Rationally Designed Mn2O3–ZnMn2O4 Hollow Heterostructures from Metal–Organic Frameworks for Stable Zn‐Ion Storage

Abstract Mn‐based oxides have sparked extensive scientific interest for aqueous Zn‐ion batteries due to the rich abundance, plentiful oxidation states, and high output voltage. However, the further development of Mn‐based oxides is severely hindered by the rapid capacity decay during cycling. Herein, a two‐step metal–organic framework (MOF)‐engaged templating strategy has been developed to rationally synthesize heterostructured Mn 2 O 3 –ZnMn 2 O 4 hollow octahedrons (MO–ZMO HOs) for stable zinc ion storage. The distinctive composition and hollow heterostructure endow MO–ZMO HOs with abundant active sites, enhanced electric conductivity, and superior structural stability. By virtue of these advantages, the MO–ZMO HOs electrode shows high reversible capacity, impressive rate performance, and outstanding electrochemical stability. Furthermore, ex situ characterizations reveal that the charge storage of MO–ZMO HOs mainly originates from the highly reversible Zn 2+ insertion/extraction reactions.