锂硫电池多硫化物溶解度的电解质调控与反应机制研究进展

Research progress on electrolyte regulation and reaction mechanism of solubility of polysulfides in lithium-sulfur batteries

  • 摘要: 锂硫电池(Lithium sulfur batteries, LSBs)因硫正极的高理论比容量和能量密度,成为储能领域着力发展的下一代高能量密度电池体系。然而,其商用化发展受限于锂硫电池充放电过程多硫化物(Polysulfide, PS)“穿梭效应”严重、硫及放电产物(Li 2S 2/Li 2S)的电导率低、充放电过程硫正极体积膨胀明显(~80%)以及锂负极锂枝晶生长等严重问题。可溶性多硫化物作为关键的液相反应中间体,是实现高效“固-液-固”转化反应路径的基础。它避免了缓慢的固-固反应,极大地提升了反应动力学和硫的利用率,是锂硫电池获得高容量的关键,然而,当溶解度过高时,大量多硫化物会扩散至锂金属负极,这直接导致活性物质不可逆流失以及电池严重的自放电,最终造成容量的快速衰减。因此,电解液设计成为本质上解决这些问题的有效策略,其通常在于通过调控多硫化物的溶解度进一步平衡反应动力学与循环稳定性,实现对硫正极中多硫化物的高效转化调控,从而实现锂硫电池高性能稳定保持。本文系统阐述了锂硫电池电解液设计的主要反应体系,聚焦硫正极中多硫化物溶解度与电解液调控机制的相互关系,揭示其当前发展应用现状和未来发展突破方向。具体而言,不溶体系通过物理/化学限域彻底阻断多硫化物溶出,以减小硫载量和反应动力学换取硫电极循环稳定;微溶体系通过重构溶剂化作用,利用高浓度锂盐或弱配位溶剂压缩自由溶剂相空间,在微量溶解平衡下实现贫电解液中的准固态转化,从根源抑制穿梭效应,同时可缓解电极动力学迟滞问题;溶解体系通过主动提高多硫化物溶解度,加快反应动力学,同时也可实现低电解液用量和高倍率性能,但需解决溶解度增加导致的穿梭效应问题。最后,我们对锂硫电池中多硫化物电解液溶解度调控面临的挑战和未来发展前景做出总结和展望。

     

    Abstract: Lithium sulfur batteries (LSBs) are emerging as the next generation of high-energy-density battery systems in the field of energy storage due to the high theoretical specific capacity and energy density of the sulfur cathode. However, their commercial development is hindered by the serious "shuttle effect" of polysulfides (PS) during charging and discharging, the low conductivity of sulfur and its discharged products (Li 2S 2/Li 2S), the significant volume expansion (~80%) of the sulfur cathode during cycling, and the growth of lithium dendrites on the lithium anode. As a key liquid-phase reaction intermediate, soluble polysulfides are the basis for achieving an efficient "solid-liquid-solid" conversion reaction path. It avoids the slow solid-solid reaction, greatly improves the reaction kinetics and sulfur utilization, and is the key to obtaining high capacity of lithium-sulfur batteries. However, when the solubility is more, a large number of polysulfides will diffuse to the lithium metal anode, which directly leads to the irreversible loss of the active material and the serious self-discharging, resulting in rapid capacity decay. In this context, electrolyte design has emerged as an effective strategy to fundamentally address these problems. This approach typically aims to further balance reaction kinetics and cycle stability by regulating the solubility of polysulfides, thereby achieving efficient conversion and regulation of polysulfides in sulfur cathodes, which is essential for achieving high and stable performance of lithium-sulfur batteries. This paper systematically reviews the main electrolyte design approaches for lithium-sulfur batteries. It focuses on the relationship between polysulfide solubility in the sulfur cathode and the regulation mechanism through electrolyte, highlighting the current development status, application landscape, and future directions. Specifically, insoluble systems completely block polysulfide dissolution via physical/chemical confinement meanwhile reducing sulfur loading and reaction kinetics to enhance the cycle stability of the sulfur electrode; conversely, by reconstructing solvation effects using high-concentration lithium salts or weakly-coordinating solvents, researchers compress the free solvent phase space, enabling quasi-solid-state conversion under lean electrolyte conditions through micro-dissolution equilibrium, which suppresses the shuttle effect at its source and mitigates electrode kinetic hysteresis. Dissoluble systems accelerate reaction kinetics by actively increasing PS solubility and can achieve low electrolyte usage and high-rate performance, but they require solutions to mitigate the shuttle effect resulting from the increased solubility. Finally, we summarize the challenges and provide a prospective outlook on the future development of PS electrolyte solubility regulation in LSBs.

     

/

返回文章
返回