Fingerprinting mean composition of lithium polysulfide standard solutions by applying high energy resolution fluorescence detected X-ray Absorption Spectroscopy

In a lithium/sulfur (Li/S) battery, the reduction of sulfur during discharge involves a particular mechanism, where the active material successively dissolves into the electrolyte to form lithium polysulfide intermediate species (Li₂S_x), with x being a function of the state of charge. In this work, sulfur K-edge resonant inelastic X-ray scattering measurements were performed for the characterization of different Li₂S_x polysulfide standard solutions. High-energy resolution fluorescence detected X-ray absorption spectroscopy allowed clear separation the pre-edge absorption peak corresponding to terminal sulfur atoms from the main absorption peak due to internal atoms and allowed quantitative evaluation of the evolution of the peak area ratio as a function of the polysulfide chain length. Results of this experimental work demonstrate that the normalized area of the pre-edge is a reliable fingerprint of the Li₂S_x mean chain length in agreement with recent theoretical predictions. As a perspective, this work confirms that operando HERFD XAS can be used to differentiate mean polysulfide composition, which is key issue in the characterization of Li/S cells.
doi.org/10.1021/acs.jpclett.0c01120