化工新型材料

化工新型材料 ›› 2026, Vol. 54 ›› Issue (6) : 71-76. DOI: 10.19817/j.cnki.issn1006-3536.2026.06.038

综述与专论

磷酸锰铁锂正极材料的改性研究进展

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作者信息 +

Research progress on modification of lithium manganese iron phosphate cathode materials

Li Yong¹, Shi Zhe¹, Tang Yi², Bo Yuyao², Cao Zhijie¹

Author information +

文章历史 +

Received
2025-07-16
Issue Date	Revised Date
2026-06-18	2025-07-16

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摘要

磷酸锰铁锂正极材料(LiMn_xFe_1-xPO₄,0<x<1,LMFP)作为磷酸铁锂正极材料(LFP)的升级方案,兼具LFP的稳定、廉价、环保以及磷酸锰锂(LMP)的高工作电压(约4.1V vs.Li⁺/Li)、高能量密度等优点,具有广阔的应用前景。然而,本征电子/离子电导率低和Jahn-Teller效应导致的结构不稳定等问题,严重制约了LMFP的实际应用。系统地综述了LMFP的结构特征、存在的问题以及改性研究进展,重点介绍了离子掺杂、粒径优化、形貌设计和表面包覆等改性策略的研究动态,并展望了LMFP未来的发展方向和应用前景。

Abstract

Lithium manganese iron phosphate cathode material (LiMn_xFe_1-xPO₄,0<x<1,LMFP),an upgraded version of lithium iron phosphate (LFP),combines the advantages of LFP such as structural stability,low cost,and environmental friendliness,with the high working voltage (～4.1V vs.Li⁺/Li) and enhanced energy density of lithium manganese phosphate(LMP),offering broad application prospects.However,its practical implementation is significantly hindered by inherently low electronic/ionic conductivity and structural instability induced by the Jahn-Teller effect.This paper systematically reviewed the structural characteristics,key challenges,and recent research progress in modifying LMFP cathode materials.It specifically focused on the advances in modification strategies,including ion doping,particle size optimization,morphology design and surface coating.Furthermore,the paper discussed the future development directions and application prospects of LMFP.

关键词

锂离子电池 / 正极材料 / 磷酸锰铁锂 / 改性

Key words

lithium-ion batteries / cathode material / LMFP / modification

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磷酸锰铁锂正极材料的改性研究进展[J]. 化工新型材料, 2026, 54(6): 71-76 DOI:10.19817/j.cnki.issn1006-3536.2026.06.038

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参考文献

原文顺序 | 出版日期 | 本文引用

[1] Chen Z M,Yang X J,Zhang H H,et al.Research on the impact of social responsibility fulfillment of new energy vehicle enterprises on competitiveness under the ‘Dual Carbon’ goal[J].Academic Journal of Business & Management,2025,7(4):130-138.
[2] 任沁沁.超3000万辆新能源车奔跑在中国道路上[N/OL].新华每日电讯,2025-01-19(002).[2025-07-16].http:www.mrdx.cn/content/20250119/Page02DK.htm.
[3] Song C H,Wang M M,Lu Y K,et al.Research progress in the preparation methods of iron phosphate materials[J].Journal of Salt Lake Research,2025,33(2):108-114.
[4] Wen Z P,Pan K,Wei Y,et al.Research progress in lithium manganese iron phosphate cathode material modification[J].Energy Storage Science and Technology,2024,13(3):770-787.
[5] Li S Z,Zhang H,Liu Y,et al.Comprehensive understanding of structure transition in LiMn_yFe_1-yPO₄ during delithiation/lithiation[J].Advanced Functional Materials,2024,34(4):2310057.
[6] Jiang F,Qu K,Wang M S,et al.Atomic scale insight into the fundamental mechanism of Mn doped LiFePO₄[J].Sustainable Energy & Fuels,2020,4(6):2741-2751.
[7] Monica Kosa,Doron Aurbach,Dan Thomas Major.First-principles evaluation of the inherent stabilities of pure Li_xMPO₄(M=Mn,Fe,Co) and mixed binary Li_xFe_yM_1-yPO₄ (M=Mn,Co) olivine phosphates[J].Materials Chemistry and Physics,2016,174:54-58.
[8] Wang L,Li Y,Wu J,et al.Synthesis mechanism and characterization of LiMn_0.5Fe_0.5PO₄/C composite cathode material for lithium-ion batteries[J].Journal of Alloys and Compounds,2020,839:155653.
[9] Wang L,Zhang H Q,Li Y,et al.Improving the rate performance of LiMn_0.5Fe_0.5PO₄/C materials by the precursor method[J].Journal of Materials Research and Technology,2022,20:4018-4025.
[10] 齐美洲,汪志全,李道聪,等.LiMn_1-xFe_xPO₄正极材料制备方法的研究进展[J].化工新型材料,2018,46(2):59-62.
[11] 刘照,刘西川,李卓航,等.磷酸锰铁锂复合正极材料的研究进展[J].辽宁化工,2025,54(1):146-149.
[12] Cho E,Jeong S,Kim D,et al.Sodium-doped LiFe_0.5Mn_0.5PO₄ using sodium gluconate as both reducing agent and a doping source in lithium-ion batteries[J].Industrial & Engineering Chemistry Research,2025,143:729-739.
[13] Hu H,Li H,Lei Y,et al.Mg-doped LiMn_0.8Fe_0.2PO₄/C nano plate as a high performance cathode material for lithium-ion batteries[J].Energy Storage,2023,73:109006.
[14] Liu W F,Liu X C,Hao R,et al.Contribution of calcium ion doping to the rate property for LiFe_0.5Mn_0.5PO₄/C[J].Journal of Electroanalytical Chemistry,2023,929:117117.
[15] Liu F F,Wu T T,Wen S Y,et al.A study on dissolution of transition metal ions and influence on the cycling performance of LiMn_0.6Fe_0.4PO₄[J].Energy Storage Science and Technology,2025,14(1):13-20.
[16] Jeong B J,Sung J Y,Jiang F,et al.Providing high stability to suppress metal dissolution in LiMn_0.5Fe_0.5PO₄ cathode materials by Zn doping[J].Energy Storage,2024,96:112552.
[17] Wang P,Zhang E,Fang Y,et al.Na/Co dual-doped olivine LiMn_0.6Fe_0.4PO₄ cathode with superior reaction kinetics for Li-ion batteries[J].Solid State Electrochemistry,2024,28:4303-4310.
[18] Zhang Q D,Liu Y Y,Chang C K,Zheng J N.Modulating the lattice structure via Cr³⁺ doping in LiFe_0.4Mn_0.6PO₄ cathode for improved rate behavior and promoted cyclic performance[J].Energy Storage,2024,01:113799.
[19] Li Z,You Y,Zhu,Z Q,et al.The synergistic enhancement of electrochemical performance in LiMn_0.5Fe_0.5PO₄ through V doping and V₂CT_x MXene coating[J].Energy Storage,2025,110:115111.
[20] Yu S,Jin H,Yang M,et al.Synthesis and modification of F-doped olivine LiFe_0.5Mn_0.5PO₄ cathode materials for Li-ion batteries[J].Chemical Industry and Engineering Progress,2024,43:302-309.
[21] Sin B C,Singh L,An J,et al.Enhanced electrochemical performance and manganese redox activity of LiFe_0.4Mn_0.6PO₄ by iodine anion substitution as cathode material for Li-ion battery[J].Power Sources,2016,313:112-119.
[22] Zhang W,Du F Y,Dai Y,Zheng J C.Strain engineering of Li ion migration in olivine phosphate cathode materials LiMPO₄(M=Mn,Fe,Co) and (LiFePO₄)_n(LiMnPO₄)_m superlattices[J].Chemical Physics,2023,25:6142-6152.
[23] Hou Y,Pan G,Sun Y,et al.LiMn_0.8Fe_0.2PO₄/C nano spheres@graphene nano ribbons prepared by the biomineralization process as the cathode for lithium-ion batteries[J].ACS Applied Materials & Interfaces,2018,10:16500-16510.
[24] Seo I,Senthilkumar B,Kim K H,et al.Atomic structural and electrochemical impact of Fe substitution on nano porous LiMnPO₄[J].Journal of Power Sources,2016,320:59-67.
[25] Yao X,Li D,Guo L,et al.Carbon-coated LiMn_0.8Fe_0.2PO₄ cathodes for high-rate lithium-ion batteries[J].Advanced Composites and Hybrid Materials,2024,7:63.
[26] Wang Y,Wu C Y,Yang H,Duh J G.Rational design of a synthetic strategy,carburizing approach and pore-forming pattern to unlock the cycle reversibility and rate capability of micro-agglomerated LiMn_0.8Fe_0.2PO₄ cathode materials[J].Journal of Materials Chemistry A,2018,6(22):10395.
[27] Wang L,Li Y,Wu J,et al.Synthesis mechanism and characterization of LiMn_0.5Fe_0.5PO₄/C composite cathode material for lithium-ion batteries[J].Journal of Alloys and Compounds,2020,839:155653.
[28] Zhang B C,Meng W,Gong Y,et al.[001] -oriented LiMn_0.6Fe_0.4PO₄/C nanorod microspheres contributing high-rate performance to olivine-structured cathode for lithium-ion battery Mater[J].Materials Today Energy,2022,30:01162.
[29] Lin W,Hu X,Wu Y,et al.Insitu self-catalyzed fabricating carbon nanotubes on[010] preferential LiMn_0.5Fe_0.5PO₄ nanoplates to achieve excellent high rate performance[J].Carbon,2024,230:119636.
[30] Ma F,Zhang X,He P,et al.Synthesis of hierarchical and bridging carbon-coated LiMn_0.9Fe_0.1PO₄ nanostructure as cathode material with improved performance for lithium ion battery[J].Power Sources,2017,359:408-414.
[31] Huang S L,Lin W Z,Li L W,et al.Pathway for high-energy density LiMnFePO₄ cathodes[J].Progress In Natural Science-materials International,2023,33:126-131.
[32] 詹皓博,刘世琦,王勤,等.锂离子电池磷酸锰铁锂正极材料研究进展[J].稀有金属,2023,47(12):1669-1688.
[33] 刘照,刘西川,李卓航,等.磷酸锰铁锂复合正极材料的研究进展[J].辽宁化工,2025,54(1):146-149.
[34] Chang L J,Wei A L,Bi X,et al.Study on the preparation of LiMn_1-xFe_xPO₄/C from pyrolusite based on first-principles and its electrochemical properties[J].Ceramics International,2023,49(22):35757-35772.
[35] Xie X,Zhang B,Hu G,et al.A new route for green synthesis of LiFe_0.25Mn_0.75PO₄/C@rGO material for lithium ion batteries[J].Journal of Alloys and Compounds,2021,853:157106.
[36] Lin W,Hu X,Wu Y,et al.In-situ self-catalyzed fabricating carbon nanotubes on[010] preferential LiMn_0.5Fe_0.5PO₄ nano plates to achieve excellent high rate performance[J].Carbon,2024,230:119636.
[37] Pan D,Liu Z,Li C,et al.Modification of LiMn_0.6Fe_0.4PO₄ lithium-ion battery cathode materials with a fluorine-doped carbon coating[J].Particuology,2024,92:278-287.
[38] Fan R Z,Fang C L,Hu Z,et al.Construction of high performance N-doped carbon coated LiMn_0.8Fe_0.2PO₄ nano crystal cathode for lithium-ion batteries[J].Journal of Alloy sand Compounds,2021,876:160090.
[39] Li H,Xiao X,Wu J,et al.Progress of LiMn_yFe_1-yPO₄ cathode materials:from mechanisms,defects,modification methods to applications[J].Carbon Neutralization,2025,4(3):e70009.
[40] Zeng T,Hu Z,Zhou Z,et al.Boron-catalyzed graphitization carbon layer enabling LiMn_0.8Fe_0.2PO₄ cathode superior kinetics and Li-storage properties[J].Small Methods,2023,7(2):e2201390.
[41] Guo Y Q,Yao Y G,Guo C,et al.Atomistic observation and transient reordering of antisite Li/Fe defects toward sustainable LiFePO₄[J].Energy & Environmental Science,2024,17:7749-7761.
[42] Gu H,Li W,Li Q,et al.Electrochemical properties of Li₄Ti₅O₁₂ coated LiMn_0.6Fe_0.4PO₄ prepared by rheological phase reaction method[J].Journal of the Electrochemical Society,2024,171:040502.
[43] Zhang B Q,Wang S Z,Liu L,et al.Enhancement of Li₂ZrO₃ modification of the cycle life of N/S-doped LiMn_0.5Fe_0.5PO₄/C composite cathodes for lithium ion batteries[J].Langmuir,2023,39:5187-5198.
[44] Chang H,Li Y,Fang Z K,et al.Construction of carbon-coated LiMn_0.5Fe_0.5PO₄@Li_0.33La_0.56TiO₃ nanorod composites for high-performance Li-ion batteries[J].ACS Applied Materials & Interfaces,2021,13:33102-33111.