Interface Analysis of LiCl as a Protective Layer of Li1.3Al0.3Ti1.7(PO4)3 for Electrochemically Stabilized All-Solid-State Li-Metal Batteries

Regardless of the superiorities of Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP), such as stability against oxygen and moisture, high ionic conductivity, and low activation energy, its practical application in all-solid-state lithium metal batteries is still impeded by the formation of ionic-resistance interphase layers. Upon contact with Li metal, electron migration from Li to LATP causes the reduction of Ti⁴⁺ in LATP. As a result, an ionic-resistance layer will be formed at the interface between the two materials. Applying a buffer layer between them is a potential measure to mitigate this problem. In this study, we analyzed the potential role of LiCl to protect the LATP solid electrolyte through a first-principle study-based density functional theory (DFT) calculation. Density-of-states (DOS) analysis on the Li/LiCl heterostructure reveals the insulating roles of LiCl in preventing electron flow to LATP. The insulating properties begin at depths of 4.3 and 5.0 Å for Li (001)/LiCl (111) and Li (001)/LiCl (001) heterostructures, respectively. These results indicate that LiCl (111) is highly potential to be applied as a protecting layer on LATP to avoid the formation of ionic resistance interphase caused by electron transfer from the Li metal anode.