A Dendrite‐Free Lithium‐Metal Anode Enabled by Designed Ultrathin MgF₂ Nanosheets Encapsulated Inside Nitrogen‐Doped Graphene‐Like Hollow Nanospheres

Abstract Uncontrolled lithium dendrite growth and dramatic volume change during cycling have long been severely impeding the practical applications of Li metal as the ultimate anode. In this work, ultrathin MgF₂ nanosheets encapsulated inside nitrogen‐doped graphene‐like hollow nanospheres (MgF₂ NSs@NGHSs) are ingeniously fabricated to address these problems by a perfect combination of atomic layer deposition and chemical vapor deposition. The uniform and continuous Li–Mg solid‐solution inner layer formed by the MgF₂ nanosheets can reduce the nucleation overpotential and induce selective deposition of Li into the cavities of the NGHSs. Furthermore, the Li deposition behavior and mechanism of the hybrid host are comprehensively explored by in situ optical microscopy at the macroscopic level, in situ transmission electron microscopy at the microscopic level, and theoretical calculations at the atomic level, respectively. Benefiting from a synergistic modulation strategy of nanosheet seed‐induced nucleation and Li‐confined growth, the designed composite demonstrates an endurance of 590 cycles for asymmetric cells and a lifespan over 1330 h for corresponding symmetric cells. When applied in LiFePO₄ full cells, it provides a reversible capacity of 90.6 mAh g⁻¹ after 1000 cycles at 1 C.