Length-Scale-Dependent Ion Dynamics in Ca-Doped Na₃PS₄

Abstract

The sodium ion conductor Na 3 PS 4 is a promising electrolyte for future all-solid-state batteries using Na + ions as ionic charge carriers. Its readily available components make it a compelling and more sustainable alternative to recent Li-ion technologies. At ambient temperature, the ionic conductivity is in the order of 10 −4 S cm −1 , which can be optimized by adjusting doping and processing parameters. Even though several studies have focused on explaining the dynamic properties of doped and undoped Na 3 PS 4 , the driving forces that lead to fast Na + exchange are not yet completely understood. Here, we synthesized nanocrystalline, defect-rich cubic Na 3 PS 4 via a solid-state synthesis route and compared its properties with those of highly crystalline Ca-doped Na 3−2x Ca x PS 4 . The interconnected effects of doping and synthesis procedure on both structure and dynamic properties are investigated. X-ray diffraction reveals that the undoped samples show clear cubic and tetragonal symmetry, while for the doped samples, a phase mixture of both polymorphs is seen. High-resolution 23 Na magic angle spinning NMR spectra acquired at temperatures as low as −60 °C clearly reveal two different Na sites when ionic motion is partially frozen out. Ion dynamics of the powder samples were analyzed using high-precision broadband impedance spectroscopy and variable-temperature, time-domain 23 Na NMR spin−lattice relaxation rate measurements. Localized Na + jumps detected by NMR showed higher energy barriers but faster Na + dynamics for the Ca-doped samples. A similar trend was observed in conductivity spectroscopy with lowest activation energy for Na-ion transport in tetragonal Na 3 PS 4 but highest attempt frequencies for the hopping motion in Ca-doped Na 3 PS 4 with x = 0.135, making the doped sample the superior ion conductor at elevated temperatures. Our study highlights the importance of breaking down ionic transport in its elemental steps to understand the complex interplay of intrinsic and extrinsic parameters in solid electrolyte materials.

Recent Progress and Prospects on Sodium-Ion Battery and All-Solid-State Sodium Battery: A Promising Choice of Future Batteries for Energy Storage

“…Located on the two crystallographic inequivalent positions in tetragonal NPS, Na + are represented by orange and purple spheres, respectively. Reproduced with permission from ref . Copyright 2024 American Chemical Society.…”

“…The Ca-doped Na 2.73 Ca 0.135 PS 4 with local tetragonal symmetry exhibits superior performance at high temperatures compared to the tetragonal NPS. Additionally, the former has higher disorder effects due to doping, making it a promising SSE for high-temperature applications …”