WO2017113820A1 - 高电压宽温锂离子电池电解液及其制备方法及应用 - Google Patents

高电压宽温锂离子电池电解液及其制备方法及应用 Download PDF

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WO2017113820A1
WO2017113820A1 PCT/CN2016/096166 CN2016096166W WO2017113820A1 WO 2017113820 A1 WO2017113820 A1 WO 2017113820A1 CN 2016096166 W CN2016096166 W CN 2016096166W WO 2017113820 A1 WO2017113820 A1 WO 2017113820A1
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lithium ion
ion battery
solvent
battery electrolyte
high voltage
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PCT/CN2016/096166
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English (en)
French (fr)
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刘鹏
田丽霞
梅银平
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石家庄圣泰化工有限公司
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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
    • H01M10/0569—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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0034—Fluorinated solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention belongs to the technical field of lithium ion battery electrolyte, and particularly relates to a high voltage wide temperature lithium ion battery electrolyte, a preparation method thereof and an application thereof.
  • the electrolyte of the invention has good stability and simple preparation method, and can be effectively applied to the battery to effectively improve the cycle life and high temperature performance of the high voltage wide temperature lithium ion battery.
  • Lithium-ion batteries have become the fastest growing and most valued new high-energy batteries due to their high specific energy, small size, light weight, no memory effect and long cycle life.
  • portable electronic devices have been rapidly developed, but the increase in hardware configuration, the increase in screen size, and the diversification of functions have placed increasing demands on the energy density of lithium-ion batteries.
  • Conventional lithium-ion batteries have been unable to meet the requirements. the needs of the people.
  • lithium-ion batteries In order to improve the energy density of lithium-ion batteries, researchers usually develop high-capacity, high-voltage positive electrode materials to solve this problem, such as increasing the working voltage of lithium-cobalt composite oxides and lithium-manganese composite oxides, and developing high operating voltages. Lithium nickel manganese composite oxide and the like. However, these positive electrode materials undergo a structural change in a solvent at a high voltage, the transition metal is easily dissolved, and is deposited on the negative electrode. In addition, a commonly used electrolyte usually decomposes at a voltage higher than 4 V to produce gas. Will result in a decrease in battery performance.
  • the invention provides a high voltage wide temperature lithium ion battery electrolyte and a preparation method thereof and application thereof for improving the energy density of a lithium ion battery and solving the damage of the battery cycle performance caused by the electrolyte solution for increasing the voltage in the prior art. .
  • a high voltage wide temperature lithium ion battery electrolyte comprising an organic solvent, a lithium salt and an additive, wherein the organic solvent is composed of a cyclic carbonate solvent, a fluorinated solvent and a carbonate solvent, and the additive is 3-fluoro -1,3 propenyl sultone, the content of the additive in the lithium ion battery electrolyte is from 0.5% to 10%.
  • the concentration of the lithium salt in the organic solvent is 1-1.5 mol/L, and the mass percentage of the fluorinated solvent in the electrolyte is 2-50%.
  • the cyclic carbonate solvent is selected from one or more of ethylene carbonate, propylene carbonate, ⁇ -butyrolactone, and ⁇ -valerolactone.
  • the fluorinated solvent is one or more selected from the group consisting of methyl trifluoroacetate, ethyl trifluoroacetate and butyl trifluoroacetate.
  • the carbonate solvent is selected from one or more of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propionate, ethyl propionate, and propyl propionate.
  • the lithium salt is one or more selected from the group consisting of LiPF 6 , LiBF 4 , LiSO 3 CF 3 , LiClO 4 , LiN(CF 3 SO 2 ) 2 , and LiC(CF 3 SO 2 ) 3 .
  • a method for preparing a high voltage wide temperature lithium ion battery electrolyte which comprises mixing a cyclic carbonate solvent, a fluorinated solvent and a carbonate solvent, removing impurities, removing water, and dissolving the lithium salt in the above mixture at room temperature. After the solvent is stirred uniformly, 3-fluoro-1,3 propene sultone is added, and the solution is dissolved and filtered to obtain the high-voltage wide-temperature lithium ion battery electrolyte.
  • the above high voltage wide temperature lithium ion battery electrolyte is used in preparing a high voltage wide temperature lithium ion battery.
  • the addition of a fluorinated solvent to the electrolyte solvent can reduce the decomposition of the electrolyte at a high voltage and improve the oxidation resistance of the electrolyte.
  • the fluorinated solvent has good wettability and improves the wetting property of the electrolyte.
  • 3-Fluoro-1,3 propane sultone can effectively protect the positive electrode, reduce the dissolution of the transition metal on the positive electrode material, and form the SEI film on the negative electrode to inhibit the deposition and reduction of the transition metal on the negative electrode. Effective protection of the negative electrode. It is beneficial to improve the cycle stability performance and high temperature cycle performance of the battery at high voltage.
  • the preparation method of the high voltage wide temperature lithium ion battery electrolyte of the invention is simple, and can simultaneously improve the interface property between the positive electrode and the negative electrode of the battery and the electrolyte, the stability of the electrolyte is good, and the cycle life and high temperature performance of the high voltage lithium ion battery can be effectively improved. .
  • the high voltage wide temperature lithium ion battery prepared by the high voltage wide temperature lithium ion battery electrolyte of the invention has long cycle life, low air expansion rate and good high temperature performance, and the working voltage of the battery can be higher than 4.5V.
  • 3-fluoro-1,3 propane sultone can also inhibit the oxidation or reductive decomposition of the electrolyte on the surface of the electrode material, reduce the damage to the electrode, and improve the compatibility of the electrolyte with the electrode.
  • Figure 1 is a graph showing the cycle performance of the present invention in comparison with a base electrolyte.
  • a high voltage wide temperature lithium ion battery electrolyte comprising an organic solvent, LiPF 6 and 3-fluoro1,3-propene sultone, wherein the organic solvent is composed of ethylene carbonate and carbonic acid in a weight ratio of 1:2:0.2.
  • Ethyl ethyl ester, ethyl trifluoroacetate composition the amount of 3-fluoro1,3-propene sultone added in the electrolyte is 2 wt.%, and the concentration of the lithium salt in the organic solvent is 1 mol/L.
  • the ethyl trifluoroacetate was 20% by mass in the electrolyte.
  • the preparation method of the above high voltage wide temperature lithium ion battery electrolyte is:
  • 3-fluoro1,3-propene sultone is prepared by dissolving 1 mol of 1,3-propene sultone in 600 mL of dichloromethane using 1,3-propene sultone as a raw material. Adding 1.05 mol of NBS in portions at 50 ° C for 10 h to obtain the intermediate 3-bromo-1,3-propene sultone, and then placing the obtained intermediate with sodium fluoride in dichloromethane. The exchange reaction was carried out in the presence of cyclodextrin to obtain the product 3-fluoro-1,3-propene sultone.
  • 3-fluoro-1,3 propylene sultone can increase the battery voltage due to the presence of F element, and can be widely used in the high voltage field of lithium ion batteries.
  • 3-Fluoro-1,3-propene sultone can also improve the high temperature cycle characteristics of current ternary battery materials and improve the cycle life of batteries.
  • the high voltage wide temperature lithium ion battery electrolyte of the present embodiment is used for a lithium cobaltate/graphite soft pack battery, and the cycle performance of the lithium cobaltate/graphite flexible packaging battery under the normal temperature environment of 3.0 to 4.95 V, 1 C rate charge and discharge is tested.
  • the capacity retention rate is above 94%.
  • the capacity retention rate is above 91%.
  • the capacity retention rate is about 90%.
  • the capacity retention rate can still be reached. More than 85%.
  • a high voltage wide temperature lithium ion battery electrolyte comprising an organic solvent, LiN(CF 3 SO 2 ) 2 and 3-fluoro1,3-propene sultone, wherein the organic solvent is 1:2:0.2 by weight ratio
  • the composition of propylene carbonate, methyl propionate and methyl trifluoroacetate, the amount of 3-fluoro1,3-propene sultone added in the electrolyte is 4 wt.%, and the lithium salt is in an organic solvent.
  • the concentration was 1.5 mol/L, and the mass percentage of ethyl trifluoroacetate in the electrolytic solution was 30%.
  • the preparation method of the above high voltage wide temperature lithium ion battery electrolyte is:
  • the high voltage wide temperature lithium ion battery electrolyte of the present embodiment is used for a lithium cobaltate/graphite soft pack battery, and the cycle performance of the lithium cobaltate/graphite flexible packaging battery under the normal temperature environment of 3.0 to 4.95 V, 1 C rate charge and discharge is tested.
  • the capacity retention rate is 93%.
  • the capacity retention rate is 90%.
  • the capacity retention rate is 89%.
  • the capacity retention rate can still reach 85% or more. .
  • a high voltage wide temperature lithium ion battery electrolyte comprising an organic solvent, LiClO 4 and 3-fluoro1,3-propene sultone, wherein the organic solvent is ⁇ -butyrolactone in a weight ratio of 1:2:0.2
  • the composition of ethyl propionate and butyl trifluoroacetate, the amount of 3-fluoro1,3-propene sultone added in the electrolyte is 6 wt.%, and the concentration of lithium salt in the organic solvent is 1.2 mol. /L, ethyl trifluoroacetate in a mass percentage of 40% in the electrolyte.
  • the preparation method of the above high voltage wide temperature lithium ion battery electrolyte is:
  • the high voltage wide temperature lithium ion battery electrolyte of the embodiment is used for lithium cobalt oxide/graphite soft package Pool, test lithium cobalt oxide / graphite flexible packaging battery in the normal temperature environment 3.0 ⁇ 4.95V, 1C rate charge and discharge cycle performance.
  • the capacity retention rate is 94%.
  • the capacity retention rate is 91%.
  • the capacity retention rate is 90%.
  • the capacity retention rate can still reach 85% or more. .
  • a high voltage wide temperature lithium ion battery electrolyte comprising an organic solvent, LiSO 3 CF 3 and 3-fluoro1,3-propene sultone, wherein the organic solvent is ⁇ -penta by weight ratio of 1:2:0.2
  • the composition of lactone, propyl propionate and methyl trifluoroacetate, the amount of 3-fluoro1,3-propene sultone added in the electrolyte is 2.5 wt.%, and the concentration of the lithium salt in the organic solvent It was 1.2 mol/L, and the ethyl trifluoroacetate was 35% by mass in the electrolytic solution.
  • the preparation method of the above high voltage wide temperature lithium ion battery electrolyte is:
  • the high voltage wide temperature lithium ion battery electrolyte of the present embodiment is used for a lithium cobaltate/graphite soft pack battery, and the cycle performance of the lithium cobaltate/graphite flexible packaging battery under the normal temperature environment of 3.0 to 4.95 V, 1 C rate charge and discharge is tested.
  • the capacity retention rate is 94%.
  • the capacity retention rate is 91%.
  • the capacity retention rate is 90%.
  • the capacity retention rate can still reach 85% or more. .
  • a high-voltage lithium ion battery electrolyte mainly comprises the following raw materials: an organic solvent, a conductive lithium salt and a functional additive;
  • the conductive lithium salt is LiPF 6 having a concentration of 1.2 mol/L in an organic solvent; and the functional additive is 2 wt.% of propylene-1,3-sultone (PES).
  • the preparation method of the above high voltage lithium ion battery electrolyte is:
  • the high voltage lithium ion battery electrolyte of the present embodiment was used for a lithium nickel manganese oxide (LiNi 0.5 Mn 1.5 O 4 ) battery.
  • the cycle performance of LiNi 0.5 Mn 1.5 O 4 battery under normal temperature environment of 3.5 to 4.95 V, 1 C rate charge and discharge was tested. After 200 weeks of cycle, the capacity retention rate was 92%. After 300 weeks of cycle, the capacity retention rate was 90%. After 400 cycles, the capacity retention rate was 88%. After 500 cycles, the capacity retention rate reached 80%.
  • the conductive lithium salt LiPF 6 has a concentration of 1.0 mol/L in an organic solvent, and the usual additive is 1.0 wt.% of vinylene carbonate and 1.0 wt.% of propane sultone.
  • the additive was 1.0 wt.% of tetrafluoroterephthalonitrile and 2.0 wt.% of 3-fluorobenzonitrile.
  • the preparation method of the above electrolyte solution is:
  • the high-voltage lithium ion battery electrolyte of the invention is applied to a lithium cobaltate/graphite flexible packaging battery, and the cycle performance of the lithium cobaltate/graphite flexible packaging battery in a normal temperature environment of 3.0-4.5 V, 1 C rate charge and discharge is tested.
  • the capacity retention rate was 90%.
  • the capacity retention rate was 85%.
  • the capacity retention rate was 80%.
  • the capacity retention rate reached 70%.

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Abstract

一种高电压宽温锂离子电池电解液，属于锂离子电池电解液的技术领域，包括有机溶剂、锂盐和添加剂，所述的有机溶剂由环状碳酸酯溶剂、氟代溶剂和碳酸酯溶剂组成，所述的添加剂为3-氟-1,3丙烯磺酸内酯，所述锂离子电池电解液中添加剂的含量为0.5％-10％。本发明还公开了该电解液的制备方法和应用。本发明的电解液稳定性良好，制备方法简单，应用到电池中能有效提高高电压宽温锂离子电池的循环寿命和高温性能。

Description

高电压宽温锂离子电池电解液及其制备方法及应用 技术领域
本发明属于锂离子电池电解液的技术领域，具体涉及高电压宽温锂离子电池电解液及其制备方法及应用。本发明的电解液稳定性良好，制备方法简单，应用到电池中能有效提高高电压宽温锂离子电池的循环寿命和高温性能。
背景技术
锂离子电池因其比能量高、体积小、质量轻、无记忆效应、循环寿命长等优点而成为目前发展最快亦最受重视的新型高能蓄电池。近年来，便携式电子设备得到快速发展，但硬件配置的攀升，屏幕尺寸的增大，功能的多样化等方面对锂离子电池的能量密度提出越来越高的要求，常规锂离子电池已经不能满足人们的需求。
目前为了提高锂离子电池的能量密度，研究者通常采用开发高容量、高工作电压的正极材料来解决此问题，如提高锂钴复合氧化物、锂锰复合氧化物的工作电压，开发高工作电压的锂镍锰复合氧化物等。然而，这些正极材料在高电压下溶剂发生结构改变，过渡金属容易发生溶解，并且会在负极上沉积，另外，常用的电解液，通常会在高于4V的电压下发生分解，产气，从而会导致电池性能的降低。为了解决以上问题，研究者通常会对正极材料进行表面保护包覆或者掺杂来提高高电压下的循环性能，但是这些方法往往会伴随着电池可容量的损失，而且制作工艺繁琐，制造成本增加。通过开发新型高电压电解液取代目前常用的电解液体系是实现高电压 锂离子电池商业化的改善途径之一。目前由于常用的提高电压的电解液，往往是增大FEC(氟代碳酸乙烯酯)的用量来提高耐受电压，然而当电压提高到4.5V以上时，继续增加FEC的用量，反而电池循环性能下降的更快，因而开发高电压用的电解液添加剂已经刻不容缓。
发明内容
本发明为了提高锂离子电池的能量密度，以及解决现有技术中为提高电压的电解液而造成电池循环性能的损害，提供了一种高电压宽温锂离子电池电解液及其制备方法及应用。
本发明为实现其目的采用的技术方案是：
一种高电压宽温锂离子电池电解液，包括有机溶剂、锂盐和添加剂，所述的有机溶剂由环状碳酸酯溶剂、氟代溶剂和碳酸酯溶剂组成，所述的添加剂为3-氟-1,3丙烯磺酸内酯，所述锂离子电池电解液中添加剂的含量为0.5％-10％。
所述锂盐在有机溶剂中的浓度为1-1.5mol/L，氟代溶剂在电解液中质量百分比为2-50％。
所述的环状碳酸酯溶剂选自碳酸乙烯酯、碳酸丙烯酯、γ-丁内酯、γ-戊内酯中一种或多种。
所述的氟代溶剂选址三氟乙酸甲酯、三氟乙酸乙酯、三氟乙酸丁酯中的一种或多种。
所述的碳酸酯溶剂选自碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯中的一种或多种。
所述的锂盐选自LiPF6、LiBF4、LiSO3CF3、LiClO4、LiN(CF3SO2)2、 LiC(CF3SO2)3中的一种或多种。
一种制备述高电压宽温锂离子电池电解液的方法，将环状碳酸酯溶剂、氟代溶剂、碳酸酯溶剂混合均匀后，除杂质，除水，于室温下将锂盐溶解在上述混合后的溶剂中，搅拌均匀，然后加入3-氟-1,3丙烯磺酸内酯，溶清后过滤，即得所述高电压宽温锂离子电池电解液。
将环状碳酸酯溶剂、氟代溶剂、碳酸酯溶剂混合均匀后，用
Figure PCTCN2016096166-appb-000001
分子筛、氢化锂除杂质，除水。
上述高电压宽温锂离子电池电解液在制备高电压宽温锂离子电池中的应用。
添加剂3-氟-1,3丙烯磺酸内酯的化学结构式如下：
Figure PCTCN2016096166-appb-000002
本发明的有益效果是：
在电解液溶剂中加入了氟代溶剂，可以减少电解液在高电压下的分解，提高了电解液的抗氧化性能，同时，氟代溶剂具有良好的浸润性，改善电解液的浸润性能，加入了3-氟-1,3丙烯磺酸内酯，可以有效的保护正极，减少过渡金属在正极材料上的溶出，同时能够在负极形成SEI膜，抑制过渡金属在负极上的沉积和还原，从而有效的保护负极。有利于提高电池在高电压下的循环稳定性能和高温循环性能。而且可有效阻止锂电池过充造成的起火、爆炸等安全问题的发生，增加了电池的安全性；充放效率高、循环性能好，能满足500次大于85％的充放要求，尤其可改善锂电池的高温循 环性能；可增加电池的储存性能，不影响锂电池的其他性能。
本发明高电压宽温锂离子电池电解液制备方法简单，能同时改善电池正极及负极与电解液的界面性质，电解液的稳定性良好，能有效提高高电压锂离子电池的循环寿命和高温性能。
本发明高电压宽温锂离子电池电解液制得的高电压宽温锂离子电池循环寿命长、气胀率低、高温性能良好，电池工作电压可高于4.5V。
其中，3-氟-1,3丙烯磺酸内酯还可以抑制电解液在电极材料表面的氧化或者还原分解，减小对电极的破坏，提高电解液与电极的兼容性。
附图说明
图1是本发明与基础电解液对比的循环性能图。
图中，▲表示基础电解液:EC：DMC＝1：2，1M LiPF6，FEC1％；■表示本发明电解液。
具体实施方式
下面结合具体实施例对本发明作进一步的说明。
实施例1
一种高电压宽温锂离子电池电解液，包括有机溶剂、LiPF6和3-氟1,3-丙烯磺酸内酯，其中有机溶剂由重量比为1:2:0.2的碳酸乙烯酯、碳酸甲乙酯、三氟乙酸乙酯组成，本电解液中加入的3-氟1,3-丙烯磺酸内酯的添加量为2wt.％，锂盐在有机溶剂中的浓度为1mol/L，三氟乙酸乙酯在电解液中质量百分比为20％。
上述高电压宽温锂离子电池电解液的制备方法是：
1)将有机溶剂混合均匀后，用
Figure PCTCN2016096166-appb-000003
分子筛、氢化锂除杂质，除水；
2)于室温下将锂盐溶解在上述混合后的溶剂中，搅拌均匀；
3)然后加入3-氟-1,3丙烯磺酸内酯，溶清后过滤，即得所述高电压宽温锂离子电池电解液。
上述添加剂3-氟1,3-丙烯磺酸内酯的制备方法是：以1,3-丙烯磺酸内酯为原料，将1mol的1,3-丙烯磺酸内酯用600mL二氯甲烷溶解，在50℃下分批加入1.05mol的NBS，反应10h，得到中间体3-溴-1,3-丙烯磺酸内酯，然后将所得中间体与氟化钠置于二氯甲烷中，在环糊精存在下进行交换反应，得到产品3-氟-1,3-丙烯磺酸内酯。3-氟-1,3丙烯磺酸内酯相较于1,3-丙烯磺酸内酯，由于F元素的存在，更加可以提高电池电压，可以广泛应用于锂离子电池高电压领域，同时，3-氟-1,3-丙烯磺酸内酯还可以改善目前三元电池材料的高温循环特性，可以改善电池的循环寿命。
将本实施例的高电压宽温锂离子电池电解液用于钴酸锂/石墨软包电池，测试钴酸锂/石墨软包装电池在常温环境下3.0～4.95V，1C倍率充放电的循环性能。循环200周后，容量保持率在94％以上，循环300周后，容量保持率在91％以上，循环400周后，容量保持率在90％左右，循环500周后，容量保持率依然可以达到85％以上。
实施例2
一种高电压宽温锂离子电池电解液，包括有机溶剂、LiN(CF3SO2)2和3-氟1,3-丙烯磺酸内酯，其中有机溶剂由重量比为1:2:0.2的碳酸丙烯酯、丙酸甲酯、三氟乙酸甲酯组成，本电解液中加入的3-氟1,3-丙烯磺酸内酯的添加量为4wt.％，锂盐在有机溶剂中的浓度为1.5mol/L，三氟乙酸乙酯在电解液中质量百分比为30％。
上述高电压宽温锂离子电池电解液的制备方法是：
1)将有机溶剂混合均匀后，用
Figure PCTCN2016096166-appb-000004
分子筛、氢化锂除杂质，除水；
2)于室温下将锂盐溶解在上述混合后的溶剂中，搅拌均匀；
3)然后加入3-氟-1,3丙烯磺酸内酯，溶清后过滤，即得所述高电压宽温锂离子电池电解液。
将本实施例的高电压宽温锂离子电池电解液用于钴酸锂/石墨软包电池，测试钴酸锂/石墨软包装电池在常温环境下3.0～4.95V，1C倍率充放电的循环性能。循环200周后，容量保持率在93％，循环300周后，容量保持率在90％，循环400周后，容量保持率在89％，循环500周后，容量保持率依然可以达到85％以上。
实施例3
一种高电压宽温锂离子电池电解液，包括有机溶剂、LiClO4和3-氟1,3-丙烯磺酸内酯，其中有机溶剂由重量比为1:2:0.2的γ-丁内酯、丙酸乙酯、三氟乙酸丁酯组成，本电解液中加入的3-氟1,3-丙烯磺酸内酯的添加量为6wt.％，锂盐在有机溶剂中的浓度为1.2mol/L，三氟乙酸乙酯在电解液中质量百分比为40％。
上述高电压宽温锂离子电池电解液的制备方法是：
1)将有机溶剂混合均匀后，用
Figure PCTCN2016096166-appb-000005
分子筛、氢化锂除杂质，除水；
2)于室温下将锂盐溶解在上述混合后的溶剂中，搅拌均匀；
3)然后加入3-氟-1,3丙烯磺酸内酯，溶清后过滤，即得所述高电压宽温锂离子电池电解液。
将本实施例的高电压宽温锂离子电池电解液用于钴酸锂/石墨软包电 池，测试钴酸锂/石墨软包装电池在常温环境下3.0～4.95V，1C倍率充放电的循环性能。循环200周后，容量保持率在94％，循环300周后，容量保持率在91％，循环400周后，容量保持率在90％，循环500周后，容量保持率依然可以达到85％以上。
实施例4
一种高电压宽温锂离子电池电解液，包括有机溶剂、LiSO3CF3和3-氟1,3-丙烯磺酸内酯，其中有机溶剂由重量比为1:2:0.2的γ-戊内酯、丙酸丙酯、三氟乙酸甲酯组成，本电解液中加入的3-氟1,3-丙烯磺酸内酯的添加量为2.5wt.％，锂盐在有机溶剂中的浓度为1.2mol/L，三氟乙酸乙酯在电解液中质量百分比为35％。
上述高电压宽温锂离子电池电解液的制备方法是：
1)将有机溶剂混合均匀后，用
Figure PCTCN2016096166-appb-000006
分子筛、氢化锂除杂质，除水；
2)于室温下将锂盐溶解在上述混合后的溶剂中，搅拌均匀；
3)然后加入3-氟-1,3丙烯磺酸内酯，溶清后过滤，即得所述高电压宽温锂离子电池电解液。
将本实施例的高电压宽温锂离子电池电解液用于钴酸锂/石墨软包电池，测试钴酸锂/石墨软包装电池在常温环境下3.0～4.95V，1C倍率充放电的循环性能。循环200周后，容量保持率在94％，循环300周后，容量保持率在91％，循环400周后，容量保持率在90％，循环500周后，容量保持率依然可以达到85％以上。
对比实施例1
一种高电压锂离子电池电解液，主要包含如下原料：有机溶剂、导电 锂盐和功能添加剂；所述有机溶剂由碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、氟代碳酸乙烯酯(FEC)和氟代醚(CF2HCF2CH2-O-CF2CF2H)组成，EC和EMC的重量比为EC：EMC＝1:2，FEC用量为10wt.％，氟代醚CF2HCF2CH2-O-CF2CF2H用量为5wt.％。所述导电锂盐为LiPF6，其在有机溶剂中的浓度为1.2mol/L；所述功能添加剂为用量2wt.％的丙烯基-1,3-磺酸内酯(PES)。
上述高电压锂离子电池电解液的制备方法是：
(1)将有机溶剂按比例混合后用
Figure PCTCN2016096166-appb-000007
分子筛、氢化钙、氢化锂纯化除杂、除水；
(2)在室温条件下，将导电锂盐溶解在上述有机溶剂中，并搅拌均匀；
(3)加入功能添加剂PES，即得所述高电压锂离子电池电解液。
将本实施例的高电压锂离子电池电解液用于镍锰酸锂(LiNi0.5Mn1.5O4)电池。测试LiNi0.5Mn1.5O4电池在常温环境下3.5～4.95V，1C倍率充放电的循环性能。循环200周后，容量保持率在92％，循环300周后，容量保持率在90％，循环400周后，容量保持率在88％，循环500周后，容量保持率达80％。
对比实施例2
一种高电压锂离子电池电解液，主要包含有机溶剂、导电锂盐和添加剂，所述有机溶剂由环状碳酸酯溶剂(碳酸乙烯酯EC)和线型碳酸酯溶剂(碳酸甲乙酯EMC和碳酸二乙酯DEC)组成，EC及线型碳酸酯的重量比为EC：EMC：DEC＝1:1：1。所述导电锂盐LiPF6在有机溶剂中的浓度为1.0mol/L，所述常用添加剂为1.0wt.％用量的碳酸亚乙烯酯和用量为1.0wt.％的丙磺酸内酯，所述添加剂为四氟对苯二甲腈用量1.0wt.％，3-氟 苯甲腈用量为2.0wt.％。
上述电解液的配制方法是：
(1)将有机溶剂按比例混合后用
Figure PCTCN2016096166-appb-000008
分子筛、氢化钙、氢化锂纯化除杂、除水；
(2)在室温条件下，将导电锂盐溶解在上述有机溶剂中，并搅拌均匀；
(3)加入常用添加剂碳酸亚乙烯酯和丙磺酸内酯，并搅拌均匀。
(4)加入添加剂四氟对苯二甲腈和3-氟苯甲腈，即得本实施例所述高电压锂离子电池电解液。
将本发明的高电压锂离子电池电解液用于钴酸锂/石墨软包装电池，测试钴酸锂/石墨软包装电池在常温环境下3.0-4.5V，1C倍率充放电的循环性能。循环200周后，容量保持率在90％，循环300周后，容量保持率在85％，循环400周后，容量保持率在80％，循环500周后，容量保持率达70％。

Claims (9)

  1. 一种高电压宽温锂离子电池电解液，包括有机溶剂、锂盐和添加剂，所述的有机溶剂由环状碳酸酯溶剂、氟代溶剂和碳酸酯溶剂组成，其特征在于：所述的添加剂为3-氟-1,3丙烯磺酸内酯，所述锂离子电池电解液中添加剂的含量为0.5％-10％。
  2. 根据权利要求1所述的一种高电压宽温锂离子电池电解液，其特征在于：所述锂盐在有机溶剂中的浓度为1-1.5mol/L，氟代溶剂在电解液中质量百分比为2-50％。
  3. 根据权利要求1所述的一种高电压宽温锂离子电池电解液，其特征在于：所述的环状碳酸酯溶剂选自碳酸乙烯酯、碳酸丙烯酯、γ-丁内酯、γ-戊内酯中一种或多种。
  4. 根据权利要求1所述的一种高电压宽温锂离子电池电解液，其特征在于：所述的氟代溶剂选自三氟乙酸甲酯、三氟乙酸乙酯、三氟乙酸丁酯中的一种或多种。
  5. 根据权利要求1所述的一种高电压宽温锂离子电池电解液，其特征在于：所述的碳酸酯溶剂选自碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯中的一种或多种。
  6. 根据权利要求1所述的一种高电压宽温锂离子电池电解液，其特征在于：所述的锂盐选自LiPF6、LiBF4、LiSO3CF3、LiClO4、LiN(CF3SO2)2、LiC(CF3SO2)3中的一种或多种。
  7. 一种制备如权利要求1所述高电压宽温锂离子电池电解液的方法，其特征在于：将环状碳酸酯溶剂、氟代溶剂、碳酸酯溶剂混合均匀后，除杂质，除水，于室温下将锂盐溶解在上述混合后的溶剂中，搅拌均匀，然 后加入3-氟-1,3丙烯磺酸内酯，溶清后过滤，即得所述高电压宽温锂离子电池电解液。
  8. 根据权利要求7所述的一种制备高电压宽温锂离子电池电解液的方法，其特征在于，将环状碳酸酯溶剂、氟代溶剂、碳酸酯溶剂混合均匀后，用
    Figure PCTCN2016096166-appb-100001
    分子筛、氢化锂除杂质，除水。
  9. 根据权利要求1-6任意一项所述高电压宽温锂离子电池电解液在制备高电压宽温锂离子电池中的应用。
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