Single-atom catalysts based on C2N for sulfur cathodes in Na-S batteries: a first-principles study.

Abstract

Several major roadblocks, including the "shuttle effect" caused by the dissolved higher-order sodium polysulfides (NaPSs), extremely poor conductivity of sulfur cathodes, and sluggish conversion kinetics of charging-discharging reactions, have hindered the commercialization of sodium-sulfur batteries (NaSBs). In our study, representative C2N-based single-atom catalysts (SACs), TM@C2N (TM = Fe, Ni and V), are proposed to improve the comprehensive performance of NaSBs. Based on first-principles calculations, we first discuss in detail the anchoring behavior of all adsorption systems, TM@C2N/(S8 and NaPSs). The results indicate that compared to pristine C2N, TM@C2N substrates exhibit a stronger capability to capture S8/NaPSs clusters through physical/chemical binding, with V@C2N showing the most outstanding capability ranging from -2.37 to -5.03 eV. The density of states analysis reveals that metallic properties can be well maintained before and after adsorption of polysulfides. More importantly, TM@C2N configurations can greatly reduce the energy barriers of charging and discharging reactions, thereby accelerating the conversion efficiency of NaSBs. It is worth mentioning that V@C2N has lower charge-discharge energy barriers and Na ion migration rates, since the embedded TM atom weakens the strong binding of Na+ in the N6 cavity of C2N. The intrinsic mechanism analysis reveals that the interaction between the d orbitals of V and the p orbitals of S leads to the weakening of Na-S bonds, which can not only effectively inhibit the shuttle effect, but also promote the dissociation of Na2S. Overall, this work not only offers excellent catalytic materials, but also provides vital guidance for designing SACs in NaSBs.