WO2019214035A1 - 一种锂金属电池的电解液 - Google Patents

一种锂金属电池的电解液 Download PDF

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WO2019214035A1
WO2019214035A1 PCT/CN2018/094687 CN2018094687W WO2019214035A1 WO 2019214035 A1 WO2019214035 A1 WO 2019214035A1 CN 2018094687 W CN2018094687 W CN 2018094687W WO 2019214035 A1 WO2019214035 A1 WO 2019214035A1
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lithium
electrolyte
organic solvent
additive
metal
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张强
闫崇
黄佳琦
程新兵
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Tsinghua University
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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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • the invention relates to an electrolyte for a lithium metal battery, and belongs to the technical field of lithium metal batteries.
  • metal lithium has become a promising negative electrode due to its lower electrode potential (-3.04V vs standard hydrogen electrode) and ultra-high theoretical specific capacity (3860mAh g -1 ). material.
  • Metal lithium is faced with technical problems that need to be solved in the process of practical application; firstly, the thermodynamic instability of metallic lithium and electrolyte easily leads to the formation of an unstable solid-liquid interface layer on the surface of metallic lithium; secondly, with charge and discharge The unstable solid-liquid interface induces uneven deposition of lithium ions, resulting in the production of lithium dendrites and dead lithium; the presence of lithium dendrites may pierce the battery separator, causing contact and short-circuit between the positive and negative electrodes, which has an explosion hazard. The presence of a dead lithium layer leads to an increase in polarization of the battery and a decrease in coulombic efficiency.
  • the object of the present invention is to provide an electrolyte for a lithium metal battery, which can form a stable ion-electron mixed interface layer on the surface of the lithium negative electrode by formulating an electrolyte containing the additive, thereby avoiding the electrolyte and the metal lithium to the utmost extent.
  • Direct contact reduces lithium dendrite growth and irreversible loss of lithium source, and achieves rapid migration of lithium ions in the interface layer and uniform deposition on the electrodes, thereby further improving the coulombic efficiency of lithium metal and the service life of the whole battery.
  • An electrolyte for a lithium metal battery comprising an organic solvent, a lithium salt and an additive, the organic solvent being an ester, ether or ether ester blend, the lithium salt being dissolved in the organic solvent, the additive being nitric acid Lithium and metal halides.
  • the molar concentration of the lithium salt in the electrolyte is 1.0 to 5.0 mol/L; and the mass fraction of lithium nitrate in the additive is 0.001 wt.% to 10.0 wt.%, based on the total mass of the electrolyte, the metal
  • the mass fraction of the halide is from 0.001 wt.% to 10.0 wt.%.
  • the metal halide is one or more of silver fluoride, copper fluoride, copper iodide, silver iodide, iron fluoride, zinc chloride, iron chloride and nickel fluoride. the mix of.
  • the ester organic solvent is ethylene carbonate or diethyl carbonate;
  • the ether organic solvent is one or two of tetraethylene glycol dimethyl ether and ethylene glycol dimethyl ether.
  • the lithium salt is one or more of lithium hexafluorophosphate, lithium bistrifluoromethylsulfonimide, and lithium bisfluorosulfonimide.
  • the invention has the following advantages and outstanding effects: 1 different from the traditional artificial solid-liquid interface layer, the additive system can form an ion-electron mixed interface layer on the surface of the metallic lithium, the ion-electron The formation of the mixed interface layer accelerates the migration rate of lithium ions at the interface; 2 the presence of the ion-electron mixed interface layer can uniformly regulate the nucleation of metallic lithium, so that the surface of the lithium negative electrode is free of dendrites; 3 ion-electron mixing The existence of the interface layer can utilize the lithium storage function of the nano interface layer to construct a buffer layer of metal lithium, thereby reducing uneven deposition due to diffusion control; 4 the cost of the additive is low, the amount in the electrolyte is low, and there is no use environment special requirements.
  • the invention provides an electrolyte for a lithium metal battery, which is prepared by adding an additive composed of a metal halide and lithium nitrate to an organic solvent in which a lithium salt-containing ester, ether or ether ester blend solution is dissolved.
  • the molar concentration of the lithium salt in the electrolyte is 1.0 to 5.0 mol/L; based on the total mass of the electrolyte, the mass fraction of lithium nitrate in the additive is 0.001 wt.% to 10.0 wt.%, and the mass fraction of the metal halide It is from 0.001 wt.% to 10.0 wt.%.
  • the metal halide in the additive is preferably a mixture of one or more of silver fluoride, copper fluoride, iron fluoride, nickel fluoride, zinc chloride, iron chloride, copper iodide and silver iodide;
  • the organic solvent in the solvent is one or more of ethylene carbonate, diethyl carbonate, tetraethylene glycol dimethyl ether, and ethylene glycol dimethyl ether.
  • the soluble lithium salt of the electrolyte is one or more of lithium hexafluorophosphate, lithium bistrifluoromethylsulfonimide and lithium bisfluorosulfonimide, and the electrolyte containing the additive is suitable for using lithium metal as a negative electrode. type of battery.
  • Example 1 preparing a solution of 1.0 wt.% lithium nitrate and a total amount of 0.001 wt.% of silver fluoride in an ethylene glycol dimethyl ether solution, the lithium salt being lithium bistrifluorosulfonimide, The molar concentration was 1.0 mol/L.
  • the electrolyte was used for a full-cell test using a lithium metal sheet as a negative electrode and sulfur as a positive electrode. After testing, it was found that the coulombic efficiency of the battery can reach 99.0%, and the cycle life can reach 500 cycles.
  • Example 2 A solution of 0.01% by weight of lithium nitrate and a solution of 1 wt.% of copper fluoride in the total mass of the electrolyte was prepared.
  • the lithium salt was lithium hexafluorophosphate and the molar concentration was 1.0 mol/L.
  • the electrolyte was used for a full-cell test using a lithium metal sheet as a negative electrode and lithium iron phosphate as a positive electrode. After testing, it was found that the coulombic efficiency of the battery can reach 99.9%, and the cycle life can reach 2000 cycles.
  • Example 3 A solution of 5.0 wt.% of lithium nitrate and a solution of 3.0 wt.% of copper iodide in a total amount of electrolyte was prepared.
  • the lithium salt was lithium hexafluorophosphate and the molar concentration was 2.0 mol/L.
  • the electrolyte was used for the full-cell test using a lithium metal sheet as a negative electrode and a nickel-cobalt-manganese ternary material as a positive electrode. After testing, the coulombic efficiency of the battery was 99.8%, and the cycle life was 1000 cycles.
  • Example 4 preparing a tetraethylene glycol dimethyl ether solution containing 2.0 wt.% of lithium nitrate and a total mass of 5.0 wt.% of silver iodide as a total mass of the electrolyte, the lithium salt being lithium bisfluorosulfonimide, molar concentration It is 5.0 mol/L.
  • the electrolyte was used for a full-cell test using a lithium metal sheet as a negative electrode and lithium iron phosphate as a positive electrode. After testing, it was found that the coulombic efficiency of the battery can reach 99.9%, and the cycle life can reach 800 cycles.
  • Example 5 preparing a solution of 5.0 wt.% lithium nitrate and an ethylene glycol dimethyl ether solution containing 0.01 wt.% of iron fluoride as a total mass of the electrolyte, the lithium salt being lithium bistrifluorosulfonimide, The molar concentration was 2.0 mol/L.
  • the electrolyte was used for a full-cell test using a lithium metal sheet as a negative electrode and sulfur as a positive electrode. After testing, it was found that the coulombic efficiency of the battery can reach 98.0%, and the cycle life can reach 600 cycles.
  • Example 6 A lithium carbonate solution containing 0.5 wt.% of lithium nitrate and 0.05 wt.% of zinc chloride as a total mass of the electrolyte was prepared, and the lithium salt was lithium hexafluorophosphate at a molar concentration of 2.0 mol/L.
  • the electrolyte was used for the full battery test using a lithium metal sheet as a negative electrode and a nickel cobalt manganese ternary material as a positive electrode. After testing, the coulombic efficiency of the battery was 99.9%, and the cycle life was 1200 cycles.
  • Example 7 A vinyl carbonate solution containing 10.0 wt.% of lithium nitrate and 5.0 wt.% of nickel fluoride based on the total mass of the electrolyte was prepared, and the lithium salt was lithium hexafluorophosphate having a molar concentration of 1.0 mol/L.
  • the electrolyte was used for the full battery test using a lithium metal sheet as a negative electrode and lithium iron phosphate as a positive electrode. After testing, it was found that the coulombic efficiency of the battery can reach 99.2%, and the cycle life can reach 400 cycles.
  • Example 8 Preparing a solution of 2.0 wt.% of lithium nitrate and a total of 1.0 wt.% of ferric chloride in a solution of divinyl carbonate and ethylene carbonate (volume ratio 1:1), the lithium salt is Lithium hexafluorophosphate having a molar concentration of 1.0 mol/L.
  • the electrolyte was used for the full battery test using a lithium metal plate as a negative electrode and lithium manganate as a positive electrode. After testing, it was found that the coulombic efficiency of the battery can reach 99.2%, and the cycle life can reach 400 cycles.
  • Example 9 Formulating a solution of 5.0 wt.% of lithium nitrate and a total of 0.5 wt.% of silver fluoride in tetraethylene glycol dimethyl ether and ethylene carbonate solution (volume ratio of 1:1)
  • the lithium salt is lithium hexafluorophosphate and has a molar concentration of 3.0 mol/L.
  • the electrolyte was used for the full battery test using a lithium metal plate as a negative electrode and lithium cobaltate as a positive electrode. After testing, it was found that the coulombic efficiency of the battery can reach 99.9%, and the cycle life can reach 1400 cycles.
  • Example 10 preparing an ethylene glycol dimethyl ether solution containing 5.0 wt.% of lithium nitrate and 3.0 wt.% of copper fluoride as a total mass of the electrolyte, and the lithium salt is lithium bistrifluorosulfonimide.
  • the molar concentration was 5.0 mol/L.
  • the electrolyte was used for a full-cell test using a lithium metal plate as a negative electrode and sulfur as a positive electrode. After testing, it was found that the coulombic efficiency of the battery can reach 99.7%, and the cycle life can reach 1000 cycles.
  • Example 11 preparing a solution of 5.0 wt.% of lithium nitrate and an ethylene glycol dimethyl ether solution containing 0.7 wt.% of iron fluoride as a total mass of the electrolyte, the lithium salt being lithium bisfluorosulfonimide, Molar
  • the concentration was 4.0 mol/L.
  • the electrolyte was used for the full battery test using a lithium metal plate as a negative electrode and lithium iron phosphate as a positive electrode. After testing, it was found that the coulombic efficiency of the battery can reach 99.9%, and the cycle life can reach 1500 cycles.
  • Example 12 A vinyl carbonate solution containing 2.0 wt.% of lithium nitrate and 5.0 wt.% of nickel fluoride as a total mass of the electrolyte was prepared, and the lithium salt was lithium hexafluorophosphate having a molar concentration of 2.0 mol/L.
  • the electrolyte was used for the full-cell test using a lithium metal sheet as a negative electrode and a nickel-cobalt-manganese ternary material as a positive electrode. After testing, the coulombic efficiency of the battery was 99.9%, and the cycle life was 1000 cycles.
  • Example 13 A lithium carbonate solution containing 1.0 wt.% of lithium nitrate and 2.0 wt.% of zinc chloride as a total mass of the electrolyte was prepared, and the lithium salt was lithium hexafluorophosphate at a molar concentration of 1.0 mol/L.
  • the electrolyte was used for the full battery test using a lithium metal sheet as a negative electrode and lithium manganate as a positive electrode. After testing, the coulombic efficiency of the battery was 99.3%, and the cycle life was 500 cycles.
  • Example 14 A solution of 2.0 wt.% of lithium nitrate and a solution of 5.0 wt.% of ferric chloride in the total mass of the electrolyte was prepared.
  • the lithium salt was lithium hexafluorophosphate and the molar concentration was 3.0 mol/L.
  • the electrolyte was used for the full battery test using a lithium metal plate as a negative electrode and lithium cobaltate as a positive electrode. After testing, it was found that the coulombic efficiency of the battery can reach 99.9%, and the cycle life can reach 1500 cycles.
  • Example 15 preparing a tetraethylene glycol dimethyl ether solution containing 1.0 wt.% of lithium nitrate and 3.0 wt.% of copper iodide as a total mass of the electrolyte, and the lithium salt is lithium bisfluorosulfonimide.
  • the molar concentration was 4.0 mol/L.
  • the electrolyte was used for the whole battery test using lithium metal sheet as the negative electrode and sulfur as the positive electrode. After testing, the coulombic efficiency of the battery was 99.7%, and the cycle life was 1500 cycles.

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Abstract

本发明提供一种锂金属电池的电解液，包含有机溶剂、锂盐和添加剂，所述有机溶剂为酯类、醚类或醚酯共混液，所述锂盐溶于所述有机溶剂，所述添加剂由硝酸锂和金属卤化物组成。将含有该添加剂的电解液用于锂金属电池，能在锂负极表面形成稳定的离子-电子混合界面层，最大限度避免电解液和金属锂的直接接触，减少锂枝晶生长和锂源的不可逆损失，实现锂离子在界面层的快速迁移和在电极上的均匀沉积，含有该添加剂的电解液能够明显提高金属锂的库伦效率及全电池的使用寿命，具有良好的应用前景。

Description

一种锂金属电池的电解液 技术领域
本发明涉及一种锂金属电池的电解液，属于锂金属电池技术领域。
背景技术
在高比能电池需求的新时代下，金属锂因其较低的电极电势(-3.04V vs标准氢电极)和超高的理论比容量(3860mAh g -1)成为一种极具潜力的负极材料。金属锂在实用化的过程中面临着亟须解决的技术问题；首先，金属锂与电解液的热力学不稳定性容易导致金属锂表面形成不稳定的固液界面层；其次，随着充放电的进行，不稳定的固液界面会诱发锂离子的不均匀沉积，导致锂枝晶和死锂的产生；锂枝晶的存在可能刺穿电池隔膜，使得正负极发生接触和短路，具有爆炸隐患；死锂层的存在导致电池的极化增大和库伦效率的下降。
因此，针对如何解决金属锂枝晶和如何提高金属锂电极的库伦效率，研究人员提出了多种解决策略：增大电极的比表面积来降低局部电流密度(专利号：CN105845891A)；通过锂硼合金的硬度和骨架来控制金属锂的外延生长(Small,2014,10,4257)；引入二氧化硅化学成分来调控锂离子的均匀沉积(Adv.Mater.2016,28,2888)；通过电解液配方的筛选来在金属锂的表面形成稳定的固液界面层(专利号：CN105870502A)；近期，有研究人员发现，能够和金属锂发生合金行为的金属或者非金属单质能够诱导锂离子的定向反应(Nature Energy,2016,1,16010)，从而控制金属锂的生长。
发明内容
本发明的目的是提供一种锂金属电池的电解液，通过配制含有添加剂的电解液，使其能在锂负极表面形成稳定的离子-电子混合界面层，最大限度地避免电解液与金属锂的直接接触，减少锂枝晶生长和锂源的不可逆损失，实现锂离子在界面层的快速迁移和在电极上的均匀沉积，从而进一步提高金属锂的库伦效率及全电池的使用寿命。
本发明的技术方案如下：
一种锂金属电池的电解液，包含有机溶剂、锂盐和添加剂，所述有机溶剂为酯类、醚类或醚酯共混液，所述锂盐溶于所述有机溶剂，所述添加剂由硝酸锂和金属卤化物组成。
优选地，所述电解液中锂盐的摩尔浓度为1.0～5.0mol/L；基于电解液总质量，所述添加剂中硝酸锂的质量分数为0.001wt.％～10.0wt.％，所述金属卤化物的质量分数为0.001wt.％～ 10.0wt.％。
上述技术方案中，优选地，所述金属卤化物为氟化银、氟化铜、碘化铜、碘化银、氟化铁、氯化锌、氯化铁和氟化镍中的一种或几种的混合。
上述技术方案中，优选地，所述酯类有机溶剂为碳酸乙烯酯或碳酸二乙酯；醚类有机溶剂为四乙二醇二甲醚和乙二醇二甲醚中的一种或两种；所述锂盐为六氟磷酸锂、双三氟甲基磺酰亚胺锂和双氟磺酰亚胺锂中的一种或几种。
本发明相比现有技术，具有如下优点及突出性效果：①区别于传统的人工固液界面层，该添加剂的体系下能够在金属锂的表面形成离子-电子混合界面层，该离子-电子混合界面层的形成加速了锂离子在界面处的迁移速率；②离子-电子混合界面层的存在，能够均匀的调控金属锂的形核，使得锂负极表面无枝晶生成；③离子-电子混合界面层的存在，能够利用纳米界面层的储锂功能构建金属锂的缓冲层，减小因扩散控制带来的不均匀沉积；④添加剂的造价低廉，在电解液中用量低，对于使用环境没有特殊要求。
具体实施方式
本发明提供的一种锂金属电池的电解液，其配制方法是将金属卤化物与硝酸锂组成的添加剂加入到溶有锂盐的酯类、醚类或醚酯共混液的有机溶剂中。所述电解液中锂盐的摩尔浓度为1.0～5.0mol/L；基于电解液总质量，所述添加剂中硝酸锂的质量分数为0.001wt.％～10.0wt.％，金属卤化物的质量分数为0.001wt.％～10.0wt.％。
所述添加剂中的金属卤化物优选采用氟化银、氟化铜、氟化铁、氟化镍、氯化锌、氯化铁、碘化铜和碘化银中的一种或几种混合；电解液中的有机溶剂为碳酸乙烯酯、碳酸二乙酯、四乙二醇二甲醚、乙二醇二甲醚中的一种或几种。电解液的可溶性锂盐为六氟磷酸锂、双三氟甲基磺酰亚胺锂和双氟磺酰亚胺锂中的一种或几种，含有该添加剂的电解液适用于以金属锂作为负极的全电池类型。
从以下实施例可进一步理解本发明，但本发明不仅仅局限于以下实施例。
实施例1：配制占电解液总质量1.0wt.％硝酸锂和占电解液总质量0.001wt.％氟化银的乙二醇二甲醚溶液，锂盐为双三氟磺酰亚胺锂，摩尔浓度为1.0mol/L。将该电解液用于以金属锂片作为负极，硫作为正极的全电池测试，经过测试发现，电池的库伦效率可以达到99.0％，循环寿命可以达到500圈。
实施例2：配制占电解液总质量0.01wt.％硝酸锂和占电解液总质量1wt.％氟化铜的碳酸乙烯酯溶液，锂盐为六氟磷酸锂，摩尔浓度为1.0mol/L。将该电解液用于以金属锂片作为负极，磷酸铁锂为正极的全电池测试，经过测试发现，电池的库伦效率可以达到99.9％，循 环寿命可以达到2000圈。
实施例3：配制占电解液总质量5.0wt.％硝酸锂和占电解液总质量3.0wt.％碘化铜的碳酸乙烯酯溶液，锂盐为六氟磷酸锂，摩尔浓度为2.0mol/L。将该电解液用于以金属锂片作为负极，镍钴锰三元材料为正极的全电池测试，经过测试发现，电池的库伦效率可以达到99.8％，循环寿命可以达到1000圈。
实施例4：配制占电解液总质量2.0wt.％硝酸锂和占电解液总质量5.0wt.％碘化银的四乙二醇二甲醚溶液，锂盐为双氟磺酰亚胺锂，摩尔浓度为5.0mol/L。将该电解液用于以金属锂片作为负极，磷酸铁锂为正极的全电池测试，经过测试发现，电池的库伦效率可以达到99.9％，循环寿命可以达到800圈。
实施例5：配制占电解液总质量5.0wt.％硝酸锂和占电解液总质量0.01wt.％氟化铁的乙二醇二甲醚溶液，锂盐为双三氟磺酰亚胺锂，摩尔浓度为2.0mol/L。将该电解液用于以金属锂片作为负极，硫作为正极的全电池测试，经过测试发现，电池的库伦效率可以达到98.0％，循环寿命可以达到600圈。
实施例6：配制占电解液总质量0.5wt.％硝酸锂和占电解液总质量0.05wt.％氯化锌的碳酸二乙酯溶液，锂盐为六氟磷酸锂，摩尔浓度为2.0mol/L。将该电解液用于以金属锂片作为负极，镍钴锰三元材料为正极的全电池测试，经过测试发现，电池的库伦效率可以达到99.9％，循环寿命可以达到1200圈。
实施例7：配制占电解液总质量10.0wt.％硝酸锂和占电解液总质量5.0wt.％氟化镍的碳酸乙烯酯溶液，锂盐为六氟磷酸锂，摩尔浓度为1.0mol/L。将该电解液用于以金属锂片作为负极，磷酸铁锂为正极的全电池测试，经过测试发现，电池的库伦效率可以达到99.2％，循环寿命可以达到400圈。
实施例8：配制占电解液总质量2.0wt.％硝酸锂和占电解液总质量1.0wt.％氯化铁的碳酸二乙烯酯和碳酸乙烯酯溶液(体积比1：1)，锂盐为六氟磷酸锂，摩尔浓度为1.0mol/L。将该电解液用于以金属锂片作为负极，锰酸锂为正极的全电池测试，经过测试发现，电池的库伦效率可以达到99.2％，循环寿命可以达到400圈。
实施例9：配制占电解液总质量5.0wt.％硝酸锂和占电解液总质量0.5wt.％氟化银的四乙二醇二甲醚和碳酸乙烯酯溶液(体积比为1：1)，锂盐为六氟磷酸锂，摩尔浓度为3.0mol/L。将该电解液用于以金属锂片作为负极，钴酸锂为正极的全电池测试，经过测试发现，电池的库伦效率可以达到99.9％，循环寿命可以达到1400圈。
实施例10：配制占电解液总质量5.0wt.％硝酸锂和占电解液总质量3.0wt.％氟化铜的乙二醇二甲醚溶液，锂盐为双三氟磺酰亚胺锂，摩尔浓度为5.0mol/L。将该电解液用于以金 属锂片作为负极，硫作为正极的全电池测试，经过测试发现，电池的库伦效率可以达到99.7％，循环寿命可以达到1000圈。
实施例11：配制占电解液总质量5.0wt.％硝酸锂和占电解液总质量7.0wt.％氟化铁的乙二醇二甲醚溶液，锂盐为双氟磺酰亚胺锂，摩尔浓度为4.0mol/L。将该电解液用于以金属锂片作为负极，磷酸铁锂为正极的全电池测试，经过测试发现，电池的库伦效率可以达到99.9％，循环寿命可以达到1500圈。
实施例12：配制占电解液总质量2.0wt.％硝酸锂和占电解液总质量5.0wt.％氟化镍的碳酸乙烯酯溶液，锂盐为六氟磷酸锂，摩尔浓度为2.0mol/L。将该电解液用于以金属锂片作为负极，镍钴锰三元材料为正极的全电池测试，经过测试发现，电池的库伦效率可以达到99.9％，循环寿命可以达到1000圈。
实施例13：配制占电解液总质量1.0wt.％硝酸锂和占电解液总质量2.0wt.％氯化锌的碳酸二乙酯溶液，锂盐为六氟磷酸锂，摩尔浓度为1.0mol/L。将该电解液用于以金属锂片作为负极，锰酸锂为正极的全电池测试，经过测试发现，电池的库伦效率可以达到99.3％，循环寿命可以达到500圈。
实施例14：配制占电解液总质量2.0wt.％硝酸锂和占电解液总质量5.0wt.％氯化铁的碳酸乙烯酯溶液，锂盐为六氟磷酸锂，摩尔浓度为3.0mol/L。将该电解液用于以金属锂片作为负极，钴酸锂为正极的全电池测试，经过测试发现，电池的库伦效率可以达到99.9％，循环寿命可以达到1500圈。
实施例15：配制占电解液总质量1.0wt.％硝酸锂和占电解液总质量3.0wt.％碘化铜的四乙二醇二甲醚溶液，锂盐为双氟磺酰亚胺锂，摩尔浓度为4.0mol/L。将该电解液用于以金属锂片作为负极，硫作为正极的全电池测试，经过测试发现，电池的库伦效率可以达到99.7％，循环寿命可以达到1500圈。

Claims (5)

  1. 一种锂金属电池的电解液，其特征在于，包含有机溶剂、锂盐和添加剂，所述有机溶剂为酯类、醚类或醚酯共混液，所述锂盐溶于所述有机溶剂，所述添加剂由硝酸锂和金属卤化物组成。
  2. 根据权利要求1所述的锂金属电池的电解液，其特征在于，所述电解液中锂盐的摩尔浓度为1.0mol/L～5.0mol/L；基于电解液总质量，所述添加剂中硝酸锂的质量分数为0.001wt.％～10.0wt.％，所述金属卤化物的质量分数为0.001wt.％～10.0wt.％。
  3. 根据权利要求1或2所述的锂金属电池的电解液，其特征在于，所述金属卤化物为氟化银、氟化铜、碘化铜、碘化银、氟化铁、氯化锌、氯化铁和氟化镍中的一种或几种的混合。
  4. 根据权利要求1或2所述的锂金属电池的电解液，其特征在于，所述酯类有机溶剂为碳酸乙烯酯或碳酸二乙酯；醚类有机溶剂为四乙二醇二甲醚和乙二醇二甲醚中的一种或两种。
  5. 根据权利要求1或2所述的锂金属电池的电解液，其特征在于，所述锂盐为六氟磷酸锂、双三氟甲基磺酰亚胺锂和双氟磺酰亚胺锂中的一种或几种。
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CN109585947B (zh) * 2018-12-04 2021-01-29 安徽盟维新能源科技有限公司 一种锂金属负极双重保护方法与应用
CN110828896A (zh) * 2019-11-21 2020-02-21 国网上海市电力公司 金属枝晶抑制添加剂的用途、含该添加剂的电解液及电池
CN111477957B (zh) * 2020-04-22 2021-04-16 浙江大学 一种含复合添加剂的锂金属电池电解液及其制备方法
CN112687960A (zh) * 2020-12-28 2021-04-20 浙江省科创新材料研究院 一种利用锌盐稳定固态电解质/金属负极界面的方法
CN113206293A (zh) * 2021-04-14 2021-08-03 华中科技大学 一种锂金属电池电解液及其制备方法与应用
CN113659203A (zh) * 2021-07-18 2021-11-16 哈尔滨工业大学 一种含复合添加剂的电解液及其应用
CN115882070A (zh) * 2021-09-28 2023-03-31 中国石油化工股份有限公司 一种电解液及含有该电解液的锂金属电池
CN114094180A (zh) * 2021-11-22 2022-02-25 浙江工业大学 一种用于锂金属电池的含有硝酸银添加剂的醚类电解液
CN114447426B (zh) * 2021-12-22 2024-08-16 清华大学 锂硫电池电解液、其制备方法及锂硫电池
CN115832430B (zh) * 2022-01-06 2025-10-28 宁德时代新能源科技股份有限公司 电解液及其制备方法、锂离子二次电池、电池模块、电池包及用电装置
CN116315101A (zh) * 2023-04-06 2023-06-23 西南交通大学 一种电解液添加剂、电解液和锂金属电池
CN120280557B (zh) * 2025-06-12 2025-08-26 东北大学 含有电极界面改性添加剂的电解液及锂离子电池

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