Efficient energy storage techniques are prerequisites for the utilization of sustainable energy. During the recent decades, the emergence of lithium-ion batteries (LIBs) has greatly promoted the development of portable electronic equipment and electrical vehicles, yet, there is still a large difference between supply and demand, especially for large-scale energy storage. Sodium-ion batteries (SIBs) are regarded as promising alternatives for LIBs based on the abundant sodium resources and the reaction pattern that is comparable with that of LIBs. Among these cathode materials, phosphate-based polyanion-type materials have attracted much attention due to their inherent advantages such as uniquely stable structures and high operating potentials. Moreover, the small structural variations that occur during the cycling process within phosphate-based materials facilitate excellent rate performance and cycling stability. However, there still exist challenging issues within phosphate-based polyanion-type materials for further application due to their intrinsically low electronic conductivity and limited energy density. Many efforts will be needed before they can be widely used as commercial SIB cathode materials. In this review, the recent progress of phosphate-based polyanion-type electrode materials is briefly summarized based on compositional structure, reaction mechanism, fundamental issues, and remaining difficulties for phosphates, pyrophosphates, NASICON-type, and fluoride phosphate types of materials. Furthermore, structural-induced high performance and the flexible manipulation of material structure toward rational design of phosphate-based polyanion-type electrodes have also been discussed. We hope this review can provide some insights into the working mechanisms of and potential improvements of phosphate-based polyanion-type electrode materials and inspires further design enhancements of SIB materials.

高效的储能技术是利用可持续能源的先决条件。近几十年来，锂离子电池（LIBs）的出现极大地推动了便携式电子设备和电动汽车的发展，但供需差距仍然很大，尤其是在大规模储能方面。钠离子电池（SIBs）因其丰富的钠资源和与LIBs相当的反应模式被认为是LIBs的有希望的替代品。在这些正极材料中，磷酸盐基聚阴离子型材料由于其独特的稳定结构和高工作电位等固有优势而备受关注。而且，磷酸盐基材料在循环过程中发生的微小结构变化有助于出色的倍率性能和循环稳定性。然而，由于磷酸盐基聚阴离子型材料固有的低电子电导率和有限的能量密度，在进一步应用中仍存在挑战性问题。在它们被广泛用作商业 SIB 正极材料之前，还需要付出很多努力。本文从磷酸盐、焦磷酸盐、NASICON 型和氟化物磷酸盐类型材料的组成结构、反应机理、基本问题和存在的困难等方面，对磷酸盐基聚阴离子型电极材料的最新进展进行了简要总结。此外，还讨论了结构诱导的高性能和材料结构的灵活操纵，以合理设计磷酸盐基聚阴离子型电极。我们希望这篇综述可以为磷酸盐基聚阴离子型电极材料的工作机制和潜在改进提供一些见解，并激发 SIB 材料的进一步设计改进。