Ab Initio Study of the Sodium Intercalation and Intermediate Phases in Na0.44MnO2 for Sodium-Ion Battery

The Na 0.44 MnO 2 structure is a promising cathode material for sodium ion batteries due to a high capacity (∼130 mAh/g) and good cycle performance. In this work, we present the results of density functional theory (DFT) calculations on the structural and electrochemical properties of Na 0.44 MnO 2, combined with experiments. Seven intermediate phases and the two-phase reactions among them were found, where the calculated voltage profile agreed well with experiments. We found that the S-shaped tunnel is not empty in the deintercalated Na 0.22 MnO 2 structure but has a partial occupancy of sodium ions. The new sodium sites were found in a limited sodium composition range ( x = 0.44–0.55) which is attributed to the electrostatic interactions between sodium ions and manganese atoms. The asymmetric lattice evolution in Na 0.44 MnO 2 as a function of sodium insertion/deinsertion is shown to be due to the Jahn–Teller effects. On the basis of this interpretation, we suggest that the Cr substitution will reduce the volume change significantly.