Thesis (Ph.D. (Physics)) -- University of Limpopo, 2019 / LiMn2O4 spinel (LMO) is a promising cathode material for secondary lithium-ion batteries which, despite its high average voltage of lithium intercalation, suffers crystal symmetry lowering due to the Jahn-Teller active six-fold Mn3+ cations. Although Ni has been proposed as a suitable substitutional dopant to improve the energy density of LiMn2O4 and enhance the average lithium intercalation voltage, the thermodynamics of Ni incorporation and its effect on the electrochemical properties of this spinel are not fully understood. Firstly, structural, electronic and mechanical properties of spinel LiMn2O4 and LiNixMn2-xO4 have been calculated out using density functional theory employing the pseudo-potential plane-wave approach within the generalised gradient approximation, together with Virtual Cluster Approximation. The structural properties included equilibrium lattice parameters; electronic properties cover both total and partial density of states and mechanical properties investigated elastic properties of all systems. Secondly, the pressure variation of several properties was investigated, from 0 GPa to 50 GPa. Nickel concentration was changed and the systems LiNi0.25Mn1.75O4, LiNi0.5Mn1.5O4 LiNi0.75Mn1.25O4 and LiNi0.875Mn1.125O4 were studied. Calculated lattice parameters for LiMn2O4 and LiNi0.5Mn1.5O4 systems are consistent with the available experimental and literature results. The average Mn(Ni)-O bond length for all systems was found to be 1.9 Å. The bond lengths decreased with an increase in nickel content, except for LiNi0.75Mn1.25O4, which gave the same results as LiNi0.25Mn1.75O4. Generally, analysis of electronic properties predicted the nature of bonding for both pure and doped systems with partial density of states showing the contribution of each metal in our systems. All systems are shown to be metallic as it has been previously observed for pure spinel LiMn2O4, and mechanical properties, as deduced from elastic properties, depicted their stabilities. Furthermore, the cluster expansion formalism was used to investigate the nickel doped LiMn2O4 phase stabilities. The method determines stable multi-component crystal structures and ranks metastable structures by the enthalpy of formation while iv maintaining the predictive power and accuracy of first-principles density functional methods. The ground-state phase diagram with occupancy of Mn 0.81 and Ni 0.31 generated various structures with different concentrations and symmetries. The findings predict that all nickel doped LMO structures on the ground state line are most likely stable. Relevant structures (Li4Ni8O16, Li12MnNi17O48, Li4Mn6Ni2O16, Li4Mn7NiO16 and Li4Mn8O16) were selected on the basis of how well they weighed the cross-validation (CV) score of 1.1 meV, which is a statistical way of describing how good the cluster expansion is at predicting the energy of each stable structure. Although the structures have different symmetries and space groups they were further investigated by calculating the mechanical and vibrational properties, where the elastic constants and phonon vibrations indicated that the structures are stable in accordance with stability conditions of mechanical properties and phonon dispersions. Lastly, a computer program that identifies different site occupancy configurations for any structure with arbitrary supercell size, space group or composition was employed to investigate voltage profiles for LiNixMn2-xO4. The density functional theory calculations, with a Hubbard Hamiltonian (DFT+U), was used to study the thermodynamics of mixing for Li(Mn1-xNix)2O4 solid solution. The results suggested that LiMn1.5Ni0.5O4 is the most stable composition from room temperature up to at least 1000K, which is in excellent agreement with experiments. It was 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. The maximum average lithium intercalation voltage of 4.8 eV was calculated for the LiMn1.5Ni0.5O4 composition which correlates very well with the experimental value. The temperature has a negligible effect on the Li intercalation voltage of the most stable composition. The approach presented here shows that moderate Ni doping of the LiMn2O4 leads to a substantial change in the average voltage of lithium intercalation, suggesting an attractive route for tuning the cathode properties of this spinel. / National Research Foundation (NRF)