P2 Structure Sodium Manganese Oxides for Na-Ion Batteries

Thursday, 30 July 2015: 10:40
Carron (Scottish Exhibition and Conference Centre)
J. M. Billaud (University of St. Andrews), G. Singh (CIC EnergiGUNE), A. R. Armstrong (University of St Andrews), E. C. Gonzalo (CIC EnergiGUNE), V. Roddatis, M. Armand (CIC Energigune), J. W. Somerville, U. Maitra, N. Tapia-Ruiz (University of Oxford), T. Rojo (Universidad del País Vasco (UPV/EHU)), and P. G. Bruce (University of Oxford, Department of Materials)
Lithium ion batteries have dominated the world of portable electronic devices over the past two decades and are making their way into the electric vehicle market due to their high energy density. However, recently sodium ion batteries have regained the interest of the scientific community due to the high and uniform abundance of sodium across the world and consequent low cost compared to lithium, making them attractive for grid storage. Various electrode materials have been studied for sodium ion batteries. Layered oxides, NaMO2, where M is one or more transition metals, represent an attractive class of cathodes for Na batteries. Here we show that Na0.67MnO2 with the P2 structure, Figure 1 a), exhibits a high capacity (175 mAhg-1), close to the best reported for a Na cathode, and with good capacity retention, in contrast to previous studies of Na0.67MnO2 where the capacity faded rapidly. [1] Due to the presence of Jahn–Teller active Mn3+ in Na0.67MnO2, the structure undergoes various structural transitions during sodiation/desodiation leading to many voltage steps in the charge/discharge profile. [2], [3] We have investigated reducing the phase transitions by substituting Mn3+ ions with electrochemically inactive dopant ions, which have a strong preference for octahedral sites in the layered oxide framework. This leads to the formation of a highly stable framework that shows a smooth charge/discharge profile with very low polarization even for a substitution level as low as 5%, Figure 1 b) and a capacity of ~ 175 mAhg-1. Such an observation is significant for the future development of sodium ion battery cathode materials.


[1]         A. Caballero, L. Hernán, J. Morales, L. Sánchez, J. Santos Peña, and M. A. G. Aranda, J. Mater. Chem., 12, 1142–1147.

[2]         N. Yabuuchi, M. Kajiyama, J. Iwatate, H. Nishikawa, S. Hitomi, R. Okuyama, R. Usui, Y. Yamada, and S. Komaba, Nat. Mater., 11, 512-517.

[3]           X. Wang, M. Tamaru, M. Okubo, and A. Yamada, J. Phys. Chem. C, 2013, 117, 15545.