Advancing Li–S full cells: integrating a freestanding interlayer and reduced TiO ₂ /S cathode with a pre-lithiated graphite anode

Abstract Progress in sulfur cathodes and separator interlayers has substantially curtailed polysulfide shuttling and sluggish kinetics in Li–S batteries. However, the instability of lithium metal anodes remains a major barrier to commercialization. Replacing lithium with mature lithiated graphite is attractive, but ether-based electrolytes used in Li–S cells induce Li ⁺ /solvent co‐intercalation and rapid failure of graphite electrodes. Building optimized interlayers and sulfur cathodes, this study focuses on making graphite fully compatible with ether electrolytes (DOL/DME). By systematically adjusting the lithium-salt concentration and LiNO ₃ additive, we found a finely tuned compositional regime in which the graphite electrode is free from solvent co-intercalation without markedly impairing cathode kinetics. This enabled the integration of an H–TiO ₂ /S cathode, a thin freestanding PVDF/MS interlayer, and a lithiated graphite anode into a full cell, which delivered 1066 mAh⋅g _sulfur ⁻¹ at 0.1 C ( N/P = 0.87). The resulting prototype demonstrates that Li–S chemistry can operate without a lithium-metal anode, offering a practical route toward safer and more commercially viable Li–S batteries.