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

Abstract Li–O 2 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 NiS 2 /NiSe 2 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 NiS 2 /NiSe 2 HHS can evidently catalyze the formation of dispersed platelet‐shape and fluffy film‐like Li 2 O 2 discharge products via the surface/solution routes due to the greatly reduced adsorption energy of the LiO 2 intermediates on the built‐in electric fields, while the NiS 2 and NiSe 2 counterparts induce the formation of Li 2 O 2 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 Li 2 O 2 formation, which holds attractive and great application prospects in the development of high‐performance LOBs.