Understanding the effect of lattice polarisability on the electrochemical properties of lithium tetrahaloaluminates, LiAlX4 (X = Cl, Br, I)

Abstract

Establishing links between the structure and physical properties of solid-state ionic conductors contributes not only to a rationale of their fundamental nature, but also provides design principles to accelerate the discovery of new materials. Lithium ion conduction in complex halides is not well-elucidated and so the interplay between lattice dynamics, electronic structure, and electrochemical properties in such halides has been explored in the isostructural family of lithium tetrahaloaluminates LiAlX₄ (X = Cl, Br, I). Using a combination of experimental methods (diffuse reflectance UV-Vis spectroscopy, pulse-echo speed of sound measurements, Raman spectroscopy, inelastic neutron scattering) and periodic Density Functional Theory (DFT) based calculations, we demonstrate that softer lattices (quantified in terms of Debye frequencies or Li-phonon band centres as a function of X) provide lower activation energies for Li⁺ migration. However, the relationship between polarisability and Li⁺ conductivity is not straightforward. In line with expectations emergent from the Meyer–Neldel rule, the activation energy for Li⁺ hopping, E_a, and the pre-exponential terms collated as σ₀ in the Arrenhius equation for activated conductivity, correlate. It is also evident that the electrochemical oxidative potential limit correlates with the X⁻ phonon band centre in the Vibrational Density of States (VDOS) and that the Electrochemical stability Window (EW) and optical band gap are interlinked, as expected.