Tailoring the p‐Band Center of NS Pair for Accelerating High‐Performance Lithium–Oxygen Battery

The local coordination environment of catalytical moieties directly determines the performance of electrochemical energy storage and conversion devices, such as Li–O2 batteries (LOBs) cathode. However, understanding how the coordinative structure affects the performance, especially for non‐metal system, is still insufficient. Herein, a strategy that introduces S‐anion to tailor the electronic structure of nitrogen–carbon catalyst (SNC) is proposed to improve the LOBs performance. This study unveils that the introduced S‐anion effectively manipulates the p‐band center of pyridinic‐N moiety, substantially reducing the battery overpotential by accelerating the generation and decomposition of intermediate products Li1–3O4. The lower adsorption energy of discharging product Li2O2 on NS pair accounts for the long‐term cyclic stability by exposing the high active area under operation condition. This work demonstrates an encouraging strategy to enhance LOBs performance by modulating the p‐band center on non‐metal active sites. Regulating the p‐band center of pyridinic‐N moiety by forming NS pair is an efficient strategy as the Li‐O2 batteries (LOBs) cathode. The NS pair not only substantially reduces the energy barrier of intermediated species to promote electrochemical activity, but also effectively decreases the Li2O2 adsorption to keep exposed condition, sustaining active sites available to boost LOBs kinetics.