Li-rich Mn-based layered oxides are among the most promising cathode materials for next-generation lithium-ion batteries, yet they suffer from capacity fading and voltage decay during cycling. The electrochemical performance of the material can be improved by doping with Mg. However, the effect of Mg doping at different positions (lithium or transition metals) remains unclear. Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ (LR) was synthesized by coprecipitation followed by a solid-state reaction. The coprecipitation stage was used to introduce Mg in TM layers (sample LR-Mg), and the solid-state reaction (st) was used to dope Mg in Li layers (LR-Mg(st)). The presence of magnesium at different positions was confirmed by XRD, XPS, and electrochemical studies. The investigations have shown that the introduction of Mg in TM layers is preferable in terms of the electrochemical performance. The sample doped with Mg at the TM positions shows better cyclability and higher discharge capacity than the undoped sample. The poor electrochemical properties of the sample doped with Mg at Li positions are due to the kinetic hindrance of oxidation of the manganese-containing species formed after activation of the Li₂MnO₃ component of the composite oxide. The oxide LR-Mg(st) demonstrates the lowest lithium-ion diffusion coefficient and the greatest polarization resistance compared to LR and LR-Mg.

This article studies the doping of Li-rich cathode materials. Aluminum and iron were chosen as dopants. Li-rich cathode materials for lithium-ion batteries, which were composed of Li_1.2Ni_0.133Mn_0.534Co_0.133O₂ with a partial replacement of cobalt (2 at %) by iron and aluminum, were synthesized. The dopants were introduced at the precursor synthesis stage by co-precipitation. The presence of Fe and Al in the composition of the synthesized samples was proved by inductively coupled plasma mass spectrometry, X-ray diffraction analysis and X-ray microanalysis. The cathode materials were tested electrochemically. The incorporation of Al and Fe into the structure of lithium-enriched materials improved the cyclability and reduced the voltage fade of the cathodes. An analysis of the electrochemical data showed that the structural changes that occur in the initial cycles are different for the doped and starting materials and affect their cycling stability. The partial cation substitution suppressed the unfavorable phase transition to lower-voltage structures and improved the electrochemical performance of the materials under study.