Unveiling the Stable Nature of the Solid Electrolyte Interphase between Lithium Metal and LiPON via Cryogenic Electron Microscopy

The solid electrolyte interphase (SEI) is regarded as the most complex but the least understood constituent in secondary batteries using liquid and solid electrolytes. The dearth of such knowledge in all-solid-state battery (ASSB) has hindered a complete understanding of how certain solid-state electrolytes, such as LiPON, manifest exemplary stability against lithium metal. By employing cryogenic electron microscopy (cryo-EM), the interphase between lithium metal and LiPON is successfully preserved and probed, revealing a multilayer-mosaic SEI structure with concentration gradients of nitrogen and phosphorus, materializing as crystallites within an amorphous matrix. This unique SEI nanostructure is less than 80 nm and is stable and free of any organic lithium-containing species or lithium fluoride components, in contrast to SEIs often found in state-of-the-art organic liquid electrolytes. Our findings reveal insights on the nanostructures and chemistry of such SEIs as a key component in lithium metal batteries to stabilize lithium metal anode.