DFT‐Informed Electrochemical Engineering of Nanoalloy Intermediates for Ultra‐Stable Lithium Storage

ABSTRACT Molybdenum disulfide (MoS 2 ) is emerging as a potential candidate for lithium‐ion storage, but usually suffers from poor cyclic stability due to the shuttle effect of polysulfides resulted by irreversible conversion reaction. The most essentially limiting factor lies in the intrinsic sulfidation resistance of Mo. Herein, we report a strategy of creating nanoalloy intermediates via electrochemical cycling to overcome the intrinsic sulfidation resistance of Mo, realizing stable MoS 2 anodes. By using work function as the pivotal descriptor, DFT‐informed screening was utilized to discover the optimal dopants. Both simulation and experimental investigations reveal that the cobalt (Co) dopants can induce the formation of CoMo nanoalloy intermediates, which remarkably enhance Li 2 S reconversion, effectively mitigating capacity fading. As expected, the Co single atoms doped MoS 2 electrode (denoted as Co SAs‐MoS 2 ) demonstrates high reversibility of conversion reaction with capacity‐retention of 93.3% at a current density of 1 A g −1 after 3500 cycles, which is superior to the vast majority of previously reported MoS 2 ‐based anodes. This work provides guidelines for the rational design of high‐performance conversion‐type anodes.