Cryo‐Electron Microscopy Reveals Na Infiltration into Separator Pore Free‐Volume as a Degradation Mechanism in Na Anode:Liquid Electrolyte Electrochemical Cells

Abstract Batteries utilizing a sodium (Na) metal anode with a liquid electrolyte are promising for affordable large‐scale energy storage. However, a deep understanding of the intrinsic degradation mechanisms is limited by challenges in accessing the buried interfaces. Here, cryogenic electron microscopy of intact electrode:separator:electrode stacks is performed and degradation and failure of symmetric Na||Na coin cells occurs through the infiltration of Na metal through the pores of the separator rather than by mechanical puncturing by dendrites is revealed. It is shown the interior structure of the cell (electrode:separator:electrode) must be preserved and deconstructing the cell into different layers for characterization results in artifacts. In intact cell stacks, minimal liquid is found between the electrodes and separator, leading to intimate electrode:separator interfaces. After electrochemical cycling, Na infiltrates into the pore free‐volume, growing through the separator to create electrical shorts and degradation. The Na infiltration occurs at interfacial regions devoid of solid‐electrolyte interphase (SEI), revealing SEI plays an important role in preventing Na from growing into the separator by being a physical barrier that the plated Na cannot penetrate. These results shed new light on the fundamental failure mechanisms in Na batteries and demonstrate the importance of preserving the cell structure and buried interfaces.