WO2015032215A1 - Additif d'électrolyte haute tension organique non aqueux, électrolyte haute tension organique non aqueux et batterie secondaire au lithium-ion - Google Patents

Additif d'électrolyte haute tension organique non aqueux, électrolyte haute tension organique non aqueux et batterie secondaire au lithium-ion Download PDF

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WO2015032215A1
WO2015032215A1 PCT/CN2014/078010 CN2014078010W WO2015032215A1 WO 2015032215 A1 WO2015032215 A1 WO 2015032215A1 CN 2014078010 W CN2014078010 W CN 2014078010W WO 2015032215 A1 WO2015032215 A1 WO 2015032215A1
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carbon atoms
aqueous organic
groups
halogenated
organic high
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PCT/CN2014/078010
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Chinese (zh)
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许梦清
邢丽丹
李伟善
杨同勇
安伟峰
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华为技术有限公司
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Non-aqueous organic high-voltage electrolyte additive, non-aqueous organic high-voltage electrolyte and lithium ion secondary battery The application request is submitted to the Chinese Patent Office on September 5, 2013, and the application number is 201310400272.6. The priority of the Chinese patent application for non-aqueous organic high-voltage electrolyte additives, non-aqueous organic high-voltage electrolytes and lithium-ion secondary batteries is hereby incorporated by reference in its entirety.
  • the present invention relates to the field of lithium ion secondary batteries, and more particularly to a nonaqueous organic high voltage electrolyte additive, a nonaqueous organic high voltage electrolyte, and a lithium ion secondary battery. Background technique
  • lithium ion secondary batteries With the expansion of the application field of lithium ion secondary batteries, including the introduction of new application scenarios such as large-scale energy storage power stations and base station power supply in recent years, the demand for high-energy lithium-ion secondary batteries has become more pressing.
  • LiCoP0 4 LiNiP0 4
  • LiNio.sMnLsC LiCoP0 4 , LiNiP0 4
  • LiNio.sMnLsC LiNio.sMnLsC
  • the charging voltage platform is close to or higher than 5V, but the matching non-aqueous organic electrolyte seriously lags behind the development of high-voltage positive electrode materials.
  • the application of lithium ion secondary batteries is limited. For example, lM LiPF 6 is dissolved in a carbonate-based solvent to form a non-aqueous organic electrolyte.
  • a first aspect of an embodiment of the present invention is directed to provide a non-aqueous organic high-voltage electrolyte additive which is oxidatively decomposed during charging of a high-voltage lithium ion secondary battery. Promoting the formation of a protective film on the surface of the positive electrode material and suppressing the oxidation of the positive electrode material to the solvent of the non-aqueous organic electrolyte.
  • a second aspect of the present invention is directed to a nonaqueous organic high voltage electrolyte comprising the above nonaqueous organic electrolyte additive, which is capable of satisfying a high voltage lithium ion secondary battery of 4.5 V or higher. use.
  • a third aspect of the embodiment of the present invention is directed to a lithium ion secondary battery comprising the above nonaqueous organic high voltage electrolyte, which has good cycle performance and discharge capacity at a high voltage.
  • an embodiment of the present invention provides a non-aqueous organic high-voltage electrolyte additive, and the chemical structural formula of the non-aqueous organic high-voltage electrolyte additive is as shown in the formula (I):
  • R a , R b , R c and R d are an oxygen or an organic group, and the organic group includes an alkyl group, an alkene group, an alkyne group, an aryl group, a halogenated alkyl group, a halogenated alkene group One of a halogenated alkyne group and a halogenated aryl group;
  • i, j, q, and t are 0 or 1
  • x, n, e, and h are integers from 1 to 4
  • f is an integer from 0 to (2e+l)
  • k is an integer from 0 to (2h+l)
  • m is an integer from 0 to (2n+l)
  • y is an integer from 0 to (2x+l).
  • the R a , R b , R c and R d are oxygen, an alkyl group having 1 to 8 carbon atoms, an alkene group having 2 to 8 carbon atoms, and an alkyne having 2 to 8 carbon atoms.
  • a hydrocarbon group an aromatic group having 6 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, a halogenated alkene group having 2 to 8 carbon atoms, a halogenated alkynyl group having 2 to 8 carbon atoms or A halogenated aromatic group having 6 to 8 carbon atoms.
  • the R a , R b , R c and R d are an alkyl group having 2 to 6 carbon atoms, an olefin group having 2 to 6 carbon atoms, an alkyne group having 2 to 6 carbon atoms, One of a halogenated alkyl group having 2 to 6 carbon atoms, a halogenated alkene group having 2 to 6 carbon atoms, and a halogenated alkyne group having 2 to 6 carbon atoms.
  • the non-aqueous organic high-voltage electrolyte additive has a chemical structural formula of one of the formulae Ia to If:
  • a non-aqueous organic high-voltage electrolyte additive provided by the first aspect of the present invention can be used in the preparation of a lithium ion secondary battery.
  • the positive electrode potential is continuously increased, and the non-aqueous organic
  • the high voltage electrolyte additive will promote the formation of a protective film on the surface of the positive electrode material; Covering the active site on the surface of the positive electrode material, blocking the direct contact between the active site on the surface of the positive electrode material and the non-aqueous organic electrolyte, inhibiting the oxidation of the positive electrode material on the non-aqueous organic electrolyte, and solving the non-aqueous in the prior art
  • the organic electrolyte is easily reacted with the positive electrode material in a high voltage (above 4.5V voltage) battery system, causing problems in the cycle performance, volume expansion, and discharge capacity of the lithium ion secondary battery, thereby increasing lithium ion at high voltage.
  • the cycle performance and discharge capacity of the secondary battery can be used in the preparation of
  • an embodiment of the present invention provides a non-aqueous organic high-voltage electrolyte, comprising: a lithium salt, a non-aqueous organic solvent, and a non-aqueous organic high-voltage electrolyte additive, and the non-aqueous organic high-voltage electrolyte additive
  • a non-aqueous organic high-voltage electrolyte comprising: a lithium salt, a non-aqueous organic solvent, and a non-aqueous organic high-voltage electrolyte additive, and the non-aqueous organic high-voltage electrolyte additive
  • R a , R b , R c and R d are an oxygen or an organic group, and the organic group includes an alkyl group, an alkene group, an alkyne group, an aryl group, a halogenated alkyl group, a halogenated alkene group, One of a haloalkynyl group and a halogenated aryl group; wherein i, j, q, and t are 0 or 1; x, n, e, and h are integers from 1 to 4, and f is 0 to (2e+l) The integer, k is an integer from 0 to (2h+l), m is an integer from 0 to (2n+l), and y is an integer from 0 to (2x+l).
  • the R a , R b , R c and R d are oxygen, an alkyl group having 1 to 8 carbon atoms, an alkene group having 2 to 8 carbon atoms, and an alkyne having 2 to 8 carbon atoms.
  • a hydrocarbon group an aromatic group having 6 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, a halogenated alkene group having 2 to 8 carbon atoms, a halogenated alkynyl group having 2 to 8 carbon atoms or A halogenated aromatic group having 6 to 8 carbon atoms.
  • the R a , R b , R c and R d are an alkyl group having 2 to 6 carbon atoms, and the number of carbon atoms is 2 ⁇ 6 an olefin group, an alkyne group having 2 to 6 carbon atoms, a halogenated alkyl group having 2 to 6 carbon atoms, a halogenated alkene group having 2 to 6 carbon atoms, and a halogenated group having 2 to 6 carbon atoms One of the alkyne groups.
  • the lithium salt is selected from the group consisting of LiPF 6 , LiBF 4 , LiC10 4 , Li ( CF 3 S0 2 ) 2 N, LiBOB (lithium bis(oxalate) borate), LiDFOB (lithium difluorooxalate borate), and LiPF 4 C 2 0 4 (four One or more of lithium fluorooxalate phosphate.
  • the non-aqueous organic solvent is selected from the group consisting of carbonates and their derivatives, ethers, sulfones, nitriles, ionic liquids.
  • the non-aqueous organic solvent is Ethylene Carbonate (EC), Propylene Carbonate (PC), 1,2-vinylene carbonate (VC), dimercaptocarbonate ( DMC), diethyl carbonate (DEC), mercaptoethyl carbonate (EMC), fluoroethylene carbonate (FEC), ⁇ -butyrolactone, mercaptoethyl ether, tetrahydrofuran, sulfolane, acetonitrile and 1- ⁇ One or more of -3-ethylimidazolium bis(trifluoroindolyl) amide.
  • the non-aqueous organic high-voltage electrolyte additive accounts for 0.1 to 10% of the non-aqueous organic high-voltage electrolyte solution by mass fraction.
  • the non-aqueous organic high-voltage electrolyte provided by the second aspect of the present invention contains the above-mentioned non-aqueous organic high-voltage electrolyte additive, and thus can satisfy the high-voltage lithium ion secondary battery of 4.5 V or higher, and has excellent electrochemistry.
  • the stability can avoid the phenomenon of gas expansion of the lithium ion secondary battery under high voltage, and improve the cycle performance and discharge capacity of the lithium ion secondary battery under high voltage.
  • an embodiment of the present invention provides a lithium ion secondary battery, including:
  • the positive electrode comprising a positive active material capable of inserting or extracting lithium ions
  • the negative electrode comprising a negative active material capable of inserting or extracting lithium ions
  • the non-aqueous organic high-voltage electrolyte comprises: a lithium salt, a non-aqueous organic solvent and a non-aqueous organic high-voltage electrolytic solution additive, and the chemical structural formula of the non-aqueous organic high-voltage electrolyte additive is as shown in the formula (I):
  • C P eH n 2e+l- F f is a formula (I), wherein R a , R b , R c and R d are an oxygen or an organic group, and the organic group includes an alkyl group, an alkene group, an alkyne group, One of an aryl group, a haloalkyl group, a halogenated alkene group, a halogenated alkyne group, and a halogenated aryl group; wherein i, j, q, and t are 0 or 1; x, n, e, and h are 1 to 4 An integer, f is an integer from 0 to (2e+l), k is an integer from 0 to (2h+l), m is an integer from 0 to (2n+l), and y is an integer from 0 to (2x+l).
  • the non-aqueous organic high-voltage electrolyte is as described in the second aspect of the embodiment of the present invention, and details are not described herein again.
  • the lithium ion secondary battery provided by the third aspect of the embodiment of the present invention has good cycle performance and discharge capacity.
  • a non-aqueous organic high-voltage electrolyte additive provided by the first aspect of the present invention can be used in the preparation of a lithium ion secondary battery.
  • the positive electrode potential is continuously increased, and the non-aqueous
  • the organic high-voltage electrolyte additive will promote the formation of a protective film on the surface of the positive electrode material; the protective film covers the active site on the surface of the positive electrode material, blocks the direct contact between the active site on the surface of the positive electrode material and the non-aqueous organic electrolyte, and suppresses the positive electrode material.
  • a non-aqueous organic high-voltage electrolyte provided by the second aspect of the present invention contains the above-mentioned non-aqueous organic high-voltage electrolyte additive, and thus can satisfy a high-voltage lithium ion secondary battery of 4.5 V or higher, and has excellent electrochemistry. Stability, can avoid the phenomenon of gas expansion of lithium ion secondary battery under high voltage.
  • the lithium ion secondary battery provided by the third aspect of the embodiment of the present invention has good cycle performance and discharge capacity.
  • Fig. 1 is a graph showing the results of charge and discharge cycles of a lithium ion secondary battery obtained in Examples 1 to 5 and Comparative Examples under a room temperature range of 3.5 to 4.9 V. detailed description
  • a first aspect of the embodiments of the present invention is directed to providing a non-aqueous organic high-voltage electrolyte additive which is oxidatively decomposed during charging of a high-voltage lithium ion secondary battery to promote the surface of the positive electrode material.
  • the formation of the protective film inhibits the oxidation of the positive electrode material to the non-aqueous organic electrolyte.
  • the second aspect of the present invention is directed to providing a non-aqueous organic electrolyte containing the non-aqueous organic electrolyte additive.
  • the voltage electrolyte can meet the high voltage lithium ion secondary battery of 4.5V and above.
  • a third aspect of the embodiment of the present invention is directed to a lithium ion secondary battery comprising the above nonaqueous organic high voltage electrolytic solution, which has good cycle performance and discharge capacity at a high voltage.
  • an embodiment of the present invention provides a non-aqueous organic high-voltage electrolyte additive, and the chemical structural formula of the non-aqueous organic high-voltage electrolyte additive is as shown in the formula (I):
  • R a , R b , R c and R d are an oxygen or an organic group, and the organic group includes an alkyl group, an alkene group, an alkyne group, an aromatic group And one of a haloalkyl group, a halogenated alkene group, a halogenated alkyne group and a halogenated aryl group; wherein i, j, q and t are 0 or 1; x, n, e and h are integers of 1 to 4, f is an integer from 0 to (2e+l), k is an integer from 0 to (2h+l), m is an integer from 0 to (2n+l), and y is an integer from 0 to (2x+l).
  • the R a , R b , R c and R d are oxygen, an alkyl group having 1 to 8 carbon atoms, an alkene group having 2 to 8 carbon atoms, and an alkyne having 2 to 8 carbon atoms.
  • the R a , R b , R c and R d are an alkyl group having 2 to 6 carbon atoms, an olefin group having 2 to 6 carbon atoms, an alkyne group having 2 to 6 carbon atoms, One of a halogenated alkyl group having 2 to 6 carbon atoms, a halogenated alkene group having 2 to 6 carbon atoms, and a halogenated alkyne group having 2 to 6 carbon atoms.
  • the non-aqueous organic high-voltage electrolyte additive has a chemical structural formula of one of the formulae Ia to If:
  • a non-aqueous organic high-voltage electrolyte additive provided by the first aspect of the present invention can be used in the preparation of a lithium ion secondary battery.
  • the positive electrode potential is continuously increased, and the high-voltage additive will be Promoting the formation of a protective film on the surface of the positive electrode material, the protective film covering the surface of the positive electrode material
  • the active site blocks the direct contact between the active site on the surface of the positive electrode material and the non-aqueous organic electrolyte, inhibits the oxidation of the positive electrode material to the non-aqueous organic electrolyte, and avoids the volume expansion of the lithium ion secondary battery and the decrease of the discharge capacity. Thereby, the cycle performance and discharge capacity of the lithium ion secondary battery at a high voltage are improved.
  • an embodiment of the present invention provides a non-aqueous organic high-voltage electrolyte, comprising: a lithium salt, a non-aqueous organic solvent, and a non-aqueous organic high-voltage electrolyte additive, and the non-aqueous organic high-voltage electrolyte additive
  • a non-aqueous organic high-voltage electrolyte comprising: a lithium salt, a non-aqueous organic solvent, and a non-aqueous organic high-voltage electrolyte additive, and the non-aqueous organic high-voltage electrolyte additive
  • R a , R b , R c and R d are an oxygen or an organic group, and the organic group includes an alkyl group, an alkene group, an alkyne group, an aryl group, a halogenated alkyl group, a halogenated alkene group, One of a haloalkynyl group and a halogenated aryl group; wherein i, j, q, and t are 0 or 1; x, n, e, and h are integers from 1 to 4, and f is 0 to (2e+l) The integer, k is an integer from 0 to (2h+l), m is an integer from 0 to (2n+l), and y is an integer from 0 to (2x+l).
  • the R a , R b , R c and R d are oxygen, an alkyl group having 1 to 8 carbon atoms, an alkene group having 2 to 8 carbon atoms, and an alkyne having 2 to 8 carbon atoms.
  • a hydrocarbon group an aromatic group having 6 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, a halogenated alkene group having 2 to 8 carbon atoms, a halogenated alkynyl group having 2 to 8 carbon atoms or A halogenated aromatic group having 6 to 8 carbon atoms.
  • the R a , R b , R c and R d are an alkyl group having 2 to 6 carbon atoms, an olefin group having 2 to 6 carbon atoms, an alkyne group having 2 to 6 carbon atoms, One of a halogenated alkyl group having 2 to 6 carbon atoms, a halogenated alkene group having 2 to 6 carbon atoms, and a halogenated alkyne group having 2 to 6 carbon atoms.
  • the non-aqueous organic high voltage electrolyte additive has a chemical structural formula of one of the formulas I a:
  • the lithium salt is selected from the group consisting of LiPF 6 , LiBF 4 , LiC10 4 , Li ( CF 3 S0 2 ) 2 N, LiBOB (lithium bis(oxalate) borate), LiDFOB (lithium difluorooxalate borate), and LiPF 4 C 2 0 4 (four One or more of lithium fluorooxalate phosphate.
  • the final concentration of the lithium salt in the non-aqueous organic electrolyte is from 0.1 to 1.5 mol/L.
  • the non-aqueous organic solvent is selected from the group consisting of carbonates and their derivatives, ethers, sulfones, nitriles, ionic liquids.
  • the non-aqueous organic solvent is Ethylene Carbonate (EC), Propylene Carbonate (PC), 1,2-vinylene carbonate (VC), dimercaptocarbonate ( DMC), diethyl carbonate (DEC), mercaptoethyl carbonate (EMC), fluoroethylene carbonate (FEC), ⁇ -butyrolactone, mercaptoethyl ether, tetrahydrofuran, sulfolane, acetonitrile or 1- ⁇ One or more of -3-ethylimidazolium bis(trifluoroindolyl) amide.
  • the non-aqueous organic high-voltage electrolyte additive accounts for 0.1 to 10% of the non-aqueous organic high-voltage electrolyte solution by mass fraction.
  • the non-aqueous organic high-voltage electrolyte additive accounts for 0.5 to 8% of the non-aqueous organic high-voltage electrolyte in terms of mass fraction.
  • the non-aqueous organic high-voltage electrolyte further includes a functional auxiliary agent, which is a high-temperature additive, a flame retardant additive or an overcharged force. Oral agent.
  • the high temperature additive is selected from one or more of 1,3 propionate, fluoroethylene carbonate (FEC) and lithium tetrafluoroborate (LiBF 4 ), and the flame retardant additive is selected from the group consisting of One or more of tridecyl phosphate, triethyl phosphate, triphenyl phosphate, tributyl phosphate and phosphazene, the overcharge additive being selected from one of biphenyl and cyclohexylbenzene or Several.
  • FEC fluoroethylene carbonate
  • LiBF 4 lithium tetrafluoroborate
  • the functional additive accounts for 0.1 to 10% of the non-aqueous organic high-voltage electrolyte in terms of mass fraction.
  • the non-aqueous organic high-voltage electrolyte provided by the second aspect of the present invention contains the above-mentioned non-aqueous organic high-voltage electrolyte additive, and thus can satisfy the high-voltage lithium ion secondary battery of 4.5 V or higher, and has excellent electrochemistry.
  • the stability can avoid the phenomenon of gas expansion of the lithium ion secondary battery under high voltage, and improve the cycle performance and discharge capacity of the lithium ion secondary battery under high voltage.
  • an embodiment of the present invention provides a lithium ion secondary battery, including:
  • the positive electrode comprising a positive active material capable of inserting or extracting lithium ions
  • the negative electrode comprising a negative active material capable of inserting or extracting lithium ions
  • the non-aqueous organic high-voltage electrolyte comprises: a lithium salt, a non-aqueous organic solvent and a non-aqueous organic high-voltage electrolyte additive, and the chemical structural formula of the non-aqueous organic high-voltage electrolyte additive is as shown in the formula (I): (I), wherein R a , R b , R c and R d are an oxygen or an organic group, and the organic group includes an alkyl group, an alkene group, an alkyne group, an aryl group, a halogenated alkyl group, a halogenated alkene group, One of a haloalkynyl group and a halogenated aryl group; wherein i, j, q, and t are 0 or 1; x, n, e, and h are integers from 1 to 4, and f is 0 to (2e+l) The integer, k is an integer from 0 to (2h
  • the positive electrode active material has a voltage platform of 4.5 V and 4.5 V or more when charged and discharged by lithium ion. More preferably, the positive active material is selected from one or more of LiCoP0 4 , LiNiP0 4 , and LiMn NiasC.
  • the lithium ion secondary battery provided in the third aspect of the embodiment of the present invention is not limited in form, and may be a square, cylindrical or soft pack battery.
  • the lithium ion secondary battery has good performance whether it is wound or laminated. Cycle performance and discharge capacity.
  • the lithium ion secondary battery is prepared by forming a positive electrode, a negative electrode, and a separator into a battery core, and injecting the non-aqueous organic high-voltage electrolyte to obtain a lithium ion secondary battery.
  • the preparation method of the lithium ion secondary battery is simple and feasible.
  • a method for preparing a non-aqueous organic high-voltage electrolyte additive comprises the following steps:
  • hexafluoroisopropanol was added to a flask containing anhydrous tetrahydrofuran (THF) (filled with two-fifths of the flask), sealed with a rubber stopper and transferred out of the glove box.
  • THF tetrahydrofuran
  • the flask was transferred to an ice bath, and under a nitrogen atmosphere, a stoichiometric ratio of n-butyllithium/n-hexane solution was taken up with a long needle, and a mixed solution containing hexafluoroisopropanol and THF was slowly added.
  • the whole reaction process was vigorously stirred and nitrogen-filled, and the reaction was stopped after about 12 hours.
  • the tetrachlorosilane solution (SiCl 4 ) was taken up with a long needle, and the mixed solution flask after the first step reaction was slowly added.
  • the molar ratio of hexafluoroisopropanol to tetrachlorosilane was 4:1.
  • the reaction was nitrogen-protected at room temperature. The reaction was stopped after about 24 hours. After the completion of the entire reaction process, the mixture was filtered through a sand funnel to remove reaction by-product residue (LiCl), and the filtrate was recovered.
  • the residual reaction solvent in the flask was removed by a rotary evaporator, including tetrahydrofuran and n-hexane, and the reaction product was concentrated.
  • the obtained concentrated product was transferred to a small flask, connected to a sublimator, and connected to circulating condensed water.
  • the target product crystals can be obtained under reduced pressure by heating in an oil bath.
  • the solid product was recovered, dried under vacuum at 110 ° C for more than 12 hours, and stored in a high-purity argon glove box for use, to obtain a non-aqueous organic high-voltage electrolyte additive such as la-silicic acid-tetra-hexafluoroisopropyl Base ester.
  • a preparation method of a non-aqueous organic high-voltage electrolyte comprising the following steps:
  • the non-aqueous organic solvent is a mixed solvent of ethylene carbonate (EC) and dinonyl carbonate (DMC) in a ratio of 1:2 by volume;
  • non-aqueous organic high-voltage electrolyte additive silicate-tetra-hexafluoroisopropyl ester as shown in Formula I a to the lithium salt solution, and stirring to obtain a non-aqueous organic electrolyte A, which is non-aqueous by mass fraction.
  • the organic high voltage electrolyte additive I a accounts for 0.5% of the non-aqueous organic electrolyte.
  • the positive electrode active material selected in the embodiment of the present invention is LiMn Nio.sO.
  • the dispersed positive electrode active material, the conductive agent carbon black powder material and the binder PVDF are mixed according to a mass ratio of 96:2:2, and then N-fluorenyl group is added.
  • the pyrrolidone (NMP) solution was prepared into an oil-based slurry, and finally the slurry was coated on both sides of the aluminum current collector to prepare a positive electrode sheet of a lithium ion secondary battery.
  • the negative active material artificial graphite powder, the binder carboxymethyl cellulose (CMC), the binder styrene butadiene rubber (SB) emulsion are mixed according to a mass ratio of 97:1.5:1.5, and then deionized water is added for preparation.
  • the water-based negative electrode slurry was finally coated on both sides of the copper current collector to form a lithium ion secondary battery negative electrode sheet, and the negative electrode sheet capacity was designed to be 1.2 times the capacity of the positive electrode sheet.
  • the non-aqueous organic high-voltage electrolyte ⁇ uses the non-aqueous organic high-voltage electrolytic solution A prepared in the foregoing embodiment of the present invention.
  • a composite separator composed of polypropylene and polyethylene is placed between the positive electrode tab and the negative electrode tab prepared above, such as a sandwich structure, and then rolled together into a 423450 square battery pole core, and finally a square-wound soft pack battery is completed. Finally, the non-aqueous organic high-voltage electrolyte A was injected to obtain a lithium ion secondary battery A.
  • the lithium ion secondary battery whether it is a square or a cylindrical or soft pack battery, whether it is a wound type or a laminated type, the same effect can be obtained by the above-described lithium ion secondary battery preparation method.
  • a method for preparing a non-aqueous organic high-voltage electrolyte additive comprises the following steps:
  • the tetrachlorosilane solution (SiCl 4 ) was taken up with a long needle, and slowly added to the mixed solution flask after the first step reaction, the molar ratio of high fluorine t-butanol to tetrachlorosilane was 4:1, and the reaction was nitrogen-protected at room temperature. The reaction was stopped after about 24 hours. After the completion of the entire reaction process, the mixture was filtered through a sand funnel to remove reaction by-product residue (LiCl), and the filtrate was recovered. The residual reaction solvent in the flask was removed by a rotary evaporator, including tetrahydrofuran and n-hexane, and the reaction product was concentrated.
  • the obtained concentrated product was transferred to a small flask, connected to a sublimator, and connected to circulating condensed water.
  • the target product crystals can be obtained under reduced pressure by heating in an oil bath.
  • the solid product is recovered, dried under vacuum at 110 ° C for more than 12 hours and stored in a high-purity argon glove box for use, to obtain a non-aqueous organic high-voltage electrolyte additive represented by lb of silicic acid-tetra-high-fluorine tert-butyl ester.
  • a preparation method of a non-aqueous organic high-voltage electrolyte comprising the following steps:
  • the lithium salt LiPF 6 is dissolved in a non-aqueous organic solvent to obtain a 1 mol/L lithium salt solution, stirred, and the stirring temperature is 28 ° C.
  • the non-aqueous organic solvent is ethylene carbonate (EC) and diterpene carbonate (DMC). a mixed solvent in which the volume ratio is 1:2;
  • non-aqueous organic high-voltage electrolyte additive silicate-tetra-fluoro-tert-butyl ester as shown in Formula 1b Adding a non-aqueous organic high-voltage electrolyte additive silicate-tetra-fluoro-tert-butyl ester as shown in Formula 1b to the lithium salt solution, and stirring to obtain a non-aqueous organic electrolyte B, which is non-aqueous organic by mass fraction.
  • the high voltage electrolyte additive lb accounts for 1% of the non-aqueous organic electrolyte additive.
  • the positive active material LiMn Nio.sO ⁇ conductive agent carbon black powder material and the binder PVDF powder material are further mixed according to a mass ratio of 96:2:2, and then N-mercaptopyrrolidone (NMP) solution is added to prepare an oil-based slurry. Finally, the slurry was coated on both sides of the aluminum current collector to form a positive electrode sheet of a lithium ion secondary battery.
  • NMP N-mercaptopyrrolidone
  • the preparation method of the non-aqueous organic high-voltage electrolyte additive of the present embodiment is the same as that of the second embodiment; the tetrachlorosilane in the second embodiment is replaced by n-hexyltrichloride, and the non-aqueous organic high represented by I c is obtained.
  • the voltage electrolyte additive is n-hexyl-tri-perfluoro-tert-butoxysilane, wherein the molar ratio of high fluorine tert-butanol to n-hexyltrichloride is 3:1,
  • a preparation method of a non-aqueous organic high-voltage electrolyte comprising the following steps:
  • the lithium salt LiDFOB is dissolved in a non-aqueous organic solvent to obtain a 1 mol/L lithium salt solution, stirred, and the stirring temperature is 20 ° C.
  • the non-aqueous organic solvent is ethylene carbonate (EC), propylene carbonate (PC) and cesium carbonate.
  • EC ethylene carbonate
  • PC propylene carbonate
  • EMC ethyl ester
  • non-aqueous organic high-voltage electrolyte additive n-hexyl-tri-fluoro-tert-butoxysilane as shown in Formula Ic Adding non-aqueous organic high-voltage electrolyte additive n-hexyl-tri-fluoro-tert-butoxysilane as shown in Formula Ic to the lithium salt solution, and stirring, to obtain a non-aqueous organic electrolyte C, by mass fraction,
  • the non-aqueous organic high-pressure electrolyte additive I c accounts for 10% of the non-aqueous organic electrolyte.
  • the preparation method of the non-aqueous organic high-voltage electrolyte additive of the present embodiment is the same as that of the second embodiment; the silicon tetrachloride in the second embodiment is replaced by the two-ply phenyl phenyl dichloride to obtain the I d
  • a preparation method of a non-aqueous organic high-voltage electrolyte comprising the following steps:
  • the lithium salt LiPF 6 and LiDFOB are dissolved in a non-aqueous organic solvent to obtain a lithium salt solution of 1 mol/L, the molar ratio of LiPF 6 and LiDFOB is 4:1, stirring, stirring temperature is 20 ° C, and the non-aqueous organic solvent is carbonic acid.
  • a non-aqueous organic high-voltage electrolyte additive as shown in Formula Id is added to the lithium salt solution, and stirred to obtain a non-aqueous organic electrolyte D.
  • the non-aqueous organic high-pressure electrolyte additive I d accounts for non-aqueous 0.1% of the organic electrolyte.
  • the preparation method of the non-aqueous organic high-voltage electrolyte additive of the present embodiment is the same as that of the second embodiment; the silicon tetrachloride in the second embodiment is replaced by triethyl silicon chloride to obtain the non-aqueous organic compound represented by I e
  • the high voltage electrolyte additive is high fluorine tert-butoxy-triethylsilane, wherein the molar ratio of high fluorine tert-butanol to triethylsilyl chloride is 1:1.
  • a preparation method of a non-aqueous organic high-voltage electrolyte comprising the following steps:
  • the lithium salt 0.8 M LiPF 6 and 0.2 M LiBOB were dissolved in a non-aqueous organic solvent to obtain a 1 mol/L lithium salt solution, and the molar ratio of LiPF 6 to LiBOB was 4:1, followed by stirring, and the stirring temperature was 20 ° C.
  • the non-aqueous organic solvent is a mixed solvent obtained by mixing ethylene carbonate (EC ) and dinonyl carbonate (DMC) in a ratio of 1:2 by volume;
  • a non-aqueous organic high-voltage electrolyte additive as shown in Formula Ie is added to the lithium salt solution, and stirred to obtain a non-aqueous organic electrolyte E. According to the mass fraction, the non-aqueous organic high-pressure electrolyte additive I e accounts for non-aqueous 3% of the organic electrolyte.
  • the preparation method of the non-aqueous organic high-voltage electrolyte additive of the present embodiment is the same as that of the second embodiment; the silicon tetrachloride in the second embodiment is replaced with heptadecafluorodecyltrichlorosilane to obtain the non-I f Water organic high voltage electrolyte additive tri-high fluorine tert-butoxy heptadecafluorodecyl silane, wherein, high fluorine tert-butanol and heptafluorosilane
  • a preparation method of a non-aqueous organic high-voltage electrolyte comprising the following steps:
  • the lithium salt 0.8 M LiPF 6 and 0.2 M LiBF 4 are dissolved in a non-aqueous organic solvent to obtain a 1 mol/L lithium salt solution, followed by stirring, the stirring temperature is 20 ° C, and the non-aqueous organic solvent is ethylene carbonate (EC). a mixed solvent of dicumyl carbonate (DMC) in a ratio of 1:3 by volume;
  • EC ethylene carbonate
  • DMC dicumyl carbonate
  • a non-aqueous organic high-voltage electrolyte additive as shown in Formula If is added to the lithium salt solution, and stirred to obtain a non-aqueous organic electrolyte F.
  • the non-aqueous organic high-pressure electrolyte additive I f accounts for non-water by mass fraction. 0.5% of the organic electrolyte.
  • the lithium salt 1 ⁇ 6 is dissolved in a non-aqueous organic solvent to obtain a 1 mol/L lithium salt solution, and stirred to obtain a non-aqueous organic electrolyte.
  • the non-aqueous organic solvent is ethylene carbonate (EC) and dinonyl carbonate. (DMC) A mixed solvent obtained by mixing in a ratio of 1:2 by volume.
  • the prepared non-aqueous organic electrolyte was injected into a square-wound lithium ion secondary soft pack battery (model number 423450-800 mAh) which has been prepared, and is referred to as a comparative example.
  • the lithium ion secondary battery prepared in the above examples and comparative examples was an experimental battery, and was subjected to a charge and discharge cycle at room temperature in a range of 3.5 to 4.9 V.
  • the test results are shown in Fig. 1.
  • the non-aqueous organic electrolyte solution provided by the first aspect of the embodiment of the present invention is added.
  • the performance of the additive lithium ion secondary battery was significantly improved. After 16 cycles, the capacity of the lithium ion secondary batteries of Examples 1 to 5 remained substantially unchanged, in contrast, the non-aqueous organic electrolysis was not added in the comparative example.
  • the lithium ion secondary battery of the liquid additive began to decrease in capacity after the fifth cycle, and after the fifteenth cycle, the lithium ion secondary battery in the comparative example was reduced from an initial capacity of 120 mAh/g to 80 mAh/g, and the capacity was decreased. It fell by 33.3%.
  • the non-aqueous organic electrolyte additive provided by the first aspect of the present invention improves the cycle performance of the lithium ion secondary battery at a high voltage, because the non-aqueous organic high-voltage electrolyte additive is secondary to lithium ions.
  • the battery is oxidized and decomposed during charging to promote the formation of a protective film on the surface of the positive electrode material.
  • the protective film covers the active site on the surface of the positive electrode material, blocks the direct contact between the active site on the surface of the positive electrode material and the non-aqueous organic electrolyte, and suppresses the positive electrode material.
  • the oxidation of the non-aqueous organic electrolyte avoids the volume expansion of the lithium ion secondary battery and the decrease in the discharge capacity, thereby improving the cycle performance of the lithium ion secondary battery at a high voltage.

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Abstract

L'invention porte sur un additif d'électrolyte haute tension, organique et non aqueux dont la structure chimique est représentée par la formule (I), dans laquelle Ra, Rb, Rc et Rd sont de l'oxygène ou un groupe organique, et le groupe organique comprend l'un sélectionné parmi l'alkyle, l'alkylène, l'alcyne, l'aryle, l'alkyle halogéné, l'alkylène halogéné, l'alcyne halogéné et l'aryle halogéné; i, j, q et t sont 0 ou 1; x, n, e et h sont des nombres entiers entre 1 et 4, f est un nombre entier entre 0 et (2e+1), k est un nombre entier entre 0 et (2h+1), m est un nombre entier entre 0 et (2n+1), et y est un nombre entier entre 0 et (2x+1). L'additif d'électrolyte haute tension, organique et non aqueux est oxydé et décomposé dans le processus de charge d'une batterie secondaire au lithium-ion haute tension, ainsi la formation d'un film de protection sur la surface d'un matériau d'anode est promue ultérieurement, afin que le fonctionnement du cycle et que la capacité de décharge de la batterie secondaire au lithium-ion sous la haute tension puissent être améliorés.
PCT/CN2014/078010 2013-09-05 2014-05-21 Additif d'électrolyte haute tension organique non aqueux, électrolyte haute tension organique non aqueux et batterie secondaire au lithium-ion WO2015032215A1 (fr)

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KR102112207B1 (ko) * 2017-01-26 2020-05-19 주식회사 엘지화학 리튬 이차전지용 비수전해액 및 이를 포함하는 리튬 이차전지
WO2018139808A1 (fr) * 2017-01-26 2018-08-02 주식회사 엘지화학 Électrolyte non aqueux pour accumulateur au lithium et accumulateur au lithium le comprenant
CN110994018B (zh) * 2019-12-20 2021-04-06 宁德新能源科技有限公司 一种电解液及电化学装置
CN113161619B (zh) * 2021-04-29 2023-04-11 厦门大学 一种弱极性体系电解液及其应用
CN114583276B (zh) * 2022-03-10 2024-04-02 东莞凯德新能源有限公司 一种高浸润性电解液及其制备方法

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