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 1D enclosed spaces. To achieve this, amorphous carbon nanotubes are employed 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 2D 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/permeability, enabled by sufficient nitrogen/oxygen doping or pre-lithiation, 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.

Centre of Polymer and Carbon Materials Polish Academy of Sciences M Curie Sklodowskiej 34 Zabrze 41 819 Poland

College of Energy Soochow Institute for Energy and Materials InnovationS Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province Soochow University Suzhou 215006 P R China

Department of Materials Science and Engineering Southern University of Science and Technology Shenzhen 518055 China

Guangdong Provincial Key Laboratory of Computational Science and Material Design Southern University of Science and Technology Shenzhen 518055 China

Helmholtzstraße 20 01069 Dresden Germany

Institute of Environmental Technology VSB Technical University of Ostrava 17 Listopadu 15 Ostrava 708 33 Czech Republic

State Key Laboratory of Photocatalysis on Energy and Environment College of Chemistry Fuzhou University Fuzhou 350002 China

State Key Laboratory of Physical Chemistry of Solid Surfaces College of Materials College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 China

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