Mphahlele Mamonamane Gratitude, Masedi Mallang Cliffton, Malatji Kemeridge Tumelo, Ngoepe Phuti Esrom, Ledwaba Raesibe Sylvia
Materials Modelling Centre, University of Limpopo, Private Bag X1106, Sovenga 0727, South Africa.
ACS Omega. 2024 May 22;9(22):23400-23409. doi: 10.1021/acsomega.3c10357. eCollection 2024 Jun 4.
LiMnO 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 LiMnO properties. In this study, the stability of the LiMn TM O 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 LiMn Ni O LiMn Co O, LiMn Cr O, and LiMn Ru O, respectively. The outcomes indicated that LiMnNiO, LiMnCoO LiMnCrO, and LiMnRuO represent the most stable doped phases within the LiMnO system. The application of Monte Carlo simulations enabled the assessment of high-temperature characteristics across the entire range of TM concentrations (0 ≤ ≤ 1), facilitating the construction of phase diagrams. The LiMn Ni O LiMn Co O, LiMn Cr O, and LiMn Ru O 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 LiMnO, offering valuable insights into conceptualizing innovative cathode materials characterized by enhanced stability and performance.
由于具有高电化学容量、成本效益和环境友好性，LiMnO作为一种潜在的阴极材料引起了广泛关注。尽管如此，其实际应用受到结构劣化的阻碍，这导致在循环过程中容量和电压迅速衰减。为了应对这些挑战，已引入阳离子掺杂剂以尽量减少结构坍塌并提高阴极材料性能。因此，迫切需要确定新颖的掺杂构型作为优化LiMnO性能的补救策略。在本研究中，使用团簇展开和蒙特卡罗模拟探索了LiMnTM O系统（TM = Ni、Co、Cr、Ru）的稳定性。通过采用团簇展开，生成了二元基态图，分别揭示了LiMnNiO、LiMnCoO、LiMnCrO和LiMnRuO中73、65、90和83个新的稳定相。结果表明，LiMnNiO、LiMnCoO、LiMnCrO和LiMnRuO代表LiMnO系统中最稳定的掺杂相。蒙特卡罗模拟的应用能够评估整个TM浓度范围（0≤≤1）内的高温特性，有助于构建相图。LiMnNiO、LiMnCoO、LiMnCrO和LiMnRuO系统分别在850、700、1700和1300 K的温度下表现出良好的混合。这些发现为优化LiMnO的性能提供了明确方向，为构思具有更高稳定性和性能的创新阴极材料提供了有价值的见解。
