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© Incorporation of various transition metals has been shown to improve the electrochemical performance of Mn–rich Na–ion cathode materials. A greater comprehension of the role of dopant ions, particularly with regard to Mn–rich layered oxides as materials for the positive electrode of Na–ion batteries, is required for their continual development. Here two similar series of Mn–rich P2 cathode materials P2–Na2/3Mn0.8M0.1M′0.1O2 (M = Fe, Zn and M′ = Cu, Al, Ti) are explored, focusing on structural analysis using high–resolution operando synchrotron X–ray diffraction. Notably, under the cycling conditions employed, no P2 to O2 phase transitions toward the charged state were identified for any of the materials investigated. Particularly stable solid solution evolution was observed for P2–Na2/3Mn0.8Zn0.1Cu0.1O2 and P2–Na2/3Mn0.8Zn0.1Al0.1O2 when cycled at 40 mA.g–1 which reflects the electrochemical properties of the materials investigated herein and illustrates that Zn is an excellent choice of dopant for Mn–rich cathode materials. Moreover, the better cyclability of P2–Na2/3Mn0.8Zn0.1Al0.1O2 compared with P2–Na2/3Mn0.8Zn0.1Cu0.1O2 is in keeping with the minimal structural changes observed. This demonstrates that although oxidation state predictions to optimize the initial Mn oxidation state are a good way of initially selecting materials, to truly exploit Mn–rich P2–type materials it is necessary to build up an in–depth understanding of both oxidation states and the associated Jahn–Teller distortion as well as the subtle interplay of synergistic and antagonistic interactions between dopants. Overall, this study illustrates the value of structural investigations to assist in the rational design and validation of novel high–performance materials; the results highlight that the interplay between dopants in addition to the average Mn oxidation state are both crucial considerations when designing high–performance Mn–rich layered oxide materials.
