WO2020248567A1 - 一种降低电池阻抗的锂二次电池电解液及其锂二次电池 - Google Patents

一种降低电池阻抗的锂二次电池电解液及其锂二次电池 Download PDF

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WO2020248567A1
WO2020248567A1 PCT/CN2019/127033 CN2019127033W WO2020248567A1 WO 2020248567 A1 WO2020248567 A1 WO 2020248567A1 CN 2019127033 W CN2019127033 W CN 2019127033W WO 2020248567 A1 WO2020248567 A1 WO 2020248567A1
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carbonate
lithium
electrolyte
secondary battery
lithium secondary
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PCT/CN2019/127033
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English (en)
French (fr)
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范伟贞
曹哥尽
范超君
余乐
赵经纬
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广州天赐高新材料股份有限公司
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Priority to US17/614,215 priority Critical patent/US20220238909A1/en
Priority to EP19933122.4A priority patent/EP3972024A4/en
Publication of WO2020248567A1 publication Critical patent/WO2020248567A1/zh

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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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—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
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • 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
    • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 lithium secondary batteries. More specifically, the present invention provides a lithium secondary battery electrolyte and a lithium secondary battery that reduce battery impedance.
  • lithium secondary batteries Because of its high energy density, long cycle life, and pollution-free characteristics, lithium secondary batteries have broad application prospects in consumer electronics, power car batteries and energy storage power supplies.
  • lithium secondary battery technology applied to automobile power has developed rapidly. Higher requirements are put forward on the performance of lithium secondary batteries.
  • the battery needs to have a longer service life, needs to be able to be used under extreme temperatures, needs to be able to charge and discharge quickly (high rate), and needs to have better safety.
  • the battery pack of an electric vehicle is generally composed of multiple batteries in series or in parallel.
  • the battery generates a certain amount of heat during normal operation.
  • the entire battery pack uses a battery thermal management system to conduct thermal management of the battery.
  • the greater the discharge rate of the battery or the greater the internal resistance of the battery the greater the heat generation of the battery. If the internal resistance of the battery can be reduced, the heat generation of the battery can be reduced. At the same time, the higher the charge and discharge rate of the battery, the greater the heat generation of the battery. If the internal resistance of the battery can be reduced, the heat generation of the battery with high charge and discharge rate can also be reduced.
  • the battery pack is composed of multiple batteries, the consistency of a single battery determines the service life of the entire battery pack. If the impedance of the battery can be reduced, the consistency of the battery can be greatly improved, thereby increasing the service life of the battery.
  • the first aspect of the present invention provides an electrolyte for a lithium secondary battery, which contains a non-aqueous solvent, a lithium salt and an additive; wherein the additive includes a sulfonate compound.
  • R 1 and R 2 are independently selected from one of aliphatic hydrocarbon groups with 1-5 carbon atoms, aryl groups, alkyl-substituted aryl groups, and silicon groups; any group can be substituted by halogen atoms .
  • R 1 and R 2 are each independently selected from methyl, ethyl, propyl, fluoromethyl, fluoroethyl, vinyl, allyl, phenyl, benzene One of methyl, fluorophenyl, trimethylsilyl, and trivinylsilyl.
  • the sulfonate compound is selected from Any one or a combination of multiple.
  • the mass of the sulfonate compound accounts for 0.1% to 5% of the total mass of the electrolyte.
  • the additive further includes a second additive selected from the group consisting of vinylene carbonate, fluoroethylene carbonate, lithium difluorophosphate, lithium dioxalate borate, and difluorooxalic acid Lithium borate, 1,3-propane sultone, triallyl isocyanurate, methylene disulfonate, vinyl sulfate, triallyl phosphate, tripropynyl phosphate, three Any one or a combination of (trimethylsilane) phosphate and tris(trimethylsilane) borate.
  • a second additive selected from the group consisting of vinylene carbonate, fluoroethylene carbonate, lithium difluorophosphate, lithium dioxalate borate, and difluorooxalic acid Lithium borate, 1,3-propane sultone, triallyl isocyanurate, methylene disulfonate, vinyl sulfate, triallyl phosphate, tripropynyl
  • the mass of the second additive accounts for 0.01% to 10% of the total mass of the electrolyte.
  • the mass of the non-aqueous solvent accounts for 67-91% of the total mass of the electrolyte.
  • the non-aqueous solvent includes cyclic ester and chain ester.
  • the cyclic ester is selected from any one or a combination of ethylene carbonate, propylene carbonate, butylene carbonate, and ⁇ -butyrolactone.
  • the chain ester is selected from dimethyl carbonate, diethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, carbonic acid Ethylene propyl, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, 2,2-difluoroethyl Any one or a combination of glycyl acetate.
  • the mass of the lithium salt accounts for 8-18% of the total mass of the electrolyte.
  • the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium bisfluorosulfonimide, and lithium bis(trifluoromethanesulfonyl)imide.
  • the second aspect of the present invention provides a lithium secondary battery, which includes a positive electrode, a negative electrode, and an electrolyte; wherein the electrolyte used is the electrolyte.
  • the lithium secondary battery is selected from any one of lithium ion batteries, lithium sulfur batteries, and lithium air batteries.
  • the active material of the positive electrode is a lithium-containing transition metal oxide and/or a lithium-containing transition metal phosphate compound.
  • the active material of the positive electrode is selected from Li 1+a (Ni x Co y M 1-xy )O 2 , Li(Ni n Mn m Co 2-nm )O 4 , LiM Any of p (PO 4 ) q ; where 0 ⁇ a ⁇ 0.3, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ x+y ⁇ 1, 0 ⁇ n ⁇ 2, 0 ⁇ m ⁇ 2, 0 ⁇ n+m ⁇ 2, M is selected from any one of Al, Fe, Ni, Co, Mn, and V, and 0 ⁇ p ⁇ 5, 0 ⁇ q ⁇ 5.
  • the active material of the negative electrode is selected from any one or a combination of lithium metal, lithium alloy, carbon material, silicon or tin and oxides thereof.
  • the present invention Compared with the prior art, the present invention has the following beneficial effects: the present invention provides an electrolyte for lithium secondary batteries.
  • the lithium secondary battery using the electrolyte has lower impedance, and at the same time has better low-temperature performance, High temperature performance and cycle life; at the same time, the present invention also discloses the use of lithium ion batteries containing the electrolyte.
  • the first aspect of the present invention provides an electrolyte for a lithium secondary battery, which contains a non-aqueous solvent, a lithium salt and an additive; wherein the additive includes a sulfonate compound.
  • the sulfonate compound is selected from at least one compound represented by the general formula (A):
  • R 1 and R 2 are independently selected from one of aliphatic hydrocarbon groups with 1-5 carbon atoms, aryl groups, alkyl-substituted aryl groups, and silicon groups; any group can be substituted by halogen atoms .
  • Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.
  • alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, new Pentyl, 1-methylbutyl, 2-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, etc.
  • alkyl groups substituted by halogen atoms include fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 1, 2-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 1-fluoro-n-propyl, 2-fluoro-n-propyl, 3-fluoro-n-propyl Propyl, 1,1-difluoro-n-propyl, 1,2-difluoro-n-propyl, 1,3-difluoro-n-propyl, 2,2-difluoro-n-propyl, 2,3-difluoro-n-propyl Propyl, 3,3-difluoro-n-propyl, 3,3,3-trifluoro-n-propyl, 2,2,3,3,3,
  • alkenyl groups include alkenyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2- Pentenyl, 3-pentenyl, 4-pentenyl and the like.
  • alkenyl groups substituted with halogen atoms include 1-fluorovinyl, 2-fluorovinyl, 1,2-difluorovinyl, 2,2-difluorovinyl, 1,2,2-trifluoroethylene, Fluorovinyl, 1-fluoro-1-propenyl, 2-fluoro-1-propenyl, 3-fluoro-1-propenyl, 1,2-difluoro-1-propenyl, 1,3-difluoro- 1-propenyl, 2,3-difluoro-1-propenyl, 3,3-difluoro-1-propenyl, 1,2,3-trifluoro-1-propenyl, 1,3,3-tri Fluoro-1-propenyl, 2,3,3-trifluoro-1-propenyl, 3,3,3-trifluoro-1-propenyl, 1,2,3,3-tetrafluoro-1-propenyl , 1,3,3,3-tetrafluoro-1-prop
  • alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl Alkynyl, 3-pentynyl, 4-pentynyl and the like.
  • alkynyl groups substituted by halogen atoms include 2-fluoroethynyl, 3-fluoro-1-propynyl, 3,3-difluoro-1-propynyl, and 3,3,3-trifluoro -1-propynyl, 3-fluoro-2-propynyl, 1-fluoro-2-propynyl, 1,1-difluoro-2-propynyl, 1,3-difluoro-2-propynyl Alkynyl, 1,1,3-trifluoro-2-propynyl, etc.
  • aryl groups include phenyl, tolyl, xylyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl, isobutyl Phenyl, tert-butylphenyl, etc.
  • phenyl substituted by alkyl examples include benzyl, ⁇ -methylbenzyl, 1-methyl-1-phenylethyl, phenethyl, 2-phenylpropyl, 2-methyl -2-phenylpropyl, 3-phenylpropyl, 3-phenylbutyl, 3-methyl-3-phenylbutyl, 4-phenylbutyl, 5-phenylpentyl, 6- Phenylhexyl and others.
  • Examples of the phenyl substituted by halogen atoms include: 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2 ,5-Difluorophenyl, 2,6-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,5,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,4, 5-tetrafluorophenyl, 2,3,4,6-tetrafluorophenyl, 2,4,5,6-tetrafluorophenyl, pentafluorophenyl.
  • R 1 and R 2 are each independently selected from methyl, ethyl, propyl, fluoromethyl, fluoroethyl, vinyl, propenyl, phenyl, tolyl, fluoro One of phenyl, trimethylsilyl, trivinyl, and silicon.
  • sulfonate compound more preferably Any one or a combination of multiple.
  • the mass of the sulfonate compound accounts for 0.1% to 5% of the total mass of the electrolyte; more preferably, the mass of the sulfonate compound accounts for 0.5% to 5% of the total mass of the electrolyte.
  • the additive further includes a second additive.
  • a carbonate compound having a carbon-carbon unsaturated bond As the second additive, a carbonate compound having a carbon-carbon unsaturated bond, a carbonate compound having a halogen atom, a fluorophosphoric acid compound, a phosphoric acid ester compound, a silicon-containing compound, a sulfonic acid ester compound, a sulfate ester compound, Compounds having isocyanate groups, etc.
  • carbonate compound having a carbon-carbon unsaturated bond as long as it is a carbonate having a carbon-carbon unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond, there are no other restrictions, and any unsaturated carbonate can be used.
  • carbonates having an aromatic ring are also included in carbonates having an unsaturated bond.
  • carbonate compounds having carbon-carbon unsaturated bonds include methyl vinyl carbonate, ethyl vinyl carbonate, divinyl carbonate, methyl propynyl carbonate, and ethyl propyne carbonate.
  • carbonate compounds having halogen atoms include fluoroethylene carbonate, chloroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, 4,4 -Dichloroethylene carbonate, 4,5-dichloroethylene carbonate, 4-fluoro-4-methylethylene carbonate, 4-chloro-4-methylethylene carbonate, 4,5-di Fluoro-4-methylethylene carbonate, 4,5-dichloro-4-methylethylene carbonate, 4-fluoro-5-methylethylene carbonate, 4-chloro-5-methylethylene carbonate Ethyl ester, 4,4-difluoro-5-methylethylene carbonate, 4,4-dichloro-5-methylethylene carbonate, 4-(fluoromethyl)ethylene carbonate, 4-( Chloromethyl) ethylene carbonate, 4-(difluoromethyl) ethylene carbonate, 4-(dichloromethyl) ethylene carbonate, 4-(trifluoromethyl) ethylene carbonate, 4- (Trichloromethyl) ethylene carbonate
  • fluoromethyl phenyl carbonate 2-fluoroethyl phenyl carbonate, 2,2-difluoroethyl phenyl carbonate, 2,2,2-trifluoroethyl phenyl carbonate , Chloromethylphenyl carbonate, 2-chloroethylphenyl carbonate, 2,2-dichloroethylphenyl carbonate, 2,2,2-trichloroethylphenyl carbonate, fluoromethyl carbonate Vinyl vinyl ester, 2-fluoroethyl vinyl carbonate, 2,2-difluoroethyl vinyl carbonate, 2,2,2-trifluoroethyl vinyl carbonate, chloromethyl vinyl carbonate , 2-chloroethyl vinyl carbonate, 2,2-dichloroethyl vinyl carbonate, 2,2,2-trichloroethyl vinyl carbonate, fluoromethyl allyl carbonate, 2 -Fluoroethyl allyl ester, 2,2-
  • fluorophosphoric acid compound examples include: lithium difluorophosphate, difluorophosphoric acid, monofluorophosphoric acid, methyl difluorophosphate, ethyl difluorophosphate, dimethyl fluorophosphate, diethyl fluorophosphate, difluoro-difluorophosphate Lithium oxalate phosphate, lithium tetrafluorooxalate phosphate, lithium trioxalate phosphate, lithium difluorooxalate borate, lithium dioxalate borate, etc.
  • Examples of phosphoric acid ester compounds include: dimethyl vinyl phosphate, diethyl vinyl phosphate, dipropyl vinyl phosphate, dibutyl vinyl phosphate, and dipentyl vinyl phosphate.
  • Vinyl compound dimethyl vinyl phosphate, diethyl vinyl phosphate, dipropyl vinyl phosphate, dibutyl vinyl phosphate, and dipentyl vinyl phosphate.
  • Phosphoric acid 2-acryloxy methyl dimethyl ester Phosphoric acid 2-acryloxy methyl dimethyl ester, phosphoric acid 2-acryloxy methyl diethyl ester, phosphoric acid 2-acryloxy methyl dipropyl ester, phosphoric acid 2-acryloxy methyl ester 2-acryloxymethyl compounds such as dibutyl phosphate and 2-acryloxymethyl dipentyl phosphate;
  • Phosphoric acid 2-acryloyloxyethyl dimethyl ester Phosphoric acid 2-acryloyloxyethyl diethyl ester, Phosphoric acid 2-acryloyloxyethyl dipropyl ester, Phosphoric acid 2-acryloyloxy ethyl 2-acryloyloxyethyl compounds such as dibutyl phosphate and 2-acryloyloxyethyl dipentyl phosphate;
  • Diallyl methyl phosphate, diallyl ethyl phosphate, diallyl phosphate, diallyl butyl phosphate, diallyl pentyl phosphate, etc. have allyl groups Compound
  • Dipropargyl methyl phosphate, dipropargyl ethyl phosphate, dipropargyl propyl phosphate, dipropargyl butyl phosphate and dipropargyl pentyl phosphate, etc. have propargyl groups Compound
  • Bis(2-acryloyloxymethyl)methyl phosphate bis(2-acryloyloxymethyl)ethyl phosphate, bis(2-acryloyloxymethyl)propyl phosphate, bis(2-acryloyloxymethyl)propyl phosphate, double phosphate
  • 2-acryloxymethyl groups such as (2-acryloyloxymethyl)butyl ester and bis(2-acryloyloxymethyl)pentyl phosphate;
  • Trivinyl phosphate Trivinyl phosphate, triallyl phosphate, tripropargyl phosphate, tris(2-acryloyloxymethyl) phosphate, tris(2-acryloyloxyethyl) phosphate, etc.
  • silicon-containing compounds include: tris(trimethylsilyl) phosphate, bis(trimethylsilyl) phosphate, mono(trimethylsilyl) phosphate, dimethyl tris Methyl silyl ester, methyl bis(trimethylsilyl) phosphate, diethyltrimethylsilyl phosphate, ethyl bis(trimethylsilyl) phosphate, dipropylene phosphate Trimethylsilyl phosphate, propyl bis(trimethylsilyl) phosphate, dibutyltrimethylsilyl phosphate, butyl bis(trimethylsilyl) phosphate, phosphoric acid Dioctyl trimethylsilyl ester, octyl bis(trimethylsilyl) phosphate, diphenyl trimethylsilyl phosphate, phenyl bis(trimethylsilyl) phosphate , Bis(trifluoroethyl)(trimethylsilyl) phosphate, trifluoroe
  • Tris(trimethylsilane) borate tris(trimethoxysilyl) borate, tris(triethylsilyl) borate, tris(triethoxysilyl) borate, tris borate (Dimethylvinylsilyl) and boric acid compounds such as tris(diethylvinylsilyl) borate;
  • Sulfonic acid compounds such as trimethylsilyl methanesulfonate and trimethylsilyl tetrafluoromethanesulfonate.
  • sulfonate compounds include: 1,3-propane sultone, 1-fluoro-1,3-propane sultone, 2-fluoro-1,3-propane sultone, 3- Fluoro-1,3-propane sultone, 1-methyl-1,3-propane sultone, 2-methyl-1,3-propane sultone, 3-methyl-1,3 -Propylene sultone, 1-propene-1,3-sultone, 2-propene-1,3-sultone, 1-fluoro-1-propene-1,3-sultone, 2-fluoro-1-propene-1,3-sultone, 3-fluoro-1-propene-1,3-sultone, 1-fluoro-2-propene-1,3-sultone , 2-fluoro-2-propene-1,3-sultone, 3-fluoro-2-propene-1,3-sultone, 1-methyl-1-propene-1,3-sulf
  • sulfate compounds include 1,2-ethylene glycol sulfate, 1,2-propanediol sulfate, 1,3-propanediol sulfate, 1,2-butanediol sulfate, 1,3-butane Glycol sulfate, 1,4-butanediol sulfate, 1,2-pentanediol sulfate, 1,3-pentanediol sulfate, 1,4-pentanediol sulfate and 1,5-pentane Glycol sulfate, ethylene sulfite, propylene sulfite, ethylene sulfate, propylene sulfate, butylene sulfate, hexylene sulfate, vinylene sulfate, 3-sulfolene, diethylene Base sulfone, dimethyl sulfate, diethyl s
  • Examples of compounds having isocyanate groups include: methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, tert-butyl isocyanate, pentyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, vinyl Isocyanate, allyl isocyanate, triallyl isocyanurate, ethynyl isocyanate, propynyl isocyanate, phenyl isocyanate, fluorophenyl isocyanate.
  • the second additive is selected from vinylene carbonate, fluoroethylene carbonate, lithium difluorophosphate, lithium dioxalate borate, lithium difluorooxalate borate, 1,3-propane sultone, triallyl iso Cyanurate, methylene methane disulfonate, vinyl sulfate, triallyl phosphate, tripropynyl phosphate, tris(trimethylsilane) phosphate, tris(trimethylsilane) boric acid Any one or a combination of esters.
  • the second additive is selected from vinylene carbonate, fluoroethylene carbonate, lithium difluorophosphate, lithium difluorooxalate borate, triallyl isocyanurate, triallyl phosphate, tripropylene Any one or a combination of alkynyl phosphates.
  • the mass of the second additive accounts for 0.01% to 10% of the total mass of the electrolyte; preferably, the mass of the second additive accounts for 0.1% to 8% of the total mass of the electrolyte; more preferably, the mass of the second additive accounts for 0.5% of the total mass of the electrolyte. % ⁇ 5.5%.
  • the mass of the non-aqueous solvent accounts for 67 to 91% of the total mass of the electrolyte; preferably, the mass of the non-aqueous solvent accounts for 77 to 87% of the total mass of the electrolyte.
  • non-aqueous solvent various non-aqueous solvents can be appropriately selected, and it is preferable to use at least one selected from a cyclic aprotic solvent and a chain aprotic solvent to improve the solubility, stability and Electrical conductivity.
  • cyclic aprotic solvent cyclic esters, cyclic sulfones, and cyclic ethers can be used.
  • cyclic sulfones include, but are not limited to, sulfolane, 2-methyl sulfolane, 3-methyl sulfolane, dimethyl sulfone, diethyl sulfone, dipropyl sulfone, methyl ethyl sulfone, methyl propyl sulfone Sulfone etc.
  • cyclic ethers include but are not limited to dioxolane.
  • cyclic esters include cyclic carbonates and cyclic carboxylic acid esters.
  • the type of cyclic carbonate is not limited, including but not limited to: methyl vinyl carbonate, ethyl vinyl carbonate, divinyl carbonate, methallyl carbonate, ethyl allyl Carbonate, diallyl carbonate, methyl propynyl carbonate, ethyl propynyl carbonate, dipropynyl carbonate, methyl phenyl carbonate, ethyl phenyl carbonate, diphenyl carbonate, etc.
  • Chain carbonates vinylene carbonate, methyl vinylene carbonate, 4,4-dimethyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, vinyl ethylene carbonate , 4,4-divinyl ethylene carbonate, 4,5-divinyl ethylene carbonate, allyl ethylene carbonate, 4,4-diallyl ethylene carbonate, 4,5-diallyl ethylene carbonate, methylene ethylene carbonate, 4,4-dimethyl-5-methylene ethylene carbonate, ethynyl ethylene carbonate, 4,4-diethynyl ethylene carbonate, 4,5-diethynyl ethylene carbonate, propynyl ethylene carbonate, 4,4-dipropynyl ethylene carbonate, 4 , 5-Dipropynyl ethylene carbonate, phenyl ethylene carbonate, 4,5-diphenyl ethylene carbonate, phenylene carbonate, fluorocarbonic acid, fluoroethylene carbonate, Trifluoroethylene carbon
  • the types of cyclic carboxylic acid esters are not limited, including but not limited to: ⁇ -butyrolactone, methyl ⁇ -butyrolactone, ethyl ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexyl Lactone, ⁇ -heptanolide, ⁇ -valerolactone, ethyl ⁇ -valerolactone, etc.
  • the cyclic ester is preferably at least one of ethylene carbonate, propylene carbonate, ⁇ -butyrolactone, and butylene carbonate.
  • chain aprotic solvent chain esters, chain ethers, etc. can be used.
  • chain esters examples include cyclic carbonates, cyclic carboxylic acid esters, and chain phosphate esters.
  • chain carboxylic acid esters are not limited, including but not limited to: dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethyl methyl carbonate, methyl acetate, ethyl acetate, Propyl acetate, methyl propionate, methyl butyrate, methyl isobutyrate, trimethyl methyl acetate, trimethyl ethyl acetate, methyl malonate, ethyl malonate, methyl succinate Ester, ethyl succinate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethylene glycol diacetate, propylene glycol diacetate, 2,2-difluoroethyl Acetate etc.
  • chain carbonates are not limited, including but not limited to: dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, ethylene propyl carbonate, dipropyl carbonate, two Ethyl carbonate and so on.
  • the type of chain phosphate is not limited, including but not limited to: trimethyl phosphate, triethyl phosphate, triphenyl phosphate and the like.
  • dimethyl carbonate, diethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethylene propyl carbonate, methyl formate, and ethyl formate are preferred.
  • the weight ratio of the cyclic ester and the chain ester is 1:(1-5); preferably, in one embodiment, the weight ratio of the cyclic ester and the chain ester is 1:( 1 ⁇ 2.5).
  • the electrolyte used in the non-aqueous electrolyte solution of the present invention is not limited, and any known electrolyte can be used as long as it is used as an electrolyte in the target non-aqueous electrolyte secondary battery.
  • a lithium salt is generally used as an electrolyte.
  • lithium salts include inorganic lithium salts such as LiPF 6 , LiBF 4 , LiClO 4 , LiAlF 4 , LiSbF 6 , LiTaF 6 , and LiWF 7 ; lithium tungstates such as LiWOF 5 ; HCO 2 Li, CH 3 CO 2 Li , CH 2 FCO 2 Li, CHF 2 CO 2 Li, CF 3 CO 2 Li, CF 3 CH 2 CO 2 Li, CF 3 CF 2 CO 2 Li, CF 3 CF 2 CF 2 CO 2 Li, CF 3 CF 2 CF 2 CO 2 Li and other carboxylic acid lithium salts; FSO 3 Li, CH 3 SO 3 Li, CH 2 FSO 3 Li, CHFSO 3 Li, CHF 2 SO 3 Li, CF 3 SO 3 Li, CF 3 CF 2 SO 3 Li, CF 3 CF 2 CF 2 SO 3 Li, CF 3 CF 2 CF 2 SO 3 Li, CF 3 CF 2 CF 2 SO 3 Li and other sulfonic acid lithium salts
  • the lithium salt is preferably at least one of LiSbF 6 , lithium bisfluorosulfonimide, and lithium bis(trifluoromethanesulfonyl)imide.
  • the mass of the lithium salt accounts for 8-18% of the total mass of the electrolyte
  • a second aspect of the present invention provides a lithium secondary battery, which includes a positive electrode, a negative electrode, and the electrolyte.
  • the lithium secondary battery in the present invention is selected from any one of lithium ion batteries, lithium sulfur batteries, and lithium air batteries; lithium ion batteries, lithium sulfur batteries and lithium air batteries are technical terms well known to those skilled in the art.
  • the shape and type of the lithium secondary battery in the present invention are not particularly limited, and may be lithium secondary batteries such as lithium ion batteries, lithium ion polymer batteries, lithium sulfur batteries, and lithium primary batteries.
  • the lithium battery can be manufactured by a manufacturing method known in the related art.
  • the positive electrode contains a positive electrode active material capable of storing and releasing lithium.
  • the positive electrode active material is not particularly limited as long as it can electrochemically store and release lithium ions.
  • a substance containing lithium and at least one transition metal is preferable, and examples thereof include lithium-transition metal composite oxides and lithium-containing transition metal phosphate compounds.
  • the transition metal of the lithium-transition metal composite oxide V, Ti, Cr, Mn, Fe, Co, Ni, Cu, etc. are preferred, and specific examples include lithium-cobalt composite oxides such as LiCoO 2 ; lithium such as LiNiO 2 -Nickel composite oxide; LiMnO 2 , LiMn 2 O 4 , Li 2 MnO 3 and other lithium-manganese composite oxides; use Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg , Ga, Zr, Si and other metals instead of a part of the transition metal atoms forming the main body of these lithium-transition metal composite oxides.
  • lithium-cobalt composite oxides such as LiCoO 2 ; lithium such as LiNiO 2 -Nickel composite oxide; LiMnO 2 , LiMn 2 O 4 , Li 2 MnO 3 and other lithium-manganese composite oxides; use Al, Ti, V, Cr, Mn, Fe, Co
  • substances obtained by substitution include, for example, LiNi 0.5 Mn 0.5 O 2 , LiNi 0.85 Co 0.10 Al 0.05 O 2 , LiNi 0.33 Co 0.33 Mn 0.33 O 2 , LiMn 1.8 Al 0.2 O 4 , LiMn 1.5 Ni 0.5 O 4 etc.
  • the transition metal of the lithium-containing transition metal phosphate compound is preferably V, Ti, Cr, Mn, Fe, Co, Ni, Cu, etc.
  • LiFePO 4 , Li 3 Fe 2 (PO 4 ) 3 Iron phosphates such as LiFeP 2 O 7 ; Cobalt phosphates such as LiCoPO 4 ; Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Nb, Si, etc.
  • the metal substitutes for a substance or the like obtained by substituting a part of the transition metal atom forming the main body of these lithium-containing transition metal phosphate compounds.
  • any one of Li 1+a (Ni x Co y M 1-xy )O 2 , Li(Ni n Mn m Co 2-nm )O 4 , and LiM p (PO 4 ) q is preferable; 0 ⁇ a ⁇ 0.3, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ x+y ⁇ 1, 0 ⁇ n ⁇ 2, 0 ⁇ m ⁇ 2, 0 ⁇ n+m ⁇ 2, M is selected from Al , Fe, Ni, Co, Mn, V, and 0 ⁇ p ⁇ 5, 0 ⁇ q ⁇ 5.
  • the binder used in the production of the positive electrode active material layer is not particularly limited. When the coating method is used, any material that can be dissolved or dispersed in the liquid medium used in the electrode production is sufficient. Specific examples include Polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, cellulose, nitrocellulose and other resin polymers; SBR (styrene-butadiene rubber ), NBR (acrylonitrile-butadiene rubber), fluororubber, isoprene rubber, butadiene rubber, ethylene-propylene rubber and other rubbery polymers; styrene-butadiene-styrene block copolymer Or its hydrogenated product, EPDM (ethylene-propylene-diene terpolymer), styrene-ethylene-butadiene-ethylene copolymer, styrene-isoprene-styrene block copolymer or its addition Hydrogen compounds and other thermoplastic e
  • the ratio of the binder in the positive electrode active material layer is too low, the positive electrode active material cannot be sufficiently maintained, the mechanical strength of the positive electrode is insufficient, and battery performance such as cycle characteristics deteriorate. On the other hand, if the proportion of the binder is too high, it may sometimes cause a decrease in battery capacity or conductivity.
  • any solvent can be used as long as it can dissolve or disperse the positive electrode active material, conductive material, binder, and thickener used as required.
  • water-based solvents can be used. Any solvent among solvents and organic solvents.
  • aqueous medium water, a mixed medium of alcohol and water, etc. are mentioned.
  • organic solvents include aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as benzene, toluene, xylene, and methyl naphthalene; heterocyclic compounds such as quinoline and pyridine; acetone, methyl ethyl ketone, cyclohexanone, etc.
  • Ketones such as methyl acetate and methyl acrylate; amines such as diethylenetriamine and N,N-dimethylaminopropylamine; ethers such as ether, propylene oxide, and tetrahydrofuran (THF); N- Amides such as methylpyrrolidone (NMP), dimethylformamide and dimethylacetamide; polar aprotic solvents such as hexamethylphosphoramide and dimethylsulfoxide.
  • NMP methylpyrrolidone
  • NMP dimethylformamide and dimethylacetamide
  • polar aprotic solvents such as hexamethylphosphoramide and dimethylsulfoxide.
  • the positive electrode can be produced by forming a positive electrode active material layer containing a positive electrode active material and a binder on a current collector.
  • the production of the positive electrode using the positive electrode active material can be performed by a conventional method.
  • the positive electrode active material and the binder, as well as the conductive materials and thickeners used as needed can be dry-mixed and made into a sheet, and then the sheet material can be pressed on the positive current collector.
  • these materials are dissolved or dispersed in a liquid medium to prepare a slurry, and the slurry is coated on a positive electrode current collector and dried to form a positive electrode active material layer on the current collector to obtain a positive electrode.
  • the negative electrode contains a negative electrode active material capable of storing and releasing lithium.
  • a transition material selected from the group consisting of metallic lithium, lithium-containing alloys, metals or alloys capable of being alloyed with lithium, oxides capable of doping/undoping lithium ions, and transitions capable of doping/undoping lithium ions can be used. At least one combination of one or more of the metal nitride and the carbon material capable of doping/undoping lithium ions.
  • the negative electrode active material is preferably any one or a combination of lithium metal, lithium alloy, carbon material, silicon or tin and oxides thereof.
  • the binder for binding the negative electrode active material is not particularly limited as long as it is a material that is stable with respect to the solvent used in the production of the non-aqueous electrolyte and the electrode.
  • resins such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, polyimide, cellulose, and nitrocellulose.
  • Polymers SBR (styrene butadiene rubber), isoprene rubber, butadiene rubber, fluororubber, NBR (nitrile rubber), ethylene propylene rubber and other rubbery polymers; styrene-butadiene-styrene embedded Block copolymer or its hydrogenated product; EPDM (ethylene-propylene-diene terpolymer), styrene-ethylene-butadiene-styrene copolymer, styrene-isoprene-styrene block copolymer Thermoplastic elastomer-like polymers or its hydrogenated products; syndiotactic 1,2-polybutadiene, polyvinyl acetate, ethylene-vinyl acetate copolymer, propy
  • any solvent that can dissolve or disperse the negative electrode active material, the binder, and the thickener and conductive material used as needed is not particularly limited, and it can be water-based Any solvent among solvents and non-aqueous solvents.
  • aqueous solvents examples include water, alcohol, etc.; examples of non-aqueous solvents include N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, and acrylic acid.
  • NMP N-methylpyrrolidone
  • a thickener in the case of using an aqueous solvent, it is preferable to use a thickener while containing a dispersant and the like, and to form a slurry with a latex such as SBR.
  • a dispersant and the like it is preferable to use a thickener while containing a dispersant and the like, and to form a slurry with a latex such as SBR.
  • these solvents may be used singly, or two or more of them may be used in any combination and ratio.
  • Thickeners are usually used to adjust the viscosity of the slurry. There are no particular restrictions on the thickener, and specific examples include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, Their salt etc. These thickeners may be used alone, or two or more of them may be used in any combination and ratio.
  • the thickener When the thickener is in an appropriate range with respect to the negative electrode active material, the decrease in battery capacity and the increase in impedance can be suppressed, and good coating properties can be ensured.
  • the production of the negative electrode of the present invention can employ any known method.
  • a slurry can be prepared by adding a binder, a solvent, a thickener, a conductive material, etc. to the negative electrode active material, and then coating the slurry on the current collector and drying it. After that, pressing is performed to form electrodes.
  • Embodiment 1 of the present invention provides a lithium secondary battery, the preparation process of which is as follows:
  • the positive electrode active material, lithium nickel cobalt manganese oxide (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ), the conductive agent Super-P, and the binder PVDF are dissolved in the solvent N-form at a mass ratio of 96:2.0:2.0
  • the negative electrode active material graphite, conductive agent Super-P, thickener CMC, and binder SBR are dissolved in the solvent deionized water at a mass ratio of 96.5:1.0:1.0:1.5 to make a negative electrode slurry, and then the negative electrode slurry Coat evenly on the current collector copper foil with a coating amount of 0.0089g/cm 2 , then dry at 85°C, then perform cold pressing, trimming, cutting, and slitting, and then dry at 110°C under vacuum for 4h , Weld the tabs to make the negative electrode sheet of the lithium secondary battery that meets the requirements.
  • the electrolyte of the lithium secondary battery uses 12.5% of the total mass of the electrolyte as the lithium salt, and the mixture of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate as the non-aqueous organic solvent, accounting for 81.5 of the total mass of the electrolyte %, wherein the mass ratio of ethylene carbonate, ethyl methyl carbonate, and diethyl carbonate is 3:5:2.
  • the lithium secondary electrolyte also contains additives, and the additive is compound 1 which accounts for 3.0% of the total mass of the lithium secondary battery electrolyte.
  • the second additive is vinylene carbonate and 1,3-propane sultone, which respectively account for 1.0% and 2.0% of the total mass of the electrolyte.
  • the positive electrode sheet, the negative electrode sheet and the separator of the lithium secondary battery prepared according to the foregoing process are made into a cell with a thickness of 8mm, a width of 60mm, and a length of 130mm through a winding process, and vacuum-baked at 75°C for 10h, Inject electrolyte, let stand for 24h, then charge to 4.2V with a constant current of 0.1C (160mA), then charge at a constant voltage of 4.2V until the current drops to 0.05C (80mA), and then use a constant current of 0.1C (160mA) Discharge to 3.0V, repeat the charge and discharge twice, and finally charge to 3.8V with a constant current of 0.1C (160mA) to complete the preparation of the lithium secondary battery.
  • Embodiment 2 of the present invention provides a lithium secondary battery, which is prepared according to the method of embodiment 1, except that the electrolyte of the lithium secondary battery uses 10.0% of the total mass of the electrolyte as lithium salt.
  • the non-aqueous organic solvent is ethylene carbonate and ethyl methyl carbonate, which account for 87.0% of the total mass of the electrolyte, and the mass ratio is 1:2.
  • Compound 2 is added, which accounts for 1.0% of the total mass of the electrolyte.
  • the second additive is lithium difluorophosphate, which accounts for 1.0% of the total mass of the electrolyte.
  • the cathode material used in the lithium secondary battery is LiNi 0.8 Co 0.1 Mn 0.1 O 2 .
  • Embodiment 3 of the present invention provides a lithium secondary battery, which is prepared according to the method of embodiment 1, except that the non-aqueous organic solvent is ethylene carbonate and ethyl methyl carbonate, which account for 83.0 of the total mass of the electrolyte. %, the mass ratio is 1:3. Compound 3 is added, which accounts for 1.0% of the total mass of the electrolyte.
  • the second additives are vinylene carbonate and fluoroethylene carbonate, which respectively account for 0.5% and 3.0% of the total mass of the electrolyte.
  • the cathode material used in the lithium secondary battery is LiNi 0.8 Co 0.15 Al 0.05 O 2 .
  • Embodiment 4 of the present invention provides a lithium secondary battery, which is prepared according to the method of embodiment 1, except that the non-aqueous organic solvent is ethylene carbonate and diethyl carbonate, which account for 84.0 of the total mass of the electrolyte. %, the mass ratio is 1:2. Compound 4 is added, which accounts for 2.5% of the total mass of the electrolyte.
  • the second additives are lithium difluorooxalate borate and fluoroethylene carbonate, which respectively account for 0.5% and 5.0% of the total mass of the electrolyte.
  • the positive electrode material used in the lithium secondary battery is LiCoO 2
  • the negative electrode material is a silicon-carbon composite material.
  • Embodiment 5 of the present invention provides a lithium secondary battery, which is prepared according to the method of embodiment 1, except that the electrolyte of the lithium secondary battery uses 15% of the total mass of the electrolyte as lithium salt.
  • Non-aqueous organic solvents are ethylene carbonate, propylene carbonate, and diethyl carbonate, accounting for 81.5% of the total mass of the electrolyte, and the mass ratio is 4:1:5.
  • Compound 5 is added, which accounts for 1.0% of the total mass of the electrolyte.
  • the second additives are vinylene carbonate and tripropynyl phosphate, which respectively account for 0.5% and 2.0% of the total mass of the electrolyte.
  • the cathode material used in the lithium secondary battery is LiNi 0.8 Co 0.15 Al 0.05 O 2
  • the anode material is lithium titanate.
  • the charge cut-off voltage of the lithium secondary battery is 2.7V.
  • Embodiment 6 of the present invention provides a lithium secondary battery, which is prepared according to the method of embodiment 1, except that the mixture of ethylene carbonate, ethyl methyl carbonate, and diethyl carbonate is non-aqueous organic
  • the solvent accounts for 83.5% of the total mass of the electrolyte, and the mass ratio is 3:5:2.
  • Compound 6 is added, which accounts for 0.5% of the total mass of the electrolyte.
  • the second additives are triallyl phosphate and fluoroethylene carbonate, which respectively account for 1.0% and 3.0% of the total mass of the electrolyte.
  • the cathode material used in lithium secondary batteries is LiCoO 2 .
  • Embodiment 7 of the present invention provides a lithium secondary battery, which is prepared according to the method of embodiment 1, except that the electrolyte of the lithium secondary battery uses 17.5% of the total mass of the electrolyte as lithium salt.
  • the electrolyte of the lithium secondary battery uses 17.5% of the total mass of the electrolyte as lithium salt.
  • the second additive is lithium difluorophosphate, which accounts for 0.5% of the total mass of the electrolyte.
  • the positive electrode material used in the lithium secondary battery is LiMn 2 O 4
  • the negative electrode material is lithium titanate. .
  • Embodiment 8 of the present invention provides a lithium secondary battery, which is prepared according to the method of embodiment 1, except that the mixture of ethylene carbonate, ethyl methyl carbonate, and diethyl carbonate is non-aqueous organic
  • the solvent accounts for 83.5% of the total mass of the electrolyte, the mass ratio is 3:5:2, and the compound 8 is added, which accounts for 1.0% of the total mass of the electrolyte.
  • the second additives are triallyl isocyanurate and lithium difluorophosphate, which respectively account for 0.5% and 3.0% of the total mass of the electrolyte.
  • the cathode material used in the lithium secondary battery is LiMnO 2 .
  • Example 9 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 1, except that the electrolyte of the lithium secondary battery uses 15% of the total mass of the electrolyte as lithium salt.
  • Non-aqueous organic solvents are ethylene carbonate, propylene carbonate, and diethyl carbonate, accounting for 77.5% of the total mass of the electrolyte, and the mass ratio is 4:1:5.
  • Compound 9 is added, which accounts for 5.0% of the total mass of the electrolyte.
  • the second additives are vinylene carbonate and tripropynyl phosphate, which respectively account for 0.5% and 2.0% of the total mass of the electrolyte.
  • the cathode material used in the lithium secondary battery is LiNi 0.8 Co 0.15 Al 0.05 O 2
  • the anode material is lithium titanate.
  • the charge cut-off voltage of the lithium secondary battery is 2.7V.
  • Embodiment 10 of the present invention provides a lithium secondary battery, which is prepared according to the method of Embodiment 2, except that the second additive is not added.
  • Embodiment 11 of the present invention provides a lithium secondary battery.
  • the lithium secondary battery is prepared according to the method of embodiment 1, except that the electrolyte of the lithium secondary battery uses 15% of the total mass of the electrolyte.
  • the imide lithium is a lithium salt
  • the non-aqueous organic solvent is ethylene carbonate, ethyl acetate, and diethyl carbonate, accounting for 81.5% of the total mass of the electrolyte, and the mass ratio is 4:1:5.
  • Compound 11 is added, which accounts for 1.0% of the total mass of the electrolyte.
  • the second additives are triallyl phosphate and methylene disulfonate, which respectively account for 0.5% and 2.0% of the total mass of the electrolyte.
  • the cathode material used in the lithium secondary battery is LiNi0.8Co0.15Al0.05O2, and the anode material is lithium titanate.
  • the charge cut-off voltage of the lithium secondary battery is 2.7V.
  • Embodiment 12 of the present invention provides a lithium secondary battery, which is prepared according to the method of embodiment 1, except that ethylene carbonate, ethyl methyl carbonate, methyl propionate, 2,2-di
  • the mixture of fluoroethyl ethyl acetate is a non-aqueous organic solvent, accounting for 83.5% of the total mass of the electrolyte, and the mass ratio is 3:4:2:1.
  • Compound 13 is added, which accounts for 0.5% of the total mass of the electrolyte.
  • the second additives are lithium dioxalate borate and tris(trimethylsilyl) phosphate, which respectively account for 1.0% and 3.0% of the total mass of the electrolyte.
  • the cathode material used in lithium secondary batteries is LiCoO2.
  • Embodiment 13 of the present invention provides a lithium secondary battery, which is prepared according to the method of embodiment 1, except that the electrolyte of the lithium secondary battery uses 17.5% of the total mass of the electrolyte.
  • Lithium imide is a lithium salt, and a mixture of ethylene carbonate, ethyl methyl carbonate, and propyl propionate is a non-aqueous organic solvent, accounting for 78.0% of the total mass of the electrolyte, and the mass ratio is 3:5:2, and compound 15 is added , Accounting for 4.0% of the total mass of the electrolyte.
  • the second additive is tris(trimethylsilyl) borate, which accounts for 0.5% of the total mass of the electrolyte.
  • the cathode material used in the lithium secondary battery is LiMn2O4, and the anode material is lithium titanate.
  • Comparative Example 1 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 1, except that Compound 1 is not added to the electrolyte of the lithium secondary battery.
  • Comparative Example 2 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 2, except that Compound 2 is not added to the electrolyte of the lithium secondary battery.
  • Comparative Example 3 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 3, except that Compound 3 is not added to the electrolyte of the lithium secondary battery.
  • Comparative Example 4 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 4, except that Compound 4 is not added to the electrolyte of the lithium secondary battery.
  • Comparative Example 5 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 5, except that Compound 5 is not added to the electrolyte of the lithium secondary battery.
  • Comparative Example 6 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 6, except that Compound 6 is not added to the electrolyte of the lithium secondary battery.
  • Comparative Example 7 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 7 except that Compound 7 is not added to the electrolyte of the lithium secondary battery.
  • Comparative Example 8 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 8 except that Compound 8 is not added to the electrolyte of the lithium secondary battery.
  • Comparative Example 9 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 9 except that Compound 9 is not added to the electrolyte of the lithium secondary battery.
  • Comparative Example 10 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 1 except that Compound 10 is added to the electrolyte of the lithium secondary battery.
  • Comparative Example 11 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 11, except that Compound 12 is added to the electrolyte of the lithium secondary battery.
  • Comparative Example 12 of the present invention provides a lithium secondary battery, which is prepared according to the method of Example 12, except that Compound 14 is added to the electrolyte of the lithium secondary battery.
  • Comparative Example 13 of the present invention provides a lithium secondary battery.
  • the lithium secondary battery is prepared according to the method of Example 13, except that compound 16 is added to the electrolyte of the lithium secondary battery.
  • Cycle experiment test the internal resistance of the batteries obtained in Comparative Examples 1-13 and Examples 1-13 at room temperature 25°C; charge and discharge at a rate of 2CC/0.5CD at 25°C; at a low temperature of -10 Charge and discharge at a rate of 0.5CC/0.2CD at °C; charge and discharge cycle test at a rate of 0.5CC/0.5CD at a high temperature of 55°C, record the last cycle discharge capacity and divide by the first cycle discharge respectively The capacity is the capacity retention rate, and the recorded results are shown in Table 1.
  • the sulfonate compound can significantly reduce the internal resistance of the battery, and the battery's low-temperature cycle, high-rate normal-temperature cycle, high-temperature cycle, and high-temperature storage expansion are all significantly improved.
  • Examples 1-13 are significantly better than the comparative examples.
  • the results of Example 10 show that without the second additive, the battery also has very low internal resistance, good low-temperature cycling, high-rate normal-temperature cycling, and high-temperature cycling. Circulation, and significantly inhibit the expansion after high temperature storage. Therefore, the battery prepared by using the electrolyte of the present invention can obtain lower internal resistance, better low temperature cycle, large rate normal temperature cycle, high temperature cycle, and lower high temperature storage expansion.

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Abstract

本发明涉及锂二次电池的技术领域，更具体地，本发明提供了一种降低电池阻抗的锂二次电池电解液及锂二次电池。本发明第一方面提供了一种锂二次电池的电解液，含有非水溶剂、锂盐以及添加剂；其中，添加剂包括磺酸酯化合物。本发明提供的锂二次电池电解液，锂二次电池具有更低的阻抗，具备更好的低温性能、高温性能和循环寿命。

Description

一种降低电池阻抗的锂二次电池电解液及其锂二次电池 技术领域
本发明涉及锂二次电池的技术领域，更具体地，本发明提供了一种降低电池阻抗的锂二次电池电解液及锂二次电池。
背景技术
锂二次电池由于具有能量密度高、循环寿命长、无污染等特点，使其在消费类电子、动力汽车电池上及储能电源上具有广阔的应用前景。
近年来，随着全球石油能源的衰竭以及新能源技术的发展，应用于汽车动力上的锂二次电池技术迅速发展。对锂二次电池的性能提出了更高的要求。如电池需要有更长的使用寿命、需要能在极端温度下使用，需要能够进行快速的充放电(高倍率)，需要有更好的安全性。
电动车的电池组一般是由多个电池串联或者并联组成的，电池在正常工作时会产生一定的热量，整个电池组会使用一套电池热管理系统对电池进行热管理。电池的放电倍率越大或者电池内阻越大，电池的产热量也会越大。如果能降低电池的内阻，电池的产热量就能降低。同时电池的充放电倍率越大，电池的产热也会更大，如果能够降低电池内阻，也能降低高倍率充放电的电池产热。
由于电池组是由多个电池构成，单个电池的一致性决定了整个电池组的使用寿命，如能降低电池的阻抗，能很大程度提高电池的一致性，从而提高电池的使用寿命。
在电池的安全性方面，如果电池的内阻过大，电池在充电过程中电压会急速上升，电池存在过充的风险，电池一旦过充，可能会出现起火、爆炸。在解决电池过充的问题上，目前大部分的解决方案是在电池电解液中添加防过充添加剂，电池一旦过充，防过充添加剂会发生聚合反应，增加电池的内阻，阻断电池内部电流，防止电池起火爆炸。但是通过电解液中添加防过充添加剂的方式，虽然在一定程度上能提升安全性能，但是电池一旦过充，对电池的损伤是不可逆的。如果能从根本上降低电池阻抗，从源头上抑制电池出现过充的情况，对电池的使用寿命、安全性会更好。
发明内容
针对上述问题，本发明第一方面提供了一种锂二次电池的电解液，含有非水溶剂、锂盐以及添加剂；其中，添加剂包括磺酸酯化合物。
作为本发明的一种优选技术方案，其中，根据权利要求1所述锂二次电池的电解液，其特征在于，磺酸酯化合物选自通式(A)表示的化合物中的至少一种化合物：
Figure PCTCN2019127033-appb-000001
其中，R 1、R 2分别独立地选自碳原子数为1-5的脂肪族烃基、芳基、烷基取代的芳基、硅基中的一种；任何基团都可以被卤原子取代。
作为本发明的一种优选技术方案，其中，R 1、R 2分别独立地选自甲基、乙基、丙基、氟甲基、氟乙基、乙烯基、烯丙基、苯基、苯甲基、氟代苯基、三甲基硅基、三乙烯基硅基中的一种。
作为本发明的一种优选技术方案，其中，磺酸酯化合物选自
Figure PCTCN2019127033-appb-000002
Figure PCTCN2019127033-appb-000003
Figure PCTCN2019127033-appb-000004
中的任一种或多种的组合。
作为本发明的一种优选技术方案，其中，磺酸酯化合物质量占电解液总质量的0.1％～5％。
作为本发明的一种优选技术方案，其中，所述添加剂还包括第二添加剂，第二添加剂选自碳酸亚乙烯酯、氟代碳酸乙烯酯、二氟磷酸锂、二草酸硼酸锂、二氟草酸硼酸锂、1,3-丙烷磺酸内酯、三烯丙基异氰脲酸酯、甲烷二磺酸亚甲酯、硫酸乙烯酯、三烯丙基磷酸酯、三丙炔基磷酸酯、三(三甲基硅烷)磷酸酯、三(三甲基硅烷)硼酸酯中的任一种或多种的组合。
作为本发明的一种优选技术方案，其中，第二添加剂质量占电解液总质量的0.01％～10％。
作为本发明的一种优选技术方案，其中，非水溶剂质量占电解液总质量的67～91％。
作为本发明的一种优选技术方案，其中，非水溶剂包含环状酯和链状酯。
作为本发明的一种优选技术方案，其中，环状酯选自碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、γ-丁内酯中的任一种或多种的组合。
作为本发明的一种优选技术方案，其中，链状酯选自碳酸二甲酯、碳酸二乙酯、二乙基碳酸酯、二丙基碳酸酯、碳酸甲乙酯、碳酸甲丙酯、碳酸乙丙酯、甲酸甲酯、甲酸乙酯、甲酸丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、2,2-二氟乙基乙酸酯中的任一种或多种的组合。
作为本发明的一种优选技术方案，其中，锂盐质量占电解液总质量的8-18％。
作为本发明的一种优选技术方案，其中，锂盐选自六氟磷酸锂、双氟磺酰亚胺锂盐、双(三氟甲烷磺酰)亚胺锂中的至少一种。
本发明的第二个方面提供了一种锂二次电池，锂二次电池包括正极、负极以及电解液；其中，所用的电解液为所述的电解液。
作为本发明的一种优选技术方案，其中，锂二次电池选自锂离子电池、锂硫电池、锂空气电池中的任一种。
作为本发明的一种优选技术方案，其中，正极的活性材料为含锂过渡金属氧化物和/或含锂过渡金属磷酸化合物。
作为本发明的一种优选技术方案，其中，正极的活性材料选自Li 1+a(Ni xCo yM 1-x-y)O 2、Li(Ni nMn mCo 2-n-m)O 4、LiM p(PO 4) q的任一种；其中0≤a≤0.3，0≤x≤1，0≤y≤1，0≤x+y≤1，0≤n≤2，0≤m≤2，0≤n+m≤2，M选自Al、Fe、Ni、Co、Mn、V中的任一种，且0＜p＜5，0＜q＜5。
作为本发明的一种优选技术方案，其中，负极的活性材料选自锂金属、锂合金、碳材料、硅或锡及其氧化物中的任一种或多种的组合。
与现有技术相比，本发明具有的有益效果为：本发明提供一种锂二次电池电解液，使用该电解液的锂二次电池具有更低的阻抗，同时具备更好的低温性能、高温性能和循环寿命；同时，本发明还公开了采用含有该电解液的锂离子电池。
具体实施方式
【非水电解液】
为解决上述技术问题，本发明的第一个方面提供了一种锂二次电池的电解液，其含有非水溶剂、锂盐以及添加剂；其中，添加剂包括磺酸酯化合物。
<添加剂>
(磺酸酯化合物)
在一种实施方式中，磺酸酯化合物选自通式(A)表示的化合物中的至少一种：
Figure PCTCN2019127033-appb-000005
其中，R 1、R 2分别独立地选自碳原子数为1-5的脂肪族烃基、芳基、烷基取代的芳基、硅基中的一种；任何基团都可以被卤原子取代。
作为脂肪族烃基，可以举出烷基、烯基、炔基。
作为烷基，可以列举出甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1-甲基丁基、2-甲基丁基、1,1-二甲基丙基、1,2-二甲基丙基等。
作为被卤原子取代的烷基，可以列举出：氟甲基、二氟甲基、三氟甲基、1-氟乙基、2-氟乙基、1，1-二氟乙基、1，2-二氟乙基、2，2-二氟乙基、2，2，2-三氟乙基、全氟乙基、1-氟正丙基、2-氟正丙基、3-氟正丙基、1，1-二氟正丙基、1，2-二氟正丙基、1，3-二氟正丙基、2，2-二氟正丙基、2，3-二氟正丙基、3，3-二氟正丙基、3，3，3-三氟正丙基、2，2，3，3，3-五氟正丙基、全氟正丙基、1-氟异丙基、2-氟异丙基、1，2-二氟异丙基、2，2-二氟异丙基、2，2’-二氟异丙基、2，2，2，2’，2’，2’-六氟异丙基、1-氟正丁基、2-氟正丁基、3-氟正丁基、4-氟正丁基、4，4，4-三氟正丁基、全氟正丁基、2-氟叔丁基、全氟叔丁基；氟甲基、二氯甲基、三氟甲基、1-氯乙基、2-氟乙基、1，1-二氯乙基、1，2-二氟乙基、2，2-二氯乙基、2，2，2-三氟乙基、全氯乙基、1-氯正丙基、2-氯正丙基、3-氯正丙基、1，1-二氯正丙基、1，2-二氯正丙基、1，3-二氯正丙基、2，2-二氯正丙基、2，3-二氯正丙基、3，3-二氯正丙基、3，3，3-三氯正丙基、2，2，3，3，3-五氯正丙基、全氯正丙基、1-氯异丙基、2-氯异丙基、1，2-二氯异丙基、2，2-二氯异丙基、2，2’-二氯异丙基、2，2，2，2’，2’，2’-六氯异丙基、1-氯正丁基、2-氯正丁基、3-氯正丁基、4-氯正丁基、4，4，4-三氯正丁基、全氯正丁基、2-氯叔丁基、全氯叔丁基等。
作为烯基，可以列举出烯基、1-丙烯基、2-丙烯基、异丙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-戊烯基、2-戊烯基、3-戊烯基、4-戊烯基等。
作为被卤原子取代的烯基，可以列举出：1-氟乙烯基、2-氟乙烯基、1，2-二氟乙烯基、2，2-二氟乙烯基、1，2，2-三氟乙烯基、1-氟-1-丙烯基、2-氟-1-丙烯基、3-氟-1-丙烯基、1，2-二氟-1-丙烯基、1，3-二氟-1-丙烯基、2，3-二氟-1-丙烯基、3，3-二氟-1-丙烯基、1，2，3-三氟-1-丙烯基、1，3，3-三氟-1-丙烯基、2，3，3-三氟-1-丙烯基、3，3，3-三氟-1-丙烯基、1，2，3，3-四氟-1-丙烯基、1，3，3，3-四氟-1-丙烯基、2，3，3，3-四氟-1-丙烯基、1，2，3，3，3-五氟-1-丙烯基、2-氟-1-甲 基乙烯基、1-氟甲基乙烯基、2-氟-1-氟甲基乙烯基、1-二氟甲基乙烯基、2，2-二氟-1-甲基乙烯基、2，2-二氟-1-氟甲基乙烯基、2-氟-1-二氟甲基乙烯基、1-三氟甲基乙烯基、2-氟-1-三氟甲基乙烯基、2，2-二氟-1-二氟甲基乙烯基、2，2-二氟-1-三氟甲基乙烯基、1-氟烯丙基、2-氟烯丙基、3-氟烯丙基、1，1-二氟烯丙基、1，2-二氟烯丙基、1，3-二氟烯丙基、2，3-二氟烯丙基、3，3-二氟烯丙基、1，1，2-三氟烯丙基、1，1，3-三氟烯丙基、1，2，3-三氟烯丙基、1，3，3-三氟烯丙基、2，3，3-三氟烯丙基、1，1，1，2-四氟烯丙基、1，1，1，3-四氟烯丙基、1，1，2，3-四氟烯丙基、1，1，3，3-四氟烯丙基、1，2，3，3-四氟烯丙基、1，1，1，2，3-五氟烯丙基、1，1，1，3，3-五氟烯丙基、1，1，2，3，3-五氟烯丙基、1，1，1，2，3，3-六氟烯丙基等。
作为炔基，可以列举出：乙炔基、1-丙炔基、2-丙炔基、1-丁炔基、2-丁炔基、3-丁炔基、1-戊炔基、2-戊炔基、3-戊炔基、4-戊炔基等。
作为被卤原子取代的炔基，可以列举出：2-氟乙炔基、3-氟-1-丙炔基、3，3-二氟-1-丙炔基、3，3，3-三氟-1-丙炔基、3-氟-2-丙炔基、1-氟-2-丙炔基、1，1-二氟-2-丙炔基、1，3-二氟-2-丙炔基、1，1，3-三氟-2-丙炔基等。
作为芳基，可列举出：苯基、甲苯基、二甲苯基、乙基苯基、正丙基苯基、异丙基苯基、正丁基苯基、仲丁基苯基、异丁基苯基、叔丁基苯基等。
作为被烷基取代的苯基，可列举出：苄基、α-甲基苄基、1-甲基-1-苯基乙基、苯乙基、2-苯基丙基、2-甲基-2-苯基丙基、3-苯基丙基、3-苯基丁基、3-甲基-3-苯基丁基、4-苯基丁基、5-苯基戊基、6-苯基己基等。
作为被卤原子取代的苯基，可以列举出：2-氟苯基、3-氟苯基、4-氟苯基、2，3-二氟苯基、2，4-二氟苯基、2，5-二氟苯基、2，6-二氟苯基、2，3，4-三氟苯基、2，3，5-三氟苯基、2，3，6-三氟苯基、2，4，5-三氟苯基、2，3，6-三氟苯基、2，5，6-三氟苯基、3，4，5-三氟苯基、2，3，4，5-四氟苯基、2，3，4，6-四氟苯基、2，4，5，6-四氟苯基、五氟苯基。
作为硅基，可举出：-Si(CH 3) 3、-Si(CH 3) 2(C 2H 5)、-Si(CH 3) 2(CH＝CH 2)、-Si(CH 3) 2(CH 2CH 2CH 3)、-Si(CH 3) 2(CH 2CH＝CH 2)、-Si(CH 3) 2(C(CH 3)＝CH 2)、-Si(CH 3) 2[CH(CH 3) 2]、-Si(CH 3) 2[(CH 2) 3CH 3)、-Si(CH 3) 2[CH 2CH(CH 3) 2]、-Si(CH 3) 2[C(CH 3) 3]、-Si(CH 3) 2(C 6H 5)、-Si(CH 3)(C 6H 5) 2、-Si(C 6H 5) 3、-Si(C 2H5) 3、-Si(CH＝CH 2) 3、-Si(CH 2CH 2CH 3) 3、-Si[CH(CH 3) 2] 3、-Si(CH 2CH＝CH 2) 3、-Si(CF 3) 3等；未被取代的剩余的氢原子均可被卤原子取代。
作为磺酸酯化合物，优选地，R 1、R 2分别独立地选自甲基、乙基、丙基、氟甲基、氟乙基、乙烯基、丙烯基、苯基、甲苯基、氟代苯基、三甲基硅基、三乙烯基、硅基中的一种。
作为磺酸酯化合物，更优选为
Figure PCTCN2019127033-appb-000006
Figure PCTCN2019127033-appb-000007
Figure PCTCN2019127033-appb-000008
中的任一种或多种的组合。
在一种优选实施方式中，磺酸酯化合物质量占电解液总质量的0.1％～5％；更优选地，磺酸酯化合物质量占电解液总质量的0.5％～5％。
在一种实施方式中，添加剂还包括第二添加剂。
作为第二添加剂，可列举出：具有碳-碳不饱和键的碳酸酯化合物、具有卤原子的碳酸酯化合物、氟磷酸化合物、磷酸酯化合物、含硅化合物、磺酸酯化合物、硫酸酯化合物、具有异氰酸酯基的化合物等。
(第二添加剂)
作为具有碳-碳不饱和键的碳酸酯化合物，只要是具有碳碳双键或碳碳三键等碳碳不饱和键的碳酸酯，则没有其他限制，可以使用任意的不饱和碳酸酯。另外，具有芳香环的碳酸酯也包含在具有不饱和键的碳酸酯中。
作为具有碳-碳不饱和键的碳酸酯化合物，可举出：碳酸甲基乙烯基酯、碳酸乙基乙烯基酯、碳酸二乙烯基酯、碳酸甲基丙炔基酯、碳酸乙基丙炔基酯、碳酸二丙炔基酯、碳酸甲基苯基酯、碳酸乙基苯基酯、碳酸二苯基酯等链状碳酸酯类；碳酸亚乙烯基酯、甲基碳酸亚乙烯基酯、4,4-二甲基碳 酸亚乙烯基酯、4,5-二甲基碳酸亚乙烯基酯、乙烯基碳酸亚乙酯、4,4-二乙烯基碳酸亚乙酯(4,4-divinylethylenecarbonate)、4,5-二乙烯基碳酸亚乙酯、乙炔基碳酸亚乙酯、4,4-二乙炔基碳酸亚乙酯、4,5-二乙炔基碳酸亚乙酯、丙炔基碳酸亚乙酯、4,4-二丙炔基碳酸亚乙酯、4,5-二丙炔基碳酸亚乙酯等环状碳酸酯类；苯基碳酸亚乙酯、4，5-二苯基碳酸亚乙酯、碳酸二苯基酯、碳酸乙基苯基酯、碳酸甲基苯基酯、碳酸叔丁基苯基酯等。
作为具有卤原子的碳酸酯化合物，可举出：氟碳酸亚乙酯、氯碳酸亚乙酯、4，4-二氟碳酸亚乙酯、4，5-二氟碳酸亚乙酯、4，4-二氯碳酸亚乙酯、4，5-二氯碳酸亚乙酯、4-氟-4-甲基碳酸亚乙酯、4-氯-4-甲基碳酸亚乙酯、4，5-二氟-4-甲基碳酸亚乙酯、4，5-二氯-4-甲基碳酸亚乙酯、4-氟-5-甲基碳酸亚乙酯、4-氯-5-甲基碳酸亚乙酯、4，4-二氟-5-甲基碳酸亚乙酯、4，4-二氯-5-甲基碳酸亚乙酯、4-(氟甲基)碳酸亚乙酯、4-(氯甲基)碳酸亚乙酯、4-(二氟甲基)碳酸亚乙酯、4-(二氯甲基)碳酸亚乙酯、4-(三氟甲基)碳酸亚乙酯、4-(三氯甲基)碳酸亚乙酯、4-(氟甲基)-4-氟碳酸亚乙酯、4-(氯甲基)-4-氯碳酸亚乙酯、4-(氟甲基)-5-氟碳酸亚乙酯、4-(氯甲基)-5-氯碳酸亚乙酯、4-氟-4，5-二甲基碳酸亚乙酯、4-氯-4，5-二甲基碳酸亚乙酯、4，5-二氟-4，5-二甲基碳酸亚乙酯、4，5-二氯-4，5-二甲基碳酸亚乙酯、4，4-二氟-5，5-二甲基碳酸亚乙酯、4，4-二氯-5，5-二甲基碳酸亚乙酯、4-氟-4-乙烯基碳酸亚乙酯、4-氟-5-乙烯基碳酸亚乙酯、4，4-二氟-5-乙烯基碳酸亚乙酯、4，5-二氟-4-乙烯基碳酸亚乙酯、4-氯-5-乙烯基碳酸亚乙酯、4，4-二氯-5-乙烯基碳酸亚乙酯、4，5-二氯-4-乙烯基碳酸亚乙酯、4-氟-4，5-二乙烯基碳酸亚乙酯、4，5-二氟-4，5-二乙烯基碳酸亚乙酯、4-氯-4，5-二乙烯基碳酸亚乙酯、4，5-二氯-4，5-二乙烯基碳酸亚乙酯、4-氟-4-苯基碳酸亚乙酯、4-氟-5-苯基碳酸亚乙酯、4，4-二氟-5-苯基碳酸亚乙酯、4，5-二氟-4-苯基碳酸亚乙酯、4-氯-4-苯基碳酸亚乙酯、4-氯-5-苯基碳酸亚乙酯、4，4-二氯-5-苯基碳酸亚乙酯、4，5-二氯-4-苯基碳酸亚乙酯、4，5-二氟-4，5-二苯基碳酸亚乙酯、4，5-二氯-4，5-二苯基碳酸亚乙酯等。
还可举出：碳酸氟甲基苯基酯、碳酸2-氟乙基苯基酯、碳酸2，2-二氟乙基苯基酯、碳酸2，2，2-三氟乙基苯基酯、碳酸氯甲基苯基酯、碳酸2-氯乙基苯基酯、碳酸2，2-二氯乙基苯基酯、碳酸2，2，2-三氯乙基苯基酯、碳酸氟甲基乙烯基酯、碳酸2-氟乙基乙烯基酯、碳酸2，2-二氟乙基乙烯基酯、碳酸2，2，2-三氟乙基乙烯基酯、碳酸氯甲基乙烯基酯、碳酸2-氯乙基乙烯基酯、碳酸2，2-二氯乙基乙烯基酯、碳酸2，2，2-三氯乙基乙烯基酯、碳酸氟甲基烯丙基酯、碳酸2-氟乙基烯丙基酯、碳酸2，2-二氟乙基烯丙基酯、碳酸2，2，2-三氟乙基烯丙基酯、碳酸氯甲基烯丙基酯、碳酸2-氯乙基烯丙基酯、碳酸2，2-二氯乙基烯丙基酯、碳酸2，2，2-三氯乙基烯丙基酯等。
还可举出：碳酸2-氟乙基甲基酯、碳酸乙基氟甲基酯、碳酸2，2-二氟乙基甲基酯、碳酸2-氟乙基氟甲基酯、碳酸乙基二氟甲基酯、碳酸2，2，2-三氟乙基甲基酯、碳酸2，2-二氟乙基氟甲基酯、 碳酸2-氟乙基二氟甲基酯、碳酸乙基三氟甲基酯、碳酸2-氯乙基甲基酯、碳酸乙基氯甲基酯、碳酸2，2-二氯乙基甲基酯、碳酸2-氯乙基氯甲基酯、碳酸乙基二氯甲基酯、碳酸2，2，2-三氯乙基甲基酯、碳酸2，2-二氯乙基氯甲基酯、碳酸2-氯乙基二氯甲基酯、碳酸乙基三氯甲基酯、碳酸乙基(2-氟乙基)酯、碳酸乙基-(2，2-二氟乙基)酯、碳酸二(2-氟乙基)酯、碳酸乙基-(2，2，2-三氟乙基)酯、碳酸2，2-二氟乙基-2’-氟乙基酯、碳酸二(2，2-二氟乙基)酯、碳酸2，2，2-三氟乙基-2’-氟乙基酯、碳酸2，2，2-三氟乙基-2’，2’-二氟乙基酯、碳酸二(2，2，2-三氟乙基)酯、碳酸乙基-(2-氯乙基)酯、碳酸乙基-(2，2-二氯乙基)酯、碳酸二(2-氯乙基)酯、碳酸乙基(2，2，2-三氯乙基)酯、碳酸2，2-二氯乙基-2’-氯乙基酯、碳酸二(2，2-二氯乙基)酯、碳酸2，2，2-三氯乙基-2’-氯乙基酯、碳酸2，2，2-三氯乙基-2’，2’-二氯乙基酯、碳酸二(2，2，2-三氯乙基)酯、：碳酸氟甲基甲基酯、碳酸二氟甲基甲基酯、碳酸三氟甲基甲基酯、碳酸二(氟甲基)酯、碳酸二(二氟甲基)酯、碳酸二(三氟甲基)酯、碳酸氯甲基甲基酯、碳酸二氯甲基甲基酯、碳酸三氯甲基甲基酯、碳酸二(氯甲基)酯、碳酸二(二氯甲基)酯、碳酸二(三氯甲基)酯。
作为氟磷酸化合物，可举出：二氟磷酸锂、二氟磷酸、单氟磷酸、二氟磷酸甲酯、二氟磷酸乙酯、氟磷酸二甲酯、氟磷酸二乙酯、二氟-二草酸磷酸锂、四氟草酸磷酸锂、三草酸磷酸锂、二氟草酸硼酸锂、二草酸硼酸锂等。
作为磷酸酯化合物，可举出：磷酸二甲基乙烯基酯、磷酸二乙基乙烯基酯、磷酸二丙基乙烯基酯、磷酸二丁基乙烯基酯及磷酸二戊基乙烯基酯等具有乙烯基的化合物；
磷酸烯丙基二甲基酯、磷酸烯丙基二乙基酯、磷酸烯丙基二丙基酯、磷酸烯丙基二丁基酯及磷酸烯丙基二戊基酯等具有烯丙基的化合物；
磷酸炔丙基二甲基酯、磷酸炔丙基二乙基酯、磷酸炔丙基二丙基酯、磷酸炔丙基二丁基酯及磷酸炔丙基二戊基酯等具有炔丙基的化合物；
磷酸2-丙烯酰氧基甲基二甲基酯、磷酸2-丙烯酰氧基甲基二乙基酯、磷酸2-丙烯酰氧基甲基二丙基酯、磷酸2-丙烯酰氧基甲基二丁基酯及磷酸2-丙烯酰氧基甲基二戊基酯等具有2-丙烯酰氧基甲基的化合物；
磷酸2-丙烯酰氧基乙基二甲基酯、磷酸2-丙烯酰氧基乙基二乙基酯、磷酸2-丙烯酰氧基乙基二丙基酯、磷酸2-丙烯酰氧基乙基二丁基酯及磷酸2-丙烯酰氧基乙基二戊基酯等具有2-丙烯酰氧基乙基的化合物；
磷酸甲基二乙烯基酯、磷酸乙基二乙烯基酯、磷酸丙基二乙烯基酯、磷酸丁基二乙烯基酯及磷酸戊基二乙烯基酯等具有乙烯基的化合物；
磷酸二烯丙基甲基酯、磷酸二烯丙基乙基酯、磷酸二烯丙基丙基酯、磷酸二烯丙基丁基酯及磷 酸二烯丙基戊基酯等具有烯丙基的化合物；
磷酸二炔丙基甲基酯、磷酸二炔丙基乙基酯、磷酸二炔丙基丙基酯、磷酸二炔丙基丁基酯及磷酸二炔丙基戊基酯等具有炔丙基的化合物；
磷酸双(2-丙烯酰氧基甲基)甲基酯、磷酸双(2-丙烯酰氧基甲基)乙基酯、磷酸双(2-丙烯酰氧基甲基)丙基酯、磷酸双(2-丙烯酰氧基甲基)丁基酯及磷酸双(2-丙烯酰氧基甲基)戊基酯等具有2-丙烯酰氧基甲基的化合物；
磷酸双(2-丙烯酰氧基乙基)甲基酯、磷酸双(2-丙烯酰氧基乙基)乙基酯、磷酸双(2-丙烯酰氧基乙基)丙基酯、磷酸双(2-丙烯酰氧基乙基)丁基酯及磷酸双(2-丙烯酰氧基乙基)戊基酯等具有2-丙烯酰氧基乙基的化合物；
磷酸三乙烯酯、磷酸三烯丙酯、磷酸三炔丙酯、磷酸三(2-丙烯酰氧基甲基)酯及磷酸三(2-丙烯酰氧基乙基)酯等。
作为含硅化合物，可举出：磷酸三(三甲基甲硅烷基)酯、磷酸二(三甲基甲硅烷基)酯、磷酸单(三甲基甲硅烷基)酯、磷酸二甲基三甲基甲硅烷基酯、磷酸甲基二(三甲基甲硅烷基)酯、磷酸二乙基三甲基甲硅烷基酯、磷酸乙基二(三甲基甲硅烷基)酯、磷酸二丙基三甲基甲硅烷基酯、磷酸丙基二(三甲基甲硅烷基)酯、磷酸二丁基三甲基甲硅烷基酯、磷酸丁基二(三甲基甲硅烷基)酯、磷酸二辛基三甲基甲硅烷基酯、磷酸辛基二(三甲基甲硅烷基)酯、磷酸二苯基三甲基甲硅烷基酯、磷酸苯基二(三甲基甲硅烷基)酯、磷酸二(三氟代乙基)(三甲基甲硅烷基)酯、磷酸三氟代乙基二(三甲基甲硅烷基)酯、前述的磷酸甲硅烷基酯的三甲基甲硅烷基被三乙基甲硅烷基、三苯基甲硅烷基、二甲基乙基甲硅烷基等取代后的化合物、磷酸甲硅烷基酯等磷酸酯化合物；
三(三甲基硅烷)硼酸酯、硼酸三(三甲氧基甲硅烷基)酯、硼酸三(三乙基甲硅烷基)酯、硼酸三(三乙氧基甲硅烷基)酯、硼酸三(二甲基乙烯基甲硅烷基)及硼酸三(二乙基乙烯基甲硅烷基)酯等硼酸化合物；
甲磺酸三甲基甲硅烷基酯、四氟甲磺酸三甲基甲硅烷基酯等磺酸化合物。
作为磺酸酯化合物，可举出：1,3-丙磺酸内酯、1-氟-1,3-丙磺酸内酯、2-氟-1,3-丙磺酸内酯、3-氟-1,3-丙磺酸内酯、1-甲基-1,3-丙磺酸内酯、2-甲基-1,3-丙磺酸内酯、3-甲基-1,3-丙磺酸内酯、1-丙烯-1,3-磺酸内酯、2-丙烯-1,3-磺酸内酯、1-氟-1-丙烯-1,3-磺酸内酯、2-氟-1-丙烯-1,3-磺酸内酯、3-氟-1-丙烯-1,3-磺酸内酯、1-氟-2-丙烯-1,3-磺酸内酯、2-氟-2-丙烯-1,3-磺酸内酯、3-氟-2-丙烯-1,3-磺酸内酯、1-甲基-1-丙烯-1,3-磺酸内酯、2-甲基-1-丙烯-1,3-磺酸内酯、3-甲基-1-丙烯-1,3-磺酸内酯、1-甲基-2-丙烯-1,3-磺酸内酯、2-甲基-2-丙烯-1,3-磺酸内酯、3-甲基-2-丙烯-1,3-磺酸内酯、1,4-丁磺酸内酯及1,5-戊磺酸内酯等磺酸内酯化合物；甲烷二磺酸亚甲酯、甲烷二磺酸亚乙酯等二磺酸酯化合物。
作为硫酸酯化合物，可举出：1,2-乙二醇硫酸酯、1,2-丙二醇硫酸酯、1,3-丙二醇硫酸酯、1,2-丁二醇硫酸酯、1,3-丁二醇硫酸酯、1,4-丁二醇硫酸酯、1,2-戊二醇硫酸酯、1,3-戊二醇硫酸酯、1,4-戊二醇硫酸酯及1,5-戊二醇硫酸酯、亚硫酸亚乙酯、亚硫酸亚丙酯、硫酸亚乙酯、硫酸亚丙酯、硫酸亚丁酯、硫酸亚己酯、硫酸亚乙烯酯、3-环丁烯砜、二乙烯基砜、硫酸二甲酯、硫酸二乙酯等。
作为具有异氰酸酯基的化合物，可举出：甲基异氰酸酯、乙基异氰酸酯、丙基异氰酸酯、异丙基异氰酸酯、丁基异氰酸酯、叔丁基异氰酸酯、戊基异氰酸酯、己基异氰酸酯、环己基异氰酸酯、乙烯基异氰酸酯、烯丙基异氰酸酯、三烯丙基异氰脲酸酯、乙炔基异氰酸酯、丙炔基异氰酸酯、苯基异氰酸酯、氟苯基异氰酸酯。
优选地，第二添加剂选自碳酸亚乙烯酯、氟代碳酸乙烯酯、二氟磷酸锂、二草酸硼酸锂、二氟草酸硼酸锂、1,3-丙烷磺酸内酯、三烯丙基异氰脲酸酯、甲烷二磺酸亚甲酯、硫酸乙烯酯、三烯丙基磷酸酯、三丙炔基磷酸酯、三(三甲基硅烷)磷酸酯、三(三甲基硅烷)硼酸酯中的任一种或多种的组合。
更优选地，第二添加剂选自碳酸亚乙烯酯、氟代碳酸乙烯酯、二氟磷酸锂、二氟草酸硼酸锂、三烯丙基异氰脲酸酯、三烯丙基磷酸酯、三丙炔基磷酸酯中的任一种或多种的组合。
第二添加剂质量占电解液总质量的0.01％～10％；优选地，第二添加剂质量占电解液总质量的0.1％～8％；更优选地，第二添加剂质量占电解液总质量的0.5％～5.5％。
<非水溶剂>
在一种实施方式中，非水溶剂质量占电解液总质量的67～91％；优选地，非水溶剂质量占电解液总质量的77～87％。
作为非水溶剂，可适当选择各种非水溶剂，优选使用选自环状的非质子性溶剂及链状的非质子性溶剂中的至少一者，提高非水溶剂的溶解能力、稳定性以及导电性能。
作为环状的非质子性溶剂，可以使用环状酯、环状砜、环状醚。
作为环状砜的例子，包括但不限于环丁砜、2-甲基环丁砜、3-甲基环丁砜、二甲基砜、二乙基砜、二丙基砜、甲基乙基砜、甲基丙基砜等。
作为环状醚的例子，包括但不限于二氧杂环戊烷。
作为环状酯，可列举的有环状碳酸酯、环状羧酸酯。
本发明中，环状碳酸酯的种类没有限制，包括但不限于：甲基乙烯基碳酸酯、乙基乙烯基碳酸酯、碳酸二乙烯酯、甲基烯丙基碳酸酯、乙基烯丙基碳酸酯、碳酸二烯丙酯、甲基丙炔基碳酸酯、乙基丙炔基碳酸酯、碳酸二丙炔酯、甲基苯基碳酸酯、乙基苯基碳酸酯、碳酸二苯酯等链状碳酸酯类；碳酸亚乙烯酯、甲基亚乙烯基碳酸酯、4,4-二甲基亚乙烯基碳酸酯、4,5-二甲基亚乙烯基碳酸酯、 碳酸乙烯亚乙酯、4,4-二乙烯基亚乙基碳酸酯、4,5-二乙烯基亚乙基碳酸酯、烯丙基亚乙基碳酸酯、4,4-二烯丙基亚乙基碳酸酯、4,5-二烯丙基亚乙基碳酸酯、亚甲基亚乙基碳酸酯、4,4-二甲基-5-亚甲基亚乙基碳酸酯、乙炔基亚乙基碳酸酯、4,4-二乙炔基亚乙基碳酸酯、4,5-二乙炔基亚乙基碳酸酯、丙炔基亚乙基碳酸酯、4,4-二丙炔基亚乙基碳酸酯、4,5-二丙炔基亚乙基碳酸酯、苯基亚乙基碳酸酯、4,5-二苯基亚乙基碳酸酯、碳酸亚苯基酯、氟代碳酸、氟碳酸亚乙酯、碳酸三氟乙烯、四氟乙烯酯、碳酸三氟丙烯酯等。
本发明中，环状羧酸酯的种类没有限制，包括但不限于：γ-丁内酯、甲基γ-丁内酯、乙基γ-丁内酯、γ-戊内酯、γ-己内酯、γ-庚内酯、δ-戊内酯、乙基δ-戊内酯等。
作为环状酯，优选碳酸乙烯酯、碳酸丙烯酯、γ-丁内酯、碳酸丁烯酯中的至少一种。
作为链状的非质子性溶剂，可使用链状酯、链状醚等。
作为链状醚，具体而言，可举出二甲氧基乙烷等。
作为链状酯，可列举的有环状碳酸酯、环状羧酸酯、链状磷酸酯。
本发明中，链状羧酸酯的种类没有限制，包括但不限于：可举出碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲乙酯、乙酸甲酯，乙酸乙酯，乙酸丙酯，丙酸甲酯、丁酸甲酯、异丁酸甲酯、三甲基醋酸甲酯、三甲基醋酸乙酯、丙二酸甲酯、丙二酸乙酯、丁二酸甲酯、丁二酸乙酯、3－甲氧基丙酸甲酯、3－甲氧基丙酸乙酯、乙二醇二乙酸酯、丙二醇二乙酸酯、2,2-二氟乙基乙酸酯等。
本发明中，链状碳酸酯的种类没有限制，包括但不限于：碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、碳酸甲丙酯、碳酸乙丙酯、二丙基碳酸酯、二乙基碳酸酯等。
本发明中，链状磷酸酯的种类没有限制，包括但不限于：磷酸三甲酯、磷酸三乙酯、磷酸三苯酯等。
作为链状酯，优选碳酸二甲酯、碳酸二乙酯、二乙基碳酸酯、二丙基碳酸酯、碳酸甲乙酯、碳酸甲丙酯、碳酸乙丙酯、甲酸甲酯、甲酸乙酯、甲酸丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、2,2-二氟乙基乙酸酯中的至少一种。
在一种实施方式中，环状酯和链状酯的重量比为1：(1～5)；优选地，在一种实施方式中，环状酯和链状酯的重量比为1：(1～2.5)。
<电解质>
本发明的非水电解液中使用的电解质没有限制，只要是目标的非水电解质二次电池中作为电解质使用，则可以任意采用公知的电解质。在锂二次电池中使用本发明的非水电解液时，通常使用锂盐作为电解质。
作为锂盐，可举出：LiPF 6、LiBF 4、LiClO 4、LiAlF 4、LiSbF 6、LiTaF 6、LiWF 7等无机锂盐；LiWOF 5 等钨酸锂类；HCO 2Li、CH 3CO 2Li、CH 2FCO 2Li、CHF 2CO 2Li、CF 3CO 2Li、CF 3CH 2CO 2Li、CF 3CF 2CO 2Li、CF 3CF 2CF 2CO 2Li、CF 3CF 2CF 2CF 2CO 2Li等羧酸锂盐类；FSO 3Li、CH 3SO 3Li、CH 2FSO 3Li、CHF 2SO 3Li、CF 3SO 3Li、CF 3CF 2SO 3Li、CF 3CF 2CF 2SO 3Li、CF 3CF 2CF 2CF 2SO 3Li等磺酸锂盐类；LiN(FCO) 2、LiN(FCO)(FSO 2)、LiN(FSO 2) 2、LiN(FSO 2)(CF 3SO 2)、LiN(CF 3SO 2) 2、LiN(C 2F 5SO 2) 2、环状1,2-全氟乙烷二磺酰亚胺锂、环状1,3-全氟丙烷二磺酰亚胺锂、LiN(CF 3SO 2)(C 4F 9SO 2)等酰亚胺锂盐类；LiC(FSO 2) 3、LiC(CF 3SO 2) 3、LiC(C 2F 5SO 2) 3等甲基化锂盐类；双(丙二酸根合)硼酸锂、二氟(丙二酸根合)硼酸锂等丙二酸根合硼酸锂盐类；三(丙二酸根合)磷酸锂、二氟双(丙二酸根合)磷酸锂、四氟(丙二酸根合)磷酸锂等丙二酸根合磷酸锂盐类；以及LiPF 4(CF 3) 2、LiPF 4(C 2F 5) 2、LiPF 4(CF 3SO 2) 2、LiPF 4(C 2F 5SO 2) 2、LiBF 3CF 3、LiBF 3C 2F 5、LiBF 3C 3F 7、LiBF 2(CF 3) 2、LiBF 2(C 2F 5) 2、LiBF 2(CF 3SO 2) 2、LiBF 2(C 2F 5SO 2) 2等含氟有机锂盐类；二氟草酸硼酸锂、双草酸硼酸锂等草酸根合硼酸锂盐类作为锂盐。
作为锂盐，优选LiSbF 6、双氟磺酰亚胺锂盐、双(三氟甲烷磺酰)亚胺锂中的至少一种。
在一种实施方式中，锂盐质量占电解液总质量的8-18％；
本发明的第二个方面提供了一种锂二次电池，锂二次电池包括正极、负极以及所述电解液。
【电池】
本发明中的锂二次电池选自锂离子电池、锂硫电池、锂空气电池中的任一种；锂离子电池、锂硫电池和锂空气电池是本领域技术人员所熟知的技术术语。本发明中锂二次电池的形状和类型没有特殊限定，可以是诸如锂离子电池、锂离子聚合物电池、锂硫电池的锂二次电池以及锂一次电池。锂电池可通过相关领域已知的制造方法制造。
＜正极活性物质＞
正极包含能够吸留、放出锂的正极活性物质。
作为正极活性物质，只要是能够以电化学方式吸留和放出锂离子的物质即可，没有特别限制。优选含有锂和至少一种过渡金属的物质，例如可列举锂-过渡金属复合氧化物、含有锂的过渡金属磷酸化合物。
作为锂-过渡金属复合氧化物的过渡金属，优选V、Ti、Cr、Mn、Fe、Co、Ni、Cu等，作为具体例子，可列举LiCoO 2等锂-钴复合氧化物；LiNiO 2等锂-镍复合氧化物；LiMnO 2、LiMn 2O 4、Li 2MnO 3等锂-锰复合氧化物；用Al、Ti、V、Cr、Mn、Fe、Co、Li、Ni、Cu、Zn、Mg、Ga、Zr、Si等其他金属来替代形成这些锂-过渡金属复合氧化物主体的过渡金属原子的一部分而得到的物质等。作为替代而得到的物质的具体例子，例如可列举LiNi 0.5Mn 0.5O 2、LiNi 0.85Co 0.10Al 0.05O 2、LiNi 0.33Co 0.33Mn 0.33O 2、LiMn 1.8Al 0.2O 4、LiMn 1.5Ni 0.5O 4等。
作为含有锂的过渡金属磷酸化合物的过渡金属，优选V、Ti、Cr、Mn、Fe、Co、Ni、Cu等，作为具体例子，例如可列举LiFePO 4、Li 3Fe 2(PO 4) 3、LiFeP 2O 7等磷酸铁类；LiCoPO 4等磷酸钴类；用Al、Ti、V、Cr、Mn、Fe、Co、Li、Ni、Cu、Zn、Mg、Ga、Zr、Nb、Si等其他金属来替代形成这些含有锂的过渡金属磷酸化合物主体的过渡金属原子的一部分而得到的物质等。
作为正极活性物质，优选Li 1+a(Ni xCo yM 1-x-y)O 2、Li(Ni nMn mCo 2-n-m)O 4、LiM p(PO 4) q的任一种；其中0≤a≤0.3，0≤x≤1，0≤y≤1，0≤x+y≤1，0≤n≤2，0≤m≤2，0≤n+m≤2，M选自Al、Fe、Ni、Co、Mn、V中的任一种，且0＜p＜5，0＜q＜5。
<粘合剂-1>
作为在制造正极活性物质层时使用的粘合剂，没有特别限定，使用涂布法时，只要是可溶解或分散在电极制造时使用的液体介质中的材料即可，作为具体例子，可列举聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、聚甲基丙烯酸甲酯、芳香族聚酰胺、纤维素、硝基纤维素等树脂类高分子；SBR(苯乙烯-丁二烯橡胶)、NBR(丙烯腈-丁二烯橡胶)、氟橡胶、异戊二烯橡胶、丁二烯橡胶、乙烯-丙烯橡胶等橡胶状高分子；苯乙烯-丁二烯-苯乙烯嵌段共聚物或其加氢物、EPDM(乙烯-丙烯-二烯烃三元共聚物)、苯乙烯-乙烯-丁二烯-乙烯共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物或其加氢物等热塑性弹性体状高分子；间规立构1,2-聚丁二烯、聚乙酸乙烯酯、乙烯-乙酸乙烯酯共聚物、丙烯-α-烯烃共聚物等软质树脂状高分子；聚偏氟乙烯(PVDF)、聚四氟乙烯、氟化聚偏氟乙烯、聚四氟乙烯-乙烯共聚物等氟类高分子；具有碱金属离子(特别是锂离子)的离子传导性的高分子组合物等。另外，这些物质可以单独使用一种，也可以以任意的组合和比例组合使用2种以上。
粘合剂在正极活性物质层中的比例太低，则不能充分保持正极活性物质，正极的机械强度不足，循环特性等电池性能恶化。另一方面，如果粘合剂的比例太高，则有时会导致电池容量或导电性降低。
<浆料形成溶剂-1>
作为用于形成浆料的溶剂，只要是可以溶解或分散正极活性物质、导电材料、粘结剂、以及根据需要而使用的增稠剂的溶剂即可，对其种类没有特殊限制，可以使用水性溶剂和有机类溶剂中的任意溶剂。作为水性介质，可列举水、醇与水的混合介质等。作为有机类溶剂，可列举例如：己烷等脂肪族烃类；苯、甲苯、二甲苯、甲基萘等芳香族烃类；喹啉、吡啶等杂环化合物；丙酮、甲乙酮、环己酮等酮类；乙酸甲酯、丙烯酸甲酯等酯类；二亚乙基三胺、N,N-二甲基氨基丙胺等胺类；乙醚、环氧丙烷、四氢呋喃(THF)等醚类；N-甲基吡咯烷酮(NMP)、二甲基甲酰胺、二甲基乙酰胺等酰胺类；六甲基磷酰胺、二甲亚砜等极性非质子溶剂等。
本发明中，正极可通过在集电体上形成含有正极活性物质和粘结剂的正极活性物质层来制作。 使用正极活性物质的正极的制造可利用常规方法进行。例如：可以将正极活性物质和粘结剂、以及根据需要而使用的导电材料及增稠剂等进行干式混合并制成片状，再将该片状材料压合在正极集电体上，或将这些材料溶解或分散在液体介质中制成浆料，将该浆料涂布于正极集电体上并进行干燥，由此在集电体上形成正极活性物质层，从而获得正极。
＜负极活性物质＞
负极包含能够吸留、放出锂的负极活性物质。
作为负极活性物质，可以使用选自由金属锂、含锂合金、能够与锂合金化的金属或合金、能够掺杂/脱掺杂锂离子的氧化物、能够掺杂/脱掺杂锂离子的过渡金属氮化物和能够掺杂/脱掺杂锂离子的碳材料中的一种或多种的组合至少1种。
作为负极活性物质，优选锂金属、锂合金、碳材料、硅或锡及其氧化物中的任一种或多种的组合。
<粘合剂-2>
作为粘结负极活性物质的粘合剂，只要是相对于非水电解液及电极制造时使用的溶剂稳定的材料即可，没有特殊限制。
作为具体例，可列举：聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、聚甲基丙烯酸甲酯、芳香族聚酰胺、聚酰亚胺、纤维素、硝基纤维素等树脂类高分子；SBR(丁苯橡胶)、异戊二烯橡胶、丁二烯橡胶、氟橡胶、NBR(丁腈橡胶)、乙丙橡胶等橡胶状高分子；苯乙烯-丁二烯-苯乙烯嵌段共聚物或其加氢产物；EPDM(乙烯-丙烯-二烯三元共聚物)、苯乙烯-乙烯-丁二烯-苯乙烯共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物或其加氢产物等热塑性弹性体状高分子；间规立构1,2-聚丁二烯、聚乙酸乙烯酯、乙烯-乙酸乙烯酯共聚物、丙烯-α-烯烃共聚物等软质树脂状高分子；聚偏氟乙烯、聚四氟乙烯、氟化聚偏氟乙烯、聚四氟乙烯-乙烯共聚物等氟类高分子；具有碱金属离子(特别是锂离子)的离子传导性的高分子组合物等。这些粘结剂可以单独使用一种，也可以以任意组合及比例组合使用两种以上。
<浆料形成溶剂-2>
作为用于形成浆料的溶剂，只要是可以溶解或分散负极活性物质、粘合剂、以及根据需要而使用的增稠剂及导电材料的溶剂即可，对其种类没有特殊限制，可以使用水性溶剂和非水溶剂中的任意溶剂。
作为水性溶剂，可列举水、醇等；作为非水溶剂，可列举N-甲基吡咯烷酮(NMP)、二甲基甲酰胺、二甲基乙酰胺、甲乙酮、环己酮、乙酸甲酯、丙烯酸甲酯、二乙基三胺、N,N-二甲基氨基丙胺、四氢呋喃(THF)、甲苯、丙酮、乙醚、六甲基磷酰胺、二甲亚砜、苯、二甲苯、喹啉、吡啶、甲基萘、 己烷等。
特别是，使用水性溶剂的情况下，优选在使用增稠剂的同时使其中含有分散剂等，并利用SBR等胶乳进行浆料化。需要说明的是，这些溶剂可以单独使用一种，也可以以任意组合及比例组合使用两种以上。
<增稠剂>
增稠剂通常用于调节浆料的粘度。作为增稠剂，并无特殊限制，具体可列举：羧甲基纤维素、甲基纤维素、羟甲基纤维素、乙基纤维素、聚乙烯醇、氧化淀粉、磷酸化淀粉、酪蛋白及它们的盐等。这些增稠剂可以单独使用一种，也可以以任意组合及比例组合使用两种以上。
增稠剂相对于负极活性物质在合适范围内时，可抑制电池容量的降低及阻抗的增大，并且能够确保良好的涂布性。
在不明显破坏本发明效果的范围内，本发明的负极电极的制造可以采用任意公知的方法。例如，可以通过向负极活性物质中添加粘合剂、溶剂、根据需要而加入的增稠剂、导电材料等，制成浆料，并将该浆料涂布在集电体上、使其干燥之后进行压制来形成电极。
下面通过实施例对本发明进行具体描述。有必要在此指出的是，以下实施例只用于对本发明作进一步说明，不能理解为对本发明保护范围的限制，该领域的专业技术人员根据上述本发明的内容做出的一些非本质的改进和调整，仍属于本发明的保护范围。
实施例
下面结合具体实施例，是对本发明的技术方案作进一步的详细说明，但不构成对本发明的任何限制。
实施例中涉及到的化合物结构式如下：
Figure PCTCN2019127033-appb-000009
Figure PCTCN2019127033-appb-000010
实施例1
本发明的实施例1提供一种锂二次电池，其制备过程如下：
(1)锂二次电池的正极片的制备
将正极活性材料镍钴锰酸锂(LiNi 1/3Co 1/3Mn 1/3O 2)、导电剂Super-P、粘接剂PVDF按质量比96:2.0:2.0溶于溶剂N-甲基吡咯烷酮中混合均匀制成正极浆料，之后将正极浆料均匀涂布在集流体铝箔上，涂布量为0.018g/cm 2，随后在85℃下烘干后进行冷压、切边、裁片、分条，之后在85℃真空条件下干燥4h，焊接极耳，制成满足要求的锂二次电池的正极片。
(2)锂二次电池的负极片的制备
将负极活性材料石墨、导电剂Super-P、增稠剂CMC、粘接剂SBR按质量比96.5:1.0:1.0:1.5溶于溶剂去离子水中混合均匀制成负极浆料，之后将负极浆料均匀涂布在集流体铜箔上，涂布量为0.0089g/cm 2，随后在85℃下烘干后进行冷压、切边、裁片、分条，之后在110℃真空条件下干燥4h，焊接极耳，制成满足要求的锂二次电池的负极片。
(3)锂二次电池的电解液的制备
锂二次电池的电解液以占电解液总质量12.5％的六氟磷酸锂为锂盐，以碳酸乙烯酯、碳酸甲乙酯、碳酸二乙酯的混合物为非水有机溶剂,占电解液总质量的81.5％，其中以碳酸乙烯酯、碳酸甲乙酯、碳酸二乙酯的质量比为3:5:2。此外，锂二次电解液中还含有添加剂，添加剂为占锂二次电池电解液总质量3.0％的化合物1。第二添加剂为碳酸亚乙烯酯、1,3-丙烷磺酸内酯，分别占电解液总质量的1.0％、2.0％。
(4)锂二次电池的制备
将根据前述工艺制备的锂二次电池的正极片、负极片以及隔离膜经过卷绕工艺制作成厚度为8mm、宽度为60mm、长度为130mm的电芯，并在75℃下真空烘烤10h、注入电解液、静置24h，之后用0.1C(160mA)的恒定电流充电至4.2V，然后以4.2V恒压充电至电流下降到0.05C(80mA)，然后以0.1C(160mA)的恒定电流放电至3.0V，重复2次充放电，最后以0.1C(160mA)的恒定电流充电至3.8V，完成锂二次电池的制备。
实施例2
本发明的实施例2提供一种锂二次电池，其依照实施例1的方法制备锂二次电池，不同的是锂二次电池的电解液以占电解液总质量10.0％的六氟磷酸锂为锂盐,非水有机溶剂为碳酸乙烯酯、碳酸甲乙酯，占电解液总质量的87.0％,质量比为1:2。添加化合物2，占电解液总质量的1.0％。第二添加剂为二氟磷酸锂，占电解液总质量的1.0％。锂二次电池所用的正极材料为LiNi 0.8Co 0.1Mn 0.1O 2。
实施例3
本发明的实施例3提供一种锂二次电池，其依照实施例1的方法制备锂二次电池，不同的是非水有机溶剂为碳酸乙烯酯、碳酸甲乙酯，占电解液总质量的83.0％,质量比为1:3。添加化合物3，占电解液总质量的1.0％。第二添加剂为碳酸亚乙烯酯、氟代碳酸乙烯酯，分别占电解液总质量的0.5％、3.0％。锂二次电池所用的正极材料为LiNi 0.8Co 0.15Al 0.05O 2。
实施例4
本发明的实施例4提供一种锂二次电池，其依照实施例1的方法制备锂二次电池，不同的是非水有机溶剂为碳酸乙烯酯、碳酸二乙酯，占电解液总质量的84.0％,质量比为1:2。添加化合物4，占电解液总质量的2.5％。第二添加剂为二氟草酸硼酸锂、氟代碳酸乙烯酯，分别占电解液总质量的0.5％、5.0％。锂二次电池所用的正极材料为LiCoO 2，负极材料为硅碳复合材料。
实施例5
本发明的实施例5提供一种锂二次电池，其依照实施例1的方法制备锂二次电池，不同的是锂二次电池的电解液以占电解液总质量15％的六氟磷酸锂为锂盐,非水有机溶剂为碳酸乙烯酯、碳酸丙 烯酯、碳酸二乙酯，占电解液总质量的81.5％,质量比为4:1:5。添加化合物5，占电解液总质量的1.0％。第二添加剂为碳酸亚乙烯酯、三丙炔基磷酸酯，分别占电解液总质量的0.5％、2.0％。锂二次电池所用的正极材料为LiNi 0.8Co 0.15Al 0.05O 2，负极材料为钛酸锂。锂二次电池的充电截止电压为2.7V。
实施例6
本发明的实施例6提供一种锂二次电池，其依照实施例1的方法制备锂二次电池，不同的是以碳酸乙烯酯、碳酸甲乙酯、碳酸二乙酯的混合物为非水有机溶剂,占电解液总质量的83.5％,质量比为3:5:2。添加化合物6，占电解液总质量的0.5％。第二添加剂为三烯丙基磷酸酯、氟代碳酸乙烯酯，分别占电解液总质量的1.0％、3.0％。锂二次电池所用的正极材料为LiCoO 2。
实施例7
本发明的实施例7提供一种锂二次电池，其依照实施例1的方法制备锂二次电池，不同的是锂二次电池的电解液以占电解液总质量17.5％的六氟磷酸锂为锂盐,以碳酸乙烯酯、碳酸甲乙酯、碳酸二乙酯的混合物为非水有机溶剂,占电解液总质量的78.0％,质量比为3:5:2,添加化合物7，占电解液总质量的4.0％。第二添加剂为二氟磷酸锂，占电解液总质量的0.5％。锂二次电池所用的正极材料为LiMn 2O 4，负极材料为钛酸锂。。
实施例8
本发明的实施例8提供一种锂二次电池，其依照实施例1的方法制备锂二次电池，不同的是以碳酸乙烯酯、碳酸甲乙酯、碳酸二乙酯的混合物为非水有机溶剂,占电解液总质量的83.5％,质量比为3:5:2,添加化合物8，占电解液总质量的1.0％。第二添加剂为三烯丙基异氰脲酸酯、二氟磷酸锂，分别占电解液总质量的0.5％、3.0％。锂二次电池所用的正极材料为LiMnO 2。
实施例9
本发明的实施例9提供一种锂二次电池，其依照实施例1的方法制备锂二次电池，不同的是锂二次电池的电解液以占电解液总质量15％的六氟磷酸锂为锂盐,非水有机溶剂为碳酸乙烯酯、碳酸丙烯酯、碳酸二乙酯，占电解液总质量的77.5％,质量比为4:1:5。添加化合物9，占电解液总质量的5.0％。第二添加剂为碳酸亚乙烯酯、三丙炔基磷酸酯，分别占电解液总质量的0.5％、2.0％。锂二次电池所用的正极材料为LiNi 0.8Co 0.15Al 0.05O 2，负极材料为钛酸锂。锂二次电池的充电截止电压为2.7V。
实施例10
本发明的实施例10提供一种锂二次电池，其依照实施例2的方法制备锂二次电池，不同的是不添加第二添加剂。
实施列11
本发明的实施例11提供一种锂二次电池，其依照实施例1的方法制备锂二次电池，不同的是锂 二次电池的电解液以占电解液总质量15％的三氟甲烷磺酰亚胺锂为锂盐,非水有机溶剂为碳酸乙烯酯、乙酸乙酯、碳酸二乙酯，占电解液总质量的81.5％,质量比为4:1:5。添加化合物11，占电解液总质量的1.0％。第二添加剂为三烯丙基磷酸酯、甲烷二磺酸亚甲酯，分别占电解液总质量的0.5％、2.0％。锂二次电池所用的正极材料为LiNi0.8Co0.15Al0.05O2，负极材料为钛酸锂。锂二次电池的充电截止电压为2.7V。
实施例12
本发明的实施例12提供一种锂二次电池，其依照实施例1的方法制备锂二次电池，不同的是以碳酸乙烯酯、碳酸甲乙酯、丙酸甲酯、2,2-二氟乙基乙酸乙酯的混合物为非水有机溶剂,占电解液总质量的83.5％,质量比为3:4:2:1。添加化合物13，占电解液总质量的0.5％。第二添加剂为二草酸硼酸锂、三(三甲基硅基)磷酸酯，分别占电解液总质量的1.0％、3.0％。锂二次电池所用的正极材料为LiCoO2。
实施例13
本发明的实施例13提供一种锂二次电池，其依照实施例1的方法制备锂二次电池，不同的是锂二次电池的电解液以占电解液总质量17.5％的三氟磺酰亚胺锂为锂盐,以碳酸乙烯酯、碳酸甲乙酯、丙酸丙酯的混合物为非水有机溶剂,占电解液总质量的78.0％,质量比为3:5:2,添加化合物15，占电解液总质量的4.0％。第二添加剂为三(三甲基硅基)硼酸酯，占电解液总质量的0.5％。锂二次电池所用的正极材料为LiMn2O4，负极材料为钛酸锂。
对比例1
本发明的对比例1提供一种锂二次电池，其依照实施例1的方法制备锂二次电池，只是在锂二次电池电解液中不添加化合物1。
对比例2
本发明的对比例2提供一种锂二次电池，其依照实施例2的方法制备锂二次电池，只是在锂二次电池电解液中不添加化合物2。
对比例3
本发明的对比例3提供一种锂二次电池，其依照实施例3的方法制备锂二次电池，只是在锂二次电池电解液中不添加化合物3。
对比例4
本发明的对比例4提供一种锂二次电池，其依照实施例4的方法制备锂二次电池，只是在锂二次电池电解液中不添加化合物4。
对比例5
本发明的对比例5提供一种锂二次电池，其依照实施例5的方法制备锂二次电池，只是在锂二次电池电解液中不添加化合物5。
对比例6
本发明的对比例6提供一种锂二次电池，其依照实施例6的方法制备锂二次电池，只是在锂二次电池电解液中不添加化合物6。
对比例7
本发明的对比例7提供一种锂二次电池，其依照实施例7的方法制备锂二次电池，只是在锂二次电池电解液中不添加化合物7。
对比例8
本发明的对比例8提供一种锂二次电池，其依照实施例8的方法制备锂二次电池，只是在锂二次电池电解液中不添加化合物8。
对比例9
本发明的对比例9提供一种锂二次电池，其依照实施例9的方法制备锂二次电池，只是在锂二次电池电解液中不添加化合物9。
对比例10
本发明的对比例10提供一种锂二次电池，其依照实施例1的方法制备锂二次电池，只是在锂二次电池电解液中添加化合物10。
对比例11
本发明的对比例11提供一种锂二次电池，其依照实施例11的方法制备锂二次电池，只是在锂二次电池电解液中添加化合物12。
对比例12
本发明的对比例12提供一种锂二次电池，其依照实施例12的方法制备锂二次电池，只是在锂二次电池电解液中添加化合物14。
对比例13
本发明的对比例13提供一种锂二次电池，其依照实施例13的方法制备锂二次电池，只是在锂二次电池电解液中添加化合物16。
性能测试
对上述所得对比例1～13和所有实施例1～13所得电池进行如下实验：
1.循环实验：将对比例1～13和实施例1～13所得电池在分别在室温25℃测试电池的内阻；在25℃下以2CC/0.5CD的倍率进行充放电；在低温-10℃下以0.5CC/0.2CD的倍率进行充放电；在高温 55℃下以0.5CC/0.5CD的充放电倍率进行充放电循环测试，分别记录最后一次循环放电容量并除以第1次循环放电容量即得容量保持率，记录结果如表1。
2.高温存储实验：将对比例1～13和实施例1～13的电池先在室温下以0.5C/0.5C的充放电倍率在3.0～4.2V充放电3次，再以0.5C充电至4.2V，记录电池的厚度。将电池放置在60℃烘箱中存储15天，记录电池的厚度。第二次记录电池的厚度除以第一次记录电池的厚度即为电池膨胀率。结果记录如表1。
表1 性能测试结果
Figure PCTCN2019127033-appb-000011
Figure PCTCN2019127033-appb-000012
通过以上数据可以明显看出，磺酸酯化合物对能够明显降低电池内阻，电池的低温循环、大倍率常温循环，高温循环，高温存储后的膨胀都有显著的改善。实施例1-13明显优于其对比例，同时实施例10结果显示，在不含第二添加剂的情况下，电池也具有很低的内阻、很好的低温循环、大倍率常温循环，高温循环，以及明显抑制高温存储后的膨胀。因此使用本发明的电解液制备的电池能获得更低的内阻、更好的低温循环、大倍率常温循环，高温循环，更低的高温存储膨胀。
前述的实例仅是说明性的，用于解释本发明所述方法的一些特征。所附的权利要求旨在要求可以设想的尽可能广的范围，且本文所呈现的实施例仅是根据所有可能的实施例的组合的选择的实施方式的说明。因此，申请人的用意是所附的权利要求不被说明本发明的特征的示例的选择限制。在权利要求中所用的一些数值范围也包括了在其之内的子范围，这些范围中的变化也应在可能的情况下解释为被所附的权利要求覆盖。

Claims (18)

  1. 一种锂二次电池的电解液，其特征在于，含有非水溶剂、锂盐以及添加剂；其中，添加剂包括磺酸酯化合物。
  2. 根据权利要求1所述锂二次电池的电解液，其特征在于，磺酸酯化合物选自通式(A)表示的化合物中的至少一种化合物：
    Figure PCTCN2019127033-appb-100001
    其中，R 1、R 2分别独立地选自碳原子数为1-5的脂肪族烃基、芳基、烷基取代的芳基、硅基中的任一种；任何基团都可以被卤原子取代。
  3. 根据权利要求2所述锂二次电池的电解液，其特征在于，R 1、R 2分别独立地选自甲基、乙基、丙基、氟甲基、氟乙基、乙烯基、烯丙基、苯基、苯甲基、氟代苯基、三甲基硅基、三乙烯基硅基中的任一种。
  4. 根据权利要求1～3任一项所述锂二次电池的电解液，其特征在于，磺酸酯化合物选自
    Figure PCTCN2019127033-appb-100002
    Figure PCTCN2019127033-appb-100003
    中的任一种或多种的组合。
  5. 根据权利要求1～4任一项所述的锂二次电池的电解液，其特征在于，磺酸酯化合物质量占电解 液总质量的0.1％～5％。
  6. 根据权利要求1～5任一项所述的锂二次电池的电解液，其特征在于，所述添加剂还包括第二添加剂，第二添加剂选自碳酸亚乙烯酯、氟代碳酸乙烯酯、二氟磷酸锂、二草酸硼酸锂、二氟草酸硼酸锂、1,3-丙烷磺酸内酯、三烯丙基异氰脲酸酯、甲烷二磺酸亚甲酯、硫酸乙烯酯、三烯丙基磷酸酯、三丙炔基磷酸酯、三(三甲基硅烷)磷酸酯、三(三甲基硅烷)硼酸酯中的任一种或多种的组合。
  7. 根据权利要求6所述的锂二次电池的电解液，其特征在于，第二添加剂质量占电解液总质量的0.01％～10％。
  8. 根据权利要求1～7任一项所述的锂二次电池的电解液，其特征在于，非水溶剂质量占电解液总质量的67～91％。
  9. 根据权利要求1～8任一项所述的锂二次电池的电解液，其特征在于，非水溶剂包含环状酯和链状酯。
  10. 根据权利要求9所述的锂二次电池的电解液，其特征在于，环状酯选自碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、γ-丁内酯中的任一种或多种的组合。
  11. 根据权利要求9～10任一项所述的锂二次电池的电解液，其特征在于，链状酯选自碳酸二甲酯、碳酸二乙酯、二乙基碳酸酯、二丙基碳酸酯、碳酸甲乙酯、碳酸甲丙酯、碳酸乙丙酯、甲酸甲酯、甲酸乙酯、甲酸丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、2,2-二氟乙基乙酸酯中的任一种或多种的组合。
  12. 根据权利要求1～11任一项所述的锂二次电池的电解液，其特征在于，锂盐质量占电解液总质量的8-18％。
  13. 根据权利要求1～12任一项所述的锂二次电池的电解液，其特征在于，锂盐选自六氟磷酸锂、双氟磺酰亚胺锂盐、双(三氟甲烷磺酰)亚胺锂中的至少一种。
  14. 一种锂二次电池，其特征在于，锂二次电池包括正极、负极以及电解液；其中，所用的电解液为权利要求1-13任一所述的电解液。
  15. 根据权利要求14所述的锂二次电池，其特征在于，锂二次电池选自锂离子电池、锂硫电池、锂空气电池中的任一种。
  16. 根据权利要求14或15所述的锂二次电池，其特征在于，正极的活性材料为含锂过渡金属氧化物和/或含锂过渡金属磷酸化合物。
  17. 根据权利要求16所述的锂二次电池，其特征在于，正极的活性材料选自Li 1+a(Ni xCo yM 1-x-y)O 2、Li(Ni nMn mCo 2-n-m)O 4、LiM p(PO 4) q的任一种；其中0≤a≤0.3，0≤x≤1，0≤y≤1，0≤x+y≤1， 0≤n≤2，0≤m≤2，0≤n+m≤2，M选自Al、Fe、Ni、Co、Mn、V中的任一种，且0＜p＜5，0＜q＜5。
  18. 根据权利要求14～17任一项所述的锂二次电池，其特征在于，负极的活性材料选自锂金属、锂合金、碳材料、硅或锡及其氧化物中的任一种或多种的组合。
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