Dona Susan Baji, Karayi Mangat Athira, Vanchiappan Aravindan
ABSTRACT The growing need for clean and sustainable energy technologies has put lithium‐ion batteries (LIBs) at the center of current energy storage systems. Among different cathode materials, olivine‐type phosphate compounds have gained consistent interest because of their inherent structural stability, high safety, and adjustable redox properties. In this group, mixed‐metal phosphates such as LiMn x Fe 1−x PO 4 (LMFP) have become notable candidates. They combined the high operating voltage of Mn‐based systems with the good kinetics and stability of Fe‐based systems. Specifically, LiMn 0.5 Fe 0.5 PO 4 strikes a strong balance between energy density, operating voltage, and safety, making it appealing for the next generation of LIBs. Despite thorough experiments and theoretical studies, the electrochemical performance of LiMn 0.5 Fe 0.5 PO 4 still faces intrinsic issues. This review addresses that gap by closely examining recent advancements in LiMn 0.5 Fe 0.5 PO 4 . It emphasizes the relationships among structure, properties, and performance and the fundamental reasons behind its electrochemical behavior. Key topics include phase transitions during cycling, inherent performance limitations, and the impacts of reducing particle size, engineering morphology, modifying surfaces, adding elements, and designing composite electrodes. Finally, the review points out ongoing challenges and suggests future research directions to enhance both the basic understanding and practical use of LiMn 0.5 Fe 0.5 PO 4 cathode materials in high‐energy LIBs.