Ce掺杂对抑制LiFe0.6Mn0.4PO4/C正极材料中Mn金属溶解的作用

doi:10.19799/j.cnki.2095-4239.2025.0582

摘要/Abstract

摘要：

磷酸锰铁锂（LiFe_xMn_1-xPO₄, LFMP）因其低成本和安全优势，兼具LiFePO₄的良好的循环性能和LiMnPO₄的高能量密度,正逐渐成为一种安全可靠的商业化锂离子电池存储材料。然而，LFMP中较严重的晶格应力及充电时Mn³⁺引起的Jahn-Teller畸变导致了其较低的锂离子扩散速率以及电导率，这限制了其进一步的工业应用。针对这一问题，本研究采用球磨辅助固相烧结的方法制备了Ce掺杂的LiFe_0.6Mn_0.4PO₄/C（LFMP/C-Ce），并分析了不同掺杂含量下材料的电化学性能。通过X射线衍射（XRD）、扫描电子显微镜（SEM）和透射电子显微镜（TEM）等技术表征了这些材料的成分、表面形貌和微观形貌，这些分析证实了Ce离子成功掺杂到橄榄石晶格过渡金属（Mn）的位点当中，减少了晶格应力，延长了Li-O键，同时缩短了Mn-O键，从而缓解了Jahn-Teller畸变。使用恒流恒压充放电测试、恒电流间歇滴定（GITT）、循环伏安法（CV）和电化学阻抗谱（EIS）等技术评估了样品的电化学性能。结果表明，掺杂1%Ce（LFMP/C-Ce1%）可获得最佳的循环性能。LFMP/C-Ce1%在1 C下经过500次循环后表现出92.6%的容量保持率。电感耦合等离子体发射光谱（ICP-OES）分析证实，该掺杂水平可有效抑制循环后Mn金属溶解，从而提高LFMP正极材料的电化学性能和稳定性。

关键词: 锂离子电池, 磷酸锰铁锂, 过渡金属溶解, 阳离子掺杂

Abstract:

LiFe_xMn_1-xPO₄ (LFMP) is gradually emerging as a safe and reliable commercial lithium battery storage material due to its low cost and safety advantages, combining the excellent cycling stability of LiFePO₄ with the high energy density of LiMnPO₄. However, severe lattice stress and the Jahn–Teller distortion caused by Mn³⁺ during charging lead to low lithium-ion diffusion rates and poor electrical conductivity in LFMP, limiting its further industrial application. To address this issue, this study synthesized Ce-doped LiFe_0.6Mn_0.4PO₄/C (LFMP/C-Ce) via ball milling-assisted solid-state sinteringand investigated the electrochemical performance of materials with different doping levels. Techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were employed to characterize the composition, surface morphology, and microstructure of the materials. The analyses confirmed the successful incorporation of Ce ions into the olivine lattice, which reduced lattice stress, elongated Li–O bonds, and shortened Mn–O bonds, thereby mitigating the Jahn–Teller distortion. The electrochemical performance of the samples was evaluated using constant current–constant voltage charge–discharge testing, galvanostatic intermittent titration technique (GITT), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The results showed that doping with 1% Ce (LFMP/C-Ce1%) achieved the best cycling performance. LFMP/C-Ce1% retained 92.6% of its capacity after 500 cycles at 1 C. Inductively coupled plasma optical emission spectrometry (ICP-OES) analysis confirmed that this doping level effectively suppresses Mn dissolution after cycling, thereby enhancing the electrochemical performance and stability of the LFMP cathode material.

Key words: Lithium-ion battery, Transition metal dissolution, Cation doping

中图分类号:

TK02

赵万炜, 杨亚东, 靳光耀, 梁闻予, 李建强, 徐睿. Ce掺杂对抑制LiFe_0.6Mn_0.4PO₄/C正极材料中Mn金属溶解的作用[J]. 储能科学与技术, doi: 10.19799/j.cnki.2095-4239.2025.0582.

Wanwei Zhao, Yadong Yang, Guangyao Jin, Wenyu Liang, Jianqiang Li, Rui Xu. Contribution of Ce-Doping to suppressing metal dissolution in LiFe_0.6Mn_0.4PO₄/C cathode materials[J]. Energy Storage Science and Technology, doi: 10.19799/j.cnki.2095-4239.2025.0582.

图/表 10

图1

表1

表2

表3

图2

图3

图4

图5

图6

表4

参考文献 29

[1]	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(2): 63.
[2]	SCHMUCH R, WAGNER R, HöRPEL G, et al. Performance and cost of materials for lithium-based rechargeable automotive batteries[J]. Nature energy, 2018, 3(4): 267-278.
[3]	WANG L, ZHANG H, LIU Q, et al. Modifying high-voltage olivine-type LiMnPO₄ cathode via Mg substitution in high-orientation crystal[J]. ACS Applied Energy Materials, 2018, 1(11): 5928-5935.
[4]	YANG H, DUH J-G, CHEN H-Y, et al. Synthesis and in-situ investigation of olivine LiMnPO₄ composites substituted with tetravalent vanadium in high-rate Li-ion batteries[J]. ACS Applied Energy Materials, 2018, 1(11): 6208-6216.
[5]	ZHANG J, WEI H, CAO Y, et al. Hierarchical LiMnPO₄·Li₃V₂(PO₄)₃/C/rGO nanocomposites as superior-rate and long-life cathodes for lithium ion batteries[J]. Journal of Alloys and Compounds, 2018, 769: 332-339.
[6]	TARASCON J-M, ARMAND M. Issues and challenges facing rechargeable lithium batteries[J]. Nature, 2001, 414(6861): 359-367.
[7]	ARMAND M, TARASCON J-M. Building better batteries[J]. Nature, 2008, 451(7179): 652-657.
[8]	LIU J, XU C, CHEN Z, et al. Progress in aqueous rechargeable batteries[J]. Green Energy & Environment, 2018, 3(1): 20-41.
[9]	HAN Q, CAI L, YANG Z, et al. New insights into the pre-lithiation kinetics of single-crystalline Ni-rich cathodes for long-life Li-ion batteries[J]. Green Energy & Environment, 2022.
[10]	SOCIETY E. Journal of the Electrochemical Society, F, 2009[C]. Electrochemical Society.
[11]	QIAN J, ZHOU M, CAO Y, et al. Template-free hydrothermal synthesis of nanoembossed mesoporous LiFePO₄ microspheres for high-performance lithium-ion batteries[J]. The Journal of Physical Chemistry C, 2010, 114(8): 3477-3482.
[12]	LI L-E, LIU J, CHEN L, et al. Effect of different carbon sources on the electrochemical properties of rod-like LiMnPO₄–C nanocomposites[J]. RSC Advances, 2013, 3(19): 6847-6852.
[13]	NORBERG N S, KOSTECKI R. The degradation mechanism of a composite LiMnPO₄ cathode[J]. Journal of the Electrochemical Society, 2012, 159(9): A1431.
[14]	WEN F, SHU H, ZHANG Y, et al. Mesoporous LiMnPO₄/C nanoparticles as high performance cathode material for lithium ion batteries[J]. Electrochimica Acta, 2016, 214: 85-93.
[15]	WANG Y, WANG F, FENG X. Porous nest-like LiMnPO₄ microstructures assembled by nanosheets for lithium ion battery cathodes[J]. Journal of Materials Science: Materials in Electronics, 2018, 29: 1426-1434.
[16]	HAN J, YANG J, LU H, et al. Effect of synthesis processes on the microstructure and electrochemical properties of LiMnPO₄ cathode material[J]. Industrial & Engineering Chemistry Research, 2022, 61(22): 7451-7463.
[17]	MARTHA S K, GRINBLAT J, HAIK O, et al. LiMn_0.8Fe_0.2PO₄: An advanced cathode material for rechargeable lithium batteries[J]. ChemInform, 2010, 41(1): i.
[18]	SUN Y K, OH S M, PARK H K, et al. Micrometer‐sized, nanoporous, high‐volumetric‐capacity LiMn_0.85Fe_0.15PO₄ cathode material for rechargeable lithium‐ion batteries[J]. Advanced Materials, 2011, 43(23): 5050-5054.
[19]	YONEMURA M, YAMADA A, TAKEI Y, et al. Comparative kinetic study of olivine Li_xMPO₄(M=Fe,Mn)[J]. Journal of the Electrochemical Society, 2004, 151(9): A1352.
[20]	WANG Y, YANG H, WU C-Y, et al. Facile and controllable one-pot synthesis of nickel-doped LiMn_0.8Fe_0.2PO₄ nanosheets as high performance cathode materials for lithium-ion batteries[J]. Journal of Materials Chemistry A, 2017, 5(35): 18674-18683.
[21]	YAN X, SUN D, WANG Y, et al. Enhanced electrochemical performance of LiMn_0.75Fe_0.25PO₄ nanoplates from multiple interface modification by using fluorine-doped carbon coating[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(6): 4637-4644.
[22]	LUO S-H, SUN Y, BAO S, et al. Synthesis of Er-doped LiMnPO₄/C by a sol-assisted hydrothermal process with superior rate capability[J]. Journal of Electroanalytical Chemistry, 2019, 832: 196-203.
[23]	LUO C, JIANG Y, ZHANG X, et al. Misfit strains inducing voltage decay in LiMn_yFe_1-yPO₄/C[J]. Journal of Energy Chemistry, 2022, 68: 206-212.
[24]	PLEUKSACHAT S, KRABAO P, PONGHA S, et al. Dynamic phase transition behavior of a LiMn_0.5Fe_0.5PO₄ olivine cathode material for lithium-ion batteries revealed through in-situ X-ray techniques[J]. Journal of Energy Chemistry, 2022, 71: 452-459.
[25]	SIN B C, SINGH L, LEE K-E, et al. Enhanced electrochemical performance of LiFe_0.4Mn_0.6(PO₄)_1-x(BO₃)_x as cathode material for lithium ion batteries[J]. Journal of Electroanalytical Chemistry, 2015, 756: 56-60.
[26]	LIU Y, CHANG C, ZHENG J. Revealing the role of Mg doping in LiFe_0.39Mg_0.01Mn_0.6PO₄/C cathode: Enhanced electrochemical performance from improved electrical conductivity and promoted lithium diffusion kinetics[J]. Journal of Energy Storage, 2024, 91: 112108.
[27]	ZHANG Q, LIU Y, CHANG C, et al. Modulating the lattice structure via Cr³⁺ doping in LiFe_0.4Mn_0.6PO₄ cathode for improved rate behavior and promoted cyclic performance[J]. Journal of Energy Storage, 2024, 101: 113799.
[28]	JIN H, ZHANG J, QIN L, et al. Dual modification of olivine LiFe_0.5Mn_0.5PO₄ cathodes with accelerated kinetics for high-rate lithium-ion batteries[J]. Industrial & Engineering Chemistry Research, 2023, 62(2): 1029-1034.
[29]	NANNAN Z, YONGSHENG L, XIAOKE Z, et al. Effect of Ce³⁺ doping on the properties of LiFePO₄ cathode material[J]. Journal of Rare Earths, 2016, 34(2): 174-180.

Materials	a(Å)	b(Å)	c(Å)	V(Å³)	Microstrain
LFMP/C-Ce0%	10.3761	6.0449	4.7153	295.755	1048.4
LFMP/C-Ce0.5%	10.3806	6.0511	4.7198	296.470	998.5
LFMP/C-Ce1%	10.3865	6.0550	4.7254	297.182	910.2
LFMP/C-Ce2%	10.3902	6.0597	4.7312	297.883	1581.6

Materials	Li-O1	Li-O2	Li-O3	Li-O4	Li-O5	Li-O6	average
LFMP/C-Ce0%	2.195	2.121	2.076	2.195	2.121	2.076	2.131
LFMP/C-Ce1%	2.072	2.203	2.145	2.072	2.203	2.145	2.140

Materials	Mn-O1	Mn-O2	Mn-O3	Mn-O4	Mn-O5	Mn-O6	average	DI(MnO₆)
LFMP/C-Ce0%	2.222	2.232	2.139	2.121	2.139	2.232	2.181	0.0483
LFMP/C-Ce1%	2.243	2.243	2.195	2.133	2.112	2.133	2.173	0.0380

Materials	Mn（ppm）
LFMP/C-Ce0%	18.34
LFMP/C-Ce1%	8.08

Ce掺杂对抑制LiFe_0.6Mn_0.4PO₄/C正极材料中Mn金属溶解的作用

Contribution of Ce-Doping to suppressing metal dissolution in LiFe_0.6Mn_0.4PO₄/C cathode materials

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 29

相关文章 15

编辑推荐

Metrics

本文评价

[1]	杨斌, 杨军, 徐浪, 温浩伟, 刘登锋, 阮殿波. 电容型锂离子电池的球头压痕对其安全性研究[J]. 储能科学与技术, 2025, 14(8): 3090-3099.
[2]	张腾, 常国峰. 基于单体特征参数差异的电池组热特性和热一致性研究[J]. 储能科学与技术, 2025, 14(8): 3194-3206.
[3]	高蕾, 顾洪汇, 张益明, 黄伟, 陆海燕, 周琳, 顾梅嵘. 超高功率锂离子电池脉冲性能研究[J]. 储能科学与技术, 2025, 14(8): 2942-2949.
[4]	徐成善, 孙烨, 杨智凯, 赵明强, 李亚伦, 冯旭宁, 王贺武, 卢兰光, 欧阳明高. 储能锂离子电池系统热失控诱发电弧研究进展[J]. 储能科学与技术, 2025, 14(8): 3037-3050.
[5]	李鹏举, 陈晓宇, 谢佳, 沈佳妮, 贺益君. 锂离子电池功率状态预测方法研究进展[J]. 储能科学与技术, 2025, 14(8): 3028-3036.
[6]	胡力月, 黄威, 周云, 周英强, 邵常政, 王柯. 基于模糊推理的储能系统锂离子电池模组热扩散概率评估方法[J]. 储能科学与技术, 2025, 14(7): 2662-2674.
[7]	王薇, 梁惠施, 李棉刚, 周奎, 王薇, 王姿尧, 史梓男. 基于迁移学习的锂电池不可逆析锂监测方法[J]. 储能科学与技术, 2025, 14(7): 2698-2706.
[8]	熊峰, 孔得朋, 平平, 张越, 任宪通, 吕耀. 电热耦合诱导三元锂离子电池热失控特性[J]. 储能科学与技术, 2025, 14(7): 2752-2760.
[9]	翁雯媛, 沈斌, 朱建功, 汪洋, 路华鹏, 何乌利雅苏, 刘浩男, 戴海峰, 魏学哲. 锂离子电池阳极危害性析锂原位检测综述[J]. 储能科学与技术, 2025, 14(7): 2575-2589.
[10]	张子敬, 原蓓蓓, 李红, 高颖. 锂离子电池热失控气体检测分析及预警[J]. 储能科学与技术, 2025, 14(7): 2820-2832.
[11]	刘佳辉, 卞伟翔, 李大伟. 锂电池石墨复合电极力-电耦合性能原位测量分析[J]. 储能科学与技术, 2025, 14(6): 2240-2247.
[12]	陈峥, 多功东, 申江卫, 沈世全, 刘昱, 魏福星. 基于容量增量分析与VMD-GWO-KELM的锂电池健康状态估计[J]. 储能科学与技术, 2025, 14(6): 2476-2487.
[13]	阮晶晶, 巫湘坤, 李勇慧, 赵冲冲, 李珅珅, 王童飞, 梁圣杰, 高桂红. 低成本干法石墨厚电极的制备与性能研究[J]. 储能科学与技术, 2025, 14(6): 2248-2255.
[14]	韩丹丹, 张武卫, 张亮, 王宗江. 核壳结构LiMn₁_-_y Fe _y PO₄/C正极材料设计与电化学性能研究[J]. 储能科学与技术, 2025, 14(6): 2215-2222.
[15]	王功瑞, 张安萍, 任萱萱, 杨铭哲, 韩宇宁, 吴忠帅. 高电压钴酸锂正极：关键挑战、改性策略与未来展望[J]. 储能科学与技术, 2025, 14(6): 2278-2319.