Accelerating Sulfur Redox Kinetics by Electronic Modulation and Drifting Effects of Pre‐Lithiation Electrocatalysts

Abstract Efficient catalyst design is crucial for addressing the sluggish multi‐step sulfur redox reaction (SRR) in lithium‐sulfur batteries (LiSBs), which are among the promising candidates for the next‐generation high‐energy‐density storage systems. However, the limited understanding of the underlying catalytic kinetic mechanisms and the lack of precise control over catalyst structures pose challenges in designing highly efficient catalysts, which hinder the LiSBs’ practical application. Here, drawing inspiration from the theoretical calculations, the concept of precisely controlled pre‐lithiation SRR electrocatalysts is proposed. The dual roles of channel and surface lithium in pre‐lithiated 1T’‐MoS₂ are revealed, referred to as the “electronic modulation effect” and “drifting effect”, respectively, both of which contribute to accelerating the SRR kinetics. As a result, the thus‐designed 1T’‐Li_xMoS₂/CS cathode obtained by epitaxial growth of pre‐lithiated 1T’‐MoS₂ on cubic Co₉S₈ exhibits impressive performance with a high initial specific capacity of 1049.8 mAh g⁻¹, excellent rate‐capability, and remarkable long‐term cycling stability with a decay rate of only 0.019% per cycle over 1000 cycles at 3 C. This work highlights the importance of precise control in pre‐lithiation parameters and the synergistic effects of channel and surface lithium, providing new valuable insights into the design and optimization of SRR electrocatalysts for high‐performance LiSBs.