Influence of Lithium Polysulfide Clustering on the Kinetics of Electrochemical Conversion in Lithium–Sulfur Batteries

The electrochemistry of lithium–sulfur (Li–S) batteries is heavily reliant on the structure and dynamics of lithium polysulfides, which dissolve into the liquid electrolyte and mediate the electrochemical conversion process during operation. This behavior is considerably distinct from the widely used lithium-ion batteries, necessitating new mechanistic insights to fully understand the electrochemical phenomena. Testing at low-temperature conditions presents a unique opportunity to glean new insights into the chemistry in kinetically constrained environments. Under such conditions, despite the low freezing point and favorable ionic conductivity of the glyme-based electrolyte, Li–S batteries exhibit counterintuitively poor performance. Here, we show that beyond just existing in single-molecule conformations, lithium polysulfides tend to cluster and aggregate in solution, particularly at low-temperature conditions, which subsequently constrains the kinetics of electrochemical conversion. Energetics and coordination implications of this behavior are extended toward a new framework for understanding the solution coordination dynamics of dissolved lithium species. Based on this framework, a favorable strongly bound lithium salt is introduced in the Li–S electrolyte to disrupt polysulfide clustered networks, enabling substantially enhanced low-temperature electrochemical performance. More broadly, this mechanistic insight heightens our understanding of polysulfide chemistry irrespective of temperature, confirming the link between the solution conformation of active material and electrochemical behavior.