Dynamic Behavior of Spatially Confined Sn Clusters and its Application in Highly Efficient Sodium Storage with High Initial Coulombic Efficiency.

Advanced battery electrodes require a cautious design of microscale particles with built-in nanoscale features to exploit the advantages of both micro- and nano-particles relative to their performance attributes. Herein, we reveal the dynamic behavior of nanosized Sn clusters and their host pores in carbon nanofibers (CNFs) during sodiation and desodiation using a state-of-the-art 3D electron microscopic reconstruction technique. For the first time, the anomalous expansion of Sn clusters after desodiation is observed owing to the aggregation of clusters/single atoms. Pore connectivity is retained despite the anomalous expansion, suggesting inhibition of solid electrolyte interface formation in the sub-2-nm pores. Taking advantage of the built-in nanoconfinement feature, the CNF film with nanometer-sized interconnected pores hosting Sn clusters (∼2 nm) enables high utilization (95% at a high rate of 1 A g -1 ) of Sn active sites while maintaining an improved initial Coulombic efficiency of 87%. Our findings provide insights into electrochemical reactions in a confined space and a guiding principle in electrode design for battery applications. This article is protected by copyright. All rights reserved.