First-Principles Study on the Effect of Lithiation in Spinel LixMn2O4 (0 ≤ x ≤ 1) Structure: Calibration of CASTEP and ONETEP Simulation Codes

Lithium-manganese-oxide (Li-Mn-O) spinel is among the promising and economically viable, high-energy density cathode materials for enhancing the performance of lithium-ion batteries. However, its commercialization is hindered by its poor cyclic performance. In computational modelling, pivotal in-depth understanding of material behaviour and properties is sizably propelled by advancements in computational methods. Hence, the current work compares traditional DFT (CASTEP) and linear-scaling DFT (ONETEP) in a LiMn2O4 electronic property study to pave way for large-scale DFT calculations in a quest to improve its electrochemical properties. The metallic behaviour of LixMn2O4 (0.25 ≤ x ≤ 1) and Li2Mn2O4 was correctly determined by both CASTEP and ONETEP code in line with experiments. Furthermore, OCV during the discharge cycle deduced by both codes is in good accordance and is between 5 V and 2.5 V in the composition range of 0 ≤ x ≤ 1. Moreover, the scaling of the ONETEP code was performed at South Africa's CHPC to provide guidelines on more productive large-scale ONETEP runs. Substantial total computing time can be saved by systematically adding the number of processors with the growing structure size. The study also substantiates that true linear scaling of the ONETEP code is achieved by a systematic truncation of the density kernel.