The role of disorder in NaO${}_2$ and its implications for Na-O${}_2$ batteries

We present a DFT study utilizing the Hubbard U correction to probe structural and magnetic disorder in $\mathrm{N}\mathrm{a}{\mathrm{O}}_2$, primary discharge product of Na-O${}_2$ batteries. We show that $\mathrm{N}\mathrm{a}{\mathrm{O}}_2$ exhibits a large degree of rotational and magnetic disorder; a 3-body Ising Model is necessary to capture the subtle interplay of this disorder. MC simulations demonstrate that energetically favorable, FM phases near room temperature consist of alternating bands of orthogonally-oriented ${\mathrm{O}}_2$ dimers. We find that bulk structures are insulating, with a subset of FM structures showing a moderate gap ($<2$ eV) in one spin channel.