X-ray diffraction and electrochemical impedance spectroscopy study of zinc coated LiNi0.5Mn1.5O4 electrodes

Coating and doping with zinc have been used to modify LiNi0.5Mn1.5O4 powders prepared at 700 and 800 °C. As previously found in the literature, surface treatment with zinc leads to a net improvement of the electrochemical performance of the 5-V electrode in lithium cells. X-ray diffraction reveals the occurrence of surface ZnO, which disappears after heating at 500 °C. This indicates that ZnO forms a coating, although zinc can also be incorporated in the LiNi0.5Mn1.5O4 framework. The electrochemical oxidation of both bare LiNi0.5Mn1.5O4 and zinc treated products has been followed by ex situ X-ray diffraction of charged electrodes. For both materials a decrease in the cubic unit cell parameter and the formation of two cubic phases during lithium extraction has been found. Lattice contraction is significantly larger in the sample modified with zinc. EIS measurements give direct evidence of the better stabilization of the electrode surface in the coated material.