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WO2018120792A1 - 电解液及二次电池 - Google Patents

电解液及二次电池 Download PDF

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Publication number
WO2018120792A1
WO2018120792A1 PCT/CN2017/093862 CN2017093862W WO2018120792A1 WO 2018120792 A1 WO2018120792 A1 WO 2018120792A1 CN 2017093862 W CN2017093862 W CN 2017093862W WO 2018120792 A1 WO2018120792 A1 WO 2018120792A1
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Prior art keywords
sulfate
bis
electrolyte
group
secondary battery
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French (fr)
Inventor
王小梅
周晓崇
付成华
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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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
    • 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
    • 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 battery technologies, and in particular, to an electrolyte and a secondary battery.
  • the cycle performance and high temperature performance of lithium ion secondary batteries are affected by many factors.
  • electrolytes as an important component of lithium ion secondary batteries, have a significant impact on their performance.
  • the electrolyte can improve the kinetic performance of the lithium ion secondary battery, and can also improve the stability of the interface between the positive and negative electrodes in the cycle and high temperature storage process, thereby achieving the purpose of improving the cycle performance and storage performance of the lithium ion secondary battery.
  • an object of the present invention is to provide an electrolyte and a secondary battery which, when applied to a secondary battery, can provide a secondary battery with low internal resistance and good Low temperature discharge performance, as well as good high temperature storage performance and high temperature cycle performance.
  • the present invention provides an electrolyte comprising an electrolyte salt, an organic solvent, and an additive.
  • the additives include silyl sulfates as well as cyclic sulfates and/or cyclic sulfonates.
  • the invention provides a secondary battery comprising an electrolyte according to an aspect of the invention.
  • the electrolyte of the present invention includes both a silyl sulfate and a cyclic sulfate and/or a cyclic sulfonate.
  • the secondary battery When applied to a secondary battery, the secondary battery can be made more synergistically under the synergistic action of the above substances. Low internal resistance, good low temperature discharge performance, and good high temperature storage performance and high temperature cycle performance.
  • the electrolytic solution according to the first aspect of the invention includes an electrolyte salt, an organic solvent, and an additive.
  • the additives include silyl sulfates as well as cyclic sulfates and/or cyclic sulfonates.
  • the silane-based sulfate has a high reduction potential, which can reduce the interface resistance of the negative electrode, thereby improving the cycle performance of the secondary battery and reducing the internal resistance of the secondary battery. It improves the low-temperature discharge performance and the high-temperature cycle performance, but it cannot suppress the high-temperature storage gas generation of the secondary battery.
  • the cyclic sulfate and the cyclic sulfonate have a high reduction potential, and can preferentially form a film on the surface of the negative electrode at a high voltage, thereby effectively suppressing high-temperature storage gas generation of the secondary battery, but when the amount of addition is high, The internal resistance of the secondary battery is increased, and the low-temperature discharge performance and high-temperature cycle performance of the secondary battery are deteriorated.
  • the secondary battery can have a low internal resistance, a good low-temperature discharge performance, and good high-temperature storage performance and cycle performance under the synergistic action of the above substances.
  • the silyl sulfate is selected from one or more of the compounds represented by Formula 1.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently selected from an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and a carbon number of One of an alkynyl group of 2 to 5 and an alkoxy group having 1 to 5 carbon atoms, and an H atom of an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group may be further represented by F, Cl, Br, I, One or more substitutions of a cyano group, a carboxyl group, or a sulfonic acid group.
  • the silane-based sulfate is selected from the group consisting of Silicate, bis(triethylsilyl)sulfate, bis(tri-n-propylsilyl)sulfate, bis(triisopropylsilyl)sulfate, bis(tri-n-butylsilyl) Sulfate, bis(triisobutylsilyl)sulfate, bis(tri-tert-butylsilyl)sulfate, bis(trimethoxysilyl)sulfate, bis(triethoxysilyl)sulfate , bis(tri-n-propoxysilyl)sulfate, bis(triisopropoxysilyl)sulfate, bis(tri-n-butoxysilyl)sulfate, bis(tri-sec-butoxysilyl) Sulfate, bis(tri-tert-butoxysilyl) sulf
  • the cyclic sulfate is selected from one or more of the compounds represented by Formula 2.
  • n is an integer within 1 to 3; and R 21 , R 22 , R 23 and R 24 are each independently selected from H, F, Cl, Br, I, an alkyl group having 1 to 10 carbon atoms.
  • R 21 , R 22 , R 23 and R 24 are each independently selected from H, F, Cl, Br, I, an alkyl group having 1 to 10 carbon atoms.
  • an alkoxy group having 1 to 10 carbon atoms wherein the H atom on the alkyl group or the alkoxy group may be substituted with one or more of F, Cl, Br, and I.
  • the cyclic sulfate is selected from one or more of the following compounds:
  • the cyclic sulfonate is selected from one or more of the compounds represented by Formula 3.
  • n is an integer within 1 to 3
  • R 31 , R 32 , R 33 , R 34 , R 35 and R 36 are each independently selected from H, F, Cl, Br, I, and the number of carbon atoms is
  • an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms may be substituted by one or more of F, Cl, Br, and I. .
  • the cyclic sulfonate is selected from one or more of the following compounds:
  • the content of the silyl sulfate is 0.5% to 10% by weight based on the total weight of the electrolytic solution, and preferably, the content of the silyl sulfate is 1% to 5% of the total weight of the electrolyte.
  • the total content of the cyclic sulfate and/or cyclic sulfonate is from 0.5% to 10% by weight based on the total weight of the electrolytic solution.
  • the total content of the cyclic sulfate and/or cyclic sulfonate is from 1% to 5% of the total weight of the electrolyte.
  • the electrolyte salt may be selected from a lithium salt, a sodium salt or a zinc salt, which varies depending on the secondary battery to which the electrolyte is applied.
  • the content of the electrolyte salt is 6.2% to 25% of the total weight of the electrolytic solution, and preferably, the content of the electrolyte salt is the electrolytic solution.
  • the total weight is from 6.25% to 18.8%, and further preferably, the content of the electrolyte salt is from 10% to 15% of the total weight of the electrolyte.
  • the specific kind of the organic solvent is not particularly limited and may be selected according to actual needs.
  • a non-aqueous organic solvent is used.
  • the non-aqueous organic solvent may include any kind of carbonate, carboxylate.
  • the carbonate may include a cyclic carbonate or a chain carbonate.
  • the non-aqueous organic solvent may also include a halogenated compound of a carbonate.
  • the organic solvent may be selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, pentylene carbonate, fluoroethylene carbonate, dimethyl carbonate (DMC), Diethyl carbonate (DEC), dipropyl carbonate, ethyl methyl carbonate (EMC), methyl formate, ethyl formate, ethyl acetate, propyl propionate, ethyl propionate, ⁇ -butyrolactone (BL One or more of tetrahydrofuran (THF).
  • EC ethylene carbonate
  • PC propylene carbonate
  • PC butylene carbonate
  • pentylene carbonate fluoroethylene carbonate
  • DMC dimethyl carbonate
  • DEC Diethyl carbonate
  • EMC dipropyl carbonate
  • EMC ethyl methyl carbonate
  • BL tetrahydrofuran
  • a secondary battery according to a second aspect of the invention includes the electrolytic solution according to the first aspect of the invention.
  • the secondary battery in addition to the electrolytic solution, further includes: a positive electrode sheet, a negative electrode sheet, and a separator.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode film disposed on the positive electrode current collector, the positive electrode film including a positive electrode active material, a binder, and a conductive material Agent.
  • the negative electrode sheet includes a negative electrode current collector and an negative electrode film disposed on the negative electrode current collector, and the negative electrode film includes a negative electrode active material, a binder, and may also include a conductive agent.
  • the separator is spaced between the positive electrode tab and the negative electrode tab.
  • the separator may be any separator material used in the existing secondary battery, such as polyethylene, polypropylene, polyvinylidene fluoride, and multilayers thereof. Composite membranes, but are not limited to these.
  • the secondary battery may be a lithium ion secondary battery, a sodium ion secondary battery, or a zinc ion secondary battery.
  • the electrolyte salt may be selected from a lithium salt
  • the lithium salt is LiPF 6 .
  • the positive active material may be selected from one or more of lithium cobaltate (LiCoO 2 ), lithium nickel manganese cobalt ternary material, lithium iron phosphate, lithium manganese oxide. kind.
  • the anode active material may be selected from metallic lithium.
  • the negative active material may also be selected from materials capable of intercalating lithium at ⁇ 2 V (vs. Li/Li + ).
  • the negative active material may be selected from natural graphite, artificial graphite, mesophase micro carbon spheres (MCMB), hard carbon, soft carbon, silicon, silicon-carbon composite, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO 2 , spinel structure lithiated TiO 2 -Li 4 Ti 5 One or more of O 12 and Li-Al alloys.
  • the secondary battery is a sodium ion secondary battery or a zinc ion secondary battery, it is only necessary to change the corresponding positive electrode active material, negative electrode active material, and electrolyte salt.
  • A1 bis(trifluoromethylsilyl) sulfate
  • the lithium ion secondary batteries of Examples 1-10 and Comparative Examples 1-3 were all prepared in the following manner.
  • the positive electrode active material lithium cobaltate (LiCoO 2 ), the binder polyvinylidene fluoride, and the conductive agent acetylene black are mixed at a weight ratio of 96:2:2, and N-methylpyrrolidone (NMP) is added under the action of a vacuum mixer.
  • NMP N-methylpyrrolidone
  • the negative electrode active material graphite, the conductive agent acetylene black, the binder styrene-butadiene rubber (SBR), and the thickener sodium carboxymethyl cellulose (CMC) are mixed at a weight ratio of 97:1:1:1, and deionized water is added.
  • the negative electrode sheet was obtained by slitting.
  • the content of LiPF 6 is 12.5% of the total weight of the electrolyte.
  • Table 1 The specific types and contents of the silyl sulfate, cyclic sulfate, and cyclic sulfonate used in the electrolytic solution are shown in Table 1.
  • Table 1 the content of the silyl sulfate, the cyclic sulfate, and the cyclic sulfonate is a weight percentage calculated based on the total weight of the electrolytic solution.
  • a 16 ⁇ m thick polypropylene separator (model C210, supplied by Celgard) was used.
  • the positive electrode sheet, the separator film and the negative electrode sheet are stacked in order, so that the separator is in a role of isolation between the positive and negative electrode sheets, and then wound to obtain a bare cell; the bare cell is placed in the outer package foil, and the electricity is placed in the outer package foil.
  • the prepared electrolyte is injected into the dried bare cell, and after vacuum encapsulation, standing, formation, shaping, etc., a lithium ion secondary battery is obtained. .
  • the lithium ion secondary battery was charged at a constant current of 1 C (nominal capacity) to a voltage of 4.45 V at 25 ° C. Further, the battery is charged at a constant voltage of 4.45 V until the current is ⁇ 0.05 C, left for 5 min, discharged at a constant current of 1 C to a voltage of 3 V, and the actual discharge capacity is recorded, and the lithium ion secondary battery is based on the discharge capacity (100% SOC). Adjust to 50% SOC.
  • the lithium ion secondary battery is allowed to stand at -25 ° C for more than 4 h, so that the temperature of the lithium ion secondary battery reaches -25 ° C, and the discharge is continued for 10 s at a current of 0.3 C, and the voltage before the discharge and the voltage at the end of the discharge are used. The difference is divided by the current to obtain the DCIR of the lithium ion secondary battery. 15 lithium ion secondary batteries were tested in each group and averaged.
  • the lithium ion secondary battery was charged at a constant current of 1 C (nominal capacity) to a voltage of 4.45 V at 25 ° C, and then charged at a constant voltage of 4.45 V until the current was less than or equal to 0.05 C. After leaving for 5 minutes, the constant current was 0.5 C.
  • the discharge to the cut-off voltage is 3V, at which time the actual discharge capacity is recorded as D0.
  • the lithium ion secondary battery was allowed to stand at -15 ° C for 1 h, charged at a constant current of 1 C to a voltage of 4.45 V, and then charged at a constant voltage of 4.45 V until the current was less than or equal to 0.05 C. After being left for 10 min, the constant current was 0.5 C. The discharge was discharged to a voltage of 3 V, and the discharge capacity at this time was recorded as D1.
  • Capacity retention rate (%) of low-temperature discharge of lithium ion secondary battery D1/D0 ⁇ 100%. 15 lithium ion secondary batteries were tested in each group and averaged.
  • the lithium ion secondary battery was charged at a constant current of 1 C to a voltage of 4.45 V at 45 ° C, further charged at a constant voltage of 4.45 V until the current was 0.05 C, and then discharged at a constant current of 1 C to a voltage of 3.0 V, which is a During the charge and discharge cycle, this discharge capacity is the discharge capacity of the first cycle.
  • the lithium ion secondary battery was subjected to 300 cycles of charge/discharge test in accordance with the above method, and the discharge capacity at the 300th cycle was detected.
  • the capacity retention ratio (%) of the lithium ion secondary battery after circulating at 45 ° C for 300 times (discharge capacity of 300 cycles of lithium ion secondary battery discharge / discharge capacity of the first cycle of lithium ion secondary battery) ⁇ 100%. 15 lithium ion secondary batteries were tested in each group and averaged.
  • the lithium ion secondary battery was charged at a constant current of 0.5 C to a voltage of 4.45 V at 25 ° C, and then charged at a constant voltage of 4.45 V to a current of 0.05 C to be fully charged at 4.45 V, at which time the lithium ion was tested.
  • the thickness of the secondary battery was recorded as h 0 ; thereafter, the lithium ion secondary battery was placed in an incubator at 60 ° C, and after 30 days of storage, it was taken out, and the thickness of the lithium ion secondary battery at this time was measured and recorded as h 1 .
  • the thickness expansion ratio of the lithium ion secondary battery after storage at 60 ° C for 30 days [(h 1 -h 0 ) / h 0 ] ⁇ 100%. Each group was tested for 15 lithium ion secondary batteries and averaged.
  • the lithium ion can be improved while reducing the internal resistance at the low temperature of the lithium ion secondary battery.
  • Two The capacity retention rate, high temperature cycle performance and high temperature storage performance of the secondary battery after low temperature discharge.

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Abstract

一种电解液及二次电池。所述电解液包括电解质盐、有机溶剂以及添加剂。所述添加剂包括：硅烷基硫酸酯以及环状硫酸酯和/或环状磺酸酯。当所述电解质应用到二次电池中后，在上述物质的协同作用下，能够使二次电池具有较低的内阻、良好的低温放电性能、以及良好的高温存储性能和高温循环性能。

Description

电解液及二次电池 技术领域
本发明涉及电池技术领域，尤其涉及一种电解液及二次电池。
背景技术
在飞速发展的信息时代中，对手机、笔记本、相机等电子产品的需求逐年增加。二次电池尤其是锂离子二次电池作为电子产品的工作电源，具有能量密度高、无记忆效应、工作电压高等特点，正逐步取代传统的Ni-Cd、MH-Ni电池。然而随着电子产品市场需求的扩大及动力、储能设备的发展，人们对锂离子二次电池的要求不断提高，开发具有高能量密度和满足快速充放电的锂离子二次电池成为当务之急。目前，有效的方法是提高电极材料的电压、压实密度和选择合适的电解液。
目前，锂离子二次电池的循环性能、高温性能受到很多因素的影响，其中，电解液作为锂离子二次电池的重要组成部分，对其性能有着重大的影响。通过电解液能够改善锂离子二次电池的动力学性能，还能改善循环及高温存储过程中正负极界面稳定性，从而达到改善锂离子二次电池的循环性能和存储性能的目的。
发明内容
鉴于背景技术中存在的问题，本发明的目的在于提供一种电解液及二次电池，当所述电解液应用到二次电池中后，能够使二次电池具有较低的内阻、良好的低温放电性能、以及良好的高温存储性能和高温循环性能。
为了达到上述目的，在本发明的一方面，本发明提供了一种电解液，其包括电解质盐、有机溶剂以及添加剂。所述添加剂包括硅烷基硫酸酯以及环状硫酸酯和/或环状磺酸酯。
在本发明的另一方面，本发明提供了一种二次电池，其包括根据本发明一方面所述的电解液。
相对于现有技术，本发明的有益效果包括，但不限于：
本发明的电解液同时包括硅烷基硫酸酯以及环状硫酸酯和/或环状磺酸酯，当其应用到二次电池中后，在上述物质的协同作用下，能够使二次电池具有较低的内阻、良好的低温放电性能、以及良好的高温存储性能和高温循环性能。
具体实施方式
下面详细说明根据本发明的电解液及二次电池。
首先说明根据本发明第一方面的电解液。
根据本发明第一方面的电解液包括电解质盐、有机溶剂以及添加剂。所述添加剂包括硅烷基硫酸酯以及环状硫酸酯和/或环状磺酸酯。
在根据本发明第一方面所述的电解液中，所述硅烷基硫酸酯具有较高的还原电位，可以减小负极界面阻抗，从而改善二次电池的循环性能并降低二次电池的内阻、提高低温放电性能和高温循环性能，但是其无法抑制二次电池的高温存储产气。环状硫酸酯和环状磺酸酯具有较高的还原电位，能优先在高电压下的负极表面成膜，从而有效抑制二次电池的高温存储产气，但是当其加入量较高时，会增大二次电池的内阻，恶化二次电池的低温放电性能以及高温循环性能。当电解液中同时包括上述物质时，在上述物质的协同作用下，能够使二次电池具有较低的内阻、良好的低温放电性能、以及良好的高温存储性能和循环性能。
在根据本发明第一方面所述的电解液中，所述硅烷基硫酸酯选自式1所示的化合物中的一种或几种。其中，R1、R2、R3、R4、R5、R6各自独立地选自碳原子数为1～5的烷基、碳原子数为2～5的烯基、碳原子数为2～5的炔基、碳原子数为1～5的烷氧基中的一种，烷基、烯基、炔基、烷氧基中的H原子还可被F、Cl、Br、I、氰基、羧基、磺酸基中的一种或几种取代。
Figure PCTCN2017093862-appb-000001
在根据本发明第一方面所述的电解液中，所述硅烷基硫酸酯选自双(三甲 基硅基)硫酸酯、双(三乙基硅基)硫酸酯、双(三正丙基硅基)硫酸酯、双(三异丙基硅基)硫酸酯、双(三正丁基硅基)硫酸酯、双(三异丁基硅基)硫酸酯、双(三叔丁基硅基)硫酸酯、双(三甲氧基硅基)硫酸酯、双(三乙氧基硅基)硫酸酯、双(三正丙氧基硅基)硫酸酯、双(三异丙氧基硅基)硫酸酯、双(三正丁氧基硅基)硫酸酯、双(三仲丁氧基硅基)硫酸酯、双(三叔丁氧基硅基)硫酸酯、双(三氟甲基硅基)硫酸酯、三甲基硅基三乙基硅基硫酸酯、双(三乙烯基硅基)硫酸酯、双(三乙炔基硅基)硫酸酯中的一种或几种。
在根据本发明第一方面所述的电解液中，所述环状硫酸酯选自式2所示的化合物中的一种或几种。在式2中，n为1～3内的整数；R21、R22、R23、R24各自独立地选自H、F、Cl、Br、I、碳原子数为1～10的烷基、碳原子数为1～10的烷氧基中的一种，其中，烷基、烷氧基上的H原子还可被F、Cl、Br、I中的一种或几种取代。
Figure PCTCN2017093862-appb-000002
在根据本发明第一方面所述的电解液中，所述环状硫酸酯选自下述化合物中的一种或几种：
Figure PCTCN2017093862-appb-000003
Figure PCTCN2017093862-appb-000004
在根据本发明第一方面所述的电解液中，所述环状磺酸酯选自式3所示的化合物中的一种或几种。在式3中，n为1～3内的整数，R31、R32、R33、R34、R35、R36各自独立地选自H、F、Cl、Br、I、碳原子数为1～10的烷基、碳原子数为1～10的烷氧基中的一种，烷基、烷氧基上的H还可被F、Cl、Br、I中的一种或几种取代。
Figure PCTCN2017093862-appb-000005
在根据本发明第一方面所述的电解液中，所述环状磺酸酯选自下述化合物中的一种或几种：
Figure PCTCN2017093862-appb-000006
Figure PCTCN2017093862-appb-000007
在根据本发明第一方面所述的电解液中，所述硅烷基硫酸酯的含量为所述电解液的总重量的0.5％～10％，优选地，所述硅烷基硫酸酯的含量为所述电解液的总重量的1％～5％。
在根据本发明第一方面所述的电解液中，所述环状硫酸酯和/或环状磺酸酯的总含量为所述电解液的总重量的0.5％～10％。优选地，所述环状硫酸酯和/或环状磺酸酯的总含量为所述电解液的总重量的1％～5％。
在根据本发明第一方面所述的电解液中，所述电解质盐可选自锂盐、钠盐或锌盐，依据所述电解液应用的二次电池的不同而不同。
在根据本发明第一方面所述的电解液中，所述电解质盐的含量为所述电解液的总重量的6.2％～25％，优选地，所述电解质盐的含量为所述电解液的总重量的6.25％～18.8％，进一步优选地，所述电解质盐的含量为所述电解液的总重量的10％～15％。
在根据本发明第一方面所述的电解液中，所述有机溶剂的具体种类并没有特别的限制，可根据实际需求进行选择。优选地，使用非水有机溶剂。所述非水有机溶剂可包括任意种类的碳酸酯、羧酸酯。碳酸酯可包括环状碳酸酯或者链状碳酸酯。所述非水有机溶剂还可包括碳酸酯的卤代化合物。具体地，所述有机溶剂可选自碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯、碳酸亚戊酯、氟代碳酸亚乙酯、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸二丙酯、碳酸甲乙酯(EMC)、甲酸甲酯、甲酸乙酯、乙酸乙酯、丙酸丙酯、丙酸乙酯、γ-丁内酯(BL)、四氢呋喃(THF)中的一种或几种。
其次说明根据本发明第二方面的二次电池。
根据本发明第二方面的二次电池包括根据本发明第一方面所述的电解液。
在根据本发明第二方面所述的二次电池中，除电解液外，所述二次电池还包括：正极片、负极片以及隔离膜。所述正极片包括正极集流体和设置于正极集流体上的正极膜片，所述正极膜片包括正极活性材料、粘接剂和导电 剂。所述负极片包括负极集流体和设置于负极集流体上的负极膜片，所述负极膜片包括负极活性材料、粘接剂，也可以包括导电剂。所述隔离膜间隔于正极片和负极片之间。
在根据本发明第二方面所述的二次电池中，所述隔离膜可以是现有二次电池中使用的任何隔离膜材料，例如聚乙烯、聚丙烯、聚偏氟乙烯以及它们的多层复合膜，但不仅限于这些。
在根据本发明第二方面所述的二次电池中，所述二次电池可为锂离子二次电池、钠离子二次电池或锌离子二次电池。
当二次电池为锂离子二次电池时，所述电解质盐可选自锂盐，所述锂盐可选自LiPF6、LiBF4、LiN(SO2F)2(简写为LiFSI)、LiN(CF3SO2)2(简写为LiTFSI)、LiClO4、LiAsF6、LiB(C2O4)2(简写为LiBOB)、LiBF2C2O4(简写为LiDFOB)、LiPO2F2、LiTFOP、LiN(SO2RF)2、LiN(SO2F)(SO2RF)中的一种或几种，其中，RF＝CnF2n+1，表示饱和全氟烷基，n为1～10内的整数。优选地，所述锂盐为LiPF6。
当二次电池为锂离子二次电池时，所述正极活性材料可选自钴酸锂(LiCoO2)、锂镍锰钴三元材料、磷酸亚铁锂、锰酸锂中的一种或几种。
当二次电池为锂离子二次电池时，所述负极活性材料可以选自金属锂。所述负极活性材料也可以选自在＜2V(vs.Li/Li+)时可以嵌入锂的材料，具体地，所述负极活性材料可选自天然石墨、人造石墨、中间相微碳球(MCMB)、硬碳、软碳、硅、硅-碳复合物、Li-Sn合金、Li-Sn-O合金、Sn、SnO、SnO2、尖晶石结构的锂化TiO2-Li4Ti5O12、Li-Al合金中的一种或几种。
当二次电池为钠离子二次电池或锌离子二次电池时，仅需改变对应的正极活性材料、负极活性材料、电解质盐即可。
下面结合实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。在实施例中仅示出二次电池为锂离子二次电池的情况，但本发明不限于此。
在以下实施例中，所用到的材料、试剂以及仪器如没有特殊说明，均可从商业途径购买获得。
为了便于说明，在下述实施例中用到的添加剂简写如下：
A1：双(三氟甲基硅基)硫酸酯
A2：三甲基硅基三乙基硅基硫酸酯
B1：硫酸乙烯酯(化合物1)
B2：1,3-丙烷磺内酯(化合物15)
实施例1-10以及对比例1-3中的锂离子二次电池均按照下述方法进行制备。
(1)正极片制备
将正极活性材料钴酸锂(LiCoO2)、粘结剂聚偏氟乙烯、导电剂乙炔黑按照重量比96:2:2进行混合，加入N-甲基吡咯烷酮(NMP)，在真空搅拌机作用下搅拌至体系成均一透明状，获得正极浆料；将正极浆料均匀涂覆于厚度为12μm的正极集流体铝箔上；将铝箔在室温晾干后转移至120℃烘箱干燥1h，然后经过冷压、分切得到正极片。
(2)负极片制备
将负极活性材料石墨、导电剂乙炔黑、粘结剂丁苯橡胶(SBR)、增稠剂羧甲基纤维素钠(CMC)按照重量比97:1:1:1进行混合，加入去离子水，在真空搅拌机作用下获得负极浆料；将负极浆料均匀涂覆在厚度为8μm的负极集流体铜箔上；将铜箔在室温晾干后转移至120℃烘箱干燥1h，然后经过冷压、分切得到负极片。
(3)电解液制备
在含水量<10ppm的氩气气氛手套箱中，将EC、PC、DEC按照体积比为EC:PC:DEC＝1:1:1进行混合，接着将充分干燥的锂盐LiPF6溶解于混合有机溶剂中，之后加入硅烷基硫酸酯、环状硫酸酯、环状磺酸酯，混合均匀后获得电解液。其中，LiPF6的含量为电解液的总重量的12.5％。电解液中所用到的硅烷基硫酸酯、环状硫酸酯、环状磺酸酯的具体种类以及含量如表1所示。在表1中，硅烷基硫酸酯、环状硫酸酯、环状磺酸酯的含量为基于电解液的总重量计算得到的重量百分数。
(4)隔离膜的制备
选用16μm厚的聚丙烯隔离膜(型号为C210，由Celgard公司提供)。
(5)锂离子二次电池的制备
将正极片、隔离膜、负极片按顺序叠好，使隔离膜处于正、负极片之间起到隔离的作用，然后卷绕得到裸电芯；将裸电芯置于外包装箔中，电芯经过75℃高温静置24h后水分符合规格后，将上述制备好的电解液注入到干燥后的裸电芯中，经过真空封装、静置、化成、整形等工序，获得锂离子二次电池。
表1 实施例1-10以及对比例1-3的添加剂及含量
Figure PCTCN2017093862-appb-000008
注：“-”表示未加入。
接下来说明锂离子二次电池的测试过程。
(1)锂离子二次电池的内阻(DCIR)测试
在25℃，将锂离子二次电池以1C(标称容量)恒流充电到电压为4.45V， 进一步以4.45V恒压充电至电流≤0.05C，搁置5min，以1C恒流放电至截至电压为3V，记录实际放电容量，并以该放电容量为基准(100％SOC)将锂离子二次电池调节至50％SOC。调节完成后，将锂离子二次电池在-25℃搁置4h以上，使得锂离子二次电池的温度达到-25℃，以0.3C的电流持续放电10s，以放电前电压及放电终止时电压之差，除以电流，即得到锂离子二次电池的DCIR。每组测试15支锂离子二次电池，取平均值。
(2)锂离子二次电池的低温放电性能测试
在25℃下，将锂离子二次电池以1C(标称容量)恒流充电到电压为4.45V，然后以4.45V恒压充电至电流小于等于0.05C，搁置5min后，以0.5C恒流放电至截至电压为3V，此时将实际放电容量记为D0。
然后将锂离子二次电池在-15℃下静置1h，以1C恒流充电到电压为4.45V，再以4.45V恒压充电至电流小于等于0.05C，搁置10min后，以0.5C恒流放电至截至电压3V，此时的放电容量记为D1。
锂离子二次电池低温放电的容量保持率(％)＝D1/D0×100％。每组测试15支锂离子二次电池，取平均值。
(3)锂离子二次电池的高温循环性能测试
在45℃下，将锂离子二次电池以1C恒流充电至电压为4.45V，进一步以4.45V恒压充电至电流为0.05C，然后以1C恒流放电至电压为3.0V，此为一个充放电循环过程，此次的放电容量为首次循环的放电容量。将锂离子二次电池按照上述方法进行300次循环充电/放电测试，检测得到第300次循环的放电容量。
锂离子二次电池45℃循环300次后的容量保持率(％)＝(锂离子二次电池循环300次的放电容量/锂离子二次电池首次循环的放电容量)×100％。每组测试15支锂离子二次电池，取平均值。
(4)锂离子二次电池的高温存储性能测试
在25℃下，将锂离子二次电池以0.5C恒流充电至电压为4.45V，然后以4.45V恒压充电至电流为0.05C，使其处于4.45V满充状态，此时测试锂离子二次电池的厚度并记为h0；之后将锂离子二次电池放入60℃的恒温箱，储存30天后取出，测试此时锂离子二次电池的厚度并记为h1。
锂离子二次电池60℃存储30天后的厚度膨胀率＝[(h1-h0)/h0]×100％。每 组测试15支锂离子二次电池，取平均值。
表2 实施例1-10以及对比例1-3的测试结果
Figure PCTCN2017093862-appb-000009
从表2的相关数据分析可以得知，对比例1中没有加入硅烷基硫酸酯以及环状硫酸酯和/或环状磺酸酯，锂离子二次电池低温下的内阻(DCIR)、低温放电后的容量保持率、高温循环性能以及高温存储性能均较差。当电解液中仅加入硅烷基硫酸酯(对比例2)时，锂离子二次电池的高温循环性能、低温下的内阻、低温放电后的容量保持率得到了改善，但锂离子二次电池的高温存储产气仍旧得不到抑制；当电解液中仅加入环状硫酸酯(对比例3)时，锂离子二次电池的高温存储产气得到明显的抑制，但锂离子二次电池低温下的内阻、低温放电后的容量保持率恶化明显。
当电解液中同时加入硅烷基硫酸酯以及环状硫酸酯和/或环状磺酸酯(实施例1-10)时，能在降低锂离子二次电池低温下的内阻的同时提高锂离子二 次电池低温放电后的容量保持率、高温循环性能及高温存储性能。

Claims (10)

  1. 一种电解液，包括：
    电解质盐；
    有机溶剂；以及
    添加剂；
    其特征在于，
    所述添加剂包括：
    硅烷基硫酸酯；以及
    环状硫酸酯和/或环状磺酸酯。
  2. 根据权利要求1所述的电解液，其特征在于，所述硅烷基硫酸酯选自式1所示的化合物中的一种或几种；
    Figure PCTCN2017093862-appb-100001
    其中，
    R1、R2、R3、R4、R5、R6各自独立地选自碳原子数为1～5的烷基、碳原子数为2～5的烯基、碳原子数为2～5的炔基、碳原子数为1～5的烷氧基中的一种，烷基、烯基、炔基、烷氧基中的H原子还可被F、Cl、Br、I、氰基、羧基、磺酸基中的一种或几种取代。
  3. 根据权利要求2所述的电解液，其特征在于，所述硅烷基硫酸酯选自双(三甲基硅基)硫酸酯、双(三乙基硅基)硫酸酯、双(三正丙基硅基)硫酸酯、双(三异丙基硅基)硫酸酯、双(三正丁基硅基)硫酸酯、双(三异丁基硅基)硫酸酯、双(三叔丁基硅基)硫酸酯、双(三甲氧基硅基)硫酸酯、双(三乙氧基硅基)硫酸酯、双(三正丙氧基硅基)硫酸酯、双(三异丙氧基硅基)硫酸酯、双(三正丁氧基硅基)硫酸酯、双(三仲丁氧基硅基)硫酸酯、双(三叔丁氧基硅基)硫酸酯、双(三氟甲基硅基)硫酸酯、三甲基硅基三乙基硅基硫酸酯、双(三乙烯基硅基)硫酸酯、双(三乙炔基硅基)硫酸酯中的一种或几种。
  4. 根据权利要求1所述的电解液，其特征在于，
    所述环状硫酸酯选自式2所示的化合物中的一种或几种：
    Figure PCTCN2017093862-appb-100002
    在式2中，n为1～3内的整数；R21、R22、R23、R24各自独立地选自H、F、Cl、Br、I、碳原子数为1～10的烷基、碳原子数为1～10的烷氧基中的一种，其中，烷基、烷氧基上的H原子还可被F、Cl、Br、I中的一种或几种取代；
    所述环状磺酸酯选自式3所示的化合物中的一种或几种：
    Figure PCTCN2017093862-appb-100003
    在式3中，n为1～3内的整数，R31、R32、R33、R34、R35、R36各自独立地选自H、F、Cl、Br、I、碳原子数为1～10的烷基、碳原子数为1～10的烷氧基中的一种，烷基、烷氧基上的H还可被F、Cl、Br、I中的一种或几种取代。
  5. 根据权利要求4所述的电解液，其特征在于，
    所述环状硫酸酯选自下述化合物中的一种或几种：
    Figure PCTCN2017093862-appb-100004
    Figure PCTCN2017093862-appb-100005
    所述环状磺酸酯选自下述化合物中的一种或几种：
    Figure PCTCN2017093862-appb-100006
  6. 根据权利要求1所述的电解液，其特征在于，所述硅烷基硫酸酯的含量为所述电解液的总重量的0.5％～10％，优选为1％～5％。
  7. 根据权利要求1所述的电解液，其特征在于，所述环状硫酸酯和/或环状磺酸酯的总含量为所述电解液的总重量的0.5％～10％，优选为1％～5％。
  8. 根据权利要求1所述的电解液，其特征在于，所述有机溶剂选自碳酸亚乙酯、碳酸亚丙酯、碳酸亚丁酯、碳酸亚戊酯、氟代碳酸亚乙酯、碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸甲乙酯、甲酸甲酯、甲酸乙酯、乙酸乙酯、丙酸丙酯、丙酸乙酯、γ-丁内酯、四氢呋喃中的一种或几种。
  9. 根据权利要求1所述的电解液，其特征在于，所述电解质盐的含量为所述电解液的总重量的6.2％～25％，优选地，所述电解质盐的含量为所述电解液的总重量的6.25％～18.8％，进一步优选地，所述电解质盐的含量为所述电解液的总重量的10％～15％。
  10. 一种二次电池，其特征在于，包括根据权利要求1-9中任一项所述的电解液。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019050167A3 (ko) * 2017-09-06 2019-05-09 삼성에스디아이 주식회사 리튬 이차 전지용 비수 전해질 및 이를 포함하는 리튬 이차 전지
CN114245943A (zh) * 2019-12-24 2022-03-25 宁德时代新能源科技股份有限公司 二次电池及含有该二次电池的装置
US20220352552A1 (en) * 2021-04-21 2022-11-03 Prime Planet Energy & Solutions, Inc. Electrolyte solution for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
US11721837B2 (en) 2017-09-06 2023-08-08 Samsung Sdi Co., Ltd. Lithium secondary battery including fluoroethylene carbonate in electrolyte
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Publication number Priority date Publication date Assignee Title
CN110808412B (zh) * 2018-08-06 2022-06-07 宁德时代新能源科技股份有限公司 电解液及锂离子电池
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CN119301792A (zh) * 2023-03-31 2025-01-10 宁德时代新能源科技股份有限公司 二次电池及用电装置

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6013394A (en) * 1998-01-20 2000-01-11 Wilson Greatbatch Ltd. Organic sulfate additives for nonaqueous electrolyte in alkali metal electrochemical cells
CN101248552A (zh) * 2005-06-23 2008-08-20 三菱化学株式会社 非水电解液及使用它的非水电解质二次电池
US20090311609A1 (en) * 2005-06-23 2009-12-17 Sanyo Electric Co., Ltd. Nonaqueous electrolyte secondary battery and nonaqueous electrolyte solution
CN102195085A (zh) * 2010-03-16 2011-09-21 三星Sdi株式会社 可再充电锂电池用电解质溶液和包括其的可再充电锂电池
CN103107355A (zh) * 2013-02-03 2013-05-15 宁德新能源科技有限公司 锂离子电池及其电解液
CN104600362A (zh) * 2015-02-05 2015-05-06 深圳市三讯电子有限公司 一种动力电池及其锂离子电解液
CN105655640A (zh) * 2016-03-28 2016-06-08 宁德新能源科技有限公司 一种非水电解液以及含有该电解液的锂离子电池
CN105914399A (zh) * 2016-05-04 2016-08-31 宁德新能源科技有限公司 一种电解液以及含有该电解液的锂离子电池
CN106159321A (zh) * 2015-03-31 2016-11-23 比亚迪股份有限公司 一种锂离子电池非水电解液和锂离子电池

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5549438B2 (ja) * 2009-07-30 2014-07-16 三菱化学株式会社 非水系電解液及びそれを用いた非水系電解液二次電池
JP2015133278A (ja) * 2014-01-15 2015-07-23 ソニー株式会社 二次電池、電池パック、電動車両、電力貯蔵システム、電動工具および電子機器
JP2015156372A (ja) * 2014-01-15 2015-08-27 旭化成株式会社 非水蓄電デバイス用電解液及びリチウムイオン二次電池
CN105609874A (zh) * 2015-12-21 2016-05-25 东莞新能源科技有限公司 电解液以及包括该电解液的锂离子电池

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6013394A (en) * 1998-01-20 2000-01-11 Wilson Greatbatch Ltd. Organic sulfate additives for nonaqueous electrolyte in alkali metal electrochemical cells
CN101248552A (zh) * 2005-06-23 2008-08-20 三菱化学株式会社 非水电解液及使用它的非水电解质二次电池
US20090311609A1 (en) * 2005-06-23 2009-12-17 Sanyo Electric Co., Ltd. Nonaqueous electrolyte secondary battery and nonaqueous electrolyte solution
CN102195085A (zh) * 2010-03-16 2011-09-21 三星Sdi株式会社 可再充电锂电池用电解质溶液和包括其的可再充电锂电池
CN103107355A (zh) * 2013-02-03 2013-05-15 宁德新能源科技有限公司 锂离子电池及其电解液
CN104600362A (zh) * 2015-02-05 2015-05-06 深圳市三讯电子有限公司 一种动力电池及其锂离子电解液
CN106159321A (zh) * 2015-03-31 2016-11-23 比亚迪股份有限公司 一种锂离子电池非水电解液和锂离子电池
CN105655640A (zh) * 2016-03-28 2016-06-08 宁德新能源科技有限公司 一种非水电解液以及含有该电解液的锂离子电池
CN105914399A (zh) * 2016-05-04 2016-08-31 宁德新能源科技有限公司 一种电解液以及含有该电解液的锂离子电池

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019050167A3 (ko) * 2017-09-06 2019-05-09 삼성에스디아이 주식회사 리튬 이차 전지용 비수 전해질 및 이를 포함하는 리튬 이차 전지
US11557791B2 (en) 2017-09-06 2023-01-17 Samsung Sdi Co., Ltd. Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same
US11721837B2 (en) 2017-09-06 2023-08-08 Samsung Sdi Co., Ltd. Lithium secondary battery including fluoroethylene carbonate in electrolyte
CN114245943A (zh) * 2019-12-24 2022-03-25 宁德时代新能源科技股份有限公司 二次电池及含有该二次电池的装置
US20220352552A1 (en) * 2021-04-21 2022-11-03 Prime Planet Energy & Solutions, Inc. Electrolyte solution for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
WO2025201436A1 (zh) * 2024-12-17 2025-10-02 惠州亿纬锂能股份有限公司 一种电解液、电池

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