In Situ X-ray Absorption Spectroscopic Study on LiNi0.5Mn0.5O2 Cathode Material during Electrochemical Cycling

Abstract: We have investigated the local electronic and atomic structure of the LiMn0.5Ni0.5O2 electrode during the first charge and discharge process using in situ X-ray absorption spectroscopy (XAS) of the Mn and Ni K-edges. The Ni K-edge structure in the XANES spectrum shifts to higher energy during charge and shifts back reversibly during discharge in the higher voltage region of ∼4 V, whereas the Mn K-edge structure does not appear to exhibit a rigid edge shift. Further Li-ion intercalation during extended discharge in the 1-V plateau leads to the reduction of Mn4+ ions suggesting that the charge compensation in this region is achieved via the reduction of Mn4+ ions to Mn2+. Mn K-edge EXAFS results indicate that a small amount of Li is found in the Ni2+/Mn4+ layers. These Li ions in the transition metal layers are primarily present in the second coordination shell of Mn and not around Ni. Ni K-edge EXAFS fitting results suggest that the oxidation process upon Li deintercalation takes place in two steps:  Ni2+ ...