WO2023015791A1 - 一种电解液及包含该电解液的电池 - Google Patents

一种电解液及包含该电解液的电池 Download PDF

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WO2023015791A1
WO2023015791A1 PCT/CN2021/137033 CN2021137033W WO2023015791A1 WO 2023015791 A1 WO2023015791 A1 WO 2023015791A1 CN 2021137033 W CN2021137033 W CN 2021137033W WO 2023015791 A1 WO2023015791 A1 WO 2023015791A1
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electrolyte
carbonate
battery
combination
formula
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PCT/CN2021/137033
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English (en)
French (fr)
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孙春胜
乔顺攀
张和平
顿温新
李俊杰
申海鹏
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湖州昆仑亿恩科电池材料有限公司
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Publication of WO2023015791A1 publication Critical patent/WO2023015791A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the embodiments of the present application relate to the technical field of batteries, for example, an electrolyte solution and a battery containing the electrolyte solution.
  • the battery electrolyte has a vital impact on the service life, storage life, capacity development, high and low temperature and safety performance of the battery.
  • the commercial electrolyte is mainly a binary or ternary mixed solvent system of cyclic carbonate and chain carbonate dissolved in lithium hexafluorophosphate (LiPF 6 ). It can form a stable solid electrolyte interface film (SEI film) and other characteristics, and is considered to be the best choice for the electrolyte solvent system.
  • SEI film solid electrolyte interface film
  • organic carbonate solvents have defects such as volatile, flammable, and insufficient oxidation resistance, which lead to a decrease in battery safety.
  • additives can be divided into SEI film-forming additives, conductive additives, flame retardant additives, overcharge protection additives, additives for improving low-temperature performance of electrolytes, additives for improving thermal stability of electrolytes, and control of acid and water content in electrolytes additives, etc.
  • CN110911750A discloses high-voltage lithium ion battery electrolyte, additive and the preparation method of this additive, and its disclosed additive is thiourea derivative salt, and its disclosed additive preparation method comprises the following steps: (1) at first solvent, catalyst and sulfur The urea is placed in a reaction vessel, the organic acid is gradually added dropwise, and the polycondensation reaction is carried out under an ice-water bath to obtain a thiourea lipid compound; (2) the by-product is separated by a water separator and high-temperature and reduced-pressure distillation to obtain a crude product of a thiourea compound (3) using a solvent to extract the product, recrystallizing and purifying, and drying to obtain a thiourea lipid compound.
  • the thiourea compound can be used as an additive to the electrolyte of a high-voltage lithium-ion battery, which can capture oxygen free radicals generated by positive electrode materials under high voltage, and can also form an SEI film.
  • CN103094616A discloses an electrolyte additive and a high-voltage electrolyte containing the electrolyte additive and a lithium-ion battery
  • the disclosed electrolyte additive is maleic anhydride C4H2O3 or one of its derivatives
  • the disclosed high-voltage electrolyte can form a stable interfacial film on the surface of the positive and negative electrodes, inhibit the reactivity of the electrode surface, reduce the oxidative decomposition of the electrolyte, and effectively inhibit flatulence, thereby improving the safety performance of lithium-ion batteries. Cycle performance and service life at high and high voltages.
  • the embodiments of the present application provide an electrolyte solution and a battery containing the electrolyte solution.
  • the electrolyte solution can improve the rate discharge performance, cycle performance, and low-temperature discharge performance of the battery.
  • the embodiment of the present application provides an electrolytic solution, the electrolytic solution includes an electrolyte, an organic solvent and an additive represented by formula I;
  • R 1 , R 2 , R 3 and R 4 each independently include: C1-C10 (such as C2, C4, C6, C8, etc.) alkyl, C6-C20 (such as C8, C10, C12, C14, C16, C18, etc.) aromatic hydrocarbon group, C3-C10 (such as C4, C6, C8, etc.) alkoxy, C2-C10 (such as C2, C4, C6, C8, etc.) alkenyl or C2-C10 (such as C2, C4, C6, Any one of C8, etc.) alkynyl groups;
  • C1-C10 such as C2, C4, C6, C8, etc. alkyl
  • C6-C20 such as C8, C10, C12, C14, C16, C18, etc.
  • aromatic hydrocarbon group such as C3-C10 (such as C4, C6, C8, etc.) alkoxy
  • C2-C10 such as C2, C4, C6, C8, etc.
  • alkenyl such as C2, C4, C
  • At least one of R 1 , R 2 , R 3 and R 4 is C2-C10 alkenyl or C2-C10 alkynyl;
  • the R 5 includes bisfluorosulfonimide (FSI), bistrifluoromethanesulfonimide (TFSI), difluorooxalate borate (DFOB), bisoxalate borate (BOB), di Either of fluorine dioxalate phosphate (DFOP) or hexafluorophosphate (PF 6 ).
  • FSI bisfluorosulfonimide
  • TFSI bistrifluoromethanesulfonimide
  • DFOB difluorooxalate borate
  • BOB bisoxalate borate
  • DFOP fluorine dioxalate phosphate
  • PF 6 hexafluorophosphate
  • This application uses the compound shown in formula I as an additive, which is beneficial to positive electrode polymerization and film formation, and can improve the rate discharge performance, cycle performance, and low-temperature discharge performance of the battery, especially for graphite, single crystal silicon and graphite
  • the composite material or oxidation Lithium-ion batteries made of composite materials of sub-silicon and graphite.
  • C1-C10 in this application means that the number of carbon atoms in the corresponding group is 1-10, and “C6-C10” is equivalent.
  • each of R 1 , R 2 , R 3 and R 4 independently includes: any one of methyl, ethyl, propyl, isopropyl, allyl or propargyl;
  • At least one of R 1 , R 2 , R 3 and R 4 is allyl or propargyl.
  • the R 1 , R 2 , R 3 and R 4 each independently include: any one of methyl, ethyl, propyl, isopropyl, allyl or propargyl;
  • At least one of R 1 , R 2 , R 3 and R 4 is allyl or propargyl
  • the R 5 includes bisfluorosulfonimide, bistrifluoromethanesulfonimide, difluorooxalate borate, bisoxalate borate, difluorodioxalate phosphate or hexafluorophosphate any kind.
  • the structural formula of the additive includes any one of formula III or formula IV;
  • the R 5 is any one of bisfluorosulfonimide, bistrifluoromethanesulfonimide or hexafluorophosphate.
  • the additive includes any one or a combination of at least two of the compounds represented by formula III or formula IV.
  • the additive includes but is not limited to the following compounds:
  • the electrolyte includes any one or a combination of at least two of lithium salts, sodium salts or potassium salts.
  • the electrolyte includes any one or a combination of at least two of XClO 4 , XPF 6 , XBF 4 , XTFSI, XFSI, XBOB, XODFB, XCF 3 SO 3 or XAsF 6 , wherein the typical but non-limiting Combinations include: the combination of XClO 4 and XPF 6 , the combination of XBF 4 , XTFSI, XFSI and XBOB, the combination of XBF 4 , XTFSI, XFSI, XBOB, XODFB, XCF 3 SO 3 and XAsF 6 , etc.;
  • X includes any one of Li, Na or K.
  • the organic solvent includes a non-aqueous organic solvent.
  • the organic solvent includes any one or a combination of at least two of carbonates, carboxylates, propionates, fluoroethers or aromatic hydrocarbons, where typical but non-limiting combinations include: carbonates and carboxylates Combination of ester, combination of carboxylate, propionate and fluoroether, combination of carboxylate, propionate, fluoroether and aromatic hydrocarbon, etc.
  • the carbonates include halogenated carbonates and/or non-halogenated carbonates.
  • the non-halogenated carbonate comprises ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC) or ethyl methyl carbonate (EMC). Any one or a combination of at least two.
  • the halogenated carbonates include fluoroethylene carbonate (FEC), difluoroethylene carbonate, difluoropropylene carbonate, ethyl trifluoroacetate, trifluoroethyl methyl carbonate, trifluoroethylene Methylethylene carbonate, 4-trifluoromethylethylene carbonate, chloroethylene carbonate, bis(2,2,2-trifluoroethyl)carbonate, methyl trifluoropropionate, 3,3, Ethyl 3-trifluoroacetate, methyl 2-trifluoromethylbenzoate, ethyl 4,4,4-trifluorobutyrate or 1,1,1,3,3,3-hexafluoroisopropyl Any one or a combination of at least two of acrylates.
  • FEC fluoroethylene carbonate
  • difluoroethylene carbonate difluoropropylene carbonate
  • ethyl trifluoroacetate trifluoroethyl methyl carbonate
  • the carboxylic acid esters include propyl butyrate (PB), propyl acetate (PA), isopropyl acetate (IPA), butyl propionate (BP), isopropyl propionate (IPP), butyl Any one or a combination of at least two of ethyl propionate (EB), methyl propionate (EM), ethyl propionate (EP) or propyl propionate (PP).
  • PB propyl butyrate
  • PA propyl acetate
  • IPA isopropyl acetate
  • BP butyl propionate
  • IPP isopropyl propionate
  • EB ethyl propionate
  • EM methyl propionate
  • EP ethyl propionate
  • PP propyl propionate
  • the fluoroether has less than 7 (eg 5, 6, etc.) carbon atoms.
  • the aromatic hydrocarbons include halogenated aromatic hydrocarbons and/or non-halogenated aromatic hydrocarbons.
  • the halogenated aromatic hydrocarbons include any one of monofluorobenzene, difluorobenzene, 1,3,5-trifluorobenzene, trifluorotoluene, 2-fluorotoluene or 2,4-dichlorotrifluorotoluene or a combination of at least two.
  • the weight percentage of the electrolyte in the electrolyte solution is 8%-49%, such as 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, etc.
  • the weight percentage of the organic solvent in the electrolyte is 40%-85%, such as 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, etc.
  • the weight percentage of the additive represented by formula I in the electrolyte is 0.01%-5%, such as 0.04%, 0.06%, 0.08%, 0.1%, 0.3%, 0.5%, 0.6%, 0.8% %, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, etc.
  • the weight percentage of the additive described in the application in the electrolyte is within the range of 0.01%-5%.
  • the electrolyte obtained is more conducive to the improvement of the overall performance of the battery.
  • the additive is less than 0.01%, the improvement effect is not obvious, and it exceeds 5%. content, the performance improvement decreases, and the cost is too expensive.
  • the electrolyte solution also includes other additives.
  • additives mentioned in this application refer to additives other than the additives shown in formula I, such as vinylene carbonate, 1,3-propane sultone and vinyl sulfate.
  • an embodiment of the present application provides a battery, which includes the electrolyte solution described in the first aspect.
  • the battery includes a lithium ion battery, a sodium ion battery, a potassium ion battery or a supercapacitor.
  • the negative electrode material of the lithium ion battery includes any one of graphite, soft carbon, hard carbon, composite material of single crystal silicon and graphite, composite material of silicon oxide and graphite, lithium titanate or niobium pentoxide one or a combination of at least two.
  • the charge-discharge cycle performance and low-temperature discharge performance of the obtained batteries are improved, and the 3C discharge rate of the batteries obtained in the examples of the present application at room temperature is below Above 80.6%, the 1C discharge rate at -20°C is above 81.0%, the capacity retention rate of 1000 cycles at room temperature is above 80.01%, and the capacity retention rate at 1000 cycles at 45°C is above 74.12%, with excellent comprehensive performance.
  • Discharge rate performance 1C current is 1.67A, 3C current is 5.01A; charge and discharge potential range is 2.75V ⁇ 4.20V.
  • the discharge rate at 3C at room temperature is the ratio of the capacity C2 discharged at 3C to the capacity C1 discharged at 1C.
  • Cycle performance charge and discharge potential range is 2.75V ⁇ 4.20V, charge current is 1C (1.67A) to 4.20V, 4.20V constant voltage charge to cut-off current ⁇ 0.02C (0.0334A), after standing for 5 minutes , 1C (1.67A) discharge to 2.75V, stand for 5 minutes; so cycle charge and discharge.
  • Example 1 85.3% 89.0%
  • Example 2 82.1% 86.4%
  • Example 3 84.2% 87.5%
  • Example 4 83.9% 87.0%
  • Example 5 82.3% 86.1%
  • Example 6 81.5% 85.7%
  • Example 7 82.4%
  • Example 8 83.2%
  • Example 9 82.5% 85.9%
  • Example 10 85.6% 85.2%
  • Example 11 80.6% 81.0%
  • Example 12 82.7% 84.6% Comparative example 1 80.0% 80.0% Comparative example 2 81.1% 79.1%
  • the present application illustrates the detailed method of the present application through the above-mentioned embodiments, but the present application is not limited to the above-mentioned detailed method, that is, it does not mean that the present application must rely on the above-mentioned detailed method to be implemented.
  • Those skilled in the art should understand that any improvement to the present application, the equivalent replacement of each raw material of the product of the present application, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present application.

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Abstract

一种电解液及包含该电解液的电池，所述电解液包括电解质、有机溶剂和式Ⅰ所示的添加剂；其中，R 1、R 2、R 3和R 4各自独立地包括：C1-C10烷基、C6-C20芳香烃基、C3-C10烷氧基、C2-C10烯基或C2-C10炔基中的任意一种；所述R 1、R 2、R 3和R 4中至少一个为C2-C10烯基或C2-C10炔基；所述R 5包括双氟代磺酰亚胺根、双三氟甲烷磺酰亚胺根、二氟草酸硼酸根、双乙二酸硼酸根、二氟二草酸磷酸根或六氟磷酸根中的任意一种。所述电解液能够提高电池的倍率放电性能，循环性能，低温放电性能。

Description

一种电解液及包含该电解液的电池 技术领域
本申请实施例涉及电池技术领域，例如一种电解液及包含该电解液的电池。
背景技术
电池电解液对电池的使用寿命、储存寿命、容量发挥、高低温和安全性能等都有至关重要的影响。目前，商业电解液主要是溶解有六氟磷酸锂(LiPF 6)的环状碳酸酯和链状碳酸酯的二元或三元混合溶剂体系，该体系具有溶解性好、离子电导率高和在石墨负极表面能形成稳定的固态电解质界面膜(SEI膜)等特点，被认为是电解液溶剂体系的最佳选择。然而，有机碳酸酯类溶剂却存在易挥发、易燃、抗氧化性不足等缺陷，导致了电池安全性下降。
在电解液中加入少量非储能物质，可以有效的改善电池的某些性能，如电解液的电导率、正负极匹配性能、电池的容量、循环效率、循环寿命、可逆容量和安全性能等。根据其作用机理，可将添加剂分为SEI成膜添加剂、导电添加剂、阻燃添加剂、过充电保护添加剂、提高电解液低温性能添加剂、改善电解液热稳定性添加剂、控制电解液中酸和水含量的添加剂等。
CN110911750A公开了高电压锂离子电池电解液、添加剂及该添加剂的制备方法，其公开的添加剂为硫脲衍生物盐，其公开的添加剂制备方法包括以下步骤：(1)首先将溶剂、催化剂和硫脲置于反应容器中，逐渐滴加有机酸，冰水浴下进行缩聚反应得到硫脲脂类化合物；(2)通过分水器和高温减压蒸馏将副产物分离得到硫脲酯类化合物粗产品；(3)采用溶剂萃取产物，重结晶提纯，干燥后得到硫脲脂类化合物。该硫脲酯类化合物可做为高压锂离子电池电解液的添加剂，可捕获正极材料在高电压下产生的氧自由基，又可以形成SEI膜。
CN103094616A公开了一种电解液添加剂和含有该电解液添加剂的高电压电解液及锂离子电池，其公开的电解液添加剂为顺丁烯二酸酐C 4H 2O 3或者其衍生物中的一种，其公开的高电压电解液可以在正负极表面形成稳定的界面膜，抑制电极表面的反应活性，减少电解液的氧化分解，有效地抑制胀气，从而提高锂离子电池的安全性能、在常压和高电压下的循环性能和使用寿命。
但是，工业生产高能量密度的需求和大容量高电压电极材料要求越来越高， 因此开发一种能够提高电池的倍率放电性能，循环性能和低温放电性能的电解液至关重要。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
针对相关技术的不足，本申请实施例提供一种电解液及包含该电解液的电池，所述电解液能够提高电池的倍率放电性能，循环性能，低温放电性能。
第一方面，本申请实施例提供一种电解液，所述电解液包括电解质、有机溶剂和式Ⅰ所示的添加剂；
Figure PCTCN2021137033-appb-000001
其中，R 1、R 2、R 3和R 4各自独立地包括：C1-C10(例如C2、C4、C6、C8等)烷基、C6-C20(例如C8、C10、C12、C14、C16、C18等)芳香烃基、C3-C10(例如C4、C6、C8等)烷氧基、C2-C10(例如C2、C4、C6、C8等)烯基或C2-C10(例如C2、C4、C6、C8等)炔基中的任意一种；
所述R 1、R 2、R 3和R 4中至少一个为C2-C10烯基或C2-C10炔基；
所述R 5包括双氟代磺酰亚胺根(FSI)、双三氟甲烷磺酰亚胺根(TFSI)、二氟草酸硼酸根(DFOB)、双乙二酸硼酸根(BOB)、二氟二草酸磷酸根(DFOP)或六氟磷酸根(PF 6)中的任意一种。
本申请采用式Ⅰ所示化合物作为添加剂，利于正极聚合成膜，能够提高电池的倍率放电性能，循环性能，低温放电性能，尤其是对于负极材料为石墨，单晶硅与石墨的复合材料或氧化亚硅与石墨的复合材料的锂离子电池。
本申请所述“C1-C10”指的是对应基团碳原子的数目为1-10，“C6-C10”等同理。
优选地，所述R 1、R 2、R 3和R 4各自独立地包括：甲基、乙基、丙基、异丙基、烯丙基或炔丙基中的任意一种；
所述R 1、R 2、R 3和R 4中至少一个为烯丙基或炔丙基。
优选地，所述添加剂的结构式如式Ⅱ所示；
Figure PCTCN2021137033-appb-000002
所述R 1、R 2、R 3和R 4各自独立地包括：甲基，乙基，丙基，异丙基，烯丙基或炔丙基中的任意一种；
所述R 1、R 2、R 3和R 4中至少一个为烯丙基或炔丙基；
所述R 5包括双氟代磺酰亚胺根、双三氟甲烷磺酰亚胺根、二氟草酸硼酸根、双乙二酸硼酸根、二氟二草酸磷酸根或六氟磷酸根中的任意一种。
上述R 5的结构式分别如下：
Figure PCTCN2021137033-appb-000003
优选地，所述添加剂的结构式包括式Ⅲ或式Ⅳ中的任意一种；
Figure PCTCN2021137033-appb-000004
所述R 5为双氟代磺酰亚胺根、双三氟甲烷磺酰亚胺根或六氟磷酸根中的任意一种。
优选地，所述添加剂包括式Ⅲ或式Ⅳ所示结构的化合物中的任意一种或至少两种的组合，例如，添加剂包括但不限于如下化合物：
Figure PCTCN2021137033-appb-000005
优选地，所述电解质包括锂盐、钠盐或钾盐中的任意一种或至少两种的组合。
优选地，所述电解质包括XClO 4、XPF 6、XBF 4、XTFSI、XFSI、XBOB、XODFB，XCF 3SO 3或XAsF 6中的任意一种或至少两种的组合，其中典型但非限制性的组合包括：XClO 4和XPF 6的组合，XBF 4、XTFSI、XFSI和XBOB的组 合，XBF 4、XTFSI、XFSI、XBOB、XODFB，XCF 3SO 3和XAsF 6的组合等；
其中，X包括Li，Na或K中的任意一种。
优选地，所述有机溶剂包括非水性有机溶剂。
优选地，所述有机溶剂包括碳酸酯、羧酸酯、丙酸酯、氟醚或芳香烃中的任意一种或至少两种的组合，其中典型但非限制性的组合包括：碳酸酯和羧酸酯的组合，羧酸酯、丙酸酯和氟醚的组合，羧酸酯、丙酸酯、氟醚和芳香烃的组合等。
优选地，所述碳酸酯包括卤代碳酸酯和/或非卤代碳酸酯。
优选地，所述非卤代碳酸酯包括碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)或碳酸甲乙酯(EMC)中的任意一种或至少两种的组合。
优选地，所述卤代碳酸酯包括氟代碳酸乙烯酯(FEC)、二氟代碳酸乙烯酯、双氟碳酸丙烯酯、三氟代乙酸乙酯、三氟乙基甲基碳酸酯、三氟甲基碳酸乙烯酯、4-三氟代甲基碳酸乙烯酯、氯代碳酸乙烯酯、二(2,2,2-三氟乙基)碳酸酯、三氟丙酸甲酯、3,3,3-三氟代乙酸乙酯、2-三氟甲基苯甲酸甲酯、4,4,4-三氟丁酸乙酯或1,1,1,3,3,3-六氟异丙基丙烯酸酯中的任意一种或至少两种的组合。
优选地，所述羧酸酯包括丁酸丙酯(PB)、乙酸丙酯(PA)、乙酸异丙酯(IPA)、丙酸丁酯(BP)、丙酸异丙酯(IPP)、丁酸乙酯(EB)，丙酸甲酯(EM)、丙酸乙酯(EP)或丙酸丙酯(PP)中的任意一种或至少两种的组合。
优选地，所述氟醚为碳原子数为7个(例如5个、6个等)以下。
优选地，所述芳香烃包括卤代芳香烃和/或非卤代芳香烃。
优选地，所述卤代芳烃包括单氟苯、双氟苯、1,3,5-三氟苯、三氟甲苯、2-氟甲苯或2,4-二氯三氟甲苯中的任意一种或至少两种的组合。
优选地，所述电解质在所述电解液中的重量百分数为8％-49％，例如10％、15％、20％、25％、30％、35％、40％、45％等。
优选地，所述有机溶剂在所述电解液中的重量百分数为40％-85％，例如45％、50％、55％、60％、65％、70％、75％、80％等。
优选地，所述式Ⅰ所示的添加剂在所述电解液中的重量百分数为0.01％-5％，例如0.04％、0.06％、0.08％、0.1％、0.3％、0.5％、0.6％、0.8％、1％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％等。
本申请所述添加剂在所述电解液中的重量百分数为0.01％-5％范围内所得的电解液更利于电池综合性能的提升，此添加剂低于0.01％时，提升作用不明显，超过5％的含量，性能提升反而下降，并且成本过于昂贵。
优选地，所述电解液还包括其他添加剂。
本申请所述其他添加剂指的是式Ⅰ所示的添加剂以外的添加剂，例如碳酸亚乙烯酯、1,3-丙磺酸内酯和硫酸乙烯酯等。
第二方面，本申请实施例提供一种电池，所述电池包括第一方面所述的电解液。
优选地，所述电池包括锂离子电池、钠离子电池、钾离子电池或超级电容器。
优选地，所述锂离子电池的负极材料包括石墨、软碳、硬碳、单晶硅与石墨的复合材料、氧化亚硅与石墨的复合材料、钛酸锂或五氧化二铌中的任意一种或至少两种的组合。
相对于相关技术，本申请具有以下有益效果：
本申请实施例所述电解液通过添加式Ⅰ所示添加剂，在电池中使用时，所得电池的充放电循环性能和低温放电性能均得以提升，本申请实施例所得电池中常温下3C放电率在80.6％以上，-20℃下1C放电率在81.0％以上，常温循环1000次1C倍率的容量保持率在80.01％以上，45℃高温1C循环1000次容量保持率在74.12％以上，综合性能优异。
在阅读并理解了详细描述后，可以明白其他方面。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
实施例1-12和对比例1-2提供的电解液的组成如表1所示：
表1
Figure PCTCN2021137033-appb-000006
Figure PCTCN2021137033-appb-000007
Figure PCTCN2021137033-appb-000008
性能测试
将实施例1-12和对比例1-2所述电解液进行如下测试：
将实施例1-9、11-12和对比例1所述电解液添加到含硅碳的负极材料(贝特瑞S420)，正极材料为NCM811镍钴锰三元材料(容百S85ES)的1.67Ah的锂离子电池；
将实施例10和对比例2所述电解液添加到负极材料为石墨材料(杉杉P15)，正极材料为NCM811镍钴锰三元材料(容百S85ES)的电池中制备得到1.67Ah的锂离子电池；
进行如下测试：
(1)放电倍率性能：1C电流为1.67A，3C电流为5.01A；充电放电电位范围为2.75V～4.20V。常温3C的放电率为3C放电的容量C2与1C放电容量C1的比率。
(2)循环性能：充电放电电位范围为2.75V～4.20V，充电电流为1C(1.67A)到4.20V，4.20V恒压充电到截止电流≤0.02C(0.0334A)，静置5分钟后，1C(1.67A)放电到2.75V，静置5分钟；如此循环充电放电。
(3)低温放电性能：常温25℃下1C(1.67A)放电容量记为C1，4.2V满 充后，-20℃下冷冻4h后，以1C(1.67A)放电到2.75V，放电容量记为C2。-20℃下的放电率为C2/C1。
测试结果汇总于表2-表4中。
表2
  常温下3C放电率 -20℃下1C放电率
实施例1 85.3％ 89.0％
实施例2 82.1％ 86.4％
实施例3 84.2％ 87.5％
实施例4 83.9％ 87.0％
实施例5 82.3％ 86.1％
实施例6 81.5％ 85.7％
实施例7 82.4％ 86.3％
实施例8 83.2％ 86.1％
实施例9 82.5％ 85.9％
实施例10 85.6％ 85.2％
实施例11 80.6％ 81.0％
实施例12 82.7％ 84.6％
对比例1 80.0％ 80.0％
对比例2 81.1％ 79.1％
表3
Figure PCTCN2021137033-appb-000009
Figure PCTCN2021137033-appb-000010
表4
Figure PCTCN2021137033-appb-000011
Figure PCTCN2021137033-appb-000012
分析表2-表4数据可知，本申请所述电解液通过添加式Ⅰ所示添加剂，在电池中使用时，所得电池的充放电循环性能和低温放电性能均得以提升，本申请所得电池中常温下3C放电率在80.6％以上，-20℃下1C放电率在81.0％以上，常温循环1000次1C倍率的容量保持率在80.01％以上，45℃高温1C循环1000次容量保持率在74.12％以上，综合性能优异。
分析对比例1与实施例1可知，对比例1性能不如实施例1，证明添加式Ⅰ所示添加剂的电解液能够提升电池的综合性能。
分析对比例2与实施例10可知有类似的结果，证明添加式Ⅰ所示添加剂的电解液利于含硅材料或石墨为负极的电池的充放电循环性能和低温放电性能。
分析实施例11-12、对比例1与实施例2可知，对比例1和实施例12的性能不如实施例2和实施例11，证明式Ⅰ所示添加剂在电解液中的重点百分数为0.01％-5％范围内利于电池综合性能的提升。
本申请通过上述实施例来说明本申请的详细方法，但本申请并不局限于上述详细方法，即不意味着本申请必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本申请的任何改进，对本申请产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本申请的保护范围和公开范围之内。

Claims (11)

  1. 一种电解液，其中，所述电解液包括电解质、有机溶剂和式Ⅰ所示的添加剂；
    Figure PCTCN2021137033-appb-100001
    其中，R 1、R 2、R 3和R 4各自独立地包括：C1-C10烷基、C6-C20芳香烃基、C3-C10烷氧基、C2-C10烯基或C2-C10炔基中的任意一种；
    所述R 1、R 2、R 3和R 4中至少一个为C2-C10烯基或C2-C10炔基；
    所述R 5包括双氟代磺酰亚胺根、双三氟甲烷磺酰亚胺根、二氟草酸硼酸根、双乙二酸硼酸根、二氟二草酸磷酸根或六氟磷酸根中的任意一种。
  2. 根据权利要求1所述的电解液，其中，所述R 1、R 2、R 3和R 4各自独立地包括：甲基，乙基，丙基，异丙基，烯丙基或炔丙基中的任意一种；
    所述R 1、R 2、R 3和R 4中至少一个为烯丙基或炔丙基。
  3. 根据权利要求1或2所述的电解液，其中，所述添加剂的结构式如式Ⅱ所示；
    Figure PCTCN2021137033-appb-100002
    所述R 1、R 2、R 3和R 4各自独立地包括：甲基、乙基、丙基、异丙基、烯丙基或炔丙基中的任意一种；
    所述R 1、R 2、R 3和R 4中至少一个为烯丙基或炔丙基；
    所述R 5包括双氟代磺酰亚胺根、双三氟甲烷磺酰亚胺根、二氟草酸硼酸根、双乙二酸硼酸根、二氟二草酸磷酸根或六氟磷酸根中的任意一种。
  4. 根据权利要求1-3任一项所述的电解液，其中，所述添加剂的结构式包括式Ⅲ或式Ⅳ中的任意一种；
    Figure PCTCN2021137033-appb-100003
    Figure PCTCN2021137033-appb-100004
    所述R 5为双氟代磺酰亚胺根、双三氟甲烷磺酰亚胺根或六氟磷酸根中的任意一种。
  5. 根据权利要求1-4任一项所述的电解液，其中，所述添加剂包括式Ⅲ或式Ⅳ所示结构的化合物中的任意一种或至少两种的组合。
  6. 根据权利要求1-5任一项所述的电解液，其中，所述电解质包括锂盐、钠盐或钾盐中的任意一种或至少两种的组合；
    优选地，所述电解质包括XClO 4、XPF 6、XBF 4、XTFSI、XFSI、XBOB、XODFB，XCF 3SO 3或XAsF 6中的任意一种或至少两种的组合；
    其中，X包括Li，Na或K中的任意一种。
  7. 根据权利要求1-6任一项所述的电解液，其中，所述有机溶剂包括非水性有机溶剂；
    优选地，所述有机溶剂包括碳酸酯、羧酸酯、丙酸酯、氟醚或芳香烃中的任意一种或至少两种的组合；
    优选地，所述碳酸酯包括卤代碳酸酯和/或非卤代碳酸酯；
    优选地，所述非卤代碳酸酯包括碳酸乙烯酯、碳酸丙烯酯、碳酸二乙酯、碳酸二甲酯或碳酸甲乙酯中的任意一种或至少两种的组合；
    优选地，所述卤代碳酸酯包括氟代碳酸乙烯酯、二氟代碳酸乙烯酯、双氟碳酸丙烯酯、三氟代乙酸乙酯、三氟乙基甲基碳酸酯、三氟甲基碳酸乙烯酯、4-三氟代甲基碳酸乙烯酯、氯代碳酸乙烯酯、二(2,2,2-三氟乙基)碳酸酯、三氟丙酸甲酯、3,3,3-三氟代乙酸乙酯、2-三氟甲基苯甲酸甲酯、4,4,4-三氟丁酸乙酯或1,1,1,3,3,3-六氟异丙基丙烯酸酯中的任意一种或至少两种的组合；
    优选地，所述羧酸酯包括丁酸丙酯、乙酸丙酯、乙酸异丙酯、丙酸丁酯、丙酸异丙酯、丁酸乙酯，丙酸甲酯、丙酸乙酯或丙酸丙酯中的任意一种或至少两种的组合；
    优选地，所述氟醚为碳原子数为7个以下；
    优选地，所述芳香烃包括卤代芳香烃和/或非卤代芳香烃；
    优选地，所述卤代芳烃包括单氟苯、双氟苯、1,3,5-三氟苯、三氟甲苯、2-氟甲苯或2,4-二氯三氟甲苯中的任意一种或至少两种的组合。
  8. 根据权利要求1-7任一项所述的电解液，其中，所述电解质在所述电解液中的重量百分数为8％-49％；
    优选地，所述有机溶剂在所述电解液中的重量百分数为40％-85％；
    优选地，所述式Ⅰ所示的添加剂在所述电解液中的重量百分数为0.01％-5％；
    优选地，所述电解液还包括其他添加剂。
  9. 一种电池，其中，所述电池包括权利要求1-8任一项所述的电解液。
  10. 根据权利要求9所述的电池，其中，所述电池包括锂离子电池、钠离子电池、钾离子电池或超级电容器。
  11. 根据权利要求9或10所述的电池，其中，所述锂离子电池的负极材料包括石墨、软碳、硬碳、单晶硅与石墨的复合材料、氧化亚硅与石墨的复合材料、钛酸锂或五氧化二铌中的任意一种或至少两种的组合。
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