WO2020052118A1 - Lithium ion battery electrolyte, and lithium ion battery containing electrolyte - Google Patents

Lithium ion battery electrolyte, and lithium ion battery containing electrolyte Download PDF

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WO2020052118A1
WO2020052118A1 PCT/CN2018/119971 CN2018119971W WO2020052118A1 WO 2020052118 A1 WO2020052118 A1 WO 2020052118A1 CN 2018119971 W CN2018119971 W CN 2018119971W WO 2020052118 A1 WO2020052118 A1 WO 2020052118A1
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lithium
ion battery
carbonate
positive electrode
lithium ion
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PCT/CN2018/119971
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French (fr)
Chinese (zh)
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朱学全
杜建委
潘立宁
黄慧聪
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东莞市杉杉电池材料有限公司
杉杉新材料（衢州）有限公司
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Publication of WO2020052118A1 publication Critical patent/WO2020052118A1/en

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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
    • 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 technical field of lithium-ion batteries, and in particular to a lithium-ion battery electrolyte and a lithium-ion battery containing the electrolyte.
  • Improving the energy density of lithium-ion batteries is the eternal pursuit of power battery products and digital or energy storage battery products.
  • the current mainstream method for developing high-energy-density lithium-ion batteries is to increase the battery's operating voltage and use positive and negative electrode active materials with higher capacity.
  • Nickel-cobalt-manganate ternary material is one of the more popular materials currently on the market. By increasing the content of nickel, the specific capacity of the material can be greatly increased, and the cost of the battery can be reduced. However, in a lithium-ion battery system using a high nickel material as a positive electrode, the electrical performance of the battery is affected as the nickel content increases, which is mainly reflected in: 1 the thermal stability of the material deteriorates, affecting the high temperature performance and safety performance of the battery; 2 The surface of the positive electrode material is enhanced in alkalinity, which is easy to absorb water and has more stringent environmental requirements; 3 Nickel mainly exists in the form of Ni 3+ in the ternary high nickel system, which can be further oxidized to Ni 4+ , thus showing a stronger The oxidizing property is easy to undergo oxidative decomposition reaction with the electrolyte.
  • the positive electrode material is prone to cracks during the charge and discharge process, and with the release of the lattice oxygen, a highly active O 2 is formed , which easily causes the battery to generate gas during use or storage. , Shorten the battery life, increase the hidden dangers in the battery use process.
  • the present invention finds that by forming a stable protective film component on the surface of the negative electrode and the positive electrode, the gas generation problem of the battery can be significantly improved.
  • the component rich in inorganic salt film has better thermal stability and suitable Impedance, small molecule organic film components have good toughness but not high temperature resistance.
  • Organic components with a certain degree of polymerization have better high temperature performance and mechanical stability.
  • the stability of the electrolyte membrane is obtained under the condition that organic components and inorganic components coexist. Promotion.
  • forming a stable passivation film at the cathode end is also important to improve the high temperature performance of the battery.
  • the passivation film produced by high temperature nickel additives in conventional high temperature additives Unstable, easily decomposed by thermal decomposition or oxidized decomposition of dissolved metal ions, showing thermal instability and electrochemical instability, or film formation of high-temperature additives is too thick, resulting in insufficient capacity and large increase in impedance.
  • the lithium ion battery electrolyte of the present invention is composed of a lithium salt, a non-aqueous organic solvent, and an additive.
  • the additive contains one or more cyclic unsaturated phosphates having a structure of M or N. Among them,
  • R 1 , R 2 , R 3 , R 4 , R 5 in M and N are each independently selected from methyl, ethyl, propyl, isopropyl, trifluoromethyl, trifluoroethyl, polyfluoroalkyl, Perfluoroalkyl, phenyl, p-methylphenyl, p-fluorophenyl, polyfluorophenyl, perfluorophenyl, propenyl, allyl, methylene.
  • the cyclic unsaturated phosphate M or N compound is added in an amount of 0.05-5% of the total weight of the electrolyte.
  • the structural formula of the cyclic unsaturated phosphate M or N compound is:
  • the additive further includes fluoroethylene carbonate, vinylene carbonate, 1,3 propane sultone, vinyl sulfate, lithium difluorooxalate borate, and bisoxalate borate
  • fluoroethylene carbonate, vinylene carbonate, 1,3 propane sultone, vinyl sulfate, lithium difluorooxalate borate, and bisoxalate borate One or more of lithium, lithium tetrafluoroborate, lithium difluorobisoxalate phosphate, ethylene ethylene carbonate, 1,3-propane sultone, lithium bisfluorosulfonylimide, and lithium difluorophosphate, More preferably, its content is 0.05-20% of the total mass of the electrolytic solution.
  • the content of the lithium salt is 8 to 20% of the total mass of the electrolytic solution.
  • the non-aqueous organic solvent includes a cyclic carbonate solvent, a chain carbonate solvent, a chain carboxylic acid ester solvent, a chain silicon-containing carbonate solvent, a chain fluorocarbonate solvent, and a cyclic fluorine-containing carbonic acid.
  • a cyclic carbonate solvent a chain carbonate solvent, a chain carboxylic acid ester solvent, a chain silicon-containing carbonate solvent, a chain fluorocarbonate solvent, and a cyclic fluorine-containing carbonic acid.
  • ester solvents One or more of the ester solvents.
  • the present invention also provides a lithium ion battery containing the electrolyte of the present invention.
  • the battery includes a positive electrode sheet, a negative electrode sheet, a separator disposed between the positive electrode sheet and the negative electrode sheet, and the electrolytic solution according to the present invention. .
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode film coated on a surface of the positive electrode current collector, and the positive electrode film includes a positive electrode active material, a positive electrode conductive agent, and a positive electrode binder.
  • the nickel-cobalt-manganese ratio in the ternary material is 424, 333, 523, 701, 811, 515.
  • the material system of the positive electrode may have a single crystal structure and secondary particles, and the surface may be coated with aluminum oxide, graphene, carbon nanotubes, carbon materials, and a conductive polymer layer, and may be further used.
  • Alkaline earth metals beryllium, magnesium, calcium, strontium, barium, rare earth metals rhenium, yttrium, lanthanum, cerium, praseodymium, neodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, thorium modified.
  • compositions, step, method, article, or device that contains the listed elements need not be limited to those elements, but may include other elements not explicitly listed or inherent to such a composition, step, method, article, or device. Elements.
  • the negative electrode active material graphite, conductive agent acetylene black, binder styrene-butadiene rubber (SBR), and thickener sodium carbon methyl cellulose (CMC) were used in a deionized water solvent system at a mass ratio of 96: 2: 1: 1. After being fully stirred and mixed uniformly, it was coated on a Cu foil, dried, and cold-pressed to obtain a negative electrode sheet.
  • Polyethylene (PE) was used as a base film (14 m), and a nano-alumina coating (2 m) was coated on the base film as a separator.
  • the battery systems and electrolyte formulations used in Examples 2-25 are configured according to Table 1 below, and are not described here one by one.

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

A lithium ion battery electrolyte, and a lithium ion battery containing the electrolyte. The lithium ion battery electrolyte consists of lithium salt, a non-aqueous organic solvent, and an additive, wherein the additive contains one or more cyclic unsaturated phosphate esters having a structure of M or N, and the added amount accounts for 0.05%-5% of the total weight of the electrolyte. The cyclic unsaturated phosphate ester can be reduced to form an SEI film at a cathode interface, and can also be decomposed to form a passivation layer at the cathode interface to inhibit the occurrence of a side reaction. The additive may further comprise vinyl fluorocarbonate, vinylidene carbonate, vinyl sulfate, lithium borate difluorooxalate, lithium borate dioxalate, lithium tetrafluoroborate, lithium phosphate difluorobioxalate, vinylidene carbonate, and 1,3-propylene sulfonate, etc. By adopting the additive, the gas production of the battery can be inhibited, the high-temperature storage performance of a high-nickel ternary battery can be improved, and the cycle stability of the battery can be improved.

Description

一种锂离子电池电解液及含有该电解液的锂离子电池Lithium ion battery electrolyte and lithium ion battery containing the same 技术领域Technical field
本发明涉及锂离子电池技术领域，具体是涉及一种锂离子电池电解液及含有该电解液的锂离子电池。The present invention relates to the technical field of lithium-ion batteries, and in particular to a lithium-ion battery electrolyte and a lithium-ion battery containing the electrolyte.
背景技术Background technique
提高锂离子电池能量密度是动力电池产品和数码或储能电池产品永恒的追求。发展高能量密度锂离子电池目前采用的比较主流的方法是提升电池的工作电压和采用容量更高的正负极活性材料。Improving the energy density of lithium-ion batteries is the eternal pursuit of power battery products and digital or energy storage battery products. The current mainstream method for developing high-energy-density lithium-ion batteries is to increase the battery's operating voltage and use positive and negative electrode active materials with higher capacity.
镍钴锰酸锂三元材料是目前市面比较受欢迎的材料之一，通过提高镍的含量能大大提升材料的比容量，同时降低电池的成本。然而，在以高镍材料为正极的锂离子电池体系中，随着镍含量的增加电池的电性能受到影响，主要体现在：①材料的热稳定变差，影响电池的高温性能和安全性能；②正极材料表面碱性增强，容易吸水同时对环境要求更严苛；③镍在三元高镍体系中主要以Ni 3+形式存在，可以进一步的被氧化为Ni 4+，从而呈现出较强的氧化性，容易与电解液发生氧化分解反应，正极材料在充放电过程中容易产生裂纹，并且伴随着晶格氧的释放形成高活性态的O 2，容易造成电池在使用或储存过程中产气，缩短了电池的使用寿命，增加了电池使用过程中的安全隐患。 Nickel-cobalt-manganate ternary material is one of the more popular materials currently on the market. By increasing the content of nickel, the specific capacity of the material can be greatly increased, and the cost of the battery can be reduced. However, in a lithium-ion battery system using a high nickel material as a positive electrode, the electrical performance of the battery is affected as the nickel content increases, which is mainly reflected in: ① the thermal stability of the material deteriorates, affecting the high temperature performance and safety performance of the battery; ② The surface of the positive electrode material is enhanced in alkalinity, which is easy to absorb water and has more stringent environmental requirements; ③ Nickel mainly exists in the form of Ni 3+ in the ternary high nickel system, which can be further oxidized to Ni 4+ , thus showing a stronger The oxidizing property is easy to undergo oxidative decomposition reaction with the electrolyte. The positive electrode material is prone to cracks during the charge and discharge process, and with the release of the lattice oxygen, a highly active O 2 is formed , which easily causes the battery to generate gas during use or storage. , Shorten the battery life, increase the hidden dangers in the battery use process.
发明内容Summary of the Invention
为了改善以高镍材料为正极的锂离子电池的性能，可通过控制电池的产气、抑制活性材料端在使用过程中内阻的增加。本发明发现通过在负极和正极表面构建稳定的保护膜组分可以明显改善电池的产气问题，按照固体电解质膜的模型，富含无机盐膜的组分具有较好的热稳定性和适宜的阻抗，小分子有机膜类组分韧性好但不耐高温，具 有一定聚合度的有机组分高温性能和力学稳定性更佳，有机组分和无机组分共存的条件下电解质膜的稳定性得到提升。在电池体系中除了在阳极端形成固体电解质保护膜之外，在阴极端形成稳定的钝化膜被对提升电池高温性能也尤为重要，常规的高温型添加剂在高镍体系中产生的钝化膜不稳定，容易被热分解或被溶出的金属离子氧化分解，呈现出热不稳定性和电化学不稳定性，或者高温添加剂成膜过于厚实导致容量发挥不够，阻抗增大较大等问题。In order to improve the performance of a lithium ion battery using a high nickel material as a positive electrode, the increase in internal resistance of the active material end during use can be suppressed by controlling the gas generation of the battery. The present invention finds that by forming a stable protective film component on the surface of the negative electrode and the positive electrode, the gas generation problem of the battery can be significantly improved. According to the model of the solid electrolyte film, the component rich in inorganic salt film has better thermal stability and suitable Impedance, small molecule organic film components have good toughness but not high temperature resistance. Organic components with a certain degree of polymerization have better high temperature performance and mechanical stability. The stability of the electrolyte membrane is obtained under the condition that organic components and inorganic components coexist. Promotion. In addition to forming a solid electrolyte protective film at the anode end in the battery system, forming a stable passivation film at the cathode end is also important to improve the high temperature performance of the battery. The passivation film produced by high temperature nickel additives in conventional high temperature additives Unstable, easily decomposed by thermal decomposition or oxidized decomposition of dissolved metal ions, showing thermal instability and electrochemical instability, or film formation of high-temperature additives is too thick, resulting in insufficient capacity and large increase in impedance.
为了实现本发明的目的，本发明的锂离子电池电解液由锂盐、非水性有机溶剂和添加剂组成，添加剂中含有结构是M或N的一种或多种环状不饱和磷酸酯，其中，In order to achieve the purpose of the present invention, the lithium ion battery electrolyte of the present invention is composed of a lithium salt, a non-aqueous organic solvent, and an additive. The additive contains one or more cyclic unsaturated phosphates having a structure of M or N. Among them,
M为
Figure PCTCN2018119971-appb-000001
N为
Figure PCTCN2018119971-appb-000002
M和N中R 1，R 2，R 3，R 4，R 5各自独立选自甲基、乙基、丙基、异丙基、三氟甲基、三氟乙基、多氟烷基、全氟烷基、苯基、对甲基苯基、对氟苯基、多氟苯基、全氟苯基、丙烯基、烯丙基、亚甲基。 M is
Figure PCTCN2018119971-appb-000001
N is
Figure PCTCN2018119971-appb-000002
R 1 , R 2 , R 3 , R 4 , R 5 in M and N are each independently selected from methyl, ethyl, propyl, isopropyl, trifluoromethyl, trifluoroethyl, polyfluoroalkyl, Perfluoroalkyl, phenyl, p-methylphenyl, p-fluorophenyl, polyfluorophenyl, perfluorophenyl, propenyl, allyl, methylene.
优选的，为达到电解液良好的性能，环状不饱和磷酸酯M或N化合物的加入量占电解液总重量的0.05-5％。Preferably, in order to achieve good performance of the electrolyte, the cyclic unsaturated phosphate M or N compound is added in an amount of 0.05-5% of the total weight of the electrolyte.
优选的，环状不饱和磷酸酯M或N化合物的结构式为：Preferably, the structural formula of the cyclic unsaturated phosphate M or N compound is:
Figure PCTCN2018119971-appb-000003
Figure PCTCN2018119971-appb-000003
优选的，为进一步改善上述电解液的性能，所述添加剂还包含氟代碳酸乙烯酯、碳酸亚乙烯酯、1,3丙烷磺酸内脂、硫酸乙烯酯、二氟草酸硼酸锂、双草酸硼酸锂、四氟硼酸锂、二氟双草酸磷酸锂、碳酸乙烯亚乙酯、1,3-丙烯磺酸内酯、双氟磺酰亚胺锂和二氟磷酸锂中的一种或多种，进一步优选的，其含量为电解液总质量的0.05～20％。Preferably, in order to further improve the performance of the above electrolyte solution, the additive further includes fluoroethylene carbonate, vinylene carbonate, 1,3 propane sultone, vinyl sulfate, lithium difluorooxalate borate, and bisoxalate borate One or more of lithium, lithium tetrafluoroborate, lithium difluorobisoxalate phosphate, ethylene ethylene carbonate, 1,3-propane sultone, lithium bisfluorosulfonylimide, and lithium difluorophosphate, More preferably, its content is 0.05-20% of the total mass of the electrolytic solution.
优选的，所述锂盐包含六氟磷酸锂、四氟硼酸锂、双草酸硼酸锂、三草酸磷酸锂、二氟草酸硼酸锂、双氟磺酰亚胺锂、双三氟甲烷磺酰亚胺锂、二氟磷酸锂、四氟磷酸锂和二氟双草酸磷酸锂中的一种或多种。Preferably, the lithium salt includes lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bisoxalate borate, lithium trioxalate phosphate, lithium difluorooxalate borate, lithium bisfluorosulfonimide, lithium bistrifluoromethanesulfonimide, One or more of lithium fluorophosphate, lithium tetrafluorophosphate, and lithium difluorobisoxalate phosphate.
进一步优选的，所述锂盐的含量为电解液总质量的8～20％。Further preferably, the content of the lithium salt is 8 to 20% of the total mass of the electrolytic solution.
优选的，所述非水性有机溶剂包含环状碳酸酯溶剂、链状碳酸酯溶剂、链状羧酸酯溶剂、链状含硅碳酸酯溶剂、链状氟代碳酸酯溶剂及环状含氟碳酸酯溶剂中的一种或多种。Preferably, the non-aqueous organic solvent includes a cyclic carbonate solvent, a chain carbonate solvent, a chain carboxylic acid ester solvent, a chain silicon-containing carbonate solvent, a chain fluorocarbonate solvent, and a cyclic fluorine-containing carbonic acid. One or more of the ester solvents.
更优选的，所述非水有机溶剂为碳酸乙烯酯、碳酸丙烯酯、碳酸二乙酯、碳酸甲乙酯、丙酸丙酯、丙酸乙酯、碳酸甲丙酯、四氢呋喃、二氧环烷、γ-丁内酯、乙酸乙酯、乙酸丙酯、乙酸甲酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、(三甲基硅基甲基)甲基碳酸酯、二(三甲基硅基甲基)、(三甲基硅基甲基)乙基碳酸酯、二(三甲基硅基甲基)乙基碳酸酯、碳酸酯中的一种或多种。More preferably, the non-aqueous organic solvent is ethylene carbonate, propylene carbonate, diethyl carbonate, ethyl methyl carbonate, propyl propionate, ethyl propionate, methyl propyl carbonate, tetrahydrofuran, dioxane , Γ-butyrolactone, ethyl acetate, propyl acetate, methyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, (trimethylsilylmethyl) methyl carbonate, bis ( One or more of trimethylsilylmethyl), (trimethylsilylmethyl) ethyl carbonate, bis (trimethylsilylmethyl) ethyl carbonate, and carbonate.
进一步优选的，所述非水有机溶剂的含量为电解液总质量的50～85％。Further preferably, the content of the non-aqueous organic solvent is 50 to 85% of the total mass of the electrolytic solution.
本发明还提供了一种含有本发明电解液的锂离子电池，该电池包括正极极片、负极极片、设置于正极极片和负极极片之间的隔膜，以及本发明所述的电解液。The present invention also provides a lithium ion battery containing the electrolyte of the present invention. The battery includes a positive electrode sheet, a negative electrode sheet, a separator disposed between the positive electrode sheet and the negative electrode sheet, and the electrolytic solution according to the present invention. .
优选的，所述正极极片包括正极集流体和涂覆于正极集流体表面的正极膜片，所述正极膜片包括正极活性物质、正极导电剂和正极粘结剂。Preferably, the positive electrode sheet includes a positive electrode current collector and a positive electrode film coated on a surface of the positive electrode current collector, and the positive electrode film includes a positive electrode active material, a positive electrode conductive agent, and a positive electrode binder.
优选的，所述正极活性物质为钴酸锂、锰酸锂、磷酸亚铁锂、镍钴锰酸铝、富锂锰基固溶体和高镍三元材料LiNi 1-x-y-zCo xMn yAl zO 2，其中：0≤x≤1，0≤y≤1，0≤z≤1且0≤x+y+z≤1， Preferably, the positive electrode active material is lithium cobaltate, lithium manganate, lithium ferrous phosphate, nickel cobalt aluminum manganate, lithium-rich manganese-based solid solution, and high nickel ternary material LiNi 1-xyz Co x Mn y Al z O 2 , where: 0≤x≤1, 0≤y≤1, 0≤z≤1, and 0≤x + y + z≤1,
更优选的，所述三元材料中镍钴锰比列为424、333、523、701、811、515。More preferably, the nickel-cobalt-manganese ratio in the ternary material is 424, 333, 523, 701, 811, 515.
优选的，所述正极的材料体系可以为单晶结构、二次颗粒，表面可以被三氧化二铝、石墨烯、碳纳米管、碳材料、导电高分子层所包覆，并且可以进一步的用碱土金属铍、镁、钙、锶、钡，稀土金属钪、钇、镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥进行掺杂改性。Preferably, the material system of the positive electrode may have a single crystal structure and secondary particles, and the surface may be coated with aluminum oxide, graphene, carbon nanotubes, carbon materials, and a conductive polymer layer, and may be further used. Alkaline earth metals beryllium, magnesium, calcium, strontium, barium, rare earth metals rhenium, yttrium, lanthanum, cerium, praseodymium, neodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, praseodymium, thorium modified.
本发明提供的含有环状不饱和磷酸酯化合物的电解液既可以在负极表面还原分解形成稳定的SEI膜组分，同时在正极表面开环聚合起到抑制材料活性的效果，抑制了高温环境下活性材料与电解液的副反应，减少电池在使用和储存过程中的产气。此外，本发明添加剂在高镍电池体系正负极界面构建稳定的保护膜结构，通过添加剂特殊组合保持界面具有良好的通透性，利于锂离子的扩散和适宜的阻抗，满足高低温和循环性能的要求。The electrolytic solution containing the cyclic unsaturated phosphate compound provided by the present invention can both reduce and decompose on the surface of the negative electrode to form a stable SEI film component, and at the same time, ring-opening polymerization on the surface of the positive electrode can inhibit the activity of the material and inhibit the high temperature environment. The side reaction between the active material and the electrolyte reduces the gas generation during battery use and storage. In addition, the additive of the present invention constructs a stable protective film structure at the positive and negative electrode interface of the high nickel battery system, and maintains the interface with good permeability through a special combination of additives, which is conducive to the diffusion of lithium ions and suitable impedance, and meets the requirements of high and low temperature and cycle performance. Claim.
具体实施方式detailed description
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。本发明的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本发明的实践了解到。应当理解，以下描述仅仅用以解释本 发明，并不用于限定本发明。In order to make the objectives, technical solutions, and advantages of the present invention clearer, the present invention is further described in detail below in combination with the embodiments. Additional aspects and advantages of the present invention will be given in part in the following description, and part of them will become apparent from the following description, or be learned through the practice of the present invention. It should be understood that the following description is only used to explain the present invention and is not intended to limit the present invention.
本文中所用的术语“包含”、“包括”、“具有”、“含有”或其任何其它变形，意在覆盖非排它性的包括。例如，包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素，而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。As used herein, the terms "comprising," "including," "having," "containing," or any other variation thereof are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or device that contains the listed elements need not be limited to those elements, but may include other elements not explicitly listed or inherent to such a composition, step, method, article, or device. Elements.
连接词“由…组成”排除任何未指出的要素、步骤或组分。如果用于权利要求中，此短语将使权利要求为封闭式，使其不包含除那些描述的材料以外的材料，但与其相关的常规杂质除外。当短语“由…组成”出现在权利要求主体的子句中而不是紧接在主题之后时，其仅限定在该子句中描述的要素；其它要素并不被排除在作为整体的所述权利要求之外。The conjunction "consisting of" excludes any unspecified element, step, or component. If used in a claim, this phrase would make the claim closed, so that it does not contain materials other than those described, except for the conventional impurities associated with it. When the phrase "consisting of" appears in a clause of a claim body rather than immediately after the subject, it is limited to the elements described in that clause; other elements are not excluded from the right as a whole Beyond the requirements.
当量、浓度、或者其它值或参数以范围、优选范围、或一系列上限优选值和下限优选值限定的范围表示时，这应当被理解为具体公开了由任何范围上限或优选值与任何范围下限或优选值的任一配对所形成的所有范围，而不论该范围是否单独公开了。例如，当公开了范围“1至5”时，所描述的范围应被解释为包括范围“1至4”、“1至3”、“1至2”、“1至2和4至5”、“1至3和5”等。当数值范围在本文中被描述时，除非另外说明，否则该范围意图包括其端值和在该范围内的所有整数和分数。When an equivalent, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a range of upper and lower preferred values, this should be understood as specifically disclosing the upper or lower limits of any range and the lower limit of any range Or all ranges formed by any pairing of preferred values, whether or not that range is disclosed separately. For example, when the range "1 to 5" is disclosed, the described range should be interpreted as including the ranges "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5" , "1 to 3 and 5", etc. When a numerical range is described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within the range.
本发明要素或组分前的不定冠词“一种”和“一个”对要素或组分的数量要求(即出现次数)无限制性。因此“一个”或“一种” 应被解读为包括一个或至少一个，并且单数形式的要素或组分也包括复数形式，除非所述数量明显只指单数形式。The indefinite articles "a" and "an" before the elements or components of the present invention have no limitation on the quantity requirements (ie, the number of occurrences) of the elements or components. Thus "a" or "an" should be construed to include one or at least one, and elements or components in the singular include the plural as well, unless the stated number clearly refers only to the singular.
而且，本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。Moreover, the technical features involved in the various embodiments of the present invention can be combined with each other as long as they do not conflict with each other.
实施例1Example 1
电解液的制备：在充满氩气的手套箱(水分＜10ppm，氧分＜1ppm)中，将碳酸乙烯酯、碳酸丙烯酯以30：70质量比混合均匀，在混合溶液中加入质量分数为1％的环状不饱和磷酸酯化合物(1)，然后再加入13.5％的LiPF 6，搅拌至其完全溶解，得到锂离子电池电解液。将该电解液注入到下述NCM622/AG-4.3V电池中，并经封装、搁置、化成、老化、二次封装、分容等工序，得到型号为高镍NCM622/AG-4.2V的三元正极材料软包锂离子电池。 Preparation of electrolyte: In a glove box full of argon (moisture <10ppm, oxygen content <1ppm), ethylene carbonate and propylene carbonate are mixed uniformly at a mass ratio of 30:70, and a mass fraction of 1 is added to the mixed solution. % Of the cyclic unsaturated phosphate compound (1), and then 13.5% of LiPF 6 was added and stirred until it was completely dissolved to obtain a lithium ion battery electrolyte. The electrolyte was injected into the following NCM622 / AG-4.3V battery, and after encapsulation, shelving, formation, aging, secondary packaging, and volume separation, etc., a ternary model of high nickel NCM622 / AG-4.2V was obtained. Lithium-ion battery with soft cathode material.
锂离子电池的制备：Preparation of lithium-ion batteries:
(1)NCM622/AG-4.3V电池制作(对比例1-5和实施例1-25的电池制作与此相同)：将正极活性物质LiNi 0.6Co 0.2Mn 0.2O 2(622)、导电剂乙炔黑、粘结剂聚偏二氟乙烯(PVDF)按质量比95：3：2在N-甲基吡咯烷酮溶剂体系中充分搅拌混合均匀后，涂覆于Al箔上烘干、冷压，得到正极极片，其压实密度为3.50g/cm 3。 (1) NCM622 / AG-4.3V battery production (Comparative Examples 1-5 and Example 1-25 were the same): the positive electrode active material LiNi 0.6 Co 0.2 Mn 0.2 O 2 (622), conductive agent acetylene The black and binder polyvinylidene fluoride (PVDF) was thoroughly stirred and mixed in the N-methylpyrrolidone solvent system at a mass ratio of 95: 3: 2, and then coated on an Al foil, dried and cold-pressed to obtain a positive electrode. The pole piece has a compacted density of 3.50 g / cm 3 .
将负极活性物质石墨、导电剂乙炔黑、粘结剂丁苯橡胶(SBR)、增稠剂碳甲基纤维素钠(CMC)按照质量比96：2：1：1在去离子水溶剂体系中充分搅拌混合均匀后，涂覆于Cu箔上烘干、冷压，得到负极极片。以聚乙烯(PE)为基膜(14μm)，并在基膜上涂覆纳米氧 化铝涂层(2μm)作为隔膜。The negative electrode active material graphite, conductive agent acetylene black, binder styrene-butadiene rubber (SBR), and thickener sodium carbon methyl cellulose (CMC) were used in a deionized water solvent system at a mass ratio of 96: 2: 1: 1. After being fully stirred and mixed uniformly, it was coated on a Cu foil, dried, and cold-pressed to obtain a negative electrode sheet. Polyethylene (PE) was used as a base film (14 m), and a nano-alumina coating (2 m) was coated on the base film as a separator.
将正极极片、隔膜、负极极片按顺序叠好，使隔膜处于正负极片中间起到隔离的作用，并卷绕得到裸电芯。将裸电芯置于外包装中，注入制备的电解液并经封装、搁置、化成、老化、二次封装、分容等工序，得到型号为高镍NCM622/AG-4.3V的三元正极材料软包锂离子电池。The positive electrode sheet, the separator, and the negative electrode sheet are stacked in order, so that the separator is in the middle of the positive and negative electrode sheets to play a role of isolation, and wound to obtain a bare cell. The bare cell was placed in an outer package, and the prepared electrolyte was injected and subjected to packaging, shelving, chemical conversion, aging, secondary packaging, and volume separation processes to obtain a ternary cathode material of high nickel NCM622 / AG-4.3V type. Soft case lithium-ion battery.
(2)NCM811/AG-4.2V电池制作(对比例1-5和实施例1-25的电池制作与此相同)：将正极活性物质LiNi 0.8Co 0.1Mn 0.1O 2(811)、导电剂乙炔黑、碳纳米管、粘结剂聚偏二氟乙烯(PVDF)按质量比95：2.8：0.2：2在N-甲基吡咯烷酮溶剂体系中在充满氮气的干燥环境中充分搅拌混合均匀后，涂覆于Al箔上烘干、冷压，得到正极极片，其压实密度为3.50g/cm 3。 (2) NCM811 / AG-4.2V battery production (Comparative Examples 1-5 and Example 1-25 are the same): the positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O 2 (811), conductive agent acetylene Black, carbon nanotubes, and binder polyvinylidene fluoride (PVDF) are mixed in a N-methylpyrrolidone solvent system in a nitrogen-filled dry environment at a mass ratio of 95: 2.8: 0.2: 2. Covered with Al foil, dried and cold-pressed to obtain a positive electrode sheet, and its compacted density was 3.50 g / cm 3 .
将负极活性物质石墨、导电剂乙炔黑、碳纳米管、粘结剂丁苯橡胶(SBR)、增稠剂碳甲基纤维素钠(CMC)按照质量比96：1.8：0.2：1：1在去离子水溶剂体系中充分搅拌混合均匀后，涂覆于Cu箔上烘干、冷压，得到负极极片。以聚乙烯(PE)为基膜(14μm)并在基膜上涂覆纳米氧化铝涂层(2μm)作为隔膜。The negative electrode active material graphite, conductive agent acetylene black, carbon nanotubes, binder styrene-butadiene rubber (SBR), and thickener sodium carbon methylcellulose (CMC) were prepared at a mass ratio of 96: 1.8: 0.2: 1: 1 in After being thoroughly stirred and mixed in the deionized water solvent system, it was coated on a Cu foil, dried and cold-pressed to obtain a negative electrode sheet. Polyethylene (PE) was used as a base film (14 μm) and a nano-alumina coating (2 μm) was coated on the base film as a separator.
将正极极片、隔膜、负极极片按顺序叠好，使隔膜处于正负极片中间起到隔离的作用，并卷绕得到裸电芯。将裸电芯置于外包装中，注入制备的电解液并经封装、搁置、化成、老化、二次封装、分容等工序，得到型号为高镍NCM811/AG-4.2V的三元正极材料软包锂离子电池。The positive electrode sheet, the separator, and the negative electrode sheet are stacked in order, so that the separator is in the middle of the positive and negative electrode sheets to play a role of isolation, and wound to obtain a bare cell. The bare cell was placed in an outer package, and the prepared electrolyte was injected and then subjected to packaging, shelving, formation, aging, secondary packaging, and volume separation processes to obtain a ternary cathode material of high nickel NCM811 / AG-4.2V type. Soft case lithium-ion battery.
对比例1Comparative Example 1
电解液的制备：在充满氩气的手套箱(水分＜10ppm，氧分＜1ppm)中，将碳酸乙烯酯、碳酸丙烯酯以30：70质量比混合均匀，在混合溶液中加入质量分数为13.5％的LiPF 6，搅拌至其完全溶解，得到锂离子电池电解液。将该电解液注入到NCM622/AG-4.3V电池中，并经封装、搁置、化成、老化、二次封装、分容等工序，得到型号为高镍NCM622/AG-4.3V的三元正极材料软包锂离子电池。 Preparation of electrolyte: In a glove box full of argon (moisture <10ppm, oxygen content <1ppm), ethylene carbonate and propylene carbonate were mixed uniformly at a mass ratio of 30:70, and a mass fraction of 13.5 was added to the mixed solution. % LiPF 6 , and stirred until it was completely dissolved to obtain a lithium ion battery electrolyte. The electrolyte was injected into the NCM622 / AG-4.3V battery, and after the steps of packaging, shelving, formation, aging, secondary packaging, and volume separation, a ternary cathode material with a high nickel type NCM622 / AG-4.3V was obtained. Soft case lithium-ion battery.
对比例2Comparative Example 2
电解液的制备：在充满氩气的手套箱(水分＜10ppm，氧分＜1ppm)中，将碳酸乙烯酯、碳酸丙烯酯以30：70质量比混合均匀，在混合溶液中加入质量分数为1％的碳酸乙烯酯，然后再加入13.5％的LiPF 6，搅拌至其完全溶解，得到锂离子电池电解液。将该电解液注入到NCM622/AG-4.3V电池中，并经封装、搁置、化成、老化、二次封装、分容等工序，得到型号为高镍NCM622/AG-4.3V的三元正极材料软包锂离子电池。 Preparation of electrolyte: In a glove box full of argon (moisture <10ppm, oxygen content <1ppm), ethylene carbonate and propylene carbonate are mixed uniformly at a mass ratio of 30:70, and a mass fraction of 1 is added to the mixed solution. % Of ethylene carbonate, and then 13.5% of LiPF 6 was added and stirred until it was completely dissolved to obtain a lithium ion battery electrolyte. The electrolyte was injected into the NCM622 / AG-4.3V battery, and after the steps of packaging, shelving, formation, aging, secondary packaging, and volume separation, a ternary cathode material with a high nickel type NCM622 / AG-4.3V was obtained. Soft case lithium-ion battery.
对比例3Comparative Example 3
电解液的制备：在充满氩气的手套箱(水分＜10ppm，氧分＜1ppm)中，将碳酸乙烯酯、碳酸丙烯酯以30：70质量比混合均匀，在混合溶液中加入质量分数为1％的氟代碳酸乙烯酯，然后再加入13.5％的LiPF 6，搅拌至其完全溶解，得到锂离子电池电解液。将该电解液注入到NCM622/AG-4.3V电池中，并经封装、搁置、化成、老化、二次封装、分容等工序，得到型号为高镍NCM622/AG-4.3V的三元正 极材料软包锂离子电池。 Preparation of electrolyte: In a glove box full of argon (moisture <10ppm, oxygen content <1ppm), ethylene carbonate and propylene carbonate are mixed uniformly at a mass ratio of 30:70, and a mass fraction of 1 is added to the mixed solution. % Of fluoroethylene carbonate, and then 13.5% of LiPF 6 was added and stirred until it was completely dissolved to obtain a lithium ion battery electrolyte. The electrolyte was injected into the NCM622 / AG-4.3V battery, and after the steps of packaging, shelving, formation, aging, secondary packaging, and volume separation, a ternary cathode material with a high nickel type NCM622 / AG-4.3V was obtained. Soft case lithium-ion battery.
对比例4Comparative Example 4
电解液的制备：在充满氩气的手套箱(水分＜10ppm，氧分＜1ppm)中，将碳酸乙烯酯、碳酸丙烯酯以30：70质量比混合均匀，在混合溶液中加入质量分数为1％的硫酸乙烯酯(DTD)，质量分数1％的双氟磺酰亚胺锂(FSI)，1％的1,3丙烷磺酸内脂，1％的二氟磷酸锂，然后再加入13.5％的LiPF 6，搅拌至其完全溶解，得到锂离子电池电解液。将该电解液注入到NCM622/AG-4.3V电池中，并经封装、搁置、化成、老化、二次封装、分容等工序，得到型号为高镍NCM622/AG-4.3V的三元正极材料软包锂离子电池。 Preparation of electrolyte: In a glove box full of argon (moisture <10ppm, oxygen content <1ppm), ethylene carbonate and propylene carbonate are mixed uniformly at a mass ratio of 30:70, and a mass fraction of 1 is added to the mixed solution. % Of ethylene sulfate (DTD), 1% of lithium bissulfonimide (FSI), 1% of 1,3 propane sultone, 1% of lithium difluorophosphate, and then 13.5% LiPF 6 was stirred until it was completely dissolved to obtain a lithium ion battery electrolyte. The electrolyte was injected into the NCM622 / AG-4.3V battery, and after the steps of packaging, shelving, formation, aging, secondary packaging, and volume separation, a ternary cathode material with a high nickel type NCM622 / AG-4.3V was obtained. Soft case lithium-ion battery.
对比例5Comparative Example 5
电解液的制备：在充满氩气的手套箱(水分＜10ppm，氧分＜1ppm)中，将碳酸乙烯酯、碳酸丙烯酯以30：70质量比混合均匀，在混合溶液中加入质量分数为1％的硫酸乙烯酯(DTD)，质量分数2％的双氟磺酰亚胺锂(FSI)，0.5％的1,3丙烷磺酸内脂，1％的二氟磷酸锂，1％的二氟双草酸磷酸锂，然后再加入13.5％的LiPF 6，搅拌至其完全溶解，得到实施例1的锂离子电池电解液。将该电解液注入到NCM811/AG-4.2V电池中，并经封装、搁置、化成、老化、二次封装、分容等工序，得到型号为高镍NCM811/AG-4.2V的三元正极材料软包锂离子电池。 Preparation of electrolyte: In a glove box full of argon (moisture <10ppm, oxygen content <1ppm), ethylene carbonate and propylene carbonate are mixed uniformly at a mass ratio of 30:70, and a mass fraction of 1 is added to the mixed solution. % Of ethylene sulfate (DTD), 2% of lithium bissulfonimide (FSI), 0.5% of 1,3 propane sultone, 1% of lithium difluorophosphate, 1% of difluoro Lithium bisoxalate, and then 13.5% LiPF 6 was added and stirred until it was completely dissolved to obtain the lithium ion battery electrolyte of Example 1. The electrolyte was injected into the NCM811 / AG-4.2V battery, and after the steps of packaging, shelving, formation, aging, secondary packaging, and volume separation, a ternary cathode material with a high nickel type NCM811 / AG-4.2V was obtained. Soft case lithium-ion battery.
实施例2-25Example 2-25
实施例2-25所使用的电池体系以及电解液配方按照下表1中进 行配置，在此不在一一叙述。The battery systems and electrolyte formulations used in Examples 2-25 are configured according to Table 1 below, and are not described here one by one.
表1对比例1-5和实施例1-25的电池体系和电解液组成Table 1 Battery systems and electrolyte compositions of Comparative Examples 1-5 and Examples 1-25
Figure PCTCN2018119971-appb-000004
Figure PCTCN2018119971-appb-000004
Figure PCTCN2018119971-appb-000005
Figure PCTCN2018119971-appb-000005
Figure PCTCN2018119971-appb-000006
Figure PCTCN2018119971-appb-000006
电池各项性能测试Various performance tests of the battery
1.常温1C/1C循环性能：对比例1-5和实施例1-25所制得电池在温度为25℃±2℃环境下，将上述正极材料为镍钴锰酸锂(镍：钴：锰＝6:2:2)电池(容量为1.2AH)和镍钴锰酸锂(镍：钴：锰＝8:1:1)电池(容量为1.5AH)分别以1.0C充恒流电至4.3V和4.2V压后改为恒压充电，至充电电流≤截止电流0.05C，静置5min，然后1.0C放电至截止电压3.0V，静置5min，按上述工序进行充放电实验，共进行500周以上循环，所得数据见表2。1. 1C / 1C cycling performance at room temperature: The batteries prepared in Comparative Examples 1-5 and Examples 1-25 under the environment of a temperature of 25 ° C ± 2 ° C, the above cathode material was lithium nickel cobalt manganate (nickel: cobalt: Manganese = 6: 2: 2) batteries (capacity 1.2AH) and nickel-cobalt lithium manganate (nickel: cobalt: manganese = 8: 1: 1) batteries (capacity 1.5AH) are charged at a constant current of 1.0C to After 4.3V and 4.2V voltage, change to constant voltage charging until the charging current ≤ cut-off current 0.05C, let stand for 5min, and then discharge at 1.0C to cut-off voltage 3.0V, let stand for 5min, charge and discharge experiments were carried out in accordance with the above procedures, a total of For more than 500 weeks, the data obtained are shown in Table 2.
2.45℃1C/1C循环测试：对比例1-5和实施例1-25所制得电池在温度为45℃±2℃环境下，将上述正极材料为镍钴锰酸锂(镍：钴：锰＝6:2:2)电池(容量为1.2AH)和镍钴锰酸锂(镍：钴：锰＝8:1:1)电池(容量为1.5AH)分别以1.0C充恒流电至4.3V和4.2V压后改为恒压充电，至充电电流≤截止电流0.05C，静置5min，然后1.0C放电至截止电压3.0V，静置5min，按上述工序进行充放电实验，共进行500周以上循环，实验所测试数据见表2。2.45 ° C 1C / 1C cycle test: The batteries prepared in Comparative Examples 1-5 and Examples 1-25 were used at a temperature of 45 ° C ± 2 ° C, and the above-mentioned cathode material was lithium nickel cobalt manganate (nickel: cobalt: manganese). = 6: 2: 2) batteries (capacity 1.2AH) and nickel-cobalt lithium manganate (nickel: cobalt: manganese = 8: 1: 1) batteries (capacity 1.5AH) were charged at a constant current of 1.0C to 4.3 After the voltage of V and 4.2V was changed to constant voltage charging, until the charging current ≤ cut-off current 0.05C, let stand for 5min, and then discharge at 1.0C to cut-off voltage 3.0V, let stand for 5min, charge and discharge experiments were carried out according to the above procedures, a total of 500 Cycle for more than one week, the test data of the laboratory are shown in Table 2.
3.高温60℃出7天：对比例1-5和实施例1-25所制得电池在温 度为25℃±2℃环境下，将上述正极材料为镍钴锰酸锂(镍：钴：锰＝6:2:2)电池(容量为1.2AH)和镍钴锰酸锂(镍：钴：锰＝8:1:1)电池(容量为1.5AH)分别以1.0C充恒流电至4.3V和4.2V至满电状态(100％SOC),然后将电池放置在环境温度为60±2℃的环境中开路搁置7天，然后立即取出电池测厚度，放置4h后恢复至常温然后以0.2C放电测试剩余容量，再以0.2C充放电测试电池的恢复容量。通过电池储存前后的厚度变化、容量变化计算得出电池的高温储存热测厚度变化、剩余容量变化率和恢复容量变化率，实验测试的数据详见表2。3. High temperature at 60 ° C for 7 days: The batteries prepared in Comparative Examples 1-5 and Examples 1-25 under the environment of a temperature of 25 ° C ± 2 ° C, the above cathode material was lithium nickel cobalt manganate (nickel: cobalt: Manganese = 6: 2: 2) batteries (capacity 1.2AH) and nickel-cobalt lithium manganate (nickel: cobalt: manganese = 8: 1: 1) batteries (capacity 1.5AH) are charged at a constant current of 1.0C to 4.3V and 4.2V to the fully charged state (100% SOC), then place the battery in an environment with an ambient temperature of 60 ± 2 ° C and leave it open for 7 days, then immediately take out the battery to measure the thickness, return to normal temperature after 4h, and then 0.2C discharge test remaining capacity, and then 0.2C charge and discharge test battery recovery capacity. The thickness change, the remaining capacity change rate, and the recovery capacity change rate of the battery at high temperature storage are calculated from the thickness change and capacity change of the battery before and after storage. The experimental test data is shown in Table 2.
4.低温-20℃-1C放电：对比例1-5和实施例1-25所制得电池在温度为25℃±2℃环境下，将上述正极材料为镍钴锰酸锂(镍：钴：锰＝6:2:2)电池(容量为1.2AH)和镍钴锰酸锂(镍：钴：锰＝8:1:1)电池(容量为1.5AH)分别以1.0C充恒流电至4.3V和4.2V至满电状态(100％SOC),然后将电池放置在环境温度为-20±2℃的环境中开路搁置4H，然后进行1C倍率的放电测试，记录低温-20℃下1C放电容量，通过计算低温-20℃的放电容量与常温放电容量的比例即为低温-20℃下1C放电效率，实验测试的数据详见表2。4. Low-temperature -20 ° C-1C discharge: The batteries prepared in Comparative Examples 1-5 and Examples 1-25 under the environment of a temperature of 25 ° C ± 2 ° C, the above-mentioned cathode material was lithium nickel cobalt manganate (nickel: cobalt : Manganese = 6: 2: 2) battery (capacity 1.2AH) and nickel-cobalt lithium manganate (nickel: cobalt: manganese = 8: 1: 1) battery (capacity 1.5AH) charge constant current at 1.0C respectively To 4.3V and 4.2V to the fully charged state (100% SOC), then place the battery in an environment with an ambient temperature of -20 ± 2 ° C and leave it open for 4H, then perform a discharge test at a rate of 1C, and record the low temperature at -20 ° C 1C discharge capacity. By calculating the ratio of the discharge capacity at low temperature -20 ℃ to the discharge capacity at normal temperature, it is the discharge efficiency at 1C at low temperature -20 ℃. The experimental test data is shown in Table 2.
下表列出了采用整理622/AG高电位4.3V和811/AG软包电池在采用上述对比例1-5和实施例1-25电解液的常温、高温45℃-1C/1C循环，60℃储存7天及低温-20℃1C放电的性能数据：The following table lists the normal-temperature, high-temperature 45 ° C-1C / 1C cycle using the finishing 622 / AG high-potential 4.3V and 811 / AG soft pack batteries using the electrolytes of Comparative Examples 1-5 and Examples 1-25 at 60 ° C and 60 ° C. Performance data for 7 days at ℃ and 1C discharge at low temperature -20 ℃:
表2.对比例1-5和实施例1-25的电池的循环性能、高温储存性能以及低温放电性能数据Table 2. Cycle performance, high-temperature storage performance, and low-temperature discharge performance data for the batteries of Comparative Examples 1-5 and Examples 1-25
Figure PCTCN2018119971-appb-000007
Figure PCTCN2018119971-appb-000007
Figure PCTCN2018119971-appb-000008
Figure PCTCN2018119971-appb-000008
Figure PCTCN2018119971-appb-000009
Figure PCTCN2018119971-appb-000009
从上表中数据可以看出：针对622/AG高电位4.3V电池体系，添加剂为碳酸亚乙烯酯的对比例2、氟代碳酸乙烯酯的对比例3，其45℃的高温循环性能相比于对比例1的更差，主要原因与VC在高电位下不稳定容易产气有关，而FEC容易脱出HF酸化电池体系而造成SEI膜的破坏和电解液的分解，在该体系加入本发明提供的环状不饱和磷酸酯化合物1％后的实施例1-3，相比上述添加剂为VC和FEC的对比例，其高温储存性能得到明显改善，60℃储存7天的厚度变化明显降低，剩余容量和回复容量明显提高，高温45℃的循环性能也得到明显提升，说明该类添加剂对622/AG-4.3V体系具有更佳的高温性能，原因是其与环状不饱和磷酸酯在负极界面形成了稳定的SEI膜，同时可以在正极界面开环聚合形成保护层钝化正极材料活性，抑 制副反应的发生。From the data in the table above, it can be seen that, for the 622 / AG high-potential 4.3V battery system, the additive is comparative example of vinylene carbonate 2 and comparative example 3 of fluoroethylene carbonate. The worse of Comparative Example 1, the main reason is that VC is unstable and easy to produce gas at high potential, and FEC is easy to take off the HF acidified battery system, which causes the destruction of the SEI film and the decomposition of the electrolyte. Adding the present invention to this system provides In Examples 1-3 after 1% of the cyclic unsaturated phosphate ester compound, compared with the above-mentioned additives of VC and FEC, the high-temperature storage performance was significantly improved. The thickness change after 7 days storage at 60 ° C was significantly reduced, and the remaining The capacity and recovery capacity are significantly improved, and the cycling performance at high temperature of 45 ° C is also significantly improved, indicating that this type of additive has better high temperature performance for the 622 / AG-4.3V system, because it is at the negative electrode interface with the cyclic unsaturated phosphate A stable SEI film is formed, and at the same time, a ring-opening polymerization at the positive electrode interface can form a protective layer to passivate the positive electrode material activity and suppress the occurrence of side reactions.
在上述体系中进一步优化添加剂的组成，采用组合型添加剂的对比例4的常温、高温性能相比于上述单组分添加剂的引入都有明显提升，显示了组合添加剂在解决高镍电池体系的效应，在对比例4的基础上进一步添加本发明的不饱和磷酸酯化合物(1)、化合物(2)和化合物(8)后，其高温性能进一步提高。从实施例5-7可以看出，当环状不饱和磷酸酯化合物(2)的添加量从0.5％提升到1％、3％后，电池的高温性能有所改善，但低温的低温放电性能下降，说明该添加剂加入过多造成低温性能降低，因为该类添加剂为不饱和官能团，形成的钝化膜阻抗增大有关，经实验，该添加剂的最佳加入量是0.1-1％。In the above system, the composition of the additives was further optimized. The room temperature and high temperature performance of Comparative Example 4 using the combined additive was significantly improved compared to the introduction of the above one-component additive, showing the effect of the combined additive in solving the high nickel battery system. After further adding the unsaturated phosphate compound (1), compound (2) and compound (8) of the present invention to Comparative Example 4, its high temperature performance is further improved. It can be seen from Examples 5-7 that when the addition amount of the cyclic unsaturated phosphate compound (2) is increased from 0.5% to 1% and 3%, the high-temperature performance of the battery is improved, but the low-temperature low-temperature discharge performance is improved. The decrease indicates that the low temperature performance is reduced due to the excessive addition of the additive, because the additive is an unsaturated functional group, and the resistance of the passivation film formed is related to the increase. The optimal amount of the additive is 0.1-1% after experiments.
进一步对比表中数据可以看出，苯取代的化合物(8)的低温性能好于甲基和氢取代的化合物(1)和(2)，这与苯的取代对电子具有离域作用有关，经过DFT计算苯取代后分子的还原电位相比锂片会提升，而氧化电位会有所下降。这一方面说明了该类添加剂可以在负极表面比溶剂更早还原而形成SEI膜，另一方面由于氧化电位比溶剂中碳酸乙烯酯的更低，因此先于溶剂发生分解而在正极界面形成保护层，同时本发明所提供是不饱和磷酸酯化合物可以在高温下开环聚合，使得电池具有较好的高温性能。进一步的在正极为镍钴锰酸锂的811电池体系进一步验证了该类添加剂的作用效果，从上表数据可以看出在对比例4的基础上进一步添加本发明所使用的环状不饱和磷酸酯后，电池的高温储存性能进一步提升、60℃储存热测厚度明显减小，在控制添加剂的量在1％以内时低温性能基本不受影响，少量的 添加剂常温循环性能方面略有提升，高温循环性能方面有明显的改善，显示了该类添加剂在高镍体系中具有较好的作用效果。By further comparing the data in the table, it can be seen that the low-temperature performance of the benzene-substituted compound (8) is better than that of the methyl and hydrogen-substituted compounds (1) and (2), which is related to the delocalization effect of benzene on electrons. DFT calculated that the reduction potential of the molecule after benzene substitution will be increased compared to the lithium sheet, while the oxidation potential will decrease. On the one hand, it shows that this type of additives can form an SEI film on the surface of the negative electrode earlier than the solvent. On the other hand, because the oxidation potential is lower than that of the ethylene carbonate in the solvent, it can decompose before the solvent and form a protection at the positive electrode interface. Layer, while the unsaturated phosphate compound provided by the present invention can be ring-opened and polymerized at high temperature, so that the battery has better high-temperature performance. Further, the effect of this type of additive was further verified in the 811 battery system with a positive electrode of nickel cobalt manganate lithium. From the data in the table above, it can be seen that the cyclic unsaturated phosphoric acid used in the present invention was further added on the basis of Comparative Example 4. After the ester, the battery's high-temperature storage performance is further improved, and the thickness at 60 ° C is significantly reduced. When the amount of additives is controlled within 1%, the low-temperature performance is basically not affected, and the small amount of additives has a slight increase in normal temperature cycling performance. Significant improvement in cycle performance has shown that this type of additive has a better effect in high nickel systems.
通过上述实施例和对比例实验可以发现，采用本发明的电解液的三元正极材料电池能够在三元高电压和高镍电池体系中正常工作，并抑制了电池在高温环境中产气，有效降低了电池的膨胀，对电池的高温循环有较好的改善作用。Through the above examples and comparative experiments, it can be found that the ternary cathode material battery using the electrolyte of the present invention can work normally in a ternary high voltage and high nickel battery system, and inhibits the battery from generating gas in a high temperature environment, effectively reducing In order to expand the battery, it can better improve the high temperature cycle of the battery.
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。Those skilled in the art can easily understand that the above description is only the preferred embodiments of the present invention and is not intended to limit the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention, All should be included in the protection scope of the present invention.

Claims (10)

  1. 一种锂离子电池电解液，其特征在于，该锂离子电池电解液由锂盐、非水性有机溶剂和添加剂组成，添加剂中含有结构是M或N的一种或多种环状不饱和磷酸酯，其中，A lithium ion battery electrolyte, characterized in that the lithium ion battery electrolyte is composed of a lithium salt, a non-aqueous organic solvent and an additive, and the additive contains one or more cyclic unsaturated phosphates having a structure of M or N ,among them,
    M为
    Figure PCTCN2018119971-appb-100001
    N为
    Figure PCTCN2018119971-appb-100002
    M和N中R 1，R 2，R 3，R 4，R 5各自独立选自甲基、乙基、丙基、异丙基、三氟甲基、三氟乙基、多氟烷基、全氟烷基、苯基、对甲基苯基、对氟苯基、多氟苯基、全氟苯基、丙烯基、烯丙基、亚甲基。     M is
    Figure PCTCN2018119971-appb-100001
    N is
    Figure PCTCN2018119971-appb-100002
    R 1 , R 2 , R 3 , R 4 , R 5 in M and N are each independently selected from methyl, ethyl, propyl, isopropyl, trifluoromethyl, trifluoroethyl, polyfluoroalkyl, Perfluoroalkyl, phenyl, p-methylphenyl, p-fluorophenyl, polyfluorophenyl, perfluorophenyl, propenyl, allyl, methylene.
  2. 根据权利要求1所述的锂离子电池电解液，其特征在于，所述环状不饱和磷酸酯M或N化合物的加入量占电解液总重量的0.05-5％。The lithium ion battery electrolyte according to claim 1, wherein the cyclic unsaturated phosphate M or N compound is added in an amount of 0.05 to 5% of the total weight of the electrolyte.
  3. 根据权利要求1或2所述的锂离子电池电解液，其特征在于，环状不饱和磷酸酯M或N化合物的结构式为：The lithium ion battery electrolyte according to claim 1 or 2, wherein the structural formula of the cyclic unsaturated phosphate M or N compound is:
    Figure PCTCN2018119971-appb-100003
    Figure PCTCN2018119971-appb-100003
    Figure PCTCN2018119971-appb-100004
    Figure PCTCN2018119971-appb-100004
  4. 根据权利要求1所述的锂离子电池电解液，其特征在于，所述添加剂还包含氟代碳酸乙烯酯、碳酸亚乙烯酯、1,3丙烷磺酸内脂、硫酸乙烯酯、二氟草酸硼酸锂、双草酸硼酸锂、四氟硼酸锂、二氟双草酸磷酸锂、碳酸乙烯亚乙酯、1,3-丙烯磺酸内酯、双氟磺酰亚胺锂和二氟磷酸锂中的一种或多种，优选的，其含量为电解液总质量的0.05～20％。The lithium ion battery electrolyte according to claim 1, wherein the additive further comprises fluoroethylene carbonate, vinylene carbonate, 1,3 propane sultone, vinyl sulfate, and difluorooxalate boric acid One of lithium, lithium bisoxalate borate, lithium tetrafluoroborate, lithium difluorobisoxalate phosphate, ethylene ethylene carbonate, 1,3-propane sultone, lithium bisfluorosulfonylimide, and lithium difluorophosphate Or more, and its content is preferably 0.05 to 20% of the total mass of the electrolytic solution.
  5. 根据权利要求1-4任一项所述的锂离子电池电解液，其特征在于，所述锂盐包含六氟磷酸锂、四氟硼酸锂、双草酸硼酸锂、三草酸磷酸锂、二氟草酸硼酸锂、双氟磺酰亚胺锂、双三氟甲烷磺酰亚胺锂、二氟磷酸锂、四氟磷酸锂和二氟双草酸磷酸锂中的一种或多种，优选的，所述锂盐的含量为电解液总质量的8～20％。The lithium ion battery electrolyte according to claim 1, wherein the lithium salt comprises lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bisoxalate borate, lithium trioxalate phosphate, lithium difluorooxalate borate, One or more of lithium bifluorosulfonylimide, lithium bistrifluoromethanesulfonylimide, lithium difluorophosphate, lithium tetrafluorophosphate, and lithium difluorobisoxalate phosphate, preferably, the lithium salt The content is 8-20% of the total mass of the electrolytic solution.
  6. 根据权利要求1-5任一项所述的锂离子电池电解液，其特征在于，所述非水性有机溶剂包含环状碳酸酯溶剂、链状碳酸酯溶剂、链状羧酸酯溶剂、链状含硅碳酸酯溶剂、链状氟代碳酸酯溶剂及环状含 氟碳酸酯溶剂中的一种或多种，优选的，所述非水有机溶剂为碳酸乙烯酯、碳酸丙烯酯、碳酸二乙酯、碳酸甲乙酯、丙酸丙酯、丙酸乙酯、碳酸甲丙酯、四氢呋喃、二氧环烷、γ-丁内酯、乙酸乙酯、乙酸丙酯、乙酸甲酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、(三甲基硅基甲基)甲基碳酸酯、二(三甲基硅基甲基)、(三甲基硅基甲基)乙基碳酸酯、二(三甲基硅基甲基)乙基碳酸酯、碳酸酯中的一种或多种，更优选的，所述非水有机溶剂的含量为电解液总质量的50～85％。The lithium ion battery electrolyte according to claim 1, wherein the non-aqueous organic solvent comprises a cyclic carbonate solvent, a chain carbonate solvent, a chain carboxylic acid ester solvent, and a chain One or more of a silicon-containing carbonate solvent, a chain fluorocarbonate solvent, and a cyclic fluorocarbonate solvent. Preferably, the non-aqueous organic solvent is ethylene carbonate, propylene carbonate, and diethyl carbonate. Esters, ethyl methyl carbonate, propyl propionate, ethyl propionate, methyl propyl carbonate, tetrahydrofuran, dioxane, γ-butyrolactone, ethyl acetate, propyl acetate, methyl acetate, methyl butyrate Esters, ethyl butyrate, propyl butyrate, (trimethylsilylmethyl) methyl carbonate, bis (trimethylsilylmethyl), (trimethylsilylmethyl) ethyl carbonate One or more of bis (trimethylsilylmethyl) ethyl carbonate, carbonate, more preferably, the content of the non-aqueous organic solvent is 50-85% of the total mass of the electrolytic solution.
  7. 一种含有权利要求1-6任一项所述电解液的锂离子电池，其特征在于，该电池包括正极极片、负极极片、设置于正极极片和负极极片之间的隔膜，以及权利要求1-6任一项所述的电解液，优选的，所述正极极片包括正极集流体和涂覆于正极集流体表面的正极膜片，所述正极膜片包括正极活性物质、正极导电剂和正极粘结剂。A lithium ion battery containing the electrolyte according to any one of claims 1 to 6, characterized in that the battery comprises a positive electrode piece, a negative electrode piece, a separator disposed between the positive electrode piece and the negative electrode piece, and The electrolytic solution according to any one of claims 1 to 6, preferably, the positive electrode sheet includes a positive electrode current collector and a positive electrode film coated on a surface of the positive electrode current collector, and the positive electrode film includes a positive electrode active material and a positive electrode. Conductive agent and positive electrode binder.
  8. 根据权利要求7所述的锂离子电池，其特征在于，所述正极活性物质为钴酸锂、锰酸锂、磷酸亚铁锂、镍钴锰酸铝、富锂锰基固溶体和高镍三元材料LiNi 1-x-y-zCo xMn yAl zO 2，其中：0≤x≤1，0≤y≤1，0≤z≤1且0≤x+y+z≤1。 The lithium ion battery according to claim 7, wherein the positive electrode active material is lithium cobaltate, lithium manganate, lithium ferrous phosphate, nickel cobalt aluminum manganate, lithium-rich manganese-based solid solution, and high nickel ternary The material LiNi 1-xyz Co x Mn y Al z O 2 , where: 0≤x≤1, 0≤y≤1, 0≤z≤1, and 0≤x + y + z≤1.
  9. 根据权利要求7所述的锂离子电池，其特征在于，所述三元材料中镍钴锰比列为424、333、523、701、811、515。The lithium-ion battery according to claim 7, wherein the nickel-cobalt-manganese ratio in the ternary material is 424, 333, 523, 701, 811, 515.
  10. 根据权利要求7所述的锂离子电池，其特征在于，所述正极的材料体系为单晶结构、二次颗粒，优选的，表面被三氧化二铝、石墨烯、碳纳米管、碳材料、导电高分子层所包覆，更优选的，进一步的用碱土金属铍、镁、钙、锶、钡，稀土金属钪、钇、镧、铈、镨、 钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥进行掺杂改性。The lithium ion battery according to claim 7, characterized in that the material system of the positive electrode has a single crystal structure and secondary particles, and preferably has a surface covered with alumina, graphene, carbon nanotubes, carbon materials, The conductive polymer layer is coated, and more preferably, it is further alkaline earth metal beryllium, magnesium, calcium, strontium, barium, rare earth metals thorium, yttrium, lanthanum, cerium, praseodymium, neodymium, praseodymium, praseodymium, thallium, thorium, thorium镝, 镝, 铒, 铒, 铥, 铥, 镱, 镥 are doped modified.
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