Reversible OP4 phase in P2–Na2/3Ni1/3Mn2/3O2 sodium ion cathode

Abstract P2–Na2/3Ni1/3Mn2/3O2 as a promising cathode material for sodium ion batteries (SIBs) has attracted much attention owing to high capacity and wide operation voltage. However, it suffers from inferior rate and cycling performances due to P2–O2 phase transition and Na+/vacancy ordering during charge/discharge process. Herein, a Fe/Ti co-substitution strategy is successfully utilized to mitigate these issues. Notably, as probed by In-situ X-ray diffraction, the substitution of Ni with Fe significantly stabilizes the interlayer framework by impeding slab glide during deep Na+ extraction, resulting in reversible P2-OP4 phase transition with smaller volume change of host structure compared to P2–O2 transition. Meanwhile, synchrotron X-ray diffraction shows that, the Na+/vacancy ordering is greatly suppressed by further replacing Mn with Ti, which breaks down the long-range ordering of Ni/Mn distribution, promoting Na ion transport. In addition, the charge compensation mechanism of Fe/Ti co-substituted P2–Na0.67Ni0.23Fe0.1Mn0.57Ti0.1O2 (NFMT) revealed by Ex-situ X-ray absorption spectroscopy demonstrates that the incorporation of Fe3+/4+ redox couple largely improve the working voltage. Consequently, the obtained NFMT cathode delivers a high energy density over 420 Wh/kg within 4.3–2.6 V, accompanied with remarkably enhanced kinetics and capacity retention. Such co-substitution strategy provides a promising approach to develop high-voltage and cycle-stable cathode materials for SIBs.