Sb掺杂O3型Na0.9Ni0.5Mn0.3Ti0.2O2钠离子电池正极材料

doi:10.15541/jim20220511

无机材料学报 ›› 2023, Vol. 38 ›› Issue (6): 656-662.DOI: 10.15541/jim20220511

Sb掺杂O3型Na_0.9Ni_0.5Mn_0.3Ti_0.2O₂钠离子电池正极材料

孔国强¹(), 冷明哲²(), 周战荣²(), 夏池¹, 沈晓芳²

1.山东非金属材料研究所, 济南 250031
2.火箭军工程大学基础部, 西安 710025

收稿日期:2022-09-01 修回日期:2022-11-14 出版日期:2022-12-09 网络出版日期:2022-12-09
通讯作者: 冷明哲, 讲师. E-mail: lmz_198810@163.com;
周战荣, 教授. E-mail: zhouzhou76@163.com
作者简介:孔国强(1986-), 男, 博士, 高级工程师. E-mail: kongguoqiang2010@163.com
基金资助:
山东省重点研发计划(2018JMRH0211);济南市创新团队项目(2021GXRC041)

Sb Doped O3 Type Na_0.9Ni_0.5Mn_0.3Ti_0.2O₂ Cathode Material for Na-ion Battery

KONG Guoqiang¹(), LENG Mingzhe²(), ZHOU Zhanrong²(), XIA Chi¹, SHEN Xiaofang²

1. Institute of Shandong Non-Metallic Materials, Jinan 250031, China
2. Department of Basic, PLA Rocket Force University of Engineering, Xi’an 710025, China

Received:2022-09-01 Revised:2022-11-14 Published:2022-12-09 Online:2022-12-09
Contact: LENG Mingzhe, lecturer. E-mail: lmz_198810@163.com;
ZHOU Zhanrong, professor. E-mail: zhouzhou76@163.com
About author:KONG Guoqiang (1986-), male, PhD, senior engineer. E-mail: kongguoqiang2010@163.com
Supported by:
Key R&D Plan of Shandong Province(2018JMRH0211);Innovation Team Project of Jinan City(2021GXRC041)

摘要/Abstract

摘要：

提高钠离子电池正极材料的循环稳定性和比容量是实现其广泛应用的关键, 基于引入特定杂元素可优化正极材料结构稳定性和比容量的策略, 本研究采用便捷的固相反应法制备O3-Na_0.9Ni_0.5-_xMn_0.3Ti_0.2Sb_xO₂(NMTSb_x, x=0, 0.02, 0.04, 0.06)系列层状氧化物正极材料, 对比研究了Sb掺杂对Na_0.9Ni_0.5Mn_0.3Ti_0.2O₂正极材料储钠性能的影响。测试结果表明, 引入Sb后过渡金属层中氧原子之间的静电斥力减小, 晶格间距扩大, 有利于Na⁺的脱嵌。且掺杂Sb所造成的强电子离域降低了整个系统的能量, 获得了更有利于循环充放电的稳定性结构。在2.0~4.2 V测试范围下, 未掺杂的NMTSb₀在1C(240 mA·g⁻¹)倍率下初始放电比容量为122.8 mAh·g^-1, 200圈循环后容量保持率仅为41.5%, 掺杂后的NMTSb_0.04在1C倍率下初始放电比容量达到135.2 mAh·g^-1, 200圈循环后容量保持率为70%, 掺杂后材料的放电容量明显提高, 循环寿命显著延长。本研究有助于推动钠离子电池的进一步发展。

关键词: Sb掺杂, O3型, 正极材料, 固相法, 宽电压, 钠离子电池

Abstract:

Cycle stability and specific capacity of cathode materials for sodium ion batteries play an important role in achieving their wide application. Based on the strategy of introducing specific heteroelements to optimize the structural stability and specific capacity of cathode materials, O3-Na_0.9Ni_0.5-_xMn_0.3Ti_0.2Sb_xO₂ (NMTSb_x, x=0, 0.02, 0.04, 0.06) was prepared by a simple solid-state reaction method, and effects of Sb doping amount on the sodium storage properties of Na_0.9Ni_0.5Mn_0.3Ti_0.2O₂ cathode materials were investigated. The characterization results show that the electrostatic repulsion force between oxygen atoms in the transition metal layer is reduced after Sb doping, while the lattice spacing is expanded, which is conducive to deintercalation of Na⁺. Meanwhile, the strong electron delocalization caused by Sb doping decreases energy of the whole system, leading to a stable structure, more conducive to cyclic charging and discharging. The electrochemical test shows that initial discharge specific capacity of undoped NMTSb₀ is 122.8 mAh·g⁻¹ at 1C(240 mA·g⁻¹), and the capacity retention rate is only 41.5% after 200 cycles. But initial discharge specific capacity of doped NMTSb_0.04 is 135.2 mAh·g⁻¹ at 1C, and the capacity retention rate is up to 70% after 200 cycles. This study shows that Sb doped O3 type Na_0.9Ni_0.5Mn_0.3Ti_0.2O₂ cathode material can significantly improve initial discharge specific capacity and capacity retention rate of sodium ion batteries. Our results suggest that Sb doping strategy might be a useful approach for preparation of high stable sodium ion batteries..

Key words: Sb doping, O3 type, cathode material, solid phase method, wide voltage, Na-ion battery

中图分类号:

TQ174

孔国强, 冷明哲, 周战荣, 夏池, 沈晓芳. Sb掺杂O3型Na_0.9Ni_0.5Mn_0.3Ti_0.2O₂钠离子电池正极材料[J]. 无机材料学报, 2023, 38(6): 656-662.

KONG Guoqiang, LENG Mingzhe, ZHOU Zhanrong, XIA Chi, SHEN Xiaofang. Sb Doped O3 Type Na_0.9Ni_0.5Mn_0.3Ti_0.2O₂ Cathode Material for Na-ion Battery[J]. Journal of Inorganic Materials, 2023, 38(6): 656-662.

图/表 11

图1 NMTSbx (x=0, 0.02, 0.04, 0.06)的XRD谱图(a)和局部放大图谱(b)

Fig. 1 Survey (a) and enlarged (b) XRD patterns of NMTSbx (x=0, 0.02, 0.04, 0.06)

图2 NMTSb0 (a)和NMTSb0.04(b)的XRD Rietveld精修图

Fig. 2 Rietveld refinement XRD patterns of NMTSb0 (a) and NMTSb0.04(b)

图3 NMTSb0 (a, b)和NMTSb0.04 (c, d)的SEM照片和EDS图谱

Fig. 3 SEM images and EDS mappings of NMTSb0 (a, b) and NMTSb0.04 (c, d)

图4 NMTSb0.04正极材料的CV曲线

Fig. 4 CV curves of NMTSb0.04 cathode material

图5 NMTSbx的电化学阻抗图谱

Fig. 5 Electrochemical impedance spectra of NMTSbx

图6 NMTSbx作为正极材料的钠离子电池性能

Fig. 6 Performance of Na-ion batteries with NMTSbx as electrodes (a) Charging and discharging curves of Na-ion batteries with samples as electrodes for the first cycle at 1C; (b) Cycling performance of Na-ion batteries with samples as electrodes at 1C for 200 cycles; (c, d) Charging and discharging curves of Na-ion batteries with samples as electrodes for initial 3 cycles at 5C; (e) Coulombic efficiencies of Na-ion batteries with NMTSbx as electrodes for 200 cycles at 1C Colorful figures are available on website

图S1 NMTSb0 (a, b)和NMTSb0.04 (c, d)的HRTEM照片,(b, d)中插图为对应的SEAD照片

Fig. S1 HRTEM images of NMT (a, b) and NMTSb0.04 (c, d) with inset in (b, d) showing corresponding SEAD images

图S2 NMTSb0和NMTSb0.04中(a)Ni2p, (b)Mn2p, (c)Ti2p和(d)Sb3d的XPS图谱

Fig. S2 (a) Ni2p, (b) Mn2p, (c) Ti2p, and (d) Sb3d XPS spectra of NMTSb0 and NMTSb0.04

图S3 NMTSb0.04作为钠离子电池正极材料循环200圈之后的XRD图谱

Fig. S3 XRD pattern of NMTSb0.04as cathode material of Na-ion battery after 200 cycles

表S1 O3-NMTSbx (x=0, 0.02, 0.04, 0.06)的ICP-AES结果(化学计量比)

Table S1 ICP-AES results of O3-NMTSbx (x=0, 0.02, 0.04, 0.06) (Stoichiometric ratio)

	Na	Ni	Mn	Ti	Sb
NMTSb₀	0.913	0.486	0.288	0.181	0
NMTSb_0.02	0.924	0.471	0.284	0.186	0.023
NMTSb_0.04	0.920	0.452	0.287	0.184	0.039
NMTSb_0.06	0.929	0.435	0.279	0.184	0.061

表S2 NMTSb0和NMTSb0.04的晶胞参数

Table S2 Lattice parameters of materials with NMTSb0and NMTSb0.04

	a/nm	b/nm	c/nm	V/nm³	R_wp/%	R_p/%
NMTSb₀	0.29812	0.29812	1.600487	0.1232	4.92	5.53
NMTSb_0.04	0.29790	0.29790	1.608391	0.1236	5.65	6.32

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Sb掺杂O3型Na_0.9Ni_0.5Mn_0.3Ti_0.2O₂钠离子电池正极材料

Sb Doped O3 Type Na_0.9Ni_0.5Mn_0.3Ti_0.2O₂ Cathode Material for Na-ion Battery

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