Nitride MXenes as sulfur hosts for thermodynamic and kinetic suppression of polysulfide shuttling: a computational study

The practical applications of lithium-sulfur (Li-S) batteries are greatly hindered by the poor conductivity of sulfur, the shuttling of lithium polysulfides (LiPSs), and the sluggish kinetics in the charge-discharge process. In order to solve these problems, here we propose the surface-functionalized V2N MXenes as the host materials to improve the electrochemical performance of Li-S batteries. Based on the density functional theory (DFT) calculations, we found that both the bare and functionalized V2NT2 (T = O, F, OH, and S) exhibit metallicity, and three of them (V2NO2, V2NF2, and V2NS2) possess moderate LiPS adsorption strength, which thermodynamically benefits the suppression of the dissolution and shuttling of LiPSs. Besides, V2NS2 shows the lowest Gibbs free energy barrier for the sulfur reduction reaction (0.49 eV) during discharge, which kinetically suppresses the dissolution and shuttling of LiPSs by expediting the decomposition process from soluble LiPSs to insoluble ones. Moreover, surface functionalized V2NT2 also exhibits outstanding catalytic ability for Li2S decomposition during charge, which decreases the energy barrier from 3.64 eV (bare V2N) to 1.55 (V2NO2) and 1.19 eV (V2NS2), and increases the charging kinetics. Based on these results, V2NS2 monolayers are suggested as promising host materials for S cathodes due to the fast charge/discharge kinetics and effective suppression of LiPS shuttling. This theoretical study provides further insight into the application of nitride MXenes and other two-dimensional materials as conductive anchoring materials for Li-S batteries.

Automated summary

The surface-functionalized V2N MXenes are proposed as host materials to enhance the electrochemical performance of Li-S batteries, improving the kinetics and suppressing the shuttling of lithium polysulfides. Theoretical calculations show that V2NS2 exhibits the lowest energy barrier for sulfur reduction reaction during discharge, while also displaying outstanding catalytic ability for Li2S decomposition during charge, suggesting its potential as a promising host material for S cathodes.