Improvement paths for the stability and safety of LiFe x Mn1–x PO4 (0 < x < 1) batteries: From failure mechanisms to comprehensive optimization strategies

doi:10.19799/j.cnki.2095-4239.2024.0915

Abstract

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

CLC Number:

TM 1.11

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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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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