Dynamic Molecular Investigation of the Solid-Electrolyte Interphase of an Anode-Free Lithium Metal Battery Using In Situ Liquid SIMS and Cryo-TEM

We use in situ liquid secondary ion mass spectroscopy, cryogenic transmission electron microscopy, and density functional theory calculation to delineate the molecular process in the formation of the solid-electrolyte interphase (SEI) layer under the dynamic operating conditions. We discover that the onset potential for SEI layer formation and the thickness of the SEI show dependence on the solvation shell structure. On a Cu film anode, the SEI is noticed to start to form at around 2.0 V (nominal cell voltage) with a final thickness of about 40-50 nm in the 1.0 M LiPF6/EC-DMC electrolyte, while for the case of 1.0 M LiFSI/DME, the SEI starts to form at around 1.5 V with a final thickness of about 20 nm. Our observations clearly indicate the inner and outer SEI layer formation and dissipation upon charging and discharging, implying a continued evolution of electrolyte structure with extended cycling.

Automated summary

We have used experimental and computational methods to study the molecular process of solid-electrolyte interphase (SEI) layer formation under practical conditions. Our findings suggest that the solvation shell structure in the electrolyte has an impact on the mechanism and thickness of the SEI layer.