Layered cathodes have been recognized as potential advanced candidates for sodium-ion batteries (SIBs), but the poor electrochemical performance has seriously hindered their further development. Herein, an ordered Na2/3[Ni2/9Mg1/9Mn5/9Ti1/9]­O2 (NMMT) is designed and investigated as a high-performance cathode for SIBs through the synergistic effect of Mg and Ti codoping. Compared to the single Mg- or Ti-doped materials, NMMT clearly exhibits superstructure ordering diffraction peaks, and neutron diffraction further confirms that the diffraction peaks can be well indexed by a larger supercell P63, rather than the common unit cell P63/mmc by X-ray diffraction (XRD). High-resolution transmission electron microscopy also approves the ordering arrangement. This material shows an obvious capacity activation process during the first cycles, thus delivering 113 mA h g–1 specific capacity at 0.1 C (close to the theoretical value). Excellent rate capability even at 15 C and cycling stability after 500 cycles between 2.0 and 4.3 V can also be achieved, indicating that an ordered cathode is still promising. Besides, a single-phase reaction mechanism is revealed by ex situ/in situ XRD experiments. This study offers some insights into the material design and characterization of layered oxide cathodes for high-performance SIBs in the future.

Though considerable Mg-doped layered cathodes have been exploited, some new differences relative to previous reports can be concluded by doping a heavy dose of Mg via two rational strategies. Unlike the common unit cell of the P63/mmc group by X-ray diffraction, neutron diffraction reveals a large supercell of the P63 group and enhanced ordering for Na11/18Mg1/18[Ni1/4Mg1/9Mn11/18]O2 with Mg occupying both the Na and Mn sites. Compared with only one obvious voltage plateau of Na0.5[Ni0.25Mn0.75]O2 (NNM), Na11/18Mg1/18[Ni1/4Mg1/9Mn11/18]O2 (NMNMM) shows more severe voltage plateaus but with excellent electrochemical performance. Na0.5[Mg0.25Mn0.75]O2 (NMM) with Mg only occupying the Ni site displays a highly reversible whole-voltage-range oxygen redox chemistry and smooth voltage curves without any voltage hysteresis. Cationic Ni2+/Ni4+ couples are responsible for the charge compensations of NNM and NMNMM, while only the oxygen anionic reaction accounts for the capacity of NMM between 2.5 and 4.3 V. Interestingly, the Mn3+/Mn4+ pair contributes all capacity for all cathodes between 1.5 and 2.5 V. All cathodes undergo a double-phase mechanism: an irreversible P2–O2 phase transition for NNM, an enhanced reversible P2–O2 phase transition for NMNMM, and a highly reversible P2–OP4 phase transition for NMM. In addition, the designed cathodes display excellent rate capability and long-term cycling stability but with a large difference in the various voltage ranges of 2.5–4.3 and 1.5–2.5 V, respectively. This work provides a good understanding of ion doping and some new insights into exploiting high-performance materials.