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WO2019080259A1 - 锂二次电池电解液及其锂二次电池 - Google Patents

锂二次电池电解液及其锂二次电池

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Publication number
WO2019080259A1
WO2019080259A1 PCT/CN2017/113956 CN2017113956W WO2019080259A1 WO 2019080259 A1 WO2019080259 A1 WO 2019080259A1 CN 2017113956 W CN2017113956 W CN 2017113956W WO 2019080259 A1 WO2019080259 A1 WO 2019080259A1
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WO
WIPO (PCT)
Prior art keywords
secondary battery
lithium secondary
electrolyte
lithium
methyl
Prior art date
Application number
PCT/CN2017/113956
Other languages
English (en)
French (fr)
Inventor
范伟贞
余乐
赵经纬
Original Assignee
广州天赐高新材料股份有限公司
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Publication date
Application filed by 广州天赐高新材料股份有限公司 filed Critical 广州天赐高新材料股份有限公司
Publication of WO2019080259A1 publication Critical patent/WO2019080259A1/zh

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the field of lithium secondary battery technology, and in particular to a lithium secondary battery electrolyte and a lithium secondary battery containing the same.
  • lithium secondary batteries have received attention and development in various industries due to their high energy density. Compared with other rechargeable batteries, lithium secondary batteries have the advantages of high energy density, high operating voltage, long cycle life, fast charge and discharge, and environmental protection. At present, lithium secondary batteries have good application prospects in portable 3C electronic devices such as mobile phones and notebook computers, high-power power batteries, and energy storage.
  • a solvent having a higher boiling point such as diethyl carbonate or ethyl methyl carbonate is generally selected as the main solvent of the electrolytic solution, but the melting point of these solvents is relatively high, and the electrolyte at a low temperature The conductivity drops very quickly and the battery impedance increases rapidly. It is difficult to meet the low-temperature discharge performance of the battery.
  • Patent CN101842349B discloses an electrolyte containing a phenyl sulfonate compound comprising 0.01-10% of a phenyl sulfonate additive. This electrolyte can improve the low temperature cycle performance of the battery, but does not improve the normal temperature, high temperature cycle and high temperature storage performance of the battery.
  • the methyl pentafluorobenzenesulfonate comprises from 0.1 to 5.0% of the total mass of the electrolyte of the lithium secondary battery.
  • the conductive lithium salt is at least one of lithium hexafluorophosphate or lithium bisfluorosulfonate; the conductive lithium salt accounts for 8.0-18.0% of the total mass of the lithium secondary battery electrolyte.
  • the organic solvent is composed of a cyclic solvent and a linear solvent, and the mass ratio of the cyclic solvent to the linear solvent is (1 to 3): 3.
  • the amount of the organic solvent is 62.0-91.8% of the total mass of the lithium secondary battery electrolyte.
  • the cyclic solvent is selected from at least one of ethylene carbonate, propylene carbonate, ⁇ -butyrolactone, and 1,4 butyl sultone.
  • the linear solvent is selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl acetate, propyl propionate, 1,1,2,2-tetrafluoroethyl. At least one of -2,2,3,3-tetrafluoropropyl ether and 2,2-difluoroethyl acetate.
  • Another object of the present invention is to provide a lithium secondary battery.
  • a lithium secondary battery comprising the above lithium secondary battery electrolyte (including a positive electrode sheet containing a positive electrode active material, a negative electrode sheet containing a negative electrode active material, and a separator).
  • the above electrolyte solution can improve the normal temperature cycle performance, high temperature storage performance and low temperature discharge performance of the electrolyte by adding methyl pentafluorobenzenesulfonate in combination with lithium difluorophosphate, vinyl sulfate, and pentafluoroethoxyphosphazene.
  • a lithium secondary battery electrolyte is composed of an organic solvent, a conductive lithium salt, methyl pentafluorobenzenesulfonate, and an additive.
  • the organic solvent accounts for 77.0% of the total mass of the lithium secondary battery electrolyte, and is composed of a cyclic solvent (ethylene carbonate) and a linear solvent (ethyl methyl carbonate), and the mass ratio of ethylene carbonate to ethyl methyl carbonate is 1 :1.
  • the conductive lithium salt is lithium hexafluorophosphate, which accounts for 18.0% of the total mass of the lithium secondary battery electrolyte.
  • the present embodiment relates to a lithium secondary battery electrolyte comprising an organic solvent, a conductive lithium salt, a methyl pentafluorobenzenesulfonate and an additive.
  • the organic solvent accounts for 81.5% of the total mass of the electrolyte of the lithium secondary battery, and is composed of a cyclic solvent (vinyl carbonate) and a linear solvent (dimethyl carbonate), and the mass ratio of the ethylene carbonate to the dimethyl carbonate is 1 :2.
  • the conductive lithium salt is lithium hexafluorophosphate, which accounts for 15.0% of the total mass of the lithium secondary battery electrolyte.
  • Methyl pentafluorobenzenesulfonate accounts for 0.5% of the total mass of the electrolyte, and the additive is lithium difluorophosphate or vinyl sulfate, which accounts for 1.0% and 2.0% of the total mass of the electrolyte, respectively.
  • the electrolytic solution of this example was used for a LiNi 0.8 Co 0.1 Mn 0.1 O 2 /silicon carbon soft pack battery.
  • a lithium secondary battery electrolyte is composed of an organic solvent, a conductive lithium salt, methyl pentafluorobenzenesulfonate, and an additive.
  • the organic solvent accounts for 85.0% of the total mass of the electrolyte of the lithium secondary battery, and is composed of a cyclic solvent (ethylene carbonate) and a linear solvent (diethyl carbonate), and the mass ratio of ethylene carbonate to diethyl carbonate is 1 :3.
  • the conductive lithium salt is lithium hexafluorophosphate, which accounts for 12.0% of the total mass of the lithium secondary battery electrolyte.
  • Methyl pentafluorobenzenesulfonate accounts for 1.0% of the total mass of the electrolyte, and the additive is vinyl sulfate and pentafluoroethoxyphosphoronitrile, which account for 1.0% and 1.5%, respectively, of the total mass of the electrolyte.
  • the electrolytic solution of this example was applied to a LiNi 0.6 Co 0.2 Mn 0.2 O 2 /silicon carbon soft pack battery.
  • the conductive lithium salt is lithium hexafluorophosphate, which accounts for 8.5% of the total mass of the lithium secondary battery electrolyte.
  • Methyl pentafluorobenzenesulfonate accounts for 1.0% of the total mass of the electrolyte
  • the additive is lithium difluorophosphate, which accounts for 1.5% of the total mass of the electrolyte.
  • the electrolytic solution of this example was applied to a LiNi 0.5 Co 0.2 Mn 0.3 O 2 /graphite soft pack battery.
  • a lithium secondary battery electrolyte is composed of an organic solvent, a conductive lithium salt, methyl pentafluorobenzenesulfonate, and an additive.
  • the organic solvent accounts for 83.5% of the total mass of the electrolyte of the lithium secondary battery, and is composed of a cyclic solvent (ethylene carbonate) and a linear solvent (ethyl methyl carbonate), and the mass ratio of ethylene carbonate and ethyl methyl carbonate is 1 :1.
  • the conductive lithium salt is lithium hexafluorophosphate, which accounts for 12.5% of the total mass of the lithium secondary battery electrolyte.
  • Methyl pentafluorobenzenesulfonate accounts for 1.0% of the total mass of the electrolyte, and the additive is pentafluoroethoxyphosphoronitrile, which accounts for 3.0% of the total mass of the electrolyte.
  • the electrolytic solution of this example was applied to a LiNi 0.5 Co 0.2 Mn 0.3 O 2 /silicon carbon soft pack battery.
  • a lithium secondary battery electrolyte is composed of an organic solvent, a conductive lithium salt, methyl pentafluorobenzenesulfonate, and an additive.
  • the organic solvent accounts for 70.0% of the total mass of the lithium secondary battery electrolyte, and is composed of a cyclic solvent (ethylene carbonate) and a linear solvent (ethyl methyl carbonate), and the mass ratio of ethylene carbonate and ethyl methyl carbonate is 1 :1.
  • the conductive lithium salt is lithium hexafluorophosphate, which accounts for 13.0% of the total mass of the lithium secondary battery electrolyte.
  • Methyl pentafluorobenzenesulfonate accounts for 2.0% of the total mass of the electrolyte, and the additive is vinyl sulfate and pentafluoroethoxyphosphoronitrile, accounting for 1.0% and 14.0% of the total mass of the electrolyte.
  • the electrolytic solution of this example was used for a LiCoO 2 /graphite soft pack battery.
  • a lithium secondary battery electrolyte is composed of an organic solvent, a conductive lithium salt, methyl pentafluorobenzenesulfonate, and an additive.
  • the organic solvent accounts for 83.0% of the total mass of the electrolyte of the lithium secondary battery, and is composed of a cyclic solvent (ethylene carbonate) and a linear solvent (ethyl methyl carbonate), and the mass ratio of ethylene carbonate and ethyl methyl carbonate is 1 :1.
  • the conductive lithium salt is lithium hexafluorophosphate, which accounts for 13.0% of the total mass of the lithium secondary battery electrolyte.
  • Methyl pentafluorobenzenesulfonate accounts for 3.0% of the total mass of the electrolyte, and the additive is vinyl sulfate, which accounts for 1.0% of the total mass of the electrolyte.
  • the electrolytic solution of this example was applied to a LiNi 0.6 Co 0.2 Mn 0.2 O 2 /silicon carbon soft pack battery.
  • a lithium secondary battery electrolyte is composed of an organic solvent, a conductive lithium salt, methyl pentafluorobenzenesulfonate, and an additive.
  • the organic solvent accounts for 80.5% of the total mass of the lithium secondary battery electrolyte, and is composed of a cyclic solvent (ethylene carbonate) and a linear solvent (ethyl methyl carbonate). The mass ratio of ethylene carbonate and ethyl methyl carbonate is 1 :1.
  • the conductive lithium salt is lithium hexafluorophosphate or lithium bisfluorosulfonimide, which accounts for 10.0% and 4.5% of the total mass of the electrolyte of the lithium secondary battery.
  • Methyl pentafluorobenzenesulfonate accounts for 4.5% of the total mass of the electrolyte, and the additive is vinyl sulfate, which accounts for 0.5% of the total mass of the electrolyte.
  • the electrolytic solution of this example was used for a LiNi 0.6 Co 0.2 Mn 0.2 O 2 /graphite soft pack battery.
  • a lithium secondary battery electrolyte is composed of an organic solvent, a conductive lithium salt, methyl pentafluorobenzenesulfonate, and an additive.
  • the organic solvent accounts for 83.5% of the total mass of the electrolyte of the lithium secondary battery, and is composed of a cyclic solvent (ethylene carbonate) and a linear solvent (ethyl methyl carbonate), and the mass ratio of ethylene carbonate and ethyl methyl carbonate is 1 :1.
  • the conductive lithium salt is lithium hexafluorophosphate or lithium bisfluorosulfonimide, which accounts for 8.0% and 3.0% of the total mass of the electrolyte of the lithium secondary battery.
  • Methyl pentafluorobenzenesulfonate accounts for 4.5% of the total mass of the electrolyte, and the additive is pentafluoroethoxyphosphazene, which accounts for 1.0% of the total mass of the electrolyte.
  • the electrolytic solution of this example was used for a LiNi 0.6 Co 0.2 Mn 0.2 O 2 /graphite soft pack battery.
  • the electrolytic solution of this comparative example was prepared in the same manner as in Example 1, except that methyl pentafluorobenzenesulfonate was not contained, and the electrolytic solution was applied to a battery in the same manner as in Example 1 to test its properties.
  • the electrolytic solution of this comparative example was prepared in the same manner as in Example 2, except that methyl pentafluorobenzenesulfonate was not contained, and the electrolytic solution was applied to a battery in the same manner as in Example 2 to test its properties.
  • the electrolytic solution of this comparative example was prepared in the same manner as in Example 3, except that methyl pentafluorobenzenesulfonate was not contained, and the electrolytic solution was applied to a battery in the same manner as in Example 3 to test its properties.
  • the electrolytic solution of this comparative example was prepared in the same manner as in Example 4, except that methyl pentafluorobenzenesulfonate was not contained, and the electrolytic solution was applied to a battery in the same manner as in Example 4 to test its properties.
  • the electrolytic solution of this comparative example was prepared in the same manner as in Example 5, except that methyl pentafluorobenzenesulfonate was not contained, and the electrolytic solution was applied to a battery in the same manner as in Example 5 to test its properties.
  • the electrolytic solution of this comparative example was prepared in the same manner as in Example 6, except that methyl pentafluorobenzenesulfonate was not contained, and the electrolytic solution was applied to a battery in the same manner as in Example 6 to test its properties.
  • the electrolytic solution of this comparative example was prepared in the same manner as in Example 7, except that methyl pentafluorobenzenesulfonate was not contained, and the electrolytic solution was applied to a battery in the same manner as in Example 7 to test its properties.
  • the electrolytic solution of this comparative example was prepared in the same manner as in Example 8, except that methyl pentafluorobenzenesulfonate was not contained, and the electrolytic solution was applied to a battery in the same manner as in Example 8 to test its properties.
  • the electrolytic solution of this comparative example was prepared in the same manner as in Example 9, except that methyl pentafluorobenzenesulfonate was not contained, and the electrolytic solution was applied to a battery in the same manner as in Example 9 to test its properties.
  • the electrolytic solution of this comparative example was prepared in the same manner as in Example 10 except that methyl pentafluorobenzenesulfonate was not contained, and the electrolytic solution was applied to a battery in the same manner as in Example 10 to test its properties.
  • the lithium secondary batteries prepared in the above Examples 1 to 10 and Comparative Examples 1 to 10 were subjected to normal temperature circulation and high. Temperature storage, low temperature discharge test.
  • Charge and discharge test conditions In order to measure the charge and discharge performance of the battery using the electrolyte prepared by the present invention, the following operations were carried out: positive and negative electrode sheets were prepared according to a conventional method, and electrolytes prepared in the respective examples were used to inject liquid in a glove box. Pole piece preparation 053048 type soft pack battery, using the Xinwei (BS-9300R type) battery test system to test the charge and discharge of the prepared 053048 type battery, and compare it with the corresponding comparative electrolyte prepared battery. The battery was placed at a normal temperature of 3.0 to 4.2 V at a rate of 1 C for a charge and discharge cycle and placed at 60 ° C for 15 days after full charge storage, and discharged at -20 ° C for 0.5 C. The capacity retention rate of the battery at a normal temperature of 300 cycles, the discharge capacity retention rate after 60 days of full-time storage at 60 ° C, and the discharge capacity retention rate of -20 ° C and 0.5 C were recorded. The results are shown in Table 1.

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Abstract

本发明涉及一种锂二次电池电解液及其锂二次电池，锂二次电池电解液包括有机溶剂、导电锂盐、五氟苯磺酸甲酯和添加剂。上述电解液通过添加五氟苯磺酸甲酯与二氟磷酸锂、硫酸乙烯酯、五氟乙氧基磷腈组合使用能够改善电解液的常温循环性能，高温存储性能和低温放电性能。

Description

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技术领域，特别是涉及一种锂二次电池电解液及其含有该电解液的锂二次电池。
背景技术
近年来，锂二次电池因其高能量密度得到了各行业领域的关注与发展。与其他可充电电池相比，锂二次电池具有能量密度高、工作电压高、循环寿命长、可快速充放电、绿色环保等优点。目前锂二次电池在移动电话、笔记本电脑等便携式3C电子设备或大功率动力电池以及储能等方面有较好的应用前景。
为了改善锂二次电池的高温性能，一般会选择碳酸二乙酯、碳酸甲乙酯等沸点较高的溶剂作为电解液的主溶剂，但是这些溶剂的熔点相对较高，在低温下电解液的电导率下降非常快，电池阻抗增加快速。很难满足电池的低温放电性能。为了改善电池的低温性能，一般会选择乙酸乙酯、丙酸乙酯等熔点较低的羧酸酯作为电解液的主溶剂，但是这些溶剂的沸点相对较低，对电池的高温性能不利。而在添加剂方面，为了改善高温性能一般使用碳酸亚乙烯酯、碳酸乙烯亚乙酯等添加剂，但是这一类添加剂会造成电池阻抗较大，尤其是在低温下，电池阻抗增加非常明显，导致电池的低温性能下降。
专利CN101842349B公开了一种含有磺酸苯酯化合物的电解液，包括0.01-10％的磺酸苯酯添加剂。此电解液能够改善电池的低温循环性能，但是对电池常温、高温循环及高温存储性能没有改善。
专利CN104684890A公开了一种可以用作锂电池用电解质溶剂的特殊磺酸酯化合物，该化合物主要作用为改善锂盐的溶解性，降低电解液的粘度，但是并未提及对电池性能的改善。要通过电解液来同时改善电池的高低温性能是一个比较难的课题。因此，有必要开发一种能同时改善电池高温和低温性能的电 解液。
发明内容
基于此，本发明的目的是提供一种锂二次电池电解液。
具体的技术方案如下：
一种锂二次电池电解液，包括有机溶剂、导电锂盐、五氟苯磺酸甲酯和添加剂。
在其中一些实施例中，所述五氟苯磺酸甲酯占锂二次电池电解液总质量的0.1-5.0％。
在其中一些实施例中，所述添加剂选自二氟磷酸锂、硫酸乙烯酯、五氟乙氧基磷腈中的至少一种，占锂二次电池电解液总质量的0.1-15.0％。
在其中一些实施例中，所述导电锂盐为六氟磷酸锂或双氟磺酰亚胺锂中的至少一种；所述导电锂盐占锂二次电池电解液总质量的8.0-18.0％。
在其中一些实施例中，所述有机溶剂由环状溶剂和线性溶剂组成，所述环状溶剂与所述线型溶剂的质量比为(1～3):3。
在其中一些实施例中，所述有机溶剂的用量占锂二次电池电解液总质量的62.0-91.8％
在其中一些实施例中，所述环状溶剂选自碳酸乙烯酯、碳酸丙烯酯、γ-丁内酯和1,4丁基磺酸内酯的至少一种。
在其中一些实施例中，所述线型溶剂选自碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、乙酸乙酯、丙酸丙酯、1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚、2,2-二氟乙基乙酸酯中的至少一种。
本发明的另一目的是提供一种锂二次电池。
一种锂二次电池，包含上述锂二次电池电解液(还包含含有正极活性材料的正极片、含有负极活性材料的负极片以及隔膜)。
在上述锂二次电池中所述正极活性材料是指含锂金属化合物，所述的含锂 金属化合物为Li1+a(NixCoyM1-x-y)O2、Li(NipMnqCo2-p-q)O4、LiMh(PO4)m的至少一种，其中0≤a≤0.3，0≤x≤1，0≤y≤1，0＜x+y≤1，0≤p≤2，0≤q≤2，0＜p+q≤2，M为Fe、Ni、Co、Mn、Al或V，0＜h＜5，0＜m＜5；所述负极活性材料为锂金属、锂合金、碳材料、硅基材料和锡基材料中的至少一种。
上述锂二次电池电解液具有如下优点及有益效果：
上述电解液通过添加五氟苯磺酸甲酯与二氟磷酸锂、硫酸乙烯酯、五氟乙氧基磷腈组合使用能够改善电解液的常温循环性能，高温存储性能和低温放电性能。
具体实施方式
为了便于理解本发明，下面将对本发明进行更全面的描述。但是，本发明可以以许多不同的形式来实现，并不限于本发明所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本发明所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。
实施例1
本实施例一种锂二次电池电解液，由有机溶剂、导电锂盐、五氟苯磺酸甲酯和添加剂构成。所述有机溶剂占锂二次电池电解液总质量的77.0％，由环状溶剂(碳酸乙烯酯)和线性溶剂(碳酸甲乙酯)组成，碳酸乙烯酯和碳酸甲乙酯的质量比为1:1。所述导电锂盐为六氟磷酸锂，占锂二次电池电解液总质量的18.0％。五氟苯磺酸甲酯占电解液总质量的5.0％。将本实施例的电解液用于LiNi0.8Co0.1Mn0.1O2/石墨软包电池。
实施例2
本实施例一种锂二次电池电解液，由有机溶剂、导电锂盐、五氟苯磺酸甲 酯和添加剂构成。所述有机溶剂占锂二次电池电解液总质量的81.5％，由环状溶剂(碳酸乙烯酯)和线性溶剂(碳酸二甲酯)组成，碳酸乙烯酯和碳酸二甲酯的质量比为1:2。所述导电锂盐为六氟磷酸锂，占锂二次电池电解液总质量的15.0％。五氟苯磺酸甲酯占电解液总质量的0.5％，所述添加剂为二氟磷酸锂、硫酸乙烯酯，分别占电解液总质量的1.0％、2.0％。将本实施例的电解液用于LiNi0.8Co0.1Mn0.1O2/硅碳软包电池。
实施例3
本实施例一种锂二次电池电解液，由有机溶剂、导电锂盐、五氟苯磺酸甲酯和添加剂构成。所述有机溶剂占锂二次电池电解液总质量的85.0％，由环状溶剂(碳酸乙烯酯)和线性溶剂(碳酸二乙酯)组成，碳酸乙烯酯和碳酸二乙酯的质量比为1:3。所述导电锂盐为六氟磷酸锂，占锂二次电池电解液总质量的12.0％。五氟苯磺酸甲酯占电解液总质量的1.0％，所述添加剂为二氟磷酸锂、五氟乙氧基磷腈，分别占电解液总质量的1.0％、1.0％。将本实施例的电解液用于LiNi0.6Co0.2Mn0.2O2/石墨软包电池。
实施例4
本实施例一种锂二次电池电解液，由有机溶剂、导电锂盐、五氟苯磺酸甲酯和添加剂构成。所述有机溶剂占锂二次电池电解液总质量的84.5％，由环状溶剂(碳酸乙烯酯、碳酸丙烯酯)和线性溶剂(碳酸甲乙酯、丙酸丙酯)组成，碳酸乙烯酯、碳酸丙烯酯、碳酸甲乙酯、丙酸丙酯的质量比为1:0.5:1:1。所述导电锂盐为六氟磷酸锂，占锂二次电池电解液总质量的12.0％。五氟苯磺酸甲酯占电解液总质量的1.0％，所述添加剂为硫酸乙烯酯、五氟乙氧基磷腈，分别占电解液总质量的1.0％、1.5％。将本实施例的电解液用于LiNi0.6Co0.2Mn0.2O2/硅碳软包电池。
实施例5
本实施例一种锂二次电池电解液，由有机溶剂、导电锂盐、五氟苯磺酸甲酯和添加剂构成。所述有机溶剂占锂二次电池电解液总质量的89.0％，由环状溶 剂(碳酸乙烯酯)和线性溶剂(碳酸甲乙酯、1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚)组成，碳酸乙烯酯、碳酸丙烯酯、碳酸甲乙酯、1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚的质量比为1:2:0.5。所述导电锂盐为六氟磷酸锂，占锂二次电池电解液总质量的8.5％。五氟苯磺酸甲酯占电解液总质量的1.0％，所述添加剂为二氟磷酸锂，占电解液总质量的1.5％。将本实施例的电解液用于LiNi0.5Co0.2Mn0.3O2/石墨软包电池。
实施例6
本实施例一种锂二次电池电解液，由有机溶剂、导电锂盐、五氟苯磺酸甲酯和添加剂构成。所述有机溶剂占锂二次电池电解液总质量的83.5％，由环状溶剂(碳酸乙烯酯)和线性溶剂(碳酸甲乙酯)组成，碳酸乙烯酯、碳酸甲乙酯的质量比为1:1。所述导电锂盐为六氟磷酸锂，占锂二次电池电解液总质量的12.5％。五氟苯磺酸甲酯占电解液总质量的1.0％，所述添加剂为五氟乙氧基磷腈，占电解液总质量的3.0％。将本实施例的电解液用于LiNi0.5Co0.2Mn0.3O2/硅碳软包电池。
实施例7
本实施例一种锂二次电池电解液，由有机溶剂、导电锂盐、五氟苯磺酸甲酯和添加剂构成。所述有机溶剂占锂二次电池电解液总质量的70.0％，由环状溶剂(碳酸乙烯酯)和线性溶剂(碳酸甲乙酯)组成，碳酸乙烯酯、碳酸甲乙酯的质量比为1:1。所述导电锂盐为六氟磷酸锂，占锂二次电池电解液总质量的13.0％。五氟苯磺酸甲酯占电解液总质量的2.0％，所述添加剂为硫酸乙烯酯、五氟乙氧基磷腈，占电解液总质量的1.0％、14.0％。将本实施例的电解液用于LiCoO2/石墨软包电池。
实施例8
本实施例一种锂二次电池电解液，由有机溶剂、导电锂盐、五氟苯磺酸甲酯和添加剂构成。所述有机溶剂占锂二次电池电解液总质量的83.0％，由环状溶剂(碳酸乙烯酯)和线性溶剂(碳酸甲乙酯)组成，碳酸乙烯酯、碳酸甲乙酯 的质量比为1:1。所述导电锂盐为六氟磷酸锂，占锂二次电池电解液总质量的13.0％。五氟苯磺酸甲酯占电解液总质量的3.0％，所述添加剂为硫酸乙烯酯，占电解液总质量的1.0％。将本实施例的电解液用于LiNi0.6Co0.2Mn0.2O2/硅碳软包电池。
实施例9
本实施例一种锂二次电池电解液，由有机溶剂、导电锂盐、五氟苯磺酸甲酯和添加剂构成。所述有机溶剂占锂二次电池电解液总质量的80.5％，由环状溶剂(碳酸乙烯酯)和线性溶剂(碳酸甲乙酯)组成，碳酸乙烯酯、碳酸甲乙酯的质量比为1:1。所述导电锂盐为六氟磷酸锂、双氟磺酰亚胺锂，占锂二次电池电解液总质量的10.0％、4.5％。五氟苯磺酸甲酯占电解液总质量的4.5％，所述添加剂为硫酸乙烯酯，占电解液总质量的0.5％。将本实施例的电解液用于LiNi0.6Co0.2Mn0.2O2/石墨软包电池。
实施例10
本实施例一种锂二次电池电解液，由有机溶剂、导电锂盐、五氟苯磺酸甲酯和添加剂构成。所述有机溶剂占锂二次电池电解液总质量的83.5％，由环状溶剂(碳酸乙烯酯)和线性溶剂(碳酸甲乙酯)组成，碳酸乙烯酯、碳酸甲乙酯的质量比为1:1。所述导电锂盐为六氟磷酸锂、双氟磺酰亚胺锂，占锂二次电池电解液总质量的8.0％、3.0％。五氟苯磺酸甲酯占电解液总质量的4.5％，所述添加剂为五氟乙氧基磷腈，占电解液总质量的1.0％。将本实施例的电解液用于LiNi0.6Co0.2Mn0.2O2/石墨软包电池。
对比例1
本对比例的电解液的制备方法与实施例1相同，所不同的是，不含五氟苯磺酸甲酯，将此电解液按照与实施例1相同的方法应用于电池中测试其性能。
对比例2
本对比例的电解液的制备方法与实施例2相同，所不同的是，不含五氟苯磺酸甲酯，将此电解液按照与实施例2相同的方法应用于电池中测试其性能。
对比例3
本对比例的电解液的制备方法与实施例3相同，所不同的是，不含五氟苯磺酸甲酯，将此电解液按照与实施例3相同的方法应用于电池中测试其性能。
对比例4
本对比例的电解液的制备方法与实施例4相同，所不同的是，不含五氟苯磺酸甲酯，将此电解液按照与实施例4相同的方法应用于电池中测试其性能。
对比例5
本对比例的电解液的制备方法与实施例5相同，所不同的是，不含五氟苯磺酸甲酯，将此电解液按照与实施例5相同的方法应用于电池中测试其性能。
对比例6
本对比例的电解液的制备方法与实施例6相同，所不同的是，不含五氟苯磺酸甲酯，将此电解液按照与实施例6相同的方法应用于电池中测试其性能。
对比例7
本对比例的电解液的制备方法与实施例7相同，所不同的是，不含五氟苯磺酸甲酯，将此电解液按照与实施例7相同的方法应用于电池中测试其性能。
对比例8
本对比例的电解液的制备方法与实施例8相同，所不同的是，不含五氟苯磺酸甲酯，将此电解液按照与实施例8相同的方法应用于电池中测试其性能。
对比例9
本对比例的电解液的制备方法与实施例9相同，所不同的是，不含五氟苯磺酸甲酯，将此电解液按照与实施例9相同的方法应用于电池中测试其性能。
对比例10
本对比例的电解液的制备方法与实施例10相同，所不同的是，不含五氟苯磺酸甲酯，将此电解液按照与实施例10相同的方法应用于电池中测试其性能。
实施例和对比例的应用实验：
将上述实施例1～10和对比例1～10制备的锂二次电池进行常温循环、高 温存储、低温放电测试。
充放电测试条件：为了测量使用本发明制得的电解液的电池充放电性能，进行以下操作：按照常规方法制备正负极片，使用各实施例制备得到电解液在手套箱中注液使用上述极片制备053048型软包电池，用新威(BS-9300R型)电池测试系统对制备的053048型电池进行充放电测试，同时与对应的对比例电解液制备的电池进行比较。电池置于常温以3.0～4.2V 1C倍率下充放电循环和置于60℃满电存储15天后放电、-20℃ 0.5C放电。记录电池常温300周循环的容量保持率、60℃满电存储15天后放电容量保持率、-20℃ 0.5C放电容量保持率。结果如表1所示。
表1实施例和对比例的充放电循环、高温存储、低温放电后测试结果：
Figure PCTCN2017113956-appb-000001
Figure PCTCN2017113956-appb-000002
由表1可以看出：实施例1～10相对于对比例1～10，向电解液中添加不同比例的五氟苯磺酸甲酯，都能够明显改善电池的循环性能、高温存储性能、低温放电性能。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (9)

  1. 一种锂二次电池电解液，其特征在于，包括有机溶剂、导电锂盐、五氟苯磺酸甲酯和添加剂。
  2. 根据权利要求1所述的锂二次电池电解液，其特征在于，所述五氟苯磺酸甲酯占锂二次电池电解液总质量的0.1-5.0％。
  3. 根据权利要求1所述的锂二次电池电解液，其特征在于，所述添加剂选自二氟磷酸锂、硫酸乙烯酯、五氟乙氧基磷腈中的至少一种。
  4. 根据权利要求1或3所述的锂二次电池电解液，其特征在于，所述添加剂占锂二次电池电解液总质量的0.1-15.0％。
  5. 根据权利要求1所述的锂二次电池电解液，其特征在于，所述导电锂盐为六氟磷酸锂或双氟磺酰亚胺锂中的至少一种，占锂二次电池电解液总质量的8.0-18.0％。
  6. 根据权利要求1所述的锂二次电池电解液，其特征在于，所述有机溶剂由环状溶剂和线性溶剂组成。
  7. 根据权利要求6所述的锂二次电池电解液，其特征在于，所述环状溶剂选自碳酸乙烯酯、碳酸丙烯酯、γ-丁内酯和1,4丁基磺酸内酯中的至少一种。
  8. 根据权利要求6所述的锂二次电池电解液，其特征在于，所述线型溶剂选自碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、乙酸乙酯、碳酸甲丙酯、丙酸丙酯、1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚、2,2-二氟乙基乙酸酯中的至少一种。
  9. 一种锂二次电池，其特征在于，包含权利要求1-8任一项所述的锂二次电池电解液。
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