A Theoretical Raman Spectra Analysis of the Effect of the Li₂S and Li₃PS₄ Content on the Interface Formation Between...

In this study, we perform density functional theory (DFT) simulations to investigate the Raman spectra of the bulk and surface phases of β-Li₃PS₄ (LPS) and Li₂S, as well as their interfaces at varying compositional ratios. This analysis is relevant given the widespread application of these materials in Li-S solid-state batteries, where Li₂S functions not only as a cathode material but also as a protective layer for the lithium anode. Understanding the interfacial structure and how compositional variations influence its chemical and mechanical stability is therefore crucial. Our results demonstrate that the LPS/Li₂S interface remains stable regardless of the compositional ratio. However, when the content of both materials is low, the Raman-active vibrational mode associated with the [PS₄]^3- tetrahedral cluster dominates the interface spectrum, effectively obscuring the characteristic peaks of Li₂S and other interfacial features. Only when sufficient amounts of both LPS and Li₂S are present does the coupling between their vibrational modes become sufficiently pronounced to alter the Raman profile and reveal distinct interfacial fingerprints.