Kinetic activation of interfacial Li₂S via zirconia membrane reactor confinement catalysis for high‐performance lithium/sulfur batteries

The slow kinetics and irreversibility of Li 2 S deposition and dissolution during the sulfur reduction/evolution reactions (SRR/SER) hinder the fast‐charging and high‐rate capabilities of lithium–sulfur (Li/S) batteries. To address this challenge, we design a zirconia membrane reactor (ZMR) composed of ZrO 2 /N‐doped carbon nanofibers (ZONC) to kinetically regulate the interfacial reversible conversion of Li 2 S. Electrochemical measurements, in situ x‐ray diffraction, and density functional theory calculations are employed to investigate the confinement catalysis of ZMR and elucidate the Li 2 S activation mechanism for enhanced rate performance and cycling stability. Operating at the cathode side, the ZMR enables the Li/S cell to deliver an initial discharge specific capacity of 1460.8 mAh g −1 at 0.1 C (corresponding to a sulfur utilization of approximately 87.2%), a high‐rate capability of 931.4 mAh g −1 at 5 C, and a capacity retention of 91.0% after 200 cycles at 3 C. Moreover, when a sandwich configuration module (ZMR‐S‐ZMR) is fabricated to support a high‐sulfur‐loading cathode, the resulting Li/S coin cell with a sulfur loading of 12.0 mg cm −2 achieves a remarkable areal capacity of 8.6 mAh cm −2 and 94.2% capacity retention after 90 cycles at 0.1 C (2.2 mA).