The stability of P2-layered sodium transition metal oxides in ambient atmospheres.

Zuo, Wenhua; Qiu, Jimin; Liu, Xiangsi; Ren, Fucheng; Liu, Haodong; He, Huajin; Luo, Chong; Li, Jialin et al. · Nat Commun · 2020

basic_science · Level V

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Abstract

Air-stability is one of the most important considerations for the practical application of electrode materials in energy-harvesting/storage devices, ranging from solar cells to rechargeable batteries. The promising P2-layered sodium transition metal oxides (P2-Na<sub>x</sub>TmO<sub>2</sub>) often suffer from structural/chemical transformations when contacted with moist air. However, these elaborate transitions and the evaluation rules towards air-stable P2-Na<sub>x</sub>TmO<sub>2</sub> have not yet been clearly elucidated. Herein, taking P2-Na<sub>0.67</sub>MnO<sub>2</sub> and P2-Na<sub>0.67</sub>Ni<sub>0.33</sub>Mn<sub>0.67</sub>O<sub>2</sub> as key examples, we unveil the comprehensive structural/chemical degradation mechanisms of P2-Na<sub>x</sub>TmO<sub>2</sub> in different ambient atmospheres by using various microscopic/spectroscopic characterizations and first-principle calculations. The extent of bulk structural/chemical transformation of P2-Na<sub>x</sub>TmO<sub>2</sub> is determined by the amount of extracted Na<sup>+</sup>, which is mainly compensated by Na<sup>+</sup>/H<sup>+</sup> exchange. By expanding our study to a series of Mn-based oxides, we reveal that the air-stability of P2-Na<sub>x</sub>TmO<sub>2</sub> is highly related to their oxidation features in the first charge process and further propose a practical evaluating rule associated with redox couples for air-stable Na<sub>x</sub>TmO<sub>2</sub> cathodes.