Lithium-sulfur (Li-S) batteries are considered to be the most promising next-generation high energy density storage systems. However, they still face challenges, such as the shuttle effect of lithium polysulfides (LiPSs) and slow sulfur oxidation-reduction kinetics. In this work, heteroatom (P and S)-doped edge-type Fe single-atom catalytic materials (FeN4S2/P2-DG) for sulfur reduction reactions (SRRs) and sulfur oxidation reactions in Li-S batteries are investigated using density functional theory calculations. Theoretical analysis suggests that compared to planar Fe-N4 fragments, the charge density accumulation around edge-type Fe-N4 fragments in S- or P-doped structures is higher. Furthermore, the doping of P or S reduces the electron filling state of Fe_3d orbitals, leading to a decrease in electron occupancy in the antibonding orbitals, which is beneficial for the formation of d-p orbital hybridization, strengthening the anchoring strength of FeN4P2/S2-DG for S8/LiPSs. Specifically, FeN4P1,2-DG showed the lowest free energy barriers (0.57 eV) for SRRs and reduced the dissociation energy barrier of Li2S from 1.85 eV (for planar FeN4-G) to 0.96 eV during the charging process, demonstrating excellent catalytic ability. Additionally, this theoretical study provides further insights into the application of graphene-supported single-atom catalyst materials as anchoring materials for Li-S batteries.
Keywords: density functional theory; d–p orbital hybridization; edge-type single-atom catalyst; electron redistribution; lithium−sulfur battery.