LiFe x Mn1–x PO4 （0<x<1）电池稳定性与安全性的提升路径：从失效机制到综合优化策略

doi:10.19799/j.cnki.2095-4239.2024.0915

储能科学与技术 ›› 2025, Vol. 14 ›› Issue (3): 965-983.doi: 10.19799/j.cnki.2095-4239.2024.0915

LiFe _x Mn₁_–_x PO₄ （0<x<1）电池稳定性与安全性的提升路径：从失效机制到综合优化策略

吉帅静¹(), 王军伟², 杜宝帅³, 徐丽⁴, 楼平⁵, 管敏渊⁵, 汤舜², 程时杰², 曹元成²()

^1.华中科技大学材料科学与工程学院
^2.华中科技大学电气学院，湖北武汉 430074
^3.国网山东省电力公司电力科学研究院，山东济南 250003
^4.北京智慧能源研究院，北京 102209
^5.国网浙江省电力有限公司湖州供电公司，浙江湖州 313000

收稿日期:2024-09-29 修回日期:2024-10-21 出版日期:2025-03-28 发布日期:2025-04-28
通讯作者: 曹元成 E-mail:d202280483@hust.edu.cn;yccao@hust.edu.cn
作者简介:吉帅静（1996—），女，博士研究生，研究方向为退役动力电池综合利用与再生修复，E-mail：d202280483@hust.edu.cn；
基金资助:
国家电网有限公司总部管理科技项目资助（退役磷酸铁锂电池低成本绿色再生利用关键技术5419-202199554A-0-5-ZN）

Improvement paths for the stability and safety of LiFe _x Mn₁_–_x PO₄ (0 < x < 1) batteries: From failure mechanisms to comprehensive optimization strategies

Shuaijing JI¹(), Junwei WANG², Baoshuai DU³, Li XU⁴, Ping LOU⁵, Minyuan GUAN⁵, Shun TAN², Shijie CHENG², Yuancheng CAO²()

^1.School of Materials Science and Engineering, Huazhong University of Science and Technology
^2.State Key Laboratory of Advanced Electromagnetic Engineering and Technology, School of Electrical and Electronic Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China
^3.State Grid Shandong Electric Power Research Institute, Jinan 250003, Shandong, China
^4.Beijing Institute of Smart Energy, Huairou Laboratory, Changping District, Beijing 102209, China
^5.Huzhou Power Supply Company, State Grid Zhejiang Electric Power Company Ltd. , Huzhou 313000, Zhejiang, China

Received:2024-09-29 Revised:2024-10-21 Online:2025-03-28 Published:2025-04-28
Contact: Yuancheng CAO E-mail:d202280483@hust.edu.cn;yccao@hust.edu.cn

摘要/Abstract

摘要：

在锂离子电池于电动汽车及储能领域广泛应用的背景下，磷酸锰锂铁(LiFe _x Mn_1-_x PO₄，0<x<1)作为正极材料，因其卓越的高安全性和高工作电压特性而备受瞩目。然而，LiFe _x Mn_1-_x PO₄(LFMP)材料存在的导电性不足及循环稳定性较差等问题，成为制约其商业化应用的关键性障碍。针对这些问题，本文深入探讨了LFMPO₄性能衰退的根源，包括Mn的Jahn-Teller畸变效应、迟缓的反应动力学以及锰基阴极材料中的歧化反应等核心问题，并深入分析了高温高压条件下产气产热的演变机制，以期揭示其失效机理。为提升LFMP的综合性能，本文总结了多种策略，如离子掺杂与碳包裹技术的结合使用、复合包覆技术以及电解质的改良等。这些策略着重于增强LFMP正极材料的电子导电性和Li⁺迁移率，稳定其相结构以抑制由Jahn-Teller效应引发的Mn溶解，减小界面应力，并提升材料的热稳定性和安全性。通过实施上述策略，不仅验证了失效机理分析的准确性，还展望了高性能锂离子电池LFMP正极材料的未来发展趋势。结合当前的研究成果，为实现高比容量、稳定的循环性能、出色的倍率性能以及高安全性，可能需要综合运用多种手段，如碳涂层、元素掺杂以及电解质优化等，以期开发出具有高能量密度、长循环寿命和热稳定性的全电池基LFMP正极材料。此外，本文还紧密结合当前的产业化研究进展，综述了不同合成工艺与Mn掺杂比例调控对LFMP材料结构和性能的具体影响，这不仅将推动LFMP基材料在高性能锂离子电池领域的广泛应用，也为其商业化进程奠定了坚实的基础。

关键词: LiFe _x Mn_1-_x PO₄(0<x<1), 失效机制, Jahn-Teller效应, 掺杂改性, 包覆改性, 电解质策略改性

Abstract:

Lithium iron phosphate (LFMP, LiFe _x Mn₁_–x PO₄, where 0<x<1) has garnered significant attention as a cathode material because of its high safety and operating voltage in lithium-ion battery applications for electric vehicles and energy storage. However, poor conductivity and suboptimal cycle stability of LFMP materials remain critical bottlenecks to their commercial use. This paper delves into the root causes of LFMP performance degradation, which include the Jahn-Teller distortion effect of Mn, sluggish reaction kinetics, and disproportionation reactions in manganese-based cathode materials, and analyzes the evolution mechanism of gas and heat production under high temperature and pressure to reveal the failure mechanism. To enhance LFMP performance, this paper summarizes various strategies, such as ion doping combined with carbon coating, composite coating technology, and electrolyte modification. These approaches aim to improve the electronic conductivity and Li⁺ migration rate, stabilize the phase structure to suppress Mn dissolution caused by the Jahn-Teller effect, reduce interfacial stress, and enhance thermal stability and safety. Implementing these strategies has verified the failure mechanism analysis and outlined future development trends for high-performance lithium-ion battery LFMP cathode materials. Based on current research findings, attaining high specific capacity, stable cycle performance, excellent rate capability, and high safety may necessitate combining carbon coating, element doping, and electrolyte optimization. Furthermore, this paper reviews the specific impacts of various synthesis processes and Mn doping ratios on the structure and performance of LFMP materials in close conjunction with current industrial research advancements. The development of LFMP-based cathode materials exhibiting high energy density, long cycle life, and thermal stability for full-cell batteries is anticipated. This advancement will promote the widespread application of LFMP-based materials in high-performance lithium-ion batteries and lay a solid foundation for their commercialization.

Key words: LiFe _x Mn₁_–x PO₄ (0<x<1), failure mechanisms, Jahn-Teller effect, doping modification, coating modification, electrolyte modification strategies

中图分类号:

TM 1.11

吉帅静, 王军伟, 杜宝帅, 徐丽, 楼平, 管敏渊, 汤舜, 程时杰, 曹元成. LiFe _x Mn₁_–_x PO₄ （0<x<1）电池稳定性与安全性的提升路径：从失效机制到综合优化策略[J]. 储能科学与技术, 2025, 14(3): 965-983.

Shuaijing JI, Junwei WANG, Baoshuai DU, Li XU, Ping LOU, Minyuan GUAN, Shun TAN, Shijie CHENG, Yuancheng CAO. Improvement paths for the stability and safety of LiFe _x Mn₁_–_x PO₄ (0 < x < 1) batteries: From failure mechanisms to comprehensive optimization strategies[J]. Energy Storage Science and Technology, 2025, 14(3): 965-983.

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材料	合成方法	比容量(0.1 C)/ (mAh/g)	参考文献
Li(Mn_0.85Fe_0.15)_0.92Ti_0.08PO₄/C	solid-state	99.9% (after 50 cycles at 170 C)	[48]
Li_0.97Na_0.03Mn_0.8Fe_0.2PO₄/C	solvothermal	96.65% (after 200 cycles at 85 C)	[64]
Li(Mn_0.9Fe_0.1)_0.95Mg_0.05PO₄/C	mechano-chemical liquid-phase activation	98.6% (after 50 cycles at 163 C)	[65]
LiFe_0.7Mn_0.25Mg_0.05PO₄/C	solvothermal	91% (after 200 cycles at 162.6 C)	[66]
LiFe_0.47Mn_0.5Ca_0.03PO₄/C	solid-state	87.84% (after 300 cycles at 160 C)	[67]
LiFe_0.5Mn_0.49Y_0.01PO₄/C	solid-state	86.7% (after 500 cycles at 158.5 C)	[61]
LiFe_0.5Mn_0.49In_0.01PO_3.97F_0.03	solvothermal	100% (after 100 cycles at 170 C)	[63]
LiFe_0.39Mg_0.01Mn_0.6PO_4/C	solid-state	100% (after 100 cycles at 170 C)	[59]
Li(Fe_0.5Mn_0.5)_0.97Mo_0.03PO₄/C	solvothermal approach	91.2% (after 200 cycles at 153 C)	[68]

Mn/Fe比	含碳量(质量分数)/%	合成方法	比容量/(mAh/g)	参考文献
0.1∶0.9	0	solvothermal	130.6(at 0.1 C)	[108]
0.1∶0.9	5	solid state	149(at 0.1 C)	[108]
0.15∶0.85	3.95	HEBM	156.5(at 0.1C)	[109]
0.2∶0.8	2-3	co-precipitation + solid state	151.1(at 0.1 C)	[110]
0.2∶0.8	33	sol-gel	160(at 0.1 C)	[111]
0.2∶0.8	2.95	spray dry	151(at 0.1 C)
0.3∶0.7	12.2	HEBM + solid-state reaction	164(at 0.05 C)	[112]
0.3∶0.7	3.2	hydrothermal	156.3(at 0.05)
0.4∶0.6	5 nm	two-step sol-gel method	150(at 0.1 C)	[113]
0.4∶0.6	8.5	ball-milling	128(at 0.1 C)	[114]
0.4∶0.6	10	sol-gel	152(at 0.1 C)	[34]
0.5∶0.5	3.16	ball-milling	138(at 0.1 C)	[115]
0.6∶0.4		solid-state		[116]
0.6∶0.4		solid-state	150(at 0.2 C)	[117]
0.75∶0.25	5	solid-state		[118]
0.8∶0.2	3	solvothermal	133(at 0.05 C)	[119]
0.8∶0.2		solid-state	155(at 0.2 C)	[120]

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LiFe _x Mn₁_–_x PO₄ （0<x<1）电池稳定性与安全性的提升路径：从失效机制到综合优化策略

Improvement paths for the stability and safety of LiFe _x Mn₁_–_x PO₄ (0 < x < 1) batteries: From failure mechanisms to comprehensive optimization strategies

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