in the art can appropriately improve process parameters by referring to the content. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention is further illustrated by the following examples:
example 1
Under the airtight protection atmosphere, the water content is 0.1ppm, the oxygen content is 0.1ppm, solvents of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are respectively and sequentially added and mixed according to the mass ratio of 1:2:1, the mixed solution is cooled by a condenser to ensure that the temperature is not higher than 10 ℃, lithium hexafluorophosphate is slowly added to ensure that the concentration of lithium salt is 1.3mol/L, then, 2.0 wt% of Vinylene Carbonate (VC) and 1.0 wt% of fluoroethylene carbonate (FEC) are respectively added according to the mass fraction of the additives, and finally, 0.5 wt% of 1- [2- (trimethylsilyl) ethoxycarbonyloxy ] pyrrolidine-2, 5-dione additive and 2.0 wt% of allyl phenyl sulfide are added and continuously stirred until the solution becomes clear.
Example 2
Under the atmosphere of nitrogen gas closed protection, the water content is 0.1ppm, the oxygen content is 0.1ppm, solvents of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are respectively and sequentially added and mixed according to the mass ratio of 1:2:1, the mixed solution is cooled by a condenser to ensure that the temperature is not higher than 10 ℃, lithium hexafluorophosphate is slowly added to ensure that the concentration of lithium salt is 1.3mol/L, then film forming additives of Vinylene Carbonate (VC) with the mass fraction of 2.0 wt% and fluoroethylene carbonate (FEC) with the mass fraction of 1.0 wt% are added, and finally 1- [2- (trimethylsilyl) ethoxycarbonyloxy ] pyrrolidine-2, 5-dione additive with the mass fraction of 1.0 wt% and 2.0 wt% allyl phenyl sulfide are added and continuously stirred until the solution becomes clear.
Example 3
Under the atmosphere of nitrogen gas closed protection, the water content is 0.1ppm, the oxygen content is 0.1ppm, solvents of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are respectively and sequentially added and mixed according to the mass ratio of 1:2:1, the mixed solution is cooled by a condenser to ensure that the temperature is not higher than 10 ℃, lithium hexafluorophosphate is slowly added to ensure that the concentration of lithium salt is 1.3mol/L, then film forming additives of Vinylene Carbonate (VC) with the mass fraction of 2.0 wt% and fluoroethylene carbonate (FEC) with the mass fraction of 1.0 wt% are added, and finally 1- [2- (trimethylsilyl) ethoxycarbonyloxy ] pyrrolidine-2, 5-dione additive with the mass fraction of 2.0 wt% and 2.0 wt% allyl phenyl sulfide are added and continuously stirred until the solution becomes clear.
Example 4
Under the atmosphere of nitrogen gas closed protection, the water content is 0.1ppm, the oxygen content is 0.1ppm, solvents of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are respectively and sequentially added and mixed according to the mass ratio of 1:2:1, the mixed solution is cooled by a condenser to ensure that the temperature is not higher than 10 ℃, lithium hexafluorophosphate is slowly added to ensure that the concentration of lithium salt is 1.3mol/L, then film forming additives of Vinylene Carbonate (VC) with the mass fraction of 2.0 wt% and fluoroethylene carbonate (FEC) with the mass fraction of 1.0 wt% are added, and finally 1- [2- (trimethylsilyl) ethoxycarbonyloxy ] pyrrolidine-2, 5-dione additive with the mass fraction of 2.0 wt% and 0.5 wt% allyl phenyl sulfide are added and continuously stirred until the solution becomes clear.
Example 5
Under the atmosphere of nitrogen gas closed protection, the water content is 0.1ppm, the oxygen content is 0.1ppm, solvents of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are respectively and sequentially added and mixed according to the mass ratio of 1:2:1, the mixed solution is cooled by a condenser to ensure that the temperature is not higher than 10 ℃, lithium hexafluorophosphate is slowly added to ensure that the concentration of lithium salt is 1.3mol/L, then film forming additives of Vinylene Carbonate (VC) with the mass fraction of 2.0 wt% and fluoroethylene carbonate (FEC) with the mass fraction of 1.0 wt% are added, and finally 1- [2- (trimethylsilyl) ethoxycarbonyloxy ] pyrrolidine-2, 5-dione additive with the mass fraction of 2.0 wt% and 1.0 wt% allyl phenyl sulfide are added and continuously stirred until the solution becomes clear.
Comparative example 1
Under the nitrogen sealed protection atmosphere, the water content is 0.1ppm, the oxygen content is 0.1ppm, solvents of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are respectively taken and sequentially added and mixed according to the mass ratio of 1:2:1, a condenser is used for cooling the mixed solution to ensure that the temperature is not higher than 10 ℃, lithium hexafluorophosphate is slowly added to ensure that the concentration of lithium salt is 1.3mol/L, then film forming additives are added, the mass fractions of the film forming additives are respectively 2.0 wt% of Vinylene Carbonate (VC) and 1.0 wt% of fluoroethylene carbonate (FEC), and the stirring is continued until the solution becomes clear.
Comparative example 2
Under the nitrogen sealed protection atmosphere, the water content is 0.1ppm, the oxygen content is 0.1ppm, solvents of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are respectively and sequentially added and mixed according to the mass ratio of 1:2:1, the mixed solution is cooled by a condenser to ensure that the temperature is not higher than 10 ℃, lithium hexafluorophosphate is slowly added to ensure that the concentration of lithium salt is 1.3mol/L, then a film forming additive with the mass fraction of 2.0 wt% of Vinylene Carbonate (VC) and 1.0 wt% of fluoroethylene carbonate (FEC) is added, finally a 1- [2- (trimethylsilyl) ethoxycarbonyloxy ] pyrrolidine-2, 5-dione additive with the mass fraction of 2.0 wt% is added, and the stirring is continued until the solution becomes clear.
Comparative example 3
Under the nitrogen sealed protection atmosphere, the water content is 0.1ppm, the oxygen content is 0.1ppm, solvents of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are respectively and sequentially added and mixed according to the mass ratio of 1:2:1, a condenser is used for cooling the mixed solution to ensure that the temperature is not higher than 10 ℃, lithium hexafluorophosphate is slowly added to ensure that the concentration of lithium salt is 1.3mol/L, then film forming additives are added, the mass fractions of the film forming additives are respectively 2.0 wt% of Vinylene Carbonate (VC) and 1.0 wt% of fluoroethylene carbonate (FEC), and finally 2.0 wt% of allyl phenyl sulfide is added and stirring is continued until the solution becomes clear.
The electrolytes prepared in the examples and the comparative examples are tested for the moisture and acidity content according to GB/T19282-2014, and the test results are shown in the following table 1.
TABLE 1
| Moisture (ppm) | Acidity (ppm) | |
| Example 1 | 3.2 | 24.5 |
| Example 2 | 4.5 | 23.8 |
| Example 3 | 4.4 | 24.3 |
| Example 4 | 3.2 | 26.8 |
| Example 5 | 3.9 | 23.9 |
| Comparative example 1 | 7.9 | 26.0 |
| Comparative example 2 | 6.5 | 26.7 |
| Comparative example 3 | 8.9 | 21.0 |
The content of moisture and acidity in the electrolyte of the lithium ion battery is always considered as a key standard for determining the quality of the battery, the requirement of the high-voltage electrolyte on the moisture and the acidity is higher, if the moisture content in the electrolyte is slightly higher, the oxidation resistance of the electrolyte is greatly reduced, and the existence of hydrofluoric acid has great influence on the capacity, the cycle life and the safety of the battery. As can be seen from Table 1, the control of moisture and acidity was acceptable, and the control of moisture and acidity in examples 2 and 3 was more suitable.
The experimental anode adopts composite conductive agent Super-P, binder PVDF-900, lithium iron phosphate anode material and solvent N-methyl pyrrolidone (NMP), the cathode adopts graphite, solvent CMC and ultrapure water in Jiangxi Zichen, conductive agent Super-P and binder SBR-A-301+ as raw materials, A slurry is prepared by A wet pulping process, the viscosity of the anode is controlled to be 10000-12000 mPa.s, the viscosity of the cathode is controlled to be 1500-3000 mPa.s, the lithium ion soft package battery is prepared by coating, cutting into large sheets, rolling, slitting, drying at 85 ℃ for 48h, sticking adhesive tapes, winding and drying at 80 ℃ for 48h, the different electrolyte formulas are injected into A battery core and sealed, standing at 45 ℃ for 24h, forming and vacuum secondary sealing, and then the battery is subjected to cycle performance and high-temperature storage performance test. The test results are shown in table 2 below.
TABLE 2
As can be seen from Table 2, the addition of the thioether additive and the silicon additive obviously improves the high-temperature cycle performance and the discharge capacity of the lithium ion battery, wherein the performance effect of the example 3 with the addition of the 1- [2- (trimethylsilyl) ethoxycarbonyloxy ] pyrrolidine-2, 5-dione additive in a mass fraction of 2.0 wt% and the allyl phenyl sulfide in a mass fraction of 2.0 wt% is better, the discharge capacity retention rate of the example 3 in 300 cycles can reach 99.22% under the test conditions of 3.0-4.45V and 45 ℃, and the discharge capacity of the example 3 in 1C is 1585.31 mAh. The thioether additive, the silicon additive, other film forming additives, Vinylene Carbonate (VC) and fluoroethylene carbonate (FEC) jointly act to promote film formation, so that the capacity retention rate of the battery can be improved, the cycle stability of the battery is obviously improved under a high voltage condition, the voltage resistance of the electrolyte is greatly improved, the electrolyte is difficult to decompose under the high voltage, HF generated by lithium salt hydrolysis can be removed by the silicon additive, and the capacity and the high-temperature and high-pressure cycle performance of the battery are integrally improved by the electrolyte formula.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. The high-voltage lithium ion electrolyte is characterized by comprising the following components in percentage by weight:
5-20 wt% of electrolyte lithium salt, 70-80 wt% of solvent, 0.1-10 wt% of thioether additive, 0.1-5 wt% of silicon additive and 0.1-5 wt% of other film-forming additive,
the thioether additive comprises any one or a mixture of several of the following components,
the silicon additive comprises any one or a mixture of several of the following components,
2. the high-voltage lithium ion electrolyte according to claim 1, wherein the electrolyte lithium salt is any one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium dioxalate borate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonate imide) imide, lithium difluorine oxalate borate, or a mixture of several of them.
3. The high voltage lithium ion electrolyte as claimed in claim 2, wherein the solvent is one or more selected from dimethyl carbonate (DMC), Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC), Propylene Carbonate (PC), Methyl Propyl Carbonate (MPC), gamma-butyrolactone (GBL), Ethyl Acetate (EA), Tetrahydrofuran (THF), Fluorobenzene (FB) and Acetonitrile (AN).
4. The high-voltage lithium ion electrolyte according to claim 3, wherein the other film-forming additive is selected from one or more of Vinylene Carbonate (VC), Biphenyl (BP), triphenyl phosphite (TPP), 1, 3-Propane Sultone (PS), 1, 4-Butane Sultone (BS), Succinic Anhydride (SA), and fluoroethylene carbonate (FEC).
5. The high voltage lithium ion electrolyte of claim 4,
a mixed solution prepared from dimethyl carbonate (DMC), Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) according to a volume ratio of 1:2:1 is used as the solvent;
the lithium salt is lithium hexafluorophosphate, and the concentration is 1.3 mol/L;
other additives were 2.0 wt% Vinylene Carbonate (VC) and 1.0 wt% fluoroethylene carbonate (FEC).
6. The high voltage lithium ion electrolyte of claim 5,
the thioether additive is 2.0 wt% of allyl phenyl thioether;
the silicon additive was 2.0 wt% 1- [2- (trimethylsilyl) ethoxycarbonyloxy ] pyrrolidine-2, 5-dione.
7. Use of a high voltage lithium ion electrolyte according to any of the above claims 1 to 6,
the high-voltage lithium ion electrolyte is applied to a ternary/silicon-carbon system, a ternary/graphite system, a lithium iron phosphate/graphite system, a lithium manganate/graphite system and a lithium cobaltate/graphite system;
the high-voltage lithium ion electrolyte is applied to lithium ion batteries, quasi-solid lithium batteries, solid lithium batteries and lithium air batteries.
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