The development of new energy storage technologies is essential for the advancement of a society increasingly dependent on energy supplies. In this context, sodium-ion batteries (SIBs) have proven to be the key to revolutionizing the global energy market, especially for large-scale stationary energy storage and light electromobility [1]. However, the achievement of the full potential of SIBs technology remains a challenge and efforts should be focused on the design of more efficient high energy density and high cycle life sodium-based positive electrodes. In this scenario, sodium-based layered oxide cathodes with general formula NaxMO2 (M = transition metal/s) are an excellent choice due to their electrochemical performance, environmental friendliness and scalability [2,3]. Prof. Claude Delmas pioneered the study of the electrochemical intercalation processes of this family of compounds, being one of the first researchers to exploit their potential in SIBs. Although the virtues of this family of materials as cathodes are clear, there are also several drawbacks such as irreversible structural phase transitions, strong Na+-vacancy ordering tendencies or poor cyclability that should be addressed to ensure the optimum operation of this material in a commercial battery.One of the peculiarities of these cathode materials lies in the diverse structures that they can adopt, being the P2 and O3 structures the most interesting from the electrochemical point of view. P2-type phases present higher rate performance and capacity retention than O3-type phases. However, they are only stable with sodium contents ≤ 0.85, which translates into higher first irreversible capacity. In O3-type phases, on the other hand, it is possible to reach the fully sodiated stoichiometry, delivering thus higher capacities but at the expense of considerable retention nested in O3-P3 phase transitions, which alter the diffusion mechanism of Na+ ions giving rise to a large energy barrier that Na+ ions must overcome.This talk will present the main advances on the development of sodium layered oxide cathodes, as well as the most successful strategies for overcoming current challenges, such as doping with electrochemically active and inactive elements [4], surface coatings [5], the use of sacrificial salts [6] or the synergetic P2/O3 combination effect [7]. Finally, the anionic redox effect and the controversy in the explanation of the extra capacity observed in certain de-sodiated transition metal oxides will also be discussed. Goikolea, T. Rojo, et al. Adv. Energy Mater. 2020, 10, 2002055H. Han, T. Rojo, et al., Energy Environ. Sci. 2015, 8, 81–102Ortiz-Vitoriano, T. Rojo, et al., Energy Environ. Sci. 2017, 10, 1051–1074Gonzalo, T. Rojo, et al. Enegy Storage Mater. 2021, 34, 682–707Zarrabeitia, T. Rojo, et al. J. Mater. Chem. A, 2019, 7, 14169–14179J. Fernández-Ropero, D. Shanmukaraj et al. ACS Appl. Mater Interfaces, 2021, 13, 11814–11821Bianchini, T. Rojo, et al. J. Mater. Chem. A, 2018, 6, 3552–3559.
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