The Impact of Microstructure on Filament Growth at the Sodium Metal Anode in All‐Solid‐State Sodium Batteries

In recent years, all‐solid‐state batteries (ASSBs) with metal anodes have witnessed significant developments due to their high energy and power density as well as their excellent safety record. While intergranular dendritic lithium growth in inorganic solid electrolytes (SEs) has been extensively studied for lithium ASSBs, comparable knowledge is missing for sodium‐based ASSBs. Therefore, polycrystalline Na‐β″‐alumina is employed as a SE model material to investigate the microstructural influence on sodium filament growth during deposition of sodium metal at the anode. The research focuses on the relationship between the microstructure, in particular grain boundary (GB) type and orientation, sodium filament growth, and sodium ion transport, utilizing in situ transmission electron microscopy (TEM) measurements in combination with crystal orientation analysis. The effect of the anisotropic sodium ion transport at/across GBs depending on the orientation of the sodium ion transport planes and the applied electric field on the current distribution and the position of sodium filament growth is explored. The in situ TEM analysis is validated by large field of view post‐mortem secondary ion mass spectrometer (SIMS) analysis, in which sodium filament growth within voids and along grain boundaries is observed, contributing to the sodium network formation potentially leading to failure of batteries. The critical role of anisotropic ion transport in solid electrolytes ! Knowledge of the intergranular dendritic growth of sodium in inorganic solid electrolytes is still lacking, especially the effect of the anisotropic ion transport due to the microstructure. It can lead to filament growth and blockade of ion transport at/across specific grain boundaries.