喷雾干燥法制备Li1+2xMn0.3+xNi0.3-3xCr0.4O2的结构与电化学性能

doi:10.3724/SP.J.1077.2013.12412

无机材料学报 ›› 2013, Vol. 28 ›› Issue (06): 616-622.DOI: 10.3724/SP.J.1077.2013.12412

喷雾干燥法制备Li_1+2xMn_0.3+xNi_0.3-3xCr_0.4O₂的结构与电化学性能

张茜¹, 刘伟伟¹, 方国清¹, 夏丙波1, 孙洪丹¹, 金子信悟¹, 杨裕生², 郑军伟¹, 李德成¹

(1. 苏州大学江苏省锂离子电池材料重点实验室, 化学电源研究所, 苏州215006; 2. 防化研究院, 北京100083)

收稿日期:2012-07-04 修回日期:2012-08-28 出版日期:2013-06-20 网络出版日期:2013-05-20
作者简介:张茜(1984–), 女, 硕士研究生. E-mail: zhq_suda@126.com
基金资助:
国家自然科学基金(20973200)

Structural and Electrochemical Performances of Li_1+2xMn_0.3+xNi_0.3-3xCr_0.4O₂ Synthesized by Spray-dry Method

ZHANG Qian¹, LIU Wei-Wei¹, FANG Guo-Qing¹, XIA Bing-Bo¹, SUN Hong-Dan¹, KANEKO Shingo¹, YANG Yu-Sheng², ZHENG Jun-Wei¹, LI De-Cheng¹

(1. Key Laboratory of Lithium Battery Materials of Jiangsu Province, Institute of Chemical Power Sources, Soochow University, Suzhou 215006, China; 2. Research Institute of Chemical Defense, Beijing 100083, China)

Received:2012-07-04 Revised:2012-08-28 Published:2013-06-20 Online:2013-05-20
About author:ZHANG Qian. E-mail: zhq_suda@126.com
Supported by:
(National Natural Science Foundation of China (20973200)

摘要/Abstract

摘要： 使用喷雾干燥法制备了Li_1+2xMn_0.3+xNi_0.3-3xCr_0.4O₂(x=1/60、1/30、1/20、1/15、1/12)系列样品, 并借助XRD, SEM, ICP, XPS, IR和Raman等手段对所制备系列样品的结构、价态及电化学性能进行了表征。研究表明, Li_1+2xMn_0.3+xNi_0.3-3xCr_0.4O₂ 系列样品均具有典型的富锂层状固溶体型的晶体结构特征, 且在其XRD图谱中未观测到任何杂相的存在。然而, XPS的数据表明Cr³⁺与Cr⁶⁺共存于各个样品中, 且由于Cr⁶⁺的存在使得样品表现出强烈的吸湿性。Cr⁶⁺可通过水洗处理去除。对于它们的电化学特征而言, 未经水洗处理的样品由于具有强烈的吸湿性, 其电化学性能很差。水洗处理后的系列样品表现出典型的三元富锂层状固溶体的电化学行为, 其首次放电比容量随着样品中Li和Mn含量的增加而增大。样品Li_1.17Mn_0.38Ni_0.05Cr_0.4O₂的首次放电比容量为203 mA h/g, 50次循环后容量保持率为71%。

关键词: 锂离子电池, 正极材料, 喷雾干燥法, 富锂层状固溶体, 电化学性质

Abstract: Lithium-rich layered solid solution materials, Li_1+2xMn_0.3+xNi_0.3-3xCr_0.4O₂(x=1/60, 1/30, 1/20, 1/15, 1/12), were synthesized by spray-drying process. Their crystal structures, element valences and the electrochemical performances were investigated by XRD, XPS, ICP, SEM, TEM and charge-discharge test. All samples have a typical solid solution feature in terms of their structure, and no impurity phase appears in their XRD profiles. Nevertheless, XPS results suggest that Cr³⁺ and Cr⁶⁺ co-exist in all samples. The presence of the Cr⁶⁺ in the as-prepared sample results in a high moisture absorption, which can be removed by water washed treatment. As to the electrochemical properties, the as-prepared samples have bad electrochemical performances due to the high moisture absorption. After washing with water, all samples exhibit solid solution behavior, and their initial specific capacities increase as the increase in the amount of Li and Mn. The discharge capacity of Li_1.17Mn_0.38Ni_0.05Cr_0.4O₂ can reach 203 mAh/g with a capacity retention of 71% after 50 cycles.

Key words: Li-ion battery, cathode materials, spray-dry, lithium-rich layered solid solution, electrochemical property

中图分类号:

TQ174

张茜, 刘伟伟, 方国清, 夏丙波, 孙洪丹, 金子信悟, 杨裕生, 郑军伟, 李德成. 喷雾干燥法制备Li_1+2xMn_0.3+xNi_0.3-3xCr_0.4O₂的结构与电化学性能[J]. 无机材料学报, 2013, 28(06): 616-622.

ZHANG Qian, LIU Wei-Wei, FANG Guo-Qing, XIA Bing-Bo, SUN Hong-Dan, KANEKO Shingo, YANG Yu-Sheng, ZHENG Jun-Wei, LI De-Cheng. Structural and Electrochemical Performances of Li_1+2xMn_0.3+xNi_0.3-3xCr_0.4O₂ Synthesized by Spray-dry Method[J]. Journal of Inorganic Materials, 2013, 28(06): 616-622.

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喷雾干燥法制备Li_1+2xMn_0.3+xNi_0.3-3xCr_0.4O₂的结构与电化学性能

Structural and Electrochemical Performances of Li_1+2xMn_0.3+xNi_0.3-3xCr_0.4O₂ Synthesized by Spray-dry Method

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