LiMn2-xCuxO4 Spineis - 5 V Cathode Materials

Abstract

ABSTRACTA series of electroactive spinel compounds, LiMn2-xCuxO4 (0.1 ≤ x ≤ 0.5) has been studied by crystallographic, spectroscopie and electrochemical methods and by electron-microscopy. These LiMn2-xCuxO4 spinels are nearly identical in structure to cubic LiMn2O4 and successfully undergo reversible Li intercalation. The electrochemical data show slight shifts to higher voltage for the delithiation reaction that normally occurs at 4.1 V in standard Li1−xMn2O4 electrodes (1 ≥ x ≥ 0) corresponding to the oxidation of Mn3+ to Mn4+. The data also show a remarkable reversible electrochemical process at 4.9 V which is attributed to the oxidation of Cu2+ to Cu3+. The inclusion of Cu in the spinel structure enhances the electrochemical stability of these materials upon cycling. The initial capacity of LiMn2-xCuxO4 spinels decreases with increasing x from 130 mAh/g in LiMn2O4 (x=0) to 70 mAh/g in “LiMn1.5Cu0.5O4”(x=0.5). Although the powder X-ray diffraction pattern of “LiMn1.5Cu0.5 O4” shows a single-phase spinel product, neutron diffraction data show a small, but significant quantity of an impurity phase, the composition and structure of which could not be identified. X-ray absorption spectroscopy was used to gather information about the oxidation states of the manganese and copper ions. The composition of the spinel component in the LiMn1.5Cu0.5O4 was determined from X-ray diffraction and XANES data to be Li1.01Mn1.67Cu0.32O4 suggesting, to a best approximation, that the impurity in the sample was a lithium-copper-oxide phase.