Modeling lithium-ion solid-state electrolytes with a pinball model

TL;DR

The paper presents a simplified, computationally inexpensive model called the 'pinball model' for simulating lithium ion diffusion in solid-state electrolytes, accurately capturing key properties while assuming frozen host lattices and ion ionization.

Contribution

The paper introduces the 'pinball model', a new efficient approach for simulating lithium diffusion that simplifies electronic interactions by freezing the host lattice and assuming full ionization.

Findings

The pinball model accurately reproduces static and dynamic lithium properties.

Frozen-lattice approximation is often sufficiently accurate for materials.

The model offers insights into charge-density and lattice vibration effects.

Abstract

We introduce a simple and efficient model to describe the potential energy surface of lithium diffusing in a solid-state ionic conductor. First, we assume that the Li atoms are fully ionized and we neglect the weak dependence of the electronic valence charge density on the instantaneous position of the Li ions. Second, we freeze the atoms of the host lattice in their equilibrium positions; consequently, also the valence charge density is frozen. We thus obtain a computational setup (the "pinball model") for which extremely inexpensive molecular dynamics simulation can be performed. To assess the accuracy of the model, we contrast it with full first-principles molecular dynamics simulations performed either with a free or frozen host lattice; in this latter case, the charge density still readjusts itself self-consistently to the actual positions of the diffusing Li ions. We show that the pinball model is able to reproduce accurately the static and dynamic properties of the diffusing Li ions - including forces, power spectra, and diffusion coefficients - when compared to the self-consistent frozen-host lattice simulations. The frozen-lattice approximation itself is often accurate enough, and certainly a good proxy in most materials. These observations unlock efficient ways to simulating the diffusion of lithium in the solid state, and provide additional physical insight into the respective roles of charge-density rearrangements or lattice vibrations in affecting lithium diffusion.