Lithium Metal Phosphate Cathodes for Energy Storage: Production Routes, Structure–Performance Relationships, Scale‐Up Challenges, and Recycling Perspectives

ABSTRACT Olivine‐type LiMPO 4 (M = Fe, Mn, Co, Ni, and mixed‐transition‐metal compositions) cathodes are among the most robust positive‐electrode families for rechargeable lithium‐ion batteries, offering high thermal stability and favorable safety characteristics for transportation and stationary energy storage. Practical performance is strongly governed by synthesis–structure–interface coupling: modest variations in particle size and morphology, anti‐site disorder, carbon topology, or surface chemistry can shift the dominant limitation from bulk diffusion to interfacial charge transfer or interphase transport. This review summarizes recent progress in LiMPO 4 production routes and relates processing parameters to microstructure and electrochemical behavior. Solid‐state, sol–gel, hydro/solvothermal, precipitation‐assisted, and rapid‐heating approaches are discussed in terms of how they control nucleation and growth and thereby determine primary‐particle geometry, secondary agglomeration, and accessible surface area. Strategies to mitigate intrinsic transport limitations are evaluated, including conductive‐carbon architectures, aliovalent and isovalent doping, mixed‐cation tuning in Li(Fe,Mn)PO 4 , defect engineering to reduce Li/Fe anti‐site formation, and interface stabilization via electrolyte/additive selection and surface coatings. Finally, electrode engineering, testing protocols, and scale‐up constraints are considered to outline practical pathways toward manufacturable LiMPO 4 cathodes with balanced rate capability, durability, and sustainability. By integrating production routes, structure–performance relationships, scale‐up constraints, and recycling perspectives, this review provides a practical framework for selecting LiMPO 4 cathode design strategies according to the dominant limitation of each chemistry.