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

Abstract

The slow kinetics and irreversibility of Li₂S 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 ZrO₂/N-doped carbon nanofibers (ZONC) to kinetically regulate the interfacial reversible conversion of Li₂S. Electrochemical measurements, in situ x-ray diffraction, and density functional theory calculations are employed to investigate the confinement catalysis of ZMR and elucidate the Li₂S 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).

Keywords

confinement catalysis / Li/S batteries / Li₂S activation / rate capability / zirconia membrane reactor (ZMR)

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