Zn2+掺杂富锂层状正极材料Li1.13Ni0.3-xMn0.57ZnxO2的合成与电化学性质

doi:10.7503/cjcu20140905

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (4): 733.doi: 10.7503/cjcu20140905

Zn²⁺掺杂富锂层状正极材料Li_1.13Ni_0.3-_xMn_0.57Zn_xO₂的合成与电化学性质

王雪, 杨丽丽, 王春忠, 陈岗(), 魏英进

吉林大学物理学院, 新型电池物理与技术教育部重点实验室, 长春 130012

收稿日期:2014-10-11 出版日期:2015-04-10 发布日期:2015-03-27
作者简介:联系人简介: 陈岗, 男, 博士, 教授, 博士生导师, 主要从事功能材料物理化学研究. E-mail: gchen@jiu.edu.cn
基金资助:
吉林省科技厅高技术发展项目(批准号: 20120310)资助

Preparation and Characterizations of Zn-doped Li_1.13Ni_0.3-_xMn_0.57Zn_xO₂ Cathode Materials for Lithium Ion Batteries^†

WANG Xue, YANG Lili, WANG Chunzhong, CHEN Gang^*(), WEI Yingjin

Key Laboratory of Physics and Technology for Advanced Batteries, Ministry of Education, College of Physics,Jilin University, Changchun 130012, China

Received:2014-10-11 Online:2015-04-10 Published:2015-03-27
Contact: CHEN Gang E-mail:gchen@jiu.edu.cn
Supported by:
† Supported by the Program of High Technology Development of Jilin Province, China(No.20120310).

摘要/Abstract

摘要：

将通过共沉淀法制备的M(OH)₂(M= Mn, Ni)前驱体与ZnO和Li₂CO₃混合, 合成了不同Zn²⁺掺杂量的Li_1.13Ni_0.3-_xMn_0.57Zn_xO₂材料. X射线衍射结果表明, Zn²⁺掺杂提升了材料的层状属性, 降低了Li⁺/Ni²⁺混排程度. 在2.0~4.8 V电压范围内, Zn²⁺掺杂材料表现出更高的可逆比容量, 并具有良好的倍率性能和循环稳定性. 示差扫描量热测试结果显示, Zn²⁺掺杂材料的热安全性能明显优于未掺杂材料. 在所合成的材料中, Li_1.13Ni_0.29Mn_0.57Zn_0.01O₂(Zn²⁺掺杂量x=0.01)具有最高的放电容量、最好的倍率性能和循环稳定性及极佳的热安全性能.

关键词: 富锂层状正极材料, 锌掺杂, 电化学性质, 示差扫描量热分析

Abstract:

Zn-doped Li_1.13Ni_0.3-_xMn_0.57Zn_xO₂ samples were synthesized by co-precipitation method. X-ray diffraction shows that Zn doping decreases the Li⁺/Ni²⁺ cation mixing of the material, increases the structure stability and expands the lattice volume of the material which provides more space for lithium ion intercalation/de-intercalation. Electrochemical experiments show that Zn doping decreases the charge transfer resistance of the electrode, improves the reversibility of lithium intercalation and de-intercalation, thus the electrochemical properties of the material are improved. Especially, the Li_1.13Ni_0.29Mn_0.57Zn_0.01O₂ material with Zn doping of x=0.01 shows the best electrochemical performance with the largest discharge capacity, best rate capability, excellent capacity retention and thermal stability.

Key words: Li-rich layered cathode material, Zinc-doping, Electrochemical property, Thermal stability

中图分类号:

TrendMD:

王雪, 杨丽丽, 王春忠, 陈岗, 魏英进. Zn²⁺掺杂富锂层状正极材料Li_1.13Ni_0.3-_xMn_0.57Zn_xO₂的合成与电化学性质. 高等学校化学学报, 2015, 36(4): 733.

WANG Xue, YANG Lili, WANG Chunzhong, CHEN Gang, WEI Yingjin. Preparation and Characterizations of Zn-doped Li_1.13Ni_0.3-_xMn_0.57Zn_xO₂ Cathode Materials for Lithium Ion Batteries^†. Chem. J. Chinese Universities, 2015, 36(4): 733.

图/表 9

Fig.1 XRD patterns of Zn-doped Li1.13Ni0.3-xMn0.57ZnxO2 a. x=0; b. x=0.01; c. x=0.02.

Table 1 Lattice parameters and intensity ratio of the (003) and (104) reflections of Zn-doped Li1.13Ni0.3-xMn0.57ZnxO2

x	a, b/nm	c/nm	c/a	I₍₀₀₃₎/I₍₁₀₄₎
0	0.28782	1.42421	4.948	1.42
0.01	0.28786	1.43025	4.968	1.47
0.02	0.28852	1.43125	4.960	1.31

Fig.2 SEM images of Zn-doped Li1.13Ni0.3-xMn0.57ZnxO2 (A) x=0; (B) x=0.01; (C) x=0.02.

Fig.3 First charge(a—c)-discharge(a'—c') curves of Zn-doped Li1.13Ni0.3-xMn0.57ZnxO2 a, a'. x=0; b, b'. x=0.01; c, c'. x=0.02.

Fig.4 Cyclic performance of Zn-doped Li1.13Ni0.3-xMn0.57ZnxO2 at a current density of 50 mA/g a. x=0; b. x=0.01; c. x=0.02.

Fig.5 Rate dependent cyclic performance of Zn-doped Li1.13Ni0.3-xMn0.57ZnxO2

Fig.6 Discharge curves of Zn-doped Li1.13Ni0.3-xMn0.57·ZnxO2 at different current densities (A) x=0; (B) x=0.01; (C) x=0.02. Current density/(mA·g-1): a. 50; b. 100; c. 500; d. 1000.

Fig.7 Nquist plots of Zn-doped Li1.13Ni0.3-xMn0.57ZnxO2 a. x=0; b. x=0.01; c. x=0.02.

Fig.8 DSC curves of Zn-doped Li1.13Ni0.3-xMn0.57ZnxO2 a. x=0; b. x=0.01; c. x=0.02.

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Zn²⁺掺杂富锂层状正极材料Li_1.13Ni_0.3-_xMn_0.57Zn_xO₂的合成与电化学性质

Preparation and Characterizations of Zn-doped Li_1.13Ni_0.3-_xMn_0.57Zn_xO₂ Cathode Materials for Lithium Ion Batteries^†

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