Microstructural Evolution of Tin Nanoparticles during In Situ Sodium Insertion and Extraction

The microstructural changes and phase transformations of tin nanoparticles during electrochemical sodiation were studied with a nanosized sodium ion battery using in situ transmission electron microscopy. It was found that the first sodiation process occurred in two steps; that is, the crystalline Sn nanoparticles were initially sodiated via a two-phase mechanism with a migrating phase boundary to form a Na-poor, amorphous Na_<i>x</i>Sn alloy (<i>x</i> ∼ 0.5), which was further sodiated to several Na-rich amorphous phases and finally to the crystallized Na₁₅Sn₄ (<i>x</i> = 3.75) via a single-phase mechanism. The volumetric expansion was about 60% in the first step and 420% after the second step. However, despite the huge expansion, cracking or fracture was not observed, which is attributed to the second step of the single-phase sodiation that accommodates large portion of the sodiation-induced stress over the entire particle. Excellent cyclability was also observed during the reversible sodiation/desodiation cycles, showing great potential of Sn nanoparticles as a robust electrode material for rechargeable batteries