WO2017113819A1 - 高电压锂离子电池电解液及其制备方法及应用 - Google Patents
高电压锂离子电池电解液及其制备方法及应用 Download PDFInfo
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- WO2017113819A1 WO2017113819A1 PCT/CN2016/096165 CN2016096165W WO2017113819A1 WO 2017113819 A1 WO2017113819 A1 WO 2017113819A1 CN 2016096165 W CN2016096165 W CN 2016096165W WO 2017113819 A1 WO2017113819 A1 WO 2017113819A1
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- ion battery
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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
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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
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- 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 ion battery electrolytes, and particularly relates to a high voltage 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 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 lithium ion battery electrolyte, a preparation method thereof and an application thereof, in order to improve the energy density of the lithium ion battery and to solve the damage of the battery cycle performance caused by the electrolyte solution for increasing the voltage in the prior art.
- a high voltage lithium ion battery electrolyte comprising an organic solvent, a lithium salt and an additive, the organic solvent being composed of a cyclic carbonate solvent, a fluorinated solvent and a carbonate solvent, the additive being 3-cyano- 1,3 propene sultone, the content of the additive in the lithium ion battery electrolyte is 0.5%-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 selected from the structural formula Fluorocarbonate, structural formula Fluorocarbonate and structural formula At least one of the fluoroethers; wherein R 1 to R 6 are both C x F y H z , 1 ⁇ x ⁇ 6, y>0, z ⁇ 0.
- 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 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 mixed state at room temperature.
- the mixture was stirred uniformly, and then 3-cyano-1,3 propene sultone was added, and the solution was filtered and filtered to obtain the high-voltage lithium ion battery electrolyte.
- the above high voltage lithium ion battery electrolyte is used in the preparation of a high voltage 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-cyano-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. Thereby effectively protecting 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 lithium ion battery electrolyte of the invention is simple, and the interface property between the positive electrode and the negative electrode of the battery and the electrolyte is improved at the same time, 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 lithium ion battery prepared by the high voltage 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-cyano-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.
- the preparation method of the above high voltage lithium ion battery electrolyte is:
- the above 3-cyano-1,3 propene sultone is prepared by dissolving 1 mol of 1,3-propene sultone in 800 mL of dichloromethane using 1,3-propene sultone as a raw material. Adding 1.08 mol of NBS in portions at 35 ° C for 7.5 h to obtain the intermediate 3-bromo-1,3-propene sultone, and then placing the obtained intermediate with sodium cyanide in dichloromethane. The exchange reaction was carried out in the presence of 15-crown-5 to give the product 3-cyano-1,3-propene sultone.
- the high-voltage lithium ion battery electrolyte of the present embodiment is used for a lithium cobaltate/graphite soft-package 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. After 200 weeks of cycle, the capacity retention rate was above 94%. After 300 weeks of cycling, the capacity retention rate was above 91%. After 400 weeks of cycle, the capacity retention rate was around 90%. After 500 cycles, the capacity retention rate was still 85. %the above.
- the preparation method of the above high voltage lithium ion battery electrolyte is:
- the high-voltage lithium ion battery electrolyte of the present embodiment is used for a lithium cobaltate/graphite soft-package 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. After 200 weeks of cycle, the capacity retention rate was 94%. After 300 weeks of cycle, the capacity retention rate was 91%. After 400 cycles, the capacity retention rate was 90%. After 500 cycles, the capacity retention rate was still above 85%.
- the preparation method of the above high voltage lithium ion battery electrolyte is:
- the high voltage lithium ion battery electrolyte of the embodiment is used for a lithium cobalt oxide/graphite soft pack battery, and the measurement is performed. Test the lithium cobalt oxide / graphite flexible packaging battery in the normal temperature environment 3.0 ⁇ 4.95V, 1C rate charge and discharge cycle performance. After 200 weeks of cycle, the capacity retention rate is 94%. After 300 weeks of cycle, the capacity retention rate is 91%. After 400 weeks of cycle, the capacity retention rate is 90%. After 500 cycles, the capacity retention rate can still reach 85% or more. .
- the preparation method of the above high voltage lithium ion battery electrolyte is:
- the high-voltage lithium ion battery electrolyte of the present embodiment is used for a lithium cobaltate/graphite soft-package 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
Description
Claims (9)
- 一种高电压锂离子电池电解液,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-氰基-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%。
- 根据权利要求1所述的一种高电压锂离子电池电解液,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%。
- 根据权利要求1所述的一种高电压锂离子电池电解液,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。
- 根据权利要求1所述的一种高电压锂离子电池电解液,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。
- 根据权利要求1所述的一种高电压锂离子电池电解液,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。
- 一种制备如权利要求1所述高电压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-氰基-1,3丙烯磺酸内酯,溶清后过滤,即得所述高电压锂离子电池电解液。
- 根据权利要求1-6任意一项所述高电压锂离子电池电解液在制备高电压锂离子电池中的应用。
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