NEW PUBLICATION: In operando study of the high voltage spinel cathode material LiNi0.5Mn1.5O4 using two dimensional full-field spectroscopic imaging of Ni and Mn
- Date: June 2015
SEM micrographs of LiNi0.5Mn1.5O4 granules sintered at 1273 K.
LiNi0.5Mn1.5O4 spinel cathode was studied during the first discharge cycle using combined full field Transmission X-ray Microscopy (TXM) and X-ray Absorption Near Edge Structure Spectroscopy (XANES) techniques to follow the chemical phase transformation as well as the microstructural evolution of cathode materials upon operation within an electrochemical cell. The spatial distribution and electrochemical process of the spinel material with spherical granules of 30 mm and 3 mm crystallite size was investigated. The spectroscopic imaging of the cathode within field of view of 40 32 mm2 and spatial resolution of 40 nm has revealed an increase of the LiNi0.5Mn1.5O4 granule size during lithiation providing an insight into the effect of the particle size and morphology on the electrochemical process. The chemical elemental distribution and the content of the different oxidation states of the two absorbing elements (Ni and Mn) have been determined in operando from the XANES imaging. A gradual increase in the content of the oxidation state Mn3+ from 8% up to 64% has been recorded during the discharge from 5 V to 2.7 V. The study of the local oxidation reduction behavior of Mn3+ reveals a reversibility aspect in the local electrochemical reaction of Mn4+ toward Mn3+ in areas located in the center of the aggregate as well as in areas closed to the electrolyte. During the discharge process, a mixture of Mn3+ and Mn4+ has been detected while only single electron valence states have been found in the case of Ni. Probing the chemical changes during the discharge using two-dimensional XANES reveals spatial differences in the electrochemical activities of the two absorbing elements Ni and Mn.