Controlling the Lithium Intercalation Voltage in the Li(Mn 1-x Ni x ) 2 O 4 Spinel Via Tuning of the Ni Concentration: A Density Functional Theory Study

LiMn 2 O 4 spinel is a promising cathode material for secondary lithium-ion batteries. However, although showing a high average voltage of lithium intercalation, the material is structurally unstable, suffering lowering of the crystal symmetry lowering due to Jahn-Teller distortion of the six-fold Mn 3+ cations. Although Ni has been proposed as a suitable substitutional dopant to improve the structural stability of LiMn 2 O 4 and enhance the average lithium intercalation voltage, the thermodynamics of the Ni incorporation and its effect on the electrochemical properties of this spinel material are not yet known. In this work, we have employed density functional theory calculations with a Hubbard Hamiltonian (DFT+ U ) to investigate the thermodynamics of mixing of the Li(Mn 1- x Ni x ) 2 O 4 solid solution. Our results suggest that LiMn 1.5 Ni 0.5 O 4 is the most stable composition from room temperature up to at least 1000K, which is in excellent agreement with experiment. We also found that the configurational entropy is much lower than the maximum entropy at 1000K, indicating that higher temperatures are required to reach a fully disordered solid solution. A maximum average lithium intercalation voltage of 4.8 eV was calculated for the LiMn 1.5 Ni 0.5 O 4 composition, which is very close to the experimental value. The temperature was found to have a negligible effect on the Li intercalation voltage of the most stable composition. The findings reported here support the application of LiMn 1.5 Ni 0.5 O 4 as a suitable cathode material for lithium-ion batteries with a highly stable voltage of intercalation under a wide range of temperatures.