High Performance Li2Ru1−yMnyO3 (0.2 ≤ y ≤ 0.8) Cathode Materials for Rechargeable Lithium-Ion Batteries: Their Understanding

• Published in: Chemistry of materials 2013-04, Vol.25
• Main Authors: Sathiya, M., Ramesha, K., Rousse, G., Foix, Dominique, Gonbeau, Danielle, Prakash, A. S., Doublet, Marie-Liesse, Hemalatha, K., Tarascon, J.-M.
• Format: Article
• Language: English
• Subjects: Condensed Matter; Materials Science; Physics
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/cm400193m

Understanding the origin of the high capacity displayed by Li2MnO3−LiMO2 (M = Ni, Co) composites is essential for improving their cycling and rate capability performances. To address this issue, the Li2Ru1−yMnyO3 series between the iso-structural layered end-members Li2MnO3 and Li2RuO3 was investigated. A complete solid solution was found, with the 0.4 ≤ y ≤ 0.6 members showing sustainable reversible capacities exceeding 220 mAh*g−1 centered around 3.6 V vs Li+/Li. The voltage−composition profiles display a plateau on the first charge as compared to an S-type curve on subsequent discharge which is maintained on the following charges/discharges, with therefore a lowering of the average voltage. We show this profile to evolve upon long cycling due to a structural phase transition as deduced from XRD measurements. Finally we demonstrate, via XPS measurements, the oxidation and reduction of ruthenium (Ru5+/Ru4+) during cycling together with a partial activity of the Mn4+/Mn3+ redox couple. Moreover, we provide direct evidence for the reversibility of the O2− → O− anionic process upon cycling, hence accounting for the high capacity displayed by these materials. This work, by capturing the main redox processes pertaining to these materials, should facilitate their development.