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

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 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.