Lan Jiaqi, Cao Yun, Geng Chuannan, Zheng Lijun, Lin Qiaowei, Wang Da-Wei, Lv Wei, Lu Jun
Shenzhen Geim Graphene Center, Engineering Laboratory for Functionalized Carbon Materials, Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen, 518055, China.
College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310058, P. R. China.
Adv Mater. 2025 Sep;37(37):e2505527. doi: 10.1002/adma.202505527. Epub 2025 Jun 25.
Lithium-sulfur (Li-S) batteries, characterized by their high energy density and cost-effectiveness, are the primary candidates for lithium-ion batteries. Yet, critical challenges persist, largely owing to the polysulfide (PS) anion shuttle and the instability of the lithium metal anode (LMA). Salt anions are indispensable in batteries, which influence the basic properties of bulk electrolytes (e.g., solubility, stability, and ion conductivity) and the electrode-electrolyte interphases. Apart from those, the intrinsic characteristics of anions are of particular importance in Li-S batteries, as PS anions are major active intermediates that directly determine the sulfur redox kinetics and reversibility. However, the anion regulation needs further investigated, especially according to the Li-S chemistry. In this regard, fundamental considerations are provided on the anion engineering of Li-S batteries. Through a comprehensive analysis, the electrochemical behaviors of anions are reviewed. Then, the recent works on anion regulation for cathodes and anodes are summarized. For sulfur cathodes, the PSs dissolution, adsorption, conversion kinetics, and pathway are discussed in detail. For LMA, the influence of anion on lithium diffusion kinetic, the formation of SEI, and the anticorrosion are summarized. Finally, insights into the future development of anion studies are provided, aiming to identify more adequate anions for Li-S batteries.
锂硫（Li-S）电池以其高能量密度和成本效益著称，是锂离子电池的主要候选者。然而，关键挑战依然存在，这主要归因于多硫化物（PS）阴离子穿梭以及锂金属负极（LMA）的不稳定性。盐阴离子在电池中不可或缺，它影响着本体电解质的基本性质（如溶解度、稳定性和离子电导率）以及电极-电解质界面。除此之外，阴离子的固有特性在锂硫电池中尤为重要，因为PS阴离子是直接决定硫氧化还原动力学和可逆性的主要活性中间体。然而，阴离子调控仍需进一步研究，尤其是基于锂硫化学。在这方面，对锂硫电池的阴离子工程进行了基本考量。通过全面分析，综述了阴离子的电化学行为。然后，总结了近期关于阴极和阳极阴离子调控的研究工作。对于硫阴极，详细讨论了PS的溶解、吸附、转化动力学及途径。对于LMA，总结了阴离子对锂扩散动力学、固体电解质界面膜（SEI）形成及防腐的影响。最后，对阴离子研究的未来发展提供了见解，旨在为锂硫电池找到更合适的阴离子。
