Effectively Modulating Oxygen Vacancies in Flower-Like δ-MnO2 Nanostructures for Large Capacity and High-Rate Zinc-Ion Storage

Highlights The flower-like δ -MnO 2 nanostructures with controlled oxygen vacancies as an extraordinary ZIBs cathode are innovatively developed. The cathode can present large capacity and high-rate zinc-ion storage. DFT analysis substantially unveils the effects of various vacancy concentrations on their electrochemical performances. In recent years, manganese-based oxides as an advanced class of cathode materials for zinc-ion batteries (ZIBs) have attracted a great deal of attentions from numerous researchers. However, their slow reaction kinetics, limited active sites and poor electrical conductivity inevitably give rise to the severe performance degradation. To solve these problems, herein, we introduce abundant oxygen vacancies into the flower-like δ -MnO 2 nanostructure and effectively modulate the vacancy defects to reach the optimal level ( δ -MnO 2− x −2.0). The smart design intrinsically tunes the electronic structure, guarantees ion chemisorption–desorption equilibrium and increases the electroactive sites, which not only effectively accelerates charge transfer rate during reaction processes, but also endows more redox reactions, as verified by first-principle calculations. These merits can help the fabricated δ -MnO 2− x −2.0 cathode to present a large specific capacity of 551.8 mAh g −1 at 0.5 A g −1 , high-rate capability of 262.2 mAh g −1 at 10 A g −1 and an excellent cycle lifespan (83% of capacity retention after 1500 cycles), which is far superior to those of the other metal compound cathodes. In addition, the charge/discharge mechanism of the δ -MnO 2− x −2.0 cathode has also been elaborated through ex situ techniques. This work opens up a new pathway for constructing the next-generation high-performance ZIBs cathode materials.