Theoretical insights into single-atom catalysts for improved charging and discharging kinetics of Na-S and Na-Se...

Dissolution of poly-sulfide/selenides (p-S/Ses) intermediates into electrolytes, commonly known as the shuttle effect, has posed a significant challenge in the development of more efficient and reliable Na-S/Se batteries. Single-atom catalysts (SACs) play a crucial role in mitigating the shuttling of Na-pS/Ses and in promoting Na₂S/Se redox processes at the cathode. In this work, single transition metal atoms Co, Fe, Ir, Ni, Pd, Pt, and Rh supported in nitrogen-deficient graphitic carbon nitride (rg-C₃N₄) are investigated to explore the charging and discharging kinetics of Na-S and Na-Se batteries using Density Functional Theory calculations. We find that SAs adsorbed on reduced g-C₃N₄ monolayers are substantially more effective in trapping higher-order Na₂X than pristine g-C₃N₄ surfaces. Moreover, our ab initio molecular dynamics calculations indicate that the structure of X₈ (X = S, Se) remains almost intact when adsorbed on Fe, Co, Ir, Ni, Pt, and Rh SACs, suggesting that there is no significant S or Se poisoning in these cases. Additionally, SACs reduce the free energies of the rate-determining step during discharge and present a lower decomposition barrier of Na₂X during charging of Na-X electrode. The underlying mechanisms behind this fast kinetics are thoroughly examined using charge transfer, bonding strength, and d-band center analysis. Our work demonstrates an effective strategy for designing single-atom catalysts and offers solutions to the performance constraints caused by the shuttle effect in sodium-sulfur and sodium-selenium batteries.