WO2021109687A1 - 一种高温型锂二次电池电解液及电池 - Google Patents

一种高温型锂二次电池电解液及电池 Download PDF

Info

Publication number
WO2021109687A1
WO2021109687A1 PCT/CN2020/117528 CN2020117528W WO2021109687A1 WO 2021109687 A1 WO2021109687 A1 WO 2021109687A1 CN 2020117528 W CN2020117528 W CN 2020117528W WO 2021109687 A1 WO2021109687 A1 WO 2021109687A1
Authority
WO
WIPO (PCT)
Prior art keywords
secondary battery
lithium secondary
electrolyte
compound
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2020/117528
Other languages
English (en)
French (fr)
Inventor
范超君
范伟贞
信勇
赵经纬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangzhou Tinci Materials Technology Co Ltd
Original Assignee
Guangzhou Tinci Materials Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangzhou Tinci Materials Technology Co Ltd filed Critical Guangzhou Tinci Materials Technology Co Ltd
Priority to US17/781,401 priority Critical patent/US12537226B2/en
Priority to EP20896075.7A priority patent/EP4071877A4/en
Publication of WO2021109687A1 publication Critical patent/WO2021109687A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • H01M10/0567—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
    • H01M10/056—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
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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 invention belongs to the technical field of lithium secondary batteries, and specifically relates to a high-temperature lithium secondary battery electrolyte and battery.
  • Lithium secondary batteries are widely used in power, energy storage, aerospace, digital and other fields because of their advantages of high energy density, high charging efficiency, and long cycle life.
  • the lithium secondary battery includes: a positive electrode composed of a transition metal oxide; a negative electrode composed of a carbon material, a silicon carbon material, or a lithium alloy; and an electrolyte composed of a lithium salt and a solvent.
  • the solvent is volatile and flammable, when it is used under excessive charge and discharge or extreme conditions, it will cause a short circuit or fire in the battery due to heat, and reduce the high temperature stability of the lithium secondary battery.
  • the lithium ion battery electrolyte of the present invention includes a lithium salt, a non-aqueous organic solvent, and additives, and the additives include isocyanate additives, film-forming additives, and fluorinated flame retardant additives.
  • the lithium ion battery electrolyte can form a stable SEI film on the surface of the electrode material by adding the first type of isocyanate type additive and the second type of film-forming additive, which is beneficial to ion conduction and can inhibit the decomposition of the electrolyte; Fluorine-like flame retardant, F atoms can not only form a film at the electrode interface, but also reduce the intermolecular force, reduce its viscosity, and improve the conductivity of the electrolyte.
  • the synergistic effect of each component makes the battery have good high temperature storage performance, normal temperature cycle performance and high temperature cycle performance under high voltage, and there is no hidden safety hazard.
  • Paragraphs 6 and 11 of its specification disclose the use of diisocyanate-based additives and monocyclic sulfate compounds to improve battery performance in high-temperature and high-pressure application environments.
  • the lithium ion battery electrolyte of the present invention includes a lithium salt, an organic solvent, and additives, wherein the additives include sulfur-containing compounds M and N as additives.
  • the additive M can participate in the formation of the passivation film at the positive and negative interfaces, improving high-temperature performance and inhibiting battery gas production.
  • Additive N has a good effect on improving battery cycle performance and adjusting impedance.
  • cyclic sulfonate compounds and isocyanate compounds contribute to the improvement of electrical properties at room temperature, high temperature, and low temperature.
  • Its main purpose is to improve the storage and cycle performance of the battery at room temperature.
  • the diisocyanate compounds and cyclic sulfates/compounds have a certain contribution to the storage and circulation performance at room temperature, high temperature, and low temperature.
  • the bicyclic sulfate compound is inferior to the combination of the bicyclic sulfate compound and the bispropenyl carbonate compound in terms of electrical properties (high-temperature storage and cycle performance).
  • the technical problem to be solved by this application is: how to further develop on the basis of the existing technology to significantly improve the electrochemical performance of the existing electrolyte.
  • the purpose of the present invention is to provide a high-temperature lithium secondary battery electrolyte, which contains an additive composition composed of diisocyanate compounds and bicyclic sulfate compounds.
  • a flexible thin and uniform SEI film is formed on the surface of the negative electrode of the secondary battery, and at the same time, the surface of the positive electrode is passivated to suppress the gas generation during high-temperature storage of the lithium secondary battery, improve high-temperature cycle performance and high-temperature storage performance, and increase cycle life.
  • Another object of the present invention is to provide a battery containing the above-mentioned high-temperature lithium secondary battery electrolyte.
  • a high-temperature lithium secondary battery electrolyte is composed of a non-aqueous solvent, a lithium salt and an additive, and the additive is a diisocyanate compound represented by general formula 1 and a bicyclic compound represented by general formula 2.
  • Composition of sulfate compounds are composed of a non-aqueous solvent, a lithium salt and an additive, and the additive is a diisocyanate compound represented by general formula 1 and a bicyclic compound represented by general formula 2.
  • R 1 is a linking group containing 4 to 12 carbon atoms
  • R 2 is a linking group containing 2 to 6 carbon atoms.
  • the R 1 is selected from alkyl, cycloalkyl, phenyl, heterocyclic group, or the halogen substituent of the above-mentioned linking group;
  • R 2 is selected from alkane Group, cycloalkyl, phenyl, or halogen substituent of the above-mentioned linking group.
  • the diisocyanate compound is at least one of the following structural compounds:
  • the diisocyanate compound is a compound containing two isocyanate groups and can be used as an additive in the electrolyte of a lithium secondary battery.
  • the diisocyanate compound can promote the formation of a thin and uniform film of the electrolyte on the positive and negative electrodes of the battery.
  • the diisocyanate compound mainly promotes the electrolyte to form a flexible solid electrolyte interface film (SEI film) on the negative electrode, which can effectively reduce the damage to the negative electrode structure caused by the insertion and extraction of lithium ions, and at the same time reduce the negative electrode and other components. The reaction between materials, thereby improving the life of the battery.
  • SEI film flexible solid electrolyte interface film
  • the isocyanate group can react with a small amount of water in the electrolyte without the formation of by-products. It has an excellent effect on stabilizing water-sensitive materials such as bicyclic sulfate and LiPF6, that is, it can improve the stability of the non-aqueous electrolyte. , Reduce high-temperature storage gas production and improve high-temperature storage performance.
  • the diisocyanate compound may be 0.03 to 3 parts by weight, preferably 0.03 to 1 part by weight, based on 100 parts by weight of the total weight of the electrolyte.
  • a stable SEI film can be formed on the negative electrode as described above, and a corresponding effect can be produced. Because when the amount of addition is too small, the formed SEI film is too thin to protect the negative electrode; but when the additive content is too high, the formed SEI film is too thick, which will increase the overall impedance of the battery and affect the battery capacity.
  • the bicyclic sulfate compound is at least one selected from Chemical Formula 2a to Chemical Formula 2h.
  • the bicyclic sulfate compound may be 0.1 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the total weight of the electrolyte.
  • the added content is too low, the improvement effect on the battery performance is not obvious; but when the added amount is too large, the chemical instability of the bicyclic sulfate compound due to the structure is serious, which will cause interaction with other components in the electrolyte. Too many side reactions, the added diisocyanate compound is not enough to stabilize its structure, resulting in serious gas production and poor high-temperature performance of the battery.
  • the non-aqueous solvent is composed of a cyclic compound and a linear compound; the non-aqueous solvent accounts for 10-90% of the total weight of the electrolyte.
  • the cyclic compound is at least one of ethylene carbonate, propylene carbonate, ⁇ -butyrolactone, sulfolane and fluoroethylene carbonate;
  • the linear compound is dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl acetate, propyl propionate, ethyl propionate, propyl acetate, methyl propionate, 1 ,At least one of 1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether and 2,2-difluoroethyl acetate.
  • the lithium salt is LiPF 6 , LiAsF 6 , LiClO 4 , LiBF 4 , LiB(C 2 O 4 ) 2 , LiBF 2 C 2 O 4 , LiN( At least one of SO 2 F) 2 , LiN(SO 2 CF 3 ) 2 , LiPO 2 F 2 , LiPF 2 (C 2 O 4 ) 2 and LiPF 4 C 2 O 4 ; the lithium salt accounts for the total electrolyte 8-20% of the weight.
  • the present invention also discloses a high-temperature lithium secondary battery.
  • the lithium secondary battery consists of a positive electrode, a negative electrode, a separator arranged between the positive and negative electrodes, and the high-temperature lithium secondary battery as described above.
  • the electrolyte composition of the secondary battery is described above.
  • the cathode materials of lithium secondary batteries include, but are not limited to, Li 1+a (Ni x Co y M 1-xy ) O 2 , Li (Ni p Mn q Co 2-pq ) O 4 and LiM h (PO 4 ) m
  • Li 1+a (Ni x Co y M 1-xy ) O 2 Li (Ni p Mn q Co 2-pq ) O 4 and LiM h (PO 4 ) m
  • Li 1+a (Ni x Co y M 1-xy ) O 2 Li (Ni p Mn q Co 2-pq ) O 4 and LiM h (PO 4 ) m
  • Li 1+a (Ni x Co y M 1-xy ) O 2 Li (Ni p Mn q Co 2-pq ) O 4 and LiM h (PO 4 ) m
  • Li 1+a (Ni x Co y M 1-xy ) O 2 Li (Ni p
  • the electrolyte additive composition of the present invention can suppress the amount of gas generated during high-temperature storage of lithium secondary batteries and improve the high-temperature cycle life.
  • a flexible thin and uniform SEI film can be formed on the surface of the negative electrode of the lithium secondary battery, and at the same time, the surface of the positive electrode can be passivated, so that the lithium secondary battery has good high temperature performance.
  • the lithium secondary battery has good high-temperature storage performance and cycle life, and has a good capacity retention rate when stored or used under high-temperature conditions.
  • an electrolyte solution (100 g) containing a solvent prepared by mixing ethylene carbonate and ethyl methyl carbonate at a mass ratio of 1:2 and 1M LiPF6 was prepared.
  • the positive electrode material is LiNi0.8Co0.1Mn0.1O2;
  • the negative electrode material is artificial graphite ;
  • the diaphragm is a polyethylene film. Assemble a soft-packed lithium secondary battery according to a conventional method.
  • an electrolyte solution (100 g) containing a solvent prepared by mixing ethylene carbonate and diethyl carbonate at a mass ratio of 1:2 and 1M LiPF6 was prepared.
  • the diisocyanate compound (0.5 g) of the above Chemical Formula 1c was added to the electrolytic solution to prepare a non-aqueous electrolytic solution.
  • the positive electrode material is LiNi0.8Co0.1Mn0.1O2; the negative electrode material is artificial graphite; the separator is a polyethylene film. Assemble a soft-packed lithium secondary battery according to a conventional method.
  • Comparative Example 3 Compared with Comparative Example 1, the difference of Comparative Example 3 is that the electrolyte does not contain a diisocyanate compound.
  • Comparative Example 4 Compared with Comparative Example 1, the difference of Comparative Example 4 is that the diisocyanate compound (1.5g) of the above chemical formula 1c was added to the non-aqueous electrolyte solution of the comparative example 5 instead of the diisocyanate compound (0.5g) of the above chemical formula 1c. ).
  • Comparative Example 5 Compared with Comparative Example 1, the difference of Comparative Example 5 is that the bicyclic sulfate compound (1.5g) of the above chemical formula 2a was added to the non-aqueous electrolyte of the comparative example 1 instead of the diisocyanate compound of the above chemical formula 1c (0.5g).
  • Comparative Example 6 Compared with Comparative Example 1, the difference of Comparative Example 6 is that the diisocyanate compound (0.5g) of the above chemical formula 1c and the vinyl sulfate (DTD) compound (1.0g) were added to the non-aqueous electrolyte of Comparative Example 1. Instead of the diisocyanate compound (0.5 g) of the above chemical formula 1c.
  • Comparative Example 7 Compared with Comparative Example 1, the difference of Comparative Example 7 is that a vinylene carbonate (VC) compound (1.0 g) was added to the non-aqueous electrolyte of Comparative Example 1 instead of the diisocyanate compound (0.5 g).
  • VC vinylene carbonate
  • High temperature cycle performance Place the lithium secondary battery in a thermostat at 45°C, charge it to 4.2V at a constant current of 1C, and then discharge it to 3.0V at a constant current of 1C, cycle for 500 weeks, and measure lithium ion The capacity retention rate of the battery.
  • High-temperature storage performance The formed lithium-ion battery is charged to 4.2V with 1C current and constant voltage at room temperature, and the initial capacity of the battery is measured; then after 30 days of storage at 60°C, discharge to 3.0V at 1C to test lithium The capacity retention rate of the secondary battery; then charge to 4.2V with a 1C current and constant voltage, and measure the capacity recovery rate of the lithium secondary battery.
  • Example 6 of the present invention can prove that not all diisocyanates can achieve good effects when combined with all additives with high temperature improvement.
  • the comparative examples 3-6 of the patent application 201711391825.0 can prove that not all bicyclic sulfate compounds can achieve good effects when combined with all additives with high temperature improvement.
  • the combination of a diisocyanate compound and a bicyclic sulfate compound has a good synergistic effect after a large number of repeated tests.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

属于锂二次电池技术领域，具体涉及一种高温型锂二次电池电解液及电池。高温型锂二次电池包含由二异氰酸酯类化合物和双环状硫酸酯类化合物组成的添加剂组合物，该组合物一起使用时通过协同作用，在锂二次电池负极表面形成具有柔性的薄而均匀的SEI膜，同时钝化正极表面，抑制锂二次电池高温存储期间的气体生成量，改善高温循环性能和高温存储性能，提高循环寿命。

Description

一种高温型锂二次电池电解液及电池 技术领域
本发明属于锂二次电池技术领域，具体涉及一种高温型锂二次电池电解液及电池。
背景技术
随着便携式电子设备的普及化，电子设备所需的二次电池趋于向小型化和轻量化发展，所以作为这些设备的电源的能量密度要求越来越高。而锂二次电池因其具有能量密度高、充电效率高、循环寿命长等优点，被广泛应用与动力、储能、航天、数码等领域。
锂二次电池包括：由过渡金属氧化物构成的正极；由碳材料、硅碳材料或锂合金构成的负极；由锂盐和溶剂构成的电解液。
由于所述溶剂易挥发、易燃，在过度充放电或极端条件下使用时，会导致电池内部因发热引起短路或起火，降低锂二次电池的高温稳定性。
申请人杉杉新材料(衢州)有限公司于2019年提出了一项专利申请CN201910199170.X，其公开了一种高温高压安全性锂离子电池电解液以及锂离子电池。本发明的锂离子电池电解液包括锂盐、非水有机溶剂、添加剂，所述添加剂包括异氰酸酯类添加剂、成膜添加剂和氟代阻燃添加剂。所述锂离子电池电解液通过添加第一类异氰酸酯类添加剂和第二类成膜添加剂，能够在电极材料表面形成稳定的SEI膜，既有利于离子传导又能够抑制电解液的分解；添加第三类氟代阻燃剂，F原子既可以在电极界面成膜，又可以减小分子间作用力，降低其粘度，改善电解液的电导率。各组分协同作用，使得电池在高电压下具有良好的高温存储性能、常温循环性能以及高温循环性能，且无安全隐患。
通过其说明书第6段、第11段公开了采用二异氰酸酯类添加剂、单环硫酸酯化合物来进行电池的高温高压应用环境下的性能改善。
通过其表1记载可知，DTD和甲苯二异氰酸酯联用(实施例7)效果在常温电性能、高温(60℃存储)电性能优于仅适用单异氰酸酯的情况。
申请人东莞市杉杉电池材料有限公司、杉杉新材料(衢州)有限公司于2019年提出一项发明专利申请CN201910104215.0，其公开了一种锂离子电池电解液及含有该电解液的锂离子电池。本发明所述锂离子电池电解液包含锂盐、有机溶剂和添加剂，其中，添加剂中包含含硫化合物M和N作为添加剂。所述添加剂M在正负极界面均能参与钝化膜的形成，提升高温 性能并抑制电池产气，添加剂N对提升电池循环性能和调节阻抗有较好的效果，通过化合物M和N的联合使用可以优化电池体系的循环性能和储存性能，并且使电池体系具有较低的阻抗，达到电池高低温性能兼顾的综合效果。
其说明书第6-7段记载可以得知，环状磺酸酯化合物、异氰酸酯化合物在改善常温、高温、低温电学性能上有所贡献。
而作为该技术节点的最初贡献者，申请人三菱化学株式会社于2012年提出了一项发明专利申请CN201280007151.9，其在说明书第25段、27段记载，其可以采用具有(A)选自具有碳-碳不饱和键的碳酸酯、通式(1)表示的化合物、亚砜类、亚硫酸酯类、砜类、磺酸酯类、磺内酯类及硫酸酯类中的至少一种化合物、(B)具有氟原子的环状碳酸酯、及(C)分子内至少具有2个异氰酸酯基的化合物。
其主要用途在于：改善电池的常温的存储和循环性能。
通过上述现有技术可以得知，对于二异氰酸酯类化合物、环状硫酸酯/化合物在常温、高温、低温的存储、循环等性能方面具有一定的贡献。
申请人深圳新宙邦科技股份有限公司于2017年提出一项发明专利申请CN201711391825.0公开了一种锂离子电池非水电解液，包括双环状硫酸酯化合物和结构式1所示的化合物A；在结构式1中，R3、R4、R5、R6、R7、R8各自独立地选自氢、氟原子或含1～5个碳原子的基团。
通过其表1记载可以得知：双环状硫酸酯化合物在电学性能(高温存储和循环性能)方面不及双环状硫酸酯化合物和双丙烯基碳酸内酯化合物的组合。
综上所述，双环状硫酸酯化合物、单异氰酸酯化合物、二异氰酸酯化合物、单环状硫酸酯化合物的任一一种单独使用均没法达到最优的表现性能。
同时，也没有任何证据直接指出二异氰酸酯化合物和双丙烯基碳酸内酯化合物具有类似的性质，具有任何可替换性。
本申请所要解决的技术问题是：如何在现有技术的基础上进一步开发，以显著提高现有电解液的电化学性能。
发明内容
本发明的目的是提供一种高温型锂二次电池电解液，包含由二异氰酸酯类化合物和双环 状硫酸酯类化合物组成的添加剂组合物，该组合物一起使用时通过协同作用，在锂二次电池负极表面形成具有柔性的薄而均匀的SEI膜，同时钝化正极表面，抑制锂二次电池高温存储期间的气体生成量，改善高温循环性能和高温存储性能，提高循环寿命。
本发明的另一目的是提供一种包含上述高温型锂二次电池电解液的电池。
本发明的技术方案为：
一种高温型锂二次电池电解液，所述电解液由非水溶剂、锂盐和添加剂组成，所述添加剂由通式一所示的二异氰酸酯类化合物和通式二所示的双环状硫酸酯类化合物组成；
O＝C＝N-R 1-N＝C＝O
通式一
Figure PCTCN2020117528-appb-000001
其中，所述R 1为包含4～12个碳原子的连接基团，R 2为包含2～6个碳原子的连接基团。
在上述的一种高温型锂二次电池电解液中，所述R 1选自烷基、环烷基、苯基、杂环基，或上述连接基团的卤素取代基；R 2选自烷基、环烷基、苯基，或上述连接基团的卤素取代基。
在上述的一种高温型锂二次电池电解液中，所述二异氰酸酯类化合物为以下结构化合物中的至少一种：
Figure PCTCN2020117528-appb-000002
Figure PCTCN2020117528-appb-000003
二异氰酸酯化合物是一种含有两个异氰酸酯基团的化合物，可作为锂二次电池电解液中的添加剂，其中所述二异氰酸酯化合物可促进电解液在电池的正极和负极形成薄而均匀的膜，具体地，所述二异氰酸酯化合物主要促进电解液在负极上形成具有柔性的固态电解液界面膜(SEI膜)，能有效地减少锂离子的嵌入和脱出对于负极结构的破坏，同时减少负极和其他材料之间的反应，从而改善电池的寿命。同时，异氰酸酯基团可与电解液中微量的水反应，无副产物生成，对于稳定双环状硫酸酯、LiPF6等对水敏感的物质具有优异的效果，即可以提高非水电解液的稳定性，减少高温存储产气，提高高温存储性能。
二异氰酸酯化合物可以以100重量份电解液的总重量的0.03至3重量份，优选0.03至1重量份。在以上范围内使用二异氰酸酯化合物的情况下，可如上所述在负极形成稳定的SEI膜，并产生相应的效果。因为添加量太少时，形成的SEI膜过薄，不能起到保护负极的效果； 但添加剂含量过高时，形成的SEI膜太厚，会使电池整体阻抗增加，影响电池容量。
在上述的一种高温型锂二次电池电解液中，所述双环状硫酸酯化合物选自化学式2a至化学式2h中的至少一种。
Figure PCTCN2020117528-appb-000004
Figure PCTCN2020117528-appb-000005
在电解液中包含双环状硫酸酯化合物的情况下，双环状硫酸酯化合物可以以基于100重量份电解液的总重量的0.1至5重量份，优选0.1至3重量份。当添加含量过低时，对电池性能的改善效果不明显；但当添加量过大时，双环状硫酸酯化合物因结构导致的化学不稳定性严重，会导致与电解液中其他组分发生过多的副反应，添加的二异氰酸酯化合物不足以稳定其结构，从而导致产气严重，电池高温性能变差。
在上述的一种高温型锂二次电池电解液中，所述非水溶剂由环状化合物和线性化合物组成；所述非水溶剂占电解液总重的10～90％。
所述环状化合物为碳酸乙烯酯、碳酸丙烯酯、γ-丁内酯、环丁砜和氟代碳酸乙烯酯中的至少一种；
所述线型化合物为碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、碳酸甲丙酯、乙酸乙酯、丙酸丙酯、丙酸乙酯、乙酸丙酯、丙酸甲酯、1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚和2,2-二氟乙基乙酸酯中的至少一种。
在上述的一种高温型锂二次电池电解液中，所述锂盐为LiPF 6、LiAsF 6、LiClO 4、LiBF 4、LiB(C 2O 4) 2、LiBF 2C 2O 4、LiN(SO 2F) 2、LiN(SO 2CF 3) 2、LiPO 2F 2、LiPF 2(C 2O 4) 2和LiPF 4C 2O 4中的至少一种；所述锂盐占电解液总重的8～20％。
同时，本发明还公开了一种高温型锂二次电池，所述锂二次电池由正极，负极，设置在所述正、负极之间的隔膜和如上任一所述的种高温型锂二次电池电解液组成。
锂二次电池的正极材料包括但不限于Li 1+a(Ni xCo yM 1-x-y)O 2、Li(Ni pMn qCo 2-p-q)O 4及LiM h(PO 4) m中的一种或几种；其中0≤a≤0.3，0≤x≤1，0≤y≤1，0＜x+y≤1；0≤p≤2，0≤q≤2，0＜p+q≤2；0＜h＜5，0＜m＜5；M为Fe、Ni、Co、Mn、Al或V。
本发明的有益效果如下：
本发明的电解液添加剂组合物可抑制锂二次电池高温存储期间的气体生成量、改善高温循环寿命。
由于二异氰酸酯和双环状硫酸酯的协同作用，锂二次电池负极表面能形成具有柔性的薄而均匀的SEI膜，同时钝化正极表面，从而使得上述锂二次电池具有良好的高温性能。该锂二次电池具有良好的高温存储性能和循环寿命，在高温条件下存储或使用，均具有良好的容量保持率。
具体实施方式
下面结合具体实施方式，对本发明的技术方案作进一步的详细说明，但不构成对本发明的任何限制。
实施例1
本实施例中，制备包含碳酸乙烯酯和碳酸甲乙酯按质量比为1:2混合而成的溶剂和1M LiPF6的电解液(100g)。在所述电解液中添加上述化学式1c的二异氰酸酯化合物(0.03g)和上述化学式2a的双环状硫酸酯化合物(1.0g)，正极材料为LiNi0.8Co0.1Mn0.1O2；负极材料为人造石墨；隔膜为聚乙烯膜。按照常规方法组装成软包锂二次电池。
实施例2
除了在实施例1的非水电解液中添加将上述化学式1c的二异氰酸酯化合物(0.5g)和上述化学式2a的双环状硫酸酯化合物(0.1g)来代替上述化学式1c的二异氰酸酯化合物(0.03g)和上述化学式2a的双环状硫酸酯化合物(1.0g)之外，以与实施例1相同的方法制备锂二次电池。
实施例3
除了在实施例1的非水电解液中添加将上述化学式1c的二异氰酸酯化合物(3.0g)和上述化学式2a的双环状硫酸酯化合物(1.0g)来代替上述化学式1c的二异氰酸酯化合物(0.03g)和上述化学式2a的双环状硫酸酯化合物(1.0g)之外，以与实施例1相同的方法制备锂 二次电池。
实施例4
除了在实施例1的非水电解液中添加将上述化学式1c的二异氰酸酯化合物(0.5g)和上述化学式2a的双环状硫酸酯化合物(5.0g)来代替上述化学式1c的二异氰酸酯化合物(0.03g)和上述化学式2a的双环状硫酸酯化合物(1.0g)之外，以与实施例1相同的方法制备锂二次电池。
实施例5
除了在实施例1的非水电解液中添加将上述化学式1c的二异氰酸酯化合物(0.5g)和上述化学式2a的双环状硫酸酯化合物(1.0g)来代替上述化学式1c的二异氰酸酯化合物(0.03g)和上述化学式2a的双环状硫酸酯化合物(1.0g)之外，以与实施例1相同的方法制备锂二次电池。
实施例6
除了在实施例1的非水电解液中添加将上述化学式1c的二异氰酸酯化合物(0.5g)和上述化学式2c的双环状硫酸酯化合物(1.0g)来代替上述化学式1c的二异氰酸酯化合物(0.03g)和上述化学式2a的双环状硫酸酯化合物(1.0g)之外，以与实施例1相同的方法制备锂二次电池。
实施例7
除了在实施例1的非水电解液中添加将上述化学式1c的二异氰酸酯化合物(0.5g)和上述化学式2d的双环状硫酸酯化合物(1.0g)来代替上述化学式1c的二异氰酸酯化合物(0.03g)和上述化学式2a的双环状硫酸酯化合物(1.0g)之外，以与实施例1相同的方法制备锂二次电池。
实施例8
除了在实施例1的非水电解液中添加将上述化学式1c的二异氰酸酯化合物(0.5g)和上述化学式2f的双环状硫酸酯化合物(1.0g)来代替上述化学式1c的二异氰酸酯化合物(0.03g)和上述化学式2a的双环状硫酸酯化合物(1.0g)之外，以与实施例1相同的方法制备锂二次电池。
实施例9
除了在实施例1的非水电解液中添加将上述化学式1e的二异氰酸酯化合物(0.2g)和上述化学式2a的双环状硫酸酯化合物(1.0g)来代替上述化学式1c的二异氰酸酯化合物(0.03g)和上述化学式2a的双环状硫酸酯化合物(1.0g)之外，以与实施例1相同的方法制备锂二次电池。
实施例10
除了在实施例1的非水电解液中添加将上述化学式1e的二异氰酸酯化合物(0.2g)和上述化学式2c的双环状硫酸酯化合物(1.0g)来代替上述化学式1c的二异氰酸酯化合物(0.03g)和上述化学式2a的双环状硫酸酯化合物(1.0g)之外，以与实施例1相同的方法制备锂二次电池。
对比例1
本对比例中，制备包含碳酸乙烯酯和碳酸二乙酯按质量比为1:2混合而成的溶剂和1M LiPF6的电解液(100g)。在所述电解液中添加上述化学式1c的二异氰酸酯化合物(0.5g)而制备了非水电解液。正极材料为LiNi0.8Co0.1Mn0.1O2；负极材料为人造石墨；隔膜为聚乙烯膜。按照常规方法组装成软包锂二次电池。
对比例2
除了在对比例1的非水电解液中添加将上述化学式2a的双环状硫酸酯化合物(1.0g)来代替上述化学式1c的二异氰酸酯化合物(0.5g)之外，以与对比例1相同的方法制备锂二次 电池。
对比例3
与对比例1相比，对比例3的不同之处在于，电解液中不含二异氰酸酯化合物。
对比例4
与对比例1相比，对比例4的不同之处在于，在对比例5的非水电解液中添加上述化学式1c的二异氰酸酯化合物(1.5g)来代替上述化学式1c的二异氰酸酯化合物(0.5g)。
对比例5
与对比例1相比，对比例5的不同之处在于，在对比例1的非水电解液中添加上述化学式2a的双环状硫酸酯化合物(1.5g)来代替上述化学式1c的二异氰酸酯化合物(0.5g)。
对比例6
与对比例1相比，对比例6的不同之处在于，在对比例1的非水电解液中添加上述化学式1c的二异氰酸酯化合物(0.5g)和硫酸乙烯酯(DTD)化合物(1.0g)来代替上述化学式1c的二异氰酸酯化合物(0.5g)。
对比例7
与对比例1相比，对比例7的不同之处在于，在对比例1的非水电解液中添加碳酸亚乙烯酯(VC)化合物(1.0g)来代替上述化学式1c的二异氰酸酯化合物(0.5g)。
2、锂二次电池高温性能测试
对实施例1～10和对比例1～7中的锂二次电池进行高温性能测试，测试方法为：
高温循环性能：将锂二次电池置于45℃的恒温箱中，以1C的电流恒流恒压充电至4.2V， 然后以1C的电流恒流放电至3.0V，循环500周，测定锂离子电池的容量保持率。
高温存储性能：将化成后的锂离子电池在常温下用1C电流恒流恒压充电至4.2V，测量电池初始容量；然后在60℃环境中储存30天后，以1C放电至3.0V，测试锂二次电池的容量保持率；再以1C电流恒流恒压充电至4.2V，测量锂二次电池的容量恢复率。
测试结果如表1所示：
表1
Figure PCTCN2020117528-appb-000006
由表1可知，实施例1-10中的锂离子电池的高温循环性能、高温存储性能、低温放电性能优于对比例1-8，说明实施例1-10中的电解液添加剂能够有效改善锂二次电池的高温性能。
具体来说：
1、通过实施例5-8和对比例1和2可以得知：单独使用二异氰酸酯化合物、双环状硫酸酯化合物均无法达到满意的电化学效果。
2、通过实施例5-8和对比例6可以得知：二异氰酸酯化合物和单环状硫酸酯复合物的组合无法达到满意的电化学效果。
3、通过实施例5-10和对比例4-5可以得知：即使调高二异氰酸酯化合物、双环状硫酸酯化合物的量并单独使用，都无法达到满意的电化学效果。
并且，本发明的实施例6可证实，二异氰酸酯并不是和所有的具有高温改善的添加剂配合都能够达到良好的效果。
专利申请201711391825.0的对比例3-6可以证明：双环状硫酸酯化合物并不是和所有的具有高温改善的添加剂配合都能够达到良好的效果。
所以，二异氰酸酯化合物、双环状硫酸酯化合物的组合是经过大量的反复的试验后才能得到其两者具有良好的协同效果。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种高温型锂二次电池电解液，其特征在于，所述电解液由非水溶剂、锂盐和添加剂组成，所述添加剂由通式一所示的二异氰酸酯类化合物和通式二所示的双环状硫酸酯类化合物组成；
    O＝C＝N-R 1-N＝C＝O
    通式一
    Figure PCTCN2020117528-appb-100001
    其中，所述R 1为包含4～12个碳原子的连接基团，R2为包含2～6个碳原子的连接基团。
  2. 根据权利要求1所述的一种高温型锂二次电池电解液，其特征在于，所述R 1选自烷基、环烷基、苯基、杂环基，或上述连接基团的卤素取代基；R 2选自烷基、环烷基、苯基，或上述连接基团的卤素取代基。
  3. 根据权利要求1所述的一种高温型锂二次电池电解液，其特征在于，所述二异氰酸酯类化合物为以下结构化合物中的至少一种：
    Figure PCTCN2020117528-appb-100002
    Figure PCTCN2020117528-appb-100003
  4. 根据权利要求1所述的一种高温型锂二次电池电解液，其特征在于，所述双环状硫酸酯化合物选自化学式2a至化学式2h中的至少一种。
    Figure PCTCN2020117528-appb-100004
    Figure PCTCN2020117528-appb-100005
  5. 根据权利要求1所述的一种高温型锂二次电池电解液，其特征在于，所述二异氰酸酯类化合物的重量是所述电解液总重量的0.03％～3％。
  6. 根据权利要求5所述的一种高温型锂二次电池电解液，其特征在于，所述二异氰酸酯类化合物的重量是所述电解液总重量的0.03％～1％。
  7. 根据权利要求1所述的一种高温型锂二次电池电解液，其特征在于，所述双环状硫酸酯类化合物的重量是所述电解液总重量的0.1％～5％。
  8. 根据权利要求6所述的一种高温型锂二次电池电解液，其特征在于，所述双环状硫酸酯类化合物的重量是所述电解液总重量的0.1％～3％。
  9. 根据权利要求1所述的一种高温型锂二次电池电解液，其特征在于，所述非水溶剂由环状化合物和线性化合物组成；所述非水溶剂占电解液总重的10％～90％。
    所述环状化合物为碳酸乙烯酯、碳酸丙烯酯、γ-丁内酯、环丁砜和氟代碳酸乙烯酯中的至少一种；
    所述线型化合物为碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯、碳酸甲丙酯、乙酸乙酯、丙酸丙酯、丙酸乙酯、乙酸丙酯、丙酸甲酯、1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚和2,2-二氟乙基乙酸酯中的至少一种；所述锂盐为LiPF 6、LiAsF 6、LiClO 4、LiBF 4、LiB(C 2O 4) 2、LiBF 2C 2O 4、LiN(SO 2F) 2、LiN(SO 2CF 3) 2、LiPO 2F 2、LiPF 2(C 2O 4) 2和LiPF 4C 2O 4中的至少一种；所述锂盐占电解液总重的8～20％。
  10. 一种高温型锂二次电池，其特征在于，所述锂二次电池由正极，负极，设置在所述正、负极之间的隔膜和权利要求1至9任一所述的种高温型锂二次电池电解液组成。
PCT/CN2020/117528 2019-12-02 2020-09-24 一种高温型锂二次电池电解液及电池 Ceased WO2021109687A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US17/781,401 US12537226B2 (en) 2019-12-02 2020-09-24 High-temperature lithium secondary battery electrolyte and battery cell
EP20896075.7A EP4071877A4 (en) 2019-12-02 2020-09-24 ELECTROLYTE OF A HIGH-TEMPERATURE LITHIUM SECONDARY BATTERY AND BATTERY CELL

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201911215997.1A CN110931869B (zh) 2019-12-02 2019-12-02 一种高温型锂二次电池电解液及电池
CN201911215997.1 2019-12-02

Publications (1)

Publication Number Publication Date
WO2021109687A1 true WO2021109687A1 (zh) 2021-06-10

Family

ID=69848411

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/117528 Ceased WO2021109687A1 (zh) 2019-12-02 2020-09-24 一种高温型锂二次电池电解液及电池

Country Status (4)

Country Link
US (1) US12537226B2 (zh)
EP (1) EP4071877A4 (zh)
CN (1) CN110931869B (zh)
WO (1) WO2021109687A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12580227B2 (en) 2019-09-23 2026-03-17 Guangzhou Tinci Materials Technology Co., Ltd. Bissulfonate compound, preparation method therefor, electrolyte solution and energy storage device

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110931869B (zh) * 2019-12-02 2022-05-27 广州天赐高新材料股份有限公司 一种高温型锂二次电池电解液及电池
CN114122491A (zh) * 2020-08-31 2022-03-01 深圳新宙邦科技股份有限公司 锂离子电池
CN114122494A (zh) * 2020-08-31 2022-03-01 深圳新宙邦科技股份有限公司 锂离子电池
KR20220048542A (ko) * 2020-10-13 2022-04-20 주식회사 엘지에너지솔루션 리튬 이차전지용 비수전해액 및 이를 포함하는 리튬 이차전지
WO2022077311A1 (zh) * 2020-10-15 2022-04-21 宁德新能源科技有限公司 电化学装置和电子装置
CN112615056B (zh) * 2020-12-22 2023-03-31 九江天赐高新材料有限公司 一种用于制备电解液的添加剂组合物、及包含添加剂组合物的电解液、锂离子二次电池
US20240097190A1 (en) * 2021-01-22 2024-03-21 Soulbrain Co., Ltd. Electrolyte solution and secondary battery including the same
WO2022158919A1 (ko) * 2021-01-22 2022-07-28 솔브레인 주식회사 전해액 및 이를 포함하는 이차전지
KR102895749B1 (ko) * 2021-01-25 2025-12-03 삼성에스디아이 주식회사 리튬 전지용 전해질 및 이를 포함하는 리튬 전지
CN114597492A (zh) * 2021-04-12 2022-06-07 深圳市研一新材料有限责任公司 非水电解液以及使用其的锂离子电池
WO2023003128A1 (ko) * 2021-07-22 2023-01-26 삼성에스디아이 주식회사 리튬 이차 전지용 전해액 및 이를 포함하는 리튬 이차 전지
ES3060465T3 (en) * 2021-07-30 2026-03-26 Contemporary Amperex Technology Hong Kong Ltd Electrolyte, secondary battery, battery module, battery pack, and electric device
CN115939511B (zh) * 2021-08-26 2025-07-11 深圳新宙邦科技股份有限公司 一种非水电解液及电池
CN113948774B (zh) * 2021-10-18 2023-12-22 九江天赐高新材料有限公司 一种功率型锂二次电池电解液及电池
EP4235874A4 (en) 2022-01-04 2024-11-13 Contemporary Amperex Technology (Hong Kong) Limited SECONDARY BATTERY, BATTERY MODULE, BATTERY PACK AND ELECTRICAL DEVICE
JP7646851B2 (ja) * 2022-04-01 2025-03-17 香港時代新能源科技有限公司 二次電池、電池モジュール、電池パック及び電気装置
CN115588779B (zh) * 2022-11-11 2023-11-28 广州天赐高新材料股份有限公司 高温型非水电解液和二次电池
JP2024093864A (ja) * 2022-12-27 2024-07-09 エルジー エナジー ソリューション リミテッド 非水系電解液の酸又は水分低減剤、それを含む非水系電解液、及び非水系電解液を含むリチウム二次電池、並びに非水系電解液の酸又は水分を低減する方法
CN116365043A (zh) * 2023-03-28 2023-06-30 浙江锂威能源科技有限公司 一种电解液以及含有该电解液的锂离子电池
WO2024197714A1 (zh) * 2023-03-30 2024-10-03 宁德时代新能源科技股份有限公司 钠离子电池用电解液、钠离子电池单体和二次电池
KR20260009923A (ko) * 2023-05-31 2026-01-20 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 비수성 전해액, 이차 전지 및 전기 장치
EP4715936A1 (en) * 2023-06-05 2026-03-25 Contemporary Amperex Technology Co., Limited Non-aqueous electrolyte, secondary battery, and electrical apparatus
KR20250062880A (ko) * 2023-10-31 2025-05-08 삼성에스디아이 주식회사 리튬 이차 전지
CN121237961A (zh) * 2024-06-28 2025-12-30 宁德时代新能源科技股份有限公司 锂二次电池和用电装置
CN121748535A (zh) * 2024-09-26 2026-03-27 广州天赐高新材料股份有限公司 一种电解液添加剂及其应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101373848A (zh) * 2007-08-23 2009-02-25 株式会社东芝 非水电解液电池
US20110091768A1 (en) * 2007-09-12 2011-04-21 Mitsubishi Chemical Corporation Nonaqueous electrolytic solution for secondary battery and nonaqueous electrolyte secondary battery
CN103339784A (zh) * 2011-01-31 2013-10-02 三菱化学株式会社 非水电解液及使用该非水电解液的非水电解质二次电池
CN106252710A (zh) * 2015-06-08 2016-12-21 Sk新技术株式会社 锂二次电池用电解质和含有其的锂二次电池
CN107851847A (zh) * 2015-08-12 2018-03-27 中央硝子株式会社 非水系电解液及使用其的非水系电解液电池
CN109755636A (zh) * 2019-03-15 2019-05-14 杉杉新材料（衢州）有限公司 一种高温高压安全性锂离子电池电解液以及锂离子电池
CN110931869A (zh) * 2019-12-02 2020-03-27 广州天赐高新材料股份有限公司 一种高温型锂二次电池电解液及电池

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010021236A1 (ja) 2008-08-20 2010-02-25 三洋電機株式会社 非水電解質二次電池
US20130316227A1 (en) * 2011-02-25 2013-11-28 Sanyo Electric Co., Ltd. Non-aqueous electrolyte secondary battery
US20130323570A1 (en) * 2011-02-28 2013-12-05 Sanyo Electric Co., Ltd. Nonaqueous electrolyte secondary battery
WO2014139986A1 (en) * 2013-03-15 2014-09-18 Basf Se Compositions for use as protective layers and other components in electrochemical cells
CN105140561A (zh) * 2015-07-08 2015-12-09 深圳新宙邦科技股份有限公司 一种锂离子电池非水电解液及锂离子电池
KR102152365B1 (ko) * 2016-02-12 2020-09-04 삼성에스디아이 주식회사 유기전해액 및 상기 전해액을 채용한 리튬 전지
JP6354964B2 (ja) * 2016-10-31 2018-07-11 株式会社Ｇｓユアサ 非水電解質二次電池
CN108258311B (zh) * 2016-12-29 2020-07-10 深圳新宙邦科技股份有限公司 锂离子电池非水电解液及锂离子电池
CN109950621B (zh) * 2017-12-21 2022-05-03 深圳新宙邦科技股份有限公司 一种锂离子电池非水电解液及锂离子电池
CN110120553B (zh) * 2018-02-05 2021-10-22 宁德新能源科技有限公司 一种电解液和锂离子电池
CN109888386A (zh) 2019-01-18 2019-06-14 东莞市杉杉电池材料有限公司 一种锂离子电池电解液及含有该电解液的锂离子电池
CN110021785A (zh) * 2019-04-15 2019-07-16 杉杉新材料（衢州）有限公司 一种三元高电压锂离子电池电解液及三元高电压锂离子电池
CN110204553A (zh) * 2019-05-22 2019-09-06 杨记 一种新型含硫电解液添加剂及其合成制备方法
CN110668978B (zh) 2019-09-23 2025-08-26 广州天赐高新材料股份有限公司 双磺酸酯化合物及其制备方法以及电解液和储能装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101373848A (zh) * 2007-08-23 2009-02-25 株式会社东芝 非水电解液电池
US20110091768A1 (en) * 2007-09-12 2011-04-21 Mitsubishi Chemical Corporation Nonaqueous electrolytic solution for secondary battery and nonaqueous electrolyte secondary battery
CN103339784A (zh) * 2011-01-31 2013-10-02 三菱化学株式会社 非水电解液及使用该非水电解液的非水电解质二次电池
CN106252710A (zh) * 2015-06-08 2016-12-21 Sk新技术株式会社 锂二次电池用电解质和含有其的锂二次电池
CN107851847A (zh) * 2015-08-12 2018-03-27 中央硝子株式会社 非水系电解液及使用其的非水系电解液电池
CN109755636A (zh) * 2019-03-15 2019-05-14 杉杉新材料（衢州）有限公司 一种高温高压安全性锂离子电池电解液以及锂离子电池
CN110931869A (zh) * 2019-12-02 2020-03-27 广州天赐高新材料股份有限公司 一种高温型锂二次电池电解液及电池

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4071877A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12580227B2 (en) 2019-09-23 2026-03-17 Guangzhou Tinci Materials Technology Co., Ltd. Bissulfonate compound, preparation method therefor, electrolyte solution and energy storage device

Also Published As

Publication number Publication date
EP4071877A1 (en) 2022-10-12
CN110931869A (zh) 2020-03-27
US12537226B2 (en) 2026-01-27
CN110931869B (zh) 2022-05-27
EP4071877A4 (en) 2024-11-13
US20230027087A1 (en) 2023-01-26

Similar Documents

Publication Publication Date Title
WO2021109687A1 (zh) 一种高温型锂二次电池电解液及电池
CN107611479B (zh) 锂离子动力电池电解液及锂离子二次电池
CN103594729B (zh) 一种用于锂离子电池的电解液
CN102569885B (zh) 锂离子电池用非水电解液及锂离子二次电池
CN102569880B (zh) 锂离子二次电池及其电解液以及酰胺类化合物的应用
CN109361017B (zh) 一种复合型锂离子电池电解液及包含该电解液的锂离子电池
CN108428940A (zh) 用于锂二次电池的电解液和包括其的锂二次电池
CN113328143A (zh) 一种锂电池用非水电解液及其制备方法和锂离子电池
JP6799085B2 (ja) リチウムイオン電池
CN111788732A (zh) 锂二次电池电解液及包含其的锂二次电池
WO2022127796A1 (zh) 电池电解液、二次电池和终端
CN105977525A (zh) 一种使用非水电解液的锂离子电池
KR102412568B1 (ko) 리튬이온 배터리 비수전해액 및 리튬이온 배터리
CN108390098B (zh) 一种高电压锂离子电池电解液及高电压锂离子电池
CN104335409A (zh) 二次电池用非水电解液和锂离子二次电池
CN107732302A (zh) 一种非水电解液及其制备方法和应用
TWI694630B (zh) 非水電解液用添加劑、非水電解液及蓄電裝置
CN108933291A (zh) 锂离子电池非水电解液和锂离子电池
CN113889671B (zh) 电解液和锂离子电池
CN111200163A (zh) 一种适用于高镍-硅碳体系无ec锂离子电池电解液
WO2025194630A1 (zh) 一种电解液及其应用
CN111640988A (zh) 一种基于全氟磺酰基乙烯基醚的锂离子电池电解液及其制备方法和应用
WO2023123841A1 (zh) 电解液添加剂和含有该添加剂的电解液及锂离子电池
CN115868057A (zh) 用于制备聚合物电解质的前驱物组合物及使用其制备的聚合物电解质和二次电池
CN118738567A (zh) 一种电解液及锂离子电池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20896075

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2020896075

Country of ref document: EP

Effective date: 20220704

WWG Wipo information: grant in national office

Ref document number: 17781401

Country of ref document: US