Design and development of high-energy, efficient, and structurally stable positive electrodes for Na-ion batteries (NIBs) have recently been focusing on layered transition metal oxides (Na x TMO2, 0 < x < 1). When doped with late transition metals, the redox reactions ensuring the charge compensation upon Na+ removal can rely on the direct participation of anionic chemistry, with encouraging outcomes in terms of both energy density and power. However, the control of reversible O2–/O– reactions is still a major issue, as the undesired release of O2 can lead to detrimental effects on cathode capacity and overall cell stability. The fine-tuning of metal–oxygen bond covalency has recently emerged as a promising strategy toward the reversible access of oxygen redox. Following the route paved by Ru-based Li-rich cathode materials, we hereby present a first-principles investigation of a Ru-doped Na x TMO2 (TM = Ru, Ni, and Mn) system and the related structural and electronic properties of interest for NIB applications. We aim to dissect the specific role of each element sublattice in compensating the electronic charge along desodiation, with a major focus on the anionic contribution. The oxygen activity is addressed in the high-voltage range (i.e.,x Na = 0.25), and the underlying mechanism is derived from PBE + U(-D3BJ) calculations. We also discuss the effects of Mn deficiency as a suitable site for the formation of low-energy superoxide species via preferential breaking of the Ni–O bond. Conversely, breaking a Ru–O bond is unlikely to occur, which assesses the key role of the Ru dopant in stabilizing the oxide lattice and enabling the desired reversible conditions. Our results also highlight the oxygen vacancy formation energy as an effective descriptor for different activities toward the O2–/O–/O2 evolution. All these theoretical insights can be useful to drive further experimental efforts toward the optimal design of efficient and high-energy NIB cathodes with enhanced practical reversible capacity.
In the search for high‐energy cathode materials for Na‐ion batteries (NIBs), Fe‐doped layered transition metal oxides have been recently proposed as promising systems that can ensure improved reversible capacity at high working voltage. Exploiting the anionic redox chemistry in this class of materials represents a great advance for the energy storage community, but uncontrolled oxidation process can lead to the formation of unbound molecular oxygen, with detrimental effects on overall capacity and stability upon cycling. The higher TM–O covalency provided by Fe doping seems to prevent oxygen loss and ensure full capacity recovery. Understanding anionic processes and the underlying mechanism with atomistic details can reinforce the experimental efforts and help to outline rational design strategies for novel high‐performing NIB cathodes. To this end, we present a state‐of‐the‐art first‐principles study on the P2‐type NaxTMO2 (TM = Fe, Ni, and Mn—NFNMO) oxide. We compare structural and electronic features of stoichiometric (NaxFe0.125Ni0.125Mn0.75O2) and Mn‐deficient (NaxFe0.125Ni0.125Mn0.68O2) NFNMO to identify and discuss the contribution of each element sublattice on charge compensation processes. Although Mn deficiency is predicted to increase the cathode working voltage, we find the charge compensation being mostly exerted by the Ni and Fe sublattices. Oxygen redox is unfold via the formation of superoxide species at low Na loads with a preferential breaking of more labile Ni–O bonds and binding to Fe atoms. Our calculations predict no release of molecular O2 upon desodiation, thus highlighting the key role of Fe dopant that provides a good TM–O bond strength, preventing oxygen loss while still enabling anionic redox reactions at high voltages with extra reversible capacity.
Post-lithium batteries are emerging as viable solutions towards the sustainable energy transition. The effective deployment in the market calls for great research efforts in the identification of novel component materials...
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