Long-term cycling behavior of Mg-doped LiCoO2 materials investigated with the help of laboratory scale X-ray absorption near-edge spectroscopy

The use of Li-ion batteries is increasing rapidly. Understanding the processes behind active material aging helps to enhance the materials, and therefore, development of new in situ methods for structural studies is important. In addition, understanding the effect of different synthesis methods on the active material properties is necessary to optimize the material cycle life. In this work, the performance of LiCoO2 doped with Mg during the lithiation step is compared to LiCoO2 prepared using an Mg-doped Co3O4 precursor. In situ laboratory-scale X-ray absorption near-edge spectroscopy is used to analyze the Co valence changes in LiCoO2 to understand the electrochemical behavior of the investigated materials. The maximum reachable Co valence state is found to decrease upon aging, a small decrease indicating a good cycle-life, and this is attributed to the enhanced stacking order, better Mg distribution in the lattice, and fine primary particle size in the material. In the synthesis conditions used in this study, Mg doping during the lithiation step is shown to perform better compared to the precursor doping. Overlithiation is shown to reduce the electrochemical performance of nondoped and precursor-doped LiCoO2 materials but not to affect the cyclability of lithiation-doped LiCoO2. [Display omitted] •Mg-doping of LCO during two process steps is compared for two Li/Co stoichiometries.•Laboratory-scale XANES is used to observe Co valence state differences upon cycling.•Doping during the lithiation step induces an even Mg distribution in LCO particles.•Synthesis ratio Li/Co = 1.05 (vs. 1.005) causes poorer stacking order and cycle life.•The capacity retention of lithiation Mg-doped LCO after 1000 cycles is 83%.