Delithiation/relithiation process of LiCoMnO4 spinel as 5 V electrode material

In this work, the LiCoMnO4 spinel has been synthesized by a two-step sol-gel based method, followed by sintering at temperatures up to 750 °C in oxygen. After structural characterization of the pristine material via synchrotron and neutron diffraction, the material was characterized via SEM and 6Li-MAS-NMR spectroscopy. 6Li-MAS-NMR spectroscopy in different states of charge revealed, that manganese and cobalt are distributed homogenously throughout the material and the delithiation primary occurs from the manganese environments. It was also shown, that it is not possible to fully delithiate the material in a practical voltage range of an electrolyte. Electrochemical cycling results reveal that about 70% of the lithium can be extracted and reinserted electrochemically in the voltage window from 4.5 to 5.4 V against lithium from/into LiCoMnO4. In situ synchrotron powder diffraction results show that lithium extraction/insertion occurs via a single-phase mechanism over the whole range of lithium contents and that the discharge capacity is mainly restricted by the voltage-window of the electrolyte. Furthermore it was shown, that the delithiation occurs up to a potential of 5.6 V.