Effect of exchange-correlation functionals on the estimation of migration barriers in battery materials

Devi R., Singh, B., Canepa P. and Gautam G. S.; npj Comp. Mater., 8 160 (2022).

Abstract

Facile ionic mobility within host frameworks is crucial to the design of high-energy-density batteries with high-power-densities, where the migration barrier (Em) is the governing factor. Here, we assess the accuracy and computational performance of generalized gradient approximation (GGA), the strongly constrained and appropriately normed (SCAN), and their Hubbard U corrections, GGA+U and SCAN+U, within the density functional theory-nudged elastic band framework, in the prediction of Em as benchmarked against experimental data. Importantly, we observe SCAN to be more accurate than other frameworks, on average, albeit with higher computational costs and convergence difficulties, while GGA is a feasible choice for ‘‘quick’’ and ‘‘qualitative’’ Em predictions. Further, we quantify the sensitivity of Em with adding uniform background charge and/or the climbing image approximation in solid electrolytes, and the Hubbard U correction in electrodes. Our findings will improve the quality of Em predictions which will enable identifying better materials for energy storage applications.