WO2018232863A1 - 一种锂硫电池电解液及其制备方法 - Google Patents

一种锂硫电池电解液及其制备方法 Download PDF

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WO2018232863A1
WO2018232863A1 PCT/CN2017/096364 CN2017096364W WO2018232863A1 WO 2018232863 A1 WO2018232863 A1 WO 2018232863A1 CN 2017096364 W CN2017096364 W CN 2017096364W WO 2018232863 A1 WO2018232863 A1 WO 2018232863A1
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lithium
sulfur battery
battery electrolyte
additive
electrolyte according
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晏成林
杨庭舟
钱涛
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Suzhou 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • H01M10/42—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
    • 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 belongs to the field of lithium sulfur batteries, and relates to a lithium sulfur battery electrolyte, in particular to a lithium sulfur battery electrolyte and a preparation method thereof.
  • lithium-ion batteries occupy a central position in today's energy storage devices due to their advantages of small self-discharge, high specific energy, long cycle life, wide charging power range and light weight.
  • Most lithium batteries use a carbon material as a negative electrode, and a lithium plate as a positive electrode, which utilizes lithium ions to shuttle back and forth between the positive and negative electrodes to contribute capacity.
  • lithium-ion batteries began to be widely used in portable electronic products such as mobile phones, notebook computers, digital cameras, etc., and with the global popularity of these products, the market demand for lithium-ion batteries has been maintained.
  • the lithium-sulfur battery system has a very high theoretical energy density and is one of the most promising secondary batteries in various energy storage systems.
  • the lithium-sulfur battery uses a natural rich sulfur element as a negative electrode material with a high theoretical specific volume (1675 mAh / g) and a high energy density (2500 Wh / kg), which is more than five times the theoretical capacity of a lithium ion battery.
  • lithium-sulfur batteries provide high capacity through a multiphase conversion redox reaction between sulfur, soluble polysulfide, and insoluble lithium sulfide.
  • the polysulfide as an intermediate can be dissolved in the organic liquid electrolyte, resulting in a severe shuttling effect, resulting in loss of the active material. At the same time, it has a serious parasitic reaction with the lithium anode, which reduces the cycle life and leads to a particularly low coulombic efficiency.
  • the lithium sulfur battery cycle life is shortened and the charging efficiency is lowered.
  • the object of the present invention is to provide a lithium sulfur battery electrolyte in order to overcome the deficiencies of the prior art.
  • the technical solution adopted by the present invention is: a lithium sulfur battery electrolyte comprising an ether organic solvent, a lithium salt and an ester additive, wherein the ester additive is selected from the group consisting of carbonates and sulfites. a mixture of one or more of the constituents.
  • the ester additive has a mass fraction of 0.5 to 5%.
  • ester additive has a mass fraction of 1 to 3%.
  • the structural formula of the ester additive is wherein Z is C or S, R 1 and R 2 are each independently alkyl or phenyl, R 3 and R 4 are each independently hydrogen or nitro, and R 5 and R 6 are independently H or F. .
  • ester additive is one or more selected from the following structural formulas,
  • the ether organic solvent is a mixture of ethylene glycol dimethyl ether and 1,3 dioxolane in a volume ratio of 1:1.
  • the concentration of the lithium salt is from 0.8 to 1.2 mol/L.
  • the lithium salt is lithium bis(trifluoromethylsulfonyl)imide.
  • Another object of the present invention is to provide a method for preparing the above lithium-sulfur battery electrolyte, which comprises the following steps:
  • step (b) A carbonate additive is added to the mixture obtained in the step (a), and the mixture is stirred and dissolved.
  • the present invention has the following advantages compared with the prior art: the lithium-sulfur battery electrolyte of the invention adopts a specific additive and an ether organic solvent and a lithium salt, so that the lithium-sulfur battery can be charged and discharged during the charging and discharging process.
  • the polysulfide generated during the charging and discharging process reacts, thereby inhibiting the shuttle back and forth of the polysulfide, effectively suppressing the shuttle effect of the lithium-sulfur battery, and improving the cycle life and coulombic efficiency of the lithium-sulfur battery.
  • FIG. 1 is a comparison diagram of average coulombic efficiency of a lithium-sulfur battery electrolyte assembled into a lithium-sulfur battery in Examples 1-5;
  • FIG. 2 is a cycle effect diagram of the lithium sulfur battery electrolyte assembled into a lithium sulfur battery in the fourth embodiment
  • Embodiment 3 is a charge and discharge curve of a lithium-sulfur battery electrolyte assembled into a lithium-sulfur battery in Embodiment 4;
  • Example 4 is a comparison diagram of coulombic efficiency in Example 2, Example 4, and Comparative Example 1 of the present invention
  • Figure 5 is a comparison diagram of Coulomb efficiency in Example 4, Comparative Example 1 and Comparative Example 2 of the present invention.
  • the lithium sulfur battery electrolyte of the present invention comprises an ether organic solvent, a lithium salt and an ester additive, the ester additive being a mixture of one or more selected from the group consisting of a carbonate and a sulfite;
  • the additive is mixed with the ether organic solvent and the lithium salt, so that it can react with the polysulfide generated during the charging and discharging process of the lithium-sulfur battery during the charging and discharging process, thereby inhibiting the back and forth shuttle of the polysulfide, and effectively suppressing the lithium-sulfur battery.
  • the shuttle effect improves the cycle life and coulombic efficiency of lithium-sulfur batteries.
  • the mass fraction of the above ester additive is preferably from 0.5 to 5%, more preferably from 1 to 3%.
  • the structural formula of the ester additive is preferably Wherein Z is C or S, R 1 and R 2 are each independently alkyl or phenyl, R 3 and R 4 are each independently hydrogen or nitro, and R 5 and R 6 are independently H or F. More preferably selected from one or more of the following structural formulas, Optimal
  • the ether organic solvent is preferably a mixture of ethylene glycol dimethyl ether and 1,3 dioxolane in a volume ratio of 1:1.
  • the concentration of the lithium salt is preferably 0.8 to 1.2 mol/L, preferably lithium bis(trifluoromethylsulfonyl)imide.
  • the method for preparing a lithium-sulfur battery electrolyte comprising the steps of: (a) adding a lithium salt to the ether organic solvent, stirring to dissolve it; and (b) adding a carbonate to the mixture obtained in the step (a). Additives, stir and dissolve.
  • the embodiment provides a lithium-sulfur battery electrolyte, and the preparation method thereof is specifically:
  • Lithium bis(trifluoromethylsulfonyl)imide is placed in a glove box for thorough drying; after sufficient drying, ethylene glycol dimethyl ether and 1,3 dioxane are added in a volume ratio of 1:1. In a mixed organic solvent of a cyclic ether, stir well until completely dissolved;
  • the present embodiment provides a lithium sulfur battery electrolyte, the preparation process of which is basically the same as that in the embodiment 1, except that the mass ratio of the additive in the mixed solution formed is 1 wt%.
  • the present embodiment provides a lithium sulfur battery electrolyte, the preparation process of which is basically the same as that in the embodiment 1, except that the mass ratio of the additive in the mixed solution formed is 2 wt%.
  • the present embodiment provides a lithium sulfur battery electrolyte, which is prepared in the same manner as in the first embodiment, except that the additive has a mass ratio of 3 wt% in the mixed solution formed.
  • the specific electrochemical test data is shown in Figure 2 and Figure 3.
  • the present embodiment provides a lithium sulfur battery electrolyte, and the preparation process thereof is basically the same as that in Embodiment 1, except that the mass ratio of the additive in the mixed solution formed is 5% by weight.
  • This embodiment provides a lithium sulfur battery electrolyte, the preparation process of which is basically the same as that in the embodiment 4, except that the additive is replaced with ethyl methyl carbonate.
  • This embodiment provides a lithium sulfur battery electrolyte, the preparation process of which is basically the same as that in the embodiment 4, except that the additive is replaced by dimethyl carbonate.
  • This embodiment provides a lithium-sulfur battery electrolyte, and the preparation process thereof is basically the same as that in Embodiment 4, except that the additive is replaced with fluoroethylene carbonate.
  • This embodiment provides a lithium sulfur battery electrolyte, the preparation process of which is basically the same as that in the embodiment 4, except that the additive is replaced with propylene carbonate.
  • the present embodiment provides a lithium sulfur battery electrolyte, which is prepared in the same manner as in the embodiment 4 except that the additive is replaced with ethylene carbonate.
  • This embodiment provides a lithium sulfur battery electrolyte, the preparation process of which is basically the same as that in the embodiment 4, except that the additive is replaced with t-butyl phenyl carbonate.
  • This embodiment provides a lithium sulfur battery electrolyte, the preparation process of which is basically the same as that in the embodiment 4, except that the additive is replaced with di-tert-amyl pyrocarbonate.
  • This embodiment provides a lithium-sulfur battery electrolyte, and the preparation process thereof is basically the same as that in the embodiment 4, except that the additive is replaced with diethyl sulfite.
  • This embodiment provides a lithium sulfur battery electrolyte, and the preparation process thereof is basically the same as that in the embodiment 4, except that the additive is replaced with ethylene sulfite.
  • the embodiment provides a lithium-sulfur battery electrolyte, and the preparation process thereof is basically the same as that in the embodiment 1, and the difference is:
  • the mass ratio of the additive in the resulting mixed solution was 0% by weight.
  • the embodiment provides a lithium-sulfur battery electrolyte, and the preparation process thereof is basically the same as that in the embodiment 4. The difference is that the additive is replaced with a lithium-sulfur battery additive lithium nitrate and a lithium nitrate in a mixed solution. It is 3 wt%.
  • the lithium-sulfur battery electrolyte in each of the above embodiments is assembled into a lithium-sulfur battery for electrochemical testing according to the existing method using a conventional sulfur-carbon mixture as an electrode material (refer to Xu, N. et al. Greatly enhanced shuttle effect for improved) Lithium battery performance through short chain intermediates. Nano Lett. 17, 538-543 (2017)).
  • FIG. 1 is a Coulomb efficiency comparison chart in Example 2, Example 4, and Comparative Example 1.
  • FIG. 5 is a comparison chart of Coulomb efficiency in Example 4, Comparative Example 1 and Comparative Example 2; apparently no additive or conventional additive is added. The resulting battery coulombic efficiency is worse than the use of the additive of the present invention.

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Abstract

一种锂硫电池电解液及其制备方法，包括醚类有机溶剂、锂盐和酯类添加剂，所述酯类添加剂为选自碳酸酯和亚硫酸酯中的一种或多种组成的混合物；采用特定的添加剂与醚类有机溶剂、锂盐进行混合，从而可以在充放电过程中与锂硫电池充放电过程中产生的多硫化物发生反应，进而抑制多硫化物的来回穿梭，有效的抑制锂硫电池的穿梭效应，提高锂硫电池的循环寿命和库伦效率。

Description

一种锂硫电池电解液及其制备方法 技术领域
本发明属于锂硫电池领域，涉及一种锂硫电池电解液，具体涉及一种锂硫电池电解液及其制备方法。
背景技术
现代社会的发展，化石能源消耗在能源消耗中占有越来越大的比例，发展可持续清洁能源迫在眉睫。如何解决环境污染问题和化石能源的持续消耗，高效的能源存储装置，作为当下最热门的研究和发展方向，是可持续再生能源工业、消费电子产业、交通行业的核心支柱。
在诸多储能方式中，锂离子电池由于自放电小、比能量高、循环寿命长、充电功率范围宽和质量轻等优点，在当今储能器件中占据核心地位。大多数的锂电池用碳材料当做负极，锂片为正极，利用锂离子在正负极之间来回穿梭贡献容量。1991年索尼首次推出商业化的锂离子电池后，锂离子电池开始广泛应用于手机、笔记本电脑、数码相机等便携式电子产品，并随着这些产品在全球的普及，锂离子电池的市场需求一直保持相当高的增长速度，市场对于锂离子电池的巨大需求也引导锂离子电池行业的继续走强并且随着全球对电动汽车的日益关注，也使锂离子电池在电动车方面的应用成为可能。经过20多年的发展，现有的锂离子电池已接近其理论容量，但仍不能满足高速发展的电子工业和新兴的电动汽车等行业的要求，寻找具有更高能量密度的电池系统迫在眉睫。
锂硫电池系统具有极高的理论能量密度，在多种储能系统中是最具潜力的一种二次电池。锂硫电池使用天然丰富的硫元素作为负极材料具有很高的理论比容(1675mAh/g)和较高能量密度(2500Wh/kg)，是锂离子电池的理论容量的五倍以上。与传统的锂离子电池机理不同，锂硫电池通过硫元素、可溶性多硫化物和不溶性硫化锂之间的多相转换氧化还原反应来提供高容量。然而，作为中间体的多硫化物，能够溶解在有机液体电解质中，导致严重的穿梭效应，造成活性物质的损失。同时，又与锂阳极发生严重寄生反应，降低循环寿命，导致特别低的库伦效率。此外，由于硫元素的绝缘性和在充放电过程中的体积膨胀(≈80％)，进一步导致锂硫电池循环寿命缩短和充电效率降低。如何提高锂硫电池的库伦效率，研究人员提出了较多的改进方案。这些方案集中于电池的负极材料，而对负极材料的改进，往往都会带来复杂的制备工艺，并且提高电池的成本。开发新的锂硫电池电解液是一个方便可行的方向之一。
发明内容
本发明目的是为了克服现有技术的不足而提供一种锂硫电池电解液。
为达到上述目的，本发明采用的技术方案是：一种锂硫电池电解液，它包括醚类有机溶剂、锂盐和酯类添加剂，所述酯类添加剂为选自碳酸酯和亚硫酸酯中的一种或多种组成的混合物。
优化地，所述酯类添加剂的质量分数为0.5～5％。
进一步地，所述酯类添加剂的质量分数为1～3％。
优化地，所述酯类添加剂的结构通式为
Figure PCTCN2017096364-appb-000001
Figure PCTCN2017096364-appb-000002
式中，Z为C或S，R1和R2相互独立地为烷基或苯基，R3和R4相互独立地为氢或硝基，R5和R6相互独立地为H或F。
进一步地，所述酯类添加剂为选自以下结构式中的一种或多种，
Figure PCTCN2017096364-appb-000003
更进一步地，所述酯类添加剂的结构式为
Figure PCTCN2017096364-appb-000004
优化地，所述醚类有机溶剂为乙二醇二甲醚和1,3二氧戊环的混合物，其体积比为1：1。
优化地，所述锂盐的浓度为0.8～1.2mol/L。
进一步地，所述锂盐为二(三氟甲基磺酰)亚胺锂。
本发明的又一目的在于提供一种上述锂硫电池电解液的制备方法，它包括以下步骤：
(a)向所述醚类有机溶剂中加入锂盐，搅拌使其溶解；
(b)向步骤(a)得到的混合物中加入碳酸酯类添加剂，搅拌使其溶解即可。
由于上述技术方案运用，本发明与现有技术相比具有下列优点：本发明锂硫电池电解液，采用特定的添加剂与醚类有机溶剂、锂盐，从而可以在充放电过程中与锂硫电池充放电过程中产生的多硫化物发生反应，进而抑制多硫化物的来回穿梭，有效的抑制锂硫电池的穿梭效应，提高锂硫电池的循环寿命和库伦效率。
附图说明
图1为实施例1-5中锂硫电池电解液组装成锂硫电池后平均库伦效率对比图；
图2为实施例4中锂硫电池电解液组装成锂硫电池后的循环效果图；
图3为实施例4中锂硫电池电解液组装成锂硫电池后充放电曲线；
图4为本发明实施例2、实施例4和对比例1中库伦效率对比图；
图5为本发明实施例4、对比例1和对比例2中库伦效率对比图。
具体实施方式
本发明锂硫电池电解液，它包括醚类有机溶剂、锂盐和酯类添加剂，所述酯类添加剂为选自碳酸酯和亚硫酸酯中的一种或多种组成的混合物；采用特定的添加剂与醚类有机溶剂、锂盐进行混合，从而可以在充放电过程中与锂硫电池充放电过程中产生的多硫化物发生反应，进而抑制多硫化物的来回穿梭，有效的抑制锂硫电池的穿梭效应，提高锂硫电池的循环寿命和库伦效率。
上述酯类添加剂的质量分数优选为0.5～5％，更优为1～3％。所述酯类添加剂的结构通式优选为
Figure PCTCN2017096364-appb-000005
式中，Z为C或S，R1和R2相互独立地为烷基或苯基，R3和R4相互独立地为氢或硝基，R5和R6相互独立地为H或F；更优为选自以下结构式中的一种或多种，
Figure PCTCN2017096364-appb-000006
Figure PCTCN2017096364-appb-000007
Figure PCTCN2017096364-appb-000008
Figure PCTCN2017096364-appb-000009
最优为
Figure PCTCN2017096364-appb-000010
所述醚类有机溶剂优选为乙二醇二甲醚和1,3二氧戊环的混合物，其体积比为1：1。所述锂盐的浓度优选为0.8～1.2mol/L，优选为二(三氟甲基磺酰)亚胺锂。上述锂硫电池电解液的制备方法，它包括以下步骤：(a)向所述醚类有机溶剂中加入锂盐，搅拌使其溶解；(b)向步骤(a)得到的混合物中加入碳酸酯类添加剂，搅拌使其溶解即可。
下面将结合实施例对本发明进行进一步说明。
实施例1
本实施例提供一种锂硫电池电解液，它的制备方法具体为：
(a)将二(三氟甲基磺酰)亚胺锂放入手套箱中进行充分干燥；充分干燥后，加入体积比为1：1的乙二醇二甲醚和1,3二氧戊环醚类混合有机溶剂中，进行充分的搅拌，直到完全溶解；
(b)向步骤(a)得到的混合物中加入添加剂双(4-硝基苯)碳酸酯(CAS号：5070-13-3，添加剂在形成的混合溶液中质量比为0.5wt％)，充分搅拌，待添加剂完全溶解后，静置24小时。
实施例2
本实施例提供一种锂硫电池电解液，其制备过程与实施例1中的基本一致，不同的是：添加剂在形成的混合溶液中质量比为1wt％。
实施例3
本实施例提供一种锂硫电池电解液，其制备过程与实施例1中的基本一致，不同的是：添加剂在形成的混合溶液中质量比为2wt％。
实施例4
本实施例提供一种锂硫电池电解液，其制备过程与实施例1中的基本一致，不同的是：添加剂在形成的混合溶液中质量比为3wt％。，具体的电化学测试数据如图2和图3所示。
实施例5
本实施例提供一种锂硫电池电解液，其制备过程与实施例1中的基本一致，不同的是：添加剂在形成的混合溶液中质量比为5wt％。
实施例6
本实施例提供一种锂硫电池电解液，其制备过程与实施例4中的基本一致，不同的是：添加剂换成了碳酸甲乙酯。
实施例7
本实施例提供一种锂硫电池电解液，其制备过程与实施例4中的基本一致，不同的是：添加剂换成了碳酸二甲酯。
实施例8
本实施例提供一种锂硫电池电解液，其制备过程与实施例4中的基本一致，不同的是：添加剂换成了氟代碳酸乙烯酯。
实施例9
本实施例提供一种锂硫电池电解液，其制备过程与实施例4中的基本一致，不同的是：添加剂换成了碳酸丙烯酯。
实施例10
本实施例提供一种锂硫电池电解液，其制备过程与实施例4中的基本一致，不同的是：添加剂换成了碳酸乙烯酯。
实施例11
本实施例提供一种锂硫电池电解液，其制备过程与实施例4中的基本一致，不同的是：添加剂换成了叔丁基苯基碳酸酯。
实施例12
本实施例提供一种锂硫电池电解液，其制备过程与实施例4中的基本一致，不同的是：添加剂换成了焦碳酸二叔戊酯。
实施例13
本实施例提供一种锂硫电池电解液，其制备过程与实施例4中的基本一致，不同的是：添加剂换成了亚硫酸二乙酯。
实施例14
本实施例提供一种锂硫电池电解液，其制备过程与实施例4中的基本一致，不同的是：添加剂换成了亚硫酸亚乙酯。
对比例1
本实施例提供一种锂硫电池电解液，其制备过程与实施例1中的基本一致，不同的是： 添加剂在形成的混合溶液中质量比为0wt％。
对比例2
本实施例提供一种锂硫电池电解液，其制备过程与实施例4中的基本一致，不同的是：添加剂换成了传统锂硫电池添加剂硝酸锂，硝酸锂在形成的混合溶液中质量比为3wt％。
将上述各实施例中的锂硫电池电解液按照现有的方法，利用传统硫碳混合物作为电极材料组装成锂硫电池进行电化学测试(参考Xu,N.et al.Greatly suppressed shuttle effect for improved lithium sulfur battery performance through short chain intermediates.Nano Lett.17,538-543(2017))。
表1 实施例4、实施例6-14中不同添加剂锂硫电池的测试数据
实施例 锂硫电池电解液添加剂 库伦效率
4 双(4-硝基苯)碳酸酯 100％
6 碳酸甲乙酯 91.5％
7 碳酸二甲酯 93.7％
8 氟代碳酸乙烯酯 92.3％
9 碳酸丙烯酯 94.7％
10 碳酸乙烯酯 95.3％
11 叔丁基苯基碳酸酯 96.1％
12 焦碳酸二叔戊酯 97.2％
13 亚硫酸二乙酯 94.1％
14 亚硫酸亚乙酯 93.5％
从图1中可以看出，当添加剂在形成的混合溶液中质量比为3wt％时，由此制得的电池平均库伦效率最高。而图4为实施例2、实施例4和对比例1中库伦效率对比图；图5为实施例4、对比例1和对比例2中库伦效率对比图；显然不加入添加剂或者采用常规的添加剂制得的电池库伦效率要差于使用本发明添加剂的。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围，凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (10)

  1. 一种锂硫电池电解液，其特征在于：它包括醚类有机溶剂、锂盐和酯类添加剂，所述酯类添加剂为选自碳酸酯和亚硫酸酯中的一种或多种组成的混合物。
  2. 根据权利要求1所述锂硫电池电解液，其特征在于：所述酯类添加剂的质量分数为0.5～5％。
  3. 根据权利要求2所述锂硫电池电解液，其特征在于：所述酯类添加剂的质量分数为1～3％。
  4. 根据权利要求1所述锂硫电池电解液，其特征在于：所述酯类添加剂的结构通式为
    Figure PCTCN2017096364-appb-100001
    式中，Z为C或S，R1和R2相互独立地为烷基或苯基，R3和R4相互独立地为氢或硝基，R5和R6相互独立地为H或F。
  5. 根据权利要求4所述的锂硫电池电解液，其特征在于：所述酯类添加剂为选自以下结构式中的一种或多种，
    Figure PCTCN2017096364-appb-100002
    Figure PCTCN2017096364-appb-100003
  6. 根据权利要求5所述的锂硫电池电解液，其特征在于：所述酯类添加剂的结构式为
    Figure PCTCN2017096364-appb-100004
  7. 根据权利要求1所述的锂硫电池电解液，其特征在于：所述醚类有机溶剂为乙二醇二甲醚和1,3二氧戊环的混合物，其体积比为1：1。
  8. 根据权利要求1所述的锂硫电池电解液，其特征在于：所述锂盐的浓度为0.8～1.2mol/L。
  9. 根据权利要求8所述的锂硫电池电解液，其特征在于：所述锂盐为二(三氟甲基磺酰)亚胺锂。
  10. 权利要求1至9中任一所述锂硫电池电解液的制备方法，其特征在于，它包括以下步骤：
    (a)向所述醚类有机溶剂中加入锂盐，搅拌使其溶解；
    (b)向步骤(a)得到的混合物中加入碳酸酯类添加剂，搅拌使其溶解即可。
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