Hierarchical Porous Carbon Spheres for High‐Performance Na–O₂ Batteries

Abstract As a new family member of room‐temperature aprotic metal–O₂ batteries, Na–O₂ batteries, are attracting growing attention because of their relatively high theoretical specific energy and particularly their uncompromised round‐trip efficiency. Here, a hierarchical porous carbon sphere (PCS) electrode that has outstanding properties to realize Na–O₂ batteries with excellent electrochemical performances is reported. The controlled porosity of the PCS electrode, with macropores formed between PCSs and nanopores inside each PCS, enables effective formation/decomposition of NaO₂ by facilitating the electrolyte impregnation and oxygen diffusion to the inner part of the oxygen electrode. In addition, the discharge product of NaO₂ is deposited on the surface of individual PCSs with an unusual conformal film‐like morphology, which can be more easily decomposed than the commonly observed microsized NaO₂ cubes in Na–O₂ batteries. A combination of coulometry, X‐ray diffraction, and in situ differential electrochemical mass spectrometry provides compelling evidence that the operation of the PCS‐based Na–O₂ battery is underpinned by the formation and decomposition of NaO₂. This work demonstrates that employing nanostructured carbon materials to control the porosity, pore‐size distribution of the oxygen electrodes, and the morphology of the discharged NaO₂ is a promising strategy to develop high‐performance Na–O₂ batteries.