共沉淀法可控制备磷酸锰铁锂正极材料研究进展

doi:10.19799/j.cnki.2095-4239.2025.0852

摘要/Abstract

摘要：

橄榄石型磷酸锰铁锂（LiMnₓFe_1-xPO₄, LMFP）作为下一代锂离子电池（LIBs）用正极材料，具有高能量密度、高安全性、低成本等优点。但LMFP本征电子电导率低、Li⁺扩散慢以及Mn³⁺引发的Jahn-Teller效应等关键因素制约其大规模应用。本文系统论述了工业化共沉淀法在可控制备LMFP材料的研究进展，重点探讨了以磷酸盐和草酸盐为代表的前驱体在实现原子尺度上的均匀混合与组分精确控制方面的显著优势；进一步阐述了共沉淀法与改性策略（如浓度梯度设计、碳包覆与离子掺）相结合对提升LMFP正极材料电导率与结构稳定性方面的协同作用。最后，本文强调了共沉淀法为高性能LMFP材料的可控制备提供可行方案，未来研究需致力于反应机理研究、工艺参数优化与多种策略的系统性整合，从而推动其在大规模储能系统中的商业化应用。

关键词: 锂离子电池（LIBs）, 磷酸锰铁锂（LiMn?Fe_1-xPO₄）, 正极材料, 共沉淀法

Abstract:

Olivine-type LiMn_xFe_1-xPO₄ (0<x<1, LMFP) is considered a promising cathode material for advanced lithium-ion batteries (LIBs) owing to its advantages of low cost, high safety, and high energy density. However, LMFP exhibits low ionic and electronic conductivity. Due to the Jahn-Teller effect, a high Mn content leads to severe Mn dissolution, which significantly hinders the large-scale application of LMFP. This review systematically summarizes recent advances in a controllable synthesis of LMFP cathodes via industrial co-precipitation methods. It highlights the significant advantages of phosphate and oxalate precursors in achieving atomic-level uniform mixing and precise compositional control. Moreover, the co-precipitation method can be effectively integrated with strategies such as concentration gradient design, carbon coating, and ion doping. These modification methods can effectively enhance the electron/ion transport pathways between material particles and improve the electrical conductivity of LMFP. Finally, based on recent advances in co-precipitation methods, this review proposes several research trends toward the commercial deployment of LMFP in large-scale energy storage systems.

Key words: lithium-ion batteries(LIBs), LiMn?Fe_1-xPO₄, cathode material, co-precipitation method

中图分类号:

O646.54

贾雨, 陈慧, 刘梦娜, 赵曦明, 屈龙. 共沉淀法可控制备磷酸锰铁锂正极材料研究进展[J]. 储能科学与技术, doi: 10.19799/j.cnki.2095-4239.2025.0852.

Yu JIA, Hui CHEN, Mengna LIU, Ximing ZHAO, Long QU. Recent advances in a controllable synthesis of LiMnₓFe_1-xPO₄ cathodes via co-precipitation methods[J]. Energy Storage Science and Technology, doi: 10.19799/j.cnki.2095-4239.2025.0852.

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前驱体类型	合成条件	产品特性	电化学性能（mAh/g）
Mn_xFe_1-xPO₄	沉淀剂：H₃PO₄ 溶剂：有机溶剂（如乙醇） pH：<2 添加剂：HNO₃、H₂O₂等做氧化剂其他：后续煅烧需H₂或还原碳	颗粒内部具有纳米尺度的孔隙结构，易于提升体积能量密度	140.3(0.1C)、79.6(5C)^[33] 140.2(0.1C)、100.3(3C)^[52] 140.4(0.1C)、109.6(5C)^[63]
(MnₓFe_1-x)₃(PO₄)₂	沉淀剂：NH₄H₂PO₄ 溶剂：水 pH：≈6.5（氨水调节）气氛：N₂	环境友好，锂化无需还原碳	140.1(0.1C)^[25] 150.6(0.1C)、110.1(5C)^[36] 151.2(0.1C)、98.8(5C)^[53]
NH₄Mn_xFe_1-xPO₄	沉淀剂：(NH₄)₂HPO₄ 溶剂：水 pH：近中性气氛：N₂	结构相容性好，转化动力学优势，离子交换高效	145.6(0.1C)、125.3(5C)^[12] 139.1(0.1C)^[55] 146.9(0.1C)、119.8(5C)^[56] 140.1(0.1C)、100.6(5C)^[59]
MnₓFe_1-xC₂O₄	沉淀剂：草酸、草酸铵、草酸钠溶剂：水 pH：≈4.5 温度：90℃（控制相分离）添加剂：抗坏血酸	分解温度低于锂化温度，且在分解过程中体积变化较小、无残留杂质，可原位掺杂	158.6(0.05C)、80.8(10C)^[37] 160.3(0.1C)、125.4(20C)^[57] 158.6(0.1C)、122.6(10C)^[61] 140.3(0.1C)、110.6(5C)^[64] 150.1(0.1C)、80.6(10C)^[65]

掺杂元素	材料组成	结构影响	电化学性能（mAh/g）	参考文献
Mg²⁺	Li(Fe_0.4Mn_0.6)_0.97Mg_0.03PO₄/C	促进Li⁺迁移，降低电荷转移电阻	153.65(0.2C)、138.83(5C)、134.68、(10C)	^[31]
Mg²⁺	LiMn_0.5978Fe_0.3522Mg_0.0506PO₄/C	提高Li⁺扩散系数，降低界面电阻，抑制Jahn-Teller效应	150.1(0.1C)141.4(1C)111.6(5C)	^[59]
Mg²⁺	LiFe_0.39Mg_0.01Mn_0.6PO₄/C	提高电导率以及Li⁺扩散系数	158.1(0.1C)、154.6(0.5C)、131.52(5C)	^[80]
Mg²⁺	LiFe_0.7Mn_0.25Mg_0.05PO₄/C	降低材料反应的阻抗和极化，从而提高其导电性和Li⁺扩散系数	163.2(0.1C)、155.2(0.2C)、142.0(1C)	^[81]
Ni²⁺	LiFe_0.4Mn_0.55Ni_0.05PO₄/C	促进Li⁺迁移，降低反应极化	142(0.1C)、139(0.2C)、110(1C)	^[24]
Ni²⁺	LiMn_0.6Fe_0.38Ni_0.02PO₄/C	降低晶体的表面能，抑制晶体的生长，从而使晶体保持在适宜尺寸和规则形貌	147.3(1C)、125.1(10C)、115.4(15C)	^[82]
Ti⁴⁺	Li(Fe_0.6Mn_0.4)_0.97Ti_0.03PO₄/C	该材料降低电位极化现象，同时其强Ti-O配位结构抑制了Jahn-Teller效应	163.53(0.1C)、140.59(1C)、94.08(5C)	^[83]
Nb⁵⁺	Li_0.98Mn_0.6Fe_0.4Nb_0.02PO₄/C	减少反位缺陷，促进Li⁺迁移,有效地抑制Jahn-Teller效应和锰溶解	155.63(0.1C)、144.03(2C)、134(5C)	^[12]
Mg²⁺-Nb⁵⁺	LiMn_0.48Fe_0.48Mg_0.03Nb_0.01PO₄/C	表面的Nb掺杂增强离子/电子传输，颗粒内部Mg掺杂改善Mn^2+/3+氧化还原反应动力学	141.0(0.1C)、129.6(1C)、120.3(5C)	^[32]
V³⁺-Ti⁴⁺	LiFe_0.6Mn_0.4PO₄-V-Ti/C	降低材料反应的阻抗和极化，增强结构稳定性，提高导电性	161.9(0.1C)、149.6(2C)、141.5(5C)	^[84]