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Capacity degradation and voltage fade of Li2MnO3 during cycling are the limiting factors for its practical use as a high-capacity lithium-ion battery cathode. Here, the simulated amorphisation and recrystallisation (A + R) technique is used, for generating nanoporous Li2MnO3 models of different lattice sizes (73 Å and 75 Å), under molecular dynamics (MD) simulations. Charging was carried out by removing oxygen and lithium ions, with oxygen charge compensated for, to restrain the release of oxygen, resulting in Li2−xMnO3−x composites. Detailed analysis of these composites reveals that the models crystallised into multiple grains, with grain boundaries increasing with decreasing Li/O content, and the complex internal microstructures depicted a wealth of defects, leading to the evolution of distorted cubic spinel LiMn2O4, Li2MnO3, and LiMnO2 polymorphs. The X-ray diffraction (XRD) patterns for the simulated systems revealed peak broadening in comparison with calculated XRD, also, the emergence of peak 2Θ ~ 18–25° and peak 2Θ ~ 29° were associated with the spinel phase. Lithium ions diffuse better on the nanoporous 73 Å structures than on the nanoporous 75 Å structures. Particularly, the Li1.00MnO2.00 shows a high diffusion coefficient value, compared to all concentrations. This study shed insights on the structural behaviour of Li2MnO3 cathodes during the charging mechanism, involving the concurrent removal of lithium and oxygen. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Li 2 MnO 3 has garnered significant interest as a potential cathode material due to its high electrochemical capacity, cost-effectiveness, and eco-friendliness. Nonetheless, its practical utilization is hindered by structural deterioration, which results in rapid capacity and voltage decay during cycling. To mitigate these challenges, cationic dopants have been incorporated to minimize structural collapse and enhance cathode material performance. Consequently, there is a strong desire to identify novel doped configurations as a remedial strategy for optimizing Li 2 MnO 3 properties. In this study, the stability of the Li 2 Mn 1- x TM x O 3 system (TM = Ni, Co, Cr, Ru) was explored using cluster expansion and Monte Carlo simulations. By employing cluster expansion, binary ground state diagrams were generated, revealing 73, 65, 90, and 83 newly stable phases in Li 2 Mn 1- x Ni x O 3, Li 2 Mn 1- x Co x O 3 , Li 2 Mn 1- x Cr x O 3 , and Li 2 Mn 1- x Ru x O 3 , respectively. The outcomes indicated that Li 2 Mn 0.83 Ni 0.17 O 3 , Li 2 Mn 0.5 Co 0.5 O 3, Li 2 Mn 0.5 Cr 0.5 O 3 , and Li 2 Mn 0.5 Ru 0.5 O 3 represent the most stable doped phases within the Li 2 MnO 3 system. The application of Monte Carlo simulations enabled the assessment of high-temperature characteristics across the entire range of TM concentrations (0 ≤ x ≤ 1), facilitating the construction of phase diagrams. The Li 2 Mn 1- x Ni x O 3, Li 2 Mn 1- x Co x O 3 , Li 2 Mn 1- x Cr x O 3 , and Li 2 Mn 1- x Ru x O 3 systems exhibited favorable mixing at temperatures of 850, 700, 1700, and 1300 K, respectively. These discoveries present a clear trajectory for optimizing the properties of Li 2 MnO 3 , offering valuable insights into conceptualizing innovative cathode materials characterized by enhanced stability and performance., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)