Single-Atom Tailored Hierarchical Transition Metal Oxide Nanocages for Efficient Lithium Storage

Mitigating the mechanical degradation and enhancing the ionic/electronic conductivity are critical but challengeable issues toward improving electrochemical performance of conversion-type anodes in rechargeable batteries. Herein, these challenges are addressed by constructing interconnected 3D hierarchically porous structure synergistic with Nb single atom modulation within a Co₃O₄ nanocage (3DH-Co₃O₄@Nb). Such a hierarchical-structure nanocage affords several fantastic merits such as rapid ion migration and enough inner space for alleviating volume variation induced by intragrain stress and optimized stability of the solid-electrolyte interface. Particularly, experimental studies in combination with theoretical analysis verify that the introduction of Nb into the Co₃O₄ lattice not only improves the electron conductivity, but also accelerates the surface/near-surface reactions defined as pesudocapacitance behavior. Dynamic behavior reveals that the ensemble design shows huge potential for fast and large lithium storage. These features endow 3DH-Co₃O₄@Nb with remarkable battery performance, delivering ≈740 mA h g⁻¹ after ultra-long cycling of 1000 times under a high current density of 5 A g⁻¹. Importantly, the assembled 3DH-Co₃O₄@Nb//LiCoO₂ pouch cell also presents a long-lived cycle performance with only ≈0.059% capacity decay per cycle, inspiring the design of electrode materials from both the nanostructure and atomic level toward practical applications.