B2O3 包覆NaNi1/3Fe1/3Mn1/3O2 正极材料制备及其电化学性能

doi:10.19799/j.cnki.2095-4239.2022.0213

储能科学与技术 ›› 2022, Vol. 11 ›› Issue (9): 2980-2988.doi: 10.19799/j.cnki.2095-4239.2022.0213

B₂O₃ 包覆NaNi_1/3Fe_1/3Mn_1/3O₂ 正极材料制备及其电化学性能

郭凯强¹(), 车海英²(), 张浩然¹, 廖建平², 周煌², 张云龙², 陈航达², 申展³, 刘海梅¹, 马紫峰²^,³

^1.上海电力大学环境与化学工程学院，上海 200090
^2.浙江钠创新能源有限公司，浙江绍兴 312000
^3.上海交通大学化学工程系，上海，200240

收稿日期:2022-04-20 修回日期:2022-05-08 出版日期:2022-09-05 发布日期:2022-08-30
通讯作者: 车海英 E-mail:gkq0412@163.com;chysyx@sjtu.edu.cn
作者简介:郭凯强（1991—），男，硕士研究生，研究方向为钠离子电池电极材料，E-mail：gkq0412@163.com；
基金资助:
国家自然科学基金项目(22005190);上海市科技启明星计划(20QB1405700)

Preparation and characterization of B₂O₃-coated NaNi_1/3Fe_1/3Mn_1/3O₂ cathode materials for sodium-ion batteries

Kaiqiang GUO¹(), Haiying CHE²(), Haoran ZHANG¹, Jianping LIAO², Huang ZHOU², Yunlong ZHANG², Hangda CHEN², Zhan SHEN³, Haimei LIU¹, Zifeng MA²^,³

^1.College of Environmental and Chemical Engineering, Shanghai University of Electric Power, Shanghai 200090, China
^2.Zhejiang NaTRIUM Energy Co. Ltd. , Shaoxing 312000, Zhejiang, China
^3.Department of Chemical Engineering, Shanghai JiaoTong University, Shanghai 200240, China

Received:2022-04-20 Revised:2022-05-08 Online:2022-09-05 Published:2022-08-30
Contact: Haiying CHE E-mail:gkq0412@163.com;chysyx@sjtu.edu.cn

摘要/Abstract

摘要：

O3型层状氧化物正极材料NaNi_1/3Mn_1/3Fe_1/3O₂具有高比容量、低成本和环境友好性等优点，被认为是最有前途的钠离子电池正极材料之一，但在充放电过程中会发生一系列复杂的相变，导致电化学性能较差。本研究报道了一种协同改性方法，以同时提高NaNi_1/3Mn_1/3Fe_1/3O₂正极材料的循环稳定性和倍率性能。通过将硼酸粉末和正极材料固相球磨混匀后低温煅烧，在NaNi_1/3Mn_1/3Fe_1/3O₂正极材料表面包覆纳米非金属氧化物B₂O₃。借助X射线衍射仪(XRD)、扫描电子显微技术(SEM)、透射电子显微镜(TEM)和电化学技术等测试手段，对比分析不同包覆量和原材料的形貌和电化学性能，筛选得到最优包覆量为2%(质量分数，余同)。该方法实现了B₂O₃的均匀包覆，并且没有改变NaNi_1/3Mn_1/3Fe_1/3O₂正极材料的晶体结构。通过电化学性能测试表明2% B₂O₃包覆材料在1 C倍率下循环200圈容量保持率从78%提升至87%。同时，2% B₂O₃包覆材料的高倍率性能也得到了改善，10 C高倍率下放电比容量从75 mAh/g提升至99 mAh/g。结果表明，这是一种有效且可靠的表面改性策略，可以增强钠离子电池层状氧化物正极材料的电化学性能。

关键词: 硼酸, B₂O₃包覆, 层状氧化物, 钠离子电池, NaNi_1/3Mn_1/3Fe_1/3O₂正极材料

Abstract:

Due to its high capacity, low cost, and environmental safety, layered oxide O₃-NaNi_1/3Mn_1/3Fe_1/3O₂ is one of the most promising cathode medium recently. However, its complicated phase transitions during the charge-discharge process lead to inferior electrochemical properties. In this study, we report a synergetic modification method to simultaneously increase the rate capacity and cycling stability of the O₃-NaNi_1/3Mn_1/3Fe_1/3O₂ cathode medium by utilizing B₂O₃-coating and B³⁺ doping. The B₂O₃-coated NaNi_1/3Fe_1/3Mn_1/3O₂ cathode was prepared using the ball milling method. Materials with different B₂O₃ contents were prepared and characterized using X-ray diffractometer, scanning electron microscope, transmission electron microscopy, and electrochemical examinations. The best performing compound was obtained when 2% B₂O₃ coating was utilized. B₂O₃ was uniformly distributed between NaNi_1/3Fe_1/3Mn_1/3O₂ particles, and the preparation process did not change the crystal structure of NaNi_1/3Fe_1/3Mn_1/3O₂. Furthermore, the charge-discharge curves indicated that the capacity retention of 2% B₂O₃-coated samples was enhanced from 78% to 87% after 200 cycles. B₂O₃-coated NaNi_1/3Mn_1/3Fe_1/3O₂ also exhibited remarkable rate capability (99 mAh/g at a high rate of 10 C, compared to 75 mAh/g for the pristine). These results indicated that the proposed approach is an effective and reliable surface modification strategy for reinforcing the electrochemical properties of layered oxide materials for sodium-ion batteries.

Key words: H₃BO₃, B₂O₃coating, layered oxide, sodium-ion batteries, NaNi_1/3Fe_1/3Mn_1/3O₂ cathode material

中图分类号:

TM 911

郭凯强, 车海英, 张浩然, 廖建平, 周煌, 张云龙, 陈航达, 申展, 刘海梅, 马紫峰. B₂O₃ 包覆NaNi_1/3Fe_1/3Mn_1/3O₂ 正极材料制备及其电化学性能[J]. 储能科学与技术, 2022, 11(9): 2980-2988.

Kaiqiang GUO, Haiying CHE, Haoran ZHANG, Jianping LIAO, Huang ZHOU, Yunlong ZHANG, Hangda CHEN, Zhan SHEN, Haimei LIU, Zifeng MA. Preparation and characterization of B₂O₃-coated NaNi_1/3Fe_1/3Mn_1/3O₂ cathode materials for sodium-ion batteries[J]. Energy Storage Science and Technology, 2022, 11(9): 2980-2988.

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参考文献 26

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活性材料	a/Å	b/Å	c/Å	V /Å³	Na—O/Å	TM—O/Å
NFM	2.976394	2.976394	16.03295	123.006	2.3531	2.0215
NFM@2%B₂O₃	2.9733	2.9733	16.07577	123.078	2.3767	2.0048

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B₂O₃ 包覆NaNi_1/3Fe_1/3Mn_1/3O₂ 正极材料制备及其电化学性能

Preparation and characterization of B₂O₃-coated NaNi_1/3Fe_1/3Mn_1/3O₂ cathode materials for sodium-ion batteries

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