Coupling MoSe2 with Non‐Stoichiometry Ni0.85Se in Carbon Hollow Nanoflowers for Efficient Electrocatalytic Synergistic Effect on Li‐O2 Batteries

Li‐O2 batteries could deliver ultra‐high theoretical energy density compared to current Li‐ion batteries counterpart. The slow cathode reaction kinetics in Li‐O2 batteries, however, limits their electrocatalytic performance. To this end, MoSe2 and Ni0.85Se nanoflakes were decorated in carbon hollow nanoflowers, which were served as the cathode catalysts for Li‐O2 batteries. The hexagonal Ni0.85Se and MoSe2 show good structural compatibility with the same space group, resulting in a stable heterogeneous structure. The synergistic interaction of the unsaturated atoms and the built‐in electric fields on the heterogeneous structure exposes abundant catalytically active sites, accelerating ion and charge transport and imparting superior electrochemical activity, including high specific capacities and stable cycling performance. More importantly, the lattice distances of the Ni0.85Se (101) plane and MoSe2 (100) plane at the heterogeneous interfaces are highly matched to that of Li2O2 (100) plane, facilitating epitaxial growth of Li2O2, as well as the formation and decomposition of discharge products during the cycles. This strategy of employing nonstoichiometric compounds to build heterojunctions and improve Li‐O2 battery performance is expected to be applied to other energy storage or conversion systems. Hollow spherical MoSe2‐Ni0.85Se@C heterostructures were synthesized by the simple hydrothermal and calcination method, which can be used as efficient cathode catalysts for Li‐O2 batteries. The coupled MoSe2 and non‐stoichiometry Ni0.85Se in porous carbon substrate introduced additional active sites and built‐in electric fields to synergistically improve the electrochemical activities, and the highly matched lattices enabled epitaxial growth of Li2O2 to effectively improve the cycling stability.