Unifying the Clustering Kinetics of Lithium Polysulfides with the Nucleation Behavior of Li2S in Lithium-Sulfur Batteries

Within the lithium-sulfur (Li-S) battery, a wide variety of soluble lithium polysulfide intermediates form during operation. Under lean-electrolyte or low-temperature conditions, the solution coordination of polysulfides dynamically shifts to highly clustered states, which is subsequently accompanied by inhibited electrochemical kinetics. In fact, it has been shown that the tendency for polysulfides to strongly aggregate is one of the dominant kinetically limiting obstacles towards achieving adequate utilization of active material under such conditions. While this association has been noted before, it is not explicitly understood what mechanism intrinsic to polysulfide clustering curtails the electrochemical utilization of active material, particularly during the conversion to insoluble Li2S. Here, we perform a series of investigations to unify and link the kinetic constraints that arise from polysulfide clustering to the nucleation and growth behavior of Li2S. We find that there is a drastic decrease in polysulfide diffusion coefficient arising from the advent of clustering, and that this decline functionally matches that seen for the nucleation and growth rate constants for Li2S deposition. Additionally, it is found that there is a less favorable minimization of energy during Li2S nucleation, arising from the altered solvation stability of polysulfide clusters. This knowledge expands our understanding of the Li-S materials chemistry and the primary factors dictating the electrochemical behavior.