湿法合成LiNixCoyMn1-x-yO2的E-pH图绘制及其电性能

doi:10.15541/jim20170192

无机材料学报 ›› 2018, Vol. 33 ›› Issue (3): 320-324.DOI: 10.15541/jim20170192 CSTR: 32189.14.10.15541/jim20170192

所属专题：离子电池材料

湿法合成LiNi_xCo_yMn_1-_x_-_yO₂的E-pH图绘制及其电性能

李玲^{1, 2}, 李运姣^{1, 2}, 徐斌³, 卢伟胜², 苏千叶^{1, 2}, 陈永祥^{1, 2}, 李林¹

1. 中南大学冶金与环境学院, 长沙 410083;
2. 中信大锰矿业有限责任公司, 南宁 530028;
3. 青海快驴高新技术有限公司, 西宁 810000

收稿日期:2017-04-20 修回日期:2017-09-06 出版日期:2018-03-20 网络出版日期:2018-03-12
作者简介:李玲(1989-),女,硕士. E-mail: 928012218@qq.com
基金资助:
广西八桂学者计划(2011A025);广西崇左市重大科技专项([2017]11)

LiNi_xCo_yMn_1-_x_-_yO₂ Cathode Material Synthesized through Construction of E-pH Diagram and Its Electrochemical Performance

LI Ling^{1, 2}, LI Yun-Jiao^{1, 2}, XU Bin³, LU Wei-Sheng², SU Qian-Ye^{1, 2}, CHEN Yong-Xiang^{1, 2}, LI Lin¹

1.School of Metallurgy and Environment, Central South University, Changsha 410083, China;
2. Citic Dameng Mining Industries Limited, Nanning 530028, China;
3. Qinghai Quick Donkey Hi Tech Co., Ltd., Xining 810000, China

Received:2017-04-20 Revised:2017-09-06 Published:2018-03-20 Online:2018-03-12
About author:LI Ling. E-mail: 928012218@qq.com
Supported by:
Glorious Laurel Scholar Program(2011A025);The major Science & Technology ([2017]11)

摘要/Abstract

摘要：

通过热力学计算获得了Li-Ni-Co-Mn-H₂O系中各物质的热力学数据, 从而绘制了25℃和200℃、离子活度为1.00下的Li-Ni-Co-Mn-H₂O系电位-pH图。热力学分析结果表明: 温度为25℃时, 在pH 3~13范围内, 水溶液中未出现LiNi_xCo_yMn_1-_x_-_yO₂稳定区域; 随着温度升高, Li-Ni-Co-Mn-H₂O系中各物质的稳定区域向低pH和低电位方向移动。在温度为200℃, pH为9.7~13.0的水溶液中出现了LiNi_xCo_yMn_1-_x_-_yO₂稳定区域。这说明在一定温度下, 水溶液中合成LiNi_xCo_yMn_1-_x_-_yO₂是可能的, 且提高温度有利于合成反应进行。进一步通过实验验证, 以(Ni_0.5Co_0.2Mn_0.3) (OH)₂前驱体和LiOH·H₂O为原料, 在水溶液中成功获得具有α-NaFeO₂层状结构的锂镍钴锰四元前驱体, 经过热处理后得到循环稳定性良好的LiNi_0.5Co_0.2Mn_0.3O₂正极材料。实验结果证明, 所绘制Li-Ni-Co-Mn-H₂O系E-pH图是可靠的, 且湿法合成LiNi_0.5Co_0.2Mn_0.3O₂正极材料具有良好的循环性能。

关键词: E-pH图, Li-Ni-Co-Mn-H₂O系, 锂离子电池, 正极材料

Abstract:

The thermodynamic data of various species in Li-Ni-Co-Mn-H₂O system is obtained by thermodynamics calculation, and E-pH diagrams for Li-Ni-Co-Mn-H₂O system with activity 1.00 at 25℃ and 200℃ were constructed. From E-pH diagrams, it shows that there is no predominant region of the LiNi_xCo_yMn_1-_x_-_yO₂ composite oxide in pH range of 3~13 at 25℃. However, the stability region of various species expands towards the low pH and low potential zones as the temperature increases. When pH is between 9.7~13.0 at 200℃, synthesis of LiNi_xCo_yMn_1-_x_-_yO₂ via aqueous process is thermodynamically possible, and high temperature is favorable. Experimental results showed that the composite precursor (LNCM) with α-NaFeO₂ structure was successfully prepared in aqueous solution by using (Ni_0.5Co_0.2Mn_0.3)(OH)₂ as precursor and LiOH·H₂O as raw material. LiNi_0.5Co_0.2Mn_0.3O₂cathode materials were then obtained by post heat treatment and following tests exhibited excellent cycling performance. These experimental results are in consistent with the information given in E-pH diagram of the Li-Ni-Co-Mn-H₂O system, and the as-prepared LiNi_0.5Co_0.2Mn_0.3O₂cathode materials show excellent cycling performance.

Key words: E-pH diagram, Li-Ni-Co-Mn-H₂O system, lithium ion battery, cathode material

中图分类号:

TM912

李玲, 李运姣, 徐斌, 卢伟胜, 苏千叶, 陈永祥, 李林. 湿法合成LiNi_xCo_yMn_1-_x_-_yO₂的E-pH图绘制及其电性能[J]. 无机材料学报, 2018, 33(3): 320-324.

LI Ling, LI Yun-Jiao, XU Bin, LU Wei-Sheng, SU Qian-Ye, CHEN Yong-Xiang, LI Lin. LiNi_xCo_yMn_1-_x_-_yO₂ Cathode Material Synthesized through Construction of E-pH Diagram and Its Electrochemical Performance[J]. Journal of Inorganic Materials, 2018, 33(3): 320-324.

图/表 5

图1 Li-Ni-Co-Mn-H2O系在25℃下的E-pH图

Fig. 1 Potential-pH diagrams of Li-Ni-Co-Mn-H2O system at 25℃

图2 Li-Ni-Co-Mn-H2O系在200℃下的E-pH图

Fig. 2 Potential-pH diagrams of Li-Ni-Co-Mn-H2O system at 200℃

图3 锂镍钴锰四元前驱体(a)和LiNi0.5Co0.2Mn0.3O2正极材料(b)的XRD图谱

Fig. 3 XRD patterns of the LNCM oxide precursor (a) and the final product LiNi0.5Co0.2Mn0.3O2 (b)

图4 175℃和250℃下所得LiNi0.5Co0.2Mn0.3O2正极材料的充/放电曲线

Fig. 4 Charge/discharge curves of the LiNi0.5Co0.2Mn0.3O2 cathode materials synthesized at 175℃ and 250℃

图5 175℃和250℃下所得LiNi0.5Co0.2Mn0.3O2正极材料在0.5C下的放电循环曲线和容量保持率曲线

Fig. 5 Discharge cycling performance and capacity retention rate of the LiNi0.5Co0.2Mn0.3O2 cathode materials synthesized at 175℃ and 250℃

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湿法合成LiNi_xCo_yMn_1-_x_-_yO₂的E-pH图绘制及其电性能

LiNi_xCo_yMn_1-_x_-_yO₂ Cathode Material Synthesized through Construction of E-pH Diagram and Its Electrochemical Performance

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