Investigation of K modified P2 Na0.7Mn0.8Mg0.2O2 as a cathode material for sodium-ion batteries

Abstract

Sodium-ion batteries (NIBs) are emerging as a potentially cheaper alternative to lithium-ion batteries (LIBs) due to the larger abundance of sodium and in some cases the similar intercalation chemistry to LIBs. Here we report the solid state synthesized K-modified P2 Na_0.7Mn_0.8Mg_0.2O₂ which adopts hexagonal P6₃/mmc symmetry. The second charge/discharge capacity for the as-prepared material is 115/111 mA h g⁻¹ between 1.5–4.2 V at a current density of 15 mA g⁻¹, which reduces to 61/60 mA h g⁻¹ after 100 cycles. Scanning transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy (STEM-EDS) analysis shows a heterogeneous distribution of K and solid state ²³Na NMR illustrates that the presence of K perturbs the local environment of Na within the P2 Na_0.7Mn_0.8Mg_0.2O₂ crystal structure. Larger scale X-ray absorption near-edge structure (XANES) data on the K L-edge also illustrate that K is present on the surface of electrodes in preference to the bulk. In situ synchrotron X-ray diffraction (XRD) data illustrates that the P2 structural motif is preserved, featuring a solid solution reaction for most of charge–discharge except at the charged and discharged states where multiple phases are present. The K-modified sample of P2 Na_0.7Mn_0.8Mg_0.2O₂ is compared with the K-free samples in terms of both structural evolution and electrochemical performance.