Unconventional catalytic kinetics of dual field regulated pyrochlore-type high-entropy ceramics towards the Li2S4 intermediate

Abstract

The electrocatalytic performance of high-entropy ceramics has been recognized as a pivotal prerequisite to realizing ultra-durability for lithium–sulfur batteries. However, the dynamics of accurately capturing Li₂S₄ remains poorly understood, and thus a comprehensive understanding of the mechanism between dynamic control factors and electrocatalytic performance remains largely unexplored. In this study, we visually present the Li₂S₄ electrocatalytic process and accurately identify that high-entropy engineering of rare earth sites leads to positive modifications in crystal field splitting energy and electronegativity. In conjunction with theoretical analysis, we demonstrate that the adsorption energy of Li₂S₄ is optimized by the electronic structure and covalency under dual-field (electric field and crystal field) regulation, leading to efficient electrocatalytic performance. These findings have enabled us to develop an ultra-durable ceramic electrocatalyst (La_0.15Nd_0.15Sm_0.40Eu_0.15Gd_0.15)₂Zr₂O₇ as a sulfur cathode (HEZO-S) with a lifespan exceeding 10 000 hours. This fundamental understanding of the intrinsic relationship provides a feasible high-entropy strategy for the design of advanced catalysts for lithium–sulfur batteries.