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Sodium (Na) metal batteries (SMBs) using Na anode are potential “beyond lithium” electrochemical technology for future energy storage applications. However, uncontrollable Na dendrite growth has plagued the application of SMBs. Understanding Na deposition mechanisms, particularly the early stage of Na deposition kinetics, is critical to enable the SMBs. In this context, we conducted in situ observations of the early stage of electrochemical Na deposition. We revealed an important electrochemical Ostwald ripening (EOR) phenomenon which dictated the early stage of Na deposition. Namely, small Na nanocrystals were nucleated randomly, which then grew. During growth, smaller Na nanocrystals were contained by bigger ones via EOR. We observed two types of EOR with one involving only electrochemical reaction driven by electrochemical potential difference between bigger and smaller nanocrystals; while the other being dominated by mass transport governed by surface energy minimization. The results provide new understanding to the Na deposition mechanism, which may be useful for the development of SMB for energy storage applications.
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