Na+/Vacancy Disordered P2-Na0.67Co1-xTixO2: High-Energy and High-Power Cathode Materials for Sodium Ion Batteries.

Abstract

Although sodium ion batteries (NIBs) have gained wide interest, their poor energy density poses a serious challenge for their practical applications. Therefore, high-energy-density cathode materials are required for NIBs to enable the utilization of a large amount of reversible Na ions. This study presents a P2-type Na0.67Co1-xTixO2 (x < 0.2) cathode with an extended potential range higher than 4.4 V to present a high specific capacity of 166 mAh g-1. A group of P2-type cathodes containing various amounts of Ti is prepared using a facile synthetic method. These cathodes show different behaviors of the Na+/vacancy ordering. Na0.67CoO2 suffers severe capacity loss at high voltages due to irreversible structure changes causing serious polarization, while the Ti-substituted cathodes have long credible cycleability as well as high energy. In particular, Na0.67Co0.90Ti0.10O2 exhibits excellent capacity retention (115 mAh g-1) even after 100 cycles, whereas Na0.67CoO2 exhibits negligible capacity retention (<10 mAh g-1) at 4.5 V cutoff conditions. Na0.67Co0.90Ti0.10O2 also exhibits outstanding rate capabilities of 108 mAh g-1 at a current density of 1000 mA g-1 (7.4 C). Increased sodium diffusion kinetics from mitigated Na+/vacancy ordering, which allows high Na+ utilization, are investigated to find in detail the mechanism of the improvement by combining systematic analyses comprising TEM, in situ XRD, and electrochemical methods.