Synthesis of hierarchical porous δ-MnO2 nanoboxes as an efficient catalyst for rechargeable Li–O2 batteries

Abstract

A rechargeable lithium–oxygen (Li–O₂) battery with a remarkably high theoretical energy storage capacity has attracted enormous research attention. However, the poor oxygen reduction and oxygen evolution reaction (ORR and OER) activities in discharge and charge processes cause low energy efficiency, poor electrolyte stability and short cycle life. This requires the development of efficient cathode catalysts to dramatically improve the Li–O₂ battery performances. MnO₂-based materials are recognized as efficient and low-cost catalysts for a Li–O₂ battery cathode. Here, we report a controllable approach to synthesize hierarchical porous δ-MnO₂ nanoboxes by using Prussian blue analogues as the precursors. The obtained products possess hierarchical pore size and an extremely large surface area (249.3 m² g⁻¹), which would favour oxygen transportation and provide more catalytically active sites to promote ORR and OER as the Li–O₂ battery cathode. The battery shows enhanced discharge capacity (4368 mA h g⁻¹@0.08 mA cm⁻²), reduced overpotential (270 mV), improved rate performance and excellent cycle stability (248 cycles@500 mA h g⁻¹ and 112 cycles@1000 mA h g⁻¹), in comparison with the battery with a VX-72 carbon cathode. The superb performance of the hierarchical porous δ-MnO₂ nanoboxes, together with a convenient fabrication method, presents an alternative to develop advanced cathode catalysts for the Li–O₂ battery.