Ex situ and in situ Synchrotron X-ray fluorescence imaging coupled with selective micro-X-ray absorption near-edge spectroscopy (μXANES) and micro-X-ray diffraction (μXRD) were used to investigate the electrochemical lithiation of the layered oxysulfide Sr 2MnO 2Cu 3.5S 3. Microfocused X-ray fluorescence (XRF) imaging was used to image the elemental components within the battery electrode while μXANES and μXRD provided information about the Cu oxidation state and phase distribution, respectively. Sr 2MnO 2Cu 3.5S 3 operates by a combined insertion/displacement mechanism. After 1 mol of Li intercalation, Cu metal extrusion is observed by μXRD, which also reveals the formation of the Sr 2MnO 2Cu 3.5-xLi xS 3 phase. Ex situ μXRF images of the electrode after 3.75 mol of Li intercalation show segregated Cu metal and Sr 2MnO 2Cu 3.5-xLi xS 3 particles, while in situ μXRF imaging experiments reveal that the Cu and Mn elemental distribution maps are highly correlated to the particle orientation giving different results when the particle is oriented either perpendicular or parallel to the incident beam. In situ electrochemical synchrotron XRF imaging has the advantage over the ex situ mode in that it allows the reaction mechanism of a single particle to be followed vs time. In situ μXRF imaging data suggest that the microstructure of the electrode, on a microscale level, is not affected by the Cu extrusion process. © 2012 American Chemical Society.
