Manipulating Quasi‐Solid‐State Sulfur Conversion in Room‐Temperature Na─S Batteries

ABSTRACT Surface‐localized quasi‐solid‐state sulfur conversion significantly enhances cyclability of room‐temperature sodium‐sulfur (RT Na─S) batteries, yet the intrinsically limited ion/electron transport within the confined reaction zone leads to high polarization and poor long‐term stability. Herein, we elaborate nitrogen‐doped hierarchical porous carbon nanoplates (N‐HPC) as a multifunctional sulfur host to kinetically manipulate surface‐localized quasi‐solid‐state sulfur conversion. The interconnected micro/mesopores provide robust physical confinement for sulfur, while the abundant N‐doping sites synergistically regulate the electronic structure of carbon matrices, thereby enhancing chemical affinity for polysulfides and catalyzing sulfur redox reactions. The resulting RT Na─S batteries achieve an ultra‐stable cycling performance over 2000 cycles at 1.0 C with a negligible capacity fading rate of 0.024% per cycle and exhibit a highrate capacity of 443.1 mA h g −1 at 2.0 C. A practical pouch cell further demonstrates a high reversible capacity of 1339.8 mA h g −1 at 0.1 C with high cycling capacity retention. This work provides a reliable strategy to regulate surface‐localized quasi‐solid‐state sulfur redox reactions, and our findings highlight the synergistic design of the electrode host and electrolyte is key to realizing durable and high‐rate RT Na─S batteries.