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Electronic Structure of Sodium Superoxide Bulk, (100) Surface, and Clusters using Hybrid Density Functional: Relevance for Na–O2 Batteries

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journal contribution
posted on 17.12.2015, 08:22 by Oier Arcelus, Chunmei Li, Teófilo Rojo, Javier Carrasco
Clarifying the electronic structure of sodium superoxide (NaO2) is a key step in understanding the electrochemical behavior of Na–O2 batteries. Here we report a density functional theory study to explore the effect of atomic structure and morphology on the electronic properties of different model systems: NaO2 bulk, (100) surface, and small (NaO2)n clusters (n = 3–8). We found that a correct description of the open-shell 2p electrons of O2 requires the use of a hybrid functional, which reveals a clear insulating nature of all of the investigated systems. This sheds light onto the capacity limitations of pure NaO2 as a discharge product and highlights the need for developing new strategies to enhance its electron transport in the optimization of Na–O2 cells.