LAUSR

Encapsulation of lithium in the confined spaces within individual nanocapsules is intriguing and highly desirable for developing high-performance Li metal anodes. This work aims for a mechanistic understanding of Li encapsulation and its confined growth kinetics inside one-dimensional enclosed spaces. To achieve this, we employ amorphous carbon nanotubes as a model host using in situ transmission electron microscopy. The carbon shells have dual roles, providing geometric/mechanical constraints and electron/ion transport channels, which profoundly alter the Li growth patterns. Li growth/dissolution takes place via atom addition/removal at the free surfaces through Li+ diffusion along the shells in the electric field direction, resulting in the formation of unusual Li structures, such as poly-crystalline nanowires and free-standing two-dimensional ultrathin (1-2 nm) Li membranes. Such confined front-growth processes are dominated by Li {110} or {200} growing faces, distinct from the root growth of single-crystal Li dendrites outside the nanotubes. Controlled experiments show that high lithiophilicity and permeability, enabled by sufficient nitrogen/oxygen doping, is critical for the stable encapsulation of lithium inside carbonaceous nanocapsules. First-principles-based calculations reveal that N/O doping can reduce the diffusion barrier for Li+ penetration, and facilitate Li filling driven by energy minimization associated with the formation of low-energy Li/C interfaces. This article is protected by copyright. All rights reserved.