Uncertainty of exchange‐correlation functionals in density functional theory calculations for lithium‐based solid electrolytes on the case study of lithium phosphorus oxynitride

Abstract Amorphous lithium phosphorus oxynitride (LIPON) has emerged as a promising solid electrolyte for all‐solid‐state thin‐film lithium batteries. In this context, the use of theoretical modeling to characterize, understand, or screen material properties is becoming increasingly important to complement experimental analysis or elucidate features at atomistic level that are difficult to obtain through experimental studies. Density functional theory (DFT) is the method of choice for quantum mechanical material modeling at the atomistic scale. The current state of the art represents DFT values, such as the formation or migration energies relevant for bulk phase of materials, as absolute numbers. Estimating the accuracy or fluctuation range of the different density functionals is challenging. In order to investigate the thermodynamic and kinetic properties of LIPON by DFT, an approach to describe the fluctuation range caused by the choice of the exchange‐correlation (XC) functional is developed. Three different model systems were chosen to characterize various structural features of amorphous LIPON, which are distinguished by the cross‐linking of the PO u N 4‐ u ‐structural units. The uncertainty Ũ is introduced as a parameter describing the fluctuation range of energy values. The uncertainty approach does not determine the accuracy of DFT results, but rather a fluctuation range in the DFT results without the need for a reference value from a higher level of theory or experiment. The uncertainty was determined for both the thermodynamic Li‐vacancy formation energies and the kinetic Li‐vacancy migration energies in LIPON. We assume that the uncertainty approach can be applied to different material systems with different density functionals.