Characterization of electrode/electrolyte interface for lithium batteries using in situ synchrotron X-ray reflectometry—A new experimental technique for LiCoO2 model electrode

A new experimental technique was developed for detecting structure changes at electrode/electrolyte interface of lithium cell using X-ray reflectometry and two-dimensional model electrodes with a restricted lattice-plane. The electrodes were constructed with an epitaxial film of LiCoO2 synthesized by pulsed laser deposition method. The orientation of the epitaxial film depends on the substrate plane; the 2D layer of LiCoO2 is parallel to the SrTiO3 (1 1 1) substrate ((0 0 3)LiCoO2//(1 1 1)SrTiO3)((0 0 3)LiCoO2//(1 1 1)SrTiO3), while the 2D layer is perpendicular to the SrTiO3 (1 1 0) substrate ((1 1 0)LiCoO2//(1 1 0)SrTiO3)((1 1 0)LiCoO2//(1 1 0)SrTiO3). The anisotropic properties were confirmed by electrochemical measurements. Ex situ X-ray reflectivity measurements indicated that the impurity layer existed on the as-grown LiCoO2 was dissolved and a new SEI layer with lower density was formed after soaking into the electrolyte. In situ X-ray reflectivity measurements indicated that the surface roughness of the intercalation (1 1 0) plane increased with applying voltages, while no significant changes in surface morphology were observed for the intercalation non-active (0 0 3) plane during the pristine stage of the charge–discharge process.