Regulating the electronic modulation configuration of MnxFeCoNiCu high entropy alloy for reliable sulfur redox kinetics

Abstract

Current research on sulfur redox catalysis primarily focuses on the adsorption and catalytic conversion of lithium polysulfides (LiPSs). However, it often neglecting the modulation of the catalysts' electronic structure, which includes charge transfer and orbital interactions that significantly affect adsorption and catalytic properties. In this work, multi-channel carbon nanotubes modified with high entropy alloy nanoparticles (MnxFeCoNiCu/MCCFs) are elaborately synthesized as hosts to reveal the relationship between the catalytic activity and surface electronic configuration for reliable sulfur electrochemistry. Combining density functional theory (DFT) calculations with detailed experimental investigations, we demonstrate that modulating the electron consumption center of this intrinsic electron transfer-replenishment mechanism, the surface charge distribution is reestablished, thereby improving the performance of multi-electron reactions. Achieving a balance between adsorption and desorption significantly enhance the catalytic efficiency for LiPSs conversion. Consequently, the as-prepared Mn1.00/MCCFs with an optimized electronic structure as sulfur host can deliver a high capacity of 938 mAh g−1, corresponding to an ultralow capacity decay of 0.013 % per cycle over 500 cycles at 1.0 C.