Demystifying Activity Origin of M–N–C Single‐Atomic Mediators Toward Expedited Rate‐Determining Step in Li–S Electrochemistry

Sluggish sulfur reduction reaction (SRR) kinetics remains a formidable challenge in Li–S electrochemistry. In this sense, the rational design of single‐atom species has become a burgeoning practice to expedite sulfur redox, where the underlying catalytic mechanism otherwise remains elusive. Herein, a class of metal single‐atom modified porous carbon nanofiber films (MSA PCNFs, M = Fe, Co, or Ni), fabricated via a generic synthetic strategy, as mediators to boost SRR kinetics is reported. Throughout electrokinetic measurement and operando instrumental probing, NiSA PCNF is evidenced to harness the catalytic superiority toward the rate‐determining step (i.e., liquid–solid conversion) of the SRR process. Density functional theory (DFT) simulations further reveal that the catalytic features of M–N–C moieties in catalyzing the Li2S precipitation rely heavily upon the coordination environments of adjacent carbon atoms and d‐orbital configurations of metal centers. In response, the thus‐derived S/NiSA PCNF cathode realizes an encouraging areal capacity of 14.12 mAh cm−2 under elevated sulfur loading (10.2 mg cm−2) and lean electrolyte usage (E/S ratio ≈ 5.5 μL mg−1). This work offers insight into the identification of exact catalytic moieties for different transition metal M–N–C single‐atom SRR mediators, showcasing a meaningful guidance and potential impact on Li–S catalysis.