锰基钠离子电池正极材料设计及电化学性能研究

doi:10.19964/j.issn.1006-4990.2023-0247

摘要/Abstract

摘要：

钠离子电池因环境友好、储量丰富等优势，成为锂离子电池的后继者，在储能材料方面有很大的应用潜力。针对钠离子电池锰基正极材料存在结构不稳定、循环稳定性差等问题，采用溶胶-凝胶法制备Na_0.7Fe _x Mn_（1-_x_）O₂（0<x<1）锰基正极材料，考察铁锰物质的量比对Na_0.7Fe _x Mn_（1-_x_）O₂材料微观结构、电化学性能的影响。结果表明：铁的掺杂稳定了材料P2相晶型且增加了钠层间距；合成的两种材料Na_0.7Fe_0.2Mn_0.8O₂和Na_0.7Fe_0.35Mn_0.65O₂在电压范围为2~4 V、放电倍率为0.5C的条件下，首次充/放电比容量分别为88.54、63.73 mA·h/g和74.02、49.01 mA·h/g，循环100次后充/放电比容量分别为51.94、51.36 mA·h/g和52.15、51.59 mA·h/g，循环效率分别为58.01%和69.7%，表现出良好的容量保持和循环性能；在倍率方面，两种材料经过2C大电流充电后，重新循环到0.5C倍率时两种材料的充/放电比容量仍可达113.82、110.25 mA·h/g和51.75、51.11 mA·h/g，两种材料都表现了较好的循环倍率性能，其中Na_0.7Fe_0.2Mn_0.8O₂材料的性能表现得更加优异。

关键词: 锰基, 正极材料：铁掺杂, P2相, 比容量

Abstract:

Sodium ion batteries have become the successor of lithium ion batteries due to their advantages of environmental friendliness and abundant reserves，and have great application potential in energy storage materials.In view of the problems of unstable structure and poor cycle stability of manganese-based cathode materials for sodium ion batteries，Na_0.7Fe _x Mn_（1-_x_）O₂（0<x<1） manganese-based cathode materials were prepared by sol-gel method.The effects of n（Fe）/n（Mn） molar ratio on the microstructure and electrochemical properties of Na_0.7Fe _x Mn_（1-_x_）O₂ materials were investigated.The results showed that the doping of iron stabilized the P2 phase crystal form of the material and increased the sodium layer spacing.The P2-phase layered cathode materials of Na_0.7Fe_0.2Mn_0.8O₂ and Na_0.7Fe_0.35Mn_0.65O₂were synthesized.The synthesized two materials of Na_0.7Fe_0.2Mn_0.8O₂and Na_0.7Fe_0.35Mn_0.65O₂ had charge/discharge specific capacities of 88.54，63.73 mA·h/g and 74.02，49.01 mA·h/g in the first cycle.After 100 cycles，the charge/discharge specific capacities were 51.94，51.36 mA·h/g and 52.15，51.59 mA·h/g，respectively，and the cycle efficiencies were 58.01% and 69.7%，respectively，showing good capacity retention and cycle performance.In terms of rate，the charge and discharge specific capacity of the two materials could still reach 113.82，110.25 mA·h/g and 51.75，51.11 mA·h/g when the two materials were charged at 2C high current and recycled to 0.5C rate.Both materials showed good cycle rate performance.In general，the performance of Na_0.7Fe_0.2Mn_0.8O₂ was more excellent.

Key words: manganese-based, cathode material, iron-doped, P2 phase, specific capacity

中图分类号:

TQ137.12

刘德新, 马腾跃, 安金玲, 刘进荣, 何伟艳. 锰基钠离子电池正极材料设计及电化学性能研究[J]. 无机盐工业, 2024, 56(3): 51-55.

LIU Dexin, MA Tengyue, AN Jinling, LIU Jinrong, HE Weiyan. Study on cathode material design and electrochemical properties of manganese-based sodium ion battery[J]. Inorganic Chemicals Industry, 2024, 56(3): 51-55.

图/表 6

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参考文献 19

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样品	a/Å	b/Å	c/Å	V/Å³
Na_0.7MnO_2.05	2.876	2.876	11.12	79.70
Na_0.7Fe_0.2Mn_0.8O₂	2.884	2.883	11.14	80.21
Na_0.7Fe_0.35Mn_0.65O₂	2.871	2.871	11.17	79.76

材料名称	元素	质量分数/%	相对原子质量	物质的量比	归一化
Na_0.7Fe_0.2Mn_0.8O₂	Na	31.47	22.99	1.37	1.23
	Fe	13.82	55.85	0.25	0.22
	Mn	47.56	54.94	0.87	0.78
Na_0.7Fe_0.35Mn_0.65O₂	Na	26.28	22.99	1.14	0.90
	Fe	25.75	55.85	0.46	0.36
	Mn	44.11	22.99	0.80	0.64

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