In operando study of the high voltage spinel cathode material LiNi0.5Mn1.5O4 using two dimensional full-field spectroscopic imaging of Ni and Mn

Abstract

LiNi_0.5Mn_1.5O₄ 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 μm and 3 μm crystallite size was investigated. The spectroscopic imaging of the cathode within field of view of 40 × 32 μm² and spatial resolution of 40 nm has revealed an increase of the LiNi_0.5Mn_1.5O₄ 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.