Unconventional Catalytic Kinetics of Dual Field Regulated Pyrochlore-type High-entropy Ceramics towards Li2S4 Intermediate

Abstract

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, 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 (La0.15Nd0.15Sm0.4Eu0.15Gd0.15)2Zr2O7, as sulfur cathode (HEZO-S) with a lifespan exceeding 10000 hours. This fundamental understanding of the intrinsic relationship provides a feasible high-entropy strategy for the design of advanced catalysts for lithium-sulfur batteries.