Li-ion conduction in the LiBH₄:LiI system from Density Functional Theory calculations and Quasi-Elastic Neutron Scattering

The hexagonal high-temperature polymorph of LiBH4 is stabilized by solid solution with LiI to exhibit superionic Li+ ionic conductivity at room temperature. Herein, the mechanisms for the Li+ diffusion are investigated for the first time by density functional theory (DFT) calculations coupled to quasi-elastic neutron scattering (QENS) measurements with and without an applied bias potential of 3 V. DFT calculations show that lithium defects such as Frenkel pairs are easily formed at room temperature (formation energy of 0.44 eV) and low energy barriers (0.2 to 0.3 eV) are found between stable defect sites, giving rise to high defect mobility. QENS results at 380 K show long-range diffusion of Li+, with jump lengths of one unit cell and jump rates in agreement with those obtained from DFT, and the application of the bias potential increases the diffusion constant by a factor of 2. At 300 K, the QENS data reveal jump events of shorter length (2 Å), which could correspond to a jump process of Li+ interstitials to an intermediate lattice site, in agreement with DFT calculations.