Effects of Chromium Substitution on the Chemical Bonding Nature and Electrochemical Performance of Layered Lithium Manganese Oxide

Abstract

Chromium-substituted LiMn1-xCrxO2 (0 ≤ x ≤ 0.15) oxides have been prepared by the ion-exchange reaction between α-NaMn1-xCrxO2 and LiBr. From the X-ray diffraction and infrared spectroscopic analyses, all of the present layered compounds are found to be crystallized with monoclinic structure. Additionally, the nitrogen adsorption−desorption isotherm measurements indicate a decrease in crystallite size induced by the replacement of Mn with Cr. According to the electrochemical measurements, the Cr-substituted compounds exhibit better electrochemical performance than the pristine LiMnO2. The effects of chromium substitution on the chemical bonding nature of LiMn1-xCrxO2 have been investigated by performing X-ray absorption spectroscopic (XAS) analyses. The Cr K-edge XAS results presented here clarify that the trivalent chromium ions are stabilized in the octahedral site of the (Mn,Cr)O2 layer before and after the electrochemical charge−discharge process. From the extended X-ray absorption fine structure analyses at the Mn K-edge, it becomes clear that the substitution 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 electrochemical performance of LiMn1-xCrxO2 can be attributed to the enhanced stability of the layered manganese oxide lattice because of the presence of a chromium ion in the octahedral site of the transition metal oxide layer, which hinders the migration of manganese ions into the interlayer lithium sites.