Evaluation of P3-type layered oxides as K-ion battery cathodes

Abstract: Given increasing energy storage demands and limited natural resources of Li, K-ion batteries (KIBs) could be promising next-generation systems having natural abundance, similar chemistry and energy density. Here, we have investigated the P3-type K${0.5}$TMO$_2$ (where TM = Ti, V, Cr, Mn, Co, or Ni) systems using density functional theory calculations, as potential positive intercalation electrodes (or cathodes) for KIBs. Specifically, we have identified the ground state configurations, and calculated the average topotactic voltages, electronic structures, on-site magnetic moments, and thermodynamic stabilities of all P3-K${0.5}$TMO$2$ compositions and their corresponding depotassiated P3-TMO$_2$ frameworks. We find that K adopts the honeycomb or zig-zag configuration within each K-layer of all P3 structures considered, irrespective of the TM. In terms of voltages, we find the Co- and Ti-based compositions to exhibit the highest (4.59 V vs. K) and lowest (2.24 V) voltages, respectively, with the TM contributing to the redox behavior upon K (de-)intercalation. We observe all P3-K${0.5}$TMO$2$ to be (meta)stable, and hence experimentally synthesizeable according to our 0 K convex hull calculations, while all depotassiated P3-TMO$_2$ configurations are unstable and may appear during electrochemical cycling. Also, we verified the stability of the prismatic coordination environment of K compared to octahedral coordination at the K${0.5}$TMO$_2$ compositions using Rouxel and cationic potential models. Finally, combining our voltage and stability calculations, we find P3-K$_x$CoO$_2$ to be the most promising cathode composition, while P3-K$_x$NiO$_2$ is worth exploring. Our work should contribute to the exploration of strategies and materials required to make practical KIBs.