Research progress of electrolyte for lithium-sulfur batteries: molecular design and application

doi:10.11949/0438-1157.20250331

Abstract

Abstract:

Lithium sulfur(Li-S) batteries, as an energy storage system with high energy density, are a key research object in the field of energy. However, problems such as the shuttle effect of soluble lithium polysulfides and slow redox kinetics during charge and discharge have seriously hampered the commercialization of Li-S batteries. As an indispensable part of the lithium sulfur battery system, the electrolyte is usually composed of lithium salts, organic solvents, and various additives. It plays a role in protecting the lithium negative electrode and conducting lithium ions during the charging and discharging process. Its function has an impact on the reaction process, cycle life, and safety performance of the battery. In recent years, electrolyte additives have attracted much attention from researchers. Adding them to electrolytes can achieve functions such as inhibiting polysulfide (LiPSs) shuttle, enhancing electrode interface stability, and improving ion conductivity. Through a survey of recent relevant literature, this article introduces the molecular design of additives containing nitrogen, fluorine, sulfur, and multi atom synergistic effects, as well as strategies and research progress to enhance the redox kinetics of battery charging and discharging and suppress the shuttle effect of polysulfides. It also analyzes the different mechanisms exhibited by these additives in regulating the interface between polysulfides and electrodes due to differences in electronegativity. At the same time, the important role of lithium salts in electrolytes was briefly explained, including providing lithium ions, participating in electrode reaction processes, maintaining charge balance, and ensuring ion conduction, which expanded the ideas for the molecular design and practical application of lithium sulfur battery electrolyte additives. Finally, we provide some perspectives on the future development of electrolyte additives for lithium-sulfur batteries.

Key words: lithium-sulfur battery, electrolytes additive, interface, kinetics, polysulfides

摘要：

锂硫（Li-S）电池作为一种具有高能量密度的储能体系，是能源领域的重点研究对象。但其在充放电过程中可溶性多硫化锂的穿梭效应及氧化还原动力学缓慢等问题，严重影响了锂硫电池的商业化发展进程。电解液作为锂硫电池体系中不可或缺的一部分，通常由锂盐、有机溶剂以及各类添加剂共同组成，在充放电过程中起到保护锂负极、传导锂离子的作用，其功能对电池的反应过程、循环寿命和安全性能等方面均产生影响。近年来，电解液添加剂备受研究者的关注，将其加入到电解液中可实现抑制多硫化物（LiPSs）穿梭、增强电极界面稳定性和提高离子电导率等功能。通过对近期相关文献的调查，介绍了含氮、氟、硫和多原子协同作用的添加剂的分子设计，及其提升电池充放电的氧化还原动力学和抑制多硫化物穿梭效应的策略及研究进展，并分析其因电负性的差异，在调控多硫化物和电极界面表现出的不同机制。简要阐述了锂盐在电解液中的重要作用，包括提供锂离子，参与电极反应过程，维持电荷平衡和保障离子传导等，为锂硫电池电解液添加剂的分子设计与实际应用拓展了思路。最后展望了锂硫电池电解液添加剂的未来发展方向。

关键词: 锂硫电池, 电解液添加剂, 界面, 动力学, 多硫化物

CLC Number:

TQ 152

Menghan WANG, Miao YU, Tong WU. Research progress of electrolyte for lithium-sulfur batteries: molecular design and application[J]. CIESC Journal, 2025, 76(12): 6196-6217.

王梦涵, 于淼, 吴桐. 锂硫电池电解液研究进展：分子设计与应用[J]. 化工学报, 2025, 76(12): 6196-6217.

Figures/Tables 17

Fig.1 Electrolyte additives and their functions for lithium-sulfur batteries

Fig.2 (a) Ultraviolet-visible spectra of Li2S8 solution with QASs, T1Br, T2Br, T3Br, T4Br, T8Br and T3TFSI; (b) Reaction equation; (c) S-K-edge Near Edge Structure (XANES) Spectrum during Positive Electrode Discharge in T3Br Electrolyte; (d) Voltage curves of the electrode during the discharge process in T3Br and blank electrolyte; (e) Schematic diagram of the influence of blank electrolytes and T3Br electrolytes on the evolution of the electrochemical interface on the lithium surface; (f) Long cycle performance of 1C (Under the corresponding current, one discharge lasts for 1 hour)[45]

Fig.3 (a) The structure of the oxazole Li2S n (n=4,6,8) complex and the schematic diagram of the oxazole compounds participating in the formation of solid electrolyte interface facial mask and inhibiting the formation of lithium dendrites; (b) Ionic conductivity and Li+transfer number; (c) S After 50 cycles, the scanning electron microscope (SEM) image of the Li | Li symmetric battery’s lithium negative electrode corresponds to the cross-sectional SEM image; (d) 0.1C, Cycle performance of high load Li-S batteries with sulfur loadings of 3.4 mg·cm-2 and 3.7 mg·cm-2 using Ta and Tta based electrolytes[46]

Fig.4 (a) Schematic diagram of the reaction between TFBCA and polysulfides; (b) Ionic conductivity of electrolytes with and without TFBCA; (c) SEI schematic diagram with and without TFBCA; (d) Cycle performance of TFBCA battery under 0.1C, sulfur load of 7.1 mg·cm-2[47]

Fig.5 (a) Schematic diagram of the effect of TFMSA additive on the electrode/electrolyte interface of lithium sulfur batteries; (b) Charge discharge curves of batteries containing blank electrolyte and TFMSA electrolyte at 0.5C rate; (c) Surface F 1s and S 2p XPS spectra after cycling with blank electrolyte and TFMSA electrolyte; (d) 0.2C, Cycle performance of lithium sulfur battery with sulfur load of 5.2 mg·cm-2[50]

Fig.6 (a) TFEB-Li2S x medium redox catalytic sulfur conversion; (b) Cyclic voltammetry of 2 mmol·L-1 Li2S8 positive electrode electrolyte with different concentrations of TFEB at 200 mV·S-1; (c) XPS spectra of circulating lithium negative electrode with and without TFEB electrolyte; (d) 0.1C, Cycle stability of lithium sulfur batteries with sulfur loading of 5 mg·cm-2 and different TFEB contents[51]

Fig.7 (a) Discharge capacity and (b) Coulombic efficiency (10 mA·g-1 LiMn2O4) of graphite/LiMn2O4 battery under the conditions of no FSE and 0.5% (mass) FSE addition, after 10 initial cycles at room temperature, the 11th to 30th cycles were carried out at 60℃[53]

Fig.8 Reaction pathway of lithium polysulfide on the positive electrode and charge discharge curve of Li-S battery (a) without additives and (c) additives; (b) napp/n diagram; (d) Electrochemical impedance spectroscopy (EIS) plots of symmetric sulfur/carbon batteries with and without thiophene batteries exhibiting a 10 mV amplitude perturbation in the frequency range of 105 to 10-2 Hz; (e) C/40, Electrochemical performance of lithium sulfur battery with sulfur loading of 3.6 mg·cm-2[62]

Fig. 9 (a) Schematic diagram of the formation of solid electrolyte interface facial mask; (b) XPS depth profiles of SEI with and without BTB additive for lithium negative electrode after 5 cycles; (c) SEM of cycling Li negative electrode with and without BTB additive in Li-S battery after 20 cycles; (d) 0.1C, Cycle performance of high load S positive electrode, low E/S ratio, and ultra-thin Li negative electrode[63]

Fig.10 (a) not included; (b) Electrospray ionization mass spectrum of Li2S4 solution added with BPD; The CV and Raman peaks at 217, 228, 234, 526, and 534 cm-1 of the sulfur carbon cathode obtained in alkaline electrolyte with 5 mmol·L-1 BPD during (c) discharge and (d) charge processes; (e) SEM of lithium negative electrode with and without the addition of 25 mmol·L-1 BPD after 0.1C cycling; (f) The cyclic performance of sulfur carbon cathode with different thiol based additives at 0.1C[64]

Fig.11 LC-MS spectra of discharged products in Li-S batteries with 4Mpy additive: (a) lithium-pyridinethiolate (Li-pyS) and (b) Li-pyS2; LC-MS spectra of recharged products: (c) 4,4-pyridinedisulfide (4,4-pyS2) and (d) 4,4-pyridinetetrasulfide (4,4-pyS4)；(e) Discharge reduction process of Li-S batteries with 4Mpy additive; (f) Cycle performance under high sulfur load of 0.05C; (g) Rate performance at 0.1C to 4C[73]

Fig.12 (a) Self extinguishing time test of different electrolytes; (b) Limit oxygen index of different electrolytes; (c) Schematic diagram of PFPN flame retardant mechanism and its influence on electrode surface SEI; (d) Combustion test of cyclic sulfur positive electrode containing PFPN in ether based electrolyte after 50 cycles; (e) 0.2C Cycle performance[74]

Table 1 Performance parameters of lithium sulfur batteries assembled using different electrolyte additives

特征原子	添加剂	面载量/ (mg·cm^-2)	放电比容量/面积容量	循环性能	文献
N	卤化季铵盐-四丙基溴化铵（T3Br）	1.5~2.0	1132 mAh·g^-1（0.1C）	1C，700次循环后放电比容量590 mAh·g^-1	[45]
	三唑（Ta）、四唑（Tta）	3.4、3.7	800 mAh·g^-1、约790 mAh·g^-1（0.1C）	0.1C，100次循环后容量保持率96.5％（Ta）87.5％（Tta）	[46]
	4-（三氟甲基）硫代苯甲酰胺（TFBCA）	7.1	8.1 mAh cm^-2 (0.2C)	0.1C，50次循环后面积容量7 mAh·cm^-2	[47]
F	三氟甲磺酰胺（TFMSA）	5.2	1000 mAh·g^-1（0.2C）	0.2C，100次循环后放电比容量828 mAh·g^-1	[50]
	三（2，2，2-三氟乙基）硼酸酯（TFEB）	5.0	1084 mAh·g^-1（0.1C）	0.1C，200次循环后容量保持率63.3％	[51]
	1，2-双（二氟甲基硅基）乙烷（FSE）（锂离子电池）	—	约90 mAh (g of LiMn₂O₄)^-1 （60℃ 10 mA (g of LiMn₂O₄)^-1）	60℃，20次循环后放容量保持率超过62％；从室温升到60℃时，电池的库仑效率立即恢复	[53]
S	噻吩	3.6	1016 mAh·g^-1（C/40）	C/40，100次循环后容量保持率74％	[62]
	3，5-双（三氟甲基）苯硫酚（BTB）	4.5	950 mAh·g^-1(0.1C)	0.1C，82次循环后放电比容量700 mAh·g^-1	[63]
	联苯-4，4′-二硫醇（BPD）	0.7~1.2	900 mAh·g^-1(0.1C)	0.1C，300次循环后放电比容量575 mAh·g^-1	[64]
N、S	4-巯基吡啶（4Mpy）	5.59	6 mAh·cm^-2（0.05C）	0.05C，50次循环后面积容量4.85 mAh·cm^-2	[73]
N、F	乙氧基（五氟）环三磷腈（PFPN）	2.3	1103.4 mAh·g^-1（0.2C）	0.2C，100次循环后放电比容量904.6 mAh·g^-1；使用PFPN电池循环50次后硫正极点燃后迅速熄灭	[74]

Fig.13 (a) Arrhenius plot of ion conductivity; (b) Thermogravimetric analysis (TGA) curve of electrolyte; (c) Schematic diagram of solid electrolyte interface facial mask formed on lithium cathode in LiTCM and LiTFSI batteries; (d) The rate performance of LiTCM/PEO electrolyte under different salt contents; (e) Comparison of cycling performance of lithium sulfur batteries using Li X /PEO (X=TCM- or TFSI-) electrolyte under the same ethylene oxide unit (EO) / Li ratio of 20[88]

Figure 14 (a) UV visible absorption spectrum; High resolution spectra of (b) Li 1s、O 2s and F 2s XPS on the surface of lithium electrode; (c) 0.3C, Long term cycling performance of Li-S batteries under different electrolytes; (d) Rate performance of Li-S batteries using dual salt medium concentration electrolyte (MCE) and a novel diluted medium concentration electrolyte (DMCE) electrolyte[89]

Fig.15 (a) Optical image of LiI gel suppression phenomenon; (b) Schematic diagram of reaction pathways of Li-S battery in blank electrolyte and LiI electrolyte; (c) 0.05C, Cycle performance of 400 Wh·kg-1 soft pack battery[90]

Table 2 Performance parameters of lithium-sulfur batteries assembled with different lithium salts

体系	锂盐	面载量/(mg·cm^-2)	放电比容量	循环性能	文献
单盐体系	三氰甲烷化物（LiTCM）^①	0.8~1.1	≈0.7 mAh·cm ^-2(0.1C)	0.2C，库仑效率约100％，保持30次循环	[88]
双盐体系	LiTFSI-LiFSI^②	2.0	682 mAh·g^-1（0.3C）	0.3C，500次循环放电比容量626 mAh·g^-1	[89]
双盐体系	LiTFSI-LiI^③	7.1（单面）	416 Wh·kg^-1（0.05C）	0.05C，16次循环保持稳定的库仑效率	[92]

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