Consolidating Lithiothermic‐Ready Transition Metals for Li2S‐Based Cathodes

Li2 S holds a promising role as a high-capacity Li-containing cathode, circumventing use of metallic lithium in constructing next-generation batteries to replace current Li-ion batteries. However, progress of Li2 S cathode has been plagued by its intrinsic drawbacks, including high activation potentials, poor rate performance, and rapid capacity fading during long cycling. Herein, a series of Li2 S/transition metal (TM) nanocomposites are synthesized via a lithiothermic reduction reaction, and it is realized that the presence of TMs in Li2 S matrix can transform electrochemical behaviors of Li2 S. On the one hand, the incorporation of W, Mo, or Ti greatly increases electronic and ionic conductivity of Li2 S composites and inhibits the polysulfide dissolution via the TMS bond, effectively addressing the drawbacks of Li2 S cathodes. In particular, Li2 S/W and Li2 S/Mo exhibit the highest ionic conductivity of solid-phase Li-ion conductors ever-reported: 5.44 × 10-2 and 3.62 × 10-2 S m-1 , respectively. On the other hand, integrating Co, Mn, and Zn turns Li2 S into a prelithiation agent, forming metal sulfides rather than S8 after the full charge. These interesting findings may shed light on the design of Li2 S-based cathode materials.