Effects of chromium substitution on the chemical bonding nature and electrochemical performance of layered lithium manganese oxide

Chromium-substituted LiMn1-xCrxO2 (0 less than or equal to x less than or e qual to 0.15) oxides have been prepared by the ion-exchange reaction betwee n alpha-NaMn1-xCrxO2 and LiBr. From the X-ray diffraction and infrared spec troscopic analyses, all of the present layered compounds are found to be cr ystallized with monoclinic structure. Additionally, the nitrogen adsorption -desorption isotherm measurements indicate a decrease in crystallite size i nduced by the replacement of Mn with Cr. According to the electrochemical m easurements, the Cr-substituted compounds exhibit better electrochemical pe rformance than the pristine LiMnO2. The effects of chromium substitution on the chemical bonding nature of LiMn1-xCrxO2 have been investigated by perf orming X-ray absorption spectroscopic (XAS) analyses. The Cr K-edge XAS res ults presented here clarify that the trivalent chromium ions are stabilized in the octahedral site of the (Mn,Cr)O-2 layer before and after the electr ochemical charge-discharge process. From the extended X-ray absorption fine structure analyses at the Mn K-edge, it becomes clear that the substitutio n of manganese with chromium gives rise to a shortening of the Mn-O bonds, leading to the stabilization of Mn in the octahedral site. On the basis of the present experimental findings, we suggest that the superior electrochem ical performance of LiMn1-xCrxO2 can be attributed to the enhanced stabilit y of the layered manganese oxide lattice because of the presence of a chrom ium ion in the octahedral site of the transition metal oxide layer, which h inders the migration of manganese ions into the interlayer lithium sites.