DFT Modelling of Explicit Solid-Solid Interfaces in Batteries: Methods and Challenges

TL;DR

This paper reviews the use of Density Functional Theory for modeling explicit solid-solid interfaces in batteries, highlighting key challenges and proposing directions for methodological development to better understand interfacial phenomena.

Contribution

It identifies critical challenges in DFT modeling of battery interfaces and suggests new computational approaches and interdisciplinary insights to address these issues.

Findings

Explicit interface models reveal contact potentials and electric fields.

Surface 'dirtiness' affects interfacial properties and modeling.

Kinetic factors govern interfacial structures, not just thermodynamics.

Abstract

Density Functional Theory (DFT) calculations of electrode material properties in high energy density storage devices like lithium batteries have been standard practice for decades. In contrast, DFT modelling of explicit interfaces in batteries arguably lacks universally adopted methodology and needs further conceptual development. In this paper, we focus on solid-solid interfaces, which are ubiquitous not just in all-solid state batteries; liquid-electrolyte-based batteries often rely on thin, solid passivating films on electrode surfaces to function. We use metal anode calculations to illustrate that explicit interface models are critical for elucidating contact potentials, electric fields at interfaces, and kinetic stability with respect to parasitic reactions. The examples emphasize three key challenges: (1) the "dirty" nature of most battery electrode surfaces; (2) voltage calibration and control; and (3) the fact that interfacial structures are governed by kinetics, not thermodynamics. To meet these challenges, developing new computational techniques and importing insights from other electrochemical disciplines will be beneficial.