Structural originations of irreversible capacity loss from highly lithiated copper oxides

We use electrochemistry, high-energy X-ray diffraction (XRD) with pair-distribution function analysis (PDF), and density functional theory (DFT) to study the instabilities of Li2CuO2 at varying state of charge. Rietveld refinement of XRD patterns revealed phase evolution from pure Li2CuO2 body-centered orthorhombic (Immm) space group to multiphase compositions after cycling. The PDF showed CuO4 square chains with varying packing during electrochemical cycling. Peaks in the G(r) at the Cu–O distance for delithiated, LiCuO2, showed CuO4 square chains with reduced ionic radius for Cu in the 3+ state. At full depth of discharge to 1.5 V, CuO was observed in fractions greater than the initial impurity level which strongly affects the reversibility of the lithiation reactions contributing to capacity loss. DFT calculations showed electron removal from Cu and O during delithiation of Li2CuO2.