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

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 Na 0.67 Co 1– x Ti x O 2 ( 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. Na 0.67 CoO 2 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, Na 0.67 Co 0.90 Ti 0.10 O 2 exhibits excellent capacity retention (115 mAh g –1 ) even after 100 cycles, whereas Na 0.67 CoO 2 exhibits negligible capacity retention (<10 mAh g –1 ) at 4.5 V cutoff conditions. Na 0.67 Co 0.90 Ti 0.10 O 2 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.