Controllable Regulation of the Oxygen Redox Process in Lithium–Oxygen Batteries by High-Configuration-Entropy Spinel with an Asymmetric Octahedral Structure

Designing bifunctional electrocatalysts to boost oxygen redox reactions is critical for high-performance lithium-oxygen batteries (LOBs). In this work, high-entropy spinel (Co_0.2Mn_0.2Ni_0.2Fe_0.2Cr_0.2)₃O₄ (HEOS) is fabricated by modulating the internal configuration entropy of spinel and studied as the oxygen electrode catalyst in LOBs. Under the high-entropy atomic environment, the Co-O octahedron in spinel undergoes asymmetric deformation, and the reconfiguration of the electron structure around the Co sites leads to the upward shift of the d-orbital centers of the Co sites toward the Fermi level, which is conducive to the strong adsorption of redox intermediate LiO₂ on the surface of the HEOS, ultimately forming a layer of a highly dispersed Li₂O₂ thin film. Thin-film Li₂O₂ is beneficial for ion diffusion and electron transfer at the electrode-electrolyte interface, which makes the product easy to decompose during the charge process, ultimately accelerating the kinetics of oxygen redox reactions in LOBs. Based on the above advantages, HEOS-based LOBs deliver high discharge/charge capacity (12.61/11.72 mAh cm^-2) and excellent cyclability (424 cycles). This work broadens the way for the design of cathode catalysts to improve oxygen redox kinetics in LOBs.