Self-Consistent-Charge Density-Functional Tight-Binding Parameters for Modeling an All-Solid-State Lithium Battery.

All-solid-state lithium-ion batteries have been a promising solution for next-generation energy storage due to their safety and potentially high energy density. In this work, we developed a density-functional tight-binding (DFTB) parameter set for modeling solid-state lithium batteries, focusing on the band alignment at electrolyte/electrode interfaces. Despite DFTB being widely applied in the simulation of large-scale systems, parametrization is usually done for single materials, and less attention is paid to band alignment among multiple materials. Band offsets at the electrolyte/electrode interfaces are key quantities determining the performance. Here, an automated global optimization method based on DFTB confinement potentials of all elements is developed, while the band offsets between electrodes and electrolytes are introduced as constraints during the optimization. The parameter set is applied to model an all-solid-state Li/Li2PO2N/LiCoO2 battery, and its electronic structure shows a good agreement with that from density-functional theory (DFT) calculations.