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WO2018120787A1 - 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
WO2018120787A1
WO2018120787A1 PCT/CN2017/093744 CN2017093744W WO2018120787A1 WO 2018120787 A1 WO2018120787 A1 WO 2018120787A1 CN 2017093744 W CN2017093744 W CN 2017093744W WO 2018120787 A1 WO2018120787 A1 WO 2018120787A1
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chloro
group
electrolyte
ethyl
secondary battery
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French (fr)
Inventor
王小梅
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
    • H01M10/056—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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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.
  • a widely used electrolyte for a lithium ion secondary battery includes a lithium hexafluorophosphate as a conductive lithium salt and a mixture of a cyclic carbonate and a chain carbonate as an organic solvent, but the above electrolyte still has many disadvantages, particularly At high voltages, lithium ion secondary batteries have poor performance, such as poor high temperature cycle performance, poor high temperature storage performance, and poor rate performance.
  • an object of the present invention is to provide an electrolyte and a secondary battery, which can simultaneously improve the rate performance of a secondary battery at a high temperature and a high voltage when the electrolyte is applied to a secondary battery. , loop performance and storage performance.
  • the present invention provides an electrolyte comprising an electrolyte salt, an organic solvent, and an additive.
  • the organic solvent includes a carboxylate compound.
  • the additives include cyclic sulfates and triphenyl phosphite.
  • the invention provides a secondary battery comprising an electrolyte according to an aspect of the invention.
  • the electrolyte of the present invention includes a carboxylate compound, a cyclic sulfate, and a triphenyl phosphite.
  • a carboxylate compound When applied to a secondary battery, the synergistic action of the three can simultaneously increase the secondary battery at a high temperature. Rate performance, cycle performance, and storage performance at voltage.
  • the electrolytic solution according to the first aspect of the invention includes: an electrolyte salt, an organic solvent, and an additive.
  • the organic solvent includes a carboxylate compound.
  • the additives include cyclic sulfates and triphenyl phosphite.
  • the carboxylate compound is used for improving the rate performance of the secondary battery, but when the carboxylate compound is applied to a secondary battery of a high voltage system, it is easily oxidized.
  • the secondary battery using the carboxylic acid ester compound is decomposed and used in a high-temperature environment, the capacity loss after repeated cycles of the secondary battery is severe, and the high-temperature storage performance of the secondary battery is seriously deteriorated.
  • the cyclic sulfate has a high reduction potential, and can preferentially form a film on the surface of the negative electrode to suppress reduction of the carboxylate compound, thereby improving the cycle performance of the secondary battery.
  • Triphenyl phosphite can react with HF to reduce the HF, thereby improving the high-temperature storage performance of the secondary battery.
  • the electrolyte includes three substances at the same time, under the synergistic action of the three, the rate performance, cycle performance and storage performance of the secondary battery at high temperature and high voltage can be simultaneously improved.
  • the carboxylic acid ester compound is selected from one or more of the compounds represented by the formula I.
  • R 1 and R 2 are each independently selected from the group consisting of an alkane group having 1 to 10 carbon atoms and a halogenated alkane group having 1 to 10 carbon atoms; and the halogen atom in the halogenated alkane group is selected from the group consisting of F and Cl.
  • the alkane group having 1 to 10 carbon atoms may be a chain alkane group or a cyclic alkane group.
  • the chain alkane group further includes a linear alkane group and a branched alkane group.
  • the cyclic alkane group may have a substituent or may not contain a substituent.
  • a preferred lower limit of the number of carbon atoms may be 1, 2, and 3, and a preferred upper limit of the number of carbon atoms may be 4, 5, 6, 7, 8, or 10.
  • R 1 and R 2 are each independently selected from a chain alkane group having 1 to 6 carbon atoms or a cyclic alkane group having 3 to 8 carbon atoms. Still more preferably, R 1 and R 2 are each independently selected from a chain alkane group having 1 to 4 carbon atoms or a cyclic alkane group having 5 to 7 carbon atoms.
  • the alkane group having 1 to 10 carbon atoms may be selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, Cyclobutyl, n-pentyl, isopentyl, tert-amyl, neopentyl, cyclopentyl, 2,2 dimethylpropyl, 1-ethylpropyl, 1-methylbutyl, 2-methyl Butyl, n-hexyl, isohexyl, 2-hexyl, 3-hexyl, cyclohexyl, 2-methylpentyl, 3-methylpentyl, 1,1,2-trimethylpropyl, 3,3 - dimethylbutyl, n-heptyl, 2-heptyl, 3-heptyl, 2-methylhexyl, 3-methylhexyl,
  • the number of substitution of the halogen atom in the halogenated alkane group having 1 to 10 carbon atoms and the position of substitution thereof are not particularly limited, and may be selected according to actual needs.
  • the number of halogen atoms may be one, two, three or four.
  • the types of the halogen atoms may be the same, or they may be completely different or partially the same.
  • the haloalkane group may be a chain haloalkane group or a cyclic haloalkane group.
  • the chain haloalkane group in turn includes a linear haloalkane group and a branched haloalkane group.
  • the cyclic haloalkane group may or may not have a substituent.
  • a preferred lower limit of the number of carbon atoms may be 1, 2, and 3, and a preferred upper limit of the number of carbon atoms may be 4, 5, 6, 7, 8, or 10.
  • R 1 and R 2 are each independently selected from a chain halogenated alkane group having 1 to 6 carbon atoms or a cyclic halogenated alkane group having 3 to 8 carbon atoms. Still more preferably, each of R 1 and R 2 is independently selected from a chain halogenated alkane group having 1 to 4 carbon atoms or a cyclic halogenated alkane group having 5 to 7 carbon atoms.
  • the halogenated alkane group having 1 to 10 carbon atoms is selected from the group consisting of chloromethyl, dichloromethyl, trichloromethyl, 1-chloroethyl, 1,2-dichloroethyl, 2-chloro-n-propyl , 2,2-dichloro-n-propyl, 1-chloroisopropyl, monochlorocyclopropyl, 1-chloro-n-butyl, 2-chloroisobutyl, monochlorocyclobutyl, 1-chloro-n-pentane Base, 2-chloro-n-pentyl, 1-chloroisopentyl, 2,2-dichloromethylpropyl, monochlorocyclopentyl, 3-chloro-2,2-dimethylpropyl, 1-chloro 1-ethylpropyl, 1-chloro-1-methylbutyl, 2-chloro-2-methylbutyl, 2-chloro-n-hexy
  • the carboxylic acid ester compound may be selected from the group consisting of methyl formate, ethyl formate, ethyl acetate, ethyl propionate, ethyl valerate, and ethyl isovalerate.
  • the cyclic sulfate is selected from one or more of the compounds represented by the formula II.
  • n is an integer within 1 to 3; and R 3 , R 4 , R 5 and R 6 are each independently selected from the group consisting of H, F, Cl, Br, I, an alkyl group having 1 to 10 carbon atoms, and a carbon atom.
  • One of the alkoxy groups having 1 to 10, wherein the H 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 triphenyl phosphite structure is as follows:
  • the volume of the carboxylate compound is 5% to 50% of the total volume of the organic solvent.
  • the volume of the carboxylic acid ester compound is from 10% to 40% of the total volume of the organic solvent.
  • the volume of the carboxylate compound is from 20% to 35% of the total volume of the organic solvent.
  • the content of the cyclic sulfate is 0.5% to 10% of the total weight of the electrolytic solution.
  • the cyclic sulfate is present in an amount of from 1% to 5% by weight based on the total weight of the electrolyte.
  • the content of the triphenyl phosphite is 0.03% to 1% of the total weight of the electrolytic solution.
  • the content of the triphenyl phosphite is from 0.1% to 0.3% 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 organic solvent may also include halogenated compounds of any kind of carbonates and carbonates.
  • the carbonate includes a cyclic carbonate and a chain carbonate.
  • the organic solvent may further include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, pentylene carbonate, fluoroethylene carbonate, dimethyl carbonate, and diethyl carbonate.
  • EC ethylene carbonate
  • PC propylene carbonate
  • butylene carbonate pentylene carbonate
  • fluoroethylene carbonate dimethyl carbonate
  • diethyl carbonate diethyl carbonate
  • ester DEC
  • dipropyl carbonate dipropyl carbonate
  • ethyl methyl carbonate ⁇ -butyrolactone
  • tetrahydrofuran tetrahydrofuran.
  • 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.
  • the content of the electrolyte salt is 6.25% to 18.8% of the total weight of the electrolyte.
  • the content of the electrolyte salt is 10% to 15% of the total weight of the electrolyte.
  • the electrolyte in the present application can be prepared by a conventional method, that is, the materials in the electrolyte are uniformly mixed.
  • 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 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 active slurry layer on the positive electrode current collector, wherein the positive electrode active slurry layer includes a positive electrode active layer material.
  • the specific type of the positive electrode active material is not particularly limited and can be selected according to requirements.
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode active slurry layer on the negative electrode current collector.
  • the negative active slurry layer includes a negative active material.
  • the specific type of the negative active material is not particularly limited and can be selected according to requirements.
  • the specific type of the separator is not affected
  • a specific limitation may be any separator material used in the existing secondary battery, such as polyethylene, polypropylene, polyvinylidene fluoride, and a multilayer composite film thereof, but is not limited thereto.
  • the secondary battery may be a lithium ion secondary battery, a sodium ion secondary battery, or a zinc ion secondary battery.
  • the positive electrode active material is selected from lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), olivine-type lithium iron phosphate (LiFePO 4 ), Olivine-type LiMPO 4 , spinel-type LiMn 2 O 4 , ternary cathode material LiNi x A y B (1-xy) O 2 and Li 1-x' (A' y' B' z' C 1 -y'-z' ) One or several of O 2 .
  • M is selected from one or more of Co, Ni, Fe, Mn, V; A and B are each independently selected from one of Co, Al, and Mn, and A and B are not the same; 0 ⁇ x ⁇ 1,0 ⁇ y ⁇ 1 and x+y ⁇ 1;0 ⁇ x' ⁇ 1,0 ⁇ y' ⁇ 1,0 ⁇ z' ⁇ 1 and y'+z' ⁇ 1;A',B', C is each independently selected from one of Co, Ni, Fe, and Mn, and A', B', and C are different.
  • the negative active material may be selected from metallic lithium, and the negative active material may also be selected from materials capable of intercalating lithium when the electrode potential of the Li/Li + equilibrium potential is ⁇ 2V.
  • the anode active material is selected from the group consisting of natural graphite, artificial graphite, mesophase micro carbon spheres (abbreviated as MCMB), hard carbon, soft carbon, silicon, silicon-carbon composite, Li-Sn alloy, Li-Sn- One or more of an O alloy, Sn, SnO, SnO 2 , a lithiated lithiated TiO 2 -Li 4 Ti 5 O 12 , Li-Al alloy.
  • the electrolyte salt may be a lithium salt, and the lithium salt may be selected from LiPF 6 , LiBF 4 , LiN(SO 2 F) 2 (abbreviated as LiFSi), LiN(CF 3 SO 2 ) 2 (abbreviated as LiTFSi), LiClO. 4 , one or more of LiAsF 6 , LiB(C 2 O 4 ) 2 (abbreviated as LiBOB), LiBF 2 C 2 O 4 (abbreviated as LiDFOB), and LiPO 2 F 2 .
  • LiPF 6 LiBF 4
  • LiN(SO 2 F) 2 abbreviated as LiFSi
  • LiTFSi LiN(CF 3 SO 2 ) 2
  • LiClO. 4 LiClO. 4
  • LiAsF 6 LiB(C 2 O 4 ) 2
  • LiBOB LiBF 2 C 2 O 4
  • LiDFOB LiBF 2 C 2 O 4
  • the lithium ion secondary batteries of Examples 1 to 11 and Comparative Examples 1 to 7 were each prepared in the following manner.
  • the positive electrode active material lithium cobaltate (LiCoO 2 ), the binder polyvinylidene fluoride, and the conductive agent acetylene black were mixed at a weight ratio of 98:1:1, and N-methylpyrrolidone (NMP) was added thereto under the action of a vacuum mixer.
  • NMP N-methylpyrrolidone
  • the negative electrode active material artificial graphite, thickener sodium carboxymethyl cellulose (CMC), binder styrene-butadiene rubber were mixed at a weight ratio of 98:1:1, deionized water was added, and the negative electrode slurry was obtained under the action of a vacuum mixer.
  • the negative electrode slurry was uniformly coated on a negative electrode current collector copper foil having a thickness of 8 ⁇ m; the copper foil was air-dried at room temperature, transferred to an oven at 120 ° C for 1 hour, and then subjected to cold pressing and slitting to obtain a negative electrode sheet.
  • the content of the carboxylate compound is a volume percentage calculated based on the total volume of the organic solvent
  • the content of the cyclic sulfate and the triphenyl phosphite is a weight percentage calculated based on the total weight of the electrolyte.
  • a 16 ⁇ m thick polypropylene separator (model A273, 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 packaging foil, The prepared electrolyte solution is injected into the dried bare cell, and subjected to vacuum encapsulation, standing, formation, shaping, and the like to obtain a lithium ion secondary battery.
  • the lithium ion secondary battery was charged at a constant current of 1 C (nominal capacity) to a voltage of 4.4 V at 25 ° C, and then charged at a constant voltage of 4.4 V until the current was less than or equal to 0.05 C. After leaving for 5 minutes, the constant current was discharged at 0.2 C. The electric current is up to the voltage of 3V, and the discharge capacity at this time is recorded as D0.
  • the lithium ion secondary battery is charged at a constant current of 1 C to a voltage of 4.4 V, and then charged at a constant voltage of 4.4 V until the current is less than or equal to 0.05 C. After being left for 5 minutes, the battery is discharged at a constant current of 2 C to a voltage of 3 V, and the discharge is performed at this time. The capacity is recorded as D1.
  • Lithium ion secondary battery 2C/0.2C rate performance D1/D0 ⁇ 100%.
  • the lithium ion secondary battery is first charged at a constant current of 1 C to a voltage of 4.4 V, further charged at a constant voltage of 4.4 V until the current is 0.05 C, and then discharged at a constant current of 1 C to a voltage of 3.0 V, which is A 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 300 cycles (discharge capacity of 300 cycles of lithium ion secondary battery / discharge capacity of the first cycle of lithium ion secondary battery) ⁇ 100%.
  • the lithium ion secondary battery was charged at a constant current of 0.5 C to a voltage of 4.4 V at 85 ° C, and then charged at a constant voltage of 4.4 V until the current was 0.05 C. At this time, the thickness of the lithium ion secondary battery was tested and recorded as h. 0 ; After that, the lithium ion secondary battery was placed in an oven at 85 ° C, and stored for 24 hours, and then 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 24 hours of storage [(h 1 -h 0 ) / h 0 ] ⁇ 100%.
  • Table 1 gives the parameters and performance test results of Examples 1-11 and Comparative Examples 1-7.
  • the lithium ion secondary battery has better rate performance, and has better high temperature cycle performance and high temperature storage performance.

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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。所述有机溶剂包括羧酸酯化合物。所述添加剂包括环状硫酸酯以及亚磷酸三苯酯。当电解液应用到二次电池后，在三者的协同作用下，能够同时提高二次电池在高温高电压下的倍率性能、循环性能以及存储性能。

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，锂离子二次电池广泛应用的电解液包括作为导电锂盐的六氟磷酸锂和作为有机溶剂的环状碳酸酯和链状碳酸酯的混合物，然而上述电解液仍存在诸多的不足，特别的是在高电压下，锂离子二次电池的性能较差，例如高温循环性能差、高温存储性能差以及倍率性能差。
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，能同时提高二次电池在高温高电压下的倍率性能、循环性能以及存储性能。
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。所述有机溶剂包括羧酸酯化合物。所述添加剂包括环状硫酸酯以及亚磷酸三苯酯。
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羧酸酯化合物、环状硫酸酯以及亚磷酸三苯酯，当其应用到二次电池中后，在三者的协同作用下，能够同时提高二次电池在高温高电压下的倍率性能、循环性能以及存储性能。
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。所述有机溶剂包括羧酸酯化合物。所述添加剂包括环状硫酸酯以及亚磷酸三苯酯。
在根据本发明第一方面所述的电解液中，所述羧酸酯化合物用于改善二次电池的倍率性能，但当羧酸酯化合物应用于高电压体系的二次电池时，容易被氧化分解，另外使用羧酸酯化合物的二次电池在高温环境下使用时，二次电池多次循环后的容量损失严重，且二次电池的高温存储性能劣化严重。环状硫酸酯具有较高的还原电位，能优先在负极表面成膜，抑制羧酸酯化合物的还原，从而改善二次电池的循环性能。亚磷酸三苯酯能与HF发生反应，起到降低HF的作用，从而改善二次电池的高温存储性能。当电解液中同时包括三种物质时，在三者的协同作用下，能够同时提高二次电池在高温高电压下的倍率性能、循环性能以及存储性能。
在根据本发明第一方面所述的电解液中，所述羧酸酯化合物选自式Ⅰ所示的化合物中的一种或几种。其中，R1、R2各自独立地选自碳原子数为1～10的烷烃基、碳原子数为1～10的卤代烷烃基中的一种；卤代烷烃基中的卤原子选自F、Cl、Br、I中的一种或几种。
Figure PCTCN2017093744-appb-000001
在根据本发明第一方面所述的电解液中，所述碳原子数为1～10的烷烃基可为链状烷烃基，也可为环状烷烃基。其中，链状烷烃基又包括直链烷烃基和支链烷烃基。另外，环状烷烃基上可以有取代基，也可以不含有取代基。 在所述烷烃基中，碳原子数的优选的下限值可为1、2、3，碳原子数的优选的上限值可为4、5、6、7、8、10。优选地，R1、R2各自独立地选自碳原子数为1～6的链状烷烃基或碳原子数为3～8的环状烷烃基。更进一步优选地，R1、R2各自独立地选自碳原子数为1～4的链状烷烃基或碳原子数为5～7的环状烷烃基。
具体地，碳原子数为1～10的烷烃基可选自甲基、乙基、正丙基、异丙基、环丙基、正丁基、异丁基、仲丁基、叔丁基、环丁基、正戊基、异戊基、叔戊基、新戊基、环戊基、2,2二甲基丙基、1-乙基丙基、1-甲基丁基、2-甲基丁基、正己基、异己基、2-己基、3-己基、环己基、2-甲基戊基、3-甲基戊基、1,1,2-三甲基丙基、3,3-二甲基丁基、正庚基、2-庚基、3-庚基、2-甲基己基、3-甲基己基、4-甲基己基、异庚基、环庚基、正辛基、环辛基、壬基、癸基中的一种。
在根据本发明第一方面所述的电解液中，所述碳原子数为1～10的卤代烷烃基中卤原子的取代个数及其取代位置并没有特别的限制，可根据实际需求进行选择。具体地，卤原子的个数可为1个、2个、3个或4个。当卤原子的个数为2个以上时，卤原子的种类可以相同，也可以完全不同，也可以部分相同。卤代烷烃基可为链状卤代烷烃基也可为环状卤代烷烃基。链状卤代烷烃基又包括直链卤代烷烃基和支链卤代烷烃基。环状卤代烷烃基上可以有取代基，也可以不含有取代基。在所述卤代烷烃基中，碳原子数的优选的下限值可为1、2、3，碳原子数的优选的上限值可为4、5、6、7、8、10。优选地，R1、R2各自独立地选自碳原子数为1～6的链状卤代烷烃基或碳原子数为3～8的环状卤代烷烃基。更进一步优选地，R1、R2各自独立地选自碳原子数为1～4的链状卤代烷烃基或碳原子数为5～7的环状卤代烷烃基。
具体地，碳原子数为1～10的卤代烷烃基选自氯甲基、二氯甲基、三氯甲基、1-氯乙基、1,2-二氯乙基、2-氯正丙基、2,2-二氯-正丙基、1-氯异丙基、一氯环丙基、1-氯正丁基、2-氯异丁基、一氯环丁基、1-氯正戊基、2-氯正戊基、1-氯异戊基、2,2-二氯甲基丙基、一氯环戊基、3-氯-2,2-二甲基丙基、1-氯-1-乙基丙基、1-氯-1-甲基丁基、2-氯-2-甲基丁基、2-氯正己基、一氯环己基、2-氯甲基戊基、3-氯-3-甲基戊基、2-氯-1,1,2-三甲基丙基、4-氯-3,3-二甲基丁基、2-氯正庚基中的一种。在上述的基团中，卤代烷烃基中的Cl原子还 可被F、Br、I中的一种或几种部分取代或全部取代。
在根据本发明第一方面所述的电解液中，所述羧酸酯化合物可选自甲酸甲酯、甲酸乙酯、乙酸乙酯、丙酸乙酯、戊酸乙酯、异戊酸乙酯、丙酸丙酯、丙酸丁酯、丙酸异丁酯、丁酸丁酯、异丁酸丁酯、丁酸戊酯、丁酸异戊酯、丙酸戊酯、丙酸异戊酯、异丙酸乙酯、丁酸乙酯、异丁酸乙酯、戊酸丙酯、异戊酸丙酯、异戊酸乙酯以及前述具体的羧酸酯化合物被F、Cl、Br、I中的一种或几种部分取代或全部取代的化合物中的一种或几种。
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Ⅱ所示的化合物中的一种或几种。其中，n为1～3内的整数；R3、R4、R5、R6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还可被F、Cl、Br、I中的一种或几种取代。
Figure PCTCN2017093744-appb-000002
在根据本发明第一方面所述的电解液中，具体地，所述环状硫酸酯选自下述化合物中的一种或几种；
Figure PCTCN2017093744-appb-000003
Figure PCTCN2017093744-appb-000004
在根据本发明第一方面所述的电解液中，所述亚磷酸三苯酯结构如下：
Figure PCTCN2017093744-appb-000005
在根据本发明第一方面所述的电解液中，所述羧酸酯化合物的体积为所述有机溶剂的总体积的5％～50％。优选地，所述羧酸酯化合物的体积为所述有机溶剂的总体积的10％～40％。进一步优选地，所述羧酸酯化合物的体积为所述有机溶剂的总体积的20％～35％。
在根据本发明第一方面所述的电解液中，所述环状硫酸酯的含量为所述电解液的总重量的0.5％～10％。优选地，所述环状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，所述亚磷酸三苯酯的含量为所述电解液的总重量的0.03％～1％。优选地，所述亚磷酸三苯酯的含量为所述电解液的总重量的0.1％～0.3％。
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。所述有机溶剂还可包括任意种类的碳酸酯及碳酸酯的卤代化合物。所述碳酸酯包括环状碳酸酯和链状碳酸酯。具体地，所述有机溶剂还可包括碳酸亚乙酯(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、碳酸二乙酯(DEC)、碳酸二丙酯、碳酸甲乙酯、γ-丁内酯、四氢呋喃中的一种或几种。
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％。
本申请中电解液采用常规方法制备即可，即将电解液中的各个物料混合均匀即可。
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，所述二次电池还包括正极片、负极片、隔离膜。
在根据本发明第二方面所述的二次电池中，所述正极片包括正极集流体和位于所述正极集流体上的正极活性浆料层，其中，所述正极活性浆料层包括正极活性材料。其中，所述正极活性材料的具体种类均不受到具体的限制，可根据需求进行选择。
在根据本发明第二方面所述的二次电池中，所述负极片包括负极集流体和位于所述负极集流体上的负极活性浆料层。所述负极活性浆料层包括负极活性材料。其中，所述负极活性材料的具体种类均不受到具体的限制，可根据需求进行选择。
在根据本发明第二方面所述的二次电池中，隔离膜的具体种类并不受到 具体的限制，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，优选地，所述正极活性材料选自钴酸锂(LiCoO2)、镍酸锂(LiNiO2)、橄榄石型的磷酸铁锂(LiFePO4)、橄榄石型的LiMPO4、尖晶石型的LiMn2O4、三元正极材料LiNixAyB(1-x-y)O2以及Li1-x’(A’y’B’z’C1-y’-z’)O2中的一种或几种。其中，M选自Co、Ni、Fe、Mn、V中的一种或几种；A、B各自独立地选自Co、Al、Mn中的一种，且A和B不相同；0<x<1，0<y<1且x+y<1；0≤x’<1，0≤y’<1，0≤z’<1且y’+z’<1；A’、B’、C各自独立地选自Co、Ni、Fe、Mn中的一种，且A’、B’、C不相同。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相对于Li/Li+平衡电位的电极电位＜2V时可以嵌入锂的材料。具体地，所述负极活性材料选自天然石墨、人造石墨、中间相微碳球(简称为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。所述电解质盐可为锂盐，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中的一种或几种。
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。
在下述实施例中，所使用到的试剂、材料以及仪器如没有特殊的说明，均可商购获得。
实施例1-11以及对比例1-7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98:1:1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
将负极活性材料人造石墨、增稠剂羧甲基纤维素钠(CMC)、粘结剂丁苯橡胶按照重量比98:1:1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，之后加入羧酸酯化合物、环状硫酸酯以及亚磷酸三苯酯，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％。电解液中所用到的羧酸酯化合物、环状硫酸酯以及亚磷酸三苯酯的具体种类以及含量如表1所示。在表1中，羧酸酯化合物的含量为基于有机溶剂的总体积计算得到的体积百分数，环状硫酸酯以及亚磷酸三苯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A273，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，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。
接下来说明锂离子二次电池的测试过程。
(1)锂离子二次电池的倍率性能测试
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4.4V，然后以4.4V恒压充电至电流小于等于0.05C，搁置5min后，以0.2C恒流放 电至截至电压3V，此时的放电容量记为D0。
然后将锂离子二次电池以1C恒流充电到电压为4.4V，再以4.4V恒压充电至电流小于等于0.05C，搁置5min后，以2C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2C/0.2C倍率性能＝D1/D0×100％。
(2)锂离子二次电池的高温循环性能测试
在45℃下，将锂离子二次电池先以1C恒流充电至电压为4.4V，进一步以4.4V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％。
(3)锂离子二次电池的高温存储性能测试
在85℃下，将锂离子二次电池以0.5C恒流充电至电压为4.4V，然后以4.4V恒压充电至电流为0.05C，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85℃的恒温箱，储存24h后取出，测试此时锂离子二次电池的厚度并记为h1。
锂离子二次电池存储24h后的厚度膨胀率(％)＝[(h1-h0)/h0]×100％。
表1给出实施例1-11和对比例1-7的参数及性能测试结果。
从表1的相关数据分析可知，对比例1中没有加入羧酸酯化合物、环状磷酸酯以及亚磷酸三苯酯，锂离子二次电池的倍率性能、高温循环性能及高温存储性能均较差；当电解液中仅含有羧酸酯化合物(对比例2)时，锂离子二次电池的倍率性能得到了改善，但是高温循环性能以及高温存储性能恶化；当电解液中仅含有环状硫酸酯(对比例3)时，锂离子二次电池的高温循环性能得到了改善，而倍率性能及高温存储性能则无明显变化；当电解液中仅含有亚磷酸三苯酯(对比例4)时，锂离子二次电池的高温存储性能得到了改善，但是倍率性能恶化；当电解液中同时加入羧酸酯化合物和环状硫 酸酯(对比例5)时，可以改善倍率性能的同时改善高温循环性能，但是高温存储性能严重恶化。当电解液中同时加入羧酸酯化合物和亚磷酸三苯酯(对比例6)时，可以兼顾倍率性能和高温存储性能，但是高温循环性能变差；当电解液中同时加入环状硫酸酯和亚磷酸三苯酯(对比例7)时，可以改善高温循环性能和高温存储性能，但是倍率性能出现恶化。
当电解液中同时含有羧酸酯化合物、环状磷酸酯以及亚磷酸三苯酯时，锂离子二次电池具有较好的倍率性能、同时兼具较好的高温循环性能及高温存储性能。
根据上述说明书的揭示，本申请所属领域的技术人员还可以对上述实施方式进行适当的变更和修改。因此，本申请并不局限于上面揭示和描述的具体实施方式，对本申请的一些修改和变更也应当落入本申请的权利要求的保护范围内。
Figure PCTCN2017093744-appb-000006

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，
    所述有机溶剂包括羧酸酯化合物；
    所述添加剂包括环状硫酸酯以及亚磷酸三苯酯。
  2. 根据权利要求1所述的电解液，其特征在于，所述羧酸酯化合物选自式Ⅰ所示的化合物中的一种或几种；
    Figure PCTCN2017093744-appb-100001
    其中，
    R1、R2各自独立地选自碳原子数为1～10的烷烃基、碳原子数为1～10的卤代烷烃基中的一种；
    卤代烷烃基中的卤原子选自F、Cl、Br、I中的一种或几种。
  3. 根据权利要求2所述的电解液，其特征在于，
    所述碳原子数为1～10的烷烃基选自甲基、乙基、正丙基、异丙基、环丙基、正丁基、异丁基、仲丁基、叔丁基、环丁基、正戊基、异戊基、叔戊基、新戊基、环戊基、2,2二甲基丙基、1-乙基丙基、1-甲基丁基、2-甲基丁基、正己基、异己基、2-己基、3-己基、环己基、2-甲基戊基、3-甲基戊基、1,1,2-三甲基丙基、3,3-二甲基丁基、正庚基、2-庚基、3-庚基、2-甲基己基、3-甲基己基、4-甲基己基、异庚基、环庚基、正辛基、环辛基、壬基、癸基中的一种；
    所述碳原子数为1～10的卤代烷烃基选自氯甲基、二氯甲基、三氯甲基、1-氯乙基、1,2-二氯乙基、2-氯正丙基、2,2-二氯-正丙基、1-氯异丙基、一氯 环丙基、1-氯正丁基、2-氯异丁基、一氯环丁基、1-氯正戊基、2-氯正戊基、1-氯异戊基、2,2-二氯甲基丙基、一氯环戊基、3-氯-2,2-二甲基丙基、1-氯-1-乙基丙基、1-氯-1-甲基丁基、2-氯-2-甲基丁基、2-氯正己基、一氯环己基、2-氯甲基戊基、3-氯-3-甲基戊基、2-氯-1,1,2-三甲基丙基、4-氯-3,3-二甲基丁基、2-氯正庚基中的一种，其中卤代烷烃基中的Cl原子还可被F、Br、I中的一种或几种部分取代或全部取代。
  4. 根据权利要求3所述的电解液，其特征在于，所述羧酸酯化合物选自甲酸甲酯、甲酸乙酯、乙酸乙酯、丙酸乙酯、戊酸乙酯、异戊酸乙酯、丙酸丙酯、丙酸丁酯、丙酸异丁酯、丁酸丁酯、异丁酸丁酯、丁酸戊酯、丁酸异戊酯、丙酸戊酯、丙酸异戊酯、异丙酸乙酯、丁酸乙酯、异丁酸乙酯、戊酸丙酯、异戊酸丙酯、异戊酸乙酯以及前述羧酸酯化合物被F、Cl、Br、I中的一种或几种部分取代或全部取代的化合物中的一种或几种。
  5. 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Ⅱ所示的化合物中的一种或几种；
    Figure PCTCN2017093744-appb-100002
    其中，
    n为1～3内的整数；
    R3、R4、R5、R6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还可被F、Cl、Br、I中的一种或几种取代。
  6. 根据权利要求5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 PCTCN2017093744-appb-100003
  7. 根据权利要求1所述的电解液，其特征在于，所述羧酸酯化合物的体积为所述有机溶剂的总体积的5％～50％，优选为10％～40％，进一步优选为20％～35％。
  8. 根据权利要求1所述的电解液，其特征在于，
    所述环状硫酸酯的含量为所述电解液的总重量的0.5％～10％，优选为 1％～5％；
    所述亚磷酸三苯酯的含量为所述电解液的总重量的0.03％～1％，优选为0.1％～0.3％。
  9. 根据权利要求1所述的电解液，其特征在于，所述有机溶剂还包括碳酸亚乙酯、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、γ-丁内酯、四氢呋喃中的一种或几种。
  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。
PCT/CN2017/093744 2016-12-26 2017-07-20 电解液及二次电池 Ceased WO2018120787A1 (zh)

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