Origin of improved Na+ ionic conductivity in the NASICON-type solid state electrolyte with Sm modification

The NASICON-type (Na1+xZr2SixP3-xO12, 0≤x ≤ 3) sodium-ion solid state electrolyte (SSE) has emerged as an alternative for liquid electrolyte due to its good chemical/electrochemical stability, high thermal stability and high safety. However, the insufficient ionic conductivity and poor understanding of Na+ transport mechanism hinder the further development of sodium-ion SSE. Herein, we report Sm modified Na3+xZr2-xSmxSi2PO12 (0≤x ≤ 0.4) electrolytes with a highest ionic conductivity of 2.25 × 10−3 S cm−1 at 25 °C when x = 0.2. The introduction of Sm element adjusts the Si/P ratio in NASICON phase and densifies the electrolyte pellets by formation of Na3Sm(PO4)2. To get a deep insight into the enhanced mechanism of Na + transport in grains, low-temperature electrochemical impedance spectra (LT-EIS) and Jonscher's power law relationship are employed to analyze the electrical behavior of grains. The results demonstrate that the regulation of Si/P ratio can evoke lower migration energy, more charge carrier concentration and higher hopping frequency, which synergistically improve the ionic conductivity in grains.