WO2022262230A1 - Non-aqueous electrolyte and secondary battery thereof - Google Patents

Non-aqueous electrolyte and secondary battery thereof Download PDF

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WO2022262230A1
WO2022262230A1 PCT/CN2021/139142 CN2021139142W WO2022262230A1 WO 2022262230 A1 WO2022262230 A1 WO 2022262230A1 CN 2021139142 W CN2021139142 W CN 2021139142W WO 2022262230 A1 WO2022262230 A1 WO 2022262230A1
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lithium
electrolyte
electrode material
electrolytic solution
aqueous
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PCT/CN2021/139142
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French (fr)
Chinese (zh)
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欧霜辉
王霹霹
白晶
毛冲
黄秋洁
戴晓兵
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珠海市赛纬电子材料股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present application relates to the field of energy storage devices, in particular to a non-aqueous electrolyte and a secondary battery thereof.
  • lithium-ion batteries are currently the most ideal and potential rechargeable batteries in the world.
  • Electrolyte as an important part of lithium-ion batteries, has a significant impact on performance degradation such as charge and discharge cycles of batteries.
  • performance degradation such as charge and discharge cycles of batteries.
  • high-voltage (4.35V-5V) cathode materials are one of the more popular research directions. It achieves high energy density of batteries by increasing the charging depth of cathode active materials.
  • the performance of the battery such as charge and discharge cycles decreases.
  • the electrolyte as an important part of the lithium-ion battery, has a major impact on the performance degradation of the battery charge and discharge cycle, and the wettability of the electrolyte to the pole piece directly affects the energy density of the battery.
  • this non-aqueous electrolytic solution can not only improve the high-temperature storage performance and cycle performance of secondary battery, and has better wettability, can satisfy high voltage ( 4.35V and above) the requirements for the use of ternary lithium-ion batteries.
  • the first aspect of the present application provides a non-aqueous electrolytic solution, including lithium salt, non-aqueous organic solvent and additive, and the additive includes the unsaturated cyclic sulfonylimide salt shown in structural formula I and structural formula Fluoroethers shown in II,
  • M + is an alkali metal ion
  • R is H or a C 1 -C 3 alkyl group
  • R 1 and R 2 are each independently a C 1 -C 6 fluorohydrocarbon.
  • the unsaturated cyclic sulfonimide salt shown in structural formula I can be polymerized at the interface of the positive and negative electrodes to form an SEI layer and improve the cycle performance and high-temperature storage performance of the battery, but due to the unsaturated cyclic sulfonimide salt in In the high-voltage system, it has a relatively high viscosity after solvation, and its wetting angle is large, which makes the diffusion rate of the electrolyte in the electrode material low, and the electrode material is difficult to be infiltrated by the electrolyte, resulting in electrochemical degradation of the electrode material. Performance is not fully utilized.
  • the -F in the fluoroether is more polar and has a lower molecular weight, which can effectively reduce the viscosity of the electrolyte and reduce the wetting angle, so that the unsaturated cyclic sulfonylimide salt can Effectively infiltrate in the electrode material so as to effectively exert the electrochemical performance of the electrode material.
  • this application adds fluoroether on the basis of unsaturated cyclic sulfonimide salt to make up for the problem that unsaturated cyclic sulfonimide salt reduces the wettability of electrolyte, thereby improving the high-voltage (4.35V) ternary Electrochemical properties such as high-temperature storage and cycling of lithium-ion batteries.
  • R in the structural formula I is a methyl group, more preferably, the mass percentage of the unsaturated cyclic sulfonimide salt in the non-aqueous electrolyte is 0.05-3.0%, specifically but not limited to 0.05%, 0.1%, 1%, 1.5%, 2%, 2.5%, 3%, unsaturated cyclic sulfonimide salts are selected from at least one of compound A to compound E,
  • all terminal hydrogens of at least one of R 1 and R 2 in the structural formula II are replaced by fluorine.
  • the mass percentage of fluoroether in the non-aqueous electrolyte is 0.05-3.0%, specifically but not limited to 0.05%, 0.08%, 0.1%, 0.5%, 1%, 1.5%, 1.8%, 2%, 2.5% %, 2.8%, 3.0%, the fluoroether is at least one selected from Compound F to Compound J.
  • the lithium salt is selected from lithium hexafluorophosphate (LiPF 6 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium bistrifluoromethanesulfonimide (LiN(CF 3 SO 2 ) 2 ) , lithium bisoxalate borate (C 4 BLiO 8 ), lithium difluorooxalate borate (C 2 BF 2 LiO 4 ), lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium difluorooxalate phosphate (LiDFBP) and lithium bisfluorosulfonyl imide (LiFSI), the concentration of the lithium salt is 0.5-1.5M.
  • LiPF 6 lithium hexafluorophosphate
  • LiCF 3 SO 3 lithium trifluoromethanesulfonate
  • LiN(CF 3 SO 2 ) 2 lithium bisoxalate borate
  • the non-aqueous organic solvent is selected from ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), propylene carbonate (PC), At least one of butyl acetate (n-Ba), ⁇ -butyrolactone ( ⁇ -Bt), propyl propionate (n-Pp), ethyl propionate (EP) and ethyl butyrate (Eb) .
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • PC propylene carbonate
  • n-Ba butyl acetate
  • ⁇ -Bt ⁇ -butyrolactone
  • n-Pp propyl propionate
  • EP ethyl propionate
  • Eb ethyl butyrate
  • the second aspect of the present application provides a secondary battery, including a positive electrode material, a negative electrode material and an electrolyte, the electrolyte is the aforementioned non-aqueous electrolyte, and the maximum charging voltage is 4.35-4.5V.
  • the additives of the non-aqueous electrolyte of the secondary battery of the present application include the unsaturated cyclic sulfonimide salt shown in structural formula I and the fluoroether shown in structural formula II, which can make up for the unsaturated cyclic The sulfonimide salt reduces the defect of electrolyte wettability, thereby improving the electrochemical performance of high-voltage (4.35V) ternary lithium-ion batteries such as high-temperature storage and cycling.
  • the positive electrode material is Li (1+a) Ni x Co y M z N 1-xyz O 2+b , wherein M is Mn or Al, and N is Mg, Cu, Zn, Sn, B, Any one of Ga, Cr, Sr, Ba, V and Ti, -0.10 ⁇ a ⁇ 0.50, 0.6 ⁇ x ⁇ 0.9, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0.6 ⁇ x+y+z ⁇ 1, -0.05 ⁇ b ⁇ 0.10.
  • the negative electrode material is at least one selected from artificial graphite, natural graphite, lithium titanate, silicon-carbon composite material and silicon oxide, preferably silicon-carbon negative electrode material (10wt.% Si).
  • LiNi 0.8 Co 0.1 Al 0.1 O 2 ternary material LiNi 0.8 Co 0.1 Al 0.1 O 2 , binder PVDF and conductive agent SuperP are uniformly mixed at a mass ratio of 98:1:1 to make lithium ions with a certain viscosity
  • the positive electrode slurry of the battery after coating the mixed slurry on both sides of the aluminum foil, drying and rolling to obtain the positive electrode sheet.
  • lithium-ion battery the positive electrode, separator and negative electrode are stacked into square batteries, packed in polymer, filled with the non-aqueous electrolyte of lithium-ion battery prepared above, and processed by chemical formation, volumetric separation, etc. Lithium-ion batteries are made after the process.
  • the synthetic route of unsaturated cyclic sulfonylimide salt compound A-E can be as follows:
  • Compound F (CAS:16627-68-2), Compound G(CAS:50807-74-4), Compound H(CAS:16627-68-2), Compound I(CAS:993-95- 3) Compound J (CAS: 16627-68-2) can be obtained commercially.
  • the lithium-ion batteries made in Examples 1-13 and Comparative Examples 1-5 were subjected to wettability test, normal temperature cycle performance, high temperature cycle performance and high temperature storage test respectively.
  • the specific test conditions are as follows, and the performance test results are shown in Table 2.
  • Wettability test At room temperature (25°C), in a glove box filled with N 2 , use a pipette gun with a volume range of 1-5 ⁇ L to fill the electrolyte solution.
  • the positive and negative electrodes, and the positive and negative electrodes have a pressure density of 3.5g/cm 3 and 1.6g/cm 3 respectively, and the liquid is dripped. Observe the time required for one drop of electrolyte to be completely absorbed by the electrode, and record it as t.
  • High temperature cycle test Under the condition of high temperature (45°C), charge and discharge the lithium-ion battery once at 1.0C/1.0C (battery discharge capacity is C0), the upper limit voltage is 4.35V, and then charge and discharge the lithium-ion battery at high temperature (45°C) Charge and discharge at 1.0C/1.0C for 500 cycles (battery discharge capacity is C1).
  • High-temperature storage performance test Under normal temperature (25°C), charge and discharge the lithium-ion battery once at 0.5C/0.5C (the discharge capacity is denoted as C0), the upper limit voltage is 4.35V, and then at 0.5C constant current and constant voltage Charge the battery to 4.35V under the same conditions, and measure the battery thickness d0; put the lithium-ion battery in a high-temperature box at 60°C for 30 days, take it out and measure the battery thickness d1; discharge it at 0.5C at 25°C (the discharge capacity is recorded as C1); Continue to charge and discharge the lithium-ion battery at 0.5C/0.5C once at room temperature (25°C) (the discharge capacity is denoted as C2), and the upper limit voltage is 4.35V.
  • C2 the discharge capacity retention rate of the lithium-ion battery
  • Thickness expansion rate d1/d0*100%
  • Examples 1-14 have better wettability while maintaining higher high-temperature storage and cycle performance. This is because the addition of fluoroether in the additive , its -F has a large polarity and a low molecular weight, which can effectively reduce the viscosity of the electrolyte and reduce the wetting angle, so that the unsaturated cyclic sulfonylimide salt can be effectively infiltrated in the electrode material to effectively play the role of the electrode. Electrochemical properties of materials.
  • Comparative Examples 1, 3, and 5 have better wettability, but poor cycle and high-temperature storage performance, which cannot meet the requirements of high-voltage (above 4.35V) ternary lithium-ion batteries.
  • comparative examples 2 and 4 although the addition of unsaturated cyclic sulfonimide salts with structural formula I can improve the cycle performance and high-temperature storage performance of the battery to a certain extent, due to the large wetting angle, the electrode material is difficult to be electrolyzed. The electrochemical performance of the electrode material cannot be fully exerted due to infiltration by the liquid.

Abstract

A non-aqueous electrolyte and a secondary battery thereof, wherein the non-aqueous electrolyte comprises a lithium salt, a non-aqueous organic solvent, and an additive. The additive comprises an unsaturated cyclic sulfimide salt represented by a structural formula I and a fluoroether represented by a structural formula II, wherein M+ is an alkali metal ion; R is H or a C1-C3 alkyl; and R1 and R2 are each independently a C1-C6 fluorohydrocarbon. An unsaturated cyclic sulfimide salt can improve the cycle performance and the high-temperature storage performance of a battery, but has a relatively high viscosity and a relatively large wetting angle after solvation in a high-voltage system, such that the diffusion rate of an electrolyte in an electrode material is relatively low, and the electrode material is difficult for the electrolyte to infiltrate, and therefore the electrochemical performance of the electrode material cannot be given full play to. However, by means of adding a fluoroether, the viscosity of the electrolyte can be effectively reduced, thereby reducing the wetting angle, and therefore the electrolyte containing an unsaturated cyclic sulfimide salt can effectively infiltrate the electrode material and thus give full play to the electrochemical performance thereof.

Description

非水电解液及其二次电池Non-aqueous electrolyte and its secondary battery 技术领域technical field
本申请涉及储能器械领域，具体涉及一种非水电解液及其二次电池。The present application relates to the field of energy storage devices, in particular to a non-aqueous electrolyte and a secondary battery thereof.
背景技术Background technique
二次电池具有比能量高、比功率大、循环寿命长、自放电小等显著优点，锂离子电池作为一种绿色环保高能电池，是目前世界上最为理想也最具有潜力的可充电电池。如今，随着纯电动汽车、混合动力汽车及便携式储能设备等对锂离子电池容量要求的不断提高，人们期待研发具有更高能量密度、功率密度的锂离子电池来实现储能及长久续航。Secondary batteries have significant advantages such as high specific energy, high specific power, long cycle life, and low self-discharge. As a green and environmentally friendly high-energy battery, lithium-ion batteries are currently the most ideal and potential rechargeable batteries in the world. Today, with the continuous improvement of lithium-ion battery capacity requirements for pure electric vehicles, hybrid vehicles and portable energy storage devices, people expect to develop lithium-ion batteries with higher energy density and power density to achieve energy storage and long-term battery life.
电解液作为锂离子电池的重要组成部分，对电池的充放电循环等性能下降有着重大的影响。除了现有材料和电池的制作工艺改进之外，高电压(4.35V-5V)正极材料是对比热门的研究方向之一，它是通过提升正极活性材料的充电深度来实现电池的高能量密度。然而三元材料电池工作电压提高后，电池的充放电循环等性能却下降。其中，电解液作为锂离子电池的重要组成部分，对电池的充放电循环等性能下降有着重大的影响，电解液对极片的浸润性直接影响电池能量密度的发挥。众多改善电池循环和存储性能的电解液添加剂大都浸润性能较差，而添加电解液浸润剂虽然会提高浸润性能但是对循环性能又产生负面性能。因此，研制出一种既能改善循环和存储性能，又能兼顾电解液浸润性的非水电解液是业界急需解决的难题。Electrolyte, as an important part of lithium-ion batteries, has a significant impact on performance degradation such as charge and discharge cycles of batteries. In addition to the improvement of existing materials and battery manufacturing processes, high-voltage (4.35V-5V) cathode materials are one of the more popular research directions. It achieves high energy density of batteries by increasing the charging depth of cathode active materials. However, after the operating voltage of the ternary material battery is increased, the performance of the battery such as charge and discharge cycles decreases. Among them, the electrolyte, as an important part of the lithium-ion battery, has a major impact on the performance degradation of the battery charge and discharge cycle, and the wettability of the electrolyte to the pole piece directly affects the energy density of the battery. Most of the electrolyte additives that improve the battery cycle and storage performance have poor wetting performance, and the addition of electrolyte wetting agents will improve the wetting performance but have negative performance on the cycle performance. Therefore, it is an urgent problem to be solved in the industry to develop a non-aqueous electrolyte that can not only improve the cycle and storage performance, but also take into account the wettability of the electrolyte.
申请内容application content
本申请的目的在于提供一种非水电解液及其二次电池，此非水电解液不仅可提高二次电池的高温存储性能和循环性能，且具有较佳的浸润性，可满足高电压(4.35V以上)三元锂离子电池的使用要求。The purpose of this application is to provide a kind of non-aqueous electrolytic solution and its secondary battery, this non-aqueous electrolytic solution can not only improve the high-temperature storage performance and cycle performance of secondary battery, and has better wettability, can satisfy high voltage ( 4.35V and above) the requirements for the use of ternary lithium-ion batteries.
为实现上述目的，本申请第一方面提供了一种非水电解液，包括锂盐、非水有机溶剂和添加剂，所述添加剂包括结构式I所示的不饱和环状磺酰亚胺盐和结构式II所示的氟代醚，In order to achieve the above object, the first aspect of the present application provides a non-aqueous electrolytic solution, including lithium salt, non-aqueous organic solvent and additive, and the additive includes the unsaturated cyclic sulfonylimide salt shown in structural formula I and structural formula Fluoroethers shown in II,
Figure PCTCN2021139142-appb-000001
Figure PCTCN2021139142-appb-000001
其中，M +为碱金属离子；R为H或C 1-C 3的烷基；R 1和R 2各自独立为C 1-C 6的氟代烃。 Wherein, M + is an alkali metal ion; R is H or a C 1 -C 3 alkyl group; R 1 and R 2 are each independently a C 1 -C 6 fluorohydrocarbon.
虽然具有结构式I所示的不饱和环状磺酰亚胺盐能在正负极界面聚合，形成SEI层而改善电池的循环性能和高温存储性能，但由于不饱和环状磺酰亚胺盐在高电压体系中溶剂化后具有相对较高的粘度，其润湿角较大，进而使电解液在电极材料中的扩散速率较低，电极材料难以被电解液所浸润，导致电极材料的电化学性能得不到完全的发挥。通过于添加剂中增加氟代醚，氟代醚中的-F极性较大，分子量较低，可以有效降低电解液的粘度而减少润湿角，故使得不饱和环状磺酰亚胺盐能有效的浸润在电极材料中从而有效的发挥电极材料的电化学性能。故，本申请于不饱和环状磺酰亚胺盐的基础上添加氟代醚以弥补不饱和环状磺酰亚胺盐降低电解液浸润性的问题，从而提高高电压(4.35V)三元锂离子电池的高温存储及循环等电化学性能。Although the unsaturated cyclic sulfonimide salt shown in structural formula I can be polymerized at the interface of the positive and negative electrodes to form an SEI layer and improve the cycle performance and high-temperature storage performance of the battery, but due to the unsaturated cyclic sulfonimide salt in In the high-voltage system, it has a relatively high viscosity after solvation, and its wetting angle is large, which makes the diffusion rate of the electrolyte in the electrode material low, and the electrode material is difficult to be infiltrated by the electrolyte, resulting in electrochemical degradation of the electrode material. Performance is not fully utilized. By adding fluoroether to the additive, the -F in the fluoroether is more polar and has a lower molecular weight, which can effectively reduce the viscosity of the electrolyte and reduce the wetting angle, so that the unsaturated cyclic sulfonylimide salt can Effectively infiltrate in the electrode material so as to effectively exert the electrochemical performance of the electrode material. Therefore, this application adds fluoroether on the basis of unsaturated cyclic sulfonimide salt to make up for the problem that unsaturated cyclic sulfonimide salt reduces the wettability of electrolyte, thereby improving the high-voltage (4.35V) ternary Electrochemical properties such as high-temperature storage and cycling of lithium-ion batteries.
较佳的，结构式I中R为甲基，更较佳的，所述不饱和环状磺酰亚胺盐于所述非水电解液中的质量百分比为0.05～3.0％，具体但不限于为0.05％、0.1％、1％、1.5％、2％、2.5％、3％，不饱和环状磺酰亚胺盐选自化合物A至化合物E中的至少一种，Preferably, R in the structural formula I is a methyl group, more preferably, the mass percentage of the unsaturated cyclic sulfonimide salt in the non-aqueous electrolyte is 0.05-3.0%, specifically but not limited to 0.05%, 0.1%, 1%, 1.5%, 2%, 2.5%, 3%, unsaturated cyclic sulfonimide salts are selected from at least one of compound A to compound E,
Figure PCTCN2021139142-appb-000002
Figure PCTCN2021139142-appb-000002
Figure PCTCN2021139142-appb-000003
Figure PCTCN2021139142-appb-000003
较佳的，结构式II中R 1和R 2中至少一个的末端氢全部被氟取代。氟代醚于所述非水电解液中的质量百分比为0.05～3.0％，具体但不限于为0.05％、0.08％、0.1％、0.5％、1％、1.5％、1.8％、2％、2.5％、2.8％、3.0％，氟代醚选自化合物F至化合物J中的至少一种。 Preferably, all terminal hydrogens of at least one of R 1 and R 2 in the structural formula II are replaced by fluorine. The mass percentage of fluoroether in the non-aqueous electrolyte is 0.05-3.0%, specifically but not limited to 0.05%, 0.08%, 0.1%, 0.5%, 1%, 1.5%, 1.8%, 2%, 2.5% %, 2.8%, 3.0%, the fluoroether is at least one selected from Compound F to Compound J.
Figure PCTCN2021139142-appb-000004
Figure PCTCN2021139142-appb-000004
较佳的，所述锂盐选自六氟磷酸锂(LiPF 6)、三氟甲基磺酸锂(LiCF 3SO 3)、双三氟甲基磺酰亚胺锂(LiN(CF 3SO 2) 2)、双草酸硼酸锂(C 4BLiO 8)、二氟草酸硼酸锂(C 2BF 2LiO 4)、高氯酸锂(LiClO 4)、四氟硼酸锂(LiBF 4)、二氟二草酸磷酸锂(LiDFBP)和双氟磺酰亚胺锂(LiFSI)中的至少一种，所述锂盐的浓度为0.5～1.5M。 Preferably, the lithium salt is selected from lithium hexafluorophosphate (LiPF 6 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium bistrifluoromethanesulfonimide (LiN(CF 3 SO 2 ) 2 ) , lithium bisoxalate borate (C 4 BLiO 8 ), lithium difluorooxalate borate (C 2 BF 2 LiO 4 ), lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium difluorooxalate phosphate (LiDFBP) and lithium bisfluorosulfonyl imide (LiFSI), the concentration of the lithium salt is 0.5-1.5M.
较佳的，所述非水有机溶剂选自碳酸乙烯酯(EC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸丙烯酯(PC)、乙酸丁酯(n-Ba)、γ-丁内酯(γ-Bt)、丙酸丙酯(n-Pp)、丙酸乙酯(EP)和丁酸乙酯(Eb)中的 至少一种。Preferably, the non-aqueous organic solvent is selected from ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), propylene carbonate (PC), At least one of butyl acetate (n-Ba), γ-butyrolactone (γ-Bt), propyl propionate (n-Pp), ethyl propionate (EP) and ethyl butyrate (Eb) .
本申请的第二方面提供了一种二次电池，包括正极材料、负极材料和电解液，所述电解液为前述的非水电解液，且最高充电电压为4.35～4.5V。本申请的二次电池的非水电解液的添加剂包括结构式I所示的不饱和环状磺酰亚胺盐和结构式II所示的氟代醚，通过氟代醚的作用可弥补不饱和环状磺酰亚胺盐降低电解液浸润性的缺陷，从而提高高电压(4.35V)三元锂离子电池的高温存储及循环等电化学性能。较佳的，所述正极材料为Li (1+a)Ni xCo yM zN 1-x-y-zO 2+b，其中，M为Mn或Al，N为Mg、Cu、Zn、Sn、B、Ga、Cr、Sr、Ba、V和Ti中的任意一种，-0.10≤a≤0.50，0.6＜x＜0.9，0＜y＜1，0<z＜1，0.6＜x+y+z≤1，-0.05≤b≤0.10。所述负极材料选自人造石墨、天然石墨、钛酸锂、硅碳复合材料和氧化亚硅中的至少一种，优选为硅碳负极材料(10wt.％Si)。 The second aspect of the present application provides a secondary battery, including a positive electrode material, a negative electrode material and an electrolyte, the electrolyte is the aforementioned non-aqueous electrolyte, and the maximum charging voltage is 4.35-4.5V. The additives of the non-aqueous electrolyte of the secondary battery of the present application include the unsaturated cyclic sulfonimide salt shown in structural formula I and the fluoroether shown in structural formula II, which can make up for the unsaturated cyclic The sulfonimide salt reduces the defect of electrolyte wettability, thereby improving the electrochemical performance of high-voltage (4.35V) ternary lithium-ion batteries such as high-temperature storage and cycling. Preferably, the positive electrode material is Li (1+a) Ni x Co y M z N 1-xyz O 2+b , wherein M is Mn or Al, and N is Mg, Cu, Zn, Sn, B, Any one of Ga, Cr, Sr, Ba, V and Ti, -0.10≤a≤0.50, 0.6<x<0.9, 0<y<1, 0<z<1, 0.6<x+y+z≤ 1, -0.05≤b≤0.10. The negative electrode material is at least one selected from artificial graphite, natural graphite, lithium titanate, silicon-carbon composite material and silicon oxide, preferably silicon-carbon negative electrode material (10wt.% Si).
具体实施方式detailed description
下面通过具体实施例来进一步说明本申请的目的、技术方案及有益效果，但不构成对本申请的任何限制。实施例中未注明具体条件者，可按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可通过市售而获得的常规产品。The purpose, technical solutions and beneficial effects of the present application will be further described below through specific examples, but this does not constitute any limitation to the present application. Those who do not indicate specific conditions in the examples can be carried out according to conventional conditions or conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all commercially available conventional products.
实施例1Example 1
(1)锂离子电池非水电解液的制备：在充满氮气的手套箱(O 2＜2ppm，H 2O＜3ppm)中，将碳酸二甲酯(EC)、碳酸甲乙酯(EMC)和碳酸二乙酯(DEC)的混和物作为有机溶剂，按照质量比2:5:2混合均匀，制得非水有机溶剂87.2g，加入0.3g化合物A、0.5g化合物F。将溶液密封打包放置急冻间(-4℃)冷冻2h之后取出，在充满氮气的手套箱(O 2＜2ppm，H 2O＜3ppm)中，向混合溶液中缓慢加入12g六氟磷酸锂，混合均匀后即制成锂离子电池非水电解液。 (1) Preparation of non - aqueous electrolyte for lithium - ion batteries: Dimethyl carbonate (EC), ethyl methyl carbonate (EMC) and A mixture of diethyl carbonate (DEC) was used as an organic solvent, and mixed uniformly according to a mass ratio of 2:5:2 to obtain 87.2 g of a non-aqueous organic solvent, and 0.3 g of compound A and 0.5 g of compound F were added. Seal the solution and place it in the freezer (-4°C) for 2 hours, then take it out, and slowly add 12g of lithium hexafluorophosphate to the mixed solution in a nitrogen-filled glove box (O 2 <2ppm, H 2 O<3ppm), and mix well That is, a non-aqueous electrolyte solution for a lithium-ion battery is made.
(2)正极的制备：将镍钴铝酸锂三元材料LiNi 0.8Co 0.1Al 0.1O 2、粘接剂PVDF和导电剂SuperP按质量比98:1:1混合均匀制成一定粘度的锂离子电池正极浆 料，将混制的浆料涂布在铝箔的两面后，烘干、辊压后得到正极片。 (2) Preparation of positive electrode: LiNi 0.8 Co 0.1 Al 0.1 O 2 ternary material LiNi 0.8 Co 0.1 Al 0.1 O 2 , binder PVDF and conductive agent SuperP are uniformly mixed at a mass ratio of 98:1:1 to make lithium ions with a certain viscosity The positive electrode slurry of the battery, after coating the mixed slurry on both sides of the aluminum foil, drying and rolling to obtain the positive electrode sheet.
(3)负极的制备：将硅碳负极材料(10wt.％Si)与导电剂SuperP、增稠剂CMC、粘接剂SBR(丁苯橡胶乳液)按质量比95:1:2:2的比例制成浆料，混合均匀，用混制的浆料涂布在铜箔的两面后，烘干、辊压后得到负极片。(3) Preparation of negative electrode: Silicon carbon negative electrode material (10wt.% Si) and conductive agent SuperP, thickener CMC, binder SBR (styrene-butadiene rubber emulsion) in a mass ratio of 95:1:2:2 The slurry is prepared, mixed uniformly, coated on both sides of the copper foil with the mixed slurry, dried and rolled to obtain a negative electrode sheet.
(4)锂离子电池的制备：将正极、隔膜以及负极以叠片的方式制成方形电芯，采用聚合物包装，灌装上述制备的锂离子电池非水电解液，经化成、分容等工序后制成锂离子电池。(4) Preparation of lithium-ion battery: the positive electrode, separator and negative electrode are stacked into square batteries, packed in polymer, filled with the non-aqueous electrolyte of lithium-ion battery prepared above, and processed by chemical formation, volumetric separation, etc. Lithium-ion batteries are made after the process.
实施例2～13和对比例1～5的电解液配方如表1所示，配制电解液的步骤同实施例1。The electrolyte formulations of Examples 2-13 and Comparative Examples 1-5 are shown in Table 1, and the steps for preparing the electrolyte are the same as in Example 1.
其中，不饱和环状磺酰亚胺盐化合物A-E的合成路线可如下：Wherein, the synthetic route of unsaturated cyclic sulfonylimide salt compound A-E can be as follows:
Figure PCTCN2021139142-appb-000005
Figure PCTCN2021139142-appb-000005
氟代醚中的化合物F(CAS:16627-68-2)、化合物G(CAS:50807-74-4)、化合物H(CAS:16627-68-2)、化合物I(CAS:993-95-3)、化合物J(CAS:16627-68-2)皆可通过市售获得。Compound F(CAS:16627-68-2), Compound G(CAS:50807-74-4), Compound H(CAS:16627-68-2), Compound I(CAS:993-95- 3) Compound J (CAS: 16627-68-2) can be obtained commercially.
表1各实施例的电解液组分The electrolyte composition of each embodiment of table 1
Figure PCTCN2021139142-appb-000006
Figure PCTCN2021139142-appb-000006
对实施例1～13和对比例1～5制成的锂离子电池分别进行浸润性测试、常温 循环性能、高温循环性能和高温存储测试，具体测试条件如下，性能测试结果如表2所示。The lithium-ion batteries made in Examples 1-13 and Comparative Examples 1-5 were subjected to wettability test, normal temperature cycle performance, high temperature cycle performance and high temperature storage test respectively. The specific test conditions are as follows, and the performance test results are shown in Table 2.
浸润性测试：在常温(25℃)条件下，于N 2填充的手套箱中，使用量程为1～5μL的移液枪盛满电解液，对
Figure PCTCN2021139142-appb-000007
的正负极片、正负极极片压密度分别为3.5g/cm 3、1.6g/cm 3进行滴液，观察1滴电解液被极片完全吸收所需要的时间，记录为t。 Wettability test: At room temperature (25°C), in a glove box filled with N 2 , use a pipette gun with a volume range of 1-5 μL to fill the electrolyte solution.
Figure PCTCN2021139142-appb-000007
The positive and negative electrodes, and the positive and negative electrodes have a pressure density of 3.5g/cm 3 and 1.6g/cm 3 respectively, and the liquid is dripped. Observe the time required for one drop of electrolyte to be completely absorbed by the electrode, and record it as t.
常温循环测试：在常温(25℃)条件下，对锂离子电池进行一次1.0C/1.0C充电和放电(电池放电容量为C0)，上限电压为4.35V，然后在常温条件下进行1.0C/1.0C充电和放电500周(电池放电容量为C1)。Normal temperature cycle test: Under normal temperature (25°C), charge and discharge the lithium-ion battery once at 1.0C/1.0C (battery discharge capacity is C0), the upper limit voltage is 4.35V, and then perform 1.0C/1.0C at normal temperature. 1.0C charge and discharge for 500 cycles (battery discharge capacity is C1).
容量保持率＝(C1/C0)*100％。Capacity retention=(C1/C0)*100%.
高温循环测试：在过高温(45℃)条件下，对锂离子电池进行一次1.0C/1.0C充电和放电(电池放电容量为C0)，上限电压为4.35V，然后在高温(45℃)条件下进行1.0C/1.0C充电和放电500周(电池放电容量为C1)。High temperature cycle test: Under the condition of high temperature (45°C), charge and discharge the lithium-ion battery once at 1.0C/1.0C (battery discharge capacity is C0), the upper limit voltage is 4.35V, and then charge and discharge the lithium-ion battery at high temperature (45°C) Charge and discharge at 1.0C/1.0C for 500 cycles (battery discharge capacity is C1).
容量保持率＝(C1/C0)*100％Capacity retention = (C1/C0)*100%
高温存储性能测试：在常温(25℃)条件下，对锂离子电池进行一次0.5C/0.5C充电和放电(放电容量记为C0)，上限电压为4.35V，然后在0.5C恒流恒压条件下将电池充电至4.35V，测量电池厚度d0；将锂离子电池置于60℃高温箱中搁置30d，取出测量电池厚度d1；在25℃下进行0.5C放电(放电容量记为C1)；继续在常温(25℃)条件下，对锂离子电池进行一次0.5C/0.5C充电和放电(放电容量记为C2)，上限电压为4.35V，利用下面公式计算锂离子电池的容量保持率、容量恢复率和厚度膨胀率。High-temperature storage performance test: Under normal temperature (25°C), charge and discharge the lithium-ion battery once at 0.5C/0.5C (the discharge capacity is denoted as C0), the upper limit voltage is 4.35V, and then at 0.5C constant current and constant voltage Charge the battery to 4.35V under the same conditions, and measure the battery thickness d0; put the lithium-ion battery in a high-temperature box at 60°C for 30 days, take it out and measure the battery thickness d1; discharge it at 0.5C at 25°C (the discharge capacity is recorded as C1); Continue to charge and discharge the lithium-ion battery at 0.5C/0.5C once at room temperature (25°C) (the discharge capacity is denoted as C2), and the upper limit voltage is 4.35V. Use the following formula to calculate the capacity retention rate of the lithium-ion battery, Capacity recovery rate and thickness expansion rate.
容量保持率＝C1/C0*100％Capacity retention = C1/C0*100%
容量恢复率＝C2/C0*100％Capacity recovery rate = C2/C0*100%
厚度膨胀率＝d1/d0*100％Thickness expansion rate = d1/d0*100%
表2锂离子电池性能测试结果Table 2 Li-ion battery performance test results
Figure PCTCN2021139142-appb-000008
Figure PCTCN2021139142-appb-000008
Figure PCTCN2021139142-appb-000009
Figure PCTCN2021139142-appb-000009
由表2的结果可知，实施例1～14相对对比例1～5而言，在维持较高的高温存储和循环性能同时还具有较佳的浸润性，这是因为于添加剂中增加氟代醚，其-F极性较大，分子量较低，可以有效降低电解液的粘度而减少润湿角，故使得不饱和环状磺酰亚胺盐能有效的浸润在电极材料中从而有效的发挥电极材料的电化学性能。对比例1、3、5中的电解液浸润性较佳，但是循环和高温存储性能较差，无法满足高电压(4.35V以上)三元锂离子电池的使用要求。对比例2、4中，添加具有结构式I的不饱和环状磺酰亚胺盐虽然可于一定程度上改善电池的循环性能和高温存储性能，但是由于润湿角较大，电极材料难以被电解液所浸润，导致电极材料的电化学性能得不到完全的发挥。From the results in Table 2, it can be seen that compared with Comparative Examples 1-5, Examples 1-14 have better wettability while maintaining higher high-temperature storage and cycle performance. This is because the addition of fluoroether in the additive , its -F has a large polarity and a low molecular weight, which can effectively reduce the viscosity of the electrolyte and reduce the wetting angle, so that the unsaturated cyclic sulfonylimide salt can be effectively infiltrated in the electrode material to effectively play the role of the electrode. Electrochemical properties of materials. The electrolytes in Comparative Examples 1, 3, and 5 have better wettability, but poor cycle and high-temperature storage performance, which cannot meet the requirements of high-voltage (above 4.35V) ternary lithium-ion batteries. In comparative examples 2 and 4, although the addition of unsaturated cyclic sulfonimide salts with structural formula I can improve the cycle performance and high-temperature storage performance of the battery to a certain extent, due to the large wetting angle, the electrode material is difficult to be electrolyzed. The electrochemical performance of the electrode material cannot be fully exerted due to infiltration by the liquid.
最后应当说明的是，以上实施例仅用以说明本申请的技术方案而非对本申请保护范围的限制，尽管参照较佳实施例对本申请作了详细说明，本领域的普通技术人员应当理解，可以对本申请的技术方案进行修改或者等同替换，而不脱离本申请技术方案的实质和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application rather than limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that Modifications or equivalent replacements are made to the technical solutions of the present application without departing from the essence and scope of the technical solutions of the present application.

Claims (10)

  1. 一种非水电解液包括锂盐、非水有机溶剂和添加剂，其特征在于，所述添加剂包括结构式I所示的不饱和环状磺酰亚胺盐和结构式II所示的氟代醚，A kind of non-aqueous electrolytic solution comprises lithium salt, non-aqueous organic solvent and additive, is characterized in that, described additive comprises unsaturated cyclic sulfonylimide salt shown in structural formula I and the fluorinated ether shown in structural formula II,
    Figure PCTCN2021139142-appb-100001
    Figure PCTCN2021139142-appb-100001
    其中，M +为碱金属离子；R为H或C 1-C 3的烷基；R 1和R 2各自独立为C 1-C 6的氟代烃。 Wherein, M + is an alkali metal ion; R is H or a C 1 -C 3 alkyl group; R 1 and R 2 are each independently a C 1 -C 6 fluorohydrocarbon.
  2. 如权利要求1所述的非水电解液，其特征在于，R为甲基；R 1和R 2中至少一个的末端氢全部被氟取代。 The non-aqueous electrolytic solution according to claim 1, wherein R is a methyl group; R1 and R2 at least one terminal hydrogen is all substituted by fluorine.
  3. 如权利要求1所述的非水电解液，其特征在于，所述不饱和环状磺酰亚胺盐于所述非水电解液中的质量百分比为0.05～3.0％，所述氟代醚于所述非水电解液中的质量百分比为0.05～3.0％。The non-aqueous electrolytic solution according to claim 1, wherein the mass percentage of the unsaturated cyclic sulfonimide salt in the non-aqueous electrolytic solution is 0.05-3.0%, and the fluoroether is The mass percentage in the non-aqueous electrolyte is 0.05-3.0%.
  4. 如权利要求1所述的非水电解液，其特征在于，所述不饱和环状磺酰亚胺盐选自化合物A至化合物E中的至少一种，The non-aqueous electrolytic solution according to claim 1, wherein the unsaturated cyclic sulfonimide salt is selected from at least one of compound A to compound E,
    Figure PCTCN2021139142-appb-100002
    Figure PCTCN2021139142-appb-100002
    Figure PCTCN2021139142-appb-100003
    Figure PCTCN2021139142-appb-100003
  5. 如权利要求1所述的非水电解液，其特征在于，所述氟代醚选自化合物F至化合物J中的至少一种，The non-aqueous electrolytic solution according to claim 1, wherein the fluoroether is selected from at least one of compound F to compound J,
    Figure PCTCN2021139142-appb-100004
    Figure PCTCN2021139142-appb-100004
  6. 如权利要求1所述的非水电解液，其特征在于，所述锂盐选自六氟磷酸锂、三氟甲基磺酸锂、双三氟甲基磺酰亚胺锂、双草酸硼酸锂、二氟草酸硼酸锂、高氯酸锂、四氟硼酸锂、二氟二草酸磷酸锂和双氟磺酰亚胺锂中的至少一种。The non-aqueous electrolytic solution according to claim 1, wherein the lithium salt is selected from lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium bistrifluoromethylsulfonimide, lithium bisoxalate borate, difluoromethanesulfonate lithium At least one of lithium oxalate borate, lithium perchlorate, lithium tetrafluoroborate, lithium difluorodioxalate phosphate, and lithium bisfluorosulfonyl imide.
  7. 如权利要求1所述的非水电解液，其特征在于，所述非水有机溶剂选自碳酸乙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸丙烯酯、乙酸丁酯、γ-丁内酯、丙酸丙酯、丙酸乙酯和丁酸乙酯中的至少一种。nonaqueous electrolytic solution as claimed in claim 1, is characterized in that, described nonaqueous organic solvent is selected from ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, butyl acetate , at least one of γ-butyrolactone, propyl propionate, ethyl propionate and ethyl butyrate.
  8. 一种二次电池，包括正极材料、负极材料和电解液，其特征在于，所述电解液为权利要求1～7任一项所述的非水电解液，且最高充电电压为4.35～4.5V。A secondary battery, comprising a positive electrode material, a negative electrode material and an electrolyte, characterized in that the electrolyte is the non-aqueous electrolyte according to any one of claims 1 to 7, and the highest charging voltage is 4.35 to 4.5V .
  9. 如权利要求8所述的二次电池，其特征在于，所述正极材料为Li (1+a)Ni xCo yM zN 1-x-y-zO 2+b，其中，M为Mn或Al，N为Mg、Cu、Zn、Sn、B、Ga、Cr、Sr、Ba、V和Ti中的任意一种，-0.10≤a≤0.50，0.6＜x＜0.9，0＜y＜1，0<z＜1，0.6＜x+y+z≤1，-0.05≤b≤0.10。 The secondary battery according to claim 8, wherein the positive electrode material is Li (1+a) Ni x Co y M z N 1-xyz O 2+b , wherein M is Mn or Al, N Any one of Mg, Cu, Zn, Sn, B, Ga, Cr, Sr, Ba, V and Ti, -0.10≤a≤0.50, 0.6<x<0.9, 0<y<1, 0<z <1, 0.6<x+y+z≤1, -0.05≤b≤0.10.
  10. 如权利要求8所述的二次电池，其特征在于，所述负极材料选自人造石墨、天然石墨、钛酸锂、硅碳复合材料和氧化亚硅中的至少一种。The secondary battery according to claim 8, wherein the negative electrode material is selected from at least one of artificial graphite, natural graphite, lithium titanate, silicon-carbon composite material and silicon oxide.
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