Tuning Redox Behavior of Sulfur Cathodes Via Ternary-Coordinated Single Fe Atom in Lithium-Sulfur Batteries

Modulating the coordination configuration of single Fe atom has been an efficient strategy to strengthen the redox dynamics for lithium-sulfur batteries (LSBs) but remains challenging. Herein, the single Fe atom is functioned with nitrogen and carbon atoms in the first shell, and simultaneously, oxidized sulfur (─SOx) in the second shell, which presents a lower antibonding state and well address the redox activity of sulfur cathodes. In the ternary-coordinated single Fe atom catalyst (FeN₂C₂-SOx-NC), the binary structure of FeN₂C₂ provides a lower Fe-S bonding strength and d-p orbital hybridization, which obviously optimizes the adsorption and desorption behavior of sulfur species during the reduction and oxidation reaction processes. Simultaneously, the ─SOx redistributes the electron density of the coordinating nitrogen atoms, which possesses high electron-withdrawing ability and develops electrocatalytic activity. As a result, the sulfur cathodes with FeN₂C₂-SOx-NC present an excellent high-rate cyclic performance, accompanied by a capacity decay rate of 0.08% per cycle for 500 cycles at 4.0 C. This study provides new insights for optimizing the redox dynamics of sulfur cathodes in LSBs at the atomic level.