WO2018094843A1 - 一种用于锂离子电池的非水电解液及锂离子电池 - Google Patents

一种用于锂离子电池的非水电解液及锂离子电池 Download PDF

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WO2018094843A1
WO2018094843A1 PCT/CN2016/113649 CN2016113649W WO2018094843A1 WO 2018094843 A1 WO2018094843 A1 WO 2018094843A1 CN 2016113649 W CN2016113649 W CN 2016113649W WO 2018094843 A1 WO2018094843 A1 WO 2018094843A1
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group
phosphate
carbonate
compound
structural formula
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French (fr)
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石桥
林木崇
胡时光
林雄贵
贠娇娇
曾长安
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Shenzhen Capchem Technology Co Ltd
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Shenzhen Capchem Technology Co Ltd
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Priority claimed from CN201611054855.8A external-priority patent/CN106953118B/zh
Priority claimed from CN201611063485.4A external-priority patent/CN108110318B/zh
Priority claimed from CN201611055698.2A external-priority patent/CN108110322A/zh
Application filed by Shenzhen Capchem Technology Co Ltd filed Critical Shenzhen Capchem Technology Co Ltd
Priority to EP16922345.0A priority Critical patent/EP3547433A4/en
Priority to US16/316,621 priority patent/US11362370B2/en
Priority to JP2018564811A priority patent/JP6814821B2/ja
Publication of WO2018094843A1 publication Critical patent/WO2018094843A1/zh
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Priority to US17/735,109 priority patent/US11757132B2/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
    • H01M10/056—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/10—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms two oxygen atoms and one sulfur atom, e.g. cyclic sulfates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/062—Organo-phosphoranes without P-C bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/113—Esters of phosphoric acids with unsaturated acyclic alcohols
    • 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
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0034—Fluorinated solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the field of lithium ion battery electrolytes, and more particularly to a nonaqueous electrolyte and a lithium ion battery for a lithium ion battery.
  • Lithium-ion batteries have the characteristics of high specific energy, large specific power and long cycle life. They are mainly used in 3C digital consumer electronics and new energy power vehicles and energy storage. With the continuous improvement of the requirements for the cruising range of new energy vehicles and the miniaturization of the size of digital consumer electronics products, high energy density has become the main development trend of lithium ion batteries. Increasing the operating voltage of lithium-ion batteries is an effective way to increase the energy density of batteries.
  • Increasing the operating voltage of a lithium-ion battery tends to degrade performance. Because at high voltage, on the one hand, there is a certain instability in the crystal structure of the positive electrode of the battery. In the process of charging and discharging, the collapse of the structure may occur and the performance is deteriorated. On the other hand, at a high voltage, the surface of the positive electrode is at a high voltage. In the high oxidation state, the activity is high, and it is easy to catalyze the oxidative decomposition of the electrolyte. The decomposition products of the electrolyte are easily deposited on the surface of the positive electrode, blocking the deintercalation channel of lithium ions, thereby deteriorating the battery performance.
  • the electrolyte is a key factor affecting the overall performance of the battery.
  • the additives in the electrolyte are particularly important for the performance of the battery. Therefore, in order to give full play to the performance of the power battery of the ternary nickel-cobalt-manganese material, the matching of the electrolyte is the key.
  • the currently practical lithium ion battery electrolyte is a non-aqueous electrolyte added with a conventional film-forming additive such as vinylene carbonate (abbreviation VC) or fluoroethylene carbonate (abbreviated as FEC), and the battery is excellent by the addition of VC and FEC. Cyclic performance.
  • VC vinylene carbonate
  • FEC fluoroethylene carbonate
  • Patent application No. 201410534841.0 discloses a novel film-forming additive for a phosphate compound containing a triple bond, which not only improves high temperature cycle performance, but also significantly improves storage performance.
  • the three-bond phosphate ester additive can not only form a film on the positive electrode, but also form a film on the negative electrode.
  • the film formation in the negative electrode will significantly increase the impedance of the negative electrode and significantly degrade the low temperature. performance.
  • the cyclic unsaturated carboxylic anhydride compound as a lithium battery electrolyte additive has also been found in some related literatures and patents.
  • the cyclic unsaturated carboxylic anhydride has similar functional characteristics to the triple bond phosphate ester, and can also significantly improve high temperature performance, but At the same time, it will increase the battery impedance, degrade the low temperature performance, and inhibit the application of non-aqueous lithium ion batteries under low temperature conditions.
  • An object of the present application is to provide a nonaqueous electrolyte for a lithium ion battery and a nonaqueous electrolyte using the lithium ion battery.
  • An aspect of the present application discloses a nonaqueous electrolyte for a lithium ion battery, comprising an unsaturated phosphate compound and an unsaturated cyclic carboxylic acid compound having the structural formula 4 structure,
  • R 13 , R 11 and R 12 are each independently selected from a hydrocarbon group having 1 to 5 carbon atoms, and at least one of R 13 , R 11 and R 12 is an unsaturated hydrocarbon group having a double bond or a triple bond;
  • the unsaturated cyclic carboxylic anhydride compound has a structure represented by Structural Formula 5,
  • R 14 is selected from an alkenylene group having 2 to 4 carbon atoms or an alkenylene group having 2 to 4 carbon atoms.
  • the technical principle of simultaneously adding an unsaturated phosphate compound and a cyclic unsaturated carboxylic anhydride compound is that during the first charging process, an unsaturated phosphate compound forms a film on the negative electrode, and a passivation film of the compound in the negative electrode is formed.
  • the poor conductivity will significantly increase the impedance of the negative electrode, resulting in a significant increase in the overall impedance of the battery and poor low temperature performance.
  • the unsaturated cyclic carboxylic anhydride compound also has a strong negative film forming function during the first charging process, which is mainly reflected in the high film forming potential of the negative electrode of the compound, and the preferential formation of the unsaturated phosphate compound in the negative electrode.
  • the unsaturated phosphate ester (Compound 1) starts to form a negative electrode at about 2.7 V during the first charging process, and the film formation at the negative electrode causes a significant increase in the impedance of the negative electrode;
  • the unsaturated unsaturated carboxylic acid anhydride compound (CA) is added to the unsaturated phosphate ester (Compound 1), and the cyclic unsaturated carboxylic acid anhydride compound (CA) preferentially forms a film on the surface of the negative electrode at about 1.5 V and 2 V, and The film formed by the cyclic unsaturated carboxylic anhydride compound (CA) preferentially inhibits the film formation of the unsaturated phosphate (Compound 1) at the subsequent 2.7 V, thereby lowering the impedance of the negative electrode.
  • the unsaturated phosphate compound represented by the above formula 1 may be selected from the compounds of the following structural formula:
  • the unsaturated phosphate compound shown in Formula 1, or the unsaturated phosphate compound of Compound 1 to Compound 6, is a preferred technical solution of the present application, and does not exclude other compounds having similar physical and chemical properties. Saturated phosphate compounds.
  • the cyclic unsaturated carboxylic anhydride represented by the above formula 2 may be one or more selected from the group consisting of maleic anhydride (abbreviated as MA) and 2-methylmaleic anhydride (abbreviated as CA).
  • the unsaturated phosphate compound accounts for 0.1% to 3%, more preferably 0.1% to 2%, based on the total weight of the nonaqueous electrolyte of the lithium ion battery.
  • the cyclic unsaturated carboxylic anhydride compound accounts for 0.1% to 3%, more preferably 0.1% to 2%, based on the total weight of the nonaqueous electrolyte of the lithium ion battery.
  • the film forming effect on the negative electrode is deteriorated, and it is difficult to effectively prevent the unsaturated phosphate compound from being formed in the negative electrode; when unsaturated When the content of the cyclic carboxylic anhydride compound is more than 2%, the film formation at the electrode interface is also thick, and the impedance at the electrode interface is increased, particularly the impedance at the interface of the negative electrode, thereby increasing the overall impedance of the battery and deteriorating the battery performance.
  • the lithium ion battery nonaqueous electrolyte of the present application further includes at least one of an unsaturated cyclic carbonate or a cyclic sultone or a cyclic sulfate.
  • the unsaturated cyclic carbonate compound is used in an amount of 0.1% to 5% by weight based on the total weight of the nonaqueous electrolyte.
  • the cyclic sultone compound is used in an amount of 0.1% to 5% by weight based on the total weight of the nonaqueous electrolyte.
  • the cyclic sulfate compound is used in an amount of from 0.1% to 5% by weight based on the total weight of the nonaqueous electrolyte.
  • the unsaturated cyclic carbonate is at least one selected from the group consisting of vinylene carbonate and ethylene carbonate.
  • the cyclic sultone is at least one selected from the group consisting of 1,3-propane sultone, 1,4-butane sultone, 1,3-propene sultone and methylene methane disulfonate. .
  • the cyclic sulfate is selected from one or both of vinyl sulfate and propylene sulfate.
  • the non-aqueous electrolyte of the present application comprises a non-aqueous organic solvent selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and methyl propylene carbonate. At least one of the esters.
  • the lithium salt is at least one selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(trifluoromethylsulfonyl)imide, and lithium bisfluorosulfonimide.
  • the other side of the application discloses a lithium ion battery comprising a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte solution, wherein the electrolyte solution is the lithium ion battery non-aqueous electrolyte solution of the present application.
  • the charge cutoff voltage of the lithium ion battery of the present application is greater than or equal to 4.3V.
  • the positive electrode is selected from the group consisting of LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiCo 1-y M y O 2 , LiNi 1-y M y O 2 , LiMn 2-y M y O at least one of 4 and LiNi x Co y Mn z M 1 -xyz O 2 ; wherein, M is selected Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr At least one of V and Ti, and 0 ⁇ y ⁇ 1, 0 ⁇ x ⁇ 1, 0 ⁇ z ⁇ 1, x + y + z ⁇ 1.
  • non-aqueous electrolyte of the present application can be applied to various lithium ion batteries, including but not limited to the types listed in the present application.
  • the lithium ion battery electrolyte uses carbonate as a solvent.
  • the carbonate solvent is oxidized and decomposed on the surface of the positive electrode material to generate gas and other decomposition products.
  • the generated gas will cause the battery to bulge, which will bring safety hazards to the battery.
  • the decomposition products will obviously increase the impedance of the battery, thereby reducing the performance of the battery. Therefore, for a high voltage lithium ion battery, it is necessary to develop a solvent having a higher oxidation potential than the carbonate.
  • fluorocarbonate can significantly improve the high temperature cycle performance of high voltage lithium ion batteries.
  • the Applicant has found that although the fluorocarbonate can improve the high temperature cycle performance, the high temperature storage of the battery is serious and has a safety hazard.
  • An electrolyte of a fluorine-substituted carboxylic acid ester is disclosed in Chinese Patent Application No. CN104704657A, which can improve the high temperature cycle performance of a high voltage lithium ion battery.
  • the applicant has found that the compatibility of the fluorocarboxylic acid ester with the carbon negative electrode material is not good.
  • Ciobium Patent No. 201410534841.0 discloses a novel film-forming additive for a phosphate compound containing a ruthenium bond, which not only improves high temperature cycle performance, but also significantly improves storage performance.
  • researchers in the field have found in the research that the passivation film formed by the phosphate ester additive containing bismuth bond at the electrode interface is poor in conductivity, resulting in large interface impedance, significantly degrading low temperature performance, and inhibiting non-aqueous lithium.
  • an aspect of the present application discloses a nonaqueous electrolyte for a lithium ion battery, comprising component A and component B; and component A comprises a fluorinated cyclic carbonic acid selected from the group consisting of structural formula 1. At least one of the esters, and at least one of the alkyl-substituted cyclic carbonates represented by the structural formula 2 or at least one of the fluorocarboxylic acid esters represented by the structural formula 3;
  • R 1 is a fluorine element or a fluorine-containing hydrocarbon group having 1 to 4 carbon atoms
  • R 2 , R 3 and R 4 are each independently selected from a hydrogen element, a fluorine element, a hydrocarbon group having 1 to 4 carbon atoms or a carbon atom. a fluorine-containing hydrocarbon group of 1-4;
  • R 5 is a hydrocarbon group having 1 to 4 carbon atoms
  • R 6 , R 7 and R 8 are each independently selected from a hydrogen element or a hydrocarbon group having 1 to 4 carbon atoms
  • R 9 and R 10 are each independently selected from a hydrocarbon group having 1 to 4 carbon atoms or a fluorohydrocarbon group having 1 to 4 carbon atoms, and at least one of R 9 and R 10 is the fluorohydrocarbon group;
  • the fluorohydrocarbyl group contains at least two fluorine atoms;
  • R 11 is an unsaturated hydrocarbon group having 1 to 4 carbon atoms
  • R 12 and R 13 are each independently selected from a saturated hydrocarbon group having 1 to 4 carbon atoms, an unsaturated hydrocarbon group having 1 to 4 carbon atoms or a fluorohydrocarbon group having from 1 to 4 carbon atoms;
  • R 14 is selected from the group consisting of an alkylene group having 2 to 4 carbon atoms, an alkenylene group, or a fluorine-containing alkylene group having 2 to 4 carbon atoms and a fluorine-containing alkenylene group.
  • the key of the non-aqueous electrolyte of the present application is that the component A and the component B are used in combination, and the two synergistically act.
  • the fluorocarbonate and the fluorocarboxylic acid ester in the component A can increase the oxidative decomposition potential of the electrolytic solution because the oxidation resistance is higher than that of the carbonate. Further, the fluorocarbonate and the fluorocarboxylic acid ester can form a passivation film on the surface of the negative electrode, thereby suppressing the decomposition reaction of the electrolytic solution.
  • the thermal stability of the passivation film is not ideal, and a large amount of gas is generated, which lowers the high-temperature storage performance of the battery.
  • the fluorocarboxylate solvent decomposes on the surface of the negative electrode to generate a large amount of gas during the first charging of the battery, resulting in poor contact between the electrode sheets, thereby degrading the performance of the battery.
  • Component B Although the unsaturated phosphate or cyclic carboxylic anhydride can form a passivation film on the surface of the positive and negative electrodes, the internal resistance of the battery is significantly increased, and the low temperature performance of the battery is remarkably lowered.
  • the component A and the component B are simultaneously used in the present application, since the component A undergoes a film forming reaction on the surface of the positive and negative electrodes, the component B also participates in the positive and negative film forming reaction, so that the positive and negative passivation layer components Both the decomposition product of component A and the decomposition product of component B are included, which improves the interface between the positive and negative electrodes.
  • the thermal stability of the negative passivation film is improved, the high temperature performance of the battery is ensured, and the battery impedance is not significantly increased, and the low temperature performance of the battery is taken into consideration.
  • the present application uses component A and component B together, and the two synergistically produce a special effect that the two do not have alone.
  • the component A content is 10-90% of the total weight of the non-aqueous electrolyte
  • the component B content is 0.1-3% of the total weight of the non-aqueous electrolyte.
  • the compound represented by Structural Formula 1 is a component which is used together with the substance of Structural Formula 2 or/ and Structural Formula 3 as a solvent. That is, according to the present invention, component A may be a compound represented by Structural Formula 1 or a compound represented by Structural Formula 2, or a compound represented by Structural Formula 1 or a compound represented by Structural Formula 3, or a compound represented by Structural Formula 1, Structural Formula 2 may be used. The compound shown and the compound of Structural Formula 3 are used together as component A.
  • the compound of the formula 1 is used in an amount of from 5% to 80% by weight based on the total weight of the nonaqueous electrolyte.
  • the compound of the formula 2 when the compound of the formula 2 is contained, it is preferred that the compound of the formula 2 is used in an amount of from 5% to 80%, more preferably from 5 to 30%, based on the total amount of the nonaqueous electrolyte.
  • the compound of the formula 3 when the compound of the formula 3 is contained, it is preferred that the compound of the formula 3 is used in an amount of from 5% to 80%, more preferably from 20 to 70%, based on the total amount of the nonaqueous electrolyte.
  • Component B is a compound of Structural Formula 4 or/and Structural Formula 5.
  • the compound of the formula 4 when the compound of the formula 4 is contained, it is preferred that the compound of the formula 4 is used in an amount of from 0.1% by weight to 3% based on the total amount of the nonaqueous electrolyte.
  • the compound of the formula 5 when the compound of the formula 5 is contained, it is preferred that the compound of the formula 5 is used in an amount of from 0.1% by weight to 3% based on the total mass of the nonaqueous electrolyte.
  • the unsaturated cyclic carbonate is at least one selected from the group consisting of vinylene carbonate and vinyl ethylene carbonate.
  • the compound represented by Structural Formula 1 is a fluorinated cyclic carbonate.
  • the compound of Structural Formula 1 is selected from one or more of the following structural formulae.
  • the compound represented by Structural Formula 2 is an alkyl-substituted cyclic carbonate.
  • the compound represented by Structure 2 is selected from one or more of the following structural formulae.
  • the hydrocarbon group having 1 to 5 carbon atoms is selected from the group consisting of methyl, ethyl, propyl and butyl; and the fluorohydrocarbon group is selected from the group consisting of a fluoromethyl group, a fluoroethyl group, and a fluorine group.
  • the hydrocarbon group having 1 to 5 carbon atoms is selected from the group consisting of methyl, ethyl, propyl and butyl
  • the fluorohydrocarbon group is selected from the group consisting of a fluoromethyl group, a fluoroethyl group, and a fluorine group.
  • Propyl, fluorobutyl is selected from the group consisting of methyl, ethyl, propyl and butyl
  • the fluorohydrocarbon group is selected from the group consisting of a fluoromethyl group, a fluoroethyl group, and a fluorine group.
  • the fluorocarboxylate compound represented by Structural Formula 3 is selected from the group consisting of H 3 CCOOCH 2 CF 2 H (3-1, abbreviated as DFEA), H 3 CH 2 CCOOCH 2 CF 2 H (3-2, abbreviated as DFEP) ), HF 2 CH 2 CCOOCH 3 (3-3, abbreviated as MDFP), HF 2 CH 2 CCOOCH 2 CH 3 (3-4, abbreviated as EDFP), HF 2 CH 2 CH 2 CCOOCH 2 CH 3 (3-5 , abbreviated as EDFB), H 3 CCOOCH 2 CH 2 CF 2 H (3-6, abbreviated as DFPA), H 3 CH 2 CCOOCH 2 CH 2 CF 2 H (3-7, abbreviated as DFPP), CH 3 COOCH 2 CF 3 (3-8, abbreviated as TFEA), HCOOCH 2 CHF 2 (3-9, abbreviated as DFEF), HCOOCH 2 CF 3 , CH
  • the saturated hydrocarbon group having a carbon number of 1 to 4 in Structural Formula 4 includes, but is not limited to, a methyl group, an ethyl group, a propyl group; and the unsaturated hydrocarbon group having 1 to 4 carbon atoms includes, but not limited to, a vinyl group, an allyl group.
  • halohydrocarbyl group including but not limited to difluoromethyl, trifluoromethyl Base, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, hexafluoroisopropyl.
  • the unsaturated phosphate compound represented by Structural Formula 4 is selected from the group consisting of tripropargyl phosphate (4-1), dipropargyl methyl phosphate (4-2), and dipropargylethyl phosphate (4).
  • the cyclic carboxylic anhydride represented by Structural Formula 5 is selected from the group consisting of succinic anhydride (5-1, abbreviated as SA), maleic anhydride (5-2, abbreviated as MA), 2-methylmaleic anhydride (5- 3, abbreviated as one or more of CA).
  • SA succinic anhydride
  • MA maleic anhydride
  • CA 2-methylmaleic anhydride
  • the nonaqueous electrolyte further includes at least one of an unsaturated cyclic carbonate, a cyclic sultone, and a cyclic sulfate.
  • the unsaturated cyclic carbonate compound is used in an amount of 0.1% to 5% by weight based on the total weight of the nonaqueous electrolyte
  • the cyclic sultone compound is used in an amount of 0.1% to 5% by weight based on the total weight of the nonaqueous electrolyte.
  • the amount of the sulfate compound is from 0.1% to 5% by weight based on the total weight of the nonaqueous electrolyte.
  • the unsaturated cyclic carbonate is at least one selected from the group consisting of vinylene carbonate and vinyl ethylene carbonate.
  • the cyclic sulfate is selected from at least one of the following:
  • the cyclic sultone is selected from the group consisting of 1,3-propane sultone (abbreviated as PS), 1,4-butane sultone (abbreviated as BS), and 1,3-propene sultone. (abbreviated as PST), at least one of methane methane disulfonate (abbreviated as MMDS).
  • PS 1,3-propane sultone
  • BS 1,4-butane sultone
  • PST 1,3-propene sultone
  • PST 1,3-propene sultone
  • MMDS methane methane disulfonate
  • the non-aqueous electrolyte further comprises at least one selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and methylpropyl carbonate.
  • the content thereof may vary within a wide range, and preferably, the content thereof is from 1% to 40% by weight based on the total weight of the nonaqueous electrolyte. It is to be understood that when a plurality of the above substances are contained, the above content ranges from the total content of the plurality of substances.
  • the other side of the application discloses a lithium ion battery comprising a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is the nonaqueous electrolyte of the lithium ion battery of the present application.
  • the active material of the positive electrode is LiNi x Co y Mn z L (1-xyz) O 2 , LiCo x ' L (1-x') O 2 and LiNi x" L' y' Mn (2-x"- Y') at least one of O 4 , wherein L is Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1 , 0 ⁇ x+y+z ⁇ 1,0 ⁇ x' ⁇ 1, 0.3 ⁇ x" ⁇ 0.6,0.01 ⁇ y' ⁇ 0.2, L' is Co, Al, Sr, Mg, Ti, Ca, Zr, Zn , Si or Fe.
  • the lithium ion battery electrolyte uses carbonate as a solvent.
  • the carbonate solvent is oxidized and decomposed on the surface of the positive electrode material to generate gas and other decomposition products.
  • the generated gas will cause the battery to bulge, which will bring safety hazards to the battery.
  • the decomposition products will obviously increase the impedance of the battery, thereby reducing the performance of the battery. Therefore, for a high voltage lithium ion battery, it is necessary to develop a solvent having a higher oxidation potential than the carbonate.
  • a nonaqueous electrolyte for a lithium ion battery comprising at least one selected from the group consisting of the first compounds of Structural Formula 3 and the second selected from Structural Formula 4. At least one of the compounds;
  • R 9 COOR 10 R 9 and R 10 are each independently selected from a hydrocarbon group having 1 to 5 carbon atoms or a fluorohydrocarbon group, and at least one of R 9 and R 10 is the fluorohydrocarbon group; At least two hydrogens in the fluorohydrocarbyl group are replaced by fluorine;
  • R 11 , R 12 and R 13 are each independently selected from a saturated hydrocarbon group having 1 to 5 carbon atoms, an unsaturated hydrocarbon group or a halogenated hydrocarbon group, and at least one of R 11 , R 12 and R 13 is unsaturated. Hydrocarbyl group.
  • the non-aqueous electrolyte solution of the present application is mainly used in that a first compound represented by Structural Formula 3 and a second compound represented by Structural Formula 4 are used in combination, and the two synergistically act.
  • the first compound can reduce the decomposition reaction of the electrolyte on the surface of the high voltage positive electrode material due to the high oxidation potential.
  • the first compound decomposes on the surface of the negative electrode, thereby generating a large amount of gas, posing a safety hazard; the second compound can be generated on the surface of the positive and negative materials during the first charging of the lithium ion battery due to the unsaturated bond in the molecular structure.
  • the polymerization reaction forms a passivation film, but the passivation film has a large impedance, which lowers the low-temperature discharge performance and rate performance of the battery.
  • the second compound can preferentially form a passivation film on the surface of the negative electrode to inhibit the decomposition reaction of the first compound on the surface of the negative electrode, thereby suppressing the lithium ion battery in In the charging process, due to the structural formula 1, the gas is decomposed on the surface of the negative electrode.
  • the first compound can also partially participate in the negative film formation reaction, improving the interface of the negative electrode.
  • the present application uses the first compound together with the second compound, and the two cooperate to produce a special effect that the two do not have alone.
  • the first compound and the second compound are used together; wherein the amount of the first compound can be added in a conventional amount, for example, preferably, the amount of the first compound is from 10% to 80% by weight based on the total weight of the nonaqueous electrolyte.
  • the second compound is used in an amount according to the conventional amount of the additive in the non-aqueous electrolyte, for example, about 0.8-1.2% of the total weight of the non-aqueous electrolyte, and generally accounts for 0.01%-5% of the total weight of the non-aqueous electrolyte.
  • the first compound may be used alone as a non-aqueous organic solvent for a non-aqueous electrolyte, or may be used in combination with other common organic solvents, and mixed with other organic solvents will be described in detail in the subsequent schemes.
  • the key to the present application is to use the first compound and the second compound in the non-aqueous electrolyte.
  • other conventional components such as lithium salts
  • other organic solvents, lithium salts and other reagents of the non-aqueous organic solvent are specifically limited, which will be described in detail in the subsequent schemes.
  • the hydrocarbon group having 1 to 5 carbon atoms includes, but not limited to, methyl, ethyl, propyl, vinyl, allyl, 3-butenyl, isobutenyl, 4-pentyl Alkenyl, ethynyl, propargyl, 3-butynyl, 1-methyl-2-propynyl; said fluorohydrocarbyl group including but not limited to difluoromethyl, trifluoromethyl, 2,2-di Fluoroethyl, 2,2,2-trifluoroethyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, hexafluoroisopropyl;
  • a saturated hydrocarbon group having 1 to 5 carbon atoms includes, but is not limited to, a methyl group, an ethyl group, a propyl group; and an unsaturated hydrocarbon group having 1 to 5 carbon atoms includes, but not limited to, a vinyl group, an allyl group.
  • the first compound is selected from the group consisting of H 3 CCOOCH 2 CF 2 H (3-1, abbreviated as DFEA), H 3 CH 2 CCOOCH 2 CF 2 H (3-2, abbreviated as DFEP), HF 2 CH 2 CCOOCH 3 (3-3, abbreviated as MDFP), HF 2 CH 2 CCOOCH 2 CH 3 (3-4, abbreviated as EDFP), HF 2 CH 2 CH 2 CCOOCH 2 CH 3 (3-5, abbreviated as EDFB), H 3 CCOOCH 2 CH 2 CF 2 H (3-6, abbreviated as DFPA), H 3 CH 2 CCOOCH 2 CH 2 CF 2 H (3-7, abbreviated as DFPP), CH 3 COOCH 2 CF 3 (3-8, abbreviation It is TFEA), HCOOCH 2 CHF 2 (3-9, abbreviated as DFEF), HCOOCH 2 CF 3 , CH 3 COOCH 2 CF 2 H (3-10, abbreviation
  • the second compound is selected from the group consisting of tripropargyl phosphate, dipropargyl methyl phosphate, dipropargyl ethyl phosphate, dipropargyl propyl phosphate, dipropargyl trifluoromethyl phosphate Ester, dipropargyl 2,2,2-trifluoroethyl phosphate, dipropargyl 3,3,3-trifluoropropyl phosphate, dipropargyl hexafluoroisopropyl phosphate, phosphoric acid Allyl ester, diallyl methyl phosphate, diallyl ethyl phosphate, diallylpropyl phosphate, diallyl trifluoromethyl phosphate, diallyl 2, 2, At least one of 2-trifluoroethyl phosphate, diallyl 3,3,3-trifluoropropyl phosphate or diallyl hexafluoroisopropyl phosphate.
  • the non-aqueous electrolyte solution further comprises one or more of an unsaturated cyclic carbonate, an unsaturated acid anhydride, a cyclic sulfate, a cyclic sultone, and a sulfone.
  • the unsaturated cyclic carbonate includes at least one of vinylene carbonate (abbreviation VC) and ethylene carbonate (abbreviation VEC);
  • the cyclic sultone lactone comprises 1,3-propane sultone (abbreviated 1,3-PS), 1,4-butane sultone (abbreviation BS), and 1,3-propene sulfone At least one of an ester (abbreviated PST) and methane methane disulfonate (abbreviated MMDS).
  • 1,3-PS 1,3-propane sultone
  • BS 1,4-butane sultone
  • MMDS methane methane disulfonate
  • the unsaturated acid anhydride includes at least one of succinic anhydride (abbreviation SA), maleic anhydride (abbreviated as MA), and 2-methylmaleic anhydride (CA).
  • SA succinic anhydride
  • MA maleic anhydride
  • CA 2-methylmaleic anhydride
  • the cyclic sulfate comprises one or both of a vinyl sulfate (abbreviated DTD) and a propylene sulfate (abbreviated TS).
  • DTD vinyl sulfate
  • TS propylene sulfate
  • the sulfones include sulfolane (abbreviation SL).
  • vinylene carbonate (abbreviation VC), ethylene carbonate (abbreviation VEC), fluoroethylene carbonate (abbreviated FEC), or 1,3-propane sultone (abbreviation 1, 3PS), 1,4-butane sultone (abbreviation BS), 1,3-propene sultone (abbreviated PST), methane methane disulfonate (abbreviated MMDS), succinic anhydride (abbreviated SA), maleic anhydride (abbreviation MA), 2-methylmaleic anhydride (abbreviation CA), vinyl sulfate (abbreviated DTD), propylene sulfate (abbreviation TS), sulfolane (abbreviation SL) and 1,4-butyrolactone (abbreviation GBL)
  • SA succinic anhydride
  • MA maleic anhydride
  • CA 2-methylmaleic anhydride
  • TS vinyl sulfate
  • the amount of VC is preferably from 0.1% to 4%, more preferably from 0.5% to 1.5%, based on the total weight of the nonaqueous electrolyte.
  • the VEC amount is from 0.1% to 3%, more preferably from 0.2% to 1.5%, based on the total weight of the nonaqueous electrolyte.
  • the amount of 1,3-PS is from 0.1% to 10%, more preferably from 1% to 3%, based on the total weight of the nonaqueous electrolyte.
  • the amount of the BS is from 0.1% to 10%, more preferably from 1% to 3%, based on the total mass of the nonaqueous electrolyte.
  • the amount of PST is from 0.1% to 3%, more preferably from 0.5% to 2%, based on the total weight of the nonaqueous electrolyte.
  • the amount of MMDS is from 0.1% to 4%, more preferably from 0.5% to 2%, based on the total weight of the nonaqueous electrolyte.
  • the amount of SA is from 0.1% to 4%, more preferably from 0.5% to 2%, based on the total weight of the nonaqueous electrolyte.
  • the amount of MA is from 0.1% to 4%, more preferably from 0.5% to 2%, based on the total weight of the nonaqueous electrolyte.
  • the amount of CA is from 0.1% to 4%, more preferably from 0.5% to 2%, based on the total weight of the nonaqueous electrolyte.
  • the amount of DTD is from 0.1% to 5%, more preferably from 0.5% to 3%, based on the total weight of the nonaqueous electrolyte.
  • the amount of TS is from 0.1% to 4%, more preferably from 0.5% to 3%, based on the total weight of the nonaqueous electrolyte.
  • the amount of SL is from 0.1% to 30% by weight based on the total weight of the nonaqueous electrolyte, and more preferably from 2 to 15%.
  • the amount of GBL is from 0.1% to 30%, more preferably from 2 to 15%, based on the total weight of the nonaqueous electrolyte.
  • the non-aqueous electrolyte further comprises a solvent selected from the group consisting of ethylene carbonate, fluoroethylene carbonate (abbreviation FEC), propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and carbonic acid. At least one of methyl propyl ester.
  • the content thereof may vary within a wide range, and preferably, the content thereof is from 1% to 40% by weight based on the total weight of the nonaqueous electrolyte. It is to be understood that when a plurality of the above substances are contained, the above content ranges from the total content of the plurality of substances.
  • the nonaqueous electrolyte further includes at least one of ethylene carbonate, fluoroethylene carbonate, and propylene carbonate.
  • Another aspect of the present application discloses the use of the non-aqueous electrolyte of the present application in a lithium ion battery or a storage capacitor.
  • the other side of the application discloses a lithium ion battery comprising a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte is the nonaqueous electrolyte of the lithium ion battery of the present application.
  • the key of the lithium ion battery of the present application is that the non-aqueous electrolyte of the present application is used to form a passivation film on the surface of the positive and negative electrodes, thereby effectively suppressing the decomposition reaction of the electrolyte on the surface of the positive and negative electrodes, and suppressing the positive electrode.
  • the material structure is destroyed, the phenomenon of lithium deposition is reduced, and the high and low temperature performance and rate performance of the battery are guaranteed.
  • other components in the lithium ion battery such as the positive electrode, the negative electrode, and the separator, reference may be made to a conventional lithium ion battery.
  • the active material of the positive electrode is specifically limited.
  • the active material of the positive electrode is LiNi x Co y Mn z L (1-xyz) O 2 , LiCo x ' L (1-x') O 2 and LiNi x" L' y' Mn (2-x"- Y') at least one of O 4 , wherein L is Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1 , 0 ⁇ x+y+z ⁇ 1,0 ⁇ x' ⁇ 1, 0.3 ⁇ x" ⁇ 0.6,0.01 ⁇ y' ⁇ 0.2, L' is Co, Al, Sr, Mg, Ti, Ca, Zr, Zn , Si or Fe.
  • the non-aqueous electrolyte of the present application is used in combination with the first compound shown in Structural Formula 1 and the second compound shown in Structural Formula 2, and the two synergistically improve the high-temperature cycle of the high-voltage lithium ion battery. Can, but also avoid the decomposition of the surface of the negative electrode and gas production. Moreover, the first compound can also partially participate in the negative film forming reaction, improve the interface of the negative electrode, and thereby ensure the low-temperature discharge performance and rate performance of the battery.
  • Example 1 is a differential diagram of a first charge capacity of a blank electrolyte, Example 6 and Comparative Example 1;
  • Example 2 is an alternating current impedance diagram of a blank electrolyte, Example 6 and Comparative Example 1.
  • electrolytes were prepared according to the components and ratios shown in Table 1, in which a plurality of non-aqueous electrolytes for lithium ion batteries of the present application were designed, and a plurality of comparative examples are shown in Table 1.
  • the lithium salt of this example is lithium hexafluorophosphate. It can be understood that the lithium salt used in this example is only a specific embodiment, and other commonly used lithium salts in the art, such as LiBF 4 , LiBOB, LiDFOB, LiPO 2 F 2 , LiSbF 6 , LiAsF 6 , LiN (SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiC(SO 2 CF 3 ) 3 and LiN(SO 2 F) 2 can also be used in this example, and are not specifically limited herein.
  • the percentages in Table 1 are percentages by weight, i.e., the percentage of the additive as a percentage of the total weight of the electrolyte.
  • the positive active material is LiNi 0.5 Co 0.2 Mn 0.3 O 2
  • the negative electrode is made of artificial graphite
  • the separator is made of a three-layer separator of polypropylene, polyethylene and polypropylene. Made of 4.35V lithium ion battery. details as follows:
  • the positive electrode preparation method is: mixing positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , conductive carbon black and binder polyvinylidene fluoride in a mass ratio of 96.8:2.0:1.2, and dispersing in N-methyl-2-pyrrolidone In the middle, the positive electrode slurry is obtained, and the positive electrode slurry is uniformly coated on both sides of the aluminum foil, dried, calendered, and vacuum dried, and the aluminum lead wire is welded by an ultrasonic welding machine to obtain a positive electrode plate, and the thickness of the electrode plate is 120. -150 ⁇ m.
  • the negative electrode is prepared by mixing graphite, conductive carbon black, binder styrene butadiene rubber and carboxymethyl cellulose in a mass ratio of 96:1:1.2:1.8, dispersing in deionized water to obtain a negative electrode slurry, and a negative electrode slurry.
  • the material is coated on both sides of the copper foil, dried, calendered and vacuum dried, and the nickel lead wire is welded by an ultrasonic welder to obtain a negative electrode plate having a thickness of 120-150 ⁇ m.
  • the separator is prepared by using a three-layer separator of polypropylene, polyethylene and polypropylene and having a thickness of 20 ⁇ m.
  • the battery assembly method is: placing a three-layer separator having a thickness of 20 ⁇ m between the positive electrode plate and the negative electrode plate, and then winding the sandwich structure composed of the positive electrode plate, the negative electrode plate and the separator, and then squashing the wound body and placing the same.
  • the aluminum foil packaging bag is vacuum-baked at 75 ° C for 48 hours to obtain a battery core to be injected; the electrolyte prepared above is injected into the battery core, and vacuum-packed and allowed to stand for 24 hours.
  • the formula for calculating the capacity retention rate at 45 ° C for 1 C cycle is as follows:
  • the 300th cycle capacity retention ratio (%) (300th cycle discharge capacity / first cycle discharge capacity) ⁇ 100%.
  • the 500th cycle capacity retention ratio (%) (500th cycle discharge capacity / first cycle discharge capacity) ⁇ 100%.
  • the test method of capacity retention rate, capacity recovery rate and thickness expansion rate after storage for 30 days at 60 ° C includes: charging the formed battery to 4.35 V at a normal temperature with a constant current of 1 C, and the current is 0.01 C. Then, use 1C constant current discharge to 3.0V, measure the initial discharge capacity of the battery, and then charge to 4.35V with 1C constant current and constant voltage, the current is 0.01C, measure the initial thickness of the battery, and then store the battery at 60 ° C for 30 days.
  • Battery capacity retention rate (%) retention capacity / initial capacity ⁇ 100%
  • Battery capacity recovery rate (%) recovery capacity / initial capacity ⁇ 100%
  • Battery thickness expansion ratio (%) (thickness after 30 days - initial thickness) / initial thickness ⁇ 100%.
  • the low temperature discharge efficiency value of -20 ° C 1 C discharge capacity (-20 ° C) / 1 C discharge capacity (25 ° C).
  • Discharge DCIR value slope value of a linear plot of different discharge currents and corresponding cutoff voltages.
  • the unsaturated phosphate ester starts to form a negative electrode at about 2.7 V during the first charging process, and the film formation at the negative electrode causes a significant increase in the impedance of the negative electrode;
  • the unsaturated unsaturated carboxylic acid anhydride compound (CA) is added to the unsaturated phosphate ester (Compound 1), and the cyclic unsaturated carboxylic acid anhydride compound (CA) preferentially forms a film on the surface of the negative electrode at about 1.5 V and 2 V, and The film formed by the cyclic unsaturated carboxylic anhydride compound (CA) preferentially inhibits film formation of the unsaturated phosphate (Compound 1) at the subsequent 2.7 V, thereby further lowering the impedance of the negative electrode.
  • the present application combines an unsaturated phosphate compound and an unsaturated cyclic carboxylic anhydride compound, and at a suitable ratio, the battery can obtain excellent high temperature performance and cycle performance as well as good low temperature performance.
  • Electrolytes were prepared according to the components and ratios shown in Table 3, in which a plurality of non-aqueous electrolytes for lithium ion batteries of the present application were designed, and a plurality of comparative examples, as shown in Table 3.
  • the electrolytic solution of this example was prepared by formulating a non-aqueous organic solvent in accordance with the volume ratio shown in Table 3, and then adding a lithium hexafluorophosphate having a final concentration of 1.0 mol/L thereto, and then adding an additive according to Table 3.
  • the percentages in Table 3 are percentages by weight, i.e., the percentage of the additive to the total weight of the electrolyte, and the lithium salt content in the electrolyte is 12.5%, with the balance being solvent-based additives.
  • the positive active material is LiNi 0.5 Co 0.2 Mn 0.3 O 2
  • the negative electrode is made of graphite and conductive carbon black
  • the separator is made of a three-layer separator of polypropylene, polyethylene and polypropylene. details as follows:
  • the positive electrode preparation method is: mixing positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , conductive carbon black and binder polyvinylidene fluoride in a mass ratio of 96.8:2.0:1.2, and dispersing in N-methyl-2-pyrrolidone In the middle, the positive electrode slurry is obtained, and the positive electrode slurry is uniformly coated on both sides of the aluminum foil, dried, calendered, and vacuum dried, and the aluminum lead wire is welded by an ultrasonic welding machine to obtain a positive electrode plate, and the thickness of the electrode plate is 120. -150 ⁇ m.
  • the preparation method of the negative electrode is as follows: mixing graphite, conductive carbon black, and viscosity at a mass ratio of 96:1:1.2:1.8
  • the butyl styrene rubber and the carboxymethyl cellulose are dispersed in deionized water to obtain a negative electrode slurry, and the negative electrode slurry is coated on both sides of the copper foil, dried, calendered, vacuum dried, and welded by an ultrasonic welding machine.
  • a negative electrode plate was obtained after the nickel lead wire was taken up, and the thickness of the electrode plate was between 120 and 150 ⁇ m.
  • the separator is prepared by using a three-layer separator of polypropylene, polyethylene and polypropylene and having a thickness of 20 ⁇ m.
  • the battery assembly method is: placing a three-layer separator having a thickness of 20 ⁇ m between the positive electrode plate and the negative electrode plate, and then winding the sandwich structure composed of the positive electrode plate, the negative electrode plate and the separator, and then squashing the wound body and placing the same.
  • the aluminum foil packaging bag is vacuum-baked at 85 ° C for 24 hours to obtain a battery core to be injected; the electrolyte prepared above is injected into the battery core, and vacuum-packed and allowed to stand for 24 hours.
  • the lithium ion battery of each electrolyte was tested, and the capacity retention rate at 400 ° C for 1 week and the capacity retention rate, capacity recovery rate, and thickness expansion ratio after storage for 30 days at 60 ° C were measured.
  • the storage at 60 ° C for 30 days means that the electrolyte of the comparative example was tested after storage at 60 ° C for 30 days, and the test was tested after storage at 60 ° C for 30 days.
  • the specific test methods are as follows:
  • Capacity retention ratio (%) (cycle discharge capacity at week 400 / cycle discharge capacity at week 1) ⁇ 100%.
  • the test method of capacity retention rate, capacity recovery rate and thickness expansion ratio after storage for 30 days at 60 ° C includes: charging the formed battery to 4.4 V at a normal temperature with a constant current of 1 C, and the off current is 0.01 C. , 1C constant current discharge to 3.0V, measure the initial discharge capacity of the battery, and then charge to 4.4V with 1C constant current and constant voltage, the current is 0.01C, measure the initial thickness of the battery, and then store the battery after 60 days at 60 °C. The thickness was then discharged to 3.0 V with a constant current of 1 C. The holding capacity of the battery was measured, and the current was discharged to a constant current of 0.01 C using a constant current of 1 C, and then discharged to 3.0 V with a current of 1 C, and the recovery capacity was measured. Calculated as follows:
  • Battery capacity retention rate (%) retention capacity / initial capacity ⁇ 100%
  • Battery capacity recovery rate (%) recovery capacity / initial capacity ⁇ 100%
  • Battery thickness expansion ratio (%) (thickness after 30 days - initial thickness) / initial thickness ⁇ 100%.
  • the formed battery was charged to 4.4 V with a constant current of 1 C at 25 ° C, then charged at a constant voltage until the current dropped to 0.01 C, and then discharged to 3.0 V with a constant current of 1 C, and the normal temperature discharge capacity was recorded. Then 1C constant The flow was charged to 4.4V, and then the constant current was charged until the current dropped to 0.01 C.
  • the battery was placed in an environment of -20 ° C for 12 h, and then discharged at a constant current of 0.2 C to 3.0 V, and a discharge capacity of -20 ° C was recorded.
  • the fluorinated solvent can improve the high-temperature cycle performance and the low-temperature discharge performance of the battery, but the high-temperature storage gas production is large, and there is a safety hazard.
  • the unsaturated phosphate ester or/and the cyclic carboxylic anhydride additive can simultaneously improve the high-temperature cycle and the high-temperature storage performance, the improvement range is limited, which needs to be further improved, and the low-temperature discharge performance is poor.
  • the high temperature storage and high temperature cycle performance of the battery can be significantly improved, while taking into account low temperature discharge performance. Since there is a certain synergistic effect between the fluorinated solvent and the unsaturated phosphate ester or / cyclic carboxylic acid anhydride, an effect which the one component does not have is produced. Further addition of an unsaturated cyclic carbonate or a cyclic sultone or a cyclic sulfate can further improve the high temperature storage and high temperature cycle performance of the battery.
  • the first compound when used as a non-aqueous organic solvent, decomposes the gas in the negative electrode, posing a safety hazard; the second compound can improve the high-temperature performance, but it is in the positive and negative electrodes.
  • the surface is polymerized to form a passivation film, which has a large impedance and reduces the low-temperature discharge performance and rate performance of the battery.
  • the present application proposes that the first compound and the second compound are used in combination, and the two synergistically overcome the advantages and functions of the first compound and the second compound.
  • the safety hazard of the first compound in the decomposition of gas produced by the negative electrode, the effect of the second compound on the low-temperature discharge performance and rate performance of the battery is alleviated, and the performance of the battery is greatly improved.
  • Electrolytes were prepared according to the components and ratios shown in Table 5, in which a plurality of non-aqueous electrolytes for lithium ion batteries of the present application were designed, and a plurality of comparative examples, as shown in Table 5.
  • the electrolytic solution of this example was prepared by dissolving a nonaqueous organic solvent in the proportions shown in Table 5, and then adding a lithium hexafluorophosphate having a final concentration of 1.0 mol/L, and then adding an additive according to Table 5.
  • the percentages in Table 5 are percentages by weight, i.e., the percentage of the additive to the total weight of the electrolyte, and the lithium salt content in the electrolyte is 12.5%, with the balance being solvent-based additives.
  • the positive active material is LiNi 0.5 Co 0.2 Mn 0.3 O 2
  • the negative electrode is made of graphite and conductive carbon black
  • the separator is made of a three-layer separator of polypropylene, polyethylene and polypropylene. details as follows:
  • the positive electrode preparation method is: mixing positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , conductive carbon black and binder polyvinylidene fluoride in a mass ratio of 96.8:2.0:1.2, and dispersing in N-methyl-2-pyrrolidone In the middle, the positive electrode slurry is obtained, and the positive electrode slurry is uniformly coated on both sides of the aluminum foil, dried, calendered, and vacuum dried, and the aluminum lead wire is welded by an ultrasonic welding machine to obtain a positive electrode plate, and the thickness of the electrode plate is 120. -150 ⁇ m.
  • the negative electrode is prepared by mixing graphite, conductive carbon black, binder styrene butadiene rubber and carboxymethyl cellulose in a mass ratio of 96:1:1.2:1.8, dispersing in deionized water to obtain a negative electrode slurry, and a negative electrode slurry.
  • the material is coated on both sides of the copper foil, dried, calendered and vacuum dried, and the nickel lead wire is welded by an ultrasonic welder to obtain a negative electrode plate having a thickness of 120-150 ⁇ m.
  • the separator is prepared by using a three-layer separator of polypropylene, polyethylene and polypropylene and having a thickness of 20 ⁇ m.
  • the battery assembly method is: placing a three-layer separator having a thickness of 20 ⁇ m between the positive electrode plate and the negative electrode plate, and then winding the sandwich structure composed of the positive electrode plate, the negative electrode plate and the separator, and then squashing the wound body and placing the same.
  • the aluminum foil packaging bag is vacuum-baked at 75 ° C for 48 hours to obtain a battery core to be injected; the electrolyte prepared above is injected into the battery core, and vacuum-packed and allowed to stand for 24 hours.
  • the lithium ion battery of each electrolyte was tested, and the cycle number of the 1C cycle capacity retention rate was reduced to 80% at 45 ° C, and the capacity retention rate, capacity recovery rate and thickness expansion ratio after storage for 14 days at 60 ° C.
  • the storage at 60 ° C for several days means that the electrolyte of the comparative example was tested after storage at 60 ° C for 7 days, and the test was tested after storage at 60 ° C for 14 days.
  • the specific test methods are as follows:
  • Capacity retention ratio (%) (Nth cycle discharge capacity / first cycle discharge capacity) ⁇ 100%.
  • the test method of capacity retention rate, capacity recovery rate and thickness expansion ratio after storage for 14 days at 60 ° C includes: charging the formed battery to 4.4 V at a normal temperature with a constant current of 1 C, and the off current is 0.01 C. , 1C constant current discharge to 3.0V, measure the initial discharge capacity of the battery, and then charge to 4.4V with 1C constant current and constant voltage, the cut-off current is 0.01C, measure the initial thickness of the battery, and then store the battery after storage at 60 °C for 14 days. The thickness was then discharged to 3.0 V with a constant current of 1 C. The holding capacity of the battery was measured, and the current was discharged to a constant current of 0.01 C using a constant current of 1 C, and then discharged to 3.0 V with a current of 1 C, and the recovery capacity was measured. Calculated as follows:
  • Battery capacity retention rate (%) retention capacity / initial capacity ⁇ 100%
  • Battery capacity recovery rate (%) recovery capacity / initial capacity ⁇ 100%
  • Battery thickness expansion ratio (%) (thickness after 14 days - initial thickness) / initial thickness ⁇ 100%.
  • the formed battery was charged to 4.4 V with a constant current of 1 C at 25 ° C, then charged at a constant voltage until the current dropped to 0.01 C, and then discharged to 3.0 V with a constant current of 1 C, and the normal temperature discharge capacity was recorded. Then 1C constant current is charged to 4.4V, and then constant voltage is charged until the current drops to 0.01C.
  • the battery is placed in the environment of -20 °C for 12h, then 0.2C constant current discharge to 3.0V, and the discharge capacity of -20 °C is recorded. .
  • Comparative Example 9 uses only the second compound as an additive, and does not use the first compound as a solvent. Therefore, the high-temperature cycle performance is weak, and the capacity retention ratio remains after 80 cycles. %, and the storage capacity and recovery capacity stored at 60 ° C for 14 days are also not satisfactory, especially the low-temperature discharge performance is relatively poor.
  • the first compound was used as the solvent, and the second compound was not used as the additive, and the high-temperature storage property and the high-temperature storage property were poor.
  • Comparative Example 11-17 using the first compound as a solvent and using saturated phosphate as an additive, and optimizing the solvent combination, although the high temperature cycle performance and high temperature storage performance of the battery were greatly improved, but Still unable to meet the requirements, it needs to be further improved.
  • the first compound was used as the solvent and the second compound as the additive, and the solvent combination and the additive combination were optimized, and the high-temperature cycle performance and the high-temperature storage and storage performance were significantly improved, while taking into consideration the low temperature. Discharge performance.
  • the high-temperature cycle performance was the best, and the capacity retention rate was able to be circulated 662 times when it was attenuated to 80%, and the high-temperature storage performance was also excellent.

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Abstract

一种用于锂离子电池的非水电解液及锂离子电池，所述非水电解液，包括不饱和磷酸酯类化合物和环状不饱和羧酸酐类化合物，所述不饱和磷酸酯类化合物具有结构式4所示结构，结构式4：其中，R 13、R 11、R 12分别独立地选自碳原子数为1-5的烃基，且R 13、R 11、R 12中至少一个为含有双键或叁键的不饱和烃基；所述不饱和环状羧酸酐类化合物具有结构式5所示结构，结构式5：其中，R 14选自碳原子数为2-4的亚烯基或氟取代碳原子数为2-4的亚烯基。所述非水电解液，通过两种化合物的协同作用，一方面具有优异的高温循环性能和存储性能，同时具有较低的阻抗，低温性能优良。

Description

一种用于锂离子电池的非水电解液及锂离子电池 技术领域
本申请涉及锂离子电池电解液领域，特别是涉及一种用于锂离子电池的非水电解液及锂离子电池。
背景技术
锂离子电池具有比能量高、比功率大、循环寿命长等特点，目前主要应用于3C数码类消费类电子产品领域和新能源动力汽车和储能领域。随着新能源汽车续航里程的要求不断提高和数码类消费电子产品的尺寸不断小型化，使得高能量密度化成为目前锂离子电池的主要发展趋势。提高锂离子电池工作电压是提高电池能量密度的有效途径。
提高锂离子电池的工作电压往往会带来性能的劣化。因为在高电压下，一方面电池正极的晶体结构存在一定的不稳定性，在充放电的过程中，会发生结构的塌陷从而导致性能的恶化；另一方面，在高电压下，正极表面处于高氧化态下，活性较高，容易催化电解液氧化分解，电解液的分解产物容易在正极表面发生沉积，堵塞锂离子的脱嵌通道，从而恶化电池性能。
电解液是影响电池综合性能的关键因素，特别地，电解液中的添加剂对电池的各项性能的发挥尤其重要。因此，要充分发挥三元镍钴锰材料的动力电池的性能，电解液的匹配是关键。目前实用化的锂离子电池电解液是添加传统的成膜添加剂如碳酸亚乙烯酯(缩写VC)或氟代碳酸乙烯酯(缩写FEC)的非水电解液，通过VC和FEC的添加保障电池优异的循环性能。但VC的高电压稳定性较差，FEC高温下容易分解产气。因此，在高电压高温条件下，这些添加剂很难满足锂离子电池在高电压下和高温下的循环的性能要求。
专利申请201410534841.0中公开了一种含三键的磷酸酯化合物新型成膜添加剂，其不仅可以改善高温循环性能，还能明显改善储存性能。但本领域的科技工作者在研究中发现，三键的磷酸酯添加剂不仅能在正极成膜，而且能在负极成膜，其在负极的成膜会明显增大负极的阻抗，明显劣化了低温性能。
而环状不饱和羧酸酐类化合物作为锂电池电解液添加剂也很早见于一些相关文献和专利中，环状不饱和羧酸酐与三键的磷酸酯功能特点类似，也是能明显改善高温性能，但同时也会增大电池阻抗，劣化低温性能，抑制了非水锂离子电池在低温条件下的应用。
发明内容
本申请的目的是提供一种用于锂离子电池非水电解液及使用该锂离子电池的非水电解液。
为了实现上述目的，本申请采用了以下技术方案：
方案一：
本申请的一方面公开了一种用于锂离子电池的非水电解液，包括不饱和磷酸酯类化合物和不饱和环状羧酸酐类化合物，所述不饱和磷酸酯类化合物具有结构式4所示结构，
结构式4：
Figure PCTCN2016113649-appb-000001
其中，R13、R11、R12分别独立地选自碳原子数为1-5的烃基，且R13、R11、R12中至少一个为含有双键或叁键的不饱和烃基；
所述不饱和环状羧酸酐类化合物具有结构式5所示结构，
结构式5：
Figure PCTCN2016113649-appb-000002
其中，R14选自碳原子数为2-4的亚烯基或氟取代碳原子数为2-4的亚烯基。
一般情况下，两类高温性能好，阻抗大，低温性能差的添加剂组合在一起使用，会使得电池进一步获得更好的高温性能，但阻抗会进一步增大，低温性能会进一步变差。但本领域的科技工作者在研究中发现，在锂离子电池非水电解液中同时添加上述三键磷酸酯类化合物和环状不饱和羧酸酐类化合物，与单独使用三键磷酸酯类化合物相比，发现高温性能得到明显改善，并且出乎预料的发现界面阻抗明显降低、低温性能明显改善。
同时添加不饱和磷酸酯类化合物和环状不饱和羧酸酐类化合物的技术原理在于：首次充电过程中，不饱和磷酸酯类化合物会在负极成膜，该类化合物在负极所成的钝化膜导电性较差，会明显增大负极阻抗，从而导致电池整体阻抗显著偏大，低温性能差。而不饱和环状羧酸酐类化合物在首次充电过程中也具有很强的负极成膜功能，主要体现在该类化合物负极的成膜电位较高，可以优先不饱和磷酸酯类化合物在负极成膜，从而抑制后续不饱和磷酸酯类化合物在负极的成膜，从而降低了电池阻抗。本申请将不饱和磷酸酯类化合物和不饱和 环状羧酸酐类化合物一起使用，两者协调作用，产生了两者单独使用不具有的特殊效果。
由上述描述，同时添加不饱和磷酸酯类化合物和环状不饱和羧酸酐类化合物的技术原理可以用图1和图2来说明，图中的Blank为空白电解液：EC/EMC/DEC＝1/1/1(体积比)，LiPF6：1M。由图1和图2可知，不饱和磷酸酯类(化合物1)在首次充电过程中，大约在2.7V左右开始于负极成膜，此时在负极成膜会导致负极的阻抗明显增大；在不饱和磷酸酯类(化合物1)基础上加入环状不饱和羧酸酐类化合物(CA)，环状不饱和羧酸酐类化合物(CA)会优先在1.5V和2V左右于负极表面形成膜，并且环状不饱和羧酸酐类化合物(CA)优先形成的膜会抑制不饱和磷酸酯类(化合物1)在后续2.7V处的成膜，从而降低负极的阻抗。
具体的，上述式一所示的不饱和磷酸酯类化合物可以选自如下结构式的化合物：
Figure PCTCN2016113649-appb-000003
可以理解，无论是式一所示的不饱和磷酸酯类化合物，还是化合物1到化合物6的不饱和磷酸酯类化合物，都是本申请的优选的技术方案，不排除其它具有相似理化特性的不饱和磷酸酯类化合物。
具体的，上述式二所示的环状不饱和羧酸酐可以选自马来酸酐(缩写为MA)、2-甲基马来酸酐(缩写为CA)中一种或多种。
可以理解，无论是式二所示的环状不饱和羧酸酐类化合物，还是MA还是CA，都是本申请的优选的技术方案，不排除其它具有相似理化特性的环状不饱和羧酸酐类化合物。
优选的，本申请的锂离子电池非水电解液中，不饱和磷酸酯类化合物占锂离子电池非水电解液总重量的0.1％～3％，更优选为0.1％～2％。
由上述描述可知，当上述不饱和磷酸酯类化合物的用量小于0.1％时，正极成膜效果变差，对正极的保护作用下降，改善性能的效果下降；当其用量大于2％时，会使电极界面的成膜偏厚，增大电极界面阻抗，特别是负极界面的阻抗，从而增大电池整体阻抗，劣化电池性能。
优选的，本申请的锂离子电池非水电解液中，环状不饱和羧酸酐类化合物占锂离子电池非水电解液总重量的0.1％～3％，更优选为0.1％～2％。
同时，由上述描述可知，当不饱和环状羧酸酐类化合物的含量小于0.1％时，其在负极的成膜效果变差，难以有效阻止不饱和磷酸酯类化合物在负极成膜；当不饱和环状羧酸酐类化合物的含量大于2％时，也会导致电极界面的成膜偏厚，增大电极界面的阻抗，特别是负极界面的阻抗，从而增大电池整体阻抗，劣化电池性能。
进一步地，本申请的锂离子电池非水电解液还包括不饱和环状碳酸酯或环状磺酸内酯或环状硫酸酯中的至少一种。
进一步地，所述不饱和环状碳酸酯化合物用量占非水电解液总重量的0.1％-5％。环状磺酸内酯化合物用量占非水电解液总重量的0.1％-5％。环状硫酸酯化合物用量占非水电解液总重量的0.1％-5％。
进一步地，所述不饱和环状碳酸酯选自碳酸亚乙烯酯、碳酸乙烯亚乙酯中的至少一种。
所述环状磺酸内酯选自1,3-丙烷磺内酯、1,4-丁烷磺内酯、1,3-丙烯磺内酯和甲烷二磺酸亚甲酯中的至少一种。
所述环状硫酸酯选自硫酸乙烯酯和硫酸丙烯酯中的一种或两种。
本申请的非水电解液中，包含非水有机溶剂，有机溶剂选自碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯和碳酸甲丙酯中的至少一种。
进一步地，本申请的非水电解液中，锂盐选自六氟磷酸锂、四氟硼酸锂、二(三氟甲基磺酰)亚胺锂和双氟磺酰亚胺锂盐中的至少一种。
本申请的另一面公开了一种锂离子电池，包括正极、负极、置于正极与负极之间的隔膜，以及电解液，其中，电解液为本申请的锂离子电池非水电解液。
本申请的锂离子电池的充电截止电压大于或等于4.3V。
进一步地，本申请的锂离子电池中，正极选自LiCoO2、LiNiO2、LiMn2O4、LiCo1-yMyO2、LiNi1-yMyO2、LiMn2-yMyO4和LiNixCoyMnzM1-x-y-zO2中的至少一种；其中，M 选自Fe、Co、Ni、Mn、Mg、Cu、Zn、Al、Sn、B、Ga、Cr、Sr、V和Ti中的至少一种，且0≤y≤1，0≤x≤1，0≤z≤1，x+y+z≤1。
需要说明的是，本申请的非水电解液，可以适用于各种锂离子电池，包括但不仅限于本申请所列举的类型。
方案二：
目前锂离子电池电解液采用碳酸酯作为溶剂，当锂离子电池的充电电压大于4.2V，碳酸酯溶剂会在正极材料表面被氧化分解，产生气体和其它分解产物。一方面，产生的气体会导致电池鼓胀，给电池带来安全隐患，另一方面，其分解产物会明显增加电池的阻抗，从而降低电池的各个性能。因此，对于高电压锂离子电池，有必要开发比碳酸酯氧化电位更高的溶剂。据文献报道(Electrochemistry Communications 44(2014)34–37)，氟代碳酸酯能够明显改善高电压锂离子电池的高温循环性能。但本申请人发现，氟代碳酸酯虽然可以改善高温循环性能，但电池高温储存产气严重，具有安全隐患。中国专利申请CN104704657A中公开了一种含氟取代的羧酸酯的电解液，能够改善高电压锂离子电池的高温循环性能。但本申请人发现，氟代羧酸酯与碳负极材料的兼容性能不好，在电池充电过程中，会在负极表面被还原分解产生大量的气体，这个电池带来极大的安全隐患，同时明显恶化电池的性能。中国专利201410534841.0公开了一种含叁键的磷酸酯化合物新型成膜添加剂，其不仅可以改善高温循环性能，还能明显改善储存性能。但本领域的科技工作者在研究中发现，含叁键的磷酸酯添加剂在电极界面所形成的钝化膜导电性较差，导致界面阻抗较大，明显劣化了低温性能，抑制了非水锂离子电池在低温条件下的应用。专利文献报道环状羧酸酐能够改善高温储存性能。但本发明者发现，环状羧酸酐在以碳酸酯为溶剂的电解液基础上，明显增加电池阻抗，降低电池低温放电性能及倍率性能。
对此，本申请的一方面公开了一种用于锂离子电池的非水电解液，包括组分A和组分B；所述组分A包括选自结构式1所示的氟代环状碳酸酯中至少一种，同时还包括结构式2所示的烷基取代环状碳酸酯中至少一种或/和结构式3所示的氟代羧酸酯中的至少一种；
结构式1：
Figure PCTCN2016113649-appb-000004
其中，R1为氟元素或碳原子数为1-4的含氟烃基，R2、R3、R4分别独立选自氢元素、氟元素、碳原子数为1-4的烃基或碳原子数为1-4的含氟烃基；
结构式2：
Figure PCTCN2016113649-appb-000005
其中R5为碳原子数为1-4的烃基，R6、R7、R8分别独立选自氢元素或碳原子数为1-4的烃基；
结构式3：R9COOR10，
其中，R9、R10分别独立的选自碳原子数为1-4的烃基或碳原子数为1-4的氟代烃基，且R9和R10中至少一个为所述氟代烃基；所述氟代烃基中至少含有两个氟原子；
结构式4
Figure PCTCN2016113649-appb-000006
其中，R11为碳原子数为1-4的不饱和烃基，R12、R13分别独立的选自碳原子数为1-4的饱和烃基、碳原子数为1-4的不饱和烃基或碳原子数为1-4的氟代烃基；
结构式5
Figure PCTCN2016113649-appb-000007
其中R14选自碳原子数为2-4的亚烷基、亚烯基、或碳原子数为2-4的含氟亚烷基、含氟亚烯基。
需要说明的是，本申请的非水电解液，其关键在于，组分A和组分B配合使用，两者协同作用。组分A中的氟代碳酸酯和氟代羧酸酯由于耐氧化性比碳酸酯高，能够提高电解液的氧化分解电位。此外，氟代碳酸酯和氟代羧酸酯能够在负极表面形成钝化膜，抑制了电解液的分解反应。但是氟代碳酸酯溶剂在电池高温储存过程中，钝化膜的热稳定性不够理想，产生大量的气体，降低了电池的高温储存性能。氟代羧酸酯溶剂在电池首次充电过程中，在负极表面分解产生大量的气体，导致电极片之间的接触变差，从而降低电池的性能。组分B 的不饱和磷酸酯或环状羧酸酐虽然能够在正负极表面形成钝化膜，但明显增加电池内阻，显著降低电池的低温性能。本申请将组分A和组分B同时使用时，由于组分A在正负极表面发生成膜反应时，组分B也会参与正负极成膜反应，使得正负极钝化层成分既包含组分A的分解产物也包含组分B的分解产物，改善了正负极界面情况。既提高了负极钝化膜的热稳定性，保证了电池高温性能，同时又不会明显增加电池阻抗，兼顾了电池的低温性能。本申请将组分A和组分B一起使用，两者协同作用，产生了两者单独使用不具有的特殊效果。
上述电解液中，组分A含量占非水电解液总重量的10-90％，组分B含量占非水电解液总重量的0.1-3％。
本发明中，结构式1所示的化合物为必含成分，其与结构式2或/和结构式3所示物质共同作为溶剂使用。即，根据本发明，组分A可为结构式1所示的化合物和结构式2所示化合物，或者结构式1所示的化合物和结构式3所示化合物，也可以采用结构式1所示的化合物、结构式2所示化合物和结构式3所示化合物共同作为组分A使用。
优选的，结构式1所示化合物用量占非水电解液总重量的5％-80％。
组分A中，当含有结构式2所示化合物时，优选的，结构式2所示化合物用量占非水电解液总重量的5％-80％，更优选为5-30％。当含有结构式3所示化合物时，优选的，结构式3所示化合物用量占非水电解液总重量的5％-80％，更优选为20-70％。
本发明中，组分B为结构式4或/和结构式5所示化合物。组分B中，当含有结构式4所示化合物时，优选的，结构式4所示化合物用量占非水电解液总重量的0.1％-3％。当含有结构式5所示化合物时，优选的，结构式5所示化合物用量占非水电解液总重量的0.1％-3％。
优选的，所述不饱和环状碳酸酯选自碳酸亚乙烯酯、碳酸亚乙烯乙酯中至少一种。
优选的，结构式1所示化合物为氟代环状碳酸酯，优选情况下，结构式1所示化合物选自下列结构式一种或多种，
Figure PCTCN2016113649-appb-000008
Figure PCTCN2016113649-appb-000009
优选的，结构式2所示化合物为烷基取代环状碳酸酯，优选情况下，结构2所示化合物选自下列结构式一种或多种，
Figure PCTCN2016113649-appb-000010
优选的，所述结构式3中，碳原子数为1-5的烃基选自甲基、乙基、丙基、丁基；所述氟代烃基选自氟代甲基、氟代乙基、氟代丙基、氟代丁基。
优选的，结构式3所示的氟代羧酸酯化合物选自H3CCOOCH2CF2H(3-1，缩写为DFEA)、H3CH2CCOOCH2CF2H(3-2，缩写为DFEP)、HF2CH2CCOOCH3(3-3，缩写为MDFP)、HF2CH2CCOOCH2CH3(3-4，缩写为EDFP)、HF2CH2CH2CCOOCH2CH3(3-5，缩写为EDFB)、H3CCOOCH2CH2CF2H(3-6，缩写为DFPA)、H3CH2CCOOCH2CH2CF2H(3-7，缩写为DFPP)、CH3COOCH2CF3(3-8，缩写为TFEA)、HCOOCH2CHF2(3-9，缩写为DFEF)、HCOOCH2CF3、CH3COOCH2CF2CF2H(3-10，缩写为TFPA)中的一种或多种。
优选的，结构式4中碳原子数为1-4的饱和烃基包括但不仅限于甲基、乙基、丙基；碳原子数为1-4的不饱和烃基包括但不仅限于乙烯基、烯丙基、3-丁烯基、异丁烯基、乙炔基、炔丙基、3-丁炔基、1-甲基-2丙炔基；所述卤代烃基包括但不仅限于二氟甲基、三氟甲基、2,2-二氟乙基、2,2,2-三氟乙基、3,3-二氟丙基、3,3,3-三氟丙基、六氟异丙基。
优选的，结构式4所示的不饱和磷酸酯化合物选自磷酸三炔丙酯(4-1)、二炔丙基甲基磷酸酯(4-2)、二炔丙基乙基磷酸酯(4-3)、二炔丙基丙基磷酸酯(4-4)、二炔丙基三氟甲基磷酸酯(4-5)、二炔丙基2,2,2-三氟乙基磷酸酯(4-6)、二炔丙基3,3,3-三氟丙基磷酸酯(4-7)、二炔丙基六氟异丙基磷酸酯(4-8)、磷酸三烯丙酯(4-9)、二烯丙基甲基磷酸酯(4-10)、二烯 丙基乙基磷酸酯(4-11)、二烯丙基丙基磷酸酯(4-12)、二烯丙基三氟甲基磷酸酯(4-13)、二烯丙基2,2,2-三氟乙基磷酸酯(4-14)、二烯丙基3,3,3-三氟丙基磷酸酯(4-15)、二烯丙基六氟异丙基磷酸酯(4-16)中的一种或多种。
优选的，结构式5所示的环状羧酸酐选自丁二酸酐(5-1，缩写为SA)，马来酸酐(5-2，缩写为MA)、2-甲基马来酸酐(5-3，缩写为CA)中一种或多种。
优选的，所述非水电解液还包括不饱和环状碳酸酯、环状磺酸内酯、环状硫酸酯中的至少一种。
优选的，所述不饱和环状碳酸酯化合物用量占非水电解液总重量的0.1％-5％，环状磺酸内酯化合物用量占非水电解液总重量的0.1％-5％，环状硫酸酯化合物用量占非水电解液总重量的0.1％-5％。
优选的，所述不饱和环状碳酸酯选自碳酸亚乙烯酯、碳酸亚乙烯乙酯中至少一种。
优选的，所述环状硫酸酯选自下列物质中的至少一种：
Figure PCTCN2016113649-appb-000011
优选的，所述环状磺酸内酯选自1,3-丙烷磺内酯(缩写为PS)、1,4-丁烷磺内酯(缩写为BS)、1,3-丙烯磺内酯(缩写为PST)、甲烷二磺酸亚甲酯(缩写为MMDS)中的至少一种。
优选的，非水电解液还包括选自碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯中的至少一种。其含量可在较大范围内变动，优选情况下，其含量占非水电解液总重量的1％-40％。可以理解的，当含有上述物质中的多种时，上述含量范围为上述多种物质的总含量所占比例。
本申请的另一面公开了一种锂离子电池，包括正极、负极、置于正极和负极之间的隔膜，以及电解液，其中，电解液为本申请的锂离子电池非水电解液。
优选的，正极的活性物质为LiNixCoyMnzL(1-x-y-z)O2、LiCox’L(1-x’)O2和LiNix”L’y’Mn(2-x”-y’)O4中的至少一种，其中，L为Al、Sr、Mg、Ti、Ca、Zr、Zn、Si或Fe，0≤x≤1，0≤y≤1，0≤z≤1，0＜x+y+z≤1，0<x’≤1，0.3≤x”≤0.6，0.01≤y’≤0.2，L’为Co、Al、Sr、Mg、Ti、Ca、Zr、Zn、Si或Fe。
方案三：
目前锂离子电池电解液采用碳酸酯作为溶剂，当锂离子电池的充电电压大于4.2V，碳酸酯溶剂会在正极材料表面被氧化分解，产生气体和其它分解产物。一方面，产生的气体会导致电池鼓胀，给电池带来安全隐患，另一方面，其分解产物会明显增加电池的阻抗，从而降低电池的各个性能。因此，对于高电压锂离子电池，有必要开发比碳酸酯氧化电位更高的溶剂。中国专利申请CN104704657A中公开了一种含氟取代的羧酸酯及磷酸酯的电解液，能够改善高电压锂离子电池的高温循环性能。但本申请人发现，氟代羧酸酯与碳负极材料的兼容性能不好，在电池充电过程中，会在负极表面被还原分解产生大量的气体，这个电池带来极大的安全隐患，同时明显恶化电池的性能。磷酸酯虽然在一定程度可以抑制氟代羧酸酯的分解，但高温循环及高温储存性能有待进一步提高。
对此，本申请的另一方面公开了一种用于锂离子电池的非水电解液，包括选自结构式3所示的第一化合物中的至少一种和选自结构式4所示的第二化合物中的至少一种；
结构式3：R9COOR10中，R9、R10分别独立的选自碳原子数为1-5的烃基或氟代烃基，且R9和R10中至少一个为所述氟代烃基；所述氟代烃基中至少有两个氢被氟取代；
结构式4：
Figure PCTCN2016113649-appb-000012
其中，R11、R12、R13分别独立的选自碳原子数为1-5的饱和烃基、不饱和烃基或卤代烃基，且R11、R12、R13中至少有一个为不饱和烃基。
需要说明的是，本申请的非水电解液，其关键在于，以结构式3所示的第一化合物和结构式4所示的第二化合物配合使用，两者协同作用。其中，第一化合物由于氧化电位高，能够降低电解液在高电压正极材料表面的分解反应， 但第一化合物会在负极表面分解，从而产生大量的气体，带来安全隐患；第二化合物由于分子结构中含有不饱和键，在锂离子电池首次充电过程中，能够在正负极材料表面发生聚合反应形成钝化膜，但该钝化膜阻抗较大，降低了电池的低温放电性能和倍率性能。本申请将第一化合物和第二化合物同时使用时，由于第二化合物能够优先在负极表面发生聚合反应形成钝化膜，抑制了第一化合物在负极表面的分解反应，从而抑制了锂离子电池在充电过程中因结构式一在负极表面分解而产气现象。此外，第一化合物也能部分参与负极成膜反应，改善了负极界面情况。本申请将第一化合物和第二化合物一起使用，两者协调作用，产生了两者单独使用不具有的特殊效果。
本申请中，第一化合物和第二化合物同时使用；其中，第一化合物用量可按常规量添加，例如，优选情况下，第一化合物用量占非水电解液总重量的10％-80％。第二化合物，其用量按照非水电解液中添加剂的常规用量即可，例如占非水电解液总重量的0.8-1.2％左右，一般占非水电解液总重量的0.01％-5％均可。第一化合物，可以单独作为非水电解液的非水有机溶剂使用，也可以与其它常见的有机溶剂混合使用，与其它有机溶剂混合使用将在后续的方案中详细介绍。
还需要说明的是，本申请的关键在于在非水电解液中使用了第一化合物和第二化合物，至于其它常规组分，例如锂盐，可以参考现有的非水电解液，甚至在非水电解液中还可以添加其它常用的试剂，以增加相应的功能，在此不做具体限定。但是，在本申请的优选方案中，为了达到更好的效果，对非水有机溶剂的其它有机溶剂、锂盐和其它试剂进行了特别限定，这将在后续的方案中详细介绍。
优选的，所述结构式一中，碳原子数为1-5的烃基包括但不仅限于甲基、乙基、丙基、乙烯基、烯丙基、3-丁烯基、异丁烯基、4-戊烯基、乙炔基、炔丙基、3-丁炔基、1-甲基-2丙炔基；所述氟代烃基包括但不仅限于二氟甲基、三氟甲基、2,2-二氟乙基、2,2,2-三氟乙基、3,3-二氟丙基、3,3,3-三氟丙基、六氟异丙基；
所述结构式二中，碳原子数为1-5的饱和烃基包括但不仅限于甲基、乙基、丙基；碳原子数为1-5的不饱和烃基包括但不仅限于乙烯基、烯丙基、3-丁烯基、异丁烯基、4-戊烯基、乙炔基、炔丙基、3-丁炔基、1-甲基-2丙炔基；碳原子数为1-5的卤代烃基包括但不仅限于二氟甲基、三氟甲基、2,2-二氟乙基、2,2,2-三氟乙基、3,3-二氟丙基、3,3,3-三氟丙基、六氟异丙基。
优选的，第一化合物选自H3CCOOCH2CF2H(3-1，缩写为DFEA)、H3CH2CCOOCH2CF2H (3-2，缩写为DFEP)、HF2CH2CCOOCH3(3-3，缩写为MDFP)、HF2CH2CCOOCH2CH3(3-4，缩写为EDFP)、HF2CH2CH2CCOOCH2CH3(3-5，缩写为EDFB)、H3CCOOCH2CH2CF2H(3-6，缩写为DFPA)、H3CH2CCOOCH2CH2CF2H(3-7，缩写为DFPP)、CH3COOCH2CF3(3-8，缩写为TFEA)、HCOOCH2CHF2(3-9，缩写为DFEF)、HCOOCH2CF3、CH3COOCH2CF2CF2H(3-10，缩写为TFPA)。
优选的，第二化合物选自磷酸三炔丙酯、二炔丙基甲基磷酸酯、二炔丙基乙基磷酸酯，二炔丙基丙基磷酸酯、二炔丙基三氟甲基磷酸酯、二炔丙基2,2,2-三氟乙基磷酸酯、二炔丙基3,3,3-三氟丙基磷酸酯、二炔丙基六氟异丙基磷酸酯、磷酸三烯丙酯、二烯丙基甲基磷酸酯、二烯丙基乙基磷酸酯，二烯丙基丙基磷酸酯、二烯丙基三氟甲基磷酸酯、二烯丙基2,2,2-三氟乙基磷酸酯、二烯丙基3,3,3-三氟丙基磷酸酯或二烯丙基六氟异丙基磷酸酯中的至少一种。
优选的，所述非水电解液中还包括不饱和环状碳酸酯、不饱和酸酐、环状硫酸酯、环状磺酸内酯、砜类中的一种或多种。
所述不饱和环状碳酸酯包括碳酸亚乙烯酯(缩写VC)、碳酸乙烯亚乙酯(缩写VEC)中的至少一种；
优选的，所述环状磺酸内酯包括1,3-丙烷磺内酯(缩写1，3-PS)、1,4-丁烷磺内酯(缩写BS)、1，3-丙烯磺内酯(缩写PST)和甲烷二磺酸亚甲酯(缩写MMDS)中的至少一种。
优选的，所述不饱和酸酐包括丁二酸酐(缩写SA)、马来酸酐(缩写MA)和2-甲基马来酸酐(CA)中的至少一种。
优选的，所述环状硫酸酯包括硫酸乙烯酯(缩写DTD)和硫酸丙烯酯(缩写TS)中的一种或两种。
优选的，所述砜类包括环丁砜(缩写SL)。
需要说明的是，碳酸亚乙烯酯(缩写VC)、碳酸乙烯亚乙酯(缩写VEC)、氟代碳酸乙烯酯(缩写FEC)，或者1,3-丙烷磺内酯(缩写1，3PS)、1,4-丁烷磺内酯(缩写BS)、1，3-丙烯磺内酯(缩写PST)、甲烷二磺酸亚甲酯(缩写MMDS)、丁二酸酐(缩写SA)、马来酸酐(缩写MA)、2-甲基马来酸酐(缩写CA)、硫酸乙烯酯(缩写DTD)、硫酸丙烯酯(缩写TS)、环丁砜(缩写SL)和1,4-丁内酯(缩写GBL)，这些都是已经报道过的用于非水电解液的常规试剂，其中有的试剂，即可以作为添加剂，也可以作为溶剂，例如FEC，其用量比较大时，被认为是非水有机溶剂，其用量比较小时被认为是添加剂。例如，在本发明中，优选情况下，VC用量占非水电解液总重量的0.1％-4％，进一步优选为0.5-1.5％。VEC用量占非水电解液总重量的0.1％-3％，进一步优选为0.2-1.5％。 1，3-PS用量占非水电解液总重量的0.1％-10％，进一步优选为1-3％。BS用量占非水电解液总重量的0.1％-10％，进一步优选为1-3％。PST用量占非水电解液总重量的0.1％-3％，进一步优选为0.5-2％。MMDS用量占非水电解液总重量的0.1％-4％，进一步优选为0.5-2％。SA用量占非水电解液总重量的0.1％-4％，进一步优选为0.5-2％。MA用量占非水电解液总重量的0.1％-4％，进一步优选为0.5-2％。CA用量占非水电解液总重量的0.1％-4％，进一步优选为0.5-2％。DTD用量占非水电解液总重量的0.1％-5％，进一步优选为0.5-3％。TS用量占非水电解液总重量的0.1％-4％，进一步优选为0.5-3％。SL用量占非水电解液总重量的0.1％-30％，进一步优选为2-15％。GBL用量占非水电解液总重量的0.1％-30％，进一步优选为2-15％。
优选的，非水电解液还包括选自碳酸乙烯酯、氟代碳酸乙烯酯(缩写FEC)、碳酸丙烯酯、碳酸丁烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯和碳酸甲丙酯中的至少一种。其含量可在较大范围内变动，优选情况下，其含量占非水电解液总重量的1％-40％。可以理解的，当含有上述物质中的多种时，上述含量范围为上述多种物质的总含量所占比例。
更优选的，非水电解液还包括碳酸乙烯酯、氟代碳酸乙烯酯和碳酸丙烯酯中的至少一种。
本申请的另一面公开了本申请的非水电解液在锂离子电池或储能电容器中的应用。
本申请的另一面公开了一种锂离子电池，包括正极、负极、置于正极和负极之间的隔膜，以及电解液，其中，电解液为本申请的锂离子电池非水电解液。
可以理解，本申请的锂离子电池，其关键在于采用了本申请的非水电解液，使得其正负极表面形成钝化膜，从而有效抑制电解液在正负极表面的分解反应，抑制正极材料结构被破坏，减小了析锂现象，保障了电池的高低温性能及倍率性能。至于锂离子电池中的其它组分，如正极、负极和隔膜可以参考常规的锂离子电池。本申请优选的方案中，对正极的活性物质进行了特别限定。
优选的，正极的活性物质为LiNixCoyMnzL(1-x-y-z)O2、LiCox’L(1-x’)O2和LiNix”L’y’Mn(2-x”-y’)O4中的至少一种，其中，L为Al、Sr、Mg、Ti、Ca、Zr、Zn、Si或Fe，0≤x≤1，0≤y≤1，0≤z≤1，0＜x+y+z≤1，0<x’≤1，0.3≤x”≤0.6，0.01≤y’≤0.2，L’为Co、Al、Sr、Mg、Ti、Ca、Zr、Zn、Si或Fe。
由于采用以上技术方案，本申请的有益效果在于：
本申请的非水电解液，以结构式一所示的第一化合物和结构式二所示的第二化合物配合使用，两者协同作用，既改善了高电压锂离子电池的高温循环性 能，又避免了负极表面分解而产气现象。并且，第一化合物也能部分参与负极成膜反应，改善负极界面情况，进而保障电池的低温放电性能和倍率性能。
附图说明
图1为空白电解液、实施例6和对比例1的首次充电容量微分图；
图2为空白电解液、实施例6和对比例1的交流阻抗图。
具体实施方式
下面通过具体实施例和附图对本申请作进一步详细说明。以下实施例仅对本申请进行进一步说明，不应理解为对本申请的限制。
方案一：
实施例
本例按照表1所示的组分和配比制备电解液，其中，设计了多个本申请的用于锂离子电池的非水电解液，以及多个对比例，详见表1。
本例的锂盐采用六氟磷酸锂。可以理解，本例所采用的锂盐只是一个具体的实施方式，本领域其它常用的锂盐，如LiBF4、LiBOB、LiDFOB、LiPO2F2、LiSbF6、LiAsF6、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiC(SO2CF3)3和LiN(SO2F)2，同样可以用于本例，在此不做具体限定。
本例的电解液的制备方法为：按照EC/EMC/DEC＝1/1/1(体积比)的体积比配制非水有机溶剂，然后向其中加入最终浓度为1.0mol/L的六氟磷酸锂，再按表1加入添加剂。表1中的百分比为重量百分比，即添加剂占电解液总重量的百分比。
表1电解液中各组分及用量
Figure PCTCN2016113649-appb-000013
Figure PCTCN2016113649-appb-000014
本例的锂离子电池，正极活性物质采用LiNi0.5Co0.2Mn0.3O2，负极采用人造石墨，隔膜采用聚丙烯、聚乙烯和聚丙烯三层隔离膜。制成4.35V锂离子电池。具体如下：
正极制备方法为：按96.8：2.0：1.2的质量比混合正极活性材料LiNi0.5Co0.2Mn0.3O2、导电碳黑和粘结剂聚偏二氟乙烯，分散在N-甲基-2-吡咯烷酮中，得到正极浆料，将正极浆料均匀涂布在铝箔的两面上，经过烘干、压延和真空干燥，并用超声波焊机焊上铝制引出线后得到正极板，极板的厚度在120-150μm之间。
负极制备方法为：按96：1：1.2：1.8的质量比混合石墨、导电碳黑、粘结剂丁苯橡胶和羧甲基纤维素，分散在去离子水中，得到负极浆料，将负极浆料涂布在铜箔的两面上，经过烘干、压延和真空干燥，并用超声波焊机焊上镍制引出线后得到负极板，极板的厚度在120-150μm之间。
隔膜制备方法为：采用聚丙烯、聚乙烯和聚丙烯三层隔离膜，厚度为20μm。
电池组装方法为：在正极板和负极板之间放置厚度为20μm的三层隔离膜，然后将正极板、负极板和隔膜组成的三明治结构进行卷绕，再将卷绕体压扁后放入铝箔包装袋，在75℃下真空烘烤48h，得到待注液的电芯；将上述制备的电解液注入电芯中，经真空封装，静止24h。
电池化成：0.05C恒流充电180min,0.1C恒流充电至3.95V，二次真空封口，45℃搁置48h，然后进一步以0.2C的电流恒流充电至4.4V，以0.2C的电流恒流放电至3.0V。
本例分别测试了各个电解液电池的45℃ 1C循环300次和常温1C循环500次容量保持率、在60℃下存储30天后的容量保持率、容量恢复率和厚度膨胀率，-20℃1C放电效率以及常低温直流阻抗。具体测试方法如下：
(1)45℃ 1C循环300周容量保持率，实际上是测量的电池的高温循环性能，具体测试方法包括：在45℃下，将化成后的电池用1C恒流恒压充至4.35V， 截至电流为0.01C，然后用1C恒流放电至3.0V。如此充/放电300次循环后，计算第300次循环后容量的保持率，以评估其高温循环性能。45℃ 1C循环300次容量保持率计算公式如下：
第300次循环容量保持率(％)＝(第300次循环放电容量/第一次循环放电容量)×100％。
(2)常温循环性能测试：在25℃下，将化成后的电池用1C恒流恒压充至4.35V，然后用1C恒流放电至3.0V。充/放电500次循环后计算第500次循环容量的保持率，以评估其常温循环性能。计算公式如下：
第500次循环容量保持率(％)＝(第500次循环放电容量/第一次循环放电容量)×100％。
(3)60℃下存储30天后的容量保持率、容量恢复率和厚度膨胀率的测试方法包括：将化成后的电池在常温下用1C恒流恒压充至4.35V，截至电流为0.01C，再用1C恒流放电至3.0V，测量电池初始放电容量，再用1C恒流恒压充电至4.35V，截至电流为0.01C，测量电池的初始厚度，然后将电池在60℃储存30天后，测量电池的厚度，再以1C恒流放电至3.0V，测量电池的保持容量，再用1C恒流恒压充电至4.35V，截至电流为0.01C，然后用1C恒流放电至3.0V，测量恢复容量。容量保持率、容量恢复率和厚度膨胀率的计算公式如下：
电池容量保持率(％)＝保持容量/初始容量×100％
电池容量恢复率(％)＝恢复容量/初始容量×100％
电池厚度膨胀率(％)＝(30天后的厚度-初始厚度)/初始厚度×100％。
(4)低温放电性能测试：在25℃下，将化成后的电池用1C恒流恒压充至4.35V，然后用1C恒流放电至3.0V，记录放电容量。然后1C恒流恒压充满，置于-20℃的环境中搁置12h后，1C恒流放电至3.0V，记录放电容量。
-20℃的低温放电效率值＝1C放电容量(-20℃)/1C放电容量(25℃)。
(5)常温直流阻抗(DCIR)性能测试：在25℃下，将化成后的电池1C充电到SOC＝50％状态，分别用0.1C，0.2C，0.5C，1C和2C充放十秒，分别记录充放电截止电压。然后，以不同倍率的充放电电流为横坐标(单位：A)，以充放电电流所对应的截止电压为纵坐标，做线性关系图(单位：mV)。
放电DCIR值＝不同放电电流与相应截止电压的线性图的斜率值。
各项测试结果如表2所示。
表2测试结果
Figure PCTCN2016113649-appb-000015
通过测试，形成空白电解液、实施例6和对比例1的首次充电容量微分图(如图1所示)和交流阻抗图(如图2所示)。
由图1和图2可知，不饱和磷酸酯类(化合物1)在首次充电过程中，大约在2.7V左右开始于负极成膜，此时在负极成膜会导致负极的阻抗明显增大；在不饱和磷酸酯类(化合物1)基础上加入环状不饱和羧酸酐类化合物(CA)，环状不饱和羧酸酐类化合物(CA)会优先在1.5V和2V左右于负极表面形成膜，并且环状不饱和羧酸酐类化合物(CA)优先形成的膜会抑制不饱和磷酸酯类(化合物1)在后续2.7V处的成膜，从而进一步降低负极的的阻抗。
通过对比例1-2的测试结果对比，可以发现不饱和磷酸酯类化合物单独使用时，循环性能和高温存储较好，但阻抗很大，低温性能很差。不饱和环状羧酸酐类化合物单独使用时，阻抗较低，低温性能较好，但循环性能和高温存储较差。
而本申请的实施例1-18的测试结果中，通过对比例1和实施例2,6,8的对 比，可以发现在不饱和磷酸酯类化合物基础上，添加不饱和环状羧酸酐类化合物，不仅仅循环性能和高温性能有明显改善，低温性能也有明显提高，阻抗也明显降低。
同时，本申请的实施例1-18的测试结果中，相对于对比例1，可以发现同时包含不饱和磷酸酯类化合物和不饱和环状羧酸酐类化合物的所有实施例的高温性能和低温性能都有所改善。通过实施例2，5,6，7对比，随着不饱和磷酸酯类化合物的增加，其高温性能有所提高，但是低温性能相对下降，特别是阻抗随着用量的增加，阻抗也随之增大。尤其是当不饱和磷酸酯类化合物含量很高而不饱和环状羧酸酐类化合物含量很低时，阻抗较大，低温性能明显不足。
综上所述，本申请将不饱和磷酸酯类化合物和不饱和环状羧酸酐类化合物配合使用，在合适的比例下，可以使电池获得优良的高温性能和循环性能以及良好的低温性能。
方案二：
按照表3所示的组分和配比制备电解液，其中，设计了多个本申请的用于锂离子电池的非水电解液，以及多个对比例，详见表3。
本例的电解液的制备方法为：按照表3所示的体积比配制非水有机溶剂，然后向其中加入最终浓度为1.0mol/L的六氟磷酸锂，再按表3加入添加剂。表3中的百分比为重量百分比，即添加剂占电解液总重量的百分比，电解液中锂盐含量为12.5％，其余为溶剂级添加剂。
表3电解液中各组分及用量
Figure PCTCN2016113649-appb-000016
Figure PCTCN2016113649-appb-000017
本例的锂离子电池，正极活性物质采用LiNi0.5Co0.2Mn0.3O2，负极采用石墨和导电炭黑，隔膜采用聚丙烯、聚乙烯和聚丙烯三层隔离膜。具体如下：
正极制备方法为：按96.8：2.0：1.2的质量比混合正极活性材料LiNi0.5Co0.2Mn0.3O2、导电碳黑和粘结剂聚偏二氟乙烯，分散在N-甲基-2-吡咯烷酮中，得到正极浆料，将正极浆料均匀涂布在铝箔的两面上，经过烘干、压延和真空干燥，并用超声波焊机焊上铝制引出线后得到正极板，极板的厚度在120-150μm之间。
负极制备方法为：按96：1：1.2：1.8的质量比混合石墨、导电碳黑、粘 结剂丁苯橡胶和羧甲基纤维素，分散在去离子水中，得到负极浆料，将负极浆料涂布在铜箔的两面上，经过烘干、压延和真空干燥，并用超声波焊机焊上镍制引出线后得到负极板，极板的厚度在120-150μm之间。
隔膜制备方法为：采用聚丙烯、聚乙烯和聚丙烯三层隔离膜，厚度为20μm。
电池组装方法为：在正极板和负极板之间放置厚度为20μm的三层隔离膜，然后将正极板、负极板和隔膜组成的三明治结构进行卷绕，再将卷绕体压扁后放入铝箔包装袋，在85℃下真空烘烤24h，得到待注液的电芯；将上述制备的电解液注入电芯中，经真空封装，静止24h。
电池化成：0.05C恒流充电180min,0.1C恒流充电至3.95V，二次真空封口，45℃搁置48h，然后进一步以0.2C的电流恒流充电至4.4V，以0.2C的电流恒流放电至3.0V。
本例分别测试了各个电解液锂离子电池，45℃ 1C循环400周容量保持率以及60℃下存储30天后的容量保持率、容量恢复率和厚度膨胀率。其中60℃下存储30天后是指，对比例的电解液，其锂离子电池在60℃下存储30天后进行测试，试验例在60℃下存储30天后进行测试。具体测试方法如下：
(1)45℃ 1C循环400周容量保持率，实际上体现的是电池的高温循环性能，具体测试方法包括：在45℃下，将化成后的电池用1C恒流恒压充至4.4V，截至电流为0.01C，然后用1C恒流放电至3.0V，如此循环400周。容量保持率计算公式如下：
容量保持率(％)＝(第400周循环放电容量/第1周循环放电容量)×100％。
(2)60℃下存储30天后的容量保持率、容量恢复率和厚度膨胀率的测试方法包括：将化成后的电池在常温下用1C恒流恒压充至4.4V，截至电流为0.01C，再1C恒流放电至3.0V，测量电池初始放电容量，再用1C恒流恒压充电至4.4V，截至电流为0.01C，测量电池的初始厚度，然后在60℃储存30天后，测量电池的厚度，再以1C恒流放电至3.0V，测量电池的保持容量，再用1C恒流恒压充截至电流为0.01C，然后以1C的电流恒流放电至3.0V，测量其恢复容量。计算公式如下：
电池容量保持率(％)＝保持容量/初始容量×100％
电池容量恢复率(％)＝恢复容量/初始容量×100％
电池厚度膨胀率(％)＝(30天后的厚度-初始厚度)/初始厚度×100％。
(3)低温放电性能测试
在25℃下，将化成后的电池用1C恒流恒压充至4.4V，然后恒压充电至电流下降至0.01C，然后用1C恒流放电至3.0V，记录常温放电容量。然后1C恒 流充至4.4V，再恒压充电至电流下降至0.01C，将电池置于-20℃的环境中搁置12h后，再0.2C恒流放电至3.0V，记录-20℃放电容量。
-20℃的低温放电效率＝0.2C放电容量(-20℃)/1C放电容量(25℃)×100％。
各项测试结果如表4所示。
表4测试结果
Figure PCTCN2016113649-appb-000018
Figure PCTCN2016113649-appb-000019
从表4的测试结果可以看出，与碳酸酯溶剂相比，氟代溶剂虽然可以改善电池的高温循环性能及低温放电性能，但高温储存产气量大，存在安全隐患。不饱和磷酸酯或/和环状羧酸酐添加剂虽然能够同时改善高温循环及高温储存性能，但改善幅度有限，有待进一步提高，且低温放电性能较差。通过将氟代溶剂与不饱和磷酸酯或/和环状羧酸酐组合，可以明显改善电池的高温储存及高温循环性能，同时兼顾低温放电性能。由于氟代溶剂与不饱和磷酸酯或/环状羧酸酐之间存在一定的协同作用，产生了单组分不具有的效果。进一步添加不饱和环状碳酸酯或环状磺内酯或环状硫酸酯，可以进一步提高电池的高温储存及高温循环性能。
方案三：
在对电解液一系列的研究中，发现第一化合物，作为非水有机溶剂使用时，在负极会分解产气，存在安全隐患；第二化合物虽然能够提高高温性能，但是，其在正负极表面发生聚合反应形成钝化膜，该钝化膜阻抗较大，降低了电池的低温放电性能和倍率性能。在经过大量的研究和试验后，本申请提出，将第一化合物和第二化合物混合使用，两者协同作用，在保留第一化合物和第二化合物各自的优点和功能的基础上，既克服了第一化合物在负极分解产气的安全隐患，又缓解了第二化合物对电池低温放电性能和倍率性能的影响，大大提高了电池的各项性能。
按照表5所示的组分和配比制备电解液，其中，设计了多个本申请的用于锂离子电池的非水电解液，以及多个对比例，详见表5。
本例的电解液的制备方法为：按照表5所示的比例配制非水有机溶剂，然后向其中加入最终浓度为1.0mol/L的六氟磷酸锂，再按表5加入添加剂。表5中的百分比为重量百分比，即添加剂占电解液总重量的百分比，电解液中锂盐含量为12.5％，其余为溶剂级添加剂。
表5电解液中各组分及用量
Figure PCTCN2016113649-appb-000020
Figure PCTCN2016113649-appb-000021
本例的锂离子电池，正极活性物质采用LiNi0.5Co0.2Mn0.3O2，负极采用石墨和导电炭黑，隔膜采用聚丙烯、聚乙烯和聚丙烯三层隔离膜。具体如下：
正极制备方法为：按96.8：2.0：1.2的质量比混合正极活性材料LiNi0.5Co0.2Mn0.3O2、导电碳黑和粘结剂聚偏二氟乙烯，分散在N-甲基-2-吡咯烷酮中，得到正极浆料，将正极浆料均匀涂布在铝箔的两面上，经过烘干、压延和真空干燥，并用超声波焊机焊上铝制引出线后得到正极板，极板的厚度在120-150μm之间。
负极制备方法为：按96：1：1.2：1.8的质量比混合石墨、导电碳黑、粘结剂丁苯橡胶和羧甲基纤维素，分散在去离子水中，得到负极浆料，将负极浆料涂布在铜箔的两面上，经过烘干、压延和真空干燥，并用超声波焊机焊上镍制引出线后得到负极板，极板的厚度在120-150μm之间。
隔膜制备方法为：采用聚丙烯、聚乙烯和聚丙烯三层隔离膜，厚度为20μm。
电池组装方法为：在正极板和负极板之间放置厚度为20μm的三层隔离膜，然后将正极板、负极板和隔膜组成的三明治结构进行卷绕，再将卷绕体压扁后放入铝箔包装袋，在75℃下真空烘烤48h，得到待注液的电芯；将上述制备的电解液注入电芯中，经真空封装，静止24h。
电池化成：0.05C恒流充电180min,0.1C恒流充电至3.95V，二次真空封口，45℃搁置48h，然后进一步以0.2C的电流恒流充电至4.4V，以0.2C的电流恒流放电至3.0V。
本例分别测试了各个电解液锂离子电池，45℃ 1C循环容量保持率衰减到80％的循环次数，以及60℃下存储14天后的容量保持率、容量恢复率和厚度膨胀率。其中60℃下存储若干天后是指，对比例的电解液，其锂离子电池在60℃下存储7天后进行测试，试验例在60℃下存储14天后进行测试。具体测试方法如下：
(1)45℃ 1C循环容量保持率衰减到80％的循环次数，实际上体现的是电 池的高温循环性能，具体测试方法包括：在45℃下，将化成后的电池用1C恒流恒压充至4.4V，截至电流为0.01C，然后用1C恒流放电至3.0V，如此循环，直至容量保持率衰减到80％，统计此时的循环次数。容量保持率计算公式如下：
容量保持率(％)＝(第N次循环放电容量/第一次循环放电容量)×100％。
(2)60℃下存储14天后的容量保持率、容量恢复率和厚度膨胀率的测试方法包括：将化成后的电池在常温下用1C恒流恒压充至4.4V，截至电流为0.01C，再1C恒流放电至3.0V，测量电池初始放电容量，再用1C恒流恒压充电至4.4V，截至电流为0.01C，测量电池的初始厚度，然后在60℃储存14天后，测量电池的厚度，再以1C恒流放电至3.0V，测量电池的保持容量，再用1C恒流恒压充截至电流为0.01C，然后以1C的电流恒流放电至3.0V，测量其恢复容量。计算公式如下：
电池容量保持率(％)＝保持容量/初始容量×100％
电池容量恢复率(％)＝恢复容量/初始容量×100％
电池厚度膨胀率(％)＝(14天后的厚度-初始厚度)/初始厚度×100％。
(3)低温放电性能测试
在25℃下，将化成后的电池用1C恒流恒压充至4.4V，然后恒压充电至电流下降至0.01C，然后用1C恒流放电至3.0V，记录常温放电容量。然后1C恒流充至4.4V，再恒压充电至电流下降至0.01C，将电池置于-20℃的环境中搁置12h后，再0.2C恒流放电至3.0V，记录-20℃放电容量。
-20℃的低温放电效率＝0.2C放电容量(-20℃)/1C放电容量(25℃)×100％。
各项测试结果如表6所示。
表6测试结果
Figure PCTCN2016113649-appb-000022
Figure PCTCN2016113649-appb-000023
根据表6的结果可以看出，对比例9仅采用了第二化合物作为添加剂，而没有采用第一化合物作为溶剂，因此，高温循环性能较弱，在290个循环后容量保持率就剩下80％，并且60℃储存14天的保持容量和恢复容量也不理想，尤其是低温放电性能比较差。对比例10采用了第一化合物作为溶剂，而没有使用第二化合物作为添加剂，其高温储存性能及高温储存性能都很差。对比例11-17，采用第一化合物作为溶剂，并采用饱和的磷酸酯作为添加剂，同时对溶剂组合也进行了优化调整，虽然电池的高温循环性能和高温储存性能都有较大的改善，但还是无法满足要求，有待进一步提高。实施例39-59同时采用了第一化合物作为溶剂和第二化合物作为添加剂，同时对溶剂组合及添加剂组合都进行了优化，其高温循环性能和高温储存存储性能均有明显的改善，同时兼顾低温放电性能。实施例59高温循环性能最好，容量保持率衰减到80％时能够循环662次，且高温储存性能也相当优异。
以上内容是结合具体的实施方式对本申请所作的进一步详细说明，不能认定本申请的具体实施只局限于这些说明。对于本申请所属技术领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干简单推演或替换，都应当视为属于本申请的保护范围。

Claims (32)

  1. 一种用于锂离子电池的非水电解液，包括组分B，其特征在于，所述组分B包括不饱和磷酸酯类化合物和环状不饱和羧酸酐类化合物，所述不饱和磷酸酯类化合物具有结构式4所示结构，
    Figure PCTCN2016113649-appb-100001
    其中，R13、R11、R12分别独立地选自碳原子数为1-5的烃基，且R13、R11、R12中至少一个为含有双键或叁键的不饱和烃基；
    所述不饱和环状羧酸酐类化合物具有结构式5所示结构，
    Figure PCTCN2016113649-appb-100002
    其中，R14选自碳原子数为2-4的亚烯基或氟取代碳原子数为2-4的亚烯基。
  2. 根据权利要求1所述的非水电解液，其特征在于，所述不饱和磷酸酯类化合物选自
    Figure PCTCN2016113649-appb-100004
    中的一种或多种。
  3. 根据权利要求1所述的非水电解液，其特征在于，所述环状不饱和羧酸酐选自马来酸酐、2-甲基马来酸酐中一种或多种。
  4. 根据权利要求1所述的非水电解液，其特征在于，所述非水电解液中，不饱和磷酸酯类化合物占锂离子电池非水电解液总重量的0.1％～3％，环状不饱和羧酸酐类化合物占锂离子电池非水电解液总重量的0.1％～3％。
  5. 根据权利要求1-4中任一项所述的非水电解液，其特征在于，所述非水电解液中还包括不饱和环状碳酸酯、环状磺酸内酯、环状硫酸酯中的至少一种。
  6. 根据权利要求5所述的非水电解液，其特征在于，所述不饱和环状碳酸酯选自碳酸亚乙烯酯、碳酸乙烯亚乙酯中的至少一种；
    所述环状磺酸内酯选自1,3-丙烷磺内酯、1,4-丁烷磺内酯、1,3-丙烯磺内酯和甲烷二磺酸亚甲酯中的至少一种；
    所述环状硫酸酯选自硫酸乙烯酯和硫酸丙烯酯中的一种或两种；
    所述不饱和环状碳酸酯化合物用量占非水电解液总重量的0.1％-5％。环状磺酸内酯化合物用量占非水电解液总重量的0.1％-5％。环状硫酸酯化合物用量占非水电解液总重量的0.1％-5％。
  7. 根据权利要求1所述的非水电解液，其特征在于，所述非水电解液包含非水有机溶剂和锂盐，所述非水有机溶剂选自碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯和碳酸甲丙酯中的至少一种；所述锂盐选自六氟磷酸锂、四氟硼酸锂、二(三氟甲基磺酰)亚胺锂和双氟磺酰亚胺锂盐中的至少一种。
  8. 一种用于锂离子电池的非水电解液，包括组分A和组分B；其特征在于，所述组分A包括选自结构式1所示的氟代环状碳酸酯中至少一种，同时还包括结构式2所示的烷基取代环状碳酸酯中至少一种或/和结构式3所示的氟代羧酸酯中的至少一种；所述组分B包括结构式4所示的不饱和磷酸酯中的至少一种或/和结构式5所示的环状羧酸酐中的至少一种；
    Figure PCTCN2016113649-appb-100005
    其中，R1为氟元素或碳原子数为1-4的含氟烃基，R2、R3、R4分别独立选自氢元素、氟元素、碳原子数为1-4的烃基或碳原子数为1-4的含氟烃基；
    Figure PCTCN2016113649-appb-100006
    其中R5为碳原子数为1-4的烃基，R6、R7、R8分别独立选自氢元素或碳原子数为1-4的烃基；
    结构式3：R9COOR10，
    其中，R9、R10分别独立的选自碳原子数为1-4的烃基或碳原子数为1-4的氟 代烃基，且R9和R10中至少一个为所述氟代烃基；所述氟代烃基中至少含有两个氟原子；
    Figure PCTCN2016113649-appb-100007
    其中，R11为碳原子数为1-4的不饱和烃基，R12、R13分别独立的选自碳原子数为1-4的饱和烃基、碳原子数为1-4的不饱和烃基或碳原子数为1-4的氟代烃基；
    Figure PCTCN2016113649-appb-100008
    其中R14选自碳原子数为2-4的亚烷基、亚烯基、或碳原子数为2-4的含氟亚烷基、含氟亚烯基。
  9. 根据权利要求8所述的非水电解液，其特征在于，组分A含量占非水电解液总重量的10-90％，组分B含量占非水电解液总重量的0.1-3％。
  10. 根据权利要求8所述的非水电解液，其特征在于，所述结构式1所示化合物用量占非水电解液总重量的5％-80％，结构式2所示化合物用量占非水电解液总重量的5％-80％，结构式3所示化合物用量占非水电解液总重量的5％-80％，结构式4所示化合物用量占非水电解液总重量的0.1％-3％，结构式5所示化合物用量占非水电解液总重量的0.1％-3％。
  11. 根据权利要求8所述的非水电解液，其特征在于，所述结构式1所示的氟代环状碳酸酯选自式1-1、式1-2、式1-3、式1-4所示物质中的一种或多种：
    Figure PCTCN2016113649-appb-100009
  12. 根据权利要求8所述的非水电解液，其特征在于，所述结构式2所示的烷基取代环状碳酸酯选自式2-1、式2-2、式2-3所示物质中的一种或多种：
    Figure PCTCN2016113649-appb-100010
  13. 根据权利要求8所述的非水电解液，其特征在于，所述结构式3中，碳原子数为1-5的烃基选自甲基、乙基、丙基、丁基；所述氟代烃基选自氟代甲基、氟代乙基、氟代丙基、氟代丁基。
  14. 根据权利要求8所述的非水电解液，其特征在于，所述结构式3所示的氟代羧酸酯选自H3CCOOCH2CF2H、H3CH2CCOOCH2CF2H、HF2CH2CCOOCH3、HF2CH2CCOOCH2CH3、HF2CH2CH2CCOOCH2CH3、H3CCOOCH2CH2CF2H、H3CH2CCOOCH2CH2CF2H、CH3COOCH2CF3、HCOOCH2CHF2、HCOOCH2CF3、CH3COOCH2CF2CF2H中的至少一种。
  15. 根据权利要求8所述的非水电解液，其特征在于：所述结构式4中，碳原子数为1-4的饱和烃基包括但不仅限于甲基、乙基、丙基；碳原子数为1-4的不饱和烃基包括但不仅限于乙烯基、烯丙基、3-丁烯基、异丁烯基、乙炔基、炔丙基、3-丁炔基、1-甲基-2丙炔基；所述卤代烃基包括但不仅限于二氟甲基、三氟甲基、2,2-二氟乙基、2,2,2-三氟乙基、3,3-二氟丙基、3,3,3-三氟丙基、六氟异丙基。
  16. 根据权利要求8所述的非水电解液，其特征在于：所述结构式4所示的不饱和磷酸酯选自化合物选自磷酸三炔丙酯、二炔丙基甲基磷酸酯、二炔丙基乙基磷酸酯、二炔丙基丙基磷酸酯、二炔丙基三氟甲基磷酸酯、二炔丙基2,2,2-三氟乙基磷酸酯、二炔丙基3,3,3-三氟丙基磷酸酯、二炔丙基六氟异丙基磷酸酯、磷酸三烯丙酯、二烯丙基甲基磷酸酯、二烯丙基乙基磷酸酯、二烯丙基丙基磷酸酯、二烯丙基三氟甲基磷酸酯、二烯丙基2,2,2-三氟乙基磷酸酯、二烯丙基3,3,3-三氟丙基磷酸酯或二烯丙基六氟异丙基磷酸酯中的至少一种。
  17. 根据权利要求8所述的非水电解液，其特征在于：所述结构式5所示的环状羧酸酐选自化合物选自马来酸酐、2-甲基马来酸酐、丁二酸酐、戊二酸酐中的至少一种。
  18. 根据权利要求8-18中任意一项所述的非水电解液，其特征在于，所述非水电解液还包括不饱和环状碳酸酯、环状磺酸内酯、环状硫酸酯中的至少一种；
    所述不饱和环状碳酸酯化合物用量占非水电解液总重量的0.1％-5％，所述环状磺酸内酯化合物用量占非水电解液总重量的0.1％-5％，所述环状硫酸酯化合物用量占非水电解液总重量的0.1％-5％。
  19. 根据权利要求18所述的非水电解液，其特征在于，所述不饱和环状碳酸酯选自碳酸亚乙烯酯、碳酸乙烯亚乙酯中的至少一种；
    所述环状磺酸内酯选自1,3-丙烷磺内酯、1,4-丁烷磺内酯、1,3-丙烯磺内酯和甲烷二磺酸亚甲酯中的至少一种；
    所述环状硫酸酯选自下述结构所示物质中的一种或多种：
    Figure PCTCN2016113649-appb-100011
  20. 根据权利要求8-19任一项所述的非水电解液，其特征在于，所述非水电解液还包括选自碳酸乙烯酯、碳酸丁烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯和碳酸甲丙酯中的至少一种。
  21. 一种用于锂离子电池的非水电解质，其特征在于，包括选自结构式3所示的第一化合物中的至少一种和选自结构式4所示的第二化合物中的至少一种；
    结构式3：R9COOR10，
    结构式3中，R9、R10分别独立的选自碳原子数为1-5的烃基或氟代烃基，且R9和R10中至少一个为所述氟代烃基；所述氟代烃基中至少有两个氢被氟取代；
    Figure PCTCN2016113649-appb-100012
    结构式4中，R11、R12、R13分别独立的选自碳原子数为1-5的饱和烃基、不饱和烃基或卤代烃基，且R11、R12、R13中至少有一个为不饱和烃基。
  22. 根据权利要求21所述的非水电解液，其特征在于，所述结构式3中，碳原子数为1-5的烃基包括但不仅限于甲基、乙基、丙基、乙烯基、烯丙基、3-丁烯基、异丁烯基、4-戊烯基、乙炔基、炔丙基、3-丁炔基、1-甲基-2丙炔基；所述氟代烃基包括但不仅限于二氟甲基、三氟甲基、2,2-二氟乙基、2,2,2-三氟乙基、3,3-二氟丙基、3,3,3-三氟丙基、六氟异丙基；
    所述结构式4中，碳原子数为1-5的饱和烃基包括但不仅限于甲基、乙基、丙基；碳原子数为1-5的不饱和烃基包括但不仅限于乙烯基、烯丙基、3-丁烯基、异丁烯基、4-戊烯基、乙炔基、炔丙基、3-丁炔基、1-甲基-2丙炔基；碳原子数为1-5的卤代烃基包括但不仅限于二氟甲基、三氟甲基、2,2-二氟乙基、2,2,2-三氟乙基、3,3-二氟丙基、3,3,3-三氟丙基、六氟异丙基。
  23. 根据权利要求21所述的非水电解液，其特征在于，所述第一化合物选自H3CCOOCH2CF2H、H3CH2CCOOCH2CF2H、HF2CH2CCOOCH3、HF2CH2CCOOCH2CH3、HF2CH2CH2CCOOCH2CH3、H3CCOOCH2CH2CF2H、H3CH2CCOOCH2CH2CF2H、CH3COOCH2CF3、HCOOCH2CHF2、HCOOCH2CF3、CH3COOCH2CF2CF2H中的至少一种。
  24. 根据权利要求21所述的非水电解液，其特征在于，所述第二化合物选自磷酸三炔丙酯、二炔丙基甲基磷酸酯、二炔丙基乙基磷酸酯，二炔丙基丙基磷酸酯、二炔丙基三氟甲基磷酸酯、二炔丙基2,2,2-三氟乙基磷酸酯、二炔丙基3,3,3-三氟丙基磷酸酯、二炔丙基六氟异丙基磷酸酯、磷酸三烯丙酯、二烯丙基甲基磷酸酯、二烯丙基乙基磷酸酯，二烯丙基丙基磷酸酯、二烯丙基三氟甲基磷酸酯、二烯丙基2,2,2-三氟乙基磷酸酯、二烯丙基3,3,3-三氟丙基磷酸酯或二烯丙基六氟异丙基磷酸酯中的至少一种。
  25. 根据权利要求21-24任一项所述的非水电解液，其特征在于，所述非水电解液中，所述第一化合物用量占非水电解液总重量的10％-80％；所述第二化合物用量占非水电解液总重量的0.01％-5％。
  26. 根据权利要求21-24任一项所述的非水电解液，其特征在于，所述非水电解液中还包括不饱和环状碳酸酯、不饱和酸酐、环状硫酸酯、环状磺酸内酯、砜类中的一种或多种。
  27. 根据权利要求26所述的非水电解液，其特征在于，所述不饱和环状碳酸酯选自碳酸亚乙烯酯、碳酸乙烯亚乙酯中的至少一种；所述不饱和酸酐选自丁二酸酐、马来酸酐和2-甲基马来酸酐中的至少一种；所述环状硫酸酯选自硫酸乙烯酯和硫酸丙烯酯中的一种或两种；所述环状磺酸内酯选自1,3-丙烷磺内酯、1,4-丁烷磺内酯、1,3-丙烯磺内酯和甲烷二磺酸亚甲酯中的至少一种；所述砜类物质为环丁砜。
  28. 根据权利要求21-24任一项所述的非水电解液，其特征在于，所述非水电解液还包括选自碳酸乙烯酯、氟代碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯和碳酸甲丙酯、1,4-丁内酯中的至少一种；优选的，非水电解液还包括碳酸乙烯酯、氟代碳酸乙烯酯和碳酸丙烯酯中的至少一种。
  29. 一种锂离子电池，其特征在于，包括正极、负极、置于正极与负极之间的隔膜，以及电解液，其中，电解液为权利要求1-28中任意一项所述的非水电解液。
  30. 根据权利要求29所述的锂离子电池，其特征在于，所述正极包括正极活性材料，所述正极活性材料选自LiCoO2、LiNiO2、LiMn2O4、LiCo1-yMyO2、LiNi1-yMyO2、LiMn2-yMyO4和LiNixCoyMnzM1-x-y-zO2中的至少一种；其中，M选自Fe、Co、Ni、Mn、Mg、Cu、Zn、Al、Sn、B、Ga、Cr、Sr、V和Ti中的至少一种，且0≤y≤1，0≤x≤1，0≤z≤1，x+y+z≤1。
  31. 根据权利要求29所述的锂离子电池，其特征在于，所述正极包括正极活性材料，所述正极活性材料为LiNixCoyMnzL(1-x-y-z)O2、LiCox’L(1-x’)O2和LiNix”L’y’Mn(2-x”-y’)O4中的至少一种，其中，L为Al、Sr、Mg、Ti、Ca、Zr、Zn、Si或Fe，0≤x≤1，0≤y≤1，0≤z≤1，0＜x+y+z≤1，0<x’≤1，0.3≤x”≤0.6，0.01≤y’≤0.2，L’为Co、Al、Sr、Mg、Ti、Ca、Zr、Zn、Si或Fe。
  32. 根据权利要求29-31任一项所述的锂离子电池，其特征在于，锂离子电池的充电截止电压大于或等于4.3V。
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