Unraveling the multilayer solid-electrolyte interphase in lithium batteries through depth-sensitive plasmon-enhanced Raman spectroscopy: A theoretical and experimental study

The solid-electrolyte interphase (SEI) plays a crucial role in determining the lithium deposition/dissolution behaviors, thus influencing the reversible operation of Li metal batteries renowned for their ultrahigh specific capacity. Recently, we developed a depth-sensitive plasmon-enhanced Raman spectroscopy (DS-PERS) method enabling the in situ and nondestructive characterization of the nanostructure and chemistry of SEI through synergistic plasmonic structures. However, a lack of comprehensive elucidation of the enhancement mechanisms has impeded a detailed understanding of the depth-resolved signal contributions. In this study, we integrate theoretical computations with experimental methodologies to systematically unravel the working principles of the synergistic plasmonic structures, demonstrating that hot spots can effectively detect Raman signals at key locations across various stages of SEI layer evolution. Following Li deposition, the hot spots transfer from the Cu interfaces to the Li interfaces. With the thickening of the deposited Li, the localized surface plasmon resonance of Cu is gradually shielded, leading to the disappearance of hot spots originated from Li-Li coupling. Subsequently, we propose the utilization of Cu@Li-multilayer shell-isolated nanoparticles to compensate and introduce new hot spots, thereby enhancing the depth sensitivity. Our work provides theoretical insights essential for achieving precise depth-resolved PERS characterization.