WO2019153635A1 - Ether-ester composite electrolyte solution for stabilizing lithium metal battery - Google Patents

Ether-ester composite electrolyte solution for stabilizing lithium metal battery Download PDF

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WO2019153635A1
WO2019153635A1 PCT/CN2018/094684 CN2018094684W WO2019153635A1 WO 2019153635 A1 WO2019153635 A1 WO 2019153635A1 CN 2018094684 W CN2018094684 W CN 2018094684W WO 2019153635 A1 WO2019153635 A1 WO 2019153635A1
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lithium
ether
ester
electrolyte
carbonate
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Chinese (zh)
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张强
张学强
闫崇
程新兵
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清华大学
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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three 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
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/0042—Four or more solvents
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to an ether ester composite electrolyte for stabilizing a lithium metal battery, and belongs to the technical field of rechargeable high-energy secondary batteries.
  • lithium metal batteries since the introduction of lithium metal batteries in the 1950s, they have always faced safety problems due to uneven deposition of lithium, hindering the commercialization of lithium metal batteries.
  • the solid electrolyte interface film formed by the reduction and degradation of the liquid electrolyte has a very significant influence on the behavior of lithium deposition, which is directly related to the cycle life and safety of the battery. Therefore, research and development of lithium metal battery electrolytes that can significantly improve lithium deposition uniformity and battery stability and safety have become current research hotspots and challenges.
  • the object of the present invention is to provide an ether ester composite electrolyte for stabilizing a lithium metal battery, which can regulate the uniformity of deposition of the lithium metal anode, inhibit the formation of lithium dendrites, and improve the life and safety of the lithium metal battery during long battery life. Sex.
  • An ether ester composite electrolyte for stabilizing a lithium metal battery comprising an ether ester mixed solvent, an electrolyte and lithium nitrate; wherein the molar concentration of the electrolyte is 0.5 to 4 mol/L; based on the ether ester
  • the composite electrolyte has a mass fraction of lithium nitrate of 0.01 to 10%.
  • the electrolyte comprises: lithium hexafluorophosphate, lithium bis(oxalate)borate, lithium bistrifluoromethanesulfonimide, lithium bisfluorosulfonimide, lithium perchlorate, lithium difluorooxalate borate and trifluoromethanesulfonate.
  • lithium hexafluorophosphate lithium bis(oxalate)borate
  • lithium bistrifluoromethanesulfonimide lithium bisfluorosulfonimide
  • lithium perchlorate lithium difluorooxalate borate
  • trifluoromethanesulfonate lithium hexafluorophosphate
  • lithium bis(oxalate)borate lithium bistrifluoromethanesulfonimide
  • lithium bisfluorosulfonimide lithium perchlorate
  • lithium difluorooxalate borate lithium trifluoromethanesulfonate
  • the volume fraction of the ether solvent is 5 to 80%; and the volume fraction of the ester solvent is 20 to 95%.
  • the ester solvent is one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, fluoroethylene carbonate, propylene carbonate and trifluoropropylene carbonate.
  • the ether solvent is ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diglyme, triethylene glycol dimethyl ether
  • the lithium ester-containing ether ester composite electrolyte improves the uniformity of lithium deposition by forming a stable solid electrolyte protective layer in situ on the surface of the metal lithium anode. And stability, effectively inhibiting the generation of lithium dendrites, thereby enhancing the cycle life and safety of the battery, reducing the loss of lithium source and electrolyte, and improving the cell coulombic efficiency to 99.9% in 1000 cycles;
  • the composite electrolyte preparation method is simple, compatible with the existing process, and is convenient for large-scale use and promotion; and the use of the high-voltage positive electrode can effectively improve the energy density of the battery.
  • the invention provides an ether ester composite electrolyte for stabilizing a lithium metal battery, which comprises an ether ester mixed solvent, an electrolyte and lithium nitrate; wherein the molar concentration of the electrolyte in the ether ester composite electrolyte is 0.5-4 mol/L Based on the total mass of the ether ester composite electrolyte, the mass fraction of lithium nitrate is 0.01 to 10%.
  • the ether ester composite electrolyte is prepared by introducing lithium nitrate as an additive in an ether ester mixed solvent containing an electrolyte.
  • the volume fraction of the ether solvent is between 5 and 80%, and the volume fraction of the ester solvent is 20 to 95%.
  • the ester solvent is a mixture of one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, fluoroethylene carbonate, propylene carbonate and trifluoropropylene carbonate.
  • the ether solvents are ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diglyme, triethylene glycol dimethyl ether and four One or several mixtures of glyme.
  • the electrolyte according to the present invention is preferably lithium hexafluorophosphate, lithium bis(oxalate)borate, lithium bistrifluoromethanesulfonimide, lithium bisfluorosulfonimide, lithium perchlorate, lithium difluorooxalate borate and lithium trifluoromethanesulfonate.
  • lithium hexafluorophosphate lithium bis(oxalate)borate, lithium bistrifluoromethanesulfonimide, lithium bisfluorosulfonimide, lithium perchlorate, lithium difluorooxalate borate and lithium trifluoromethanesulfonate.
  • the lithium nitrate according to the present invention is an additive, and the lithium nitrate is based on the whole ether ester composite electrolyte, and has a mass fraction of 0.01 to 10%.
  • the prepared ether ester composite electrolyte is applied to a lithium battery or a lithium-containing current collector as a negative electrode, and is a full battery in which lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate or lithium cobalt oxide is used as a positive electrode. , to detect the cycle stability of the battery.
  • the electrolytic solution was tested in a coin cell battery using lithium iron phosphate as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 670 cycles.
  • An electrolyte solution of lithium nitrate was used for testing in a coin cell using nickel cobalt cobalt manganate as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 440 cycles.
  • An electrolyte of lithium fluorosulfonimide and 5 wt% of lithium nitrate was used in a coin cell using lithium nickel cobalt manganese oxide as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C.
  • its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 310 cycles.
  • the electrolyte of % lithium nitrate was used in a button cell using lithium iron phosphate as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 660 cycles.
  • the electrolyte of % lithium nitrate was used in a button cell using lithium iron phosphate as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 540 cycles.
  • An electrolyte of wt% lithium nitrate was used in a coin cell battery using lithium iron phosphate as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 570 cycles.
  • its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 430 cycles.
  • An electrolyte of lithium amine and 0.5 wt% of lithium nitrate was used for testing in a coin cell using lithium iron phosphate as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 350 cycles.

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Abstract

The present invention relates to the technical field of high-specific-energy secondary batteries that can be charged and discharged. Disclosed is an ether-ester composite electrolyte solution for stabilizing a lithium metal battery. The ether-ester composite electrolyte solution comprises an ether-ester mixed solvent, an electrolyte, and lithium nitrate, wherein the molar concentration of the electrolyte is 0.5-4 mol/L, and the mass fraction of the lithium nitrate is 0.01-10% of the ether-ester compound electrolyte solution. The ether-ester composite electrolyte solution is prepared by introducing lithium nitrate as an additive into the ether-ester mixed solvent containing the electrolyte. According to the present invention, a metal lithium negative electrode can be effectively protected, and in a lithium metal battery using lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, or lithium cobalt oxide as a positive electrode, the cycle life of the battery can be obviously improved, good high and low temperature performance is achieved, and the ether-ester composite electrolyte solution is an electrolyte solution having great research value and industrialization potential.

Description

一种用于稳定锂金属电池的醚酯复合电解液Ether ester composite electrolyte for stabilizing lithium metal battery 技术领域Technical field
本发明涉及一种用于稳定锂金属电池的醚酯复合电解液，属于可充放的高比能二次电池技术领域。The invention relates to an ether ester composite electrolyte for stabilizing a lithium metal battery, and belongs to the technical field of rechargeable high-energy secondary batteries.
背景技术Background technique
在能源的生产和有效使用过程中，储能技术扮演着极其重要的角色，其中可充放的二次电池是最重要的储能技术之一。随着便携式消费电子的快速发展、新能源汽车的大力推广以及智能电网的建设，现有的锂离子电池已经不能满足国家和社会的需求。具有更高比能的、安全的二次电池成为全社会关注的焦点。新的突破需要从材料体系上创新；因此，科学研究人员又重新把目光聚焦在以金属锂为负极的锂金属电池领域。金属锂用作负极具有天然的优势，比如最负的电极电势(-3.040V)、极高的理论容量(3860mAh g -1)，这些特殊的性质使得锂金属电池的能量密度可能达到500Wh kg -1，从而满足日益增长的社会需求。 Energy storage technology plays an extremely important role in the production and efficient use of energy. Among them, rechargeable secondary batteries are one of the most important energy storage technologies. With the rapid development of portable consumer electronics, the promotion of new energy vehicles and the construction of smart grids, existing lithium-ion batteries can no longer meet the needs of the country and society. A safe secondary battery with higher specific energy has become the focus of attention of the whole society. New breakthroughs need to be innovated from the material system; therefore, scientific researchers have refocused their attention on the field of lithium metal batteries with lithium metal as the negative electrode. The use of lithium metal as a negative electrode has natural advantages, such as the most negative electrode potential (-3.040V) and extremely high theoretical capacity (3860mAh g -1 ). These special properties make the energy density of lithium metal batteries reach 500Wh kg - 1 to meet the growing social needs.
然而，锂金属电池自20世纪50年代被提出以来，始终面临着由于锂沉积不均匀带来的安全问题，阻碍着锂金属电池的商业化。在使用液态电解液的锂金属电池中，由液态电解液还原降解生成的固态电解质界面膜对锂沉积的行为有着极其显著的影响，直接关系到电池的循环寿命和安全型。因此，研发能显著提高锂沉积均匀性和电池稳定性、安全性的锂金属电池电解液成为当下的研究热点和挑战。However, since the introduction of lithium metal batteries in the 1950s, they have always faced safety problems due to uneven deposition of lithium, hindering the commercialization of lithium metal batteries. In a lithium metal battery using a liquid electrolyte, the solid electrolyte interface film formed by the reduction and degradation of the liquid electrolyte has a very significant influence on the behavior of lithium deposition, which is directly related to the cycle life and safety of the battery. Therefore, research and development of lithium metal battery electrolytes that can significantly improve lithium deposition uniformity and battery stability and safety have become current research hotspots and challenges.
发明内容Summary of the invention
本发明的目的在于提供一种用于稳定锂金属电池的醚酯复合电解液，可调控金属锂负极沉积的均匀性，抑制锂枝晶生成，提高锂金属电池在长续航过程中的寿命以及安全性。The object of the present invention is to provide an ether ester composite electrolyte for stabilizing a lithium metal battery, which can regulate the uniformity of deposition of the lithium metal anode, inhibit the formation of lithium dendrites, and improve the life and safety of the lithium metal battery during long battery life. Sex.
本发明的技术方案如下：The technical solution of the present invention is as follows:
一种用于稳定锂金属电池的醚酯复合电解液，所述醚酯复合电解液包含醚酯类混合溶剂、电解质和硝酸锂；其中，电解质的摩尔浓度为0.5～4mol/L；基于醚酯复合电解液，硝酸锂的质量分数为0.01～10％。An ether ester composite electrolyte for stabilizing a lithium metal battery, the ether ester composite electrolyte comprising an ether ester mixed solvent, an electrolyte and lithium nitrate; wherein the molar concentration of the electrolyte is 0.5 to 4 mol/L; based on the ether ester The composite electrolyte has a mass fraction of lithium nitrate of 0.01 to 10%.
上述技术方案中，所述电解质包括：六氟磷酸锂、二草酸硼酸锂、双三氟甲烷磺酰亚胺锂、双氟磺酰亚胺锂、高氯酸锂、二氟草酸硼酸锂和三氟甲磺酸锂中的一种或两种的混合。In the above technical solution, the electrolyte comprises: lithium hexafluorophosphate, lithium bis(oxalate)borate, lithium bistrifluoromethanesulfonimide, lithium bisfluorosulfonimide, lithium perchlorate, lithium difluorooxalate borate and trifluoromethanesulfonate. One or a mixture of two of lithium acid.
优选地，所述醚酯类混合溶剂中，醚类溶剂体积分数为5～80％；酯类溶剂的体积分数为20～95％。Preferably, in the ether ester mixed solvent, the volume fraction of the ether solvent is 5 to 80%; and the volume fraction of the ester solvent is 20 to 95%.
优选地，所述的酯类溶剂为碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸乙烯酯、氟代碳酸乙烯酯、碳酸丙烯酯和三氟丙烯碳酸酯中的一种或几种的混合溶剂。所述的醚类溶剂为 乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、二甘醇二甲醚、三甘醇二甲醚和四甘醇二甲醚的一种或几种混合溶剂。Preferably, the ester solvent is one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, fluoroethylene carbonate, propylene carbonate and trifluoropropylene carbonate. Kind of mixed solvent. The ether solvent is ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diglyme, triethylene glycol dimethyl ether One or several mixed solvents of ether and tetraglyme.
本发明相比现有技术，具有如下优点及突出性效果：含硝酸锂的醚酯复合电解液通过在金属锂负极表面原位形成一层稳定的固态电解质保护层，从而提高锂沉积的均匀性和稳定性，有效地抑制了锂枝晶的产生，进而增强电池的循环寿命和安全性，减少锂源和电解液的损失，在1000次循环内可提升电池库仑效率至99.9％；该醚酯复合电解液制备方法简单，与现有工艺兼容，便于大规模使用和推广；配合高压正极使用，能有效提升电池的能量密度。Compared with the prior art, the invention has the following advantages and outstanding effects: the lithium ester-containing ether ester composite electrolyte improves the uniformity of lithium deposition by forming a stable solid electrolyte protective layer in situ on the surface of the metal lithium anode. And stability, effectively inhibiting the generation of lithium dendrites, thereby enhancing the cycle life and safety of the battery, reducing the loss of lithium source and electrolyte, and improving the cell coulombic efficiency to 99.9% in 1000 cycles; the ether ester The composite electrolyte preparation method is simple, compatible with the existing process, and is convenient for large-scale use and promotion; and the use of the high-voltage positive electrode can effectively improve the energy density of the battery.
具体实施方式Detailed ways
本发明提供的一种用于稳定锂金属电池的醚酯复合电解液，其含有醚酯类混合溶剂、电解质和硝酸锂；其中，醚酯复合电解液中电解质的摩尔浓度为0.5～4mol/L，基于醚酯复合电解液总质量，硝酸锂的质量分数为0.01～10％。The invention provides an ether ester composite electrolyte for stabilizing a lithium metal battery, which comprises an ether ester mixed solvent, an electrolyte and lithium nitrate; wherein the molar concentration of the electrolyte in the ether ester composite electrolyte is 0.5-4 mol/L Based on the total mass of the ether ester composite electrolyte, the mass fraction of lithium nitrate is 0.01 to 10%.
该醚酯复合电解液通过在含有电解质的醚酯混合溶剂中引入硝酸锂作为添加剂的办法来制备。The ether ester composite electrolyte is prepared by introducing lithium nitrate as an additive in an ether ester mixed solvent containing an electrolyte.
所述醚酯类混合溶剂中，醚类溶剂的体积分数介于5～80％之间，酯类溶剂的体积分数为20～95％。所述的酯类溶剂为碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸乙烯酯、氟代碳酸乙烯酯、碳酸丙烯酯和三氟丙烯碳酸酯中的一种或几种的混合溶剂。醚类溶剂为乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、二甘醇二甲醚、三甘醇二甲醚和四甘醇二甲醚的一种或几种混合。In the ether ester-based mixed solvent, the volume fraction of the ether solvent is between 5 and 80%, and the volume fraction of the ester solvent is 20 to 95%. The ester solvent is a mixture of one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, fluoroethylene carbonate, propylene carbonate and trifluoropropylene carbonate. Solvent. The ether solvents are ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diglyme, triethylene glycol dimethyl ether and four One or several mixtures of glyme.
本发明所述的电解质优选为六氟磷酸锂、二草酸硼酸锂、双三氟甲烷磺酰亚胺锂、双氟磺酰亚胺锂、高氯酸锂、二氟草酸硼酸锂和三氟甲磺酸锂中的一种或两种，但不限于此，其摩尔浓度介于0.5～4mol/L之间。The electrolyte according to the present invention is preferably lithium hexafluorophosphate, lithium bis(oxalate)borate, lithium bistrifluoromethanesulfonimide, lithium bisfluorosulfonimide, lithium perchlorate, lithium difluorooxalate borate and lithium trifluoromethanesulfonate. One or both of them, but are not limited thereto, and have a molar concentration of between 0.5 and 4 mol/L.
本发明所述的硝酸锂为添加剂，所述硝酸锂基于整体醚酯复合电解液，其质量分数为0.01～10％。The lithium nitrate according to the present invention is an additive, and the lithium nitrate is based on the whole ether ester composite electrolyte, and has a mass fraction of 0.01 to 10%.
将所配制的醚酯复合电解液应用于以金属锂或含锂的集流体做负极，以磷酸铁锂、镍钴锰酸锂、镍钴铝酸锂或钴酸锂中为正极的全电池中，检测电池的循环稳定性。The prepared ether ester composite electrolyte is applied to a lithium battery or a lithium-containing current collector as a negative electrode, and is a full battery in which lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate or lithium cobalt oxide is used as a positive electrode. , to detect the cycle stability of the battery.
下面结合几个具体实例对本发明做进一步的描述，但本发明的保护范围不局限于以下的实施例，其中，wt％为质量分数。The present invention will be further described below in connection with a few specific examples, but the scope of protection of the present invention is not limited to the following examples, wherein wt% is a mass fraction.
实施例1：配制组成为碳酸乙烯酯：碳酸二乙酯：二乙二醇二甲醚＝4:4:2(体积比)，含有1.0mol/L六氟磷酸锂和1.5wt％硝酸锂的电解液，并将其使用在以磷酸铁锂为正极，金属锂为负极的纽扣电池中进行测试，测试倍率为1C。当其比容量衰减至初始比容量的80％时，其循环寿命为545圈。Example 1: Formulation of ethylene carbonate: diethyl carbonate: diethylene glycol dimethyl ether = 4:4:2 (volume ratio), an electrolyte containing 1.0 mol/L lithium hexafluorophosphate and 1.5 wt% lithium nitrate, The test was carried out in a button battery using lithium iron phosphate as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 545 cycles.
实施例2：配制组成为碳酸丙烯酯：碳酸二甲酯：乙二醇二甲醚＝3.5:3.5:3(体积比)， 含有1.0mol/L二氟草酸硼酸锂和1.0wt％硝酸锂的电解液，并将其使用在以磷酸铁锂为正极，金属锂为负极的纽扣电池中进行测试，测试倍率为1C。当其比容量衰减至初始比容量的80％时，其循环寿命为670圈。Example 2: The composition was propylene carbonate: dimethyl carbonate: ethylene glycol dimethyl ether = 3.5: 3.5: 3 (volume ratio), containing 1.0 mol/L lithium difluorooxalate borate and 1.0 wt% lithium nitrate The electrolytic solution was tested in a coin cell battery using lithium iron phosphate as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 670 cycles.
实施例3：配制组成为氟代碳酸乙烯酯：碳酸二乙酯：四乙二醇二甲醚＝1:5:4(体积比)，含有0.5mol/L双三氟甲烷磺酰亚胺锂,0.5mol/L二草酸硼酸锂和4.0wt％硝酸锂的电解液，并将其使用在以磷酸铁锂为正极，金属锂为负极的纽扣电池中进行测试，测试倍率为1C。当其比容量衰减至初始比容量的80％时，其循环寿命为325圈。Example 3: The composition was prepared as fluoroethylene carbonate: diethyl carbonate: tetraethylene glycol dimethyl ether = 1:5:4 (volume ratio), containing 0.5 mol/L lithium bistrifluoromethane sulfonimide An electrolyte of 0.5 mol/L lithium dioxalate borate and 4.0 wt% lithium nitrate was used in a coin cell battery using lithium iron phosphate as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 325 cycles.
实施例4：配制组成为三氟丙烯碳酸酯：碳酸二乙酯：二乙二醇二甲醚＝2:2:6(体积比)，含有1.0mol/L双三氟甲烷磺酰亚胺锂和8wt％硝酸锂的电解液，并将其使用在以磷酸铁锂为正极，金属锂为负极的纽扣电池中进行测试，测试倍率为1C。当其比容量衰减至初始比容量的80％时，其循环寿命为879圈。Example 4: Formulation of trifluoropropene carbonate: diethyl carbonate: diethylene glycol dimethyl ether = 2:2:6 (volume ratio), containing 1.0 mol/L lithium bistrifluoromethane sulfonimide And an electrolyte of 8 wt% lithium nitrate, and it was tested in a coin cell using lithium iron phosphate as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 879 cycles.
实施例5：配制组成为氟代碳酸乙烯酯：碳酸二乙酯：三乙二醇二甲醚＝1:1:8(体积比)，含有1.0mol/L六氟磷酸锂和10wt％硝酸锂的电解液，并将其使用在以钴酸锂为正极，金属锂为负极的纽扣电池中进行测试，测试倍率为1C。当其比容量衰减至初始比容量的80％时，其循环寿命为620圈。Example 5: Formulation of fluoroethylene carbonate: diethyl carbonate: triethylene glycol dimethyl ether = 1:1: 8 (volume ratio), electrolyte containing 1.0 mol/L lithium hexafluorophosphate and 10 wt% lithium nitrate And it was tested in a coin cell with lithium cobaltate as the positive electrode and metallic lithium as the negative electrode, and the test magnification was 1C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 620 cycles.
实施例6：配制组成为碳酸丙烯酯：碳酸二乙酯：碳酸二甲酯：二乙二醇二甲醚＝4:1:1:4(体积比)，含有1.0mol/L六氟磷酸锂和6wt％硝酸锂的电解液，并将其使用在以镍钴锰酸铝为正极，金属锂为负极的纽扣电池中进行测试，测试倍率为1C。当其比容量衰减至初始比容量的80％时，其循环寿命为440圈。Example 6: Formulation composition was propylene carbonate: diethyl carbonate: dimethyl carbonate: diethylene glycol dimethyl ether = 4:1:1:4 (volume ratio), containing 1.0 mol/L lithium hexafluorophosphate and 6 wt% An electrolyte solution of lithium nitrate was used for testing in a coin cell using nickel cobalt cobalt manganate as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 440 cycles.
实施例7：配制组成为碳酸乙烯酯：碳酸甲乙酯：四乙二醇二甲醚＝4:2:4(体积比)，含有0.6mol/L二氟草酸硼酸锂，0.6mol/L双氟磺酰亚胺锂和5wt％硝酸锂的电解液，并将其使用在以镍钴锰酸锂为正极，金属锂为负极的纽扣电池中进行测试，测试倍率为1C。当其比容量衰减至初始比容量的80％时，其循环寿命为310圈。Example 7: The composition was prepared to be ethylene carbonate: ethyl methyl carbonate: tetraethylene glycol dimethyl ether = 4:2:4 (volume ratio), containing 0.6 mol/L lithium difluorooxalate borate, 0.6 mol/L double An electrolyte of lithium fluorosulfonimide and 5 wt% of lithium nitrate was used in a coin cell using lithium nickel cobalt manganese oxide as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 310 cycles.
实施例8：配制组成为氟代碳酸乙烯酯：碳酸甲乙酯：四乙二醇二甲醚＝4:2:4(体积比)，含有4.0mol/L双氟磺酰亚胺锂和3wt％硝酸锂的电解液，并将其使用在以磷酸铁锂为正极，金属锂为负极的纽扣电池中进行测试，测试倍率为1C。当其比容量衰减至初始比容量的80％时，其循环寿命为660圈。Example 8: Formulation composition was fluoroethylene carbonate: ethyl methyl carbonate: tetraethylene glycol dimethyl ether = 4:2:4 (volume ratio), containing 4.0 mol/L lithium bisfluorosulfonimide and 3 wt The electrolyte of % lithium nitrate was used in a button cell using lithium iron phosphate as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 660 cycles.
实施例9：配制组成为碳酸乙烯酯：碳酸二甲酯：乙二醇二甲醚＝5:2:3(体积比)，含有1.0mol/L高氯酸锂和0.5wt％硝酸锂的电解液，并将其使用在以磷酸铁锂为正极，金属锂为负极的纽扣电池中进行测试，测试倍率为1C。当其比容量衰减至初始比容量的80％时，其循环寿命为520圈。Example 9: Formulation of ethylene carbonate: dimethyl carbonate: ethylene glycol dimethyl ether = 5:2:3 (volume ratio), electrolysis containing 1.0 mol/L lithium perchlorate and 0.5 wt% lithium nitrate The solution was tested in a coin cell using lithium iron phosphate as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 520 cycles.
实施例10：配制组成为氟代碳酸乙烯酯：碳酸二甲酯：二甘醇二甲醚＝3:3:4(体积比)， 含有0.5mol/L六氟磷酸锂和1.5wt％硝酸锂的电解液，并将其使用在以钴酸锂为正极，金属锂为负极的纽扣电池中进行测试，测试倍率为1C。当其比容量衰减至初始比容量的80％时，其循环寿命为584圈。Example 10: Formulation of fluoroethylene carbonate: dimethyl carbonate: diglyme = 3:3:4 (volume ratio), electrolyte containing 0.5 mol/L lithium hexafluorophosphate and 1.5 wt% lithium nitrate And it was tested in a coin cell with lithium cobaltate as the positive electrode and metallic lithium as the negative electrode, and the test magnification was 1C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 584 cycles.
实施例11：配制组成为三氟丙烯碳酸酯：碳酸二乙酯：四甘醇二甲醚＝5:4.5:0.5(体积比)，含有1.0mol/L二氟草酸硼酸锂和0.1wt％硝酸锂的电解液，并将其使用在以磷酸铁锂为正极，预沉积锂的铜集流体为负极的纽扣电池中进行测试，测试倍率为1C。当其比容量衰减至初始比容量的80％时，其循环寿命为110圈。Example 11: Formulation composition is trifluoropropene carbonate: diethyl carbonate: tetraglyme dimethyl ether = 5: 4.5: 0.5 (volume ratio), containing 1.0 mol/L lithium difluorooxalate borate and 0.1 wt% nitric acid A lithium electrolyte was used and tested in a coin cell in which lithium iron phosphate was used as a positive electrode and a copper current collector in which lithium was pre-deposited as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 110 cycles.
实施例12：配制组成为氟代碳酸乙烯酯：碳酸二甲酯：三乙二醇二甲醚＝2:6:2(体积比)，含有1.0mol/L三氟甲磺酸锂和0.5wt％硝酸锂的电解液，并将其使用在以磷酸铁锂为正极，金属锂为负极的纽扣电池中进行测试，测试倍率为1C。当其比容量衰减至初始比容量的80％时，其循环寿命为540圈。Example 12: Formulation composition is fluoroethylene carbonate: dimethyl carbonate: triethylene glycol dimethyl ether = 2:6:2 (volume ratio), containing 1.0 mol/L lithium trifluoromethanesulfonate and 0.5 wt The electrolyte of % lithium nitrate was used in a button cell using lithium iron phosphate as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 540 cycles.
实施例13：配制组成为碳酸乙烯酯：碳酸甲乙酯：三甘醇二甲醚＝3:4:3(体积比)，含有2.0mol/L双氟磺酰亚胺锂和0.2wt％硝酸锂的电解液，并将其使用在以磷酸铁锂为正极，金属锂为负极的纽扣电池中进行测试，测试倍率为1C。当其比容量衰减至初始比容量的80％时，其循环寿命为670圈。Example 13: Formulation composition was ethylene carbonate: ethyl methyl carbonate: triethylene glycol dimethyl ether = 3:4:3 (volume ratio), containing 2.0 mol/L lithium bisfluorosulfonimide and 0.2 wt% nitric acid An electrolyte of lithium was used in a coin cell battery using lithium iron phosphate as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 670 cycles.
实施例14：配制组成为三氟丙烯碳酸酯：碳酸二乙酯：四乙二醇二甲醚＝3:5:2(体积比)，含有3.0mol/L双氟磺酰亚胺锂和0.01wt％硝酸锂的电解液，并将其使用在以磷酸铁锂为正极，金属锂为负极的纽扣电池中进行测试，测试倍率为1C。当其比容量衰减至初始比容量的80％时，其循环寿命为570圈。Example 14: Formulation composition was trifluoropropene carbonate: diethyl carbonate: tetraethylene glycol dimethyl ether = 3:5:2 (volume ratio), containing 3.0 mol/L lithium bisfluorosulfonimide and 0.01 An electrolyte of wt% lithium nitrate was used in a coin cell battery using lithium iron phosphate as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 570 cycles.
实施例15：配制组成为氟代碳酸乙烯酯：碳酸二甲酯：二乙二醇二甲醚＝5:2:3(体积比)，含有0.6mol/L双三氟甲烷磺酰亚胺锂，0.6mol/L双氟磺酰亚胺锂和2.5wt％硝酸锂的电解液，并将其使用在以镍钴锰酸锂为正极，金属锂为负极的纽扣电池中进行测试，测试倍率为1C。当其比容量衰减至初始比容量的80％时，其循环寿命为430圈。Example 15: Formulation composition is fluoroethylene carbonate: dimethyl carbonate: diethylene glycol dimethyl ether = 5:2:3 (volume ratio), containing 0.6 mol/L lithium bistrifluoromethane sulfonimide , 0.6mol / L lithium bisfluorosulfonimide and 2.5wt% lithium nitrate electrolyte, and used in the nickel-cobalt-manganese oxide as the positive electrode, metal lithium as the negative electrode of the button battery test, the test rate 1C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 430 cycles.
实施例16：配制组成为碳酸乙烯酯：碳酸甲乙酯：三乙二醇二甲醚＝6:2:2(体积比)，含有0.7mol/L六氟磷酸锂，0.3mol/L双氟磺酰亚胺锂和0.5wt％硝酸锂的电解液，并将其使用在以磷酸铁锂为正极，金属锂为负极的纽扣电池中进行测试，测试倍率为1C。当其比容量衰减至初始比容量的80％时，其循环寿命为350圈。Example 16: Formulation composition was ethylene carbonate: ethyl methyl carbonate: triethylene glycol dimethyl ether = 6:2:2 (volume ratio), containing 0.7 mol/L lithium hexafluorophosphate, 0.3 mol/L difluorosulfonamide An electrolyte of lithium amine and 0.5 wt% of lithium nitrate was used for testing in a coin cell using lithium iron phosphate as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 350 cycles.
实施例17：配制组成为三氟丙烯碳酸酯：碳酸二乙酯：三乙二醇二甲醚＝4:3:3(体积比)，含有0.5mol/L高氯酸锂，0.5mol/L双氟磺酰亚胺锂和2wt％硝酸锂的电解液，并将其使用在以钴酸锂为正极，金属锂为负极的纽扣电池中进行测试，测试倍率为1C。当其比容量衰减至初始比容量的80％时，其循环寿命为350圈。Example 17: Formulation composition is trifluoropropene carbonate: diethyl carbonate: triethylene glycol dimethyl ether = 4:3:3 (volume ratio), containing 0.5 mol/L lithium perchlorate, 0.5 mol/L An electrolyte of lithium difluorosulfonimide and 2 wt% lithium nitrate was used in a coin cell battery using lithium cobaltate as a positive electrode and metallic lithium as a negative electrode, and the test magnification was 1 C. When its specific capacity is attenuated to 80% of the initial specific capacity, its cycle life is 350 cycles.

Claims (5)

  1. 一种用于稳定锂金属电池的醚酯复合电解液，其特征在于：所述醚酯复合电解液包含醚酯类混合溶剂、电解质、以及硝酸锂；其中，所述电解质的摩尔浓度为0.5～4mol/L；基于所述醚酯复合电解液，所述硝酸锂的质量分数为0.01～10％。An ether ester composite electrolyte for stabilizing a lithium metal battery, characterized in that the ether ester composite electrolyte comprises an ether ester mixed solvent, an electrolyte, and lithium nitrate; wherein the molar concentration of the electrolyte is 0.5 ～ 4 mol/L; based on the ether ester composite electrolyte, the mass fraction of the lithium nitrate is 0.01 to 10%.
  2. 如权利要求1所述的一种用于稳定锂金属电池的醚酯复合电解液，其特征在于：所述电解质包括：六氟磷酸锂、二草酸硼酸锂、双三氟甲烷磺酰亚胺锂、双氟磺酰亚胺锂、高氯酸锂、二氟草酸硼酸锂和三氟甲磺酸锂中的一种或两种的混合。The ether ester composite electrolyte for stabilizing a lithium metal battery according to claim 1, wherein the electrolyte comprises: lithium hexafluorophosphate, lithium dioxalate borate, lithium bistrifluoromethanesulfonimide, and difluoro A mixture of one or both of lithium sulfonimide, lithium perchlorate, lithium difluorooxalate borate, and lithium trifluoromethanesulfonate.
  3. 如权利要求1或2所述的一种用于稳定锂金属电池的醚酯复合电解液，其特征在于：所述醚酯类混合溶剂中，醚类溶剂的体积分数为5～80％，酯类溶剂的体积分数为20～95％。The ether ester composite electrolyte for stabilizing a lithium metal battery according to claim 1 or 2, wherein in the ether ester mixed solvent, the volume fraction of the ether solvent is 5 to 80%, and the ester The volume fraction of the solvent-like solvent is 20 to 95%.
  4. 如权利要求3所述的一种用于稳定锂金属电池的醚酯复合电解液，其特征在于：所述的酯类溶剂为碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸乙烯酯、氟代碳酸乙烯酯、碳酸丙烯酯和三氟丙烯碳酸酯中的一种或几种的混合溶剂。The ether ester composite electrolyte for stabilizing a lithium metal battery according to claim 3, wherein the ester solvent is dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or ethylene carbonate. A mixed solvent of one or more of ester, fluoroethylene carbonate, propylene carbonate and trifluoropropylene carbonate.
  5. 如权利要求3所述的一种用于稳定锂金属电池的醚酯复合电解液，其特征在于：所述的醚类溶剂为乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、二甘醇二甲醚、三甘醇二甲醚和四甘醇二甲醚的一种或几种的混合。The ether ester composite electrolyte for stabilizing a lithium metal battery according to claim 3, wherein the ether solvent is ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethyl ethane Mixing one or more of glycol dimethyl ether, tetraethylene glycol dimethyl ether, diglyme, triethylene glycol dimethyl ether, and tetraglyme.
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