Impacts of vacancy-induced polarization and distortion on diffusion in solid electrolyte Li3OCl. (29th November 2021)

• Record Type: Journal Article
• Authors: Mehmedović, Zerina; Wei, Vanessa; Grieder, Andrew; Shea, Patrick; Wood, Brandon C.; Adelstein, Nicole
• Is Part Of: Philosophical transactions. Volume 379:Number 2211(2021)
• Publication Date: 2021-11-29
• Subjects: superionic -- correlated motion -- solid-state battery; Physical sciences -- Periodicals; Engineering -- Periodicals; Mathematics -- Periodicals; 500
• DOI: 10.1098/rsta.2019.0459
• Languages: English
• ISSNs: 1364-503X

Abstract

Abstract : Lithium-rich oxychloride antiperovskites are promising solid electrolytes for enabling next-generation batteries. Here, we report a comprehensive study varying Li + concentrations in Li 3 OCl using ab initio molecular dynamics simulations. The simulations accurately capture the complex interactions between Li + vacancies (V Li ′ ), the dominant mobile species in Li 3 OCl . The V Li ′ polarize and distort the host lattice, inducing additional non-vacancy-mediated diffusion mechanisms and correlated diffusion events that reduce the activation energy barrier at concentrations as low as 1.5% V Li ′ . Our analyses of discretized diffusion events in both space and time illustrate the critical interplay between correlated dynamics, polarization and local distortion in promoting ionic conductivity in Li 3 OCl . This article is part of the Theo Murphy meeting issue 'Understanding fast-ion conduction in solid electrolytes'.