WO2022082759A1 - Sulphate compound and non-aqueous electrolyte and power storage device containing same - Google Patents

Sulphate compound and non-aqueous electrolyte and power storage device containing same Download PDF

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Publication number
WO2022082759A1
WO2022082759A1 PCT/CN2020/123361 CN2020123361W WO2022082759A1 WO 2022082759 A1 WO2022082759 A1 WO 2022082759A1 CN 2020123361 W CN2020123361 W CN 2020123361W WO 2022082759 A1 WO2022082759 A1 WO 2022082759A1
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Prior art keywords
carbonate
aqueous electrolyte
lithium salt
combinations
compound
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PCT/CN2020/123361
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French (fr)
Chinese (zh)
Inventor
王仁和
余乐
赵卫军
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远景动力技术(江苏)有限公司
远景睿泰动力技术(上海)有限公司
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Priority to CN202080108127.9A priority Critical patent/CN116648804A/en
Priority to PCT/CN2020/123361 priority patent/WO2022082759A1/en
Publication of WO2022082759A1 publication Critical patent/WO2022082759A1/en

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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
    • H01M10/052—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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the technical field of batteries, in particular to a sulfate compound, a non-aqueous electrolyte containing the same, and a power storage device.
  • the electrolyte contains lithium salts, non-aqueous solvents and additives, and a small amount of additives can specifically solve the technical problems such as short cycle life and safety hazards that are common in current lithium-ion batteries.
  • VC ethylene carbonate
  • EC ethylene carbonate
  • PC 1,3-propanesulfonic acid
  • DEC diethyl carbonate
  • CN201847750A discloses a flame retardant electrolyte for a rechargeable lithium battery, comprising a lithium salt, a linear carbonate-based solvent, at least one ammonium cation, a phosphoric acid-based solvent, and an additive comprising oxalate borate, with improved thermal stability , flame retardancy, and electrochemical properties such as high rate and cycle life performance.
  • CN107293784A discloses an electrolyte and lithium ion battery, including lithium salt, organic solvent and additives, wherein the additives include silane phosphate compound and/or silane borate compound, fluorocarbon surfactant and anti-overcharge additive, lithium ion
  • the battery has high temperature storage performance, high temperature cycle performance, overcharge performance and rate performance.
  • CN105830271A discloses a phosphonoformic acid compound, a non-aqueous electrolyte solution containing the compound, and a power storage device.
  • the non-aqueous electrolyte solution has the functions of maintaining high-load charge-discharge cycles at high temperatures, suppressing the decrease in thermal stability of negative electrodes, and improving power storage.
  • Device safety features discloses a trifluoromethylbenzene compound, a non-aqueous electrolyte solution and a power storage device containing the compound, and the non-aqueous electrolyte solution can improve electrochemical properties in a temperature range.
  • the present invention provides compounds of formula (I)
  • Each R is independently selected from halogen, halogenated C 1-10 alkyl, halogenated C 3-10 cycloalkyl;
  • n is an integer from 1 to 3;
  • n 1 or 2;
  • M is a counter cation.
  • the counter cation is a metal cation or a quaternary amine group.
  • the compound is selected from
  • M m+ is a metal cation or a quaternary amine group as defined above
  • n is an integer of 1-3.
  • the compound is selected from
  • the present invention provides an additive for a non-aqueous electrolyte solution comprising the compound represented by the formula (I) of the present invention.
  • the present invention provides a non-aqueous electrolyte solution comprising the compound represented by the formula (I) of the present invention and an additive for non-aqueous electrolyte solutions comprising the same.
  • the present invention provides an electrical storage device comprising the compound represented by the formula (I) of the present invention or the non-aqueous electrolyte solution of the present invention.
  • the present invention provides the use of the compound represented by formula (I) as a non-aqueous electrolyte additive.
  • the present invention provides an electric device including the power storage device of the present invention.
  • C 1-10 alkyl represents an alkyl group having 1-10 carbon atoms, covering 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and any combination of any two values Subranges such as 1-8, 2-7, 3-6.
  • C 3-10 cycloalkyl represents an alkyl group having 3-10 carbon atoms, covering 3, 4, 5, 6, 7, 8, 9, 10, and any subrange consisting of any two values, For example 3-8, 4-7, 5-6.
  • the terms "optional” or “optionally” mean that the subsequently described event or circumstance may or may not occur, and that the description includes the occurrence and non-occurrence of said event or circumstance.
  • the terms “one or more” or “at least one” refer to one, two, three, four, five, six, seven, eight, nine or more.
  • the terms “combinations thereof” and “mixtures thereof” refer to multi-component mixtures of the elements in question, such as two, three, four and up to the maximum possible multi-component mixtures.
  • halo or "halogen” or “halo” are to be understood to mean fluorine (F), chlorine (Cl), bromine (Br) or iodine (I) atoms, preferably fluorine, chlorine, bromine atoms.
  • alkyl refers to a straight or branched chain saturated aliphatic hydrocarbon group consisting of carbon and hydrogen atoms attached to the rest of the molecule by a single bond.
  • Alkyl may have 1-10 carbon atoms, i.e. "C 1 -C 10 alkyl", eg C 1 -C 4 alkyl, C 1 -C 3 alkyl, C 1 -C 2 alkyl, C 3 alkyl, C 4 alkyl, C 3 -C 6 alkyl.
  • alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2- Methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-di Methylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl, or their isomers body.
  • Subunit refers to a group obtained by removing a hydrogen atom from a carbon atom containing a free valence electron and having two attachment sites to the rest of the molecule.
  • alkylene or “alkylidene” refers to a saturated linear or branched divalent hydrocarbon radical.
  • alkylene examples include, but are not limited to, such as methylene ( -CH2- ), ethylene ( -C2H4- ), propylene ( -C3H6- ), butylene ( - C 4 H 8 -), pentylene (-C 5 H 10 -), hexylene (-C 6 H 12 -), 1-methylethylene (-CH(CH 3 )CH 2 -), 2 - methyl ethylene (-CH 2 CH(CH 3 )-), methyl propylene or ethyl propylene and the like.
  • cycloalkyl refers to a saturated non-aromatic monocyclic or polycyclic (such as bicyclic) hydrocarbon ring (eg, monocyclic, such as cyclopropyl, cyclobutyl, etc.) , cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl; or bicyclic, including spiro, fused or bridged systems (such as bicyclo[1.1.1]pentyl, bicyclo[2.2.1] heptyl, bicyclo[3.2.1]octyl or bicyclo[5.2.0]nonyl, decalinyl, etc.).
  • C 3-10 cycloalkyl refers to a group having 3-10 ring carbon atoms (such as 3, 4, 5, 6, 7, 8, 9 or 10) cycloalkyl.
  • the compounds of the present invention may be in the form of anions, forming salts of the compounds of the present invention with cations.
  • the cations include, but are not limited to, metal cations, ammonium ions, quaternary amine groups.
  • counterion refers to a species having an opposite charge to the compounds of the present application, which can be a charged ion, such as a metal cation or ammonium ion, or a charged group, such as a quaternary amine group.
  • chain ester refers to ester compounds having a straight chain structure, examples of which include but are not limited to methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, Methyl butyrate, ethyl butyrate, methyl ethyl carbonate, methyl propyl carbonate, dimethyl carbonate, diethyl carbonate, ethyl propyl carbonate, dipropyl carbonate and the like.
  • cyclic ester refers to an ester compound having a cyclic structure, examples of which include, but are not limited to, ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 4 -Fluoro-1,3-dioxolane-2-one, trans or cis-4,5-difluoro-1,3-dioxolane-2-one, fluoroethylene carbonate , vinylene carbonate, vinyl ethylene carbonate, propylene carbonate, ethylene carbonate, butylene carbonate.
  • electrolytic capacitor is a medium used by chemical batteries, electrolytic capacitors, etc., which can provide ions for the normal operation of chemical batteries, electrolytic capacitors, and the like.
  • non-aqueous electrolytic solution refers to an electrolytic solution using a non-aqueous solvent.
  • electrolyte salt refers to an ionic salt that is at least partially soluble in the solvent of the electrolyte composition and at least partially dissociated into ions in the solvent of the electrolyte composition to form a conductive electrolyte composition.
  • Lithium salts are preferably used as electrolyte salts.
  • anode refers to the electrode of an electrochemical cell in which oxidation occurs.
  • galvanic cells such as batteries
  • the anode is the negatively charged electrode.
  • secondary batteries ie, rechargeable batteries
  • the anode is the electrode in which oxidation occurs during discharge and reduction occurs during charge.
  • cathode refers to the electrode of an electrochemical cell where reduction occurs.
  • galvanic cells such as batteries
  • the cathode is the positively charged electrode.
  • secondary batteries ie, rechargeable batteries
  • the cathode is the electrode in which reduction occurs during discharge and oxidation occurs during charge.
  • lithium ion battery refers to a type of rechargeable battery in which lithium ions move from anode to cathode during discharge and from cathode to anode during charge.
  • second battery refers to an electrochemical cell in which the electrochemical reaction is reversible, and also refers to a cell that can be recharged or rechargeable for use by repeated charging and discharging over its useful life.
  • the term "formation” refers to the process of charging and discharging the battery with a small current after the battery is obtained during the battery preparation process.
  • the chemical formation treatment is beneficial to stabilize the electrical properties of the battery.
  • aging refers to the operation of standing at a certain temperature for a period of time after the battery is assembled and filled with liquid and undergoes the first chemical conversion treatment during the battery preparation process.
  • the aging treatment of the battery helps to reorganize the SEI structure to form a loose and porous membrane, which makes the battery performance more stable.
  • SEI or "SEI film” refers to the reaction between the electrode material and the electrolyte at the solid-liquid interface during the first charge and discharge of the battery to form a passivation layer covering the surface of the electrode material.
  • electric vehicle refers to a vehicle powered by electricity, and examples of an electric vehicle include, but are not limited to, an electric vehicle (EV), a hybrid electric vehicle (HEV), a plug-in hybrid electric vehicle (PHEV), and the like.
  • EV electric vehicle
  • HEV hybrid electric vehicle
  • PHEV plug-in hybrid electric vehicle
  • electric two-wheeled vehicle refers to a two-wheeled vehicle powered by electricity
  • examples of an electric two-wheeled vehicle include, but are not limited to, E-bikes and E-scooters.
  • the present invention provides compounds of formula (I):
  • R is independently selected from halogen, halogenated C 1-10 alkyl, halogenated C 3-10 cycloalkyl; m is an integer of 1-3; n is 1 or 2; M is a counter cation .
  • each R is independently selected from halogen. In a more preferred embodiment, each R is independently selected from fluoro, chloro or bromo. In a particularly preferred embodiment, R is selected from fluoro.
  • m corresponds to an integer of 1-3.
  • the counter cation M m+ is a lithium ion (Li + )
  • m corresponds to 1 and R is a substituent as defined above.
  • the counter cation M m+ is calcium ion (Ca 2+ )
  • m corresponds to 2.
  • the counter cation M m+ is a quaternary amine group, m corresponds to 1.
  • the compound is selected from
  • M m+ is a metal cation or a quaternary amine group as described above, and m is an integer of 1-3.
  • the compound is selected from
  • TBA + is represented as the quaternary amine group tetrabutylamine, i.e. therefore can also be expressed as
  • Counter cations in the compounds herein include, but are not limited to, metal cations, ammonium ions, quaternary amine groups, and the like.
  • the counter cation is a metal cation or a quaternary amine group.
  • the counter cation is a metal cation.
  • Metal cations may include alkali metal cations, alkaline earth metal cations, transition metal cations, and the like.
  • the metal cation contained in the compound of formula (I) is an alkali metal cation or an alkaline earth metal cation.
  • the metal cation contained in the compound of formula (I) is selected from the group consisting of lithium ion, sodium ion, potassium ion, calcium ion, magnesium ion and combinations thereof.
  • the metal cation contained in the compound of formula (I) is a lithium ion.
  • the counter cation is a quaternary amine group.
  • the quaternary amine group contained in the compound of formula (I) is selected from the group consisting of tetramethylamine, tetraethylamine, tetrapropylamine, and tetrabutylamine.
  • the quaternary amine group contained in the compound of formula (I) is tetrabutylamine.
  • the present invention provides an additive for a non-aqueous electrolyte solution, characterized by containing the compound represented by the above formula (I).
  • the present invention provides a non-aqueous electrolyte solution comprising the compound represented by the formula (I) of the present invention.
  • the non-aqueous electrolyte solution of the present invention may contain one or more compounds represented by the formula (I) of the present invention, that is, one compound represented by the formula (I) may be used, or more than one compound may be used A mixture or combination of compounds of formula (I).
  • the compound represented by the formula (I) can be reduced to form a film at the negative electrode, passivate the electrode surface, allow lithium ions to freely enter and exit the electrode, and the solvent molecules cannot pass through, thereby preventing the solvent molecules from co-inserting into the counter electrode.
  • the destruction of the non-aqueous electrolyte improves the cycle efficiency and reversible capacity of the battery containing the non-aqueous electrolyte.
  • the compound of formula (I) has a high reduction voltage, can be preferentially reduced to a film at the negative electrode, improves the high temperature performance of the battery containing the non-aqueous electrolyte, and improves the cycle stability of the battery.
  • the compound of formula (I) is present in the non-aqueous electrolyte in an amount of about 0.1 to 10% by weight, based on the total weight of the non-aqueous electrolyte. In a preferred embodiment, the compound of formula (I) is present in the non-aqueous electrolyte in an amount of about 0.2 to 7% by weight, based on the total weight of the non-aqueous electrolyte. In a more preferred embodiment, the content of the compound of formula (I) in the non-aqueous electrolyte is about 1% by weight based on the total weight of the non-aqueous electrolyte.
  • the non-aqueous electrolyte may contain a non-aqueous solvent.
  • the non-aqueous solvent used is selected from the group consisting of cyclic esters, chain esters and combinations thereof.
  • Cyclic esters include, but are not limited to, cyclic carbonates, lactones.
  • the non-aqueous solvent used is a cyclic carbonate.
  • cyclic carbonates include, but are not limited to, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), fluoroethylene carbonate (FEC), vinylene carbonate (VC), carbonic acid 1,2-Butene ester, 2,3-butene carbonate, vinylene carbonate, vinylethylene carbonate (VEC), trans or cis 4,5-difluoro-1,3-dioxa Cyclopentan-2-one (both collectively referred to as "DFEC"), 4-ethynyl-1,3-dioxolane-2-one (EEC), propylene carbonate, ethylene carbonate, butylene carbonate Ester, etc.
  • DFEC 4-ethynyl-1,3-dioxolane-2-one
  • EEC 4-ethynyl-1,3-dioxolane-2-one
  • propylene carbonate ethylene carbonate
  • butylene carbonate Ester etc.
  • the non-aqueous solvent used is selected from the group consisting of ethylene carbonate, propylene carbonate, 1,2-butene carbonate, propylene carbonate and combinations thereof.
  • the non-aqueous solvent used is ethylene carbonate.
  • the non-aqueous solvent used in another preferred embodiment, is a cyclic carbonate containing unsaturated bonds such as carbon-carbon double bonds or carbon-carbon triple bonds.
  • the non-aqueous solvent used in the non-aqueous electrolyte of the present invention, is selected from vinylene carbonate, vinylethylene carbonate, 4-ethynyl-1,3-dioxa Cyclopentan-2-ones and combinations thereof.
  • the non-aqueous solvent used is vinylene carbonate.
  • the non-aqueous electrolyte used in yet another preferred embodiment, is a cyclic carbonate containing a fluorine atom. In a more preferred embodiment, in the non-aqueous electrolyte of the present invention, the non-aqueous electrolyte used is selected from fluoroethylene carbonate, trans or cis 4,5-difluoro-1,3-di Oxolan-2-ones and combinations thereof.
  • a suitable content of the unsaturated bond-containing cyclic carbonate nonaqueous solvent helps to improve the low temperature and high temperature characteristics of a battery containing the nonaqueous electrolyte solution, and to improve the load characteristics after high-temperature charge storage. Excessive content of cyclic carbonate containing unsaturated bonds will increase the viscosity of the electrolyte, reduce the charge transfer efficiency in the battery, and reduce the efficiency of the battery. Too low content of cyclic carbonate containing unsaturated bonds will reduce the conductivity of the battery and reduce the efficiency of the battery.
  • An appropriate content of the nonaqueous solvent of the fluorine atom-containing cyclic carbonate helps to improve the low temperature and high temperature characteristics of a battery containing the nonaqueous electrolyte solution, and to improve the load characteristics after high-temperature charge storage.
  • An excessively high content of cyclic carbonate containing fluorine atoms will increase the viscosity of the electrolyte, reduce the charge transfer efficiency in the battery, and reduce the efficiency of the battery. Too low cyclic carbonate content of fluorine atoms will reduce the conductivity of the battery and reduce the efficiency of the battery.
  • the non-aqueous solvent is a single cyclic carbonate solvent.
  • the non-aqueous solvent is a mixed solvent.
  • the non-aqueous solvent contains two or more cyclic carbonate solvents.
  • the electrochemical performance at high temperature of the battery containing this non-aqueous electrolyte solution can be further improved.
  • the non-aqueous solvent contains three or more cyclic carbonate solvents.
  • Combinations of mixed cyclic carbonates include, but are not limited to, cyclic carbonates and cyclic carbonates containing unsaturated bonds, cyclic carbonates and cyclic carbonates containing fluorine atoms, and cyclic carbonates containing unsaturated bonds and cyclic carbonates.
  • the selection of the fluorine atom-containing cyclic carbonate is as described above.
  • Chain esters include, but are not limited to, chain carbonates, chain sulfonates.
  • the non-aqueous solvent used is a chain carbonate.
  • chain carbonates include, but are not limited to, ethyl methyl carbonate (EMC), methyl propyl carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl propyl carbonate, dicarbonate Propyl ester etc.
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • ethyl propyl carbonate dicarbonate Propyl ester etc.
  • the non-aqueous electrolyte used is preferably selected from ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, ethyl propyl carbonate, carbonic acid Dipropyl esters and combinations thereof.
  • the non-aqueous electrolyte used is preferably selected from ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate and combinations thereof.
  • a suitable chain carbonate content helps to obtain good battery performance. Excessive chain carbonate content will reduce the conductivity of the battery and reduce the efficiency of the battery. Too low chain carbonate content will increase the viscosity of the electrolyte, reduce the charge transfer efficiency in the battery, and reduce the efficiency of the battery.
  • the non-aqueous solvent is a single chain carbonate solvent.
  • the non-aqueous solvent is a mixed solvent.
  • the non-aqueous solvent contains two or more kinds of chain carbonate solvents.
  • the electrochemical performance at high temperature of the battery containing this non-aqueous electrolyte solution can be further improved.
  • the non-aqueous solvent contains three or more kinds of chain carbonate solvents.
  • the lactone as the non-aqueous solvent is selected from the group consisting of gamma-butyrolactone, gamma-valerolactone, and alpha-angelica lactone, and combinations thereof.
  • the ether as the non-aqueous solvent is selected from cyclic rings such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 1,3-dioxane and 1,4-dioxane Ethers, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, and combinations thereof.
  • the amide as the non-aqueous solvent is dimethylformamide.
  • the phosphate ester as the non-aqueous solvent is selected from the group consisting of trimethyl phosphate, tributyl phosphate, trioctyl phosphate, and combinations thereof.
  • the nitrile as the non-aqueous solvent is selected from the group consisting of acetonitrile, propionitrile, succinonitrile, glutaronitrile or adiponitrile, pimeliconitrile, and combinations thereof.
  • non-aqueous solvents may be used in combination.
  • the non-aqueous solvent used is a combination of cyclic carbonate and chain carbonate, wherein the selection of cyclic carbonate and chain carbonate are as above described in the text.
  • a combination can improve low-temperature and high-temperature cycle characteristics and load characteristics after high-temperature charge storage for batteries containing the non-aqueous electrolyte.
  • a suitable mass ratio of cyclic carbonate to chain carbonate helps to obtain good battery performance.
  • the mass ratio of the cyclic carbonate solvent to the chain carbonate solvent is 3:7.
  • An excessively high mass ratio of the cyclic carbonate solvent to the chain carbonate solvent will increase the viscosity of the electrolyte, reduce the charge transfer efficiency in the battery containing the non-aqueous electrolyte, and reduce the efficiency of the battery.
  • An excessively low mass ratio of the cyclic carbonate solvent to the chain carbonate solvent will reduce the electrical conductivity of the battery and reduce the efficiency of the battery.
  • Electrolyte salt refers to an ionic salt that is at least partially soluble in the solvent of the electrolyte composition and at least partially dissociated into ions in the solvent of the electrolyte composition to form a conductive electrolyte composition.
  • a lithium salt or an onium salt is used as the electrolyte salt.
  • a lithium salt is used as the electrolyte salt.
  • Lithium salts refer to salts having lithium as a cation.
  • the lithium ions of the electrolyte lithium salt play the role of transporting ions between the positive and negative electrodes of the battery, which is crucial to the performance of the battery.
  • the type, purity, and content of the electrolyte lithium salt in the battery, as well as the combination of the lithium salt and other substances can affect the capacity, charge-discharge performance, lifespan, and safety of the battery to varying degrees.
  • the used lithium salt includes a first lithium salt and a second lithium salt, wherein the first lithium salt is an inorganic lithium salt, and the second lithium salt is a lithium salt containing an organic group.
  • the first lithium salt used is selected from LiPF 6 , LiBF 4 , LiBCl 4 , LiAsF 6 , LiClO 4 , LiAlO 2 , LiCl, LiI, LiSbF 6 and the like. combination.
  • the first lithium salt used is selected from LiPF 6 , LiBF 4 and combinations thereof.
  • the first lithium salt usually has good ionization ability and is easy to ionize in the solvent, so as to obtain a large amount of free lithium ions. Therefore, a suitable first lithium salt helps to provide a sufficient content of lithium ions for the non-aqueous electrolyte, improving the Conductivity of non-aqueous electrolytes.
  • the content of the first lithium salt is about 8-16% by weight. In a preferred embodiment, the content of the first lithium salt is about 10-14% by weight. In a more preferred embodiment, the content of the first lithium salt is about 13-13.5% by weight.
  • Excessive content of the first lithium salt may increase the viscosity of the non-aqueous electrolyte, reduce the charge transfer efficiency in the battery including the non-aqueous electrolyte, and thereby reduce the efficiency of the battery.
  • Lithium salts containing boron oxalate complexes as anions include, but are not limited to, lithium bis-oxalate difluorophosphate (LiODFP), lithium difluorooxalate borate (LiODFB), lithium borate (LiBOB), and the like.
  • the second lithium salt used is selected from LiPO 2 F 2 , Li 2 PO 3 F, LiODFB, LiODFP, LiBOB, LiTFSI, LiFSI, and combinations thereof.
  • the second lithium salt used is selected from LiPO 2 F 2 , LiODFB, LiODFP, LiBOB, LiTFSI, LiFSI, and combinations thereof.
  • a suitable second lithium salt can also participate in electrode film formation while providing a small amount of lithium ions, which helps to improve the performance of the battery containing the non-aqueous electrolyte.
  • the second lithium salt is present in an amount of about 0.5-5% by weight, and in a preferred embodiment, the second lithium salt is present in an amount of about 1.5-4% by weight. In a more preferred embodiment, the second lithium salt is present in an amount of about 1.9-3% by weight.
  • an excessively low content of the second lithium salt cannot improve the performance of the battery containing the non-aqueous electrolyte.
  • a combination of the first lithium salt and the second lithium salt is used as the electrolyte lithium salt. Such a combination helps to improve the thermal stability of the negative electrode of the battery and improve the permeability of lithium ions.
  • a suitable total content of the first lithium salt and the second lithium salt helps the lithium salt to interact with other additives to achieve the effects of reducing impedance and suppressing gas generation, and is also conducive to improving electrode film formation.
  • the total content of the first lithium salt and the second lithium salt is about 10-20 wt %.
  • the total content of the first lithium salt and the second lithium salt is about 12-17.6 wt %.
  • the total content of the first lithium salt and the second lithium salt is about 15.4-16.3 wt %.
  • additives selected from the group consisting of linear carbonates, cyclic carbonates, cyclic sulfonates, or combinations thereof may be optionally included.
  • linear carbonates and cyclic carbonates are as described above, wherein linear carbonates and cyclic carbonates are selected from carbonates other than solvents.
  • cyclic sulfonates include, but are not limited to, 1,3-propane sultone (PS), vinyl sulfate (DTD), and the like.
  • the non-aqueous electrolyte of the present invention further comprises one or more additives selected from the group consisting of vinylene carbonate, fluoroethylene carbonate, dimethyl carbonate, 1,3- propane sultone, vinyl sulfate, propylene carbonate.
  • the content of the other additives is about 0-10% by weight. In a preferred embodiment, in the non-aqueous electrolyte of the present invention, the content of the other additives is about 3-6% by weight. In a more preferred embodiment, in the non-aqueous electrolyte of the present invention, the content of the other additives is about 4.5-6% by weight. Appropriate content of other additives is beneficial to improve the performance of the battery, such as the high temperature stability, low temperature stability and film formation stability of the battery.
  • adding vinyl sulfate to the non-aqueous electrolyte of the present invention can effectively improve the low-temperature performance of the battery containing the non-aqueous electrolyte, and is beneficial to high-temperature cycle performance and high-temperature storage performance.
  • the present invention provides an electrical storage device comprising the compound represented by the formula (I) of the present invention, or the non-aqueous electrolyte solution of the present invention.
  • the power storage device is a secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte in which an electrolyte salt is dissolved in a non-aqueous solvent.
  • components such as positive electrodes and negative electrodes other than the non-aqueous electrolyte solution of the present invention can be used without particular limitations.
  • the active material of the positive electrode may be a composite metal oxide composed of lithium and one or more selected from cobalt, manganese, and nickel.
  • the positive active material is a single component.
  • the positive electrode active material is a mixture of the above composite metal oxides.
  • the lithium composite metal oxide used in the present invention is selected from LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , LiCo 1-x Ni x O 2 (0.01 ⁇ x ⁇ 1), LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.65 Co 0.15 Mn 0.2 O 2 , LiNi 0.55 Co 0.15 Mn 0.3 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNi 0.55 Co 0.1 Mn 0.35 O 2 , LiNi 1/ 2 Mn 3/2 O 4 , LiCo 0.98 Mg 0.02 O 2 and combinations thereof.
  • the lithium composite metal oxide used in the present invention is selected from LiNi 0.65 Co 0.15 Mn 0.2 O 2 , LiNi 0.55 Co 0.15 Mn 0.3 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 or LiNi 0.55 Co 0.1 Mn 0.35 O 2 and combinations thereof.
  • a part of the lithium mixed metal oxide may be substituted with other elements.
  • part of cobalt, manganese, and nickel may be substituted with at least one element such as Sn, Mg, Fe, Ti, Al, Zr, Cr, V, Ga, Zn, Cu, Bi, Mo, and La, or Substitute a part of O with S or F, or cover compounds containing these other elements.
  • lithium composite metal oxides such as LiCoO 2 , LiMn 2 O 4 , and LiNiO 2 that can be used when the charge potential of the positive electrode is 4.3 V or more in terms of Li in a fully charged state are preferable. More preferably, it is a lithium composite metal oxide that can be used in a solid solution above 4.4V, such as LiCo 1-x M x O 2 (wherein M is selected from Sn, Mg, Fe, Ti, Al, Zr, Cr, V , at least one element of Ga, Zn, Cu, 0.001 ⁇ x ⁇ 0.05), LiNi 1/3 Mn 1/3 Co 1/3 O 2 , LiNi 0.65 Co 0.15 Mn 0.2 O 2 , LiNi 0.55 Co 0.15 Mn 0.3 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 or LiNi 0.55 Co 0.1 Mn 0.35 O 2 , LiNi 1/2 Mn 3/2 O 4 , Li 2 MnO 3 and LiMO 2 (M is Co, Ni, Mn,
  • the electrochemical characteristics of the electrode at particularly high temperatures are likely to be degraded due to its reaction with the electrolyte during charging, but in the secondary battery of the present invention These reductions in electrochemical properties can be suppressed.
  • the resistance of the battery tends to increase due to the elution of Mn ions from the positive electrode, and therefore the electrochemical properties of the electrode tend to decrease when used in a wide temperature range.
  • the use of the above-mentioned materials as the positive electrode material of the battery can suppress the reduction of these electrochemical properties.
  • the positive electrode can be prepared by the following exemplary method: combining the above-mentioned positive electrode active material with conductive agents such as acetylene black and carbon black, and copolymers of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene and butadiene (SBR), copolymer of acrylonitrile and butadiene (NBR), carboxymethyl cellulose (CMC), ethylene-propylene-diene terpolymer and other binders are mixed, and 1-methyl- After kneading a high boiling point solvent such as 2-pyrrolidone to form a positive electrode mixture, the positive electrode mixture is coated on an aluminum foil or a stainless steel strip of the current collector, dried, and press-molded at about 50-250 °C. Heat treatment is performed at a temperature of °C under vacuum for about 2 hours.
  • conductive agents such as acetylene black and carbon black
  • conductive agents such as acet
  • the active material of the negative electrode can be a carbon material that can intercalate or deintercalate lithium in lithium metal or lithium alloy, including but not limited to easily graphitizable carbon and difficult graphitizable carbon with a crystal plane distance of (002) plane of 0.37 nm or more. , graphite and the like whose crystal plane distance of the (002) plane is 0.34 nm or less.
  • the negative electrode active material may be a lithium titanate compound such as tin (elemental), tin compound, silicon (elemental), silicon compound, Li 4 Ti 5 O 12 , and combinations thereof.
  • the negative electrode active material used in the electricity storage device of the present invention is selected from silicon element, silicon compound, artificial graphite, natural graphite or silicon-oxygen composite artificial graphite. In a more preferred embodiment, the negative electrode active material used in the electricity storage device of the present invention is selected from artificial graphite, natural graphite or silicon-oxygen composite artificial graphite.
  • the negative electrode can be prepared by using the same conductive agent, binder, and high-boiling point solvent as those used for the production of the positive electrode described above, kneading to obtain a negative electrode mixture, and then applying the negative electrode mixture to the copper foil of the current collector, etc. After drying and press molding, heat treatment is performed under vacuum at a temperature of about 50-250°C for about 2 hours.
  • the secondary battery of the present invention can be prepared by the following exemplary methods:
  • the positive and negative electrode sheets and the human separator made of polyethylene are stacked in the manner of negative electrode, separator, positive electrode and separator, and the negative electrode is terminated to obtain a bare cell.
  • the bare cell is hot-pressed so that the polyvinylidene fluoride (PVDF) on the surface of the diaphragm bonds the pole pieces together.
  • PVDF polyvinylidene fluoride
  • the pre-packaged battery is placed in a vacuum furnace to be fully baked and dried, a certain amount of electrolyte is injected from the liquid injection port, and the liquid injection port is packaged in a vacuum environment to obtain a secondary battery.
  • the secondary battery of the present invention can be tested by the following method.
  • the prepared battery was placed on the jig, and the battery was charged to 4.3V at a first constant current at 25°C, and then discharged to 2.8V at a second constant current.
  • a third charge-discharge cycle is performed, wherein after charging to 4.3V at a third constant current, charging at a constant voltage of 4.3V until the current value reaches 0.05C current, and discharging to 2.8V at a fifth constant current .
  • a fourth charge-discharge cycle is performed, wherein after the sixth constant current is charged to 4.3V, the charge is performed at a constant voltage of 4.3V until the current value reaches 0.05C, and the seventh constant current is discharged to 2.8V.
  • the first to seventh constant currents can be 1C, 5C, 0.1C, 0.2C and so on. 1C represents the current value for discharging the battery at the reference capacity in 1 hour, 5C represents 5 times the above-mentioned current value, and 0.1C and 0.2C represent 1/10 and 1/5 of the above-mentioned current value, respectively.
  • Cycle charge and discharge with a current of 1C within the specified potential range record the capacity of each cycle, and end the test when the battery capacity reaches 80% of the capacity of the first cycle.
  • the battery is discharged to 50% SOC (state of charge, reflecting the remaining capacity of the battery) at a current of 1C, the current is increased to 4C, and maintained for 30s, and the difference between the updated stable voltage and the original platform voltage is detected. , the ratio of its value to the 3C current value is the DC resistance of the battery.
  • the DCR growth rate was obtained by comparing the DCR at the end of the cycle with the DCR at the beginning of the cycle.
  • the secondary battery was fixed with a string, it was completely immersed in water at 25°C, the weight difference before and after the immersion was recorded, and the volume difference was converted according to the density of water at 25°C.
  • the charged secondary battery was placed in an environment of 60° C. for 60 days, and the reversible capacity after 60 days was measured to obtain the capacity recovery rate compared to that before 60 days.
  • the secondary battery of the present invention has an initial direct current resistance (DCR) of about 1.10-1.30 mohm.
  • the initial direct current resistance (DCR) of the secondary battery of the present invention is preferably about 1.12-1.27 mohm.
  • DCR direct current resistance
  • the initial direct current resistance (DCR) of the secondary battery of the present invention is preferably about 1.12-1.27 mohm.
  • DCR direct current resistance
  • the initial direct current resistance (DCR) of the secondary battery of the present invention is preferably about 1.12-1.27 mohm.
  • DCR initial direct current resistance
  • the initial direct current resistance (DCR) of the secondary battery of the present invention is preferably about 1.12-1.27 mohm.
  • the DC resistance growth rate of the secondary battery of the present invention is about 15% to about 35% after the above-mentioned four charge-discharge cycles. In a preferred embodiment, after the above-mentioned four charge-discharge cycles, the DC resistance growth rate of the secondary battery of the present invention is about 20% to about 32%. For example about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29%, about 30%, about 31%, about 32%.
  • the secondary battery of the present invention produces a volume growth rate of about 5% to about 20%. In a preferred embodiment, after the above-mentioned four charge-discharge cycles, the secondary battery of the present invention produces a volume growth rate of about 8% to about 14%. For example, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%.
  • the DC resistance growth rate of the secondary battery is about 5% to about 75%. In a preferred embodiment, after the secondary battery of the present invention is placed in an environment of 60° C. for 60 days, the DC resistance growth rate of the secondary battery is about 5% to about 70%. For example, about 5%, about 10%, about 15%.
  • the secondary battery of the present invention has a capacity recovery rate of about 90% to about 98% after being placed in a 60° C. environment for 60 days. In a preferred embodiment, after the secondary battery of the present invention is placed in an environment of 60° C. for 60 days, the capacity recovery rate of the secondary battery is about 94% to about 97%.
  • the growth rate of the volume of gas generated by the secondary battery is about 1% to about 50%.
  • the volume growth rate of the gas generated by the secondary battery is about 1% to about 50%. For example, about 1%, about 2%, about 3%, about 50%.
  • the secondary battery of the present invention has a DC resistance growth rate of about 7% after the above-mentioned four charge-discharge cycles are placed in an environment of -30°C.
  • the secondary battery of the present invention has a number of turns of about 1750-2800 when it reaches 80% SOH. In a preferred embodiment, the secondary battery of the present invention has a number of turns of about 1894-2781 when it reaches 80% SOH.
  • the present invention provides an electric device, characterized in that the electric device includes the power storage device of the present invention.
  • the electric device is selected from the group consisting of electric vehicles, electric two-wheelers, and power storage systems.
  • the electric device is an electric vehicle, which is preferably selected from an electric vehicle (EV), a hybrid electric vehicle (HEV), and a plug-in hybrid electric vehicle (PHEV).
  • EV electric vehicle
  • HEV hybrid electric vehicle
  • PHEV plug-in hybrid electric vehicle
  • the present invention also relates to the use of a compound of formula (I) as an additive for non-aqueous electrolytes.
  • the compound of formula (I) as the additive of the non-aqueous solvent electrolyte can improve the negative electrode film formation of the secondary battery of the present invention, so that the cycle stability of the secondary battery of the present invention can be improved. After the secondary battery is charged and discharged for many times, the DC resistance of the secondary battery and the growth rate of the generated gas volume are relatively low.
  • the high temperature performance of the secondary battery such as high temperature stability, etc., can also be improved. Among them, after the secondary battery of the present invention is placed in an environment of 60° C.
  • the DC resistance growth rate and the growth rate of the generated gas volume of the secondary battery have only a small change, and the capacity recovery rate is as high as 95% or more.
  • the low temperature performance of the secondary battery can also be improved.
  • Charger and discharger purchased from Shenghong (BTS0510C80-HP)
  • reagents used in this paper such as ethylene carbonate, ethyl methyl carbonate, diethyl carbonate and LiPF 6 , were purchased from Shanghai Sinopharm or Sigma-Aldrich.
  • the structures of the compounds were determined by nuclear magnetic resonance ( 19 F NMR) and liquid chromatography-mass spectrometry (HPLC-MS).
  • Liquid chromatography uses ion chromatography.
  • Chromatographic column Metrosep ASUPP7-250 (4.0mm inner diameter ⁇ 250mm).
  • the detector used a Metrohm Model 819 conductance detector.
  • the ion chromatography detection conditions are as follows:
  • Chromatographic column temperature 45 °C; flow rate: 0.7 mL/min; eluent: 10 mM sodium carbonate (Na 2 CO 3 ) solution, 35% acetonitrile by volume; injection volume: 100 ⁇ L; Range scale: 100 ⁇ S/s.
  • Mass spectrometry was performed using an Agilent 6410 triple quadrupole mass spectrometer.
  • the mass spectrometry detection conditions are as follows:
  • the mass spectrometer type is electrospray ionization (ESI); nebulizer pressure: 45 psig; drying gas flow rate: 12 L/min; drying gas temperature: 350° C.; capillary voltage: 1750V; fragmentation voltage: 120V; collision energy: 30V.
  • ESI electrospray ionization
  • nebulizer pressure 45 psig
  • drying gas flow rate 12 L/min
  • drying gas temperature 350° C.
  • capillary voltage 1750V
  • fragmentation voltage 120V
  • collision energy 30V.
  • LiF was dissolved in difluoromethane to prepare a 1 mM solution, and SO 2 F 2 gas was passed into the above solution at a temperature of -55°C, and the gas pressure was maintained at 1 atm. After sufficient salt formation for 12 hours, the above-mentioned compound was obtained by slow distillation at a temperature of -40° C. to remove the solvent and excess gas.
  • LiF was dissolved in difluoromethane to prepare a 1 mM solution, and SOF 4 gas was introduced into the above solution at a temperature of -55°C, and the gas pressure was maintained at 1 atm. After sufficient salt formation for 12 hours, the above-mentioned compound was obtained by slow distillation at a temperature of -40° C. to remove the solvent and excess gas.
  • the positive electrode of the secondary battery of the present invention can be prepared by the following method
  • the positive active material, acetylene black and polyvinylidene fluoride (PVDF) were added to anhydrous N-methylpyrrolidone solvent and mixed to make a slurry, wherein the positive active material, acetylene black and polyvinylidene fluoride (PVDF)
  • the mass ratio is 90:5:5.
  • the obtained slurry was coated on one side of an aluminum foil pre-coated with a conductive assistant, wherein the thickness of the aluminum foil was 15 ⁇ m. After drying the aluminum foil, the thickness of the aluminum foil was extended to 80 ⁇ m with a roll press.
  • the obtained pole piece was then cut into a shape in which the active material layer was 30 mm wide and 40 mm long, and the uncoated portion was 5 mm wide and 9 mm long.
  • the obtained product is the positive pole piece of the secondary battery.
  • the negative electrode of the secondary battery of the present invention can be prepared by the following method.
  • the negative electrode active material Mix the negative electrode active material, an aqueous dispersion of sodium carboxymethyl cellulose with a mass fraction of 1%, and an aqueous dispersion of styrene-butadiene rubber with a mass fraction of 50% to prepare a slurry, in which the negative electrode active material is mixed.
  • the mass ratio of the substance, the aqueous dispersion of sodium carboxymethylcellulose and the aqueous dispersion of styrene-butadiene rubber is 98:100:2.
  • the obtained slurry was coated on one side of a copper foil having a thickness of 10 ⁇ m.
  • the copper foil was dried, it was rolled with a roll press, and the obtained pole piece was cut into the following shape, in which the active material layer was 30 mm wide and 40 mm long, and the uncoated part was 5 mm wide and 9 mm long.
  • the obtained product is the negative pole piece of the secondary battery.
  • the electrolytic solution of the secondary battery of the present invention can be prepared by the following method.
  • the secondary battery of the present invention can be produced by the following method.
  • the positive pole piece, the negative pole piece and the human separator made of polyethylene are stacked in the manner of negative electrode, separator, positive electrode, and separator, and the negative electrode is terminated to obtain a bare cell.
  • the bare cell is hot-pressed so that the PVDF on the surface of the diaphragm bonds the pole pieces together. After the hot-pressed bare cell is welded with tabs, it is placed in an aluminum-plastic film with a punched hole, and hot-melt packaging is performed to obtain a pre-packaged battery with a liquid injection port.
  • the pre-packaged battery is placed in a vacuum furnace to be fully baked and dried, a certain amount of electrolyte is injected from the liquid injection port, and the liquid injection port is packaged in a vacuum environment to obtain the secondary battery of the present invention.
  • the secondary batteries of Examples 1-10 were prepared according to the above method.
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:5:2.
  • the sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 13.0% by weight.
  • the following components were added: 1.5% LiPF 2 O 2 (lithium difluorophosphate) and 1% LiFSI (lithium bisfluorosulfonimide salt) as the second lithium salt, 4 % of VC (vinylene carbonate), 0.5% of PS (1,3-propane sultone), and 1% of LiSO 2 F 3 to obtain a non-aqueous electrolyte.
  • the secondary battery was prepared according to the above method, wherein the positive electrode active material was LiNi 0.65 Co 0.15 Mn 0.2 O 2 , and the negative electrode active material was artificial graphite.
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:5:2.
  • the sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 13.0% by weight.
  • the following components were added: 1.5% LiPF 2 O 2 (lithium difluorophosphate) and 1% LiFSI (lithium bisfluorosulfonimide salt) as the second lithium salt, 4 % of VC (vinylene carbonate), 0.5% of PS (1,3-propane sultone), 0.2% of LiSO 2 F 3 and 0.8% of TBASO 2 F 3 to obtain a non-aqueous electrolyte.
  • the secondary battery was prepared according to the above method, wherein the positive electrode active material was LiNi 0.65 Co 0.15 Mn 0.2 O 2 , and the negative electrode active material was artificial graphite.
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:5:2.
  • the sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 13.0% by weight.
  • the following components were added: 1.5% LiPF 2 O 2 (lithium difluorophosphate) and 1% LiFSI (lithium bisfluorosulfonimide salt) as the second lithium salt, 4 % of VC (vinylene carbonate), 0.5% of PS (1,3-propane sultone), and 1% of LiSOF 5 to obtain a non-aqueous electrolyte.
  • the secondary battery was prepared according to the above method, wherein the positive electrode active material was LiNi 0.65 Co 0.15 Mn 0.2 O 2 , and the negative electrode active material was artificial graphite.
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:5:2.
  • the sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 13.0% by weight.
  • the following components were added: 1.5% LiPF 2 O 2 (lithium difluorophosphate) and 1% LiFSI (lithium bisfluorosulfonimide salt) as the second lithium salt, 4 % of VC (vinylene carbonate), 0.5% of PS (1,3-propane sultone), 0.2% of LiSOF 5 and 0.8% of TBASOF 5 to obtain a non-aqueous electrolyte.
  • the secondary battery was prepared according to the above method, wherein the positive electrode active material was LiNi 0.65 Co 0.15 Mn 0.2 O 2 , and the negative electrode active material was artificial graphite.
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:5:2.
  • the sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 13.0% by weight.
  • LiPF 2 O 2 lithium difluorophosphate
  • LiFSI lithium bisfluorosulfonimide
  • LiTFSI bisfluorosulfonimide
  • Lithium trifluoromethylsulfonyl)amide second lithium salt
  • 4% DTD vinyl sulfate
  • 0.5% VC vinyl carbonate
  • PS 1,3-propanesulfonic acid
  • 0.8% LiSO 2 F 3 and 0.2% LiSOF 5 to obtain a non-aqueous electrolyte.
  • a secondary battery was prepared according to the above method, wherein the positive electrode active material was LiNi 0.55 Co 0.15 Mn 0.3 O 2 , and the negative electrode active material was artificial graphite.
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:6:1.
  • the sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolyte solution was 13.5 wt %.
  • LiPF 2 O 2 lithium difluorophosphate
  • LiODFP lithium bis-oxalate difluorophosphate
  • 0.4% LiBF 4 as a second Lithium salt
  • 0.5% DTD vinyl sulfate
  • 4% PC acrylate
  • 0.5% VC vinyl carbonate
  • PS 1,3-propane sultone
  • 0.5 % LiSO 2 F 3 and 0.5% LiSOF 5 wherein the positive active material is LiNi 0.55 Co 0.15 Mn 0.3 O 2 , and the negative active material is natural graphite.
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:5:2.
  • the sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 14% by weight.
  • the following components were added: 1% LiPF 2 O 2 (lithium difluorophosphate) and 0.5% LiODFB (lithium difluorooxalate borate) as the second lithium salt, 3% FEC (Fluoroethylene carbonate), 1% PS (1,3-propane sultone), 3% LiSO 2 F 3 and 3% LiSOF 5 , wherein the positive active material is LiNi 0.8 Co 0.1 Mn 0.1 O 2.
  • the negative electrode active material is silicon-oxygen composite artificial graphite.
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:4:3.
  • the sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 14% by weight.
  • LiPF 2 O 2 lithium difluorophosphate
  • LiFSI lithium bisfluorosulfonimide
  • 4% DMC dimethyl carbonate
  • 0.5% VC vinyl carbonate
  • 1.5% PS 1,3-propane sultone
  • 0.5% LiSO 2 F 3 and 0.5% LiSOF 5 wherein the positive active material is LiNi 0.65 Co 0.15 Mn 0.3 O 2 , and the negative active material is natural graphite.
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:5:2.
  • the sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 10% by weight.
  • LiFSI lithium bisfluorosulfonimide
  • LiTFSI lithium bis(trifluoromethylsulfonyl)amide
  • the positive active material is LiNi 0.55 Co 0.1 Mn 0.35 O 2
  • the negative electrode active material is artificial graphite.
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:5:2.
  • the sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 13% by weight.
  • LiPO 2 F 2 lithium difluorophosphate
  • LiFSI lithium bisfluorosulfonimide salt
  • PS polypropane sultone
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:5:2.
  • the sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 14% by weight.
  • the following components were added: 1% LiPO 2 F 2 (lithium difluorophosphate) and 0.5% LiODFB (lithium difluorooxalate borate) as the second lithium salt, 3% FEC (fluoroethylene carbonate), 1% PS (1,3-propane sultone), wherein the positive active material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 , and the negative active material is silicon-oxygen composite artificial graphite.
  • LiPO 2 F 2 lithium difluorophosphate
  • LiODFB lithium difluorooxalate borate
  • FEC fluoroethylene carbonate
  • PS 1,3-propane sultone
  • the secondary battery of the present invention can be tested by the following method.
  • the prepared battery was subjected to chemical aging treatment and placed on the fixture. At 25°C, the activated battery was charged to 4.3V with a current of 1C, and the current was constant voltage to 0.05C, and then discharged to 2.8V at 1C. , and record the discharge capacity.
  • the initial DCR of the battery is recorded in the first cycle of discharge, and then the cycle test is performed until the battery discharge capacity is 80% of the capacity of the first cycle, and the DCR, DCR growth rate of the battery after the end of the cycle, and the cycle when the battery reaches 80% SOH (battery state of health) are recorded. and gas production volume changes.
  • the DC resistance of the secondary battery and the change in the volume of the generated gas are measured by the following methods:
  • the battery is discharged to 50% SOC (state of charge, reflecting the remaining capacity of the battery) at a current of 1C, the current is increased to 4C, and maintained for 30s, and the difference between the updated stable voltage and the original platform voltage is detected. , the ratio of its value to the 3C current value is the DC resistance of the battery.
  • the DCR growth rate was obtained by comparing the DCR at the end of the cycle with the DCR at the beginning of the cycle.
  • the secondary battery was fixed with a string, it was completely immersed in water at 25°C, the weight difference before and after the immersion was recorded, and the volume difference was converted according to the density of water at 25°C.
  • the activated batteries were charged to 4.3V with a current of 1C at 25°C, and the current was maintained at a constant voltage of 0.05C.
  • the secondary battery was then placed in an environment of 60°C for 60 days, and the 60-day capacity recovery rate was recorded.
  • the activated batteries were charged to 4.25V at a current of 1C at 60°C, and the current was maintained at a constant voltage of 0.05C, and then discharged to 3.0 at 1C. V, record the discharge capacity.
  • the initial DCR of the battery was recorded in the first cycle of discharge, and then the cycle test was performed until the battery discharge capacity was 80% of the first cycle capacity, and the DCR, DCR growth rate and gas production volume change of the battery were recorded after the cycle.
  • Example 6 After chemical aging of Example 6, the activated battery was charged to 4.25V at a current of 1C at -30°C, and the current was maintained at a constant voltage of 0.05C, and then discharged to 3.0V at 1C, and the discharge capacity was recorded. The initial DCR of the battery was recorded in the first cycle of discharge, and then the cycle test was performed until the battery discharge capacity was 80% of the capacity of the first cycle, and the DCR growth rate of the battery after the cycle was recorded.
  • Table 1 shows the results of the initial discharge capacity test, cycle test, direct current resistance (DCR) test, and gas generation volume change test of the secondary batteries of Examples 1-9.
  • Table 2 shows the test results of the capacity recovery rate of the secondary batteries of Examples 5-7 at 60°C and -30°C.
  • Example SOH turns a Initial DCR (mohm) DCR growth rateb Gas volume growth rate 1 2523 1.17 20% 8% 2 2530 1.25 twenty two% 12% 3 2431 1.2 twenty one% 9% 4 2444 1.27 twenty four% 13% 5 2781 1.21 twenty two% 9% 6 2341 1.18 twenty three% 10% 7 2009 1.21 32% 14% 8 2054 1.23 27% 12% 9 1894 1.12 twenty four% 12%
  • the secondary batteries of Examples 1-9 had lower initial DC resistances of only about 1.12-1.27 mohm. After the charge-discharge cycle, the DC resistance growth rate of the secondary batteries of Examples 1-9 is also relatively reduced, only about 20% to about 32%, and the growth rate of the gas volume generated by the secondary battery is even lower, only about 20% to 32%. About 8% - about 14%. It can be seen that, using the compound of formula (I) as an additive, the secondary battery of the present invention has good stability. The volume doesn't change much. In addition, when the secondary batteries of Examples 1-9 reached 80% SOH, they had a relatively high number of turns, ranging from 1894 to 2781. It can be seen that, with the compound of formula (I) as an additive, the secondary battery of the present invention has a longer service life.
  • Examples 5-7 other additives DTD (vinyl sulfate), PC (acrylate) or FEC (fluoroethylene carbonate) are added to act together with the compound of formula (I), which is beneficial to improve the high temperature stability of the battery properties or low temperature stability.
  • DTD vinyl sulfate
  • PC acrylate
  • FEC fluoroethylene carbonate
  • Table 2 the secondary battery of the present invention has excellent high-temperature performance. After repeated charging and discharging at high temperature (for example, about 60° C.), the DC resistance growth rate of the secondary battery is only 5%-15%, and the capacity of the secondary battery is only 5%-15%. The recovery rate can reach 94%-97%, and the growth rate of gas production volume is only 2-3%.
  • the DC resistance growth rate of the secondary battery is only 7% at low temperature (eg, about -30° C.) after repeated charging and discharging. It can be seen that using the compound of formula (I) as an additive and acting together with other additives is beneficial to further improve the high temperature and low temperature stability of the secondary battery.
  • Table 3 shows the results of the initial discharge capacity test, cycle test, direct current resistance (DCR) test, gas volume change test and capacity recovery rate test results of the secondary battery at 60°C of the secondary battery of the comparative example.
  • the test conditions are the same as those in Table 1. used the same.
  • Table 4 shows the test results of DCR growth rate, capacity recovery rate and gas production volume growth rate of the secondary battery of Comparative Example 2 at 60° C.
  • the test conditions are the same as those used in Table 2.
  • the secondary battery of Comparative Example 2 had a significantly higher DCR growth rate and a relatively lower capacity recovery rate after being placed in an environment of 60°C for 60 days. Therefore, the compound of formula (I) can improve the high temperature performance of the secondary battery as an additive.

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Abstract

The present invention relates to the compound shown in formula (I), a non-aqueous electrolyte additive, a non-aqueous electrolyte, and a power storage device containing same, and a use for same in a non-aqueous electrolyte additive.

Description

硫酸盐类化合物、包含其的非水电解液及蓄电设备Sulfate-based compound, non-aqueous electrolyte solution containing same, and power storage device 技术领域technical field
本发明涉及电池技术领域，具体涉及一种硫酸盐类化合物、包含其的非水电解液及蓄电设备。The present invention relates to the technical field of batteries, in particular to a sulfate compound, a non-aqueous electrolyte containing the same, and a power storage device.
背景技术Background technique
在非水电解液二次电池中，电解液包含锂盐、非水溶剂和添加剂，而少量的添加剂能够针对性的解决当前锂离子电池普遍存在的循环寿命较短和安全隐患等技术难题。In non-aqueous electrolyte secondary batteries, the electrolyte contains lithium salts, non-aqueous solvents and additives, and a small amount of additives can specifically solve the technical problems such as short cycle life and safety hazards that are common in current lithium-ion batteries.
目前，在非水电解液二次电池中，VC(碳酸亚乙烯酯)被认为是最佳成膜添加剂，其还原电位高于EC(碳酸亚乙酯)、PC(1,3-丙磺酸酯)和DEC(碳酸二乙酯)等，可在碳负极上优先还原。但VC难以生产，价格较高，且高温性能有待提高。因此有待开发一种性能更佳优异的电解液添加剂，其能改善负极的成膜，以及改善电池的高温性能，并提高电池的循环稳定性。Currently, in non-aqueous electrolyte secondary batteries, VC (ethylene carbonate) is considered as the best film-forming additive, and its reduction potential is higher than EC (ethylene carbonate), PC (1,3-propanesulfonic acid) Ester) and DEC (diethyl carbonate), etc., can be preferentially reduced on the carbon negative electrode. However, VC is difficult to produce, the price is high, and the high temperature performance needs to be improved. Therefore, it is necessary to develop an electrolyte additive with better performance, which can improve the film formation of the negative electrode, improve the high temperature performance of the battery, and improve the cycle stability of the battery.
CN201847750A公开了一种可再充电锂电池的阻燃电解质，包括锂盐、直链碳酸酯类溶剂、至少一种铵阳离子、磷酸类溶剂和包含草酸硼酸盐的添加剂，具有改善的热稳定性、阻燃性以及诸如高速率和循环寿命性能的电化学特性。CN107293784A公开了一种电解液及锂离子电池，包括锂盐、有机溶剂及添加剂，其中添加剂包括硅烷磷酸酯化合物和/或硅烷硼酸酯化合物、氟碳表面活性剂和防过充添加剂，锂离子电池具有高温存储性能、高温循环性能、过充性能及倍率性能。CN105830271A公开了一种膦酰基甲酸化合物以及包含所述化合物的非水电解液和蓄电设备，该非水电解液具有维持高温下高负荷充放电循环、抑制负极热稳定性的降低、提高蓄电装置安全性的特性。CN103493277A公开了一种三氟甲基苯化合物以及包含所属化合物的非水电解液和蓄电设备，该非水电解液可以提高温度范围内的电化学特性。CN201847750A discloses a flame retardant electrolyte for a rechargeable lithium battery, comprising a lithium salt, a linear carbonate-based solvent, at least one ammonium cation, a phosphoric acid-based solvent, and an additive comprising oxalate borate, with improved thermal stability , flame retardancy, and electrochemical properties such as high rate and cycle life performance. CN107293784A discloses an electrolyte and lithium ion battery, including lithium salt, organic solvent and additives, wherein the additives include silane phosphate compound and/or silane borate compound, fluorocarbon surfactant and anti-overcharge additive, lithium ion The battery has high temperature storage performance, high temperature cycle performance, overcharge performance and rate performance. CN105830271A discloses a phosphonoformic acid compound, a non-aqueous electrolyte solution containing the compound, and a power storage device. The non-aqueous electrolyte solution has the functions of maintaining high-load charge-discharge cycles at high temperatures, suppressing the decrease in thermal stability of negative electrodes, and improving power storage. Device safety features. CN103493277A discloses a trifluoromethylbenzene compound, a non-aqueous electrolyte solution and a power storage device containing the compound, and the non-aqueous electrolyte solution can improve electrochemical properties in a temperature range.
发明内容SUMMARY OF THE INVENTION
在一方面，本发明提供式(I)所示的化合物In one aspect, the present invention provides compounds of formula (I)
Figure PCTCN2020123361-appb-000001
Figure PCTCN2020123361-appb-000001
其特征在于，It is characterized in that,
R各自独立地选自卤素、卤代C 1-10烷基、卤代C 3-10环烷基； Each R is independently selected from halogen, halogenated C 1-10 alkyl, halogenated C 3-10 cycloalkyl;
m为1-3的整数；m is an integer from 1 to 3;
n为1或2；n is 1 or 2;
M为反荷阳离子。M is a counter cation.
在一个实施方案中，所述反荷阳离子为金属阳离子或季胺基团。In one embodiment, the counter cation is a metal cation or a quaternary amine group.
在一个优选的实施方案中，所述化合物选自In a preferred embodiment, the compound is selected from
Figure PCTCN2020123361-appb-000002
及其组合，
Figure PCTCN2020123361-appb-000002
and its combination,
其中M和m如上文所定义；wherein M and m are as defined above;
特别地，M m+为如上述所定义的金属阳离子或季胺基团， In particular, M m+ is a metal cation or a quaternary amine group as defined above,
m为1-3的整数。m is an integer of 1-3.
在一个更优选的实施方案中，所述化合物选自In a more preferred embodiment, the compound is selected from
Figure PCTCN2020123361-appb-000003
及其组合。
Figure PCTCN2020123361-appb-000003
and its combinations.
在另一方面，本发明提供一种非水电解液用添加剂，其包含本发明的式(I)所示的化合物。In another aspect, the present invention provides an additive for a non-aqueous electrolyte solution comprising the compound represented by the formula (I) of the present invention.
在又一方面，本发明提供一种非水电解液，其包含本发明的式(I)所示的化合物和包含其的非水电解液用添加剂。In yet another aspect, the present invention provides a non-aqueous electrolyte solution comprising the compound represented by the formula (I) of the present invention and an additive for non-aqueous electrolyte solutions comprising the same.
在另一方面，本发明提供一种蓄电设备，其包含本发明的式(I)所示的化合物或本发明的非水电解液。In another aspect, the present invention provides an electrical storage device comprising the compound represented by the formula (I) of the present invention or the non-aqueous electrolyte solution of the present invention.
在还一方面，本发明提供式(I)所示的化合物用于非水电解液添加剂的用途。In yet another aspect, the present invention provides the use of the compound represented by formula (I) as a non-aqueous electrolyte additive.
在另一方面，本发明提供一种电动装置，其包含本发明的蓄电设备。In another aspect, the present invention provides an electric device including the power storage device of the present invention.
具体实施方式Detailed ways
以下将对本发明进一步详细说明。这样的描述为说明目的，而非限制本发明。本领域技术人员可由本说明书公开的内容容易地了解本发明的其他优点与功效。本发明也可以通过其他不同的具体实施例加以施行或应用。本领域技术人员在不背离本发明的精神前提下，进行各种修饰与变更。The present invention will be described in further detail below. Such descriptions are for illustrative purposes, not for limiting the invention. Other advantages and functions of the present invention can be readily appreciated by those skilled in the art from the disclosure of this specification. The present invention can also be implemented or applied in other different specific embodiments. Those skilled in the art can make various modifications and changes without departing from the spirit of the present invention.
一般定义和术语General Definitions and Terminology
如果没有另行指出，在此所提及的所有出版物、专利申请、专利和其他参考文献通过援引以其全部并入本文。All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless otherwise indicated.
除非另有定义，本文使用的所有技术和科学术语具有与本发明所属领域技术人员通常理解的相同的含义。若存在矛盾，则以本文提供的定义为准。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the definitions provided herein will control.
除非另有说明，所有的百分比、份数、比例等都是按重量计的。All percentages, parts, ratios, etc. are by weight unless otherwise indicated.
当以范围、优选范围或者优选的数值上限以及优选的数值下限的形式表述某个量、浓度或其他值或参数的时候，应当理解相当于具体揭示了通过将任意一对范围上限或优 选数值与任意范围下限或优选数值结合起来的任何范围，而不考虑该范围是否具体揭示。除非另外指出，本文所列出的数值范围旨在包括范围的端点，和该范围之内的所有整数和分数。本发明的范围并不限制于当定义范围时所引用的特定数值。例如“1-8”涵盖1、2、3、4、5、6、7、8以及由其中任何两个值组成的任何亚范围，例如2-6、3-5。又例如，C 1-10烷基表示具有1-10个碳原子的烷基，涵盖1、2、3、4、5、6、7、8、9、10，以及任何两个值组成的任何亚范围，例如1-8、2-7、3-6。又例如，C 3-10环烷基表示具有3-10个碳原子的烷基，涵盖3、4、5、6、7、8、9、10，以及任何两个值组成的任何亚范围，例如3-8、4-7、5-6。 When an amount, concentration, or other value or parameter is expressed in terms of a range, preferred range, or preferred upper numerical limit and preferred lower numerical limit, it should be understood that it is equivalent to a specific disclosure by combining any pair of upper range or preferred values with Any range combined with any lower range limit or preferred numerical value, regardless of whether or not the range is specifically disclosed. Unless otherwise indicated, the numerical ranges recited herein are intended to include the endpoints of the range, and all integers and fractions within that range. The scope of the invention is not to be limited by the specific numerical values recited when defining the range. For example, "1-8" encompasses 1, 2, 3, 4, 5, 6, 7, 8, and any subrange consisting of any two values therein, such as 2-6, 3-5. As another example, C 1-10 alkyl represents an alkyl group having 1-10 carbon atoms, covering 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and any combination of any two values Subranges such as 1-8, 2-7, 3-6. As another example, C 3-10 cycloalkyl represents an alkyl group having 3-10 carbon atoms, covering 3, 4, 5, 6, 7, 8, 9, 10, and any subrange consisting of any two values, For example 3-8, 4-7, 5-6.
除非另外说明，本文中的百分比、份数、比值等均是按重量计。Unless otherwise stated, the percentages, parts, ratios, etc. herein are by weight.
术语“约”、“大约”当与数值变量并用时，通常指该变量的数值和该变量的所有数值在实验误差内(例如对于平均值95％的置信区间内)或在指定数值的±10％内，或更宽范围内。The terms "about", "approximately" when used in conjunction with a numerical variable generally mean that the numerical value of that variable and all numerical values of that variable are within experimental error (eg, within a 95% confidence interval for the mean) or within ±10% of the specified numerical value. %, or within a wider range.
术语“包括”、“包含”、“具有”、“含有”或“涉及”及其在本文中的其他变体形式为包含性的或开放式的，且不排除其他未列举的元素或方法步骤。本领域技术人员应当理解，上述术语如“包括”涵盖“由…组成”的含义。表述“由…组成”排除未指明的任何元素、步骤或成分。表述“基本上由…组成”指范围限制在指定的元素、步骤或成分，加上任选存在的不会实质上影响所要求保护的主题的基本和新的特征的元素、步骤或成分。应当理解，表述“包含”涵盖表述“基本上由…组成”和“由…组成”。The terms "comprising", "comprising", "having", "containing" or "involving" and other variations thereof herein are inclusive or open-ended and do not exclude other unrecited elements or method steps . It should be understood by those skilled in the art that the above-mentioned terms such as "comprising" encompass the meaning of "consisting of". The expression "consisting of" excludes any element, step or ingredient not specified. The expression "consisting essentially of" means that the scope is limited to the specified elements, steps or components, plus optional elements, steps or components that do not materially affect the basic and novel characteristics of the claimed subject matter. It should be understood that the expression "comprising" encompasses the expressions "consisting essentially of" and "consisting of".
术语“选自…”是指在后面所列的组中的一个或多个元素，独立地加以选择，并且可以包括两个或更多个元素的组合。The term "selected from..." refers to one or more elements of the following listed group, selected independently, and may include combinations of two or more elements.
本文所使用的术语“任选”或“任选地”是指随后描述的事件或情况可能发生或可能不发生，该描述包括发生所述事件或情况和不发生所述事件或情况。As used herein, the terms "optional" or "optionally" mean that the subsequently described event or circumstance may or may not occur, and that the description includes the occurrence and non-occurrence of said event or circumstance.
当在本文中描述数值或范围端值时，应理解所公开的内容包括所引用的特定值或端值。When numerical values or range endpoints are described herein, it is to be understood that the disclosure includes the particular value or endpoint recited.
本文所使用的术语“一种或多种”或“至少一种”指一种、两种、三种、四种、五种、六种、七种、八种、九种或更多种。As used herein, the terms "one or more" or "at least one" refer to one, two, three, four, five, six, seven, eight, nine or more.
除非另有说明，术语“其组合”及“其混合物”，表示所述各元素的多组分混合物，例如两种、三种、四种以及直到最大可能的多组分混合物。Unless otherwise specified, the terms "combinations thereof" and "mixtures thereof" refer to multi-component mixtures of the elements in question, such as two, three, four and up to the maximum possible multi-component mixtures.
术语“卤”或“卤素”或“卤代”应理解为表示氟(F)、氯(Cl)、溴(Br)或碘(I)原子，优选氟、氯、溴原子。The terms "halo" or "halogen" or "halo" are to be understood to mean fluorine (F), chlorine (Cl), bromine (Br) or iodine (I) atoms, preferably fluorine, chlorine, bromine atoms.
术语“烷基”是指由碳原子和氢原子组成的直链或支链的饱和的脂肪烃基团，其通过单键与分子的其余部分连接。“烷基”可以具有1-10个碳原子，即“C 1-C 10烷基”，例如C 1-C 4烷基、C 1-C 3烷基、C 1-C 2烷基、C 3烷基、C 4烷基、C 3-C 6烷基。烷基的非限制性实例包括但不限于甲基、乙基、丙基、丁基、戊基、己基、异丙基、异丁基、仲丁基、叔丁基、异戊基、2-甲基丁基、1-甲基丁基、1-乙基丙基、1,2-二甲基丙基、新戊基、1,1-二甲基丙基、4-甲基戊基、3-甲基戊基、2-甲基戊基、1-甲基戊基、2-乙基丁基、1-乙基丁基、3,3-二甲基丁基、2,2-二甲基丁基、1,1-二甲基丁基、2,3-二甲基丁基、1,3-二甲基 丁基或1,2-二甲基丁基，或者它们的异构体。“亚基”是指在含有自由价电子的碳原子上再去掉一个氢原子而得到的，具有两个与分子其他部分连接的连接位点的基团。例如“亚烷基”或“烷基亚基”指饱和的直链或支链的二价烃基。“亚烷基”的实例包括但不限于如亚甲基(-CH 2-)、亚乙基(-C 2H 4-)、亚丙基(-C 3H 6-)、亚丁基(-C 4H 8-)、亚戊基(-C 5H 10-)、亚己基(-C 6H 12-)、1-甲基亚乙基(-CH(CH 3)CH 2-)、2-甲基亚乙基(-CH 2CH(CH 3)-)、甲基亚丙基或乙基亚丙基等。 The term "alkyl" refers to a straight or branched chain saturated aliphatic hydrocarbon group consisting of carbon and hydrogen atoms attached to the rest of the molecule by a single bond. "Alkyl" may have 1-10 carbon atoms, i.e. "C 1 -C 10 alkyl", eg C 1 -C 4 alkyl, C 1 -C 3 alkyl, C 1 -C 2 alkyl, C 3 alkyl, C 4 alkyl, C 3 -C 6 alkyl. Non-limiting examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2- Methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-di Methylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl, or their isomers body. "Subunit" refers to a group obtained by removing a hydrogen atom from a carbon atom containing a free valence electron and having two attachment sites to the rest of the molecule. For example "alkylene" or "alkylidene" refers to a saturated linear or branched divalent hydrocarbon radical. Examples of "alkylene" include, but are not limited to, such as methylene ( -CH2- ), ethylene ( -C2H4- ), propylene ( -C3H6- ), butylene ( - C 4 H 8 -), pentylene (-C 5 H 10 -), hexylene (-C 6 H 12 -), 1-methylethylene (-CH(CH 3 )CH 2 -), 2 - methyl ethylene (-CH 2 CH(CH 3 )-), methyl propylene or ethyl propylene and the like.
术语“环烷基”，在本文中单独或与其他基团组合使用时，指饱和的非芳族单环或多环(诸如双环)烃环(例如单环，如环丙基、环丁基、环戊基、环己基、环庚基、环辛基、环壬基；或双环，包括螺环、稠合或桥连***(诸如双环[1.1.1]戊基、双环[2.2.1]庚基、双环[3.2.1]辛基或双环[5.2.0]壬基、十氢化萘基等)。例如，术语“C 3-10环烷基”指具有3-10个环碳原子(如3、4、5、6、7、8、9或10个)的环烷基。 The term "cycloalkyl", as used herein, alone or in combination with other groups, refers to a saturated non-aromatic monocyclic or polycyclic (such as bicyclic) hydrocarbon ring (eg, monocyclic, such as cyclopropyl, cyclobutyl, etc.) , cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl; or bicyclic, including spiro, fused or bridged systems (such as bicyclo[1.1.1]pentyl, bicyclo[2.2.1] heptyl, bicyclo[3.2.1]octyl or bicyclo[5.2.0]nonyl, decalinyl, etc.). For example, the term "C 3-10 cycloalkyl" refers to a group having 3-10 ring carbon atoms ( such as 3, 4, 5, 6, 7, 8, 9 or 10) cycloalkyl.
本发明的化合物可以为阴离子的形式，与阳离子形成本发明化合物的盐。所述阳离子包括，但不限于金属阳离子、铵根离子、季胺基团。The compounds of the present invention may be in the form of anions, forming salts of the compounds of the present invention with cations. The cations include, but are not limited to, metal cations, ammonium ions, quaternary amine groups.
术语“反荷离子”是指带有与本申请的化合物相反电荷的物质，其可以是带电离子，例如金属阳离子或铵根离子，也可以是带电基团，例如季胺基团。The term "counterion" refers to a species having an opposite charge to the compounds of the present application, which can be a charged ion, such as a metal cation or ammonium ion, or a charged group, such as a quaternary amine group.
术语“链状酯”是指具有直链状结构的酯类化合物，其实例包括但不限于甲酸甲酯、甲酸乙酯、乙酸甲酯、乙酸乙酯、丙酸甲酯、丙酸乙酯、丁酸甲酯、丁酸乙酯、碳酸甲乙酯、甲基丙基碳酸酯、碳酸二甲酯、碳酸二乙酯、乙基丙基碳酸酯、碳酸二丙酯等。The term "chain ester" refers to ester compounds having a straight chain structure, examples of which include but are not limited to methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, Methyl butyrate, ethyl butyrate, methyl ethyl carbonate, methyl propyl carbonate, dimethyl carbonate, diethyl carbonate, ethyl propyl carbonate, dipropyl carbonate and the like.
术语“环状酯”是指具有环状结构的酯类化合物，其实例包括但不限于碳酸亚乙酯、碳酸亚丙酯、碳酸1,2-亚丁酯、碳酸2,3-亚丁酯、4-氟-1,3-二氧杂环戊烷-2-酮、反式或顺式4,5-二氟-1,3-二氧杂环戊烷-2-酮、氟代碳酸乙烯酯、碳酸亚乙烯酯、碳酸乙烯基亚乙酯、碳酸丙烯酯、碳酸乙烯酯、碳酸丁烯酯。The term "cyclic ester" refers to an ester compound having a cyclic structure, examples of which include, but are not limited to, ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 4 -Fluoro-1,3-dioxolane-2-one, trans or cis-4,5-difluoro-1,3-dioxolane-2-one, fluoroethylene carbonate , vinylene carbonate, vinyl ethylene carbonate, propylene carbonate, ethylene carbonate, butylene carbonate.
术语“电解液”是化学电池、电解电容等使用的介质，其可以为化学电池和电解电容等的正常工作提供离子。The term "electrolyte" is a medium used by chemical batteries, electrolytic capacitors, etc., which can provide ions for the normal operation of chemical batteries, electrolytic capacitors, and the like.
术语“非水电解液”是指使用非水溶剂的电解液。The term "non-aqueous electrolytic solution" refers to an electrolytic solution using a non-aqueous solvent.
术语“电解质盐”是指离子盐，其至少部分地可溶于电解质组合物的溶剂并且在电解质组合物的溶剂中至少部分地解离成离子，以形成导电性电解质组合物。优选使用锂盐作为电解质盐。The term "electrolyte salt" refers to an ionic salt that is at least partially soluble in the solvent of the electrolyte composition and at least partially dissociated into ions in the solvent of the electrolyte composition to form a conductive electrolyte composition. Lithium salts are preferably used as electrolyte salts.
术语“阳极”是指电化学电池的电极，在其中发生氧化。在原电池，诸如电池中，阳极为带负电的电极。在二次电池(即，可再充电电池)中，阳极是其中在放电期间发生氧化并且在充电期间发生还原的电极。The term "anode" refers to the electrode of an electrochemical cell in which oxidation occurs. In galvanic cells, such as batteries, the anode is the negatively charged electrode. In secondary batteries (ie, rechargeable batteries), the anode is the electrode in which oxidation occurs during discharge and reduction occurs during charge.
术语“阴极”是指电化学电池的电极，在其中发生还原。在原电池，诸如电池中，阴极为带正电的电极。在二次电池(即，可再充电电池)中，阴极是其中在放电期间发生还原并且在充电期间发生氧化的电极。The term "cathode" refers to the electrode of an electrochemical cell where reduction occurs. In galvanic cells, such as batteries, the cathode is the positively charged electrode. In secondary batteries (ie, rechargeable batteries), the cathode is the electrode in which reduction occurs during discharge and oxidation occurs during charge.
术语“锂离子电池”是指一种可再充电电池类型，其中锂离子在放电期间从阳极移动至阴极，并且在充电期间从阴极移动至阳极。The term "lithium ion battery" refers to a type of rechargeable battery in which lithium ions move from anode to cathode during discharge and from cathode to anode during charge.
术语“二次电池”是指其中电化学反应可逆的电化学电池，也是指能够再充电或可再 充电以用于在使用寿命中通过重复充电和放电而使用的电池。The term "secondary battery" refers to an electrochemical cell in which the electrochemical reaction is reversible, and also refers to a cell that can be recharged or rechargeable for use by repeated charging and discharging over its useful life.
术语“化成”是指在电池制备过程中，获得电池后对电池进行小电流充放电的处理。化成处理有利于稳定电池的电性能。The term "formation" refers to the process of charging and discharging the battery with a small current after the battery is obtained during the battery preparation process. The chemical formation treatment is beneficial to stabilize the electrical properties of the battery.
术语“老化”是指在电池制备过程中，电池装配注液完成并经历第一次化成处理后，在一定温度下静置一段时间的操作。电池的老化处理有助于SEI结构重组，形成宽松多孔的膜，使得电池的性能更加稳定。The term "aging" refers to the operation of standing at a certain temperature for a period of time after the battery is assembled and filled with liquid and undergoes the first chemical conversion treatment during the battery preparation process. The aging treatment of the battery helps to reorganize the SEI structure to form a loose and porous membrane, which makes the battery performance more stable.
术语“SEI”或“SEI膜”是指电池首次充放电过程中，电极材料与电解液在固液相界面上发生反应，形成一层覆盖于电极材料表面的钝化层。The term "SEI" or "SEI film" refers to the reaction between the electrode material and the electrolyte at the solid-liquid interface during the first charge and discharge of the battery to form a passivation layer covering the surface of the electrode material.
术语“电动汽车”是指以电力为动力源的汽车，电动汽车的实例包括但不限于电动车(EV)、混合动力车(HEV)、插电式混合动力车(PHEV)等。The term "electric vehicle" refers to a vehicle powered by electricity, and examples of an electric vehicle include, but are not limited to, an electric vehicle (EV), a hybrid electric vehicle (HEV), a plug-in hybrid electric vehicle (PHEV), and the like.
术语“电动两轮车”是指以电力为动力源的两轮车，电动两轮车的实例包括但不限于E-自行车和E-踏板车。The term "electric two-wheeled vehicle" refers to a two-wheeled vehicle powered by electricity, examples of an electric two-wheeled vehicle include, but are not limited to, E-bikes and E-scooters.
式(I)的化合物Compounds of formula (I)
在一方面，本发明提供式(I)化合物：In one aspect, the present invention provides compounds of formula (I):
Figure PCTCN2020123361-appb-000004
Figure PCTCN2020123361-appb-000004
其特征在于，R各自独立地选自卤素、卤代C 1-10烷基、卤代C 3-10环烷基；m为1-3的整数；n为1或2；M为反荷阳离子。 It is characterized in that, R is independently selected from halogen, halogenated C 1-10 alkyl, halogenated C 3-10 cycloalkyl; m is an integer of 1-3; n is 1 or 2; M is a counter cation .
在一优选的实施方案中，R各自独立地选自卤素。在一更优选的实施方案中，R各自独立地选自氟、氯或溴。在一特别优选的实施方案中，R选自氟。In a preferred embodiment, each R is independently selected from halogen. In a more preferred embodiment, each R is independently selected from fluoro, chloro or bromo. In a particularly preferred embodiment, R is selected from fluoro.
根据反荷阳离子M m+的价态，m对应为1-3的整数。例如反荷阳离子M m+为锂离子(Li +)时，m对应为1，R为如上文所限定的取代基。又例如反荷阳离子M m+为钙离子(Ca 2+)时，m对应为2。又例如，反荷阳离子M m+为季胺基团时，m对应为1。 According to the valence state of the counter cation M m+ , m corresponds to an integer of 1-3. For example when the counter cation M m+ is a lithium ion (Li + ), m corresponds to 1 and R is a substituent as defined above. For another example, when the counter cation M m+ is calcium ion (Ca 2+ ), m corresponds to 2. For another example, when the counter cation M m+ is a quaternary amine group, m corresponds to 1.
在一优选的实施方案中，所述化合物选自In a preferred embodiment, the compound is selected from
Figure PCTCN2020123361-appb-000005
及其组合，其中M和m如上文所定义；
Figure PCTCN2020123361-appb-000005
and combinations thereof, wherein M and m are as defined above;
特别地，M m+为如上所述的金属阳离子或季胺基团，m为1-3的整数。 In particular, M m+ is a metal cation or a quaternary amine group as described above, and m is an integer of 1-3.
在一更优选的实施方案中，所述化合物选自In a more preferred embodiment, the compound is selected from
Figure PCTCN2020123361-appb-000006
(在本文中又表示为LiSO 2F 3)、
Figure PCTCN2020123361-appb-000007
(在本文中又表 示为LiSOF 5)、
Figure PCTCN2020123361-appb-000008
(在本文中又表示为TBASO 2F 3)、
Figure PCTCN2020123361-appb-000009
(在本文中又表示为TBASOF 5)及其组合。在本文中，TBA +表示为季胺基团四丁基胺，即
Figure PCTCN2020123361-appb-000010
因此
Figure PCTCN2020123361-appb-000011
又可以表示为
Figure PCTCN2020123361-appb-000012
Figure PCTCN2020123361-appb-000006
(Also referred to herein as LiSO 2 F 3 ),
Figure PCTCN2020123361-appb-000007
(Also denoted as LiSOF 5 herein),
Figure PCTCN2020123361-appb-000008
(also referred to herein as TBASO 2 F 3 ),
Figure PCTCN2020123361-appb-000009
(also referred to herein as TBASOF5 ) and combinations thereof. In this paper, TBA + is represented as the quaternary amine group tetrabutylamine, i.e.
Figure PCTCN2020123361-appb-000010
therefore
Figure PCTCN2020123361-appb-000011
can also be expressed as
Figure PCTCN2020123361-appb-000012
反荷阳离子counter cation
本文的化合物中的反荷阳离子包括但不限于金属阳离子、铵根离子、季胺基团等。Counter cations in the compounds herein include, but are not limited to, metal cations, ammonium ions, quaternary amine groups, and the like.
在一优选的实施方案中，所述反荷阳离子为金属阳离子或季胺基团。In a preferred embodiment, the counter cation is a metal cation or a quaternary amine group.
在一更优选的实施方案中，所述反荷阳离子为金属阳离子。金属阳离子可以包括碱金属阳离子、碱土金属阳离子、过渡金属阳离子等。在一优选的实施方案中，所述式(I)化合物包含的金属阳离子为碱金属阳离子或碱土金属阳离子。在一更优选的实施方案中，所述式(I)化合物包含的金属阳离子选自锂离子、钠离子、钾离子、钙离子、镁离子及其组合。在一特别优选的实施方案中，所述式(I)化合物包含的金属阳离子为锂离子。In a more preferred embodiment, the counter cation is a metal cation. Metal cations may include alkali metal cations, alkaline earth metal cations, transition metal cations, and the like. In a preferred embodiment, the metal cation contained in the compound of formula (I) is an alkali metal cation or an alkaline earth metal cation. In a more preferred embodiment, the metal cation contained in the compound of formula (I) is selected from the group consisting of lithium ion, sodium ion, potassium ion, calcium ion, magnesium ion and combinations thereof. In a particularly preferred embodiment, the metal cation contained in the compound of formula (I) is a lithium ion.
在另一更优选的实施方案中，所述反荷阳离子为季胺基团。在一优选的实施方案中，所述式(I)化合物包含的季胺基团选自四甲基胺、四乙基胺、四丙基胺、四丁基胺。在一更优选择实施方案中，所述式(I)化合物包含的季胺基团为四丁基胺。In another more preferred embodiment, the counter cation is a quaternary amine group. In a preferred embodiment, the quaternary amine group contained in the compound of formula (I) is selected from the group consisting of tetramethylamine, tetraethylamine, tetrapropylamine, and tetrabutylamine. In a more preferred embodiment, the quaternary amine group contained in the compound of formula (I) is tetrabutylamine.
非水电解液用添加剂Additives for non-aqueous electrolytes
在另一方面，本发明提供一种非水电解液用添加剂，其特征在于，含有上述式(I)所示的化合物。In another aspect, the present invention provides an additive for a non-aqueous electrolyte solution, characterized by containing the compound represented by the above formula (I).
包含式(I)化合物的非水电解液Non-aqueous electrolyte containing compound of formula (I)
在另一方面，本发明提供一种非水电解液，其包含本发明的式(I)所示的化合物。在本发明的非水电解液中，可以包含一种或多种本发明的式(I)所示的化合物，即，可以使用一种式(I)所示的化合物，也可以使用一种以上的式(I)所示的化合物的混合物或组合。In another aspect, the present invention provides a non-aqueous electrolyte solution comprising the compound represented by the formula (I) of the present invention. The non-aqueous electrolyte solution of the present invention may contain one or more compounds represented by the formula (I) of the present invention, that is, one compound represented by the formula (I) may be used, or more than one compound may be used A mixture or combination of compounds of formula (I).
式(I)所示的化合物作为非水电解液中的添加剂，可以在负极还原成膜，钝化电极表面，允许锂离子自由的进出电极而溶剂分子无法穿越，从而阻止溶剂分子共插对电极的 破坏，提高包含该非水电解液的电池的循环效率和可逆容量等性能。此外，式(I)化合物具有较高的还原电压，可以在负极优先被还原成膜，改善包含该非水电解液的电池的高温性能，并提高电池的循环稳定性。As an additive in the non-aqueous electrolyte, the compound represented by the formula (I) can be reduced to form a film at the negative electrode, passivate the electrode surface, allow lithium ions to freely enter and exit the electrode, and the solvent molecules cannot pass through, thereby preventing the solvent molecules from co-inserting into the counter electrode. The destruction of the non-aqueous electrolyte improves the cycle efficiency and reversible capacity of the battery containing the non-aqueous electrolyte. In addition, the compound of formula (I) has a high reduction voltage, can be preferentially reduced to a film at the negative electrode, improves the high temperature performance of the battery containing the non-aqueous electrolyte, and improves the cycle stability of the battery.
在一个实施方案中，基于非水电解液的总重量，式(I)化合物在非水电解液中的含量为约0.1-10重量％。在一个优选的实施方案中，基于非水电解液的总重量，式(I)化合物在非水电解液中的含量为约0.2-7重量％。在一个更优选的实施方案中，基于非水电解液的总重量，式(I)化合物在非水电解液中的含量为约1重量％。例如约0.1重量％、约0.2重量％、约0.3重量％、约0.5重量％、约0.8重量％、约1重量％、约3重量％、约2重量％、约3重量％、约4重量％、约5重量％、约6重量％、约7重量％、约8重量％、约8重量％、约9重量％、约10重量％。过低的式(I)化合物的含量不能有效地改善包含该非水电解液的电池的循环寿命。而过高的式(I)化合物的含量会使包含该非水电解液的电池在高温工作时，产生过量气体，引起电池膨胀的问题。In one embodiment, the compound of formula (I) is present in the non-aqueous electrolyte in an amount of about 0.1 to 10% by weight, based on the total weight of the non-aqueous electrolyte. In a preferred embodiment, the compound of formula (I) is present in the non-aqueous electrolyte in an amount of about 0.2 to 7% by weight, based on the total weight of the non-aqueous electrolyte. In a more preferred embodiment, the content of the compound of formula (I) in the non-aqueous electrolyte is about 1% by weight based on the total weight of the non-aqueous electrolyte. For example, about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.5 wt%, about 0.8 wt%, about 1 wt%, about 3 wt%, about 2 wt%, about 3 wt%, about 4 wt% , about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 8 wt%, about 9 wt%, about 10 wt%. An excessively low content of the compound of formula (I) cannot effectively improve the cycle life of the battery containing the non-aqueous electrolyte. When the content of the compound of formula (I) is too high, when the battery containing the non-aqueous electrolyte solution is operated at high temperature, excess gas is generated, causing the problem of battery swelling.
非水溶剂non-aqueous solvent
在一个实施方案中，非水电解液可以包含非水溶剂。可以使用的非水溶剂的实例包括但不限于环状酯、链状酯、醚、酰胺、磷酸酯、砜、腈、含S＝O键的化合物等。In one embodiment, the non-aqueous electrolyte may contain a non-aqueous solvent. Examples of non-aqueous solvents that can be used include, but are not limited to, cyclic esters, chain esters, ethers, amides, phosphate esters, sulfones, nitriles, S=O bond-containing compounds, and the like.
在一个优选的实施方案中，在本发明的非水电解液中，使用的非水溶剂选自环状酯、链状酯及其组合。In a preferred embodiment, in the non-aqueous electrolyte of the present invention, the non-aqueous solvent used is selected from the group consisting of cyclic esters, chain esters and combinations thereof.
环状碳酸酯Cyclic carbonate
环状酯包括但不限于环状碳酸酯、内酯。在一个优选的实施方案中，在本发明的非水电解液中，使用的非水溶剂为环状碳酸酯。Cyclic esters include, but are not limited to, cyclic carbonates, lactones. In a preferred embodiment, in the non-aqueous electrolyte of the present invention, the non-aqueous solvent used is a cyclic carbonate.
环状碳酸酯的实例包括但不限于碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸丁烯酯(BC)、氟代碳酸乙烯酯(FEC)、碳酸亚乙烯酯(VC)、碳酸1,2-丁烯酯、碳酸2,3-丁烯酯碳酸亚乙烯酯、碳酸乙烯基亚乙酯(VEC)、反式或顺式4,5-二氟-1,3-二氧杂环戊烷-2-酮(两者统称为“DFEC”)、4-乙炔基-1,3-二氧杂环戊烷-2-酮(EEC)、碳酸丙烯酯、碳酸乙烯酯、碳酸丁烯酯等。Examples of cyclic carbonates include, but are not limited to, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), fluoroethylene carbonate (FEC), vinylene carbonate (VC), carbonic acid 1,2-Butene ester, 2,3-butene carbonate, vinylene carbonate, vinylethylene carbonate (VEC), trans or cis 4,5-difluoro-1,3-dioxa Cyclopentan-2-one (both collectively referred to as "DFEC"), 4-ethynyl-1,3-dioxolane-2-one (EEC), propylene carbonate, ethylene carbonate, butylene carbonate Ester, etc.
在一个优选的实施方案中，在本发明的非水电解液中，使用的非水溶剂选自碳酸乙烯酯、碳酸丙烯酯、碳酸1,2-丁烯酯、碳酸丙烯酯及其组合。在一个更优选的实施方案中，在本发明的非水电解液中，使用的非水溶剂为碳酸乙烯酯。In a preferred embodiment, in the non-aqueous electrolyte of the present invention, the non-aqueous solvent used is selected from the group consisting of ethylene carbonate, propylene carbonate, 1,2-butene carbonate, propylene carbonate and combinations thereof. In a more preferred embodiment, in the non-aqueous electrolyte of the present invention, the non-aqueous solvent used is ethylene carbonate.
在另一个优选的实施方案中，在本发明的非水电解液中，使用的非水溶剂为含有碳-碳双键或碳-碳三键等不饱和键的环状碳酸酯。在一个更优选的实施方案中，在本发明的非水电解液中，使用的非水溶剂选自碳酸亚乙烯酯、碳酸乙烯基亚乙酯、4-乙炔基-1,3-二氧杂环戊烷-2-酮及其组合。在一个特别优选的实施方案中，在本发明的非水电解液中，使用的非水溶剂为碳酸亚乙烯酯。In another preferred embodiment, in the non-aqueous electrolyte of the present invention, the non-aqueous solvent used is a cyclic carbonate containing unsaturated bonds such as carbon-carbon double bonds or carbon-carbon triple bonds. In a more preferred embodiment, in the non-aqueous electrolyte of the present invention, the non-aqueous solvent used is selected from vinylene carbonate, vinylethylene carbonate, 4-ethynyl-1,3-dioxa Cyclopentan-2-ones and combinations thereof. In a particularly preferred embodiment, in the non-aqueous electrolyte of the present invention, the non-aqueous solvent used is vinylene carbonate.
在又一个优选的实施方案中，在本发明的非水电解液中，使用的非水电解液为含有氟原子的环状碳酸酯。在一个更优选的实施方案中，在本发明的非水电解液中，使用的非水电解液选自氟代碳酸乙烯酯、反式或顺式4,5-二氟-1,3-二氧杂环戊烷-2-酮及其组合。In yet another preferred embodiment, in the non-aqueous electrolyte of the present invention, the non-aqueous electrolyte used is a cyclic carbonate containing a fluorine atom. In a more preferred embodiment, in the non-aqueous electrolyte of the present invention, the non-aqueous electrolyte used is selected from fluoroethylene carbonate, trans or cis 4,5-difluoro-1,3-di Oxolan-2-ones and combinations thereof.
合适的含有不饱和键的环状碳酸酯非水溶剂的含量有助于提高包含该非水电解液的电池的低温和高温特性，并提高高温充电保存后的负荷特性。过高的含有不饱和键的环状碳酸酯含量会提高电解液的黏度，降低电池中的电荷移动效率，降低电池的效率。过低的含有不饱和键的环状碳酸酯含量会降低电池的电导率，降低电池的效率。A suitable content of the unsaturated bond-containing cyclic carbonate nonaqueous solvent helps to improve the low temperature and high temperature characteristics of a battery containing the nonaqueous electrolyte solution, and to improve the load characteristics after high-temperature charge storage. Excessive content of cyclic carbonate containing unsaturated bonds will increase the viscosity of the electrolyte, reduce the charge transfer efficiency in the battery, and reduce the efficiency of the battery. Too low content of cyclic carbonate containing unsaturated bonds will reduce the conductivity of the battery and reduce the efficiency of the battery.
合适的含有氟原子的环状碳酸酯的非水溶剂的含量有助于提高包含该非水电解液的电池的低温和高温特性，并提高高温充电保存后的负荷特性。过高的含有氟原子的环状碳酸酯含量会提高电解液的黏度，降低电池中的电荷移动效率，降低电池的效率。过低的氟原子的环状碳酸酯含量会降低电池的电导率，降低电池的效率。An appropriate content of the nonaqueous solvent of the fluorine atom-containing cyclic carbonate helps to improve the low temperature and high temperature characteristics of a battery containing the nonaqueous electrolyte solution, and to improve the load characteristics after high-temperature charge storage. An excessively high content of cyclic carbonate containing fluorine atoms will increase the viscosity of the electrolyte, reduce the charge transfer efficiency in the battery, and reduce the efficiency of the battery. Too low cyclic carbonate content of fluorine atoms will reduce the conductivity of the battery and reduce the efficiency of the battery.
在一些实施方案中，非水溶剂为单一环状碳酸酯溶剂。In some embodiments, the non-aqueous solvent is a single cyclic carbonate solvent.
在另一些实施方案中，非水溶剂为混合溶剂。在一个优选的实施方案中，所述非水溶剂包含2种以上环状碳酸酯溶剂。使用混合溶剂时，可以进一步提高包含该非水电解液的电池的高温下的电化学性能。在另一个优选的实施方案中，所述非水溶剂包含3种以上环状碳酸酯溶剂。混合环状碳酸酯的组合包括但不限于环状碳酸酯与含不饱和键的环状碳酸酯、环状碳酸酯与含氟原子的环状碳酸酯、含不饱和键的环状碳酸酯与含氟原子的环状碳酸酯或环状碳酸酯与含不饱和键的环状碳酸酯与含氟原子的环状碳酸酯等，其中环状碳酸酯、含不饱和键的环状碳酸酯、含氟原子的环状碳酸酯的选择如上所述。In other embodiments, the non-aqueous solvent is a mixed solvent. In a preferred embodiment, the non-aqueous solvent contains two or more cyclic carbonate solvents. When a mixed solvent is used, the electrochemical performance at high temperature of the battery containing this non-aqueous electrolyte solution can be further improved. In another preferred embodiment, the non-aqueous solvent contains three or more cyclic carbonate solvents. Combinations of mixed cyclic carbonates include, but are not limited to, cyclic carbonates and cyclic carbonates containing unsaturated bonds, cyclic carbonates and cyclic carbonates containing fluorine atoms, and cyclic carbonates containing unsaturated bonds and cyclic carbonates. Fluorine atom-containing cyclic carbonate or cyclic carbonate and unsaturated bond-containing cyclic carbonate and fluorine atom-containing cyclic carbonate, etc., wherein cyclic carbonate, unsaturated bond-containing cyclic carbonate, The selection of the fluorine atom-containing cyclic carbonate is as described above.
链状碳酸酯Chain carbonate
链状酯包括但不限于链状碳酸酯、链状磺酸酯。在一个优选的实施方案中，在本发明的非水电解液中，使用的非水溶剂为链状碳酸酯。Chain esters include, but are not limited to, chain carbonates, chain sulfonates. In a preferred embodiment, in the non-aqueous electrolyte of the present invention, the non-aqueous solvent used is a chain carbonate.
链状碳酸酯的实例包括但不限于碳酸甲乙酯(EMC)、甲基丙基碳酸酯、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、乙基丙基碳酸酯、碳酸二丙酯等。Examples of chain carbonates include, but are not limited to, ethyl methyl carbonate (EMC), methyl propyl carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl propyl carbonate, dicarbonate Propyl ester etc.
在一个优选的实施方案中，在本发明的非水电解液中，使用的非水电解液优选选自碳酸甲乙酯、碳酸二甲酯、碳酸二乙酯、乙基丙基碳酸酯、碳酸二丙酯及其组合。在一个更优选的实施方案中，在本发明的非水电解液中，使用的非水电解液优选选自碳酸甲乙酯、碳酸二甲酯、碳酸二乙酯及其组合。In a preferred embodiment, in the non-aqueous electrolyte of the present invention, the non-aqueous electrolyte used is preferably selected from ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, ethyl propyl carbonate, carbonic acid Dipropyl esters and combinations thereof. In a more preferred embodiment, in the non-aqueous electrolyte of the present invention, the non-aqueous electrolyte used is preferably selected from ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate and combinations thereof.
对于包含该非水电解液的电池，合适的链状碳酸酯含量有助于获得良好的电池性能。过高的链状碳酸酯含量会降低电池的电导率，降低电池的效率。过低的链状碳酸酯含量会使得电解液的黏度提高，降低电池中的电荷移动效率，降低电池的效率。For batteries containing this non-aqueous electrolyte, a suitable chain carbonate content helps to obtain good battery performance. Excessive chain carbonate content will reduce the conductivity of the battery and reduce the efficiency of the battery. Too low chain carbonate content will increase the viscosity of the electrolyte, reduce the charge transfer efficiency in the battery, and reduce the efficiency of the battery.
在一些实施方案中，非水溶剂为单一链状碳酸酯溶剂。In some embodiments, the non-aqueous solvent is a single chain carbonate solvent.
在另一些实施方案中，非水溶剂为混合溶剂。在一个优选的实施方案中，所述非水溶剂包含2种以上链状碳酸酯溶剂。使用混合溶剂时，可以进一步提高包含该非水电解液的电池的高温下的电化学性能。在另一个优选的实施方案中，所述非水溶剂包含3种以上链状碳酸酯溶剂。当非水溶剂电解液的非水溶剂为链状碳酸酯的混合物时，其选择如上文所述。In other embodiments, the non-aqueous solvent is a mixed solvent. In a preferred embodiment, the non-aqueous solvent contains two or more kinds of chain carbonate solvents. When a mixed solvent is used, the electrochemical performance at high temperature of the battery containing this non-aqueous electrolyte solution can be further improved. In another preferred embodiment, the non-aqueous solvent contains three or more kinds of chain carbonate solvents. When the non-aqueous solvent of the non-aqueous solvent electrolyte is a mixture of chain carbonates, its selection is as described above.
其他溶剂other solvents
内酯Lactone
在一个实施方案中，作为非水溶剂的内酯选自γ-丁内酯、γ-戊内酯及α-当归内酯及其组合。In one embodiment, the lactone as the non-aqueous solvent is selected from the group consisting of gamma-butyrolactone, gamma-valerolactone, and alpha-angelica lactone, and combinations thereof.
醚ether
在一个实施方案中，作为非水溶剂的醚选自四氢呋喃、2-甲基四氢呋喃、1,3-二氧杂戊环、1,3-二噁烷及1,4-二噁烷等环状醚，1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、1,2-二丁氧基乙烷及其组合。In one embodiment, the ether as the non-aqueous solvent is selected from cyclic rings such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 1,3-dioxane and 1,4-dioxane Ethers, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, and combinations thereof.
酰胺Amide
在一个实施方案中，作为非水溶剂的酰胺为二甲基甲酰胺。In one embodiment, the amide as the non-aqueous solvent is dimethylformamide.
磷酸酯Phosphate
在一个实施方案中，作为非水溶剂的磷酸酯选自磷酸三甲酯、磷酸三丁酯、磷酸三辛酯及其组合。In one embodiment, the phosphate ester as the non-aqueous solvent is selected from the group consisting of trimethyl phosphate, tributyl phosphate, trioctyl phosphate, and combinations thereof.
腈Nitrile
在一个实施方案中，作为非水溶剂的腈选自乙腈、丙腈、琥珀腈、戊二腈或己二腈、庚二腈及其组合。In one embodiment, the nitrile as the non-aqueous solvent is selected from the group consisting of acetonitrile, propionitrile, succinonitrile, glutaronitrile or adiponitrile, pimeliconitrile, and combinations thereof.
含S＝O键的化合物Compounds containing S=O bonds
在一个实施方案中，作为非水溶剂的含S＝O键的化合物选自1,3-丙烷磺内酯、1,3-丁烷磺内酯及1,4-丁烷磺内酯等的磺内酯化合物，亚硫酸亚乙酯、六氢苯并[1,3,2]二氧硫杂环戊烷-2-氧化物(也称作1,2-环己二醇环状亚硫酸酯)、5-乙烯基-六氢-1,3,2-苯并二氧硫醇-2-氧化物等的环状亚硫酸酯化合物，1,2-乙二醇二甲烷磺酸酯、1,2-丙二醇二甲烷磺酸酯、1,3-丙二醇二甲烷磺酸酯、1,4-丁二醇二甲烷磺酸酯、1,5-戊二醇二甲烷磺酸酯、甲烷磺酸2-丙炔酯及亚甲基甲烷二磺酸酯等的磺酸酯化合物，二乙烯基砜、1,2-双(乙烯基磺酰基)乙烷、双(2-乙烯基磺酰基乙基)及其组合。In one embodiment, the S=O bond-containing compound as the non-aqueous solvent is selected from the group consisting of 1,3-propane sultone, 1,3-butane sultone, 1,4-butane sultone, and the like Sultone compounds, ethylene sulfite, hexahydrobenzo[1,3,2]dioxolane-2-oxide (also known as 1,2-cyclohexanediol cyclic sulfite ester), cyclic sulfite compounds such as 5-vinyl-hexahydro-1,3,2-benzodioxythiol-2-oxide, 1,2-ethylene glycol dimethanesulfonate, 1,2-propanediol dimethanesulfonate, 1,3-propanediol dimethanesulfonate, 1,4-butanediol dimethanesulfonate, 1,5-pentanediol dimethanesulfonate, methanesulfonate Sulfonate compounds such as 2-propynyl acid and methylene methane disulfonate, divinyl sulfone, 1,2-bis(vinylsulfonyl)ethane, bis(2-vinylsulfonylethyl) base) and their combinations.
为了实现适当的物理性质，上述的非水溶剂可以混合使用。其中混合使用的非水溶剂选自环状碳酸酯、链状碳酸酯、醚、酰胺、磷酸酯、砜、腈、含S＝O键的化合物，环状碳酸酯、链状碳酸酯、醚、酰胺、磷酸酯、砜、腈和含S＝O键的化合物的选择如上文所述。In order to achieve appropriate physical properties, the above-mentioned non-aqueous solvents may be used in combination. The non-aqueous solvent used in combination is selected from cyclic carbonate, chain carbonate, ether, amide, phosphate, sulfone, nitrile, compound containing S=O bond, cyclic carbonate, chain carbonate, ether, The selection of amides, phosphates, sulfones, nitriles and compounds containing S=O bonds is as described above.
在一个优选的实施方案中，在本发明的非水电解液中，使用的非水溶剂为环状碳酸酯与链状碳酸酯的组合，其中环状碳酸酯和链状碳酸酯的选择均如上文所述。对于包含该非水电解液的电池，这样的组合可以提高低温和高温循环特性及高温充电保存后的负荷特性。In a preferred embodiment, in the non-aqueous electrolyte of the present invention, the non-aqueous solvent used is a combination of cyclic carbonate and chain carbonate, wherein the selection of cyclic carbonate and chain carbonate are as above described in the text. Such a combination can improve low-temperature and high-temperature cycle characteristics and load characteristics after high-temperature charge storage for batteries containing the non-aqueous electrolyte.
对于，包含该非水电解液的电池，合适的环状碳酸酯与链状碳酸酯的质量比有助于获得良好的电池性能。在一个优选的实施方案中，在本发明的非水电解液中，环状碳酸酯溶剂与链状碳酸酯溶剂的质量比为3:7。过高的环状碳酸酯溶剂与链状碳酸酯溶剂的质量比会使得电解液的黏度提高，降低包含该非水电解液的电池中的电荷移动效率，降低电池的效率。过低的环状碳酸酯溶剂与链状碳酸酯溶剂的质量比会降低电池的电导率，降低电池的效率。For batteries containing this non-aqueous electrolyte, a suitable mass ratio of cyclic carbonate to chain carbonate helps to obtain good battery performance. In a preferred embodiment, in the non-aqueous electrolyte of the present invention, the mass ratio of the cyclic carbonate solvent to the chain carbonate solvent is 3:7. An excessively high mass ratio of the cyclic carbonate solvent to the chain carbonate solvent will increase the viscosity of the electrolyte, reduce the charge transfer efficiency in the battery containing the non-aqueous electrolyte, and reduce the efficiency of the battery. An excessively low mass ratio of the cyclic carbonate solvent to the chain carbonate solvent will reduce the electrical conductivity of the battery and reduce the efficiency of the battery.
电解质盐Electrolyte salt
电解质盐是指离子盐，其至少部分地可溶于电解质组合物的溶剂并且在电解质组合物的溶剂中至少部分地解离成离子，以形成导电性电解质组合物。Electrolyte salt refers to an ionic salt that is at least partially soluble in the solvent of the electrolyte composition and at least partially dissociated into ions in the solvent of the electrolyte composition to form a conductive electrolyte composition.
在一个实施方案中，在本发明的非水电解液中，使用锂盐或鎓盐作为电解质盐。在一个更优选的实施方案中，在本发明的非水电解液中，使用锂盐作为电解质盐。In one embodiment, in the non-aqueous electrolyte of the present invention, a lithium salt or an onium salt is used as the electrolyte salt. In a more preferred embodiment, in the non-aqueous electrolyte solution of the present invention, a lithium salt is used as the electrolyte salt.
锂盐Lithium salt
锂盐是指具有锂作为阳离子的盐。在电池工作过程中，电解质锂盐的锂离子在电池正负极之间起传输离子的作用，对电池性能的发挥至关重要。另外，电池中电解质锂盐的种类、纯度、含量以及锂盐与其他物质的组合可以不同程度地影响电池的容量、充放电性能、寿命及安全性等。Lithium salts refer to salts having lithium as a cation. During the working process of the battery, the lithium ions of the electrolyte lithium salt play the role of transporting ions between the positive and negative electrodes of the battery, which is crucial to the performance of the battery. In addition, the type, purity, and content of the electrolyte lithium salt in the battery, as well as the combination of the lithium salt and other substances, can affect the capacity, charge-discharge performance, lifespan, and safety of the battery to varying degrees.
在本发明的非水电解液中，使用的锂盐包括第一锂盐和第二锂盐，其中第一锂盐为无机锂盐，第二锂盐为含有有机基团的锂盐。In the non-aqueous electrolyte of the present invention, the used lithium salt includes a first lithium salt and a second lithium salt, wherein the first lithium salt is an inorganic lithium salt, and the second lithium salt is a lithium salt containing an organic group.
第一锂盐first lithium salt
在一个实施方案中，在本发明的非水电解液中，使用的第一锂盐选自LiPF 6、LiBF 4、LiBCl 4、LiAsF 6、LiClO 4、LiAlO 2、LiCl、LiI、LiSbF 6及其组合。在一个优选的实施方案中，在本发明的非水电解液中，使用的第一锂盐选自LiPF 6、LiBF 4及其组合。 In one embodiment, in the non-aqueous electrolyte of the present invention, the first lithium salt used is selected from LiPF 6 , LiBF 4 , LiBCl 4 , LiAsF 6 , LiClO 4 , LiAlO 2 , LiCl, LiI, LiSbF 6 and the like. combination. In a preferred embodiment, in the non-aqueous electrolyte of the present invention, the first lithium salt used is selected from LiPF 6 , LiBF 4 and combinations thereof.
第一锂盐通常具有很好的电离能力，在溶剂中易于电离，从而获得大量的游离的锂离子，因此合适的第一锂盐有助于为非水电解液提供足够含量的锂离子，提高非水电解液的电导率。在一个实施方案中，第一锂盐的含量为约8-16重量％。在一个优选的实施方案中，第一锂盐的含量为约10-14重量％。在一个更优选的实施方案中，第一锂盐的含量为约13-13.5重量％。例如约8重量％、约8.5重量％、约9重量％、约9.5重量％、约10重量％、约10.5重量％、约11重量％、约11.5重量％、约12重量％、约12.5重量％、约13重量％、约13.5重量％、约14重量％、约14.5重量％、约15重量％、约15.5重量％、约16重量％。过多的第一锂盐含量会使得非水电解液的粘度提高，降低包含该非水电解液的电池中的电荷移动效率，从而降低电池的效率。The first lithium salt usually has good ionization ability and is easy to ionize in the solvent, so as to obtain a large amount of free lithium ions. Therefore, a suitable first lithium salt helps to provide a sufficient content of lithium ions for the non-aqueous electrolyte, improving the Conductivity of non-aqueous electrolytes. In one embodiment, the content of the first lithium salt is about 8-16% by weight. In a preferred embodiment, the content of the first lithium salt is about 10-14% by weight. In a more preferred embodiment, the content of the first lithium salt is about 13-13.5% by weight. For example, about 8 wt%, about 8.5 wt%, about 9 wt%, about 9.5 wt%, about 10 wt%, about 10.5 wt%, about 11 wt%, about 11.5 wt%, about 12 wt%, about 12.5 wt% , about 13 wt%, about 13.5 wt%, about 14 wt%, about 14.5 wt%, about 15 wt%, about 15.5 wt%, about 16 wt%. Excessive content of the first lithium salt may increase the viscosity of the non-aqueous electrolyte, reduce the charge transfer efficiency in the battery including the non-aqueous electrolyte, and thereby reduce the efficiency of the battery.
第二锂盐second lithium salt
在一个实施方案中，在本发明的非水电解液中，使用的第二锂盐选自含P＝O结构的锂盐、含-S(＝O) 2-结构的锂盐、含硼草酸络合物作为阴离子的锂盐及其组合。 In one embodiment, in the non-aqueous electrolyte of the present invention, the second lithium salt used is selected from the group consisting of lithium salts containing P=O structure, lithium salts containing -S(=O) 2 - structure, boron-containing oxalic acid Lithium salts of complexes as anions and combinations thereof.
含P＝O结构的锂盐包括但不限于二氟磷酸锂(LiPO 2F 2)、单氟磷酸锂(Li 2PO 3F)等。 Lithium salts containing a P=O structure include, but are not limited to, lithium difluorophosphate (LiPO 2 F 2 ), lithium monofluorophosphate (Li 2 PO 3 F), and the like.
含-S(＝O) 2-结构的锂盐包括但不限于含-S(＝O) 2O结构的锂盐、含-S(＝O) 2-N --S(＝O) 2-结构的锂盐等。在一个优选的实施方案中，含-S(＝O) 2-结构的锂盐为含-S(＝O) 2-N --S(＝O) 2-结构的锂盐。在一个更优选的实施方案中，含-S(＝O) 2-N --S(＝O) 2-结构的锂盐选自双氟磺酰亚胺锂(LiFSI)、双(三氟甲基磺酰)氨基锂(LiTFSI)等。 Lithium salts containing -S(=O) 2 -structure include but are not limited to lithium salts containing -S(=O) 2 O structure, -S(=O) 2 -N - -S(=O) 2 - Structure of lithium salts, etc. In a preferred embodiment, the lithium salt containing the -S(=O) 2 - structure is a lithium salt containing the -S(=O) 2 -N - -S(=O) 2 - structure. In a more preferred embodiment, the lithium salt containing -S(=O) 2 -N - -S(=O) 2 - structure is selected from lithium bisfluorosulfonimide (LiFSI), bis(trifluoromethane) sulfonyl) lithium amide (LiTFSI) and the like.
含硼草酸络合物作为阴离子的锂盐包括但不限于双草酸二氟磷酸锂(LiODFP)、二氟草酸硼酸锂(LiODFB)、硼酸锂(LiBOB)等。Lithium salts containing boron oxalate complexes as anions include, but are not limited to, lithium bis-oxalate difluorophosphate (LiODFP), lithium difluorooxalate borate (LiODFB), lithium borate (LiBOB), and the like.
在一个优选的实施方案中，在本发明的非水电解液中，使用的第二锂盐选自 LiPO 2F 2、Li 2PO 3F、LiODFB、LiODFP、LiBOB、LiTFSI、LiFSI及其组合。在一个更优选的实施方案中，在本发明的非水电解液中，使用的第二锂盐选自LiPO 2F 2、LiODFB、LiODFP、LiBOB、LiTFSI、LiFSI及其组合。 In a preferred embodiment, in the non-aqueous electrolyte of the present invention, the second lithium salt used is selected from LiPO 2 F 2 , Li 2 PO 3 F, LiODFB, LiODFP, LiBOB, LiTFSI, LiFSI, and combinations thereof. In a more preferred embodiment, in the non-aqueous electrolyte of the present invention, the second lithium salt used is selected from LiPO 2 F 2 , LiODFB, LiODFP, LiBOB, LiTFSI, LiFSI, and combinations thereof.
合适的第二锂盐在提供少量锂离子的同时，还能够参与电极成膜，有助于提高包含该非水电解液的电池的性能。在一个实施方案中，第二锂盐的含量为约0.5-5重量％、在一个优选的实施方案中，第二锂盐的含量为约1.5-4重量％。在一个更优选的实施方案中，第二锂盐的含量为约1.9-3重量％。例如约0.5重量％、约0.8重量％、约1重量％、约1.5重量％、约1.9重量％、约2重量％、约2.3重量％、约2.5重量％、约2.8重量％、约3重量％、约3.3重量％、约3.5重量％、约3.6重量％、约4重量％、约4.5重量％、约5重量％。过高的第二锂盐含量会提高电解液的黏度，降低电池中的电荷移动效率，降低电池的效率。过低的第二锂盐含量则不能够起到提高包含该非水电解液的电池的性能作用。在一个实施方案中，在本发明的非水电解液中，使用第一锂盐与第二锂盐的组合作为电解质锂盐。这样的组合有助于提高电池负极的热稳定性，并提高锂离子的透过性。A suitable second lithium salt can also participate in electrode film formation while providing a small amount of lithium ions, which helps to improve the performance of the battery containing the non-aqueous electrolyte. In one embodiment, the second lithium salt is present in an amount of about 0.5-5% by weight, and in a preferred embodiment, the second lithium salt is present in an amount of about 1.5-4% by weight. In a more preferred embodiment, the second lithium salt is present in an amount of about 1.9-3% by weight. For example, about 0.5 wt%, about 0.8 wt%, about 1 wt%, about 1.5 wt%, about 1.9 wt%, about 2 wt%, about 2.3 wt%, about 2.5 wt%, about 2.8 wt%, about 3 wt% , about 3.3 wt%, about 3.5 wt%, about 3.6 wt%, about 4 wt%, about 4.5 wt%, about 5 wt%. An excessively high content of the second lithium salt will increase the viscosity of the electrolyte, reduce the charge transfer efficiency in the battery, and reduce the efficiency of the battery. An excessively low content of the second lithium salt cannot improve the performance of the battery containing the non-aqueous electrolyte. In one embodiment, in the non-aqueous electrolyte of the present invention, a combination of the first lithium salt and the second lithium salt is used as the electrolyte lithium salt. Such a combination helps to improve the thermal stability of the negative electrode of the battery and improve the permeability of lithium ions.
合适的第一锂盐和第二锂盐的总含量有助于锂盐与其他添加剂相互作用，实现减低阻抗、抑制气体产生的效果，同时也有利于改善电极成膜。在一个实施方案中，在本发明的非水电解液中，第一锂盐和第二锂盐的总含量为约10-20重量％。在一个优选的实施方案中，在本发明的非水电解液中，第一锂盐和第二锂盐的总含量为约12-17.6重量％。在一个更优选的实施方案中，在本发明的非水电解液中，第一锂盐和第二锂盐的总含量为约约15.4-16.3重量％。例如约10重量％、约11重量％、约12重量％、约12.5重量％、约13重量％、约13.5重量％、约14重量％、约15重量％、约15.4重量％、约15.5重量％、约16重量％、、约16.3重量％、约16.5重量％、约17重量％、约17.5重量％、约17.6重量％、约18重量％、约19重量％、约20重量％。过高的第一锂盐和第二锂盐的总含量会提高电解液的黏度，降低电解液中的电荷移动效率，降低电导率。过低的第一锂盐和第二锂盐的总含量则不能实现其用于提高电解液电导率的作用。A suitable total content of the first lithium salt and the second lithium salt helps the lithium salt to interact with other additives to achieve the effects of reducing impedance and suppressing gas generation, and is also conducive to improving electrode film formation. In one embodiment, in the non-aqueous electrolyte of the present invention, the total content of the first lithium salt and the second lithium salt is about 10-20 wt %. In a preferred embodiment, in the non-aqueous electrolyte of the present invention, the total content of the first lithium salt and the second lithium salt is about 12-17.6 wt %. In a more preferred embodiment, in the non-aqueous electrolyte of the present invention, the total content of the first lithium salt and the second lithium salt is about 15.4-16.3 wt %. For example, about 10%, about 11%, about 12%, about 12.5%, about 13%, about 13.5%, about 14%, about 15%, about 15.4%, about 15.5% by weight , about 16 wt%, about 16.3 wt%, about 16.5 wt%, about 17 wt%, about 17.5 wt%, about 17.6 wt%, about 18 wt%, about 19 wt%, about 20 wt%. An excessively high total content of the first lithium salt and the second lithium salt will increase the viscosity of the electrolyte, reduce the charge transfer efficiency in the electrolyte, and reduce the electrical conductivity. If the total content of the first lithium salt and the second lithium salt is too low, the effect of improving the conductivity of the electrolyte cannot be achieved.
其他添加剂Other additives
在本发明的非水电解液中，还可以任选地包含选自如下的其他添加剂：直链碳酸酯、环状碳酸酯、环状磺酸酯或其组合。In the non-aqueous electrolyte of the present invention, other additives selected from the group consisting of linear carbonates, cyclic carbonates, cyclic sulfonates, or combinations thereof may be optionally included.
直链碳酸酯和环状碳酸酯的选择如上文所述，其中直链碳酸酯和环状碳酸酯选自除溶剂以外的其他碳酸酯。The selection of linear carbonates and cyclic carbonates is as described above, wherein linear carbonates and cyclic carbonates are selected from carbonates other than solvents.
环状磺酸酯的实例包括但不限于1,3-丙磺酸内酯(PS)、硫酸乙烯酯(DTD)等。Examples of cyclic sulfonates include, but are not limited to, 1,3-propane sultone (PS), vinyl sulfate (DTD), and the like.
在一个实施方案中，在本发明的非水电解液中，还包含选自以下的一种或多种的添加剂：碳酸亚乙烯酯、氟代碳酸乙烯酯、碳酸二甲酯、1,3-丙磺酸内酯、硫酸乙烯酯、碳酸丙烯酯。In one embodiment, the non-aqueous electrolyte of the present invention further comprises one or more additives selected from the group consisting of vinylene carbonate, fluoroethylene carbonate, dimethyl carbonate, 1,3- propane sultone, vinyl sulfate, propylene carbonate.
在一个实施方案中，在本发明的非水电解液中，所述其他添加剂含量为约0-10重量％。在一个优选的实施方案中，在本发明的非水电解液中，所述其他添加剂含量为约 3-6重量％。在一个更合优选的实施方案中，在本发明的非水电解液中，所述其他添加剂含量为约4.5-6重量％。适的其他添加剂含量有利于提高电池的性能，例如电池的高温稳定性、低温稳定性和成膜稳定性等。例如，向本发明的非水电解液中加入硫酸乙烯酯，能够有效改善包含该非水电解液的电池的低温性能，同时有利于高温循环性能和高温储存性能。In one embodiment, in the non-aqueous electrolyte of the present invention, the content of the other additives is about 0-10% by weight. In a preferred embodiment, in the non-aqueous electrolyte of the present invention, the content of the other additives is about 3-6% by weight. In a more preferred embodiment, in the non-aqueous electrolyte of the present invention, the content of the other additives is about 4.5-6% by weight. Appropriate content of other additives is beneficial to improve the performance of the battery, such as the high temperature stability, low temperature stability and film formation stability of the battery. For example, adding vinyl sulfate to the non-aqueous electrolyte of the present invention can effectively improve the low-temperature performance of the battery containing the non-aqueous electrolyte, and is beneficial to high-temperature cycle performance and high-temperature storage performance.
蓄电设备Power storage equipment
在又一方面，本发明提供一种蓄电设备，其包含本发明的式(I)所示的化合物，或者本发明的非水电解液。In yet another aspect, the present invention provides an electrical storage device comprising the compound represented by the formula (I) of the present invention, or the non-aqueous electrolyte solution of the present invention.
在一个优选的实施方案中，所述蓄电设备为二次电池，其包含正极、负极和在非水溶剂中溶解有电解质盐的非水电解液。在本发明中，除本发明的非水电解液以外的正极、负极等构成部件可以没有特别限制地使用。In a preferred embodiment, the power storage device is a secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte in which an electrolyte salt is dissolved in a non-aqueous solvent. In the present invention, components such as positive electrodes and negative electrodes other than the non-aqueous electrolyte solution of the present invention can be used without particular limitations.
正极材料Positive electrode material
正极的活性物质可以为含有选自钴、锰及镍中的一种以上的与锂构成的复合金属氧化物。在一个实施方案中，所述正极活性物质为单一组分。在另一个实施方案中，所述正极活性物质为以上复合金属氧化物的混合物。The active material of the positive electrode may be a composite metal oxide composed of lithium and one or more selected from cobalt, manganese, and nickel. In one embodiment, the positive active material is a single component. In another embodiment, the positive electrode active material is a mixture of the above composite metal oxides.
在一个优选的实施方案中，本发明使用的锂复合金属氧化物选自LiCoO 2、LiMn 2O 4、LiNiO 2、LiCo 1-xNi xO 2(0.01<x<1)、LiNi 1/3Co 1/3Mn 1/3O 2、LiNi 0.65Co 0.15Mn 0.2O 2、LiNi 0.55Co 0.15Mn 0.3O 2、LiNi 0.8Co 0.1Mn 0.1O 2、LiNi 0.55Co 0.1Mn 0.35O 2、LiNi 1/2Mn 3/2O 4、LiCo 0.98Mg 0.02O 2及其组合。在一个更优选的实施方案中，本发明使用的锂复合金属氧化物选自LiNi 0.65Co 0.15Mn 0.2O 2、LiNi 0.55Co 0.15Mn 0.3O 2、LiNi 0.8Co 0.1Mn 0.1O 2或LiNi 0.55Co 0.1Mn 0.35O 2及其组合。 In a preferred embodiment, the lithium composite metal oxide used in the present invention is selected from LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , LiCo 1-x Ni x O 2 (0.01<x<1), LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.65 Co 0.15 Mn 0.2 O 2 , LiNi 0.55 Co 0.15 Mn 0.3 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNi 0.55 Co 0.1 Mn 0.35 O 2 , LiNi 1/ 2 Mn 3/2 O 4 , LiCo 0.98 Mg 0.02 O 2 and combinations thereof. In a more preferred embodiment, the lithium composite metal oxide used in the present invention is selected from LiNi 0.65 Co 0.15 Mn 0.2 O 2 , LiNi 0.55 Co 0.15 Mn 0.3 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 or LiNi 0.55 Co 0.1 Mn 0.35 O 2 and combinations thereof.
此外，为了提高过充电时的安全性或循环特性、或者能够在4.3V以上的充电电位下使用，锂复合金属氧化物的一部分也可以以其他元素置换。例如，也可以将钴、锰、镍的一部分以Sn、Mg、Fe、Ti、Al、Zr、Cr、V、Ga、Zn、Cu、Bi、Mo、La等至少1种以上的元素置换，或者将O的一部分以S或F置换，或者覆盖含有这些其他元素的化合物。In addition, in order to improve safety and cycle characteristics during overcharge, or to enable use at a charging potential of 4.3 V or more, a part of the lithium mixed metal oxide may be substituted with other elements. For example, part of cobalt, manganese, and nickel may be substituted with at least one element such as Sn, Mg, Fe, Ti, Al, Zr, Cr, V, Ga, Zn, Cu, Bi, Mo, and La, or Substitute a part of O with S or F, or cover compounds containing these other elements.
其中，优选为满充电状态下，正极的充电电位以Li基准计为4.3V以上时能够使用的锂复合金属氧化物，例如LiCoO 2、LiMn 2O 4、LiNiO 2。更优选为固熔体可在4.4V以上使用的锂复合金属氧化物，例如LiCo 1-xM xO 2(其中，M为选自Sn、Mg、Fe、Ti、Al、Zr、Cr、V、Ga、Zn、Cu中的至少1种以上的元素、0.001≤x≤0.05)、LiNi 1/3Mn 1/3Co 1/3O 2、LiNi 0.65Co 0.15Mn 0.2O 2、LiNi 0.55Co 0.15Mn 0.3O 2、LiNi 0.8Co 0.1Mn 0.1O 2或LiNi 0.55Co 0.1Mn 0.35O 2、LiNi 1/2Mn 3/2O 4、Li 2MnO 3与LiMO 2(M为Co、Ni、Mn、Fe等过渡金属)。若使用在高充电电压下工作的锂复合金属氧化物，由于其在充电时的与电解液进行反应，电极在特别高温下的电化学特性容易降低，但在本发明所述的二次电池中能够抑制这些电化学特性降低。特别是在包含Mn的正极的情况下，由于存在伴随来自正极的Mn离子的溶出， 电池的电阻显示出容易增加的倾向，因此在宽温度范围内使用时，电极的电化学特性显示出容易降低的倾向，而在本发明所述的二次电池中，使用上述材料作为电池的正极材料，能够抑制这些电化学特性的降低。 Among them, lithium composite metal oxides such as LiCoO 2 , LiMn 2 O 4 , and LiNiO 2 that can be used when the charge potential of the positive electrode is 4.3 V or more in terms of Li in a fully charged state are preferable. More preferably, it is a lithium composite metal oxide that can be used in a solid solution above 4.4V, such as LiCo 1-x M x O 2 (wherein M is selected from Sn, Mg, Fe, Ti, Al, Zr, Cr, V , at least one element of Ga, Zn, Cu, 0.001≤x≤0.05), LiNi 1/3 Mn 1/3 Co 1/3 O 2 , LiNi 0.65 Co 0.15 Mn 0.2 O 2 , LiNi 0.55 Co 0.15 Mn 0.3 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 or LiNi 0.55 Co 0.1 Mn 0.35 O 2 , LiNi 1/2 Mn 3/2 O 4 , Li 2 MnO 3 and LiMO 2 (M is Co, Ni, Mn, transition metals such as Fe). If a lithium composite metal oxide operating at a high charging voltage is used, the electrochemical characteristics of the electrode at particularly high temperatures are likely to be degraded due to its reaction with the electrolyte during charging, but in the secondary battery of the present invention These reductions in electrochemical properties can be suppressed. In particular, in the case of a positive electrode containing Mn, the resistance of the battery tends to increase due to the elution of Mn ions from the positive electrode, and therefore the electrochemical properties of the electrode tend to decrease when used in a wide temperature range. In the secondary battery according to the present invention, the use of the above-mentioned materials as the positive electrode material of the battery can suppress the reduction of these electrochemical properties.
正极可以通过以下示例性方法制备：将上述的正极活性物质与乙炔黑、碳黑等导电剂及聚四氟乙烯(PTFE)、聚偏氟乙烯(PVDF)、苯乙烯与丁二烯的共聚物(SBR)、丙烯腈与丁二烯的共聚物(NBR)、羧甲基纤维素(CMC)、乙烯-丙烯-双烯三元共聚物等粘结剂混合，在其中添加1-甲基-2-吡咯烷酮等高沸点溶剂进行混炼而制成正极合剂后，将该正极合剂涂布到集电体的铝箔或不锈钢制的条板等上，干燥，加压成型后，在约50-250℃的温度下、真空下进行2小时左右的加热处理。The positive electrode can be prepared by the following exemplary method: combining the above-mentioned positive electrode active material with conductive agents such as acetylene black and carbon black, and copolymers of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene and butadiene (SBR), copolymer of acrylonitrile and butadiene (NBR), carboxymethyl cellulose (CMC), ethylene-propylene-diene terpolymer and other binders are mixed, and 1-methyl- After kneading a high boiling point solvent such as 2-pyrrolidone to form a positive electrode mixture, the positive electrode mixture is coated on an aluminum foil or a stainless steel strip of the current collector, dried, and press-molded at about 50-250 ℃. Heat treatment is performed at a temperature of °C under vacuum for about 2 hours.
负极材料Anode material
负极的活性物质可以为能够嵌入或脱嵌锂金属或锂合金中的锂的碳材料，其包括但不限于易石墨化碳、(002)面的晶面距离为0.37nm以上的难石墨化碳、(002)面的晶面距离为0.34nm以下的石墨等。此外，负极活性物质也可以为锡(单质)、锡化合物、硅(单质)、硅化合物、Li 4Ti 5O 12等钛酸锂化合物及其组合。 The active material of the negative electrode can be a carbon material that can intercalate or deintercalate lithium in lithium metal or lithium alloy, including but not limited to easily graphitizable carbon and difficult graphitizable carbon with a crystal plane distance of (002) plane of 0.37 nm or more. , graphite and the like whose crystal plane distance of the (002) plane is 0.34 nm or less. In addition, the negative electrode active material may be a lithium titanate compound such as tin (elemental), tin compound, silicon (elemental), silicon compound, Li 4 Ti 5 O 12 , and combinations thereof.
在一个优选的实施方案中，本发明的蓄电设备使用的负极活性物质选自硅单质、硅化合物、人造石墨、天然石墨或硅氧复合人造石墨。在一个更优选的实施方案中，本发明的蓄电设备使用的负极活性物质选自人造石墨、天然石墨或硅氧复合人造石墨。In a preferred embodiment, the negative electrode active material used in the electricity storage device of the present invention is selected from silicon element, silicon compound, artificial graphite, natural graphite or silicon-oxygen composite artificial graphite. In a more preferred embodiment, the negative electrode active material used in the electricity storage device of the present invention is selected from artificial graphite, natural graphite or silicon-oxygen composite artificial graphite.
负极可以通过如下方法制备：使用与上述的正极的制作同样的导电剂、粘结剂、高沸点溶剂进行混炼而制成负极合剂后，将该负极合剂涂布到集电体的铜箔等上，干燥，加压成型后，在约50-250℃左右的温度下、在真空下进行2小时左右的加热处理。The negative electrode can be prepared by using the same conductive agent, binder, and high-boiling point solvent as those used for the production of the positive electrode described above, kneading to obtain a negative electrode mixture, and then applying the negative electrode mixture to the copper foil of the current collector, etc. After drying and press molding, heat treatment is performed under vacuum at a temperature of about 50-250°C for about 2 hours.
二次电池的制造Manufacture of secondary batteries
本发明的二次电池可以通过如下示例性方法制备：The secondary battery of the present invention can be prepared by the following exemplary methods:
将正负极片与聚乙烯制成的人隔膜按照负极、隔膜、正极、隔膜的方式进行堆叠，并以负极收尾，得到裸电芯。将裸电芯进行热压，使隔膜表面聚偏氟乙烯(PVDF)将各极片粘接在一起。将热压后的裸电芯进行极耳焊接后，置于冲好坑的铝塑膜中，并进行热熔封装，得到留有注液口的预封装后的电池。将预封装的电池置于真空炉中进行充分烘烤干燥后，从注液口注入一定量的电解液，并在真空环境下对注液口进行封装，得到二次电池。The positive and negative electrode sheets and the human separator made of polyethylene are stacked in the manner of negative electrode, separator, positive electrode and separator, and the negative electrode is terminated to obtain a bare cell. The bare cell is hot-pressed so that the polyvinylidene fluoride (PVDF) on the surface of the diaphragm bonds the pole pieces together. After the hot-pressed bare cell is welded with tabs, it is placed in an aluminum-plastic film with a punched hole, and hot-melt packaging is performed to obtain a pre-packaged battery with a liquid injection port. After the pre-packaged battery is placed in a vacuum furnace to be fully baked and dried, a certain amount of electrolyte is injected from the liquid injection port, and the liquid injection port is packaged in a vacuum environment to obtain a secondary battery.
二次电池的性能Performance of Secondary Batteries
本发明的二次电池可以通过如下方法进行测试。The secondary battery of the present invention can be tested by the following method.
(1)二次电池初放电容量测试(1) Initial discharge capacity test of secondary battery
将制备好的电池置于夹具之上，于25℃将该电池以第一恒定电流充电至4.3V，然后第二恒定电流放电至2.8V。任选地，重复上述操作进行第二个循环，以使电池稳定。任选地，进行第三个充放电循环，其中以第三恒定电流充电至4.3V后，以4.3V的恒 定电压实施充电直至电流值达到0.05C电流，并以第五恒定电流放电至2.8V。任选地，进行第四个充放电循环，其中以第六恒定电流充电至4.3V后，以4.3V的恒定电压实施充电直至电流值达到0.05C，并以第七恒定电流放电至2.8V。经过上述操作后，最终可得到初期放电容量。其中第一至第七恒定电流可以为1C、5C、0.1C、0.2C等。1C表示以1小时将电池的基准容量放电的电流值，5C表示上述电流值的5倍，0.1C和0.2C分别表示上述电流值的1/10和1/5。The prepared battery was placed on the jig, and the battery was charged to 4.3V at a first constant current at 25°C, and then discharged to 2.8V at a second constant current. Optionally, repeat the above operation for a second cycle to stabilize the battery. Optionally, a third charge-discharge cycle is performed, wherein after charging to 4.3V at a third constant current, charging at a constant voltage of 4.3V until the current value reaches 0.05C current, and discharging to 2.8V at a fifth constant current . Optionally, a fourth charge-discharge cycle is performed, wherein after the sixth constant current is charged to 4.3V, the charge is performed at a constant voltage of 4.3V until the current value reaches 0.05C, and the seventh constant current is discharged to 2.8V. After the above operations, the initial discharge capacity can be finally obtained. The first to seventh constant currents can be 1C, 5C, 0.1C, 0.2C and so on. 1C represents the current value for discharging the battery at the reference capacity in 1 hour, 5C represents 5 times the above-mentioned current value, and 0.1C and 0.2C represent 1/10 and 1/5 of the above-mentioned current value, respectively.
(2)二次电池循环测试(2) Secondary battery cycle test
以1C的电流在指定电位区间内进行循环充放电，记录每一圈的容量，当电池容量到达首圈容量80％时结束测试。Cycle charge and discharge with a current of 1C within the specified potential range, record the capacity of each cycle, and end the test when the battery capacity reaches 80% of the capacity of the first cycle.
(3)二次电池直流电阻(DCR)测试(3) Secondary battery DC resistance (DCR) test
在指定温度下，将电池以1C电流放电至50％SOC(荷电状态，反映电池的剩余容量)时，将电流调高至4C，并保持30s，检测更新的稳定电压与原平台电压的差，其数值与3C电流值的比值即为电池的直流电阻。将循环结束后的DCR与循环开始时的DCR进行比较得到DCR的增长率。At the specified temperature, when the battery is discharged to 50% SOC (state of charge, reflecting the remaining capacity of the battery) at a current of 1C, the current is increased to 4C, and maintained for 30s, and the difference between the updated stable voltage and the original platform voltage is detected. , the ratio of its value to the 3C current value is the DC resistance of the battery. The DCR growth rate was obtained by comparing the DCR at the end of the cycle with the DCR at the beginning of the cycle.
(4)二次电池产生气体体积变化测试(4) Volume change test of gas generated by secondary battery
将二次电池用细绳固定后完全浸泡入到25℃的水中，记录浸泡前后的重量差，根据25℃下水的密度换算得到体积差。After the secondary battery was fixed with a string, it was completely immersed in water at 25°C, the weight difference before and after the immersion was recorded, and the volume difference was converted according to the density of water at 25°C.
(5)二次电池在60℃时的容量恢复率测试(5) Capacity recovery rate test of secondary battery at 60°C
将充电后的二次电池置于60℃环境中，并放置60天，测量60天后的可逆容量，得到相比60天前的容量恢复率。The charged secondary battery was placed in an environment of 60° C. for 60 days, and the reversible capacity after 60 days was measured to obtain the capacity recovery rate compared to that before 60 days.
在一个实施方案中，本发明的二次电池的初始直流电阻(DCR)为约1.10-1.30mohm。在一个优选的实施方案中，本发明的二次电池的初始直流电阻(DCR)优选为约1.12-1.27mohm。例如约1.10mohm、约1.12mohm、约1.15mohm、约1.17mohm、约1.2mohm、约1.21mohm、约1.22mohm、约1.23mohm、约1.24mohm、约1.25mohm、约1.26mohm、约1.27mohm、约1.28mohm、约1.29mohm、约1.30mohm。In one embodiment, the secondary battery of the present invention has an initial direct current resistance (DCR) of about 1.10-1.30 mohm. In a preferred embodiment, the initial direct current resistance (DCR) of the secondary battery of the present invention is preferably about 1.12-1.27 mohm. For example about 1.10mohm, about 1.12mohm, about 1.15mohm, about 1.17mohm, about 1.2mohm, about 1.21mohm, about 1.22mohm, about 1.23mohm, about 1.24mohm, about 1.25mohm, about 1.26mohm, about 1.27mohm, about 1.28mohm, about 1.29mohm, about 1.30mohm.
在一个实施方案中，经过上述四个充放电循环后，本发明的二次电池的直流电阻增长率为约15％-约35％。在一个优选的实施方案中，经过上述四个充放电循环后，本发明的二次电池的直流电阻增长率为约20％-约32％。例如约20％、约21％、约22％、约23％、约24％、约25％、约26％、约27％、约28％、约29％、约30％、约31％、约32％。In one embodiment, the DC resistance growth rate of the secondary battery of the present invention is about 15% to about 35% after the above-mentioned four charge-discharge cycles. In a preferred embodiment, after the above-mentioned four charge-discharge cycles, the DC resistance growth rate of the secondary battery of the present invention is about 20% to about 32%. For example about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29%, about 30%, about 31%, about 32%.
在一个实施方案中，经过上述四个充放电循环后，本发明的二次电池产生气体体积的增长率为约5％-约20％。在一个优选的实施方案中，经过上述四个充放电循环后，本发明的二次电池产生气体体积的增长率为约8％-约14％。例如为约8％、约9％、约10％、约11％、约12％、约13％、约14％。In one embodiment, after the above-mentioned four charge-discharge cycles, the secondary battery of the present invention produces a volume growth rate of about 5% to about 20%. In a preferred embodiment, after the above-mentioned four charge-discharge cycles, the secondary battery of the present invention produces a volume growth rate of about 8% to about 14%. For example, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%.
在一个实施方案中，将本发明的二次电池放置在60℃环境中60天后，二次电池的直流电阻增长率为约5％-约75％。在一个优选的实施方案中，将本发明的二次电池放置在60℃环境中60天后，二次电池的直流电阻增长率为约5％-约70％。例如约5％、约10％、约15％。In one embodiment, after the secondary battery of the present invention is placed in a 60° C. environment for 60 days, the DC resistance growth rate of the secondary battery is about 5% to about 75%. In a preferred embodiment, after the secondary battery of the present invention is placed in an environment of 60° C. for 60 days, the DC resistance growth rate of the secondary battery is about 5% to about 70%. For example, about 5%, about 10%, about 15%.
在一个实施方案中，将本发明的二次电池放置在60℃环境中60天后，二次电池的容量恢复率为约90％-约98％。在一个优选的实施方案中，将本发明的二次电池放置在60℃环境中60天后，二次电池的容量恢复率为约94％-约97％。In one embodiment, the secondary battery of the present invention has a capacity recovery rate of about 90% to about 98% after being placed in a 60° C. environment for 60 days. In a preferred embodiment, after the secondary battery of the present invention is placed in an environment of 60° C. for 60 days, the capacity recovery rate of the secondary battery is about 94% to about 97%.
在一个实施方案中，将本发明的二次电池放置在60℃环境中60天后，二次电池产生气体体积的增长率为约1％-约50％。在一个优选的实施方案中，本发明的二次电池放置在60℃环境中60天后，二次电池产生气体体积的增长率为约1％-约50％。例如约1％、约2％、约3％、约50％。In one embodiment, after the secondary battery of the present invention is placed in an environment of 60° C. for 60 days, the growth rate of the volume of gas generated by the secondary battery is about 1% to about 50%. In a preferred embodiment, after the secondary battery of the present invention is placed in an environment of 60° C. for 60 days, the volume growth rate of the gas generated by the secondary battery is about 1% to about 50%. For example, about 1%, about 2%, about 3%, about 50%.
在一个实施方案中，将本发明的二次电池放置在-30℃环境中，进行上述四个充放电循环后，本发明的二次电池的直流电阻增长率为约7％。In one embodiment, the secondary battery of the present invention has a DC resistance growth rate of about 7% after the above-mentioned four charge-discharge cycles are placed in an environment of -30°C.
在一个实施方案中，本发明的二次电池达到80％SOH时，其圈数为约1750-2800。在一个优选的实施方案中，本发明的二次电池达到80％SOH时，其圈数为约1894-2781。In one embodiment, the secondary battery of the present invention has a number of turns of about 1750-2800 when it reaches 80% SOH. In a preferred embodiment, the secondary battery of the present invention has a number of turns of about 1894-2781 when it reaches 80% SOH.
电动装置Electric device
在一个方面，本发明提供一种电动装置，其特征在于，所述电动装置包含本发明的蓄电设备。In one aspect, the present invention provides an electric device, characterized in that the electric device includes the power storage device of the present invention.
在一个优选的实施方案中，所述电动装置选自电动汽车、电动两轮车和电力存储***。In a preferred embodiment, the electric device is selected from the group consisting of electric vehicles, electric two-wheelers, and power storage systems.
在一个更优选的实施方案中，所述电动装置为电动汽车，所述电动汽车优选选自电动车(EV)、混合动力车(HEV)、插电式混合动力车(PHEV)。In a more preferred embodiment, the electric device is an electric vehicle, which is preferably selected from an electric vehicle (EV), a hybrid electric vehicle (HEV), and a plug-in hybrid electric vehicle (PHEV).
在又一方面，本发明还涉及式(I)化合物用于非水电解液添加剂的用途。In a further aspect, the present invention also relates to the use of a compound of formula (I) as an additive for non-aqueous electrolytes.
有益效果beneficial effect
以式(I)化合物为非水溶剂电解液的添加剂，能够改善本发明的二次电池的负极成膜，使得本发明的二次电池的循环稳定性可以得到提高。二次电池在经过多次充放电后，二次电池的直流电阻和产生气体体积的增长率均相对较低。另外，在二次电池的非水溶剂电解液中加入式(I)化合物后，二次电池的高温性能，例如高温稳定性等也可以得到改善。其中，将本发明的二次电池放置在60℃环境中60天后，二次电池的直流电阻增长率和产生气体体积的增长率仅有少量变化，并且容量恢复率高达95％以上。此外，在二次电池的非水溶剂电解液中加入式(I)化合物后，二次电池的低温性能同样可以得到改善。Using the compound of formula (I) as the additive of the non-aqueous solvent electrolyte can improve the negative electrode film formation of the secondary battery of the present invention, so that the cycle stability of the secondary battery of the present invention can be improved. After the secondary battery is charged and discharged for many times, the DC resistance of the secondary battery and the growth rate of the generated gas volume are relatively low. In addition, after adding the compound of formula (I) to the non-aqueous solvent electrolyte of the secondary battery, the high temperature performance of the secondary battery, such as high temperature stability, etc., can also be improved. Among them, after the secondary battery of the present invention is placed in an environment of 60° C. for 60 days, the DC resistance growth rate and the growth rate of the generated gas volume of the secondary battery have only a small change, and the capacity recovery rate is as high as 95% or more. In addition, after adding the compound of formula (I) to the non-aqueous solvent electrolyte of the secondary battery, the low temperature performance of the secondary battery can also be improved.
实施例Example
需要说明的是，以下实施例仅仅是为清楚地说明本发明的技术方案所作的举例，而并非对本发明的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其他不同形式的变化或变动，这里无需也无法对所有的实施方式予以穷举，而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。It should be noted that the following examples are only examples for clearly illustrating the technical solutions of the present invention, rather than limiting the present invention. For those of ordinary skill in the art, other different forms of changes or changes can also be made on the basis of the above description, and it is not necessary and impossible to list all the implementations here, and it is obvious from the above. Changes or changes are still within the protection scope of the present invention.
除非另外指明，本文所用的仪器设备和试剂材料均为可商购的。Instrumentation and reagent materials used herein are commercially available unless otherwise indicated.
仪器instrument
温度箱：购自巨孚仪器工业股份有限公司(EEPCT-408-40-SSP-AR)Temperature box: purchased from Jufu Instrument Industry Co., Ltd. (EEPCT-408-40-SSP-AR)
充放电机：购自盛弘(BTS0510C80-HP)Charger and discharger: purchased from Shenghong (BTS0510C80-HP)
材料Material
本文所使用的试剂，例如碳酸乙烯酯、碳酸甲乙酯、碳酸二乙酯和LiPF 6等购自上海国药或Sigma-Aldrich公司。 The reagents used in this paper, such as ethylene carbonate, ethyl methyl carbonate, diethyl carbonate and LiPF 6 , were purchased from Shanghai Sinopharm or Sigma-Aldrich.
化合物的结构通过核磁共振( 19F NMR)和液相色谱-质谱(HPLC-MS确定。 The structures of the compounds were determined by nuclear magnetic resonance ( 19 F NMR) and liquid chromatography-mass spectrometry (HPLC-MS).
19F NMR用Bruker 500MHz AVANCE III核磁仪测定，测定溶剂为氘代氯仿(CDCl 3)，内标为氘代氟仿(CDF 3)，化学位移(δ)以10 -6(ppm)作为单位给出。 19 F NMR was measured by Bruker 500MHz AVANCE III nuclear magnetic instrument, the solvent was deuterated chloroform (CDCl 3 ), the internal standard was deuterated fluoroform (CDF 3 ), and the chemical shift (δ) was given in units of 10 -6 (ppm). out.
液相色谱采用离子色谱。色谱柱：Metrosep ASUPP7-250(4.0mm内径×250mm)。检测器使用Metrohm Model 819电导检测器。离子色谱检测条件如下：Liquid chromatography uses ion chromatography. Chromatographic column: Metrosep ASUPP7-250 (4.0mm inner diameter×250mm). The detector used a Metrohm Model 819 conductance detector. The ion chromatography detection conditions are as follows:
色谱柱温：45℃；流速：0.7mL/min；洗脱剂：10mM的碳酸钠(Na 2CO 3)溶液，35％体积浓度的乙腈；进样体积：100μL；电导检测器检测范围及满量程刻度：100μS/s。 Chromatographic column temperature: 45 °C; flow rate: 0.7 mL/min; eluent: 10 mM sodium carbonate (Na 2 CO 3 ) solution, 35% acetonitrile by volume; injection volume: 100 μL; Range scale: 100μS/s.
质谱使用Agilent 6410三重四极杆质谱进行测定。质谱检测条件如下：Mass spectrometry was performed using an Agilent 6410 triple quadrupole mass spectrometer. The mass spectrometry detection conditions are as follows:
质谱类型为电喷雾离子源(ESI)；雾化器压力：45psig；干燥气体流速：12L/min；干燥气体温度：350℃；毛细管电压：1750V；碎裂电压：120V；碰撞能量：30V。The mass spectrometer type is electrospray ionization (ESI); nebulizer pressure: 45 psig; drying gas flow rate: 12 L/min; drying gas temperature: 350° C.; capillary voltage: 1750V; fragmentation voltage: 120V; collision energy: 30V.
合成实施例Synthesis Example
化合物
Figure PCTCN2020123361-appb-000013
(在本文中又表示为LiSO 2F 3)的合成 compound
Figure PCTCN2020123361-appb-000013
(also referred to herein as LiSO 2 F 3 ) synthesis
将LiF溶于二氟甲烷，以配制成1mM的溶液，在-55℃的温度下，向上述溶液中通入SO 2F 2气体，气压保持在1atm。充分成盐12小时后，在-40℃的温度下，缓慢蒸馏以除去溶剂和多余的气体，得到上述化合物。 LiF was dissolved in difluoromethane to prepare a 1 mM solution, and SO 2 F 2 gas was passed into the above solution at a temperature of -55°C, and the gas pressure was maintained at 1 atm. After sufficient salt formation for 12 hours, the above-mentioned compound was obtained by slow distillation at a temperature of -40° C. to remove the solvent and excess gas.
MS m/z(ESI):121[M] - MS m/z(ESI): 121[M] -
19F NMR(471MHz,CDCl 3)δ:108。 19 F NMR (471 MHz, CDCl 3 ) δ: 108.
化合物
Figure PCTCN2020123361-appb-000014
(在本文中又表示为LiSOF 5)的合成 compound
Figure PCTCN2020123361-appb-000014
(Also referred to herein as LiSOF 5 ) Synthesis
将LiF溶于二氟甲烷，以配制成1mM的溶液，在-55℃的温度下，向上述溶液中通入SOF 4气体，气压保持在1atm。充分成盐12小时后，在-40℃的温度下，缓慢蒸馏以除去溶剂和多余的气体，得到上述化合物。 LiF was dissolved in difluoromethane to prepare a 1 mM solution, and SOF 4 gas was introduced into the above solution at a temperature of -55°C, and the gas pressure was maintained at 1 atm. After sufficient salt formation for 12 hours, the above-mentioned compound was obtained by slow distillation at a temperature of -40° C. to remove the solvent and excess gas.
MS m/z(ESI):143[M] - MS m/z(ESI): 143[M] -
19F NMR(471MHz,CDCl 3)δ:305.5。 19 F NMR (471 MHz, CDCl 3 ) δ: 305.5.
化合物
Figure PCTCN2020123361-appb-000015
(在本文中又表示为TBASO 2F 3)通过与化合物
Figure PCTCN2020123361-appb-000016
相似的方法合成。 compound
Figure PCTCN2020123361-appb-000015
(also referred to herein as TBASO 2 F 3 ) by combining with the compound
Figure PCTCN2020123361-appb-000016
synthesized in a similar manner.
MS m/z(ESI):121[M] - MS m/z(ESI): 121[M] -
19F NMR(471MHz,CDCl 3)δ:108。 19 F NMR (471 MHz, CDCl 3 ) δ: 108.
化合物
Figure PCTCN2020123361-appb-000017
(在本文中又表示为TBASOF 5)通过与化合物
Figure PCTCN2020123361-appb-000018
相似的方法合成。 compound
Figure PCTCN2020123361-appb-000017
(also referred to herein as TBASOF 5 ) by combining with the compound
Figure PCTCN2020123361-appb-000018
synthesized in a similar manner.
MS m/z(ESI):143[M] - MS m/z(ESI): 143[M] -
19F NMR(471MHz,CDCl 3)δ:305.5。 19 F NMR (471 MHz, CDCl 3 ) δ: 305.5.
制备实施例Preparation Examples
二次电池正极的制备Preparation of secondary battery positive electrode
本发明的二次电池的正极可以通过如下方法制备The positive electrode of the secondary battery of the present invention can be prepared by the following method
将正极活性物质、乙炔黑和聚偏氟乙烯(PVDF)加入到无水N-甲基吡咯烷酮溶剂中并混合，以制成浆料，其中正极活性物质、乙炔黑和聚偏氟乙烯(PVDF)的质量比为90:5:5。将获得的浆料涂布在预先涂布有导电助剂的铝箔的一面，其中铝箔的厚度为15μm。对铝箔进行干燥处理后，用辊压机将铝箔的厚度延为80μm。随后将获得的极片裁切为如下的形状，其中活性物质层宽30mm、长40mm，未涂布的部分宽5mm、长9mm。获得的产品即为二次电池的正极极片。The positive active material, acetylene black and polyvinylidene fluoride (PVDF) were added to anhydrous N-methylpyrrolidone solvent and mixed to make a slurry, wherein the positive active material, acetylene black and polyvinylidene fluoride (PVDF) The mass ratio is 90:5:5. The obtained slurry was coated on one side of an aluminum foil pre-coated with a conductive assistant, wherein the thickness of the aluminum foil was 15 μm. After drying the aluminum foil, the thickness of the aluminum foil was extended to 80 μm with a roll press. The obtained pole piece was then cut into a shape in which the active material layer was 30 mm wide and 40 mm long, and the uncoated portion was 5 mm wide and 9 mm long. The obtained product is the positive pole piece of the secondary battery.
二次电池负极的制备Preparation of negative electrode for secondary battery
本发明的二次电池的负极可以通过如下方法制备。The negative electrode of the secondary battery of the present invention can be prepared by the following method.
将负极活性物质、质量分数为1％的羧甲基纤维素钠的水性分散液及质量分数为50％的苯乙烯-丁二烯橡胶的水性分散液混合，以制成浆料，其中负极活性物质、羧甲基纤维素钠的水性分散液和苯乙烯-丁二烯橡胶的水性分散液的质量比为98:100:2。将获得的浆料涂布在厚度为10μm的铜箔的一面。对铜箔进行干燥处理后，用辊压机进行辊压，并将获得的极片裁切为如下的形状，其中活性物质层宽30mm、长40mm，未涂布的部分宽5mm、长9mm。获得的产品即为二次电池的负极极片。Mix the negative electrode active material, an aqueous dispersion of sodium carboxymethyl cellulose with a mass fraction of 1%, and an aqueous dispersion of styrene-butadiene rubber with a mass fraction of 50% to prepare a slurry, in which the negative electrode active material is mixed. The mass ratio of the substance, the aqueous dispersion of sodium carboxymethylcellulose and the aqueous dispersion of styrene-butadiene rubber is 98:100:2. The obtained slurry was coated on one side of a copper foil having a thickness of 10 μm. After the copper foil was dried, it was rolled with a roll press, and the obtained pole piece was cut into the following shape, in which the active material layer was 30 mm wide and 40 mm long, and the uncoated part was 5 mm wide and 9 mm long. The obtained product is the negative pole piece of the secondary battery.
二次电池电解液的制备Preparation of Secondary Battery Electrolyte
本发明的二次电池的电解液可以通过如下方法制备。The electrolytic solution of the secondary battery of the present invention can be prepared by the following method.
在干燥的氩气的气氛中，取不同的非水溶剂并进行混合，随后向混合溶剂中加入充分干燥的锂盐和添加剂，并加入其他添加剂以获得非水电解液。In an atmosphere of dry argon gas, different non-aqueous solvents were taken and mixed, and then fully dried lithium salts and additives were added to the mixed solvent, and other additives were added to obtain a non-aqueous electrolyte.
二次电池的制备Preparation of secondary batteries
本发明的二次电池可以通过如下方法制备。The secondary battery of the present invention can be produced by the following method.
将正极极片、负极极片以及聚乙烯制成的人隔膜按照负极、隔膜、正极、隔膜的方式进行堆叠，并以负极收尾，得到裸电芯。将裸电芯进行热压，使隔膜表面的PVDF将各极片粘接在一起。将热压后的裸电芯进行极耳焊接后，置于冲好坑的铝塑膜中，并进行热熔封装，以获得含有注液口的预封装后的电池。将预封装的电池置于真空炉中进行充分烘烤干燥后，从注液口注入一定量的电解液，并在真空环境下对注液口进行封装，获得本发明的二次电池。The positive pole piece, the negative pole piece and the human separator made of polyethylene are stacked in the manner of negative electrode, separator, positive electrode, and separator, and the negative electrode is terminated to obtain a bare cell. The bare cell is hot-pressed so that the PVDF on the surface of the diaphragm bonds the pole pieces together. After the hot-pressed bare cell is welded with tabs, it is placed in an aluminum-plastic film with a punched hole, and hot-melt packaging is performed to obtain a pre-packaged battery with a liquid injection port. The pre-packaged battery is placed in a vacuum furnace to be fully baked and dried, a certain amount of electrolyte is injected from the liquid injection port, and the liquid injection port is packaged in a vacuum environment to obtain the secondary battery of the present invention.
根据上述方法制备实施例1-10的二次电池。The secondary batteries of Examples 1-10 were prepared according to the above method.
实施例1Example 1
在干燥的氩气氛围中，将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按照3:5:2质量比混合。加入充分干燥的第一锂盐LiPF 6，以使其在非水电解液中的含量为13.0重量％。基于非水电解液的总重量，分别加入以下组分：1.5％的LiPF 2O 2(二氟磷酸锂)和1％的LiFSI(双氟磺酰亚胺锂盐)作为第二锂盐，4％的VC(碳酸亚乙烯酯)、0.5％的PS(1,3-丙磺酸内酯)和1％的LiSO 2F 3，以获得非水电解液。根据上述方法制备二次电池，其中正极活性物质为LiNi 0.65Co 0.15Mn 0.2O 2，负极活性物质为人造石墨。 In a dry argon atmosphere, ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:5:2. The sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 13.0% by weight. Based on the total weight of the non-aqueous electrolyte, the following components were added: 1.5% LiPF 2 O 2 (lithium difluorophosphate) and 1% LiFSI (lithium bisfluorosulfonimide salt) as the second lithium salt, 4 % of VC (vinylene carbonate), 0.5% of PS (1,3-propane sultone), and 1% of LiSO 2 F 3 to obtain a non-aqueous electrolyte. The secondary battery was prepared according to the above method, wherein the positive electrode active material was LiNi 0.65 Co 0.15 Mn 0.2 O 2 , and the negative electrode active material was artificial graphite.
实施例2Example 2
在干燥的氩气氛围中，将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按照3:5:2质量比混合。加入充分干燥的第一锂盐LiPF 6，以使其在非水电解液中的含量为13.0重量％。基于非水电解液的总重量，分别加入以下组分：1.5％的LiPF 2O 2(二氟磷酸锂)和1％的LiFSI(双氟磺酰亚胺锂盐)作为第二锂盐，4％的VC(碳酸亚乙烯酯)、0.5％的PS(1,3-丙磺酸内酯)、0.2％的LiSO 2F 3和0.8％的TBASO 2F 3，以获得非水电解液。根据上述方法制备二次电池，其中正极活性物质为LiNi 0.65Co 0.15Mn 0.2O 2，负极活性物质为人造石墨。 In a dry argon atmosphere, ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:5:2. The sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 13.0% by weight. Based on the total weight of the non-aqueous electrolyte, the following components were added: 1.5% LiPF 2 O 2 (lithium difluorophosphate) and 1% LiFSI (lithium bisfluorosulfonimide salt) as the second lithium salt, 4 % of VC (vinylene carbonate), 0.5% of PS (1,3-propane sultone), 0.2% of LiSO 2 F 3 and 0.8% of TBASO 2 F 3 to obtain a non-aqueous electrolyte. The secondary battery was prepared according to the above method, wherein the positive electrode active material was LiNi 0.65 Co 0.15 Mn 0.2 O 2 , and the negative electrode active material was artificial graphite.
实施例3Example 3
在干燥的氩气氛围中，将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按照3:5:2质量比混合。加入充分干燥的第一锂盐LiPF 6，以使其在非水电解液中的含量为13.0重量％。基于非水电解液的总重量，分别加入以下组分：1.5％的LiPF 2O 2(二氟磷酸锂)和1％的LiFSI(双氟磺酰亚胺锂盐)作为第二锂盐，4％的VC(碳酸亚乙烯酯)、0.5％的PS(1,3-丙磺酸内酯)和1％的LiSOF 5，以获得非水电解液。根据上述方法制备二次电池，其中正极活性物质为LiNi 0.65Co 0.15Mn 0.2O 2，负极活性物质为人造石墨。 In a dry argon atmosphere, ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:5:2. The sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 13.0% by weight. Based on the total weight of the non-aqueous electrolyte, the following components were added: 1.5% LiPF 2 O 2 (lithium difluorophosphate) and 1% LiFSI (lithium bisfluorosulfonimide salt) as the second lithium salt, 4 % of VC (vinylene carbonate), 0.5% of PS (1,3-propane sultone), and 1% of LiSOF 5 to obtain a non-aqueous electrolyte. The secondary battery was prepared according to the above method, wherein the positive electrode active material was LiNi 0.65 Co 0.15 Mn 0.2 O 2 , and the negative electrode active material was artificial graphite.
实施例4Example 4
在干燥的氩气氛围中，将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按照3:5:2质量比混合。加入充分干燥的第一锂盐LiPF 6，以使其在非水电解液中的含量为13.0重量％。基于非水电解液的总重量，分别加入以下组分：1.5％的LiPF 2O 2(二氟磷 酸锂)和1％的LiFSI(双氟磺酰亚胺锂盐)作为第二锂盐，4％的VC(碳酸亚乙烯酯)、0.5％的PS(1,3-丙磺酸内酯)、0.2％的LiSOF 5和0.8％的TBASOF 5，以获得非水电解液。根据上述方法制备二次电池，其中正极活性物质为LiNi 0.65Co 0.15Mn 0.2O 2，负极活性物质为人造石墨。 In a dry argon atmosphere, ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:5:2. The sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 13.0% by weight. Based on the total weight of the non-aqueous electrolyte, the following components were added: 1.5% LiPF 2 O 2 (lithium difluorophosphate) and 1% LiFSI (lithium bisfluorosulfonimide salt) as the second lithium salt, 4 % of VC (vinylene carbonate), 0.5% of PS (1,3-propane sultone), 0.2% of LiSOF 5 and 0.8% of TBASOF 5 to obtain a non-aqueous electrolyte. The secondary battery was prepared according to the above method, wherein the positive electrode active material was LiNi 0.65 Co 0.15 Mn 0.2 O 2 , and the negative electrode active material was artificial graphite.
实施例5Example 5
在干燥的氩气氛围中，将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按照3:5:2质量比混合。加入充分干燥的第一锂盐LiPF 6，以使其在非水电解液中的含量为13.0重量％。基于非水电解液的总重量，分别加入以下组分：1％的LiPF 2O 2(二氟磷酸锂)、1％的LiFSI(双氟磺酰亚胺锂盐)和1％的LiTFSI(双(三氟甲基磺酰)氨基锂)作为第二锂盐，4％的DTD(硫酸乙烯酯)、0.5％的VC(碳酸亚乙烯酯)、1％的PS(1,3-丙磺酸内酯)、0.8％的LiSO 2F 3和0.2％的LiSOF 5，以获得非水电解液。根据上述方法制备二次电池，其中正极活性物质为LiNi 0.55Co 0.15Mn 0.3O 2，负极活性物质为人造石墨。 In a dry argon atmosphere, ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:5:2. The sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 13.0% by weight. Based on the total weight of the non-aqueous electrolyte, the following components were added: 1% LiPF 2 O 2 (lithium difluorophosphate), 1% LiFSI (lithium bisfluorosulfonimide), and 1% LiTFSI (bisfluorosulfonimide) (Lithium trifluoromethylsulfonyl)amide) as second lithium salt, 4% DTD (vinyl sulfate), 0.5% VC (vinylene carbonate), 1% PS (1,3-propanesulfonic acid) lactone), 0.8% LiSO 2 F 3 and 0.2% LiSOF 5 to obtain a non-aqueous electrolyte. A secondary battery was prepared according to the above method, wherein the positive electrode active material was LiNi 0.55 Co 0.15 Mn 0.3 O 2 , and the negative electrode active material was artificial graphite.
实施例6Example 6
在干燥的氩气氛围中，将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按照3:6:1质量比混合。加入充分干燥的第一锂盐LiPF 6，以使其在非水电解液中的含量为13.5重量％。基于非水电解液的总重量，分别加入以下组分：1％的LiPF 2O 2(二氟磷酸锂)、0.5％的LiODFP(双草酸二氟磷酸锂)和0.4％的LiBF 4作为第二锂盐，0.5％的DTD(硫酸乙烯酯)、4％的PC(丙烯酸酯)、0.5％的VC(碳酸亚乙烯酯)、1％的PS(1,3-丙磺酸内酯)、0.5％的LiSO 2F 3和0.5％的LiSOF 5，其中正极活性物质为LiNi 0.55Co 0.15Mn 0.3O 2，负极活性物质为天然石墨。 In a dry argon atmosphere, ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:6:1. The sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolyte solution was 13.5 wt %. Based on the total weight of the non-aqueous electrolyte, the following components were added: 1% LiPF 2 O 2 (lithium difluorophosphate), 0.5% LiODFP (lithium bis-oxalate difluorophosphate), and 0.4% LiBF 4 as a second Lithium salt, 0.5% DTD (vinyl sulfate), 4% PC (acrylate), 0.5% VC (vinylene carbonate), 1% PS (1,3-propane sultone), 0.5 % LiSO 2 F 3 and 0.5% LiSOF 5 , wherein the positive active material is LiNi 0.55 Co 0.15 Mn 0.3 O 2 , and the negative active material is natural graphite.
实施例7Example 7
在干燥的氩气氛围中，将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按照3:5:2质量比混合。加入充分干燥的第一锂盐LiPF 6，以使其在非水电解液中的含量为14重量％。基于非水电解液的总重量，分别加入以下组分：1％的LiPF 2O 2(二氟磷酸锂)和0.5％的LiODFB(二氟草酸硼酸锂)作为第二锂盐，3％的FEC(氟代碳酸乙烯酯)、1％的PS(1,3-丙磺酸内酯)、3％的LiSO 2F 3和3％的LiSOF 5，其中正极活性物质为LiNi 0.8Co 0.1Mn 0.1O 2，负极活性物质为硅氧复合人造石墨。 In a dry argon atmosphere, ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:5:2. The sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 14% by weight. Based on the total weight of the non-aqueous electrolyte, the following components were added: 1% LiPF 2 O 2 (lithium difluorophosphate) and 0.5% LiODFB (lithium difluorooxalate borate) as the second lithium salt, 3% FEC (Fluoroethylene carbonate), 1% PS (1,3-propane sultone), 3% LiSO 2 F 3 and 3% LiSOF 5 , wherein the positive active material is LiNi 0.8 Co 0.1 Mn 0.1 O 2. The negative electrode active material is silicon-oxygen composite artificial graphite.
实施例8Example 8
在干燥的氩气氛围中，将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按照3:4:3质量比混合。加入充分干燥的第一锂盐LiPF 6，以使其在非水电解液中的含量为14重量％。基于非水电解液的总重量，分别加入以下组分：1％的LiPF 2O 2(二氟磷酸锂)、1.5％的LiFSI(双氟磺酰亚胺锂盐)、0.1％的LiBF 4和1％的LiTFSI(双(三氟甲基磺酰)氨基锂)作为第二锂盐，4％的DMC(碳酸二甲酯)、0.5％的VC(碳酸亚乙烯酯)、1.5％的PS(1,3-丙磺酸内酯)、0.5％的LiSO 2F 3和0.5％的LiSOF 5，其中正极活性物质为LiNi 0.65Co 0.15Mn 0.3O 2，负极活性物质为天然石墨。 In a dry argon atmosphere, ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:4:3. The sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 14% by weight. Based on the total weight of the non-aqueous electrolyte, the following components were added: 1% LiPF 2 O 2 (lithium difluorophosphate), 1.5% LiFSI (lithium bisfluorosulfonimide), 0.1% LiBF 4 and 1% LiTFSI (lithium bis(trifluoromethylsulfonyl)amide) as the second lithium salt, 4% DMC (dimethyl carbonate), 0.5% VC (vinylene carbonate), 1.5% PS ( 1,3-propane sultone), 0.5% LiSO 2 F 3 and 0.5% LiSOF 5 , wherein the positive active material is LiNi 0.65 Co 0.15 Mn 0.3 O 2 , and the negative active material is natural graphite.
实施例9Example 9
在干燥的氩气氛围中，将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC) 按照3:5:2质量比混合。加入充分干燥的第一锂盐LiPF 6，以使其在非水电解液中的含量为10重量％。基于非水电解液的总重量，分别加入以下组分：1％的LiFSI(双氟磺酰亚胺锂盐)和1％的LiTFSI(双(三氟甲基磺酰)氨基锂)作为第二锂盐，2％的VC(碳酸亚乙烯酯)、1％的PS(1,3-丙磺酸内酯)、2％的LiSO 2F 3和2％的LiSOF 5，其中正极活性物质为LiNi 0.55Co 0.1Mn 0.35O 2，负极活性物质为人造石墨。 In a dry argon atmosphere, ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:5:2. The sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 10% by weight. Based on the total weight of the non-aqueous electrolyte, the following components were added respectively: 1% LiFSI (lithium bisfluorosulfonimide) and 1% LiTFSI (lithium bis(trifluoromethylsulfonyl)amide) as the second Lithium salt, 2% VC (vinylene carbonate), 1% PS (1,3-propane sultone), 2% LiSO 2 F 3 and 2% LiSOF 5 , wherein the positive active material is LiNi 0.55 Co 0.1 Mn 0.35 O 2 , and the negative electrode active material is artificial graphite.
对比例1Comparative Example 1
在干燥的氩气氛围中，将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按照3:5:2质量比混合。加入充分干燥的第一锂盐LiPF 6，以使其在非水电解液中的含量为13重量％。基于非水电解液的总重量，分别加入以下组分：1.5％的LiPO 2F 2(二氟磷酸锂)和1％的LiFSI(双氟磺酰亚胺锂盐)作为第二锂盐，、4％的VC(碳酸亚乙烯酯)、0.5％的PS(1,3-丙磺酸内酯)，其中正极活性物质为LiNi 0.65Co 0.15Mn 0.2O 2，负极活性物质为人造石墨。 In a dry argon atmosphere, ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:5:2. The sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 13% by weight. Based on the total weight of the non-aqueous electrolyte, the following components were added: 1.5% LiPO 2 F 2 (lithium difluorophosphate) and 1% LiFSI (lithium bisfluorosulfonimide salt) as the second lithium salt, 4% VC (vinylene carbonate), 0.5% PS (1,3-propane sultone), wherein the positive active material is LiNi 0.65 Co 0.15 Mn 0.2 O 2 , and the negative active material is artificial graphite.
对比例2Comparative Example 2
在干燥的氩气氛围中，将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按照3:5:2质量比混合。加入充分干燥的第一锂盐LiPF 6，以使其在非水电解液中的含量为14重量％。基于非水电解液的总重量，分别加入以下组分：1％的LiPO 2F 2(二氟磷酸锂)和0.5％的LiODFB(二氟草酸硼酸锂)作为第二锂盐，3％的FEC(氟代碳酸乙烯酯)、1％的PS(1,3-丙磺酸内酯)，其中正极活性物质为LiNi 0.8Co 0.1Mn 0.1O 2，负极活性物质为硅氧复合人造石墨。 In a dry argon atmosphere, ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a mass ratio of 3:5:2. The sufficiently dried first lithium salt LiPF 6 was added so that its content in the non-aqueous electrolytic solution was 14% by weight. Based on the total weight of the non-aqueous electrolyte, the following components were added: 1% LiPO 2 F 2 (lithium difluorophosphate) and 0.5% LiODFB (lithium difluorooxalate borate) as the second lithium salt, 3% FEC (fluoroethylene carbonate), 1% PS (1,3-propane sultone), wherein the positive active material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 , and the negative active material is silicon-oxygen composite artificial graphite.
测试test
本发明的二次电池可以通过如下方法进行测试。The secondary battery of the present invention can be tested by the following method.
(1)二次电池初放电容量及循环测试(1) Initial discharge capacity and cycle test of secondary battery
将制备好的电池进行化成老化处理后置于夹具之上，在25℃下，以1C的电流将活化后的电池充电至4.3V，并恒压至0.05C电流，再以1C放电至2.8V，记录放电容量。首圈放电记录电池初始DCR，其后进行循环测试至电池放电容量为首圈容量的80％时停止，记录循环结束后电池的DCR、DCR增长率、电池达到80％SOH(电池健康状态)的圈数和产气体积变化。The prepared battery was subjected to chemical aging treatment and placed on the fixture. At 25°C, the activated battery was charged to 4.3V with a current of 1C, and the current was constant voltage to 0.05C, and then discharged to 2.8V at 1C. , and record the discharge capacity. The initial DCR of the battery is recorded in the first cycle of discharge, and then the cycle test is performed until the battery discharge capacity is 80% of the capacity of the first cycle, and the DCR, DCR growth rate of the battery after the end of the cycle, and the cycle when the battery reaches 80% SOH (battery state of health) are recorded. and gas production volume changes.
其中二次电池的直流电阻以及产生气体体积的变化分别通过如下方法进行测定：The DC resistance of the secondary battery and the change in the volume of the generated gas are measured by the following methods:
(i)二次电池直流电阻(DCR)测试(i) Secondary battery DC resistance (DCR) test
在指定温度下，将电池以1C电流放电至50％SOC(荷电状态，反映电池的剩余容量)时，将电流调高至4C，并保持30s，检测更新的稳定电压与原平台电压的差，其数值与3C电流值的比值即为电池的直流电阻。将循环结束后的DCR与循环开始时的DCR进行比较得到DCR的增长率。At the specified temperature, when the battery is discharged to 50% SOC (state of charge, reflecting the remaining capacity of the battery) at a current of 1C, the current is increased to 4C, and maintained for 30s, and the difference between the updated stable voltage and the original platform voltage is detected. , the ratio of its value to the 3C current value is the DC resistance of the battery. The DCR growth rate was obtained by comparing the DCR at the end of the cycle with the DCR at the beginning of the cycle.
(ii)二次电池产生气体体积变化测试(ii) Test of volume change of gas generated by secondary battery
将二次电池用细绳固定后完全浸泡入到25℃的水中，记录浸泡前后的重量差，根据25℃下水的密度换算得到体积差。After the secondary battery was fixed with a string, it was completely immersed in water at 25°C, the weight difference before and after the immersion was recorded, and the volume difference was converted according to the density of water at 25°C.
(2)二次电池在60℃时的容量恢复率测试(2) Capacity recovery rate test of secondary battery at 60°C
将实施例5、6、7、对比例2进行老化处理后，在25℃下，以1C的电流将活化后的电池充电到4.3V，并恒压至0.05C电流。再将二次电池置于60℃环境60天，记录其60天容量恢复率。After aging treatment of Examples 5, 6, 7, and Comparative Example 2, the activated batteries were charged to 4.3V with a current of 1C at 25°C, and the current was maintained at a constant voltage of 0.05C. The secondary battery was then placed in an environment of 60°C for 60 days, and the 60-day capacity recovery rate was recorded.
(3)二次电池在60℃下的循环测试(3) Cycle test of secondary battery at 60°C
将实施例5、6和7、对比例2进行老化处理后，在60℃下，以1C的电流将活化后的电池充电到4.25V，并恒压至0.05C电流，再以1C放电至3.0V，记录放电容量。首圈放电记录电池初始DCR，其后进行循环测试至电池放电容量为首圈容量的80％时停止，记录循环结束后电池的DCR、DCR增长率和产气体积变化。After the aging treatment of Examples 5, 6 and 7, and Comparative Example 2, the activated batteries were charged to 4.25V at a current of 1C at 60°C, and the current was maintained at a constant voltage of 0.05C, and then discharged to 3.0 at 1C. V, record the discharge capacity. The initial DCR of the battery was recorded in the first cycle of discharge, and then the cycle test was performed until the battery discharge capacity was 80% of the first cycle capacity, and the DCR, DCR growth rate and gas production volume change of the battery were recorded after the cycle.
(4)二次电池在-30℃下的循环测试(4) Cycle test of secondary battery at -30°C
将实施例6化成老化后，在-30℃下以1C的电流将活化后的电池充电到4.25V，并恒压至0.05C电流，再以1C放电至3.0V，记录放电容量。首圈放电记录电池初始DCR，其后进行循环测试至电池放电容量为首圈容量的80％时停止，记录循环结束后电池的DCR增长率。After chemical aging of Example 6, the activated battery was charged to 4.25V at a current of 1C at -30°C, and the current was maintained at a constant voltage of 0.05C, and then discharged to 3.0V at 1C, and the discharge capacity was recorded. The initial DCR of the battery was recorded in the first cycle of discharge, and then the cycle test was performed until the battery discharge capacity was 80% of the capacity of the first cycle, and the DCR growth rate of the battery after the cycle was recorded.
结果result
表1为实施例1-9的二次电池的初放电容量测试、循环测试、直流电阻(DCR)测试、产生气体体积变化测试的结果。表2为实施例5-7的二次电池在60℃和-30℃时的容量恢复率测试结果。Table 1 shows the results of the initial discharge capacity test, cycle test, direct current resistance (DCR) test, and gas generation volume change test of the secondary batteries of Examples 1-9. Table 2 shows the test results of the capacity recovery rate of the secondary batteries of Examples 5-7 at 60°C and -30°C.
表1Table 1
实施例Example SOH圈数 a SOH turns a 初始DCR(mohm)Initial DCR (mohm) DCR增长率 b DCR growth rateb 产气体积增长率Gas volume growth rate
11 25232523 1.171.17 20％20% 8％8%
22 25302530 1.251.25 22％twenty two% 12％12%
33 24312431 1.21.2 21％twenty one% 9％9%
44 24442444 1.271.27 24％twenty four% 13％13%
55 27812781 1.211.21 22％twenty two% 9％9%
66 23412341 1.181.18 23％twenty three% 10％10%
77 20092009 1.211.21 32％32% 14％14%
88 20542054 1.231.23 27％27% 12％12%
99 18941894 1.121.12 24％twenty four% 12％12%
a25℃下，电池达到80％SOH的圈数； b循环末期DCR增长率 a The number of turns for the battery to reach 80% SOH at 25°C; b DCR growth rate at the end of the cycle
如表1所示，实施例1-9的二次电池具有较低的初始直流电阻，仅为约1.12-1.27mohm。在经过充放电循环后，实施例1-9的二次电池的直流电阻增长率也相对降低，仅为约20％-约32％，并且二次电池产生气体体积的增长率更低，仅为约8％-约14％。由此可见，以式(I)的化合物为添加剂，本发明的二次电池具有较好的稳定性，经过多次 充放电循环后，二次电池的直流电阻仅有少量升高，产生气体的体积变化不大。另外，实施例1-9的二次电池达到80％SOH时，具有较高的圈数，为1894-2781。由此可见，以式(I)的化合物为添加剂，本发明的二次电池具有较长时间的使用寿命。As shown in Table 1, the secondary batteries of Examples 1-9 had lower initial DC resistances of only about 1.12-1.27 mohm. After the charge-discharge cycle, the DC resistance growth rate of the secondary batteries of Examples 1-9 is also relatively reduced, only about 20% to about 32%, and the growth rate of the gas volume generated by the secondary battery is even lower, only about 20% to 32%. About 8% - about 14%. It can be seen that, using the compound of formula (I) as an additive, the secondary battery of the present invention has good stability. The volume doesn't change much. In addition, when the secondary batteries of Examples 1-9 reached 80% SOH, they had a relatively high number of turns, ranging from 1894 to 2781. It can be seen that, with the compound of formula (I) as an additive, the secondary battery of the present invention has a longer service life.
表2Table 2
实施例Example DCR增长率 a DCR growth ratea 容量恢复率 b Capacity recovery rateb 产气体积增长率 c Gas production volume growth rate c DCR增长率 d DCR growth rate d
55 10％10% 96％96% 2％2%   
66 5％5% 97％97% 2％2% 7％7%
77 15％15% 94％94% 3％3%   
a60℃下60天后DCR增长率； b60℃下60天后容量恢复率； c60℃下60天后产气体积增长率； d-30℃循环结束DCR增长率； a DCR growth rate after 60 days at 60°C; b capacity recovery rate after 60 days at 60°C; c gas production volume growth rate after 60 days at 60°C; d DCR growth rate at the end of -30°C cycle;
在实施例5-7中，加入其他添加剂DTD(硫酸乙烯酯)、PC(丙烯酸酯)或FEC(氟代碳酸乙烯酯)，与式(I)的化合物共同作用，有利于提高电池的高温稳定性或低温稳定性。如表2所示，本发明的二次电池具有优秀的高温性能，在高温(例如约60℃)下经过多次充放电，二次电池的直流电阻增长率仅为5％-15％，容量恢复率可达94％-97％，且产气体积增长率仅为2-3％。而在低温(例如约-30℃)下经过多次充放电，二次电池的直流电阻增长率仅为7％。此可见，以式(I)的化合物为添加剂，与其他添加剂共同作用，有利于进一步提高二次电池的高温和低温稳定性。In Examples 5-7, other additives DTD (vinyl sulfate), PC (acrylate) or FEC (fluoroethylene carbonate) are added to act together with the compound of formula (I), which is beneficial to improve the high temperature stability of the battery properties or low temperature stability. As shown in Table 2, the secondary battery of the present invention has excellent high-temperature performance. After repeated charging and discharging at high temperature (for example, about 60° C.), the DC resistance growth rate of the secondary battery is only 5%-15%, and the capacity of the secondary battery is only 5%-15%. The recovery rate can reach 94%-97%, and the growth rate of gas production volume is only 2-3%. However, the DC resistance growth rate of the secondary battery is only 7% at low temperature (eg, about -30° C.) after repeated charging and discharging. It can be seen that using the compound of formula (I) as an additive and acting together with other additives is beneficial to further improve the high temperature and low temperature stability of the secondary battery.
表3为对比例的二次电池的初放电容量测试、循环测试、直流电阻(DCR)测试、产生气体体积变化测试和二次电池在60℃时的容量恢复率测试结果，测试条件与表1所用的相同。Table 3 shows the results of the initial discharge capacity test, cycle test, direct current resistance (DCR) test, gas volume change test and capacity recovery rate test results of the secondary battery at 60°C of the secondary battery of the comparative example. The test conditions are the same as those in Table 1. used the same.
表3table 3
对比例Comparative ratio SOH圈数 a SOH turns a 初始DCR(mohm)Initial DCR (mohm) DCR增长率 b DCR growth rateb 产气体积增长率Gas volume growth rate
11 12971297 1.431.43 40％40% 37％37%
22 573573 1.591.59 70％70% 90％90%
a25℃下，电池达到80％SOH的圈数； b循环末期DCR增长率 a The number of turns for the battery to reach 80% SOH at 25°C; b DCR growth rate at the end of the cycle
如表3所示，相比实施例3和7，对比例1和2未加入式(I)的化合物，得到的二次电池达到80％SOH时，其具有的圈数仅为573-1297，远低于实施例1-9。由此可见，式(I)化合物作为添加剂，能够有效地提高二次电池的使用寿命。另外，相比实施例1-9，对比例1-2具有相对较高的DCR，电池工作效率降低。此外，对比例1-2具有明显提高的DCR增长率和产气体积增长率。由此可见，式(I)化合物作为添加剂，能有效提高二次电池的稳定性，降低DCR增长率和产气体积增长率。As shown in Table 3, compared with Examples 3 and 7, when the compound of formula (I) was not added in Comparative Examples 1 and 2, when the obtained secondary battery reached 80% SOH, the number of turns was only 573-1297, Much lower than Examples 1-9. It can be seen that the compound of formula (I) can effectively improve the service life of the secondary battery as an additive. In addition, compared with Examples 1-9, Comparative Examples 1-2 have relatively higher DCR, and the battery operating efficiency is reduced. In addition, Comparative Examples 1-2 have significantly improved DCR growth rates and gas production volume growth rates. It can be seen that, as an additive, the compound of formula (I) can effectively improve the stability of the secondary battery and reduce the DCR growth rate and the gas production volume growth rate.
表4为对比例2的二次电池在60℃时的DCR增长率、容量恢复率和产气体积增长率测试结果，测试条件与表2所用的相同。Table 4 shows the test results of DCR growth rate, capacity recovery rate and gas production volume growth rate of the secondary battery of Comparative Example 2 at 60° C. The test conditions are the same as those used in Table 2.
表4Table 4
对比例Comparative ratio DCR增长率 a DCR growth ratea 容量恢复率 b Capacity recovery rateb 产气体积增长率 c Gas production volume growth rate c
22 6767 8484 23twenty three
a60℃下60天后DCR增长率； b60℃下60天后容量恢复率； c60℃下60天后产气体积增长率 a DCR growth rate after 60 days at 60°C; b capacity recovery rate after 60 days at 60°C; c gas production volume growth rate after 60 days at 60°C
如表4所示，相比实施例7，将对比例2的二次电池置于60℃的环境下60天后，二次电池具有明显更高的DCR增长率和相对较低的容量恢复率，因此式(I)化合物作为添加剂可以提高二次电池的高温性能。As shown in Table 4, compared with Example 7, the secondary battery of Comparative Example 2 had a significantly higher DCR growth rate and a relatively lower capacity recovery rate after being placed in an environment of 60°C for 60 days. Therefore, the compound of formula (I) can improve the high temperature performance of the secondary battery as an additive.
以上所述仅为本发明的具体实施例，并非因此限制本发明的专利范围，凡是利用本发明作的等效变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围之中。The above are only specific embodiments of the present invention, and are not intended to limit the scope of the present invention. All equivalent transformations made by the present invention, or directly or indirectly applied in other related technical fields, are similarly included in the present invention. within the scope of patent protection.

Claims (20)

  1. 式(I)所示的化合物：The compound represented by formula (I):
    Figure PCTCN2020123361-appb-100001
    Figure PCTCN2020123361-appb-100001
    其特征在于，It is characterized in that,
    R各自独立地选自卤素、卤代C 1-10烷基、卤代C 3-10环烷基； Each R is independently selected from halogen, halogenated C 1-10 alkyl, halogenated C 3-10 cycloalkyl;
    m为1-3的整数；m is an integer from 1 to 3;
    n为1或2；n is 1 or 2;
    M为反荷阳离子。M is a counter cation.
  2. 权利要求1所述的化合物，其特征在于，The compound of claim 1, wherein
    R各自独立地选自卤素，优选氟、氯或溴，更优选为氟。R is each independently selected from halogen, preferably fluorine, chlorine or bromine, more preferably fluorine.
  3. 权利要求1或2所述的化合物，其特征在于，The compound of claim 1 or 2, characterized in that,
    所述反荷阳离子为金属阳离子或季胺基团。The counter cation is a metal cation or a quaternary amine group.
  4. 权利要求3所述的化合物，其特征在于，The compound of claim 3, wherein
    所述金属阳离子选自锂离子、钠离子、钾离子、钙离子、镁离子及其组合，优选为锂离子；The metal cation is selected from lithium ion, sodium ion, potassium ion, calcium ion, magnesium ion and combinations thereof, preferably lithium ion;
    所述季胺基团选自四甲基胺、四乙基胺、四丙基胺、四丁基胺，优选为四丁基胺。The quaternary amine group is selected from tetramethylamine, tetraethylamine, tetrapropylamine, tetrabutylamine, preferably tetrabutylamine.
  5. 权利要求1-4中任一项所述的化合物，其特征在于，The compound of any one of claims 1-4, characterized in that,
    所述式(I)的化合物选自The compound of formula (I) is selected from
    Figure PCTCN2020123361-appb-100002
    及其组合，
    Figure PCTCN2020123361-appb-100002
    and its combination,
    其中M和m如权利要求1-4之一所定义；wherein M and m are as defined in one of claims 1-4;
    特别地，M m+为权利要求3或4所定义的金属阳离子或季胺基团， In particular, M m+ is a metal cation or a quaternary amine group as defined in claim 3 or 4,
    m为1-3的整数。m is an integer of 1-3.
  6. 权利要求1-5中任一项所述的化合物，其特征在于，The compound of any one of claims 1-5, characterized in that,
    所述式(I)的化合物选自The compound of formula (I) is selected from
    Figure PCTCN2020123361-appb-100003
    Figure PCTCN2020123361-appb-100004
    及其组合。
    Figure PCTCN2020123361-appb-100003
    Figure PCTCN2020123361-appb-100004
    and its combinations.
  7. 一种非水电解液用添加剂，其含有权利要求1-6中任一项所述的式(I)所示的化合物。An additive for a non-aqueous electrolyte solution, comprising the compound represented by the formula (I) according to any one of claims 1-6.
  8. 一种非水电解液，其包含权利要求1-6中任一项所述的式(I)所示的化合物或者权利要求7所述的添加剂。A non-aqueous electrolyte solution comprising the compound represented by the formula (I) according to any one of claims 1 to 6 or the additive according to claim 7 .
  9. 权利要求8所述的非水电解液，其特征在于，The non-aqueous electrolyte according to claim 8, characterized in that,
    基于非水电解液的总重量，式(I)所示的化合物在所述非水电解液中的含量为约0.1-10重量％，优选为约0.2-7重量％，更优选为约1重量％。Based on the total weight of the non-aqueous electrolyte, the content of the compound represented by the formula (I) in the non-aqueous electrolyte is about 0.1-10% by weight, preferably about 0.2-7% by weight, more preferably about 1% by weight %.
  10. 权利要求8或9所述的非水电解液，其特征在于，The non-aqueous electrolyte according to claim 8 or 9, characterized in that,
    所述非水电解液还包含非水溶剂，The non-aqueous electrolyte also contains a non-aqueous solvent,
    其中，非水溶剂选自环状酯、链状酯及其组合；Wherein, the non-aqueous solvent is selected from cyclic esters, chain esters and combinations thereof;
    所述环状酯优选为环状碳酸酯；The cyclic ester is preferably a cyclic carbonate;
    所述链状酯优选为链状碳酸酯。The chain ester is preferably a chain carbonate.
  11. 权利要求12所述的非水电解液，其特征在于，The non-aqueous electrolyte of claim 12, wherein
    所述环状碳酸酯选自碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、碳酸1,2-丁烯酯、碳酸2,3-丁烯酯、4-氟-1,3-二氧杂环戊烷-2-酮、反式或顺式4,5-二氟-1,3-二氧杂环戊烷-2-酮、氟代碳酸乙烯酯、碳酸亚乙烯酯、碳酸乙烯基亚乙酯及其组合，优选选自碳酸乙烯酯、碳酸丙烯酯、碳酸亚乙烯酯、氟代碳酸乙烯酯或碳酸丁烯酯及其组合，更优选选自碳酸乙烯酯、碳酸亚乙烯酯、氟代碳酸乙烯酯及其组合。The cyclic carbonate is selected from ethylene carbonate, propylene carbonate, butene carbonate, 1,2-butene carbonate, 2,3-butene carbonate, 4-fluoro-1,3-dioxa Cyclopentan-2-one, trans or cis 4,5-difluoro-1,3-dioxolane-2-one, fluoroethylene carbonate, vinylene carbonate, vinylene carbonate Ethyl carbonate and combinations thereof, preferably selected from ethylene carbonate, propylene carbonate, vinylene carbonate, fluoroethylene carbonate or butylene carbonate and combinations thereof, more preferably selected from ethylene carbonate, vinylene carbonate, fluorine Substituted ethylene carbonate and combinations thereof.
  12. 权利要求10或11所述的非水电解液，其特征在于，所述链状酯选自甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸丁酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸丁酯、碳酸甲乙酯、甲基丙基碳酸酯、碳酸二甲酯、碳酸二乙酯、乙基丙基碳酸酯、碳酸二丙酯及其组合，优选选自碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯及其组合。The non-aqueous electrolyte according to claim 10 or 11, wherein the chain ester is selected from methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate ester, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, ethyl methyl carbonate , methylpropyl carbonate, dimethyl carbonate, diethyl carbonate, ethylpropyl carbonate, dipropyl carbonate and combinations thereof, preferably selected from dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and its combinations.
  13. 权利要求8-12中任一项所述的非水电解液，其特征在于，The non-aqueous electrolyte solution according to any one of claims 8-12, characterized in that,
    所述非水电解液还包含第一锂盐；The non-aqueous electrolyte also includes a first lithium salt;
    所述第一锂盐优选选自LiPF 6、LiBF 4、LiBCl 4、LiAsF 6、LiClO 4、LiAlO 2、LiF、LiCl、LiBr、LiI、LiSbF 6及其组合，更优选选自LiPF 6、LiBF 4及其组合。 The first lithium salt is preferably selected from LiPF 6 , LiBF 4 , LiBCl 4 , LiAsF 6 , LiClO 4 , LiAlO 2 , LiF, LiCl, LiBr, LiI, LiSbF 6 and combinations thereof, more preferably selected from LiPF 6 , LiBF 4 and its combinations.
  14. 权利要求8-13中任一项所述的非水电解液，其特征在于，The non-aqueous electrolyte solution according to any one of claims 8-13, characterized in that,
    所述非水电解液还包含第二锂盐，其选自含P＝O结构的锂盐、含-S(＝O) 2-结构的锂盐、含硼草酸络合物作为阴离子的锂盐及其组合； The non-aqueous electrolyte further comprises a second lithium salt selected from the group consisting of a lithium salt containing a P=O structure, a lithium salt containing a -S(=O) 2 - structure, and a lithium salt containing a boron oxalic acid complex as an anion and combinations thereof;
    所述第二锂盐优选选自LiPO 2F 2、Li 2PO 3F、LiODFB、LiODFP、LiBOB、LiTFSI、LiFSI及其组合，更优选选自LiPO 2F 2、LiODFB、LiODFP、LiBOB、LiTFSI、LiFSI及其组合。 The second lithium salt is preferably selected from LiPO 2 F 2 , Li 2 PO 3 F, LiODFB, LiODFP, LiBOB, LiTFSI, LiFSI and combinations thereof, more preferably selected from LiPO 2 F 2 , LiODFB, LiODFP, LiBOB, LiTFSI, LiFSI and combinations thereof.
  15. 权利要求8-14中任一项所述的非水电解液，其特征在于，The non-aqueous electrolyte solution according to any one of claims 8-14, characterized in that,
    所述第一锂盐和第二锂盐的总含量为约10-20重量％，优选为约12-17.6重量％，更优选为约15.4-16.3重量％；The total content of the first lithium salt and the second lithium salt is about 10-20% by weight, preferably about 12-17.6% by weight, more preferably about 15.4-16.3% by weight;
    优选第一锂盐的含量为约8-16重量％，更优选约10-14重量％，特别优选为约13-13.5重量％。Preferably, the content of the first lithium salt is about 8-16% by weight, more preferably about 10-14% by weight, and particularly preferably about 13-13.5% by weight.
  16. 权利要求8-15中任一项所述的非水电解液，其特征在于，所述非水电解液还任选地包含选自以下的一种或多种的添加剂：碳酸亚乙烯酯、氟代碳酸乙烯酯、碳酸二甲酯、1,3-丙磺酸内酯、硫酸乙烯酯、碳酸丙烯酯。The non-aqueous electrolyte solution according to any one of claims 8-15, wherein the non-aqueous electrolyte solution also optionally comprises one or more additives selected from the group consisting of: vinylene carbonate, fluorine Ethylene carbonate, dimethyl carbonate, 1,3-propane sultone, ethylene sulfate, propylene carbonate.
  17. 权利要求16所述的非水电解液，其特征在于，所述添加剂的含量为约0-10重量％，优选为约3-6重量％，更优选为约4.5-6重量％。The non-aqueous electrolyte solution of claim 16, wherein the content of the additive is about 0-10% by weight, preferably about 3-6% by weight, more preferably about 4.5-6% by weight.
  18. 一种蓄电设备，其特征在于，An electrical storage device, characterized in that:
    所述蓄电设备包含权利要求1-6中任一项所述的式(I)所示的化合物或者权利要求8-17任一项所述的非水电解液；The electrical storage device comprises the compound represented by the formula (I) according to any one of claims 1-6 or the non-aqueous electrolyte solution according to any one of claims 8-17;
    优选地，所述蓄电设备为二次电池。Preferably, the power storage device is a secondary battery.
  19. 一种电动装置，其特征在于，An electric device, characterized in that:
    所述电动装置包含权利要求18所述的蓄电设备；The electric device includes the power storage device of claim 18;
    优选地，所述电动装置选自电动汽车、电动两轮车和电力存储***；Preferably, the electric device is selected from an electric vehicle, an electric two-wheeled vehicle and a power storage system;
    所述电动汽车优选选自电动车、混合动力车、插电式混合动力车。The electric vehicle is preferably selected from an electric vehicle, a hybrid vehicle, and a plug-in hybrid vehicle.
  20. 权利要求1-6中任一项所述的式(I)所示的化合物用于非水电解液添加剂的用途。Use of the compound represented by the formula (I) according to any one of claims 1 to 6 for a non-aqueous electrolyte additive.
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