磷酸盐系正极材料在锂离子电池中的应用进展

史姗姗; 沈建博; 彭操; 叶罕章; 张星; 白依冉; 王国栋; 许希军

doi:10.7536/PC20260216

化学进展 ›› :0- DOI: 10.7536/PC20260216

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磷酸盐系正极材料在锂离子电池中的应用进展

史姗姗 ¹ ,
沈建博 ² ,
彭操 ¹ ,
叶罕章 ¹ ,
张星 ¹ ,
白依冉 ¹ ,
王国栋 ¹^,^* ,
许希军 ³^,^*

作者信息 +

Shanshan Shi ¹ ,
Jianbo Shen ² ,
Peng Cao ¹ ,
Hangzhang Ye ¹ ,
Xing Zhang ¹ ,
Yiran Bai ¹ ,
Wang Guodong ¹^,^* ,
Xu Xijun ³^,^*

Author information +

文章历史 +

摘要

随着能源危机的日益加重，锂离子二次电池被认为是最具发展前景的能源存储装置。相比于三元材料，磷酸盐系正极材料由于其低廉的价格、优异的安全性、较高的循环稳定性和环境友好性而备受关注。橄榄石型LiMn_xFe_1-xPO₄（LMFP）作为高性能锂离子电池的正极材料，兼具磷酸铁锂LiFePO₄的高安全性与磷酸锰锂LiMnPO₄的高能量密度。然而，由于其较低的电子电导率、离子电导率，导致磷酸盐系正极材料在动力电池市场的应用仍然面临诸多挑战。本文首先分析了磷酸盐系正极材料在锂离子电池应用中所面临的限制因素，详细阐述了影响内部离子传输和电子传导的体相特性，包括相变机制、晶格畸变、点缺陷、元素掺杂、Fe/Mn比例和颗粒形态。并深入探讨了改善磷酸盐系正极材料放电比容量、放电电压和循环稳定性的方法，具体包括表面包覆、颗粒尺寸的调控、离子掺杂和形貌调控等。另外，对磷酸盐系正极材料的合成工艺与电化学性能之间的关系进行了探究，以了解各种工艺路线的优缺点，从而制备具有预期功能的材料。最后，展望了高性能磷酸盐系正极材料结构调控策略及其在锂离子电池中的应用前景。

Abstract

To address the global energy crisis, lithium-ion batteries (LIBs) have emerged as one of the most promising candidates for large-scale energy storage. Among various cathode materials, olivine-type phosphate compounds, particularly LiMnₓFe₁₋ₓPO₄ (LMFP), have attracted considerable attention owing to their distinct advantages over conventional layered ternary oxides, including lower cost, superior thermal and structural stability, extended cycling life, and enhanced environmental compatibility. By synergistically integrating the exceptional safety and long-term cyclability of LiFePO₄ with the high theoretical energy density of LiMnPO₄, LMFP represents a compelling candidate for next-generation LIB cathodes. Nevertheless, its intrinsic limitations of notably low electronic and ionic conductivity, which hindered its widespread application in high-power electronics. This manuscript provides a systematic investigation into the key factors affecting the electrochemical performance of phosphate cathode materials in LIBs, including (i) bulk material properties that govern ion transport and electron conduction; (ii) phase evolution during delithiation; (iii) lattice distortions induced by cationic substitution; (iv) thermodynamic and kinetic characteristics of point defect formation; (v) elemental doping strategies; (vi) optimization of the Fe/Mn molar ratio; and (vii) the influence of primary particle morphology on charge-transfer kinetics. Moreover, the synthesis techniques including solid-state reaction, sol-gel, hydrothermal, co-precipitation, and spray-drying, and their respective influences on microstructural characteristics and electrochemical performance were investigated. Additionally, this review evaluates critical engineering approaches aimed at improving practical discharge capacity, average voltage, and long-term cycling stability of phosphate cathodes. These strategies encompass surface modifications (e.g., conductive carbon or metal oxide coatings), precise control of particle size and distribution, targeted ionic doping (both cationic and anionic), and the rational design of hierarchical or composite particle architectures. By comparing the strengths, limitations, and scalability of these methods, it offers guidance for the rational design and scalable production of LMFP cathodes with optimized properties. Finally, outlines future directions for structural tuning of phosphate cathodes, including atomic-level doping and defect control, nanoscale morphology optimization, and macroscale electrode architecture design. These strategies are discussed with emphasis on their potential to enhance both the performance and practical applicability of LIBs.

关键词

磷酸盐系正极材料 / 锂离子电池 / 性能调控 / 电化学性能 / 合成工艺

Key words

Phosphate cathode materials / lithium-ion batteries / structural regulation / electrochemical performance / synthesis process

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史姗姗, 沈建博, 彭操, 叶罕章, 张星, 白依冉, 王国栋, 许希军. 磷酸盐系正极材料在锂离子电池中的应用进展[J]. 化学进展, , (): 0 DOI:10.7536/PC20260216

Shanshan Shi, Jianbo Shen, Peng Cao, Hangzhang Ye, Xing Zhang, Yiran Bai, Wang Guodong, Xu Xijun. Progress in Chemistry 0 DOI:10.7536/PC20260216

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Received	Published	Revised
2026-02-24	2026-07-24	2026-04-24
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