For samples which undergo a series of heat treatment processes, a more p-type condition could oxidise the pre-formed Mn 3+ back to Mn 4+ , reducing the total number of redox active centers and leading to reduced capacity. Synthesis techniques that can take the advantage of the inherent defect chemistry of the material are more likely to achieve the fine tuning of electrochemical performance with target features. For example, Lee et al. utilised the preference for Li Ni antisite formation (on the 4b sites) to block the Mn/Ni ordering transition pathways during the annealing process of the Li-doped LMNO samples. Their Li-doped LMNO "Mn 3+ -free" samples annealed at 700 °C exhibited increased Mn/Ni disordering and showed enhanced cycling stability. In this case, the undesirable effects from Mn 3+ had been suppressed, as the Mn 3+ generated during the first (900 °C) treatment were re-oxidised to Mn 4+ when annealed at 700 °C. Unfortunately, the high concentration of Li Ni defects leads to a reduced capacity. The defect chemistry of LMNO therefore plays a crucial role in affecting the electrochemical performance. To design LMNO with optimum electrochemical performance, it is important to account for defect behaviour and effectively utilise it when developing synthesis methods.