Investigation of Low-Energy Lattice Dynamics and Their Role in Superionic Na Diffusion and Ultralow Thermal Conductivity of Na3PSe4 as a Solid-State Electrolyte

Abstract

The atomic dynamics of Na3PSe4 were investigated using a combination of neutron scattering experiments and ab initio and machine-learned molecular dynamics simulations to probe the interplay of fast ionic diffusion with atomic vibrations (phonons) of the host lattice. Our results reveal the existence of low-energy vibrational modes, simultaneously involving motions of Na+ ions and framework polyanion subunits, and show that these modes become strongly overdamped in the superionic regime as they couple with the Na+ hopping process. In particular, the Na+ migration energy landscape is strongly impacted by low-energy phonons derived from a soft acoustic branch of the host lattice, which modulates the diameter of the Na+ diffusion channel at the bottleneck. We find that an additional factor for the enhanced Na+ conductivity in Na3PSe4 is the presence of Na-vacancies, which also affect the low-frequency dynamics and thermal vibration amplitudes, pointing to an interplay between Na+ vacancies and host dynamics, jointly enhancing ionic diffusivity. Finally, we investigate the origin of ultralow thermal conductivities in Na3PSe4 and Na3PS4 using Green–Kubo simulations and find that low-energy acoustic phonon modes of the overall crystal framework provide a dominant contribution to the thermal conductivity.