氟掺杂对LiMn0.8Fe0.2PO4/C正极材料电化学性能的影响

doi:10.19964/j.issn.1006-4990.2024-0054

摘要/Abstract

摘要：

随着新能源汽车和锂离子电池的普及和推广，磷酸锰铁锂材料作为锂离子电池正极材料，其电化学性能亟待进一步优化。在诸多磷酸锰铁锂改性手段中，阴离子位取代的研究较少。LiF作为掺杂剂，通过F^-取代PO₄^3-部分氧位的改性方法可提高磷酸锰铁锂的电化学性能。以Li₂CO₃、LiF、MnCO₃、FeC₂O₄·2H₂O、NH₄H₂PO₄和蔗糖为原料，通过高温固相法制备LiMn_0.8Fe_0.2PO_4-_X F₂_X /C（X=0.003、0.005、0.01、0.02）材料，并研究了不同氟掺杂量对LiMn_0.8Fe_0.2PO₄/C正极材料电化学性能的影响。结果表明，氟的掺入仅对LiMn_0.8Fe_0.2PO₄/C的晶格参数有轻微的改变，而对粒径影响不大；在电化学方面，氟掺杂使LiMn_0.8Fe_0.2PO₄/C具有良好的可逆容量和倍率性能，LiMn_0.8Fe_0.2PO_3.99F_0.02/C表现出最高的初始容量和最佳的倍率性能，0.1C和5C倍率下的放电比容量分别为155.1 mA·h/g和128.6 mA·h/g。相较于未掺杂的LiMnFePO₄，LiMn_0.8Fe_0.2PO_3.99F_0.02/C在1C下循环500次后容量保持率从73.3%提高到96.1%。

关键词: 电化学性能, 磷酸锰铁锂, 正极材料, 氟掺杂

Abstract:

With the popularization and promotion of new energy vehicles and lithium-ion batteries，the electrochemical performance of lithium manganese iron phosphate as cathode material for lithium-ion batteries needs to be further optimized.Among the modification methods of lithium ferromanganese phosphate，there are few studies on anion substitution.By the modification method of F^- replacing PO₄^3- partial oxygen site，LiF was used as a dopant to improve the electrochemical performance of lithium manganese iron phosphate.LiMn_0.8Fe_0.2PO_4-_X F₂_X /C（X=0.003，0.005，0.01，0.02） materials were prepared by high temperature solid state method using Li₂CO₃，LiF，MnCO₃，FeC₂O₄·2H₂O，NH₄H₂PO₄ and sucrose as raw materials，and the effects of different fluorine doping contents on the electrochemical properties of LiMn_0.8Fe_0.2PO₄/C cathode materials were studied.The analyses demonstrated that fluorine could be incorporated into LiMn_0.8Fe_0.2PO₄/C without altering the olivinestructure，but slightly changing the lattice parameters and having little effect on the particle sizes.The results of electrochemical measurement showed that fluorine doping in LiMn_0.8Fe_0.2PO₄/C resulted in good reversible capacity and rate capability.LiMn_0.8Fe_0.2PO_3.99F_0.02/C exhibited highest initial capacity and best rate performance.Its discharge capacities at 0.1C and 5C rates were 155.1 mA·h/g and 128.6 mA·h/g，respectively.After 500 cycles at 1C，the capacity retention was increased from 73.3% to 96.1% compared with the unmodified materials.

Key words: electrochemical performance, LiMn_0.8Fe_0.2PO₄, cathode material, F-doping

中图分类号:

TM911

刘佳盛, 罗晓强, 侯翠红, 薛灵伟. 氟掺杂对LiMn_0.8Fe_0.2PO₄/C正极材料电化学性能的影响[J]. 无机盐工业, 2024, 56(11): 45-50.

LIU Jiasheng, LUO Xiaoqiang, HOU Cuihong, XUE Lingwei. Effects of fluorine doping on electrochemical behavior of LiMn_0.8Fe_0.2PO₄/C cathode materials[J]. Inorganic Chemicals Industry, 2024, 56(11): 45-50.

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X	a/Å	b/Å	c/Å	V/Å³
0	6.033 97	10.441 92	4.691 01	295.56
0.003	6.029 95	10.411 56	4.694 47	294.72
0.005	6.047 55	10.357 42	4.703 92	294.64
0.010	6.059 33	10.351 02	4.730 51	294.47
0.020	6.026 84	10.353 23	4.708 76	293.81

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氟掺杂对LiMn_0.8Fe_0.2PO₄/C正极材料电化学性能的影响

Effects of fluorine doping on electrochemical behavior of LiMn_0.8Fe_0.2PO₄/C cathode materials

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