On the P2-NaxCo1-y(Mn2/3Ni1/3)yO2 Cathode Materials for Sodium-Ion Batteries: Synthesis, Electrochemical Performance, and Redox Processes Occurring during the Electrochemical Cycling.

P2-type NaMO2 sodiated layered oxides with mixed transition metals are receiving considerable attention for use as cathodes in sodium-ion batteries. A study on solid solution (1 - y)P2-NaxCoO2-(y)P2-NaxMn2/3Ni1/3O2 (y = 0, 1/3, 1/2, 2/3, 1) reveals that changing the composition of the transition metals affects the resulting structure and the stability of pure P2 phases at various temperatures of calcination. For 0 ≤ y ≤ 1.0, the P2-NaxCo(1-y)Mn2y/3Niy/3O2 solid-solution compounds deliver good electrochemical performance when cycled between 2.0 and 4.2 V versus Na+/Na with improved capacity stability in long-term cycling, especially for electrode materials with lower Co content (y = 1/2 and 2/3), despite lower discharge capacities being observed. The (1/2)P2-NaxCoO2-(1/2)P2-NaxMn2/3Ni1/3O2 composition delivers a discharge capacity of 101.04 mAh g-1 with a capacity loss of only 3% after 100 cycles and a Coulombic efficiency exceeding 99.2%. Cycling this material to a higher cutoff voltage of 4.5 V versus Na+/Na increases the specific discharge capacity to ≈140 mAh g-1 due to the appearance of a well-defined high-voltage plateau, but after only 20 cycles, capacity retention declines to 88% and Coulombic efficiency drops to around 97%. In situ X-ray absorption near-edge structure measurements conducted on composition NaxCo1/2Mn1/3Ni1/6O2 (y = 1/2) in the two potential windows studied help elucidate the operating potential of each transition metal redox couple. It also reveals that at the high-voltage plateau, all of the transition metals are stable, raising the suspicion of possible contribution of oxygen ions in the high-voltage plateau.

Passivation Layer and Cathodic Redox Reactions in Sodium-Ion Batteries Probed by HAXPES.

The cathode material P2-Nax Co2/3 Mn2/9 Ni1/9 O2, which could be used in Na-ion batteries, was investigated through synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES). Nondestructive analysis was made through the electrode/electrolyte interface of the first electrochemical cycle to ensure access to information not only on the active material, but also on the passivation layer formed at the electrode surface and referred to as the solid permeable interface (SPI). This investigation clearly shows the role of the SPI and the complexity of the redox reactions. Cobalt, nickel, and manganese are all electrochemically active upon cycling between 4.5 and 2.0 V; all are in the 4+ state at the end of charging. Reduction to Co(3+), Ni(3+), and Mn(3+) occurs upon discharging and, at low potential, there is partial reversible reduction to Co(2+) and Ni(2+). A thin layer of Na2 CO3 and NaF covers the pristine electrode and reversible dissolution/reformation of these compounds is observed during the first cycle. The salt degradation products in the SPI show a dependence on potential. Phosphates mainly form at the end of the charging cycle (4.5 V), whereas fluorophosphates are produced at the end of discharging (2.0 V).