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

TL;DR

This study uses cryogenic electron microscopy to reveal a stable, multilayer nanostructure of the solid electrolyte interphase between lithium metal and LiPON, providing insights into its stability in all-solid-state batteries.

Contribution

It demonstrates the first detailed cryo-EM characterization of the Li/LiPON interface, uncovering a stable, multilayer SEI structure with specific elemental gradients and crystallites.

Findings

SEI is less than 80 nm thick with a multilayer mosaic structure.

The SEI contains no organic lithium compounds or lithium fluoride.

The structure is stable and free of reactive species, unlike in liquid electrolytes.

Abstract

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 nanostructures of SEIs were recently reported to be equally important to the chemistry of SEIs for stabilizing Li metal in liquid electrolyte. However, 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 Li metal. Characterizing such solid-solid interfaces is difficult due to the buried, highly reactive, and beam-sensitive nature of the constituents within. By employing cryogenic electron microscopy (cryo-EM), the interphase between Li metal and LiPON is successfully preserved and probed, revealing a multilayer mosaic SEI structure with concentration gradients of nitrogen and phosphorous, materializing as crystallites within an amorphous matrix. This unique SEI nanostructure is less than 80 nm and is shown 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 Li metal anode.