First principle calculations on structural, electronic and transport properties of Li2TiS3 and Li3NbS4 positive electrode materials

First principle calculations based on density functional theory have been performed on lithium containing transition metal sulfides Li 2 TiS 3 and Li 3 NbS 4 which are recently identified as novel positive electrode materials for rechargeable Li + batteries. The calculations were performed to investigate the structural stability, electronic and transport properties of Li 2 TiS 3 and Li 3 NbS 4 along with their corresponding delithiated phases LiTiS 3 and Li 2 NbS 4 . In this study it has been observed that these lithium containing sulfur materials maintain their face-centered cubic structure upon extraction of Li + . To calculate the structural stability and volume change due to lithium extraction, the total energies of Li 2 TiS 3 , Li 3 NbS 4 and their corresponding delithiated phases LiTiS 3 and Li 2 NbS 4 have been computed by applying full potential linearized augmented plane wave (FP-LAPW) method implemented in WIEN2K. The equilibrium structural parameters for all the phases were determined by achieving total energy convergence. These electrode materials exhibit very small percentage of volume change with change in Li + concentration which accounts for excellent structural stability. The computed band structure along high symmetry lines in the Brillouin zone, total and partial density of states clearly reveals that the extraction lithium from these electrode materials does not change their metallic nature. The electronic conductivities of both lithiated and delithiated phases have been calculated by employing BoltzTrap which can be interfaced with WIEN2K. The topological distributions of electron charge density at various critical points within the system were analyzed with the use of CRITIC code which is based on Bader’s theory of atoms in molecules (AIM). From the charge density calculations, it was observed that, there is strong ionic bond and weak covalent bond between atoms of the compounds Li 2 TiS 3 and Li 3 NbS 4 . But the ionic bond nature was found to decrease in the delithiated phases LiTiS 3 and Li 2 NbS 4 . The calculated values of electronic conductivities and discharge voltages for both electrodes are found to be in accordance with the recent experimental reports.