The development of cobalt-free P2-Na2/3Ni1/3Mn2/3O2 cathodes is hampered by poor electrochemical performance, resulting from structural instability during high-voltage cycling. Herein, Li+ and F− ions are introduced simultaneously via a simple sol–gel method. The F not only enters the lattice but forms chemically stable NaF on the surface. The modified electrode delivered significantly better electrochemical performance than the pristine one, including much-enhanced capacity retention (64% vs. 36%, 100 cycles) at 0.5 C and a four-time higher capacity output at 10 C. The ex situ XRD and in situ Raman analysis revealed cyclability enhancement mechanisms in terms of inhibiting the P2–O2 phase transition and Na+/vacancy ordering. The conductivity measurements (based on AC impedance and DC polarization) and GITT analysis proved, on both bulk material and electrode levels, that Na+ conduction and, thus, rate performance is notably promoted by doping. The individual contribution of Li and F to the overall performance improvement was also discussed. Furthermore, a solid-state sodium-metal battery was successfully demonstrated with the modified cathode. The above results verify that Li+/F− incorporation can enable enhancements in both cyclability and rate capability of the P2-Na2/3Ni1/3Mn2/3O2 cathodes and are expected to provide a new perspective for the rational design of high-performance layered oxide cathode materials for progressive sodium-ion batteries.
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