Interfacial Electron Redistribution on Lattice‐Matching NiS2/NiSe2 Homologous Heterocages with Dual‐Phase Synergy to Tune the Formation Routes of Li2O2

Abstract Li–O2 batteries (LOBs) exhibit ultrahigh theoretical energy density, but sluggish reaction kinetics and adverse parasitic reactions seriously hinder their further development. It is thus urgent to exploit cost‐effective and durable electrocatalysts to perfect LOBs performance and promote their practical application. In this work, lattice‐matching composites are synthesized based on homologous heterostructure (HHS) with hollow nanocage‐like architecture. As expected, the unique architecture with built‐in electric fields of NiS2/NiSe2 HHS enables the rapid transfer of electron/ions, favorable electrolyte permeation on the cathode surfaces, and provides sufficient active sites for oxygen evolution reaction and oxygen reduction reaction. Moreover, the constructs NiS2/NiSe2 HHS can evidently catalyze the formation of dispersed platelet‐shape and fluffy film‐like Li2O2 discharge products via the surface/solution routes due to the greatly reduced adsorption energy of the LiO2 intermediates on the built‐in electric fields, while the NiS2 and NiSe2 counterparts induce the formation of Li2O2 films by the surface path, limiting its electrocatalytic activities. These results suggest that lattice‐matching HHS engineering of cathode catalysts can be an effective approach to tuning the Li2O2 formation, which holds attractive and great application prospects in the development of high‐performance LOBs.