Lithium-sulfur (Li-S) all-solid-state batteries (ASSBs) hold great promise for next-generation safe, durable and energy-dense battery technology. However, solid-state sulfur conversion reactions are kinetically sluggish and primarily constrained to the restricted three-phase boundary area of sulfur, carbon and solid electrolytes, making it challenging to achieve high sulfur utilization. Here we develop and implement mixed ionic-electronic conductors (MIECs) in sulfur cathodes to replace conventional solid electrolytes and invoke conversion reactions at sulfur-MIEC interfaces in addition to traditional three-phase boundaries. Microscopic and tomographic analyses reveal the emergence of mixed-conducting domains embedded in sulfur at sulfur-MIEC boundaries, helping promote the thorough conversion of active sulfur into Li2S. Consequently, substantially improved active sulfur ratios (up to 87.3%) and conversion degrees (>94%) are achieved in Li-S ASSBs with high discharge capacity (>1,450 mAh g-1) and long cycle life (>1,000 cycles). The strategy is also applied to enhance the active material utilization of other conversion cathodes.
© 2025. The Author(s), under exclusive licence to Springer Nature Limited.