Controlled Experiments and Optimized Theory of Absorption Spectra of Li Metal and Salts

Investigation of Li metal and ionic compounds through experimental and theoretical spectroscopy has been of tremendous interest due to their prospective applications in Li–metal and Li-ion batteries. Li K-edge soft X-ray absorption spectroscopy (sXAS) provides the most direct spectroscopic characterization; unfortunately, due to the low core-level energy and the highly reactive surface, Li–K sXAS of Li metal has been extremely challenging, as evidenced by many controversial reports. Here, through controlled and ultra-high energy resolution experiments of two kinds of in situ prepared samples, we report the intrinsic Li–K sXAS of Li–metal that displays a prominent leading peak that has not been revealed before. Furthermore, theoretical simulations show that, due to the low number of valence electrons in Li, the Li–K sXAS is strongly affected by the response of the valence electrons to the core hole. We successfully reproduce the Li–K sXAS by state-of-the-art calculations with considerations of a number of relevant parameters such as temperature, energy resolution, and, especially, contributions from transitions which are forbidden in the single-particle treatment. Such a comparative experimental and theoretical investigation is further extended to a series of Li ionic compounds, which highlight the importance of considering the total and single-particle energies for obtaining an accurate alignment of the spectra. Our work provides the first reliable Li–K sXAS of the Li metal surface with advanced theoretical calculations. The experimental and theoretical results provide a critical benchmark for studying Li chemistry in both metallic and ionic states.