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CN118156587A - Preparation method and application of low-temperature electrolyte for lithium metal battery - Google Patents

Preparation method and application of low-temperature electrolyte for lithium metal battery Download PDF

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CN118156587A
CN118156587A CN202410365888.2A CN202410365888A CN118156587A CN 118156587 A CN118156587 A CN 118156587A CN 202410365888 A CN202410365888 A CN 202410365888A CN 118156587 A CN118156587 A CN 118156587A
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lithium metal
lithium
temperature electrolyte
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CN118156587B (en
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陈桢
王茜
王雪莹
陈明华
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Harbin University of Science and Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0567Liquid materials characterised by the additives
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0569Liquid materials characterised by the solvents
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0017Non-aqueous electrolytes
    • H01M2300/0025Organic electrolyte
    • H01M2300/0028Organic electrolyte characterised by the solvent
    • H01M2300/0037Mixture of solvents
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

A preparation method and application of low-temperature electrolyte for lithium metal batteries relate to a preparation method and application of electrolyte. The invention provides a method for preparing low-temperature electrolyte and application of the method to a lithium metal battery; according to the invention, the lithium salt, the solvent and the additive are co-dissolved to obtain the low-temperature electrolyte for the lithium metal battery, so that the cycle life of the lithium metal battery at low temperature is obviously prolonged; the low-temperature electrolyte for the lithium metal battery is subjected to electrochemical performance test, and a freezing experiment result shows that the freezing point of the electrolyte is lower than-60 ℃, the ionic conductivity can be kept at 0.54mScm ‑1 at-40 ℃, the electrolyte can have a wide electrochemical window of 4.88V at-30 ℃, and the assembled Li Cu battery can show average coulomb efficiency of 90.7% at-30 ℃. The lithium metal battery electrolyte provided by the invention has better low-temperature performance. A low-temperature electrolyte for a lithium metal battery is applied to the lithium metal battery.

Description

一种锂金属电池用低温电解液的制备方法和应用Preparation method and application of low-temperature electrolyte for lithium metal battery

技术领域Technical Field

本发明涉及一种电解液的制备方法和应用。The invention relates to a preparation method and application of an electrolyte.

背景技术Background technique

锂离子电池在近几十年来取得了巨大的成功。不同的气候和恶劣的应用场景,如电动汽车、极地科学研究、军事设备和暴露在超低温度下的空间探索,给电池操作构成了越来越严峻的挑战。在温度低于-30℃下,电池的界面阻抗明显增大,容量严重衰减,造成巨大的能量损失。增加电池系统的能量密度,减少能量损失同时优化界面动力学可以在很大程度上解决低温条件下的焦虑问题。用锂金属取代传统的石墨阳极可以保证电池能量密度超过400Whkg-1。然而,目前对锂离子(Li+)在低温下传输和界面反应的动力学屏障的识别和调节还很有限,特别是在锂金属电池中,这阻碍了锂金属电池在低温下的实际可行性。Lithium-ion batteries have achieved great success in recent decades. Different climates and harsh application scenarios, such as electric vehicles, polar scientific research, military equipment, and space exploration exposed to ultra-low temperatures, pose increasingly severe challenges to battery operation. At temperatures below -30°C, the interfacial impedance of the battery increases significantly, the capacity decays severely, and huge energy losses occur. Increasing the energy density of the battery system, reducing energy losses, and optimizing the interface dynamics can largely solve the anxiety problem under low temperature conditions. Replacing the traditional graphite anode with lithium metal can ensure a battery energy density of more than 400Whkg -1 . However, the identification and regulation of the kinetic barriers to lithium ion (Li + ) transport and interfacial reactions at low temperatures are still limited, especially in lithium metal batteries, which hinders the practical feasibility of lithium metal batteries at low temperatures.

目前低温锂金属电池面临三个挑战:(1)电解液在低温下变得更加粘稠,甚至冻结,导致离子电导下降,电极润湿性变差;(2)由于固有的晶界电阻以及金属离子在无机晶格内的缓慢扩散,电极中的电荷转移变得更加困难;(3)固体电解质间层(SEI)对Li+的渗透性较低。大多数问题都与电解液高度相关。低温电解液的初期研究主要集中在选择低熔点共溶剂和功能性电解质添加剂(如液化气体、羧酸酯和碳酸二氟乙烯),旨在促进电解液和中的离子运输。近年来,人们开始关注界面反应动力学障碍,来解释锂金属电池在低温下的劣势。在低温条件下,脱溶过程是主要的界面动力学势垒,其贡献远超过其他过程。因此,通过调节溶剂与溶质的相互作用来设计合理的低温电解液,可加速脱溶过程的动力学。Currently, low-temperature lithium metal batteries face three challenges: (1) the electrolyte becomes more viscous or even freezes at low temperatures, resulting in a decrease in ionic conductivity and poor electrode wettability; (2) charge transfer in the electrode becomes more difficult due to inherent grain boundary resistance and slow diffusion of metal ions in the inorganic lattice; (3) the solid electrolyte interlayer (SEI) has low permeability to Li + . Most of the problems are highly related to the electrolyte. Initial research on low-temperature electrolytes focused on the selection of low-melting point co-solvents and functional electrolyte additives (such as liquefied gases, carboxylates, and difluoroethylene carbonate) to promote ion transport in the electrolyte and. In recent years, people have begun to pay attention to interfacial reaction kinetic barriers to explain the disadvantages of lithium metal batteries at low temperatures. Under low temperature conditions, the desolvation process is the main interfacial kinetic barrier, and its contribution far exceeds that of other processes. Therefore, the kinetics of the desolvation process can be accelerated by designing a reasonable low-temperature electrolyte by adjusting the interaction between the solvent and the solute.

发明内容Summary of the invention

本发明为了解决上述存在的技术问题,而提供一种锂金属电池用低温电解液的制备方法和应用。In order to solve the above-mentioned technical problems, the present invention provides a preparation method and application of a low-temperature electrolyte for lithium metal batteries.

一种锂金属电池用低温电解液的制备方法,具体是按以下步骤完成的:A method for preparing a low-temperature electrolyte for a lithium metal battery is specifically completed by the following steps:

一、物理脱水:1. Physical dehydration:

向溶剂和添加剂中分别加入分子筛进行物理脱水,得到物理脱水后的溶剂和物理脱水后的添加剂;Adding molecular sieves to the solvent and the additive respectively for physical dehydration to obtain a physically dehydrated solvent and a physically dehydrated additive;

步骤一中所述的溶剂为二氟乙酸甲酯和氢氟醚中的一种或两种;The solvent in step 1 is one or both of methyl difluoroacetate and hydrofluoroether;

步骤一中所述的添加剂为全氟丁基磺酰氟和氟代碳酸乙烯酯中的一种或两种;The additive in step 1 is one or both of perfluorobutylsulfonyl fluoride and fluoroethylene carbonate;

二、将物理脱水后的溶剂和物理脱水后的添加剂混合均匀,再加入锂盐,磁力搅拌一段时间,锂盐充分溶解,得到锂金属电池用低温电解液;2. Evenly mix the physically dehydrated solvent and the physically dehydrated additive, add lithium salt, and stir magnetically for a period of time until the lithium salt is fully dissolved to obtain a low-temperature electrolyte for lithium metal batteries;

步骤二中所述的锂盐为六氟磷酸锂、四氟硼酸锂、双三氟甲烷磺酰亚胺锂和双氟磺酰亚胺锂盐中的一种或几种。The lithium salt described in step 2 is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(trifluoromethanesulfonyl imide) and lithium bis(fluorosulfonyl imide).

一种锂金属电池用低温电解液在锂金属电池中应用。A low-temperature electrolyte for lithium metal batteries is used in lithium metal batteries.

本发明的优点:Advantages of the present invention:

一、本发明提供了一种配制低温电解液的方法并应用在锂金属电池上;该发明通过将锂盐与溶剂(二氟乙酸甲酯和氢氟醚中的一种或两种)和添加剂(添加剂为全氟丁基磺酰氟和氟代碳酸乙烯酯中的一种或两种;)共溶,得到锂金属电池用低温电解液,显著提升了锂金属电池在低温下的循环寿命;1. The present invention provides a method for preparing a low-temperature electrolyte and applying it to a lithium metal battery; the present invention obtains a low-temperature electrolyte for a lithium metal battery by dissolving a lithium salt with a solvent (one or both of methyl difluoroacetate and hydrofluoroether) and an additive (the additive is one or both of perfluorobutylsulfonyl fluoride and fluoroethylene carbonate), thereby significantly improving the cycle life of the lithium metal battery at low temperatures;

二、对本发明得到的锂金属电池用低温电解液进行电化学性能测试,冷冻实验结果表明该电解液凝固点低于-60℃,在-40℃时离子电导率可保持在0.54mS cm-1,在-30℃下可具有4.88V的宽电化学窗口,组装的Li||Cu电池在-30℃时可表现出90.7%的平均库伦效率。当与NCM811阴极配合时,在-30℃下以0.2C的倍率循环200圈,这说明本发明提供的锂金属电池电解液具有较好的低温性能。Second, the electrochemical performance of the low-temperature electrolyte for lithium metal batteries obtained by the present invention was tested. The freezing test results showed that the freezing point of the electrolyte was lower than -60°C, the ion conductivity could be maintained at 0.54mS cm -1 at -40°C, and it had a wide electrochemical window of 4.88V at -30°C. The assembled Li||Cu battery showed an average coulomb efficiency of 90.7% at -30°C. When combined with the NCM811 cathode, it was cycled 200 times at a rate of 0.2C at -30°C, which shows that the lithium metal battery electrolyte provided by the present invention has good low-temperature performance.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

图1为实施例1制备的1M LiTFSI-MPFT低温电解液在-60℃下保持1小时后的图像;FIG1 is an image of the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1 after being kept at -60° C. for 1 hour;

图2为实施例1制备的1M LiTFSI-MPFT低温电解液和1M LiTFSI-EC/DEC/DMC电解液的接触角测试图;FIG2 is a contact angle test diagram of the 1M LiTFSI-MPFT low-temperature electrolyte and the 1M LiTFSI-EC/DEC/DMC electrolyte prepared in Example 1;

图3中(a)为实施例1制备的1M LiTFSI-MPFT低温电解液在60℃到-40℃温度下的离子电导率,(b)为在实施例1制备的1M LiTFSI-MPFT低温电解液中,组装锂||不锈钢电池,通过线性扫描伏安法(LSV)以0.2mV/s的扫速在0-7V区间内测试电池的电化学稳定窗口;(c)为在实施例1制备的1M LiTFSI-MPFT低温电解液中,组装锂||铝箔电池,通过线性扫描伏安法(LSV)以0.2mV/s的扫速在0-7V区间内测试电池的电化学稳定窗口;In Figure 3, (a) is the ionic conductivity of the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1 at a temperature of 60°C to -40°C, (b) is a lithium||stainless steel battery assembled in the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1, and the electrochemical stability window of the battery is tested in the range of 0-7V by linear sweep voltammetry (LSV) at a scan rate of 0.2mV/s; (c) is a lithium||aluminum foil battery assembled in the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1, and the electrochemical stability window of the battery is tested in the range of 0-7V by linear sweep voltammetry (LSV) at a scan rate of 0.2mV/s;

图4为利用实施例1制备的1M LiTFSI-MPFT低温电解液组装的Li||Cu电池在室温和-30℃下的平均库伦效率图,图中(a)为室温,(b)为-30℃;FIG4 is a graph showing the average coulombic efficiency of a Li||Cu battery assembled using the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1 at room temperature and -30°C, where (a) is room temperature and (b) is -30°C;

图5为利用实施例1制备的1M LiTFSI-MPFT低温电解液组装的Li||Li对称电池在-30℃的低温条件下,在0.5、1、1.5、2mAcm-2的电流密度下的倍率性能图;FIG5 is a graph showing the rate performance of a Li||Li symmetric battery assembled using the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1 at current densities of 0.5, 1, 1.5, and 2 mA cm -2 under low temperature conditions of -30°C;

图6为利用实施例1制备的1M LiTFSI-MPFT低温电解液组装的Li||LiCoNiMnO4(NCM811)全电池在0.2C倍率下的循环性能曲线图。FIG6 is a cycle performance curve of a Li||LiCoNiMnO 4 (NCM811) full battery assembled using the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1 at a rate of 0.2C.

具体实施方式Detailed ways

具体实施方式一:本实施方式一种锂金属电池用低温电解液的制备方法,具体是按以下步骤完成的:Specific implementation method 1: This implementation method is a method for preparing a low-temperature electrolyte for a lithium metal battery, which is specifically completed by the following steps:

一、物理脱水:1. Physical dehydration:

向溶剂和添加剂中分别加入分子筛进行物理脱水,得到物理脱水后的溶剂和物理脱水后的添加剂;Adding molecular sieves to the solvent and the additive respectively for physical dehydration to obtain a physically dehydrated solvent and a physically dehydrated additive;

步骤一中所述的溶剂为二氟乙酸甲酯和氢氟醚中的一种或两种;The solvent in step 1 is one or both of methyl difluoroacetate and hydrofluoroether;

步骤一中所述的添加剂为全氟丁基磺酰氟和氟代碳酸乙烯酯中的一种或两种;The additive in step 1 is one or both of perfluorobutylsulfonyl fluoride and fluoroethylene carbonate;

二、将物理脱水后的溶剂和物理脱水后的添加剂混合均匀,再加入锂盐,磁力搅拌一段时间,锂盐充分溶解,得到锂金属电池用低温电解液;2. Evenly mix the physically dehydrated solvent and the physically dehydrated additive, add lithium salt, and stir magnetically for a period of time until the lithium salt is fully dissolved to obtain a low-temperature electrolyte for lithium metal batteries;

步骤二中所述的锂盐为六氟磷酸锂、四氟硼酸锂、双三氟甲烷磺酰亚胺锂和双氟磺酰亚胺锂盐中的一种或几种。The lithium salt described in step 2 is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(trifluoromethanesulfonyl imide) and lithium bis(fluorosulfonyl imide).

具体实施方式二:本实施方式与具体实施方式一不同点是:步骤一中所述的溶剂的纯度为99.99wt%。其它步骤与具体实施方式一相同。Specific implementation method 2: This implementation method is different from specific implementation method 1 in that the purity of the solvent in step 1 is 99.99 wt %. The other steps are the same as those in specific implementation method 1.

具体实施方式三:本实施方式与具体实施方式一或二之一不同点是:步骤一中所述的添加剂的纯度为99.99wt%。其它步骤与具体实施方式一或二相同。Specific implementation method 3: This implementation method is different from specific implementation methods 1 or 2 in that the purity of the additive in step 1 is 99.99 wt %. The other steps are the same as those in specific implementation methods 1 or 2.

具体实施方式四:本实施方式与具体实施方式一至三之一不同点是:步骤一中向溶剂和添加剂中分别加入分子筛进行物理脱水,将溶剂和添加剂中的水分控制在0ppm~20ppm。其它步骤与具体实施方式一至三相同。Specific embodiment 4: This embodiment differs from specific embodiments 1 to 3 in that: in step 1, molecular sieves are added to the solvent and additives for physical dehydration to control the water content of the solvent and additives to 0 ppm to 20 ppm. The other steps are the same as those of specific embodiments 1 to 3.

具体实施方式五:本实施方式与具体实施方式一至四之一不同点是:步骤一中所述的氢氟醚为1,1,2,2-四氟乙基-2,2,2-三氟乙基醚。其它步骤与具体实施方式一至四相同。Specific embodiment 5: This embodiment differs from specific embodiments 1 to 4 in that the hydrofluoroether in step 1 is 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether. The other steps are the same as those in specific embodiments 1 to 4.

具体实施方式六:本实施方式与具体实施方式一至五之一不同点是:步骤二中所述的锂金属电池用低温电解液中锂盐的浓度0.5mol/L~3mol/L。其它步骤与具体实施方式一至五相同。Specific embodiment 6: This embodiment differs from specific embodiments 1 to 5 in that the concentration of lithium salt in the low-temperature electrolyte for lithium metal batteries described in step 2 is 0.5 mol/L to 3 mol/L. The other steps are the same as those of specific embodiments 1 to 5.

具体实施方式七:本实施方式与具体实施方式一至六之一不同点是:步骤二中所述的物理脱水后的溶剂与物理脱水后的添加剂的体积比(6~8):(2~4)。其它步骤与具体实施方式一至六相同。Specific embodiment 7: This embodiment differs from specific embodiments 1 to 6 in that the volume ratio of the solvent after physical dehydration to the additive after physical dehydration in step 2 is (6 to 8): (2 to 4). The other steps are the same as those of specific embodiments 1 to 6.

具体实施方式八:本实施方式与具体实施方式一至七之一不同点是:步骤二中所述的磁力搅拌的速度为100r/min~400r/min,磁力搅拌的时间为20min~40min。其它步骤与具体实施方式一至七相同。Specific embodiment 8: This embodiment differs from specific embodiments 1 to 7 in that the speed of the magnetic stirring in step 2 is 100 r/min to 400 r/min, and the time of the magnetic stirring is 20 min to 40 min. The other steps are the same as those of specific embodiments 1 to 7.

具体实施方式九:本实施方式是一种锂金属电池用低温电解液在锂金属电池中应用。Specific implementation method 9: This implementation method is an application of a low-temperature electrolyte for lithium metal batteries in lithium metal batteries.

采用以下实施例验证本发明的有益效果:The following examples are used to verify the beneficial effects of the present invention:

实施例1:一种锂金属电池用低温电解液的制备方法,具体是按以下步骤完成的:Example 1: A method for preparing a low-temperature electrolyte for a lithium metal battery is specifically completed by the following steps:

一、物理脱水:1. Physical dehydration:

向溶剂和添加剂中分别加入分子筛进行物理脱水,将溶剂和添加剂中的水分控制在0ppm,得到物理脱水后的溶剂和物理脱水后的添加剂;Adding molecular sieves to the solvent and the additive respectively for physical dehydration, controlling the water content of the solvent and the additive to 0 ppm, and obtaining a physically dehydrated solvent and a physically dehydrated additive;

步骤一中所述的溶剂的纯度为99.99wt%;The purity of the solvent in step 1 is 99.99wt%;

步骤一中所述的添加剂的纯度为99.99wt%;The purity of the additive in step 1 is 99.99wt%;

步骤一中所述的溶剂为二氟乙酸甲酯(MDFA)和1,1,2,2-四氟乙基-2,2,2-三氟乙基醚(TTE);The solvent described in step 1 is methyl difluoroacetate (MDFA) and 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (TTE);

步骤一中所述的添加剂为全氟丁基磺酰氟(PBF)和氟代碳酸乙烯酯(FEC);The additives described in step 1 are perfluorobutylsulfonyl fluoride (PBF) and fluoroethylene carbonate (FEC);

二、将物理脱水后的溶剂和物理脱水后的添加剂混合均匀,再加入锂盐,在磁力搅拌的速度为300r/min下磁力搅拌30min,锂盐充分溶解,得到1M LiTFSI-MPFT低温电解液;2. Evenly mix the physically dehydrated solvent and the physically dehydrated additive, add lithium salt, and stir magnetically for 30 min at a speed of 300 r/min until the lithium salt is fully dissolved to obtain a 1M LiTFSI-MPFT low-temperature electrolyte;

步骤二中所述的锂金属电池用低温电解液中二氟乙酸甲酯(MDFA)、1,1,2,2-四氟乙基-2,2,2-三氟乙基醚(TTE)、全氟丁基磺酰氟(PBF)和氟代碳酸乙烯酯(FEC)的体积比为4:4:1:1;The volume ratio of methyl difluoroacetate (MDFA), 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (TTE), perfluorobutylsulfonyl fluoride (PBF) and fluoroethylene carbonate (FEC) in the low-temperature electrolyte for lithium metal batteries described in step 2 is 4:4:1:1;

步骤二中所述的锂盐为双三氟甲烷磺酰亚胺锂(LiTFSI);The lithium salt described in step 2 is lithium bis(trifluoromethanesulfonyl)imide (LiTFSI);

步骤二中所述的锂金属电池用低温电解液中锂盐的浓度1mol/L。The concentration of lithium salt in the low-temperature electrolyte for lithium metal batteries described in step 2 is 1 mol/L.

对比例:1MLiTFSI-EC/DEC/DMC电解液的制备方法是按以下步骤完成的:将LiTFSI溶于有机溶剂碳酸乙烯酯(EC)、碳酸二乙酯(DEC)和碳酸二甲酯(DMC)的混合溶液中,在300r/min下磁力搅拌30min,锂盐充分溶解,得到1MLiTFSI-EC/DEC/DMC低温电解液,1MLiTFSI-EC/DEC/DMC低温电解液中LiTFSI的浓度为1mol/L;按体积百分比计,有机溶剂EC:DMC:DMC=1:1:1。Comparative Example: The preparation method of 1MLiTFSI-EC/DEC/DMC electrolyte is completed according to the following steps: dissolving LiTFSI in a mixed solution of organic solvents of ethylene carbonate (EC), diethyl carbonate (DEC) and dimethyl carbonate (DMC), and magnetically stirring at 300r/min for 30min to fully dissolve the lithium salt to obtain 1MLiTFSI-EC/DEC/DMC low-temperature electrolyte, wherein the concentration of LiTFSI in the 1MLiTFSI-EC/DEC/DMC low-temperature electrolyte is 1mol/L; in terms of volume percentage, the organic solvents EC:DMC:DMC=1:1:1.

图1为实施例1制备的1M LiTFSI-MPFT低温电解液在-60℃下保持1小时后的图像;FIG1 is an image of the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1 after being kept at -60° C. for 1 hour;

从图1可以看出:实施例1制备的1M LiTFSI-MPFT低温电解液在-60℃仍保持液体状态,说明所配置的低温电解液具有低的凝固点,可满足极端环境条件下的测试。As can be seen from FIG. 1 , the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1 remains in a liquid state at -60° C., indicating that the configured low-temperature electrolyte has a low freezing point and can meet the test requirements under extreme environmental conditions.

两种电解液在NCM811正极和聚丙烯(PP)隔膜上的润湿角测试结果见图2所示;The wetting angle test results of the two electrolytes on the NCM811 positive electrode and polypropylene (PP) separator are shown in Figure 2;

图2为实施例1制备的1M LiTFSI-MPFT低温电解液和1M LiTFSI-EC/DEC/DMC电解液的接触角测试图;FIG2 is a contact angle test diagram of the 1M LiTFSI-MPFT low-temperature electrolyte and the 1M LiTFSI-EC/DEC/DMC electrolyte prepared in Example 1;

从图2可知:实施例1制备的1M LiTFSI-MPFT低温电解液在隔膜上的润湿角为9°,而1MLiTFSI-EC/DEC/DMC电解液在隔膜上的润湿角为19°,表明:实施例1制备的1MLiTFSI-MPFT低温电解液对正极片和隔膜具有良好的润湿性,可以确保电解液与正极片和隔膜之间的良好接触,促进离子传输和电化学反应。As can be seen from Figure 2, the wetting angle of the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1 on the diaphragm is 9°, while the wetting angle of the 1MLiTFSI-EC/DEC/DMC electrolyte on the diaphragm is 19°, indicating that the 1MLiTFSI-MPFT low-temperature electrolyte prepared in Example 1 has good wettability to the positive electrode sheet and the diaphragm, which can ensure good contact between the electrolyte and the positive electrode sheet and the diaphragm, and promote ion transport and electrochemical reactions.

图3中(a)为实施例1制备的1M LiTFSI-MPFT低温电解液在60℃到-40℃温度下的离子电导率,(b)为在实施例1制备的1M LiTFSI-MPFT低温电解液中,组装锂||不锈钢电池,通过线性扫描伏安法(LSV)以0.2mV/s的扫速在0-7V区间内测试电池的电化学稳定窗口;(c)为在实施例1制备的1M LiTFSI-MPFT低温电解液中,组装锂||铝箔电池,通过线性扫描伏安法(LSV)以0.2mV/s的扫速在0-7V区间内测试电池的电化学稳定窗口;In Figure 3, (a) is the ionic conductivity of the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1 at a temperature of 60°C to -40°C, (b) is a lithium||stainless steel battery assembled in the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1, and the electrochemical stability window of the battery is tested in the range of 0-7V by linear sweep voltammetry (LSV) at a scan rate of 0.2mV/s; (c) is a lithium||aluminum foil battery assembled in the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1, and the electrochemical stability window of the battery is tested in the range of 0-7V by linear sweep voltammetry (LSV) at a scan rate of 0.2mV/s;

图3中锂||不锈钢电池组装方法:正极为不锈钢片,负极为锂片,隔膜为聚丙烯隔膜,电解液为实施例1制备的1M LiTFSI-MPFT低温电解液,用量为70μL。锂||铝电池组装方法:正极为铝箔,负极为锂片,隔膜为聚丙烯隔膜,电解液为实施例1制备的1M LiTFSI-MPFT低温电解液,用量为70μL。The lithium||stainless steel battery assembly method in Figure 3: the positive electrode is a stainless steel sheet, the negative electrode is a lithium sheet, the diaphragm is a polypropylene diaphragm, and the electrolyte is the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1, and the amount used is 70μL. The lithium||aluminum battery assembly method: the positive electrode is an aluminum foil, the negative electrode is a lithium sheet, the diaphragm is a polypropylene diaphragm, and the electrolyte is the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1, and the amount used is 70μL.

从图3a可知:实施例1制备的1M LiTFSI-MPFT低温电解液的离子电导率随着温度的下降而逐渐降低,即使在-40℃时仍保持在0.54mScm-1。通过线性扫描伏安法对不锈钢||锂电池的电化学稳定窗口进行了测试,如图3b所示;从图3b可知:实施例1制备的1MLiTFSI-MPFT低温电解液的氧化电位高达4.88V,能够满足锂电池正极材料的工作需要。当测试铝电极,实施例1制备的1M LiTFSI-MPFT低温电解液的电位增加到5.8V以上,表明这种电解液能有效抑制铝腐蚀。As shown in Figure 3a, the ionic conductivity of the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1 gradually decreases with the decrease in temperature, and remains at 0.54mScm -1 even at -40°C. The electrochemical stability window of the stainless steel||lithium battery was tested by linear sweep voltammetry, as shown in Figure 3b; As shown in Figure 3b, the oxidation potential of the 1MLiTFSI-MPFT low-temperature electrolyte prepared in Example 1 is as high as 4.88V, which can meet the working requirements of the positive electrode material of the lithium battery. When the aluminum electrode was tested, the potential of the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1 increased to above 5.8V, indicating that this electrolyte can effectively inhibit aluminum corrosion.

为了揭示低温电解液与锂金属阳极的相容性,首先对Li||Cu电池的库伦效率(CE)进行了评价。To reveal the compatibility of low-temperature electrolytes with lithium metal anodes, the coulombic efficiency (CE) of Li||Cu batteries was first evaluated.

Li||Cu电池组装方法:正极为铜箔,负极为锂片,隔膜为聚丙烯隔膜,电解液为实施例1制备的1M LiTFSI-MPFT低温电解液,用量为70μL。Li||Cu battery assembly method: the positive electrode is copper foil, the negative electrode is lithium sheet, the diaphragm is polypropylene diaphragm, and the electrolyte is 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1, with a dosage of 70 μL.

图4为利用实施例1制备的1M LiTFSI-MPFT低温电解液组装的Li||Cu电池在室温和-30℃下的平均库伦效率图,图中(a)为室温,(b)为-30℃;FIG4 is a graph showing the average coulombic efficiency of a Li||Cu battery assembled using the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1 at room temperature and -30°C, where (a) is room temperature and (b) is -30°C;

从图4可知:采用改进的Aurbach方法,在室温下,利用实施例1制备的1M LiTFSI-MPFT低温电解液组装的Li||Cu电池的平均CE值为97.9%。当测试温度进一步降至-30℃时,Li||Cu电池表现出90.7%的平均库伦效率。证明了这种电解液的优越性,可以在-30℃的低温下实现高度可逆的锂镀/剥离。As shown in Figure 4, the average CE value of the Li||Cu battery assembled using the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1 at room temperature using the improved Aurbach method is 97.9%. When the test temperature is further reduced to -30°C, the Li||Cu battery exhibits an average coulombic efficiency of 90.7%. This demonstrates the superiority of this electrolyte, which can achieve highly reversible lithium plating/stripping at a low temperature of -30°C.

Li||Li电池组装方法:正、负极为锂片,隔膜为聚丙烯隔膜,电解液为实施例1制备的1M LiTFSI-MPFT低温电解液,用量为70μL。Li||Li battery assembly method: the positive and negative electrodes are lithium sheets, the separator is a polypropylene separator, and the electrolyte is the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1, with a dosage of 70 μL.

图5为利用实施例1制备的1M LiTFSI-MPFT低温电解液组装的Li||Li对称电池在-30℃的低温条件下,在0.5、1、1.5、2mAcm-2的电流密度下的倍率性能图;FIG5 is a graph showing the rate performance of a Li||Li symmetric battery assembled using the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1 at current densities of 0.5, 1, 1.5, and 2 mA cm -2 under low temperature conditions of -30°C;

从图5可知:利用实施例1制备的1M LiTFSI-MPFT低温电解液组装的Li||Li对称电池在-30℃的低温条件下,在0.5、1、1.5、2mAcm-2的电流密度下均具有良好的抗极化行为,界面副反应缓慢。As shown in Figure 5, the Li||Li symmetric battery assembled using the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1 has good anti-polarization behavior at current densities of 0.5, 1, 1.5, and 2 mA cm-2 under low temperature conditions of -30°C, and the interface side reactions are slow.

LiCoNiMnO4(NCM811)正极片:正极活性材料为镍钴锰酸锂;导电剂为超级碳(Super P);粘结剂为聚偏氟乙烯(PVDF);其中,正极活性材料:导电剂:粘结剂的重量百分比为96%:2%:2%。Li||LiCoNiMnO4(NCM811)全电池组装方法:正极为NCM811电极片、负极为锂片,隔膜为聚丙烯隔膜,电解液为实施例1制备的1M LiTFSI-MPFT低温电解液,用量为100μL。LiCoNiMnO 4 (NCM811) positive electrode sheet: the positive electrode active material is lithium nickel cobalt manganese oxide; the conductive agent is super carbon (Super P); the binder is polyvinylidene fluoride (PVDF); wherein the weight percentage of the positive electrode active material: the conductive agent: the binder is 96%: 2%: 2%. Li||LiCoNiMnO 4 (NCM811) full battery assembly method: the positive electrode is an NCM811 electrode sheet, the negative electrode is a lithium sheet, the separator is a polypropylene separator, and the electrolyte is the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1, and the amount used is 100 μL.

图6为利用实施例1制备的1M LiTFSI-MPFT低温电解液组装的Li||LiCoNiMnO4(NCM811)全电池在0.2C倍率下的循环性能曲线图;FIG6 is a cycle performance curve of a Li||LiCoNiMnO 4 (NCM811) full battery assembled using the 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1 at a rate of 0.2C;

从图6可知:NCM811电极的活性物质NCM811的质量负载为~10mgcm-2。Li||From Figure 6, we can see that the mass loading of the active material NCM811 in the NCM811 electrode is ~10 mg cm -2 . Li||

LiCoNiMnO4(NCM811)全电池的初始放电比容量约为110.64mAhg–1,在经历200圈的循环后下降到44.36mAhg–1,容量保留率为40%,表明使用实施例1制备的1MLiTFSI-MPFT低温电解液组装的电池可以在-40℃低温下提供很好的放电比容量和循环寿命。The initial discharge capacity of the LiCoNiMnO 4 (NCM811) full cell is about 110.64 mAhg –1 , which drops to 44.36 mAhg –1 after 200 cycles, with a capacity retention rate of 40%, indicating that the battery assembled using the 1MLiTFSI-MPFT low-temperature electrolyte prepared in Example 1 can provide good discharge capacity and cycle life at a low temperature of -40°C.

商业NCM811全电池组装方法:正极为商业NCM811电极片(活性物质NCM811负载~17.5mgcm-2)、负极为锂片,隔膜为聚丙烯隔膜,电解液为实施例1制备的1MLiTFSI-MPFT低温电解液,用量为100μL。Commercial NCM811 full battery assembly method: the positive electrode is a commercial NCM811 electrode sheet (active material NCM811 loading ˜17.5 mg cm −2 ), the negative electrode is a lithium sheet, the separator is a polypropylene separator, and the electrolyte is the 1MLiTFSI-MPFT low-temperature electrolyte prepared in Example 1, with a dosage of 100 μL.

利用实施例1制备的1M LiTFSI-MPFT低温电解液组装商业NCM811全电池在低温-20℃下0.1C的初始放电容量为145.35mAhg-1,在低温-30℃下0.1C的初始放电容量为120.74mAhg-1,在低温-40℃下0.1C的初始放电容量为107.52mAhg-1The commercial NCM811 full battery assembled with 1M LiTFSI-MPFT low-temperature electrolyte prepared in Example 1 has an initial discharge capacity of 145.35 mAhg -1 at 0.1C at -20°C, 120.74 mAhg -1 at -30°C, and 107.52 mAhg -1 at -40°C.

实施例2:本实施例与实施例1的不同点是:步骤二中所述的锂金属电池用低温电解液中二氟乙酸甲酯(MDFA)、1,1,2,2-四氟乙基-2,2,2-三氟乙基醚(TTE)、全氟丁基磺酰氟(PBF)和氟代碳酸乙烯酯(FEC)的体积比为4:6:0:0。即省略使用全氟丁基磺酰氟(PBF)和氟代碳酸乙烯酯(FEC)。其它步骤及参数与实施例1均相同。Example 2: The difference between this example and Example 1 is that the volume ratio of methyl difluoroacetate (MDFA), 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (TTE), perfluorobutylsulfonyl fluoride (PBF) and fluoroethylene carbonate (FEC) in the low-temperature electrolyte for lithium metal batteries described in step 2 is 4:6:0:0. That is, perfluorobutylsulfonyl fluoride (PBF) and fluoroethylene carbonate (FEC) are omitted. The other steps and parameters are the same as those in Example 1.

利用实施例2制备的低温电解液组装商业NCM811全电池在-20℃下0.1C的初始放电容量为125mAhg-1The initial discharge capacity of a commercial NCM811 full battery assembled with the low-temperature electrolyte prepared in Example 2 at 0.1C at -20°C was 125 mAhg -1 .

实施例3:本实施例与实施例1的不同点是:步骤二中所述的锂金属电池用低温电解液中二氟乙酸甲酯(MDFA)、1,1,2,2-四氟乙基-2,2,2-三氟乙基醚(TTE)、全氟丁基磺酰氟(PBF)和氟代碳酸乙烯酯(FEC)的体积比为4:5:1:0。即省略使用氟代碳酸乙烯酯(FEC)。其它步骤及参数与实施例1均相同。Example 3: The difference between this example and Example 1 is that the volume ratio of methyl difluoroacetate (MDFA), 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (TTE), perfluorobutylenesulfonyl fluoride (PBF) and fluoroethylene carbonate (FEC) in the low-temperature electrolyte for lithium metal batteries described in step 2 is 4:5:1:0. That is, the use of fluoroethylene carbonate (FEC) is omitted. The other steps and parameters are the same as those in Example 1.

利用实施例3制备的低温电解液组装商业NCM811全电池在-40℃下0.1C的初始放电容量为81.65mAhg-1The initial discharge capacity of a commercial NCM811 full battery assembled with the low-temperature electrolyte prepared in Example 3 at 0.1C at -40°C was 81.65 mAhg -1 .

实施例4:本实施例与实施例1的不同点是:步骤二中所述的锂金属电池用低温电解液中二氟乙酸甲酯(MDFA)、1,1,2,2-四氟乙基-2,2,2-三氟乙基醚(TTE)、全氟丁基磺酰氟(PBF)和氟代碳酸乙烯酯(FEC)的体积比为4:5:0:1。即省略使用全氟丁基磺酰氟(PBF)。其它步骤及参数与实施例1均相同。Example 4: The difference between this example and Example 1 is that the volume ratio of methyl difluoroacetate (MDFA), 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (TTE), perfluorobutylsulfonyl fluoride (PBF) and fluoroethylene carbonate (FEC) in the low-temperature electrolyte for lithium metal batteries described in step 2 is 4:5:0:1. That is, perfluorobutylsulfonyl fluoride (PBF) is omitted. The other steps and parameters are the same as those in Example 1.

利用实施例4制备的低温电解液组装商业NCM811全电池在所得的低温锂离子电池中,低温-20℃下0.1C的初始放电容量为120.61mAhg-1,低温-30℃下0.1C的初始放电容量为93.62mAhg-1,低温-40℃下0.1C的初始放电容量为74.33mAhg-1The low-temperature electrolyte prepared in Example 4 was used to assemble a commercial NCM811 full cell. In the resulting low-temperature lithium-ion battery, the initial discharge capacity at 0.1C at -20°C was 120.61 mAhg -1 , the initial discharge capacity at 0.1C at -30°C was 93.62 mAhg -1 , and the initial discharge capacity at 0.1C at -40°C was 74.33 mAhg -1 .

Claims (9)

1. The preparation method of the low-temperature electrolyte for the lithium metal battery is characterized by comprising the following steps of:
1. Physical dehydration:
Molecular sieve is respectively added into the solvent and the additive for physical dehydration, so as to obtain the solvent after physical dehydration and the additive after physical dehydration;
the solvent in the first step is one or two of methyl difluoroacetate and hydrofluoroether;
the additive in the first step is one or two of perfluorobutyl sulfonyl fluoride and fluoroethylene carbonate;
2. Uniformly mixing the physically dehydrated solvent and the physically dehydrated additive, adding lithium salt, magnetically stirring for a period of time, and fully dissolving the lithium salt to obtain a low-temperature electrolyte for the lithium metal battery;
The lithium salt in the second step is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bistrifluoro methane sulfonyl imide and lithium bistrifluoro sulfonyl imide.
2. The method for preparing a low-temperature electrolyte for a lithium metal battery according to claim 1, wherein the purity of the solvent in the first step is 99.99wt%.
3. The method for preparing a low-temperature electrolyte for a lithium metal battery according to claim 1, wherein the purity of the additive in the step one is 99.99wt%.
4. The method for preparing a low-temperature electrolyte for lithium metal batteries according to claim 1, wherein in the first step, molecular sieves are added to the solvent and the additive, respectively, to carry out physical dehydration, and the moisture in the solvent and the additive is controlled to be 0ppm to 20ppm.
5. The method for preparing a low-temperature electrolyte for a lithium metal battery according to claim 1, wherein the hydrofluoroether used in the first step is 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether.
6. The method for preparing a low-temperature electrolyte for a lithium metal battery according to claim 1, wherein the concentration of lithium salt in the low-temperature electrolyte for a lithium metal battery in the second step is 0.5mol/L to 3mol/L.
7. The method for preparing a low-temperature electrolyte for a lithium metal battery according to claim 1, wherein the volume ratio of the physically dehydrated solvent to the physically dehydrated additive in the second step is (6-8) (2-4).
8. The method for preparing a low-temperature electrolyte for a lithium metal battery according to claim 1, wherein the magnetic stirring speed in the second step is 100-400 r/min, and the magnetic stirring time is 20-40 min.
9. The use of a low-temperature electrolyte for lithium metal batteries prepared by the preparation method according to claim 1, wherein the low-temperature electrolyte for lithium metal batteries is used in lithium metal batteries.
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