P06 - Accurate Electronic Properties and Intercalation Voltages of Li-Ion Cathode Materials from Extended Hubbard Functionals
DescriptionThe design of novel cathode materials for Li-ion batteries requires accurate first-principles predictions of their properties. Density-functional theory (DFT) with standard (semi-)local functionals fails due to the strong self-interaction errors of partially filled d shells of transition-metal (TM) elements. Here, we show for phospho-olivine and spinel cathodes that DFT with extended Hubbard functionals correctly predicts the "digital" change in oxidation states of the TM ions for the mixed-valence phases occurring at intermediate Li concentrations, leading to voltages in remarkable agreement with experiments [1,2]. This is achieved thanks to the use of onsite and intersite Hubbard parameters computed from density-functional perturbation theory with Lowdin-orthogonalized atomic orbitals . We thus show that the inclusion of intersite Hubbard interactions is essential for the accurate prediction of thermodynamic quantities when electronic localization occurs in the presence of inter-atomic orbital hybridization. This work paves the way for reliable first-principles studies of other families of cathode materials without relying on empirical fitting or calibration procedures.
 I. Timrov et al., PRX Energy 1, 033003 (2022).
 I. Timrov et al., arXiv:2301.11143 (2023).
 I. Timrov et al., PRB 103, 045141 (2021).
TimeTuesday, June 2719:30 - 21:30 CEST