The olivine-structured lithium ion phosphate (LiFePO4) is one of the most competitive candidates of cathode materials for the sustainable lithium ion battery (LIB) systems. However, the major drawback of olivine-structured LiFePO4 is the poor intrinsic electronic and lithium ion conductivities arising from the lack of mixed valency and the onedimensional lithium ion diffusion, which influence its high electrochemical performance, especially high rate capability. Nano-structured LiFePO4 materials offer a potential solution to enhance surface-to-volume ratio and reduce transport length for mobile charges, but they have high interfacial energy, aggregate easily and need more agglutinant in electrode, which seriously impact the electrochemical performance and practical applications of LiFePO4. Furthermore they continue to experience limitations as energy and power requirements escalate with the evolution of technology. Recently, three-dimensional (3D) porous LiFePO4 architectures have been widely designed and studied. This has led to increased interest in the development of cathode materials and processing capabilities necessary to enable high-performance, nextgeneration LIB system that can deliver large amounts of energy at high rates. In this review, we focus on 3D porous LiFePO4 architectures for high power LIBs, summarize and discuss its structure, synthesis, electrochemical behaviors, mechanism, and the problems encountered in its application. The major goal is to highlight the recent progress of 3D porous LiFePO4 architectures with high rate capability, high energy density and application.
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