Soft Anharmonic Coupled Vibrations of Li and SiO4 Enable Li-ion Diffusion in Amorphous Li2Si2O5

TL;DR

This study combines neutron scattering experiments and molecular dynamics simulations to reveal how low-energy vibrational modes and SiO4 polyhedral dynamics facilitate Li+ diffusion in amorphous Li2Si2O5, highlighting the role of vibrational coupling.

Contribution

It uncovers the atomic vibrational mechanisms, especially low-energy modes, that enable Li+ diffusion in amorphous Li2Si2O5, integrating experimental and simulation insights.

Findings

Low-energy vibrational modes are present in amorphous phase but absent in crystalline phase.

Li+ diffusion is enhanced by coupling with SiO4 vibrational modes.

Vibrational dynamics drive vitrification and phase transition at high temperatures.

Abstract

We present the investigations on atomic dynamics and Li+ diffusion in crystalline and amorphous Li2Si2O5 using quasielastic (QENS) and inelastic neutron scattering (INS) studies supplemented by ab-initio molecular dynamics simulations (AIMD). The QENS measurements in the amorphous phase of Li2Si2O5 show a narrow temperature window (700 < T < 775 K), exhibiting significant quasielastic broadening corresponding to the fast Li+ diffusion and relaxation of SiO4 units to the crystalline phase. Our INS measurements clearly show the presence of large phonon density of states (PDOS) at low energy (low-E) in the superionic amorphous phase, which disappear in the non-superionic crystalline phase, corroborating the role of low-E modes in Li+ diffusion. The frustrated energy landscape and host flexibility (due to random orientation and vibrational motion of SiO4 polyhedral units) play an essential role in diffusing the Li+. We used AIMD simulations to identify that these low-E modes involve a large amplitude of Li vibrations coupled with SiO4 vibrations in the amorphous phase. At elevated temperatures, these vibrational dynamics accelerate the Li+ diffusion via a paddle-wheel like coupling mechanism. Above 775 K, these SiO4 vibrational dynamics drive the system into the crystalline phase by locking SiO4 and Li+ into deeper minima of the free energy landscape and disappear in the crystalline phase. Both experiments and simulations provide valuable information about the atomic level stochastic and vibrational dynamics in Li2Si2O5 and their role in Li+ diffusion and vitrification.