High Voltage Mg-Doped Na 0.67 Ni 0.3 − x Mg x Mn 0.7 O 2 ( x = 0.05, 0.1) Na- Ion Cathodes with Enhanced Stability and Rate Capability

Abstract

Magnesium substituted P2-structure Na0.67Ni0.3Mn0.7O2 materials have been prepared by a facile solid-state method and investigated as cathodes in sodium-ion batteries. The Mg-doped materials described here were characterized by Xray diffraction (XRD), Na-23 solid-state nuclear magnetic resonance (SS-NMR), and scanning electron microscopy (SEM). The electrochemical performance of the samples was tested in half cells vs Na metal at room temperature. The Mg-doped materials operate at a high average voltage of ca. 3.3 V vs Na/Na+ delivering specific capacities of similar to 120 mAh g(-1), which remain stable up to 50 cycles. Mg doping suppresses the well-known P2-O2 phase transition observed in the undoped composition by stabilizing the reversible OP4 phase during charging (during Na removal). GITT measurements showed that the Na-ion mobility is improved by 2 orders of magnitude with respect to the parent P2-Na0.67Ni0.3Mn0.7O2 material. The fast Na-ion mobility may be the cause of the enhanced rate performance.