WO2023116005A1 - 一种非水电解液及含有该非水电解液的锂离子电池 - Google Patents

一种非水电解液及含有该非水电解液的锂离子电池 Download PDF

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WO2023116005A1
WO2023116005A1 PCT/CN2022/113913 CN2022113913W WO2023116005A1 WO 2023116005 A1 WO2023116005 A1 WO 2023116005A1 CN 2022113913 W CN2022113913 W CN 2022113913W WO 2023116005 A1 WO2023116005 A1 WO 2023116005A1
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electrolytic solution
group
additive
sultone
methyl
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English (en)
French (fr)
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秦虎
时二波
陈晓琴
甘朝伦
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张家港市国泰华荣化工新材料有限公司
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Publication of WO2023116005A1 publication Critical patent/WO2023116005A1/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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/0568—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the technical field of lithium batteries, and in particular relates to a nonaqueous electrolytic solution and a lithium ion battery containing the nonaqueous electrolytic solution.
  • lithium batteries are currently being developed from three aspects.
  • One is to seek new material systems, such as lithium cobalt oxide, lithium-rich manganese base, ternary high-nickel and other positive electrode materials, silicon carbon and other negative electrode materials, etc.; the second is to increase the cut-off charging voltage of existing materials, such as 4.4V, 4.45V , 4.6V high-voltage lithium cobalt oxide cathode materials, etc.; the third is to improve the surface density and compaction density or use thinner current collectors, tapes, and aluminum-plastic cases by changing the battery process.
  • new material systems such as lithium cobalt oxide, lithium-rich manganese base, ternary high-nickel and other positive electrode materials, silicon carbon and other negative electrode materials, etc.
  • the second is to increase the cut-off charging voltage of existing materials, such as 4.4V, 4.45V , 4.6V high-voltage lithium cobalt oxide cathode materials, etc.
  • the third is to improve the surface density and compaction density or use thinner current collectors, tapes, and aluminum-plastic cases by changing the battery process
  • patent CN201610218844.2, patent CN201610518477.8 and patent CN201210098386.5 use three types of main additive compositions such as fluoroethylene carbonate, nitrile compounds and other additives to improve the high-temperature storage performance of lithium cobalt oxide batteries.
  • main additive compositions such as fluoroethylene carbonate, nitrile compounds and other additives to improve the high-temperature storage performance of lithium cobalt oxide batteries.
  • the patent CN200580017212.X found that when a nitrile-containing compound is added to the electrolyte, it will lead to the problem of battery swelling and a significant reduction in recovery capacity under high-temperature storage conditions.
  • the object of the present invention is to provide a non-aqueous electrolyte with well-balanced comprehensive properties in terms of cycle performance, high temperature performance and rate performance.
  • Another object of the present invention is to provide a lithium ion battery containing the above-mentioned non-aqueous electrolyte.
  • One aspect of the present invention provides a kind of non-aqueous electrolytic solution, comprises organic solvent, electrolyte salt and additive, and described additive comprises the first additive, and described first additive is selected from the material shown in general formula (1) and general formula (2) One or more of the substances indicated,
  • G 1 and G 2 are independently bonds, oxygen, sulfur, nitrogen, silicon or phosphorus, and at least one of G 1 and G 2 is oxygen,
  • R 1 is an alkylene group, a haloalkylene group or a silylalkylene group (-Si(CH 3 ) 2 CH 2 -),
  • R is alkyl, fluoroalkyl, alkenyl, fluoroalkenyl, alkynyl, fluoroalkynyl or cyano
  • R 3 is hydrogen, halogen, alkyl, haloalkyl, cyano, siloxane ((CH 3 ) 3 Si—O—), alkoxy or haloalkoxy,
  • X, Y, Z are independently carbon, oxygen, sulfur, nitrogen or phosphorus, and at least one is oxygen, sulfur, nitrogen or phosphorus,
  • n is an integer between 2-6.
  • the "bond" in the present invention refers to a chemical bond, for example, when G is a bond, R can be connected to the carbon atom on the carbonyl through a chemical bond, or when G is a bond, R can be connected to The carbon atoms on the carbonyl group are connected.
  • one of said G 1 and said G 2 is oxygen, and the other is a bond.
  • said R 1 is a C 1 -C 5 alkylene group or a C 1 -C 5 haloalkylene group.
  • said R 1 is a C 1 -C 4 alkylene group or a C 1 -C 4 haloalkylene group.
  • said R 1 is a C 1 -C 3 alkylene group or a C 1 -C 3 haloalkylene group.
  • said R 1 does not contain branched chains.
  • the R 2 is C 1 -C 5 alkyl, C 1 -C 5 fluoroalkyl, C 1 -C 5 alkenyl or C 1 -C 5 fluoroalkenyl.
  • said R 2 is C 1 -C 4 alkyl, C 1 -C 4 fluoroalkyl, C 1 -C 4 alkenyl or C 1 -C 4 fluoroalkenyl.
  • said R 2 is C 1 -C 3 alkyl, C 1 -C 3 fluoroalkyl, C 1 -C 3 alkenyl or C 1 -C 3 fluoroalkenyl.
  • said R 3 is hydrogen or C 1 -C 5 alkyl.
  • said R 3 is hydrogen, methyl, ethyl or propyl.
  • said R 3 is hydrogen or C 1 -C 5 linear alkyl.
  • said R 3 is hydrogen or unsubstituted C 1 -C 5 linear alkyl.
  • any one of X, Y, Z is nitrogen, and the rest are carbon.
  • n 3, 4 or 5.
  • the first additive is 1H-imidazole-1-ethyl acetate, 2-(3-methylpyrazol-1-yl) ethyl acetate, 1-piperidine ethyl acetate or 2-(1H One or more of -imidazol-1-yl) ethyl methacrylate.
  • the feeding amount of the first additive is 0.01-5% of the total mass of the electrolyte solution.
  • the feeding amount of the first additive is 0.1-5% of the total mass of the electrolyte solution.
  • the feeding amount of the first additive is 0.1-2% of the total mass of the electrolyte solution.
  • the feeding amount of the first additive is 0.1-1% of the total mass of the electrolyte solution.
  • the additives also include a second additive, and the second additive is a cyclic carbonate with a carbon-carbon unsaturated bond, a cyclic carbonate with a fluorine atom, a cyclic sulfonate compound, or a compound with One or more of the cyano compounds.
  • the second additive is a cyclic carbonate with a carbon-carbon unsaturated bond, a cyclic carbonate with a fluorine atom, a cyclic sulfonate compound, or a compound with One or more of the cyano compounds.
  • the cyclic carbonates with carbon-carbon unsaturated bonds include but are not limited to vinylene carbonate, methyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, phenylcarbonate Vinylene ester, 4,5-diphenyl vinylene carbonate, vinyl vinylene carbonate, 4,5-divinyl vinylene carbonate, allyl vinylene carbonate, 4,5-diallyl Vinylene carbonate, 4-fluoro vinylene carbonate, 4-fluoro-5-methyl vinylene carbonate, 4-fluoro-5-phenyl vinylene carbonate, 4-fluoro-5-vinyl vinylene carbonate Vinyl ester, 4-allyl-5-fluorovinylene carbonate; Vinyl ethylene carbonate, 4,5-divinyl ethylene carbonate, 4-methyl-5-vinyl ethylene carbonate, 4-allyl-5-vinyl ethylene carbonate, ethynyl ethylene carbonate, 4,5-diethynyl ethylene carbonate,
  • the cyclic carbonate having a carbon-carbon unsaturated bond is one or more of vinylene carbonate, vinyl ethylene carbonate or phenyl vinylene carbonate.
  • the cyclic carbonates with fluorine atoms include but are not limited to monofluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, 4- Fluoro-4-methylethylene carbonate, 4,5-difluoro-4-methylethylene carbonate, 4-fluoro-5-methylethylene carbonate, 4,4-difluoro-5-methyl Ethylene carbonate, 4-(fluoromethyl)-ethylene carbonate, 4-(difluoromethyl)-ethylene carbonate, 4-(trifluoromethyl)-ethylene carbonate, 4-( Fluoromethyl)-4-fluoroethylene carbonate, 4-(fluoromethyl)-5-fluoroethylene carbonate, 4-fluoro-4,5-dimethylethylene carbonate, 4,5-di Fluoro-4,5-dimethylethylene carbonate, 4,4-difluoro-5,5-dimethylethylene carbonate, and the like.
  • the cyclic carbonate with fluorine atoms is fluoroethylene carbonate and/or 4,5-difluoroethylene carbonate.
  • the cyclic sulfonate compound includes but not limited to 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-propane 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
  • the cyclic sulfonate compound is one of 1,3-propane sultone, 1-fluoro-1,3-propane sultone or methylene disulfonate or Various.
  • the compounds with cyano groups include but are not limited to acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile, isovaleronitrile, lauronitrile, 2-methylbutyronitrile, trimethylacetonitrile, Hexanonitrile, cyclopentacarbonitrile, cyclohexanecarbonitrile, acrylonitrile, methacrylonitrile, crotononitrile, 3-methylcrotononitrile, 2-methyl-2-butenenitrile, 2-pentenenitrile, 2- Methyl-2-pentenenitrile, 3-methyl-2-pentenenitrile, 2-hexenenitrile, fluoroacetonitrile, difluoroacetonitrile, trifluoroacetonitrile, 2-fluoropropionitrile, 3-fluoropropionitrile, 2 ,2-difluoropropionitrile, 2,3-difluoropropionitrile,
  • the compound having a cyano group is succinonitrile and/or adiponitrile.
  • the second additive is vinylene carbonate, succinonitrile, fluorovinylene carbonate, vinyl sulfate, 1,3-propane sultone, 1,4-butane Sultone, vinyl sulfite, 1,3-(1-propene) sultone, 2-sulfobenzoic anhydride, methylene methanedisulfonate, vinyl vinyl sulfite, propylene sulfate, One or more of propylene sulfite and butenyl sulfite.
  • the ratio of the first additive to the second additive is 1:1-5.
  • the electrolyte salt is LiBF 4 , LiPF 6 , LiAsF 6 , LiClO 4 , LiN(SO 2 F) 2 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiSO One or more of 3 CF 3 , LiC 2 O 4 BC 2 O 4 , LiFC 6 F 5 BC 2 O 4 , Li 2 PO 2 F 2 , LiBOB or LiODFB.
  • the molar concentration of the electrolyte salt is 0.5-2 mol/L.
  • the molar concentration of the electrolyte salt is 0.5-1.5 mol/L.
  • the organic solvent is ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, butylene carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, methyl formate, ethyl formate, propyl formate, butyl methyl, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propyl, One or more of ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate.
  • the present invention also provides a lithium ion battery, which includes a positive pole, a negative pole and a non-aqueous electrolyte, and the non-aqueous electrolyte is the non-aqueous electrolyte.
  • the positive active material is a layered transition state metal oxide, an olivine-type phosphate compound or a spinel-type manganese-containing compound.
  • the negative electrode active material is graphite.
  • the voltage range of the lithium ion battery is 4.35-4.6V.
  • the present invention has the following advantages compared with the prior art:
  • the electrolytic solution of the present invention can comprehensively improve the normal temperature cycle performance, rate performance and high temperature performance of the high-voltage lithium battery by using the nitrogen-containing heterocyclic compound represented by the general formula (1) and/or the general formula (2) as an additive,
  • cyclic carbonates with fluorine atoms, cyclic sulfonate compounds or compounds with cyano groups further Improve its overall performance.
  • Lithium-ion batteries need to have all the properties of high energy density, high-temperature cycle, high-temperature storage, cycleability, and rate charge-discharge performance. accomplish.
  • the non-aqueous electrolyte battery uses a non-aqueous electrolytic solution having a nitrogen-containing heterocyclic compound, a positive electrode and a negative electrode capable of absorbing and releasing metal ions, and the negative electrode has a negative electrode active material comprising graphite particles and metal particles capable of forming an alloy with Li,
  • the voltage range is between 4.35-4.6V.
  • a kind of non-aqueous electrolytic solution comprises organic solvent, electrolytic salt and additive, and described additive comprises the first additive, and described first additive is selected from the material shown in general formula (1) and general formula (2 ), one or more of the substances indicated in ),
  • G 1 and G 2 are independently bonds, oxygen, sulfur, nitrogen, silicon or phosphorus, and at least one of G 1 and G 2 is oxygen,
  • R 1 is an alkylene group, a haloalkylene group or a silylalkylene group
  • R is alkyl, fluoroalkyl, alkenyl, fluoroalkenyl, alkynyl, fluoroalkynyl or cyano
  • R is hydrogen, halogen, alkyl, haloalkyl, cyano, siloxane, alkoxy or haloalkoxy,
  • X, Y, Z are independently carbon, oxygen, sulfur, nitrogen or phosphorus, and at least one is oxygen, sulfur, nitrogen or phosphorus,
  • n is an integer between 2-6.
  • the additive also includes a second additive, and the second additive is selected from the group consisting of cyclic carbonates with carbon-carbon unsaturated bonds, cyclic carbonates with fluorine atoms, and cyclic sulfonate compounds Or one or more of compounds having a cyano group.
  • the dosages of the first additive and the second additive are respectively 0.01-5% of the total mass of the electrolyte.
  • the dosage ratio of the first additive to the second additive is 1:1-5.
  • the electrolyte salt is lithium salt.
  • the molar concentration of the electrolyte salt is 0.5-2 mol/L.
  • the organic solvent is a carbonate compound.
  • the anode layered transition metal oxide compound capable of occluding and releasing metal ions is LiCoO 2 , especially a high-voltage lithium cobaltate anode material with a voltage range of 4.35-4.6V.
  • the non-aqueous electrolytic solution of the present invention also contains nitrogen-containing heterocyclic compounds represented by general formula (1) and/or general formula (2) or is further used in conjunction with the second additive while containing electrolyte and non-aqueous solvent, While improving the cycle performance and rate discharge performance of the non-aqueous electrolyte battery, the high-temperature storage property can be improved, the amount of gas generated can be reduced, and the battery expansion can be avoided.
  • the "battery swelling" of the non-aqueous electrolyte battery means that after the initial adjustment of the battery, the thickness of the initial battery is compared with the thickness of the battery after the high-temperature cycle test. The battery is swollen".
  • Positive electrode active material 4.35V (or 4.45V) LiCoO 2 mass content 95%, acetylene black 3% as conductive material, and polyvinylidene fluoride (PVDF) 2% as binder material in N-methylpyrrolidone solvent Mix with a disperser to prepare a slurry. The slurry was uniformly coated on both sides of the aluminum foil, dried, and then pressed to produce a positive electrode.
  • active material 4.35V (or 4.45V) LiCoO 2 mass content 95%, acetylene black 3% as conductive material, and polyvinylidene fluoride (PVDF) 2% as binder material in N-methylpyrrolidone solvent Mix with a disperser to prepare a slurry. The slurry was uniformly coated on both sides of the aluminum foil, dried, and then pressed to produce a positive electrode.
  • PVDF polyvinylidene fluoride
  • Negative electrode 95% of the mass content of active material artificial graphite, 2% of SP (conductive carbon black) as conductive material, and 3% of sodium carboxymethyl cellulose (CMC) as binding material, utilize disperser to mix, Make the slurry. The slurry was evenly coated on both sides of the copper foil, dried, and then pressed to produce a negative electrode.
  • SP conductive carbon black
  • CMC sodium carboxymethyl cellulose
  • the above-mentioned positive electrode, negative electrode, and polyolefin separator are laminated in the order of positive and negative, separator, and negative electrode.
  • the thus-obtained battery element was packaged with an aluminum film, vacuum-sealed after injecting the non-aqueous electrolytic solution, and a non-aqueous electrolyte secondary battery was produced.
  • Battery room temperature test 4.35V lithium cobalt oxide is used as the positive electrode, and the assembled battery is first formed.
  • the formation conditions are: at room temperature of 25°C, charge with a constant current of 0.1C to 4.35V, charge with a constant voltage of 4.35V for 2 hours, and let it stand 10min, then discharge to 3.0V with a constant current of 0.2C.
  • room temperature 25°C charge to 4.35V with 1C constant current, then charge with 4.35V constant voltage for 2h, let stand for 10min, discharge with 1C constant current to 3.0V, record the discharge capacity of the first week as W 1 , let stand for 10min .
  • the number of cycles was set as 300 cycles, and the discharge capacity at the 300th cycle was recorded as W 300 .
  • Capacity retention rate at week 300 W 300 /W 1 *100%.
  • Battery rate test 4.35V lithium cobalt oxide is used as the positive electrode, and the assembled battery is first formed.
  • the formation conditions are: at room temperature 25°C, charge at a constant current of 0.1C to 4.35V, then charge at a constant voltage of 4.35V for 2 hours, statically Leave it on for 10 minutes, then discharge to 3.0V at a constant current of 0.2C, and record the discharge capacity as W 0.2c .
  • Battery high temperature test 4.45V lithium cobaltate is used as the positive electrode, and the assembled battery is first formed.
  • the formation conditions are: at room temperature at 25°C, charge at a constant current of 0.1C to 4.45V, then charge at a constant voltage of 4.45V for 2 hours, statically Set it for 10min, then discharge it to 3.0V with a constant current of 0.2C.
  • the test conditions for the high-temperature cycle performance of lithium-ion batteries are: at a high temperature of 45°C, charge with a constant current of 1C to 4.45V, then charge with a constant voltage of 4.45V for 2 hours, let it stand for 10 minutes, and discharge with a constant current of 1C to 3.0V.
  • A1 1H-imidazole-1-ethyl acetate (CAS: 17450-34-9 );
  • A2 2-(3-methylpyrazol-1-yl) ethyl acetate (CAS: 934172-61-9 );
  • A3 1-piperidine ethyl acetate (CAS: 23853-10-3, );
  • PC propylene carbonate
  • EMC ethyl methyl carbonate
  • PS 1,3-propane sultone
  • FEC Fluorinated vinylene carbonate
  • Table 1 shows that using A1, A2, A3, A4 alone or combining A1, A2, A3 or A4 with a second additive (either one or both of VC, PS, FEC and SN) can improve the non- The normal temperature cycle and rate performance of the aqueous electrolyte lithium battery (4.35V),
  • Table 2 shows that the combination of A1, A2, A3 or A4 with the second additive (any one or more of VC, PS, FEC and SN) Use, the high temperature performance of the non-aqueous electrolyte lithium battery (4.45V) is significantly improved.

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Abstract

本发明涉及一种非水电解液及含有该非水电解液的锂离子电池。为了解决现有高压锂电池无法同时兼具高能量密度、高温循环和存储性、常温循环性及倍率充放性等综合性能的问题，本发明提出一种非水电解液，其含有所示物质，其中，G1、G2独立地为键、氧、硫、氮、硅或磷，且G1和G2中至少一个为氧，R1为亚烷基、卤代亚烷基或硅基亚烷基，R2为烷基、氟代烷基、烯基、氟代烯基、炔基、氟代炔基或氰基，R3为氢、卤素、烷基、卤代烷基、氰基、硅氧烷基、烷氧基或卤代烷氧基，X、Y、Z独立地为碳、氧、硫、氮或磷，且至少一个为氧、硫、氮或磷，n为2～6之间的整数，可同时改善锂电池的循环性能、高温性能和倍率性能。

Description

一种非水电解液及含有该非水电解液的锂离子电池 技术领域
本发明属于锂电池技术领域，具体涉及一种非水电解液及含有该非水电解液的锂离子电池。
背景技术
随着手机、平板电脑、智能穿戴以及ETC等新兴消费领域的出现，用电模块功耗的不断上升，常规的锂离子电池已经很难满足用户的使用需求。为提高市场发展及客户需求，锂电池目前主要从三个方面进行开发。一是寻求新的材料体系，如钴酸锂、富锂锰基、三元高镍等正极材料、硅碳等负极材料等；二是提高现有材料的截止充电电压，如4.4V、4.45V、4.6V高电压钴酸锂正极材料等；三是通过改变电池工艺，提高面密度和压实密度或使用更薄的集流体、胶带和铝塑壳等。
近年来，随着电池技术的发展飞速的提高，广阔的市场提供了更多发展机遇的同时也带来了更大的挑战，对电池使用环境适应性提出了更高的要求，需要电池在不同苛刻环境下均能保持较好的性能，因此，扩大电池使用温度范围成为了电池发展的一个重要课题。为了解决这一问题，人们在电池材料上需要取得更大的进步。电解液作为电池的血液，对电池的高低温性能影响非常大，根据文献，通常会通过在电池电解液中加入成膜添加剂来提高电池的循环性能。例如专利CN201610218844.2、专利CN201610518477.8和专利CN201210098386.5采用氟代碳酸乙烯酯、腈类化合物和其他添加剂等三类主要添加剂组合物来改善钴酸锂电池的高温存储性能。不过专利CN200580017212.X发现当电解液中加入含腈基化合物时，会导致电池存在在高温存储条件下电池溶胀现象和恢复容量显著降低的问题。
因此，为了促进高电压锂电池的发展，需要开发更多能够同时兼顾电池的循环及倍率性能和高温性能的非水电解液。
发明内容
本发明的目的在于提供一种在循环性、高温性和倍率性等方面综合性能平衡良好的非水电解液。
本发明的另一个目的是提供一种含有上述非水电解液的锂离子电池。
为实现上述目的，本发明采取的技术方案如下：
本发明的一个方面提供一种非水电解液，包括有机溶剂、电解质盐和添加剂，所述的添 加剂包括第一添加剂，所述的第一添加剂选自通式(1)所示物质和通式(2)所示物质中的一种或多种，
Figure PCTCN2022113913-appb-000001
其中，G 1、G 2独立地为键、氧、硫、氮、硅或磷，且G 1和G 2中至少一个为氧，
R 1为亚烷基、卤代亚烷基或硅基亚烷基(-Si(CH 3) 2CH 2-)，
R 2为烷基、氟代烷基、烯基、氟代烯基、炔基、氟代炔基或氰基，
R 3为氢、卤素、烷基、卤代烷基、氰基、硅氧烷基((CH 3) 3Si-O-)、烷氧基或卤代烷氧基，
X、Y、Z独立地为碳、氧、硫、氮或磷，且至少一个为氧、硫、氮或磷，
n为2～6之间的整数。
通常情况下，本发明中的“键”指化学键，例如当G 1为键时，R 1可通过化学键与羰基上的碳原子相连接，或者当G 2为键时，R 2可通过化学键与羰基上的碳原子相连接。
优选地，所述的G 1和所述的G 2中一个为氧，另一个为键。
优选地，所述的R 1为C 1～C 5亚烷基或C 1～C 5卤代亚烷基。
进一步优选地，所述的R 1为C 1～C 4亚烷基或C 1～C 4卤代亚烷基。
更进一步优选地，所述的R 1为C 1～C 3亚烷基或C 1～C 3卤代亚烷基。
进一步优选地，所述的R 1不含支链。
优选地，所述的R 2为C 1～C 5烷基、C 1～C 5氟代烷基、C 1～C 5烯基或C 1～C 5氟代烯基。
进一步优选地，所述的R 2为C 1～C 4烷基、C 1～C 4氟代烷基、C 1～C 4烯基或C 1～C 4氟代烯基。
更进一步优选地，所述的R 2为C 1～C 3烷基、C 1～C 3氟代烷基、C 1～C 3烯基或C 1～C 3氟代烯基。
优选地，所述的R 3为氢或C 1～C 5烷基。
例如，所述的R 3为氢、甲基、乙基或丙基。
进一步优选地，所述的R 3为氢或C 1～C 5直链烷基。
再进一步优选地，所述的R 3为氢或未取代的C 1～C 5直链烷基。
优选地，X、Y、Z中任意一个为氮，其余为碳。
优选地，n为3、4或5。
优选地，所述的第一添加剂为1H-咪唑-1-乙酸乙酯、2-(3-甲基吡唑-1-基)乙酸乙酯、1-哌啶乙酸乙酯或2-(1H-咪唑-1-基)异丁烯酸乙酯中的一种或多种。
优选地，所述的第一添加剂的投料量为所述的电解液的总质量的0.01～5％。
进一步优选地，所述的第一添加剂的投料量为所述的电解液的总质量的0.1～5％。
再进一步优选地，所述的第一添加剂的投料量为所述的电解液的总质量的0.1～2％。
更进一步优选地，所述的第一添加剂的投料量为所述的电解液的总质量的0.1～1％。
优选地，所述的添加剂还包括第二添加剂，所述的第二添加剂为具有碳-碳不饱和键的环状碳酸酯、具有氟原子的环状碳酸酯、环状磺酸酯化合物或具有氰基的化合物中的一种或多种。
进一步优选地，所述的具有碳-碳不饱和键的环状碳酸酯包括但不限于碳酸亚乙烯酯、甲基碳酸亚乙烯酯、4,5-二甲基碳酸亚乙烯酯、苯基碳酸亚乙烯酯、4,5-二苯基碳酸亚乙烯酯、乙烯基碳酸亚乙烯酯、4,5-二乙烯基碳酸亚乙烯酯、烯丙基碳酸亚乙烯酯、4,5-二烯丙基碳酸亚乙烯酯、4-氟碳酸亚乙烯酯、4-氟-5-甲基碳酸亚乙烯酯、4-氟-5-苯基碳酸亚乙烯酯、4-氟-5-乙烯基碳酸亚乙烯酯、4-烯丙基-5-氟碳酸亚乙烯酯；乙烯基碳酸亚乙酯、4,5-二乙烯基碳酸亚乙酯、4-甲基-5-乙烯基碳酸亚乙酯、4-烯丙基-5-乙烯基碳酸亚乙酯、乙炔基碳酸亚乙酯、4,5-二乙炔基碳酸亚乙酯、4-甲基-5-乙炔基碳酸亚乙酯、4-乙烯基-5-乙炔基碳酸亚乙酯、苯基碳酸亚乙酯、4,5-二苯基碳酸亚乙酯、4-苯基-5-乙烯基碳酸亚乙酯、4-烯丙基-5-苯基碳酸亚乙酯、烯丙基碳酸亚乙酯、4,5-二烯丙基碳酸亚乙酯、4-甲基-5-烯丙基碳酸亚乙酯等中的一种或多种。
进一步优选地，所述的具有碳-碳不饱和键的环状碳酸酯为碳酸亚乙烯酯、乙烯基碳酸亚乙酯或苯基碳酸亚乙烯酯中的一种或多种。
进一步优选地，所述的具有氟原子的环状碳酸酯包括但不限于单氟碳酸亚乙酯、4,4-二氟碳酸亚乙酯、4,5-二氟碳酸亚乙酯、4-氟-4-甲基碳酸亚乙酯、4,5-二氟-4-甲基碳酸亚乙酯、4-氟-5-甲基碳酸亚乙酯、4,4-二氟-5-甲基碳酸亚乙酯、4-(氟甲基)-碳酸亚乙酯、4-(二氟甲基)-碳酸亚乙酯、4-(三氟甲基)-碳酸亚乙酯、4-(氟甲基)-4-氟碳酸亚乙酯、4-(氟甲基)-5-氟碳酸亚乙酯、4-氟-4,5-二甲基碳酸亚乙酯、4,5-二氟-4,5-二甲基碳酸亚乙酯、4,4-二氟-5,5-二甲基碳酸亚乙酯等。
进一步优选地，所述的具有氟原子的环状碳酸酯为氟代碳酸乙烯酯和/或4，5-二氟碳酸乙烯酯。
进一步优选地，所述的环状磺酸酯化合物包括但不限于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、1-氟-1,4-丁磺酸内酯、2-氟-1,4-丁磺酸内酯、3-氟-1,4-丁磺酸内酯、4-氟-1,4-丁磺酸内酯、1-甲基-1,4-丁磺酸内酯、2-甲基-1,4-丁磺酸内酯、3-甲基-1,4-丁磺酸内酯、4-甲基-1,4-丁磺酸内酯、1-丁烯-1,4-磺酸内酯、2-丁烯-1,4-磺酸内酯、3-丁烯-1,4-磺酸内酯、1-氟-1-丁烯-1,4-磺酸内酯、2-氟-1-丁烯-1,4-磺酸内酯、3-氟-1-丁烯-1,4-磺酸内酯、4-氟-1-丁烯-1,4-磺酸内酯、1-氟-2-丁烯-1,4-磺酸内酯、2-氟-2-丁烯-1,4-磺酸内酯、3-氟-2-丁烯-1,4-磺酸内酯、4-氟-2-丁烯-1,4-磺酸内酯、1-氟-3-丁烯-1,4-磺酸内酯、2-氟-3-丁烯-1,4-磺酸内酯、3-氟-3-丁烯-1,4-磺酸内酯、4-氟-3-丁烯-1,4-磺酸内酯、1-甲基-1-丁烯-1,4-磺酸内酯、2-甲基-1-丁烯-1,4-磺酸内酯、3-甲基-1-丁烯-1,4-磺酸内酯、4-甲基-1-丁烯-1,4-磺酸内酯、1-甲基-2-丁烯-1,4-磺酸内酯、2-甲基-2-丁烯-1,4-磺酸内酯、3-甲基-2-丁烯-1,4-磺酸内酯、4-甲基-2-丁烯-1,4-磺酸内酯、1-甲基-3-丁烯-1,4-磺酸内酯、2-甲基-3-丁烯-1,4-磺酸内酯、3-甲基-3-丁烯-1,4-磺酸内酯、4-甲基-3-丁烯-1,4-磺酸内酯、1,5-戊磺酸内酯、1-氟-1,5-戊磺酸内酯、2-氟-1,5-戊磺酸内酯、3-氟-1,5-戊磺酸内酯、4-氟-1,5-戊磺酸内酯、5-氟-1,5-戊磺酸内酯、1-甲基-1,5-戊磺酸内酯、2-甲基-1,5-戊磺酸内酯、3-甲基-1,5-戊磺酸内酯、4-甲基-1,5-戊磺酸内酯、5-甲基-1,5-戊磺酸内酯、1-戊烯-1,5-磺酸内酯、2-戊烯-1,5-磺酸内酯、3-戊烯-1,5-磺酸内酯、4-戊烯-1,5-磺酸内酯、1-氟-1-戊烯-1,5-磺酸内酯、2-氟-1-戊烯-1,5-磺酸内酯、3-氟-1-戊烯-1,5-磺酸内酯、4-氟-1-戊烯-1,5-磺酸内酯、5-氟-1-戊烯-1,5-磺酸内酯、1-氟-2-戊烯-1,5-磺酸内酯、2-氟-2-戊烯-1,5-磺酸内酯、3-氟-2-戊烯-1,5-磺酸内酯、4-氟-2-戊烯-1,5-磺酸内酯、5-氟-2-戊烯-1,5-磺酸内酯、1-氟-3-戊烯-1,5-磺酸内酯、2-氟-3-戊烯-1,5-磺酸内酯、3-氟-3-戊烯-1,5-磺酸内酯、4-氟-3-戊烯-1,5-磺酸内酯、5-氟-3-戊烯-1,5-磺酸内酯、1-氟-4-戊烯-1,5-磺酸内酯、2-氟-4-戊烯-1,5-磺酸内酯、3-氟-4-戊烯-1,5-磺酸内酯、4-氟-4-戊烯-1,5-磺酸内酯、5-氟-4-戊烯-1,5-磺酸内酯、1-甲基-1-戊烯-1,5-磺酸内酯、2-甲基-1-戊烯-1,5-磺酸内酯、3-甲基-1-戊烯-1,5-磺酸内酯、4-甲基-1-戊烯-1,5-磺酸内酯、5-甲基-1-戊烯-1,5-磺酸内酯、1-甲基-2-戊烯-1,5-磺酸内酯、2-甲基-2-戊烯-1,5-磺酸内酯、3-甲基-2-戊烯-1,5-磺酸内酯、4-甲基-2-戊烯-1,5-磺酸内酯、5-甲基-2-戊烯-1,5-磺酸内酯、1-甲基-3-戊烯-1,5-磺酸内酯、2-甲基-3-戊烯-1,5- 磺酸内酯、3-甲基-3-戊烯-1,5-磺酸内酯、4-甲基-3-戊烯-1,5-磺酸内酯、5-甲基-3-戊烯-1,5-磺酸内酯、1-甲基-4-戊烯-1,5-磺酸内酯、2-甲基-4-戊烯-1,5-磺酸内酯、3-甲基-4-戊烯-1,5-磺酸内酯、4-甲基-4-戊烯-1,5-磺酸内酯、5-甲基-4-戊烯-1,5-磺酸内酯；1,3-(1-丙烯)磺内酯、2-磺基苯甲酸酐、硫酸丙烯酯、亚硫酸丙烯酯、亚硫酸丁烯酯、乙烯基亚硫酸乙烯酯、硫酸亚甲酯、硫酸亚乙酯、硫酸亚丙酯、甲烷二磺酸亚甲酯或甲烷二磺酸亚乙酯中的一种或多种。
进一步优选地，所述的环状磺酸酯化合物为1,3-丙磺酸内酯、1-氟-1,3-丙磺酸内酯或甲烷二磺酸亚甲酯中的一种或多种。
进一步优选地，所述的具有氰基的化合物包括但不限于乙腈、丙腈、丁腈、异丁腈、戊腈、异戊腈、月桂腈、2-甲基丁腈、三甲基乙腈、己腈、环戊甲腈、环己甲腈、丙烯腈、甲基丙烯腈、巴豆腈、3-甲基巴豆腈、2-甲基-2-丁烯腈、2-戊烯腈、2-甲基-2-戊烯腈、3-甲基-2-戊烯腈、2-己烯腈、氟乙腈、二氟乙腈、三氟乙腈、2-氟丙腈、3-氟丙腈、2,2-二氟丙腈、2,3-二氟丙腈、3,3-二氟丙腈、2,2,3-三氟丙腈、3,3,3-三氟丙腈、3,3’-氧联二丙腈、3,3’-硫联二丙腈、1,2,3-丙三甲腈、1,3,5-戊三甲腈、五氟丙腈；丙二腈、丁二腈、戊二腈、己二腈、庚二腈、辛二腈、壬二腈、癸二腈、十一烷二腈、十二烷二腈、甲基丙二腈、乙基丙二腈、异丙基丙二腈、叔丁基丙二腈、甲基丁二腈、2,2-二甲基丁二腈、2,3-二甲基丁二腈、2,3,3-三甲基丁二腈、2,2,3,3-四甲基丁二腈、2,3-二乙基-2,3-二甲基丁二腈、2,2-二乙基-3,3-二甲基丁二腈、联环己烷-1,1-二腈、联环己烷-2,2-二腈、联环己烷-3,3-二腈、2,5-二甲基-2,5-己烷二腈、2,3-二异丁基-2,3-二甲基丁二腈、2,2-二异丁基-3,3-二甲基丁二腈、2-甲基戊二腈、2,3-二甲基戊二腈、2,4-二甲基戊二腈、2,2,3,3-四甲基戊二腈、2,2,4,4-四甲基戊二腈、2,2,3,4-四甲基戊二腈、2,3,3,4-四甲基戊二腈、顺丁烯二腈、反丁烯二腈、1,4-二氰基戊烷、2,6-二氰基庚烷、2,7-二氰基辛烷、2,8-二氰基壬烷、1,6-二氰基癸烷、1,2-二氰基苯、1,3-二氰基苯、1,4-二氰基苯、3,3’-(亚乙基二氧)二丙腈、3,3’-(亚乙基二硫)二丙腈；环己三甲腈、三氰基乙胺、三氰基乙氧基丙烷、三氰基乙烯、戊三甲腈、丙三甲腈或庚三甲腈中的一种或多种。
进一步优选地，所述的具有氰基的化合物为丁二腈和/或己二腈。
根据一些具体且优选的实施例，所述的第二添加剂为碳酸亚乙烯酯、丁二腈、氟代碳酸亚乙烯酯、硫酸乙烯酯、1,3-丙烷磺内酯、1,4-丁磺酸内酯、亚硫酸乙烯酯、1,3-(1-丙烯)磺内酯、2-磺基苯甲酸酐、甲烷二磺酸亚甲酯、乙烯基亚硫酸乙烯酯、硫酸丙烯酯、亚硫酸丙烯酯、亚硫酸丁烯酯中的一种或多种。
优选地，所述的第一添加剂和所述的第二添加剂的投料量比为1:1～5。
优选地，所述的电解质盐为LiBF 4、LiPF 6、LiAsF 6、LiClO 4、LiN(SO 2F) 2、LiN(SO 2CF 3) 2、LiN(SO 2C 2F 5) 2、LiSO 3CF 3、LiC 2O 4BC 2O 4、LiFC 6F 5BC 2O 4、Li 2PO 2F 2、LiBOB或LiODFB中的一种或多种。
优选地，所述的电解质盐的摩尔浓度为0.5～2mol/L。
进一步优选的，所述的电解质盐的摩尔浓度为0.5～1.5mol/L。
优选地，所述的有机溶剂为碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酯甲乙酯、碳酸丁烯酯、γ-丁内酯、γ-戊内酯、δ-戊内酯、ε-己内酯、甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酯丁酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、丙酯甲酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸丁酯的一种或多种。
本发明还提供一种锂离子电池，其包括正极、负极和非水电解液，所述的非水电解液为所述的非水电解液。
优选地，所述的正极活性物质为层状过渡态金属氧化物，橄榄石型磷酸盐化合物或尖晶石型含锰化合物。
优选地，所述的负极活性物质为石墨。
优选地，所述的锂离子电池的电压范围为4.35-4.6V。
由于上述技术方案运用，本发明与现有技术相比具有下列优点：
本发明的电解液通过使用通式(1)和/或通式(2)所示的具有含氮杂环化合物作为添加剂，能够综合提高高电压锂电池的常温循环性能、倍率性能、高温性能，
进一步地，通过与具有碳-碳不饱和键的环状碳酸酯、具有氟原子的环状碳酸酯、环状磺酸酯化合物或具有氰基的化合物中的一种或多种联用，进一步提高其综合性能。
具体实施方式
下面结合实施例对本发明作进一步描述。但本发明并不限于以下实施例。实施例中采用的实施条件可以根据具体使用的不同要求做进一步调整，未注明的实施条件为本行业中的常规条件。本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
近年来对于3C数码等领域使用的锂离子电池特性要求越来越高，锂离子要电池需要同时具有高能量密度、高温循环、高温存储性、循环性、倍率充放性等所有性能，但尚未实现。
为解决上述技术问题，本发明的发明人进行了深入研究和大量实验，得以提出一种锂离子非水电解液及使用该非水电解液的锂离子二次电池。该非水电解质电池使用具有含氮杂环 化合物的非水电解液、能够吸留和放出金属离子的正极及负极，并且负极具有包含石墨粒子和能够与Li形成合金的金属粒子的负极活性物质，电压范围在4.35-4.6V之间。
根据本发明，一种非水电解液，包括有机溶剂、电解质盐和添加剂，所述的添加剂包括第一添加剂，所述的第一添加剂选自通式(1)所示物质和通式(2)所示物质中的一种或多种，
Figure PCTCN2022113913-appb-000002
其中，G 1、G 2独立地为键、氧、硫、氮、硅或磷，且G 1和G 2中至少一个为氧，
R 1为亚烷基、卤代亚烷基或硅基亚烷基，
R 2为烷基、氟代烷基、烯基、氟代烯基、炔基、氟代炔基或氰基，
R 3为氢、卤素、烷基、卤代烷基、氰基、硅氧烷基、烷氧基或卤代烷氧基，
X、Y、Z独立地为碳、氧、硫、氮或磷，且至少一个为氧、硫、氮或磷，
n为2～6之间的整数。
根据本发明，所述的添加剂还包括第二添加剂，所述的第二添加剂选自具有碳-碳不饱和键的环状碳酸酯、具有氟原子的环状碳酸酯、环状磺酸酯化合物或具有氰基的化合物中的一种或多种。
根据本发明，所述的第一添加剂和所述的第二添加剂的投料量分别为所述的电解液的总质量的0.01～5％。
根据本发明，所述的第一添加剂和所述的第二添加剂的投料量比为1:1～5。
根据本发明，所述的电解质盐为锂盐。
根据本发明，所述的电解质盐的摩尔浓度为0.5～2mol/L。
根据本发明，所述的有机溶剂为碳酸酯类化合物。
根据本发明，能够吸留和放出金属离子的正极为层状过渡金属氧化合物为LiCoO 2，尤其是电压范围在4.35-4.6V之间的高电压钴酸锂正极材料。
本发明的非水电解液通过在含有电解质及非水溶剂的同时还含有通式(1)和/或通式(2)所示的具有含氮杂环化合物或进一步与第二添加剂配合使用，在提高非水电解质电池的循环性能和倍率放电性能的同时，提高高温保存性，可以减少气体产生量、避免电池膨胀。这里，非水电解质电池的所述的“电池膨胀”是指，在进行电池的初始调节之后，将初期的电池厚 度与高温循环试验后的电池厚度进行比较，其厚度增加，即表明发生了“电池膨胀”。
下面结合实施例对本发明作进一步描述。但本发明并不限于以下实施例。实施例中采用的实施条件可以根据具体使用的不同要求做进一步调整，未注明的实施条件为本行业中的常规条件。本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
正极：活性物质4.35V(或4.45V)LiCoO 2的质量含量95％，作为导电材料的乙炔黑3％，及作为粘结材料聚偏氟乙烯烯(PVDF)2％在N-甲基吡咯烷酮溶剂中利用分散混合器进行混合，制作浆料。将该浆料均匀涂布在铝箔的两面并进行干燥之后中，进行压制制作正极。
负极：活性物质人造石墨的质量含量95％，作为导电材料的SP(导电炭黑)2％，及作为粘结材料的羧甲基纤维素钠(CMC)3％，利用分散混合器进行混合，制作浆料。将该浆料均匀涂布在铜箔的两面并进行干燥之后中，进行压制制作负极。
非水电解液的制备：
在充氩气的手套箱中(H 2O含量<10ppm)，将EC和EMC以30：70的体积比混合均匀或将DEC，EC和EMC以20：30：50的体积比混合均匀或将EC、PC、EP和PP以20：10：30：40的体积比混合均匀或EC、PC和PP以20：10：70的体积比混合均匀，在混合溶液中加入终浓度为1mol/L的LiPF 6，制得电解液，将其称为基准电解液并作为对比例1，其他实施例和对比例的非水电解液配方见表1和表2，其中，在没有特别说明的情况下，“wt”指质量分数。
非水电解质电池的制备：
将上述正极、负极、聚烯烃隔膜按照正负、隔膜、负极的顺序叠层。利用铝膜包装由此得到电池元件，注入非水电解液之后进行真空密封，制作了非水电解质二次电池。
非水电解液二次电池的评价：
电池常温测试：正极采用4.35V钴酸锂，组装好的电池首先进行化成，化成条件为：常温25℃条件下，以0.1C恒流充电至4.35V，以4.35V恒压充电2h，静置10min，再以0.2C恒流放电至3.0V。常温25℃条件下，以1C恒流充电至4.35V，再以4.35V恒压充电2h，静置10min，以1C恒流放电至3.0V，记录第一周放电容量为W 1，静置10min。循环次数设定为300周，第300周放电容量记录为W 300。第300周容量保持率＝W 300/W 1*100％。
电池倍率测试：正极采用4.35V钴酸锂，组装好的电池首先进行化成，化成条件为：常温25℃条件下，以0.1C恒流充电至4.35V，接着以4.35V恒压充电2h，静置10min，再以0.2C恒流放电至3.0V，放电容量记录为W 0.2c。然后以0.2C恒流充电至4.35V，接着以4.35V 恒压充电2h，静置10min，再以3.0C恒流放电至3.0V，放电容量记录为W 3.0c；然后以0.2C恒流充电至4.35V，接着以4.35V恒压充电2h，静置10min，再以5.0C恒流放电至3.0V，放电容量记录为W 5.0C。3C倍率放电保持率＝W 3.0C/W 0.2c*100％；5C倍率放电保持率＝W 5.0C/W 0.2c*100％。
电池高温测试：正极采用4.45V钴酸锂，组装好的电池首先进行化成，化成条件为：常温25℃条件下，以0.1C恒流充电至4.45V，接着以4.45V恒压充电2h，静置10min，再以0.2C恒流放电至3.0V。锂离子电池高温循环性能的测试条件为：高温45℃条件下，以1C恒流充电至4.45V，再以4.45V恒压充电2h，静置10min，以1C恒流放电至3.0V，放电容量记录为W 1，静置10min，电池厚度记录为L 1。循环次数设定为300周，第300周放电容量记录为W 300，电池厚度记录为L 300。第300周容量保持率＝W 300/W 1*100％；第300周的电池膨胀率＝(L 300-L 1)/L 1*100％。
表1非水电解液锂电池(4.35V)的常温循环及倍率性能
Figure PCTCN2022113913-appb-000003
Figure PCTCN2022113913-appb-000004
表2非水电解液锂离子电池(4.45V)的高温性能
Figure PCTCN2022113913-appb-000005
Figure PCTCN2022113913-appb-000006
Figure PCTCN2022113913-appb-000007
A1：1H-咪唑-1-乙酸乙酯(CAS:17450-34-9
Figure PCTCN2022113913-appb-000008
)；
A2：2-(3-甲基吡唑-1-基)乙酸乙酯(CAS:934172-61-9
Figure PCTCN2022113913-appb-000009
)；
A3：1-哌啶乙酸乙酯(CAS:23853-10-3，
Figure PCTCN2022113913-appb-000010
)；
A4：2-(1H-咪唑-1-基)异丁烯酸乙酯(CAS:62037-81-4
Figure PCTCN2022113913-appb-000011
DEC：碳酸二乙酯；
EC：碳酸乙烯酯；
PC：碳酸丙烯酯；
EMC：碳酸甲乙酯；
EP：丙酸乙酯；
PP：丙酸丙酯；
VC：碳酸亚乙烯酯；
PS：1,3-丙磺酸内酯；
FEC：氟代碳酸亚乙烯酯；
SN：丁二腈；
DTD：硫酸乙烯酯。
表1显示，单独使用A1、A2、A3、A4或将A1、A2、A3或A4与第二添加剂(VC、PS、FEC和SN中的任一一个或两个)组合使用，可以改善非水电解液锂电池(4.35V)的常温循环及倍率性能，表2显示，将A1、A2、A3或A4与第二添加剂(VC、PS、FEC和SN中的任意一种或多种)组合使用，非水电解液锂电池(4.45V)高温性能显著提高。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围，凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (15)

  1. 一种非水电解液，包括有机溶剂、电解质盐和添加剂，其特征在于，所述的添加剂包括第一添加剂，所述的第一添加剂选自通式(1)所示物质和通式(2)所示物质中的一种或多种，
    Figure PCTCN2022113913-appb-100001
    其中，G 1、G 2独立地为键、氧、硫、氮、硅或磷，且G 1和G 2中至少一个为氧，
    R 1为亚烷基、卤代亚烷基或硅基亚烷基，
    R 2为烷基、氟代烷基、烯基、氟代烯基、炔基、氟代炔基或氰基，
    R 3为氢、卤素、烷基、卤代烷基、氰基、硅氧烷基、烷氧基或卤代烷氧基，
    X、Y、Z独立地为碳、氧、硫、氮或磷，且至少一个为氧、硫、氮或磷，
    n为2～6之间的整数。
  2. 根据权利要求1所述的非水电解液，其特征在于，
    所述的G 1和所述的G 2中一个为氧，另一个为键，
    和/或，所述的R 1为C 1～C 5亚烷基或C 1～C 5卤代亚烷基；
    和/或，所述的R 2为C 1～C 5烷基、C 1～C 5氟代烷基、C 1～C 5烯基或C 1～C 5氟代烯基；
    和/或，所述的R 3为氢或C 1～C 5烷基；
    和/或，X、Y、Z中任意一个为氮，其余为碳；
    和/或，n为3、4或5。
  3. 根据权利要求2所述的非水电解液，其特征在于，
    所述的R 1为C 1～C 3亚烷基或C 1～C 3卤代亚烷基；和/或，
    所述的R 2为C 1～C 3烷基、C 1～C 3氟代烷基、C 1～C 3烯基或C 1～C 3氟代烯基；和/或，
    所述的R 3为氢或C 1～C 5直链烷基。
  4. 根据权利要求1所述的非水电解液，其特征在于，所述的第一添加剂选自1H-咪唑-1-乙酸乙酯、2-(3-甲基吡唑-1-基)乙酸乙酯、1-哌啶乙酸乙酯或2-(1H-咪唑-1-基)异丁烯酸乙酯中的一种或多种。
  5. 根据权利要求1所述的非水电解液，其特征在于，所述的第一添加剂的投料量为所述的电解液的总质量的0.01～5％。
  6. 根据权利要求5所述的非水电解液，其特征在于，所述的第一添加剂的投料量为所述的电解液的总质量的0.1～5％。
  7. 根据权利要求1所述的非水电解液，其特征在于，所述的添加剂还包括第二添加剂，所述的第二添加剂选自具有碳-碳不饱和键的环状碳酸酯、具有氟原子的环状碳酸酯、环状磺酸酯化合物或具有氰基的化合物中的一种或多种。
  8. 根据权利要求7所述的非水电解液，其特征在于，所述的第二添加剂的投料量为所述的电解液的总质量的0.01～5％。
  9. 根据权利要求7所述的非水电解液，其特征在于，所述的第二添加剂选自碳酸亚乙烯酯、丁二腈、氟代碳酸亚乙烯酯、硫酸乙烯酯、1-3丙烷磺内酯、1,4-丁磺酸内酯、亚硫酸乙烯酯、1,3-(1-丙烯)磺内酯、2-磺基苯甲酸酐、甲烷二磺酸亚甲酯、乙烯基亚硫酸乙烯酯、硫酸丙烯酯、亚硫酸丙烯酯、亚硫酸丁烯酯中的一种或多种。
  10. 根据权利要求1所述的非水电解液，其特征在于，所述的电解质盐选自LiBF 4、LiPF 6、LiAsF 6、LiClO 4、LiN(SO 2F) 2、LiN(SO 2CF 3) 2、LiN(SO 2C 2F 5) 2、LiSO 3CF 3、LiC 2O 4BC 2O 4、LiFC 6F 5BC 2O 4、Li 2PO 2F 2、LiBOB或LiODFB中的一种或多种。
  11. 根据权利要求1所述的非水电解液，其特征在于，所述的电解质盐的摩尔浓度为0.5～2mol/L。
  12. 根据权利要求1所述的非水电解液，其特征在于，所述的有机溶剂选自碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酯甲乙酯、碳酸丁烯酯、γ-丁内酯、γ-戊内酯、δ-戊内酯、ε-己内酯、甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酯丁酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、丙酯甲酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸丁酯的一种或多种。
  13. 一种锂离子电池，其包括正极、负极和非水电解液，其特征在于，所述的非水电解液为权利要求1所述的非水电解液。
  14. 根据权利要求13所述的锂离子电池，其特征在于，所述正极的活性物质为层状过渡态金属氧化物，橄榄石型磷酸盐化合物或尖晶石型含锰化合物，
    和/或，所述负极的活性物质为石墨。
  15. 根据权利要求13所述的锂离子电池，其特征在于，所述的锂离子电池的电压范围为4.35-4.6V。
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