Tailored Reaction Route by Micropore Confinement for Li–S Batteries Operating under Lean Electrolyte Conditions

Lithium‐sulfur (Li–S) batteries are one of the most promising alternative energy storage systems beyond Li‐ion batteries. However, the sluggish kinetics of the nucleation and growth of the solid discharge product of Li2S/Li2S2 in the lower discharge plateau has been recently identified as a critical hurdle for attaining high specific capacity in Li–S batteries with high sulfur loadings under lean electrolyte conditions. Herein, a new strategy of breaking the charge‐transport bottleneck by successful generation of experimentally verified stable Li2S2 and a reservoir of quasi‐solid lithium polysulfides within the micropores of activated carbon fiber cloth as a high‐sulfur‐loading host is proposed. The developed Li–S cell is capable of delivering a highly sustainable areal capacity of 6.0 mAh cm−2 under lower electrolyte to sulfur ratios (<3.0 mLE gS−1). Micropore confinement leads to generation of solid Li2S2 that enables high utilization of the entire electroactive area by its inherent self‐healing capacity. This strategy opens a new avenue for rational material designs for Li–S batteries under lean electrolyte condition.