Kinetic Monte Carlo Simulations of Sodium Ion Transport in NaSICON Electrodes

Abstract: The development of high-performance sodium (Na) ion batteries requires improved electrode materials. The energy and power densities of Na superionic conductor (NaSICON) electrode materials are promising for large-scale energy storage applications. However, several practical issues limit the full utilization of the theoretical energy densities of NaSICON electrodes. A pressing challenge lies in the limited sodium extraction in low Na content NaSICONs, e.g., $\rm Na_1V^{IV}V^{IV}(PO_4)_3 \leftrightarrow V^{V}V^{IV}(PO_4)_3 + 1e^- + 1Na^+$. Hence, it is important to quantify the Na-ion mobility in a broad range of NaSICON electrodes. Using a kinetic Monte Carlo approach bearing the accuracy of first-principles calculations, we elucidate the variability of Na-ion transport vs. Na content in three important NaSICON electrodes, Na${\rm x}$Ti${2}$(PO${4}$)${3}$, Na${\rm x}$V${2}$(PO${4}$)${3}$, and Na${\rm x}$Cr${2}$(PO${4}$)${3}$. Our study suggests that Na$^+$ transport in NaSICON electrodes is almost entirely determined by the local electrostatic and chemical environment set by the transition metal and the polyanionic scaffold. The competition with the ordering-disordering phenomena of Na-vacancies also plays a role in influencing Na-transport. We link the variations in the Na$^+$ kinetic properties by analyzing the competition of ligand field stabilization transition metal ions and their ionic radii. We interpret the limited Na-extraction at $x = 1$ observed experimentally by gaining insights into the local Na-vacancy interplay. We propose that targeted chemical substitutions of transition metals disrupting local charge arrangements will be critical to reducing the occurrence of strong Na$^+$-vacancy orderings at low Na concentrations, thus, expanding the accessible capacities of these electrode materials.