From structure to electrochemistry: the influence of transition metal ordering on Na$^+$ /vacancy orderings in P2-type Na$_x$MO$_2$ cathode materials for sodium-ion batteries

P2-type layered oxides are attractive cathode active materials for sodium-ion batteries, however, these materials typically suffer from detrimental Na+/vacancy orderings. In this work, we investigate the origin as well as the influence of the transition metal ratio on Na+/vacancy orderings in P2-type cathode materials. A combination of X-ray diffraction (XRD), neutron diffraction, advanced electrochemical methods, operando XRD and DFT calculations is applied to study Na+/vacancy orderings in P2-NaxNi1/3Mn2/3O2 and P2-NaxMn3/4Ni1/4O2. In P2-NaxNi1/3Mn2/3O2, a honeycomb Ni/Mn superstructure leads to charge ordering within the transition metal slab and pronounced Na+/vacancy orderings, causing distinct voltage jumps at specific sodium contents (x = 2/3, 1/2 and 1/3). For P2-Na0.60Mn3/4Ni1/4O2, the Ni/Mn superstructure is disrupted, resulting in more complex charge orderings within the transition metal slab, partially suppressed Na+/vacancy orderings and an overall smoother potential profile. Based on our findings, guidelines to suppress Na+/vacancy orderings in P2-type cathode materials for sodium-ion batteries are postulated and discussed with respect to electrochemical measurements of various transition metal compositions. ... mehrThese guidelines can serve to predict the tendency towards Na+/vacancy orderings for a given cathode composition or to design new cathode compositions for enhanced cycle life based on the absence of Na+/vacancy orderings.