富锂锰基Li1.2[Co0.13Ni0.13Mn0.54]O2锂离子正极材料的磷改性研究

doi:10.11868/j.issn.1001-4381.2019.000595

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摘要

为提高高比容量的层状富锂锰基Li_1.2[Co_0.13Ni_0.13Mn_0.54]O₂材料的电化学性能，对材料添加了不同含量的NH₄H₂PO₄，并对其进行相关研究。主要是对原样和改性后的材料进行X射线衍射（XRD）、高分辨透射电镜（HRTEM）等物理化学性能测试，以及电化学阻抗谱（EIS）、首次充放电性能和倍率性能等电化学性能测试。结果表明：添加0.3%（质量分数，下同）磷元素材料（LMNCOP-03）的综合性能最优，首次放电比容量为280 mAh·g^-1，1 C容量为212.2 mAh·g^-1，3 C容量为170.6 mAh·g^-1。同时EIS测试表明引入0.3%磷的材料具有较低的表面阻抗R_sf和电荷传递电阻R_ct。

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	班丽卿
	高敏
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	柏祥涛
	李钊
	庄卫东

关键词 ：锂离子电池, 富锂锰基材料, 改性, 磷, 倍率性能

Abstract：

The enhanced electrochemical performance of the lithium-rich solid solution Li_1.2[Co_0.13Ni_0.13Mn_0.54]O₂ (LMNCO) cathode was enhanced by phosphorus incorporation. The various phosphorus contents were introduced by adding NH₄H₂PO₄ into the raw materials. The pristine sample and the sulfur incorporated samples were characterized by X-ray diffraction(XRD), high resolution transmission electron microscopy(HRTEM), electrochemical impedance spectroscopy(EIS). Electrochemical performance was assessed by measuring parameters such as charge and discharge capacity, rate capability in lithium ion cells. The results show that the LMNCOP-03 material has the best initial discharge capacity of 280 mAh·g^-1. Moreover, it has about 212.2 mAh·g^-1 and 170.6 mAh·g^-1 at 1.0 C and 3.0 C rate, respectively. The LMNCOP-03 material shows an improved rate performance attributed to the enhanced electrical conductivity and lithium ion diffusion, which is proved by EIS tests.

Key words： lithium-ion battery Li-rich and Mn-based material modification phosphorus rate perform-ance

收稿日期: 2019-06-24 出版日期: 2020-07-21

中图分类号:	O646.21
	TM912.9

基金资助:国家自然科学基金-联合基金(U1764255);北京市自然科学基金(L182023)

通讯作者: 庄卫东 E-mail: wdzhuang@126.com

作者简介: 庄卫东(1969-), 男, 教授, 博士, 研究方向为锂离子电池正极材料, 联系地址:北京市怀柔区雁栖开发区雁栖南西街12号有研粉末新材料有限公司(101407), E-mail:wdzhuang@126.com

引用本文:

班丽卿, 高敏, 庞国耀, 柏祥涛, 李钊, 庄卫东. 富锂锰基Li_1.2[Co_0.13Ni_0.13Mn_0.54]O₂锂离子正极材料的磷改性研究[J]. 材料工程, 2020, 48(7): 103-110.
Li-qing BAN, Min GAO, Guo-yao PANG, Xiang-tao BAI, Zhao LI, Wei-dong ZHUANG. Phosphorus modification of Li-rich and Mn-based Li_1.2[Co_0.13Ni_0.13Mn_0.54]O₂ cathode material for lithium-ion battery. Journal of Materials Engineering, 2020, 48(7): 103-110.

链接本文:

http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2019.000595 或 http://jme.biam.ac.cn/CN/Y2020/V48/I7/103

Fig.1 LMNCO材料和引入不同比例磷的LMNCOP材料的SEM图
(a)LMNCOP-00;(b)LMNCOP-01;(c)LMNCOP-03;(d)LMNCOP-05;(e)LMNCOP-07;(f)LMNCOP-09；(1)20 K; (2)50 K

Table 1 LMNCOP材料的粒径大小统计

Fig.2 LMNCO材料和引入不同比例磷的LMNCOP材料的XRD图(a)LMNCOP-00和LMNCOP-09;(b)所有LMNCOP材料

Fig.3 LMNCOP-03材料的TEM图

Fig.4 LMNCOP-03材料的电子衍射图和HRTEM图(a)电子衍射图; (b)明场视图; (c)HRTEM(500 K); (d)HRTEM(250 K)

Fig.5 LMNCOP-03材料的HRTEM图和EDS图谱
(a)HRTEM(250 K)；(b)析出的第一区域EDS表征(对应于图 5(a)中的1)；(c)析出的第二区域EDS表征(对应于图 5(a)中的2)

Fig.6 LMNCOP-03材料的示意图

Table 2 LMNCOP-03材料P，O的EDS元素分析

Fig.7 LMNCO材料和引入不同比例磷的LMNCOP材料的首次充放电曲线

Fig.8 LMNCO材料和引入不同比例磷的LMNCOP材料的倍率性能曲线

Table 3 LMNCO材料和引入不同比例磷的LMNCOP材料的首次充放电数据

Fig.9 LMNCO材料和引入不同比例磷的LMNCOP的EIS图(a)和对应的等效电路图(b)

Table 4 LCNMO材料和引入不同比例磷的LCNMOP材料的等效电路图测定的参数

1	LIM J H , CHUNG C G , SUNG Y W , et al. Electrochemical characterization of Li₂MnO₃-Li[Ni_1/3Co_1/3Mn_1/3]O₂-LiNiO₂ cathode synthesized via co-precipitation for lithium secondary batteries[J]. Journal of Power Sources, 2009, 189 (1): 571- 575.
2	班丽卿, 庄卫东, 卢华权, 等. 层状锂镍钴锰氧化物正极材料的改性研究进展[J]. 稀有金属, 2013, 37 (5): 820- 833.
2	BAN L Q , ZHUANG W D , LU H Q , et al. Progress in modification of layered cathode material Li-Ni-Co-Mn-O[J]. Chinese Journal of Rare Metals, 2013, 37 (5): 820- 833.
3	GUO R , SHI P , CHNEG X , et al. Effect of ZnO modification on the performance of LiNi_0.5Co_0.25Mn_0.25O₂ cathode material[J]. Electrochimica Acta, 2009, 54 (24): 5796- 5803.
4	GAO J , KIM J , MANTHIRAM A . High capacity Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂-V₂O₅ composite cathodes with low irreversible capacity loss for lithium ion batteries[J]. Electrochemistry Communications, 2009, 11 (1): 84- 86.
5	BETTGE M , LI Y , SANKARAN B , et al. Improving high-capacity Li_1.2Ni_0.15Mn_0.55Co_0.1O₂ based lithium-ion cells by modifying the positive electrode with alumina[J]. Journal of Power Sources, 2013, 233 (4): 346- 357.
6	LIU Y , NING D , ZHENG L , et al. Improving the electrochemical performances of Li-rich Li_1.20Ni_0.13Co_0.13Mn_0.54O₂ through a cooperative doping of Na⁺ and PO₄^3- with Na₃PO₄[J]. Journal of Power Sources, 2018, 375 (1): 1- 10.
7	MA L , MAO L , ZHAO X , et al. Improving the structural stability of Li-rich layered cathode materials by constructing an antisite defect nanolayer through polyanion doping[J]. Chem Electro Chem, 2017, 4 (12): 3068- 3074.
8	BAN L Q , YIN Y P , ZHUANG W D , et al. Electrochemical performance improvement of Li_1.2[Mn_0.54Ni_0.13Co_0.13]O₂ cathode material by sulfur incorporation[J]. Electrochemical Acta, 2015, (187): 212- 218.
9	CHO J , KIM Y W , KIM B , et al. A breakthrough in the safety of lithium secondary batteries by coating the cathode material with AlPO₄ nanoparticles[J]. Angewandte Chemie International Edition, 2003, 42, 1618- 1621.
10	LIU H , CHEN C , DU C , et al. Lithium-rich Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ oxide coated by Li₃PO₄ and carbon nanocomposite layer as a high performance cathode material for lithium ion batteries[J]. Journal of Materials Chemistry A, 2015, 3 (6): 2634- 2641.
11	NGOC H V , JONG C I , SANJITH U , et al. Synergic coating and doping effects of Ti-modified integrated layered-spinel Li_1.2Mn_0.75Ni_0.25O_2+d as a high capacity and long lifetime cathode material for Li-ion batteries[J]. Journal of Materials Chemistry A, 2018, 6 (5): 2200- 2211.
12	LIU S , LIU Z , SHEN X , et al. Surface doping to enhance structural integrity and performance of Li-rich layered oxide[J]. Advanced Energy Materials, 2018, 8 (31): 1802105.
13	HUANG J , LIU H , HU T , et al. Enhancing the electrochemical performance of Li-rich layered oxide Li_1.13Ni_0.3Mn_0.57O₂ via WO₃ doping and accompanying spontaneous surface phase formation[J]. Journal of Power Sources, 2018, 375 (1): 21- 28.
14	MU K , CAO Y , HU G , et al. Enhanced electrochemical performance of Li-rich cathode Li_1.2Ni_0.2Mn_0.6O₂ by surface modification with WO₃ for lithium ion batteries[J]. Electrochimica Acta, 2018, 273, 88- 97.
15	LI X , ZHANG K , MITLIN D , et al. Fundamental insight into Zr modification of Li⁺ and Mn-rich cathodes:combined transmission electron microscopy and electrochemical impedance spectroscopy study[J]. Chemistry of Materials, 2018, 30 (8): 2566- 2573.
16	刘祥欢, 庄卫东, 彭敏, 等. 锂离子电池富锂锰基正极材料的研究进展[J]. 稀有金属, 2017, 41 (5): 534- 552.
16	LIU X H , ZHUANG W D , PENG M , et al. Research progress in Li-rich manganese-based cathode material for Li-ion battery[J]. Chinese Journal of Rare Metals, 2017, 41 (5): 534- 552.

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